基于胆碱类离子液体的高纯甲壳素一步提取分离

doi:10.11949/0438-1157.20240600

化工学报 ›› 2024, Vol. 75 ›› Issue (11): 4286-4297.DOI: 10.11949/0438-1157.20240600

基于胆碱类离子液体的高纯甲壳素一步提取分离

冯咪¹^,²^,⁴(), 张杰³(), 吕兴梅¹()

^1.中国科学院过程工程研究所，北京 100190
^2.郑州中科新兴产业技术研究院龙子湖新能源实验室，河南郑州 450000
^3.北京邦维高科新材料科技股份有限公司，北京 100043
^4.武汉纺织大学化学化工学院，生物质纤维与生态染整湖北省重点实验室，湖北武汉 430200

收稿日期:2024-06-03 修回日期:2024-08-14 出版日期:2024-11-25 发布日期:2024-12-26
通讯作者: 吕兴梅
作者简介:冯咪（1992—），女，博士研究生，副研究员，fengmi@ipe.ac.cn
张杰（1980—），男，博士研究生，高级工程师，zjbw@techtextile.com.cn
基金资助:
国家自然科学基金重点项目(22238011);国家自然科学基金面上项目(22178343);国家自然科学基金青年项目(22308360);河南省科技攻关项目(232102231061);生物质纤维与生态染整湖北省重点实验室开放基金（武汉纺织大学）项目(STRZ202310)

One-step extraction and separation of high purity chitin based on choline ionic liquid

Mi FENG¹^,²^,⁴(), Jie ZHANG³(), Xingmei LYU¹()

^1.Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^2.Longzihu New Energy Laboratory, Zhengzhou Institute of Emerging Industrial Technology, Zhengzhou 450000, Henan, China
^3.Beijing BW Techtextile Company Limited by Shares, Beijing 100043, China
^4.Hubei Key Laboratory of Biomass Fibers and Eco-dyeing & Finishing, College of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan 430200, Hubei, China

Received:2024-06-03 Revised:2024-08-14 Online:2024-11-25 Published:2024-12-26
Contact: Xingmei LYU

摘要/Abstract

摘要：

针对传统甲壳素制备工艺污染大、水耗高等缺点，提出了基于离子液体的高纯甲壳素制备绿色新方法。结果表明，所用离子液体中1-乙基-3-甲基咪唑醋酸盐（［Emim］OAc）、甲烷磺酸胆碱（［Ch］Ms）可分别通过溶解-再生两步法、溶解-分离一步法制备得甲壳素，纯度分别达到90.7%、97.4%，收率分别达到38.1%、63.9%。相比于［Emim］OAc提取体系，水含量对［Ch］Ms提取甲壳素影响较小，当水含量增大至50%时，甲壳素纯度仍达94.3%，收率维持在60%。此外，［Ch］Ms分离所得甲壳素结构未发生明显变化，仍保持为α构型，但［Emim］OAc分离所得甲壳素构型转变为半α构型。提出了［Ch］Ms阴、阳离子协同作用脱除蛋白质、碳酸钙，制备甲壳素机理。相比于［Emim］OAc体系，［Ch］Ms提取甲壳素具有低成本、易分离、流程短及产品纯度高等优势，更有利于大规模应用。

关键词: 离子液体, 生物质, 溶解, 分离, 甲壳素

Abstract:

In view of the shortcomings of traditional chitosan preparation process such as high pollution and high water consumption, this paper proposes a new green method for preparing high-purity chitosan based on ionic liquids. The results showed that the [Emim]OAc and [Ch]Ms can respectively prepare chitin with purities of 90.7% and 97.4%, and yields of 38.1% and 63.9% through a two-step dissolution-regeneration method and a one-step dissolution-separation method. Compared with the 1-ethyl-3-methylimidazolium acetate ([Emim]OAc) extraction system, the water content has less influence on chitin extraction by choline methanesulfonate [Ch]Ms. When the water content increases to 50%, the chitin purity still reached 94.3%, and the yield remained at 60%. Additionally, the chitin structure obtained from the [Ch]Ms separation remained in the α form, while the chitin obtained from the [Emim]OAc separation transitioned to a semi-α form. The preliminary mechanism indicated that the synergistic action of the cations and anions in [Ch]Ms effectively removed protein and calcium carbonate, resulting in high-purity chitin. Compared to the [Emim]OAc system, the [Ch]Ms system offered advantages such as lower cost, easier separation, and shorter processing time, making it more suitable for large-scale applications.

Key words: ionic liquid, biomass, dissolution, separation, chitin

中图分类号:

TQ 028.8

冯咪, 张杰, 吕兴梅. 基于胆碱类离子液体的高纯甲壳素一步提取分离[J]. 化工学报, 2024, 75(11): 4286-4297.

Mi FENG, Jie ZHANG, Xingmei LYU. One-step extraction and separation of high purity chitin based on choline ionic liquid[J]. CIESC Journal, 2024, 75(11): 4286-4297.

图/表 15

图1 本文所用离子液体结构式

Fig.1 The structure of used ionic liquids

表1 所用离子液体对虾壳的溶解率及再生率

Table 1 Dissolution rate and regeneration rate of shrimp shells by the used ionic liquids

离子液体	溶解率/%	再生率/%
[Ch]OAc	58.0	<5.0
[Emim]OAc	63.0	19.0
[Ch]Ms	70.5	<5.0
[Emim]Ms	38.8	<5.0

图2 不同离子液体对虾壳组分的溶解情况

Fig.2 The dissolution behavior to shrimp shells of different ILs

表2 所用离子液体处理虾壳不溶物、再生物及甲壳素收率

Table 2 The yield of precipitate， regenerated product and chitin using different ILs treatment

离子液体	不溶物收率/%	不溶物中甲壳素收率/%	再生物收率/%	再生物中甲壳素收率/%
[Ch]OAc	42.0	73.7	<5	—
[Emim]OAc	37.0	48.8	19	38.1
[Ch]Ms	29.5	63.9	<5	—
[Emim]Ms	61.2	87.7	<5	—

图3 不同酸含量[Ch]OAc/HOAc体系对甲壳素提取的影响

Fig.3 The effect of HOAc content in [Ch]OAc/HOAc on the preparation of chitin

图4 不同水含量[Ch]Ms水溶液对甲壳素提取的影响

Fig.4 The effect of [Ch]Ms aqueous solutions with different water contents on chitin extraction

表3 不同离子液体提取甲壳素对比

Table 3 Comparison of chitin extraction using different ionic liquids

提取体系	生物质原料	提取条件	甲壳素纯度/%	甲壳素收率/%	甲壳素分子量	甲壳素DA值/%
[Amim]Br + 柠檬酸水溶液^[12]	蟹壳	120℃ 24 h	>99	12.6	1.5×10⁵	94
[DIPEA][Ac] + 柠檬酸水溶液^[13]	虾壳	110℃ 36 h	>98	14.8	7.1×10⁴	98.67
[DIPEA][P] + 柠檬酸水溶液^[13]	虾壳	110℃ 30 h	>98	11.5	5.6×10⁴	98.33
[DMBA][Ac] + 柠檬酸水溶液^[13]	虾壳	110℃ 30 h	>98	13.7	6.3×10⁴	98.99
[NH₃(CH₂)₂OH][OAc]^[20]	处理虾壳	90℃ 2 h	46	81	—	—
[NH₃OH][OAc]^[20]	虾壳	100℃ 8 h	76	96	—	83
[NH₃OH][OAc]^[20]	处理虾壳	100℃ 8 h	78	100	—	68
[DBNH][OAc]-AcOH^[30]	虾壳	120℃ 30 h	91	30		83
硫酸镍水溶液+[Emim]Cl^[21]	虾壳	130℃ 24 h + 150℃ 24 h	96.5	72.5	1.3×10⁵	—
[Ch]Ms（本工作）	虾壳	110℃ 7 h	97.4	63.9	1.17×10⁵	95.5

图5 样品红外谱图及[Ch]Ms回收实验

Fig.5 The FT-IR spectra of sample and the recycling of [Ch]Ms

图6 离子液体处理所得不溶物、再生物及甲壳素标样红外谱图a—甲壳素标样;b—[Ch]Ms处理虾壳所得不溶物;c—[Ch]OAc处理虾壳所得不溶物;d—[Emim]Ms处理虾壳所得不溶物;e—[Emim]OAc处理虾壳所得不溶物;f—[Emim]OAc处理虾壳所得再生物

Fig.6 The FT-IR spectra of obtained precipitate, regenerated product and chitin

图7 离子液体处理所得不溶物甲壳素、再生物甲壳素及甲壳素标样固体13C NMR谱图a—[Emim]OAc处理所得再生物甲壳素；b—[Ch]Ms处理所得不溶物甲壳素；c—甲壳素标样

Fig.7 The solid 13C NMR spectra of precipitated chitin, regenerated chitin, and chitin

图8 甲壳素标样及所得甲壳素拉曼光谱a—甲壳素标样；b—[Ch]Ms处理所得不溶物甲壳素

Fig.8 Raman spectra of chitin and obtained chitin

图9 甲壳素标样及所得甲壳素XRD谱图a—甲壳素标样；b—[Emim]OAc处理所得再生物标样；c—[Ch]Ms处理所得不溶物标样

Fig.9 XRD pattern of chitin and obtained chitin

图10 甲壳素标样及所得甲壳素同步X光源辐射谱

Fig.10 Synchrotron X-ray of obtained chitin and chitin

图11 甲壳素标样及处理所得甲壳素DSC曲线a—甲壳素标样;b—[Ch]Ms处理所得不溶物甲壳素

Fig.11 The DSC curves of the chitin and obtained chitin

图12 [Ch]Ms脱除虾壳中碳酸钙和蛋白质的示意图

Fig.12 Scheme of demineralization and deproteinization of [Ch]Ms to shrimp shell

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基于胆碱类离子液体的高纯甲壳素一步提取分离

One-step extraction and separation of high purity chitin based on choline ionic liquid

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