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Design consideration of dimethyl succinate production process

Article in Chemical Papers · December 2014

DOI: 10.2478/s11696-014-0580-4

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 Chemical Papers
Design consideration of dimethyl succinate production process
--Manuscript Draft--

Manuscript Number:

Full Title: Design consideration of dimethyl succinate production process

Article Type: Kossaczký 90

Corresponding Author: Jozef Markoš

Slovak University of Technology
Bratislava, SLOVAKIA

Corresponding Author Secondary

Information:

Corresponding Author's Institution: Slovak University of Technology

Corresponding Author's Secondary

Institution:

First Author: Jozef Dudáš

First Author Secondary Information:

Order of Authors: Jozef Dudáš

Marcel Kotora

Michal Bradáč

Jozef Markoš

Order of Authors Secondary Information:

Abstract: Esterification of succinic acid to form dimethyl succinate has been analysed and the
process design is presented in this paper. The process analysis and design are based
on our own experimental data (kinetics), information from open literature and own
mathematical models and computer programs for process simulation and evaluation.
Reactive distillation and a tubular reactor followed by separation of components from
the reaction mixture were considered and evaluated. An economic analysis indicated
that operational costs dominate over the capital ones in the costs estimation and that
the integration of partial processes into one vessel (reactive distillation) is
advantageous. However, according to the analysis of the process conditions
(temperature and pressure) for the reaction and distillation, it is impossible to execute
the process in one vessel. Therefore, a fixed bed reactor combined with distillation was
proposed and the technology has been developed.

Suggested Reviewers: Jiří Hanika, prof.

ICPF Prague, CZ
jiri.hanika@vscht.cz
published several paper about reactive distillation

Péter Mizsey, prof.

Budapest University of Technology
mizsey@ch.bme.hu
experience with rectification processes

Stevan Popov, prof.

University of Novi Sad
pop@uns.ac.rs
experience with biorefinery technologies, renewable biomass conversion...

Author Comments:

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Click here to download Manuscript: Chem_Pap_DMS_3_po B.docx

1 Design consideration of dimethyl succinate production process

2
3 Jozef Dudáš, Marcel Kotora, Michal Bradáč, Jozef Markoš1
4
5 Institute of Chemical and Environmental Engineering, Faculty of Chemical and Food
6 Technology, Slovak University of Technology, Radlinského 9, 812 97 Bratislava, Slovakia
7
8 Abstract:
9
10 Esterification of succinic acid to form dimethyl succinate has been analysed and the process
11 design is presented in this paper. The process analysis and design are based on our own
12 experimental data (kinetics), information from open literature and own mathematical models
13 and computer programs for process simulation and evaluation. Reactive distillation and a
14 tubular reactor followed by separation of components from the reaction mixture were
15 considered and evaluated. An economic analysis indicated that operational costs dominate
16 over the capital ones in the costs estimation and that the integration of partial processes into
17 one vessel (reactive distillation) is advantageous. However, according to the analysis of the
18 process conditions (temperature and pressure) for the reaction and distillation, it is impossible
19 to execute the process in one vessel. Therefore, a fixed bed reactor combined with distillation
20 was proposed and the technology has been developed.
21
22 Introduction
23
24 In the past two decades, the biorefinery concept based on biotechnological (biocatalytical)
25 conversion of renewable biomass to many high added value products has seemed to be a
26 promising way of substituting fossil fuels, mainly petroleum (Budarin et al., 2007, Demirbas,
27 2009). Biosynthesis of carboxylic acids, often followed by their esterification by (bio)ethanol
28 or methanol provides useful and required raw materials or intermediates of commercial
29 interest (Orjuela et al., 2011). Among these, the increasing attention is attracted to the
30 production of succinic acid and its dialkylesters. Dialkyl succinates are important chemicals
31 for industries producing food and pharmaceutical products, surfactants and detergents, green

1
correspondingauthor, jozef.markos@stuba.sk

1
32 solvents, biodegradable plastics and also ingredients to stimulate animal and plant growth and
33 many others.
34
35 Information about diethyl succinate production can be found in open literature (Benedict et
36 al., 2006, Budarin et al., 2007, Orjuela et al., 2011, Orjuela et al, 2012); however, there is a
37 lack of information about the design of dimethyl succinate process. Esterification of succinid
38 acid (SA) with methanol (MeOH) producing dimethyl succinate (DMS) proceeds by two
39 equilibrium reactions, with water (W) and an intermediate of monomethyl succinate (MMS)
40 as the side product according to the following reaction scheme:
41 SA  MeOH MMS  W (1)
42 MMS  MeOH DMS  W (2)
43 Esterification is typically catalysed by strong mineral acids or acidic ion exchange resins but
44 the process is also autocatalysed by succinic acid. High conversion of SA with high yield
45 towards DMS and high purity of the final product, DMS (99.0 mass % and higher), is required
46 in industrial processes. According to our knowledge, no information about the dimethyl
47 succinate production process can be found in open literature.
48 In the past decade, strong academic and industrial interest was devoted to hybrid
49 reactive – separation systems. The process can save raw material and shift chemical
50 equilibrium towards the desired product; moreover, the integration of a chemical reactor and
51 the separation process into one integrated unit also saves capital and operational costs
52 (Krishna, 2002, Blahušiak et al., 2010, Mihaľ et al., 2012, 2013). Nowadays, esters of
53 carboxylic acids are very often produced in hybrid reactive systems, especially in reactive
54 (catalytic) distillation or catalytic distillation coupled with membrane separation (Hanika et
55 al., 1999, Buchaly et al., 2007, Kotora et al., 2008, Kotora et al., 2009, Tavan and Hosseini,
56 2013).
57 The advantages of reactive (catalytic) distillation are well known: chemical
58 equilibrium limitations can be overcome, higher selectivity achieved, the heat of the reaction
59 can be used in-situ for distillation, hot spots and run-away can be avoided, azeotropic or
60 closely boiling mixtures can be more easily separated. Disadvantages and constraints of the
61 process due to component volatilities (reactants and products must have suitable volatility to
62 maintain high concentration of reactants and low concentrations of products in the reaction
63 zone), residence time requirements (long residence time for the reaction requires large column
64 size and tray liquid hold-ups), process conditions mismatch (in some processes, the optimum
65 conditions of the distillation temperature and pressure can be far from optimal conditions for
2
66 the reaction and vice versa) etc., must also be considered in the application of reactive
67 distillation (Taylor & Krishna., 2000).
68 Despite the number of papers in open literature dealing with modelling and application
69 of specific hybrid systems, there are practically no general rules for the selection and decision
70 whether the hybrid system is suitable for a specific process. Mitkowski et al. (2009) presented
71 a methodology for the analysis and design of hybrid processes, applied later for ethyl lactate
72 synthesis (Mitkowski, 2011). Another analysis of the suitability of reactive distillation for a
73 reaction – separation system was done by Schembecker and Tlatlik (2003). According to their
74 analysis, the first condition is that a reaction system has to be suitable for the reactive
75 separation process. Parameters like residence time, heat of reaction, reaction equilibrium
76 limitations, relative volatility of components etc. have to be taken into account in the process
77 evaluation. Only then it is considered whether the separation unit enhances the overall
78 chemical process effectiveness. The individual processes integration leads to the integration
79 of their constraints and it needs to be considered. An example of the windows of operational
80 conditions for a hybrid process with different optimum conditions for distillation and reaction
81 kinetics is presented in Fig. 1. The window with suitable operational conditions for both
82 processes is significantly smaller comparing the individual processes. Another factor which
83 needs to be considered is given by the equipment characteristics as it is shown in Fig.1. This
84 simple example indicates that hybrid processes are not a universal solution and relevant
85 analysis is required for decision making.
86
chemical separation chemical apparatus separation chemical
operation operation operation operation operation operation
window window window window window window
temperature

temperature

temperature

pressure pressure pressure

Overlaping area in which the RD process

may be feasible
Fig.1. Superposition area of operation conditions in process integration (Schembecker and Tlatlik,
2003)
87

3
 88 The process of dimethyl succinate production is analysed and its design is presented in this
89 paper. The process analysis and design is based on our own experimental data, information
90 from open literature and own mathematical models and computer programs for process
91 simulation and evaluation. The flow sheet diagram as well as the main process characteristics
92 and dimensions of the main equipment are provided in the present paper.
93
94 Thermodynamic analysis of DMS synthesis

95
96 Thermodynamic analysis of the process is based on physico-chemical properties of
97 compounds involved in the process. Available databases, like DIPPR-801 (Rowley et al.,
98 2011) provided data only for SA, DMS, MeOH and W. Since the thermodynamic properties
99 of monomethyl succinate are not available, they were estimated using the following group of
100 contribution methods proposed by Reid et al. (1986):
101 - Joback method - critical properties, ideal gas standard enthalpy of formation, ideal gas
102 standard Gibbs energy of formation and boiling point,
103 - Missenard group contribution method - liquid heat capacity.
104
105 Table 1. Physical properties of compounds involved in the process

SA MMS DMS MeOH W

MW kg/mol 0.118 0.132 0.1461 0.032 0.018

 f H liq
0
,298 kJ/mol -940,0 -901.6 -845,1 -239.1 -285.83

 f Gliq
0
,298 kJ/mol -744.4 -689 -627.8 -166.9 -237,2

 vap H 343 kJ/mol 97.81 83.45 56.7 34,79 42.12

Tb °C 317.85 244.35 196.15 64.6 100
106
107 The model of ideal gas and non-ideal liquid phase was considered for vapour – liquid
108 equilibrium and the Wilson’s equation was used for the prediction of liquid phase activity
109 coefficients. Binary parameters for most mixtures were estimated using the UNIFAC method,
110 except for the methanol – water equilibrium obtained from the DECHEMA database.
111
112 Normal boiling points of components involved in the system are very different: from
113 317.9°C for succinic acid to 64.6°C for methanol. Since SA decomposes in the temperature

4
114 range close to normal boiling point, the separation of unreacted SA and MMS from the
115 reaction mixture via vacuum distillation was considered.
116
117 The SA is a crystalline material (its melting point is 187.5°C), with relatively low
118 solubility in methanol, water and even in the reaction products (MMS and DMS).
119 Experimental solubility data indicate that the solubility of succinic acid depends mostly on
120 temperature. It has been experimentally proven that complete dissolution of succinic acid in
121 methanol at the molar ratio of 1:5 can be achieved at temperatures above 50oC. The presence
122 of water, MMS and DMS has no significant effect on the SA solubility.
123
124 The values of reaction enthalpies (calculated using standard heats of formation, Table 1) at
125 298 K indicate that:
126 - the first reaction is slightly exothermic,  r1H liq ,298  8.43kJ mol-1 ,

127 - the second reaction is slightly endothermic,  r1H liq ,298  9.78kJ mol-1 ,

128 - temperature dependence of the reaction enthalpies for both reactions can be neglected.
129
130 Based on the thermodynamic data, equilibrium composition of the reaction mixture for a
131 given temperature and initial composition of reaction mixture (MeOH: SA molar ratio) can be
132 obtained solving two nonlinear algebraic equations:
5 5
K a , j    i j ,i  xi j ,i , j  1, 2
 
133 (3)
i 1 i 1

134 Theoretical equilibrium conversion of SA was higher than 0.99 and the yield of the
135 desired product (DMS) was higher than 0,89 in the investigated temperature and reactants
136 ratio interval (Fig. 2. )
137

5
 1.00

0.98

0.96

equilibrium yield 0.94

0.92

0.90

0.88
335 340 345 350 355 360 365
T/K

Fig 2: Calculated equilibrium yield vs. reaction temperature at different initial molar ratios of MeOH
and SA: R0  2 - long dashed line; R0  3.5 – solid line; R0  5.5 – dot-dashed line; R0  10 – short
dashed line.
138
139 Thermodynamic analysis indicated that the synthesis of DMS should be carried out in the
140 temperature range of 90°C – 100°C and at the methanol excess R0  5 .
141
142 Experimental part – estimation of kinetic parameters
143
144 Both, homogeneous and heterogeneous catalysis can be considered for the esterification
145 process. General advantage of homogeneous catalysis is the high efficiency of the process;
146 however, it is difficult to separate the catalyst from the post reaction mixture, which leads to
147 the catalyst loss. Acidic ion exchange resins are recommended catalysts for the esterification
148 of carboxylic acids. Delgado et al. (2007), Buchaly, et al. (2007), and Orjuela et al. (2011)
149 used this kind of catalysts for diethyl succinate synthesis. Therefore, the strong acidic ion
150 exchange resin Dowex DR-2030 has been identified as a suitable catalyst for the dimethyl
151 succinate synthesis. Maximum temperature of 100 – 110°C is allowed for most commercial
152 acidic ion exchange resins formed by sulphonated copolymers of styrene and divinylbenzene.
153
154 Kinetic experiments were carried out in two laboratory batch reactors:
155 - Mechanical stirred externally heated glass round bottom flask at the mixture boiling point
156 under a reflux. The boiling point temperature of the mixture was changing during the
157 experiment due to the changing reaction mixture composition. The temperature increase

6
158 was considered in the determination of the kinetic parameters. The reactions started (by an
159 addition of the catalyst) once the temperature of the reaction mixture reached 50°C and and
160 finished at the temperature of 74 – 75°C. Determination of the reaction kinetic parameters
161 was based on the reaction mixture composition (HPLC analysis) and the temperature
162 during the process.
163 - Isothermal autoclave, i.e., a stirred tank pressure reactor allowing to perform experiments
164 at the elevated temperature 100oC and pressure of 320 kPa.
165
166 The reaction mixture was analysed for succinic acid, monomethyl and dimethyl succinate and
167 the concentration profile was obtained. Analytical conditions: HPLC system equipped with a
168 gradient pump, autosampler, column thermostat and diode-array detector; Column Gemini C18,
169 4.6 x 150 mm, particle size 5 μm (Phenomenex, USA); mobile phase A : 0.025 M HCl in water,
170 B: 100% acetonitrile, flow rate of 1 mL min-1, column temperature of 40 °C, injection volume of
171 10 μl, detection: UV at the wavelength of 210 nm, calibration using external standards of succinic
172 acid, monomethyl succinate and dimethyl succinate. Water was analysed by the Fisher method.
173
174 The reaction was carried out until equilibrium was reached to estimate the equilibrium
175 composition. Several kinetic experiments (12 in total) were conducted in both reactors to
176 study the following effects on the acid catalysed esterification reaction of succinic acid with
177 methanol:
178 - effect of reaction temperature,
179 - catalyst loading defined as mass of the catalyst to the mass of the reaction mixture
180 ratio, w , (kg cat / kg liq ) ,

181 - initial reactants ratio defined as R0  n0, MeOH / n0, SA , where n0,MeOH and n0,SA represent

182 the initial molar ratio of methanol and succinic acid in the batch.
183 Both, the temperature and the R0 interval were chosen for the thermodynamic analysis.
184
185 To describe the reaction kinetics, a pseudo-homogeneous model, neglecting the internal
186 diffusion inside the catalyst particle, was used. Rates of reactions (1) and (2) were in the
187 following form:
188

 E  x x 
189 r1  wk1 exp   1   xSA xMeOH  MMS W  (4)
 RT   K x1 

7
  E  xDMS xW 
190 r2  wk2 exp   2   xMMS xMeOH   (5)
 RT  Kx2 

191 where rj represents the rate of the j-th reaction (kmol m-3s-1 ) , w is the catalyst loading

192 3
  
(kg cat / kg liq ) , k j the frequency factor for the j-th rate constant kmol/m /s kg liq /kg cat , E j

193 the activation energy for the j-th reaction, xi , i  SA, MMS, DMS, MeOH, W are the molar

194 fractions and K xj is the equilibrium constant of the j-th reaction defined as:
*
xMMS xW*
195 K x1  * *
(6)
xSA xMeOH

196 and
*
xDMS xW*
197 K x2  * *
(7)
xMMS xMeOH

198 In Figs 3, 4 and 5, typical concentration time profiles for the three experiments at different
199 conditions are presented. Experimental data are compared with the simulated ones obtained
200 using the estimated values of kinetic parameters summarised in Table 2.
201

202 Table 2. Kinetic parameters estimated from kinetic experiments

k1  kmol/m3 /s   kg liq /kg cat  1.186×1010

E1  kJ/kmol  72855

k2   kmol/m3 /s   kg liq /kg cat  4.741×1010

E2  kJ/kmol  78646

K x ,1 0.1509×T – 6.567

K x ,2 0.0263×T – 1.128

203

8
 0.25

0.2

0.15

0.1

0.05

0
0 2 4 6 8 10 12
time /h

Fig 3: Comparison of experimental (points) and calculated (lines) kinetic data. Initial temperature:
323 K, final temperature: 347 K, R0  6 , w  0,0367 , W: dash-dot-dotted line, square; SA: full line,
triangle; MMS: short dashed line, cross; DMS: long dashed line, circle
204
205
0.20

0.18

0.15

0.13

x 0.10

0.08

0.05

0.03

0.00
0 2 4 6 8 10 12
time/h

Fig 4 Comparison of experimental (points) and calculated (lines) kinetic data. Initial temperature: 323
K, final temperature: 343 K, R0  9 , w  0,0367 , W: dash-dot-dotted line, square; SA: full line,
triangle; MMS: short dashed line, cross; DMS: long dashed line, circle
206

9
207
0.20

0.18

0.16

0.14

0.12

x 0.10
0.08

0.06

0.04

0.02

0.00
0 1 2 3 4 5 6
time/h

Fig 5 Comparison of experimental (points) and calculated (lines) kinetic data. Initial temperature: 373
K, final temperature: 373 K, R0  9 , w  0,0367 , W: dash-dot-dotted line, square; SA: full line,
triangle; DMS: short dashed line, cross; MMS: long dashed line, circle.
208
209
210 Experimental data presented in the figures indicate that the reactant mole ratio R0  6 is more

211 beneficial than R0  9 since in the same reaction time, more MMS and DMS is produced in
212 the sane volume of the reaction mixture and the conversion of SA remains the same. The
213 higher catalyst loading leads to shorter time needed to reach the equilibrium. The reaction
214 time of 11 hours was required to reach the equilibrium at the catalyst concentration of 3.67
215 mass % dropped to 4 hours at 13.17 mass % of the catalyst in the reaction mixture. Higher
216 temperature (100°C) has very positive effect on the reaction time and conversion of SA as
217 well as on the DMS yield. On the other hand, at temperatures above 90°C, elevated pressure
218 is required to keep the reaction mixture in the liquid phase. All these results are in very good
219 agreement with theoretical prediction using “a priori” estimated physico-chemical properties
220 of MMS based on different semi-empirical correlations and group of contributions methods.
221
222 The comparison of calculated and experimental data in Figs. 3 – 5 indicates that the proposed
223 kinetic model (4) and (5) fitted the experimental data over the entire interval of experimental
224 conditions very well. The temperature dependence of experimental equilibrium constants

10
225 shows that the equilibrium constants slightly increase with the temperature, indicating that the
226 endothermic reaction effect slightly dominates in the system.
227
228 Selection of reactor type
229
230 A common requirement for industrial processes is continuous mode of operation. Therefore,
231 three types of reactors were considered for the esterification process:
232 - continuous isothermal stirred tank reactor, CSTR,
233 - reactive distillation column, RDC,
234 - isothermal tubular reactor.
235
236 From kinetic experiments and analysis of experimental results follows that to achieve high
237 efficiency of the esterification, the catalyst loading is a very important parameter. It is also
238 very important to keep the catalyst/reaction mixture ratio as high as possible. Since it is
239 difficult to operate a stirred tank reactor at high catalyst loadings in the reactor, this type of
240 reactor was excluded from further considerations for heterogeneous esterification.
241
242
243 Reactive distillation
244
245 Since the DMS synthesis requires high excess of methanol, it is important to recycle
246 unreacted methanol back into the process. Because of this fact and also taking into account
247 that existing industrial esterification processes, including the design of SA esterification by
248 ethanol described by Orjuela et al., 2011, 2012, reactive (catalytic) distillation was assumed as
249 another candidate for the DMS synthesis. Schematic flow sheet diagram of RDC considered
250 for the DMS process in this work is depicted in Fig. 6.
251

11
 W, MeOH

SA, MeOH
R0  5 T  60 C

W, MMS, DMS, SA

Fig. 6. Schematic flow sheet of a reactive distillation column for SA esterification by MeOH
252
253 The following facts must be taken into consideration in the design of RDC for the DMS
254 synthesis:
255 - Low solubility of SA in methanol requires high excess of methanol in the feed ( R0
256 should be higher than 5) and temperatures above 50 – 60 °C. Since the temperature is
257 close to the normal boiling point of methanol, elevated pressure is required to keep
258 methanol in the liquid phase; otherwise, the methanol vapour leaves the reactive
259 section of the column and limits the reaction extend.
260 - Water is a by-product of esterification and it is the second most volatile component in
261 the reaction mixture. It means that water removal is connected with the removal of the
262 reactant, methanol, as well. This is significant for the production system design
263 because to keep the excess of methanol in the liquid phase in the reactive section
264 requires higher concentration of methanol in the feed and/or an increase in the
265 pressure in the column. On the other hand, separation of the water – methanol mixture
266 from the reaction mixture can be easily executed in the following distillation column.
267 The only problem could arise from the huge excess of methanol with respect to water.
268 Since recycled methanol should be of high purity, the column for water removal in
269 methanol regeneration has to be large.

12
270 - The main product (DMS), intermediate MMS and unreacted SA with traces of water
271 are collected in the reboiler of the RDC. At normal pressure, the temperature in the
272 reboiler is close to the boiling point of DMS, approximately 190 – 200 °C. At elevated
273 pressure (approx. 300 kPa) methanol is in the liquid phase at 90°C, which is the
274 optimum temperature for chemical reaction kinetics but due to the high pressure, the
275 temperature of the mixture in the reboiler increases above 200 °C. Such a high
276 temperature can impose thermal degradation of SA and the esters. Product degradation
277 can be suppressed at certain level of water concentration in the reboiler. In this case,
278 reactive distillation loses the advantage of shifting the equilibrium towards the final
279 product; additionally, in the presence of water in the reboiler, reversible reactions
280 catalysed by SA could proceed.
281 - Entire process requires further steps for purification of the final product as well as
282 methanol for recirculation. In other words, even if the reactive distillation process is
283 suitable for the esterification, two more distillation columns are needed to fulfil the
284 quality indicators of the products.
285 The process of DMS synthesis was evaluated with regard to the suitability of the reaction
286 distillation for chemical reaction and separation according to Schembecker and Tlatlik
287 (2003). The diagram presenting experimental windows of reaction and separation
288 conditions is presented in Fig. 7. Since the operational windows for reaction and
289 separation are far from each other it can be concluded that the reactive distillation concept
290 is not convenient for dimethyl succinate process.
291
separation operational
window

250

T ( C)
chemical operation
window
150

50

100 200 300

P (kPa)
Fig. 7. Reactive distillation for DMS production – „overlapping“ of separation and chemical operation
windows

13
292
293 Tubular reactor
294
295 The third identified option to be considered for the reaction was the use of a continuous
296 tubular reactor with a fixed bed of catalyst. The reaction mixture contains products and by-
297 products of the reaction as well as unreacted reactants. It is obvious that this type of reactor is
298 followed by distillation to separate volatile and heavy compounds from the post reaction
299 mixture to achieve similar stream compositions as in reactive distillation. Therefore, the entire
300 technology consisted of three distillation columns as it is depicted in Fig.8.
301
302 Briefly: the reaction mixture is prepared in a mixer, where fresh and recycled methanol,
303 succinic acid and recycled unreacted SA, MMS and DMS are mixed to a homogeneous
304 solution and introduced into the tubular reactor. The mixer is a heated stirred tank in which
305 the SA is dissolved and the reaction mixture is preheated to 90 °C.
306 The temperature of 90 °C and pressure of 300kPa are proposed for the esterification reaction.
307 Since the reaction heat of both reactions is low, the reactor can be operated as an adiabatic
308 one.
309

MeOH, W
K2
7

3
9 W, MeOH, DMS
1 SA
60°C 5 90°C, 300kPa 6

mixer tubular fixed-bed K1 10 DMS, MMS, W

reactor
8
2 MeOH
K3
4

SA, MMS, DMS

Fig. 8. Flow sheet diagram for dimethyl succinate synthesis in a fixed bed tubular reactor and
distillation columns.
310
311 Separation of components from the post reaction mixture is performed in distillation columns.
312 The first rectification column, K1, separates unreacted methanol and water formed during the

14
313 reaction (distillate, stream 7) from DMS, MMS and unreacted SA (reboiler, stream 8).
314 Methanol is purified in column K2 (distillate, stream 3), and recycled back to the mixer. The
315 bottom stream from K1 is introduced into column K3 for separation of the final product
316 (DMS) from unreacted SA and MMS. Design considerations of conventional process
317 technology are discussed in the following text.
318
319 Size of tubular fixed bed reactor
320 The reactor volume depends on the reaction thermodynamics and kinetics for known molar
321 flow rates of all components. These values are strongly affected by the molar flows of both
322 recycled streams which are related to the performance of distillation columns K1, K2 and K3
323 and to the requirements on quality of the distillation products.
324
325 The isothermal plug flow model of the fixed bed reactor was developed and used for
326 reactor simulation. Further simplifying assumptions were used in the reactor simulation:
327 - x9, DMS  x9, MeOH  0 - no losses of DMS and methanol in column K2 ,

328 - x10, MMS  x10,W  0 - no losses of MMS from distillate from column K3 and no water

329 leaving column K1 in distillate ,

330 - x4, DMS  0 - no recycling of DMS from the reboiler of column K3.

331
332 Results of the simulations for different methanol to water ratios ( x3,W  0.01 or

333 x3,W  0.05 ) in recycled stream 3 and different ratios of R0 (from 5 to 10) in stream 5 are

334 presented in Fig 7 together with the calculated concentration profiles of components in the
335 reactor.
336 The concentration profiles indicate that, irrespective to the feed composition, the
337 reaction equilibrium is reached and the composition of the output stream is practically equal
338 to the equilibrium composition at the same reactor volume considered (Table 3). The
339 equilibrium composition was calculated by solving equations (6) and (7) using experimentally
340 determined equilibrium constants at the relevant temperature in the reactor.
341
342 Results of the simulation based on thermodynamic and experimental data indicate that
343 the reactor volume of 0.3 – 0.4 m3, with the catalyst bulk density of 700 kg m-3 and the
344 temperature of 90 °C, for different composition of the feed is working practically as an
345 equilibrium reactor (in the range of the investigated parameters). Detailed results of the
15
346 simulation are summarised in Table 3. This results are very important for the design of a
347 separation system.
348
0.4 0.4

0.35 0.35

0.3 0.3

0.25 0.25

0.2 0.2

x x
0.15 0.15

0.1 0.1

0.05 0.05

0 0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4
V (m^3) V (m^3)

R0  5, T  90 C, x 3,W  0, 01 R0  10, T  90 C , x 3,W  0, 05

Fig 7. Concentration profiles of SA –short dashed line, MMS – dotted line, DMS – solid line, W –
long dashed line, in a tubular reactor with plug flow.
349
350
351 Table 3. Simulation results from tubular reactor
Reactor: T  90 °C P  300 kPa V  0.3m3 w  2.7

Simulation 1 Simulation 2
R0  5 R0  10
x3,W  0.01 x3,W  0.05

stream 6 eq. comp. stream 6 eq. comp.

SA 0.0002 0.0002 3.8x10-5 3.59x10-5
MMS 0.0132 0.0131 0.00392 0.0039
DMS 0.1635 0.1635 0.0872 0.0872
MeOH 0.4913 0.4912 0.6978 0.698
W 0.3318 0.3320 0.21107 0.2111
352
353 Characteristics of distillation columns
354 The simplified conditions applied for the simulation of the fixed bed reactor are too strict for
355 the design of the distillation columns. To obtain zero concentration of methanol in the reboiler
356 of distillation column K2 is impossible at real conditions due to the requirements on the

16
357 height and diameter of the column (high capital and operational costs). Similar situation is
358 with column K1. To reach zero concentration of water in the reboiler of column K1 is very
359 difficult within reasonable dimensions of the column. Therefore, to design the distillation
360 columns, more realistic assumptions have to be assumed:
361 1. concentration of water from K3 of 1%mol,
362 2. concentration of MeOH in the reboiler of K2 of less or equal to 1 % mol,
363 3. concentration of DMS recycled from the reboiler of K3 of 1% mol,
364 4. maximum concentration of MMS in the distillate from K3 of 1 % mol.
365
366 The simple MESH model (Seader and Henley, 2006) with ideal vapour phase and non ideal
367 liquid phase at the pressure of 100 kPa was used to simulate the K1 and K2 distillation
368 columns. Activity coefficients of all compounds were estimated using the Wilson´s equation,
369 binary parameters were estimated using the UNIFAC group contribution method (except of
370 the known binary parameters of the MeOH – W mixture). The pressure in K3 was 60 kPa to
371 lower the temperature in the reboiler, preventing thus the DMS, MMS and unreacted SA
372 thermal decomposition. The condenser of K1 was assumed to be a partial one, while those in
373 K2 and K3 were total ones.
374
375 The first constrain, x10,W  0, 01 causes an appearance of DMS in the distillate from column
,
376 K1 and subsequently in the reboiler of K2. The second assumption, the concentration of
377 methanol in bottoms of K2 up to 1%mol, is limited by the maximum allowed concentration of
378 methanol in the stream entering a biological waste water treatment plant. Traces of DMS and
379 MeOH in the reboiler of K2 are the loss of the process, which is compensated by smaller
380 dimensions of the column (capital) and operating costs.
381 Allowed amount of water in the bottoms from K1 and consequently in the distillate from K3
382 implicate the need of an additional separation step after K3, drying of the final product. The
383 dimensions of K3 depend on the allowed concentration of MMS in the distillate stream and of
384 DMS in the recycled stream from the reboiler of K3 back into the mixer. On the other hand,
385 the presence of MMS in the product stream decreases the purity of the final product.
386
387 Also, the amount of recycled water in stream 3 strongly affects the columns’ dimensions and
388 operational costs of column K2. It is obvious that waste containing MeOH and DMS, stream

17
389 9, requires the addition of fresh methanol and SA into the system. These accepted component
390 concentration limits affect also the dimensions of the fixed bed reactor.
391
392
393 Table 4. Characteristics of distillation columns and process conditions for two initial reactants’ ratios
394 and concentrations of water in the recycle stream
R0  5 R0  10
x3, w  0.05 x3, w  0.01

Distillation column RK1 RK2 RK3 RK1 RK2 RK3

Number of trays 18 12 25 9 40 25
Reflux ratio 0.15 1.22 0.31 0.415 0.956 0.26
Temperature in condenser (°C) 82 65 147 72.3 64 151
Temperature in reboiler (°C) 183 98 227 175 98 225
Condenser duty (kW) 70 542 138 38 1280 131
Reboiler duty (kW) 589 103 135 900 428 212
Pressure (kPa) 100 100 60 100 100 60
Diameter (m) 1 1 0.7 1.33 1.61 0.67
395
396 Separation processes conditions are summarised in Table 4. The data indicate that the smaller
397 methanol to succinic acid ratio and higher concentration of water in recycled methanol from
398 RK2 back to the mixer have a positive effect on the columns’ dimensions and also on the
399 reboiler and condenser duties. The analysis of capital and operational costs indicates the
400 dominant effect of the operational costs and therefore the process economy dictates the
401 maximum heat integration in the system.
402

403 Conclusion
404
405 Analysis of the esterification process with the perspective of using reactive distillation as an
406 excellent option of process integration is presented. Dimethyl succinate production was
407 considered as the case study. Three continuous process concepts of the reaction and
408 separation systems were analysed.
409 A CSTR reactor followed by a separation system was rather a theoretical option and because
410 of the high catalyst to reactants ratio required, it was excluded from a more detailed analysis.

18
411 The reactive distillation concept, commonly considered for esterification processes, was
412 analysed. An attempt to recognise a priori if the process is suitable for reactive distillation,
413 based on reaction and separation conditions is presented. An optimum experimental window
414 (temperature and pressure) for the reaction and separation were found and compared. Since
415 the optimum temperatures and pressures for the reaction and separation are different it is very
416 difficult to realise these two processes in one RD column and the reactive distillation concept
417 is thus not suitable for this particular process. The obtained experimental data and process
418 simulation for dimethyl succinate production proved that the a priori analysis (Schembecker
419 & Tlatlik, 2003) is a reasonable method for the prediction of the suitability of reactive
420 distillation as a promising system for the process.
421 The traditional technology, a combination of a tubular fixed bed reactor and separation, was
422 recognised as the best option for the dimethyl succcinate production. The fixed bed reactor is
423 relatively simple and cheap and the separation of components from the post reaction mixture
424 by distillation is a standard process. The system requires three distillation columns, the first
425 one for the separation of volatile components from those with high boiling points, the second
426 one for the regeneration of methanol and the third one for the purification of the final product.
427 The estimated capital and operational costs are closely related to the requirements for
428 distillates’ and bottoms’ components concentrations. An economic analysis indicated that
429 operational costs dominate in the costs estimation and that an integration of partial processes
430 into one vessel (reactive distillation) is advantageous. However, according to the process
431 conditions for the reaction and distillation, this option is not perspective for this particular
432 process.
433
434 Acknowledgements
435 This contribution is the result of the project implementation: National Centre for Research and
436 Application of Renewable Energy Sources, ITMS 26240120016, supported by the Research
437 and Development Operational Programme funded by the ERDF, and by the Slovak Research
438 and Development Agency under the Contract No. APVV-0656-11.
439
440

19
441 List of symbols
442
E activation energy J mol-1
 f Gliq
0
,298
standard Gibbs energy of formation J mol-1

 f H liq
0
,298
standard enthalpy of formation J mol-1

 r H liq ,298 standard reaction enthalpy J mol-1

 vap H 343 enthalpy of vaporisation J mol-1

Ka thermodynamic equilibrium constant

Kx concentration equilibrium constant

k rate constant  kmol/m /s   kg

3
liq /kg cat 

k j frequency factor for rate constant  kmol/m /s   kg

3
liq /kg cat 

MW molar weight kg mol-1

n molar amount mol

P pressure Pa
R0 molar MeOH/SA ratio in the feed to reactor
r reaction rate kmol m -3s -1
T temperature K
Tb normal boiling point K
w catalyst loading kg cat / kg liq

x molar fraction
x* molar fraction at equilibrium

 activity coefficient in liquid phase

443
444 Abbreviations
DMS dimethyl succinate
K1, K2, K3 distillation columns
MeOH methanol
MMS monomethyl succinate
RDC reactive distillation column

20
 SA succinic acid
W water
445
446

21
447 References
448
449 Blahušiak, M., Š. Schlosser, J. Marták, Simulation of a hybrid fermentation – separation
450 process for production of butyric acid, Chemical Papers, 2010, (64), 213 – 222, doi:
451 10.2478/s1169-009-0114-7
452
453 Buchaly, C., P. Kreis, A. Górak, Hybrid separation processes – combination of reactive
454 distillation with membrane separation, Chemical Engineering and Processing, 2007, (46), 790
455 – 799, doi: 10.1016/j.cep.2007.05.023
456
457 Budarin, V., R. Luque, D., J., Macquarrie and J., H., Clark, Towards a bio – based industry:
458 bening catalytic esterification of succinic acid in the presence of water, Chemistry, A
459 European Journal, 2007, (13), 6914 – 6919, doi: 10:1002/chm.200700037
460
461 Delgado, P., Sanz, M., T., Beltrán, S., 2007, Kinetic study for esterification of lactic acid with
462 ethanol and hydrolysis of lactate using an ion-exchange resin catalyst, Chemical Engineering
463 Journal, 126, 111 - 118
464
465 Demirbas, A., Bioegineeries: Current activities and future developments, Energy Conversion
466 and Management, 2009, (50), 2782 – 2801, doi: 10.1016/j.enconman.2009.06.035
467
468 Hanika, J., J. Kolena, Q. Smejkal, Butylacetate via reactive distillation – modelling and
469 experiment, Chemical Engineering Science, 1999, (54), 5205 - 5209
470
471 Kotora, M., C. Buchaly, P. Kreis, A. Górak, J. Markoš, Reactive distillation – experimental
472 data for n-propyl propionate synthesis, Chemical Papers, 2008, (61), 65 – 69, doi:
473 10.2478/s11696-007-0080-x
474
475 Kotora, M., Z. Švandová, J. Markoš, Three phase nonequilibrium model for catalytic
476 distillation, Chemical Papers, 2009, (63), 197 – 204, DOI: 10.2478/s11696-009-0004-z
477
478 Krishna, R., Reactive separation: more ways to skin a cat, Chemical Engineering Science,
479 2002, (57), 1491 - 1504
480

22
481 Mihaľ, M., R. Vereš, J. Markoš, V. Štefuca, Intensification of 2-phenyl production in fed –
482 batch hybrid bioreactor: Biotransformation and simulations, Chemical Engineering and
483 Processing: Process Intensification, 2012, (57-58), 75 – 85, doi: 10.1016/j.cep.2012.03.006
484
485 Mihaľ, M., Ľ. Krištofíková, J. Markoš, Production of 2-phenylethanol in hybrid system using
486 airlift reactor and immersed hollow fiber membrane module, Chemical Engineering and
487 Processing: Process Intensification, 2013, (72) 144 – 152, doi: 10.1016/j.cep.2013.08.008
488
489 Mitkowski, P. T., C. Buchaly, P. Kreis, G. Jonsson, A. Górak, R. Gani, Computer design,
490 analysis and experimental investigation of membrane assisted batch reaction – separation
491 systems, Computers and Chemical Engineering, 2009, (33), 551 – 574, doi:
492 10.1016/j.compchemeng.2008.07.012
493
494 Mitkowski, P.T., Hybrid process scheme for the synthesis of ethyl lactate: conceptual design
495 and analysis, Chemical Papers, 2001, (65), 412 – 426, doi: 10.2478/s11696-011-0036-z
496
497 Orjuela, A., A. Kolah, C. T. Lira, D. J. Miller, Mixed succinic acid/acetic acid esterification
498 with ethanol by reactive distillation, Industrial and Engineering Chemistry Research, 2011,
499 (50), 9209 – 9220, doi: 10.1021/ie200133w
500
501 Orjuela, A., A. Kolah, X. Hong, C. T. Lira, D. J. Miler, Diethyl succinate synthesis by
502 reactive distillation, Separation and purification technology, 2012, (88), 151 – 162, doi:
503 10.1016/j.seppur.2011.11.033
504
505 Reid, R. C., J. M. Prausnitz, T. K., Sherwood,TheProperties of Gases and Liquids, 4thedition,
506 McGraw-Hill, New York, 1986
507
508 Rowley, R.L., W.V. Wilding, J.L. Oscarson, N.F. Giles, DIPPR-801 Data Compilation of
509 Pure Chemical Properties, Design Institute for Physical Properties, http://dippr.byu.edu,
510 Brigham Young University, Provo, Utah, 2011.
511
512 Schembecker, G. and S. Tlatlik, Process synthesis for reactive separations.Chemical
513 Engineering and Processing, 2003. 42(3): p. 179-189
514

23
515 Seader, J. D. and E. J. Henley, Separation Process Principles, 2nd Edition, John Wiley and
516 Sons, Inc., 2006
517
518 Tavan, Y., S. H. Hoseini, Design and simulation of a reactive distillation process to produce
519 high – purity ethyl acetate, Journal of the Taiwan Institute of Chemical Engineers, 2013, (44),
520 577 – 585, doi: 10.1016/j.jtice.2012.12.023
521
522 Taylor, R. and R. Krishna, Modelling reactive distillation, Chemical Engineering Science,
523 2000, (55) 5183-5229

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