WO2024254469A1 - Polyamides produits à partir de pneus usagés - Google Patents

Polyamides produits à partir de pneus usagés Download PDF

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Publication number
WO2024254469A1
WO2024254469A1 PCT/US2024/033035 US2024033035W WO2024254469A1 WO 2024254469 A1 WO2024254469 A1 WO 2024254469A1 US 2024033035 W US2024033035 W US 2024033035W WO 2024254469 A1 WO2024254469 A1 WO 2024254469A1
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WIPO (PCT)
Prior art keywords
tire
feedstock
ethanol
rubber
butadiene
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Pending
Application number
PCT/US2024/033035
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English (en)
Inventor
Terrence E. Hogan
Mark W. Smale
William S. Niaura
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Bridgestone Americas Tire Operations LLC
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Bridgestone Americas Tire Operations LLC
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Publication of WO2024254469A1 publication Critical patent/WO2024254469A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
    • C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/0042—Reinforcements made of synthetic materials
    • 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
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • 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

Definitions

  • Embodiments of the present invention are directed toward a process for converting used tires to polyamides such as nylon 6,6.
  • the nylon can be used in the manufacture of tire cord fabric that is useful in the manufacture of tire components.
  • Used tires include a significant amount of carbonaceous material. Recycling the carbon into other carbon-based materials presents numerous challenges due, at least in part, to the fact that a majority of the carbon is tied up in a vulcanized network. As a result, technologically efficient modes of recycling used tire is fairly limited and includes, for example, mechanically grinding the vulcanized rubber product and using the ground rubber for various uses such as filler within composites. With an eye toward carbon efficiency, other modes of recycling carbon are desired.
  • One or more embodiments of the present invention provide a process comprising [a] providing a feedstock that includes carbonaceous materials; [b ] gasifying the feedstock to produce a gaseous stream including carbon monoxide, hydrogen, and carbon dioxide; [c] converting at least a portion of the carbon monoxide, hydrogen, and carbon dioxide to butadiene; (d) converting at least a portion of the butadiene to at least one of 1,6- hexamethylenediamine and adipic acid; and (e) polymerizing the at least one of the 1,6- hexamethylenediamine and the adipic acid, optionally together with alternate sources of 1,6- hexamethylenediamine or adipic acid, to produce a polyamide.
  • Embodiments of the invention are based, at least in part, on the discovery of a process for consuming used tires in the production of polyamides, particularly nylon 6,6.
  • the polyamides can advantageously be used to produce tire cord fabric that can be used to manufacture tire components.
  • Embodiments of the invention therefore provide a methodology for converting used tires back to useful tires or tire components.
  • used tires are thermally decomposed to form a gaseous stream. One or more components of this gaseous stream are then converted to polyamides. One or more components of the gaseous stream are converted to ethanol, and the ethanol is then converted to butadiene.
  • the butadiene is then converted to at least one of 1,6- hexamethylenediamine and adipic acid, and then at least one of the 1,6- hexamethylenediamine and adipic acid can then be used to synthesize the polyamide via conventional condensation polymerization.
  • the process of the present invention provides a feedstock, which may include tire feedstock, and the feedstock is converted, via thermal decomposition, to a gaseous stream that includes hydrogen, carbon monoxide, and optionally carbon dioxide.
  • This gaseous stream which may be referred to as synthesis gas or syngas, is then converted to ethanol by using biological fermentation processes.
  • the ethanol is then converted to butadiene.
  • the synthesis of butadiene from ethanol can proceed by direct conversion or via a two-step synthesis that produces acetaldehyde as an intermediate product.
  • the butadiene is then converted to 1,6-hexamethylenediamine by using known techniques such as reacting the butadiene with hydrogen cyanide to form adiponitrile, which can then be reduced with hydrogen to form the 1,6-hexamethylenediamine.
  • the butadiene can also be converted to adipic acid by reacting the butadiene with hydrogen and carbon monoxide.
  • both the hydrogen and carbon monoxide used in synthesizing the adipic acid are obtained from the thermal decomposition of the feedstock.
  • the 1,6-hexamethylenediamine and the adipic acidic can then be polymerized to form polyamides using conventional condensation polymerization techniques.
  • the feedstock that is thermally decomposed to form the gaseous stream may include 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 yarn 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 in 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 1 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 pretreatment 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 non-passenger 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 tire 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.
  • 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, 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 is substantially, and in certain embodiments exclusively, comprised of those carbonaceous materials identified above other than tire feedstock; i.e. the feedstock is substantially or exclusively comprised of the co-feed materials identified above.
  • the feedstock includes greater than 80 wt %, in other embodiments greater than 90 wt %, and in other embodiments greater than 99 wt % municipal solid waste.
  • the feedstock includes greater than 80 wt %, in other embodiments greater than 90 wt %, and in other embodiments greater than 99 wt % biomass.
  • the feedstock (which may include tire feedstock and optionally co-feed) is 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 or gasification reactions as disclosed in U.S. Publication Nos. 2021/0207037; 2019/0295734; 2019/0249089; 2018/0273415; 2017/0009162; 2017/0002271; 2016/0107913; 2016/0068773; 2016/0024404; 2014/0182205; 2014/0157667; and 2014/0100294, which are incorporated herein by reference.
  • 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 i.e. the tire feedstock and the co-feed
  • the two feedstocks i.e. the tire feedstock and the co-feed
  • the two feedstocks i.e. the tire feedstock and the co-feed
  • the gaseous product stream produced by thermal decomposition of the feedstock 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 converting the gaseous stream to ethanol.
  • the gaseous product stream from thermal decomposition may be pressurized.
  • pressurization of the gaseous stream achieves sufficient pressure to overcome counter forces within the bioreactor. As the skilled person understands, this will permit flow of the gas through the bioreactor 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.
  • the gaseous stream can be cooled, for example, within a heat exchanger such as 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 bioreactor.
  • the gaseous stream is cooled to a temperature of from about 25 to about 45 °C prior to delivery to the bioreactor.
  • the gaseous stream can be treated to remove undesirable constituents that may be entrained within the stream.
  • the gaseous stream can be treated within a scrubber prior to being introduced to the bioreactor.
  • 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).
  • Exemplary systems for removing hydrogen sulfide from gaseous streams include those available from EcoVapor (Denver, Colorado). Other methods include the use of caustic such as those systems available from DMT under the tradename Sulfurex BF (Netherlands).
  • constituents of the gaseous stream are converted to ethanol that is contained within an ethanol-containing stream; i.e. a product stream that includes ethanol.
  • the gaseous stream is supplemented with hydrogen prior to converting the gaseous stream to an ethanol-containing stream.
  • the gaseous stream is converted to ethanol via biosynthetic techniques.
  • syngas can be converted to ethanol by fermentation utilizing microorganisms, such as bacteria.
  • the microorganisms may be acetogenic autotrophic microbes.
  • Acetogenic microbes i.e. bacteria
  • the acetyl-CoA is then converted to organic products, such as acetic acid and ethanol.
  • microorganisms can reduce the acetic acid (e.g. an organic acid) into an alcohol (e.g. ethanol).
  • This acetogenic mechanism, as well as the microorganism chosen, may be considered relative to preferentially producing ethanol.
  • Microorganisms other than acetogens may be suitable with different pathways to reaching ethanol.
  • One or more useful microorganisms may simultaneous uptake both CO and H 2 in the syngas.
  • certain microorganisms can reduce C02 to CO in the presence of excess hydrogen.
  • useful microorganisms and techniques for their use are disclosed in "A Techno-Economic Assessment of Bioethanol Production from Switchgrass Through Biomass Gasification and Syngas Fermentation” Regis et al, Energy 274, 127318, (2023).
  • the syngas is converted to ethanol via thermochemical techniques.
  • 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. Pat. No. 9,115,046, which is incorporated herein by reference.
  • the resultant ethanol is contained with an ethanol- containing stream.
  • a crude ethanol-containing stream which is obtained directly from the bioreactor in which the ethanol is synthesized, is delivered to downstream steps.
  • the ethanol-containing stream is purified to produce an ethanol-containing stream that is higher in ethanol content.
  • the ethanol-containing stream exiting the step wherein syngas is converted to ethanol i.e.
  • the bioreactor and delivered to the downstream steps where ethanol is further converted (optionally after purification) includes greater than 80 wt %, in other embodiments greater than 90 wt %, and in other embodiments greater than 95 wt % ethanol based upon the entire weight of the ethanol-containing stream.
  • 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.
  • ethanol within the ethanol-containing stream can be converted to butadiene (e.g. 1,3-butadiene] by a two-step synthesis, wherein acetaldehyde is synthesized as an intermediate.
  • the acetaldehyde which is contained within an acetaldehyde-containing stream, is isolated before being delivered to downstream synthesis steps.
  • the acetaldehyde-containing stream as a crude stream, is delivered to downstream synthesis steps.
  • the acetaldehyde is reacted with ethanol in a second step to yield the desired 1,3-butadiene.
  • ethanol can be converted to acetaldehyde by oxidative dehydrogenation of the ethanol.
  • the conversion of ethanol to acetaldehyde generally proceeds 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. In one or more embodiments, the first step of partial dehydrogenation of ethanol to acetaldehyde to achieve an ethanol-acetaldehyde mixture, and a second step for converting the ethanol-acetaldehyde mixture to butadiene. This may include supplementing the ethanol-acetaldehyde mixture with additional ethanol and/or acetaldehyde as to achieve a desirable ratio.
  • the mixture of ethanol and acetaldehyde may then be converted to butadiene using catalyst known in the art such as tantalum oxide, zirconium oxide, silver oxide and combinations thereof. This process may be referred to as an Ostromislensky process.
  • constituents of the gaseous stream are converted directly to butanediol rather than ethanol.
  • the butanediol is then converted to butadiene.
  • the butanediol is contained with a butanediol-containing stream; i.e. a product stream that includes butanediol.
  • the gaseous stream is supplemented with hydrogen prior to converting the gaseous stream to a butanediol- containing stream.
  • the gaseous stream can be treated to remove undesirable constituents prior to converting the gaseous stream to a butanediol-containing stream.
  • certain additives can be introduced to the gaseous stream to thereby remove (e.g. scavenge) sulfur and other impurities.
  • the gaseous stream is converted to a butanediol- containing stream via biosynthetic techniques.
  • syngas can be converted to butanediol by microorganisms (i.e. a microbial catalyst).
  • microorganisms include C. autoethanogenum, C. ljungdahlii, and C. ragsdalei. These microorganisms generally utilize the Wood-Ljungdahl metabolic pathway to achieve the butanediol. Other microorganisms that produce butanediol by different pathways may also be suitable.
  • the resultant butanediol is contained with a butanediol- containing stream.
  • 1,3-butanediol is the targeted butanediol isomer; i.e., 1,3-butanediol is preferred relative to 2,3-butanediol.
  • the use of the feedstock of the present invention leads to production of the favored 1,3-butanediol.
  • the butanediol within the butanediol- containing stream includes greater than 30, in other embodiments greater than 40, in other embodiments greater than 50, in other embodiments greater than 60, in other embodiments greater than 70, and in other embodiments greater than 80 weight %, of 1,3-butanediol based on the total weight of butanediol within the butanediol-containing stream.
  • a crude butanediol-containing stream which is obtained directly from the bioreactor in which the butanediol is synthesized, is delivered to downstream steps.
  • the butanediol-containing stream is purified to produce a butanediol-containing stream that is higher in butanediol content.
  • the butanediol-containing stream exiting the step wherein syngas is converted to butanediol and delivered to the downstream steps where butanediol is converted (optionally after purification) includes greater than 80 wt %, in other embodiments greater than 90 wt %, and in other embodiments greater than 95 wt % butanediol based upon the entire weight of the butanediol-containing stream.
  • butanediol e.g. 1,3-butanediol
  • butadiene e.g. 1,3-butadiene
  • this is accomplished by a dehydration reaction.
  • Methods for the dehydration of butanediol to butadiene are well known. For example, useful methodologies are disclosed in U.S. Patent No. 9,434,659, which is incorporated herein by reference.
  • aluminosilicate catalysts may advantageously be adjusted in order to preferentially produce butadiene.
  • the SiC ⁇ /A ⁇ C ⁇ ratio and pore architecture of the aluminosilicate catalyst may be adjusted and/or it may be desirable to utilize relatively low acid-site densities in the aluminosilicate catalyst.
  • the dehydration of butanediol to butadiene takes place at temperatures of from about 200 to about 300 °C, or in other embodiments from about 200 to about 270 °C.
  • butanediol is dehydrated to butadiene in the gas phase.
  • butadiene within the butadiene-containing stream can be converted to 1,6 hexamethylenediamine.
  • Processes for converting butadiene, particularly 1,3-butadiene, to 1,6-hexamethylenediamine are known.
  • butadiene is reacted with hydrogen cyanide, which may also be referred to as hydrocyanic acid, to form adiponitrile.
  • hydrogen cyanide which may also be referred to as hydrocyanic acid
  • this reaction which is essentially the hydrocyanation of diolefin, takes place in the presence of an appropriate catalyst.
  • hydrocyanation via the nickel-catalyzed Drinkard catalysts is well known.
  • Several other catalysts have been proposed, as disclosed in U.S. Patent No.
  • Exemplary catalysts include organic nickel complexes such as those include phosphines, arsines, stibines, phosphites, arsenites, or antimonites. These reactions can take place in the presence or absence of a solvent.
  • the resulting adiponitrile which is also referred to as hexanedinitrile, is then reduced with hydrogen (i.e. hydrogenated) to form the 1,6 hexamethylenediamine.
  • hydrogenation catalyst such as Raney nickel or cobalt catalysts, as disclosed in U.S. Publication No. 2009-0069603, which is incorporated herein by reference.
  • the product stream obtained from the step of converting butadiene to 1,6-hexamethylenediamine is a crude stream obtained directly from the reactor used to produce the 1,6-hexamethylenediamine.
  • the 1,6- hexamethylenediamine-containing stream is purified to produce a 1,6- hexamethylenediamine-containing stream that is higher in 1,6-hexamethylenediamine content; for example, the 1,6-hexam ethylenediamine-containing stream can be subjected to distillation as described above.
  • the 1,6- hexamethylenediamine-containing product stream obtained from this step e.g.
  • the optionally purified includes greater than 80 wt %, in other embodiments greater than 90 wt %, and in other embodiments greater than 95 wt % 1,6-hexamethylenediamine based upon the entire weight of the 1,6-hexamethylenediamine-containing stream.
  • butadiene within the butadiene-containing stream can be converted to adipic acid.
  • Processes for converting butadiene, particularly 1,3-butadiene, to adipic acid are known. For example, a two-step carbonylation of the butadiene with carbon monoxide and methanol yields adipic acid dimethyl ester, which can then be hydrolyzed to convert the ester in to adipic ester.
  • butadiene can be reacted with hydrogen and carbon monoxide to produce and intermediate that can then be oxidized (e.g. by ozone] to form adipic acid.
  • Exemplary processes for the conversion of butadiene to adipic acid are disclosed, for example, within U.S. Patent No. 3,876,695, which is incorporated herein by reference.
  • constituents of the gaseous stream e.g. hydrogen and carbon monoxide
  • the thermal decomposition of the feedstock or at least a portion thereof
  • adipic acid intermediate that can then be oxidized to form adipic acid
  • the product stream obtained from the step of converting butadiene to adipic acid is a crude stream obtained directly from the reactor used to produce the adipic acid.
  • the adipic acid-containing stream is purified to produce an adipic acid-containing stream that is higher in adipic acid content; for example, the adipic acid-containing stream can be subjected to distillation as described above.
  • the adipic acid-containing product stream obtained from this step includes greater than 80 wt %, in other embodiments greater than 90 wt %, and in other embodiments greater than 95 wt % adipic acid based upon the entire weight of the adipic acid-containing stream.
  • 1,6-hexamethylenediamine within the 1,6- hexamethylenediamine-containing stream and adipic acid within the adipic acid-containing stream can be reacted within a condensation polymerization to form a polyamide such as nylon 6,6.
  • Condensation polymerization reactions for producing polyamides such as nylon 6,6 from 1,6-hexamethylenediamine and adipic acid are well known.
  • known processes may employ acid catalysts to promote the condensation reaction.
  • the reaction can be conducted under vacuum, which removes water from the polymerization and thereby drives the reaction to completion.
  • These reactions are generally known as disclosed, for example, within U.S. Patent Nos. 2,130,523 and 8,697,902, which are incorporated herein by reference.
  • only one of the monomers employed in the condensation polymerization i.e. one of 1,6-hexamethylenediamine and adipic acid
  • the complementary monomer is obtained from other sources.
  • practice of the present invention can produce a variety of polyamides beyond nylon 6,6.
  • the product stream (i.e. the polyamide) obtained from the step of polymerizing 1,6-hexamethylenediamine and polyamide is a crude stream obtained directly from the reactor used to produce the polyamide.
  • the polyamide-containing stream is purified to produce a polyamide-containing stream that is higher in polyamide content; for example, the polyamide-containing stream can be subjected to distillation as described above.
  • the polyamide- containing product stream obtained from this step includes greater than 80 wt %, in other embodiments greater than 90 wt %, and in other embodiments greater than 95 wt % polyamide based upon the entire weight of the polyamide-containing stream.
  • the polyamides (e.g. nylon 6,6) produced by practice of the present invention is formed into yarns, which may then be twisted into cords. For example, two yarns may be twisted into a cord.
  • the cords can be fabricated (e.g. weaved) into fabrics, which may be referred to as tire cord fabric.
  • the nature of the yarn, cords, and the resulting fabric are adapted for use as tire cord fabric for use in tire components.
  • the tire cord fabric is surface treated, for example, by using known dipping techniques, prior to being incorporated into a tire.
  • the tire cord fabric can be calendared, which usually involves sandwiching the fabric between layers of rubber, to form a reinforced ply that is incorporated into a pneumatic tire.
  • the skilled person also appreciates that techniques are well known for spinning polymers into fibers. Generally, this includes forcing the polymer material through a spinneret or die under appropriate conditions. The fibers can then be fabricated into yarns and twisted into cords, and woven into fabric by using known techniques.
  • the present invention provides a method by which waste material, in particular waste material from used tires, is converted back to useful tires.
  • a tire recycling or tire circularity method is provided by the present invention.
  • the nylon tire cord fabric synthesized and used in the practice of this invention may be referred to as circular nylon tire cord fabric.
  • Practice of the present invention not only offers a method for recycling tires by employing used tires as a feedstock to produce nylon that can be incorporated back into tires as nylon tire cord fabric, 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 nylon tire cord 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 tire cord incorporated into 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 nylon tire cord fabric, which includes nylon produced according to embodiments of the present invention.
  • the tire various rubber or rubber-containing components of a tire are produced by preparing and vulcanizing rubber compositions, which are often referred to as vulcanizable rubber compositions or simply rubber compositions.
  • the vulcanizable rubber compositions include a rubber component, filler, wax, and curative.
  • Other ingredients that may be included in the vulcanizable rubber composition include extender oils, processing oils, and resins.
  • the rubber component of the vulcanizable rubber compositions includes a vulcanizable elastomer, which may also be referred to as an elastomer, a vulcanizable rubber, or simply as a rubber.
  • a vulcanizable elastomer which may also be referred to as an elastomer, a vulcanizable rubber, or simply as a rubber.
  • the vulcanizable elastomer is capable of being cured, which may also be referred to as vulcanized, to form an elastomeric composition.
  • the rubber component includes one or more synthetic polymers.
  • These synthetic polymers may include, for example and 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.
  • the rubber component of the vulcanizable rubber compositions of this invention includes one or more circular synthetic rubbers, which is vulcanizable rubber produced from used tires. These circular synthetic rubbers may be used alone as the rubber component or in combination with synthetic polymers.
  • the rubber component may include one or more natural rubbers.
  • Natural rubber may be used alone as the rubber component or in combination with synthetic polymers and/or circular synthetic rubber.
  • synthetic 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.
  • 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.
  • organic fillers include carbon black and starch.
  • inorganic fillers include silica, aluminum hydroxide, magnesium hydroxide, mica, talc (hydrated magnesium silicate], and clays (hydrated aluminum silicates].
  • 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 may be 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, N.J.], Rhodia Silica Systems (Cranbury, N.J.], and J.M. Huber Corp. (Edison, N.J.].
  • 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 of rubber curing agents may be 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. WAX
  • the rubber composition may include one or more 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 rubber compositions of this invention include threshold amounts of sustainable waxes, which includes natural waxes. 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. In certain embodiments, the rubber composition includes sustainable waxes only.
  • oils sustainable oils, which include plant-based oils and biobased 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 %.
  • 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.
  • 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. TIRE REINFORCEMENTS
  • tires produced according to the present invention include fabric reinforcement made by using nylon tire cord produced by the practice of this invention
  • the nylon tire cords only include nylon yarns produced from nylon synthesized according the present invention.
  • the nylon cord includes nylon yarns from the present invention in combination with one or more other yarns.
  • These other yarns can include sustainable fibers such as, but not limited to, mechanically-recycled fibers, chemically recycled fibers, or bio-based fibers.
  • the other yarns may include those fibers obtained from petroleum-derived resins.
  • Composite cords are also contemplated wherein the cords include chemically distinct yarns such as, for example, nylon yarn produced by the present invention in combination with PET yarn.
  • the tire cord fabrics can be woven from only nylon yarns produced in accordance with this invention; i.e. the cords of the fabric include only fibers produced by the present invention.
  • the fabrics include cord obtained from the present invention and cords obtained from other sources.
  • a fabric can be woven using nylon cord produced by the present invention and other cord obtained from other sources.
  • These other cords may include, for example, cords made from natural fibers or recycled fibers.
  • the other cords include those fabricated from petroleum-derived fibers.
  • 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 (a) la fourniture d'une matière première qui comprend des matières carbonées ; (b) la gazéification de la matière première pour produire un flux gazeux comprenant du monoxyde de carbone, de l'hydrogène et du dioxyde de carbone ; (c) la conversion d'au moins une partie du monoxyde de carbone, de l'hydrogène et du dioxyde de carbone en butadiène ; (d) la conversion d'au moins une partie du butadiène en au moins l'un parmi la 1,6-hexaméthylènediamine et l'acide adipique ; et (e) la polymérisation de la 1,6-hexaméthylènediamine et/ou de l'acide adipique, éventuellement conjointement avec des sources alternées de 1,6-hexaméthylènediamine ou d'acide adipique, pour produire un polyamide.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100216958A1 (en) * 2009-02-24 2010-08-26 Peters Matthew W Methods of Preparing Renewable Butadiene and Renewable Isoprene
US20110124927A1 (en) * 2009-11-24 2011-05-26 Range Fuels, Inc. Selective process for conversion of syngas to ethanol
US20150166439A1 (en) * 2013-12-16 2015-06-18 Uop Llc Integration of mto with on purpose butadiene
US20210095210A1 (en) * 2013-01-23 2021-04-01 Sekisui Chemical Co., Ltd. Method for producing recycled material, and tire and method for producing tire
WO2023041710A1 (fr) * 2021-09-16 2023-03-23 Evonik Operations Gmbh Polyamide 12 et copolymères

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100216958A1 (en) * 2009-02-24 2010-08-26 Peters Matthew W Methods of Preparing Renewable Butadiene and Renewable Isoprene
US20110124927A1 (en) * 2009-11-24 2011-05-26 Range Fuels, Inc. Selective process for conversion of syngas to ethanol
US20210095210A1 (en) * 2013-01-23 2021-04-01 Sekisui Chemical Co., Ltd. Method for producing recycled material, and tire and method for producing tire
US20150166439A1 (en) * 2013-12-16 2015-06-18 Uop Llc Integration of mto with on purpose butadiene
WO2023041710A1 (fr) * 2021-09-16 2023-03-23 Evonik Operations Gmbh Polyamide 12 et copolymères

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