Direct catalytic conversion of alcohols to olefins of higher carbon number with reduced ethylene production
A catalyst composition for converting an alcohol to olefins, the catalyst composition comprising the following components: (a) a support (e.g., particles) comprising silicon and oxygen; (b) at least one of copper and silver residing on and/or incorporated into said support; and (c) at least one lanthanide element residing on and/or incorporated into said support. The catalyst may also further include component (d), which is zinc. Also described herein is a method for converting an alcohol to one or more olefinic compounds (an olefin fraction) by contacting the alcohol with a catalyst at a temperature of at least 100° C. and up to 500° C. to result in direct conversion of the alcohol to an olefin fraction containing one or more olefinic compounds containing at least three carbon atoms; wherein ethylene and propylene are produced in a minor proportion of the olefin fraction, and butenes and higher olefins are produced in major proportion.
1. A catalyst composition for converting an alcohol to olefins, the catalyst composition comprising the following components:
(a) support particles comprising silicon (Si) and oxygen (O);
(b) at least one of copper (Cu) and silver (Ag) residing on and/or incorporated into said support particles; and
(c) at least one lanthanide element residing on and/or incorporated into said support particles.
2. The catalyst composition of claim 1 , wherein all support particles have the same composition.
3. The catalyst composition of claim 2 , wherein a portion of the support particles contains component (b) and not component (c), and a portion of the support particles contains component (c) and not component (b).
4. The catalyst composition of claim 2 , wherein all support particles contain component (b) and component (c).
5. The catalyst composition of claim 1 , wherein the support particles comprise at least a first set of support particles and a second set of support particles having different compositions.
6. The catalyst composition of claim 5 , wherein the first set of support particles contains component (b) and not component (c), and the second set of support particles contains component (c) and not component (b).
7. The catalyst composition of claim 5 , wherein at least the first set of support particles and the second set of support particles contain component (b) and component (c).
8. The catalyst composition of claim 1 , wherein at least a portion of the support particles has a silica composition.
9. The catalyst composition of claim 1 , wherein at least a portion of the support particles includes aluminum atoms and has a zeolite composition.
10. The catalyst composition of claim 9 , wherein the zeolite composition is at least partially dealuminated and has a silicon to aluminum ratio of at least 10.
11. The catalyst composition of claim 9 , wherein said zeolite is a Beta zeolite.
12. The catalyst composition of claim 11 , wherein the Beta zeolite is at least partially dealuminated and has a silicon to aluminum ratio of at least 5.
13. The catalyst composition of claim 1 , wherein component (b) is present by weight of support particles in an amount of 0.5-20 wt %.
14. The catalyst composition of claim 1 , wherein component (c) is present by weight of support particles in an amount of 0.5-30 wt %.
15. The catalyst composition of claim 1 , wherein the at least one lanthanide element is selected from the group consisting of lanthanum, cerium, gadolinium, ytterbium, and combinations thereof.
16. The catalyst composition of claim 1 , further comprising: (d) zinc, either in combination with component (b), or component (c), or with both components (b) and (c).
17. A method for converting an alcohol to one or more olefinic compounds, the method comprising contacting the alcohol with a catalyst at a temperature of at least 100° C. and up to 500° C. to result in direct conversion of said alcohol to an olefin fraction comprising one or more olefinic compounds containing at least three carbon atoms; wherein ethylene is produced in an amount of no more than 5 vol % in said olefin fraction; wherein propene is produced in an amount of no more than 25 vol % in said olefin fraction; and wherein butenes are produced in an amount of least 20 vol % in said olefin fraction;
wherein said catalyst comprises the following components:
(a) support particles comprising silicon (Si) and oxygen (O);
(b) at least one of copper and silver residing on and/or incorporated into said support particles; and
(c) at least one lanthanide element residing on and/or incorporated into said support particles.
18. The method of claim 17 , wherein paraffins are optionally produced along with the olefin fraction in an amount of no more than 3 vol %.
19. The method of claim 17 , wherein aromatics are optionally produced along with the olefin fraction in an amount of no more than 2 vol %.
20. The method of claim 17 , wherein said butenes are produced in an amount of at least 30 vol % in said olefin fraction.
21. The method of claim 17 , wherein olefins containing at least five carbon atoms are present in said olefin fraction in an amount of at least 40 vol %.
22. The method of claim 17 , wherein said alcohol has one to four carbon atoms.
23. The method of claim 17 , wherein said alcohol comprises ethanol.
24. The method of claim 17 , wherein said alcohol is in aqueous solution in a concentration of no more than 50 vol %.
25. The method of claim 17 , wherein said alcohol is a component of a fermentation stream when contacted with said catalyst.
26. The method of claim 17 , wherein said alcohol is a component of an acetone-butanol-ethanol (ABE) fermentation stream when contacted with said catalyst.
27. The method of claim 17 , wherein 1,3-butadiene is co-produced along with said one or more olefinic compounds during the direct conversion of said alcohol to the one or more olefinic compounds.
28. A method for converting an alcohol to a jet or diesel hydrocarbon fraction, the method comprising:
(i) converting an alcohol to an olefin fraction, the method comprising contacting the alcohol with a conversion catalyst at a temperature of at least 100° C. and up to 500° C. to result in direct conversion of said alcohol to said olefin fraction, wherein said olefin fraction comprises one or more olefinic compounds containing at least three carbon atoms; wherein ethylene is produced in an amount of no more than 5 vol % in said olefin fraction; wherein propene is produced in an amount of no more than 25 vol % in said olefin fraction; and wherein butenes are produced in an amount of least 20 vol % in said olefin fraction; wherein said conversion catalyst comprises the following components:
(a) support particles comprising silicon (Si) and oxygen (O);
(b) at least one of copper and silver residing on and/or incorporated into said support particles; and
(c) at least one lanthanide element residing on and/or incorporated into said support particles;
(ii) subjecting said first mixed olefin fraction to an oligomerization process in which the first mixed olefin fraction is contacted with an oligomerization catalyst at a temperature of at least 40° C. and up to 400° C. to result in an oligomerized product containing a C 6 + , C 7 + , or C 8 + partially unsaturated fraction; and
(iii) contacting the partially unsaturated fraction with a precious metal-containing hydrogenation catalyst in the presence of hydrogen gas at a temperature of at least 100° C. and up to 500° C. to produce a jet fuel or diesel hydrocarbon fraction, wherein the jet fuel or diesel hydrocarbon fraction contains a C 6 + , C 7 + , or C 8 + paraffin fraction with substantially no olefin or aromatic fraction.