CA2292584A1 - Supported catalyst used in the production of cycloalkadienes in a metathesis reaction - Google Patents
Supported catalyst used in the production of cycloalkadienes in a metathesis reaction Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/36—Rhenium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/122—Metal aryl or alkyl compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
- C07C6/06—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond at a cyclic carbon-to-carbon double bond
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/54—Metathesis reactions, e.g. olefin metathesis
- B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/74—Rhenium
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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
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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
- 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
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/32—Manganese, technetium or rhenium
- C07C2523/36—Rhenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
Abstract
The invention relates to a supported catalyst used in the production of cycloalkadienes in a metathesis reaction containing a) .gamma.-Al2O3 as supporting material; b) 2-20 wt.% Re2O7; c) 0.5-5 wt.% B2O3; d) 0-20 wt.% SnR4 or SnO2, or a mixture of SnR4 and SnO2, in which R stands for an alkyl or aryl radical. The invention also relates to a method for producing cycloalkadienes in the liquid phase by metathesis reaction of cycloalkenes, cyclopolyenes, linear polyenes and their mixtures in the presence of the supported catalyst.
Description
~e ~~c Supported catalyst for use in preparing cycloalkadienes in a metathesis reaction The present invention relates to a supported catalyst for use in preparing cycloalkadienes in a metathesis reaction and also to a process for preparing cycloalkadienes in the liquid phase by a metathesis reaction of cycloalkenes, cyclopolyenes, linear polyenes and mixtures of these in the presence of the supported catalyst.
Cycloalkadienes with a ring size from 12 to 18 carbon atoms are used, inter alia, in preparing macrocyclic oxo compounds. Macrocyclic ketones and epoxides are of particular interest here, and are used as valuable musk fragrances. Another application sector for these macrocyclic oxo compounds is their use as selective complexing agents in preparing y-cyclodextrin.
It is known from cUH-A 1105565 that cycloalkadienes, such as cyclohexadecadiene, can be prepared by a metathesis reaction of cyclooctene on a Re20~/y-A1203 contact catalyst. The type of reaction on which the process mentioned is based can be described as a dimerization of the starting material. The yields are given as 6~ by weight, based on the cyclooctene used. The unsatisfactory yield is attributable to the fact that the progress of the reaction is unsatisfactory in relation to dimerization and the majority of the products formed are higher oligomers or polymers, which may be cyclic or acyclic.
From EP-A 182333 (US-A 4668836) it is known that the selectivity of the metathesis reaction to give the desired dimer can be significantly increased if the reaction is executed at high dilutions. Using the catalyst system Re20~/y-A1203/SnR4, where R is an alkyl radical, selectivities of up to 50 mold can be obtained using dilute, 0.01 - 0.05 molar cycloolefin solutions in a solvent which is inert with respect to metathesis.
Preferred reaction temperatures are in the range from 0 to 50°C. According to EP-B 343437, the starting __.... _.____ ~ _ Co 9707/Sc materials which can be used in preparing cycloalkadienes by a metathesis reaction in the presence of a Re20~/A1203/SnR4 catalyst include oligomeric and polymeric cycloolefins, and also mixtures of these with corresponding monomeric cycloolefins.
However, the catalyst system described in EP-A 182333 and EP-B 343437 has the disadvantage of becoming rapidly deactivated at temperatures above 50°C, whereas reaction temperatures above 50°C would be highly advantageous, since they would markedly raise the productivity of the process, i.e. the space-time yield.
The object was therefore to provide a supported catalyst and a process with which the preparation of cycloalkadienes by a metathesis reaction takes place with high selectivity, even at relatively high reaction temperatures.
The invention provides a supported catalyst for use in preparing cycloalkadienes in a metathesis reaction, comprising a) y-A1203 as support, b) from 2 to 20~ by weight of RezO~, c) from 0.5 to 5$ by weight of Bz03, and d) from 1 to 20~ by weight of SnRa or Sn02 or of a mixture of SnR4 and Sn02, where R is an alkyl or aryl radical and the data in ~ by weight are in each case based on Y-A12O3.
The support material used in the supported catalysts is y-A1203 with a BET specific surface area of from 100 to 300 m2/g (Brunauer, Emmett and Teller method of determination). The support material used is in the form of moldings; preferably as extrudates, beads, cylinders, cubes or moldings of tapered shape.
The proportion of Re20~ by weight is preferably from 2 to 10~ by weight, based on the aluminum oxide content.
A significant factor for prolonging the operating time of the supported catalyst at relatively high reaction temperatures is the doping of the same AMENDED PAGE
_ _ .
Co 9707/Sc - 3 -with boron oxide. The boron oxide content is from 0.5 to 5~ by weight, based on the aluminum oxide content.
According to the invention, the catalyst is doped with the tin compounds mentioned under d).
Surprisingly, it has been found that the prolongation of operating time of the supported catalyst resulting from boron oxide doping can be further raised in the presence of component d). Suitable components d) are SnR4 compounds in which R is identical or different substituents selected from the class consisting of C1-C6 alkyl and phenyl radicals. Examples of these are tetramethyltin, tetraethyltin and tetra-n-butyltin.
Preferred components d) are mixtures of the SnR4 compounds mentioned with Sn02, or Sn02 as sole component d). The content of component d) in the make up of the supported catalyst is preferably from 1 to 20a by weight, particularly preferably from 1 to 10~ by weight, based on the aluminum oxide content.
The catalyst is prepared using procedures known to the skilled worker. Usually, the aluminum oxide support is impregnated with aqueous solutions of a water--soluble rhenium compound, such as ammonium perrhenate, and with a water-soluble boron compound, such as boric acid. It is also possible to use a mixture made from water and a water-miscible organic solvent, such as dioxane, to dissolve the compounds.
The sequence of the impregnation with the aqueous solutions of the rhenium compound and, respectively, of the boron compound here is as desired. The preferred procedure is to apply the rhenium compound and the boron compound in an impregnating solution to the aluminum oxide support in one step. For impregnating, the aqueous mixture of support component, rhenium compound and boron compound is heated for a number of hours, generally from 6 to 12 hours, to boiling point, and the liquid phase is removed, for example by decanting. The impregnated support is then dried.
AMENDED PAGE
.._ . _. ___~
I
To activate the catalyst, i.e. to convert the rhenium compound and, respectively, boron compound into the active components b) and c), the impregnated support is heated in an oxygen-containing atmosphere, generally air, for from 1 to 3 hours, at from 500 to 600°C. After the calcination, the support is heated for a further 1 - 3 hours under an inert gas, such as nitrogen or argon, and cooled to room temperature in an inert gas atmosphere.
The procedure for doping using an SnR4 compound is that the supported catalyst is impregnated, in a further step, with a solution of the appropriate tin compound in an organic solvent, such as petroleum ether. For this, a mixture made from supported catalyst and the solution of the tin compound may be stirred for a number of hours, as in the abovementioned procedure for the impregnation. Another possible procedure is for the supported catalyst to be impregnated directly prior to the metathesis. reaction. For this, the supported catalyst is charged to the reactor and a pump is used to circulate a solution of the tin compound in the reactor for a number of hours.
After use in the metathesis reaction, the supported catalyst may be regenerated and reused. For regeneration, the catalyst is removed from the metathesis reactor and washed with an inert organic solvent, such as toluene, cyclohexane or methylene chloride. The supported catalyst is then dried and calcined as described above for activation of the catalyst. To this, the supported catalyst is heated in an oxygen-containing atmosphere, generally air, for from 1 to 3 hours, at from 500 to 600°C. Care has to be taken here that the temperature of 600°C is not exceeded within the catalyst. If appropriate, the oxygen content of the regeneration air must be reduced by adding an inert gas, such as nitrogen or argon.
After oxidative regeneration, the support is heated for a further 1 - 3 hours under an inert gas, such as nitrogen or argon, and cooled to room temperature in an ~ _..._.____.._.. -_.~-__. .
Co 9707/Sc - 5 -inert gas atmosphere. The regeneration does not result in any change in the content of Re20~ and, respectively, Bz03 ; the SnR4 component is converted to SnOz . On reuse of a regenerated supported catalyst initially doped with a tin alkyl compound. it has now been found, surprisingly, that after the regeneration there is a marked improvement in the increased operating time obtained with the boron oxide doping. This effect could well be attributable to a synergistic interaction between boron oxide component and tin oxide component.
An alternative procedure for the regeneration of a supported catalyst containing tin alkyl compounds, for doping using Sn02, is for the aluminum oxide support to be impregnated with a water-soluble tin salt, such as tin(IV) chloride, as in the procedure for the impregnation with a rhenium compound and, respectively, boron compound.
The invention also provides a process for preparing cycloalkadienes in the liquid phase by a metathesis reaction of cycloalkenes, cyclopolyenes, linear polyenes and mixtures thereof in the presence of a supported catalyst at a reaction temperature of from 0 to 100°C, which comprises using a supported catalyst comprising 2 5 a ) y-A1203 as support , b) from 2 to 20~ by weight of ReZO~, c) from 0.5 to 5~ by weight of B?03, and d) from 1 to 20$ by weight of SnR4 or Sn02 or of a mixture of SnR4 and Sn02, where R is an alkyl or aryl radical and the data in % by weight are in each case based on y-A1z03.
Suitable starting materials are those selected from the class of cycloolefins and having a ring size of from 4 to 12 carbon atoms. Preference is given to cyclopentene, cycloheptene, cyclooctene, cyclooct-adiene, cyclodecene and cyclododecene. Particular preference is given to cycloheptene and cyclooctene.
AMENDED PAGE
Co 9707/Sc - 5a -Suitable cyclopolyenes or linear polyenes are those which are obtained using the cycloolefins mentioned, AMENDED PAGE
__ for example as byproducts of metathetic dimerizations.
The cyclopolyenes and the linear polyenes generally have a degree of polymerization of from 3 to 20. It is also possible to use mixtures of two or more compounds selected from the class consisting of cycloolefins, cyclopolyenes and linear polyenes.
The starting materials are used as a solution r of from 0.01 to 0.1 molar strength, preferably from 0.03 to 0.06 molar strength, in an inert organic solvent. Examples of suitable solvents are pentane, hexane " heptane, cyclopentane, cyclohexane, petroleum ether, methylene chloride, chloroform and carbon tetrachloride. In principle, the reaction may be carried out at temperatures of from 0 to 100°C.
However, the novel supported catalyst provides for the first time a metathesis catalyst which has the operating times required in industry, even at relatively high reaction temperatures, associated with a correspondingly improved space-time performance. For the reaction temperature, therefore, the range from 50 to 100°C is strongly preferred, in particular in the range from 60 to 100°C. When solvents are used whose boiling point is below the reaction temperature, it is also possible to use superatmospheric pressure. The pressure is generally from 1 bar abs. to 10 bar abs.
The metathesis reaction is generally carried out in a fixed-bed reactor, for example in a vertically positioned tubular reactor charged with supported catalyst, and the solution of the starting materials flows in a vertical direction through the reactor. The flow rate here is set in such a way as to give residence times of from 10 to 600 seconds, preferably from 10 to 200 seconds. The reaction mixture leaving the reactor is passed to distillation equipment and separated into its components. The target product is produced as a relatively high-boiling fraction. For practical purposes continuous operation is mostly maintained, with solvent and also, if desired, unconverted starting material, circulated and returned r _ .__..__.__ _ 7 _ into the reactor after supplementation with new starting material. In the case of continuous operation, the evaporation/condensation of the solvent mixture may be achieved in a conventional manner (e. g. evaporators operated using steam and condensers operated using coolants). However, it is advantageous to use lower-energy processes, such as vapor compression, since this significantly reduces energy costs and allows the process to be carried out more cost-effectively.
The Examples below serve to describe the invention in greater detail:
Example 1 (Comparative Example):
Preparation of the comparative catalyst ( y-A1203 / Re20~ / Sn ( CH3 ) a ) NH4Re04 ( 5 . 5~ by weight , based on A1203 ) was dissolved in a dioxane/water mixture (80/20 v/v), and the y-A1z03 added to this as extrudates of length from 3 to 8 mm and diameter from 1.5 to 1.8 mm and BET surface area of 190 mz/g. The mixture was then heated to boiling. After an impregnation time of about 10 hours, the liquid phase was decanted and the catalyst pre-dried at 120°C. Activation was by treatment with air for 2 hours at from 500 to 600°C. The temperature was then held while the air was replaced by nitrogen. After a further 2 hours, the material was cooled to room temperature, taking care that no oxygen reached the catalyst. The content of Re20~ was 3.7~ by weight. The supported catalyst was then treated with a pentane solution of Sn(CH3)4, with impregnation taking place directly in the metathesis reactor. The content of Sn(CH3)4 was 2.5~ by weight. The data in ~ by weight are based in each case on aluminum oxide.
Example 2 r I
_ .8 _ Preparation of a catalyst comprising boron oxide ( y-A1203 / Re20~ / Bz03 / Sn ( CH3 ) a ) Boric acid (11.7 by weight, based on A1z03) was dissolved in water. NH4Re04 (5.5~ by weight, based on A1203) was then dissolved in this solution. Dioxane was then added to this solution until the dioxane/water ratio was 85/15 v/v. The A1203 extrudates as in Example 1 were then added, and the impregnation, calcination and Sn(CH3)4 treatment were carried out as in Example 1.
The content of Re20~ was 3.7~~by weight, the boron oxide content was 1.8~ by weight, and the Sn(CH3)4 content was 2.5~ by weight. The data in ~ by weight are based in each case on aluminum oxide.
Example 3 (Comparative Example):
Metathesis of a cyclopolyoctenylene mixture with the boron-oxide-free catalyst from Example 2 at 60°C
A vertically arranged reactor which could be heated (length 500 mm, internal diameter 26.5 mm) was charged with 200 g of catalyst from Example 1. The reactor was then heated to 60°C, and a 0.048 molar solution (concentration data based on the monoolefin unit cyclooctene) of a cyclopolyoctenylene mixture in pentane was passed through the catalyst bed. The pressure in the reactor was set to 6 bar abs. to prevent boiling of the pentane. The make up of the cyclopolyoctenylene mixture is given in Table 1:
Table 1:
Degree of polymerization Proportion (g by weight) 3 42.5 4 23.8 5 13.3 6 7.9 7 and above 10.1 ~___. _.. _._ _ The average residence time of the mixture in the reactor was 80 seconds. The reaction mixture leaving the reactor was fed to distillation equipment, where the n-pentane was distilled off and refed to the reactor after charging with fresh cyclopolyoctenylene mixture. Table 2 gives the average concentrations of 1,9-cyclohexadecadiene (CHDD concentrations) in the reaction mixture as a function of the duration of the experiment. Samples were taken directly downstream of the reactor.
Table 2:
Duration of experiment (h) CHDD content (g/1) 1 1.1 60 1.0 110 0.94 160 0.86 230 0.69 290 0.59 330 0.54 360 0.46 Example 4:
Metathesis of a cyclopolyoctenylene mixture with the catalyst from Example 2 comprising boron oxide, at 60°C
The procedure was as in Example 3 except that the catalyst prepared in Example 2 was used.
Table 3 gives the CHDD concentrations measured as a function of the duration of the experiment.
Table 3:
Duration of experiment (h) CHDD content (g/1) 1 1.2 110 1.0 300 0.85 400 0.80 500 0.76 ...._...~___...._....-..t.._ .~.._.. -.._-. _....
690 0.70 850 0.67 910 0.64 Example 5:
Metathesis of a cyclopolyoctenylene mixture with a regenerated catalyst comprising boron oxide and tin oxide, at 60°C
The catalyst used in Example 4 was removed from the reactor and washed with toluene. The catalyst was then dried at 100°C and calcined for 2 hours in air and for a further 2 hours in nitrogen, in each case at from 500 to 600°C, and then cooled to room temperature. The content of rhenium oxide and of boron oxide remained the same. The tetramethyltin had been converted into tin oxide. The Sn02 content was 0.53 by weight, based on aluminum oxide.
The catalyst regenerated in this way was then treated with a tetramethyltin-pentane solution as in Example 3 (2.5$ by weight of Sn(CH3)9) and used for the metathesis of a cyclooctenylene mixture as in Example 3.
Table 4 gives the CHDD concentrations as a function of the duration of the experiment.
Table 4:
Duration of experiment (h) CHDD content (g/1) 1 1.3 60 1.2 200 1.1 300 1.1 450 1.1 600 1.1 700 1.1 850 1.1 970 1.1 1150 1.0 _.. . ..
The results from the metathesis reactions as in Comparative Example 3 (Table 2) and as in the inventive Examples 4 (Table 3) and 5 (Table 4) are given diagrammatically in Figure 1. It can be seen clearly that, compared with conventional metathesis catalysts (Example 3: A1z03/Re20~/Sn(CH3)4) boron oxide doping (Example 4) gives significantly higher operating times, and these can be increased still further by means of Sn02 doping (Example 5).
Cycloalkadienes with a ring size from 12 to 18 carbon atoms are used, inter alia, in preparing macrocyclic oxo compounds. Macrocyclic ketones and epoxides are of particular interest here, and are used as valuable musk fragrances. Another application sector for these macrocyclic oxo compounds is their use as selective complexing agents in preparing y-cyclodextrin.
It is known from cUH-A 1105565 that cycloalkadienes, such as cyclohexadecadiene, can be prepared by a metathesis reaction of cyclooctene on a Re20~/y-A1203 contact catalyst. The type of reaction on which the process mentioned is based can be described as a dimerization of the starting material. The yields are given as 6~ by weight, based on the cyclooctene used. The unsatisfactory yield is attributable to the fact that the progress of the reaction is unsatisfactory in relation to dimerization and the majority of the products formed are higher oligomers or polymers, which may be cyclic or acyclic.
From EP-A 182333 (US-A 4668836) it is known that the selectivity of the metathesis reaction to give the desired dimer can be significantly increased if the reaction is executed at high dilutions. Using the catalyst system Re20~/y-A1203/SnR4, where R is an alkyl radical, selectivities of up to 50 mold can be obtained using dilute, 0.01 - 0.05 molar cycloolefin solutions in a solvent which is inert with respect to metathesis.
Preferred reaction temperatures are in the range from 0 to 50°C. According to EP-B 343437, the starting __.... _.____ ~ _ Co 9707/Sc materials which can be used in preparing cycloalkadienes by a metathesis reaction in the presence of a Re20~/A1203/SnR4 catalyst include oligomeric and polymeric cycloolefins, and also mixtures of these with corresponding monomeric cycloolefins.
However, the catalyst system described in EP-A 182333 and EP-B 343437 has the disadvantage of becoming rapidly deactivated at temperatures above 50°C, whereas reaction temperatures above 50°C would be highly advantageous, since they would markedly raise the productivity of the process, i.e. the space-time yield.
The object was therefore to provide a supported catalyst and a process with which the preparation of cycloalkadienes by a metathesis reaction takes place with high selectivity, even at relatively high reaction temperatures.
The invention provides a supported catalyst for use in preparing cycloalkadienes in a metathesis reaction, comprising a) y-A1203 as support, b) from 2 to 20~ by weight of RezO~, c) from 0.5 to 5$ by weight of Bz03, and d) from 1 to 20~ by weight of SnRa or Sn02 or of a mixture of SnR4 and Sn02, where R is an alkyl or aryl radical and the data in ~ by weight are in each case based on Y-A12O3.
The support material used in the supported catalysts is y-A1203 with a BET specific surface area of from 100 to 300 m2/g (Brunauer, Emmett and Teller method of determination). The support material used is in the form of moldings; preferably as extrudates, beads, cylinders, cubes or moldings of tapered shape.
The proportion of Re20~ by weight is preferably from 2 to 10~ by weight, based on the aluminum oxide content.
A significant factor for prolonging the operating time of the supported catalyst at relatively high reaction temperatures is the doping of the same AMENDED PAGE
_ _ .
Co 9707/Sc - 3 -with boron oxide. The boron oxide content is from 0.5 to 5~ by weight, based on the aluminum oxide content.
According to the invention, the catalyst is doped with the tin compounds mentioned under d).
Surprisingly, it has been found that the prolongation of operating time of the supported catalyst resulting from boron oxide doping can be further raised in the presence of component d). Suitable components d) are SnR4 compounds in which R is identical or different substituents selected from the class consisting of C1-C6 alkyl and phenyl radicals. Examples of these are tetramethyltin, tetraethyltin and tetra-n-butyltin.
Preferred components d) are mixtures of the SnR4 compounds mentioned with Sn02, or Sn02 as sole component d). The content of component d) in the make up of the supported catalyst is preferably from 1 to 20a by weight, particularly preferably from 1 to 10~ by weight, based on the aluminum oxide content.
The catalyst is prepared using procedures known to the skilled worker. Usually, the aluminum oxide support is impregnated with aqueous solutions of a water--soluble rhenium compound, such as ammonium perrhenate, and with a water-soluble boron compound, such as boric acid. It is also possible to use a mixture made from water and a water-miscible organic solvent, such as dioxane, to dissolve the compounds.
The sequence of the impregnation with the aqueous solutions of the rhenium compound and, respectively, of the boron compound here is as desired. The preferred procedure is to apply the rhenium compound and the boron compound in an impregnating solution to the aluminum oxide support in one step. For impregnating, the aqueous mixture of support component, rhenium compound and boron compound is heated for a number of hours, generally from 6 to 12 hours, to boiling point, and the liquid phase is removed, for example by decanting. The impregnated support is then dried.
AMENDED PAGE
.._ . _. ___~
I
To activate the catalyst, i.e. to convert the rhenium compound and, respectively, boron compound into the active components b) and c), the impregnated support is heated in an oxygen-containing atmosphere, generally air, for from 1 to 3 hours, at from 500 to 600°C. After the calcination, the support is heated for a further 1 - 3 hours under an inert gas, such as nitrogen or argon, and cooled to room temperature in an inert gas atmosphere.
The procedure for doping using an SnR4 compound is that the supported catalyst is impregnated, in a further step, with a solution of the appropriate tin compound in an organic solvent, such as petroleum ether. For this, a mixture made from supported catalyst and the solution of the tin compound may be stirred for a number of hours, as in the abovementioned procedure for the impregnation. Another possible procedure is for the supported catalyst to be impregnated directly prior to the metathesis. reaction. For this, the supported catalyst is charged to the reactor and a pump is used to circulate a solution of the tin compound in the reactor for a number of hours.
After use in the metathesis reaction, the supported catalyst may be regenerated and reused. For regeneration, the catalyst is removed from the metathesis reactor and washed with an inert organic solvent, such as toluene, cyclohexane or methylene chloride. The supported catalyst is then dried and calcined as described above for activation of the catalyst. To this, the supported catalyst is heated in an oxygen-containing atmosphere, generally air, for from 1 to 3 hours, at from 500 to 600°C. Care has to be taken here that the temperature of 600°C is not exceeded within the catalyst. If appropriate, the oxygen content of the regeneration air must be reduced by adding an inert gas, such as nitrogen or argon.
After oxidative regeneration, the support is heated for a further 1 - 3 hours under an inert gas, such as nitrogen or argon, and cooled to room temperature in an ~ _..._.____.._.. -_.~-__. .
Co 9707/Sc - 5 -inert gas atmosphere. The regeneration does not result in any change in the content of Re20~ and, respectively, Bz03 ; the SnR4 component is converted to SnOz . On reuse of a regenerated supported catalyst initially doped with a tin alkyl compound. it has now been found, surprisingly, that after the regeneration there is a marked improvement in the increased operating time obtained with the boron oxide doping. This effect could well be attributable to a synergistic interaction between boron oxide component and tin oxide component.
An alternative procedure for the regeneration of a supported catalyst containing tin alkyl compounds, for doping using Sn02, is for the aluminum oxide support to be impregnated with a water-soluble tin salt, such as tin(IV) chloride, as in the procedure for the impregnation with a rhenium compound and, respectively, boron compound.
The invention also provides a process for preparing cycloalkadienes in the liquid phase by a metathesis reaction of cycloalkenes, cyclopolyenes, linear polyenes and mixtures thereof in the presence of a supported catalyst at a reaction temperature of from 0 to 100°C, which comprises using a supported catalyst comprising 2 5 a ) y-A1203 as support , b) from 2 to 20~ by weight of ReZO~, c) from 0.5 to 5~ by weight of B?03, and d) from 1 to 20$ by weight of SnR4 or Sn02 or of a mixture of SnR4 and Sn02, where R is an alkyl or aryl radical and the data in % by weight are in each case based on y-A1z03.
Suitable starting materials are those selected from the class of cycloolefins and having a ring size of from 4 to 12 carbon atoms. Preference is given to cyclopentene, cycloheptene, cyclooctene, cyclooct-adiene, cyclodecene and cyclododecene. Particular preference is given to cycloheptene and cyclooctene.
AMENDED PAGE
Co 9707/Sc - 5a -Suitable cyclopolyenes or linear polyenes are those which are obtained using the cycloolefins mentioned, AMENDED PAGE
__ for example as byproducts of metathetic dimerizations.
The cyclopolyenes and the linear polyenes generally have a degree of polymerization of from 3 to 20. It is also possible to use mixtures of two or more compounds selected from the class consisting of cycloolefins, cyclopolyenes and linear polyenes.
The starting materials are used as a solution r of from 0.01 to 0.1 molar strength, preferably from 0.03 to 0.06 molar strength, in an inert organic solvent. Examples of suitable solvents are pentane, hexane " heptane, cyclopentane, cyclohexane, petroleum ether, methylene chloride, chloroform and carbon tetrachloride. In principle, the reaction may be carried out at temperatures of from 0 to 100°C.
However, the novel supported catalyst provides for the first time a metathesis catalyst which has the operating times required in industry, even at relatively high reaction temperatures, associated with a correspondingly improved space-time performance. For the reaction temperature, therefore, the range from 50 to 100°C is strongly preferred, in particular in the range from 60 to 100°C. When solvents are used whose boiling point is below the reaction temperature, it is also possible to use superatmospheric pressure. The pressure is generally from 1 bar abs. to 10 bar abs.
The metathesis reaction is generally carried out in a fixed-bed reactor, for example in a vertically positioned tubular reactor charged with supported catalyst, and the solution of the starting materials flows in a vertical direction through the reactor. The flow rate here is set in such a way as to give residence times of from 10 to 600 seconds, preferably from 10 to 200 seconds. The reaction mixture leaving the reactor is passed to distillation equipment and separated into its components. The target product is produced as a relatively high-boiling fraction. For practical purposes continuous operation is mostly maintained, with solvent and also, if desired, unconverted starting material, circulated and returned r _ .__..__.__ _ 7 _ into the reactor after supplementation with new starting material. In the case of continuous operation, the evaporation/condensation of the solvent mixture may be achieved in a conventional manner (e. g. evaporators operated using steam and condensers operated using coolants). However, it is advantageous to use lower-energy processes, such as vapor compression, since this significantly reduces energy costs and allows the process to be carried out more cost-effectively.
The Examples below serve to describe the invention in greater detail:
Example 1 (Comparative Example):
Preparation of the comparative catalyst ( y-A1203 / Re20~ / Sn ( CH3 ) a ) NH4Re04 ( 5 . 5~ by weight , based on A1203 ) was dissolved in a dioxane/water mixture (80/20 v/v), and the y-A1z03 added to this as extrudates of length from 3 to 8 mm and diameter from 1.5 to 1.8 mm and BET surface area of 190 mz/g. The mixture was then heated to boiling. After an impregnation time of about 10 hours, the liquid phase was decanted and the catalyst pre-dried at 120°C. Activation was by treatment with air for 2 hours at from 500 to 600°C. The temperature was then held while the air was replaced by nitrogen. After a further 2 hours, the material was cooled to room temperature, taking care that no oxygen reached the catalyst. The content of Re20~ was 3.7~ by weight. The supported catalyst was then treated with a pentane solution of Sn(CH3)4, with impregnation taking place directly in the metathesis reactor. The content of Sn(CH3)4 was 2.5~ by weight. The data in ~ by weight are based in each case on aluminum oxide.
Example 2 r I
_ .8 _ Preparation of a catalyst comprising boron oxide ( y-A1203 / Re20~ / Bz03 / Sn ( CH3 ) a ) Boric acid (11.7 by weight, based on A1z03) was dissolved in water. NH4Re04 (5.5~ by weight, based on A1203) was then dissolved in this solution. Dioxane was then added to this solution until the dioxane/water ratio was 85/15 v/v. The A1203 extrudates as in Example 1 were then added, and the impregnation, calcination and Sn(CH3)4 treatment were carried out as in Example 1.
The content of Re20~ was 3.7~~by weight, the boron oxide content was 1.8~ by weight, and the Sn(CH3)4 content was 2.5~ by weight. The data in ~ by weight are based in each case on aluminum oxide.
Example 3 (Comparative Example):
Metathesis of a cyclopolyoctenylene mixture with the boron-oxide-free catalyst from Example 2 at 60°C
A vertically arranged reactor which could be heated (length 500 mm, internal diameter 26.5 mm) was charged with 200 g of catalyst from Example 1. The reactor was then heated to 60°C, and a 0.048 molar solution (concentration data based on the monoolefin unit cyclooctene) of a cyclopolyoctenylene mixture in pentane was passed through the catalyst bed. The pressure in the reactor was set to 6 bar abs. to prevent boiling of the pentane. The make up of the cyclopolyoctenylene mixture is given in Table 1:
Table 1:
Degree of polymerization Proportion (g by weight) 3 42.5 4 23.8 5 13.3 6 7.9 7 and above 10.1 ~___. _.. _._ _ The average residence time of the mixture in the reactor was 80 seconds. The reaction mixture leaving the reactor was fed to distillation equipment, where the n-pentane was distilled off and refed to the reactor after charging with fresh cyclopolyoctenylene mixture. Table 2 gives the average concentrations of 1,9-cyclohexadecadiene (CHDD concentrations) in the reaction mixture as a function of the duration of the experiment. Samples were taken directly downstream of the reactor.
Table 2:
Duration of experiment (h) CHDD content (g/1) 1 1.1 60 1.0 110 0.94 160 0.86 230 0.69 290 0.59 330 0.54 360 0.46 Example 4:
Metathesis of a cyclopolyoctenylene mixture with the catalyst from Example 2 comprising boron oxide, at 60°C
The procedure was as in Example 3 except that the catalyst prepared in Example 2 was used.
Table 3 gives the CHDD concentrations measured as a function of the duration of the experiment.
Table 3:
Duration of experiment (h) CHDD content (g/1) 1 1.2 110 1.0 300 0.85 400 0.80 500 0.76 ...._...~___...._....-..t.._ .~.._.. -.._-. _....
690 0.70 850 0.67 910 0.64 Example 5:
Metathesis of a cyclopolyoctenylene mixture with a regenerated catalyst comprising boron oxide and tin oxide, at 60°C
The catalyst used in Example 4 was removed from the reactor and washed with toluene. The catalyst was then dried at 100°C and calcined for 2 hours in air and for a further 2 hours in nitrogen, in each case at from 500 to 600°C, and then cooled to room temperature. The content of rhenium oxide and of boron oxide remained the same. The tetramethyltin had been converted into tin oxide. The Sn02 content was 0.53 by weight, based on aluminum oxide.
The catalyst regenerated in this way was then treated with a tetramethyltin-pentane solution as in Example 3 (2.5$ by weight of Sn(CH3)9) and used for the metathesis of a cyclooctenylene mixture as in Example 3.
Table 4 gives the CHDD concentrations as a function of the duration of the experiment.
Table 4:
Duration of experiment (h) CHDD content (g/1) 1 1.3 60 1.2 200 1.1 300 1.1 450 1.1 600 1.1 700 1.1 850 1.1 970 1.1 1150 1.0 _.. . ..
The results from the metathesis reactions as in Comparative Example 3 (Table 2) and as in the inventive Examples 4 (Table 3) and 5 (Table 4) are given diagrammatically in Figure 1. It can be seen clearly that, compared with conventional metathesis catalysts (Example 3: A1z03/Re20~/Sn(CH3)4) boron oxide doping (Example 4) gives significantly higher operating times, and these can be increased still further by means of Sn02 doping (Example 5).
Claims (5)
1. A supported catalyst for use in preparing cycloalkadienes in a metathesis reaction, comprising a) .gamma.-A12O3 as support, b) from 2 to 20% by weight of Re2O7, c) from Ø5 to 5% by weight of B2O3, and d) from 1 to 20% by weight of SnR4 or SnO2 or of a mixture of SnR4 and SnO2, where R is an alkyl or aryl radical and the data in % by weight are in each case based on .gamma.-Al2O3.
2. A supported catalyst as claimed in claim 1, wherein from 1 to 10% by weight, based on the aluminum oxide content, of SnO2, if desired in a mixture with SnR4 compounds, are present, in which R are identical or different substituents selected from the class consisting of C1-C6-alkyl. and phenyl radicals.
3. A supported catalyst as claimed in claim 1, wherein from 1 to 10% by weight, based on the aluminum oxide content, of a mixture of SnO2 and SnR4 compound are present.
4. A process for preparing cycloalkadienes in the liquid phase by a metathesis reaction of cycloalkenes, cyclopolyenes, linear polyenes, and also mixtures of these, at a reaction temperature of from 0 to 100°C in the presence of a supported catalyst as claimed in claims 1 to 3.
5. The process as claimed in claim 4, wherein the reaction temperature is from 50 to 100°C and the pressure is from 1 bar abs. to 10 bar abs.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19727256A DE19727256A1 (en) | 1997-06-26 | 1997-06-26 | A supported catalyst for use in the production of cycloalkadienes in a metathesis reaction |
| DE19727256.8 | 1997-06-26 | ||
| PCT/EP1998/003689 WO1999000189A1 (en) | 1997-06-26 | 1998-06-18 | Supported catalyst used in the production of cycloalkadienes in a metathesis reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2292584A1 true CA2292584A1 (en) | 1999-01-07 |
Family
ID=7833771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002292584A Abandoned CA2292584A1 (en) | 1997-06-26 | 1998-06-18 | Supported catalyst used in the production of cycloalkadienes in a metathesis reaction |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0991467B1 (en) |
| JP (1) | JP2000513271A (en) |
| CA (1) | CA2292584A1 (en) |
| DE (2) | DE19727256A1 (en) |
| WO (1) | WO1999000189A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3041812A4 (en) * | 2013-09-04 | 2017-08-16 | California Institute of Technology | Functionalized linear and cyclic polyolefins |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10142033A1 (en) * | 2001-08-28 | 2003-03-20 | Haarmann & Reimer Gmbh | metathesis |
| DE10142032A1 (en) * | 2001-08-28 | 2003-03-20 | Haarmann & Reimer Gmbh | Process for the preparation of cycloalkadienes |
| DE10142035A1 (en) * | 2001-08-28 | 2003-03-20 | Haarmann & Reimer Gmbh | Modified supported metathesis catalysts |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1377161A (en) * | 1972-09-08 | 1974-12-11 | British Petroleum Co | Disproportionation catalyst and process |
| CA994815A (en) * | 1973-03-01 | 1976-08-10 | Takasago Perfumery Co. | Process for producing cycloalkenes |
| DE4006540A1 (en) * | 1990-03-02 | 1991-09-05 | Huels Chemische Werke Ag | CATALYSTS FOR THE METATHESIS OF OLEFINS AND FUNCTIONALIZED OLEFINS |
| US5055628A (en) * | 1990-09-11 | 1991-10-08 | Ethyl Corporation | Preparation of alpha-olefin by ethenolysis |
| JPH08176022A (en) * | 1994-12-19 | 1996-07-09 | Sumitomo Chem Co Ltd | Production of 1,6-hepatdiene or 1,6-octadiene |
-
1997
- 1997-06-26 DE DE19727256A patent/DE19727256A1/en not_active Withdrawn
-
1998
- 1998-06-18 JP JP11505257A patent/JP2000513271A/en active Pending
- 1998-06-18 WO PCT/EP1998/003689 patent/WO1999000189A1/en active IP Right Grant
- 1998-06-18 DE DE59800673T patent/DE59800673D1/en not_active Expired - Fee Related
- 1998-06-18 CA CA002292584A patent/CA2292584A1/en not_active Abandoned
- 1998-06-18 EP EP98937499A patent/EP0991467B1/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3041812A4 (en) * | 2013-09-04 | 2017-08-16 | California Institute of Technology | Functionalized linear and cyclic polyolefins |
| US9890239B2 (en) | 2013-09-04 | 2018-02-13 | California Institute Of Technology | Functionalized linear and cyclic polyolefins |
| US10619003B2 (en) | 2013-09-04 | 2020-04-14 | California Institute Of Technology | Functionalized linear and cyclic polyolefins |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1999000189A1 (en) | 1999-01-07 |
| DE19727256A1 (en) | 1999-01-07 |
| JP2000513271A (en) | 2000-10-10 |
| DE59800673D1 (en) | 2001-06-07 |
| EP0991467B1 (en) | 2001-05-02 |
| EP0991467A1 (en) | 2000-04-12 |
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