Integrated capture and conversion of CO
A process for producing methanol includes combining a hydrogenation catalyst, hydrogen, and CO 2 with a condensed phase solution comprising an amine under conditions effective to form methanol and water. A process for coproduction of methanol and a glycol includes combining an epoxide, a hydrogenation catalyst, hydrogen, and CO 2 with a condensed phase solution comprising an amine under conditions effective to form methanol and a glycol.
1. A process, comprising:
producing methanol and a glycol by combining an epoxide, a hydrogenation catalyst, hydrogen, and CO 2 with a condensed phase comprising an amine under conditions effective to provide a reaction between the epoxide, hydrogen, and CO 2 to form methanol and the glycol, wherein at least 10 mol % of the epoxide is consumed in the reaction.
2. The process of claim 1 , wherein the condensed phase is a condensed phase solution further comprising the CO 2 .
3. The process of claim 2 , further comprising preparing the condensed phase solution by contacting a gas stream comprising CO 2 with an amine-containing solvent or solution prior to combining the epoxide, the hydrogenation catalyst, and the hydrogen with the condensed phase solution.
4. The process of claim 3 , wherein contacting the gas stream with the amine-containing solvent or solution is performed:
(i) at a temperature T′ within a range of from 20° C. to 60° C.; or
(ii) at an initial pressure P′ within a range of from 0.1 MPa to 5 MPa; or
(iii) both (i) and (ii).
5. The process of claim 1 , wherein the conditions effective to form methanol and the glycol comprise:
(i) a temperature T MG within a range of from 50° C. to 170° C.; or
(ii) an initial pressure P MG within a range of from 3 MPa to 10 MPa; or
(iii) a time t MG within a range of from 3 seconds to 36 hours; or
(iv) any combination of (i), (ii), and (iii).
6. The process of claim 1 , further comprising:
(i) combining the epoxide, the CO 2 , and the condensed phase under cycloaddition conditions effective to form a cyclic carbonate, thereby producing a cyclic carbonate-containing mixture, and
subsequently combining the cyclic carbonate-containing mixture with the hydrogenation catalyst and hydrogen under conditions effective to form methanol and the glycol; or
(ii) forming a mixture by combining the epoxide, the hydrogen catalyst, and the CO 2 with the condensed phase,
exposing the mixture to cycloaddition conditions effective to form a cyclic carbonate, thereby producing a cyclic carbonate-containing mixture, and
combining the cyclic carbonate-containing mixture with hydrogen under conditions effective to form methanol and the glycol.
7. The process of claim 6 , wherein the cycloaddition conditions effective to form a cyclic carbonate comprise:
(i) a temperature T C within a range of from 25° C. to 180° C.; or
(ii) an initial pressure P C within a range of from 0.1 MPa to 2 MPa; or
(iii) a time t C within a range of from 3 seconds to 36 hours; or
(iv) any combination of (i), (ii), and (iii).
8. The process of claim 1 , wherein:
the epoxide comprises
and
the glycol comprises R—CH(OH)—CH(R′) (OH),
where R and R′ independently are H or aliphatic, or R and R′ together with the carbon atoms to which they are attached form a cycloaliphatic ring.
9. The process of claim 8 , wherein R is methyl and R′ is H.
10. The process of claim 1 , further comprising:
(i) cooling the methanol and the glycol to a temperature within a range of from −100° C. to 30° C.; or
(ii) separating the methanol and the glycol from the condensed phase; or
(iii) separating the methanol and glycol from the condensed phase, and subsequently separating the methanol and the glycol; or
(iv) both (i) and (ii) or both (i) and (iii).
11. The process of claim 1 , wherein:
(i) the amine comprises a 1° amine group, a 2° amine group, a 3° amine group, or any combination thereof; or
(ii) wherein the CO 2 is adsorbed, absorbed, covalently bound, or ionically bound to the amine; or
(iii) both (i) and (ii).
12. The process of claim 11 , wherein the amine comprises a polyamine, a tertiary amine, a compound according to Formula I, or any combination thereof, the compound according to Formula I having a structure R 1 (R 2 )N-L 1 -NH—R 3 where each of R 1 and R 2 independently is aliphatic or cycloaliphatic or R 1 and R 2 together with the nitrogen to which they are attached form a heterocyclyl ring, L 1 is aliphatic or cycloaliphatic or L 1 and R 1 together with the nitrogen to which they are attached form a heterocyclyl ring, and R 3 is aliphatic, cycloaliphatic, cycloalkylalkyl or alkoxyalkyl.
13. The process of claim 12 , wherein the amine comprises polyethyleneimine (PEI), a compound according to Formula I, a tertiary amine, or any combination thereof.
14. The process of claim 1 , wherein the condensed phase solution:
(i) further comprises a nonaqueous solvent; or
(ii) comprises from 0-10 wt % water; or
(iii) both (i) and (ii).
15. The process of claim 1 , wherein the hydrogenation catalyst comprises:
(i) Ru, Pt, Pd, Rh, Ir, Ni, Co, Fe, Cu, Zn, a catalyst supported on alumina, carbon, silica, chromite, or a magnesium aluminum spinel, or any combination thereof; or
(ii) a pincer ligand; or
(iii) both (i) and (ii).
16. The process of claim 15 , wherein the hydrogenation catalyst comprises
or a combination thereof.
17. The process of claim 1 , wherein:
(i) a molar ratio of H 2 to CO 2 is within a range of from 2:1 to 10:1; or
(ii) the CO 2 is adsorbed, absorbed, covalently bound, or ionically bound to the amine, and the process is performed in an absence of CO 2 overpressure; or
(iii) both (i) and (ii).
18. The process of claim 1 , wherein:
(i) the hydrogenation catalyst is disposed in a fixed bed or fluidized bed; or
(ii) the process is a continuous process; or
(iii) both (i) and (ii).
19. A process, comprising:
producing methanol by combining a hydrogenation catalyst, hydrogen, and CO 2 with a condensed phase comprising an amine under conditions effective to provide a reaction between the hydrogen and CO 2 to form methanol and water, wherein at least 10 mol % of the CO 2 is consumed in the reaction;
separating the methanol and water from the amine; and
separating the methanol and water.
20. The process of claim 19 , wherein the conditions effective to provide a reaction between the hydrogen and CO 2 to form methanol and water comprise:
(i) a temperature T M within a range of from 50-180° C.; or
(ii) an initial pressure P M within a range of from 1 MPa to 10 MPa; or
(iii) a time t M within a range of from 3 seconds to 36 hours; or
(iv) any combination of (i), (ii), and (iii).