EP0000054B1 - Process for the preparation of olefinic unsaturated aliphatic or cycloaliphatic hydrocarbons - Google Patents
Process for the preparation of olefinic unsaturated aliphatic or cycloaliphatic hydrocarbons Download PDFInfo
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- 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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- 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
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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
- C07C1/2078—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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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.
Description
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von olefinisch ungesättigten aliphatischen oder cycloaliphatischen Kohlenwasserstoffen durch Erhitzen von Alkancarbonsäuren mit 3 bis 20 Kohlenstoffatomen, Alkandicarbonsäuren mit 4 bis 20 Kohlenstoffatomen oder 5- oder 6-gliedrigen Cycloalkancarbonsäuren oder der jeweiligen Alkyl-, Cycloalkyl-, Aralkyl- oder Phenylester auf Temperaturen von 250 bis 800°C in der Gasphase in Gegenwart von Katalysatoren.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.
Häufig ist es erwünscht aus Carbonsäuren, die beispielsweise bei Oxidationsverfahren erhalten werden oder aus Carbonsäuren oder deren Estern, die bei Carbonylierungsverfahren als Nebenprodukte anfallen, die entsprechenden Olefine durch Decarbonylierung zu gewinnen. Die Decarbonylierung von Carbonsäuren oder deren Ester ist dann von besonderem Interesse, wenn schwerzugängliche Olefine aus leichter zugänglichen Carbonsäuren oder deren Estern hergestellt werden können.It is often desirable to obtain the corresponding olefins by decarbonylation from carboxylic acids obtained, for example, in oxidation processes or from carboxylic acids or their esters, which are obtained as by-products in carbonylation processes. The decarbonylation of carboxylic acids or their esters is of particular interest if olefins which are difficult to access can be prepared from more accessible carboxylic acids or their esters.
Aus der DT-AS 1 158 050 ist zwar schon bekannt, daß man Carbonsäuren durch Erhitzen auf 250 bis 800°C, in der Gasphase in Gegenwart von Katalysatoren aus Oxiden, Hydroxiden . und Phosphaten der 2. bis 4. Hauptgruppe und der 3. bis 8. Nebengruppe des Periodensystems in Säureanhydride und/oder Ketone überführen kann. Diese Arbeitsweise gestattet es jedoch nicht, zu den entsprechenden Olefinen zu. gelangen.From DT-AS 1 158 050 it is already known that carboxylic acids are heated to 250 to 800 ° C. in the gas phase in the presence of catalysts made from oxides and hydroxides. and phosphates of the 2nd to 4th main group and the 3rd to 8th subgroup of the periodic table can be converted into acid anhydrides and / or ketones. However, this procedure does not allow to go to the corresponding olefins. reach.
Es war deshalb die technische Aufgabe gestellt, ein Verfahren zur Verfügung zu stellen, bei dem man aus Carbonsäuren oder deren Estern durch Decarbonylierung die entsprechenden Olefine zu erhalten.The technical problem was therefore to provide a process in which the corresponding olefins are obtained from carboxylic acids or their esters by decarbonylation.
Diese Aufgabe wird gelöst in einem Verfahren zur Herstellung von olefinisch ungesättigten aliphätischen oder cycloaliphatischen Kohlenwasserstoffen durch Erhitzen von Alkancarbonsäuren mit 3 bis 20 Kohlenstoffatomen, Alkandicarbonsäuren mit 4 bis 20 Kohlenstoffatomen oder 5- bis 6- gliedrigen Cycloalkancarbonsäuren oder der jeweiligen Alkyl-, Cycloalkyl-, Aralkyl- oder Phenylester auf Temperaturen von 250 bis 800°C in der Gasphase in Gegenwart von Katalysatoren, wobei man Katalysatoren verwendet deren katalytisch aktive Masse aus Bortrioxid, Borsäure und/oder Bornitrid sowie mindenstens aus einem der Oxide von Aluminium, Silicium, Zinn, Blei, Titan oder Zirkonium besteht.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. in the gas phase in the presence of catalysts, 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.
Das neue Verfahren hat den Vorteil, daß auf einfache Weise Carbonsäuren oder deren Ester in Olefine übergeführt werden können. Ferner hat das neue Verfahren den Vorteil, daß es leicht in einen technischen Maßstab übertragbar ist und mit guten Ausbeuten und Umsätzen verläuft.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.
Bevorzugt geht man von Alkancarbonsäuren mit 3 bis 16 Kohlenstoffatomen, Alkandicarbonsäuren mit 4 bis 12 Kohlenstoffatomen der Cyclohexancarbonsäure aus. Geeignet sind auch deren Alkyl-, Cycloalkyl-, Aralkyl- oder Phenylester. Insbesondere deren C,- bis C8-Alkylester, Cyclohexylester, Benzylester oder Phenylester. Besonders bevorzugt werden die freien Carbonsäuren oder die entsprechenden Methylester als Ausgangsstoffe verwendet. Besondere technische Bedeutung hat das neue Verfahren für die Herstellung von Cyclohexen aus Hexahydrobenzoesäure oder deren Estern. Geeignete Ausgangsstoffe sind beispielsweise Propionsäure, Propionsäuremethylester, Isobuttersäure, oder Isobuttersäurebutylester, Capronsäure, Capronsäuremethylester, Dekancarbonsäure, Palmitinsäure, Palmitinsäuremethylester, Adipinsäuredimethylester, Methylglutarsäuredimethylester, . Cyclopentancarbonsäuremethylester, Hexahydrobenzoesäure, Hexahydrobenzoesäuremethylester, Hexahydrobenzoesäurecyclohexylester, Hexahydrobenzoesäurephenylester oder Hexahydrobenzoesäurebenzylester.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,. Methyl cyclopentane carboxylate, hexahydrobenzoic acid, methyl hexahydrobenzoate, cyclohexyl hexahydrobenzoate, phenyl hexahydrobenzoate or benzyl hexahydrobenzoate.
Es versteht sich, daß man bei der Decarbonylierung von Monocarbonsäuren oder deren Ester zu einfach olefinisch ungesättigte Verbindungen mit einem Kohlenstoffatom weniger gelangt, während man bei der Decarbonylierung von Dicarbonsäuren zu Diolefinen mit 2 Kohlenstoffatomen weniger gelangt.It is understood that the decarbonylation of monocarboxylic acids or their esters leads to simple olefinically unsaturated compounds with one carbon atom less, while the decarbonylation of dicarboxylic acids leads to diolefins with 2 carbon atoms less.
Die Umsetzung wird in der Gasphase durchgeführt. Zweckmäßig verdampft man die als Ausgangsstoffe verwendeten Carbonsäuren oder deren Ester. Gegebenenfalls verwendet man, um die Ausgangsstoffe besser in der Gasphase anwenden zu können, zusätzlich Inertgase wie Stickstoff, Edelgase, Kohlendioxid, Kohlenmonoxid, Wasserdampf oder Rauchgase. Die Menge der mitverwendeten Inertgase ist nicht kritisch, da sie lediglich als Trägergase dienen.The reaction is carried out in the gas phase. The carboxylic acids or their esters used as starting materials are expediently evaporated. If necessary, in order to be able to use the starting materials better in the gas phase, 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.
Vorteilhaft führt man die Umsetzung bei Atmosphärendruck, geringem Überdruck oder vermindertem Druck z.B. bis zu 26,5 mbar durch. Besonders bewährt hat sich ein Druckbereich von Atmosphärendruck bis 133 mbar.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.
Die Umsetzung verläuft bei Temperaturen von 250 bis 800°C. Vorteilhaft wendet man Temperaturen von 250 bis 700°C an.The reaction takes place at temperatures of 250 to 800 ° C. Temperatures of 250 to 700 ° C are advantageously used.
Die Umsetzung wird in Gegenwart von Katalysatoren durchgeführt, deren katalytisch aktive Masse aus Bortrioxid, Borsäure und/oder Bornitrid sowie mindestens einem der Oxide von Aluminium, Silizium, Blei, Titan oder Zirkonium besteht. Bevorzugte katalytische Massen enthalten 10 bis 60, insbesondere 20 bis 55 Gewichtsprozent an Bortrioxid, Borsäure undoder Bornitrid. Der Rest der katalytisch aktiven Masse besteht dann aus einem der genannten Oxide. Besonders bewährt haben sich katalytische Massen, die Bortrioxid oder Borsäure insbesondere Bortrioxid enthalten.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.
Zu den bevorzugten Oxiden, die außerdem in der katalytisch aktiven Massen enthalten sind, gehören Aluminiumoxid wie Hydrargillit, Böhmit oder Bayerit sowie deren Entwässerungsprodukte, z.B. r, E, oder 8-Aluminiumoxid, ferner Zinndioxid, Titandioxid oder Kieselsäuregel. Be sonders bevorzugt werden Aluminiumoxid und Titandioxid, in der Anatasmodifikation, verwendet. Besondere technische Bedeutung hat α-Aluminiumoxid erlangt, da es die Isomerisierung der gebildeten olefinisch ungesättigten Kohlenwasserstoffe vermindert.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. Α-Alumina has gained particular technical importance because it reduces the isomerization of the olefinically unsaturated hydrocarbons formed.
Erfindungsgemäße Katalysatoren sind auch solche, die durch Phasenbildung einer der verwendeten Borverbindungen mit den genannten Oxiden entstanden sind, z.B. aus Bortrioxid und Aluminiumoxid wie Verbindungen der Summenformel 9 AI203 . 2 B203 oder 2 A'203 . B203. Röntgenographisch läßt sich in solchen Phasen Aluminiumoxid nicht mehr nachweisen.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.
Vorteilhaft enthalten die katalytisch aktiven Massen zusätzlich mindestens eines der Elemente der VIII. Gruppe. des Periodensystems Mangan, Chrom, Kupfer, Zink, Cadmium, Silber und/oder Gold. Vorzugsweise sind die genannten Elemente in den katalytisch aktiven Massen enthalten in Mengen von 0,1 bis 10 Gewichtsprozent, bezogen auf die katalytisch aktive Masse, berechnet als Metall.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.
Geeignete Katalysatoren werden beispielsweise hergestellt, indem man Aluminiumoxid sowie Bortrioxid oder Borsäure gegebenenfalls unter Zusatz von Verbindungen der oben genannten Schwermetalle, wie Mangannitrat, Manganacetat, Kobaltnitrat, Kobaltacetat, Nickelnitrat, Rhodiumchlorid, Tris(triphenylphosphin)chlorrhodium, Iridiumchlorid, Palladiumnitrat, Platinchlorid, Zinknitrat, Cadmiumnitrat, Kupfernitrat, Silbernitrat oder Goldchlorid mischt, gegebenenfalls mit Wasser anteigt und verknetet und zu Formlingen wie Pillen, Tabletten oder Strängen verformt. Vorteilhaft wird die Masse anschließend getrocknet und zweckmäßig bei Temperaturen bis 400°C getempert. Falls die katalytisch aktive Masse als Wirbelschichtkatalysator verwendet werden soll, ist es empfehlenswert, die Formlinge auf die gewünschte Teilchengröße, z.B. auf eine Durchschnittskorngröße von 0,01 bis 2 mm, insbesondere 0,2 bis 1 mm, zu brechen. Anschließend wird die Katalysatormasse auf Temperaturen von 600 bis 1500, vorzugsweise 700 bis 1300, insbesondere 1000 bis 1200°C über einen Zeitraum von 15 Minuten bis 20 Stunden, insbesondere 30 Minuten bis 5 Stunden erhitzt.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. 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.
Nach einer anderen vorteilhaften Arbeitsweise gelangt man zu den erfindungsgemäßen katalytisch aktiven Massen, indem man beispielsweise Aluminiumoxid oder eines der anderen genannten Oxide, die bereits eine Körnung von 0,1 bis 2 mm haben, unter Druck mit Bortrioxid oder Borverbindungen, die unter den Herstellungsbedingungen des Katalysators in Bortrioxid oder Borsäure übergehen, unter Mitverwendung von Solvatisierungsmitteln bei erhöhter Temperatur unter Druck tränkt. Als Solvatisierungsmittel eignet sich vorteilhaft Wasser, gegebenenfalls unter Zusatz geringer Mengen an Ammoniak oder Mineralsäuren wie Chlorwasserstoffsäure oder Perchlorsäure, ferner sind geeignete Solvatisierungsmittel Alkohöle wie Methanol, Äthanol oder Glycerin. Vorteilhaft tränkt man die Oxide unter erhöhtem Druck, z.B. 1,1 bis 20 bar bei erhöhter Temperatur, z.B. 50 bis 250°C. Das Gewichtsverhältnis von Lösungsmittel zu den verwendeten Ausgangsstoffen beträgt vorteilhaft 1:1 bis 10:1. Insbesondere verwendet man gleiche Gewichtsteile Lösungsmittel und Ausgangsstoffe. Einen solchen sogenannten Tränkkatalysator trocknet man anschließend bei Temperaturen von 50 bis 200°C und erhitzt anschließend auf Temperaturen von 600 bis 1500°C. Die Katalysatoren können als Vollkatalysatoren oder auf Träger aufgebracht angewandt werden.According to another advantageous procedure, 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. 1.1 to 20 bar at elevated temperature, e.g. 50 to 250 ° C. The weight ratio of solvent to the starting materials used is advantageously 1: 1 to 10: 1. In particular, 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.
Die Katalysatoren können fest angeordnet verwendet werden. Vorteilhaft wendet man die Katalysatoren jedoch in ab- und aufwerbeinder Bewegung in einem Wirbelbett an. Es hat sich als vorteilhaft erwiesen, wenn man bei der Umsetzung Verweilzeiten von 0,01 bis 50 Sekunden am Katalysator einhält.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.
Das Verfahren wird beispielsweise ausgeführt, indem man einen feinkörnigen Trägerkatalysator, beispielsweise Aluminiumoxid, das Bortrioxid enthält, in einer zur Erzeugung eines Wirbelbetts geeigneten Vorrichtung wirbelt, auf die angegebenen Temperaturen erhitzt und von unten Carbonsäureester oder Carbonsäuren in gasförmiger Form, gegebenenfalls zusammen mit Trägergasen durch das Katalysatorbett leitet. Selbstverständlich kann die Carbonsäure oder der Ester auch flüssig , in das erhitzte Katalysatorbett eingeleitet wenden.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. Of course, the carboxylic acid or the ester can also be introduced in liquid form into the heated catalyst bed.
Das erhaltene Gasgemisch wird abgekühlt und hierbei Olefine nichtumgesetzte Ausgangsstoffe und gegebenenfalls bei der Verwendung von Estern die entsprechenden Alkohole kondensiert. Die inerten gasförmigen Anteile können wieder als Trägergas verwendet werden. Desgleichen können nichtumgesetzte Ausgangsstoffe wieder der Reaktion zugeführt werden. Gegebenenfalls ist es notwendig, die anfallenden Olefine von den als Nebenprodukten erzeugten Alkoholen abzutrennen, z.B. durch Destillation.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. Likewise, 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.
Olefinisch ungesättigte Kohlenwasserstoffe, die nach dem Verfahren der Erfindung hergestellt werden, eignen sich beispielsweise zur Herstellung von Aldehyden nach der Oxosynthese. Cyclohexen, das man nach dem Verfahren der Erfindung erhält, eignet sich zur Herstellung von Cyclohexanol, wie beispielsweise in der GB--PS 339 592 beschrieben wird.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.
Das Verfahren nach der Erfindung sei in folgenden Beispielen veranschaulicht.The method according to the invention is illustrated in the following examples.
Aus einem Verdampfer wurden 200 g Hexahydrobenzoesäure je Stunde in einen auf 550°C beheizten Wirbelschichtreaktor eingeleitet, der mit 630 g Katalysator, bestehend aus 52,3 Gewichtsprozent γ―Al2O3 und 45,5 Gewichtsprozent B203 mit einer Korngröße von 0,1 bis 0,3 mm und einem Schüttgewicht von 0,63 kg je Liter beschickt war. Die Wirbelung des Katalysators wurde durch den Hexahydrobenzoesäuredampf, einen schwachen Stickstoffstrom, sowie durch Aufrechterhaltung eines Unterdruckes von 480 mbar gewährleistet. Die entstandenen Reaktionsdämpfe wurden kondensiert. Nach 3-stündigem Betrieb wurden folgende Produkte isoliert: 86 g Wasser, 384 g einer organischen Phase. Die organische Phase wurde mit wäßriger Natriumbicarbonat-Lösung gewaschen, um Spuren nicht umgesetzter Hexahydrobenzoesäure zu entfernen, und anschließend destilliert. Die gaschromatographische Untersuchung des Destillats ergab folgende Zusammensetzung: 63 Gewichtsprozent Cyclohexen, 29 Gewichtsprozent 1-Methyl- cyclopenten (1), 4 Gewichtsprozent 3-Methylcyclopenten (1) und 4 Gewichtsprozent. 4-Methylcyclopenten (1).From an evaporator, 200 g of hexahydrobenzoic acid per hour were introduced into a fluidized bed reactor heated to 550 ° C., which was equipped with 630 g of catalyst consisting of 52.3% by weight γ ― Al 2 O 3 and 45.5% by weight B 2 0 3 with a particle size of 0.1 to 0.3 mm and a bulk density of 0.63 kg per liter was loaded. The turbulence of the catalyst was ensured by the hexahydrobenzoic acid vapor, a weak nitrogen flow and by maintaining a negative pressure of 480 mbar. The reaction vapors formed were condensed. After 3 hours of operation, the following products were isolated: 86 g of water, 384 g of an organic phase. 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).
Es wurde analog Beispiel 1 verfahren, mit dem Unterschied, daß der im Beispiel 1 verwendete Katalysator vor Verwendung 4 Stunden auf 1150°C erhitzt wurde. Nach 7- stündigem Betrieb wurden 61 g Wasser sowie 356 g einer organischen Phase, bestehend nach Aufarbeitung gemäß Beispiel 1 aus 72 Gewichtstprozent Cyclohexen und 23 Gewichtsprozent 1-Methyl-cyclopenten (1), erhalten.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.
Es wurde analog Beispiel 1 verfahren, mit dem Unterschied, daß der in Beispiel 1 verwendete Katalysator zusätzlich 1,3 Gewichtsprozent Rhodium enthält. Nach 3-stündigem Betrieb wurden 69 g Wasser und 366 g einer organischen Phase, bestehend nach Aufarbeitung gemäß Beispiel 1 aus 74 Gewichtsprozent Cyclohexen, 19,6 Gewichtsprozent 1-Methyl- cyclopenten (1) und 5,5 Gewichtsprozent Benzol, erhalten.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.
Aus einem Verdampfer wurden 300 g Hexahydrobenzoesäure je Stunde in einen auf Reaktionstemperatur (480°C) beheizten Wirbelschichtreaktor eingeleitet, der mit 795 g Katalysator, bestehend aus 35 Gewichtsprozent γ―Al2O3, 45 Gewichtsprozent B201 und 20 Gewichtsprozent Sn02 mit einer Korngröße von 0,1 bis 0,3 mm und einem Schüttgewicht von 0,795 kg je Liter beschickt war. Die Wirbelung des Katalysators wurde durch den Hexahydrobenzosäuredampf, einen schwachen Stickstoffstrom, sowie durch Aufrechterhaltung eines Unterdruckes von 480 mbar gewährleistet. Die entstehenden Reaktionsdämpfe wurden kondensiert. Nach 4-stündigem Betrieb wurden 186 g Wasser und 813 g einer organischen Phase, bestehend nach Aufarbeitung gemäß Beispiel 1 aus 68,3 Gewichtsprozent Cyclohexen und 19,2 Gewichtsprozent 1-Methylcyclopenten (1) isoliert.From an evaporator, 300 g of hexahydrobenzoic acid per hour were introduced into a fluidized bed reactor heated to the reaction temperature (480 ° C.), which was equipped with 795 g of catalyst consisting of 35 percent by weight γ ― Al 2 O 3 , 45 percent by weight B 2 0 1 and 20 percent by weight Sn0 2 was loaded with a grain size of 0.1 to 0.3 mm and a bulk density of 0.795 kg per liter. The turbulence of the catalyst was ensured by the hexahydrobenzoic acid vapor, a weak stream of nitrogen, and by maintaining a negative pressure of 480 mbar. The resulting reaction vapors were condensed. After 4 hours of operation, 186 g of water and 813 g of an organic phase, consisting, after working up according to Example 1, of 68.3% by weight of cyclohexene and 19.2% by weight of 1-methylcyclopentene (1) were isolated.
Aus einem Verdampfer wurden 200 g Hexahydrobenzoesäuremethylester je Stunde in 'einen auf Reaktionstemperatur (550°C) beheizten Wirbelschichtreaktor eingeleitet, der mit 630 g Katalysator, bestehend aus 52,3 Gewichtsprozent γAl2O3 und, 45,5. Gewichtsprozent B203 mit einer Korngröße von 0,1 bis 0,3 mm und einem Schüttgewicht von 0,63 kg je Liter beschickt war. Die Wirbelung des Kontaktes wurde durch den Hexahydrobenzoesäuremethylesterdampf, einen schwachen Stickstoffstrom, sowie durch Aufrechterhaltung eines Unterdruckes von 480 mbar gewährleistet. Die entstandenen Reaktionsdämpfe wurden kondensiert. Nach 3- stündigem Betrieb der Anlage wurden 184 g einer organischen Phase, bestehend nach Wasserwäsche und Destillation aus 82,3 Gewichtsprozent Cyclohexen und 17,7 Gewichtsprozent 1-Methylcyclopenten (1), isoliert.An evaporator 200 g of Hexahydrobenzoesäuremethylester g with 630 catalyst consisting of 52.3 weight percent γAl 2 O 3 and 45.5 were per hour in 'initiated heated to reaction temperature (550 ° C) fluidized bed reactor. Weight percent B 2 0 3 was loaded with a grain size of 0.1 to 0.3 mm and a bulk density of 0.63 kg per liter. The swirling of the contact was ensured by the hexahydrobenzoic acid methyl ester vapor, a weak stream of nitrogen and by maintaining a negative pressure of 480 mbar. The reaction vapors formed were condensed. After the plant had been in operation for 3 hours, 184 g of an organic phase consisting of 82.3% by weight of cyclohexene and 17.7% by weight of 1-methylcyclopentene (1) after water washing and distillation were isolated.
Es wurde analog Beispiel 3 verfahren, außer daß die Reaktionstemperatur 700°C betrug. Nach 3-stündigem Betrieb der Anlage wurden 265 g einer organischen Phase, bestehend nach Wasserwäsche und Destillation aus 74 Gewichtsprozent Cyclohexen und 25 Gewichtsproztent 1-Methylcyclopenten (1), isoliert.The procedure was analogous to Example 3, except that the reaction temperature was 700 ° C. After the plant had been in operation for 3 hours, 265 g of an organic phase consisting of 74% by weight of cyclohexene and 25% by weight of 1-methylcyclopentene (1) after water washing and distillation were isolated.
Aus einem Verdampfer wurden 200 g Hexahydrobenzoesäurecyclohexylester je Stunde in einen auf Reaktionstemperatur (600°C) beheizten Wirbelschichtreaktor eingeleitet, der mit 630 g Katalysator, bestehend aus 52,3 Gewichtsprozent γ―Al2O3 und 45,5 Gewichtsprozent B20, mit einer Korngröße von 0,1 bis 0,3 mm und einem Schüttgewicht von 0,63 kg je Liter, beschickt war. Die Wirbelung des Kontaktes wurde durch den Hexahydrobenzoesäurecyclohexylesterdampf, einen schwachen Stickstoffstrom, sowie durch Aufrechterhaltung eines Unterdruckes von 480 mbar gewährleistet. Die entstandenen Reaktionsdämpfe wurden kondensiert. Nach 3-stündigem Betrieb der Anlage wurden 440 g einer organischen Phase erhalten, welche nach Wasserwäsche und Destillation aus 54 Gewichtsprozent 1-Methylcyclopenten (1) und 42,6 Gewichtsprozent Cyclohexen bestand.From an evaporator, 200 g of hexahydrobenzoic acid cyclohexyl ester per hour were introduced into a fluidized bed reactor heated to the reaction temperature (600 ° C.), which was charged with 630 g of catalyst consisting of 52.3 percent by weight γ ― Al 2 O 3 and 45.5 percent by weight B 2 0 a grain size of 0.1 to 0.3 mm and a bulk density of 0.63 kg per liter. The swirling of the contact was ensured by the hexahydrobenzoic acid cyclohexyl ester vapor, a weak stream of nitrogen and by maintaining a negative pressure of 480 mbar. The reaction vapors formed were condensed. After operating the plant for 3 hours, 440 g of an organic phase were obtained which, after water washing and distillation, consisted of 54% by weight of 1-methylcyclopentene (1) and 42.6% by weight of cyclohexene.
Es wurde analog Beispiel 4 verfahren, außer daß als Ester Hexahydrobenzoesäurephenylester eingesetzt wurde und die Reaktionstemperatur 700°C betrug. Nach 3-stündigem Betrieb der Anlage wurden 243 g Phenol, und 266 g einer organischen Phase, bestehend nach Wasserwäsche und Destillation aus 62 Gewichtsprozent 1-Methylcyclopenten (1) und 32 Gewichtsprozent Cyclohexen, isoliert.The procedure was analogous to Example 4, except that hexahydrobenzoic acid phenyl ester was used and the reaction temperature was 700 ° C. After the plant had been in operation for 3 hours, 243 g of phenol and 266 g of an organic phase consisting of 62% by weight of 1-methylcyclopentene (1) and 32% by weight of cyclohexene after water washing and distillation were isolated.
Es wurde analog Beispiel 4 verfahren, außer daß als Ester Hexahydrobenzoesäurebenzylester eingesetzt wurde und die Reaktionstemperatur 700°C betrug. Nach 3-stündigem Betrieb wurden 77 g Toluol, 31 g Benzaldehyd, 51 g Benzylalkohol, und 122 g einer organischen Phase, bestehend nach Wasserwäsche und Destillation aus 44 Gewichtsprozent 1-Methylcyclopenten (1) und 36 Gewichtsprozent Cyclohexen, isoliert.The procedure was analogous to Example 4, except that benzyl hexahydrobenzoate was used as the ester and the reaction temperature was 700 ° C. After 3 hours of operation, 77 g of toluene, 31 g of benzaldehyde, 51 g of benzyl alcohol and 122 g of an organic phase consisting of 44% by weight of 1-methylcyclopentene (1) and 36% by weight of cyclohexene after water washing and distillation were isolated.
Aus einem Verdampfer wurden 200 g Capronsäure je Stunde in einen auf Reaktionstemperatur (550°C) beheizten Wirbelschichtreaktor eingeleitet, der mit 630 g Katalysator bestehend aus 50 Gewichtsprozent B203 und 50 Gewichtsprozent γ―Al2O3 mit einer Korngröße von 0,1 bis 0,3 mm und einem Schüttgewicht von 0,63 kg pro Liter beschickt war. Die Wirbelung des Katalysators wurde durch den Capronsäuredampf, einen schwachen Stickstoffstrom sowie durch Aufrechterhaltung eines Unterdruckes von 480 mbar gewährleistet. Die entstandenen Reaktionsdämpfe wurden kondensiert. Nach 3-stündigem Betrieb der Anlage wurden 229 g einer organischen Phase, bestehend aus 1,5 Gewichtsprozent 3-Methylbuten (1),. 14,3 Gewichtsprozent Penten (1), 10 Gewichtsprozent 2-Methyl-buten (1), 30 Gewichtsprozent Penten (2) trans, 17,2 Gewichtsprozent Penten (2) cis, 21 Gewichtsprozent 2-Methyl-buten (2), isoliert.From an evaporator, 200 g of caproic acid per hour were introduced into a fluidized bed reactor heated to the reaction temperature (550 ° C.), which was equipped with 630 g of catalyst consisting of 50% by weight of B 2 0 3 and 50% by weight of γ ― Al 2 O 3 with a particle size of 0. 1 to 0.3 mm and a bulk density of 0.63 kg per liter was loaded. The turbulence of the catalyst was ensured by the caproic acid vapor, a weak nitrogen flow and by maintaining a negative pressure of 480 mbar. The reaction vapors formed were condensed. After the plant had been in operation for 3 hours, 229 g of an organic phase consisting of 1.5% by weight of 3-methylbutene (1). 14.3 percent by weight pentene (1), 10 percent by weight 2-methyl-butene (1), 30 percent by weight pentene (2) trans, 17.2 percent by weight pentene (2) cis, 21 percent by weight 2-methyl-butene (2) .
Claims (9)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2726106 | 1977-06-10 | ||
| DE2726106A DE2726106C3 (en) | 1977-06-10 | 1977-06-10 | Process for the production of olefinically unsaturated aliphatic or cycloaliphatic hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000054A1 EP0000054A1 (en) | 1978-12-20 |
| EP0000054B1 true EP0000054B1 (en) | 1980-10-29 |
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ID=6011133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100096A Expired EP0000054B1 (en) | 1977-06-10 | 1978-06-06 | Process for the preparation of olefinic unsaturated aliphatic or cycloaliphatic hydrocarbons |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4178317A (en) |
| EP (1) | EP0000054B1 (en) |
| JP (1) | JPS545902A (en) |
| DE (2) | DE2726106C3 (en) |
| IT (1) | IT1104729B (en) |
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|---|---|---|---|---|
| NL7811732A (en) * | 1978-11-30 | 1980-06-03 | Stamicarbon | METHOD FOR CONVERSION OF DIMETHYL ETHER |
| JPS606334B2 (en) * | 1979-07-16 | 1985-02-18 | 三菱レイヨン株式会社 | Production method of high purity isobutylene |
| US4393260A (en) * | 1980-08-01 | 1983-07-12 | The Standard Oil Company | Preparation of cyclohexenyl compounds |
| EP0154829B1 (en) * | 1982-03-27 | 1987-01-07 | BASF Aktiengesellschaft | Process for the preparation of olefines from methanol/dimethyl ether |
| FR2551056B1 (en) * | 1983-08-25 | 1985-11-29 | Inst Francais Du Petrole | NOVEL PROCESS FOR THE MANUFACTURE OF LINEAR OLEFIN FROM FATTY ACID OR SATURATED FATTY ACID ESTER |
| DE3813147A1 (en) * | 1988-04-20 | 1989-11-02 | Basf Ag | METHOD FOR THE PRODUCTION OF OLEFINICALLY UNSATURATED, END-STANDING CARBOXYLIC ACID ESTERS |
| US5077447A (en) * | 1990-09-28 | 1991-12-31 | Henkel Research Corporation | Process for making olefins |
| JPH04102559U (en) * | 1991-02-04 | 1992-09-03 | ソニー株式会社 | Button alkaline battery |
| JP3089974B2 (en) * | 1995-02-13 | 2000-09-18 | 日本ビクター株式会社 | Signal recording method and video signal processing device |
| JP2011168529A (en) * | 2010-02-18 | 2011-09-01 | Kao Corp | Method of producing olefin |
| JP2011168528A (en) * | 2010-02-18 | 2011-09-01 | Kao Corp | Method of producing olefin |
| JP6027437B2 (en) * | 2012-12-28 | 2016-11-16 | 花王株式会社 | Production method of olefin |
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| 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 (en) * | 1960-08-22 | 1961-10-27 | Idemitsu Kosan Kabushikikaisha | Process for preparing isoprene and acetic acid by catalytic decomposition of methyl-3-butene-3-ol-1 acetate and isoprene-glycol diacetate |
| US4024171A (en) * | 1975-06-30 | 1977-05-17 | Union Oil Company Of California | Aluminum borate catalyst compositions and use thereof in chemical conversions |
-
1977
- 1977-06-10 DE DE2726106A patent/DE2726106C3/en not_active Expired
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1978
- 1978-05-19 US US05/907,678 patent/US4178317A/en not_active Expired - Lifetime
- 1978-06-06 EP EP78100096A patent/EP0000054B1/en not_active Expired
- 1978-06-06 DE DE7878100096T patent/DE2860251D1/en not_active Expired
- 1978-06-07 JP JP6785578A patent/JPS545902A/en active Pending
- 1978-06-08 IT IT49772/78A patent/IT1104729B/en active
Also Published As
| Publication number | Publication date |
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| DE2726106C3 (en) | 1980-06-26 |
| DE2726106B2 (en) | 1979-07-26 |
| US4178317A (en) | 1979-12-11 |
| DE2860251D1 (en) | 1981-01-29 |
| JPS545902A (en) | 1979-01-17 |
| DE2726106A1 (en) | 1978-12-14 |
| IT7849772A0 (en) | 1978-06-08 |
| EP0000054A1 (en) | 1978-12-20 |
| IT1104729B (en) | 1985-10-28 |
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