碱预处理小麦秸秆制备乙酰丙酸甲酯的工艺

doi:10.16085/j.issn.1000-6613.2020-0695

化工进展 ›› 2021, Vol. 40 ›› Issue (2): 1106-1113.DOI: 10.16085/j.issn.1000-6613.2020-0695

碱预处理小麦秸秆制备乙酰丙酸甲酯的工艺

郭鹏坤¹(), 李攀¹^,², 邓琳¹, 常春¹^,³(), 徐桂转⁴, 石晓华¹(), 方书起¹^,²

^1.郑州大学化工学院，河南郑州 450001
^2.河南省杰出外籍科学家工作室，河南郑州 450001
^3.河南省生物基化学品绿色制造重点实验室，河南濮阳 457000
^4.河南农业大学机电工程学院，河南郑州 450001

收稿日期:2020-04-28 修回日期:2020-08-18 出版日期:2021-02-05 发布日期:2021-02-09
通讯作者: 常春,石晓华
作者简介:郭鹏坤（1994—），男，硕士研究生，研究方向为生物质能源化工。E-mail：1209427664@qq.com。
基金资助:
河南省生物基化学品绿色制造重点实验室开放课题;河南省杰出外籍科学家工作室生物质资源加工与高效利用(GZS2018004)

Preparation of methyl levulinate by pretreatment of wheat straw with alkali

Pengkun GUO¹(), Pan LI¹^,², Lin DENG¹, Chun CHANG¹^,³(), Guizhuan XU⁴, Xiaohua SHI¹(), Shuqi FANG¹^,²

^1.School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, Henan, China
^2.Henan Outstanding Foreign Scientists’ Workroom, Zhengzhou 450001, Henan, China
^3.Henan Key Laboratory of Green Manufacturing of Biobased Chemicals, Puyang 457000, Henan, China
^4.College of Mechanical and Electrical Engineering, Henan Agricultural University, Zhengzhou 450002, Henan, China

Received:2020-04-28 Revised:2020-08-18 Online:2021-02-05 Published:2021-02-09
Contact: Chun CHANG,Xiaohua SHI

摘要/Abstract

摘要：

小麦秸秆作为一种农业副产品，是制备生物质化学品的重要原料。乙酰丙酸甲酯（methyl levulinate，ML）是一种具有广泛应用前景的生物质化学品。本文以碱液预处理后的小麦秸秆为原料，硫酸铜为催化剂，研究了制备ML的工艺，考察了反应温度、反应时间、催化剂用量等对ML产率的影响。经过工艺优化，在反应温度183℃、反应时间3.3h、催化剂用量0.53g条件下，ML的收率达到23.0%（质量分数）。硫酸铜重复使用后仍具有良好的催化活性，在重复使用5次后ML收率达到18.7%（质量分数）。在相同的优化条件下，所开发的工艺比未处理小麦秸秆制备ML的收率提高了8.6%（质量分数）。

关键词: 乙酰丙酸甲酯, 秸秆, 热化学转化, 催化

Abstract:

As a kind of agricultural by-product, wheat straw can be used as raw material for the preparation of biobased chemicals. Methyl levulinate (ML) is a kind of biobased chemical with wide applications. Using wheat straw pretreated with alkali as raw material and copper sulfate as catalyst, the process of preparing ML was studied. The effects of reaction temperature, reaction time and catalyst dosage on the yield of ML were investigated. Through optimization, the ML yield of 23.0%(mass fraction) was achieved under the reaction conditions of temperature 183℃, reaction time 3.3h and catalyst dosage 0.53g. Meanwhile, copper sulfate had good catalytic activity after repeated use, and the ML yield reached 18.7%(mass fraction) after five times of use. Under the same optimized conditions, the developed process improved the ML yield by 8.6%(mass fraction) compared with the ML yield from unpretreated wheat straw.

Key words: methyl levulinate, wheat straw, thermochemical conversion, catalyst

中图分类号:

S216.2

郭鹏坤, 李攀, 邓琳, 常春, 徐桂转, 石晓华, 方书起. 碱预处理小麦秸秆制备乙酰丙酸甲酯的工艺[J]. 化工进展, 2021, 40(2): 1106-1113.

Pengkun GUO, Pan LI, Lin DENG, Chun CHANG, Guizhuan XU, Xiaohua SHI, Shuqi FANG. Preparation of methyl levulinate by pretreatment of wheat straw with alkali[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 1106-1113.

图/表 13

参考文献 28

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因素	水平
因素	-1	0	1
X₁（催化剂用量）/g	0.3	0.5	0.7
X₂（反应温度）/℃	160	180	200
X₃（反应时间）/h	1	3	5

因素	水平
因素	-1	0	1
X₁（催化剂用量）/g	0.3	0.5	0.7
X₂（反应温度）/℃	160	180	200
X₃（反应时间）/h	1	3	5

编号	催化剂类型	ML收率/%
1	无	约0.02
2	Na₂SO₄	0.8
3	MgSO₄	1.1
4	Al₂(SO₄)₃	10.4
5	CuSO₄	14.5
6	ZnSO₄	1.3
7	Fe₂(SO₄)₃	10.0
8	MnSO₄	0.6
9	Ti(SO₄)₂	12.4

编号	催化剂类型	ML收率/%
1	无	约0.02
2	Na₂SO₄	0.8
3	MgSO₄	1.1
4	Al₂(SO₄)₃	10.4
5	CuSO₄	14.5
6	ZnSO₄	1.3
7	Fe₂(SO₄)₃	10.0
8	MnSO₄	0.6
9	Ti(SO₄)₂	12.4

编号	X₁	X₂	X₃	ML收率/%
1	1	1	0	18.7
2	0	1	1	19.8
3	-1	1	0	11.7
4	1	0	1	22.0
5	-1	0	-1	0.10
6	-1	-1	0	0.00
7	0	-1	-1	0.40
8	0	-1	1	12.6
9	-1	0	1	6.20
10	0	0	0	22.4
11	1	-1	0	13.6
12	0	1	0	12.2
13	0	0	0	22.1
14	0	0	0	20.4
15	1	0	-1	12.4
16	0	0	0	20.6
17	0	0	0	21.3

碱预处理小麦秸秆制备乙酰丙酸甲酯的工艺

Preparation of methyl levulinate by pretreatment of wheat straw with alkali

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图/表 13

参考文献 28

相关文章 15

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Metrics

本文评价

来源	平方和	自由度	均方	F 值	P 值	是否显著
模型	1028.93	9	114.33	62.18	<0.0001	显著
残差	12.87	7	1.84
失拟项	9.74	3	3.25	4.15	0.1016	不显著
决定系数	0.9876
纯误差	3.13	4	0.87
X₁	296.46	1	296.46	161.25	<0.0001
X₂	160.20	1	160.20	87.14	<0.0001
X₃	157.53	1	157.53	85.68	<0.0001
X₁X₂	10.89	1	10.89	5.92	0.0452
X₁X₃	3.06	1	3.06	1.67	0.2378
X₂X₃	5.29	1	5.29	2.88	0.1337
X₁²	137.64	1	137.64	74.87	<0.0001
X₂²	90.75	1	90.75	49.36	0.0002
X₃²	125.87	1	125.87	68.46	<0.0001

原料	催化剂	产物	收率	文献
小麦秸秆	H₂SO₄	EL	17.91%（质量分数）	[6]
竹子	H₂SO₄	ML	30.75 %（质量分数）	[8]
浮萍	H₂SO₄	EL	55.2%	[9]
小麦秸秆	磺酸盐离子液体	EL	16.28%（质量分数）	[11]
纤维素	H-USY	ML	54%	[12]
预处理后的小麦秸秆	CuSO₄	ML	22.9%（质量分数）	本实验

过程	原料	质量/kg	单价/CNY	共计/CNY
未处理小麦秸秆
支出	小麦秸秆	1000.00	0.30	300
	CuSO₄	48.00	9.26	444.48
	甲醇	4620.00	2.65	12243
收入	ML	152.00	92.64	14081.28
共计				1093.8
预处理小麦秸秆
支出	小麦秸秆	1000.00	0.30	300
	CuSO₄	29.40	9.93	291.94
	甲醇	3074.82	2.65	8148.27
	NaOH	479.75	1.99	954.7
	HCl	506.00	1.12	566.72
收入	ML	146.30	92.64	13553.23
收入	木质素	131.30	2.32	304.62
共计				3596.22

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