柠檬腈的合成工艺研究

doi:10.3969/j.issn.0253-2417.2022.06.011

Abstract

Abstract:

The synthesis process of geranyl nitrile from citral by catalytic ammoxidation was optimized. The factors affecting the conversion rate of citral and the yield of geranyl nitrile, including ammonia(NH₃·H₂O) dosage, hydrogen peroxide(H₂O₂) dosage, reaction time, reaction temperature, the type and dosage of catalyst, and solvent type were investigated. Through univariate and onthogonal experiments, the optimal synthesis conditions for geranyl nitrile was citral 35 mmol, n(citral)∶n(NH₃·H₂O)∶n(H₂O₂)∶n(CuCl)=1∶2.7∶5.5∶0.045, H₂O₂ as oxidant, CuCl as catalyst, 36 mL isopropanol as solvent, and the reaction time of 5 h, the reaction temperature of 10-15 ℃. At these synthesis conditions, the conversion ratio of citral was 97.50% and the yield of geranyl nitrile was 94.59%. When the conditions were amplified by 2, 3 and 5 times, the conversion rates of citral were 95.75%, 95.05% and 95.00%, and the yields of geranyl nitrile were 92.88%, 92.20% and 92.15%, respectively.

Key words: citral, geranyl nitrile, ammoxidation, process optimization

CLC Number:

TQ35

Jiulong WANG, Hongyan SI, Shangxing CHEN, Xiaoping RAO, Zongde WANG, Shengliang LIAO. The Optimization of Synthesis Process of Geranyl Nitrile[J]. Chemistry and Industry of Forest Products, 2022, 42(6): 77-83.

Figures/Tables 7

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References 16

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	项目 items	柠檬醛转化率/% citral conversion rate	柠檬腈产率/% geranyl nitrile yield
溶剂类型 solvent types	异丙醇isopropanol	94.12	91.30
	乙醇ethyl alcohol	7.90	7.68
	乙二醇glycol	72.16	70.00
溶剂用量 solvent dosage	18 mL	91.05	88.32
	27 mL	92.04	89.28
	36 mL	94.12	91.30
	72 mL	91.25	88.52
催化剂类型 catalyst types	CuCl	94.12	91.30
	CuSO₄	68.42	66.37
	FeCl₃	24.47	23.74
	CuCl₂	93.12	90.33
	Cu(NO₃)₂	69.89	67.80
	4H₂O·FeCl₂	14.10	13.68
反应温度 reaction temp.	5~10 ℃	92.09	89.33
	10~15 ℃	94.65	91.82
	15~20 ℃	91.92	89.16
	20~25 ℃	84.12	81.60
	25~30 ℃	82.59	80.12
反应时间 reaction time	3 h	91.89	89.14
	4 h	92.19	89.43
	5 h	93.61	90.81
	6 h	93.62	90.82
	7 h	93.65	90.85
	8 h	93.36	90.56
	9 h	92.90	90.12

试验号 No.	n(柠檬醛)/n(NH₃·H₂O) n(citral)/n(NH₃·H₂O)	n(柠檬醛)/n(H₂O₂) n(citral)/n(H₂O₂)	n(柠檬醛)/n(CuCl) n(citral)/n(CuCl)	柠檬醛转化率/% citral conversion rate	柠檬腈产率/% geranyl nitrile yield
1	1∶2.7	1∶4.5	1∶0.03	93.83	91.02
2	1∶2.7	1∶5.0	1∶0.045	91.81	89.06
3	1∶2.7	1∶5.5	1∶0.06	92.48	89.71
4	1∶2.9	1∶5.0	1∶0.06	82.10	79.64
5	1∶2.9	1∶5.5	1∶0.03	92.91	90.13
6	1∶2.9	1∶4.5	1∶0.045	95.40	92.54
7	1∶3.1	1∶5.5	1∶0.045	92.51	89.74
8	1∶3.1	1∶4.5	1∶0.06	79.62	77.24
9	1∶3.1	1∶5.0	1∶0.03	92.57	89.80
k₁	92.74	89.62	93.10
k₂	90.14	88.83	93.24
k₃	88.23	92.63	84.73
R	4.51	3.80	8.51
k₁′	89.93	86.93	90.32
k₂′	87.44	86.17	90.45
k₃′	85.59	89.86	82.20
R′	4.34	3.69	8.25

放大倍数 magnification	试剂用量reagent dosage/mmol				柠檬醛转化率/% citral conversion rate	柠檬腈产率/% geranyl nitrile yield
放大倍数 magnification	柠檬醛citral	NH₃·H₂O	CuCl	H₂O₂	柠檬醛转化率/% citral conversion rate	柠檬腈产率/% geranyl nitrile yield
1	35	101.5	1.57	175	97.58	94.66
2	70	203.0	3.15	350	95.75	92.88
3	105	304.5	4.72	525	95.05	92.20
5	175	507.5	7.87	875	95.00	92.15

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The Optimization of Synthesis Process of Geranyl Nitrile

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