木质素炭与ZSM-5联合催化热解木质素制备芳烃实验研究

赵勃; 吴凯; 仲惟鹏; 魏刚; 胡宗华; 郑文广; 阮慧锋; 严新明; 马颖; 王博; 江天霖; 张会岩

doi:10.1016/S1872-5813(21)60015-4

木质素炭与ZSM-5联合催化热解木质素制备芳烃实验研究

doi: 10.1016/S1872-5813(21)60015-4

赵勃^1,,
吴凯¹,
仲惟鹏²,
魏刚²,
胡宗华²,
郑文广^{3, 4},
阮慧锋^{3, 4},
严新明²,
马颖²,
王博²,
江天霖²,
张会岩^1, ,

1.
东南大学能源与环境学院能源热转换及过程测控教育部重点实验室，江苏南京 210096
2.
华电广西公司，广西南宁 530029
3.
华电电力科学研究院有限公司，浙江杭州 310030
4.
浙江省蓄能与建筑节能技术重点实验室，浙江杭州 310030

基金项目: 国家重点研发项目（2019YFD1100602），国家优秀青年科学基金（51822604）和江苏省杰出青年基金（BK20180014）资助

详细信息

通讯作者:
Tel: 025-83790667，E-mail: hyzhang@seu.edu.cn

中图分类号: TK6
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出版历程
- 收稿日期: 2020-10-19
- 修回日期: 2020-11-19
- 网络出版日期: 2021-03-19
- 刊出日期: 2021-03-19

Experimental study on catalytic pyrolysis of lignin under char and ZSM-5 for preparation of aromatics

1.
Key Laboratory of Energy Thermal Conversion and Control Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, China
2.
China Huadian Guangxi Company, Nanning 530029, China
3.
Huadian Electric Power Research Institute Co.Ltd, Hangzhou 310030, China
4.
Key Laboratory of Energy Storage and Building Energy-saving Technology of Zhejiang Province, Hangzhou 310030, China

Funds: The project was supported by the National Key Research and Development Program of China (2019YFD1100602), the National Nature Science Fund for Excellent Young Scholar (China) (51822604) and the Nature Science Fund of Jiangsu Province for Distinguished Young Scholar (China) (BK20180014)

摘要

摘要: 为了提高木质素催化热解所得芳烃的产率，本研究以碱木质素为原料，在碱木质素炭和ZSM-5的二元催化体系下进行快速热解实验，选取催化剂比例、热解温度、热解时间等为实验变量，探究碱木质素热解产物中芳烃的变化规律以及碱木质素炭和ZSM-5协同催化作用机理。结果表明，碱木质素催化热解所得芳烃的产量从17 mg/g（未加炭）提高到33 mg/g（炭添加量为1 g），产率增加了近一倍。通过不同工况研究发现，碱木质素快速热解制备芳烃的最佳条件是：碱木质素∶碱木质素炭∶ZSM-5 = 1∶1∶1, 热解温度为500 ℃，热解时间为10 min。机理分析表明，热解过程中碱木质素炭主要起断键作用，而ZSM-5起择形芳构化作用，两者协同作用得到更高的芳烃产率。
- 碱木质素 /
- 碱木质素炭 /
- 二元催化体系 /
- 芳烃 /
- 协同作用
Abstract: In order to improve yield of aromatics from catalytic pyrolysis of lignin, alkali lignin was used for rapid pyrolysis experiments under a binary catalysis system of alkali lignin char and ZSM-5. Influence of catalyst ratio and pyrolysis temperature as well as pyrolysis time on aromatics quantity and mechanism of synergistic catalysis of alkali lignin char and ZSM-5 were investigated. The results show that quantity of aromatics has increased from 17 mg/g (without char) to 33 mg/g (with char addition of 1 g), which is about doubled. The optimal conditions for preparation of aromatics are under alkali lignin∶alkali lignin char∶ZSM-5=1∶1∶1 at 500℃ for 10 min. Meanwhile, the mechanism analysis shows that alkali lignin char mainly plays a role in bond breaking during pyrolysis, while ZSM-5 can act as selective aromatization to obtain higher aromatics yield, whose synergistic effects result in higher aromatic yield.
- alkali lignin /
- alkali lignin char /
- binary catalytic system /
- aromatics /
- synergy

HTML全文

FIG. 554. FIG. 554.

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图 1 木质素快速热解实验装置示意图

Figure 1 Schematic diagram of experimental device for fast pyrolysis of lignin

1: nitrogen; 2: air; 3: mass flow controller; 4: furnace; 5: quartz hanging basket; 6: stainless steel tube; 7: thermocouple; 8: temperature controller; 9: ice-bath condenser; 10: drying tube; 11: gas bag

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图 2 不同木质素炭添加量下热解产物分布

Figure 2 Distribution of pyrolysis products under different lignin char additions

(a): yield distribution of solid-liquid-gas three-phase products; (b): yield distribution of aromatics; (c): yield distribution of gas

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图 3 不同ZSM-5添加量下热解产物分布

Figure 3 Distribution of pyrolysis products under different ZSM-5 additions

(a): yield distribution of solid-liquid-gas three-phase products; (b): yield distribution of aromatics; (c): yield distribution of gas

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图 4 不同热解温度下热解产物分布

Figure 4 Distribution of pyrolysis products at different temperatures

(a): yield distribution of solid-liquid-gas three-phase products; (b): yield distribution of aromatics; (c): yield distribution of gas

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图 5 不同热解时间下热解产物分布

Figure 5 Distribution of pyrolysis products under different pyrolysis time

(a): yield distribution of solid-liquid-gas three-phase products; (b): yield distribution of aromatics; (c): yield distribution of gas

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图 6 碱木质素炭与ZSM-5协同催化推测机理

Figure 6 Possible Routes for preparation of aromatics by catalytic pyrolysis of alkali lignin

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表 1 生物油主要成分的GM-MS分析

Table 1 GM-MS analysis of major compositions of bio-oil

RT.(min)	Compound	Peak area of compounds/ (× 10⁷)
RT.(min)	Compound	1∶0∶0	1∶1∶0	1∶1∶1
acid
6.742	acetic acid	0.70	0.78	0.85
phenol
14.019	phenol	2.91	2.67	2.42
methoxy phenol
15.099	phenol,2-methoxy-	3.93	2.51	1.13
17.315	phenol,2-methoxy-4-methyl-	2.77	1.41	0.90
19.192	phenol,4-ethyl-2-methoxy-	2.67	1.78	1.23
20.388	phenol,2-methoxy-4-vinyl	1.96	1.56	0.76
21.498	phenol,2,6-dimethoxy-	2.03	0.98	0.39
21.782	3-methoxy-5-methylphenol	0.41	0.52	−
23.658	phenol,4-methoxy- 3-(methoxymethyl)-	1.83	0.84	0.76
Total		15.60	9.60	5.17
alkyl phenol
15.026	phenol,2-methyl-	−	0.91	0.63
15.775	phenol,4-methyl-	2.01	1.95	1.61
16.834	phenol,2,4-dimethyl-	0.72	1.16	1.23
17.616	phenol,4-ethyl-	3.17	3.71	−
18.701	phenol,3-ethyl-5-methyl-	0.85	1.28	0.93
20.623	2-Allylphenol	−	0.56	−
total		6.75	9.57	4.4
aromatics
8.094	toluene	−	−	1.35
9.996	p-xylene	−	−	1.86
16.545	naphthalene	−	−	5.20
19.037	naphthalene,1-methyl-	−	−	3.91
total		−	−	12.32

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参考文献(28)

[1]	赵宏志. 锰基钙钛矿型氧化物制备及其催化热解甘蔗渣木质素性能研究[D]. 大庆: 东北石油大学, 2019. ZHAO Hong-zhi. Preparation of manganese based perovskite oxide and its catalytic pyrolysis Performance of Bagasse Lignin[D]. Daqing: Northeast Petroleum University, 2019.
[2]	JOFFRES B, LORENTZ C, VIDALIE M, LAURENTI D, QUOINEAUD A A, CHARON N, DAUDIN A, QUIGNARD A, GEANTET C. Catalytic hydroconversion of a wheat straw soda lignin: Characterization of the products and the lignin residue[J]. Appl Catal B: Environ,2014,145:167−176.
[3]	黄煜乾, 吴宇婷, 郑安庆, 赵增立, 李海滨. 基于Py-GC-MS的木质素与褐煤共热解特性研究[J]. 新能源进展,2017,5(5):333−340. doi: 10.3969/j.issn.2095-560X.2017.05.002 HUANG Yi-qian, WU Yu-ting, ZHENG An-qing, ZHAO Zeng-li, LI Hai-bin. Co-pyrolysis characteristics of lignin and lignite: Analytical Py-GC-MS study[J]. Adv New Renewable Energy,2017,5(5):333−340. doi: 10.3969/j.issn.2095-560X.2017.05.002
[4]	王霏, 郑云武, 郑志锋. 云南松热解及其热解产物的研究[J]. 生物质化学工程,2015,49(4):14−18. doi: 10.3969/j.issn.1673-5854.2015.04.003 WANG Fei, ZHENG Yun-wu, ZHENG Zhi-feng. Yields and compositions of products by pyrolysis of Yunnan pine[J]. Biomass Chem Eng,2015,49(4):14−18. doi: 10.3969/j.issn.1673-5854.2015.04.003
[5]	王则祥, 李航, 谢文銮, 胡斌, 李凯, 陆强. 木质素基本结构、热解机理及特性研究进展[J]. 新能源进展,2020,8(1):6−14. doi: 10.3969/j.issn.2095-560X.2020.01.002 WANG Ze-xiang, LI Hang, XIE Wen-luan, HU Bin, LI Kai, LU Qiang. Progress in basic structure, pyrolysis mechanism and characteristics of lignin[J]. Adv New Renewable Energy,2020,8(1):6−14. doi: 10.3969/j.issn.2095-560X.2020.01.002
[6]	李金鑫. Fe基水滑石固体碱制备过程调控及其催化解聚木质素磺酸钙性能研究[D]. 大庆: 东北石油大学, 2019. LI Jin-xin. Regulation on preparation process of Iron based hydrotalcites solid alkali oxides and its catalytic performance for the depolymerization of calcium lignosulfonate[D]. Daqing: Northeast Petroleum University, 2019.
[7]	MA Z Q, TROUSSARD E, BOKHOVEN J A V. Controlling the selectivity to chemicals from lignin via catalytic fast pyrolysis[J]. Appl Catal A: Gen,2012,423:130−136.
[8]	蒋丽群, 郑安庆, 王小波, 赵增立, 李海滨. 生物质定向快速热解制备左旋葡聚糖和芳烃的研究进展[J]. 新能源进展,2018,6(5):402−409. doi: 10.3969/j.issn.2095-560X.2018.05.010 JIANG Li-qun, ZHENG An-qing, WANG Xiao-bo, ZHAO Zeng-li, LI Ha-bin. Progress of biomass fast pyrolysis to produce levoglucosan and aromatics[J]. Adv New Renewable Energy,2018,6(5):402−409. doi: 10.3969/j.issn.2095-560X.2018.05.010
[9]	舒日洋, 徐莹, 张琦, 马隆龙, 王铁军. 木质素催化解聚的研究进展[J]. 化工学报,2016,67(11):4523−4532. SHU Ri-yang, XU Ying, ZHANG Qi, MA Long-long, WANG Tie-jun. Progress in catalytic depolymerization of lignin[J]. J Chem Ind Eng,2016,67(11):4523−4532.
[10]	郑云武. 木质生物质催化热解重整制备芳烃化合物的研究[D]. 哈尔滨: 东北林业大学, 2017. ZHENG Yun-wu. Study on aromatics production from catalytic pyrolysis upgraded of ligncellulose[D]. Haerbin: Northeast Foresttry University, 2017.
[11]	ZHANG M, RESENDE F L P, MOUTSOGLOU A. Catalytic fast pyrolysis of aspen lignin via Py-GC/MS[J]. Fuel,2014,116:358−369.
[12]	杨海平, 陈汉平, 杜胜磊, 陈应泉, 王贤华, 张世红. 碱金属盐对生物质三组分热解的影响[J]. 中国电机工程学报,2009,29(17):70−75. doi: 10.3321/j.issn:0258-8013.2009.17.012 YANG Hai-ping, CHEN Han-ping, DU Sheng-lei, CHEN Ying-quan, WANG Xian-hua, ZHANG Shi-hong. Influence of alkali salts on the pyrolysis of biomass three components[J]. Proc CSEE,2009,29(17):70−75. doi: 10.3321/j.issn:0258-8013.2009.17.012
[13]	刘心明. Ca/Fe强化生物质炭催化重整玉米秸秆挥发分的试验研究[D]. 包头: 内蒙古科技大学, 2019. LIU Xin-ming. Expeimental Study on pyrolysis of volatiles from corn straw by Ca/Fe enhanced biomass carbon catalytic reforming[D]. Baotou: Inner Mongolia University Science and Technology, 2019.
[14]	KUMAR G R, DUBEY M, KHAREL P, GU Z R, FAN Q H. Biochar activated by oxygen plasma for supercapacitors[J]. J Power Sources,2015,274(C):1300−1305.
[15]	SUN K, HUANG Q X, CHI Y, YAN J H. Effect of ZnCl₂-activated biochar on catalytic pyrolysis of mixed waste plastics for producing aromatic-enriched oil[J]. Waste Manage,2018,81:128−137.
[16]	NGUYEN H K D, PHAM V V, DO H T. Preparation of Ni/biochar catalyst for hydrotreating of bio-oil from microalgae biomass[J]. Catal Lett,2016,146(11):2381−2391.
[17]	ZHONG C L, WEI X M. A comparative experimental study on the liquefaction of wood[J]. Energy,2004,29(11):1731−1741.
[18]	于树峰, 仲崇立. 农作物废弃物液化的实验研究[J]. 燃料化学学报,2005,33(2):205−210. doi: 10.3969/j.issn.0253-2409.2005.02.016 YU Shu-feng, YU Chong-li. Experimental study on liquefaction of agricultural residue[J]. J Fuel Chem Technol,2005,33(2):205−210. doi: 10.3969/j.issn.0253-2409.2005.02.016
[19]	LIU S Y, XIE Q L, ZHANG B, CHENG Y L, LIUY H, CHEN P, RUAN R. Fast microwave-assisted catalytic co-pyrolysis of corn stover and scum for bio-oil production with CaO and HZSM-5 as the catalyst[J]. Bioresour Technol,2016,204:164−170.
[20]	DICKERSON T, SORIA J. Catalytic Fast Pyrolysis: A Review[J]. Energies,2013,6(1):514−538.
[21]	MULLEN C A, BOATENG A A. Catalytic pyrolysis-GC/MS of lignin from several sources[J]. Fuel Process Technol,2010,91(11):1446−1458.
[22]	LIU Q Y, HU C S, PENG B, LIU C, LI Z W, WU K, ZHANG H Y, XIAO R. High H₂/CO ratio syngas production from chemical looping co-gasification of biomass and polyethylene with CaO/Fe₂O₃ oxygen carrier[J]. Energy Conv Manag,2019,199:111951.
[23]	JACKSON M A, COMPTON D L, BOATENG A A. Screening heterogeneous catalysts for the pyrolysis of lignin[J]. J Anal Appl Pyrolysis,2008,85(1):226−230.
[24]	李润东, 张杨, 李秉硕, 刘合鑫, 开兴平, 烟征, 杨天华. 玉米秸秆催化液化制备生物油实验研究[J]. 燃料化学学报,2016,44(1):69−75. doi: 10.3969/j.issn.0253-2409.2016.01.010 LI Run-dong, ZHANG Yang, LI Bing-shuo, LIU He-xin, KAI Xing-ping, YAN Zheng, YANG Tian-hua. Hydrothe rmal catalytic lique faction of corn stalk for preparation of bio-oil[J]. J Fuel Chem Technol,2016,44(1):69−75. doi: 10.3969/j.issn.0253-2409.2016.01.010
[25]	TOOR S S, ROSENDAHL L, RUDOLF A. Hydrothermal liquefaction of biomass: A review of subcritical water technologies[J]. Energy,2011,36(5):2328−2342.
[26]	IOANNIDOU O, ZABANIOTOU A, ANTONAKOU E V, PAPAZISI K M, LAPPAS A A, ATHANASSIOU C. Investigating the potential for energy, fuel, materials and chemicals production from corn residues (cobs and stalks) by non-catalytic and catalytic pyrolysis in two reactor configurations[J]. Renewable Sustainable Energy Rev,2008,13(4):750−762.
[27]	JIN S H, LEE H W, RYU C, JEON J K, PARK Y K. Catalytic fast pyrolysis of Geodae-Uksae 1 over zeolites[J]. Energy,2015,81:41−46.
[28]	LEE H W, KIM Y M, JAE J, SUNG B H, JUNG S C, KIM J K, CHAI J S, PARK Y K. Catalytic pyrolysis of lignin using a two-stage fixed bed reactor comprised of in-situ natural zeolite and ex-situ HZSM-5[J]. J Anal Appl Pyrolysis,2016,122:282−288.