碳基固体酸催化纤维素热解制备左旋葡聚糖和左旋葡萄糖酮

doi:10.11949/0438-1157.20211393

化工学报 ›› 2022, Vol. 73 ›› Issue (3): 1166-1172.DOI: 10.11949/0438-1157.20211393

• 催化、动力学与反应器 • 上一篇下一篇

碳基固体酸催化纤维素热解制备左旋葡聚糖和左旋葡萄糖酮

徐飞翔^1,²(),蒋丽群^1,³(),郑安庆¹,赵增立¹

^1.中国科学院可再生能源重点实验室，广东省新能源和可再生能源研究开发与应用重点实验室，中国科学院广州能源研究所，广东广州 510640
^2.中国科学院大学，北京 100049
^3.广东省科学院生物与医学工程研究所，广东广州 510316

收稿日期:2021-09-27 修回日期:2021-11-16 出版日期:2022-03-15 发布日期:2022-03-14
通讯作者: 蒋丽群
作者简介:徐飞翔（1997—），男，硕士研究生，xufx@ms.giec.ac.cn
基金资助:
广东省基础与应用基础研究基金项目(2021A1515012063);广东省科学院打造产业技术创新中心行动专项资金(2022GDASZH-2022010110);广东省科学院2020年度建设国内一流研究机构专项资金项目(GDASYL-20200102010);中国科学院青年创新促进会人才项目(2021350)

Carbon-based solid acid catalyzed the pyrolysis of cellulose to produce levoglucosan and levoglucosenone

Feixiang XU^1,²(),Liqun JIANG^1,³(),Anqing ZHENG¹,Zengli ZHAO¹

^1.Chinese Academy of Sciences Key Laboratory of Renewable Energy, Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^2.University of Chinese Academy of Sciences, Beijing 100049, China
^3.Institute of Biological and Medical Engineering, Guangdong Academy of Sciences, Guangzhou 510316, Guangdong, China

Received:2021-09-27 Revised:2021-11-16 Online:2022-03-15 Published:2022-03-14
Contact: Liqun JIANG

摘要/Abstract

摘要：

将纤维素快速热解转化为高价值的左旋葡聚糖和左旋葡萄糖酮是国内外研究热点之一。通过制备及表征碳基固体酸，并优化纤维素催化热解的实验条件，在350℃下，Fe₃O₄/C₇₀₀-H₃PO₄与纤维素以1∶3的比例混合，可以显著提高热解过程中左旋葡聚糖[40.7%（质量）]和左旋葡萄糖酮[13.5%（质量）]的产率，分别比纯纤维素热解提高了2倍和22倍。该研究对纤维素的定向高值化转化具有指导意义。

关键词: 催化剂, 固体酸, 左旋葡聚糖, 左旋葡萄糖酮, 热解, 生物质, 催化剂, 固体酸, 左旋葡聚糖, 左旋葡萄糖酮

Abstract:

The fast pyrolysis of cellulose into high-value levoglucosan and levoglucosenone is one of the research hotspots at home and abroad. In this paper, carbon-based solid acids catalysts were prepared and characterized, and the experimental conditions of cellulose catalytic pyrolysis were optimized. At 350℃, Fe₃O₄/C₇₀₀-H₃PO₄ mixed with cellulose at a ratio of 1∶3 could significantly increase the yield of levoglucosan [40.7%(mass)] and levoglucosenone [(13.5%(mass)], which were 2 times and 22 times higher than that of non-catalytic cellulose pyrolysis, respectively. This study was a guide for the directional value-added utilization of cellulose.

Key words: biomass, catalyst, levoglucosan, levoglucosenone, pyrolysis, biomass, catalyst, solid acid, levoglucosan, levoglucosenone

中图分类号:

TQ 317

徐飞翔, 蒋丽群, 郑安庆, 赵增立. 碳基固体酸催化纤维素热解制备左旋葡聚糖和左旋葡萄糖酮[J]. 化工学报, 2022, 73(3): 1166-1172.

Feixiang XU, Liqun JIANG, Anqing ZHENG, Zengli ZHAO. Carbon-based solid acid catalyzed the pyrolysis of cellulose to produce levoglucosan and levoglucosenone[J]. CIESC Journal, 2022, 73(3): 1166-1172.

图/表 9

图1 催化剂的SEM图

Fig.1 SEM images of catalysts

图2 催化剂的XRD分析

Fig.2 XRD analysis of catalysts

表1 不同催化剂的NH3-TPD分析

Table 1 NH3-TPD analysis of different catalysts

样品	酸度/(mmol/g)
Fe₃O₄/C₅₀₀-H₃PO₄	3.2
Fe₃O₄/C₆₀₀-H₃PO₄	2.7
Fe₃O₄/C₇₀₀-H₃PO₄	5.5
Fe₃O₄/C₈₀₀-H₃PO₄	4.5

图3 不同催化剂与纤维素混合的热重分析

Fig.3 TG analysis of cellulose mixed with different catalysts

表2 不同催化剂与纤维素混合的热重特征温度

Table 2 TG characteristic temperature of cellulose mixed with different catalysts

样品	热解初始温度/℃	热解结束温度/℃	最大失重速率对应温度/℃	最大失重速率^①/(%/℃)
纤维素	309	410	346	-2.7
Fe₃O₄/C₅₀₀-H₃PO₄+纤维素	257	546	300	-9.7
Fe₃O₄/C₆₀₀-H₃PO₄+纤维素	273	520	305	-10.6
Fe₃O₄/C₇₀₀-H₃PO₄+纤维素	296	507	329	-14.0
Fe₃O₄/C₈₀₀-H₃PO₄+纤维素	258	513	294	-9.0

图4 不同催化剂对纤维素热解产物的影响

Fig.4 Effects of different catalysts on cellulose pyrolysis products

图5不同热解温度对纤维素热解产物的影响

Fig.5 Effects of different pyrolysis temperatures on cellulose pyrolysis products

图6 不同催化剂/纤维素比例对热解产物的影响

Fig.6 Effects of different catalyst / cellulose ratio on pyrolysis products

图7 纤维素催化热解产物分布

Fig.7 Cellulose catalytic pyrolysis products distribution

参考文献 31

1	Akhtar J, Saidina Amin N. A review on operating parameters for optimum liquid oil yield in biomass pyrolysis[J]. Renewable and Sustainable Energy Reviews, 2012, 16(7): 5101-5109.
2	Wang G Y, Dai Y J, Yang H P, et al. A review of recent advances in biomass pyrolysis[J]. Energy & Fuels, 2020, 34(12): 15557-15578.
3	Rahman M M, Liu R H, Cai J M. Catalytic fast pyrolysis of biomass over zeolites for high quality bio-oil — a review[J]. Fuel Processing Technology, 2018, 180: 32-46.
4	Zhu X Q, Tong S, Li X, et al. Conversion of biomass into high-quality bio-oils by degradative solvent extraction combined with subsequent pyrolysis[J]. Energy & Fuels, 2017, 31(4): 3987-3994.
5	Zhang C, Zhang Z C. Essential quality attributes of tangible bio-oils from catalytic pyrolysis of lignocellulosic biomass[J]. The Chemical Record, 2019, 19(9): 2044-2057.
6	Nallar M, Wong H W. Enhanced levoglucosan yields from the copyrolysis of cellulose and high-density polyethylene[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(10): 9480-9488.
7	Wu K, Wu H, Zhang H Y, et al. Enhancing levoglucosan production from waste biomass pyrolysis by Fenton pretreatment[J]. Waste Management, 2020, 108: 70-77.
8	Alcazar-Ruiz A, Dorado F, Sanchez-Silva L. Fast pyrolysis of agroindustrial wastes blends: hydrocarbon production enhancement[J]. Journal of Analytical and Applied Pyrolysis, 2021, 157: 105242.
9	Zhang H Y, Meng X, Liu C, et al. Selective low-temperature pyrolysis of microcrystalline cellulose to produce levoglucosan and levoglucosenone in a fixed bed reactor[J]. Fuel Processing Technology, 2017, 167: 484-490.
10	Lusi A, Radhakrishnan H, Hu H Y, et al. Plasma electrolysis of cellulose in polar aprotic solvents for production of levoglucosenone[J]. Green Chemistry, 2020, 22(22): 7871-7883.
11	Liu J J, Hou Q D, Ju M T, et al. Biomass pyrolysis technology by catalytic fast pyrolysis, catalytic co-pyrolysis and microwave-assisted pyrolysis: a review[J]. Catalysts, 2020, 10(7): 742.
12	Zhou Y C, Chen Z Z, Gong H J, et al. Study on the feasibility of using monolithic catalyst in the in situ catalytic biomass pyrolysis for syngas production[J]. Waste Management, 2021, 120: 10-15.
13	Ren S J, Lei H W, Wang L, et al. Hydrocarbon and hydrogen-rich syngas production by biomass catalytic pyrolysis and bio-oil upgrading over biochar catalysts[J]. RSC Advances, 2014, 4(21): 10731-10737.
14	Wang K G, Kim K H, Brown R C. Catalytic pyrolysis of individual components of lignocellulosic biomass[J]. Green Chemistry, 2014, 16(2): 727-735.
15	Kawamoto H, Saito S, Hatanaka W, et al. Catalytic pyrolysis of cellulose in sulfolane with some acidic catalysts[J]. Journal of Wood Science, 2007, 53(2): 127-133.
16	Kudo S, Zhou Z W, Norinaga K, et al. Efficient levoglucosenone production by catalytic pyrolysis of cellulose mixed with ionic liquid[J]. Green Chemistry, 2011, 13(11): 3306-3311.
17	张智博, 董长青, 叶小宁, 等. 利用固体磷酸催化热解纤维素制备左旋葡萄糖酮[J]. 化工学报, 2014, 65(3): 912-920.
	Zhang Z B, Dong C Q, Ye X N, et al. Preparation of levoglucosenone by catalytic pyrolysis of cellulose over solid phosphoric acid[J]. CIESC Journal, 2014, 65(3): 912-920.
18	Kudo S, Goto N, Sperry J, et al. Production of levoglucosenone and dihydrolevoglucosenone by catalytic reforming of volatiles from cellulose pyrolysis using supported ionic liquid phase[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(1): 1132-1140.
19	Nieva M L, Volpe M A, Moyano E L. Catalytic and catalytic free process for cellulose conversion: fast pyrolysis and microwave induced pyrolysis studies[J]. Cellulose, 2015, 22(1): 215-228.
20	Sui X W, Wang Z, Liao B, et al. Preparation of levoglucosenone through sulfuric acid promoted pyrolysis of bagasse at low temperature[J]. Bioresource Technology, 2012, 103(1): 466-469.
21	Shaik S M, Sharratt P N, Tan R B H. Influence of selected mineral acids and alkalis on cellulose pyrolysis pathways and anhydrosaccharide formation[J]. Journal of Analytical and Applied Pyrolysis, 2013, 104: 234-242.
22	Dobele G, Rossinskaja G, Telysheva G, et al. Cellulose dehydration and depolymerization reactions during pyrolysis in the presence of phosphoric acid[J]. Journal of Analytical and Applied Pyrolysis, 1999, 49(1/2): 307-317.
23	Halpern Y, Riffer R, Broido A. Levoglucosenone (1, 6-anhydro-3, 4-dideoxy-Δ³-β-D-pyranosen-2-one). Major product of the acid-catalyzed pyrolysis of cellulose and related carbohydrates[J]. The Journal of Organic Chemistry, 1973, 38(2): 204-209.
24	Ohnishi A, Kato K, Takagi E. Curie-point pyrolysis of cellulose[J]. Polymer Journal, 1975, 7(4): 431-437.
25	陆强, 朱锡锋. 利用固体超强酸催化热解纤维素制备左旋葡萄糖酮[J]. 燃料化学学报, 2011, 39(6): 425-431.
	Lu Q, Zhu X F. Production of levoglucosenone from pyrolysis of cellulose catalyzed by solid superacids[J]. Journal of Fuel Chemistry and Technology, 2011, 39(6): 425-431.
26	Mullen C A, Boateng A A. Catalytic pyrolysis-GC/MS of lignin from several sources[J]. Fuel Processing Technology, 2010, 91(11): 1446-1458.
27	Lu Q, Hu B, Zhang Z X, et al. Mechanism of cellulose fast pyrolysis: the role of characteristic chain ends and dehydrated units[J]. Combustion and Flame, 2018, 198: 267-277.
28	Kawamoto H. Reactions and molecular mechanisms of cellulose pyrolysis[J]. Mokuzai Gakkaishi, 2015, 61(1): 1-24.
29	Easton M W, Nash J J, Kenttämaa H I. Dehydration pathways for glucose and cellobiose during fast pyrolysis[J]. The Journal of Physical Chemistry A, 2018, 122(41): 8071-8085.
30	Shafizadeh F, Furneaux R H, Stevenson T T, et al. Acid-catalyzed pyrolytic synthesis and decomposition of 1,4:3,6-dianhydro-α-D-glucopyranose[J]. Carbohydrate Research, 1978, 61(1): 519-528.
31	王树荣, 郑赟, 骆仲泱, 等. 生物质组分热裂解动力学研究[J]. 浙江大学学报(工学版), 2007, 41(4): 585-588, 602.
	Wang S R, Zheng Y, Luo Z Y, et al. Kinetic study on pyrolysis of biomass components[J]. Journal of Zhejiang University (Engineering Science), 2007, 41(4): 585-588, 602.

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碳基固体酸催化纤维素热解制备左旋葡聚糖和左旋葡萄糖酮

Carbon-based solid acid catalyzed the pyrolysis of cellulose to produce levoglucosan and levoglucosenone

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