Ni-ZSM-5分子筛对神东煤热解产物分布的影响

doi:10.16085/j.issn.1000-6613.2019-0087

化工进展 ›› 2019, Vol. 38 ›› Issue (10): 4511-4519.DOI: 10.16085/j.issn.1000-6613.2019-0087

Ni-ZSM-5分子筛对神东煤热解产物分布的影响

兰婷玮^1,²(),高婷^1,²,强路遥^1,²,孙午亮^1,²,王涛^1,²,张壮壮^1,²,常慧^1,²,马晓迅^1,²()

1. 西北大学化工学院，国家碳氢资源清洁利用国际科技合作基地，陕北能源先进化工利用技术教育部工程研究
2. 中心，陕西省洁净煤转化工程技术研究中心，陕北能源化工产业发展协同创新中心，陕西西安 710069

收稿日期:2019-01-14 出版日期:2019-10-05 发布日期:2019-10-05
通讯作者: 马晓迅
作者简介:兰婷玮（1995—），女，硕士研究生，研究方向为煤催化热解。E-mail：ltw_nwu@163.com。
基金资助:
国家自然科学基金重点项目(21536009);陕西省科技计划(2017ZDCXL-GY-10-03)

Effect of Ni-ZSM-5 zeolites on product distribution of Shendong coal pyrolysis

Tingwei LAN^1,²(),Ting GAO^1,²,Luyao QIANG^1,²,Wuliang SUN^1,²,Tao WANG^1,²,Zhuangzhuang ZHANG^1,²,Hui CHANG^1,²,Xiaoxun MA^1,²()

1. School of Chemical Engineering, Northwest University, International Science and Technology Cooperation Base of MOST for Clean Utilization of Hydrocarbon Resources, Chemical Engineering Research Center of the Ministry of Education for Advanced Use Technology of Shanbei Energy, Shaanxi Research Center of Engineering Technology for Clean Coal Conversion, Collaborative Innovation Center for Shanbei Energy and Chemical Industry Development, Xi’an 710069, Shaanxi, China

Received:2019-01-14 Online:2019-10-05 Published:2019-10-05
Contact: Xiaoxun MA

摘要/Abstract

摘要：

利用原位合成法、等体积浸渍法分别向全硅ZSM-5催化剂中引入5%的过渡金属Ni进行改性，并使用X射线衍射仪、扫描电镜、等离子发射光谱仪、全自动化学吸附仪等仪器对合成的催化剂进行表征，利用粉-粒流化床热解实验装置考察了不同金属引入方式对神东煤热解产物分布的影响。结果表明：催化剂对半焦收率的影响很小，对液体收率和气体收率的影响较明显。与非催化热解相比，全硅ZSM-5催化剂使液体产物收率降低了13.2%，但提高了焦油中脂肪烃和单环芳烃的相对含量。与全硅ZSM-5催化剂相比，浸渍改性的催化剂显著提高了气体产物中H₂、CO的生成量，并使焦油中脂肪烃的相对含量增加了31.5%；原位合成改性的催化剂使焦油中酚类物质相对含量减少，萘类物质相对含量增加，芳烃明显富集。

关键词: 流化床, 热解, ZSM-5, 镍, 催化作用, 产物分布

Abstract:

The thesis is to explore the effects of two different metal introduction methods on the catalytic pyrolysis product distribution of Shendong coal by introducing 5% transition metal Ni into the all-silicon ZSM-5 catalyst respectively with in-situ synthesis and equal volume impregnation. The synthesized catalysts are characterized by XRD, SEM, ICP and NH₃-TPD, etc. The results show that catalysts have little effect on the semi coke yield, but observable effect on the liquid yield and the gas yield. In comparison with the non-catalytic process, the all-silicon ZSM-5 catalyst reduces the liquid yield by 13.2%, while it increases the relative content of aliphatic hydrocarbons and monocyclic aromatic hydrocarbons in tar. Compared with the all-silicon ZSM-5 catalyst, the catalyst after equal volume impregnation significantly increases the production of H₂, CO in gas product, meanwhile increases the relative content of aliphatic hydrocarbons by 31.5% in tar; the in-situ synthesis of the metal-incorporated catalyst reduces the relative content of phenolic compounds, increases the relative content of naphthalene compounds and enriches the aromatic hydrocarbons in tar.

Key words: fluidized bed, pyrolysis, ZSM-5, Ni, catalysis, product distribution

中图分类号:

TQ53

兰婷玮,高婷,强路遥,孙午亮,王涛,张壮壮,常慧,马晓迅. Ni-ZSM-5分子筛对神东煤热解产物分布的影响[J]. 化工进展, 2019, 38(10): 4511-4519.

Tingwei LAN,Ting GAO,Luyao QIANG,Wuliang SUN,Tao WANG,Zhuangzhuang ZHANG,Hui CHANG,Xiaoxun MA. Effect of Ni-ZSM-5 zeolites on product distribution of Shendong coal pyrolysis[J]. Chemical Industry and Engineering Progress, 2019, 38(10): 4511-4519.

图/表 19

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催化剂	Ni
催化剂	X₁/mg?g^-1	X₂/mg?g^-1	X₂?X₁^-1/%
5% Ni浸渍Z5	37.4	34.85	93.2
5% Ni原位合成Z5	37.4	34.72	92.8

催化剂	Ni
催化剂	X₁/mg?g^-1	X₂/mg?g^-1	X₂?X₁^-1/%
5% Ni浸渍Z5	37.4	34.85	93.2
5% Ni原位合成Z5	37.4	34.72	92.8

样品	a/nm	b/nm	c/nm	晶胞体积/nm³	相对结晶度/%
全硅ZSM-5原粉	2.0012	2.0172	1.3368	5.3964	100.00
5% Ni浸渍Z5	2.0011	2.0167	1.3369	5.3952	99.10
5% Ni原位合成Z5	2.0046	2.0185	1.3372	5.4107	94.15

样品	a/nm	b/nm	c/nm	晶胞体积/nm³	相对结晶度/%
全硅ZSM-5原粉	2.0012	2.0172	1.3368	5.3964	100.00
5% Ni浸渍Z5	2.0011	2.0167	1.3369	5.3952	99.10
5% Ni原位合成Z5	2.0046	2.0185	1.3372	5.4107	94.15

样品	比表面积/m²·g^-1			孔容/cm³·g^-1
样品	总孔	微孔	介孔	总孔	微孔	介孔
全硅ZSM-5原粉	408.2	396.3	11.9	0.21	0.19	0.02
5% Ni浸渍Z5	403.1	383.6	19.5	0.21	0.18	0.03
5% Ni原位合成Z5	408.6	385.2	23.4	0.23	0.18	0.05

Ni-ZSM-5分子筛对神东煤热解产物分布的影响

Effect of Ni-ZSM-5 zeolites on product distribution of Shendong coal pyrolysis

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床料	半焦/%	液体/%	气体/%	积炭/%
SiO₂	68.60	11.03	20.37	—
全硅ZSM-5原粉	68.82	9.57	20.40	1.21
5% Ni浸渍Z5	68.40	7.87	22.12	1.61
5% Ni原位合成Z5	68.43	9.47	20.93	1.17

床料	各组分含量/mmol·g^-1
床料	H₂	CO	CH₄	CO₂	C₂，C₃	总和
SiO₂	0.48	1.26	1.14	0.55	0.39	3.82
全硅ZSM-5原粉	0.24	1.16	1.18	0.79	0.43	3.8
5% Ni浸渍 Z5	4.57	1.72	0.85	0.85	0.22	8.21
5% Ni原位合成Z5	1.14	1.34	1.24	0.83	0.46	5.01

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