减压蜡油加氢脱氮宏观反应动力学模型

 针对原料油加氢精制的反应特征,根据减压蜡油(VGO)在催化剂 RN-32上 HDN 中试试验数据,考察了各反应条件对 VGO HDN 反应产物氮含量的影响,详细分析了不同减压蜡油原料性质对 HDN 活化能的影响,建立了减压蜡油 HDN 反应动力学模型。验证实验结果表明,该模型是成功的。     

Mechanism of the Direct Hydrodenitrogenation of Naphthylamine on Sulfided NiMo/Al2O3

The hydrodenitrogenation of 1-naphthylamine was studied over a sulfided NiMo/Al₂O₃ catalyst between 300 and 350 °C. 1-Naphthylamine reacted to tetralin, naphthalene, 1,2-dihydronaphthalene and 5,6,7,8-tetrahydro-1-naphthylamine. To elucidate the reaction mechanism, the reactions of the intermediates 1,2,3,4-tetrahydro-1-naphthylamine, 1,2-dihydronaphthalene and 5,6,7,8-tetrahydro-1-naphthylamine were studied as well. The results show that 1-naphthylamine reacts through hydrogenation to 1,2,3,4-tetrahydro-1-naphthylamine, which reacts by NH₃ elimination to 1,2-dihydronaphthalene. The latter molecule subsequently reacts by hydrogenation to tetralin as well as by dehydrogenation to naphthalene. In addition, naphthalene is formed by direct denitrogenation from 1-naphthylamine. This direct denitrogenation may take place by hydrogenation of 1-naphthylamine to 1,2-dihydro-1-naphthylamine, followed by NH₃ elimination or followed by a Bucherer-type NH₂–SH exchange, dehydrogenation and C–S bond hydrogenolysis.     

Hydrotreating of Heavy Gas Oil Derived from Athabasca Bitumen Over Co–Mo/γ-Al2O3 Catalyst Prepared by Sonochemical Method

Co–Mo/γ-Al₂O₃ oxide containing 9.8 wt% Mo and 2.9 wt% Co was prepared by high-intensity ultrasonic irradiation of Mo(CO)₆, Co₂(CO)₈, and γ-Al₂O₃ in decahydronapthalene under air flow. The oxidic Co–Mo catalyst thus formed was characterized by elemental analysis, BET N₂ adsorption and XRD. The surface sites on the sulfided Co–Mo/γ-Al₂O₃ catalyst were characterized by infrared spectroscopy of CO adsorption. Hydrodenitrogenation (HDN) and hydrodesulfurization (HDS) activities were evaluated for heavy gas oil derived from Athabasca bitumen in a trickle bed reaction system using the following conditions: temperatures ranging from 370 to 400 °C, a pressure of 8.8 MPa, a liquid hourly space velocity of 1 h⁻¹, and a H₂/feed ratio of 600 ml/ml. The dispersion, nature of active sites and hydrotreating activity of this catalyst were compared with the conventionally prepared Co–Mo/γ-Al₂O₃ catalyst containing similar wt% of Mo and Co. The Co–Mo catalyst prepared by sonochemical method has higher HDN and HDS rate constants than the conventional catalyst due to an improved dispersion of MoS₂.     

加氢脱氮反应与加氢脱氮催化剂的研究进展

介绍石油馏分中主要含氮组分和其结构特性，以及典型含氮化合物的加氢脱氮反应网络、反应机理、反应动力学，阐述了加氢脱氮催化剂改性的不同途径：载体的改性、活性组分和助剂的选择、活化方法的改进等。     

脂肪酸甲酯加氢脱氧和加氢脱氮制备生物烷烃

以源于废弃油脂的脂肪酸甲酯(FAMEs)为原料,以Ni Mo/Al2O3为催化剂,采用加氢脱氧和加氢脱氮两步法制备生物烷烃并对反应工艺进行了优化。结果表明,加氢脱氧的最佳反应条件为:反应温度380℃、氢气压力2 MPa、氢气和FAMEs体积比为1000,空速1h–1;加氢脱氮的最佳反应条件为:反应温度310℃、氢气压力2 MPa、氢气和烷烃体积比为2000,空速0.25 h–1。在该优化反应条件下,硫化后的Ni Mo/Al2O3催化FAMEs加氢脱氧能够获得正构烷烃质量分数高于97%的生物烷烃,所得产品采用Ni Mo/Al2O3催化剂进行二次加氢脱氮能够进一步移除超过90%的含氮化合物。硫化后的Ni Mo/Al2O3催化剂在FAMEs加氢脱氧反应中具有良好的结构稳定性和抗积碳性能,使用1000 h后其晶相结构无明显改变且表面积碳量仅为3.18%。     

新型加氢裂化预处理催化剂的研制与工业应用

FF-16催化剂是抚顺石油化工研究院研制的新型高活性加氢裂化预处理催化剂,该催化剂具有脱氮活性高,金属分散性好,活性金属易于硫化等特点。2003年9月在上海石油化工股份有限公司1．50ML／a加氢裂化装置工业应用,结果表明：FF-16催化剂加氢脱氮活性和稳定性好,原料适应性强,其脱氮率达到99％以上,加氢脱氮活性明显优于3996催化剂。     

FH-40A催化剂对煤油加氢装置的适应性试验

为了考察抚顺石化公司石油三厂分子筛脱蜡装置煤油加氢单元换用国产加氢精制催化剂的可行性,采用抚顺石油化工研究院新近开发的FH-40A轻质馏分油加氢精制催化剂,以石油三厂煤油为原料油,在装置工况条件下分别考察了拔头后的煤油和全馏分煤油采用FH-40A催化剂的可能性.试验结果标明:FH-40A催化剂具有优异的加氢脱硫、加氢脱氮和芳烃饱和性能,可以使精制油的硫质量分数＜0.5 μg/g,氮的质量分数＜1 μg/g,溴指数＜150 mg/100 g,芳烃的体积分数＜5 %,满足分子筛脱蜡装置进料质量的要求.     

Synthesis, characterization and hydrotreating performance of supported tungsten phosphide catalysts

Supported tungsten phosphide catalysts were prepared by temperature-programmed reduction of their precursors (supported phospho-tungstate catalysts) in H₂ and characterized by X-ray diffraction (XRD), BET, temperature-programmed desorption of ammonia (NH₃-TPD) and X-ray photoelectron spectroscopy (XPS). The reduction-phosphiding processes of the precursors were investigated by thermogravimetry and differential thermal analysis (TG-DTA) and the suitable phosphiding temperatures were defined. The hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities of the catalysts were tested by using thiophene, pyridine, dibenzothiophene, carbazole and diesel oil as the feedstock. The TiO₂, γ-Al₂O₃ supports and the Ni, Co promoters could remarkably increase and stabilize active W species on the catalyst surface. A suitable amount of Ni (3%–5%), Co (5%–7%) and V (1%–3%) could increase dispersivity of the W species and the BET surface area of the WP/γ-Al₂O₃ catalyst. The WP/γ-Al₂O₃ catalyst possesses much higher thiophene HDS and carbazole HDN activities and the WP/TiO₂ catalyst has much higher dibenzothiophene (DBT) HDS and pyridine HDN activities. The Ni, Co and V can obviously promote the HDS activity and inhibit the HDN activity of the WP/γ-Al₂O₃ catalyst. The G-Ni5 catalyst possesses a much higher diesel oil HDS activity than the sulphided industrial NiW/γ-Al₂O₃ catalyst. In general, a support or promoter in the WP/γ-Al₂O₃ catalyst which can increase the amount and dispersivity of the active W species can promote its HDS and HDN activities.     

MoP/TiO2-ZrO2催化剂制备及加氢脱氮性能考察

采用溶胶-凝胶法制备了TiO₂-ZrO₂复合载体,并用共浸渍法制备负载型MoP/TiO₂-ZrO₂催化剂,通过原位还原技术对催化剂进行还原处理后,在连续固定床反应器上进行活性评价。结果表明, TiO₂和ZrO₂物质的量比以及Mo负载量对催化剂活性有较大影响,当n(Ti)∶n(Zr)=4∶1和Mo负载质量分数为20%时,MoP/TiO₂-ZrO₂催化剂的加氢脱氮效果最好,并且TiO₂-ZrO₂复合载体比TiO₂-Al₂O₃复合载体的活性提高12.4个百分点。     

FF-56加氢裂化预处理催化剂的制备及其性能

合成了新一代加氢裂化预处理催化剂FF-56,选择了制备该催化剂的适宜载体,并利用有机助剂优化了活性相结构,通过氮吸附、FTIR、DSC、TPR、XPS和TEM等方法对催化剂进行了表征。FF-56催化剂以大孔径氧化铝为载体,载体的孔体积和平均孔径均较大;表征结果显示,FF-56催化剂具有较高的总酸量和B酸含量,表面Ni的分散度明显高于参比催化剂FF-46,FF-56催化剂中活性金属与载体间的相互作用适度增强,层数大于7的MoS_2片晶数明显少于FF-46催化剂,FF-56催化剂所选有机助剂的热分解温度比FF-46催化剂所选有机助剂的热分解温度提高近1 00℃,使生产更易控制;装置评价结果表明,FF-56催化剂是一种脱氮活性高、稳定性好的加氢裂化预处理催化剂。