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1. 发明授权

US4239658A Catalysts for the conversion of relatively low molecular weight hydrocarbons to higher molecular weight hydrocarbons and the regeneration of the catalysts 失效
标题翻译：用于将相对低分子量烃转化为较高分子量烃的催化剂和催化剂的再生
公开(公告)号：US4239658A
公开(公告)日：1980-12-16
申请号：US27246
申请日：1979-04-05
申请人： Howard L. Mitchell, III , Robert H. Waghorne
发明人： Howard L. Mitchell, III , Robert H. Waghorne
IPC分类号： B01J23/64 , B01J23/68 , B01J23/85 , C07C2/00 , B01J21/04 , B01J23/10 , B01J23/58
CPC分类号： B01J23/64 , B01J23/683 , B01J23/85 , C07C2/00 , C07C2521/04 , C07C2521/06 , C07C2521/10 , C07C2523/02 , C07C2523/24 , C07C2523/40 , C07C2523/48 , C07C2523/755 , Y02P20/52 , Y02P20/582 , Y02P20/584 , Y10S502/524 , Y10S585/943
摘要： Novel regenerable catalyst-reagents, and a new and improved process utilizing said regenerable catalyst-reagents, for the conversion, and oligomerization of hydrocarbons, notably methane, at relatively low temperatures to produce products rich in ethylene or benzene, or both, usually in admixture with other hydrocarbons; and process for the regeneration of said catalyst-reagents. (a) The catalyst-reagents are multi-functional and are comprised of (1) a Group VIII noble metal having an atomic number of 45 or greater, nickel, or a Group I-B noble metal having an atomic number of 47 or greater; (2) a Group VI-B metal oxide which is capable of being reduced to a lower oxide, or admixture of metal oxides which includes one or more of such metal oxides; and, (3) a Group II-A metal selected from the group consisting of magnesium and strontium, composited with a suitably passivated, spinel-coated refractory support, notably an inorganic oxide support, preferably alumina; preferably calcium, composited with a suitably passivated, non-zinc containing spinel coated refractory support, notably an inorganic oxide support, preferably alumina.
摘要翻译：新型可再生催化剂试剂，以及利用所述可再生催化剂试剂的新的和改进的方法，用于在相对较低的温度下转化和低聚烃，特别是甲烷以生产富含乙烯或苯的产物，或两者，通常为混合物与其他碳氢化合物; 以及所述催化剂试剂再生的方法。（a）催化剂试剂是多功能的，并且包含（1）原子序数为45以上的Ⅷ族贵金属，镍或原子序数为47以上的I-B族贵金属; （2）能够还原成低氧化物的VI-B族金属氧化物，或包含这些金属氧化物中的一种或多种的金属氧化物的混合物; 和（3）选自镁和锶的II-A族金属，与适当钝化的尖晶石涂覆的耐火载体，特别是无机氧化物载体，优选氧化铝复合。优选钙，与合适钝化的非锌含尖晶石涂层的耐火载体，特别是无机氧化物载体，优选氧化铝复合。

2. 发明授权

US4205194A Process for the conversion of relatively low molecular weight hydrocarbons, to higher molecular weight hydrocarbons, catalyst-reagents for such use in such process, and the regeneration thereof 失效
标题翻译：相对低分子量烃转化为较高分子量烃的方法，用于此类方法的催化剂试剂及其再生方法
公开(公告)号：US4205194A
公开(公告)日：1980-05-27
申请号：US970540
申请日：1978-12-18
申请人： Howard L. Mitchell, III , Robert H. Waghorne
发明人： Howard L. Mitchell, III , Robert H. Waghorne
IPC分类号： B01J23/00 , B01J23/652 , B01J23/68 , B01J23/85 , C07C1/32 , C07C3/44
CPC分类号： B01J23/85 , B01J23/005 , B01J23/652 , B01J23/683 , C07C1/325 , C07C2521/04 , C07C2523/02 , C07C2523/26 , C07C2523/28 , C07C2523/30 , C07C2523/42 , C07C2523/44 , C07C2523/46 , Y02P20/52 , Y02P20/582 , Y02P20/584
摘要： Novel regenerable catalyst-reagents, and a new and improved process utilizing said regenerable catalyst-reagents, for the conversion, and oligomerization of hydrocarbons, notably methane, at relatively low temperatures to produce products rich in ethylene or benzene, or both, usually in admixture with other hydrocarbons; and process for the regeneration of said catalyst-reagents. (a) The catalyst-reagents are multi-functional and are comprised of (1) a Group VIII noble metal having an atomic number of 45 or greater, nickel, or a Group 1-B noble metal having an atomic number of 47 or greater; (2) a Group VI-B metal oxide which is capable of being reduced to a lower oxide, or admixture of metal oxides which includes one or more of such metal oxides; and, (3) a Group II-A metal or alkaline-earth metal, composited with a suitably passivated, spinel-coated refractory support, notably an inorganic oxide support, preferably alumina. (b) The process is one wherein a hydrocarbon feed, notably methane, is contacted and reacted with a catalyst-reagent as characterized in (a), supra, at temperature ranging from about 1150.degree. F. to about 1600.degree. F.; and also embodies (c) a process for regeneration of said catalyst-reagent which has become inactivated as by use in the process characterized in (b), supra, by contact thereof in an exothermic reaction with water, oxygen or an oxygen-containing gas, preferably air, at temperatures sufficient to reoxidize the Group VI-B metal oxide, and preferably also sufficient to provide the required sensible heat for the operation of said novel hydrocarbon conversion process (b), supra, on recycle of the catalyst-reagent.
摘要翻译：新型可再生催化剂试剂，以及利用所述可再生催化剂试剂的新的和改进的方法，用于在较低温度下转化和低聚烃，特别是甲烷，以生产富含乙烯或苯的产物，或两者，通常为混合物与其他碳氢化合物; 以及所述催化剂试剂再生的方法。（a）催化剂试剂是多官能的，并且包含（1）原子序数为45以上的Ⅷ族贵金属，镍或原子序数为47以上的1族B族贵金属 ; （2）能够还原成低氧化物的VI-B族金属氧化物，或包含这些金属氧化物中的一种或多种的金属氧化物的混合物; 和（3）II-A族金属或碱土金属，与适当钝化的尖晶石涂层耐火载体，特别是无机氧化物载体，优选氧化铝复合。（b）该方法是其中烃进料，特别是甲烷与催化剂试剂接触并与其反应，其特征在于（a），同上，温度范围为约1150°F至约1600°F; 并且还体现了（c）如上述（b）所述的方法，通过在与水，氧气或含氧气体的放热反应中与其接触而使已经失活的所述催化剂试剂的再生方法，优选空气，在足以再次氧化VI-B族金属氧化物的温度下，优选还足以为上述新型烃转化方法（b）在催化剂 - 试剂的再循环中的操作提供所需的显热。

3. 发明授权

US4172810A Catalysts for the conversion of relatively low molecular weight hydrocarbons to high molecular weight hydrocarbons and the regeneration of the catalysts 失效
标题翻译：用于将相对低分子量烃转化为高分子量烃的催化剂和催化剂的再生
公开(公告)号：US4172810A
公开(公告)日：1979-10-30
申请号：US903814
申请日：1978-05-08
申请人： Howard L. Mitchell, III , Robert H. Waghorne
发明人： Howard L. Mitchell, III , Robert H. Waghorne
IPC分类号： B01J23/00 , B01J23/652 , B01J23/68 , B01J23/85 , C07C1/32 , B01J21/04 , B01J23/58 , B01J23/64 , B01J23/78
CPC分类号： C07C1/325 , B01J23/005 , B01J23/652 , B01J23/683 , B01J23/85 , C07C2521/04 , C07C2523/02 , C07C2523/26 , C07C2523/28 , C07C2523/30 , C07C2523/42 , C07C2523/44 , C07C2523/46 , Y02P20/52 , Y02P20/582 , Y02P20/584 , Y10S502/524 , Y10S585/943
摘要： Novel regenerable catalyst-reagents, and a new and improved process utilizing said regenerable catalyst-reagents, for the conversion, and oligomerization of hydrocarbons, notably methane, at relatively low temperatures to produce products rich in ethylene or benzene, or both, usually in admixture with other hydrocarbons; and process for the regeneration of said catalyst-reagents. (a) The catalyst-reagents are multi-functional and are comprised of (1) a Group VIII noble metal having an atomic number of 45 or greater, nickel, or a Group I-B noble metal having an atomic number of 47 or greater; (2) a Group VI-B metal oxide which is capable of being reduced to a lower oxide, or admixture of metal oxides which includes one or more of such metal oxides; and, (3) a Group II-A metal or alkaline-earth metal, composited with a suitably passivated, spinel-coated refractory support, notably an inorganic oxide support, preferably alumina.
摘要翻译：新型可再生催化剂试剂，以及利用所述可再生催化剂试剂的新的和改进的方法，用于在较低温度下转化和低聚烃，特别是甲烷，以生产富含乙烯或苯的产物，或两者，通常为混合物与其他碳氢化合物; 以及所述催化剂试剂再生的方法。（a）催化剂试剂是多功能的，并且包含（1）原子序数为45以上的Ⅷ族贵金属，镍或原子序数为47以上的I-B族贵金属; （2）能够还原成低氧化物的VI-B族金属氧化物，或包含这些金属氧化物中的一种或多种的金属氧化物的混合物; 和（3）II-A族金属或碱土金属，与适当钝化的尖晶石涂层耐火载体，特别是无机氧化物载体，优选氧化铝复合。

4. 发明授权

US4540481A Catalysts from molybdenum polysulfide precursors, their preparation and use 失效
标题翻译：来自钼多硫化物前体的催化剂，其制备和用途
公开(公告)号：US4540481A
公开(公告)日：1985-09-10
申请号：US551594
申请日：1983-11-14
申请人： Willard H. Sawyer , Howard L. Mitchell, III
发明人： Willard H. Sawyer , Howard L. Mitchell, III
IPC分类号： B01J23/28 , B01J27/04 , C10G45/04 , C10G45/08
CPC分类号： C10G49/04 , B01J23/28 , B01J27/04
摘要： A process for the preparation of novel highly active, highly selective hydrotreating catalysts. These catalysts are prepared, in bulk or in supported form, by contacting together and decomposing, in the presence of hydrogen, hydrocarbon, and sulfur, a catalyst precursor characterized by the formula B.sub.x [Mo.sub.3 S.sub.z ] where B is an ammonium ion, polyammonium ion, tertiary or quaternary phosphonium ion, or a hydrocarbyl substituted ammonium ion, hydrocarbyl substituted polyammonium ion, or hydrocarbyl substituted tertiary or quaternary phosphonium ion, x is 1 where B is a divalent cationic moiety, or 2 where B is a monovalent cationic moiety, [Mo.sub.3 S.sub.z ] is a divalent anionic moiety wherein z is an integer ranging from about 10 to about 46. A preferred precursor catalyst species is Mo.sub.3 (S.sub.2).sub.6 S.
摘要翻译：一种制备新型高活性，高选择性加氢处理催化剂的方法。这些催化剂以体积或负载形式通过在氢，烃和硫的存在下接触并分解，其特征在于式Bx [Mo 3 S z]的催化剂前体，其中B是铵离子，聚铵离子，叔或季鏻离子或烃基取代的铵离子，烃基取代的多铵离子或烃基取代的叔或鏻离子，x是1，其中B是二价阳离子部分，或2其中B是一价阳离子部分[Mo 3 Sz ]是二价阴离子部分，其中z是约10至约46的整数。优选的前体催化剂种类是Mo 3（S 2）6 S。

5. 发明授权

US4542121A Catalysts from molybdenum polysulfide precursors, their preparation and use 失效
标题翻译：来自钼多硫化物前体的催化剂，其制备和用途
公开(公告)号：US4542121A
公开(公告)日：1985-09-17
申请号：US570364
申请日：1984-01-13
申请人： Howard L. Mitchell, III , Willard H. Sawyer
发明人： Howard L. Mitchell, III , Willard H. Sawyer
IPC分类号： B01J23/28 , B01J27/04 , B01J27/02 , B01J27/24 , B01J31/02 , C01G37/00
CPC分类号： B01J23/28 , B01J27/04
摘要： A process for the preparation of novel highly active, highly selective hydrotreating catalysts. These catalysts are prepared, in bulk or in supported form, from a catalyst precursor characterized by the formula B.sub.x [Mo.sub.3 S.sub.z ] where B is an ammonium ion, polyammonium ion, tertiary or quaternary phosphonium ion, or a hydrocarbyl substituted ammonium ion, hydrocarbyl substituted polyammonium ion, or hydrocarbyl substituted tertiary or quaternary phosphonium ion, x is 1 where B is a divalent cationic moiety, or 2 where B is a monovalent cationic moiety, [Mo.sub.3 S.sub.z ] is a divalent anionic moiety wherein z is an integer greater than 15. The catalyst precursor is dispersed in an ammonium sulfide or dilute ammonium polysulfide solution and heated to remove sulfur from said catalyst precursor to provide a z value of 15 or less. Carbon is also removed from the catalyst precursor and, where B of the B.sub.x [Mo.sub.3 S.sub.z ] catalyst precursor is a non-carbon containing moiety, the finished catalyst will contain an atomic ratio of C/Mo of less than about 0.05. Decomposition of the catalyst precursor in the presence of hydrogen, hydrocarbon and sulfur forms the highly active hydrotreating catalyst.
摘要翻译：一种制备新型高活性，高选择性加氢处理催化剂的方法。这些催化剂以体积或负载形式由特征为式Bx [Mo 3 S z]的催化剂前体制备，其中B是铵离子，聚铵离子，叔或季鏻离子或烃基取代的铵离子，烃基取代的聚铵离子或烃基取代的叔或季鏻离子，x是1，其中B是二价阳离子部分，或2其中B是一价阳离子部分，[Mo 3 S z]是二价阴离子部分，其中z是大于15的整数。催化剂前体分散在硫化铵或多硫化铵溶液中并加热以从所述催化剂前体中除去硫以提供15或更小的az值。碳也从催化剂前体中除去，并且其中Bx [Mo3Sz]催化剂前体的B是不含碳的部分，成品催化剂将含有小于约0.05的C / Mo的原子比。在氢，烃和硫存在下分解催化剂前体形成高活性加氢处理催化剂。

6. 发明授权

US4522932A Phosphine and phosphonium compounds and catalysts 失效
标题翻译：膦和鏻化合物和催化剂
公开(公告)号：US4522932A
公开(公告)日：1985-06-11
申请号：US603141
申请日：1984-04-23
申请人： Howard L. Mitchell, III
发明人： Howard L. Mitchell, III
IPC分类号： B01J31/18 , B01J31/24 , C01B3/16 , C07C5/03 , C07C45/50 , C07F7/00 , C07F7/30 , C07F9/54 , C07F9/72 , C07F9/74 , C07F11/00 , C07F13/00 , C07F15/00 , C07F15/02 , C07F15/04 , C07F15/06 , C07F17/02 , B01J31/12
CPC分类号： C07F17/02 , B01J31/24 , C01B3/16 , C07C45/50 , C07C5/03 , C07F11/005 , C07F13/005 , C07F15/004 , C07F15/0053 , C07F15/0066 , C07F15/008 , C07F15/0093 , C07F15/025 , C07F15/045 , C07F15/065 , C07F7/006 , C07F7/30 , C07F9/54 , C07F9/72 , C07F9/743 , B01J2231/321 , B01J2531/845 , B01J31/1895 , C07C2531/24 , Y02P20/52
摘要： Novel ligand materials and transition metal complexes thereof are disclosed which are useful as solvents and/or catalysts for various processes, including catalytic conversion processes for the conversion of hydrocarbons or carbon monoxide, such as the hydrocarbonylation of olefins, hydrogenation using H.sub.2 or CO and H.sub.2 O, dehydrogenation, hydrocarbon synthesis, alcohol synthesis, and water-gas disproportionation catalysis. Among the novel ligand materials disclosed are compositions containing phosphine and arsine coordinating groups along with, e.g., groups comprising fluorines, ethynyl or ethenyl groups, quaternary ammonium, arsonium and/or phosphonium groups. Ligands containing M-O-L linkages and complexes thereof are also disclosed wherein M is selected from, for example, Si or Ti and L is selected from P or As. Also, various ion-exchanged ligand compositions, photoreactive compositions and the uses of such compositions are also described.
摘要翻译：公开了新的配体材料和其过渡金属络合物，其可用作各种方法的溶剂和/或催化剂，包括用于转化烃或一氧化碳的催化转化方法，例如烯烃的烃基化，使用H 2或CO和H 2 O的氢化，脱氢，烃合成，醇合成和水煤气歧化催化。所公开的新型配体材料包括含有膦和胂配位基团以及例如包含氟，乙炔基或乙烯基，季铵，ium和/或鏻基的基团的组合物。还公开了含有M-O-L键的配体及其配合物，其中M选自例如Si或Ti，L选自P或As。此外，还描述了各种离子交换的配体组合物，光反应性组合物和这些组合物的用途。

7. 发明授权

US4473505A Phosphine and phosphonium compounds and catalysts 失效
标题翻译：膦和鏻化合物和催化剂
公开(公告)号：US4473505A
公开(公告)日：1984-09-25
申请号：US423641
申请日：1982-09-27
申请人： Howard L. Mitchell, III
发明人： Howard L. Mitchell, III
IPC分类号： B01J31/24 , C07C45/50 , C07F11/00 , C07F15/00 , C07F15/02 , C07F15/04 , C07F17/02
CPC分类号： B01J31/1845 , B01J31/1865 , B01J31/1875 , B01J31/20 , B01J31/2295 , B01J31/24 , B01J31/2404 , C07C45/50 , C07F11/005 , C07F15/0006 , C07F15/02 , C07F15/04 , C07F17/02 , B01J2231/321 , B01J2531/0205 , B01J2531/16 , B01J2531/17 , B01J2531/18 , B01J2531/60 , B01J2531/70 , B01J2531/821 , B01J2531/824 , B01J2531/825 , B01J2531/828 , B01J2531/842 , B01J2531/847 , B01J2531/96 , B01J2540/22 , B01J2540/54 , B01J2540/64 , C07C2101/14
摘要： Novel ligand materials and transition metal complexes thereof are disclosed which are useful as solvents and/or catalysts for various processes, including catalytic conversion processes for the conversion of hydrocarbons or carbon monoxide, such as the hydrocarbonylation of olefins, hydrogenation using H.sub.2 or CO and H.sub.2 O, dehydrogenation, hydrocarbon synthesis, alcohol synthesis, and water-gas disproportionation catalysis. Among the novel ligand materials disclosed are compositions containing phosphine and arsine coordinating groups along with, e.g., groups comprising fluorines, ethynyl or ethenyl groups, quaternary ammonium, arsonium and/or phosphonium groups. Ligands containing M--O--L linkages and complexes thereof are also disclosed wherein M is selected from, for example, Si or Ti and L is selected from P or As. Also, various ion-exchanged ligand compositions, photoreactive compositions and the uses of such compositions are also described.
摘要翻译：公开了新的配体材料和其过渡金属络合物，其可用作各种方法的溶剂和/或催化剂，包括用于转化烃或一氧化碳的催化转化方法，例如烯烃的烃基化，使用H 2或CO和H 2 O的氢化，脱氢，烃合成，醇合成和水煤气歧化催化。所公开的新型配体材料包括含有膦和胂配位基团以及例如包含氟，乙炔基或乙烯基，季铵，ium和/或鏻基的基团的组合物。还公开了含有M-O-L键的配体及其配合物，其中M选自例如Si或Ti，L选自P或As。此外，还描述了各种离子交换的配体组合物，光反应性组合物和这些组合物的用途。

8. 发明授权

US4430442A Catalysts from molybdenum polysulfide precursors and their preparation 失效
标题翻译：钼多硫化物前体催化剂及其制备
公开(公告)号：US4430442A
公开(公告)日：1984-02-07
申请号：US399947
申请日：1982-07-20
申请人： Willard H. Sawyer , Howard L. Mitchell, III
发明人： Willard H. Sawyer , Howard L. Mitchell, III
IPC分类号： B01J23/28 , B01J27/051 , B01J27/02 , B01J27/24 , B01J31/12
CPC分类号： B01J23/28 , B01J27/051
摘要： A process for the preparation of novel highly active, highly selective hydrotreating catalysts. These catalysts are prepared, in bulk or in supported form, by contacting together and decomposing, in the presence of hydrogen, hydrocarbon, and sulfur, a catalyst precursor characterized by the formula B.sub.x [Mo.sub.3 S.sub.z ] where B is an ammonium ion, polyammonium ion, tertiary or quaternary phosphonium ion, or a hydrocarbyl substituted ammonium ion, hydrocarbyl substituted polyammonium ion, or hydrocarbyl substituted tertiary or quaternary phosphonium ion, x is 1 where B is a divalent cationic moiety, or 2 where B is a monovalent cationic moiety, [Mo.sub.3 S.sub.z ] is a divalent anionic moiety wherein z is an integer ranging from about 10 to about 46. A preferred precursor catalyst species is Mo.sub.3 (S.sub.2).sub.6 S.
摘要翻译：一种制备新型高活性，高选择性加氢处理催化剂的方法。这些催化剂通过在氢气，烃和硫的存在下接触并分解而制备，其特征在于以下公式的催化剂前体：其中B是铵离子，其中B是铵离子，聚铵离子，叔或季鏻离子或烃基取代的铵离子，烃基取代的多铵离子或烃基取代的叔或季鏻离子，x是1，其中B是二价阳离子部分，或2其中B是一价阳离子部分， Mo 3 S z]是二价阴离子部分，其中z是约10至约46的整数。优选的前体催化剂种类是Mo 3（S 2）6 S。

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