EP0000054B1 - Procédé pour la préparation d'hydrocarbures oléfiniques aliphatiques ou cycloaliphatiques - Google Patents

Procédé pour la préparation d'hydrocarbures oléfiniques aliphatiques ou cycloaliphatiques Download PDF

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Publication number
EP0000054B1
EP0000054B1 EP78100096A EP78100096A EP0000054B1 EP 0000054 B1 EP0000054 B1 EP 0000054B1 EP 78100096 A EP78100096 A EP 78100096A EP 78100096 A EP78100096 A EP 78100096A EP 0000054 B1 EP0000054 B1 EP 0000054B1
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EP
European Patent Office
Prior art keywords
weight
catalysts
catalytically active
acid
percent
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EP78100096A
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German (de)
English (en)
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EP0000054A1 (fr
Inventor
Peter Dr. Horn
Otto-Alfred Dr. Grosskinsky
Hugo Dr. Fuchs
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BASF SE
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BASF SE
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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
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C07C1/213—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by splitting of esters
    • 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
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C07C1/2078—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)-O- moiety is eliminated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • 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
    • C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the invention relates to a process for the preparation of olefinically unsaturated aliphatic or cycloaliphatic hydrocarbons by heating alkane carboxylic acids having 3 to 20 carbon atoms, alkane dicarboxylic acids having 4 to 20 carbon atoms or 5- or 6-membered cycloalkane carboxylic acids or the respective alkyl, cycloalkyl, aralkyl or phenyl ester at temperatures of 250 to 800 ° C in the gas phase in the presence of catalysts.
  • the technical problem was therefore to provide a process in which the corresponding olefins are obtained from carboxylic acids or their esters by decarbonylation.
  • This object is achieved in a process for the preparation of olefinically unsaturated aliphatic or cycloaliphatic hydrocarbons by heating alkanecarboxylic acids having 3 to 20 carbon atoms, alkanedicarboxylic acids having 4 to 20 carbon atoms or 5- to 6-membered cycloalkanecarboxylic acids or the respective alkyl, cycloalkyl, aralkyl - or phenyl esters at temperatures of 250 to 800 ° C.
  • catalysts being used whose catalytically active composition consists of boron trioxide, boric acid and / or boron nitride and at least one of the oxides of aluminum, silicon, tin, lead, Titanium or zirconium.
  • the new process has the advantage that carboxylic acids or their esters can be converted into olefins in a simple manner. Furthermore, the new process has the advantage that it can easily be transferred to an industrial scale and runs with good yields and conversions.
  • Alkane carboxylic acids with 3 to 16 carbon atoms, alkane dicarboxylic acids with 4 to 12 carbon atoms of cyclohexane carboxylic acid are preferably used as starting materials.
  • Their alkyl, cycloalkyl, aralkyl or phenyl esters are also suitable. In particular, their C 1 -C 8 -alkyl esters, cyclohexyl esters, benzyl esters or phenyl esters.
  • the free carboxylic acids or the corresponding methyl esters are particularly preferably used as starting materials.
  • the new process is of particular technical importance for the production of cyclohexene from hexahydrobenzoic acid or its esters.
  • Suitable starting materials are, for example, propionic acid, methyl propionate, isobutyric acid or butyl isobutyrate, caproic acid, methyl caproate, decanecarboxylic acid, palmitic acid, methyl palmitate, dimethyl adipate, methyl glutarate,.
  • the reaction is carried out in the gas phase.
  • the carboxylic acids or their esters used as starting materials are expediently evaporated.
  • inert gases such as nitrogen, noble gases, carbon dioxide, carbon monoxide, water vapor or flue gases are also used.
  • the amount of inert gases used is not critical since they only serve as carrier gases.
  • the reaction is advantageously carried out at atmospheric pressure, slight excess pressure or reduced pressure, e.g. up to 26.5 mbar.
  • a pressure range from atmospheric pressure to 133 mbar has proven particularly useful.
  • the reaction takes place at temperatures of 250 to 800 ° C. Temperatures of 250 to 700 ° C are advantageously used.
  • the reaction is carried out in the presence of catalysts whose catalytically active composition consists of boron trioxide, boric acid and / or boron nitride and at least one of the oxides of aluminum, silicon, lead, titanium or zirconium.
  • Preferred catalytic compositions contain 10 to 60, in particular 20 to 55 percent by weight of boron trioxide, boric acid and or boron nitride.
  • the rest of the catalytically active mass then consists of one of the oxides mentioned. Kataly has proven particularly successful tables masses containing boron trioxide or boric acid, in particular boron trioxide.
  • the preferred oxides which are also present in the catalytically active compositions include aluminum oxide such as hydrargillite, boehmite or bayerite and their drainage products, for example r, E or 8-aluminum oxide, and also tin dioxide, titanium dioxide or silica gel.
  • Aluminum oxide and titanium dioxide are particularly preferably used in the anatase modification.
  • ⁇ -Alumina has gained particular technical importance because it reduces the isomerization of the olefinically unsaturated hydrocarbons formed.
  • Catalysts according to the invention are also those which are formed by phase formation of one of the boron compounds used with the oxides mentioned, for example from boron trioxide and aluminum oxide, such as compounds of the molecular formula 9 Al 2 O 3 . 2 B 2 0 3 or 2 A ' 2 0 3 . B 2 0 3 . In such phases, aluminum oxide can no longer be detected by X-ray analysis.
  • the catalytically active compositions advantageously additionally comprise at least one of the elements of group VIII. of the periodic table manganese, chromium, copper, zinc, cadmium, silver and / or gold.
  • the elements mentioned are preferably present in the catalytically active compositions in amounts of 0.1 to 10 percent by weight, based on the catalytically active composition, calculated as metal.
  • Suitable catalysts are prepared, for example, by adding aluminum oxide and boron trioxide or boric acid, optionally with the addition of compounds of the abovementioned heavy metals, such as manganese nitrate, manganese acetate, cobalt nitrate, cobalt acetate, nickel nitrate, rhodium chloride, tris (triphenylphosphine) chlorine rhodium, iridium chloride, palladium nitrate, platinum chloride, zinc chloride, Cadmium nitrate, copper nitrate, silver nitrate or gold chloride mixes, if necessary pasted and kneaded with water and shaped into moldings such as pills, tablets or strands.
  • heavy metals such as manganese nitrate, manganese acetate, cobalt nitrate, cobalt acetate, nickel nitrate, rhodium chloride, tris (triphenylphosphine) chlorine rho
  • the mass is then advantageously dried and expediently tempered at temperatures up to 400.degree. If the catalytically active mass is to be used as a fluidized bed catalyst, it is advisable to adjust the moldings to the desired particle size, e.g. to break down to an average grain size of 0.01 to 2 mm, in particular 0.2 to 1 mm.
  • the catalyst mass is then heated to temperatures of 600 to 1500, preferably 700 to 1300, in particular 1000 to 1200 ° C. over a period of 15 minutes to 20 hours, in particular 30 minutes to 5 hours.
  • the catalytically active compositions according to the invention are obtained by, for example, aluminum oxide or one of the other oxides mentioned, which already have a grain size of 0.1 to 2 mm, under pressure with boron trioxide or boron compounds which are produced under the conditions of manufacture Transfer catalyst into boron trioxide or boric acid, soaked with the use of solvating agents at elevated temperature under pressure.
  • Water is advantageously suitable as the solvating agent, if appropriate with the addition of small amounts of ammonia or mineral acids such as hydrochloric acid or perchloric acid, and suitable solvating agents are also alcohol oils such as methanol, ethanol or glycerol.
  • the oxides are advantageously impregnated under increased pressure, e.g.
  • the weight ratio of solvent to the starting materials used is advantageously 1: 1 to 10: 1.
  • the same parts by weight of solvent and starting materials are used.
  • Such a so-called impregnation catalyst is then dried at temperatures from 50 to 200 ° C. and then heated to temperatures from 600 to 1500 ° C.
  • the catalysts can be used as unsupported catalysts or supported.
  • the catalysts can be used in a fixed arrangement. However, it is advantageous to use the catalysts in a fluidized bed in a moving up and down motion. It has proven to be advantageous if the reaction times of the catalyst are from 0.01 to 50 seconds.
  • the process is carried out, for example, by swirling a fine-grained supported catalyst, for example aluminum oxide, which contains boron trioxide in a device suitable for producing a fluidized bed, heating it to the temperatures indicated and, from below, carboxylic acid esters or carboxylic acids in gaseous form, optionally together with carrier gases by means of the Catalyst bed conducts.
  • a fine-grained supported catalyst for example aluminum oxide, which contains boron trioxide
  • carboxylic acid esters or carboxylic acids in gaseous form, optionally together with carrier gases by means of the Catalyst bed conducts.
  • the carboxylic acid or the ester can also be introduced in liquid form into the heated catalyst bed.
  • the gas mixture obtained is cooled and olefins unreacted starting materials and, if appropriate, the corresponding alcohols are condensed when using esters.
  • the inert gaseous components can again be used as carrier gas.
  • unreacted starting materials can be returned to the reaction. It may be necessary to separate the resulting olefins from the alcohols produced as by-products, e.g. by distillation.
  • Olefinically unsaturated hydrocarbons which are produced by the process of the invention are suitable, for example, for the production of aldehydes after oxosynthesis.
  • Cyclohexene which is obtained by the process of the invention, is suitable for the preparation of cyclohexanol, as described for example in GB - PS 339 592.
  • the organic phase was washed with aqueous sodium bicarbonate solution to remove traces of unreacted hexahydrobenzoic acid, and then distilled.
  • the gas chromatographic examination of the distillate showed the following composition: 63 percent by weight of cyclohexene, 29 percent by weight of 1-methylcyclopentene (1), 4 percent by weight of 3-methylcyclopentene (1) and 4 percent by weight. 4-methylcyclopentene (1).
  • Example 2 The procedure was analogous to Example 1, with the difference that the catalyst used in Example 1 was heated to 1150 ° C. for 4 hours before use. After 7 hours of operation, 61 g of water and 356 g of an organic phase, consisting of 72% by weight of cyclohexene and 23% by weight of 1-methylcyclopentene (1) after working up according to Example 1, were obtained.
  • Example 2 The procedure was analogous to Example 1, with the difference that the catalyst used in Example 1 additionally contains 1.3 percent by weight of rhodium. After 3 hours of operation, 69 g of water and 366 g of an organic phase consisting, after working up according to Example 1, of 74% by weight of cyclohexene, 19.6% by weight of 1-methylcyclopentene (1) and 5.5% by weight of benzene were obtained.

Claims (9)

1. Procédé de préparation d'hydrocarbures à insaturation oléfinique aliphatiques ou cy- cloaliphatiques, par chauffage d'acides alcane- carboxyliques comportant 3 à 20 atomes de carbone, d'acides alcanedicarboxyliques comportant 4 à 20 atomes de carbone, ou d'acides cycloalcanecarboxyliques à 5 ou 6 membres, ou leurs alkyl-cycloalkyl-aralkyl- ou phénylesters, à des températures de 250 à 800°, en phase gazeuse, en présence de ca talyseurs, caractérisé par le fait que l'on utilise des catalyseurs dont la masse active catalytique est constituée de trioxyde de bore, d'acide borique et de nitrure de bore, ou seulement de nitrure de bore, ainsi qu'au moins un des oxydes d'aluminium, silicium, étain, plomb, titane ou zirconium.
2. Procédé selon la revendication 1, dans lequel on maintient des températures de 250 à 700°C.
3. Procédé selon l'une des revendications 1 et 2, dans lequel les catalyseurs ont une teneur de 10 à 60% en poids de trioxyde de bore, d'acide borique et de nitrure de bore ou seulement de nitrure de bore, rapportée à la masse catalytique active.
4. Procédé selon l'une des revendications 1 à 3, dans lequel on utilise du trioxyde de bore.
5. Procédé selon l'une des revendications 1 à 4, dans lequel la masse active catalytique contient en plus au moins un des éléments du Vlllème groupe tu tableau périodique, manganèse, chrome, cuivre, zinc, cadmium, argent ou or.
6. Procédé selon l'une des revendications 1 à 4, dans lequel on utilise de l'oxyde d'aluminium.
7. Procédé selon l'une des revendications 1 à 4, dans lequel on utilise de l'oxyde d'aluminium-α.
8. Procédé selon l'une des revendications 1 à 7, dans lequel on utilise des acides hexahyd- robenzoïques ou leurs alkyl-, cycloalkyl-, aralkyl- ou phénylesters comme produit de départ.
9. Procédé selon l'une des revendications 1 à 7, dans lequel la phase mélange des catalyseurs correspond à la composition 9 Al2O3.2 B203 ou 2 Al2O3.B2O3.
EP78100096A 1977-06-10 1978-06-06 Procédé pour la préparation d'hydrocarbures oléfiniques aliphatiques ou cycloaliphatiques Expired EP0000054B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2726106 1977-06-10
DE2726106A DE2726106C3 (de) 1977-06-10 1977-06-10 Verfahren zur Herstellung von olefinisch ungesättigten aliphatischen oder cycloaliphatischen Kohlenwasserstoffen

Publications (2)

Publication Number Publication Date
EP0000054A1 EP0000054A1 (fr) 1978-12-20
EP0000054B1 true EP0000054B1 (fr) 1980-10-29

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EP78100096A Expired EP0000054B1 (fr) 1977-06-10 1978-06-06 Procédé pour la préparation d'hydrocarbures oléfiniques aliphatiques ou cycloaliphatiques

Country Status (5)

Country Link
US (1) US4178317A (fr)
EP (1) EP0000054B1 (fr)
JP (1) JPS545902A (fr)
DE (2) DE2726106C3 (fr)
IT (1) IT1104729B (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7811732A (nl) * 1978-11-30 1980-06-03 Stamicarbon Werkwijze voor de omzetting van dimethylether.
JPS606334B2 (ja) * 1979-07-16 1985-02-18 三菱レイヨン株式会社 高純度イソブチレンの製造法
US4393260A (en) * 1980-08-01 1983-07-12 The Standard Oil Company Preparation of cyclohexenyl compounds
EP0154829B1 (fr) * 1982-03-27 1987-01-07 BASF Aktiengesellschaft Procédé pour la préparation d'oléfines à partir de méthanol/diméthyléther
FR2551056B1 (fr) * 1983-08-25 1985-11-29 Inst Francais Du Petrole Nouveau procede de fabrication d'olefine lineaire a partir d'acide gras ou d'ester d'acide gras sature
DE3813147A1 (de) * 1988-04-20 1989-11-02 Basf Ag Verfahren zur herstellung von olefinisch ungesaettigten, endstaendigen carbonsaeureestern
US5077447A (en) * 1990-09-28 1991-12-31 Henkel Research Corporation Process for making olefins
JPH04102559U (ja) * 1991-02-04 1992-09-03 ソニー株式会社 ボタン型アルカリ電池
JP3089974B2 (ja) * 1995-02-13 2000-09-18 日本ビクター株式会社 信号記録方法及び映像信号処理装置
JP2011168529A (ja) * 2010-02-18 2011-09-01 Kao Corp オレフィンの製造法
JP2011168528A (ja) * 2010-02-18 2011-09-01 Kao Corp オレフィンの製造法
JP6027437B2 (ja) * 2012-12-28 2016-11-16 花王株式会社 オレフィンの製造法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2304872A (en) * 1939-05-20 1942-12-15 Eastman Kodak Co Decomposition of esters
US2310762A (en) * 1939-08-09 1943-02-09 Daumiller Guenther Production of aromatic vinyl compounds
US2383205A (en) * 1942-11-16 1945-08-21 Universal Oil Prod Co Manufacture of butadiene
FR1274507A (fr) * 1960-08-22 1961-10-27 Idemitsu Kosan Kabushikikaisha Procédé de préparation d'isoprène et d'acide acétique par décomposition catalytique d'acétate de méthyl-3-butène-3-ol-l et de diacétate d'isoprène-glycol
US4024171A (en) * 1975-06-30 1977-05-17 Union Oil Company Of California Aluminum borate catalyst compositions and use thereof in chemical conversions

Also Published As

Publication number Publication date
IT1104729B (it) 1985-10-28
US4178317A (en) 1979-12-11
EP0000054A1 (fr) 1978-12-20
DE2860251D1 (en) 1981-01-29
DE2726106B2 (de) 1979-07-26
IT7849772A0 (it) 1978-06-08
DE2726106A1 (de) 1978-12-14
JPS545902A (en) 1979-01-17
DE2726106C3 (de) 1980-06-26

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