Aspen VCM Report

AspenTech Report
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VCM PLANT MODEL
SINOPEC Qilu Petrochemical

Company
May 2002
SINOPEC Qilu Petrochemical Company
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This report contains proprietary information of

SINOPEC Qilu Petrochemical Company and Aspen Technology, Inc.
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SINOPEC Qilu Petrochemical Company VCM Model
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Table of Contents
1 Summary................................................................................3
2 VCM Manufacture and Project Goals.........................................4
3 Section 100 – Direct Chlorination..............................................7
4 Section 200 – Oxychlorination..................................................9
5 Section 300 – EDC Purification................................................16
6 Section 400 – EDC Pyrolysis....................................................18
7 Section 500 – VCM Purification................................................22
References.....................................................................................................26
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1 Summary
This report documents the Aspen Plus models for SINOPEC Qilu Petrochemical
Company’s balanced vinyl chloride monomer (VCM) plant developed by AspenTech
with assistance of three engineers from the Qilu Petrochemical Company (QPC). The
three QPC engineers are ZhengHua Cai, YuChu Guo and WeiQiang Xu.
Effective models for VCM (and other chemical) facilities require accurate and reliable
foundation models (for thermodynamic properties, reaction kinetics and heat transfer),
flexible and robust models for the process equipment (for example, reactors, heat
exchangers, flash separators and distillation columns) and robust schemes to converge the
process flowsheets. The VCM process is especially challenging because it contains
nonideal mixtures, electrolytes, complex reactors and integrated flowsheets. This project
used the combination of the deep process-modeling knowledge of AspenTech personnel
and the intimate knowledge of the VCM plant of the QPC process engineers to develop
effective steady-state models of the QPC VCM plant. The joint project also served as the
basis for AspenTech to train the QPC engineers to model VCM and other chemical plants.
The QPC VCM plant uses the balanced process and is divided into five sections: direct
chlorination, oxychlorination, ethylene dichloride (EDC) purification, EDC pyrolysis and
VCM purification sections (see Figure 1). All these five sections have been modeled in
this project and the models are documented in this report.
This report is organized in the following way. Chapter 2 provides background

information on VCM manufacture and the broad approach taken in the project. Chapters
3-7 describe the simulation models developed for the five plant sections. Chapter 8
provides instructions on running the AspenTech VCM models using Aspen Plus. A
chapter called References provides citations for the technical literature on the VCM
process that are cited in this report.
The VCM models will enable analysis to understand, trouble-shoot and improve plants,
and will serve as the basis for planning and executing future plant expansions.
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2 VCM Manufacture and Project Goals
The QCP VCM plant uses the balanced process based upon ethylene and chlorine (Cowfer
and Gorensek, 1996; Ullmann’s, 1999). The reactions for each component process are
shown in equations 1-3 and the overall reaction is given by equation 4:
Direct Chlorination CH2=CH2 + Cl2  ClCH2CH2Cl (1)

EDC Pyrolysis 2ClCH2CH2Cl  2CH2=CHCl + 2HCl (2)
Oxychlorination CH2=CH2 + 2HCl + ½O2  ClCH2CH2Cl + H2O (3)
Overall reaction 2CH2=CH2 + Cl2 + ½O2  2CH2=CHCl + H2O (4)
In a typical balanced plant producing VCM from EDC, all the HCl produced in the EDC
pyrolysis is used as the feed for the oxychlorination. On this basis, EDC production is
about evenly split between direct chlorination and oxychlorination, and there is no net
production or consumption of HCl. The three principal reaction steps and the associated
separation and heat-integration steps are shown in Figure 1.
HCl Recycle
O2
Oxychlorination Light ends
H2O Ethylene Ethylene Vinyl

C2H4 dichloride dichloride chloride Vinyl
purification pyrolysis purification chloride
Ethylene dichloride recycle
Direct
chlorination Heavy ends
Cl2
Figure 1. Principal Steps in a Balanced Vinyl Chloride Process
In the QPC plant, the principle steps are designated as section numbers as follows:
Section Process Step

Section 100 Direct Chlorination
Section 200 Oxychlorination
Section 300 Ethylene Dichloride (EDC) Purification
Section 400 EDC Pyrolysis
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Section 500 Vinyl Chloride (VCM) Purification
The goal of the project was to develop rigorous kinetic models for the Oxychlorination
(Section 200) and EDC Pyrolysis (Section 400) reactors and a stoichiometric conversion
model for the Direct Chlorination (Section 100) reactor, to develop effective models for the
various flash separation, heat exchange and distillation models used in the process and to
combine these building blocks into flowsheet models for each of the five sections of the
QPC VCM plant.
The modeling approach taken was, as far as possible, to use standard models within Aspen
Plus. Thus, the reactor kinetics were described using POWERLAW (power law) or LLHW
(Langmuir-Hinschelwood-Hougen-Watson) kinetics. Because of this approach, most of the
models developed in this project are described by the standard Aspen Plus documentation.
The only exception to this is the model developed for the radiative heat transfer in the EDC
Pyrolysis reactor. In this case a user subroutine needed to be developed. The use of this
model, together with general comments on running Aspen Plus models is presented in
Chapter 8.
In this report it is assumed that the reader is familiar with the use of Aspen Plus, and
especially advanced features like electrolyte thermodynamics, reactor models and advanced
distillation. Brief training was provided to QPC engineers in the use of these advanced
features. It is recommended that engineers who use and further develop the VCM
simulation models take the appropriate courses from AspenTech.
It is expected that the VCM models will achieve the following objectives:
 Design optimal process configurations and plant operations to maximize production rate
and minimize production costs.
 Assist in scaling up and debottlenecking of existing production lines, including reactor
and flowsheet modifications.
 Explore operating conditions for new catalysts.
 Train operators to better operate the plant and handle plant upsets.
 Support the study of capital investment projects to design and revamp the plant.
Based upon AspenTech’s past experience, expected benefits of the VCM modeling project
will be as follows:
 Material consumption will be reduced by 2%.

 Utility consumption will be reduced by 2%.
In addition to the direct benefits, several indirect benefits are expected to be achieved:
 Production rate will be increased.
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 Engineers will be trained to better understand the technology of building process models
and to apply process models.
 Operators will be trained to better operate plants and to understand the process.
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3 Section 100 – Direct Chlorination
Direct chlorination of ethylene is conducted in liquid EDC in a bubble column reactor.

Ethylene and chlorine dissolve in the liquid phase and combine in a homogeneous
catalytic reaction to form EDC. Under typical process conditions, the reaction rate is
controlled by mass transfer, with absorption of ethylene as the limiting factor. The
catalyst, ferric chloride, is highly efficient for the chlorination reaction. The product is
extracted from the vapor phase. In the Aspen Plus model developed in this project the
reactor is modeled simply as an RSTOIC model in which the conversion to EDC and the
various side products is specified.
The components used in the Section 100 model are as follows:
ID Component name Formula

C2H4 ETHYLENE C2H4
C2H6 ETHANE C2H6
C3H6 PROPYLENE C3H6-2
CL2 CHLORINE CL2
O2 OXYGEN O2
HCL HYDROGEN-CHLORIDE HCL
H2 HYDROGEN H2
N2 NITROGEN N2
LIGHTS ETHYL-CHLORIDE C2H5CL
EDC 1,2-DICHLOROETHANE C2H4CL2-2
C2H3CL3 1,1,2-TRICHLOROETHANE C2H3CL3
HEAVIES 1,1,2,2-TETRACHLOROETHANE C2H2CL4-D2
H2O WATER H2O
C2CL4 TETRACHLOROETHYLENE C2CL4
The physical property method NRTL-RK is used. This method uses the NRTL activity-
coefficient model to describe the nonideality of the liquid phase and the Redlich-Kwong
model to describe the nonideality of the vapor phase. It is appropriate for the mixtures
and conditions of the Direct Chlorination section.
The Direct Chlorination reactor has been described using an RSTOIC model with the
following reactions and specified conversions:
Rxn Key Fractional

No. Stoichiometry Component Conversion
1 C2H4 + CL2 --> EDC CL2 0.9984
2 C2H4 + 4 CL2 --> C2CL4 + 4 HCL CL2 0.0002
3 EDC + CL2 --> C2H3CL3 + HCL CL2 0.001
4 2 C2H4 + 2 CL2 --> LIGHTS + C2H3CL3 CL2 0.0004
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The first reaction in the above table is Equation (1) in Chapter 1. The other reactions
describe the main side reactions. The reactions and conversions were chosen based upon
the information published in VCM references (Cowfer and Gorensek, 1996; Ullmann’s,
1999) and the experience of the AspenTech and QPC personnel.
Using the Direct Chlorination reactor described above, an Aspen Plus model for Section
100 of the plant was developed as shown in Figure 2.
E101
F101G V 122
121
105
107 106 E102
117
FA 101
104 G B101 119
DC101
102 116
FA 102
110
108A
120A
EA 103
108 120
FS PLI T
109
G A101 G A103
111
Figure 2. Section 100 – Direct Chlorination
The reactor described above has been implemented in Aspen Plus as DC101. The other
blocks in Section 100 are standard Aspen Plus models and will not be described further.
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4 Section 200 – Oxychlorination
In oxychlorination, ethylene reacts with dry HCl and either air or pure oxygen (the QPC
VCM plant uses pure oxygen) to produce EDC and water (Equation (3) of Chapter 1). The
catalyst contains cupric chloride as the active ingredient. The reaction is highly exothermic
and thus good temperature control is very important. The QPC plant uses a fluidized bed
with internal cooling coils containing hot water for heat removal. The by-products from the
reactor include unreacted HCl and also CO2, and this section contains distillation columns to
remove them. Since these compounds and the absorbing chemicals form electrolytes, an
ionic model is necessary for the development of an effective model.
The components used in Section 2 are as follows:

C2H2 ACETYLENE C2H2
VCM VINYL-CHLORIDE C2H3CL
C4H5CL CHLOROPRENE C4H5CL
LB ETHYL-CHLORIDE C2H5CL
TEC 1,1,2-TRICHLOROETHANE C2H3CL3
HB 1,1,2,2-TETRACHLOROETHANE C2H2CL4-D2
NAOH SODIUM-HYDROXIDE NAOH
H2O WATER H2O
NA+ NA+ NA+
H3O+ H3O+ H3O+
OH- OH- OH-
CL- CL- CL-
NACL SODIUM-CHLORIDE NACL
NA2CO3 SODIUM-CARBONATE NA2CO3
NACLO3 SODIUM-CHLORATE NACLO3
NA2SO4 SODIUM-SULFATE NA2SO4
H2SO4 SULFURIC-ACID H2SO4
CO2 CARBON-DIOXIDE CO2
HSO4- HSO4- HSO4-
HCO3- HCO3- HCO3-
CLO3- CLO3- CLO3-
CO3-- CO3-- CO3-2
SO4-- SO4-- SO4-2
N2 NITROGEN N2
O2 OXYGEN O2
CO CARBON-MONOXIDE CO
C2H4 ETHYLENE C2H4
C3H8 PROPANE C3H8
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H2 HYDROGEN H2
C2H6 ETHANE C2H6
CO2-IN CARBON-DIOXIDE CO2
Three physical-property models are used in this section: NRTL-RK, ELECNRTL, and
STEAMNBS. NRTL-RK uses the NRTL activity-coefficient model to describe the
nonideality of the liquid phase and the Redlich-Kwong model to describe the nonideality
of the vapor phase. It is appropriate for the mixtures and conditions of the
Oxychlorination section containing non-electrolyte mixtures. For mixtures containing
electrolytes, the ELECNRTL option is used. This option is similar to the NRTL-RK
model, but is also able to describe mixtures containing ions. ELECNRTL defaults to
NRTL-RK when the concentration of ionic species becomes zero. The STEAMNBS
model is a highly accurate model for pure water and is used for the cooling circuit of the
reactor.
The main reaction of oxychlorination is given by Equation (3) of Chapter 1. Several

other by-products are also formed in this reactor. We have chosen the following seven
reactions based upon the recent literature (Cowfer and Gorensek, 1996; Ullmann, 1999;
Carrubba and Spencer, 1970; Wachi and Asai, 1994; Prasad, Prasad and Ananth, 2001;
Al-Zahrani, 2001):
1. C2H4 + 2 HCL + .5 O2  EDC + H2O

2. C2H4 + 3 HCL + O2  TEC + 2 H2O
3. C2H4 + HCL  LB
4. C2H4 + 4 HCL + 1.5 O2  HB + 3 H2O
5. C2H4 + 3 O2  2 CO2 + 2 H2O
6. C2H4 + 2 O2  2 CO + 2 H2O
7. C2H4 + HCL + .5 O2  VCM + H2O
Reaction 1 is the main oxychlorination reaction. Reactions 2, 3, 4 and 7 produce undesired

chlorinated compounds and Reactions 5 and 6 produce CO2 and CO, respectively. For
Reaction 1, we have adopted a rate expression similar to the one proposed by Wachi and
Asai (1994):
k T  * K a * CC 2H 4 * C HCl * CO0.2038
R1  (5)
1  K a * CC 2 H 4
where, C refers to composition in terms of molarity (kmol/m3 in SI units) and Ka is equal to

0.63 m3/mol, according to Wachi and Asai (1994).
Actually, Wachi and Asai (1994) did not use the dependence on the concentrations of HCl
and O2 shown in Equation (5). Wachi and Asai did propose a linear dependence on the
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concentration of the catalyst, cupric chloride, which we have assumed to be equivalent to

the concentration of HCl. We added a weak dependence on the concentration of O 2
(exponent = 0.038). Essentially all the oxygen fed to Section 200 is consumed in the
Oxychlorination Reactor, but there is a small amount of oxygen in the exit stream from the
reactor. The weak dependence on the composition of O 2 is a semi-empirical way to capture
this effect. We note that the work of Carrubba and Spencer (1970) indicates that the
oxychlorination reaction does depend on the oxygen concentration.
The temperature dependence of the rate constant is given by the usual Arrhenius rate
expression:
 E  1 1 
k T   k 0 * exp      (6)
 R T T 0  
where,
To - Convenient reference temperature, chosen here to be 150C (or 423.15 K)

E - Activation Energy, determined to be 37,800 kJ/kmol by Wachi and Asai (1994)
K0 - Reaction rate constant at T0
The other reactions are assumed to have similar rate expressions. All seven reactions have
been implemented into the LLHW (Langmuir-Hinschelwood-Hougen-Watson) model in
Aspen Plus, with the following general expression:
 E  1 1 
k T   k 0 * exp      * Concentration  / 1  Adsorption (6)
 R T T0  
The implementation for each term is described in the following table:
Reaction K0 Concentration Adsorption

1. C2H4 + 2 HCL + .5 O2  EDC + 6.0*10-5 CC 2H 4C HCl CO0.2038 K a CC 2H 4
H2O
2. C2H4 + 3 HCL + O2  TEC + 2 1.2*10-7 CC 2H 4C HCl CO0.2038 K a CC 2H 4
H2O
3. C2H4 + HCL  LB 1.4*10-7 K a CC 2H 4
4. C2H4 + 4 HCL + 1.5 O2  HB + 3 1.2*10-7 CC 2H 4C HCl CO0.2038 K a CC 2H 4
H2O
5. C2H4 + 3 O2  2 CO2 + 2 H2O 5.0*10-7 CC 2H 4CO0.2038 0
6. C2H4 + 2 O2  2 CO + 2 H2O 1.0*10 -7
CC 2H 4C 0.038
O2
0
7. C2H4 + HCL + .5 O2  VCM + 2.5*10 -9
CC 2H 4C HCl C 0.038
O2
K a CC 2H 4
H2O
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The values of k0 were determined through data supplied by QPC engineers, and may need to
be adjusted as the catalyst activity changes. The reaction set has been implemented into an
LHHW model named OXYCHLOR.
A schematic of the Oxychlorination reactor is presented in Figure 3.
Cyclone
Heat Water
Cool Water
33
32
31
Baffle
3
2 Gas Distributor
1
3
2
1
PF
HCl
201
S.L
Recycle Gas
C2H4
EA205
O2
EA206
Figure 3. Oxychlorination Redactor
Several schemes were investigated for modeling the reactor. It was finally decided to model
the reactor simply as a constant temperature plug-flow reactor with 3.84712 m and length
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3.415 m. The constant temperature was set to 230C and the heat produced in the reactor is
used to heat the cooling water through the use of a heat stream.
The Oxychlorination reactor has cyclones to recover the catalyst particles. AspenTech did
supply QPC engineers with approximate models to describe the performance of the
cyclones, but this unit is not included in the formal models developed for this project.
The Aspen Plus model developed for Section 200 is presented as Figure 4.
207A
235A
2WL
135
15
01
19
20
21
27
30
23
6
2 50 EA2 07
2 28 A
FA208
2 47
2 28
EA203 EA2 04 SPLIT1

2 49 C O2 -C2 225
RS T OI C
215A 2 22
FA2 07
D A202
4 18
FA2 01
PF201
CO2 -C1
207 RS T OI C
222A
GB2 01
2 03
2 04
5
EA2 05 DA2 01
103
223A
D C2 0 1
GA203 FA2 04 PF2 03 FA205
EA206 PF202
206 238
218 FA2 05 S BL
2 01 A FSP LI T
237
212 GA205
2 36
229
Figure 4. Section 200 – Oxychlorination
The Oxychlorination reactor described above has been implemented as the RPLUG model
DC201. A heat stream from the reactor DC201 is used to determine the temperature rise in
the cooling-water system.
The outlet from DC201 enters distillation column DA201 in which the aqueous HCl is
separated from the other components in the stream. This column has been modeled using
the Radfrac block. The column has a rather complex heat-exchanger network, which has
been modeled using pumparounds. Aqueous HCl must be modeled using an electrolyte
model. A single reaction describing the ionic dissociation of HCl has been used in a
Chemistry model named HCL:
HCL + H2O  H3O+ + CL- (7)
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The Radfrac simulation of DA201 has been done in the apparent mode. The simulation
allowed the presence of two liquid phases, but only a single liquid phase was found.
The vapor from DA201 is further processed in another distillation column, DA202, in which
the CO2 is absorbed in a sodium hydroxide solution. A more complete Chemistry model,
named GLOBAL is required to describe the acid-base chemistry that occurs in DA202:
CO2 + 2.0 H2O  H3O+ + HCO3- (8)

HCL + H2O  H3O+ + CL- (9)
NAOH  NA+ + OH- (10)
2. H2O  H3O+ + OH- (11)
HCO3- + H2O  CO3-- + H3O+ (12)
Similar to DA201, DA202 is modeled as a Radfrac block in the apparent mode and allowing
the presence of two liquid phases. In this case, two liquid phases are predicted in the
simulation and this is in accordance with plant observation.
The amount of caustic is sufficient to completely remove the CO2, but in practice a rate-
based process, probably gas-phase mass transfer, limits the CO2 removal. Radfrac does not
have the capability to describe processes that are controlled by mass-transfer limitations and
hence we have implemented an approximate, but effective, approach. It is assumed that the
CO2 is initially in the form of an “inert CO2” (CO2-IN) that does not participate in the
Chemistry GLOBAL (Equations (8) – (12)); CO2-IN has also been forced to be only
sparingly soluble in the liquid phase by declaring it to be HENRY component with a large
Henry’s Law constant. Now a REACTIONS model, named CO2-MT converts CO2-IN.
The scheme has been implemented through an RSTOIC block CO2-C1 that converts all the
incoming CO2 to CO2-IN. In the distillation column DA202, CO2-MT converts CO2-IN
to CO2, but its finite rate limits the amount of absorption of CO2. The vapor phase from the
top of DA202 converts any remaining CO2-IN back to CO2 and thus the presence of CO2-
IN is limited to the region around DA202. The formulation adopted to describe the mass-
transfer of CO2 is similar to one proposed by Miller (1987) for nitric-acid columns. Finally,
we note that his scheme provides results that are in good agreement with plant observations.
The vapor effluent from DA202 goes through a series of condensers to remove the heavier
components and finally to produce the recycle gas (Stream 229) that returns to the reactor.
These pieces of equipment have been modeled as HEATER, FLASH2, COMPR and
FSPLIT blocks as appropriate.
The liquid effluent from DA202 is processed by a series of decanters and washes to produce
the EDC product and waste water streams. These pieces of equipment have been modeled
as PUMP, MIXER, DECANTER and FSPLIT blocks as appropriate.
Convergence of this plant section is difficult because of the interdependency and complex
connections of the various streams and slow convergence of the blocks (caused by
electrolyte chemistry and liquid-liquid equilibrium. However, convergence can be reliably
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obtained by providing increasingly good guesses for the tear streams (using the Reconcile
capability in Aspen Plus).
The results of the Aspen Plus simulation of Section 200 have been judged by QPC engineers
to be in good agreement with the plant observations.
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5 Section 300 – EDC Purification
Section 300 consists of three distillation columns and associated pumps, heat exchangers
and flash separators designed to produce purified EDC as a feed for the EDC Pyrolysis unit.
The components used in the Aspen Plus model for Section 300 are:
ID Component Name Formula

C2H4 ETHYLENE C2H4
C2H3CL VINYL-CHLORIDE C2H3CL
C2H5CL ETHYL-CHLORIDE C2H5CL
P-CCL2 1,1-DICHLOROETHYLENE C2H2CL2-D1
F-CCL2 TRANS-1,2-DICHLOROETHYLENE C2H2CL2-D3
1,1EDC 1,1-DICHLOROETHANE C2H4CL2-1
1,1,1-01 1,1,1-TRICHLOROETHANE C2H3CL3-D0
CHCL3 CHLOROFORM CHCL3
CH2CL2 DICHLOROMETHANE CH2CL2
CCL4 CARBON-TETRACHLORIDE CCL4
CIS-1-01 CIS-1,2-DICHLOROETHYLENE C2H2CL2-D2
C6H6 BENZENE C6H6
C2HCL3 TRICHLOROETHYLENE C2HCL3
1,2-EDC 1,2-DICHLOROETHANE C2H4CL2-2
C2CL4 TETRACHLOROETHYLENE C2CL4
1,1,2-02 1,1,2-TRICHLOROETHANE C2H3CL3
H2O WATER H2O
N2 NITROGEN N2
and conditions of the EDC Pyrolysis section.
The Aspen Plus flowsheet developed for Section 300 is presented in Figure 5.
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313L
314
N2
320
GA308
325A
325
E304G E313G
315 GV
EA304 EA313
EA311 EA312
301 323
510 313
E304L
FA301 DA304
E312L
239 301 239A

DA301 DA303
DA302
F301L
308 317
326
330 321
309
109 317A 321A
GA302 GA303 GA305

GA301
D301BL
Figure 5. Section 300 – EDC Purification
There are four distillation columns in Section 300 (DA301, DA302, DA303 and DA304),
which have all been modeled using the Radfrac model in Aspen Plus. DA301 is specified to
allow two liquid phases, but a second liquid phase was not found. DA302 has a design-spec
to vary the distillate rate in order to obtain a top tray temperature of 60C. Columns DA303
and DA304 do not have any special features. All four Radfrac blocks converge robustly.
All other Aspen Plus blocks chosen to represent the process equipment in this section are
straightforward application of standard Aspen Plus blocks.
The Broyden method has been chosen to converge this Aspen Plus model. Due to the
integrated nature of the flowsheet is important to ensure tight tolerances on the individual
blocks to obtain overall convergence of the Aspen Plus simulation. Hence the flash
tolerance under Setup/Simulation Options/Flash Convergence has been set to 1.E-6, and the
Radfrac tolerance has also been set to the same value (i.e., 1.E-6). It is also important to
start with good guesses for the tear streams (308 and 325). With these practices, the
flowsheet convergence is robust. It is recommended that QPC engineers follow these
practices and the simulation model is modified in the future.
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6 Section 400 – EDC Pyrolysis
EDC decomposes on heating to VCM and HCl. The reaction is endothermic and thus the
reactor is a direct-fired tubular furnace. In the QPC plant, the reactor is fired using butane as
the fuel. A schematic diagram of the reactor is presented in Figure 6.
VCM
STM
EDC Preheater
CM (EA412)
EDC Cracker
Heat Exchanger
(EA411)
EDC
C4
Figure 6. EDC Pyrolysis Reactor

C2H2 ACETYLENE C2H2
HB TETRACHLOROETHYLENE C2CL4
H2O WATER H2O
N2 NITROGEN N2
O2 OXYGEN O2
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• • • • • • • • • • • • • • • • • • • •
CO CARBON-MONOXIDE CO
C2H4 ETHYLENE C2H4
C3H8 PROPANE C3H8
H2 HYDROGEN H2
C2H6 ETHANE C2H6
BENZ BENZENE C6H6
CARBON CARBON-GRAPHITE C
NC4 N-BUTANE C4H10-1
IC4 ISOBUTANE C4H10-2
ARGON ARGON AR
A composite model has been developed to describe the reaction and heat exchange depicted
in Figure 6. The POWERLAW model describes the pyrolysis reactions that occur inside the
tubes. In the POWERLAW model, the rate expression is as follows:
 E  1 1 
Rate  k 0 * exp      *  Partial Pr essure (13)
 R T T0  
In the implementation for EDC pyrolysis, T0 has been set to 500 K and E has been set to
93,600 kJ/kmol for all reactions. A set of seven reactions has been used to describe the
pyrolysis kinetics, as described in the table below.
Reaction K0 Partial Pressure

1. EDC  VCM + HCL 6.00E-12 PEDC
2. EDC  C2H2 + 2 HCL 1.00E-14 PEDC
3. EDC + H2  LB + HCL 5.00E-18 PEDC PH 2
4. EDC + 2 HCL  HB + 3 H2 1.00E-20 PEDC PHCl 2
2
5. 2 EDC  C4H5CL + 3 HCL 3.00E-21 PEDC
2
6. 3 EDC  BENZ + 6 HCL 1.00E-20 PEDC
7. EDC + HCL  TEC + H2 1.00E-20 PEDC PHCl 2
In the above table, the partial pressures are in SI units, i.e., Pa.
The choice of the reactions, the form of the POWERLAW correlations and the kinetic
parameters were based upon information in the literature (for example, Cowfer and
Gorensek, 1996; Ullmann’s, 1999; Holbrook, Walker and Watson, 1971; Incavo, 1996), as
well as the experience of AspenTech personnel and the QPC engineers. The POWERLAW
model has been implemented in Aspen Plus as a Reactions model named EDCPR.
____________________________________________________________________ 20
• • • • • • • • • • • • • • • • • • • •
Radiative heat transfer of the combustion of butane heats the endothermic EDC pyrolysis
reaction. Aspen Plus does not have a radiative heat-transfer model and thus the mechanism
has been implemented as a user heat-transfer model.
The overall heat-transfer process may be approximated as radiative heat transfer from the
flame to the tube wall (proportional to the fourth power of the temperature) and convective
heat transfer from the tube wall to the process fluid.

Q  UR T F   T 
4 W 4
U C
(T W  T P ) (14)
where,
Q - Heat-transfer flux, J/m2.K

UR - Radiative heat-transfer coefficient, J/m2.K4
UC - Convective heat-transfer coefficient, J/m2.K
TF - Temperature of flame, K
TW - Temperature of wall, K
TP - Temperature of process fluid, K
The above model has been implemented in a user Fortran heat-transfer subroutine named
EDCHT that has three real input variables as follows:
REAL(1) - Wall temperature, Tw

REAL(2) - Convective heat-transfer coefficient (J/m2.K), UC
REAL(3) - Radiative heat-transfer coefficient (J/m2.K4), UR
EDCHT first solves Equation (14) to find the wall temperature and then computes the heat
flux, Q.
The combination of reactor and flame is simulated by using an RPLUG block with the
EDCPR kinetic model and an RSTOIC model for the butane combustion. A Calculator
block named EDCPYR passes the temperature of the flame to REAL(1) of the RPLUG
model and a design-spec named EDCREACT varies the temperature of the flame such that
the heat generated in the combustion equals the heat transferred to the reactor.
and conditions of the EDC Pyrolysis section.
____________________________________________________________________ 21
• • • • • • • • • • • • • • • • • • • •
410
G2
EA402
G3
DUPLI C 404A 404B
M ULT
DA401 EA403
EA412 T UB1 418 503
402 402A
451
403 411
451B 404C
E411
409
T UB2
FA402
451C
G1
451A EDCREACT
COMB
AIR BUT ANE
Figure 7. Section 400 – EDC Pyrolysis
In the Aspen Plus model depicted in Figure 7, the reactor of Figure 6 consists of the
combustion (COMB), the tubular reactor (EDCREACT) and the heat-recovery exchangers
(TUB1, TUB2 and E411).
The remainder of the Section 400 simulation is a straightforward application of Aspen Plus
models. The separator DA401 is treated as a 2-stage Radfrac block with a large
pumparound. The MULT block, named DUPLIC, is intended to simulate the fact that two
reactor trains enter this part of the plant. EA403 and FA402 simulate the heat exchanger and
flash separator in this section.
____________________________________________________________________ 22
• • • • • • • • • • • • • • • • • • • •
7 Section 500 – VCM Purification
Section 500 consists of three distillation columns and associated pumps, heat exchangers
and flash separators designed to produce the purified product VCM.

C2H2 ACETYLENE C2H2
HB TETRACHLOROETHYLENE C2CL4
NAOH SODIUM-HYDROXIDE NAOH
H2O WATER H2O
NA+ NA+ NA+
H3O+ H3O+ H3O+
OH- OH- OH-
CL- CL- CL-
NACL SODIUM-CHLORIDE NACL
NA2CO3 SODIUM-CARBONATE NA2CO3
NACLO3 SODIUM-CHLORATE NACLO3
NA2SO4 SODIUM-SULFATE NA2SO4
H2SO4 SULFURIC-ACID H2SO4
HSO4- HSO4- HSO4-
HCO3- HCO3- HCO3-
CLO3- CLO3- CLO3-
CO3-- CO3-- CO3-2
SO4-- SO4-- SO4-2
Two physical-property models are used in this section: NRTL-RK and ELECNRTL.
NRTL-RK uses the NRTL activity-coefficient model to describe the nonideality of the
liquid phase and the Redlich-Kwong model to describe the nonideality of the vapor
phase. It is appropriate for the mixtures and conditions of the Oxychlorination section
containing non-electrolyte mixtures. For mixtures containing electrolytes, the
ELECNRTL option is used. This option is similar to the NRTL-RK model, but is also
able to describe mixtures containing ions. ELECNRTL defaults to NRTL-RK when the
concentration of ionic species becomes zero.
____________________________________________________________________ 23
• • • • • • • • • • • • • • • • • • • •
505IN
511A
513A
508
513
503
511
VCMP ROD
M-E A506
FA 505
409
MIX ER2
P F501 514
FA504 M I XER
GA503
505
DA 501 DA502
410 WATE R
DA 503
M-GA 5O2
411 504
519
512
517A
510
MIX ER1 FS PLIT

519A M I XER 517B FSPLI T 517P
Figure 8. Section 500 – VCM Purification
There are three distillation columns in Section 500. DA501 removes the components lighter
than VCM, DA502 removes those heavier than VCM and DA503 provides final purification
of the VCM. In all three columns, the physical property option NRTL-RK is used. DA501
has a design-spec that sets the temperature of Stage 31 by varying the reboiler duty. This
design-spec is hard to attain and may depend strongly on the minor species in the column.
This design-spec is achieved in the current simulation, but QPC engineers are advised to
perform sensitivity studies to determine the effect of minor species on the column
temperature profile. Columns DA502 and DA503 converge without difficulty.
The portion of the simulation downstream of DA503 consists of a caustic wash to remove
the purified VCM from the aqueous phase. This portion of the simulation has been
simulated using the ELECNRTL model.
____________________________________________________________________ 24
• • • • • • • • • • • • • • • • • • • •
8 Running AspenTech VCM Models Developed for QPC
The VCM plant models contain bkp or apw files and associated Fortran subroutines
supplying the user models (typically the kinetics of heat-transfer models). In this case
only the EDC Pyrolysis reactor has a user Fortran subroutine, the heat-transfer model
called EDCHT.
In order to run any one of the models, save the set of files into a chosen directory. Note
that the bkp and apw files are equivalent. bkp files are upwardly compatible with new
versions of Aspen Plus, while the apw files are not. apw files retain more graphical
information than the bkp files. It is recommended that both bkp and apw files be
retained. Compile the Fortran subroutines using standard Aspen Plus procedures. Now
run the bkp file or the apw file.
It is usually easier to create dll files that contain the Fortran subroutines. A .dll file
allows distribution of Fortran subroutines to customers who do not have a Fortran
compiler. The customer simply follows the instructions outlined below under
"Instructions for Using MYDLL.DLL” in order to call the subroutine from his model
within the Aspen Plus GUI.
Creating .dll Files
Creating a .dll file requires a Fortran compiler. You do not need to do this step if a .dll
file has already been created. Follow these instructions to create a .DLL file:
1. Open the “Aspen Plus Simulation Engine” window. This is done through the
“Start” button in Windows. This action sets the correct environment variables and
default directories.
2. Compile the Fortran subroutines you want included so as to create the
corresponding .OBJ files. Example:
ASPCOMP MYSUBR.FOR creates MYSUBR.OBJ
3. Place all your .OBJ files in a directory and from there execute the following
command:
ASPLINK MYDLL
These commands create file MYDLL.DLL, which includes all .OBJ file in the current
directory.
After successful completion of Step 3, MYDLL.DLL is ready for distribution and use.
____________________________________________________________________ 25
• • • • • • • • • • • • • • • • • • • •
Instructions for Using MYDLL.DLL
MYDLL.DLL is a file that allows the use of compiled Fortran without a compiler. For
example, MYDLL.DLL might contain subroutine "USRKIN" that calculates reaction
kinetics. Follow these steps to set up your system to include MYDLL.DLL in your
Aspen Plus simulation:
1. Create a new text file with the name RUN.OPT.

2. In RUN.OPT type the path where MYDLL.DLL resides. Example:
c:\MyData\MySimulations\MYDLL.DLL
3. In ASPEN-PLUS go to RUN/SETTINGS and type the path pointing to RUN.OPT
in the field labeled "Linker Options". Example:
c:\MyData\MySimulations\RUN.OPT
Note that lines starting with “#” are treated as comment lines. Also, RUN.OPT
may have multiple lines identifying several DLL’s used in the simulation.
You are now ready to run your Aspen Plus simulation that makes use of MYDLL.DLL.
AspenTech has created dll’s containing the VCM models for QPC’s use. This file is
called edcpyr.dll. The use of the dll’s is the preferred way to run the simulation models.
____________________________________________________________________ 26
• • • • • • • • • • • • • • • • • • • •
References
Al-Zahrani, S.M.; Aljodai, A.M.; Wagialla, K.M., “Modelling and Simulation of 1,2-
Dichloroethane Production by Ethylene Oxychlorination in Fluidized-Bed Reactor,”
Chem. Eng. Sci., 56, 621 (2001).
Carrubba, R.V.; Spencer, J.L., “Kinetics of the Oxychlorination of Ethylene,” Ind. Eng.
Chem. Proc. Des. Dev., 9, 414 (1970).
Cowfer, J.A.; Gorensek, M.B.; “Vinyl Chloride,” Kirk-Othmer Encyclopedia of Chemical
Technology, 4th Edition, 1996.
Holbrook, K.A.; Walker, R.W.; Watson, W.R.; “The Pyrolysis of 1,2-Dichloroethane,” J.
Chem. Soc. B, 577 (1971).
Incavo, J.A., “ A Detailed Quantitative Study of 1,2-Dichloroethane Cracking to Vinyl
Chloride by a Gas Chromatographic Pyrolysis Device,” Ind. Eng. Chem. Res., 35, 931
(1996).
Miller, D.N., "Mass Transfer in Nitric Acid Absorption," AIChE J., 33, 1351-1358,
(1987).
Prasad, P.S.S.; Prasad, K.B.S.; Ananth, M.S., “Parameter Estimation in a Fixed-Bed
Reactor Operating Under Unsteady State: Oxychlorination of Ethylene,” Ind. Eng.
Chem. Res., 40, 5487 (2001).
Ullmann’s Encyclopedia of Industrial Chemistry, 5th Completely Revised Edition, Volume
A6: Ceramics to Chlorohydrins, pages 262-389, John Wiley & Sons (1999).
Wachi, S.; Asai, Y., “Kinetics of 1,2-Dichloroethane Formation from Ethylene and Cupric
Chloride,” Ind. Eng. Chem. Res., 33, 259 (1994).
____________________________________________________________________ 27

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AspenTech Report

VCM PLANT MODEL

SINOPEC Qilu Petrochemical

This report contains proprietary information of

2 VCM Manufacture and Project Goals.........................................4

3 Section 100 – Direct Chlorination..............................................7

4 Section 200 – Oxychlorination..................................................9

5 Section 300 – EDC Purification................................................16

6 Section 400 – EDC Pyrolysis....................................................18

7 Section 500 – VCM Purification................................................22

This report is organized in the following way. Chapter 2 provides background

2 VCM Manufacture and Project Goals

Direct Chlorination CH2=CH2 + Cl2  ClCH2CH2Cl (1)

H2O Ethylene Ethylene Vinyl

Ethylene dichloride recycle

Figure 1. Principal Steps in a Balanced Vinyl Chloride Process

Section Process Step

Section 500 Vinyl Chloride (VCM) Purification

 Material consumption will be reduced by 2%.

 Production rate will be increased.

3 Section 100 – Direct Chlorination

Direct chlorination of ethylene is conducted in liquid EDC in a bubble column reactor.

The components used in the Section 100 model are as follows:

ID Component name Formula

Rxn Key Fractional

Figure 2. Section 100 – Direct Chlorination

4 Section 200 – Oxychlorination

The components used in Section 2 are as follows:

ID Component name Formula

C3H6 PROPYLENE C3H6-2

The main reaction of oxychlorination is given by Equation (3) of Chapter 1. Several

1. C2H4 + 2 HCL + .5 O2  EDC + H2O

Reaction 1 is the main oxychlorination reaction. Reactions 2, 3, 4 and 7 produce undesired

where, C refers to composition in terms of molarity (kmol/m3 in SI units) and Ka is equal to

concentration of the catalyst, cupric chloride, which we have assumed to be equivalent to

To - Convenient reference temperature, chosen here to be 150C (or 423.15 K)

The implementation for each term is described in the following table:

Reaction K0 Concentration Adsorption

A schematic of the Oxychlorination reactor is presented in Figure 3.

Figure 3. Oxychlorination Redactor

EA203 EA2 04 SPLIT1

Figure 4. Section 200 – Oxychlorination

HCL + H2O  H3O+ + CL- (7)

CO2 + 2.0 H2O  H3O+ + HCO3- (8)

5 Section 300 – EDC Purification

ID Component Name Formula

239 301 239A

GA302 GA303 GA305

Figure 5. Section 300 – EDC Purification

6 Section 400 – EDC Pyrolysis

Figure 6. EDC Pyrolysis Reactor

ID Component name Formula

Reaction K0 Partial Pressure

Q - Heat-transfer flux, J/m2.K

REAL(1) - Wall temperature, Tw

AIR BUT ANE

Figure 7. Section 400 – EDC Pyrolysis

7 Section 500 – VCM Purification

ID Component name Formula

MIX ER1 FS PLIT

Figure 8. Section 500 – VCM Purification

8 Running AspenTech VCM Models Developed for QPC

Creating .dll Files