By Dehydrogenation Patents (Class 585/654)
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Patent number: 6488838Abstract: The present invention is a chemical reactor and method for catalytic chemical reactions having gas phase reactants. The chemical reactor has reactor microchannels for flow of at least one reactant and at least one product, and a catalyst material wherein the at least one reactant contacts the catalyst material and reacts to form the at least one product. The improvement, according to the present invention is: the catalyst material is on a porous material having a porosity that resists bulk flow therethrough and permits molecular diffusion therein. The porous material further has a length, a width and a thickness, the porous material defining at least a portion of one wall of a bulk flow path through which the at least one reactant passes.Type: GrantFiled: August 17, 1999Date of Patent: December 3, 2002Assignee: Battelle Memorial InstituteInventors: Anna Lee Y. Tonkovich, Yong Wang, Sean P. Fitzgerald, Jennifer L. Marco, Gary L. Roberts, David P. Vanderwiel, Robert S. Wegeng
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Patent number: 6476261Abstract: A process for the oxidation of a C2 to C4 alkane to produce the corresponding alkene and carboxylic acid which process comprises contacting in an oxidation reaction zone, said alkane, molecular oxygen-containing gas, and optionally, at least one of the corresponding alkene and water, in the presence of at least two catalysts each active, with different selectivities, for the oxidation of the alkane to the corresponding alkene and carboxylic acid, to produce a product stream comprising said alkene, carboxylic acid and water, and in which process the molar ratio of alkene to carboxylic acid produced in said oxidation reaction zone is adjusted or maintained at a pre-determined value by controlling the relative proportions of the at least two catalysts in said oxidation reaction zone. Such an oxidation process may be used in an integrated process, such as for the manufacture of ethyl acetate or vinyl acetate.Type: GrantFiled: September 28, 2001Date of Patent: November 5, 2002Assignee: BP Chemicals LimitedInventors: Brian Ellis, Mark Stephen Roberts
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Patent number: 6475464Abstract: The present invention concerns a process for preparing a zeolite with structure type MTT comprising at least one element X selected from silicon and germanium and at least one element T selected from iron, aluminium, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese, characterized in that seeds of at least one zeolitic material are used comprising at least one element X′ selected from silicon and germanium and at least one element T′ selected from iron, aluminium, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese, said seeds being different from the zeolite with structure type MTT being synthesised. The present invention also concerns the use of the zeolite obtained as a catalyst in a process for converting hydrocarbon-containing feeds, as an adsorbent to control pollution and as a molecular sieve for separation.Type: GrantFiled: September 29, 2000Date of Patent: November 5, 2002Assignee: Institut Francais du PetroleInventors: Loïc Rouleau, Frédéric Kolenda, Eric Benazzi
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Patent number: 6472577Abstract: A method increases the feed throughput for a process of dehydrogenating light hydrocarbons without loss of conversion or selectivity by increasing the catalyst volume in only the final reactor of at least three reaction zones. The catalyst volume of the final reactor may be increased relative to the other reactors by extending the inner and outer screens that define a radial flow bed therein. Maintaining a low LHSV by increasing the catalyst volume in only the final reactor greatly reduces the expense of improving the capacity and yield of such a process. This method provides the most benefit to moving bed reactor systems since modifications are limited to the last reactor. A further benefit is derived from the simplified method of raising only a section of the last reactor to increase the catalyst volume.Type: GrantFiled: December 10, 1999Date of Patent: October 29, 2002Assignee: UOP LLCInventors: Joseph E. Zimmermann, Paul R. Cottrell, Michael J. Vetter
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Patent number: 6425998Abstract: A process for using a hydrogen sensor in a liquid metal heat exchange loop in a hydrocarbon conversion process with high hydrogen permeation. The hydrogen sensor of the present invention consists essentially of a hollow nickel membrane probe in intimate contact with liquid metal. A vacuum chamber in fluid communication with the hollow nickel membrane probe through which hydrogen permeates, wherein the vacuum chamber is initially evacuated to a vacuum pressure and is in equilibrium with the vacuum chamber. The hydrogen sensor is useful for measuring the partial pressure of the hydrogen in the liquid metal to provide advisory control for the removal of hydrogen from the liquid metal exchange loop to avoid the problem of metal hydride formation and associated plugging problems.Type: GrantFiled: February 23, 2000Date of Patent: July 30, 2002Assignee: UOP LLCInventor: Donald Cholewa
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Patent number: 6417422Abstract: Catalysts and method for alkane dehydrogenation are disclosed. The catalysts of the invention generally comprise (i) nickel or a nickel-containing compound and (ii) at least one or more of titanium (Ti), tantalum (Ta), niobium (Nb), hafnium (Hf), tungsten (W), yttrium (Y), zinc (Zn), zirconium (Zr), or aluminum (Al), or a compound containing one or more such element(s). In preferred embodiments, the catalyst is a supported catalyst, the alkane or substituted alkane is selected from the group consisting of ethane, propane, isobutane, butane and ethyl chloride, molecular oxygen is co-fed with the alkane or substituted alkane to a reaction maintained at a temperature ranging from about 250° C. and about 350° C., and the ethane is oxidatively dehydrogenated to form the corresponding alkene with an alkene conversion of at least about 10% and an alkene selectivity of at least about 70%.Type: GrantFiled: February 22, 2000Date of Patent: July 9, 2002Assignee: Symyx Technologies, Inc.Inventor: Yumin Liu
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Publication number: 20020087042Abstract: A process and catalyst for the partial oxidation of paraffinic hydrocarbons, such as ethane, propane, naphtha, and natural gas condensates, to olefins, such as ethylene and propylene. The process involves contacting a paraffinic hydrocarbon with oxygen in the presence of a catalyst under autothermal process conditions. The catalyst comprises a Group 8B metal and, optionally, a promoter metal, such as tin or copper, supported on a fiber monolith support, preferably a ceramic fiber mat monolith. In another aspect, the invention is a process of oxidizing a paraffinic hydrocarbon to an olefin under autothermal conditions in the presence of a catalyst comprising a Group 8B metal and, optionally, a promoter metal, the metals being loaded onto the front face of a monolith support. An on-line method of synthesizing and regenerating catalysts for autothermal oxidation processes is also disclosed. This divisional case covers the catalyst composition and the method of preparing an olefin using the catalyst.Type: ApplicationFiled: December 5, 2001Publication date: July 4, 2002Inventors: Lanny D. Schmidt, Ashish Bodke
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Patent number: 6414209Abstract: The invention relates to a calcinated catalyst for converting paraffinic hydrocarbon into corresponding olefin through dehydrogenation. The catalyst is an oxidic, heat-stable carrier material and contains a catalytic active constituent, which is applied on the carrier material and has the following composition (in wt. % in relation to the entire weight of the catalyst): a) 0.2 to 2.0% of at least one element of the groups Pt and Ir and, acting as a promoter, a combination of elements from the six following groups of substances: b) 0.2 to 5.0% of at least one of the following elements Ge, Sn, Pb, Ga, In, Tl; c) 0.1 to 5.0% of at least one of the following elements Li, Na, K, Rb, Cs, Fr; d) 0.2 to 5.0% of at least one of the following elements Fe, Co, Ni, Pd; e) 1.0 to 5.0% P; f) 0.2 to 5.0% of at least one of the following elements Be, Mg, Ca, Sr, Ba, Ra and lanthanides and g) 0.1 to 2.0% Cl.Type: GrantFiled: September 25, 2000Date of Patent: July 2, 2002Assignees: Mannesman AG, K.T.I. Group B.V.Inventors: Mordechay Herskowitz, Shimson Kogan
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Patent number: 6392113Abstract: The performance of an endothermic catalytic dehydrogenation process is increased without requiring additional catalyst regeneration and reheat air flow and compression by partially prereacting the preheated hydrocarbon feed and then reheating the partially dehydrogenated effluent from the prereactor to the same hydrocarbon preheat temperature prior to the main catalytic reactor. The preferable source of the heat for reheating is the effluent air from the reheat and regeneration of the catalyst in the main reactor. This same effluent air is used to regenerate the catalyst in the prereactor as needed.Type: GrantFiled: October 3, 2000Date of Patent: May 21, 2002Assignee: ABB Lummus Global Inc.Inventor: Robert J. Gartside
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Patent number: 6388152Abstract: A process for producing polymers from olefins selectively produced from a catalytically cracked or thermally cracked naphtha stream is disclosed herein. The naphtha stream is introduced into a process unit comprised of a reaction zone, a stripping zone, a catalyst regeneration zone, and a fractionation zone. The naphtha feedstream is contacted in the reaction zone with a catalyst containing from about 10 to 50 wt. % of a crystalline zeolite having an average pore diameter less than about 0.7 nanometers at reaction conditions which include temperatures ranging from about 500° to 650° C. and a hydrocarbon partial pressure from about 10 to 40 psia. Vapor products are collected overhead and the catalyst particles are passed through the stripping zone on the way to the catalyst regeneration zone. Volatiles are stripped with steam in the stripping zone and the catalyst particles are sent to the catalyst regeneration zone where coke is burned from the catalyst, which is then recycled to the reaction zone.Type: GrantFiled: March 2, 2000Date of Patent: May 14, 2002Assignee: ExxonMobil Chemical Patents Inc.Inventors: Paul K. Ladwig, John E. Asplin, Gordon F. Stuntz, Tan-Jen Chen
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Patent number: 6362385Abstract: A process for obtaining light olefins by the dehydrogenation of corresponding paraffins, by reacting the paraffins with a catalytic system containing chromium oxide, tin oxide, at least one alkali metal oxide, and an alumina-silica carrier, and then regenerating the catalytic system in a regenerator by burning coke deposited on its surface at a temperature higher than the average temperature of the reactor.Type: GrantFiled: July 23, 1998Date of Patent: March 26, 2002Assignees: Siamprogetti S.p.A., Oao Nil YarsintezInventors: Rodolfo Iezzi, Andrea Bartolini, Franco Buonomo, Gueorgui Kotelnikov, Vladimir Bespalov
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Patent number: 6355854Abstract: Processes for oxidative dehydrogenation of alkane to one or more olefins, exemplified by ethane to ethylene, are disclosed using novel catalysts. The catalysts comprise a mixture of metal oxides having as an important component nickel oxide (NiO), which give high conversion and selectivity in the process. The catalyst can be used to make ethylene by contacting it with a gas mixture containing ethane and oxygen. The gas mixture may optionally contain ethylene, an inert diluent such as nitrogen, or both ethylene and an inert diluent.Type: GrantFiled: February 22, 1999Date of Patent: March 12, 2002Assignee: Symyx Technologies, Inc.Inventor: Yumin Liu
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Patent number: 6339180Abstract: A process for producing polypropylene from olefins selectively produced from a catalytically cracked or thermally cracked naphtha stream is disclosed herein. The naphtha stream is contacted with a catalyst containing from about 10 to 50 wt. % of a crystalline zeolite having an average pore diameter less than about 0.7 nanometers at reaction conditions which include temperatures from about 500° C. to 650° C. and a hydrocarbon partial pressure from about 10 to 40 psia.Type: GrantFiled: March 2, 2000Date of Patent: January 15, 2002Assignee: ExxonMobil Chemical Patents, Inc.Inventors: Paul K. Ladwig, John E. Asplin, Gordon F. Stuntz, William A. Wachter, B. Erik Henry
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Publication number: 20010049460Abstract: A method comprising:Type: ApplicationFiled: February 9, 2001Publication date: December 6, 2001Inventor: Charles Herzog
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Patent number: 6326523Abstract: Process for the dehydrogenation of a hydrocarbon feed comprising a step of dehydrogenating the hydrocarbon feed and a step of removing hydrogen being formed by dehydrogenation reactions, wherein the dehydrogenation and hydrogen removal steps are performed simultaneously in presence of a dehydrogenation catalyst being combined with a metal compound being reduced in presence of hydrogen.Type: GrantFiled: March 28, 2000Date of Patent: December 4, 2001Assignee: Haldor Topsoe A/SInventors: Anni Stahl, Niels Jørgen Blom, Jens Perregaard, Poul Erik Højlund Nielsen
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Publication number: 20010047119Abstract: A solid acid-base catalyst contains vanadium pentoxide hydrate.Type: ApplicationFiled: March 15, 1999Publication date: November 29, 2001Inventors: NOBUJI KISHIMOTO, ETSUSHIGE MATSUNAMI
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Patent number: 6300537Abstract: Disclosed are silicoaluminates (SAPOs) having unique silicon distributions, a method for their preparation and their use as naphtha cracking catalysts. More particularly, the new SAPOs have a high silica:alumina ratio and favorable Si atom distribution.Type: GrantFiled: May 20, 1999Date of Patent: October 9, 2001Assignee: Exxon Research and Engineering CompanyInventors: Karl G. Strohmaier, David E. W. Vaughan, Tan Jen Chen, Philip A. Ruziska, Brian Erik Henry, Gordon F. Stuntz, Stephen M. Davis
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Publication number: 20010025129Abstract: Processes for oxidative dehydrogenation of alkane to one or more olefins, exemplified by ethane to ethylene, are disclosed using novel catalysts. The catalysts comprise a mixture of metal oxides having as an important component nickel oxide (NiO), which give high conversion and selectivity in the process. For example, the catalyst can be used to make ethylene by contacting it with a gas mixture containing ethane and oxygen. The gas mixture may optionally contain ethylene, an inert diluent such as nitrogen, or both ethylene and an inert diluent.Type: ApplicationFiled: March 22, 2001Publication date: September 27, 2001Applicant: Symyx Technologies, Inc.Inventor: Yumin Liu
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Patent number: 6291686Abstract: An exothermic oxidation process wherein a rotating bed containing a variable oxidation state material is cycled through a succession of stages including an oxidative regeneration stage including a step wherein an oxidising fluid is passed through the bed, and a reaction stage wherein feedstock is passed through the bed, whereby said feedstock is oxidised to give products stream with the concurrent reduction of the convertible material to its lower oxidation state. The process can further include a stage wherein cooling fluid is passed through the bed.Type: GrantFiled: March 22, 2000Date of Patent: September 18, 2001Assignee: Imperial Chemical Industries PLCInventors: Samuel David Jackson, Frank King, David Graham Shipley, Edmund Hugh Stitt
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Patent number: 6288298Abstract: Disclosed are silicoaluminophosphates (SAPOs) having unique silicon distributions, a method for their preparation and their use as catalysts for the catalytic cracking of hydrocarbon feedstocks. More particularly, the new SAPOs have a high silica:alumina ratio, and are prepared from microemulsions containing surfactants.Type: GrantFiled: May 20, 1999Date of Patent: September 11, 2001Assignee: ExxonMobil Chemical Patents Inc.Inventors: Javier Agundez Rodriguez, Joaquin Perez Pariente, Antonio Chica Lara, Avelino Corma Canos, Tan Jen Chen, Philip A. Ruziska, Brian Erik Henry, Gordon F. Stuntz, Stephen M. Davis
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Patent number: 6288295Abstract: A novel catalyst comprises at least one support and at least one metal from group VIII or the periodic table e.g. palladium and is characterized in that the metal particles deposited on the support are not isolated from each other, e.g. at least 50% of the particles have a point of contact with one other particle.Type: GrantFiled: August 28, 1998Date of Patent: September 11, 2001Assignee: Institut Francais du PetroleInventors: Blaise Didillon, Denis Uzio, Elisabeth Merlen, Thierry Pages
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Patent number: 6218589Abstract: A method for improving the operation of a propane-propylene splitter in a process for the dehydrogenation of propane wherein the propane is dehydrogenated to produce a stream containing propylene and trace quantities of methyl acetylene and propadiene compounds and which stream is selectively hydrogenated to selectively saturate at least a majority of the trace quantities of methyl acetylene and propadiene compounds. The resulting effluent from the selective hydrogenation zone is fractionated in a propane-propylene splitter to produce a high-purity propylene product stream, an unconverted propane stream which is introduced to the dehydrogenation zone and a small slip stream or side-cut containing methyl acetylene and propadiene compounds which is introduced into the selective hydrogenation zone.Type: GrantFiled: January 14, 2000Date of Patent: April 17, 2001Assignee: UOP LLCInventor: Paul R. Cottrell
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Patent number: 6198012Abstract: A catalyst composition suitable for the conversion of n-butane to butenes. The same catalyst composition that with chlorination is further suitable, when used in the conversion of n-butane, for the production of an increased amount of BTX (benzene-toluene-xylene) and greater selectivity to the production of isobutylenes than attained with the unchlorinated catalyst. A process for the preparation of catalyst compositions suitable for the conversion of n-butane. Use of the catalyst compositions in processes for the conversion of n-butane.Type: GrantFiled: June 22, 2000Date of Patent: March 6, 2001Assignee: Phillips Petroleum CompanyInventors: An-hsiang Wu, Charles A. Drake
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Patent number: 6191332Abstract: The specification describes a method and a fixed bed apparatus for producing olefinic hydrocarbons from a charge of saturated aliphatic hydrocarbons with 2 to 20 carbon atoms and hydrogen in a chamber 1 comprising a plurality of parallel tubes 3 filled with a catalyst and arranged in rows. A so-called reaction phase and a catalyst-regenerating phase are carried out in the tubes of the chamber. The tubes are heated by appropriate radiant heating means 6, arranged in layers substantially perpendicular to the tubes. These layers heat a first part of the tubes (at the feed side) with a heat flux greater than the mean heat flux of the chamber and a second, subsequent part with a mean flux no more than equal to the mean heat flux, so that the isothermicity of the catalyst is substantially maintained, using appropriate control means.Type: GrantFiled: February 23, 1998Date of Patent: February 20, 2001Assignee: Institut Francais du PetroleInventors: Didier Duee, Larry Mank, Pierre Renard, Jean-Piere Burzynski, Gerard Leger, Philippe Vacher, Ari Minkkinen
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Patent number: 6187984Abstract: A catalyst composition suitable for the conversion of n-butane to butenes. The same catalyst composition that with chlorination is further suitable, when used in the conversion of n-butane, for the production of an increased amount of BTX (benzene-toluene-xylene) and greater selectivity to the production of isobutylenes than attained with the unchlorinated catalyst. A process for the preparation of catalyst compositions suitable for the conversion of n-butane. Use of the catalyst compositions in processes for the conversion of n-butane.Type: GrantFiled: June 22, 2000Date of Patent: February 13, 2001Assignee: Phillips Petroleum CompanyInventors: An-hsiang Wu, Charles A. Drake
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Patent number: 6175048Abstract: A catalyst composition and a process for using of the catalyst composition in a hydrocarbon conversion process are disclosed. The composition comprises an inorganic support, a Group VA metal or metal oxide, and optionally a Group IVA metal or metal oxide and a Group VIII metal or metal oxide. The process comprises contacting a fluid which comprises at least one saturated hydrocarbon with the catalyst composition under a condition sufficient to effect the conversion of the hydrocarbon to an olefin. Also disclosed is a process for producing the catalyst composition.Type: GrantFiled: November 29, 1999Date of Patent: January 16, 2001Assignee: Phillips Petroleum CompanyInventors: An-hsiang Wu, Charles A. Drake
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Patent number: 6165352Abstract: A continuous process for the dehydrogenation of a hydrocarbon and/or oxygenated hydrocarbon feed, comprising contacting the hydrocarbon and/or oxygenated hydrocarbon feed with a dehydrogenation catalyst at elevated temperature in a reaction zone characterised in that the catalyst is capable of retaining hydrogen and (a) is contacted with a feed to form a dehydrogenated product and hydrogen, at least some of the hydrogen formed being adsorbed by the catalyst and/or reacting therewith to reduce at least part of the catalyst; (b) the dehydrogenated product and any unadsorbed/unreacted hydrogen is removed from the reaction zone; (c) at least some of the adsorbed hydrogen is removed from the catalyst and/or at least some of the reduced catalyst is oxidised; and (d) reusing the catalyst from step (c) in step (a).Type: GrantFiled: March 12, 1998Date of Patent: December 26, 2000Assignee: BP Chemicals LimitedInventors: Jeremy Bernard Cooper, Jonathon Charles Frost, Stephen Roy Partington
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Patent number: 6159358Abstract: A process and apparatus produces reaction products by indirectly preheating and heating reactants by indirect heat exchange. The use of the preheating step simplifies the reaction zone design by eliminating the need for external exchangers and is particularly suited for an arrangement of plates that defines narrow channels for indirect heat exchange. The narrow channels are preferably defined by corrugated plates. The primary reaction channels will contain a catalyst for the promotion of the desired reaction product from the principal reactants. The heating fluid passes through adjacent heating channels defined by shared partition plates to provide indirect heating. At least a portion of the heating channels exchange heat with a non-catalytic portion of the reaction channels to preheat the reactants ahead of a catalytic section of the reaction channels. Catalytic combustion within the heating channels may provide in-situ heat input for the heating medium.Type: GrantFiled: September 8, 1998Date of Patent: December 12, 2000Assignee: UOP LLCInventors: Robert C. Mulvaney, III, Hemant W. Dandekar
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Patent number: 6143943Abstract: A channel reactor arrangement and a process uses a heat exchange fluid with a high thermal density to indirectly heat or cool the reactants by indirect heat exchange. The system brings the efficiency of plate reactor arrangements to the effectiveness of high heat capacity heat exchange fluids such as molten salts and liquid metals. The channel reactor arrangement maintains a limited temperature gradient through the channels at all points to improve process selectivity. This type of arrangement is of a particular advantage where the reaction zone uses a heterogeneous catalyst system within a heat exchanging reaction section. The plate and channel heat transfer arrangement is particularly beneficial because of its high surface area provided per unit volume of channels.Type: GrantFiled: September 8, 1998Date of Patent: November 7, 2000Assignee: UOP LLCInventors: Anil R. Oroskar, Robert C. Mulvaney, III
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Patent number: 6118038Abstract: A channel reactor arrangement and a process that uses a high heat capacity heat exchange liquid to indirectly heat or cool by indirect heat exchange. The channel reactor arrangement maintains a pressure gradient through the channels and a pressure differential between the reaction channels and the heat exchange channels at all points to preserve the integrity of the plates defining the channels and to prevent any leakage of high heat capacity liquids into the reaction channels. The system brings the efficiency of plate reactor arrangements to the effectiveness of high heat capacity heat exchange fluids such as molten salts and liquid metals. The process overcomes the problem of low heat exchange pressure drop in combination with high reactant pressure drop by creating a negative pressure differential from reactant channels to the heat exchange channels.Type: GrantFiled: September 8, 1998Date of Patent: September 12, 2000Assignee: UOP LLCInventors: Steven P. Lankton, Joseph E. Zimmermann, Robert C. Mulvaney, III
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Patent number: 6110325Abstract: An apparatus and method are provided in which a vaporizer vaporizes a liquid feed for introduction to a feed conversion unit such as a steam active reformer. A condenser condenses vaporized feed from the vaporizer when introduction of feed to the feed conversion unit is stopped. Condensed, liquid feed is passed back into the vaporizer and is conserved rather than going to flare.Type: GrantFiled: July 8, 1997Date of Patent: August 29, 2000Assignee: Krupp UHDE GmbHInventor: Martin K. Lyons
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Patent number: 6107534Abstract: An improved zeolite catalyst containing an acid-treated zeolite, a boron component and a zinc component manufactured by a novel method having certain process steps necessary for providing the improved zeolite catalyst. The process steps include a first steam treatment of an acid-treated zeolite, followed by incorporation of such zeolite with a boron component and a zinc component, followed by a second steam treatment. Processes are also disclosed for using the improved zeolite catalyst in the conversion of hydrocarbons, preferably non-aromatic hydrocarbons, to lower olefins (such as ethylene and propylene) and aromatic hydrocarbons (such as benzene, toluene, and xylene).Type: GrantFiled: August 25, 1999Date of Patent: August 22, 2000Assignee: Phillips Petroleum CompanyInventors: Charles A. Drake, An-hsiang Wu
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Patent number: 6103103Abstract: A process and catalyst are provided for dehydrogenating a hydrocarbon feedstock and producing an olefinic product. The process comprises contacting the feedstock at dehydrogenation conditions with a dehydrogenation catalyst comprising from about 0.01 weight percent to about 5.0 weight percent of a platinum group metal, from about 0.02 weight percent to about 10.0 weight percent of zinc, and a support component comprising borosilicate and an alkali metal.Type: GrantFiled: February 16, 1999Date of Patent: August 15, 2000Assignee: BP Amoco CorporationInventors: Bruce D. Alexander, George A. Huff, Jr., Mark P. Kaminsky
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Patent number: 6100436Abstract: A process and apparatus for contacting reactants with a particulate catalyst while indirectly heating the reactants with a heat exchange medium improves temperature control by using an intermediate heat exchange fluid and system to prevent overheating of reactants and maintain parallel heating characteristics through multiple reaction-heat exchange zones. The internal flow path minimizes the circulation of the reaction zone heat exchange fluid by incorporating interstage reheating of the reaction zone heat exchange fluid as it passes in series flow. A particularly useful application of the process and apparatus is in the dehydrogenation of ethyl benzene to produce styrene. The process and apparatus can also be used with simultaneous exchange of catalyst particles by an operation that restricts reactant flow while moving catalyst through reaction stacks in which the reactant flow has been restricted.Type: GrantFiled: September 8, 1998Date of Patent: August 8, 2000Assignee: UOP LLCInventors: William Wiede, Jr., Kevin J. Brandner, Bruce Allen Briggs, Donald Eelch, Constante P. Tagamolila
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Patent number: 6093867Abstract: A process for selectively producing C.sub.3 olefins from a catalytically cracked or thermally cracked naphtha stream. The naphtha stream is introduced into a process unit comprised of a reaction zone, a stripping zone, a catalyst regeneration zone, and a fractionation zone. The naphtha feedstream is contacted in the reaction zone with a catalyst containing from about 10 to 50 wt. % of a crystalline zeolite having an average pore diameter less than about 0.7 nanometers at reaction conditions which include temperatures ranging from about 500.degree. to 650.degree. C. and a hydrocarbon partial pressure from about 10 to 40 psia. Vapor products are collected overhead and the catalyst particles are passed through the stripping zone on the way to the catalyst regeneration zone. Volatiles are stripped with steam in the stripping zone and the catalyst particles are sent to the catalyst regeneration zone where coke is burned from the catalyst, which is then recycled to the reaction zone.Type: GrantFiled: May 5, 1998Date of Patent: July 25, 2000Assignee: Exxon Research and Engineering CompanyInventors: Paul K. Ladwig, John Ernest Asplin, Gordon F. Stuntz, Tan-Jen Chen
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Patent number: 6087545Abstract: An improved supported catalyst containing mixed strontium and other alkaline earth oxides deposited on a sintered low surface area porous catalyst carrier (or support) precoated with mixed lanthanum and other rare earth oxides, represented by the formula:A.sub.a SrO.sub.b (x) /R.sub.c LaO.sub.d (y) /S,wherein, A is alkaline earth element selected from Be, Mg, Ca, Ba or a mixture thereof; Sr is strontium, O is oxygen; R is rare earth element selected from Ce, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or a mixture thereof; La is lanthanum; S is catalyst support selected from sintered low surface area porous refractory inert solids comprising of alumina, silica, silica-alumina, silicon carbide, zirconia, hafnia or a mixture thereof; a is A/Sr mole ratio in the range of about 0.01 to about 10; b is number of oxygen atoms needed to fulfill the valence requirement of alkaline earth elements (A.sub.a Sr); c is R/La mole ratio in the range of about 0.Type: GrantFiled: July 14, 1997Date of Patent: July 11, 2000Assignee: Council of Scientific & Industrial ResearchInventors: Vasant Ramchandra Choudhary, Balu Shivaji Uphade, Shafeek Abdul Rashid Mulla
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Patent number: 6072097Abstract: A process for the production of a mono-olefin from a gaseous paraffinic hydrocarbon having at least two carbon atoms or mixtures thereof comprising reacting said hydrocarbons and molecular oxygen in the presence of a platinum catalyst. The catalyst consists essentially of platinum modified with Sn or Cu and supported on a ceramic monolith.Type: GrantFiled: September 3, 1998Date of Patent: June 6, 2000Assignee: Regents of the University of MinnesotaInventors: Chikafumi Yokoyama, Sameer S. Bharadwaj, Lanny D. Schmidt
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Patent number: 6045688Abstract: The invention relates ro a method of converting hydrocarbons. According to the method, a gaseous or liquid hydrocarbon feed is passed into a circulating fluidized-bed reactor, wherein the feed is converted at a high temperatue under the influence of particulate matter kept in a fluidized state, and the converted hydrocarbon products are removed from the reactor in a gaseous phase. According to the invention, a circulating fluidized-bed reactor (1-3; 41-43) is used having an axially annular cross section and being equipped with a multiport cyclone (14,17; 52,63) for the separation of the particulate matter from the gas-phase reaction products. The reaction space comprises an intershell riser space (13; 50) formed between two concentrically located cylindrical and/or conical envelope surfaces. The separation of particulate matter from the gas-phase reaction products is performed by means of a multiport cyclone equipped with louvered vanes (14; 63).Type: GrantFiled: August 29, 1997Date of Patent: April 4, 2000Assignee: Neste OYInventors: Seppo Ruottu, Kari Kaariainen, Jyrki Hiltunen
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Patent number: 6028027Abstract: Catalysts comprising iron and potassium and, if desired, further elements, which catalysts are suitable for dehydrogenating hydrocarbons to give the corresponding olefinically unsaturated hydrocarbons, are prepared by calcining a finely divided dry or aqueous mixture of an iron compound with a potassium compound and, if desired, compounds of further elements in a first step that agglomerates having a diameter of from 5 to 50 .mu.m and formed from smaller individual particles are obtained and, in a second step, preferably after shaping, calcining it at from 300 to 1000.degree. C., with the maximum calcination temperature in the second step preferably being at least 30.degree. below the calcination temperature in the first step. The catalysts thus prepared are useful, in particular, for dehydrogenating ethylbenzene to give styrene.Type: GrantFiled: March 17, 1998Date of Patent: February 22, 2000Assignee: BASF AktiengesellschaftInventors: Michael Baier, Christopher William Rieker, Otto Hofstadt, Wolfgang Buchele, Wolfgang Jurgen Popel, Hermann Petersen, Norbert Neth
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Patent number: 6020533Abstract: Hydrocarbon conversion processes using a new family of crystalline manganese phosphate compositions is disclosed. These compositions have an extended network; which network can be a one-, two-, or three-dimensional network. The composition has an empirical formula of:(A.sup.a+).sub.v (Mn.sup.b+)(M.sup.c+).sub.x P.sub.y O.sub.zwhere A is a templating agent such as an alkali metal, M is a metal such as Al, Fe.sup.3+ and "b" is the average manganese oxidation state and varies from greater than 3.0 to about 4.0.Type: GrantFiled: July 10, 1998Date of Patent: February 1, 2000Assignee: UOP LLCInventors: Gregory J. Lewis, Paula L. Bogdan
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Patent number: 5997724Abstract: A shale oil modifier is made of a crude shale oil dehydrogenated sufficiently to attain a viscosity of between about 1200-1800 poise at 60.degree. C. The crude shale oil has sufficient basic nitrogen content so that the dehydrogenated crude shale oil exhibits non-Newtonian properties when mixed with asphalt cements. Preferably, the basic nitrogen content is about 2%-2.5% by weight. The shale oil modifier is made by a process which includes providing a crude shale oil and subjecting the crude shale oil to a two stage distillation followed by a vacuum distillation and collecting the residual fraction. The residual fraction is dehydrogenated with air until a select viscosity, preferably between about 1200-1800 poise at 60.degree. C. is obtained.Type: GrantFiled: June 16, 1997Date of Patent: December 7, 1999Assignee: The New Paraho CorporationInventor: Larry A Lukens
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Patent number: 5994606Abstract: A method for dehydrogenation of a hydrocarbon, which comprises selectively oxidizing hydrogen in a gas mixture which is obtained by subjecting a feed hydrocarbon to a dehydrogenation reaction in the presence of a dehydrogenation catalyst and which comprises a dehydrogenated hydrocarbon, an unreacted feed hydrocarbon and hydrogen, by contacting the gas mixture with an oxygen-containing gas in the presence of an oxidation catalyst, and further subjecting a hydrocarbon-containing gas obtained by the oxidation reaction to a dehydrogenation reaction, wherein a catalyst comprising a component having platinum and/or palladium supported on a carrier obtained by calcining at least one member selected from the group consisting of tin oxide, titanium oxide, tantalum oxide and niobium oxide, at a temperature of from 800.degree. C. to 1,500.degree. C., is used as the oxidation catalyst.Type: GrantFiled: May 8, 1997Date of Patent: November 30, 1999Assignee: Mitsubishi Chemical CorporationInventors: Tomoatsu Iwakura, Makoto Takiguchi
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Patent number: 5959170Abstract: A method for converting methane to higher hydrocarbon products and coproduct water wherein a gas comprising methane and a gaseous oxidant are contacted with a nonacidic catalyst at temperatures within the range of about 700 to 1200.degree. C. A preferred catalyst comprises an alkali component associated with a support material. Results obtained over alkali-promoted solids are enhanced when the contacting is conducted in the presence of halogen promoters.Type: GrantFiled: May 24, 1985Date of Patent: September 28, 1999Assignee: Atlantic Richfield CompanyInventor: Howard P. Withers, Jr.
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Patent number: 5922925Abstract: A process for dehydrogenating dehydrogenatable C.sub.2-30 hydrocarbons includes contacting the hydrocarbons under dehydrogenating conditions in one or more reaction zones with a solid catalyst. The solid catalyst includes at least a Group VIII noble metal, a Group IVA metal, and a carrier of a mixed oxide of magnesium and aluminum.Type: GrantFiled: May 18, 1998Date of Patent: July 13, 1999Assignee: Den norske stats oljeselskap a.s.Inventors: Duncan Akporiaye, Morten Ronnekleiv, Preben Hasselgard, Age Solbakken, deceased
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Patent number: 5912394Abstract: A catalyst for the dehydrogenation of C.sub.6 -C.sub.15 paraffins is disclosed. The catalyst contains, on support, at least one platinum group component, at least one promoter component from the group tin, germanium and lead, and at least one additional modifier. The additional modifier contains at least one alkaline earth metal. The stability of the catalyst is essentially higher than that achieved by conventional use of an alkali metal.Type: GrantFiled: October 9, 1998Date of Patent: June 15, 1999Assignee: Degussa-Huels AktiengesellschaftInventors: Hans Lansink Rotgerink, Thomas Tacke, Reinhold Brand, Peter Panster
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Patent number: 5905180Abstract: A process for the production of a mono-olefin from a gaseous paraffinic hydrocarbon having at least two carbon atoms or mixtures thereof comprising reacting said hydrocarbons and molecular oxygen in the presence of a platinum catalyst. The catalyst consists essentially of platinum modified with Sn or Cu and supported on a ceramic monolith.Type: GrantFiled: September 30, 1996Date of Patent: May 18, 1999Assignee: Regents of the University of MinnesotaInventors: Chikafumi Yokoyama, Sameer S. Bharadwaj, Lanny D. Schmidt
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Patent number: 5895829Abstract: In a process for preparing olefinically unsaturated compounds such as styrene by oxidative dehydrogenation of corresponding hydrocarbons using a previously oxidized oxygen transferer acting as catalyst in the absence of molecular oxygen and reoxidation of the oxygen transferer in at least two reactors, the dehydrogenation and regeneration takes place alternately in time in the two reactors and the reactors are connected to one another in terms of heat via heat exchangers and a common circuit for heat transfer medium.Type: GrantFiled: June 18, 1997Date of Patent: April 20, 1999Assignee: BASF AktiengesellschaftInventors: Wolfgang Jurgen Popel, Alfred Hagemeyer, Wolfgang Buchele, Axel Deimling, Wolfgang Hoffmann
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Patent number: 5877369Abstract: A catalyst composition and a process for using of the catalyst composition in a hydrocarbon conversion process are disclosed. The composition comprises an inorganic support, a Group VA metal or metal oxide, and optionally a Group IVA metal or metal oxide and a Group VIII metal or metal oxide. The process comprises contacting a fluid which comprises at least one saturated hydrocarbon with the catalyst composition under a condition sufficient to effect the conversion of the hydrocarbon to an olefin. Also disclosed is a process for producing the catalyst composition.Type: GrantFiled: October 23, 1997Date of Patent: March 2, 1999Assignee: Phillips Petroleum CompanyInventors: An-hsiang Wu, Charles A. Drake
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Patent number: 5877381Abstract: The present invention provides a fluidized bed catalyst for the synthetic reaction of organic compounds which has a reduced catalyst loss. A fluidized bed catalyst for organic compound synthetic reaction, characterized in that 90% or more of the catalyst particles is in the range of 5-500 .mu.m on the weight-based particle size distribution and 90% or more of the 20-75 .mu.m particles has a crushing strength which satisfies the following equation:CS>A.multidot.d.sub..alpha.wherein CS represents a crushing strength ?g-weight/particle!,A represents a constant 0.001,d represents a particle diameter ?.mu.m!, and.alpha. represents a constant 2.Type: GrantFiled: July 1, 1996Date of Patent: March 2, 1999Assignee: Nitto Kagaku Kogyo Kabushiki KaishaInventors: Yutaka Sasaki, Hiroshi Yamamoto, Kiyoshi Moriya, Yoshimi Nakamura
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Patent number: 5877387Abstract: A preparation of a Pb-substituted hydroxyapatite catalyst for oxidative coupling of methane represented by the formula Ca.sub.10-x pb.sub.x (PO.sub.4).sub.6 (OH).sub.2 wherein 0<X<10 or preferably 0<X<3, includes dissolving calcium nitrate tetrahydrate ?Ca(NO.sub.3).sub.2 4H.sub.2 O!, lead nitrate ?Pb(NO.sub.3).sub.2 ! and monobasic ammonium phosphate ?NH.sub.4 H.sub.2 PO.sub.4 ! in a distilled water at room temperature to have over 0.01M concentration and pH 9 and maintaining a resultant precipitate for 5 to 20 hours for aging and then calcining the resultant. A method for producing C.sub.2 compounds using the thusly produced catalyst includes reacting a mixed gas composed of methane, oxygen and helium in the presence of 5.about.20 g.multidot.min/L of the Pb-substituted hydroxyapatite catalyst according to the present invention, at a high temperature of at least 600.degree. C.Type: GrantFiled: May 23, 1997Date of Patent: March 2, 1999Assignee: Korea Institute of Science and TechnologyInventors: Tae-Jin Park, Dong Jin Suh, Kwan-Young Lee