温控相分离纳米Ir催化α，β-不饱和醛、酮选择加氢

doi:10.11949/0438-1157.20190486

摘要/Abstract

摘要：

将温控相分离Ir纳米催化剂用于α,β-不饱和醛、酮的选择性加氢反应中，系统考察了其催化加氢性能。在优化的反应条件下，Ir纳米催化剂对α,β-不饱和醛的C═O键加氢选择性大于99%，对α,β-不饱和酮的C═C键加氢选择性大于99%。 Ir纳米催化剂经简单分离可直接循环使用5次，选择性均大于99%。TEM表征结果显示反应四次后的Ir纳米催化剂的平均粒径变为(1.9 ± 0.2) nm，比新制备的Ir纳米催化剂的平均粒径（1.3 ± 0.1）nm有所增大。ICP-AES测试结果表明Ir流失低于仪器检测下限（检测下限为5 μg/L）。

关键词: 温控相分离催化, Ir纳米催化剂, 催化加氢, α,β-不饱和醛, α,β-不饱和酮

Abstract:

Thermo regulated phase-separable Ir nano catalyst was applied to the selective hydrogenation of α, β-unsaturated aldehydes and ketones and its catalytic hydrogenation performance was systematically investigated. Under the optimized reaction conditions, the Ir nano catalyst exhibited high selectivity of C═O bond for α, β-unsaturated aldehydes (>99%), while high selectivity of C═C bond for α, β-unsaturatedketones (>99%). The catalyst can be simply separated and directly reused for 5 times with the selectivity remaining >99%. Furthermore, the results of TEM showed that the particle size of Ir nano catalyst after four cycles was (1.9 ± 0.2) nm, which increased a little compared with the Ir nano catalyst newly prepared. The results of ICP-AES showed that the leaching of Ir in the upper organic phase was below the detection limit (the detection limit is 5 μg/L).

Key words: thermo regulated phase-separable catalysis, Ir nano catalyst, catalytic hydrogenation, α, β-unsaturated aldehydes, α, β-unsaturated ketones

中图分类号:

O 622.4

张茜, 王艳华. 温控相分离纳米Ir催化α，β-不饱和醛、酮选择加氢[J]. 化工学报, 2019, 70(9): 3396-3403.

Qian ZHANG, Yanhua WANG. Selective hydrogenation of α, β-unsaturated aldehydes and ketones over thermo regulated phase-separable Ir nano catalyst[J]. CIESC Journal, 2019, 70(9): 3396-3403.

图/表 9

图1 离子液体CILPEG-CD750的合成

Fig.1 Synthesis of ionic liquid CILPEG-CD750

图2 新制备的Ir纳米催化剂的TEM图和粒径分布

Fig.2 TEM micrograph and particle size distribution of freshly prepared Ir nanocatalyst

表1 不同的酸添加剂对查尔酮选择性加氢反应的影响

Table 1 Effect of different acid additives on selective hydrogenation of chalcone

Entry	Acid	Conversion^①/%	Selectivity^①,②/%
1	—^③	83	>99
2	HCOOH	23	>99
3	CH₃COOH	>99	>99
4	CH₃CH₂COOH	93	>99

表2 查尔酮选择性加氢反应条件的优化

Table 2 Optimization of conditions for selective hydrogenation of chalcone

Entry	(CH₃COOH/chalcone)/(mol/mol)	T /℃	$P H 2$ /MPa	t /h	(chalcone/Ir)/(mol/mol)	Conversion^①/%	Selectivity^①,②/%
1	1:1	130	3	6	200:1	88	>99
2	3:1	130	3	6	200:1	90	>99
3	5:1	130	3	6	200:1	>99	>99
4	5:1	100	3	6	200:1	89	>99
5	5:1	110	3	6	200:1	91	>99
6	5:1	120	3	6	200:1	95	>99
7	5:1	130	0.5	6	200:1	79	>99
8	5:1	130	1	6	200:1	80	>99
9	5:1	130	2	6	200:1	88	>99
10	5:1	130	3	3	200:1	89	>99
11	5:1	130	3	4	200:1	95	>99
12	5:1	130	3	5	200:1	96	>99
13	5:1	130	3	6	250:1	88	>99
14	5:1	130	3	6	300:1	85	>99

表2 查尔酮选择性加氢反应条件的优化

Table 2 Optimization of conditions for selective hydrogenation of chalcone

Entry	(CH₃COOH/chalcone)/(mol/mol)	T /℃	$P H 2$ /MPa	t /h	(chalcone/Ir)/(mol/mol)	Conversion^①/%	Selectivity^①,②/%
1	1:1	130	3	6	200:1	88	>99
2	3:1	130	3	6	200:1	90	>99
3	5:1	130	3	6	200:1	>99	>99
4	5:1	100	3	6	200:1	89	>99
5	5:1	110	3	6	200:1	91	>99
6	5:1	120	3	6	200:1	95	>99
7	5:1	130	0.5	6	200:1	79	>99
8	5:1	130	1	6	200:1	80	>99
9	5:1	130	2	6	200:1	88	>99
10	5:1	130	3	3	200:1	89	>99
11	5:1	130	3	4	200:1	95	>99
12	5:1	130	3	5	200:1	96	>99
13	5:1	130	3	6	250:1	88	>99
14	5:1	130	3	6	300:1	85	>99

表3 温控相分离Ir纳米催化剂的循环使用效果

Table 3 Reusability of Ir nanocatalyst for selective hydrogenation of chalcone

Entry	t /h	Conversion^①/%	Selectivity^①,②/%
1	6	>99	>99
2	6	99	>99
3	6	92	>99
4	6	83	>99
5	8	92	>99

图3 Ir纳米催化剂循环使用4次后的TEM图和粒径分布

Fig.3 TEM micrograph and particle size distribution of Ir nanocatalyst after four cycles

表4 不同的碱添加剂对肉桂醛选择性加氢反应的影响

Table 4 Effect of different base additives on selective hydrogenation of CAL

Entry	Base	Conversion^①/%	Selectivity^①,②/%
1	—^③	50	60
2	triethylamine	>99	>99
3	trioctylamine	79	>99
4	triisooctylamine	77	95

表5 肉桂醛选择性加氢反应的条件优化

Table 5 Optimization of conditions for selective hydrogenation of CAL

Entry	(triethylamine/CAL)/(mol/mol)	T/℃	$P H 2$ /MPa	t /h	(CAL/Ir)/(mol/mol)	Conversion^①/%	Selectivity^①,②/%
1	1∶1	70	5	7	200∶1	73	96
2	4∶1	70	5	7	200∶1	96	99
3	5∶1	70	5	7	200∶1	>99	>99
4	5∶1	60	5	7	200∶1	60	93
5	5∶1	80	5	7	200∶1	>99	91
6	5∶1	90	5	7	200∶1	>99	90
7	5∶1	70	1	7	200∶1	74	>99
8	5∶1	70	3	7	200∶1	81	>99
9	5∶1	70	4	7	200∶1	90	>99
10	5∶1	70	5	4	200∶1	90	>99
11	5∶1	70	5	5	200∶1	93	>99
12	5∶1	70	5	6	200∶1	98	>99
13	5∶1	70	5	7	250∶1	95	91
14	5∶1	70	5	7	300∶1	87	90

表5 肉桂醛选择性加氢反应的条件优化

Table 5 Optimization of conditions for selective hydrogenation of CAL

Entry	(triethylamine/CAL)/(mol/mol)	T/℃	$P H 2$ /MPa	t /h	(CAL/Ir)/(mol/mol)	Conversion^①/%	Selectivity^①,②/%
1	1∶1	70	5	7	200∶1	73	96
2	4∶1	70	5	7	200∶1	96	99
3	5∶1	70	5	7	200∶1	>99	>99
4	5∶1	60	5	7	200∶1	60	93
5	5∶1	80	5	7	200∶1	>99	91
6	5∶1	90	5	7	200∶1	>99	90
7	5∶1	70	1	7	200∶1	74	>99
8	5∶1	70	3	7	200∶1	81	>99
9	5∶1	70	4	7	200∶1	90	>99
10	5∶1	70	5	4	200∶1	90	>99
11	5∶1	70	5	5	200∶1	93	>99
12	5∶1	70	5	6	200∶1	98	>99
13	5∶1	70	5	7	250∶1	95	91
14	5∶1	70	5	7	300∶1	87	90

表6 不同α, β-不饱和醛、酮的选择性加氢反应

Table 6 Selective hydrogenation of different α, β-unsaturated aldehydes and ketones

Entry	t	Conversion^③/%	Selectivity^③/%
1^①	7 h	>99	>99
2^①	10 min	>99	>99
3^①	3 h	>99	>99
4^①	20 min	>99	>99
5^①	20 min	>99	>99
6^②	10 h	>99	>99
7^②	7 h	>99	>99

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