Kim 2016

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Article
Dynamic Optimization of a Dual Pressure Swing Adsorption
Process for Natural Gas Purification and Carbon Capture
Seungnam Kim, Daeho Ko, and Il Moon
Ind. Eng. Chem. Res., Just Accepted Manuscript DOI: 10.1021/acs.iecr.5b04157 Publication Date (Web): 17 Oct 2016
Downloaded from http://pubs.acs.org on October 24, 2016
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Page 1 of 36 Industrial & Engineering Chemistry Research
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Dynamic Optimization of a Dual Pressure Swing
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12 Adsorption Process for Natural Gas Purification and
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Carbon Capture
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21 Seungnam Kima, Daeho Kob*, Il Moona*
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25 Department of Chemical and Biomolecular Engineering, Yonsei University, Yonsei-ro 50, Seodaemun-
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28 gu, Seoul, 03722, Korea
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32 e-mail: ilmoon@yonsei.ac.kr
*
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GS E&C, Gran Seoul, Jongro 33, Jongno-gu, Seoul, 03159, Korea
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40 *e-mail: daeho.ko@gsconst.co.kr or daehoko@hotmail.com
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ACS Paragon Plus Environment
Industrial & Engineering Chemistry Research Page 2 of 36
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4 ABSTRACT. With an increased emphasis on reduced carbon emissions, many research efforts focused
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7 on various carbon capture techniques have concurrently expanded in application. Pressure swing
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adsorption (PSA) is one of the key processes for carbon capture and storage (CCS). During the natural
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gas sweetening operation of PSA processes, a high volume of carbon dioxide is included in the waste
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flow (heavy product). To improve the CO2 purity of the waste flow, this work firstly performs the dynamic
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optimization of a general four-step dual PSA process. The objective of the rectifying unit is to maximize
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21 methane recovery while the objective of the stripping unit is to maximize carbon dioxide purity for CCS.
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24 In brief, decision variables for the rectifying unit are the step times, P/F ratios, and feeding velocities of
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27 each unit; the length of the bed is added as a decision variable for the stripping unit. Optimization
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30 results indicate that carbon dioxide purity increases from 41.4 % to 76.3 % and methane recovery
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33 increases from 78.5 % to 95.4 %.
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KEYWORDS. Pressure swing adsorption (PSA), Dynamic optimization, Modeling, Dual PSA, Carbon
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4 1. INTRODUCTION
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8 Among several proposed strategies to reduce carbon emissions, 1 carbon capture and storage (CCS)
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has emerged as a key approach.2 To support CCS, pressure swing adsorption (PSA) has been widely
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used in separating or purifying mixed gases including natural gas, synthetic gas, landfill (LF) gas, coal
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bed methane (CBM), and other gases.3 PSA, generally available for carbon capture, operates over a
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wide range of pressure and temperature, and offers a competitive power consumption rate in the
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separating field.4 Given these advantages, significant research have focused on carbon capture using
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25 various PSA processes.5-6 Dantas et al. simulated a conventional four-step Skarstrom cycle PSA process
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28 to analyze carbon dioxide purity and recovery during CO2/N2 separation.7 Modified PSA processes have
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31 also demonstrated efficient carbon capture. Li et al. used a dual reflux (DR) PSA process to increase
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34 carbon purity.8 Grande and Blom analyzed the separation efficiency of a dual PSA process during carbon
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37 capture.9 In this study, we focus on this dual PSA process. This process consists of two units: (1) a
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40 rectifying unit and (2) a stripping unit. The additional PSA (stripping) unit purifies the waste flow from
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43 the conventional PSA (rectifying) unit. The feed gas is composed of 85% methane and 15% carbon
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46 dioxide. The rectifying unit produces high purity methane. The stripping unit separates the waste flow
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49 of the rectifying unit into carbon dioxide.
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53 Optimization of PSA processes has been the significant subject of researches over the past few
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56 decades.10 In 1990, Smith and Westerberg optimized a simple PSA process by minimizing capital and
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4 operating costs using time-averaged values in their balance equations.11-12 Nilchan and Pantelides
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7 established one-bed rapid and two-bed PSA models to minimize average power consumption.13 Ko et
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al. developed PSA optimization algorithms to be easily implemented in gPROMS modeling system and
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performed optimizations of PSA processes to separate flue gas (CO2 and N2) in view of design and
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operation.14-15 In 2012, Hasan et al. optimized PSA and vacuum PSA processes using different feed
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compositions to minimize total annual costs.16 In contrast to these prior studies, we carried out the
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21 optimization of the dual PSA process simultaneously maximizing the purity of the heavy product (carbon
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24 dioxide) and the recovery of light product (methane) by obtaining optimal operating strategies. A
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27 general four-step Skarstrom cycle is adopted and the axial domains of the adsorption beds are
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30 discretized by using partial differential algebraic equations (PDAEs) including mass balance, momentum
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33 balance, and adsorption kinetic. To gain optimal operational strategies at the cyclic steady state (CSS),
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36 the initial values of all CSS-related variables (i.e., temperature, gaseous and solid concentrations in the
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39 bed) are treated as decision variables. In this study, CSS is defined as the differences between the initial
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42 state variables at the beginning of the cycle and the final state variables at the end of the cycle are
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45 constrained by a very small positive variable, in a similar way of the previous studies.17-19
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4 2. MATHEMATICAL MODELING OF DUAL PSA
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8 Five key steps support the PSA modeling process: (1) Describe the adsorption and desorption
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equilibrium using an adsorption isotherm based on reliable data and parameters. (2) Describe the flow
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patterns and their effects on performance indicators, such as purity and recovery of components. (3)
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Establish dynamic balance equations that reflect time dependent variables. (4) Establish partial
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differential balance equations that consider axial dispersion. (5) Confirm the existence of CSS and define
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22 it mathematically.
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26 These steps are typical for modeling all separation processes using a kinetic adsorbent and often
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29 lead to complex models. Although a detailed mathematical description is desirable, the computational
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32 burden resulting from these complex equationvariable relationships cannot be ignored during
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35 optimization. To ease the computational burden, the following several assumptions are adopted in this
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38 study:
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42 Ideal gas law is applied.
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44 Radial dispersion in concentration, momentum, and temperature is neglected.
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46 A linear driving force (LDF) model is used to describe the adsorption phenomena.
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The LangmuirFreundlich (LF) isotherm is used to describe the adsorption and desorption
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50 equilibrium.
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52 The particle size, bed void, and catalyst porosity in the beds are constant.
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55 All inlet flow velocities are calculated using the valve equation except the feed flow at the
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4 The inlet purge flow velocity is calculated using the product velocity and the P/F ratio.
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6 The pressure at the bottom of the column is atmospheric at depressurization and regeneration
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steps.
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10 The selection of proper adsorbents is still a matter of contention. 20 In this study, a carbon molecular
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13 sieve (CMS) is used. The CMS type adsorbent is already popular in PSA process and has a good pressure
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16 resistance compared to the zeolites while the zeolites has a good adsorption efficiency at the vacuum
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19 circumstance.21-24 To apply accurate adsorption isotherm to the model, the CMS from the research of
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22 Bae and Lee is adopted.25 In 2005, they analyzed adsorption isotherms of a CMS type adsorbent. They
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25 estimated the LangmuirFreundlich isotherm parameter values and analyzed CH4/CO2 separation
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28 performance using PSA processes and their results are listed in Table S1. To apply temperature
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dependencies of adsorption isotherms, all parameters for two components are modified to linear
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algebraic equation forms in terms of the temperature. This modification is performed by least square
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method using MATLAB and the results are described in Figure S1 and Table S2.
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40 Table S3 lists the governing equations commonly used to describe the adsorption process,15, 21, 26-28
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43 which are consistent with the previous described PSA modeling process steps and assumptions. Table
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46 S4 lists the boundary conditions for adsorption.
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50 Each unit has four flows in this dual PSA process. Equations (1) to (4) can be used to determine the
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53 total moles of each flow during a single cycle. The binary variables for each step (yPR , yAD , yDP , and
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56 yRG ) have values of 0 or 1.14-15 At its own step, the value of each variable is 1. For example, y = 1
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4 when the pressurization step starts, while y = 0 at other steps.
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t
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M_Feed(i) = 0 cycle(yPR + yAD )u0 bed Abed Ci,0 dt (2)
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16 Using the total moles of each flow, Equations (5) and (6) are used to determine the purity and
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19 recovery, respectively.
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M_Prod_out(i)
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i M_Prod_out(i)
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25 M_prod_out(i)M_purge_in(i)
26 Recovery(i) = (6)
M_Feed(i)
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28 In a dual PSA process, the heavy product in the rectifying unit is fed to the stripping unit where it is
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31 separated again to obtain a high-purity carbon dioxide gas. The feed flow into the rectifying unit
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34 consists of 85% methane and 15% carbon dioxide, as is the recycle flow from the stripping unit. The
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37 methane purity of the light product is given as 97% for pipeline quality.29 Similarly, the purge flows (in
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40 and out) for the rectifying unit are composed of 97% methane and 3% carbon dioxide because all beds
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43 are rinsed with part of their product. The purge flows (in and out) for the stripping unit are comprised
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46 of 85% methane and 15% carbon dioxide for the same reason. The heavy product composition from
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49 the rectifying unit determined by the optimization is the same as the feed composition entering into
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52 the stripping unit. Table S5 lists the model parameters and their associated values. The bed length (Lbed )
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55 of the stripping unit is not fixed. Instead, it acts as a decision variable during optimizations because the
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4 feed flow rate into the stripping unit is often considerably less than the feed flow rate into the rectifying
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unit.
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4 3. OPTIMIZATION STRATEGIES
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8 As mentioned in the previous chapter, PSA bed models are established with PDAEs with a second
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order centered finite difference method (CFDM) in this study. Because the PSA models are highly
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nonlinear, transient, and spatially discretized to be used for simulation and optimization, they are
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difficult to converge especially in optimization calculations. To avoid the difficulties in simultaneous
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optimization convergences of the PSA models involving the rectifying unit and the stripping unit, we
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22 employ an optimization framework for the dual PSA processes as illustrated in Figure 1.
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26 Although the basic mathematical models of both units are identical, they have different objective and
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29 constraints, which are added to their own models at each Variable & constraint defining step. After
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32 the rectifying unit is optimized, select optimal values are extracted from the results to be used for the
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35 stripping unit optimization. With those optimal values and a few constraints for stripping unit, the
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38 optimization of stripping unit is performed. The simulations and optimizations are performed by using
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41 gPROMS custom modeling system (Processbuilder version 1.0.0.).
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45 As noted previously, the purpose and features of the rectifying unit alone in a dual PSA process are
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48 the same as those of a conventional PSA process for the purification of a light product (weak adsorbate).
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51 The key performance indicator in a conventional PSA process is primary component recovery in the
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54 light product stream. Similarly, the objective for the rectifying unit in a dual PSA process is to maximize
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57 methane recovery in the light product stream.30 To maximize methane recovery, the feeding velocity at
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4 the adsorption step, the P/F ratio and each step time are adopted as decision variables; the methane
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purity in the light product stream is fixed as 97% to meet the specification for pipelines.
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For the stripping unit, the methane purity constraint in the light product stream is 85% to be identical
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to the methane mole fraction of the rectifying feed stream. Two additional constraints are included in
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the stripping unit optimization procedure: (1) the total cycle time for the stripping unit is set equal to
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the rectifying unit cycle time for operational convenience, and (2) the total moles of feed in the stripping
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22 unit is set equal to the total moles of heavy product in the rectifying unit.
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26 The scheme of this process is described in Figure 2. The compositions of each stream are fixed or
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29 constrained to the corresponding values, except two streams which are marked as To Be Optimized
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32 (TBO); the feed and heavy product streams of stripping unit. Information of those streams are obtained
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35 from the optimization results of rectifying unit and transferred to the stripping unit model during the
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38 optimization.
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42 Compared to the rectifying unit, an additional and important decision variable, i.e., the bed length
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45 (STR. Lbed ), is included in the stripping unit. Because the feed molar flow rate of the stripping unit is
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48 typically less than that of the rectifying unit, the bed length must be shorter. Therefore, an optimal bed
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51 length is determined in conjunction with other decision variables during the stripping unit optimization.
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Two additional constraints are applied to both optimization procedures (for the rectifying and
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stripping units). First, both units are modeled as a two-bed model in which each unit is assumed to
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4 have interconnected twin beds that result in partial sharing of their light product as a rinsing gas. The
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7 P/F ratio determines the amount of rinsing gas from the light product flow, which subsequently affects
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the rinsing efficiency and product purities. For this reason, the adsorption step time and regeneration
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step time are assumed to be same. The pressurization step time and depressurization step time are
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also the same.
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19 Second, CSS conditions must be satisfied. Tens or even hundreds of simulated pre-CSS cycles are
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22 typically required for a PSA process to reach CSS and optimal operation.31-33 These extensive calculations
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25 result in considerable computational burden. Thus, select research have attempted to optimize PSA
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28 processes without simulating the pre-CSS cycles. Ko et al. proposed a mathematical description for CSS
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31 when optimizing PSA processes.15 Their approach eliminates the needs for pre-CSS simulations and
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34 instead, they uses an algorithm that determines initial CSS values in their optimization model. Equation
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37 (9) defines the CSS as follows:
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=0 (, z) = (, z) , = 1, , (9)
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43 where includes the temperature, the gaseous component concentration, and the solid component
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46 concentrationall indicators of CSS; and is given as a very small, positive variable (10-2 or 10-5)
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49 reflecting a sufficiently small difference between initial and final values18-19, 34
, while Ko et al.(2005)
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52 minimize by including as a penalty term in the objective function. To satisfy CSS conditions, the initial
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55 values of temperature, gaseous concentration, and solid concentration of the cycle are also treated as
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4 decision variables in the model15. Table 1 summarizes the optimization models for the rectifying and
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stripping units.
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4 RESULTS
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6 By the aforementioned optimization framework for Dual-PSA, the optimal operating strategies and
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9 associated values are obtained. Before discussing the optimization results, the CSS should be discussed
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12 first. For smooth conversion of optimizations, the normalized value (between 0 and 1) for gaseous
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15 component (Cnorm,i ) and temperature (Tnorm,i ) are defined. The solid phase loadings for each component
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18 (qi ) are not normalized because their values are already located similar range with Cnorm,i and Tnorm,i .
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21 The differences between the initial and final value of these normalized variables are defined to check
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24 the CSS tolerance. The PSA model in this study discretized into eleven nodes along the axial direction.
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27 Except the top and bottom point, because they are one of the boundary conditions, nine nodes are
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30 participating to check the CSS. Nine nodes with gaseous concentration, solid loading for two
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33 components, and temperature make 45 individual constraints for each unit which are working for CSS
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analysis and the values are listed in Table S6. The absolute mean value of the CSS tolerance is 3.57
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106 , therefore, the attainment of CSS is accomplished. The initial P, T values are listed in Table S7. In
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addition, the pressure and temperature profile and gaseous component concentration profile of both
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side of beds are described in Figure S2 and Figure S3, respectively.
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48 Table 2 lists the optimized recovery and purity of components for both conventional (stand-alone
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51 rectifying unit) and dual PSA process. The dual PSA process is regarded as a rectifying unit with a
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54 supplemented stripping unit. In other words, the conventional PSA and stand-alone rectifying unit are
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57 same in this work. The performances at the dual PSA process are compared to those of the conventional
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4 stand-alone PSA process. In the conventional stand-alone PSA process, the methane recovery is 78.5 %,
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7 and the carbon dioxide purity and recovery in the waste flow are 41.4 % and 86.2 %, respectively. Table
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3 provides the detailed optimization results of the rectifying and stripping units. The dual PSA process
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has substantially higher carbon dioxide purity and methane recovery than the conventional stand-alone
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PSA process.
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19 The first case study is performed to ensure the optimization results, we check the effect of adsorption
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22 step time on the methane purity and recovery in rectifying, where the variables other than the
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25 adsorption step time are maintained at the fixed values as shown in Table S8.
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29 As expected, a trade-off between methane purity and recovery of rectifying unit is observed. As the
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32 adsorption step time increases, the methane recovery also increases, but the methane purity decreases.
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35 Referring to Figure S4, the recovery in Cases 4 and 5 is higher than the optimal results (Case 3). However,
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38 neither case meets the lower purity limit of 97%. Comparatively, the purity in Cases 1 and 2 is higher
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than the optimal results (Case 3) but the recovery is lower in each case. Providing the optimal balance
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between purity and recovery, Case 3 is regarded as the optimal case.
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47 The stripping unit optimization relies upon select optimal variable values extracted from the rectifying
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50 unit optimization results. Cycle time (394 s) and each mole of heavy product in the rectifying unit are
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56 length, the bed length in the stripping unit is not fixed and determined through the optimization.
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4 Most notable in these results is the increased carbon dioxide purity. The optimized value of the
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7 objective is 0.763, representing a 34.9 % increase in carbon dioxide purity in the heavy product following
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the stripping unit process. On the other hand, the optimized carbon dioxide recovery by the post-
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stripping is 83.3%, representing a small decrease from the 86.2 % value observed from the result of the
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conventional PSA process (without a stripping unit). The total mole of light product of the rectifying
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unit increased by the optimization, on the other hand, the total mole of carbon dioxide in heavy product
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21 of the stripping unit decreased.
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25 To analyze the effect of variation on the bed length of stripping unit, the second case study is
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28 performed by five additional optimizations. The results are described in Figure 3. In certain, the purity
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31 of Case 8 (optimal case) has the highest value. From the results, we can infer that the decision variables
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34 have specific influence over the carbon dioxide purity. Figure 3(b) shows that the P/F ratio and feed
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37 velocity decrease as the bed length increases. Generally, a longer bed length means an extension of
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40 contact time, which increases the purity of light product. The increase of P/F ratio also leads to higher
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43 purity of light product because the adsorbent is regenerated better in high P/F ratio than in low P/F
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46 ratio. For this case, because the purity of light product is fixed value (85% for methane), the purity
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49 improvement by the extension of bed length was offset by reduced feed velocity and P/F ratio.
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52 Considering above results and detailed data in Table S8, the decreases in carbon dioxide purity on both
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55 sides Case 8 can be demonstrated by:
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4 1. According to increase of the bed length from 0.593 m to 0.659 m (from Case 6 to Case 8) in the
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7 stripping unit when the CH4 purity in light product stream is fixed at 85%, the effect of bed length
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and feed gas velocity on the CO2 purity in heavy product stream is smaller than that of P/F ratio.
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Thus the CO2 purity increases as to the increase of the bed length in Case 6 to Case 8.
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16 2. For the Case 8 through Case 11, the influence of the P/F ratio on CO2 purity in heavy product
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19 stream is smaller than that of the bed length and feed gas velocity. So the CO2 purity decreases
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22 according to the increases of the bed length from 0.659 m to 0.757 m (from Case 8 to Case 11).
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26 Judging from the above analyses, when we fix the purity of light product stream, the purity of heavy
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29 product stream shows different trend, as to the bed length, feed flow rate, and P/F ratio, from when
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32 the light product purity is not fixed. The general behaviors of PSA processes without fixing the CH4
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35 purity in light product stream show that (1) methane purity of light product stream and carbon dioxide
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38 purity of heavy product stream increase as to the increase of the bed length and the decreases of the
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feed gas flow rate and P/F ratio, and (2) the purity of carbon dioxide in heavy product stream is
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proportional to the recovery of carbon dioxide in the same stream, while the purity of methane in light
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product stream is inversely proportional to the recovery of methane in the same stream.
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50 To obtain optimal ratio of the bed length of the stripping unit (STR. Lbed ) to the rectifying unit
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53 (REC. Lbed ), one more case study is conducted. Additional four cases are processed through the
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56 optimization framework supposed in this study. The methane composition varies 83 % to 87 % and the
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4 detailed results are listed in Table S10. The ratio trend with varying feed composition is described in
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7 Figure 4. As the methane composition increases, the methane recovery and total cycle time increase
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whereas the carbon dioxide recovery, carbon dioxide purity of heavy product stream and bed length of
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stripping unit decrease. The increase of methane recovery and total cycle time comes from the higher
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methane composition of the feed stream. On the contrary, the higher total mole of carbon dioxide in
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STR.feed decreasing makes the other variables decrease.
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4 4. CONCLUSIONS
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8 In this study, a dual PSA process for separating natural gas is modeled and optimized using various
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operational and design decision variables to maximize carbon dioxide purity and methane recovery.
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Figure 5 depicts these optimized operational strategies. Under these optimized conditions, the carbon
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dioxide (secondary product) purity greatly improves to 76.3 % from the feed gas consisting of the 85%
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methane and 15% carbon dioxide, with the 97% methane purity as the light product specification. In
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the rectifying unit, maximizing methane recovery in the light product stream is the objective. In the
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25 stripping unit, maximizing carbon dioxide purity in the heavy product stream is the objective. Individual
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28 optimizations are performed for each unit with different objectives and constraints. In addition, the dual
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31 PSA optimization procedure is introduced to efficiently solve the huge model including the rectifying
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34 unit and stripping unit as well as different objective functions for each unit.
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38 As the results of the optimization, carbon dioxide purity increases from 41.4 % to 76.3 % and methane
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41 recovery increases from 78.5 % to 95.4 % compared to the stand-alone PSA process. Contributing to
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44 these operational gains, optimal values for the step times, P/F ratio, feeding velocity, and bed length
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47 are attained. To investigate the effects of decision variables on the performances, two types of sensitivity
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50 analyses are performed by simulating five cases (Cases 1 5) and optimizing six cases (Cases 6 11).
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53 The optimization and the sensitivity analyses of this work are helpful in enhancing the understanding
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56 of the effects and interactions of the variables on the performances such as the purity and recovery. In
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4 addition, the bed length ratio of stripping unit with varying methane composition of feed stream is
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7 optimized. Although the trend of ratio is obtained based on conceptual design of this study, these
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results can be applied to specific fields.
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4 Supporting Information
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6 Prediction results for LF isotherm parameters and linearized equation form in terms of temperature;
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trade-off between purity and recovery; initial pressure and temperature profiles; dynamic pressure and
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9 temperature profile of both side of the beds; PSA modeling governing equations and boundary
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11 conditions; model parameters; CSS tolerance checking data; case study results for varying bed length
12 and feed composition
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15 This information is available free of charge via the Internet at http: //pubs.acs.org.
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ACKNOWLEDGEMENT
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This research has been supported by Korea Evaluation Institute of Industrial Technology (KEIT) under
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the Ministry of Trade, Industry & Energy (MOTIE) of Korea government and GS E&C.
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4 NOMENCLATURE
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11 Abed bed area, m2
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14 Ci gas concentration of component i, mol/m3
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16 Cini,i initial gas concentration of component i, mol/m3
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19 Cfianl,i final gas concentration of component i, mol/m3
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22 Dx axial dispersion coefficient, m2 /s
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25 uI interstitial velocity of flow, m/s
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27 uS superficial velocity of flow, m/s
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30 bed bed density, kg/m3
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33 bed bed void
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35 gas gas viscosity, kg/(m s)
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38 R particle particle radius, m
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41 particle particle density, kg/m3
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44 particle particle void
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47 gas gas density, kg/m3
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ki mass transfer coefficient for component i
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52 Ci gaseous concentration for component i, mol/m3
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55 Cini,i initial gaseous concentration for component i, mol/m3
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58 qi solid phase loading for component i, mol/kg
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3 qini,i initial solid phase loading for component i, mol/kg
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6 qfinal,i final solid phase loading for component i, mol/kg
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9 qeq,i adsorbed phase concentration in equilibrium of component i, mol/kg
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12 Cpg gas-phase heat capacity, J/(kg K)
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Cps adsorbent heat capacity, J/(kg K)
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17 Kl effective axial thermal conductivity, J/(m s K)
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20 Hi adsorption heat of component i, J/mol
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23 hwall heat transfer coefficient between gas phase and wall, J/(m2 s K)
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25 M_Light_prodi total mole of component i in light product, mol
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28 M_Feedi total feed mole of component i, mol
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31 M_Purge_ini total purge-in mole of component i, mol
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M_Heavy_prodi total mole of component i in heavy product, mol
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36 yPR a binary variable for pressurization step
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39 yAD a binary variable for adsorption step
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yDP a binary variable for depressurization step
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44 yRG a binary variable for regeneration step
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47 yprod,CH4 methane purity in light product
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50 yprod,CO2 carbon dioxide purity in heavy product
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T gas temperature, K
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55 Tini initial gas temperature, K
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3 Tfinal final gas temperature, K
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6 t cycle total cycle time, s
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4 REFERENCES
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7 (1) Ebner, A. D.; Ritter, J. A. State-of-the-art Adsorption and Membrane Separation Processes for Carbon Dioxide
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9 Production from Carbon Dioxide Emitting Industries. Sep. Sci. Technol. 2009, 44, 1273.
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11
12 (2) Katzer, J.; Ansolabehere, S.; Beer, J.; Deutch, J.; Ellerman, A.; Friedmann, S.; Herzog, H.; Jacoby, H.; Joskow, P.;
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14 McRae, G. The Future of Coal: Options for a carbon-constrained world. Massachusetts Institute of Technology
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16 2007, 39.
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18 (3) Agarwal, A.; Biegler, L. T.; Zitney, S. E. A Superstructure-Based Optimal Synthesis of PSA Cycles for Post-
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20 Combustion CO2 Capture. AIChE J. 2010, 56, 1813.
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23 (4) Jee, J. G.; Lee, S. J.; Kim, M. B.; Lee, C. H. Three-bed PVSA Process for High-purity O-2 Generation from
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25 Ambient Air. AIChE J. 2005, 51, 2988.
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27 (5) Reynolds, S. P.; Ebner, A. D.; Ritter, J. A. Stripping PSA Cycles for CO2 Recovery from Flue Gas at High
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29 Temperature using a Hydrotalcite-like Adsorbent. Ind. Eng. Chem. Res. 2006, 45, 4278.
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(6) Liu, Z.; Grande, C. A.; Li, P.; Yu, J. G.; Rodrigues, A. E. Multi-bed Vacuum Pressure Swing Adsorption for Carbon
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Dioxide Capture from Flue Gas. Sep. Purif. Technol. 2011, 81, 307.
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36 (7) Dantas, T. L. P.; Luna, F. M. T.; Silva, I. J.; Torres, A. E. B.; de Azevedo, D. C. S.; Rodrigues, A. E.; Moreira, R.
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38 F. P. M. Carbon Dioxide-Nitrogen Separation through Pressure Swing Adsorption. Chem. Eng. J. 2011, 172,
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(8) Li, D. D.; Zhou, Y.; Shen, Y. H.; Sun, W. N.; Fu, Q.; Yan, H. Y.; Zhang, D. H. Experiment and Simulation for
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44 Separating CO2/N-2 by Dual-Reflux Pressure Swing Adsorption Process. Chem. Eng. J. 2016, 297, 315.
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47 (9) Grande, C. A.; Blom, R. Dual Pressure Swing Adsorption Units for Gas Separation and Purification. Ind. Eng.
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49 Chem. Res. 2012, 51, 8695.
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51 (10) Jiang, L.; Biegler, L. T.; Fox, V. G. Design and Optimization of Pressure Swing Adsorption Systems with Parallel
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53 Implementation. Comput. Chem. Eng. 2005, 29, 393.
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56 (11) Smith, O. J.; Westerberg, A. W. Mixed-Integer Programming for Pressure Swing Adsorption Cycle Scheduling.
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3 (12) Smith, O. J.; Westerberg, A. W. The Optimal-Design of Pressure Swing Adsorption Systems. Chem. Eng. Sci.
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8 (13) Nilchan, S.; Pantelides, C. C. On the Optimisation of Periodic Adsorption Processes. Adsorption 1998, 4, 113.
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10 (14) Ko, D.; Siriwardane, R.; Biegler, L. T. Optimization of a Pressure-Swing Adsorption Process using Zeolite 13X
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12 for CO2 Sequestration. Ind. Eng. Chem. Res. 2003, 42, 339.
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15 (15) Ko, D.; Siriwardane, R.; Biegler, L. T. Optimization of Pressure Swing Adsorption and Fractionated Vacuum
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17 Pressure Swing Adsorption Processes for CO2 Capture. Ind. Eng. Chem. Res. 2005, 44, 8084.
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19 (16) Hasan, M. M. F.; Baliban, R. C.; Elia, J. A.; Floudas, C. A. Modeling, Simulation, and Optimization of
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21 Postcombustion CO2 Capture for Variable Feed Concentration and Flow Rate. 1. Chemical Absorption and
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23 Membrane Processes. Ind. Eng. Chem. Res. 2012, 51, 15642.
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26 (17) Agarwal, A.; Biegler, L. T.; Zitney, S. E. Simulation and Optimization of Pressure Swing Adsorption Systems
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Using Reduced-Order Modeling. Ind. Eng. Chem. Res. 2009, 48, 2327.
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30 (18) Dowling, A. W.; Vetukuri, S. R. R.; Biegler, L. T. Large-Scale Optimization Strategies for Pressure Swing
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32 Adsorption Cycle Synthesis. AIChE J. 2012, 58, 3777.
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(19) Khajuria, H.; Pistikopoulos, E. N. Optimization and Control of Pressure Swing Adsorption Processes Under
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Uncertainty. AIChE J. 2013, 59, 120.
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39 (20) Fatehi, A. I.; Loughlin, K. F.; Hassan, M. M. Separation of Methane-Nitrogen Mixtures by Pressure Swing
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41 Adsorption Using a Carbon Molecular-Sieve. Gas. Sep. Purif. 1995, 9, 199.
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43 (21) Ko, D. Development of a Simulation Model for the Vacuum Pressure Swing Adsorption Process To Sequester
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45 Carbon Dioxide from Coalbed Methane. Ind. Eng. Chem. Res. 2016, 55, 1013.
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48 (22) Ko, D. Optimization of Vacuum Pressure Swing Adsorption Processes to Sequester Carbon Dioxide from Coalbed
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50 Methane. Ind. Eng. Chem. Res. 2016, 55, 8967.
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52 (23) Jayaraman, A.; Chiao, A. S.; Padin, J.; Yang, R. T.; Munson, C. L. Kinetic Separation of Methane/Carbon Dioxide
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54 by Molecular Sieve Carbons. Sep. Sci. Technol. 2002, 37, 2505.
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57 (24) Stanciu, V.; David, E.; Stefanescu, D. Carbon Dioxide Separation from Carbon in the Natural Gas, by Carbon
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3 Molecular Sieves Adsorption. Revista De Chimie 1996, 47, 19.
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6 (25) Bae, Y. S.; Lee, C. H. Sorption Kinetics of Eight Gases on a Carbon Molecular Sieve at Elevated Pressure. Carbon
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8 2005, 43, 95.
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10 (26) Chou, C. T.; Huang, W. C. Incorporation of a Valve Equation into the Simulation of a Pressure Swing Adsorption
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12 Process. Chem. Eng. Sci. 1994, 49, 75.
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15 (27) Nikolic, D.; Giovanoglou, A.; Georgiadis, M. C.; Kikkinides, E. S. Generic Modeling Framework for Gas
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17 Separations using Multibed Pressure Swing Adsorption Processes. Ind. Eng. Chem. Res. 2008, 47, 3156.
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19 (28) Santos, M. P. S.; Grande, C. A.; Rodrigues, A. E. Dynamic Study of the Pressure Swing Adsorption Process for
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21 Biogas Upgrading and Its Responses to Feed Disturbances. Ind. Eng. Chem. Res. 2013, 52, 5445.
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23
24 (29) Shao, P. H.; Dal-Cin, M.; Kumar, A.; Li, H. B.; Singh, D. P. Design and Economics of a Hybrid Membrane-
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26 Temperature Swing Adsorption Process for Upgrading Biogas. J. Membr. Sci. 2012, 413, 17.
27
28 (30) Fong, J. C. L. Y.; Anderson, C. J.; Xiao, G. K.; Webley, P. A.; Hoadley, A. F. A. Multi-objective Optimisation of
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30 a Hybrid Vacuum Swing Adsorption and Low-temperature Post-combustion CO2 Capture. Journal of Cleaner
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32 Production 2016, 111, 193.
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34
(31) Kvamsdal, H. M.; Hertzberg, T. Optimization of PSA systems - Studies on Cyclic Steady State Convergence.
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Comput. Chem. Eng. 1997, 21, 819.
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38
39 (32) Ko, D.; Moon, I. Optimization of Start-up Operating Condition in RPSA. Sep. Purif. Technol. 2000, 21, 17.
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41
(33) Zilinskas, A.; Fraga, E. S.; Beck, J.; Varoneckas, A. Visualization of Multi-Objective Decisions for the Optimal
42
43 Design of a Pressure Swing Adsorption System. Chemom. Intell. Lab. Syst. 2015, 142, 151.
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45
46 (34) Jiang, L.; Fox, V. G.; Biegler, L. T. Simulation and Optimal Design of Multiple-Bed Pressure Swing Adsorption
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48 Systems. AIChE J. 2004, 50, 2904.
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1
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4 List of Tables
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7 Table 1. Optimization models for the rectifying and stripping units
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9 Table 2. Optimized performance indicators for conventional and dual PSA processes
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11 Table 3. Optimized decision variables for the rectifying and stripping units
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4 Table 1. Optimization models for the rectifying and stripping units
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6 Rectifying unit Stripping unit
7 Objective max z = recoveryCH4 max z = yprod,CO2
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9 Lower Boun Upper Bo Lower Boun Upper Boun
10 d und d d
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12 t PR (s) 1 30 t PR (s) 1 100
13 t AD (s) 30 400 t AD (s) 30 400
14 t DP (s) 1 30 t DP (s) 1 100
Decision vari t RG (s) 30 400 t RG (s) 30 400
15 ables uad (m/s) 1.16 1.74 uad (m/s) 0.12 0.81
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P/F ratio 0.01 0.30 P/F ratio 0.01 0.30
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STR. Lbed (m) 0.5 1.5
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27 0.00001 yprod,CH4 0.85 0.00001
28 0.00001 yprod,CH4 0.97 0.00001
0.0001 t PR t DP 0.0001
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30 0.0001 t PR t DP 0.0001 0.0001 t AD t RG 0.0001
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0.0001 t AD t RG 0.0001 Cini,i,z Cfinal,i,z
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33 Tini,z Tfinal,z
34 Cini,i,z Cfinal,i,z
Constraints qini,i,z qfinal,i,z
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36 Tini,z Tfinal,z 0.0001 STR. M_feed(i)
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38 qini,i,z qfinal,i,z REC. M_Heavy_prod(i)
39 0.0001
40 (i = CH4 , CO2 )
41 0.0001 t cycle,STR t cycle,REC 0.0001
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4 Table 2. Optimized performance indicators for conventional and dual PSA processes
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6 LP: Light Product Conventional PSA process
7 Dual PSA process Difference
HP: Heavy Product (stand-alone rectifying unit)
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9 Product CH4 (LP) 78.5% 95.4% 16.9%
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11 recovery CO2 (HP) 86.2% 83.3% -2.97%
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14 Product CH4 (LP) 97.0% 97.0% -
15
purity CO2 (HP) 41.4% 76.3%
16 34.9%
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Table 3. Optimized decision variables for the rectifying and stripping units
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24 Rectifying unit Stripping unit
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26 CH4 recovery CO2 purity
27 Objective
28 78.5% 76.3%
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30
(s) 9 8
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33 (s) 187 188
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35 (s) 9 8
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38 (s) 187 188
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40 394 394
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42 P/F ratio 0.109 0.045
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44 (m/s) 1.160 0.339
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47 (m) 1.55 0.659
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4 List of Figures
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6 Figure 1. Optimization procedure for dual PSA process
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8 Figure 2. Scheme of Dual PSA process including stream information and cycle diagram
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10 Figure 3. Comparative optimization results for various bed lengths in stripping unit: (a) CO 2 purity
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trends and (b) optimal P/F ratio and feed velocity trends
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14 Figure 4. Ratio of optimal bed length of Stripping unit to Rectifying unit
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16 Figure 5. Optimal dual PSA operational strategies that maximize CH4 recovery and CO2 purity
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46 Figure 1. Optimization procedure for dual PSA process
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49 Figure 2. Scheme of Dual PSA process including stream information and cycle diagram
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24 (a)
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27 0.06 0.342
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29 0.341
30 0.05
31 0.34
32
0.04 0.339
Feed Velocity
33
P/F ratio
34 0.338
35 0.03
36 0.337
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38 0.02 0.336
39 P/F ratio
40 0.335
41 0.01 Feed velocity
42 0.334
43
0 0.333
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45 CASE6 CASE7 CASE8 CASE9 CASE10 CASE11
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48 (b)
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50 Figure 3. Comparative optimization results for various bed lengths in stripping unit: (a) CO2 purity
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trends and (b) optimal P/F ratio and feed velocity trends
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4 0.470
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6 0.460
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8 0.450
STR L_bed ratio
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0.440
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13 0.430
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15 0.420
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17 0.410
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19 0.400
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21 0.83 0.84 0.85 0.86 0.87
22 Feed CH4 composition
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26 Figure 4. Ratio of optimal bed length of Stripping unit to Rectifying unit
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39 Figure 5. Optimal dual PSA operational strategies that maximize CH4 recovery and CO2 purity
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