65 7 Vol.65 No.

7
2014 7 CIESC Journal 2717
July 2014

-

100190

(MMA)-- MMA
MMA(1)+(2)+(3)+(4)MMA(1)+(2)+(3)+(4)
/
UNIQUAC

DOI10.3969/j.issn.0438-1157.2014.07.032
TQ 028.4 A 04381157201407271707

Liquid-liquid equilibrium for double solvent extraction of methyl methacrylate

from methanol

GUO WeiYAN RuiyiZHOU Qing, ZHANG Suojiang

(Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China)

AbstractMethyl methacrylate (MMA) is an important monomer, which is widely used for producing acrylic
resins or polymer dispersions. The two-step selective oxidation process which selectively oxidizes isobutylene to
MMA via methacrolein is regarded as a promising process for its high atomic efficiency. In the process, separation
of MMA is a critical technique due to high methanol concentration in the reaction. Traditional distillation could
not be used for separation of MMA from methanol because of azeotrope mixture. Double solvent extraction is a
good alternative. The liquid-liquid equilibrium (LLE) data for MMA-methanol-hexane-water quaternary system
were determined at 293.15 K and 303.15 K under atmospheric pressure. N-Hexane-water solvent system and
cyclohexane-water solvent system were used for the MMA extraction from methanol. The activity coefficient
model of universal quasi-chemical (UNIQUAC) was used to regress the LLE data of the investigated systems. The
parameters of the UNIQUAC model were obtained.

Key wordsmethyl methacrylate; methanol; double solvent; extraction

MMA [4-6]

MMA MMA

[1-3] MMA

2014-05-04 2014-05-14 Received date: 2014-05-04.

1985
Corresponding author: Prof. ZHANG Suojiang, sjzhang@ipe.ac.cn
(2012AA062903) Foundation item: supported by the National High Technology Research
and Development Program of China (2012AA062903).
2718 65

MMA MMA
[7-9] MMA
MMA 25%
MMA MMA

MMA MMA-
MMA-
MMA MMA

[10]
1
1.1
[11-12]
MMA 99.5%
MMA-- 98%
95%

[13] 99.5%


MMA 1 MMA
MMA

1 1.2
6890N
0.0001 g DMA5000
/ 0.01 K5106 gcm3
MMA SHA-C 0.1 K
MMA 1.3

1:1 6

1 298.15 K MMA (1)+(2)+/(3)

Fig.1 Ternary phase diagram of MMA(1)+methanol(2)+ n-hexane or cyclohexane(3) system at 298.15 K
7 - 2719

1
Table 1 Comparison of experimental densities of solvents
with literature values 0.1 K
Solvent T/K exp/gcm3 lit/gcm3 FID 30 m320
0.8048[14]
methanol 293.15 0.7996
m1.80 m DB-624 25 mlmin1
0.790[15]
303.15 0.7870 0.7853[14]
400 mlmin1 40 mlmin1
MMA 293.15 0.9392 0.943[14] 40 4 min 8min1 5
303.15 0.9290 0.930[14] min 25min1 1.6 min 120
n-hexane 293.15 0.6569 0.6572[14] 2 min 200
0.6599[16]
280
0.6594[17]
303.15 0.6521 0.6508[16]
0.999
0.65844[17] 1.4
cyclohexane 293.15 0.7810 0.778[14]
0.7786[16]
K=wi / wi
[14]
303.15 0.7708 0.769
wiwi i
0.7692[18]
0.76918[19]

MMA: : / 1:1:0.5 =( wi/ wi)/( wj/ wj)

1:1:11:1:2 3 wiwj ij

10%15%25% wiwj ij

E= m/m0
10 min 2 h m MMA m0 MMA

2 MMA (1)+(2)+(3)+(4)
Table 2 Experimental data of phase equilibria of MMA(1)+methanol(2)+n-hexane(3)+water(4) system
Proportion/%(mass) Phase separation
No. T/K Organic phase/% Aqueous phase/%
w1 w2 w3 w4
w1 w2 w3 w4 w1 w2 w3 w4
1 293.15 35.98 35.98 17.99 10.04 44.70 10.21 43.34 1.75 34.09 44.55 7.92 13.44
2 293.15 33.99 33.99 16.99 15.04 50.26 7.68 40.02 2.04 25.93 47.95 2.63 23.49
3 293.15 29.97 29.97 14.99 25.07 58.98 5.24 33.77 2.01 12.06 45.61 0.30 42.03
4 293.15 30.00 30.00 30.00 10.00 39.64 6.17 54.31 0.12 26.63 51.95 4.30 17.12
5 293.15 28.22 28.22 28.22 15.34 40.37 4.66 53.67 1.30 17.28 51.11 1.03 30.58
6 293.15 25.00 25.00 25.00 25.01 43.50 2.70 49.10 4.70 7.25 45.03 0.15 47.57
7 293.15 22.50 22.50 44.99 10.01 28.74 2.95 66.53 1.78 14.72 56.67 1.56 27.05
8 293.15 21.25 21.25 42.51 14.98 27.81 1.75 67.90 2.54 7.82 51.26 0.31 40.61
9 293.15 18.75 18.75 37.50 25.00 32.63 1.34 62.83 3.20 4.12 41.70 0.04 54.14
10 303.15 35.96 35.96 17.98 10.10 43.96 12.42 40.42 3.20 33.65 43.81 8.22 14.32
11 303.15 33.97 33.97 16.99 15.07 50.14 8.64 39.11 2.11 25.31 47.86 2.78 24.05
12 303.15 29.98 29.98 14.99 25.04 54.46 6.09 33.39 6.06 12.96 45.99 0.33 40.72
13 303.15 30.00 30.00 30.00 10.00 36.55 5.37 56.58 1.50 22.62 53.36 3.30 20.72
14 303.15 28.33 28.33 28.33 15.00 36.88 5.90 57.16 0.06 14.00 52.75 0.96 32.29
15 303.15 25.00 25.00 25.00 25.00 39.9 2.33 54.75 3.02 6.43 43.43 0.11 50.03
16 303.15 22.50 22.50 45.00 9.99 25.05 2.29 71.44 1.22 10.89 57.57 0.91 30.63
17 303.15 21.23 21.23 42.47 15.07 26.58 1.70 71.10 0.62 6.55 50.35 0.23 42.87
18 303.15 18.75 18.75 37.49 25.01 27.43 1.15 68.36 3.06 3.10 38.73 0.03 58.14
2720 65

2 293.15 KMMA
1:1:2 1.95 7.92
2.1 MMA(1)+(2) +(3)+(4)
37.51 246.46

MMA
293.15 K 303.15 K MMA(1)+(2)+

(3)+(4) 2
3
2 MMA
1 10
3 3
293.15 K 303.15 K
MMA MMA
1.31

9 18 293.15 K
293.15 K 10%
303.15 K 7.92 8.85
1.31 1.95
2 10%15% 25%
5.72 37.51

MMA

3 MMA
Table 3 Partition coefficients and selectivity coefficients of
MMA
MMA
No. T/K KMMA MMA

1 293.15 1.31 5.72
2 293.15 1.94 12.10 MMA
3 293.15 4.89 42.57
4 293.15 1.49 12.53 2.2 MMA (1) +(2)+(3) +(4)
5 293.15 2.34 25.62
4 MMA (1)+(2)+(3)+(4)
6 293.15 6.00 100.07
7 293.15 1.95 37.51 293.15303.15 K
8 293.15 3.56 104.17 5 MMA (1)+
9 293.15 7.92 246.46 (2)+(3)+(4)
10 303.15 1.31 4.61
MMA MMA
11 303.15 1.98 10.97
12 303.15 4.20 31.73
13 303.15 1.62 16.056 MMA
14 303.15 2.63 23.55 MMA (1) +(2) +(3) +(4)
15 303.15 6.20 115.66

16 303.15 2.30 57.83
17 303.15 4.06 120.19 3 10%15% 25%
18 303.15 8.85 298.00 MMA-

2 298.15 K MMA (1)-(2)-(3)

Fig.2 Effects of water on ternary phase diagram of MMA(1)-methanol(2)-n-hexane(3) system at 298.15 K
7 - 2721

4 MMA (1)+(2)+(3)+(4)
Table 4 Experiment data of phase equilibria of MMA(1)+methanol(2)+cyclohexane(3)+water(4) system
Proportion/%(mass) Phase separation
No. T/K Organic phase/% Aqueous phase/%
w1 w2 w3 w4
w1 w2 w3 w4 w1 w2 w3 w4
1 293.15 36.02 36.02 18.01 9.96 43.52 12.78 40.34 3.36 31.62 44.08 9.76 14.54
2 293.15 33.94 33.94 16.99 15.13 48.05 9.24 36.23 6.48 25.03 50.16 3.76 21.05
3 293.15 29.97 29.97 14.98 25.08 55.20 6.23 33.13 5.44 11.07 47.73 0.48 40.72
4 293.15 30.02 30.02 30.02 9.95 38.69 5.81 54.76 0.74 22.00 53.51 4.68 19.81
5 293.15 28.22 28.22 28.22 15.33 40.49 4.26 50.51 4.38 16.16 52.42 1.68 29.74
6 293.15 24.95 24.95 24.95 25.15 45.21 3.15 48.28 3.36 7.95 45.49 0.31 46.25
7 293.15 22.50 22.50 44.99 10.02 27.00 2.63 68.14 2.23 13.09 56.33 2.14 28.44
8 293.15 21.24 21.24 42.49 15.03 28.80 1.99 67.10 2.11 7.88 52.46 0.72 38.94
9 293.15 18.75 18.75 37.51 24.99 30.52 1.21 65.97 2.30 3.31 39.61 0.09 56.99
10 303.15 35.92 35.92 17.96 10.20 42.93 13.63 38.21 5.23 34.36 41.53 11.91 12.20
11 303.15 33.95 33.95 16.97 15.14 44.64 10.00 38.58 6.78 24.45 47.55 3.93 24.07
12 303.15 30.00 30.00 15.00 25.00 47.23 5.65 37.40 9.72 15.19 57.81 0.82 26.18
13 303.15 29.95 29.95 29.95 10.14 35.88 8.13 49.40 6.59 23.41 51.41 5.99 19.19
14 303.15 28.31 28.31 28.31 15.06 39.90 5.58 49.87 4.65 16.16 53.1 2.06 28.68
15 303.15 24.99 24.99 24.99 25.02 44.98 3.77 47.45 3.80 7.56 46.63 0.39 45.42
16 303.15 22.50 22.50 44.98 10.02 26.57 3.01 65.63 4.79 13.76 56.93 2.46 26.85
17 303.15 21.27 21.27 42.55 14.91 27.57 2.41 64.44 5.58 7.99 52.53 0.55 38.93
18 303.15 18.71 18.71 37.40 25.18 29.51 1.54 64.50 4.45 3.36 40.60 0.06 55.98

5 MMA
Table 5 Partition coefficients and selectivity coefficients
of MMA
No. T/K KMMA MMA [20]
1 293.15 1.38 4.75
UNIQUAC 1[21-22]
2 293.15 1.92 10.42
i z
3 293.15 4.99 38.20 ln i = ln + qi ln i qiln ti
xi 2 i
4 293.15 1.76 16.20 (1)
i
5 293.15 2.50 30.83 qi j
j ij / ti + li + qi

j x jl j
xi
6 293.15 5.69 82.12
7 293.15 2.06 44.18 Aspen Plus
8 293.15 3.65 96.35 2
9 293.15 9.22 301.84
ij=exp(aij+bij/T) (2)
10 303.15 1.25 3.81
11 303.15 1.82 8.68
aijbij T
12 303.15 3.11 31.81 Ordinary Least SquaresBritt-Luecke
13 303.15 1.53 9.69 Deming 6
14 303.15 2.47 23.49 2.4
15 303.15 5.95 73.59
MMA-
16 303.15 1.93 36.52
17 303.15 3.45 75.21 -293.15 K
18 303.15 8.78 231.54
-- 7
7 MMA
81.60% 2.70%
2.3 43.50%
UNIQUAC
2722 65

3 298.15 K MMA (1)-(2)-(3)

Fig.3 Effects of water on ternary phase diagram of MMA(1)-methanol(2)-cyclohexane(3) system at 298.15 K

6 UNIQUAC
Table 6 Values of UNIQUAC binary parameters regressed from LLE data of
MMA(1)+methanol(2)+n-hexane/cyclohexane(3) +water(4) system
MMA(1)+methanol(2)+n-hexane(3) +water(4) system MMA(1)+methanol(2)+cyclohexane(3) +water(4) system
i-j 293.15 K 303.15 K 293.15 K 303.15 K
ij ji ij ji ij ji ij ji
1-2 37.80 0.76 1.95 1.62 44.54 0.74 1.22 1.77
1-3 1.82 0.50 0.64 3.66 0.21 1.64 1.08 1.40
1-4 2.85 0.85 4.43 0.03 1.53 0.45 2.20 0.28
2-3 0.47 53.59 0.15 0.13 0.91 9.45 2.96 0.24
2-4 1.65 58.00 5.25 1.57 1.65 94.83 2.39 1.16
3-4 1.62 0.34 3.25 10.28 0.36 0.54 1.36 0.02

7 MMA
Table 7 Two-stage extraction efficiency for MMA
Organic phase/% Aqueous phase/%
Extraction stage KMMA MMA E/%
MMA Methanol MMA Methanol
1 43.50 2.70 7.25 45.03 6.00 100.07 81.60
2 46.19 0.28 0.89 4.01 51.90 743.28 80.70
2* 13.13 0.50 4.40 56.35 26.26 336.30 15.15

2 2

- MMA
0.28%MMA - MMA
80.70%
0.50%MMA 13.13% MMA MMA-
MMA 95.85% MMA
MMA

E MMA , %
/- MMA-
KMMA MMA , %
T , K
/MMA w1w2w3w4 MMA
MMA , %
MMA MMA , %
7 - 2723

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