Metathesis process

Abstract

A process of metathesizing a feedstock in the presence of a metathesis catalyst and at least one catalyst enhancer. The catalyst enhancer can be selected from a sacrificial catalyst or a non-catalyst enhancer. The process exhibits improved reaction times and/or the metathesis catalyst can be used at very low concentrations.

Claims

1. A process of metathesising a feedstock, wherein the feedstock comprises unsaturated fatty acids and/or esters of unsaturated fatty acids, in the presence of a metathesis catalyst and at least one catalyst enhancer compound in a reaction mixture, wherein the at least one catalyst enhancer is selected from the group consisting of a sacrificial catalyst and a non-catalyst enhancer, wherein the sacrificial catalyst is selected from the group consisting of dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium(II), dichloro-(3-phenyl-1H-inden-1-ylidene)bis(isobutylphobane)ruthenium(II), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(pyridyl)ruthenium(II), [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitro-phenolyl]chloro-[3-phenyl-indenylidene]ruthenium(II), and [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(2-methylphenyl)imino]methyl]-phenolyl]chloro-(3-phenyl-indenylidene)ruthenium(II), wherein the non-catalyst enhancer is selected from the group consisting of a Lewis acid and a titanium based compound, wherein the process is carried out without a solvent or in a solvent consisting of hydrocarbons and/or alcohols, wherein the metathesis catalyst efficiency is less than 100.

2. The process according to claim 1 wherein at least 40 wt. % of the feedstock is metathesized.

3. The process according to claim 1 wherein the process reaches equilibrium in less than 20 minutes.

4. The process according to claim 1 wherein the metathesis catalyst is present in an amount less than 100 ppm with respect to the reaction mixture.

5. The process according to claim 4 wherein the metathesis catalyst is present in an amount less than 10 ppm with respect to the reaction mixture.

6. The process according to claim 1 wherein the metathesis catalyst efficiency is less than 10.

7. The process according to claim 1 wherein the metathesis catalyst retains over 75% of its activity after 30 minutes.

8. The process according to claim 1 wherein no chemical treatment of the feedstock or starting material to remove catalyst poisons is performed.

9. The process according to claim 1 wherein the sacrificial catalyst is a sacrificial metathesis catalyst different from the metathesis catalyst.

10. The process according to claim 1 wherein the sacrificial catalyst is present in an amount ranging from 1 ppm to 100 ppm with respect to the reaction mixture.

11. The process according to claim 1 wherein the non-catalyst enhancer is a Lewis acid.

12. The process according to claim 1 wherein the non-catalyst enhancer is a titanium based compound.

13. The process according to claim 1 wherein the non-catalyst enhancer is selected from the group consisting of titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) propoxide, titanium (IV) isopropoxide, titanium (IV) butoxide, titanium (IV) tert-butoxide, titanium (IV) 2-ethylhexoxide, titanium (IV) 2-ethyl-1,3-hexanediolate, titanium (IV) tetrachloride, titanium (IV) tetrabromide, titanium (IV) tetrafluoride, titanium (IV) tetraiodide, and mixtures thereof.

14. The process according to claim 1 wherein the non-catalyst enhancer is present in an amount ranging from 10 ppm to 1,000 ppm with respect to the reaction mixture.

15. A process of metathesising a feedstock, wherein the feedstock comprises unsaturated fatty acids and/or esters of unsaturated fatty acids, in the presence of a metathesis catalyst and at least one catalyst enhancer compound in a reaction mixture, wherein the at least one catalyst enhancer is selected from the group consisting of a sacrificial catalyst and a non-catalyst enhancer, wherein the sacrificial catalyst is selected from the group consisting of dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium(II), dichloro-(3-phenyl-1H-inden-1-ylidene)bis(isobutylphobane)ruthenium(II), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(pyridyl)ruthenium(II), [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitro-phenolyl]chloro-[3-phenyl-indenylidene]ruthenium(II), and [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(2-methylphenyl)imino]methyl]-phenolyl]chloro-(3-phenyl-indenylidene)ruthenium(II), wherein the non-catalyst enhancer is selected from the group consisting of copper iodide, sodium iodide, tetrabutylgermanium, tetraethylsilicon, tin oxide, tin octoate, tin oxalate, dibutyltin dilaurate, tin(IV) chloridetetrabutyl orthotitanate, palladium acetate, tris(dibenzylideneacetone)palladium, tetrakis(triphenylphosphine)palladium, bis(diphenylferrocenyl)palladium dichloride, nickel chloride, bis(cyclooctadiene)nickel, nickelocene iron chloride, iron bromide, ferrocene, silver chloride, silver iodide, silver oxide, iodine, silver trifluoromethanesulfonate, sodium borohydride, boric acid, zinc ethylhexanoate, zircon (IV) oxide chloride octahydrate, acetic acid, butylated hydroxytoluene (BHT), quinones, activated charcoal, alumina, bleaching earth, titanium compounds having the general formula Ti.[Q].sub.4 wherein each Q independently represents hydrogen, a C.sub.1 to C.sub.10 alkoxy group, a C.sub.4 to C.sub.8 aryl group, a C.sub.12 to C.sub.18 fatty alcohol, or a C.sub.6 to C.sub.18 fatty acid, wherein the non-catalyst enhancer is present in an amount ranging from 10 ppm to 1,000 ppm with respect to the reaction mixture.

16. The process according to claim 15 wherein the metathesis catalyst is present in an amount less than 100 ppm with respect to the reaction mixture.

17. The process according to claim 15 wherein the metathesis catalyst efficiency is less than 100.

18. The process according to claim 15 wherein no chemical treatment of the feedstock or starting material to remove catalyst poisons is performed.

19. The process according to claim 15 wherein the sacrificial catalyst is present in an amount ranging from 1 ppm to 100 ppm with respect to the reaction mixture.

20. The process according to claim 15 wherein the non-catalyst enhancer is a titanium compound having the general formula Ti.[Q].sub.4 wherein each Q independently represents hydrogen, a C.sub.1 to C.sub.10 alkoxy group, a C.sub.4 to C.sub.8 aryl group, a C.sub.12 to C.sub.18 fatty alcohol, or a C.sub.6 to C.sub.18 fatty acid.

21. The process according to claim 15 wherein the non-catalyst enhancer is selected from the group consisting of titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) propoxide, titanium (IV) isopropoxide, titanium (IV) butoxide, titanium (IV) tert-butoxide, titanium (IV) 2-ethylhexoxide, titanium (IV) 2-ethyl-1,3-hexanediolate, and mixtures thereof.

22. A process of metathesising a feedstock, wherein the feedstock comprises unsaturated fatty acids and/or esters of unsaturated fatty acids, in the presence of a metathesis catalyst and at least one catalyst enhancer compound in a reaction mixture, wherein the at least one catalyst enhancer is selected from the group consisting of a sacrificial catalyst and a non-catalyst enhancer, wherein the sacrificial catalyst is selected from the group consisting of dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium(II), dichloro-(3-phenyl-1H-inden-1-ylidene)bis(isobutylphobane)ruthenium(II), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(pyridyl)ruthenium(II), [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitro-phenolyl]chloro-[3-phenyl-indenylidene]ruthenium(II), and [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(2-methylphenyl)imino]methyl]-phenolyl]chloro-(3-phenyl-indenylidene)ruthenium(II), wherein the non-catalyst enhancer is selected from the group consisting of a Lewis acid and a titanium based compound, wherein the process is carried out without a solvent or in a solvent consisting of hydrocarbons and/or alcohols, wherein the metathesis catalyst retains over 75% of its activity after 30 minutes.

23. A process of metathesising a feedstock, wherein the feedstock comprises unsaturated fatty acids and/or esters of unsaturated fatty acids, in the presence of a metathesis catalyst and at least one catalyst enhancer compound in a reaction mixture, wherein the at least one catalyst enhancer is selected from the group consisting of a sacrificial catalyst and a non-catalyst enhancer, wherein the sacrificial catalyst is selected from the group consisting of dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium(II), dichloro-(3-phenyl-1H-inden-1-ylidene)bis(isobutylphobane)ruthenium(II), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(pyridyl)ruthenium(II), [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitro-phenolyl]chloro-[3-phenyl-indenylidene]ruthenium(II), and [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(2-methylphenyl)imino]methyl]-phenolyl]chloro-(3-phenyl-indenylidene)ruthenium(II), wherein the non-catalyst enhancer is selected from the group consisting of titanium compounds having the general formula Ti.[Q].sub.4 wherein each Q independently represents hydrogen, a C.sub.1 to C.sub.10 alkoxy group, a C.sub.4 to C.sub.8 aryl group, a C.sub.12 to C.sub.18 fatty alcohol, or a C.sub.6 to C.sub.18 fatty acid.

Description

EXAMPLE 1

(1) A number of experiments were conducted using non-catalyst enhancer compounds (Ti(O.sup.iPr).sub.4) and BF.sub.3. The starting material was also treated with an antioxidant (TBHQ). The results are shown in Table 1.

(2) TABLE-US-00001 TABLE 1 A B C Methyl Oleate (g) 50 50 50 Metathesis Catalyst 5 3 5 (ppm) Ti(O.sup.iPr).sub.4 (ppm) 200 200 0 BF.sub.3 (ppm) 0 0 200 Conversion 50% 46% 41%

(3) Metathesis catalyst used was ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyliden]dichloro[(2-isopropoxy)(5-isobutoxyacetamido)benzyliden]]ruthenium(II)).

(4) Improvements were seen on addition of non-catalyst enhancer compound. In example A addition of 200 ppm gave 50% conversion whilst using only 5 ppm of metathesis catalyst. Example B used lower concentration of metathesis catalyst (3 ppm) which resulted in 46% conversion. Example C shows use of BF.sub.3 as another non-catalyst enhancer compound with similar results.

EXAMPLE 2

(5) Feedstock used was methyl oleate which was stabilised by 100 ppm of tert-butylhydroquinone (97%)/TBHQ and transferred to cold storage (4 C.) for 60 days without further pre-treatment.

(6) The metathesis catalyst was added as a stock solution in tetrahydrofuran to reduce weighing inaccuracies, since only milligram quantities are needed for these experiments. The amount added is given in ppm (mol/mol).

(7) Activity towards metathesis of stabilised feedstock with catalyst enhancer addition was determined using the following conditions:

(8) 50 g stabilised methyl oleate (MeOI) was heated to 100 C. while bubbling through N.sub.2. Once the reaction temperature had been reached, the catalyst enhancer was added and stirred for 10 minutes; followed by the addition of [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro[5-(isobutoxycarbonylamido)-2-isopropoxybenzylidene]ruthenium(II) metathesis catalyst solution.

(9) The progression of the reaction was followed over time. A small sample was removed from the reaction flask using a pipette, and any residual catalyst activity was quenched by addition of a few drops of ethyl vinyl ether. The resulting samples were directly analysed by GC (FID detection).

(10) The efficacy of catalyst enhancers in lowering metathesis catalyst loadings are given in Tables 2 to 6.

(11) TABLE-US-00002 TABLE 2 Titanium Isopropoxide Addition A C D E MeOl (g) 50 50 50 50 Metathesis 5 5 5 3 Catalyst (ppm) Ti(OiPr).sub.4 (ppm) 100 200 200 Conversion 2% 21% 50% 46%

(12) From results in Table 1 it can be seen that the blank sample A with 5 ppm catalyst and no addition of Ti(OiPr).sub.4 reached only 2% conversion. Improvements were seen by the addition of 100 ppm Ti(OiPr).sub.4 converted to 21% (C) and 200 ppm Ti(OiPr).sub.4 gave equilibrium conversion (D). This result is similar to experiment E when 3 ppm catalyst and 200 ppm Ti(OiPr).sub.4, and 46% conversion was reached.

(13) TABLE-US-00003 TABLE 3 Boron Trifuoride Addition A B MeOl (g) 50 50 Metathesis 5 5 Catalyst (ppm) BF3(ppm) 200 Conversion 0% 41%

(14) As shown in Table 3, experiment A with no addition of BF.sub.3 gave no conversion at all. Upon addition of 200 ppm of BF.sub.3, conversion went up to 41% (B).

(15) TABLE-US-00004 TABLE 4 Titanium (IV) Ethoxide Addition A B MeOl (g) 50 50 50 Metathesis 5 5 3 Catalyst (ppm) TiEthoxide (ppm) 200 200 Conversion 2% 49% 48%

(16) As shown in Table 4, at 200 ppm levels of titanium ethoxide, both 3 ppm (B) and 5 ppm (A) of metathesis catalyst loading were effective.

(17) TABLE-US-00005 TABLE 5 Titanium (IV) 2-Ethylhexoxide Addition A B MeOl (g) 50 50 50 Metathesis Catalyst 5 5 3 (ppm) TiEthylhexoxide 200 200 (ppm) Conversion 2% 49% 44%

(18) Table 5 shows that the addition of 200 ppm titanium (IV) 2-ethylhexoxide with 5 ppm and 3 ppm metathesis catalyst reached 49% (A) and 44% (B) conversion.

(19) TABLE-US-00006 TABLE 6 Sacrificial Catalyst Addition A B C D MeOl (g) 50 50 50 50 Metathesis 5 5 5 3 Catalyst (ppm) Sacrificial 20 40 40 Catalyst (ppm) Conversion 0% 47% 50% 30%

(20) Sacrificial catalyst used was dichloro(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium(II).

(21) As shown in Table 6, experiment B with 5 ppm metathesis catalyst and 20 ppm of sacrificial catalyst reached 47% conversion; experiment C with 5 ppm metathesis catalyst and 40 ppm sacrificial catalyst also reached full conversion. The combination of 3 ppm metathesis catalyst and 40 ppm sacrificial catalyst reached 30% conversion (D), similarly to other experiments at 3 ppm metathesis catalyst levels. Previous screening experiments using only sacrificial catalyst showed it to be very slow, needing several hours to reach noticeable conversions. From this it was concluded that the metathesis reaction is not being catalyzed by the sacrificial catalyst, but is exclusively due to the presence of the metathesis catalyst.

(22) It is to be understood that the invention is not to be limited to the details of the above embodiments, which are described by way of example only. Many variations are possible.