Effect of preparation method on the structure and properties of coal tar model compound cracking catalyst Ni/Al2O3
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摘要: 采用等体积浸渍法、浸渍沉淀法和机械化学法(市售载体和自制载体)制备了Cat-1、Cat-2、Cat-3和Cat-4四种催化剂,通过BET、H2-TPR、XRD、XPS和NH3-TPD等表征催化剂的结构特征,考察了各催化剂对煤焦油模型化合物甲苯和芘(3%,质量分数)裂解反应性能的影响。结果表明,四种催化剂均为介孔材料,且Cat-4的介孔有序度更高,比表面积最大,达235 m2/g。Cat-4催化剂中,NiAl2O4尖晶石的还原峰面积最高,占总面积的85.2%,还原后Ni的分散度最大,粒径最小,约为10.0 nm,意味着活性位点多。实验表明,除Cat-1外,其他催化剂对芘的裂解活性基本相当,其中,Cat-4作用下的析碳量最低,为10.84%,经Cat-1、Cat-2和Cat-3裂解后,体系中的析碳量分别较Cat-4增加了35.0%、74.7%和45.7%。可见,机械化学法制备的催化剂不仅具有最高的比表面积利于活性组分分散,而且NiAl2O4尖晶石含量最高,可抑制裂解过程中积炭的生成,因而最适宜于甲苯+芘裂解体系。
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关键词:
- 制备方法 /
- Ni/Al2O3催化剂 /
- 模型化合物 /
- 裂解性能
Abstract: Cat-1, Cat-2, Cat-3 and Cat-4 catalysts were synthesized via different preparation methods that are incipient wetness, impregnation-precipitation and mechanochemical method (carriers from market and homemade for comparison), and then characterized by BET, H2-TPR, XRD, XPS and NH3-TPD. The cracking behavior of toluene and pyrene (3%, mass fraction) (coal tar model compounds) were investigated to evaluate the catalytic performance of the stated catalysts. The catalyst characterization showed that the pore size of all the catalysts belonged to mesoporous range, and Cat-4 catalyst exhibited higher ordered mesoporous and larger surface area than others, up to 235 m2/g. Besides, the peak area of NiAl2O4 spinel reached up to the highest value of 85.2%. The dispersion of Ni in the reduced Cat-4 was the highest and its particle size was the lowest value, about 10.0 nm. Which means that there are more active sites. The catalytic performance results showed that the cracking rate of pyrene varied little for other catalysts, except for Cat-1, but the lowest carbon deposition of 10.84% was obtained under the action of Cat-4, while the carbon deposition of Cat-1, Cat-2 and Cat-3 increased by 35.0%, 74.7% and 45.7% respectively compared with that of Cat-4. Thus, Cat-4 prepared by mechanochemical method is more suitable for the cracking of toluene and pyrene system because of highest BET surface area, which is favorable for the dispersion of active component, and at the same time, the highest content of NiAl2O4 can inhibit the formation of carbon.-
Key words:
- preparation method /
- Ni/Al2O3 catalyst /
- model compound /
- cracking performance
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图 1 催化剂评价装置示意图
1: N2 cylinder; 2: flowmeter; 3: pump; 4: sample bulb; 5: thermocouple; 6: vaporizer; 7: pyrolyzer; 8: product sorage tank; 9: wet type flowmeter; 10: drying tower; 11: reservoir bag; 12: gas chromatograph; 13: cold hydrazine
Figure 1 Schematic diagram of the catalytic evaluation device
表 1 催化剂的EDX表征
Table 1 EDX results of the catalysts
Catalyst Ni w /% Loading ratio/% experimental value theoretical value Cat-1 14.66 15.00 97.73 Cat-2 14.57 97.13 Cat-3 14.35 95.67 Cat-4 14.32 95.47 表 2 催化剂的孔结构特征
Table 2 Pore characteristics of the catalysts
Catalyst ABET /(m2·g-1) d /nm v /(cm3·g-1) Cat-1 123 11.41 0.32 Cat-2 123 10.78 0.33 Cat-3 107 10.83 0.29 Cat-4 235 8.20 0.48 表 3 不同Ni物种的分散度和还原峰面积比例
Table 3 Dispersion of different Ni species and the proportion of reduction peak area
Catalyst tm /℃ Fraction of total area /% Ni metal area /(m 2·g -1) Dispersion /% Ni metal particle size d/nm β γ β γ Cat-1 702 895 25.7 74.3 1.6 1.6 18.8 Cat-2 700 891 28.3 71.7 4.1 4.2 15.2 Cat-3 776 886 26.5 73.5 4.0 4.2 14.8 Cat-4 737 859 14.8 85.2 4.4 4.6 10.0 表 4 催化剂对模型化合物催化裂解产率的影响
Table 4 Catalytic cracking yield of the model compounds over the catalysts
Catalyst Model compound Liquid yield/% Gasyield/% Yield of carbondeposition/% Cracking yieldof pyrene/% Pyrene production rate/(mg·g -1) Cat-1 toluene 83.83 1.56 14.60 - 0.11 toluene + pyrene 83.81 1.56 14.63 62.14 - Cat-2 toluene 78.35 2.78 18.87 - 0.00 toluene + pyrene 78.27 2.79 18.94 66.30 - Cat-3 toluene 82.11 2.13 15.76 - 0.32 toluene + pyrene 82.06 2.15 15.79 66.41 - Cat-4 toluene 86.67 2.51 10.82 - 0.93 toluene + pyrene 86.51 2.65 10.84 66.98 - 表 5 裂解反应液体产物GC-MS谱图的定性分析
Table 5 Qualitative analysis of GC-MS spectrum of liquid product from the cracking reaction
Peak Name Structure Peak Name Structure 1 toluene 8 m-methylbiphenyl 2 p-xylene 9 2, 2′-dimethylbiphenyl 3 o-xylene 10 3, 3′-dimethylbiphenyl 4 m-xylene 11 cis-stilbene 5 naphthalene 12 phenanthrene 6 2-ethenylnaphthalene1 13 pyrene 7 diphenylmethane 表 6 试样表面积炭的Raman特性
Table 6 Raman property of carbon deposition on the catalysts after evaluation experiment
Catalyst Average carbon formation rate /(mgc ·gcat-1·min-1) Relative intensity ratio of D and G bands on Raman apectra (ID/ IG) Cat-1 0.0197 1.237 Cat-2 0.0231 1.098 Cat-3 0.0214 1.199 Cat-4 0.0132 0.970 -
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