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

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K₂CO₃对兰炭催化气化特性的影响

Catalysis effects of K₂CO₃ for gasification of semi-coke

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