环己醇精馏残液催化加氢分离二环己基醚工艺研究

doi:10.11949/0438-1157.20191212

摘要/Abstract

摘要：

针对环己醇精馏残液中各组分沸点相近，常规分离方法分离难度大等技术问题，采用催化加氢的方法将环己醇精馏残液中的3-环己基环己烯、1-环己基环己烯和环己亚基环己烷还原为双环己烷，扩大分离组分间的沸点差，经减压精馏分离，得到高纯度的双环己烷和二环己基醚。以Pd/C为催化剂，通过对比实验获得了环己醇精馏残液中的3-环己基环己烯、1-环己基环己烯和环己亚基环己烷催化加氢转化为双环己烷的最佳工艺条件：反应温度120℃、反应压力4 MPa、反应时间4 h、搅拌速度550 r/min、Pd/C催化剂用量为物料质量的0.4%，原料转化率为98.7%，双环己烷的选择性大于99.5%；经减压精馏分离后，双环己烷和二环己基醚的纯度大于99.5%。

关键词: 环己醇精馏残液, 二环己基醚, 双环己烷, 加氢, 分离, 优化

Abstract:

In order to solve the key technical problems such as similar boiling points of cyclohexanol distillation residues and the difficulty of separation by conventional separation methods, the 3-cyclohexylcyclohexene, 1-cyclohexylcyclohexene and dicyclohexylidene were reduced to cyclohexylcyclohexane by catalytic hydrogenation and the boiling point difference between the two components was enlarged. High purity cyclohexylcyclohexane and dicyclohexyl ether were obtained by vacuum distillation. Using Pd/C as catalyst, the optimum conditions for catalytic hydrogenation of 3-cyclohexylcyclohexene, 1-cyclohexylcyclohexene and dicyclohexylidene to cyclohexylcyclohexane in residual solution were obtained. The reaction temperature was 120℃, the reaction time was 4 h, the reaction pressure was 4 MPa, the stirring speed was 550 r/min, the amount of Pd/C catalyst was 0.4% of the mass of the material, the selectivity was more than 99.5% and the conversion rate of the materials was 98.7%. After vacuum distillation, the purity of cyclohexylcyclohexane and dicyclohexyl ether is more than 99.5%.

Key words: residual liquid of cyclohexanol distillation tower, dicyclohexyl ether, cyclohexylcyclohexane, hydrogenation, separation, optimization

中图分类号:

O 624.11

霍二福, 李迎春, 杨帅, 冯明, 程伟琴, 王柏楠, 魏新军. 环己醇精馏残液催化加氢分离二环己基醚工艺研究[J]. 化工学报, 2020, 71(7): 3132-3139.

Erfu HUO, Yingchun LI, Shuai YANG, Ming FENG, Weiqin CHENG, Bonan WANG, Xinjun WEI. Study on separation process of dicyclohexyl ether by catalytic hydrogenation from cyclohexanol distillation residue[J]. CIESC Journal, 2020, 71(7): 3132-3139.

图/表 12

图1 环己醇精馏残液气相色谱-质谱联用分析色谱图

Fig.1 Analysis of the chromatogram of cyclohexanol distillation by gas chromatography-mass spectrometry

图2 环己醇精馏残液气相色谱-质谱联用分析质谱图

Fig.2 Mass spectroscopic analysis of residual liquid in cyclohexyl alcohol distillation by GC-MS

表1 环己醇精馏残液GC-MS分析TIC峰

Table 1 TIC peak for GC-MS analysis of cyclohexyl alcohol distillation residual liquid

峰号	保留时间/min	峰面积	峰面积/%	组分名称
合计		72866518	100
1	5.923	2017550	2.77	杂质
2	6.208	3489646	4.79	3-环己基环己烯
3	6.478	3900132	5.35	1-环己基环己烯
4	7.021	4102632	5.63	环己亚基环己烷
5	7.784	59356558	81.46	二环己基醚

图3 催化加氢反应物和产物的结构式

Fig.3 Structural formula of reactants and product of catalyst hydrogenation

表2 反应温度对催化加氢反应效果的影响

Table 2 Effect of reaction temperature on catalytic hydrogenation reaction

序号	反应温度/℃	原料的转化率/%	双环己烷的选择性/%
1	80	80.4	99.6
2	100	92.9	99.6
3	120	98.7	99.6
4	140	94.6	99.6
5	160	90.3	99.3

表3 反应压力对催化加氢反应效果的影响

Table 3 Effect of reaction pressure on catalytic hydrogenation reaction

序号	反应压力/MPa	原料的转化率/%	双环己烷的选择性/%
1	3.0	76.9	99.6
2	3.5	90.9	99.6
3	4.0	98.7	99.6
4	4.5	99.1	99.6
5	5.0	99.5	99.6

表4 反应时间对催化加氢反应效果的影响

Table 4 Effect of reaction time on catalytic hydrogenation reaction

序号	反应时间/h	原料的转化率/%	双环己烷的选择性/%
1	2.0	73.2	99.8
2	3.0	83.1	99.8
3	3.5	95.6	99.8
4	4.0	98.7	99.6
5	4.5	98.9	99.6
6	5.0	99.3	99.5

表5 搅拌速度对催化加氢反应效果的影响

Table 5 Effect of mixing speed on catalytic hydrogenation reaction

序号	搅拌速度/（r/min）	原料的转化率/%	双环己烷的选择性/%
1	350	68.7	99.1
2	400	77.9	99.4
3	450	88.9	99.6
4	500	92.7	99.6
5	550	98.7	99.6
6	600	98.9	99.6

表6 催化剂用量对催化加氢反应效果的影响

Table 6 Effect of catalytic amount on catalytic hydrogenation reaction

序号	催化剂加入质量分数/%	原料的转化率/%	双环己烷的选择性/%
1	0.1	73.9	99.6
2	0.2	80.2	99.6
3	0.3	91.6	99.6
4	0.4	98.7	99.6
5	0.5	98.7	99.6

图4 Pd/C催化剂重复使用次数对加氢反应效果的影响

Fig.4 Effect of repeated use of Pd/C catalyst on hydrogenation

表7 真空度对二环己基醚分离效果的影响

Table 7 Effect of vacuum on separation of dicyclohexyl ether

序号	真空度/Pa	二环己基醚纯度/%
1	1000	98.1
2	800	98.4
3	600	98.9
4	300	99.3
5	200	99.6
6	100	98.7
7	50	97.6

表8 回流比对分离二环己基醚效果的影响

Table 8 Effect of reflux ratio on separation of dicyclohexyl ether

序号	回流比	双环己烷纯度/%	二环己基醚纯度/%
1	6∶1	99.99	99.94
2	5∶1	99.96	99.82
3	4∶1	99.95	99.75
4	3∶1	99.89	99.63
5	2∶1	99.12	99.18
6	1∶1	98.56	98.32

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