Synthesis of fuels and feedstocks
Disclosed herein are embodiments of a method for making fuels and feedstocks from readily available alcohol starting materials. In some embodiments, the method concerns converting alcohols to carbonyl-containing compounds and then condensing such carbonyl-containing compounds together to form oligomerized species. These oligomerized species can then be reduced using by-products from the conversion of the alcohol. In some embodiments, the method further comprises converting saturated, oligomerized, carbonyl-containing compounds to aliphatic fuels.
1. A method, comprising:
exposing an alcohol or a mixture of alcohols to a dehydrogenation catalyst capable of dehydrogenating the alcohol or the mixture of alcohols to produce H 2 and a carbonyl-containing compound, or a mixture of carbonyl-containing compounds;
exposing the carbonyl-containing compound or mixture of carbonyl-containing compounds to a solid acid catalyst to produce a condensation product comprising an α,β-unsaturated carbonyl group, wherein the condensation product is converted to a saturated oligomerized carbonyl-containing compound in the presence of H 2 produced from dehydrogenating the alcohol or mixture of alcohols;
wherein the dehydrogenation catalyst is selected from
wherein each of L, R, and R′ independently can be selected from alkyl, aryl, H, or ER″ n (wherein n is 1, 2, 3, or 4, E is selected from B, C, O, N, P, S, or Si, and R″ is selected from hydrogen, alkyl, or aryl); E is selected from B, C, O, N, P, S, or Si; R″ is selected from hydrogen, alkyl, or aryl, each n is an integer selected from 0 to 4, and M is selected from Mn, Fe, Co, or Cr.
2. The method of claim 1 , wherein the method further comprises exposing the saturated oligomerized carbonyl-containing compound to a metal catalyst, a solid acid catalyst, or a combination thereof at a temperature below 200° C. to form an aliphatic compound.
3. The method of claim 1 , wherein M is selected from cobalt, manganese, or iron.
4. The method of claim 1 , wherein the carbonyl-containing compound has a structure satisfying a formula
wherein each of R 1 and R 2 is hydrogen or aliphatic, and n ranges from 0 to 50.
5. The method of claim 1 , wherein the condensation product is formed by a condensation reaction between two carbonyl-containing compounds having the same structure and wherein the condensation product has a structure satisfying a formula
wherein each R 1 and R 2 is hydrogen or aliphatic, and each n ranges from 0 to 50.
6. The method of claim 1 , wherein the condensation product is formed by a condensation reaction between a mixture of carbonyl-containing compounds having different structures and wherein the condensation product has a structure satisfying a formula
wherein each R 1 , R 1′ , R 2 , and R 2′ independently is selected from hydrogen or aliphatic; and each of n and n′ independently is selected from 0 to 50.
7. The method of claim 1 , wherein exposing the carbonyl-containing compound or mixture of carbonyl-containing compounds to the solid acid catalyst comprises reacting the carbonyl-containing compound or mixture of carbonyl-containing compounds with a styrene-divinylbenzene polymer acid or a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer.
8. The method of claim 1 , wherein the condensation product is converted to the saturated oligomerized carbonyl-containing compound by exposing the condensation product to H 2 produced from dehydrogenating the alcohol or mixture of alcohols by transferring H 2 from a first reaction vessel wherein the alcohol or mixture of alcohols has been dehydrogenated to a second reaction vessel comprising the condensation product.
9. The method of claim 1 , wherein the condensation product is converted to the saturated oligomerized carbonyl-containing compound by adding the solid acid catalyst into a reaction vessel comprising the H 2 produced by dehydrogenation of the alcohol or mixture of alcohols and the carbonyl-containing compound or the mixture of carbonyl-containing compounds.
10. The method of claim 1 , further comprising repeating the step of exposing the carbonyl-containing compound or mixture of carbonyl-containing compounds to a solid acid catalyst in the presence of H 2 to obtain a saturated oligomerized carbonyl-containing compound having a structure satisfying a formula
wherein each R 1 , R 1′ , R 2 , and R 2′ independently is selected from hydrogen or aliphatic; each of n and n′ independently is selected from 0 to 50; and each m independently is selected from 1-24.
11. The method of claim 1 , further comprising adding an alcohol solvent to convert the condensation product comprising an α,β-unsaturated carbonyl group to an acetal-containing product.
12. The method of claim 1 , further comprising adding an alcohol solvent to convert the saturated oligomerized carbonyl-containing compound to a saturated oligomerized acetal-containing compound.
13. The method of claim 10 , further comprising exposing the saturated oligomerized carbonyl-containing compound to a supported metal catalyst selected from Pd/C, Pd/Al 2 O 3 , CuO/Al 2 O 3 , Ru/C, and Ni/SiO 2 —Al 2 O 3 ; H 2 ; a styrene-divinylbenzene polymer acid, a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer; or any combination thereof at a temperature below 200° C. to form an aliphatic oligomerized compound having a structure satisfying a formula
or an alcohol-containing oligomerized compound having a structure satisfying a formula
14. A method, comprising:
exposing an alcohol or mixture of alcohols to a dehydrogenation catalyst capable of dehydrogenating the alcohol or the mixture of alcohols to produce a carbonyl-containing compound having a structure satisfying a formula
or a mixture thereof, and H 2 ;
exposing the carbonyl-containing compound or mixture thereof to a styrene-divinylbenzene polymer acid or a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer to produce an oligomerized condensation product having a structure satisfying a formula
wherein the oligomerized condensation product is converted to a saturated oligomerized carbonyl-containing compound in the presence of H 2 produced from the dehydrogenation of the alcohol or mixture of alcohols, wherein the saturated oligomerized carbonyl-containing compound has a structure satisfying a formula
wherein each R 1 , R 1′ , R 2 , and R 2′ independently is selected from hydrogen or aliphatic; each of n and n′ independently is selected from 0 to 50; and each m independently is selected from 1-24;
wherein the dehydrogenation catalyst is selected from
wherein each of L, R, and R′ independently can be selected from alkyl, aryl, H, or ER″ n (wherein n is 1, 2, 3, or 4, E is selected from B, C, O, N, P, S, or Si, and R″ is selected from hydrogen, alkyl, or aryl); E is selected from B, C, O, N, P, S, or Si; R″ is selected from hydrogen, alkyl, or aryl, each n is an integer selected from 0 to 4, and M is selected from Mn, Fe, Co, or Cr.
15. The method of claim 14 , further comprising repeating the method to obtain a saturated oligomerized carbonyl-containing compound having a structure satisfying a formula
wherein each R 1 , R 1′ , R 2 , and R 2′ independently is selected from hydrogen or aliphatic; each of n and n′ independently is selected from 0 to 50; and each m independently is selected from 1-24.
16. The method of claim 15 , further comprising exposing the saturated oligomerized carbonyl-containing compound to a supported metal catalyst selected from Pd/C, Pd/Al 2 O 3 , CuO/Al 2 O 3 , Ru/C, and Ni/SiO 2 —Al 2 O 3 ; H 2 ; a styrene-divinylbenzene polymer acid, a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer; or any combination thereof at a temperature below 200° C. to form an aliphatic oligomerized compound having a structure satisfying a formula
or an alcohol-containing oligomerized compound having a structure satisfying a formula
17. The method of claim 14 , further comprising adding an alcohol solvent to convert the oligomerized condensation product to an oligomerized acetal-containing compound.
18. The method of claim 14 , further comprising adding an alcohol solvent to convert the saturated oligomerized carbonyl-containing compound to a saturated oligomerized acetal-containing compound.