废轮胎热解炭低温催化焦油重整制备富氢气体的研究

doi:10.11949/0438-1157.20190831

摘要/Abstract

摘要：

以全钢型废旧轮胎为原料，通过热解、活化、浸渍、焙烧的流程制备了三种热解炭催化剂，分别为轮胎热解炭（Raw char）、轮胎热解活性炭（AC）和负载Zn的活性炭（Zn/AC）。采用N₂吸/脱附、SEM、EDS、XRD等表征方法对催化剂进行了一系列表征和分析，发现CO₂/H₂O活化可显著提高催化剂BET比表面积，最高可达380 m²·g^-1，有效改善催化剂表面结构性质，同时浸渍法使催化剂表面负载大量ZnO活性位。对三种催化剂在纤维素热解焦油重整制氢过程中的催化性能进行了研究，发现Raw char（600℃）具有最佳催化效果，相较于空白组（500℃），热解气中H₂体积分数提高了12.4%，达到19.3%，其次为Zn/AC（500℃）组的17.8%，实现了低温下催化纤维素焦油热解制得高产率H₂。

关键词: 废旧轮胎, 催化剂载体, 纤维素, 催化重整, 热解, 制氢

Abstract:

Three pyrolysis carbon catalysts were prepared by pyrolysis, activation, impregnation and calcination using all-steel waste tires as raw materials, namely Raw char, raw pyrolytic activated carbon (AC) and Zn modified activated carbon (Zn/AC). The catalysts were characterized by N₂ adsorption/desorption, SEM, EDS, XRD and other characterization methods. It was found that CO₂/H₂O activation significantly increase the BET specific surface area of the catalyst up to 380 m²·g^-1, effectively improving the surface structure of the catalyst. Meanwhile, a large number of ZnO was loaded onto the surface by impregnation method. The catalytic performance of three catalysts was studied in the process of cellulose pyrolysis tar reforming to produce hydrogen. Results indicated that Raw char (600℃) has the best catalytic effect compared with the blank group (500℃). The volume fraction of H₂ in gas production increased by 12.4% to 19.3%, followed by 17.8% of the Zn/AC (500℃) group, which achieved high yield of H₂ by catalyzing cellulose tar at low temperatures.

Key words: waste tire, catalyst support, cellulose, catalytic reforming, pyrolysis, hydrogen production

中图分类号:

TE 992.3

杨殿才, 潘宇涵, 黄群星, 蒋旭光, 王飞, 严建华. 废轮胎热解炭低温催化焦油重整制备富氢气体的研究[J]. 化工学报, 2020, 71(2): 642-650.

Diancai YANG, Yuhan PAN, Qunxing HUANG, Xuguang JIANG, Fei WANG, Jianhua YAN. Study on catalytic reforming of tar at low temperature to produce hydrogen-rich gas by tire pyrolysis char[J]. CIESC Journal, 2020, 71(2): 642-650.

图/表 13

图1 催化剂制备及纤维素热解焦油在线催化重整流程图

Fig.1 Flow chart of catalyst preparation and cellulose pyrolytic tar in-situ cracking

表1 废旧轮胎工业分析和元素分析

Table 1 Proximate and ultimate analysis of waste tire

Proximate analysis/%(mass)				Ultimate analysis/%(mass)
M_ad	A_ad	V_ad	FC_ad	C_ad	H_ad	O_ad^①	N_ad	S_ad
1.02	10.39	62.10	26.49	75.51	5.11	4.95	0.72	2.30

图2 不同升温速率下废旧轮胎的热重(TG)和微分热重 (DTG) 曲线

Fig.2 TG and DTG curves of waste tire at different heating rates

图3 生物质焦油在线催化重整反应装置

Fig.3 Schematic layout for in-situ catalytic reforming of biomass tar1—N2;2—flowmeter;3—cellulose;4—catalyst;5—tubular fumace;6—gas-sealed bottle;7—gas chromatograph

图4 氮气等温吸附/脱附曲线

Fig.4 Nitrogen adsorption/desorption isotherms

表2 比表面积、孔体积及平均孔径

Table 2 Specific surface area, total pore volume and average pore size

Sample	S_BET/ (m²·g^-1)	S_mic/ (m²·g^-1)	S_mes/ (m²·g^-1)	V_total/ (cm³·g^-1)	D_avg/nm
Raw char	65	7	58	0.14	23.50
AC	380	180	200	0.47	13.28
Zn/AC	189	95	94	0.23	20.73
Zn/AC-used	94	21	73	0.16	20.76

图5 Raw char, AC, Zn/AC和Zn/AC-used的SEM和EDS结果

Fig.5 SEM and EDS results of Raw char, AC, Zn/AC and Zn/AC-used

图6 Raw char,AC,Zn/AC和Zn/AC-used的XRD谱图

Fig.6 XRD patterns of Raw char, AC, Zn/AC and Zn/AC-used

图7 不同催化剂及温度工况下气体产物产率

Fig.7 Yield of gas under different catalyst and temperature conditions

图8 不同催化剂及温度工况下氢气产率

Fig.8 Yield of hydrogen under different catalyst and temperature conditions

图9 不同催化剂及温度工况下氢气体积分数

Fig.9 Volume fraction of H2 under different catalyst and temperature conditions

图10 使用后Zn/AC和Ni/Al2O3的催化性能

Fig.10 Catalytic performance of used Zn/AC and Ni/Al2O3

图11 废旧轮胎热解炭催化剂改性提质过程及其催化机理

Fig.11 Modification and upgrading of waste tire carbon and its catalytic mechanism

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