# US 11,028,188 B2 · Processes for recovering rubber from aged briquettes > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,028,188 B2 - Document ID: US11028188B2 - Status: Granted - Kind: B2 - Application number: 16/433,590 - Filed: 2019-06-06 - Published: 2019-09-19 - Granted: 2021-06-08 - Earliest claimed: 2012-03-06 - Assignees: Bridgestone Corporation - Applicants: Bridgestone Corporation - Inventors: Yingyi Huang; Mark W. Smale; Robert W. White; Hiroshi Mouri; William M. Cole - Web page: https://patentgrep.com/patent/US11028188B2 ## CPC - C08C 3/02: Purification - C08C 1/04: Purifying; Deproteinising - C08C 2/02: Purification - C08C 2/06: Winning of rubber from solutions - C08G 83/00: Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00 - C08J 11/08: using selective solvents for polymer components - C08L 97/02: Lignocellulosic material, e.g. wood, straw or bagasse {(manufacture of articles made from lignocellulosic material by dry processes B27N)} - C08J 2307/00: Characterised by the use of natural rubber - C08L 2205/03: containing three or more polymers in a blend - C08C: TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract Provided herein are organic solvent-based processes for the removal of rubber from aged briquettes made from compressed plant matter (briquettes) of non-Hevea plants. ## Claims ### Claim 1 A method of recovering rubber from rubber-containing briquettes comprising: a. utilizing aged briquettes comprising at least one antioxidant and chopped guayule plant matter that contains bagasse, rubber, resin and less than 5 weight % leaves of guayule plant, wherein the briquettes have been aged for about 21-200 days after formation; b. mixing the briquettes with (i) at least one non-polar organic solvent and (ii) at least one polar organic solvent to produce a slurry where the total amount of (i) and (ii) is 50-90% by weight of the slurry, the briquettes comprise 10-50% by weight of the slurry, and the slurry contains 0.5-10 weight % water; c. removing a majority of the bagasse from the slurry to produce a miscella and a first bagasse portion; d. optionally adding additional polar organic solvent, non-polar solvent or a combination thereof to the miscella to form a reduced viscosity miscella, wherein any additional polar organic solvent and non-polar organic solvent that is added is the same or different than those utilized in (a) and the amount of any additional polar organic solvent added is less than the amount that causes the rubber contained with the reduced viscosity miscella to coagulate; e. removing 80-95 weight % bagasse (based upon the total weight of bagasse present in the reduced viscosity miscella) from the miscella produced in (c) or (d) thereby forming a purified miscella and a second bagasse fraction, wherein a majority of the bagasse that is removed has a particle size of less than 105 microns; f. optionally treating the purified miscella to remove additional bagasse thereby producing a clarified rubber solution that contains 0.01-1% by weight bagasse (based on the total weight of bagasse present in the slurry) thereby producing a clarified rubber solution; g. increasing the relative amount of polar solvent as compared to non-polar solvent within the purified miscella or clarified rubber solution so as to coagulate the rubber; and h. producing solid purified rubber from the coagulated rubber where when said solid purified rubber contains 0.8% volatile matter it also contains 0.05-0.5 weight % dirt, 0.2-1.5 weight % ash and 0.1-4 weight % resin, wherein at least (b)-(f) are conducted at a temperature or temperatures of 10-80° C. and a pressure of 35 to 1000 kPa. ### Claim 2 (depends on 1) The method of claim 1, wherein: the at least one polar organic solvent and additional polar organic solvent are selected from the group consisting of alcohols having 1 to 8 carbon atoms; ethers and esters having from 2 to 8 carbon atoms; cyclic ethers having from 4 to 8 carbon atoms; ketones having from 3 to 8 carbon atoms; and combinations thereof; and the at least one non-polar organic solvent is selected from the group consisting of alkanes having from 4 to 9 carbon atoms; cycloalkanes and alkyl cycloalkanes having from 5 to 10 carbon atoms; aromatics and alkyl substituted aromatics having from 6 to 12 carbon atoms; and combinations thereof. ### Claim 3 (depends on 1) The method of claim 1, wherein the at least one polar organic solvent and additional polar organic solvent comprise ketones having 3 carbon atoms, and the at least one non-polar organic solvent comprises alkanes having 6 carbon atoms, cycloalkanes having 6 carbon atoms, and combinations thereof. ### Claim 4 (depends on 1) The method of claim 1, wherein the slurry in step (a) contains 25-50% by weight of material from the briquettes and 50-75% by weight non-polar organic solvent and polar organic solvent. ### Claim 5 (depends on 1) The method of claim 1, wherein the (i) at least one non-polar organic solvent of (b); and the (ii) at least one polar organic solvent of (b) are present in relative weight amounts of 50-90% and 10-50%, respectively. ### Claim 6 (depends on 1) The method of claim 1, wherein at least 90% by weight of undersize material of less than 595 microns (30 mesh) has been removed from the chopped guayule plant matter prior to forming the briquette. ### Claim 7 (depends on 1) The method of claim 1, wherein the amount of bagasse that is removed from the slurry in (c) is 60-95% by weight of the bagasse contained within the slurry. ### Claim 8 (depends on 1) The method of claim 1, wherein at least one of (c) or (e) comprises the use of a centrifuge. ### Claim 9 (depends on 8) The method of claim 8, wherein the centrifuge comprises a decanter centrifuge. ### Claim 10 (depends on 8) The method of claim 8, wherein (e) comprises a disk centrifuge. ### Claim 11 (depends on 1) The method of claim 1, wherein the slurry of (c) is subjected to a centrifuging process in order to remove 70-95 weight % bagasse (based on the total weight of bagasse in the slurry) to produce a miscella. ### Claim 12 (depends on 1) The method of claim 1, wherein (b) comprises the use of a counter-current extractor. ### Claim 13 (depends on 1) The method of claim 1, wherein (c) comprises the use of a screw press. ### Claim 14 (depends on 1) The method of claim 1, wherein the coagulation of (g) is controlled so that higher molecular weight rubber having a molecular weight of least 1,000,000 coagulates and lower molecular weight rubber remains in solution. ### Claim 15 (depends on 14) The method of claim 14, wherein a fractionator is used to separate the higher molecular weight rubber from the lower molecular weight rubber. ### Claim 16 A method of recovering rubber from rubber-containing briquettes comprising: a. utilizing aged briquettes comprising at least one antioxidant and chopped guayule plant matter that contains bagasse, rubber, resin and less than 5 weight % leaves of guayule plant, wherein the briquettes have been aged for about 21-200 days after formation; b. mixing the briquettes with (i) at least one non-polar organic solvent and (ii) at least one polar organic solvent to produce a slurry where the total amount of (i) and (ii) is 50-90% by weight of the slurry, the briquettes comprise 10-50% by weight of the slurry, and the slurry contains 0.5-10 weight % water; c. removing a majority of the bagasse from the slurry to produce a miscella and a first bagasse portion; d. optionally adding additional polar organic solvent, non-polar solvent or a combination thereof to the miscella to form a reduced viscosity miscella, wherein any additional polar organic solvent and non-polar organic solvent that is added is the same or different than those utilized in (a) and the amount of any additional polar organic solvent added is less than the amount that causes the rubber contained with the reduced viscosity miscella to coagulate; e. removing 80-95 weight % bagasse (based upon the total weight of bagasse present in the reduced viscosity miscella) from the miscella produced in (c) or (d) thereby forming a purified miscella and a second bagasse fraction, wherein a majority of the bagasse that is removed has a particle size of less than 105 microns; f. optionally treating the purified miscella to remove additional bagasse thereby producing a clarified rubber solution that contains 0.01-1% by weight bagasse (based on the total weight of bagasse present in the slurry) thereby producing a clarified rubber solution; g. increasing the relative amount of polar solvent as compared to non-polar solvent within the purified miscella or clarified rubber solution so as to coagulate the rubber; and h. producing solid purified rubber from the coagulated rubber where when said solid purified rubber contains 0.8% volatile matter it also contains 0.05-0.5 weight % dirt, 0.2-1.5 weight % ash and 0.1-4 weight % resin, wherein at least (b)-(f) are conducted at a temperature or temperatures of 10-80° C. and a pressure of 35 to 1000 kPa, and wherein: the at least one polar organic solvent and additional polar organic solvent are selected from the group consisting of alcohols having 1 to 8 carbon atoms; ethers and esters having from 2 to 8 carbon atoms; cyclic ethers having from 4 to 8 carbon atoms; ketones having from 3 to 8 carbon atoms; and combinations thereof; and the at least one non-polar organic solvent is selected from the group consisting of alkanes having from 4 to 9 carbon atoms; cycloalkanes and alkyl cycloalkanes having from 5 to 10 carbon atoms; aromatics and alkyl substituted aromatics having from 6 to 12 carbon atoms; and combinations thereof. ### Claim 17 (depends on 16) The method of claim 16, wherein at least one of (c) or (e) comprises the use of a centrifuge. ### Claim 18 (depends on 16) The method of claim 16, wherein (b) comprises the use of a counter-current extractor. ### Claim 19 (depends on 16) The method of claim 16, wherein (c) comprises the use of a screw press. ### Claim 20 A method of recovering rubber from rubber-containing briquettes comprising: a. utilizing aged briquettes comprising at least one antioxidant and chopped guayule plant matter that contains bagasse, rubber, resin and less than 5 weight % leaves of guayule plant, wherein the briquettes have been aged for about 21-200 days after formation; b. mixing the briquettes with (i) at least one non-polar organic solvent and (ii) at least one polar organic solvent to produce a slurry where the total amount of (i) and (ii) is 50-90% by weight of the slurry, the briquettes comprise 10-50% by weight of the slurry, the slurry contains 0.5-10 weight % water, and the (i) at least one non-polar organic solvent and the (ii) at least one polar organic solvent are present in relative weight amounts of 50-90% and 10-50%, respectively, in the slurry; c. removing 60-95 weight % of the bagasse from the slurry to produce a miscella and a first bagasse portion; d. optionally adding additional polar organic solvent, non-polar solvent or a combination thereof to the miscella to form a reduced viscosity miscella, wherein any additional polar organic solvent and non-polar organic solvent that is added is the same or different than those utilized in (a) and the amount of any additional polar organic solvent added is less than the amount that causes the rubber contained with the reduced viscosity miscella to coagulate; e. removing 80-95 weight % bagasse (based upon the total weight of bagasse present in the reduced viscosity miscella) from the miscella produced in (c) or (d) thereby forming a purified miscella and a second bagasse fraction, wherein a majority of the bagasse that is removed has a particle size of less than 105 microns; f. optionally treating the purified miscella to remove additional bagasse thereby producing a clarified rubber solution that contains 0.01-1% by weight bagasse (based on the total weight of bagasse present in the slurry) thereby producing a clarified rubber solution; g. increasing the relative amount of polar solvent as compared to non-polar solvent within the purified miscella or clarified rubber solution so as to coagulate the rubber; and h. producing solid purified rubber from the coagulated rubber where when said solid purified rubber contains 0.8% volatile matter it also contains 0.05-0.5 weight % dirt, 0.2-1.5 weight % ash and 0.1-4 weight % resin, wherein at least (b)-(f) are conducted at a temperature or temperatures of 10-50° C. and a pressure of 35 to 1000 kPa, and wherein: the at least one polar organic solvent and additional polar organic solvent are selected from the group consisting of alcohols having 1 to 8 carbon atoms; ethers and esters having from 2 to 8 carbon atoms; cyclic ethers having from 4 to 8 carbon atoms; ketones having from 3 to 8 carbon atoms; and combinations thereof; and the at least one non-polar organic solvent is selected from the group consisting of alkanes having from 4 to 9 carbon atoms; cycloalkanes and alkyl cycloalkanes having from 5 to 10 carbon atoms; aromatics and alkyl substituted aromatics having from 6 to 12 carbon atoms; and combinations thereof. ### Claim 21 (depends on 20) The method of claim 20, wherein at least one of (c) or (e) comprises the use of a centrifuge. ### Claim 22 (depends on 20) The method of claim 20, wherein (b) comprises the use of a counter-current extractor. ### Claim 23 (depends on 20) The method of claim 20, wherein (c) comprises the use of a screw press.