不同催化剂上有机质加氢热解行为及催化作用机理研究

刘洋; 何坤; 李贤庆; 韩蕊; 王哲; 徐红卫

不同催化剂上有机质加氢热解行为及催化作用机理研究

刘洋^{1, 2, 3},
何坤³,
李贤庆^{1, 2, ,},
韩蕊²,
王哲^{1, 2},
徐红卫^{1, 2}

1.
中国矿业大学(北京) 煤炭资源与安全开采国家重点实验室, 北京 100083
2.
中国矿业大学(北京) 地球科学与测绘工程学院, 北京 100083
3.
中国石油勘探开发研究院油气地球化学重点实验室, 北京 100083

基金项目:

国家自然科学基金 41572125

"十二五"国家科技重大专项课题 2011ZX05007-002

"十二五"国家科技重大专项课题 2011ZX05033-004

国家公益性行业科研专项基金 201311022

煤炭资源与安全开采国家重点实验室自主科研课题 SKLCRSM10B04

详细信息

通讯作者:
李贤庆, Tel: 010-62331854-8131, E-mail: lixq@cumtb.edu.cn

中图分类号: TQ530.2
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- 被引次数: 0
出版历程
- 收稿日期: 2015-07-28
- 修回日期: 2015-11-09
- 网络出版日期: 2022-03-23
- 刊出日期: 2016-01-01

Performance of various catalysts in hydropyrolysis of organic matters and reaction mechanisms

LIU Yang^{1, 2, 3},
HE Kun³,
LI Xian-qing^{1, 2
, ,},
HAN Rui²,
WANG Zhe^{1, 2},
XU Hong-wei^{1, 2}

1.
State Key Laboratory of Coal Resources and Safe Mining, China University of Mining and Technology (Beijing), Beijing 100083, China
2.
College of Geoscience and Surveying Engineering, China University of Mining and Technology (Beijing), Beijing 100083, China
3.
Key Laboratory of Petroleum Geochemistry, China National Petroleum Corporation, Beijing 100083, China

Funds:

The project was supported by the National Natural Science Foundation of China 41572125

Important National Science & Technology Specific Projects of China during the 12th Five-year Plan Period 2011ZX05007-002

Important National Science & Technology Specific Projects of China during the 12th Five-year Plan Period 2011ZX05033-004

National Special Fund for Research in the Public Interest 201311022

Independent Scientific Research Project of State Key Lab-oratory of Coal Resources and Safe Mining SKLCRSM10B04

More Information

Corresponding author: LI Xian-qing, Tel: 010-62331854-8131, E-mail: lixq@cumtb.edu.cn

摘要

摘要: 对不同类型催化剂如ZnCl₂、NiCl₂、Fe₂O₃、Y型沸石(NaY) 及MoS₂上有机质的催化加氢热解行为及反应机理进行了研究。结果表明, 有机质加氢液态产物收率和组成受控于催化剂类型, 但不同催化剂上加氢热解所得到的产物生标参数差异不大; 同时, 对于不同成熟度和类型的有机质样品, 各催化剂所体现的催化效果也不尽相同。基于固体残渣元素组成、红外光谱和X射线衍射分析结果发现, 不同类型催化剂上的加氢作用机制也存在明显差异。与NiCl₂相比, ZnCl₂体系中除存在催化裂解和催化加氢作用外, 还存在质量传递效应; Fe₂O₃催化剂主要是通过其表面的活性O吸收H₂中的H形成H自由基而加速有机质的加氢反应; MoS₂体系存在过渡金属Mo的催化加氢和中间产物H₂S的自由基引发作用两种催化机制。
- 有机质 /
- 加氢热解 /
- 生物标志物 /
- 催化反应机理
Abstract: The hydropyrolysis of organic matters was comparatively conducted over various catalysts including ZnCl₂, NiCl₂, Fe₂O₃, NaY and MoS₂ and the reaction mechanisms over different catalysts were then investigated. The results indicate that the yield and composition of liquid products from hydropyrolysis are related to the type of catalyst, though various catalysts do not have significant difference in the product biomarker parameters. Meanwhile, for the organic matters with different maturities and types, various catalysts are also quite different in their actual performance. The element analysis, infrared spectra and X-ray diffractograms of the solid residues illustrate that various catalysts are obviously different in the catalytic reaction mechanism. In comparison with NiCl₂, mass transfer is an important factor in the ZnCl₂ system, besides the catalytic cracking and catalytic hydrogenation. With Fe₂O₃ as the catalyst, the formation of H free radical by the adsorption of H₂ at the surface active O sites may promote the hydrogenation of organic matters. MoS₂ as the catalyst may involve two mechanisms, viz., the hydrogenation over transition metal Mo and the initiation of free radicals from H₂S intermediates.
- organic matters /
- hydropyrolysis /
- biomarkers /
- catalytic reaction mechanism

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图 1 不同催化条件下饱和烃和芳烃产率

Figure 1 Yields of saturated hydrocarbons and aromatics obtained over different catalysts

(a): Kerogen of Du-13; (b): Kerogen of Zhaoshen-5; (c): Fuxin coal

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图 2 油中饱和烃(a) 和芳烃(b) 的总离子质量色谱图

Figure 2 Total ion chromatograms of saturated hydrocarbons (a) and aromatics (b) in oil fractions

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图 3 油中饱和烃的m/z 83质量色谱图

Figure 3 m/z 83 chromatograms for saturates in oils

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图 4 阜新煤单独与催化加氢液化的总转化率及液态产物产率

Figure 4 Total conversion and liquids yields for the catalytic hydropyrolysis of Fuxin coal

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图 5 原阜新煤和液化残余物的红外光谱谱图

Figure 5 Transmission infrared (FT-IR) spectra of the initial coal and residues

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图 6 原阜新煤和液化残余物的X衍射谱图

Figure 6 XRD patterns of the initial coal and residues

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表 1 催化加氢热解样品的地球化学特征

Table 1 Geochemical characteristic of the organic matters for catalytic hydropyrolysis

Sample	Depth L/m	Layer	TOC w/%	R₀ w/%	Elemental compostion of kerogen w/%
Sample	Depth L/m	Layer	TOC w/%	R₀ w/%	C	H	O	N
Du-13	1 408.5	K	3.14	0.84	60.44	1.231	6.61	1.65
Zhaoshen-5	4 331	C-P	-	2.06	72.99	0.296	2.17	1.83
Fuxin coal	surface	J	71.24	0.55	73.52	5.68	-	1.23

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表 2 不同催化剂条件下有机质加氢热解的液体产物产率及组成特征

Table 2 Yields and compositions of liquid products from catalytic hydropyrolysis of organic matters over different catalysts

Sample	Catalyst	Overall yield of liquid hydrocarbons w/(mg·g^-1)	Group composition w/%
Sample	Catalyst	Overall yield of liquid hydrocarbons w/(mg·g^-1)	saturates	aromatics	NSO compounds and asphaltenes
Kerogen of Du-13	ZnCl₂	292.0	30.2	54.8	15.0
	Al₂O₃	258.0	29.6	55.1	15.3
	NaY	298.4	23.2	57.1	19.7
	MoS₂	390.9	35.5	39.6	24.9
Kerogen of Zhaoshen-5	ZnCl₂	40.2	18.1	62.8	19.1
	Fe₂O₃	16.0	25.0	60.5	14.5
	Al₂O₃	17.6	17.0	62.5	20.5
	MoS₂	18.0	37.5	43.8	18.7
Fuxin coal	alone	162.8	14.9	13.9	71.2
	ZnCl₂	606.0	16.6	25.5	57.9
	NiCl₂	541.5	15.1	23.8	61.1
	Fe₂O₃	503.6	19.1	28.6	60.3
	MoS₂	237.8	29.7	15.8	54.5

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表 3 阜新煤不同催化加氢热解产物的生标参数

Table 3 Biomarker parameters of pyrolysis products from Fuxin coal over different catalysts

Biomarker parameter	Extracts^*	Catalyst free	Catalytic conditions
Biomarker parameter	Extracts^*	Catalyst free	ZnCl₂	NiCl₂	Fe₂O₃	MoS₂
Pr/Ph	7.85	5.47	6.30	4.13	4.32	4.70
Pr/ nC₁₇	4.01	0.68	1.23	0.59	0.51	0.93
Ph/ nC₁₈	0.57	0.12	0.21	0.14	0.11	0.19
CPI	1.87	1.20	1.43	1.22	1.15	1.21
OEP-1	1.34	1.05	1.13	1.06	1.04	1.06
C₂₂/C₂₁ tricyclic terpane	0.43	0.37	0.47	0.34	0.32	0.32
Ts/(Ts+Tm)	0.36	0.33	-	0.23	0.22	0.29
C₂₉ βα /C₂₉ αβ	0.52	0.38	0.45	0.35	0.37	0.42
C₃₀ βα /C₃₀ αβ	0.48	0.41	0.50	0.45	0.46	0.51
C₃₁αβ 22S/(22S+22R)	0.57	0.52	0.49	0.51	0.48	0.46
C₃₂αβ 22S/(22S+22R)	0.56	0.53	0.48	0.50	0.43	0.47
C₂₉ 20S/(20S+20R)	0.23	0.26	0.22	0.25	0.24	0.19
C₂₉ ββ/(ββ+αα)	0.23	0.24	0.20	0.24	0.15	0.15
MPI-1	0.33	0.71	0.56	0.65	0.62	0.58
MNR	1.08	2.37	2.16	2.54	2.08	2.00
ENR	0.23	0.24	0.39	0.37	0.44	0.40
^*: extracts represent the liquid products obtained by extraction of organic matters

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表 4 阜新煤样加氢热解后固体残余物的元素分析

Table 4 Elemental compositions of solid residues

Reaction condition	Content w/%					C/H^*
Reaction condition	C	H	O	S	N	C/H^*
Catalyst free	77.04	4.32	6.94	1.02	1.39	1/1.75
ZnCl₂	63.57	3.12	5.84	1.43	0.96	1/1.13
NiCl₂	62.88	3.17	4.30	1.03	1.03	1/1.20
Fe₂O₃	45.76	2.34	3.66	1.40	0.82	1/1.11
MoS₂	72.39	5.09	6.89	2.81	1.48	1/1.07
^*: C/H represents the ratio of carbon conversion to hydrogen in the hydropyrolysis

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