Preparation and characterization of Ni/TPC catalyst and applied in straw pyrolysis gas reforming
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摘要: 以废弃汽车外轮胎热解后的副产物轮胎热解焦（Tyre pyrolysis char，TPC）为原料，利用均匀沉淀法制备以轮胎焦为载体的负载型Ni/TPC催化剂，采用EDX、SEM、XRD、TG、BET手段对催化剂进行了表征与分析，同时使用管式炉测试了Ni/TPC催化剂在秸秆热解燃气重整中的催化性能，并考察了热解温度、保温时间、镍负载量及催化时间对秸秆热解燃气重整效果的影响。研究结果表明，TPC富含焦和金属，Ni/TPC催化剂分散均匀，热稳定性好，比表面积为62 m2/g。催化剂活性测试显示，Ni/TPC催化剂用于作物秸秆热解燃气重整具有很强的催化活性，可显著提高燃气中可燃气体含量；热解温度在750℃、保温时间10 min、30%的Ni负载量时Ni/TPC催化剂的催化效率最高，连续使用850 min后，燃气中的H2含量仍相对提高到50%以上，长时间使用后活性结构由Ni3ZnC0.7转变成FeNi3，催化活性依然较强且趋于稳定，TPC可以作为良好的新型镍基催化剂载体。Abstract: Tire pyrolysis char (TPC) was used as a carrier to prepare Ni/TPC catalyst by homogeneous precipitation method. The characteristic of synthetic catalyst was determined by EDX, SEM, XRD, TG and BET. Meanwhile, the performance of Ni/TPC catalyst including reforming temperature, holding time, nickel loading and usage time on the straw pyrolysis gas reforming was investigated in a tube furnace. The results showed that TPC was rich in char and metal. Ni was well loaded on TPC which had a good thermal stability with a specific surface area of 62 m2/g. The Ni/TPC catalyst could obviously improve the burning gas content. The highest catalytic efficiency was obtained at reforming temperature of 750 ℃ and 10 min holding time with 30% Ni loading. The content of H2 in the gas was high and relatively increased by 50% after using the catalyst for 850 min. The Ni3ZnC0.7 active component structure converted to FeNi3 after long-term used with high and stable catalytic activity. TPC had the ability to be a new type of carrier for nickel catalyst.
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Key words:
- biomass pyrolysis /
- gas reforming /
- carrier /
- Ni catalyst /
- catalyst life
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Figure 1 Flow scheme of bench scale reactor for catalytic pyrolysis of straws biomass
1: nitrogen; 2: pyrolysis gasifier and thermocouples; 3: insulation brick; 4: porcelain boat; 5: catalytic bed and catalyst; 6: temperature controller; 7: waterproof valve; 8: water channel; 9: particle filter; 10: gas dryer (silica gel); 11: pump; 12: gas buffer package; 13: flowmeter; 14: gas analyzer; 15: fire prevention
Figure 2 XRD patterns of TPC and Ni/TPC and waste Ni/TPC
(a): TPC; (b): Ni/TPC; (c): waste Ni/TPC
■: ZnS; ●: Ni3ZnC0.7; ▲: FeNi3
Figure 3 SEM images of TPC, Ni/TPC and waste Ni/TPC
(a): TPC; (b): Ni/TPC; (c): waste Ni/TPC
Table 1 Ultimate and proximate analyses of wheat straw sample
Ultimate analysis w/% Proximate analysis w/% C H O N S M A V FC 33.65 4.91 51.88 0.89 0.15 11.15 8.43 78.1 2.69 
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Table 2 EDX element analysis of three samples
Sample Main composition and content w/% Ni C S Zn Si Ca Fe K TPC - 61.49 15.47 13.94 5.85 1.16 0.93 0.73 30% Ni/TPC 28.44 42.81 11.25 10.46 4.66 0.86 0.71 0.54 Waste Ni/TPC 27.91 43.75 11.44 9.96 4.61 0.82 0.65 0.55
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Table 3 BET surface area of TPC and Ni/TPC waste Ni/TPC
Sample TPC Ni/TPC Waste Ni/TPC BET surface area A/(m2·g-1) 84 62 49
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