CENG 100 Chemical Process Project Description

Plant for Production of Vinyl Chloride (PVC Precursor)

Introduction:
Polyvinyl chloride (PVC) is one of the worlds most versatile thermoplastics, having a wider
range of uses than any other plastic material. It can be made as a hard plastic, used in pipes and
window fixtures, or can be made small, to be used in clothing, hoses, flooring, etc. Not only is it
versatile, but it is cheap, nontoxic, and inert. The feedstock for PVC production is the vinyl
chloride monomer (VCM). Due to the extensive use of PVC, VCM production is one of the top
20 largest petrochemical industries in the world. Approximately 13 billion kg of VCM are
produced annually, mostly in the U.S. and China, and production is only expected to increase as
PVC demand increases.

Your Assignment:
Analyze the provided plant design to determine the amount of vinyl chloride product that can be
produced under the conditions provided. You will utilize material and energy balances, as learned
during CENG 100, to determine flow rates, concentrations, and heat/work requirements
throughout the process. Our goal is to determine whether the current setup of the plant will be
profitable and result in a product that is at least 90% pure vinyl chloride.

Project Goal:
The purpose of this project is to introduce you to a complete process in a plant and tie together
all the concepts taught in CENG 100. You will determine how this plant operates under idealized
conditions (ideal reactors, ignoring kinetics, ideal separation units, ideal heat transfer). You will
be re-introduced to this project throughout your curriculum in CENG at UCSD to correct these
simplified assumptions and model this plant more accurately.

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Process Description:
The first large-scale plants producing vinyl chloride utilized the hydrochlorination of acetylene.
However, since the mid 1950s, production from ethylene (as this precursor became more readily
available) has become the primary synthesis route. Now, 95% of all vinyl chloride is produced
from a series of reactions starting with chlorine, ethylene, and air. Ethylene (C2H4) and chlorine
(Cl2) directly react to produce dichloroethane (C2H4Cl2, DCE). The DCE intermediate is then
sent to a cracking furnace where it is pyrolyzed to vinyl chloride monomer (VCM) and hydrogen
chloride (HCl). So the HCl does not go to waste, it is separated and sent to another reactor where
it reacts with additional fresh ethylene and oxygen to produce additional DCE and water. The
additional DCE is combined with the original DCE when fed to the pyrolysis furnace. The
product is separated, with the DCE recycled and the VCM collected as product for later
processing into PVC.

Process Steps:
Direct Chlorination of Ethylene:
Fresh ethylene gas is typically fed with purified chlorine gas (in slight excess) into the direct
chlorination reactor (R1), where the following reaction takes place:
Direct Chlorination (DC):

C2H4 + Cl2 C2H4Cl2

(1)

This reaction is typically conducted with an iron(III) chloride catalyst. The reaction is
exothermic and is typically cooled by use of cooling water.
In our system, the reactor operates at a constant P = 10 bar and T = 183 C.
The reaction goes almost to completion, thus requiring no separation or recycle.
Prior to entering the reactor, the streams are combined, pre-heated and compressed.

Oxychlorination of Ethylene:
Additional fresh ethylene is fed with air (or pure oxygen) and recycled HCl from later in the
process into the oxychlorination reactor (R2). The following reaction takes place:
Oxychlorination (OC):

C2H4 + 0.5 O2 + 2HCl C2H4Cl2 + H2O (2)

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This reaction is highly exothermic and requires significant cooling to prevent runaway
temperatures and unwanted side-reactions.
The reaction takes place over a copper(II) chloride catalyst.
In our system, the reactor operates at a constant P = 10 bar and T = 260C.
The recycled HCl is provided entirely from the subsequent reactor.
The oxygen is fed such that the HCl is in 2% excess so all oxygen can be consumed.
In reality, some side-reactions inevitably take place that produce poly-chlorinated alkanes.

DCE Separation and Purification:

The effluent from R2 is sent through a separator to vent off N2 and any other gaseous inerts. A
minimal amount of reactants/products are lost at this point. This separator also collects and
recycles any solid catalyst from R2 that may have passed out of the reactor. Once the two reactor
effluent streams are combined, they are passed through a scrubbing column, where the products
come in contact with a dilute NaOH solution to remove chloral and various other chlorinated
byproducts. After the addition of a DCE recycle stream, the materials enter a series of separator
columns to remove all materials other than DCE and VCM.

Pyrolysis of Dichloroethane:
The resulting reactor feed enters a pyrolysis furnace operating at a high temperature and pressure
where the DCE decomposes into vinyl chloride and HCl.
DCE Pyrolysis/VC Synthesis (VCS):

C2H4Cl2 C2H3Cl + HCl

(3)

Conversion is moderate requiring recycle of all unused DCE for higher overall conversion.
The reaction is highly endothermic, needing to be carried out in a fired heater. This heat is
provided by the combustion of methane.
In our system, the reactor operates at a constant P = 20 bar and T = 500C.
Since VCM is not very stable at the operating temperature, the residence time of the reactor is
kept low and the effluent stream must be immediately quenched.

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Final VCM Purification:

Subsequently, HCl is stripped out of the R3 effluent and recycled to the oxychlorination reactor.
The bottoms stream of the stripping column is sent to a series of distillation columns where the
final purified VCM product is collected. The DCE-rich bottoms streams are recycled to the
pyrolysis furnace. In our process, since we are not familiar with distillation, we will utilize a
single flash column operating at 105C and 12 bar.

Energy Considerations:
Energy integration is of key importance in modern vinyl chloride synthesis plants. The students
will be asked to determine various energy/work requirements throughout the process.

Special Note: The side-reactions that have thus far been neglected are accounted for via the
purification steps described above. Instead of losing unreacted raw materials, these separators are
designed to also remove all undesired byproducts from the reactors.

Process Flow Diagram:

See the following pages for the plant design and a list of specific design features.

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HCl Recycle (R)

Air (A)

OxyChlorination
Reactor (R2)

E2
Vent
Gases (V)

Separator
Ethylene (F)

VCM
Product (P)

RF

DCE
Cracking
Furnace (R3)

E3

Column

Stripper

Dryer &
Separator

Dilute
NaOH (N)

H
W J
DCE Recycle (D)

Note: Stream labels are provided in the diagram.

E1

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Scrubber

Chlorine (C)

Direct
Chlorination
Reactor (R1)

Process Design Features:

(1)

The ethylene feed is split 55:45 between reactors R1 and R2.

(2)

Chlorine in stream C is fed in 5% excess to reactor R1.

(3)

In R1, the ethylene and chlorine start at 25C and 1 bar, but are compressed to 10 bar.

(4)

The direct chlorination reactor (R1) operates at 183C and 10 bar.

(5)

Reactor R1 is designed such that the conversion of ethylene to DCE is 99% with a typical
residence time between 60 and 75 seconds.

(6)

The ethylene feed to reactor R2 and the air feed also start at 25C, but are pre-heated to
150C and then compressed to 10 bar.

(7)

All HCl fed to R2 comes from stream R and is fed in 2% excess relative to the oxygen.

(8)

The oxygen is entirely consumed and all potential side-reactions are ignored.

(9)

The oxychlorination reactor operates at 260C and 10 bar.

(10)

Typical residence times for R2 are 160 to 200 seconds.

(11)

In the first separator, all N2 and 10% of the ethylene in E2 are removed and vented in V.

(12)

In the scrubber, the byproducts removed to H will be modeled as 10% of the Cl2, C2H4,
and H2O, 50% of the HCl and 1% of the DCE.

(13)

In the dryer and separator, all remaining water is removed in stream W, with all other
byproducts removed in junk stream, J. This leaves stream RF with only DCE & VC.

(14)

Reactor R3 operates at 500C and 20 bar, with a residence time between 2-30 seconds.

(15)

All HCl is perfectly removed from E3 and is recycled in stream R.

(16)

The flash column operates at 105C and 12 bar, where the product vapor stream is
collected and the bottoms stream is entirely recycled.

(17)

The quality of the fluid within the flash drum after reaching phase equilibrium is 0.53.

(18)

ALL VAPORS CAN BE TREATED AS IDEAL GASES.

(19)

ALL PHASE EQUILIBRIA CAN BE MODELED USING RAOULTS LAW.

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PROJECT:
Answer the questions on the following pages. Prior to Thanksgiving, a sheet will be provided
that you can print out and simply write down your final answer in the provided locations.

To show work, provide hand-written sample calculations for each part. In other words, for
streams with seven components (as an example), write out and solve a species/material balance
for at least one component.
- If you use MATLAB to help you solve, provide the code you used for each question, with clear
labels for all equations defined. Ask instructors for more details.
- If you use Excel to help you solve, provide print-outs of all your data calculations, but clearly
box and label sections for different calculations. Ask instructors for details.
- If you complete all calculations by hand, please write out all species balances for all your
calculations and provide all necessary solutions to these balances that are relevant to answer the
questions on the following pages.

GROUPS:
You are allowed (AND ENCOURAGED) to work on this project in groups as large as 5 or 6.
Groups CANNOT be any larger. Also, NO ONE can work alone. This is supposed to be a
collaborative effort, so you have to find at least one other person to work with. All group
members are expected to contribute equally and the work provided should label clearly which
person contributed to what parts.
Each group is expected to turn in a single completed project.

NOTE: LEGIBILITY AND CLEAR ORGANIZATION OF SOLUTIONS ARE NECESSARY

FOR PROPER GRADING.

WORTH: 10% of the overall course grade. DO NOT WAIT UNTIL THE LAST MINUTE TO
START THIS PROJECT. YOU WILL REGRET IT.

DUE: Wednesday, December 10, beginning of class.

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Material Balance Questions: Let F = 100 mol/s unless stated otherwise

1. Based on the direct chlorination reactor effluent (E1), what range of volumes should be
designed for the reactor, R1?

2. (a.) How much air is fed to the reactor? (b.) What is the conversion of ethylene in the
reactor? (c.) What is the conversion of HCl in the reactor? (d.) Give a size range for the
reactor, based on the reactor effluent. (e.) How would this volume range change if pure
oxygen were used instead of air?

3. (a.) What is the volumetric flow rate of the vent gases, stream V? (b.) What is the mass flow
rate of material removed in the scrubber?

4. (a.) What is the volumetric flow rate of liquid water removed in the dryer? (b.) What is the
mass flow rate of the junk stream, J, in kg/s and kg/day?

5. (a.) What is the single-pass conversion of DCE in the cracking furnace? (b.) What is the
overall conversion of DCE around the DCE recycle loop? (c.) Based on the exhaust flow rate
(E3), give a size range for this reactor.

6. How much HCl is removed in the stripping column and recycled back to R2?

7. (a.) How much of the product stream, P, is produced? (b.) What is the composition of this
stream? (c.) What is the mass ratio of vinyl chloride produced to ethylene fed to the process?

8. (a.) If the plant must produce 1200 metric tons per day of this product stream, how much
ethylene feed is necessary in metric tons per day? (b.) How much of the junk stream, J, is
produced under these conditions in metric tons per day?

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Energy Balance Questions: Let F = 100 mol/s unless stated otherwise

9. If the feed to R1 starts at 25C and 1 bar,: (a.) How much work (total) is needed to compress
the feed to 10 bar adiabatically? (b.) What is the final temperature after the compression?
Assume the volumetric flow rate is reduced to 1/6 its initial rate during compression.
10. (a.) How much heat is removed from the direct chlorination reactor if the exhaust exits at
183C? (b.) The heat is removed by cooling water, which starts at 10C and 1 atm. If the
water cannot be heated beyond 60C (for later water recycle purposes), how much water in
kg/s is required? Assume negligible pressure change.
11. The ethylene and air enter R2 at 25C and 1 bar. (a.) How much work (total) is needed to
compress the feed to 10 bar adiabatically? (b.) What is the final temperature after the
compression? Assume the volumetric flow rate is reduced to 1/6 its initial rate.
12. The HCl recycle, R, is already at 150C and 10 bar when combined with the other feed
streams. (a.) How much heat must be removed from the reactor if the exhaust temperature is
260C? (b.) Another cooling water stream (starting at 10C) is used for heat removal. Again,
if the water cannot be heated beyond 60C, how much water in kg/s is required?
13. For efficient operation of the scrubber, dryer, and second separator, the process stream (L)
must be cooled to 100C. How much heat must be removed?
14. (a.) How much work is necessary to compress stream RF to 20 bar (initially at 10 bar and
100C) adiabatically? The final volumetric flow rate is 60% of the inlet. (b.) What is the final
temperature after compression? (c.) How much heat is needed to then heat the stream up to
500C?
15. (a.) How much heat must be added to the cracking furnace, R3, to keep it isothermal? (b.)
Heat is provided by the 100% combustion of methane with 20% excess air. If half of this

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combustion heat can be readily used by R3 and the combustion products exit at 900C, how
much methane and air in m3/s are necessary? Assume combustion feed enters at 1 bar, 25C.
16. Stream E3 must be quenched to a much lower temperature or the vinyl chloride decomposes.
(a.) How much heat must be removed to cool the stream to 250C? (b.) The stream is then
expanded from 20 bar to 12 bar before entering the stripper. How much work can be removed
in this process if the volumetric flow rate increases by 50%? (c.) What is the final
temperature of the stream before entering the stripper?
17. How much heat must be removed from stream B (at the temperature from 17c) to cool the
stream to 105C for the flash unit?
18. The product stream is typically stored as a liquid at room temperature (25C). What is the
minimum pressure the product must be stored at to guarantee it is entirely liquid?

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