Академический Документы
Профессиональный Документы
Культура Документы
Jeffrey MacDonald
Richard Roda
Michael Beresford
List of Figures............................................................................................................................... iv
List of Tables ................................................................................................................................ iv
1 Introduction ....................................................................................................................... 1
1.1 Ethyl Benzene Reaction System .................................................................................... 1
1.2 Methods of Producing Ethyl Benzene............................................................................ 2
1.2.1 Gas-phase Production Using Zeolite Catalysts (Mobil/Badger) ................................ 2
1.2.2 Liquid Phase Production with AlCl3: Friedel-Crafts/Alcar Process.......................... 4
1.2.3 Liquid Phase Reaction Using Zeolite Catalyst in a Fixed Bed (Lummus/UOP
EBOneTM)................................................................................................................................ 7
1.2.4 Process Selection ...................................................................................................... 11
2 Process Simulation .......................................................................................................... 12
2.1 HYSYS Simulation Fluid Property Package ............................................................... 12
2.2 Reaction Kinetics ......................................................................................................... 12
2.3 HYSYS Process Flow Diagram .................................................................................... 14
2.4 Section 1: Feed Preparation......................................................................................... 16
2.5 Section 2: Alkylation Reaction and Effluent Cooling .................................................. 19
2.6 Section 3: Benzene and Ethyl Benzene Separation .................................................... 22
2.7 Section 4: Transalkylation ........................................................................................... 25
2.8 Section 5: Cooling Water System................................................................................. 27
2.9 Energy Requirement Summary ................................................................................... 28
3 Market Survey ................................................................................................................. 29
3.1 UOP Process................................................................................................................. 29
3.2 Styrenics Industry (Nova Chemicals).......................................................................... 29
3.3 Plant Location .............................................................................................................. 30
3.4 Raw Material Availability ........................................................................................... 31
3.4.1 Ethylene20 ................................................................................................................. 32
3.4.2 Benzene .................................................................................................................... 33
3.4.3 Operating Results, 2003 versus 200220 .................................................................... 34
3.5 Demand ........................................................................................................................ 35
3.6 Outlook ......................................................................................................................... 36
4 Costs ................................................................................................................................. 37
4.1 Equipment Costs.......................................................................................................... 37
4.2 Capital Costs ................................................................................................................ 39
4.3 Direct Operating Costs ................................................................................................ 40
4.4 Profitability .................................................................................................................. 41
5 Environmental Considerations........................................................................................ 43
5.1 Plant Design Considerations ....................................................................................... 43
5.1.1 Greenhouse Gas Emissions...................................................................................... 43
5.1.2 Vapour Flaring ......................................................................................................... 44
5.1.3 Process and Waste Water Treatment: Oily Water Sewer ....................................... 45
5.2 Environmental Regulation: Plant Operation Considerations..................................... 45
5.2.1 Canadian Environmental Protection Act ................................................................ 46
5.2.2 National Pollutant Release Inventory ..................................................................... 47
5.3 ISO Certification .......................................................................................................... 48
5.4 Material Concerns........................................................................................................ 50
5.5 Case Study: Texas Nova Chemical Plant Explosion and Release............................... 51
6 Safety ............................................................................................................................... 52
6.1 Chemical Properties..................................................................................................... 52
ii
6.1.1 Ethylene ................................................................................................................... 53
6.1.2 Benzene .................................................................................................................... 54
6.1.3 Ethyl Benzene .......................................................................................................... 56
6.1.4 Di-ethyl Benzene and Tri-ethyl Benzene................................................................. 58
6.1.5 Toluene ..................................................................................................................... 58
Y-zeolite Catalyst ................................................................................................................. 59
6.1.6 Chemical Property Summary: Explosion Characteristics....................................... 60
6.2 Material Storage .......................................................................................................... 61
6.2.1 Compressed Gas Storage ......................................................................................... 61
6.2.2 Liquid Storage .......................................................................................................... 64
6.2.3 Catalyst Solids Storage ............................................................................................ 65
6.2.4 Storage related hazards ........................................................................................... 65
6.2.5 Inherently Safer Material Storage .......................................................................... 66
6.3 Material Transportation .............................................................................................. 67
6.4 Hazard Analysis........................................................................................................... 69
6.4.1 Dow Fire & Explosion Index .................................................................................... 69
6.4.2 Chemical Exposure Index ........................................................................................ 70
6.4.3 Hazard Analysis: What-if......................................................................................... 72
6.5 Case Studies................................................................................................................. 73
6.5.1 Benzene and Ethylene Explosions........................................................................... 73
6.5.2 Short Term Ethyl Benzene Exposure ...................................................................... 75
6.5.3 Long Term Benzene Exposure ................................................................................. 75
6.5.4 Lessons to be learned ............................................................................................... 76
7 Conclusions ...................................................................................................................... 78
8 Recommendations ............................................................................................................ 80
8.1 Process Recommendations ........................................................................................... 80
8.2 Safety and Environmental Recommendations ............................................................ 80
8.3 Economical Recommendations..................................................................................... 81
References.................................................................................................................................... 82
References.................................................................................................................................... 82
A. Economics Spreadsheet ................................................................................................... 86
B. Sample Equipment Cost Calculations............................................................................. 88
C. Glossary............................................................................................................................ 90
D. What-if? Analysis............................................................................................................. 91
E. F&EI Sample Calculations .............................................................................................. 94
F. CEI Sample Calculations............................................................................................... 102
G. HYSYS Workbook Output ............................................................................................. 105
iii
List of Figures
List of Tables
Table 2-1: Operation-section key ................................................................................................ 14
Table 2-2: Plant section description. ........................................................................................... 16
Table 2-3: Section 1 conditions.................................................................................................... 17
Table 2-4: Section 2 reactor conditions. ...................................................................................... 20
Table 2-5: Recycle 2 and E2 Inlet stream data. .......................................................................... 20
Table 2-6: Section 4 conditions.................................................................................................... 26
Table 2-7: Energy requirements summary. ................................................................................ 28
Table 3-1: Yearly North American production of EB.25 .............................................................. 36
Table 4-1: Equipment costs (all equipment is carbon steel)....................................................... 38
Table 4-2: Capital costs (EB = 156,000 tonne/yr). ...................................................................... 39
Table 4-3: Direct operating costs (EB = 156,000 tonne/yr)......................................................... 40
Table 4-4: Indirect operating costs (EB = 156,000 tonne/yr)...................................................... 41
Table 5-1: CEPA 200 regulatory limits.32 ................................................................................... 47
Table 6-1: NFPA codes for chemicals used in the production of EB. ......................................... 53
Table 6-2: Ethylene exposure limits.40 ........................................................................................ 53
Table 6-3: Benzene exposure limits data.45................................................................................. 55
Table 6-4: Ethyl benzene recommended exposure limits.49 ........................................................ 57
Table 6-5: PPE material and break through time.49 ................................................................... 58
Table 6-6: Important explosion chemical properties for design considerations......................... 61
Table 6-7: Dow F&EI for the EB plant. ...................................................................................... 69
Table 6-8: CEI calculated values................................................................................................. 71
iv
Executive Summary
An ethyl benzene plant has been designed using a liquid phase alkylation of benzene
with ethylene. The process is to be implemented at the Nova Chemical styrene plant
gas-phase process, the Alcar/AlCl3 liquid phase process, and the Lummus/UOP
EBOneTM liquid phase process. The EBOneTM process was selected as a basis because
it uses a safe and less expensive fixed bed catalyst, moderate operating conditions, and
columns is used to separate benzene and EB from the main process stream. Benzene is
recycled to the alkylation feed and transalkylation section. The transalkylation reactor
is then used in conjunction with a recycled benzene feed to convert separated DEB to
additional EB. This stream is recycled to the entrance of the separations system. The
HYSYS 3.2 simulation software package was used to model the necessary unit
Based on the current simulation and a plant capacity of 18,000 kg/h (156,000 tonne/a)
of EB, the plant has a positive net present value of US$ 7.2 million, based on a MARR
of 20% with an IRR of 27%. The plant capital investment is estimated at US$ 23
million, with total operating costs at approximately US$ 160 million. Product revenue
is estimated at US$ 175 million in EB sales, at a current selling price of US$ 1.12/kg.
The vast majority of un-reacted benzene is recycled, and a negligible amount is purged
v
The selling price of EB to turn a profit at a MARR of 20% is US$ 1.09/kg. This was
determined by calculating the effect of EB selling price on rate of return. The effect of
EB production with respect to equipment cost and operational costs was also
benzene cost of US$ 1.05/kg. It is difficult to predict benzene cost as the value has
Chemical plant of 150,000 tonne/a. The benzene-ethylene ratio of 5:1 fed into the
through the recycle streams of the plant. Complications with the HYSYS 3.2 software
makes this change difficult, and other designs may be required to lower this ratio.
This benzene increases reboiler duty costs, column costs, and large amounts of
circulated benzene.
Dow F&EI and CEI analysis indicated the areas of highest risk in the plant. The most
notable area is the alkylation assembly feed, which had a CEI of 1120 and Dow F&EI
of 165. The design must be modified to minimize the amount of hazardous material in
this section of the plant. Decreasing the benzene-ethylene ratio should reduce the
amount of recycled benzene and decrease the overall flow rate into the reactor
assembly.
vi
1 Introduction
The reaction of benzene with ethylene produces ethyl benzene and by-product di-ethyl
Chemical Corporation has contracted to update their existing ethyl benzene synthesis
resulting from subsequent yearly losses prompted Nova Chemical to evaluate new
There are multiple technologies in current practice in the styrene industry. The
fundamental differences are related to the reaction phase and vessel system. In the
determine which technologies offer the best combination of profitability and inherent
safety.
The proposed plant design involves creating ethyl benzene from the raw components of
benzene and ethylene. The chemical reaction to create ethyl benzene is:
C6 H 6 + C 2 H 4 → C6 H 5 C 2 H 5 (1.1)
Eq.(1.1) for the reaction of benzene and ethylene to form EB is accompanied by five
side reactions. Three of them are shown in Eq. (1.2), (1.3), and (1.4).
C6 H 6 + 2C 2 H 4 → C6 H 4 (C 2 H 5 )2 (1.2)
C6 H 5C 2 H 5 + C 2 H 4 → C6 H 4 (C 2 H 5 )2 (1.3)
C6 H 6 + C6 H 4 ( C 2 H 5 ) 2 2C6 H 5C 2 H 5 (1.4)
1
The reaction illustrated in Eq. (1.2) and (1.3) produces an undesired product, DEB.
Proper use of LeChatelier’s Principle can force the equilibrium reaction described by
Eq. (1.4) to yield as much desired product (EB) as possible. Eq. (1.5) and (1.6) show
two further side reactions, but are negligible for simulation purposes.
C6 H 5C 2 H 5 + C2 H 4 → (CH 3 )2 C6 H 3C 2 H 5 (1.6)
The kinetics for these two reactions were not found to be documented in literature.
However it has been shown that the reaction extents for both reactions are negligible
when simulating the process.1 As such, Eq. (1.1)-(1.4) shall be used for design in
HYSYS. Several process designs can be implemented to favour the production of EB.
Several methods for creating ethyl benzene are discussed in the proceeding section.
conversion.1 The three methods discussed in this report include the creation of ethyl
benzene in the gas-phase reaction (Mobil/Badger), in the liquid phase using an AlCl3
acid catalyst, and a liquid phase reaction in fixed bed reactors using a zeolite catalyst.
The gas-phase reaction to create ethyl benzene using a zeolite catalyst is referred to as
the Mobil/Badger process. The mechanism for creating EB differs from the AlCl3 and
Alcar process (see Section 1.2.2), since the zeolite catalyst produces a carbonium ion
quickly attacked by benzene. This in turn causes a faster reaction; however, more by-
2
products are produced as well which have to be recycled and converted back to useful
Approximate operating conditions are 675-725 K and 200-400 psig. The operating
conditions are significantly higher than those for the liquid phase process, resulting in
approximately 8-16 by mole fraction for the gas-phase reaction. Such a large ratio is
needed since the catalyst used is highly deactivated by the presence of ethylene as
Catalyst life using a gas-phase reaction is a major downfall of the gas-phase process.
The catalyst requires regeneration every two to four weeks. To maintain steady state
operation, it is typical to run two reactors in parallel. Because of this, the costs
associated with this process are high as shutdown costs, catalyst costs, and
deactivated catalyst disposal are high. In addition, because the B/E ratio is high, the
costs of operation are higher in order to retrieve and recycle the excess benzene.
The gas-phase reaction does have some positive aspects. The zeolite catalyst is safer
environmentally and disposal costs are not as high. Also, the catalyst is non-corrosive
and therefore special materials, which are required for the AlCl3 and Alcar process,
are not required. However, the catalyst life problem is a major issue with this process.
The AlCl3, Alcar, and liquid process using zeolite catalysts resolve this issue. Figure
3
1.2.2 Liquid Phase Production with AlCl3: Friedel-Crafts/Alcar Process
presence of an aluminum chloride acid catalyst (AlCl3). This reaction occurs in the
AlCl3 (cat) R
R X
-HX
Where
R = Ethylene group
X = Chlorine atom
With this process, the AlCl3 is injected as fine particles into the alkylator reactor
where the ethyl benzene is formed. The AlCl3 is quite often promoted with HCl or
ethylene chloride to reduce the amount of AlCl3 required for the reaction. Once
through the reactor, the AlCl3 is filtered out of the product by water washing and then
sent for disposal or regeneration. To recover the unwanted di-ethyl benzene and other
The liquid phase process has several advantages over the gas-phase process because
temperatures and pressures are reduced which lead to saving in operating costs. In
addition, the operation is safer since operating conditions are not as severe. Typical
running conditions for temperature and pressure are between 420-470 K and 70-150
4
5
Figure 1-2: Mobil/Badger Process.2
Having a lower B/E ratio reduces the operation costs associated with removing the un-
reacted benzene and provides a more economical plant operation.2 Another positive
aspect of the liquid phase reaction is that the catalyst is not subjected to high
deactivation rates. However, this type of catalyst does have some downfalls.
The catalyst used in the AlCl3 process is an acid, which tends to corrode the operating
equipment unless the internals of the equipment are lined with special materials
(such as brick or glass). The use of such materials increase construction costs and may
be expensive to maintain as some are quite fragile. In addition, the catalyst is injected
and removed from the process on a continuous basis, leading to higher operation costs
in water and filtration when the catalyst is separated from the process stream.
Finally, the AlCl3 catalyst is hazardous to the environment and there are relatively
Further process designs, such as the Alcar Process from Universal Oil Products (UOP)
resolved some of the downfalls of the AlCl3 process. It used a fixed bed of BF3 catalyst
which had reduced corrosion concerns and eliminated the need for continuous catalyst
removal. However, the Alcar process did require much higher operating pressures of
approximately 500 psig and therefore increasing operating costs. Also, the problem of
the AlCl3 catalyst disposal was also present when using the BF3 catalyst. The AlCl3
and Alcar processes are shown in Figures 1-3 and 1-4, respectively.
Research continues for the use of a zeolite catalyst in a fixed bed for a liquid phase
6
1.2.3 Liquid Phase Reaction Using Zeolite Catalyst in a Fixed Bed
(Lummus/UOP EBOneTM)
Similiar to the Mobil/Badger process, the liquid phase reaction uses a zeolite catalyst
which does not require special material for reactor internals, piping, or in other parts
of the process. In addition, the zeolite catalyst is not as harmful to the environment
which saves in disposal costs. There are several patents for this type of reaction,
however, the Lummus/UOP EBOne is the most recent and provides the most benefits.3
This process, like the preceding AlCl3 and Alcar process, requires an alkylator and a
that of the AlCl3 process. The B/E alkylator feed ratios range from 1.5-2.0 on a molar
basis. Since temperatures and pressures are not extreme and B/E ratios are relatively
low, there are large savings available in operational costs when compared to the
Mobil/Badger process. Further, since the catalyst is contained in fixed beds there are
reduced operational costs when compared to the AlCl3 and Alcar process because the
catalyst does not have to be continuously removed from the process using a filter and
washing.
7
8
Figure 1-3: Production of EB using AlCl3 process.2
9
Figure 1-4: Production of EB using the Alcar process.2
The most positive aspect of the EBOne process is that catalyst life is claimed to be at
least five years for the alkylator and the transalkylator when using the EBZ-500™
and EBZ-100™ as the fixed bed catalyst, respectively. Also, these catalysts may be
regenerated for at least three cycles. Therefore, they constitute a more economical
alternative to conventional catalyst. Further savings are realized since shutdowns are
less frequent to change out the catalyst in the fixed beds of the reactors. A diagram of
As Figure 1-5 shows, the main reaction takes place in the “Alkylation Section” in the
presence of the EBZ-500™ catalyst in fixed beds. The ethylene and benzene react to
form the product ethyl benzene and other unwanted products. The top product of this
reactor flows to the “Benzene Column” where the excess benzene is removed from the
product stream and then sent back as recycle with “Fresh Benzene”. The remaining
gas is then sent to a “Lights Removal Column” where any un-reacted ethylene is sent
10
to a flaring system. Any un-separated benzene is also combined with the recycled
benzene stream.
The bottoms of the “Benzene Column” are sent to the midsection of the “Ethyl Benzene
Column”. The ethyl benzene product is separated from the other unwanted products
as distillate and then sent to storage. The bottoms of the “Ethyl Benzene Column” are
sent to the mid section of the “Poly-ethyl Benzene Column”. The distillate of this
column is condensed and combined with some recycle benzene and then sent to the
“Transalkylation Section”.
In the “Transalkylation Section” the side reaction (DEB and TEB) products are
reacted in the presence of the EBZ-100™ catalyst in fixed beds to form more ethyl
benzene. The top product of “Transalkylation Section” is then combined with the top
product of the “Alkylation Section”, where it repeats the process loop. The bottom
product of the “Poly-ethyl Benzene Column” is mostly a viscous tar material which is
The EBOne process offers the best economical benefits, operating conditions, safety,
and environmental considerations. The EBOne process has been successfully used in
15 fully operational plants with capacities ranging from 65,000 tonne/yr to 200,000
tonne/yr. Five more plants are in the construction phase licensing the EBOne process.
The first plant has being operating at full capacity for 12 years.3 Low operating
conditions, liquid phase reactions, and the environmentally friendly zeolite catalyst
were the primary determinants in selecting this process for a design basis.
11
2 Process Simulation
The Peng-Robinson property fluid package was used for this simulation. It utilizes the
Peng-Robinson (PR) equation of state model which can be seen in the HYSYS help
manual. It was chosen because the PR model gives good results for non-polar systems,
and has a wide range of materials that can be used for accurate results. All the
components used in the production of EB are either non-polar or contain very weak
dipole moments. It was also noted that HYSYS contained all the necessary interaction
Kinetics for the “Alkylation Section” are taken from Qi and Zhang (2004)1. The
kinetics takes into account the use of zeolite catalyst. The reaction of benzene with
The reaction of benzene with two moles of ethylene to produce di-ethyl benzene is as
follows:
The reaction of ethyl benzene with ethylene to produce di-ethyl benzene is as follows:
C6 H5C2H5 + C2H4 → C6 H4 (C2 H5 )2 r3 =8.5×10-7 exp( -86.4 )CE1.77 CEB 0.35 (2.9)
RT
The three kinetic equations above have the units of kgmole/m3s. The activation
energies given in Qi and Zhang (2004) did not contain information on units. A second
source indicated that the units were kcal/mol.7 The results of a conversion of the
activation values into kJ/kgmol are shown above in Eq. (2.7)-(2.9). The equilibrium
12
reaction of benzene with di-ethyl benzene to form two moles of ethyl benzene is as
follows:
276.6
C6 H 6 + C 6 H 4 ( C 2 H 5 ) 2 2C6 H 5 C2 H 5 ln ( K EQ ) = -0.3599 (2.10)
T
The reactions for the “Transalkylator Section” were modeled using the equilibrium
Ho 1 1
K(
ln K ′ =-) -
R T T′ (2.11)
Where
The reference temperature and equilibrium constant were given in Qi and Zhang
(2004). These values had a K value of 0.883 and a T value of 571 K.1 The standard
Eq. (2.11) and substituting the appropriate values in for variables yields Eq. (2.10).
presented discussing each major unit operation with its function, parameters such as
13
2.3 HYSYS Process Flow Diagram
Figure 2-1 shows the HYSYS process flow diagram in its entirety. There are 14 main
process operations contained in five sections of the plant. Table 2-1 summarizes the
PFD labels of these operations with descriptions of the equipment and the section of
the plant in which they are contained. Table 2-2 shows a summary of each of the five
14
15
Figure 2-1: HYSYS simulation PFD.
Table 2-2: Plant section description.
Section
Brief Description
Number
Section 1 Feed preparation section of the plant. Its purpose is to
prepare the feed components for the reactions in Section 2.
Section 2 Alkylation section of the plant which is divided into two
trains of reactors. The purpose of this section is to form
ethyl benzene from ethylene and benzene raw components.
It contains four real reactors, a reducing valve and an
effluent cooling water heat exchanger.
Section 3 Benzene and ethyl benzene separation section of the plant.
It contains two distillation columns and a flash drum.
Section 4 Transalkylation section of the plant. Converts some of the
diethyl benzene to ethyl benzene using C-1 benzene recycle
Section 5 Cooling water section of the plant. It provides the plant
with the required cooling water needed in the distillation
columns, reactor cooling jackets, and the three cooling
water heat exchangers.
further detail.
The purpose of this section of the ethyl benzene plant is to prepare the feed
reaction occurs. This section handles a large recycle benzene stream which is
Section 1 of the EB plant includes the fresh feed streams of benzene and
ethylene, the benzene feed pump (P-1), the benzene recycle pump (P-2), and
16
the R-1/R-2 assembly feed heat exchanger (E-1). The raw ethylene arrives on
1.8 MPa before entering the main plant. The feed and recycle are mixed then
cooled using a cooling water shell and tube heat exchanger (E-1). The tube
side of the exchanger contains the cooled product which then proceeds to
Figure 2-2.
Table 2-3 summarizes the composition, operating conditions, and flow rates
17
To pump the fresh benzene to the reactor conditions of 1.8 MPa, the pump
HYSYS simulation became unstable for any attempts to decrease the ratio. If
this ratio is decreased any further than 1.4, the deactivation of the zeolite
catalysts in the R-1 assembly becomes a major issue requiring the shutdown
benzene conversion, however HYSYS does not take catalyst deactivation into
account, and as such, the simulation is bound to this constraint.9 The desired
B/E ratio from the reactor inlet steam (Train Feed) is controlled in the
Calculations”).
The E-1 heat exchanger is simulated with a complex shell and tube heat
exchanger. The process stream flows on the tube side of the exchanger and
the cooling water passes through the shell side. Heat integration was not
the re-boilers in the distillation columns (where heat integration is not used).
18
2.5 Section 2: Alkylation Reaction and Effluent Cooling
reactor assembly which forms the product compound of ethyl benzene and
other by-products such as diethyl benzene. The assembly is divided into two
trains, Train 1 and Train 2. Each train consists of two CSTR reactors and two
the highest yield and level of safety as possible. A schematic of this section of
The two trains are identical to each other in terms of mass flow rate,
19
details for each reactor while the conditions for the Recycle 2 and E2 Inlet
Recycle 2 E2 In
Temperature (°C) 20 115
Pressure (kPa) 500 500
Mass Flow Rate (kg/h) 22,540 100,000
Benzene Mole Frac. 0.846 0.826
Ethylene Mole Frac. 0.007 0.018
EB Mole Frac 0.135 0.016
DEB Mole Frac. 0.012 0.016
The volume of each CSTR model is approximately 35m3 , which are ordered in
reaches its size limit around 250 m3. The reactor volume had a negligible
20
35m3 was the smallest volume to which HYSYS would converge without
At steady state, the R-1 assembly runs at 125°C and 1700 kPa in which there
is a 13°C exotherm in the second R-1 of each train. These process conditions
are based on U.S. Patent 6,504,071 and most conditions fall within the
proposed ranges.10 To improve heat efficiency of the plant, the reactors were
cool the reactant contents. The reactor outlets are cooled just enough to
maintain them in the liquid phase. As a result, the reactant outlets do not
E-2 was simulated using a complex shell and tube heat exchanger. The
process stream flows in the tube side of the exchanger and is cooled by water
passing through the shell side of the exchanger. Again heat integration was
not possible as there are no process streams that require heating other than
In order to obtain a respectable life of the EBZ-500TM catalyst, the B/E ratio
limiting reagent, and therefore limiting its interaction with the catalyst and
21
causing deactivation. As previously stated, the deactivation of the catalyst
replacement and regeneration. However, this ratio must also be kept as low
Section 3 of the ethyl benzene plant consists of two distillation columns (C-1
and C-2) and a flash drum (C-3). This section of the plant is used to separate
benzene and ethyl benzene from the main process stream. A schematic of this
22
The benzene separation occurs in C-1 in which the distillate stream is 99.7%
benzene (m.f.). A portion of the distillate proceeds to C-3 for flaring and to
invoking a 40 kPa pressure drop allowing some of the process stream to flash
off. The remainder is recycled back to the feed section of the plant for further
reaction in the R-1 assembly. The bottoms of the column proceed to C-2 for
further separation. Process details of C-1 inlets and outlets are detailed in
Table 2-6 and the process details of C-3 can be seen in Table 2-7.
Benzene to Benzene to
Out-4
Tankage Transalk
Temperature [°C] 83 82 82
Pressure [kPa] 400 360 360
Mass Flow Rate [kg/h] 19,820 47 19,770
Benzene Mole Frac. 0.977 0.311 0.991
Ethylene Mole Frac. 0.022 0.689 0.007
EB Mole Frac. 0.002 0.00 0.002
DEB Mole Frac. 0.00 0.00 0.00
23
C-1 is approximately 16.3 m high, has a diameter of approximately 3.4 m,
and contains 27 actual trays (assuming a tray efficiency of 60%). The feed
stage is on tray number 19, where the column is numbered from top to
bottom. C-1 removes 99.5% of the benzene from the process stream. The
reflux ratio is 15.8 and the column has a pressure drop of 70 kPa.
The bottoms of C-1 are sent to C-2 where ethyl benzene is separated from
and contains 33 trays assuming 60% tray efficiency. C-2 removes 99.9% of the
ethyl benzene from the process stream. Table 2-8 illustrates the process
details of C-2. The distillate stream of C-2 is the product stream of ethyl
benzene while the bottoms of the column are mainly diethyl benzene which is
C-2-Distillate C-2-Liq
Temperature [°C] 185 240
Pressure [kPa] 360 360
Mass Flow Rate [kg/h] 18,770 2700
Benzene Mole Frac. 0.042 0.0
Ethylene Mole Frac. 0.0 0.0
EB Mole Frac. 0.978 0.007
DEB Mole Frac. 0.0 0.993
Table 2-8 shows a summary of the design specifications of C-1 and C-2.
24
Table 2-8: Section 3 C1 and C2 design summary.
C-1 C-2
Height (m) 16.3 20.3
Width (m) 3.4 2.3
Number of Actual Trays 27 33
(60% Efficiency)
Reflux Ratio 0.7 2.1
Re-boiler Duty (kW) 16 5
Condenser Duty (kW) 16 5
Feed Stage 11 19
25
Table 2-6: Section 4 conditions.
The Transalkylator (R-3-1A & R-3-1B) makes use of the equilibrium and
required for this plant design, it is logical that lower temperatures are
The reactor has been sized at 30 m3. The simulation did not converge at lower
volumes, and the conversion achieved at higher volumes was negligible. The
bottoms of C-2 is mixed with the benzene recycle and cooled to 25°C and
26
amount of EB formed, however this is related to the high benzene-ethylene
ratio entering the R-1/R-2 assembly. There is too much unreacted benzene
Section 5 of the EB plant consists of the upper and lower cooling water
headers for the plant. Figure 2-6 shows the upper header inlet and lower
header.
Cooling water at 22°C and 100 psig enters the upper header and exits the
plant at 55°C and 100 psig. Approximately 633,000 kg/h of cooling water is
27
2.9 Energy Requirement Summary
The energy requirements for the plant are summarized in Table 2-7. It is
readily apparent that the largest utility costs are the condenser and re-boiler
of the columns C-1 and C-2. Steam is used for the re-boiler requirements as
the temperatures are not unrealistically large. Relatively low pressures are
28
3 Market Survey
Over 99.9% of the ethyl benzene produced in the world is used in the
500 catalyst for the alkylation of benzene with ethylene to produce EB.19 The
1990 by the Nippon Styrene Monomer Corporation (Japan). The plant used
the UOC-4120 zeolite catalyst manufactured by UOP for both the alkylation
Japan in 1994, this time, using the newly developed EBZ-100 transalkylation
catalyst. By 1997, full-scale plants were using EBZ-500 (the catalyst proposed
Styrene is produced from ethyl benzene, which in turn, is made from benzene
and ethylene. All of the ethylene and a significant portion of the benzene
requirements for the styrene facility in Sarnia are supplied from the
29
Corunna, Ontario olefins facility. The remaining benzene feedstock is
Limited in 1996, 1998 and 2000, respectively, resulted in Nova being net
production by 500 million kg. In a tight market, this allows for maximum
styrenic polymer sales. It also allows for the sale of scarce monomer at high
prices in the spot market. However, when demand for styrene and
The geographical location of a plant can play a pivotal role in the design of a
30
a conclusion can be drawn on the best site. Although, there can be major
environmental aspects to be concerned with, the major factor is for the most
temperatures. 13
Valley, about 230 km west of Toronto, Ontario. Figure 3-1 depicts a map of
the location with respect to several of the Great Lakes and Detroit, Michigan.
The Sarnia site supplies styrene to Nova Chemicals' Montreal, Quebec and
as does the majority benzene feed. Both arrive on-site via pipeline. The
31
3.4.1 Ethylene20
Nova Chemical owns two ethylene facilities in Canada. The major plant is
located in Joffre, Alberta and accounts for 75% of their total ethylene
their primary feedstock. Natural gas is purchased to replace the energy loss
The Joffre site is the largest ethylene complex in the world and runs more
economically than its similar counterparts in the US. In 2003 and 2002, this
and down from a 14-year historical average of $0.13/kg (Figure 3-2). In 2002
and for most of 2003, excess supply reduced the price for ethane relative to
natural gas on the U.S. Gulf Coast (USGC) and caused the cost advantage to
decline. In the second half of 2004, demand for ethane began to improve on
the USGC and for 2004, the average ethylene advantage increased to
32
The ethylene plant in Corunna has the flexibility to switch part of its
feedstock slate between natural gas liquids and crude oil derivatives,
model that calculates the most profitable mix of end products that can be
3.4.2 Benzene
A worldwide shortage of benzene, combined with strong demand for the key
raw material has sent prices skyrocketing in 2004. Prices have more than
doubled to record highs of $4.25 per US gallon for spot product and $3.95 per
US gallon for contract benzene earlier this year. Current benzene price is
Rapidly increasing benzene pricing (see Figure 3-3) could hurt the US styrene
Export pricing on styrene monomer does support these higher benzene levels,
especially since ethylene and natural gas prices have moderated. Currently,
33
Ethylene (US contracts; cts/lb) Benzene (US spot; $/gal)
45 4.5
40 4.0
35 3.5
30 3.0
25 2.5
20 2.0
15 1.5
10 1.0
5 0.5
0 0.0
Oct-03 Nov-03 Jan-04 Mar-04 Apr-04 Jun-04 Aug-04 Sep-04 Nov-04 Dec-04 Oct-03 Nov-03 Jan-04 Mar-04 Apr-04 Jun-04 Aug-04 Sep-04 Nov-04 Dec-04
70 100
90
60
80
50 70
40 60
50
30 40
20 30
20
10 10
0 0
Oct-03 Nov-03 Jan-04 Mar-04 Apr-04 Jun-04 Aug-04 Sep-04 Nov-04 Dec-04 Oct-03 Nov-03 Jan-04 Mar-04 Apr-04 Jun-04 Aug-04 Sep-04 Nov-04 Dec-04
Figure 3-3: Selling prices for ethylene, benzene, and styrene for 2003-
2004.23
Nova’s styrenics business results declined in 2003, bringing their net loss to
$130 million from a $102 million loss in 2002. Price increases implemented
throughout 2003 kept pace with rapidly rising feedstock costs but were more
well as the negative impact of the outage on the Bayport, Texas styrene
and continued to rise in early 2004, styrene prices continue to increase. These
price increases were announced for styrene monomer and the full slate of
styrenic polymers in both North America and Europe. The price increased by
feedstock costs. Price increases have varying degrees of success. They are
34
typically phased in and can differ by product or market. Benchmark price
3.5 Demand
The current global market is stable for styrene, but is poised to tighten
first two quarters of 2004. A possible roadblock to any run-up in styrene is its
main feedstock benzene, which has seen its price rise because of higher
North American demand for ethyl benzene is shown in Figure 3-4. The
presently more ethyl benzene being produced than the market can support.
35
6500
$6,119 $6,128
6000 $5,858
5000
$4,819
4500
4000
1998 1999 2000 2001 2002 2003
Figure 3-4: Demand for ethyl benzene since 1998 (in millions of kg).
Capacity
Producer
[millions of kg/yr]
BP Chemicals, Texas City, TX 500
Chevron, St. James, LA 800
Cos-Mar, Carville, LA 1,000
Dow, Freeport, TX 850
Huntsman, Odessa, TX 150
Lyondell Chemical, Channelview, TX 1,350
Nova, Bayport, TX 650
Sterling, Texas City, TX 900
Westlake, Lake Charles, LA 150
Nova Chemicals, Sarnia, Ont. 430
Total 6,780
3.6 Outlook
Ethyl benzene’s market growth depends highly on the demand for styrene. At
36
2% in the long term. Accordingly, ethyl benzene is only expected to increase
by 2%.
World demand for ethyl benzene in 2001 was about 23 million metric tons.
4.6% from 2001 to 2006 (or 3.4% from 2000 to 2006), resulting in global ethyl
expected to grow the fastest in the Middle East and South America.16
4 Costs
The current NPV of the plant is US$ 7 million. This value is based on the
assumed 20-year life of the plant and a MARR of 20%. A new process
determined to be 27%.
Equipment costs have been calculated for the current plant design based on
installation costs are shown in Table 4-1. For economical reasons, carbon
steel was selected for equipment construction. Carbon steel has suitable
37
Total purchasing costs in 2004 amount to US$ 3.6 million and total
installation costs are US$ 2.3 million. The two distillation columns (C-1 and
C-2) account for the largest portion (60%) of the equipment costs.
Purchase Install
Ref
Equipment Description Cost, Cost, Cost Formula
(P&T)
US $ US $
CSTR (R-1) 35 m3; CS 121,800 54,800 21,000(V)0.529 p. 628
jacketed; 300
psia
CSTR Motor (R-1) 35 m3 2,600 1,200 P = 0.08(V) 3 p. 520
380(P)0.53
CSTR (R-1) 35 m3; CS 121,800 54,800 21,000(V)0.529 p. 628
jacketed; 300
psia
CSTR Motor (R-1) 35 m3 2,600 1,200 P = 0.08(V) 3 p. 520
380(P)0.53
CSTR (R-1) 35 m3; CS 121,800 54,800 21,000(V)0.529 p. 628
jacketed; 300
psia
CSTR Motor (R-1) 35 m3 2,600 1,200 P = 0.08(V) 3 p. 520
380(P)0.53
Pump (P-1) 16 m3/h 5,600 2,400 2,048(v) 0.36 p. 519
Pump Motor (P-1) 10 kW 1,300 600 380(P)0.53 p. 520
Pump (P-2) 68 m3/h 9,300 4,000 2,048(v) 0.36 p. 519
Pump Motor (P-2) 39 kW 2,600 1,100 380(P)0.53 p. 520
Pump (P-3) 26 m3/h 6,600 2,800 2,048(v) 0.36 p. 519
Pump Motor (P-3) 2 kW 500 200 380(P)0.53 p. 520
Separator 3.3 m3 33,400 15,000 15,000(V) 0.67 p. 864
Heat Exchanger (E-1) 26.9 m2 8,279 3,312 1,290(A)0.565 p. 682
Heat Exchanger (E-2) 35.4 m2 9,684 3,873 1,290(A)0.565 p. 682
Heat Exchanger (E-3) 34.6 m2 9,546 3,818 1,290(A)0.565 p. 682
Dist Col (C-1) 3.4 m diameter; 1,051,200 788,400 1,230(D)1.39 × Ntray p. 794
27 trays; 16.3 m 4,050(D)1.39 × H
height, = 0.6
Condenser (C-1) 59E6 kJ/h; 104,800 78,600 A = Q/(1500 × TL ) p. 682
212 m2 7,400(A)0.70
Reboiler (C-1) 59E6 kJ/h; 245,100 110,300 A = Q/(4000 × T) p. 682
713 m2 7,400(A)0.70
38
Dist Col (C-2) 2.3 m diameter; 977,300 733,000 1,230(D)1.39 × Ntray p. 794
33 trays; 20.3 m 4,050(D)1.39 × H
height, = 0.6
Condenser (C-2) 18E6 kJ/h; 115,100 86,300 A = Q/(1500 × TL ) p. 682
242 m2 2,470(A)0.70
Reboiler (C-2) 18E6 kJ/h; A = Q/(4000 × T) p. 682
368 m2 154,100 69,400 2,470(A)0.70
Totals (2002) 3,345,000 2,178,000 M&S = 1117
Totals (3Q 2004) 3,576,000 2,328,000 M&S = 1194
The capital costs for the preliminary plant design are shown in Table 4-2.
39
4.3 Direct Operating Costs
The projected direct operating costs are summarized in Table 4-3. Since
catalyst is purchased once every five years, an annual equivalent rate was
calculated. Approximately 96% of the annual cost is associated with the raw
The indirect operating costs, or fixed costs, are represented in Table 4-4. The
projected total operating costs (direct and indirect) for the EB plant is
Cost ,
Item Rate Basis Reference
US $/yr
Benzene 14,200 kg/yr 1.05 129,717,000 Ref 23
Ethylene 4,770 kg/yr 0.484 20,081,900 Ref 23
Catalyst 43,500 kg/5yr 0.05 12,400 Ref 26
Power 50 kW $0.055/kwh 24,000 Ref 27
Water 633,000kg/yr $8E-6/kg (20°C) 44,100 P&T, p. 266
Steam $7.70E-3/kg
4,160 kg/yr (P=100psia) 2,769,000 P&T, p. 266
Labour - $25/h 2,175,000 P&T, p. 265
Supervision 0.15 (L) - 326,300 P&T, p. 270
Maint. &
repair 0.07 (FCI) - 1,306,900 P&T, p. 266
Oper. Supplies 0.15 (M&R) - 196,000 P&T, p. 268
Labour
supplies 0.15 (L) 326,300 P&T, p. 204
40
Table 4-4: Indirect operating costs (EB = 156,000 tonne/yr).
4.4 Profitability
The current plant design is economically viable. Figure 4-1 shows the
the current EB selling price of $1.12/kg.71 Note that all other variables (e.g.
purchasing price of raw material) are held constant in the calculation. Figure
4-1 indicates that EB can be sold for $1.02/kg to break even and $1.09/kg to
100
90
80
Rate of Return (%)
70
60
50
40
30 ROR = 27%
20
Current = $1.12/kg
10
0
0.9 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8
Selling Price of EB ($)
Figure 4-1: Rate of return as a function of selling price.
Figure 4-2 shows the relationship of total capital cost (TCI) in $/tonne-year
41
the current production rate of 156,000 tonne/yr, the TCI and TOC are
190.0 1,000.0
Total Operating Cost
170.0
$ TCI/tonne-year
800.0
$ TOC/tonne
150.0
Total Capital Investment 600.0
130.0
110.0 400.0
90.0
200.0
70.0
50.0 0.0
110,000 120,000 130,000 140,000 150,000 160,000 170,000 180,000
EB Production (tonne/yr)
Figure 4-2: Relationship of total capital cost and total operating cost
as a function of EB production.
Figure 4-3 shows the relationship between ROR and ethyl benzene
50
45
$1.20/kg
40
35
$1.15/kg
30
ROR (%)
15
10
$1.05/kg
5
Current Rate = 156,000 tonne/yr
0
50,000 70,000 90,000 110,000 130,000 150,000 170,000 190,000 210,000 230,000 250,000
EB Production (tonne/yr)
42
5 Environmental Considerations
There are two main concerns that should be taken into consideration for the
plant design and costing: green house gas emissions and waste water
treatment.
gas. This natural gas shall be bought within Nova Chemical’s pipeline near
Sarnia. Combustion of the natural gas will produce greenhouse gas emissions
regulation guidelines. Two possibilities for managing CO2 emissions are CO2
atmosphere. There are three main sinks: biospheres (oceans and forests),
43
geological formations (coal beds and active or depleted oil and gas reservoirs),
from a waste stream and either direct it to a natural sink or store it for
industrial use. Modern industry dictates that the safest and most reliable
sink is to store CO2 in natural gas and oil reservoir. Based on the current
natural gas will be needed to supply the energy requires for the process.28
sequestered.
The vent gas from column C-1 that cannot be recovered will have to be
vented. An alternative is to flare the gas. Flaring the gas will burn the
released ethylene and benzene, producing CO2. While this may increase the
amount of CO2 exiting the plant, a high efficiency flare can reduce or
It is important to ensure that the flare gas does not contain liquid droplets,
as they will not necessarily combust upon exit from the plant. The release of
benzene is of most concern, as it may exit as liquid droplets in the vent gas. It
must be ensured that a high efficiency flare system is designed, along with
44
other preventative measures such as a scrubbing section to eliminate other
vent gas impurities. A centralized vent system could be designed around the
plant equipment such that vent gases exit a common flare system. This could
run off, waste water, process water, and sewage from the plant must all be
illegal. Process water used for heating and cooling must be treated before
One hazard associated with oily water sewers is H2S release. Hot process
water containing dissolved H2S enters the sewer system, and as the
This can poison plant employees and release into the environment. Design
45
substances, enforce penalties for environmental misconduct, and enforce
Environment Canada.
at this time, the most notable guideline from the act is outlined in CEPA 200.
Canada concerning the chemicals outlined in the act that break concentration
and storage threshold limits proposed by CEPA 200.32 For the purposes of
Environment Canada. Regulation thresholds are detailed in Table 5-1 for the
It is interesting to note that DEB was not present in the regulatory list. This
expected that the threshold limits will be breached and as such, detailed
46
Table 5-1: CEPA 200 regulatory limits.32
Threshold Storage
Molar Conc.
CAS # UN # Quantity
[%]
[tonnes]
Benzene 71-43-2 1114 1.0 10
Ethylene 100-41-4 1175 1.0 7000
EB 74-85-1 1038 & 1962 1.0 4.5
Toluene 108-85-3 1294 1.0 2500
legal requirement for companies to follow the NPRI reporting system subject
environment)
(PAH’s)
(HCB)
47
o Part 4 Substances – Criteria air contaiminants (CAC’s)
If any one of the criteria is met, then an NPRI report is required. The NPRI
also provides a standard for reporting substance releases. The legal basis for
disaster management.34
All main process chemicals used in this plant fall under Part 1A. The
required. It is expected that NPRI reporting will be required for this plant
once in operation.
applications. The ISO 9000 and 14000 standards families are generic
48
The ISO 9000 standard family is a standard centered on quality
plant condition quality. It will be the basis for the quality control team
Do)
49
• Program improvement (Act)
Both ISO 9000 and 14000 are designed around the principles of Plan, Do,
Check, and Act. These methods are generic to all business practices and are
not specific to any one process. Since Nova Chemical is an ISO 9001:2000
The health and explosion hazards presented by the aromatic compounds and
As mentioned in the Plant Safety section, the chemicals used in this process
present significant human health hazards. Benzene, EB, DEB, and toluene
are also toxic to plants and animals. Furthermore, benzene can contaminate
50
ground water and soil. EB and DEB degrade over a span of three days;
environmental policy.
On June 11th 2003, a fire broke out at the Nova Chemical plant in Bayport,
Texas. The heat from the fire ruptured pipes carrying EB. The EB ignited,
causing an explosion that sent EB soaring into the air and damaged
surrounding equipment.
body made remediation difficult. Several workers were exposed to high levels
of EB, causing skin irritation, redness, and swelling. The surrounding area,
EB.
Late testing done by Nova Chemical indicated that there was no EB soil
contamination. Independent testing indicated that not only were there levels
of 34 ppb above the regulation soil contamination limit, but the soil also
51
contained significantly higher levels of benzene, which is much more
The Nova Chemical explosion illustrates the need for proper substance
information on soil sampling in the allotted time cost Nova Chemical $25,000
per day until they were released. Legal costs and losses in production
accounting could have prevented the release of benzene into the surrounding
the ISO 14000 standard, could be useful in conjunction with NRPI reporting
6 Safety
The following sections address health and safety concerns associated with the
chemical transportation.
52
6.1.1 Ethylene
with lower and upper explosion limits of 3.1% to 32.0%, lower and upper
asphyxiant. Its boiling point is -103.0°C. Table 6-1 shows NFPA hazard codes
Table 6-1: NFPA codes for chemicals used in the production of EB.
Health 0 2 2 2 2 0 = No
Hazard
Flammability 4 3 3 2 3 1 = Slight
2 = Moderate
Reactivity 0 0 0 0 0 3 = Serious
4 = Severe
Table 6-2.
53
19.5% is maintained to prevent asphyxiation. There are three main safety
• Flammability
• Gas compression
• Asphyxiation
compressed gas storage, and health concerns in the event that there is an
ethylene leak. Ethylene gas leaks could cut off oxygen to plant workers,
causing severe injury or death. Compressed gas requires specific storage and
handling procedures, while fire fighting systems must be installed that can
effectively deal with an ethylene explosion or fire.40 Water spray and fog
techniques supported by alcohol resistant foam, dry chemical, and CO2 are
6.1.2 Benzene
a chemical formula of C6H6. Benzene vapours are flammable and will ignite
at lower and upper explosion limits of 1.0% to 6.7%, and a flammability range
the temperature becomes too high. The NFPA hazard codes for benzene are
54
Benzene poses extreme health hazards to plant workers if not properly
Moderate periods of exposure can cause cancer (leukemia). It can enter the
body through inhalation, ingestion, and skin absorption. Benzene has a very
high absorption rate through the skin.44 Table 6-3 outlines the exposure
organizations.
It should be noted that the odor threshold for benzene is 12 ppm, much
• Flammability
• Worker exposure / health risks
55
Fire prevention and suppression techniques will be important as flames can
travel along the vapour trail above liquid benzene to the source, such as a
storage tank. Dry chemical, alcohol resistant foam and CO2 extinguishing
media should be used. Water is only effective for cooling the source. The
severe impact of benzene on the human body means that strict procedures,
formula is C6H5C2H5. Apart from a higher boiling point of 136°C, it has very
flammability limits of 1.0% to 6.7%. EB, like benzene, is stable and non-
reactive. The NFPA hazard codes for EB are displayed in Table 6-1.
skin irritation, reddening, blistering, and dermatitis. EB can also cause sister
chromatid exchange. Table 6-4 outlines some occupational health and safety
exposure limits. It is important to note that the odor threshold is well below
56
the recommended exposure limits. The level at which one can detect the odor
is much less than the recommended threshold limit, so employees can detect
• Flammability
• Worker exposure / health risks
extinguishers. Water may be used to cool the area near the source of the fire.
Larger fires may also be controlled using water spray or fog techniques.
Proper PPE must be worn. Specific materials must be used for PPE, as
degradation can occur rapidly. The table below shows various materials and
57
Table 6-5: PPE material and break through time.49
Breakthrough Time
Material
[h]
Barricade >8
Viton >8
Teflon >4
Butyl Rubber <1
Natural Rubber <1
Neoprene <1
Nitrile Rubber <1
Polyethylene <1
Polyvinyl Alcohol <1
Polyvinyl Chloride <1
Saranex <1
DEB and TEB chemical properties are similar to EB. Both are flammable and
marginally increase as more ethyl groups are added to the benzene ring.
Fire hazards and health risks shall be handled in a similar fashion to EB and
benzene. The hazards of adding more ethyl groups to the benzene ring to
create EB, DEB, and TEB seem to decrease slightly, while boiling points
increase.
6.1.5 Toluene
has similar LFL-UFL limits (1.0%-7.0%) and a wider LEL-UEL range (3.3%-
19.0%). Due to the added functional group attached to the benzene ring, it
58
has a higher boiling and flash point (111°C and 7°C).52 The NFPA hazard
The most notable risks associated with toluene are the same as benzene:
• Flammability
• Worker exposure / health risks
all required for smaller fires. Water will not be useful for direct fire
suppression techniques. A water mist or fog can be used for larger fires to
suppress vapours.54
Toluene presents the same health risks as benzene. The IARC warns that
attack the central nervous system of the body, with multiple points of entry.43
Y-zeolite Catalyst
The Y-zeolite catalyst used for the alkylator and transalkylator are the EBZ-
59
spherical catalyst particles is 2.2 mm. It has a density of 740 kg/m3 and does
not contain any precious metals. The catalyst does not pose any safety
hazard. It is inert in storage and the dust explosion risk is minimal. The
catalyst is stored in 210 L steel drums in a cool dry area. Substances such as
water, oxygenates, olefins, chlorides, and sulfur poison the catalyst. The
catalyst has a long cycle length of 3 to 5 years per regeneration, and can last
for three regeneration cycles.55 The y-zeolite catalysts from UOP are safe and
environmentally friendly, thus the risk associated with storage and use is
minimal.
major chemicals present in ethyl benzene production. Table 6-6 is useful for
60
Table 6-6: Important explosion chemical properties for design
considerations.
Vapour
Boiling Flash
LFL-UFL LEL-UEL Pressure
Substance Point Point
[%] [%] [mmHG]
[°C] [°C]
@ 20°C
Ethylene -103.7 - 2.7-36.0 3.1-32.0 -a
Benzene 80.1 -11.0 1.3-7.1 1.0-6.7 166.5
Ethyl benzene 136.2 18.056 1.0-6.7 1.0-6.7 7.1
Di-ethyl 180.0 58.0 0.8-6.0 0.8-6.0 1.1b
benzene
Toluene57 111.0 7.0 1.0-7.0 3.3-19.0 22.0
a…above critical pressure
b…value determined at 25°C
Storage will also be an issue, as there are requirements for compressed gas
storage, which has its own set of problems, as outlined in Section 6.2. The
properties in Table 6-6 and the health risks associated with each substance
or fire. The construction should be designed such that not only could the tank
store ethylene under high pressure, but could reduce risk in the event of
61
system should be non-sparking and explosion proof. All lines associated with
the ethylene system should be earth grounded and bonded to minimize the
materials.40 This may eliminate the possibility of oxygen entering the tank,
This limits gas leak velocity and reduces the likelihood a gas cylinder will
become airborne.58
62
Figure 6-1: Typical ethylene storage tank.
This vessel can store between 6,000 to 80,000 gallons, and stores ethylene
liquid60. It should be noted that at 175 psig, ethylene must be kept below -
using R-22 as a refrigerant. Tanks are insulated and double walled using
system can be installed for fire suppression. A flare can be installed for the
63
explosion barrier was installed as an engineered safety device to help protect
Limited. Tank construction cost, inert gas material costs, and energy costs for
Benzene and ethyl benzene are both liquids at room temperature. While
discussed.
Benzene and ethyl benzene must be stored in a cool, dry area. It is important
that the area is well ventilated to decrease the likelihood that vapours could
explosion air mixture. Inerting a storage tank with nitrogen can be used to
explosion or fire.62
64
charge, if allowed to increase, can ignite benzene vapours and cause an
charge build up. Reducing the flow rate in transfer operations as well as
Data on catalyst properties and storage was difficult to obtain as most of the
raw materials benzene and ethylene, and as such storage will be on a much
smaller scale.
The following points are hazards that arise from the storage of the raw
materials for the process. They shall only be mentioned here, and expanded if
65
• Extreme cold from cryogenic gas
that the pressure relief systems cannot handle the overpressure from
A storage area could be made safer through use of the principles of inherent
Ethylene poses the greatest explosion risk. It may be prudent to design the
storage system to use several smaller storage tanks. This will minimize the
amount of ethylene available for combustion in the event of a fire. This can be
wise to limit the amount of R-22 stored at the facility. There is no sense in
storing enough R-22 to last several years when it would be safer to store
optimization of the R-22 refrigeration system could reduce the amount of new
66
could be studied to measure profitability whether the increase in safety is
ventilation systems should be such that natural heat convection and plant
Heat from reactors and boilers creates a natural convection air current,
which could be utilized to aid in ventilation of the plant. Since much of the
plant should be such that confined spaces and areas where vapours could be
trapped is at a minimum.
Storage conditions are such that it is not practical to move storage conditions
storage of ethylene is not practical. Cryogenic storage is safe such that the
Nova Chemical has an ethylene plant in Joffre, Alberta, and another plant in
Corunna, Ontario, that also produces ethylene. The Sarnia plant receives
67
both benzene and ethylene feed stocks from the Corunna plant directly via
pipeline.64
Pipelines are covered under many regulatory bodies, such as the Office of
Pipeline Safety for the Department of Transport in the U.S. The TPSSC
safety for the U.S. Such standards include codes for areas of high residential
• Length
• Material fluid
• Throughput
• Geography and climate
• Construction material
Temperatures in the pipeline can affect fluid flow and pipeline integrity. The
length of the pipeline can in part reflect the energy requirements for
is needed, and pumping requirements. The size of the pipeline depends on the
flow rate that is desired as well as the velocity of the fluid through the pipe.
68
Higher velocities can put unnecessary forces on the pipeline. The pipeline
hazards.
The Dow Fire and Explosion indices were used to identify the areas of highest
fire and explosion potential in the plant design. An index was created for the
major unit operations: each R-1/R-2 assembly reactor, R-3, C-1, and C-2. A
It is clear that the feed into the main alkylation section R-1/R-2 has the most
potential for explosion and fire. The main contributing factor to the high
value calculated for each reactor in the R-1/R-2 assembly is the large volume
of benzene flowing, mainly from the C-1 recycle. The R-1/R-2 assembly also
contains the largest amount of ethylene, which requires the use of a higher
material safety factor than R-3, which contains very little ethylene.
69
The columns have a low index. This is partly due to the fact that the columns
are outside, designed with proper drainage control systems, and do not
contain any reactions. These traits minimize the general process hazard
the operation and the size of the columns. The moderate pressures contribute
It should be noted that although C-1 and C-2 have the lowest indices,
business interruption costs the plant $US 10 million as opposed to $US 2.9
million from the R-1/R-2 assembly. C-1 and C-2 contain more product. Fires
and explosions from C-1 or C-2 would result in loss of product and a much
It can be concluded from the Dow F&EI that the R-1/R-2 assembly will
require further hazard analysis. Detail of the Dow F&EI can be seen in
Appendix E.
A Chemical Exposure Index was calculated for each of the major units and
70
Table 6-8: CEI calculated values.
The CEI values calculated were extremely high. This can be partially
liquid, but at a temperature above its boiling point. Any loss in pressure
71
The concentric circles represent increasing hazard distances for the R-1/R-2
assembly feed in the event of a worst cast exposure. The prevailing wind for
the area and direction of flow of the nearby St. Clair River is also shown72.
Benzene exposure concentrations of 1.5 ppm, 2.5 ppm, and 5 ppm correspond
amount benzene in each unit is directly related to the CEI, where a higher
amount of benzene yields a large CEI. It was determined that the R-1/R-2
actions required for a variety of scenarios that can take place around the R-1/
R-2 assembly. The what-if analysis can be seen in Appendix D. The following
72
sewers, and chemical level sensor systems should be implemented. Fire
of the plant, as well as a HAZOP once chemical data and design becomes
finalized.
The following case studies demonstrate the hazards associated with handling
industrial safety and loss management principles could have been used to
On November 24th, 2001, a Louisiana polymer plant exploded. The source was
caused the safety valve to rupture, causing the leak. The vapours found an
ignition source and exploded. Action was quickly taken to stop further vapour
leak, and the fires burnt out once the leak was stopped.66
73
On November 4th, 1985 at Petroleum Stripping Inc., two employees were
stripping a benzene barge that was not bonded to prevent static sparking. A
spark ignited the vapours, causing an explosion. Both employees were killed
These case studies point out the severity of a leak leading to an explosion for
both ethylene and benzene. The ethylene explosion was deemed an accident.
The safety valve may not have been properly sized for the operation. It is
possibility that they were not informed of the hazards of a flammable vapour
design and construction phase of the plant will avoid incorrect equipment
74
6.5.2 Short Term Ethyl Benzene Exposure
space. A plastic enclosure was used to control dust in the work area.
difficulty. The contractor workers and plant employees began to evacuate the
building as more and more people began to suffer the effects of exposure to
the leaking sealant. A strong negative pressure within the plant forced
sealant vapours through holes in the plastic enclosure and into the plant
stock room, which circulated vapours throughout the plant. No MSDS sheet
vapours and provide MSDS sheets should have been considered. This is an
hazard would have been identified using any of the appropriate hazard
result of long term exposure to benzene. The employee was a pen-ruler for the
print shop. He used different dyes and inks for custom orders such as county
75
ledgers. The pen-ruling machines were old, dating back to the early 1900’s.
He used a mist sprayer apply to benzene, alcohol, and other solvents to clean
the ink pens. He did not make use of proper PPE. There was no local exhaust
system, nor was he trained in the proper use and handling of benzene. A
drum of benzene had be left near the work area for years. No labeling or
was diagnosed with a plastic anemia in early 1988, and died April 11th 1988
This is a prime example of the effect of long term benzene exposure. The
worker was unaware that benzene posed a significant hazard to his health.
substitution.
These cast studies document accidents that could have been avoided. They
management principles:
76
• It is important to incorporate as many effective inherently safer
account, and as such valves, piping, and other equipment may not be
determine the hazards associated with all plant systems, from loading
scope of the operation and the hazards associated with their job.
plant. Many of these shall be considered in the design stage of the EB plant.
77
7 Conclusions
production plants.
Ethyl benzene plants are generally uneconomical; however gains are made in
Given the small relative price difference between benzene and EB, large
tonne/yr.
The current NPV of the plant is US$ 7 million, based on the assumed 20-year
life of the plant and a MARR of 20%. An MARR of 20% was selected since a
The R-1/R-2 reactor assembly contains two trains of reactors, each consisting
of two alkylation reactors. Running the reactors in this fashion reduces the
78
volumetric flow rate through each reactor, allowing for reasonably sized
The largest operational cost in the plant is the amount of raw benzene being
used in the process. A recycle system has been implemented in the simulation
in order to reduce the amount of purged benzene from 24,000 kg/h to 26 kg/h.
79
8 Recommendations
design.
• The underlying problem affecting many areas of the plant is the high
plant design:
feed streams are mixed before being cooled to the appropriate reaction
80
• Plant layout should be considered using supporting data from Dow
each piece of equipment will also be necessary for a full economic analysis.
81
References
82
23. CW price report, Chemical Week; Nov 17, 2004; 166, 38; ABI/INFORM
Global, pg. 27
24. Brown. R., Styrene Poised for Tight First Half of 2004, Chemical
Market Reporter; Dec 1, 2003; 264, 19; ABI/INFORM Global, pg. 1
25. http://www.the-innovation-group.com/ChemProfiles/Ethyl benzene.htm
26. http://www.ars.usda.gov/research/publications/Publications.htm?seq_n
o_115=137352
27. Green Power Suppliers,
http://www.electricitychoices.org/greenpower.html
28. Environment Canada: Greenhouse Gas Emissions:
http://www.ec.gc.ca/energ/oilgas/co2/co2_general_e.htm
29. Environment Canada: Vapour Flaring:
http://www.ec.gc.ca/energ/oilgas/flaring/flaring_general_e.htm
30. Local Hazardous Waste Management in King County: Oily Water:
http://www.govlink.org/hazwaste/business/wastedirectory/wastedetails.
cfm?wasteid=142
31. Department of Justice, Canada: Canadian Environmental Protection
Act: http://laws.justice.gc.ca/en/C-15.31/
32. Environment Canada: CEPA 200 Substance Reporting:
http://www.ec.gc.ca/CEPARegistry/guidelines/impl_guid/x4.cfm
33. Environment Canada: National Pollutant Release Inventory:
http://www.ec.gc.ca/pdb/npri/2003Guidance/Guide2003/NPRI_Guide_2
003.pdf#page=104
34. NFPA 1600 Standard: Disaster Emergency Planning & Business
Continuity Standard:
http://www.cheminst.ca/divisions/psm/CEPA200/MacKay%20CEPA%2
0200%20Preparedness%20%20Response%20Feb.%2004.ppt#262,12,NF
PA%201600
35. ISO (International Standards Organization) http://www.iso.org
36. ISO 14000 Environmental Management System:
http://www.iso.org/iso/en/prods-services/otherpubs/iso14000/model.pdf
37. Nova Chemical Explosion Bayport, Texas:
http://www.texasbucketbrigade.org/newsletter/june%20newsletter.html
38. Nova Chemical Explosion Bayport, Texas: Release Information:
http://kpft.igc.org/news/070203story5.html
39. Engineering Tool Box - http://www.engineeringtoolbox.com/9_423.html
40. BOC Gases – MSDS – Ethylene – http://www.vngas.com/pdf/g33.pdf
41. Physical and Theoretical Chemistry Laboratory
http://physchem.ox.ac.uk/MSDS/BE/benzene.html
42. MSDS - Benzene -
http://www.ril.com/cmshtml/msdsben.pdf?page_id=516
43. International Agency for Research on Cancer - http://www-
cie.iarc.fr/monoeval/crthall.html
83
44. MSDS – Ethyl benzene -
http://www.osha.gov/SLTC/healthguidelines/ethyl
benzene/recognition.html
45. Petro Canada – Benzene MSDS Sheet
46. MSDS Benzene -
http://www.ejnet.org/plastics/polystyrene/benzene.html
47. CHEMREST – Comprehensive guide to Chemical Resistant Best
Gloves
http://www.chemrest.com/Toxicity%20and%20Risk%20Codes/Ethyl%20
Benzene.htm
48. International Agency for Research on Cancer - http://www.iarc.fr/
49. MSDS - Ethyl benzene -
http://www.osha.gov/SLTC/healthguidelines/ethyl
benzene/recognition.html
50. MSDS – DEB - https://fscimage.fishersci.com/msds/38247.htm
51. CPChemTM MSDS – Chevron Phillips Chemical Company LP
52. Mallinckrodt Chemicals -
http://www.jtbaker.com/msds/englishhtml/t3913.htm
53. ScienceStuff.com - http://www.sciencestuff.com/msds/C2881.html
54. Mallinckrodt Chemicals -
http://www.jtbaker.com/msds/englishhtml/t3913.htm
55. UOP – http://www.uop.com
56. International Training Organization -
http://www.itcilo.it/actrav/actrav-english/telearn/osh/ic/100414.htm
57. Mallinckrodt Chemicals -
http://www.jtbaker.com/msds/englishhtml/t3913.
58. Canadian Center for Occupational Health & Safety -
http://www.ccohs.ca/oshanswers/chemicals/compressed/compress.html
59. Universal Industrial Gases Inc. -
http://www.uigi.com/lng_eth_tanks.html
60. Larsen & Toubro Limited -
http://www.lntenc.com/lntenc/services/industries/chemical/cryogenic.htm
61. Larsen & Toubro Limited -
http://www.lntenc.com/projects/chemical/cryogenicprojects.htm
62. Petro Canada – Benzene MSDS Sheet
63. Canadian Center for Occupational Health and Safety -
http://www.ccohs.com/oshanswers/chemicals/chem_profiles/benzene/wo
rking_ben.html
64. Nova Chemical,
http://www.novachem.com/03_locations/03_manufacturing_f.html
65. USDOT – Office of Pipeline Safety - http://ops.dot.gov/
66. Louisiana polymer plant explosion: http://www.acusafe.com
84
67. Petroleum Stripping Inc. benzene explosion:
http://www.osha.gov/pls/imis/accidentsearch.accident_detail?id=144984
63
68. Automotive Switch Co.: EB employee exposure:
http://www.osha.gov/pls/imis/accidentsearch.accident_detail?id=675231
69. C.F. Hoekel Company: Long term benzene exposure:
http://www.osha.gov/pls/imis/accidentsearch.accident_detail?id=145060
59
70. Nova Chemicals 2004 Annual Report,
http://www.novachem.com/AnnualReport04/nova.htm
71. Viswanathan, P., ACN: Asian Chemical News, Mar 14-Mar 20, 2005.
Vol.11, Iss. 482; pg. 25
72. Sarnia Prevailing Winds, http://www.theweathernetwork.com
85
Appendices
A. Economics Spreadsheet
ITEM VALUE ITEM VALUE $/kg
Labour (4 operators) $25/h Project Start Sept 2006
Plant Start-up Sept 2007 Ethylene ($/lb) 0.22 0.484
Plant life 20 a Income Tax 60.0% Benzene ($/gal) 3.5 1.05
Hours/year 8700 Styrene ($/lb) 0.64
Feed water $0.008/kg Ethylbenzene ($/lb) 0.5104 1.12288
86
Total Plant Cost $ 23,720,434.22
FCI $18,670,673
Products Products
EB ($/kg) $ 1.12 EB (kg/hr) 17,956.70
Total Working Capital
Interest
Interest Rate (%) 20% P&T (p. 322) Medium Level of Risk Year Charge Payment Balance
Tax Rate (%) 60% 0 8 36652.54988 7,116,130.27
Economic life (# Years) 20 1 8 36652.54988 7,648,768.14
Hours/year 8700 2 8 36652.54988 8,224,017.04
Year 0 1 2 3 4 5 6 7
87
Operating Costs $156,979,035.63 $156,979,035.63 $156,979,035.63 $156,979,035.63 $156,979,035.63 $156,979,035.63 $156,979,035.63
Product sales $175,420,023.54 $175,420,024 $175,420,024 $175,420,024 $175,420,024 $175,420,024
Gross Revenue -$23,720,434.22 $0.00 $18,440,987.91 $18,440,987.91 $18,440,988 $18,440,988 $18,440,988 $18,440,988
Depreciation $933,533.66 $933,533.66 $933,533.66 $933,533.66 $933,533.66 $933,533.66
Gross Profit -$23,720,434.22 $0.00 $17,507,454 $17,507,454 $17,507,454 $17,507,454 $17,507,454 $17,507,454
Tax $10,504,472.55 $10,504,472.55 $10,504,472.55 $10,504,472.55 $10,504,472.55 $10,504,472.55 $10,504,472.55
Net Profit -$23,720,434.22 $0.00 $7,936,515 $7,936,515 $7,936,515 $7,936,515 $7,936,515 $7,936,515
C = Co (size)n (B.1)
Where:
C = cost of equipment
Co = a constant
n = cost exponent
Co and n are found knowing two values of cost and size. Taking the natural
log (ln) of Eq. (B.1.):
ln
C2
= n ln
(size)2
C1 (size)1 (B.3)
Description: Carbon steel, 300 psia (2070 kPa) {current process is at 260 psia}
6.0 m3 = $40,000
0.2 m3 = $5,000
So,
40,000 6
ln = n ln (B4)
5,0001 0 .2
Solve for n:
n = 0.611
Co = 13,880
∴ cost = 13,880(Volume)0.611
88
Cost of Heat Exchanger
5 m2 = $3,000
400 m2 = $30,000
So,
30,000 400
ln = n ln (B.6)
3,0001 5
Solve for n:
n = 0.525
Co = 12,900
∴ cost = 12,900(Area)0.525
89
C. Glossary
ACGIH- American Conference of Governmental Industrial Hygienists
TLV Threshhold Limit Value
DEB Di-ethyl benzene
EB Ethyl benzene
IARC International Agency for the Research on Cancer
IRIS Integrated Risk Information System
IRR Internal rate of return
LD50/LC50 Lethal Dose/ Concentration Kill 50%
LDLo/LCLo Lowest published lethal dose
LEL-UEL Lower and upper explosive limits
LFL-UFL Lower and upper flammability limits
NFPA National Fire Prevention Association
NIOSH- National Institute for Occupational Health and Safety
REL Recommended Exposure Limit
NTP National Toxicology Program
OSHA-PEL Occupational Health and Safety Association Permissible
Exposure Limit
ROR Rate of return
STEL Short Term Exposure Limit (15 min)
TEB Tri-ethyl benzene
TWA Time weighted average
90
D. What-if? Analysis
EXISTING SAFE-
WHAT-IF CONSEQUENCE(S) RECOMMENDATIONS
GUARDS
1) What if • Flammable vapors • Safety shower, fire • Ensure that safety devices
there is a within 1.3 vol% or blankets, and such as safety showers,
Benzene spill below or 8 vol% high CO2/Dry Chemical extinguishers, and remote
from a surge may ignite off the surge extinguishers are control are operational and
drum in the R- drum pumps or other present near the maintained.
1 assembly? ignition source. Causing surge drum and • Safety courses (WHMIS)
Harm or loss to process, every 20 meters to ensure employees are
personnel and/or thereafter. aware of the hazards.
environment. • Level controls • Inspection of process to
• Human exposure to a present on the surge minimize benzene or other
carcinogenic chemical drum with operator chemical spill from unit
alarms and control operations.
options via a remote • Ensure the process
source. controller is functioning
• Chemical sewers properly or calibrated
and proper correctly on a regular basis.
treatment of sewage. • Investigate and control the
amount of raw benzene
contained in the plant site.
2) What if • Exposure to a • See existing • Ensure that PPE is in
there is human carcinogenic substance safeguards for surge good working condition.
exposure to which may result in drum spill. • Ensure that procedures for
benzene near burns to the eyes and • PPE such as safety evacuation and cleanup are
the R-1 face and increase glasses, coveralls and up to date and in practices.
assembly? potential of cancer. safety gloves.
• Safety procedures
for cleanup and
evacuation.
3) What if • Possible loss to • Fire codes • Ensure codes are in
there is a fire property, process, enforced, and practice
near the R-1 people and practiced by fire hall • Ensure MSDS’s of
assembly? environment. or department. flammable components are
(includes: • Safety awareness on site (for hazard
benzene, by management to awareness)
ethylbenzene, employees regarding • Quarterly fire drill
and ethylene) fire hazards of improvement plans by fire
chemicals used on hall and management
plants.
• Fire alarms on site
• Fire retardant
construction and
materials.
91
4) What if a • Property Damage • Explosion • Proper emergency
reactor in the • Injury/death barricades procedural training
R-1 assembly • Halted production • Proper plant layout practices regularly
explodes? • Fire can spread to where reactors are • Ensure adequate PPE is
other parts of the plant outside minimum readily accessible in the
range for explosion event of an explosion (for
(Dow F&EI) Benzene exposure, smoke
• Sprinkler/ CO2/ etc.)
Chemical • Install Properly
Extinguishers functioning explosion
• Water curtain venting to direct explosive
• Emergency shut-off force
valve system
• High strength
materials
construction for the
reactors
5) What if the • Ethylene/ benzene • None currently • Redundant compressors
reactor section flash present in simulation and pumps
looses pressure • Possible leak of gas • Water curtain to • Vapor collection and
(pressure into plant / atmosphere contain any large recycle systems
decrease)? • Vapors enter vapor release
downstream operations
/ pumps
• Heat exchanger
efficiency will decrease
as a result of vapors in
tubes (poor contact,
heat transfer properties
of vapor))
• Distillation column
operating conditions
will be affected
6) What-if • Reactor pressure • Pressure Safety • Ensure engineered safety
reactor causes explosion Release/ Valve items are incorporated into
pressure/ • Temperature runway • temperature process, and ensure all are
temperature degrades tubes controlled jacket in proper working condition
increases well • Temperature and around reactor • Update or create more
above desired pressure damages • appropriate unit rigorous safety inspections
operational reactor internals operations upstream and protocols for reactor
values? • Temperature causes to control reactor maintenance
(exothermic coking (fine particles feed • Inspect process control to
reaction) degrades catalyst) • appropriate process ensure it is properly tuned.
• Possible loss to People control in place to • Follow proper
• Loss to process during control reactor maintenance schedule and
shutdown. conditions equipment strategies
• Possible loss to
environment due to
92
reactor spillage or
vapors released into air.
7) What if • process shut down • Properly labeled • investigate whether non-
there is an • non-sparking or storage area and sparking or ignition unit
Ethylene feed ignition components tanks operations are used
system installed (unit • NO SMOKING • Incorporate a maintenance
complication? operations) signs appropriately schedule to ensure tight
(explosion, fire, • Storage tanks ignite placed seals on fittings and assess
etc.) and exploding, causing • Explosion degradation of storage area.
damage to the property barricades protecting • Reduce the amount of
and halting process. existing equipment Ethylene stored in one place.
People and environment • Chemical • Install proper ventilation
may also be harmed. monitoring and system to avoid gas buildup.
alarm systems both • Possible redundant feed
portable and fixed. system design
• Fire retardant
construction and
materials.
93
E. F&EI Sample Calculations
R-1/R-2 Assembly Material Factor: Ethylene 24.00
Penalty Penalty
Factor Factor
1 General Process Hazards Range Used
94
1. Process Control Credit Factors (C1)
Credit Credit
Factor Factor
Feature Used Feature Used
C1 Value 0.57
Credit Credit
Factor Factor
Feature Used Feature Used
C2 Value 0.84
Credit Credit
Factor Factor
Feature Used Feature Used
C3 Value 0.54
95
R-3 Material Factor: Benzene 16.00
Penalty
Penalty Factor Factor
1 General Process Hazards Range Used
Hc (BTU/lb) 18,000
96
1. Process Control Credit Factors (C1)
Credit Credit
Factor Factor
Feature Used Feature Used
C1 Value 0.57
Credit Credit
Factor Factor
Feature Used Feature Used
C2 Value 0.84
Credit Credit
Factor Factor
Feature Used Feature Used
C3 Value 0.54
97
C-1 Material Factor: Benzene 16.00
Penalty Penalty
Factor Factor
1 General Process Hazards Range Used
98
1. Process Control Credit Factors (C1)
Credit Credit
Factor Factor
Feature Used Feature Used
C1 Value 0.57
Credit Credit
Factor Factor
Feature Used Feature Used
C2 Value 0.84
Credit Credit
Factor Factor
Feature Used Feature Used
C3 Value 0.54
99
C-2 Material Factor: Benzene 16.00
Penalty Penalty
Factor Factor
1 General Process Hazards Range Used
100
1. Process Control Credit Factors (C1)
Credit Credit
Factor Factor
Feature Used Feature Used
C1 Value 0.57
Credit Credit
Factor Factor
Feature Used Feature Used
C2 Value 0.84
Credit Credit
Factor Factor
Feature Used Feature Used
C3 Value 0.54
101
F. CEI Sample Calculations
A sample calculation for the CEI is shown below, using the feed to the R-1/R-
2 assembly. The Chemical Exposure Index (CEI) was calculated using the
procedure on page 3 of the “Chemical Exposure Index Guide, September
1993, 2nd edition.
Step One: Define the chemical being investigated and the conditions at
which the scenario is taking place. In our case this is not a
scenario, it is a real event.
Chemical Name: Benzene (Gas): Assume that all the liquid vaporized
Temperature: 83°C
Pressure: 400 kPa at C-1 assembly
Rate of Release: 60,000 kg/hr × 1 hr/60 min=1,000 kg/min=2,200 lb/min
Step Three: Determine the Airborne Quantity (AQ) using a gas relationship
and US/BRIT Units.
Where:
AQ is the Airborne Quantity
D is the diameter of the hole (inches)
Pa is the absolute pressure (Pg +14.7)
Pg is the gauge pressure (PSIG)
102
The result of the AQ calculation is as follows:
Where:
CEI is the Chemical Exposure Index
ERPG-2 is the Emergency Exposure Planning Guideline (ppm)
The value of this CEI is quite high. The guide states on page i, a CEI greater
then 200 for a facilities will require further risk analysis. The calculation of
the Hazard Distance (HD) using US/Brits units is done using the following
expression.
HD=9,243 AQ/ERPG(MW)
Where:
HD is the Hazard Distance (ft)
AQ is the Airborne Quantity (ppm)
ERPG is the Emergency Exposure Planning Guideline
MW is the molecular weight
103
The result for the HD expression for ERPG-2 is as follows:
104
G. HYSYS Workbook Output
105