Bek MDP

Vinyl Chloride Production
CHEN 4520 Chemical Process Synthesis
December 9th, 2016
Developed for Thomas K. Belval
by Group 10
Lucas Karasek Bruce Kirkpatrick Aaron Lipsey Kaela Siahpush

EXECUTIVE SUMMARY
This report is first and foremost a comparison of two process units producing vinyl chloride.
The baseline process consisted of a direct chlorination followed by thermal cracking; we attempted to design
and plan a process to produce the same amount of vinyl chloride more efficiently through an oxychlorination-
to-thermal cracking approach. We used Aspen to generate working models of both processes, and saw that
adding a recycle to the new oxychlorination process would result in a vastly improved plant.
We then conducted several analyses to illustrate our success and were able to successfully demonstrate the
improved environmental impact, utility cost, and profitability of our new reaction scheme. We created models
of the process units so that they both produced 5250 kg/hr of vinyl chloride, with nearly identical purities (by
mass) of 98% for oxychlorination and 97.6% for direct chlorination.
It is important that both models have the same capacity, as much of the environmental impact of a process is
driven by mass flow (especially when the processes are this similar). With equal mass flows of vinyl chloride, we
were able to conduct an environmental assessment of both processes. Using Biwer’s method of environmental
assessment, we determined that the increased conversion of hydrogen chloride afforded by the recycle greatly
reduced the environmental impact of the process. However, the more important addition may have been the
implementation of the 1,2-dichloroethane recycle. The additional recycle stream improved conversion of the
pyrolysis reaction to over 99%. By far, the most volatile and hazardous compounds in this process are the
intermediate products, and any addition to the process that almost entirely eliminates such products is bound
to result in a much smaller environmental impact.
We compared the potential profit offered by both processes. The first step in determining the financial viability
of each design was to calculate the Total Capital Investment. The oxychlorination process immediately provided
savings, with a TCI of $10.5MM compared to $11.76MM for the direct chlorination reaction. Over the production
lifetime of the plant, the oxychlorination provides nearly three times the profit, with a cumulative Present Value
of $42.26MM after 15 years compared to just $15.41MM for the direct chlorination.
We also analyzed utility requirements using the composite curve method, and prepared a stream matching
chart. The results showed that the oxychlorination process had smaller hot and cold utility requirements. The
oxychlorination process had a hot utility of 5.5  106 kJ/hr compared to of 1.15  107 kJ/hr for direct chlorination.
Similarly, oxychlorination needed only 1.54  107 of cold utility compared to 2.5  107 kJ/hr in the direct
chlorination process. The resulting heat integration showed why this was the case, as the oxychlorination
process was able to match six streams compared to five for the direct chlorination process.
When comparing the two processes, the only positive presented by the direct chlorination was the simpler
process design (the oxychlorination process has six extra streams). However, this report will demonstrate how
an increase in complexity can increase efficiency and profit. This new plant might even allow our group to ascend
beyond vinyl chloride, to the high stakes polyvinyl chloride business!
Table of Contents
Executive Summary ...........................................................................................................................................................................2
Objective ...........................................................................................................................................................................................4
Design Basis.......................................................................................................................................................................................4
Direct Chlorination Process Design ....................................................................................................................................................1
Direct Chlorination Simulation Development Summary .................................................................................................................................... 2
Oxychlorination Process Design.........................................................................................................................................................3

Oxychlorination Simulation Development Summary ........................................................................................................................................ 5
Utility Requirements .........................................................................................................................................................................6
Direct Chlorination Composite Curve ................................................................................................................................................................ 6
Oxychlorination Composite Curve .................................................................................................................................................................... 6
Utilities Summary ............................................................................................................................................................................................. 7
Direct Chlorination ................................................................................................................................................................................................. 7
Oxychlorination ...................................................................................................................................................................................................... 7
Comparison ............................................................................................................................................................................................................ 7
Environmental Sustainability Assessment .........................................................................................................................................7
Biwer’s Method Overview ................................................................................................................................................................................ 7
Environmental Analysis .................................................................................................................................................................................... 8
Financial Sustainability Assessment ..................................................................................................................................................9

Equipment Costs .............................................................................................................................................................................................10
Equipment Sizing .............................................................................................................................................................................................10
Bare-Module Costing .......................................................................................................................................................................................11
Total Capital Investment .................................................................................................................................................................................11
Total Production Cost ......................................................................................................................................................................................12
Profitability Analysis .......................................................................................................................................................................................13
Return on Investment and Payback Period .......................................................................................................................................................... 13
Net Present Value (NPV) and Investor’s Rate of Return (IRR) .............................................................................................................................. 13
Summary of Profitability Analysis ........................................................................................................................................................................ 14
Direct Chlorination Net Present Value Sensitivity Analysis .............................................................................................................. 15

Bibliography .................................................................................................................................................................................... 16
Appendices ...................................................................................................................................................................................... 18
Appendix A: Process Design.............................................................................................................................................................................18
Reaction Schemes – Direct Chlorination .............................................................................................................................................................. 18
Reaction Schemes – Oxychlorination ................................................................................................................................................................... 19
Process Motivation .............................................................................................................................................................................................. 20
Modeling .............................................................................................................................................................................................................. 21
Appendix B: Stream Matching Diagrams..........................................................................................................................................................22
Direct chlorination ............................................................................................................................................................................................... 22
Oxychlorination .................................................................................................................................................................................................... 23
Appendix C: Environmental Sustainability .......................................................................................................................................................24
Environmental Factor Tables – Direct Chlorination ............................................................................................................................................. 25
Environmental Factor Tables – Oxychlorination .................................................................................................................................................. 27
Biwer Rating Rationale – Direct Chlorination ....................................................................................................................................................... 31
Biwer Rating Rationale – Oxychlorination ............................................................................................................................................................ 32
Appendix D: Financial Sustainability ................................................................................................................................................................33
Estimate of Total Capital Investment ................................................................................................................................................................... 33
Estimate of Total Production Costs ...................................................................................................................................................................... 34
Profitability .......................................................................................................................................................................................................... 35
Sensitivity of IRR................................................................................................................................................................................................... 37
Cost Sheet for Direct Chlorination Model ............................................................................................................................................................ 38
Cost Sheet for Oxychlorination Model ................................................................................................................................................................. 39
OBJECTIVE
The primary objective of this project is to develop a well-conceived design of an oxychlorination process with
the capacity to produce a total of 40 million kilograms of vinyl chloride per year (5,000 kg/hr for 8,000 hr/year).
In order to maintain a standard of quality that will keep the plant profitable, we must deliver a product that is
at least 95% pure. During the development of the process design, we are constantly striving to minimize
environmental impact and financial risk, while maximizing safety and efficiency. To accomplish this, we will
design an oxychlorination process that is superior to the baseline direct chlorination process and is more
sustainable than the baseline process (USA Patent No. 2929852, 1950; UK Patent No. 938824, 1963).
Our plan to design such a process focuses on limiting the amount of HCl exiting the oxychlorination process. This
will not only reduce our environmental impact by reducing the amount of caustic HCl leaving our system, but
also make the plant more profitable by increasing the conversion of the same component. We will implement
Biwer’s method (Biwer, 2004) of environmental assessment to monitor sustainability and compare the relative
environmental impacts of the two processes. In order to determine financial sustainability, we will conduct Total
Capital Investment and cash flow analyses. These methods require extensive sizing and pricing data, which will
be acquired via both a rigorous simulation and literature consultation. By the end of this report, we will have
provided a detailed and comprehensive plan for producing vinyl chloride at a reasonable rate of return.
Vinyl chloride is not itself a useful product (Armstrong, 2014). It’s a commodity chemical, as its primary use is as
a precursor of polyvinyl chloride plastics. The fact that we are not actually producing an end-product means that
there are several objectives that we may want to set for ourselves after constructing our new vinyl chloride
plant. First, there is the obvious wasted profit potential of manufacturing our own PVC. Instead of selling our
supply of a high purity, low cost vinyl chloride to other manufacturers, we could simply re-invest that capital in
our own plant for even greater returns. Furthermore, now that we’re expanding our floor plan anyway, there
are myriad products that could utilize spare HCl. Even with the recycle, there is a great deal of unreacted HCl
leaving our process; valuable capital simply being flushed away (Santos, 2014)!
DESIGN BASIS
1. The plant needs to make 5,000 kg/hr of vinyl 12. Oxychlorination column design recycles 1,1,2-
chloride for 8000 hr/yr trichloroethane and 1,4-dichlorobutane entirely (negligible
2. The process is continuous amounts of these compounds exist in the outlet streams)
3. Plant has 3 year start up time 13. SRK Thermodynamic Package (Pro/II, 1992)
4. Plant has a 15 year production run 14. Cash reserves accounted for 8.33% of the annual
cost of manufacture.
5. Selling price of vinyl chloride = 1200 $/metric ton 15. Inventory amounted to 1.92% of annual sales of
6. Plant runs at 90% capacity after start-up liquid and solid products
7. Income tax rate = 40% 16. Accounts receivable amounted to 8.33% of all
8. There is no need to purchase land annual sales.
17. Accounts payable amounted to 8.33% of annual
9. The existing utilities supporting direct chlorination
feedstock costs.
processing units have enough extra capacity to cover the
18. Decanter estimated as a horizontal pressure vessel
needs of the oxychlorination processing unit.
in model
10. The warehouse, QC lab, and staff facilities have
enough space to cover the needs of the new processing unit 19. ∆Tmin at pinch point = 10
11. Thermal cracking reaction has approx.. 65% 20. Both direct and oxy chlorination reactors treated as
conversion PFRs
DIRECT CHLORINATION PROCESS DESIGN
The direct chlorination method of vinyl chloride production begins with its namesake: the direct chlorination of
ethylene to produce 1,2-dichloroethane. Ethylene and chlorine (streams 1 and 2) are fed in stoichiometric
amounts at 25°C and 1 atm to a 1.5 atm bubble column reactor (R-100) that circulates the reactant gases via
sparger dispersion through liquid 1,2-dichloroethane that is maintained at 90°C by a cold water stream (E-100).
The bubble column reactor design maximizes ethylene mass transfer and its use in industry is well-characterized
(Orejas, 2001). The product stream exiting the direct chlorination reactor is a 97% pure 1,2-dichloroethane
stream (stream 3) with limited side reaction and unreacted feed compounds (see Appendix A for a thorough
description of process unit designs and a discussion of the various reactions and kinetics involved with this
system). R-100 also contains ferric chloride that acts as a Lewis acid catalyst, polarizing chlorine to increase its
electrophilic activity and encourage attack on ethylene’s double bond (Wachi & Asai, Kinetics of 1,2-
Dichloroethane Formation from Ethylene and Cupric Chloride, 1994).
The 1,2-dichloroethane stream is joined by a recycle (producing stream 4) and fed through a centrifugal pump
(P-100; stream 5) and a fired-heat evaporator (E-101; stream 6) to achieve pressurization to 26 atm, complete
vaporization, and a temperature increase to 500°C. This stream is flown into a pyrolysis furnace at the same
temperature and pressure, where it is primarily converted to vinyl chloride. Although a catalytic pyrolysis
method exists, similar conversion levels can be reached without a catalyst, making the non-catalytic approach
a simpler, less expensive, and more favorable method (Dreher, Torkelson, & Beutel, 2012; Rus, 2013). The
furnace contents are transferred to a quench tank (V-100; stream 7), which is maintained at 6°C and 12 atm by
Figure DC.1 – EFD for direct chlorination process. Numbered streams correspond to Table DC.1.
circulating the liquid condensate exiting the pyrolysis furnace through a refrigerant-cooled condenser system
(P-101, E-102). The quench tank is a vital component of this process: Without rapid cooling the pyrolysis reaction
will continue, degrading desirable vinyl chloride and producing additional unwanted side products.
The quench contents are fed to a 7-stage distillation column above stage 2 at 12 atm (T-100; stream 8) where
HCl is recovered at 97% purity in the distillate (stream 9) and the remainder of the pyrolysis products are fed in
the bottoms stream to a second, similar, 9-stage distillation column above stage 3 at 4.8 atm (T-101; stream 10).
This column yields a 97.6% pure vinyl chloride stream in the distillate (stream 11) and the 1,2-dichloroethane-
rich bottoms stream is recycled ahead of the centrifugal pump (stream 12).
Figure DC.2 – PFD for direct chlorination process. Mass flow rates and utility values generated by Aspen Plus.
Direct Chlorination Simulation Development Summary
Aspen Plus was used to design and simulate the baseline direct chlorination process. Briefly, the direct
chlorination reactor was sized using the formation kinetics of 1,2-dichloroethane and 1,1,2-trichloroethane
(Wachi & Morikawa, Liquid-Phase Chlorination of Ethylene and 1,2-Dichloroethane, 1996) and the temperature
and pressure shown in the conceptual process PFD. These conditions produced an ethylene conversion of
approximately 98%, which is conservatively in agreement with literature (Benyahia, 2005). Pumps and coolers
were sized based on stream requirements given in the conceptual PFD.
The pyrolysis furnace was modeled as a catalyst-packed PFR with shell-and-tube innards, which is a very typical
furnace design for these simulations (Dreher, Torkelson, & Beutel, 2012). The furnace included several reaction
sets that required complex rate law modeling (Dimian & Bildea, 2008); the model resulted in an approximate
60% single-pass conversion of 1,2-dichloroethane, which is also in agreement with literature. The quench was
modeled as a refrigerant-cooled circulating vessel in accordance with the conceptual PFD. The columns were
modeled with RadFrac distillation towers, allowing for realistic simulation based on volatility and desired
distillate flowrate. Column T-100 was run at a reflux ratio of 0.8 and a boilup ratio of 1.25 and column T-101 was
run at a reflux ratio of 0.9 and a boilup ratio of 1.90. The recycle line results in a 98.6% 1,2-dichloroethane multi-
pass conversion, which is similar to reported literature values. See Appendix A for an in-depth discussion of the
modeling process.
Table DC.1 – Stream summaries for direct chlorination process.
Stream Number 1 2 3 4 5 6
Temperature (°C) 25 25 90 94.5 181.9 242
Pressure (Atm) 1 1 1.5 1.5 26 26
Vapor fraction 1 1 0.11 0.14 0 1
Mass flow (kg/hr) 2,500 6,000 8,500 14,000 14,000 14,000
Molar flow (kmol/hr) 86 86 87 142 142 142
Component molar flow (kmol/hr):
Ethylene 85.9 0 1.3 1.3 1.3 1.3
Chlorine 0 85.9 0.9 0.9 0.9 0.9
1,2-dichloroethane 0 0 84.2 137.2 137.2 137.2
Hydrogen chloride 0 0 0.4 0.4 0.4 0.4
1,1,2-trichloroethane 0 0 0.4 2.2 2.2 2.2
Vinyl chloride 0 0 0 0 0 0
= 1,4-dichlorobutane 0 0 0 0.1 0.1 0.1
Stream Number 7 8 9 10 11 12
Temperature (°C) 500 6 -21.3 94.2 30.8 144.5
Pressure (Atm) 26 12 12 12 4.8 4.8
Vapor fraction 1 0 1 0 0 0
Mass flow (kg/hr) 14,000 14,000 3,250 10,750 5,250 5,500
Molar flow (kmol/hr) 225 225 86 139 84 55
Component molar flow (kmol/hr)
Ethylene 1.3 1.3 1.3 0 0 0
Chlorine 0.3 0.3 0 0.3 0.3 0
1,2-dichloroethane 54.2 54.2 0 54.2 1.2 53
Hydrogen chloride 84.1 84.1 83.6 0.6 0.6 0
1,1,2-trichloroethane 1.7 1.7 0 1.7 0 1.7
Vinyl chloride 83.1 83.1 1.1 82 82 0
1,4-dichlorobutane 0.1 0.1 0 0.1 0 0.1
The stream summary table shows the individual component mole flows, allowing for closer inspection of the
material balances. Conveniently, our column design recycles 1,1,2-trichloroethane and 1,4-dichlorobutane
entirely (negligible amounts of these compounds exist in the outlet streams, 9 and 11). Additionally, the
simulation yields 5,125 kg/hr of vinyl chloride, which translates to an 95.4% overall conversion of feed ethylene
to outlet vinyl chloride.
OXYCHLORINATION PROCESS DESIGN

The oxychlorination process design is highly comparable to the direct chlorination method, with many shared
downstream operations (Benyahia, 2005). It begins with preheated (from storage at 25°C) near-stoichiometric
feeds of pure ethylene, oxygen, and hydrogen chloride (streams 1,2, and 3; stream 3 joins with a recycle stream
to form stream 4) entering an oxychlorination reactor (R-200). Oxychlorination reactors are gas phase reactors,
which avoid corrosion by aqueous acid solutions (a classic pitfall of direct chlorination reactors) (Magistro &
Cowfer, 1986). To maintain a vapor fraction of 1, the reactor is held at 260°C and 10 atm.
The oxychlorination products (stream 5) are flown to a decanter (D-200), which removes gas (stream 6) and
water (stream 7). The bottoms stream from the decanter, stream 8, is joined by a recycle (to form stream 9)
before entering a centrifugal pump and heating system in preparation for pyrolysis (F-200; streams 10 and 11).
As with the direct chlorination method, the pyrolysis furnace runs at 500°C and 26 atm before opening into a
quench tank (V-200; stream 12) at 12 bar and 6°C. The quench tank temperature is maintained by continuous
material circulation in contact with a refrigerant stream. After cooling, the products travel to distillation columns
that are essentially identical to those in the direct chlorination process (T-200 and T-201; streams 13 and 15),
which one major deviation. In the oxychlorination model, the distillate HCl from T-200 (stream 14) is recycled
upstream to enter the oxychlorination reactor alongside the pure components. Similar to the direct chlorination
process, the distillate from T-201 (stream 16) is 98% pure vinyl chloride at 13°C and 4.8 atm while the bottoms
(stream 17), which is primarily water and 1,2-dichloroethane, is recycled to merge with the enriched 1,2-
dichloroethane exiting the bottom of the decanter.
Figure OC.1 – EFD for oxychlorination process. Numbered streams correspond to Table OC.1.
Figure OC.2 – PFD for oxychlorination process. Mass flow rates and utility values generated by Aspen Plus.
Oxychlorination Simulation Development Summary
Aspen Plus was also used to design and simulate the oxychlorination process. Briefly, the oxychlorination reactor
was sized using the formation kinetics of 1,2-dichloroethane and 1,1,2-trichloroethane (Wachi & Morikawa,
Liquid-Phase Chlorination of Ethylene and 1,2-Dichloroethane, 1996; Moreira & Pires, 2010) and the
temperature described in literature (Moreira & Pires, 2010). These conditions produced an ethylene conversion
of approximately 97%, which is conservatively in agreement with literature (Benyahia, 2005; Magistro & Cowfer,
1986). Pumps and coolers were sized based on stream requirements, as the downstream process (outside of
the recycles) is the same as in the direct chlorination model. For an extensive discussion of this process, its unit
operations, the reactions involved, and the modeling scheme, see Appendix A.
Table OC.1 – Stream summaries for oxychlorination process.
Stream Number 1 2 3 4 5 6 7 8 9
Temperature (°C) 250 250 250 120.9 260 -35.2 -35.2 -35.2 -8.7
Pressure (Atm) 10 10 9.9 9.9 10 1 1 1 1
Vapor fraction 1 1 1 1 1 1 0 0 0
Mass flow (kg/hr) 1,500 2,500 3,750 7,250 11,250 750 1,750 8,750 14,500
Molar flow (kmol/hr) 44 89 104 196 194 13 85 96 164
Ethylene 0 88.5 0 0.7 3.3 2.6 0 0.7 0.7
Hydrogen chloride 0 0 103.7 194.9 16.3 8.6 0 7.7 7.7
Oxygen 44.3 0 0 0 1.3 1.3 0 0 0
1,2-dichloroethane 0 0 0 0 85.9 0 0 85.9 138.7
Water 0 0 0 0 86 0 84.6 1.4 12.7
Vinyl chloride 0 0 0 0.8 0.8 0.1 0 0.8 3.8
Chlorine 0 0 0 0 0.1 0 0 0.1 0.1
1,1,2-trichloroethane 0 0 0 0 0 0 0 0 0.05
1,4-dichlorobutane 0 0 0 0 0 0 0 0 0.05
Stream Number 10 11 12 13 14 15 16 17 18
Temperature (°C) -0.2 242 500 6 -22.4 79.1 13.1 111.4 33.5
Pressure (Atm) 26 26 26 12 12 12 4.8 4.8 4.8
Vapor fraction 0 1 1 0 1 0 0 0 0
Mass flow (kg/hr) 14,500 14,500 14,500 14,500 3,500 11,000 5,250 5,750 5,750
Molar flow (kmol/hr) 164 164 244 244 93 140 84 67 67
Ethylene 0.7 0.7 0.7 0.7 0.7 0 0 0 0
Hydrogen chloride 7.7 7.7 91.2 91.2 91.2 0 0 0 0
Oxygen 0 0 0 0 0 0 0 0 0
1,2-dichloroethane 138.7 138.7 53 53 0 53 0.1 52.8 52.8
Water 12.7 12.7 12.3 12.3 0 11.3 1 11.3 11.3
Vinyl chloride 3.8 3.8 86.2 86.2 0.8 85.4 82.4 3 3
Chlorine 0.1 0.1 0.05 0.05 0 0.05 0.05 0 0
1,1,2-trichloroethane 0.05 0.05 0.05 0.05 0 0.05 0 0.05 0.05
1,4-dichlorobutane 0.05 0.05 0.05 0.05 0 0.05 0 0.05 0.05
As before, individual component flows can be viewed in the stream summary table. With our dual-recycle
process, we again minimize the amount of harmful side products like 1,4-dichlorobutane and 1,1,2-
trichloroethane that leave the system. Inside the recycle, the single-pass conversion of HCl across the
oxychlorination reactor is roughly 92%; literature predicts conversion values ranging 80-97% (Moreira & Pires,
2010). Adding the 1,2-dichloroethane recycle (stream 17) improved the overall conversion of the desired
pyrolysis reaction to over 99%.
UTILITY REQUIREMENTS
We calculated the minimum utilities for the plant using the pinch method. This method of heat integration
ensures our heat exchanger network will have no heat transferred from a hot stream with a temperature above
the pinch point to a cold stream with a temperature below the pinch point. Using the composite curves below,
we were able to determine the minimum hot and cold duties of the whole process by finding the difference in
the endpoints of the hot and cold composite curves.
Direct Chlorination Composite Curve
Figure UR.1 – Composite curves for direct chlorination process.

Oxychlorination Composite Curve
Figure UR.2 – Composite curves for oxychlorination process.

Utilities Summary
Direct Chlorination Table UR.1 – Utilities summary for direct chlorination process.
Heat Exchanger Type Base Duty [kJ/hr] Hot Inlet Temperature [C] Hot Outlet Temperature [C] Cold Inlet Temperature [C] Cold Outlet Temperature [C]
V-100 Quench tank Cooler -1.22E+07 500 6 -25 -24
E-104 HCl column reboiler Heater 3.53E+06 125 124 76.3 94.2
F-100 Pyrolysis furnace Cooler -9.83E+04 500 499.5 249 250
E-105 VC column condenser Cooler -3.22E+06 42.8 30.8 20 25
E-103 HCl column condenser Cooler -1.39E+06 2.9 -21.3 -25 -24
R-100 Direct chlorination reactor Cooler -1.75E+07 90 89.5 30 35
E-106 VC column reboiler Heater 3.10E+06 175 174 144 144.5
E-101 Evaporator Heater 4.23E+06 280 250 181.9 242
F-100 Pyrolysis furnace Heater 6.42E+03 3000 2999 500 500.5
Oxychlorination Table UR.2 – Utilities summary for oxychlorination process.
Heat Exchanger Type Base Duty [kJ/hr] Hot Inlet Temperature [C] Hot Outlet Temperature [C] Cold Inlet Temperature [C] Cold Outlet Temperature [C]
V-200 Quench tank Cooler 1.29E+07 500 6 -25 -24
E-203 HCl column reboiler Heater 3.37E+06 125 124 41.8 79.1
E-205 VC column reboiler Heater 3.07E+06 125 124 74.5 111.4
F-200 Pyrolysis furnace Heater 1.03E+07 1000 400 242 500
F-200 Pyrolysis furnace Cooler 1.68E+04 500 499.5 249 250
E-204 VC column condenser Cooler 3.72E+06 31.9 13.1 -25 -24
E-202 HCl column condenser Cooler 1.12E+06 -0.2 -22.4 -40 -39
R-200 Oxychlorination reactor Cooler 1.98E+07 260 259.5 249 250
E-206 Recycle cooler Cooler 8.13E+05 132.4 33.5 20 25
F-200 Pyrolysis furnace Heater 6.60E+03 3000 2999 500 500.5
Comparison
The total hot utility requirements for the oxychlorination process amounts to 5.5  106 kJ/hr and a total cold
utility of 1.54  107 kJ/hr. The direct chlorination process requires a hot utility of 1.15  107 kJ/hr, and a cold
utility of 2.5  107 kJ/hr, indicating that the oxychlorination process is much more efficient with energy. The
operation in both processes that required the most cooling utility was the cooling of the stream as it exits the
final pyrolysis reactor (when the hot stream cools from 500°C to 6°C. The stream matching (see Appendix B),
which was performed by Aspen, shows how the integration differs between the two processes. Mainly, there is
an extra cold stream to match for the oxychlorination process. This additional heat sink explains the much lower
cold utility for the oxychlorination process.
ENVIRONMENTAL SUSTAINABILITY ASSESSMENT
Biwer’s Method Overview
When developing a process design, the environmental impact of the reactant and product materials must be
taken into account. Determining the environmental impact of a process will ensure that a facility abides by
governmental regulations and does not produce unnecessary risk for employees. The method for assessing
environmental sustainability that we applied was developed by Biwer et al. (2004). Biwer’s method is aimed at
shortening the amount of time it takes to assess the environmental impact and sustainability during the
development of a process. This method is only applicable during early stage process development for
conceptually comparing processes.
Biwer’s method uses 14 environmental impact categories to classify each compound in the process, which vary
depending on whether the component is an input or output of the process. All of the reaction components are
classified as input or output components. Then each component is rated for its environmental relevance to each
applicable impact category. These impact categories are assigned an environmental impact rating, which is an
alphabetical rating of each group corresponding to numerical defined by Biwer (A=1, B=0.3, C=0). These ratings
represent the weight of impact that the compound has on each group. Once rated, the 14 impact categories are
divided into their designated impact groups, where the rating of each impact group is the same as the highest,
most extreme impact rating of the categories in that group. This practice ensures a conservative estimate of
environmental impact. Each alphabetical rating correlates to a distinct numerical value, which is used in
conjunction with the input or output component’s mass flow to calculate the environmental factors.
For input components the impact categories are: Raw Material Availability (Avb), Complexity of Synthesis (CS),
Critical Materials Used (CM), Thermal Risk (ThR), Acute Toxicity (AT), Chronic Toxicity (ChT), and Endocrine
Disruption (ED). The impact categories for output components are Thermal Risk (ThR), Acute Toxicity (AT),
Chronic Toxicity (ChT), Endocrine Disruption (ED), Global Warming Potential (GWP), Ozone Depletion Potential
(ODP), Acidification Potential (AP), Photochemical Ozone Creation Potential (POCP), Odour (Od), Eutrophication
Potential (EP), and Organic Carbon Pollution Potential (OCPP). Each component’s impact category is given an A,
B or C rating based on the scientific relevance and intensity of the compound’s effect.
The next step is to assign the impact categories to one of six impact groups: Resources, Grey Input, Component
Risk, Organisms, Air, or Water/Soil. How impact categories are grouped into impact groups is shown in Appendix
C. Once each component’s impact categories are placed into their respective impact groups, the impact groups
are given the highest rated impact letter of that group. For example, if an impact group had three categories,
with two Cs and one A, the impact group would be assigned a rating of A.
The arithmetic average of all of the component’s impact ratings is the component’s Environmental Factor Value
(EF). The Environmental Index (EI) of each component is the EF multiplied by the ratio of component mass flow
rate to desired product mass flow rate. The total Environmental Index of the process (EIproc) is calculated by
taking the sum of the EI components (EIcomp) involved in the process (inputs and outputs).
Environmental Analysis
To assess the environmental impact of the chemicals involved in the production of vinyl chloride, we calculated
the Environmental Index of each process using Biwer’s Environmental Factor Method. The total EIproc of any
components that appeared in both the inlet and outlet streams was calculated by summing the EIcomp values.
This method ensures a conservative estimate when dealing with environmental impact, hopefully precluding
the possibility of an environmental disaster. To identify the highest impact compounds, we look for the
components with the highest EIcomp values. For both the direct chlorination and oxy-chlorination processes, vinyl
chloride was the highest impact component. The other high impact molecules were hydrogen chloride, and
chlorine, which was only present in the direct chlorination process. Prior to adding the hydrogen chloride
recycle, the oxychlorination process had a higher environmental impact than direct chlorination. After installing
the recycle, the resulting lack of waste dropped the environmental impact of the oxychlorination process lower
than that of the direct chlorination.
Table ES.1 – Component EI fraction values for direct chlorination process.
Input Total
Component EI of Component EI of Input EI fraction Component EI of Component EI of Process EI fraction
Ethylene 0.226 0.378 Ethylene 0.231 0.148
Chlorine 0.371 0.622 1,2-dichloroethane 0.015 0.009
Total input 0.60 1.000 Vinyl chloride 0.650 0.416
Hydrogen chloride 0.293 0.187
Chlorine 0.374 0.239
Output Total process 1.56 1.000
Component EI of Component EI of Output EI fraction
Ethylene 0.005 0.005
1,2-dichloroethane 0.015 0.015
*For compounds used in both reactions or compounds that enter and exit, the
Vinyl chloride 0.650 0.674
highest EI of component was used to calculate the conservative estimate of the
EI of the process
Chlorine 0.003 0.003
Total output 0.965 1.000
Table ES.2 – Component EI fraction values for oxychlorination process.

Input Total
Component EI of Component EI of Input EI fraction Component EI of Component EI of Process EI fraction
Ethylene 0.226 0.344 Ethylene 0.235 0.174
Hydrogen chloride 0.411 0.624 1,2-dichloroethane 0.001 0.001
Oxygen 0.021 0.033 Oxygen 0.022 0.016
Total input 0.658 1.000 Water 0.000 0.000
Vinyl chloride 0.650 0.482
Output Hydrogen chloride 0.441 0.327
Component EI of Component EI of Output EI fraction Total process 1.35 1.000

Ethylene 0.009 0.013
1,2-dichloroethane 0.001 0.002
Vinyl chloride 0.650 0.941 These asterisk comments aren’t
*For compounds used in both reactions or compounds that enter and exit, the
highest EI of componentaccurate and were a formatting
was used to calculate the conservative estimate of the
Water 0.000 0.000
Oxygen 0.000 0.000 error
EI of the process
Total output 0.69 1.000
The EI tables show that, from an environmental standpoint, the oxychlorination process is a superior method of
producing vinyl chloride than direct chlorination. The EIproc of direct chlorination came to 1.64, compared to the
oxychlorination EIproc of 1.35.
Appendix C shows that since the two processes have very similar compounds, mass flow has the largest effect
on total environmental impact of the process. Adding the recycle greatly reduced the mass of hydrogen chloride
leaving the oxy-chlorination process, and thus greatly reduced the overall environmental impact.
FINANCIAL SUSTAINABILITY ASSESSMENT

Both the baseline and modified plants were modeled as continuous fluids processes operating at moderate
capacity. Using various estimation methods and guidelines for the cost of equipment, the total capital
investment and total production were defined. Profitability metrics were assessed and discussed to determine
which process was more financially sustainable. Further detail regarding the estimation of costs and profitability
metrics such as return on investment, payback period, net present value, and the investor’s rate of return can
be found in Appendix D.
Equipment Costs
Given that a pre-optimized process design (the baseline concept) was provided for direct chlorination, a
preliminary estimate based on the Individual Factors Method was carried out for each process (Guthrie, 1974).
The purchase costs of major process equipment were used in estimating the total capital investment.
Equipment List for Direct Chlorination Process (Including Purchase Costs)
C P , f.o.b. Purchase
Equipment Name Equipment Label Material of Construction Size Design Pressure (psig)
Cost (MS Index = 596)
Direct chlorination reactor and

reactor condenser R-100 / E-100 Stainless Steel 2.5 ft diam / 11.5 ft height 35 $ 45,810.85
Reactor centrifugal pump P-100 Cast Steel 372 hp 367 $ 106,674.54
Evaporator E-101 Carbon Steel 400 ft2 273 $ 97,245.81
Pyrolysis furnace F-100 Stainless Steel 1727 ft2 417 $ 294,996.08
Quench tank V-100 / P-101 / E-102 Stainless Steel 480 ft2 187 $ 76,959.49
HCl column T-100 Carbon Steel 2.5 ft diam / 28 ft height 187 $ 63,114.24
VC column T-101 Carbon Steel 3 ft diam / 32 ft height 81 $ 76,899.62
HCl column condenser E-103 Stainless Steel 336 ft2 187 $ 95,753.03
VC column condenser E-105 Stainless Steel 337 ft2 81 $ 93,616.91
HCl column reboiler E-104 Stainless Steel 201 ft2 187 $ 38,025.01
VC column reboiler E-106 Stainless Steel 491 ft2 81 $ 45,496.75
HCl column reflux drum E-103 Carbon Steel 3 ft diam / 6 ft height 187 $ 26,645.07
VC column reflux drum E-105 Carbon Steel 3 ft diam / 9 ft height 81 $ 21,803.16
(Note that the reactor condenser (E-100) is included in the pricing of R-100 and consists of circulating cold water to maintain the reaction temperature in the forming 1,2-dichloroethane.)
The major equipment for the direct chlorination process consists of a centrifugal pump, evaporator, a direct
chlorination reactor, condenser, pyrolysis furnace, and two distillation columns. The modified baseline process
includes the same components along with a decanter as well as an additional condenser. Sizing information was
obtained from Aspen Plus, and the equipment price values were determined using purchase cost equations
found in Chapter 22 of Seider and Seader (S&S). Below is an equipment table listing pertinent information on
major process equipment. To update the purchase costs, recent Marshall and Swift index values were
incorporated in the table (Seider, Seader, Lewin, & Widagdo, 2009). More detailed guidelines on the deriving
the purchase cost for various equipment can be found in Appendix D.
Equipment Sizing
Using the volumetric flow rate and pump head information, a cast steel centrifugal pump was selected to ensure
proper compression in the chemical process. Using the heat transfer surface area, the cost of the evaporator
and condenser were approximated. The pyrolysis furnace was costed using the heat duty provided in Aspen
Plus. The decanter was estimated as a horizontal pressure vessel given the diameter, length, and weight of the
tank from the simulation model.
For reactor sizing, both direct chlorination and oxy-chlorination reactors were treated as plug flow reactors
(PFRs). Each plug flow reactor can be approximated as a pressure vessel. Using diameter, length, and weight
values from Aspen Plus, each reactor was sized and costed appropriately.
Using the inside diameter and tangent-to-tangent length data from Aspen Plus, the cost of each distillation
tower was estimated. Sieve trays were used along with Carbon steel to construct each tower. The condensers
and reboilers were costed as Kettle vaporizer and U-tube heat exchangers, respectively. Each reflux drum was
estimated as a horizontal pressure vessel and constructed from Stainless steel.
Bare-Module Costing
After outlining the necessary equipment costing information, the bare-module cost from Guthrie’s method was
determined. Using the appropriate bare-module factor, FBM, and multiplying it by each purchase cost, a bare-
module cost, CBM, was determined. Bare-module factors for various processing equipment can be found in Table
22.11 of S&S. These factored costs account for delivery, insurance, taxes, and direct materials and labor for
installation (Verwijs, 1995). The total bare-module cost, CTBM, was obtained by summing the bare-module costs
of the processing equipment. This amount was used in finding the total capital investment of each chemical
process.
Capital Cost Estimate of Bare-Module Equipment Cost for a
Vinyl Chloride Plant - Costs in Millions of U.S. Dollars
Direct Chlorination Process Oxychlorination Process Cp FBM CBM
Cp FBM CBM
Fabricated Equipment Fabricated Equipment
Heat Exchangers 0.45 3.17 1.42 Heat Exchangers 0.49 3.17 1.55
Pressure Vessels 0.08 3.05 0.24 Pressure Vessels 0.08 3.05 0.24
Distillation Columns 0.14 4.30 0.60 Distillation Columns 0.13 4.3 0.57
Pyrolysis Furnace 0.29 2.19 0.65 Pyrolysis Furnace 0.32 2.19 0.71
Reactors 0.16 4.16 0.68 Reactors 0.05 4.16 0.19
Process Machinery
Process Machinery
Pumps 0.02 3.3 0.05
Pumps 0.11 3.30 0.35
Total bare-module cost for Total bare-module cost

on-site equipment 3.93 for on-site equipment 3.31
Total Capital Investment
The total capital investment (TCI) provides an in-depth look at the costing necessary to deliver the product,
calculated as a one-time investment in chemical plant startup. This vinyl chloride plant was modeled as an
addition to an existing integrated complex. A TCI table was created based on Table 22.9 of S&S (Seider, Seader,
Lewin, & Widagdo, 2009). The formulas and estimates used in creating the table can be found in the appendix.
As an addition to an existing complex, no land purchase costs were necessary (with the exception of site
preparation). Storage tanks for raw materials were considered and the existing utilities will support the need of
installed processing unit, negating the need for allocated costs (Bureau, 2015). Service facilities were also
accounted for and the cost of the computers, software, and associated items are included within the total bare-
module cost for on-site equipment.
Total Capital Investment for Vinyl Chloride Plant - Cost in Millions of U.S. Dollars ($MM/yr) Direct Chlorination Process
Total bare-module costs for on-site equipment 3.93
Total bare-module costs for spares 0.11
Total bare-module costs for storage and surge tanks 0.58
Total bare-module costs for comupters and software, including distributed control systems, instruments, and alarms
Total bare-module investment, TBM 4.62
Cost of site preparation 0.18
Cost of service facilities 0
Allocated costs for utility plants and related facilities 0
Total of direct permanent investment, DPI 4.80
Cost of contingencies and contractor's fee 0.86
Total depreciable capital, TDC 5.67
Cost of plant startup 0.57
Total permanent investment, TPI 6.23
Working capital 5.52
Total capital investment, TCI 11.76
Total Capital Investment for Vinyl Chloride Facility - Cost in Millions of U.S. Dollars ($MM/yr) Oxychlorination Process
Total bare-module costs for on-site equipment 3.31
Total bare-module costs for spares 0.02
Total bare-module costs for storage and surge tanks 0.50
Total bare-module costs for comupters and software, including distributed control systems, instruments, and alarms
Total bare-module investment, TBM 3.82
Cost of site preparation 0.15
Cost of service facilities 0.00
Allocated costs for utility plants and related facilities 0.00
Total of direct permanent investment, DPI 3.98
Cost of contingencies and contractor's fee 0.72
Total depreciable capital, TDC 4.69
Cost of land
Cost of royalties
Cost of plant startup 0.47
Total permanent investment, TPI 5.16
Working capital 5.34
Total capital investment, TCI 10.50
Using the assumptions above, as well as estimates given by S&S, the total capital investment for the baseline
process was $11.76 million. The oxychlorination process was similar, estimated at $10.50 million. The increase
in efficiency can be attributed to the decrease in cost.
Total Production Cost
The total production cost outlines the viability of implementing a new chemical process. Much like Table 23.1
of S&S, a cost sheet has been developed for the baseline as well as modified process (Seader, 2009). The cost
sheet for each process can be found in Appendix D, as well as an outline of methods to estimate factors. A basis
of 90% capacity for the year is considered when determining cost factors. Additionally, depreciation is modeled
as a 10-year straight-line depreciation. Any general expenses have been omitted due to lack of information.
From the total production cost, the working capital can be calculated, shown in the previous table of the TCI.
The production cost for the direct chlorination process was $39.38 million per year, whereas the modified
process had a total production cost of $24.57 million per year. Although it used more raw materials, the
oxychlorination process was more efficient and yielded a lower production cost.
Profitability Analysis
To assess the profitability of each process, principal measures such as the return on investment and payback
period were analyzed. To observe the feasibility of each process over time, the net present value and investor’s
rate of return were determined and compared.
Return on Investment and Payback Period
To appropriately measure the “economic goodness” of the vinyl chloride plant, the percent return on
investment was developed (Seader, 2009). A capacity of 90% from the first year of production, 40% income tax
rate, and $1,200 per metric ton of vinyl chloride was specified. Along with these constants, the total depreciable
cost, and total production cost, the annual earnings were determined. Dividing these earnings by the total
capital investment yielded a return on investment of 61% per year for the direct chlorination process and 147%
per year for the oxychlorination process.
The time it took for the annual earnings to equal the original investment was computed. This is commonly called
the payback period. Using the total depreciable capital along with the net cash flow, a payback period was
estimated. For the baseline process, it will take 0.77 years for the investment to be paid off. For the modified
process, the payoff period will take 0.37 years. With rapid development and increasing competition, periods
greater than four years should not be considered. Fortunately, both cases are well below this value.
Net Present Value (NPV) and Investor’s Rate of Return (IRR)
The net present value sums the cash flows across a plant’s projected life-span. This can provide quantitative
data for comparing the required capital against competing processes. For the vinyl chloride plant, a construction
period of three years was specified. The total depreciable capital was distributed into three equal parts during
construction. Production began at 30% capacity, followed by 60% in the second year and 90% capacity for the
remainder of production. After fifteen years of production, the plant will be sold for salvage and the working
capital recovered. An interest rate of 15% per year and an income tax rate of 40% per year were used. The
depreciation was modeled as a 10-year straight-line depreciation. For the baseline process, the final NPV was
$15.41 million. For the modified process, the final NPV was $42.26 million. The next page contains a table of the
cash flows in millions of dollars per year for the baseline as well as the modified process. Development of the
sheet can be found in Appendix D.
Using the same outline for the NPV, the IRR was determined. This is defined as the interest rate which will yield
a NPV of zero in the final year. For the baseline process, this was found to be 36.1%. For the modified process,
an IRR of approximately 62.0% was found. This is justified by the fact that both cases provided positive final
NPVs, so an interest rate higher than the specified 15% will be produced to reach an NPV of zero.
Calculation of Cash Flows (Millions of Dollars) for Vinyl Chloride Plant (Nominal interest rate = 15%) Direct Chlorination Process
Year fC(TDC) C(WC) D C(Excl. Dep) S Net Earnings Discounted Cash Flow Cash Flow (PV) Cum. PV
1 2016 -1.89 0.00 -1.89 -1.89 -1.89
2 2017 -1.89 0.00 -1.89 -1.43 -3.32
3 2018 -1.89 -5.52 0.00 -7.41 -4.87 -8.19
4 2019 0.57 13.13 16.90 1.92 2.49 1.42 -6.77
5 2020 0.57 26.25 33.80 4.19 4.76 2.36 -4.40
6 2021 0.57 39.38 50.70 6.45 7.02 3.03 -1.37
7 2022 0.57 39.38 50.70 6.45 7.02 2.64 1.27
8 2023 0.57 39.38 50.70 6.45 7.02 2.29 3.57
9 2024 0.57 39.38 50.70 6.45 7.02 2.00 5.56
10 2025 0.57 39.38 50.70 6.45 7.02 1.74 7.30
11 2026 0.57 39.38 50.70 6.45 7.02 1.51 8.81
12 2027 0.57 39.38 50.70 6.45 7.02 1.31 10.12
13 2028 0.57 39.38 50.70 6.45 7.02 1.14 11.26
14 2029 39.38 50.70 6.79 6.79 0.96 12.22
15 2030 39.38 50.70 6.79 6.79 0.83 13.05
16 2031 39.38 50.70 6.79 6.79 0.73 13.78
17 2032 39.38 50.70 6.79 6.79 0.63 14.41
18 2033 5.52 39.38 50.70 6.79 12.31 1.00 15.41
Calculation of Cash Flows (Millions of Dollars) for Vinyl Chloride Plant (Nominal interest rate = 15%) Oxychlorination Process
Year fC(TDC) C(WC) D C(Excl. Dep) S Net Earnings Discounted Cash Flow Cash Flow (PV) Cum. PV
1 2016 -1.56 0.00 -1.56 -1.56 -1.56
2 2017 -1.56 0.00 -1.56 -1.18 -2.75
3 2018 -1.56 -5.34 0.00 -6.90 -4.54 -7.29
4 2019 0.47 8.19 16.36 4.62 5.09 2.91 -4.38
5 2020 0.47 16.38 32.72 9.52 9.99 4.97 0.59
6 2021 0.47 24.57 49.09 14.43 14.89 6.44 7.03
7 2022 0.47 24.57 49.09 14.43 14.89 5.60 12.63
8 2023 0.47 24.57 49.09 14.43 14.89 4.87 17.50
9 2024 0.47 24.57 49.09 14.43 14.89 4.23 21.73
10 2025 0.47 24.57 49.09 14.43 14.89 3.68 25.42
11 2026 0.47 24.57 49.09 14.43 14.89 3.20 28.62
12 2027 0.47 24.57 49.09 14.43 14.89 2.78 31.40
13 2028 0.47 24.57 49.09 14.43 14.89 2.42 33.82
14 2029 24.57 49.09 14.71 14.71 2.08 35.90
15 2030 24.57 49.09 14.71 14.71 1.81 37.71
16 2031 24.57 49.09 14.71 14.71 1.57 39.28
17 2032 24.57 49.09 14.71 14.71 1.37 40.65
18 2033 5.34 24.57 49.09 14.71 20.05 1.62 42.26
Summary of Profitability Analysis
After assessing financial sustainability, the modified process concept based on oxychlorination is the more
financially attractive of the two models. With comparable capital costs, the direct chlorination process has a
substantially higher production cost per year. The modified process outperforms the baseline with a higher
return on investment and shorter payback period. The profitability of the final net present value at an interest
rate of 15% for the oxychlorination concept is much greater than the baseline concept, at $42.26 million
compared to $15.41 million. With a high IRR of 62.0%, the process based on oxychlorination is highly favorable
for implementation. From a financial perspective, efforts focused on generating the greatest profit should
construct the modified process concept replacing direct chlorination with oxychlorination.
DIRECT CHLORINATION NET PRESENT VALUE SENSITIVITY ANALYSIS

The following plot shows how NPV over 15 years of vinyl chloride production reacts to changes in various factors.
The plots all show linear relationships between NPV and change in TCI, capacity, and selling price of vinyl
chloride. Looking at the slopes of these graphs and examining their magnitude allows us to assess the sensitivity
of profits to each factor.
A steeper slope indicates that the factor has a greater effect on NPV, so NPV is more sensitive to that factor.
This analysis tells us the degree to which we should be confident in our projections for the future of the plant.
Any factors that have a high sensitivity reveal an element of risk that we cannot control, and may even give
future investors pause. The chart was prepared with the following data:
Table SA.1 – Effect of %TCI, %Capacity, and %Price of vinyl chloride on net present value.
%TCI NPV % Capacity NPV % Price of VC NPV

50% 17.31 50% -27.85 50% -33.25
75% 16.36 70% -6.22 75% -8.92
100% 15.41 90% 15.41 100% 15.41
150% 13.5 150% 64.07
Figure SA.1 – Effect of %TCI, %Capacity, and %Price of vinyl chloride on net present value.
The magnitudes of the slopes show that our model is relatively unscathed by changes in TCI. In order to make
this venture unprofitable, we would have to increase our investment by 500%. In comparison, the slopes of the
capacity and vinyl chloride price graphs should give us pause. A mere 6% drop in the price of vinyl chloride erases
our healthy $15.41M profit. Predictably, any drop in capacity results in a precipitous drop in profit, indicating
that changes in capacity have the most severe effect out of the factors we analyzed. In order to break even, the
plant must run at least at 75% capacity over the 15 years of production. These projections indicate that it might
be prudent to decrease our investment in the production of vinyl chloride, as it offers a decrease in risk at
relatively low cost. Alternatively, to reduce dependence on the price of vinyl chloride, we could invest in a plant
that processes the vinyl chloride monomer into PVC plastic. This course of action would completely remove our
dependence on the relatively unstable commodity chemical, and place it in a more reliable end-product.
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APPENDICES
Appendix A: Process Design
Reaction Schemes – Direct Chlorination
Direct chlorination in a liquid phase of 1,2-dichloroethane involves two primary reactions:
C2H4 + Cl2 –(R1) C2H4Cl2 (A1)
C2H4Cl2 + Cl2 –(R2) C2H3Cl3 + HCl (A2)
Experimentally, R1 has been shown to follow the form R1 = kR1[ethylene][chlorine] and R2 closely follows the
form R2 = kR2[ethylene][chlorine]2 (Wachi & Morikawa, Liquid-Phase Chlorination of Ethylene and 1,2-
Dichloroethane, 1996). The production of 1,2-dichloroethane (A1) can have selectivity approaching 100%,
depending on the operating conditions in the reaction vessel. Sparger efficiency plays a major role in improving
conversion, since this reaction is somewhat unique: It occurs in a bath of the product material. Chlorine is more
soluble than ethylene in 1,2-dichloroethane, and direct chlorination is a liquid-phase reaction so the absorption
rate of the reactants is important.
Wachi et al. propose experimentally derived kR1 and kR2 values of 0.132 m3 mol-1 s-1 and 0.0239 m6 mol-2 s-1,
respectively (which is in alignment with our expectations, since we’re anticipating a high conversion to 1,2-
dichloroethane).
After undergoing a series of temperature, pressure, phase, and component (recycle merges and splits) changes,
the 1,2-dichloroethane formed in reaction A1 reaches the pyrolysis reactor and experiences some new
reactions:
C2H4Cl2 –(R3) C2H3Cl + HCl (A3)
C2H3Cl –(R4) C2H2 + HCl (A4)
C2H4Cl2 –(R5) C2H4 + Cl2 (A5)
From (Dimian & Bildea, 2008), we know these reactions can be modeled with the rate model Ri=kici with pre-
exponential factor and activation energy data as follows:
Reaction Pre-exponential factor [s-1] Activation energy [cal/mol]

A3 1.14 x 1014 58000
A4 5.00 x 1014 69000
A5 1.00 x 1013 72000
As one might expect, the pyrolysis reactor produces some larger side-products (next page).
C2H2 + C2H3Cl –(R6) C4H5Cl (A6)
2 C2H4Cl2 –(R7) C4H8Cl2 (A7)
Where reactions A3-A5 broke down 1,2-dichloroethane and vinyl chloride into their constituent pieces like
acetylene, ethylene, chlorine, and hydrogen chloride, reactions A6 and A7 produce larger molecules like
chloroprene (C4H5Cl) and 1,4-dichlorobutane. However, acetylene is required for reaction A6 and it is produced
in negligible quantities in reaction A4 in a well-optimized system, so chloroprene flow rates are typically
negligible. The conversion of reaction A7 is governed by its selectivity, as stated by (Dimian & Bildea, 2008):
Conversion of 1,2-dichloroethane = 1-S = 1-(0.989 + 0.0506X – 0.0652X2) where X is the conversion in reactions A3-A5.
Finally, various tri-chlorine molecules are made in small quantities in the pyrolysis reactor:
C2H3Cl + Cl2 –(R8) C2H3Cl3 (A8)
C2H4Cl2 + Cl2 –(R9) C3H3Cl3 + HCl (A9)
C2H2 + 2 Cl2 –(R10) C2HCl3 + HCl (A10)
(Dimian & Bildea, 2008) gives chlorine conversions of 50%, 20%, and 30% for A8, A9, and A10, respectively.
Reaction Schemes – Oxychlorination
Oxychlorination follows the same scheme as direct chlorination, but it produces 1,2-dichloroethane differently.
Instead of a liquid-phase phase reaction (like direct chlorination), the oxychlorination process occurs entirely in
the gas phase (Rosen, 2014). An oxychlorination reactor contains a heterogeneous catalyst like CuCl2 to achieve
the following reactions:
C2H4 + 2 HCl + 0.5 O2 –(R11) C2H4Cl2 + H2O (A11)
C2H4Cl2 + HCl + 0.5 O2 –(R12) C2H3Cl3 (A12)
Which are governed by the rate expressions (Carrubba, 1970):
R11 = (k11KaCcPC2H4) / (RT + KaPC2H4)
R12 = k12PC2H4Cl2 * sqrt(PCl2)
These expressions, in combination with the kinetic parameters given in (Moreira & Pires, 2010), allow for
rigorous differential modeling of each reactor.
Process Motivation
Reactors:
When designing our chlorination reactors, we had to make a decision between a fixed-bed reactor or a fluidized-
bed reactor. Fixed-bed reactors have catalyst packed in vertical tubes, which provides a large surface area for
heat to transfer to a cooling medium. However, the reaction is exothermic, and the fixed bed leads to
inconsistent catalyst activity. Fluidized-bed reactors provide a solution to this problem. A fluidized-bed reactor
introduces the catalyst as a fine powder. The small particle size ensures that kinetics are close to ideal, which
results in a more uniform temperature profile in the reactor. In our case, the fluidized-bed does not serve our
purposes, because back-mixing in the fluidized reactor leads to a decrease in efficiency. Since we intend to run
the process continuously, decreases in efficiency over time could be fatal from a business standpoint. As such,
we used a fixed bed reactor.
The reaction conditions differ greatly between the direct and oxychlorination reactors. For direct chlorination,
the chlorination takes place exclusively in the liquid phase, and employs a Lewis acid catalyst. The aqueous
catalyst is important, as it means that all the reactants are dissolved by the product 1,2-dichlorethane. This can
lead to problems with mole flow, as the ethylene being fed to the reactor is less soluble in DCE than chlorine.
This means the chlorine will enter solution faster than the ethylene, possibly leading to a buildup of ethylene in
the reactor. This offers a stark contrast to the oxychlorination process, which chlorinates in the gas phase, thus
avoiding the corrosive problems associated with aqueous acids. In order to facilitate the gas phase reaction,
the oxychlorination reactor employs solid cupric chloride, CuCl2 . The cupric chloride is introduced as a fine
powder to allow for maximum surface area.
Reactor feed:
There are decisions to be made about the feed to the reactor as well. Namely, we can feed oxygen to the
reaction either as a pure O2 stream, or simply feed the reactor air. Air has the obvious benefit of being cheaper.
No one ever has to buy air. Furthermore, the nitrogen in the air stream adds quite a few inert molecules, which
allows for greater temperature control. In the end, it is the excess nitrogen that precludes our design from
incorporating air based oxychlorination. All that nitrogen can make the stream up to a 100 times larger, making
the rest of the process far too expensive. Pure O2 may have an overhead, but greatly improves our yields.
However, there is the additional cost associated with the fact that oxygen based oxychlorination requires a
higher excess of HCl, which will certainly add to our raw material cost.
Quench:
The quench is a crucial process unit as it quickly cools the gas coming from the pyrolysis furnace, halting any
further pyrolysis and vinyl chloride decomposition. It also serves as the first separation, flushing heavy impurities
generated by the furnace out of the system. For more information about the quench, see Modeling.
Decanter:
The decanter is a horizontal pressure vessel that acts as a liquid-liquid vapor separator; it was chosen for the
efficacy with which it could remove water from a stream. See the Modeling section for more on the decanter.
Distillation train:
The entire objective of this process is to produce high purity vinyl chloride monomer. Achieving that purity will
require a number of separations. Following separation heuristics, the lightest component is the first separation
target. In this case of the oxychlorination reactor, the lightest component is HCl. The lightest compound actually
must be separated first, due to the high pressure of the stream leaving the pyrolysis reactor. The temperature
would be too high at the bottom of the column, where the heaviest components are, which means the heavy
key (vinyl chloride) would not be properly separated from the heavy non-key, 1,2-dichloroethane, and would
require another separation. Once the first column removes most of the HCl in the distillate, the second column
can target the heavy key, vinyl chloride. Our vinyl chloride is condensed in the distillate, while the heavy non-
key 1,2-dichloroethane is taken to be recycled in the bottoms product.
Modeling
Reactor modeling: The direct chlorination reactor was modeled as an idealized CSTR (since adding a sparger in
Aspen is a seemingly fruitless quest) with near-entire conversion of ethylene to 1,2-dichloroethane. The reactor
was held at the bubble point of the mixture such that freshly synthesized 1,2-dichloroethane evaporates and
condenses during its residence. Because this reaction (A1 and A2) is very exothermic (∆H = 218 kJ/mol), the
flowing 1,2-dichloroethane serves as a temperature mediator. Conversion calculations result in approximately
99.5% conversion to 1,2-dichloroethane and 0.5% conversion to 1,1,2-trichloroethane. The size of the vessel
was determined by Aspen and can be viewed in the Equipment Sizing section.
(Moreira & Pires, 2010) contains a method by which the reactor can be manually sized through calculating a
series of differential equations relating to the height of a rising bubble inside the vessel.
The oxychlorination reactor was modeled as a shell-and-tube heat exchanger achieving 98% conversion of
ethylene to 1,2-dichloroethane and 0.5% conversion of ethylene to 1,1,2-trichloroethylene and hydrogen
chloride. Adding an HCl recycle upstream of the reactor (coming from the first distillation tower) improves both
Environmental Impact and system efficiency considerably.
Heat exchanger modeling: Heating units were added to streams with the necessary calculated duty to achieve
desired stream conditions (see Utilities Summary). Resultant duty values from Aspen Plus were imported into
Aspen Energy Analyzer to generate composite curve and stream matching data. See the PFDs in Process Design
for specific duties per unit. Calculations performed in the Financial Sustainability Assessment section translate
these duty and surface area values into costing information.
Decanter modeling: The decanter was modeled as an equilibrated flash drum with given splits based on known
solubility data. Specifically, 1,2-dichloroethane is reported to have 0.81% solubility by mass in water at 20°C and
the solubility of water under the same conditions in 1,2-dichloroethane is 0.15% by mass. This data was used to
perform what is essentially a LLE calculation to find the splits coming out of the decanter.
Appendix B: Stream Matching Diagrams
Direct chlorination
Oxychlorination
Appendix C: Environmental Sustainability
All non-original tables and charts come from (Biwer, 2004).
At right is a map of how the impact categories and impact

groups were sectioned together, and which categories are
used for input or output environmental factors.
To calculate the environmental impact of all of the

chemicals involved in the reaction, we looked up literature
for the factor values from the Environmental Protection
Agency, along with other governmental and independent
research agencies (CDC, NIOSH, US Human Health and
Safety).
These formulas were provided in the paper describing Biwer’s assessment method: They provide the equations to
calculate the Environmental Factors and Environment Indices for each component and overall process.
Environmental Factor Tables – Direct Chlorination
Input Components
Inlets:
Component Ethylene
Impact Category Impact Group Impact Group

Impact Category Impact Group EF Value
ABC Rating ABC Rating Numerical Rating
Avb B Resources B 0.3 0.475
CS B Grey Input B 0.3
CM B Grey input
AT B Organisms B 0.3
ChT B Organisms
ED B Organisms
A A 1
ThR Component risk
Component Chlorine
Impact Category Impact Group Impact Group
ABC Rating ABC Rating Numerical Rating
Avb C Resources C 0 0.325

CS C Grey Input C 0
CM C Grey input
AT B Organisms A 1
ChT A Organisms
ED C Organisms
B B 0.3
ThR Component risk
Outlets: Output Components
Component Ethylene
Impact Group
Impact Impact Category Impact Group
Impact Group Numerical EF Value
Category ABC Rating ABC Rating
Rating
AT B Organisms B 0.3 0.65

ChT B Organisms
ED B Organisms
ThR A Component A 1
GWP B Air A 1
ODP B Air
AP A Air
POCP C Air
OD C Air
EP B Water/soil B 0.3
OCPP B Water/soil
Component 1,2 Dichloroethane
Impact Group
Rating
AT B Organisms A 1 0.65
ChT A Organisms
ED B Organisms
Component
ThR A A 1
risk
GWP C Air B 0.3
ODP C Air
AP C Air
POCP B Air
OD C Air
OCPP B Water/soil
Component Vinyl Chloride
Impact Group
Rating
ChT A Organisms
ED B Organisms
Component
ThR A A 1
risk
GWP B Air B 0.3
ODP B Air
AP B Air
POCP C Air
OD B Air
EP C Water/soil B 0.3
OCPP B Water/soil
Component Hydrogen Chloride
Impact Group
Rating
AT A Organisms A 1 0.5
ChT B Organisms
ED C Organisms
Component
ThR C C 0
risk
GWP C Air A 1
ODP C Air
AP A Air
POCP C Air
OD C Air
EP C Water/soil C 0
OCPP C Water/soil
(Cameo, 2016; U.S., 2001)
Component Chlorine
Impact Group
Rating
ChT A Organisms
ED C Organisms
Component
ThR B B 0.3
risk
GWP C Air A 1
ODP C Air
AP A Air
POCP C Air
OD B Air
OCPP C Water/soil
(Center, International Chemical Safety Cards: Chlorine- Lung Damaging Agent, 2003; National, Compound
Summary for CID 24526 CHLORINE, 2005; U.S., Health Effects Fact Sheet: Chlorine, 2000)
Environmental Factor Tables – Oxychlorination
Inlets:
Component Ethylene
Impact Category ABC Impact Group Impact Group

Rating ABC Rating Numerical Rating

CS B Grey Input B 0.3
CM B Grey input
ChT B Organisms
ED B Organisms
ThR A Component risk A 1


CS C Grey Input C 0
CM C Grey input
AT B Organisms A 1
ChT A Organisms
ED B Organisms

Component Oxygen

Avb C Resources C 0 0.075

CS C Grey Input C 0
CM C Grey input
ChT B Organisms
ED C Organisms
ThR C Component risk C 0
(Universal, 2015)
Outlets:
Component Ethylene
Impact Category ABC Impact Group ABC Impact Group

Rating Rating Numerical Rating

ChT B Organisms
ED B Organisms
GWP B Air A 1
ODP B Air
AP A Air
POCP C Air
OD C Air
OCPP B Water/soil
Component 1,2 Dichloroethane

ChT A Organisms
ED B Organisms
GWP C Air B 0.3
ODP C Air
AP C Air
POCP B Air
OD C Air
OCPP B Water/soil
(Center, 1,2-Dichloroethane, 2014; Ghanta, Fahey, & Subramaniam, 2014; National, Compound Summary for CID 6325 ETHYLENE,
2004; U.S., Health Effects of Ethylene Dichloride (1,2-Dichloroethane), 2002)
OCPP B Water/soil
Component Vinyl Chloride

ChT A Organisms
ED B Organisms
GWP B Air B 0.3
ODP B Air
AP B Air
POCP C Air
OD B Air
EP C Water/soil B 0.3
OCPP B Water/soil

AT A Organisms A 1 0.5
ChT B Organisms
ED C Organisms
GWP C Air A 1
ODP C Air
AP A Air
POCP C Air
OD C Air
EP C Water/soil C 0
OCPP C Water/soil
Component Oxygen


ChT B Organisms
ED C Organisms
GWP C Air C 0
ODP C Air
AP C Air
POCP C Air
OD C Air
EP C Water/soil C 0
OCPP C Water/soil
(Dreher, Torkelson, & Beutel, 2012; U.S., Health Effects of Vinyl Chloride, 2000)
Component Water

AT C Organisms C 0 0
ChT C Organisms
ED C Organisms
GWP C Air C 0
ODP C Air
AP C Air
POCP C Air
OD C Air
EP C Water/soil C 0
OCPP C Water/soil
Direct Chlorination Biwer Impact Rating
and Rationale
Inputs Ethylene Chlorine
Outputs 1,2-dichlorethane Chlorine Ethylene Vinyl chloride Hydrogen chloride
Impact Vinyl Chloride Hydrogen chloride Hydrogen chloride
Ethylene Rating Ethylene Rating Rationale Chlorine Rating Chlorine Rating Rationale 1,2-dichlorethane Rating 1,2-dichlorethane Rating Rationale Vinyl Chloride Rating Rationale
Category Rating Rating Rating Rationale
Ethylene is made from fossil
Not created with fossil fuels, and DCE made from ethylene which is
fuels, but resevoirs will not run
Avb B C no known extinction any time soon B a non renewable resource from (Input specifications)
out within the next 10 years
(PubChem, CID:24526, 2016) fossil fuels
(Ghanta et al, 2013)
There are multiple ways to
Synthesis of Chlorine simple, does Synthesis of DCE fairly simple,
produce ethylene, all of which
CS B C not require more than a couple C does not require too many steps to
require over 3 process steps to
steps in a process produce (Benedict et al)
synthesize (Ghanta et al, 2013)
Some critical materials such Chlorine easily produced and is
as...are used and made when present with other molecules in No Critical Compounds involved
CM B C C
creating ethylene (Ghanta et al, nature, no rare or critical materials (Benedict et al)
2013) used in synthesis
There are no known studies
proving that ethylene is highly Based on Biwer scoring system Can cause temporary
Contact may cause burns and can
AT B toxic to humans, but studies have B B and EPA scoring system. (US B incapacitation or injury (US EPA- A
be fatal if inhaled (US EPA, 2000)
shown ethylene is metabolized EPA, 2002 & CDC/NIOSH, 2014) VC, 2002)
into ethylene oxide (a known
Ehtylene is relatively toxic to its LC50 for AT listed as 200-2000 Toxicity range on EPA website
environment and would not be mg/m3 on EPA website- which is B designates class A - Probable Scores came from the EPA rating
ChT B A A A B
okay to breath chronically, but CT is listed as extremely high Carcinogen (US EPA, 2002 & of toxicity (US EPA-VC, 2002)
does not present high toxicity (.00006 mg/m3 reference CDC/NIOSH, 2014)
No known effect on humans but EPA has classified VC as a human
No information present on effect of
known to decrease fertitlity in rats carcinogen. Case studies suggest
inhalation or ingestion when
and listed as probable carcinogen correlation of increased birth
dealing with the endocrine system,
ED B Known Carcinogen C B of humans- There being a B defects, and decreased fertility rate C
Also not classifiable as a human
possibility of carcinogen, is a good in women, but studies have not
carcinogen (PubChem,
enough reason to list it as a class proven causation ( US EPA- Vinyl
CID:24526, 2016)
B (US EPA, 2002) Chloride, 2002)
Chlorine is not combustible but Flash point of DCE very low- Flashpoint of Vinyl Chloride is very
Highly Flammable, Flashpoint
ThR A B increases the reactivity of other A presents a risk in flash evaporating A low, the product is very very C
Biwer Rating Rationale – Direct Chlorination
very low (PubChem, 2016) Data given in Biwer et

substaces it interacts with (US Dept HHS, 2001) flammable (CameoChemicals,
al
Ehtylene is a hydrocarbon with a All global warming and ozone Vinyl Chloride is a kind of VOC
No information present on effect of
GWP B GWP less than 20 (Ghanta et al, C C depletion data found did not list B which contributes to ozone C
chlorine on the atmomsphere or its
2013) chlorinated compounds, must depletion and global warming but is
contribution to global warming. It is
assume if they have potential it is not a huge cause like florinated
assumed its contribution is
negligable compared their hydrocarbons (US EPA,
negligable
florinated counterparts 2002&CameoChemicals, 2016)
In fossil fuel, and compound adds
ODP B to Ozone depletion, but is not C C B C
florinated comound Table1
The process that makes ethylene
A life cycle assessment done on
and ethylene itself has a very In water, chlorine is a strong acid No information present on the
AP A A C B VC showed that the AP=1.5E-2 A
high potential to acidify the (PubChem, CID:24526, 2016) partioning or acidifcation
(Armstrong World Industries, 2014)
medium it is in, damaging to
Photochemically degrades to From same life cycle assessment
Is not a major contributor to No evidence of chlorine
POCP C C B hydroxyl radicals, and is not C POCP=1.6E-3 (Armstrong World C
ozone creation contributing to ozone creation
significantly removed by ozone or Industries, 2014)
Odor Threshold in water is 20 Vinyl chloride is a VOC which is
Ethylene is fairly odorless Chlorine has a suffocating odor
OD C B C mg/L which is greater than 300 B known to have a relatively strong C
(PubChem, 2016) (US EPA, 2000)
mg/m^3 (CDC/NIOSH, 2014) smell (CameoChemicals, 2016)
Although the compound itself Chlorine toxic in water or soil, Is not known to concentrate in soil
EP B does not contain P or N, it is B however does not contain N or P B or aquatic organisms, but chemical C No N or P present in compound C
relatively toxic to the environment (US EPA, 2000 & PubChem, spill has proven toxic in water
Ethlyene is an organic compound VC is a VOC which classifies as a
in petrol oil, and therefore adds to Hazardous Air pollutant in many carbon polluter, but is not a main
OCPP B C No organic compound present B B C
carbon pollution (Ghanta et al, US states (CDC/NIOSH, 2014) contributer to polution, as CO2 is
2013 & PubChem, 2016) (Cameo Chemicals, 2016)
Oxychlorination
Biwer Impact Rating
and Rationale
Inputs Ethylene Hydrogen chloride Oxygen
Outputs 1,2-dichloroethane water Ethylene Vinyl chloride Hydrogen chloride Oxygen
1,2-dichloroethane Rating Vinyl Chloride Hydrogen Chloride Hydrogen Chloride Water Rating
Ethylene Rating Ethylene Rating Rationale Oxygen Rating Oxygen Rating Rationale 1,2-dichloroethane Rating Vinyl Chloride Rating Rationale Water Rating
Impact Category Rationale Rating Rating Rating Rationale Rationale
Ethylene is made from fossil
DCE made from ethylene which is
fuels, but resevoirs will not run One of the most abundant
B C B a non renewable resource from (Input specifications) C
out within the next 10 years chemicals on earth
Avb fossil fuels
There are multiple ways to
Synthesis of DCE fairly simple,
produce ethylene, all of which Minimal steps involved in the
B C C does not require too many steps to C
require over 3 process steps to creation of oxygen
produce
CS synthesize (Ghanta et al,
Some critical materials are
No critical materials used in the
B used and made when creating C C No Critical Compounds involved C
making of O2
ethylene (Ghanta et al, 2014)
CM
There are no known studies
proving that ethylene is highly
toxic to humans, but studies When exposed to oxygeen levels Can cause temporary
Score came from rating on EPA
B have shown ethylene is B >75% can cause lung irritation B B incapacitation or injury (Cameo A C
website (US EPA-DCE, 2002)
metabolized into ethylene (UIGI, 2015) Chemicals-VC, 2016)
oxide (a known carcinogen)
AT (Ghanta et al, 2014)
Ehtylene is relatively toxic to
Can cause lung damage, but need
its environment and would not Toxicity range on EPA website
to be exposed to high oxygen Scores came from the EPA rating
B be okay to breath chronically, B A designates class A - Probable A B C
levels for long periods of time to of toxicity
but does not present high Carcinogen
get damage (UIGI, 2015)
ChT toxicity (PubChem, 2016)
No known effect on humans but
EPA has classified VC as a human
known to decrease fertitlity in rats
carcinogen. Case studies suggest
and listed as probable carcinogen
Known Carcinogen (Ghanta et No known endocrine effects (UIGI, correlation of increased birth
B C B of humans- There being a B C C
al, 2014) 2015) defects, and decreased fertility rate
possibility of carcinogen, is a good
in women, but studies have not
enough reason to list it as a class
proven causation
B
ED Scores from Biwer et Scores came from
Flash point of DCE very low- Flashpoint of Vinyl Chloride is very al Biwer et al
Highly Flammable, Flashpoint No/ minimal hazard of flammability
A C A presents a risk in flash evaporating A low, the product is very very C C
very low (PubChem, 2016) by MSDS (UIGI, 2015)
ThR (US Dept HHS, 2001) flammable (Cameo Chemicals-VC,
Biwer Rating Rationale – Oxychlorination
Ehtylene is a hydrocarbon with All global warming and ozone Vinyl Chloride is a kind of VOC
B a GWP less than 20 (Ghanta C O2 has negligable effects on C depletion data found did not list B which contributes to ozone C C
et al, 2014) global warming and ozone chlorinated compounds, must depletion and global warming but is
depletion, no data on global assume if they have potential it is not a huge cause like florinated
warming and oxygen negligable compared their hydrocarbons (Cameo Chemicals-
GWP
florinated counterparts VC, 2016)
In fossil fuel, and compound
B adds to Ozone depletion, but C C B C C
ODP is not florinated comound
The process that makes
ethylene and ethylene itself A life cycle assessment done on
No information present on the
A has a very high potential to C Oxygen is an oxidizer (UIGI, 2015) C B VC showed that the AP=1.5E-2 A C
partioning or acidifcation
acidify the medium it is in, (Armstrong World Industries, 2014)
AP damaging to biological factors
There is no solid evidence to Negligable if any contribution to Photochemically degrades to From same life cycle assessment
C suppoort ethylene having a C ozone creation, O2 reacts to form B hydroxyl radicals, and is not C POCP=1.6E-3 (Armstrong World C C
POCP POCP value O3 but does not directly add to significantly removed by ozone or Industries, 2014)
Odor Threshold in water is 20
Ethylene is fairly odorless
C C Oxygen is a colorless odorless gas C mg/L which is greater than 300 B From Armstrong World Industries C C
OD mg/m^3 (US Dept HHS, 2001)
Although the compound itself Is not known to concentrate in soil
Non-toxic and compound does not
B does not contain P or N, it is C B or aquatic organisms, but chemical C No N or P present in compound C C
contain N or P
EP relatively toxic to the spill has proven toxic in water (US
Ethlyene is an organic VC is a VOC which classifies as a
compound in petrol oil, and Hazardous Air pollutant in many carbon polluter, but is not a main
B C Not an organic compound B B C C
therefore adds to carbon US states (US Dept HHS, 2001) contributer to polution, as CO2 is
OCPP pollution (PubChem 2016) (Cameo Chemicals-VC, 2016)
Appendix D: Financial Sustainability
Figure D.1 – Bare model factors of Guthrie (1974). From (Seider, Seader, Lewin, & Widagdo, 2009).
Estimate of Total Capital Investment
An assessment of the Capital Investment was made to determine the expenses occurring within the primary
year of production. From the calculated purchase costs, the total bare-module investment can be prepared to
use in capital estimation. The bare-module factors for each type of equipment can be found in Bare-Module
Costing. Bare-module costs, CBM, for each piece of equipment can be calculated by the following equation:
𝐶𝐵𝑀 = 𝐹𝐵𝑀 𝐶𝑃
Using the total bare-module cost, an estimate of the total capital investment from (Seider, 2009) is produced.
Various costs were summed to achieve the final capital investment (US, 2002). Capital costs for spare items of
equipment, Cspare, were taken as the replacement cost of process machinery such as pumps. Costs for storage
tanks, Cstorage, were modeled after the rate of production. Cone roof storage tanks were used after obtaining the
volume of raw material or product needed per week. It was assumed that at least 7 days of materials would be
needed for storage.
1 𝑤𝑒𝑒𝑘 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙
𝑀𝑎𝑠𝑠 𝐹𝑙𝑜𝑤 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑤 𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝑜𝑟 𝑃𝑟𝑜𝑑𝑢𝑐𝑡 ∗ 7 𝑑𝑎𝑦𝑠 ∗ 24 ℎ𝑜𝑢𝑟𝑠 ∗ =
7 𝑑𝑎𝑦𝑠 𝑤𝑒𝑒𝑘
𝐶𝐸2016
𝐶𝑜𝑛𝑒 𝑅𝑜𝑜𝑓: 𝐶𝑃 = 265𝑉 0.51
𝐶𝐸2006
The previous costs can be summed to obtain the true total bare-module investment. Other investment costs
such as site preparation, Csite, were taken to be in the range of 4-6% as recommended by (Seider, 2009) for an
addition to an existing integrated complex. Service facilities and Allocated costs were omitted from capital
investment calculations as it was specified that the existing utilities can support new processing units and the
warehouse on site will have enough space. The sum of these costs yields the direct permanent investment, CDPI.
Once a recommended contingency fee of 18% is applied to this sum, the total depreciable capital, C TDC, is
obtained. No royalties or licensing fees were incurred, but a cost of startup was associated with the plant. As a
moderate chemical process, an estimate of 10% of the CTDC was taken as the startup cost, Cstartup. Working capital
funds can be determined with factors found in the operating “cost sheet” that estimates the total cost of
production. The total sum of these factors can be described as the total capital investment, CTCI. A summary of
the costs can be found in the financial sustainability section of the report.
Sample storage tank calculation:
Cone roof Flows DC process

Chlorine 117072.9 139550.8 g/wk 999.08 gal/hr 153704.6154 gal/wk HCl 3781.96 kg/hr
Ethylene 94459.85 112596.1 g/wk 655.9 gal/hr 100907.6923 Ethylene 2482.88 kg/hr
VC 135427.8 161429.9 g/wk 1329.3 gal/hr 204507.6923 VC 5113.06 kg/hr
HCl 70929.12 84547.51 g/wk 374 gal/hr 57538.46154 O2 1416 kg/hr
Total 417889.6 498124.4 g/wk
0.41789 indexed
0.498124 g/wk
Estimate of Total Production Costs
The continuing costs associated with the operation of a plant can be described by a cost sheet of representative
unit cost factors (Donati, 1997). When summed, these factors yield the total cost of production, C TPC. A major
consideration in these unit factors are the feedstock and utilities costs. To determine the feedstock and utility
costs, the operating factor for the plant was specified as 8000 hours per year, and indexed costs of raw materials
and utilities were found in (Seider, 2009). The following equations were then used. Cost factors for the resulting
costs are outlined within the cost sheet as recommended by (Seider, 2009). No general expenses were
associated with the total production cost.
𝑘𝑔 ℎ𝑟 $ $
𝑀𝑎𝑠𝑠 𝐹𝑙𝑜𝑤 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑤 𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 ∗ 8000 ∗ 𝐶𝑜𝑠𝑡 𝑜𝑓 𝑅𝑎𝑤 𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 = 𝐹𝑒𝑒𝑑𝑠𝑡𝑜𝑐𝑘 𝐶𝑜𝑠𝑡
ℎ𝑟 𝑦𝑟 𝑘𝑔 𝑦𝑟
𝑈𝑛𝑖𝑡 ℎ𝑟 $ $
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑈𝑡𝑖𝑙𝑖𝑡𝑦 (𝐹𝑟𝑜𝑚 𝐴𝑠𝑝𝑒𝑛 𝑃𝑙𝑢𝑠) ∗ 8000 ∗ 𝐶𝑜𝑠𝑡 𝑜𝑓 𝑈𝑡𝑖𝑙𝑖𝑡𝑦 = 𝑈𝑡𝑖𝑙𝑖𝑡𝑦 𝐶𝑜𝑠𝑡
ℎ𝑟 𝑦𝑟 𝑈𝑛𝑖𝑡 𝑦𝑟
Upon completion of the cost sheet for total production cost, the working capital for each plant can be
determined. The working capital is then added to the total capital investment to reflect a more accurate
estimation. The following equation defines working capital.
𝐶𝑊𝐶 = 𝑐𝑎𝑠ℎ 𝑟𝑒𝑠𝑒𝑟𝑣𝑒𝑠 + 𝑖𝑛𝑣𝑒𝑛𝑡𝑜𝑟𝑦 + 𝑎𝑐𝑐𝑜𝑢𝑛𝑡𝑠 𝑟𝑒𝑐𝑖𝑒𝑣𝑎𝑏𝑙𝑒 − 𝑎𝑐𝑐𝑜𝑢𝑛𝑡𝑠 𝑝𝑎𝑦𝑎𝑏𝑙𝑒
For the basis of this calculation, the following parameters were assumed from (Sieder, 2009).
1. Cash reserves accounted for 8.33% of the annual cost of manufacture.
2. Inventory amounted to 1.92% of annual sales of liquid and solid products
3. Accounts receivable amounted to 8.33% of all annual sales.
4. Accounts payable amounted to 8.33% of annual feedstock costs.
Profitability
ROI and PBP:
The return on investment (ROI) of a process plant can be defined as a percentage return per year. The total
capital investment divided the annual earnings yields the annual interest rate made by the profits on the original
investment (Guthrie, 1974). For simplicity, the depreciation in ROI is computed using straight-line depreciation
for 10 years. Also, the plant is assumed to operate each year, including the first, at 90% capacity with a 40%
income tax rate. Using these guidelines, the ROI can be computed using the following equations. S is defined as
the total sales revenue, C is the annual production cost, and D is the annual depreciation.
𝑛𝑒𝑡 𝑒𝑎𝑟𝑛𝑖𝑛𝑔𝑠 (1 − 𝑡)(𝑆 − 𝐶)

𝑅𝑂𝐼 = =
𝑇𝑜𝑡𝑎𝑙 𝐶𝑎𝑝𝑖𝑡𝑎𝑙 𝐼𝑛𝑣𝑒𝑠𝑡𝑚𝑒𝑛𝑡 𝐶𝑇𝐶𝐼
𝐶𝑇𝐶𝐼 = 𝐶𝑇𝐷𝐶 + 𝐶𝑊𝐶

The payback period (PBP) is the time required for the annual earnings to equal the original investment. Using
the same guidelines applied to the ROI, the PBP can be calculated. Due to rapid progress of technology, a PBP
𝑇𝐷𝐶 𝐶
of more than 4 years will indicate that the project is not recommended. 𝑃𝐵𝑃 = (1−𝑡)(𝑆−𝐶)+𝐷
Sample calculation of ROI and PBP (PP):

ROI
TPC w/ depreciation 39.37611
Pre-tax earnings 0.61904
Income taxes 0.247616
After-tax earnings 0.371424
TCI (TDC + WC) 10.09153
ROI 4%
eqn 23.7
PP 6.04 yrs
eqn 23.8
NPV and IRR:
Net present value (NPV) is the sums of discounted cash flows over a plant’s lifespan. These cash flows are
compared against a set interest rate. The interest rate for this plant’s company is specified at 15%. For the first
3 years, including permitting, a third of the capital investment was used each year. For NPV purposes, the first
year of production occurred at 30% capacity, the second year at 60%, and the 3 and subsequent years at 90%.
The plant’s production life-span is approximately 15 years. After the 15th year, the working capital is recovered
and the plant is sold for salvage. To compute the cash flows, a 10-year straight-line depreciation was considered.
A chart of cash flows is presented in the Profitability assessment of the report. The calculations of cash flows
are presented in the following equations.
𝑁𝑒𝑡 𝐸𝑎𝑟𝑛𝑖𝑛𝑔𝑠 = (𝑆 − 𝐶𝐸𝑥𝑐𝑙. 𝐷𝑒𝑝. − 𝐷) ∗ (1 − 𝑖𝑛𝑐𝑜𝑚𝑒 𝑡𝑎𝑥 𝑟𝑎𝑡𝑒)
𝐷𝑖𝑠𝑐𝑜𝑢𝑛𝑡𝑒𝑑 𝐶𝑎𝑠ℎ 𝐹𝑙𝑜𝑤 = 𝑁𝑒𝑡 𝐸𝑎𝑟𝑛𝑖𝑛𝑔𝑠 + 𝐷
𝐴𝑛𝑛𝑢𝑎𝑙 𝐶𝑎𝑠ℎ 𝐹𝑙𝑜𝑤 = 𝐶 = (𝑁𝑒𝑡 𝐸𝑎𝑟𝑛𝑖𝑛𝑔𝑠 + 𝐷) − 𝑓𝐶𝑇𝐷𝐶 − 𝐶𝑊𝐶
The annual cash flows can then be summed to obtain the cumulative present value of discounted cash flows.
The internal rate of return is defined as the point at which the NPV is zero. This is done by adjusting the tax
interest rate until the investment in repaid at the end of the project. The IRR was calculated with the same
methods as the NPV, but iteratively solving for the point at which the cumulative present value was zero. Excel
solver was used to compute this value.
Sample Calculation of IRR:

Using the above Solver method, we were able to examine the sensitivity of %IRR to changes in TCI, capacity, and
price of vinyl chloride (Ogle, 2014).
Sensitivity of IRR
The graph shows sensitivity of the internal rate of return to the price of vinyl chloride, capacity, and TCI. While
TCI maintains a linear relationship the IRR appears to vary logarithmically with both the capacity and price of
vinyl chloride. No IRR was possible at relative price of VC below 79%, or a plant capacity below 71%. Below those
thresholds, there was no interest rate that would allow the plant to break even in 15 years of production.
%TCI %IRR % Capacity %IRR % Price of VC %IRR
50% 46% 71% 2% 79% 2%
75% 40% 75% 13% 94% 30%
100% 36% 90% 36% 100% 36%
125% 33% 125% 54%
150% 30% 150% 67%
Cost Item Cost Factor Annual Cost (MM$/yr) Unit Cost ($/metric ton of VC) Comment
*Indexed cost as MS Index =
Feedstocks (raw materials) 596 for 2016 (Seader, 2016)
Chlorine $0.38/kg 18.52 438.25 *
Ethylene $0.88/kg 16.96 401.54 *
Total Feedstocks
Utilities
Steam, 150 psig $12.57/Metric Ton 0.32 7.47 *
Electricity $0.06/kW-hr 0.03 0.78 *
Refrigerant $12.21/GJ 0.12 2.90 *
Total Utilities 0.47 11.15
Modeled as moderate-
capacity continuous fluids
Operations (O) process
30 shift operators w/ 5
Direct wages and benefits (DW & B) $35/operator-hr 1.09 25.85 shifts/day
Direct salaries and benefits 15% of DW&B 0.16 3.88
Operating supplies and services 6% of DW&B 0.07 1.55
Technical assistance to manufacturing $60,000/(operator/shift)-yr 0.30 7.10
Control laboratory $65,000/(operator/shift)-yr 0.33 7.69
Total Operations (O) 1.95 46.07
Maitenance (M)
Wages and benefits (MW & B) 3.5% of TDC 0.20 4.70
Salaries and benefits 25% of MW&B 0.05 1.17
Materials and services 100% of MW&B 0.20 4.70
Maintenance overhead 5% of MW&B 0.01 0.23
Cost Sheet for Direct Chlorination Model
Total Maintenance 0.46 10.80

Total of M&O - SW&B 1.50 35.59
Operation overhead
General plant overhead 7.1% of M&O-SW&B 0.11 2.53
Mechanical department services 2.4% of M&O-SW&B 0.04 0.85
Employee relations department 5.9% of M&O-SW&B 0.09 2.10
Business services 7.4% of M&O-SW&B 0.11 2.63
Total operating overhead 0.34 8.12
Property taxes and insurance 2% of TDC 0.11 2.68
Depreciation 10-year SL depreciation
Direct plant 10% of TDC 0.57 13.41
Allocated plant 6% of Calloc 0.00 0.00
Total depreciation 0.57 13.41
Total Cost of Manufacture (COM)
General Expenses
Total Product Cost (TPC) 39.38
Cost Item Cost Factor Annual Cost (MM$/yr) Unit Cost ($/metric ton of VC) Comment
*Indexed cost as MS Index =
Feedstocks (raw materials) 596 for 2016 (Seader, 2016)
HCl $0.09/kg 2.72 66.570 *
Ethylene $0.88/kg 17.48 427.324 *
Oxygen $0.06/kg 0.68 16.616 *
Total Feedstocks 20.88 510.51
Utilities
Steam, 150 psig $12.57/Metric Ton 0.32 7.84 *
Electricity $0.06/kW-hr 0.04 0.93 *
Cooling Water (cw) $0.019/m^3 0.01 0.26 *
Refrigerant $12.21/GJ 0.10 2.51 *
Total Utilities 0.47 11.54
Modeled as moderate-capacity
Operations (O) continuous fluids process
30 shift operators w/ 5
Direct wages and benefits (DW & B) $35/operator-hr 1.09 26.70 shifts/day
Direct salaries and benefits 15% of DW&B 0.16 4.00
Operating supplies and services 6% of DW&B 0.07 1.60
Technical assistance to manufacturing $60,000/(operator/shift)-yr 0.30 7.33
Control laboratory $65,000/(operator/shift)-yr 0.33 7.95
Total Operations (O) 1.95 47.58
Maitenance (M)
Wages and benefits (MW & B) 3.5% of TDC 0.16 4.02
Salaries and benefits 25% of MW&B 0.04 1.00
Materials and services 100% of MW&B 0.16 4.02
Maintenance overhead 5% of MW&B 0.01 0.20
Cost Sheet for Oxychlorination Model
Total Maintenance 0.38 9.24

Total of M&O - SW&B 1.46 35.72
Operation overhead
General plant overhead 7.1% of M&O-SW&B 0.10 2.54
Mechanical department services 2.4% of M&O-SW&B 0.04 0.86
Employee relations department 5.9% of M&O-SW&B 0.09 2.11
Business services 7.4% of M&O-SW&B 0.11 2.64
Total operating overhead 0.33 8.14
Property taxes and insurance 2% of TDC 0.09 2.29
Depreciation 10-year SL depreciation
Direct plant 10% TDC 0.47 11.47
Allocated plant 6% of Calloc 0.00 0.00
Total depreciation 0.47 11.47
Total Cost of Manufacture (COM) 24.57
General Expenses
Total Product Cost (TPC) 24.57

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Vinyl Chloride Production

CHEN 4520 Chemical Process Synthesis

December 9th, 2016

Developed for Thomas K. Belval

Lucas Karasek Bruce Kirkpatrick Aaron Lipsey Kaela Siahpush

Oxychlorination Process Design.........................................................................................................................................................3

Financial Sustainability Assessment ..................................................................................................................................................9

Direct Chlorination Net Present Value Sensitivity Analysis .............................................................................................................. 15

Direct Chlorination Simulation Development Summary

OXYCHLORINATION PROCESS DESIGN

Direct Chlorination Composite Curve

Figure UR.1 – Composite curves for direct chlorination process.

Figure UR.2 – Composite curves for oxychlorination process.

Oxychlorination Table UR.2 – Utilities summary for oxychlorination process.

ENVIRONMENTAL SUSTAINABILITY ASSESSMENT

Biwer’s Method Overview

Table ES.2 – Component EI fraction values for oxychlorination process.

Component EI of Component EI of Output EI fraction Total process 1.35 1.000

FINANCIAL SUSTAINABILITY ASSESSMENT

Direct chlorination reactor and

Total bare-module cost for Total bare-module cost

Total Capital Investment

Total Production Cost

Return on Investment and Payback Period

Net Present Value (NPV) and Investor’s Rate of Return (IRR)

Summary of Profitability Analysis

DIRECT CHLORINATION NET PRESENT VALUE SENSITIVITY ANALYSIS

%TCI NPV % Capacity NPV % Price of VC NPV

Appendix A: Process Design

Reaction Schemes – Direct Chlorination

Direct chlorination in a liquid phase of 1,2-dichloroethane involves two primary reactions:

C2H4 + Cl2 –(R1) C2H4Cl2 (A1)

C2H4Cl2 + Cl2 –(R2) C2H3Cl3 + HCl (A2)

C2H4Cl2 –(R3) C2H3Cl + HCl (A3)

C2H3Cl –(R4) C2H2 + HCl (A4)

C2H4Cl2 –(R5) C2H4 + Cl2 (A5)

Reaction Pre-exponential factor [s-1] Activation energy [cal/mol]

2 C2H4Cl2 –(R7) C4H8Cl2 (A7)

C2H3Cl + Cl2 –(R8) C2H3Cl3 (A8)

C2H4Cl2 + Cl2 –(R9) C3H3Cl3 + HCl (A9)

C2H2 + 2 Cl2 –(R10) C2HCl3 + HCl (A10)

Reaction Schemes – Oxychlorination

C2H4Cl2 + HCl + 0.5 O2 –(R12) C2H3Cl3 (A12)

Which are governed by the rate expressions (Carrubba, 1970):

R11 = (k11KaCcPC2H4) / (RT + KaPC2H4)

R12 = k12PC2H4Cl2 * sqrt(PCl2)

Appendix B: Stream Matching Diagrams

All non-original tables and charts come from (Biwer, 2004).

At right is a map of how the impact categories and impact

To calculate the environmental impact of all of the

Impact Category Impact Group Impact Group

Avb C Resources C 0 0.325

Outlets: Output Components

AT B Organisms B 0.3 0.65

Component Vinyl Chloride

Component Hydrogen Chloride

Environmental Factor Tables – Oxychlorination

Impact Category ABC Impact Group Impact Group

Avb B Resources B 0.3 0.475