A Practical, Applied, Rigorous Ethylene Dichloride Pyrolysis Furnace Model

A Basis for Operational Improvement, Control, and Optimization

Aspen Technology, Inc. 2500 CityWest Boulevard Houston, Texas 77042

Table of Contents Introduction........................................................................................................................1 Components........................................................................................................................3 Reactions.............................................................................................................................4 Reaction types..................................................................................................................4 Rate Limiting Steps for EDC Conversion.......................................................................5 Kinetics...............................................................................................................................7 Arrhenius Reaction Rate Relationships...........................................................................7 Reversible Reaction Rates...............................................................................................7 Thermodynamic Properties..............................................................................................8 Heat Transfer Rate Relationships....................................................................................9 Pressure Drop Relationships..........................................................................................12 Coking Rate and Run Length Relationships.................................................................14 Software............................................................................................................................19 Appendix A.......................................................................................................................21 Components - Molecular Species..................................................................................21 Components - Free Radical Species..............................................................................22 Appendix B.......................................................................................................................23 Reaction Network..........................................................................................................23 Molecular Elimination...................................................................................................23 Beta Scission..................................................................................................................23 Initiation/Termination....................................................................................................24 Disproportination...........................................................................................................24 Hydrogen Abstraction....................................................................................................25 Chlorine Abstraction......................................................................................................26 Molecular Growth..........................................................................................................27 Appendix C.......................................................................................................................28 Literature References.....................................................................................................28

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Ethylene Di-Chloride Pyrolysis Furnace Model

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Introduction
Vinyl chloride monomer (VCM) is commercially produced by pyrolysis (thermal cracking) of 1,2 dichloroethane, known as ethylene dichloride or EDC. Many VCM plant production rates are limited by the EDC cracking furnaces or the downstream separation distillation towers separating the cracking furnace effluent into VCM product, byproduct HCl, and recycle EDC. Additional VCM can be produced or energy usage per ton of product can be reduced if the typical per pass conversion depth of EDC to VCM of 5558% is raised, depending on where equipment and economic constraints exist. Energy savings come from reduced distillation tower heat and cooling loads at the lower recycle ratios of EDC that occur at higher conversions. Operation at higher conversion will reduce furnace run lengths because of higher coking rates. Economic trade off of operating condition effects on production, energy, and decoking costs can be quantified with a high fidelity model of the process. The EDC pyrolysis furnace model developed by Aspen Technology, Inc. determines the best operating conditions that maximize operating profit by trading off the benefits and debits of changing conversion, throughput, pressure, and all independent operating conditions, while honoring all operating constraints such as maximum allowable tube metal temperatures and minimum allowable furnace run lengths. Model input includes measured operating conditions, allowable limits, and feed, fuel, and product prices. Optimal conditions are not static since they depend on equipment performance (i.e. convection section and radiant section fouling) as well as ambient conditions (combustion air temperature) and feed, fuel, and product prices. Furthermore, the active constraint set in the furnaces and downstream separation units has a very significant effect on the optimal conditions. For example, the HCL separation tower overhead cooling system many times becomes constraining, and affects the optimal operating condition values. The EDC cracking furnace model is comprehensive and includes: Reaction kinetics in the radiant section passes and in the transfer lines Fuel/air/fluegas combustion stoichiometry, material balances and heat balances Radiant and convection section heat transfer rate relationships Pressure drop relationships Tube metal temperature calculations Coking rate and furnace run length calculations

The model is configurable so that it represents specific furnace geometry and dimensions. The model is typically configured to model each individual pass rather than represent multiple passes as a lumped, average pass. Tube and transfer line length, inside and outside diameter are inputs. Radiant firing profiles represent burner placement (floor, wall, ceiling, or combinations). Measurements are configured with specific plant tag names and are connected to the model where they exist in the plant. The model is specified to represent the control system. Specifications set which variables are
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Ethylene Di-Chloride Pyrolysis Furnace Model

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independent and which are dependent. Independent measurements include flow, temperature, and pressure indicator/controllers (FICs, TICs, and PICs) while dependent measurements include indicators with no final control elements (FIs, TIs, PIs). Proper specification of model variables is important since only a properly specified model will have the correct dependent variables respond to changes in independent variables. Proper response is required for optimization results to be meaningful. The EDC cracking model can be used most effectively to impact plant profitability in an on-line environment, coupled closely with a multi-variable, predictive advanced control system. The model used in such an application can be thought of as a soft sensor or inferential calculator, since it elucidates each furnace and furnace pass conversion from measured conditions that are not direct measures of pass-by-pass conversion. Furthermore, the model optimizes and trades-off non-linear and comprehensive effects that cannot today be determined by any controller technology. The process model brings clarity to the optimal solutions. The reasons for each optimal solution can only be fully understood from the context of a model that accurately represents the process, plant equipment, constraints, and economics. The model can of course be used off-line to answer what if questions, and to investigate design changes.

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Ethylene Di-Chloride Pyrolysis Furnace Model

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Components
Both molecular and free radical species are modeled. Literature sources (References 1, 2, 3) list over 70 molecular species and over 60 free radical species for some reaction networks. These literature sources have been analyzed to establish the components required for a reaction network of sufficient resolution to capture effects on industrial importance, including conversion, byproduct yields, and coking. Numerical sensitivity analysis was done on the models built with full component and reaction sets across conditions of industrial importance. Components that had essentially no effect on the EDC cracking furnace results were eliminated from the super set of components found in the literature. Thirty seven (37) molecular species and thirty four (34) free radical species remain as components required to capture all the effects of the literature models with essentially no degradation of functionality. The components used in the Aspen Technology EDC pyrolysis model are listed in Appendix A.

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Reactions
The apparent overall reaction occurring in EDC pyrolysis furnaces is: EDC VCM + HCL

Additionally, small amounts of byproducts are produced including coke, methyl chloride, ethyl chloride, mono-vinyl acetylene, butadiene, and chloroprene. Selectivity (moles VCM/mole EDC) is quite high, typically over 99.5%. Production of VCM does not proceed by the apparent reaction, but by numerous steps, primarily free radical mechanisms with some molecular elimination (Reference 4) and some molecular growth reactions. The model reaction network consists of mechanistic steps, including about 150 reactions. The reaction network is listed in Appendix B. The intermediate free radical species are explicitly modeled. These reactions are of several types, with hydrogen abstraction reactions making up the majority.

Reaction types
Several reaction types are included in the mechanism, including: Molecular elimination Beta scission Initiation/Termination Disproportination Hydrogen abstraction Chlorine abstraction Molecular growth

Examples of reactions of different types: Molecular Elimination EDC VCM Initiation EDC Hydrogen Abstraction EDC + CL C2H3CL2 + HCL CH2CL + CH2CL VCM C2H2 + + HCL HCL

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Ethylene Di-Chloride Pyrolysis Furnace Model Beta Scission C2H3CL2 Termination CHCL2 + CHCL2 C2H2CL4 VCM + CL

Aspen Technology, Inc.

Molecular Growth VCM + C2H3 C4H6 + CL

The reactions and the rate parameters are derived from several literature sources (References 1, 2, 3). Rigorous sensitivity analysis and analysis of reaction pathway networks were carried out across conditions of industrial importance. Numerous reactions from the literature were found to only effect effluent concentrations by fractions of parts per million or less, below measurable thresholds and far below levels of concern of byproduct contamination of product and recycle streams. After eliminating reactions which had no practical effects on effluent concentrations, a reaction network of about 150 reactions remained. Kinetics for these reactions have been validated with respect to observed EDC conversion response to furnace outlet temperature and other operating condition changes. The kinetics of important trace byproducts such as methyl chloride, ethyl chloride, mono-vinyl acetylene, butadiene, and chloroprene have been focused on and further developed to match observed values and gains (changes with respect to independent variables such as furnace outlet temperature or conversion) observed in industrial furnaces from on-line analysis. Finally, coking reactions were developed based on literature sources and on industrial tube metal temperature and pressure drop data.

Rate Limiting Steps for EDC Conversion

The generation of the C2H3CL2 radical, through hydrogen abstraction, and the decomposition of the C2H3CL2 radical are the rate limiting steps in the overall process of EDC to VCM conversion. EDC C2H3CL2 + CL C2H3CL2 VCM + + HCL CL

The CL radical plays a pivotal role in the mechanism. Several rate enhancing feed additives, such as CCL4 and CL2 (Reference 2), have been used with different degrees of success, depending in part on furnace conditions and design configurations. These additives generate additional CL radicals which allow conversion to occur at lower temperatures. Lower temperatures cause lower coking rates, all other things being equal. However, the rate of producing coke precursors and therefore the coking rate itself is affected by the higher CL radical concentration.

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Each component (molecular and free radical) composition profile can be plotted from the model output.

Composition Profiles 1.0 0.9 0.8 0.7 Mole Fraction 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0.0 50.0 100.0 150.0 Coil Length (m eters) 200.0 250.0 300.0

EDC HCL VCM

Byproducts are important from product quality and coking standpoints, but are present in quite small concentrations. Consequently selectivity is very high, with vinyl chloride monomer (VCM) and HCL molar concentrations are almost equal, resulting in very nearly coincident concentration profiles, as shown above.

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Ethylene Di-Chloride Pyrolysis Furnace Model

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Kinetics
Arrhenius Reaction Rate Relationships
All the reactions are homogeneous, occurring in the gas phase. A three-parameter Arrhenius rate coefficient (rate constant) form is used. The three parameters are frequency factor (A), temperature exponent (n), and activation Energy (Ea).
nj a E j R e T

k j = AjT

Since the reactions are fundamental, the reaction rate concentration dependency is to the molecularity order of the reactions (order based on stoichiometric coefficients of reactants). The reaction rate is determined from reactant concentrations, stoichiometry, and the Arrhenius rate constant:

rj = k j i
i R j

j NR

where: rj kj [i] i Rj NR - rate of reaction j - rate constant of reaction j - concentration of species i - stoichiometric coefficient for species i - set of reactants of reaction j - set of reactions

The aforementioned reaction rate form is applied using a reference temperature and a reference rate constant, as shown below. This reference form exhibits more favorable numerical characteristics under some conditions.
k = k ref exp( E / R ref ( 1 Tref / T )) a T

Reversible Reaction Rates

All reactions except coking reactions are considered reversible. Each reverse rate constant (kr) is calculated using the forward rate constant (kf) and the equilibrium constant (K) for the reaction at the temperature of the rate evaluation. k r = kf K

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Ethylene Di-Chloride Pyrolysis Furnace Model

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This relationship reflects microscopic reversibility and imposes a thermodynamic constraint on the net rate of the reaction. The concentration dependency of the forward and reverse reactions is based on the molecularity of the reactants for the forward rate and of the products for the reverse rate. The calculated molar rate of reaction is the net rate of the combined forward and reverse reactions. Equilibrium constants for each reaction are functions of temperature. Heat capacity, standard free energy change of reaction, and heat of formation of each participating species, as well as reaction stoichiometry, are used to calculate the equilibrium constants (Reference 5).

Thermodynamic Properties
Thermodynamic properties for the EDC cracking model are retrieved from Aspen Plus property data sets, and include user entered properties. Properties related to the reacting components and their products are entered as user properties, using values and parameters from Borsas PhD thesis (Reference 1, Appendices D & E ) to maintain consistency, especially with respect to properties of free radicals and derived relationships, such as equilibrium constants. Borsa references the ultimate sources of this thermodynamic information.

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Ethylene Di-Chloride Pyrolysis Furnace Model

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Heat Transfer Rate Relationships

Heat transfer rate plays an important part in any process furnace. The EDC pyrolysis reactions are highly endothermic and require substantial heat input to bring the feed up to temperatures at which free radical initiation reaction rates are sufficiently fast to begin pyrolysis. Once initiated, the reactions require heat input to sustain the net endothermic heat requirements to achieve desired conversion depth. Heat transfer across the radiant section tubes is governed by several mechanisms including convection, conduction, and radiation. Convection heat transfer coefficients are accounted for both inside the tubes as well as outside the tubes. Conduction is calculated across the coke thickness and through the tube wall metal. Radiation is calculated using methods described in Kern, Process Heat Transfer (Reference 6). The inside film heat transfer coefficient for the radiant tubes is calculated by the DittusBoelter correlation (Reference 7):
Nu = h film Di k fluid = 0.023 Re 0.8 Pr 0.3 (

) 0

where: Nu hfilm Di k fluid Re = Nusselt number = inside heat transfer coefficient = inside tube diameter = bulk process fluid thermal conductivity = Reynolds number

Re =
v Pr

Di v

= fluid velocity = bulk fluid viscosity = fluid viscosity at the wall temperature = Prandtl number
Pr = Cp k fluid

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Ethylene Di-Chloride Pyrolysis Furnace Model

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The method used for modeling the radiant heat transfer rate is derived from methods listed in Chapter 19 of Kern (Reference 6) and Wimpress (Reference 8).

Q = * F * * Acp* (Tg 4 - Tff 4) + hc*Ao*(Tg - Ts)

Radiant Convective where:

= total heat transferred = Stefan-Boltzmann constant = Overall view (exchange) factor (See Kern, Figure 19.15) = Cold plane effectiveness factor (See Kern, Figure 19.11) = Cold plane area (of both sides of tube bank, or row) = Effective temperature of radiating gas, absolute = Temperature of tube front face (surface), absolute = Outside convective heat transfer coefficient = Outside area of tube = Average outside tube surface temperature, absolute = Ts * PMDF

Acp
Tg Tff hc Ao Ts Tff

PMDF = Peripheral maldistribution factor (Accounts for circumferential heat flux maldistribution) This equation is essentially Equation 19.9 from Kern, modified to allow for variation of conditions along the tube length. The furnace model integrates this heat transfer relationship along the length of the tube, while simultaneously solving the kinetics, pressure drop relationships, and all other equations related to the problem posed (which typically included several EDC cracking furnaces and downstream separation towers). The effective gas radiating profile as a function of length is related to the burner placement in the firebox, as well as to the relative burner firing rates.

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Ethylene Di-Chloride Pyrolysis Furnace Model

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The net result of all the heat effects, including the heats of reactions, sensible heat changes, and heat transfer rates are manifested in temperature and heat flux profiles.

500

Tem perature and Heat Flux Profiles

1 0.0

9.0

450

8.0

7.0

Temperature (Deg C)

5.0

350

4.0

3.0

Process Bulk Temperature

300 2.0

Outside Tube Heat Flux

250 0.0 50.0 1 00.0 1 50.0 200.0 250.0 300.0

1 .0

0.0

Coil Length (m eters)

The radiant tubes and transfer lines are modeled in detail all along their length. The radiant coil tube metal temperature is calculated, as well as the bulk process fluid temperature (the temperature plotted above), and the temperatures at the film-coke and coke-tube metal boundaries.

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Temperature Pro f (length)

Heat Flux (kcal/m2-s)

400

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Ethylene Di-Chloride Pyrolysis Furnace Model

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Pressure Drop Relationships

Pressure drop is modeled in all the equipment so that pressure and pressure drop effects and limitations are taken into account. In the EDC cracking and downstream separation area of a VCM plant, the furnaces typically are operating on back pressure from controlled downstream pressure, such as the HCL tower overhead pressure. As throughput is increased the furnace pressure rises for a constant downstream pressure, due to increased pressure drop. Pressure affects rates of reactions by changing the process fluid density and therefore residence times in the radiant coils and transfer lines. Additionally pressure affects reaction rates because it changes concentration driving forces and equilibrium driving forces. The furnace and transfer line pressure drops are modeled with the classic skin friction relationship:
d p d l = 4 f 1 D v2 2 c g

where: p l f D v gc = pressure = length = friction factor = inside tube or inside coke diameter = velocity of process fluid = gravitational constant conversion factor = density of process fluid

The coke layer reduces the inside diameter used in the pressure drop relationship. Coking occurs at different rates along the length of the radiant coil and transfer line due to temperature and coke precursor composition profiles. Consequently the coke layer and its build up rate calculations result in a non-uniform coke layer. Radiant coil designs typically include numerous straight runs connected by 180 U bends. The pressure drop relationship above is applicable for straight runs but can be modified to include the effects of the U bends. One method is to increase the length over which the pressure drop relationship is applied, using an equivalent length of the actual coil that is longer than the actual length. This method can be employed when only pressure effects are of interest, but will change the residence time and heat transfer relationships inappropriately if applied to a model accounting for all these effects. Schlichting (Reference 9) on page 590 shows that the straight-run friction factor can be modified to account for bends of any radius.
f bend = f straight

(1 + 0.075 R

1/ 4

( R / r )1 / 2 )

where: R r = radius of tube = radius of bend

12

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Ethylene Di-Chloride Pyrolysis Furnace Model

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The friction factor affects only the pressure drop calculations, so this method of accounting for bends if preferable to employing any equivalent length method. Furthermore the theoretically sound relationship between the friction factor of a bend and the straight pipe friction factor is a multiplier. The overall effect of the total number of bends in any coil design can be determined by calculating the proportion of the overall coil length that the bends constitute and applying a length averaged friction factor.

f co il

w ith b n s ed

f stra h ig t

* Lstra h ig t

(Lstraight

+ fbn ed + Lb n s ed

* Lb n s ed

The EDC cracking model has a multiplier parameter applied to the pressure drop relationship which is used to force the calculated pressure drop to equal the observed pressure drop. This parameter accounts for the U bend friction factor multiplier as well as for any other flow resistances not accounted for in the straight run pressure drop relationship. Additionally the parameter absorbs any measurement error effects on pressure drop. Flow rate, pressure, and temperature measurements affect pressure drop. For existing furnaces with pressure drop measurements back calculating the pressure drop parameter precludes the need to employ the friction factor length average method. For new furnace designs the effect of the bends can be predicted by use of the aforementioned relationships for bends.

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Ethylene Di-Chloride Pyrolysis Furnace Model

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Coking Rate and Run Length Relationships

Coking rate kinetics are affected most by several coke precursor species including acetylene, butadiene, and chloroprene (References 2, 10, 11, 12). Feedback from observed furnace run lengths, tube metal temperature rates of increase, and pressure drop rates of increase is used to establish the best coking rate kinetic parameters. Operating condition upsets and short excursions into high and low coking rate conditions demand that feedback be used. Models that do not incorporate such feedback are not capable of trading off the positive effects of increased conversion and the negative effects of coking in a practical manner. The EDC cracking furnace model is for the most part a steady state model. Coke buildup is by its time dependent nature a dynamic process. Several time dependent relationships are solved along with the mainly steady state relationships. These are used to project the effects of coking in time to determine how far ahead in time the coke thickness will result in tube metal temperatures attaining their maximum allowable values. Coking Rate Is Determined By Kinetics (Coking rate = Moles/(Volume-Time)) Coke Thickness Rate Of Change = f (Coking Rate, Tube Area/Tube Volume) Tube Metal Temperature Rate Of Change = f (Coke Thickness Rate of Change, Operating Conditions) Run Length Remaining = f (Present Tube Metal Temperature, Max. Allowable Tube Metal Temperature, Tube Metal Temperature Rate of Change)
oe Ck T i k es hc ns M TT

Coke ThicknessEOR = Coke ThicknessNow + (TMTMax Allowable TMTNow)* where:

EOR stands for End Of Run TMT is the Tube Metal Temperature (outside surface (front face) nearest burners) The same modeling approach has been used successfully extensively in on-line, real-time optimization applications on olefins steam crackers. Since the rate at which coke lays down on the radiant coil and transfer line walls is an extremely small fraction of the total mass flow rate in the furnace, the coking reaction calculations have been set up to have no effect on the flow rates of any process species. Coking rates are calculated all along the radiant coil and in the transfer line. When the furnace model is run successively in a fully configured real time system it lays down coke all along the coil and transfer line by the amount determined by the coking rates and
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Ethylene Di-Chloride Pyrolysis Furnace Model

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the elapsed time between the time of its last execution and the present time. Offline executions can be done successively by artificially incrementing the time inputs to simulate elapsed time and coking over that time. As time is incremented in this manner all the effects of coking are calculated, including effects on tube metal temperature and pressure drop. Coking rates are calculated at the inside surface of the radiant coil and of the transfer line, although a parameter allows the coking rate temperature to be manipulated between this surface temperature and the lower bulk process fluid temperature. This surface is initially clean metal, and is then the inside coke surface early in the furnace run as coke is laid down. The inside surface is the hottest temperature that the process is exposed to in the radiant coil, since there is considerable (typically more than 150 Deg F) temperature difference across the convective film across which the heat is transferred into the coil. The transfer line is very close to adiabatic, so there is essentially no difference between the bulk process fluid and the inside surface of the metal or coke in the transfer line. The coking rate in the transfer line due to reaction at the surface temperature therefore drops considerably from the rate in the radiant coil. However, the coke thickness at the end of the transfer line is observed to be quite similar to the thickness observed at the end of the radiant coil. Another mechanism is invoked to account for this observation which is consistent with mechanisms discussed in numerous literature articles (Reference 12, Chapters 9 & 10). That mechanism is the effective condensation of coke formed in the bulk process fluid onto the surface. The proportion of coke formed in the transfer line is assumed to completely lay down on the surface, whereas the proportion of the coke formed in the radiant coil assumed to lay down on the surface has been calculated to force the model to best match the observed end of run coke thickness. That proportion, or lay down factor in the radiant coil is about 0.50. The following figure shows the coke buildup as a function of the radiant coil and the transfer line position over a furnace run of about 300 days. The coke profile begins as zero thickness all along the coil and transfer line (clean conditions) and ends with about 0.5 inches of coke at the thickest point, the coil outlet at which the temperature is the hottest. The illustrated coke profiles were determined by running 27 Parameter cases, that is cases using actual plant data, from start of run until end of run, over a 305 day plant run length. Therefore the operating conditions of the furnace are different in each of the 27 cases. The coking rate is not adjusted with feedback from measured tube metal temperatures. Tube metal temperatures are inherently inaccurate, so using them for feedback would be problematic. At will discussed later in this section, the model can be used to predict when, and under what conditions, tube metal temperatures will approach their maximum allowable values, how much run time remains before that limit is reached, and how operating conditions can be manipulated to trade off operating profit and run length debits.

Coke build up at the radiant coil outlet position (the hottest temperature) is illustrated in the following chart.
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Ethylene Di-Chloride Pyrolysis Furnace Model

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The following charts illustrate, for the same aforementioned 27 cases using plant data, how well the tube metal temperatures calculated by the model match measured tube metal temperatures.

1300 1250 1200

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1150

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1300
The following chart shows the effect of skewing the same total amount of fuel

1250 1200 1300 1150

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1250
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Ethylene Di-Chloride Pyrolysis Furnace Model

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The absolute model-measurement match is not very important, since the furnace model includes measurement models of all the tube metal temperatures with Plant, Model, and Offset values. The specifications of these measurement model variables after all connections and specification groups are applied (configuring the model correctly) have the Plant value as a dependent measurement (a Meas specification) and the Offset as a Param specification. The Param is kept fixed during simulation or optimization executions of the model, so the Plant values change as the model variables change. Therefore we can judge how well the model will predict changes of tube metal temperatures with changes in conditions by observing how well the calculated TMTs match the measured TMTs profiles across the 27 cases in which conditions and coke thicknesses are changing. Another way of looking at the model fidelity in this area is looking at the trends of the TMT measurement Offsets. The more constant the Offsets, the better the model will be able to predict, for precise measurements. Variations in Offsets are due in part to measurement errors, and in part to model errors. The previous charts show that the model and measured TMT profiles match quite well across the entire furnace run length. The projected remaining time on line is primarily dependent on the measured TMT that will become limiting first, and on the calculated coking rate.

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Ethylene Di-Chloride Pyrolysis Furnace Model

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Software
The EDC cracking model is an Aspen Plus model that is dragged and dropped from the Aspen Plus graphical user interface (GUI) toolbar into the flowsheet the same way any other model is handled. The EDC pyrolysis model is a USER3 Aspen Plus model, designated as an Aspen EO (Equation Oriented) model of EORXR type. Its EORXR type is selected from a dialog box list from the Input section. The model has inlet and outlet ports that are totally compatible with Aspen Plus streams, and are connected to upstream and downstream models. All Aspen Plus versions include the EORXR USER3 model type. The EORXR model is a generic reactor model that requires configuration and reaction mechanism input. The configuration file (filename.CFG) is pointed to in the Parameters\Run Control tab associated with the block in the GUI data browser. The mechanism file (filename.MCH) is pointed to from the configuration file. The configuration file defines reactor features with keywords, including reactor type (plug flow, catalyst packed tube, etc.), heat transfer environment (adiabatic, radiant heat transfer, etc.), and others. Dimensions are entered in the configuration file as initial values. Dimensions are read as model variables that can be changed before and even during execution (for design problems, for instance) of the model. The mechanism file contains the entire set of reactions for the reactor, including stoichiometry. Reaction rate and equilibrium constant parameters are model variables, initialized from values in the mechanism file. The configuration and reaction mechanism input, including reaction rate parameters, are not supplied with Aspen Plus versions, but are purchased separately from Aspen Technology. The overall furnace model is constructed from numerous Aspen Plus blocks, including typically more than one EORXR model for each furnace pass (depending on the complexity of the radiant coil and the firebox), an EORXR model for the transfer line, heat exchanger models for the convection section passes, extent of reaction models for combusting fuel, analyzer models (for example for stack oxygen) and measurement models representing flow, temperature, pressure, and composition sensing devices. Since reaction rate relationships are differential equations they must be integrated to arrive at the solution. Integration is handled by an approximate integration method, global spline collocation, described by Villadsen and Michaelson (Reference 13). This method yields results that are essentially indistinguishable from analytic integration solutions when applied with sufficient resolution, that is, with a sufficient number of splines placed appropriately. Global spline collocation poses the integration relationships using algebraic equations which are solved simultaneously with the rest of the overall Aspen Plus flowsheet problem. This method is very efficient compared to closed form integration methods, especially when the model is used as the basis for optimization. Furthermore, variables all along the integration variable domain (furnace coil length in the case of the EDC pyrolysis model) are model variables that can be specified, constrained, connected to, and otherwise exploited. The openness of the collocated
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integration problem makes it easy to pose any desired boundary conditions, even specifying conditions, such as tube metal temperatures, anywhere along the furnace coil length.

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Appendix A
Components - Molecular Species
Number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 Component H2 HCL CL2 CH3CL CH2CL2 CHCL3 CCL4 C2H5CL EDC C2H4CL2B C2H4 C2H3CL3A VCM C2H2CL4 C2H2CL2A C2H2CL2B C2H2CL2C C2H2 C2HCL3 C2HCL C2CL4 C2CL2 C3H6 C3H5CLC C3H4CL4B C3H4CL2E C3H3CL5A C3H3CL3F C3H2CL4A C4H6CL4 C4H6CL2C C4H6 C4H5CL3 C4H5CLA C4H5CLB C4H4 BENZENE

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Components - Free Radical Species

Number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 Component H CL CH2CL CHCL2 CCL3 CCL2 C2H3 C2H4CLA C2H4CLB C2H3CL2A C2H3CL2B C2H3CL2C C2H2CLA C2H2CLB C2H C2CL3 C2CL C3H5 C3H4CL3 C3H4CLD C3H3CL4B C3H2CL3A C4H7CL2 C4H6CL3A C4H6CL3B C4H6CLC C4H6CLA C4H6CLB C4H5CL2B C4H5CL2C C4H5CL2D C4H5CL2E C4H5B C4H5A

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Appendix B
Reaction Network Molecular Elimination
C2H4CL2B EDC VCM C4H6CL2C C4H6CL2C CHCL3 CCL2 C2H2CL2B C2H2CL2C C2H5CL C4H6 C2H3CL3A C2H2CL4 C2H4 C2H2 Molecular Elimination <=> VCM <=> VCM <=> C2H2 <=> C4H5CLB <=> C4H5CLA <=> CCL2 EDC <=> C3H4CL4B <=> C2HCL <=> C2HCL <=> C2H4 <=> C2H2 <=> C2H2CL2C <=> HCL C4H6 <=> BENZENE C4H6 <=> BENZENE + + + + + + + + + + + + + + HCL HCL HCL HCL HCL HCL HCL HCL HCL C2H4 HCL C2HCL3 H2 + H2 H2

+ +

Beta Scission
C2H4CLB H CL CL CL C2CL2 C4H6CL3A C4H6CL3B C4H5CL2E C4H5CL2B C4H5CL2C C4H6CLC C4H6CLA C4H6CLB C4H7CL2 C4H5CL2D Beta Scission <=> C2H4 VCM <=> C2H4CLA C2H4 <=> C2H4CLA VCM <=> C2H3CL2A C2H2 <=> C2H2CLB CL <=> C2CL3 <=> C4H5CL3 <=> C4H6CL2C <=> C4H5CLA <=> C4H5CLB <=> C4H5CLA <=> C4H6 <=> C4H6 <=> C4H5CLB <=> C4H6CL2C <=> C4H5CLB + CL

+ + + + +

+ + + + + + + + + +

H CL CL CL CL CL CL H H CL

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Aspen Technology, Inc.

Initiation/Termination
C2H4CLA CL2 CL2 CL2 C2H3CL2A C2H3CL2A CCL3 C3H3CL4B EDC CL CCL3 H C2H3 CL CHCL2 + + + + + + + Initiation/Termimation CL <=> EDC EDC <=> CL VCM <=> CL HCL <=> CL C2H3CL2A <=> C4H6CL4 C2H3CL2A <=> C2H3CL3A C2H3CL2A <=> C3H3CL5A <=> C2HCL3 <=> CH2CL VCM <=> C2H3CL2C C2H2 <=> C3H2CL3A VCM <=> C2H4CLB C2H2 <=> C4H5A C4H5CL2C <=> C4H5CL3 CHCL2 <=> C2H2CL4

+ + + + + +

CL CL CL VCM

+ EDC + VCM + HCL

CH2CL CH2CL

+ + + + + +

Disproportination
C4H5CL2D CL CL CL CL C2H2CLA + + + + + + Disproportination C2H3CL2A <=> C4H5CLB C2H3CL2A <=> VCM C2CL3 <=> C2CL2 C4H5CL2C <=> C4H5CLA C4H5CL2D <=> C4H5CLB C4H5A <=> C4H4 + + + + + + C2H3CL3A CL2 CL2 CL2 CL2 VCM

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Ethylene Di-Chloride Pyrolysis Furnace Model

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Hydrogen Abstraction
CHCL2 CCL3 C2H3CL2A C2H3CL2A C2H3CL2A C2H3CL2A C2H4CLB C2H2CLA CH3CL C2H5CL C2H5CL C2H4CL2B C2H4CL2B VCM VCM VCM EDC VCM VCM C2H2CLB C2H2CLA C2H4CLA C2H4 C4H6CL2C C4H6CL2C C4H6CL2C C4H6CL2C CCL3 CHCL3 C2HCL3 C3H4CL4B C4H5B CL CCL3 C2H3CL2A C2H3CL2A C2H2CLA C2CL3 C2H3CL2B C2H3CL2B CL CL C2H3CL2A C3H5 C3H5 C3H5 + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + Hydrogen Abstraction EDC <=> CH2CL2 VCM <=> CHCL3 C2H4CL2B <=> EDC C2H4CL2B <=> EDC C2H3CL3A <=> EDC C2H2CL4 <=> EDC EDC <=> C2H5CL C2H2CL4 <=> VCM CL <=> CH2CL CL <=> C2H4CLA CL <=> C2H4CLB CL <=> C2H3CL2B CL <=> C2H3CL2C CH2CL <=> C2H2CLB CH2CL <=> C2H2CLA H <=> C2H3 CL <=> C2H3CL2A CL <=> C2H2CLB CL <=> C2H2CLA EDC <=> VCM EDC <=> VCM EDC <=> C2H5CL CL <=> C2H3 CL <=> C4H5CL2E CL <=> C4H5CL2B C2H3CL2A <=> C4H5CL2E C2H3CL2A <=> C4H5CL2B EDC <=> CHCL3 CL <=> CCL3 CL <=> C2CL3 CL <=> C3H3CL4B EDC <=> C2H3CL2A C2H2 <=> C2H C2H2 <=> C2H C2H2 <=> EDC C2HCL <=> EDC C2H2 <=> VCM C2H2 <=> C2HCL3 C2H2 <=> C2H C2HCL <=> C2CL C3H5CLC <=> HCL C3H3CL3F <=> HCL C3H4CL4B <=> EDC EDC <=> C2H3CL2A VCM <=> C2H2CLB C2H4CL2B <=> C2H3CL2C + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + C2H3CL2A C2H2CLA C2H3CL2B C2H3CL2C C2H2CL2C + CL C2HCL3 + CL C2H3CL2A C2HCL3 + CL HCL HCL HCL HCL HCL CH3CL CH3CL HCL HCL HCL HCL C2H3CL2A C2H3CL2A C2H3CL2A HCL HCL HCL EDC EDC C2H3CL2A HCL HCL HCL C4H6 HCL CHCL3 C2H C2CL C2H C2H C2H4CL2B C2H4CL2B C3H4CLD C3H2CL3A C3H3CL4B C3H6 C3H6 C3H6

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Ethylene Di-Chloride Pyrolysis Furnace Model

Aspen Technology, Inc.

Chlorine Abstraction
CL CL CL EDC C2H2CLB C2H2CLA C2H3CL2A C2H3 C2H3CL2A C2H2CLA C2H2CLB C4H6CL2C C4H6CL2C CCL4 C2H2CLB C2H2CLB CH2CL C4H5CLB C4H5CLB C2HCL C2H3CL2A C2H3CL2A C2H2CLA C2CL3 CCL3 C2H3CL2A C3H4CLD C3H2CL3A CL C3H4CLD C3H2CL3A + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + Chlorine Abstraction C2H3CL3A <=> HCL C2H2CL4 <=> HCL EDC <=> CL2 H <=> C2H4CLA EDC <=> C2H2CL2B EDC <=> C2H2CL2A EDC <=> C2H3CL3A EDC <=> VCM CL2 <=> C2H3CL3A CL2 <=> C2H2CL2A CL2 <=> C2H2CL2B C2H3CL2A <=> C4H6CLC C2H3CL2A <=> C4H6CLA C2H3CL2A <=> CCL3 CL2 <=> C2H2CL2C EDC <=> C2H2CL2C EDC <=> CH3CL C2H2CLA <=> C4H5B C2H3CL2A <=> C4H5B CCL3 <=> C2H C2HCL <=> C2H C2CL2 <=> C2CL C2CL2 <=> C2CL C2CL2 <=> C2CL C3H4CL4B <=> CCL4 C3H4CL4B <=> C2H3CL3A EDC <=> C2H4CLA EDC <=> C2H4CLA CL <=> CL2 VCM <=> C2H3 VCM <=> C2H3 + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + C2H2CL2C + CL C2HCL3 + CL C2H4CLA HCL C2H4CLA C2H4CLA C2H4CLA C2H4CLA CL CL CL C2H3CL3A C2H3CL3A C2H3CL3A CL C2H4CLA C2H3CL2A C2H2CL2A C2H3CL3A CCL4 C2H3CL3A C2H3CL3A C2H2CL2A C2CL4 C3H4CL3 C3H4CL3 C3H4CL2E C3H2CL4A C3H4CL2E C3H2CL4A

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Ethylene Di-Chloride Pyrolysis Furnace Model

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Molecular Growth
CL CL C2H3CL2A C2H3CL2A C2H3CL2A C2H3CL2A C2H2CLA C2H2CLA VCM VCM C2H3CL2A C2H3CL2A VCM VCM + + + + + + + + + + + + + + Molecular Growth C2H2 <=> VCM <=> VCM <=> VCM <=> VCM <=> VCM <=> C2H4 <=> C2H4 <=> C2H3 <=> C2H3 <=> C2H4 <=> C2H4 <=> C2H2CLA <=> C2H2CLA <=> C2H2CLA C2H3CL2B C4H6CL3A C4H6CL3B C4H6CL2C C4H5CL3 C4H5CLB C4H6CLB C4H6CLC C4H6 C4H7CL2 C4H6CL2C C4H5CL2D C4H5CLB

+ + +

CL H H

+ + +

CL H CL

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Ethylene Di-Chloride Pyrolysis Furnace Model

Aspen Technology, Inc.

Appendix C
Literature References
1. Borsa, A. G., Industrial Plant/Laboratory Investigation and Computer
Modeling of 1,2 Dichloroethane Pyrolysis, PhD Thesis, Colorado School of Mines, Department of Chemical and Petroleum Refining Engineering, (1999)

2. Choi, B.S., OH, J.S., Lee, S.W., Kim, H., Yi, J., Simulation of the Effects of
CCL4 on Ethylene Dichloride Pyrolysis Process, Ind. Eng. Chem. Res., Vol. 40, pages 4040-4049, (2001)

3. Borsa, Alessandro G., Herring, Andrew M., McKinnon, Thomas, McCormick,

Robert L., Ko, Glen H., Coke and Byproduct Formation During 1,2 Dichloroethane Pyrolysis in a Laboratory Tubular Reactor, Ind. Eng. Chem. Res., Vol. 40, pages 2428-2436, (2001)

4. Rajakumar, B., Reddy, K. P.J., Arunan, E., Umimolecular HCL Elimination

from 1,2-Dichloroethane: A Single Pulse Shock Tube and ab Initio Study, J. Phys. Chem. A, Vol. 106, pages 8366-8373, (2002)

5. Smith, J.M., Van Ness, H.C, Introduction to Chemical Engineering

Thermodynamics, McGraw-Hill, New York (Second Edition 1959)

6. Kern, D. Q., Process Heat Transfer, McGraw-Hill, New York (1950, 1990) 7. Greenkorn, R.A., Kessler, D.P., Transfer Operations, McGraw-Hill, New York
(1972)

8. Wimpress, N., Generalized Method Predicts Fired-Heater Performance,

Chemical Engineering, May (1978).

9. Schlichting, H., Boundary-Layer Theory, McGraw-Hill, New York (1968) 10. Borsa, A.G., Herring, A.M., McKinnon, J.T., McCormick, R.L., Ko, G.H., Coke
and Byproduct Formation During 1,2-Dichloroethane Pyrolysis in a Laboratory Tubular Reactor, Ind. Eng. Chem. Res., Vol. 40, pages 2428-2436, (2001)

11. Xu, X., Pacey, P.D., An Induction Period in the Pyrolysis of Acetylene,
Phys. Chem. Chem. Phys., Vol. 3, pages 2836-2844, (2001)

12. Albright, L.F., Crynes, B.L., Corcoran, W.H., Pyrolysis: Theory and Industrial
Practice, Academic Press, New York, New York (1993)

13. Villadsen, J., Michaelson, M.L., Solution of Differential Equation Models by

Polynomial Approaximation, Prentice Hall, Englewood Cliffs, New York (1978)
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Ethylene Di-Chloride Pyrolysis Furnace Model

Aspen Technology, Inc.

Differentiating Features
Features of Aspen Technologys Ethylene Di-Chloride (EDC) Cracking Model Based Optimization and Advanced Process Control Solution That Differentiate It From Competitors Solutions
1. Aspen Techs on-line operations improvement solution in the ethylene di-chloride
cracking and downstream purification area of vinyl chloride monomer (VCM) plants is comprehensive, addressing the minute-by-minute advanced process control (APC) control issues, as well as the overall economic real-time optimization (RTO) optimization issues. The APC and RTO applications run in a tightly synchronized way, sharing consistent constraints, operating conditions, external targets, and economic goals.

2. Aspen Techs solution is scalable, allowing the APC and RTO applications to be
implemented in a phased approach, and over the most appropriate breadth of the plant.

3. The APC/RTO solution can include, and is most effective when it encompasses,
the EDC crackers as well as the HCl, EDC, VCM, and byproduct purification columns, as well as the recycled EDC.

4. The APC application stabilizes operation, rejects disturbances, while determining

the best set of operating conditions and active constraints to the best ability of the linear programming (LP) optimizer. The RTO application further improves the operating profit of the EDC crackers and separation columns by exploiting nonlinear trade-offs that the APC application cannot fully recognize. These non-linear trade-offs include, for example, the net effects of conversion versus run length (as affected by coking rate), throughput versus energy consumption, and optimal nonlinear exploitation of all the degrees of freedom while honoring all imposed constraints.

5. The EDC cracking furnace model is rigorous and comprehensive. It includes the
inside-the-tube kinetics (free radical, homogeneous), as well as the firebox, convection section, and the fuel/air systems associated with each furnace, all tightly integrated. Each furnace is modeled explicitly. Our competitors models are typically less comprehensive, and less tightly integrated, especially with regard to the tube-side and firebox models. 6. The EDC cracking model and the downstream separation columns (if included) are solved simultaneously. This feature has numerous advantages:

o The same model that is used to back out present performance, with
feedback from on-line measurements, is used to optimize operating conditions. Performance evaluation (equipment monitoring) is a valuable byproduct of the RTO application, providing heat exchanger, distillation column, and furnace performance parameters from consistent on-line data, numerous times per day.

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Ethylene Di-Chloride Pyrolysis Furnace Model

o

Aspen Technology, Inc.

The simultaneous solution formulation is an open formulation, with essentially all variables available to specify as measurements, to specify as parameters, to optimize, to reconcile, and/or to constrain. Few, if any, models of our competitors offer this powerful and essentially required for RTO feature. The plant variables are directly specified reflecting the control system configuration. The dependent variables to independent variable gains are readily available at each solution through sensitivity analysis.

o Component material balances, measured indirectly by feed, recycle and

product flows, allow for tracking of EDC to VCM conversion and selectivity, and allow for feedback into the cracking furnace models, through parameter updating, that keep the models accurate. Many competitors applications do not employ this kind of feedback that is essential to the success of on-line optimization systems. 7. Aspen Tech licenses the EDC cracking model to clients in a manner that allows full access to the kinetic reaction rate relationships, as well as rate parameters. Clients are bound by the license agreement to not share these relationships or parameters with any third party. This approach allows plant operations, clients research and development, and Aspen Tech to communicate well. 8. The RTO system brings engineering and economic clarity to the optimal solutions. The results include the economic shadow prices (partial derivatives of the operating profit objective function with respect to a unit move of each active constraint), which alert operations to the economic importance of each active constraint. This information is directly translatable into prioritizing relaxation of constraints. Many can be relaxed due to their soft nature, while others may take capital investment along with sufficient benefits to relax.

9. Aspen Techs APC/RTO solution has been implemented many times on quite
similar processes, addressing all of the issues present in the EDC cracking and downstream purification section of a VCM plant. These processes include steam cracking in olefins plants, cracking of acetic acid to ketene, steam reformers, as well as many other process furnaces.

10. Aspen Techs APC and RTO implementation personnel are highly skilled at
assessing, defining, executing, delivering, and supporting on-line applications.

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