Methods for producing olefins

Abstract

Methods for producing olefins from a carbonaceous feedstock and a fossil hydrocarbon feedstock, where the methods utilize a moving bed reactor, a regenerator vessel, and a solid oxygen carrier.

Description

METHODS FOR PRODUCING OLEFINSField of Disclosure

[0001] This disclosure relates methods for producing olefins from a carbonaceous feedstock and a fossil hydrocarbon feedstock, where the methods utilize a moving bed reactor, a regenerator vessel, and a solid oxygen carrier.Background

[0002] Olefins, which may be referred to as alkenes, are hydrocarbons having at least one carbon-carbon double bond in their molecular structure. Olefins are unsaturated hydrocarbons. Olefins are utilized for a number of applications including plastics applications, synthetic fiber applications, chemical intermediates, and fuel applications, among others. There exists a continuing need for new methods of producing olefins.Summary

[0003] The present disclosure provides various embodiments, including the following. A method for producing olefins, the method including: transferring a carbonaceous feedstock to a moving bed reactor; transferring a fossil feedstock to the moving bed reactor; converting the fossil hydrocarbon feedstock in the moving bed reactor to produce olefins; steam cracking the carbonaceous feedstock in the moving bed reactor to produce olefins and hydrogen; combusting hydrogen in the moving bed reactor utilizing a solid oxygen carrier to produce a reduced solid oxygen carrier; transferring the reduced solid oxygen carrier from the moving bed reactor to a regenerator vessel; generating heat by oxidizing the reduced solid oxygen carrier in the regenerator vessel; and transferring the oxidized solid oxygen carrier from the regenerator vessel to the moving bed reactor.Brief Description of the Drawing

[0004] The Figure illustrates an example of a portion of a system in accordance with one or more embodiments of the present disclosure.Detailed Description

[0005] Methods for producing olefins from a carbonaceous feedstock and a fossil hydrocarbon feedstock are disclosed herein. The methods utilize a system 101 to produce olefins. The Figure illustrates an example of a portion of a system in accordance with one or more embodiments of the present disclosure. The system 101 includes a moving bed reactor 103 and a regenerator vessel 105. The methods utilize a solid oxygen carrier. Embodiments provide that the solidoxygen carrier is selective for combustion of hydrogen in the presence of steam and hydrocarbons.

[0006] Previous methods of producing olefins have utilized pyrolysis of waste plastics to liquid cracker feedstock or gasification of waste plastics to syngas and subsequent conversion of the syngas to olefins. However, the previous methods utilize multistep processes to produce olefins. Other methods of producing olefins have utilized fluidized steam cracking; however, this fluidized steam cracking requires a significant energy input and generates an undesirable process CO2 footprint. For instance, fluidized steam cracking can be performed in dual fluidized bed reactors (either two separated fluidized bed vessels or a fluidly connected dual chamber configuration), where heat for the steam cracking reaction is provided by circulating an inert material, such as sand and / or dolomite, that is heated in a combustion section via burning a carbonaceous byproduct, e.g., fixed carbon, coke, tar, and / or fuel gas, and / or an external fuel. However, this combustion creates a flue gas stream containing CO2 at low partial pressure, which is therefore difficult and / or expensive to capture.

[0007] Advantageously, the methods disclosed herein can produce olefins. Further, the methods disclosed herein can provide a reduced CO2 footprint. The reduced CO2 footprint can be achieved by providing heat through in-situ combustion of hydrogen produced by steam cracking, i.e. , the cracking reaction, and / or converting of the fossil feedstock leading to a lower additional fuel demand of the system. Additionally, residual CO2 is generated in the product gas stream at partial pressures where conventional carbon capture techniques may advantageously be effectively utilized.

[0008] As discussed further herein, the methods for producing olefins utilize the system 101, including the moving bed reactor 103 and the regenerator vessel 105, and a bed material that comprises a solid oxygen carrier. Embodiments provide that the solid oxygen carrier is steam tolerant. In other words, the solid oxygen carrier can selectively combust H2 in the presence of steam and hydrocarbons. One or more embodiments provide that the bed material may comprise a solid oxygen carrier and a steam tolerant dehydrogenation catalyst, e.g., a dehydrogenation catalyst can be transferred to the moving bed reactor. Steam tolerant dehydrogenation catalysts are known. Different steam tolerant dehydrogenation catalysts may be utilized for various applications.

[0009] Embodiments provide that combustion of H2, as well as other hydrocarbons, produced by conversion, dehydrogenation, or steam cracking in the moving bed reactor 103 can provide energy, e.g. all or a portion of, required for endothermic steam cracking of the carbonaceous feedstock, endothermic conversion of the fossil hydrocarbon feedstock, and related process heat applications. Further, embodiments provide that heat can be generated in the regenerator vessel 105 via oxidation of the solid oxygen carrier, thereby reducing the fuel demand of the system 101 and the associated CO2 footprint of flue gas. One or more embodiments provide that heat can be generated by combustion of an additional heat generating combustible fuel, when utilized, in the regenerator. The additional heat generating combustible fuel can be hydrogen, methane, ethane, propane, coke or any fuel that when combusted will create the desired energy.

[0010] Advantageously, the system 101 provides that one or more components, e.g., the solid oxygen carrier, in the moving bed reactor 103 can be transferred to the regenerator vessel 105 and that one or more components, e.g., the solid oxygen carrier, in the regenerator vessel 105 can be transferred to the moving bed reactor 103. In other words, the solid oxygen carrier can be circulated between the moving bed reactor 103 and the regenerator vessel 105.

[0011] As mentioned, embodiments provide that the methods disclosed herein include a moving bed reactor 103. One or more embodiments provide that the moving bed reactor can be anaerobic. Moving bed reactors are known. In the moving bed reactor, one or more components in the reactor can move downwards, e.g. under the influence of gravity, through the reactor. Embodiments provide the moving bed reactor 103 can be utilized for steam cracking of the carbonaceous feedstock, conversion of the fossil hydrocarbon feedstock, and combustion of H2 in the reactor. Different moving bed reactors can be utilized for various applications. For instance, the moving bed reactor can have various dimensions and / or various geometries for different applications. One or more embodiments provide that no external heating is utilized to maintain the temperature of the moving bed reactor.

[0012] While the Figure illustrates a single moving bed reactor 103, embodiments are not so limited. For instance, one or more embodiments provide that a plurality of moving bed reactors, e.g., moving bed reactors in parallel, are utilized. Various materials, as discussed herein, can be input to different moving bed reactors for different applications. As an example, one or more embodiments provide that the carbonaceous feedstock and steam can be transferred to a firstmoving bed reactor while the fossil hydrocarbon feedstock is transferred to a second moving bed reactor, which is operated in parallel to the first moving bed reactor. In such embodiments, the solid oxygen carrier can be circulated between the moving bed reactors and the regenerator vessel.

[0013] Embodiments provide that one or more carbonaceous feedstocks may be utilized for different applications. Examples of the carbonaceous feedstocks include polymeric materials such as polymers, plastics, and combinations thereof. One or more embodiments provide that the carbonaceous feedstock comprises a waste-derived feedstock. Examples of waste-derived feedstock include mixed plastic waste, comprising a number of polymers such as polyethylene, polypropylene, polystyrene, polyethyleneterephtalate, polyamide, and polyvinylchloride. Other examples of waste-derived feedstock include materials categorized under the “Deutsche Gesellschaft fur Kreislaufwirtschaft und Rohstoffe GmbH”), including DKR 310, DKR 320, DKR 321, DKR 322, DKR 323, DKR 324, DKR 329, DKR 350, DKR 351, DKR 352, and DKR 361. The carbonaceous feedstock can include non-polymeric post-consumer residues, as discussed in a number of the DKR specifications. One or more embodiments provide that the carbonaceous feedstock contains reclaimed polymers. As used herein, the term “reclaimed polymer” refers to a polymer that has been used for a previous purpose and then recovered for further processing. For instance, “reclaimed polymer” can refer to polymers recovered from post-consumer material as defined by ISO 14021, polymers recovered from pre-consumer material as defined by ISO 14021, and combinations thereof. The generic term post-consumer material includes blends of polymers recovered from materials generated by households or by commercial, industrial, and institutional facilities in their role as end-users of the material, which can no longer be used for its intended purpose. The generic term post-consumer material also includes blends of polymers recovered from returns of materials from the distribution chain. The generic term pre-consumer material includes blends of polymers recovered from materials diverted from the waste stream during a manufacturing process. The reclaimed polymer may include a polymer or a blend of polymers recovered from post-consumer material, pre-consumer material, post-industrial material, or combinations thereof.

[0014] Reclaimed polymer, as used herein, is distinct from virgin polymer. “Virgin polymer” refers to polymers that can be characterized as “primary (virgin) raw material,” as defined by ISO 18604. The term virgin polymer can include polymers that have never been processed into any form of end-use product.

[0015] A carbonaceous feedstock, e.g., reclaimed polymer, can be collected and processed prior to being utilized in the methods disclosed herein. For instance, the carbonaceous feedstock can be shredded, be washed, undergo metals reduction, e.g., removal, be density separated, be dried, be pyrolyzed, and / or be sorted.

[0016] The carbonaceous feedstock can comprise various polymeric materials. The polymeric material, e.g., reclaimed polymer, can be a homopolymer, a copolymer, ora combination thereof. Examples of reclaimed polymer include polyolefins, such as polyethylene and polypropylene, polyesters, such as poly(ethylene terephthalate), vinyl polymers, such as poly(vi nyl chloride), acrylonitrile, butadiene and styrene homopolymer and interpolymers, polyurethanes, polyesters, such as polyethylene terephthalate) and poly(bisphenol-A carbonate), polyamides, such as Nylon 66, polycarbonates, such as poly(bisphenol-A carbonate), acrylics, such as poly(methyl methacrylate), fluorocarbon polymer, polyethers, polysaccharides, thermoplastic elastomers, such as ethylene-propylene rubber, among others. One or more embodiments provide that the carbonaceous feedstock comprises polyolefins.

[0017] Embodiments provide that the carbonaceous feedstock can include one or more heteroatoms, e.g., atoms that are non-carbon and non-hydrogen. Examples of hetero-atoms include oxygen, nitrogen, sulfur, chlorine, fluorine, and bromine.

[0018] One or more embodiments provide that the carbonaceous feedstock include less than or equal to 20 weight percent of oxygen based on a total weight of the carbonaceous feedstock. For example, when oxygen is included, the carbonaceous feedstock can include from 0.01 to 20 weight percent of oxygen based upon a total weight of the carbonaceous feedstock.

[0019] One or more embodiments provide that the carbonaceous feedstock include less than or equal to 1 weight percent of nitrogen based on a total weight of the carbonaceous feedstock. For example, when nitrogen is included, the carbonaceous feedstock can include from 0.001 to 1 weight percent of nitrogen based upon a total weight of the carbonaceous feedstock.

[0020] One or more embodiments provide that the carbonaceous feedstock include less than or equal to 1 weight percent of sulfur based on a total weight of the carbonaceous feedstock. For example, when sulfur is included, the carbonaceous feedstock can include from 0.001 to 1 weight percent of sulfur based upon a total weight of the carbonaceous feedstock.

[0021] One or more embodiments provide that the carbonaceous feedstock include less than or equal to 1 weight percent of halides based on a total weight of the carbonaceous feedstock. For example, when halides are included, the carbonaceous feedstock can include from 0.001 to 1weight percent of halides based upon a total weight of the carbonaceous feedstock. Examples of halides include chlorine, fluorine, bromine, and combinations thereof.

[0022] Embodiments provide that the moving bed reactor 103 includes a material input 107. While the Figure illustrates a single material input 107, embodiments are not so limited. One or more embodiments provide that the moving bed reactor 103 includes a plurality of material inputs. Different number of inputs may be utilized for various applications.

[0023] As shown in the Figure, the material input 107, can be located in at an upper section 104 of the moving bed reactor 103. However, embodiments are not so limited. Embodiments provide that a material input can be located in the upper section 104, in a middle section 106, and / or in a lower section 108 of the moving bed reactor. As used herein, the upper section refers to a top third of the moving bed reactor, the middle section refers to an intermediate section of the moving bed reactor between the upper section and the lower section, and the lower section refers to a bottom section of the moving bed reactor based, upon a total vertical height 110 of the of the moving bed reactor.

[0024] The carbonaceous feedstock can be transferred to the moving bed reactor 103 via a material input, e.g., material input 107. Embodiments provide that different carbonaceous feedstock transfer processes may be utilized for various applications. For instance, the carbonaceous feedstock, among other materials discussed herein, can be transferred to the moving bed reactor 103 via the material input 107 continuously or intermittently. One or more embodiments provide that a pyrolyzed carbonaceous feedstock, e.g., gas phase, is transferred to the moving bed reactor 103.

[0025] The fossil hydrocarbon feedstock can be transferred to the moving bed reactor 103 via a material input, e.g., material input 107. As used herein, “fossil hydrocarbon feedstock’’ refers to a material derived from fossil materials, such as natural gas, petroleum, and / or coal, that can be utilized as a raw material for the methods disclosed herein. In other words, the fossil hydrocarbon feedstock, e.g. all or a portion of, can be endothermically converted in the moving bed reactor 103. The fossil hydrocarbon feedstock can be endothermically converted to produce olefins, such as ethylene, propylene, butene, styrene and pentene.

[0026] Embodiments provide that different fossil hydrocarbon feedstocks can be utilized for various applications. One or more embodiments provide that the fossil hydrocarbon feedstock comprises ethane, propane, n-butane, iso-butane, ethyl-benzene, naphtha, or combinations thereof. One or more embodiments provide that the fossil hydrocarbon feedstock comprisesethane, propane, butane, or combinations thereof. One or more embodiments provide that the fossil hydrocarbon feedstock comprises ethane, propane, or combinations thereof. One or more embodiments provide that the fossil hydrocarbon feedstock is ethane.

[0027] Embodiments provide that the fossil hydrocarbon feedstock can be from 20 to 99 weight percent (wt%) based upon a total weight (100 wt%) of the fossil hydrocarbon feedstock and the carbonaceous feedstock transferred to the moving bed reactor. All individual values and subranges from 20 to 99 wt% are included; for example, the fossil hydrocarbon feedstock can be a lower limit of 20, 21 , 22, 23, 24, or 25 wt% to an upper limit of 99, 95, 90, 85, 80, or 75 wt% based upon the total weight of the fossil hydrocarbon feedstock and the carbonaceous feedstock. One or more embodiments provide that the fossil hydrocarbon feedstock is equal to or greater than 20 weight percent of a total weight of the fossil hydrocarbon feedstock and the carbonaceous feedstock transferred to the moving bed reactor. One or more embodiments provide that the fossil hydrocarbon feedstock can be 25 wt% and the carbonaceous feedstock can be 75 wt% based upon the total weight of the fossil hydrocarbon feedstock and the carbonaceous feedstock. One or more embodiments provide that the fossil hydrocarbon feedstock can be 50 wt% and the carbonaceous feedstock can be 50 wt% based upon the total weight of the fossil hydrocarbon feedstock and the carbonaceous feedstock. One or more embodiments provide that the fossil hydrocarbon feedstock can be 75 wt% and the carbonaceous feedstock can be 25 wt% based upon the total weight of the fossil hydrocarbon feedstock and the carbonaceous feedstock.

[0028] One or more embodiments provide that steam can be transferred to the moving bed reactor 103 via a material input, e.g., material input 107. The steam can be utilized for steam cracking the carbonaceous feedstock and / or converting the fossil hydrocarbon feedstock in the moving bed reactor.

[0029] One or more embodiments provide that steam is not transferred to moving bed reactor 103. For these embodiments, steam can be generated in-situ, as discussed herein.

[0030] Embodiments provide that the moving bed reactor 103 can have an operational temperature, e.g., a steady state temperature, from 550 to 850 °C. All individual values and subranges from 550 to 850 °C are included; for example, the moving bed reactor can have an operational temperature from a lower limit of 550, 600, 650, or 700 °C to an upper limit of 850, 800, 775, or 750 °C. Operational temperature can be determined as an outlet temperature of the product gas from the moving bed reactor.

[0031] Embodiments provide that the moving bed reactor 103 can have an operational pressure, e.g., a steady state pressure, from 1 to 10 bara. All individual values and subranges from 1 to 10 bara are included; for example, the moving bed reactor can have an operational pressure from a lower limit of 1, 1.2, or 1.5 bara to an upper limit of 10, 5, 4, or 3 bara.Operational pressure can be determined as an outlet pressure of the product gas from the moving bed reactor.

[0032] One or more embodiments provide that the moving bed reactor 103 can have a steam to combination of feedstocks mass flow ratio (kg steam input to the reactor / kg of a combination of carbonaceous feedstock and fossil hydrocarbon feedstock input to the reactor, which may be referred to dilution steam ratio) from 0.1 to 3 kg / kg combination of feedstocks. As used herein, “combination of feedstocks” refers to the combination of carbonaceous feedstock and fossil hydrocarbon feedstock input to the reactor. All individual values and subranges from 0.1 to 3 kg / kg of the combination of feedstocks are included; for example, the moving bed reactor can have a steam to combination of feedstocks mass flow ratio from a lower limit of 0.1 , 0.3, or 0.4 kg / kg of the combination of feedstocks to an upper limit of 3, 2.5, 2, or 1.5 kg / kg of the combination of feedstocks.

[0033] Embodiments provide that the fluidized bed reactor 103 can have a solid oxygen carrier to the combination of feedstocks ratio from 1 to 200 kilograms solid oxygen carrier per kilogram of the combination of feedstocks transferred to the reactor. All individual values and subranges from 1 to 200 kg / kg the combination of feedstocks are included; for example, the fluidized bed reactor can have a solid oxygen carrier to the combination of feedstocks ratio from a lower limit of 1 , 5, 10, 15, or 20 to an upper limit of 200, 150, 100, 50, or 35 kg / kg of the combination of feedstocks.

[0034] Embodiments provide that the moving bed reactor 103 can provide an average carbonaceous feedstock gas residence time from 2 to 120 seconds. All individual values and subranges from 2 to 120 seconds are included; for example, the moving bed reactor can provide an average carbonaceous feedstock gas residence time from a lower limit of 2, 3, or 4 seconds to an upper limit of 120, 100, 80, 50, or 30 seconds. Average residence time can be determined as a quotient of an amount of carbonaceous feedstock gas in the reactor and a flow rate of carbonaceous feedstock through the reactor.

[0035] As mentioned, embodiments provide for steam cracking of the carbonaceous feedstock and conversion of the fossil hydrocarbon feedstock in the moving bed reactor 103. As such, themoving bed reactor can include a number of steam cracking products and conversion products, including primary products and byproducts. For example, for various embodiments the moving bed reactor can include a number of the following: olefins, e.g., ethylene, propylene, butene, styrene and pentene; aromatic compounds, e.g., benzene, toluene, and xylenes; paraffins, e.g., methane, ethane, and propane; alkyl aromatics, ethylbenzene; heavier hydrocarbons, e.g., tars (Cs+compounds); dienes, e.g. propadiene, butadiene; acetylenes; hydrogen; carbon monoxide; and carbon dioxide. As used herein, “butene” refers to 1-butene, 2-butene, and isobutylene. As used herein, “pentene” refers to 1-pentene, cis-2-pentene, trans-2-pentene, and other isomers, The moving bed reactor can include different concentrations of the number of steam cracking and conversion products for various applications.

[0036] As discussed further herein, the solid oxygen carrier, e.g., the redox-active transition metal oxide, can undergo reduction in the presence of a reducing agent, e.g., hydrogen as generated by the steam cracking.

[0037] Advantageously, embodiments provide that the hydrogen can be combusted in the moving bed reactor 103 to provide energy, e.g. all or a portion of, utilized for endothermic steam cracking of the carbonaceous feedstock and / or endothermic conversion of the fossil hydrocarbon feedstock. As mentioned, embodiments utilize a solid oxygen carrier. Oxygen present in the solid oxygen carrier may be utilized as the source of oxygen for combustion in the moving bed reactor.

[0038] As used herein “solid oxygen carrier” refers to a solid material that may be utilized as the source of oxygen for combustion in the moving bed reactor. Embodiments provide that the solid oxygen carrier is selective to combust hydrogen in an environment, e.g., moving bed reactor 103, that includes hydrogen, steam, and a number of hydrocarbons. One or more embodiments provide that the hydrocarbon molecules include from 1 to 4 carbon atoms. Examples of the hydrocarbon include olefins, e.g., light olefins such as ethylene and propylene, and paraffins. Different solid oxygen carriers can be utilized for various applications.

[0039] The solid oxygen carrier can include a redox-active transition metal oxide. One or more embodiments provides that the solid oxygen carrier can include one or more alkali metals, alkaline-earth metals, or combinations thereof, which may be referred to as promoters. The promoter is any material or element that increases the selectivity for combustion of hydrogen in the presence of steam and hydrocarbons. The solid oxygen carrier can include a support material, which may include one or more metal oxides.

[0040] Solid oxygen carriers are discussed in patent application publication U.S. 2021 / 0317004 Al. U.S. 2021 / 0317004 Al is incorporated herein by reference. In one or more embodiments, the solid oxygen carrier consumes heat upon reduction under operating conditions in the moving bed reactor 103. In one or more embodiments, the solid oxygen carrier generates heat upon reduction under operating conditions in the moving bed reactor. Advantageously, embodiments disclosed herein provide that the solid oxygen carrier generates heat upon oxidation under operating conditions in the regenerator vessel 105.

[0041] As mentioned, the solid oxygen carrier includes a redox-active transition metal oxide. The redox-active transition metal oxide is capable of oxygen carrying functionality by which oxygen atoms can be removed and replaced from a solid lattice. The redox-active transition metal oxide may include binary, ternary, or other mixed metal oxides capable of undergoing reduction in the presence of a reducing agent, e.g., hydrogen, and oxidation in the presence of oxidizing agent, e.g., oxygen or air. In one or more embodiments, the redox-active transition metal oxide may include oxides of nickel, iron, cobalt, tungsten, manganese, copper. It should be understood that, as used herein, the redox-active transition metal oxide includes metals in various oxidation states. In some embodiments, the redox-active transition metal oxide may comprise more than one metal oxide, and individual metals within the redox-active transition metal oxide may have different oxidation states. Thus, the redox-active transition metal oxide is not limited to compromising metal oxides with homogeneous oxidation states. Some examples of the redox-active transition metal oxide are MnO, Mn2C>3, Fe2C>3, FeO, CO3O4, CoO, CU2O, (LaSr)CoC>3, (LaSr)MnC>3, MggMnOg, MgMnOs, MnC>2, FesOzp MnsOzi, CuO, WO3, WO2, Ce2C>3, CeC>2, W2O5, MoO2, MOO3, NiO, and combinations thereof.

[0042] As mentioned, the solid oxygen carrier can include a promoter. Examples of such promoters include one or more alkali metal, alkaline-earth metal, or combinations thereof. Alkali metals include lithium, sodium, potassium, and cesium. Alkaline-earth metals include magnesium, calcium, strontium, and barium. In one or more embodiments, a combination of a redox-active transition metal and a promotor provides for the formation of mixed metal oxides.

[0043] A number of suitable solid oxygen carriers are discussed in U.S. Patent Number 11,794,181, U.S. Patent Number 12,151,233, U.S. Patent Number. 5,430,209, U.S. Patent Number 7,122,495, and / or WO 2018 / 232133, each of which are incorporated by reference in their entireties.

[0044] One or more embodiments provide that the solid oxygen carrier includes a support material, which may also be referred to as a binder material. In such embodiments, a number of components, e.g., the promoter, of the solid oxygen carrier may be supported, e.g. bound, by the support material. The support material may include one or more inorganic bulk metal oxides, such as silica (SiO2), alumina (AI2O3), silica and alumina, zirconia (ZrC>2), titania (TiC>2), other metal oxides, or combinations of metal oxides. One or more embodiments provide that the one or more components may be supported and / or bound on a surface of the support material and / or incorporated into the support material. The support material can provide mechanical stability to the solid oxygen carrier.

[0045] Example of solid oxygen carriers include Fe2C>3 (45 wt. %) / K2WC>4 (10 wt. %) / TiC>2 (45 wt. %), Fe2<D3 (40 wt. %) / Mn2C>3 (5 wt. %) / K2WC>4 (10 wt. %) / TiC>2 (45 wt. %), Fe2C>3 (40 wt. %) / Co3O4(5 wt. %) / K2WO4(10 wt. %) / TiO2(45 wt. %), Fe2O3(40 wt. %) / CuO (5 wt.%) / K2WO4 (10 wt. %) / TiC>2 (45 wt. %), Fe2C>3 (38 wt. %) / CeC>2 (9 wt. %) / K2WO4 (10 wt. %) / TiO2(43 wt. %), Fe2O3(68 wt. %) / K2WO4(10 wt. %) / SiO2(22 wt. %), Fe2O3(69 wt.%) / K2WO4 (9 wt. %) / AI2C>3 (22 wt. %), MnC>2 (45 wt. %) / KH2PO4 (10 wt. %) / ZrC>2 (45 wt. %), Mn3O4(45 wt. %) / K2WO4(10 wt. %) / AI2O3(45 wt. %), Mn3O4(45 wt. %) / K2WO4 (10 wt. %) / MgAl2C>4 (45 wt. %), CaMnC>3 (99 wt. %) / K2SO4 (1 wt. %), Cag 5Srg sMnOg (99 wt.%) / Na2O(SiC>2) (1 wt. %), Lag gSrg ^FeOg (50 wt. %) / SiC>2 (50 wt. %), and LaFeOg (48 wt. %) / K2O (2 wt. %) / SiC>2 (50 wt. %), among other solid oxygen carriers.

[0046] One or more embodiments provide that the solid oxygen carrier can have a hydrogen combustion selectivity from 70 to 99%. Different hydrogen combustion selectivities can be utilized for various applications. Hydrogen combustion selectivity can be determined by:((reaction rate of hydrogen combustion) / (reaction rate of hydrogen combustion + reaction rate of hydrocarbon combustion)) x 100.

[0047] Known components and known processes may be utilized to make the solid oxygen carrier.

[0048] Embodiments provide that the moving bed reactor 103 includes a gas output 111. As previously mentioned, carbonaceous feedstock steam cracking products and fossil hydrocarbon feedstock conversion products, which may be referred to herein as products, are generated in the moving bed reactor. Embodiments provide that a number of the products are gaseous. Gaswithin the moving bed reactor, which may be referred to as cracked gas, may be discharged via the gas output 111.

[0049] Embodiments provide that gas, i.e. , products including olefins, can be discharged via the gas output 111. Advantageously, as previously mentioned utilizing the solid oxygen carrier can provide that hydrogen produced by steam cracking can be combusted in the moving bed reactor 103.

[0050] As illustrated in the Figure, the gas output 111 can be located in the lower section 108 of the moving bed reactor 103, however, embodiments are not so limited. For example, one or more embodiments provide that the gas output 111 can be located in the middle section 106 of the moving bed reactor 103.

[0051] One or more embodiments of the present disclosure provide that the moving bed reactor can provide an ethylene mass flow ratio, i.e. a yield, from 100 to 800 grams of ethylene per kilogram of the combination of feedstocks transferred to the reactor. All individual values and subranges from 100 to 800 g / kg of the combination of feedstocks, are included; for example, the ethylene mass flow ratio can be from a lower limit of 100, 150, 200, or 250 g / kg of the combination of feedstocks to an upper limit of 800, 750, 600, 550, or 500 g / kg the combination of feedstocks. Ethylene can be discharged from the moving bed reactor 103 via gas output 111.

[0052] One or more embodiments of the present disclosure provide that the moving bed reactor can provide a propylene mass flow ratio, i.e. a yield, from 10 to 500 grams of propylene per kilogram of the combination of feedstocks transferred to the reactor. All individual values and subranges from 10 to 500 g / kg of the combination of feedstocks, are included; for example, the propylene mass flow ratio can be from a lower limit of 10, 20, 35, or 50 g / kg of the combination of feedstocks to an upper limit of 500, 450, 400, 300, or 200 g / kg of the combination of feedstocks. Propylene can be discharged from the moving bed reactor 103 via gas output 111.

[0053] Embodiments of the present disclosure can provide an improved, i.e., increased, hydrogen combustion as compared to other processes, where the hydrogen is produced by steam cracking. This increased hydrogen combustion indicates that hydrogen produced by the cracking reaction is combusted in the moving bed reactor 103 at advantageously greater mole percents, as compared to other processes.

[0054] Embodiments of the present disclosure provide that the moving bed reactor 103 can provide hydrogen combustion from 50 to 100 mole percent of hydrogen produced by steam cracking. In other words, from 50 to 100 mole percent of the hydrogen produced by steamcracking can be combusted in the moving bed reactor. All individual values and subranges from 50 to 100 mole percent, are included; for example, the hydrogen combustion can be from a lower limit of 50, 60, 70, or 75 mole percent to an upper limit of 100, 99, or 98 mole percent of the hydrogen produced by steam cracking. Hydrogen, when not combusted, can be discharged from the moving bed reactor 103 via gas output 111.

[0055] Embodiments provide that the system 101 includes a first transfer conduit 113.Embodiments provide that the first transfer conduit is configured to transfer the reduced solid oxygen carrier from the moving bed reactor 103 to the regenerator vessel 105. As previously mentioned, the solid oxygen carrier can undergo reduction in the presence of hydrogen produced by steam cracking in the moving bed reactor 103.

[0056] The first transfer conduit 113 can be configured to transfer the reduced solid oxygen carrier from the moving bed reactor 103 to the regenerator vessel 105 utilizing known components. Different components can be utilized for various applications. Examples of components that may be utilized to configure the first transfer conduit include, but are not limited to, dip legs, standpipes, valves, orifices, weirs, cyclone separators, loop seals, seal pots, air locks, inclined pipes, and vertical pipes.

[0057] As shown in the Figure, the first transfer conduit 113 can be configured to transfer the reduced solid oxygen carrier from the lower section 108 of the moving bed reactor 103 to the regenerator vessel 105; however, embodiments are not so limited.

[0058] Embodiments provide that the first transfer conduit 113 can have a temperature from 550 to 850 °C. All individual values and subranges from 550 to 850 °C are included; for example, the first transfer conduit can have a temperature from a lower limit of 550, 600, 650, or 700 °C to an upper limit of 850, 800, 775, or 750 °C.

[0059] One or more embodiments provide that the regenerator 105 is a fluidized bed vessel, i.e., a fluidized bed regenerator. One or more embodiments provide that the regenerator is a moving bed vessel, i.e., a moving bed regenerator. Fluidized bed vessels are known. Moving bed vessels are known. Embodiments provide the regenerator vessel 105 can be utilized for oxidation of the reduced solid oxygen carrier transferred to the regenerator vessel 105 from the moving bed reactor 103. Different regenerator vessels can be utilized for various applications. For instance, the regenerator vessel can have various dimensions and / or various geometries for different applications. A number of suitable regenerator vessels are discussed in publicationsWO 2024 / 059600 A1, WO 2024 / 059551 A1, WO 2024 / 059552 A1, WO 2024 / 059552 A1, and / or EP 3844134, each of which is incorporated by reference, in its entirety, herein.

[0060] Embodiments provide that the regenerator vessel 105 an have an operational temperature, e.g., a steady state temperature, from 650 to 925 °C. All individual values and subranges from 650 to 925 °C are included; for example, the regenerator vessel can have an operational temperature from a lower limit of 650, 675, or 700 °C to an upper limit of 925, 900, 800, or 775 °C. One or more embodiments provides that the regenerator vessel has a greater operational temperature than the moving bed reactor 103. Operational temperature can be determined as an outlet temperature of the flue gas from the regenerator vessel.

[0061] Embodiments provide that the regenerator vessel 105 can have an operational pressure, e.g., a steady state pressure, from 1 to 10 bara. All individual values and subranges from 1 to 10 bara are included; for example, the regenerator vessel can have an operational pressure from a lower limit of 1, 1.2, or 1.5 bara to an upper limit of 10, 5, 4, or 3 bara. Operational pressure can be determined as an outlet pressure of the flue gas from the regenerator vessel.

[0062] Embodiments provide that the regenerator vessel 105 includes an oxidizing agent input 115. An oxidizing agent can be transferred to the regenerator vessel via the oxidizing agent input 115. One or more embodiments provide the oxidizing agent is air, enriched air, oxygen, or combinations thereof. One or more embodiments provide the oxidizing agent is air. The air can be atmospheric air, which may be referred to as ambient air. The oxidizing agent can be utilized for oxidation of the reduced solid oxygen carrier transferred to the regenerator vessel 105 from the moving bed reactor 103. One or more embodiments provide that heat can be generated by oxidizing an additional heat generating combustible fuel in the regenerator vessel.

[0063] Advantageously, the oxidation of the reduced solid oxygen carrier, which is an exothermic process, can generate heat that, in turn, can be utilized for the endothermic steam cracking of the carbonaceous feedstock and the endothermic conversion of the fossil hydrocarbon feedstock in the moving bed reactor 103. Heat generated in the regenerator vessel 105 by oxidation of the reduced solid oxygen carrier can reduce the fuel demand of the system 101.

[0064] Heat transfer is known. Heat that is generated by oxidation of the reduced solid oxygen carrier can be transferred by various methods for different applications. For instance, heated and oxidized solid oxygen carrier can be transferred from the regenerator vessel 105 to the moving bed reactor 103.

[0065] Further advantageously, because the amount of fuel e.g., additional heat generating combustible fuel, added to the system 101 is reduced and / or eliminated entirely, there is a correspondingly reduced fuel combustion. As the fuel combustion is reduced and / or eliminated entirely, CO2 generated from fuel combustion is also reduced and / or eliminated entirely. Purity hydrogen supplemental fuel can be used to provide CO2 free energy input.

[0066] One or more embodiments provide that the system 101 includes an additional heat generating combustible fuel input, while not shown in the Figure. The additional heat generating combustible fuel can be a fossil fuel, such as natural gas or light hydrocarbons, or hydrogen produced from hydrocarbon reforming. The additional heat generating combustible fuel can also be a low GHG footprint “green” fuel, such as, for example, hydrogen generated from electrolysis using low carbon footprint electricity or renewable electricity. One or more embodiments provide that the additional heat generating combustible fuel is natural gas. Different additional heat generating combustible fuels can be utilized for various applications. Different amounts of the additional heat generating combustible fuels can be utilized for various applications.Embodiments provide that the additional heat generating combustible fuel input can be into the moving bed reactor 103 and / or regenerator vessel 105. One or more embodiments provide that the additional heat generating combustible fuel input can be into the moving bed reactor 103. One or more embodiments provide that the additional heat generating combustible fuel input can be into the regenerator vessel 105.

[0067] One or more embodiments provide that an additional heat generating combustible fuel can be provided to the fluidized bed system 101. One or more embodiments provide that an additional heat generating combustible fuel, when utilized, can be from 0.0001 to 0.0100 kg per kg of the combination of feedstocks input to the reactor. All individual values and subranges from 0.0001 to 0.0100 kg / kg combination of feedstocks, are included; for example, the additional heat generating combustible fuel can be from a lower limit of 0.0001 , 0.0005, or 0.0010 to an upper limit of 0.0100, 0.0800, 0.0050, 0.0040, or 0.0030 kg / kg combination of feedstocks.

[0068] One or more embodiments provide that no, i.e. , zero, additional heat generating combustible fuel is utilized. In other words, all heat utilized for endothermic steam cracking of the carbonaceous feedstock and the endothermic hydrogenation of the fossil hydrocarbon feedstock the moving bed reactor 103 is provided by combustion of in-situ produced products,e.g., H2, in the moving bed reactor 103 and / or by oxidation of the reduced solid oxygen carrier in the regenerator vessel 105.

[0069] Embodiments provide that the system 101 includes a second transfer conduit 117. Embodiments provide that the second transfer conduit is configured to transfer the oxidized solid oxygen carrier from the regenerator vessel 105 to the moving bed reactor 103. As previously mentioned, the solid oxygen carrier can undergo oxidation in the presence of an oxidizing agent in the regenerator vessel 105.

[0070] The second transfer conduit 117 can be configured to transfer the oxidized solid oxygen carrier from the regenerator vessel 105 to the moving bed reactor 103 utilizing known components. Different components can be utilized for various applications. Examples of components that may be utilized to configure the second transfer conduit include, but are not limited to, dip legs, standpipes, valves, orifices, weirs, cyclone separators, loop seals, seal pots, air locks, inclined pipes, and vertical pipes.

[0071] As shown in the Figure, the second transfer conduit 117 can be configured to transfer the oxidized solid oxygen carrier from the regenerator vessel 105 to the upper section 104 of the moving bed reactor 103; however, embodiments are not so limited.

[0072] One or more embodiments provide that that the carbonaceous feedstock, the fossil hydrocarbon feedstock, the oxidized solid oxygen carrier, and steam are transferred to the moving bed reactor 103 in the upper section 104. As such, contents of the moving bed reactor 103 can travel from a relatively higher point to a relatively lower point, e.g. from the upper section 104 to the middle section 106 and then from the middle section 106 to the lower section 108.

[0073] Embodiments provide that the system 101 includes a flue gas output 119. A gas stream can exit the regenerator vessel 105 via the flue gas output 119.

[0074] One or more embodiments provide that the fossil hydrocarbon feedstock and the oxidized solid oxygen carrier are transferred to the moving bed reactor 103 in the upper section 104, while the carbonaceous feedstock is transferred to the moving bed reactor in middle section 106. Such embodiments can provide that the fossil hydrocarbon feedstock is converted, e.g., ethane is converted to ethylene, as the components flow down the moving bed reactor. As conversion occurs, hydrogen that is produced can be combusted and steam can be generated. As such, the location in the middle section 106 where the carbonaceous feedstock is transferred to the moving bed reactor can be steam rich, e.g., where the partial pressure of steam is at ornear a maximum. Advantageously, this in-situ steam generation can lower, e.g. completely or partially, steam input to the moving bed reactor, while still providing that olefins are produced. Accordingly, lowering, e.g. completely or partially, of steam input to the moving bed reactor can lower an overall energy utilization and CO2 footprint of the system 101. One or more embodiments provide that no, i.e. zero, steam is input to the moving bed reactor; in other words, all steam utilized by the process for steam cracking of the carbonaceous feedstock is generated in-situ.

[0075] One or more embodiments provide that the fossil hydrocarbon feedstock and the carbonaceous feedstock are transferred to moving bed reactor 103 to provide a counter-current flow relative to a downward flow of the solid oxygen carrier. For example, fossil hydrocarbon feedstock and the oxidized solid oxygen carrier can be transferred to the moving bed reactor 106 in the upper section 104 while the carbonaceous feedstock is transferred to the moving bed reactor in the lower portion 108. For such embodiments, the fossil hydrocarbon feedstock can flow downward with the oxidized solid oxygen carrier to be converted to ethylene, with in-situ steam generation occurring due to selective hydrogen combustion. For such embodiments, a gas output can be located in the middle section 106 to remove olefins from the moving bed reactor. Then, as the reduced solid oxygen carrier continues to travel downwards in the moving bed reactor, the carbonaceous feedstock moving counter-currently to the reduced solid oxygen carrier can undergo cracking to produce olefins, which may also be collected at the gas output located in the middle section 106.

[0076] Gas removed from the flue gas output 119 can include depleted air. As used herein, “depleted air” refers to air having a lower concentration of oxygen, as compared to atmospheric air, e.g., air that is input to the regenerator vessel 105 by oxidizing agent input 119.

[0077] Embodiments provide that gas exiting via the flue gas output 119 can have an improved, i.e., reduced, CO2 footprint (kg CO2 / kg combination of feedstocks), as compared to other processes for identical combination of feedstocks.

[0078] The following examples are provided for illustration but are not intended to limit the scope. All parts and percentages are by weight unless otherwise indicated.EXAMPLES

[0079] Aspen Plus V14 (obtained from Aspen Technology) was utilized to perform computations for methods for producing olefins. For the computations, a PSRK (Predictive Soave-Redlich-Kwong) equation of state model was used. The parameters for the chemicalcomponents modeled were extracted from the Aspen databank. Comparative Example A-1 was modeled as discussed in publication US 2022 / 0145194 A1. For Comparative Example A-1 , a bench scale bubbling fluidized bed gasifier was utilized and a mixture of dolomite and sand (dolomite : sand was 50:50 weight percent) was used as a bed material, where the dolomite was modeled using US Geological Survey reported property data and the sand was modeled using properties of SiC>2 reported by NIST.

[0080] In the model, a carbonaceous feedstock (polyethylene) feed was gasified with steam at a temperature of 705 °C and a fluidizing velocity of 0.31 m / s; residence time in the gasifier was about 4 to 8 seconds. For Comparative Example A-1, carbonaceous feedstock (polyethylene; 25 wt%) and fossil hydrocarbon feedstock (ethane; 75 wt%), based upon a total weight of the carbonaceous feedstock and the fossil hydrocarbon feedstock, was modeled as feed to the reactor.

[0081] The hydrogen combustion and product component yields per polyethylene material feed, as dry product gas are reported in Tables 2-5. Utilizing the data from Comparative Example A-1 , Mass and Heat of Reaction balances were determined for the reactor and a regenerator.Comparative Examples A-2 and A-3 were performed as Comparative Example A-1 with changes in the carbonaceous feedstock / ethane weight percents shown in the respective tables, the results are reported in Tables 2-5.

[0082] Polyethylene combustion was estimated to be 45,000 kJ / kg. Polyethylene number average molecular weight (n = 1 ,000) was 28,050 g / mol. Input energy was -55,300.00 kJ / mole polyethylene.

[0083] Example 1-1 was performed as follows. Utilizing the data from Comparative Example A, with the change that a moving bed reactor was modeled and a solid oxygen carrier (MnO^Mn3C>4) was used rather than the mixture of dolomite and sand. It is understood by those skilled in the art, as mentioned earlier, that the selectivity of the solid oxygen carrier for hydrogen combustion can be modified as necessary through the selection and optimization of reducible metal oxides and the addition of promoters. The modelled solid oxygen carrier in the examples serves as a proxy for the final material, which is intended to contain a promoter and, in some embodiments, a support material. Mass, and Heat of Reaction balances were determined for the reactor and a fluidized bed regenerator. Examples 1-2 and 1-3 were performed as Example 1-1 with changes in the carbonaceous feedstock / ethane weight percents shown in the respective tables, the results are reported in Tables 2-5. It was assumed that thematerial was completely oxidized when it left the regenerator; the regenerator had a maximum operating temperature of 900 °C and a maximum operating pressure of 5 bara.

[0084] Example 2-1 was performed as follows. Utilizing the data from Comparative Example A, with the change that a moving bed reactor was modeled and a solid oxygen carrier (MnO^Mn C^) was used rather than the mixture of dolomite and sand, Yield, Mass and Heat of Reaction balances were determined for the reactor and a regenerator. Examples 2-2 and 2-3 were performed as Example 2-1 with changes in the carbonaceous feedstock / ethane weight percents shown in the respective tables, the results are reported in Tables 2-5. It was assumed that the material was completely oxidized when it left the regenerator; the regenerator had a maximum operating temperature of 900 °C and a maximum operating pressure of 5 bara, the results are reported in Tables 2-5.

[0085] Molar mass, Standard Enthalpy of Formation, Standard Enthalpy of Combustion, and Energy Output are reported in Table 1.Table 1Table 2TABLE 3

[0086] The data of Table 3 show that Example 1-1 and Example 2-1 each had an improved, i.e. reduced, CO2 flue gas concentration as compared to Comparative Example A-1.TABLE 4

[0087] The data of Table 4 show that Example 1-2 and Example 2-2 each had an improved, i.e. reduced, CO2 flue gas concentration as compared to Comparative Example A-2.TABLE 5

[0088] The data of Table 5 show that Example 1-3 and Example 2-3 each had an improved, i.e. reduced, CO2 flue gas concentration as compared to Comparative Example A-3.

[0089] As shown for Examples 1-1, 1-2, and 1-3, combustion of hydrogen produced by steam cracking of the carbonaceous feedstock generated approximately 100% of the energy for the endothermic steam cracking reaction and the endothermic conversion reaction. In this analysis, the energy balance for the reactor and the regenerator were considered, which included the heat of vaporization of the reactant (assumed to be pyrolysis oil), generation of dilution steam, and heating up with the reactant (polyethylene and ethane) to the reaction temperature, heat transfer to and from circulating solid, heat recovery from the reactor product and the regenerator flue gas, and heating up the combustion air and fuel for the regenerator. For Examples 1-1, 1-2, 1-3, 2-1, 2-2, and 2-3, the heat of reduction and heat of oxidation of the solid oxygen carrier (MnO^Mn3C>4) was also considered. For Examples 1-1, 1-2, and 1-3, it was assumed that there was 100% combustion of the H2 produced from the cracking of the carbonaceousfeedstock and conversion of ethane to ethylene. This in-situ heat generation advantageously lowered the solids circulation flow and lowered the net fuel demand in the regenerator. The regenerator fuel demand was further lowered by the heat released upon re-oxidation of the reduced solid oxygen carrier. The CO2 released in the flue gas of the regenerator was reduced by up to 97 to 99%, in contrast to the respective Comparative Examples, depending upon the carbonaceous feedstock / ethane feed ratio.

[0090] As shown for Examples 2-1 , 2-2, and 2-3, heat was generated in the reactor through combustion of a portion of the tar generated from the cracking of the carbonaceous feedstock. Advantageously, this additional heat can compensate for the natural gas demand for the regenerator. Although combustion of a portion of the tar does increase the net CO2 selectivity, in comparison to respective Examples 1-1, 1-2, 1-3, the CO2 was present in the process gas stream, where it can be more easily captured with conventional acid gas removal means from hydrocarbon streams, as compared to capturing the CO2 from low-pressure flue gas.

Claims

AMENDED CLAIMSreceived by the International Bureau on24 August 2026 (24.08.2026)What is claimed is:

1. A method for producing olefins, the method comprising:transferring a carbonaceous feedstock comprising polymeric materials to a moving bed reactor;transferring a fossil feedstock comprising ethane, propane, n-butane, iso-butane, ethylbenzene, naphtha, or combinations thereof to the moving bed reactor;converting the fossil hydrocarbon feedstock in the moving bed reactor to produce olefins; steam cracking the carbonaceous feedstock in the moving bed reactor to produce olefins and hydrogen;combusting the hydrogen in the moving bed reactor utilizing a solid oxygen carrier to produce a reduced solid oxygen carrier;transferring the reduced solid oxygen carrier from the moving bed reactor to a regenerator vessel;generating heat by oxidizing the reduced solid oxygen carrier in the regenerator vessel; andtransferring the oxidized solid oxygen carrier from the regenerator vessel to the moving bed reactor.

2. The method of claim 1 , wherein the fossil hydrocarbon feedstock comprises ethane, propane, n-butane, isobutane, ethylbenzene, naphtha, or combinations thereof.

3. The method of any one of the preceding claims, wherein the solid oxygen carrier comprises a redox-active transition metal oxide.

4. The method of claim 3, wherein the solid oxygen carrier comprises a promoter.

5. The method of any one of the preceding claims, wherein the fossil hydrocarbon feedstock is equal to or greater than 20 weight percent based upon a total weight of the fossil hydrocarbon feedstock and the carbonaceous feedstock transferred to the moving bed reactor.

6. The method of any one of the preceding claims, wherein the carbonaceous feedstock comprises polyethylene.

7. The method of any one of the preceding claims, comprising transferring an oxidizing agent to the regenerator vessel.

8. The method of any one of the preceding claims, wherein the fossil hydrocarbon feedstock comprises ethane or propane and the fossil hydrocarbon feedstock is converted by dehydrogenation.

9. The method of any one of the preceding claims, comprising transferring a dehydrogenation catalyst to the moving bed reactor.

9. The method of any one of the preceding claims, comprising transferring an additional heat generating combustible fuel to the regenerator vessel.

10. The method of any one of the preceding claims, wherein the moving bed reactor has an operational temperature from 550 to 850 °C and an operational pressure from 1 to 10 bara and the regenerator vessel has an operational temperature from 650 to 925 °C and an operational pressure from 1 to 10 bara.

11. The method of any one of the preceding claims, wherein combusting the hydrogen in the moving bed reactor produces heat.

12. The method of any one of the preceding claims, comprising transferring steam to the moving bed reactor.

13. The method of any one of the preceding claims, wherein the moving bed reactor has a solid oxygen carrier to carbonaceous feedstock ratio from 1 to 200 kilograms solid oxygen carrier per kilogram of a combination of the carbonaceous feedstock and the fossil hydrocarbon feedstock transferred to the reactor.

14. The method of any one of the preceding claims, wherein from 50 to 100 mole percent of the hydrogen is combusted in the moving bed reactor.

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