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Article
Reactive Distillation Columns with Multiple Reactive Sections: A
Case Study on the Disproportionation of Trichlorosilane to Silane
Xinxiang Zang, Kejin Huang, Yang Yuan, Haisheng Chen, Liang Zhang, Shaofeng Wang, and Kun Wang
Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.6b03715 • Publication Date (Web): 03 Jan 2017
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Page 1 of 29 Industrial & Engineering Chemistry Research

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4 Research paper submitted to Industrial & Engineering Chemistry Research
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13 Reactive Distillation
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15 Columns with Multiple Reactive Sections:
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17 A Case Study on the Disproportionation of Trichlorosilane to Silane
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21 Xinxiang Zang, Kejin Huang,∗ Yang Yuan,
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23 Haisheng Chen, Liang Zhang, Shaofeng Wang, and Kun Wang
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25 College of Information Science and Technology,
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Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China
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4 ABSTRACT
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With reference to the disproportionation of trichlorosilane to silane, a three-stage consecutive reversible reaction with
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rather unfavorable reaction kinetics of a near zero thermodynamic conversion, in-depth comparison in steady-state
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11 performance is performed between the reactive distillation column with a single reactive section (RDC-SRS) and those
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13 with multiple reactive sections (RDC-MRS), under the assumptions of the same total number of stages and the same total
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15 amount of catalyst employed. With the incremental arrangement of reactive sections, the RDC-MRS shows a steady
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17 improvement in steady-state performance with considerably reduced operating cost and capital investment as compared
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19 with the RDC-SRS. The great advantages originate essentially from the additional degrees of freedom resulted from the
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21 arrangement of multiple reactive sections in process synthesis and design. Apart from the coordination effect to the
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23 three-stage consecutive reversible reactions processed, the additional degrees of freedom serve also to reinforce internal
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25 mass integration and internal energy interaction between the reaction operations and the separation operations involved.
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Arrangement of side-condensers is also examined towards the RDC-MRS and the outcomes reveal the thermodynamic
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rational to adopt multiple reactive sections in process development. Although these findings are derived from the specific
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32 case study chosen, it should be considered to be of general significance for the synthesis and design of reactive distillation
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34 columns separating complicated reacting mixtures involving multiple reversible reactions.
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42 Keywords: Reactive distillation column, Multiple reactive sections, Internal mass integration, Internal energy integration,
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44 Process synthesis, Process design
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4 1. INTRODUCTION
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As shown in Figure 1a, reactive distillation columns with a single reactive section (RDC-SRS) are generally characterized
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by a common structure with a single reactive section in between their rectifying section and stripping section. For the
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11 separations of reacting mixtures with favorable thermodynamics and reaction kinetics (e.g., A + B ↔ C + D with αC > αA >
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13 αB > αD), such kind of process intensification facilitates generally the simultaneous occurrence of the reaction operations and
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15 separation operations involved and can bring about significant benefits in the aspect of capital investment and operating cost as
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17 compared with its conventional counterparts, e.g., a continuous stirred tank reactor followed by a number of distillation
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19 columns. 3−5 For the separations of reacting mixtures with unfavorable thermodynamics and reaction kinetics (e.g., A + B ↔ C
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21 + D with αA > αC > αD > αB), such kind of process intensification may, however, not be well suitable for the simultaneous
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23 occurrence of the reaction operations and separation operations involved and is likely to lose its competition with its
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25 conventional counterparts in the aspect of capital investment and operating cost. 6−8 The realities, in fact, reveal a serious
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drawback of the common configuration of the RDC-SRS, i.e., the low flexibility to cope with the unfavorable thermodynamics
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and reaction kinetics, and for the purpose of extending its applications, careful modifications must be made during process
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32 synthesis and design. One of the potential strategies is to adopt multiple reactive sections in process development and this gives
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34 rise to a novel configuration of reactive distillation columns with multiple reactive sections (RDC-MRS), as shown in Figure
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36 1b. The arrangement of multiple reactive sections renders apparently more flexibilities than in the RDC-SRS for not only
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38 counteracting the negative effects of the unfavorable thermodynamics and reaction kinetics but also reinforcing internal mass
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40 integration and/or internal energy interaction between the reaction operations and the separation operations involved. In the
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42 case of separating the unfavorable quaternary reacting mixtures (i.e., A + B ↔ C + D with αA > αC > αD > αB), Tung and Yu
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44 firstly advocated employing two reactive sections at the top and the bottom ends (including condenser and reboiler as well),
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46 respectively, to take into account the unfavorable relative volatilities and this lead to the derivation of the reactive distillation
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48 columns with double reactive sections (RDC-DRS). 9 Zhang et al. demonstrated further the advantages of the RDC-DRS over
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the RDC-SRS in the separations of these kinds of reacting mixtures and pointed out that the locations of the two reactive
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sections as well as feed splitting could play pivot roles in strengthening internal mass integration and/or internal energy
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55 interaction between the reaction operations and the separation operations involved. Chen et al. recently found that an
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Phone: +86 10 64437805. Fax: +86 10 64437805. E-mail: huangkj@mail.buct.edu.cn.
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4 external recycle between the top and bottom ends could also serve to enhance the performance of the RDC-DRS due to its
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favorable impact to internal mass integration and/or internal energy interaction between the reaction operations and the
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separation operations involved. 12, 13 In the case of separating two-stage consecutive reversible reactions, such as A + B ↔ C +
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11 D, C + B ↔ E + D with αD > αB > αC > αA > αE and Dimethyl Carbonate + Ethanol ↔ Ethyl Methyl Carbonate + Methanol,
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13 Ethyl Methyl Carbonate + Ethanol ↔ Diethyl Carbonate + Methanol, Yu et al. showed that the two reactive sections could also
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15 be arranged in the middle of the RDC-DRS and worked effectively to coordinate the interactions between the two consecutive
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17 reversible reactions involved. Mueller and Kenig once indicated the possibility of employing dividing-wall distillation
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19 columns to construct the RDC-DRS. 15 In order to achieve the reactive separations of cyclohexene/cyclohexane binary mixtures
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21 with water as reactive entrainer, Yu devised a novel and effective RDC-DRS with the aid of a dividing wall, in which the two
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23 reactive sections were located at the both sides of the wall. 16
Note that the above researches focused exclusively on the
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25 synthesis and design of the RDC-DRS, i.e., the simplest structure of the RDC-MRS. In the case of separating reacting mixtures
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with much more unfavorable thermodynamics and much more complicated reaction kinetics (e.g., the three-stage consecutive
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reversible reaction to be studied in the current work), the RDC-MRS should certainly be reinforced with more than two
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32 reactive sections during process synthesis and design. For such kind of process designs, they are quite likely to be more
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34 thermodynamically efficient than the RDC-SRS and worth a detailed evaluation, especially regarding the relationship between
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36 the number of reactive sections and steady-state performance of the RDC-MRS. Unfortunately, so far no systematic studies
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38 have been conducted and reported, yet.
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40 In this paper, a case study on the disproportionation of trichlorosilane to silane is chosen to evaluate the steady-state
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42 performance of the RDC-MRS. The reaction system features a fairly unfavorable reaction kinetics involving a three-stage
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44 consecutive reversible reaction with a near zero thermodynamic conversion, thereby representing an extremely challenging
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46 example for the applications of reactive distillation columns. In terms of in-depth comparison with the RDC-SRS, the favorable
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48 effect of arranging multiple reactive sections in the RDC-MRS is clearly demonstrated. Arrangements of side-condensers are
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also conducted to reveal the thermodynamic reasonability of adopting multiple reactive sections in process synthesis and
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design. Some concluding remarks are finally summarized in the last section of this article.
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57 2. A CASE STUDY ON THE DISPROPORTIONATION OF TRICHLOROSILANE TO SILANE
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4 2.1. Problem Description. With resin Amberlyst A-21 as the heterogeneous catalyst, the disproportionation of
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trichlorosilane to silane proceeds through three consecutive reversible reactions with the involvement of five components,
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including silicon tetrachloride (STC), trichlorosilane (TCS), dichlorosilane (DCS), monochlorosilane (MCS), and silane (SIL).
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11 The detailed reaction kinetics can be described as below. 17, 18
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13 2TCS ↔ STC + DCS ∆Ηr = 6402kJ/kmol (1)
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15 2DCS ↔ TCS + MCS ∆Ηr = 2226 kJ/kmol (2)
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17 2MCS ↔ DCS + Silane ∆Ηr =–248 kJ/kmol (3)
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19 The reaction rates for the first-, second-, and third-stage reactions are expressed with the following equations.
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21 r1=k1(x2TCS−xSTCxDCS/K1) (4)
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23 r2=k2(x2DCS−xTCSxMCS/K2) (5)
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25 r3=k3(x2MCS−xDCSxSIL/K3) (6)
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where xSTC, xTCS, xDCS, xMCS, and xSIL represent the mole fractions of STC, TCS, DCS, MCS, and silane, respectively; r is the
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reaction rate for each stage reaction involved.
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32 The rate constants of the forward reactions (k) and chemical equilibrium constant (K) are described as follows.
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34 k=k0exp(−E/RT) (7)
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36 K=K0exp(−∆H/RT) (8)
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38 where k0 and K0 denote the pre-exponential factors, respectively; E is the activation energy of the forward reactions, and ∆H,
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40 the thermal heat of reactions.
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42 Table 1 lists the physicochemical properties and operating conditions of the RDC-SRS and RDC-MRS to be developed.
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44 Note that the five reacting components exhibit an ascending order of boiling-points as shown in eq. 9. It seems then to be
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46 reasonable to carry out the three-stage consecutive reversible reactions by means of a reactive distillation column and extract
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48 the lightest component silane and the heaviest component STC as top and bottom products, respectively, while keeping the rest
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components within its reactive section. Huang et al. showed firstly the feasibility of obtaining a high purity of silane over 99 %
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(mol) and approaching a complete conversion of TCS in a RDC-SRS. They indicated further the great potential to employ
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55 side-condensers to improve steady-state economics. Through an iterative simulation-optimization procedure, Alcántara-Ávila et
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57 al. proposed a multitask RDC-SRS with intermediate heat exchangers that was flexible to switch between the production of
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4 silane, MCS, and DCS and found dramatic improvement in steady-state economics.19, 20 Ramírez-Márquez et al. examined the
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dynamics and control of the multitask RDC-SRS and demonstrated that the process could be operated smoothly with a
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decentralized control structure comprised of either temperature, composition, or temperature/composition cascade loops.
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11 Owing to the fairly unfavorable reaction kinetics of a near zero thermodynamic conversion and the strong interactive nature of
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13 the three consecutive reversible reactions, the RDC-MRS is considered to be potentially more attractive than the RDC-SRS and
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15 this remains to be the primary purpose of the current study. Steady-state simulation is performed in the environment of Aspen
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17 Plus, and the module of RacFrac is adopted to represent the behaviors of the RDC-SRS and RDC-MRS. 19 As the reacting
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19 mixture is nonpolar, the Peng-Robinson equation of state is chosen to calculate the required thermodynamic properties. Huang
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21 et al. regressed the binary interaction coefficients and yielded an acceptable estimation of the vapor-liquid equilibrium
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23 relationship.18 The model was also frequently adopted by others in the modeling and simulation of the RDC-SRS for the
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25 disproportionation of trichlorosilane to silane.
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silane (161K) < MCS (243.15K) < DCS (281.45K) < TCS (305K) < STC (330K) (9)
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2.2. Synthesis and Design of the RDC-SRS and RDC-MRS. In view of the fact that the disproportionation of
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32 trichlorosilane to silane is a three-stage consecutive reversible reaction, it is then reasonable and sufficient to assume here that
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34 the RDC-MRS accommodates up to three reactive sections, namely, including the options for the RDC-DRS and the reactive
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36 distillation columns with triple reactive sections (RDC-TRS). In order to establish a fair basis for the comparison of the
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38 RDC-SRS, RDC-DRS, and RDC-TRS, we specify here the total number of stages and the total number of reactive stages to be
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40 60 (including condenser and reboiler as well) and 31 (each reactive stage is assumed to contain 60.25 mole of resin Amberlyst
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42 A-21), respectively, for the three process designs to be examined. In fact, these values are slightly different from those of
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44 reference 18. Although the process designs and their operating conditions are designated somewhat arbitrarily, they do not
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46 influence the reasonability and conclusions of the current work. Under these assumptions, the condenser heat duty can simply
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48 be adopted as an effective metric for the comparison of their steady-state performance (because the normal boiling-point of
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silane is quite low (i.e., only 161 K) and the required coolant in condenser is much more expensive than the heating medium in
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reboiler), thereby avoiding the complicated estimations of capital investment and operating cost in case that total annual cost is
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55 chosen as a performance index. A simple grid-search method is adopted to synthesize and design the RDC-SRS, RDC-DRS,
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4 process design and this is why so many researchers have adopted it in process development. 2, 9, 14
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For the RDC-SRS, it contains two separating sections (i.e., the rectifying section and stripping section) and one reactive
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section and the structural decision variables for process synthesis and design include the number of stages in the two separating
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11 sections and the feed location of TCS (Throughout the current work, the reflux flow rate and condenser heat duty are employed,
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13 respectively, to keep the top and bottom products on their specifications and are not addressed here as operating decision
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15 variables). Figure 2 shows the relationship between the condenser heat duty and those structural decision variables. Note that
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17 the first separating section should contain 13 stages and moving away from this value elicits increases in the heat duty of
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19 condenser (c.f., Figure 2a). The influence of the number of reactive stages in the reactive section is also examined here and the
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21 optimum value is confirmed to be 31, i.e., the exact value as we assumed in the preceding paragraph (c.f., Figure 2b). The feed
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23 of TCS should be introduced onto stage 23, above which an enlarged heat duty of condenser is aroused (c.f., Figure 2c). The
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25 resultant optimum design of the RDC-SRS is depicted in Figure 5a, with the heat duties of condenser and reboiler as 412.6 kW
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and 453.8 kW, respectively.
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For the RDC-DRS, it involves three separating sections (i.e., the rectifying section, one intermediate separating section,
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32 and stripping section) and two reactive sections and the structural decision variables comprise the number of stages in the three
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34 separating sections, the number of reactive stages in the two reactive sections, and the feed location of TCS. Figure 3 shows the
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36 relationship between the condenser heat duty and those structural decision variables. While the three separating sections
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38 accommodate, respectively, 4, 10, and 15 stages (c.f., Figures 3a and 3c), the two reactive sections 7 and 24 stages, respectively
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40 (c.f., Figure 3b). In particular, a high degree of sensitivity is noticed between the number of stages in the upper reactive section
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42 and the heat duty of condenser, implying the great impact by the arrangement of two reactive sections. The feed of TCS enters
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44 now onto stage 24 due to the adoption of two reactive sections in process configuration (c.f., Figure 3d). The optimum design
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46 of the RDC-DRS is sketched in Figure 5b, with the heat duties of condenser and reboiler shrunk to be 376.4 kW and 417.7 kW,
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For the RDC-TRS, it consists of four separating sections (i.e., the rectifying section, two intermediate separating sections,
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and stripping section) and three reactive sections and the structural decision variables include the number of stages in the four
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55 separating sections, the number of reactive stages in the three reactive sections, and the feed location of TCS. Figure 4 shows
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4 accommodate, respectively, 4, 3, 8, and 14 stages (c.f., Figures 4a, 4c, and 4e), the three reactive sections 1, 5, and 25 stages,
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respectively (c.f., Figures 4b and 4d). Again, a relatively high degree of sensitivity is observed between the number of stages in
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the upper and middle reactive sections and the heat duty of condenser, implying the great impact by the arrangement of three
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11 reactive sections. The feed of TCS still enters onto stage 24 in spite of the adoption of three reactive sections (c.f., Figure 4f).
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13 The optimum design of the RDC-TRS is depicted in Figure 5c, with the heat duties of condenser and reboiler dropped further
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15 to be 367.6 kW and 408.8 kW, respectively.
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17 2.3. RDC-SRS versus RDC-MRS. Table 2 details the comparison of steady-state performance between the RDC-SRS,
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19 RDC-DRS, and RDC-TRS. With the adoption of two reactive sections, the RDC-DRS diminishes the heat duties of condenser
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21 and reboiler by 8.77 % and 7.96 %, respectively, as compared with the RDC-SRS. Likewise, with the adoption of three reactive
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23 sections, the RDC-TRS abates the heat duties of condenser and reboiler by 10.91 % and 9.92 %, respectively, as compared with
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25 the RDC-SRS. The dramatic declines in operating cost highlight the favorable effect by the arrangement of multiple reactive
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sections in the RDC-DRS and RDC-TRS. It is worth noting here that the great improvement in steady-state performance
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implies also a great reduction of capital investment by the arrangement of multiple reactive sections in process synthesis and
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32 design.
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34 2.4. Roles of Multiple Reactive Sections in the RDC-MRS. In Figure 6, the steady-state profiles of liquid compositions
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36 are shown for the RDC-SRS, RDC-DRS, and RDC-TRS. Note that the separation between STC and TCS is mainly conducted
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38 near the bottom end and there exists almost no differences between the three process designs examined there. As for the top end,
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40 sharp differences can, however, be readily observed. In the case of the RDC-SRS (c.f., Figure 6a), the steady-state profile of
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42 MCS exhibits a fairly high and wide plateau with a value nearly to one from stage 3 to stage 11 (which forms essentially a
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44 pinch zone there) and this may incur great difficulties in the purification of silane because their relative volatilities are adjacent
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46 to each other within the five components involved (The stages are counted from the top down to the bottom, with the condenser
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48 as stage 1 and the reboiler as stage 60). The drawback is apparently related to the adoption of a single reactive section in
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process synthesis and design that makes the RDC-SRS unable to effectively coordinate the three consecutive reversible
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reactions involved. Huang et al. also reported an extremely similar phenomenon for the RDC-SRS and attempted to rely on the
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55 applications of side-condensers to counteract its negative effect, however, only slight improvement was gained. Regarding
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4 suppressed in that area as compared with that of the RDC-SRS and this results in the ascending of the peak of the DCS
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composition. The difficulty in the purification of silane is thus greatly alleviated because the separation now occurs mainly
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between silane, MCS, and DCS in this situation. As far as the RDC-TRS is concerned (c.f., Figure 6c), owing to the
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11 arrangement of three reactive sections, the peaks of the steady-state profiles of MCS and DCS are slightly enhanced as
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13 compared with those of the RDC-DRS and this adjustment helps to generate more silane and MCS at the top ends of the
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15 intermediate and upper reactive sections, thereby presenting a favorable impact to the purification of silane in the rectifying
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17 section.
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19 In Figure 7, the steady-state profiles of net reaction rates for the three consecutive reversible reactions involved in the
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21 disproportionation of trichlorosilane to silane are shown, respectively, for the RDC-SRS, RDC-DRS, and RDC-TRS. In the
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23 case of the RDC-SRS, because all of the three consecutive reversible reactions compete within the single reactive section, the
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25 three curves intersect each other and this signifies rather strong couplings between them (c.f., Figure 7a). With regard to the
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RDC-DRS, while the first-stage reaction occurs almost completely and independently in the lower reactive section, the second-
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and third-stage reactions take place almost completely in the upper reactive section (c.f., Figure 7b). In particular, in the upper
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32 reactive section the second-stage reaction proceeds primarily at the bottom end and the third-stage reaction at the top end,
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34 sharing a common area between stages 6 and 10. The intersection of the two curves still implies the existence of rather strong
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36 coupling between the two reactions and the need to adopt an additional reactive section to further alleviate it. In the case of the
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38 RDC-TRS, the three consecutive reversible reactions involved now proceed almost independently (c.f., Figure 7c), with the
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40 first-stage reaction occurring almost completely in the lower reactive section, the second-stage reaction occurring almost
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42 completely in the middle reactive section, and the third-stage reaction occurring almost completely in the upper reactive section.
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44 The changing pattern of the profiles of net reaction rates from the RDC-SRS to the RDC-DRS and RDC-TRS highlights the
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46 pivotal role of adopting multiple reactive sections in coordinating the three consecutive reversible reactions involved in the
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48 disproportionation of trichlorosilane to silane.
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3. DISCUSSION
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55 Apart from the rather unfavorable reaction kinetics of a near zero thermodynamic conversion, the disproportionation of
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57 trichlorosilane to silane is also characterized by a fairly interactive nature because TCS, DCS, and MCS function as both
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4 reactants (or intermediate reactants) and intermediate products in the three-stage consecutive reversible reaction processed.
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This feature implies strong coupling between the three consecutive reversible reactions involved and a careful coordination
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must be made between them in order to seek the potentials of reactive distillation columns. It should be stressed here that it also
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11 represents a key issue that is closely related to the reinforcement of internal mass integration and internal energy integration
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13 between the reaction operations and the separation operations involved. It is, therefore, of great importance to
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15 effectively tackle this issue during the stage of process synthesis and design. The RDC-SRS fails to tackle that issue effectively
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17 due to the shortage of structural design variables and this is why it requires the highest heat duties in condenser and reboiler.
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19 With the arrangement of two reactive sections, the RDC-DRS receives two degrees of freedom more than the RDC-SRS in
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21 coordinating the three consecutive reversible reactions involved and this gives rise consequently to great reductions in the heat
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23 duties of condenser and reboiler. With the arrangement of three reactive sections, the RDC-TRS gains further two degrees of
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25 freedom more than the RDC-DRS and the additional flexibility permits further reductions in the heat duties of condenser and
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reboiler. The varying tendency indicates clearly the favorable effect by the incremental adoption of reactive sections in the
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synthesis and design of reactive distillation columns and confirms definitely the number of reactive sections can work as
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32 important and effective decision variables to enhance their steady-state performance. Although the interpretation has been
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34 derived from the current example system studied, it should be considered to be of general significance to the synthesis and
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36 design of any other reactive distillation columns because all of our research results obtained so far have been in excellent
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38 accordance with this deduction. It is worthy to mention here the fact that the RDC-MRS (i.e., the RDC-DRS and
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40 RDC-TRS) has been derived based on exactly the same operating conditions as the RDC-SRS. This signifies that no
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42 prerequisites are needed at all for the application of the novel scheme as compared with its conventional analogues, thereby
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44 permitting wide applicability and great advantages in process synthesis and design.
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46 The disproportionation of trichlorosilane to silane by various reactive distillation columns features a common drawback of
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48 high refrigeration requirement because the normal boiling-point of silane is quite low (i.e., only 161 K) and this makes the
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application of side-condensers a frequently adopted strategy to improve the thermodynamic efficiency of these processes. 18 For
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the RDC-MRS, the unique cascade structure of separating sections and reactive sections may even simplify the arrangement of
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55 side-condensers to its rectifying section (which behaves essentially as a heat source in the light of the second law of
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57 thermodynamics). Because the side-condensers usually locate in the separating sections, the search of their locations becomes
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4 relatively easier in the RDC-MRS than in the RDC-SRS. Figure 8 shows the arrangement of two side-condensers to the
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RDC-DRS in case of their heat duties being assumed uniformly to be 100 kW. For the top side-condenser (where the bottom
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side-condenser has been fixed arbitrarily at stage 18), it should be located at stage 4 since further descending its location
9
10
11 introduces relatively small increase of temperature (The higher the temperature is, the cheaper the coolant of the
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13 side-condenser becomes) and relatively great increase of condenser heat duty (c.f., Figure 8a). For the bottom side-condenser
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15 (where the top side-condenser has been fixed at stage 4), it should be located at stage 22 because moving away from the stage
16
17 leads to either relatively small increase of temperature or relatively great increase in condenser heat duty (c.f., Figure 8b). The
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19 resultant design of the RDC-DRS with two side-condensers is sketched in Figure 8c. Note the fact that the two side-condensers
20
21 are connected, respectively, to two specific stages of the top two separating sections. Figure 9 shows the arrangement of three
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23 side-condensers to the RDC-TRS in case of their heat duties being assumed uniformly to be 100 kW. Extremely similar to the
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25 situation of Figure 8a, the top side-condenser should again be located at stage 4 when the intermediate and bottom
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side-condensers have been fixed arbitrarily at stages 8 and 18, respectively (c.f., Figure 9a). In terms of Figure 9b (where the
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top and bottom side-condensers have been fixed at stages 4 and 18, respectively), the intermediate side-condenser should be
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32 located at stage 7 because further lowering its position arouses relatively great augment of condenser heat duty. With reference
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34 to Figure 9c (where the top and intermediate side-condensers have been fixed, respectively, at stages 4 and 8), the bottom
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36 side-condenser should be located at stage 21 because moving away from this stage results in either relatively small or relatively
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38 great increase in temperature and condenser heat duty (c.f., Figure 9c). The resultant design of the RDC-TRS with three
39
40 side-condensers is delineated in Figure 9d. Note again the fact that the three side-condensers are connected, respectively, to
41
42 three specific stages of the top three separating sections. These interesting results help also to reveal the thermodynamic
43
44 rational of adopting multiple reactive sections in the synthesis and design of reactive distillation columns separating
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46 complicated reacting mixtures involving multiple reversible reactions. Although not shown explicitly in the current work, the
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48 stage temperatures in the reactive sections of the RDC-SRS, RDC-DRS, and RDC-TRS are all below the thermal resistance
49
50
temperature of the resin Amberlyst A-21 (i.e., 373.15 K). With the arrangement of two and three side-condensers to the
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RDC-DRS and RDC-TRS, respectively, the resultant temperatures and compositions of silane in the reactive sections display
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55 only slight changes as compared with their original values.
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4 4. CONCLUSIONS
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Adopting multiple reactive sections allows the RDC-MRS to have more degrees of freedom for process synthesis and
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8
design than the RDC-SRS. These additional degrees of freedom can be employed to reinforce internal mass integration and/or
9
10
11 internal energy interaction between the reaction operations and the separation operations involved, leading frequently to great
12
13 improvement in system performance as compared with the RDC-SRS. In the case of the separations of multiple-stage
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15 consecutive reversible reactions, these additional degrees of freedom can also be used to coordinate the potentially intricate
16
17 couplings between the multiple consecutive reversible reactions involved, yielding again a favorable effect to the steady-state
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19 performance of the RDC-MRS. With reference to the disproportionation of trichlorosilane to silane, the potential advantages of
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21 the RDC-MRS has been clearly demonstrated through the in-depth comparison of steady-state performance between the
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23 RDC-SRS, RDC-DRS, and RDC-TRS. With the incremental arrangement of reactive sections, the heat duties of condenser and
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25 rebolier display a downward trend from the RDC-SRS to the RDC-DRS and then the RDC-TRS. Arrangements of
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side-condensers have also been attempted to the RDC-DRS and RDC-TRS and they all have been found to locate in the
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separating sections above the feed of TCS. Since these separating sections are essentially heat sources, the outcomes have
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32 shown the thermodynamic rational of adopting multiple reactive section in process synthesis and design. Although these
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34 findings have been derived from the specific case study chosen, it should be viewed to be of general significance for the
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36 development of reactive distillation columns separating complicated reacting mixtures involving multiple reversible reactions.
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38
39
40 ACKNOWLEDGEMENTS
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42 The current work is financially supported by The National Natural Science Foundation of China under the grant numbers
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44 of 21076015, 21376018, 21576014, and 21676011 and The Fundamental Research Funds for the Central Universities under the
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46 grant number of ZY1503.
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48
49
50
NOTATION
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52
A, B, C, D = hypothetical reacting components
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55 DCS = dichlorosilane
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57 F = feed flow rate, kmol/s
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5 ∆Ηr =reaction heat, kJ/kmol
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k = rate constant of forward reactions
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K = chemical equilibrium constant
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11 MCS = monochlorosilane
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13 NF = feed stage
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15 NR, I = number of stages in the ith reactive section
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17 NS, I = number of stages in the ith separating section
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19 P = pressure, Pa
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21 Q = heat duty, kW
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23 r = reaction rate, kmol/s
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25 R = reactive section
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RDC-DRS = reactive distillation column with double reactive sections
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RDC-MRS = reactive distillation column with multiple reactive sections
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32 RDC-SRS = reactive distillation column with a single reactive section
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34 RDC-TRS = reactive distillation column with triple reactive sections
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36 RR = reflux ratio
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38 S = separating section
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40 SIL = silane
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42 STC = silicon tetrachloride
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44 T = temperature, K
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46 TCS = trichlorosilane
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48 x = liquid composition
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50
α = relative volatility
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52
Subscripts
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55 COND = condenser
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57 REB = reboiler
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59 13
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6
LITERATURE CITED
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(1) Taylor, R.; Krishna, R. Modeling Reactive Distillation. Chem. Eng. Sci. 2000, 55, 5183.
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11 (2) Luyben, W. L.; Yu, C. C. Reactive Distillation Design and Control. New Jersey: John Wiley & Sons, Inc., 2008.
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13 (3) Malone, M. F.; Doherty, M. F. Reactive Distillation. Ind. Eng. Chem. Res. 2000, 39, 3953.
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15 (4) Kaymak, D. B.; Luyben, W. L. Quantitative Comparison of Reactive Distillation with Conventional Multiunit
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17 Reactor/Column/Recycle Systems for Different Chemical Equilibrium Constants. Ind. Eng. Chem. Res. 2004, 43, 2493.
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19 (5) Huang, K.; Nakaiwa, M.; Wang, S. J.; Tsutsumi, A. Reactive Distillation Design with Considerations of Heats of
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21 Reaction. AIChE J. 2006, 52, 2518.
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23 (6) Kaymak, D. B.; Luyben, W. L. Effect of Relative Volatility on the Quantitative Comparison of Reactive Distillation
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25 and Conventional Multi-unit Systems. Ind. Eng. Chem. Res. 2004, 43, 3151.
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(7) Chen, C. S.; Yu, C. C. Effects of Relative Volatility Ranking on Design and Control of Reactive Distillation
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Systems with Ternary Decomposition Reactions. Ind. Eng. Chem. Res. 2008, 47, 4830.
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32 (8) Thotla, S.; Mahajani, S. Reactive Distillation with Side Draw. Chem. Eng. Proc. 2009, 48, 927.
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34 (9) Tung, S.T.; Yu, C.C. Effects of Relative Volatility Ranking to the Design of Reactive Distillation. AIChE J. 2007, 53,
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36 1278.
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38 (10) Zhang, L.; Chen, H.; Yuan, Y.; Yu, J.; Wang, S.; Huang, K. Synthesis and Design of Reactive Distillation Columns
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40 with Two Reactive Sections. Chem. Eng. Res. Des. 2015, 100, 311.
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42 (11) Zhang, L.; Chen, H.; Yuan, Y.; Wang, S.; Huang, K. Adopting Feed Splitting in Design of Reactive Distillation
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44 Columns with Two Reactive Sections. Chem. Eng. Proc. 2015, 89, 9.
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46 (12) Chen, H.; Huang, K.; Liu, W.; Zhang, L.; Wang, S.; Wang, S. J. Enhancing Mass and Energy Integration by
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48 External Recycle in Reactive Distillation Columns. AIChE J. 2013, 59, 2015.
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(13) Chen, H.; Zhang, L.; Huang, K.; Yuan Y.; Zong, X.; Wang, S.; Liu, L. Reactive Distillation Columns with Two
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Reactive Sections: Feed Splitting plus External Recycle. Chem. Eng. Proc. 2016, 108, 189.
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55 (14) Yu, C.; Yao, X.; Huang, K.; Zhang, L.; Wang, S.; Chen, H. A Reactive Distillation Column with Double Reactive
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57 Sections for the Separations of Two-Stage Consecutive Reversible Reactions. Chem. Eng. Proc. 2014, 79, 56.
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59 14
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4 (15) Mueller, I.; Kenig, E. V. Reactive Distillation in a Dividing Wall Column: Rate-Based Modeling and Simulation.
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Ind. Eng. Chem. Res. 2007, 46, 3709.
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(16) Yu, J.; Shi, L.; Yuan, Y.; Chen, H.; Wang, S.; Huang, K. Thermally Coupled Reactive Distillation System for the
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11 Separations of Cyclohexene/Cyclohexane Mixtures. Ind. Eng. Chem. Res. 2016, 55, 311.
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13 (17) Union Carbide. Feasibility of the Silane Process for Producing Semiconductor Grade Silicon. Final Report (Phases
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15 I and II), JPL Contract 954334; U.S. DOE, 1979.
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17 (18) Huang, X.; Ding, W.; Yan, J.; Xiao, W. Reactive Distillation Column for Disproportionation of Trichlorosilane to
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19 Silane: Reducing Refrigeration Load with Intermediate Condensers. Ind. Eng. Chem. Res. 2013, 52, 6211.
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21 (19) Alcántara-Ávila, J. R.; Sillas-Delgado, H. A.; Segovia-Hernández, J. G.; Gómez-Castro, F. I.; Cervantes-Jauregui, J.
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23 A. Optimization of a Reactive Distillation Process with Intermediate Condensers for Silane Production. Comput. Chem. Eng.
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25 2015, 78, 85.
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(20) Alcántara-Ávila, J. R.; Tanaka, M.; Ramírez-Márquez, C.; Gómez-Castro, F. I.; Segovia-Hernández, J. G.; Sotowa,
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K. I.; Horikawa, T. Design of a Multitask Reactive Distillation with Intermediate Heat Exchangers for the Production of Silane
30
31
32 and Chlorosilane Derivates. Ind. Eng. Chem. Res. 2016, 55, 10968.
33
34 (21) Ramírez-Márquez, C.; Sánchez-Ramírez, E.; S.; Quiroz-Ramírez, J. J.; Gómez-Castro, F. I.; Ramíre-Corona, N.
35
36 Cervantes-Jauregui, J. A.; Segovia-Hernández, J. G. Dynamic Behavior of a Multi-tasking Reactive Distillation Column for
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38 Production of Silane, Dichlorosilane and Monochlorosilane. Chem. Eng. Proc. 2016, 108, 125.
39
40 (22) Wang, K. Synthesis and Design of Reactive Distillation Columns with Multiple Reactive Sections. Master Thesis of
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42 Beijing University of Chemical Technology. 2015.
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4 Figure Captions
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Figure 1. Schemes of the RDC-SRS and RDC-MRS: (a) RDC-SRS, (b) RDC-MRS.
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Figure 2. Relationship between condenser heat duty and relevant decision variables for the RDC-SRS.
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11 Figure 3. Relationship between condenser heat duty and relevant decision variables for the RDC-DRS.
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13 Figure 4. Relationship between condenser heat duty and relevant decision variables for the RDC-TRS.
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15 Figure 5. Optimum process designs for the disproportionation of trichlorosilane to silane: (a) RDC-SRS, (b) RDC-DRS, (c)
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17 RDC-TRS.
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19 Figure 6. Profiles of liquid compositions: (a) RDC-SRS, (b) RDC-DRS, (c) RDC-TRS.
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21 Figure 7. Profiles of reaction rates: (a) RDC-SRS, (b) RDC-DRS, (c) RDC-TRS.
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23 Figure 8. Arrangement of two side-condensers to the RDC-DRS: (a) impact of the top side-condenser, (b) impact of the
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25 bottom side-condenser, (c) RDC-DRS with two side-condensers.
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27
Figure 9. Arrangement of three side-condensers to the RDC-TRS: (a) impact of the top side-condenser, (b) impact of the
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intermediate side-condenser, (c) impact of the bottom side-condenser, (d) RDC-TRS with three side-condensers.
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Figure 1
57 Xinxiang Zang, Kejin Huang, Yang Yuan, Haisheng Chen, Liang Zhang, Shaofeng Wang, and Kun Wang
58 Reactive Distillation Columns with Multiple Reactive Sections: A Case Study for the Disproportionation of Trichlorosilane to Silane
59 17
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427
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8

QCOND (kW)
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11 425
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15 424
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17 NS, 1
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19 (a)
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24 430
QCOND (kW)

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32 29 30 31 32 33
33 NR, 1
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36 418
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40 416
QCOND (kW)

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44 414
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48 412
49 21 22 23 24 25
50 NF
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Figure 2
57 Xinxiang Zang, Kejin Huang, Yang Yuan, Haisheng Chen, Liang Zhang, Shaofeng Wang, and Kun Wang
58 Reactive Distillation Columns with Multiple Reactive Sections: A Case Study on the Disproportionation of Trichlorosilane to Silane
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QCOND (kW)

QCOND (kW)
8 384
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10 380
11 379

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13 374 374
14 2 3 4 5 6 5 6 7 8 9
NS, 1 NR, 1
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16 (a) (b)
17 380 377.3
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20 379
377.0
21
QCOND (kW)

QCOND (kW)
22 378
23
24 376.7
377
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27 376 376.4
8 9 10 11 12 22 23 24 25 26
28 NS, 2 NF
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30 (b) (d)
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Figure 3
57 Xinxiang Zang, Kejin Huang, Yang Yuan, Haisheng Chen, Liang Zhang, Shaofeng Wang, and Kun Wang
58 Reactive Distillation Columns with Multiple Reactive Sections: A Case Study on the Disproportionation of Trichlorosilane to Silane
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QCOND (kW)

QCOND (kW)
380 376
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9 375 373
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11 370 370
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13 365 367
14 2 3 4 5 6 1 2 3 4 5
NS, 1 NR, 1
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16 (a) (b)
17 370 382
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20 378
369

QCOND (kW)
21
QCOND (kW)

22 374
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24 368
370
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27 367 366
28 1 2 3 4 5 3 4 5 6 7
NS, 2 NR, 2
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30 (c) (d)
31 371 368.6
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370
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368.2
QCOND (kW)

35
QCOND (kW)

36 369
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367.8
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368
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41 367 367.4
6 7 8 9 10 22 23 24 25 26
42 NS, 3 NF
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44 (e) (f)
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56 Figure 4
57 Xinxiang Zang, Kejin Huang, Yang Yuan, Haisheng Chen, Liang Zhang, Shaofeng Wang, and Kun Wang
58 Reactive Distillation Columns with Multiple Reactive Sections: A Case Study on the Disproportionation of Trichlorosilane to Silane
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Figure 5
57 Xinxiang Zang, Kejin Huang, Yang Yuan, Haisheng Chen, Liang Zhang, Shaofeng Wang, and Kun Wang
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57 Figure 6
Xinxiang Zang, Kejin Huang, Yang Yuan, Haisheng Chen, Liang Zhang, Shaofeng Wang, and Kun Wang
58 Reactive Distillation Columns with Multiple Reactive Sections: A Case Study on the Disproportionation of Trichlorosilane to Silane
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57 Figure 7
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58 Reactive Distillation Columns with Multiple Reactive Sections: A Case Study on the Disproportionation of Trichlorosilane to Silane
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Condenser heat duty Condenser heat duty
5 Temperature Temperature
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7
192 196 350
8
QCOND (kW)

QCOND (kW)
287
9

T (K)

T (K)
10 269
11 191 192 344
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190 233 188 338
15 3 4 5 6 16 19 22 25
16 Stage number Stage number

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56 Figure 8
57 Xinxiang Zang, Kejin Huang, Yang Yuan, Haisheng Chen, Liang Zhang, Shaofeng Wang, and Kun Wang
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Temperature Temperature
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298 323
7 89
283 313
8

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QCOND (kW)

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9

T (K)
T (K)
268 87 303
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88
11 253 293
12 85
86 283
13 238

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84 223
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22 91 352
Condenser heat duty
23 Temperature
24 89 349

25
QCOND (kW)

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T (K)

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28 85 343

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81 337
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Figure 9
57 Xinxiang Zang, Kejin Huang, Yang Yuan, Haisheng Chen, Liang Zhang, Shaofeng Wang, and Kun Wang
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5 Table 1. Physicochemical Properties and Operating Conditions for the Disproportionation of Trichlorosilane to Silane
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Table 2. Comparison between the RDC-SRS, RDC-DRS, and RDC-TRS
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4 Table 1. Physicochemical Properties and Operating Conditions for the Disproportionation of Trichlorosilane to Silane
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6 Parameter Value
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8 Top stage pressure (atm) 5.0
9
10 Stage pressure drop (kPa) 0.5
11
12 Top product specification (Silane, mol %) 99
13
14 Bottom product specification (STC, mol %) 99
15
16 First-stage reaction 30045
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18 Reaction activation energy, EA (kJ/kmol) Second-stage reaction 51083
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20 Third-stage reaction 26320
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22
First-stage reaction 73.5
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24
Reaction frequency factor, K0 (1/s) Second-stage reaction 949466.4
25
26
Third-stage reaction 1176.9
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28
First-stage reaction 0.1856
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31 Reaction equilibrium constant Second-stage reaction 0.7669
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33 Third-stage reaction 0.6890
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35 STC 330
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37 TCS 305
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39 Boiling temperatures at atmospheric pressure (K) DCS 281.45
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41 MCS 243.15
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43 Silane 161
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4 Table 2. Comparison between the RDC-SRS, RDC-DRS, and RDC-TRS
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6 Process design RDC-SRS RDC-DRS RDC-TRS
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8 QCOND (kW) 412.6 376.4 367.6
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10 Comparison 100 % 91.23 % 89.09 %
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12 QREB (kW) 453.8 417.7 408.8
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14 Comparison 100 % 92.04 % 90.08 %
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57 Xinxiang Zang, Kejin Huang, Yang Yuan, Haisheng Chen, Liang Zhang, Shaofeng Wang, and Kun Wang
58 Reactive Distillation Columns with Multiple Reactive Sections: A Case Study on the Disproportionation of Trichlorosilane to Silane
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