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Chemical Process Design Problem Set 1

Gabriel S. Gusmão Dr. Tam CHE 175A Problem Set 1 Due date: 02/02/12

1. A plant employs 1500 full time workers in a process with a FAR of 5. How many industrial related deaths are expected per year?

FAR is an acronym for Fatal Accident Rate which consists in the number of fatalities based on 1000 employees active their whole lifetimes; according to Crownl and Lovar 1 , FAR is defined as:

10

The fatality rate (FR) comprehends the number of expected fatalities per person per year.

Assuming that a fulltime worker works 8 hours per day and 300 days per year, it follows that:

5

100,000,000

8 300 1.2 ⋅ 10

1

1500 0.18

1 See ref. I

Gabriel S. Gusmão Dr. Tam CHE 175A Problem Set 1 Due date: 02/02/12

2. Estimate the flash point of a solution of 50 mol% water and 50 mol% ethanol.

From Perry’s Chemical Engineering Handbook, 7 th edition, the vapor pressure of ethanol and water from DIPPR method are given by:

exp

Table 1.1 – Parameters for DIPPR Vapor Pressure Equation 2

Substance

 Water 73.649 ‐ 7258.2 ‐ 7.3037 4.1653 × 10 ‐ 6 2 Ethanol 74.475 ‐ 7164.3 ‐ 7.327 3.1340 × 10 ‐ 6 2

Given the extremely strong intermolecular hydrogen bond interaction between water and ethanol the non ideal mixture shall be described through Gamma/Phi approach with fugacity coefficient for the gas phase, which may be taken as one due to the low pressure considered, and activity coefficient for the liquid phase calculated from simple Margules equation with parameters taken from Perry’s Handbook.

ln γ A 2 A A x ⋅x

ln γ A 2 A A x ⋅x

Table 1.2 – Margules Equation Parameter for VLE of Ethanol(1) and Water(2) 3

 Parameter Value ̅ 1.6022 ̅ 1.493

Given that it is a binary equimolar mixture and the parameters were given, both activity coefficients can be calculated:

Table 1.3 – Activity Coefficient of Ethanol(1) and Water(2) in Mixture

Parameter

Value

γ

γ

1.22

0.7947

2 from Perry et al., Table 2 6

3 From Perry et al., Table 13 2

Gabriel S. Gusmão Dr. Tam CHE 175A Problem Set 1 Due date: 02/02/12

For mixtures with only one flammable component, like water ethanol, the flash point temperature of the mixture is situated at the temperature in which the flammable component vapor pressure in the mixture is equal to its vapor pressure as pure component at its flash point.

From anhydrous ethanol MSDS sheet 4 from PHARMCOAAPER consulted at <www.msds.com> website, its flash point is 14°C – closed cup. At flash point, 14°C (287.15K), ethanol vapor pressure is given from DIPPR equation.

287.15 4.076

Through the Gamma/Phi approach for VLE at low pressures:

⋅ 1.22

For equimolar mixture, letting partial vapor pressure of ethanol equal to its flash and solving DIPPR equation numerically (through Mathcad 15 5 ) for temperature, it leads to:

4.076 0.5 ⋅ 1.22

295.23 22.08°

3. Estimate the LFL and the UFL of the following mixture of hexane (1%), methane (1%), ethylene (1%), and air (97%).

As there are only non polar components being regarded and their intermolecular interaction are far due to only mutual induction, the ideal equilibrium hypothesis shall estimate the real mixture behavior. From Daniel et al. 6 , the Lower Flammable Limit for the combustible components are given below.

Table 1.4 – Lower and Upper Flammable Limit and Concentration of Components

Component

Concentration

(vol. %)

Mole fraction on combustible basis

LFL

(vol. %)

UFL

(vol. %)

 Hexane 1 1/3 1.2 7.5 Methane 1 1/3 5.3 15 Ethylene 1 1/3 3.1 32.0 Air 97 ‐ ‐ ‐

4 Material Safety Data Sheet from PHARCO AAPER, see ref. II

5 PTC Mathcad 15, see ref. III

6 Reference 1, Appendix B

Gabriel S. Gusmão Dr. Tam CHE 175A Problem Set 1 Due date: 02/02/12

Knowing that Mole fraction on combustible basis is given by dividing the number of moles of the respective combustible specie by the total number of moles of combustible species. Something that can be done easily if assuming ideal gas behavior; where the volume concentration corresponds to the mole concentration. This assumption should estimate the real behavior of the gas phase because in this case low pressures (1atm) are being considered. Consequently, through Le Chatelier’s Principle, it comes that:

1

/

3

1

1.2 5.3 3.1

1

1

1

2.23%

Likewise, the Upper Flammable Limit (FLF ) for the mixture can be denoted as following.

1

/

3

1

1

1

32 12.97%

1

7.5 15

4. Do some research, the links to California and Federal regulations have been provided in lecture class. Cite your sources of information.

a. According to the Department of Transportation Office of Hazardous Material Safety, how many incidents occurred in 2011 for all modes of the transportation process?

From data available in Hazmat Intelligence Portal 7 redirected from PHMSA, U.S. Department of Transportation Pipeline and Hazardous Materials Safety Administration website 8 , there happened a total of 14,491 accidents related to transportations process, among different phases such as: in transit, in transit storage, loading and unloading.

7 From <https://hip.phmsa.dot.gov>; accessed in 01/31/12, at 10:45 p.m.

8 From < http://www.phmsa.dot.gov/hazmat/library/data stats/incidents>; accessed in 01/31/12, at 10:45 p.m.

Gabriel S. Gusmão Dr. Tam CHE 175A Problem Set 1 Due date: 02/02/12

Table 1.5 – Incidents for All Modes of the Transportation Process in California, 2011*

Transportation

Phase

Incidents Hospitalized

Non‐ Hospitalized Fatalities Damages

 In Transit 3,718 13 58 9 \$89,528,663 In Transit Storage 550 2 6 0 \$885,807 Loading 2,747 0 22 2 \$833,719 Unloading 7,476 10 38 0 \$17,831,190 Grand Total 14,491 25 124 11 \$109,079,379

*Source: Hazmat Intelligence Portal, U.S. Department of Transportation. Data as of 2/1/2012

Figure 1.1 – Incidents by Transportation Phase in California, 2011*

*Source: Hazmat Intelligence Portal, U.S. Department of Transportation. Data as of 2/1/2012

Through the chart, is noteworthy that most accidents occur in transit or when unloading the material; hence, is presumable that disturbs during transit and lack of attention when unloading may be causes of these incidents.

Gabriel S. Gusmão Dr. Tam CHE 175A Problem Set 1 Due date: 02/02/12

b. Provide information on hydrogen sulfide (H2S) regarding:

Following data are from MSDS datasheet from the Hardy Research Group, Department of Chemistry, The University of Akron 9

i) Physical State and Appearance: “Colorless gas with strong odor of rotten eggs. Fatigues the sense of smell which cannot be counted on to warn of the continued presence of the gas.”

ii) Physical Dangers: “Compound is heavier than air and may travel a considerable distance to source of ignition and flash back. It forms explosive mixtures with air over a wide range.”

iii) Chemical Dangers: “Reacts explosively with bromine pentafluoride, chlorine trifluoride, nitrogen triiodide, nitrogen trichloride, oxygen difluoride, and phenyl diazonium chloride. When heated to decomposition, it emits highly toxic fumes of oxides of sulfur. Incompatible with many materials including strong oxidizers, metals, strong nitric acid, bromine pentafluoride, chlorine trifluoride, nitrogen triiodide, nitrogen trichloride, oxygen difluoride and phenyl diazonium chloride.”

Data below are from the United States Department of Labor, Occupational Safety and Health Administration, OSHA 10

iv) TLV, STEL (assuming REL), PEL (and including IDLH):

American Conference of Governmental Industrial Hygienists (ACGIH) Threshold Limit Value (TLV):

(TLV TWA): 1 ppm, 14 mg/m³

(TLV STEL): 15 ppm, 21 mg/m³

9 From < http://ull.chemistry.uakron.edu/erd/Chemicals/8000/6567.html>; accessed on 01/31/12, at 11:39 p.m.; see ref. IX.

10 From OSHA: < http://www.osha.gov/dts/chemica lsampling/data/CH_246800.html>; accessed on 02/01/12, at 12:55 a.m., see ref. VIII.

OSHA Permissible Exposure Limit (PEL):

Gabriel S. Gusmão Dr. Tam CHE 175A Problem Set 1 Due date: 02/02/12

General Industry:(PEL C): 20 ppm (ceiling) with the following exception: if no other measurable exposure occurs during the 8 hour work shift, exposures may exceed 20 ppm, but not more than 50 ppm (peak), for a single time period up to 10 minutes.

Construction Industry (PEL TWA): 10 ppm, 15 mg/m³

Maritime (PEL TWA): 10 ppm, 15 mg/m³

National Institute for Occupational Safety and Health (NIOSH) Recommended Exposure Limit (REL):

Limit (REL): 10 ppm, 15 mg/m³ Ceiling (10 Minutes)

NIOSH Immediately Dangerous to Life or Health Concentration (IDLH): 100 ppm

(IDLH): 100 ppm

v) Effects of ShortTerm Exposure:

“The substance is irritating to the eyes and the respiratory tract. The substance may cause effects on the central nervous system. Exposure may result in unconsciousness. Exposure may result in death. Inhalation of gas may cause lung edema. The effects may be delayed. Medical observation is indicated. Rapid evaporation of the liquid may cause frostbite.”

vi) Effects of LongTerm Exposure:

So far studies were not reliable 11 and there is no evidence whether long term exposure may cause any harm.

“Long term H2S exposure has mainly been associated with nervous and respiratory system and eye effects. However, controversy exists as to whether or not long term exposure to H2S causes any significant health effects. The disagreement centers on the quality of the research and the nature of some of the reported symptoms, which include fatigue, headache, dizziness, irritability, and loss of appetite. These symptoms are not specific to H2S exposure and could be due to a number of other causes.

11 From CCOHS: <http://www.ccohs.ca/products/databases/samples/cheminfo.html>, accessed in 02/01/12, at 01:25 a.m.; see ref. VII.

Gabriel S. Gusmão Dr. Tam CHE 175A Problem Set 1 Due date: 02/02/12

There are a few studies that have evaluated the potential effects of long term environmental exposure to H2S. These studies are not reviewed here, since they are limited by factors such as concurrent exposures to many other chemicals, and self reporting biases.”

c. What types of workers are covered under OSHA? (For example: private sector workers, state and local government workers, federal government workers, selfemployed workers, etc.?)

Private Sector Workers: As OSHA covers all 50 states, the District of Columbia and other U.S. jurisdiction directly or through state program state programs approved by its requirements, most employees in the United States are covered by its laws; in addition, state programs concerning healthy and safety must be however as effective as the Federal OSHA program.

State and Local Government Workers: Not covered by Federal OSHA, but they are covered by OSH Act protections if the state where they work has a program approved by OSHA. States in the U.S. that have OSHA approved programs that cover employees of public sector are: Illinois, Connecticut, New Jersey, New York, and the Virgin Islands; moreover, private sector workers in the four states stated are under Federal OSHA coverage.

Federal Government Workers: The United States Postal Service, USPS, is covered by OSHA. American federal agencies have to provide safety and health programs at the same level of precaution OSHA offers. Although feral employees are not covered by OSHA, their requirements regarding laws comprised by OSHA are attended.

Self employed people, immediate family relatives of farm employers that do not employ outside employees and Workplace Hazards regulated by another Federal agency (for example, the Mine Safety and Health Administration, the Federal Aviation Administration, the Coast Guard) are NOT covered by OSHA.

12 From OSHA: < http://www.osha.gov/workers.html>, accessed in 02/01/12, at 01:41 a.m.

Gabriel S. Gusmão Dr. Tam CHE 175A Problem Set 1 Due date: 02/02/12

5. After reading the two articles from the Supplemental Readings section in the Course Materials folder of iLearn, answer the following questions.

a. What is LOPA? SIL 4?

In FrontEnd Engineering Phase

As the hazard and operability (HAZOP), LOPA, which is an acronym for Layer of Protection Analysis, is one of the current tools that aid a professional identifying Inherently Safer Design, ISD, necessities and alternatives during the FrontEnd Engineering and Design, FEED, stage. Based on equipment reliability statistics, through LOPA, it is possible to estimate the probability of an unexpected disturb event to happen and the capability of different layers of protection system to damp its consequences. By analyzing the expected frequencies of disturbs and its modeled projected consequences, the designer should be able to decide where to modify the process;, either by locating the sources of disturbs and reducing its likeability to happen or changing the process downstream so that the consequences of the events are diminished.

In Detailed Design Phase

At this point of the design process more information regarding process parameters and variables that should be concerned as HAZOP focus are available; consequently, specific parts of the project where unexpected events, of considerably danger consequences may happen, becomes more obvious. However, as process matures, it turns more difficult to undertake great modifications, and applications of LOPA in this stage generally focus on defining the necessary Safety Integrity Level, SIL, based on the necessity or not of decreasing the likelihood or probability of an event to happen to a tolerable level. LOPA does not provide any concernment about modifications in the process; nonetheless, it is an indicator that redesigning the process through Inherently Safer Design modifications may be more feasible than just accreting redundant safety instrument systems, SIS. As the requirements on safety increases, so does SIL, and it implies including more expensive and robust safety instrument system; for instance, at SIL 4 are comprehended nuclear facilities so that, due its complexities and potential dangerousness, the reliability required in terms of process safety are far beyond the level that general chemical Industries requires. Concluding, LOPA is a tool that indicates whether ISD modifications in the process are worth or when simply adding SIS is more costeffective.

Gabriel S. Gusmão Dr. Tam CHE 175A Problem Set 1 Due date: 02/02/12

b. What changes did DuPont implement to their process of insecticide production after the Bhopal, India incident?