Aliphatic amine and nitrile synthesis through catalytic CO hydrogenation in the presence of ammonia
A process for manufacturing aliphatic amines and nitriles by using the Fischer Tropsch synthesis (FTS), in the production of chain-lengthened hydrocarbons from CO and H 2 and their terminal nitrogen functionalization using ammonia. The method can include activating a catalyst with a feed gas, wherein the feed gas comprises H 2 /CO mixtures; providing a temperature between 180° C. and 300° C. under a pressure between 1 bar to 25 bar; wherein the nitrogenates include at least one aliphatic amine and/or nitrile; and setting or adjusting the H 2 /CO ratio to selectively synthesize amines and/or nitriles over other nitrogen containing compounds.
1 . A reactor-based hydrogenation process for producing nitrogen containing hydrocarbons, comprising
activating one or more cobalt-based catalysts with a synthesis gas comprising carbon monoxide (CO) and hydrogen (H 2 ) to form Co 2 C on one or more activated cobalt-based catalysts;
reacting the CO and H 2 under Fischer-Tropsch reaction conditions in a presence of ammonia and the one or more activated cobalt-based catalysts to produce at least one aliphatic amine and/or nitrile, and
during reacting, controlling a ratio of the H 2 to the CO to 0.3:1 to 7:1 to selectively form the at least one aliphatic amine and/or nitrile.
2 . The process according to claim 1 , wherein the reaction is performed in a fixed bed reactor at a reaction temperature of between 180° C. to 300° C.
3 . The process according to claim 1 , wherein the reaction is performed at a pressure between 1 to 25 bar.
4 . The process according to claim 1 , wherein the ratio of the H 2 to the CO is adjusted from an initial ratio to the controlled ratio of 0.3:1 to 7:1 after the one or more cobalt-based catalysts are activated.
5 . The process according to claim 1 , wherein the ratio of the H 2 to the CO is controlled at to 0.3:1 to 0.5:1 for selectively producing nitriles over other nitrogen containing compounds.
6 . The process according to claim 1 , wherein the ratio of the H 2 to the CO is controlled at 2:1 to 3:1 for selectively producing amines over other nitrogen containing compounds.
7 . The process according to claim 1 , wherein the reacting is performed in a fixed bed reactor, and wherein the ratio of the H 2 to the CO is set to a first ratio of 0.3:1 to 0.5:1 for selectively producing nitriles in the fixed bed reactor and is subsequently adjusted to a second ratio of 2:1 to 3:1 for selectively producing amines in the fixed bed reactor.
8 . The process according to claim 7 , wherein the step of activating the one or more cobalt-based catalysts is performed in the fixed bed reactor when the ratio is set to the first ratio for a sufficient amount of time.
9 . The process according to claim 8 , wherein the sufficient amount of time is 20-30 hours.
10 . The process according to claim 1 , wherein the one or more cobalt-based catalysts include a combination of a dispersant promoter selected from an oxide or a metal of Mn, Ti, Mg, Cr, Ca, Si, Al, Zn, Cu or combinations thereof, and a promoter for influencing product selectivity selected from an alkali oxide, K, Li, Na, Cs or combinations thereof.
11 . The process according to claim 1 , wherein the one or more cobalt-based catalysts are precipitated, sintered, impregnated or dispersed onto a support, wherein the support is selected from an oxide of Ti, Mn, Si, Al or combinations thereof.
12 . The process according to claim 1 , wherein the one or more cobalt-based catalysts comprise Co x Mn y K z , wherein x is 2-4, y is 1-5 and z is 0.1-0.3.
13 . The process according to claim 12 , wherein the Co x Mn y K z is synthesized via oxalate precipitation to form Co 4 Mn 1 K 0.1 .
14 . The process according to claim 1 , further comprising removing ammonia from the synthesis gas after the reacting step.
15 . The process according to claim 1 , wherein the at least one aliphatic amine or nitrile is at a terminal position of the nitrogen containing hydrocarbons.
16 . The process according to claim 1 , wherein the at least one aliphatic amine or nitrile is not produced by a non-catalyzed reaction of ammonia and oxygenates in a gas phase.
17 . The process according to claim 16 , wherein the oxygenates are alcohols, aldehydes and carboxylic acids.
18 . A method to catalytically synthesize chain-lengthened hydrocarbons with terminal nitrogen functionalization, comprising:
activating a cobalt-based catalyst with a feed gas, wherein the feed gas comprises carbon monoxide (CO) and hydrogen (H 2 ), and the activation forms Co 2 C on the cobalt-based catalyst,
wherein the activating step includes performing a reaction at a first H 2 /CO ratio of 0.3:1 up to 0.5:1 for at least 24 hours in a presence of a promoter in order to generate the Co 2 C;
providing a temperature between 180° C. and 300° C. under a pressure between 1 bar to 25 bar in a reaction vessel containing the activated cobalt based-catalyst; and
combining ammonia with the CO and the H 2 in the reaction vessel and reacting the CO and the H 2 to produce nitrogen-containing compounds which comprises at least one aliphatic amine and/or nitrile.
19 . The method of claim 18 , wherein the activated catalyst is synthesized via oxalate precursors.
20 . The method of claim 18 , wherein the activated catalyst includes at least one Mn-oxide or Zr-oxide-promoting transition metal or rare-earth metal.
21 . The method of claim 18 , wherein the activated catalyst is further promoted by alkali.
22 . The method of claim 18 , in which the formation of oxygenates such as alcohols and aldehydes is suppressed.
23 . The method of claim 18 , wherein the formation of alkanes and iso products is inhibited.
24 . The method of claim 18 , wherein the formation of methane is inhibited.
25 . The method of claim 18 , wherein the ratio of hydrogen to carbon monoxide is varied from 0.5:1 to 7:1.
26 . The method of claim 18 , wherein the step is performed at a second H 2 /CO ratio between 2:1 up to 3:1 to selectively form amines, or the first H 2 /CO ratio of about 0.3:1 to 0.5: to selectively form nitriles.