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WO1995030635A1 - Production d'olefines par transhydrogenation - Google Patents

Production d'olefines par transhydrogenation Download PDF

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Publication number
WO1995030635A1
WO1995030635A1 PCT/US1995/005084 US9505084W WO9530635A1 WO 1995030635 A1 WO1995030635 A1 WO 1995030635A1 US 9505084 W US9505084 W US 9505084W WO 9530635 A1 WO9530635 A1 WO 9530635A1
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WO
WIPO (PCT)
Prior art keywords
compound
cofeed
zsm
catalyst
metal
Prior art date
Application number
PCT/US1995/005084
Other languages
English (en)
Inventor
Ralph Moritz Dessau
Randall David Partridge
Original Assignee
Mobil Oil Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mobil Oil Corporation filed Critical Mobil Oil Corporation
Priority to AU24609/95A priority Critical patent/AU2460995A/en
Publication of WO1995030635A1 publication Critical patent/WO1995030635A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/50—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with an organic compound as an acceptor
    • C07C5/52—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with an organic compound as an acceptor with a hydrocarbon as an acceptor, e.g. hydrocarbon disproportionation, i.e. 2CnHp -> CnHp+q + CnHp-q

Definitions

  • the present invention is directed to a process for the production of olefins by transhydrogenation.
  • Dehydrogenation catalysts suggested in Parris include heterogeneous catalysts such as supported and unsupported metals, metal oxides, and mixtures thereof, and homogeneous catalysts such as organometallic complexes.
  • a process for producing, by transhydrogenation, an unsaturated analog of a feed compound containing an aliphatic moiety having 2 to 5 carbon atoms, and a saturated analog of a cofeed compound which is a light olefin the process comprising contacting the feed compound and the cofeed compound with a non-acidic catalyst, said catalyst comprising a dehydrogenation metal and a non- acidic crystalline microporous material containing a metal modifier selected from Sn, In, Pb and Tl to dehydrogenate at least a portion of the feed compound and hydrogenate at least a portion of the cofeed compound.
  • One of the major advantages of the transhydrogenation process of the invention is that it reduces the magnitude of the temperature drop in the reaction zone, while also providing a higher per pass yield of desirable olefins.
  • the heat generated by transhydrogenation of olefins such as propylene greatly reduces the overall endothermicity of the dehydrogenation process.
  • the transhydrogenation process also permits operation at lower temperatures and higher pressures. Olefins may be cofed into the middle of the catalyst bed.
  • Non-acidic intermediate pore size zeolites such as ZSM-5, which contain noble metals such as Pt, and base metals such as tin, are found to be advantageous in transhydrogenation processes which operate in the absence of added hydrogen, due to their stability under low partial pressure hydrogen conditions.
  • Metals on large pore zeolites or on amorphous supports age rapidly in the absence of cofed hydrogen invention whereas the ctalyst of the invention resists aging because the base metal is present within the zeolite and effectively protected from bulky coke precursors.
  • Noble metals such as Pt or Pd can tolerate low hydrogen pressure.
  • solid, amorphous transalkylation catalysts are found to be more likely than crystalline microporous materials, such as zeolites, to result in side-reactions such as cracking which tend to accelerate in coking and/or aging of the catalyst, necessitating more frequent regeneration procedures.
  • the feedstocks comprise at least one straight or branched chain aliphatic compound in which the aliphatic moiety has two to five carbon atoms.
  • Other compounds effective in the instant invention include ethyl benzene, cumene and para-methyl ethyl toluene.
  • dehydrogenation of the aliphatic moiety occurs to yield the unsaturated analog.
  • the substituents can be aryls, substituted or unsubstituted.
  • the class of reactants includes alkanes of 2 to 5 carbon atoms including propane, butane, isobutane, pentane and 2-methylbutane. Aromatics having aliphatic chains of 2 to 5 carbon atoms may also be used in the instant invention.
  • Light olefins are added to the reactor in the instant invention as a cofeed.
  • Ethene and propene and mixtures thereof are the primary olefins used, although light FCC gas which contains impurities may also be used.
  • Olefins are usually cofed in a ratio of from 0.05-0.5 moles olefin to 1 mole alkane.
  • Light olefins may be combined with the feed and introduced into the reaction zone (usually an adiabatic reactor) at the top. Alternately, the catalyst bed may be split into two portions and the olefin cofeed may be added between the portions.
  • Catalvst Catalvst
  • the catalyst for the catalytic dehydrogenation of the invention comprises a non-acidic composition including a hydrogenation/dehydrogenation metal and a non-acidic, crystalline microporous material containing a metal modifier selected from Sn, In, Tl and Pb.
  • a suitable catalyst is further disclosed in U.S. Patent No. 4,886,926.
  • the hydrogenation/dehydrogenation metal can be any Group VIII noble metal.
  • the metal may be Pt or Pd, most preferably Pt.
  • the catalyst may also contain Ir and Rh.
  • the amount of hydrogenation/dehydrogenation metal in the catalyst can range from 0.01 to 30 wt.% and preferably from 0.02 to 10 wt.% of the catalyst.
  • the metal modifier content of the catalyst can range from 0.01 to 20 wt.%, preferably 0.1 to 10 wt.%, of the crystalline microporous material.
  • the crystalline microporous material is preferably an intermediate pore zeolite having a constraint index of 1- 12, such as ZSM-5, ZSM-11, ZSM-22, ZSM-23 and ZSM-35. Most preferably the zeolite is ZSM-5 modified with Sn.
  • the zeolite is non-acidic and preferably has an Al content less than 0.5 wt% and more preferably less than 0.2 wt%.
  • the crystalline microporous material of the instant invention can contain other elements including boron, iron, chromium and gallium. These elements, can be present in amounts ranging from 0 to 10 wt.%.
  • the catalyst prefeably includes a silica binder.
  • Catalytic dehydrogenation conditions include pressures varying from subatmospheric, to atmospheric to greater than atmospheric. Preferred pressures range from 0.1 atmosphere to atmospheric (10 to 100 kPa) . However, pressures up to 500 psig (3550 kPa) can be employed.
  • the dehydrogenation is conducted at elevated temperatures ranging from 450°C to 700°C, and most preferably from 500 to 600°C.
  • the liquid hourly space velocity is 0.1 to 50, preferably 0.2 to 10. Under these conditions, the catalytic dehydrogenation of the invention exhibits reduced selectivity for hydrogenolysis and for isomerization.
  • Dehydrogenation in the instant invention, is generally conducted in the absence of added hydrogen. However, diluents inert to conditions of catalytic dehydrogenation, such as nitrogen and methane, may be added.
  • Isobutane was introduced at the top of the reactor, while the olefin was cofed with the isobutane at the top of the bed.
  • Reactor effluents were monitored by on-line gas chromatography. Regenerations were conducted in flowing hydrogen at 60 psig (515 kPa) and 500°C for 4-24 hours.
  • the catalyst was also added at the top of the bed.
  • One reason for the use of the Pt/Sn-ZSM-5 catalyst is that modification with tin is known to lessen olefin inhibition. Additionally, an equimolar amount of propylene was used as cofeed, instead of ethylene. At 500°C and about 1 hour on stream, a 9.9 wt% yield (normalized) of isobutene was observed.
  • Example 2 In the experiments of this example, the olefin being cofed was introduced into the middle of the catalyst bed, where some hydrogen had already formed by dehydrogenation of isobutane.
  • the catalyst a silica-bound Pt/SnZSM-5 (as described in Example 1) was divided into two 0.5 g beds separated by vycor. Isobutane was passed through the entire reactor at 100 cc/min, while the olefin was introduced between the two beds. The results obtained are shown in Table 1, below.
  • Table 1 illustrates that significant amounts of transhydrogenation were observed for both ethylene or propene cofeeds.
  • the degree of transhydrogenation was measured by the amount of cofed olefin saturated per mole of isobutane dehydrogenated to isobutenes. The accuracy of these values was confirmed by direct determination of the molecular hydrogen produced. The decrease in hydrogen observed agreed quite well the amount of propane produced by transhydrogenation of propene.
  • Example 3 In this example lower ratios of olefins were used so that all the hydrogen generated would not be consumed. In these experiments, 20 cc/min propene was added between the two catalyst beds, at 550"C and an isobutane flow of 50 cc/min.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Procédé de production par transhydrogénation d'un analogue non saturé d'un composé de départ contenant une fraction aliphatique comprenant 2 à 5 atomes de carbone, et d'un analogue saturé d'un composé de départ adjoint qui est une oléfine légère. Ce procédé consiste à mettre le composé de départ et le composé de départ adjoint en contact avec un catalyseur non acide qui est lui-même constitué d'un métal de déshydrogénation et d'une matière microporeuse cristalline non acide contenant un modificateur métallique sélectionné parmi Sn, In, Pb et Tl dans des conditions permettant de déshydrogéner au moins une partie du composé de départ et au moins une partie du composé de départ adjoint.
PCT/US1995/005084 1994-05-09 1995-05-03 Production d'olefines par transhydrogenation WO1995030635A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU24609/95A AU2460995A (en) 1994-05-09 1995-05-03 Production of olefins by transhydrogenation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US24005394A 1994-05-09 1994-05-09
US240,053 1994-05-09

Publications (1)

Publication Number Publication Date
WO1995030635A1 true WO1995030635A1 (fr) 1995-11-16

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/005084 WO1995030635A1 (fr) 1994-05-09 1995-05-03 Production d'olefines par transhydrogenation

Country Status (2)

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AU (1) AU2460995A (fr)
WO (1) WO1995030635A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105121450A (zh) * 2013-03-27 2015-12-02 株式会社可乐丽 双(6-甲基-3-磺苯基)苯基膦及其铵盐、以及它们的制造方法
EP2960223A1 (fr) * 2014-06-25 2015-12-30 Borealis AG Processus de déshydrogénation catalytique de phase de gaz endothermique
EP3197852A1 (fr) * 2014-09-23 2017-08-02 Borealis AG Procédé de déshydrogénation catalytique endothermique en phase gazeuse

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4546204A (en) * 1983-11-07 1985-10-08 Imperial Chemical Industries Australia Limited Process for the manufacture of methyl t-butyl ether
US4886926A (en) * 1988-06-24 1989-12-12 Mobil Oil Corporation Catalytic dehydrogenation of hydrocarbons over tin-containing crystalline microporous materials
US5227552A (en) * 1992-04-27 1993-07-13 Mobil Oil Corporation Process for hydrogenating alkenes in the presence of alkanes and a heterogeneous catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4546204A (en) * 1983-11-07 1985-10-08 Imperial Chemical Industries Australia Limited Process for the manufacture of methyl t-butyl ether
US4886926A (en) * 1988-06-24 1989-12-12 Mobil Oil Corporation Catalytic dehydrogenation of hydrocarbons over tin-containing crystalline microporous materials
US5227552A (en) * 1992-04-27 1993-07-13 Mobil Oil Corporation Process for hydrogenating alkenes in the presence of alkanes and a heterogeneous catalyst

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105121450A (zh) * 2013-03-27 2015-12-02 株式会社可乐丽 双(6-甲基-3-磺苯基)苯基膦及其铵盐、以及它们的制造方法
CN105121450B (zh) * 2013-03-27 2017-09-15 株式会社可乐丽 双(6‑甲基‑3‑磺苯基)苯基膦及其铵盐、以及它们的制造方法
US10696701B2 (en) 2013-03-27 2020-06-30 Kuraray Co., Ltd. Bis(6-methyl-3-sulphophenyl)phenylphosphine, ammonium salt thereof, and method for producing same
EP2960223A1 (fr) * 2014-06-25 2015-12-30 Borealis AG Processus de déshydrogénation catalytique de phase de gaz endothermique
EP3197852A1 (fr) * 2014-09-23 2017-08-02 Borealis AG Procédé de déshydrogénation catalytique endothermique en phase gazeuse
EP3197852B1 (fr) * 2014-09-23 2023-11-22 Borealis AG Processus de déshydrogénation catalytique de phase de gaz endothermique

Also Published As

Publication number Publication date
AU2460995A (en) 1995-11-29

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