Integrated process for the production of methanol and methyl acetate
View Patent ↗Integrated process for the production of methyl acetate and methanol. The process is carried out by carbonylating dimethyl ether with synthesis gas, recovering methyl acetate and unreacted synthesis gas and supplying unreacted synthesis gas and fresh synthesis gas for methanol synthesis.
1. An integrated process for the production of methyl acetate and methanol which process comprises:
(i) supplying a first synthesis gas and dimethyl ether to a carbonylation reaction zone and reacting therein the dimethyl ether and the synthesis gas in the presence of a carbonylation catalyst to form a gaseous carbonylation reaction product comprising methyl acetate and a synthesis gas enriched in hydrogen gas relative to the hydrogen content of the feed synthesis gas and wherein the carbonylation catalyst is an aluminosilicate zeolite which comprises at least one channel which is defined by an 8-membered ring;
(ii) withdrawing carbonylation reaction product from the carbonylation reaction zone and recovering therefrom a methyl acetate-rich liquid stream and a synthesis gas stream which synthesis gas stream is split into a major portion and a minor portion and wherein the major portion is recycled to the carbonylation reaction zone and the minor portion is scrubbed with a scrubbing solvent; and
(iii) supplying the minor portion of the synthesis gas and a second synthesis gas to a methanol synthesis zone and contacting therein the synthesis gas with a methanol synthesis catalyst to form a methanol synthesis product comprising methanol and unconverted synthesis gas.
2. A process according to claim 1 which further comprises the steps of
(iv) withdrawing the methanol synthesis product from the methanol synthesis zone and recovering therefrom a methanol-rich liquid stream and a synthesis gas stream; and
(v) recycling at least a portion of the synthesis gas stream recovered from the methanol synthesis product to the methanol synthesis zone.
3. A process according to claim 1 wherein the first synthesis gas has a stoichiometric number SN and SN=(H 2 —CO 2 )/(CO+CO 2 ) of 1.1 or less (including any recycles).
4. A process according to claim 3 wherein the first synthesis gas has a stoichiometric number in the range 0.05 to 1.1.
5. A process according to claim 1 wherein the first synthesis gas comprises synthesis gas recovered from the carbonylation reaction product.
6. A process according to claim 1 wherein the second synthesis gas and the synthesis gas recovered from the carbonylation reaction product has a combined stoichiometric number which is higher than the stoichiometric number of the first synthesis gas.
7. A process according to claim 6 wherein the combined stoichiometric number is in the range 1.5 to 2.5.
8. A process according to claim 1 wherein at least one of the first and second synthesis gas comprises carbon dioxide (including any recycles).
9. A process according to claim 8 wherein carbon dioxide is present in at least one of the first and second synthesis gas in an amount in the range 0.5 to 12 mol %.
10. A process according to claim 1 wherein the aluminosilicate zeolite has a framework structure type selected from MOR, FER, OFF and GME.
11. A process according to claim 10 wherein the zeolite has a framework structure type MOR and is a mordenite.
12. A process according to claim 1 wherein the first synthesis gas and dimethyl ether are reacted in the carbonylation reaction zone under conditions of a temperature in the range 250° C. to 350° C. and a total pressure in the range 50 to 100 barg (5000 kPa to 10,000 kPa).
13. A process according to claim 1 wherein the major portion is 75 to 99 mol % of the synthesis gas recovered from the carbonylation reaction product.
14. A process according to claim 1 wherein the synthesis gas is scrubbed with a scrubbing solvent comprising methanol.
15. A process according to claim 14 wherein the scrubbing solvent further comprises one or more of water and dimethyl ether.
16. A process according to claim 14 wherein the scrubbing solvent is at least a portion of the methanol-rich liquid stream recovered from the methanol synthesis product.
17. A process according to claim 1 wherein carbon dioxide is introduced into the methanol synthesis zone and such carbon dioxide is obtained from one or more of the first synthesis gas and the second synthesis gas.
18. A process according to claim 1 wherein the methanol synthesis catalyst comprises copper.
19. A process according to claim 1 wherein synthesis gas is contacted with the methanol synthesis catalyst under conditions of a temperature of from 210° C. to 270° C. and a total pressure in the range 50 to 100 barg (5000 kPa to 10,000 kPa).
20. A process according to claim 1 wherein methanol is recovered from one or more of the methanol synthesis product withdrawn from the methanol synthesis zone and liquid solvent streams comprising methanol obtained from scrubbing of synthesis gas recovered from the carbonylation reaction product.
21. A process according to claim 2 wherein methanol is recovered from the methanol-rich liquid stream.
22. A process according to claim 2 wherein a portion of the synthesis gas stream recycled to the methanol synthesis zone is vented as a purge stream.
23. A process according to claim 1 wherein methyl acetate is recovered from at least a portion of the methyl acetate-rich liquid stream and the recovered methyl acetate is converted to acetic acid.
24. A process according to claim 1 wherein each of the carbonylation reaction and the methanol synthesis is conducted as a heterogeneous vapour phase reaction.
25. A process according to claim 1 wherein the process is operated as a continuous process.