Thermodynamics Study on the Separation Process of Cresols from

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Thermodynamics Study on the Separation Process of Cresols from Hexane via Deep Eutectic Solvent Formation Tiantian Jiao, Hongyan Wang, Fei Dai, Chunshan Li, and Suojiang Zhang Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.6b00649 • Publication Date (Web): 01 Jul 2016 Downloaded from http://pubs.acs.org on July 10, 2016

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Industrial & Engineering Chemistry Research

Thermodynamics Study on the Separation Process of Cresols from Hexane via Deep Eutectic Solvent Formation Tiantian Jiaoa,b, Hongyan Wanga,b, Fei Daia,b, Chunshan Lia,*, Suojiang Zhanga,* a

Beijing Key Laboratory of Ionic Liquids Clean Process, State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, PR China b College of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, PR China

Abstract Phenolic compounds could be separated through their formation of deep eutectic solvent (DES). This process was different from normal liquid-liquid extraction and was more efficient and environmental. In this work, the thermodynamic process of this kind of separation was studied. Ternary liquid-liquid equilibrium data were systematically measured at atmospheric pressure and temperatures from 303.15 to 313.15 K. The experimental data were regressed by NRTL and UNIQUAC models, and the validated results revealed that NRTL model presented better consistent with experimental data. Above-mentioned parameters could be used to predict ternary mixture interactions and then applied insubsequent design and optimization of the separation process of corresponding systems. This extraction process was further optimized using Aspen Plus with NRTL as thermodynamic model. The simulation results were in well agreement with the experimental outcomes. Keywords: cresol; DES; thermodynamics; ternary phase diagram; optimization *

Corresponding author:

Chunshan Li. TEL/FAX: +86-10-82544800; E-mail: [email protected] Suojiang Zhang. TEL/FAX: +86-10-82627080; E-mail: [email protected]

ACS Paragon Plus Environment


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1. Introduction Phenols, as the important raw material, are widely used in chemical industry. Majority of them could be obtained from coal tar and coal liquefied oil, also petroleum 1. The traditional separation method for phenols is alkaline wash, which brings environmental damage. Liquid-liquid extraction becomes a promising method due to its large capacity and easy operation. The solvents that used were organic solvents 2, ionic liquids3,4, and deep eutectic solvents 5,6. Deep eutectic solvents, as a new kind of solvent, could be easily formed by mixing two compounds together. They get lower melting points than each individual component and are used in liquid form. The physic-chemical properties of DES are highly similar to ionic liquids

7,8

. Since Abbott 9 et al. first defined and prepared DES

using chloride and urea with a mole ratio of 1:2, a variety of DES were synthesized, and applied to many fields, such as electrochemistry10,11,12, nanomaterial13,14, biochemistry15,16,17, and separation 18,19. DES can be used in separation process in two approaches. Firstly, they can be employed as usual extraction agent that the ready-prepared DES mixed with the separation system in liquid form. Secondly, the separation could be processed through the formation of DES. As we know, DES can be synthesized by mixing hydrogen-bonding acceptor (HBA) and hydrogen-bond donor (HBD) at a certain mole ratio. If the separation system contained HBA or HBD, DES formed after the addition of HBD or HBA. If the formed DES is insoluble with the separation system, they can


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be separated. Most of the separation process used DES through the first approach. They were successfully used in the separation of glycerol from biodiesel

20,21,22

,

toluene from toluene/heptane mixtures 23,24,25, aromatics from aliphtatics and n-octane 26

, alcohols from esters 27, bovine serum albumin (BSA) 28,29, bitumen from oil sand 30,

hydroxynethylfurfural from 2, 5-diformylfuran 31, caechin from green tea 32. This kind of separation achieved relative good results, and then the second separation approach was found to be able to conduct. Hou et al.

33

found that quaternary ammonium salts

could form DES with certain kinds of benzene poly (carboxylic acid), and then the isomers could be separated, and hydrogen bond formed between them. Pang et al. 5 found that phenols could be separated through the formation of DES with choline chloride with the extraction efficiency more than 90%. The homologous compounds of choline chloride were studied by Guo et al. 34, a variety of quaternary ammouium were investigated in this article, tetraethylammonium chloride was selected as the optimum extraction agent that almost all phenols could be separated. In our previous works, imidazole (IMZ) 35, nicotinamide 36 and their homologous compounds could be used as HBD to separate phenols from hexane through the formation of DES with phenols removal efficiencies more than 95%, FT-IR and molecular simulation proved the existence of hydrogen bond. The application of DES in separation process presented rapidly increasing tendency. However, minor research attention has been focused on the thermodynamics study related to DES separation process. Kareem et al. 23, 24 investigated the separation process of toluene from hydrocarbons mixture using DES, in which the liquid-liquid



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equilibrium(LLE) data were detected systematically at 30, 40, 50, 60 oC and correlated by non-random two liquid (NRTL) model. Mulyono et al.

26

measured the

equilibrium data of BTEX (benzene, toluene, ethylbenzene and m-xylene) aromatics, n-octane, and DES at 25

o

C and correlated them using NRTL model. In

above-mentioned thermodynamic researches, DES was all utilized as usual solvent, few studies were involved in the formation of DES during the separation process. In this work, the thermodynamics study is carried out for the separation of cresols from model oil using imidazole by the formation of DES. The ternary phase concept diagram is proposed and the whole separation process could be interpreted on the basis of the concept diagram. Liquid-liquid equilibrium data of cresols (o-cresol, m-cresol), imidazole, and hexane are systematically measured at 303.15 K and 313.15 K and atmospheric pressure. The experiment data are correlated using NRTL and UNIQUAC model, and the binary interaction parameters are obtained. NRTL presented better consistency with the experimental data and is selected for the subsequent optimization of extraction equipment with the thermodynamic as theoretical basis. This process could effectively improve the cresols extraction efficiency and be important for the subsequent process optimization. 2. Phase behavior of the ternary mixtures During the experimental process, as imidazole added into the model oil (hexane and phenols), a series of transformation could be observed. (1) Singe Liquid phase When the mole ratio of IMZ to phenols was low, there was no stratification. That


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is to say, single-phase region existed in this system at a low mole ratio of IMZ to phenols. (2) Liquid-Liquid phases Then, as the increase addition amount of IMZ, the remained model oil that DES dissolved in got saturated, and the undissolved DES was separated out at the lower layer. Then two layers appeared, the system turned into liquid-liquid phases region. This may attribute to the limited solubility of DES formed by phenols and IMZ in existing phenols oil. (3) Liquid-Liquid-Solid phases As the continuously increased addition of IMZ, the formed DES with phenols increased simultaneously. As known from the experiment that DES was synthesized by mixing two or more compounds at a certain proportion. When the addition amount of IMZ achieved the maximum point, the continued addition of IMZ would be existed in solid form at the bottom of the tube. Under this condition, there would be three phases existed in this system: two liquid phases and the remained solid IMZ. When IMZ was sufficiently combined with phenols to form DES, the continuously added IMZ would not affect the concentrations of the upper and lower layers 37. A solid phase area appeared in the ternary phase diagram, which is unlike the usual diagram, and the liquid-liquid area appeared upon the solid phase. As discussed above, ternary phase diagram of the separation process of cresols from model oil through the formation of DES could be seen from Figure 1 as below 38.



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Figure 1. The ternary phase diagram of the separation process through DES formation As shown in Figure 1, three different processes represented as the increased addition of IMZ: single liquid phase, liquid-liquid phases, liquid-liquid and the remaining solid phases. This phase diagram could be applied to the common separation process on the basis of forming DES. The ternary phase diagrams were all in the same form like Figure 1, but their DES ultimate formation point might be different. The distribution coefficient (di) for hexane and cresol in this ternary system, also the separation factor (S) could be used to evaluate the ability of IMZ for the separation of cresol from model oil. The specific calculating formulas are as follow:

=

(1)

S =

(2)

In Eqs. 1 and 2, the subscript i denoted the component number (1 was for IMZ, 2 was for m-cresol and o-cresol, 3 was for hexane); xi referred to the mass fraction of i component; xi1 and xi3 represented the mass fraction of i component in the DES and hexane phases, respectively. 3. Experiment 3.1 Chemicals Table 1. The chemicals used in the experimental process In all cases, the percentage purities mentioned in Table 1 refer to mass fraction as reported by the suppliers. All the chemicals were used in the experiment without further purification.


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3.2 Experiment apparatus The LLE data were measured by an experimental facility which was purchased from Zhejiang University. The facility mainly included thermometer, upper sampling point, lower sampling point, magnetic stirrer, and thermostatic water. And the temperature could be maintained within ± 0.1 K. The experiments were performed as follows: the different proportions of hexane, cresols and IMZ mixtures were prepared and transferred into the LLE still. The still was an incubator shaker with the stirring speed of 400 rpm. The extraction was conducted more than 60 min in order to guarantee their complete reaction. Then two layers formed and were allowed to stand for more than 60 min. Finally, the samples of the upper layer and lower layers were took out, and analyzed. 3.3 Analysis methods This article used a gas chromatograph (SHIMADZU) with BID detector to detect the component content of the upper and lower layer. The chromatographic column used in GC was a 50 m × 0.20 mmφ capillary column (Restek Rtx-Wax). The chromatographic conditions were 220 °C for the oven and 250 °C for the injector and detector. The cresol and IMZ mass fractions of both upper and lower layer could be detected and calculated by GC, and their standard curves were as follow: o-cresol y=5.499×108 x, R2=0.999

(3a)

m-cresol y=5.457×108 x, R2=0.999

(3b)

Imidazole y=4.3095×108 x, R2=0.999

(3c)



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The hexane mass fraction could be obtained on the basis of the mass fraction normalization method. 3.4 Error analysis The errors of experimental process encompassed inherent error and statistical/random error. Inherent error mainly included the instrumental error and calculation error. And random error could be eliminated through parallel experiments. Analytical balance was used to weigh the mass of reagent with an accuracy degree of ±0.001 g. The constant temperature water bath shaker was used to keep the constancy of temperature with a controller within ±0.1 K. GC was used to measure the mass fractions of these components, and the mass fraction values were corrected to four decimal places. For each experimental data, the experiments were repeated three times under the same conditions. Due to the high concentration of cresol and imidazole in the DES layer, it was diluted to about 1 in 20 and then detected using GC. The mean absolute deviation (MAD) of the experimental data was used to evaluate the central tendency of the experimental data and their precision, which could be seen from Table 2, the calculation equation was shown as Eq. 4.

, , MAD(xi)= ( ) ∑ − , ,

(4)

Where xexp represented experimental mass fraction, represented for the

average experimental mass fraction; n means the phase number, its values were 1 for upper layer and 2 for lower layer; i represented the compounds kinds, their values 1, 2, 3 represented IMZ, m-cresol or o-cresol, and hexane, respectively; j means the


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experimental data number, N is the total number of experimental data. Table 2. The MAD of experimental data for the ternary system: IMZ (1) + m-cresol, o-cresol (2) + hexane(3) at different temperature. As shown in Table 2, the MADs of the experimental data were relatively low. But as the increasing of reaction temperature, the MADs of both m-cresol and o-cresol increased to a certain degree. Due to the treatment of lower layer before detection, the MADs of the lower layer were much larger than upper layer. The absolute deviation(AD) for each experimental data could be seen from Supplementary material Table 1. 4. Results and discussion 4.1 LLE experimental data The LLE data of two systems [IMZ-(o-cresol)-hexane, IMZ-(m-cresol)-hexane] were measured at 303.15 and 313.15 K and atmospheric pressure. And the ternary phase diagrams were shown in Figures 2 and 3.

Figure 2. Ternary phase diagrams of LLE for the ternary system: IMZ + m-cresol + hexane at T= 303.15 K (Figure 2a) and 313.15 K (Figure 2b), x1, x2 and x3 mean mass fractions of IMZ, m-cresol and hexane.

Figure 3. Ternary phase diagrams of LLE for the ternary system: IMZ + o-cresol + hexane at T= 303.15 K (Figure 3a) and 313.15 K (Figure 3b), x1, x2 and x3 mean mass fractions of IMZ, o-cresol and hexane. As shown in Figures 2 and 3, the ternary phase diagrams of IMZ, cresols and hexane were in consistent with the phase diagram that proposed in section 2. As the increasing addition of IMZ, the IMZ mass fraction of the lower layers increased and the cresols mass fractions of the lower layer firstly increased to more than 0.6 then



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decreased until around 0.5; the hexane mass fractions of the lower layer decreased rapidly at first and then slowly down. In the upper layer, the IMZ mass fraction maintained low level, and the mass fraction of cresols and hexane decreased as the increasing addition of IMZ. The separation could achieve pretty good results at a not-too-much IMZ addition (the mole ratio of IMZ to cresols about 0.8:1). After this point, the decrease ranges of hexane and cresols were limited, that was consistent with our previous experiment where the cresol concentration changed little when the mole ratio of IMZ to cresols arrived 0.8:1. According to the solubility law, the liquid-liquid phase area should be decreased as the temperature increasing. But the ternary phase diagrams of 303.15 and 313.15 K had no significantly difference that might due to the minor temperature difference. This was also consistent with the experiment that the cresols removal efficiencies slightly decreased when the temperature increased from 303.15 to 313.15 K. Then, the di and S were calculated and listed in Table 2, which indicated the excellent extraction ability of IMZ on cresols. The specific cresols extraction performance at 303.15 and 313.15 K were shown in Figures 4 and 5. As can be seen from Table 3 and Figures 4 and 5, IMZ could separate cresols from hexane with high-efficiency. The di and S of m-cresol were a bit larger than o-cresol, which means the extraction efficiency of m-cresol would be higher than o-cresol under the same condition. This conclusion was agreed with experiment results. This might due to the different replacement positions of methyl substituent on phenol. When methyl substituent was replaced at ortho-position, the steric hindrance


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might be greater for the hydrogen-bond interaction between phenolic hydroxyl group of cresol and amine group of IMZ than meta-substitution. Furthermore, the di and S for both m-cresol and o-cresol changed little within the investigated temperature that was also consistent to experimental process. Table 3. di of hexane (i=3) and cresols (i=2) and S along the cresols concentrations in hexane (x23)

Figure 4. Distribution coefficients of o-cresol and m-cresol (d2) as a function of the mass fraction of o-cresol or m-cresol in hexane phase (x23).

Figure 5. Separation factor of o-cresol and m-cresol (S) as a function of the mass fraction of o-cresol or m-cresol in hexane phase (x23). 4.2 LLE experimental data correlation Liquid-liquid equilibrium data could be fitted using appropriate thermodynamic model, and binary interaction parameters were able to obtain. Nonrandom two-liquid (NRTL) model and universal quasi-chemical correlation activity coefficient method (UNIQUAC) model could be used to describe the liquid-liquid equilibrium. They were widely used in LLE processes, and represented satisfactory result. The LLE data were regressed through these two models, and their reliabilities were verified via the comparison between experimental data and the calculated data. The calculation model of NRTL with n components in solution was shown as follow 39:

∑ ! ! In = +$ % ∑" !" " ∑" !" " ! = exp+−,

- , !

= exp+−,

- ,

Where T is the absolute temperature K,

∑& & & !& ' − ∑" " !" =

./ 0.

and

12

parameters of NRTL.


=

3/ 2

, , = , .

(5)

are the binary interaction


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UNIQUAC model which was developed by Abrams and Prausnitz 40 could be seen as follow:

∅ 8 ; In = 56 + : 56 − :′ In $ ; ′ 2 ∅ = /

∅ = ∑>

/? =/ /

AB

3/

, ; = ∑>

@

/? @/ /

= exp C D , E = − C 2

− @ ’

, ;′ = ∑>

F/ 0F 1

:′ ∑ ; ′ ∅ ∑ 99.0% w

Sinopharm Chemical Reagent Co., Ltd

Hexane

110-54-3

>95.0% w


Imidazole

288-32-4

>99.0% w

J&K Scientific Co., Ltd

Ethanol

64-17-5

>99.7% w




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Table 2 MAD (M-cresol-IMZ-Hexane) T

x1

Ⅰ

x2

Ⅰ

303.15 K 313.15 K

0.0003 0.0004

0.0008 0.0021

303.15 K 313.15 K

0.0005 0.0005

0.0018 0.0025

x3

Ⅰ

0.0010 0.0022

x1

Ⅱ

0.0065 0.0068

x2

Ⅱ

x3

Ⅱ

0.0066 0.0106

0.0071 0.0111

0.0069 0.0085

0.0089 0.0112

MAD (O-cresol-IMZ-Hexane) 0.0019 0.0029

0.0056 0.0080


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Table 3. x23

d3

d2

S

x23

d3

d2

S

o-cresol at 313.15 K

o-cresol at 303.15 K 0.006

0.042

74.51

1759

0.006

0.051

79.61

1556

0.008 0.011

0.042 0.032

61.19 47.60

1465 1504

0.008 0.011

0.039 0.037

64.37 40.85

1652 1116

0.022

0.031

27.84

901

0.019

0.026

31.18

1194

0.039

0.066

16.86

254.5

0.018

0.031

31.34

1026

0.039

0.367

13.70

37.4

0.029

0.056

20.7

370.3

0.059

0.207

10.80

52.3

0.044

0.136

14.19

104.7

0.067

0.247

9.36

37.8

0.086

0.208

7.586

36.5

0.108

0.276

5.76

20.9

0.157

0.374

3.879

10.4

29.7

0.089

0.326

6.99

21.5

0.046

m-cresol at 303.15 K 0.397 11.80

m-cresol at 313.15 K

0.059

0.320

9.94

31

0.044

0.181

14.98

83

0.040 0.034 0.023 0.015 0.008 0.004

0.266 0.177 0.132 0.063 0.026 0.020

15.61 18.98 28.02 43.71 77.96 119.80

58.6 107.4 212.2 693.1 3031 5943

0.017 0.009 0.007 0.005 0.003 0.002

0.117 0.072 0.045 0.023 0.030 0.040

35.81 65.16 86.5 103.3 143.3 195.1

305.7 902.5 19068 45088 48478 4908



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Table 4 NRTL 303.15 K Component （i,j）

τij

313.15 K τji

Component （i,j）

α

1,2

0.3956

32.99

1,3

-0.9704

1.1360

2,3

-0.2278

-0.2000

0.2

τij

τji

1,2

-3.919

-1.335

1,3

1.203

0.8790

2,3

0.6629

0.2259

α

0.2

UNIQUAC Component （i,j）

τij

τji

1,2

0.2107

341.1

1,3

0.9990

0.0963

2,3

1.6463

0.2054

z

Component （i,j）

τij

τji

1,2

0.0061

1010

1,3

0.4705

6.501

2,3

2.294

0.0951

10

z

10

AAD/NRTL

T

T

x1

Ⅰ

x2

Ⅰ

x3

Ⅰ

x1

Ⅱ

x2

Ⅱ

x3

Ⅱ

303.15 K

1.235

0.0001

0.0012

0.0011

0.0129

0.0214

0.0287

313.15 K

0.225

0.0000

0.0008

0.0007

0.0143

0.0175

0.0127

AAD/UNIQUAC 303.15 K

0.7905

0.0008

0.0056

0.0055

0.0620

0.1166

0.0554

313.15 K

0.5305

0.0007

0.0033

0.0031

0.0606

0.1168

0.0729


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Table 5 303.15 K

313.15 K NRTL

Component （i,j）

τij

τji

1,2

-1.639

0.5093

1,3

2.236

-4.635

2,3

30.22

3.390

α

Component （i,j）

0.2

τij

τji

1,2

-1.091

0.5801

1,3

1.741

-4.197

2,3

31.93

2.923

α

0.2

UNIQUAC Component （i,j） 1,2

τij

τji

0.0034

3.781E+07

1,3

0.7056

2,3

1.3511 T

2.149E+06 0.4435

z

10

Component （i,j） 1,2

τij

τji

3.740E-05

2.810E+13

1,3

0.3895

2,3

1.387

2.439E+12 0.4250

z

10

AAD/NRTL T

x1

Ⅰ

x2

Ⅰ

x3

Ⅰ

x1

Ⅱ

x2

Ⅱ

x3

Ⅱ

303.15 K

0.6348

0.0003

0.0018

0.0015

0.0117

0.0116

0.0120

313.15 K

0.6649

0.0008

0.0051

0.0043

0.0394

0.0342

0.0181

AAD/UNIQUAC 303.15 K

0.1736

0.0008

0.0072

0.0067

0.0669

0.1168

0.0499

313.15 K

0.17056

0.0012

0.0110

0.0102

0.0641

0.0952

0.0364



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Figure 1.


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Figure 2.



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Figure 3.


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Figure 4.



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Figure 5.


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Figure 6



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Figure 7


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Figure 8



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Figure 9


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Table of content (TOC)


Thermodynamics Study on the Separation Process of Cresols from

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