Treatment of biomass tar by CO2 plasma

doi:10.11949/0438-1157.20200879

Abstract

Abstract:

The tar produced in the process of biomass gasification would not only corrode the pipelines and equipment, but also reduce the efficiency of biomass gasification. Traditional methods, such as physical treatment and thermal cracking, have deficiencies which severely restrict their application. This article achieved efficient transformation (carbon yield >90%) from benzene and naphthalene, regarded as model compounds of biomass tar, to syngas using CO₂ plasma on self-designed rotating arc plasma torch, proving the feasibility of CO₂ plasma treatment of biomass tar. Further analysis on the composition of practical biomass tar and the investigation of biomass tar gasification were carried out. Water content in biomass tar could be used as gasification agent and control the H₂/CO scale (0.3—1). The above results provide new ideas for the development of biomass tar harmlessness and resource utilization technology.

Key words: rotating arc plasma, biomass tar, gasification, carbon dioxide, syngas

摘要：

生物质气化过程中副产的焦油不仅有腐蚀设备、堵塞管道等危害，而且会降低生物质气化效率，传统的物理处理与热裂解处理方法存在诸多不足。本文基于旋转弧热等离子体反应装置，以二氧化碳作为等离子介质，选取苯及苯萘混合物作为生物质焦油的模型化合物进行了气化实验，实现了向合成气的高效转化（碳收率可达到90%以上），初步显示了该路线的可行性。进一步分析了真实生物质焦油的物质组成，考察了二氧化碳等离子体对焦油的气化性能，焦油内的水分可作为气化剂，调节合成气中H₂/CO的比例（0.3~1）。上述结果为生物质焦油无害化、资源化利用技术的发展提供了新的思路。

关键词: 旋转弧等离子体, 生物质焦油, 气化, 二氧化碳, 合成气

CLC Number:

TQ 039⁺.3

Ming ZHANG, Lehao LI, Rulong LI, Jianhua WU, Baogen SU, Guangdong WEN, Qiwei YANG, Qilong REN. Treatment of biomass tar by CO₂ plasma[J]. CIESC Journal, 2020, 71(10): 4773-4782.

张铭, 李乐豪, 李如龙, 吴剑骅, 苏宝根, 闻光东, 杨启炜, 任其龙. 二氧化碳等离子体处理生物质焦油[J]. 化工学报, 2020, 71(10): 4773-4782.

Figures/Tables 17

Fig.1 Operation system of 50 kW plasma torch

Table 1 GC analyzing results of product gas

H₂	CO	CO₂	CH₄	C₂H₂	∑C_xH_y(x≥3)
15%~45%	50%~80%	0~10%	<0.01%	<0.01%	<0.01%

Table 2 Effects of CO2 flow rate on benzene gasification

$Q C O 2$ /(m³/h)	Concentration/%			Q_出/(m³/h)		SEC/ (kW·h/m³)	H₂/CO	X/%
$Q C O 2$ /(m³/h)	H₂	CO	CO₂	CO	H₂	SEC/ (kW·h/m³)	H₂/CO	X/%
0.60	31.1	68.9	0	0.84	0.38	11.0	0.45	51.8
0.69	30.3	69.7	0	1.04	0.45	8.94	0.44	60.9
0.78	28.2	71.8	0	1.23	0.48	7.76	0.39	68.6
0.96	22.9	77.1	0	1.73	0.51	5.96	0.30	87.3
1.14	19.5	79.6	0.91	1.78	0.44	6.02	0.24	83.6
1.23	18.3	80.2	1.50	1.66	0.38	6.53	0.23	75.1

Table 2 Effects of CO2 flow rate on benzene gasification

$Q C O 2$ /(m³/h)	Concentration/%			Q_出/(m³/h)		SEC/ (kW·h/m³)	H₂/CO	X/%
$Q C O 2$ /(m³/h)	H₂	CO	CO₂	CO	H₂	SEC/ (kW·h/m³)	H₂/CO	X/%
0.60	31.1	68.9	0	0.84	0.38	11.0	0.45	51.8
0.69	30.3	69.7	0	1.04	0.45	8.94	0.44	60.9
0.78	28.2	71.8	0	1.23	0.48	7.76	0.39	68.6
0.96	22.9	77.1	0	1.73	0.51	5.96	0.30	87.3
1.14	19.5	79.6	0.91	1.78	0.44	6.02	0.24	83.6
1.23	18.3	80.2	1.50	1.66	0.38	6.53	0.23	75.1

Fig.2 Effects of CO2 flow rate on gas composition

Fig.3 Effects of CO2 flow rate on SEC and X

Table 3 Effects of input power on benzene gasification

Input power/ kW	Concentration/%			Q_出/(m³/h)		SEC/ (kW·h/m³)	H₂/CO	X/%
Input power/ kW	H₂	CO	CO₂	CO	H₂	SEC/ (kW·h/m³)	H₂/CO	X/%
10.31	18.8	80.3	0.95	1.27	0.30	6.59	0.23	65.1
11.86	20.5	78.4	1.11	1.56	0.41	6.04	0.26	80.1
12.96	19.9	79.3	0.84	1.81	0.45	5.73	0.25	92.8
14.69	19.7	79.4	0.94	1.70	0.42	6.94	0.25	89.1
16.10	20.0	79.2	0.86	1.66	0.42	7.74	0.25	85.3
17.60	21.0	78.6	0.41	1.54	0.41	9.02	0.27	78.5

Fig.4 Effects of input power on gas composition

Fig.5 Effects of input power on SEC and X

Fig.6 X for the gasification of benzene-naphthalene mixtures with different naphthalene mass fractions

Fig.7 SEC for the gasification of benzene-naphthalene mixtures with different naphthalene mass fraction

Fig.8 FTIR spectra of biomass tar

Table 4 Identifiable component analysis of biomass tar by GC/MS

No.	Retention time/min^①	Retention time ST/min^②	Compound	Molecular formula	Mole fraction/%
1	2.336	2.334	苯并呋喃	C₈H₆O	2.10
2	3.451	3.448	萘	C₁₀H₈	31.52
3	4.059	4.065	2-甲基萘	C₁₁H₁₀	6.23
4	4.142	4.168	1-甲基萘	C₁₁H₁₀	4.24
5	4.459	4.445	联苯	C₁₂H₁₀	1.11
6	4.713	4.697	2-乙烯基萘	C₁₂H₁₀	0.98
7	4.810	4.808	苊烯	C₁₂H₈	8.26
8	5.096	5.073	苯并呋喃	C₁₂H₈O	0.63
9	5.342	5.332	芴	C₁₃H₁₀	3.92
10	6.028	6.016	菲	C₁₄H₁₀	4.62
11	6.079	6.052	蒽	C₁₄H₁₀	1.80
12	7.148	7.139	芘	C₁₆H₁₀	1.92

Fig.9 GC/MS total ion chromatogram of biomass tar

Table 5 Effects of CO2 flow rate on the gasification of the mixture of biomass tar and benzene

$Q C O 2$ /(m³/h)	Concentration/%			Q_出/(m³/h)		SEC/ (kW·h/m³)	H₂/CO
$Q C O 2$ /(m³/h)	H₂	CO	CO₂	CO	H₂	SEC/ (kW·h/m³)	H₂/CO
0.43	30.8	69.2	0	0.67	0.30	14.1	0.44
0.51	30.2	69.8	0	0.87	0.38	10.9	0.43
0.60	26.0	72.8	1.26	1.02	0.36	9.83	0.36
0.69	24.7	70.5	4.81	1.10	0.39	9.13	0.35
0.86	20.6	74.3	5.05	1.21	0.34	8.80	0.28
0.95	17.8	73.9	8.34	1.19	0.29	9.22	0.24

Table 5 Effects of CO2 flow rate on the gasification of the mixture of biomass tar and benzene

$Q C O 2$ /(m³/h)	Concentration/%			Q_出/(m³/h)		SEC/ (kW·h/m³)	H₂/CO
$Q C O 2$ /(m³/h)	H₂	CO	CO₂	CO	H₂	SEC/ (kW·h/m³)	H₂/CO
0.43	30.8	69.2	0	0.67	0.30	14.1	0.44
0.51	30.2	69.8	0	0.87	0.38	10.9	0.43
0.60	26.0	72.8	1.26	1.02	0.36	9.83	0.36
0.69	24.7	70.5	4.81	1.10	0.39	9.13	0.35
0.86	20.6	74.3	5.05	1.21	0.34	8.80	0.28
0.95	17.8	73.9	8.34	1.19	0.29	9.22	0.24

Fig.10 Effects of CO2 flow rate on the gasification of the mixture of biomass tar and benzene

Table 6 Comparison of optimal gasification results among mixtures with different water contents

含水率/%	$Q C O 2$ /(m³/h)	Concentration/%			SEC/ (kW·h/m³)	H₂/CO
含水率/%	$Q C O 2$ /(m³/h)	H₂	CO	CO₂	SEC/ (kW·h/m³)	H₂/CO
13.3	0.69	24.7	70.5	4.81	9.13	0.35
27.1	0.43	37.3	61.9	0.81	8.88	0.60
46.0	0.43	42.8	53.7	3.58	9.11	0.80

Table 6 Comparison of optimal gasification results among mixtures with different water contents

含水率/%	$Q C O 2$ /(m³/h)	Concentration/%			SEC/ (kW·h/m³)	H₂/CO
含水率/%	$Q C O 2$ /(m³/h)	H₂	CO	CO₂	SEC/ (kW·h/m³)	H₂/CO
13.3	0.69	24.7	70.5	4.81	9.13	0.35
27.1	0.43	37.3	61.9	0.81	8.88	0.60
46.0	0.43	42.8	53.7	3.58	9.11	0.80

Fig.11 CO and H2 concentration in product gas for the gasification of mixtures with different water contents

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Treatment of biomass tar by CO₂ plasma

二氧化碳等离子体处理生物质焦油

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