Production of hydrocarbons from plant oil and animal fat
Oils from plants and animal fats are hydrolyzed to fatty acids for a Kolbe reaction. The invention relates to a high productivity Kolbe reaction process for electrochemically decarboxylating C4-C28 fatty acids derived from sources selected based on their saturated and unsaturated fatty acid content in order to lower anodic passivation voltage during synthesis of C6-C54 hydrocarbons. The C6-C54 hydrocarbons may undergo olefin metathesis and/or hydroisomerization reaction processes to synthesize heavy fuel oil, diesel fuel, kerosene fuel, lubricant base oil, and linear alpha olefin products useful as precursors for polymers, detergents, and other fine chemicals.
1. A method of producing C6-C54 hydrocarbons comprising:
(a) combining one or more C4-C28 unsaturated fatty acids and one or more C4-C28 saturated fatty acids with a solvent; and
(b) performing a Kolbe electrolysis reaction on the combined reaction mixture prepared in (a) to produce one or more C6 to C54 hydrocarbons,
wherein the combined reaction mixture of the unsaturated and saturated fatty acids has a combined saturation score (S) of greater than 1.0, where:
S =(2 w s +w mu )/( w mu +2 w du +3 w tu )
and w s , w mu , w du and w tu are weight percent of fatty acids that are saturated (w s ), and having one (w mu ), two (w du ) or three (w tu ) double bonds, respectively.
2. The method of claim 1 , wherein the saturation score of the combined reaction mixture is greater than approximately 1.2.
3. The method of claim 1 , wherein:
(a) the solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, water, and a mixture thereof, and wherein the solvent is a mixture which contains between about 0.5 percent to about 50 percent water by volume;
(b) the reaction mixture for the Kolbe electrolysis reaction is not a solution at room temperature;
(c) the one or more C4-C28 fatty acids in the solvent are reacted with a base to form an amount of a salt of the one or more C4-C28 fatty acids;
(d) the Kolbe electrolysis reaction is conducted at a temperature in a range of about 15° C. to about 100° C.;
(e) the Kolbe electrolysis reaction is performed under a pressure greater than atmospheric pressure to reduce a rate of loss of the solvent or to reduce a rate of loss of a volatile fatty acid;
(f) the combined reaction mixture comprises a solvent and a base from a preceding hydrolysis reaction of a triglyceride; and/or
(g) an electrical current supplied to electrodes used in the Kolbe electrolysis reaction is 0.05-1.0 amperes per cm 2 area of the electrodes.
4. The method of claim 1 , wherein an electrolyte is added to the reaction mixture to improve electrical conductivity of the Kolbe electrolysis reaction, and wherein the electrolyte is selected from the group consisting of a perchlorate salt, a p-toluenesulfonate salt, a tetrafluoroborate salt, and mixtures thereof.
5. The method of claim 1 , wherein the reacting surface of an anode electrode used in the Kolbe electrolysis reaction is a platinum group metal, which includes platinum, iridium, palladium, ruthenium, rhodium, and osmium; or a carbon material, which includes graphite, glassy carbon, baked carbon; or mixture of the platinum group metal and the carbon material.
6. The method of claim 1 , further comprising:
performing an olefin metathesis reaction on a hydrocarbon product of the Kolbe electrolysis reaction using a C2-C5 aliphatic alkene or a mixture of C2-C5 aliphatic alkenes, wherein the olefin metathesis reaction modifies a chain length of the hydrocarbon product.
7. The method of claim 1 , further comprising:
performing an ethenolysis reaction on a hydrocarbon product of the Kolbe electrolysis reaction using ethene to obtain 1-decene, 1-heptene, 1-butene, 1-octene, 1-hexene, or 1,4-pentadiene.
8. The method of claim 7 , further comprising:
separating the products of the ethenolysis reaction to obtain 1-decene, 1-heptene, 1-butene, 1-octene, 1-hexene, 1,4-pentadiene, a diesel fuel, and/or a heavy fuel oil.
9. The method of claim 1 , further comprising:
hydroisomerizing at least some of the products from the Kolbe electrolysis reaction to produce, a lubricant base oil, diesel fuels, jet fuel or gasoline-type products.
10. The method of claim 9 , wherein the hydroisomerization reaction uses a catalyst which is a silica/alumina-based zeolite containing impregnated platinum, a reaction temperature between about 250° C. to about 400° C., a reaction pressure between about 10 bar to about 400 bar, and a hydrogen gas to a hydrocarbon ratio between about 2 to about 50.
11. A method of increasing productivity of a Kolbe electrolysis reaction forming one or more C6 to C54 hydrocarbons, the method comprising:
(a) combining one or more C4-C28 unsaturated fatty acids with a solvent to create a reaction mixture;
(b) adding one or more C4-C28 saturated fatty acids to the reaction mixture; and
(c) performing a Kolbe electrolysis reaction on the combined reaction mixture to produce one or more C6 to C54 hydrocarbons,
wherein the saturated fatty acids are added to lower a passivation voltage of an electrode used in the Kolbe electrolysis reaction, and wherein the combined reaction mixture has a combined saturation score (S) of greater than 1.0, where:
S =(2 w s +w mu )/( w mu +2 w du +3 w tu )
and w s , w mu , w du and w tu are weight percent of fatty acids that are saturated (w s ), and having one (w mu ), two (w du ) or three (w tu ) double bonds, respectively.
12. The method of claim 11 , wherein the saturation score of the combined reaction mixture is greater than approximately 1.2.
13. The method of claim 11 , wherein:
(a) the solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, water, and a mixture thereof, and wherein the solvent is a mixture which contains between about 0.5 percent to about 50 percent water by volume;
(b) the reaction mixture for the Kolbe electrolysis reaction is not a solution at room temperature;
(c) the one or more C4-C28 fatty acids in the solvent are reacted with a base to form an amount of a salt of the one or more C4-C28 fatty acids;
(d) the Kolbe electrolysis reaction is conducted at a temperature in a range of about 15° C. to about 100° C.;
(e) the Kolbe electrolysis reaction is performed under a pressure greater than atmospheric pressure to reduce a rate of loss of the solvent or to reduce a rate of loss of a volatile fatty acid;
(f) the combined reaction mixture comprises a solvent and a base from a preceding hydrolysis reaction of a triglyceride; and/or
(g) an electrical current supplied to electrodes used in the Kolbe electrolysis reaction is 0.05-1.0 amperes per cm 2 area of the electrodes.
14. The method of claim 11 , wherein an electrolyte is added to the reaction mixture to improve electrical conductivity of the Kolbe electrolysis reaction, and wherein the electrolyte is selected from the group consisting of a perchlorate salt, a p-toluenesulfonate salt, a tetrafluoroborate salt, and mixtures thereof.
15. The method of claim 11 , wherein the reacting surface of an anode electrode used in the Kolbe electrolysis reaction is a platinum group metal, which includes platinum, iridium, palladium, ruthenium, rhodium, and osmium; or a carbon material, which includes graphite, glassy carbon, baked carbon; or mixture of the platinum group metal and the carbon material.
16. The method of claim 11 , further comprising:
performing an olefin metathesis reaction on a hydrocarbon product of the Kolbe electrolysis reaction using a C2-C5 aliphatic alkene or a mixture of C2-C5 aliphatic alkenes, wherein the olefin metathesis reaction modifies a chain length of the hydrocarbon product.
17. The method of claim 11 , further comprising:
performing an ethenolysis reaction on a hydrocarbon product of the Kolbe electrolysis reaction using ethene to obtain 1-decene, 1-heptene, 1-butene, 1-octene, 1-hexene, or 1,4-pentadiene.
18. The method of claim 17 , further comprising:
separating the products of the ethenolysis reaction to obtain 1-decene, 1-heptene, 1-butene, 1-octene, 1-hexene, 1,4-pentadiene, a diesel fuel, and/or a heavy fuel oil.
19. The method of claim 11 , further comprising:
hydroisomerizing at least some of the products from the Kolbe electrolysis reaction to produce a lubricant base oil, diesel fuels, jet fuel or gasoline-type products.
20. The method of claim 19 , wherein the hydroisomerization reaction uses a catalyst which is a silica/alumina-based zeolite containing impregnated platinum, a reaction temperature between about 250° C. to about 400° C., a reaction pressure between about 10 bar to about 400 bar, and a hydrogen gas to a hydrocarbon ratio between about 2 to about 50.