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

doi:10.11949/0438-1157.20240600

Abstract

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

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

CLC Number:

TQ 028.8

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.

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.

Figures/Tables 15

Fig.1 The structure of used ionic liquids

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

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

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	—

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

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

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

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

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

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

Fig.8 Raman spectra of chitin and obtained chitin

Fig.9 XRD pattern of chitin and obtained chitin

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

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

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

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