# US 12,110,261 B2 · Free radical process for making low molecular weight compounds useful for making high octane fuels > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,110,261 B2 - Document ID: US12110261B2 - Status: Granted - Kind: B2 - Application number: 17/256,767 - Filed: 2019-07-15 - Published: 2021-09-02 - Granted: 2024-10-08 - Earliest claimed: 2018-07-16 - Assignees: Keen Process Technologies, LLC - Applicants: Keen Process Technologies, LLC - Inventors: Brian T. Keen - Web page: https://patentgrep.com/patent/US12110261B2 ## CPC - C07C 2/56: Addition to acyclic hydrocarbons - C07C 29/44: increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond (C07C29/16 takes precedence) - C10G 29/205: {by reaction with hydrocarbons added to the hydrocarbon oil} - C10L 1/04: essentially based on blends of hydrocarbons - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES - C10L: FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS ## Abstract The present invention relates to free radical reaction methods in which low molecular weight, C2 to C6, unsaturated organic compounds such as ethylene and/or propylene are reacted with low molecular weight, C1 to C15, preferably C1 to C10 saturated organic compounds to form low molecular weight, linear or branched C3 to C24, preferably C3 to C12 organic compounds. The present invention is based at least in part upon the concept of carrying out the free radical reaction in the presence of a typically low concentrations of the unsaturated reactant(s) in the reaction zone(s). By doing this, chain transfer mechanisms are more favored while chain extension mechanisms are less favored. In some embodiments, principles of the present invention are helpful to create conditions under which chain transfer to form more stable, secondary or tertiary branched radicals is favored over olefin addition via chain extension. ## Claims ### Claim 1 A continuous method of making one or more C3 to C12 organic compounds, comprising the step of free radically reacting reactants comprising at least one C2 to C6 unsaturated organic compound and at least one C1 to C10 chain transfer agent in a reaction zone in the presence of at least one free radical initiator under conditions effective to form a reaction product comprising the one or more C3 to C12 organic compounds, wherein: i) the at least one C2 to C6 unsaturated organic compound is fed to the reaction zone in a manner effective to limit the concentration of the at least one C2 to C6 unsaturated organic compound in the reaction zone to 2 weight percent or less based on the total weight of the at least one C2 to C6 unsaturated organic compound and the at least one chain transfer agent in the reaction zone; ii) the at least one C2 to C6 unsaturated organic compound is reacted in the reaction zone at a rate equal to or greater than the rate at which the at least one C2 to C6 unsaturated organic compound is fed to the reaction zone; and iii) the at least one C2 to C6 unsaturated organic compound and the at least one C1 to C10 chain transfer agent are reacted in the reaction zone in a manner such that the molar conversion of the at least one C2 to C6 unsaturated organic compound is greater than the molar conversion of the at least one C1 to C10 chain transfer agent. ### Claim 2 (depends on 1) The method of claim 1, wherein the at least one C2 to C6 unsaturated organic compound comprises ethylene. ### Claim 3 (depends on 2) The method of claim 2, wherein the at least one chain transfer agent comprises methanol and the product comprises 1-propanol. ### Claim 4 (depends on 2) The method of claim 2, wherein the chain transfer agent comprises isobutane and the product comprises dimethyl butane and trimethyl pentane. ### Claim 5 (depends on 1) The method of claim 1, wherein the at least one C2 to C6 unsaturated organic compound comprises propylene. ### Claim 6 (depends on 5) The method of claim 5, wherein the at least one chain transfer agent comprises methanol and the product comprises 1-butanol. ### Claim 7 (depends on 1) The method of claim 1, wherein the at least one C2 to C6 unsaturated organic compound comprises a hydrocarbon and wherein the at least one chain transfer agent comprises a hydrocarbon. ### Claim 8 (depends on 1) The method of claim 1, wherein the molar ratio of the at least one C2 to C6 unsaturated organic compound to the total moles of the at least one free radical initiator fed to the reaction is in the range from 40:1 to 2000:1. ### Claim 9 (depends on 1) The method of claim 1, wherein the concentration of the at least one C2 to C6 unsaturated organic compound in the reaction zone is in the range from 10 ppm to 1.2 weight percent based on the total weight of the at least one C2 to C6 unsaturated organic compound and the at least one chain transfer agent in the reaction zone. ### Claim 10 (depends on 1) The method of claim 1, wherein the steady state weight ratio of the at least one chain transfer agent to the at least one C2 to C6 unsaturated organic compound in the reaction zone is higher than the feed weight ratio. ### Claim 11 (depends on 1) The method of claim 1, further comprising recovering one or more desired products from the product and recycling a remainder to the reaction zone. ### Claim 12 (depends on 1) The method of claim 1, wherein the reaction occurs in a reaction vessel in which the surface to volume ratio is less than 0.5 cm−1. ### Claim 13 (depends on 1) The method of claim 1, wherein the reaction zone includes a surface that comprises one or more of a fluoropolymer, quartz, a nitride, a carbide, and combinations of these. ### Claim 14 (depends on 1) The method of claim 1, wherein the step of free radically reacting the reactants comprises free radically reacting the reactants in a plurality of reaction zones, and wherein the concentration of the at least one C2 to C6 unsaturated organic compound in the reaction zone is 2 weight percent or less based on the total weight of the at least one C2 to C6 unsaturated organic compound and the at least one chain transfer agent in one or more reaction zones. ### Claim 15 (depends on 1) The method of claim 1, wherein metal is excluded from the reaction zone. ### Claim 16 (depends on 1) The method of claim 1, wherein the reaction zone has surfaces in contact with the at least one of ethylene and/or propylene and the at least one C1 to C10 alcohol reactant and wherein the surfaces are substantially inert with respect to the at least one of ethylene and/or propylene and the at least one C1 to C10 alcohol reactant. ### Claim 17 A method of making one or more C3 to C12 alcohols, comprising the step of free radically reacting reactants comprising at least one of ethylene and/or propylene and at least one C1 to C10 alcohol reactant in a reaction zone in the presence of at least one free radical initiator under conditions effective to form a reaction product comprising the one or more C3 to C12 alcohols, wherein: i) the concentration of the ethylene if any and propylene if any in the reaction zone is 2 weight percent or less based on the total weight of the ethylene if any and propylene if any and the at least one alcohol reactant in the reaction zone; ii) the at least one of ethylene and/or propylene is reacted in the reaction zone at a rate equal to or greater than the rate at which the at least one of ethylene and/or propylene is fed to the reaction zone; and iii) the at least one of ethylene and/or propylene and the at least one C1 to C10 alcohol reactant are reacted in the reaction zone in a manner such that the molar conversion of the at least one of ethylene and/or propylene is greater than the molar conversion of the at least one C1 to C10 alcohol reactant. ### Claim 18 (depends on 17) The method of claim 17, wherein the concentration of the ethylene if any and propylene if any in the reaction zone is in the range from 10 ppm to 1.2 weight percent based on the total weight of the ethylene if any and propylene if any and the at least one chain transfer agent in the reaction zone.