用LIM加氢处理工业废催化剂CO-Mo/Al2O3的氧化焙烧

Y. Sokolova, Anton N. Chepikov
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摘要

研究了工业用废催化剂Co-Mo/Al2O3在空气气氛中氧化焙烧用于石灰加氢柴油的工艺。通过差热分析(DTA)、热重分析(TG)和x射线物相分析发现,在焙烧过程中,硫氧化物和碳氧化物形成CaSO4和CaCO3, Mo转化为钼酸钙。采用过滤固定床对焙烧动力学进行了研究。结果表明,在550 ~ 600℃的温度范围内,空气供气量为3l /min,对接地和非接地的催化剂,该过程在38 ~ 44 min内结束。确定了焙烧过程中硫氧化物吸附的最佳参数(石灰用量、焙烧温度和焙烧时间)。硫氧化物和碳氧化物的吸附度分别为96%和36%。提出利用未磨废催化剂将焙烧产物分离成小馏分(含CaSO4、CaCO3和CaO的混合物)和粗馏分(含Al2O3、CaMoO4和CoO),并对其进行分离处理。研究表明,用碳酸钠溶液对焙烧馏分进行分离处理,可以分别得到氧化铝(催化剂碱)和氧化钴、含钼溶液,也可以得到硫酸盐、碳酸盐和氧化钙的混合物。采用石灰焙烧加氢处理废催化剂的方法,可以处理3-4级危险废物,而不产生危险废气成本。它允许人们在进一步加工过程中获得钼和钴化合物,以及精细划分的氧化铝。
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OXIDATIVE ROASTING OF INDUSTRIAL SPENT CATALYSTS CO-Mo/Al2O3 HYDROPROCESSING WITH LIM
The oxidative roasting of industrial spent catalyst Co-Mo/Al2O3 for the hydrotreatment of diesel fuel with lime in an air atmosphere was studied. Using the data of DTA, TG and X-ray phase analysis, it was found that during roasting, the sulfur and carbon oxides forms CaSO4 and CaCO3, and Mo is converted to calcium molybdate. Using the filtering fixed bed of reagents, the kinetics of roasting was studied. It was found that in the temperature range of 550 – 600 °C with air, supply rate of 3 l/min the process ends in 38 - 44 min for ground and non-ground catalyst. The optimal parameters (lime consumption, temperature, and time of roasting) of the absorption of sulfur oxides during roasting were determined. The degree of sulfur and carbon oxides adsorption is 96 and 36%, respectively. Separation of roasting products using unmilled spent catalyst is proposed into a small fraction (contains a mixture of CaSO4, CaCO3 and CaO) and a coarse (consists of Al2O3, CaMoO4, CoO) fractions, and their separate processing. It has been shown that in the separate processing of roast fractions by a sodium carbonate solution, it is possible to separately obtain alumina (catalyst base) with cobalt oxide, a molybdenum-containing solution, and also a mixture of sulfate, carbonate and oxide calcium. The used method of roasting the spent hydrotreating catalyst with lime will allow hazardous waste of hazard class 3-4 to be disposed of without hazardous waste gas costs. It allows one to obtain, during further processing, molybdenum and cobalt compounds, as well as finely divided alumina.
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