WO2025014849A2 - Catalyst compositions and methods for converting carbon into carbon oxides - Google Patents
Catalyst compositions and methods for converting carbon into carbon oxides Download PDFInfo
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- WO2025014849A2 WO2025014849A2 PCT/US2024/036996 US2024036996W WO2025014849A2 WO 2025014849 A2 WO2025014849 A2 WO 2025014849A2 US 2024036996 W US2024036996 W US 2024036996W WO 2025014849 A2 WO2025014849 A2 WO 2025014849A2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/06—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by pressure distillation
- C10G9/08—Apparatus therefor
- C10G9/12—Removing incrustation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Definitions
- the disclosed technology provides catalyst compositions and methods of use thereof. More specifically, the disclosed technology relates to compositions and methods for converting carbon into carbon oxides in low temperature as well as in high temperature petrochemical, hydrocarbon, carbon production and carbon processing applications, for degrading per- or polyfluoroalkyl substances (PFAS) during incineration of waste materials, and for mitigating process and/or equipment fouling.
- PFAS per- or polyfluoroalkyl substances
- Example of the surfaces that experience coking are, for example, but not limited to, the refinery crude unit, the vacuum unit, the fluid catalytic cracker unit (FCC), the delayer coker unit, the visbreaker unit, and ethylene dichloride-vinyl chloride monomer units (EDC-VCM). These units experience fouling in the temperature range of about 300°C to about 1200°C, wherein the current solutions (e.g. antifoulant additives, coatings, metallurgy/mechanical design) are not effective nor economical, especially at temperatures of about 300°C to about 600°C (z.e. “low-temperature” processes).
- the current solutions e.g. antifoulant additives, coatings, metallurgy/mechanical design
- Loss of heat transfer and subsequent charge outlet temperature decrease is a result of the low thermal conductivity of the coke deposition layer or layers which is generally lower than the thermal conductivity of the fluids or conduction wall. As a result of this lower thermal conductivity, the overall thermal resistance to heat transfer is increased and the effectiveness and thermal efficiency of heat exchangers are reduced. These cumulative effects lead to a loss of efficiency and profitability in the operations of these facilities.
- compositions and methods for treating and mitigating coke deposition and coke associated fouling in low temperature, as well as in high temperature petrochemical and hydrocarbon processing applications are needed in the art.
- a catalyst composition comprising a perovskite material of formula A a BbCcDdO x -s, wherein 0 ⁇ a ⁇ 3.2, 0 ⁇ b ⁇ l.2, 0.9 ⁇ a+b ⁇ 3.2, 0 ⁇ c ⁇ l.2, 0.0 ⁇ d ⁇ l.2, 0.9 ⁇ c+d ⁇ L2, 3 ⁇ x ⁇ 9.2, and -0.5 ⁇ 8 ⁇ 0.5; wherein (i) A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; (ii) B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; (iii) C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt
- A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof.
- B is selected from scandium (Sc) yttrium (Y), and/or a combination thereof.
- C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof.
- D is selected from cerium (Ce), tungsten (W), and/or a combination thereof.
- the perovskite material is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03,
- BaZr(0.1)Ce(0.7)Y(0.2)03 and/or a combination thereof.
- a method for converting carbon into carbon oxides in processing systems selected from petrochemical, hydrocarbon, carbon production and carbon processing systems comprising: applying a catalyst composition to the processing system, the catalyst composition comprising a perovskite having the formula A a BbC c DdO x -6, wherein 0 ⁇ a ⁇ 3.2, O ⁇ b ⁇ l.2, 0.9 ⁇ a+b ⁇ 3.2, O ⁇ c ⁇ l.2, O.O ⁇ d ⁇ l.2, 0.9 ⁇ c+d ⁇ L2, 3 ⁇ x ⁇ 9.2, and -0.5 ⁇ 5 ⁇ 0.5 is disclosed.
- A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof;
- B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof;
- C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (
- A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof.
- B is selected from scandium (Sc), yttrium (Y), and/or a combination thereof.
- C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof.
- D is selected from cerium (Ce), tungsten (W), and/or a combination thereof.
- the catalyst composition is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03,
- BaZr(0.1)Ce(0.7)Y(0.2)03 and/or a combination thereof.
- the processing system is selected from a refinery crude unit; a vacuum unit; a fluid catalytic cracker; a delayer coker; a hydrotreating unit; a visbreaker unit; a LC-Finer; an EDC-VCM; a steam cracker of hydrocarbons or biomass; a reforming unit of hydrocarbons or biomass; a pyrolysis unit for hydrocarbons or biomass; a unit for the pyrolysis and/or gasification of plastic, biomass, hydrocarbons, coal, petroleum coke, and/or municipal solid waste; a facility for the production of carbon, including, but not limited to, a facility for the production of carbon black, and a facility for the production of carbon nanotubes; and/or a unit for the incineration of waste materials.
- the processing system is a unit for the incineration of waste materials, wherein the waste materials comprise per- or polyfluoroalkyl substances (PFAS).
- PFAS per- or polyfluoroalkyl substances
- the processing system is selected from the group consisting of a coker unit furnace, a crude unit furnace, a coker unit heat exchanger and a crude unit heat exchanger, or a combination thereof.
- the processing system operates in the temperature range from about 300°C to about 1200°C. In some embodiments, the petrochemical or hydrocarbon processing system operates in the temperature range from about 300°C to about 600°C.
- the catalyst composition gasifies coke deposits on the hydrocarbon, petrochemical, carbon production or carbon processing system surfaces.
- a method for converting carbon into carbon oxides in processing systems selected from petrochemical, hydrocarbon, carbon production and carbon processing systems comprising: providing a slurry or a catalyst support system, wherein the slurry or catalyst support system comprises a perovskite material of formula A a BbC e DdO x -5, wherein 0 ⁇ a ⁇ 3.2, O ⁇ b ⁇ l.2, 0.9 ⁇ a+b ⁇ 3.2, 0 ⁇ c ⁇ l.2, O.O ⁇ d ⁇ l.2, 0.9 ⁇ c+d ⁇ L2, 3 ⁇ x ⁇ 9.2, and -0.5 ⁇ 5 ⁇ 0.5; wherein A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination
- the hydrocarbon, petrochemical, carbon production, or carbon processing system is selected from a refinery crude unit; a vacuum unit; a fluid catalytic cracker; a delayer coker; a hydrotreating unit; a visbreaker unit; a LC-Finer; an EDC-VCM; a steam cracker of hydrocarbons or biomass; a reforming unit of hydrocarbons or biomass; a pyrolysis unit for hydrocarbons or biomass; a unit for the pyrolysis and/or gasification of plastic, biomass, hydrocarbons, coal, petroleum coke, and/or municipal solid waste; a facility for the generalized production of carbon, including, but not limited to, a facility for the production of carbon black; and a facility for the production of carbon nanotubes; and/or a unit for the incineration of waste materials.
- the processing system is a unit for the incineration of waste materials, wherein the waste materials comprise per- or polyfluoroalkyl substances (PFAS).
- PFAS per- or polyfluoroalkyl substances
- the catalyst support system comprises silica or alumina, or metallics.
- a method for the degradation of PFAS during incineration of a waste material comprising: applying a catalyst composition to the waste material, the catalyst composition comprising a perovskite having the formula A a BbC c DdOx-8, wherein 0 ⁇ a ⁇ 3.2, 0 ⁇ b ⁇ l.2, 0.9 ⁇ a+b ⁇ 3.2, 0 ⁇ c ⁇ l.2, 0.0 ⁇ d ⁇ l.2, 0.9 ⁇ c+d ⁇ L2, 3 ⁇ x ⁇ 9.2, and 0.5 ⁇ 5 ⁇ 0.5 is disclosed.
- A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof;
- B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof;
- C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (
- A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof.
- B is selected from scandium (Sc), yttrium (Y), and/or a combination thereof.
- C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof.
- D is selected from cerium (Ce), tungsten (W), and/or a combination thereof.
- the catalyst composition is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03,
- BaZr(0. l)Ce(0.7)Y(0.2)03 and/or a combination thereof.
- a method for the mitigation of process and/or equipment fouling comprising: applying a catalyst composition to the process and/or equipment, the catalyst composition comprising a perovskite having the formula AaBbCcDdO x -6, wherein 0 ⁇ a ⁇ 3.2, O ⁇ b ⁇ l.2, 0.9 ⁇ a+b ⁇ 3.2, O ⁇ c ⁇ l.2, O.O ⁇ d ⁇ l.2, 0.9 ⁇ c+d ⁇ l.2, 3 ⁇ x ⁇ 9.2, and -0.5 ⁇ b ⁇ 0.5 is disclosed.
- A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof;
- B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof;
- C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (
- A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof.
- B is selected from scandium (Sc), yttrium (Y), and/or a combination thereof.
- C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof.
- D is selected from cerium (Ce), tungsten (W), and/or a combination thereof.
- the catalyst composition is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03,
- BaZr(0. l)Ce(0.7)Y(0.2)03 and/or a combination thereof.
- FIG. 1 provides experimental results of an illustrative embodiment of the disclosed technology.
- Approximating language may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about” is not to be limited to the precise value specified. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value.
- range limitations may be combined and/or interchanged; such ranges are identified and include all the sub-ranges contained therein unless context or language indicates otherwise.
- the term “or” is not meant to be exclusive and refers to at least one of the referenced components (for example, a material) being present and includes instances in which a combination of the referenced components may be present, unless the context clearly dictates otherwise.
- the terms “may” and “may be” indicate a possibility of an occurrence within a set of circumstances; a possession of a specified property, characteristic or function; and/or qualify another verb by expressing one or more of an ability, capability, or possibility associated with the qualified verb. Accordingly, usage of “may” and “may be” indicates that a modified term is apparently appropriate, capable, or suitable for an indicated capacity, function, or usage, while taking into account that in some circumstances, the modified term may sometimes not be appropriate, capable, or suitable. For example, in some circumstances, an event or capacity can be expected, while in other circumstances, the event or capacity cannot occur. This distinction is captured by the terms “may” and “may be”.
- coal refers to, but is not limited to, carbonaceous solid or liquid or particulates or macromolecules forming the carbonaceous solid or liquid, which are derived from coal, petroleum, wood, hydrocarbons and other materials containing carbon, and which include, for example, carbon black, carbon nanotubes, tar, and pyrolytic coke existing in hydrocarbon, petrochemical, carbon production or carb processing units.
- coking refers to, but is not limited to, the deposition of coke or a layer of coke on the surface of a hydrocarbon, petrochemical, carbon production or carbon processing unit.
- the disclosed technology generally provides for catalyst compositions and methods for converting carbon into carbon oxides in petrochemical, hydrocarbon, carbon production, and carbon processing systems. More specifically, the disclosed technology relates to compositions and methods for converting carbon into carbon oxides in low temperature as well as in high temperature petrochemical, hydrocarbon, carbon production, and carbon processing applications.
- a catalyst composition for converting carbon into a carbon oxide or carbon oxides in a petrochemical, hydrocarbon, carbon production and/or carbon processing system is provided.
- the catalyst composition provides for the inhibition of coking and coke associated fouling in such processing systems by providing catalyst compositions comprising perovskite materials.
- the perovskite materials of the disclosed technology have proved beneficial in the conversion of carbon into carbon oxides. Without being bound by theory, it is believed that when coke forms on the surfaces of the disclosed perovskite compositions, the coke is converted immediately to a carbon oxide, wherein these carbon oxides immediately gasify and dissipate. Examples of such carbon oxides, include, but are not limited to, carbon monoxide and carbon dioxide.
- the disclosed technology minimizes and/or mitigates unwanted fouling and/or coking of process and/or equipment, including, but not limited to, heat exchange equipment (e.g. shell and tube exchangers, furnace tubes, etc.) that causes heat transfer loss leading to higher fuel/energy consumption (and thus higher CO2 emissions), pressure drop, and carburization of substrate metallurgy in petrochemical, hydrocarbon, carbon production and carbon processing system applications. It also offers reduction in deactivation of other process catalysts, such as for reforming, hydrotreating, pyrolysis, and gasification.
- heat exchange equipment e.g. shell and tube exchangers, furnace tubes, etc.
- the disclosed technology may help reduce the temperature required to adequately degrade per- and polyfluoroalkyl substances (PF AS) in waste materials.
- PF AS per- and polyfluoroalkyl substances
- the catalyst compositions of the disclosed technology may facilitate easier mineralization of fluorine chemistry by enabling formation of organo fluoride radicals at lower temperatures due to coordination defects/cleavage (leading to high electron density at defective sites) on the surface of the catalyst due to heat treatment during incineration processes. This aspect may be further accelerated by the presence of transition metal compositions in the catalyst composition of the disclosed technology as well as transition metal impurities, such as iron, on the surface.
- oxygen vacancy in the structure of the catalyst composition, such vacancy could not only help accelerate oxidation reactions, including conversion of any CO to CO2, but could also help with hydrodefluorination when an oxidant such as steam, CO2, air, or oxygen is available, due to abstraction of oxygen from the oxidant by the oxygen vacancy.
- the catalyst composition comprises a perovskite material of formula A a BbC c DdO x -s, wherein 0 ⁇ a ⁇ 3.2, 0 ⁇ b ⁇ l.2, 0.9 ⁇ a+b ⁇ 3.2, O ⁇ c ⁇ l.2, O.O ⁇ d ⁇ l .2, 0.9 ⁇ c+d ⁇ L2, 3 ⁇ x ⁇ 9.2, and -0.5 ⁇ 5 ⁇ 0.5; wherein (i) A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; (ii) B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; (iii) C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni
- the catalyst composition comprises A, wherein A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof.
- the catalyst composition comprises B, wherein B is selected from scandium (Sc) yttrium (Y), and/or a combination thereof.
- the catalyst composition comprises C, wherein C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof.
- the catalyst composition comprises D, wherein D is selected from cerium (Ce), tungsten (W), and/or a combination thereof.
- D is tungsten (W)-based, wherein D is selected from tungstate, tungsten ion, and/or a combination thereof.
- the catalyst composition comprises a perovskite material that is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03,
- the catalyst composition comprises tungsten. It is believed that tungsten or tungsten-based materials are effective as catalysts at low or high temperature due to the oxide ion conductivity.
- a method for converting carbon into carbon oxides in petrochemical, hydrocarbon, carbon production and/or carbon processing systems comprises applying a catalyst composition to the petrochemical, hydrocarbon, carbon production and/or carbon processing system and/or unit, wherein the catalyst composition comprises a perovskite having the formula A a BbCcDdOx- «. wherein 0 ⁇ a ⁇ 3.2, 0 ⁇ b ⁇ l.2, 0.9 ⁇ a+b ⁇ 3.2, 0 ⁇ c ⁇ l.2, O.O ⁇ d ⁇ l.2, 0.9 ⁇ c+d ⁇ L2, 3 ⁇ x ⁇ 9.2, and -0.5 ⁇ 5 ⁇ 0.5.
- the catalyst composition of the present technology may be applied by any conventional means known or recognized in the art.
- the catalyst composition may be applied to the processing system by painting, spraying, and/or dipping and drying methods.
- the catalyst composition may be applied to the processing system during manufacturing or retrofitting.
- the catalyst composition of the disclosed method comprises A, wherein A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (P
- A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof.
- B is selected from scandium (Sc), yttrium (Y), and/or a combination thereof.
- C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof.
- D is selected from cerium (Ce), tungsten (W), and/or a combination thereof.
- D is tungsten (W)-based, wherein D is selected from tungstate, tungsten ion, and/or a combination thereof.
- the catalyst composition of the disclosed method is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03, BaZr(0.1)Ce(0.7)Y(0.2)03, and/or a combination thereof.
- the present method further provides for a petrochemical, hydrocarbon, carbon production or carbon processing system.
- a petrochemical, hydrocarbon, carbon production or carbon processing system It should be understood that coking occurs in such systems because the temperature and the hydrocarbon, petrochemical, or carbon residence time are higher than the stability limitations of these materials. As such, formation of coke or coke-like material increases dramatically as local metal contact temperatures exceed about 300°C. Operational factors can influence coke formation, such as hot shutdowns, which promote coke build up. Even under normal operating conditions, coking can occur under standard operating conditions for various units within petrochemical, hydrocarbon, carbon production, or carbon processing systems.
- the hydrocarbon, petrochemical, carbon production or carbon processing system of the present method comprises a refinery crude unit; a refinery vacuum unit; a fluid catalytic cracker; a delayer coker; a hydrotreating unit; a visbreaker unit; a LC-Finer; an EDC-VCM; a steam cracker of hydrocarbons or biomass; transfer line exchangers following the steam cracker in ethylene production; a reforming unit of hydrocarbons or biomass; a pyrolysis unit for hydrocarbons or biomass; a unit for the pyrolysis and/or gasification of plastic, biomass, hydrocarbons, coal, petroleum coke, and/or municipal solid waste; a facility for the generalized production of carbon, including, but not limited to, a facility for the production of carbon black; a facility for the production of carbon nanotubes, and/or a unit for the incineration of waste materials, such as municipal sludge/waste that comprise PFAS and/or other waste materials that include
- the hydrocarbon or petrochemical processing system of the present method is selected from the group consisting of a coker unit furnace, a crude unit furnace, a coker unit heat exchanger and a crude unit heat exchanger, or a combination thereof.
- the petrochemical, hydrocarbon, carbon production or carbon processing system of the present method operates in the temperature range from about 300°C to about 1200°C. At temperatures about and above 300°C, fouling precursors such as asphaltenes in crude oil or unsaturated hydrocarbons from thermal cracking further dehydrogenate to produce coke or coke-like material.
- the petrochemical, hydrocarbon, carbon production or carbon processing system and/or unit of the disclosed method operates in the temperature range from about 300°C to about 600°C. It is believed that in this low temperature range, the activation energy available to gasify coke or coke-like material is lower, and thus is more challenging.
- Examples are heat exchanges and/or furnaces in a refinery crude unit; a refinery vacuum unit; a fluid catalytic cracker; a delayer coker; a hydrotreating unit; a visbreaker unit; a LC-Finer; an EDC-VCM; transfer line exchangers following the steam cracker in ethylene production; a pyrolysis unit for hydrocarbons or biomass and/or municipal solid waste; feed heaters in a carbon black production unit.
- the catalyst composition of the present method gasifies coke deposits on or within the hydrocarbon, petrochemical, carbon production, or carbon processing system unit surfaces.
- the catalyst composition is effective at gasifying coke in the temperature range from about 300°C to about 1200°C, and in other embodiments from about 300°C to about 600°C.
- a method for converting carbon into carbon oxides in petrochemical, hydrocarbon, carbon production and/or carbon processing systems is provided.
- the method comprises, providing a slurry or a catalyst support system, where the slurry or catalyst support system comprises a perovskite material of formula A a BbC c DdO x -8, wherein 0 ⁇ a ⁇ 3.2, 0 ⁇ b ⁇ l.2, 0.9 ⁇ a+b ⁇ 3.2, 0 ⁇ c ⁇ l .2, 0.0 ⁇ d ⁇ l.2, 0.9 ⁇ c+d ⁇ L2, 3 ⁇ x ⁇ 9.2, and -0.5 ⁇ 5 ⁇ 0.5; wherein A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel
- the slurry or catalyst support system is applied to the hydrocarbon, petrochemical, carbon production or carbon processing system selected from a refinery crude unit; a vacuum unit; a fluid catalytic cracker; a delayer coker; a hydrotreating unit; a visbreaker unit; a LC-Finer; an EDC-VCM; a steam cracker of hydrocarbons or biomass; a reforming unit of hydrocarbons or biomass; a pyrolysis unit for hydrocarbons or biomass; a unit for the pyrolysis and/or gasification of plastic, biomass, hydrocarbons, coal, petroleum coke, and/or municipal solid waste; a facility for the generalized production of carbon, including, but not limited to, a facility for the production of carbon black; facility for the production of carbon nanotubes; and/or a unit for the incineration of waste materials, such as municipal sludge/waste that comprise PF AS and/or other waste materials that include PFAS.
- waste materials such as municipal sludge/waste that comprise
- a method for degrading PFAS during incineration of a waste material comprises applying a catalyst composition to the waste material, wherein the catalyst composition comprises a perovskite having the formula A a BbC c DdO x -8, wherein 0 ⁇ a ⁇ 3.2, O ⁇ b ⁇ l.2, 0.9 ⁇ a+b ⁇ 3.2, O ⁇ c ⁇ l.2, 0.0 ⁇ 1.2, 0.9 ⁇ c+d ⁇ L2, 3 ⁇ 9.2, and -0.5 ⁇ 8 ⁇ 0.5.
- the catalyst composition of the disclosed method comprises A, wherein A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (P
- A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof.
- B is selected from scandium (Sc), yttrium (Y), and/or a combination thereof.
- C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof.
- D is selected from cerium (Ce), tungsten (W), and/or a combination thereof.
- D is tungsten (W)-based, wherein D is selected from tungstate, tungsten ion, and/or a combination thereof.
- the catalyst composition of the disclosed method is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03, BaZr(0.1)Ce(0.7)Y(0.2)03, and/or a combination thereof.
- a method for mitigation of process and/or equipment fouling comprises applying a catalyst composition to the process and/or equipment, wherein the catalyst composition comprises a perovskite having the formula AaBbCcDdOx.g, wherein 0 ⁇ a ⁇ 3.2, 0 ⁇ b ⁇ l .2, 0.9 ⁇ a+b ⁇ 3.2, 0 ⁇ c ⁇ l .2, O.O ⁇ d ⁇ l .2, 0.9 ⁇ c+d ⁇ l.2, 3 ⁇ x ⁇ 9.2, and -0.5 ⁇ 8 ⁇ 0.5.
- the catalyst composition of the disclosed method comprises A, wherein A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (P
- A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof.
- B is selected from scandium (Sc), yttrium (Y), and/or a combination thereof.
- C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof.
- D is selected from cerium (Ce), tungsten (W), and/or a combination thereof.
- D is tungsten (W)-based, wherein D is selected from tungstate, tungsten ion, and/or a combination thereof.
- the catalyst composition of the disclosed method is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03, BaZr(0.1)Ce(0.7)Y(0.2)03, and/or a combination thereof.
- Testing was conducted according to the following procedure.
- a 10:1 (w/w) Perovskite:Carbon Black sample was tested using a Thermal Gravimetric Analyzer (Jump to 100°C; Equilibrate at 100°C; Switch to Air; Ramp 50°C /min to 400°C; Ramp 5°C /min to 950°C).
- Temperature at 50% weight loss (T50) that is, 50% of the original carbon in the sample is oxidized, was used as the key measure of gasification capability of the example perovskite materials.
- a positive difference in T50 between Carbon Black and a 10:1 (w/w) Example Perovskite:Carbon Black mixture indicates positive coke/carbon gasification efficacy with which the perovskite material is able to convert any coke that comes into contact with a surface, deposited/coated with the perovskite material, of a hydrocarbon or a petrochemical processing system, to oxides of carbon and thus minimize fouling/coking.
- the disclosed example perovskites, particularly, tungstate-based perovskite materials E and F gasify coke (i.e.
- temperatures indicated in FIG. 1 are surface temperatures that are typically much higher than the bulk process temperatures.
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Abstract
A catalyst composition, the composition having a perovskite material of formula AaBbCcDdOx-δ, wherein 0<a<3.2, 0≦b≦1.2, 0.9<a+b≦3.2, 0≦c≦1.2, 0.0≦d≦1.2, 0.9<c+d≦1.2, 3≦x≦9.2, and -0.5<δ<0.5. A method for converting carbon into carbon oxides in processing systems selected from petrochemical, hydrocarbon, carbon production and carbon processing systems, the method provides applying a catalyst composition to a petrochemical or hydrocarbon processing unit, the catalyst composition comprising a perovskite having the formula AaBbCcDdOx-δ, wherein 0<a<3.2, 0≦b≦1.2, 0.9<a+b≦3.2, 0≦c≦1.2, 0.0≦d≦1.2, 0.9<c+d≦1.2, 3≦x≦9.2, and-0.5<δ<0.5. A method for converting carbon into carbon oxides in processing systems selected from petrochemical, hydrocarbon, carbon production and carbon processing systems, the method providing a slurry or a catalyst support system having a perovskite material of formula AaBbCcDdOx-δ, wherein 0<a<3.2, 0≦b≦1.2, 0.9<a+b≦3.2, 0≦c≦1.2, 0.0≦d≦1.2, 0.9<c+d≦1.2, 3≦x≦9.2, and -0.5<δ<0.5.
Description
CATALYST COMPOSITIONS AND METHODS FOR CONVERTING CARBON INTO CARBON OXIDES
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent Application No. 63/513,116 filed on July 12, 2023 and U.S. Provisional Patent Application No. 63/567,164 filed on March 19, 2024 and U.S. Provisional Patent Application No. 63/632,810 filed on April 1 1 , 2024, all of which are incorporated by reference herein in its entirety.
FIELD
[0002] The disclosed technology provides catalyst compositions and methods of use thereof. More specifically, the disclosed technology relates to compositions and methods for converting carbon into carbon oxides in low temperature as well as in high temperature petrochemical, hydrocarbon, carbon production and carbon processing applications, for degrading per- or polyfluoroalkyl substances (PFAS) during incineration of waste materials, and for mitigating process and/or equipment fouling.
BACKGROUND
[0003] In the processing of petrochemicals and hydrocarbons, surfaces of such processing units and equipment can become fouled due to the formation of fouling deposits on exposed surfaces. These fouling deposits may be in the form of undesired byproducts from the petrochemical or hydrocarbon processes. One such undesired byproduct is coke or coke-like material. The deposition of coke on these surfaces is commonly known as coking. The coking of these processing units leads to inefficiencies in the operation of petrochemical and hydrocarbon processing facilities.
[0004] Example of the surfaces that experience coking are, for example, but not limited to, the refinery crude unit, the vacuum unit, the fluid catalytic cracker unit (FCC), the delayer coker unit, the visbreaker unit, and ethylene dichloride-vinyl chloride monomer units (EDC-VCM). These units experience fouling in the temperature range of about 300°C to about 1200°C, wherein the current solutions (e.g. antifoulant additives,
coatings, metallurgy/mechanical design) are not effective nor economical, especially at temperatures of about 300°C to about 600°C (z.e. “low-temperature” processes).
[0005] Major detrimental effects of coke deposition and coke associated fouling include loss of heat transfer as indicated by charge outlet temperature decrease and pressure drop. Other detrimental effects of coke deposition and coke associated fouling may also include blocked process pipes, under-deposit corrosion and pollution. Where the heat flux is high, as in steam generators, coke deposition and coke associated fouling can lead to local hot spots resulting ultimately in mechanical failure of the heat transfer surface. Such effects lead in most cases to production losses and increased maintenance costs.
[0006] Loss of heat transfer and subsequent charge outlet temperature decrease is a result of the low thermal conductivity of the coke deposition layer or layers which is generally lower than the thermal conductivity of the fluids or conduction wall. As a result of this lower thermal conductivity, the overall thermal resistance to heat transfer is increased and the effectiveness and thermal efficiency of heat exchangers are reduced. These cumulative effects lead to a loss of efficiency and profitability in the operations of these facilities.
[0007] Thus, what is needed in the art is/are compositions and methods for treating and mitigating coke deposition and coke associated fouling in low temperature, as well as in high temperature petrochemical and hydrocarbon processing applications.
SUMMARY
[0008] In one aspect of the present technology, a catalyst composition, the composition comprising a perovskite material of formula AaBbCcDdOx-s, wherein 0<a<3.2, 0^b^l.2, 0.9<a+b^3.2, 0^c^l.2, 0.0^d^l.2, 0.9<c+d^L2, 3^x^9.2, and -0.5<8<0.5; wherein (i) A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; (ii) B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; (iii) C is selected from titanium (Ti), vanadium (V),
chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), hafnium (Hf), tantalum (Ta), thallium (Tl), lead (Pb) and any combination thereof; and (iv) D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu) hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), and any combination thereof is disclosed.
[0009] In some embodiments, A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof. In some embodiments, B is selected from scandium (Sc) yttrium (Y), and/or a combination thereof. In some embodiments, C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof. In some embodiments, D is selected from cerium (Ce), tungsten (W), and/or a combination thereof.
[0010] In some embodiments, the perovskite material is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03,
BaZr(0.1)Ce(0.7)Y(0.2)03, and/or a combination thereof.
[0011] In yet another aspect of the present technology, a method for converting carbon into carbon oxides in processing systems selected from petrochemical, hydrocarbon, carbon production and carbon processing systems, the method comprising: applying a catalyst composition to the processing system, the catalyst composition comprising a perovskite having the formula AaBbCcDdOx-6, wherein 0<a<3.2, O^b^l.2, 0.9<a+b^3.2, O^c^l.2, O.O^d^ l.2, 0.9<c+d^L2, 3^x^9.2, and -0.5<5<0.5 is disclosed.
[0012] In some embodiments, A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium
(Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), hafnium (Hf), tantalum (Ta), thallium (Tl), lead (Pb) and any combination thereof; and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu) hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), and any combination thereof.
[0013] In some embodiments, A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof. In some embodiments, B is selected from scandium (Sc), yttrium (Y), and/or a combination thereof. In some embodiments, C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof. In some embodiments, D is selected from cerium (Ce), tungsten (W), and/or a combination thereof.
[0014] In some embodiments, the catalyst composition is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03,
BaZr(0.1)Ce(0.7)Y(0.2)03, and/or a combination thereof.
[0015] In some embodiments, the processing system is selected from a refinery crude unit; a vacuum unit; a fluid catalytic cracker; a delayer coker; a hydrotreating unit; a visbreaker unit; a LC-Finer; an EDC-VCM; a steam cracker of hydrocarbons or biomass; a reforming unit of hydrocarbons or biomass; a pyrolysis unit for hydrocarbons or biomass; a unit for the pyrolysis and/or gasification of plastic, biomass, hydrocarbons, coal, petroleum coke, and/or municipal solid waste; a facility for the production of carbon, including, but not limited to, a facility for the production of carbon black, and a facility
for the production of carbon nanotubes; and/or a unit for the incineration of waste materials.
[0016] In some embodiments, the processing system is a unit for the incineration of waste materials, wherein the waste materials comprise per- or polyfluoroalkyl substances (PFAS).
[0017] In some embodiments, the processing system is selected from the group consisting of a coker unit furnace, a crude unit furnace, a coker unit heat exchanger and a crude unit heat exchanger, or a combination thereof.
[0018] In some embodiments, the processing system operates in the temperature range from about 300°C to about 1200°C. In some embodiments, the petrochemical or hydrocarbon processing system operates in the temperature range from about 300°C to about 600°C.
[0019] In some embodiments, the catalyst composition gasifies coke deposits on the hydrocarbon, petrochemical, carbon production or carbon processing system surfaces.
[0020] In yet another aspect of the present technology, a method for converting carbon into carbon oxides in processing systems selected from petrochemical, hydrocarbon, carbon production and carbon processing systems, the method comprising: providing a slurry or a catalyst support system, wherein the slurry or catalyst support system comprises a perovskite material of formula AaBbCeDdOx-5, wherein 0<a<3.2, O^b^l.2, 0.9<a+b^3.2, 0^c^l.2, O.O^d^l.2, 0.9<c+d^L2, 3^x^9.2, and -0.5<5<0.5; wherein A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), hafnium (Hf), tantalum (Ta), thallium (Tl), lead (Pb), and any combination thereof; and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr),
neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu) hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), and any combination thereof, and applying the slurry or the catalyst support system to the processing system is disclosed.
[0021] In some embodiments, the hydrocarbon, petrochemical, carbon production, or carbon processing system is selected from a refinery crude unit; a vacuum unit; a fluid catalytic cracker; a delayer coker; a hydrotreating unit; a visbreaker unit; a LC-Finer; an EDC-VCM; a steam cracker of hydrocarbons or biomass; a reforming unit of hydrocarbons or biomass; a pyrolysis unit for hydrocarbons or biomass; a unit for the pyrolysis and/or gasification of plastic, biomass, hydrocarbons, coal, petroleum coke, and/or municipal solid waste; a facility for the generalized production of carbon, including, but not limited to, a facility for the production of carbon black; and a facility for the production of carbon nanotubes; and/or a unit for the incineration of waste materials.
[0022] In some embodiments, the processing system is a unit for the incineration of waste materials, wherein the waste materials comprise per- or polyfluoroalkyl substances (PFAS).
[0023] In some embodiments, the catalyst support system comprises silica or alumina, or metallics.
[0024] In yet another aspect of the present technology, a method for the degradation of PFAS during incineration of a waste material, the method comprising: applying a catalyst composition to the waste material, the catalyst composition comprising a perovskite having the formula AaBbCcDdOx-8, wherein 0<a<3.2, 0^b^l.2, 0.9<a+b^3.2, 0^c^l.2, 0.0^d^l.2, 0.9<c+d^L2, 3^x^9.2, and 0.5<5<0.5 is disclosed.
[0025] In some embodiments, A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y),
lutetium (Lu), and any combination thereof; C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), hafnium (Hf), tantalum (Ta), thallium (Tl), lead (Pb) and any combination thereof; and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu) hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), and any combination thereof.
[0026] In some embodiments, A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof. In some embodiments, B is selected from scandium (Sc), yttrium (Y), and/or a combination thereof. In some embodiments, C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof. In some embodiments, D is selected from cerium (Ce), tungsten (W), and/or a combination thereof.
[0027] In some embodiments, the catalyst composition is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03,
BaZr(0. l)Ce(0.7)Y(0.2)03, and/or a combination thereof.
[0028] In yet another aspect of the present technology, a method for the mitigation of process and/or equipment fouling comprising: applying a catalyst composition to the process and/or equipment, the catalyst composition comprising a perovskite having the formula AaBbCcDdOx-6, wherein 0<a<3.2, O^b^l.2, 0.9<a+b^3.2, O^c^l.2, O.O^d^l.2, 0.9<c+d^l.2, 3^x^9.2, and -0.5<b<0.5 is disclosed.
[0029] In some embodiments, A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y),
lutetium (Lu), and any combination thereof; C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), hafnium (Hf), tantalum (Ta), thallium (Tl), lead (Pb) and any combination thereof; and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu) hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), and any combination thereof.
[0030] In some embodiments, A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof. In some embodiments, B is selected from scandium (Sc), yttrium (Y), and/or a combination thereof. In some embodiments, C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof. In some embodiments, D is selected from cerium (Ce), tungsten (W), and/or a combination thereof.
[0031] In some embodiments, the catalyst composition is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03,
BaZr(0. l)Ce(0.7)Y(0.2)03, and/or a combination thereof.
BRIEF DESCRIPTION OF THE FIGURES
[0032] These and other features of the disclosed technology, and the advantages, are illustrated specifically in embodiments now to be described, by way of example, with reference to the accompanying diagrammatic drawings. Those of skill in the art will understand that the figure, described below, is for illustrative purposes only. The figure is not intended to limit the scope of the present teachings in any way.
[0033] FIG. 1 provides experimental results of an illustrative embodiment of the disclosed technology.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0034] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art to which this disclosure belongs. The use of “including”, “comprising” or “having” and variations thereof herein are meant to encompass the items listed thereafter and equivalents thereof as well as additional items.
[0035] Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about” is not to be limited to the precise value specified. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Here and throughout the specification and claims, range limitations may be combined and/or interchanged; such ranges are identified and include all the sub-ranges contained therein unless context or language indicates otherwise.
[0036] In the specification and the claims, the singular forms “a”, “an” and “the” include plural referents unless the context clearly dictates otherwise. Moreover, the suffix “(s)” as used herein is usually intended to include both the singular and the plural of the term that it modifies, thereby including one or more of that term.
[0037] As used herein, the term “or” is not meant to be exclusive and refers to at least one of the referenced components (for example, a material) being present and includes instances in which a combination of the referenced components may be present, unless the context clearly dictates otherwise.
[0038] As used herein, the terms “may” and “may be” indicate a possibility of an occurrence within a set of circumstances; a possession of a specified property, characteristic or function; and/or qualify another verb by expressing one or more of an ability, capability, or possibility associated with the qualified verb. Accordingly, usage
of “may” and “may be” indicates that a modified term is apparently appropriate, capable, or suitable for an indicated capacity, function, or usage, while taking into account that in some circumstances, the modified term may sometimes not be appropriate, capable, or suitable. For example, in some circumstances, an event or capacity can be expected, while in other circumstances, the event or capacity cannot occur. This distinction is captured by the terms “may” and “may be”.
[0039] As used herein the term “coke” refers to, but is not limited to, carbonaceous solid or liquid or particulates or macromolecules forming the carbonaceous solid or liquid, which are derived from coal, petroleum, wood, hydrocarbons and other materials containing carbon, and which include, for example, carbon black, carbon nanotubes, tar, and pyrolytic coke existing in hydrocarbon, petrochemical, carbon production or carb processing units.
[0040] Likewise, as used herein the term “coking” refers to, but is not limited to, the deposition of coke or a layer of coke on the surface of a hydrocarbon, petrochemical, carbon production or carbon processing unit.
[0041] Reference throughout the specification to “some embodiments”, and so forth, means that a particular element (e.g., feature, structure, and/or characteristic) described in connection with the invention is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described inventive features may be combined in any suitable manner in the various embodiments.
[0042] The disclosed technology generally provides for catalyst compositions and methods for converting carbon into carbon oxides in petrochemical, hydrocarbon, carbon production, and carbon processing systems. More specifically, the disclosed technology relates to compositions and methods for converting carbon into carbon oxides in low temperature as well as in high temperature petrochemical, hydrocarbon, carbon production, and carbon processing applications.
[0043] In one aspect of the present technology, a catalyst composition for converting carbon into a carbon oxide or carbon oxides in a petrochemical, hydrocarbon, carbon production and/or carbon processing system is provided. The catalyst composition
provides for the inhibition of coking and coke associated fouling in such processing systems by providing catalyst compositions comprising perovskite materials. The perovskite materials of the disclosed technology have proved beneficial in the conversion of carbon into carbon oxides. Without being bound by theory, it is believed that when coke forms on the surfaces of the disclosed perovskite compositions, the coke is converted immediately to a carbon oxide, wherein these carbon oxides immediately gasify and dissipate. Examples of such carbon oxides, include, but are not limited to, carbon monoxide and carbon dioxide.
[0044] As such, the disclosed technology minimizes and/or mitigates unwanted fouling and/or coking of process and/or equipment, including, but not limited to, heat exchange equipment (e.g. shell and tube exchangers, furnace tubes, etc.) that causes heat transfer loss leading to higher fuel/energy consumption (and thus higher CO2 emissions), pressure drop, and carburization of substrate metallurgy in petrochemical, hydrocarbon, carbon production and carbon processing system applications. It also offers reduction in deactivation of other process catalysts, such as for reforming, hydrotreating, pyrolysis, and gasification.
[0045] Additionally, the disclosed technology may help reduce the temperature required to adequately degrade per- and polyfluoroalkyl substances (PF AS) in waste materials. Without being bound by theory, the catalyst compositions of the disclosed technology may facilitate easier mineralization of fluorine chemistry by enabling formation of organo fluoride radicals at lower temperatures due to coordination defects/cleavage (leading to high electron density at defective sites) on the surface of the catalyst due to heat treatment during incineration processes. This aspect may be further accelerated by the presence of transition metal compositions in the catalyst composition of the disclosed technology as well as transition metal impurities, such as iron, on the surface. Furthermore, due to the presence of oxygen vacancy in the structure of the catalyst composition, such vacancy could not only help accelerate oxidation reactions, including conversion of any CO to CO2, but could also help with hydrodefluorination when an oxidant such as steam, CO2, air, or oxygen is available, due to abstraction of oxygen from the oxidant by the oxygen vacancy.
[0046] In some embodiments the catalyst composition comprises a perovskite material of formula AaBbCcDdOx-s, wherein 0<a<3.2, 0^b^l.2, 0.9<a+b^3.2, O^c^l.2, O.O^d^l .2, 0.9<c+d^L2, 3^x^9.2, and -0.5<5<0.5; wherein (i) A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; (ii) B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; (iii) C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), hafnium (Hf), tantalum (Ta), thallium (Tl), lead (Pb), and any combination thereof; and (iv) D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu) hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), and any combination thereof.
[0047] In some embodiments, the catalyst composition comprises A, wherein A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof. In some embodiments, the catalyst composition comprises B, wherein B is selected from scandium (Sc) yttrium (Y), and/or a combination thereof. In some embodiments, the catalyst composition comprises C, wherein C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof. In some embodiments, the catalyst composition comprises D, wherein D is selected from cerium (Ce), tungsten (W), and/or a combination thereof. In some embodiments, D is tungsten (W)-based, wherein D is selected from tungstate, tungsten ion, and/or a combination thereof.
[0048] In some embodiments, the catalyst composition comprises a perovskite material that is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03,
BaCe(0.5)Zr(0.5)03, BaZr(0.1)Ce(0.7)Y(0.2)03, and/or a combination thereof. It was
shown that such disclosed catalyst compositions gasify coke (i.e. carbon) to a higher degree at lower temperatures.
[0049] In some embodiments, the catalyst composition comprises tungsten. It is believed that tungsten or tungsten-based materials are effective as catalysts at low or high temperature due to the oxide ion conductivity.
[0050] In another aspect of the disclosed technology, a method for converting carbon into carbon oxides in petrochemical, hydrocarbon, carbon production and/or carbon processing systems is provided. The method of the disclosed technology comprises applying a catalyst composition to the petrochemical, hydrocarbon, carbon production and/or carbon processing system and/or unit, wherein the catalyst composition comprises a perovskite having the formula AaBbCcDdOx-«. wherein 0<a<3.2, 0^b^l.2, 0.9<a+b^3.2, 0^c^l.2, O.O^d^l.2, 0.9<c+d^L2, 3^x^9.2, and -0.5<5<0.5.
[0051] It should be understood that the catalyst composition of the present technology may be applied by any conventional means known or recognized in the art. For example, the catalyst composition may be applied to the processing system by painting, spraying, and/or dipping and drying methods. In some embodiments, the catalyst composition may be applied to the processing system during manufacturing or retrofitting.
[0052] In some embodiments, the catalyst composition of the disclosed method comprises A, wherein A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), hafnium (Hf), tantalum (Ta), thallium (Tl), lead (Pb), and any combination thereof; and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd),
terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu) hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), and any combination thereof.
[0053] In other embodiments, A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof. In some embodiments, B is selected from scandium (Sc), yttrium (Y), and/or a combination thereof. In some embodiments, C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof. In some embodiments, D is selected from cerium (Ce), tungsten (W), and/or a combination thereof. In some embodiments, D is tungsten (W)-based, wherein D is selected from tungstate, tungsten ion, and/or a combination thereof.
[0054] In some embodiments, the catalyst composition of the disclosed method is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03, BaZr(0.1)Ce(0.7)Y(0.2)03, and/or a combination thereof.
[0055] The present method further provides for a petrochemical, hydrocarbon, carbon production or carbon processing system. It should be understood that coking occurs in such systems because the temperature and the hydrocarbon, petrochemical, or carbon residence time are higher than the stability limitations of these materials. As such, formation of coke or coke-like material increases dramatically as local metal contact temperatures exceed about 300°C. Operational factors can influence coke formation, such as hot shutdowns, which promote coke build up. Even under normal operating conditions, coking can occur under standard operating conditions for various units within petrochemical, hydrocarbon, carbon production, or carbon processing systems.
[0056] In some embodiments, the hydrocarbon, petrochemical, carbon production or carbon processing system of the present method comprises a refinery crude unit; a refinery vacuum unit; a fluid catalytic cracker; a delayer coker; a hydrotreating unit; a visbreaker unit; a LC-Finer; an EDC-VCM; a steam cracker of hydrocarbons or biomass; transfer line exchangers following the steam cracker in ethylene production; a reforming unit of hydrocarbons or biomass; a pyrolysis unit for hydrocarbons or biomass; a unit for
the pyrolysis and/or gasification of plastic, biomass, hydrocarbons, coal, petroleum coke, and/or municipal solid waste; a facility for the generalized production of carbon, including, but not limited to, a facility for the production of carbon black; a facility for the production of carbon nanotubes, and/or a unit for the incineration of waste materials, such as municipal sludge/waste that comprise PFAS and/or other waste materials that include PFAS.
[0057] In other embodiments, the hydrocarbon or petrochemical processing system of the present method is selected from the group consisting of a coker unit furnace, a crude unit furnace, a coker unit heat exchanger and a crude unit heat exchanger, or a combination thereof.
[0058] The petrochemical, hydrocarbon, carbon production or carbon processing system of the present method operates in the temperature range from about 300°C to about 1200°C. At temperatures about and above 300°C, fouling precursors such as asphaltenes in crude oil or unsaturated hydrocarbons from thermal cracking further dehydrogenate to produce coke or coke-like material.
[0059] As such, in some embodiments, the petrochemical, hydrocarbon, carbon production or carbon processing system and/or unit of the disclosed method operates in the temperature range from about 300°C to about 600°C. It is believed that in this low temperature range, the activation energy available to gasify coke or coke-like material is lower, and thus is more challenging. Examples, are heat exchanges and/or furnaces in a refinery crude unit; a refinery vacuum unit; a fluid catalytic cracker; a delayer coker; a hydrotreating unit; a visbreaker unit; a LC-Finer; an EDC-VCM; transfer line exchangers following the steam cracker in ethylene production; a pyrolysis unit for hydrocarbons or biomass and/or municipal solid waste; feed heaters in a carbon black production unit.
[0060] In some embodiments, the catalyst composition of the present method gasifies coke deposits on or within the hydrocarbon, petrochemical, carbon production, or carbon processing system unit surfaces. In some embodiments, the catalyst composition is effective at gasifying coke in the temperature range from about 300°C to about 1200°C, and in other embodiments from about 300°C to about 600°C.
[0061] In yet another aspect of the present technology, a method for converting carbon into carbon oxides in petrochemical, hydrocarbon, carbon production and/or carbon processing systems is provided. The method comprises, providing a slurry or a catalyst support system, where the slurry or catalyst support system comprises a perovskite material of formula AaBbCcDdOx-8, wherein 0<a<3.2, 0^b^l.2, 0.9<a+b^3.2, 0^c^l .2, 0.0^d^l.2, 0.9<c+d^L2, 3^x^9.2, and -0.5<5<0.5; wherein A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), hafnium (Hf), tantalum (Ta), thallium (Tl), lead (Pb), and any combination thereof; and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu) hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), and any combination thereof, and applying the slurry or the catalyst support system to a hydrocarbon, petrochemical, carbon production or carbon processing system. It should be understood that the slurry or catalyst support system of the present technology may be applied by any conventional means known or recognized in the art. In some embodiments, the catalyst support system comprises ceramics such as silica or alumina, or metallics.
[0062] In some embodiments, the slurry or catalyst support system is applied to the hydrocarbon, petrochemical, carbon production or carbon processing system selected from a refinery crude unit; a vacuum unit; a fluid catalytic cracker; a delayer coker; a hydrotreating unit; a visbreaker unit; a LC-Finer; an EDC-VCM; a steam cracker of hydrocarbons or biomass; a reforming unit of hydrocarbons or biomass; a pyrolysis unit
for hydrocarbons or biomass; a unit for the pyrolysis and/or gasification of plastic, biomass, hydrocarbons, coal, petroleum coke, and/or municipal solid waste; a facility for the generalized production of carbon, including, but not limited to, a facility for the production of carbon black; facility for the production of carbon nanotubes; and/or a unit for the incineration of waste materials, such as municipal sludge/waste that comprise PF AS and/or other waste materials that include PFAS.
[0063] In another aspect of the disclosed technology, a method for degrading PFAS during incineration of a waste material is provided. The method of the disclosed technology comprises applying a catalyst composition to the waste material, wherein the catalyst composition comprises a perovskite having the formula AaBbCcDdOx-8, wherein 0<a<3.2, O^b^l.2, 0.9<a+b^3.2, O^c^l.2, 0.0^ 1.2, 0.9<c+d^L2, 3^9.2, and -0.5<8<0.5.
[0064] In some embodiments, the catalyst composition of the disclosed method comprises A, wherein A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), hafnium (Hf), tantalum (Ta), thallium (Tl), lead (Pb), and any combination thereof; and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu) hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), and any combination thereof.
[0065] In other embodiments, A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof. In some embodiments, B is selected from
scandium (Sc), yttrium (Y), and/or a combination thereof. In some embodiments, C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof. In some embodiments, D is selected from cerium (Ce), tungsten (W), and/or a combination thereof. In some embodiments, D is tungsten (W)-based, wherein D is selected from tungstate, tungsten ion, and/or a combination thereof.
[0066] In some embodiments, the catalyst composition of the disclosed method is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03, BaZr(0.1)Ce(0.7)Y(0.2)03, and/or a combination thereof.
[0067] In a further aspect of the of the disclosed technology, a method for mitigation of process and/or equipment fouling is provided. The method of the disclosed technology comprises applying a catalyst composition to the process and/or equipment, wherein the catalyst composition comprises a perovskite having the formula AaBbCcDdOx.g, wherein 0<a<3.2, 0^b^l .2, 0.9<a+b^3.2, 0^c^l .2, O.O^d^l .2, 0.9<c+d^l.2, 3^x^9.2, and -0.5<8<0.5.
[0068] In some embodiments, the catalyst composition of the disclosed method comprises A, wherein A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), hafnium (Hf), tantalum (Ta), thallium (TI), lead (Pb), and any combination thereof; and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu) hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re),
osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), and any combination thereof.
[0069] In other embodiments, A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof. In some embodiments, B is selected from scandium (Sc), yttrium (Y), and/or a combination thereof. In some embodiments, C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof. In some embodiments, D is selected from cerium (Ce), tungsten (W), and/or a combination thereof. In some embodiments, D is tungsten (W)-based, wherein D is selected from tungstate, tungsten ion, and/or a combination thereof.
[0070] In some embodiments, the catalyst composition of the disclosed method is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03, BaZr(0.1)Ce(0.7)Y(0.2)03, and/or a combination thereof.
EXAMPLES
[0071] The present technology will be further described in the following examples, which should be viewed as being illustrative and should not be construed to narrow the scope of the disclosed technology or limit the scope to any particular embodiments.
[0072] Testing was conducted according to the following procedure. A 10:1 (w/w) Perovskite:Carbon Black sample was tested using a Thermal Gravimetric Analyzer (Jump to 100°C; Equilibrate at 100°C; Switch to Air; Ramp 50°C /min to 400°C; Ramp 5°C /min to 950°C). Temperature at 50% weight loss (T50), that is, 50% of the original carbon in the sample is oxidized, was used as the key measure of gasification capability of the example perovskite materials. A positive difference in T50 between Carbon Black and a 10:1 (w/w) Example Perovskite:Carbon Black mixture indicates positive coke/carbon gasification efficacy with which the perovskite material is able to convert any coke that comes into contact with a surface, deposited/coated with the perovskite material, of a hydrocarbon or a petrochemical processing system, to oxides of carbon and thus minimize fouling/coking.
[0073] As shown in FIG. 1, it was shown that the disclosed example perovskites, particularly, tungstate-based perovskite materials E and F gasify coke (i.e. carbon) to the same degree (that is, 50% weight loss) at much lower temperatures of 588.5 °C and 592.1°C respectively, which is a direct indication of the capability of these materials to minimize fouling/coking of heat transfer surfaces in both low and high temperature hydrocarbon or petrochemical processing systems. It is to be noted that the temperatures indicated in FIG. 1 are surface temperatures that are typically much higher than the bulk process temperatures.
[0074] While embodiments of the disclosed technology have been described, it should be understood that the present disclosure is not so limited and modifications may be made without departing from the disclosed technology. The scope of the disclosed technology is defined by the appended claims, and all devices, processes, and methods that come within the meaning of the claims, either literally or by equivalence, are intended to be embraced therein.
Claims
1. A catalyst composition, the composition comprising a perovskite material of formula AaBbCcDdOx-s, wherein 0<a<3.2, O^b^l.2, 0.9<a+b^3.2, 0^c^l.2, 0.0^ 1.2, 0.9<c+d^L2, 3^x^9.2, and -0.5<8<0.5; wherein
(i) A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof;
(ii) B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof;
(iii) C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), hafnium (Hf), tantalum (Ta), thallium (Tl), lead (Pb) and any combination thereof; and
(iv) D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu) hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), and any combination thereof.
2. The catalyst composition of Claim 1, wherein A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof.
3. The catalyst composition of Claim 1, wherein B is selected from scandium (Sc) yttrium (Y), and/or a combination thereof.
4. The catalyst composition of Claim 1, wherein C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof.
5. The catalyst composition of Claim 1, wherein D is selected from cerium (Ce), tungsten (W), and/or a combination thereof.
6. The catalyst composition of Claim 1, wherein the perovskite material is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03, BaZr(0.1)Ce(0.7)Y(0.2)03, and/or a combination thereof.
7. A method for converting carbon into carbon oxides in processing systems selected from petrochemical, hydrocarbon, carbon production and carbon processing systems, the method comprising: applying a catalyst composition to the processing system, the catalyst composition comprising a perovskite having the formula AaBbCcDdOx-5, wherein 0<a<3.2, 0^b^l.2, 0.9<a+b^3.2, 0^c^l.2, O.O^d^l.2, 0.9<c+d^L2, 3^x^9.2, and -0.5<5<0.5.
8. The method of Claim 7, wherein A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), hafnium (Hf), tantalum (Ta), thallium (TI), lead (Pb) and any combination thereof; and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm),
ytterbium (Yb), and lutetium (Lu) hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), and any combination thereof.
9. The method of Claim 8, wherein A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof.
10. The method of Claim 8, wherein B is selected from scandium (Sc), yttrium (Y), and/or a combination thereof.
11. The method of Claim 8, wherein C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof.
12. The method of Claim 8, wherein D is selected from cerium (Ce), tungsten (W), and/or a combination thereof.
13. The method of Claim 7, wherein the catalyst composition is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03,
BaZr(0.1)Ce(0.7)Y(0.2)03, and/or a combination thereof.
14. The method of Claim 7, wherein the processing system is selected from a refinery crude unit; a vacuum unit; a fluid catalytic cracker; a delayer coker; a hydrotreating unit; a visbreaker unit; a LC-Finer; an EDC-VCM; a steam cracker of hydrocarbons or biomass; a reforming unit of hydrocarbons or biomass; a pyrolysis unit for hydrocarbons or biomass; a unit for the pyrolysis and/or gasification of plastic, biomass, hydrocarbons, coal, petroleum coke, and/or municipal solid waste; a facility for the production of carbon black; a facility for the production of carbon nanotubes; and/or a unit for the incineration of waste materials.
15. The method of Claim 14, wherein the processing system is a unit for the incineration of waste materials, wherein the waste materials comprise per- or polyfluoroalkyl substances (PFAS).
16. The method of Claim 7, wherein the processing system is selected from the group consisting of a coker unit furnace, a crude unit furnace, a coker unit heat exchanger and a crude unit heat exchanger, or a combination thereof.
17. The method of Claim 7, wherein the processing system operates in the temperature range from about 300°C to about 1200°C.
18. The method of Claim 17, wherein the processing system operates in the temperature range from about 300°C to about 600°C.
19. The method of Claim 7, wherein the catalyst composition gasifies coke deposits on the process system surfaces.
20. A method for converting carbon into carbon oxides in processing systems selected from hydrocarbon, petrochemical, carbon production and carbon processing systems, the method comprising: providing a slurry or a catalyst support system, wherein the slurry or catalyst support system comprises a perovskite material of formula AaBbCcDdOx-5, wherein 0<a<3.2, 0^b^l.2, 0.9<a+b^3.2, 0^c^l.2, 0.0^d^l.2, 0.9<c+d^l.2, 3^x^9.2, and -0.5<8<0.5; wherein A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), hafnium (Hf), tantalum (Ta), thallium (Tl), lead (Pb), and any
combination thereof; and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu) hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), and any combination thereof, and applying the slurry or the catalyst support system to the processing system.
21. The method of Claim 20, wherein the processing system is selected from a refinery crude unit; a vacuum unit; a fluid catalytic cracker; a delayer coker; a hydrotreating unit; a visbreaker unit; a LC-Finer; an EDC-VCM; a steam cracker of hydrocarbons or biomass; a reforming unit of hydrocarbons or biomass; a pyrolysis unit for hydrocarbons or biomass; a unit for the pyrolysis and/or gasification of plastic, biomass, hydrocarbons, coal, petroleum coke, and/or municipal solid waste; a facility for the production of carbon black; a facility for the production of carbon nanotubes; and/or a unit for the incineration of waste materials.
22. The method of Claim 21, wherein the processing system is a unit for the incineration of waste materials, wherein the waste materials comprise per- or polyfluoroalkyl substances (PF AS).
23. The method of Claim 19, the catalyst support system comprises silica or alumina, or metallics.
24. A method for degradation of per- or polyfluoroalkyl substances (PFAS) during incineration of a waste material, the method comprising: applying a catalyst composition to the waste material, the catalyst composition comprising a perovskite having the formula AaBbCcDdOx-s, wherein 0<a<3.2, O^b^l.2, 0.9<a+b^3.2, O^c^ l.2, O.O^d^l.2, 0.9<c+d^L2, 3^x^9.2, and -0.5<8<0.5.
25. The method of Claim 24, wherein A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), hafnium (Hf), tantalum (Ta), thallium (Tl), lead (Pb) and any combination thereof; and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu) hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), and any combination thereof.
26. The method of Claim 25, wherein A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof.
27. The method of Claim 25, wherein B is selected from scandium (Sc), yttrium (Y), and/or a combination thereof.
28. The method of Claim 25, wherein C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof.
29. The method of Claim 25, wherein D is selected from cerium (Ce), tungsten (W), and/or a combination thereof.
30. The method of Claim 25, wherein the catalyst composition is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03,
BaCe(O.72)Zr(0.3)03 , BaC e(0.3 )Zr(0.7)03 , BaCe(0.5)Zr(0.5)03,
BaZr(0.1)Ce(0.7)Y(0.2)03, and/or a combination thereof.
31. A method for mitigation of process and/or equipment fouling, the method comprising: applying a catalyst composition to the process and/or equipment, the catalyst composition comprising a perovskite having the formula AaBbCcDdOx-8, wherein 0<a<3.2, 0^b^l.2, 0.9<a+b^3.2, O^c^l.2, 0.0^d^l.2, 0.9<c+d^L2, 3^x^9.2, and -0.5<8<0.5.
32. The method of Claim 31, wherein A is selected from lithium (Li), beryllium (Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium (Sr), barium (Ba), and any combination thereof; B is selected scandium (Sc), yttrium (Y), lutetium (Lu), and any combination thereof; C is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), hafnium (Hf), tantalum (Ta), thallium (Tl), lead (Pb) and any combination thereof; and D is selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu) hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), and any combination thereof.
33. The method of Claim 32, wherein A is selected from calcium (Ca), strontium (Sr), barium (Ba), and/or a combination thereof.
34. The method of Claim 32, wherein B is selected from scandium (Sc), yttrium (Y), and/or a combination thereof.
35. The method of Claim 32, wherein C is selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and/or a combination thereof.
36. The method of Claim 32, wherein D is selected from cerium (Ce), tungsten (W), and/or a combination thereof.
37. The method of Claim 32, wherein the catalyst composition is selected from the group consisting of Ba3Y2WO9, Ba2CaWO6, BaSrY4O8, BaCe(0.7)Zr(0.3)03, BaCe(0.72)Zr(0.3)03, BaCe(0.3)Zr(0.7)03, BaCe(0.5)Zr(0.5)03,
BaZr(0.1)Ce(0.7)Y(0.2)03, and/or a combination thereof.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202363513116P | 2023-07-12 | 2023-07-12 | |
| US63/513,116 | 2023-07-12 | ||
| US202463567164P | 2024-03-19 | 2024-03-19 | |
| US63/567,164 | 2024-03-19 | ||
| US202463632810P | 2024-04-11 | 2024-04-11 | |
| US63/632,810 | 2024-04-11 |
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| WO2025014849A2 true WO2025014849A2 (en) | 2025-01-16 |
| WO2025014849A3 WO2025014849A3 (en) | 2025-03-20 |
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| PCT/US2024/036996 Pending WO2025014849A2 (en) | 2023-07-12 | 2024-07-08 | Catalyst compositions and methods for converting carbon into carbon oxides |
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| JP5190897B2 (en) * | 2008-08-20 | 2013-04-24 | 草津電機株式会社 | Method for decomposing waste plastics and organic substances using titanium oxide granules with optimum particle characteristics |
| CN102260519B (en) * | 2010-05-31 | 2017-03-01 | 通用电气公司 | Hydrocarbon cracking method and reaction unit |
| CN102557855B (en) * | 2010-12-22 | 2015-11-25 | 通用电气公司 | The coating process of hydrocarbon cracking method and reaction unit and hydrocarbon cracking reaction unit |
| CN109562360A (en) * | 2016-07-29 | 2019-04-02 | 巴斯夫库德克有限公司 | Catalyst coatings, Its Preparation Method And Use |
| CN116408066A (en) * | 2021-12-30 | 2023-07-11 | 中国石油天然气集团有限公司 | Catalyst for catalytic combustion of VOCs and preparation method thereof |
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