二氧化碳等离子体处理生物质焦油

doi:10.11949/0438-1157.20200879

摘要/Abstract

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

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

中图分类号:

TQ 039⁺.3

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.

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.

图/表 17

图1 50 kW等离子炬实验系统1—阴极; 2—直流电源; 3—阳极; 4—励磁线圈; 5—热交换器; 6—气相色谱; 7—蠕动泵

Fig.1 Operation system of 50 kW plasma torch

表1 裂解气气相色谱分析结果

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%

表2 CO2流量对苯气化过程的影响

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

表2 CO2流量对苯气化过程的影响

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

图2 CO2流量对产品气组成的影响

Fig.2 Effects of CO2 flow rate on gas composition

图3 CO2流量对比能耗和碳转化率的影响

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

表3 输入功率对苯气化过程的影响

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

图4 输入功率对产品气组成的影响

Fig.4 Effects of input power on gas composition

图5 输入功率对比能耗和碳转化率的影响

Fig.5 Effects of input power on SEC and X

图6 不同萘质量分数的苯萘混合物气化实验的碳转化率

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

图7 不同萘质量分数的苯萘混合物气化实验的比能耗

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

图8 生物质焦油傅里叶红外光谱图

Fig.8 FTIR spectra of biomass tar

表4 生物质焦油可辨识化学成分GC/MS分析结果

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

图9 生物质焦油总离子色谱图

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

表5 CO2流量对焦油-苯混合物气化过程的影响

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

表5 CO2流量对焦油-苯混合物气化过程的影响

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

图10 CO2流量对混合物气化的影响实验

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

表6 不同含水率混合物的最优结果对比

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

表6 不同含水率混合物的最优结果对比

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

图11 不同含水率的混合物气化产品气中CO与H2浓度

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

参考文献 34

1	王久臣, 戴林, 田宜水, 等. 中国生物质能产业发展现状及趋势分析[J]. 农业工程学报, 2007, 23(9): 276-282.
	Wang J C, Dai L, Tian Y S, et al. Analysis of the development status and trends of biomass energy industry in China [J]. Transactions of the CSAE, 2007, 23(9): 276-282.
2	李景明, 薛梅. 中国生物质能利用现状与发展前景[J]. 农业科技管理, 2010, 29(2): 1-4.
	Li J M, Xue M. Current status and development prospects of biomass energy utilization in China [J]. Management of Agricultural Science and Technology Energy, 2010, 29(2): 1-4.
3	许小骏. 林业生物质能源发展现状及展望[J]. 山西农业科学, 2008, 36(8): 88-89.
	Xu X J. Development and prospects of forestry biological energy [J]. Journal of Shanxi Agricultural Sciences, 2008, 36(8): 88-89.
4	陈冠益, 高文学, 颜蓓蓓, 等. 生物质气化技术研究现状与发展[J]. 燃气气源与加工利用, 2006, 26(7): 20-26.
	Chen G Y, Gao W X, Yan B B, et al. Present research status and development of biomass gasification technologies [J]. Gas Source and Process and Utilization, 2006, 26(7): 20-26.
5	边轶, 刘石彩, 简相坤. 生物质热解焦油的性质与化学利用研究现状[J]. 生物质化学工程, 2011, 45(2): 51-55.
	Bian Y, Liu S C, Jian X K. The state art of view of research progress on characteristics and chemical utilization of tar from biomass pyrolysis [J]. Biomass Chemical Engineering, 2011, 45(2): 51-55.
6	鲍振博, 靳登超, 刘玉乐, 等. 生物质气化中焦油的产生及处理方法[J]. 农机化研究, 2011, 33(8): 172-176.
	Bao Z B, Jin D C, Liu Y L, et al. Generation and treatment of tar in biomass gasification gas [J]. Journal of Agricultural Mechanization Research, 2011, 33(8): 172-176.
7	吴文广, 罗永浩, 陈祎, 等. 生物质焦油净化方法研究进展[J]. 工业加热, 2008, 37(2): 1-5.
	Wu W G, Luo Y H, Chen Y, et al. The progress in tar reduction method research [J]. Industrial Heating, 2008, 37(2): 1-5.
8	袁惠新, 王宁, 付双成, 等. 生物质焦油的特性及其去除方法的研究现状[J]. 过滤与分离, 2011, (3): 45-48.
	Yuan H X, Wang N, Fu S C, et al. Research on characteristics of biomass tar and the methods of its removal [J]. Journal of Filtration & Separation, 2011, (3): 45-48.
9	吴悠, 赵立欣, 孟海波, 等. 生物质热解焦油脱除方法研究进展[J]. 化工环保, 2016, 36(1): 17-21.
	Wu Y, Zhao L X, Meng H B, et al. Research progress on removal methods of biomass pyrolysis tar[J]. Chemical Environmental Protection, 2016, 36(1): 17-21.
10	马帅, 胡笑颖, 董长青, 等. 生物质焦油模型化合物脱除研究进展[J]. 林产化学与工业, 2019, 39(4): 1-8.
	Ma S, Hu X Y, Dong C Q, et al. Research progress in the removal of biomass tar model compounds[J]. Chemistry and Industry of Forest Products. 2019, 39(4): 1-8.
11	孙云娟, 蒋剑春. 生物质气化过程中焦油的去除方法综述[J]. 生物质化学工程, 2006, 40(2): 31-35.
	Sun Y J, Jiang J C. A review of measures for tar elimination in biomass gasification processes [J]. Biomass Chemical Engineering, 2006, 40(2): 31-35.
12	鲍振博, 靳登超, 刘玉乐, 等. 生物质气化中焦油的产生及其危害性[J]. 安徽农业科学, 2011, 39(4): 2243-2244.
	Bao Z B, Jin D C, Liu Y L, et al. Tar generation and its harmfulness in the process of biomass gasification [J]. Journal of Anhui Agricultural Sciences, 2011, 39(4): 2243-2244.
13	刘玉环, 朱普琪, 王允圃, 等. 生物质气化焦油处理技术的最新研究进展[J]. 现代化工, 2013, 33(11): 24-29.
	Liu Y H, Zhu P Q, Wang Y P, et al. Advance in tar removal technology of biomass gasification [J]. Modern Chemical Industry, 2013, 33(11): 24-29.
14	Rabou L. Biomass tar recycling and destruction in a CFB gasifier [J]. Fuel, 2005, 84(5): 577-581.
15	Seshadri K S, Shamsi A. Effects of temperature, pressure, and carrier gas on the cracking of coal tar over a char-dolomite mixture and calcined dolomite in a fixed-bed reactor [J]. Industrial & Engineering Chemistry Research, 1998, 37(10): 3830-3837.
16	Heo D H, Lee R, Hwang J H, et al. The effect of addition of Ca, K and Mn over Ni-based catalyst on steam reforming of toluene as model tar compound [J]. Catalysis Today, 2016, 265: 95-102.
17	Behnia I, Yuan Z, Charpentier P, et al. Production of methane and hydrogen via supercritical water gasification of renewable glucose at a relatively low temperature: effects of metal catalysts and supports [J]. Fuel Processing Technology, 2016, 143: 27-34.
18	Oh G, Park S Y, Seo M W, et al. Ni/Ru–Mn/Al₂O₃ catalysts for steam reforming of toluene as model biomass tar [J]. Renewable Energy, 2016, 86: 841-847.
19	Nestler F, Burhenne L, Amtenbrink M J, et al. Catalytic decomposition of biomass tars: the impact of wood char surface characteristics on the catalytic performance for naphthalene removal [J]. Fuel Processing Technology, 2016, 145: 31-41.
20	Nair S A, Pemen A J M, Yan K, et al. Tar removal from biomass-derived fuel gas by pulsed corona discharges [J]. Fuel Processing Technology, 2003, 84(1): 161-173.
21	Fourcault A, Marias F, Michou U. Modelling of thermal removal of tars in a high temperature stage fed by a plasma torch [J]. Biomass and Bioenergy, 2010, 34(9): 1363-1374.
22	Nunnally T, Tsangaris A, Rabinovich A, et al. Gliding arc plasma oxidative steam reforming of a simulated syngas containing naphthalene and toluene [J]. International Journal of Hydrogen Energy, 2014, 39(23): 11976-11989.
23	Chun Y N, Kim S C, Yoshikawa K. Decomposition of benzene as a surrogate tar in a gliding arc plasma [J]. Environmental Progress & Sustainable Energy, 2013, 32(3): 837-845.
24	Jzmroz P, Kordylewski W, Wnukowski M. Microwave plasma application in decomposition and steam reforming of model tar compounds [J]. Fuel Processing Technology, 2018, 169: 1-14.
25	Rodrigo M E, Manoel F M N, Argemiro S S S, et al. Tar reforming under a microwave plasma torch [J]. Energy & Fuels, 2013, 27: 1174-1181.
26	Zhu T, Li J, Jin Y, et al. Decomposition of benzene by non-thermal plasma processing: photocatalyst and ozone effect [J]. International Journal of Environmental Science & Technology, 2008, 5(3): 375-384.
27	Saleem F, Zhang K, Harvety A. Role of CO₂ in the conversion of toluene as a tar surrogate in a non-thermal plasma dielectric barrier discharge reactor[J]. Energy & Fuels, 2018, 32(4): 5164-5170.
28	Liu L, Wang Q, Song J, et al. Dry reforming of model biomass pyrolysis products to syngas by dielectric barrier discharge plasma[J]. International Journal of Hydrogen Energy, 2018, 43(22): 10281-10293.
29	Saleem F, Zhang K, Harvety A. Temperature dependence of non-thermal plasma assisted hydrocracking of toluene to lower hydrocarbons in a dielectric barrier discharge reactor[J]. Chemical Engineering Journal, 2019, 356: 1062-1069.
30	Wang B, Yao S, Peng Y, et al. Toluene removal over TiO₂-BaTiO₃ catalysts in an atmospheric dielectric barrier discharge[J]. Journal of Environmental Chemical Engineering, 2018, 6(4): 3819-3826.
31	王青. 微波诱导金属放电催化转化生物质焦油的研究[D]. 济南: 山东大学, 2018.
	Wang Q. Study on catalytic conversion of biomass tar by microwave induced metal discharge[D]. Jinan: Shandong University, 2018.
32	甘蓉丽, 罗光前, 许洋, 等. 低温等离子体协同铜铈催化剂脱除甲苯[J]. 化工进展, 2018, 37(9): 3416-3423.
	Gan R L, Luo G Q, Xu Y, et al. Low temperature plasma collaborative copper cerium catalyst removal of toluene[J]. Chemical Industry and Engineering Progress, 2018, 37(9): 3416-3423.
33	Devi L, Ptasinski K J, Janssen F J J G, et al. Catalytic decomposition of biomass tars: use of dolomite and untreated olivine [J]. Renewable Energy, 2005, 30(4): 565-587.
34	Chun Y N, Kim S C, Yoshikawa K. Destruction of anthracene using a gliding arc plasma reformer [J]. Korean Journal of Chemical Engineering, 2011, 28(8): 1713-1720.

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