ZnCl2催化生物质热解液化制呋喃类及醛类化学品研究

doi:10.3969/j.issn.0253-2417.2020.02.016

摘要/Abstract

摘要：

以油菜秸秆、玉米秸秆和樟木粉为原料，选择ZnCl₂为催化剂，在水平管式炉反应器上热解液化，以所得生物油中呋喃类和醛类化学品组分产率，以及糠醛、多聚甲醛和5-甲基糠醛3种高附加值化学品的产率为指标，探讨不同反应条件对生物油中主要呋喃类和醛类组分分布及产率的影响。研究结果表明：无催化剂时，樟木粉热解所得生物油产率最高，达51.76%，当加入与生物质原料质量比为1:1的ZnCl₂催化剂时，3种原料热解所得生物油的产率均有所降低，其中樟木粉的生物油产率（30.50%）降低最为明显；玉米秸秆和樟木粉所得生物油中醛类组分的产率均有增加，产率分别为0.48%和0.84%。与未加入催化剂相比，油菜秸秆、玉米秸秆和樟木粉催化热解后所得生物油中呋喃类组分的产率增加明显，增长幅度分别为253.72%、85.05%和202.32%；糠醛的产率增长幅度分别为470.41%、313.87%和340.99%，5-甲基糠醛的产率增长幅度分别为318.18%、200.00%和213.04%；同时玉米秸杆催化热解所得生物油中多聚甲醛产率略有提升。

关键词: 生物质, 快速热解, 化学品, ZnCl₂, 糠醛(FF), 呋喃类

Abstract:

Using rape straw, corn straw and camphor wood powder as raw materials, ZnCl₂ was selected as a catalyst to carry out catalytic pyrolysis experiments in a horizontal tubular furnace reactor. The yields of the high value-added chemicals, e.g. furfural (FF), paraformaldehyde and 5-methylfurfural, in the bio-oil were taken as evaluation indexes. The results showed that the bio-oil yield of camphor wood powder was the highest, up to 51.76%, without catalyst. When ZnCl₂ was the catalyst with a mass ratio of 1:1 in the pyrolysis, the bio-oil yield of the three raw materials decreased. And the bio-oil yield of camphor wood powder (30.50%) decreased significantly. The yield of aldehydes in the bio-oil obtained from corn straw and camphor wood powder increased to 0.48% and 0.84%, respectively. After catalytic pyrolysis of rape straw, corn straw and camphor wood powder, the yield of furans in the bio-oil increased by 253.72%, 85.05%, and 202.32%, respectively. The yield of FF in bio-oil increased by 470.41%, 313.87%, and 340.99%, respectively. The yield of 5-methylfurfural increased by 318.18%, 200.00%, and 213.04%, respectively. Meanwhile, the yield of paraformaldehyde in the bio-oil obtained from the catalytic pyrolysis of corn straw by ZnCl₂ increased increased slightly.

Key words: biomass, rapid pyrolysis, chemicals, ZnCl₂, furfural, furans

中图分类号:

TQ35
TK6

李泊铮,毕冬梅,李永军,姜梅. ZnCl₂催化生物质热解液化制呋喃类及醛类化学品研究[J]. 林产化学与工业, 2020, 40(2): 117-124.

Bozheng LI,Dongmei BI,Yongjun LI,Mei JIANG. Catalytic Pyrolysis of Biomass to Produce Specific High Value-added Furans and Aldehydes Chemicals[J]. Chemistry and Industry of Forest Products, 2020, 40(2): 117-124.

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原料 samples	纤维素 cellulose	半纤维素 hemicellulose	木质素 lignin	元素分析elemental analysis(w_d)				工业分析ultimate analysis(w_d)
原料 samples	纤维素 cellulose	半纤维素 hemicellulose	木质素 lignin	C	H	O^*	N	固定炭 fixed carbon	挥发分 volatiles	灰分 ash
油菜秸秆rape straw	35.41	17.84	21.64	48.52	5.74	45.23	0.51	15.27	79.18	5.55
玉米秸秆corn straw	32.54	18.34	22.02	47.46	5.78	46.32	0.44	12.26	80.59	7.15
樟木粉camphor wood powder	37.62	12.65	34.74	53.16	6.12	40.34	0.38	13.35	86.14	0.51

原料 samples		化合物 compounds	GC含量GC content/%
原料 samples		化合物 compounds	无催化剂catalyst-free	ZnCl₂
油菜秸秆 rape straw	醛类 aldehyde	多聚甲醛paraformaldehyde	0.63	0.35
		二乙醇缩甲醛diethoxy methane	—	1.16
		羟基乙醛hydroxy-acetaldehyde	1.42	—
		丁二醛butanedial	2.58	—
		5-乙酰氧基甲基-2-呋喃醛5-acetoxymethylfurfural		1.05
	呋喃类 furan	糠醛furfural	3.81	29.49
		糠醇furanmethanol	1.99	—
		5-甲基糠醛5-methylfurfural	0.42	2.45
		2(5H)呋喃酮2(5H)-furanone	1.11	1.27
玉米秸秆 corn straw	醛类 aldehyde	多聚甲醛paraformaldehyde	—	0.58
	醛类 aldehyde	二乙醇缩甲醛diethoxy methane	—	1.93
	呋喃类 furan	糠醛furfural	5.54	29.30
		糠醇furanmethanol	2.96	—
		5-甲基糠醛5-methylfurfural	0.96	3.54
		5-羟甲基糠醛5-hydroxymethylfurfural	3.38	—
		2(5H)呋喃酮2(5H)-furanone	1.01	2.55
樟木粉 camphor wood powder	醛类 aldehyde	多聚甲醛paraformaldehyde	0.97	1.57
		二乙醇缩甲醛diethoxy methane	—	3.92
		4-羟基-3, 5-二甲氧基-苯甲醛syringaldehyde	1.11	—
	呋喃类 furan	糠醛furfural	4.46	46.22
		糠醇furanmethanol	1.55	—
		5-甲基糠醛5-methylfurfural	0.33	4.65
		5-羟甲基糠醛5-hydroxymethylfurfural	0.59	—

催化剂 catalyst	油菜秸秆rape straw		玉米秸秆corn straw		樟木粉camphor wood powder
催化剂 catalyst	醛类 aldehyde	呋喃类 furan	醛类 aldehyde	呋喃类 furan	醛类 aldehyde	呋喃类 furan
无催化剂catalyst-free	1.19	1.88	—	3.68	0.78	2.59
ZnCl₂	0.51	6.65	0.48	6.81	0.84	7.83

原料samples	多聚甲醛 paraformaldehydel		糠醛furfural		5-甲基糠醛5-methylfurfural
原料samples	无催化剂 catalyst-free	ZnCl₂	无催化剂 catalyst-free	ZnCl₂	无催化剂 catalyst-free	ZnCl₂
油菜秸秆rape straw	0.16	0.11	0.98	5.59	0.11	0.46
玉米秸秆corn straw	—	0.07	1.37	5.67	0.23	0.69
樟木粉camphor wood powder	0.35	0.24	1.61	7.10	0.23	0.72

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ZnCl₂催化生物质热解液化制呋喃类及醛类化学品研究

Catalytic Pyrolysis of Biomass to Produce Specific High Value-added Furans and Aldehydes Chemicals

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