GB2227250A - Preparation of conjugated diene - Google Patents

Preparation of conjugated diene Download PDF

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Publication number
GB2227250A
GB2227250A GB9001184A GB9001184A GB2227250A GB 2227250 A GB2227250 A GB 2227250A GB 9001184 A GB9001184 A GB 9001184A GB 9001184 A GB9001184 A GB 9001184A GB 2227250 A GB2227250 A GB 2227250A
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United Kingdom
Prior art keywords
conjugated diene
preparation
dehydration
carbonyl compound
copper chromite
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GB9001184A
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GB2227250B (en
GB9001184D0 (en
Inventor
Donald George Timms
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Enichem Elastomers Ltd
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Enichem Elastomers Ltd
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Publication of GB9001184D0 publication Critical patent/GB9001184D0/en
Publication of GB2227250A publication Critical patent/GB2227250A/en
Application granted granted Critical
Publication of GB2227250B publication Critical patent/GB2227250B/en
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Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/72—Copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/86—Chromium

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  • 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

A process for the preparation of a conjugated diene by dehydration of the corresponding carbonyl compound comprises passing the carbonyl compound over copper chromite dispersed on an inert support at a temperature of 300 DEG C to 500 DEG C.

Description

PREPARATION OF CONJUGATED DIENE This invention relates to the preparation of a conjugated diene by dehydration of the corresponding carbonyl compound with the same number of carbon atoms.
Conjugated dienes, in particular butadiene and isoprene, are essential raw materials for the synthetic rubber industry. Polybutadiene and styrene butadiene rubbers/latices absorb about 70% of total butadiene production and polyisoprene is the major end use for isoprene monomer. These monomers may be produced by dehydrogenation, by recovery from hydrocarbon streams or by synthesis from other hydrocarbons. Isoprene is mainly produced by extraction from C5 streams but a variety of synthetic processes have been devised, several of which have been used in commercial production.
Recently, interest has been renewed in the synthesis of isoprene from n-butenes by hydroformylation and dehydration. The aldehyde dehydration stage was first proposed by Kyriakides and others (see U.S. Patent No.
1,033,180). Recent publications have disclosed the use of an acidic dehydration catalyst, especially boron phosphate (see G.B. Patent No.
1,385,348 and USSR Inventors Certificate No. 721,116 and U.S. Patents Nos.
4,524,233, 4,587,372, 4,632,913 and 4,628,140). Other catalysts proposed are magnesium ammonium phosphate (G.B. Patent No. 2,093,060), alum (G.B. Patent No. 2,063,297), zeolites (U.S. Patent No. 4,560,822 and European Patent No. 210-42 and molecular sieves (U.S. Patent No. 4,734,538 and European Patent No. 272662).
According to the present invention a conjugated diene is prepared by dehydration of the corresponding carbonyl compound having the same number of carbon atoms by passage over copper chromite dispersed on an inert support at a temperature of 300"C to 5000C.
As mentioned above, the usual dehydration catalysts are acidic whereas copper chromite is usually used in hydrogenation/dehydrogenation reactions or in oxidation processes.
The invention is particularly useful to prepare 1,3-butadiene, 2-methyl 1,3-butadiene (isoprene) and corresponding higher conjugated dienes. A preferred process is the preparation of isoprene by dehydration of 2-methyl butyraldebyde (2-methyl butanal) or methyl isopropyl ketone.
The support is necessary for practical application of the process since unsupported in a pellet form the catalyst is friable and rapidly disintegrates, blocking the reactor.
Examples of suitable inert supports are acid washed pumice or corundum granules but the support used is not critical since it plays no part in the dehydration reaction and does not affect catalyst activity.
The use of copper chromite is quite critical since other chromites (e.g.
nickel and zinc chromite) give only trace amounts of conjugated diene.
The following example illustrates the invention.
Example Copper chromite was prepared according to the recipe given in Organic Syntheses, collected Vol. 2 p 142 (Wiley & Sons 1943/1961). One gram was moistened then mixed with 10ml 16-30 mesh acid washed pumice. After drying the catalyst was transferred to an electrically heated pyrex glass reactor of 12mm bore. Nitrogen saturated with 2 methyl butanal at 250C was passed through the reactor. The reactor was heated stepwise and the gaseous products were analysed by gas chromatography using tri tolyl phosphate stationary phase. The system was allowed to equilibriate for about 1 hour after each change in temperature.
Conversion was 8.5% at 3000C and increased rapidly with increasing temperature. At 441it conversion was 67% with selectivity to isoprene 64%.
The trial was repeated but corundum granules were used to support the catalyst. Results were similar, showing that the support did not affect catalyst activity. (The supports were shown to be inactive in separate trials).
In a further experiment, copper chromite was prepared according to the same recipe except that barium was omitted and replaced with the equivalent of copper nitrate. Its performance was similar to that of the previous catalyst.

Claims (3)

Claims
1. A process for the preparation of a conjugated diene by dehydration of the corresponding carbonyl compound having the same number of carbon atoms comprising passing the carbonyl compound over copper chromite dispersed on an inert support at a temperature of 3000C to 5000C.
2. A process according to claim 1 in which the support comprises acid washed pumice or corundum granules.
3. A process according to claim 1 or claim 2 substantially as herein described with reference to the Example.
GB9001184A 1989-01-19 1990-01-18 Preparation of conjugated diene Expired - Lifetime GB2227250B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB898901185A GB8901185D0 (en) 1989-01-19 1989-01-19 Preparation of conjugated dienes

Publications (3)

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GB9001184D0 GB9001184D0 (en) 1990-03-21
GB2227250A true GB2227250A (en) 1990-07-25
GB2227250B GB2227250B (en) 1992-01-02

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GB9001184A Expired - Lifetime GB2227250B (en) 1989-01-19 1990-01-18 Preparation of conjugated diene

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021126421A1 (en) 2019-12-19 2021-06-24 Dow Technology Investments Llc Processes for preparing isoprene and mono-olefins comprising at least six carbon atoms

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3651121A (en) * 1970-08-10 1972-03-21 Marathon Oil Co Oxydehydrogenation process for preparation of dienes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3651121A (en) * 1970-08-10 1972-03-21 Marathon Oil Co Oxydehydrogenation process for preparation of dienes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021126421A1 (en) 2019-12-19 2021-06-24 Dow Technology Investments Llc Processes for preparing isoprene and mono-olefins comprising at least six carbon atoms
US11976017B2 (en) 2019-12-19 2024-05-07 Dow Technology Investments Llc Processes for preparing isoprene and mono-olefins comprising at least six carbon atoms

Also Published As

Publication number Publication date
GB2227250B (en) 1992-01-02
GB9001184D0 (en) 1990-03-21
GB8901185D0 (en) 1989-03-15

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PE20 Patent expired after termination of 20 years

Expiry date: 20100117