Advancements and obstacles in the production of nitrogen-containing bio-based chemicals from chitin biomass

doi:10.11949/0438-1157.20240863

Abstract

Abstract:

The energy security and environmental pollution issues brought about by the exploitation and utilization of large amounts of fossil resources have attracted widespread attention.The exploitation of renewable resources and the advancement of renewable energy and green chemicals are pivotal aspects of sustainable development. Biomass stands as the sole sustainable carbon resource, with its conversion and utilization representing a crucial pathway towards accomplishing the dual carbon goals. Chitin, being the second largest biomass, constitutes the sole nitrogen-containing polysaccharide. Hence, the process of converting chitin for the preparation of nitrogen-containing chemicals holds distinctive theoretical and practical significance. Remarkable strides have been made in recent years with regards to chitin conversion for the production of nitrogen-containing chemicals. This article primarily delves into the nitrogen-containing structural features of chitin, outlining the most recent research progress in chitin hydrolysis for the generation of oligomers and monosaccharide N-acetylglucosamine, the transformation of chitin and monosaccharides for the production of furan compounds, hybrid nitrogen-containing chemicals, and other nitrogen-containing chemicals. Particularly, the advancements and principles of catalytic conversion of chitin and monomers for the preparation of 3-acetylamino-5-acetylfuran are summarized. In addressing these advancements, the article also presents the existing issues and challenges, while offering a glimpse of the research direction in this field, in an effort to advance the high-quality development of chitin catalytic conversion for the preparation of nitrogen-containing chemicals and to aid in achieving the dual carbon goals.

Key words: biomass, chemical process, catalysis, chitin, nitrogen-containing chemicals

摘要：

大量化石资源开采和利用带来的能源安全和环境污染问题已经引起广泛关注。利用可再生资源，发展可再生能源和绿色化学品是可持续发展的重要方向。生物质是唯一可持续发展碳资源，其转化利用是实现“双碳”目标的重要途径之一。几丁质作为第二大生物质，是唯一含氮多糖；将几丁质转化制备含氮化学品具有独特的理论和应用意义。近年来，将几丁质转化制备含氮化学品取得较大进展。主要针对几丁质含氮结构特点，总结了几丁质水解生成寡聚物和单糖N-乙酰氨基葡萄糖，以及几丁质及单糖转化制备呋喃化合物、杂环含氮化学品和其他含氮化学品的最新研究进展。重点归纳了几丁质及单体催化转化制备3-乙酰氨基-5-乙酰基呋喃的进展和规律。针对这些进展，还提出了该领域存在的问题和挑战，并展望了该领域的发展方向，以期推动几丁质催化转化制备含氮化学品高质量发展，助力实现“双碳”目标。

关键词: 生物质, 化学过程, 催化, 几丁质, 含氮化学品

CLC Number:

TQ 95

Qishun LIU, Deyu CHU, Jinjing MA, Heng YIN. Advancements and obstacles in the production of nitrogen-containing bio-based chemicals from chitin biomass[J]. CIESC Journal, 2024, 75(11): 4065-4081.

刘启顺, 褚德育, 马金晶, 尹恒. 几丁质生物质制备含氮生物基化学品进展及挑战[J]. 化工学报, 2024, 75(11): 4065-4081.

Figures/Tables 10

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反应体系	反应溶剂	底物浓度	催化剂	反应温度/℃	反应时间/h	收率/%	文献
水	38% HCl	20% (质量分数)	HCl	30 (超声处理)	4	65	[33]
离子液体	[C₄MIM]Cl	1% (质量分数)	6% (质量分数) [C₃SO₃HMIM]OTf	120	5	15	[21]
熔盐水合物	50% CaCl₂-H₂O	50 g/L	10% ZnBr₂	120	1	66.8	[39]
熔盐水合物	60% LiCl-H₂O	50 g/L	40 mmol/L HCl	120	0.5	71.5	[38]
熔盐水合物	60% LiCl-H₂O	25 g/L	SAPO-34 （20 g/L）	130	2	63	[40]
熔盐水合物	60% LiCl-H₂O	25 g/L	Hβ （20 g/L）	130	2	约20	[40]
熔盐水合物	60% LiCl-H₂O	25 g/L	HUSY （20 g/L）	130	2	约45	[40]
熔盐水合物	60% LiCl-H₂O	25 g/L	ZSM-5 （20 g/L）	130	2	约60	[40]
水	机械球磨	底物/催化剂=2.0	H₂SO₄	170	1	53	[43]
甲醇	机械球磨	底物/催化剂=4.1	H₂SO₄	170	1	70 (产物为1-O-甲基-N- 乙酰氨基葡萄糖)	[43]
水	机械球磨	底物/催化剂=1.25	氧化活性炭	40~50	12	可溶物72% (其中NAG 8.3%，寡糖66%)	[48]
水	机械球磨	底物/催化剂=1.25	ZSM-5	40~50	12	可溶物23% (其中NAG1.6%，寡糖9.3%)	[48]
水	机械球磨	底物/催化剂=4.0	H₂SO₄	40~50	2	可溶物95%，其中NAG 7.3%，寡糖62%	[48]
水	机械球磨	底物/催化剂=1.0	高岭土	—	4	可溶物75.8% (其中NAG 5.1%，二聚物3.9%)	[47]
非极性溶剂	乙二醇∶水=4∶1 (体积比)	15% (质量分数)	8% H₂SO₄(相对溶剂)	165	1.5	可溶物75% (其中30%为HADP和HAADP)	[49]

反应体系	反应溶剂	底物浓度	催化剂	反应温度/℃	反应时间/h	收率/%	文献
水	38% HCl	20% (质量分数)	HCl	30 (超声处理)	4	65	[33]
离子液体	[C₄MIM]Cl	1% (质量分数)	6% (质量分数) [C₃SO₃HMIM]OTf	120	5	15	[21]
熔盐水合物	50% CaCl₂-H₂O	50 g/L	10% ZnBr₂	120	1	66.8	[39]
熔盐水合物	60% LiCl-H₂O	50 g/L	40 mmol/L HCl	120	0.5	71.5	[38]
熔盐水合物	60% LiCl-H₂O	25 g/L	SAPO-34 （20 g/L）	130	2	63	[40]
熔盐水合物	60% LiCl-H₂O	25 g/L	Hβ （20 g/L）	130	2	约20	[40]
熔盐水合物	60% LiCl-H₂O	25 g/L	HUSY （20 g/L）	130	2	约45	[40]
熔盐水合物	60% LiCl-H₂O	25 g/L	ZSM-5 （20 g/L）	130	2	约60	[40]
水	机械球磨	底物/催化剂=2.0	H₂SO₄	170	1	53	[43]
甲醇	机械球磨	底物/催化剂=4.1	H₂SO₄	170	1	70 (产物为1-O-甲基-N- 乙酰氨基葡萄糖)	[43]
水	机械球磨	底物/催化剂=1.25	氧化活性炭	40~50	12	可溶物72% (其中NAG 8.3%，寡糖66%)	[48]
水	机械球磨	底物/催化剂=1.25	ZSM-5	40~50	12	可溶物23% (其中NAG1.6%，寡糖9.3%)	[48]
水	机械球磨	底物/催化剂=4.0	H₂SO₄	40~50	2	可溶物95%，其中NAG 7.3%，寡糖62%	[48]
水	机械球磨	底物/催化剂=1.0	高岭土	—	4	可溶物75.8% (其中NAG 5.1%，二聚物3.9%)	[47]
非极性溶剂	乙二醇∶水=4∶1 (体积比)	15% (质量分数)	8% H₂SO₄(相对溶剂)	165	1.5	可溶物75% (其中30%为HADP和HAADP)	[49]

原料	溶剂	催化剂/添加剂	反应温度/℃	反应时间/min	3A5AF收率/%	文献
NAG	DMAc	B(OH)₃/NaCl	220	15	62	[60]
NAG	DMF	AlCl₃/－	120	30	30	[61]
NAG	NMP	MgCl₂/B₂O₃	180	60	41	[62]
几丁质	NMP	B(OH)₃/NaCl	215	90	7	[72]
几丁质（球磨预处理）	[BMIM]Cl	B(OH)₃/HCl	180	10	28	[73]
NAG	[BMIM]Cl	B(OH)₃/－	180	60	60	[63]
NAG	[BMIM]Cl	－/－	180	3	25	[63]
NAG	[Gly]Cl	CaCl₂/－	200	10	52	[64]
NAG	DMAc	[Pyz]Cl/B(OH)₃-CaCl₂	190	60	69	[65]
NAG	NMP	[PDCMPi]Cl/－	180	20	42	[66]
NAG	DMAc	(ChCl-CA)/CaCl₂	210	20	47	[67]
NAG	DES	(ChCl-PEG-B(OH)₃)/－	180	15	18	[68]
NAG	DMAc	(ChCl-Gly-B(OH)₃)/－	140	150	39	[69]
NAG	NMP	[CMPy]Cl/B₂O₃/CaCl₂	180	20	67	[75]
NAG	DMF	NH₄Cl/LiCl	160	5	43	[70]
NAG	GVL	NH₄SCN/HCl	140	120	75	[71]
NAG	DMAc	Al-Mont/NaCl	160	120	14	[76]
NAG	DMAc	H-ZSM-5/NaCl	160	120	9	[76]
NAG	1,4-二氧六环	La₂O₃/－	180	180	21	[77]

原料	溶剂	催化剂/添加剂	反应温度/℃	反应时间/min	3A5AF收率/%	文献
NAG	DMAc	B(OH)₃/NaCl	220	15	62	[60]
NAG	DMF	AlCl₃/－	120	30	30	[61]
NAG	NMP	MgCl₂/B₂O₃	180	60	41	[62]
几丁质	NMP	B(OH)₃/NaCl	215	90	7	[72]
几丁质（球磨预处理）	[BMIM]Cl	B(OH)₃/HCl	180	10	28	[73]
NAG	[BMIM]Cl	B(OH)₃/－	180	60	60	[63]
NAG	[BMIM]Cl	－/－	180	3	25	[63]
NAG	[Gly]Cl	CaCl₂/－	200	10	52	[64]
NAG	DMAc	[Pyz]Cl/B(OH)₃-CaCl₂	190	60	69	[65]
NAG	NMP	[PDCMPi]Cl/－	180	20	42	[66]
NAG	DMAc	(ChCl-CA)/CaCl₂	210	20	47	[67]
NAG	DES	(ChCl-PEG-B(OH)₃)/－	180	15	18	[68]
NAG	DMAc	(ChCl-Gly-B(OH)₃)/－	140	150	39	[69]
NAG	NMP	[CMPy]Cl/B₂O₃/CaCl₂	180	20	67	[75]
NAG	DMF	NH₄Cl/LiCl	160	5	43	[70]
NAG	GVL	NH₄SCN/HCl	140	120	75	[71]
NAG	DMAc	Al-Mont/NaCl	160	120	14	[76]
NAG	DMAc	H-ZSM-5/NaCl	160	120	9	[76]
NAG	1,4-二氧六环	La₂O₃/－	180	180	21	[77]

原料	溶剂	反应温度/℃	时间/s	反应压力/bar（或催化剂）	产物（收率/%）	文献
NAG	硼酸缓冲液(pH 7)	100	2	—	3, 6-AGF（10.2），3, 6-AMF（9.8）	[82]
NAG	高温水	220	39	250	色原Ⅰ（23），色原Ⅲ（23.1）	[84]
NAG	高温水	280	34	250	色原Ⅰ（37），色原Ⅲ（34.5）	[86]
几丁质	高温水	390	3600	250	色原Ⅰ（2.6）	[87]
几丁质	NaOH溶液	300	300	CuO	吡咯（6）	[18]