催化型多孔陶瓷球制备及催化玉米秸秆热解

doi:10.16085/j.issn.1000-6613.2021-1833

摘要/Abstract

摘要：

针对生物质热解液化过程中生物油品质差的问题，本文以陶瓷球作热载体为研究基础，制备了5种负载金属氧化物（ZnO、NiO、CeO₂、Cr₂O₃、Fe₂O₃）的多孔陶瓷球，在固定床反应器上研究多孔陶瓷球催化剂对玉米秸秆热解过程的催化效果。结果表明：多孔陶瓷球基体在热解过程中有一定催化活性，经浸渍改性处理后，都能促进生物油产率的提高，其中Ni基多孔陶瓷球热解的产率高达41.62%。多孔陶瓷球负载的5种金属氧化物可促使生物油中酚类、呋喃类物质的含量明显增加，酸类物质的含量明显降低，且种类减少，其中CeO₂降酸效果显著，降低幅度为37.15%。此外，催化型多孔陶瓷球的引入促进了不可冷凝气中C _n H _m （n≥2）的生成，烯烃类中乙烯的增长幅度最大，为50.53%，同时生物炭的理化特性在一定程度上得到改善和提高。

关键词: 多孔陶瓷球, 催化热解, 生物质, 生物油

Abstract:

In order to solve the problems of poor product quality in the process of biomass pyrolysis liquefaction, the research was based on the ceramic ball as a heat carrier, porous ceramic balls loaded with (ZnO, NiO, CeO₂, Cr₂O₃, and Fe₂O₃) were produced, and the catalytic effect of porous ceramic balls catalyst in the pyrolysis process of corn stover was investigated on a fixed bed reactor. The results indicated that the prepared porous ceramic balls matrix had catalytic activity in the pyrolysis of corn stover. All modified porous ceramic balls could improve the production rate of bio-oil, and the Ni-based porous ceramic balls had the highest production rate of 41.62%. The five metal oxides supported by the porous ceramic balls could increase the content of phenols and furans obviously and reduce the acid substances in bio-oil and its types. Among them, the acid reduction effect of Ce-based porous ceramic balls was significant, with a reduction of 37.15%. The addition of catalytic porous ceramic balls promoted the production of C _n H _m (n≥2) in non-condensable gases, and among the olefins the ethylene increases the most, which was 50.53%. Meanwhile, the physicochemical properties of biochar were improved. The research would provide an important reference for the efficient preparation of liquid fuels and fine chemicals by the catalytic pyrolysis of biomass.

Key words: porous ceramic balls, catalytic pyrolysis, biomass, bio-oil

中图分类号:

李玉峰, 王绍庆, 张安东, 毕冬梅, 李志合, 高亮, 万震. 催化型多孔陶瓷球制备及催化玉米秸秆热解[J]. 化工进展, 2022, 41(7): 3597-3607.

LI Yufeng, WANG Shaoqing, ZHANG Andong, BI Dongmei, LI Zhihe, GAO Liang, WAN Zhen. Preparation of catalytic porous ceramic balls and catalytic pyrolysis of corn stover[J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3597-3607.

图/表 14

参考文献 29

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元素分析 w_d/%					工业分析 w_d/%				组分分析 w_d/%
N	C	H	O^*		灰分	挥发分	固定碳		纤维素	半纤维素	木质素
0.63	43.87	5.57	40.11		9.82	71.31	18.87		31.98	29.23	2.84

元素分析 w_d/%					工业分析 w_d/%				组分分析 w_d/%
N	C	H	O^*		灰分	挥发分	固定碳		纤维素	半纤维素	木质素
0.63	43.87	5.57	40.11		9.82	71.31	18.87		31.98	29.23	2.84

生物油组分	相对峰面积/%
生物油组分	无催化	PCB	Zn/PCB	Ni/PCB	Ce/PCB	Cr/PCB	Fe/PCB
醛类
甲醛	1.27	0.71	0.25	0.36	0.32	0.22	0.28
甲基乙二醛	0.60	0.77	1.22	1.62	1.40	2.50	1.80
2-甲基十一醛	—	—	1.53	1.33	1.81	1.36	1.40
3-羟基苯甲醛	0.88	0.81	1.44	1.52	1.67	1.51	1.37
醇类
甲醇	4.91	4.26	2.48	2.02	1.53	2.33	2.18
1，7，7-三甲基-双环［2，2，1］庚烷-2，3-二醇	1.25	1.59	—	—	—	—	—
酮类
2，3-丁二酮	1.78	1.65	—	—	—	—	—
1-羟基-2-丙酮	6.29	6.42	5.06	5.26	4.42	4.35	5.18
1-乙酰氧基-2-丁酮	1.87	1.66	1.50	1.38	1.29	1.12	1.28
1-乙酰氧基-2-丙酮	1.70	1.52	1.21	1.26	1.23	1.07	1.34
2-甲基-1-戊烯-1酮	0.88	0.93	1.60	1.60	1.95	1.42	1.01
3-甲基-1，2-环戊二酮	—	—	1.45	1.57	1.67	1.20	1.52
酸类
甲酸	1.27	0.54	—	—	—	—	—
乙酸	22.9	23.05	19.39	20.37	17.54	20.09	24.82
丙酸	2.62	2.57	1.33	1.60	1.41	1.20	1.68
亚甲基环丙烷羧酸	1.95	2.03	—	—	—	—	—
酯类
2-氧代丙酸甲酯	1.11	0.91	0.61	0.52	0.53	0.41	0.52
丁内酯	0.97	1.22	1.18	1.41	1.36	1.32	1.47
酚类
苯酚	3.48	4.01	3.81	4.08	3.69	3.73	4.07
2-甲基苯酚	1.39	1.56	1.12	1.10	1.03	1.06	1.11
对甲酚	1.85	2.14	2.43	2.23	2.25	2.23	2.45
4-乙基苯酚	1.91	2.55	2.47	2.58	2.32	2.17	2.23
邻苯二酚	—	—	1.96	1.67	1.94	0.43	0.72
对苯二酚	—	—	1.33	1.33	1.38	1.39	1.30
呋喃类
糠醛	6.02	6.25	3.08	3.22	3.23	3.64	4.22
2-呋喃甲醇	—	—	1.43	1.51	1.39	1.41	1.44
3-甲基-2，5-呋喃二酮	0.94	0.89	1.79	1.38	1.55	2.02	1.79
2，3-二氢苯并呋喃	4.06	4.92	7.04	6.81	6.94	7.71	7.00
5-羟甲基糠醛	1.10	0.94	1.87	1.65	1.89	1.94	1.90
糖类
1，4：3，6-二脱水-α-D-吡喃葡萄糖	—	—	1.67	1.56	1.70	1.70	1.78
1，6-脱水-β-D-吡喃葡萄糖	1.57	1.44	2.61	2.59	3.22	3.65	2.14

生物油组分	相对峰面积/%
生物油组分	无催化	PCB	Zn/PCB	Ni/PCB	Ce/PCB	Cr/PCB	Fe/PCB
醛类
甲醛	1.27	0.71	0.25	0.36	0.32	0.22	0.28
甲基乙二醛	0.60	0.77	1.22	1.62	1.40	2.50	1.80
2-甲基十一醛	—	—	1.53	1.33	1.81	1.36	1.40
3-羟基苯甲醛	0.88	0.81	1.44	1.52	1.67	1.51	1.37
醇类
甲醇	4.91	4.26	2.48	2.02	1.53	2.33	2.18
1，7，7-三甲基-双环［2，2，1］庚烷-2，3-二醇	1.25	1.59	—	—	—	—	—
酮类
2，3-丁二酮	1.78	1.65	—	—	—	—	—
1-羟基-2-丙酮	6.29	6.42	5.06	5.26	4.42	4.35	5.18
1-乙酰氧基-2-丁酮	1.87	1.66	1.50	1.38	1.29	1.12	1.28
1-乙酰氧基-2-丙酮	1.70	1.52	1.21	1.26	1.23	1.07	1.34
2-甲基-1-戊烯-1酮	0.88	0.93	1.60	1.60	1.95	1.42	1.01
3-甲基-1，2-环戊二酮	—	—	1.45	1.57	1.67	1.20	1.52
酸类
甲酸	1.27	0.54	—	—	—	—	—
乙酸	22.9	23.05	19.39	20.37	17.54	20.09	24.82
丙酸	2.62	2.57	1.33	1.60	1.41	1.20	1.68
亚甲基环丙烷羧酸	1.95	2.03	—	—	—	—	—
酯类
2-氧代丙酸甲酯	1.11	0.91	0.61	0.52	0.53	0.41	0.52
丁内酯	0.97	1.22	1.18	1.41	1.36	1.32	1.47
酚类
苯酚	3.48	4.01	3.81	4.08	3.69	3.73	4.07
2-甲基苯酚	1.39	1.56	1.12	1.10	1.03	1.06	1.11
对甲酚	1.85	2.14	2.43	2.23	2.25	2.23	2.45
4-乙基苯酚	1.91	2.55	2.47	2.58	2.32	2.17	2.23
邻苯二酚	—	—	1.96	1.67	1.94	0.43	0.72
对苯二酚	—	—	1.33	1.33	1.38	1.39	1.30
呋喃类
糠醛	6.02	6.25	3.08	3.22	3.23	3.64	4.22
2-呋喃甲醇	—	—	1.43	1.51	1.39	1.41	1.44
3-甲基-2，5-呋喃二酮	0.94	0.89	1.79	1.38	1.55	2.02	1.79
2，3-二氢苯并呋喃	4.06	4.92	7.04	6.81	6.94	7.71	7.00
5-羟甲基糠醛	1.10	0.94	1.87	1.65	1.89	1.94	1.90
糖类
1，4：3，6-二脱水-α-D-吡喃葡萄糖	—	—	1.67	1.56	1.70	1.70	1.78
1，6-脱水-β-D-吡喃葡萄糖	1.57	1.44	2.61	2.59	3.22	3.65	2.14

催化剂	比表面积/m²·g^-1	孔容/10^-3cm³·g^-1	孔径/nm
无	3.78	6.75	13.54
PCB	4.44	6.89	11.53
Zn/PCB	4.96	7.71	7.93
Ni/PCB	5.43	7.77	7.12
Ce/PCB	5.11	9.52	7.79
Cr/PCB	8.28	14.99	7.45
Fe/PCB	9.37	15.91	7.03