Catalyst composition for selective hydrogenation with improved characteristics
This invention relates to heterogeneous catalysts useful for selective hydrogenation of unsaturated hydrocarbons, comprising palladium and optionally a promoter, supported on a substrate, having an uncoated BET surface area of ≤9 m 2 /g, the surface being coated with an ionic liquid. Also described are methods of making the catalysts and methods of selective hydrogenation of acetylene and/or dienes in front-end mixed olefin feed streams.
1. A method of selective hydrogenation of acetylene in front-end mixed olefin feed streams, comprising catalyzing said hydrogenation with a heterogeneous shell catalyst, the heterogeneous catalyst comprising:
(i) a porous solid substrate having an uncoated BET surface area of less than 9 m 2 /g and an internal pore volume of 0.007 to 0.04 ml/g;
(ii) the porous solid substrate having a metal or metal-alloy shell comprising palladium and optionally at least one promoter, the metal or metal-alloy shell having a thickness of 100 μm to 500 μm; and
(iii) the porous solid substrate also having a shell consisting of 0.1% to 5% by weight of the heterogeneous catalyst of one or more ionic liquids coated on a pore surface of the substrate having the internal pore volume in a quantity that is less than the internal pore volume, the ionic liquid shell having a thickness of 10 μm to 2000 μm, wherein a total quantity of the one or more ionic liquids used is between 0.01% to 5% by weight of the heterogeneous shell catalyst,
wherein the one or more ionic liquids consist of one or more compounds of the formula:
[A] n + [Y] n − ,
wherein:
n=1 or 2;
[A] n + comprises an imidazolium cation of the formula (III)
wherein R, R 1 , and R 2 are independently selected from the group consisting of hydrogen and linear or branched C 1 -C 12 -alkyl groups, or [A] n + is selected from the group consisting of 1-butyl-1-methylpyrrolidinium, 1-ethyl-3-methylpyridinium, ethyldimethyl-(2-methoxyethyl)-ammonium, tributylmethylammonium, tricyclohexyltetradecylphosphonium, and mixtures thereof; and
[Y] n − is selected from the group consisting of bis(trifluoromethylsufonyl)imide, dicyanamide, ethylsulfate, methylphosphonate, methylsulfate, octylsulfate, tetracyanoborate, tetrafluoroborate, tricyanomethane, triflate, tris(pentafluoroethyl)trifluorophosphate, and mixtures thereof.
2. The method of claim 1 , wherein the selective hydrogenation occurs in a gas phase.
3. The method of claim 1 , wherein the selective hydrogenation occurs in a liquid phase.
4. The method of claim 1 , wherein the BET surface area is ≤8 m 2 /g.
5. The method of claim 4 , wherein the BET surface area is ≤6 m 2 /g.
6. The method of claim 1 , wherein the palladium-supported heterogeneous catalyst further comprises a promoter selected from the group consisting of Ag, Au, Zn, Sn, Cd, Pb, Cu, Bi, K, Ga, and mixtures thereof.
7. The method of claim 6 , wherein the promoter comprises Ag.
8. The method of claim 6 , wherein the heterogeneous catalyst has a mass ratio of Pd:promoter of 1:5-3:1.
9. The method of claim 1 , wherein the heterogeneous catalyst has a Pd loading of 10 to 1000 ppm.
10. The method of claim 1 , wherein
[A] + is selected from the group consisting of 1-butyl-1-methylpyrrolidinium, 1-butyl-2,3-dimethylimidazolium, 1-butyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-methyl-3-octylimidazolium, ethyldimethyl-(2-methoxyethyl) ammonium, tributylmethylammonium, tricyclohexyltetradecylphosphonium, and mixtures thereof.
11. The method of claim 1 , wherein the ionic liquid consists of one or more selected from the group consisting of 1-butyl-3-methylimidazolium triflate, 1-ethyl-3-methylpyridinium ethylsulfate, 1-butyl-1-methylpyrrolidinium triflate, 1-butyl-2,3-dimethylimidazolium triflate, 1-butyl-3-methylimidazolium tricyanomethane, 1-butyl-3-methylimidazolium methylsulfate, 1-butyl-3-methylimidazolium octylsulfate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium ethylsulfate, 1-ethyl-3-methylimidazolium methylphosphonate, 1-ethyl-3-methylimidazolium triflate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsufonyl)imide, 1-butyl-1-methylpyrrolidinium tetracyanoborate, 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, 1-butyl-3-methylimidazolium bis(trifluoromethylsufonyl)imide, 1-ethyl-3-methylpyridinium bis(trifluoromethylsufonyl)imide, 1-ethyl-3-methylimidazolium tetracyanoborate, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, 1-methyl-3-octylimidazolium triflate, ethyldimethyl-(2-methoxyethyl) ammonium tris(pentafluoroethyl)trifluorophosphate, tributylmethylammonium dicyanamide, tricyclohexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate, 1-ethyl-3-methylimidazolium bis(trifluoromethylsufonyl)imide, and mixtures thereof.
12. The method of claim 1 , wherein the heterogeneous catalyst has an ionic liquid loading of 0.1% to 5% by weight.
13. The method of claim 12 , wherein the heterogeneous catalyst has an ionic liquid loading of 0.2% to 3% by weight.
14. The method of claim 13 , wherein the heterogeneous catalyst has an ionic liquid loading of 0.3% to 1.5% by weight.
15. The method of claim 1 , wherein the heterogeneous catalyst has a cleanup temperature of less than 80° C. and an operating window of greater than 25° C. when tested with a simulated de-ethanizer feed containing 0.35 mol % acetylene, 20 mol % hydrogen, 0.02 mol % CO, 45 mol % ethylene, and balance methane being passed over a 25 ml catalyst bed at 500 psig (35.5 bar) in total pressure and 7000 h −1 in Gas Hourly Space Velocity (GHSV), while the bed temperature is increased from about 35° C., the “clean up temperature” is defined as the temperature at which the outlet reaches <25 ppm acetylene, the runaway temperature is defined as the temperature at which the outlet ethane concentration is >2% and the operation window is defined as the difference between the runaway temperature and the clean up temperature.
16. The method of claim 1 , wherein the heterogeneous catalyst has the internal pore volume without the presence of the at least one ionic liquid in the range of 0.009 to 0.02 ml/g.
17. The method of claim 16 , wherein the internal pore volume of the heterogeneous catalyst without the presence of said at least one ionic liquid is within a range of 0.007 to 0.04 ml/g.
18. The method of claim 17 , wherein the internal pore volume of the heterogeneous catalyst without the presence of said at least one ionic liquid is within a range of 0.009 to 0.02 ml/g.
19. The method of claim 1 , wherein the heterogeneous catalyst has a selectivity of >25% at clean up temperature, when tested with a simulated de-ethanizer feed containing 0.35 mol % acetylene, 20 mol % hydrogen, 0.02 mol % CO, 45 mol % ethylene, and balance methane being passed over a 25 ml catalyst bed at 500 psig (35.5 bar) in total pressure and 7000 h −1 in Gas Hourly Space Velocity (GHSV), while the bed temperature is increased from about 35° C., the “clean up temperature” being defined as the temperature at which the outlet reaches <25 ppm acetylene.
20. The method of claim 1 , wherein the one or more ionic liquids coated on the pore surface have a volume smaller than the internal pore volume of the catalyst and is provided via use of a quantity of the one or more ionic liquids that is less than the internal pore volume.
21. The method of claim 1 , wherein the one or more ionic liquids are deposited such that a body of the heterogenous shell catalyst is externally dry.