Production of ethanol from synthesis gas
A process for producing ethanol from synthesis gas by reacting the hydrogen and carbon monoxide of the synthesis gas to provide methanol, which then is subjected to dehydration to produce at least one ether, such as dimethyl ether. The ether, such as dimethyl ether, then is subjected to carbonylation with unreacted carbon monoxide from the synthesis gas to provide at least one acetate, such as methyl acetate. The acetate then is subjected to hydrogenolysis to produce ethanol.
1. A process for producing ethanol from synthesis gas, comprising:
(a) reacting synthesis gas, said synthesis gas containing hydrogen and carbon monoxide, under conditions to provide a first reaction product including at least one ether, methanol, water, unreacted hydrogen, and unreacted carbon monoxide;
(b) condensing said first reaction product to produce a first condensate stream comprising water and methanol and a second stream comprising said at least one ether, said unreacted hydrogen, said unreacted carbon monoxide, and water;
(c) contacting said first condensate stream of step (b) with a desiccant, thereby removing water from said first condensate stream, thereby providing a stream comprising methanol;
(d) contacting said second stream of step (b) with a desiccant, thereby removing water from said second stream of step (b), thereby providing a stream comprising said at least one ether, said unreacted hydrogen, and said unreacted carbon monoxide;
(e) passing said stream comprising said at least one ether, said unreacted hydrogen, and said unreacted carbon monoxide of step (d) to a carbonylation/hydrogenolysis reactor, wherein said carbonylation/hydrogenolysis reactor contains a plurality of fixed catalyst beds, which contain said carbonylation catalyst and said hydrogenolysis catalyst, whereby said at least one ether, said unreacted hydrogen, and said unreacted carbon monoxide are reacted in the presence of a carbonylation catalyst selected from the group consisting of H-mordenite and Group VII metals, and a hydrogenolysis catalyst selected from the group consisting of copper chromite, copper oxide, and zinc oxide to provide a first ethanol product stream containing ethanol, methanol, methyl acetate, ethyl acetate, unconverted at least one ether, and unconverted synthesis gas;
(f) condensing said first ethanol product stream to provide an ethanol condensate stream comprising ethanol, methanol, methyl acetate, and ethyl acetate, and an unconverted material stream comprising unconverted at least one ether and unconverted synthesis gas;
(g) recycling said unconverted material stream of step (f) to step (e);
(h) distilling said ethanol condensate stream to provide a second ethanol product stream comprising ethanol and a first distillate stream comprising methanol, methyl acetate, and ethyl acetate;
(i) distilling said first distillate stream to produce a methanol stream comprising methanol and a second distillate stream comprising methyl acetate and ethyl acetate; and
(j) recycling second distillate stream of step (i) to step (e).
2. The process of claim 1 , and further comprising:
recycling said stream comprising methanol of step (c) to step (a).
3. The process of claim 1 , and further comprising:
recycling said methanol stream of step (i) to step (a).
4. The process of claim 1 wherein said hydrogen and said carbon monoxide of said synthesis gas of step (a) are reacted at a pressure of from about 250 psi to about 2,000 psi.
5. The process of claim 4 wherein said hydrogen and said carbon monoxide of said synthesis gas of step (a) are reacted at a pressure of from about 300 psi to about 900 psi.
6. The process of claim 1 wherein said hydrogen and said carbon monoxide of said synthesis gas of step (a) are reacted at a temperature of from about 100° C. to about 400° C.
7. The process of claim 6 wherein said hydrogen and said carbon monoxide of said synthesis gas of step (a) are reacted at a temperature of from about 150° C. to about 350° C.
8. The process of claim 1 wherein said hydrogen and said carbon monoxide are reacted in step (a) at a molar ratio of hydrogen to carbon monoxide of from about 0.6 to about 3.0.
9. The process of claim 1 wherein said at least one ether is dimethyl ether.
10. The process of claim 1 wherein step (a) comprises:
(i) reacting said hydrogen with said carbon monoxide of said synthesis gas to produce methanol; and
(ii) converting said methanol to said at least one ether, thereby providing said first reaction product including said at least one ether, said unreacted hydrogen, said unreacted carbon monoxide, unreacted methanol, and water.
11. The process of claim 10 wherein step (a) is conducted in the presence of a catalyst.
12. The process of claim 11 wherein said catalyst is selected from the group consisting of copper chromite, copper oxide, zinc oxide, and mixtures thereof.
13. The process of claim 12 wherein said catalyst is supported on a support selected from the group consisting of alumina and zeolites.
14. The process of claim 12 wherein said catalyst further includes a transition metal.
15. The process of claim 1 wherein step (e) comprises:
(i) reacting said at least one ether with carbon monoxide to produce at least one acetate comprising methyl acetate and ethyl acetate; and
(ii) subjecting said at least one acetate to hydrogenolysis to produce ethanol and methanol.
16. The process of claim 9 wherein, in step (e), said carbon monoxide and said dimethyl ether are fed to said carbonylation/hydrogenolysis reactor at a molar ratio of carbon monoxide to dimethyl ether of from about 1:1 to about 20:1.
17. The process of claim 16 wherein, in step (e), said carbon monoxide and said dimethyl ether are fed to said carbonylation/hydrogenolysis reactor at a molar ratio of carbon monoxide to dimethyl ether of from about 5:1 to about 10:1.
18. The process of claim 9 wherein, in step (e), said hydrogen and said dimethyl ether are fed to said carbonylation/hydrogenoysis reactor at a molar ratio of hydrogen to dimethyl ether of from about 1:1 to about 20:1.
19. The process of claim 18 wherein, in step (e), said hydrogen and said dimethyl ether are fed to said carbonylation/hydrogenolysis reactor at a molar ratio of hydrogen to dimethyl ether of from about 5:1 to about 10:1.
20. The process of claim 1 wherein, in step (e), carbon monoxide is fed to said carbonylation/hydrogenolysis reactor at a gas hourly space velocity of from about 250 I/hr. to about 20,000 I/hr. per liter of catalyst.
21. The process of claim 20 wherein, in step (e), said carbon monoxide is fed to said carbonylation/hydrogenolysis reactor at a gas hourly space velocity of from about 2,000 I/hr. to about 8,000 I/hr. per liter of catalyst.
22. The process of claim 1 , wherein, in step (e), said hydrogen and said carbon monoxide are fed to said carbonylation/hydrogenolysis reactor at a molar ratio of hydrogen to carbon monoxide of from about 0.6 to about 3.0.