Ca1-xPrxFeO3催化热解甘蔗渣木质素制备酚类化合物

doi:10.7503/cjcu20190439

摘要/Abstract

摘要：

采用溶胶-凝胶法合成了一系列镨掺杂的铁酸钙氧化物(Ca_1-_xPr_xFeO₃, 简称CPF-x), 优化了其焙烧机制, 研究了其对甘蔗渣木质素(BL)的催化热解作用, 考察了其再生性能. 研究结果表明, CPF-x适宜的合成及焙烧参数分别为: x=0.5, 焙烧温度为800 ℃, 焙烧时间为6 h, 在该条件下得到的CPF-0.5-800-6呈立方晶相, 为疏松多孔结构; 掺杂Pr后, 其比表面积提高了近3倍. CPF-0.5-800-6对BL催化热解最佳工艺参数为: m(CPF-0.5-800-6)∶m(BL)=1∶3, 热解温度为650 ℃, 液相收率最大可达20.73%, 其中主要产物为紫丁香酚类、苯酚类及愈创木酚类, 其总选择性为63.21%. 以CPF-0.5-800-6为催化剂, 紫丁香酚类化合物选择性由20.60%增大到29.59%, 实现了提高BL催化热解中某种单酚化合物的选择性. CPF-0.5-800-6经5次催化热解-再生循环反应后, 仍具有良好的反应活性和结构稳定性.

关键词: 紫丁香, 酚类化合物, 甘蔗渣木质素, 溶胶-凝胶法, 钙钛矿, 催化热解, 镨掺杂的铁酸钙氧化物

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

中图分类号:

O643

TrendMD:

韩洪晶,葛芹,陈彦广,王海英,赵宏志,王怡真,张亚男,邓冀童,宋华,张梅. Ca₁_-xPr_xFeO₃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, 2020, 41(2): 331.

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 $O 3 †$ . Chem. J. Chinese Universities, 2020, 41(2): 331.

图/表 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)

Table 1 Parameters of CF and CPF-0.5-800-6 determined by BET

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

Table 2 Contents of aromatic compounds in liquid products by GC/MS analyses

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

Table 3 Content of every type compounds(%)

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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Ca₁_-xPr_xFeO₃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 Ca₁_-xPr_xFe $O 3 †$

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