Mo/ZSM-5催化作用下生物质快速热解制生物油实验研究

doi:10.11949/0438-1157.20190305

摘要/Abstract

摘要：

采用等体积浸渍法制备Mo/ZSM-5催化剂，并应用于生物质快速热解制备生物油。采用Py-GC/MS装置，重点研究了Mo负载量、反应温度、反应时间和催化剂与木粉质量比等参数对生物油产率和组成的影响规律。实验结果表明，与纯木粉热解相比较，ZSM-5和Mo/ZSM-5催化作用下生物油的产率大幅提高；在反应温度为600℃、反应时间为25 s、催化剂与木粉质量比为10/1的条件下，10Mo/ZSM-5催化作用下生物油中芳香烃类化合物的产率和相对含量达到最大值。根据生物油产率和组成的变化，可以得出Mo负载的ZSM-5催化剂强化促进酸类、醛酮类等含氧化合物转化为芳香烃类化合物，有效实现了生物质热解生物油品质的提升。

关键词: 生物质, 快速热解, 催化作用, 沸石, 生物油

Abstract:

The Mo/ZSM-5 catalyst was prepared by an equal volume impregnation method and applied to the rapid pyrolysis of biomass to prepare bio-oil. The effects of Mo loadings, reaction temperature, reaction time and catalyst/biomass mass ratio on the yields and composition of bio-oils were researched. Compared to the pyrolysis of sawdust, the yields of bio-oils were greatly increased by ZSM-5 and Mo/ZSM-5 catalysts. Under the reaction condition of T=600℃, t=25 s, catalyst/biomass mass ratio=10/1, the yields and amounts of aromatic hydrocarbons in bio-oil reached the maximum by 10Mo/ZSM-5 catalysts. According to the variations of products in bio-oils, Mo/ZSM-5 catalysts promoted the conversion of oxygenated compounds, such as acids, aldehydes and ketones, into aromatic hydrocarbons, which could effectively upgrade the bio-oils.

Key words: biomass, fast pyrolysis, catalysis, zeolite, bio-oils

中图分类号:

TK 6

孙来芝, 陈雷, 赵保峰, 杨双霞, 谢新苹, 孟凡军, 司洪宇. Mo/ZSM-5催化作用下生物质快速热解制生物油实验研究[J]. 化工学报, 2019, 70(8): 3160-3166.

Laizhi SUN, Lei CHEN, Baofeng ZHAO, Shuangxia YANG, Xinping XIE, Fanjun MENG, Hongyu SI. Experiment research on catalytic fast pyrolysis of biomass into bio-oils over Mo/ZSM-5 catalyst[J]. CIESC Journal, 2019, 70(8): 3160-3166.

图/表 7

表1 不同催化剂的比表面积、孔径和孔体积

Table 1 Surface area, pore size and volume of catalysts

催化剂	比表面积/(m²/g)	孔径/nm	孔体积/(cm³/g)
ZSM-5	313	2.33	0.18
5Mo/ZSM-5	219	2.16	0.12
10Mo/ZSM-5	223	2.48	0.13
15Mo/ZSM-5	225	2.47	0.13

图1 不同催化剂的H2-TPR谱图

Fig.1 H2-TPR of catalysts

图2 不同Mo/ZSM-5催化剂作用下生物油产率和组成的变化

Fig.2 Effects of Mo loading of Mo/ZSM-5 on yields and compositions of bio-oils

表2 不同催化剂作用下芳香烃化合物的组成和相对含量变化

Table 2 Effects of catalysts on compositions and amounts of aromatic hydrocarbons/%

催化剂	单环芳烃						稠环芳烃
催化剂	苯	甲苯	乙基苯	二甲苯	茚	其他	萘	蒽	菲
ZSM-5	6.27	22.2	1.02	22.4	1.96	3.54	36.5	3.37	2.74
5Mo/ZSM-5	10.5	29.0	1.30	22.9	2.60	1.37	29.2	1.25	1.88
10Mo/ZSM-5	8.32	26.7	1.75	18.1	0.83	31.0	13.2	0	0
15Mo/ZSM-5	14.4	37.4	2.07	26.2	0.76	2.17	17.0	0	0

图3 不同反应温度下10Mo/ZSM-5催化作用下生物油产率和组成的变化

Fig.3 Effects of reaction temperature on yields and compositions of bio-oils with 10Mo/ZSM-5 catalysts

图4 不同反应时间下10Mo/ZSM-5催化作用下生物油产率和组成的变化

Fig.4 Effects of reaction time on yields and compositions of bio-oils with 10Mo/ZSM-5 catalysts

图5 不同催化剂与木粉质量比对10Mo/ZSM-5催化作用下生物油产率和组成的影响

Fig.5 Effects of catalyst/biomass mass ratio on yields and compositions of bio-oils with 10Mo/ZSM-5 catalysts

参考文献 32

1	Bulushev D A , Rossulian J R H . Catalysis for conversion of biomass to fuels via pyrolysis and gasification: a review [J]. Catalysis Today, 2011, 171: 1-13.
2	隋海清, 李攀, 王贤华, 等 . 生物质热解气分级冷凝对生物油特性的影响[J]. 化工学报, 2015, 66(10): 4138-4144.
	Sui H Q , Li P , Wang X H , et al . Influence on bio-oil by fractional condensation of biomass pyrolysis vapor [J]. CIESC Journal, 2015, 66(10): 4138-4144.
3	Dabros T M H , Zingler S M , Martin H , et al . Transportation fuels from biomass fast pyrolysis, catalytic hydrodeoxygenation, and catalytic fast hydropyrolysis [J]. Progress in Energy and Combustion Science, 2018, 68: 268-309.
4	Bridgwater A V . Review of fast pyrolysis of biomass and product up-grading [J]. Biomass Bioenergy, 2012, 38: 68- 94.
5	王超, 陈冠益, 兰维娟, 等 . 生物质快速热解制油试验及流程模拟[J]. 化工学报, 2014, 65(2): 679-683.
	Wang C , Chen G Y , Lan W J , et al . Experimental research and process simulation on biomass fast pyrolysis for production of bio-oil [J]. CIESC Journal, 2014, 65(2): 679-683.
6	Dhyani V , Bhaskar T . A comprehensive review on the pyrolysis of lignocellulosic biomass [J]. Renewable Energy, 2018, 129: 695-716.
7	Lu Q , Zhang Z F , Dong C Q , et al . Catalytic upgrading of biomass fast pyrolysis vapors with nano metal oxides: an analytical Py-GC/MS study [J]. Energies, 2010, 3: 1805-1820.
8	Qureshi K M , Kay L A N , Khan S , et al . A technical review on semi-continuous and continuous pyrolysis process of biomass to bio-oil [J]. Journal of Analytical and Applied Pyrolysis, 2018, 131: 52-57.
9	Wang S R , Dai G X , Yang H P , et al . Lignocellulosic biomass pyrolysis mechanism: a state-of-the-art review [J]. Progress in Energy and Combustion Science, 2017, 62: 33-86.
10	Kubilay T . Hydrothermal conversion of Russian olive seeds into crude bio-oil using a CaO catalyst derived from waste mussel shells [J]. Energy Fuels, 2015, 29 (7): 4382–4392
11	宋锵, 于凤文, 王佳, 等 . La/P/Ni改性分子筛催化裂解生物油模型化合物[J]. 农业工程学报, 2016, 32(S1): 284-289.
	Song Q , Yu F W , Wang J , et al . Catalytic pyrolysis of bio-oil model compounds over La/P/Ni modified ZSM-5 [J]. Transactions of the Chinese Society of Agricultural Engineering, 2016, 32(S1): 284-289.
12	Shantanu K , Christopher M S , Kevin A , et al . A survey of catalysts for aromatics from fast pyrolysis of biomass [J]. Applied Catalysis B: Environmental, 2015, 174: 85-95.
13	Park Y K , Yoo M L , Jin S H , et al . Catalytic fast pyrolysis of waste pepper stems over HZSM-5 [J]. Renewable Energy, 2015, 79: 20-27.
14	王芸, 邵珊珊, 张会岩, 等 . 生物质模化物催化热解制取烯烃和芳香烃[J]. 化工学报, 2015, 66(8): 3022-3028.
	Wang Y , Shao S S , Zhang H Y , et al . Catalytic pyrolysis of biomass model compounds to olefins and aromatic hydrocarbons [J]. CIESC Journal, 2015, 66(8): 3022-3028.
15	Ohra-Aho T , Linnekoski J . Catalytic pyrolysis of lignin by using analytical pyrolysis-GC–MS [J]. Journal of Analytical and Applied Pyrolysis, 2015, 113: 186-192.
16	Zhang M , Resende F L P , Moutsoglou A . Catalytic fast pyrolysis of aspen lignin via Py-GC/MS [J]. Fuel, 2014, 116: 358-369.
17	季祥, 刘彬, 李湘萍, 等 . 金属改性ZSM-5催化剂对黄丝藻提油后藻渣催化热解的影响[J]. 太阳能学报, 2017, (11): 3104-3110.
	Ji X , Liu B , Li X P , et al . Catalytic pyrolysis of lipid-extracted residue of tribonema minus using metal-modified ZSM-5 catalysts [J]. Acta Energiae Solaris Sinica, 2017, (11): 3104-3110.
18	Park Y K , Yoo M L , Jin S H , et al . Catalytic fast pyrolysis of waste pepper stems over HZSM-5 [J]. Renewable Energy, 2015, 79: 20-27.
19	Lu Q , Guo H Q , Zhou M X , et al . Monocyclic aromatic hydrocarbons production from catalytic cracking of pine wood-derived pyrolytic vapors over Ce-Mo₂N/HZSM-5 catalyst [J]. Science of the Total Environment, 2018, 634: 141-149.
20	Lu Q , Zhou M X , Li W T , et al . Catalytic fast pyrolysis of biomass with noble metal-like catalysts to produce high-grade bio-oil: analytical Py-GC/MS study [J]. Catalysis Today, 2018, 302: 169-179.
21	王霏, 郑云武, 黄元波, 等 . ZSM-5催化生物质三组分和松木热解生物油组分分析[J]. 农业工程学报, 2016, 32(S2): 331-337.
	Wang F , Zheng Y W , Huang Y B , et al . Component analysis of pyrolysis bio-oil from three major components of biomass and Pinus yunnanensis by ZSM-5 catalytic [J]. Transactions of the Chinese Society of Agricultural Engineering, 2016, 32(S2): 331-337.
22	Mihalcik D J , Mullen C A , Boateng A A . Screening acidic zeolites for catalytic fast pyrolysis of biomass and its components [J]. Journal of Analytical and Applied Pyrolysis, 2011, 92(1): 224-232.
23	Iliopoulou E F , Stefanidis S D , Kalogiannisk G , et al . Catalytic upgrading of biomass pyrolysis vapors using transition metal modified ZSM-5 zeolite [J]. Applied Catalysis B: Environmental, 2012, 127: 281-290.
24	Zhang H Y , Zheng J , Xiao R . Catalytic pyrolysis of willow wood with Me/ZSM-5 (Me = Mg, K, Fe, Ga, Ni) to produce aromatics and olefins [J]. BioResources, 2013, 8(4): 5612-5621.
25	Li P , Li D , Yang H , et al . Effects of Fe-, Zr-, and Co-modified zeolites and pretreatments on catalytic upgrading of biomass fast pyrolysis vapors [J]. Energy Fuels, 2016, 30(4): 3004-3013.
26	Sun L Z , Zhang X D , Chen L , et al . Comparison of catalytic fast pyrolysis of biomass to aromatic hydrocarbons over ZSM-5 and Fe/ZSM-5 catalysts [J]. Journal of Analytical and Applied Pyrolysis, 2016, 121: 342-346.
27	孙来芝, 田数娥, 张晓东, 等 . 利用Py-GC/MS研究温度和时间对杨木粉催化热解制芳烃的影响[J]. 可再生能源, 2018, 36(11): 12-16.
	Sun L Z , Tian S E , Zhang X D , et al . Effect of temperature and time on poplar sawdust catalytic pyrolysis into aromatic hydrocarbons by Py-GC/MS [J]. Renewable Energy Resources, 2018, 36(11): 12-16.
28	Lu Q , Yang X C , Dong C Q , et al . Influence of pyrolysis temperature and time on the cellulose fast pyrolysis products: analytical Py-GC/MS study [J]. Journal of Analytical and Applied Pyrolysis, 2011, 92: 430-438.
29	Lu Q , Guo H , Zhou M , et al . Selective preparation of monocyclic aromatic hydrocarbons from catalytic cracking of biomass fast pyrolysis vapors over Mo₂N/HZSM-5 catalyst [J]. Fuel Processing Technology, 2018, 173: 134-142.
30	Hameed S , Sharma A , Pareek V , et al . A review on biomass pyrolysis models: kinetic, network and mechanistic models [J]. Biomass and Bioenergy, 2019, 123: 104-122.
31	Īilknur D , Sevgi S . Fixed-bed pyrolysis of hazelnut (Corylus avellana L) bagasse: influence of pyrolysis parameters on product yields [J]. Energy Sources, 2006, 28(12): 1149-1158.
32	Wang K G , Brown R C . Catalytic pyrolysis of microalgae for production of aromatics and ammonia [J]. Green Chemistry, 2013, 15: 675-681.

[1]	郑佳丽, 李志会, 赵新强, 王延吉. 离子液体催化合成2-氰基呋喃反应动力学研究[J]. 化工学报, 2023, 74(9): 3708-3715.
[2]	陈佳起, 赵万玉, 姚睿充, 侯道林, 董社英. 开心果壳基碳点的合成及其对Q235碳钢的缓蚀行为研究[J]. 化工学报, 2023, 74(8): 3446-3456.
[3]	吴文涛, 褚良永, 张玲洁, 谭伟民, 沈丽明, 暴宁钟. 腰果酚生物基自愈合微胶囊的高效制备工艺研究[J]. 化工学报, 2023, 74(7): 3103-3115.
[4]	董茂林, 陈李栋, 黄六莲, 吴伟兵, 戴红旗, 卞辉洋. 酸性助水溶剂制备木质纳米纤维素及功能应用研究进展[J]. 化工学报, 2023, 74(6): 2281-2295.
[5]	杨峥豪, 何臻, 常玉龙, 靳紫恒, 江霞. 生物质快速热解下行式流化床反应器研究进展[J]. 化工学报, 2023, 74(6): 2249-2263.
[6]	蔺彩虹, 王丽, 吴瑜, 刘鹏, 杨江峰, 李晋平. 沸石中碱金属阳离子对CO₂/N₂O吸附分离性能的影响[J]. 化工学报, 2023, 74(5): 2013-2021.
[7]	葛泽峰, 吴雨青, 曾名迅, 查振婷, 马宇娜, 侯增辉, 张会岩. 灰化学成分对生物质气化特性的影响规律[J]. 化工学报, 2023, 74(5): 2136-2146.
[8]	包嘉靖, 别洪飞, 王子威, 肖睿, 刘冬, 吴石亮. 正庚烷对冲扩散火焰中添加长链醚类对碳烟前体生成特性的影响[J]. 化工学报, 2023, 74(4): 1680-1692.
[9]	刘海芹, 李博文, 凌喆, 刘亮, 俞娟, 范一民, 勇强. 羟基-炔点击化学改性半乳甘露聚糖薄膜的制备及性能研究[J]. 化工学报, 2023, 74(3): 1370-1378.
[10]	祖凌鑫, 胡荣庭, 李鑫, 陈余道, 陈广林. 木质生物质化学组分的碳释放产物特征和反硝化利用程度[J]. 化工学报, 2023, 74(3): 1332-1342.
[11]	郑杰元, 张先伟, 万金涛, 范宏. 丁香酚环氧有机硅树脂的制备及其固化动力学研究[J]. 化工学报, 2023, 74(2): 924-932.
[12]	熊昊, 梁潇予, 张晨曦, 白浩隆, 范晓宇, 魏飞. 重质油直接制化工品：多级逆流下行催化裂解技术[J]. 化工学报, 2023, 74(1): 86-104.
[13]	陈健鑫, 朱瑞杰, 盛楠, 朱春宇, 饶中浩. 纤维素基生物质多孔炭的制备及其超级电容器性能研究[J]. 化工学报, 2022, 73(9): 4194-4206.
[14]	郝泽光, 张乾, 高增林, 张宏文, 彭泽宇, 杨凯, 梁丽彤, 黄伟. 生物质与催化裂化油浆共热解协同作用研究[J]. 化工学报, 2022, 73(9): 4070-4078.
[15]	张东旺, 杨海瑞, 周托, 黄中, 李诗媛, 张缦. 生物质锅炉对流受热面积灰冷态模拟实验研究[J]. 化工学报, 2022, 73(8): 3731-3738.