K2CO3对兰炭催化气化特性的影响

doi:10.11949/j.issn.0438-1157.20181224

化工学报 ›› 2019, Vol. 70 ›› Issue (S1): 99-109.DOI: 10.11949/j.issn.0438-1157.20181224

• 催化、动力学与反应器 • 上一篇下一篇

K₂CO₃对兰炭催化气化特性的影响

孟繁锐¹(),李伯阳¹,李先春^1,²(),邱爽²

1. 辽宁科技大学先进煤焦化及煤资源的高效利用工程技术中心，辽宁鞍山114051
2. 辽宁科技大学化工学院，辽宁鞍山 114051

收稿日期:2018-10-18 修回日期:2018-11-23 出版日期:2019-03-31 发布日期:2019-03-31
通讯作者: 李先春
作者简介:<named-content content-type="corresp-name">孟繁锐</named-content>（1987—），女，博士，讲师，<email>mengfanrui1025@163.com</email>|李先春（1972—），男，博士，教授，<email>askd1972@163.com</email>
基金资助:
中国辽宁攀登学者开放基金项目(USTLKFZD201633);辽宁省自然科学基金项目(201602397)

Catalysis effects of K₂CO₃ for gasification of semi-coke

Fanrui MENG¹(),Boyang LI¹,Xianchun LI^1,²(),Shuang QIU²

1. Engineering Research Center of Advanced Coal & Coking Technology and Efficient Utilization of Coal Resources, the Education Department of Liaoning Province, University of Science and Technology Liaoning, Anshan 114051, Liaoning, China
2. School of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051, Liaoning, China

Received:2018-10-18 Revised:2018-11-23 Online:2019-03-31 Published:2019-03-31
Contact: Xianchun LI

摘要/Abstract

摘要：

在固定床中考察了不同K₂CO₃植入浓度和不同温度条件下兰炭催化气化特性。结果表明，5%的催化剂植入浓度主要起到填充孔隙的作用，当植入浓度增加到10%以后，催化剂发生堆积会使颗粒表面及内部形成较多孔隙。提高气化温度可提高兰炭转化率，超过750℃之后碳转化率增幅减缓，催化剂饱和装载浓度为10%。在颗粒表面和开放孔隙中的高浓度C(O)才具有较高的脱附速率，并提高CO生成速率。在非催化条件下，随着气化的进行CO/CO₂下降，而H₂/(2CO₂+CO)先增后减。在催化条件下，H₂/(2CO₂+CO)稳定在1.5～1.7。催化剂兰炭样品中出现了K₂Ca(CO₃)₂双金属碳酸盐、K₂O、KO₂等活性组分，并随催化剂植入浓度的增加而增加。催化剂植入浓度的增加会导致失活现象加重，但兰炭在750℃条件下气化1 h 催化剂没有完全失活。

关键词: 固定床, 催化剂, 兰炭, 制氢, 气化

Abstract:

Steam gasification of potassium-loaded semi-coke has been carried out with a fixed-bed laboratory gasifier at atmospheric pressure. With the K₂CO₃ loading increased the micropore area decreased. At a loading of 5% (mass), the K₂CO₃ mainly plays the role of filling pores. Above the loading of 10% (mass), the accumulation of catalyst will lead to more pores on the surface and interior of the particles. Increasing the gasification temperature could increase the carbon conversion rate, but above 750℃ the carbon conversion rate increased indistinctively. The loading values above which the effect was negligible were 10% (mass). High concentration of C(O) on the surface of particles and in open pores has a higher desorption rate and led to the generation rate of CO increase. Under non-catalytic conditions, CO/CO₂ decreased as gasification time increasing, while H₂/(2CO₂+CO) increased first and then decreased. Under catalytic conditions, H₂/(2CO₂+CO) was stable at 1.5－1.7. The active components, such as K₂Ca(CO₃)₂, K₂O, and KO₂, appeared in the catalyst semi-coke samples and increased with the catalyst loading increasing. Catalyst deactivation phenomenon was aggravated due to the loading increasing, but it was not completely inactivation under the condition of gasification 1 h at 750℃.

Key words: fixed-bed, catalyst, semi-coke, hydrogen production, gasification

中图分类号:

TQ 536.1

孟繁锐, 李伯阳, 李先春, 邱爽. K₂CO₃对兰炭催化气化特性的影响[J]. 化工学报, 2019, 70(S1): 99-109.

Fanrui MENG, Boyang LI, Xianchun LI, Shuang QIU. Catalysis effects of K₂CO₃ for gasification of semi-coke[J]. CIESC Journal, 2019, 70(S1): 99-109.

图/表 9

表1 兰炭工业分析与元素分析

Table 1 Proximate and ultimate analysis of semi-coke coal

Sample	Proximate analysis/%				Ultimate analysis /%
Sample	M_ad	V_ad	A_ad	FC_ad	C_d	H_d	N_d	S_d
semi-coke	3.64	18.66	5.63	72.07	79.78	1.44	0.85	0.11

图1 兰炭催化气化实验装置

Fig.1 Schematic diagram of experimental set-up

图2 兰炭颗粒表观形貌SEM照片

Fig.2 SEM images of K2CO3/semi-coke particles

表2 不同装载浓度K2CO3/兰炭以及气化后残焦的比表面积和孔容分布

Table 2 Specific surface area and pore volume of K2CO3/semi-coke at different loading and residual coke

Sample, K₂CO₃/%	Surface area /(m²/g)	Micropore area /(m²/g)	External surface area /(m²/g)	Pore volume/(ml/g)
0	17.76	5.71	12.05	0.004
5	1.57	0	1.57	0.002
10	2.51	0.13	2.38	0.002
15	5.95	1.55	4.40	0.002
0-ash	598.13	398.44	199.70	0.148
5-ash	338.97	269.89	69.08	0.035
10-ash	189.57	163.39	26.18	0.009
15-ash	52.60	43.10	9.50	0.004

图3 不同气化温度条件下主要气体产率分布

Fig.3 Gas yield distribution at different gasification temperature（10%K2CO3/semi-coke，steam flow 0.6 ml/min）

图4 不同催化剂装载浓度条件下气化中气体产率分布

Fig.4 Gas yield distribution at different catalyst loading(gasification temperature750℃，steam flow 0.6 ml/min)

表3 不同装载浓度K2CO3/兰炭气化中CO/CO2和H2/(2CO2+CO)值的变化

Table 3 Changes of CO/CO2 and H2/(2CO2+CO) at different catalyst loading during gasification

Sample, K₂CO₃/%	10 min		20 min		30 min		40 min		50 min
Sample, K₂CO₃/%	CO/CO₂	H₂/(2CO₂+CO)	CO/CO₂	H₂/(2CO₂+CO)	CO/CO₂	H₂/(2CO₂+CO)	CO/CO₂	H₂/(2CO₂+CO)	CO/CO₂	H₂/(2CO₂+CO)
0	2.13	1.06	1.22	1.86	1.20	2.36	0.66	2.23	0.46	2.05
5	0.63	0.90	1.38	2.02	1.00	1.40	0.95	1.57	1.61	1.56
10	4.18	1.95	0.95	0.91	0.84	1.65	1.11	1.56	0.58	1.52
15	6.02	1.66	1.54	1.58	0.56	1.51	0.71	1.52	0.65	1.63

图5 不同催化剂装载浓度下兰炭及气化残焦的FTIR谱图

Fig.5 FTIR spectrum of samples at different catalyst loading (gasification temperature750℃，steam flow 0.6 ml/min)

图6 不同催化剂装载浓度下兰炭及气化残焦的XRD谱图

Fig.6 XRD patterns of samples at different catalyst loading(gasification temperature750℃，steam flow 0.6 ml/min

参考文献 36

1	汪寿建. 兰炭固定床连续气化制备清洁燃料气的应用与实践[J]. 化肥设计, 2017, 55(5): 5-10.
	WangS J. Application and practice of continous preparation of clean fuel gas though coal gasification in semi-coke fixed bed[J]. Chemical Fertilizer Design, 2017, 55(5): 5-10.
2	SharmaA, TakanohashiT, SaitoI, et al. Effect of catalyst addition on gasification reactivity of HyperCoal and coal with steam at 775—700℃[J]. Fuel, 2008, 87(12): 2686-2690.
3	ZhangF, XuD, WangY, et al. Catalytic CO₂ gasification of a Powder River Basin coal[J]. Fuel, 2013, 103(130): 161-170.
4	McKeeD W, SpiroC L, KoskyP G, et al. Catalysis of coal char gasification by alkali metal salts [J]. Fuel, 1983, 62(2): 217-220.
5	AkyurtluJ F, AkyurtluA. Catalytic gasification of Pittsburgh coal char by potassium sulphate and ferrous sulphate mixtures[J]. Fuel Processing Technology, 1988, 43(1): 71-86.
6	SongB H, YongW J, YunS B, et al. Steam gasification of a bituminous char catalyzed by a salt mixture of potassium sulfate and nikel nitrate[J]. Korean Chemical Engineering Research, 2003, 41(3): 349-356.
7	MurakamiK, SatoM, TsubouchiN, et al. Steam gasification of Indonesian subbituminous coal with calcium carbonate as a catalyst raw material[J]. Fuel Processing Technology, 2015, 129(129): 91-97.
8	WoodB , SancierK. The mechanism of the catalytic gasification of coal char: a critical review[J]. Catalysis Reviews, 1984, 26(2): 233-279.
9	KapteijnF, MoulijnJ A. Kinetics of the CO₂ gasification of activated carbon[J]. Fuel, 1983, 62(2): 221-225.
10	陈彦, 张济宇.福建无烟煤Na₂CO₃催化气化过程的比表面变化特性[J].化工学报, 2012, 63(8): 2443-2452.
	ChenY, ZhangJ Y. Variation of specific surface area in catalytic gasification process of Fujian anthracite with Na₂CO₃ catalyst[J]. CIESC Journal, 2012, 63(8): 2443-2452.
11	KarimiA, GrayM R. Effectiveness and mobility of catalysts for gasification of bitumen coke[J]. Fuel, 2011, 90(1): 120-125.
12	陈彦，张济宇. Na₂CO₃催化剂对福建高变质无烟煤比表面及气化反应特性的影响[J]. 化工学报,2011, 62(10): 2768-2775.
	ChenY, ZhangJ Y. Effects of catalyst loading of Na₂CO₃ on specific surface area and gasification characteristics of Fujian high-metamorphous anthracite[J]. CIESC Journal, 2011, 62(10): 2768-2775.
13	HurtR H, SarofimA F, LongwellJ P. The role of microporous surface area in the gasification of chars from a sub-bituminous coal[J]. Fuel, 1991, 70(9): 1079-1082.
14	YokoyamaS Y, TanakaK I, ToyoshimaI, et al. X-ray photoelectron spectroscopic study of the surface of carbon doped with potassium carbonate[J]. Chemistry Letters, 1980, 16(5): 599-602.
15	KopyscinskiJ, RahmanM, GuptaR, et al. K₂CO₃ catalyzed CO₂ gasification of ash-free coal. Interactions of the catalyst with carbon in N₂ and CO₂ atmosphere[J]. Fuel, 2014, 117(1): 1181-1189.
16	WangY, WangZ, HuangJ, et al. Catalytic gasification activity of Na₂CO₃ and comparison with K₂CO₃ for a high-aluminum coal char[J]. Energy & Fuels, 2015, 29(11): 6988-6998.
17	WangJ, JiangM, YaoY, et al. Steam gasification of coal char catalyzed by K₂CO₃ for enhanced production of hydrogen without formation of methane[J]. Fuel, 2009, 88(9): 1572-1579.
18	ChenS G, YangR T. Unified mechanism of alkali and alkaline earth catalyzed gasification reactions of carbon by CO₂ and H₂O[J]. Energy & Fuels, 1997, 11(2): 421-427.
19	XuK, HuS, SuS, et al. Study on char surface active sites and their relationship to gasification reactivity[J]. Energy & Fuels, 2013, 27(1): 118-125.
20	CerfontainM B, MoulijnJ A. Alkali-catalysed gasification reactions studied by in situ FTIR spectroscopy[J]. Fuel, 1983, 62(2): 256-258.
21	ZhangF, XuD, WangY, et al. CO₂ gasification of Powder River Basin coal catalyzed by a cost-effective and environmentally friendly iron catalyst[J]. Applied Energy, 2015, 145: 295-305.
22	SamsD A, ShadmanF. Catalytic effect of potassium on the rate of char-CO₂ gasification[J]. Fuel, 1983, 62(8): 880-882.
23	SaberJ M, KesterK B, FalconerJ L, et al. A mechanism for sodium oxide catalyzed CO₂ gasification of carbon[J]. Journal of Catalysis, 1988, 109(2): 329-346.
24	WigmansT, ElfringM, MoulijnJ A, et al. On the mechanism of the potassium catalysed gasification of activated carbon: differences in physical behaviour of sodium- and potassium-carbonate[J]. Carbon, 1982, 20(2): 140.
25	MoulijnJ A, KapteijnF. Towards a unified theory of reactions of carbon with oxygen-containing molecules[J]. Carbon, 1995, 33(8): 1155-1165.
26	TahmasebiA, YuJ, HanY, et al. A study of chemical structure changes of Chinese lignite during fluidized-bed drying in nitrogen and air[J]. Fuel Process. Technol., 2012, 101: 85-93.
27	IbarraJ, MuñozE, MolinerR, et al. FTIR study of the evolution of coal structure during the coalification process[J]. Org. Geochem., 1996, 24(6/7): 725-735.
28	ShangJ Y, WolfE E. FTIR studies of potassium catalyst-treated gasified coal chars and carbons[J]. Fuel, 1983, 62(2): 252-255.
29	XieA J, ShenY H, LiX Y, et al. The role of Mg²⁺ and Mg²⁺ /amino acid in controlling polymorph and morphology of calcium carbonate crystal[J]. Materials Chemistry & Physics, 2007, 101(1): 87-92.
30	RamasamyV, RajkumarP, PonnusamyV, et al. Depth wise analysis of recently excavated Vellar river sediments through FTIR and XRD studies[J]. Indian Journal of Physics, 2009, 83(9): 1295-1308.
31	MakreskiP, JovanovskiG, DimitrovskaS, et al. Minerals from Macedonia (): Identification of some sulfate minerals by vibrational (infrared and Raman) spectroscopy[J]. Vibrational Spectroscopy, 2005, 39(2): 229-239.
32	WangJ, DuJ, ChangL, et al. Study on the structure and pyrolysis characteristics of Chinese western coals[J]. Fuel Process. Technol., 2010, 91(4): 430-433.
33	PereiraP, CsencsitsR, SomorjaiG A, et al. Steam gasification of graphite and chars at temperatures <1000 K over potassium-calcium-oxide catalysts[J]. Journal of Catalysis, 1989, 123(2): 463-476.
34	PereiraP, SomorjaiG A, HeinemannH, et al. Catalytic steam gasification of coals[J]. Energy & Fuels, 1992, 6(4): 407-410.
35	JiangM Q, ZhouR, HuJ, et al. Calcium-promoted catalytic activity of potassium carbonate for steam gasification of coal char: influences of calcium species[J]. Fuel, 2012, 99(9): 64-71.
36	BrunoG, BuroniM, CarvaniL, et al. Water-insoluble compounds formed by reaction between potassium and mineral matter in catalytic coal gasification[J]. Fuel, 1988, 67(1): 67-72.

编辑推荐 0

Metrics

阅读次数

全文

576

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
0	0	5	0	0	571

来源	本网站	其他网站

次数	143	433
比例	25%	75%

摘要

378

最新录用	在线预览	正式出版

0	0	378

来源	本网站	其他网站

次数	217	161
比例	57%	43%

[1]	黄琮琪, 吴一梅, 陈建业, 邵双全. 碱性电解水制氢装置热管理系统仿真研究[J]. 化工学报, 2023, 74(S1): 320-328.
[2]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[3]	陈哲文, 魏俊杰, 张玉明. 超临界水煤气化耦合SOFC发电系统集成及其能量转化机制[J]. 化工学报, 2023, 74(9): 3888-3902.
[4]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[5]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[6]	吴雷, 刘姣, 李长聪, 周军, 叶干, 刘田田, 朱瑞玉, 张秋利, 宋永辉. 低阶粉煤催化微波热解制备含碳纳米管的高附加值改性兰炭末[J]. 化工学报, 2023, 74(9): 3956-3967.
[7]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[8]	盛冰纯, 于建国, 林森. 铝基锂吸附剂分离高钠型地下卤水锂资源过程研究[J]. 化工学报, 2023, 74(8): 3375-3385.
[9]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[10]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[11]	韩晨, 司徒友珉, 朱斌, 许建良, 郭晓镭, 刘海峰. 协同处理废液的多喷嘴粉煤气化炉内反应流动研究[J]. 化工学报, 2023, 74(8): 3266-3278.
[12]	涂玉明, 邵高燕, 陈健杰, 刘凤, 田世超, 周智勇, 任钟旗. 钙基催化剂的设计合成及应用研究进展[J]. 化工学报, 2023, 74(7): 2717-2734.
[13]	张琦钰, 高利军, 苏宇航, 马晓博, 王翊丞, 张亚婷, 胡超. 碳基催化材料在电化学还原二氧化碳中的研究进展[J]. 化工学报, 2023, 74(7): 2753-2772.
[14]	余娅洁, 李静茹, 周树锋, 李清彪, 詹国武. 基于天然生物模板构建纳米材料及集成催化剂研究进展[J]. 化工学报, 2023, 74(7): 2735-2752.
[15]	李盼, 马俊洋, 陈志豪, 王丽, 郭耘. Ru/α-MnO₂催化剂形貌对NH₃-SCO反应性能的影响[J]. 化工学报, 2023, 74(7): 2908-2918.

K₂CO₃对兰炭催化气化特性的影响

Catalysis effects of K₂CO₃ for gasification of semi-coke

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 36

相关文章 15

编辑推荐 0

Metrics

本文评价