Rotating gliding arc plasma assisted hydrogen production from methane decomposition in argon
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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。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.
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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)
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)
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
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
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
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
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 Eu/eV gu 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
plasmaKGA
plasmaRGA
plasmaNon-thermal
plasmaTe /eV 1-10 1.0-1.5 1.0-2.0 1.0-3.0 Ne /cm-3 1015-1019 1011-1014 1015 109-1011 Tg /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
gasPower
sourceFlow rate
/(L·min-1)CH4
concentration
/%CH4
conversion
x/%Product selectivity s/% Energy
consumption
/(kJ·L-1)H2 C2H2 [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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