NiO-Fe2O3/PG-γ-Al2O3催化剂的制备及其在秸秆热解中的应用

史训旺; 李建芬; 辛馨; 李红霞; 路遥; 刘照; 程群鹏

NiO-Fe₂O₃/PG-γ-Al₂O₃催化剂的制备及其在秸秆热解中的应用

武汉轻工大学化学与环境工程学院, 湖北武汉 430023

基金项目:

公益性行业（农业）科研专项 201503135

湖北省高校优秀科技创新团队项目 T201407

详细信息

中图分类号: TK16
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- 被引次数: 0
出版历程
- 收稿日期: 2017-07-15
- 修回日期: 2017-10-20
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-12-10

Preparation of NiO-Fe₂O₃/PG-γ-Al₂O₃ catalysts and its application in pyrolysis of biomass straw

School of Chemical and Environmental Engineering, Wuhan Polyteclmic University, Wuhan 430023, China

Funds:

the Public Welfare Industry (agriculture) Research special 201503135

the Project of College Outstanding Technological Innovation in Hubei Province T201407

More Information

Corresponding author: LI Jian-fen, E-mail:lijfen@163.com

摘要

摘要: 通过沉积沉淀法与均匀沉淀法制备以坡缕石与伽马氧化铝（Palygorskite-Gamma Alumina，PG-γ-Al₂O₃）为复合载体的负载型NiO-Fe₂O₃/PG-γ-Al₂O₃催化剂，采用了EDX、XRD、SEM、N₂等温吸附-脱附等手段对催化剂进行了表征与分析。同时利用管式炉考察了NiO-Fe₂O₃/PG-γ-Al₂O₃催化剂在作物秸秆热解中的催化性能和再生使用寿命及抗积炭能力，并与两种单载体催化剂（NiO-Fe₂O₃/PG，NiO-Fe₂O₃/γ-Al₂O₃）进行了比较。结果表明，PG-γ-Al₂O₃复合载体比表面积达134.21 m²/g，平均孔径为39.65 nm。NiO-Fe₂O₃/PG-γ-Al₂O₃催化剂活性组分负载均匀，分散较好且催化剂中同时存在镍铁合金与镍铝尖晶石结构。催化剂活性测试显示，NiO-Fe₂O₃/PG-γ-Al₂O₃催化剂用于作物秸秆热解具有极高的催化活性，能够显著提高产品燃气品质、燃气中的CO与H₂含量和燃气热值；相比单载体催化剂其催化活性好，再生效果佳，抗积炭能力较强。
- 生物质 /
- 热解 /
- 催化剂 /
- 再生
Abstract: The supported NiO-Fe₂O₃/Palygorskite and Gamma Alumina(NiO-Fe₂O₃/PG-γ-Al₂O₃) catalysts were prepared by deposition-precipitation and homogeneous-precipitation methods using PG-γ-Al₂O₃ as a carrier, and different approaches including EDX, XRD, SEM and N₂ isothermal adsorption-desorption were used to characterize the synthetic catalysts. Meanwhile, the catalytic pyrolysis of biomass straw was conducted to test the catalytic activity, the regenerative service life and the anti-carbon capacity of NiO-Fe₂O₃/PG-γ-Al₂O₃ catalyst in a tube furnace, and to compare with the catalytic properties of single carrier catalysts. The results indicate that the prepared PG-γ-Al₂O₃ carriers have a high specific surface area of 134.21 m²/g and the average pore size is 39.65 nm. The active components are loaded uniformly and in a good dispersion over NiO-Fe₂O₃/PG-γ-Al₂O₃ catalyst, meanwhile, the Ni-Fe alloy and the nickel-aluminum spinel structure exist simultaneously in the catalyst. The catalytic activity testing shows that the NiO-Fe₂O₃/PG-γ-Al₂O₃ catalysts have a very high catalytic activity in pyrolysis of biomass straw. It could obviously improve the quality of the gas such as the content of H₂ and CO and the calorific value. The catalytic activity, regeneration effect and anti-carbon deposition ability of NiO-Fe₂O₃/PG catalyst are better than that with single carrier catalyst.
- biomass /
- pyrolysis /
- catalyst /
- regeneration

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图 1 生物质热解气化反应流程示意图

Figure 1 Flow chart of the reactor for pyrolysis and gasification of biomass

1: nitrogen; 2: valve; 3: gas pipe; 4: flowmeter; 5: flange; 6: pyrolysis tube; 7: pyrolysis furnace; 8: temperature control panel; 9: pressure valve; 10: scrubbing device; 11: gas bag; 12: gas analyzer; 13: computer

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图 2 三种催化剂和坡缕石的XRD谱图

Figure 2 XRD patterns of three catalysts and palygorskite

(a): PG; (b): NFP; (c): NFA; (d): NFPA
■: SiO₂; ▲: NiFe₂O₄; ●: NiO; ▼: NiAl₂O₄; ◆: MgNiO₂

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图 3 三种催化剂的SEM照片

Figure 3 SEM images of the three catalysts

(a): NFP; (b): NFA; (c): NFPA

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图 4 生物质秸秆气化和催化气化的燃气组成

Figure 4 Gas composition of biomass gasification with and without catalyst

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图 5 NiO-Fe₂O₃/PG-γ-Al₂O₃催化剂的寿命

Figure 5 Lifetime test of NiO-Fe₂O₃/PG-γ-Al₂O₃ catalyst

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表 1 秸秆的元素分析和工业分析

Table 1 Ultimate and proximate analyses of straw sample

Ultimate analysis w/%					Proximate analysis w/%
C	H	O^*	N	S	M	A	V	FC
33.98	4.73	51.97	0.81	0.12	11.2	8.39	77.7	2.71
^*: by difference

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表 2 三种催化剂和PG的EDX元素分析

Table 2 EDX elemental analysis of PG and three catalysts

Catalyst	Main composition and content w/%
Catalyst	NiO	Fe₂O₃	Al₂O₃	SiO₂	MgO	K₂O	TiO₂	CaO	MnO
PG	-	4.23	10.56	63.84	10.47	3.51	1.84	1.53	1.31
NFP	27.71	9.25	6.64	44.95	6.00	2.22	1.26	0.97	0.83
NFA	27.12	8.67	63.61	-	0.07	0.09	-	0.04	-
NFPA	25.20	8.01	36.18	22.82	3.92	1.48	0.73	0.59	0.45

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表 3 三种催化剂载体的比表面积、孔容和孔径分布

Table 3 BET surface area, pore volume, pore size of three catalyst carriers

Sample	BET surface area A/(cm²·g^-1)	Pore volume v/(cm³·g ^-1)	Pore diameter d/nm
PG	103.36	0.119	19.29
γ-Al₂O₃	121.35	0.248	17.12
PA	134.21	0.325	39.65

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表 4 生物质秸气化和催化气化产物产率比较

Table 4 Comparison of product yields from biomass straw pyrolysis with and without catalysts

Catalyst	No catalyst	NP	NFP	NFA	NFPA
Gas yield w/(m³·kg^-1)	0.18	0.29	0.31	0.32	0.35
H₂ production w/(g·kg^-1)	5.21	8.04	9.07	10.16	11.72
Q_LHV/(MJ·m^-3)	6.41	7.07	7.49	8.09	9.01

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表 5 催化剂的C元素含量

Table 5 Carbon content of catalysts

Catalyst	NFP	NFA	NFPA
C content w/%	1.51	0.90	1.01

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