Production of Phenolic Compounds from Bagasse Lignin via Catalytic Pyrolysis of CaZr1-xFexO3†

doi:10.7503/cjcu20160515

Abstract

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

CLC Number:

O643

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2017, 38(2): 252.

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

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