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Industrial & Engineering Chemistry Research
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Model-based optimization of an Acetylene Hydrogenation

reactor to improve overall ethylene plant economics
Journal: Industrial & Engineering Chemistry Research
Manuscript ID ie-2017-05234d.R2
Manuscript Type: Article
Date Submitted by the Author: 29-May-2018
Complete List of Authors: Aeowjaroenlap, Hattachai; SCG Chemicals Co Ltd, Process Technology
Center
Chotiwiriyakun, Kritsada; SCG Chemicals Co Ltd, Process Technology
Center
Tiensai, Nattawat; SCG Chemicals Co Ltd, Process Technology Center
Tanthapanichakoon, Wiwut; SCG Chemicals Co Ltd, Process Technology
Center
Spatenka, Stepan; Process Systems Enterprise Ltd
Cano, Alejandro; Process Systems Enterprise Ltd
ACS Paragon Plus Environment

Page 1 of 30 Industrial & Engineering Chemistry Research
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Model-based optimization of an Acetylene
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Hydrogenation reactor to improve overall ethylene
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plant economics
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Hattachai Aeowjaroenlap*a, Kritsada Chotiwiriyakuna, Nattawat Tiensaia, Wiwut
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23 Tanthapanichakoona, Stepan Spatenkab, Alejandro Canob
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a
26 SCG Chemicals Co., Ltd, 271 Sukhumvit Rd., Map Ta Phut, Muang Rayong, Thailand 21150
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28 b
Process Systems Enterprise Ltd, 26-28 Hammersmith Grove, London, W6 7HA, United
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31 Kingdom
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34 Keywords: acetylene hydrogenation, kinetics, modeling, optimization
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37 ABSTRACT
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40 The steam cracking process is a common technology for producing ethylene from
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naphtha. However, one of the major contaminants in the ethylene product stream is acetylene,
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45 which poisons catalysts used in downstream polymerization processes and needs to be converted
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47 to ethylene by selective catalytic hydrogenation in order to upgrade product quality and increase
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overall ethylene yield. The selective hydrogenation process is usually carried out in a multi-stage
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52 fixed-bed catalytic reactor with internal cooling between stages to ensure that the outlet
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54 concentration of acetylene does not exceed 1 ppm. Nevertheless, side reactions also take place,
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60 ACS Paragon Plus Environment
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Industrial & Engineering Chemistry Research Page 2 of 30
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3 including total hydrogenation to ethane which increases energy consumption at the recycle
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6 furnace and decreases overall plant productivity. Moreover, in a tail-end hydrogenation process,
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8 the catalyst surface often becomes covered by so-called Green Oil generated from acetylene
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10 oligomerization, which causes catalyst deactivation and lowers the selectivity to ethylene. A key
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challenge of the tail-end acetylene hydrogenation process is to maximize the selectivity to
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15 ethylene while maintaining a full conversion of acetylene and maximizing the run-length
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17 between catalyst regenerations. In this work, a model of the tail-end 3-stage fixed-bed catalytic
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selective hydrogenation reactor was developed and validated to accurately predict the reactor
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22 outlet composition and other important variables. To achieve the optimum operating policy, the
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24 model-based dynamic optimization was applied to maximize overall process economics through
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26 enhancement of selectivity to production of ethylene. Implementation of the optimal operating
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29 policy on a commercial acetylene hydrogenation reactor resulted in a 13% improvement of
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31 ethylene selectivity and 10% increase of overall process economics while simultaneously
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33 decreasing the rate of catalyst deactivation. This modelling and optimization approach should be
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applicable to other fixed-bed hydrogenation processes, such as hydrogenation of methyl
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38 acetylene and propadiene (MAPD) in propylene product stream.
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41 INTRODUCTION
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44 Olefins plants produce ethylene and propylene from naphtha and LPG feedstock in steam
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crackers. The steam cracking process also produces a certain amount of acetylene impurity in the
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49 ethylene product that is subsequently sent to a downstream polymerization process. A small
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51 amount of acetylene can be a major cause of deactivation in the polymerization catalyst, and also
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leads to undesired properties in the polymer products. To avoid such problems, the concentration
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2
1
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3 of acetylene impurity in the polymerization feed stream needs to be maintained at less than 1
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6 ppm.
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9 Acetylene is conventionally removed using selective hydrogenation to ethylene, which
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11 also helps to increase overall plant ethylene yield. An acetylene hydrogenation unit is typically
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located at either of two major locations in ethylene plant unit: front-end or tail-end (or back-end).
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16 The front-end units are upstream from the demethanizer unit and the feed to these reactors
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18 therefore includes all hydrogen produced in the cracking furnaces. The tail-end units require
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hydrogen injection into the reactor feed. While both configurations have advantages and
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23 disadvantages, the tail-end configuration is generally suitable, less demanding on the equipment,
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25 catalyst and operation, and results in higher ethylene yields over the long term (Kaiser et al.,
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27 1999).
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31 The tail-end reactor is typically a multi-stage fixed-bed catalytic reactor consisting of
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33 multiple stages with inter-stage cooling and inter-stage hydrogen injection. In a three-stage setup,
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35 essentially all of the acetylene conversion takes place in the first two beds, with the last bed
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providing protection to ensure that the acetylene is converted to the levels required for product
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40 purity (a finishing bed). The conventionally used modern catalyst for acetylene hydrogenation is
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42 a palladium catalyst promoted by silver on alumina support (Pachulski et al. 2012).
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Numerous side reactions take place and result in loss of selectivity to ethylene. Over-
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48 hydrogenation leads to ethane formation, which requires separation and recycle to the gas
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50 cracker, thereby decreasing overall plant capacity and increasing energy consumption. In tail-end
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52 acetylene hydrogenation units, the oligomerization of acetylene produces so-called Green Oil
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55 (GO) (Vignola et al., 2018) which deposits on the catalyst surface, reducing the overall catalytic
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3
1
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3 activity and increasing overall operating costs (Zhang et al., 2018). A decrease in activity
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6 towards acetylene hydrogenation can be compensated by operating the reactor under more
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8 aggressive conditions – for example, higher temperature and higher hydrogen feed rates – but
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10 this in turn can cause catalyst deactivation to accelerate, leading to an increase in undesired
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ethane production. Eventually, the degree of catalyst deactivation is such that continued
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15 operation is uneconomical and it becomes necessary to take the reactor out of service in order to
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17 regenerate the catalyst. Optimal determination of operating policy throughout the hydrogenation
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cycle can improve process economics by prolonging catalyst activity and selectivity towards the
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22 main reaction while lowering catalyst deactivation rates. The challenge in operating the
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24 acetylene hydrogenation reactor is thus to maximize the overall economics by enhancing
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26 acetylene conversion and selectivity to ethylene while maintaining the product quality and run-
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29 length. In order to maintain the optimized state of the reactor over time, the operating conditions
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31 need to be carefully adjusted hourly, or at least daily, in order to avoid loss of selectivity and
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33 conversion.
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This paper describes the application of an advanced process modelling and dynamic
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39 optimization approach to a typical tail-end acetylene hydrogenation process in order to determine
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41 optimal inter-bed conditions that maximize the selectivity of the desired reaction over an entire
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operation cycle. A pseudo-stationary reactor model was constructed in the gPROMS
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46 ProcessBuilder® simulation and optimization software in order to simulate the reactor behavior
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48 and determine the optimal operating policy for maximizing process economics. The analysis
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50 demonstrated that, by altering on a daily basis the inlet conditions and thus the conversion in
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53 each of the three beds, it was possible to realize a 13% increase in ethylene gain from the process
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55 and a 10% improvement in process economics.
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3 MODEL-BASED OPTIMIZATION APPROACH
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6 The approach described here involves creating a pseudo-stationary model of the reactor
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8 catalyst beds capable of predicting to a high degree of accuracy how reaction rates and catalyst
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10 deactivation rates are affected by composition, temperatures and other important attributes. The
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kinetic model for the main hydrogenation reactions and for catalyst deactivation were proposed
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15 and validated against historical plant data to ensure the model accuracy across the range of
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17 conditions to be investigated. The validated model is then used within gPROMS dynamic
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optimization framework to determine optimal operating conditions over the operation cycle.
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22 Multiple decision variables are varied to determine the combination of values that maximize the
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24 overall economics of the process. In this case, the decision variables are the time-varying inlet
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26 temperature to each bed, and the time-varying hydrogen feed rate to each bed, with constraints
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29 including the maximum bed temperatures and outlet C2H2 concentration.
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31 FIXED-BED REACTOR MODEL
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33 The commercial acetylene hydrogenation unit considered in this work is a multi-stage
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fixed-bed reactor with solid catalyst operated under adiabatic conditions. The reactor model
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38 therefore needs to consider variations in reaction conditions along the length of each bed, while
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40 variations of reaction conditions in radial direction can occur only due to mal-distribution of the
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feed or non-uniform properties of the bed, i.e. phenomena that are difficult to predict based on
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45 first-principles. As such a one-dimensional model of the bed is adequate, assuming no variations
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47 of temperature, composition and pressure over the bed cross sectional area. The catalyst bed
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49 model is assumed to be pseudo-stationary, with a slow deactivation process being the only
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52 dynamic phenomenon considered in the model to be dependent on time.
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3 The commercial catalyst loaded in the reactor studied in this work was in a form of
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6 spherical alumina pellets coated with a thin catalytically active layer (i.e. egg-shell type catalyst).
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8 Initial test simulations with a distributed pellet model confirmed negligible mass transfer
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10 limitations in such thin layers. This enables simplification of the catalyst model to consider a
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lumped catalyst layer, neglecting concentration and temperature distribution across the layer of
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15 active catalyst.
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18 Since axial dispersion and heat conduction in the bed have negligible effect in industrial
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scale catalytic bed reactors, the required model can be reduced to a pseudo-stationary plug flow
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23 adiabatic heterogeneous catalytic bed model. Such model is described, for example, in (Froment
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25 and Bischoff, 1990) and can be represented by the following equations:
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28 For component i in the gas phase and gas temperature inside each bed:
29

30
− +
− = 0
31

(1)
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33

− + ℎ
− = 0
34

35 (2)
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38 with boundary conditions at inlet (z=0):
39
= , ; =
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43 For solid phase:
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46 , =
− (3)
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48
−∆, = ℎ
−
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50 (4)
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6
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3 The pressure profile in each bed is calculated using Ergun’s equation for pressure drop
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6 over bed of catalyst pellets (Froment and Bischoff, 1990).
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9 This model was configured in gPROMS ProcessBuilder using the Advanced Model
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11 Library for fixed bed reactors (AML: FBCR) by choosing the appropriate simplifying options.
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Figure 1 shows an example of specifying catalyst geometry and properties settings in a one-
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16 dimensional model of a tube uniformly packed with catalyst particles. The model setup in a
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18 flowsheeting environment of gPROMS ProcessBuilder is shown in Figure 2.
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41 Figure 1. Catalyst geometry and properties specification
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45 The inputs to the reactor model included feed flowrate, feed composition, hydrogen
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47 injection rate (or H2/C2H2 ratio) to each bed and inlet temperature and pressure for each bed. The
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49 key outputs calculated by the model included product composition, acetylene conversion,
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52 ethylene gain, temperature profile in the beds and economic gain from the process.
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31 Figure 2. Reactor flowsheet model setup in gPROMS ProcessBuilder.
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35 REACTION KINETICS
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38 A key challenge in building a predictive catalytic reactor model is to determine the
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40 reaction kinetics, i.e. the rate laws and kinetic parameters. Several researchers have reported the
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kinetics and mechanism of acetylene selective hydrogenation over the typical Pd/Al2O3 catalyst
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45 (Menshchikov et al. 1975); Bos et al. 1993; Schbib et al, 1996; Molero et al. 1999; Borodzinski
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47 and Cybulski, 2000; Mostoufi et al. 2005; Borodzinski and Bond, 2006; Borodzinski and Bond,
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2008) and to much lower extent the Ag-promoted Pd/Al2O3 catalyst (Khan et al. 2006; Huang et
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52 al. 2007; Pachulski et al. 2012). However, the reaction pathways and kinetic parameters reported
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54 in literature are not only different but also not directly applicable to modeling of the present
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8
1
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3 industrial reactor since they were obtained at laboratory conditions which often differ
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6 significantly from plant operating, and values of some model parameters are often missing. Most
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8 importantly, the models were not validated against data obtained at industrial scale.
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10 The approach for kinetic model development adopted in this work involved testing
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various expressions identified in the literature by tuning the key kinetic parameters against
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15 historical plant data. The reaction scheme was formulated such that it at least includes all
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17 components that were measured in the plant, which included C2H2, C2H4, C2H6, C4H8 and C6H12.
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19
The reaction scheme as adopted is shown in Figure 3. Two different active sites are considered:
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22 A-site for reactions directly involving acetylene and E-site for hydrogenation of ethylene to
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24 ethane (Borodzinski and Cybulski, 2000). Butadiene is generally accepted as an intermediate
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26 product in oligomerization reactions (Ahn et al., 2007; Egorova et al., 2009), but since butadiene
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29 was not measured in the plant, overall reactions are adopted for production of C4s and C6s from
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31 acetylene (Sheth et al., 2003). Although the amount of Green Oil (“GO”) was not directly
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33 measured, its formation is included in the model and it is considered as a precursor for formation
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36
of carbonaceous deposits deactivating the catalyst (Yang et al, 2014; Zhivonitko et al., 2016).
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38 However, since the amount of GO formed in the bed is negligible compared to the amount of
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40 process gas, it is assumed that the GO formation reaction does not affect the mass and energy
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balances in the bed (Gislason et al., 2002).
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9
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16 Figure 3. The adopted reaction scheme for acetylene hydrogenation in industrial reactor.
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19 The results of testing various reaction rate expressions from literature did not show
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22 significant differences in model predictions, which is in agreement with conclusions by Bos et al.
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24 (Bos et al., 1993) where the authors concluded that the rate expressions should be regarded as
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26 empirical correlations to be used for the prediction of the rates of reaction within the range of
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29
experimental conditions. In addition, the plant data on its own do not provide enough
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31 information for a model discrimination or for estimation of a large number of parameters.
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33 The reaction rate equation for acetylene hydrogenation to ethylene and ethylene
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35
hydrogenation to ethane, as shown in the equation (5) and (6), were adapted from Bos et al. (Bos
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38 et al., 1993). To account for the combined effect of catalyst deactivation and imperfect
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40 regeneration, activity parameters
and
! were incorporated in the rate expressions. The
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42 formation of C4s and C6s was considered to take place on active site A and the rate equations
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45 assume a similar form as the acetylene hydrogenation reaction (5) (Pachulski et al., 2012). The
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47 adapted rate expressions for reactions from the scheme depicted in Figure 3 are summarized in
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49 equations (5) to (9).
50
$% &' ()*) *)
" =
51
"+,% %
()*) ()*) "+,*) *)
52 Acetylene Hydrogenation; (5)
53
$. &) ()*/ *)
- =
54
. 12
Ethylene Hydrogenation; . .
(6)
55 0"+,()*) ()*) +,()*/ ()*/ +,*) *)
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57
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59
10
1
2
$% &2 ()*) *)
3 =
3
"+,% %
()*) ()*) "+,*) *)
4 Butene Formation; (7)
5
$% &/ ()*) *)
6 4 = % %
"+,()*) ()*) "+,*)
Hexene Formation; (8)
7 *)
8
9 All rate constants and adsorption constants in equations (5) to (8) where considered to
10
11 have an Arrhenius-type temperature dependency:
12
13
14 .:,; ' '
89 = 8 BC
= 7
56
15 < > >?@A
16 for reaction i = 1 – 4 and GO (9)
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18 ∆*:EF,G ' '
89 = 8 BC
D = D 7
19 56 < > >?@A
for all adsorbing components (10)
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21
22
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24
25 CATALYST DEACTIVATION MODEL
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28 Another modeling challenge represents the fact that none of the published literature
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30
describe a mechanistic model for the combined effect of catalyst deactivation and imperfect
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33 regeneration (Kuhn et al. 2015). There are basically 5 intrinsic mechanisms of catalyst decay:
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35 poisoning; fouling; thermal degradation (including sintering); loss of catalytic phases by vapor-
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37 solid and/or solid-solid reactions (including formation of volatile compounds); and attrition
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39
40 (Butt, 1972; Bartholomew et al. 2006). In addition, a catalyst activity drop was observed after
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42 each regeneration cycle due to inevitable imperfect regeneration or irreversible changes in
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44 catalyst properties (Pachulski et al., 2011). Here the main deactivation mechanism is considered
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47 to be fouling by carbon deposition as well as incomplete regeneration (Mosafer et al., 2016). For
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49 practical reason, the approach taken in this work involved application of a semi-empirical model
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51 similar to that of Smith et al. (Smith et al. 2003) and its tuning together with the reaction kinetics
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53
using historical plant data from multiple operation cycles.
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55
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59
11
1
2
3 The model assumes that the catalyst activity depends on amount of Green Oil
4
5
6 accummulated on the catalyst, as shown in equations (11) to (14). However, since there was no
7
8 suitable reaction rate equation for GO formation reported in literature, the model development
9
10 approach involved testing various expressions against the historical plant data. The best results in
11
12
13
terms of fit to data and confidence in model parameters were obtained when assuming the GO
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15 formation to be a first order with respect to acetylene and C6s, and a zero order with respect to
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17 hydrogen. The drop in activity for both active sites is accounted for by empirical terms that
18
19
consider the number of operation cycles already performed on the current catalyst (HI ) and the
20
21
22 deactivation effect represented by CGO, the cumulative Green Oil concentration in the catalyst
23
24 pellets.
25
26
27 Rate of Green Oil formation: JK =
JK LI-M- LINM"- (11)
28
OIPQ
= JK
29
OR
30 Green Oil accumulation: (12)
31
32 Activity for sites A:
= 7 8&( ( 8" 7 8&% IPQ (13)
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34 Activity for sites E:
! = 7 8&( ( 8" 7 8&. IPQ S
!T + 1 −
!T 1 − 7 8&. IPQ V (14)
35
36
37
38
39 PARAMETER ESTIMATION AND KINETIC MODEL VALIDATION
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42 Kinetic parameters in selected reaction rate expressions need to be fixed based on
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44 evidence from the literature or established from available experimental data. Ideally the kinetic
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47 model development is supported by a large number of laboratory experiments with a small
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49 sample of catalyst pellets, under well-defined and reproducible conditions. However, in this
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51 work it was not realistic to support the model development with small-scale experimentation. For
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54
operational reasons it was also not practical or safe to conduct a series of experiments with the
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56 target industrial-scale reactor. The challenge was therefore to develop a useful model based only
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59
12
1
2
3 on evidence from literature and on a detailed model-based analysis of historical plant data from a
4
5
6 number of historical cycles from the existing two reactors.
7
8
9
The controlled variables in the plant data, used as model inputs, included trajectories in
10
11
12 time for the feed rate, feed composition and pressure, as well as the inlet temperature and H2
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14 flow to each bed. The measured variables, used for model validation, included trajectories in
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16 time for C2H2 and H2 concentrations at the outlet from each bed, temperature measurements at
17
18
19 the outlet of and inside each bed, and the C4s and C6s product flowrates.
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22
The reaction kinetic parameters together with deactivation parameters were estimated
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25 simultaneously in gPROMS ProcessBuilder using plant data from several cycles. The attempt
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27 was originally made to estimate a single set of parameters for all three reactor beds. However, it
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29 was not possible to satisfactorily reproduce the behavior of all three beds with a single model,
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31
32 and different rate expressions and parameters had to be applied in the third bed. This suggests
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34 that the rate expressions are not representing all important aspects of the reaction mechanism.
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36 Moreover, the evidence in the literature suggests that there could be a significant shift in reaction
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38
39
mechanism at around 2000 ppm of acetylene (Pachulski et al. 2012). The inlet concentration of
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41 acetylene to Bed 1 ranged from 13,000 to 16,000 ppm, whereas its outlet concentration from Bed
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43 2 ranged from 500 to 1,000 ppm. Obviously, Bed 3 mainly served as the finishing bed to ensure
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45
that the final acetylene concentration is less than 1 ppm, which had negligible impact on the
46
47
48 overall process economics. In addition, optimization of this unit would require an extremely
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50 accurate, predictive model (to <1 ppm levels) and even if such model is available, changes in
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52 operating policy of the third bed represents a high risk of acetylene leakage. For the ultimate
53
54
55 purpose of hydrogenation rector optimization, it is therefore reasonable to take account of only
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59
13
1
2
3 Bed 1 and Bed 2. As a result, the operating policy for Bed 3 remained unchanged and all
4
5
6 limitation and constraints, including outlet concentration of acetylene, were considered at outlet
7
8 Bed 2 instead. In conclusion, the following model parameters were estimated for the first and
9
10 second bed:
T! , W , , ! , JK
T
, X$,JK , ",T , -,T , 3,T , 4,T , DI-M- , DM- , DI-M-
!
, DM-
!
. The published
11
12
13 values were used for the remaining parameters as shown in Table 1.
14
15
16
17 Table 1: Kinetic parameters used in parameter estimation. (Reference temperature (Tref) for rate
18 constants and adsorption constants is 310K.)
19
20 Reference for
Parameters Unit Estimated value Initial value
21 initial value
22
23
T! - 0.02 – 1 - -
24
25 I - 0.3 – 15 - -
26
27 - 0.01 – 0.5 - -
28
29 ! - 0.1 – 1.3 - -
30
31 "T mol. kgcat-1.s-1.bar-2 0.015 – 0.025 15.8 Bos, 1993
32
33 -T mol. kgcat-1.s-1.bar-2 0.5 – 1.5 15.6x10-3 Bos, 1993
34
35 3T mol. kgcat-1.s-1.bar-2 8.3x10-4 - -
36
37
4T mol. kgcat-1.s-1.bar-2 8.5x10-4 - -
38
JK
T
39
40
mol. kgcat-1.s-1.bar-2 135 - -
DI-M-
41
42 bar-1 38 1800 Bos, 1993
DM-
43
44 bar-1 1.4 3.95 Bos, 1993
DI-M-
!
45
46 bar-1 1.1 28.7 Bos, 1993
DI-M4
47
!
48 bar-1 0.009 0.04 Bos, 1993
DM-
49
! bar-1 0.001 4.15 Bos, 1993
50
51
52 X$," kJ.mol-1 10.1 10.1 Bos, 1993
53
54 X$,- kJ.mol-1 26.9 26.9 Bos, 1993
55
56
57
58
59
14
1
2
X$,3
3 Pachulski,
4 kJ.mol-1 30 16.3
5
2012
X$,4 16.3 (same as X$,3 )

6
7 kJ.mol-1 30 -
X$,JK
8
9 kJ.mol-1 (-100) – 0 0 -
∆$O ,I-M-
10
11 kJ.mol-1 -14.4 -14.4 Bos, 1993
12
13 ∆$O ,M- kJ.mol-1 0 0 Bos, 1993
14
15 ∆$O ,I-M-
!
kJ.mol-1 -8.0 -8.0 Bos, 1993
16
17
∆$O ,I-M4
!
kJ.mol-1 -36.4 -36.4 Bos, 1993
18
19
20
21
22
In accordance with best practice, the parameter estimation was performed using a subset
23
24 of the available data, with other data reserved for model validation of predictions using the
25
26 estimated parameters. Comparisons with plant data showed that the model reproduced historical
27
28
cycles sufficiently well to be used in subsequent optimization. As an example of model
29
30
31 validation, Figure 4(a) shows the comparison between simulated results of the model against the
32
33 measurements from plant data, in a fitting stage, for concentration of C2H2, H2 and temperature
34
35 at the outlet of Beds 1 and 2 respectively as a function of days on stream (DOS) over a run. In
36
37
38 order to validate the model, figure 4(b) shows the prediction results of the model with tuned
39
40 kinetic parameters in comparison with another set of plant data.
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38 Figure 4. Comparison plots of the results from the model (solid blue line) versus historical data
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41 (red dots) (a) in the fitting stage and (b) in the validating stage.
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45
USING THE MODEL TO SIMULATE OPERATIONAL SCENARIOS
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49 The developed model was initially used to explore various operating scenarios by
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51 performing a series of dynamic simulations of the remainder of an ongoing operation cycle. The
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53 objective was to understand an effect of changing key manipulated variables. For example, the
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56 inlet temperature profile and feed H2 to C2H2 ratio were varied to see the effect on product stream
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3 compositions, the product outlet conditions, catalyst performance and in particular ethylene gain.
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6 As an example, after operating the reactor for a period, the model was used to simulate the effect
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8 of changing some operating conditions, i.e. H2 to C2H2 ratio, on Ethylene Gain. Figure 5 shows
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10 the effects of maintaining the same temperature profile but decreasing the H2 to C2H2 ratio in the
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feed. This resulted in an ethylene gain of 5% in the initial change of the run, compared to
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15 operating with the existing condition.
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Figure 5. Simulation-based analysis
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43 The simulation results in Figure 5 also show that, although a lower H2 to C2H2 ratio can
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45 initially result in a higher ethylene gain (higher selectivity), it also enhances catalyst deactivation
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47 and therefore affects the selectivity later in the cycle. This emphasizes the fact that the whole
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50 operation cycle need to be considered which requires the dynamic optimization runs (Bilimoria
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52 and Bailey, 1978).
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1
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3 OPTIMIZING OPERATING POLICY
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6 The model was applied to determine the optimal operating policy for an operation cycle
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8 via dynamic optimization in gPROMS. As discussed above, only Bed 1 and Bed 2 were
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10 considered in the optimization. Any optimization problem is defined by an objective function,
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decision variables and constraints (Shin et al. 20017; Bäumer et al. 2007).
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15 The objective function to be maximized was the overall economics of the process
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17 (Economic Gain, ECG) over the whole operation cycle, defined by Equation 15 as an average
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profit from operation cycle minus the fixed costs calculated per day.
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$ 1 f
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22 XY Z ] = _ S`I-M4 × Xbℎ\c7d7 Le7
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\ ^ T
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25 + g × `I-M4 × Xbℎ
d7 Le7
6 W$R
26 (15)
27 − `M- × \eh7d edij7V b − −
28 ^ ^HRkR
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l
30 −
31 ^
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33 The Economic Gain considers the profit from produced ethylene, partially profit from
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35 produced ethane which is recycled back to cracking furnaces, cost of hydrogen injection and the
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37 fixed costs for catalyst regeneration, for new catalyst and for switching between the reactors.
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40 The decision variables (controls) were the inlet temperature and inlet H2/C2H2 ratio for
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42 each bed varied over the whole cycle. The time horizon was divided into a number of intervals
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44 i.e. daily, weekly or biweekly basis, and the optimizer would optimize values for the decision
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47 variables in each interval. The process constraints over the whole run were maximum
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49 temperatures in the beds and maximum C2H2 concentration at Bed 2 outlet.
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51 OPTIMIZATION APPROACH
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Initially, the approach was first demonstrated on historical cycles. The model inputs
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56 (flowrate, feed composition, pressure) were read from historical data, then the manipulated
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3 parameters i.e. inlet temperature and inlet H2/C2H2 ratio were optimized retroactively for the
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6 whole run length. Figure 6(a) shows the example results of the control parameters i.e. outlet
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8 concentration of C2H2 and H2 at Bed 1 which were still in the operating window during the
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10 optimization. This approach also demonstrated the expected increase of Economic Gain if the
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selected historical cycle had been operated optimally.
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49 Figure 6. Demonstration of optimization results of the control parameters (not to scale) based on
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52 (a) historical plant data and (b) initial portion of plant data
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3 In order to perform offline optimization of a current (ongoing) cycle, inputs are read from
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6 historical data until the current time. From the current time onwards, the model inputs are
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8 assumed fixed (feed rate, feed composition) and the manipulated parameters are optimized. The
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10 simulated results of the optimized control parameters were shown in Figure 6 (b). In this way an
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advice can be provided on the operation of the remainder of the run, including optimal run length
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15 prediction. For the optimization of a new cycle, the time profile of key inputs, such as flowrate
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17 and feed composition, need to be assumed and the manipulated parameters are optimized during
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the whole run.
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22 For the current operating cycle described above, the optimization was performed for the
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24 remainder of the operation cycle after 20 days since start of run. The optimization was repeated
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26 on a daily basis based on actual values for model inputs – flowrate, feed composition and
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29 pressure. Because of possible long-term effect of some changing operating conditions, the
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31 optimized results from the model needed to be carefully discussed with plant operators before
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33 implementation, as it might result in accelerated deactivation of the catalyst in long term.
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Therefore, during the optimization runs, a weekly meeting with plant operators was set up in
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38 order to review the optimization results before implementation.
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40 OPTIMIZATION RESULTS
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After careful discussion with the plant operators, the model and its recommended optimal
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45 operation policy were tested and validated successfully and then put to real use in the industrial
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47 reactor. Figure 7 shows optimized trajectories for the manipulated variables after implementing
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49 the identified optimal strategy in a new cycle. The optimized new cycle is compared to the
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52 immediately preceding (base case) cycle run without any optimization. The results show that the
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54 optimal trajectories are to operate at a lower temperature than the usual operating policy for an
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3 initial period before increasing the temperature when conversion and selectivity in the bed
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6 decrease. The lower temperature increases selectivity in the first bed, thus reducing production of
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8 unwanted ethane and Green Oil. It also reduces conversion in the first bed, which is taken up by
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10 spare capacity in the second bed. The lower temperature and corresponding lower rates of
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reaction in the first bed have the effect of reducing catalyst deactivation, hence extending
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15 catalyst lifetime.
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17 The optimization results suggested to initially decrease the inlet temperature of Bed 1
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while increasing temperature in Bed 2 and appropriately adjusting the H2/C2H2 inlet ratios for
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22 both beds. This resulted in a shift of some conversion of acetylene from Bed 1 to Bed 2 due to a
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24 significantly higher selectivity of the acetylene hydrogenation to ethylene in Bed 2 when
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26 compared to Bed 1. The insights obtained in the optimization allowed development of a new
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29 operating policy that generally reduced loss of ethylene by reducing acetylene conversion in the
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31 first bed and increasing the conversion in the second bed, thereby achieving a better balance in
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33 their conversion duty.
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6 (a)
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12 (b)
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21 (c)
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28 Figure 7. The optimized operating policy and results compared to baseline after implementation.
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31 (a) Bed 1 (b) Bed 2 and (c) Total Ethylene Gain
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33 As shown in Figure 7 (c), by implementing the optimized policy on the new operation,
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35 total ethylene gain was estimated to improve by 13%, which corresponded to a 10% increase in
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38 economic gain. The total benefit realized was estimated to be approximately 1.0 MUSD/year.
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40 CONCLUSION
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42 In this work, a realistic model of the industrial acetylene hydrogenation unit was
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45 developed in gPROMS ProcessBuilder, validated against historical data from several operation
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47 cycles, and then used to optimize the operating policy. The optimized operating policy included a
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49 predicted benefit of 1 MUSD/year when compared to a preceding cycle operation. An important
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additional benefit realized from the optimization is a prolonged duration of the operation cycles.
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54 The major benefit of developing and optimizing the model is that it identifies significant
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56 improvements in economic gain without the need for capital expenditure. The knowledge gained,
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3 as well as the model itself, can be applied to other fixed bed reactors, such as hydrogenation of
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6 methyl acetylene and propadiene (MAPD) in propylene product stream. There is also potential to
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8 connect the model to the process historian for a real-time monitoring of catalyst activity.
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10 NOMENCLATURE
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a, a0 catalyst activity and initial (start-of-run) activity
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15 av catalyst surface to bed volume ratio (m2/m3)
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17 C molar concentration (mol/m3)
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Ccat cost of catalyst replacement ($)
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22 CGO moles of Green Oil per mass of catalyst (mol/kgcat)
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24 cp specific heat of the process gas (J/kg.K)
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26 Creg cost of regeneration cycle ($)
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29 Csw switching cost (loss of ethylene) per cycle ($)
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31 Ea activation energy (J/mol)
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33 ECG economic gain from the reactor operation ($/day)
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36
GO Green Oil
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38 Hads heat of adsorption (J/mol.K)
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40 hf gas-solid heat transfer coefficient (J/s.m2.K)
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K adsorption constant (for active site A/E and component i) at Tref
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45 k0 reaction rate constant at Tref
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47 kA, kE deactivation parameters (m3/mol)
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49 kC kinetic constant for a deactivation due to regeneration
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52 kg gas-solid mass transfer coefficient (m/s)
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54 NC number of operation cycles on the same catalyst (= number of regenerations - 1)
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3 p partial pressure (bar)
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6 P selling price of each product ($/tonne)
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8 r rate of reaction (kmol/kg cat.s)
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10 R gas constant (J/mol.K)
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T temperature (K)
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15 ug gas superficial velocity (m/s)
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17 Y furnace yield of ethylene from cracking ethane
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z distance from inlet to the reactor bed (m)
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22 Greek letters
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24 catalyst density (kg/m3)
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26 τ run length of an operation cycle (days)
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29 Subscripts and superscripts
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31 A active site A
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33 E active site E
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g gas phase
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38 i component i
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40 S solid (catalyst) phase
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42
43
44
45 REFERENCES
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47 (1) Kaiser ,V.; Laugier, J. P.; DiCinto, R.; Picciotti, M. Acetylene Removal from Cracked
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50 General, 2011, 400, 14–24
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1
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3 GRAPHICAL ABSTRACT
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Industrial & Engineering Chemistry Research

Model-based optimization of an Acetylene Hydrogenation

Journal: Industrial & Engineering Chemistry Research

Manuscript Type: Article

Date Submitted by the Author: 29-May-2018

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