GB2201159A - Process and apparatus for the dehydrogenation of organic compounds - Google Patents

Process and apparatus for the dehydrogenation of organic compounds Download PDF

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Publication number
GB2201159A
GB2201159A GB8629135A GB8629135A GB2201159A GB 2201159 A GB2201159 A GB 2201159A GB 8629135 A GB8629135 A GB 8629135A GB 8629135 A GB8629135 A GB 8629135A GB 2201159 A GB2201159 A GB 2201159A
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dehydrogenation
zone
permeate
hydrogen
compound
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GB8629135A
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GB8629135D0 (en )
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Johan George Albert Bitter
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Shell International Research Mij BV
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Shell International Research Mij BV
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333Catalytic processes
    • C07C5/3332Catalytic processes with metal oxides or metal sulfides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J15/00Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00Feed or outlet devices; Feed or outlet control devices
    • B01J4/04Feed or outlet devices; Feed or outlet control devices using osmotic pressure using membranes, porous plates
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333Catalytic processes
    • C07C5/3335Catalytic processes with metals
    • C07C5/3337Catalytic processes with metals of the platinum group

Abstract

The dehydrogenation of organic compounds is carried out in a dehydrogenation zone containing a dehydrogenation catalyst and comprising a wall which includes a ceramic membrane which is selectively permeable to hydrogen and separates the dehydrogenation zone from a permeate zone; the wall may optionally be heated by conducting an electric current therethrough.

Description

PROCESS AND APPARATUS FOR THE DEHYDROGENATION OF ORGANIC COMPOUNDS The invention relates to a process for the dehydrogenation of a dehydrogenatable organic compound. The invention further relates to a dehydrogenation reactor.

It is described in US patent specification 3,450,500 to dehydrogenate an organic compound in the presence of steam by using a membrane about which a bed of granular dehydrogenation catalyst is disposed and which membrane is formed from a metal selectively permeable to hydrogen. The preferred membranes are-those fabricated from platinum and palladium and their alloys. These metals, however, are very expensive.

According to US patent specification 3,290,406 gas phase reactions wherein hydrogen is a product of the reaction are effected in the presence of a membrane which is selectively permeable to hydrogen; the hydrogen produced during the reaction is continuously removed from the reaction zone by permeation through the selectively permeable membrane. As a result thereof it becomes possible to utilize more economical reaction conditions. The diffused hydrogen is then contacted with a gas containing free oxygen to effect combustion thereof at the surface of the membrane. This known process can be effected in a tubular reactor constructed of a hydrogen-permeable material such as palladium or palladium-containing alloys. The dehydrogenation may be promoted by packing the tubular reactor with a dehydrogenation catalyst. Again, palladium is a very expensive metal.

Another disadvantage of palladium-containing membranes is that they may suffer from hydrogen embrittlement, which renders their life relatively short.

It is an object of the present invention to provide a process in which a membrane is used which-is relatively cheap and has a relatively long life.

Accordingly, the present invention provides a process for the dehydrogenation of a dehydrogenatable organic compound, which process comprises: (a) dehydrogenating said dehydrogenatable organic compound in the gaseous phase in a dehydrogenation zone in the presence of a dehydrogenation catalyst, thus forming a reaction mixture comprising dehydrogenated organic compound, hydrogen and unreacted dehydrogenatable organic compound, said dehydrogen ation zone comprising a wall being a ceramic membrane which separates said dehydrogenation zone from a permeate zone, which membrane is in contact with said reaction mixture and through which hydrogen selectively permeates, (b) withdrawing a retentate from said dehydrogenation zone, and (c) withdrawing a hydrogen-containing permeate from said permeate zone.

The invention further provides a dehydrogenation reactor comprising a dehydrogenation zone having a feed inlet and a product outlet, and a permeatezone having a permeate out?et, said dehydrogenation zone comprising a wall being a ceramic membrane which is selectively permeable to hydrogen and which separates the dehydrogenation zone from the permeate zone.

Ceramic membranes can withstand relatively high temperatures, which makes it possible to apply them in the dehydrogenation of dehydrogenatable organic compounds The invention will now be described by way of example in more detail with reference to the drawings, wherein Figure 1 schematically shows an embodiment of the process according to the present invention and Figure 2 schematically shows a preferred dehydrogenation reactor.

Reference is now made to Figure 1 showing a dehydrogenation reactor 1 provided with a dehydrogenation zone 2 charged with dehydrogenation catalyst indicated by means of the shaded area. The dehydrogenation zone 2 suitably consists of a number of tubes, four of which are shown in Figure 1, and which are preferably cylindrical.

The dehydrogenation zone 2 has an inlet 3 and a product outlet 4 indicated by means of dashed lines, and a permeate zone 5. The product outlet 4 serves as the wall of the dehydrogenation zone 2 and comprises a ceramic membrane which is selectively permeable to hydrogen and which separates the dehydrogenation zone 2 from the permeate zone 5.

The wall of the dehydrogenation zone 2 does not contain dehydrogenation catalyst. The arrows from the dehydrogenation zone 2 to the permeate zone 5 indicate the selective flow of hydrogen during normal operation. As hydrogen is continuously removed from the reaction mixture present in the dehydrogenation zone 2 the chemical equilibrium shifts to the right hand side and, hence, more organic compound is dehydrogenated.

Figure 1 shows that the hydrogen-containing retentate is removed from the dehydrogenation zone 2 via a retentate outlet 6 and that the hydrogen-containing permeate is removed from the permeate zone 5 via a permeate outlet 7. The retentate is relatively poor in hydrogen which facilitates the recovery therefrom of hydrogen-containing organic compound and of the organic compound that has been formed by the dehydrogenation.

The gaseous feed comprising said hydrogen-containing organic compound may be free from or may contain molecular hydrogen. The dehydrogenatable organic compound being introduced into the dehydrogenation zone is preferably-present in a reaction mixture formed by pre-dehydrogenation of the dehydrogenatable organic compound. This pre-dehydrogenation is suitably carried out until chemical equilibrium at the prevailing conditions is obtained.

Figure 1 shows that the dehydrogenatable organic compound supplied via a line 8 is introduced into a pre-dehydrogenation zone 9 charged with dehydrogenation catalyst indicated by means of the shaded area. Gaseous feed comprising said dehydrogenatable organic compound and also molecular hydrogen is withdrawn from the predehydrogenation zone 9 and conducted via a line 10 to the inlet 3 of the dehydrogenation zone 2. The dehydrogenatable organic compound supplied via the line 8 may contain steam to dilute the mixture and to supply heat.

The hydrogen-containing permeate removed via the permeate outlet 7 also contains starting dehydrogenatable organic compound and is not in chemical equilibrium. Therefore, in a further preferred embodiment of the present invention a hydrogen-containing permeate is withdrawn from the permeate zone and then subjected to an after-dehydrogenation. Figure 1 shows that the hydrogen-containing permeate withdrawn from the permeate outlet 7 is conducted via a line 11 and introduced into a permeate dehydrogenation zone 12 charged with dehydrogenation catalyst indicated by means of the shaded area and in which zone the after-dehydrogenation is carried out. The product obtained by means of the after-dehydrogenation is withdrawn from the permeate dehydrogenation zone 12 via a product outlet 13.

The process according to the present invention is preferably carried out by introducing steam into the permeate zone, thus supplying heat.

Asc.ordillg to another suitable embodiment of the present invention the dehydrogenation reactor further comprises a separate pre-dehydrogenation zone charged with dehydrogenation catalyst and having a feed inlet, which pre-dehydrogenation zone is in fluid communication with the dehydrogenation zone. Suitably, the dehydrogenation reactor further comprises a separate permeate dehydrogena- tion zone charged with dehydrogenation catalyst, communicating with the permeate outlet and having a product outlet. According to a much preferred embodiment the pre-dehydrogenation zone is arranged below the dehydrogenation zone, and according to another much preferred embodiment the permeate dehydrogenation zone is arranged below the pre-dehydrogenation zone. The permeate zone suitably has a steam inlet.

In Figures 1 and 2 the elements indicated with the same reference number have the same meaning. Figure 2 shows that the dehydrogenation reactor 1 comprises the pre-dehydrogenation zone 9 as a separate zone and that this zone is in fluid communication with the dehydrogenation zone 2; that the dehydrogenation reactor 1 comprises the permeate dehydrogenation zone 12 as a separate zone communicating with the permeate outlet 7; that the pre-dehydrogenation zone 9 is arranged below the dehydrogenation zone 2; and that the permeate dehydrogenation zone 12 is arranged below the predehydrogenation zone 9. The permeate zone 5 has a steam inlet 14.

Ceramic membranes which are selectively permeable to hydrogen may be crystalline or substantially amorphous and may be made of alumina and can be manufactured as described in, for example, "Preparation, structure and separation characteristics of ceramic alumina membranes", thesis byA.F.M. Leenaars, 1984, Technical University Twente, the Netherlands. The membranes are suitably supported on a permeable wall. The ceramic membrane has a thickness which may vary substant, depending on the particular dehydrogenation being carried out and is suitably in the range of from 2 to 20 vm. The membrane suitably contains pores having a modal diameter in the range of from 0.003 to 0.05 vm. Ceramic membranes can also be made of SiC ceramics or of high temperature resistant quartz glass.

The process according to the present invention can be carried out by using a great variety of dehydrogenation catalysts. A suitable catalyst described in British patent specification 2,091,757 has a spinel structure and contains one or more oxides of sodium, potassium, rubidium and cesium as promoter and vanadium oxide as an additional promoter. - Another suitable catalyst described in French patent application 85 19324 comprises iron oxide and, as promoters, an alkali metal compound, not more than 10% by weight of a compound of a rare earth metal, calculated as M02 on the total catalyst, M representing the rare earth metal, and a calcium compound.

The process according to the present invention can be carried out at a molar ratio steam to hydrogen-containing organic compound, temperature, pressure and liquid hourly space velocity which are not critical and may vary within wide ranges. Suitably, the process is conducted using a molar ratio steam to hydrogen-containing organic compound in the range of from 2 to 20 and preferably of from 5 to 13, a temperature in the range of from 400 CC to 750 OC and preferably of from 600 to 635 OC, a pressure in the range of from 0.1 to 10 bar and preferably of from 0.5 to 5 bar and a liquid hourly space velocity in the range of from 0.1 to 5 litre hydrogencontaining organic compound (measured as liquid) per litre catalyst per hour.The pressure differential applied between the one side of the ceramic membrane on the dehydrogenation zone and the other side on the permeate zone is suitably from 0.5 to 10 bar. If desired, the process is carried out in the absence of a diluting gas such as steam or nitrogen.

Heat- required for the dehydrogenation can be supplied in any desired manner. The use of ceramic membranes, however, allows supplying heat electrically, ceramics being sufficiently electrically conductive at the temperatures at which the dehydrogenation is carried out. Therefore, heat required for the dehydrogenation is preferably provided by conducting an electric current through the permeable wall. The walls of the dehydrogenation zone are therefore preferably provided with means iil order to conduct an electric current therethrough, the installation of such means being a very simple procedure.

A great variety of dehydrogenatable organic compounds may be used in the process according to the present invention. Usually, this compound has the general formula , <img class="EMIRef" id="027134830-00060001" />

wherein R1 and R2 each represent an alkyl, an alkenyl or a phenyl group or a hydrogen atom, in which case the dehydrogenation results in the formation of a compound of the general formula <img class="EMIRef" id="027134830-00060002" />

in which R1 and R2 have the same meaning as described for the former general formula. R may represent a phenyl group carrying one or more methyl groups as substituents. Preferably, R1 represents an unsubstituted phenyl group and R a hydrogen atom or a methyl group. Ethylbenzene is a very suitable starting compound.

Alkanes and alkenes are other suitable starting compounds and preferably have in the range of from 3 to 20 and particularly 3 to 8 carbon atoms per molecule; examples are propane, butane, 2-methylbutane, 1-butene, 2-butene, 2-methyl-1-butene and 3-methyl-butene.

Catalysts having a highly porous structure and a low specific surface area are highly active in catalytic dehydrogenation.

Various methods are known to form highly porous catalysts. For example, combustible materials, such as sawdust, carbon or wood flour may be added durinf catalyst formation, and then burned out after the pellet has been formed. If desired, the catalyst may be used supported on a carrier, for example zinc aluminate. The catalyst may be used in the form of, for example, pellets, tablets, spheres, pills, saddles, trilobes or tetralobes.

The following Examples further illustrate the invention. In each of the examples thewgaseous mixtures withdrawn from the pre-dehydrogenation zone 9 via the line 10 and from the permeate dehydrogenation zone 12 via the line 13 are in equilibrium.

EXAMPLE 1 This example describes the dehydrogenation of propane according to Figure 1.

Propane is conducted at a temperature of 575 "C, a pressure of 1 bar and a liquid hourly space velocity of 0.5 kg propane per kg catalyst per hour through the pre-dehydrogenation zone 9 charged with particles of alumina impregnated with 20% by weight of chromium oxide, calculated as Cr203 on total catalyst. The particles are, cylindrical, having a height of 4 mm and a diameter of 2 mm.

The dehydrogenation zone 2 and the permeate dehydrogenation zone 12 are charged with the same dehydrogenation catalyst as present in the pre-dehydrogenation zone 9. The walls of the dehydrogenation zone 2, which walls serve as the product outlet 4, have a thickness of 4 mm and consist of porous aluminium oxide having a pore size of 1 pm and covered with a layer of a ceramic aluminium oxide membrane having a thickness of 4-10 um and containing pores having a modal diameter of 0.01 vm. The pressure in the permeate zone is 0.25 bar.

The composition of five gas streams is presented in Table 1 hereinafter. The selectivity to propene was 90%.

Table 1 Gas stream in line Composition, mmol Propane Propylene Hydrogen 8 1000 0 0 10 599 401 401 11 i84 147 303 13 133 198 354 6 409 389 169 All of the propylene formed is present in lines 6 and 13 and is equivalent to a propane conversion of 58.7%. In the absence of the ceramic membrane only the amount of propylene present in line 10 would have been formed, which would have been equivalent to a propane conversion of only 40.1%.

EXAMPLE 2 This example describes the dehydrogenation of a mixture of 2-methyl-1-butene and 3-methyl-i-butene according to Figure 2.

A mixture of 2-methylbutenes and steam is conducted at a temperature of 550 ec, a pressure of 4 bar and a liquid hourly space velocity of 0.45 kg 2-methylbutenes per kg catalyst per hour through the pre-dehydrogenation zone 9 charged with particles of zinc aluminate promoted with platinum and tin.

The dehydrogenation zone 2 and the permeate dehydrogenation zone 12 are charged with the same dehydrogenation catalyst as present in the pre-dehydrogenation zone 9, and the walls of the dehydrogenation zone 2 are the same as those used in Example 1.

The composition of four gas streams is presented in Table 2 hereinafter. The selectivity to isoprene is 85%.

Table 2 Gas stream in line Composition, mol 2-Methyl-2-butenes Steam Isoprene Hydrogen 8 1,000 15,000 0 0 14 0 1,000 0 0 13 172 7,170 130 258 6 455 8,850 243 114 All of the isoprene formed is present in lines 6 and 13 and is equivalent to a conversion of 2-methylbutenes of 37.3Z. In the absence of the ceramic membrane the conversion of the 2-methylbutenes would have been only 27.3%.

EXAMPLE 3 This example describes the dehydrogenation of ethylbenzene according to Figure 2.

A mixture of ethylbenzene and steam is conducted at a tempera- ture of 625 OC, a pressure of 4 bar and a liquid hourly space velocity of 0.65 litres ethylbenzene per litr catalyst per hour through the pre-dehydrogenation zone 9 charged with particles of a catalyst having a spinel structure with the formula Lio 5Fe2 4Cro 1 4 containing 12% by weight of K20 and 3% by weight of vanadium pentoxide, both calculated on the total catalyst. This catalyst consists of cylindrical particles with a diameter of 3 mm and a height of 5 mm.

The dehydrogenation zone 2 and the permeate dehydrogenation zone 12 are charged with the same dehydrogenation catalyst as present in the pre-dehydrogenation zone 9, and the walls of the dehydrogenation zone 2 are the same as those used in Example 1. The pressure in the permeate dehydrogenation zone 12 is 1 bar.

The composition of four gas streams is presented in Table 3 hereinafter. The selectivity to ethylbenzene was 94%.

Table 3 Gas stream in line Composition, mol Ethylbenzene Steam Styrene Hydrogen 8 1,000 4,000 0 0 14 0 100 0 0 13 100 2,272 231 506 6 248 1,811 421 146 All of the styrene formed is present in lines 6 and 13 and is equivalent to a conversion of ethylbenzene of 65.2. In the absence of the ceramic membrane the conversion of ethylbenzene would have been only 50.7%.

Claims (17)

1. Process for the dehydrogenation of a dehydrogenatable organic compound, which process comprises: (a) dehydrogenating said dehydrogenatable organic compound in the gaseous phase in a dehydrogenation zone in the presence of a dehydrogenation catalyst, thus forming a reaction mixture comprising dehydrogenated organic compound, hydrogen and unreacted dehydrogenatable organic compound, said dehydrogen ation zone comprising a wall being a ceramic membrane which separates said dehydrogenation zone from a permeate zone, which membrane is in contact with said reaction mixture and through which hydrogen selectively permeates, (b) withdrawing a retentate from said dehydrogenation zone, and (c) withdrawing a hydrogen-containing permeate from said permeate zone.
2. Process as claimed in claim 1 in which the dehydrogenatable organic compound being introduced into the dehydrogenation zone is present in a reaction mixture formed by pre-dehydrogenation of the dehydrogenatable organic compound.
3. Process as claimed in claim 1 or 2 in which the hydrogen-containing permeate withdrawn from the permeate zone is subjected to an after-dehydrogenation.
4. Process as claimed in any one of the preceding claims in which steam is introduced into the permeate zone.
5. Process as claimed in any one of the preceding claims in which heat required for the dehydrogenation is provided by conducting an electric current through the ceramic membrane.
6. Process as claimed in any one of the preceding claims in which the dehydrogenatable organic compound is a hydrocarbon.
7. Dehydrogenation reactor comprising a dehydrogenation zone having a feed inlet and a product outlet, and a permeate zone having a permeate outlet, said dehydrogenation zone comprising a wall being a ceramic membrane which is selectively permeable to hydrogen and which separates the dehydrogenation zone from the permeate zone.
8. Dehydrogenation reactor as claimed in claim 7 which reactor further comprises a separate pre-dehydrogenation zone charged with dehydrogenation catalyst and having a feed inlet, which pre-dehydrogenation zone is in fluid communication with the dehydrogenation zone.
9. Dehydrogenation reactor as claimed in claim 7 or 8 which reactor further comprises a separate permeate dehydrogenation zone charged with dehydrogenation catalyst, communicating with the permeate outlet and having a product outlet.
10. Dehydrogenation reactor as claimed in claim 8 or 9 in which the pre-dehydrogenation zone is arranged below the dehydrogenation zone.
11. Dehydrogenation reactor as claimed in any one of claims 8 to 10 in which the permeate dehydrogenation zone is arranged below the pre-dehydrogenation zone.
12. Dehydrogenation reactor as claimed in any one of claims 7 to 11 in which the permeate zone has a steam inlet.
13. Dehydrogenation reactor as claimed in any one of claims 7 to 12 in which the ceramic membrane is supported on a permeable wall.
14. Dehydrogenation reactor as claimed in any one of claims 7 to 13 in which the wall of the dehydrogenation zone is provided with means in order to conduct an electric current therethrough.
15. Process as claimed in claim 1 substantially as hereinbefore described with reference to the Examples.
16. Dehydrogenated organic compounds whenever prepared by a process as claimed in any one of the preceding claims.
17. Dehydrogenation reactor as claimed in claim 7 substantially as hereinbefore described with reference to Figure 1 or 2.
GB8629135A 1986-12-05 1986-12-05 Dehydrogenation of organic compounds Pending GB8629135D0 (en)

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GB8629135A GB8629135D0 (en) 1986-12-05 1986-12-05 Dehydrogenation of organic compounds

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991006520A1 (en) * 1989-10-27 1991-05-16 Medalert Incorporated Process for production of ethylene from ethane
US5262198A (en) * 1991-04-08 1993-11-16 Aluminum Company Of America Method of producing a carbon coated ceramic membrane and associated product
DE19953641A1 (en) * 1999-11-09 2001-06-07 Metallgesellschaft Ag A process for the catalytic dehydrogenation of hydrocarbons in tubular reactor
EP1163952A1 (en) * 2000-06-14 2001-12-19 Ecole Polytechnique Fédérale de Lausanne (EPFL) Fixed bed structure containing microchannels suitable for a cylindrical reactor
US6958427B2 (en) 2002-03-04 2005-10-25 Korea Research Institute Of Chemical Technology Method for catalytic dehydrogenation of hydrocarbons using carbon dioxide as a soft oxidant
US20120078024A1 (en) * 2010-09-24 2012-03-29 Fina Technology Inc. Removal of Hydrogen From Dehydrogenation Processes
EP2505573A1 (en) 2011-03-29 2012-10-03 Stamicarbon B.V. acting under the name of MT Innovation Center Method for olefins production
WO2016140574A1 (en) * 2015-03-05 2016-09-09 Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center System and method for the production of alkenes by the dehydrogenation of alkanes

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3290406A (en) * 1962-05-15 1966-12-06 Engelhard Ind Inc Process for dehydrogenation
US3450500A (en) * 1965-08-03 1969-06-17 United Aircraft Corp Method for catalytically reforming hydrogen-containing carbonaceous feed-stocks by simultaneous abstractions through a membrane selectively permeable to hydrogen
US4268278A (en) * 1978-05-16 1981-05-19 Monsanto Company Inorganic anisotropic hollow fibers
US4313013A (en) * 1980-08-01 1982-01-26 Phillips Petroleum Company Palladium or a palladium alloy hydrogen diffusion membrane treated with a volatile compound of silicon is used to separate hydrogen from a mixture of it with a hydrocarbon
US4482360A (en) * 1982-05-29 1984-11-13 Nippon Steel Corporation Porous materials for concentration and separation of hydrogen or helium, and process therewith for the separation of the gas
US4548619A (en) * 1984-10-11 1985-10-22 Uop Inc. Dehydrocyclodimerization process

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3290406A (en) * 1962-05-15 1966-12-06 Engelhard Ind Inc Process for dehydrogenation
US3450500A (en) * 1965-08-03 1969-06-17 United Aircraft Corp Method for catalytically reforming hydrogen-containing carbonaceous feed-stocks by simultaneous abstractions through a membrane selectively permeable to hydrogen
US4268278A (en) * 1978-05-16 1981-05-19 Monsanto Company Inorganic anisotropic hollow fibers
US4313013A (en) * 1980-08-01 1982-01-26 Phillips Petroleum Company Palladium or a palladium alloy hydrogen diffusion membrane treated with a volatile compound of silicon is used to separate hydrogen from a mixture of it with a hydrocarbon
US4482360A (en) * 1982-05-29 1984-11-13 Nippon Steel Corporation Porous materials for concentration and separation of hydrogen or helium, and process therewith for the separation of the gas
US4548619A (en) * 1984-10-11 1985-10-22 Uop Inc. Dehydrocyclodimerization process

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991006520A1 (en) * 1989-10-27 1991-05-16 Medalert Incorporated Process for production of ethylene from ethane
US5202517A (en) * 1989-10-27 1993-04-13 Medalert Incorporated Process for production of ethylene from ethane
US5262198A (en) * 1991-04-08 1993-11-16 Aluminum Company Of America Method of producing a carbon coated ceramic membrane and associated product
DE19953641A1 (en) * 1999-11-09 2001-06-07 Metallgesellschaft Ag A process for the catalytic dehydrogenation of hydrocarbons in tubular reactor
EP1163952A1 (en) * 2000-06-14 2001-12-19 Ecole Polytechnique Fédérale de Lausanne (EPFL) Fixed bed structure containing microchannels suitable for a cylindrical reactor
WO2001096008A1 (en) * 2000-06-14 2001-12-20 Sulzer Chemtech Ag Fixed bed which is located in a tubular reactor part
US6958427B2 (en) 2002-03-04 2005-10-25 Korea Research Institute Of Chemical Technology Method for catalytic dehydrogenation of hydrocarbons using carbon dioxide as a soft oxidant
US20120078024A1 (en) * 2010-09-24 2012-03-29 Fina Technology Inc. Removal of Hydrogen From Dehydrogenation Processes
EP2505573A1 (en) 2011-03-29 2012-10-03 Stamicarbon B.V. acting under the name of MT Innovation Center Method for olefins production
WO2012134284A1 (en) 2011-03-29 2012-10-04 Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center Method for olefins production
US9776935B2 (en) 2011-03-29 2017-10-03 Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center Method for olefins production
WO2016140574A1 (en) * 2015-03-05 2016-09-09 Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center System and method for the production of alkenes by the dehydrogenation of alkanes

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