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％。     

助剂对Ni/Al2O3催化剂芳烃加氢热稳定性和抗硫性能的影响

考察了助剂Mg、La、Mo、Ti和Th的加入对Ni/Al2O3催化剂芳烃加氢热稳定性和抗硫性能的影响。结果表明，除Mo以外，其他少量助剂的加入均有助于催化剂活性的提高，其中以Mg效果最好。Mg的加入使Ni原子的电子云密度升高，提高了活性组分Ni的分散度，从而提高了催化剂的催化活性和使用寿命；Mo对催化剂的加氢活性和抗硫性能没有帮助，可能是由于没有形成作为主要抗硫相的钼酸镍或钼镍合金。     

乙二胺四乙酸对NiMo/Al_2O_3催化剂加氢脱氮性能的影响

以氧化铝为载体,Ni和Mo为金属活性组分,添加不同含量乙二胺四乙酸,采用等体积浸渍法制备系列Ni Mo(x)/Al_2O_3(x为乙二胺四乙酸与Ni物质的量比)重质油加氢处理催化剂,考察乙二胺四乙酸加入量对催化剂加氢脱氮性能的影响,并采用N_2物理吸附-脱附、XRD和HRTEM等对催化剂进行表征。结果表明,乙二胺四乙酸的加入增强了金属组分与氧化铝载体间的相互作用,降低了MoS_2活性相的堆垛层数和片层长度,促进了活性相的分散。乙二胺四乙酸与Ni物质的量比为0.5时,MoS_2活性相堆垛层数和片层长度达到良好的结合,对应的催化剂Ni Mo(0.5)/Al_2O_3具有最优的加氢脱氮性能。     

WP/γ-Al2O3催化剂的制备、表征及加氢脱硫和加氢脱氮活性

Two series of WP/Al2O3 catalyst precursors with WP mass loading in the range 18.5%-37.1% were prepared using the impregnation method and mixing method, respectively, and the catalysts were then obtained by temperature-programmed reduction of supported tungsten phosphate (precursor of WP/Al2O3 catatlysts) in H2 at 650℃ for 4h. The catalysts were characterized by XRD, BET, TG/DTA, XPS and 31p MAS-NMR. The activities of these catalysts were tested in the hydrodenitrogenation (HDN) of pyridine and hydrodesulfurization (HDS) of thiophene at 340℃ and 3.0MPa. The results showed that owing to the stronger interaction of the support with the active species, the precursor of WP/Al2O3 catalyst was more difficultly phosphided and a greater amount of W species was in a high valence state W6 on the surface of the catalyst prepared by the impregnation method than that by the mixing method. 31p MAS-NMR results indicated that 31p shift from 85% H3PO4 of 2.55 × 10-4 for WP and 2.57 × 10-4 for WP/γ-Al2O3 catalysts prepared by mixing method. Such WP/Al2O3 catalysts showed higher HDN activities and lower HDS activities than those prepared by the impregnation method under the same loading of WP.WP/γ-Al2O3 catalysts with weak interaction between support and active species were favorable for HDN reaction while the WP/γ-Al2O3 catalysts with strong interaction were favorable for HDS reaction.     

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。     

Zr改性对NiW/Al2O3催化剂加氢性能的影响

引言随着原油重质化趋势的不断加剧和环保法规对轻质油品质量要求的不断提高,劣质重油轻质化及清洁化生产成为石油加工技术发展的主要方向。溶剂脱沥青是重油脱碳改质工艺之一,得到的脱沥青油一般作为催化裂化的掺炼原料,脱沥青油中较高的硫氮含量及稠环芳烃含量容易造成催化裂化催化     

基于助剂改性的水热处理对加氢处理催化剂及其反应性能的影响

采用XRD、BET、NH3-TPD、H2-TPR、CO-IR、Raman等表征方法,详细考察了水热处理温度及助剂改性对加氢处理催化剂性质的影响,并以催化柴油为原料,评价了水热处理温度及助剂改性对加氢处理催化剂加氢脱硫、脱氮活性的影响。结果表明：基于助剂改性的水热处理可以有效地改善催化剂表面活性金属的存在状态,催化剂表面更容易形成八面体的Mo物种。评价结果表明,水热处理后的催化剂孔结构更为畅通,其加氢脱硫、脱氮活性显著提高;SRC-2和SRC-3的HDS活性明显提高,分别在93%和94%左右,较SRC-1的脱硫率提高了3～4个百分点。SRC-5的产物中,总芳烃质量分数最低为69.2%,总饱和烃质量分数最高为30.8%,其总饱和烃质量分数相比于原料和SRC-1的加氢产物分别提高11.3、7.3个百分点。     

助剂对沸腾床渣油加氢催化剂结构性能的影响

考察了单一助剂和复合助剂组合对沸腾床渣油加氢催化剂结构性能的影响。结果表明助剂的加入显著改善了催化剂的加氢活性及转化率,可以选择不同的助剂组合来制备适用于沸腾床工艺的渣油加氢催化剂。     

助剂对沸腾床渣油加氢催化剂性能的影响

制备含有不同助剂的沸腾床渣油加氢催化剂,对催化剂进行系统地表征,同时在高压釜上进行活性评价,以考察助剂对沸腾床渣油加氢催化剂性能的影响。结果表明：助剂的加入改变了催化剂酸强度分布、还原性质及金属分散性质,加入助剂P制备的催化剂其加氢性能较好。     

ＦＨ-５Ａ型加氢精制催化剂在缓和反应条件下的性能考察

在大型柴油加氢装置上对ＦＨ-５Ａ型精制催化剂的性能进行了考察。结果表明,由不同比例的重油催化柴油、焦化柴油和高含硫直馏柴油组成的多种混合原料,在缓和的反应条件下,采用ＦＨ-５Ａ加氢精制催化剂都能生产出符合环保要求的低硫优质柴油。     

NiMo/Al2O3加氢精制催化剂上操作变量对HDN和HDS反应性能的影响

Using the JQ-Ⅱ high pressure hydrogenation micro-reactor unit, the reactivity of Athabasca bitumen derived heavy gas oil was studied over commercial and homemade hydrotreating catalysts. The effects of catalyst preparation variables and the influences of operation conditions, such as pressure, temperature, hydrogen/oil ratio and space velocity were also examined. It was shown that the optimal concentrations of the active components were 5% of NiO, 20% of MoO3 and 3.5% of phosphorus (by mass), and the suitable operation conditions were determined experimentally.     

Mechanism of carbon-nitrogen bond cleavage during amylamine hydrodenitrogenation over a sulphided NiMo/Al2O3 catalyst

By comparison of the hydrodenitrogenation rate of amylamine with those of neopentylamine and tert-amylamine over a conventional catalyst, it was evidenced that the hydrogen atoms of the carbon in the position with respect to the nitrogen atom participate in the C-N bond cleavage. A detailed mechanism including the interaction with the catalyst is proposed for this reaction.     

Si改性对NiMo/Al2O3催化剂加氢脱硫性能的影响

以中和法合成的不同SiO₂含量的改性氧化铝为载体,本文制备系列Si改性的NiMo/Al₂O₃催化剂,采用X射线衍射（XRD）、N₂物理吸附（BET）、程序升温脱附（NH₃-TPD）、吡啶吸附红外光谱（Py-IR）、程序升温还原（H₂-TPR）、高分辨透射电镜（HRTEM）和X射线光电子能谱（XPS）等分析手段进行详细表征。表征结果显示,引入Si减弱了活性金属与载体之间的相互作用,改善了催化剂的孔结构与表面酸性分布,提高了活性相分散度和金属硫化度,促使形成更多的II类NiMoS活性相。以二苯并噻吩（DBT）为模型化合物,在固定床加氢装置上考察了系列催化剂的加氢脱硫（HDS）性能,结果表明,引入Si可降低DBT的加氢反应活化能,提高反应速率常数,进而提高催化剂的加氢脱硫活性。对比DBT转化率在50%时的脱硫产物分布表明引入Si可影响催化剂的反应路径选择性,直接脱硫路径（DDS）选择性从83.69%增加至92.89%,证实了催化剂的表征规律。     

W/SiO_2-Al_2O_3催化剂对高黏度润滑油基础油的加氢精制

制备以SiO_2-Al_2O_3为载体、W为活性组分的加氢精制W/SiO_2-Al_2O_3催化剂,并考察了温度、氢压、氢油体积比和空速的影响。研究了在W/SiO_2-Al_2O_3催化剂作用下,润滑油基础油的加氢精制效果。结果表明,在精制温度260℃、氢压9.0 MPa、氢油体积比700:1和空速1.25 h^(-1)条件下,氮含量从63.4μg·g^(-1)降至0.9 μg·g^(-1),硫含量从110.2μg·g^(-1)降至0.32 μg·g^(-1),液体油收率92.7%,运动黏度、闪点、凝点与原料油相比变化不大,加氢精制效果较理想。     

FH-40系列轻质馏分油加氢精制催化剂研制及工业应用

成功开发出性能优异的FH-40A/FH-40B和FH-40C新一代轻质馏分油加氢精制催化剂，该系列催化剂具有孔容大、比表面积高、加氢活性好及堆积密度小等特点。在同等工艺条件下，达到相同精制效果，FH-40系列催化剂比国内外参比催化剂活性高［（10～15） ℃］。工业应用结果表明，FH-40系列催化剂对原料适应性强，具有优异的加氢脱硫和加氢脱氮活性，是加工轻质馏分油的理想催化剂。     

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.     

LH-03型中馏份油加氢精制催化剂的活性评价

LH-03型催化剂是针对国内大量掺炼国外高硫原油,导致馏份油硫含量超标,而专门研制出的新一代中馏份油加氢精制专用催化剂。该催化剂表现出较高的脱硫、脱氮活性及较好的芳烃饱和性能。本文介绍该催化剂对精蜡、粗蜡、轻柴油及催化柴油的加氢精制效果。     

B_2O_3／Al_2O_3催化剂结构和性能的研究

采用溶胶凝胶法和浸渍法,在500℃下焙烧2 h,制备不同组成的B2O3／Al2O3催化剂。通过X射线衍射、热失重、傅立叶红外光谱等测试方法对所制备的催化剂的结构进行表征。通过催化剂与二苯甲酰基甲烷(DBM)配位情况对催化剂的性能表征。研究表明:焙烧获得的主催化剂晶型为γ-Al2O3,添加第二组分B2O3,可以提高与DBM的配位能力,以改善Al2O3的催化活性。