Selective hydrogenation methods
The present disclosure relates to methods for selectively hydrogenating acetylene, to methods for starting up a selective hydrogenation reactor, and to hydrogenation catalysts useful in such methods. In one aspect, the disclosure provides a variety of methods for starting up reactors for use in methods for selectively hydrogenating acetylene using a catalyst composition comprises a porous support, palladium, and one or more ionic liquids.
1. A method of starting up a selective hydrogenation reactor, the selective hydrogenation reactor housing one or more catalyst beds each containing a catalyst suitable for selectively hydrogenating acetylene in a process gas comprising at least 10 mol. % ethylene, at least 1 ppm acetylene, calculated on a molar basis, and at least 5 mol. % hydrogen, the method comprising
providing the one or more catalyst beds at no more than a first temperature, the catalyst of the one or more catalyst beds comprising at least one ionic liquid and being in contact with a first gas, the first gas including less than 2% hydrogen, calculated on a molar basis, and being non-reactive in the presence of the catalyst at the first temperature;
in the presence of the first gas, heating the one or more catalyst beds to at least a second temperature, the second temperature being at least 20° C. greater than the first temperature, the first gas being non-reactive in the presence of the catalyst at the second temperature; and then
replacing the first gas in contact with the catalyst by introducing the process gas to the selective hydrogenation reactor to be in contact with the catalyst, while the one or more catalyst beds is at least at the second temperature; and
allowing the process gas to flow through the one or more catalyst beds until a concentration of acetylene at an outlet of the selective hydrogenation reactor is less than 1 ppm, calculated on a molar basis.
2. The method of claim 1 , wherein
the catalyst of the one or more catalyst beds has not been contacted in the selective hydrogenation reactor with carbon monoxide in an amount in excess of 100 ppm, calculated on a molar basis;
the process gas is provided from an effluent of a cracking process, from an overhead stream of a de-propanizer, from an overhead stream of a de-ethanizer, or from a refinery off-gas stream; and
no additional carbon monoxide is added to the provided process gas.
3. The method according to claim 1 , wherein
the first temperature is no more than 40° C.; and
the second temperature is within a range of 40° C. to 140° C.
4. The method according to claim 1 , wherein
the first temperature is in a range of 31−45° C.; and
the selective hydrogenation is conducted at the second temperature within a range of 40° C. to 140° C.
5. The method according to claim 1 , wherein the selective hydrogenation is conducted at a gas hourly space velocity in a range of 7,500 h −1 to 40,000 h −1 .
6. The method according to claim 1 , wherein
ethylene is present in the process gas in an amount of at least 20 mol. %;
acetylene is present in the process gas in an amount of at least 500 ppm, calculated on a molar basis; and
hydrogen is present in the process gas in an amount in a range of 5 mol. % to 35 mol. %.
7. The method according to claim 1 , wherein the process gas contains no more than 5 mol. % of carbon-containing components other than C 1 components, C 2 components and C 3 components.
8. The method according to claim 1 , wherein the catalyst comprises a porous support selected from alumina, silica, titania, and mixtures thereof, present in the catalyst composition in an amount within a range of 90 wt. % to 99.9 wt. %.
9. The method according to claim 1 , wherein the catalyst comprises palladium in an amount of at least 0.02 wt. %.
10. The method according claim 1 , wherein the catalyst comprises the at least one ionic liquid in a total amount up to 10 wt. %.
11. The method according to claim 1 , wherein the at least one ionic liquid is selected from 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(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidinium tetracyanoborate, 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium tricyanomethane, 1-ethyl-3-methylpyridinium bis(trifluoromethylsulfonyl)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, and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.
12. The method according to claim 1 , wherein the catalyst comprises:
a porous support, present in the catalyst in an amount within a range of 90 wt. % to 99.9 wt. %;
palladium, present in the catalyst in an amount within a range of 0.02 wt. % to 0.5 wt. %, calculated on an elemental mass basis; and
one or more ionic liquids, present in the catalyst in a combined amount up to 10 wt. %.
13. The method according to claim 1 , wherein
the process gas comprises 0 ppm to 190 ppm carbon monoxide, calculated on a molar basis; and
the selective hydrogenation is conducted at a gas hourly space velocity (GHSV) within a range of 2,000 h −1 to 40,000 h −1 .
14. The method according to claim 1 , wherein, before introducing the process gas, the catalyst of the one or more catalyst beds has not been contacted in the selective hydrogenation reactor with carbon monoxide in an amount in excess of 100 ppm, calculated on a molar basis.
15. A method of starting up a selective hydrogenation reactor, the selective hydrogenation reactor housing one or more catalyst beds each containing a catalyst suitable for selectively hydrogenating acetylene in a process gas comprising at least 10 mol. % ethylene, at least 1 ppm acetylene, calculated on a molar basis, and at least 5 mol. % hydrogen, the method comprising
providing the one or more catalyst beds at no more than a first temperature, the catalyst of the one or more catalyst beds comprising at least one ionic liquid and being in contact with the process gas;
in the presence of the process gas, heating the one or more catalyst beds to at least a second temperature, the second temperature being at least 20° C. greater than the first temperature, the heating of the one or more catalyst beds being performed at a rate in a range of 3-20° C./hour; and
allowing the process gas to flow through the one or more catalyst beds until
a concentration of acetylene at an outlet of the selective hydrogenation reactor is less than 1 ppm, calculated on a molar basis;
at least 90% of the acetylene present in the process gas is hydrogenated; and
no more than 1 mol. % of the total acetylene and ethylene present in the process gas is converted to ethane.
16. A method of starting up a selective hydrogenation reactor, the selective hydrogenation reactor housing one or more catalyst beds each containing a catalyst suitable for selectively hydrogenating acetylene in a process gas comprising at least 10 mol. % ethylene, at least 1 ppm acetylene, calculated on a molar basis, and at least 5 mol. % hydrogen, the method comprising:
providing the selective hydrogenation reactor with the one or more catalyst beds at a first temperature, the catalyst of the one or more catalyst beds comprising at least one ionic liquid and being in contact with a first gas at the first temperature, the first gas including less than 2% hydrogen, calculated on a molar basis, and being non-reactive in the presence of the catalyst at the first temperature, wherein the catalyst has not been contacted in the selective hydrogenation reactor with a carbon monoxide-containing gas having a carbon monoxide concentration in excess of 2000 ppm, calculated on a molar basis; and
introducing a flow of the process gas to the one or more catalyst beds, and refraining from adding carbon monoxide to the process gas.
17. The method of claim 16 , further comprising raising the temperature of the one or catalyst beds from the first temperature to at least a second temperature.
18. The method according to claim 16 , wherein, before introducing the process gas, the catalyst of the one or more catalyst beds has not been contacted in the selective hydrogenation reactor with carbon monoxide in an amount in excess of 100 ppm, calculated on a molar basis.
19. A method of starting up a selective hydrogenation reactor, the selective hydrogenation reactor housing one or more catalyst beds each containing a catalyst suitable for selectively hydrogenating acetylene in a process gas comprising at least 10 mol. % ethylene, at least 1 ppm acetylene, calculated on a molar basis, and at least 5 mol. % hydrogen, the method comprising
drying the one or more catalyst beds at a temperature of at least 50° C.; then
cooling the one or more dried catalyst beds to a first temperature less than the drying temperature, in a range of 31-50° C., and contacting the catalyst of the one or more catalyst beds with the process gas at the first temperature; then
in the presence of the process gas, heating the one or more catalyst beds to at least a second temperature, the second temperature being at least 20° C. greater than the first temperature; and
allowing the process gas to flow through the one or more catalyst beds until
a concentration of acetylene at an outlet of the selective hydrogenation reactor is less than 1 ppm, calculated on a molar basis;
at least 90% of the acetylene present in the process gas is hydrogenated; and
no more than 1 mol. % of the total acetylene and ethylene present in the process gas is converted to ethane.
20. The method according to claim 19 , wherein, before introducing the process gas, the catalyst of the one or more catalyst beds has not been contacted in the selective hydrogenation reactor with carbon monoxide in an amount in excess of 100 ppm, calculated on a molar basis.