New generation of hydrotreating catalysts

Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 2, pp. 2–4, February, 1991.     

Hydrotreating of waste lube oil by rejuvenated spent hydrotreating catalyst

Large quantities of catalysts are used in the Egyptian refining industry for the purification and upgrading of various petroleum streams. These catalysts gradually lose activity through deactivation with time and the spent catalysts were usually discarded as solid waste. On the other hand, waste lube oil contains heavy metals coming from undergirded base oil and additives, these metals have carcinogenic effect and cause serious environmental problems. Studies are conducted on the reclamation of metals, rejuvenation and reuse of the spent hydrotreating catalyst (Mo–Ni/Al) which have been used in re-refining of waste lube oil at Alexandria Petroleum Company. Three leaching solvents were used: oxidized oxalic acid, benzoic acid and boric acid at different concentrations (4%, 8% and 16%), different oxidizing agents (H₂O₂ and Fe(NO₃)₃) and different modes of addition of oxidizing agents (batch and continuous). The results indicated that 4% oxalic acid + 5% Fe(NO₃)₃ at continuous addition of oxidizing agents was the most efficient leaching solvent to facilitate metal removal and rejuvenate catalyst. The fresh catalyst was applied for re-refining of waste lube oil under different reaction temperatures (320–410) °C in order to compare the hydrodesulphurization (HDS) activity with both the fresh, treated and spent catalysts. The results indicated that the rejuvenation techniques introduce a catalyst have HDS activity nearly approach to that the fresh of the same type.     

渣油加氢催化剂的再生

在管式炉内对工业渣油加氢主催化剂(脱硫剂和脱残炭剂)进行再生,利用BET,XRD,TPR等分析手段对再生前后的催化剂进行表征,考察了再生后催化剂的性能。表征结果显示,再生后脱硫剂和脱残炭剂孔体积分别达到了新鲜催化剂的87.6%和95.6%,比表面积分别达到了新鲜催化剂的91.1%和96.8%;再生后脱硫剂和脱残炭剂均有少量的镍铝尖晶石生成,使催化剂的活性降低。试验结果表明,再生后脱硫剂和脱残炭剂的活性金属H2还原温度分别比新鲜催化剂提高了35℃和27℃,催化剂的活性大幅下降。因此,需进一步研究,降低反应温度、提高再生催化剂的活性,使再生催化剂具备利用价值。     

螯合剂对加氢精制催化剂的影响

分析了螯合剂的作用机理及不同类型螯合剂对加氢精制催化剂的影响。在加氢精制催化剂的制备过程中引入螯合剂是提高催化剂加氢活性的一种非常有效的技术手段。螯合剂具有减弱活性组分与载体之间相互作用、提高活性组分在载体上的分散度、延迟助剂金属硫化等作用,可以促进高活性TypeⅡCo-Mo-S相的生成。螯合剂配齿数量与螯合能力的不同使得金属螯合物结构和螯合常数不同,从而导致了催化剂中Co或Ni活性相结构的不同。不同类型螯合剂的引入会对加氢精制催化剂产生不同程度的影响,螯合剂改性的加氢催化剂较传统的加氢催化剂加氢活性有明显的提高。最后提出了螯合剂在加氢催化剂的应用研究中存在的问题,分析了今后的研究方向。     

催化裂化柴油加氢精制催化剂及其工艺条件

利用氧化铝与分子筛复合载体负载硝酸镍和偏钨酸铵得到催化裂化柴油超低硫加氢精制催化剂,采用XRD,BET,XRF等方法对催化剂进行表征。表征结果显示,催化剂的表面具有L酸和B酸,孔径主要为4～10 nm,活性组分为W-Ni,助剂SiO_2,TiO_2,P_2O_5等促进了活性组分的高度分散并提高了催化剂的加氢性能。在200 mL加氢装置上考察了工艺条件对催化剂加氢活性的影响。实验结果表明,该催化剂在进行选择加氢脱硫和多环芳烃饱和反应时,较佳的工艺条件为:液态空速1.0 h~(-1),氢油体积比500∶1、氢分压8.0 MPa、反应温度不低于350℃。经2 000 h活性稳定性实验后,生成油的硫含量始终小于10μg/g,多环芳烃含量始终小于11%(φ),加氢脱硫、多环芳烃饱和性能稳定。     

Experience in use of zeolitic catalysts in hydrotreating processes

Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 6, pp. 14–15, June, 1988.     

Recovery of vanadium from spent hydrocracking catalysts

Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 9, pp. 12–13, September, 1989.     

Improvement of gas-air regeneration of catalysts in hydrotreating vacuum distillate

Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 5, pp. 12–14, September–October, 1995.