Methyl acetate–methanol mixture separation by extractive distillation: Economic aspects

doi:10.1007/s11705-018-1769-9

Front. Chem. Sci. Eng.

2018, Vol. 12

Issue (4) : 670-682 https://doi.org/10.1007/s11705-018-1769-9

RESEARCH ARTICLE

Methyl acetate–methanol mixture separation by extractive distillation: Economic aspects

Elena Graczová(

), Branislav Šulgan, Samuel Barabas, Pavol Steltenpohl

Institute of Chemical and Environmental Engineering, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, 81237 Bratislava, Slovakia

Download: PDF(237 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

Methyl acetate is considered low toxicity volatile solvent produced either as a by-product during methanol carbonylation or via acetic acid esterification with methanol. In both cases, pure methyl acetate has to be isolated from the reaction mixture. Simulation of methyl acetate separation from its mixture with methanol by extraction distillation was carried out in ASPEN+ software. In total three case studies were assumed using two different extraction solvents and two solvent regeneration strategies. In case A, novel extraction solvent 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid, was considered. Raw material separation was achieved in an extraction distillation column while the solvent regeneration was accomplished in a second distillation column in this case. In case study B, the same extraction solvent was used; however, its regeneration was carried out in a single-effect evaporator. Dimethyl sulfoxide was the second extraction solvent selected. Its use in methyl acetate-methanol separation is presented in case study C. As high purity of dimethyl sulfoxide was required for the methyl acetate-methanol azeotrope breaking, its regeneration was carried out in the second distillation column only. To simulate the ternary methyl acetate–methanol–extraction solvent mixtures separation, vapor–liquid equilibrium was predicted based on the NRTL equation. Further, unknown properties of the considered ionic liquid and variation of these properties with temperature were predicted and introduced into the ASPEN+ components properties database. Based on these data, optimum operation parameters of the respective separation equipment were established. In all case studies, the same condition had to be fulfilled, namely minimum methyl acetate content in the distillate from the extraction distillation column of 99.5mol-%. Results of simulations using the respective optimum operation parameters were employed in the economic evaluation of the three separation unit designs studied. It was found that the least energy-demanding design corresponds to the case study B in terms of both capital as well as operation expenses.

Keywords methyl acetate 1-ethyl-3-methylimidazolium trifluoromethanesulfonate extraction distillation dimethyl sulfoxide economic evaluation

Corresponding Author(s): Elena Graczová

Just Accepted Date: 09 August 2018 Online First Date: 21 December 2018 Issue Date: 03 January 2019

Cite this article:

Elena Graczová,Branislav Šulgan,Samuel Barabas, et al. Methyl acetate–methanol mixture separation by extractive distillation: Economic aspects[J]. Front. Chem. Sci. Eng., 2018, 12(4): 670-682.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-018-1769-9
https://academic.hep.com.cn/fcse/EN/Y2018/V12/I4/670

Tab.1 Overview of ionic liquids used for the MA–ME azeotropic mixture separation

Fig.1 ASPEN+ flow sheet of a unit for MA–ME mixture separation by extraction distillation. Solvent regeneration is carried out in (a) a distillation column or (b) a single-effect evaporator. C1: Column for extraction distillation (including reboiler and condenser); C2: Regeneration equipment; EX1–EX4: Heat exchange equipment; MIX: Mixer; P1: Pump; VLV1: Throttle valve

Tab.2 Selected properties of ionic liquid [EMIM][Triflate]

Tab.3 Parameters of the Antoine equation (Eq. (6)) for [EMIM][Triflate] (values of parameters C₃–C₇ in Eq. (6) were set to 0)

Tab.4 Parameters of Eq. (8) for [EMIM][Triflate] molar enthalpy of vaporization calculation (?_vh_IL/(kJ·kmol^–1))

Tab.5 NRTL equation parameters (Eqs. (2–5)) for the chosen binary systems

x_S,IL	$n ˙ S / n ˙ F$	N	f_F	R
1.00	1.1	23	7	1.36
0.99	1.1	23	7	1.61
0.98	1.1	23	8	1.90

Tab.6 Optimized values of column C1 construction and operation parameters computed for three levels of extraction solvent (IL) purity (x_S,IL)*

Fig.2 MA–ME mixture separation in the presence of IL at P = 101.325 kPa; Variation of the MA content in distillate from extraction distillation column D2 with the solvent-to-feed mole ratio for different extraction solvent purities, x_S,IL = 1.00 (red curve), x_S,IL = 0.99 (green curve), and x_S,IL = 0.98 (blue curve).

Tab.7 Optimized values of column C2 parameters (considering [EMIM][Triflate] IL as extraction solvent)

Parameter	F0	F1	S0	S1	S2	D1	W1	F21	F22	D2	W21	W22	W23	W24
$n ˙$ /(kmol·h^–1)	10.00		0.00	11.00		6.73	14.27	14.27		3.27	11.00	11.00
x(MA)	0.670		0	0.000		0.995	0.001	0.001		0.002	0.000	0.000
x(ME)	0.330		0	0.020		0.005	0.244	0.244		0.998	0.020	0.020
x(IL)	0		1	0.980		0.000	0.755	0.755		0.000	0.980	0.980
t/°C	20.0	53.5	20.0	116.5	60.0	56.9	123.7	107.8^a)	149.8^b)	28.2	176.6	176.8	126.7	116.6
P/kPa	101.3		101.3	101.3		101.3	101.3	20		20	20	101.3

Tab.8 Separation of MA–ME mixture in the presence of IL, characteristics of material streams presented in Fig. 1(a) (extraction distillation column combined with regeneration distillation column)

Parameter	F0	F1	S0	S1	S2	D1	W1	F21	F22	D21	D22	W21	W22	W23	W24
$n ˙$ /(kmol·h^–1)	10.00		0.00	11.00		6.73	14.27	14.27		3.27		11.00	11.00
x(MA)	0.670		0	0.000		0.995	0.001	0.001		0.002		0.000	0.000
x(ME)	0.330		0	0.020		0.005	0.244	0.244		0.998		0.020	0.020
x(IL)	0		1	0.980		0.000	0.755	0.755		0.000		0.980	0.980
t/°C	20.0	53.5	20.0	104.7	60.0	56.9	123.7	107.8^a)	160.0^b)	176.6	28.2	176.6	176.8	115.0	104.7
P/kPa	101.3		101.3	101.3		101.3	101.3	20		20		20	101.3

Tab.9 Separation of MA–ME mixture in the presence of IL, characteristics of material streams presented in Fig. 1(b) (extraction distillation column combined with single-effect vacuum evaporator)

Column	P/kPa	$n ˙ S / n ˙ F$	N	f_S	f_F	R
C1	101.3	1.5	18	2	12	1.49
C2	20	–	5	–	3	0.65

Tab.10 Optimized values of parameters of distillation columns C1 and C2 considering DMSO as extraction solvent

Parameter	F0	F1	S0	S1	S2	D1	W1	F21	D2	W21	W22	W23
$n ˙$ /(kmol·h^–1)	10.00		0.02	15.03	15.03	6.70	18.33	18.33	3.32	15.01	15.01
x(MA)	0.670		0	0.000		0.995	0.002	0.002	0.010	0.000	0.000
x(ME)	0.330		0	0.002		0.005	0.180	0.180	0.985^b)	0.002	0.002
x(DMSO)	0		1	0.998		0.000	0.818	0.818	0.005	0.998	0.998
t/°C	20.0	53.5	20.0	113.4	83.4	56.9	129.0	96.9^a)	27.7	132.3	132.5	113.5
P/kPa	101.3		101.3	101.3		101.3	101.3	20	20	20	101.3

Tab.11 Characteristics of material streams presented in Fig. 1(a) (extraction distillation column combined with regeneration distillation column), simulation results for the operation parameters given in Table 10

Tab.12 Calculated heat duties of heat equipment and power duty of pump P1 shown in Fig. 1

Tab.13 Prices of commodities used in economic calculations

Tab.14 Selected capital investments including purchase and installation expenses for the three case studies assumed

Tab.15 Comparison of energy media consumption for the three case studies assumed

Tab.16 Comparison of selected economic indices for the three case studies assumed

Tab.17 Feed (F1) state, column C1 reflux ratio and the reboiler and condenser duties for different heat fluxes in the heat exchangers EX1 and EX2

1	V HAgreda, L R Partin, W H Heise. High-purity methyl acetate via reactive distillation. Chemical Engineering Progress, 1990, 86(2): 40–46
2	R SHuss, F R Chen, M F Malone, M F Doherty. Reactive distillation for methyl acetate production. Computers & Chemical Engineering, 2003, 27(12): 1855–1866 https://doi.org/10.1016/S0098-1354(03)00156-X
3	AGiwa. Methyl acetate reactive distillation process modeling, simulation and optimization using ASPEN Plus. Journal of Engineering and Applied Sciences (Asian Research Publishing Network), 2013, 8(5): 386–392
4	CRohde, R Marr, MSiebenhofer. Investigation of methyl acetate production by reactive extraction. In: Proceedings of the AIChE Annual Meeting 2004. Austin: AIChE, 2004, 5113–5118
5	SLux, T Winkler, MSiebenhofer. Synthesis and isolation of methyl acetate through heterogeneous catalysis with liquid–liquid extraction. Industrial & Engineering Chemistry Research, 2010, 49(21): 10274–10278 https://doi.org/10.1021/ie1005433
6	Y JCao, M Li, YWang, T RZhao, XLi, Z Y Zhu, Y L Wang. Effect of feed temperature on economics and controllability of pressure-swing distillation for separating binary azeotrope. Chemical Engineering and Processing: Process Intensification, 2016, 110: 160–171 https://doi.org/10.1016/j.cep.2016.10.011
7	LBerg, A I Yeh. The separation of methyl acetate from methanol by extractive distillation. Chemical Engineering Communications, 1984, 30(1–2): 113–117 https://doi.org/10.1080/00986448408911119
8	Z GLei, C Y Li, B H Chen. Extractive distillation: A review. Separation and Purification Reviews, 2003, 32(2): 121–213 https://doi.org/10.1081/SPM-120026627
9	TMahdi, A Ahmad, M MNasef, ARipin. State-of-the-art technologies for separation of azeotropic mixtures. Separation and Purification Reviews, 2015, 44(4): 308–330 https://doi.org/10.1080/15422119.2014.963607
10	BSchuur. Selection and design of ionic liquids as solvents in extractive distillation and extractive processes. Chemical Papers, 2015, 69(2): 245–253 https://doi.org/10.1515/chempap-2015-0016
11	M T GJongmans, EHermens, MRaijmakers, J I WMaassen, BSchuur, A Bde Haan. Conceptual process design of extractive distillation processes for ethylbenzene/styrene separation. Chemical Engineering Research & Design, 2012, 90(12): 2086–2100 https://doi.org/10.1016/j.cherd.2012.05.019
12	M T GJongmans, JTrampé, BSchuur, A Bde Haan. Solute recovery from ionic liquids: A conceptual design study for recovery of styrene monomer from [4-mebupy][BF4]. Chemical Engineering and Processing: Process Intensification, 2013, 70: 148–161 https://doi.org/10.1016/j.cep.2013.04.007
13	G ZLi, P Bai. New operation strategy for separation of ethanol-water by extractive distillation. Industrial & Engineering Chemistry Research, 2012, 51(6): 2723–2729
14	EQuijada-Maldonado, T A MAelmans, G WMeindersma, A Bde Haan. Pilot plant validation of a rate-based extractive distillation model for water–ethanol separation with the ionic liquid [emim][DCA] as solvent. Chemical Engineering Journal, 2013, 223: 287–297 https://doi.org/10.1016/j.cej.2013.02.111
15	H J PGutierrez. Extractive distillation with ionic liquids as solvents: Selection and conceptual process design. Dissertation for the Doctoral Degree. Eindhoven: Eindhoven University of Technology, 2013, 137–139
16	G WMeindersma, EQuijada-Maldonado, MJongmans, A Bde Haan. Extractive distillation with ionic liquids: Pilot plant experiments and conceptual process design. In: Ionic Liquids for Better Separation Processes. Berlin: Springer, 2016, 11–38
17	JDhanalakshmi, P S T Sai, A R Balakrishnan. Study of ionic liquids as entrainers for the separation of methyl acetate–methanol and ethyl acetate–ethanol systems using the COSMO-RS model. Industrial & Engineering Chemistry Research, 2013, 52(46): 16396–16405 https://doi.org/10.1021/ie402854k
18	Z GZhang, A G Hu, T Zhang, Q QZhang, M YSun, D ZSun, W XLi. Separation of methyl acetate+ methanol azeotropic mixture using ionic liquids as entrainers. Fluid Phase Equilibria, 2015, 401: 1–8 https://doi.org/10.1016/j.fluid.2015.04.018
19	A VOrchillés, P JMiguel, EVercher, AMartínez-Andreu. Isobaric vapor–liquid equilibria for methyl acetate+ methanol+ 1-ethyl-3-methylimidazolium trifluoromethanesulfonate at 100 kPa. Journal of Chemical & Engineering Data, 2007, 52(3): 915–920 https://doi.org/10.1021/je600518s
20	J LCai, X B Cui, Y Zhang, RLi, T YFeng. Vapor–liquid equilibrium and liquid–liquid equilibrium of methyl acetate+ methanol+ 1-ethyl-3-methylimidazolium acetate. Journal of Chemical & Engineering Data, 2011, 56(2): 282–287 https://doi.org/10.1021/je100932m
21	J LCai, X B Cui, Y Zhang, RLi, T YFeng. Isobaric vapor liquid equilibrium for methanol+ methyl acetate+ 1-octyl-3-methylimidazolium hexafluorophosphate at 101.3 kPa. Journal of Chemical & Engineering Data, 2011, 56(2): 2884–2888 https://doi.org/10.1021/je2000588
22	HMatsuda, K Tochigi, VLiebert, JGmehling. Vapor–liquid equilibria of ternary systems with 1-ethyl-3-methylimidazolium ethyl sulfate using headspace gas chromatography. Fluid Phase Equilibria, 2011, 307(2): 197–201 https://doi.org/10.1016/j.fluid.2011.05.016
23	VDohnal, E Baránková, ABlahut. Separation of methyl acetate+ methanol azeotropic mixture using ionic liquid entrainers. Chemical Engineering Journal, 2014, 237: 199–208 https://doi.org/10.1016/j.cej.2013.10.011
24	Z GZhang, A G Hu, T Zhang, Q QZhang, Z QYang, W XLi. Isobaric vapor–liquid equilibrium for methyl acetate+ methanol system containing different ionic liquids at 101.3 kPa. Fluid Phase Equilibria, 2016, 408: 20–26 https://doi.org/10.1016/j.fluid.2015.07.045
25	JCao, G G Yu, X C Chen, A A Abdeltawab, A M Al-Enizi. Determination of vapor–liquid equilibrium of methyl acetate+ methanol+ 1-alkyl-3-methylimidazolium dialkylphosphates at 101.3 kPa. Journal of Chemical & Engineering Data, 2017, 62(2): 816–824 https://doi.org/10.1021/acs.jced.6b00852
26	X MZhang, H P Liu, Y X Liu, C G Jian, W Wang. Experimental isobaric vapor–liquid equilibrium for the binary and ternary systems with methanol, methyl acetate and dimethyl sulfoxide at 101.3 kPa. Fluid Phase Equilibria, 2016, 408: 52–57 https://doi.org/10.1016/j.fluid.2015.08.014
27	C THsieh, M J Lee, H M Lin. Vapor–liquid–liquid equilibria for aqueous systems with methyl acetate, methyl propionate, and methanol. Industrial & Engineering Chemistry Research, 2008, 47(20): 7927–7933 https://doi.org/10.1021/ie800840r
28	A GCrawford, G Edwards, D SLindsay. The ternary system, methanol–methyl acetate–water. Journal of the Chemical Society, 1949: 1054–1058 https://doi.org/10.1039/JR9490001054
29	JGmehling, U. Onken Vapor–Liquid Equilibrium Data Collection. Chemistry Data Series, Vol. I, Part 1. Frankfurt/Main: DECHEMA, 1977, 37–76, 258–264
30	A BPereiro, J M M Araújo, J M S S Esperança, I M Marrucho, L P N Rebelo. Ionic liquids in separations of azeotropic systems—A review. Journal of Chemical Thermodynamics, 2012, 46: 2–28 https://doi.org/10.1016/j.jct.2011.05.026
31	R DRogers, K R Seddon. Ionic liquids—solvents of the future? Science, 2003, 302(5646): 792–793 https://doi.org/10.1126/science.1090313
32	J GHuddleston, A EVisser, W MReichert, H DWillauer, G ABroker, R DRogers. Characterization and comparison of hydrophilic and hydrophobic room temperature ionic liquids incorporating the imidazolium cation. Green Chemistry, 2001, 3(4): 156–164 https://doi.org/10.1039/b103275p
33	J LHumphrey, G E II Keller. Separation Process Technology. New York: McGraw-Hill, 1997, 1
34	MBlahušiak, A AKiss, KBabic, S R AKersten, GBargeman, BSchuur. Insights into the selection and design of fluid separation processes. Separation and Purification Technology, 2018, 194: 301–318 https://doi.org/10.1016/j.seppur.2017.10.026
35	P Steltenpohl, EGraczová. Optimization of extraction solvent-to-feed ratio: Aqueous ethanol mixture separation using [TDTHP][NTf2] ionic liquid. Chemical Engineering Research & Design, 2017, 121: 200–206 https://doi.org/10.1016/j.cherd.2017.02.017
36	Jde Riva, V R Ferro, D Moreno, IDiaz, JPalomar. Aspen Plus supported conceptual design of the aromatic–aliphatic separation from low aromatic content naphtha using 4-methyl-N-butylpyridinium tetrafluoroborate ionic liquid. Fuel Processing Technology, 2016, 146: 29–38 https://doi.org/10.1016/j.fuproc.2016.02.001
37	MLarriba, J de Riva, PNavarro, DMoreno, NDelgado-Mellado, JGarcía, V RFerro, FRodríguez, JPalomar. COSMO-based/Aspen Plus process simulation of the aromatic extraction from pyrolysis gasoline using the {[4empy][NTf2] + [emim][DCA]} ionic liquid mixture. Separation and Purification Technology, 2018, 190: 211–227 https://doi.org/10.1016/j.seppur.2017.08.062
38	EGraczová, D Dobcsányi, PSteltenpohl. Separation of methyl acetate–methanol azeotropic mixture using 1-ethyl-3-methylimidazolium trifluoromethanesulfonate. Chemical Engineering Transactions, 2017, 61: 1183–1188
39	J FBoston, S L Sullivan Jr. A new class of solution methods for multicomponent, multistage separation processes. Canadian Journal of Chemical Engineering, 1974, 52(1): 52–63 https://doi.org/10.1002/cjce.5450520108
40	J DSeader, E J Henley, D K Roper. Separation Process Principles. 3rd ed. New Jersey: Wiley, 2010, 400–412
41	HRenon, J M Prausnitz. Local compositions in thermodynamic excess functions for liquid mixtures. AIChE Journal. American Institute of Chemical Engineers, 1968, 14(1): 135–144 https://doi.org/10.1002/aic.690140124
42	J OValderrama, L AForero, R ERojas. Critical properties and normal boiling temperature of ionic liquids. Update and a new consistency test. Industrial & Engineering Chemistry Research, 2012, 51(22): 7838–7844 https://doi.org/10.1021/ie202934g
43	M MPapari, S Amighi, MKiani, DMohammad-Aghaie, BHaghighi. Modification of a statistical mechanically-based equation of state: Application to ionic liquids. Journal of Molecular Liquids, 2012, 175: 61–66 https://doi.org/10.1016/j.molliq.2012.08.013
44	S JZhang, X M Lu, Q Zhou, X HLi, X PZhang, S CLi. Ionic liquids. Physicochemical properties. Amsterdam: Elsevier, 2009, 47
45	D HZaitsau, G J Kabo, A A Strechan, Y U Paulechka, A Tschersich, S PVerevkin, AHeintz. Experimental vapor pressures of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides and a correlation scheme for estimation of vaporization enthalpies of ionic liquids. Journal of Physical Chemistry A, 2006, 110(22): 7303–7306 https://doi.org/10.1021/jp060896f
46	K GJoback, R C Reid. Estimation of pure-component properties from group-contributions. Chemical Engineering Communications, 1987, 57(1-6): 233–243 https://doi.org/10.1080/00986448708960487
47	Retrieved from the website of Alibaba (methyl-acetate), January 10, 2018
48	Retrieved from the website of Intratec (methanol), January 10, 2018
49	Retrieved from the website of Alibaba (DMSO), January 10, 2018

Viewed

Full text

Abstract

Cited

Shared

Discussed