钼钒同多酸催化降解纤维素制备甲酸的性能研究

doi:10.3969/j.issn.0253-2417.2022.02.011

摘要/Abstract

摘要：

以合成的钼钒同多酸Na₆[α-Mo₆V₂O₂₆]·16H₂O为催化剂，对甲苯磺酸为酸催化剂，在水相介质和O₂气氛中，考察了钼钒同多酸将纤维素选择性转化为甲酸(FA)的催化性能。实验结果表明：合成的钼钒同多酸催化剂表现出较强的氧化性。在纤维素0.2 g，Na₆[α-Mo₆V₂O₂₆]·16H₂O 0.1 g，对甲苯磺酸0.15 g，去离子水10 mL，O₂压力为1 MPa，温度140℃条件下反应3 h，纤维素转化率为98%，甲酸的产率为47%。此外研究了该催化剂将单糖类(木糖和葡萄糖)转化为甲酸的催化性能，其中以木糖为底物时的甲酸产率最高，达到63%。

关键词: 钼钒同多酸, 纤维素, 对甲苯磺酸, 甲酸

Abstract:

Using the synthesized molybdenum-vanadium homopolyacid Na₆[α-Mo₆V₂O₂₆]·16H₂O as catalyst and p-toluene sulfonic acid as acid catalyst, the catalytic performance of the molybdenum-vanadium homopolyacid for the selective conversion of cellulose to formic acid(FA) was investigated under aqueous medium and O₂ atmosphere. The experimental results showed that the synthesized molybdenum-vanadium homopolyacid exhibited strong oxidizing property. Under the conditions of 0.2 g of cellulose, 0.1 g of Na₆[α-Mo₆V₂O₂₆]·16H₂O, 0.15 g of p-toluene sulfonic acid, 10 mL of deionized water, O₂ pressure of 1 MPa, and temperature of 140 ℃ were reacted for 3 h, the conversion rate of cellulose reached 98%, and the yield of formic acid was 47%. In addition, catalytic performance of the catalyst for the conversion of monosaccharides(xylose and glucose) into formic acid was studied, and the conversion of xylose to formic acid had the highest yield of 63%.

Key words: molybdenum-vanadium polyoxometalate, cellulose, p-toluene sulfonic acid, formic acid

中图分类号:

TQ35

陈秀强, 段喜鑫, 时君友. 钼钒同多酸催化降解纤维素制备甲酸的性能研究[J]. 林产化学与工业, 2022, 42(2): 80-86.

Xiuqiang CHEN, Xixin DUAN, Junyou SHI. Investigation on Degradation of Cellulose to Formic Acid Catalyzed by Molybdenum-vanadium Polyoxometalates[J]. Chemistry and Industry of Forest Products, 2022, 42(2): 80-86.

图/表 4

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图3

表1

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序号 No.	原料 raw material	催化剂/g catalyst	时间/h time	温度/℃ temp.	O₂压力/MPa O₂ pressure	转化率/% conversion	FA产率/% FA yield	文献 document
1	木糖 xylose	0.1 g Na₆[α-Mo₆V₂O₂₆]	0.5	140	1	100	63	本研究 this study
2	葡萄糖 glucose	0.1 g Na₆[α-Mo₆V₂O₂₆]	0.5	140	1	100	60	本研究 this study
3	对甲苯磺酸 p-toluene sulfonic acid	0.1 g Na₆[α-Mo₆V₂O₂₆]	4	140	1	0	0	本研究 this study
4	纤维素 cellulose	0.1 g Na₆[α-Mo₆V₂O₂₆]	3	140	1	52	8.6	本研究 this study
5	纤维素 cellulose	0.1 g Na₆[α-Mo₆V₂O₂₆]+ 0.15 g对甲苯磺酸 p-toluene sulfonic acid	3	140	1	98	47	本研究 this study
6	纤维素 cellucosse	0.4 g H₅PV₂Mo₁₀O₄₀	9	170	空气air	100	34	[23]
7	纤维素 cellucose	1.82 g H₈PV₅Mo₇O₄₀	24	90	3	76	28	[24]
8	纤维素 cellucose	0.05 g NH₄VO₃/ZSM-5	8	180	3	—	19	[14]
9	纤维素 cellucose	0.02 g VOSO₄	2	160	2	—	39	[13]
10	杨木木屑 poplar	0.07 g H₅PV₂Mo₁₀O₄₀	26	80	3	—	11	[25]
11	榉木 beech	0.12 g K₅V₃W₃O₁₉	72	115	5	50	12.5	[26]

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