Catalytic effect of biomass ash on the hydrogasification of coal char
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摘要: 以小麦秸秆、马尾藻和山苦荬等三种富含碱金属和碱土金属的生物质为原料，研究了在500、600和815℃下制得的生物质灰对神府煤焦加氢气化的催化作用。结果表明，随着制灰温度由500℃升高至815℃，灰产量减少，且灰中的碱金属和氯元素的含量降低；当制灰温度达到815℃，生物质灰出现明显的熔融现象；600℃灰样对神府煤焦加氢气化具有较好的催化作用，催化效果随灰样添加比例增大而增强。山苦荬灰催化作用较好，而马尾藻灰催化作用较弱。小麦秸秆灰中较高的硅含量和马尾藻灰中较高的氯含量是其催化作用较弱的主要原因；氯元素会加剧碱金属的挥发，弱化与其结合的碱金属的催化效果，对碱金属催化所产生的抑制作用比相同摩尔数的硅更加明显。Abstract: Biomass ashes were prepared from three rich in alkaline and alkaline earth metal materials, viz., wheat straw (WS), sea grape (SG) and ixeris chinensis (IC), at different temperatures of 500, 600 and 815℃; the catalytic effect of biomass ash on the hydro-gasification of Shenfu coal (SF) char was then investigated. The results show that the ash yield and the content of alkali metals and chlorine reduce with increasing ashing temperature from 500 to 815℃; significant ash melting can be observed at high temperature near 815℃. The biomass ashes obtained at 600℃ exhibits the best catalytic effect on the gasification of coal char; the more the ash is loaded with the char, the stronger exhibit the promoting effect on the gasification is. The ash from IC performs best in catalyzing the coal char gasification, whereas the SG ash is the worst catalyst. The high content of silica in the WS ash and the high content of chlorine in the SG ash may explain their poor catalytic effect on the char gasification; chlorine can aggravate the volatilization of alkali metal and lead to a severer inhibiting effect on the coal char hydrogasification than silica with the same molar quantity.
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Key words:
- coal char /
- hydro-gasification /
- biomass ash /
- silica /
- chlorine
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图 1 固定床反应系统示意图
Figure 1 Schematic diagram of the fixed-bed reactor system
1: mass flow controller; 2: pressure gage; 3: flow meter; 4: flange; 5: thermocouple; 6: metal mesh; 7: electric furnace; 8: corundum tube; 9: liquid/gas separator; 10: gas drying bottle; 11: non-return value; 12: gas analyzer; 13: computer
图 2 不同温度下山苦荬灰样的XRD谱图
Figure 2 XRD patterns of IC ash obtained under different temperatures
图 4 负载600、815 ℃灰样下神府煤焦加氢气化气体产量
Figure 4 Gas yields from the gasification of SF coal in the presence of various ashes (WS, SG and IC) obtained at 600 and 815 ℃
图 5 负载不同种类生物质灰下神府煤焦加氢气化的甲烷释放速率
Figure 5 CH4 release rate for the hydrogasification of SF coal with the addition of different biomass ashes
图 6 负载不同生物质灰下神府煤焦加氢气化的气体产量
Figure 6 Gas yields from the gasification of coal in the presence of various biomass ashes
图 7 负载掺混Cl和SiO2的钾基催化剂下神府煤焦加氢气化的气体产量
Figure 7 Gas yields from the gasification of SF coal when potassium-based catalysts were loaded with Cl and SiO2
图 8 神府煤焦及其负载不同含量ICA下气化残渣的SEM照片
Figure 8 SEM images of SF coal char and the residues from the gasification with various amount of IC ash
图 9 负载不同比例生物质灰下神府煤焦加氢气化的气体产量
Figure 9 Gas yields as the function of ash loading in the feed mixture
表 1 样品的工业分析和元素分析
Table 1 Proximate and ultimate analyses of Shenfu coal (SF), wheat straw (WS), sea grape (SG) and ixeris chinensis (IC)
Sample Proximate analysis wd /% Ultimate analysis wd /% V FC A C H N S O* SF 33.29 58.65 8.06 74.20 4.21 0.97 0.63 11.93 IC 64.63 10.74 24.63 32.58 3.83 3.25 0.49 35.22 WS 72.07 17.91 10.02 38.76 5.91 0.83 5.33 39.15 SG 48.85 11.60 37.93 23.74 3.21 0.98 1.26 32.88 *: O was calculated by the difference 
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表 2 不同灰化温度下生物质灰灰收率
Table 2 Ash yield of various biomass materials obtained at different temperatures
t /℃ Yield w/% WSA SGA ICA 500 11.51 48.00 20.80 600 11.46 43.10 15.49 815 10.20 38.90 12.60
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表 3 生物质灰成分分析
Table 3 XRF results of ashes obtained from various biomass materials at different temperatures
Sample Ashing temp. t/ ℃ Content w/% Al2O3 CaO Fe2O3 SiO2 MgO Na2O K2O Cl SO3 undet. WSA 500 2.02 8.58 1.19 44.05 2.58 0.51 24.56 7.89 6.89 1.73 600 2.67 8.98 1.85 45.31 3.72 0.59 22.11 6.43 6.64 1.70 815 2.86 10.89 1.30 45.60 3.41 0.70 19.06 3.76 10.08 2.34 SGA 500 1.10 11.89 1.06 4.41 2.46 19.66 21.10 30.78 6.99 0.55 600 1.85 17.29 0.97 8.41 6.41 16.21 15.08 23.64 9.71 0.43 815 1.95 18.82 1.14 9.10 7.07 16.03 12.56 20.22 9.55 3.56 ICA 500 1.01 11.41 0.98 4.08 6.66 6.92 35.40 21.30 6.60 5.64 600 1.04 8.73 0.77 7.80 8.44 4.07 32.93 17.84 9.21 9.17 815 2.64 17.85 1.35 10.58 9.68 3.66 24.06 12.97 9.22 7.99
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