WO2024254485A1 - Production de butadiène à partir de pneus usagés - Google Patents

Production de butadiène à partir de pneus usagés Download PDF

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Publication number
WO2024254485A1
WO2024254485A1 PCT/US2024/033059 US2024033059W WO2024254485A1 WO 2024254485 A1 WO2024254485 A1 WO 2024254485A1 US 2024033059 W US2024033059 W US 2024033059W WO 2024254485 A1 WO2024254485 A1 WO 2024254485A1
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Prior art keywords
stream
product stream
ethanol
acetaldehyde
hydrogen
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English (en)
Inventor
Terrence E. Hogan
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Bridgestone Americas Tire Operations LLC
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Bridgestone Americas Tire Operations LLC
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Priority to CN202480040274.5A priority Critical patent/CN121335874A/zh
Publication of WO2024254485A1 publication Critical patent/WO2024254485A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C07C1/2072—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by condensation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/12—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by dry-heat treatment only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2317/00—Characterised by the use of reclaimed rubber

Definitions

  • Embodiments of the present invention are directed toward a process for converting used tires to butadiene monomer.
  • Butadiene monomer is polymerized to polybutadiene and butadiene copolymers such as poly(styrene-co-butadiene), poly(isoprene-co-butadiene), and poly(styrene-co-isoprene-co- butadiene). While these polymers have many uses, they are significantly used in the manufacture of tires. Used tires, on the other hand, are not easily recycled and have been landfilled or incinerated for fuel value. Methods have been proposed to thermally decompose tires into syngas, and then convert the syngas to useful materials. These methods lack industrial applicability, and therefore improvements to this general pathway are desired.
  • One or more embodiments of the present invention provide a process comprising (a) providing used tire feedstock; (b) gasifying the used tire feedstock to produce a gaseous stream, where the gaseous stream includes carbon monoxide, hydrogen, and carbon dioxide; (cj thermochemically converting at least a portion of the carbon monoxide, hydrogen, and carbon dioxide within the gaseous stream to produce a first product stream; (d) converting at least a portion of the first product stream to a second product stream, where the second product stream includes acetaldehyde and hydrogen; [e] routing a portion of the hydrogen within the second product stream to said step of thermochemically converting at least a portion of the carbon monoxide, hydrogen, and carbon dioxide within the gaseous stream; and (f) converting at least a portion acetaldehyde to butadiene monomer.
  • Still other embodiments of the present invention provide a vulcanizable composition of matter comprising the polybutadiene or butadiene copolymer prepared by the process as provided above.
  • Yet other embodiments of the present invention provide a tire component prepared from the vulcanizable composition as provided above.
  • FIG. 1 is a schematic view of a system for practicing embodiments of the invention.
  • Embodiments of the invention are based, at least in part, on the discovery of a process for consuming used tires in the production of butadiene and optionally acetaldehyde.
  • used tires are thermally decomposed to form a gaseous stream that is then converted to ethanol by thermochemical processes.
  • the ethanol is then converted to acetaldehyde, which reaction produces a hydrogen by-product stream that is used in the upstream production of ethanol.
  • the acetaldehyde can be purified and/or converted to butadiene monomer by reacting it with ethanol. It has been discovered that the overall process efficiency and economics depends on the amount of hydrogen available during the production of ethanol.
  • the present invention which provides down-stream production of hydrogen in the absence of carbon by-products, provides for overall carbon efficiency.
  • This is particularly advantageous in the present invention since used tires are the primary feedstock, and used tires include a higher molar ratio of carbon to hydrogen than do other feedstock such as biomass.
  • the butadiene is polymerized to form polybutadiene or butadiene copolymers that are used in the preparation of vulcanizable compositions that are fabricated into tire components.
  • System 20 includes a thermal decomposition unit 31 that is followed in series by a reactor 51, which may be referred to as a thermo-chemical reactor 51.
  • Thermal decomposition unit 31 is in fluid communication, either directly or indirectly, with reactor 51 via gas stream conduit 33.
  • An acetaldehyde synthesis unit 71 which may also be referred to as acetaldehyde production unit 71, which is downstream of reactor 51, is in fluid communication, either directly or indirectly, with reactor 51 via ethanol product conduit 53.
  • a butadiene synthesis unit 91 which may also be referred to as butadiene production unit 91, is downstream of acetaldehyde synthesis unit 71 and is in fluid communication, either directly or indirectly, with acetaldehyde synthesis unit 71 via acetaldehyde product conduit 73.
  • Acetaldehyde synthesis unit 71 is also in fluid communication, either directly or indirectly, with hydrogen by-product conduit 75, which is in fluid communication with reactor 51.
  • thermal decomposition unit 31 is adapted to receive tire feedstock, and optionally co-feed, and thermally treat the same to produce a gaseous stream that includes carbon monoxide (CO), hydrogen gas (H2), and optionally carbon dioxide (CO2).
  • Reactor 51 includes one or more catalysts that are adapted to convert the carbon monoxide, hydrogen gas, and optionally carbon dioxide to ethanol in the presence of heat.
  • the ethanol is transferred to acetaldehyde synthesis unit 71 where the ethanol is converted to acetaldehyde with the byproduct production of hydrogen.
  • the acetaldehyde can be transferred to butadiene synthesis unit 91 where the acetaldehyde is converted to butadiene.
  • the byproduct hydrogen from acetaldehyde synthesis unit 71 can be transferred to reactor 51 via conduit 75 or via conduit 99, which is in fluid communication, either directly or indirectly, with butadiene synthesis unit 91.
  • the gaseous stream exiting thermal decomposition unit 31 is treated prior to being introduced to reactor 51.
  • the gaseous product stream can be cooled within a heat exchanger 41.
  • heat exchanger can receive cooling water from one or more downstream processes or units such as a distillation column 61, which will be described in greater detail below.
  • the gaseous stream can be treated to remove one or more constituents prior to being introduced to reactor 51.
  • the gaseous stream can be treated with a scrubber 45.
  • carbon monoxide, hydrogen, and optionally carbon dioxide are converted to ethanol within reactor 51.
  • reactor 51 can include external inputs of hydrogen gas and water.
  • the ethanol produced in reactor 51 is transferred from reactor 51 within a crude product via conduit 53.
  • the crude ethanol product stream can be filtered as it exits reactor 51 or downstream thereof by employing, for example, a filtration unit 55.
  • the crude ethanol stream Prior to introducing the crude ethanol product stream to acetaldehyde synthesis unit 71, the crude ethanol stream can be concentrated or otherwise purified.
  • ethanol can be separated from the crude ethanol product stream within a distillation unit 61 where the overhead (i.e. distillate), which includes concentrated ethanol, is directed to acetaldehyde synthesis unit 71 via conduit 65 and/or butadiene production unit 91 via conduit 67, and the bottoms from the distillation can be recycled back to, for example, reactor 51 via aqueous bottoms conduit 63.
  • Ethanol is converted to acetaldehyde within acetaldehyde production unit 71, which may be referred to as acetaldehyde synthesis unit 71 or acetaldehyde reactor 71.
  • Acetaldehyde synthesis produces a crude product stream that includes acetaldehyde and hydrogen bybyproduct.
  • the crude acetaldehyde product stream can be transferred, either directly or indirectly, through conduit 73, to butadiene synthesis unit 91.
  • the crude acetaldehyde is transferred, either directly or indirectly, via conduit 79, to a separation unit 81 (e.g.
  • distillation column which may also be referred to as purification unit 81
  • purification unit 81 where the by-product hydrogen is separated from the acetaldehyde.
  • the by-product hydrogen can be routed, either directly or indirectly, back to reactor 51 via conduit 75.
  • the acetaldehyde stream from separation unit 81 can be routed to market sources via conduit 83 or to butadiene reactor 91 via conduit 85.
  • Acetaldehyde is converted to butadiene within synthesis unit 91 to produce a crude butadiene product stream, which can exit synthesis unit 91, directly or indirectly, via conduit 93.
  • butadiene is separated from the crude butadiene stream within a distillation column 95 to produce a purified butadiene stream that can be removed from the system via conduit 97.
  • purification unit 95 e.g. distillation unit 95
  • acetaldehyde synthesis unit 71 and/or butadiene production unit 91 can be supplemented with an external source of ethanol via conduit 77.
  • This external source can be from, for example, the fermentation of agricultural crops such as corn.
  • this external source can be from cellulose ethanol produced from grasses, wood, algae, or other plants.
  • gasification unit 31 and reactor 51 are located at a first facility, and acetaldehyde production unit 71 and butadiene production unit 91 are located at a second facility.
  • the first facility e.g. gasification 31 and reactor 51
  • the second facility e.g. acetaldehyde reactor 71 and butadiene reactor 91
  • a pipeline that can transport ethanol from the first facility to the second facility.
  • ethanol can be transported from the first facility to the second facility via other forms of transportation including truck or railcar.
  • hydrogen produced at acetaldehyde reactor 71 can be communicated back to reactor 51 (i.e. from the second facility to the first facility) by pipeline, tanker, truck, or through exchange with local sources of hydrogen.
  • indirect fluid communication will be understood to encompass these connections between the various units.
  • the feedstock fed to thermal decomposition unit 31 includes tire feedstock from used tires, which may also be referred to as used tire feedstock or simply tire feedstock.
  • tire feedstock may include vulcanized polymer, carbon black filler, silica, resins, oils, fibrous yarn, and metal.
  • the vulcanized polymer may include the sulfur-crosslinked residue of natural rubber and/or one or more synthetic elastomers including diene polymers and copolymers.
  • the used tire feedstock may include shredded or otherwise ground tires with one or more constituents of the used tire removed.
  • the tire feedstock may be treated to remove metal by methods known in the art (e.g. magnetic separation).
  • the used tire feedstock may be optionally treated to remove fibrous reinforcement such as fiber yard or cord, which the skilled person understands is often found in conjunction with the vulcanized rubber within many tire components.
  • the used tire feedstock may be optionally treated to remove inorganic materials such as silica filler, which the skilled person appreciates is often found used tire components.
  • the tire feedstock can be processed into tire shreds, tire chips, or ground or crumb rubber and fed to the thermal decomposition unit.
  • the tire feedstock is characterized by relatively low amounts of metal, which low amounts may result from pre-treatment of the tire feedstock to remove at least a portion of the metal that is typically present in used tires.
  • the tire feedstock may include less than 25 wt %, in other embodiments less than 15 wt %, and in other embodiments less than 1 wt % metal based on the entire weight of the feedstock fed to thermal decomposition in accordance with the present invention.
  • the tire feedstock is characterized by relatively low amounts of fibrous yarn or cord, which low amounts may result from pre-treatment of the tire feedstock to remove at least a portion of the fibrous yarn or cord that is typically present in used tires.
  • the tire feedstock following pre-treatment, includes less than 5 wt %, in other embodiments less than 4 wt %, in other embodiments less than 3 wt %, in other embodiments less than 2 wt %, and in other embodiments less than 3 wt % fibrous yarn or cord based on the entire weight of the feedstock fed to thermal decomposition in accordance with the present invention.
  • the tire feedstock is characterized by relatively low amounts of inorganic filler (e.g. silica), which low amounts may result from pre-treatment of the tire feedstock to remove at least a portion of the inorganic filler that is typically present in used tires.
  • the tire feedstock following pre-treatment, includes less than 30 wt %, in other embodiments less than 20 wt %, in other embodiments less than 10 wt %, and in other embodiments less than 5 wt % inorganic filler based on the entire weight of the feedstock fed to thermal decomposition in accordance with the present invention.
  • the used tire feedstock includes tire remains from passenger tires. In other embodiments, the used tire feedstock includes tire remains from nonpassenger tires such as, but not limited to, truck and bus tires, off-road vehicle tires, agricultural tires, and race tires.
  • the used tires are mechanically treated (e.g. ground or shredded) to form a ground or shredded material (i.e. the feedstock is ground or shredded).
  • This ground or shredded material i.e. the feedstock
  • crumb may be characterized by an advantageous compacted density.
  • the feedstock may have a compacted density of greater than 640 kg/m 3 , in other embodiments greater than 720 kg/m 3 , and in other embodiments greater than 770 kg/m 3 , where density is determined by ASTM D 698-07.
  • the feedstock provided to the thermal decomposition unit includes used tires and optionally complementary feedstock.
  • the complementary feedstock which may also be referred to as co-feed, includes carbonaceous materials other than the tire feed stock.
  • Carbonaceous material refers to any carbon material whether in solid, liquid, gas, or plasma state.
  • Non-limiting examples of carbonaceous materials include carbonaceous liquid product, industrial liquid recycle, municipal solid waste (MSW or msw) including municipal solid waste with higher biomass content and/or with decreased recyclable material content, urban waste, agricultural material, forestry material, wood waste, construction material, vegetative material, industrial waste, fermentation waste, petrochemical coproducts, alcohol production coproducts, coal, plastics, waste plastic, coke oven tar, lignin, black liquor, polymers, waste polymers, polyethylene terephthalate (PETA), polystyrene (PS), sewage sludge, animal waste, crop residues, energy crops, forest processing residues, wood processing residues, livestock wastes, poultry wastes, food processing residues, ethanol coproducts, spent grain, spent microorganisms, municipal waste, construction waste, demolition waste, biomedical waste, hazardous waste, or their combinations.
  • MSW or msw municipal solid waste with higher biomass content and/or with decreased recyclable material content
  • urban waste agricultural material, forestry material, wood waste, construction
  • the carbonaceous material includes biomass.
  • the biomass is bagasse including, but not limited to, the bagasse of sugar cane, sorghum, and guayule plant.
  • the feedstock includes a blend of used tires and municipal solid waste, wherein the municipal solid waste can include biomass.
  • the feedstock includes used tires and municipal solid waste that is substantially exclusive of biomass (i.e. substantially petroleum-based solid municipal waste).
  • the feedstock includes used tires and biomass.
  • the feedstock includes used tires and municipal solid waste that has had most of the recyclable plastics removed (i.e. substantially exclusive of recyclable plastics).
  • recyclable glass and metal is also substantially removed from the municipal solid waste component.
  • the guayule bagasse is produced as the result of a process to extract rubber and resin from the guayule plant, such as described in U.S. Publication No. 2022/0356273 Al, which is incorporated herein by reference. Methods for the desolventization of guayule bagasse are described in U.S. Patent No. 10,132,563, which is also incorporated herein by reference.
  • the guayule bagasse contains no more than 1 wt % organic solvent (based upon the total weight of the dried bagasse).
  • the dried bagasse contains no more than 0.5 wt % organic solvent (based upon the total weight of the dried bagasse).
  • the dried bagasse may contain a quantity of water and higher boiling point terpenes. In certain embodiments, the total quantity of water and higher boiling point terpenes in the dried bagasse may be higher than the content of organic solvents.
  • the co-feed e.g. biomass or municipal waste
  • the co-feed may be characterized by a compacted density of less than 600 kg/m 3 , in other embodiments less than 580 kg/m 3 , and in other embodiments less than 560 kg/m 3 , where density is determined by ASTM D 698-07.
  • the feedstock may be characterized by the amount of co-feed (e.g. biomass or municipal waste).
  • the feedstock includes from about 0_to about 95, in other embodiments from about 1 to about 75, and in other embodiments from about 2 to about 55 wt % co-feed with the balance including used tire.
  • the feedstock includes less than 95, in other embodiments less than 80, and in other embodiments less than 70 wt % co-feed.
  • the feedstock includes greater than 10, in other embodiments greater than 20, in other embodiments greater than 30, in other embodiments greater than 40, in other embodiments greater than 50, and in other embodiments greater than 70 wt % used tires, with the balance including complementary feedstock.
  • the feedstock (which includes tire feedstock and optionally co-feed) are thermally decomposed into gaseous streams including hydrogen, carbon monoxide, and optionally carbon dioxide by employing techniques that are generally known in the art.
  • these processes may include gasification processes, and it is also known that these processes can be tailored to control the chemical nature of the resulting gaseous stream.
  • the degree of combustion can be controlled by controlling the amount of oxygen present during thermal decomposition.
  • the step of thermal decomposition takes place in a substantially inert environment.
  • Processes that may be used for the thermal decomposition step may include pyrolysis reactions as disclosed in U.S. Publication Nos. 20210207037; 20190295734; 20190249089; 20180273415; 20170009162; 20170002271; 20160107913; 20160068773; 20160024404; 20140182205; 20140157667; and 20140100294, which are incorporated herein by reference.
  • the feedstock includes both tire feedstock and co-feed
  • the tire feedstock and the co-feed can be introduced to the same thermal decomposition unit simultaneously.
  • the tire feedstock and the co-feed can be pre-mixed at a desired ratio to form the feedstock that is fed to the thermal decomposition unit.
  • separate streams of tire feedstock and co-feed can be separately and individually fed to the thermal decomposition unit at a desired rate.
  • the two feedstocks i.e. the tire feedstock and the co-feed
  • the two feedstocks can be treated within separate thermal decomposition units operating in parallel, and the then the gaseous streams produced by the respective units can be combined to attain the desired ratio of gaseous constituents.
  • the gaseous product stream produced by thermal decomposition unit 31 includes carbon monoxide, hydrogen and optionally carbon dioxide.
  • the gaseous product stream includes from about 5 to about 50, or in other embodiments from about 7 to about 25, or in other embodiments from about 8 to about 15 volume percent carbon dioxide.
  • the gaseous product stream includes from about 10 to about 85, or in other embodiments from about 20 to about 65, or in other embodiments from about 25 to about 45 volume percent hydrogen.
  • the gaseous product stream includes from about 20 to about 85, or in other embodiments from about 30 to about 75, or in other embodiments from about 40 to about 60 volume percent carbon monoxide.
  • the gaseous product stream produced by thermal decomposition includes from about 40 to about 80 wt %, in other embodiments from about 45 to about 75 wt %, and in other embodiments from about 50 to about 70 wt % carbon (i.e. carbon within carbon-based compounds] based on the total weight of the gaseous product stream.
  • the gaseous stream is conditioned (i.e. treated] prior to providing the stream to the reactor 21.
  • the gaseous product stream from thermal decomposition, which is carried by conduit 33 may be pressurized.
  • pressurization of the gaseous stream achieves sufficient pressure to overcome counter forces within the reactor. As the skilled person understands, this will permit flow of the gas through the reactor and allow inert gases (e.g. nitrogen] within the gaseous stream to enter the head space of the reactor.
  • the gaseous stream is pressurized to a pressure of from about 5 to about 20 barr.
  • the gaseous stream can be cooled at heat exchanger 41.
  • heat exchanger 41 may include a water-cooled unit.
  • the gaseous stream is cooled to a temperature below that which would otherwise have a deleterious impact on the microorganism culture within the reactor.
  • the gaseous stream is cooled to a temperature of from about 25 to about 45 °C prior to delivery to the reactor.
  • the gaseous stream can be treated with scrubber 45 prior to being introduced to the reactor.
  • this may include the use of a catalyst (e.g. iron oxide] to remove sulfur compounds such as hydrogen sulfide.
  • the stream may also be treated to remove acids (e.g. treatment with calcium or sodium carbonate with particular interest in removing hydrogen cyanides].
  • thermochemical techniques exist to convert syngas to ethanol.
  • two-step processes exist whereby syngas can be converted to methanol using a hydrogen to carbon monoxide ratio of 2: 1. These reactions typically take place in the gas phase using copper-based catalysts.
  • the resulting product stream which is typically saturated with water, can be purified by using known distillation techniques.
  • the methanol can then be catalytically converted to ethanol.
  • One-step catalytic techniques are also known.
  • An exemplary thermochemical process for converting syngas to ethanol is described in U.S. Patent No. 9,115,046, which is incorporated herein by reference.
  • ethanol exits reactor 51 within an ethanol product stream.
  • This ethanol product stream can be treated, such as filtered, at unit 55.
  • the ethanol-containing product stream can be treated to separate ethanol from the other constituents within the stream. This may include distilling the ethanol-containing stream within separation unit 61. According to these embodiments, ethanol can be collected as an overhead stream that may be characterized by an ethanol concentration of greater than 80 wt %, in other embodiments greater than 90 wt %, and in other embodiments greater than 93 wt %. In these or other embodiments, the overhead stream (i.e. the ethanol-containing stream] may include less than 10 wt %, in other embodiments less than 8 wt %, and in other embodiments less than 1 wt % water.
  • the overhead ethanol stream can optionally be further treated to purify the ethanol stream prior to introducing the ethanol to acetaldehyde production unit 71.
  • the ethanol stream can be dehydrated or dried by treating the stream in one or more water adsorption beds that include a drying material such as molecular sieves.
  • ethanol is converted to acetaldehyde within production unit 71.
  • substantially all of the ethanol produced in reactor 51 i.e. substantially all of the ethanol within the ethanol-containing product stream
  • ethanol obtained from outside of the process of the present invention e.g. ethanol from fermentation of agricultural crops
  • the weight ratio of ethanol supplied to acetaldehyde production unit 71 from reactor 51 to the ethanol supplied to acetaldehyde production unit 71 from other sources is from about 1:0 to about 1:10, in other embodiments from about 1:0.3 to about 1:7, and in other embodiments from about 1:1 to about 1:5.
  • acetaldehyde involves the partial dehydrogenation of ethanol to yield a hydrogen by-product stream.
  • the hydrogen can be routed to reactor 51, which can advantageously offset the hydrogen deficiencies of the process.
  • reactor 51 can advantageously offset the hydrogen deficiencies of the process.
  • ethanol from sources outside of the reactor process (i.e. outside of reactor 51) will further alleviate hydrogen deficiencies within reactor 51 if the additional ethanol is converted to acetaldehyde, which will allow for greater production of hydrogen.
  • the ethanol undergoes dehydrogenation at elevated temperatures over an appropriate catalyst, such as a copper-based catalyst.
  • an appropriate catalyst such as a copper-based catalyst.
  • the reaction can take place within a fixed-bed reactor.
  • dehydrogenation of ethanol within unit 71 takes place at a temperature of from about 200 to about 350 °C, or in other embodiments from about 250 to about 300.
  • ethanol can be converted to acetaldehyde by oxidative dehydrogenation of the ethanol.
  • the conversion of ethanol to acetaldehyde may proceed by partial oxidation of the ethanol in an exothermic reaction. In this partial oxidation process, the reaction may be conducted over a silver catalyst at about 500 °C to about 650 °C.
  • the conversion of ethanol to acetaldehyde may include avoiding or inhibiting the production of acetic acid relative to the acetaldehyde. This can be accomplished by selecting catalysts and/or reaction conditions that are known to avoid the production of acetic acid relative to the acetaldehyde.
  • the conversion of ethanol to acetaldehyde takes place in the absence of evaporating the acetaldehyde. In one or more embodiments, the conversion of ethanol to acetaldehyde takes place at relatively low pressure and in the gas-phase as to increase selectivity for acetaldehyde.
  • acetaldehyde produced in unit 71 is converted to butadiene monomer within butadiene production unit 91.
  • butadiene production includes reacting ethanol and acetaldehyde to produce 1,3-butadiene by utilizing reaction techniques generally known in the art as for example described by Zhang, Mechanistic Insight into the Meerwein-Ponndorf-Verley Reaction and Relative Side Reactions over MgO in the Process of Ethanol to 1,3-butadiene: a DFT Study, IND. ENG. CHEM. RES., 2021, 60, 2871- 2880.
  • this reaction can be conducted over an appropriate catalyst, such as a tantalum-promoted porous silica catalyst, at elevated temperatures.
  • an appropriate catalyst such as a tantalum-promoted porous silica catalyst
  • other catalysts for converting the acetaldehyde and ethanol to butadiene are known in the art and can be used including tantalum oxide, zirconium oxide, silver oxide and combinations thereof. This process may be referred to as an Ostromislensky process.
  • this reaction is conducted within a fixed-bed reactor operating at temperatures of from about at 300 to about 450 °C, or in other embodiments, or in other embodiments from about 350 to about 400.
  • the process may include supplementing the ethanol-acetaldehyde mixture with additional ethanol and/or acetaldehyde as to achieve a desirable ratio.
  • the reactant feed into butadiene production unit 91 includes an ethanol to acetaldehyde molar ratio (i.e. moles of ethanol to moles of acetaldehyde) of at least 1:1, in other embodiments at least 2:1, in other embodiments at least 2.5:1, in other embodiments at least 4:1, and in other embodiments within the range of from about 1:1 to about 5:1.
  • an ethanol to acetaldehyde molar ratio i.e. moles of ethanol to moles of acetaldehyde
  • the feed into butadiene production unit 91 is characterized by low levels of impurities
  • the feed stream into butadiene production unit 91 includes less than 10, in other embodiments less than 5, and in other embodiments less than 2 wt % impurities based on the total weight of the input stream.
  • the crude butadiene stream exiting butadiene reactor 91 via conduit 93 generally includes 1,3-butadiene monomer, unreacted ethanol, unreacted acetaldehyde, water, which is a by-product of the reaction, and other side products.
  • yield of 1,3- butadiene, based upon acetaldehyde is greater than 20 mol %, in other embodiments greater than 30 mol %, and in other embodiments greater than 40 mol %.
  • yield of 1,3-butadiene, based upon acetaldehyde is less than 70 mol %, in other embodiments less than 60 mol %, and in other embodiments less than 55 mol %.
  • the crude butadiene product stream undergoes a first separation, which may include a distillation.
  • a first separation which may include a distillation.
  • butadiene is separated as an overhead stream and the remaining constituents of the stream are separated as a bottoms stream.
  • the bottoms stream can then undergo further separation to separate the ethanol and acetaldehyde from the water and other constituents of the stream.
  • the ethanol and acetaldehyde which can be separated as an overhead stream, can then be recycled back to butadiene production unit 91 for conversion to butadiene.
  • ethanol within the ethanol-containing stream can be converted to butadiene (e.g. 1,3-butadiene) by a one-step synthesis, which may also be referred to as a direct synthesis.
  • the direct synthesis of ethanol to butadiene takes place as a condensation reaction in the presence of a polyfunctional catalyst, including those disclosed in U.S. Patent No. 8,921,635, which is incorporated herein by reference.
  • Another known synthesis for converting ethanol directly to butadiene is the Lebedev process.
  • Still other processes for directly converting ethanol to butadiene include those marketed by ETB Catalytic Technologies and those techniques marketed by Synthos.
  • the direct conversion of ethanol to butadiene may include the use of a two-stage extractive distillation that utilizes n-methyl pyrrolidone (NMP) as solvent.
  • Direct conversion techniques may also include conventional distillation for recovering the butadiene.
  • the butadiene monomer (e.g. 1,3-butadiene) produced by the methods of this invention can be used in the production of polybutadiene or butadiene copolymers (which may also be referred to as polybutadiene copolymers).
  • these polymers may be referred to as circular synthetic rubber, or circular synthetic polybutadiene to butadiene copolymers.
  • this circular synthetic rubber can be used in the manufacture of tire components.
  • practice of the present invention provides a method by which waste material, in particular that waste material from used tires, is converted back to useful tires. In other words, a tire recycling or tire circularity method is provided.
  • polystyrene resin polystyrene resin
  • polybutadiene or polybutadiene copolymers from butadiene monomer can be accomplished by using several synthetic routes (i.e. polymerization mechanisms and techniques].
  • the monomer can be polymerized by free-radical emulsion polymerization, anionic polymerization, or coordination catalysis using, for example, nickel or neodymium-based catalyst systems.
  • comonomers that can be copolymerized with butadiene to form polybutadiene copolymers include, but are not limited to, vinyl aromatic monomer such as styrene, as well as other diene monomer such as isoprene.
  • the comonomer is a sustainable comonomer.
  • styrene can be obtained from bio-synthesized feedstock, such as bioethanol, that is subsequently converted to styrene; see, e.g. U.S. Patent No. 9,663,445.
  • styrene can be synthesized from bio-based materials such as cinnamic acid or hydrocinnamic acid; see, U.S. Patent No. 9,868,853.
  • bio-based materials such as cinnamic acid or hydrocinnamic acid
  • examples include styrene obtained from the depolymerization of polystyrene from post-consumer waste; see U.S. Publication No. 2022/0411351.
  • the skilled person also understands that styrene can be obtained from those processes that are mass balanced to qualify as bio-based, bio-circular, or circular as designated by the International Sustainability and Carbon Certification ISCC.
  • the polybutadiene polymers prepared by polymerizing the butadiene of the present invention have a relatively high percentage of mer units deriving from the butadiene produced by the invention, and therefore the polybutadiene polymers of this invention have a relatively high sustainable content.
  • the polybutadiene polymers synthesized by polymerizing the butadiene of the present invention include greater than 50 mol %, in other embodiments greater than 60 mol %, in other embodiments greater than 70 mol %, in other embodiments greater than 80 mol %, in other embodiments greater than 90 mol %, in other embodiments greater than 95 mol %, and in other embodiments greater than 99 mol % sustainable mer units, which obtained from polymerization of butadiene obtained by the present invention (i.e. mer units obtained from monomer that is synthesized from a gaseous stream obtained by gasification of carbonaceous materials].
  • the resulting polybutadiene copolymer has a relatively high sustainable content.
  • the polybutadiene copolymers synthesized by polymerizing the butadiene of the present invention together with sustainable comonomer include greater than 50 mol %, in other embodiments greater than 60 mol %, in other embodiments greater than 70 mol %, in other embodiments greater than 80 mol %, in other embodiments greater than 90 mol %, in other embodiments greater than 95 mol %, and in other embodiments greater than 99 mol % sustainable mer units (i.e. mer units that are obtained from monomer synthesized from a gaseous stream obtained by gasification of carbonaceous materials and other sustainable comonomer).
  • the polymers synthesized from butadiene monomer produced by embodiments of the invention may be referred to as vulcanizable polymers, or as elastomeric polymers, and generally include polydienes and polydiene copolymers.
  • Specific of polymers that can be produced and used in the manufacture of tires include, but are not limited to, polybutadiene, poly(styrene-co- butadiene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), and functionalized derivatives thereof.
  • the polybutadiene and polybutadiene copolymers produced by the present invention exhibit excellent viscoelastic properties and are particularly useful in the manufacture of various tire components including, but not limited to, tire treads, sidewalls, subtreads, and bead fillers. These polymers can be used as all or part of the elastomeric component of a tire stock. When the polymers produced by the present invention are used in conjunction with other vulcanizable polymers to form the elastomeric component of a tire stock, these other vulcanizable polymers may include natural rubber, synthetic rubbers, and mixtures thereof.
  • Examples of synthetic rubber include polyisoprene, poly(styrene-co-butadiene), and other polybutadienes with low and/or cis-l,4-linkage content, poly(styrene-co-butadiene-co-isoprene), and mixtures thereof.
  • the polymers of this invention can also be used in the manufacture of hoses, belts, shoe soles, window seals, other seals, vibration damping rubber, and other industrial products.
  • Practice of the present invention not only offers a method for recycling tires by employing used tires as a feedstock to produce polymer that can be formulated back into tires, but the practice of the present invention also advantageously provides a method whereby a tire is produced that has a relatively high content of sustainable constituents, which include recycled materials, naturally-derived materials and/or materials synthesized from bio-synthesized feedstock or bio-based materials.
  • these tires or tire components include threshold amounts of circular synthetic rubber while being characterized by high sustainable content.
  • the tires or tire components of the present invention can include greater than 40 wt %, in other embodiments greater than 50 wt %, and in other embodiments greater than 60 wt % sustainable materials.
  • the tire or tire components include from about 40 to about 90 wt %, in other embodiments from about 45 to about 85 wt %, and in other embodiments from about 50 to about 80 wt % sustainable material.
  • the rubber component of the tires or tire components of the present invention include greater than 10 wt %, in other embodiments greater than 20 wt %, in other embodiments greater than 30 wt %, in other embodiments greater than 40 wt %, in other embodiments greater than 45 wt %, and in other embodiments greater than 50 wt % circular synthetic rubber, which includes synthetic rubber produced according to embodiments of the present invention.
  • the vulcanizable compositions of this invention include a rubber component.
  • This rubber component includes the circular synthetic rubber produced according to aspects of this invention.
  • the rubber component may also include other synthetic rubber, such as synthetic rubber that derives from petroleum-based raw materials and has not been recycled, synthetic rubber that derives from other sustainable processes, as well as natural rubber.
  • natural rubber is synthesized by and obtained from plant life.
  • natural rubber can be obtained from Hevea rubber trees, guayule shrub, gopher plant, mariola, rabbitbrush, milkweeds, goldenrods, pale Indian plantain, rubber vine, Russian dandelions, mountain mint, American germander, and tall bellflower.
  • Other synthetic polymers can include, without limitation, synthetic polyisoprene, polybutadiene, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co- propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co- butadiene], poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, and mixtures thereof.
  • These elastomers can have a myriad of macromolecular structures including linear, branched, and star-shaped structures.
  • the rubber compositions of this invention include from about 30 to about 65 wt %, in other embodiments from about 35 to about 60 wt %, and in other embodiments from about 40 to about 55 wt % elastomer, based on the total weight of the tire component.
  • the rubber compositions include fillers such as organic and inorganic fillers. Examples of organic fillers include carbon black and starch. Examples of inorganic fillers include silica, aluminum hydroxide, magnesium hydroxide, mica, talc (hydrated magnesium silicate), and clays (hydrated aluminum silicates). In certain embodiments, a mixture of different fillers may be advantageously employed.
  • the amount of total filler employed in the rubber compositions can be up to about 150 parts by weight per 100 parts by weight of rubber (phr), with about 30 to about 125 phr, or about 40 to about 110 phr being typical. In certain embodiments the total filler content is greater than about 100 phr. In other embodiments, the total filler content is from about 50 to about 100 phr, and in in further embodiments from about 55 to about 95 phr.
  • carbon blacks include furnace blacks, channel blacks, and lamp blacks. More specific examples of carbon blacks include super abrasion furnace blacks, intermediate super abrasion furnace blacks, high abrasion furnace blacks, fast extrusion furnace blacks, fine furnace blacks, semi-reinforcing furnace blacks, medium processing channel blacks, hard processing channel blacks, conducting channel blacks, and acetylene blacks.
  • the carbon blacks may have a surface area (EMSA) of at least 20 m 2 /g and in other embodiments at least 35 m 2 /g; surface area values can be determined by ASTM D-1765 using the cetyltrimethylammonium bromide (CTAB) technique.
  • the carbon blacks maybe in a pelletized form or an unpelletized flocculent form. The preferred form of carbon black may depend upon the type of mixing equipment used to mix the rubber compound.
  • carbon black can be sourced from a recycled material.
  • Such recycled material can include reclaimed or recycled vulcanized rubber, whereby the vulcanized rubber is typically reclaimed from manufactured articles such as a pneumatic tire, an industrial conveyor belt, a power transmission belt, and a rubber hose.
  • the recycled carbon black may be obtained by a pyrolysis process or other methods known for obtaining recycled carbon black.
  • a recycled carbon black can be formed from incomplete combustion of recycled rubber feedstock or rubber articles.
  • the recycled carbon black can be formed from the incomplete combustion of feedstock including oil resulting from the tire pyrolysis process.
  • the carbon blacks utilized in the preparation of the vulcanizable elastomeric compositions can be in pelletized form or an unpelletized flocculent mass.
  • the amount of carbon black employed in the rubber compositions can be up to about 75 parts by weight per 100 parts by weight of rubber (phr), with about 5 to about 60 phr, or about 10 to about 55 phr being typical.
  • the rubber composition can further include filler in the form of one or more recycled rubbers in a particulate form.
  • Recycled particulate rubber is typically broken down and reclaimed (or recycled) by any of a plurality of processes, which can include physical breakdown, grinding, chemical breakdown, devulcanization, cryogenic grinding, a combination thereof, etc.
  • the term recycled particulate rubber can relate to both vulcanized and devulcanized rubber, where devulcanized recycle or recycled rubber (reclaim rubber) relates to rubber which has been vulcanized, ground into particulates and may have further undergone substantial or partial devulcanization.
  • the recycled particulate rubber used in the rubber composition is essentially free of recycled rubber resulting from devulcanization.
  • the "recycled particulate rubber” comprises cured, i.e., vulcanized (crosslinked) rubber that has been ground or pulverized into particulate matter having a mean average particle size as discussed below.
  • Certain silicas may be considered sustainable materials.
  • Some commercially available silicas which may be used as sustainable materials for the current invention include Hi-Sil 215,
  • Hi-Sil 233, and Hi-Sil 190 PPG Industries, Inc.; Pittsburgh, Pa.
  • Other suppliers of commercially available silica include Grace Davison (Baltimore, Md.), Degussa Corp. (Parsippany, NJ.), Rhodia Silica Systems (Cranbury, N.J.), andJ.M. Huber Corp. (Edison, NJ.).
  • Other sustainable silicas include those derived from rice husk ash.
  • silicas may be characterized by their surface areas, which give a measure of their reinforcing character.
  • the Brunauer, Emmet and Teller (“BET”) method (described in J. Am. Chem. Soc., 1939, vol. 60, 2 p. 309-319) is a recognized method for determining the surface area.
  • the BET surface area of silica is generally less than 450 m 2 /g.
  • Useful ranges of surface area include from about 32 to about 400 m 2 /g, about 100 to about 250 m 2 /g, and about 130 to about 240 m 2 /g, and about 170 to about 220 m 2 /g.
  • the silica may have a BET surface area of 190 to about 280 m 2 /g.
  • the pH’s of the silicas are generally from about 5 to about 7 or slightly over 7, or in other embodiments from about 5.5 to about 6.8.
  • a coupling agent and/or a shielding agent may be added to the rubber compositions during mixing in order to enhance the interaction of silica with the elastomers.
  • a coupling agent and/or a shielding agent are disclosed in U.S. Patent Nos.
  • the amount of silica employed in the rubber compositions can be from about 1 to about 150 phr or in other embodiments from about 5 to about 130 phr.
  • the useful upper range is limited by the high viscosity imparted by silicas.
  • the silica employed in the rubber composition is derived from rice husk ash only, and in other embodiments the rubber compositions do not include silica from non-rice husk ash derived processes.
  • silica is used together with carbon black, the amount of the silica or carbon black individually can be as low as about 1 phr.
  • the amounts of coupling agents and shielding agents range from about 4 wt % to about 20 wt % based on the weight of silica used.
  • the weight ratio or silica to total filler may be from about 5 wt % to about 99 wt % of the total filler, in other embodiments from about 10 wt % to about 90 wt % of the total filler, or in yet other embodiments from about 50 wt % to about 85 wt % of the total filler.
  • the silica and carbon black fillers employed in the rubber composition are selected from the group consisting of sustainable pyrolysis carbon black and/or rice husk ash derived silica.
  • a multitude ofrubber curing agents (also called vulcanizing agents) maybe employed, including sulfur or peroxide-based curing systems. Curing agents are described in Kirk-Othmer, ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, Vol. 20, pgs. 365-468, (3 rd Ed. 1982), particularly Vulcanization Agents and Auxiliary Materials, pgs. 390-402, and A.Y. Coran, Vulcanization, ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, (2 nd Ed. 1989), which are incorporated herein by reference. Vulcanizing agents may be used alone or in combination.
  • Other ingredients that are typically employed in rubber compounding may also be added to the rubber compositions. These include accelerators, accelerator activators, oils, plasticizer, waxes, scorch inhibiting agents, processing aids, zinc oxide, tackifying resins, reinforcing resins, fatty acids such as stearic acid, peptizers, and antidegradants such as antioxidants and antiozonants.
  • oils sustainable oils, which include plant-based oils and bio-based oils
  • Plant-based oils may include plant-based triglycerides.
  • Exemplary oils include, without limitation, palm oil, soybean oil (also referred to herein as soy oil), rapeseed oil, sunflower seed, peanut oil, cottonseed oil, oil produced from palm kernel, coconut oil, olive oil, corn oil, grape seed oil, hemp oil, linseed oil, rice oil, safflower oil, sesame oil, mustard oil, flax oil.
  • oils obtained from beech nuts, cashews, mongongo nuts, macadamia nuts, pine nuts, hazelnuts, chestnuts, acorns, almonds, pecans, pistachios, walnuts, or brazil nuts.
  • these oils can be produced by any suitable process such as mechanical extraction (e.g., using an oil mill), chemical extraction (e.g., using a solvent, such as hexane or carbon dioxide), pressure extraction, distillation, leaching, maceration, purification, refining, hydrogenation, sparging, etc.
  • Bio-based oils can include oils produced by a recombinant cell.
  • bio-oils produced by recombinant cells can be produced using a select strain of algal cells that are fed with a supply of sugars (e.g., sucrose) and then allowed to ferment and produce a bio-oil with a selected profile; after sufficient growth or fermentation has taken place, the bio-oil is isolated from the cells and collected.
  • sugars e.g., sucrose
  • the rubber compositions of this invention can include from about 1 to about 70 parts by weight, or in other embodiments from about 5 to about 50 parts weight total oil per 100 parts by weight rubber.
  • the amount of sustainable oil, relative to the total weight of oil included, may be from about 1 wt % to about 99 wt %, or in other embodiment from about 20 wt % to about 80 wt %.
  • the rubber compositions can include one or more sustainable waxes, which include natural waxes.
  • a natural wax, or one with no petroleum as its raw material can include carnauba wax, candelilla wax (e.g., extracted from candelilla flowers), rice wax (e.g., separated from rice bran oil) and Japan wax (e.g., extracted from Japanese wax tree).
  • the rubber compositions of this invention include from about 1 to about 20 parts by weight, or in other embodiments from about 2 to about 15 parts by weight total wax per 100 parts by weight rubber.
  • the amount of sustainable wax, relative to the total weight of wax included, may be from about 1 wt % to about 99 wt %, or in other embodiment from about 20 wt % to about 80 wt % of the total wax.
  • the rubber composition includes sustainable waxes only.
  • All ingredients of the rubber compositions can be mixed with standard mixing equipment such as Banbury or Brabender mixers, extruders, kneaders, and two-rolled mills.
  • the ingredients are mixed in two or more stages.
  • a so-called masterbatch which typically includes the rubber component and filler, is prepared.
  • the masterbatch may exclude vulcanizing agents.
  • the masterbatch may be mixed at a starting temperature of from about 25 °C to about 125 °C with a discharge temperature of about 135 °C to about 180 °C.
  • the vulcanizing agents may be introduced and mixed into the masterbatch in a final mixing stage, which is typically conducted at relatively low temperatures so as to reduce the chances of premature vulcanization.
  • additional mixing stages sometimes called remills, can be employed between the masterbatch mixing stage and the final mixing stage.
  • remill stages are often employed where the rubber composition includes silica as the filler.
  • Various ingredients including the polymers of this invention can be added during these remills.
  • the mixing procedures and conditions particularly applicable to silica-filled tire formulations are described in U.S. Patent Nos. 5,227,425; 5,719,207; and 5,717,022, as well as European Patent No. 890,606, all of which are incorporated herein by reference.
  • the initial masterbatch is prepared by including the polymer and silica in the substantial absence of coupling agents and shielding agents.
  • the polymers are mixed with various other ingredients (e.g. filler and curative) to produce a rubber composition (also referred to as vulcanizable composition), and the vulcanizable composition is then processed into tire components according to ordinary tire manufacturing techniques, which generally include standard rubber shaping and molding techniques.
  • the tire components may include, but are not limited to, tire treads, sidewalls, subtreads, body ply skims, and bead filler.
  • the various tire components are then assembled into a green tire (i.e. an uncured tired), placed within a mold, and then vulcanized.
  • vulcanization is effected by heating the vulcanizable composition in a mold; e.g., it may be heated to about 140 °C to about 180 °C.
  • Cured or crosslinked rubber compositions may be referred to as vulcanizates, which generally contain three-dimensional polymeric networks that are thermoset.
  • the other ingredients, such as fillers and processing aids, may be evenly dispersed throughout the crosslinked network.
  • Pneumatic tires can be made as discussed in U.S. Patent Nos. 5,866,171; 5,876,527; 5,931,211; and 5,971,046, which are incorporated herein by reference.
  • the tires can include fabric reinforcement made by using non-petroleum materials in place of synthetic fibers.
  • non-petroleum materials for example, mechanical recycled fibers, chemical recycled fibers, or bio-based fibers can be used.
  • the tires can include metal reinforcement made from recycled steel and/or other circular or sustainable metals. These non-petroleum fabrics and recycled metals can be used exclusively within the tires or in combination with traditional fabric and/or metal reinforcement.

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Abstract

L'invention concerne un procédé comprenant les étapes consistant à : (a) mettre à disposition une charge d'alimentation de pneu usé ; (b) gazéifier la charge d'alimentation de pneu usé pour produire un flux gazeux, le flux gazeux comprenant du monoxyde de carbone, de l'hydrogène et du dioxyde de carbone ; (c) convertir thermochimiquement au moins une partie du monoxyde de carbone, de l'hydrogène et du dioxyde de carbone dans le flux gazeux pour produire un premier flux de produit ; (d) convertir au moins une partie du premier flux de produit en un second flux de produit, le second flux de produit comprenant de l'acétaldéhyde et de l'hydrogène ; (e) acheminer une partie de l'hydrogène dans le second flux de produit vers ladite étape de conversion thermochimique d'au moins une partie du monoxyde de carbone, de l'hydrogène et du dioxyde de carbone dans le flux gazeux ; et (f) convertir au moins une partie d'acétaldéhyde en monomère de butadiène.
PCT/US2024/033059 2023-06-07 2024-06-07 Production de butadiène à partir de pneus usagés Pending WO2024254485A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7452392B2 (en) * 2003-11-29 2008-11-18 Nick Peter A Process for pyrolytic heat recovery enhanced with gasification of organic material
US20120073292A1 (en) * 2010-09-27 2012-03-29 Saudi Arabian Oil Company Process for the gasification of waste tires with residual oil
KR20170041024A (ko) * 2015-10-06 2017-04-14 서울시립대학교 산학협력단 폐타이어 처리용 2 단 열분해 장치, 이를 이용한 폐타이어 처리 방법 및 시스템
US20170267604A1 (en) * 2014-09-19 2017-09-21 IFP Energies Nouvelles Method for the production of butadiene from ethanol in one low-water- and low-energy-consumption reaction step
US20210095210A1 (en) * 2013-01-23 2021-04-01 Sekisui Chemical Co., Ltd. Method for producing recycled material, and tire and method for producing tire

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7452392B2 (en) * 2003-11-29 2008-11-18 Nick Peter A Process for pyrolytic heat recovery enhanced with gasification of organic material
US20120073292A1 (en) * 2010-09-27 2012-03-29 Saudi Arabian Oil Company Process for the gasification of waste tires with residual oil
US20210095210A1 (en) * 2013-01-23 2021-04-01 Sekisui Chemical Co., Ltd. Method for producing recycled material, and tire and method for producing tire
US20170267604A1 (en) * 2014-09-19 2017-09-21 IFP Energies Nouvelles Method for the production of butadiene from ethanol in one low-water- and low-energy-consumption reaction step
KR20170041024A (ko) * 2015-10-06 2017-04-14 서울시립대학교 산학협력단 폐타이어 처리용 2 단 열분해 장치, 이를 이용한 폐타이어 처리 방법 및 시스템

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