| PATENT ASSIGNEE'S COUNTRY | France |
| UPDATE | 08.00 |
| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | 15.08.00 |
| PATENT TITLE |
Catalytic composition and a process for converting ethylene to light alpha olefins |
| PATENT ABSTRACT |
A catalytic composition for the production of light alpha olefins by ethylene oligomerisation is produced by mixing a zirconium compound with an organic compound selected from the group formed by acetals and ketals, with an aluminium hydrocarbyl compound selected from the group formed by chlorine-containing or bromine-containing aluminium hydrocarbyl compounds and with an aluminium hydrocarbyl compound selected from tris-(hydrocarbyl)-aluminium compounds. Addition of a tris-(hydrocarbyl)-aluminium compound greatly increases the activity. A process for producing light alpha olefins by ethylene oligomerisation is also claimed. |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | 25.02.98 |
| PATENT FOREIGN APPLICATION PRIORITY DATA | This data is not available for free |
| PATENT REFERENCES CITED | This data is not available for free |
| PATENT CLAIMS |
What is claimed is: 1. An improved catalytic composition, characterized in that said improved catalytic composition is obtained by mixing: at least one zirconium compound with formula ZrX.sub.x Y.sub.y O.sub.z, where X is a chlorine or bromine atom, Y is a radical selected from the group consisting of alkoxy RO.sup.-, amido R.sub.2 N.sup.-, and carboxylate RCOO.sup.- groups, where R is a hydrocarbyl radical containing 1 to 30 carbon atoms, x and y have whole number values of 0 to 4 and z is equal to 0 or 0.5, the sum x+y+2z being equal to 4; with at least one organic compound with formula (R.sub.1 ')(R.sub.2 ')C(OR.sub.1)(OR.sub.2) where R.sub.1 ' and R.sub.2 ' are constituted by a hydrogen atom or a hydrocarbyl radical containing 1 to 30 carbon atoms, R.sub.1 and R.sub.2 being hydrocarbyl radicals containing 1 to 30 carbon atoms; with at least one aluminium compound with formula AlR".sub.n X.sub.3-n where R" is a hydrocarbyl radical containing 1 to 6 carbon atoms, X is a chlorine or bromine atom, and n is a number in the range 1 to 2; and with at least one trishydrocarbyl aluminium compound with formula AlR'".sub.3 where R'" is a hydrocarbyl radical containing 1 to 6 carbon atoms. 2. An improved catalytic composition according to claim 1, further containing at least one solvent selected from the group consisting of aliphatic, cycloaliphatic and aromatic hydrocarbons, and high oligomers. 3. An improved catalytic composition according to claim 2, wherein the solvent is at least one aromatic hydrocarbon. 4. An improved catalytic composition according to claim 2, claim 1, wherein the solvent is ortho-xylene. 5. An improved catalytic composition according to claim 2, wherein the solvent is used during mixing of the compounds. 6. An improved catalytic composition according to claim 1, wherein the zirconium compound and the organic compound are mixed, the product obtained then being mixed with the aluminium compounds. 7. An improved catalytic composition according to claim 1, wherein the organic compound is selected from the group consisting of diethoxymethane, diisopropoxymethane, 1,1-diethoxyethane, 1,1-diisobutoxyethane, 1,1-dimethoxydecane, 2-nonyl-1,3-dioxolane, 2,2-dimethoxyoctane, 1,1-dimethoxycyclohexane, 2,2-dimethoxypropane, 2,2-dibutoxypropane, 2,2-dihexyloxypropane, 2,2-dioctoxypropane, and 2,2-di-(2-ethylhexyloxy)-propane. 8. An improved catalytic composition according to claim 1, wherein the zirconium compound is zirconium tetrachloride. 9. An improved catalytic composition according to claim 8, wherein the two aluminum Compounds are ethylaluminium sesquichloride and triethylaluminium. 10. An improved catalytic composition according to claim 9, wherein the molar ratio between the chlorine-containing or bromine-containing aluminium hydrocarbyl and the zirconium compound is in the range 1:1 to 100:1. 11. An improved catalytic composition according to claim 10, wherein the molar ratio between the tris-(hydrocarbyl)-aluminium compound and the zirconium compound is in the range 0.01:1 to 10:1. 12. An improved catalytic composition according to claim 11, wherein the molar ratio between the organic compound and the zirconium compound is in the range 0.1:1 to 5:1. 13. An improved catalytic composition according to claim 1, wherein the two aluminium compounds are ethylaluminium sesquichloride and triethylaluminium. 14. An improved catalytic composition according to claim 13, wherein the organic compound is 2,2-di-(2-ethylhexyloxy)-propane. 15. An improved catalytic composition according to claim 1, wherein the molar ratio between the organic compound and the zirconium compound is in the range 0.1:1 to 5:1. 16. An improved catalytic composition according to claim 1, wherein the molar ratio between the chlorine-containing or bromine-containing aluminium hydrocarbyl and the zirconium compound is in the range 1:1 to 100:1. 17. An improved catalytic composition according to claim 1, wherein the molar ratio between the tris-(hydrocarbyl)-aluminium compound and the zirconium compound is in the range 0.01:1 to 10:1. 18. An improved catalytic composition according to claim 1, wherein the catalyst components are mixed at a temperature which is in the range -10.degree. C. to 180.degree. C. 19. A composition according to claim 1, wherein said trishydrocarbyl aluminum compound is triethylaluminum. -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
The present invention relates to an improved catalytic composition used for the production of light alpha olefins by ethylene oligomerisation. The Ziegler type improved catalytic composition is produced by mixing a zirconium compound with an organic compound selected from the group formed by acetals and ketals, with an aluminium hydrocarbyl compound selected from the group formed by chlorine-containing or bromine-containing aluminium hydrocarbyl compounds and with an aluminium hydrocarbyl compound selected from tris-(hydrocarbyl)-aluminium compounds. The invention also relates to a process for producing light alpha olefins by oligomerisation of ethylene. BACKGROUND OF THE INVENTION A number of zirconium compounds have been used to oligomerise ethylene to alpha olefins, generally associated with various other ligands. Examples are the use of zirconium halides associated with esters, ketones, ethers, amines, nitrites, anhydrides, acid chlorides, amides or aldehydes, described in United States patent U.S. Pat. No. 4,855,525 and International patent application WO 91 02707, or the use of the same zirconium halides associated with ligands selected from the group formed by sulphur-containing, phosphorous-containing or nitrogen-containing compounds, described in European patents EP-A-0 241 596 and EP-A-0 328 728. The products obtained with the catalytic formulae given above are principally constituted by alpha olefins with a chain length of between C.sub.10 and C.sub.18. U.S. Pat. No. 5,345,023 describes a process for producing light alpha olefms, principally 1-butene, 1-hexene, 1-octene and 1-decene, by oligomerising ethylene, using a catalytic composition obtained by mixing a zirconium compound with an organic compound selected from the group formed by acetals and ketals and with a chlorine-containing or bromine-containing aluminium hydrocarbyl compound. The teaching of this patent is included in the present application. SUMMARY OF THE INVENTION We have now discovered that the addition of a tris-(hydrocarbyl)-aluminium to the above catalytic composition can greatly increase the activity. More precisely, the improved catalytic composition is obtained by mixing: at least one zirconium compound with formula ZrX.sub.x Y.sub.y O.sub.z, where X is a chlorine or bromine atom, Y is a radical selected from the group formed by alkoxy RO.sup.-, amido R.sub.2 N.sup.-, or carboxylate RCOO.sup.- groups, where R is a hydrocarbyl radical containing 1 to 30 carbon atoms, x and y have whole number values of 0 to 4 and z is equal to 0 or 0.5, the sum x+y+2z being equal to 4; with at least one organic compound with formula (R,')(R.sub.2 ')C(OR.sub.1)(OR.sub.2) where R.sub.1 ' and R.sub.2 ' are constituted by a hydrogen atom or a hydrocarbyl radical containing 1 to 30 carbon atoms, R.sub.1 and R.sub.2 being hydrocarbyl radicals containing 1 to 30 carbon atoms; with at least one aluminium compound with formula AlR".sub.n X.sub.3-n where R" is a hydrocarbyl radical containing 1 to 6 carbon atoms, X is a chlorine or bromine atom, and n is a number in the range 1 to 2; and with at least one aluminium compound with formula AlR'".sub.3 where R'" is a hydrocarbyl radical containing 1 to 6 carbon atoms. Preferably, the composition also comprises at least one solvent, advantageously selected from the group formed by aliphatic, cycloaliphatic and aromatic hydrocarbons, and compounds corresponding to by-products of oligomerisation such as high oligomers. The solvent is preferably selected from aromatic hydrocarbons; ortho-xylene is particularly suitable. Reference should be made to U.S. Pat. No. 5,345,023 for the preparation of the catalytic composition. Examples of zirconium compounds are zirconium halides such as zirconium tetrachloride ZrC.sub.4, zirconium tetrabromide ZrBr.sub.4, alcoholates such as zirconium tetrapropylate Zr(OC.sub.3 H.sub.7).sub.4, zirconium tetrabutylate Zr(OC.sub.4 H.sub.9).sub.4, carboxylates such as zirconium 2-tetraethyl hexanoate Zr(OCOC.sub.7 H.sub.15).sub.4 or oxocarboxylates such as dizirconium 2-oxohexaethyl hexanoate [Zr(OCOC.sub.7 H.sub.15).sub.3 ].sub.2 O. The organic compounds selected from the group formed by acetals and ketals used in the invention result from condensing an aldehyde or ketone with a mono-alcohol or a poly-alcohol, for example a glycol. They have the following general formula: (R.sub.1 ')(R.sub.2 ')C(OR.sub.1)(OR.sub.2) where R.sub.1 ' and R.sub.2 ' are constituted by a hydrogen atom or a hydrocarbyl radical containing 1 to 30 carbon atoms and R.sub.1 and R.sub.2 are hydrocarbyl groups containing 1 to 30 carbon atoms. The two radicals R.sub.1 ' and R.sub.2 ' and the two radicals R.sub.1 and R.sub.2 may be identical or different. They can also form a ring. Examples are diethoxymethane, diisopropoxymethane, 1,1-diethoxyethane, 1,1-diisobutoxyethane, 1,1-dimethoxydecane, 2-nonyl-1,3-dioxolane, 2,2-dimethoxyoctane, 1,1-dimethoxycyclohexane, and preferably 2,2-dimethoxypropane, 2,2-dibutoxypropane, 2,2-dihexyloxypropane, 2,2-dioctoxypropane, and 2,2-di-(2-ethylhexyloxy)-propane. Examples of the aluminium compounds used in the invention represented by general formula AlR".sub.n X.sub.3-n are chlorodiethylaluminium, dichloroethylaluminium, and preferably ethylaluminium sesquichloride, or mixtures thereof. Examples of the aluminium compounds used in the invention represented by general formula AlR'".sub.3 are trimethylaluminium, tributylaluminium, trihexylaluminium, and preferably triethylaluminium. Particularly advantageously, the catalyst so resulting from the interaction of a mixture of at least one zirconium compound, such as zirconium tetrachloride, and at least one organic compound selected from the group formed by acetals and ketals, resulting from condensing an aldehyde or a ketone with a mono-alcohol or a poly-alcohol, such as 2,2-di-(2-ethylhexyloxy)-propane, with at least one chlorine-containing or bromine-containing aluminium hydrocarbyl compound, such as ethylaluminium sesquichloride, and with at least one tris-(hydrocarbyl)-aluminium, such as triethylaluminium. The catalyst components can be brought into contact in any order in a solvent selected from the group formed by aliphatic hydrocarbons and cycloaliphatic hydrocarbons such as hexane, cyclohexane or heptane, aromatic hydrocarbons such as toluene or xylenes, and by-products of oligomerisation such as high oligomers. Advantageously, aromatic hydrocarbons are used, preferably ortho-xylene. The zirconium compound is preferably first mixed with the acetal or ketal then the aluminium compounds are added to the mixture, in any order or themselves as a mixture. The molar ratio between the acetal or ketal and the zirconium compound is 0.1:1 to 5:1, preferably 0.5:1 to 2:1. The molar ratio between the chlorine-containing or bromine-containing aluminium hydrocarbyl and the zirconium compound is 1:1 to 100:1, preferably 5:1 to 50:1. The molar ratio between the tris-(hydrocarbyl)-aluminium and the zirconium compound is 0.01:1 to 10:1, preferably 0.1:1 to 2:1. The concentration of zirconium in the catalytic solution so prepared is advantageously in the range 10.sup.-4 to 1 mole per litre, preferably 10.sup.-3 to 0.5 moles per litre. The temperature at which the four components are mixed is normally in the range -10.degree. C. to 180.degree. C., preferably in the range 0.degree. C. to +150.degree. C., for example a temperature close to ambient temperature (15.degree. C. to 30.degree. C.). The mixture can be formed in an atmosphere of ethylene or an inert gas. The composition of the invention can be used in processes for converting ethylene to light alpha olefins. The solution or catalytic composition produced as above can be used as it is to carry out the oligomerisation reaction, or it can be diluted by adding a solvent selected from the group formed by aliphatic, cycloaliphatic and aromatic hydrocarbons, and by-products of oligomerisation such as high oligomers. Aromatic hydrocarbons are preferably used, preferably ortho-xylene. The process is carried out under oligomerisation conditions, at pressures of 0.5 to 15 MPa, and at temperatures of 20-180.degree. C. In a process for carrying out batchwise catalytic oligomerisation, the required volume of the catalytic solution prepared as described above is introduced into a reactor provided with the usual stirring and cooling systems, then pressurised with ethylene to a pressure which is generally in the range 0.5 to 15 MPa, preferably in the range 1 to 10 MPa, and the temperature is generally maintained between 20.degree. C. and 180.degree. C., preferably between 40.degree. C. and 150.degree. C. The oligomerisation reactor is supplied with ethylene at a constant pressure until the total volume of liquid produced represents between 2 and 50 times the volume of the catalytic solution originally introduced. The catalyst is then destroyed, for example by injecting an amine into the reactor, then the reaction products and any solvent are extracted and separated from any solvent. The operation of a continuous process is preferably as follows: the catalytic solution is injected into the reactor at the same time as the ethylene, the reactor being stirred by conventional mechanical means or by external re-circulation. The catalyst components can also be injected separately into the reaction medium, for example the product of the interaction of the zirconium compound with the acetal or ketal, and the mixture of the two aluminium compounds. The temperature is kept between 20.degree. C. and 180.degree. C., preferably between 40.degree. C. and 150.degree. C., and the pressure is generally adjusted to between 0.5 and 15 MPa, preferably between 1 and 10 MPa. The liquid level in the reactor is kept constant. Ethylene is introduced via an inlet valve, which is pressure controlled, which keeps it constant. The reaction mixture is extracted from the reaction zone using a valve controlled by the liquid level. This mixture is sent to a catalyst destruction zone which comprises injection of an amine, for example, then vaporisation of the effluent treated with the amine, either by raising the temperature, or by reducing the pressure, or by simultaneous action on the temperature and the pressure, to recover the products in the vaporised fraction. The products and any solvent are then separated in a system of distillation columns. The unreacted ethylene can be returned to the reactor. The catalyst residues included in a heavy fraction can be incinerated. |
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