减压蒸馏法从生物质水解液中分离提纯乙酰丙酸

doi:10.3969/j.issn.1673-5854.2020.01.002

生物质化学工程 ›› 2020, Vol. 54 ›› Issue (1): 9-15.doi: 10.3969/j.issn.1673-5854.2020.01.002

减压蒸馏法从生物质水解液中分离提纯乙酰丙酸

龚晨¹,曹雪娟¹,唐兴^1,^2,*(),曾宪海^1,²,孙勇^1,²,林鹿^1,²

1. 厦门大学能源学院; 厦门市生物质清洁高值化利用重点实验室, 福建厦门 361102
2. 福建省生物质清洁高值化技术工程研究中心, 福建厦门 361102

收稿日期:2018-11-09 出版日期:2020-01-30 发布日期:2020-02-11
通讯作者: 唐兴 E-mail:x.tan@xmu.edu.cn
作者简介:龚晨(1994-),男,湖北武汉人,硕士生,主要从事木质生物质高值化转化的研究工作
基金资助:
国家自然科学基金资助项目(21676223);国家自然科学基金资助项目(21706223);中国石油天然气集团有限公司创新基金(2018D-5007-0503)

Separation and Purification of Levulinic Acid from Hydrolysate of Biomass by Using Compression Vacuum Distillation

Chen GONG¹,Xuejuan CAO¹,Xing TANG^1,^2,*(),Xianhai ZENG^1,²,Yong SUN^1,²,Lu LIN^1,²

1. Xiamen Key Laboratory of Clean and High-valued Utilization for Biomass, College of Energy, Xiamen University, Xiamen 361102, China
2. Fujian Engineering and Research Center of Clean and High-valuedTechnologies for Biomass, Xiamen 361102, China

Received:2018-11-09 Online:2020-01-30 Published:2020-02-11
Contact: Xing TANG E-mail:x.tan@xmu.edu.cn
Supported by:
国家自然科学基金资助项目(21676223);国家自然科学基金资助项目(21706223);中国石油天然气集团有限公司创新基金(2018D-5007-0503)

摘要/Abstract

摘要：

以乙酰丙酸（LA）/硫酸溶液模拟生物质水解液，探讨了硫酸用量、氢离子物质的量、硫酸根物质的量以及蒸馏温度对LA提纯效果的影响，并进一步考察了碱中和对LA提纯的促进作用。实验结果表明：硫酸的存在不利于LA的分离提纯，模拟水解液中氢离子物质的量是影响LA回收率的主要因素；在氢离子物质的量一定时，较高的硫酸根物质的量有利于LA的分离；最佳的蒸馏温度为170~180℃，利用氢氧化钠中和模拟水解液中的氢离子，可以得到较高纯度和回收率的LA。在100 mL水、0.1 mol LA、0.03 mol硫酸、0.06 mol NaOH（碱中和）和蒸馏温度170℃下，LA的回收率为84.5%，纯度为93.3%。在固体碱活性氧蒸煮（CAOSA）竹浆制得的LA水解液中，加入氢氧化钠中和后进行LA的减压蒸馏分离提纯，当NaOH与硫酸根的物质的量比值为1.4时，LA回收率高达91.8%（纯度93.5%）。

关键词: 乙酰丙酸, 碱中和, 分离提纯, 生物质

Abstract:

The simulative hydrolysate containing levulinic acid(LA) and sulfuric acid was used to study the effect of sulfuric acid on LA distillation and purification. The effect of H⁺ concentration, the sulfate concentration and the distillation temperature were comprehensively studied for the separation of LA. Further investigation of the alkali neutralization revealed that the neutralization of H⁺ by sodium hydroxide could effectively increase the recovery of LA. The presence of sulfuric acid was not conducive to the separation and purification of LA, and the concentration of H⁺ was the main negative factor for LA recovery. The higher concentration of sulfate was beneficial to the LA recovery to a certain extent and the optimal distillation temperature was 170-180℃ at a constant H⁺ concentration. Using sodium hydroxide to neutralize hydrogen ions in the simulated hydrolysate, desirable LA recovery with high purity could be expected. When the simulative hydrolysate contained 100 mL water, 0.1 mol LA and 0.03 mol sulfuric acid, LA recovery of 84.5% with the purity of 93.3% could be obtained with the addition of 0.06 mol NaOH and distillation in vacuum at 170℃. Furthermore, the separation of LA from the hydrolysate derived from the acid-catalyzed hydrolysis of raw biomass was also studied. The separation of LA was carried out after the neutralization by adding sodium hydroxide, and the final recovery rate of LA(purity 93.5%) up to 91.8% was achieved when the molar ratio of NaOH to sulfate was 1.4.

Key words: levulinic acid, alkali neutralization, separation and purification, biomass

中图分类号:

TQ35

龚晨,曹雪娟,唐兴,曾宪海,孙勇,林鹿. 减压蒸馏法从生物质水解液中分离提纯乙酰丙酸[J]. 生物质化学工程, 2020, 54(1): 9-15.

Chen GONG,Xuejuan CAO,Xing TANG,Xianhai ZENG,Yong SUN,Lu LIN. Separation and Purification of Levulinic Acid from Hydrolysate of Biomass by Using Compression Vacuum Distillation[J]. Biomass Chemical Engineering, 2020, 54(1): 9-15.

图/表 7

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序号 No.	硫酸用量/mmol sulfuric acid dosage	蒸馏时间/min distillation time	残渣质量/g mass of residue	馏分质量/g mass of fraction	纯度/% purity	回收率% recovery
1	0	7	0	11.1	99.1	94.8
2	1	8	1.4	10.1	97.4	84.8
3	2	8	1.9	9.5	94.7	77.6
4	3	10	2.6	9.1	94.3	74.0
5	4	9	3.4	8.6	93.9	69.6
6	5	13	4.1	8.0	90.1	62.1
7	6	14	4.6	7.7	79.9	53.0
8	7	14	4.9	7.3	81.8	51.5
9	8	12	5.2	6.9	82.0	48.8
10	9	15	5.8	6.4	79.0	43.6
11	10	18	6.1	6.1	72.2	38.0

序号 No.	硫酸用量/mmol sulfuric acid dosage	硫酸钠用量/mmol Na₂SO₄ dosage	蒸馏时间/min distillation time	馏分质量/g mass of fraction	纯度/% purity	回收率/% recovery
1	0	10	7	11.1	99.2	94.9
2	1	9	7	11.0	97.3	92.3
3	2	8	8	10.6	95.4	87.2
4	3	7	9	10.2	94.7	83.3
5	4	6	10	9.3	92.1	73.8
6	5	5	9	8.9	90.6	69.5
7	6	4	10	8.7	85.3	64.0
8	7	3	13	8.1	81.1	56.6
9	8	2	13	7.2	77.3	48.0
10	9	1	16	6.7	78.6	45.4
11	10	0	18	6.1	72.4	38.1

序号 No.	硫酸钠用量/mmol Na₂SO₄ dosage	蒸馏时间/min distillation time	馏分质量/g mass of fraction	纯度/% purity	回收率/% recovery
1	1	14	7.4	81.7	52.1
2	3	13	8.1	81.5	56.9
3	5	14	8.8	82.0	62.2
4	7	15	9.2	84.9	67.3
5	9	14	9.4	89.8	72.8
6	11	13	9.6	89.1	73.7
7	13	13	9.6	91.6	75.8

序号 No.	蒸馏温度/℃ distillation temperature	蒸馏时间/min distillation time	蒸气温度/℃ vapor temperature	馏分质量/g mass of fraction	纯度/% purity	回收率/% recovery
1	140	22	109	3.5	76.1	23.0
2	150	17	115	5.6	80.7	39.0
3	160	14	118	6.5	83.5	46.8
4	170	13	123	7.3	82.3	51.8
5	180	9	126	7.5	85.7	55.4
6	190	9	130	7.6	84.1	55.1

序号 No.	氧化钙用量/mmol CaO dosage	蒸馏时间/min distillation time	馏分质量/g mass of fraction	纯度/% purity	回收率/% recovery
1	24	12	1.7	82.7	12.1
2	27	10	3.5	85.5	25.8
3	30	11	5.0	86.3	37.2
4	33	11	6.5	86.7	48.6
5	36	10	4.9	85.9	36.3

减压蒸馏法从生物质水解液中分离提纯乙酰丙酸

Separation and Purification of Levulinic Acid from Hydrolysate of Biomass by Using Compression Vacuum Distillation

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序号 No.	氢氧化钠用量/mmol NaOH dosage	蒸馏时间/min distillation time	馏分质量/g mass of fraction	纯度/% purity	回收率/% recovery
1	48	11	8.7	85.4	64.1
2	54	10	9.5	88.9	72.8
3	60	10	10.5	93.3	84.5
4	66	9	10.1	94.7	82.5
5	72	11	9.9	91.6	78.2

序号 No.	投加比¹⁾/% proportion	蒸馏时间/min distillation time	馏分质量/g mass of fraction	纯度/% purity	回收率/% recovery
1	0.7	20	4.0	83.7	39.3
2	0.8	18	6.0	85.6	60.0
3	0.9	20	6.1	86.2	61.1
4	1	19	6.1	85.9	61.7
5	1.1	18	6.7	87.7	68.4
6	1.2	17	7.5	89.3	78.4
7	1.3	17	8.3	92.1	89.0
8	1.4	16	8.5	93.5	91.8
9	1.5	16	8.4	91.7	90.2

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