# US 10,308,784 B2 · Thermochemical process for recovering fiberglass reinforced plastics waste matter > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,308,784 B2 - Document ID: US10308784B2 - Status: Granted - Kind: B2 - Application number: 15/119,011 - Filed: 2015-03-04 - Published: 2017-08-03 - Granted: 2019-06-04 - Earliest claimed: 2014-03-04 - Assignees: KOREC S.r.l. - Applicants: KOREC S.r.l. - Inventors: Elio Santacesaria; Riccardo Tesser; Salvatore Mallardo; Rosa Vitiello; Martino Di Serio; Antonello Dimiccoli; Laura Saviano - Web page: https://patentgrep.com/patent/US10308784B2 ## CPC - C08J 11/12: by dry-heat treatment only - C10B 5/00: Coke ovens with horizontal chambers - C10B 53/07: {of solid raw materials consisting} of synthetic polymeric materials, e.g. tyres (recovery or working-up of waste materials of organic macromolecular compounds or compositions based thereon by dry-heat treatment for obtaining partially depolymerised materials C08J11/10; production of liquid hydrocarbon mixtures from rubber or rubber waste C10G1/10) - C10G 1/10: from rubber or rubber waste - C08J 2331/02: Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids - C08J 2367/06: Unsaturated polyesters - Y02P 20/143: the feedstock being recycled material, e.g. plastics - 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) - C10B: DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS (cracking oils C10G; underground gasification of minerals E21B43/295) - 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 - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract The invention relates to a pyrolysis process carried out in the presence of a controlled carbon dioxide environment that allows recovering both the organic portion and the inorganic portion (glass fibers) of a fiberglass-reinforced plastic waste, at an organic yield recovered even higher than 95% by weight and with a suitable for manufacturing new articles, in particular fiberglass-reinforced plastic articles, which provides a profitable to the disposal in dump areas. In particular, the recovered organic products can be mixed as such, at a percentage as high as 20% and more, with a fresh unsaturated polyester resins that is normally used to manufacture common fiberglass-reinforced plastic articles, without worsening its features with respect to articles made starting from fresh resin alone. The glass fibers, which are fully recovered in a combustion treatment after the pyrolysis, are reused fully replacing the corresponding virgin glass fibers, since they are unbroken and perfectly clean in a final step of the process. ## Claims ### Claim 1 A process for treating a fiberglass-reinforced plastic waste comprising: a matrix of an unsaturated polyester resin; reinforcement glass fibers incorporated in said matrix, said process comprising the steps of: prearranging a reactor comprising a pyrolysis chamber; feeding said fiberglass-reinforced plastic waste into said pyrolysis chamber; removing oxygen from said pyrolysis chamber down to a predetermined residual oxygen concentration; creating a CO2-containing environment in said pyrolysis chamber, at a 30% minimum CO2 volume concentration; heating said fiberglass-reinforced plastic waste in said pyrolysis chamber and reaching a pyrolysis temperature set between 350° C. and 550° C.; wherein said step of removing oxygen and said step of reaching a pyrolysis temperature are carried out in such a way that said residual oxygen concentration is attained before reaching said pyrolysis temperature; maintaining said CO2-containing environment and said pyrolysis temperature in said pyrolysis chamber for a predetermined residence time, obtaining a gas mixture containing products of pyrolysis of said unsaturated polyester resin, and a solid residue comprising said glass fibers; extracting said gas mixture from said pyrolysis chamber; condensing said pyrolysis products from said gas mixture in a condensation chamber, obtaining a condensate liquid phase comprising a product of pyrolysis that is separated from the uncondensed gas, such that said organic liquid can be recycled to a production process of fiberglass-reinforced plastics as a mixture with commercial unsaturated resins; and extracting said solid residue from said pyrolysis chamber. ### Claim 2 (depends on 1) The process according to claim 1, wherein said CO2 volume concentration is higher than 50%. ### Claim 3 (depends on 1) The process according to claim 1, wherein said step of creating a CO2-containing environment, and said step of removing oxygen, are carried out at the same time by a step of maintaining a substantially pure CO2 flow through said pyrolysis chamber. ### Claim 4 (depends on 1) The process according to claim 1, wherein said step of creating a CO2-containing environment, and said step of removing oxygen, comprise alternating in said pyrolysis chamber: one or more steps of supplying an amount of an inert gas, or of substantially pure CO2, with one or more steps of creating a vacuum degree, and a final step of supplying a final amount of substantially pure CO2 at a predetermined pressure after alternating said steps of supplying and of creating a vacuum degree. ### Claim 5 (depends on 1) The process according to claim 1, wherein said residual oxygen concentration is lower than 10%. ### Claim 6 (depends on 1) The process according to claim 1, wherein said pyrolysis temperature is set between 400 and 500° C. ### Claim 7 (depends on 1) The process according to claim 1, wherein said pyrolysis temperature is set between 400° C. and 450° C. ### Claim 8 (depends on 7) The process according to claim 7, wherein said residence time is set between 1 and 2 hours. ### Claim 9 (depends on 1) The process according to claim 1, wherein said step of maintaining said CO2-containing environment and said pyrolysis temperature in said pyrolysis chamber is carried out at a pressure set between 0.2 and 20 bar absolute. ### Claim 10 (depends on 1) The process according to claim 1, wherein said step of maintaining said CO2-containing environment and said pyrolysis temperature in said pyrolysis chamber is carried out at a pressure higher than 6 bar absolute. ### Claim 11 (depends on 1) The process according to claim 1, wherein said step of maintaining said CO2-containing environment and said pyrolysis temperature in said pyrolysis chamber is carried out at a pressure higher than 73 bar absolute. ### Claim 12 (depends on 1) The process according to claim 1, wherein said unsaturated polyester resin is selected from the group consisting of: an isophthalic polyester resin; an orthophthalic polyester resin; a vinylester resin; and a combination thereof. ### Claim 13 (depends on 1) The process according to claim 1, comprising: a step of collecting a non-condensable gas left by said step of condensing said gas mixture containing pyrolysis products, said non-condensable gas including CO2, and a step of recycling said non-condensable gas into said pyrolysis chamber carried out during said step of creating a CO2-containing environment and/or during said step of maintaining the CO2-containing environment and the pyrolysis temperature. ### Claim 14 (depends on 13) The process according to claim 13, comprising a step of removing a vapor residue of said pyrolysis products from said non-condensable gas, wherein said step of removing is carried out before said step of recycling said non-condensable gas. ### Claim 15 (depends on 14) The process according to claim 14, wherein said step of removing a vapor residue of said pyrolysis products comprises a combustion step to which said non-condensable gas is fed. ### Claim 16 (depends on 13) The process according to claim 13, comprising a step of removing moisture from said non-condensable gas, wherein said step of removing moisture is carried out before said step of recycling said non-condensable gas. ### Claim 17 (depends on 16) The process according to claim 16, wherein said step of removing moisture comprises a condensation step to which said non-condensable gas is fed. ### Claim 18 (depends on 1) The process according to claim 1, comprising a step of washing said pyrolysis chamber and/or said condensation chamber with a solvent, carried out after said step of extracting said gas mixture from said pyrolysis chamber, so as to form a solution of further pyrolysis products in said solvent, and a step of removing said solution from said pyrolysis chamber. ### Claim 19 (depends on 18) The process according to claim 18, wherein said solvent is selected from the group consisting of÷ acetone; methyl-ethyl-ketone; tetrahydrofuran; and mixtures thereof. ### Claim 20 (depends on 18) The process according to claim 18, comprising: a step of separating said solvent from said further pyrolysis products, and a step of mixing said further pyrolysis products, recovered in said step of separating said solvent, with said pyrolysis products recovered in said step of condensing from said gas mixture. ### Claim 21 (depends on 18) The process according to claim 18, wherein said solvent is selected between methyl methacrylate and styrene. ### Claim 22 (depends on 21) The process according to claim 21, comprising a step of mixing said solution of said further pyrolysis products, which contains methyl-methacrylate and/or styrene, with said pyrolysis products recovered in said step of condensing from said gas mixture. ### Claim 23 (depends on 22) The process according to claim 22, wherein said step of mixing is carried out so as to obtain a mixture having a predetermined iodine number and/or viscosity. ### Claim 24 (depends on 1) The process according to claim 1, further comprising forming an article by combining the pyrolysis products, obtained after the extracting step, with an unsaturated thermosetting polyester resin. ### Claim 25 (depends on 1) The process according to claim 1, wherein said solid residue also comprises an amount of a solid organic deposit, and said process comprises a step of separating said solid organic deposit from said glass fibers. ### Claim 26 (depends on 25) The process according to claim 25, wherein said step of separating said solid organic deposit from said glass fibers comprises a step of heating and treating said solid residue in air at a treatment temperature set between 500° C. and 750° C. for a predetermined time, so as to cause a combustion of said solid organic deposit and to set said glass fibers free from said solid organic deposit. ### Claim 27 (depends on 26) The process according to claim 26, wherein said treatment temperature is set between 600° C. and 700° C. ### Claim 28 (depends on 26) The process according to claim 26, comprising: a step of collecting a combustion gas produced in said step of heating and treating said solid residue, and a step of recycling said combustion gas into said pyrolysis chamber carried out during said step of creating a CO2-containing environment and/or during said step of maintaining. ### Claim 29 (depends on 28) The process according to claim 28, comprising a step of removing moisture from said combustion gas, wherein said step of removing moisture is carried out before said step of recycling said combustion gas. ### Claim 30 (depends on 29) The process according to claim 29, wherein said step of removing moisture comprises a condensation step to which said combustion gas is fed. ### Claim 31 (depends on 1) The process according to claim 1, further comprising forming an article by combining the glass fibers of the solid residue with a polymeric material. ### Claim 32 (depends on 1) The process according to claim 1, wherein said step of prearranging a pyrolysis reactor comprises a step of arranging a bed of an inert filling material into said pyrolysis chamber, at an inlet zone of said CO2 proximate to an inlet port of said CO2, through which said CO2 is supplied into said pyrolysis chamber, said filling material arranged to allow said CO2 to flow from said inlet port to a zone in said pyrolysis chamber free from said filling material, and arranged to transmit an amount of heat to said CO2 so as to preheat said CO2. ### Claim 33 (depends on 1) The process according to claim 1, wherein said step of maintaining said CO2-containing environment and said pyrolysis temperature comprises a step of continuously feeding substantially pure CO2 into said pyrolysis chamber, and said step of extracting said gas mixture from said pyrolysis chamber is carried out continuously during said step of maintaining, in order to keep a predetermined pressure within said pyrolysis chamber. ### Claim 34 (depends on 1) The process according to claim 1, wherein said step of feeding said fiberglass-reinforced plastic waste into said pyrolysis chamber is carried out continuously during said step of maintaining. ### Claim 35 (depends on 34) The process according to claim 34, wherein said step of extracting said solid residue from said pyrolysis chamber is carried out continuously during said step of maintaining. ### Claim 36 (depends on 34) The process according to claim 34, wherein said step of continuously feeding CO2, said step of extracting, and said step of feeding said fiberglass-reinforced plastic waste are carried out in such a way that a countercurrent flow is maintained within said pyrolysis chamber of: a stream that, when entering into the pyrolysis chamber, is substantially formed by said CO2 as supplied and that, by flowing within the pyrolysis chamber, becomes richer in pyrolysis products forming said gas mixture containing pyrolysis products, on the one hand, and a solid stream turning from said fiberglass-reinforced plastic waste into said solid residue, on the other hand. ### Claim 37 A process for treating an unsaturated polyester resin waste comprising the steps of: prearranging a reactor comprising a pyrolysis chamber; feeding said unsaturated polyester resin waste into said pyrolysis chamber; removing oxygen from said pyrolysis chamber down to a predetermined residual oxygen concentration; creating a CO2-containing environment in said pyrolysis chamber, at a 30% minimum CO2 volume concentration; heating said unsaturated polyester resin waste in said pyrolysis chamber and reaching a pyrolysis temperature set between 350° C. and 550° C., wherein said step of removing oxygen and said step of reaching a pyrolysis temperature are carried out in such a way that said residual oxygen concentration is attained before reaching said pyrolysis temperature (Tp); maintaining said CO2-containing environment and said pyrolysis temperature in said pyrolysis chamber for a predetermined residence time, obtaining a gas mixture containing products of pyrolysis of said unsaturated polyester resin; and extracting said gas mixture from said pyrolysis chamber; condensing said pyrolysis products from said gas mixture in a condensation chamber, obtaining a condensate liquid phase, comprising a product of pyrolysis that is separated from the uncondensed gas, such that said organic liquid can be recycled as such to a production process of fiberglass-reinforced plastics as a mixture with commercial unsaturated resins. ### Claim 38 (depends on 24) The process according to claim 24, wherein the pyrolysis products obtained after the extracting step are present in the condensate liquid phase obtained from the condensing.