CaZr1-xFexO3催化热解甘蔗渣木质素制备酚类化合物

doi:10.7503/cjcu20160515

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (2): 252.doi: 10.7503/cjcu20160515

CaZr_1-_xFe_xO₃催化热解甘蔗渣木质素制备酚类化合物

陈彦广^1,²(), 王新惠^1,², 韩洪晶^1,², 王海英^1,², 安宏宇^1,², 宋华^1,², 公旭中³(), 张健^1,²

1. 东北石油大学化学化工学院, 2. 石油与天然气化工省重点实验室, 大庆 163318
3. 中国科学院过程工程研究所, 北京 100190

收稿日期:2016-07-18 出版日期:2017-02-10 发布日期:2017-01-16
作者简介:联系人简介: 陈彦广, 男, 博士, 教授, 博士生导师, 主要从事废弃物资源化利用与能源化工方面的研究. E-mail: ygchen79310@126.com; 公旭中, 男, 博士, 副研究员, 主要从事能源催化转化利用方面的研究. E-mail: xzgong@home.ipe.ac.cn
基金资助:
黑龙江省新世纪优秀人才计划(批准号: 1254-NCET-004)和国家自然科学基金(批准号: 51674089)资助

Production of Phenolic Compounds from Bagasse Lignin via Catalytic Pyrolysis of CaZr_1-_xFe_xO₃^†

CHEN Yanguang^1,^2,^*(), WANG Xinhui^1,², HAN Hongjing^1,², WANG Haiying^1,², AN Hongyu^1,², SONG Hua^1,², GONG Xuzhong^3,^*(), ZHANG Jian^1,²

1. College of Chemistry & Chemical Engineering,2. Provincial Key Laboratory of Oil & Gas Chemical Technology, Northeast Petroleum University,Daqing 163318, China
3. Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Received:2016-07-18 Online:2017-02-10 Published:2017-01-16
Contact: CHEN Yanguang,GONG Xuzhong E-mail:ygchen79310@126.com;xzgong@home.ipe.ac.cn
Supported by:
† Supported by the Program for New Century Excellent Talents in University of Heilongjiang Province, China(No.1254-NCET-004) and the National Natural Science Foundation of China(No.51674089)

摘要/Abstract

摘要：

采用固相反应法制备了一系列钙钛矿型混合离子电子导体CaZr_1-_xFe_xO₃(CZFO-x, x=0, 0.2, 0.4, 0.6, 0.8, 1.0). 通过X射线衍射(XRD)、扫描电子显微镜(SEM)及X射线光电子能谱(XPS)对其晶型、形貌和金属赋存价态进行了表征. 采用热重分析仪(TG)测试了其催化苷蔗渣木质素(BL)热解性能, 并采用固定床微型反应器对其催化热解BL制备酚类化合物性能进行了评价, 利用气相色谱/质谱(GC/MS)对BL催化热解的气相和液相产物进行分析. 研究结果表明, CZFO-x呈粒状或层状致密结构, 随着Fe掺杂量的增加, 其特征衍射峰强度增大, 且衍射峰位置向大角度偏移, 晶胞体积及晶粒尺寸减小. 固定床反应结果显示, 在CaZr_0.8Fe_0.2O₃(CZFO-0.2)催化下, BL热解液相产物收率可达23.71%, 其中酚类化合物主要包括苯酚类、愈创木基类、邻苯二酚类和紫丁香基类, 其选择性分别为35.19%, 6.18%, 10.68%和14.21%, 其余产物为苯类和甲氧基芳香化合物. 反应后催化剂经氧化再生后, 仍然具有较高的催化活性和结构稳定性. 对BL催化热解气体产物进行分析发现, CZFO-0.2促进了芳香烃烷基侧链的断裂, 致使气相产物组成中C_mH_n和CH₄含量增加.

关键词: CaZr_1-xFe_xO₃, 甘蔗渣木质素, 催化热解, 酚类化合物

Abstract:

Chemical conversion is an important approach to obtain chemical products from bagasse lignin(BL) which favors in resource and high-value utilization of lignin. A series of perovskite-type mixed ionic and electronic conductors CaZr_1-_xFe_xO₃(CZF-x; x=0, 0.2, 0.4, 0.8, 1.0) were prepared via the solid state reaction method. The crystal form, morphology, metal valence state and thermal stability were characterized by X-ray diffraction(XRD), scanning electron microscope(SEM), X-ray photoelectric spectroscopy(XPS) and thermogravimetric analysis and differential thermal analysis(TG-DTA). Catalytic performance for producing phenolic compounds from bagasse lignin via catalytic pyrolysis was evaluated in a fixed bed micro-reactor. The results show that the CaZr_1-_xFe_xO₃ pellets after calcinations deposit randomly in the form of irregular grains of flake with compact structure. As the doping amount of Fe increases, the characteristic peaks of mixed ionic and electronic conductor shift to large angle, the cell volume of crystal and the grain size decrease. Moreover, the pyrolysis temperature of BL was significantly reduced under the action of CaZr_0.2Fe_0.8O₃(CZFO-0.2). In the test of fixed bed micro-reactor, the yield of liquid product was 23.71%. The phenolic product was mainly consisting with phenols, guaiacyl groups, catechol and syringyl groups; their selectivities were 35.19%, 6.18%, 10.68% and 14.21% respectively. The rest of liquid products were benzenes and methoxy aromatics. The deactivated catalyst was regenerated by oxidation to removing the coke coated on the surface and exhibited the high structural stability and the better catalytic activity. Due to the enhancement of breakage for aromatic alkyl side chain by CZFO-0.2, the contents of CH₄ and C_mH_n in BL pyrolysis gas increased.

Key words: CaZr_1-xFe_xO₃, Bagasse lignin, Catalytic pyrolysis, Phenolic compound

中图分类号:

O643

TrendMD:

陈彦广, 王新惠, 韩洪晶, 王海英, 安宏宇, 宋华, 公旭中, 张健. CaZr_1-_xFe_xO₃催化热解甘蔗渣木质素制备酚类化合物. 高等学校化学学报, 2017, 38(2): 252.

CHEN Yanguang, WANG Xinhui, HAN Hongjing, WANG Haiying, AN Hongyu, SONG Hua, GONG Xuzhong, ZHANG Jian. Production of Phenolic Compounds from Bagasse Lignin via Catalytic Pyrolysis of CaZr_1-_xFe_xO₃^†. Chem. J. Chinese Universities, 2017, 38(2): 252.

图/表 13

Table 1 Ultimate and proximate analyses(%, mass fraction) for BL*

Material	Ultimate analysis(%)					Proximate analysis(%)
Material	C	H	O	N	S	M_ad	A_ad	V_ad	FC_ad
BL	61.55	6.32	30.15	0.79	1.19	7.15	3.63	75.02	14.20

Fig.1 SEM image of BL sample

Fig.2 FTIR spectrum of raw BL

Fig.3 XRD patterns of CZFO-x oxidesx: a. 0; b. 0.2; c. 0.4; d. 0.6; e. 0.8; f. 1.0.(B) Enlarged pattern of Fig.3(A).

Fig.4 SEM images of CZFO-x catalystsx: (A) 0; (B) 0.2; (C) 0.4; (D) 0.6; (E) 0.8; (F) 1.0.

Fig.5 TG(a, b) and DTG(c, d) curves of BL(a, c) and BL under the action of CZFO-0.2(b, d)

Fig.6 Effect of mass ratio of BL to CZF-0.2 on the product yield

Fig.7 Effect of mass ratio of BL to CZF-0.2 on liquid products selectivitya. Benzene type; b. phenol type; c. guaiacyl type; d. catechol type; e. syringyl type; f. methoxy aromatics.

Fig.8 Effect of CZFO-0.2 recycle on the selectivities of liquid productsa. Benzene type; b. phenol type; c. guaiacyl type; d. catechol type; e. syringyl type; f. methoxy aromatics.

Fig.9 XRD patterns of CZFO-0.2 catalyst a. Fresh; b. after reaction; c. regenerated.

Fig.10 Fe2p XPS spectra of fresh CZFO-0.2(A) and CZFO-0.2 after reaction(B)

Fig.11 SEM images(A—C) and corresponding EDS patterns(A'—C') of CZFO-0.2 (A, A') Fresh; (B, B') after reaction; (C, C') regenerated.

Fig.12 Gas composition derived from BL pyrolysis and BL with CZF-0.2 catalytic pyrolysis

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CaZr_1-_xFe_xO₃催化热解甘蔗渣木质素制备酚类化合物

Production of Phenolic Compounds from Bagasse Lignin via Catalytic Pyrolysis of CaZr_1-_xFe_xO₃^†

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