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A PLANNING MODEL FOR THE OPTIMAL PRODUCTION OF A REAL-WORLD ETHYLENE PLANT

1 Petroqumica Unio Department of Chemical Engineering, University of So Paulo 3 Othmer Department of Chemical and Biological Sciences and Engineering, Polytechnic University 2

F. Gubitoso1,2 , J. M. Pinto2,3,*

Abstract. This paper addresses the production planning of a real-world ethylene plant. The problem is formulated as a Non Linear Programming (NLP) model. The NLP is validated on a petrochemical plant whose main product is ethylene and to a lesser extent many other economical-valued products that are obtained using naphtha as feedstock. The volume of each product can be modified, to a certain extent, through the use of specific units, the production of gasoline blends or the adjustment of cracking severity. This operational flexibility justifies the use of optimization techniques for the production planning. The objective is to minimize a cost function calculated as the difference between product values subtracted from feedstock and utilities costs. The resulting model is nonconvex and involves bilinear terms for the flow rates of individual components and their ratios. The model is applied under typical scenarios found in the operation of the plant, such as processing naphtha with different properties and formulating gasoline blends, among others. Finally, the model is coupled with a short cut model to determine more precisely utility consumption. This is illustrated with the simulation of a xylene tower that calculates steam consumption for this unit.

Keywords: Production Planning, Nonlinear Programming, Ethylene

1. Introduction
Operational optimization of either sectors or entire real-world chemical plants has been a task of growing interest in the chemical industry (Diaz and Bandoni, 1996). In which concerns ethylene plants, Diaz and Bandoni (1996) developed a Mixed Integer Non Linear Programming (MINLP) model that is solved with the OuterApproximation method (Viswanathan and Grossmann, 1990) and interfaced with a tailored process simulator. Tjoa et al. (1997) addressed the multiperiod production scheduling problem of an ethylene plant by considering feedstock supplies, plant operating conditions, plant inventories and demands simultaneously. The determination of a maintenance policy for cracking furnaces, taking into account the interactions between the entire process plant operation and furnace performance has been reported by Schulz et al. (2000). With respect to oil refineries, one of the first contributions to consider non-linearity in the production planning is that of Pinto and Moro (2000). According to their approach, every unit is represented as an entity and the complete refinery topology is defined by connecting unit streams. Nonlinearity arises mainly from blending equations and physical properties. This same modeling framework was later converted into a multiperiod and multiscenario model by Neiro and Pinto (2004). Similarly to the Pinto and Moro approach, the model addressed is based on a fixed topology, with nodes representing units or operations and arcs representing streams. There is, nevertheless, a difference in the way that the multicomponent flows are formulated. While in Pinto and Moro the

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To whom correspondence should be addressed. Address: Othmer Department of Chemical and Biological Sciences and Engineering, Polytechnic University Six Metrotech Center, Brooklyn NY 11201, USA E-mail: jpinto@poly.edu
*

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mass balance equations are based on total flows and component compositions for each stream, in this model the mass balances are expressed with flows of individual components through the nodes. The representation based on the flow of individual components has the advantage that it involves a smaller number of nonlinear equations. However, the modeling of the splitter units involves bilinear terms to impose the condition that the ratios of flows between components be the same for the different streams (Quesada and Grossmann, 1995). The objective of this paper is to present an optimization model for the operational planning of a real ethylene plant with fixed topology. The volume of each product can be modified, to a certain extent, through the use of specific units, by the production of gasoline blends or by the adjustment of cracking severity. The remainder of this paper is structured in the following manner. Section 2 describes the ethylene plant regarding olefin and aromatic production. Section 3 presents the formulation of the NLP model. Section 4 introduces some typical problems that arise in a petrochemical plant to be used as case studies for the optimal planning. In section 5 the solution strategy is presented. Section 6 shows the numerical results, whereas section 7 presents the main conclusions and suggests directions for further development.

2. Process Description
The ethylene plant under study uses naphtha in different grades as feedstock. Initially naphtha is diluted with steam and then briefly heated in furnaces. The reaction temperature is over 800C and the effluent from the furnaces is quenched by contact with a cooler fluid. The products from the reaction depend on the composition of the feed and on the cracking severity. Light hydrocarbon feeds yield product streams that are rich in the lighter alkenes, including ethylene, propylene, and butadiene. Heavier hydrocarbon feeds generate some of these, but also products that are rich in aromatic hydrocarbons and hydrocarbons suitable for blending in gasoline. The lighter phase of the furnace effluent is compressed in the cracked gas compressor and then is cooled to about 100C before entering the separation train. Ethane, obtained as the bottom stream of the ethane-ethylene splitter, is recycled to the pyrolysis furnace. Naphtha is also fed to the naphtha fractionation unit to produce mediumgrade naphtha, suitable to the reformer unit. Figure 1 shows a schematic representation of the olefin section.
FULL RANGE NAPHTHA

Naphtha fractionation unit

MEDIUM NAPHTHA

Ethylene production unit

Section A Pyrolisis (cracking heaters)

PYROLISIS RESIDUUM CHARGE GAS TO SECTION B

Pre heater HEAVY NAPHTHA + LIGHT NAPHTHA+ FULL RANGE NAPHTHA HYDROGEN

Quench

CHARGE GAS FROM SECTION A

Section B

METHANE

ETHANE RECYCLE ETHYLENE

PYROLISIS GASOLINE BUTADIENE

Ethylene fractionator Compression / Drying CC4

Chilling

Demethanizer

Deethanizer

Depropanizer

Debutanizer

Butadiene extraction unit

Propylene stripper

Propylene column BUTENES

PROPYLENE CHEMICAL GRADE

LPG

PROPYLENE POLYMER GRADE

Fig.1. Schematic Representation of Olefin Production

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The steam cracking of naphtha yields pyrolysis gasoline as a by-product that contains significant quantities of aromatics in which benzene and toluene are the primary constituents. Non-aromatics have a relatively high content of olefins and diolefins. In addition, sulphur compounds, especially thiophene, are present. To produce marketable aromatics, the pyrolysis gasoline has to be treated by two-stage hydrogenation in the Pyrolysis Gasoline Hydrogenation (PGH) unit. Another source for the aromatics mixtures is catalytical reformed naphtha. Reformate streams usually contain a higher concentration of xylene than benzene. The separation of aromatics from non-aromatics is possible through the use of liquid-liquid extraction with subsequent extractive distillation. The heavier reformate (C8+) has a low level of non-aromatic content and can be sent directly to the aromatic fractionation train after having been separated from the light reformate in the deheptanizer column. C9+ aromatics are used to produce alkyl benzene solvents in a batch operation. HDA is a thermal hydrodealkylation process for conversion of alkylated monoaromatics (basically toluene) to high purity benzene. The xylene isomerization unit increases the ortho-xylene concentration in a mixed xylene stream. Figure 2 shows the simplified aromatic production plant.

BENZENE REFORMATE RAFFINATE HDA PGH RAFFINATE

Isomerization

TOLUENE BENZENE RESIDUUM LIGHT ENDS

C5C9+ FROM ETHYLENE PRODUCTION UNIT Pyrolisis Gasoline AC9+ Rerun column PGH Unit Medium naphtha RESIDUUM

MIXED XYLENES ORTHO XYLENES

C6-C8 CUT

Aromatic Extraction

A D

B
AROMATICS FRACTIONATION

LIGHT REFORMATE HDS Catalytic Reforming REFORMATE

FROM NAPHTHA FRACTIONATION UNIT

C9+ A- BENZENE AND TOLUENE COLUMNS B- MIXED XYLENE COLUMN C- ORTHO XYLENE COLUMN D- DEHEPTANIZER COLUMN

Aromatic Solvents

AB-9 AB-10 AB-11 RESIDUUM

Fig. 2. Schematic Representation of Aromatic Production

3. Mathematical Formulation
The petrochemical plant has been modeled considering two main sections. The olefin sections include, basically, the ethylene, propylene, C4 fractions, pyrolysis gasoline, residue gas, naphtha distillation and reformate production. The aromatic section models the production of benzene, toluene, xylene (ortho and mixed isomers xylene) and alkyl benzene solvents. Different streams from both sections are used for the production of gasoline blends.

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The following notation is used for the optimization model: Sets

C I N Na Nd Nu N feed NI n NO n
Indices

=chemicals =utilities =all nodes =accumulation nodes =splitters and mixed-splitters nodes =nodes with utilities consumption =feed nodes

n' that reach node n =nodes n' that are reached by node n
=nodes =chemical =utility =node

c i n
Variables

cp n,c f n ', n , c Qn QC n,c QG n

Parameters

=mass fraction of chemical c in feed node n =mass fraction of chemical c inlet node n' that is diverted to node n = total mass flow rate of feed node n =mass flow rate of chemical c through node n = total mass flow rate of node n

Pi PV n TX n ,i

=unit cost for utility i =unit cost for raw material (with minus) and product inlet node n =utility consumption per unit of feed flow rate of

i in node n

3.1. Model Structure A known network consisting of a set of N nodes interconnected by arcs represents the process. This network also involves a set of C chemicals that are processed in nodes n N . Nodes n are classified in subsets according to their function in the network: N feed for feed sources, N d for splitters and N a for accumulators. Each node n N feed can be interconnected by one or more arcs from one or more nodes
'

n Na .
The input to the network is defined for each n N feed by Qn , that represents the total mass flow rate and

cp n ,c , the mass fraction of component c C . Variable QC n ,c represents the flow rate of component c that is
processed in node n N .The distribution of c inlet

n ' , defined for each n downstream n ' N a , is governed

by the value of f n ' , n ,c . QGn denotes the total flow rate of each node n N and is the summation of all component flow rates processed in n .

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The unit cost of utilities is Pi , defined for each utility i I which is consumed at a rate TX n ,i per unit of feed flow rate in node n defined for each N consumption. Since the flows through the system are calculated at the inlet of each node rather than for each stream, it is useful to assign auxiliary nodes for every stream whose flow rate is not evident, that is, at the streams that come out of splitters and are directed to mixers. Differently from the model proposed by Daz and Bandoni (1996) this model is not interfaced with process simulators for solving, for example, detailed models of the pyrolysis furnaces, the cracked gas compressor or the steam and power generation system. Thus we propose a simplified model based on the premise that the utilities consumption is proportional to the mass flow rate in the units or equipment such that no optimization is performed at the utilities section. This model also differs from the work of Pinto and Moro (2000) since it does not consider blending relationships and the mass balance is based on the flow of individual components through the nodes rather than the overall flow rate and component composition through the arcs. 3.2. NLP Formulation The model is represented by the following equations:

N u . N u is a subset of N and represents nodes with utility

Max

n( N feed N a )

PVn .QG n

nN u ,iI

P .QG .TX
i n

n ,i

(1)

subject to: QCn ,c = Qn .cpn ,c

QC n ,c =
n 'NI n

n N feed , c
n ', c

(2)
(3) (4) (5) (6)

QC
=1

. f n ', n , c

n N feed , c c, n' N d c, n' N a

f n ',n ,cref = f n ',n ,c | n NOn ' c ref C

nNOn '

n ', n , c

QG n = QC n,c
cC

n N
n N a n N a , c n N a , c n N feed , c
n N

Qn , QCn ,c + f n ',n ,c
0.0 f n ',n ,c 1.0 0.0 cpn,c 1.0
U QG nL QG n QG n

(7) (8) (9) (10) (11)

The objective function (1) is calculated as the difference between product values minus feedstock and utilities costs. In this equation, raw material price coefficients are negative since these are consumed, whereas saleable product cost coefficients are positive. Utilities consumption is a linear function of each unit or

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equipment feed rate. Equations (2) and (3) define how much of component c reaches node n. Equation (2) is used for feed nodes whereas Equation (3) is applied for all nodes other than the feed node. NI n is the set of all nodes n that send material to node n. Equation (4) enforces the same fraction in each outlet stream of a splitter for all components. The summation of all fractions of component c outlet node n is 1, as showed in Equation (5). In these equations, NOn represents all nodes n' that receive material from node n . Equation (6) represents the total flow inlet node n. In (7) and (8) the domain of the decision variables is defined. Finally, constraints (9), (10) and (11) denote the bounds for the fractions, compositions and flow rates, respectively. This model is, therefore, nonlinear and nonconvex. The sources of nonconvexities are the material balance equations for multicomponent streams, represented by equation (3), with utilities consumption being calculated as a simple linear relationship of the total flow rate that goes through each node. If a more rigorous calculation of utilities consumption in a certain node is required, an iterative procedure is proposed in order to get a more precise estimation.
'

4. Case Studies
The application of the NLP to the real-world ethylene plant resulted in a model with 2246 constraints and 2628 variables. Overall, 172 nodes are used to represent the whole plant with 8 components being considered in the aromatic section, where the reformate and pyrolysis gasoline stream compositions are known. The model is applied under typical scenarios found in the operation of an ethylene plant as described in table 1. Numerical results, considering the different scenarios described in table 1, are presented in section 6.

5. Solution Strategy
Although the equations that represent the units are apparently simple, the system is nonconvex and its solution presents some difficulties. The main source of nonconvexities is the material balance equations for multicomponent streams. In order to avoid the problem of getting trapped in suboptimal solutions or to avoid convergence failures with NLP solvers, a less rigorous solution strategy is first used in order to obtain an initial estimate. This is done through the use of a pre-processing algorithm that takes into consideration only overall flows in the network, resulting in the following steps for the resolution: I. Based just on yields and overall flows, the olefin area (cracking of naphtha and separation of main streams), pyrolysis gasoline hydrogenation, naphtha fractionation, reformer and butadiene units are inittially solved. Recycle streams, originated in other units, are assumed constant in this step. II. With the pyrolysis gasoline and reformate flow rates defined in step 1, the remaining processing units are solved taking into consideration the composition of these streams and overall flows. III. Results obtained from the solution of steps I and II are the initial estimate for the rigorous solution of the model, now considering a multicomponent system with the desired problem specification. IV. The result obtained in step III can be used as an initial point to the recalculation of the utility consumption through the application of a more rigorous model. This step is applied if a more rigorous calculation of

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utility consumption is required. In this case, an iterative algorithm is started and finishes when the consumption rate used in item III is sufficiently near the rate calculated by the model. Table 1. Case studies Case A Scenario Processing naphthas with different properties: naphtha types contain paraffin, olefins, naphthenes and aromatics under different concentrations and that has a direct effect on the product yield. Pyrolysis of lighter naphtha produces higher ethylene yield and less heavy byproducts such as gasoline and it generally costs more than heavier naphtha. For the application of the model it is necessary a previous knowledge of the relation between naphtha characteristics and yields. Pyrolysis cracking severity adjustment: besides naphtha composition, the severity, measured by the total production ratio of C3/C1 at the outlet of the pyrolysis furnaces, affects significantly the yields. The severity can be adjusted changing operational conditions, such as coil outlet temperature (COT). The relation between severity and yields must be known in advance. Best formulation for the gasoline blend: different streams, with different properties, can be blended to constitute the same kind of gasoline. The identification of the best mixture is accomplished through the use of binary variables and, in this case, the model becomes a mixed integer non linear programming (MINLP). Ethane to fuel gas: eventually it can be advantageous not to recycle the ethane produced in the pyrolysis in order to admit more feed (naphtha) and, consequently, to produce more propylene and less ethylene. The unrecycled ethane is sent to the fuel gas system. Evaluation of the operation of the xylene isomerization unit in order to produce more ortho-xylene from a mixed xylene stream. Evaluation of the hydrodealkylation unit in order to produce more benzene from alkylated aromatics, mainly from toluene. Evaluation of the naphtha fractionation and reformer unit in order to increase aromatic production from medium naphtha. In all cases, utility consumption is calculated as a linear relationship of the total flow rate that goes through each node. The only exception is steam consumption in the mixed xylene tower. Step IV is applied for the calculation of the steam consumption in this tower since it is strongly influenced by the operation of the xylene isomerization unit. For this reason, the steam consumption for this specific column is modeled through the use of a short cut model (Underwood, 1948). The modeling system GAMS version 21.3 (Brooke et al., 1998) was used to implement the model which was solved using the CONOPT solver in items I to III and the SNOPT algorithm in the recalculation of the steam consumption in the xylene splitter column (item IV). Although not applied in this work, an alternative to obtain an initial point for the model, which makes it independent of heuristic initialization strategies, is the application of the reformulation and linearization technique for bilinear programming models proposed by Sherali and Alameddine (1992).

E F G

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6. Numerical Results
A base case representing a typical plant operation condition was used to establish a reference for the numerical results. For the base case, the following conditions were assumed: Naphtha with 61.4wt% of total paraffins and cracking severity of 0.8; All units operate at maximum capacity; Gasoline blend production with a pre-established formulation; Demands for all products.

For the base case, no degree of freedom is available and the objective function returned the plant hourly gross profit observed in a typical plant operation. The simulation requires approximately 2 minutes on a Pentium III, 128M RAM. The different scenarios described in table 1 were investigated using approximated cost values at the time of this study (2003) for products, raw materials and utilities. In order to create a user-friendly interface and help in checking the solution, main data and results were gathered in a spreadsheet that contains input data (upper and lower bounds, prices, utility consumption and yields) and reads the solution from the output file generated by the GAMS software. Case A: Considering the base case as reference (naphtha with 61.4 wt% of total paraffin), an improvement of 10.76% in gross profit has been found for a naphtha with 85.0 wt% total paraffin and a decrease of 11.94% for a naphtha with 50 wt% total paraffin. Constraints in the olefin separation train causes the inflection observed in the range of 65-70 wt% on figure 3 and also explain the lower improvement rate in gross profit for the region of higher paraffin concentration (higher than 75 wt%).
15 variation in gross profit (%) 10 5 0 -5 -10 -15 50 55 60 65 70 75 80 85 naphtha paraffinicity (wt%)

Fig. 3. Influence of naphtha paraffinicity in the gross profit

Case B: Based on correlations between severity and yield, the best solution found was a ratio C3/C1 = 0.96 for the severity, favoring aromatics, C3 and C4 production. Operation with a severity of 0.80 decreases the gross profit in US$1059.78/h (US$763039.20/month), as depicted in figure 4. .

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variation in gross profit (US$/h)

0 -200 -400 -600 -800 -1000 -1200 0.75

0.80

0.85

0.90

0.95

1.00

severity of pyrolysis furnaces

Fig. 4. Influence of the pyrolysis severity in the gross profit

Case C: Considering a fixed production of 12 t/h of gasoline and different possibilities for the formulation, with the use of each formulation represented by a binary variable, the MINLP resulting problem selects the optimal values for the binary variables and, by consequence, the best mixture of streams for the gasoline production. If no gasoline is produced, a decrease of US$3,058.60/h (US$2,202,192.00/month) was found, considering the base case as reference. Case D: In normal operation all ethane produced is completely recycled to the pyrolysis furnaces, increasing ethylene production. Depending on the relative costs of fuel gas, ethane, ethylene and propylene it can be advantageous to send ethane to the fuel gas system instead of recycling it to the furnaces. Therefore, it is possible to process more naphtha, decreasing the ethylene yield and increasing, for example, propylene production. In order to test the model, an upper bound in ethylene production was considered and the relative prices adjusted. The optimal solution resulted in an increase in gross profit of US$461.69/h (US$332,419.20/month) that sends ethane to the fuel gas system. Case E: If no upper bound is imposed to the xylene production, the optimal solution suggests the shutdown of the isomerization unit. The normal situation, nevertheless, is a restriction in the xylene local market. The excess xylene can be exported at a lower price or can be sent to the isomerization unit, increasing the ortho-xylene production. Considering the prices at the time of this study (2003) and a local market of 1 ton/h from 9 ton/h of mixed xylene available for sale, putting the isomerization in operation resulted in an increase in gross profit of US$512.58/h (369,057.60/month). Figure 5 shows the optimal operation condition of the isomerization unit as a function of the maximum local market demand for mixed xylenes considering the feasible range of 20 to 33 ton/h for the isomerization unit feed rate. It can be noted that if the local market has a demand greater than 7 ton/h the optimal solution is obtained through the shutdown of the isomerization unit.
1400 variation in gross profit (US$/h) 1200 1000 800 600 400 200 0 1 2 3 4 5 6 7 8 9 maximum local market demand (ton/h) 35 30 25 20 15 10 5 0 isomerization unit feed rate (ton/h)

Fig. 5. Optimal feed rate to the isomerization unit

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Cases F and G: The production of more aromatic compounds by the reformer unit and also more benzene from toluene through the hydrodealkylation unit were tested simultaneously by the optimization of the base case that resulted in an increase in the gross profit of US$3,614.83/h (US$2,602,680.00/month). At the optimal solution, the reformer unit operates at maximum capacity and no toluene is sent to the hydrodealkylation unit.

7. Conclusions
This paper addressed the development and application of a nonlinear programming model for the operational planning of a real-world ethylene production plant. The plant is composed of two main sections, namely olefins and aromatics and is represented by a network with nodes representing units or operations and arcs representing streams. Utility consumption is considered as a linear function of the flow rate in each node or, in special cases, can be calculated through the application of an iterative process. Several case studies that represent the typical operation of the plant were studied. First, a base case with no degrees of freedom was solved. Results show that the economic benefits of using this tool can be significant with the solution being reached in a very short time. Finally, it is important to note that the model was transformed into a decision support tool for the operational planning of Petroqumica Unio in which the NLP is interfaced with a spreadsheet that contains information such as flow rates, yields, prices and bounds and run on a monthly basis by the production scheduler.

References
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