# US 12,006,286 B2 · Method for transesterification of carboxylic acid esters > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,006,286 B2 - Document ID: US12006286B2 - Status: Granted - Kind: B2 - Application number: 16/981,858 - Filed: 2019-03-19 - Published: 2021-04-29 - Granted: 2024-06-11 - Earliest claimed: 2018-03-23 - Assignees: Omya International AG - Applicants: Omya International AG - Inventors: Jamal Ftouni; Matthias Welker; Samuel Rentsch - Web page: https://patentgrep.com/patent/US12006286B2 ## CPC - C07C 67/03: by reacting an ester group with a hydroxy group - B01J 23/02: of the alkali- or alkaline earth metals or beryllium - B01J 35/40: characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77) - B01J 35/613: {10-100 m2/g} - B01J 35/615: {100-500 m2/g} - B01J 37/082: {Decomposition and pyrolysis} - B01J 37/088: {Decomposition of a metal salt} - C01F 11/06: of carbonates - C01F 11/185: {After-treatment, e.g. grinding, purification, conversion of crystal morphology} - C10L 1/02: essentially based on components consisting of carbon, hydrogen, and oxygen only - C10L 1/026: {for compression ignition} - B01J 2235/05: Nuclear magnetic resonance [NMR] - B01J 2235/15: X-ray diffraction - B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy - C01P 2004/51: Particles with a specific particle size distribution - C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer - C01P 2004/62: Submicrometer sized, i.e. from 0.1-1 micrometer - C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer - C01P 2006/12: Surface area - C01P 2006/14: Pore volume - C01P 2006/16: Pore diameter - Y02E 50/10: Biofuels, e.g. bio-diesel - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - C01F: COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts of peroxyacids C01B15/00; sulfides or polysulfides of magnesium, calcium, strontium, or barium C01B17/42; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds other than ammonia or cyanogen containing nitrogen and non-metals and optionally metals C01B21/082; amides or imides of silicon C01B21/087}; metal {imides or} amides C01B21/092, {C01B21/0923}; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanic acid C01C3/14; salts of cyanamide C01C3/16; thiocyanates C01C3/20; {double sulfates of magnesium with sodium or potassium C01D5/12; with other alkali metals C01D15/00, C01D17/00}) - 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 - C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION ## Abstract The present invention relates to a method for transesterification of carboxylic acid esters by heterogeneous catalysis using a catalyst that is obtainable by calcination of surface-reacted calcium carbonate. The invention further relates to the use of said method in the production of fuel or fuel components, such as biodiesel. Further aspects of the present invention relate to the transesterified ester obtainable by the inventive method and to its use as fuel or as fuel component. Still another aspect of the present invention relates to a corresponding transesterification catalyst and to its use in transesterification reactions. ## Claims ### Claim 1 A transesterification catalyst comprising partially or fully calcined surface-reacted calcium carbonate, wherein the calcination is carried out at a calcination temperature of at least 650° C., wherein the transesterification catalyst has a specific surface area of from 15 to 200 m2/g, measured using nitrogen and the BET method according to ISO 9277:2010, and wherein the surface-reacted calcium carbonate is a reaction product of ground natural calcium carbonate containing mineral (GNCC) or precipitated calcium carbonate (PCC) with carbon dioxide and one or more H3O+ ion donors and wherein the carbon dioxide is formed in situ by a reaction with the H3O+ ion donors and/or is supplied from an external source, and wherein the surface-reacted calcium carbonate has a specific surface area of from 15 to 200 m2/g, measured using nitrogen and the BET method according to ISO 9277:2010. ### Claim 2 (depends on 1) The transesterification catalyst according to claim 1, characterized in that the transesterification catalyst has: (i) a d50(vol) of from 1 to 75 μm; and/or (ii) a d98(vol) of from 2 to 150 μm. ### Claim 3 (depends on 1) The transesterification catalyst according to claim 1, characterized in that the transesterification catalyst has: (i) a d50(vol) of from 3 to 15 μm; and/or (ii) a d98(vol) of 10 to 30 μm. ### Claim 4 (depends on 1) The transesterification catalyst according to claim 1, characterized in that the transesterification catalyst has a specific surface area of from 25 to 180 m2/g, measured using nitrogen and the BET method according to ISO 9277:2010. ### Claim 5 (depends on 1) The transesterification catalyst according to claim 1, characterized in that the transesterification catalyst has a specific surface area of from 30 to 150 m2/g, measured using nitrogen and the BET method according to ISO 9277:2010. ### Claim 6 (depends on 1) A method for transesterification of carboxylic acid esters by heterogeneous catalysis, the method comprising the following steps: (a) providing a substrate comprising a first carboxylic acid ester; (b) providing a first alcohol; (c) providing a catalyst according to claim 1; and (d) reacting the substrate provided in step (a) and the first alcohol provided in step (b) in the presence of the catalyst provided in step (c) to obtain a reaction mixture comprising a second carboxylic acid ester and a second alcohol. ### Claim 7 (depends on 6) The method according to claim 6, characterized in that the substrate is a fat or a fatty oil. ### Claim 8 (depends on 6) The method according to claim 6, characterized in that the first carboxylic acid ester is a triglyceride. ### Claim 9 (depends on 6) The method according to claim 6, characterized in that the first alcohol is a monohydric alcohol. ### Claim 10 (depends on 6) The method according to claim 6, characterized in that the surface-reacted calcium carbonate has: (i) a d50(vol) of from 0.5 to 50 μm; and/or (ii) a d98(vol) of from 1 to 120 μm. ### Claim 11 (depends on 6) The method according to claim 6, characterized in that the surface-reacted calcium carbonate has a specific surface area of from 25 to 180 m2/g, measured using nitrogen and the BET method according to ISO 9277:2010. ### Claim 12 (depends on 6) The method according to claim 6, characterized in that: (i) the ground natural calcium carbonate-containing mineral is selected from the group consisting of marble, chalk, dolomite, limestone and mixtures thereof; and/or (ii) the precipitated calcium carbonate comprises aragonitic, vateritic or calcitic mineralogical crystal forms or mixtures thereof. ### Claim 13 (depends on 6) The method according to claim 6, characterized in that the catalyst is obtainable by calcination of surface-reacted calcium carbonate, wherein calcination is carried out: (i) at a calcination temperature of at least 680; ° C., and/or (ii) at a calcination time of at least 5 mins. ### Claim 14 (depends on 6) The method according to claim 6, characterized in that in step (d): the first alcohol is used as reaction medium; and/or the catalyst is used in an amount of from 0.01 to 20 wt. %, based on a total weight of the substrate; and/or the alcohol and the catalyst are contacted in a first step and the substrate is then added in a second step. ### Claim 15 (depends on 6) The method according to claim 6, characterized in that step (d) is carried out at a temperature of at least 20° C. ### Claim 16 (depends on 6) The method according to claim 6, characterized in that the method further comprises step (e) of separating the second carboxylic acid ester from the reaction mixture obtained in step (d). ### Claim 17 (depends on 6) The method according to claim 6, characterized in that the substrate is a vegetable oil. ### Claim 18 (depends on 1) A method of producing fuel or a fuel component, comprising: (a) providing a substrate comprising a first carboxylic acid ester; (b) providing a first alcohol; (c) providing a catalyst according to claim 1; and (d) reacting the substrate provided in step (a) and the first alcohol provided in step (b) in the presence of the catalyst provided in step (c) to obtain a reaction mixture comprising a second carboxylic acid ester and a second alcohol; wherein the second carboxylic acid ester is the fuel or fuel component.