不同硅铝比HZSM-5分子筛对煤热解挥发物催化提质的影响

王德亮; 陈兆辉; 余剑; 高士秋

doi:10.1016/S1872-5813(21)60030-0

不同硅铝比HZSM-5分子筛对煤热解挥发物催化提质的影响

doi: 10.1016/S1872-5813(21)60030-0

王德亮^{1, 2,},
陈兆辉¹,
余剑¹,
高士秋^1, ,

1.
中国科学院过程工程研究所多相复杂系统国家重点实验室，北京 100190
2.
中国石化集团经济技术研究院有限公司，北京 100029

基金项目: 国家重点研发计划（2016YFB0600304）和国家自然科学基金（21878310）资助

详细信息

作者简介:
王德亮：wangdl2007@126.com

通讯作者:
E-mail: sqgao@ipe.ac.cn

中图分类号: TQ643.1
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出版历程
- 收稿日期: 2020-12-22
- 修回日期: 2021-01-14
- 网络出版日期: 2021-03-30
- 刊出日期: 2021-05-28

Effect of Si/Al ratio of HZSM-5 zeolites on catalytic upgrading of coal pyrolysis volatiles

WANG De-liang^{1, 2
,},
CHEN Zhao-hui¹,
YU Jian¹,
GAO Shi-qiu^{1
, ,}

1.
State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
2.
Sinopec Economics & Development Research Institute Company Limited, Beijing 100029, China

Funds: The project was supported by the National Key Research and Development Program of China (2016YFB0600304) and the National Natural Science Foundation of China (21878310)

摘要

摘要: 采用不同硅铝比的HZSM-5作为煤热解挥发物提质催化剂，研究了催化剂酸性特征对挥发物提质后的焦油品质、催化剂积炭的影响。结果表明，随着硅铝比的增加，HZSM-5的强酸和弱酸量均降低；硅铝比从23增大到310时，催化剂积炭量从120.1 mg/g-catalyst降到23.9 mg/g-catalyst。并且，HZSM-5中强酸与弱酸位点的比值越高，焦油中轻质组分的含量越高。随硅铝比的降低，HZSM-5酸性增强，所得焦油中芳烃组分含量逐渐提高，这表明，HZSM-5在催化煤热解过程中促进了挥发物的氢转移、环化、芳构化反应，从而生成了更多的芳烃组分。
- 分子筛 /
- 酸性 /
- 煤热解 /
- 催化提质 /
- 积炭
Abstract: The effects of SiO₂/Al₂O₃ ratio of HZSM-5 on the tar quality and coke formation during catalytic upgrading of coal pyrolysis volatiles were investigated. The results showed that the carbon deposition amount decreased with the increase of the SiO₂/Al₂O₃ ratio of HZSM-5 due to the decrease of strong and weak acid amount. When the SiO₂/Al₂O₃ ratio increased from 23 to 310, the carbon deposition amount decreased from 120.1 mg/g-catalyst to 23.9 mg/g-catalyst. Moreover, the higher ratio of strong and weak acid amount led to lighter fraction in tar. With the decrease of SiO₂/Al₂O₃ ratio, the acid strength was enhanced so that the aromatics content in the tars decreased, indicating that the stronger acidic sites promoted the dehydrogenation, cyclization and aromatization reactions of volatiles, thus leading to higher yield of aromatics during catalytic coal pyrolysis.
- zeolite /
- acidity /
- coal pyrolysis /
- catalytic upgrading /
- coke deposition

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FIG. 654. FIG. 654.

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图 1 实验装置示意图

Figure 1 Schematic diagram of the experimental apparatus

1: mass flow meter; 2,3,5,15: valve; 4: feeder; 6,10: thermocouple; 7,9: quartz sieve plate; 8: electric furnace; 11: condenser; 12: acetone trap; 13: NaHCO₃ (aq) trap; 14: dry silica gel bottle; 16: volumetric flowmeter

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图 2 不同硅铝比HZSM-5的XRD谱图

Figure 2 XRD patterns of HZSM-5 with different SiO₂/Al₂O₃ ratio

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图 3 不同硅铝比HZSM-5的NH₃-TPD谱图

Figure 3 NH₃-TPD profiles of HZSM-5 with different SiO₂/Al₂O₃ ratio

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图 4 不同硅铝比HZSM-5催化煤热解挥发物热解产物

Figure 4 Product distribution (a), tar quality (b) and pyrolysis gas component yield (c) over HZSM-5 with different SiO₂/Al₂O₃ ratio (t_py = 600 ℃, t_cr = 500 ℃, catalyst: 10% of the tested coal)

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图 5 不同硅铝比HZSM-5酸性特征与焦油品质的关系

Figure 5 The relationship between tar quality and the acidity of HZSM-5 with different SiO₂/Al₂O₃ ratio

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表 1 淖毛湖煤的工业分析和元素分析

Table 1 Proximate and ultimate analyses of Naomaohu coal

Proximate analysis (dry base) w/%			Ultimate analysis (dry and ash-free base) w/%
A	V	FC	C	H	S	N	O^a
7.16	47.78	45.06	74.77	5.67	0.27	0.93	18.36
^a: by difference

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表 2 不同硅铝比的HZSM-5的酸性位点数量特征对比

Table 2 Acidity of HZSM-5 with different SiO₂/Al₂O₃ ratio

Catalyst	Weak acid		Strong acid		Ratio of quantity of strong and weak acidic sites
Catalyst	temperature at maximum/℃	quantity /(μmol∙g⁻¹)	temperature at maximum/℃	quantity /(μmol∙g⁻¹)	Ratio of quantity of strong and weak acidic sites
HZ23	139.7	2285	387.7	602.4	0.264
HZ50	124.3	1438	384.7	313.2	0.218
HZ80	118.5	891.3	378.8	268.3	0.301
HZ280	115.6	415.5	357.0	191.9	0.462
HZ310	141.4	396.4	356.5	171.8	0.433

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表 3 不同硅铝比HZSM-5的结构特征

Table 3 Structural characters of HZSM-5 with different SiO₂/Al₂O₃ ratio

Catalyst	Specific surface area A/(m²∙g⁻¹)			Pore volume v/(cm³∙g⁻¹)
Catalyst	S_BET^a	S_micro^b	S_meso^c	Pore volume v/(cm³∙g⁻¹)
HZ23	422.3	308.1	114.2	0.089
HZ50	414.6	243.2	171.4	0.136
HZ80	489.8	264.4	225.4	0.174
HZ280	407.9	224.6	183.3	0.153
HZ310	588.6	435.0	153.6	0.243
^a: BET method; ^b: t-plot method; ^c: S_meso = S_BET − S_mirco

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表 4 不同硅铝比HZSM-5上的积炭量

Table 4 Carbon deposition over HZSM-5 with different SiO₂/Al₂O₃ ratio

Catalyst	HZ23	HZ50	HZ80	HZ280	HZ310
Specific C deposition/（mg·g⁻¹） *	120.1	99.0	73.8	26.5	23.9
*: specific C deposition refers to the deposited carbon in mg on per gram HZSM-5

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表 5 不同硅铝比HZSM-5积炭的丙酮可溶物GC-MS表征

Table 5 The acetone-soluble matter of coke over HZSM-5 with different SiO₂/Al₂O₃ ratio

Name	Formula	Content w/%
Name	Formula	HZ23	HZ50	HZ80	HZ280	HZ310
4-methyl-3-penten-2-one	C₆H₁₀O	42.91	84.24	34.76	12.37	20.23
4-methyl-4-penten-2-one	C₆H₁₀O	3.79	3.38	3.91	2.46	3.32
Tetramethyl-oxirane	C₆H₁₂O	53.26	9.28	61.15	85.14	76.4
Toluene	C₇H₈	0.03	0.15	0.02	0.02	0.03
2,3,4-trimethyl-pentane	C₈H₁₈	0.01	0.07		0.01	0.02
Others			2.88	0.16

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表 6 HZSM-5催化煤热解所得焦油的元素分析

Table 6 Ultimate analysis of tars obtained over HZSM-5 with different SiO₂/Al₂O₃ ratio

Catalyst	Uitimate analysis w/%					H/C (mol ratio)
Catalyst	C	H	O ^a	N	S	H/C (mol ratio)
Without catalyst	78.31	8.991	11.39	0.881	0.428	1.378
HZ23	82.02	8.648	8.454	0.686	0.192	1.265
HZ50	80.37	8.263	10.40	0.728	0.239	1.234
HZ80	78.22	8.163	12.57	0.835	0.213	1.252
HZ280	80.53	8.612	9.84	0.814	0.214	1.283
HZ310	79.97	8.605	10.42	0.819	0.186	1.291
^a: by difference

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表 7 HZSM-5催化煤热解所得焦油中组分分布

Table 7 The component distribution of tars obtained over HZSM-5 with different SiO₂/Al₂O₃ ratio

Catalyst	Content w/%
Catalyst	SAHs	USHs	AHs	HCHs
Without catalyst	38.1	10.6	13.1	38.2
HZ23	11.4	0.5	56.4	31.7
HZ50	10.6	0.4	58.4	30.6
HZ80	13.7		52.7	33.6
HZ280	21.9		46.6	31.5
HZ310	16.3		35.8	47.9

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