Butadiene production from used tires

Abstract

The present invention provides a process comprising: (a) providing used tire feed material; (b) gasifying the used tire feed material to generate a gas stream containing carbon monoxide, hydrogen, and carbon dioxide; (c) thermochemically converting at least a portion of the carbon monoxide, hydrogen, and carbon dioxide in the gas stream to generate a first production stream; (d) converting at least a portion of the first production stream into a second production stream containing acetaldehyde and hydrogen; (e) sending a portion of the hydrogen in the second production stream to the aforementioned step of thermochemically converting at least a portion of the carbon monoxide, hydrogen, and carbon dioxide in the gas stream; and (f) converting at least a portion of the acetaldehyde into a butadiene monomer.

Description

[Technical Field]

[0001] Embodiments of the present invention relate to a process for converting used tires into butadiene monomer. [Background technology]

[0002] Butadiene monomers are polymerized into polybutadiene and butadiene copolymers such as poly(styrene-co-butadiene), poly(isoprene-co-butadiene), and poly(styrene-co-isoprene-co-butadiene). These polymers have many applications, but are heavily used in tire manufacturing. However, used tires are not readily recycled and have been landfilled or incinerated for fuel value. Methods have been proposed to pyrolyze tires to produce synthesis gas, which is then converted into useful materials. These methods lack industrial applicability, and therefore, improvements to this common route are desired. [Overview of the Initiative]

[0003] One or more embodiments of the present invention provide a process comprising: (a) providing used tire feed material; (b) gasifying the used tire feed material to produce a gas stream containing carbon monoxide, hydrogen, and carbon dioxide; (c) thermochemically converting at least a portion of the carbon monoxide, hydrogen, and carbon dioxide in the gas stream to produce a first production stream; (d) converting at least a portion of the first production stream into a second production stream containing acetaldehyde and hydrogen; (e) sending a portion of the hydrogen in the second production stream to the aforementioned step of thermochemically converting at least a portion of the carbon monoxide, hydrogen, and carbon dioxide in the gas stream; and (f) converting at least a portion of the acetaldehyde into a butadiene monomer.

[0004] Other embodiments of the present invention include (a) providing used tire feedstock, (b) optionally providing a co-supply containing carbonaceous materials other than used tire feedstock, (c) gasifying the used tire feedstock and the optional co-supply to generate a gas stream containing carbon monoxide, hydrogen, and carbon dioxide, (d) introducing the gas stream into a thermochemical reactor so that carbon monoxide, hydrogen, and carbon dioxide are converted into a first production stream, (e) converting the first production stream into a second production stream containing acetaldehyde and hydrogen, and (f) separating hydrogen from the second production stream to form a hydrogen stream. (g) Converting acetaldehyde into a final product stream containing butadiene, It provides a process that includes this.

[0005] A further embodiment of the present invention provides a vulcanizable composition comprising a polybutadiene or butadiene copolymer prepared by the above process.

[0006] Yet another embodiment of the present invention provides tire components prepared from the above-described vulcanizable composition.

[0007] Another embodiment of the present invention provides a tire prepared by using the above-described tire components. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 is a schematic diagram of a system for carrying out an embodiment of the present invention. [Modes for carrying out the invention]

[0009] Embodiments of the present 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. According to one or more embodiments, used tires are thermally decomposed to form a gaseous flow, which is then converted to ethanol by a thermochemical process. Ethanol is then converted to acetaldehyde, and this reaction produces a hydrogen byproduct flow used in the upstream production of ethanol. Acetaldehyde can be purified and / or converted to butadiene monomer by reacting with ethanol. It has been found that the overall process efficiency and economics depend on the amount of hydrogen available during the production of ethanol. Therefore, the present invention, which provides downstream production of hydrogen without carbon byproducts, provides overall carbon efficiency. This is particularly advantageous in the present invention because used tires are the primary feedstock, and used tires contain a higher carbon-to-hydrogen molar ratio than other feedstocks such as biomass. In one or more embodiments, butadiene is polymerized to form polybutadiene or butadiene copolymers used in the preparation of vulcanizable compositions that are processed into tire components.

[0010] Process System and Overview Embodiments of the present invention can be described with reference to a diagram showing a system 20 for converting used tires into butadiene and optionally acetaldehyde. The system 20 includes a pyrolysis unit 31 followed in series by a reactor 51, sometimes called a thermochemical reactor 51. The pyrolysis unit 31 is in direct or indirect fluid communication with the reactor 51 via a gas flow conduit 33. An acetaldehyde synthesis unit 71 (may also be called an acetaldehyde production unit 71), located downstream of the reactor 51, is in direct or indirect fluid communication with the reactor 51 via an ethanol product conduit 53. A butadiene synthesis unit 91, also called a butadiene production unit 91, is located downstream of the acetaldehyde synthesis unit 71 and is in direct or indirect fluid communication with the acetaldehyde synthesis unit 71 via an acetaldehyde product conduit 73. The acetaldehyde synthesis unit 71 is also in direct or indirect fluid communication with a hydrogen byproduct conduit 75, which is in fluid communication with the reactor 51.

[0011] According to embodiments of the present invention, the pyrolysis unit 31 is adapted to receive tire feed material and optionally co-feed, and to heat-treat it to produce a gas stream containing carbon monoxide (CO), hydrogen gas (H2), and optionally carbon dioxide (CO2). The reactor 51 includes one or more catalysts adapted to convert carbon monoxide, hydrogen gas, and optionally carbon dioxide into ethanol. The ethanol is transferred to the acetaldehyde synthesis unit 71, where it is converted to acetaldehyde and hydrogen is produced as a by-product. The acetaldehyde can be transferred to the butadiene synthesis unit 91, where it is converted to butadiene. The by-product hydrogen from the acetaldehyde synthesis unit 71 can be transferred to the reactor 51 via conduit 75 or via conduit 99 which is in direct or indirect fluid communication with the butadiene synthesis unit 91.

[0012] In one or more embodiments, the gas stream leaving the pyrolysis unit 31 is treated before being introduced into the reactor 51. For example, as shown in the figure, the gas product stream can be cooled in a heat exchanger 41. In one or more embodiments, the 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 more detail below. The gas stream may also be treated to remove one or more components before being introduced into the reactor 51. For example, as shown in the figure, the gas stream can be treated in a scrubber 45.

[0013] In any case, carbon monoxide, hydrogen, and optionally carbon dioxide are converted to ethanol within the reactor 51. As shown in the figure, the reactor 51 may include external inputs of hydrogen gas and water. In one or more embodiments, the ethanol produced in the reactor 51 is transferred from the reactor 51 to the crude product via the conduit 53. In one or more embodiments, the crude ethanol product stream may be filtered as it exits the reactor 51 or downstream thereof, for example by using a filtration unit 55.

[0014] Before introducing the crude ethanol product stream into the acetaldehyde synthesis unit 71, the crude ethanol stream can be concentrated or purified by other means. For example, ethanol can be separated from the crude ethanol product stream in the distillation unit 61, where the top of the column (i.e., distillate) containing concentrated ethanol is sent via conduit 65 to the acetaldehyde synthesis unit 71 and / or via conduit 67 to the butadiene production unit 91, and the bottom of the column from the distillation can be recycled back to the reactor 51, for example, via an aqueous bottom conduit 63.

[0015] Ethanol is converted to acetaldehyde in an acetaldehyde-producing unit 71, which may be called an acetaldehyde-producing unit 71 or acetaldehyde reactor 71. Acetaldehyde synthesis produces a crude product stream containing acetaldehyde and hydrogen byproducts. In one or more embodiments, the crude acetaldehyde product stream can be transferred directly or indirectly to a butadiene synthesis unit 91 through a conduit 73. In other embodiments, the crude acetaldehyde is transferred directly or indirectly to a separation unit 81 (which may also be called a distillation column, e.g., a purification unit 81) via a conduit 79, where byproduct hydrogen is separated from the acetaldehyde. The byproduct hydrogen can be returned directly or indirectly to the reactor 51 via a conduit 75. The acetaldehyde stream from the separation unit 81 can be sent to a market source via a conduit 83 or to the butadiene reactor 91 via a conduit 85.

[0016] Acetaldehyde is converted to butadiene in the synthesis unit 91 to produce a crude butadiene product stream, which can exit the synthesis unit 91 directly or indirectly via the conduit 93. In one or more embodiments, butadiene is separated from the crude butadiene stream in the distillation column 95 to produce a purified butadiene stream, which can be removed from the system via the conduit 97. In embodiments in which a crude acetaldehyde stream containing hydrogen is supplied to the butadiene production unit 91, the purification unit 95 (e.g., the distillation unit 95) produces a by-product hydrogen stream, which can be returned to the reactor 51 via the conduit 99.

[0017] As shown in the figure, the acetaldehyde synthesis unit 71 and / or the butadiene production unit 91 can be replenished via the conduit 77 with an external source of ethanol. This external source may be derived from the fermentation of crops such as corn. In another embodiment, this external source may be derived from cellulose ethanol produced from grass, wood, algae, or other plants.

[0018] Although the systems and processes of the present invention are presented as a single integrated system in which each unit is directly or indirectly in fluid communication with other units upstream and / or downstream, those skilled in the art can easily envision systems and methods that are not so directly connected but are still integrated. For example, there may be a system in which a gasification unit 31 and a reactor 51 are located in a first facility, and an acetaldehyde production unit 71 and a butadiene production unit 91 are located in a second facility. The first facility (e.g., gasification 31 and reactor 51) can be indirectly connected to the second facility (e.g., acetaldehyde reactor 71 and butadiene reactor 91) via a pipeline that can transport ethanol from the first facility to the second facility, for example. Alternatively, ethanol can be transported from the first facility to the second facility via other forms of transport, including trucks or rail vehicles. Similarly, the hydrogen produced in the acetaldehyde reactor 71 can be returned to the reactor 51 (i.e., from the second facility to the first facility) by pipeline, tanker, truck, or through exchange with a local hydrogen source. In this specification, unless otherwise specified, indirect fluid communication is understood to encompass these connections between various units.

[0019] Characteristics of tires and carbonaceous material supply raw materials In one or more embodiments, the feedstock supplied to the pyrolysis unit 31 includes a tire feedstock from used tires, which may be referred to as used tire feedstock or simply tire feedstock. As will be understood by those skilled in the art, the tire feedstock may include a vulcanized polymer, a carbon black filler, silica, resin, oil, fiber yarns, and metal. The vulcanized polymer may include sulfur crosslink residues of one or more synthetic elastomers including natural rubber and / or diene polymers and copolymers. In one or more embodiments, the used tire feedstock may include tires from which one or more components of the used tires have been removed, shredded, or otherwise ground. For example, the tire feedstock may be processed to remove metal by methods known in the art (e.g., magnetic separation). Alternatively, or in combination, the used tire feedstock may optionally be processed to remove fiber reinforcements such as fiber yarns or cords, and those skilled in the art understand that this is often seen in conjunction with the vulcanized rubber in many tire components. Alternatively, or in combination, the used tire feedstock may optionally be processed to remove inorganic materials such as silica fillers, and those skilled in the art understand that this is often seen in used tire components. In any case, the tire feedstock may be processed into tire fragments, tire chips, or shredded or crumb rubber and supplied to the pyrolysis unit.

[0020] In one or more embodiments, the tire feedstock is characterized by a relatively low amount of metal resulting from a pretreatment of the tire feedstock to remove at least a portion of the metal typically present in used tires. In one or more embodiments, after pretreatment of the used tires to remove metal, the tire feedstock may contain less than 25% by weight, in other embodiments less than 15% by weight, and in other embodiments less than 1% by weight of metal, based on the total weight of the feedstock supplied to the pyrolysis according to the present invention.

[0021] In one or more embodiments, the tire feedstock can be characterized by a relatively small amount of fiber yarns or cords, which can result from a pretreatment of the tire feedstock to remove at least a portion of the fiber yarns or cords typically present in used tires. In one or more embodiments, after pretreatment, the tire feedstock contains 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% of fiber yarns or cords, based on the total weight of the feedstock supplied for pyrolysis according to the present invention.

[0022] In one or more embodiments, the tire feedstock can be characterized by a relatively small amount of inorganic fillers (e.g., silica), which can result from a pretreatment of the tire feedstock to remove at least a portion of the inorganic fillers typically present in used tires. In one or more embodiments, after pretreatment, the tire feedstock contains 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% of inorganic fillers, based on the total weight of the feedstock supplied for pyrolysis according to the present invention.

[0023] In one or more embodiments, the used tire feedstock includes tire residues from passenger car tires. In other embodiments, the used tire feedstock includes tire residues from non - passenger car tires such as, but not limited to, truck and bus tires, off - road vehicle tires, agricultural tires, and race tires.

[0024] In one or more embodiments, the used tire is mechanically processed (e.g., shredded or chopped) to form a shredded or chopped material (i.e., the feedstock is shredded or chopped). This shredded or chopped material (i.e., the feedstock), also called crumb, can be characterized by a favorable compression density. For example, the feedstock is over 640 kg / m 3 3, in other embodiments over 720 kg / m 3 3, and in other embodiments over 770 kg / m 3It may have a very high compressive density, which is determined by ASTM D 698-07.

[0025] In one or more embodiments, the feedstock provided to the pyrolysis unit includes used tires and optionally complementary feedstock. In one or more embodiments, the complementary feedstock, which may also be referred to as co-feed, includes carbonaceous materials other than the tire feedstock. Carbonaceous materials refer to any carbon material, whether in solid, liquid, gaseous, or plasma state. Non-limiting examples of carbonaceous materials include carbonaceous liquid products, industrial liquid recycling, solid waste (MSW or msw) from municipalities with higher biomass content and / or lower recyclable material content, urban waste, agricultural materials, forestry materials, wood waste, building materials, plant materials, industrial waste, fermentation waste, petrochemical by-products, alcohol production by-products, coal, plastics, waste plastics, coke oven tar, lignin, black liquor, polymers, waste polymers, polyethylene terephthalate (PETA), polystyrene (PS), sewage sludge, animal waste, crop residues, energy crops, forest treatment residues, wood treatment residues, livestock waste, poultry waste, food treatment residues, ethanol by-products, spent grains, spent microorganisms, waste from municipalities, construction waste, demolition waste, biomedical waste, hazardous waste, or combinations thereof. In one or more embodiments, the carbonaceous material includes biomass. In one or more embodiments, the biomass includes, but is not limited to, residues of sugarcane, sorghum, and guayure plants. In one or more embodiments, the feedstock comprises a blend of used tires and municipal solid waste, the municipal solid waste may include biomass. In other embodiments, the feedstock comprises used tires and municipal solid waste substantially free of biomass (i.e., substantially petroleum-based municipal solid waste). In yet another embodiment, the feedstock comprises used tires and biomass. In yet another embodiment, the feedstock comprises used tires and municipal solid waste from which most of the recyclable plastics have been removed (i.e., substantially free of recyclable plastics). In its sub-embodiments, recyclable glass and metals are also substantially removed from the municipal solid waste components.

[0026] In further embodiments, the guayule residue is produced as a result of a process for extracting rubber and resin from the guayule plant, as described in U.S. Publication No. 2022 / 0356273(A1), which is incorporated herein by reference. A method for desolvating the guayule residue is described in U.S. Patent No. 10,132,563, which is also incorporated herein by reference. In one or more embodiments, the guayule residue contains 1% by weight or less of an organic solvent (based on the total weight of the dry residue). In certain embodiments, the dry residue contains 0.5% by weight or less of an organic solvent (based on the total weight of the dry residue). In one or more embodiments, the dry residue may contain some amount of water and higher boiling terpenes. In certain embodiments, the total amount of water and higher boiling terpenes in the dry residue may be higher than the amount of organic solvent.

[0027] In one or more embodiments, the co-supplied material (e.g., biomass or waste from a municipality) is 600 kg / m³. 3 Less than 580 kg / m³ in other embodiments. 3 Less than, and in other embodiments, 560 kg / m³ 3 It may also be characterized by a compressive density of less than a certain value, which is determined by ASTM D 698-07.

[0028] The supply material may be characterized by the amount of co-supply (e.g., biomass or waste from municipalities). In one or more embodiments, the supply material includes co-supply in about 0 to about 95% by weight, in other embodiments about 1 to about 75% by weight, in other embodiments about 2 to about 55% by weight, with the remainder being used tires. In one or more embodiments, the supply material includes co-supply in less than 95% by weight, in other embodiments less than 80% by weight, in other embodiments less than 70% by weight. In these embodiments or other embodiments, the supply material includes more than 10% by weight, in other embodiments more than 20% by weight, in other embodiments more than 30% by weight, in other embodiments more than 40% by weight, in other embodiments more than 50% by weight, in other embodiments more than 70% by weight, with the remainder being complementary supply material.

[0029] Tires and, optionally, biomass pyrolysis According to embodiments of the present invention, the feedstock (including tire feedstock and optionally co-feeds) is pyrolyzed into a gaseous stream containing hydrogen, carbon monoxide, and optionally carbon dioxide by using techniques commonly known in the art. As those skilled in the art will understand, these processes may include gasification processes, and it is also known that these processes can be tuned to control the chemical properties of the resulting gaseous stream. For example, the degree of combustion can be controlled by controlling the amount of oxygen present during pyrolysis. In one or more embodiments, the pyrolysis step is carried out in a substantially inert environment.

[0030] Processes that may be used for the pyrolysis step may be prepared as described in U.S. Publications 20210207037, 20190295734, 20190249089, 20180273415, 20170009162, 20170002271, 20160107913, 20160068773, 20160024404, 20140182205, 20140157667, and 20140100294, which are incorporated herein by reference.

[0031] In one or more embodiments, where the feedstock includes both tire feedstock and co-feed, the tire feedstock and co-feed can be introduced simultaneously into the same pyrolysis unit. For example, the tire feedstock and co-feed can be pre-mixed in a desired ratio to form the feedstock supplied to the pyrolysis unit. Alternatively, separate flows of the tire feedstock and co-feed can be supplied separately and individually to the pyrolysis unit at a desired rate. In yet another embodiment, the two feedstocks (i.e., tire feedstock and co-feed) can be processed continuously within the same pyrolysis unit. In yet another embodiment, the two feedstocks (i.e., tire feedstock and co-feed) can be processed in separate pyrolysis units operating in parallel, and then the gas flows generated by each unit can be combined to achieve a desired ratio of gas components.

[0032] Characteristics of gas product flow As described above, the gas product stream produced by the pyrolysis unit 31 contains carbon monoxide, hydrogen, and optionally carbon dioxide. In one or more embodiments, the gas product stream contains about 5 to about 50 weight percent, in other embodiments about 7 to about 25 weight percent, and in other embodiments about 8 to about 15 weight percent of carbon dioxide. In one or more embodiments, the gas product stream contains about 10 to about 85 weight percent, in other embodiments about 20 to about 65 weight percent, and in other embodiments about 25 to about 45 weight percent of hydrogen. In one or more embodiments, the gas product stream contains about 20 to about 85 weight percent, in other embodiments about 30 to about 75 weight percent, and in other embodiments about 40 to about 60 weight percent of carbon monoxide. In one or more embodiments, the gas product stream produced by pyrolysis contains about 40 to about 80 weight percent, in other embodiments about 45 to about 75 weight percent, and in other embodiments about 50 to about 70 weight percent of carbon (i.e., carbon in carbonaceous compounds), based on the total weight of the gas product stream.

[0033] Adjusting gas flow In one or more embodiments, the gas flow is conditioned (i.e., treated) before being supplied to the reactor 21. In one or more embodiments, the gas product flow from pyrolysis carried by the conduit 33 may be pressurized. In one or more embodiments, the pressurization of the gas flow achieves a pressure sufficient to overcome the opposing forces within the reactor. As those skilled in the art will understand, this allows the gas to flow through the reactor and allows inert gases (e.g., nitrogen) in the gas flow to enter the reactor's headspace. In one or more embodiments, the gas flow is pressurized to a pressure of about 5 to about 20 bar.

[0034] Furthermore, the gas flow can be cooled in a heat exchanger 41. As those skilled in the art will understand, the heat exchanger 41 may include a water cooling unit. In one or more embodiments, the gas flow is cooled to a temperature lower than what would otherwise have a detrimental effect on the microbial culture in the reactor. In one or more embodiments, the gas flow is cooled to a temperature of about 25 to about 45°C before being delivered to the reactor.

[0035] Furthermore, the gas stream can be treated in a scrubber 45 before being introduced into the reactor. In one or more embodiments, this may involve the use of a catalyst (e.g., iron oxide) to remove sulfur compounds such as hydrogen sulfide. This stream can also be treated to remove acids (e.g., treatment with calcium carbonate or sodium carbonate, which is particularly relevant to removing hydrogen cyanide).

[0036] Synthesis gas to ethanol As described above, synthesis gas is converted to ethanol by thermochemical techniques within reactor 51. Those skilled in the art will understand that several thermochemical techniques exist for converting synthesis gas to ethanol. For example, there is a two-step process that can convert synthesis gas to methanol using a hydrogen-to-carbon monoxide ratio of 2:1. These reactions are typically carried out in the gas phase using a copper-based catalyst. The resulting product stream is typically saturated with water and can be purified by known distillation techniques. Methanol can then be catalytically converted to ethanol. A one-step catalytic technique is also known. An exemplary thermochemical process for converting synthesis gas to ethanol is described in U.S. Patent No. 9,115,046, which is incorporated herein by reference.

[0037] Ethanol-containing product flow from the reactor As described above, the ethanol exits the reactor 51 in the ethanol product stream. This ethanol product stream can be processed in unit 55, for example, by filtration.

[0038] Ethanol concentration / separation As described above, following any processing in unit 55, the ethanol-containing product stream can be processed to separate ethanol from other components in the stream. This may include distilling the ethanol-containing stream in separation unit 61. According to these embodiments, ethanol can be collected as a top stream characterized by an ethanol concentration of more than 80% by weight, more than 90% by weight in other embodiments, and more than 93% by weight in other embodiments. In these or other embodiments, the top stream (i.e., the ethanol-containing stream) may contain less than 10% by weight of water, less than 8% by weight in other embodiments, and less than 1% by weight in other embodiments.

[0039] In one or more embodiments, the top ethanol stream may optionally be further treated to purify the ethanol stream before introducing the ethanol into the acetaldehyde generation unit 71. For example, the ethanol stream may be dehydrated or dried by treating it in one or more water adsorption beds containing a drying material such as molecular sieves.

[0040] Acetaldehyde production As shown above, ethanol is converted to acetaldehyde in the production unit 71. In one or more embodiments, substantially all of the ethanol produced in the reactor 51 (i.e., substantially all of the ethanol in the ethanol-containing product stream) is introduced into the acetaldehyde production unit 71. In these or other embodiments, ethanol obtained from outside the process of the present invention (e.g., ethanol from crop fermentation) is also introduced into the acetaldehyde production unit 71 to supplement the production of acetaldehyde. In one or more embodiments, the weight ratio of ethanol supplied from the reactor 51 to the acetaldehyde production unit 71 to ethanol supplied from another source to the acetaldehyde production unit 71 (e.g., ethanol from crop fermentation) is about 1:0 to about 1:10, about 1:0.3 to about 1:7 in other embodiments, and about 1:1 to about 1:5 in other embodiments.

[0041] As those skilled in the art will understand, the synthesis of acetaldehyde involves the partial dehydrogenation of ethanol to obtain a hydrogen byproduct stream. As described above, hydrogen can be supplied to reactor 51, which can favorably offset the hydrogen deficiency of the process. Those skilled in the art will understand that if additional ethanol is converted to acetaldehyde, the introduction of ethanol from a source outside the reactor process (i.e., outside reactor 51) will further alleviate the hydrogen deficiency within reactor 51, which will allow for the production of more hydrogen.

[0042] In one or more embodiments, within the acetaldehyde generation unit 71, ethanol is dehydrogenated at a high temperature on a suitable catalyst, such as a copper-based catalyst. For example, the reaction can be carried out in a fixed-bed reactor. In one or more embodiments, the dehydrogenation of ethanol within the unit 71 is carried out at a temperature of about 200 to about 350°C, or in other embodiments, about 250 to about 300°C.

[0043] In one or more embodiments, ethanol can be converted to acetaldehyde by oxidative dehydrogenation of ethanol. In one or more embodiments, the conversion of ethanol to acetaldehyde may proceed by partial oxidation of ethanol in an exothermic reaction. In this partial oxidation process, the reaction may take place on a silver catalyst at about 500°C to about 650°C. In one or more embodiments, the conversion of ethanol to acetaldehyde may involve avoiding or inhibiting the formation of acetic acid compared to acetaldehyde. This can be achieved by selecting a catalyst and / or reaction conditions known to avoid the formation of acetic acid compared to acetaldehyde. In one or more embodiments, the conversion of ethanol to acetaldehyde is carried out without evaporating acetaldehyde. In one or more embodiments, the conversion of ethanol to acetaldehyde is carried out in the gas phase at relatively low pressure to increase the selectivity of acetaldehyde.

[0044] Acetaldehyde to butadiene In one or more embodiments, the acetaldehyde produced in unit 71 is converted to a butadiene monomer in the butadiene production unit 91. In one or more embodiments, butadiene production involves reacting ethanol with acetaldehyde to produce 1,3-butadiene by utilizing reaction techniques commonly known in the art, such as those 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. As those skilled in the art will understand, this reaction can be carried out at high temperatures on a suitable catalyst, such as a tantalum-accelerated porous silica catalyst. Other catalysts for converting acetaldehyde and ethanol to butadiene are also known in the art and may include tantalum oxide, zirconium oxide, silver oxide, and combinations thereof. This process can be called the Stromislenski process.

[0045] In one or more embodiments, the reaction is carried out in a fixed-bed reactor operating at a temperature of about 300 to about 450°C, or in other embodiments, about 350 to about 400°C. In one or more embodiments, the process may include supplementing the ethanol-acetaldehyde mixture with additional ethanol and / or acetaldehyde to achieve a desired ratio.

[0046] In one or more embodiments, the reactant feed to the butadiene production unit 91 includes an ethanol-to-acetaldehyde molar ratio (i.e., moles of ethanol to moles of acetaldehyde) in the range of at least 1:1, at least 2:1 in other embodiments, at least 2.5:1 in other embodiments, at least 4:1 in other embodiments, and in other embodiments, in the range of about 1:1 to about 5:1.

[0047] The feed to the butadiene production unit 91 is characterized by low levels of impurities (i.e., components other than acetaldehyde and ethanol). In one or more embodiments, the feed stream to the butadiene production unit 91 contains impurities of less than 10% by weight, less than 5% by weight in other embodiments, and less than 2% by weight in other embodiments, based on the total weight of the feed stream.

[0048] The crude butadiene stream exiting the butadiene reactor 91 via the conduit 93 generally contains 1,3-butadiene monomer, unreacted ethanol, unreacted acetaldehyde, water which is a by-product of the reaction, and other by-products. In one or more embodiments, the yield of 1,3-butadiene based on acetaldehyde is greater than 20 mol%, greater than 30 mol%, and greater than 40 mol%. In these or other embodiments, the yield of 1,3-butadiene based on acetaldehyde is less than 70 mol%, less than 60 mol%, and less than 55 mol%.

[0049] In one or more embodiments, the crude butadiene product stream undergoes a first separation, which may include distillation. In one or more embodiments, butadiene is separated as the top stream, and the remaining components of the product stream are separated as the bottom stream. The bottom stream can then be further separated to separate ethanol and acetaldehyde from the water and other components of this stream. The ethanol and acetaldehyde that can be separated as the top stream can then be recycled back to the butadiene production unit 91 for conversion to butadiene.

[0050] In alternative embodiments, ethanol in an 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 direct synthesis. In one or more embodiments, the direct synthesis of ethanol to butadiene is carried out 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 synthetic method for directly converting ethanol to butadiene is the Lebedev process. Still other methods for directly converting ethanol to butadiene include those commercially available from ETB Catalytic Technologies and the technology commercially available from Synthos.

[0051] As those skilled in the art will understand, the direct conversion of ethanol to butadiene may involve the use of two-step extraction distillation utilizing n-methylpyrrolidone (NMP) as the solvent. The direct conversion technique may also include conventional distillation for the recovery of butadiene. [Industrial applicability]

[0052] In one or more embodiments, the butadiene monomer (e.g., 1,3-butadiene) produced by the method of the present invention can be used in the production of polybutadiene or butadiene copolymer (which may also be referred to as polybutadiene copolymer). For the purposes of this specification, these polymers may be referred to as cyclic synthetic rubber or cyclic synthetic polybutadiene-butadiene copolymer. In one or more embodiments, this cyclic synthetic rubber can be used in the manufacture of tire components. As a result, the implementation of the present invention provides a method for converting waste materials, particularly waste materials from used tires, into useful tires. In other words, a tire recycling or cyclic method is provided.

[0053] The synthesis of polybutadiene or polybutadiene copolymers from butadiene monomers is well known and can be achieved by using several synthetic routes (i.e., polymerization mechanisms and techniques). For example, monomers can be polymerized by free radical emulsion polymerization, anionic polymerization, or coordination catalysts using, for example, nickel or neodymium-based catalyst systems.

[0054] As those skilled in the art will understand, comonomers that can copolymerize with butadiene to form polybutadiene copolymers include, but are not limited to, vinyl aromatic monomers such as styrene, and other diene monomers such as isoprene. In one or more embodiments, the comonomer is a sustainable comonomer. For example, styrene can be obtained from a biosynthesized raw material such as bioethanol, which is then converted to styrene. See, for example, U.S. Patent No. 9,663,445. Alternatively, styrene can be synthesized from bio-based materials such as cinnamic acid or hydrocinnamic acid. See, for example, U.S. Patent No. 9,868,853. Yet another example is styrene obtained from the depolymerization of polystyrene from spent waste. See, U.S. Publication No. 2022 / 0411351. Those skilled in the art will also understand that styrene can be obtained from a mass-balanced process that is qualified as a bio-based, bio-circular, or circular process, as designated by the International Sustainability and Carbon Certification (ISCC).

[0055] It should be understood that the polybutadiene polymers prepared by polymerizing the butadiene of the present invention have a relatively high proportion of mer units derived from the butadiene produced by the present invention, and therefore the polybutadiene polymers of the present invention have a relatively high sustainable content. In one or more embodiments, the polybutadiene polymers synthesized by polymerizing the butadiene of the present invention contain more than 50 mol%, more than 60 mol%, more than 70 mol%, more than 80 mol%, more than 90 mol%, more than 95 mol%, and more than 99 mol% of sustainable mer units obtained from the polymerization of butadiene obtained by the present invention (i.e., mer units obtained from monomers synthesized from gaseous streams obtained by gasification of carbonaceous materials). Similarly, if the synthesized polymer is a polybutadiene copolymer obtained by copolymerizing the butadiene monomer obtained by the implementation of the present invention with a sustainable comonomer, the resulting polybutadiene copolymer has a relatively high sustainable content. In one or more embodiments, the polybutadiene copolymer synthesized by polymerizing the butadiene of the present invention together with a sustainable comonomer contains more than 50 mol%, more than 60 mol%, more than 70 mol%, more than 80 mol%, more than 90 mol%, more than 95 mol%, and more than 99 mol% of sustainable Mer units (i.e., monomer units obtained from monomers synthesized from gaseous streams obtained by gasification of carbonaceous materials and other sustainable comonomers).

[0056] Polymers synthesized from butadiene monomers produced according to embodiments of the present invention may be called vulcanizable polymers or elastomer polymers, and generally include polydienes and polydiene copolymers. Specific polymers that can be produced and used in tire manufacturing include, but are not limited to, polybutadiene, poly(styrene-co-butadiene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), and their functionalized derivatives.

[0057] 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, sub-treads, and bead fillers. These polymers can be used as all or part of the elastomer components of tire stock. When the polymers produced by the present invention are used together with other vulcanizable polymers to form the elastomer components of tire stock, these other vulcanizable polymers may be natural rubber, synthetic rubber, or mixtures thereof. Examples of synthetic rubbers include polyisoprene, poly(styrene-co-butadiene), and other polybutadienes, poly(styrene-co-butadiene-co-isoprene) having low and / or cis-1,4-bond content, and mixtures thereof. The polymers of the present invention can also be used in the manufacture of hoses, belts, shoe soles, window seals, other seals, vibration damping rubber, and other industrial products.

[0058] The embodiment of the present invention not only provides a method for recycling tires by using used tires as a feedstock to produce polymers that can be compounded back into tires, but also advantageously provides a method for producing tires with a relatively high content of sustainable components, including recycled materials, naturally derived materials, and / or biosynthetic feedstocks or bio-based materials. Furthermore, these tires or tire components include a threshold amount of cyclic synthetic rubber, characterized by a high sustainable content. For example, the tires or tire components of the present invention may include more than 40% by weight, more than 50% by weight in other embodiments, and more than 60% by weight in other embodiments, of sustainable materials. In one or more embodiments, the tires or tire components include about 40 to about 90% by weight, about 45 to about 85% by weight in other embodiments, and about 50 to about 80% by weight in other embodiments, of styrene. In combination therewith, the rubber component of the tires or tire components of the present invention includes more than 10% by weight, more than 20% by weight in other embodiments, more than 30% by weight in other embodiments, more than 40% by weight in other embodiments, more than 45% by weight in other embodiments, and more than 50% by weight in other embodiments, of cyclic synthetic rubber, which includes synthetic rubber produced according to embodiments of the present invention.

[0059] As described above, the vulcanizable composition of the present invention contains a rubber component. This rubber component includes cyclic synthetic rubber produced according to embodiments of the present invention. The rubber component may also include other synthetic rubbers, such as synthetic rubber derived from petroleum-based raw materials and not recycled, synthetic rubber derived from other sustainable processes, and natural rubber. As those skilled in the art will understand, natural rubber is synthesized by and obtained from plants. For example, 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.

[0060] Other synthetic polymers that may be used include, but are not limited to, 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 countless macromolecular structures, including linear, branched, and star-shaped structures.

[0061] Generally, the rubber composition of the present invention contains, based on the total weight of the tire components, about 30 to about 65% by weight of elastomer in other embodiments, about 35 to about 60% by weight in other embodiments, and about 40 to about 55% by weight in other embodiments.

[0062] As suggested above, the rubber composition includes 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 clay (hydrated aluminum silicate). In certain embodiments, mixtures of different fillers may be advantageously used.

[0063] The total amount of filler used in the rubber composition may be up to about 150 parts by weight per 100 parts by weight (phr) of rubber, and is typically about 30 to about 125 phr, or about 40 to about 110 phr. In certain embodiments, the total filler content is greater than about 100 phr. In other embodiments, the total filler content is about 50 to about 100 phr, and in further embodiments, it is about 55 to about 95 phr.

[0064] Conventional carbon blacks generally known in the art can be used. In one or more embodiments, the carbon blacks include furnace black, channel black, and lamp black. More specific examples of carbon blacks include ultra-abrasive furnace black, intermediate ultra-abrasive furnace black, high abrasion furnace black, high-speed extruded furnace black, fine furnace black, semi-reinforced furnace black, medium-machined channel black, hard-machined channel black, conductive channel black, and acetylene black.

[0065] In certain embodiments, the carbon black has a surface area (EMSA) of at least 20 m². 2 / g, in other embodiments at least 35m 2The value may be / g, and the surface area value can be determined using the cetyltrimethylammonium bromide (CTAB) technique according to ASTM standard D-1765. The carbon black may be in pelletized form or in unpelleted cotton form. The preferred form of carbon black may depend on the type of mixing equipment used to mix the rubber compound.

[0066] In one or more embodiments, recycled materials may be used for the carbon black. Such recycled materials may include recycled or recycled vulcanized rubber, which is typically recycled from manufactured articles such as pneumatic tires, industrial conveyor belts, power transmission belts, and rubber hoses. Recycled carbon black can be obtained by a pyrolysis process or by other known methods for obtaining recycled carbon black. In one embodiment, recycled carbon black may be formed from the incomplete combustion of recycled rubber feedstock or rubber articles. In another embodiment, recycled carbon black can be formed from the incomplete combustion of feedstock containing oil resulting from a tire pyrolysis process. The carbon black used in the preparation of the vulcanizable elastomer composition may be in pelletized form or in non-pelletized cottony mass.

[0067] The total amount of filler used in the rubber composition may be up to about 75 parts by weight per 100 parts by weight (phr) of rubber, and is typically about 5 to about 60 phr, or about 10 to about 55 phr.

[0068] The rubber composition may further include fillers in the form of one or more recycled rubbers in particulate form. Recycled particulate rubber is typically broken down and regenerated (or recycled) by one of several processes, which may include physical decomposition, grinding, chemical decomposition, desulfurization, cryogenic grinding, or a combination thereof. The term recycled particulate rubber may relate to both vulcanized rubber and desulfurized rubber, with desulfurized recycled rubber or recycled rubber (recycled rubber) relating to rubber that has been vulcanized, ground into particles, and may further undergo substantial or partial desulfurization. In one example, recycled particulate rubber used in a rubber composition does not essentially contain recycled rubber resulting from desulfurization. Where the vulcanized rubber contains wires or textile fiber reinforcements, such wires or fiber reinforcements may be removed by an optional preferred process such as magnetic separation, air suction and / or air flotation steps. In certain embodiments, “recycled particulate rubber” includes cured, i.e., vulcanized (crosslinked) rubber that has been ground or powdered into particulate matter having an average particle size as discussed below.

[0069] Certain silicas can be considered sustainable materials. Commercially available silicas that may be used in this 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, NJ), and JMHuber Corp. (Edison, NJ). Other sustainable silicas include those derived from rice husk ash.

[0070] In one or more embodiments, silica can be characterized by its surface area, which is a measure of its reinforcing properties. The Brunauer, Emmet, and Teller (“Brunauer, Emmet and Teller, BET”) method (described in J. Am. Chem. Soc., 1939, vol. 60, 2 p. 309-319) is an accepted method for determining 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, from about 100 to about 250 m 2 / g, and from about 130 to about 240 m 2 / g, and from about 170 to about 220 m 2 / g. In certain embodiments, silica can have a BET surface area of from 190 to about 280 m 2 / g. The pH of silica is generally from about 5 to about 7, or slightly higher than 7, or in other embodiments, from about 5.5 to about 6.8.

[0071] In one or more embodiments, when silica is used as a filler (alone or in combination with other fillers), a coupling agent and / or a masking agent may be added to the rubber composition during mixing to enhance the interaction between the silica and the elastomer. Useful coupling agents and masking agents are disclosed in U.S. Patent Nos. 3,842,111, 3,873,489, 3,978,103, 3,997,581, 4,002,594, 5,580,919, 5,583,245, 5,663,396, 5,674,932, 5,684,171, 5,684,172, 5,696,197, 6,608,145, 6,667,362, 6,579,949, 6,590,017, 6,525,118, 6,342,552, and 6,683,135, which are incorporated herein by reference.

[0072] The amount of silica used in the rubber composition may be about 1 to about 150 phr, or in other embodiments, about 5 to about 130 phr. The useful upper limit is limited by the high viscosity provided by the silica. In certain embodiments, the silica used in the rubber composition is derived solely from rice husk ash, and in other embodiments, the rubber composition does not contain silica from non-rice husk ash-derived processes. When silica is used with carbon black, the amount of silica or carbon black can be reduced to about 1 phr each. Generally, the amounts of binders and shielding agents range from about 4% to about 20% by weight, based on the weight of silica used. In one or more embodiments in which carbon black and silica are used in combination as fillers, the weight ratio of silica to total fillers may be about 5% to about 99% by weight of total fillers, in other embodiments, about 10% to about 90% by weight of total fillers, or in yet another embodiment, about 50% to about 85% by weight of total fillers. In certain embodiments, the silica and carbon black fillers used in the rubber composition are selected from the group consisting of sustainably pyrolytic carbon black and / or silica derived from rice husk ash.

[0073] Numerous rubber curing agents (also called vulcanizing agents) containing sulfur or peroxide-based curing systems may be used. (See Kirk-Othmer, Encyclopedia of Chemical Technology, Vol.20, pgs.365-468, (3) rd Ed.1982), especially Vulcanization Agents and Auxiliary Materials, pgs.390-402, and AYCoran, Vulcanization, Encyclopedia of Polymer Science and Engineering, (2 nd These are described in Ed. 1989, and are incorporated herein by reference. The vulcanizing agents may be used alone or in combination.

[0074] Other components typically used in rubber compounding can also be added to the rubber composition. These include accelerators, surfactants, oils, plasticizers, waxes, anticorrosion agents, processing aids, zinc oxide, tackifying resins, reinforcing resins, fatty acids such as stearic acid, reconstituters, and antioxidants and ozone degradation inhibitors.

[0075] With regard to oils, sustainable oils, including vegetable oils and bio-based oils, may be used. Vegetable oils may contain vegetable triglycerides. Exemplary oils, but not limited to, include palm oil, soybean oil (also known herein as soybean oil), rapeseed oil, sunflower seed oil, peanut oil, cottonseed oil, oil derived from palm kernels, coconut oil, olive oil, corn oil, grape seed oil, hemp oil, linseed oil, rice oil, safflower oil, sesame oil, mustard oil, and flaxseed oil. Other examples include nut-derived oils such as those obtained from beech, cashew, mongono, macadamia, pine, hazelnut, chestnut, acorn, almond, pecan, pistachio, walnut, or Brazil nut. As those skilled in the art will understand, 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, dissociation, refining, purification, hydrogenation, and sparging.

[0076] Bio-oils, also known as bio-oils, can include oils produced by recombinant cells. For example, recombinant cell-produced bio-oils are created using selected strains of algal cells that have been given sugars (e.g., sucrose), which are then fermented to produce a bio-oil with a selected profile. Once sufficiently grown or fermented, the bio-oil is separated from the cells and recovered.

[0077] Generally, the rubber composition of the present invention may contain about 1 to about 70 parts by weight of total oil per 100 parts by weight of rubber, or in other embodiments, about 5 to about 50 parts by weight of total oil. The amount of sustainable oil may be about 1% to about 99% by weight of the total weight of the oil contained, or in other embodiments, about 20% to about 80% by weight.

[0078] With respect to wax, rubber compositions may include one or more sustainable waxes, including natural waxes. Examples of natural waxes, or those that do not contain petroleum as a raw material, include carnauba wax, candelilla wax (e.g., extracted from candelilla flowers), rice wax (e.g., isolated from rice bran oil), and wood wax (e.g., extracted from sumac).

[0079] Generally, the rubber composition of the present invention contains about 1 to about 20 parts by weight of total wax per 100 parts by weight of rubber, or in other embodiments, about 2 to about 15 parts by weight of total wax. The amount of sustainable wax may be about 1% to about 99% by weight of total wax, or in other embodiments, about 20% to about 80% by weight of total wax, relative to the total weight of the wax contained. In certain embodiments, the rubber composition contains only sustainable wax.

[0080] All components of a rubber composition can be mixed using standard mixing equipment, such as a Banbury or Bravender mixer, extruder, kneader, and two-roll mill. In one or more embodiments, the components are mixed in two or more stages. In the first stage (often also called the masterbatch mixing stage), a so-called masterbatch (typically containing rubber components and fillers) is prepared. To prevent premature vulcanization (also known as scorching), the vulcanizing agent may be removed from the masterbatch. The masterbatch may be mixed at a starting temperature of about 25°C to about 125°C and an extrusion temperature of about 135°C to about 180°C. Once the masterbatch is prepared, in the final mixing stage, the vulcanizing agent may be introduced into the masterbatch and mixed. This final mixing stage is typically carried out at a relatively low temperature to reduce the possibility of premature vulcanization. Optionally, an additional mixing stage, often called a re-mill, can be used between the masterbatch mixing stage and the final mixing stage. If silica is included as a filler in the rubber composition, one or more re-mill stages are often used. Various components, including the polymer of the present invention, can be added during these remilling processes.

[0081] Mixing procedures and conditions particularly applicable to silica-filled tire formulations are described in U.S. Patents No. 5,227,425, 5,719,207, and 5,717,022, and European Patent No. 890,606, all of which are incorporated herein by reference. In one embodiment, the preparation of the initial masterbatch is carried out by incorporating the polymer and silica substantially in the absence of coupling agents and shielding agents.

[0082] To manufacture tire components using the polymer produced by the present invention, those skilled in the art will understand that the polymer is mixed with various other components (e.g., fillers and curing agents) to produce a rubber composition (also called a vulcanizable composition), and that the vulcanizable composition is then processed into tire components according to conventional tire manufacturing techniques, which generally include standard rubber molding, molding, and curing techniques. Tire components may include, but are not limited to, tire treads, sidewalls, sub-treads, body ply skims, and bead fillers. The various tire components are then assembled into a green tire (i.e., an uncured tire), placed in a mold, and then vulcanized. Typically, vulcanization is carried out by heating the vulcanizable composition in a mold, which may be heated to, for example, about 140°C to about 180°C. The cured or crosslinked rubber composition may also be called a vulcanized product, which generally contains a thermosetting three-dimensional polymer network structure. Other components, such as fillers and processing aids, may be uniformly dispersed throughout the crosslinked network structure. Pneumatic tires may be manufactured as described in U.S. Patents 5,866,171, 5,876,527, 5,931,211, and 5,971,046, which are incorporated herein by reference.

[0083] In one or more embodiments, the tire may include fiber reinforcements made by using non-petroleum materials instead of synthetic fibers. For example, mechanically recycled fibers, chemically recycled fibers, or bio-based fibers may be used. Similarly, the tire may include metal reinforcements made from recycled steel and / or other circular or sustainable metals. These non-petroleum fibers and recycled metals may be used exclusively within the tire or in combination with conventional fiber and / or metal reinforcements.

[0084] Various modifications and changes that do not depart from the scope and spirit of the present invention will be apparent to those skilled in the art. The present invention is not formally limited to the exemplary embodiments described herein.

Claims

1. It is a process, (a) To provide used tire supply material, (b) Gasifying the used tire supply material to generate a gas stream containing carbon monoxide, hydrogen, and carbon dioxide, (c) Thermochemically converting at least a portion of the carbon monoxide, hydrogen, and carbon dioxide in the gas stream to generate a first production stream, (d) Converting at least a portion of the first production flow into a second production flow containing acetaldehyde and hydrogen, (e) Sending a portion of the hydrogen in the second production flow to the step of thermochemically converting at least a portion of the carbon monoxide, hydrogen, and carbon dioxide in the gas flow, (f) Converting at least a portion of the acetaldehyde into butadiene monomer, A process that includes this.

2. The process according to claim 1, wherein the first production logistics comprises ethanol.

3. The process according to claim 1 or 2, further comprising polymerizing the butadiene monomer to form polybutadiene or polybutadiene copolymer.

4. The process according to any one of claims 1 to 3, further comprising producing a tire component using the polybutadiene or polybutadiene copolymer.

5. The process according to any one of claims 1 to 4, wherein the gasification step comprises gasifying a used tire supply material and a co-supply containing carbonaceous materials other than the used tire supply material.

6. It is a process, (a) To provide used tire supply material, (b) Optionally, provide a co-supply containing carbonaceous materials other than used tire supply raw materials, (c) Gasifying the used tire supply material and any co-supplied materials to generate a gas stream containing carbon monoxide, hydrogen, and carbon dioxide, (d) Introducing the gas flow into a thermochemical reactor, wherein the carbon monoxide, hydrogen, and carbon dioxide are converted into the first production flow, (e) Converting the first production flow to a second production flow containing acetaldehyde and hydrogen, (f) Separating the hydrogen from the second production flow described above, thereby forming a hydrogen stream, (g) Converting the acetaldehyde into a final product stream containing butadiene, A process that includes this.

7. The first production logistics is the process according to any one of claims 1 to 6, comprising ethanol.

8. The process according to any one of claims 1 to 7, wherein the ethanol is converted into the second production logistics.

9. The process according to any one of claims 1 to 8, further comprising separating the ethanol from the first production flow.

10. The process according to any one of claims 1 to 9, further comprising separating the butadiene from the final product stream.

11. The process according to any one of claims 1 to 10, wherein the gasification step is carried out by plasma-induced oxidation.

12. The process according to any one of claims 1 to 11, wherein the gas flow is neutralized before being introduced into the aqueous medium.

13. The process according to any one of claims 1 to 12, wherein the gas flow is cooled.

14. The process according to any one of claims 1 to 13, wherein the step of converting the synthesis gas to ethanol is performed at a high temperature.

15. The process according to any one of claims 1 to 14, wherein the step of separating the ethanol from the first productive flow comprises distilling the ethanol from the first productive flow as a top flow, and further comprising sending the bottom flow from the step of distillation into a recirculation flow.

16. The process according to any one of claims 1 to 15, further comprising introducing the recirculated flow into the bioreactor.

17. The process according to any one of claims 1 to 16, further comprising introducing the recirculating flow into the step of cooling the gas flow.

18. The process according to any one of claims 1 to 17, further comprising introducing the recirculated flow into the step of neutralizing the gas flow.

19. The process according to any one of claims 1 to 18, further comprising filtering the first productive logistics before the step of converting the first productive logistics to a second productive logistics and removing microorganisms from the first productive logistics.

20. The process according to any one of claims 1 to 19, wherein the hydrogen stream is introduced into the aqueous medium.

21. The process according to any one of claims 1 to 20, further comprising the step of introducing a second hydrogen stream into the reactor.

22. The process according to any one of claims 1 to 21, wherein the step of converting the ethanol into a second production flow is carried out in an acetaldehyde reactor, and further comprises introducing a second ethanol flow into the acetaldehyde reactor from an external source.

23. The process according to any one of claims 1 to 22, wherein the step of converting the ethanol to acetaldehyde further comprises introducing the ethanol into the second production logistics before the step of converting more than 90 mole percent of the ethanol to acetaldehyde and converting the acetaldehyde to butadiene.

24. The process according to any one of claims 1 to 23, further comprising converting the butadiene to polybutadiene or a butadiene copolymer.

25. The process according to any one of claims 1 to 24, further comprising producing a tire material from the polybutadiene or butadiene copolymer.

26. The process according to any one of claims 1 to 25, wherein the gasification step includes gasifying the tire supply material and co-supply.

27. The process according to any one of claims 1 to 26, wherein the co-supplied material includes biomass.

28. The process according to any one of claims 1 to 27, wherein the biomass includes residue.

29. The process according to any one of claims 1 to 28, wherein the residue is the residue of a guayule plant.

30. The process according to any one of claims 1 to 29, wherein, prior to the gasification step, the tire supply material and co-supply material are mixed to form a mixture.

31. The process according to any one of claims 1 to 30, characterized in that the mixture of used tire supply material and co-supplied material contains less than 25% by weight of metal based on the total weight of the mixture.

32. The process according to any one of claims 1 to 31, characterized in that the mixture of used tire supply material and co-supplied material contains less than 5% by weight of fiber yarn or cord based on the total weight of the mixture.

33. The process according to any one of claims 1 to 32, characterized in that the mixture of used tire supply material and co-supplied material contains less than 30% by weight of inorganic filler based on the total weight of the mixture.

34. The aforementioned mixture was measured at 640 kg / m³ according to ASTM 698-07. ３ The process according to any one of claims 1 to 33, having an ultracompressible density.

35. The process according to any one of claims 1 to 34, wherein the mixture comprises about 1 to about 75% by weight of co-feed, and the remainder comprises used tires.

36. A vulcanizable composition comprising a polybutadiene or butadiene copolymer prepared by the process described in any one of claims 1 to 35.

37. A vulcanizing composition according to any one of claims 1 to 36, further comprising a filler, an oil, and a rubber curing agent.

38. The vulcanizable composition according to any one of claims 1 to 37, wherein the filler comprises silica.

39. The vulcanizable composition according to any one of claims 1 to 38, wherein the filler contains silica derived from rice husk ash.

40. The filler comprises recycled carbon black, and is a vulcanizable composition according to any one of claims 1 to 39.

41. The vulcanizable composition according to any one of claims 1 to 40, wherein the oil comprises a bio-oil or a vegetable oil.

42. A vulcanizable composition according to any one of claims 1 to 41, further comprising a natural wax.

43. The vulcanizable composition according to any one of claims 1 to 42, wherein the vulcanizable composition comprises about 30 to about 65% by weight of rubber based on the total weight of the vulcanizable composition, and more than 10% by weight of the rubber is polybutadiene or polybutadiene copolymer prepared according to any one of claims 1 to 42.

44. The vulcanizable composition according to any one of claims 1 to 43, wherein the vulcanizable composition comprises about 30 to about 150 parts by weight of a filler per 100 parts by weight of rubber, and the filler comprises carbon black and silica in a weight ratio of about 5 to about 99% by weight of the filler.

45. The vulcanizing composition according to any one of claims 1 to 44, wherein the vulcanizing composition contains about 1 to about 70 parts by weight of oil per 100 parts by weight of rubber, and at least 1% by weight of the oil is bio-oil or vegetable oil.

46. A vulcanizable composition according to any one of claims 1 to 45, comprising about 1 to about 20 parts by weight of wax per 100 parts by weight of rubber, wherein at least 1% by weight of the wax is natural wax.

47. A tire component prepared from a vulcanizable composition according to any one of claims 1 to 46.

48. A tire manufactured by using the tire components described in any one of claims 1 to 47.

49. A tire according to any one of claims 1 to 48, comprising more than 40% by weight of sustainable materials.

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