Fe/CaO催化剂对脱灰徐州烟煤热解特性的影响

doi:10.16085/j.issn.1000-6613.2019-0801

化工进展 ›› 2020, Vol. 39 ›› Issue (2): 561-566.DOI: 10.16085/j.issn.1000-6613.2019-0801

Fe/CaO催化剂对脱灰徐州烟煤热解特性的影响

王东(),马士伟,向文国(),陈时熠

东南大学能源与环境学院，能源热转换及过程测控教育部重点实验室，江苏南京 210096

收稿日期:2019-05-16 出版日期:2020-02-05 发布日期:2020-03-12
通讯作者: 向文国
作者简介:王东（1986—），男，博士研究生，研究方向为煤气化制氢。E-mail: astutive@126.com。
基金资助:
国家自然科学基金(51576042);江苏省自然科学基金(BK20160672)

Pyrolysis characteristics of ash-free Xuzhou bituminous coal withFe/CaO catalyst

Dong WANG(),Shiwei MA,Wenguo XIANG(),Shiyi CHEN

Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, Jiangsu, China

Received:2019-05-16 Online:2020-02-05 Published:2020-03-12
Contact: Wenguo XIANG

摘要/Abstract

摘要：

煤热解是一种重要的煤炭分质利用技术，但热解过程中产生的副产物焦油危害极大，催化改质是高效清洁利用煤焦油的方法之一。本文采用溶胶凝胶法制备Fe/CaO催化剂，在管式炉反应器上对脱灰徐州烟煤进行了催化热解实验，对研究催化裂解煤焦油具有重要的意义。结果表明：Fe/CaO催化剂可以明显促进热解气的产生，热解气中CO₂、CO和CH₄的产量均不断增加。Fe/CaO催化剂促进了液体产物的催化裂解，导致液体产率明显下降。Fe/CaO催化剂促进焦油中的稠环芳烃向脂肪烃和轻质芳烃转化，此外，Fe/CaO催化剂还对萘类化合物的产生有促进作用。Fe/CaO催化剂催化后焦油中两环化合物的含量增多，三环及以上的化合物含量减少，焦油分子量呈减少的趋势。

关键词: 煤热解, 催化改质, Fe/CaO催化剂

Abstract:

Pyrolysis is an important utilization technology for coal, but the by-product tar is extremely harmful, and catalytic upgrading is one of the efficient and clean utilization methods of coal tar. In this paper, the catalytic pyrolysis experiments of ash-free Xuzhou bituminous coal were carried out in a tube furnace reactor on Fe/CaO catalyst prepared by sol-gel method. The results showed that Fe/CaO catalyst could promote the production of pyrolysis gas significantly, and the yields of CO₂, CO and CH₄ increased gradually. Fe/CaO catalyst promoted the catalytic cracking of liquid product, resulting in a significant decrease in liquid yield. Fe/CaO catalyst promoted the conversion of polycyclic aromatic hydrocarbons to aliphatic hydrocarbons and light aromatics. In addition, the production of naphthalene compounds was also promoted by Fe/CaO catalyst. The contents of bicyclic compounds in tar increased while that of the tricyclic and polycyclic compounds decreased, the molecular weight of the tar presented a declining tendency.

Key words: coal pyrolysis, catalytic upgrading, Fe/CaO catalyst

中图分类号:

TQ530.2

王东,马士伟,向文国,陈时熠. Fe/CaO催化剂对脱灰徐州烟煤热解特性的影响[J]. 化工进展, 2020, 39(2): 561-566.

Dong WANG,Shiwei MA,Wenguo XIANG,Shiyi CHEN. Pyrolysis characteristics of ash-free Xuzhou bituminous coal withFe/CaO catalyst[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 561-566.

图/表 9

表1 酸洗前后徐州烟煤的工业和元素分析

煤种	工业分析（质量分数，ad）/%				元素分析（质量分数，daf）/%
煤种	M	A	V	FC	C	H	O	N	S
徐州烟煤(XZ)	2.29	17.00	30.68	50.03	75.43	4.87	17.79	1.34	0.57
脱灰徐州煤（DXZ）	5.00	2.00	29.80	63.20	81.67	4.38	11.44	1.76	0.75

图1 管式炉热解流程示意图

图2 Fe/CaO催化剂XRD谱图

图3 不同Ca/Fe摩尔比催化剂的H2-TPR谱图

表2 不同Ca/Fe摩尔比催化剂的H2-TPR还原峰特性参数

催化剂	主还原峰位置/℃	氢气消耗量 $C H 2$ /mmol·g^-1
Ca10Fe0.5	811	7.58
Ca10Fe1.2	803	18.20
Ca10Fe2	796	30.41

表2 不同Ca/Fe摩尔比催化剂的H2-TPR还原峰特性参数

催化剂	主还原峰位置/℃	氢气消耗量 $C H 2$ /mmol·g^-1
Ca10Fe0.5	811	7.58
Ca10Fe1.2	803	18.20
Ca10Fe2	796	30.41

图4 脱灰徐州烟煤热解气体产量

图5 气液固三相产物的收率分布

图6 催化前后焦油中化合物组分含量比较

表3 PAHs环数相对含量分布

环数	脱灰煤/%	CaO/%	Ca10Fe0.5/%	Ca10Fe1.2/%	Ca10Fe2/%
两环	18	52	34	42	38
三环	36	13	43	15	23
四环	35	28	18	37	33
五环及以上	11	6	4	5	6

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Fe/CaO催化剂对脱灰徐州烟煤热解特性的影响

Pyrolysis characteristics of ash-free Xuzhou bituminous coal withFe/CaO catalyst

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