工业NiW/Al2O3催化剂上喹啉的加氢脱氮宏观动力学

以喹啉为含氮模型化合物,在高压滴流床反应装置中考察了工业NiW/Al2O3催化剂RN-10上的加氢脱氮动力学规律,研究了反应温度330～420℃、氢分压1.2～5.2MPa、氢油比200～800(v/v)、重量空速(WHSV)20～70 h-1等反应条件对喹啉的加氢脱氮反应结果的影响.结果表明,反应温度对喹啉的脱氮率影响较大,提高反应温度可有效提高喹啉的脱氮率;同时,氢分压也是喹啉加氢脱氮的一个重要的影响因素,但是,当氢分压和氢油比较大时,氢分压和氢油比的变化对喹啉的脱氮率基本无影响.采用修正的n(n＜1)级反应动力学模型对实验数据进行拟合,求得了喹啉加氢脱氮反应的表观活化能为180.4 kJ·mol-1.经检验,模型计算结果与实验结果能较好地吻合.     

W-Mo-Ni-Cr/Al2O3催化剂的表征及其加氢脱氮性能研究

采用分步浸渍法制备了负载型W-Mo-Ni-Cr催化剂。并采用X射线衍射（XRD）、差热分析（TG/DTA）、氮气吸附（BET）、程序升温脱附（TPD）、程序升温还原（TPR）和红外光谱（IR）等方法对其进行表征。以吡啶为模型化合物进行了加氢脱氮活性试验，在反应温度180 ℃，反应时间1 h时，催化剂的催化性能最佳。实验条件下，吡啶的单次转化率可达88.5％。     

Effect of EDTA on hydrotreating activity of CoMo/γ-Al2O3 catalyst

γ-Al₂O₃ supported Co (0–4.5 wt%) Mo (9.0 wt%) sulfide catalysts were prepared in the presence and the absence of ethylenediaminetetraacetic acid (EDTA). The hydrodenitrogenation (HDN) activity of these catalysts was studied in the model reaction of 2,6-dimethylaniline (DMA) at 300 °C under 4 MPa. The CoMo/Al₂O₃ catalysts prepared with the EDTA showed higher HDN of DMA than those prepared without EDTA. The maximum of 36% increase in rate constant of HDN of DMA was observed over the catalyst with 3% Co prepared using EDTA. The FT-IR spectroscopy of adsorbed CO on CoMo catalysts showed that EDTA addition promoted the formation of catalytically active “CoMoS” phase as evidenced from increases in intensity of band at 2070 cm⁻¹, which is maximum for 3% Co loaded catalysts. The HDN and hydrodesulfurization (HDS) activity of 3% Co loaded catalyst prepared using EDTA was tested and compared with those catalyst prepared without EDTA in a trickle bed reactor using heavy gas oil derived from Athabasca bitumen in the temperature range 370–400 °C and 8.8 MPa. Improved HDN and HDS conversion of heavy gas oil was obtained for the catalyst prepared with EDTA.     

新型FZC-42渣油加氢脱氮催化剂的开发

介绍了新型FZC 42渣油加氢脱氮催化剂的开发概况。对实验室和工业试生产催化剂进行的评价试验表明，新催化剂具有良好的加氢脱氮活性及活性稳定性。同时，因制备工艺简单，使新催化剂在制备成本方面更具市场竞争力。     

过渡金属磷化物的加氢精制催化性能研究进展

由于全球更加严格的环境法规的要求，开发新型深度加氢脱硫（HDS）和加氢脱氮（HDN）催化剂已经引起了人们的极大关注。过渡金属磷化物由于具有与过渡金属氮化物和碳化物相似的物理性质和优异的加氢脱硫、脱氮活性及催化选择性成为新型催化材料研究领域的一个热点。笔者论述了过渡金属磷化物的结构、制备、表征和催化性能方面的研究进展，侧重介绍了中国科学院大连化学物理研究所最近在这方面的研究情况。从目前的研究来看，过渡金属磷化物，特别是Ni2P，是具有潜在应用前景的一种新型深度加氢精制催化材料。     

Determination of the nature of distinct catalytic sites in hydrodenitrogenation by competitive adsorption

The inhibitive effect of nitrogen-containing compounds on hydrodenitrogenation was studied over NiMo(P)/Al₂O₃ catalysts. From the differences in the adsorption constants it is concluded that at least four distinct catalytic sites are involved in the elementary hydrodenitrogenation steps. The catalytic site for the cleavage of aliphatic C(sp³)-N bonds is acidic and most probably an SH species on a surface Mo or Ni site. The catalytic site for the hydrogenation of a phenyl group is different from that for alkene hydrogenation, the former being more coordinately unsaturated than the latter, with two or three sulphur vacancies. A fourth site is responsible for the hydrogenolysis of the C(sp²)-N bond of anilines. It is characterised by a more reduced environment of Mo and by phosphorus promotion. This revised version was published online in July 2006 with corrections to the Cover Date.     

加氢脱氮催化剂载体的研究

介绍了加氢脱氮催化剂载体的特点和性能,总结了加氢脱氮催化剂载体的发展趋势,提出了高活性加氢脱氮催化剂载体的研究思路和途径。     

重整原料预加氢催化剂的性能评价

为了考察086-11-46催化剂（W-Ni/SiO₂-Al₂O₃）加氢脱硫、加氢脱氮性能以及处理劣质原料油的能力,分别以直馏石脑油、加入吡啶的直馏石脑油和加入催化汽油的直馏石脑油为原料油,进行了086-11-46催化剂与国内某重整原料预加氢催化剂（Mo-Co/γ-Al₂O₃）的对比评价,并以直馏石脑油为原料,考察其稳定性。结果表明,086-11-46催化剂的加氢脱硫和加氢脱氮性能均优于对比剂,更加适合处理氮含量及烯烃含量较高的劣质原料油。086-11-46催化剂在入口温度低于对比剂15 ℃的条件下,产品与对比剂相当,稳定性优于对比剂。     

加氢精制催化剂载体的研究进展

综述了单组分氧化物、复合氧化物、碳材料、介孔材料和分子筛等载体在加氢精制催化剂方面的应用。单组分氧化物做载体时,TiO_2和ZrO_2载体比传统的γ-Al2O_3载体制得的催化剂活性高;复合氧化物载体主要包括含Al_2O_3的复合载体、含TiO_2的复合载体、含ZrO_2的复合载体和含ZnO的复合载体,其中TiO_2-Al_2O_3是研究最多的复合氧化物载体;活性炭负载的加氢催化剂有较高的加氢活性和较低的结焦倾向;介孔材料和分子筛载体由于具有大比表面积,是加氢催化剂载体的研究热点。     

The effect of phosphorus on the HDN reaction of piperidine,decahydroquinoline and ortho-propylaniline over Ni-MoS2/Al2O3 catalysts

The hydrodenitrogenation (HDN) of piperidine, decahydroquinoline (DHQ) and orthopropylaniline (OPA) has been studied over NiMo(P)/Al₂O₃ catalysts at 593 K and 3.0 MPa in order to understand the effect of phosphorus on the elementary HDN reaction steps. Phosphorus exhibited a negative effect on the HDN of piperidine and DHQ, both on the C-N bond cleavage reaction and on the subsequent hydrogenation reaction of alkene to alkane. A P/Al₂O₃ catalyst showed no HDN activity at all, neither with piperidine, nor with DHQ. A positive effect of phosphorus was observed in the HDN of OPA, where hydrogenation of the aromatic ring is needed and is rate limiting. It is suggested that introduction of phosphorus to NiMo/Al₂O₃ catalysts on the one hand decreases the available support surface area, and as a consequence the dispersion of the Ni-Mo-S phase and thus the capacity for C-N bond breaking and olefin hydrogenation. On the other hand, phosphorus induces either new or more active sites for the hydrogenation of aromatics.