Analysis of Phase Equilibrium Diagrams of Cyclohexene + Water +

Jan 31, 2018 - The experimental and calculated data were found to be in a good agreement. The analysis of phase diagrams showed that the simplest diag...
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Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Analysis of Phase Equilibrium Diagrams of Cyclohexene + Water + Cyclohexanone + Solvent System Anastasia V. Frolkova,* Mark A. Mayevskiy, and Alla K. Frolkova Department of Chemistry and Technology of Basic Organic Synthesis, Moscow Technological University, Vernadskogo prospect 86, Moscow, 119571, Russia ABSTRACT: Vapor−liquid and liquid−liquid equilibrium of quaternary systems that can form in the production of cyclohexanone by oxidation of cyclohexene in the presence of different solvents water + dimethylformamide (dimethyl sulfoxide, dimethylacetamide) were studied using mathematic modeling and NRTL model. The experimental and calculated data were found to be in a good agreement. The analysis of phase diagrams showed that the simplest diagram (two binary szeotropes and one distillation region) is observed for systems containing dimethyl sulfoxide and dimethylacetamide. It makes possible to separate cyclohexanone from catalyst and high boiling solvents by distillation.

1. INTRODUCTION Cyclohexanone (CHON) is one the important products in the technology of organic and petrochemical synthesis. The majority of cyclohexanone (95%) is an intermediate in processes for producing adipic acid, caprolactam, polyamides nylon-6, and nylon-66.1−6 There are different methods of obtaining cyclohexanone:7 oxidation of cyclohexane, phenol hydrogenation, dehydrogenation and oxidation of cyclohexanol, the oxidation of cyclohexene. The industrial methods are oxidation of cyclohexane (American company DuPont8), obtaining CHON from phenol (a Dutch company DSM9), and oxidation of cyclohexanol (a Japanese company Asahi9). One of the promising methods is oxidation of cyclohexene (CHEN) to cyclohexanone with n-benzoquinone in waterorganic solutions of cationic complexes of palladium(II).10,11 This process is characterized by high parameters of chemical reaction (conversion, selectivity) as well as soft conditions (298−373 K, atmospheric pressure). Literature review has shown that acetonitrile (AN), dimethyl sulfoxide (DMSO), dimethylformamide (DMFA), or dimethylacetamide (DMAA) can be used as solvent for this reaction.10,11 The development of new technology involves the creation of both catalytic and separation constituent. Separation flowsheet depends on the characteristic of chemical reaction and on qualitative and quantitative composition of the reactive mixture. At the same time if separation flowsheet is complex and energyintensive, the implementation of the technology can become inappropriate. Thus, the reaction and the separation constituents must be considered together. The joint analysis of both constituents of cyclohexanone production by oxidation of cyclohexene in the presence of water + acetonitrile12,13 showed that there is no possibility to separate cyclohexanone from solvents and catalytic system due to its high boiling temperature. Besides phase diagram of © XXXX American Chemical Society

quaternary system CHON + CHEN + Water + AN contains four binary and one ternary azeotrope, separatrix manifold that divides the diagram for two distillation regions, and a region of three-liquid phases.12−14 The catalytic system is redistributed among liquid phases that also has a negative impact on the separation process. The search for other solvents (with boiling point higher than 428.57 K), which will allow to separate the mixture and to get cyclohexanone of high purity in the distillate of the column, is relevant. The present work is devoted to the study of phase equilibrium of quaternary systems CHON + CHEN + Water + solvent (DMFA, DMSO, DMAA) that were recommended as solvents for chemical reaction and to the prediction of process separation. The method of studying is mathematical modeling.

2. COMPUTATIONAL METHODS Mathematical modeling of phase equilibrium of the quaternary systems was based on the NRTL15 equation using AspenTech ln γi =

∑j xiτjiGji ∑k xkGki

+

∑ j

⎛ ∑ x τ G ⎞ ⎜⎜τij − m m mj mj ⎟⎟ ∑k xkGkj ⎝ ∑k xkGkj ⎠ xjGij

where Gij = exp(−αijτil); τij = αij +

bij T

(1)

+ eij ln T + fij T ; αij = cij

+ dij(T − 273.15 K); τii = 0; Gii = 1. To check the adequacy of mathematical modeling we compared experimental and calculated results for next the parameters: boiling temperature of pure components, azeotrope characteristics (composition and boiling temperature), Received: October 3, 2017 Accepted: January 22, 2018

A

DOI: 10.1021/acs.jced.7b00870 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 1. Isobaric Experimental and Calculated Azeotropic Data for Systems Cyclohexene (CHEN) + Cyclohexanone (CNON) + Water (W) + Solvent (DMSO, DMFA, DMAA) at 101.325 kPa12,16−19 pure component/azeotrope

X1cal (mole frac)

X1exp (mole frac)

U (mole frac)

ur

Tcal (K)

Texp (K)

u (K)

ur

CHEN CHON W DMSO DMFA DMAA CHEN + W CHON + W CHON + DMFA

1 1 1 1 1 1 0.6822 0.1355 0.4329

1 1 1 1 1 1 0.6910 0.1320 0.4411

0 0 0 0 0 0 0.0088 0.0035 0.0082

0 0 0 0 0 0 0.0127 0.0265 0.0186

355.95 428.57 373.17 463.89 424.92 439.10 343.90 370.97 421.28

355.29 428.55 373.15 462.15 426.15 438.65 343.95 368.16 423.16

0.66 0.02 0.02 1.74 1.23 0.45 0.05 1.29 1.88

0.0019 0.00005 0.00005 0.0038 0.0029 0.0010 0.0001 0.0035 0.0044

Table 2. Experimental and Calculated LLE Data for Systems Cyclohexene (CHEN) + Water (W) and Cyclohexanone (CNON) + Water (W) at 101.325 kPa and 293.15 K12,20−26 binary system

X′1 (cal) (mole frac.)

X1″ (cal) (mole frac.)

X1′ (exp) (mole frac.)

X1″ (exp) (mole frac.)

u (X1′ ) (mole frac.)

ur

u (X1′ ) (mole frac.)

ur

W + CHEN W + CHON CHEN + DMSO

5.0 × 10−5 0.2527 0.9547

0.9985 0.9820 0.0453

5.0 × 10−5 0.2540

0.9981 0.9820

0.0 0.0013

0.0 0.0051

0.0004 0.0

0.0004 0.0

Figure 1. Phase diagrams of quaternary systems: cyclohexene (CHEN) + cyclohexanone (CNON) + water (W) + solvent (DMFA (a), DMSO (b), DMAA (c)) at 101.325 kPa.

the Euler characteristics which is equal to 0 for quaternary systems. Structures of composition tetrahedrons are given in Figure 1. Table 3 presents information about types and Poincare indexes for composition tetrahedrons. The balance of the Poincare indexes corresponds to the azeotropy rule and consequently diagrams have been constructed correctly.

and compositions of liquid phases corresponding to liquid− liquid (Tables 1 and 2). The relative standard uncertainty of description of phase equilibrium VLE, LLE is less than 0.03. The rest binary systems are zeotropic.12,17,27−31 There are no ternary and quaternary azeotropes in systems discussed. All solvents except for DMFA (its boiling temperature is lower than 428.55) meet the requirements. However, system with DMFA will be also considered as the solvent was also recommended for chemical reaction.10,11

Table 3. Types and Poincare Indexes of Singular Points of Concentration Tetrahedrons

3. THEORETICAL ANALYSIS The next step was the analysis of phase diagram of quaternary systems. Thermodynamical-topological analysis was used for this purpose.32−34 For each system, the type and Poincare indexes of all singular points were determined and structures of VLE diagrams were checked for compliance with the azeotropy rule

system

3

2(N4+ + S4+ − N4− − S4−) +

∑ (Nk+ + Sk+ − Nk− − Sk−) = E k=1

(2)

where N is the number of singular points of node type, S is the number of singular points of saddle type, ± is the the sign of the Poincare index, k is the boundary singular points, and E is B

CHEN + CHON + W + DMFA

CHEN + CHON + W + DMSO

CHEN + CHON + W + DMMA

singular point

type

i

type

i

type

i

CHEN CHON W DMSO DMFA DMAA CHEN + W CHON + W CHON + DMFA Σ

SN N+ SN

0 +1 0

SN SN SN N+

0 0 0 +1

SN SN SN

0 0 0

N+

+1

N− S SN

−1 −1 0 0

N− SN

−1 0

N+ N− SN

+1 −1 0

0

0

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Figure 2. Flowsheets of CHEN + CHON + W + solvent (DMSO, DMAA) mixture separation: (a,b) distillation columns and decanter; (c,d) distillation colunms.

Mixture can be also separated in flowsheet containing two simple distillation columns (or extractive distillation and simple distillation columns) due to the extractive effect of DMSO (DMAA30). Flowsheets are given in Figure 2. Mixture of water and cyclohexene should be returned to the chemical reaction stage or it can be separated in complex of two columns and decanter.

As can be seen from Figure 1 all phase diagrams contain twoliquid phase region (shaded field). Phase diagrams of systems with DMSO and DMAA contain two binary heterogeneous azeotropes and separatrix of first dimension and therefore there is one distillation region in which solvents are presented as stable nodes. System with DMFA contains one (homogeneous) azeotrope more, CHON + DMFA, and is characterized by the presence of twodimensional separatrix manifold that divides the diagram for two distillation regions. Such thermodynamic limitation will not allow separating the system for pure components, namely isolating of the reaction product (CHON) from solvent (DMFA) and catalytic system. The preliminary calculation of extractive effect of DMSO and DMAA showed that both solvents increase the volatility of CHEN relative to water and water relative to CHON. If the concentration of solvent in initial mixture is less than 25% it is necessary to use extractive distillation for mixture separation (both solvent can be used as extractive agents). If solvent concentration is higher than 25% a simple distillation column can be used. We can propose several flowsheets of separation of systems with DMSO and DMAA. For example, solvent containing catalytic system can be separated from ternary mixture CHEN + CHON + W by distillation. Depending on the composition of initial mixture (F0), it is possible to isolate CHON completely from CHEN and water by distillation or to use complex of columns and decanter. On the other hand, it is possible to separate first binary azeotrope CHEN + W (unstable node) and then separate ternary mixture CHEN + CHON + solvent in two distillation columns (or ternary mixture W + CHON + solvent in three distillation columns and decanter).

4. CONCLUSION The analysis of solvent (acetonitrile, dimethylformamide, dimethyl sulfoxide, and dimethylacetamide) properties that can be used in reaction of cyclohexene oxidation to cyclohexanone has shown that DMSO and DMAA are more promising compared to AN and DMFA. Both solvent have a boiling temperature higher than the target product (CHON). They do not form azeoptropes with components of initial mixture (CHEN, CHON, W), while AN and DMFA form new azeotropes that cause the appearance of separatic manifold. Therefore, the structure of VLE diagram for systems with DMSO and DMAA is simpler and contains just one distillation region. Such structure of phase diagram makes it possible to isolate solvent with high-boiling catalytic system from mixture that is not possible for AN and DMFA (in both systems CHON is singular point with maximum boiling temperature). All mixtures contain components of limited mutual solubility that form splitting regions in composition tetrahedrons. The presence of AN leads to the formation of region with three liquid phases (that intersects separatrix manifold). On one hand, this property can be used for separation of azeotropic mixture, but at the same time, we will observe the redistribution of catalytic system among liquid layers that may complicate separation process or lead to catalyst losses. C

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(4) Haritonov, A. S.; Ivanov, A. A.; Chernyavsky, V. S.; Piryutko, L. V. Method of cyclohexanol and cyclohexanone production. RUS. Pat. RF 2402520, 2009. (5) Haritonov, A. S.; Shubnikov, K. S.; Chernyavsky, V. S.; Ivanov, A. A. Method of cyclohexanol and cyclohexanone production. RUS. Pat. RF 2409548, 2009. (6) Parton, R. F. M. J.; Tinge, J. T. Cyclohexanone production process with impurities removal. U.S. Pat. Appl. Publ. US 2011/ 0028763, 2008. (7) Frolkova, A. K.; Maevskiy, M. A.; Oshanina, I. V.; Frolkova, A. V. Cyclohexanone. The main methods of obtaining and isolation of target product from the reaction mixture. Chimicheskaya Technologiya 2017, 18, 242−252. (8) Besmar, U. N.; Lyon, J. B.; Miller, F.; Musser, M. T. Preparation of cyclohexanone and cyclohexanol. US Pat. Appl. Publ. US 4720592, 1986. (9) Musser, M.; Cyclohexanol and cyclohexanone; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, 2005. (10) Temkin, O. N.; Bruk, L. G.; Zakharova, D. S.; Odincov, K. Yu.; Kacman, E. A.; Petrov, I. V.; Istomina, O. Yu. Kinetics of Cyclohexene Oxidation by p-Quinones in Aqueous-Organic Solutions of Cationic Palladium (II) Complexes. Kinet. Catal 2010, 51, 1−13. (11) Temkin, O. N.; Bruk, L. G.; Frolkova, A. V. The influence of composition of binary solvent CH3CN−H2O on the kinetics of oxidation of cyclohexene by p-BENZOQUINONES in solutions of cationic palladium(II) complexes. Fine Chemical Technologies 2015, 10, 77−84. (12) Frolkova, A. V.; Balbenov, S. A.; Frolkova, A. K.; Akishina, A. A. Phase equilibrium in the system water−acetonitrile−cyclohexene− cyclohexanone.Russ. Russ. Chem. Bull. 2015, 64, 2330−2336. (13) Frolkova, A. V.; Akishina, A. A.; Frolkova, A. K.; et al. Illarionova Ye.V. The Method of Study of Liquid−Liquid−Liquid Equilibrium in Quaternary Systems. J. Chem. Eng. Data 2017, 62, 1348−1354. (14) Frolkova, A. V.; Zakharova, D. S.; Frolkova, A. K.; et al. Balbenov S. A. Liquid−liquid and liquid−liquid equilibrium for ternary system water− acetonitrile−cyclohexene at 298.15 K. Fluid Phase Equilib. 2016, 408, 10−14. (15) Renon, H.; Prausnitz, J. M. Local compositions in thermodynamic excess functions for liquid mixtures. AIChE J. 1968, 14, 135−144. (16) Gmehling, J.; Boelts, R. Azeotropic Data for Binary and Ternary Systems at Moderate Pressures. J. Chem. Eng. Data 1996, 41, 202−209. (17) Ogorodnikov, S. K.; Lesteva, T. M.; Kogan, V. B. Azeotropic mixtures; Khimiya: Leningrad, 1971 (in Russian). (18) Marchenko, I. M.; Repina, L. N.; Misko, I. G. The research and development of heteroazeotropic distillation of mixture dimethylformamid - cyclohexanone in the presence of water. Zh. Prikl. Khim. 1990, 63, 1367−1372. (19) Steyer, F.; Sundmacher, K. VLE and LLE Data for the System Cyclohexane + Cyclohexene + Water + Cyclohexanol. J. Chem. Eng. Data 2004, 49, 1675−1681. (20) Polak, J.; Lu, B. C.-Y. Mutual Solubilities of Hydrocarbons and Water at 0 and 25 C. Can. J. Chem. 1973, 51, 4018−4023. (21) McBain, J. W.; Lissant, K. J. The solubilization of four typical hydrocarbons in aqueous solution by three typical detergents. J. Phys. Chem. 1951, 55, 655−662. (22) Haynes, W. M. Handbook of Chemistry and Physics, 92nd ed.; Taylor and Francis Group: Boca Raton, 2011. (23) Hauschild, T.; Knapp, H. Vapor-Liquid and Liquid-Liquid Equilibria of Water, 2-Methoxyethanol and Cyclohexanone: Experiment and Correlation. J. Solution Chem. 1994, 23, 363−377. (24) Gong, X.; Wang, Q.; Lei, F.; Shen, B. Measurements and Correlation of Liquid−Liquid Equilibria for the Ternary System Water + Cyclohexanol + Cyclohexanone. J. Chem. Eng. Data 2014, 59, 1651− 1655. (25) Pei, Y.; Wang, Q.; Gong, X.; Lei, F.; Shen, B. Distribution of cyclohexanol and cyclohexanone between water and cyclohexane. Fluid Phase Equilib. 2015, 394, 129−139.

Flowsheets discussed in this paper showed the possibility of separation of mixtures containing DMSO and DMAA in complexes of distillation columns and decanter. Besides extractive distillation can be considered as alternative method of separation. Simulation of distillation process and comparison of separation flowsheets in terms of energy consumption, as well as a comparison of chemical reaction parameters is planned in the nearest future.

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AUTHOR INFORMATION

Corresponding Author

*Tel.: +7 916 6658397. E-mail: [email protected]. ORCID

Anastasia V. Frolkova: 0000-0001-5675-5777 Funding

The work was carried out under support of Russian Science Foundation 16-19-10632. Notes

The authors declare no competing financial interest.

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SYMBOLS

AN Acetonitrile Az azeotrop CHON Cyclohexanone DMSO Dimethyl sulfoxide DMFA Dimethylformamide DMAA Dimethylacetamide i Poincare index components in a system LLE liquid- liquid equilibrium N singular point of node type S singular point of saddle type SN singular point of saddle-node type u standard uncertainty ur relative standard uncertainty VLE vapor−liquid equilibrium W Water x mole fraction of component in liquid phase

■

SUBSCRIPTS i components in a system j liquid phasein a system k tie-line

■

SUPERSCRIPT exp experimental data cal calculated data + stable node − unstable node

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REFERENCES

(1) Kirk, R. E.; Othmer, D. F. Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed.; Wiley: New York, 2001; Volume 7. (2) HIS Markit. Chemical Economics Handbook. https://www.ihs. com/products/cyclohexanol-chemical-economics-handbook.html (accessed July 2017). (3) Lebedev, N. N. Chemistry and technology of basic organic and petrochemical synthesis; Chimiya Publisher: Moscow, 1988 (in Russian). D

DOI: 10.1021/acs.jced.7b00870 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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(26) Wang, C.; Liu, X.; Wang, P.; Yang, P. Determination and Correlation of Liquid−Liquid Equilibrium Data for the Ternary Dichloromethane + Water + N,N-Dimethylacetamide System. J. Chem. Eng. Data 2014, 59, 1733−1736. (27) Carli, A.; Cave, S.; Sebastiani, E. Thermodynamic characterization of vapour-liquid equilibria of mixtures acetic acid-dimethylacetamide and water-dimethyacetamide. Chem. Eng. Sci. 1972, 27, 993− 1001. (28) Tochigi, K.; Akimoto, K.; Ochi, K.; Liu, F.; Kawase, Y. Isothermal Vapor-Liquid Equilibria for Water + 2-Aminoethanol + Dimethyl Sulfoxide and Its Constituent Three Binary Systems. J. Chem. Eng. Data 1999, 44, 588−590. (29) Zhang, Z.; Lv, M.; Huang, D.; Jia, P.; Sun, D.; Li, W. Isobaric Vapor−Liquid Equilibrium for the Extractive Distillation of Acetonitrile + Water Mixtures Using Dimethyl Sulfoxide at 101.3 kPa. J. Chem. Eng. Data 2013, 58, 3364−3369. (30) Mi, W.; Tong, R.; Hua, C.; Yue, K.; Jia, D.; Lu, P.; Bai, F. Vapor−Liquid Equilibrium Data for Binary Systems of N,NDimethylacetamide with Cyclohexene, Cyclohexane, and Benzene Separately at Atmospheric Pressure. J. Chem. Eng. Data 2015, 60, 3063−3068. (31) Radhamma, M.; Venkatesu, P.; Prabhakara Rao, M. V.; Prasad, D. H. L. Excess enthalpies and (vapour + liquid) equilibrium data for the binary mixtures of dimethylsulfoxide with ketones. J. Chem. Thermodyn. 2007, 39, 1661−1666. (32) Serafimov, L. A. Thermodynamical-topological analysis and separation of multicomponent polyazeotropic mixtures. Theor. Found. Chem. Eng. 1987, 21, 44−54. (33) Serafimov, L. A. Mathematical method in contemporary chemistry. Chapter 10. Thermodynamical and topological analysis of liquid-vapor phase equilibrium diagrams and problems rectification of multicomponent mixtures; Gordon and Brierch: New York, 1996. (34) Serafimov, L. A.; Frolkova, A. V.; Medvedev, D. V.; Semin, G. A. Determining the structure of the distillation line diagram from its geometric development for four-component mixtures. Theor. Found. Chem. Eng. 2012, 46, 120−127.

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DOI: 10.1021/acs.jced.7b00870 J. Chem. Eng. Data XXXX, XXX, XXX−XXX