公开(公告)号：US4003957A

公开(公告)日：1977-01-18

申请号：US655661

申请日：1976-02-05

申请人： George J. Antos

发明人： George J. Antos

IPC分类号： B01J23/89 ,  C07C5/41 ,  C10G35/09 ,  C07C3/04 ,  B01J27/08 ,  C10G23/04

CPC分类号： B01J23/8986 ,  C07C5/417 ,  C10G35/09 ,  C07C2521/04 ,  C07C2523/02 ,  C07C2523/04 ,  C07C2523/14 ,  C07C2523/36 ,  C07C2523/42 ,  C07C2523/44 ,  C07C2523/46 ,  C07C2523/75 ,  C07C2523/89 ,  Y02P20/52

摘要： Dehydrocyclizable hydrocarbons are converted to aromatics by contacting them at dehydrocyclization conditions with an acidic multi-metallic catalytic composite comprising a combination of catalytically effective amounts of a platinum group component, a rhenium component, a cobalt component, and a halogen component with a porous carrier material. The platinum group component, rhenium component, cobalt component, and halogen component are present in the multimetallic catalyst in amounts respectively, calculated on an elemental basis, corresponding to about 0.01 to about 2 wt. % platinum group metal, about 0.1 to about 5 wt. % cobalt, about 0.01 to about 2 wt. % rhenium, and about 0.1 to about 3.5 wt. % halogen. Moreover, the catalytically active sites induced by these metallic components are uniformly dispersed throughout the porous carrier material and these metallic components are present in the catalyst in carefully controlled oxidation states such that substantially all of the platinum group component is present therein in the elemental metallic state and substantially all of the rhenium and catalytically available cobalt components are present in the elemental metallic state or in a state which is reducible to the elemental metallic state under dehydrocyclization conditions, or in a mixture of these states. A specific example of dehydrocyclization method disclosed herein is a method for converting a feed mixture of n-hexane and n-heptane to a product mixture of benzene and toluene which involves contacting the feed mixture and a hydrogen stream with the acidic multimetallic catalyst disclosed herein at dehydrocyclization conditions.

摘要翻译： 将脱氢可环化烃转化为芳族化合物，使其在脱氢环化条件下与酸性多金属催化复合物接触，酸性多金属催化复合材料包含催化有效量的铂族组分，铼组分，钴组分和卤素组分与多孔载体材料 。 铂族组分，铼组分，钴组分和卤素组分分别以基于元素计算的量存在于多金属催化剂中，相当于约0.01至约2重量％ ％铂族金属，约0.1至约5wt。 ％钴，约0.01至约2重量％ ％铼，和约0.1至约3.5wt。 ％卤素。 此外，由这些金属组分诱导的催化活性位点均匀地分散在整个多孔载体材料中，并且这些金属组分以仔细控制的氧化态存在于催化剂中，使得基本上所有的铂族组分存在于元素金属状态 并且基本上所有的铼和催化可用的钴组分都以元素金属状态存在，或以脱氢环化条件或这些状态的混合物可还原成元素金属状态的状态存在。 本文公开的脱氢环化方法的具体实例是将正己烷和正庚烷的进料混合物转化为苯和甲苯的产物混合物的方法，其包括使进料混合物和氢气流与本文公开的酸性多金属催化剂接触 脱氢环化条件。

公开(公告)号：US3972806A

公开(公告)日：1976-08-03

申请号：US593086

申请日：1975-07-03

申请人： George J. Antos

发明人： George J. Antos

IPC分类号： B01J23/89 ,  C10G35/09 ,  C10G35/08 ,  C07C3/34 ,  C10G13/10

CPC分类号： C10G35/09 ,  B01J23/896 ,  Y10S585/906

摘要： Hydrocarbons are converted by contacting them at hydrocarbon conversion conditions with an acidic multimetallic catalytic composite comprising a combination of catalytically effective amounts of a platinum group component, a gallium component, a cobalt component, and a halogen component with a porous carrier material. The platinum group component, gallium component, cobalt component, and halogen component are present in the multimetallic catalyst in amounts respectively, calculated on an elemental basis, corresponding to about 0.01 to about 2 wt. % platinum group metal, about 0.01 to about 5 wt. % gallium, about 0.05 to about 5 wt. % cobalt, and about 0.1 to about 3.5 wt. % halogen. Moreover, these metallic components are uniformly dispersed throughout the porous carrier material in carefully controlled oxidation states such that substantially all of the platinum group metal is present therein in the elemental metallic state, substantially all of the catalytically available cobalt component is present in the elemental metallic state or in a state which is reducible to the elemental metallic state under hydrocarbon conversion conditions or in a mixture of these states, while substantially all of the gallium is present therein in an oxidation state above that of the elemental metal. A specific example of the type of hydrocarbon conversion process disclosed is a process for the catalytic reforming of a low-octane gasoline fraction wherein the gasoline fraction and a hydrogen stream are contacted with the acidic multimetallic catalyst disclosed herein at reforming conditions.

摘要翻译： 通过在烃转化条件下与含有催化有效量的铂族组分，镓组分，钴组分和卤素组分的组合的多元载体材料的酸性多金属催化复合物接触来转化烃。 铂族组分，镓组分，钴组分和卤素组分分别以基于元素计算的量存在于多金属催化剂中，相当于约0.01至约2重量％ ％铂族金属，约0.01至约5wt。 ％镓，约0.05至约5wt。 ％钴，和约0.1至约3.5wt。 ％卤素。 此外，这些金属组分在仔细控制的氧化状态下均匀地分散在整个多孔载体材料中，使得基本上所有的铂族金属存在于元素金属状态中，基本上所有的催化可用的钴组分存在于元素金属 状态或在烃转化条件下或这些状态的混合物中可还原成元素金属状态的状态，而基本上所有的镓以比元素金属高的氧化态存在于其中。 所公开的烃转化方法的具体实例是一种低辛烷值汽油馏分的催化重整方法，其中汽油馏分和氢气流在重整条件下与本文公开的酸性多金属催化剂接触。

公开(公告)号：US4420649A

公开(公告)日：1983-12-13

申请号：US464437

申请日：1983-02-07

申请人： George J. Antos

发明人： George J. Antos

IPC分类号： B01J23/46 ,  C10G35/09 ,  C07C5/36 ,  B01J27/08 ,  C07C5/40

CPC分类号： C10G35/09 ,  B01J23/46

摘要： Dehydrogenatable hydrocarbons are dehydrogenated by contacting them at hydrocarbon dehydrogenation conditions with a multimetallic catalytic composite comprising a combination of a catalytically effective amount of a pyrolyzed ruthenium carbonyl component with a porous carrier material containing a uniform dispersion of catalytically effective amounts of a platinum group component maintained in the elemental metallic state, and of a rhenium component. An optional non-acidic multimetallic catalytic composite disclosed herein is a combination of a catalytically effective amount of a pyrolyzed ruthenium carbonyl component with a porous carrier material containing a uniform dispersion of catalytically effective amounts of a platinum group component which is maintained in the elemental metallic state during the incorporation of the ruthenium carbonyl component, a rhenium component, and an alkali or alkaline earth component.

公开(公告)号：US4416804A

公开(公告)日：1983-11-22

申请号：US385589

申请日：1982-06-07

申请人： George J. Antos ,  Tai-Hsiang Chao

发明人： George J. Antos ,  Tai-Hsiang Chao

IPC分类号： B01J23/89 ,  B01J27/185 ,  C10G35/09 ,  B01J27/14

CPC分类号： B01J27/1856 ,  B01J23/8966 ,  C10G35/09

摘要： Hydrocarbons are converted by contacting them at hydrocarbon conversion conditions with an acidic multimetallic catalytic composite comprising a combination of catalytically effective amounts of a platinum group component, a cobalt component, a tin component, a phosphorus component and a halogen component with a porous carrier material. The platinum group, cobalt, tin, phosphorus and halogen components are present in the multimetallic catalyst in amounts respectively, calculated on an elemental basis, corresponding to about 0.01 to about 2 wt. % platinum group metal, about 0.05 to about 5 wt. % cobalt, about 0.01 to about 5 Wt. % tin, about 0.01 to about 5 wt. % phosphorus and about 0.1 to about 3.5 wt. % halogen. A specific example of the type of hydrocarbon conversion process disclosed is a process for the catalytic reforming of a low-octane gasoline fraction wherein the gasoline fraction and a hydrogen stream are contacted with the acidic multimetallic catalyst disclosed herein at reforming conditions.

摘要翻译： 通过在碳氢化合物转化条件下与含有催化有效量的铂族组分，钴组分，锡组分，磷组分和卤素组分与多孔载体材料的组合的酸性多金属催化复合物接触来转化碳氢化合物。 铂族，钴，锡，磷和卤素组分分别以基于元素计算的量存在于多金属催化剂中，相当于约0.01至约2重量％ ％铂族金属，约0.05至约5wt。 ％钴，约0.01至约5Wt。 ％锡，约0.01至约5wt。 ％磷和约0.1至约3.5重量％ ％卤素。 所公开的烃转化方法的具体实例是一种低辛烷值汽油馏分的催化重整方法，其中汽油馏分和氢气流在重整条件下与本文公开的酸性多金属催化剂接触。

公开(公告)号：US4343724A

公开(公告)日：1982-08-10

申请号：US209552

申请日：1980-11-24

申请人： George J. Antos

发明人： George J. Antos

IPC分类号： B01J23/656 ,  C10G35/09 ,  B01J23/64

CPC分类号： B01J23/6567 ,  C10G35/09

摘要： Dehydrogenatable hydrocarbons are dehydrogenated by contacting them, at hydrocarbon dehydrogenation conditions, with a novel attenuated superactive multimetallic catalytic composite comprising a combination of a catalytically effective amount of a pyrolyzed rhenium carbonyl component with a porous carrier material containing a uniform dispersion of catalytically effective amounts of a platinum group component maintained in the elemental metallic state, and of an iron component. An example of the attenuated superactive nonacidic multimetallic catalytic composite disclosed herein is a combination of a catalytically effective amount of a pyrolyzed rhenium carbonyl component with a porous carrier material containing a uniform dispersion of catalytically effective amounts of an alkali or alkaline earth component, an iron component, and of a platinum group component which is maintained in the elemental metallic state during the incorporation of the rhenium carbonyl component.

摘要翻译： 可脱氢烃通过在烃脱氢条件下与新型减毒超活性多金属催化复合材料接触来脱氢，该催化复合材料包含催化有效量的热解铼羰基组分与多孔载体材料的组合，所述多孔载体材料含有催化有效量的 维持在元素金属状态的铂族组分和铁组分。 本文公开的减毒超活性非酸性多金属催化复合物的实例是催化有效量的热解的铼羰基组分与多孔载体材料的组合，所述多孔载体材料含有催化有效量的碱金属或碱土金属组分的均匀分散体，铁组分 ，以及在引入羰基铼组分期间保持元素金属状态的铂族组分。

公开(公告)号：US4329259A

公开(公告)日：1982-05-11

申请号：US198731

申请日：1980-10-20

申请人： George J. Antos

发明人： George J. Antos

IPC分类号： B01J23/89 ,  C10G35/09 ,  B01J27/08 ,  B01J27/10

CPC分类号： B01J23/8953 ,  C10G35/09

摘要： An acidic multimetallic catalytic composite especially useful for converting hydrocarbons comprises a combination of catalytically effective amounts of a platinum component, a nickel component, a cadmium component, and a halogen component with a porous carrier material. The platinum, nickel, cadmium, and halogen components are present in the multimetallic catalyst in amounts respectively, calculated on an elemental basis, corresponding to about 0.01 to about 2 wt. % platinum, about 0.05 to about 5 wt. % nickel, about 0.01 to about 5 wt. % cadmium, and about 0.1 to about 3.5 wt. % halogen. Moreover, these metallic components are uniformly dispersed throughout the porous carrier material in carefully controlled oxidation states such that substantially all of the platinum component is present therein in the elemental metallic state, substantially all of the catalytically available nickel component is present in the elemental metallic state or in a state which is reducible to the elemental metallic state under hydrocarbon conversion conditions, or in a mixture of these states, while substantially all of the cadmium component is present in an oxidation state above that of the elemental metal.

摘要翻译： 特别适用于转化烃的酸性多金属催化复合物包括催化有效量的铂组分，镍组分，镉组分和卤素组分与多孔载体材料的组合。 铂，镍，镉和卤素组分分别以基于元素计算的量存在于多金属催化剂中，相当于约0.01至约2重量％ ％铂，约0.05至约5wt。 ％镍，约0.01至约5wt。 ％镉和约0.1至约3.5wt。 ％卤素。 此外，这些金属组分在仔细控制的氧化态下均匀地分散在整个多孔载体材料中，使得基本上所有的铂组分都存在于元素金属状态中，基本上所有的催化可用的镍组分以元素金属状态存在 或者在碳氢化合物转化条件下还原成元素金属状态的状态下，或以这些状态的混合状态，而基本上所有的镉成分的氧化态都高于元素金属。

公开(公告)号：US4312789A

公开(公告)日：1982-01-26

申请号：US197044

申请日：1980-10-15

申请人： George J. Antos

发明人： George J. Antos

IPC分类号： B01J23/656 ,  C10G35/09 ,  B01J27/08 ,  B01J23/62 ,  B01J27/10

CPC分类号： C10G35/09 ,  B01J23/6567 ,  C07C2521/04 ,  C07C2523/36 ,  C07C2523/42 ,  C07C2523/44 ,  C07C2523/656 ,  C07C2527/126

摘要： A novel attenuated superactive multimetallic catalytic composite especially useful for converting hydrocarbons comprises a combination of a catalytically effective amount of a pyrolyzed rhenium carbonyl component with a porous carrier material containing a uniform dispersion of catalytically effective amounts of a platinum group component, which is maintained in the elemental metallic state during the incorporation and pyrolysis of the rhenium carbonyl component, and of a tin component. In a highly preferred embodiment, this novel catalytic composite also contains a catalytically effective amount of a halogen component. The platinum group component, pyrolyzed rhenium carbonyl component, tin component and optional halogen component are preferably present in the multimetallic catalytic composite in amounts, calculated on an elemental basis, corresponding to about 0.01 to about 2 wt. % platinum group metal, about 0.01 to about 5 wt. % rhenium, about 0.005 to about 5 wt. % tin and about 0.1 to about 3.5 wt. % halogen. A key feature associated with the preparation of the subject catalytic composite is reaction of a rhenium carbonyl complex with a porous carrier material containing a uniform dispersion of a tin component and of a platinum group component maintained in the elemental state, whereby the interaction of the rhenium moiety with the platinum group moiety is maximized due to the platinophilic (i.e. platinum-seeking) propensities of the carbon monoxide ligands associated with the rhenium reagent.

摘要翻译： 特别适用于转化烃的新型减毒超活性多金属催化复合物包括催化有效量的热解铼羰基组分与含有催化有效量的铂族组分的均匀分散体的多孔载体材料的组合，其保持在 在羰基铼组分和锡组分的引入和热解期间的元素金属状态。 在一个非常优选的实施方案中，该新型催化复合材料还含有催化有效量的卤素组分。 铂族组分，热解的铼羰基组分，锡组分和任选的卤素组分优选以基于元素计算的量存在于多金属催化复合物中，相当于约0.01至约2重量％ ％铂族金属，约0.01至约5wt。 ％铼，约0.005至约5wt。 ％锡和约0.1至约3.5重量％ ％卤素。 与本发明的催化复合材料的制备相关的主要特征是羰基钌合物与含有均匀分散的锡组分和保持在元素状态的铂族组分的多孔载体材料的反应，由此铼的相互作用 与铂族部分的部分由于与铼试剂相关的一氧化碳配体的铂嗜性（即铂寻求）倾向而最大化。

公开(公告)号：US4304950A

公开(公告)日：1981-12-08

申请号：US203016

申请日：1980-11-03

申请人： George J. Antos

发明人： George J. Antos

IPC分类号： B01J23/89 ,  C07C5/32 ,  C07C5/333 ,  C07C5/367 ,  C10G35/09 ,  C07C5/18

CPC分类号： C10G35/09 ,  B01J23/898 ,  C07C5/325 ,  C07C5/3337 ,  C07C5/367 ,  C07C2521/04 ,  C07C2523/02 ,  C07C2523/04 ,  C07C2523/20 ,  C07C2523/42 ,  C07C2523/44 ,  C07C2523/46 ,  C07C2523/75 ,  C07C2523/89 ,  Y02P20/52

摘要： Dehydrogenatable hydrocarbons are dehydrogenated by contacting them, at dehydrogenation conditions, with a nonacidic catalytic composite comprising a combination of catalytically effective amounts of a platinum group component, a cobalt component, a tantalum component, and an alkali or alkaline earth component with a porous carrier material in amounts sufficient to result in a composite containing, on an elemental basis, about 0.01 to about 2 wt. % platinum group metal, about 0.05 to about 5 wt. % cobalt, about 0.01 to about 5 wt. % tantalum, and about 0.1 to about 5 wt. % alkali metal or alkaline earth metal.

摘要翻译： 可脱氢烃通过在脱氢条件下与含有催化有效量的铂族组分，钴组分，钽组分和碱金属或碱土金属组分的组合的非酸催化复合物与多孔载体材料 其量足以导致在元素基础上含有约0.01至约2wt。 ％铂族金属，约0.05至约5wt。 ％钴，约0.01至约5wt。 ％的钽，和约0.1至约5wt。 ％碱金属或碱土金属。

公开(公告)号：US4298462A

公开(公告)日：1981-11-03

申请号：US207825

申请日：1980-11-17

申请人： George J. Antos

发明人： George J. Antos

IPC分类号： B01J23/89 ,  C07C5/41 ,  C10G35/09 ,  B01J27/08

CPC分类号： B01J23/8953 ,  C07C5/417 ,  C10G35/09 ,  C07C2521/04 ,  C07C2523/02 ,  C07C2523/04 ,  C07C2523/06 ,  C07C2523/56 ,  C07C2523/755 ,  C07C2523/889 ,  Y02P20/52

摘要： Dehydrocyclizable hydrocarbons are converted to aromatics by contacting them at hydrocarbon dehydrocyclization conditions with an acidic multimetallic catalytic composite comprising a combination of catalytically effective amounts of a platinum group component, a nickel component, a zinc component, and a halogen component with a porous carrier material. The platinum group, nickel, zinc and halogen components are present in the multimetallic catalyst in amounts respectively, calculated on an elemental basis, corresponding to about 0.01 to about 2 wt. % platinum group metal, about 0.05 to about 5 wt. % nickel, about 0.01 to about 5 wt. % zinc, and about 0.1 to about 3.5 wt. % halogen. Moreover, the catalytically active sites induced by these metallic components are uniformly dispersed throughout the porous carrier material and these metallic components are present in the catalyst in carefully controlled oxidation states such that substantially all of the platinum group component is in the elemental metallic state, substantially all of the zinc component is preferably in an oxidation state above that of the elemental metal, and substantially all of the catalytically available nickel component is present in the elemental metallic state or in a state which is reducible to the elemental metallic state under hydrocarbon dehydrocyclization conditions, or in a mixture of these states. A specific example of the dehydrocyclization method disclosed herein is a method for converting a feed mixture of n-hexane and n-heptane to a product mixture of benzene and toluene which involves contacting the feed mixture and a hydrogen stream with the acidic multimetallic catalyst disclosed herein at hydrocarbon dehydrocyclization conditions.

摘要翻译： 通过使烃脱氢环化条件与包含催化有效量的铂族组分，镍组分，锌组分和卤素组分的组合的酸性多金属催化复合物与多孔载体材料接触，将可脱氢可环化的烃转化为芳族化合物。 铂族，镍，锌和卤素组分分别以基于元素计算的量存在于多金属催化剂中，相当于约0.01至约2wt。 ％铂族金属，约0.05至约5wt。 ％镍，约0.01至约5wt。 ％锌，和约0.1至约3.5重量％ ％卤素。 此外，由这些金属组分诱导的催化活性位点均匀地分散在整个多孔载体材料中，并且这些金属组分以仔细控制的氧化态存在于催化剂中，使得基本上所有的铂族组分都处于元素金属状态， 所有的锌组分优选地处于高于元素金属的氧化态，并且基本上所有的催化可用镍组分以元素金属状态存在，或者在烃脱氢环化条件下可以还原成元素金属状态 ，或这些状态的混合。 本文公开的脱氢环化方法的具体实例是将正己烷和正庚烷的进料混合物转化为苯和甲苯的产物混合物的方法，其包括使进料混合物和氢气流与本文公开的酸性多金属催化剂接触 在烃脱氢环化条件下。

公开(公告)号：US4268377A

公开(公告)日：1981-05-19

申请号：US82436

申请日：1979-10-05

申请人： George J. Antos

发明人： George J. Antos

IPC分类号： B01J23/40 ,  B01J31/20 ,  C10G35/09 ,  C10G35/08

CPC分类号： C10G35/09 ,  B01J23/40 ,  B01J23/462 ,  B01J27/13

摘要： Hydrocarbons are converted by contacting them at hydrocarbon conversion conditions with a novel activated multimetallic catalytic composite comprising a combination of a catalytically effective amount of a pyrolyzed ruthenium carbonyl component with a porous carrier material containing a uniform dispersion of a catalytically effective amount of a platinum group component, which is maintained in the elemental metallic state during the incorporation and pyrolysis of the ruthenium carbonyl component, and of a rhenium component. In a highly preferred embodiment, this novel catalytic composite also contains a catalytically effective amount of a halogen component. The platinum group component, pyrolyzed ruthenium carbonyl component, rhenium component and optional halogen component are preferably present in the multimetallic catalytic composite in amounts, calculated on an elemental basis, corresponding to about 0.01 to about 2 wt. % of the uniformly dispersed platinum group metal, about 0.01 to about 2 wt. % of carbonyl-derived ruthenium, about 0.01 to about 5 wt. % rhenium and about 0.01 to about 3.5 wt. % of halogen. A key feature associated with the preparation of the subject catalytic composite is reaction of a ruthenium carbonyl complex with a porous carrier material containing a uniform dispersion of a rhenium component and of a platinum group component maintained in the elemental state, whereby the interaction of the ruthenium moiety with the platinum group moiety is maximized due to the platinophilic (i.e. platinum-seeking) propensities of the carbon monoxide ligand used in the ruthenium reagent. A specific example of the type of hydrocarbon conversion process disclosed herein is a process for the catalytic reforming of a low octane gasoline fraction wherein the gasoline fraction and a hydrogen stream are contacted with the subject activated multimetallic catalytic composite at reforming conditions.