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1.发明授权
公开(公告)号：US4960506A
公开(公告)日：1990-10-02
申请号：US325727
申请日：1989-03-20
IPC分类号： B01J27/049 , B01J31/34 , B01J37/20
CPC分类号： B01J31/1616 , B01J27/049 , B01J31/1845 , B01J31/185 , B01J31/2295 , B01J31/34 , B01J37/20 , B01J21/04 , B01J2231/641 , B01J2531/0208 , B01J2531/84 , B01J27/047
摘要： Hydrocarbon feedstocks are selectively hydrodesulfurized by contacting the feedstock in the presence of hydrogen with a predecessor catalyst comprising molybdenum or tungsten sulfide which has been promoted by reaction with a transition metal containing organo-metallic complex wherein the valence of the metal is 0 or +1 at the time of reaction and the contacting is done at a temperature and pressure sufficient to substantially hydrodesulfurize the hydrocarbon.
摘要翻译： 烃原料通过在氢气存在下使原料与包含钼或硫化钨的前驱催化剂接触来选择性加氢脱硫，其通过与含过渡金属的有机金属络合物反应而促进，其中金属的化合价为0或+1 反应时间和接触在足以使烃基本加氢脱硫的温度和压力下进行。
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2.发明授权
公开(公告)号：US4839326A
公开(公告)日：1989-06-13
申请号：US725662
申请日：1985-04-22
IPC分类号： B01J27/049 , B01J31/34 , B01J37/20
CPC分类号： B01J31/1616 , B01J27/049 , B01J31/1845 , B01J31/185 , B01J31/2295 , B01J31/34 , B01J37/20 , B01J21/04 , B01J2231/641 , B01J2531/0208 , B01J2531/84 , B01J27/047
摘要： This invention relates to a process for the preparation of promoted molybdenum and tungsten sulfide catalysts, the catalysts prepared by such process, and to the use of such catalysts for hydroprocessing processes, particularly hydrotreating. More particularly, this invention relates to the preparation and use of promoted catalysts useful for hydroprocessing processes such as hydrotreating wherein said catalysts are formed by treating molybdenum and tungsten sulfide-containing material (which may be supported) with a low valence promoter metal selected from transition metals particularly the group of Fe, Co, Ni.
摘要翻译： 本发明涉及一种制备促进的钼和硫化钨催化剂的方法，通过这种方法制备的催化剂以及这种催化剂用于加氢处理方法，特别是加氢处理方法。 更具体地说，本发明涉及可用于加氢处理方法如加氢处理的促进催化剂的制备和用途，其中所述催化剂是通过用选自过渡金属的低价促进剂金属（可以负载的）处理形成的 金属特别是Fe，Co，Ni组。
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3.发明授权Hydrotreating using self-promoted molybdenum and tungsten sulfide catalysts formed from bis(tetrathiometallate) precursors 失效使用由双（四金属硫酸盐）前体形成的自身促进的钼和硫化钨催化剂进行加氢处理
公开(公告)号：US4581125A
公开(公告)日：1986-04-08
申请号：US518361
申请日：1983-07-29
摘要： Hydrocarbon feeds are upgraded by contacting same, at elevated temperature and in the presence of hydrogen, with a self-promoted catalyst formed by heating one or more carbon-containing, bis(tetrathiometallate) catalyst precursor salts selected from the group consisting of (NR.sub.4).sub.2 [M(WS.sub.4).sub.2 ], (NR.sub.4).sub.x [M(MoS.sub.4).sub.2 ] and mixtures thereof wherein R is one or more alkyl groups, aryl groups or mixture thereof, wherein promoter metal M is covalently bound in the anion and is Ni, Co or Fe and wherein x is 2 if M is Ni and x is 3 if M is Co or Fe composite in a non-oxidizing atmosphere in the presence of sulfur, hydrogen, and a hydrocarbon to form said supported catalyst.
摘要翻译： 通过在升高的温度和氢气存在下使其与通过加热一种或多种选自（NR 4）的含碳的双（四金属氧酸盐）催化剂前体盐形成的自促进催化剂相接触来提高烃进料， 2 [M（WS4）2]，（NR4）x [M（MoS4）2]及其混合物，其中R是一个或多个烷基，芳基或其混合物，其中助催化剂金属M共价键合在阴离子中， Ni，Co或Fe，其中如果M是Ni，x是2，如果M是在非氧化性气氛中，在硫，氢和烃的存在下，M是Co或Fe复合物，则x是3，以形成所述负载的催化剂。
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4.发明授权Transition metal tris-dithiolene and related complexes as precursors to active catalysts 失效过渡金属三 - 二硫戊烯和相关络合物作为活性催化剂的前体
公开(公告)号：US5026473A
公开(公告)日：1991-06-25
申请号：US521952
申请日：1990-05-11
CPC分类号： B01J31/1805 , B01J27/04 , B01J31/226 , B01J2231/641 , B01J2531/64 , B01J2531/66 , B01J2531/74 , B01J2540/22
摘要： The present invention is based on the discovery that certain transition metal containing complexes thermally decompose to form solids containing the transition metal, sulfur and carbon and that these transition metal, sulfur and carbon containing solids are particularly suitable as catalysts for hydrodesulfurization, hydrodenitrogenation and aromatics hydrogenation. The transition metal complexes that are thermally decomposed to novel catalysts are complexes of the type represented by the general formula ML.sup.n 3, wherein M is selected from Mo, W, Re and mixtures thereof, L is a dithiolene or aminobenzenethiolate ligand, and n represents the total charge of the metal complexes, and is 0, -1, or -2.
摘要翻译： 本发明基于以下发现：某些含过渡金属的络合物热分解形成含有过渡金属，硫和碳的固体，并且这些过渡金属，硫和碳的固体特别适合作为加氢脱硫，加氢脱氮和芳烃氢化的催化剂 。 被热分解成新型催化剂的过渡金属络合物是由通式MLn3表示的类型的络合物，其中M选自Mo，W，Re及其混合物，L是二硫醇或氨基苯硫酚配体，n代表总量 金属配合物的电荷，为0，-1或-2。
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5.发明授权Transition metal tris-dithiolene and related complexes as precursors to active catalysts 失效过渡金属三 - 二硫戊烯和相关络合物作为活性催化剂的前体
公开(公告)号：US4962077A
公开(公告)日：1990-10-09
申请号：US378565
申请日：1989-07-11
CPC分类号： B01J31/1805 , B01J27/04 , B01J31/226 , B01J2231/641 , B01J2531/64 , B01J2531/66 , B01J2531/74 , B01J2540/22
摘要： The present invention is based on the discovery that certain transition metal containing complexes thermally decompose to form solids containing the transmission metal, sulfur and carbon and that these transition metal, sulfur and carbon containing solids are particularly suitable as catalysts for hydrodesulfurization, hydrodenitrogenation and aromatics hydrogenation. The transition metal complexes that are thermally decomposed to novel catalysts are complexes of the type represented by the general formula ML.sup.n.sbsp.3, wherein M is selected from Mo, W, Re and mixtures thereof, L is a dithiolene or aminobenzenethiolate ligand, and n represents the total charge of the metal complexes, and is 0, -1, or -2.
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公开(公告)号：US4604183A
公开(公告)日：1986-08-05
申请号：US741993
申请日：1985-06-06
CPC分类号： C10G1/086
摘要： An improved hydroconversion process for carbonaceous materials wherein an ammonium or hydrocarbyl substituted ammonium salt of a metal-sulfur analog of cubane having an anion with a core structure of M.sub.4 S.sub.4 is used as a catalyst precursor. In the general formula, M may be the same or a different metal having hydrogenation catalytic activity when used as a sulfide and capable of occupying one or more vertices in a cubane structure. The metal may also have the capability of bridging one or more such structures. The improved process is effective for both normally solid and normally liquid carbonaceous materials and for carbonaceous materials which are either solid or liquid at the conversion conditions. The hydroconversion will be accomplished at a temperature within the range from about 500.degree. to about 900.degree. F., at a total pressure within the range from about 500 to about 7000 psig and at a hydrogen partial pressure within the range from about 400 to about 5000 psig.
摘要翻译： 用于含碳材料的改进的加氢转化方法，其中使用具有核心结构为M4S4的阴离子的立方烷金属 - 硫类似物的铵或烃基取代的铵盐作为催化剂前体。 在通式中，当用作硫化物并且能够占据立方体结构中的一个或多个顶点时，M可以是相同或不同的具有氢化催化活性的金属。 金属也可以具有桥接一个或多个这样的结构的能力。 改进的方法对于常规固体和常规含碳材料以及在转化条件下为固体或液体的碳质材料都是有效的。 加氢转化将在约500至约900°F范围内的温度下进行，总压力范围为约500至约7000psig，氢分压为约400至约 5000 psig
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7.发明授权Self-promoted molybdenum and tungsten sulfide hydrotreating catalysts from bis(tetrathiometallate) precursors 失效自助钼和硫化钨加氢处理催化剂由双（四金属氧酸盐）前体
公开(公告)号：US4510260A
公开(公告)日：1985-04-09
申请号：US518363
申请日：1983-07-29
IPC分类号： B01J23/85 , B01J27/04 , B01J27/049 , B01J31/02 , B01J31/34 , C10G45/08 , B01J27/02 , B01J31/12
CPC分类号： C10G45/08 , B01J23/85 , B01J27/04 , B01J27/049 , B01J31/0239 , B01J31/0254 , B01J31/34
摘要： Self-promoted molybdenum and tungsten sulfide hydrotreating catalyst are formed by heating one or more carbon-containing, bis(tetrathiometallate) catalyst precursor hydrogen with a supported, self-promoted catalyst salts selected from the group consisting of (NR.sub.4).sub.2 [M(WS.sub.4).sub.2 ], (NR.sub.4).sub.x [M(MoS.sub.4).sub.2 ] and mixtures thereof wherein R is one or more alkyl groups, aryl groups or mixture thereof, wherein promoter metal M is convalently bound in the anion and is Ni, Co or Fe and wherein x is 2 if M is Ni and x is 3 if M is Co or Fe in a non-oxidizing atmosphere in the presence of sulfur hydrogen, and hydrocarbon.
摘要翻译： 通过加热一种或多种含碳的双（四金属金属盐）催化剂前体氢与负载的自促进的催化剂盐形成自促进的钼和硫化钨加氢处理催化剂盐，所述催化剂盐选自（NR4）2 [M（WS4） ）2]，（NR4）x [M（MoS4）2]及其混合物，其中R是一个或多个烷基，芳基或其混合物，其中助催化剂金属M在阴离子中被共价结合，并且是Ni，Co或Fe 并且其中如果M是Ni，x是2，如果在硫的氢气和烃存在下，在非氧化气氛中M是Co或Fe，x是3。
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8.发明授权Amorphous, iron promoted Mo and W sulfide hydroprocessing catalysts and process for their preparation 失效无定形，铁促进的Mo和W硫化物加氢催化剂及其制备方法
公开(公告)号：US4820677A
公开(公告)日：1989-04-11
申请号：US687536
申请日：1984-12-28
IPC分类号： B01J27/049 , B01J27/051 , C10G45/08
CPC分类号： C10G45/08 , B01J27/049 , B01J27/0515
摘要： Hydrocarbon feeds are upgraded by contacting a feed, at elevated temperature and in the presence of hydrogen, with a catalyst comprising an amorphous sulfide of iron and a metal selected from the group consisting of Mo, W and mixture thereof. The catalysts are prepared by heating one or more catalyst precursor salts under oxygen-free conditions in the presence of sulfur at a temperature of at least about 250.degree. C. The precursor salts will contain a thiometallate anion of Mo, W or mixture thereof and a cation comprising iron as a promoter metal and, optionally, additional divalent promoter metals, wherein said promoter metal or metals are chelated by at least one neutral, nitrogen-containing polydentate ligand and wherein said additional promoter metal is selected from the group consisting of Ni, Co, Mn, Zn, Cu and mixture thereof.
摘要翻译： 通过在升高的温度和在氢的存在下使进料接触的催化剂与包含铁的无定形硫化物和选自Mo，W及其混合物的金属的催化剂进行升级。 催化剂是通过在至少约250℃的温度下在硫的存在下在无氧条件下加热一种或多种催化剂前体盐来制备的。前体盐将含有Mo，W或其混合物的硫代金属阴离子和 包含铁作为助催化剂金属的阳离子和任选的另外的二价助催化剂金属，其中所述促进剂金属或金属由至少一种中性含氮多齿配体螯合，并且其中所述另外的助催化剂金属选自Ni， Co，Mn，Zn，Cu及其混合物。
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9.发明授权Amorphous sulfide catalysts of trivalent chromium and promoter metals and method of making same 失效三价铬和助催化剂金属的无定形硫化物催化剂及其制备方法
公开(公告)号：US4716139A
公开(公告)日：1987-12-29
申请号：US846219
申请日：1986-03-31
IPC分类号： B01J27/047 , C10G49/04 , B01J31/00 , B01J27/049 , B01J27/051
CPC分类号： B01J27/047 , C10G49/04
摘要： A catalyst composition comprising an amorphous sulfide of trivalent chromium and at least one metal selected from the group consisting of (a) molybdenum, tungsten and mixture thereof and (b) mixtures of (a) with Fe, Ni, Co, Mn, Cu, Zn and mixture thereof is prepared by heating one or more precursors at a temperature of at least about 200.degree. C. under oxygen-free conditions in the presence of a sulfur, wherein said precursor is selected from the group consisting of [Cr.sub.1-z M.sub.z LX.sub.y ](MoS.sub.4).sub.n, [Cr.sub.1-z M.sub.z LX.sub.y ](WS.sub.4).sub.n and mixtures thereof, wherein M is one or more divalent promoter metals selected from the group consisting of Mn, Fe, Co, Ni, Cu, Zn and mixtures thereof, wherein L is one or more neutral nitrogen-containing ligands, wherein ligand X is a singly-charged anionic species and wherein 1>z.gtoreq.0, 1-z.gtoreq.y.gtoreq.0, and wherein n equals (3-z-y)/2. These compositions have been found to be good hydroprocessing catalysts, particularly hydrotreating catalysts exhibiting a very high hydrodenitrogenation activity and/or selectivity in nitrogen and sulfur-containing hydrocarbon feeds.
摘要翻译： 一种催化剂组合物，其包含三价铬的无定形硫化物和选自（a）钼，钨及其混合物的至少一种金属和（b）（a）与Fe，Ni，Co，Mn，Cu， Zn及其混合物通过在无硫条件下在硫存在下在至少约200℃的温度下加热一种或多种前体而制备，其中所述前体选自[Cr1-zMzLXy] （MoS4）n，[Cr1-zMzLXy]（WS4）n及其混合物，其中M是一种或多种选自Mn，Fe，Co，Ni，Cu，Zn的二价助催化剂金属及其混合物，其中L 是一种或多种中性含氮配体，其中配体X是单电荷阴离子物质，并且其中n等于（3-zy） ）/ 2。 已经发现这些组合物是良好的加氢处理催化剂，特别是在含氮和含硫烃进料中表现出非常高的加氢脱氮活性和/或选择性的加氢处理催化剂。
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公开(公告)号：US4626339A
公开(公告)日：1986-12-02
申请号：US656090
申请日：1984-09-28
CPC分类号： C10G49/04 , B01J27/047 , B01J37/20
摘要： Supported hydroprocessing catalysts comprising a sulfide of trivalent chromium and molybdenum or tungsten which optionally may contain one or more promotor metals such as Co, Fe, Ni and mixture thereof. These catalysts are obtained by comprising a preselected quantity of support material with a precursor salt containing a tetrathiometallate anion of Mo or W and a cation comprising trivalent chromium and, optionally, one or more promoter metals wherein both said trivalent chromium and promoter metal are chelated by at least one neutral, nitrogen-containing polydentate ligand and heating the composite in the presence of sulfur and hydrogen in an oxygen-free atmosphere. These catalysts have high selectivity for nitrogen removal. The chromium and promoter metal do not have to be in the same cation.
摘要翻译： 包括三价铬硫化物和钼或钨的负载型加氢处理催化剂，其任选地可以含有一种或多种助催化剂金属如Co，Fe，Ni及其混合物。 这些催化剂通过包含预选量的载体材料而获得，其前体盐含有Mo或W的四金属硫酸盐阴离子和包含三价铬的阳离子，以及任选的一种或多种助催化剂金属，其中所述三价铬和助催化剂金属都被 至少一种中性的含氮多齿配体，并在无氧气氛中在硫和氢的存在下加热复合物。 这些催化剂对脱氮具有高选择性。 铬和助催化剂金属不必在同一阳离子中。
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