旋转滑动弧氩等离子体裂解甲烷制氢

张浩; 朱凤森; 李晓东; 吴昂键; 薄拯; 岑可法

旋转滑动弧氩等离子体裂解甲烷制氢

基金项目:

国家自然科学基金 51576174

高等学校博士学科点专项科研基金 20120101110099

中央高校基本科研业务费专项资金 2015FZA4011

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出版历程
- 收稿日期: 2015-06-09
- 修回日期: 2015-09-14

Rotating gliding arc plasma assisted hydrogen production from methane decomposition in argon

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Corresponding author: Tel: 0571-87952037, Fax: 0571-87952438, E-mail: lixd@zju.edu.cn

摘要

摘要: 采用切向气流和磁场协同驱动的旋转滑动弧氩等离子体, 先通过光谱分析法计算了其电子温度和电子密度, 了解其物理特性, 将其应用于甲烷裂解制氢, 研究了进气流量和CH₄/Ar比对反应效果的影响。结果表明, 该滑动弧系统电子温度为1.0-2.0 eV, 电子密度高达10¹⁵ cm^-3, 是介于热与低温等离子体之间的一种等离子体形式, 具有独特的物理特性, 可以在达到较高反应效率的同时, 保持较大的处理量; 在CH₄裂解制氢实验中, CH₄转化率可达22.1%-70.2%, 并随进气流量和CH₄/Ar比的增大均逐渐降低; H₂选择性为21.2%-61.2%, 并随进气流量的增大先基本不变后有所增大, 随CH₄/Ar比的增大逐渐降低; 与应用于甲烷裂解的不同形式的低温等离子体对比 (如微波、射频、介质阻挡放电等) 可以发现, 旋转滑动弧在获得较高甲烷转化率、较高H₂选择性和较低制氢能耗的同时, 还可以保持较大的处理量, 即进气流量可达6-20 L/min。
- 旋转滑动弧 /
- 等离子体 /
- 光谱分析 /
- 甲烷裂解 /
- 氢气
Abstract: A kind of rotating gliding arc (RGA) argon plasma co-driven by tangential flow and magnetic field was investigated and used for hydrogen production from methane decomposition.In order to obtain insights into the physical characteristics of the RGA plasma, optical emission spectroscopy (OES) analysis was used to determine the electron temperature and electron density.In addition, the effects of feed flow rate and CH₄/Ar ratio on the performance of the methane decomposition process in this RGA plasma were also investigated.Results have shown that, the RGA plasma is a kind of unique plasma between thermal and non-thermal plasma, with electron temperature of 1.0-2.0 eV and electron density of 10¹⁵ cm^-3.In this system, the CH₄ conversion could be 22.1%-70.2% and it increased with the increase of flow rate or CH₄/Ar ratio.The H₂ selectivity varied from 21.2% to 61.2%, and with the augment of flow rate, the H₂ selectivity first varied slightly and then increased.A comparison of different non-thermal plasmas (e.g., microwave, radio frequency, and dielectric barrier discharge) showed that the RGA plasma could provide a relatively high CH₄ conversion and H₂ selectivity, as well as a relatively low energy consumption for H₂ production, while maintaining a high flow rate (i.e., processing capacity) of 6-20 L/min.
- rotating gliding arc (RGA) /
- plasma /
- optical emission spectroscopy (OES) /
- methane decomposition /
- hydrogen

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图 1 实验装置系统流程示意图

Figure 1. Schematic of experimental setup

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图 2 旋转滑动弧反应器结构示意图

Figure 2. Schematic of the RGA reactor

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图 3 Ar 696.54nm谱线典型的玻尔兹曼曲线 (Q=2和4L/min)

Figure 3. Typical boltzmann plot of Ar 696.54nm (Q=2 and 4L/min)

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图 4 Ar 696.54nm谱线典型的Voigt拟合结果 (Q=2L/min)

Figure 4. Typical voigt fit of spectral line in Ar 696.54nm (Q=2L/min)

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图 5 电子温度和电子密度随进气流量的变化

Figure 5. Electron temperature and density as a function of feed flow rate

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图 6 CH₄转化率和输入能量密度随进气流量的变化

Figure 6. CH₄ conversion and input energy density as a function of feed flow rate

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图 7 产物选择性和制氢电耗随进气流量的变化

Figure 7. Products' selectivities and specific energy consumption as a function of feed flow rate

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图 8 输入能量密度、CH₄转化率、产物选择性和制氢电耗随CH₄/Ar比的变化

Figure 8. Input energy density, CH₄ conversion and products' selectivities as a function of CH₄/Ar ratio

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表 1 采用的谱线及其光谱学参数

Table 1. Selected spectral lines and parameters

λ/nm	A/s^-1	E_u/eV	g_u
357.66	2.75×10⁸	23.01	8
427.22	7.97×10⁵	14.52	3
430.01	3.77×10⁵	14.51	5
433.20	1.92×10⁷	19.31	2
442.60	8.17×10⁷	19.55	6
476.49	6.40×10⁷	19.87	4
518.77	1.38×10⁶	15.30	5
696.54	6.39×10⁶	13.32	3
706.72	3.80×10⁶	13.30	5
727.29	1.83×10⁶	13.33	3
738.40	8.47×10⁶	13.30	5

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表 2 滑动弧氩等离子体与典型热和低温等离子体特性对比^[25]

Table 2. Typical parameters for the GAD, thermal and non-thermal plasmas^[25]

Parameter	Thermal plasma	KGA plasma	RGA plasma	Non-thermal plasma
T_e /eV	1-10	1.0-1.5	1.0-2.0	1.0-3.0
N_e /cm^-3	10¹⁵-10¹⁹	10¹¹-10¹⁴	10¹⁵	10⁹-10¹¹
T_g /K	10⁴-10⁵	300-3000	480	300-600

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表 3 不同低温等离子体用于甲烷裂解效果对比

Table 3. Comparison of decomposition of methane assisted by different non-thermal plasmas

Reference	Reactor	Carrier gas	Power source	Flow rate /(L·min^-1)	CH₄ concentration /%	CH₄ conversion x/%	Product selectivity s/%		Energy consumption /(kJ·L^-1)
Reference	Reactor	Carrier gas	Power source	Flow rate /(L·min^-1)	CH₄ concentration /%	CH₄ conversion x/%	H₂	C₂H₂	Energy consumption /(kJ·L^-1)
^[32]	microwave	N₂	3-5kW	93.75-225	22.2-46.7	9.5-13.2	-	-	4.3-32.5
^[33]	microwave	-	200W	0.009-0.047	100	85.7-93.8	-	75.4-97.4	-
^[34]	RF	Ar	50-120W	0.05	5-20	30.2-89.0	-	13.1-24.3	-
^[35]	DBD	-	AC	0.01-0.047	100	≈0.5-3.7	-	≈10	-
	DBD	He	12-23kV	0.1	10-37	≈0.05-3.6	-	-	-
^[36]	DBD					4-25	-	≈2	-
	corona	-	DC, 15kV	0.006-0.03	100	4-25	-	15	-
	spark					4-65	-	85	-
^[37]	pulsed	-	12W	0.01-0.037	100	29-69	19-51	22-54	43-73.1
	spark
^{[8, 9]}	KGA	Ar	4-12W,	0.125-0.2	5-35	≈15-45	≈70-78	70-90	-
			50Hz
		-	110-190W,	1.5	100	40-50	≈32-40	20	-
			10-20kHz
^[10]	KGA	Ar or	120-170W	1	15-100	≈50-62	≈45-70	≈6-20	-
		He	20kHz
		N₂	135-163W	1	15-100	≈45-65	≈40-65	≈20-60	-
			20kHz
^[7]	KGA	Ar	17W, 10kHz	0.6 or 1	4	≈55-75	-	≈35	-
This work	RGA	Ar	DC, 10kV	6-20	4.8-28.6	22.1-70.2	21.2-61.2	10.2-18.0	16.3-30.9

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