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Application of HAZOP, LOPA and SIL to the

alkylation unit catalyzed with hydrofluoric acid at


Ecopetrol Refinery in Cartagena – Colombia
Stefanny Paola Figueroa Jimenez
Stefany Carolina Lombana Carmona
Ingry Raquel Ruiz De La Cruz

Report to the internship in the Mary Kay O’Connor Process Safety Center
Texas A&M University
1. PROJECT IDENTIFICATION

1.1 GENERAL INFORMATION


Report Type: Partial Final X Report No. _2_ of 2015

Delivery Date of Report


Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid at Ecopetrol
PROJECT TITLE
Refinery in Cartagena – Colombia

Code
Advisor Dr. Sam Mannan

Researchers Stefanny Paola Figueroa Jimenez, Stefany Carolina Lombana Carmona, Ingry Raquel Ruiz De La Cruz

Financial entity Mary Kay O’Connor Process Safety Center- Texas A&M University
Project Start Date January 12 to Jun 30 of 2015
City/ Country College Station Texas – United States

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OUTLINE
3. INTRODUCTION ....................................................................................................................................................................................................6
4. OBJECTIVE ...........................................................................................................................................................................................................7
4.1. General Objective ...........................................................................................................................................................................................7
4.2. Specific Objectives .........................................................................................................................................................................................7
ACHIEVEMENT OF GOALS............................................................................................................................................................................................8
Achievement of general objective .....................................................................................................................................................................................8
Achievement of specific objective - ...................................................................................................................................................................................9
5. BACKGROUND ...................................................................................................................................................................................................14
6. METHODOLOGY .................................................................................................................................................................................................15
7. LITERATURE REVIEW .........................................................................................................................................................................................28
7.1. HF ALKYLATION .........................................................................................................................................................................................28
7.2. HAZARD AND OPERABILITY “HAZOP” .........................................................................................................................................................31
7.3. LAYER OF PROTECTION ANALYSIS “LOPA” ................................................................................................................................................33
7.4. SAFETY INTEGRITY LEVEL “SIL” .................................................................................................................................................................38
8. DEFINITION OF THE PROBLEM...........................................................................................................................................................................40
9. IDENTIFICATION OF IMPORTANT ISSUES ..........................................................................................................................................................41
10. ANALYSIS OF ISSUES.....................................................................................................................................................................................42
10.1. HAZOP ........................................................................................................................................................................................................42
10.2. LOPA & SIL .................................................................................................................................................................................................62
11. CONCLUSIONS ...............................................................................................................................................................................................84
12. FUTURE WORKS ............................................................................................................................................................................................85

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13. SCHEDULE .....................................................................................................................................................................................................86
14. ABBREVIATIONS AND ACRONYMS .................................................................................................................................................................88
15. ACKNOWLEDGMENTS ....................................................................................................................................................................................90
16. REFERENCES.................................................................................................................................................................................................91
17. LIST OF ANNEXES ..........................................................................................................................................................................................94

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LIST OF ANNEX

Annex 1 Application of HAZOP methodology to Selective Hydrogenation Section...............................................................................94


Annex 2 Application of HAZOP methodology to Charge and Drying section ......................................................................................117
Annex 3 Application of HAZOP methodology to Reaction section .....................................................................................................128
Annex 4 Application of HAZOP methodology to Acid Storage section ...............................................................................................134
Annex 5 Application of HAZOP methodology to Cooling Water Tower – TAE- section ......................................................................137
Annex 6 Application of HAZOP methodology to Isostripper section ...................................................................................................139
Annex 7 Application of HAZOP methodology to Depropanizer and HF Stripper section ....................................................................147
Annex 8 Application of HAZOP methodology to Propane Treatment section .....................................................................................159
Annex 9 Application of HAZOP methodology to Debutanization and Alkylate Treatment section ......................................................166
Annex 10 Application of HAZOP methodology to N-Butane Treatment section .................................................................................173
Annex 11 Application of HAZOP methodology to ALKAD Regeneration section ................................................................................184
Annex 12 Application of HAZOP methodology to HF Regeneration section.......................................................................................192
Annex 13 Application of HAZOP methodology to Effluent Treatment section ....................................................................................206
Annex 14 Application of LOPA and SIL methodology to Selective Hydrogenation section .................................................................213
Annex 15 Application of LOPA and SIL methodology to Charge and Drying section .........................................................................214
Annex 16 Application of LOPA and SIL methodology to Reaction section .........................................................................................215
Annex 17 Application of LOPA and SIL methodology to Propane Treatment section.........................................................................216
Annex 18 Application of LOPA and SIL methodology to Debutanization and Alkylate Treatment section ..........................................217
Annex 19 Application of LOPA and SIL methodology to N-Butane Treatment section .......................................................................218
Annex 20 Application of LOPA and SIL methodology to Cooling Water Tower -TAE- section ............................................................219
Annex 21 Application of LOPA and SIL methodology to HF Regeneration section ............................................................................220
Annex 22 Application of LOPA and SIL methodology to Effluent Treatment section ..........................................................................223

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2. SUMMARY

In a refinery, an alkylation unit is the process of producing gasoline range material (alkylate) from olefins such as propylene, butylenes and amylene, and
isobutene. This unit comes after a fluid catalytic cracking unit (FCCU) with the purpose of convert the high molecular weight hydrocarbons into smaller particles
and more volatile compounds. The alkylation process is used to comply with specific requirements through the conversion of octane in a component of high octane
gasoline. Usually the feed stream to the alkylation unit comes from the FCC, but the components react in the presence of a strong catalyst as hydrofluoric acid or
sulfuric acid. Ecopetrol's refinery in Cartagena Colombia use hydrofluoric acid as catalyst. The HF is a very corrosive and toxic inorganic acid. The HF is used in
the production of aluminum and chlorofluorocarbons, and in the glass etching and chemical industries. Acute (short-term) inhalation exposure to gaseous
hydrogen fluoride can cause severe respiratory damage in humans, including severe irritation and pulmonary edema, severe ocular irritation and dermal burns
may occur following eye or skin exposure in humans [US EPA, 2000]; for these reason it is necessary to treat with extreme care, especially in process which water
is used for cleaning process.

Considering the safety of the plant, hydrofluoric acid raises the most issues due to its properties and the effects to humans, flora, and fauna. One of the most
relevant properties of the hydrofluoric acid is the low vapor pressure, so it is easily vaporized if leak occurs in the units. HF can travel significant distance
downward as a dense vapor. Even though a small concentration of hydrofluoric acid is used in the reaction, it is still enough to cause human and environmental
problems. The objective of this research was to decrease the HF hazards applying HAZOP, LOPA and SIL methodologies. This study is based on the assumption
that the process always operating inside intended design, thus the risks and operability problems are unlikely to occur. The methodology used is to guide words to
identify deviations in the process including the design of the HF alkylation unit.

We evaluated potentially hazardous scenarios and generated recommendations to mitigate these consequences or improve operational capability. Hazardous
scenarios and any associated recommendations were categorized during the research was: safety, environmental and financial; each topic was also risk ranked to
assess the strength of existing safeguards. These causes were identified including human error, equipment failure and external events. Severity of deviations was
evaluated without any protection or safeguards.

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HF alkylation plant has 13 units which were evaluated and studied and we obtained1092 possible deviations or causes and recommendations in the HAZOP study.
24 of these scenarios are considered significant and high risk and were analyzed in detailed analysis applying LOPA and SIL methodologies. These analysis
providing layers protections to mitigate the hazardous scenarios founded in the HAZOP study, then is necessary identify which of these layer protection are
considered independent protection layer and assign a value of PFD (probability of failure on demand) of each safeguards that was used to get the SIL range.

The detailed issues about the safety study in the unit is provided in this report to show a summary with the recommendations and conclusions obtained through the
study generating a worksheet which has the possible causes, safeguards and risk ranking were evaluated.

3. INTRODUCTION

The petroleum refining industry has always accepted the potential for hazard created by the alkylation units due to uses two systems, either Sulfuric acid or
Hydrofluoric acid, both are considered hazardous substances and has been consistently secured, by the mechanical, metallurgical specifications and operational
practice utilized in the design, construction and the operation of these units which it has achieved a high level of security. [Ecopetrol, 2014]

In this study is evaluated the alkylation process catalyzed with hydrofluoric acid. The alkylation unit performs an important role due to that it produces a high-value
alkylate, which is used as a gasoline blending component. Consequently, refineries operating HF alkylation units are under increasing pressure to maximize the
safety of the unit, product quality, the operational procedures and decreasing of the environmental impact. The efficient operation of alkylation units with HF is a
difficult task and subject to the most testing of operating regimes. This is due to a number of industry-specific constraints and operating issues that stretch the
processing capability of the plant. [Simpson, et al. 2007]

Ecopetrol´s Cartagena Colombia refining has an alkylation plant catalyzed with HF which represents a potential hazards. This kind of process required a detailed
study about the safety and the best operability practices; HAZOP methodology is used to identify major process hazards or operability issues related to the
process design, the most hazardous scenarios include the release of hazardous materials and/or energy like hydrofluoric acid.

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The aim of this research is analyze the different incidents present in the unit which may impact on health and public safety, worker safety in the workplace,
economic losses, the environment and the company’s reputation. It is required a SIL/ LOPA study since these serves to assess the adequacy of the Safety
Protection Layers (SPLs) or Safeguards that are in place to mitigate events hazardous relating with the process hazards, identify those SPLs or Safeguards that
they are not sufficient to reduce this scenario and to suggest reasonable recommendations which can hazard generates a residual risk that needs further risk
reduction. This is done by defining the tolerable frequency (TF) [Binghman, et al. 2004]. The TF of the process deviation is a number which is derived from the
level of the risk identified from the HAZOP study and we can get it in the risk matrix that Ecopetrol Works. It indicates the period of occurrence, in terms of years, of
the process deviation. The TF values are showing it in the table 2.

4. OBJECTIVE

4.1. General Objective


To develop a study to identify and review best safety practices for proper operation and performance of the alkylation unit catalyzed with hydrofluoric
acid (HF) at the Ecopetrol Refinery in Cartagena-Colombia applying HAZOP, LOPA and SIL methodologies.

4.2. Specific Objectives


 Make a literature review to get information about the process operating and general information of the alkylation unit catalyzed with

hydrofluoric acid.

 Develop a detailed study concerning the alkylation process, how it works and find the principals variables of the process.

 Identify the operating principles of the alkylation unit to select the corresponding nodes which they will be evaluated in detail in each

section of the unit.

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 Generate an Excel document that contain the recommendations and analysis obtained from the investigation divided by the nodes

selected and principals variables

 Identify the criteria and process safety mechanisms used in the alkylation plant with hydrofluoric acid and compare with the results

obtained to ensure that they are optimal for its operation.

 Publish articles in index journals from the results obtained in the investigation

ACHIEVEMENT OF GOALS

Achievement of general objective


GENERAL To develop a study to identify and review best safety practices for proper operation and
performance of the alkylation unit catalyzed with hydrofluoric acid (HF) at the Ecopetrol % of compliance: 100%
OBJECTIVE:
Refinery in Cartagena-Colombia using HAZOP, LOPA and SIL methodologies.
ANNEX, DEVELOPMENT SUPPORT AND
RESULTS DIFFICULTIES OBSERVATIONS
RESULTS

Study of the HAZOP, LOPA and SIL Worksheets that contain The detailed study and information Is important before to start a
methodologies the recommendations and final Project report to about the process a part of this the study about this kind of the
HAZOP, LOPA and Mary Kay O’Connor Process Safety Center and personal training in the safety process plant take care with the
SIL to generate the San Buenaventura Committee. topic. selected nodes and the
best safety practices principals variables that affect
in the HF alkylation the process directly.
Unit

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Achievement of specific objective -

Make a literature review to get information about the process operating


SPECIFIC OBJECTIVE: 1 and general information of the alkylation unit catalyzed with hydrofluoric % of compliance: 100%
acid

PRODUCT ANNEX, DEVELOPMENT


RESULT OBSERVATIONS
(if applicable) SUPPORT AND RESULTS

Resolve doubt about the Report submitted to Report that contain part of the When realized this kind of review is
process and personal training in Universidad de San literature review used in the project. recommendable get information
alkylation units catalyzed with Buenaventura Cartagena and about similar plants and process
hydrofluoric acid and process personal training. safety methodologies.
safety methodologies.

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Develop a detailed study concerning the alkylation process, how it
SPECIFIC OBJECTIVE: 2 % of compliance: 100%
works and find the principals variables of the process.

PRODUCT ANNEX, DEVELOPMENT


RESULT OBSERVATIONS
(if applicable) SUPPORT AND RESULTS

Study of the process with the 3 Report submitted to Process safety management Take different curses about process
methodologies selected which Universidad de San course to help us to get the safety and resolve any doubt about
are: HAZOP, LOPA and SIL Buenaventura Cartagena and necessary information to select the the procedures in the methodologies
personal training. best safety methodologies. selected.

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Identify the operating principles of the alkylation unit to select the
SPECIFIC OBJECTIVE: 3 corresponding nodes which they will be evaluated in detail in each % of compliance: 100%
section of the unit.

PRODUCT ANNEX, DEVELOPMENT


RESULT OBSERVATIONS
(if applicable) SUPPORT AND RESULTS

The nodes that help us to divide HAZOP, LOPA and SIL studies Worksheets and reports that Take care when choosing the nodes
each section of the unit and development at Excel contain the selected nodes and the due to them could do more ease or
develop a detailed study of documents. recommendations generated from difficult our study.
them. them attachment at this report

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Generate an Excel document that contain the recommendations and
SPECIFIC OBJECTIVE: 4 analysis obtained from the investigation divided by the nodes selected % of compliance: 100%
and principals variables

PRODUCT ANNEX, DEVELOPMENT


RESULT OBSERVATIONS
(if applicable) SUPPORT AND RESULTS

Recommendations from the Excel documents when the Excel with worksheets that contain Did a study about the general
detailed study to generate the person can get the detailed the selected nodes, principal worksheet used in this methodologies
conclusions necessary to the study and the recommendations variables and possible scenarios (HAZOP, LOPA and SIL).
project. that we got from each possible that were used to get the
scenario of the process. recommendations about the best
safety practices in the process
attachment at this report.

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Identify the criteria and process safety mechanisms used in the alkylation
SPECIFIC OBJECTIVE: 5 plant with hydrofluoric acid and compare with the results obtained to % of compliance: 100%
ensure that they are optimal for its operation.

PRODUCT ANNEX, DEVELOPMENT


RESULT OBSERVATIONS
(if applicable) SUPPORT AND RESULTS

A report that contain the This document and other report Reports to the Mary Kay O’Connor Did a specific study about the
conclusions and delivered to Mary Kay O’Connor Process Safety Center and San methodologies used by Ecopetrol
recommendations generates process safety center which are Buenaventura University Committee Refinery and the methodologies used
during the investigation has some conclusions and to show all information generated for international refineries.
recommendations about the best from the project and the results
safety practices in the HF
alkylation unit embodied at
recommendations generated from
HAZOP, LOPA and SIL analysis

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Publish articles in index journals from the results obtained in the
SPECIFIC OBJECTIVE: 6 % of compliance: 50%
investigation

PRODUCT ANNEX, DEVELOPMENT


RESULT OBSERVATIONS
(if applicable) SUPPORT AND RESULTS

Publication of articles from the Developing In this moment we are developing the
results obtained of the article to send it to some scientific
investigations journals

5. BACKGROUND

The HAZOP, LOPA and SIL studies are excellent tools to analyze and provide recommendations and good practices for prevent accidents and risks in a work
place or plant. The scope of this study included all process equipment, piping, and instrumentation for the systems defined using the Process Flow Diagrams
(PFDs), Piping & Instrument Diagrams (P&lDs) and operating under normal steady state conditions or in response to a process variation.

The hazard scenarios were categorized during the research as being:

• Safety (S): including catastrophic events such as explosions or fires, other personnel injury events, and off-site consequences.
• Environmental (E): including any legal or company violation.

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• Financial (F): including equipment damage or operability issues.

Each scenario was also risk ranked to assess the strength of existing safeguards. When employed properly, a risk ranking system helps to identify gaps in
process safety.

6. METHODOLOGY

The methodology used to elaborate HAZOP, LOPA and SIL study are described below:

The P&IDs were divided into manageable sections called nodes. These systems were systematically analyzed. The HF alkylation unit study contains forty eight
(48) nodes. The details of these nodes are show in the Worksheet in a excel document which are attached with this documents.

HAZOP analysis is a process hazard analysis method which has been widely used in chemical process industries, especially in some complex process plants.
Processes, human operations, many pieces of equipment, a mass of material, a number of instruments, several control systems, safety and environment, etc.,
interweave to form a complex process plant. Human operations always play a tremendous role in running the plant. In an analysis process, P&ID of the complex
process plant should be examined by a multi-disciplinary team of experts systematically, and all conceivable deviations far from design intentions in the plant can
be identified and all the possible abnormal causes and the adverse consequences of these deviations can be determined.

The considerations of the experts are provided in the following two aspects: 1) determining whether a given operation or activity has the potential to give rise to a
hazardous situation, 2) determining the range of hazardous events that the operation or activity could present.

In the process we found some of the possible causes that can divert the conditions of the process, which are::

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 Failure in the equipment, instrumentation, or in the piping. Equipment failures were not considered at a specific level. For example, the form that the
equipment fails including the instruments control that this has.
 Human error such as performing a wrong operation, failing to perform a required operation, misdiagnosing an operating problem, performing an operation
at the wrong time, mal-operation of equipment, and administrative failure in which a faulty system causes a hazard
 External events such as loss of utilities to the process unit (electrical power, steam, cooling water, instrument air), climatic conditions (e.g. solar heating),
or external fire
 Long-term processes which, if ignored, could cause potential hazardous deviations. Examples fouling in exchangers, corrosion/erosion possibilities. If this
not is ensured could represent a hazardous for the unit
 Previous incidents

When we based if occur a deviation from equipment and process design was necessary follow these steps to identify possible consequences and generate
recommendations to mitigate the deviations.

1. First consider that the consequences don't have any safeguards, that is for studying the worst case scenario and generate the correctly
recommendations that can avoid that this consequence occur
2. Take the most severity consequence. In some cases, that might be considering the most consequence and lower likelihood, while in other cases it might
be most likely but less consequential outcome.
3. Consequences shall be identified according to Safety, Environmental, and Financial.

We document the safeguards for prevention and/or mitigation of the consequences. The unit has a system which is defined between the P&IDs, PFD and general
information about it, that for know how to prevent or mitigate the hazard from the recommendations that was found:

1. Safeguards (engineering and administrative controls)


2. Typical safeguards that prevent or minimize consequences and likelihoods which include:

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• Process design
• Control (basic process control systems, process alarms, operating procedures, Operator intervention)
• Prevention (safety critical process alarms, safety instrumented systems)

Each cause-consequence combination which constitutes a hazard scenario was ranked, wherever possible, by us according to its estimated severity and likelihood
of occurrence. Most causes have multiple consequences where each consequence has a likelihood of occurrence.

Specifically ranking the likelihood of different consequences recognizes that a hazardous scenario may be interrupted or mitigated by shutdown instrumentation,
operator intervention, or emergency response before the hazard can fully develop.

Thus, while the severity level of consequences can increase dramatically as each consequence is considered, the likelihood of occurrence may decrease
significantly.

The company uses 5 levels severities which were assigned to each consequence, assuming that any safeguards within the process unit did not respond as
designed. However, the likelihoods were assigned assuming that safeguards function fully and work as designed. The definitions for the severity levels used in the
study are given in Table 1, and the definitions for the likelihood levels are given in Table 2.

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Table 1. Severity code desviations

Table 2. Likelihood Definitions

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The severity and likelihood are considered jointly using a Risk Ranking Matrix to determine appropriate prioritization of the scenarios and associated
recommendations as shown in Table 3 below.

Table 3. Risk Matrix

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The risk ranking has a meaning depending of the color which will show in the table 4.

Table 4. Risk Ranking Definitions

Layers of protection analysis (LOPA) is a powerful analytical tool for assessing the adequacy of protection layers used to mitigate process risk. LOPA builds upon
well-known process hazards analysis techniques, applying semi-quantitative measures to the evaluation of the frequency of potential incidents and the probability
of failure of the protection layers.

However, risks of incidents caused by reactive chemicals have not been well addressed due partly to sparse failure frequency data. In this paper, the semi-
quantitative layer of protection analysis (LOPA) approach is used to estimate reactive chemical risk, and the probabilities or frequencies of failure scenarios are
addressed. Using LOPA, reactive risks can be evaluated with respect to predefined criteria, and the effectiveness of risk reduction measures can be assessed

In other words, the concept of layers of protection is illustrated in Figure 1. The combined effects of the protection layers and the consequences are compared
against some risk tolerance criteria that for Ecopetrol S.A. is 1x10^-8/years.

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Figure 1. Layers of protection to lower the frequency of a specific accident

Community
Community Emergency
Emergency Response
Response

Plant Emergency
Plant EmergencyResponse
Response

Post-Response Physical Protection

Physicalprotection
Physical protection (Relief
(ReliefDevices)
Devices)

Safety Instrumented Functions

Critical Alarms and Human

Basic Process Control Sytems

Process Design

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The major steps for LOPA study include:

 Extract the possible causes from HAZOP study which are categorized in High and Significant risk.
 Estimate the potential risk (severity, frequency, exposition factor …) of event no mitigated.
 Define tolerable risk (tolerable maximum frequency of mitigated event).
 Analyze the layers protections and establish the independent protection layers and assign a risk factor reduction.
 Estimate the overall consequence frequency multiplying the value of PFD of each safeguards and frequency to comparison with acceptable risk
criteria that in this case the value is 1x10^-8/years.
 Evaluate and repeat the process if is necessary. If the value of the overall consequence is higher than the acceptable risk criteria is necessary reduce
it suggesting others independent protection layer (IPL) and calculate a new overall consequence until the value is lower or equal to the acceptable
risk criteria.

All these steps are repeated for the scenarios categorized in high and significant risk.

Layers protection

The safeguards identified during the HAZOP study, then establish which of these safeguards are consider independent protection layers (IPLs):

 Process control system


 Alarms and operator actions
 Active barriers:
- Security events
- Sprinklers, dikes, water curtains….
 It’s possible that all of these layers not be independent protection layers.

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Frequency

Performing a LOPA study we determined the failure frequency of the initiating event from table 2 worked in the company, this table it was assigned due to value
obtained in the HAZOP study, so, from this value it was related in the table 2 and in this form assigned the frequency of this possible cause.

The failure frequencies for the common initiating events of an accident scenario are show in table 5.

Table 5. Typical Frequency Values Assigned to Initiating Eventsa

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A part of these PFDs it was necessary included PFDs for passive IPLs that are show in table 6 and PFDs for active IPLs and Human Actions that are show in table
7.

Table 6. PFDs for Passive IPLs

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Table 7. PFDs for Active IPLs and Human Factors

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From these values it was possible obtain the PFDs of each safeguards and with the frequency we could calculate the overall consequence frequency and compare
with the acceptable risk criteria to know if the deviation needed other IPL to mitigate the hazardous.

The deviations that not exceeded the value assigned for the refinery it was necessary to generate more recommendations or suggest some safeguards to mitigate
the risk.

The last method that we used is Safety integrity level (SIL), which is verification plays a critical role in reliability assessment of safety related systems. In the
industry they ask, to what extent can a process be expected to perform safely? And, in the event of a failure, to what extent can the process be expected to fail
safely? These questions are answered through the assignment of a target Safety Integrity Level (SIL). SILs are measures of the safety risk of a given process.

Safety Integrity Level is a way to indicate the tolerable failure rate of a particular safety function. Standards require the assignment of a target SIL for any new or
retrofitted SIF within the SIS. The assignment of the target SIL is a decision requiring the extension of the Hazards Analysis. The SIL assignment is based on the
amount of risk reduction that is necessary to maintain the risk at an acceptable level. All of the SIS design, operation and maintenance choices must then be
verified against the target SIL. This ensures that the SIS can mitigate the assigned process risk.

Historically, safety thinking categorized a process as being either safe or unsafe. For the new standards, however, safety isn’t considered a binary attribute; rather,
it is stratified into four discrete levels of safety. Each level represents an order of magnitude of risk reduction. The higher the SIL level, the greater the impact of a
failure and the lower the failure rate that is acceptable. In the table 8 shown these level which are accepted in the chemical process industry.

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Table 8. SIL values
SIL Availability PFDavg Risk Reduction Qualitative Consequences
4 >99.99% 10-5 to <10-4 100,000 to 10,000 Potential for fatalities in the
community
3 99.9% 10-4 to <10-3 10,000 to 1,000 Potential for multiple on-site
fatalities
2 99 to 99.9% 10-3 to <10-2 1,000 to 100 Potential for major on-site injuries
1 90 to 99% 10-2 to <10-1 100 to 10 Potential for minor on-site injuries

This value is obtained from equation 1 when the deviation no exceeded the acceptable risk criteria; if this exceeded this value that is mean the process has the
enough safeguards to mitigate the deviation.

In this case the maximum value for SIL that we obtained was SIL 1 and SIL2

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7. LITERATURE REVIEW

7.1. HF ALKYLATION

ALKYLATION CURRENT EVENTS, Pam Pryor, 2001

<http://www2.dupont.com/Clean_Technologies/es_MX/assets/downloads/AlkyCurrentEvents2001.pdf>

Alkylation’s importance to refiners continues to grow as alkylate has been termed “liquid gold” for reformulated gasoline. Although well established in the United
States, growth in alkylation capacity has continued through the last decade as U.S. refiners have revamped and expanded existing units, replaced obsolete units,
and in a few cases, added new grassroots units.

Alkylation capacity outside the United States continues to grow as well. Increasing conversion capacity plus increasing demand for gasoline in many areas of the
world has led to the installation of new grassroots alkylation units. Coupled with the need for more gasoline is the need for cleaner gasoline. We see alkylate filling
those needs.

ISOBUTANE ALKYLATION: RECENT DEVELOPMENTS AND FUTURE PERSPECTIVES, Sven Ivar Hommeltoft, 2001

<http://www.sciencedirect.com/science/article/pii/S0926860X01008171>

Alkylation serves to dispose of the C3–C4 cut from the FCC unit by converting much of this cut into alkylate, which is a valuable blending component for the
gasoline pool. The alkylate contains no olefins or aromatics but consists exclusively of isoalkanes. It has a low vapor pressure and a high octane number.There is
little doubt that as long as cars are operatedon high-octane gasoline, isobutane alkylate willcontinue to be a desirable blending component. The trend in motor
gasoline formulation as forced by the legislative requirements has been and will probably continue to be to lower the content of olefins and aromatics and
impurities such as sulfur and nitrogen compounds in order to make the fuel more environmentally friendly.

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HYDROFLUORIC ACID ALKYLATION, ABB and ConocoPhillips develop a critical new process analysis tool, Michael B. Simpson, Michael
Kester, 2007

<http://www09.abb.com/global/scot/scot271.nsf/veritydisplay/1b9c3c80511554ef8325734b004198cf/$file/22-26%203M774_ENG72dpi.pdf>

The HF alkylation unit (HFU) remains of key importance to this day. It plays a critical role in providing one of the most important feeds to the final pro duct gasoline
blending pool. Its significancehas grown side by side withthe increasing number of fluid catalyticcracking (FCC) units in refineries.The FCC adds value to the heavy
endof crude distillation by catalytically cracking heavy feeds into lighter products such as light cycle oil and FCC gasoline, which can be used either directly or after
hydrotreating in final product blending operations. The downside of this process is that light olefins, typically butene and propene, are also produced in FCC
operations. These are essentially worthless as feedstock. Similarly, in any crude distillation process an excess of light end products such as butane tend to be
produced that are of limited use. N-butane can easily be converted to iso-butane, and in this form it joins the FCC c3 or c4 olefins (butene or propene) as the
combined feeds to the HF alkylation unit.

ABB–ConocoPhillips solution for HFU reactor optimization offers ABB multivariable control technology underpinned by a unique capability for rapid online
characterization of HF acid, recycle iC4, olefin/iC4 makeup feeds and alkylate. Thesolution delivers the following significantoperating improvements to HFalkylation
reactors:

 Feed rates, alkylate yield, and alkylate octane are maximized to an economic optimum, subject to operating constraints
 Isobutane:olefin (I:O) ratio and energy consumption can be reduced while meeting alkylate quality and yield targets with minimum acid consumption.
 Isobutane makeup rate can be optimized while respecting iC4 inventory constraints

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FUNDAMENTALS OF PETROLEUM REFINING, Chapter 10 – Alkylation, Mohamed A. Fahim, Taher A. Alsahhaf, AmalElkilani, 2010

<http://www.sciencedirect.com/science/article/pii/B9780444527851000103>

This chapter describes alkylation, a process of producing gasoline range material (alkylates) from olefins such as propylene, butylenes and amylene, and
isobutane. Butylene is the most widely used olefin because of the high quality of the alkylate produced. The current trend toward elimination of methyl tertiary butyl
ether has resulted in increased attention to alkylation technology. In alkylation, refinery gases produced from different units are collected and sent to the gas plant.
Olefins and isobutanes are separated and used as a feed to the alkylation plant. Olefins are sent to the polymerization unit. Both alkylation and polymerization
units produce gasoline, which can be sent to the gasoline pool.

The alkylation process consists of running the hydrocarbons in liquid form (enough pressure is used to ensure that) and at low temperature and with a high
isobutane (iC4) to olefin ratio. The reaction products are sent to an acid settler where the acid is recycled back to the reactor. Products are then separated into
gaseous LPG propane and n-butane and the desired product of alkylate.

A RISK TOO GREAT: HYDROFLUORIC ACID IN U.S. REFINERIES, Gary Beevers, Teddy Bender, Kristin Bradley-Bul, et al. 2013

<http://www.usw.org/workplaces/oil/A-Risk-Too-Great.pdf>

Fifty U.S. oil refineries use large volumes of highly concentrated hydrofluoric acid (HF) as chemical catalysts in a process called alkylation. Alkylation creates
additives that boost the octane of gasoline. On average, these 50 refineries each store 212,000 pounds of HF. If released in the atmosphere, HF rapidly forms
dense vapor clouds that hover near land and can travel great distances. Like other powerful acids, HF can cause deep severe burns and damage the eyes, skin,
nose, throat and respiratory system. But the fluoride ion is also poisonous. Entering the body through a burn or by the lungs, it can cause internal damage
throughout the body. At high enough exposures, HF can kill. The Occupational Safety and Health Administration (OSHA) and the Environmental Protection Agency
(EPA) regulate HF as highly toxic.

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7.2. HAZARD AND OPERABILITY “HAZOP”

HAZARD AND OPERABILITY (HAZOP) ANALYSIS. A LITERATURE REVIEW, JordiDunjó, VasilisFthenakis, Juan A. Vílchez, JosepArnaldos,
2009

<http://www.sciencedirect.com/science/article/pii/S0304389409013727 >

Hazard and operability (HAZOP) methodology is a Process Hazard Analysis (PHA) technique used worldwide for studying not only the hazards of a system, but
also its operability problems, by exploring the effects of any deviations from design conditions.

Our paper is the first HAZOP review intended to gather HAZOP-related literature from books, guidelines, standards, major journals, and conference proceedings,
with the purpose of classifying the research conducted over the years and define the HAZOP state-of-the-art.

A NEW INTELLIGENT ASSISTANT SYSTEM FOR HAZOP ANALYSIS OF COMPLEX PROCESS PLANT, Feng Wang, , JinjiGao, Huaqing Wang,
2012

<http://www.sciencedirect.com/science/article/pii/S0950423012000228>

HAZOP analysis is a process hazard analysis method which has been widely used in chemical process industries, especially in some complex process plants.
Processes, human operations, many pieces of equipment, a mass of material, a number of instruments, several control systems, safety and environment, etc.,
interweave to form a complex process plant. Human operations always play a tremendous role in running the plant. In an analysis process, P&ID of the complex
process plant should be examined by a multi-disciplinary team of experts systematically, and all conceivable deviations far from design intentions in the plant can
be identified and all the possible abnormal causes and the adverse consequences of these deviations can be determined.

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The considerations of the experts are provided in the following four aspects: 1) determining whether a given operation or activity has the potential to give rise to a
hazardous situation, 2) determining the range of hazardous events that the operation or activity could present.

HAZOP STUDY TRAINING FROM THE 1970S TO TODAY, Brian J. Tyler, 2012

<http://www.sciencedirect.com/science/article/pii/S0957582012000869>

The role of Trevor Kletz in the development of several safety methods is well known and widely acknowledged. These methods include HAZOP study, HAZAN and
inherent safety. Indeed, HAZOP study has been adopted worldwide1 to the point where it is probably the most widely used hazard study method in the process
industry. Less well known is the influence of Kletz on the training methods used for HAZOP study. This paper records his early contributions and continued
influence as well as describing some important developments during the last 40 years. It is based on my experience of organising, since 1978, over 50 public
courses on HAZOP study for the IChemE, over 100 in-company courses for 50 different companies and, most recently, creating an e-learning course in HAZOP
study which has been made available through the IChemE.

PROCESS SAFETY DATA MANAGEMENT PROGRAM BASED ON HAZOP ANALYSIS AND ITS APPLICATION TO AN ETHYLENE
OXIDE/ETHYLENE GLYCOL PLANT, FengWanga, Yankun Zhao, Ou Yang, JingboCai, Mei Deng, 2013

<http://www.sciencedirect.com/science/article/pii/S0950423013001757>

HAZOP analysis is a process hazard analysis method that has been widely applied both within and outside the chemical processing industries. This paper
presents a design method for a process safety data management program for petrochemical plants based on HAZOP analysis and demonstrates the steps of
application involved in building a process safety data management system for an ethylene oxide/ethylene glycol production plant. Firstly, the production data files
and relevant documents of the plants should be classified and stored in the program database as reference documents and treatment schemes for coping with
abnormal situations should be collected and summarized as guidance documents. Secondly, the HAZOP analysis method is employed to identify all the dangerous
deviations possibly existing in the production process of the ethylene oxide/ethylene glycol plant. Then, the relationships among the deviations, the reference
documents and the guidance documents should be considered and evaluated.

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Finally, each dangerous deviation will be given a corresponding reference document and guidance document. The reference documents and guidance documents
stored in the expert system can be utilized to help operators solve the corresponding technical problems and cope with abnormal situations. The process safety
data management program will contribute to the identification, analysis and resolution of operation problems. When an abnormal situation occurs, according to the
deviations exhibited in the system, the necessary reference documents and guidance documents will be quickly consulted by the operators, and an appropriate
decision will be made to address the abnormal situation. Therefore, by using the process safety data management program, plant security and human safety in the
petrochemical industries will be improved.

7.3. LAYER OF PROTECTION ANALYSIS “LOPA”

SCENARIO IDENTIFICATION AND EVALUATION FOR LAYERS OF PROTECTION ANALYSIS, Kenneth First, 2000

<http://www.sciencedirect.com/science/article/pii/S095042301000094X>

The identification and screening of scenarios has been identified as a source of variation in Layers of Protection Analysis (LOPA). Often the experience of the
analyst is a significant factor in determining what scenarios are evaluated and the worst credible consequences. This paper presents a simplified chemical process
risk analysis that is effective in providing a semi-quantitative measure of consequence that may include human harm and is independent of the analyst. This
process may be used in evaluation of Management of Change, inherently safer design decisions for capital projects and LOPA re-validation.

Conditional and relational logic may be captured with the use of simple spreadsheets to further improve overall efficiency. For example, this method minimizes the
overall time required for scenario development and re-validation relative to Hazard and Operability studies (HAZOP). The technique simplifies established models
used by engineers engaged in the operation or design of a chemical manufacturing facility without special software or training. The results of this technique are
realistic and may be directly compared with corporate or regulatory guidelines for risk of fatality or injury. At each step in the risk analysis process, more detailed or
sophisticated methods may be used to refine the technique. Furthermore, results from any step may indicate that the hazard from a specific scenario case is not
sufficient to continue with subsequent analysis steps.

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INTRODUCTION TO LAYERS OF PROTECTION ANALYSIS, Angela E. Summers, 2003

<http://www.sciencedirect.com/science/article/pii/S0304389403002425>

Layers of protection analysis (LOPA) is a powerful analytical tool for assessing the adequacy of protection layers used to mitigate process risk. LOPA builds upon
well-known process hazards analysis techniques, applying semi-quantitative measures to the evaluation of the frequency ofpotential incidents and the probability
of failure of the protection layers. This paper will provide anoverview of the LOPA process, highlighting the key considerations.

LAYER OF PROTECTION ANALYSIS FOR REACTIVE CHEMICAL RISK ASSESSMENT, Chunyang Wei, William J. Rogers and M. Sam Mannan,
2008

<http://www.sciencedirect.com/science/article/pii/S0304389408009898>

Reactive chemical hazards have been a significant concern for the chemical process industries (CPI). Without sufficient control and mitigation of chemical reaction
hazards, reactive incidents have led to severe consequences, such as release of flammable and toxic materials, fires and explosions, and threats to human lives,
properties, and the environment. Consequence of reactive hazards can bewell understood through calorimetric testing and computational techniques.

However, risks of incidents caused by reactive chemicals have not been well addressed due partly to sparse failure frequency data. In this paper, the semi-
quantitative layer of protection analysis (LOPA) approach is used to estimate reactive chemical risk, and the probabilities or frequencies of failure scenarios are
addressed. Using LOPA, reactive risks can be evaluated with respect to predefined criteria, and the effectiveness of risk reduction measures can be assessed.
The hydroxylamine (HA) production system is employed as a case study to demonstrate the application of LOPA to reactive chemical risk assessment

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RISK ASSESSMENT OF LNG IMPORTATION TERMINALS USING THE: BAYESIAN–LOPA METHODOLOGY, GeunWoong Yun, William J. Rogers
and M. Sam Mannan, 2009

<http://www.sciencedirect.com/science/article/pii/S0950423008001344>

In order to meet the fast growing LNG (Liquefied Natural Gas) demand, many LNG importation terminals are now in operation. Therefore, it is important to estimate
potential risks of LNG terminals using LOPA (Layer of Protection Analysis), which can provide quantified results with less time and effort than other methods. For
LOPA applications, failure data are essential to compute risk frequencies. However, available failure data from the LNG industry are sparse and often statistically
unreliable. Therefore, Bayesian estimation, which can update generic failure data with plant-specific failure data, was used to compensate for insufficient LNG
system failure data. This paper shows the need for the Bayesian–LOPA methodology, how to develop the method, and a case study to demonstrate application of
the method. Finally, this paper proposes that the Bayesian–LOPA method is a powerful tool for risk assessment of not only the LNG industry but also in other
industries, such as petrochemical, nuclear, and aerospace.

ExSys-LOPA FOR THE CHEMICAL PROCESS INDUSTRY, Adam S. Markowski and M. Sam Mannan, 2010

<http://www.sciencedirect.com/science/article/pii/S0950423010000525>

The chemical process industries are characterized by the use, processing, and storage of large amounts of dangerous chemical substances and/or energy. Among
different missions of chemical plants there are two very important ones, which: 1. provide a safe work environment, 2. fully protect the environment. These
important missions can be achieved only by design of adequate safeguards for identified process hazards.

Layer of Protection Analysis (LOPA) can successfully answer this question. This technique is a simplified process of quantitative risk assessment, using the order
of magnitude categories for initiating cause frequency, consequence severity, and the likelihood of failure of independent protection layers to analyze and assess
the risk of particular accident scenarios. LOPA requires application of qualitative hazard evaluation methods to identify accident scenarios, including initiating
causes and appropriate safeguards. This can be well fulfilled, e.g., by HAZOP Studies or What-If Analysis.

35
However, those techniques require extensive experience, efforts by teams of experts as well as significant time commitments, especially for complex chemical
process units. In order to simplify that process, this paper presents another strategy that is a combination of an expert system for accident scenario identification
with subsequent application of LOPA. The concept is called ExSys-LOPA, which employs, prepared in advance, values from engineering databases for
identification of loss events specific to the selected target process and subsequently an accident scenario barrier model developed as an input for LOPA.

Such consistent rulesfor the identification of accident scenarios to be analyzed can facilitate and expedite the analysis andthereby incorporate many more
scenarios and analyze those for adequacy of the safeguards. An associated computer program is under development. The proposed technique supports and
extends the Layer of Protection Analysis application, especially for safety assurance assessment of risk-based determination for the process industries. A case
study concerning HF alkylation plant illustrates the proposed method.

A FORMULATION TO OPTIMIZE THE RISK REDUCTION PROCESS BASED ON LOPA, ClementinaRamírez-Marengo, Julio de Lira-Flores,
AntiocoLópez-Molina, RichartVázquez-Román, Victor Carreto-Vázquez and M. Sam Mannan, 2013

<http://www.sciencedirect.com/science/article/pii/S0950423012001052>

LOPA is a semi-quantitative methodology used in risk analysis. LOPA assesses the scenarios such as loss of containment, which can lead into major accidents,
and it also proposes a series of hierarchically organized protective layers. Protective layers are placed to lower the frequency of undesired consequences. The
methodology typically uses order of magnitude to express the initial event frequency, the probability of failure on demand of the independent protection layers and
the magnitude of the consequence.

LOPA methodology typically builds on the information developed during a qualitative hazard evaluation. Then, layers of protection are intended to independently
comply with three main functions: Prevention, protection and mitigation. To be considered as independent protection layers (IPL’s), safeguards need to satisfy
some characteristics: independence, specificity, dependability and auditability (Summers, 2003).

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LAYER OF PROTECTION ANALYSIS E QUANTIFYING HUMAN PERFORMANCE IN INITIATING EVENTS AND INDEPENDENT PROTECTION
LAYERS, Philip M. Myers, 2013

<http://www.sciencedirect.com/science/article/pii/S095042301200099X>

Layer of Protection Analysis (LOPA) is a highly valued, semiquantitative risk methodology embraced by the process industries and in widespread use. LOPA uses
a relatively simple, scenariobased approach that can effectively address many risk related issues, providing a timely and cost-effective tool to conduct engineering
analyses as an aid to decision making. LOPA is typically used to determine if existing layers of protection are sufficient, and to develop risk reduction measures for
specific scenarios of concern.

A LOPA scenario consists of a single, unique initiating event consequence pair. Generally used for high consequence or high risk scenarios, LOPA generates
additional support and a greater degree of confidence in decisions made as compared to those relying on the use of purely qualitative tools such as Process
Hazard Analysis (PHA). Over the years since the introduction of LOPA to the process industries (CCPS,1993; Dowell,1997), and with the requirements of industry
standards for functional safety (ISA, 2004), it has been used extensively, with a wealth of application experience gained.

There are now many variations of LOPA in practice e some are highly simplified, order-of-magnitude approaches with simple calculations, while others are more
detailed and complex with extensions to quantitative techniques such as Human Reliability Analysis (HRA), Event Tree Analysis (ETA), Fault Tree Analysis (FTA),
and Quantitative Risk Analysis (QRA). LOPA has been stretched in many respects, with new developments in and applications for the methodology, and also
limitations and problems encountered in practical use of LOPA (HSE, 2009a, 2009b; Myers, 2010).

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7.4. SAFETY INTEGRITY LEVEL “SIL”

DERIVATION OF AN EQUATION FOR QUANTITATIVE SIL ASSIGNMENT, Edward M. Marszal, 2003

<http://www.sciencedirect.com/science/article/pii/S0019057807601220>

As engineers become more experienced with the application of safety instrumented systems (SIS’s), quantitative risk analysis for selection of safety integrity levels
(SIL’s) is becoming more and more common. SIS practitioners have found that qualitative methods for selecting SIL’s are unsatisfactory because they are overly
conservative. The inflated requirements yielded by these qualitative methods are unnecessarily increasing both the capital expense and the ongoing maintenance
cost of SIS’s.

To address the high equipment costs and poor results associated with qualitative selection methods, many sophisticated users of SIS’s are turning to quantitative
methods such as layer of protection analysis and full quantitative risk analysis. Procedures for applying quantitative methods to the SIL selection problem are in the
early stages of development. Literature explaining the use of fully quantitative methods for SIL selection is virtually nonexistent. For these two reasons, many
engineers are forced to use ad hoc methods for the selection process, arriving at equations through questionable methods, some of which are mathematically
incorrect.

A SIL QUANTIFICATION APPROACH BASED ON AN OPERATING SITUATION MODEL FOR SAFETY EVALUATION IN COMPLEX GUIDED
TRANSPORTATION SYSTEMS, J. Beugin, D. Renaux and L. Cauffriez, 2007

<http://www.sciencedirect.com/science/article/pii/S0951832006002201>

Safety analysis in guided transportation systems is essential to avoid rare but potentially catastrophic accidents. This article presents a quantitative probabilistic
model that integrates Safety Integrity Levels (SIL) for evaluating the safety of such systems. The standardized SIL indicator allows the safety requirements of each
safety subsystem, function and/or piece of equipment to be specified, making SILs pivotal parameters in safety evaluation. However, different interpretations of SIL
exist, and faced with the complexity of guided transportation systems, the current SIL allocation methods are inadequate for the task of safety assessment.

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To remedy these problems, the model developed in this paper seeks to verify, during the design phase of guided transportation system, whether or not the safety
specifications established by the transport authorities allow the overall safety target to be attained (i.e., if the SIL allocated to the different safety functions are
sufficient to ensure the required level of safety). To meet this objective, the model is based both on the operating situation concept and on Monte Carlo simulation.
The former allows safety systems to be formalized and their dynamics to be analyzed in order to show the evolution of the system in time and space, and the latter
make it possible to perform probabilistic calculations based on the scenario structure obtained.

A NOVEL METHOD FOR SIL VERIFICATION BASED ON SYSTEM DEGRADATION USING RELIABILITY BLOCK DIAGRAM, Long Ding, Hong
Wang, Kai Kang and Kai Wang, 2014

<http://www.sciencedirect.com/science/article/pii/S0951832014001604>

Safety integrity level (SIL) verification plays a critical role in reliability assessment of safety related systems. However, current methods available for SIL verification
are too complicated to be applied in practice. Therefore, a novel method for SIL verification, which is based on system degradation using reliability block diagram
(RBD) is proposed in this paper. The key idea of the method proposed is to perform RBD analysis and calculation of average probability of dangerous failure on
demand (PFDG) at each stage of system degradation, which is caused by failures of redundant channels. The method has been applied to several classical
redundant architectures of safety related systems, and could make the SIL verification process simpler. Further, the formulae obtained are identical with those
given in IEC 61508.

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8. DEFINITION OF THE PROBLEM

In the early days of oil refining in the 20s and 30s of last century, most gasoline blending components were composed of materials obtained directly from the crude
distillation unit. The situation changed significantly during World War II when there was a great need for aviation gasoline high octane. One response to this need
for high-octane gasoline was the development of a conversion unit refinery: the alkylation unit with hydrofluoric acid (HF), which currently remains as a key process
in the production of fuels with high standards.

Ecopetrol refinery is located at the industrial area of Mamonal and is one of the largest in the country and Latin America (Ecopetrol, 2014) features an alkylation
unit with hydrofluoric acid. This is one of the new units at the refinery expansion project. Since, alkylation processes catalyzed by concentrated sulfuric acid or
hydrofluoric acid are associated to problems of pollution and environmental safety (Xueqi, et al, 2012), it is important to follow an adequate safety system for the
operation of the hydrofluoric acid alkylation plant, because it represents a potentially high risk to the people who operate and to the process itself.

In the unit there are several chemicals that are potentially harmful to health and environment such as hydrofluoric acid (HF), which acts as a catalyst in the
alkylation reaction, acid water, alkylate, alumina, beta-picoline (ALKAD) , slaked lime, fuel gas, combustion gas, liquefied gases, liquid hydrocarbons, hydrogen,
potassium hydroxide (KOH), carbon monoxide (CO) in the flue gas, nitrogen and vapor. This is why environmental laws and regulations related to these processes
are increasingly stringent. Due to the potential impact area of an unplanned leak of any of the above mentioned chemicals, especially hydrofluoric acid, whose
corrosive properties make it toxic by ingestion, inhalation and dermal exposure causing serious and irreversible damage to the body (Gad and Sullivan, 2014), it is
necessary to optimize the safety system and practices, that meet the requirements for a safe, clean and profitable process (Ecopetrol, 2014).

Alkylation unit at the Ecopetrol’s refinery in Cartagena has thirteen sections which are:

• Selective Hydrogenation
• Charge and Drying
• Reaction
• Acid Storage

40
• Cooling Water Tower TAE
• Isostripper
• Depropanizer and HF Stripper
• Propane treatment
• Debutanization and Alkylate treatment
• N-Butane treatment
• ALKAD Regeneration
• HF Regeneration
• Effluent Treatment

Due to the high risk presented by the alkylation unit will apply three different methodologies which are HAZOP, LOPA and SIL which help to reduce risks and
improve the safety of the plant. During these times these methodologies have been implemented and have shown excellent results.

9. IDENTIFICATION OF IMPORTANT ISSUES

The refinery in Cartagena Colombia applies the alkylation unit to produce gasoline range material from olefins catalyzed by a strong acid in this case hydrofluoric.
The hydrofluoric acid is a dangerous inorganic acid, can cause severe corrosive effects and systemic toxicity (Xingang, 2014)

When comparing hydrofluoric and sulfuric acid, many differences can be noted, including costs, additional utilities, hazards, and inconveniences. Some alkylation
processes already use hydrofluoric acid as catalyst, making it difficult and costly to change the catalyst to sulfuric acid. When choosing which acid catalyst to use
in an alkylation processing units, companies mostly rely on the economic analysis rather than the safety aspects. Supporters of the hydrofluoric acid process argue
that both capital and total operating costs are less than those of sulfuric acid processes (Akpabio and Neeka, 2013) for the following reasons:

41
1. Smaller and simpler reactor designs are feasible.

2. Cooling water can be used instead of refrigeration.

3. Smaller settling devices are needed for emulsions.

4. Essentially complete regeneration of the hydrofluoric acid catalyst occurs. Hence, hydrofluoric acid consumption and costs are very low. Disposal of
spent acid is not necessary.

5. There is increased flexibility of operation relative to temperature, external ratio of isobutane to olefin, etc.

6. There is decreased need for turbulence or agitation when acid and hydrocarbon streams are combined.

This executive report presents the results of the application of Hazard and Operability Analysis (HAZOP), Layer of Protection Analysis (LOPA) and Safety Integrity
Level (SIL) to the alkylation unit catalyzed with hydrofluoric acid to isolate the risk in the alkylation plant and identify why the safety practices in it.

10. ANALYSIS OF ISSUES

The unit counts with fourteen section and we are apply the methodologies above mentioned, the results shown below are the recommendations obtained for the
scenarios studied, so it is which of these were the most significant identified and are LOPA and SIL methodology applied to reduce the risk of possible causes
occurred. The results have been organized in each of the methodologies studied.

10.1. HAZOP

The simulation and analysis through the HAZOP methodology in alkylation unit catalyzed with hydrofluoric acid allowed to determine the possible failures of
operability and how these failures are can affect the process based on the risk matrix used by Ecopetrol described above in table 3. It also allows obtaining

42
recommendations for the unit studied. In the unit 1092 scenarios were studied in 13 units of 14 because not have the P&IDs of one of them, recommendations for
each of the scenarios were obtained and in this part a summary of these is presented.

In all the unit some lines counts with the necessary safeguards but it is important to realize periodic maintenance and monitoring to the vessels, pipes, existing
safeguards, indicators, valves, equipment and immediately report about the real state of the vessel and to prevent that indicators or controllers send a bad signal to
the control room or valve. Do a schedule to realize the action requires and delegate people to do the scheduled activity. Likewise make constant operator
procedures, monitoring, training and sampling procedures when it’s necessary.

The process generally has a security system such as bypass and relief or vent system to avoid potential explosion for overpressure in the vessels or pipes, so is
important realize constant check to TEA system, bypass and vent system to avoid leak and ensure the correct operability. In the same manner the good
communication between employees is critical to mitigate the consequences of possible causes analyzed and is recommendable realize training to all employees to
behavior based safety to ensure the best practices and implement it in the refinery.

The process started with a selective hydrogenation. The charges for this section are diolefins, olefins and hydrogen. The objective is decrease the content of
diolefins and increases the concentration olefins with the purpose to obtain the best quality of the charge from the unit. Hydrogen reacts with hydrocarbon in
presence of a catalyzer for obtain the olefins and also of this obtain oily water. In this section four nodes were identify.

The first one is the feed surge drum D-201 The process parameter studied by the team are temperature, pressure and level with high, less and no as deviation, the
HAZOP team identify some recommendations in this node as shown below:

- Install a temperature, pressure and flow indicators which works with an indicator controls and create a control loops to ensure the correct performance
- Install additional temperature, pressure and flow sensor in some parts of the process
- Consider an automation of the oily water drainage system to avoid an overpressure and presence of pollutants
- Installation a pressure indicator that worked with some pressure indicators valves to ensure that the pressure profile don't change
- Constant check to TEA, bypass and vent system to avoid leak and ensure the correct operability
- Good communication between employees and is recommendable implementing behavior based safety to ensure the best practices

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The second node is the heat exchangers E-201 and the same parameters studied in the first node are studied in this node with the same deviations. The
recommendations obtain in this node are:

- Install an analyzer in the inlet pipe to heat exchangers E-201 for check the quality of the stream and prevent the generation of possible pollutants
- Constant maintenance and check the driers heat exchangers E-201 to prevent possible fails and inform the real state of the equipment
- Implement control loops that working with a temperature, pressure and flow indicator to ensure the correct operation range
- Considerer install a bypass system due to this can prevent possible injures if the control valve fail
- Installation of temperature, pressure and flow Indicator and in some case indicator control or indicator alarm due to the process required more control in
this part.
- Periodic checks to pipeline where we can get the correct status of them for avoid possible changes or risk in the process

The third node is the condenser D – 204 and the recommendations for this equipment are:

- Constant maintenance the pipeline to prevent ruptures, leaks or hold for corrosion or external events and contamination of the other streams of the
process
- Due to the process has an important safety system is recommendable activate bypass system and the valve that before control valve to stabilize the
process
- Installation of temperature, pressure and flow Indicator and in some case indicator control or indicator alarm due to the process required more control

The fourth node is the reactors R-201/202 and the same parameters were studied. The recommendations founds for the HAZOP team were:

- Constant monitoring to the operation conditions and reactors R-201/202 to prevent ruptures, leaks or hold for corrosion or external events and
contamination of the other streams of the process
- Periodic checks to pipeline where we can get the correct status of them for avoid possible changes or risk in the process
- Install a sampling point FY in some stream to prevent presence of contaminants that can affect the process
- Periodic reactivation of catalyst to ensure the correct conversion and the reaction time

44
- Implement a cooling system to the reactor for control the temperature runway
- Install a Flow Indicator in the hydrogen line to prevent losses or possible deactivation of the catalyst and deviations in the process
- Maintenance to the hydrogen filters to ensure the correct convert and reaction time
- Installation of temperature, pressure and flow Indicator and in some case indicator control or indicator alarm due to the process required more control in
this part
- Install an analyzer in the inlet of the process to prevent changes and deviations due to contaminants

The last node is the stripper T-201. The recommendations found for the team studying the same parameters and deviations are:

- Increase and decrease the flow in the inputs and outputs of the tower V-02 including reflux flow depending on what is required for the process for maintain
constant the variables like temperature, pressure and level in the process
- Is required some controllers like pressure, temperature and level indicator controls (PI – TI – LI) having a constant monitoring of the loops control to avoid
possible fails.
- Installation of temperature, pressure and flow Indicator and in some case indicator control or indicator alarm due to the process required more control in
this part.
- Periodic checks to pipeline where we can get the correct status of them for avoid possible changes or risk in the process

The olefins obtain in the selective hydrogenation go to the second step which is the charge and drying section to remove humidity and obtained the olefins and
oily water, this step is a pretreatment section. In this section identifies four nodes and obtains some recommendations for each one analyzing three operational
variable as temperature, pressure and level with deviation high and less.

The recommendations obtain in the first node, surge drum D-02, and are:

- Install a Temperature Indicator in the inlet line to the drum D-02 to monitoring this operational variable in the control room
- Consider install a Flow Indicator after valve FV 1000 or changing the location of FIC 1000
- Install a Flow Indicator in the drain line of oily water and in the inlet and outlet line

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- Consider to install a flow indicator with lower and higher alarm in the drum.
- Consider adding a low flow alarm on FIC 1000
- Consider install a PT/PI with high pressure alarm on surge drum D-02
- Consider adding an HF/Water acid analyzer on the E-28/E-28A reactor acid circulation loop

The second and third nodes are the olefins feed dryers in use/regenerating. The parameters studied in this part are temperature, pressure, water
concentration in the inlet stream, water concentration in the outlet stream, inlet flow with deviation less and high and the recommendations obtain for the team in
these nodes are:

- Install a pressure indicator in each dryer and a manual valve after valves XV 1352/1353.
- In the inlet line consider install a pressure indicator
- Install a flow indicator control (FIC) which works with a control valve in the inlet stream to monitoring the flow in the dryer, an analyzer, bypass system
- If it is possible install a FI in the inlet line in the E-01 and other one after valves 1346/1347 to monitoring the flow in the inlet stream
- Install a PDI in each olefins feed driers
- Install a bypass system around valves 1346/1347 and around the valves XV 1350/1351
- Install a analyzer in the inlet pipe and realize sampling procedures in the stream

The fourth one is the condenser D-24 the recommendation obtains is:

- Install a temperature indicator and a flow indicator in the inlet steam line and the inlet of the D-24.

The last one is the coalesce D-01, the team evaluates the same parameters, temperature, pressure and level with the same deviation, the recommendation obtain
are:

- Install a flow indicator control in the inlet stream of each trim condenser and operator monitoring to these flow indicators.
- Install a flow indicator in the inlet line of olefin regenerantcoalescer.

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The dryers olefins go to the reaction section which is the third segment in the unit, is consider such as the heart of the unit due to the olefins and isobutene reacts
in presence of hydrofluoric acid as catalyzer for obtain the alkylate. The acid will enters in the reactors comes of acid storage and additive originated in the additive
regeneration section ALKAD. This additive is added to acid with the end of decrease the volatility, in this form; minimize the vaporization when the acid is in contact
with the atmosphere in case of a leak. The reactors have always been the equipment that should have more security in an alkylation unit. In this section identifies
two nodes and analyzes temperature, pressure, level, and relation isobutene/olefins as operational variables with deviation less and high.

The first node is the reactors E28/28A, this node is the heart of the unit and count with a lot of safeguards. The recommendations found by the team are:

- Install a Flow Indicator in the inlet line when the streams are mixed to verify that the flow is correct
- Flow Indicator and Low Flow Alarm to provide an immediate indication of cooling loss
- High Temperature Alarm to alert the operator in the event of cooling function loss
- Pressure Indicator Control PIC in the exit of the cooling pipe to control the pressure from the control room
- Flow Indicator with higher and lower Alarm in case that the valve fails closed and show the inlet flow of the reactors and maintain the relation
isobutane/olefins and HF/HC
- Flow Indicator Control after the HV 1908/1056 and loops work which work with those valves.
- Install a high temperature shutdown system that would automatically shut down the process in the event of a high reactor temperature. The shutdown
temperature would be higher than the alarm temperature to provide the operator with the opportunity to restore cooling before the reactor is shut down
and realize evaluation of the cooling water source to consider any possible interruption and contamination of the supply.
- In the process is necessary monitoring the flow of olefins, butane, isobutane and acid to maintain the operation in case of fails in the reactor and close the
valves FV 1047/1900 and FV 1059/1903 to cut the inlet flow
- Periodic monitoring of the controllers to avoid undesirable reactions and maintain the production of alkylate, of the Cooling System to maintain the
operation temperature in the range of operating, of the cooling pipe and PSV valve to avoid an incident and maintain the good operation in the reactors
and analyze when is necessary the activate bypass system to control of the flow in case that fails valves.

The second node is the acid settler D-04, the parameters studied were temperature, pressure and level and the recommendations found in this drum are:

47
- Install some controllers such as a Temperature Indicator Alarm Control in the inlet stream of the D-04 to avoid the reduction of the sedimentation time
- Install a Temperature Indicator (TI) in the streams from the isostripper to maintain the temperature of operation in the D-04
- Install a Low Level Alarm to alert the operator in the event of leak or hole in the tank and a Flow Indicator in the inlet pipe
- Install a high level alarm to avoid HF losses and maintain the process in the unit and a pressure Indicator in the outside of line to prevent operational
problems in the next section and avoid contamination of the stream and Pressure Indicator in the pipe to show that the pipe no is obstructed
- In the process is necessary an increasing of the inlet flow to maintain the level in the D-04 and a decreasing the inlet flow to maintain the level in the D-04
in case the level is from top to toe

The acid storage section has the objective to receive the unreacted acid from the reaction section and send acid to reactors. This sections are compound for
drums and some of the scenarios studied have enough safeguards and only recommended do a periodic maintenance and monitoring to the controls, valves,
pipes, equipment and the existing safeguards. Sometimes is necessary reestablishing the set point of some controllers and loops controls. Eliminate the presence
of water in the vessels and pipes to avoid corrosion and possible release of acid in the plant. Also, realize operator procedures, inspections, training and sampling
procedures.

The first node of this section is the HF acid container (truck) the parameters analyzed were pressure, level and temperature but in the case of temperature was
considered but nothing significant identified and the recommendation found are:

- Eliminate the presence of pollutants in the HF acid container (truck) to avoid sedimentation in the pipe.
- Install a high level alarm in it and install a pressure indicator in the top of the tank to monitoring this property.

The second node is the acid storage drum D-30 and the same parameters were considered and the recommendations obtain are:

- Consider install a humidity analyzer in the inlet stream to the acid storage drum and a bypass system in the line were located the valve XV 1045
- Consider install a flow indicator in the inlet line after valve XV 1045 to monitoring the flow in this line.

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The third node is the acid dump drum and the pressure, level and temperature was analyze but for the temperature nothing significant issues were identified and
the recommendation found for the others parameters are:

- Install a flow indicator in the outlet pipe and a pressure indicator in the top and in the inlet stream of acid dump drum to monitoring these properties
constantly in the control room.
- Install o replace the PI 1081 for a PIC which works in a loop control with valve XV 1077 to avoid human error.
- Install a shutdown system to cut the inlet flow of N2 in the tank and a high level alarm in the acid dump drum. Install a PSV to send the acid to another
vessel (header).

The isostripper section is the section in which the different fractions generated in the reaction are separated. In the top the light hydrocarbons go out such as
propane, isobutene and all traces of HF which is drawn with the hydrocarbon and in the bottom the heavy compounds like alkylate and butane go out. This section
was divide in four nodes which are the principals equipment’s.

The first node is the isostripper surge drum D-05 and the parameters temperature, pressure and level with deviation less and high are studied and found these
recommendations:

- Install some controllers such as a Temperature Indicator (TI), Pressure Indicator (PI) and Flow Indicator (FI) to maintain the operation in the Isostripper V-
02
- Is indispensable the monitoring of the pressure and flow controllers to avoid fails in the operation in the isostripper surge drum D-05 and prevent that
these controllers send bad signal to the valves or control room

The second node is the isostripper tower V-02 and the same parameters were studied with the same deviations, the team found these recommendations:

- Increase and decrease the flow in the inputs and outputs of the tower V-02 including reflux flow depending on what is required for the process for maintain
stabilize of the variables like temperature, pressure and level.

49
- Is required in some controllers like pressure, temperature and level indicator controls (PI – TI – LI) requiring a constant monitoring of the loops control to
avoid possible fails.
- In some parts of the isostripper install flow, temperature and pressure indicator alarm (FA-TA-PA) due to the process required most control and
immediately actions if some cause could occur
- Install a bypass and relief system where the process is requires like in flow indicator controls due to this system is one of the best safeguards.
- Due to furnace H-01 is one of the principal heat sources of the tower V-02 is necessary increase and decrease the flow when the process is requires
stabilizing operating conditions.
- In some cases is necessary decrease and increase the steam generated from reboiler stabilizing operating conditions
- Maintenance of the heat exchanger and reboiler of the isostripper tower V-02 to maintain the temperature of operation and a good separation inside of the
tower V-02.
- Install a Flow Indicator Alarm in the reflux inlet in case of have a problems before the FV 2319 valve

The third one is the depropanizer feed settler D-12, the team considers that in this part is appropriate:

- Install a Temperature indicator (TI) and Pressure Indicator (PI) due to that are parameters important in the process of the tank and is necessary the
control
- Install a Bypass system in the depropanizer feed settler D-12 to control the flow to avoid operational problems in this tank
- Monitoring and maintenance to the heat exchanger to prevent that temperature is less or high and maintain the separation in the depropanizer feed
settler D-12, also the pipes of inlet and exit and controllers are very important due to that maintains the good operation in the tank D-12
- Feedback to employees on good operating practices and application of the Behaviour Based Safety (BBS)

In the depropanizer and HF stripper section enters the light hydrocarbon like propane and HF traces with the purpose to recover the non-reactant propane and
ensure complete removal of HF acid of the hydrocarbon recirculation. In this section is obtained stripping isobutane and propane. In this section five node were
studied and analyzed.

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The first node is the depropanizer V-04 and the recommendations were got by the team are:

- Review of the process in the isostripper V-02 to maintain the temperature of the inlet stream of the Depropanizer V-04 and avoid bad separation in this
tower
- Decreasing the inlet flow and reflux flow in the tower to maintain the right temperature in the Depropanizer V-04
- It is necessary install some controllers such as a Temperature Indicator Alarm (TIA), Flow Indicator (FI), Flow Indicator Alarm (FIA) and an Alarm in case
that the temperature or flow is less or high and do the right procedures to avoid operational problems in the Depropanizer V-04 and the next sections
causing a decreasing in the efficiency of the process
- Increasing the inlet flow and reflux flow in the tower to maintain the right temperature in the V-04

The second node is the depropanizer receiver D-13 and the recommendations obtain for the parameters studied are:

- Constantly monitoring to the cooling system to maintain the heat transfer in the heat exchanger, also the controllers is necessary to avoid bad signal in
the control room or valve and prevent operational problems in the depropanizer receiver D-13
- Is important to install some controller to maintain better the operation, in this equipment is necessary to install a Flow Indicator (FI), Flow Indicator Control
(FIC), Pressure Indicator (PI) and Pressure Indicator Alarm (PIA) to avoid problems in the tank and maintain the efficiency of the process
- Control of the process variable in the depropanizer and HF Stripper to avoid possible damage in the next equipments and prevent the decreasing of the
efficiency of the process in the next sections of the unit

The third one is the isobutene flush filter S-04A/B and the only recommendation were obtain in this node is realize constantly monitoring of the filter to maintain the
operation and to avoid that the isobutane stream comes with pollutants.

The fourth node is the HF stripper V-05. For this node is indispensable the monitoring of the Depropanizer and receiver D-13, Pressure Safety Valve (PSV) and
controllers of flow and level to avoid fails in the operation in the HF stripper, prevent that these controllers send bad signal to the valves or control room and obtain
propane in a good condition. The other recommendations are:

51
- Increasing of the steam in the reboiler to maintain of the operating temperature in the tower
- Install other controllers as a Temperature Indicator (TI), Flow Indicator Alarm (FIA) and Flow Indicator (FI) to maintain of the operation parameters of the
process and avoid problems in the unit

The last one is the propane flush filter S-06A/B and the team consider that filters counts with enough safeguards, the controllers and indicators are located in the
correct place, only need to realize constantly monitoring of the process in the HF stripper V-05 to avoid that the propane stream come with contaminant.

The propane recover in the depropanizer enter to the next step which is propane treatment to remove possible traces of acid in the stream. In this section the
parameters consider were temperature, pressure and level in the three nodes.

The first node is the exchanger E-25 and the recommendations were obtain are:

- Review constant of the operation in the HF stripper, flow and heat exchangers to avoid problems in the remove of the organic fluorides and maintain of
the operation
- Install other controllers to maintain of the operation in the section
- Install a Flow Indicator Alarm (FIA) and Pressure Indicator Control (PIC) to avoid operational problems and obtain a good propane

The second node is the propane alumina treaters D- 14 A/B and the recommendations were obtained are:

- Review of the operation in the heat exchanger E-25 to maintain the removing of the fluorides in the treaters
- To maintain the good operation in the treaters is necessary install a pressure Indicator (PI) and Flow Indicator (FI) to show that the flow and pressure is
right to maintain of the operation in the propane treatment
- In this section is necessary apply monitoring to the controllers and valves to avoid fails in the process to maintain the operation in the D-14 A/B and
propane KOH treater

The third node is the propane KOH treaters D-15 and the recommendations were obtained are:

52
- In the propane KOH treaters D-15 is important a monitoring constantly of the cooling system, HF stripper and pipes to verify that the process variables are
right and avoid an incident in the plant
- In this equipment is necessary install a Flow Indicator (FI) to verify that the flow is right and avoid problems in the process of the Propane KOH Treaters
D-15

Alkylate and butane stream enter to other step in the unit which are the debutanizer and alkylate treatment, in this part the normal butane is removed from the
alkylate, after that the stream is conditioned and contaminants are removed. The butane stream proceeds to step for remove any part of acid and is sent to another
unit.

The first node is debutanizer tower V-01 and the recommendations obtain when the parameters were analyzed are:

- Increase and decrease the flow that inputs and outputs of the tower depending on what is required for the process for maintain stabilize of the variables
like temperature, pressure and level.
- In some cases is necessary decrease and increase the steam generated from reboiler E-09 stabilizing operating conditions due to this is the principal
equipment in the hot generation to tower V-01
- Installation a Pressure Indicator Alarm PIA, Temperature indicator alarm TIA, flow indicator alarm FIA, due to process required in some parts of him for
prevent possible leak, rupture, hold or release to control this fail
- Installation bypass and relief system where the process is requires due to this system is one of the best safeguards

The second node is reflux drum D-08 and the recommendations obtain are:

- Decrease or increase the flow of secondary water that coming in into 08 A/B Exchanger for increase or decrease the temperature of vapors and liquid in
the tower for controlling the operational range.
- Increase and decrease the flow in that inputs and outputs of the reflux drum D-08 depending on what is required for the process for maintain stabilize of
the variables like temperature, pressure and level.
- Decrease the flow outside the column V-01 in the bottoms part for decrease the temperature, pressure and level and stabilize the profile.

53
- Due to the process has a security system in some parts of him which is bypass and relief system is recommendable if the possible cause occur activate
bypass and relief system for mitigate or prevent injuries or risk
- Installation of temperature, pressure and flow Indicator and in some case indicator control or indicator alarm due to the process required more control in
this part to control better.

The third node is alkylate filters S-05A/B and we obtained the follow recommendations:

- Installation a Pressure Indicator Alarm PIA, Temperature indicator alarm TIA, flow indicator alarm FIA, due to process required in some parts of him for
prevent possible leak, rupture, hold or release to control this fail
- Due to the process has a security system in some parts of him which is bypass and relief system is recommendable if the possible cause occur activate
bypass and relief system for mitigate or prevent injuries or risk

The last one is the alkylate treatment drum D-06 and is important to realize constant maintenance to the pipeline and drum D-06 to prevent ruptures, leaks or hold
for corrosion or external events and contamination of the other streams of the process. Due to the process has a security system in some parts of him which is
bypass and relief system is recommendable if the possible cause occur activate bypass and relief system for mitigate or prevent injuries or risk.

The normal-butane treatment has the objective to remove possible traces of HF acid in the stream to send the normal butane to another unit in the refinery. In this
part the temperature, pressure and level were analyzed and five nodes are identified.

The first one is the heat exchangers E-14/14A and condenser D 27/27A. In this section the process count with a bypass and relief system therefore is
recommendable if the pressure or temperature increase inside the vessels activate these system for mitigate or prevent injuries or risk. Others recommendations
obtain for these nodes are:

- Installation a flow indicator control with lower and higher alarm due to process required in some parts of it for prevent possible leak, rupture, hold or
release to control this fail
- Decrease the cooling water that enter in the heat exchanger D 27/27A for decrease the temperature of the flow that coming out

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The second node is the treaters with alumina D-09A-D and the team found the following recommendations:

- Decrease the flow that enter to alumina treaters D-09A-D and increase the steam flow in the heat exchanger E-14/14A for stabilize the variables like
temperature, pressure and level and maintain the operability process.
- Installation a Pressure Indicator Alarm PIA, Temperature indicator alarm TIA, flow indicator alarm FIA, due to process required in some parts of him for
prevent possible leak, rupture, hold or release to control this fail
- Feedback to employees on good operating practices and is recommendable using behavior based safety for prevent human errors
- Due to the process has a security system in some parts of him which is bypass and relief system is recommendable if the possible cause occur activate
bypass and relief system for mitigate or prevent injuries or risk
- Install a flow indicator system in the inlet stream which is for control the flow that enter in the alumina treaters additional to this is required a constant
monitoring for prevent possible malfunctions and risk to process and employees

The third node is the coalescers D-10/10A and the recommendations obtain for these vessels are:

- Install a flow indicator system in the inlet stream for control the flow and level in the tank because this depends on the separation of substances and
prevents possible contaminants
- Due to heat exchangers has the responsibility of control the temperature that enter in the coalescer is necessary increase the cool secondary water in the
heat exchangers E-16/16A for maintenance the temperature
- Installation of temperature, pressure and flow Indicator and in some case indicator control or indicator alarm due to the process required more control in
this part to control better.
- Installation a bypass system due to is the most effective system for control tamponed or fails in the valves and taking into account that if the valve is
important and the flow is dangerous if this is in contact with the environment

For the fourth node the KOH treatments drum D-11/11A the recommendations obtain are:

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- Installation of temperature, pressure and flow Indicator and in some case indicator control or indicator alarm due to the process required more control in
this part.
- Due to N-Butane sometimes contain more water than normal is necessary decrease the inlet flow at treatments drum D 11/11A for avoid possible
damages
- In some parts he process has a manual valves which are can activate if the principal valve fails in this case is recommendable activate manual valves

The last one is the additive treatments for this node the recommendations are:

- Installation of temperature, pressure and flow Indicator and in some case indicator control or indicator alarm due to the process required more control in
this part to control better.
- Decrease the flow and increase the temperature in the coalesce D 10/10A for remove complete the pollutants
- Installation of a pressure indicator that worked with some pressure indicators valves to ensure that the pressure profile don't change
- Constant maintenance to the state of the additive treatments to ensure proper operation and avoid possible operational problems and is recommendable
have a constant report about the tank state

Other important part in this unit is the HF regenerator. The purpose in this part is removing soluble contaminants in the acid and thus maintains the purity of the
acid also enters isobotune stripping. For this section four nodes were obtained and analyzed.

The team evaluates the first node which is the acid regenerator V-03 including the IsobutaneSuperheater E-17 and IsobutaneSuperheater Condensate Pot D-28
and obtains the follow recommendation:

- Install a FIC in the inlet stream which works with FIC 1180 to regulate the steam flow rate to ensure the correct inlet temperature and another one in the
inlet line of the regenerator V-03 (after valve FV 1171) which works with a flow valve in the intermittent inlet line to increase the flow rate in case of this
valve or FIC 1171 which regulate the valve fails and maintain the operational range (626 BDP)
- Install a TIC in each line (Regeneration isobutane from the depropanizer and HF stripper and HF from the Reaction section) to monitoring the inlet
temperature and do a loop control with a valve which controls the inlet flow rate to hot isobutane in the bottom of the column V-03.

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- Change the location of the existing FI in the line after valve TV1168 and install a higher temperature alarm in the TIC which controls this valve.
- Install a manual valve and FI in the line from ALKAD regeneration section and close the intermittent flow and also install another FI in the outlet pipe in the
bottom of the regenerator and consider if it is possible install other in the inlet pipe (in the bottom of the tower).
- Change the manual valve GBCF22 in the top of the regenerator for a security valve (PSV) with a bypass system and send the stream to flare header to
reduce the risk for the employees to contaminate with HF and install a pressure indicator in the top of the column.

The second node is the polymer surge drum D-16 and the team consider necessary:

- Install a temperature indicator and flow indicator in the inlet line (steam line and polymer from V-03 line) and only flow indicator in the nitrogen line and a
flow indicator control with a flow valve to control the inlet flow from the alkad section D-101, if it is possible install a temperature valve in the steam line
which works with a TIC located in the polymer from V-03 line to regulate the steam flow.
- Replace the manual valve LWCS01 for a temperature valve controlled by TIC to avoid human errors and consider install a pressure indicator in the top of
the drum to control the pressure inside the vessel and avoid possible explosion and potential fire.

The third one is the polymer neutralizer D-17 and the recommendation obtain for this node are show below.

- Install a flow indicator in the nitrogen line and in the inlet line to the polymer neutralizer D-17 from D-16
- Install a pressure indicator in the top of the drum and a level indicator control with high and low level alarm with control these variable in the vessel
- Consider if it is necessary the manual valve GWCS07 in the vessel

The last node is the closed drain drum D-404 and the recommendations are:

- Consider moving the PI-2714 and restrictive orifice (RO) in the nitrogen line to D-404 vent downstream of the bypass PCV-2700.
- Install a pressure indicator in the top of the drum with the objective of monitoring this operational variable and revising the design pressure of the D-404
Closed Drain Drum because the maximum nitrogen pressure on the purge to the drum and vent piping is approximately 95 psig and the current design
pressure of the drum is 50 psig.

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- Change the TI 2704 for a TIC and consider change the location of TI 2704 or install another temperature indicator in the vessel and higher temperature
alarm
- Install a temperature valve in the inlet steam pipe which works with this controller.
- Consider install a TI in the vessel and consider installing a bypass system in the inlet steam pipe line. Install a flow indicator in the line to monitoring this
operational variable.
- Consider if it is necessary the manual valve GWCS03 in the vessel and analyze if this valve can change for a safety valve (PSV)

The effluent treatment in the section has the purpose to recollect all the oily water produced in the unit and performed a proper treatment of these streams
efficiently and safely, minimizing the risk inherent a possible discharge of hazardous substances. In general realize periodic maintenance to equipment, existing
safeguards and operator procedures in the plant, training and sampling procedures and check the NPSH with the objective to avoid mechanical damage in pumps.
Delegate the function to check the status of the pump and do a schedule to realize the monitoring procedures.

The first node is liquid knockout drum D-18 and the analyze parameters such as temperature, pressure and level but when the temperature and pressure were
considered but nothing significant identified. Only found one recommendation in this node which is install a manual or control valve in the inlet line of liquid
knockout drum and change the LI 1272 for a LIC and this controller works with the level valve.

The second node is the neutralizing drum D-19 and the recommendations are:

- Install a flow indicator in the steam line


- Install an acid analyzer in the inlet line in the neutralizing drum to control the presence of acid in this section and a high temperature alarm in TI 2540.

The third node is the relief gas scrubber V-06 and the recommendations are:

- Consider install a temperature indicator control in the relief gas scrubber which works with a temperature valve localized in the inlet steam line to control
the temperature inside.

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- Change the GACF06 in the relief gas scrubber for a safety valve to avoid human error and overpressure in the vessel with potential fire, spill of substance
in the unit and risk to employees

The fourth node is the KOH regeneration tank D-20 and the recommendations were found are:

- Consider install a flow indicator in the inlet line to the KOH regeneration tank to control the flow rate which enters in the reboiler and a hydrometer to
confirm the KOH solution density
- Install a shutdown system in the eductor S-03 which works with a temperature indicator to control the temperature inside the tank
- Ensure there is a gap between the Regeneration Tank drain line and the Neutralization Basin to see if there is plugging in the drain line and to minimize
KOH losses

The last node is the neutralizing basin TK-001A/B in this node the parameter pressure is not applicable because this tank is open to atmosphere and the
temperature was analyzed but nothing important significant identify. Thus, for the level the recommendations found are:

- Determine the means to clean and how to handle solids that might accumulate in the Neutralizing Basin
- Provide a line to divert the AWS water from the Neutralizing Basin to the potentially contaminated storm water sump

The KOH mixer tank D-22 was analyzed and nothing important issues were found, for this reason was not analyzed such a node in this part.

The section counts which its own cooling water tower to recovers the refrigerant properties of primary cooling water tower, in this section only one node
was identified and the parameter studied are temperature, pressure, level and composition (water purity), in general the team recommended the following items:

- Realize constant check of the process to ensure the adequate functioning of the unit. Check all the procedures with the same goal include the cooling
water system failures
- Constant check of the parameters studied to avoid the spill of water and revision of the existing safeguards.
- Periodic sampling procedures in the treatment procedures and training to the operator to do these procedures safely.

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- Check the pressure in each cooling water exchanger to guarantee the correct operation of this and avoid damage in the exchangers
- Install a low pressure alarm on PI 1382 in the high pressure steam supply and a measuring element level low (LEL) in the cooling system.

The last section analyze was the Alkad regeneration and four node were identify. The objective in this section is regenerate the additive with isobutene stripping
which is added to the reaction section to decrease the volatility, in this form; minimize the vaporization when the acid is in contact with the atmosphere in case of a
leak.

The first node is the fresh additive charge and additive storage drum D-103. The recommendations for this node are:

- Due to the process count with a relief system which is one of the most important safety systems is required opened if the pressure increase inside the
vessel
- Considering install a bypass system for avoid problems if the principal valve fails
- Periodic maintenance of pumps P-104A because an inopportune damage of this can generate large overpressures in pipes and equipment

The second node is the additive stripper T-101. Analyzing the possible causes the team found the following recommendation:

- Decrease the acid stream that passes through the heat exchangers E-104A-D for control de temperature and avoid possible injures due to an acid relief
- Due to the process has a security system in some parts of him which is bypass and relief system is recommendable if the possible cause occur activate
bypass and relief system for mitigate or prevent injuries or risk
- Increase and decrease the flow in that inputs and outputs of the Drum D-103 including reflux flow depending on what is required for the process for
maintain stabilize of the variables like temperature, pressure and level.
- In some cases is recommendable close or open the manual valve which is before or after the control valve depends of the possible deviation for mitigate
the risk
- Installation of temperature, pressure and flow Indicator and in some case indicator control or indicator alarm due to the process required more control in
this part to control better.

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- Constant maintenance the pipeline and additive stripper T-101 to prevent ruptures, leaks or hold for corrosion or external events and contamination of the
other streams of the process.
- Installation of temperature, pressure and flow Indicator and in some case indicator control or indicator alarm due to the process required more control in
this part to control better.

The third node is additive stripper receiver D-102 and the recommendation that the team found are:

- Periodic check to the equipment stripper D-102 and pipeline where we can get the correct status of them for avoid possible changes or risk in the process
- In some cases is recommendable close or open the manual valve which is before or after the control valve depends of the possible deviation for mitigate
the risk
- Due to the process has a security system in some parts of him which is bypass and relief system is recommendable if the possible cause occur activate
bypass and relief system for mitigate or prevent injuries or risk

The fourth node is the additive stripper bottoms separator D-101 and the recommendations are:

- Install a flow indicator FI in the Cooling Water system to ensure the temperature profile in the column and avoid pollutants in the outside streams
- Periodic check to the stripper D-101 and pipeline where we can get the correct status of them for avoid possible changes or risk in the process
- Periodic maintenance of pump P-101 because an inopportune damage of this can generate large overpressures in pipes and equipment
- Considered install a turbine for generate more energy in the pump P-101 and ensure their function
- Due to the process has a security system in some parts of him which is bypass and relief system is recommendable if the possible cause occur activate
bypass and relief system for mitigate or prevent injuries or risk
- Stop Polymer flow to the Polymer Surge Drum for decrease the level until stabilize the temperature and pressure for avoid possible loss of the product

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10.2. LOPA & SIL

The LOPA and SIL report show the results obtain in the study of alkylation unit with hydrofluoric acid. A risk tolerance criterion of 10 -8 is stated in the LOPA as

applying for all risks environmental, financial and safety. This risk tolerance criteria description is unclear and may be inappropriate for the following reasons:

- Environmental, financial and safety risks should be assessed separately and relevant criteria applied.

- This LOPA dos not state what the risk tolerance criteria are, for example, risk of what, to what and from what.

- It is not clear whether the Individual Risk (IR) target represent s all risks the hypothetical individual person faces on site or just those associated with a

single tank and single hazard.

- No justification for the chosen criteria is presented in the LOPA assessment report.

For do LOPA the significant and high risks obtained in HAZOP were chosen, thus obtaining 24 scenarios divided into selective hydrogenation, reaction, propane

treatment, debutanization and alkylate treatment, N-Butane treatment, HF Regeneration, Cooling water and Effluent treatment unit.

For each scenarios were identified the independent protection layer (IPL) and using the methodology described above. Using the values of PFDs for each

safeguards show in tables 5, 6 and 7, we create a table 9 with the most common values for do this study.

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Table 9. Typical Protection Layer used in this study

INDEPENDENT PROTECTION LAYER PFD

Process Design (Indicator of Temperature, Pressure and Flow)

Process Design (Manual valve; Bypass system)

BPCS (Control Loop)

Alarm

Procedures Table 7

SIS

Relief Device (Pressure Safety Valve)

Emergency Response (Fires)

Using the frequency we could calculate the overall consequence frequency and compare with acceptable risk criteria to know if the deviation needed another IPL

to mitigate the hazardous scenarios. The deviations that not exceeded or is the same value assigned for the refinery it was necessary to generate more

recommendations to mitigate the risk. The safety integrity level (SIL) focuses on the adequacy of safeguards to mitigate hazardous scenarios (ACM Facility Safety,

2006)

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SELECTIVE HYDROGENATION

In the Selective Hydrogenation section we were obtained 176 scenarios in the HAZOP study of which 4 were evaluated with a significant risk and was analyze in

the LOPA and SIL study, these are:

The first one cause was in the Feed Surge Drum D-201,the process parameter is pressure with a deviation Less and the possible cause was “PIC 4007 fails

opened PV 4007A due to malfunctions” which has the following safeguards “Pressure of Nitrogen is 95 psig and pressure of the drum is 180 psig using for

decrease the pressure inside the tank, Relief valve (Fuel gas purges to the refinery flare system), Bypass system (LWCS01), Manual valves before and after PV

4007A (GWCS01) and Operator procedures and training and response”

With this possible cause we obtained a Severity of 5, Frequency of 3 and Risk of 15 S. In this part were acquired 3 Independents Protection Layers which are:

- Process Design

- Procedures

- Emergency Response

The overall consequence frequency for this deviation was this value is lower than so the hazard from this equipment generates with this

deviation was mitigated with the safeguards that the process has.

64
The second and third one cause were in the Reactors R-201/202, the process parameter is pressure with a deviation High and the possible cause was “The valve

PSV 4037 or PSV 4047 fails open due to malfunctions” which has the following safeguards “Manual valve GBCF03 and Operator procedures and training and

response”

With this possible cause we obtained a Severity of 5, Frequency of 3 and Risk of 15 S. In this part were acquired 3 Independents Protection Layers which are:

- Process Design

- Procedures

- Emergency Response

The overall consequence frequency for this deviation was this value is lower than so the hazard from this equipment generates with this

deviation was mitigated with the safeguards that the process has.

The process parameter for the other to other deviation for this equipment was High and the possible cause was “Due to malfunctions the PCV 4149 fails opened

increased the nitrogen flow” which has the following safeguards “Relief valve (Fuel gas purges to the refinery flare system) and Operator procedures and training

and response”

With this possible cause we obtained a Severity of 5, Frequency of 3 and Risk of 15 S. In this part were acquired 3 Independents Protection Layers which are:

- Procedures

- Relief device

65
- Emergency response

The overall consequence frequency for this deviation was this value is equal to so the hazard from this equipment generates with this

deviation was mitigated with the safeguards that the process has.

The last one cause were Stripper T-201, the process parameter is temperature with a deviation High, the possible cause was “Due to malfunctions the PV 4051

fails closed interrupting the olefins flow” which has the following safeguards “ Bypass System (LBCF01), manual valves GBCF01 before and after at pressure valve

and operator procedures, training and response”

With this possible cause we obtained a Severity of 3, Frequency of 4 and Risk of 12 S. In this part were acquired 2 Independents Protection Layers which are:

- Procedures

- Emergency response

The overall consequence frequency for this deviation was this value is less than so the hazard from this equipment generates with this

deviation was mitigated with the safeguards that the process has.

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CHARGE AND DRYING

In the charge and drying section we obtained one hundred thirteen scenarios which three scenarios of these were applied the LOPA and SIL methodologies.

These three scenarios are found in the surge drum D-02.

In the first initiating event the process parameter was Level and the deviation was Less. The possible cause was “Rupture or leak in the principle inlet line to D-02”

which has the following safeguards “Manuals valves CBCF01/ LWCS03/ LBCF06 to close the inlet flow for each streams, XV 2453, FV1006, Operator procedures,

training and response, and Emergency response”.

With this possible cause we obtained a Severity of 4, Frequency of 3 and Risk of 12S. In this part were acquired 5 Independent Protection Layers which are:

- Process Design

- BPCS

- Procedures

- SIS

- Emergency Response

Performing the different calculations the Overall Consequence Frequency was , in this case is not necessary suggest any recommendation to mitigate

this possible cause due to the existing independent protection layer may mitigate completely this possible cause.

67
In the second initiating event the process parameter was Level and the deviation was Less. The possible cause was “Rupture or leak in the outlet lines of the drum

D-02” which has the following safeguards “LI 1005 with low level and low-low alarm, Manual valve GWCS03, XV 1516, Operator procedures, training and

response, and Emergency response”.

With this possible cause we obtained a Severity of 4, Frequency of 3 and Risk of 12 S. In this part were acquired 6 Independent Protection Layers which are:

- Process Design

- BPCS

- Alarm

- Procedures

- SIS

- Emergency Response

Performing the different calculations the Overall Consequence Frequency was , in this case is not necessary suggest any recommendation to mitigate

this possible cause due to the existing independent protection layer may mitigate completely this possible cause.

In the third initiating event the process parameter was Level and the deviation was High. The possible cause was “LV 1004 fails closed for example bad transmitter

or loss of instrument air” which has the following safeguards “Bypass system around valve LV 1004 with manual valve LWCS03, LI 1005 with low level and low-low

alarm and high level and high - high alarm”.

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With this possible cause we obtained a Severity of 4, Frequency of 3 and Risk of 12 S. In this part were acquired 4 Independent Protection Layer which are:

- Process Design

- Alarm

- Procedures

- Emergency Response

Performing the different calculations the Overall Consequence Frequency was , in this case is not necessary suggest any recommendation to mitigate

this possible cause due to the existing independent protection layer may mitigate completely this possible cause.

REACTION SECTION

In the reaction section we obtained fifty scenarios which one scenarios it was applied the LOPA methodologies. This cause it was in the reactors E28/28A, the

process parameter was Temperature and the deviation was High. The possible cause was “The cooling flow is interrupted due to the FBCF01 fails closed” which

has the following safeguards “TI 1548; PI1546; Operator procedure training and response”.

With this possible cause we obtained a Severity of 4, Frequency of 3 and Risk of 12 S. In this part were acquired 3 Independent Protection Layers which are:

- Process Design

- Procedures

- Relief Device

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- Emergency

Performing the different calculations the Overall Consequence Frequency was , in this case is no necessary suggest some recommendation to mitigate

this possible cause but we consider apply this recommendation which was:

- Install a Flow Indicator Control with Low Flow Alarm which is located in the inlet pipe of the cooling water to maintain the process flow in the reactors

Performing the new calculations the New Overall was , I mean, that applying these recommendations may mitigate completely this possible cause.

PROPANE TREATMENT SECTION

In the next section which is Propane Treatment we obtained sixty two scenarios therefore two scenarios go to the LOPA analysis. These scenarios were acquired

in the node 3 which is the Propane KOH Treaters D-15. The LOPA analysis to these two scenarios was in the process parameter of Level.

The first deviation was Less, the possible cause was “PV-2417 valve fails open due to malfunctions” which count with the next safeguards “FIC-2415 with low flow

alarm, Operator procedures and training, GBCF 16 Manual valve located after of the PV 2417”. With this scenario we obtained a Severity of 4, Frequency of 3 and

Risk of 12 S. The independent protection layers to this possible cause were 5 which are:

- Process Design

- BPCS

- Alarm

- Procedures

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- Emergency Response

Performing the different calculations the Overall Consequence Frequency was , in this case no is necessary suggest some recommendation due to

that this scenario account whit the enough safeguards to mitigate this possible cause.

The second deviation was High, the possible cause was “PV-2417 fails closed due to malfunctions” which count with the next safeguards “Bypass around PV-

2417, FIC-2415 minimum flow controller with low flow alarm, PSV-2414 on the KOH treater, PSV-2407/2408 on the Alumina treater, Operator procedures and

training”. With this scenario we obtained a Severity of 4, Frequency of 3 and Risk of 12 S. The independent protection layers to this possible cause were 6 which

are:

- Process Design

- BPCS

- Alarm

- Procedures

- Relief Device

- Emergency Response

Performing the different calculations the Overall Consequence Frequency was , in this case no is necessary suggest some recommendation due to

that this scenario account whit the enough safeguards to mitigate this possible cause.

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DEBUTANIZATION AND ALKYLATE TREATMENT

In the Debutanization and Alkylate Treatment section we were obtained 72 scenarios in the HAZOP study of which 1 was evaluated with a significant risk and was

analyze in the LOPA and SIL study, these is:

In the first node in the equipment Alkylate Filter S-05 A/B with Level as process parameter and a deviation Less, the possible cause was “Loss of turbine pump P-

04A from either mechanical damage or loss of steam if using turbine as primary pump” which has the following safeguards “Pumps status in the PCS connected to

loops control, FI 2538, separate pump with separate power sources and operator procedures, training and response”

With this possible cause we obtained a Severity of 3, Frequency of 4 and Risk of 12 S. In this part were acquired 3 Independents Protection Layers which are:

- Procedures

- BPCS

- Emergency response

The overall consequence frequency for this deviation was this value is less than so the hazard from this equipment generates

with this deviation was mitigated with the safeguards that the process has.

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N-BUTANE TREATMENT

In the N-Butane treatments section we were obtained 103 scenarios in the HAZOP study of which 2 were evaluated with a significant risk and was analyze in the

LOPA and SIL study, these are:

The first one was in the Theaters with alumina D-09 A-D with Pressure as process parameter and High as deviation; the possible cause was “Manual valve

GBCF13 it will close due to human factors” which has the following safeguards “Operator procedures, training and response”

With this possible cause we obtained a Severity of 3, Frequency of 4 and Risk of 12 S. In this part was acquired 1 Independent Protection Layer which is:

- Emergency response

Performing the different calculations the Overall Consequence Frequency was , in this case is necessary suggest some recommendation to mitigate

this possible cause, which was:

- Is necessary install a loop control (BPCS) that worked with a flow valve worked with a Bypass System that worked between pressure control valve to avoid

problems

Performing the new calculations the New Overall was therefore this new result means that applying these recommendations may mitigate completely

this possible cause, hence the acceptable criteria of risk tolerated by the company is .

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The last one was N-butane coalescers D10/10A with pressure as process parameter and High as deviation; the possible cause was “Tamponed in the outside

pipeline of the N-Butane exit due to presence of impurities in the stream and bad maintenance of the piping” which has the following safeguards “PIC 1219/ 1984

worked with a control valve and operator procedures, training and response”.

With this possible cause we obtained a Severity of 4, Frequency of 3 and Risk of 12 S. In this part were acquired 2 Independents Protection Layers which are:

- BPCS

- Emergency Response

Performing the different calculations the Overall Consequence Frequency was , in this case is necessary suggest some recommendation to mitigate

this possible cause, which was:

- Is required a bypass system between pressure indicator control to avoid problems due to overpressure that can cause risks.

Performing the new calculations the New Overall was therefore this new result means that applying these recommendations may mitigate completely

this possible cause, hence the acceptable criteria of risk tolerated by the company is .

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HF REGENERATION

In the HF Regeneration section we obtained one hundred twelve scenarios which five scenarios of these were applied the LOPA and SIL methodologies. Three of

these scenarios are found in the acid regenerator V-03 and the other two scenarios are found in the closed drain drum D-404.

In the first initiating event the process parameter was Temperature and the deviation was High. The possible cause was “FV 1171 fails closed” which has the

following safeguards “Intermittent flow from ALKAD section, Lab sampling, hand wheel on FV 1171, TIC 1168 which will add reflux to maintain the overhead

temperature of the regenerator, Operator procedures, training and response”.

With this possible cause we obtained a Severity of 4, Frequency of 3 and Risk of 12 S. In this part were acquired 5 Independent Protection Layers which are:

- Process Design

- BPCS

- Procedures

Performing the different calculations the Overall Consequence Frequency was , in this case is not necessary suggest any recommendation to mitigate

this possible cause due to the existing independent protection layer may mitigate completely this possible cause.

In the second initiating event the process parameter was Temperature and the deviation was High. The possible cause was “TV 1168 malfunctions closed” which

has the following safeguards “FI-1170 flow indication, TI-1625 temperature indication, Hand wheel on TV-1168, Operator procedures, training and response”.

With this possible cause we obtained a Severity of 4, Frequency of 3 and Risk of 12 S. In this part were acquired 2 Independent Protection Layers which are:

75
- Process Design

- Procedures

Performing the different calculations the Overall Consequence Frequency was , in this case is no necessary suggest any recommendation to mitigate

this possible cause due to the existing independent protection layer may mitigate completely this possible cause.

In the third initiating event the process parameter was Pressure and the deviation was Less. The possible cause was “Manual valve GBCF22 in the top of the

regenerator is open” which has the following safeguards “Operator procedures, training and response”.

With this possible cause we obtained a Severity of 4, Frequency of 3 and Risk of 12 S. In this part were acquired 2 Independent Protection Layer which are:

- Procedures

- Emergency Response

Performing the different calculations the Overall Consequence Frequency was , in this case is necessary suggest some recommendation to mitigate

this possible cause, which was:

- Change the manual valve located in the top of the vessel for a relief valve to prevent air pollution and system from exceeding specified overpressure. The

effectiveness of this device is sensitive to service and experience.

Performing the new calculations the New Overall was therefore this new result means that applying these recommendations may mitigate completely

this possible cause, hence the acceptable criteria of risk tolerated by the company is .

76
In the fourth initiating event the process parameter was Pressure and the deviation was High in the closed drum D-404. The possible cause was “Bypass system of

PCV 2700 is opened increasing the nitrogen flow rate” which has the following safeguards “PI 2714, RO2716, Operator procedures, training and response”.

With this possible cause we obtained a Severity of 5, Frequency of 4 and Risk of 20 H. In this part were acquired 3 Independent Protection Layer which are:

- Process Design

- Procedures

- Emergency Response

Performing the different calculations the Overall Consequence Frequency was , in this case is necessary suggest some recommendation to mitigate

this possible cause, which was:

- Install a high pressure alarm with the existing pressure indicator

Performing the new calculations the New Overall was therefore this new result means that applying these recommendations may mitigate completely

this possible cause, hence the acceptable criteria of risk tolerated by the company is .

In the fifth initiating event the process parameter was Pressure and the deviation was High in the closed drum D-404. The possible cause was “PCV 2700 fails

opened increasing the N2 inlet flow” which has the following safeguards “PI 2714, RO2716, Operator procedures, training and response”.

With this possible cause we obtained a Severity of 5, Frequency of 4 and Risk of 20 H. In this part were acquired 3 Independent Protection Layers which are:

77
- Process Design

- Procedures

- Emergency Response

Performing the different calculations the Overall Consequence Frequency was , in this case is necessary suggest some recommendation to mitigate

this possible cause, which was:

- Install a high pressure alarm with the existing pressure indicator

Performing the new calculations the New Overall was therefore this new result means that applying these recommendations may mitigate completely

this possible cause, hence the acceptable criteria of risk tolerated by the company is .

COOLING WATER

In the cooling water section we obtained fifteen scenarios which only one scenario it was applied the LOPA and SIL methodologies. This initiating event was in the

cooling tower CT-401, the process parameter was composition (water purity) and the deviation was less. The possible cause was “Leak of hydrocarbon” which has

the following safeguards “AI 2003, Interlock UC 31, AIC 2026, AI 2027, Additive to maintain equipment integrity, Sampling procedures, Operator procedures,

training and response”.

With this possible cause we obtained a Severity of 4, Frequency of 3 and Risk of 12 S. In this part were acquired 3 Independent Protection Layers which are:

- BPCS

78
- Procedures

- Emergency Response

Performing the different calculations the Overall Consequence Frequency was , in this case is not necessary suggest any recommendation to mitigate

this possible cause.

EFFLUENT TREATMENT

In the effluent treatment section we obtained seventy one scenarios which five scenarios of these were applied the LOPA and SIL methodologies. Two of these

scenarios are found in the relief gas scrubber V-06 and other three are found in the neutralizing basin TK-001A/B.

In the first initiating event the process parameter was Pressure and the deviation was less in the relief gas scrubber V-06. The possible cause was “Manual valve

GACF06 is open” which has the following safeguards “Operator procedures, training and response”.

With this possible cause we obtained a Severity of 4, Frequency of 3 and Risk of 12 S. In this part was acquired 1 Independent Protection Layer which is:

- Procedures

Performing the different calculations the Overall Consequence Frequency was , in this case is necessary suggest some recommendation to mitigate

this possible cause, which was:

79
- Change the manual valve located in the top of the vessel for a relief valve to prevent air pollution and system from exceeding specified overpressure. The

effectiveness of this device is sensitive to service and experience.

Performing the new calculations the New Overall was therefore this new result means that applying these recommendations may mitigate completely

this possible cause, hence the acceptable criteria of risk tolerated by the company is .

In the second initiating event the process parameter was Level and the deviation was less in the relief gas scrubber V-06. The possible cause was “P-11A/B

pumps shut down from either mechanical damage or loss of power.” which has the following safeguards “FIC 1290 with low flow alarm, Operator procedures,

training and response”.

With this possible cause we obtained a Severity of 5, Frequency of 3 and Risk of 15 S. In this part were acquired 3 Independent Protection Layer which are:

- BPCS

- Alarm

- Procedures

Performing the different calculations the Overall Consequence Frequency was , in this case is necessary suggest some recommendation to mitigate

this possible cause, which was:

- Due to is a damage in the pump recommend to install an active IPL as Human action with no more than 20 min of response time to simple well-documented

action with clear and reliable indications that the action is required.

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Performing the new calculations the New Overall was therefore this new result means that applying these recommendations may mitigate completely

this possible cause, hence the acceptable criteria of risk tolerated by the company is .

In the third initiating event the process parameter was Level and the deviation was high in the neutralizing basin TK-001A/B. The possible cause was “LIC 1725

fails stopping the pump P-13A/B.” which has the following safeguards “HS, Pump status with local start/stop, LT 1725 Ultrasonic, Operator procedures, training

and response”

With this possible cause we obtained a Severity of 4, Frequency of 4 and Risk of 16 S. In this part were acquired 2 Independent Protection Layer which are:

- Process design

- Procedures

Performing the different calculations the Overall Consequence Frequency was , in this case is necessary suggest some recommendation to mitigate

this possible cause, which was:

- Consider installing a passive IPL like a dike or underground drainage system to reduce the frequency of large consequences (widespread spill) of a tank

overfill.

Performing the new calculations the New Overall was therefore this new result means that applying these recommendations may mitigate completely

this possible cause, hence the acceptable criteria of risk tolerated by the company is .

81
In the fourth initiating event the process parameter was Level and the deviation was high in the neutralizing basin TK-001A/B. The possible cause was “Flooding in

the unit and the neutralizing basin area due to heavy rain” which has the following safeguards “Operator procedures, training and response”

With this possible cause we obtained a Severity of 4, Frequency of 4 and Risk of 16 S. In this part was acquired 1 Independent Protection Layer which are:

- Procedures

Performing the different calculations the Overall Consequence Frequency was , in this case is necessary suggest some recommendation to mitigate

this possible cause, which was:

- Consider installing a passive IPL like a dike or underground drainage system to reduce the frequency of large consequences (widespread spill) of a tank

overfill.

Performing the new calculations the New Overall was therefore this new result means that applying these recommendations cannot mitigate

completely this possible cause, so is necessary apply or suggest other recommendation to mitigate the initiating event, which was:

- Install a level indicator with a high alarm in the neutralizing basin tank

Performing the new calculations the New Overall was therefore this new result means that applying these recommendations may mitigate completely

this possible cause, hence the acceptable criteria of risk tolerated by the company is .

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In the fifth initiating event the process parameter was Level and the deviation was high in the neutralizing basin TK-001A/B. The possible cause was “Pumps P-

13A/B shut down” which has the following safeguards “HS, Pump status with local start/stop, LT 1725 Ultrasonic, Operator procedures, training and response”

With this possible cause we obtained a Severity of 4, Frequency of 4 and Risk of 16 S. In this part were acquired 2 Independent Protection Layers which are:

- Process design

- Procedures

Performing the different calculations the Overall Consequence Frequency was , in this case is necessary suggest some recommendation to mitigate

this possible cause, which was:

- Consider installing a passive IPL like a dike or underground drainage system to reduce the frequency of large consequences (widespread spill) of a tank

overfill.

Performing the new calculations the New Overall was therefore this new result means that applying these recommendations can mitigate completely

this possible cause, hence the acceptable criteria of risk tolerated by the company is .

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11. CONCLUSIONS

As a result of our research we can conclude that through the application of HAZOP, LOPA and SIL methodologies which were identified possible risks that may

occur in the Alkylation unit at the Ecopetrol’s refinery in Cartagena - Colombia.

Through the study of HAZOP which is a technique of risk identification based on the assumption that the risks, accidents or operability problems, occurring as a

consequence of a deviation of process variables with respect to normal parameters of operation in a given system and a determined stage, that’s mean, evaluate

in all lines and on all equipment’s the consequences of the possible deviations in all sections of the process. In our research we identified and analyzed the causes

and consequences of each of the deviations from the most important process variables which were temperature, pressure, level and concentration developed

through of guides’ words which are less, high and no. With this study were obtained 1092 scenarios found in thirteen section of the alkylation plant.

Furthermore, the scenarios that had significant and high risk were studied and sent to LOPA and SIL analysis. The LOPA analysis is a technique of risk

assessment which aims to determine the frequency of an undesired consequence that can be avoided through a set of protection layers. The approach evaluates

the worst case scenario, where all the protection layers must be failing for the consequence occurs; the frequency of this consequence is calculated using the

probability of failure on demand (PFD) of the different protection layers. With LOPA analysis 24 scenarios were found in nine units of the alkylation plant. Each of

these scenarios were calculated the frequency of the undesired consequence and compared with the acceptable risk criteria to identified the risk reduction

required, then the appropriate SIL level is selected.

This study also allowed fulfilling the overall objective of this research which was identified and reviews the best safety practices applying HAZOP, LOPA and SIL

for proper operation and performance of the Alkylation Unit catalyzed with Hydrofluoric Acid at the Ecopetrol’s Refinery in Cartagena- Colombia. To get the desired

84
result was necessary to make a review of the literature in order to obtain all the information about the process and how operate the alkylation unit including the

operational principles. Also a detailed analysis of hydrofluoric acid to consider all possible consequences if a leak occur in this study was done. Furthermore, we

found that the unit has a safety system considered fairly and count with the enough controllers and protection layers to prevent risks but in some parts of the plant

is necessary implement more safeguards to mitigate these hazardous scenarios.

12. FUTURE WORKS

We recommend perform the next activities for this research:

• Create an operational manual from of the recommendations obtained in the HAZOP, LOPA and SIL analysis
• Perform a study of Human Factor in the unit
• Evaluate the process design of the equipment’s
• Participation in international and national events
• Elaboration of papers for publication in indexed journals

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13. SCHEDULE
EXECUTION DATE
ACTIVITIES OBJECTIVE RELATED
Year: 2015

Make a literature review to get information about the process operating


Literature review about HF
and general information of the alkylation unit catalyzed with January 15 to January 20
Alkylation unit
hydrofluoric acid.

Development a detailed study about the how process worked and


Study detailed of the process found the principals variables. January 20 to January 30

Select the principals variables like


pressure, temperature, level, etc.
Development a detailed study about the how process worked and January 25 to January 27
to develop the safety study found the principals variables.

Identify and establish the nodes for Identify the operating principles of the alkylation unit to select the
corresponding nodes which they will be evaluated in detail in each
each section of the plant January 27 to May 15
section of the unit..

Create the HAZOP worksheet on Generate an Excel document that contain the recommendations and
Excel analysis obtained from the investigation divided by the nodes selected
and principals variables. February 2 to February 4

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Development of the HAZOP study
divided in the selected nodes Identify the criteria and process safety mechanisms used in the
alkylation plant with hydrofluoric acid and compare with the results
obtained to ensure that they are optimal for its operation. February 4 to May 15

Generate an Excel document that contain the recommendations and


Create the LOPA and SIL
analysis obtained from the investigation divided by the nodes selected May 16
worksheet on Excel
and principals variables.

Development of LOPA and SIL


Identify the criteria and process safety mechanisms used in the May 16 to May 30
study from the most significant
alkylation plant with hydrofluoric acid and compare with the results
scenarios obtained in HAZOP
obtained to ensure that they are optimal for its operation.
study

Analysis of results obtained to


make conclusions and Publish articles in index journals from the results obtained in the May 30 to Jun 5
recommendations of the project investigation.

Made a report to Mary Kay


O’Connor Process Safety Center
that includes general information Publish articles in index journals from the results obtained in the
investigation Jun 2 to Jun 13
about the project, the results,
conclusion, recommendations and
future work.

87
Development a report to Publish articles in index journals from the results obtained in the July 31 to August 5
Universidad de San Buenaventura investigation.
based in the results and
information about the process.

14. ABBREVIATIONS AND ACRONYMS

ALKAD: beta-picoline

BBS: Behavior Based Safety

BPD: Barrels equivalent per day

CO: carbon monoxide

CPI: chemical process industries

E: Environmental

ETA: Event Tree Analysis

F: Financial

FCCU: fluid catalytic cracking unit

FTA: Fault Tree Analysis

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HA: hydroxylamine

HAZAN: Hazard Analysis

HAZOP: Hazard and Operability Study

HF: hydrofluoric acid

HRA: Human Reliability Analysis

IPL: Independent protection layer

IR: Individual Risk

KOH: potassium hydroxide

LEL: element level low

LNG: Liquefied Natural Gas

LOPA: Layer of Protection Analysis

PFD: probability of failure on demand

PFDs: Process Flow Diagrams

PFDG: probability of dangerous failure on demand

PHA: Process Hazard Analysis

89
P&lDs: Piping & Instrument Diagrams

QRA: Quantitative Risk Analysis

RBD: reliability block diagram

RO: Restrictive Orifice

S: Safety

SIL: Safety Integrity Level

SIS’s: safety instrumented systems

SPLs: Safety Protection Layers

TF: tolerable frequency

15. ACKNOWLEDGMENTS

The authors are grateful to Dr. Sam Mannan and Ms.Valerie Green for the opportunity to they gave us to perform this internship at the center, for their support,
understanding and all the lessons learned who gave us during these six months so that this experience was rewarding and will be held with success each of the
objectives. Likewise we want to say thank you to all the members of the Mary Kay O'Connor Process Safety (MKOPSC) especially to Dr. Sonny Sachdeva, Dr. Yi
Liu, Dr. Richart Vazquez and Dr. Chad Mashuga.

Also, we want to say thanks to the Universidad de San Buenaventura-Cartagena for the formation that they gave us during our major and our mentor Dr. Juliana
Puello.

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Engineer Jorge Espinosa from Ecopetrol S.A for his collaboration, providing information to complete the project and especially for being available to give us
necessary information and each of the engineers who took some time to explain some things about the process that was studied.

Finally we want to say thanks to our parents who gave us their unconditional support, for supporting us financially in this process, to always be there guiding us
and encouraging us at difficult times. Likewise for providing the best legacy than they can give us: education.

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cartagena-de-indias-colombia/>

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Meyer E. Chemistry of Hazardous Materials. Regents/Prentice Hall. Englewood Cliffs, New Jersey OPEN CHEMESTRY DATABASE. Hydrofluoric Acid. Date: 04-
01-2015

Peterson R., 1998. Alkylate is key for cleaner burning gasoline. STRATCO, Inc. [https://web.anl.gov/PCS/acsfuel/preprint%20archive/Files/41_3_ORLANDO_08-
96_0916.pdf] Date: 04-02-2015

Producción Grupo Empresarial Alcanza los 750 mil barriles por Dia en junio. 2014 copyright wpadimn. Accessed March 11 2015 <
http://www.ecopetrol.com.co/wps/portal/es/ecopetrol-web/>

Refinería de Cartagena. 2015 COLPRENSA. Accessed March 11 2015 < http://www.elcolombiano.com/refineria-de-cartagena-iniciaria-operaciones-en-segundo-


semestre-de-2015-ecopetrol-DY1414306>

92
Ricardo R., 2011, Petroleum Refining. Atlantic international university. Honolulu, Hawaii. SIGMA-ALDRICH. 339261 - Hydrofluoric acid. Date: 03-30-2015

Simpson M y Kester M. (2007).Hydrofluric acid alkylation. ABB and ConocoPhilips develop a critical new process analysis tool. Texas: ConocoPhillips

UNC Environment, Health & Safety.Hydrofluoric Acid – Chemical Safety Information. Date:04-01-2015

UNITED STATES DEPARTMENT OF LABOR. OSHA Occupational Chemical Database: Hydrogen Fluoride. Date: 04-01-2015

U.S. EPA.Hydrogen Fluoride Study. Report to Congress, Section 112. Clean Air Act As Amended

Universidad de San Buenaventura Cartagena, n. d. Photograph. Accessed March 12 2015.http://www.guiaacademica.com/sitios/s408/index.aspx?id=408

Xueqi X, Guoying Z, Jianzhong C y Suojiang Z. (2012). Isobutane alkylation using acidic ionic liquid catalysts. China: Department of chemestry, Tianjin University.

93
17. LIST OF ANNEXES
Annex 1 Application of HAZOP methodology to Selective Hydrogenation Section

HAZOP WORKSHEET - ANNEX 1


Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
The Temperature Indicator (TI 4152)
Decrease in the works with a flow valve control in the
Temperature Indicator
separation time inlet stream.
with electrical signal in
1.1 .1 between Change the TI 4152 for a Temperature
the inlet stream (TI
hydrocarbon and Indicator Alarm Control to ensure the
Temperature of 4152)
water. correct control of the temperature and
inlet is cooler than 1 1 1-L
avoid possible fails
normal (<110°F)
Injection of N2
Constantly monitoring of the PIC 4007
due to the less
and valve PV-4007A for avoid possibles
1.1.2 Same as 1.1.1 pressure in the
ruptures and other damages that can
Surge Drum (D-
affect the separation
201)
Stream Consider install a Temperature
temperature from Same as 1.1.1 and Indicator Control in the stream from P-
1.1.3 TI 4008 1 1 1-L
LESS P-201A/B is cooler 1.1.2 201A/B to avoid possibles fails and
than normal losses of the olefins
TE 4152 failed and
send a wrong Install an additional temperature
Same as 1.1.1 and
1.1.4 signal to the TI Same as 1.1.1 1 1 1-L sensor (TE) with an electrical signal
1.1.2
4152 due to after of the TE 4152.
malfunctions
Install an additional pressure
FEED SURGE DRUM
1 TEMPERATURE transmitter (PT) conect with the PIC
D-201
Decrease in the 4007 to control the process and the
pressure tank (<75 Pressure Indicator Increase in the N2 operational profile
1.1.5 1 1 1-L
psig) due to Control (PIC 4007) flow into the tank Constantly monitoring of the PIC 4007
external events for avoid possible damages and
deviations of the process due to
external events
Temperature Indicator Separation time
Temperature of
with electrical signal in between
1.2.1 inlet is higher than 1 1 1-L Same as 1.1.1
the inlet stream (TI hydrocarbon and
normal (>110°F)
4152) water is higher.
Stream
temperature from
1.2.2 Same as 1.2.1 Same as 1.2.1 1 5 5-M Same as 1.1.3
P-201AA/B is
higher than normal
HIGH
TE 4152 failed and
send a wrong
1.2.3 Same as 1.2.1 Same as 1.2.1 1 1 1-L Same as 1.1.4
signal to the TI
4152
Increase in the Air pollution due
pressure tank due to an increase in
1.2.4 Same as 1.1.5 2 3 6-M Same as 1.1.5.
to generation the gas stream to
vapor (>75psig) the TEA system.

94
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Pressure Indicator
Control (PIC 4007); Install a Flow Indicator after valve PV
bypass system in the 4007 A and is recommendable make a
Break in the N2
valve PV 4007B Air pollution with control loops to ensure the correct
line after valve PV
(LWXS01) with two nitrogen and performance
1.3.1 4007A due to 3 2 6-M
manual valves before possible potential Constantly monitoring in the pipeline
corrosion or
and after control valve fire where we can get the correct status of
human factors
(GWSC01); Manual them for avoid possible changes or risk
valve in the enter of in the process
the tank GWCY01
Higher flow rate
of Nitrogen to the
Pressure of Nitrogen
flare to the plant
is 95 psig and pressure
flare header.
of the drum is 180 psig
Potential impact
using for decreasse
to the flare (loss
the pressure inside
of the flare).
FEED SURGE DRUM PIC 4007 fails the tank
1 PRESSURE LESS Releasing to the
D-201 opened PV 4007A Relief valve (Fuel gas Constant check if the Nitrogen purge
1.3.3 atmosphere 5 3 15-S
due to purges to the refinery flow worked in the permits limits
unburnt
malfunctions flare system)
Hydrocarbons,
Bypass system
potential ground
(LWCS01)
fires.
Manual valves before
Environmental
and after PV 4007A
issue and
(GWCS01)
potential for
personnel injury.
Bypass system in the
Due to the process count with
valve PV 4007B
excellent safety system is convenient
PIC 4007 fails (LWXS01) with two All Gas into the
activate bypass system until flow is
opening PV 4007B manual valves before tank is sent to the
1.3.4 5 1 5-M stabilize
due to and after control valve TEA system.
Constant check to the pipeline to
malfunctions (GWSC01); Manual Implode the tank
guarantee that the process operated in
valve in the enter of
the operational range
the tank GWCY01

95
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Increase the PIC 4007; TI 4152;
Same as 1.3.3.
temperature Safety valve PSV 4005 Hydrocarbon
Constant check of the TEA systen for
1.4.1 inside the tank due with a bypass system traces to the TEA 1 5 5-M
avoid leak of the olefins and the
to a desviation in (LWSC01) with two system
correct operability
the operation manual valves GACF04

LIC 4003; bypass


system in the valve PV
Gas accumulation
4007B (LWXS01) with
PIC 4007 fails into the tank
two manual valves
closing PV 4007B generating
1.4.2 before and after 5 1 5-M Same as 1.3.3
due to possible
control valve
malfunctions explosion due to
FEED SURGE DRUM (GWSC01); Manual
1 PRESSURE HIGH overpressure
D-201 valve in the enter of
the tank GWCY01
Increase in the
LIC 4003; LI 4001; Constant monitoring of level indicator
level of the tank
manual valves in the Entrainment of control LIC 4003 - 4001 to ensure the
(overfill tank) due
water exit of the tank fraction liquid correct level in this case 50% and the
1.4.3 to possibles 1 2 2-L
GBCF03 and a XV 4126 into the TEA correct separation
desviation in the
with a SIS UC30 system system. Opening the valves located in the exit
process like a
in the olefins exit of the tank until have the level range
damages in valves
Decrease in the
Impurities (volatile PIC 4007; FI 4000; XV Consider install a FY to get a sampling
diolefins flow at
1.4.4 impurities) in the 4125 with a SIS UC29 2 2 4-L wich worked to control of pollutants in
the out stream.
inlet stream system the stream
Air pollution

96
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Decrease in the
pressure tank.
FIC 4013 fails Bypass LWCS 01 with Due to the process count with
The NPSH is less
closing the valve two manial valves excellent safety system is convenient
1.5.1 than normal and 1 4 4-L
FV 4013 due to before and after activate bypass system until flow is
cause cavitation in
malfunctions control valve (GDCF01) stabilize
the pump P
201A/B.
Bypass system LWCS01
with two manual
LIC 4003 fails
valves before and
closing the valve
1.5.2 after GBCF01; Same as 1.5.2 1 4 4-L Same as 1.5.1
LV 4003 due to
Desviation system
malfunctions
SP0230 contected with
bypass system
Trawl Consider an automation of the oily
LI 4001 fails Manual valves located
hydrocarbon to water drainage system to avoid a
1.5.3 sending a wrong in the exit of the tank 1 1 1-L
system effluent overpressure and presence of
signal GWCS01
FEED SURGE DRUM treatment. pollutants
1 LEVEL LESS
D-201
Valve LWCS 01 that
Constantly check of the manual valve
located in the exit
LWCS 01 and LI 4001 is recommendable
of the oly water
1.5.4 Same as 1.5.3 Same as 1.5.4 1 1 1-L apply behavior based safety to ensure
fails complently
a good comunication between
open due to
employees
human errors
Tamponade in the Is recommendable close the XV 4125
inlet pipes due to Rupture due to to checnk the state of the pipeline and
prescence of overpressure in avoid possibles ruptures
XV 4125 with relief
1.5.5 impurities in the the inlet pipe 4 2 10-M Same as 1.3.2.
system and SIS UC29
stream and causing possible Install a Pressure Indicator in the inlet
incorrect potential fire. pipeline to avoid ruptures or leaks due
maintenance to a possible a overpressure
XV 4125 fails Due to the process has a security
completely closed Vent System and SIS Same 1.5.9 and sistem wich is bypass system is
1.5.6 4 1 4-L
due to UC29 1.5.2 recommendable if this consequences
malfunctions occur activate it

97
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Rupture due to Activate a PSV valve to stabilize the flow and
LIC 4003; LI 4001; Safety
overpressure in the outlet considere install a flow indicator before the
Tamponade in the valve PSV 4005 with a bypass
pipe causing possible pumps P 201A/B to avoid possibles
olefins exit piping system LWSC01 and two
1.6.1 potential fire. The NPSH is 4 2 8-M cavitations due to a increase or decrease of
due to prescence of manual valves before and
less than requested and the flow Periodic
impurities after safety valve (GWCY01
cause cavitation in the maintenance to the pipeline and reporting
and GACF04)
pump P 201A/B. the real state
Activate a PSV valve to stabilize the flow and
Bypass system LWCS01 with Entrainment of fraction considere install a flow indicator before the
LIC 4003 fails two manual valves before liquid into the TEA pumps P 201A/B to avoid possibles
opening the valve LV and after GBCF01; system. cavitations due to a increase or decrease of
1.6.2 5 2 10-M
4003 due to Desviation system SP0230 Overpressure in the tank the flow. Considere install a Flow Indicator
malfunctions contected with bypass causing possible Alarm before XV 4125 to control the flow that
system explosion. enter and avoid a overpressure and increase
of the temperature
LIC 4003; LI 4001; Safety
Tamponade in the valve PSV 4005 with a bypass
Same as 1.6.2. Install a Flow indicator in the oily water drain
oily water drain line system LWSC01 and two
1.6.3 Entrainment of oily water 3 3 9-M line to ensure the correct separation and
due to prescence of manual valves before and
FEED SURGE DRUM in the process stream. avoid of presence of possible contaminants
1 LEVEL HIGH impurities after safety valve (GWCY01
D-201
and GACF04)
FIC 4013 fails
Bypass LWCS 01 with two Due to the process count with excellent
opening the valve FV
1.6.4 manial valves before and Same as 1.6.2. 5 1 5-M safety system is convenient activate bypass
4013 due to
after control valve (GDCF01) system until flow is stabilize
malfunctions
Increase in the Install a flow indicator control which works
olefins and diolefins Same as 1.6.2. with valve XV 4125 to ensure the correct
1.6.5 XV 4125; LIC 4003; FIC 4013 5 2 10-M
flow that enter to Economic losses separation and avoid of presence of possible
tank contaminants
LI 4001 fails due to
LIC 4003; Manual valves
malfunctions
1.6.6 located in the exit of the Same as 1.6.3 3 1 3-M Same as 1.5.4
sending a wrong
tank GWCS01
signal
XV 4126 fails Install a flow indicator before the pumps P
1.6.7 completely closed No safeguard Same as 1.6.1 5 2 10-M 201A/B which works in a loop with valve XV
due to malfunctions 4126.
XV 4125 fails Due to the process has a security sistem wich
1.6.8 completely open Vent System and SIS UC29 Same as 1.6.2 5 2 10-M is bypass system is recommendable if this
due to malfunctions consequences occur activate it

98
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
FEED SURGE DRUM
1 1.7.1 LEVEL NO Same as Less Same as less Same as less Same as less
D-201
∆T in the Heat Exchanger Due to the process has a security sistem wich
decrease Break in the is bypass system is recommendable if this
XV 4026 fails closed pipe before the valve for consequences occur activate it considere
2.1.1 Vent System and SIS UC28 1 3 3-L
due to malfunctions overpressure. install a Flow Indicator Alarm after valve XV
Drawg of steam to the head 4026 to prevent that the flow increase or
condensate
decrease due to a fail
Decrease of the surface
Tamponade in the Implement a differential pressure gauge to
area
2.1.2 pipes of the heat PP; LIC 4108 1 2 2-L work with the input and output currents for
Break or leak in the pipes
exchanger the steam side
for overpressure
Periodic inspection and immediately report
about the real state of the heat exchangers
TI 4148 fails sending TW 4147; XV4026 with a Vent No important for avoid possible damages and deviations of
2.1.3 1 1 1-L
wrong signal System and SIS UC28 consequences the process due to external events
HEAT EXCHANGER Install a flow alarm indicator that works with
2 TEMPERATURE LESS
E-201 the temperture indicator TU 4148
TI 4144 fails sending
TW 4150 and manual valves
2.1.4 a wrong signal due to Same as 2.1.5 1 1 1-L Same as 2.15
GWCY01
malfunctions
The olefins Maintenance of the loops control between TI
2.1.5 temperature is lower TI 4144; TW 4150 Same as 2.1.2 1 3 3-L 4144 and valve XV 4026 for control the vapor
than normal flow to prevent possibles fails
Increase the temperature
Decrease in the inlet Implement a flow indicator which worked
XV4026 with a Vent System of the out the stream
2.1.6 stream flow of the 1 2 2-L with the valve XV 4026 to ensure the correct
and SIS UC28 ∆T in the Heat Exchanger
olefins control of the flow in this part of the section
decrease
Bypass system LWSS01 with
FIC 4020 fails closing Decrease in the inlet Due to the process has a security sistem wich
two manual valves before
2.1.7 the valve FV 4020 stream flow 1 2 2-L is bypass system is recommendable if this
and after contol valve
due to malfunctions Same as 2.1.8 consequences occur activate it
(GWSS01)

99
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
∆T in Heat Exchanger
increase causing a higher
temperature in the
olefins stream.
XV 4026 fails opened Economic losses due to
2.2.1 Vent System and SIS UC28 2 2 4-L Same as 2.1.1
due to malfunctions unnecesary use of steam
rate.
Increase in the pressure.
Increase in the condenser
level.
The steam
∆T in Heat Exchanger
temperature is
increase causing a higher
higher than
2.2.2 HEAT EXCHANGER Same as 2.1.2 temperature in the 1 2 2-L Same as 2.1.2
2 TEMPERATURE HIGH operating
E-201 olefins stream.
temperature (>307
Increase in the pressure.
°F)
The olefins
∆T in Heat Exchanger
2.2.3 temperature is Same as 2.1.7 1 3 3-L Same as 2.1.5
increase
higher than normal

Increase in the inlet Same as 2.2.3


XV4026 with a Vent System
2.2.4 stream flow of the Decrease the temperature 1 2 2-L Same as 2.1.6
and SIS UC28
olefins in the out stream.

FIC 4020 fails


opening the valve Increase in the inlet
2.2.5 Same as 2.1.7 1 2 2-L Same as 2.1.7
FV4020 due to stream flow. Same as 2.2.4
malfunctions

100
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSEEXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Lower production of
The temperature steam in the Periodic maintenance to the Heat
of inlet stream is condenser. Exchanger E-201 to ensure the correct
3.1.1 lower than Same as 2.1.7 More production of 1 4 4-L temperature to prevent possible fails
operating liquid phase in the that can change the operational
temperature. drum (Increase in the profile
out flow rate).
Increase of the ∆T
due to decrease in
LESS the inlet
TI 4148; TI 4133; TI
3.1.2 temperature of Same as 3.1.1 1 4 4-L Same as 3.1.1
4145
diolefins and
olefins in the heat
exchanger E-201
Maintenance to the valve XV 4026 to
XV 4026 fails
GWCS 01; Vent prevent ruptures, leaks or hold for
closed decreasing
3.1.3 System and SIS Same as 3.1.1 1 4 4-L corrosion or external events and
CONDENSER the steam flow
3 TEMPERATURE UC28 contamination of the other streams of
D-204 rate.
the process
Increase in the
The temperature pressure causing more
of inlet stream is production of steam.
PSV 4105; GWCS
3.2.1 higher than Increase in the flow 1 3 3-L Same as 3.1.1
01
operating rate of vapour in the
temperature. inlet of the heat
exchanger E-201.
Decrease of the ∆T
HIGH Same as 3.2.1.
due to increase in
More production of
the inlet
TI 4148; TI 4133; TI steam in the
3.2.2 temperature of 1 5 5-M Same as 3.1.1
4145 condenser and lower
diolefins and
production of liquid
olefins in the heat
phase.
exchanger E-201
XV 4026 fails GWCS 01; Vent Economic losses due to
3.2.3 opened due to System and SIS unnecesary use of 2 4 8-M Same as 3.1.3
malfunctions UC28 steam.

101
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSEEXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Decrease or NO
PI 4104; LIC 4108; Install a flow indicator in the inlet
steam flow due to
3.3.1 FIC 4027; PSV No exist condesation 1 2 2-L steam stream due to the process
error in the heat
4105 required more control in this part
exchanger
PI 4104; LIC 4108;
Decrease in the
3.3.2 FIC 4027; PSV No important 1 4 4-L Same as 3.1.1
inlet stream flow
4105 consequences
Decrease in the
Decrease in the steam
3.3.3 inlet stream Same as 3.3.2 1 3 3-L Same as 3.1.1
production
temperature
PSV 4105 fails Manual valve Maintance to the valve security valve
3.3.4 opened due to GWCS 01 located 2 4 8-M PSV 4105 to prevent possibles fails if a
CONDENSER malfunctions before PSV Same as 3.3.4 desviation can occur
3 PRESSURE LESS
D-204 Bypass system Due to the process has a important
LIC 4108 fails
LWCS01; manual safety system is recomendable
opening FV 4027 Decrease the level in
3.3.5 valves before and 1 3 3-L activate closing bypass system and
due to the condenser
after conrol valve the valve that before control valve to
malfunctions
(GWCS01) stabilize the process
Constant maintenance the pipeline to
prevent ruptures, leaks or hold for
Tamponade in the
Same as 3.3.7 corrosion or external events and
inlet piping due to
LIC 4108; FIC 4027; Overpressure in the contamination of the other streams of
3.3.6 prescence of 2 3 6-M
FV4027 inlet pipe and the heat the process Install
impurities in the
exchanger tubes. a flow indicator in the inlet stream
stream
due to the process required more
control

102
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Manual valves GBCF01 Explosion in the
XV 4026 fails Close the manual valve that located
GWCS 01; Vent condenser due to
3.4.1 opened due to 3 2 6-M before the control valve until process
System PSV 4105; PI overpressure inside
malfunctions is stabilize
4104 the vessel.
Bypass system Due to the process has a important
LIC 4108 fails Increase in the level
LWCS01; manual safety system is recomendable
closing FV 4027 causing dawg of
3.4.2 valves before and 1 2 2-L activate closing bypass system and
due to condensate to the
after conrol valve the valve that before control valve to
malfunctions steam line.
(GWCS01) stabilize the process
Increase in the
Install a flow indicator in the inlet
inlet flow stream
3.4.3 LIC 4108 Same as 3.4.2 1 4 4-L steam stream due to the process
due to external
required more control in this part
events
CONDENSER
3 PRESSURE HIGH Manual valve located
D-204 PSV 4105 fails
3.4.4 before the safety Same as 3.4.1 3 2 6-M Same as 3.3.6
closed.
valve GWCS 01
Increase in the
Periodic maintenance to the Heat
inlet stream
More production of Exchanger E-201 to ensure the correct
temperature due
3.4.5 PI 4104 steam in the 1 4 4-L temperature to prevent possible fails
to malfunctions in
condenser. that can change the operational
the heat
profile
exchanger
Tamponade in the Constant maintenance the pipeline to
exit piping due to prevent ruptures, leaks or hold for
FIC 4027; LIC 4108; PI
3.4.6 prescence of Same as 3.4.2 2 3 6-M corrosion or external events and
4104
impurities in the contamination of the other streams of
stream the process

103
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION

LIC 4108 fails Bypass system LWCS01;


Parcial condenser, Close the manual valve that located
opening FV 4027 manual valves before
3.5.1 disminution of the 1 4 4-L before the control valve until process
due to and after conrol valve
temperature of olefin is stabilize
malfunctions (GWCS01)
outside of E-201
FIC 4027 fails Due to the process has a security
Bypass system LWCS01
opening FV 4027 sistem wich is bypass system is
3.5.2 with two manual valves 1 2 2-L
due to recommendable closing if this
GWCS01 ; FE 4027
malfunctions Same as 3.5.1 consequences occur activate it
LESS
XV 4026 fails Manual valves GBCF01 Disminution of the
3.5.3 closed due to GWCS 01; Vent System temperature of olefin 1 4 4-L Same as 3.5.2
malfunctions PSV 4105; PI 4104 oustide of E-201

The olefins
Install a valve than worked with the TI
temperature is
4144 if is necessary increase or
high normal / The TI 4144; LIC 4108; FIC
3.5.4 Parcial condenser 1 3 3-L decrease the flow and control the
inlet stream of the 4027
variables like temperature, presure
D-204 is liquid-
and flow
vapour phase
Decreased heat
CONDENSER transfer.
3 LEVEL Increase in the
D-204 Overpressure in the D-
inlet stream to D-
204 and E-201. Install a Flow Control in the inlet of
204 due to LIC 4108; FIC 4027;
3.6.1 Liquid draw to the 3 1 3-L the D-204 to check the correct flow
malfunctions in FV4027
steam inlet. into the tank
the heat
Acumulation of the
exchanger
water condensate in
the E-201
Due to the process has a important
Bypass system LWCS01;
LIC 4108 fails safety system is recomendable
HIGH manual valves before
3.6.2 closing the valve Same as 3.6.1 3 1 3-L activate opening bypass system and
and after conrol valve
FV 4027 the valve that before control valve to
(GWCS01)
stabilize the process

XV 4026 fails Manual valves GBCF01


3.6.3 opened due to GWCS 01; Vent System Overpressure in the D-204
3 and
1 E-201
3-L Same as 3.6.2
malfunctions PSV 4105; PI 4104

Due to the process has a security


FIC 4027 fails Bypass system LWCS01
sistem wich is bypass system is
3.6.4 closing the valve with two manual valves 3 1 3-L
recommendable opening if this
FV 4027 GWCS01 ; FE 4027
Same as 3.6.1 consequences occur activate it
3.7.1 NO Same as Less

104
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Wrong operation in
the reactor due to Constant monitoring to the operation
Decrease in the
differents process conditions and equipments to
temperature in the
TIC 4022; TIC 4023; TI conditions. prevent ruptures, leaks or hold for
4.1.1 inlet stream of the 2 3 6-M
4044 Promote the corrosion or external events and
reactors 201/202
undesirable reactions contamination of the other streams of
(< 175⁰F)
decreasing the the process
lifetime of the
Promote the
undesirable reactions
TI 4043 A.B.C; TI 4044;
decreasing the
Decrease in the TAHH 4043
lifetime of the
4.1.2 hydrogenation A.B.C/4042/4044; TI 3 2 6-M Same as 4.1.1
catalyst. Economic
reactions 4053A.B.C; TI 4054; TAHH
losses due to decrease
4053 A.B.C/4054/4052.
in the desirable
(olefins).
Decrease in the
Increase in the non- lifetime of the
exhotermic Same as 4.1.2. catalyst.
4.1.3 2 2 4-L Same as 4.1.1
undesirable PI 4038; PI 4048. Production of
reaction undesirable
compounds
No reactions due Economic losses due to
4.1.4 to damages in the Same as 4.1.3 decrease in the 3 2 6-M Same as 4.1.1
catalyst desirable (olefins).
REACTORS PSV 4037 or PSV
4 TEMPERATURE LESS Same as 4.1.1 .
R-201/202 4047 fail opened
PI 4038; PI 4048; GACF Same as 4.1.1. Periodic maintenance to the safety
4.1.5 decreasing the 3 2 6-M
04; GBCF 03; GBCF 01 Air pollution valve PSV 4037/4047 to prevent fails
pressure in the
if a deviation can occur
reactor
The inlet stream Install a FY in the inlet stream to
4.1.6 has different FY 4014A/B. 3 2 6-M prevent precence of contaminants
composition Same as 4.1.2 that can affect the process
The ratio Decrease the all Periodic monitoring to the results of
Hydrogen/diolefin reaction causing FY 4014A/B to prevent prescence of
4.1.7 Same as 4.1.6 2 2 4-L
s is less than decrease in the heat contaminants that can affect the
normal produced. process
Decrease in the Periodic reactivation of catalyst to
Decrease in the Same as 4.1.2.
4.1.8 hydrogenation 3 2 6-M ensure the correct convertion and the
catalyst activity PDI 4041 /4051
reaction. reaction time
Increase in the Install a flow indicator control in the
GBCF01 with bypass
4.1.9 fresh charge to the Decrease the 1 2 2-L inlet stream which work with a
system LWCS01
reactor residence time control valve
Increase in the heat
absortion causing a
Increase in the
4.1.10 Same as 4.1.9 decrease in the 1 2 2-L Same as 4.1.9
inlet flow
average temperature
in the catalyst bed.
Increase in the FIC 4059: FV 4059:
4.1.11 Same as 4.1.10 1 2 2-L Same as 4.1.9
recirculation flow LBCF01: GBCF01

105
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Promote all reaction
due to increase in the
average temperature
in the catalyst bed.
Increase in the
Increase in the Implement a cooling system to the
polymerization of
4.2.1 inlet temperature Same as 4.1.1 3 2 6-M reactor for control the temperature
diolefins.
(>220⁰F) runway.
Increase the
desactivation rate of
catalyst causing
decrease in the
lifetime of it.
Promote the
hydrogenation
reaction (exhotermic
reaction) causing
Increase in the GBCF01 with bypass
4.2.2 increase in the average 2 3 6-M Same as 4.1.6
diolefins flows system LWCS01
temperature in the
catalyst bed.
Higher consume of the
hydrogen flow
Increase in the
composition of
4.2.3 Same as 4.1.6 Same as 4.2.2 2 2 4-L Same as 4.1.6
diolefins and
olefins
Increase the residence
REACTORS Decrease in the
4 TEMPERATURE HIGH time.
4.2.4 R-201/202 fresh charge to the Same as 4.1.9. 2 1 2-L Same as 4.1.9
Decrease in the heat
reactor
absortion.
The ratio
Hydrogen/diolefin
4.2.5 Same as 4.1.6 3 2 6-M Same as 4.1.7
s is higher than
normal Same as 4.2.1
4.2.6 Increase in the catalyst activity
Same as 4.1.8 Same as 4.2.2 2 2 4-L Same as 4.1.8
Decrease in the
4.2.7 charge flow to the Same as 4.2.4 2 1 2-L Same as 4.1.9
reactor Same as 4.2.4
Decrease in the
4.2.8 Same as 4.1.11 2 2 4-L Same as 4.1.9
recirculation flow Same as 4.2.4
Increase in the
hydrogenation
severity causing an
Periodic monitoring of the flow
Increase in the increase in the
indicator controls to prevent
hydrogen flow in temperature in the
4.2.9 FIC 4020/4046 3 3 9-M ruptures, leaks or hold for corrosion
the inlet of the R- reactors and potential
or external events and contamination
201 or R-202 catalyst damage.
of the other streams of the process
Economic losses due to
unnecessary use of the
hydrogen
PSV 4037 or PSV Same as 4.1.1.
4047 fails closed Overpressure in the R-
4.2.10 Same as 4.1.5 5 3 15-S Same as 4.1.5
due to 201 with possible
malfunctions explosion.

106
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Decrease in the
hydrogen flow in FIC 4014; FIC 4020; FV
4.3.1 Same as 4.1.1 3 2 6-M Same as 4.2.9
the inlet of the R- 4020; FIC 4046; FV 4046
201/202
Error in the control of
PI 4041A or PIC PID 4041; PI 4041B; PDI Install other PI or PIC in the inlet
pressure in the
4.3.2 4051A fails sending 4051; PIC 4051B - NO 3 2 6-M stream in case that fails PI 4041A or
reactor.
wrong signal SAFEGUARD PIC 4051A
Same as 4.1.1

PI 4041B or PIC Install other PI or PIC in the inlet


PID 4041; PI 4041A; PDI
4.3.3 LESS 4051B fails sending Same as 4.3.2 3 3 9-M stream in case that fails PI 4041B or
4051; PIC 4051A
wrong signal PIC 4051B

Bypass system LWCS01 Release of hydrogen to


The valve PSV 4037 Periodic monitoring of the safety
with two manual valves the atmosphere
4.3.4 or PSV 4047 fails 4 3 12-S valves PSV 4037 or PSV 4047 to
before and after safety causing air pollution.
open prevent desviation and possibles risks
valve (GBCF03)
Decrease in the Install a Flow Indicator in the inlet of
inlet stream of the reactor for prevent possible leak,
4.3.5 Delta PDI 4041 and 4051 Same as 4.1.1 1 5 5-M
olefins and rupture, hold or release to control
diolefins. this fail
Increase in the
REACTORS hydrogen flow in Same as 4.1.1
4 4.4.1 PRESSURE Same as 4.3.1 3 3 9-M Same as 4.3.1
R-201/202 the inlet of the R- Economic losses.
201 or R-202
Increase of the vapor
PSV 4037 or PSV
inside the reactor
4047 fails closed
4.4.2 Same as 4.3.5 impacting the reaction. 4 2 8-M Same as 4.3.5
due to
Overpressure.
malfunctions
Same as 4.2.1
Increase in the Constant maintenance to prevent
Obstruction in the PI 4041A-B; PDI 4041; PIC polymeritation. Coke ruptures, leaks or hold for corrosion
4.4.3 1 4 4-L
catalyst bed 4051A-B; PDI 4051 accumulation in the or external events and contamination
HIGH bed. Same as 4.1.9 of the other streams of the process
PI 4041A or PIC
4.4.4 4051A fails sending Same as 4.3.2 Same as 4.4.3 1 4 4-L Same as 4.3.2
wrong signal

PI 4041B or PIC
4.4.5 4051B fails sending Same as 4.3.3 Same as 4.4.3 1 4 4-L Same as 4.3.3
wrong signal

Increase in the
inlet stream of
4.4.6 Same 4.3.5 Same as 4.1.1 2 4 8-M Same as 4.3.7
olefins and
diolefins.

107
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Implement a process indicator control
LI 4040 or 4050 fails PIC worked with LI 4040/4050 to
PI 4038 - 4048; TI4043/
4.5.1 sendind wrong Increase in the reaction temperature
2 2 4-L ensure the real level and avoid
4053 A-B-C
signal overpressure and ensure the correct
separation
Tamponade in the
inlet stream due to Install a flow indicator in the inlet
LI 4040 - 4050; manual Same as 4.5.1
LESS prescence of pipe line of the reactors to ensure
4.5.2 valves LWCS01 and SP Overpressure in the 1 2 2-L
impurities in the the correct flow in the reactors to
0176 inlet line.
stream and bad prevent problems in the reactor
maintenance
FY 4014 a fails Bypass system LWSS01
LEVEL Due to the process has a excellent
closed FIC 4020 - with two manual valves
4.5.3 Same as 4.5.1 2 2 4-L safety system is recommendable
4026 due to before and after contol
opening to stabilize the process
malfunctions valve (GWSS01)

More nitrogen to the


flare header.
Potencial impact to the Constant monitoring and
PCV 4149 fails Relief valve (Fuel gas
flare (loss of the flare). maintenance of the valves and
4.5.4 HIGH opened increased purges to the refinery 5 3 15- S
Possible risk to constant check of the correct
the nitrogen flow flare system)
employees procedures
Enviromental
contaminant

Bypass with valve No occurs the desired


FY 4014 A/B fails LWSS01 with Manual reaction Periodic maintance to the FY 4014 A/B
REACTORS
4 4.6.1 partially closing FV valve located before (hydrogenation 3 2 6-M to prevent the increase or the
R-201/202
4020/4046 control valve GWSS01 ; reaction). contaminants in the flows
FT 4020/4046 Same as 4.1.4
Potential damaged to
the catalyst due to
catalyst poison.
Decrease in the Maintenance to the hydrogen filters
Promote the
4.6.2 purity of Hydrogen FIL 201A/B; PDI 4030 3 2 6-M to ensure the correct convert and
undesirable reactions.
stream reaction time
Increase in the
residence time in the
reactor
XV4024A/B fails Due to the process have a security
HYDROGEN
LESS partially closed FIC 4020; FT 4020; FE sistem wich is bypass system is
4.6.3 CONCENTRATION Same as 4.6.1 3 1 3-L
due to 4020 recommendable if this consequences
malfunctions occur activate it
Decrease the efficient
filtration causing
increase in the
Decrease in the
suspended solids in
4.6.4 quality of filter PDI 4030 3 2 6-M Same as 4.6.2
the stream.
material.
Potential damaged to
the catalyst due to
catalyst poison.
Decrease the efficient
Decrease in the install a flow indicator control in the
FIC 4020/4046 ; FT filtration. Reduce the
4.6.5 Hydrogen charge 2 1 2-L inlet stream due to the process
4020/4046 quality of sovent
flow. required more control in this part
circulated.

108
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Promote the desirable
Bypass with valve reaction and decrease
FY 4014 A/B fails
LWSS01 with Manual the diolefins
4.7.1 opening FV 2 2 4-L Same as 4.6.1
valve located before polimerization.
4020/4046
control valve GWSS01 Increase the life time
of the catalyst.
High purity of
4.7.2 No safeguard Same as 4.7.1 2 2 4-L Any important recommendation
Hydrogen
Increase the hydrogen
FIC 4020/4046 ; FT
flow and cause
HIGH XV4024A/B fails 4020/4046; FV
4.7.3 overpressure in the 4 2 8-M The system has enough safeguards
opened 4020/4046; FE 4020; PI
line with possible
4028
rupture of the pipe.
REACTORS HYDROGEN Increase the hydrogen
4
R-201/202 CONCENTRATION High quality of purity and promotes
4.7.4 PDI 4030 1 2 2-L Any important recommendation
filter material the hydrogenation
reaction.
Increase in the
4.7.5 hydrogen charge Same as 4.6.5 Same as 4.7.1 2 1 2-L Same as 4.6.5
flow
FY 4014 A/B fails
4.8.1 completely closing Same as 4.6.1 Same as 4.6.1 3 2 6-M Same as 4.6.1
FV 4020/4046
NO
XV4024A/B fails
completely closed
4.8.2 Same as 4.6.3 Same as 4.6.6 4 2 8-M Same as 4.6.3
due to
malfunctions

109
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Decrease in the
hydrogenation
reaction. Decrease in
the heat produced.
The feed stream of
Decrease in the bed Install a Concentration Indicator in
the process comes TI 4043/ 4053A-B-C; PI
temperature.Formatio the inlet of the process to prevent
4.9.1 with less diolefins 4041A-B; PDI 4041/ 4051; 1 5 5-M
n of undesired changes and desviations due to
and olefins PIC 4051A-B
reactions. contaminants
concentrations
Decrease in the
product quality.
Increase of the
hydrogen
The manual valve Opened bypass system until flow is
GBCF01 located in stabilize. Periodic inspection in the
the enter of the manual valve valve GBCF01 to prevent
4.9.2 LESS Bypass systrem LWCS01 Same as 4.8.1 1 3 3-L
reactors fails possibles human errors. It is
closed due to recommendable have a good
malfunctions communication between employees
Same as 4.8.1.
The feed stream of Increase the polymer
the process comes formation. Decrease in
with less diolefins the lifetime of the
and olefins catalyst. Formation of
concentration and H2S due at the reaction
4.9.3 Same as 4.9.1 2 4 8-M Same as 4.9.1
more contaminant sulfur and hydrogen.
such as sulfur, Inhibition of the
heavy metals, catalyst. Catalyst
DIOLEFINS AND
REACTORS water and caustic poisoning due to the
4 OLEFINS
R-201/202 soda. presence of heavy
CONCENTRATION
metals.
Increase in the
hydrogenation
reaction. Increase in
the heat produced.
Increase in the bed
temperature.
The feed stream of Increased hydrogen
the process comes consumption.
with higher Decrease in the H2
4.10.1 Same as 4.9.1 1 4 4-L Same as 4.9.1
diolefins and concentration.
olefins Insufficiency of
concentrations hydrogen in the
reactor. Increase of
HIGH
diolefins in the out
stream. Tamponade in
the reactor. Decrease
in the lifetime of the
catalyst.
Closed bypass system until flow is
The valve manual stabilize, is recommendable install a
GBCF01 located in loops control that worked with
the enter of the manual valve. Periodic inspection in
4.10.2 Bypass systrem LWCS01 Same as 4.9.1 1 5 5-M
reactors fails the manual valve valve GBCF01 to
opened due to prevent possibles human errors
malfunctions Is recommendable have a good
communication between employees

110
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Canalization in the
catalytic bed, catalyser
FIC 4014 fails desactivation,
Same as 4.10.1 and constant
closed FV 4014 - Bypass system LDCF01 - nonuniform
4.11.1 3 3 9-M monitoring to the TE 4043 A-B-C to
4020 - 4046 due to Bypass system LWSS01 distribution in the
ensure the correct temperature
malfunctions catalyser and decrease
un the quality of the
products
Due to process has a excellent safety
XV 4024 a/b valve
system is recommedable active
4.11.2 fails closed due to Same as 4.11.1 Same as 4.11.1 3 3 9-M
bypass system until process system is
malfunctions
stabilize
FIC 4059 fails
4.11.3 LESS Same as 4.11.1 Same as 4.11.1 3 3 9-M Same as 4.11.2
closed FV 4059
FY 4014 A-B fails
4.11.4 closed FV 4020 - Same as 4.11.1 Same as 4.11.1 3 3 9-M Same as 4.11.2
4046
Decrease in the Same as 4.11.2 and install a flow
Same as 4.11.1 and
charge flow in the indicator in the intlet stream due to
4.11.5 Same as 4.11.1 cavitation in the P-201 3 4 12-M
olefin charge drum the process required more control in
A/B pumps
D-201 this part
Tamponade in the
Same as 4.11.2,
inlet pipe line due
overpressure in the
4.11.6 to prescence of Same as 4.5.2 3 2 6-M Same as 4.5.2
line, posible explosion
impurities in the
fire
stream
The space velocity
LHSV is high than Due to process has a excellent safety
REACTORS
4 FLOW FIC 4014 fails normal, catalyser system is recommedable active
R-201/202
opened FV 4014 - Bypass system LDCF01 - desactivation, bypass system until process system is
4.12.1 2 4 8-M
4020 - 4046 due to Bypass system LWSS01 decrease in the quality stabilize and constant monitoring to
malfunctions of the products, the TE 4043 A-B-C to ensure the
decrease in the correct temperature
resident time.
Constant monitoring and Periodic
maintenance to pipeline to ensure
XV 4024 A/B valve proper operation of the process
XY 4024 A/B; bypass
4.12.2 fails opened due Same as 4.12.1 2 2 4-L Installation a pressure indicator that
system and SIS UC30
to malfunctions worked with some pressure
indicators valves to ensure that the
pressure profile don't change
HIGH FIC 4059 fails Due to process has a excellent safety
opened FV 4059 Bypass system LBCF01 system is recommedable active
4.12.3 Same as 4.12.1 2 3 6-M
due to with two manual valves bypass system until process system is
malfunctions stabilize
FY 4014 A-B fails Bypass system LWSS01
opened FV 4020 - with two manual valves
4.12.4 Same as 4.12.1 2 2 4-L Same as 4.11.3
4046 due to before and after contol
malfunctions valve (GWSS01)
FIC 4014 fails
Monitoring the vent system to
opened FV 4014
4.12.5 Same as 4.12.4 Same as 4.12.1 2 2 4-l prevent possibles fails and ensure the
due to
correct performance
malfunctions
Increase in the
XV 4125 with vent Constant monitoring to the charge
charge flow in the
4.12.6 system; FV 4013; bypass Same as 4.12.1 2 2 4-L flow to ensure proper operation of
olefin charge drum
system the process
D-201

111
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION

Drecrease in the The stripper would


temperature in the need more heat
inlet of stripper sumistred for reboiler Constant monitoring of the operated
due to an increase E203. system. Increase the recirculation
5.1.1 in the ∆T heat TIC 4017; TI 4139; 4063 Condensing of the 1 5 5-M flow from reboiler E-203. Increase the
exchanger E 202 vapor to ascend inside flow to reboiler E-203 and condenser
because the D-203 the stripper. drum D-203.
presented More procuct of lungs
changes. in the bottom.

Close the manual valve that located


PV 4051 fails TI 4135; bypass system Same as 5.1.1 before GBCF01 until process is
5.1.2 opened due to LBCF01 with two manual Flooding in the column 1 5 5-M stabilize
malfunctions valves GBCF01 Economic losses Decrease of recirculation flow in the
top and in the bottom.
The bypass system
fails due to TV
ZSO 4017B; VENT SYSTEM
5.1.3 4017B fails opened Same as 5.1.2 1 5 5-M Same as 5.1.2
XY 4017B
due to
malfunctions

TIC 4017 fails


opened the valves ZSC 4017A; ZSO 4017B;
5.1.4 Same as 5.1.2 1 5 5-M Same as 5.1.2
TV 4017 A/B due to XY 4017 A/B
malfunctions
STRIPPER
5 TEMPERATURE LESS
T-201 Partial condensation of
the steam
hydrocarburs in the
inlet of the column.
Decrease in the
Condensed of the
steam on the line LIC 4128; FIC 4127; FV Constant monitoring of the operating
5.1.5 vapor to ascend inside 1 4 4-L
of the condensates 4127 systems than work with D-203
the stripper.
drum D-203
More product of lungs
in the bottom.
Increase of level in the
bottom.

Condensing of the
vapor to ascend inside
Decrease in the the stripper. Decrease of the flow in the inlet of
5.1.6 recirculation flow PI 4116; TI4117 More product of lungs 2 4 8-M stripper to stablish the temperature
in the bottom in the bottom. operability profile
Flooding in the column
Economic losses

Potencial flooding.
Increase in the charge
Increase in the Decrease of the flow in the bottom
LIC 4083; FIC 4073; PDI o heat exchanger.
5.1.7 recirculation flow 2 4 8-M Constant monitoring of the operated
4064 More product of lungs
in the top system
in th bottom.
Economic losses.

112
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION

Decrease in the propane Increase of the steam flow in the bottom


Presence of water in
LIC 4078; LIC 4083; FIC concentration. Presence of from reboiler E-203.
5.1.8 the olefins stream 1 5 5-M
4073 lungs in the bottom. Cavitation Decrease of the flow in the inlet
outside of the D-202
in the P -203 A/B pumps. stripper.
Same as 5.1.6. Overpressure in
the line pipe. Flooded in the
exchanger generating a high
Install a alarm indicator worked with TI
level in the condensed drum D-
Tamponade in the 4115 due to the process required more
203 with partial condensation of
5.1.9 outside stream of the TI 4115; PDI 4164 5 2 10-M control in this part
the vapor. Possible fire
reboiler E-203 Constat monitoring to ensure proper
explosion due a overpressure
operation of the process
generating a risk to the
employees, enviroment and
equipment.
LESS
Sane as 5.1.6
Flooded in the exchanger
generating a high level in the
condensed drum D-203 with
Rupture in the outside
partial condensation of the
5.1.10 stream of the reboiler E- TI 4115; PDI 4164 5 2 10-M Same as 5.1.9
vapor. Possible fire explosion
203
due a overpressure generating a
risk to the employees,
enviroment and equipment.
Air pollution
Same as 5.1.6
Decrease in the olefins
Presence of vapor in the heat
5.1.11 inlet stream of the heat PV 4051: TI 4063 1 2 2-L Same 5.1.7
exchanger otside to condensate
exchanger E-203
drum.
STRIPPER
5 TEMPERATURE The stripper would need less
T-201 Increase in the
heat from reboiler E-203 Constant monitoring of the operated
temperature in the
Presence of hydrocarbon system.
inlet of stripper due to
vaporised in the top of the Decrease the recirculation flow from
5.2.1 an decrease in the ∆T of TIC 4017; TI 4139; 4063 1 5 5-L
issostroppier. Hydrogen reboiler E-203.
the heat exchanger E
contamination. Decrease in the Decrease the flow to reboiler E-203 and
202 because the D-203
propane concentration. condenser drum D-203.
presented changes.
Economic losses
Same as 5.2.1
Overpressure in the pipe line. Constant monitoring of the operated
Flooded in the exchanger E-202. system.
TIC 4017 fails closed the ZSC 4017A; ZSO 4017B;
5.2.2 Possible fire explosion 5 2 10-M Decrease the recirculation flow from
valves TV 4017 A/B XY 4017 A/B
generating a risk to the reboiler E-203.
employees, enviroment and Increase in the flow of the top.
HIGH equipment.

The stripper would need less


heat from reboiler E-203.
Presence of hydrocarbon
vaporised in the top of the
issostroppier. Hydrogen
Constant monitoring of the operated
Bypass System (LBCF01) contamination. Decrease in the
PV 4051 fails closed system.
Manual valves GBCF01 propane concentration.
5.2.3 interrupting the olefins 5 3 15-S Decrease the recirculation flow from
before and after at Economic losses. Overpressure
flow reboiler E-203.
pressure valve in the line pipe. Possible
Increase in the flow of the top.
rupture of the pipe line due the
overpressure causing a posible
fire explosion generating risk
for the employees, enviroment
and equipment.

113
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Same as 5.2.1 Inccrease the flow in the line of heat
The bypass system fails
ZSO 4017B; VENT SYSTEM Overpressure in the line. exchanger E-202.
5.2.4 due to TV 4017B fails 2 1 2-L
XY 4017B Interruptiom of flow after the Increase the olefins steam in the
closed
valve. bottoms of stroppier.
Increase in the Presence of hydrocarbon Decrease of the flow in the inlet of
temperature of olefins TI 4115; PDY 4064; LIC vaporised in the top of the stroppier.
5.2.5 2 2 4-L
inlent steam in the 4069; TI 4070 issostroppier. Increase the recirculation flow in the
bottoms. Economic losses top.
Increase of vapor in the top. Decrease in the recirulation flow in the
Decrease in the
TEMPERATURE HIGH Decrease in the quality bottoms.
5.2.6 recirculation flow in the FIC 4073 3 4 12-S
separation and charge of Increase in the flow of charge to
top.
olefins. stroppier.
Decrease in the recirculation flow in the
Decrease in the olefins bottoms.
5.2.7 PV 4051 Same as 5.2.1 2 4 8-M
charge of stripper Increase in the recirculation flow in the
top.
Increase in the steam Presence of hydrocarbon Increase of the flow of charge to
on the line of the LIC 4128; FIC 4127; FV vaporised on the top of the stroppier.
5.2.8 2 2 4
condensates drum D- 4127 stroppier. Decresse in the recirculation flow of the
STRIPPER 203 Economic losses. top.
5
T-201
Flooding in the column.
Increase the outside flow to reboiler.
Presence of lungs in the bottom.
Increase in the charge Increase de steam flow in the condenser.
5.3.1 PV 4051; TI 4063 Decreasse in the quality of 2 3 6-M
flow Decrease the recriculation flow in the
olefins. Hydrogen
top.
contamination. Economic losses

Decrease in the
Decrease the charge flow until flow is
5.3.2 recirculation flow in the TI 4115; TI 4070; LIC 4069 Same as 5.3.1 3 4 12-S
stabilize
bottoms
Decrease the charge flow.
PRESSURE LESS The tea system fails
PI 4064; PI 4065; PSV Losses of hydrogen. Decrease the recirculation flow in the
5.3.3 opened due to 3 2 6-M
4066 Air pollution botoms.
malfunctions
Open the security valves.
Potencial flooding.
Increase in the Increase in the charge o heat
LIC 4083; FIC 4073; PDI Increase in the recirculation flow in the
5.3.4 recirculation flow in the exchanger. More product 2 3 6-M
4064 bottoms
top of lungs in th bottom.
Economic losses.
Presence of water in Same as 5.3.1
LI 4078; LIC 4083; FIC
5.3.5 the hydrocarbon reflux The stripper would need more 2 2 4-L Same as 5.3.4
4073; PDI 4064
stream in the top heat from reboiler E-203

114
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Presence of hydrocarbon in the
Decrease of the recirculation flow in the
top of the column.
Decrease in the charge bottoms.
5.4.1 PV 4051: TI 4063 Hydrogen contamination. 2 3 6-M
flow Increase of the recirculation flow in the
Decrease in the olefins quality.
top.
Economic losses
Increase in the Decrease of the recirculation flow in the
PI 4064; PI 4065; PSV
5.4.2 recirculation flow in the Same as 3.4.1 2 3 6-M top.
4066
bottoms Decrease the charge flow
Decrease in the
LIC 4083; FIC 4073; PDI Same as 3.4.1
5.4.3 recirculation flow in the 2 3 6-M Same as 5.3.4
4064 Increase of steam in the top
PRESSURE HIGH top
Possible floofing into the
The tea system fails PI 4064; PI 4065; PSV stripper. Open the safe valve GBCF01 and GACF04
5.4.4 4 2 8-M
clossed 4066 Overpressure. to stabilize the pressure in the tower
Losses of olefins.
Increase the olefinsin the
STRIPPER Decrease the charge flow.
5 bottoms.
T-201 Tamponade in the Decrease the recirculation flow in the
Overpressure into stripper.
5.4.5 outside stream in the LIC 4069; TI 4079 5 1 5-M top.
Potencial flooding.
bottoms Decrease the steam flow in the
Hydrogen contamination.
condenser D 203
Economic losses.
Same as 5.5.1
Tamponade in the Overpressure in the pipe line Same as 5.4.1
PV 5051; TI 4063; LBCF01;
5.5.1 charge line of the Possible fire explosion with 5 2 10-M Constant monitoring to the system
LIC 4069
stripper possible risk to employees, controls
enviroment and equipment
5.5.2 PV 4051 fails closed LBCF01; TI 4063; LIC 4069 Same as 5.5.3 5 1 5-M Same as 5.5.3
LEVEL LESS
Same as 5.5.2
Rupture in the outside TI 4070; GWC01 - PP; LIC
5.5.3 Economic losses 5 2 10-M Same as 5.4.5
line in the bottom 4069
Escape of lighs
Tamponade in the Same as 5.2.6
Same as 5.5.3
5.5.4 recirculation line of the FIC 4073; PDI 4064 5 1 5-M Monitoring constant to the control
Same as 5.5.6
top systems

115
HAZOP WORKSHEET - ANNEX 1
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the removal of diolefins and light fractions of the olefins stream Study Section: Selective Hydrogenation
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Same as 5.4.1 Open the safe valve LBCF01 to stabilize
5.6.1 PV 4051 fails opened LBCF01; TI 4063; LIC 4069 4 1 4-L
Flooding in the column the operability profile
TV 4017 A/B fails
5.6.2 TI 4139; TI 4063; PV 4051 Same as 5.6.1 4 1 4-L Same as 5.3.1
opened
Overpressure in the D-201
Open the safe valve LWCS01 to stabilize
5.6.3 FIC 4073 fails closed LWCS01; SP 0182 Posible rupture of the pipe line 4 1 4-L
the operability profile
due to overpressute
LEVEL HIGH
Tamponade in the
Same as 5.4.5
5.6.4 outside line in the TI 4070; TW4179 5 2 10-M Same as 5.4.3
Decreasse in the olefins quality
bottom
Same as 5.6.1
LIC 4069 fails closed fv Same as 5.6.4 Open the safe valve LBCF01 to stabilize
5.6.5 Same as 5.6.1 5 1 5-M
4061 Increase the charge for the the operability profile
reboiler E 203
Decrease in the temperature
STRIPPER profile.
5 The feed stream of the
T-201 PDY 4064; LIC 4069; TI Decrease in the molecular
5.7.1 process comes with 2 2 4-L Same as 4.9.1
4115 weight on the plates along of
some diolefins
towel.
Decrease in the olefins quality
LESS The feed stream of the
process comes with less
CHARGE Constant monitoring and Periodic
diolefins and olefins Same as 5.7.1
COMPOSITION maintenance to pipeline and
5.7.2 concentration and more Same as 5.7.1 Contamination of the finale 2 3 6-M
equipments to ensure proper operation
contaminant such as product
of the process
sulfur, heavy metals,
water and caustic soda.
Decresse in the sensible heat.
Increase in the Constant monitoring to the variables like
Decrease in the molecular wight
5.8.1 HIGH molecular weight of the Same as 5.7.1 3 2 6-M pressure, flow and temeprature to
in the products of top and
charge prevent chances in the composition
bottom

116
Annex 2 Application of HAZOP methodology to Charge and Drying section

HAZOP WORKSHEET - ANNEX 2


Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is to remove humidity of the charge currents the unit Study Section: Charge and Drying
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S L R RECOMMENDATION
Install an Temperature Indicator in the
Temperature of inlet is Increase in the separation
inlet line to surge drum D-02 to
1.1.1 cooler than normal TI 4062; TI/TE 1001, TI 2495 time between hydrocarbon 1 1 1-L
monitoring this operational variable in
(<110°F) and water.
LESS the control room
Realize constant operator procedures,
Decrease in the pressure
1.1.2 PI 1364 Same as 1.1.1 1 3 3-L monitoring and training. Do a schedule
tank (<75 psig)
to realice the activities in this section.
Temperature of inlet is Decrease in the separation
TEMPERATURE
1.2.1 higher than normal Same as 1.1.1 time between hydrocarbon 1 4 4-L Same as 1.1.1
(>110°F) and water
Same as 1.2.1
HIGH Increase in the NPSH
Increase in the pressure
causing mechanical
1.2.2 tank due to generation Same as 1.1.2; PSV 1002 2 2 4-L Same as 1.1.2
damage in the pump P-
vapor (>75psig)
01A/B. Overpressure in the
drum D-02
Hydrocarbon spill to
Realize periodic maintenance and
atmosphere causing air
monitoring to the surge drum and
Manual valve GWCS03 is pollution and potential
1.3.1 PDI 1003; PI 1364/1021 5 2 10-M manual valves inmediatly report about
opened fire. Risk to the employees
1 SURGE DRUM D-02 the real state of the tank. Do a schedule
and the equipments.
to realice that action.
Economic losses.
Hydrocarbon spill to
atmosphere causing air
LESS pollution and potential
Realize a periodic maintance to the
fire. Risk to the employees
valve PSV 1002 to avoid this kind of
1.3.2 The PSV 1002 fails opened GACF04, PDI 1003, PI1364 and the equipments. 4 2 8-M
causes in the unit and is convenient do a
PRESSURE Economic losses. Decrease
schedule to realice this type of actions
in the NPSH causing
cavitation in the pump P-
01A/B
Manual Valve GBCF18 is
1.3.3 PI 2450, PDI 1003 Same as 1.3.2 4 2 8-M Same as 1.3.1
opened
The outlet stream is The surge drum count with the
Increase in the
Same as 1.1.1. PSV 1002; PI contaminated with vapor necessary safeguards, realize constant
1.4.1 temperature inside the D- 2 2 4-L
1364, TEA system of water. Potential fire and monitoring of pressures and
02
HIGH explosion in the drum temperature indicator.
Overpressure in the drum
The PSV 1002 fails closed or Bypass system around PSV
1.4.2 D-02. Potential explosion 3 2 6-M Same as 1.3.2
malfunctions 1002; PI 1364,
of the drum

117
HAZOP WORKSHEET - ANNEX 2
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is to remove humidity of the charge currents the unit Study Section: Charge and Drying
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S L R RECOMMENDATION
If this valve fails more than
30 minutes is potential to
LI 1005 with low level and
shutdown the Alkylation Consider adding a low flow alarm on FIC
FV 1000 fails closed or low-low alarm; Bypass
1.5.1 unit or go on isubutane 3 3 9-M 1000 and realice operator procedures,
malfunctions around FV 1000 valve with
circulation. Economic trainig and response
manual valve LWCS03
losses due to loss of
production.
Intall a Flow Indicator in the inlet line of
Same as 1.5.1. Increase the
the Surge Drum to monitoring the inlet
The FIC 4061 and/or LIC level in the bottom of
flow to the drum. Periodic maintenance
1.5.2 4069 fails closing the valve Same as 1.5.1. stripper T-201 causing 4 2 8-M
to the existing safeguards and valves.
FV 4061 overpressure and potential
Realize operator procedures and
explosion of the vessel.
training
LI 1005 with low level and Realize monitoring and constant
XV 2453 fails closed or low-low alarm; Position maintenance to the valve XV 2453 and
1.5.3 Same as 1.5.1 3 2 6-M
malfunctions indication (ZIC 2453) on XV operator procedures, training and
2453 response.
FV 1006 fails closed or Same as 1.5.1; FE 1006,
1.5.4 Same as 1.5.1 3 3 9-M Same as 1.5.2
malfunctions FT/FIC 1006
PI 1364, LIC/LT 1004, LG Same as 1.5.1
1009 for operator to verify Potential to send
Intall a Flow Indicator in the drain line of
LV 1004 fails opened or level in boot, LI 1005 with isobutane/olefin feed to
1.5.5 3 3 9-M oily water. Do periodic monitoring to
malfunctions low level and low-low the neutralizer drum D-19.
the state of the plant.
alarm, Bypass around LV Potential loss of feed.
1004 Economic losses
Potential fire and
explosion.Hydrocarbon
spill to atmosphere causing Install a Flow Indicator in the inlet line
air pollution. Risk to the of surge drum and flow indicator with
Manuals valves CBCF01/
employees and the lower and higher Alarm in the drum.
Rupture or leak in the LWCS03/ LBCF06 to close
1.5.6 equipments. Economic 4 3 12-S Constantly check of the pipe and realize
principle inlet line to D-02 the inlet flow for each
losses. Decrease in the maintenance to the pipes and vessels
streams; XV 2453; FV1006
1 SURGE DRUM D-02 LEVEL LESS NPSH causing cavitation in and training to the operator if this cause
the pump P-01A/B. occurs.
Decrease in the pressure
tank

Position valve indication


on XV 1516; FIC
1059C/1903C with low flow
Periodic maintenance to the XV 1516
alarm on E-28/E28A reactor
and realice operator procedures,
XV 1516 fails opened or feed lines; PSV 1002 on D-
1.5.7 Same as 1.5.1 2 3 6-M training and response. Consider install a
malfunctions 02 set at 170 psig, design
PT/PI with high pressure alarm on surge
pressure of vessel is higher
drum D-02
than maximum expected,
LI 1005 with high level and
low - low alarm
LI 1005 with low level and Install a Flow Indicator in the outlet line
Rupture in the outlet lines
1.5.8 low-low alarm, Manual Same as 1.5.6 4 3 12-S of the surge drum. Realize operator
of the drum D-02
valve GWCS03, XV 1516 procedures and training
Rupture or break in the oily Same as 1.5.6
1.5.9 Same as 1.5.8 5 2 10-M Same as1.5.5
water drain line Hydrocarbon load loss
Rupture in the inlet line
due to overpressure in it
causing possible potential
Tamponade in the inlet LI 1005 with low level and fire. Decrease in the NPSH
1.5.10 5 2 10-M Same as 1.5.6
pipes low-low alarm causing cavitation in the
pump P-01A/B
Decrease in the pressure
tank
Loss of inlet flow from Potential to shutdown
stripper bottoms trim alkylation unit or go on Consider adding a low flow alarm on FIC
LI 1005 with low level and
1.5.11 cooler, butamer unit, D-01, isobutane circulation. 3 3 9-M 1000 and realice operator procedures,
low-low alarm
D-12, P-07A/B, P-06A/B, E- Economic losses due to training and response
06A/B loss of production

118
HAZOP WORKSHEET - ANNEX 2
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is to remove humidity of the charge currents the unit Study Section: Charge and Drying
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S L R RECOMMENDATION
Higher consumption of
Acid in the reaction
section. Drag of acid to the
Isostripper section.
LI 1005 with low level and
Overpressure in the tank
FV 1000 fails opened or low-low alarm and high
1.6.1 causing possible explosion. 5 2 10-M Same as 1.5.1
malfunctions level and high - high
Drag of hydrocarbon to the
alarm, XV2453; PI 1364
TEA system Decrease in
the separation time
between hydrocarbon and
water
The FIC 4061 and/or LIC
1.6.2 4069 fails opening the Same as 1.5.1 Same as 1.6.1 5 2 10-M Same as 1.5.2
valve FV 4061
The valve XV 2453 fails
1.6.3 Same as 1.5.3 Same as 1.6.1 5 2 10-M Same as 1.5.3
opened or malfunctions
FV 1006 fails opened or Same as 1.5.1; FE 1006,
1.6.4 Same as 1.6.1 5 2 10-M Same as 1.5.2
malfunctions FT/FIC 1006
Drag the acid to the
Isostripper section
Overpressure in the tank
causing possible explosion.
Drag of hydrocarbon to the
TEA system. Drag of water
1 SURGE DRUM D-02 LEVEL HIGH
to the dryers D-03A/B.
Increase in the corrosion
Bypass system around
of equipments. Loss of acid
valve LV 1004 with manual Periodic maintenance to the bypass line,
LV 1004 fails closed for due to the increase of
valve LWCS03; LI 1005 with pipes an surge drum. Consider adding an
1.6.5 example bad transmitter or water. Potential for water 4 3 12-S
low level and low-low HF/Water acid analyzer on the E-28/E-
loss of instrument air buildup and water
alarm and high level and 28A reactor acid circulation loop
carryover to the dryer
high - high alarm
leading to potential
corrosion in downstream
system. Overtime, possible
leaks of acid in
downstream equipments
with possible exposure to
employees. Economic
losses

Rupture due to
overpressure in the outlet
pipe causing possible
LI 1005 with low level and potential fire. The NPSH is
Tamponade in the outlet
1.6.6 low-low alarm and high less than requested and 4 2 8-M Same as 1.5.8
pipes
level and high - high alarm cause cavitation in the
pump P-01A/B Drag of
hydrocarbon to the TEA
system

119
HAZOP WORKSHEET - ANNEX 2
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is to remove humidity of the charge currents the unit Study Section: Charge and Drying
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S L R RECOMMENDATION
Rupture due to
overpressure in the oily
water drain pipe causing
possible potential fire.
LI 1005 with low level and
Drag of hydrocarbon to the
low-low alarm and high
Tamponade in the oily TEA system
1.6.7 level and high - high 4 2 8-M Same as 1.5.5
water drain line Drag of water to the dryers
alarm, bypass system
D-03A/B. Increase in the
aroun valve LWCS03
corrosion of equipments.
Loss of acid due to the
increase of water.
Economic losses
LI 1005 with low level and
low-low alarm and high
level and high - high
1.6.8 Increase in the inlet flow alarm, Manuals valves Same as 1.6.1 5 2 10-M Same as 1.5.2
CBCF01/ LWCS03/ LBCF06
to close the inlet flow for
each stream
The NPSH is less than
HIGH Position valve indication requested and cause
1 SURGE DRUM D-02 LEVEL
on XV 1516; FIC cavitation in the pump P-
1059C/1903C with low flow 01A/B Drag of hydrocarbon
Periodic maintenance to the XV 1516
alarm on E-28/E28A reactor to the TEA system
The valve XV 1516 fail and realice operator procedures,
feed lines; PSV 1002 on D- Overpressure in the tank
1.6.9 closed on suction of P- 5 2 10-M training and response. Consider install a
02 set at 170 psig, design causing possible explosion.
01A/B feed pumps PT/PI with high pressure alarm on surge
pressure of vessel is higher Potential for loss of flow to
drum D-02
than maximum expected, reactor E-28 and EE-28A
LI 1005 with high level and leading to loss of
low - low alarm production. Possible
economic impact.

Potential for loss of


Pump run status indication; pressure on reactor feed
FIC 1006 with low flow header and loss of flow to
alarm; FIC 1059C/1903C reactors E-28/E-28A leading
Consider install a PT/PI with high
Damage in P-01A/B with low flow alarm, PSV of production. Potential 5 2 10-M
pressure alarm on surge drum D-02
1002, Design pressure of overpressure in the D-02
vessel, LI 1005 with high with loss of containment,
and high high level alarm. potential fire and
employees injuries

1.7.1 NO Same as Less Same as Less Same as Less Same as less

120
HAZOP WORKSHEET - ANNEX 2
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is to remove humidity of the charge currents the unit Study Section: Charge and Drying
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S L R RECOMMENDATION
Inlet temperature is lower The inlet line has enough safeguards but
2.1.1 LESS than operating TI 1025/1026 No significant consequences 1 1 1-L is necessary realize periodic
temperature (<102°F) maintenance to the indicators.

Decrease in the efficiency


of removal water from
olefins.
Inlet temperature is higher
Increase in the moisture
2.2.1 than operating Same as 2.1.1 2 2 4-L Same as 2.1.1
into dryers causing
TEMPERATURE temperature (>102°F)
saturation in the molecular
HIGH sieves and decrease the
drying cycle operation

Realice periodic maintenance to the


Increase the friction in the
2.2.2 Same as 2.1.1 Same as 2.2.1 2 2 4-L pipes and operator procedures and
inlet pipe
training.
Same as 2.2.2. Intall a pressure indicator
2.2.3 Increase in the pressure PSV 1027/1028 Same as 2.2.1 2 1 2-L
in each dryer.
Increase in the lifetime of
molecular sieves due to
decrease in the moisture
into dryers but decrease
XV 1350/1351 fails closed
the charge to the reaction
or malfunctions decreasing Same as 2.2.2. Install a flow indicator
2.3.1 XV 1352, XV 1353 step. 3 3 9-M
the inlet flowto olefins after valve 1350/1351
Possible fire explosion and
feed driers D-03A/B
leak of hydrocarbon due to
overpressure in the inlet
OLEFIN FEED DRIERS
2 pipe.
IN USE D-03A/B LESS
Economic losses
Air pollution due to
GACF 04, Bypass system hydrocaron escape. Injures
PSV 1027/1028 fails opened
2.3.2 around valves PSV to employees and 2 3 6-M Same as 2.2.2
or malfunctions
1027/1028 equipment. Economic
losses.
Decrease in the level due
XV 1352/1353 fails opened
Drain line with manual to reverse flow of olefins
2.3.3 PRESSURE depending of what dryer is 1 2 2-L Same as 2.3.3
valve GWCS03 which are sending to the
using
coalescer
Install a flow indicator control (FIC)
Increase in the charge to which works with a control valve in the
2.4.1 XV 1350/1351 Same as 2.2.1 2 2 4-L
the dryer inlet stream to monitoring the flow in
the dryer.
Possible fire explosion and
leak of hydrocarbon due to
Tamponade in the outlet overpressure in the outlet
2.4.2 PI 2548 5 2 10-M Same as 2.2.2
pipe. pipe.
HIGH
Decrease in the charge to
the reaction step.
Posible explosion due to
2.4.3 PSV 1027/1028 fails closed Bypass with valve LBCF06 overpressure into the tank 4 2 8-M Same as 2.3.3
.
Increase in the inlet
2.4.4 temperature to olefins TT/T1025, TT/TI1026 Same as 2.2.1 2 2 4-L Install a PDI in each olefins feed driers
feed driers

121
HAZOP WORKSHEET - ANNEX 2
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is to remove humidity of the charge currents the unit Study Section: Charge and Drying
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S L R RECOMMENDATION
Increase in the lifetime of
molecular sieves due to Install a analyzer in the inlet pipe and
Good separation in the decrease in the moisture realice sampling procedures in the
2.5.1 LESS No safeguards 2 3 6-M
charge drum D-02 into dryer. stream.Periodic operator procedures
Increase in the drying cycle and training.
operation.
WATER CONCENTRATION IN
LIC 1004 fails closing the
THE INLET STREAM
valve LV 1004 causing
2.6.1 Same as 1.6.5 Same as 2.2.1 2 2 4-L Same as 1.6.5
water drag in the olefins
HIGH stream.
Bad separation in the
2.6.2 charge drum D-02 due to Same as 1.2.2 Same as 2.2.1 2 2 4-L Same as 1.1.1
high temperature
Molecular sieves recently No hydrate formation in
2.7.1 AI 1030 2 1 2-L No important comments to do
regenerated the reaction
Install a analyzer in the inlet pipe and
Increase in the lifetime of
Decrease in the moisture realice sampling procedures in the
2.7.2 LESS Same as 2.7.1 molecular sieves. 1 1 1-L
of the inlet stream stream.Periodic operator procedures
Same as 2.7.1
and training.
Decrease in the sieves
2.7.3 No safeguards Same as 2.7.2 1 2 2-L No important comments to do
WATER CONCENTRATION IN operation time
OLEFIN FEED DRIERS THE OUTLET STREAM Increase in the sieves Decrease in the lifetime of
2 2.8.1 No safeguards 2 1 2-L No important comments to do
IN USE D-03A/B operation time molecular sieves.
Saturation of molecular Increase in the operational Schedule the regeneration of the
2.8.2 Same as 2.7.1 2 2 4-L
sieves cost due to constant dryer molecular sieves.
HIGH
2.8.3 Increase in the inlet flow Same as 2.4.1 regeneration. 2 1 2-L Same as 2.4.1
Hydrate formation in the Realize sampling procedures in the inlet
Increase in the moisture in
2.8.4 No safeguards (drum) reaction step. Acid 2 3 6-M stream and periodic maintenance to the
the inlet stream
losses. pipes and drum
Install a bypass system around the
2.9.1 XV 1350/1351 fails closed No safeguards Same as 2.3.1 2 3 6-M
valves XV 1350/1351
Leak or rupture in the inlet Install a flow indicator in the inlet pipe.
2.9.2 No safeguards Same as 2.3.2 3 3 9-M
pipe Periodic pipe maintenance
Possible fire explosion and
LESS Tamponade in the inlet Drain line with manual leak of hydrocarbon due to Same as 2.2.2. Install a pressure
2.9.3 4 2 8-M
pipe. valve GWCS03 overpressure in the inlet indicator in the inlet pipe.
INLET FLOW pipe.
XV 1352/1353 fails opened Install a manual valve after valves XV
2.9.4 depending of what dryer is No safeguards Same as 2.3.4 1 2 2-L 1352/1353 and do periodic maintenance
using to the valves, equipments and drum.
Increase the moisture into
the dryers. Decrease the
2.10.1 HIGH XV 1350/1351 fails opened No safeguards 2 2 4-L No important comments to do
lifetime of molecular
sieves.

122
HAZOP WORKSHEET - ANNEX 2
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is to remove humidity of the charge currents the unit Study Section: Charge and Drying
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S L R RECOMMENDATION
Realice periodic maintenance to the
FV 1023 fails opened Decrease in the valve FV 1023. Consider if it is possible
3.1.1 increasing the inlet flow FT 1023, GWCS03 regeneration efficiency to 1 2 2-L install a FI in the inlet line in the E-01 to
olefins in the E-01 the D-03A/B. control of the inlet flow in the control
room
TI 1540, FIC 1024, Bypass The line has enough safeguards but
TIC 1022 fails closing the
3.1.2 system with manual valve Same as 3.1.1 1 1 1-L realize constant monitoring to the
valve FV 1024
LESS LWCS 02 controllers, pipes and valves
FIC 1024 fails closing the
TIC 1022; Bypass system
3.1.3 valve FV 1024 decreasing Same as 3.1.1 1 2 2-L Same as 3.1.2
with manual valve LWCS 02
the inlet flow of steam
Decrease the heat transfer
Constant monitoring to the LIC 2455 and
Level in the condenser in the E-01.
3.1.4 LIC 2455 2 2 4-L valve LV 2455 and do an operator
increase Overpressure in the E-01.
procedures.
Same as 3.1.1
TEMPERATURE IN THE INLET
Inefficient use of steam.
STEAM
Possible increase in the
pressure of D-02 and D-
FV 1023 fails closed
FT 1023; Bypass system 03A/B.
3.2.1 decreasing the inlet flow 2 2 4-L Same as 3.1.1
with manual valve LWCS02 Increase in the
of olefins in the E-01
regeneration time due to
cooling time required for
it.
HIGH
Inefficient use of steam.
Difficulty in separating the
OLEFIN FEED DRIERS TIC 1022 fails opening the
3.2.2 TI 1540, FIC 1024,GDCF04. water from the olefins due 1 2 2-L Same as 3.1.2
3 IN REGENERATION D- valve FV 1024
to increase the coalescer
03A/B
temperature.
FIC 1024 fails opening the
3.2.3 valve FV 1024 decreasing TIC 1022; GDCF04 Same as 3.2.2 1 2 2-L Same as 3.1.2
the inlet flow of steam
Periodic maintenance to the valve XV
1346/1347. Install a flow indicator after
XV 1346/1347 fails closed No safeguards Same as 3.1.1 1 4 4-L valves 1346/1347 to monitoring the flow
in the inlet stream. Install a bypass
3.3.1 system around valves 1346/1347.
Bypass in the inlet lines of
LESS olefin regenerant heater E-
FV 1023/1024 fails closed or
3.3.2 01 around valves FV Same as 3.1.1 1 1 1-L Same as 3.1.1
malfunctions
1023/1024 with manual
valve LWCS 03
FLOW IN THE INLET STREAM Periodic maintenance to the pipes and
Tamponade in the inlet Drain line with manual
3.3.3 Same as 3.1.1 1 4 4-L consider install a pressure indicator or
pipe of olefin driers valve GBCF18
flow indicator in the inlet stream.
Increases the rate of
FV 1023 fails opened and removal of moisture
the regeneration steam go resulting in improved
3.4.1 GWCS 03 1 4 4-L Same as 3.1.1
out to the E-01 to the regeneration cycle.
HIGH
operational temperature. Increase regeneration
cycle time
XV 1346/1347 fails opened
3.4.2 No safeguards Same as 3.4.1 1 4 4-L Same as 3.3.1
or malfunctions

123
HAZOP WORKSHEET - ANNEX 2
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is to remove humidity of the charge currents the unit Study Section: Charge and Drying
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S L R RECOMMENDATION
Lower production of steam
in the condenser
More production of liquid
The temperature of inlet Preheating in E-01, TI1549 Install a temperature indicator to
phase in the drum
4.1.1 stream is lower than with low temperature 2 2 4-L monitoring this property in the control
(Increase in the out flow
operating temperature. alarm room. Realize operator procedures
rate) Decrease in the
pressure inside the
condenser
LESS
Increase of the ∆T due to
decrease in the inlet TI1549 with low
4.1.2 Same as 4.1.1 2 2 4-L Same as 4.1.1
temperature of olefins in temperature alarm
the heat exchanger E-01
Periodic maintenance and monitoring to
FV 1024 fails closed or TI 1540 with low Loss of heat input to E-01.
the valve FV 1024 and the control of it to
4.1.3 malfunctions on steam to E- temperature alarm, Delay the regeneration 1 1 1-L
avoid that this control send a wrong
21 Bypass around FV 1024 process.
signal to the control room.
TEMPERATURE
Increase in the pressure
causing more production of
The temperature of inlet
TI1549 with low steam
4.2.1 stream is higher than 1 2 2-L Same as 4.1.1
temperature alarm More production of steam
operating temperature.
in the condenser and lower
production of liquid phase

Decrease of the ∆T due to


HIGH
increase in the inlet
TI1549 with low
4.2.2 temperature of diolefins Same as 4.2.1 2 2 4-L Same as 4.1.2
temperature alarm
4 CONDENSER D-24 and olefins in the heat
exchanger E-01
TI 1540 with low
Economic losses due to
FV 1024 fails opened or temperature alarm,
4.2.3 unnecesary use of steam. 1 2 2-L Same as 4.1.3
malfunctions Bypass around FV 1024,
Same as 4.2.1
manual valve GDCF04
Install a flow indicator in the inlet steam
4.3.1 Decrease or NO steam flow PI 1357 No exist condesation 1 1 1-L line and realize monitoring in the line
and the pressure indicator.
Drag of steam to head
Decrease in the inlet Install a Flow Indicator in the inlet of
4.3.2 No safeguards condensate. Economic 1 2 2-L
stream flow the D-24
losses
Preheating in E-01, TI1549
Decrease in the inlet
4.3.3 with low temperature Same as 4.1.1 2 3 6-M Same as 4.1.1
stream temperature
alarm
Same as 4.3.1. Do periodic maintenance
Risk to the employees and
4.3.4 PRESSURE LESS Break in the steam pipe No safeguards 4 2 8-M to the pipes and operator procedures in
the atmosphere
the unit
Manual valve GWCS02
Realize monitoring and constant
4.3.6 PSV 2496 fails opened located before valve PSV Same as 4.3.4 2 3 6-M
maintenance to the valve PSV 2496.
2496
LV 2455 fails opened or Manual valve GWCS02 Decrease the level in the
4.3.7 3 3 9-M Same as 3.1.4
malfunctions located after valve LV 2455 condenser Same as 4.3.2
Rupture due to
Same as 4.3.2. Periodic maintenance to
Tamponade in the inlet overpressure in the inlet
4.3.8 No safeguard 4 2 8-M the pipes and consider install a pressure
pipe pipe causing possible
indicator
injuries to employees

124
HAZOP WORKSHEET - ANNEX 2
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is to remove humidity of the charge currents the unit Study Section: Charge and Drying
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S L R RECOMMENDATION
Increase in the level
Bypass system around
LV 2455 fails closed or causing dawg of
4.4.1 valve LV 2455; PI 1357; PSV 1 2 2-L Same as 3.1.4
malfunctions condensate to the steam
2496, LIC 2455, LG 2454
line.
Increase in the inlet flow
4.4.2 No safeguard Same as 4.4.1 1 4 4-L Same as 4.3.2
stream

Drain line in the top of the Explosion in the condenser


4.4.3 PSV 2496 fails closed. condenser, Design due to overpressure inside 3 3 9-M Same as 4.3.6
procedures the vessel.
PRESSURE HIGH

More production of steam


Increase in the inlet stream
4.4.4 PI 4104 ; PSV 2496 in the condenser and lower 1 3 3-L Same as 4.1.1. Same as 4.1.2
temperature
production of liquid phase

Same as 4.4.1
Rupture due to
Tamponade in the outlet Periodic maintenance to the pipes and
4.4.5 LIC 2455; PI 1357, LG 2454 overpressure in the outlet 3 3 9-M
pipe operator procedures and training
pipe causing possible
injuries to employees
LV 2455 fails opened or Manual valve GWCS02
4.5.1 Same as 4.3.2 2 2 4-L Same as 3.1.4
malfunctions located after valve LV 2455
TI 1540 with low
4 CONDENSER D-24 FV 1024 fails closed or Monitoring of the control FIC 1024 and
temperature alarm, Same as 4.3.1
4.5.2 LESS malfunctions on steam to E- 1 2 2-L valve FV 1024 and periodic maintenance
Bypass around FV 1024, PI Same as 4.1.3
21 to the existing safeguards.
1357
Decrease in the inlet
4.5.3 No safeguards Same as 4.3.2 1 2 2-L Same as 4.3.2
stream to the D-24
Decreased heat transfer.
Overpressure in the D-24
Increase in the inlet stream and E-01.
4.6.1 LIC 2455, LG 2454 2 1 2-L Same as 4.3.2
to the D-24 Acumulation of the water
LEVEL condensate in the E-01
Same as 4.3.2
Bypass system around
LV 2455 fails closed or
4.6.2 valve LV 2455; PI 1357; PSV Same as 4.6.1 2 1 2-L Same as 3.1.4
HIGH malfunctions
2496, LIC 2455, LG 2454
Same as 4.6.1
Increase of the condensate
TI 1540 with low
causing liquid drag to the
FV 1024 fails opened or temperature alarm,
4.6.3 steam line 2 2 4-L Same as 4.5.2
malfunctions Bypass around FV 1024,
Inefficient use of steam
manual valve GDCF04
Economic losses

4.7.1 NO Same as Less Same as Less Same as Less Same as Less

125
HAZOP WORKSHEET - ANNEX 2
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is to remove humidity of the charge currents the unit Study Section: Charge and Drying
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S L R RECOMMENDATION
PP in each inlet line and
outler to trim condenser,
Decrease in the time of
TW 1529/2502 in each inlet Install a flow indicator control in the
Increase in the secondary separation between the
line to trim condenser, TW inlet stream of each trim condenser.
5.1.1 cooling water flow to E- water and olefins. 1 2 2-L
1524/2500 in each outlet Operator monitoring to these flow
03/E-03A Presence of olefins in the
line to trim condenser, TI indicators.
oil water. Economic losses.
1013 with high
LESS
temperature alarm
Damage in the E-03/E-03A
5.1.2 decreasing the heat Same as 5.1.1 Same as 5.1.1 2 2 4-L Same as 5.1.1
TEMPERATURE transfer
Decrease in the inlet
TI 1013 with high Constant operator procedures and
5.1.3 stream temperature from E- Same as 5.1.1 1 2 2-L
temperature alarm monitoring to the existing safeguard
03/E-03A
Increase in the time of
Decrease in the secondary
separation between the
5.2.1 cooling water flow to E- Same as 5.1.1 1 2 2-L Same as 5.1.1
water and olefins.
03/E-03A
HIGH Economic losses.
Increase in the inlet stream Same as 5.2.1
5.2.2 temperature from E-03/E- Same as 5.1.3 Increase in the use of 2 2 4-L Same as 5.1.3
03A secondary cooling water
5 COALESCER D-01 Possible vaporization of
PV 1018 fails opened or PDI 1014; PI 1017;Manual light hydrocarbons. Periodic operator procedures, training
5.3.1 1 2 2-L
malfunctions Valve LWCS03/GWCS03 Inefficiency in the removal and response.
of water
PDI 1014; PI 1017, LIC 1015
Decrease in the level of
5.3.2 LESS with low and high level Same as 5.3.1 2 2 4-L Same as 5.3.1
the condenser
alarm, LG 1019
PSV 1016 fails opened or
5.3.3 Manual valve GACF04 Same as 5.3.1 2 2 4-L Same as 5.3.1
malfunctions
Manual valve GWCS03
5.3.4 No safeguards Same as 5.3.1 2 2 4-L Same as 5.3.1
PRESSURE opened
PV 1018 fails closed or Overpressure in the D-01
5.4.1 Same as 5.3.1 3 2 6-M Same as 5.3.1
malfunctions and E-03 A/B
Increase the level in the Same as 5.4.1
5.4.2 condenser due to increase Same as 5.3.2 Drag to Hydrocarbons to 2 3 6-M Same as 5.3.1
in the inlet flow rate the flare header
HIGH Increase in the
5.4.3 temperature inside the D- Same as 5.1.3 Same as 5.4.1 1 2 2-L Same as 5.3.1
01
Manual valve GWCY03
5.4.4 opened allowing the inlet Same as 5.1.3 Same as 5.4.1 3 2 6-M Same as 5.3.1
of Nitrogen in the vessel

126
HAZOP WORKSHEET - ANNEX 2
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is to remove humidity of the charge currents the unit Study Section: Charge and Drying
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S L R RECOMMENDATION
Presence of hydrocarbons
Manual valve GWCS03,
in the effluent treatment
Bypass system around
LV 1015 fails opened or section.
5.5.1 valve LV 1015, LG 1019, LIC 2 2 4-L Same as 5.3.1
malfunctions Increase of pollutants in
1015 with high an low leval
the effluent water.
alarm
Economic losses
Install a flow indicator in the inlet line of
Decrease in the inlet flow Same as 5.3.1
5.5.2 Same as 5.3.2 2 2 4-L olefin regenerant coalescer. Realize
rate to condenser D-01 Same as 5.5.1
operator procedures.
LESS
Overpressure in the outlet
PP in the inlet line to
XV 1353 fails closed or line to olefin feed driers. Constant operator procedures and
5.5.3 olefin regenerant 2 3 6-M
malfunctions Increase in the level of the monitoring to the existing safeguard
condenser E-02
driers. Same as 5.5.2
Release of hydrocarbon.
LEVEL
Potential explosion and
Manual valve GWCS03 LIC 1015 with low and high
5.5.4 fire. Potential risk to 3 2 6-M Same as 5.5.3
opened level alarm, LG 1019
employees and plant.
Economic losses
Presence of water in D-02.
Decrease in the lifetime of
the olefin feed driers D-03
LV 1015 fails closed or
5.6.1 Same as 5.5.1 A/B due an increase in the 2 2 4-L Open the manual valve LWCS03
malfunctions
water present in the
HIGH
stream .
Economic losses.
PP in the inlet line to Overpressure in the pipe
XV 1353 fails opened or
5.6.2 olefin regenerant line. Same as 3 2 6-M Same as 5.5.3
malfunctions
condenser E-02 5.6.1

127
Annex 3 Application of HAZOP methodology to Reaction section

HAZOP WORKSHEET - ANNEX 3


Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: Explains the reaction between the olefins and isobutane in the presence of hydrofluoric acid to obtain the alkylate Study Section: Reaction
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
DESCRIPTION
NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
NODE
Economically inefficient operation.
Increase in the inlet flow
Possible acid drag to isostripper section Install a flow indicator in the inlet
from of the Charge and Drying
1.1.1 FIC1059C/1903C due to speedup in reactors. Decrease in 2 1 2-L line when the streams are mixed to
section due to problem
the alkylate octanaje. Increase in the verify that the flow is right
operational
polymer production and pollutans.
The inlet stream of HF more
cooler than normal due to Periodic inspection and maintenance
1.1.2 operational problems in the TI1055/1907 Economically inefficient operation. 3 1 3-L of temperature indicators to avoid
ALKAD section or Acid settler operational problems in the reactors
D-04
The inlet stream of
Isobutane/Olefins more
Increase the production of organics
LESS cooler than normal due to
1.1.3 PI 1053/1905 fluorides. 3 1 3-L Same as 1.1.2
operational problems in the
Loss of acid
Charge and Drying section or
Isostripper section
Installation of a cooling water flow
REACTOR
1 TEMPERATURE Much cooling causing reactor cool. indicator and low flow alarm to
E28/28A
Increase in the primary Possible rupture in the pipes due to provide an immediate indication of
1.1.4 FI1328, TI1330, PI1332, TI 1548, PI1546 4 1 4-L
cooling water inlet flow rate overpressure. Economically inefficient cooling loss. Periodic inspections
operation and maintenance of the cooling
system to insure its integrity.
Economically inefficient operation.
Increase in the isobutene
1.1.5 TI1054/1906; FIC1047/1900 Possible acid drag to isostripper section 3 1 3-L Same as 1.1.2
recirculation flow rate
due to speedup in reactors.
Generation of polymer and pollutants Periodic inspection and maintenance
Decreasing in the isobutene causing a decreasing the octanaje of of the controllers to prevent that
1.2.1 FIC1047/1900 4 2 8-M
stream of recirculation alkylate.Secondary reaction in downstream send bad signal to the control room
equipment. or valve

HIGH Increasing of the temperature


1.2.2 Same as 1.1.2 Same as 1.2.1 4 2 8-M Same as 1.1.2
of the inlet stream of HF

Increasing of the temperature


1.2.3 of the inlet stream of the Same as 1.1.3 Same as 1.2.1 4 2 8-M Same as 1.1.2
isobutane and olefins

128
HAZOP WORKSHEET - ANNEX 3
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: Explains the reaction between the olefins and isobutane in the presence of hydrofluoric acid to obtain the alkylate Study Section: Reaction
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
DESCRIPTION
NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
NODE
Installation of a cooling water flow
indicator and low flow alarm to
provide an immediate indication of
cooling loss. Periodic inspections
and maintenance of the cooling
system to insure its integrity.
Installation of a high temperature
alarm to alert the operator in the
event of cooling function loss.
Runaway reaction with subsequent Installation of a high temperature
The cooling flow is
increase in the vessel pressure possibly shutdown system, that would
1.2.4 TEMPERATURE HIGH interrupted due to the FBCF01 TI 1548, PI1546 4 3 12-S
leading to a rupture or explosion of the automatically shutdown the process
fails closed
vessel in the event of a high reactor
temperature. The shutdown
temperature would be higher than
the alarm temperature to provide
the operator with the opportunity to
restore cooling before the reactor is
shutdown. Evaluation of the cooling
REACTOR
1 water source to consider any
E28/28A
possible interruption and
contamination of the supply.
Constantly monitoring of the
PI 1905 or PI 1053 fails send a Decrease in the operation conditions controllers to avoid undesirable
1.3.1 LESS PI 1052; PI 1904 2 2 4-L
bad signal causing inefficiency in the reactor reactions and maintain the
production of alkylate

Increasing of the temperature Overpressure in the reactors


Same as 1.3.1
in the reactors due the inlet Increase of the production polymer and
Monitoring of the cooling system to
1.4.1 stream is more higher than TI 1054/1548/1055, PI 1053/1052/1546 contaminants 4 1 4-L
maintain the operation temperature
normal or the cooling streams Increased loss of acid
PRESSURE in the range of operating
is less than normal Economic losses
HIGH Monitoring of the cooling pipe and
PSV valve to avoid an incident and
Rupture in the cooling pipe causing water
PSV 1048/1915 fails closed maintain the good operation in the
spill and problems in the operation
1.4.2 causing an overpressure in PI 1547/1916, TI 1049/1917 3 2 6-M reactors
condition. Problems in
the cooling pipe Install a PIC in the exit of the cooling
the operation condition of the reactors
pipe to control the pressure from the
control room

129
HAZOP WORKSHEET - ANNEX 3
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: Explains the reaction between the olefins and isobutane in the presence of hydrofluoric acid to obtain the alkylate Study Section: Reaction
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
DESCRIPTION
NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
NODE
Activate bypass system to control of
Decrease of octane alkylate product
Bypass system LBCF06 located in each the flow in case that fails
FIC 1059C/1903C fails closed Increase in the end point of alkylate
1.5.1 reactor around of the FV 1059/1903 5 2 10-M Constant monitoring of the pipeline
the FV 1059/1903 valve Increase in the polymer material
valve to avoid tamponade due to the
Increase of acid lost
contaminants

Same as 1.5.1
Isobutane flow FIC 1047/1900 Bypass system LBCF09 located in each
Increase in the temperature
1.5.2 fails closed the FV 1047/1900 reactor around of the FV 1047/ 1900 5 2 10-M Same as 1.5.1
Could occur secundary reactions in the acid
valve valve
settler and in the top of the isostripper

Decreasing of the flow of olefins and


butane to maintain the operation
Maintenance the pipe to avoid
Acid and aditive HC 1056 and
FE 1057/1909; FIC 1059C/1903C; TI tamponade or leak
1.5.3 1908 fails closed the HV Point increase in volatility acid 3 3 9-M
1056/1907 Install an alarm flow indicator and a
1056/1908 valves
bypass sistem in case that the valve
fails closed and maintain the flow in
the reactors
Constant monitoring to the pipe line
to avoid rupture and prevent an
Same as 1.5.2
incident
Rupture or hole in the pipe of Posible fire explosion
Decrease of the flow of olefins and
1.5.4 the Isubutane stream due to FIC 1047/1900 - PI 1053/1905 Air pollution Personal 5 1 5-M
isobutane to prevent an incident
the corrosion or overpressure Injures
Close the valves FV 1047/1900 to cut
Economic losses
the flow input

Constant monitoring to the pipe line


REACTOR to avoid rupture and prevent an
1 LEVEL LESS Same as 1.5.1 Posible fire
E28/28A incident
Rupture or hole in the pipe of explosion Air
Decrease of the flow of olefins to
1.5.5 the olefins stream due to the FIC 1059C/1905 - PI 1053/ 1905 pollution Personal 5 1 5-M
prevent an incident
corrosion or overpressure Injures
Close the valves FV 1059/1903 to cut
Economic losses
the flow input

Constant monitoring to the pipe line


to maintain the operation and avoid
Rupture or hole in the pipe of Same as 1.5.3 Catastrophic
a rupture
1.5.6 the HF and aditive stream due HC 1056/1908 events like, personal injuries event with 5 2 10-M
Install a bypass system and alarm
to corrosion or overpressure fatalities
flow indicator in case that the valve
fails closed and show the inlet flow

Tamponade in the pipe of the


Same as 1.5.6 Overpresure Constant monitoring to the pipe line
streams of HF and Additive
1.5.7 HC 1056/1908 in the line Posible fire 5 1 5-M to maintain the operation and avoid
due to the accumulation of
explision a tamponade
the contaminants

Total loss of acid flow to


both reactors leading to
uncontrolled ratio of HC/acid. With
continued HC feed flow,
Both pumps P-02A/C stop this can result in the potential
Maintenance of the pumps to avoid
from loss of power (Normally for polymer formation and
1.5.8 FI 1057/1909; Pump run status in PCS 4 2 8-M stop of operation and maintain the
operate two eventually acid runaway.
feed of the acid to the reactors
pumps). Potential for increased
corrosive environment which
could result in leaks in process, with
possible
personnel exposure to HF

130
HAZOP WORKSHEET - ANNEX 3
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: Explains the reaction between the olefins and isobutane in the presence of hydrofluoric acid to obtain the alkylate Study Section: Reaction
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
DESCRIPTION
NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
NODE
Install FI after the FV 1903/1059 valve
Decrease in the flow rate of isobutane/
Bypas system, GBCF16 Manual valve to show the flow inlet in the reactors
The controllers of the Olefins olefins flow
located after of the FV1059 valve; and maintain the relation
stream which are FIC 1059 Decrease of octane final product
1.6.1 GBCF 16 Manual valve located after of 3 1 3-L isobutane/olefins and HF/HC
C/1903 C fails, opening the FV Increase in the alkylate final point
the FV 1903 valve; TI 1051/1911; PI Constantly monitoring to the
1059/1903 valves Increase in the polimeric material
1053/1905 controllers to avoid fails in the
Increase acid losess
operation
Increase of octane of the alkylate product
LEVEL HIGH The controllers of the GBCF22 Manual valve located after of
decrease in the polimeric material
Isobutane stream which are the FV 1047 valve; GBCF 22 Manual
1.6.2 Economic operation inefficient 4 1 4-L Same as 1.6.1
FIC 1047/1900 fails opening valve located after of the FV 1900
Acid escape to the destilation separation
the FV 104771900 valves valve
column
The controllers of the Acid
Install FIC after the HV 1908/1056 and
and aditive stream which are
1.6.3 Same as 1.5.3 Catalyst deactivation 3 3 9-M loops work which work with those
HC 1056/1908 fails opening
valves
the HV 1056/1908 valves
Posible fire explosion Air pollution
Decrease in the alkylate product Constant maintenance of the pipe
GBCF 22 Manual valve located in each
Rupture or hole in the charge Decrease in the generation of polynmeric line to prevent rupture or fails in the
reactor before of the PI 1052/1904; XV
1.7.1 and drying pipe line due to materials Decrease in the 5 2 10-M process
1060 / 1902; PI 1052 / 1904; PI 1053 /
the overpressure or corrosion alkylate product Increase in Activate bypass system and interrupt
1905
the temperature of the E-28/28A the inlet flow
REACTOR Economic losses
1
E28/28A Tamponade in the inlet pipe Constant maintenance of the pipe
Overpressure in the pipe line
1.7.2 due to the accumulation of PI 1052/ 1904; PI 1053/1905 5 2 10-M line to prevent rupture or fails in the
Same as 1.7.1
contaminants in the pipe process
Decrease of octane alkylate product
Increased loss of acid
Maintenance of the Bypass system to
FIC 1047/1900 fails closed the Bypass system LBCF 09; GBCF22 Presence of secondary reactions in the
1.7.3 4 1 4-L maintain the flow and prevent
FV 1047/1900 valve Desviation valve; FE 1047/1900 equipment D-04, D-05 and top of the tower
operational problems in the reactors
RELATION ISOBUTANE - V-02 Same as
LESS
OLEFINS 1.7.2
The line from of Charge and
Drying of the controllers FIC Increase of octane alkylate product
1.7.4 Bypass system LBCF06; FE 1059/1903 5 1 5-M Same as 1.7.3
1059C/1903C fails, closed the Same as 1.7.2
FV 1059/1903 valve
Fails in the relacionador of
Decrease in the octane of product alkylate
Isobutane to Olefins XI Constant monitoring of loops control
Bypass system LBCF 06/09, TI Increasse in the final point of alkylate
1.7.5 2508/2512 closing the 3 2 6-M to avoid fails in the process and
1051/1911; PI 1053/1905 Generation of polymer material
FV1059C / 1903C or FV prevent that the valves fails closed
Increase in the acid lost
1047/1900 valves

Maintenance of the XV 1060/1902


The XV 1060/1902 valve of
valve to avoid a decreasing of the
1.7.6 the pipe from of the Charge FE 1059/1903 Same as 1.7.4 3 2 6-M
relation of the olefins and isobutane
and Drying section fails closed
and maintain the alkylate quality

131
HAZOP WORKSHEET - ANNEX 3
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: Explains the reaction between the olefins and isobutane in the presence of hydrofluoric acid to obtain the alkylate Study Section: Reaction
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
DESCRIPTION
NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
NODE
Increase of octane alkylate product
Decrease in the end point
GBCF 22 Manual valve located after of Decrease in the generation of polymeric
FIC 1047/1900 fails opened Decreasing the acid flow and
1.8.1 the FV 1047/1900 valve; TI 1051/1911; material 4 1 4-L
the FV 1047/1900 valve recycling the unreacted product
PI 1053/1905 Economically inefficient operation
Acid leakage to issostropier due increasse
in the reactors velocity
Fails in the relacionador of
REACTOR RELATION ISOBUTANE - Isobutane to Olefins XI
1 HIGH Same as 1.7.5 Economic
1.8.2 E28/28A OLEFINS 2508/2512 opening the TI 1051/1911; PI 1053/1905 2 3 6-M Same as 1.7.5
operation inefficient
FV1059C / 1903C or FV
1047/1900 valves
Decrease in the relation isubotane flow
The line from of Charge and between olefins flow
Drying of the controllers FIC The GBCF16 manual valve located Decrease of octane alkylate product
1.8.3 4 2 8-M Same as 1.8.1
1059C/1903C fails, opened the after the FV 1059/1903 Increase in the end point
FV 1059/1903 valve Increase in the generation of polymeric
materials
Increases acid viscosity causing decrease in Install Temperature Indicator Alarm
the sedimentation time of the acid Control in the inlet stream of the D-
Trawl of the acid to the isostripper section 04 to avoid decrease the
The exit stream from the The hydrocarbon stream contaminated sedimentation time of the acid in the
2.1.1 reactor comes is colder than TI 1051/1911 Increase the consumption of acid 4 1 4-L D-04
normal (<100°F) Increase the corrosion of the equipment Check of the operatin variable
LESS
due the acid Economic losses Monitoring of the operating
variables to maintain a good process
of separation in the D-04
The exit stream from the
2.1.2 Isostripper comes is colder TI 2359; PI 2537 same as 2.1.1 4 2 8-M Same as 2.1.1
TEMPERATURE
than normal (<100°F)
Install a Temperature Indicator (TI) in
the streams from the isostripper to
The exit stream from the Increase the sedimentation time causing maintain the temperature of
2.2.1 reactor comes is hotter than Same as 2.1.1 possibel trawl of acid to the isostripper 2 1 2-L operation in the D-04
ACID SETTLER normal (>100°F) section Monitoring of the operating
2 HIGH
D-04 variables to maintain a good process
of separation in the D-04
The exit stream from the
2.2.2 isostripper comes is hotter Same as 2.1.2 Same as 2.2.1 2 2 4-L Same as 2.2.1
than normal (>100°F)
Hydrocarbon drags to acid circulation
Install a low level alarm to alert the
Decreasing of the inlet flow system increasing the formation of
operator in the event of leak or hole
due to problems operational polymers and pollutants.
in the tank.
2.3.1 in the reaction section TI 1051/1911; DI 1071; LI 1072 Hydrocarbon spill to atmosphere. Potential 4 2 8-M
Periodic inspection and maintenance
causing a decreasing of the fire. Risk to the
to controllers to avoid fails and
PRESSURE LESS level employees and the equipments.
prevent that send bad signal
Economic losses.

Possible fire explosion Air


Rupture or leak in the outlet Constant maintenance of the acid
XV 1066/1067/1918 located before of pollution Risk to
2.3.2 stream of the acid due to the 5 2 10-M pipe to avoid a catastrophic incident
the pump P-02 A-C the employees and the equipments.
corrosion in the plant
Economic losses.

132
HAZOP WORKSHEET - ANNEX 3
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: Explains the reaction between the olefins and isobutane in the presence of hydrofluoric acid to obtain the alkylate Study Section: Reaction
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
DESCRIPTION
NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
NODE
Maintenance of the acid pipe to
Tamponade in the outlet pipe Hydrofluoric acid drags to isostripper
avoid accumulation of contaminant
2.4.1 (draining HF pipe) causing LI 1072; PI 1069 section Overpressure in the 4 2 8-M
in the pipe and prevent operational
increase in the acid level D-04
problems in the reaction section
Maintenance of the alkylate and
Tamponade in the outlet pipe Higher content of polymer in the stream. isobutane pipe to avoid
2.4.2 (draining alkylate and PI 1069 Low density making efficient separation of 3 2 6-M accumulation of contaminant in the
isobutane pipe) emulsion Overpressure in the D-04 pipe and prevent operational
PRESSURE HIGH
problems in the next section
Increase the level in the vessel causing
The XV 2461 valve located in Monitoring of the XV 2461 valve to
trawl of isobutane and alkylate to the
2.4.3 the isobutane and alkylate Same as 2.4.2 2 3 6-M avoid fails closed and maintain the
reaction section
pipe fails closed operation in the next section
Overpressure in the D-04
Maintenance of the PSV 1990 to
LBCF09 deviates the flow to the HF Overpressure in the D-04. Increasing of the
2.4.4 PSV 1990 fails closed 3 2 6-M prevent that fails closed and avoid a
Acid Blowdown temperature inside of the D-04
explosion due to the overpressure
Posible fire explotion Constant monitoring in the pipeline
Rupture in the inlet pipe of Air pollution due an acid escape to avoid problems in the process
2.5.1 the D-04 due to the TI 1051/1911 Equipment damage Risk to 5 2 10-M Install a pressure indicator in the line
overpressure in the pipe the employees to show the pressure and maintain
Economic losses the operation
Damages mechanic in the pumps Monitoring of the XV 1066 valve to
XV 1066 valve located before
Operational problems in the reactors E- avoid fails closed and maintain the
2.5.2 of the pump P-02A fails Same as 2.4.1 5 2 10-M
28/28A operation in the reactors to obtain a
opened
ACID SETTLER Cavitation in the pumps good alkylate
2
D-04 Decreasing of the inlet stream Bad separation of the acid in the D-04
Monitoring of the proces in the
LESS compound with acid, Inefficiency in the separation in the
reactors E-28/28A to maintain the
2.5.3 isobutane and alkylate is less Same as 2.1.1 isostripper section 5 2 10-M
production of alkylate and reduce
due to operational problems Trawl of hydrocarbon to the reaction
fails in the D-04
in the reactors section
Rupture or leak in the outlet
2.5.4 stream of the acid due to the Same as 2.3.2 Same as 2.3.2 4 2 8-M Same as 2.3.2
corrosion
LEVEL
Tamponade in the inlet pipe Operational problems in the reactors E-
Install a pressure indicator in the
of the D-04 due to the 28/28A Decreasing of the
2.5.6 Same as 2.5.1 3 2 6-M inlet pipe to show that the pipe no is
increase of contaminants in quality of the alkylate
obstructed
the pipe Overpressure in the pipeline
Increasing of the inlet stream
Trawl of acid to the Isostripper scetion
compound with acid,
Bad separation in the D-04
2.6.1 isobutane and alkylate is less Same as 2.1.1 4 1 4-L Same as 2.5.3
Contamination of the stream that enter to
due to operational problems
the reaction section
in the reactors
Trawl of acid to the isostripper section Monitoring of the XV 1066 valve to
HIGH Contamination of the alkylate and avoid fails opened and maintain the
2.6.2 XV 1066 valve fails closed Same as 2.4.1 3 3 9-M
isobutane stream operation in the reactors to obtain a
Economic losses good alkylate
Trawl of alkylate and isobutane to the Constant monitoring of the XV 2460
reaction section valve to avoid that fails closed and
2.6.3 XV 2461 valve fails closed PI 1069; LI 1072; PSV 1990; DI 1071 3 2 6-M
Operational problems in the isostripper prevent bad control in the reactors E-
section 28/28A

133
Annex 4 Application of HAZOP methodology to Acid Storage section

HAZOP WORKSHEET - ANNEX 4


Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: Describe the storage system, recirculation and drainage of hydrofluoric acid Study Section: Acid Storage
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
PIC 1033, PI 1034, Bypass The line has enough safeguards.
system around valve PV Inefficient displacement Periodic maintenance to the
PV 1033 fails closed or
1.1.1 1033, PI 1035 with high and of HF causing increase in 1 4 4-L controls and valves. Also, operator
malfunctions
lower pressure alarm, XI the level in the truck procedures, inspections and
LESS
1037 reference of level training.
Consider if it is possible install a
PSV 1032 fails opened or Nitrogen to ATM at safe
1.1.2 Manual valve GWCS03 1 3 3-L bypass system around safety valve
malfunctions location. Same as 1.1.1
PSV 1032
Overpressure in the
Same as 1.1.1. Confirm that the HF
system. Shutdown safety
Acid vendor container has
valve to D-30, increase in
overpressure protection.
PV 1033 fails opened or PIC 1033, XV 1039, interlock the losses of acid. HF can
1.2.1 2 2 4-L Note: UOP recommends using the
PRESSURE malfunctions UC03, emergency shutdown escape by breaking the
minimum design pressure of the
flexible lines, HF leak in
vendor container 125 psig assuming
the truck for the block
a 95 psig Nitrogen design pressure.
valves.
HIGH Increase in the truck level
causing overpressure in
Periodic maintenance to the pipe
the system. Possible
HF ACID CONTAINER and eliminate the presence of
1 Tamponade in the outlet explosion due to
(TRUCK) PI 1035 with high and lower pollutants in the tank to avoid
1.2.2 pipe causing level overpressure and release 3 2 6-M
pressure alarm, PI 1036 sedimentation in the pipe. Periodic
increase in the truck of HF with potential risk o
operator procedures, inspections
employees and
and training.
sourronding areas.
Economic losses
Considered but nothing
1.3.1 LESS
significant identified
PIC 1033, PI 1034, Bypass
Rupture in the N2 line or
1.4.1 system around valve PV Same as 1.1.1 1 4 4-L Same as 1.1.1
NO flow of nitrogen
1033
Tamponade in the outlet PI 1035 with high and lower
1.4.2 Same as 1.2.2 3 2 6-M Same as 1.2.2
pipe pressure alarm, PI 1036
LEVEL
Expose the container to Confirm that the HF Acid vendor
HIGH
the full nitrogen supply container has overpressure
pressure resulting in protection.
XV 1040 malfunctions PI 1035 with high and lower
1.4.3 potential overpressure 3 2 6-M Note: UOP recommends using the
closed pressure alarm, PSV 1032
leading to possible leaks minimum design pressure of the
of HF. Personnel safety vendor container 125 psig assuming
issues a 95 psig Nitrogen design pressure.

134
HAZOP WORKSHEET - ANNEX 4
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: Describe the storage system, recirculation and drainage of hydrofluoric acid Study Section: Acid Storage
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Air pollution. Potential
Manual valve GBCF22 in
Operator procedures, fire or injuries to Schedule the monitoring of this
2.1.1 the top of the acid 2 2 4-L
training and response employees and valve for operators
storage drum opened
sourronding areas
LESS
No important
Manual valves Periodic maintenance of valves.
PSV 1041 fails opened or consequences occurs if
2.1.2 GACF16/GBCF 22, Drain line 1 2 2-L Periodic operator procedures,
malfunctions this possible cause come
with manual valve GBCF22 inspections and training.
about
Damage in the pump P-
Periodic maintenance and
14A allowinfg the
2.2.1 P-14B Same as 1.2.2 2 2 4-L monitoring to pump P-14 A to avoid
increase the acid level in
mechanical damages in it.
the drum D-30
Constant monitoring to DI 1037.
PRESSURE Presence to
DI 1037, System display and Possible explosion and Periodic operator procedures,
2.2.2 hydrocarbons in the 4 2 8-M
remmote command nit potential fire inspections and training. Do
drum D-30
sampling procedures.
Unable to get the HF
HIGH
transferred into the
PI 1035 with high and lower Confirm that the HF Acid vendor
storage drum delaying
pressure alarm, Check valve container has overpressure
unloading. Potential to
between storage drum and protection.
Increase in the flow get storage tank contents
2.2.3 vendor container, PSV 1032 3 2 6-M Note: UOP recommends using the
from the process into the vendor container
set at 95 psig, Operator minimum design pressure of the
resulting overpressure
activated interlock U03 vendor container 125 psig assuming
leading to possible leaks
closes XV 1039/1040 a 95 psig Nitrogen design pressure.
of HF. Potential risk to the
employees
ACID STORAGE DRUM Expose the truck container
2
D-30 to the full nitrogen supply
pressure resulting in
XV 1040 malfunctions PI 1035 with high and lower Install a low level alarm in the acid
2.3.1 potential overpressure 3 2 6-M
closed pressure alarm, PSV 1032 storage drum D-30
leading to possible leaks
of HF. Personnel safety
issues

Increase in the level of Constant monitoring and inspection


the truck and to indicator and pipes.
Tamponade in the inlet
2.3.2 LESS PI 1035 overpressure in it with 4 2 8-M Eliminate the presence of water in
stream
potential explosion and the tank to avoid corrosion in the
HF release to atmosphere. pipe.

LEVEL Install a bypass system in this line


Same as 2.3.2.Possible and consider installing a flow
XV 1045 fails closed or mechanical damage to indicator in the inlet line after valve
2.3.3 No safeguards 4 2 8-M
malfunctions pump 14A. XV 1045 to monitoring the flow in
Reverse flow to D-30 this line. Periodic maintenance to
the valve and operator procedures.

Injection of Nitrogen , LAH Periodic maintenance and


The extraction nozzles No important
2.4.1 1038, PSV 1041 set at 300 1 1 1-L inspection to the controls, valves
are tamponade consequences
psig and alarms
Possible mechanical
HIGH Same as 2.4.1. Same as 2.2.1
damage to pump P-14A
Tamponade in the outlet Recirculation streams, LAH Install a flow indicator in the outlet
2.4.2 because is not working in 3 2 6-M
stream 1038 pipe to monitoring it constantly in
operational range.
the control room.
Economic losses

135
HAZOP WORKSHEET - ANNEX 4
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: Describe the storage system, recirculation and drainage of hydrofluoric acid Study Section: Acid Storage
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Periodic monitoring to the pressure
The acid is send to control to avoid the open of PSV
3.1.1 PSV 1079 fails opened Manual valve GBCF22 blowdown causing 1 2 2-L 1079 and do maintenance to the
economic losses. safety valve. Reestablish the
set point
LESS
Inefficient displacement Install o replace the PI 1081 for a PIC
Decrease in the inlet N2
3.1.2 PI 1080, PI 1081 of HF causing increase the 1 4 4-L which works in a loop control with
stream flow rate
level valve XV1077 to avoid human error

Manual Valve GBCF22, FI Increase the level in the


3.1.3 XV 1077 fails opened 1 1 1-L Same as 3.1.2
2516 acid dump header
Displacement of HF to the
acid dump header.
Possible explosion in the
Increase in the inlet N2 drum causing HF release Install a shutdown system to cut the
3.2.1 PSV 1079. PI 1080, PI 1081 2 2 4-L
stream flow rate and possible injuries to inlet flow of N2. Same as 3.1.2
the employees. Air
pollution. Economic
losses.
PRESSURE
HF drag to HF
blowdown.Possible
LAH 1083 and LAHH 1078 explosion in the drum
radioactive high level causing HF release. Install a high level alarm in the tank.
Increase in the level alarm, LI 1082 with high Unable to remove the acid Also, install a pressure indicator in
3.2.2 HIGH inside the drum or dump level from the system during an 4 2 8-M the top of the tank to monitoring
is full alarm on D-23, PI-1081 with emergency dump. If there this property. Verify the dump drum
high pressure alarm PI 1061 is a leak, there is greater capacity
, PI 1080 potential for personnel
injury. Air pollution.
Economic losses
3 ACID DUMP DRUM
Inadvertently have block
valves closed(these Unable to remove the acid
valves must be open Valves are designed to from the system during an
Consider install a bypass system
when the unit is running be locked open (LO), the emergency dump. If there
3.2.3 4 2 8-M around blck valves and realize
but can be closed during refinery has a safety is a leak, there is greater
periodic operator procedures
startup for example isolation system potential
during a dryout for personnel injury.
operation).
Once the piping design has been
completed, isometrics are to be
Can't get all the acid out. If sent to UOP to address timing for
The time is preset based there is a leak, there is dumping acid from equipment. UOP
Insufficient time for
3.3.1 on design inventory greater 3 3 9-M to verify and approve the unit dump
dumping a system.
calculations. potential for personnel timing based on inventory and
injury. piping layout. Flow test the acid
dump/pumpout system to verify the
timing of the dump sequence.
LESS

LEVEL Overpressure in the line


causing vibration in it with
possible explosion and
Install a pressure indicator in the
Tamponade in the inlet potential release of acid.
3.3.2 FI 2516 2 3 6-M inlet stream and a PSV to send the
stream Potential risk to
acid to another vessel (header).
employees and
sourronding areas. Air
pollution. Economic losses

XV 1077, FI 2516, LAHH 1078


Increase in the inlet
3.4.1 HIGH radioactive high level Same as 3.2.2 4 2 8-M Same as 3.2.2
flow rate
alarm

136
Annex 5 Application of HAZOP methodology to Cooling Water Tower – TAE- section

HAZOP WORKSHEET - ANNEX 5


Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: Discusses the cooling system of the cooling water of unit Study Section: Cooling Water Tower TAE
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Considered but nothing
1.1.1 LESS
significant identified
Higher cooling water
temperature. Potential
Constant check of the process to
Pressure safety valves, run overpressure of the
TEMPERATURE ensure the adequate functioning of
Bad functioning of cooling status indicators for fan alkylation unit leading to
1.2.1 HIGH 5 2 10-M the unit. Check all the procedures
tower fans motors, TI 1374, TI 1330, , TI flange leaks, loss of
with the same goal include the
1379, TI 1335, Shutdown. containment causing
cooling water system failures.
potential fire and
personnel injury.
PI-2036 with low pressure
alarm on the cooling water
header, Pressure Safety
Valves, Pressure Safety
Valves, Electrical power is
provided by two separate Potential for lower cooling
busses, Two of the electric water supply pressure
COOLING TOWER CT- motor driven pumps are resulting in lower flow
1
401 connected to the rates to the Alkylation
emergency power supply, Unit. Potential to Install a low pressure alarm on PI 1382
1.3.1 LESS Decrease in the inlet flow 5 2 10-M
Selection and sizing of the overpressure leading to in the high pressure steam supply
pump allows adequate flange leaks, loss of
cooling, even while three containment with
PRESSURE
pumps are running potential for
although with less pressure fire and employees injury.
cooling water system and
return temperatures higher
(normal operation is four
pumps in service), Two
steam turbines P-400A/E.
Potential overpressure
due to increase in the Check the pressure in each cooling
Cooling water supply PSVs in each heat
temperature of the water exchanger to guarantee the
1.4.1 HIGH blocked in exchangers with exchanger provided in the 2 2 4-L
cooling water side of the correct operation of this and avoid
heat still on exchangers cooling water side.
heat exchanger causing damage in the exchangers.
damage in it (leak).

137
HAZOP WORKSHEET - ANNEX 5
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: Discusses the cooling system of the cooling water of unit Study Section: Cooling Water Tower TAE
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Loss of cooling due to
decrease in the cooling
water basin level. Possible
overpressure and
explosions or leaks
PI 2036 with low pressure
causing loss of Constant check of this parameter and
LV 2004 fails closed alarm in the header, LI 2010
containment with revision of the existing safeguards.
1.5.1 decreasing the flow of with low level alarm, 5 2 10-M
potential fire and injuries Training to the operators to avoid
filtered water Bypass system, FI 2005,
to the employees and human errors.
PSVs.
equipments. Decrease in
the flow rate due to
decrease in the pressure
causing damage in other
LESS sections in the unit.
Grow up of biomass
Decrease in the flow rate of Periodic sampling procedures in the
Sampling, other treatment afecting the operability in
1.5.2 chlorinated cooling water 2 2 4-L treatment procedures. Training to the
procedures. the unit. Increase in the
LEVEL makeup operator to do this procedures safely.
fouling factor.
Bypass system, Sampling Potential grow uo of
procedures of the cooling contaminants in the
1.5.3 AV 2026 fails closed 2 2 4-L Same as 1.5.2
water. Other treatment cooling water. Increase in
procedures. the fouling factor.
Sampling procedures of the
1.5.4 XV 2014 fails closed cooling water. Other Same as 1.5.3 2 2 4-L Same as 1.5.2
treatment procedures.
1.5.5 XV 2013 fails closed Same as 1.5.4 Same as 1.5.3 2 2 4-L Same as 1.5.2
COOLING TOWER CT-
1 1.5.6 XV 2012 fails closed Same as 1.5.4 Same as 1.5.3 2 2 4-L Same as 1.5.2
401
Increase in the flow of
filtered water causing
LI 2010, high level alarm, potencial spill of this Periodic maintenance to the
1.6.1 HIGH LV 2004 fails open Bypass system with a block water in the cooling tower 2 2 4-L safeguards and check the parameters
valve, FI 2005 basin. Risk to the to avoid the spill of water.
employees and
environmental damage.
Increase in the pH causing
toxic environment in the
Periodic realization of sampling
Content of acid in the cooling water. Possible
1.7.1 Sampling procedures. 3 2 6-M procedures and constantly measure
cooling water system corrosion in the
of ph.
equipment. Risk to the
employees.
AI 2003, interlock UC 31, AIC
Presence of hydrocarbon
2026, AI 2027, Additive to
in the cooling water Install a measuring element level low
1.7.2 LESS Leak of hydrocarbon maintain equipment 4 3 12-S
COMPOSITION (WATER system. Possible fire and (LEL) in the cooling system
integrity, sampling
PURITY) employees injury.
procedures.
Presence of hydrocarbon
and acid in the cooling
AI 1050, AI 1912, AI 2028,, AI water system causing Maintenance to the reactor and
1.7.3 Leak in the reactor 3 2 6-M
2003 corrosion. Potential fire in monitoring of the fluoride analyzer.
the section and
employees injuries.
Considered but nothing
1.8.1 HIGH
significant identified

138
Annex 6 Application of HAZOP methodology to Isostripper section

HAZOP WORKSHEET - ANNEX 6


Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the separation of the various fractions generated in the reaction section Study Section: Isostripper
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Temperature of inlet
Install a Temperature Indicator (TI) in
streams from of the Possible fails in the V-02
1.1.1 LESS TI 1927; PI 1069 1 4 4-L each inlet streams to check and
reaction system is cooler causing bad separtion
maintain the operation temperature
than normal (<100°F)
TEMPERATURE
Temperature of inlet
The exit the heavy hydrocarbon
streams from of the
1.2.1 HIGH Same as 1.1.1 for the top of the D-05 1 4 4-L Same as 1.1.1
reaction system is hotter
Pump cavitation
than normal (<100°F)
Trawl the acid to isostripper
section
Vaporization of light
Maintenance of the D-05 to avoid
hydrocarbons causing
equipment damage
instability in the reaction
Install a Pressure Indicator in the tank
PIC 1921 fails closed the PV PI 1922; Bypass System section
1.3.1 3 3 9-M to control better the pressure of the
1921 valve LBCF09 Low suction pressure at the
D-05 Monitoring
pumps P-03A/B
of the pressure controller to avoid
Pumping instability
fails in the operation
Decreasing the inlet flow of
LESS
lateral isobutane from of the
isostripper tower
Maintenance of the D-05 to avoid
equipment damage
ISOSTRIPPER SURGE
1 GBCF22 Manual valve Install a Pressure Indicator in the tank
DRUM D-05 PSV 1923 fails opened
located before of the to control better the pressure of the
1.3.2 located in the top of the D- Same as 1.3.1 3 3 9-M
PSV 1923; GFCS05 D-05
05
Manual valve Monitoring and maintenance of the
PRESSURE PSV 1923 valve to prevent that failed
open
Maintenance of the D-05 to avoid
equipment damage
Overpressure in the reactors Install a Pressure Indicator in the tank
PSV 1923 fails closed
GFCS05 Manual valve; E28/28A and Drum D-04 to control better the pressure of the
1.4.1 located in the top of the D- 2 3 6-M
LFCS05 Manual valve The flow of hydrocarbon could D-05
05
return to the reaction section Monitoring and maintenance of the
PSV 1923 valve to prevent that failed
closed
HIGH Maintenance of the D-05 to avoid
Increase of temperature in
equipment damage
the tank due to that stream
1.4.2 Same as 1.1.1 Same as 1.4.1 2 4 8-M Install a Pressure Indicator in the tank
come more hotter than
to control better the pressure of the
normal
D-05
Same as 1.4.1 Increasing
PIC 1921 fails opened the the inlet flow of lateral
1.4.3 Same as 1.3.1 2 3 6-M Same as 1.3.1
PV 1921 valve isobutane from of the
isostripper tower

139
HAZOP WORKSHEET - ANNEX 6
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the separation of the various fractions generated in the reaction section Study Section: Isostripper
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION

Bypass LBCF09 located increasing the inlet flow of


PIC 1921 fails closed the PV Monitoring constantly of the PIC 1921
1.5.1 in the inlet pipe of the lateral isobutane from of the 2 2 4-L
1921 valve controller to prevent fails operating
top of the D-05; PI 1922 isostripper tower

GBCF22 Manual valve Operation problems in the Install a Flow Indicator (FI) in the
LIC 1924 or FIC 1933 fails
1.5.2 located before of the isostripper section causing bad 1 3 3-L inlet of the isostripper to show
opened the FV 1933 valve
FV 1933 separation correct flow for a good operation
Bypass LBCF09 located
FIC 1932 fails closed the FV Monitoring constantly of the FIC 1932
1.5.3 in the reflux pipe of Same as 1.5.2 1 2 2-L
1932 valve controller to prevent fails operating
the D-05
Maintenance of the valve to avoid a
Same as 1.5.2 decreasing in the level of the D-05
1.5.4 XV 2461 fails closed PI 1069 3 2 6-M
Same as 1.5.1 Install a Bypass system to maintain
LESS
the flow to the D-05
Tamponade of the inlet
Maintenance of the pipe to avoid
pipe in the top due to Same as 1.5.1
1.5.5 PIC 1921; PI1922 3 3 9-M rupture of the pipe due to the
accumulation of the Overpressure in the tank
overpressure and an incident
contaminants
Tamponade of the inlet
1.5.6 pipe in the bottom of the D- TI 1927 Same as 1.5.5 3 2 6-M Same as 1.5.6
05
Possible fire explosion
Air pollution
ISOSTRIPPER SURGE Rupture in the inlet pipe of
1 1.5.7 LEVEL PI 1069 Injuries to the employees 5 3 15-S Same as 1.5.6
DRUM D-05 the bottom of the D-05
Equipment damage
Economic losses
Instability in the control of the
pressure in the reaction section
Trawl of liquid hydrocarbon to
PIC 1921 fails opened the
1.6.1 Same as 1.3.1 the Blowdown system 3 3 9-M Same as 1.5.1
PV 1921 valve
Pump gavitation
Operation problems in the
isostripper section

Bypass system LBCF09


LIC 1924 or FIC 1933 fails
1.6.2 located after of the FE Same as 1.6.1 2 3 6-M Same as 1.5.2
HIGH closed the FV 1933 valve
1933
GBCF 22 Manual valve
FIC 1932 fails opened the FV
1.6.3 located after of the FV Same as 1.6.1 3 3 9-M Same as 1.5.3
1932 valve
1932 valve
1.6.4 XV 2461 fails opened Same as 1.5.7 Same as 1.6.1 3 2 6-M Same as 1.5.4
TI 1927; GBCF 22
Same as 1.6.1 Maintenance of the valve to avoid a
1.6.5 XV 1928/1930 fails closed Manual valve located 3 1 3-L
Damage to the pump increasing in the level of the D-05
before of the TI 1927
Tamponade in the exit pipe
1.6.6 TI 1927 Same as 1.6.5 3 2 6-M Same as 1.5.5
of the D-05
1.7.1 NO Same as Less Same as Less Same as Less Same as Less

140
HAZOP WORKSHEET - ANNEX 6
Project Title: Application of HAZOP, LOPA and SIL to the alkylation unit catalyzed with hydrofluoric acid Date: Febrary to June Page 1 of 1
Process: The objective is the separation of the various fractions generated in the reaction section Study Section: Isostripper
HAZOP Team: Figueroa Stefanny, Lombana Stefany and Ruiz Ingry Meeting days: All days of Febrary to June
NODE DESCRIPTION NODE PROCESS PARAMETERS DEVIATION POSSIBLE CAUSE EXISTING SAFEGUARDS CONSEQUENCES S F R RECOMMENDATION
Light leakage at the bottom
Alkylate pollution with HF
Increase the flow in the E-11/11 A ,
Temperature of inlet Increase the reflux flow in the
the reboiler E-12 and the furnace H-
2.1.1 stream is cooler than TI 1562; TI 1563 bottom 3 3 9-M
01
normal (&l