神府长焰煤加氢增黏反应中催化剂及氢传递机理

doi:10.16085/j.issn.1000-6613.2020-1579

化工进展 ›› 2021, Vol. 40 ›› Issue (7): 3711-3718.DOI: 10.16085/j.issn.1000-6613.2020-1579

神府长焰煤加氢增黏反应中催化剂及氢传递机理

刘守军¹^,²^,³(), 王钊¹^,³, 演康¹^,³, 杨颂¹^,³(), 上官炬²^,³, 杜文广²^,³, 常志伟²^,³, 刘月华²^,³

^1.太原理工大学化学化工学院，山西太原 030024
^2.太原理工大学煤科学与技术教育部和山西省重点实验室，山西太原 030024
^3.山西省民用洁净燃料工程研究中心，山西太原 030024

收稿日期:2020-08-10 修回日期:2020-11-06 出版日期:2021-07-06 发布日期:2021-07-19
通讯作者: 杨颂
作者简介:刘守军（1963—），男，博士，副教授，研究方向为洁净煤技术。E-mail: 13303460889@163.com。
基金资助:
国家自然科学基金(21878210);山西省高等学校科技创新项目(2019L0313);山西省专利推广实施资助计划(20200719)

Catalyst and hydrogen transport mechanism of catalytic hydrogenation of Shenfu long-flame coal

LIU Shoujun¹^,²^,³(), WANG Zhao¹^,³, YAN Kang¹^,³, YANG Song¹^,³(), SHANGGUAN Ju²^,³, DU Wenguang²^,³, CHANG Zhiwei²^,³, LIU Yuehua²^,³

^1.College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^3.Shanxi Engineering Center of Civil Clean Fuel, Taiyuan 030024, Shanxi, China

Received:2020-08-10 Revised:2020-11-06 Online:2021-07-06 Published:2021-07-19
Contact: YANG Song

摘要/Abstract

摘要：

我国炼焦煤资源短缺且分布不均匀，而低阶煤储量丰富，价格低廉，具有低灰、低硫等特点，但其黏结性几近为零。催化加氢增黏是一种有效提高低阶煤黏结性的方法。本文通过对长焰煤进行催化加氢增黏，对原煤及增黏煤进行元素分析、红外分析、电子顺磁共振分析和反应中氢耗计算研究催化加氢增黏反应中催化剂及氢传递机理。结果表明：长焰煤黏结性显著增强，在炼焦过程中可部分替代炼焦煤使用；加氢增黏可以去除长焰煤中部分含氧官能团及烷基侧链，降低煤分子的交联程度；催化剂主要作用是活化氢气，其次可以促进煤分子解聚并且促进四氢萘到煤的氢传递。当催化剂存在时，催化加氢增黏反应氢传递路径主要是从氢气直接至煤分子，而不是通过供氢溶剂至煤分子。

关键词: 低阶煤, 催化（作用）, 氢传递, 溶剂萃取, 自由基

Abstract:

China's coking coal resources are scarce and unevenly distributed. However, the low-grade coal in China is rich in reserves, low in price, and has the characteristics of low ash and low sulfur, near-zero caking index. Catalytic hydrogenation is an effective method to improve the caking property of low-grade coal. In this paper, the catalytic hydrogenation of long-flame coal was carried out, and elemental analysis, infrared analysis, electron paramagnetic resonance analysis, and reaction hydrogen consumption calculation were performed for the raw coal and modified coal to study the role of catalyst and the hydrogen transport mechanism. The results indicated that the caking property of long-flame coal was significantly enhanced, which could partially replace coking coal in the coking process. Hydrogenation can remove part of the oxygen-containing functional groups and alkyl side chains in the long-flame coal, and reduce the degree of crosslinking of coal molecules. The main function of the catalyst is to activate hydrogen, and secondly to promote the depolymerization of coal molecules and promote the hydrogen transport of tetralin to coal. In the presence of a catalyst, the dominant hydrogen transport path of the catalytic hydrogenation reaction is directly from hydrogen to coal molecules instead of from hydrogen donor solvent to coal.

Key words: low-rank coal, catalysis, hydrogen transport, solvent extraction, radical

中图分类号:

TQ536.1

刘守军, 王钊, 演康, 杨颂, 上官炬, 杜文广, 常志伟, 刘月华. 神府长焰煤加氢增黏反应中催化剂及氢传递机理[J]. 化工进展, 2021, 40(7): 3711-3718.

LIU Shoujun, WANG Zhao, YAN Kang, YANG Song, SHANGGUAN Ju, DU Wenguang, CHANG Zhiwei, LIU Yuehua. Catalyst and hydrogen transport mechanism of catalytic hydrogenation of Shenfu long-flame coal[J]. Chemical Industry and Engineering Progress, 2021, 40(7): 3711-3718.

图/表 13

表1 样品的煤质分析（质量分数）

样品	元素分析（daf）/%						工业分析/%			G_RI
样品	C	H	N	S	O^a		M_ad	A_d	V_daf	G_RI
长焰煤	80.64	4.95	1.17	0.48	12.76		4.73	8.34	37.32	0

图1 改性煤溶剂抽提实验

图2 氮气气氛下不同溶剂添加或不添加催化剂的煤转化率和产物产率T-without cat—溶剂为四氢萘、不添加催化剂的反应；T-with cat—溶剂为四氢萘、添加催化剂的反应

图3 在加氢增黏过程中加或不加催化剂的氢耗及产生的氢量H.C. Without cat—不添加催化剂反应中氢消耗量；H.C. With cat—添加催化剂反应中氢消耗量；H.G. Without cat—不添加催化剂反应中氢生成量；H.G. With cat—添加催化剂反应中氢生成量

图4 氢气气氛下不同溶剂添加或不添加催化剂的煤转化率和产物产率T-without cat—溶剂为四氢萘、不添加催化剂的反应；T-with cat—溶剂为四氢萘、添加催化剂的反应

图5 氢气气氛下加氢增黏添加或不添加催化剂的氢耗S.H.C without cat—不添加催化剂反应中溶剂氢消耗量；S.H.C with cat—添加催化剂反应中溶剂氢消耗量；H2.H.C without cat—不添加催化剂反应中氢气氢消耗量；H2.H.C with cat—添加催化剂反应中氢气氢消耗量）

表2 溶剂为1-甲基萘时回收溶剂检测组分及其含量

溶剂	N₂质量分数/%		H₂质量分数/%
溶剂	不加催化剂	加入催化剂	不加催化剂	加入催化剂
四氢萘	0.32	0.83	0.66	2.01
1-甲基萘	97.90	97.07	97.68	95.63
5-甲基四氢化萘	0.94	0.92	0.88	0.76
萘	0.84	1.18	0.78	1.60

表3 当溶剂为1-甲基萘和四氢萘时检测结果

序号	反应气氛	催化剂	溶剂	煤转化率/%	产率/%		氢耗/g·（100g coal）^-1
序号	反应气氛	催化剂	溶剂	煤转化率/%	PAA	Oil+Gas	H₂	Solvent
1	N₂	无	1-MN	12.5	7.2	5.3	—	—
2	N₂	无	THN	37.9	22.1	15.8	—	0.75
3	N₂	有	1-MN	8.5	5.2	3.3	—	—
4	N₂	有	THN	44.3	26.6	17.7	—	1.06
5	H₂	无	1-MN	14.5	8.4	6.1	0.34	—
6	H₂	无	THN	41.3	26.2	15.1	0.16	0.72
7	H₂	有	1-MN	41.4	15.6	25.8	0.92	—
8	H₂	有	THN	53.3	30.9	22.4	0.64	0.75

图6 长焰煤和改性煤的傅里叶红外谱图

表4 长焰煤和改性煤的元素分析和工业分析（质量分数）

样品	元素分析（daf）/%					工业分析/%
样品	C	H	N	S	O^a	M_ad	A_d	V_daf
长焰煤	80.64	4.95	1.17	0.48	12.76	4.73	8.34	37.32
改性煤	85.51	5.68	0.93	0.82	7.06	3.72	8.75	35.23

图7 长焰煤和改性煤EPR谱图

表5 长焰煤和改性煤的电子顺磁共振谱图参数

样品	自由基浓度N_g/spin·g^-1	线宽?H_pp/Gs	G_RI
长焰煤	1.02×10¹⁷	5.6	0
改性煤	0.98×10¹⁷	5.4	32

图8 长焰煤催化加氢增黏机理

参考文献 36

1	黄文辉, 杨起, 唐修义, 等. 中国炼焦煤资源分布特点与深部资源潜力分析[J]. 中国煤炭地质, 2010, 22(5): 1-6.
	HUANG Wenhui, YANG Qi, TANG Xiuyi, et al. Analysis on distribution characteristics and deep resource potential of coking coal in China [J]. Coal Geology of China, 2010, 22(5): 1-6.
2	黄澎. 低变质烟煤温和加氢改性过程试验研究[J]. 中国煤炭, 2017, 43(6): 97-101.
	HUANG Peng. Experimental study on mild hydrogenation of low metamorphic bituminous coal [J]. China's Coal, 2017, 43(6): 97-101.
3	NANDI B N, TERNAN M, BELINKO K. Conversion of non-coking coals to coking coals by thermal hydrogenation [J]. Fuel, 1981, 60(4): 347-354.
4	SHUI Hengfu, LI Haiping, CHANG Hongtao. Modification of sub-bituminous coal by steam treatment: caking and coking properties [J]. Fuel Processing Technology, 2011, 92(12): 2299-2304.
5	MUKHERJEE D, SENGUPTA A, CHOUDHURY D. Effect of hydrothermal treatment on caking propensity of coal [J]. Fuel, 1996, 75(4): 477-482.
6	SEKI H, ITO O, IINO M. Effect of acetylation on caking properties of bituminous coals [J]. Energy Fuels, 1990, 4(4): 352-355.
7	库哈连科 T A. 烟煤的初步加氢是认识和改变烟煤本性的方法[M]. 郑志永, 译. 北京: 地质出版社, 1959: 45-46.
	KUHARENKO T A. The preliminary hydrogenation of bituminous coal is a way to understand and change the nature of bituminous coal [M]. ZHENG Zhiyong, trans. Beijing: Geological Press, 1959: 45-46.
8	郝爱民, 李新生, 宋永玮. 煤的改性提质对水煤浆成浆性的影响[J]. 煤炭转化, 2001, 24(3): 47-50.
	HAO Aimin, LI Xinsheng, SONG Yongwei. Influence of coal modification and coal water slurry (CWS) quality on its slurry forming property [J]. Coal Conversion, 2001, 24(3): 47-50.
9	郑明东, 李正秋, 单海燕, 等. 高挥发分不黏煤的预热改质与成焦行为研究[J]. 燃料与化工, 2010, 41(2): 10-14.
	ZHENG Mingdong, LI Zhengqiu, SHAN Haiyan, et al. Study on preheating modification and coke forming behavior of high volatile non-sticky coal [J]. Fuel and Chemical Industry, 2010, 41(2): 10-14.
10	WANG Zhicai, SHUI Hengfu, PEI Zhanning. Study on the hydrothermal treatment of Shenhua coal [J]. Fuel, 2008, 87(4/5): 527-533.
11	SHUI Hengfu, WANG Zhicai, WANG Gaoqiang. Effect of hydrothermal treatment on the extraction of coal in the CS₂/NMP mixed solvent [J]. Fuel, 2006, 85(12/13): 1798-1802.
12	胡德生, 水恒福, 孙维周, 等. 神府煤水热处理方法: CN102140356A [P]. 2011-08-03.
	HU Desheng, SHUI Hengfu, SUN Weizhou, et al. Shenfu coal water heat treatment method: CN102140356A [P]. 2011-08-03.
13	王东升. 低变质烟煤加氢增塑产物的工艺性质分析[J]. 煤质技术, 2010(6): 15-17.
	WANG Dongsheng. Analysis of process properties of hydroplasticized products of low metamorphic bituminous coal [J]. Coal Quality Technology, 2010(6): 15-17.
14	王东升, 黄澎, 白向飞. 低变质烟煤加氢增塑改质的试验研究[J]. 煤炭科学技术, 2008, 6(7): 104-106.
	WANG Dongsheng, HUANG Peng, BAI Xiangfei. Experimental study on hydroplasticizing and upgrading of low metamorphic bituminous coal [J]. Coal Science and Technology, 2008, 6(7): 104-106.
15	ZHU Jisheng, YANG Jianli, LIU Zhenyu, et al. Improvement and characterization of an impregnated iron-based catalyst for direct coal liquefaction [J]. Fuel Processing Technology, 2001, 72(3): 199-214.
16	GUIN J A, ZHAN Xiaodong, LINHART R S. Coal liquefaction using a dispersed phase nanoscale iron oxyhydroxide catalyst [J]. Energy Fuel, 1994, 8(1): 105-112.
17	PAINTER P, CETIER R, PULATI N, et al. Dispersion of liquefaction catalysts in coal using ionic liquids [J]. Energy Fuel, 2010, 24: 3086-3092.
18	ZHAO Jianmin, FENG Zhen, HUGGINS F E, al at. Binary iron oxide catalysts for direct coal liquefaction [J]. Energy Fuel, 1994, 8(1): 38-43.
19	IKENGA N, TANGCHI H, WATANABLE A, et al. Sulfiding behavior of iron based coal liquefaction catalyst [J]. Fuel, 2000, 79: 273-283.
20	JIN Lijun, HAN Keming, WANG Jianyou, et al. Direct liquefaction behaviors of Bulianta coal and its macerals [J]. Fuel Processing Technology, 2014, 128: 232-237.
21	CUGISH A V, KRASTAN D, LETT R G, et al. Development of a dispersed iron catalyst for first stage coal liquefication [J]. Catalysis Today, 1994, 19(3): 395-407.
22	MPOCHI I, SAKANISH K. Catalysis in coal liquefaction [J]. Advances in Catalysis, 1994, 40(1): 39-85.
23	MOCHIDA I, SAKANISH K, SUZUK N, et al. Progresses of coal liquefaction catalysts in Japan [J]. Catalysis Surveys from Asia, 1998, 2(1): 17-30.
24	KANEKO T, TAZAWA K, OKOMA N. Effect of highly dispersed iron catalyst on direct liquefaction of coal [J]. Fuel, 2000, 79(3/4): 263-271.
25	LI Liang, HUANG Sheng, WU Shiyong, et al. Roles of Na₂CO₃ in lignite hydro-liquefaction with Fe-based catalyst [J]. Fuel Processing Technology, 2015, 138: 109-115.
26	CURRAN G P, STRUCK R T, GORIN E. Mechanism of hydrogen-transfer process to coal and coal extract [J]. Industrial & Engineering Chemistry Process Design and Development, 1967, 6(2): 166-173.
27	DING Weibing, LIANG Jing, ANDERSON L L. Kinetics of thermal and catalytic coal liquefaction with plastic-derived liquids as solvent [J]. Industrial & Engineering Chemistry Research, 1997, 36(5): 1444-1452.
28	SHARMA R K, YANG Jianli, ZONDLO J W, et al. Effect of process conditions on co-liquefaction kinetics of waste tire and coal [J]. Catalysis Today, 1998, 40(4): 307-320.
29	GRIEVA E N, PANCHENKO S S, KOROBKOV V Y, et al. Correlation between structure and reactivity of diarylmethanes as coal-related model substances [J]. Fuel Processing Technology, 1994, 41(1): 39-53.
30	ARTOK L, ERBATUR O, SCHOBERT H H. Reaction of dinaphthyl and diphenyl ethers at liquefaction conditions [J]. Fuel Processing Technology, 1996, 47(2): 153-176.
31	WANG Zhicai, WANG Qian, HU Runan, et al. Effect of thermal extraction on hydro-liquefaction property of residual coal [J]. Fuel, 2019, 251: 474-481.
32	黄澎, 杜铭华, 李克健. 神华煤加氢增塑的研究[J]. 煤炭学报, 2009, 34(5): 683-687.
	HUANG Peng, DU Minghua, LI Kejian. Study on the caking improvement of Shenhua coal by hydrogenation [J]. Journal of China Coal Society, 2009, 34(5): 683-687.
33	UEBERSFEID J, ÉTIENNE A, COMBRISSON J. Paramagnetic resonance, a new property of coal-like materials [J]. Nature, 1954, 174: 614.
34	成茂, 王胜春, 张德祥. 煤转化过程自由基研究进展[J]. 煤炭转化, 2012, 12(4): 94-98.
	CHENG Mao, WANG Shengchun, ZHANG Dexiang. The research progress on free radicals in coal conversion process [J]. Coal Conversion, 2012, 12(4): 94-98.
35	邱冠周, 刘国根, 胡善亭, 等. 煤的ESR波谱研究[J]. 中南工业大学学报， 1997, 28(5)： 427-429.
	QIU Guanzhou, LIU Guogen, HU shanting, et al. A study on ESR spectrum of caol[J]. Journal of Central South Universty of Technology, 1997, 28(5)： 427-429.
36	CHENG H N, WARTELLE L H, THOMAS K K. Solid-state NMR and ESR studies of activated carbons produced from pecan shells [J]. Carbon, 2010, 48(3): 2455-2469.

[1]	钱思甜, 彭文俊, 张先明. PET熔融缩聚与溶液解聚形成环状低聚物的对比分析[J]. 化工进展, 2023, 42(9): 4808-4816.
[2]	白志华, 张军. 二乙烯三胺五亚甲基膦酸/Fenton体系氧化脱除NO[J]. 化工进展, 2023, 42(9): 4967-4973.
[3]	吴海波, 王希仑, 方岩雄, 纪红兵. 3D打印催化材料开发与应用进展[J]. 化工进展, 2023, 42(8): 3956-3964.
[4]	徐沛瑶, 陈标奇, KANKALA Ranjith Kumar, 王士斌, 陈爱政. 纳米材料用于铁死亡联合治疗的研究进展[J]. 化工进展, 2023, 42(7): 3684-3694.
[5]	包进, 宋永辉, 董萍, 李一凡, 朱荣燕, 廖龙. 氰化尾渣矿浆电解液中铁离子的萃取富集[J]. 化工进展, 2023, 42(1): 517-525.
[6]	王庆宏, 姜晨旭, 王鑫, 余美琪, 朱帅, 李一鸣, 陈春茂. 天然矿物催化氧化水中难降解有机污染物研究进展[J]. 化工进展, 2023, 42(1): 417-434.
[7]	叶玉玺, 丁晓茜, 池华睿, 朱楷伦, 刘杨, 王凌云, 郭庆杰. 疏水性低共熔溶剂氢键交互作用调控及萃取铜性能[J]. 化工进展, 2022, 41(S1): 397-406.
[8]	胡文德, 王仰东, 王传明. 合成气直接催化转化制低碳烯烃研究进展[J]. 化工进展, 2022, 41(9): 4754-4766.
[9]	伊学农, 李京梅, 高玉琼. 紫外-高铁酸盐体系氧化降解水中的萘普生[J]. 化工进展, 2022, 41(8): 4562-4570.
[10]	潘杰, 王明新, 高生旺, 夏训峰, 韩雪. 氮硫掺杂生物炭/过一硫酸盐体系降解水中磺胺异唑[J]. 化工进展, 2022, 41(8): 4204-4212.
[11]	张喻, 高宁博, 全翠, 王凤超. 低阶煤热解高温油气除尘技术进展[J]. 化工进展, 2022, 41(4): 1814-1824.
[12]	熊哲, 邓伟, 刘佳, 汪雪棚, 徐俊, 江龙, 苏胜, 汪一, 胡松, 向军. 生物油非催化热转化过程中受热结焦特性研究进展[J]. 化工进展, 2022, 41(4): 1802-1813.
[13]	甄建政, 聂士松, 潘世元, 吕维扬, 姚玉元. 多维度碳基负载金属催化剂活化PMS降解水中污染物的研究进展[J]. 化工进展, 2022, 41(4): 1858-1872.
[14]	刘鸿益, 杨光星, 余皓. 电磁感应加热用于可持续催化技术的研究进展[J]. 化工进展, 2022, 41(3): 1440-1452.
[15]	徐铭骏, 郭兆春, 李立, 朱紫琦, 张倩, 洪俊明. 纳米片状Mn₂O₃@α-Fe₃O₄活化过碳酸盐降解偶氮染料[J]. 化工进展, 2022, 41(2): 1043-1053.

神府长焰煤加氢增黏反应中催化剂及氢传递机理

Catalyst and hydrogen transport mechanism of catalytic hydrogenation of Shenfu long-flame coal

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 36

相关文章 15

编辑推荐

Metrics

本文评价