原甲酸三甲酯-醋酸萃取精馏全局多目标优化

doi:10.11949/0438-1157.20220747

摘要/Abstract

摘要：

在生产杀菌剂嘧菌酯中间体过程中，反应物原甲酸三甲酯（TMOF）与生成物醋酸（HAc）发生共沸，导致反应物堆积和原料损耗。为解决共沸物分离问题，使用Hayden-O'Connell修正的UNIFAC基团贡献法研究其汽液平衡，设计常规萃取精馏（CED）、侧线萃取精馏（SED）、隔壁塔萃取精馏（EDWC）三种工艺，以分离组分摩尔纯度、再沸器热负荷（Q）、年度总费用（TAC）为目标，运用灵敏度耦合箱线图响应面法（S-BBD）对三种工艺参数分别优化。结果表明，优化方法预测值与实际值存在较优拟合关系， CED、SED、EDWC对TAC和Q的预测误差均不超过1%。分离纯度相同时，SED较CED节约10.37%TAC和6.88%热负荷，EDWC较CED节约10.65%TAC和10.53%热负荷，三种工艺方案均可为化工实际生产提供理论基础。

关键词: 共沸物, 计算机模拟, 经济, 基团贡献法, 萃取精馏, 多目标优化

Abstract:

The highest azeotrope exists between the reactant trimethyl orthoformate (TMOF) and the product acetic acid (HAc) in the production of 3- (methoxy methotenyl) - 2 (3H) benzofuranone, which leads to the accumulation of reactants and the loss of raw materials and is not conducive to the forward reaction. For TMOF-HAc system, vapor-liquid equilibrium was calculated and analyzed by Hayden-O'Connell's UNIFAC group contribution method with modified fugability coefficient. After error verification, NRTL-HOC model was used as the basis of simulation distillation. The azeotrope can be separated by empirical extractive distillation. The entrainment performance of HAc with N-methyl acetamide (NMA) and N-methyl pyrrolidone (NMP) was compared, and NMP was selected as the extractant. Conventional extractive distillation (CED), side-stream (liquid) extractive distillation (SED) and extractive dividing-wall column (EDWC) were designed with the objective of molar purity of system recovered components, reboiler thermal load (Q) and annual total cost (TAC). Sensitivity analysis was used to adjust the parameters of the three processes in advance. Based on the multi-objective constraints, the optimal parameter range was divided as the initial data of Box-Behnken response surface method (BBD-RSM) optimization, and then the global optimization of the three processes was further conducted by BBD within the specified range. The most economical scheme was formulated by optimizing the data regression multi-objective equation, and the mole purity was 99.8% HAc and 99.9% TMOF. The results show that EDWC and SED can save more economic input and reboiler heat load than CED under the same separation purity condition. SED can save 10.37% TAC and 6.88% heat load, and EDWC can save 10.65% TAC and 10.53% heat load. The results show that there is a good fitting relationship between the predicted value and the actual value, and the prediction errors of TAC and Q by CED, SED and EDWC are all less than 1%. All three process schemes can provide theoretical basis for actual chemical production.

Key words: azeotrope, computer simulation, economics, group contribution method, extractive distillation, multi-objective optimization

中图分类号:

TQ 028.3

柳旭, 许松林, 王燕飞. 原甲酸三甲酯-醋酸萃取精馏全局多目标优化[J]. 化工学报, 2022, 73(10): 4518-4526.

Xu LIU, Songlin XU, Yanfei WANG. Global multi-objective optimization of trimethyl orthoformate-acetic acid extractive distillation[J]. CIESC Journal, 2022, 73(10): 4518-4526.

图/表 17

表1 UNIFAC基团体积RK、表面积参数QK

Table 1 UNIFAC group volume RK and group surface area QK

基团	R_K	Q_K
CH—	0.4469	0.228
CH₃O—	1.1450	1.088
CH₃—	0.9011	0.848
COOH—	1.3013	1.224

表2 UNIFAC基团交互参数

Table 2 Interaction parameters of UNIFAC groups

基团	CH—	CH₃O—	CH₃—	COOH—
CH—	0	251.5	0	663.5
CH₃O—	83.36	0	83.36	664.6
CH₃—	0	251.5	0	663.5
COOH—	315.3	-338.5	315.3	0

表3 UNIFAC基团贡献法HAc-TMOF汽液平衡数据

Table 3 HAc-TMOF vapor-liqid equilibrium data of UNIFAC group contribution method

温度/K	x₁	x₂	y₁	y₂	γ₁	γ₂
391.581	0.98	0.02	0.99	0.01	0.9998	0.5819
391.985	0.96	0.04	0.97	0.03	0.9990	0.5972
392.366	0.94	0.06	0.96	0.04	0.9977	0.6128
392.721	0.92	0.08	0.94	0.06	0.9960	0.6285
393.046	0.90	0.10	0.93	0.07	0.9936	0.6444
393.336	0.88	0.12	0.91	0.09	0.9908	0.6605
393.589	0.86	0.14	0.89	0.11	0.9874	0.6766
393.833	0.70	0.30	0.66	0.34	0.9399	0.8057
393.605	0.68	0.32	0.63	0.37	0.9314	0.8215
392.557	0.62	0.38	0.52	0.48	0.9027	0.8673
389.704	0.52	0.48	0.35	0.65	0.8452	0.9376
386.690	0.44	0.56	0.23	0.77	0.7933	0.9856
385.882	0.42	0.58	0.21	0.79	0.7800	0.9961
374.159	0.06	0.94	0.01	0.99	0.9008	1.0118
373.763	0.04	0.96	0.01	0.99	1.0038	1.0060

图1 不同压力下TMOF-HAc T-xy图

Fig.1 T-xy diagram of TMOF-HAc at different pressures

图2 有/无萃取剂条件下HAc的x-y图

Fig.2 x-y diagram of HAc with/without extractant

表4 CED灵敏度分析工艺参数范围

Table 4 CED sensitivity analysis process parameters range and results

N_T	R	N_F	S	N_S	N_T′	N_F′	R′
25~35	0.4~1.0	9~13	0.8~1.6	4~8	20~30	6~12	2.5~3.5

表5 CED工艺参数优化结果

Table 5 CED process parameters optimization results

N_T	S	R	N_F	N_S	N_T′	N_F′	R′
34	1.02	0.40	13	6	20	7	2.50

图3 侧线萃取精馏工艺流程示意图

Fig.3 Schematic diagram of lateral extraction distillation process

表6 SED灵敏度分析工艺参数范围

Table 6 Process parameters range and results of SED sensitivity analysis

N₁	R₁	N_A	S₁	N	L/(kmol/h)	N_L	N₂	N_A′	R₂
36~40	0.4~0.6	8~10	1.0~1.2	5~7	80~100	30~34	16~20	6~10	1.4~2.5

表7 SED工艺参数优化结果

Table 7 Optimization results of SED process parameters

N₁	S₁	R₁	N	N_A	L/(kmol/h)	N_L	N₂	$N A'$	R₂
37	1.01	0.42	7	8	83	31	17	6	1.47

表7 SED工艺参数优化结果

Table 7 Optimization results of SED process parameters

N₁	S₁	R₁	N	N_A	L/(kmol/h)	N_L	N₂	$N A'$	R₂
37	1.01	0.42	7	8	83	31	17	6	1.47

图4 L、NL变化TAC响应曲线与等高线

Fig.4 TAC response curve and coutour of L and NL changes

图5 EDWC工艺流程图

Fig.5 Process diagram of EDWC

表8 EDWC灵敏度分析工艺参数范围与结果

Table 8 Process parameters range and results of EDWC sensitivity analysis

N_M	R_W	N_W	S_W	$N W'$	V/(kmol/h)	N_V	N_R
38~40	0.3~0.5	9~11	0.85~1.00	5~7	60~70	28~30	16~20

表8 EDWC灵敏度分析工艺参数范围与结果

Table 8 Process parameters range and results of EDWC sensitivity analysis

N_M	R_W	N_W	S_W	$N W'$	V/(kmol/h)	N_V	N_R
38~40	0.3~0.5	9~11	0.85~1.00	5~7	60~70	28~30	16~20

图6 V、NV变化TAC响应曲线与等高线

Fig.6 TAC response curve and coutour of V and NV changes

图7 MC塔板位置与组分摩尔分数曲线

Fig.7 MC tray position and component molar fraction curve

表9 EDWC工艺参数优化结果

Table 9 Optimization results of EDWC process parameters

N_M	S_W	R_W	N_W	$N W'$	V/(kmol/h)	N_V	N_R
38	0.88	0.38	11	6	65	29	18

表9 EDWC工艺参数优化结果

Table 9 Optimization results of EDWC process parameters

N_M	S_W	R_W	N_W	$N W'$	V/(kmol/h)	N_V	N_R
38	0.88	0.38	11	6	65	29	18

表11 BBD响应面优化结果

Table 11 Optimization results of BBD response surface

工艺	响应值	平方和	自由度	均方	F值	R²
CED	TMOF 摩尔纯度	3.00×10^-4	44	7.11×10^-6	46.16	0.96
	HAc 摩尔纯度	3.60×10^-3		1.00×10^-4	18.86	0.92
	NMP 摩尔纯度	1.00×10^-4		3.24×10^-6	21.46	0.93
	TAC	5.90×10¹¹		1.34×10¹⁰	9.84	0.85
	Q	8.24×10⁶		1.03×10⁶	74.75	0.85
SED	TMOF 摩尔纯度	8.00×10^-4	65	0	13.32	0.89
	HAc 摩尔纯度	7.00×10^-3		1.00×10^-4	6.91	0.81
	NMP 摩尔纯度	7.00×10^-4		0	7.92	0.83
	TAC	3.38×10¹¹		5.20×10⁹	337.24	0.99
	Q	4.65×10⁶		7.15×10⁴	344.64	0.99
EDWC	TMOF 摩尔纯度	2.00×10^-4	44	4.19×10^-6	21.84	0.97
	HAc 摩尔纯度	1.00×10^-3		0	20.45	0.97
	NMP 摩尔纯度	0		5.49×10^-7	78.61	0.99
	TAC	5.97×10¹⁰		1.36×10⁹	10.80	0.94
	Q	7.08×10⁵		1.61×10⁴	11.28	0.94

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