Production of Phenolic Compounds from Bagasse Lignin via Catalytic Pyrolysis of Ca1-xPrxFe       O   3     †

doi:10.7503/cjcu20190439

Abstract

Abstract:

A series of calcium ferrite oxides with different loading of praseodymium(Ca_1-_xPr_xFeO₃, CPF-x) was synthesized by sol-gel method. The calcination mechanism was optimized, its catalytic pyrolysis effect on bagasse lignin(BL) was evaluated, and its regeneration performance was investigated. The results showed that the suitable synthesis and calcination parameters of CPF-x were as follows: x=0.5, the calcination temperature was 800 ℃, and the calcination time was 6 h. The CPF-0.5-800-6 obtained under this condition presented cubic crystal phase, porous structure, and the specific surface area increased by nearly 3 times with the addition of Pr into CaFeO₃. The optimal technological parameters for catalytic pyrolysis of BL by CPF-0.5-800-6 were as follows: m(CPF-0.5-800-6)∶m(BL) was 1∶3, the pyrolysis temperature was 650 ℃, and the liquid phase yield was up to 20.73%. The main phenolic compounds are syringols, phenolics and guaiacols typed compounds. The total selectivity was 63.21%. The selectivity of syringols increased from 20.60% to 29.59% with CPF-0.5-800-6 as catalyst. The selectivity of a certain phenol compound in BL catalytic pyrolysis was improved. CPF-0.5-800-6 still has nice selectivity and structural stability even after 5 catalytic pyrolysis and regeneration cycles.

Key words: Syringols, Phenolic compounds, Bagasse lignin, Sol-gel method, Perovskite, Catalytic pyrolysis, Calcium ferrite oxide with loading of praseodymium

CLC Number:

O643

TrendMD:

HAN Hongjing,GE Qin,CHEN Yanguang,WANG Haiying,ZHAO Hongzhi,WANG Yizhen,ZHANG Yanan,DENG Jitong,SONG Hua,ZHANG Mei. Production of Phenolic Compounds from Bagasse Lignin via Catalytic Pyrolysis of Ca₁_-xPr_xFe $O 3 †$ [J]. Chem. J. Chinese Universities, 2020, 41(2): 331.

Figures/Tables 16

Fig.1 XRD patterns of metal oxides and Ca1-xPrxFeO3 with different Pr loading a. Fe2O3; b. CaO; c. Pr6O11; d. CPF-0; e. CPF-0.1; f. CPF-0.3; g. CPF-0.5; h. CPF-0.7.

Fig.2 SEM images of Ca1-xPrxFeO3 samples x: (A) 0; (B) 0.3; (C) 0.5; (D) 0.7.

Fig.3 XRD patterns of CPF-0.5 samples calcined under different temperatures Temperature/℃: a. 400; b. 600; c. 800; d. 900; e. 1000.

Fig.4 SEM images of CPF-0.5 samples calcined under different temperatures Temperature/℃: (A) 600; (B) 800; (C) 1000.

Fig.5 XRD patterns of CPF-0.5-800 samples at different calcination times Time/h: a. 2; b. 4; c. 6; d. 8; e. 10.

Fig.6 SEM images of CPF-0.5-800 samples at different calcination times Time/h: (A) 2; (B) 6; (C) 10.

Fig.7 N2 Adsorption-desorption curves of CF(a) and CPF-0.5-800-6(b)

Sample	S_BET/(m²·g^-1)	V_p/(cm³·g^-1)	D_p/nm
CF	17.37	0.1155	26.60
CPF-0.5	66.65	0.3800	22.80

Fig.8 FTIR spectra of bagasse lignin (B) Enlarge pattern of the circle in (A).

Fig.9 Yields of gas, liquid and solid products with different ratio of m(CPF-0.5-800-6):m(BL)

Fig.10 Yields of solid, liquid and gas products under different pyrolysis temperatures

No.	t/min	Compound	Type	Content of liquid product(%)
No.	t/min	Compound	Type	BL	BL+CPF-0.5-800-6
1	7.467		Phenolic	2.73	3.82
2	8.687		Phenolic	——	1.32
3	9.017		Phenolic	——	1.86
4	9.229		Phenolic	9.41	10.18
5	10.098		Ether	——	2.30
6	10.434		Phenolic	——	1.27
7	10.62		Guaiacol	——	1.04
8	10.831		Guaiacol	2.37	3.61
9	11.195		Ether	7.37	4.89
10	11.476		Ether	——	1.43
11	12.084		Ether	3.02	2.39
12	12.574		Ketone	3.22	11.47
No.	t/min	Compound	Type	Content of liquid product(%)
No.	t/min	Compound	Type	BL	BL+CPF-0.5-800-6
13	13.069		Syringol	14.79	22.63
14	13.733		Guaiacol	2.45	2.18
15	13.742		Ether	2.39	——
16	14.317		Phenolic	5.06	3.82
17	14.374		Guaiacol	——	2.06
18	15.393		Ketone	4.66	——
19	15.78		Ketone	2.34	1.74
20	16.228		Syringol	——	1.29
21	16.307		Ester	——	1.03
22	16.901		Guaiacol	——	2.46
23	17.344		Syringol	——	1.73
24	17.717		Syringol	3.57	1.38
25	18.118		Syringol	2.24	2.56
26	20.046		Ester	——	1.37

Compound	BL	BL+CPF-015-800-6
Phenolics	17.20	22.27
Guaiacols	4.82	11.35
Syringols	20.60	29.59
Ketones	10.22	13.21
Ethers	12.78	11.01
Others	34.38	12.57

Fig.11 Selectivities of various components in liquid products under different pyrolysis conditions a. Phenolics; b. guaiacols; c. syringols; d. ketones; e. ethers; f. others.

Fig.12 Liquid yields of catalytic pyrolysis of BL by CPF-0.5-800-6 after 5 redox recycles(A) and selectivities of various components in liquid products at 1st and 5th pyrolysis reaction(B) a. Phenolics; b. guaiacols; c. syringols; d. ketones; e. ethers; f. others.

Fig.13 XRD patterns(A) and SEM images(B, C) of fresh(a, B) and regenerated(b, C) CPF-0.5-800-6

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Production of Phenolic Compounds from Bagasse Lignin via Catalytic Pyrolysis of Ca₁_-xPr_xFe $O 3 †$

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