US20160289143A1 - Advanced oxidative coupling of methane - Google Patents
Advanced oxidative coupling of methane Download PDFInfo
- Publication number
- US20160289143A1 US20160289143A1 US14/868,911 US201514868911A US2016289143A1 US 20160289143 A1 US20160289143 A1 US 20160289143A1 US 201514868911 A US201514868911 A US 201514868911A US 2016289143 A1 US2016289143 A1 US 2016289143A1
- Authority
- US
- United States
- Prior art keywords
- product stream
- ocm
- methane
- compounds
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/152—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by forming adducts or complexes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K23/00—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids
- F01K23/02—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled
- F01K23/06—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle
- F01K23/067—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle the combustion heat coming from a gasification or pyrolysis process, e.g. coal gasification
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
- F01K25/08—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours
- F01K25/10—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours the vapours being cold, e.g. ammonia, carbon dioxide, ether
- F01K25/103—Carbon dioxide
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K5/00—Plants characterised by use of means for storing steam in an alkali to increase steam pressure, e.g. of Honigmann or Koenemann type
-
- H01L35/30—
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
- H10N10/13—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the heat-exchanging means at the junction
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
- Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Definitions
- aspects of the present disclosure provide processes for recovering olefins from a stream containing mix of hydrocarbons by utilizing techniques based the use of adsorbents.
- systems and methods enable the separation, pre-separation, purification and/or recovery of hydrocarbons, including, but not limited to, olefins, ethylene, propylene, methane, and ethane, and CO 2 , from a multicomponent hydrocarbon stream such as an effluent stream from an oxidative coupling of methane (OCM) reactor or an ethylene-to-liquids (ETL) reactor.
- OCM oxidative coupling of methane
- ETL ethylene-to-liquids
- the hydrocarbon stream can also be the feed to the OCM or ETL reactor in certain cases.
- the feed to the ETL reactor is the effluent from OCM reactor.
- a separation process utilizing adsorbents can be used to purify and pre-treat existing hydrocarbon streams (such as refinery off-gases, cracker off-gas, streams from NGL plants, and others), followed by use of the resulting olefin rich stream (e.g., PSA tail gas) as the ETL feed.
- the present disclosure provides various improvements in OCM and ETL processes, such as, without limitation, a separation and pre-separation process to recover desired or predetermined components from an OCM reactor effluent, CO 2 recovery and capture techniques, enhanced heat recovery methods to utilize the OCM reaction heat more efficiently, and techniques and technologies to further reduce the carbon footprint of the OCM process.
- An aspect of the present disclosure provides a method for generating higher hydrocarbon(s) from a stream comprising compounds with two or more carbon atoms (C 2+ ), comprising introducing methane and an oxidant (e.g., O 2 ) into an oxidative coupling of methane (OCM) reactor that has been retrofitted into a system comprising an ethylene-to-liquids (ETL) reactor.
- OCM oxidative coupling of methane
- ETL ethylene-to-liquids
- the first product stream can then be directed to a pressure swing adsorption (PSA) unit that recovers at least a portion of the C 2+ compounds from the first product stream to yield a second product stream comprising the at least the portion of the C 2+ compounds.
- PSA pressure swing adsorption
- the second product stream can then be directed to the ETL reactor.
- the higher hydrocarbon(s) can then be generated from the at least the portion of the C 2+ compounds in the ETL reactor.
- the first product stream is directed to other intermediate units before the PSA, such as a post-bed cracking (PBC) unit that generates alkenes from alkanes.
- PBC post-bed cracking
- the alkenes can be included in the first product stream, which can then be directed to the PSA.
- the present disclosure provides a method for generating higher hydrocarbon(s) from a stream comprising compounds with two or more carbon atoms (C 2+ ), comprising: (a) introducing methane and an oxidant into an oxidative coupling of methane (OCM) reactor that has been retrofitted into a system comprising an ethylene-to-liquids (ETL) reactor, where the OCM reactor reacts the methane with the oxidant to generate a first product stream comprising the C 2+ compounds; (b) directing the first product stream to a pressure swing adsorption (PSA) unit that recovers at least a portion of the C 2+ compounds from the first product stream to yield a second product stream comprising the at least the portion of the C 2+ compounds; (c) directing the second product stream to the ETL reactor; and (d) generating the higher hydrocarbon(s) from the at least the portion of the C 2+ compounds in the ETL reactor.
- OCM oxidative coupling of methane
- ETL ethylene
- the method further comprises: (e) recovering a light stream comprising (i) hydrogen and (ii) carbon monoxide (CO) and/or carbon dioxide (CO 2 ) from the PSA unit and recycling the light stream to the OCM reactor; (f) directing at least a portion of the light stream into a methanation unit that reacts the hydrogen and the CO and/or CO 2 to produce a methanation product stream comprising methane; and (g) directing the methanation product stream into the OCM reactor.
- the method further comprises recovering C 2 and/or C 3 compounds from the second product stream and directing the C 2 and/or C 3 compounds to the OCM reactor.
- the OCM reactor further comprises a post-bed cracking (PBC) unit.
- the present disclosure provides a method for generating compounds with two or more carbon atoms (C 2+ compounds), comprising: (a) directing oxygen (O 2 ) and methane (CH 4 ) into an oxidative coupling of methane (OCM) reactor that reacts the O 2 and CH 4 in an OCM process to yield a product stream comprising (i) C 2+ compounds including ethylene (C 2 H 4 ) and (ii) carbon monoxide (CO) and/or carbon dioxide (CO 2 ); and (b) directing the product stream from the OCM reactor into a separations system that employs a refrigeration unit having a refrigerant that includes methane from the product stream, to enrich the C 2+ compounds in the product stream.
- OCM methane
- the product stream is directed into the separations system through one or more additional units.
- the method further comprises separating methane from the product stream for use in the refrigeration unit. In some embodiments, the method further comprises directing CO and/or CO 2 from the product stream to a methanation reactor that reacts the CO and/or CO 2 to yield a methanation product stream comprising methane. In some embodiments, the method further comprises directing at least a portion of the methane in the methanation product stream to the OCM reactor. In some embodiments, the method further comprises separating the product stream into (i) an ethylene product stream comprising ethylene and (ii) a C 3+ product stream comprising compounds with three or more carbon atoms (C 3+ compounds). In some embodiments, the method further comprises directing ethane from the product stream to the OCM reactor. In some embodiments, the method further comprises prior to directing the product stream into the separations system, compressing the product stream.
- the present disclosure provides a method for generating compounds with two or more carbon atoms (C 2+ compounds), comprising: (a) directing oxygen (O 2 ) and methane (CH 4 ) into an oxidative coupling of methane (OCM) reactor that reacts the O 2 and CH 4 in an OCM process to yield a product stream comprising (i) C 2+ compounds including ethylene (C 2 H 4 ) and (ii) carbon monoxide (CO) and/or carbon dioxide (CO 2 ); and (b) directing the product stream from the OCM reactor into a separations system that employs a complexation unit having a complexation catalyst that forms pi complexes with the ethylene in the product stream, to enrich the C 2+ compounds in the product stream.
- OCM methane
- the product stream is directed into the separations system through one or more additional units.
- the method further comprises using the complexation unit to remove one or more impurities from the product stream, where the impurities are selected from the group consisting of CO 2 , sulfur compounds, acetylenes, and hydrogen.
- the complexation catalyst includes one or more metals selected from the group consisting of silver and copper.
- the method further comprises directing CO and/or CO 2 from the product stream to a methanation reactor that reacts the CO and/or CO 2 to yield a methanation product stream comprising methane.
- the method further comprises directing the methane in the methanation product stream to the OCM reactor.
- the method further comprises separating the product stream into (i) an ethylene product stream comprising ethylene and (ii) a C 3+ product stream comprising compounds with three or more carbon atoms (C 3+ compounds).
- the method further comprises directing ethane from the product stream to the OCM reactor.
- the method further comprises prior to directing the product stream into the separations system, compressing the product stream.
- the present disclosure provides a method for generating compounds with two or more carbon atoms (C 2+ compounds), comprising: (a) directing oxygen (O 2 ) and methane (CH 4 ) into an oxidative coupling of methane (OCM) reactor that reacts the O 2 and CH 4 in an OCM process to yield a product stream comprising (i) C 2+ compounds including ethylene (C 2 H 4 ) and (ii) carbon dioxide (CO 2 ); and (b) directing the product stream from the OCM reactor into a separations system that employs a CO 2 separation unit to separate the CO 2 from the product stream, to enrich the C 2+ compounds in the product stream, which CO 2 separation unit employs (i) sorbent or solvent separation of CO 2 , (ii) membrane separation of CO 2 , or (iii) cryogenic or low temperature separation of CO 2 having an operating temperature greater than a boiling point of methane and less than a boiling point of CO 2 .
- the product stream is directed into the separations system through one or more additional units.
- the sorbent or solvent separation of CO 2 employs an amine based absoprtion system.
- the sorbent or solvent separation of CO 2 employs a Benfield process.
- the sorbent or solvent separation of CO 2 employs diethanolamine.
- the sorbent or solvent separation of CO 2 employs glycol dimethylether.
- the sorbent or solvent separation of CO 2 employs propylene carbonate.
- the sorbent or solvent separation of CO 2 employs Sulfinol.
- the sorbent or solvent separation of CO 2 employs a zeolite. In some embodiments, the sorbent or solvent separation of CO 2 employs active carbon. In some embodiments, the CO 2 separation system comprises a membrane CO 2 separation system. In some embodiments, the membrane separation of CO 2 employs a polymeric membrane. In some embodiments, the membrane separation of CO 2 employs a metallic membrane. In some embodiments, the membrane separation of CO 2 employs a ceramic membrane. In some embodiments, the membrane separation of CO 2 employs a hybrid membrane comprising a membrane supporting a solvent or sorbent. In some embodiments, the membrane separation of CO 2 employs a poly ionic liquid membrane. In some embodiments, the membrane separation of CO 2 employs a supported ionic liquid membrane. In some embodiments, the membrane separation of CO 2 employs a polyetherimide membrane.
- the method further comprises directing the CO 2 from the product stream to a methanation reactor that reacts the CO 2 to yield a methanation product stream comprising methane. In some embodiments, the method further comprises directing the methane in the methanation product stream to the OCM reactor. In some embodiments, the method further comprises separating the product stream into (i) an ethylene product stream comprising ethylene and (ii) a C 3+ product stream comprising compounds with three or more carbon atoms (C 3+ compounds). In some embodiments, the method further comprises directing ethane from the product stream to the OCM reactor. In some embodiments, the method further comprises prior to directing the product stream into the separations unit, compressing the product stream.
- the present disclosure provides a method for generating compounds with two or more carbon atoms (C 2+ compounds), comprising: (a) directing water into an electrolysis unit that electrolyzes the water to yield oxygen (O 2 ) and hydrogen (H 2 ); (b) directing the O 2 from the electrolysis unit and methane (CH 4 ) into an oxidative coupling of methane (OCM) reactor that reacts the O 2 and CH 4 in an OCM process to yield a product stream comprising (i) C 2+ compounds, including ethylene (C 2 H 4 ) and (ii) carbon monoxide (CO) and/or carbon dioxide (CO 2 ); (c) directing at least a portion of the CO and/or CO 2 from the product stream and the H 2 from the electrolysis unit into a methanation reactor that reacts the H 2 and the CO and/or CO 2 to yield CH 4 ; and (d) directing at least a portion of the CH 4 from the methanation reactor to the OCM reactor.
- OCM methane
- the electrolysis unit comprises an alkaline water electrolysis system. In some embodiments, the electrolysis unit comprises a proton exchange membrane electrolysis system. In some embodiments, the electrolysis unit comprises a steam electrolysis system.
- the present disclosure provides a method for generating compounds with two or more carbon atoms (C 2+ compounds), comprising: (a) directing oxygen (O 2 ) and methane (CH 4 ) into an oxidative coupling of methane (OCM) reactor that reacts the O 2 and CH 4 in an OCM process to yield a product stream comprising (i) C 2+ compounds including ethylene (C 2 H 4 ) and (ii) carbon dioxide (CO 2 ); (b) directing the product stream from the OCM reactor into a separations system that employs a CO 2 separation unit that separates the CO 2 from the product stream to enrich the C 2+ compounds in the product stream; and (c) directing at least a portion of the CO 2 separated in (b) to the OCM reactor.
- OCM methane
- the product stream is directed into the separations system through one or more additional units.
- the present disclosure provides a method for generating compounds with two or more carbon atoms (C 2+ compounds), comprising: (a) directing oxygen (O 2 ) and methane (CH 4 ) into an oxidative coupling of methane (OCM) reactor that reacts the O 2 and CH 4 in an OCM process to yield a product stream comprising C 2+ compounds including ethylene (C 2 H 4 ) and heat; (b) using an evaporator to transfer at least a portion of the heat from the product stream to an organic working fluid in a closed fluid flow cycle as part of an organic Rankine cycle (ORC) system, to evaporate the organic working fluid, which closed fluid flow cycle includes the evaporator, a turbine, a condenser, and a pump; (c) directing the organic working fluid evaporated in (b) to the turbine to generate power; (d) directing the organic working fluid from the turbine to the condenser that condenses the organic working fluid; and (e) directing the organic working fluid condensed in
- the organic working fluid is selected from the group consisting of hydrocarbons, silicon oils, and perfluorocarbons. In some embodiments, a boiling point of the organic working fluid is less than a boiling point of water.
- the present disclosure provides a method for generating compounds with two or more carbon atoms (C 2+ compounds), comprising: (a) directing oxygen (O 2 ) and methane (CH 4 ) into an oxidative coupling of methane (OCM) reactor that reacts the O 2 and CH 4 in an OCM process to yield a product stream comprising (i) C 2+ compounds including ethylene (C 2 H 4 ) and heat; (b) transferring at least a portion of the heat from the product stream to a thermoelectric power generator; and (c) with the aid of the heat, using the thermoelectric power generator to generate power.
- OCM methane
- thermoelectric generator comprises a thin film thermoelectric module. In some embodiments, the thermoelectric generator comprises a micro thermoelectric module.
- FIG. 1 shows a typical oxidative coupling of methane (OCM) system with advanced separation
- FIG. 2 shows an OCM system with auto refrigeration (e.g., methane refrigeration);
- FIG. 3 shows an exemplary OCM system with a silver complexation ethylene recovery subsystem
- FIG. 4 shows an exemplary pressure swing adsoprtion (PSA) system
- FIG. 5A shows a schematic of CO 2 separation methods
- FIG. 5B shows a schematic of CO 2 separation methods
- FIG. 5C shows a schematic of CO 2 separation methods
- FIG. 6 shows typical CO 2 distillation system
- FIG. 7 shows a water electrolysis sub system
- FIG. 8 shows an OCM system with CO 2 as a quench medium
- FIG. 9 shows an organic Rankine cycle (ORC) subsystem
- FIG. 10 shows an exemplary typical OCM system
- FIG. 11 shows an exemplary OCM system with a single stage PSA unit
- FIG. 12 shows an exemplary OCM system with a multi stage PSA unit
- FIG. 13 shows an exemplary retrofit of OCM to a cracker, with a single stage PSA unit
- FIG. 14 shows an exemplary retrofit of OCM to a cracker, with a multi stage PSA unit
- FIG. 15 shows exemplary configurations of ethylene to liquids (ETL) systems without PSA
- FIG. 16 shows exemplary configurations of ETL systems with PSA
- FIG. 17 shows an exemplary PSA unit integrated with an OCM-ETL system for a midstream application
- FIG. 18 shows an exemplary PSA unit integrated with an OCM-ETL system in a natural gas liquids (NGL) application;
- FIG. 19 shows an exemplary PSA unit integrated with an OCM-ETL system for a refining application
- FIG. 20 shows an exemplary alternate scheme for a PSA unit integrated with an OCM-ETL system for a refining application.
- high hydrocarbon generally refers to a higher molecular weight and/or higher chain hydrocarbon.
- a higher hydrocarbon can have a higher molecular weight and/or carbon content that is higher or larger relative to starting material in a given process (e.g., OCM or ETL).
- a higher hydrocarbon can be a higher molecular weight and/or chain hydrocarbon product that is generated in an OCM or ETL process.
- ethylene is a higher hydrocarbon product relative to methane in an OCM process.
- a C 3+ hydrocarbon is a higher hydrocarbon relative to ethylene in an ETL process.
- a C 5+ hydrocarbon is a higher hydrocarbon relative to ethylene in an ETL process.
- a higher hydrocarbon is a higher molecular weight hydrocarbon.
- OCM process generally refers to a process that employs or substantially employs an oxidative coupling of methane (OCM) reaction.
- An OCM reaction can include the oxidation of methane to a higher hydrocarbon and water, and involves an exothermic reaction.
- methane can be partially oxidized and coupled to form one or more C 2+ compounds, such as ethylene.
- an OCM reaction is 2CH 4 +O 2 ⁇ C 2 H 4 +2H 2 O.
- An OCM reaction can yield C 2+ compounds.
- An OCM reaction can be facilitated by a catalyst, such as a heterogeneous catalyst. Additional by-products of OCM reactions can include CO, CO 2 , H 2 , as well as hydrocarbons, such as, for example, ethane, propane, propene, butane, butene, and the like.
- non-OCM process generally refers to a process that does not employ or substantially employ an oxidative coupling of methane reaction.
- processes that may be non-OCM processes include non-OCM hydrocarbon processes, such as, for example, non-OCM processes employed in hydrocarbon processing in oil refineries, a natural gas liquids separations processes, steam cracking of ethane, steam cracking or naphtha, Fischer-Tropsch processes, and the like.
- C 2+ and C 2+ compound generally refer to a compound comprising two or more carbon atoms.
- C 2+ compounds include, without limitation, alkanes, alkenes, alkynes and aromatics containing two or more carbon atoms.
- C 2+ compounds can include aldehydes, ketones, esters and carboxylic acids.
- Examples of C 2+ compounds include ethane, ethene, acetylene, propane, propene, butane, and butene.
- non-C 2+ impurities generally refers to material that does not include C 2+ compounds.
- non-C 2+ impurities which may be found in certain OCM reaction product streams, include nitrogen (N 2 ), oxygen (O 2 ), water (H 2 O), argon (Ar), hydrogen (H 2 ) carbon monoxide (CO), carbon dioxide (CO 2 ) and methane (CH 4 ).
- small scale generally refers to a system that generates less than or equal to about 250 kilotons per annum (KTA) of a given product, such as an olefin (e.g., ethylene).
- KTA kilotons per annum
- the term “world scale,” as used herein, generally refers to a system that generates greater than about 250 KTA of a given product, such as an olefin (e.g., ethylene). In some examples, a world scale olefin system generates at least about 1000, 1100, 1200, 1300, 1400, 1500, or 1600 KTA of an olefin.
- a given product such as an olefin (e.g., ethylene).
- a world scale olefin system generates at least about 1000, 1100, 1200, 1300, 1400, 1500, or 1600 KTA of an olefin.
- item of value generally refers to money, credit, a good or commodity (e.g., hydrocarbon). An item of value can be traded for another item of value.
- carbon efficiency generally refers to the ratio of the number of moles of carbon present in all process input streams (in some cases including all hydrocarbon feedstocks, such as, e.g., natural gas and ethane and fuel streams) to the number of moles of carbon present in all commercially (or industrially) usable or marketable products of the process.
- Such products can include hydrocarbons that can be employed for various downstream uses, such as petrochemical or for use as commodity chemicals.
- Such products can exclude CO and CO 2 .
- the products of the process can be marketable products, such as C 2+ hydrocarbon products containing at least about 99% C 2+ hydrocarbons and all sales gas or pipeline gas products containing at least about 90% methane.
- Process input streams can include input streams providing power for the operation of the process.
- power for the operation of the process can be provided by heat liberated by an OCM reaction.
- the systems or methods of the present disclosure have a carbon efficiency of at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, or at least about 90%.
- the systems or methods of the present disclosure have a carbon efficiency of between about 50% and about 85%, between about 55% and about 80%, between about 60% and about 80%, between about 65% and about 85%, between about 65% and about 80%, or between about 70% and about 80%.
- C 2+ selectivity generally refers to the percentage of the moles of methane that are converted into C 2+ compounds.
- specific oxygen consumption generally refers to the mass (or weight) of oxygen consumed by a process divided by the mass of C 2+ compounds produced by the process.
- specific CO 2 emission generally refers to the mass of CO 2 emitted from the process divided by the mass of C 2+ compounds produced by the process.
- PSA technology can be used in a large variety of applications: Hydrogen purification, air separation, CO 2 removal, noble gases purification, methane upgrading, n-iso paraffin separation and so forth. While new applications for gas separations by adsorption are continually being developed, the most important applications have been air separation (for production of O 2 and N 2 ) and hydrogen separation (from fuel gas). Approximately 20% of O 2 and N 2 are currently produced by PSA. The increasing industrial applications for adsorption have stimulated a growing interest in research and new applications.
- Processes of the present disclosure can employ a variety of different separations techniques, alone or in combination.
- OCM processes can employ amine and caustic systems for CO 2 removal, molecular sieve guard beds for water removal, and cryogenic distillation or other separation techniques for recovery and purification of hydrocarbon components.
- Cryogenic separation can refer to separations using temperature levels below 120 K or about ⁇ 153° C.
- Other techniques include SelexolTM and RectisolTM processes for CO 2 removal.
- OCM product effluent can comprise a mixture of hydrocarbons including but not limited to methane, ethane, ethylene, propane, propylene, butanes, butenes, and higher hydrocarbons.
- OCM product effluent can also comprise varying amounts of other components such as H 2 , N 2 , CO, CO 2 and H 2 O.
- the product of an OCM reaction can include ethylene.
- the ethylene product can be polymer grade, refinery grade or chemical grade. Depending on the purity level required, different separation and/or purification techniques can be employed with the OCM process. To recover high purity ethylene, separation methods such as those discussed herein can be used to remove a wide range of components.
- Advantages of the advanced OCM processes described herein can include reducing the cost, reducing the number of unit operations (“units”) used, and hence improving the overall process for producing high purity polymer grade ethylene. Overall conversion and carbon efficiency can also be improved. The separation methods disclosed herein can also improve the overall conversion and carbon efficiency.
- the different separation and purification techniques discussed herein can be used to separate the OCM product effluent (e.g., process gas) into a plurality of streams, including but not limited to a first stream comprising methane, hydrogen, carbon monoxide and other lighter inerts and a second stream comprising ethane, ethylene, propylene, and higher hydrocarbons.
- Separation systems or subsystems employed can include those discussed herein, such as a cryogenic demethanizer, a membrane separation system, or a PSA based system.
- the separation techniques discussed herein can be employed to remove CO 2 , such as from an OCM product effluent stream.
- One or more separations techniques can be used to remove CO 2 including but not limited to absorption, adsorption, CO 2 distillation, and membrane separation.
- the separation technique can be non-cryogenic.
- FIG. 1 shows a block flow diagram for an exemplary OCM process.
- Oxygen 110 and methane 121 can be fed into an OCM reactor 101 for conversion into higher hydrocarbon compounds including ethylene.
- the OCM product stream 111 can be directed to a compressor 102 , and the compressed product stream 112 can be fed into a separations system 103 .
- the separations system can include pretreatment units 104 , such as impurity and CO 2 removal units, as well as separations units 105 , such as cryogenic, non-cryogenic, complexation, membrane, and other separations units.
- the separations system can be a combination of more than one separation techniques, such as those discussed in this application.
- the separation system can replace CO 2 removal, moisture removal, and cryogenic separation systems of existing OCM process systems.
- the compressor system may not be required for some types of separation processes.
- CO 2 can be vented 113
- ethane 114 can be recovered, for example for recycling to the OCM reactor
- ethylene product 115 can be recovered
- C 3+ products 116 can be recovered.
- CO 2 117 and methane 118 can be directed from the separations system into a methanation unit 106 .
- the methanation unit can produce methane from the CO 2 , for recycling 119 back to the OCM reactor.
- Additional methane 120 can be added to the OCM reactor supply stream 121 .
- OCM process systems can use refrigeration subsystems to condense overhead vapors, for example from a demethanizer, a deethanizer, and/or a C 2 splitter.
- the temperatures employed can be in the range from about 12° C. to about ⁇ 100° C. These low temperatures can be achieved through the use of multiple refrigeration systems, such as ethylene refrigeration and propylene refrigeration systems, to provide different levels of refrigeration. These can be similar to those employed in existing steam crackers.
- an open loop methane refrigeration system can be employed to provide refrigeration for a demethanizer OCM product effluent can comprise methane as the major component, for example at a concentration of at least about 50 mol %, 60 mol %, 70 mol %, 80 mol %, or 90 mol %.
- the demethanizer can have the lowest temperature requirements in the entire separations unit.
- Use of methane refrigeration e.g., auto-refrigeration
- can provide benefits such as elimination of the need for an additional refrigeration system (e.g., new) for any added capacity. For grassroots or greenfield OCM applications, this can considerably reduce refrigeration compressor sizes needed. In some cases, an entire refrigeration system can be eliminated.
- FIG. 2 shows a block flow diagram for an exemplary open loop methane refrigeration system, such as can be used in gas processing plants and steam crackers to produce chilling for condensing overhead vapors from a demethanizer
- the separations unit 205 can include an open loop methane refrigeration system to provide cooling for the separations.
- the system can be combined with a single or multiple stage (e.g., two-stage) expansion system (e.g., Joule Thompson) to chill the incoming feed.
- a single or multiple stage e.g., two-stage expansion system (e.g., Joule Thompson) to chill the incoming feed.
- multiple separate lighter products are recovered, such as a light H 2 -rich stream, a low pressure methane rich stream, and a high pressure methane rich stream.
- the mixed refrigerant can be, for example, a mix of methane, ethylene and propylene.
- the mixed refrigerant can be a mix of ethane and propane.
- a wide range of possible mixed refrigerants can be employed, and can be selected based on, for example, the availability of certain components and the degree of refrigeration required.
- a mixed refrigerant system can provide advantages for use with an OCM reactor system, including the use of only one refrigeration sub system. Rather than two refrigeration systems each comprising multiple stages of refrigerant compressor, associated vessels, exchangers, and other components, the process can use a single refrigeration system. This can substantially reduce capital cost. This can also reduce equipment count, which can be a benefit especially for OCM retrofits at places where plot space may be a concern.
- Pi complexation techniques can be used to separate alkenes from alkanes. Some metal ions complex selectively with unsaturated organic compounds. Some of these complexes are reversible while others are irreversible. For example, aqueous silver salt in solution forms reversible complexes with olefins, and forms irreversible complexes with acetylenes. This property can be employed in an OCM process to recover ethylene and propylene from OCM reactor effluent.
- separation of ethylene and/or propylene by metal complexation can be divided into three major sections: absorption, purification or venting of impurities, and desorption.
- An exemplary process is provided for separation of ethylene and/or propylene from a purified multi-component gas stream from the OCM reactor.
- FIG. 3 shows a process for purifying a stream containing ethylene using an aqueous silver nitrate solution.
- Metal complexation e.g., silver or cuprous ion complexation
- OCM comprising C 2 compounds, C 3 compounds, and lighter components such as hydrogen and nitrogen.
- the multi-component gas stream 310 can be introduced into an absorber 301 with aqueous silver salt solution, such that the ethylene and/or propylene undergo absorption or complexing with the silver metal ions, and such that trace acetylenes react with the silver metal ions.
- Vent gas 311 can be removed from the absorber.
- the silver salt solution stream 312 can be vented 313 in a vent column 302 at reduced pressure to remove any dissolved low molecular weight components.
- the resulting silver salt solution stream can be treated in a stripper 303 to separate the absorbed or complexed ethylene and/or propylene from the silver salt solution, and further treated in a treatment unit 304 to release the trace acetylenes.
- Purified ethylene 316 can be recovered, and some product can be recycled 317 .
- the aqueous silver salt stream 318 can then be recycled to the first step, in some cases after regeneration in a regeneration unit 305 with AgMnO 4 320 .
- MnO 2 321 can be removed from the regeneration unit.
- H 2 O 2 319 can be added to the solvent stream being returned to the absorber.
- Useful adsorbents include but are not limited to metal compounds, such as silver or copper, supported on high surface area carriers with a plurality of pores. These adsorbents can be used in pressure swing adsorption or temperature swing adsorption processes. When operating pressure and/or temperature is changed, the silver or copper compound can release the alkene-rich component from the adsorbent. These adsorbents can be very effective for selective adsorption of alkenes such as ethylene, propylene, and mixtures of these from gaseous mixtures.
- the loading of the gas can be affected by its partial pressure and the temperature and the concentration of the complexing ions in the solution. Therefore, by changing the physical conditions separately or collectively, the active gaseous component can either be formed into or out of the solution. Adjusting or swinging one or more physical parameters can be used to carry out an ethylene or propylene separation using an aqueous silver nitrate solution. Purification or venting of impurities can result in a product stream that is free or substantially free of impurities including but not limited to CO 2 , sulfur compounds, acetylenes, and hydrogen. Acetylene and hydrogen can cause operational problems and so the process gas can be treated to bring the concentration of such impurities to within an acceptable limit.
- Metal complexation can be used in combination with other processes, such as membrane based processes.
- Membranes can be used to perform a variety of separations, such as separations of olefins and paraffins, or separations of CO 2 .
- a membrane can be essentially a barrier that separates two phases and restricts transport of various chemicals in a selective manner.
- Polymer membranes can be used to separate mixtures such as propylene/propane mixtures and ethylene/butene mixtures. Separations in polymeric membranes are dependent on the solubility and diffusion of the species through the membrane. While zeolite-based separations are predominantly depended on molecular size differences, the differing permeation of olefins through a polymeric membrane can be largely attributed to differences in solubility, which can depend on the critical temperature and the kinetic diameter. Membrane separations can be employed even when there are small molecular size differences.
- the OCM process can utilize a membrane based separation process to further enhance the efficiency and energy consumption of the process.
- Cryogenic distillation can be used for the separation of alkenes, but is highly energy intensive.
- Membrane based separations can be used for a variety of purposes in the context of an OCM process, such as to separate and purify ethylene product from OCM reactor effluent, to separate a stream rich in CO 2 , to separate a stream containing lighter hydrocarbons and inerts, or to separate C 2 compounds from C 1 and lighter compounds.
- Membranes can include but are not limited to isotropic membranes, anisotropic membranes, and electrically charged membranes.
- a membrane can be a ceramic membrane, a metal membrane, or a liquid membrane.
- An isotropic membrane can be a microporous membrane or a non-porous dense membrane.
- Membranes can be used for separations including but not limited to CO 2 separation, paraffin-olefin separation, or selective recovery of pure ethylene from the OCM reactor effluent.
- Polymer derived carbon molecular sieve membranes can be used to separate paraffins from olefins. These membranes can be used, for example, to separate ethylene from a mix of methane and ethane.
- Membrane separations can be used in combination with other types of separation and purification subsystems to remove other impurities such as acid gases, hydrogen, and nitrogen.
- a driving force can be a pressure differential or a concentration (activity) gradient across the membrane.
- Membrane based separation techniques can be used in an OCM process by applying either of the above mentioned driving forces.
- a membrane based separation can also be a component of a hybrid separation set-up, such as a membrane and an absorption system (e.g., a membrane contactor) or a membrane in a pressure swing adsorption (PSA) or a temperature swing adsorption (TSA) system.
- a membrane and an absorption system e.g., a membrane contactor
- PSA pressure swing adsorption
- TSA temperature swing adsorption
- An OCM reactor can employ membranes as a part of the reactor system to effectively separate the ethylene product within the reactor system itself.
- a section of the reactor can include membranes that aid in recovering the ethylene product, with a methane rich stream being recycled to a methanation system and eventually to the OCM reactor.
- Such a system can also use advanced heat recovery or quench methods so as to facilitate the use of membranes.
- PSA Pressure Swing Adsorption
- Cryogenic separation can be used for the recovery of ethylene, propylene, and other components from olefin plants, refinery gas streams, and other sources. These separations can be difficult to accomplish because of the close relative volatilities, and can have significant temperature and pressure requirements for operation.
- the ethane/ethylene distillation can be performed at about ⁇ 25° C. and 320 pounds per square inch gauge (psig) in a column containing over 100 trays.
- Distillation of propane and propylene can be performed at about ⁇ 30° C. and 30 psig. These can be some of the most energy intensive distillations in the chemical and petrochemical industry. In general, the use of distillation towers to separate recover and purify components is an energy intensive process.
- the present disclosure provides the use of adsorbents that can achieve separation and purification of olefin rich streams.
- the present disclosure applies the use of PSA-based adsorbent systems to separate, purify, and recover olefins like ethylene and propylene from streams containing one or more impurities such as methane, hydrogen, carbon monoxide, carbon dioxide, ethane, or others.
- the streams, or parts of the streams can be generated via an OCM process, an ETL process, or combinations thereof.
- the streams can be final product streams where PSA is used to recover and purify the final product.
- the streams can be intermediate streams which are purified prior to use as a feed in a subsequent process, such as an ETL process, an ethylene cracker (steam cracker), a refining unit, a fuel gas system, a natural gas recovery plant or any other product fractionation or product treatment unit.
- a subsequent process such as an ETL process, an ethylene cracker (steam cracker), a refining unit, a fuel gas system, a natural gas recovery plant or any other product fractionation or product treatment unit.
- PSA Pressure Swing Adsorption
- a pressure swing adsorption (PSA) process cycle is one in which desorption takes place at a different (e.g., lower) pressure than the adsorption pressure. Reduction of pressure can be used to shift the adsorption equilibrium and affect regeneration of the adsorbent. Low pressure may not be as effective as temperature elevation in totally reversing adsorption, unless very high feed to purge pressure ratios are applied. Therefore, most PSA cycles are characterized by high residual loadings and thus low operating loadings. These low capacities at high concentration require that cycle times be short for reasonably sized beds (e.g., seconds to minutes). These short cycle times are attainable because particles of adsorbent respond quickly to changes in pressure.
- Major uses for PSA processes include purification as well as applications where contaminants are present at high concentrations.
- the PSA system can comprise two fixed bed adsorbers 401 and 402 undergoing a cyclic operation of four steps—adsorption, blowdown, purge, and pressurization.
- the PSA system can receive a feed 410 and produce a product stream 411 , with a PSA off gas stream 412 .
- additional operation steps can be employed such as pressure equalization, product pressurization, and co-current depressurization.
- the number of beds can be modified to achieve the optimal operation and multi-bed processes can be used in commercial applications like hydrogen recovery.
- a TSA system can be used where a swing in temperature causes the sorption and desorption.
- PSA cycles are used primarily for purification of wet gases and of hydrogen.
- High pressure hydrogen employed in processes such as hydrogenation, hydrocracking, and ammonia and methanol production can be produced by PSA beds compounded of activated carbon, zeolites and carbon molecular sieves.
- Other exemplary applications include: air separation, methane enrichment, iso/normal separations, and recovery of CO and CO 2 .
- Adsorbents can be natural or synthetic materials, such as those having amorphous or microcrystalline structure.
- exemplary adsorbents useful for large scale operation include but are not limited to activated carbon, molecular sieves, silica gels, and activated alumina.
- Other useful adsorbents include pi complexation sorbents, silver and copper complexation adsorbents, zeolites, synthetic zeolites, mesoporous materials, activated carbons, high surface area coordination polymers, molecular sieves, carbon molecular sieves (CMS), silica gels, MCM, activated alumina, carbon nanotubes, pillared clays, and polymeric resins.
- adsorbents For systems where the incoming stream is a multi-component mixture of gases and the number of compounds to be separated cannot be removed by a single adsorbent, different layers of adsorbents can be used.
- hydrogen purification from a methane stream in a reforming operation where H 2 is contaminated with H 2 O, CO 2 , CO, and unconverted CH 4 , can employ activated carbon to remove H 2 O and CO 2 in combination with additional layers of different adsorbents used to increase the loading of CO.
- Zeolites, molecular sieves, and carbon molecular sieves can be used for most industrial separations employing PSA.
- Inorganic materials, like special kinds of titanosilicates, can be used for kinetic separations.
- exemplary types of adsorbents include zeolites/molecular sieves and pi complexation sorbents.
- Zeolites/molecular sieves can be used for kinetic separation, such as separation based on higher diffusivity of olefins over that of paraffins.
- 4 A zeolite is one such example.
- Pi complexation sorbents such as AgNO 3 /SiO 2 , can give excellent results as compared to 4 A zeolite.
- PSA units as discussed herein can employ a range of different sorbents, including but not limited to a zeolite/molecular sieve sorbent, a pi complexation based sorbent, a carbon molecular sieve sorbent or any other form of activated carbon, carbon nanotubes, polymeric resin based sorbents, or other sorbents.
- sorbents including but not limited to a zeolite/molecular sieve sorbent, a pi complexation based sorbent, a carbon molecular sieve sorbent or any other form of activated carbon, carbon nanotubes, polymeric resin based sorbents, or other sorbents.
- Adsorbents can be selected based on a number of different criteria.
- Adsorbent selection criteria can include capacity for the target components (e.g., affinity for the desired components to be separated from the multi-component feed stream), selectivity between components competing for same adsorption sites, regenerability of the adsorbent, (e.g., the ability of the adsorbent to release the adsorbed target components at a reasonable pressure rate of gas diffusion into the adsorbent—this can also affect the size of the bead that is chosen and consequently the pressure drop across the bed; an insufficient diffusion rate can require smaller diameter beads that can result in higher pressure drop and hence increased operating costs), and chemical compatibility (e.g., selecting an adsorbent resistant to chemical attack that may poison or destroy the adsorbent, such as liquid hydrocarbons causing physical breakdown of the adsorbent resulting in loss of efficiency and back pressure).
- FIG. 5A , FIG. 5B , and FIG. 5C show exemplary schematics of different separation methods available to separate CO 2 from a process gas or a flue gas.
- OCM processes can utilize an amine based absorption system for CO 2 removal, which can be followed by use of a caustic scrubber to obtain high degree of separation.
- the amine system is prone to corrosion, solvent degradation, and above all, has high energy requirements.
- Separations with sorbents and/or solvents can involve placing the CO 2 containing gas in intimate contact with a liquid absorbent or a solid sorbent that is capable of capturing the CO 2 .
- a stream with CO 2 510 can be directed into a capture vessel 501 , where it contacts sorbent which captures CO 2 from the stream.
- the stream, with reduced or removed CO 2 can then exit 511 the vessel.
- Sorbent 512 loaded with captured CO 2 can be transferred to a sorbent regeneration vessel 502 where it releases the CO 2 after being heated (e.g., with the use of energy 513 ), after a pressure decrease, or after any other change in the conditions around the sorbent, thereby regenerating the sorbent.
- Spent sorbent 515 and CO 2 516 can be removed from the vessel, and make up sorbent 513 can be added.
- the sorbent can be sent back to capture more CO 2 in a cyclic process.
- the sorbent can be a solid.
- Solid sorbent can remain in a single vessel rather than being cycled between vessels; sorption and regeneration can be achieved by cyclic changes (e.g., in pressure or temperature) in the vessel where the sorbent is contained. A make-up flow of fresh sorbent can be used to compensate for natural loss of activity and/or sorbent losses.
- Amine scrubbing technology can be used to remove acid gases from process gases.
- Primary amines e.g., MEA, DGA
- secondary amines e.g., DEA, DIPA
- tertiary e.g., MDEA, TEA
- sterically hindered amines chilled ammonia, potassium carbonate, and other compounds
- Traditional amine based systems can be characterized by high energy requirements and solvent degradation.
- Improved solvents which can require less energy for regeneration of the solution, include the Benfield process and two stage diethanolamine.
- Combination with an OCM process can reduce the energy consumption of amine scrubbing processes.
- Improved solvents can reduce the energy requirements by as much as 40% compared to the traditional MEA solvents. This has the potential of reducing the energy, and hence steam, consumption of the OCM process, thereby increasing the amount of steam available for export from the OCM, or making alternative waste heat recovery methods feasible.
- Physical absorption solvents used can include but are not limited to glycol dimethylethers (e.g., Selexol) and propylene carbonate (e.g., IPTS/EC). Regeneration of the solution can be performed by vacuum flashing and air stripping; this approach can consume significantly less energy than in chemical absorption. In using physical solvents CO 2 can be released mainly by depressurization, thereby avoiding the high heat of consumption of amine scrubbing processes.
- glycol dimethylethers e.g., Selexol
- IPTS/EC propylene carbonate
- Mixed or hybrid solvents can include but are not limited to SulfinolTM (sulfolane, water, and amine), such as Sulfinol-M and Sulfinol-X.
- SulfinolTM sulfolane, water, and amine
- Solid adsorbents such as zeolites and activated carbon, can be used to separate CO 2 from gas mixtures.
- PSA pressure swing adsorption
- a gas mixture can flow through a packed bed of adsorbent at elevated pressure until the concentration of the desired gas approaches equilibrium. The bed can be regenerated by reducing the pressure.
- TSA temperature swing adsorption
- the adsorbent can be regenerated by raising its temperature.
- adsorption is not yet considered attractive for large scale separation of CO 2 because the capacity and CO 2 selectivity of available adsorbents are low.
- an adsorbent based separation method can be used to separate bulk CO 2 followed by consuming the remaining CO 2 in a methanation reactor system, or by using a caustic scrubber to treat the remaining CO 2 .
- FIG. 5B shows an exemplary schematic of separation of CO 2 from a gas stream 530 in a separation vessel 520 using a membrane 521 .
- CO 2 can be removed from the stream via the membrane, and CO 2 and other gases can exit the vessel in separate streams 531 and 532 .
- the main limitation of currently existing membranes is the occurrence of severe plasticization of the membrane in the presence of high pressure CO 2 . Due to excessive swelling of the polymer membrane upon exposure to CO 2 , the performance (e.g., selectivity) can decrease significantly, thus reducing the purity of the CO 2 and consequently reducing the possibilities for reuse of the gas.
- membrane technology can use 70-75 kWh per ton of recovered CO 2 compared to significantly higher values for pressure swing adsorption (e.g., 160-180 kWh), cryogenic distillation (e.g., 600-800 kWh), or amine absorption (e.g., 330-340 kWh), making membrane technology an attractive option for integration with OCM for CO 2 separation.
- pressure swing adsorption e.g. 160-180 kWh
- cryogenic distillation e.g., 600-800 kWh
- amine absorption e.g., 330-340 kWh
- Micro-porous hollow fiber membranes can be used for CO 2 separation using amine-based chemical absorption processes.
- Micro-porous membranes can be used in a gas-liquid unit where the amine solution is contacted with CO 2 containing gas. Using the membrane can lead to a reduction in the physical size and weight of the gas-liquid contacting unit. The separation is based on reversible chemical reaction, and mass transfer occurs by diffusion of the gas through the gas/liquid interface as in traditional contacting columns.
- Such a hybrid membrane contactor can provide a high contact area between gas and liquid, reduce or essentially eliminate foaming and flooding problems, and give better operational flexibility while reducing solvent degradation problems.
- a membrane contactor can combine the advantages of membrane technology and solvent absorption for CO 2 separation.
- a membrane contactor is a combination of advanced membrane techniques with an effective absorption process.
- a membrane contactor is a hybrid mass exchanger where a porous membrane separates two phases. The selective sorbent performs the separation while the membrane facilitates the mass exchange process by expanding the phase contact surface area. The modified surface properties can improve the selectivity of the process by selectively inhibiting the transport of one of the mixture constituents.
- membranes can allow for up to five times increase in yield per unit volume. Since the sorptive liquid flows within capillaries and both phases are not directly contacting each other, membrane absorbers can operate in any spatial configuration (horizontal or vertical) and at any flux rations between both phases.
- Membranes used can be micromembranes or ultrafiltration membranes made a variety of different polymer and ceramic materials.
- Polypropylene fiber membranes can be used to separate CO 2 from CH 4 , for example by using amines like MEA as absorption liquid.
- Hollow fiber membranes, such as porous polypropylene, perfluoroalkoxy (PFS), and asymmetric poly(phenylene oxide) hollow fiber membranes with a dense ultrathin skin at the outside of the membrane can also be used.
- absorption liquids such as aqueous sarcosine salt solutions, for example in a gas-liquid membrane contactor system.
- a membrane contactor can be used to separate the CO 2 from the OCM effluent in which CH 4 is the major component.
- Membrane contactors can also be used for separation of olefins and paraffins, and the separation of CO 2 from light gases.
- An activator such as piperazine, diethanolamine, and arsenic trioxide, can be used to further enhance the effectiveness of CO 2 capture.
- DGA and tertiary amines may provide more improvement than primary or secondary amines.
- Gas selective poly ionic liquid membranes which are polymerized room temperature ionic liquids (RTIL), can be used to be highly selectively separate CO 2 .
- RTILs can be synthesized as a monomer and subsequently polymerized to obtain gas selective membranes.
- the ionic nature of the polymers can result in tight arrangements between the oppositely charged ionic domains in the poly RTIL, which can eventually prevent the membrane from excessive swelling and deterioration of its performance at increased pressure and/or temperature.
- This intrinsic property of poly RTIL can be used to increase the resistance against plasticization and to restrict strong swelling of the polymer membrane to maintain its permeation properties in the presence of a strong plasticizing agent such as CO 2 at higher pressures.
- an imidazolium-based poly RTIL can be used as base material and the length of the alkyl chain can serves to strengthen or weaken the ionic interactions within the poly RTIL.
- Ionic liquids are molten salts with a very low melting point (many are liquids at room temperature). Many ionic liquids show a high solubility for carbon dioxide and hence can be highly suitable for use with an OCM process.
- ionic liquids can include but are not limited to imidazolium, pyrollidinium, pyridinium, cuanidinium, phosphonium, morpholinium, piperidinium, sulfonium, ammonium, hexafluorophosphate, tetraflouroborate, alkylsulphate, triflate, dicyanamide, bis(trifluoromethylsulfonyl)imide, and combinations thereof.
- Specific advantages of ionic liquids include very low to negligible vapor pressure, good dissolution characteristics for many substances, and lack of flammability or toxicity. Ionic liquids can have good thermal, mechanical and chemical stability as well as favorable densities and viscosities.
- Ionic liquids can be used as chemical solvents, catalysts, electrolytes in fuel cells as well as for gas-separation and storage by absorption.
- Ionic liquid membrane systems can comprise an adequate porous support material, e.g. a polymer film, coated by ionic liquids. The system separated CO 2 and sulfur compounds from different gas mixtures. Competitive selectivity and permeability are obtained for the separations.
- Novel membrane materials such as polyetherimides, can be used as membrane material with improved plasticization resistance for CO 2 removal, for example with an OCM process.
- Other membrane materials that can be used include polymeric membranes based on polyamides, polysemicarbazides, polycarbonates, polyarylates, polyaniline, poly(phenylen oxide), polysulfones, and polypyrrolones.
- the polymeric membrane is solvent resistant and can reduce the plasticization effects of hydrocarbons in the feed stream, e.g., polyketone, polyether ketone, polyarylene ether ketone, polyimide, polyetherimide, and polyphenylene sulphide, which have intrinsic solvent inertness and can therefore withstand organic rich operation conditions.
- An adequate porous support material e.g. a polymer film, coated by ionic liquids can be used in continuous separation of CO 2 and sulfur compounds from different gas mixtures, including a methane rich stream. This separation can improve the efficiency of OCM processes.
- the OCM reactor effluent can enter the supported ionic liquid separation subsystem, and CO 2 and other contaminants can be removed from the process gas.
- Other contaminants can include but are not limited to traces of sulfur compounds, inerts, CO, SO 2 , H 2 S, and tetrahydrothiophene (THT).
- CO 2 can be separated from other gases by cooling and condensation, for example as shown in FIG. 5C .
- a stream containing CO 2 550 can be compressed in a compressor 540 , and the compressed stream 551 can be directed to a distillation column 541 .
- Some components can be recovered from the overhead stream 552 , with heat recovered in a heat exchanger 542 .
- Other components can be recovered from the bottoms 555 .
- Cryogenic separation is widely used commercially for streams that already have a high concentration of CO 2 (typically greater than 90%).
- Cryogenic separation of CO 2 has the advantage that it enables direct production of high purity liquid CO 2 that can be used as a feedstock to convert the carbon to higher value hydrocarbons, or otherwise be captured. The amount of energy required can be high, and water may need to be removed before the feed gas is cooled.
- Low temperature distillation can give better results when there is a high concentration of CO 2 in the feed gas.
- the CO 2 concentration can be increased by, for example, having a recycle stream, or by using a modified OCM reactor where excess CO 2 is used as a quench medium for the reaction heat.
- Low temperature separation can refer to separations using temperature levels above ⁇ 90° C.
- FIG. 6 shows a schematic of CO 2 separation using distillation.
- OCM reactor effluent 606 can be fed to a treatment unit 601 , such as a molecular sieve dryer, a sulfur removal bed, or an acetylene removal bed.
- the treated gas is fed to the first distillation column 602 that separates the bulk of the methane from the CO 2 and other heavier hydrocarbons.
- the bottom stream 608 may contain 50%, 60%, 70%, 80%, 90% (or anywhere in between) of the incoming CO 2 .
- the overhead from 607 contains majority of the methane and other light gases and is fed to the column 603 .
- Column 603 further recovers methane rich gas 611 , which can be the feed to a methanation system.
- the bottoms product 616 may be recycled or sent as a purge to the fuel gas system.
- the CO 2 rich gas 608 is distilled in the CO 2 column 604 to recover pure CO 2 609 in the overhead.
- the bottoms product 610 can contain some methane along with ethane, ethylene, and other heavier hydrocarbons, and can be sent to recover the ethylene product in a separator 605 .
- the CO 2 product can be sent to methanation unit, and a part of the CO 2 can be recycled to achieve the desired concentration of CO 2 in the feed stream 606 .
- Such a CO 2 distillation sub system can offer many benefits, including but not limited to reducing the loop size of the OCM process considerably, as the function of the existing cryogenic demethanizer can be reduced by a large extent. Additionally, amine and caustic systems can be replaced by cryogenic or low temperature distillation systems.
- Alkaline salt-based processes can be used for carbon dioxide removal. These processes can utilize the alkali salts of various weak acids, such as sodium carbonate and potassium carbonate. These processes can provide advantages such as low cost and minimal solvent degradation. Processes that can be used for H 2 S and CO 2 absorption include those using aqueous solutions of sodium or potassium compounds. For example, potassium carbonate can absorb CO 2 at high temperatures, an advantage over amine-based solvents.
- Hot potassium carbonate (K 2 CO 3 ) solutions can be used for the removal of CO 2 from high-pressure gas streams, among other applications.
- Potassium carbonate has a low rate of reaction.
- mass transfer promoters such as piperazine, diethanolamine, and arsenic trioxide can be used.
- Less toxic promoters such as borate can also be used, for example with flue gas streams (see, e.g., Ghosh et al., “Absorption of carbon dioxide into aqueous potassium carbonate promoted by boric acid”, Energy Procedia, pages 1075-1081, February 2009, which is hereby incorporated by reference in its entirety).
- inhibitors can be added. These systems can be known as activated hot potassium carbonate systems.
- Licensed hot activated potassium carbonate systems include the BenfieldTM and the CatacarbTM process. The processes can be used for bulk CO 2 removal from high-pressure streams, but can also produce high-purity CO 2 .
- Flue gas impurities such as SOx and NOx can reduce the operational efficiency of the potassium carbonate as a solvent. SO 2 and NO 2 may not able to be released from the solvent under industrial conditions. Selective precipitation of the impurity salts formed by SOx and NOx can be used to remove such compounds (see, e.g., Smith et al., “Recent developments in solvent absorption technologies at the CO2CRC in Australia” Energy Procedia, pages 1549-1555, February 2009, which is hereby incorporated by reference in its entirety).
- CO 2 sorbents through chemical reactions and physical absorptions, including but not limited to soda-lime, active carbon, zeolites, molecular sieves, alkali metal oxides, silver oxide, lithium oxide, lithium silicate, carbonates, silica gel, alumina, amine solid sorbents, metal organic frameworks and others.
- CO 2 -reactive polymers such as tetraethylene pentamine or polyethyleneimine
- a porous support such as alumina, pumice, clay or activated carbon
- Amine based sorbents can be easily regenerated.
- a mixture of an amine compound with a polyol compound can be impregnated in a porous support.
- the polyol compound can be used to increase the CO 2 desorption rate of the amine.
- the supported amine-polyol sorbent can comprise from about 1 wt % to about 25 wt % amine and from about 1 wt % to about 25 wt % polyol, with the balance being the support.
- Solid sorbent can adsorb and desorb CO 2 a relatively high rates at ambient temperatures Enhanced CO 2 cyclic removal capacities in either dry or humid air flows can further be achieved by using a solid sorbent at an increased amine concentration of amines from about 35 wt % to about 75 wt %.
- Solid sorbents that can selectively remove multiple gases can be used to remove CO 2 , H 2 O, nitrogen oxides, and hydrocarbons. This can be achieved by using composite adsorbents, for example by using a mixed adsorbent of alumina and zeolite to remove CO 2 and H 2 O simultaneously.
- CO 2 can be separated from flue gas using an ion pump method instead of relying on large temperature and pressure changes to remove CO 2 from a solvent.
- Ion pump methods can dramatically increase the overlying vapor pressure of CO 2 .
- the CO 2 can be removed from the downstream side of the ion pump as a pure gas.
- the ion pumping can be obtained from techniques including but not limited to reverse osmosis, electro dialysis, thermal desalination methods, or an ion pump system having an oscillation flow in synchronization with an induced electric field.
- Synthetic analogues of enzymes as a polymer thin film supported on micro-porous substrates can be used to separate CO 2 from gas mixtures.
- a polymer thin film containing carbonic anhydrase mimicking sites can supported on a porous substrate and can separate CO 2 from a stream containing O 2 and N 2 .
- the system can be, for example, about 30% lower in cost compared to amine-based systems.
- Electrolysis can be used to produce industrial hydrogen.
- OCM processes can have a lot of synergistic benefit from deploying a water electrolysis subsystem with the OCM process.
- the water electrolysis unit can replace an air separation unit (ASU) to supply the oxygen required for the OCM process.
- ASU air separation unit
- the products from the electrolytic unit can be consumed within the OCM process: oxygen can be consumed within the OCM reactor and hydrogen can be used in a methanation reactor.
- Availability of more hydrogen in the methanation unit has the potential to increase the carbon efficiency to about 100%, by converting the CO 2 produced in the OCM reaction to methane, which can be recycled back to the OCM reactor.
- the OCM unit can be a net exporter of high purity excess hydrogen, after consuming the entirety of the CO 2 produced in the OCM Process.
- the water electrolysis subsystem can be an electrolytic cell employing alkaline water electrolysis, a proton exchange membrane electrolysis system, or a steam electrolysis system.
- the electricity source to the electrolytic sub system can be renewable, such as photo voltaic/solar power, which can make the entire system 100% carbon efficient with a zero carbon footprint.
- a storage system for oxygen, or a backup power supply, may be used to ensure the continuous supply of oxygen and hydrogen.
- FIG. 7 depicts an exemplary electrolysis subsystem combined with an OCM system.
- the electrolysis subsystem 701 can take water 710 and electric power 711 as inputs and generate pure oxygen 712 and hydrogen 713 as products.
- the oxygen can be fed into an OCM reactor 702 with a methane feed 714 , for conversion to higher hydrocarbon products including ethylene.
- the OCM product stream can be compressed in a compressor 704 and separated in a separations unit 705 .
- Higher hydrocarbon products 716 can be recovered from the separations unit, and other compounds such as methane and CO 2 can be recycled 717 and/or purged 718 .
- the recycle stream can be directed to a methanation unit 703 , which can generate methane 715 using the hydrogen from the electrolysis subsystem.
- the extra hydrogen that is now available to the methanation unit can enable the conversion of most or all of the CO 2 produced in the OCM process to methane, which can drive the process to a higher efficiency.
- the process can also be almost 100% emission free.
- the CO 2 produced in the process that may be discarded as waste may be converted to methane and hence to ethylene in the OCM reactor.
- FIG. 8 shows an exemplary system where CO 2 814 is removed from an OCM product stream 812 (generated in an OCM unit 801 from an oxygen stream 810 and a methane stream 811 ) in a CO 2 separation unit 802 and recycled from back to the OCM reactor 801 .
- a waste gas or purge stream 815 can also be removed from the CO 2 separation unit.
- the OCM product stream 813 can then be separated in a separations unit 803 into a product stream 816 comprising ethylene and a purge and/or recycle stream 817 . Separation methods can include low temperature separation, membrane separation, or other separation methods discussed herein.
- the OCM loop can be decreased to just a CO 2 recycle stream.
- the system can also comprise a methanation unit (not shown).
- Waste heat from the OCM process can be used to generate superheated high pressure steam that can be used in the process, exported to other users on site, or can be used to generate power. Excess process heat can also be used to preheat the feed streams. Other uses for excess heat can be less capital intensive, and offer a greater operational flexibility and low maintenance. Thermoelectric energy conversion can be used to convert waste heat to power.
- Example uses for waste heat include single fluid rankine cycles (e.g., steam cycle, hydrocarbons, and ammonia), binary/mixed fluid cycles (e.g., ammonia/water or mixed hydrocarbon cycle).
- the organic Rankine cycle can be used to generate power from heat.
- ORC organic Rankine cycle
- an organic component is used instead of water.
- the organic compound can be a refrigerant, a hydrocarbon (e.g., butane, pentane, hexane), silicon oil, or a perfluorocarbon.
- the boiling point of the organic fluid can be lower than that of water, which can allow recovering heat at a lower temperature than in the traditional steam Rankine cycle.
- the ORC system can be deployed as a waste heat recovery method for use with OCM. Waste heat at relatively low temperature can be recovered by an intermediate heat transfer loop and used to evaporate the working fluid of the ORC.
- FIG. 9 shows an exemplary OCM system with an ORC subsystem.
- the working fluid can be chosen which can be condensed with cooling water or air at normal atmospheric pressure.
- FIG. 9 shows the heat source as the OCM reaction heat from an OCM unit 901 .
- Heat can be recovered from the OCM product stream 910 in an evaporator 902 , and the product stream 911 can then be directed for downstream processing from the OCM unit.
- the heat recovered in the evaporator can be used to evaporate a working fluid stream 912 , which can then be directed to a turbine 903 to generate power in a generator 904 .
- the working fluid 913 can be directed to a condenser 905 and cooled using a cooling medium 914 .
- the cooled working fluid 915 can then be pumped by a pump 906 in a stream 916 back to the evaporator.
- the OCM process can make use of a heat exchanger with thermoelectric (TE) generators for heat recovery.
- TE thermoelectric
- a Thermoelectric Power Generator (TPG) can have four basic components: Heat source, P and N type semiconductor stack (or a TE module), heat sink (cold side), and an electrical load (output voltage).
- the TE module can include two or more of P-type and N-type semiconductor pellets connected in series or parallel depending on the served load.
- the TE devices can be solid state engines that do not require any working fluid.
- Thermoelectric materials can provide efficiencies of up to 15% or greater.
- Thermoelectric generators coupled with heat exchangers can produce electricity even at temperatures as low as 350 K with low maintenance.
- TE modules can be used with OCM including large bulk TE modules and thin film or micro TE modules.
- micro TE modules can be used for high temperatures. Micro TE modules can also have low equipment weights. TE devices can be very reliable, scalable, and modular. Some TE modules can give best results at small scales.
- the OCM process can generate medium level waste heat that is highly suitable for a TE device to generate power.
- PSA technology can be applied to processes including those involving a hydrocarbon stream containing a mix of the following hydrogen, carbon dioxide, carbon monoxide, methane, ethane, ethylene, propane, propylene, butanes, butenes and/or other higher hydrocarbons needing to be purified or separated into desirable products (e.g., ethylene, methane, hydrogen, or propylene).
- Hydrocarbon streams can be produced via traditional refining and petrochemical processes. Hydrocarbon streams can be produced from OCM or ETL reactor systems.
- the present disclosure provides the use of PSA in processes and systems for oxidative coupling of methane (OCM) and ethylene-to-liquids (ETL) operations, and the application of adsorbent based processes used in conjunction with OCM and ETL processes to generate significant process improvements and enhance the economic value of the processes.
- OCM systems are described in, for example, U.S. patent application Ser. No. 14/592,668, which is entirely incorporated herein by reference.
- ETL systems are described in, for example, U.S. patent application Ser. No. 14/591,850, which is entirely incorporated herein by reference.
- An OCM system can include an OCM or OCM-post-bed-cracking (PBC) reactor 1002 , a process gas compression system 1003 , a process gas treatment system 1004 , a cryogenic separations system, and a methanation system 1001 .
- the feed to the OCM system can be an oxygen feed 1012 and a methane source feed 1011 (such as a natural gas feed stream or other methane source).
- a methane source feed 1011 such as a natural gas feed stream or other methane source.
- additional ethane feed can be supplied to the PBC section of the OCM reactor, where paraffins such as ethane in the OCM product stream and/or additional ethane can be cracked to olefins such as ethylene.
- the separations sub-system can comprise a series of fractionation towers, like a demethanizer 1005 , deethanizer 1006 , C 2 splitter 1007 , depropanizer 1008 , debutanizer, and others.
- Overhead 1013 from the demethanizer can be directed into the methanation system along with hydrogen or natural gas 1010 to produce additional methane.
- the bottoms stream 1014 from the demethanizer can be directed to the deethanizer.
- the overhead stream 1015 from the deethanizer can be directed to the C 2 splitter, and there split into ethylene 1016 and ethane 1017 streams.
- the bottoms stream 1018 from the deethanizer can be directed to the depropanizer, and there split into a C 3 product stream 1019 and a C 4+ product stream 1020 .
- the cryogenic separations system can comprise additional ethylene and propylene refrigeration sub-systems to provide for the chilling requirements of the system.
- the separations section of the OCM system can be eliminated, or partially eliminated, by utilizing an advanced separations method as discussed in this application.
- the advanced separation method can be a PSA unit or a membrane based method, or a cryogenic system.
- FIG. 11 shows an exemplary schematic of OCM with a PSA unit.
- the PSA unit can separate methane, CO 2 , CO, and/or H 2 from ethane, ethylene, propane, propylene, and/or higher hydrocarbons.
- Methane 1111 and oxygen 1112 can be directed into an OCM reactor 1102 and reacted to produce higher hydrocarbon products including ethylene.
- the OCM product can be compressed in a process gas compression system 1103 , treated in a process gas treatment system 1104 , and separated in the PSA 1105 into a product stream 1113 and a recycle stream 1114 .
- the recycle stream can be directed to a methanation unit 1101 , which can also receive a natural gas stream 1110 and produce methane for the OCM reactor.
- the extent of separation and degree of recovery can depend on the type of adsorbent(s), pressure differential, and number of PSA stages employed.
- the feed to the PSA unit can have one or more of the following components: H 2 , N 2 , O 2 , CO, CO 2 , CH 4 , ethane, ethylene, acetylene, propane, propylene, butanes, butenes, butadiene, water, and higher paraffinic and olefinic components.
- the PSA product gas can comprise components including but not limited to: H 2 , N 2 , CO, CO 2 , CH 4 , O 2 , ethane, ethylene and acetylene.
- PSA product gas can comprise components from 0% to 99.99% recovery.
- the PSA tail gas can comprise 99.99%, 90%, 80%, 70%, 60%, 50% ethylene.
- the PSA tail gas can comprise at least 99.99%, 90%, 80%, 70%, 60%, 50% ethylene.
- the PSA tail gas can comprise about 99%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, 0% ethane.
- the PSA tail gas can comprise at least about 99%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, 0% ethane.
- the PSA tail gas can comprise about 60%, 50%, 40%, 30%, 20%, 10%, 0% methane, hydrogen, acetylene, N 2 , O 2 , H 2 O or CO 2 .
- the PSA tail gas can comprise at least about 60%, 50%, 40%, 30%, 20%, 10%, 0% methane, hydrogen, acetylene, N 2 , O 2 , H 2 O or CO 2 . Based on the process configuration, including the type of adsorbents employed, pressure differential and the operation, various different recoveries are possible.
- the PSA unit can comprise one or more adsorbent materials that can be suitable to achieve the component recoveries.
- the sorbent can be a zeolite/molecular sieve based material, a carbon based sorbent, or a ⁇ -complexation sorbent.
- the sorbent material can be a polymeric resin, carbon nanotubes, and carbon fibers.
- the PSA unit can be configured to have layers of different sorbents so as to result in high recoveries from the multi-component feed streams to the desired products.
- the PSA can be a multi stage unit (see, e.g., FIG. 12 ).
- an OCM reactor 1202 can receive a methane stream 1211 and an oxygen stream 1212 , and react the methane and oxygen to produce higher hydrocarbon products including ethylene in an OCM product stream.
- the OCM product stream can be compressed in a first compressor 1203 and directed to a first PSA separation 1204 .
- the tail gas 1214 from the first PSA can be compressed in a second compressor 1205 and fed to a second PSA separation 1206 , the tail gas 1216 from which can be compressed in a third compressor 1207 and separated in a third PSA separation 1208 .
- the tail gas from the third PSA can be the final purified stream 1217 containing ethylene up to 99.9% purity.
- PSA product streams 1213 , 1215 , and 1218 can be directed to recycle, such as via a methanation unit 1201 along with a natural gas stream 1210 .
- Each PSA stage can be a dual-bed PSA or a multi-bed PSA system.
- the process requirements can dictate that only a limited amount of recovery is required in the PSA unit and subsequent recovery and purification is performed in a fractionation column or the gas is a feed for a downstream process unit.
- the downstream process unit can be an ETL system, an ethylene steam cracker system, a gas processing plant, NGL extraction plant, a refinery off-gas separations system, or other process unit.
- OCM can be employed to convert a feedstock comprising methane to ethylene and other olefins.
- ethylene has been produced via steam cracking of gaseous or liquid hydrocarbon feedstocks like ethane, propane, LPG, or naphtha.
- a steam cracking operation can involve a cryogenic fractionation or a separations section that consists of a series of fractionation columns to successively recover various components at high product purity.
- the present disclosure includes the application of PSA processes to an OCM retrofit of an existing ethylene cracker (e.g., steam cracker).
- an existing ethylene cracker e.g., steam cracker
- An example application for OCM combined with a PSA unit involves an existing petrochemical plant such as a steam cracker is considering low cost ways to add ethylene capacity.
- a typical revamp to add capacity could include addition of, or debottlenecking of, the existing fractionation towers for the entire flow addition for the revamp.
- FIG. 13 the use of a PSA unit as disclosed herein can provide a low cost alternative to traditional revamps.
- An OCM unit with a PSA unit retrofitted to an existing steam cracker can be an effective way of adding ethylene capacity at a low marginal cost.
- the advantages of adding a PSA unit include that no additional cryogenic separation is required for the added capacity.
- one of the key areas during debottlenecking may be the refrigeration systems and/or the fractionation columns, but utilizing the PSA to separate or pre-separate the additional product stream can result in a simpler and easier debottlenecking.
- the tail gas from the PSA can be sent to the cracker system where the ethylene is recovered.
- FIG. 13 shows an example of an OCM process integrated with an existing ethylene cracker using a PSA system for separations.
- the OCM reactor 1301 takes in methane 1310 and oxygen 1311 and produces an OCM effluent 1312 having CO 2 , CH 4 and C 2 H 4 , in some cases amongst other components, such as H 2 and CO.
- the OCM reaction can be exothermic and can produce steam 1313 .
- the OCM effluent can be compressed in a compressor 1302 and optionally treated in an acid gas removal system 1303 , and fed into a pressure swing adsorption (PSA) unit 1304 .
- PSA pressure swing adsorption
- the acid gas removal system may have an additional knock out drum to condense and separate any condensates and water.
- the PSA unit can produce a product stream that can include H 2 , CH 4 , ethane, CO 2 and CO.
- the overhead stream 1315 can be fed into a methanation subsystem 1305 (e.g., methanation reactor) to provide methane for the OCM reactor, and some of the overhead stream can be purged 1316 to a fuel gas system, for example. Additional methane can be provided by way of a natural gas stream or other methane stream.
- the PSA tail gas 1317 can comprise most of the ethylene, the content of which may range from 50% to 99.9% depending on the process configuration and operation of the PSA system.
- the PSA tail gas can also comprise H 2 , CO, CO 2 , CH 4 , ethane, propane, propylene, butanes, butenes, and other components.
- the process of FIG. 13 can further include an existing ethylene cracker 1306 .
- the PSA tail gas can be fractionated using existing separations capacity in the ethylene cracker.
- the heavy components can be processed in the fractionation towers of the ethylene cracker, optionally first being compressed in the existing process gas compressor of the ethylene cracker. In some cases, the heavy components stream can be routed to the CO 2 removal unit of the existing ethylene cracker subsystem to meet the CO 2 specification.
- the OCM reactor can receive a C 2 recycle stream 1319 from the cracker complex.
- the combination of a new OCM unit and an existing ethylene cracker can provide synergistic benefits. It can provide for a low cost alternative to add ethylene capacity to the existing cracker.
- the entire overhead from the existing demethanizer is used as fuel gas, and can now be available as one of the feeds to the methanation unit.
- the demethanizer overhead off-gas comprises up to 95% methane, which can be converted to ethylene in the OCM reactor, hence increasing the total ethylene capacity.
- the hydrogen content in the existing demethanizer overhead is substantial, and may be enough to meet the hydrogen requirement of the methanation unit.
- retrofitting an ethylene cracker with OCM reduces (or allows for reduction of) the severity of cracking in the existing cracker, enabling value addition by increasing the production of pyrolysis gasoline components in the cracker effluent, as the OCM reactor produces the ethylene that may be needed to achieve the total system capacity.
- the cracker can then be operated on high propylene mode to produce more propylene and at the same time meeting the ethylene production rate by the new OCM unit.
- This retrofit can result in greater flexibility for the ethylene producer with respect to the existing cracker operation.
- the overall carbon efficiency can be increased as the methane and hydrogen from the existing demethanizer off-gases can be utilized to convert the carbon dioxide and carbon monoxide to methane, which is fed to the OCM reactor.
- ethane and/or propane recycle streams from the existing cracker can be routed to the OCM unit (e.g., instead of the cracking furnaces). These recycle streams are typically routed to the cracking furnaces where they are cracked to extinction. This can provide an advantage over routing the recycle streams to OCM over the cracking furnace, such as higher selectivity to ethylene in the OCM process.
- An OCM reactor 1402 can receive a methane stream 1410 and an oxygen stream 1411 , and react the methane and oxygen to produce higher hydrocarbon products including ethylene in an OCM product stream.
- the OCM product stream can be compressed in a first compressor 1403 and directed to a first PSA separation 1404 .
- the tail gas 1412 from the first PSA can be compressed in a second compressor 1405 and fed to a second PSA separation 1406 , the tail gas 1414 from which can be compressed in a third compressor 1407 and separated in a third PSA separation 1408 .
- the tail gas from the third PSA can be the final purified stream 1417 can be directed to a cracker unit, such as an existing cracker unit, where it can be processed and separated into an ethylene product stream 1418 , a propylene product stream 1419 , and an additional product stream 1420 .
- PSA product streams 1413 , 1415 , and 1416 can be directed to recycle, such as via a methanation unit 1401 , along with a demethanizer off gas stream 1421 from the cracker unit.
- Each PSA stage can be a dual-bed PSA or a multi-bed PSA system.
- FIG. 15 shows various exemplary configurations for an OCM-ETL process.
- FIG. 15 shows a stand alone skimmer configuration, where a methane stream 1505 can be directed into an OCM reactor 1501 with an oxygen feed 1506 and optionally an ethane feed 1507 .
- the OCM reactor product stream can be directed into a compressor 1502 and then into an ETL reactor 1503 .
- the ETL product stream can be directed into a gas separations unit 1504 , where it can be separated into a C 2+ product stream 1508 , a C 5+ product stream 1509 , and an overhead stream 1510 comprising methane which can be returned to a pipeline, sold to a consumer, or otherwise used.
- FIG. 15 shows a stand alone skimmer configuration, where a methane stream 1505 can be directed into an OCM reactor 1501 with an oxygen feed 1506 and optionally an ethane feed 1507 .
- the OCM reactor product stream can be directed into a compressor 1502 and then into an
- a methane feed stream 1518 (e.g., from a natural gas pipeline) is directed into a treatment unit 1511 and then into a separations system (e.g., cryogenic) 1512 .
- a methane feed stream 1519 can be directed to an OCM reactor 1513 , while another methane stream 1520 can be purged or used for power generation.
- a C 2+ stream 1521 can also be recovered from the separations system.
- An oxygen feed stream 1522 and optionally an ethane stream 1523 can also be directed into the OCM reactor, and the reactor can produce an OCM product stream.
- the OCM product stream can be directed into a compressor 1514 and then into an ETL reactor 1515 .
- the ETL product stream can be processed in a knockout drum 1516 or other separator to remove a C 5+ product stream 1524 .
- the remaining ETL product stream can be directed to a compressor 1517 and recycled to the treatment unit.
- FIG. 15 shows a hosted skimmer configuration, where a methane stream 1532 can be directed from a separations system 1526 (e.g., cryogenic) into an OCM reactor 1527 with an oxygen feed 1533 and optionally an ethane feed 1534 .
- the OCM reactor product stream can be directed into a compressor 1528 and then into an ETL reactor 1529 .
- the ETL product stream can be directed into a gas separations unit 1530 , where it can be separated into a C 2+ product stream 1535 , a C 5+ product stream 1536 , and an overhead stream 1537 comprising methane which can be returned to a recompressor 1531 .
- FIG. 15 shows a hosted recycle configuration, where a methane stream is directed into a treatment unit 1538 and then into a separations system (e.g., cryogenic) 1539 .
- a methane feed stream 1546 can be directed to an OCM reactor 1541 , while another methane stream can be directed to a recompressor 1540 .
- a C 2+ stream 1551 can also be recovered from the separations system.
- An oxygen feed stream 1547 and optionally an ethane stream 1548 can also be directed into the OCM reactor, and the reactor can produce an OCM product stream.
- the OCM product stream can be directed into a compressor 1542 and then into an ETL reactor 1543 .
- the ETL product stream can be processed in a knockout drum 1544 or other separator to remove a C 5+ product stream 1549 .
- the remaining ETL product stream can be directed to a compressor 1545 and recycled 1550 to the treatment unit.
- FIG. 16 shows similar configurations as FIG. 15 , with an added pressure swing adsoprtion (PSA) unit to pre-separate the OCM effluent to remove most of the methane, hydrogen, CO and CO 2 from the olefinic stream, which is then fed to the ETL reactor.
- PSA pressure swing adsoprtion
- a methane stream 1606 can be directed into an OCM reactor 1601 with an oxygen feed 1607 and optionally an ethane feed 1608 .
- the OCM reactor product stream can be directed into a compressor 1602 and then into a PSA unit 1603 .
- a light stream 1609 comprising methane, hydrogen, CO and CO 2 can be directed from the PSA back to a pipeline, sold to a consumer, or otherwise used.
- An olefinic stream can be directed from the PSA to an ETL reactor 1604 .
- the ETL product stream can be directed into a gas separations unit 1605 , where it can be separated into a C 2+ product stream 1610 , a C 5+ product stream 1611 , and an overhead stream 1612 comprising methane which can be returned to a pipeline, sold to a consumer, or otherwise used.
- FIG. 16 shows a stand alone recycle configuration, where a methane feed stream 1628 (e.g., from a natural gas pipeline) is directed into a treatment unit 1620 and then into a separations system (e.g., cryogenic) 1621 .
- a methane feed stream 1629 can be directed to an OCM reactor 1622 , while another methane stream 1630 can be purged or used for power generation.
- a C 2+ stream 1631 can also be recovered from the separations system.
- An oxygen feed stream 1632 and optionally an ethane stream 1633 can also be directed into the OCM reactor, and the reactor can produce an OCM product stream.
- the OCM product stream can be directed into a compressor 1623 , and at least a portion 1634 of the OCM product stream can be directed from the compressor into a PSA unit 1624 .
- a light stream 1635 comprising methane, hydrogen, CO and CO 2 can be directed from the PSA back to the treatment unit.
- An olefinic stream 1636 can be directed from the PSA to an ETL reactor 1625 .
- the ETL product stream can be processed in a knockout drum 1626 or other separator to remove a C 5+ product stream 1637 .
- FIG. 16 shows a hosted skimmer configuration, where a methane stream 1647 can be directed from a separations system 1640 (e.g., cryogenic) into an OCM reactor 1641 with an oxygen feed 1648 and optionally an ethane feed 1649 .
- the OCM reactor product stream can be directed into a compressor 1642 and then into and then into a PSA unit 1643 .
- a light stream 1650 comprising methane, hydrogen, CO and CO 2 can be directed from the PSA to a recompressor 1646 .
- An olefinic stream can be directed from the PSA to an ETL reactor 1644 .
- the ETL product stream can be directed into a gas separations unit 1645 , where it can be separated into a C 2+ product stream 1651 , a C 5+ product stream 1652 , and an overhead stream 1653 comprising methane which can be returned to the recompressor.
- FIG. 16 shows a hosted recycle configuration, where a methane stream is directed into a treatment unit 1660 and then into a separations system (e.g., cryogenic) 1661 .
- a methane feed stream 1669 can be directed to an OCM reactor 1663 , while another methane stream can be directed to a recompressor 1662 .
- a C 2+ stream 1677 can also be recovered from the separations system.
- An oxygen feed stream 1670 and optionally an ethane stream 1671 can also be directed into the OCM reactor, and the reactor can produce an OCM product stream.
- the OCM product stream can be directed into a compressor 1664 and at least a portion 1672 of the OCM product stream can be directed from the compressor into a PSA unit 1665 .
- a light stream 1673 comprising methane, hydrogen, CO and CO 2 can be directed from the PSA back to the treatment unit.
- An olefinic stream 1674 can be directed from the PSA to an ETL reactor 1666 .
- the ETL product stream can be processed in a knockout drum 1667 or other separator to remove a C 5+ product stream 1675 .
- the remaining ETL product stream can be directed to a compressor 1668 and recycled 1676 to the treatment unit.
- the ETL reactor can be a tubular, packed bed, moving bed, fluidized bed, or other reactor type.
- An ETL reactor can be an isothermal or adiabatic reactor.
- the ETL system can benefit from a feed concentrated in olefins.
- the ETL reactor system can use a recycle stream to control and moderate the temperature increase in the reactor bed due to the highly exothermic nature of the ETL reactions.
- ETL systems are described in, for example, U.S. patent application Ser. No. 14/591,850, which is entirely incorporated herein by reference.
- one or more of the fractionation towers can be deemed redundant if using the PSA, as an example, a demethanizer may not be required and the sales gas or purge gas to fuel can be sent from the PSA itself.
- Systems such as those of FIG. 17 , can be integrated with an existing gas processing plant where one or more of the existing subsystems can be utilized.
- the utilization may arise from the fact that the existing subsystems are no longer used, or have an additional capacity available to allow for the integration.
- FIG. 17 shows an exemplary application of an OCM-ETL system using a PSA system for pre-separations to an existing gas processing plant, where one or more existing sub systems may be utilized.
- the existing separations sub-system can be integrated with the OCM-ETL system to add value by converting natural gas to higher value liquid hydrocarbons.
- the PSA unit can be used to pre-separate the lighter components like methane, hydrogen, carbon monoxide, carbon dioxide, ethane, and other components, and the olefin rich stream can be sent to the ETL reactor that converts the olefins to higher molecular weight liquid hydrocarbons.
- a natural gas stream 1720 can be directed to a treatment unit 1701 and then into a separations system (e.g., cryogenic) 1702 . At least portion of a methane stream 1724 from the separations unit can be directed to an OCM reactor 1705 , while a portion of the methane stream can be directed to a compressor 1703 and used as sales gas 1721 or other purposes.
- a separations system e.g., cryogenic
- a higher hydrocarbon stream can be directed from the separations system to a C 2 removal unit 1704 , which can produce a natural gas liquids stream 1722 and a C 2 stream 1723 .
- the C 2 stream can be fed into the OCM reactor with the methane stream and an oxygen stream 1725 , and reacted to form higher hydrocarbon products including ethylene.
- the OCM product stream can be directed into a heat recovery system 1706 , which can generate a high pressure superheated (HPSH) steam stream 1726 .
- HPSH high pressure superheated
- the OCM product stream can then be directed to a knockout drum to recover a condensate stream 1727 .
- the OCM product stream can then be directed to a compressor 1708 , which can operate using the HPSH steam stream.
- the OCM product stream can be directed to a PSA unit 1709 .
- PSA unit From the PSA unit, light stream comprising methane, hydrogen, CO and CO 2 can be directed to a methanation unit 1710 , and an olefinic stream can be directed to an ETL reactor 1711 and reacted to form higher hydrocarbon products.
- the ETL product stream can be directed to a heat recovery unit 1712 , where boiler feed water (BFW) 1728 can be heated, at least a portion of which can be fed 1729 to the heat recovery unit 1706 .
- BFW boiler feed water
- the ETL product stream can then be directed to another knockout drum 1713 .
- the overhead stream from the knockout drum can be directed to a low temperature separations unit 1714 , while the bottoms stream from the knockout drum can be directed to a C 4 removal unit 1715 , which can produce a C 4 stream 1730 and a C 5+ stream 1731 .
- Overhead from the low temperature separations unit, as well as product from the methanation reactor, can be directed back to the compressor 1703 .
- OCM-ETL systems of the present disclosure can be integrated into and combined into conventional NGL extraction and NGL fractionation sections of a midstream gas plant. Where NGLs in the gas stream are declining (or gas is dry), the deployment of OCM-ETL can utilize an existing facility to produce additional liquid streams.
- the implementation of OCM-ETL can allow for the generation of on specification “pipeline gas.”
- the products from the facility can be suitable for use (or on specification or “spec”) as pipeline gas, gasoline product, hydrocarbon (HC) streams with high aromatic content, and mixed C 4 products.
- the PSA systems discussed above can be employed to separate, pre-separate or purify the hydrocarbon feed streams in the integrated NGL OCM-ETL system.
- FIG. 18 shows an exemplary NGL extraction facility integrated with an OCM-ETL system.
- the feed to the PSA 1802 can be the net incoming gas from the treatment system 1801 , which can treat a methane stream (e.g., natural gas) 1810 .
- the PSA system can separate the feed to the OCM reactor 1803 , which is mostly methane and lighter components with some ethane to utilize a PBC section of the OCM reactor, and the feed to the ETL reactor 1805 , which can first be processed in a natural gas liquids extraction system 1804 .
- the feed to the ETL system can be the PSA tail gas and OCM effluent comprising ethylene, propylene, ethane, propane, hydrogen, methane, and other components.
- the OCM effluent can be directly fed to the ETL reactor. In some cases the OCM effluent is hydrogenated and fed to the ETL system. In some cases, as shown for example in FIG. 18 , the OCM effluent is fed back to the PSA unit for separation; additional natural gas 1811 can be added, and a stream can be recovered 1812 (e.g., for use as pipeline gas).
- the system may have a methanation unit that takes in the effluent from ETL reactor or OCM reactor and converts the CO, CO 2 and H 2 to methane, thereby further increasing the carbon efficiency of the process.
- the existing NGL extraction and product fractionation 1806 sub-systems can then be used to fractionate the final products, including into a mixed C 4 stream 1814 and a C 5+ product stream 1815 .
- Refinery gas typically contains valuable components like hydrogen, methane, ethane, ethylene, propane, propylene, and butane.
- refinery off-gases ROG
- the OCM-ETL process can be used to improve the value of products as the OCM converts the methane to ethylene and the ETL converts olefins (e.g., those existing in the ROG and those generated by OCM) to higher value liquids as C 4 components, gasoline blends, or aromatic components.
- FIG. 19 shows an exemplary PSA unit integrated to a refinery process scheme.
- a refinery gas plant 1901 can receive gas 1910 from cracking or other units.
- the PSA unit 1903 (after, for example, treatment of the gas in a treatment unit 1902 ) can separate components in refinery gas plant off gas to methane and a C 2+ cut which contains most or all of the olefinic materials.
- the methane can be used as refinery fuel 1911 and/or directed to an OCM unit 1904 with post-bed cracking
- the OCM feed can be supplemented with additional natural gas 1912 .
- the olefinic materials can be directed to an ETL reactor 1905 .
- the OCM effluent can also be routed to the PSA where the olefins produced in the OCM are also sent to the ETL reactor.
- the OCM effluent can be routed to the ETL reactor.
- the OCM effluent may be hydrogenated before being sent to the PSA unit or ETL reactor.
- the product stream can contain methane, ethane, CO, CO 2 , and other components, with of each component from 1 to 99%.
- a C 3+ stream 1913 from the refinery gas plant can be directed to a product fractionation system 1906 , which can provide a C 2 /C 3 stream 1914 (which can be directed to the OCM reactor), an iC 4 stream 1915 , a gasoline blend stream 1916 , and/or a kerosene/jet stream 1917 .
- the system can have a methanation unit to further improve the carbon efficiency of the process.
- a refinery gas plant 2001 can receive gas 2010 from cracking or other units.
- the PSA unit 2003 (after, for example, treatment of the gas in a treatment unit 2002 ) can separate components in refinery gas plant off gas to methane and a C 2+ cut which contains most or all of the olefinic materials.
- the methane can be used as refinery fuel 2011 and/or directed to a methanation unit 2004 , and then to an OCM reactor 2005 with post-bed cracking
- the methanation feed can be supplemented with additional natural gas 2012 .
- the olefinic materials can be directed to an ETL reactor 2006 .
- the OCM effluent can be routed to the ETL reactor.
- the OCM effluent can also be routed to the PSA where the olefins produced in the OCM are also sent to the ETL reactor.
- the OCM effluent may be hydrogenated before being sent to the PSA unit or ETL reactor.
- the product stream can contain methane, ethane, CO, CO 2 , and other components, with of each component from 1 to 99%.
- a C 3+ stream 2013 from the refinery gas plant can be directed to a product fractionation system 2007 , which can provide a C 2 /C 3 stream 2014 (which can be directed to the OCM reactor), an iC 4 stream 2015 , a gasoline blend stream 2016 , and/or a kerosene/jet stream 2017 .
Abstract
The present disclosure provides a method for generating higher hydrocarbon(s) from a stream comprising compounds with two or more carbon atoms (C2+), comprising introducing methane and an oxidant (e.g., O2) into an oxidative coupling of methane (OCM) reactor that has been retrofitted into a system comprising an ethylene-to-liquids (ETL) reactor. The OCM reactor reacts the methane with the oxidant to generate a first product stream comprising the C2+ compounds. The first product stream can then be directed to a pressure swing adsorption (PSA) unit that recovers at least a portion of the C2+ compounds from the first product stream to yield a second product stream comprising the at least the portion of the C2+ compounds. The second product stream can then be directed to the ETL reactor. The higher hydrocarbon(s) can then be generated from the at least the portion of the C2+ compounds in the ETL reactor.
Description
- This application claims priority to U.S. Provisional Patent Application Ser. No. 62/141,789, filed Apr. 1, 2015, which is entirely incorporated herein by reference.
- The modern refining and petrochemical industry makes extensive use of fractionation technology to produce and separate various desirable compounds from crude oil. The conventional fractionation technology is energy intensive and costly to install and operate. Cryogenic distillation has been in use for over a hundred years to separate and recover hydrocarbon products in various refining and petrochemical industries. However, there is a need for non-cryogenic separation methods and systems, particularly for oxidative coupling of methane (OCM) processes.
- Aspects of the present disclosure provide processes for recovering olefins from a stream containing mix of hydrocarbons by utilizing techniques based the use of adsorbents. In some embodiments, systems and methods enable the separation, pre-separation, purification and/or recovery of hydrocarbons, including, but not limited to, olefins, ethylene, propylene, methane, and ethane, and CO2, from a multicomponent hydrocarbon stream such as an effluent stream from an oxidative coupling of methane (OCM) reactor or an ethylene-to-liquids (ETL) reactor. The hydrocarbon stream can also be the feed to the OCM or ETL reactor in certain cases. In certain cases, the feed to the ETL reactor is the effluent from OCM reactor. In some cases, a separation process utilizing adsorbents can be used to purify and pre-treat existing hydrocarbon streams (such as refinery off-gases, cracker off-gas, streams from NGL plants, and others), followed by use of the resulting olefin rich stream (e.g., PSA tail gas) as the ETL feed.
- The present disclosure provides various improvements in OCM and ETL processes, such as, without limitation, a separation and pre-separation process to recover desired or predetermined components from an OCM reactor effluent, CO2 recovery and capture techniques, enhanced heat recovery methods to utilize the OCM reaction heat more efficiently, and techniques and technologies to further reduce the carbon footprint of the OCM process.
- An aspect of the present disclosure provides a method for generating higher hydrocarbon(s) from a stream comprising compounds with two or more carbon atoms (C2+), comprising introducing methane and an oxidant (e.g., O2) into an oxidative coupling of methane (OCM) reactor that has been retrofitted into a system comprising an ethylene-to-liquids (ETL) reactor. The OCM reactor reacts the methane with the oxidant to generate a first product stream comprising the C2+ compounds. The first product stream can then be directed to a pressure swing adsorption (PSA) unit that recovers at least a portion of the C2+ compounds from the first product stream to yield a second product stream comprising the at least the portion of the C2+ compounds. The second product stream can then be directed to the ETL reactor. The higher hydrocarbon(s) can then be generated from the at least the portion of the C2+ compounds in the ETL reactor.
- In some cases, the first product stream is directed to other intermediate units before the PSA, such as a post-bed cracking (PBC) unit that generates alkenes from alkanes. The alkenes can be included in the first product stream, which can then be directed to the PSA.
- In an aspect, the present disclosure provides a method for generating higher hydrocarbon(s) from a stream comprising compounds with two or more carbon atoms (C2+), comprising: (a) introducing methane and an oxidant into an oxidative coupling of methane (OCM) reactor that has been retrofitted into a system comprising an ethylene-to-liquids (ETL) reactor, where the OCM reactor reacts the methane with the oxidant to generate a first product stream comprising the C2+ compounds; (b) directing the first product stream to a pressure swing adsorption (PSA) unit that recovers at least a portion of the C2+ compounds from the first product stream to yield a second product stream comprising the at least the portion of the C2+ compounds; (c) directing the second product stream to the ETL reactor; and (d) generating the higher hydrocarbon(s) from the at least the portion of the C2+ compounds in the ETL reactor.
- In some embodiments, the method further comprises: (e) recovering a light stream comprising (i) hydrogen and (ii) carbon monoxide (CO) and/or carbon dioxide (CO2) from the PSA unit and recycling the light stream to the OCM reactor; (f) directing at least a portion of the light stream into a methanation unit that reacts the hydrogen and the CO and/or CO2 to produce a methanation product stream comprising methane; and (g) directing the methanation product stream into the OCM reactor.
- In some embodiments, the method further comprises recovering C2 and/or C3 compounds from the second product stream and directing the C2 and/or C3 compounds to the OCM reactor. In some embodiments, the OCM reactor further comprises a post-bed cracking (PBC) unit.
- In another aspect, the present disclosure provides a method for generating compounds with two or more carbon atoms (C2+ compounds), comprising: (a) directing oxygen (O2) and methane (CH4) into an oxidative coupling of methane (OCM) reactor that reacts the O2 and CH4 in an OCM process to yield a product stream comprising (i) C2+ compounds including ethylene (C2H4) and (ii) carbon monoxide (CO) and/or carbon dioxide (CO2); and (b) directing the product stream from the OCM reactor into a separations system that employs a refrigeration unit having a refrigerant that includes methane from the product stream, to enrich the C2+ compounds in the product stream.
- In some embodiments, the product stream is directed into the separations system through one or more additional units.
- In some embodiments, the method further comprises separating methane from the product stream for use in the refrigeration unit. In some embodiments, the method further comprises directing CO and/or CO2 from the product stream to a methanation reactor that reacts the CO and/or CO2 to yield a methanation product stream comprising methane. In some embodiments, the method further comprises directing at least a portion of the methane in the methanation product stream to the OCM reactor. In some embodiments, the method further comprises separating the product stream into (i) an ethylene product stream comprising ethylene and (ii) a C3+ product stream comprising compounds with three or more carbon atoms (C3+ compounds). In some embodiments, the method further comprises directing ethane from the product stream to the OCM reactor. In some embodiments, the method further comprises prior to directing the product stream into the separations system, compressing the product stream.
- In another aspect, the present disclosure provides a method for generating compounds with two or more carbon atoms (C2+ compounds), comprising: (a) directing oxygen (O2) and methane (CH4) into an oxidative coupling of methane (OCM) reactor that reacts the O2 and CH4 in an OCM process to yield a product stream comprising (i) C2+ compounds including ethylene (C2H4) and (ii) carbon monoxide (CO) and/or carbon dioxide (CO2); and (b) directing the product stream from the OCM reactor into a separations system that employs a complexation unit having a complexation catalyst that forms pi complexes with the ethylene in the product stream, to enrich the C2+ compounds in the product stream.
- In some embodiments, the product stream is directed into the separations system through one or more additional units. In some embodiments, the method further comprises using the complexation unit to remove one or more impurities from the product stream, where the impurities are selected from the group consisting of CO2, sulfur compounds, acetylenes, and hydrogen. In some embodiments, the complexation catalyst includes one or more metals selected from the group consisting of silver and copper. In some embodiments, the method further comprises directing CO and/or CO2 from the product stream to a methanation reactor that reacts the CO and/or CO2 to yield a methanation product stream comprising methane. In some embodiments, the method further comprises directing the methane in the methanation product stream to the OCM reactor. In some embodiments, the method further comprises separating the product stream into (i) an ethylene product stream comprising ethylene and (ii) a C3+ product stream comprising compounds with three or more carbon atoms (C3+ compounds). In some embodiments, the method further comprises directing ethane from the product stream to the OCM reactor. In some embodiments, the method further comprises prior to directing the product stream into the separations system, compressing the product stream.
- In another aspect, the present disclosure provides a method for generating compounds with two or more carbon atoms (C2+ compounds), comprising: (a) directing oxygen (O2) and methane (CH4) into an oxidative coupling of methane (OCM) reactor that reacts the O2 and CH4 in an OCM process to yield a product stream comprising (i) C2+ compounds including ethylene (C2H4) and (ii) carbon dioxide (CO2); and (b) directing the product stream from the OCM reactor into a separations system that employs a CO2 separation unit to separate the CO2 from the product stream, to enrich the C2+ compounds in the product stream, which CO2 separation unit employs (i) sorbent or solvent separation of CO2, (ii) membrane separation of CO2, or (iii) cryogenic or low temperature separation of CO2 having an operating temperature greater than a boiling point of methane and less than a boiling point of CO2.
- In some embodiments, the product stream is directed into the separations system through one or more additional units. In some embodiments, the sorbent or solvent separation of CO2 employs an amine based absoprtion system. In some embodiments, the sorbent or solvent separation of CO2 employs a Benfield process. In some embodiments, the sorbent or solvent separation of CO2 employs diethanolamine. In some embodiments, the sorbent or solvent separation of CO2 employs glycol dimethylether. In some embodiments, the sorbent or solvent separation of CO2 employs propylene carbonate. In some embodiments, the sorbent or solvent separation of CO2 employs Sulfinol.
- In some embodiments, the sorbent or solvent separation of CO2 employs a zeolite. In some embodiments, the sorbent or solvent separation of CO2 employs active carbon. In some embodiments, the CO2 separation system comprises a membrane CO2 separation system. In some embodiments, the membrane separation of CO2 employs a polymeric membrane. In some embodiments, the membrane separation of CO2 employs a metallic membrane. In some embodiments, the membrane separation of CO2 employs a ceramic membrane. In some embodiments, the membrane separation of CO2 employs a hybrid membrane comprising a membrane supporting a solvent or sorbent. In some embodiments, the membrane separation of CO2 employs a poly ionic liquid membrane. In some embodiments, the membrane separation of CO2 employs a supported ionic liquid membrane. In some embodiments, the membrane separation of CO2 employs a polyetherimide membrane.
- In some embodiments, the method further comprises directing the CO2 from the product stream to a methanation reactor that reacts the CO2 to yield a methanation product stream comprising methane. In some embodiments, the method further comprises directing the methane in the methanation product stream to the OCM reactor. In some embodiments, the method further comprises separating the product stream into (i) an ethylene product stream comprising ethylene and (ii) a C3+ product stream comprising compounds with three or more carbon atoms (C3+ compounds). In some embodiments, the method further comprises directing ethane from the product stream to the OCM reactor. In some embodiments, the method further comprises prior to directing the product stream into the separations unit, compressing the product stream.
- In another aspect, the present disclosure provides a method for generating compounds with two or more carbon atoms (C2+ compounds), comprising: (a) directing water into an electrolysis unit that electrolyzes the water to yield oxygen (O2) and hydrogen (H2); (b) directing the O2 from the electrolysis unit and methane (CH4) into an oxidative coupling of methane (OCM) reactor that reacts the O2 and CH4 in an OCM process to yield a product stream comprising (i) C2+ compounds, including ethylene (C2H4) and (ii) carbon monoxide (CO) and/or carbon dioxide (CO2); (c) directing at least a portion of the CO and/or CO2 from the product stream and the H2 from the electrolysis unit into a methanation reactor that reacts the H2 and the CO and/or CO2 to yield CH4; and (d) directing at least a portion of the CH4 from the methanation reactor to the OCM reactor.
- In some embodiments, the electrolysis unit comprises an alkaline water electrolysis system. In some embodiments, the electrolysis unit comprises a proton exchange membrane electrolysis system. In some embodiments, the electrolysis unit comprises a steam electrolysis system.
- In another aspect, the present disclosure provides a method for generating compounds with two or more carbon atoms (C2+ compounds), comprising: (a) directing oxygen (O2) and methane (CH4) into an oxidative coupling of methane (OCM) reactor that reacts the O2 and CH4 in an OCM process to yield a product stream comprising (i) C2+ compounds including ethylene (C2H4) and (ii) carbon dioxide (CO2); (b) directing the product stream from the OCM reactor into a separations system that employs a CO2 separation unit that separates the CO2 from the product stream to enrich the C2+ compounds in the product stream; and (c) directing at least a portion of the CO2 separated in (b) to the OCM reactor.
- In some embodiments, the product stream is directed into the separations system through one or more additional units.
- In another aspect, the present disclosure provides a method for generating compounds with two or more carbon atoms (C2+ compounds), comprising: (a) directing oxygen (O2) and methane (CH4) into an oxidative coupling of methane (OCM) reactor that reacts the O2 and CH4 in an OCM process to yield a product stream comprising C2+ compounds including ethylene (C2H4) and heat; (b) using an evaporator to transfer at least a portion of the heat from the product stream to an organic working fluid in a closed fluid flow cycle as part of an organic Rankine cycle (ORC) system, to evaporate the organic working fluid, which closed fluid flow cycle includes the evaporator, a turbine, a condenser, and a pump; (c) directing the organic working fluid evaporated in (b) to the turbine to generate power; (d) directing the organic working fluid from the turbine to the condenser that condenses the organic working fluid; and (e) directing the organic working fluid condensed in (d) to the pump.
- In some embodiments, the organic working fluid is selected from the group consisting of hydrocarbons, silicon oils, and perfluorocarbons. In some embodiments, a boiling point of the organic working fluid is less than a boiling point of water.
- In another aspect, the present disclosure provides a method for generating compounds with two or more carbon atoms (C2+ compounds), comprising: (a) directing oxygen (O2) and methane (CH4) into an oxidative coupling of methane (OCM) reactor that reacts the O2 and CH4 in an OCM process to yield a product stream comprising (i) C2+ compounds including ethylene (C2H4) and heat; (b) transferring at least a portion of the heat from the product stream to a thermoelectric power generator; and (c) with the aid of the heat, using the thermoelectric power generator to generate power.
- In some embodiments, the thermoelectric generator comprises a thin film thermoelectric module. In some embodiments, the thermoelectric generator comprises a micro thermoelectric module.
- Additional aspects and advantages of the present disclosure will become readily apparent to those skilled in this art from the following detailed description, wherein only illustrative embodiments of the present disclosure are shown and described. As will be realized, the present disclosure is capable of other and different embodiments, and its several details are capable of modifications in various obvious respects, all without departing from the disclosure. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
- All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference.
- The novel features of the invention are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings or figures (also “FIG.” and “FIGs.” herein), of which:
-
FIG. 1 shows a typical oxidative coupling of methane (OCM) system with advanced separation; -
FIG. 2 shows an OCM system with auto refrigeration (e.g., methane refrigeration); -
FIG. 3 shows an exemplary OCM system with a silver complexation ethylene recovery subsystem; -
FIG. 4 shows an exemplary pressure swing adsoprtion (PSA) system; -
FIG. 5A shows a schematic of CO2 separation methods; -
FIG. 5B shows a schematic of CO2 separation methods; -
FIG. 5C shows a schematic of CO2 separation methods; -
FIG. 6 shows typical CO2 distillation system; -
FIG. 7 shows a water electrolysis sub system; -
FIG. 8 shows an OCM system with CO2 as a quench medium; -
FIG. 9 shows an organic Rankine cycle (ORC) subsystem; -
FIG. 10 shows an exemplary typical OCM system; -
FIG. 11 shows an exemplary OCM system with a single stage PSA unit; -
FIG. 12 shows an exemplary OCM system with a multi stage PSA unit; -
FIG. 13 shows an exemplary retrofit of OCM to a cracker, with a single stage PSA unit; -
FIG. 14 shows an exemplary retrofit of OCM to a cracker, with a multi stage PSA unit; -
FIG. 15 shows exemplary configurations of ethylene to liquids (ETL) systems without PSA; -
FIG. 16 shows exemplary configurations of ETL systems with PSA; -
FIG. 17 shows an exemplary PSA unit integrated with an OCM-ETL system for a midstream application; -
FIG. 18 shows an exemplary PSA unit integrated with an OCM-ETL system in a natural gas liquids (NGL) application; -
FIG. 19 shows an exemplary PSA unit integrated with an OCM-ETL system for a refining application; and -
FIG. 20 shows an exemplary alternate scheme for a PSA unit integrated with an OCM-ETL system for a refining application. - While various embodiments of the invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions may occur to those skilled in the art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described herein may be employed.
- The term “higher hydrocarbon,” as used herein, generally refers to a higher molecular weight and/or higher chain hydrocarbon. A higher hydrocarbon can have a higher molecular weight and/or carbon content that is higher or larger relative to starting material in a given process (e.g., OCM or ETL). A higher hydrocarbon can be a higher molecular weight and/or chain hydrocarbon product that is generated in an OCM or ETL process. For example, ethylene is a higher hydrocarbon product relative to methane in an OCM process. As another example, a C3+ hydrocarbon is a higher hydrocarbon relative to ethylene in an ETL process. As another example, a C5+ hydrocarbon is a higher hydrocarbon relative to ethylene in an ETL process. In some cases, a higher hydrocarbon is a higher molecular weight hydrocarbon.
- The term “OCM process,” as used herein, generally refers to a process that employs or substantially employs an oxidative coupling of methane (OCM) reaction. An OCM reaction can include the oxidation of methane to a higher hydrocarbon and water, and involves an exothermic reaction. In an OCM reaction, methane can be partially oxidized and coupled to form one or more C2+ compounds, such as ethylene. In an example, an OCM reaction is 2CH4+O2→C2H4+2H2O. An OCM reaction can yield C2+ compounds. An OCM reaction can be facilitated by a catalyst, such as a heterogeneous catalyst. Additional by-products of OCM reactions can include CO, CO2, H2, as well as hydrocarbons, such as, for example, ethane, propane, propene, butane, butene, and the like.
- The term “non-OCM process,” as used herein, generally refers to a process that does not employ or substantially employ an oxidative coupling of methane reaction. Examples of processes that may be non-OCM processes include non-OCM hydrocarbon processes, such as, for example, non-OCM processes employed in hydrocarbon processing in oil refineries, a natural gas liquids separations processes, steam cracking of ethane, steam cracking or naphtha, Fischer-Tropsch processes, and the like.
- The terms “C2+” and “C2+ compound,” as used herein, generally refer to a compound comprising two or more carbon atoms. For example, C2+ compounds include, without limitation, alkanes, alkenes, alkynes and aromatics containing two or more carbon atoms. C2+ compounds can include aldehydes, ketones, esters and carboxylic acids. Examples of C2+ compounds include ethane, ethene, acetylene, propane, propene, butane, and butene.
- The term “non-C2+ impurities,” as used herein, generally refers to material that does not include C2+ compounds. Examples of non-C2+ impurities, which may be found in certain OCM reaction product streams, include nitrogen (N2), oxygen (O2), water (H2O), argon (Ar), hydrogen (H2) carbon monoxide (CO), carbon dioxide (CO2) and methane (CH4).
- The term “small scale,” as used herein, generally refers to a system that generates less than or equal to about 250 kilotons per annum (KTA) of a given product, such as an olefin (e.g., ethylene).
- The term “world scale,” as used herein, generally refers to a system that generates greater than about 250 KTA of a given product, such as an olefin (e.g., ethylene). In some examples, a world scale olefin system generates at least about 1000, 1100, 1200, 1300, 1400, 1500, or 1600 KTA of an olefin.
- The term “item of value,” as used herein, generally refers to money, credit, a good or commodity (e.g., hydrocarbon). An item of value can be traded for another item of value.
- The term “carbon efficiency,” as used herein, generally refers to the ratio of the number of moles of carbon present in all process input streams (in some cases including all hydrocarbon feedstocks, such as, e.g., natural gas and ethane and fuel streams) to the number of moles of carbon present in all commercially (or industrially) usable or marketable products of the process. Such products can include hydrocarbons that can be employed for various downstream uses, such as petrochemical or for use as commodity chemicals. Such products can exclude CO and CO2. The products of the process can be marketable products, such as C2+ hydrocarbon products containing at least about 99% C2+ hydrocarbons and all sales gas or pipeline gas products containing at least about 90% methane. Process input streams can include input streams providing power for the operation of the process. In some cases, power for the operation of the process can be provided by heat liberated by an OCM reaction. In some cases, the systems or methods of the present disclosure have a carbon efficiency of at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, or at least about 90%. In some cases, the systems or methods of the present disclosure have a carbon efficiency of between about 50% and about 85%, between about 55% and about 80%, between about 60% and about 80%, between about 65% and about 85%, between about 65% and about 80%, or between about 70% and about 80%.
- The term “C2+ selectivity,” as used herein, generally refers to the percentage of the moles of methane that are converted into C2+ compounds.
- The term “specific oxygen consumption,” as used herein, generally refers to the mass (or weight) of oxygen consumed by a process divided by the mass of C2+ compounds produced by the process.
- The term “specific CO2 emission,” as used herein, generally refers to the mass of CO2 emitted from the process divided by the mass of C2+ compounds produced by the process.
- Various non-cryogenic separation techniques have been increasingly employed for gas separations, purifications and recovery of hydrocarbons. Membrane based processes and adsorbents have been intensively studied for large scale applications for olefins recovery. Since the development of synthetic adsorbents and pressure swing adsorption (PSA) cycles, adsorption has been playing an increasingly important role in gas separation and purification.
- PSA technology can be used in a large variety of applications: Hydrogen purification, air separation, CO2 removal, noble gases purification, methane upgrading, n-iso paraffin separation and so forth. While new applications for gas separations by adsorption are continually being developed, the most important applications have been air separation (for production of O2 and N2) and hydrogen separation (from fuel gas). Approximately 20% of O2 and N2 are currently produced by PSA. The increasing industrial applications for adsorption have stimulated a growing interest in research and new applications.
- Processes of the present disclosure can employ a variety of different separations techniques, alone or in combination. For example, OCM processes can employ amine and caustic systems for CO2 removal, molecular sieve guard beds for water removal, and cryogenic distillation or other separation techniques for recovery and purification of hydrocarbon components. Cryogenic separation can refer to separations using temperature levels below 120 K or about −153° C. Other techniques include Selexol™ and Rectisol™ processes for CO2 removal.
- OCM product effluent can comprise a mixture of hydrocarbons including but not limited to methane, ethane, ethylene, propane, propylene, butanes, butenes, and higher hydrocarbons. OCM product effluent can also comprise varying amounts of other components such as H2, N2, CO, CO2 and H2O. The product of an OCM reaction can include ethylene. The ethylene product can be polymer grade, refinery grade or chemical grade. Depending on the purity level required, different separation and/or purification techniques can be employed with the OCM process. To recover high purity ethylene, separation methods such as those discussed herein can be used to remove a wide range of components.
- Advantages of the advanced OCM processes described herein can include reducing the cost, reducing the number of unit operations (“units”) used, and hence improving the overall process for producing high purity polymer grade ethylene. Overall conversion and carbon efficiency can also be improved. The separation methods disclosed herein can also improve the overall conversion and carbon efficiency.
- The different separation and purification techniques discussed herein can be used to separate the OCM product effluent (e.g., process gas) into a plurality of streams, including but not limited to a first stream comprising methane, hydrogen, carbon monoxide and other lighter inerts and a second stream comprising ethane, ethylene, propylene, and higher hydrocarbons. Separation systems or subsystems employed can include those discussed herein, such as a cryogenic demethanizer, a membrane separation system, or a PSA based system.
- The separation techniques discussed herein can be employed to remove CO2, such as from an OCM product effluent stream. One or more separations techniques can be used to remove CO2 including but not limited to absorption, adsorption, CO2 distillation, and membrane separation. The separation technique can be non-cryogenic.
-
FIG. 1 shows a block flow diagram for an exemplary OCM process.Oxygen 110 andmethane 121 can be fed into anOCM reactor 101 for conversion into higher hydrocarbon compounds including ethylene. TheOCM product stream 111 can be directed to acompressor 102, and thecompressed product stream 112 can be fed into aseparations system 103. The separations system can includepretreatment units 104, such as impurity and CO2 removal units, as well asseparations units 105, such as cryogenic, non-cryogenic, complexation, membrane, and other separations units. The separations system can be a combination of more than one separation techniques, such as those discussed in this application. The separation system can replace CO2 removal, moisture removal, and cryogenic separation systems of existing OCM process systems. The compressor system may not be required for some types of separation processes. From the separations system, CO2 can be vented 113,ethane 114 can be recovered, for example for recycling to the OCM reactor,ethylene product 115 can be recovered, and C3+ products 116 can be recovered. Additionally,CO 2 117 andmethane 118 can be directed from the separations system into amethanation unit 106. The methanation unit can produce methane from the CO2, for recycling 119 back to the OCM reactor.Additional methane 120 can be added to the OCMreactor supply stream 121. - OCM process systems can use refrigeration subsystems to condense overhead vapors, for example from a demethanizer, a deethanizer, and/or a C2 splitter. The temperatures employed can be in the range from about 12° C. to about −100° C. These low temperatures can be achieved through the use of multiple refrigeration systems, such as ethylene refrigeration and propylene refrigeration systems, to provide different levels of refrigeration. These can be similar to those employed in existing steam crackers.
- Alternatively, an open loop methane refrigeration system can be employed to provide refrigeration for a demethanizer OCM product effluent can comprise methane as the major component, for example at a concentration of at least about 50 mol %, 60 mol %, 70 mol %, 80 mol %, or 90 mol %. The demethanizer can have the lowest temperature requirements in the entire separations unit. Use of methane refrigeration (e.g., auto-refrigeration) can provide benefits such as elimination of the need for an additional refrigeration system (e.g., new) for any added capacity. For grassroots or greenfield OCM applications, this can considerably reduce refrigeration compressor sizes needed. In some cases, an entire refrigeration system can be eliminated.
FIG. 2 shows a block flow diagram for an exemplary open loop methane refrigeration system, such as can be used in gas processing plants and steam crackers to produce chilling for condensing overhead vapors from a demethanizer Most elements ofFIG. 2 correspond to the description inFIG. 1 ; theseparations unit 205 can include an open loop methane refrigeration system to provide cooling for the separations. The system can be combined with a single or multiple stage (e.g., two-stage) expansion system (e.g., Joule Thompson) to chill the incoming feed. In certain cases, multiple separate lighter products are recovered, such as a light H2-rich stream, a low pressure methane rich stream, and a high pressure methane rich stream. - Another alternative to ethylene and propylene refrigeration subsystems is the use of a mixed refrigeration system. The mixed refrigerant can be, for example, a mix of methane, ethylene and propylene. The mixed refrigerant can be a mix of ethane and propane. A wide range of possible mixed refrigerants can be employed, and can be selected based on, for example, the availability of certain components and the degree of refrigeration required. A mixed refrigerant system can provide advantages for use with an OCM reactor system, including the use of only one refrigeration sub system. Rather than two refrigeration systems each comprising multiple stages of refrigerant compressor, associated vessels, exchangers, and other components, the process can use a single refrigeration system. This can substantially reduce capital cost. This can also reduce equipment count, which can be a benefit especially for OCM retrofits at places where plot space may be a concern.
- Pi complexation techniques can be used to separate alkenes from alkanes. Some metal ions complex selectively with unsaturated organic compounds. Some of these complexes are reversible while others are irreversible. For example, aqueous silver salt in solution forms reversible complexes with olefins, and forms irreversible complexes with acetylenes. This property can be employed in an OCM process to recover ethylene and propylene from OCM reactor effluent.
- As shown in
FIG. 3 , separation of ethylene and/or propylene by metal complexation can be divided into three major sections: absorption, purification or venting of impurities, and desorption. An exemplary process is provided for separation of ethylene and/or propylene from a purified multi-component gas stream from the OCM reactor.FIG. 3 shows a process for purifying a stream containing ethylene using an aqueous silver nitrate solution. Metal complexation (e.g., silver or cuprous ion complexation) can be used to separate ethylene and/or propylene from a purified multi-component gas stream produced via OCM comprising C2 compounds, C3 compounds, and lighter components such as hydrogen and nitrogen. First, themulti-component gas stream 310 can be introduced into anabsorber 301 with aqueous silver salt solution, such that the ethylene and/or propylene undergo absorption or complexing with the silver metal ions, and such that trace acetylenes react with the silver metal ions.Vent gas 311 can be removed from the absorber. Then, the silversalt solution stream 312 can be vented 313 in avent column 302 at reduced pressure to remove any dissolved low molecular weight components. Then, the resulting silver salt solution stream can be treated in astripper 303 to separate the absorbed or complexed ethylene and/or propylene from the silver salt solution, and further treated in atreatment unit 304 to release the trace acetylenes.Purified ethylene 316 can be recovered, and some product can be recycled 317. The aqueoussilver salt stream 318 can then be recycled to the first step, in some cases after regeneration in aregeneration unit 305 withAgMnO 4 320.MnO 2 321 can be removed from the regeneration unit. H2O2 319 can be added to the solvent stream being returned to the absorber. - Useful adsorbents include but are not limited to metal compounds, such as silver or copper, supported on high surface area carriers with a plurality of pores. These adsorbents can be used in pressure swing adsorption or temperature swing adsorption processes. When operating pressure and/or temperature is changed, the silver or copper compound can release the alkene-rich component from the adsorbent. These adsorbents can be very effective for selective adsorption of alkenes such as ethylene, propylene, and mixtures of these from gaseous mixtures.
- When a gaseous component solubilizes in a liquid and complexes with its ions, the loading of the gas can be affected by its partial pressure and the temperature and the concentration of the complexing ions in the solution. Therefore, by changing the physical conditions separately or collectively, the active gaseous component can either be formed into or out of the solution. Adjusting or swinging one or more physical parameters can be used to carry out an ethylene or propylene separation using an aqueous silver nitrate solution. Purification or venting of impurities can result in a product stream that is free or substantially free of impurities including but not limited to CO2, sulfur compounds, acetylenes, and hydrogen. Acetylene and hydrogen can cause operational problems and so the process gas can be treated to bring the concentration of such impurities to within an acceptable limit.
- Metal complexation can be used in combination with other processes, such as membrane based processes.
- Membranes can be used to perform a variety of separations, such as separations of olefins and paraffins, or separations of CO2. A membrane can be essentially a barrier that separates two phases and restricts transport of various chemicals in a selective manner. Polymer membranes can be used to separate mixtures such as propylene/propane mixtures and ethylene/butene mixtures. Separations in polymeric membranes are dependent on the solubility and diffusion of the species through the membrane. While zeolite-based separations are predominantly depended on molecular size differences, the differing permeation of olefins through a polymeric membrane can be largely attributed to differences in solubility, which can depend on the critical temperature and the kinetic diameter. Membrane separations can be employed even when there are small molecular size differences.
- The OCM process can utilize a membrane based separation process to further enhance the efficiency and energy consumption of the process. Cryogenic distillation can be used for the separation of alkenes, but is highly energy intensive. Membrane based separations can be used for a variety of purposes in the context of an OCM process, such as to separate and purify ethylene product from OCM reactor effluent, to separate a stream rich in CO2, to separate a stream containing lighter hydrocarbons and inerts, or to separate C2 compounds from C1 and lighter compounds.
- Membranes can include but are not limited to isotropic membranes, anisotropic membranes, and electrically charged membranes. A membrane can be a ceramic membrane, a metal membrane, or a liquid membrane. An isotropic membrane can be a microporous membrane or a non-porous dense membrane. Membranes can be used for separations including but not limited to CO2 separation, paraffin-olefin separation, or selective recovery of pure ethylene from the OCM reactor effluent. Polymer derived carbon molecular sieve membranes can be used to separate paraffins from olefins. These membranes can be used, for example, to separate ethylene from a mix of methane and ethane.
- Membrane separations can be used in combination with other types of separation and purification subsystems to remove other impurities such as acid gases, hydrogen, and nitrogen.
- Transport through a membrane can take place when a driving force is applied to the components in the feed. A driving force can be a pressure differential or a concentration (activity) gradient across the membrane. Membrane based separation techniques can be used in an OCM process by applying either of the above mentioned driving forces. A membrane based separation can also be a component of a hybrid separation set-up, such as a membrane and an absorption system (e.g., a membrane contactor) or a membrane in a pressure swing adsorption (PSA) or a temperature swing adsorption (TSA) system.
- An OCM reactor can employ membranes as a part of the reactor system to effectively separate the ethylene product within the reactor system itself. A section of the reactor can include membranes that aid in recovering the ethylene product, with a methane rich stream being recycled to a methanation system and eventually to the OCM reactor. Such a system can also use advanced heat recovery or quench methods so as to facilitate the use of membranes.
- Cryogenic separation (e.g., distillation) can be used for the recovery of ethylene, propylene, and other components from olefin plants, refinery gas streams, and other sources. These separations can be difficult to accomplish because of the close relative volatilities, and can have significant temperature and pressure requirements for operation. The ethane/ethylene distillation can be performed at about −25° C. and 320 pounds per square inch gauge (psig) in a column containing over 100 trays. Distillation of propane and propylene can be performed at about −30° C. and 30 psig. These can be some of the most energy intensive distillations in the chemical and petrochemical industry. In general, the use of distillation towers to separate recover and purify components is an energy intensive process.
- The present disclosure provides the use of adsorbents that can achieve separation and purification of olefin rich streams. In particular, the present disclosure applies the use of PSA-based adsorbent systems to separate, purify, and recover olefins like ethylene and propylene from streams containing one or more impurities such as methane, hydrogen, carbon monoxide, carbon dioxide, ethane, or others. The streams, or parts of the streams, can be generated via an OCM process, an ETL process, or combinations thereof. The streams can be final product streams where PSA is used to recover and purify the final product. The streams can be intermediate streams which are purified prior to use as a feed in a subsequent process, such as an ETL process, an ethylene cracker (steam cracker), a refining unit, a fuel gas system, a natural gas recovery plant or any other product fractionation or product treatment unit.
- A pressure swing adsorption (PSA) process cycle is one in which desorption takes place at a different (e.g., lower) pressure than the adsorption pressure. Reduction of pressure can be used to shift the adsorption equilibrium and affect regeneration of the adsorbent. Low pressure may not be as effective as temperature elevation in totally reversing adsorption, unless very high feed to purge pressure ratios are applied. Therefore, most PSA cycles are characterized by high residual loadings and thus low operating loadings. These low capacities at high concentration require that cycle times be short for reasonably sized beds (e.g., seconds to minutes). These short cycle times are attainable because particles of adsorbent respond quickly to changes in pressure. Major uses for PSA processes include purification as well as applications where contaminants are present at high concentrations.
- As shown in
FIG. 4 , the PSA system can comprise two fixedbed adsorbers feed 410 and produce aproduct stream 411, with a PSA offgas stream 412. For improving the performance of the basic Skarstrom™ cycle (FIG. 4 ), additional operation steps can be employed such as pressure equalization, product pressurization, and co-current depressurization. Besides these steps, the number of beds can be modified to achieve the optimal operation and multi-bed processes can be used in commercial applications like hydrogen recovery. Similarly, a TSA system can be used where a swing in temperature causes the sorption and desorption. - PSA cycles are used primarily for purification of wet gases and of hydrogen. High pressure hydrogen employed in processes such as hydrogenation, hydrocracking, and ammonia and methanol production can be produced by PSA beds compounded of activated carbon, zeolites and carbon molecular sieves. Other exemplary applications include: air separation, methane enrichment, iso/normal separations, and recovery of CO and CO2.
- Adsorbents can be natural or synthetic materials, such as those having amorphous or microcrystalline structure. Exemplary adsorbents useful for large scale operation include but are not limited to activated carbon, molecular sieves, silica gels, and activated alumina. Other useful adsorbents include pi complexation sorbents, silver and copper complexation adsorbents, zeolites, synthetic zeolites, mesoporous materials, activated carbons, high surface area coordination polymers, molecular sieves, carbon molecular sieves (CMS), silica gels, MCM, activated alumina, carbon nanotubes, pillared clays, and polymeric resins.
- For systems where the incoming stream is a multi-component mixture of gases and the number of compounds to be separated cannot be removed by a single adsorbent, different layers of adsorbents can be used. For example, hydrogen purification from a methane stream in a reforming operation, where H2 is contaminated with H2O, CO2, CO, and unconverted CH4, can employ activated carbon to remove H2O and CO2 in combination with additional layers of different adsorbents used to increase the loading of CO.
- Zeolites, molecular sieves, and carbon molecular sieves (CMS) can be used for most industrial separations employing PSA. Inorganic materials, like special kinds of titanosilicates, can be used for kinetic separations.
- For systems specifically configured to separate ethane/ethylene and propane/propylene, exemplary types of adsorbents include zeolites/molecular sieves and pi complexation sorbents. Zeolites/molecular sieves can be used for kinetic separation, such as separation based on higher diffusivity of olefins over that of paraffins. The use of 4 A zeolite is one such example. Pi complexation sorbents, such as AgNO3/SiO2, can give excellent results as compared to 4 A zeolite. PSA units as discussed herein can employ a range of different sorbents, including but not limited to a zeolite/molecular sieve sorbent, a pi complexation based sorbent, a carbon molecular sieve sorbent or any other form of activated carbon, carbon nanotubes, polymeric resin based sorbents, or other sorbents.
- Adsorbents can be selected based on a number of different criteria. Adsorbent selection criteria can include capacity for the target components (e.g., affinity for the desired components to be separated from the multi-component feed stream), selectivity between components competing for same adsorption sites, regenerability of the adsorbent, (e.g., the ability of the adsorbent to release the adsorbed target components at a reasonable pressure rate of gas diffusion into the adsorbent—this can also affect the size of the bead that is chosen and consequently the pressure drop across the bed; an insufficient diffusion rate can require smaller diameter beads that can result in higher pressure drop and hence increased operating costs), and chemical compatibility (e.g., selecting an adsorbent resistant to chemical attack that may poison or destroy the adsorbent, such as liquid hydrocarbons causing physical breakdown of the adsorbent resulting in loss of efficiency and back pressure).
- There are many technologies available for CO2 capture, such as from flue gases, natural gas, or from any process gas rich in CO2. Various processes for post-combustion or pre-combustion capture can be used reduce CO2 emissions.
FIG. 5A ,FIG. 5B , andFIG. 5C show exemplary schematics of different separation methods available to separate CO2 from a process gas or a flue gas. - OCM processes can utilize an amine based absorption system for CO2 removal, which can be followed by use of a caustic scrubber to obtain high degree of separation. The amine system is prone to corrosion, solvent degradation, and above all, has high energy requirements. Separations with sorbents and/or solvents can involve placing the CO2 containing gas in intimate contact with a liquid absorbent or a solid sorbent that is capable of capturing the CO2. As shown in
FIG. 5A , a stream withCO 2 510 can be directed into acapture vessel 501, where it contacts sorbent which captures CO2 from the stream. The stream, with reduced or removed CO2, can then exit 511 the vessel.Sorbent 512 loaded with captured CO2 can be transferred to asorbent regeneration vessel 502 where it releases the CO2 after being heated (e.g., with the use of energy 513), after a pressure decrease, or after any other change in the conditions around the sorbent, thereby regenerating the sorbent. Spent sorbent 515 andCO 2 516 can be removed from the vessel, and make upsorbent 513 can be added. After the regeneration step the sorbent can be sent back to capture more CO2 in a cyclic process. The sorbent can be a solid. Solid sorbent can remain in a single vessel rather than being cycled between vessels; sorption and regeneration can be achieved by cyclic changes (e.g., in pressure or temperature) in the vessel where the sorbent is contained. A make-up flow of fresh sorbent can be used to compensate for natural loss of activity and/or sorbent losses. - Amine scrubbing technology can be used to remove acid gases from process gases. Primary amines (e.g., MEA, DGA), secondary amines (e.g., DEA, DIPA), tertiary (e.g., MDEA, TEA), sterically hindered amines, chilled ammonia, potassium carbonate, and other compounds can be used to remove CO2 from process gases. Traditional amine based systems can be characterized by high energy requirements and solvent degradation. Improved solvents, which can require less energy for regeneration of the solution, include the Benfield process and two stage diethanolamine. Combination with an OCM process can reduce the energy consumption of amine scrubbing processes. Improved solvents can reduce the energy requirements by as much as 40% compared to the traditional MEA solvents. This has the potential of reducing the energy, and hence steam, consumption of the OCM process, thereby increasing the amount of steam available for export from the OCM, or making alternative waste heat recovery methods feasible.
- Physical absorption solvents used can include but are not limited to glycol dimethylethers (e.g., Selexol) and propylene carbonate (e.g., IPTS/EC). Regeneration of the solution can be performed by vacuum flashing and air stripping; this approach can consume significantly less energy than in chemical absorption. In using physical solvents CO2 can be released mainly by depressurization, thereby avoiding the high heat of consumption of amine scrubbing processes.
- Mixed or hybrid solvents can include but are not limited to Sulfinol™ (sulfolane, water, and amine), such as Sulfinol-M and Sulfinol-X.
- Solid adsorbents, such as zeolites and activated carbon, can be used to separate CO2 from gas mixtures. In pressure swing adsorption (PSA), a gas mixture can flow through a packed bed of adsorbent at elevated pressure until the concentration of the desired gas approaches equilibrium. The bed can be regenerated by reducing the pressure. In temperature swing adsorption (TSA), the adsorbent can be regenerated by raising its temperature. In general usage, adsorption is not yet considered attractive for large scale separation of CO2 because the capacity and CO2 selectivity of available adsorbents are low. However, when the OCM process is a recycle process, an adsorbent based separation method can be used to separate bulk CO2 followed by consuming the remaining CO2 in a methanation reactor system, or by using a caustic scrubber to treat the remaining CO2.
- Many different types of membrane materials (e.g., polymeric, metallic, ceramic) can be used for CO2 capture to preferentially separate CO2 from a range of process streams.
FIG. 5B shows an exemplary schematic of separation of CO2 from agas stream 530 in aseparation vessel 520 using amembrane 521. CO2 can be removed from the stream via the membrane, and CO2 and other gases can exit the vessel inseparate streams - Membrane and amine technologies can be combined to form a hybrid process to capture CO2. Micro-porous hollow fiber membranes can be used for CO2 separation using amine-based chemical absorption processes. Micro-porous membranes can be used in a gas-liquid unit where the amine solution is contacted with CO2 containing gas. Using the membrane can lead to a reduction in the physical size and weight of the gas-liquid contacting unit. The separation is based on reversible chemical reaction, and mass transfer occurs by diffusion of the gas through the gas/liquid interface as in traditional contacting columns. Such a hybrid membrane contactor can provide a high contact area between gas and liquid, reduce or essentially eliminate foaming and flooding problems, and give better operational flexibility while reducing solvent degradation problems.
- A membrane contactor can combine the advantages of membrane technology and solvent absorption for CO2 separation. A membrane contactor is a combination of advanced membrane techniques with an effective absorption process. A membrane contactor is a hybrid mass exchanger where a porous membrane separates two phases. The selective sorbent performs the separation while the membrane facilitates the mass exchange process by expanding the phase contact surface area. The modified surface properties can improve the selectivity of the process by selectively inhibiting the transport of one of the mixture constituents. Compared to a conventional column device, membranes can allow for up to five times increase in yield per unit volume. Since the sorptive liquid flows within capillaries and both phases are not directly contacting each other, membrane absorbers can operate in any spatial configuration (horizontal or vertical) and at any flux rations between both phases. Also, there is no flooding or uneven packing moisturization. Since the system operates with unchanging yields, independent of the diameter and height; scaling up is fairly simple. Membranes used can be micromembranes or ultrafiltration membranes made a variety of different polymer and ceramic materials. Polypropylene fiber membranes can be used to separate CO2 from CH4, for example by using amines like MEA as absorption liquid. Hollow fiber membranes, such as porous polypropylene, perfluoroalkoxy (PFS), and asymmetric poly(phenylene oxide) hollow fiber membranes with a dense ultrathin skin at the outside of the membrane can also be used. Besides amines as absorption liquid, other absorption liquids may be used, such as aqueous sarcosine salt solutions, for example in a gas-liquid membrane contactor system. A membrane contactor can be used to separate the CO2 from the OCM effluent in which CH4 is the major component. Membrane contactors can also be used for separation of olefins and paraffins, and the separation of CO2 from light gases.
- An activator, such as piperazine, diethanolamine, and arsenic trioxide, can be used to further enhance the effectiveness of CO2 capture. DGA and tertiary amines may provide more improvement than primary or secondary amines.
- Gas selective poly ionic liquid membranes, which are polymerized room temperature ionic liquids (RTIL), can be used to be highly selectively separate CO2. RTILs can be synthesized as a monomer and subsequently polymerized to obtain gas selective membranes. The ionic nature of the polymers can result in tight arrangements between the oppositely charged ionic domains in the poly RTIL, which can eventually prevent the membrane from excessive swelling and deterioration of its performance at increased pressure and/or temperature. This intrinsic property of poly RTIL can be used to increase the resistance against plasticization and to restrict strong swelling of the polymer membrane to maintain its permeation properties in the presence of a strong plasticizing agent such as CO2 at higher pressures. For example, an imidazolium-based poly RTIL can be used as base material and the length of the alkyl chain can serves to strengthen or weaken the ionic interactions within the poly RTIL. High pressure mixed CO2/CH4 gas separation measurements at different temperatures.
- Gas components like CO2, from N2 or CH4 can be separated with supported ionic liquid membranes. Ionic liquids are molten salts with a very low melting point (many are liquids at room temperature). Many ionic liquids show a high solubility for carbon dioxide and hence can be highly suitable for use with an OCM process. For example, ionic liquids can include but are not limited to imidazolium, pyrollidinium, pyridinium, cuanidinium, phosphonium, morpholinium, piperidinium, sulfonium, ammonium, hexafluorophosphate, tetraflouroborate, alkylsulphate, triflate, dicyanamide, bis(trifluoromethylsulfonyl)imide, and combinations thereof. Specific advantages of ionic liquids include very low to negligible vapor pressure, good dissolution characteristics for many substances, and lack of flammability or toxicity. Ionic liquids can have good thermal, mechanical and chemical stability as well as favorable densities and viscosities. The required specifications can be adjusted easily by the large number of possible combinations of anions and cations when formulating an ionic liquid. Ionic liquids can be used as chemical solvents, catalysts, electrolytes in fuel cells as well as for gas-separation and storage by absorption. Ionic liquid membrane systems can comprise an adequate porous support material, e.g. a polymer film, coated by ionic liquids. The system separated CO2 and sulfur compounds from different gas mixtures. Competitive selectivity and permeability are obtained for the separations.
- Novel membrane materials, such as polyetherimides, can be used as membrane material with improved plasticization resistance for CO2 removal, for example with an OCM process. Other membrane materials that can be used include polymeric membranes based on polyamides, polysemicarbazides, polycarbonates, polyarylates, polyaniline, poly(phenylen oxide), polysulfones, and polypyrrolones. In some cases, the polymeric membrane is solvent resistant and can reduce the plasticization effects of hydrocarbons in the feed stream, e.g., polyketone, polyether ketone, polyarylene ether ketone, polyimide, polyetherimide, and polyphenylene sulphide, which have intrinsic solvent inertness and can therefore withstand organic rich operation conditions.
- An adequate porous support material, e.g. a polymer film, coated by ionic liquids can be used in continuous separation of CO2 and sulfur compounds from different gas mixtures, including a methane rich stream. This separation can improve the efficiency of OCM processes. The OCM reactor effluent can enter the supported ionic liquid separation subsystem, and CO2 and other contaminants can be removed from the process gas. Other contaminants can include but are not limited to traces of sulfur compounds, inerts, CO, SO2, H2S, and tetrahydrothiophene (THT).
- CO2 can be separated from other gases by cooling and condensation, for example as shown in
FIG. 5C . Astream containing CO 2 550 can be compressed in acompressor 540, and thecompressed stream 551 can be directed to adistillation column 541. Some components can be recovered from theoverhead stream 552, with heat recovered in aheat exchanger 542. Other components can be recovered from thebottoms 555. Cryogenic separation is widely used commercially for streams that already have a high concentration of CO2 (typically greater than 90%). Cryogenic separation of CO2 has the advantage that it enables direct production of high purity liquid CO2 that can be used as a feedstock to convert the carbon to higher value hydrocarbons, or otherwise be captured. The amount of energy required can be high, and water may need to be removed before the feed gas is cooled. - Low temperature distillation can give better results when there is a high concentration of CO2 in the feed gas. For the OCM process gas, the CO2 concentration can be increased by, for example, having a recycle stream, or by using a modified OCM reactor where excess CO2 is used as a quench medium for the reaction heat. Low temperature separation can refer to separations using temperature levels above −90° C.
-
FIG. 6 shows a schematic of CO2 separation using distillation.OCM reactor effluent 606 can be fed to atreatment unit 601, such as a molecular sieve dryer, a sulfur removal bed, or an acetylene removal bed. The treated gas is fed to thefirst distillation column 602 that separates the bulk of the methane from the CO2 and other heavier hydrocarbons. Depending on the CO2 concentration in thestream 606, thebottom stream 608 may contain 50%, 60%, 70%, 80%, 90% (or anywhere in between) of the incoming CO2. The overhead from 607 contains majority of the methane and other light gases and is fed to thecolumn 603.Column 603 further recovers methanerich gas 611, which can be the feed to a methanation system. Thebottoms product 616 may be recycled or sent as a purge to the fuel gas system. The CO2rich gas 608 is distilled in the CO2 column 604 to recoverpure CO 2 609 in the overhead. Thebottoms product 610 can contain some methane along with ethane, ethylene, and other heavier hydrocarbons, and can be sent to recover the ethylene product in aseparator 605. The CO2 product can be sent to methanation unit, and a part of the CO2 can be recycled to achieve the desired concentration of CO2 in thefeed stream 606. Such a CO2 distillation sub system can offer many benefits, including but not limited to reducing the loop size of the OCM process considerably, as the function of the existing cryogenic demethanizer can be reduced by a large extent. Additionally, amine and caustic systems can be replaced by cryogenic or low temperature distillation systems. - Alkaline salt-based processes can be used for carbon dioxide removal. These processes can utilize the alkali salts of various weak acids, such as sodium carbonate and potassium carbonate. These processes can provide advantages such as low cost and minimal solvent degradation. Processes that can be used for H2S and CO2 absorption include those using aqueous solutions of sodium or potassium compounds. For example, potassium carbonate can absorb CO2 at high temperatures, an advantage over amine-based solvents.
- Hot potassium carbonate (K2CO3) solutions can be used for the removal of CO2 from high-pressure gas streams, among other applications. Potassium carbonate has a low rate of reaction. To improve CO2 absorption, mass transfer promoters such as piperazine, diethanolamine, and arsenic trioxide can be used. Less toxic promoters such as borate can also be used, for example with flue gas streams (see, e.g., Ghosh et al., “Absorption of carbon dioxide into aqueous potassium carbonate promoted by boric acid”, Energy Procedia, pages 1075-1081, February 2009, which is hereby incorporated by reference in its entirety). To limit corrosion, inhibitors can be added. These systems can be known as activated hot potassium carbonate systems. Licensed hot activated potassium carbonate systems include the Benfield™ and the Catacarb™ process. The processes can be used for bulk CO2 removal from high-pressure streams, but can also produce high-purity CO2.
- Flue gas impurities such as SOx and NOx can reduce the operational efficiency of the potassium carbonate as a solvent. SO2 and NO2 may not able to be released from the solvent under industrial conditions. Selective precipitation of the impurity salts formed by SOx and NOx can be used to remove such compounds (see, e.g., Smith et al., “Recent developments in solvent absorption technologies at the CO2CRC in Australia” Energy Procedia, pages 1549-1555, February 2009, which is hereby incorporated by reference in its entirety).
- A variety of materials can be used as CO2 sorbents through chemical reactions and physical absorptions, including but not limited to soda-lime, active carbon, zeolites, molecular sieves, alkali metal oxides, silver oxide, lithium oxide, lithium silicate, carbonates, silica gel, alumina, amine solid sorbents, metal organic frameworks and others.
- Physical impregnation of CO2-reactive polymers, such as tetraethylene pentamine or polyethyleneimine, inside a porous support, such as alumina, pumice, clay or activated carbon, can be used for CO2 removal. Amine based sorbents can be easily regenerated. Alternatively, a mixture of an amine compound with a polyol compound can be impregnated in a porous support. The polyol compound can be used to increase the CO2 desorption rate of the amine. The supported amine-polyol sorbent can comprise from about 1 wt % to about 25 wt % amine and from about 1 wt % to about 25 wt % polyol, with the balance being the support. Solid sorbent can adsorb and desorb CO2 a relatively high rates at ambient temperatures Enhanced CO2 cyclic removal capacities in either dry or humid air flows can further be achieved by using a solid sorbent at an increased amine concentration of amines from about 35 wt % to about 75 wt %.
- Solid sorbents that can selectively remove multiple gases can be used to remove CO2, H2O, nitrogen oxides, and hydrocarbons. This can be achieved by using composite adsorbents, for example by using a mixed adsorbent of alumina and zeolite to remove CO2 and H2O simultaneously.
- CO2 can be separated from flue gas using an ion pump method instead of relying on large temperature and pressure changes to remove CO2 from a solvent. Ion pump methods can dramatically increase the overlying vapor pressure of CO2. As a result, the CO2 can be removed from the downstream side of the ion pump as a pure gas. The ion pumping can be obtained from techniques including but not limited to reverse osmosis, electro dialysis, thermal desalination methods, or an ion pump system having an oscillation flow in synchronization with an induced electric field.
- By making use of energy such as renewable or nuclear energy, carbon dioxide and water can be recycled into sustainable hydrocarbon fuels in a non-biological process. Various pathways can enable such a conversion, for example by H2O and CO2 dissociation followed by fuel synthesis. The methods of dissociation can include heat, electricity, and solar driven methods such as thermolysis, thermochemical loops, electrolysis, and photoelectrolysis. High temperature electrolysis can make efficient use of electricity and heat, provide high reaction rates, and integrate well with fuel synthesis.
- Synthetic analogues of enzymes as a polymer thin film supported on micro-porous substrates can be used to separate CO2 from gas mixtures. For example, a polymer thin film containing carbonic anhydrase mimicking sites can supported on a porous substrate and can separate CO2 from a stream containing O2 and N2. The system can be, for example, about 30% lower in cost compared to amine-based systems.
- Electrolysis can be used to produce industrial hydrogen. OCM processes can have a lot of synergistic benefit from deploying a water electrolysis subsystem with the OCM process. The water electrolysis unit can replace an air separation unit (ASU) to supply the oxygen required for the OCM process. The products from the electrolytic unit can be consumed within the OCM process: oxygen can be consumed within the OCM reactor and hydrogen can be used in a methanation reactor. Availability of more hydrogen in the methanation unit has the potential to increase the carbon efficiency to about 100%, by converting the CO2 produced in the OCM reaction to methane, which can be recycled back to the OCM reactor. The OCM unit can be a net exporter of high purity excess hydrogen, after consuming the entirety of the CO2 produced in the OCM Process.
- The water electrolysis subsystem can be an electrolytic cell employing alkaline water electrolysis, a proton exchange membrane electrolysis system, or a steam electrolysis system. The electricity source to the electrolytic sub system can be renewable, such as photo voltaic/solar power, which can make the entire system 100% carbon efficient with a zero carbon footprint. A storage system for oxygen, or a backup power supply, may be used to ensure the continuous supply of oxygen and hydrogen.
- With steam electrolysis, a substantial part of the energy needed for the electrolysis process can be added as heat, which can be much cheaper than electric energy, and which the OCM reactor can produce in abundance. Therefore, integration of steam electrolysis can take advantage of the extra heat from the OCM reactor to provide energy for the steam electrolysis. This can be of particular benefit to OCM deployments where no additional steam or power is required.
-
FIG. 7 depicts an exemplary electrolysis subsystem combined with an OCM system. Theelectrolysis subsystem 701 can takewater 710 andelectric power 711 as inputs and generatepure oxygen 712 andhydrogen 713 as products. The oxygen can be fed into anOCM reactor 702 with amethane feed 714, for conversion to higher hydrocarbon products including ethylene. The OCM product stream can be compressed in acompressor 704 and separated in aseparations unit 705. Higher hydrocarbon products 716 can be recovered from the separations unit, and other compounds such as methane and CO2 can be recycled 717 and/or purged 718. The recycle stream can be directed to amethanation unit 703, which can generatemethane 715 using the hydrogen from the electrolysis subsystem. The extra hydrogen that is now available to the methanation unit can enable the conversion of most or all of the CO2 produced in the OCM process to methane, which can drive the process to a higher efficiency. The process can also be almost 100% emission free. The CO2 produced in the process that may be discarded as waste may be converted to methane and hence to ethylene in the OCM reactor. - The OCM reaction is highly exothermic. Various quenching media can be used to extract the OCM reaction heat. For example, CO2 can be injected to extract the heat, which results in the OCM effluent containing excess CO2; such effluent can be suitable for the advanced CO2 recovery methods described herein.
FIG. 8 shows an exemplary system whereCO 2 814 is removed from an OCM product stream 812 (generated in anOCM unit 801 from anoxygen stream 810 and a methane stream 811) in a CO2 separation unit 802 and recycled from back to theOCM reactor 801. A waste gas orpurge stream 815 can also be removed from the CO2 separation unit. TheOCM product stream 813 can then be separated in aseparations unit 803 into aproduct stream 816 comprising ethylene and a purge and/or recyclestream 817. Separation methods can include low temperature separation, membrane separation, or other separation methods discussed herein. The OCM loop can be decreased to just a CO2 recycle stream. The system can also comprise a methanation unit (not shown). - Such an approach can provide advantages including a smaller recycle loop and more efficient CO2 removal methods, resulting in lower capital expenditure (CAPEX). This can also result in the feasibility of small distributed scale OCM units, since after the removal of excess CO2, the relatively richer ethylene stream needs fewer treatment and recovery steps.
- Waste heat from the OCM process can be used to generate superheated high pressure steam that can be used in the process, exported to other users on site, or can be used to generate power. Excess process heat can also be used to preheat the feed streams. Other uses for excess heat can be less capital intensive, and offer a greater operational flexibility and low maintenance. Thermoelectric energy conversion can be used to convert waste heat to power. Example uses for waste heat include single fluid rankine cycles (e.g., steam cycle, hydrocarbons, and ammonia), binary/mixed fluid cycles (e.g., ammonia/water or mixed hydrocarbon cycle).
- The organic Rankine cycle (ORC) can be used to generate power from heat. In ORC, an organic component is used instead of water. The organic compound can be a refrigerant, a hydrocarbon (e.g., butane, pentane, hexane), silicon oil, or a perfluorocarbon. The boiling point of the organic fluid can be lower than that of water, which can allow recovering heat at a lower temperature than in the traditional steam Rankine cycle.
- Owing to the exothermicity of the OCM reaction, the ORC system can be deployed as a waste heat recovery method for use with OCM. Waste heat at relatively low temperature can be recovered by an intermediate heat transfer loop and used to evaporate the working fluid of the ORC.
-
FIG. 9 shows an exemplary OCM system with an ORC subsystem. The working fluid can be chosen which can be condensed with cooling water or air at normal atmospheric pressure.FIG. 9 shows the heat source as the OCM reaction heat from anOCM unit 901. Heat can be recovered from theOCM product stream 910 in anevaporator 902, and theproduct stream 911 can then be directed for downstream processing from the OCM unit. The heat recovered in the evaporator can be used to evaporate a workingfluid stream 912, which can then be directed to aturbine 903 to generate power in agenerator 904. From the turbine, the workingfluid 913 can be directed to acondenser 905 and cooled using acooling medium 914. The cooled workingfluid 915 can then be pumped by apump 906 in astream 916 back to the evaporator. - The OCM process can make use of a heat exchanger with thermoelectric (TE) generators for heat recovery. A Thermoelectric Power Generator (TPG) can have four basic components: Heat source, P and N type semiconductor stack (or a TE module), heat sink (cold side), and an electrical load (output voltage). The TE module can include two or more of P-type and N-type semiconductor pellets connected in series or parallel depending on the served load.
- The TE devices can be solid state engines that do not require any working fluid. Thermoelectric materials can provide efficiencies of up to 15% or greater. Thermoelectric generators coupled with heat exchangers can produce electricity even at temperatures as low as 350 K with low maintenance. TE modules can be used with OCM including large bulk TE modules and thin film or micro TE modules.
- For high temperatures, micro TE modules can be used. Micro TE modules can also have low equipment weights. TE devices can be very reliable, scalable, and modular. Some TE modules can give best results at small scales. The OCM process can generate medium level waste heat that is highly suitable for a TE device to generate power.
- OCM and ETL Systems with Advanced Separations Sub-Systems
- PSA technology can be applied to processes including those involving a hydrocarbon stream containing a mix of the following hydrogen, carbon dioxide, carbon monoxide, methane, ethane, ethylene, propane, propylene, butanes, butenes and/or other higher hydrocarbons needing to be purified or separated into desirable products (e.g., ethylene, methane, hydrogen, or propylene).
- Hydrocarbon streams can be produced via traditional refining and petrochemical processes. Hydrocarbon streams can be produced from OCM or ETL reactor systems.
- The present disclosure provides the use of PSA in processes and systems for oxidative coupling of methane (OCM) and ethylene-to-liquids (ETL) operations, and the application of adsorbent based processes used in conjunction with OCM and ETL processes to generate significant process improvements and enhance the economic value of the processes. OCM systems are described in, for example, U.S. patent application Ser. No. 14/592,668, which is entirely incorporated herein by reference. ETL systems are described in, for example, U.S. patent application Ser. No. 14/591,850, which is entirely incorporated herein by reference.
- An OCM system, such as that shown in
FIG. 10 , can include an OCM or OCM-post-bed-cracking (PBC)reactor 1002, a processgas compression system 1003, a processgas treatment system 1004, a cryogenic separations system, and amethanation system 1001. The feed to the OCM system can be anoxygen feed 1012 and a methane source feed 1011 (such as a natural gas feed stream or other methane source). In some cases, additional ethane feed can be supplied to the PBC section of the OCM reactor, where paraffins such as ethane in the OCM product stream and/or additional ethane can be cracked to olefins such as ethylene. The separations sub-system can comprise a series of fractionation towers, like ademethanizer 1005, deethanizer 1006, C2 splitter 1007, depropanizer 1008, debutanizer, and others.Overhead 1013 from the demethanizer can be directed into the methanation system along with hydrogen ornatural gas 1010 to produce additional methane. The bottoms stream 1014 from the demethanizer can be directed to the deethanizer. Theoverhead stream 1015 from the deethanizer can be directed to the C2 splitter, and there split intoethylene 1016 andethane 1017 streams. The bottoms stream 1018 from the deethanizer can be directed to the depropanizer, and there split into a C3 product stream 1019 and a C4+ product stream 1020. The cryogenic separations system can comprise additional ethylene and propylene refrigeration sub-systems to provide for the chilling requirements of the system. - OCM process standalone with advanced separations systems
- In certain cases, the separations section of the OCM system can be eliminated, or partially eliminated, by utilizing an advanced separations method as discussed in this application. The advanced separation method can be a PSA unit or a membrane based method, or a cryogenic system.
FIG. 11 shows an exemplary schematic of OCM with a PSA unit. The PSA unit can separate methane, CO2, CO, and/or H2 from ethane, ethylene, propane, propylene, and/or higher hydrocarbons.Methane 1111 andoxygen 1112 can be directed into anOCM reactor 1102 and reacted to produce higher hydrocarbon products including ethylene. The OCM product can be compressed in a processgas compression system 1103, treated in a processgas treatment system 1104, and separated in thePSA 1105 into a product stream 1113 and arecycle stream 1114. The recycle stream can be directed to amethanation unit 1101, which can also receive anatural gas stream 1110 and produce methane for the OCM reactor. The extent of separation and degree of recovery can depend on the type of adsorbent(s), pressure differential, and number of PSA stages employed. The feed to the PSA unit can have one or more of the following components: H2, N2, O2, CO, CO2, CH4, ethane, ethylene, acetylene, propane, propylene, butanes, butenes, butadiene, water, and higher paraffinic and olefinic components. The PSA product gas can comprise components including but not limited to: H2, N2, CO, CO2, CH4, O2, ethane, ethylene and acetylene. PSA product gas can comprise components from 0% to 99.99% recovery. The PSA tail gas can comprise 99.99%, 90%, 80%, 70%, 60%, 50% ethylene. The PSA tail gas can comprise at least 99.99%, 90%, 80%, 70%, 60%, 50% ethylene. The PSA tail gas can comprise about 99%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, 0% ethane. The PSA tail gas can comprise at least about 99%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, 0% ethane. The PSA tail gas can comprise about 60%, 50%, 40%, 30%, 20%, 10%, 0% methane, hydrogen, acetylene, N2, O2, H2O or CO2. The PSA tail gas can comprise at least about 60%, 50%, 40%, 30%, 20%, 10%, 0% methane, hydrogen, acetylene, N2, O2, H2O or CO2. Based on the process configuration, including the type of adsorbents employed, pressure differential and the operation, various different recoveries are possible. - As discussed above, the PSA unit can comprise one or more adsorbent materials that can be suitable to achieve the component recoveries. The sorbent can be a zeolite/molecular sieve based material, a carbon based sorbent, or a π-complexation sorbent. In some cases the sorbent material can be a polymeric resin, carbon nanotubes, and carbon fibers. The PSA unit can be configured to have layers of different sorbents so as to result in high recoveries from the multi-component feed streams to the desired products.
- In certain cases the PSA can be a multi stage unit (see, e.g.,
FIG. 12 ). In such a unit, anOCM reactor 1202 can receive amethane stream 1211 and anoxygen stream 1212, and react the methane and oxygen to produce higher hydrocarbon products including ethylene in an OCM product stream. The OCM product stream can be compressed in afirst compressor 1203 and directed to afirst PSA separation 1204. Thetail gas 1214 from the first PSA can be compressed in asecond compressor 1205 and fed to asecond PSA separation 1206, thetail gas 1216 from which can be compressed in athird compressor 1207 and separated in athird PSA separation 1208. The tail gas from the third PSA can be the finalpurified stream 1217 containing ethylene up to 99.9% purity.PSA product streams methanation unit 1201 along with anatural gas stream 1210. Each PSA stage can be a dual-bed PSA or a multi-bed PSA system. - In certain cases, the process requirements can dictate that only a limited amount of recovery is required in the PSA unit and subsequent recovery and purification is performed in a fractionation column or the gas is a feed for a downstream process unit. The downstream process unit can be an ETL system, an ethylene steam cracker system, a gas processing plant, NGL extraction plant, a refinery off-gas separations system, or other process unit.
- OCM can be employed to convert a feedstock comprising methane to ethylene and other olefins. Historically, ethylene has been produced via steam cracking of gaseous or liquid hydrocarbon feedstocks like ethane, propane, LPG, or naphtha. As in most of the refining and petrochemical operations, a steam cracking operation can involve a cryogenic fractionation or a separations section that consists of a series of fractionation columns to successively recover various components at high product purity.
- The present disclosure includes the application of PSA processes to an OCM retrofit of an existing ethylene cracker (e.g., steam cracker).
- An example application for OCM combined with a PSA unit involves an existing petrochemical plant such as a steam cracker is considering low cost ways to add ethylene capacity. A typical revamp to add capacity could include addition of, or debottlenecking of, the existing fractionation towers for the entire flow addition for the revamp. However, as shown in
FIG. 13 , the use of a PSA unit as disclosed herein can provide a low cost alternative to traditional revamps. An OCM unit with a PSA unit retrofitted to an existing steam cracker can be an effective way of adding ethylene capacity at a low marginal cost. The advantages of adding a PSA unit include that no additional cryogenic separation is required for the added capacity. For ethylene revamps, one of the key areas during debottlenecking may be the refrigeration systems and/or the fractionation columns, but utilizing the PSA to separate or pre-separate the additional product stream can result in a simpler and easier debottlenecking. As in shown inFIG. 13 , for example, the tail gas from the PSA can be sent to the cracker system where the ethylene is recovered. -
FIG. 13 shows an example of an OCM process integrated with an existing ethylene cracker using a PSA system for separations. TheOCM reactor 1301 takes inmethane 1310 andoxygen 1311 and produces anOCM effluent 1312 having CO2, CH4 and C2H4, in some cases amongst other components, such as H2 and CO. The OCM reaction can be exothermic and can produce steam 1313. The OCM effluent can be compressed in acompressor 1302 and optionally treated in an acidgas removal system 1303, and fed into a pressure swing adsorption (PSA)unit 1304. In some cases the acid gas removal system may have an additional knock out drum to condense and separate any condensates and water. It also can include a drier to remove water. The PSA unit can produce a product stream that can include H2, CH4, ethane, CO2 and CO. Theoverhead stream 1315 can be fed into a methanation subsystem 1305 (e.g., methanation reactor) to provide methane for the OCM reactor, and some of the overhead stream can be purged 1316 to a fuel gas system, for example. Additional methane can be provided by way of a natural gas stream or other methane stream. ThePSA tail gas 1317 can comprise most of the ethylene, the content of which may range from 50% to 99.9% depending on the process configuration and operation of the PSA system. The PSA tail gas can also comprise H2, CO, CO2, CH4, ethane, propane, propylene, butanes, butenes, and other components. The process ofFIG. 13 can further include an existingethylene cracker 1306. The PSA tail gas can be fractionated using existing separations capacity in the ethylene cracker. The heavy components can be processed in the fractionation towers of the ethylene cracker, optionally first being compressed in the existing process gas compressor of the ethylene cracker. In some cases, the heavy components stream can be routed to the CO2 removal unit of the existing ethylene cracker subsystem to meet the CO2 specification. The OCM reactor can receive a C2 recycle stream 1319 from the cracker complex. - The combination of a new OCM unit and an existing ethylene cracker can provide synergistic benefits. It can provide for a low cost alternative to add ethylene capacity to the existing cracker. In some cases, prior to retrofit of an ethylene cracker with OCM, the entire overhead from the existing demethanizer is used as fuel gas, and can now be available as one of the feeds to the methanation unit. In some cases, the demethanizer overhead off-gas comprises up to 95% methane, which can be converted to ethylene in the OCM reactor, hence increasing the total ethylene capacity. In some cases, the hydrogen content in the existing demethanizer overhead is substantial, and may be enough to meet the hydrogen requirement of the methanation unit.
- In some cases, retrofitting an ethylene cracker with OCM reduces (or allows for reduction of) the severity of cracking in the existing cracker, enabling value addition by increasing the production of pyrolysis gasoline components in the cracker effluent, as the OCM reactor produces the ethylene that may be needed to achieve the total system capacity. The cracker can then be operated on high propylene mode to produce more propylene and at the same time meeting the ethylene production rate by the new OCM unit. This retrofit can result in greater flexibility for the ethylene producer with respect to the existing cracker operation.
- In some instances, the overall carbon efficiency can be increased as the methane and hydrogen from the existing demethanizer off-gases can be utilized to convert the carbon dioxide and carbon monoxide to methane, which is fed to the OCM reactor.
- In some instances, ethane and/or propane recycle streams from the existing cracker can be routed to the OCM unit (e.g., instead of the cracking furnaces). These recycle streams are typically routed to the cracking furnaces where they are cracked to extinction. This can provide an advantage over routing the recycle streams to OCM over the cracking furnace, such as higher selectivity to ethylene in the OCM process.
- In certain cases, more than one stages or PSA columns may be employed to achieve higher recovery and higher product purity. As in shown
FIG. 14 , for example, up to 99.9% recovery is possible using the multi stage PSA units. AnOCM reactor 1402 can receive amethane stream 1410 and anoxygen stream 1411, and react the methane and oxygen to produce higher hydrocarbon products including ethylene in an OCM product stream. The OCM product stream can be compressed in afirst compressor 1403 and directed to afirst PSA separation 1404. Thetail gas 1412 from the first PSA can be compressed in asecond compressor 1405 and fed to asecond PSA separation 1406, thetail gas 1414 from which can be compressed in athird compressor 1407 and separated in athird PSA separation 1408. The tail gas from the third PSA can be the finalpurified stream 1417 can be directed to a cracker unit, such as an existing cracker unit, where it can be processed and separated into anethylene product stream 1418, apropylene product stream 1419, and anadditional product stream 1420.PSA product streams methanation unit 1401, along with a demethanizer offgas stream 1421 from the cracker unit. Each PSA stage can be a dual-bed PSA or a multi-bed PSA system. - The application of a PSA unit to OCM systems, standalone or retrofits to existing facilities exhibits immense potential in terms of cost savings and ease of integration and retrofit to existing facilities.
-
FIG. 15 shows various exemplary configurations for an OCM-ETL process. In the upper left,FIG. 15 shows a stand alone skimmer configuration, where amethane stream 1505 can be directed into anOCM reactor 1501 with anoxygen feed 1506 and optionally anethane feed 1507. The OCM reactor product stream can be directed into acompressor 1502 and then into anETL reactor 1503. The ETL product stream can be directed into agas separations unit 1504, where it can be separated into a C2+ product stream 1508, a C5+ product stream 1509, and anoverhead stream 1510 comprising methane which can be returned to a pipeline, sold to a consumer, or otherwise used. In the upper right,FIG. 15 shows a stand alone recycle configuration, where a methane feed stream 1518 (e.g., from a natural gas pipeline) is directed into atreatment unit 1511 and then into a separations system (e.g., cryogenic) 1512. Amethane feed stream 1519 can be directed to anOCM reactor 1513, while another methane stream 1520 can be purged or used for power generation. A C2+ stream 1521 can also be recovered from the separations system. Anoxygen feed stream 1522 and optionally anethane stream 1523 can also be directed into the OCM reactor, and the reactor can produce an OCM product stream. The OCM product stream can be directed into acompressor 1514 and then into anETL reactor 1515. The ETL product stream can be processed in aknockout drum 1516 or other separator to remove a C5+ product stream 1524. The remaining ETL product stream can be directed to acompressor 1517 and recycled to the treatment unit. In the lower left,FIG. 15 shows a hosted skimmer configuration, where amethane stream 1532 can be directed from a separations system 1526 (e.g., cryogenic) into an OCM reactor 1527 with an oxygen feed 1533 and optionally anethane feed 1534. The OCM reactor product stream can be directed into a compressor 1528 and then into anETL reactor 1529. The ETL product stream can be directed into agas separations unit 1530, where it can be separated into a C2+ product stream 1535, a C5+ product stream 1536, and anoverhead stream 1537 comprising methane which can be returned to arecompressor 1531. In the lower right,FIG. 15 shows a hosted recycle configuration, where a methane stream is directed into atreatment unit 1538 and then into a separations system (e.g., cryogenic) 1539. Amethane feed stream 1546 can be directed to an OCM reactor 1541, while another methane stream can be directed to arecompressor 1540. A C2+ stream 1551 can also be recovered from the separations system. Anoxygen feed stream 1547 and optionally anethane stream 1548 can also be directed into the OCM reactor, and the reactor can produce an OCM product stream. The OCM product stream can be directed into a compressor 1542 and then into an ETL reactor 1543. The ETL product stream can be processed in a knockout drum 1544 or other separator to remove a C5+ product stream 1549. The remaining ETL product stream can be directed to acompressor 1545 and recycled 1550 to the treatment unit. -
FIG. 16 shows similar configurations asFIG. 15 , with an added pressure swing adsoprtion (PSA) unit to pre-separate the OCM effluent to remove most of the methane, hydrogen, CO and CO2 from the olefinic stream, which is then fed to the ETL reactor. This can result in a feed to the ETL reactor that is concentrated in olefins. Though the process remains similar, the entire ETL and separations train becomes considerably smaller; that is, larger capacities can be achieved in the same set-up or same footprint. In some cases this can improve the ETL reaction operation. In the upper left,FIG. 16 shows a stand alone skimmer configuration, where amethane stream 1606 can be directed into anOCM reactor 1601 with anoxygen feed 1607 and optionally anethane feed 1608. The OCM reactor product stream can be directed into acompressor 1602 and then into aPSA unit 1603. Alight stream 1609 comprising methane, hydrogen, CO and CO2 can be directed from the PSA back to a pipeline, sold to a consumer, or otherwise used. An olefinic stream can be directed from the PSA to anETL reactor 1604. The ETL product stream can be directed into agas separations unit 1605, where it can be separated into a C2+ product stream 1610, a C5+ product stream 1611, and anoverhead stream 1612 comprising methane which can be returned to a pipeline, sold to a consumer, or otherwise used. In the upper right,FIG. 16 shows a stand alone recycle configuration, where a methane feed stream 1628 (e.g., from a natural gas pipeline) is directed into atreatment unit 1620 and then into a separations system (e.g., cryogenic) 1621. Amethane feed stream 1629 can be directed to anOCM reactor 1622, while anothermethane stream 1630 can be purged or used for power generation. A C2+ stream 1631 can also be recovered from the separations system. Anoxygen feed stream 1632 and optionally anethane stream 1633 can also be directed into the OCM reactor, and the reactor can produce an OCM product stream. The OCM product stream can be directed into acompressor 1623, and at least aportion 1634 of the OCM product stream can be directed from the compressor into aPSA unit 1624. Alight stream 1635 comprising methane, hydrogen, CO and CO2 can be directed from the PSA back to the treatment unit. Anolefinic stream 1636 can be directed from the PSA to anETL reactor 1625. The ETL product stream can be processed in aknockout drum 1626 or other separator to remove a C5+ product stream 1637. The remaining ETL product stream can be directed to acompressor 1627 and recycled to the treatment unit. In the lower left,FIG. 16 shows a hosted skimmer configuration, where amethane stream 1647 can be directed from a separations system 1640 (e.g., cryogenic) into an OCM reactor 1641 with anoxygen feed 1648 and optionally anethane feed 1649. The OCM reactor product stream can be directed into acompressor 1642 and then into and then into aPSA unit 1643. Alight stream 1650 comprising methane, hydrogen, CO and CO2 can be directed from the PSA to arecompressor 1646. An olefinic stream can be directed from the PSA to an ETL reactor 1644. The ETL product stream can be directed into agas separations unit 1645, where it can be separated into a C2+ product stream 1651, a C5+ product stream 1652, and anoverhead stream 1653 comprising methane which can be returned to the recompressor. In the lower right,FIG. 16 shows a hosted recycle configuration, where a methane stream is directed into atreatment unit 1660 and then into a separations system (e.g., cryogenic) 1661. Amethane feed stream 1669 can be directed to anOCM reactor 1663, while another methane stream can be directed to arecompressor 1662. A C2+ stream 1677 can also be recovered from the separations system. Anoxygen feed stream 1670 and optionally anethane stream 1671 can also be directed into the OCM reactor, and the reactor can produce an OCM product stream. The OCM product stream can be directed into acompressor 1664 and at least aportion 1672 of the OCM product stream can be directed from the compressor into aPSA unit 1665. Alight stream 1673 comprising methane, hydrogen, CO and CO2 can be directed from the PSA back to the treatment unit. Anolefinic stream 1674 can be directed from the PSA to anETL reactor 1666. The ETL product stream can be processed in aknockout drum 1667 or other separator to remove a C5+ product stream 1675. The remaining ETL product stream can be directed to acompressor 1668 and recycled 1676 to the treatment unit. - The ETL reactor can be a tubular, packed bed, moving bed, fluidized bed, or other reactor type. An ETL reactor can be an isothermal or adiabatic reactor. The ETL system can benefit from a feed concentrated in olefins. The ETL reactor system can use a recycle stream to control and moderate the temperature increase in the reactor bed due to the highly exothermic nature of the ETL reactions. ETL systems are described in, for example, U.S. patent application Ser. No. 14/591,850, which is entirely incorporated herein by reference.
- In certain embodiments, one or more of the fractionation towers can be deemed redundant if using the PSA, as an example, a demethanizer may not be required and the sales gas or purge gas to fuel can be sent from the PSA itself.
- Systems, such as those of
FIG. 17 , can be integrated with an existing gas processing plant where one or more of the existing subsystems can be utilized. The utilization may arise from the fact that the existing subsystems are no longer used, or have an additional capacity available to allow for the integration. -
FIG. 17 shows an exemplary application of an OCM-ETL system using a PSA system for pre-separations to an existing gas processing plant, where one or more existing sub systems may be utilized. As shown inFIG. 17 , the existing separations sub-system can be integrated with the OCM-ETL system to add value by converting natural gas to higher value liquid hydrocarbons. The PSA unit can be used to pre-separate the lighter components like methane, hydrogen, carbon monoxide, carbon dioxide, ethane, and other components, and the olefin rich stream can be sent to the ETL reactor that converts the olefins to higher molecular weight liquid hydrocarbons. One advantage of using a PSA system is the reduction in net additional feed to the existing separation system, which can be de-bottlenecked easily. If the separation system is no longer in use, addition of a PSA can bring about larger total capacities that can be achieved by adding larger OCM-ETL systems. Anatural gas stream 1720 can be directed to atreatment unit 1701 and then into a separations system (e.g., cryogenic) 1702. At least portion of amethane stream 1724 from the separations unit can be directed to anOCM reactor 1705, while a portion of the methane stream can be directed to acompressor 1703 and used assales gas 1721 or other purposes. A higher hydrocarbon stream can be directed from the separations system to a C2 removal unit 1704, which can produce a natural gas liquids stream 1722 and a C2 stream 1723. The C2 stream can be fed into the OCM reactor with the methane stream and anoxygen stream 1725, and reacted to form higher hydrocarbon products including ethylene. The OCM product stream can be directed into aheat recovery system 1706, which can generate a high pressure superheated (HPSH)steam stream 1726. The OCM product stream can then be directed to a knockout drum to recover acondensate stream 1727. The OCM product stream can then be directed to acompressor 1708, which can operate using the HPSH steam stream. From the compressor, the OCM product stream can be directed to aPSA unit 1709. From the PSA unit, light stream comprising methane, hydrogen, CO and CO2 can be directed to amethanation unit 1710, and an olefinic stream can be directed to anETL reactor 1711 and reacted to form higher hydrocarbon products. The ETL product stream can be directed to aheat recovery unit 1712, where boiler feed water (BFW) 1728 can be heated, at least a portion of which can be fed 1729 to theheat recovery unit 1706. The ETL product stream can then be directed to anotherknockout drum 1713. The overhead stream from the knockout drum can be directed to a lowtemperature separations unit 1714, while the bottoms stream from the knockout drum can be directed to a C4 removal unit 1715, which can produce a C4 stream 1730 and a C5+ stream 1731. Overhead from the low temperature separations unit, as well as product from the methanation reactor, can be directed back to thecompressor 1703. - OCM-ETL systems of the present disclosure can be integrated into and combined into conventional NGL extraction and NGL fractionation sections of a midstream gas plant. Where NGLs in the gas stream are declining (or gas is dry), the deployment of OCM-ETL can utilize an existing facility to produce additional liquid streams. The implementation of OCM-ETL can allow for the generation of on specification “pipeline gas.” The products from the facility can be suitable for use (or on specification or “spec”) as pipeline gas, gasoline product, hydrocarbon (HC) streams with high aromatic content, and mixed C4 products. The PSA systems discussed above can be employed to separate, pre-separate or purify the hydrocarbon feed streams in the integrated NGL OCM-ETL system.
FIG. 18 shows an exemplary NGL extraction facility integrated with an OCM-ETL system. As shown inFIG. 18 , for example, the feed to thePSA 1802 can be the net incoming gas from thetreatment system 1801, which can treat a methane stream (e.g., natural gas) 1810. The PSA system can separate the feed to theOCM reactor 1803, which is mostly methane and lighter components with some ethane to utilize a PBC section of the OCM reactor, and the feed to theETL reactor 1805, which can first be processed in a natural gasliquids extraction system 1804. The feed to the ETL system can be the PSA tail gas and OCM effluent comprising ethylene, propylene, ethane, propane, hydrogen, methane, and other components. In some cases, the OCM effluent can be directly fed to the ETL reactor. In some cases the OCM effluent is hydrogenated and fed to the ETL system. In some cases, as shown for example inFIG. 18 , the OCM effluent is fed back to the PSA unit for separation; additionalnatural gas 1811 can be added, and a stream can be recovered 1812 (e.g., for use as pipeline gas). In some examples, the system may have a methanation unit that takes in the effluent from ETL reactor or OCM reactor and converts the CO, CO2 and H2 to methane, thereby further increasing the carbon efficiency of the process. The existing NGL extraction andproduct fractionation 1806 sub-systems can then be used to fractionate the final products, including into a mixed C4 stream 1814 and a C5+ product stream 1815. - Refinery gas typically contains valuable components like hydrogen, methane, ethane, ethylene, propane, propylene, and butane. Most commonly, refinery off-gases (ROG) are exported to the fuel gas system, thereby losing the value of the components contained therein. The OCM-ETL process can be used to improve the value of products as the OCM converts the methane to ethylene and the ETL converts olefins (e.g., those existing in the ROG and those generated by OCM) to higher value liquids as C4 components, gasoline blends, or aromatic components.
-
FIG. 19 shows an exemplary PSA unit integrated to a refinery process scheme. Arefinery gas plant 1901 can receivegas 1910 from cracking or other units. The PSA unit 1903 (after, for example, treatment of the gas in a treatment unit 1902) can separate components in refinery gas plant off gas to methane and a C2+ cut which contains most or all of the olefinic materials. The methane can be used asrefinery fuel 1911 and/or directed to anOCM unit 1904 with post-bed cracking The OCM feed can be supplemented with additionalnatural gas 1912. The olefinic materials can be directed to anETL reactor 1905. The OCM effluent can also be routed to the PSA where the olefins produced in the OCM are also sent to the ETL reactor. In some cases, the OCM effluent can be routed to the ETL reactor. In some cases, the OCM effluent may be hydrogenated before being sent to the PSA unit or ETL reactor. Some techniques may dictate the use of a cryogenic demethanizer in place of the PSA, but the application of PSA to pre-separate the refinery off-gas into a product stream and a tail gas stream containing the heavier hydrocarbons which is the feed to ETL reactor can result in significant cost savings. The product stream can contain methane, ethane, CO, CO2, and other components, with of each component from 1 to 99%. A C3+ stream 1913 from the refinery gas plant can be directed to aproduct fractionation system 1906, which can provide a C2/C3 stream 1914 (which can be directed to the OCM reactor), an iC4 stream 1915, agasoline blend stream 1916, and/or a kerosene/jet stream 1917. - As shown in
FIG. 20 , in some cases the system can have a methanation unit to further improve the carbon efficiency of the process. Arefinery gas plant 2001 can receivegas 2010 from cracking or other units. The PSA unit 2003 (after, for example, treatment of the gas in a treatment unit 2002) can separate components in refinery gas plant off gas to methane and a C2+ cut which contains most or all of the olefinic materials. The methane can be used asrefinery fuel 2011 and/or directed to amethanation unit 2004, and then to anOCM reactor 2005 with post-bed cracking The methanation feed can be supplemented with additionalnatural gas 2012. The olefinic materials can be directed to anETL reactor 2006. The OCM effluent can be routed to the ETL reactor. In some cases, the OCM effluent can also be routed to the PSA where the olefins produced in the OCM are also sent to the ETL reactor. In some cases, the OCM effluent may be hydrogenated before being sent to the PSA unit or ETL reactor. Some techniques may dictate the use of a cryogenic demethanizer in place of the PSA, but the application of PSA to pre-separate the refinery off-gas into a product stream and a tail gas stream containing the heavier hydrocarbons which is the feed to ETL reactor can result in significant cost savings. The product stream can contain methane, ethane, CO, CO2, and other components, with of each component from 1 to 99%. A C3+ stream 2013 from the refinery gas plant can be directed to aproduct fractionation system 2007, which can provide a C2/C3 stream 2014 (which can be directed to the OCM reactor), an iC4 stream 2015, agasoline blend stream 2016, and/or a kerosene/jet stream 2017. - Methods and systems of the present disclosure can be combined with or modified by other methods and systems, such as those described in U.S. patent application Ser. No. 14/591,850, filed Jan. 7, 2015, now published as U.S. Patent Pub. No 2015/0232395; U.S. patent application Ser. No. 13/936,783, filed Jul. 8, 2013, now published as U.S. Patent Pub. No. 2014/0012053; U.S. patent application Ser. No. 13/936,870, filed Jul. 8, 2013, now published as U.S. Patent Pub. No. 2014/0018589; U.S. patent application Ser. No. 13/900,898, filed May 23, 2013, now published as U.S. Patent Pub. No 2014/0107385; U.S. patent application Ser. No. 14/553,795, filed Nov. 25, 2014, now published as U.S. Patent Pub. No. 2015/0152025; U.S. patent application Ser. No. 14/592,668, filed Jan. 8, 2015, now published as U.S. Patent Pub. No. 2015/0210610; and U.S. patent application Ser. No. 14/789,953, filed Jul. 1, 2015, each of which is entirely incorporated herein by reference.
- While preferred embodiments of the present invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. It is not intended that the invention be limited by the specific examples provided within the specification. While the invention has been described with reference to the aforementioned specification, the descriptions and illustrations of the embodiments herein are not meant to be construed in a limiting sense. Numerous variations, changes, and substitutions will now occur to those skilled in the art without departing from the invention. Furthermore, it shall be understood that all aspects of the invention are not limited to the specific depictions, configurations or relative proportions set forth herein which depend upon a variety of conditions and variables. It should be understood that various alternatives to the embodiments of the invention described herein may be employed in practicing the invention. It is therefore contemplated that the invention shall also cover any such alternatives, modifications, variations or equivalents. It is intended that the following claims define the scope of the invention and that methods and structures within the scope of these claims and their equivalents be covered thereby.
Claims (43)
1. A method for generating higher hydrocarbon(s) from a stream comprising compounds with two or more carbon atoms (C2+), comprising:
(a) introducing methane and an oxidant into an oxidative coupling of methane (OCM) reactor that has been retrofitted into a system comprising an ethylene-to-liquids (ETL) reactor, wherein said OCM reactor reacts said methane with said oxidant to generate a first product stream comprising said C2+ compounds;
(b) directing said first product stream to a pressure swing adsorption (PSA) unit that recovers at least a portion of said C2+ compounds from said first product stream to yield a second product stream comprising said at least said portion of said C2+ compounds;
(c) directing said second product stream to said ETL reactor; and
(d) generating said higher hydrocarbon(s) from said at least said portion of said C2+ compounds in said ETL reactor.
2. The method of claim 1 , further comprising:
recovering a light stream comprising (i) hydrogen and (ii) carbon monoxide (CO) and/or carbon dioxide (CO2) from said PSA unit and recycling said light stream to said OCM reactor;
directing at least a portion of said light stream into a methanation unit that reacts said hydrogen and said CO and/or CO2 to produce a methanation product stream comprising methane; and
directing said methanation product stream into said OCM reactor.
3. The method of claim 1 , further comprising recovering C2 and/or C3 compounds from said second product stream and directing said C2 and/or C3 compounds to said OCM reactor.
4. The method of claim 1 , wherein said OCM reactor further comprises a post-bed cracking (PBC) unit.
5. A method for generating compounds with two or more carbon atoms (C2+ compounds), comprising:
(a) directing oxygen (O2) and methane (CH4) into an oxidative coupling of methane (OCM) reactor that reacts said O2 and CH4 in an OCM process to yield a product stream comprising (i) C2+ compounds including ethylene (C2H4) and (ii) carbon monoxide (CO) and/or carbon dioxide (CO2); and
(b) directing said product stream from said OCM reactor into a separations system that employs a refrigeration unit having a refrigerant that includes methane from said product stream, to enrich said C2+ compounds in said product stream.
6. The method of claim 5 , wherein said product stream is directed into said separations system through one or more additional units.
7. The method of claim 5 , further comprising separating methane from said product stream for use in said refrigeration unit.
8. The method of claim 5 , further comprising directing CO and/or CO2 from said product stream to a methanation reactor that reacts said CO and/or CO2 to yield a methanation product stream comprising methane.
9. The method of claim 8 , further comprising directing at least a portion of said methane in said methanation product stream to said OCM reactor.
10. The method of claim 5 , further comprising separating said product stream into (i) an ethylene product stream comprising ethylene and (ii) a C3+ product stream comprising compounds with three or more carbon atoms (C3+ compounds).
11. The method of claim 5 , further comprising directing ethane from said product stream to said OCM reactor.
12. The method of claim 5 , further comprising, prior to directing said product stream into said separations system, compressing said product stream.
13. A method for generating compounds with two or more carbon atoms (C2+ compounds), comprising:
(a) directing oxygen (O2) and methane (CH4) into an oxidative coupling of methane (OCM) reactor that reacts said O2 and CH4 in an OCM process to yield a product stream comprising (i) C2+ compounds including ethylene (C2H4) and (ii) carbon monoxide (CO) and/or carbon dioxide (CO2); and
(b) directing said product stream from said OCM reactor into a separations system that employs a complexation unit having a complexation catalyst that forms pi complexes with said ethylene in said product stream, to enrich said C2+ compounds in said product stream.
14. The method of claim 13 , wherein said product stream is directed into said separations system through one or more additional units.
15. The method of claim 13 , further comprising using said complexation unit to remove one or more impurities from said product stream, wherein said impurities are selected from the group consisting of CO2, sulfur compounds, acetylenes, and hydrogen.
16. The method of claim 13 , wherein said complexation catalyst includes one or more metals selected from the group consisting of silver and copper.
17. The method of claim 13 , further comprising directing CO and/or CO2 from said product stream to a methanation reactor that reacts said CO and/or CO2 to yield a methanation product stream comprising methane.
18. The method of claim 17 , further comprising directing said methane in said methanation product stream to said OCM reactor.
19. The method of claim 13 , further comprising separating said product stream into (i) an ethylene product stream comprising ethylene and (ii) a C3+ product stream comprising compounds with three or more carbon atoms (C3+ compounds).
20. The method of claim 13 , further comprising directing ethane from said product stream to said OCM reactor.
21. The method of claim 13 , further comprising, prior to directing said product stream into said separations system, compressing said product stream.
22. A method for generating compounds with two or more carbon atoms (C2+ compounds), comprising:
(a) directing oxygen (O2) and methane (CH4) into an oxidative coupling of methane (OCM) reactor that reacts said O2 and CH4 in an OCM process to yield a product stream comprising (i) C2+ compounds including ethylene (C2H4) and (ii) carbon dioxide (CO2); and
(b) directing said product stream from said OCM reactor into a separations system that employs a CO2 separation unit to separate said CO2 from said product stream, to enrich said C2+ compounds in said product stream, which CO2 separation unit employs (i) sorbent or solvent separation of CO2, (ii) membrane separation of CO2, or (iii) cryogenic or low temperature separation of CO2 having an operating temperature greater than a boiling point of methane and less than a boiling point of CO2.
23. The method of claim 22 , wherein said product stream is directed into said separations system through one or more additional units.
24. The method of claim 22 , wherein said sorbent or solvent separation of CO2 employs an amine based absorption system, a Benfield process, diethanolamine, glycol dimethylether, propylene carbonate, Sulfinol, a zeolite, or active carbon.
25.-31. (canceled)
32. The method of claim 22 , wherein said CO2 separation system comprises a membrane CO2 separation system.
33. The method of claim 22 , wherein said membrane separation of CO2 employs a polymeric membrane, metallic membrane, ceramic membrane, poly ionic liquid membrane, supported ionic liquid membrane, polyetherimide membrane, or hybrid membrane comprising a membrane supporting a solvent or sorbent.
34.-39. (canceled)
40. The method of claim 22 , further comprising directing said CO2 from said product stream to a methanation reactor that reacts said CO2 to yield a methanation product stream comprising methane.
41. The method of claim 40 , further comprising directing said methane in said methanation product stream to said OCM reactor.
42. The method of claim 22 , further comprising separating said product stream into (i) an ethylene product stream comprising ethylene and (ii) a C3+ product stream comprising compounds with three or more carbon atoms (C3+ compounds).
43. The method of claim 22 , further comprising directing ethane from said product stream to said OCM reactor.
44. The method of claim 22 , further comprising, prior to directing said product stream into said separations unit, compressing said product stream.
45. A method for generating compounds with two or more carbon atoms (C2+ compounds), comprising:
(a) directing water into an electrolysis unit that electrolyzes said water to yield oxygen (O2) and hydrogen (H2);
(b) directing said O2 from said electrolysis unit and methane (CH4) into an oxidative coupling of methane (OCM) reactor that reacts said O2 and CH4 in an OCM process to yield a product stream comprising (i) C2+ compounds, including ethylene (C2H4) and (ii) carbon monoxide (CO) and/or carbon dioxide (CO2);
(c) directing at least a portion of said CO and/or CO2 from said product stream and said H2 from said electrolysis unit into a methanation reactor that reacts said H2 and said CO and/or CO2 to yield CH4; and
(d) directing at least a portion of said CH4 from said methanation reactor to said OCM reactor.
46.-48. (canceled)
49. A method for generating compounds with two or more carbon atoms (C2+ compounds), comprising:
(a) directing oxygen (O2) and methane (CH4) into an oxidative coupling of methane (OCM) reactor that reacts said O2 and CH4 in an OCM process to yield a product stream comprising (i) C2+ compounds including ethylene (C2H4) and (ii) carbon dioxide (CO2);
(b) directing said product stream from said OCM reactor into a separations system that employs a CO2 separation unit that separates said CO2 from said product stream to enrich said C2+ compounds in said product stream; and
(c) directing at least a portion of said CO2 separated in (b) to said OCM reactor.
50. (canceled)
51. A method for generating compounds with two or more carbon atoms (C2+ compounds), comprising:
(a) directing oxygen (O2) and methane (CH4) into an oxidative coupling of methane (OCM) reactor that reacts said O2 and CH4 in an OCM process to yield a product stream comprising C2+ compounds including ethylene (C2H4) and heat;
(b) using an evaporator to transfer at least a portion of said heat from said product stream to an organic working fluid in a closed fluid flow cycle as part of an organic Rankine cycle (ORC) system, to evaporate said organic working fluid, which closed fluid flow cycle includes said evaporator, a turbine, a condenser, and a pump;
(c) directing said organic working fluid evaporated in (b) to said turbine to generate power;
(d) directing said organic working fluid from said turbine to said condenser that condenses said organic working fluid; and
(e) directing said organic working fluid condensed in (d) to said pump.
52. (canceled)
53. (canceled)
54. A method for generating compounds with two or more carbon atoms (C2+ compounds), comprising:
(a) directing oxygen (O2) and methane (CH4) into an oxidative coupling of methane (OCM) reactor that reacts said O2 and CH4 in an OCM process to yield a product stream comprising (i) C2+ compounds including ethylene (C2H4) and heat;
(b) transferring at least a portion of said heat from said product stream to a thermoelectric power generator; and
(c) with the aid of said heat, using said thermoelectric power generator to generate power.
55. (canceled)
56. (canceled)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/868,911 US20160289143A1 (en) | 2015-04-01 | 2015-09-29 | Advanced oxidative coupling of methane |
PCT/US2016/024195 WO2016160563A1 (en) | 2015-04-01 | 2016-03-25 | Advanced oxidative coupling of methane |
CA2975743A CA2975743C (en) | 2015-04-01 | 2016-03-25 | Advanced oxidative coupling of methane |
US16/445,562 US11186529B2 (en) | 2015-04-01 | 2019-06-19 | Advanced oxidative coupling of methane |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201562141789P | 2015-04-01 | 2015-04-01 | |
US14/868,911 US20160289143A1 (en) | 2015-04-01 | 2015-09-29 | Advanced oxidative coupling of methane |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/445,562 Continuation US11186529B2 (en) | 2015-04-01 | 2019-06-19 | Advanced oxidative coupling of methane |
Publications (1)
Publication Number | Publication Date |
---|---|
US20160289143A1 true US20160289143A1 (en) | 2016-10-06 |
Family
ID=57004566
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/868,911 Abandoned US20160289143A1 (en) | 2015-04-01 | 2015-09-29 | Advanced oxidative coupling of methane |
US16/445,562 Active 2035-10-21 US11186529B2 (en) | 2015-04-01 | 2019-06-19 | Advanced oxidative coupling of methane |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/445,562 Active 2035-10-21 US11186529B2 (en) | 2015-04-01 | 2019-06-19 | Advanced oxidative coupling of methane |
Country Status (3)
Country | Link |
---|---|
US (2) | US20160289143A1 (en) |
CA (1) | CA2975743C (en) |
WO (1) | WO2016160563A1 (en) |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9527784B2 (en) | 2012-01-13 | 2016-12-27 | Siluria Technologies, Inc. | Process for separating hydrocarbon compounds |
US20160376148A1 (en) * | 2015-06-23 | 2016-12-29 | Sabic Global Technologies, B.V. | Method for Producing Hydrocarbons by Oxidative Coupling of Methane without Catalyst |
US9556086B2 (en) | 2012-05-24 | 2017-01-31 | Siluria Technologies, Inc. | Oxidative coupling of methane systems and methods |
US9567269B2 (en) | 2015-03-17 | 2017-02-14 | Siluria Technologies, Inc. | Efficient oxidative coupling of methane processes and systems |
US20170058711A1 (en) * | 2015-08-24 | 2017-03-02 | Saudi Arabian Oil Company | Organic Rankine Cycle Based Conversion of Gas Processing Plant Waste Heat into Power and Cooling |
US9670113B2 (en) | 2012-07-09 | 2017-06-06 | Siluria Technologies, Inc. | Natural gas processing and systems |
US9701597B2 (en) | 2014-01-09 | 2017-07-11 | Siluria Technologies, Inc. | Oxidative coupling of methane implementations for olefin production |
US9944573B2 (en) | 2016-04-13 | 2018-04-17 | Siluria Technologies, Inc. | Oxidative coupling of methane for olefin production |
WO2018128983A1 (en) * | 2017-01-06 | 2018-07-12 | Sabic Global Technologies, B.V. | An integrated process utilizing methane oxidative conversion heat for ethylene and methanol production |
US10047020B2 (en) | 2013-11-27 | 2018-08-14 | Siluria Technologies, Inc. | Reactors and systems for oxidative coupling of methane |
US10301977B2 (en) | 2015-08-24 | 2019-05-28 | Saudi Arabian Oil Company | Kalina cycle based conversion of gas processing plant waste heat into power |
US10329215B2 (en) | 2017-10-24 | 2019-06-25 | Sabic Global Technologies, B.V. | Process for converting a natural gas feedstock with inert content to chemical intermediates |
US20190193027A1 (en) * | 2017-10-26 | 2019-06-27 | Marc Privitera | Mobile Extraction Array with brine constituent separation, purification and concentration |
US10377682B2 (en) | 2014-01-09 | 2019-08-13 | Siluria Technologies, Inc. | Reactors and systems for oxidative coupling of methane |
US10787398B2 (en) | 2012-12-07 | 2020-09-29 | Lummus Technology Llc | Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products |
US10793490B2 (en) | 2015-03-17 | 2020-10-06 | Lummus Technology Llc | Oxidative coupling of methane methods and systems |
US10836689B2 (en) | 2017-07-07 | 2020-11-17 | Lummus Technology Llc | Systems and methods for the oxidative coupling of methane |
US10865165B2 (en) | 2015-06-16 | 2020-12-15 | Lummus Technology Llc | Ethylene-to-liquids systems and methods |
US10870810B2 (en) * | 2017-07-20 | 2020-12-22 | Proteum Energy, Llc | Method and system for converting associated gas |
US10894751B2 (en) | 2014-01-08 | 2021-01-19 | Lummus Technology Llc | Ethylene-to-liquids systems and methods |
US10960343B2 (en) | 2016-12-19 | 2021-03-30 | Lummus Technology Llc | Methods and systems for performing chemical separations |
US11001542B2 (en) | 2017-05-23 | 2021-05-11 | Lummus Technology Llc | Integration of oxidative coupling of methane processes |
US11001543B2 (en) | 2015-10-16 | 2021-05-11 | Lummus Technology Llc | Separation methods and systems for oxidative coupling of methane |
US20210172076A1 (en) * | 2017-02-27 | 2021-06-10 | Honeywell International Inc. | Electrochemical carbon dioxide converter and liquid regenerator |
CN112973584A (en) * | 2021-02-07 | 2021-06-18 | 中国科学院过程工程研究所 | Fluidized bed reaction device and application thereof |
US11085124B2 (en) * | 2018-03-20 | 2021-08-10 | Kabushiki Kaisha Toshiba | Electrochemical reaction device |
US11186529B2 (en) | 2015-04-01 | 2021-11-30 | Lummus Technology Llc | Advanced oxidative coupling of methane |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107100808B (en) * | 2017-05-27 | 2019-06-14 | 集美大学 | Solar energy supercritical carbon dioxide circulating generation couples water vapour electrolytic hydrogen production system |
CA3123243A1 (en) | 2018-12-14 | 2020-06-18 | Enhanced Energy Group LLC | Improved semi-closed cycle with turbo membrane o2 source |
WO2021250002A2 (en) | 2020-06-10 | 2021-12-16 | Total Se | Thermal oxidative coupling of methane process using renewable energy with possible co-production of hydrogen |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5015799A (en) * | 1989-07-06 | 1991-05-14 | Amoco Corporation | Oxidative coupling process for converting methane and/or natural gas to more transportable products |
US6096934A (en) * | 1998-12-09 | 2000-08-01 | Uop Llc | Oxidative coupling of methane with carbon conservation |
US7687048B1 (en) * | 2006-09-28 | 2010-03-30 | Uop Llc | Amine treatment in light olefin processing |
Family Cites Families (531)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR649429A (en) | 1927-01-28 | 1928-12-21 | Ig Farbenindustrie Ag | Process for the continuous separation of liquid mixtures |
US2324172A (en) | 1940-10-31 | 1943-07-13 | Standard Oil Co | Processing well fluids |
US2486980A (en) | 1946-02-01 | 1949-11-01 | Phillips Petroleum Co | Catalytic vapor phase hydration of ethylene |
US2577701A (en) | 1946-05-20 | 1951-12-04 | Shell Dev | Fractionation process |
US2643216A (en) | 1950-08-10 | 1953-06-23 | Phillips Petroleum Co | Device and process for converting hydrocarbons |
US2579601A (en) | 1950-08-16 | 1951-12-25 | Shell Dev | Olefin hydration process |
US2621216A (en) | 1950-08-17 | 1952-12-09 | Shell Dev | Production of ethylene |
GB733336A (en) | 1951-06-20 | 1955-07-13 | Ici Ltd | Improvements in and relating to the production of lower alkenes |
US2673221A (en) | 1952-01-18 | 1954-03-23 | Eastman Kodak Co | Process of producing ethyl alcohol by hydration of ethylene |
US2943125A (en) | 1954-08-07 | 1960-06-28 | Ziegler | Production of dimers and low molecular polymerization products from ethylene |
US2880592A (en) | 1955-11-10 | 1959-04-07 | Phillips Petroleum Co | Demethanization of cracked gases |
US2906795A (en) | 1957-07-31 | 1959-09-29 | Texaco Inc | Recovery and utilization of normally gaseous olefins |
US2926751A (en) | 1958-09-22 | 1960-03-01 | Fluor Corp | Organic carbonate process for carbon dioxide |
US3094569A (en) | 1958-10-20 | 1963-06-18 | Union Carbide Corp | Adsorptive separation process |
US3128317A (en) | 1961-01-13 | 1964-04-07 | Texaco Inc | Selective hydrogenation of acetylene in ethylene with a zeolitic catalyst |
GB1016049A (en) | 1964-04-10 | 1966-01-05 | Lummus Co | A process for the liquefaction of a gas |
US3325556A (en) | 1964-05-18 | 1967-06-13 | Universal Oil Prod Co | Selective hydrogenation of acetylene in a mixture of acetylene and other unsaturated hydrocarbons |
US3459678A (en) | 1966-01-03 | 1969-08-05 | Eastman Kodak Co | Olefin hydration catalyst |
US3516262A (en) | 1967-05-01 | 1970-06-23 | Mc Donnell Douglas Corp | Separation of gas mixtures such as methane and nitrogen mixtures |
DE1551612B1 (en) | 1967-12-27 | 1970-06-18 | Messer Griesheim Gmbh | Liquefaction process for gas mixtures by means of fractional condensation |
US3584071A (en) | 1968-03-01 | 1971-06-08 | Gulf Research Development Co | Telomerization of ethylene |
US3686334A (en) | 1969-01-13 | 1972-08-22 | Exxon Research Engineering Co | Direct hydration of ethylene to ethanol |
DE1905517B2 (en) | 1969-02-05 | 1977-01-27 | Hoechst Ag, 6000 Frankfurt | DEVICE FOR THE PRODUCTION OF 1,2-DICHLORAETHANE |
GB1312974A (en) | 1969-05-29 | 1973-04-11 | Toyo Soda Mfg Co Ltd | Process and catalyst for dimerization of alpha-olefins |
JPS4823056B1 (en) | 1969-08-20 | 1973-07-11 | ||
US3702886A (en) | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
US3709669A (en) | 1970-12-28 | 1973-01-09 | Texaco Development Corp | Methane production |
US3761540A (en) | 1971-04-30 | 1973-09-25 | Phillips Petroleum Co | Alkylation of isoparaffin with ethylene and a higher olefin |
US3754052A (en) | 1972-01-14 | 1973-08-21 | Sun Research Development | Ethylene alkylation resulting in alkylate with high proportion of 2,3-dimethylbutane |
US3862257A (en) | 1972-04-17 | 1975-01-21 | Exxon Research Engineering Co | Modified ziegler catalyst for alpha olefin wax synthesis |
US3900526A (en) | 1972-05-02 | 1975-08-19 | Phillips Petroleum Co | Selective removal of 1,2 polyenes and acetylenic compounds from conjugated-diene feed using a nickel, iron or cobalt arsenide catalyst |
US3751878A (en) | 1972-10-20 | 1973-08-14 | Union Carbide Corp | Bulk separation of carbon dioxide from natural gas |
US3966644A (en) | 1973-08-03 | 1976-06-29 | American Cyanamid Company | Shaped catalyst particles |
US4012452A (en) | 1973-12-17 | 1977-03-15 | National Distillers And Chemical Corporation | Olefin hydration process |
DE2429770C3 (en) | 1974-06-21 | 1981-04-16 | Deutsche Texaco Ag, 2000 Hamburg | Process for the production of lower alcohols by direct catalytic hydration of lower olefins |
US4090949A (en) | 1974-07-31 | 1978-05-23 | Mobil Oil Corportion | Upgrading of olefinic gasoline with hydrogen contributors |
US3931349A (en) | 1974-09-23 | 1976-01-06 | Mobil Oil Corporation | Conversion of methanol to gasoline components |
DE2540257B2 (en) | 1975-09-10 | 1977-06-02 | Hoechst Ag, 6000 Frankfurt | PROCESS FOR THE PRODUCTION OF 1,2-DICHLORAETHANE |
US4115086A (en) | 1975-12-22 | 1978-09-19 | Fluor Corporation | Recovery of light hydrocarbons from refinery gas |
SU681032A1 (en) | 1976-02-23 | 1979-08-25 | Грозненский филиал Охтинского научно-производственного объединения "Пластполимер" | Process for the preparation of dimers and codimers of alpha-olefins |
GB1572168A (en) | 1976-04-06 | 1980-07-23 | Ici Ltd | Hydrogenation catalyst and process |
US4132745A (en) | 1976-06-25 | 1979-01-02 | Institut Francais Du Petrole | Process for isomerizing 1-butene to 2-butene |
US4140504A (en) | 1976-08-09 | 1979-02-20 | The Ortloff Corporation | Hydrocarbon gas processing |
US4107224A (en) | 1977-02-11 | 1978-08-15 | Mobil Oil Corporation | Manufacture of ethyl benzene |
US4367353A (en) | 1977-12-21 | 1983-01-04 | Imperial Chemical Industries Limited | Catalytic hydrogenation and purification |
US4232177A (en) | 1979-02-21 | 1980-11-04 | Chemical Research & Licensing Company | Catalytic distillation process |
JPS5918374B2 (en) | 1978-11-14 | 1984-04-26 | 三井東圧化学株式会社 | Selective method for producing ortho-alkylated phenols using anisole as a starting material |
USRE31010E (en) | 1979-04-09 | 1982-08-10 | Chem Systems Inc. | Preparation of carboxylic acid esters with BF3 complex catalyst |
US4211885A (en) | 1979-05-15 | 1980-07-08 | Phillips Petroleum Company | High octane gasoline components from catalytic cracking gasoline, propylene, and isobutane by disproportionation, cleavage and alkylation |
FR2458524A1 (en) | 1979-06-08 | 1981-01-02 | Inst Francais Du Petrole | METHOD FOR SELECTIVE HYDROGENATION OF A FRACTION OF HYDROCARBONS CONTAINING 2 OR 3 CARBON ATOMS BY MOLECULE |
EP0029321B1 (en) | 1979-11-20 | 1983-09-21 | Imperial Chemical Industries Plc | Hydrogenation catalyst material, a precursor thereto, method of making the latter and use of the catalyst for selective hydrogenation |
US4311851A (en) | 1979-12-19 | 1982-01-19 | Chem Systems Inc. | Preparation of carboxylic acid esters with BF3 -alcohol complex catalyst |
US4314090A (en) | 1980-08-18 | 1982-02-02 | The Dow Chemical Company | Linear alpha olefin production |
US4418045A (en) | 1980-09-19 | 1983-11-29 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method for disposal of waste gas and apparatus therefor |
US4328130A (en) | 1980-10-22 | 1982-05-04 | Chevron Research Company | Shaped channeled catalyst |
US4394303A (en) | 1981-05-12 | 1983-07-19 | Chevron Research Company | Large pore shaped hydroprocessing catalysts |
US4370156A (en) | 1981-05-29 | 1983-01-25 | Standard Oil Company (Indiana) | Process for separating relatively pure fractions of methane and carbon dioxide from gas mixtures |
US4469905A (en) | 1981-11-04 | 1984-09-04 | Union Oil Company Of California | Process for producing and extracting C2 to C6 alcohols |
US4439213A (en) | 1981-12-30 | 1984-03-27 | The C. M. Kemp Manufacturing Co. | Nitrogen generation system |
US4523049A (en) | 1984-04-16 | 1985-06-11 | Atlantic Richfield Company | Methane conversion process |
US4629718A (en) | 1982-08-30 | 1986-12-16 | Atlantic Richfield Company | Alkali promoted manganese oxide compositions containing silica and/or alkaline earth oxides |
US4567307A (en) | 1982-08-30 | 1986-01-28 | Atlantic Richfield Company | Two-step methane conversion process |
US4554395A (en) | 1982-08-30 | 1985-11-19 | Atlantic Richfield Company | Methane conversion |
DK147705C (en) | 1982-09-07 | 1985-05-13 | Haldor Topsoe As | METHOD FOR MANUFACTURING CARBON HYDRADES FROM SYNTHESE GAS |
US4552644A (en) | 1982-09-30 | 1985-11-12 | Stone & Webster Engineering Corporation | Duocracking process for the production of olefins from both heavy and light hydrocarbons |
DE3406751A1 (en) | 1982-10-07 | 1985-08-29 | Baerns, Manfred, Prof. Dr., 4630 Bochum | Process for the oxidative coupling of methane to C2-hydrocarbons, process for the preparation of the catalysts and arrangements for carrying out the oxidative coupling |
US4765883A (en) | 1982-10-20 | 1988-08-23 | Stone & Webster Engineering Corporation | Process for the production of aromatics benzene, toluene, xylene (BTX) from heavy hydrocarbons |
US4440956A (en) | 1982-10-25 | 1984-04-03 | The Dow Chemical Company | Selective hydrogenation of acetylenes in the presence of butadiene and catalyst used in the hydrogenation |
US5003124A (en) | 1982-11-17 | 1991-03-26 | Chemical Research & Licensing Company | Oligomerization process |
US4433185A (en) | 1983-04-04 | 1984-02-21 | Mobil Oil Corporation | Two stage system for catalytic conversion of olefins with distillate and gasoline modes |
US4465887A (en) | 1983-06-27 | 1984-08-14 | Standard Oil Company (Indiana) | Process for producing butylene polymers having molecular weights in the range of from about 400 to 5000 molecular weight |
US4777313A (en) | 1983-08-12 | 1988-10-11 | Atlantic Richfield Company | Boron-promoted reducible metal oxides and methods of their use |
US4519824A (en) | 1983-11-07 | 1985-05-28 | The Randall Corporation | Hydrocarbon gas separation |
US4511747A (en) | 1984-02-01 | 1985-04-16 | Mobil Oil Corporation | Light olefin conversion to heavier hydrocarbons with sorption recovery of unreacted olefin vapor |
US4551438A (en) | 1984-04-11 | 1985-11-05 | Chevron Research Company | Oligomerization of liquid olefin over a nickel-containing silicaceous crystalline molecular sieve and hydrocarbyl aluminum halide |
US4489215A (en) | 1984-04-16 | 1984-12-18 | Atlantic Richfield Company | Methane conversion |
DE3587895T2 (en) | 1984-05-03 | 1994-12-01 | Mobil Oil Corp | Catalytic dewaxing of light and heavy oils in two parallel reactors. |
DE3575550D1 (en) | 1984-10-02 | 1990-03-01 | Standard Oil Co Ohio | PROCESS FOR IMPLEMENTING LOW MOLECULAR WEIGHT ALKANS. |
US5055627A (en) | 1985-01-07 | 1991-10-08 | Chemical Research & Licensing Company | Process for the preparation of cumene |
US4751336A (en) | 1985-02-28 | 1988-06-14 | Amoco Corporation | Conversion of a lower alkane |
US4754093A (en) | 1985-02-28 | 1988-06-28 | Amoco Corporation | Conversion of a lower alkane |
US4754091A (en) | 1985-02-28 | 1988-06-28 | Amoco Corporation | Conversion of a lower alkane |
US4814539A (en) | 1985-02-28 | 1989-03-21 | Amoco Corporation | Conversion of a lower alkane |
US4895823A (en) | 1985-03-19 | 1990-01-23 | Phillips Petroleum Company | Composition of matter for oxidative conversion of organic compounds |
US5959170A (en) | 1985-05-24 | 1999-09-28 | Atlantic Richfield Company | Methane conversion process |
NZ216388A (en) | 1985-06-14 | 1990-01-29 | Grace W R & Co | Catalytic conversion of methane into hydrogen and higher hydrocarbons |
US4717782A (en) | 1985-09-13 | 1988-01-05 | Mobil Oil Corporation | Catalytic process for oligomerizing ethene |
US4891457A (en) | 1985-09-13 | 1990-01-02 | Hartley Owen | Multistage process for converting olefins to heavier hydrocarbons |
US5080872A (en) | 1985-09-26 | 1992-01-14 | Amoco Corporation | Temperature regulating reactor apparatus and method |
DE3534530A1 (en) | 1985-09-27 | 1987-04-09 | Manfred Prof Dr Baerns | Continuous process for the oxidative coupling of methane to C2+ hydrocarbons in the presence of catalysts |
US4673664A (en) | 1985-10-07 | 1987-06-16 | American Cyanamid Company | Shape for extruded catalyst support particles and catalysts |
GB8600260D0 (en) | 1986-01-07 | 1986-02-12 | British Petroleum Co Plc | Chemical process |
DE3770647D1 (en) | 1986-01-09 | 1991-07-18 | Light Oil Utilization Res Ass | PRODUCTION OF A MIXED STOCK FOR HIGH OCTANE GASOLINE. |
GB2191212B (en) | 1986-06-05 | 1990-02-07 | British Petroleum Co Plc | Integrated process for the production of liquid hydrocarbons from methane |
US5473027A (en) | 1986-06-20 | 1995-12-05 | Chevron Chemical Company | Production of blow molding polyethylene resin |
FR2600556A1 (en) | 1986-06-27 | 1987-12-31 | Rhone Poulenc Chim Base | New catalyst based on nickel and/or cobalt, its preparation and its use for the production of methane |
US4822944A (en) | 1986-07-11 | 1989-04-18 | The Standard Oil Company | Energy efficient process for upgrading light hydrocarbons and novel oxidative coupling catalysts |
US5012028A (en) | 1986-07-11 | 1991-04-30 | The Standard Oil Company | Process for upgrading light hydrocarbons using oxidative coupling and pyrolysis |
US4801762A (en) | 1987-02-13 | 1989-01-31 | Atlantic Richfield Company | Methane conversion process |
SE460642B (en) | 1987-03-06 | 1989-11-06 | Flaekt Ab | PROCEDURES FOR ABSORPING GAS GAS COMPONENTS FROM FORECURATED SMOKE GASES |
US5591315A (en) | 1987-03-13 | 1997-01-07 | The Standard Oil Company | Solid-component membranes electrochemical reactor components electrochemical reactors use of membranes reactor components and reactor for oxidation reactions |
US4822477A (en) | 1987-06-11 | 1989-04-18 | Mobil Oil Corporation | Integrated process for gasoline production |
US4769047A (en) | 1987-06-29 | 1988-09-06 | Shell Oil Company | Process for the production of ethylene oxide |
FR2618786B1 (en) | 1987-07-31 | 1989-12-01 | Bp Chimie Sa | PROCESS FOR THE POLYMERIZATION OF GASEOUS OLEFINS IN A FLUIDIZED BED REACTOR |
EP0303438A3 (en) | 1987-08-14 | 1989-12-27 | DAVY McKEE CORPORATION | Production of synthesis gas from hydrocarbonaceous feedstock |
US4865820A (en) | 1987-08-14 | 1989-09-12 | Davy Mckee Corporation | Gas mixer and distributor for reactor |
US4855524A (en) | 1987-11-10 | 1989-08-08 | Mobil Oil Corporation | Process for combining the operation of oligomerization reactors containing a zeolite oligomerization catalyst |
US4831203A (en) | 1987-12-16 | 1989-05-16 | Mobil Oil Corporation | Integrated production of gasoline from light olefins in a fluid cracking process plant |
US4855528A (en) | 1988-02-05 | 1989-08-08 | Exxon Chemical Patents Inc. | Catalysts and process for oligomerization of olefins with nickel-containing zeolite catalysts |
US4950311A (en) | 1988-03-07 | 1990-08-21 | White Jr Donald H | Heaterless adsorption system for combined purification and fractionation of air |
FR2629451B1 (en) | 1988-04-05 | 1991-07-12 | Inst Francais Du Petrole | PROCESS FOR PRODUCING OLEFINS FROM NATURAL GAS |
US4966874A (en) | 1988-05-18 | 1990-10-30 | Exxon Chemical Patents Inc. | Process for preparing linear alpha-olefins using zirconium adducts as catalysts |
US4849571A (en) | 1988-05-20 | 1989-07-18 | Atlantic Richfield Company | Hydrocarbon production |
US4835331A (en) | 1988-05-23 | 1989-05-30 | Uop | Process for the oligomerization of olefinic hydrocarbons |
US4962261A (en) | 1988-06-20 | 1990-10-09 | Uop | Process for upgrading methane to higher carbon number hydrocarbons |
US5024984A (en) | 1988-08-17 | 1991-06-18 | Amoco Corporation | Catalysts for the oxidative conversion of methane to higher hydrocarbons |
US4939311A (en) | 1988-08-17 | 1990-07-03 | Amoco Corporation | Catalysts for the oxidative conversion of methane to higher hydrocarbons |
US5034565A (en) | 1988-09-26 | 1991-07-23 | Mobil Oil Corporation | Production of gasoline from light olefins in a fluidized catalyst reactor system |
US4889545A (en) | 1988-11-21 | 1989-12-26 | Elcor Corporation | Hydrocarbon gas processing |
US4935568A (en) | 1988-12-05 | 1990-06-19 | Mobil Oil Corporation | Multistage process for oxygenate conversion to hydrocarbons |
FR2641531B1 (en) | 1989-01-06 | 1991-05-03 | Inst Francais Du Petrole | PROCESS FOR PRODUCING OLEFINS FROM NATURAL GAS |
US4900347A (en) | 1989-04-05 | 1990-02-13 | Mobil Corporation | Cryogenic separation of gaseous mixtures |
US5118898A (en) | 1989-06-30 | 1992-06-02 | The Broken Hill Proprietary Company Limited | Process for the production of olefins by combined methane oxidative coupling/hydrocarbon pyrolysis |
NZ234289A (en) | 1989-06-30 | 1992-03-26 | Broken Hill Pty Co Ltd | Catalyst for oxidative coupling of methane, containing clay and an oxide or carbonate of an alkaline earth metal |
US5004852A (en) | 1989-08-24 | 1991-04-02 | Mobil Oil Corp. | Two-stage process for conversion of olefins to high octane gasoline |
DE3930533C1 (en) | 1989-09-13 | 1991-05-08 | Degussa Ag, 6000 Frankfurt, De | |
CA2041874C (en) | 1990-01-09 | 1999-04-06 | Richard T. Maurer | Separation of ethane from methane by pressure swing adsorption |
US5041405A (en) | 1990-02-22 | 1991-08-20 | The Texas A & M University System | Lithium/magnesium oxide catalyst and method of making |
DE4039960A1 (en) | 1990-03-23 | 1991-09-26 | Hoechst Ag | 1,2-di:chloroethane prodn. - by reaction of chlorine and ethylene in di:chloro-ethane circulating in specified reactor-condenser system |
US5057468A (en) | 1990-05-21 | 1991-10-15 | Chemical Research & Licensing Company | Catalytic distillation structure |
US5057638A (en) | 1990-06-22 | 1991-10-15 | Chevron Research And Technology Company | Process for making 1-hexene from 1-butene |
US5263998A (en) | 1990-08-22 | 1993-11-23 | Imperial Chemical Industries Plc | Catalysts |
GB9018409D0 (en) | 1990-08-22 | 1990-10-03 | Ici Plc | Catalysts |
US5168090A (en) | 1990-10-04 | 1992-12-01 | Monsanto Company | Shaped oxidation catalyst structures for the production of maleic anhydride |
US5132472A (en) | 1990-10-17 | 1992-07-21 | Sun Refining And Marketing Company | Catalytic oxidation of alkanes |
US5414157A (en) | 1990-10-17 | 1995-05-09 | Sun Company, Inc. (R&M) | Catalytic oxidation of alkanes |
FR2669921B1 (en) | 1990-12-04 | 1995-07-21 | Inst Francais Du Petrole | PROCESS FOR THE CONVERSION OF ETHYLENE INTO LIGHT ALPHA OLEFINS. |
GB9028034D0 (en) | 1990-12-24 | 1991-02-13 | Isis Innovation | Improved processes for the conversion of methane to synthesis gas |
US5240474A (en) | 1991-01-23 | 1993-08-31 | Air Products And Chemicals, Inc. | Air separation by pressure swing adsorption with a high capacity carbon molecular sieve |
US5449850A (en) | 1991-03-12 | 1995-09-12 | Exxon Chemical Patents Inc. | Process for oligomerizing C3 and higher olefins using zirconium adducts as catalysts (CS-467) |
JPH07502049A (en) | 1991-05-02 | 1995-03-02 | エクソン リサーチ アンド エンジニアリング カンパニー | Catalytic cracking method and equipment |
US5179056A (en) | 1991-05-06 | 1993-01-12 | Union Carbide Chemicals & Plastics Technology Corporation | Production of alkenyl alkanoate catalysts |
FR2676748B1 (en) | 1991-05-21 | 1993-08-13 | Inst Francais Du Petrole | PROCESS FOR PRODUCING LIQUID HYDROCARBONS FROM NATURAL GAS, IN THE PRESENCE OF A ZEOLITE AND GALLIUM-BASED CATALYST. |
ES2125902T3 (en) | 1991-07-08 | 1999-03-16 | Huntsman Spec Chem Corp | HIGH PRODUCTIVITY PROCEDURE FOR THE PRODUCTION OF MALEIC ANHYDRIDE. |
US5196634A (en) | 1991-10-11 | 1993-03-23 | Amoco Corporation | Hydrocarbon conversion |
US5198596A (en) | 1991-10-11 | 1993-03-30 | Amoco Corporation | Hydrocarbon conversion |
US5245109A (en) | 1991-10-11 | 1993-09-14 | Amoco Corporation | Hydrocarbon conversion |
US5811618A (en) | 1991-10-16 | 1998-09-22 | Amoco Corporation | Ethylene trimerization |
US5254781A (en) | 1991-12-31 | 1993-10-19 | Amoco Corporation | Olefins process which combines hydrocarbon cracking with coupling methane |
US5599510A (en) | 1991-12-31 | 1997-02-04 | Amoco Corporation | Catalytic wall reactors and use of catalytic wall reactors for methane coupling and hydrocarbon cracking reactions |
US5395981A (en) | 1992-06-22 | 1995-03-07 | Uop | Hydrocarbon conversion by catalytic distillation |
US5849973A (en) | 1992-07-08 | 1998-12-15 | Gas Research Institute | Oxidative coupling catalyst |
FR2693455B1 (en) | 1992-07-09 | 1994-09-30 | Inst Francais Du Petrole | Process for the production of light alpha olefins by oligomerization of ethylene. |
US5336825A (en) | 1992-07-10 | 1994-08-09 | Council Of Scientific & Industrial Research | Integrated two step process for conversion of methane to liquid hydrocarbons of gasoline range |
US5306854A (en) | 1992-07-10 | 1994-04-26 | Council Of Scientific & Industrial Research | Two step process for production of liquid hydrocarbons from natural gas |
IT1255710B (en) | 1992-10-01 | 1995-11-10 | Snam Progetti | INTEGRATED PROCEDURE TO PRODUCE OLEFINS FROM GASEOUS MIXTURES CONTAINING METHANE |
IT1256156B (en) | 1992-10-06 | 1995-11-29 | Montecatini Tecnologie Srl | GRANULES CATALYST PARTICULARLY FOR THE OXIDATIVE DEHYDROGENATION OF METHANOL TO FORMALDEHYDE |
US5861353A (en) | 1992-10-06 | 1999-01-19 | Montecatini Tecnologie S.R.L. | Catalyst in granular form for 1,2-dichloroethane synthesis |
IT1255945B (en) | 1992-10-30 | 1995-11-17 | Eniricerche Spa | PROCEDURE AND CATALYST FOR THE TRANSFORMATION OF METHANE INTO HIGHER HYDROCARBON PRODUCTS. |
US5817904A (en) | 1992-12-11 | 1998-10-06 | Repsol Petroleo S.A. | Method for the conversion of methane into longer chain hydrocarbons |
US5763722A (en) | 1992-12-11 | 1998-06-09 | Repsol Petroleo S.A. | Method for the methane chemical conversion into C2 hydrocarbons |
KR960003790B1 (en) | 1992-12-31 | 1996-03-22 | 한국과학기술원 | Modified magnesium oxide catalyst and the process for manufacture thereof |
US5414170A (en) | 1993-05-12 | 1995-05-09 | Stone & Webster Engineering Corporation | Mixed phase front end C2 acetylene hydrogenation |
EP0634211A1 (en) | 1993-07-16 | 1995-01-18 | Texaco Development Corporation | Oxidative coupling of methane on manganese oxide octahedral molecular sieve catalyst |
FR2711136B1 (en) | 1993-10-15 | 1996-02-02 | Inst Francais Du Petrole | Process for producing at least one alkyl tert-butyl ether from natural gas. |
US5659090A (en) | 1993-10-15 | 1997-08-19 | Institut Francais Du Petrole | Steps in a process for the production of at least one alkyl tertiobutyl ether from natural gas |
DE4338414C1 (en) | 1993-11-10 | 1995-03-16 | Linde Ag | Process for the preparation of linear olefins |
DE4338416C1 (en) | 1993-11-10 | 1995-04-27 | Linde Ag | Soluble catalyst for the preparation of linear alpha -olefins by oligomerisation of ethylene |
US6355093B1 (en) | 1993-12-08 | 2002-03-12 | Eltron Research, Inc | Two component-three dimensional catalysis |
US5510306A (en) | 1993-12-29 | 1996-04-23 | Shell Oil Company | Process for isomerizing linear olefins to isoolefins |
FR2715154B1 (en) | 1994-01-14 | 1996-04-05 | Inst Francais Du Petrole | Process for the production of light alpha olefins of improved purity by oligomerization of ethylene. |
US5462583A (en) | 1994-03-04 | 1995-10-31 | Advanced Extraction Technologies, Inc. | Absorption process without external solvent |
US5714657A (en) | 1994-03-11 | 1998-02-03 | Devries; Louis | Natural gas conversion to higher hydrocarbons |
US5712217A (en) | 1995-06-05 | 1998-01-27 | Council Of Scientific & Industrial Research | Supported catalyst with mixed lanthanum and other rare earth oxides |
FR2721837B1 (en) | 1994-07-01 | 1996-08-30 | Inst Francais Du Petrole | HIGH TEMPERATURE RESISTANT OXIDATION CATALYST, PREPARATION METHOD THEREOF, AND COMBUSTION METHOD USING SUCH CATALYST |
EP0722822B1 (en) | 1994-07-15 | 2002-04-10 | Idemitsu Petrochemical Co., Ltd. | Highly rigid polypropylene resin and blow molding product made therefrom |
WO1996010548A1 (en) | 1994-10-03 | 1996-04-11 | Sanyo Petrochemical Co., Ltd. | Process for producing aromatic hydrocarbon |
US5568737A (en) | 1994-11-10 | 1996-10-29 | Elcor Corporation | Hydrocarbon gas processing |
JP2925963B2 (en) | 1994-12-05 | 1999-07-28 | 石油公団 | Method and apparatus for oxidative coupling of methane |
GB9424547D0 (en) | 1994-12-06 | 1995-01-25 | Bp Chem Int Ltd | Ethylene conversion process |
GB9502342D0 (en) | 1995-02-07 | 1995-03-29 | Exxon Chemical Patents Inc | Hydrocarbon treatment and catalyst therefor |
US7576296B2 (en) | 1995-03-14 | 2009-08-18 | Battelle Energy Alliance, Llc | Thermal synthesis apparatus |
US6821500B2 (en) | 1995-03-14 | 2004-11-23 | Bechtel Bwxt Idaho, Llc | Thermal synthesis apparatus and process |
US5749937A (en) | 1995-03-14 | 1998-05-12 | Lockheed Idaho Technologies Company | Fast quench reactor and method |
US6303092B1 (en) | 1995-04-10 | 2001-10-16 | Air Products And Chemicals, Inc. | Process for operating equilibrium controlled reactions |
JP2906086B2 (en) | 1995-04-27 | 1999-06-14 | エービービー ルーマス グローバル インコーポレイテッド | Conversion of olefinic hydrocarbons using spent FCC catalysts |
US5679241A (en) | 1995-05-17 | 1997-10-21 | Abb Lummus Global Inc. | Olefin plant recovery system employing catalytic distillation |
US5819555A (en) | 1995-09-08 | 1998-10-13 | Engdahl; Gerald | Removal of carbon dioxide from a feed stream by carbon dioxide solids separation |
DE19533484A1 (en) | 1995-09-12 | 1997-03-13 | Basf Ag | Monomodal and polymodal catalyst supports and catalysts with narrow pore size distributions and their manufacturing processes |
DE19533486A1 (en) | 1995-09-12 | 1997-03-13 | Basf Ag | Monomodal and polymodal catalyst supports and catalysts with narrow pore size distributions and their manufacturing processes |
US5656064A (en) | 1995-10-04 | 1997-08-12 | Air Products And Chemicals, Inc. | Base treated alumina in pressure swing adsorption |
DE19601750A1 (en) | 1996-01-19 | 1997-07-24 | Basf Ag | Process for the oxidation and oxydehydrogenation of hydrocarbons in the fluidized bed |
US5897945A (en) | 1996-02-26 | 1999-04-27 | President And Fellows Of Harvard College | Metal oxide nanorods |
FR2748020B1 (en) | 1996-04-26 | 1998-06-26 | Inst Francais Du Petrole | IMPROVED PROCESS FOR CONVERTING ETHYLENE INTO BUTENE-1 WITH THE USE OF ADDITIVES BASED ON POLYETHYLENEGLYCOLS AND THEIR DERIVATIVES |
FR2748018B1 (en) | 1996-04-26 | 1998-06-26 | Inst Francais Du Petrole | IMPROVED PROCESS FOR THE CONVERSION OF ETHYLENE TO LIGHT ALPHA OLEFINS WITH THE USE OF ADDITIVES BASED ON QUATERNARY AMMONIUM SALTS |
US5780003A (en) | 1996-08-23 | 1998-07-14 | Uop Llc | Crystalline manganese phosphate compositions |
US5877363A (en) | 1996-09-23 | 1999-03-02 | Catalytic Distillation Technologies | Process for concurrent selective hydrogenation of acetylenes and 1,2 butadine in hydrocarbon streams |
US6486373B1 (en) | 1996-11-05 | 2002-11-26 | Mobil Oil Corporation | Shape selective zeolite catalyst and its use in aromatic compound conversion |
GB9626324D0 (en) | 1996-12-19 | 1997-02-05 | Bp Chem Int Ltd | Process |
FR2759922B1 (en) | 1997-02-25 | 1999-05-07 | Inst Francais Du Petrole | IMPROVED CATALYTIC COMPOSITION FOR THE CONVERSION OF ETHYLENE TO LIGHT ALPHA OLEFINS |
US5936135A (en) | 1997-05-02 | 1999-08-10 | Council Of Scientific & Industrial Research | Process for the preparation of hydrocarbons |
US5856257A (en) | 1997-05-16 | 1999-01-05 | Phillips Petroleum Company | Olefin production |
GB9712165D0 (en) | 1997-06-11 | 1997-08-13 | Air Prod & Chem | Processes and apparatus for producing a gaseous product |
FR2764524B1 (en) | 1997-06-17 | 1999-07-16 | Inst Francais Du Petrole | CATALYTIC COMPOSITION AND PROCESS FOR THE OLIGOMERIZATION OF ETHYLENE, IN PARTICULAR BUTENE-1 AND / OR HEXENE-1 |
US6153149A (en) | 1997-08-06 | 2000-11-28 | The Trustees Of Princeton University | Adaptive feedback control flow reactor |
AU734708B2 (en) | 1997-10-08 | 2001-06-21 | Shell Internationale Research Maatschappij B.V. | Flameless combustor process heater |
US20020182124A1 (en) | 1997-10-14 | 2002-12-05 | William M. Woodard | Olefin production process |
US6048472A (en) | 1997-12-23 | 2000-04-11 | Air Products And Chemicals, Inc. | Production of synthesis gas by mixed conducting membranes |
DE19809532C1 (en) | 1998-03-05 | 1999-04-15 | Karlsruhe Forschzent | Selective electrochemical carboxylation of terminal alkyne to 2-alkynoic acid |
US6114400A (en) | 1998-09-21 | 2000-09-05 | Air Products And Chemicals, Inc. | Synthesis gas production by mixed conducting membranes with integrated conversion into liquid products |
US6379586B1 (en) | 1998-10-20 | 2002-04-30 | The Boc Group, Inc. | Hydrocarbon partial oxidation process |
US6602920B2 (en) | 1998-11-25 | 2003-08-05 | The Texas A&M University System | Method for converting natural gas to liquid hydrocarbons |
DE19910964A1 (en) | 1999-03-12 | 2000-09-21 | Krupp Uhde Gmbh | Process for the production of ethylene dichloride (EDC) |
EP1063013B1 (en) | 1999-06-24 | 2005-10-12 | ENI S.p.A. | Catalytic composition for the aromatization of hydrocarbons |
CN1100028C (en) | 1999-07-22 | 2003-01-29 | 中国石油化工集团公司 | Isoalkane and alkylation method of olefine |
US6146549A (en) | 1999-08-04 | 2000-11-14 | Eltron Research, Inc. | Ceramic membranes for catalytic membrane reactors with high ionic conductivities and low expansion properties |
US7663011B2 (en) | 1999-09-07 | 2010-02-16 | Lummus Technology Inc. | Mesoporous material with active metals |
US6303841B1 (en) | 1999-10-04 | 2001-10-16 | Uop Llc | Process for producing ethylene |
DE19959873A1 (en) | 1999-12-10 | 2001-06-13 | Basf Ag | Oxidation reactions using mixed conducting oxygen selective membranes |
FR2802833B1 (en) | 1999-12-24 | 2002-05-10 | Inst Francais Du Petrole | CATALYTIC COMPOSITION AND PROCESS FOR THE OLIGOMERIZATION OF ETHYLENE, PARTICULARLY HEXENE-1 |
US6380451B1 (en) | 1999-12-29 | 2002-04-30 | Phillips Petroleum Company | Methods for restoring the heat transfer coefficient of an oligomerization reactor |
US6726850B1 (en) | 2000-01-14 | 2004-04-27 | Sebastian C. Reyes | Catalytic partial oxidation using staged oxygen addition |
IT1317757B1 (en) | 2000-02-03 | 2003-07-15 | Enitecnologie Spa | METHOD FOR THE PREPARATION OF HYDROGENATED HYDROCARBONS. |
US6455015B1 (en) | 2000-02-16 | 2002-09-24 | Uop Llc | Fluid-solid contacting chambers having multi-conduit, multi-nozzle fluid distribution |
DE10009017A1 (en) | 2000-02-25 | 2001-09-06 | Basf Ag | Molded catalysts |
AU2001244333A1 (en) | 2000-04-06 | 2001-10-23 | Bp Chemicals Limited | Process for the gas phase polymerisation of olefins |
US6596912B1 (en) | 2000-05-24 | 2003-07-22 | The Texas A&M University System | Conversion of methane to C4+ aliphatic products in high yields using an integrated recycle reactor system |
GB0016895D0 (en) | 2000-07-11 | 2000-08-30 | Bp Chem Int Ltd | Olefin oligomerisation |
US6660812B2 (en) | 2000-07-13 | 2003-12-09 | Exxonmobil Chemical Patents Inc. | Production of olefin derivatives |
US6447745B1 (en) | 2000-08-01 | 2002-09-10 | Exxonmobil Research And Engineering Company | Catalytic oxidation process |
WO2002014854A1 (en) | 2000-08-14 | 2002-02-21 | Chevron U.S.A. Inc. | Use of microchannel reactors in combinatorial chemistry |
US6726832B1 (en) | 2000-08-15 | 2004-04-27 | Abb Lummus Global Inc. | Multiple stage catalyst bed hydrocracking with interstage feeds |
US6468501B1 (en) | 2000-09-14 | 2002-10-22 | Chevrontexaco Corporation | Method for heteroatom lattice substitution in large and extra-large pore borosilicate zeolites |
US6518476B1 (en) | 2000-09-18 | 2003-02-11 | Union Carbide Chemicals & Plastics Technology Corporation | Methods for manufacturing olefins from lower alkans by oxidative dehydrogenation |
US6403523B1 (en) | 2000-09-18 | 2002-06-11 | Union Carbide Chemicals & Plastics Technology Corporation | Catalysts for the oxidative dehydrogenation of hydrocarbons |
CA2422567A1 (en) | 2000-09-20 | 2003-03-18 | Hideki Kurimura | Method for partial oxidation of methane using dense, oxygen selective permeation ceramic membrane |
US6538169B1 (en) | 2000-11-13 | 2003-03-25 | Uop Llc | FCC process with improved yield of light olefins |
US6660894B1 (en) | 2000-11-21 | 2003-12-09 | Phillips Petroleum Company | Process for upgrading an oligomerization product |
DE10101695A1 (en) | 2001-01-15 | 2002-07-18 | Basf Ag | Heterogeneous catalyzed gas phase production of (meth)acrolein and/or meth(acrylic acid) using mixed oxide catalyst formed into geometrically shaped article of specific geometric characteristics |
US6669916B2 (en) | 2001-02-12 | 2003-12-30 | Praxair Technology, Inc. | Method and apparatus for purifying carbon dioxide feed streams |
US6509292B1 (en) | 2001-03-30 | 2003-01-21 | Sud-Chemie Inc. | Process for selective hydrogenation of acetylene in an ethylene purification process |
ITMI20010782A1 (en) | 2001-04-12 | 2002-10-12 | Enitecnologie Spa | PROCEDURE FOR OBTAINING A DIESEL CUTTING FUEL BY THE OLIGOMERIZATION OF OLEFINS OR THEIR MIXTURES |
US6683019B2 (en) | 2001-06-13 | 2004-01-27 | Abb Lummus Global Inc. | Catalyst for the metathesis of olefin(s) |
US6635103B2 (en) | 2001-07-20 | 2003-10-21 | New Jersey Institute Of Technology | Membrane separation of carbon dioxide |
US7316804B2 (en) | 2001-08-02 | 2008-01-08 | Ineos Usa Llc | Flow reactors for chemical conversions with heterogeneous catalysts |
US6703429B2 (en) | 2001-08-23 | 2004-03-09 | Chevron U.S.A. Inc. | Process for converting synthesis gas into hydrocarbonaceous products |
FR2829707B1 (en) | 2001-09-19 | 2003-12-12 | Air Liquide | METHOD AND DEVICE FOR MIXING TWO REACTIVE GASES |
US6921516B2 (en) | 2001-10-15 | 2005-07-26 | General Motors Corporation | Reactor system including auto ignition and carbon suppression foam |
US6783659B2 (en) | 2001-11-16 | 2004-08-31 | Chevron Phillips Chemical Company, L.P. | Process to produce a dilute ethylene stream and a dilute propylene stream |
US6764602B2 (en) | 2001-11-29 | 2004-07-20 | Exxonmobil Chemical Patents Inc. | Process of removing oxygenated contaminants from an olefin composition |
US6747066B2 (en) | 2002-01-31 | 2004-06-08 | Conocophillips Company | Selective removal of oxygen from syngas |
US6768035B2 (en) | 2002-01-31 | 2004-07-27 | Chevron U.S.A. Inc. | Manufacture of high octane alkylate |
JP4245298B2 (en) | 2002-02-27 | 2009-03-25 | ダイセル化学工業株式会社 | Gas reaction component supply control method and control apparatus |
US6610124B1 (en) | 2002-03-12 | 2003-08-26 | Engelhard Corporation | Heavy hydrocarbon recovery from pressure swing adsorption unit tail gas |
AU2003214197A1 (en) | 2002-03-19 | 2003-10-08 | Energy Technologies Group, Inc. | Gas to liquid conversion process |
US6713657B2 (en) | 2002-04-04 | 2004-03-30 | Chevron U.S.A. Inc. | Condensation of olefins in fischer tropsch tail gas |
US20030189202A1 (en) | 2002-04-05 | 2003-10-09 | Jun Li | Nanowire devices and methods of fabrication |
US7093445B2 (en) | 2002-05-31 | 2006-08-22 | Catalytica Energy Systems, Inc. | Fuel-air premixing system for a catalytic combustor |
FR2840607A1 (en) | 2002-06-10 | 2003-12-12 | Bp Lavera | Production of ethane for olefins such as ethylene, involves contacting methane with metal catalyst chosen from metal hydride and/or metal organic compound |
US6759562B2 (en) | 2002-07-24 | 2004-07-06 | Abb Lummus Global Inc. | Olefin plant recovery system employing a combination of catalytic distillation and fixed bed catalytic steps |
US6964934B2 (en) | 2002-08-28 | 2005-11-15 | Albemarle Netherlands B.V. | Process for the preparation of doped pentasil-type zeolite using doped seeds |
JP2006520317A (en) | 2002-09-18 | 2006-09-07 | ボード オブ リージェンツ ユニバーシティ オブ テキサス システム | Peptide-mediated synthesis of metal and magnetic materials |
CN1182038C (en) | 2002-10-11 | 2004-12-29 | 清华大学 | Synthesis process of nanostring and nanopowder of RE hydroxide or oxide |
JP2006516265A (en) | 2002-12-20 | 2006-06-29 | サソル テクノロジー (ピーティーワイ) リミテッド | Olefin trimerization |
US7484385B2 (en) | 2003-01-16 | 2009-02-03 | Lummus Technology Inc. | Multiple reflux stream hydrocarbon recovery process |
US20040158113A1 (en) | 2003-02-06 | 2004-08-12 | Girish Srinivas | Catalysts and process for converting fuel gases to gasoline |
US8277525B2 (en) | 2003-02-07 | 2012-10-02 | Dalton Robert C | High energy transport gas and method to transport same |
US20130025201A1 (en) | 2003-02-07 | 2013-01-31 | Dalton Robert C | High energy transport gas and method to transport same |
US7196238B2 (en) | 2003-03-10 | 2007-03-27 | Fortum Oyj | Process for dimerizing light olefins |
US7932296B2 (en) | 2003-03-16 | 2011-04-26 | Kellogg Brown & Root Llc | Catalytic partial oxidation reforming for syngas processing and products made therefrom |
CA2427722C (en) | 2003-04-29 | 2007-11-13 | Ebrahim Bagherzadeh | Preparation of catalyst and use for high yield conversion of methane to ethylene |
GB0311774D0 (en) | 2003-05-22 | 2003-06-25 | Bp Chem Int Ltd | Production of olefins |
KR101110800B1 (en) | 2003-05-28 | 2012-07-06 | 도꾸리쯔교세이호진 상교기쥬쯔 소고겡뀨죠 | Process for producing hydroxyl group-containing compound |
CN1261216C (en) | 2003-05-30 | 2006-06-28 | 中国石油化工股份有限公司 | Hydrocarbon cracking catalyst with molecular sieve and preparing method thereof |
US7214841B2 (en) | 2003-07-15 | 2007-05-08 | Abb Lummus Global Inc. | Processing C4 olefin streams for the maximum production of propylene |
JP3785543B2 (en) | 2003-08-26 | 2006-06-14 | 松下電器産業株式会社 | Manufacturing method of manganese oxide nanostructure and oxygen reduction electrode using the manganese oxide nanostructure |
US7208647B2 (en) * | 2003-09-23 | 2007-04-24 | Synfuels International, Inc. | Process for the conversion of natural gas to reactive gaseous products comprising ethylene |
US7183451B2 (en) | 2003-09-23 | 2007-02-27 | Synfuels International, Inc. | Process for the conversion of natural gas to hydrocarbon liquids |
US7223895B2 (en) | 2003-11-18 | 2007-05-29 | Abb Lummus Global Inc. | Production of propylene from steam cracking of hydrocarbons, particularly ethane |
US7199273B2 (en) | 2003-11-24 | 2007-04-03 | Exxonmobil Chemical Patents, Inc. | Selective hydrogenation of alkynes and/or diolefins |
JP2005161225A (en) | 2003-12-03 | 2005-06-23 | Nissan Motor Co Ltd | Catalyst for purifying exhaust gas |
US7923109B2 (en) | 2004-01-05 | 2011-04-12 | Board Of Regents, The University Of Texas System | Inorganic nanowires |
US7589041B2 (en) | 2004-04-23 | 2009-09-15 | Massachusetts Institute Of Technology | Mesostructured zeolitic materials, and methods of making and using the same |
US20130292300A1 (en) | 2004-04-23 | 2013-11-07 | Massachusetts Institute Of Technology | Mesostructured zeolitic materials suitable for use in hydrocracking catalyst compositions and methods of making and using the same |
US7375048B2 (en) | 2004-04-29 | 2008-05-20 | Basf Catalysts Llc | ZSM-5 additive |
US7550644B2 (en) | 2004-05-10 | 2009-06-23 | Precision Combustion, Inc. | Isobutane alkylation |
DE102004029147B4 (en) | 2004-06-17 | 2008-01-03 | Uhde Gmbh | Process and apparatus for the preparation of 1,2-dichloroethane by direct chlorination |
FR2873116B1 (en) | 2004-07-15 | 2012-11-30 | Inst Francais Du Petrole | OLEFIN OLIGOMERIZATION METHOD USING SILICA-ALUMINATED CATALYST |
US7207192B2 (en) | 2004-07-28 | 2007-04-24 | Kellogg Brown & Root Llc | Secondary deethanizer to debottleneck an ethylene plant |
US7141705B2 (en) | 2004-08-05 | 2006-11-28 | Catalytic Distillation Technologies | Etherification process |
US20060283780A1 (en) | 2004-09-01 | 2006-12-21 | Sud-Chemie Inc., | Desulfurization system and method for desulfurizing a fuel stream |
EP1632467A1 (en) | 2004-09-06 | 2006-03-08 | Research Institute of Petroleum Industry | Improved catalyst for direct conversion of methane to ethane and ethylene |
US20060084830A1 (en) | 2004-10-20 | 2006-04-20 | Catalytic Distillation Technologies | Selective hydrogenation process and catalyst |
US7361622B2 (en) | 2005-11-08 | 2008-04-22 | Rohm And Haas Company | Multi-staged catalyst systems and process for converting alkanes to alkenes and to their corresponding oxygenated products |
DE102004061772A1 (en) | 2004-12-22 | 2006-07-06 | Basf Ag | Process for the preparation of propene from propane |
US7683227B2 (en) | 2004-12-22 | 2010-03-23 | Exxonmobil Chemical Patents Inc. | Production of aromatic hydrocarbons from methane |
DE102004063090A1 (en) | 2004-12-22 | 2006-07-06 | Uhde Gmbh | Process for the preparation of 1,2-dichloroethane by direct chlorination |
FR2880018B1 (en) | 2004-12-27 | 2007-02-23 | Inst Francais Du Petrole | PROPYLENE PRODUCTION USING DIMERIZATION OF ETHYLENE TO BUTENE-1, HYDRO-ISOMERISATION TO BUTENE-2 AND ETHYLENE METATHESIS |
US20060173224A1 (en) | 2005-02-01 | 2006-08-03 | Catalytic Distillation Technologies | Process and catalyst for selective hydrogenation of dienes and acetylenes |
US7525002B2 (en) | 2005-02-28 | 2009-04-28 | Exxonmobil Research And Engineering Company | Gasoline production by olefin polymerization with aromatics alkylation |
US7566428B2 (en) | 2005-03-11 | 2009-07-28 | Saint-Gobain Ceramics & Plastics, Inc. | Bed support media |
US7888541B2 (en) | 2005-04-15 | 2011-02-15 | Catalytic Distillation Technologies | Double bond hydroisomerization of butenes |
DE102005019596A1 (en) | 2005-04-27 | 2006-11-02 | Süd-Chemie AG | Cylindrical catalyst body, used for steam reforming hydrocarbons, comprises extent surface, which is parallel to longitudinal axis of catalyst body running grooves and between grooves exhibiting running webs |
GB0512377D0 (en) | 2005-06-17 | 2005-07-27 | Exxonmobil Chem Patents Inc | Oligomerisation of olefins with zeolite catalyst |
ES2335035T3 (en) | 2005-07-27 | 2010-03-18 | Chevron Phillips Chemical Company Lp | METHOD FOR MANUFACTURING AND USING A SELECTIVE HYDROGENATION CATALYST. |
EP1748039B1 (en) | 2005-07-29 | 2013-01-23 | Linde AG | Method for deactivation of an organometallic catalyst |
EP1749806B1 (en) | 2005-07-29 | 2008-10-15 | Linde AG | Method for preparing linear alpha-olefins with improved heat removal |
EP1749807A1 (en) | 2005-08-02 | 2007-02-07 | Linde AG | Method for producing linear alpha-olefins with improved product distribution |
DK200600854A (en) | 2005-09-02 | 2007-03-03 | Topsoe Haldor As | Process and catalyst for hydrogenation of carbon oxides |
US20070083073A1 (en) | 2005-09-02 | 2007-04-12 | Ebrahim Bagherzadeh | Catalyst and method for converting low molecular weight paraffinic hydrocarbons into alkenes and organic compounds with carbon numbers of 2 or more |
EP1945350A1 (en) | 2005-10-07 | 2008-07-23 | Midwest Research Institute, Inc. | Attrition resistant fluidizable reforming catalyst |
DE102005050388A1 (en) | 2005-10-20 | 2007-04-26 | Linde Ag | Recovery system for the further processing of a cracked gas stream of an ethylene plant |
CN101316807B (en) | 2005-10-28 | 2012-11-28 | 巴斯夫欧洲公司 | Method for the synthesis of aromatic hydrocarbons from C1-C4 alkanes, and utilization of a C1-C4 alkane-containing product flow |
US7550638B2 (en) | 2005-11-16 | 2009-06-23 | Equistar Chemicals, Lp | Integrated cracking and metathesis process |
DE102005061897A1 (en) | 2005-12-23 | 2007-06-28 | Degussa Gmbh | Process for the preparation of powdered solids |
US7521394B2 (en) | 2005-12-29 | 2009-04-21 | The Board Of Trustees Of The University Of Illinois | Nanoparticles containing titanium oxide |
JP5330635B2 (en) | 2006-01-20 | 2013-10-30 | 豊田通商株式会社 | Propylene production method, catalyst regeneration method, solid acid catalyst |
US7993599B2 (en) | 2006-03-03 | 2011-08-09 | Zeropoint Clean Tech, Inc. | Method for enhancing catalyst selectivity |
CN101460432B (en) | 2006-04-21 | 2013-04-03 | 埃克森美孚化学专利公司 | Production of aromatics from methane |
US7659437B2 (en) | 2006-04-21 | 2010-02-09 | Exxonmobil Chemical Patents Inc. | Process for methane conversion |
US7781636B2 (en) | 2006-04-21 | 2010-08-24 | Exxonmobil Chemical Patents Inc. | Process for methane conversion |
US7977519B2 (en) | 2006-04-21 | 2011-07-12 | Exxonmobil Chemical Patents Inc. | Production of aromatic hydrocarbons from methane |
US7795490B2 (en) | 2006-04-21 | 2010-09-14 | Exxonmobil Chemical Patents Inc. | Production of aromatics from methane |
GB0608277D0 (en) | 2006-04-27 | 2006-06-07 | Accentus Plc | Process for preparing liquid hydrocarbons |
EP2016127B1 (en) | 2006-05-02 | 2010-03-17 | Dow Global Technologies Inc. | High-density polyethylene compositions, method of making the same, articles made therefrom, and method of making such articles |
WO2007141288A1 (en) | 2006-06-07 | 2007-12-13 | Basf Se | Process for codimerizing olefins |
DE102006027334A1 (en) | 2006-06-13 | 2008-01-10 | Evonik Degussa Gmbh | Process for the preparation of metal oxide powders |
DE102006027335A1 (en) | 2006-06-13 | 2008-01-10 | Evonik Degussa Gmbh | Process for the preparation of mixed metal oxide powders |
DE102006027302A1 (en) | 2006-06-13 | 2008-01-10 | Evonik Degussa Gmbh | Process for the preparation of mixed oxide powders |
TWI397446B (en) | 2006-06-21 | 2013-06-01 | Cambrios Technologies Corp | Methods of controlling nanostructure formations and shapes |
EP1886985B1 (en) | 2006-07-31 | 2009-09-02 | Saudi Basic Industries Corporation | Process for oligomerization of ethylene and/or alpha-olefins |
WO2008022147A1 (en) | 2006-08-14 | 2008-02-21 | Mayo Foundation For Medical Education And Research | Rare earth nanoparticles |
CN101134913B (en) | 2006-08-31 | 2011-05-18 | 中国石油化工股份有限公司 | Hydrocarbons catalytic conversion method |
US7824574B2 (en) | 2006-09-21 | 2010-11-02 | Eltron Research & Development | Cyclic catalytic upgrading of chemical species using metal oxide materials |
DE102006055973A1 (en) | 2006-11-24 | 2008-05-29 | Borsig Gmbh | Heat exchanger for cooling cracked gas |
ES2319007B1 (en) | 2006-12-07 | 2010-02-16 | Rive Technology, Inc. | METHODS FOR MANUFACTURING MESOSTRUCTURED ZEOLITICAL MATERIALS. |
US9103586B2 (en) | 2006-12-16 | 2015-08-11 | Kellogg Brown & Root Llc | Advanced C2-splitter feed rectifier |
CA2672449A1 (en) | 2006-12-19 | 2008-06-26 | Jean-Marie Basset | Process for converting methane into a higher alkane mixture |
US7586018B2 (en) | 2006-12-21 | 2009-09-08 | Uop Llc | Oxygenate conversion to olefins with dimerization and metathesis |
EA016012B1 (en) | 2007-02-16 | 2012-01-30 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Method and apparatus for reducing additives in a hydrocarbon stream |
US7589246B2 (en) | 2007-04-04 | 2009-09-15 | Exxonmobil Chemical Patents Inc. | Production of aromatics from methane |
EP2152408A2 (en) | 2007-04-25 | 2010-02-17 | HRD Corp | Catalyst and method for converting natural gas to higher carbon compounds |
US20090043141A1 (en) | 2007-05-30 | 2009-02-12 | Terry Mazanec | Oxidative coupling of methane |
EP2014635A1 (en) | 2007-06-12 | 2009-01-14 | Bp Oil International Limited | Process for converting ethane into liquid alkane mixtures |
US7799209B2 (en) | 2007-06-29 | 2010-09-21 | Uop Llc | Process for recovering power from FCC product |
US7879119B2 (en) | 2007-07-20 | 2011-02-01 | Kellogg Brown & Root Llc | Heat integration and condensate treatment in a shift feed gas saturator |
US20100185034A1 (en) | 2007-08-03 | 2010-07-22 | Mitsui Chemicals , Inc | Process for producing aromatic hydrocarbon |
US9617196B2 (en) | 2007-08-03 | 2017-04-11 | Hitachi Zosen Corporation | Catalyst for methanation of carbon oxides, preparation method of the catalyst and process for the methanation |
FI120627B (en) | 2007-08-24 | 2009-12-31 | Neste Oil Oyj | Process for oligomerization of olefins |
TW200918486A (en) | 2007-09-18 | 2009-05-01 | Asahi Kasei Chemicals Corp | Process for production of propylene |
EP2045013A1 (en) | 2007-10-03 | 2009-04-08 | Bp Oil International Limited | Solid metal compound, preparations and uses thereof |
US8206498B2 (en) | 2007-10-25 | 2012-06-26 | Rive Technology, Inc. | Methods of recovery of pore-forming agents for mesostructured materials |
WO2009071463A2 (en) | 2007-12-03 | 2009-06-11 | Basf Se | Oxidative methane coupling via membrane reactor |
EP2225033B1 (en) | 2007-12-12 | 2017-10-04 | Saudi Basic Industries Corporation | Catalyst composition for oligomerization of ethylene oligomerization process and method for its preparation |
US8404189B2 (en) | 2007-12-14 | 2013-03-26 | Dow Technology Investments Llc | Oxygen/hydrocarbon rapid (high shear) gas mixer, particularly for the production of ethylene oxide |
CN100563829C (en) | 2008-02-03 | 2009-12-02 | 山东省科学院能源研究所 | Integral supported carbon molecular sieve catalyst and preparation method thereof is used |
US7847140B2 (en) | 2008-02-13 | 2010-12-07 | Karl Chuang | Process for making higher olefins |
CN101945841B (en) | 2008-02-18 | 2014-07-16 | 国际壳牌研究有限公司 | Process for the conversion of ethane to aromatic hydrocarbons |
US8071063B2 (en) | 2008-02-21 | 2011-12-06 | Exxonmobile Research And Engineering Company | Separation of hydrogen from hydrocarbons utilizing zeolitic imidazolate framework materials |
US7687041B2 (en) | 2008-02-27 | 2010-03-30 | Kellogg Brown & Root Llc | Apparatus and methods for urea production |
US8071836B2 (en) | 2008-03-13 | 2011-12-06 | Fina Technology, Inc. | Process for toluene and methane coupling in a microreactor |
EP2103586A1 (en) | 2008-03-20 | 2009-09-23 | Bp Oil International Limited | Process for converting methane into ethane in a membrane reactor |
US8742189B2 (en) | 2008-04-08 | 2014-06-03 | Basf Se | Catalyst for the dehydroaromatisation of methane and mixtures containing methane |
US9908093B2 (en) | 2008-04-09 | 2018-03-06 | Velocys, Inc. | Process for converting a carbonaceous material to methane, methanol and/or dimethyl ether using microchannel process technology |
JP5290403B2 (en) | 2008-04-29 | 2013-09-18 | レイセオン カンパニー | Small aperture interrogator antenna system using sum-difference orientation discrimination technique |
US7968020B2 (en) | 2008-04-30 | 2011-06-28 | Kellogg Brown & Root Llc | Hot asphalt cooling and pelletization process |
US20090277837A1 (en) | 2008-05-06 | 2009-11-12 | Chunqing Liu | Fluoropolymer Coated Membranes |
US20110160508A1 (en) | 2008-05-21 | 2011-06-30 | Ding Ma | Production of aromatics from methane |
US8293805B2 (en) | 2008-05-29 | 2012-10-23 | Schlumberger Technology Corporation | Tracking feedstock production with micro scale gas-to-liquid units |
BRPI0803895B1 (en) | 2008-07-03 | 2018-08-14 | Oxiteno S.A. Indústria E Comércio | PROCEDURE FOR THE PRODUCTION OF LIGHT HYDROCARBONS FROM METHANIC RICH GASES, STATES THE SOLID OXIDE FUEL USED FOR THE PRODUCTION OF LIGHT HYDROCARBONS, AND, CATALYST FOR LEVES GARDEN RIOBON GARS In Methane |
US20100000153A1 (en) | 2008-07-07 | 2010-01-07 | Kyrogen Usa, Llc | Remote micro-scale gtl products for uses in oil- and gas-field and pipeline applications |
US7993500B2 (en) | 2008-07-16 | 2011-08-09 | Calera Corporation | Gas diffusion anode and CO2 cathode electrolyte system |
US8163070B2 (en) | 2008-08-01 | 2012-04-24 | Wolfgang Georg Hees | Method and system for extracting carbon dioxide by anti-sublimation at raised pressure |
KR101273124B1 (en) | 2008-08-12 | 2013-06-13 | 루머스 테크놀로지 인코포레이티드 | Integrated propylene production |
GB0816703D0 (en) | 2008-09-12 | 2008-10-22 | Johnson Matthey Plc | Shaped heterogeneous catalysts |
US8119848B2 (en) | 2008-10-01 | 2012-02-21 | Catalytic Distillation Technologies | Preparation of alkylation feed |
TWI468223B (en) | 2008-10-20 | 2015-01-11 | Huntsman Petrochemical Llc | Modified trilobe shape for maleic anhydride catalyst and process for preparing maleic anhydride |
CN101387019B (en) | 2008-10-24 | 2012-05-09 | 上海应用技术学院 | Method for preparing mesoporous silica molecular sieve fiber |
DE102008064275A1 (en) | 2008-12-20 | 2010-07-01 | Bayer Technology Services Gmbh | Process for the oxidative coupling of methane and production of synthesis gas |
US7790012B2 (en) | 2008-12-23 | 2010-09-07 | Calera Corporation | Low energy electrochemical hydroxide system and method |
US20110036728A1 (en) | 2008-12-23 | 2011-02-17 | Calera Corporation | Low-energy electrochemical proton transfer system and method |
US8912109B2 (en) | 2008-12-29 | 2014-12-16 | Fina Technology, Inc. | Catalyst with an ion-modified binder |
US8524625B2 (en) | 2009-01-19 | 2013-09-03 | Rive Technology, Inc. | Compositions and methods for improving the hydrothermal stability of mesostructured zeolites by rare earth ion exchange |
US8815080B2 (en) | 2009-01-26 | 2014-08-26 | Lummus Technology Inc. | Adiabatic reactor to produce olefins |
US8178053B2 (en) | 2009-02-20 | 2012-05-15 | H R D Corporation | System and method for gas reaction |
US20100229725A1 (en) | 2009-03-10 | 2010-09-16 | Kasra Farsad | Systems and Methods for Processing CO2 |
US8399527B1 (en) | 2009-03-17 | 2013-03-19 | Louisiana Tech University Research Foundation; A Division Of Louisiana Tech University Foundation, Inc. | Bound cobalt nanowires for Fischer-Tropsch synthesis |
US8748681B2 (en) | 2009-03-31 | 2014-06-10 | Uop Llc | Process for oligomerizing dilute ethylene |
US8710286B2 (en) * | 2009-03-31 | 2014-04-29 | Fina Technology, Inc. | Oxidative coupling of hydrocarbons as heat source |
US8575410B2 (en) | 2009-03-31 | 2013-11-05 | Uop Llc | Process for oligomerizing dilute ethylene |
US8021620B2 (en) | 2009-03-31 | 2011-09-20 | Uop Llc | Apparatus for oligomerizing dilute ethylene |
WO2010128644A1 (en) | 2009-05-08 | 2010-11-11 | 三菱化学株式会社 | Method for producing propylene |
CN102438999A (en) | 2009-05-20 | 2012-05-02 | 巴斯夫欧洲公司 | System and method for producing superior hydrocarbons from methane |
US8715392B2 (en) | 2009-05-21 | 2014-05-06 | Battelle Memorial Institute | Catalyzed CO2-transport membrane on high surface area inorganic support |
US9089832B2 (en) | 2009-06-29 | 2015-07-28 | Fina Technology, Inc. | Catalysts for oxidative coupling of hydrocarbons |
US8450546B2 (en) | 2009-06-29 | 2013-05-28 | Fina Technology, Inc. | Process for the oxidative coupling of hydrocarbons |
US8912381B2 (en) | 2009-06-29 | 2014-12-16 | Fina Technology, Inc. | Process for the oxidative coupling of methane |
DE102009031305A1 (en) | 2009-06-30 | 2011-01-05 | Uhde Gmbh | Catalyst-coated support, process for its preparation, a reactor equipped therewith and its use |
ES2439261T3 (en) | 2009-07-24 | 2014-01-22 | Linde Ag | Preparation procedure for linear alpha-olefins |
US8592732B2 (en) | 2009-08-27 | 2013-11-26 | Korea University Research And Business Foundation | Resistive heating device for fabrication of nanostructures |
DE102009039149A1 (en) | 2009-08-31 | 2011-03-03 | Uhde Gmbh | Catalytic membrane material coating |
WO2011029071A1 (en) | 2009-09-03 | 2011-03-10 | Christopher Brown | Improved adsorption process for the dehydration of alcohol |
EP2295474A1 (en) | 2009-09-11 | 2011-03-16 | Total Petrochemicals Research Feluy | Process for recycling product streams separated from a hydrocarbon-containing feed stream. |
CN102548657B (en) | 2009-09-30 | 2015-01-21 | 埃克森美孚化学专利公司 | Production of aromatics from methane |
WO2011050359A1 (en) | 2009-10-23 | 2011-04-28 | Massachusetts Institute Of Technology | Biotemplated inorganic materials |
CN102093157A (en) | 2009-12-09 | 2011-06-15 | 中国科学院兰州化学物理研究所 | Joint process for preparing ethylene and synthesis gas by direct conversion of methane |
GB0921875D0 (en) | 2009-12-15 | 2010-01-27 | Lucite Int Uk Ltd | A continuous process for the carbonylation of ethylene |
CN101747927B (en) | 2009-12-31 | 2012-08-08 | 金浦新材料股份有限公司 | Coke inhibitor for ethylene cracking |
US20110171121A1 (en) | 2010-01-08 | 2011-07-14 | Rive Technology, Inc. | Compositions and methods for making stabilized mesoporous materials |
US8658750B2 (en) | 2010-03-09 | 2014-02-25 | Exxonmobil Chemical Patents Inc. | System and method for selective trimerization |
US20110257454A1 (en) | 2010-04-20 | 2011-10-20 | Fina Technology, Inc. | Use of an Additive in the Coupling of Toluene with a Carbon Source |
US8399726B2 (en) | 2010-04-20 | 2013-03-19 | Fina Technology Inc | Reactors and processes for the oxidative coupling of hydrocarbons |
US8722950B2 (en) | 2010-04-26 | 2014-05-13 | Saudi Basic Industries Corporation | Process for producing propylene and aromatics from butenes by metathesis and aromatization |
DK2569492T3 (en) | 2010-05-10 | 2015-10-05 | Autoprod Oy | Method and device for producing a timber structure, which is made of rod-like elements |
FR2960234B1 (en) | 2010-05-18 | 2013-11-01 | Inst Francais Du Petrole | A METHOD FOR DIMERIZING ETHYLENE TO BUTENE-1 USING A COMPOSITION COMPRISING A TITANIUM-BASED COMPLEX AND A HETEROATOMY-FUNCTIONALIZED ALCOXY LIGAND |
US9718054B2 (en) | 2010-05-24 | 2017-08-01 | Siluria Technologies, Inc. | Production of ethylene with nanowire catalysts |
KR20130038901A (en) | 2010-06-24 | 2013-04-18 | 럿거스, 더 스테이트 유니버시티 오브 뉴저지 | Spinel catalysts for water and hydrocarbon oxidation |
US8282709B2 (en) | 2010-06-29 | 2012-10-09 | The Governors Of The University Of Alberta | Removal of ethane from natural gas at high pressure |
US8585802B2 (en) | 2010-07-09 | 2013-11-19 | Arnold Keller | Carbon dioxide capture and liquefaction |
CA2804409A1 (en) | 2010-07-09 | 2012-01-12 | John Bøgild Hansen | Process for converting biogas to a gas rich in methane |
US20120197053A1 (en) | 2010-09-21 | 2012-08-02 | Synfuels International., Inc. | System and method for the production of liquid fuels |
FR2964982B1 (en) | 2010-09-22 | 2013-03-08 | Commissariat Energie Atomique | PROCESS FOR REMOVING METAL CATALYST RESIDUES ON SURFACE OF CATALYTICALLY GROWN-WIRE PRODUCTS |
DK2625251T3 (en) | 2010-10-06 | 2021-02-15 | Exelus Inc | Preparation of a high octane alkylate of ethylene and isobutane |
US8395005B2 (en) | 2010-10-13 | 2013-03-12 | Equistar Chemicals, Lp | Production of 1-butene and propylene from ethylene |
RU2447048C1 (en) | 2010-10-14 | 2012-04-10 | Закрытое акционерное общество "ШАГ" | Combined method of producing ethylene and derivatives thereof and electrical energy from natural gas |
US20130270180A1 (en) | 2010-10-28 | 2013-10-17 | Novarials Corporation | Ceramic nanowire membranes and methods of making the same |
BR112013011951A2 (en) | 2010-11-16 | 2016-08-30 | Rhodia Operations | alumina catalyst support |
CN102125825B (en) | 2010-12-02 | 2012-05-23 | 河北工业大学 | Preparation method of ZrO2 nanotube supported B2O3 catalyst |
MX337727B (en) | 2010-12-17 | 2016-03-16 | Univation Tech Llc | Systems and methods for recovering hydrocarbons from a polyolefin purge gas product. |
EP2655559A4 (en) | 2010-12-24 | 2014-07-23 | Sapphire Energy Inc | Production of aromatics from renewable resources |
US8871670B2 (en) | 2011-01-05 | 2014-10-28 | The Board Of Trustees Of The University Of Illinois | Defect engineering in metal oxides via surfaces |
US20120215045A1 (en) | 2011-02-22 | 2012-08-23 | Fina Technology, Inc. | Staged Injection of Oxygen for Oxidative Coupling or Dehydrogenation Reactions |
WO2012118888A2 (en) | 2011-03-02 | 2012-09-07 | Aither Chemicals, Llc | Methods for integrated natural gas purification and products produced therefrom |
WO2012122233A2 (en) | 2011-03-07 | 2012-09-13 | The Regents Of The University Of California | Metal-organic framework adsorbants for composite gas separation |
WO2012138910A2 (en) | 2011-04-08 | 2012-10-11 | Rive Technology, Inc. | Mesoporous framework-modified zeolites |
EA029867B1 (en) | 2011-05-24 | 2018-05-31 | Силурия Текнолоджиз, Инк. | Catalysts for petrochemical catalysis |
US9394215B2 (en) | 2011-07-19 | 2016-07-19 | Uop Llc | Processes for making Cx-Cy olefins from C5 and C6 paraffins |
US20130023079A1 (en) | 2011-07-20 | 2013-01-24 | Sang Won Kang | Fabrication of light emitting diodes (leds) using a degas process |
WO2013010662A1 (en) | 2011-07-21 | 2013-01-24 | Saudi Basic Industries Corporation | Catalyst for the preparation of aromatic hydrocarbons and use thereof |
DE102011080294A1 (en) | 2011-08-02 | 2013-02-07 | Technische Universität Berlin | Process for the oxidative conversion of gaseous alkanes in a fluidized bed membrane reactor and a reactor for carrying out this process |
CA2856310C (en) | 2011-11-29 | 2021-09-21 | Siluria Technologies, Inc. | Nanowire catalysts and methods for their use and preparation |
WO2013082110A1 (en) | 2011-12-02 | 2013-06-06 | Bio2Electric, Llc | Reactor, process, and system for the oxidation of gaseous streams |
US20130172649A1 (en) | 2011-12-30 | 2013-07-04 | Sivadinarayana Chinta | Supported nano sized zeolite catalyst for alkylation reactions |
KR101294592B1 (en) | 2012-01-11 | 2013-08-09 | 한국과학기술연구원 | Catalyst for oxidative coupling reaction of methane, method for preparing the same, and method for oxidative coupling reaction of methane using the same |
US9376324B2 (en) | 2012-01-13 | 2016-06-28 | Rive Technology, Inc. | Introduction of mesoporosity into zeolite materials with sequential acid, surfactant, and base treatment |
US9133079B2 (en) | 2012-01-13 | 2015-09-15 | Siluria Technologies, Inc. | Process for separating hydrocarbon compounds |
KR101566650B1 (en) | 2012-01-20 | 2015-11-05 | 신닛테츠스미킨 카부시키카이샤 | Continuous fixed-bed catalyst reaction device and catalyst reaction method using same |
US9446397B2 (en) | 2012-02-03 | 2016-09-20 | Siluria Technologies, Inc. | Method for isolation of nanomaterials |
AR090777A1 (en) | 2012-04-23 | 2014-12-03 | Shell Int Research | A PROCESS FOR THE AROMATIZATION OF A GAS CURRENT CONTAINING METHANE |
WO2013169462A1 (en) | 2012-05-07 | 2013-11-14 | Exxonmobil Chemical Patents Inc. | Process for the production of xylenes and light olefins |
DE102012208417A1 (en) | 2012-05-21 | 2013-11-21 | INGEN GTL Ltd. | Process for the preparation of an isoparaffinic hydrocarbon mixture |
AU2013266189B2 (en) | 2012-05-24 | 2018-01-04 | Lummus Technology Llc | Catalysts comprising catalytic nanowires and their use |
WO2013177433A2 (en) | 2012-05-24 | 2013-11-28 | Siluria Technologies, Inc. | Oxidative coupling of methane systems and methods |
US9969660B2 (en) | 2012-07-09 | 2018-05-15 | Siluria Technologies, Inc. | Natural gas processing and systems |
US9610565B2 (en) | 2012-08-20 | 2017-04-04 | Purdue Research Foundation | Catalysts for oxidative coupling of methane and solution combustion method for the production of the same |
DE102012018602A1 (en) | 2012-09-20 | 2014-03-20 | Linde Aktiengesellschaft | Plant and process for the production of ethylene |
CN107663461A (en) | 2012-09-28 | 2018-02-06 | 埃迪亚贝拉科技有限公司 | For making the method and composition of composition desulfurization |
EA201590400A1 (en) | 2012-11-06 | 2015-09-30 | Эйч А Ди Корпорейшн | TURNING NATURAL GAS TO ORGANIC COMPOUNDS |
WO2014074458A1 (en) | 2012-11-06 | 2014-05-15 | H R D Corporation | Reactor and catalyst for converting natural gas to organic compounds |
US20140135553A1 (en) | 2012-11-12 | 2014-05-15 | Uop Llc | Process for recycling oligomerate to oligomerization |
US9663415B2 (en) | 2012-11-12 | 2017-05-30 | Uop Llc | Process for making diesel by oligomerization of gasoline |
US9441173B2 (en) | 2012-11-12 | 2016-09-13 | Uop Llc | Process for making diesel by oligomerization |
US10577291B2 (en) | 2012-11-12 | 2020-03-03 | Uop Llc | Methods for producing jet-range hydrocarbons |
WO2014089479A1 (en) | 2012-12-07 | 2014-06-12 | Siluria Technologies, Inc. | Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products |
US9055313B2 (en) | 2012-12-20 | 2015-06-09 | Hulu, LLC | Device activation using encoded representation |
US9688591B2 (en) | 2013-01-10 | 2017-06-27 | Equistar Chemicals, Lp | Ethylene separation process |
US20150376527A1 (en) | 2013-02-21 | 2015-12-31 | Jianguo Xu | Co2 capture from co2-rich natural gas |
WO2014131435A1 (en) | 2013-02-27 | 2014-09-04 | Haldor Topsøe A/S | Reactor for an auto-poisoning proces |
US9545610B2 (en) | 2013-03-04 | 2017-01-17 | Nova Chemicals (International) S.A. | Complex comprising oxidative dehydrogenation unit |
US8765660B1 (en) | 2013-03-08 | 2014-07-01 | Rive Technology, Inc. | Separation of surfactants from polar solids |
WO2014143880A1 (en) | 2013-03-15 | 2014-09-18 | Siluria Technologies, Inc. | Catalysts for petrochemical catalysis |
US20140275619A1 (en) | 2013-03-15 | 2014-09-18 | Celanese International Corporation | Process for Producing Acetic Acid and/or Ethanol By Methane Oxidation |
EP3008153B1 (en) | 2013-06-14 | 2020-08-05 | University Of Pretoria | Apparatus for endothermic reactions |
US9346721B2 (en) | 2013-06-25 | 2016-05-24 | Exxonmobil Chemical Patents Inc. | Hydrocarbon conversion |
WO2015000061A1 (en) | 2013-07-04 | 2015-01-08 | Nexen Energy Ulc | Olefins reduction of a hydrocarbon feed using olefins- aromatics alkylation |
US9446343B2 (en) | 2013-07-08 | 2016-09-20 | Exxonmobil Research And Engineering Company | Simulated moving bed system for CO2 separation, and method of same |
TWI633206B (en) | 2013-07-31 | 2018-08-21 | 卡利拉股份有限公司 | Electrochemical hydroxide systems and methods using metal oxidation |
WO2015021177A1 (en) | 2013-08-06 | 2015-02-12 | Massachusetts Institute Of Technology | Production of non-sintered transition metal carbide nanoparticles |
WO2015031366A1 (en) | 2013-08-30 | 2015-03-05 | Exxonmobil Chemical Patents Inc. | Oxygen storage and catalytic alkane conversion |
US10377117B2 (en) | 2013-09-25 | 2019-08-13 | Avery Dennison Corporation | Tamper evident security labels |
CN105517978B (en) | 2013-10-16 | 2017-11-14 | 沙特基础工业公司 | The method that methane is changed into ethene |
US10035127B2 (en) | 2013-11-04 | 2018-07-31 | The Regents Of The University Of California | Metal-organic frameworks with a high density of highly charged exposed metal cation sites |
US10047020B2 (en) | 2013-11-27 | 2018-08-14 | Siluria Technologies, Inc. | Reactors and systems for oxidative coupling of methane |
US9682900B2 (en) | 2013-12-06 | 2017-06-20 | Exxonmobil Chemical Patents Inc. | Hydrocarbon conversion |
CN110655437B (en) | 2014-01-08 | 2022-09-09 | 鲁玛斯技术有限责任公司 | System and method for ethylene to liquids |
US20150218786A1 (en) | 2014-01-08 | 2015-08-06 | Saundra Sue CULLEN | Sink insert with cleaning surface |
US10377682B2 (en) | 2014-01-09 | 2019-08-13 | Siluria Technologies, Inc. | Reactors and systems for oxidative coupling of methane |
US20180215682A1 (en) | 2014-01-09 | 2018-08-02 | Siluria Technologies, Inc. | Efficient oxidative coupling of methane processes and systems |
US9701597B2 (en) | 2014-01-09 | 2017-07-11 | Siluria Technologies, Inc. | Oxidative coupling of methane implementations for olefin production |
GB201403788D0 (en) | 2014-03-04 | 2014-04-16 | Johnson Matthey Plc | Catalyst arrangement |
CA2947483C (en) | 2014-05-02 | 2023-08-01 | Siluria Technologies, Inc. | Heterogeneous catalysts |
WO2015177066A1 (en) | 2014-05-19 | 2015-11-26 | Shell Internationale Research Maatschappij B.V. | Process for recovering methane from a gas stream comprising methane and ethylene |
EA201790244A1 (en) | 2014-07-22 | 2017-07-31 | Хальдор Топсёэ А/С | RECIRCULATION LINE IN THE METHOD OF PRODUCING HYDROCARBONS BY METHANE OXIDATIVE COMBINATION (METM) |
US9950971B2 (en) | 2014-07-23 | 2018-04-24 | Exxonmobil Chemical Patents Inc. | Process and catalyst for methane conversion to aromatics |
EP3825001A1 (en) | 2014-09-17 | 2021-05-26 | Lummus Technology LLC | Catalysts for natural gas processes |
KR101728809B1 (en) | 2014-09-25 | 2017-04-21 | 한국화학연구원 | Nanoporous inorganic-organic hybrid materials with nitrogen sorption selectivity and a method for selective separation of nitrogen-containing gas mixtures using the same |
EP3029019B1 (en) | 2014-12-05 | 2017-10-04 | Linde Aktiengesellschaft | Method for the production of hydrocarbons |
CN107001056B (en) | 2014-12-11 | 2019-04-02 | 瑞弗科技有限公司 | Mesoporous zeolite is prepared with the processing of reduction |
US9334204B1 (en) | 2015-03-17 | 2016-05-10 | Siluria Technologies, Inc. | Efficient oxidative coupling of methane processes and systems |
US10793490B2 (en) | 2015-03-17 | 2020-10-06 | Lummus Technology Llc | Oxidative coupling of methane methods and systems |
ES2833079T3 (en) | 2015-03-17 | 2021-06-14 | Lummus Technology Inc | Oxidative coupling of methane methods and systems |
US20160289143A1 (en) | 2015-04-01 | 2016-10-06 | Siluria Technologies, Inc. | Advanced oxidative coupling of methane |
EP3081292A1 (en) | 2015-04-15 | 2016-10-19 | Air Products And Chemicals, Inc. | Perforated adsorbent particles |
US20160318828A1 (en) | 2015-04-30 | 2016-11-03 | Exxonmobil Chemical Patents Inc. | Catalytic Alkane Dehydrogenation |
DE112016002573T5 (en) | 2015-06-08 | 2018-03-22 | Sabic Global Technologies B.V. | Oxidative methane coupling with La-Ce catalysts |
WO2016200504A1 (en) | 2015-06-08 | 2016-12-15 | Sabic Global Technologies B.V. | Low inlet temperature for oxidative coupling of methane |
US20180305273A1 (en) | 2015-06-16 | 2018-10-25 | Siluria Technologies, Inc. | Ethylene-to-liquids systems and methods |
WO2016205411A2 (en) | 2015-06-16 | 2016-12-22 | Siluria Technologies, Inc. | Ethylene-to-liquids systems and methods |
US9328297B1 (en) | 2015-06-16 | 2016-05-03 | Siluria Technologies, Inc. | Ethylene-to-liquids systems and methods |
DK3310480T3 (en) | 2015-06-22 | 2020-09-07 | Exelus Inc | IMPROVED CATALYZED ALKYLATION, ALKYLATION CATALYSTS AND METHODS OF PREPARING ALKYLATION CATALYSTS |
WO2016209507A1 (en) | 2015-06-23 | 2016-12-29 | Sabic Global Technologies, B.V. | A method for producing hydrocarbons by oxidative coupling of methane without catalyst |
EP3322522A2 (en) | 2015-07-15 | 2018-05-23 | SABIC Global Technologies B.V. | Silver promoted catalysts for oxidative coupling of methane |
US20170022125A1 (en) | 2015-07-21 | 2017-01-26 | Uop Llc | Processes for producing polymer grade light olefins from mixed alcohols |
WO2017034949A1 (en) | 2015-08-25 | 2017-03-02 | Sabic Global Technologies, B.V. | A method for producing hydrocarbons by oxidative coupling of methane with a heavy diluent |
JP6517631B2 (en) | 2015-08-26 | 2019-05-22 | Jxtgエネルギー株式会社 | Method of producing lubricating base oil |
CA2904477A1 (en) | 2015-09-14 | 2017-03-14 | Nova Chemicals Corporation | Heat dissipating diluent in fixed bed reactors |
EP3362425B1 (en) | 2015-10-16 | 2020-10-28 | Lummus Technology LLC | Separation methods and systems for oxidative coupling of methane |
US20170190638A1 (en) | 2016-01-04 | 2017-07-06 | Sabic Global Technologies, B.V. | Ethylbenzene Production with Ethylene from Oxidative Coupling of Methane |
CA3017274A1 (en) | 2016-03-16 | 2017-09-21 | Siluria Technologies, Inc. | Catalysts and methods for natural gas processes |
WO2017180910A1 (en) | 2016-04-13 | 2017-10-19 | Siluria Technologies, Inc. | Oxidative coupling of methane for olefin production |
CN107335386B (en) | 2016-04-29 | 2021-01-22 | 中国科学院大连化学物理研究所 | Configuration and preparation of catalytic reactor and method for directly synthesizing ethylene by catalyzing methane under anaerobic condition |
US20190233349A1 (en) | 2016-07-06 | 2019-08-01 | Sabic Global Technologies B.V. | Enhanced selectivity to c2+hydrocarbons by addition of hydrogen in feed to oxidative coupling of methane |
WO2018026501A1 (en) | 2016-08-01 | 2018-02-08 | Sabic Global Technologies, B.V. | Oxidative coupling of methane process with enhanced selectivity to c2+ hydrocarbons by addition of h2o in the feed |
WO2018085820A1 (en) | 2016-11-07 | 2018-05-11 | Sabic Global Technologies, B.V. | Sr-Ce-Yb-O CATALYSTS FOR OXIDATIVE COUPLING OF METHANE |
EP3548456A4 (en) | 2016-12-02 | 2020-10-28 | Lummus Technology LLC | Ethylene-to-liquids systems and methods |
US20180169561A1 (en) | 2016-12-19 | 2018-06-21 | Siluria Technologies, Inc. | Methods and systems for performing chemical separations |
WO2018114900A1 (en) | 2016-12-20 | 2018-06-28 | Shell Internationale Research Maatschappij B.V. | Oxidative dehydrogenation (odh) of ethane |
US11148985B2 (en) | 2017-01-31 | 2021-10-19 | Sabic Global Technologies, B.V. | Process for oxidative conversion of methane to ethylene |
WO2018217924A1 (en) | 2017-05-23 | 2018-11-29 | Siluria Technologies, Inc. | Integration of oxidative coupling of methane processes |
AU2018298234B2 (en) | 2017-07-07 | 2022-11-17 | Lummus Technology Llc | Systems and methods for the oxidative coupling of methane |
WO2019055220A1 (en) | 2017-09-15 | 2019-03-21 | Exxonmobil Research And Engineering Company | Modified trilobe and quadrilobe shaped catalyst extrudates |
-
2015
- 2015-09-29 US US14/868,911 patent/US20160289143A1/en not_active Abandoned
-
2016
- 2016-03-25 CA CA2975743A patent/CA2975743C/en active Active
- 2016-03-25 WO PCT/US2016/024195 patent/WO2016160563A1/en active Application Filing
-
2019
- 2019-06-19 US US16/445,562 patent/US11186529B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5015799A (en) * | 1989-07-06 | 1991-05-14 | Amoco Corporation | Oxidative coupling process for converting methane and/or natural gas to more transportable products |
US6096934A (en) * | 1998-12-09 | 2000-08-01 | Uop Llc | Oxidative coupling of methane with carbon conservation |
US7687048B1 (en) * | 2006-09-28 | 2010-03-30 | Uop Llc | Amine treatment in light olefin processing |
Cited By (54)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9527784B2 (en) | 2012-01-13 | 2016-12-27 | Siluria Technologies, Inc. | Process for separating hydrocarbon compounds |
US11254626B2 (en) | 2012-01-13 | 2022-02-22 | Lummus Technology Llc | Process for separating hydrocarbon compounds |
US9556086B2 (en) | 2012-05-24 | 2017-01-31 | Siluria Technologies, Inc. | Oxidative coupling of methane systems and methods |
US9969660B2 (en) | 2012-07-09 | 2018-05-15 | Siluria Technologies, Inc. | Natural gas processing and systems |
US11242298B2 (en) | 2012-07-09 | 2022-02-08 | Lummus Technology Llc | Natural gas processing and systems |
US9670113B2 (en) | 2012-07-09 | 2017-06-06 | Siluria Technologies, Inc. | Natural gas processing and systems |
US11168038B2 (en) | 2012-12-07 | 2021-11-09 | Lummus Technology Llc | Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products |
US10787398B2 (en) | 2012-12-07 | 2020-09-29 | Lummus Technology Llc | Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products |
US10927056B2 (en) | 2013-11-27 | 2021-02-23 | Lummus Technology Llc | Reactors and systems for oxidative coupling of methane |
US11407695B2 (en) | 2013-11-27 | 2022-08-09 | Lummus Technology Llc | Reactors and systems for oxidative coupling of methane |
US10047020B2 (en) | 2013-11-27 | 2018-08-14 | Siluria Technologies, Inc. | Reactors and systems for oxidative coupling of methane |
US10894751B2 (en) | 2014-01-08 | 2021-01-19 | Lummus Technology Llc | Ethylene-to-liquids systems and methods |
US11254627B2 (en) | 2014-01-08 | 2022-02-22 | Lummus Technology Llc | Ethylene-to-liquids systems and methods |
US9701597B2 (en) | 2014-01-09 | 2017-07-11 | Siluria Technologies, Inc. | Oxidative coupling of methane implementations for olefin production |
US11208364B2 (en) | 2014-01-09 | 2021-12-28 | Lummus Technology Llc | Oxidative coupling of methane implementations for olefin production |
US11008265B2 (en) | 2014-01-09 | 2021-05-18 | Lummus Technology Llc | Reactors and systems for oxidative coupling of methane |
US10377682B2 (en) | 2014-01-09 | 2019-08-13 | Siluria Technologies, Inc. | Reactors and systems for oxidative coupling of methane |
US10829424B2 (en) | 2014-01-09 | 2020-11-10 | Lummus Technology Llc | Oxidative coupling of methane implementations for olefin production |
US9790144B2 (en) | 2015-03-17 | 2017-10-17 | Siluria Technologies, Inc. | Efficient oxidative coupling of methane processes and systems |
US11542214B2 (en) | 2015-03-17 | 2023-01-03 | Lummus Technology Llc | Oxidative coupling of methane methods and systems |
US9567269B2 (en) | 2015-03-17 | 2017-02-14 | Siluria Technologies, Inc. | Efficient oxidative coupling of methane processes and systems |
US10787400B2 (en) | 2015-03-17 | 2020-09-29 | Lummus Technology Llc | Efficient oxidative coupling of methane processes and systems |
US10793490B2 (en) | 2015-03-17 | 2020-10-06 | Lummus Technology Llc | Oxidative coupling of methane methods and systems |
US11186529B2 (en) | 2015-04-01 | 2021-11-30 | Lummus Technology Llc | Advanced oxidative coupling of methane |
US10865165B2 (en) | 2015-06-16 | 2020-12-15 | Lummus Technology Llc | Ethylene-to-liquids systems and methods |
US20160376148A1 (en) * | 2015-06-23 | 2016-12-29 | Sabic Global Technologies, B.V. | Method for Producing Hydrocarbons by Oxidative Coupling of Methane without Catalyst |
US10125640B2 (en) | 2015-08-24 | 2018-11-13 | Saudi Arabian Oil Company | Modified goswami cycle based conversion of gas processing plant waste heat into power and cooling with flexibility |
US10174640B1 (en) | 2015-08-24 | 2019-01-08 | Saudi Arabian Oil Company | Modified Goswami cycle based conversion of gas processing plant waste heat into power and cooling with flexibility |
US20170058711A1 (en) * | 2015-08-24 | 2017-03-02 | Saudi Arabian Oil Company | Organic Rankine Cycle Based Conversion of Gas Processing Plant Waste Heat into Power and Cooling |
US10113448B2 (en) | 2015-08-24 | 2018-10-30 | Saudi Arabian Oil Company | Organic Rankine cycle based conversion of gas processing plant waste heat into power |
US10577981B2 (en) | 2015-08-24 | 2020-03-03 | Saudi Arabian Oil Company | Modified Goswami cycle based conversion of gas processing plant waste heat into power and cooling |
US10480352B2 (en) | 2015-08-24 | 2019-11-19 | Saudi Arabian Oil Company | Organic Rankine cycle based conversion of gas processing plant waste heat into power and cooling |
US10227899B2 (en) * | 2015-08-24 | 2019-03-12 | Saudi Arabian Oil Company | Organic rankine cycle based conversion of gas processing plant waste heat into power and cooling |
US10995636B2 (en) | 2015-08-24 | 2021-05-04 | Saudi Arabian Oil Company | Organic Rankine cycle based conversion of gas processing plant waste heat into power |
US10301977B2 (en) | 2015-08-24 | 2019-05-28 | Saudi Arabian Oil Company | Kalina cycle based conversion of gas processing plant waste heat into power |
US11073050B2 (en) | 2015-08-24 | 2021-07-27 | Saudi Arabian Oil Company | Kalina cycle based conversion of gas processing plant waste heat into power |
US11001543B2 (en) | 2015-10-16 | 2021-05-11 | Lummus Technology Llc | Separation methods and systems for oxidative coupling of methane |
US9944573B2 (en) | 2016-04-13 | 2018-04-17 | Siluria Technologies, Inc. | Oxidative coupling of methane for olefin production |
US10870611B2 (en) | 2016-04-13 | 2020-12-22 | Lummus Technology Llc | Oxidative coupling of methane for olefin production |
US11505514B2 (en) | 2016-04-13 | 2022-11-22 | Lummus Technology Llc | Oxidative coupling of methane for olefin production |
US10960343B2 (en) | 2016-12-19 | 2021-03-30 | Lummus Technology Llc | Methods and systems for performing chemical separations |
WO2018128983A1 (en) * | 2017-01-06 | 2018-07-12 | Sabic Global Technologies, B.V. | An integrated process utilizing methane oxidative conversion heat for ethylene and methanol production |
US20210172076A1 (en) * | 2017-02-27 | 2021-06-10 | Honeywell International Inc. | Electrochemical carbon dioxide converter and liquid regenerator |
US20210172075A1 (en) * | 2017-02-27 | 2021-06-10 | Honeywell International Inc. | Electrochemical carbon dioxide converter and liquid regenerator |
US11519080B2 (en) * | 2017-02-27 | 2022-12-06 | Honeywell International Inc. | Electrochemical carbon dioxide converter and liquid regenerator |
US11519079B2 (en) * | 2017-02-27 | 2022-12-06 | Honeywell International Inc. | Electrochemical carbon dioxide converter and liquid regenerator |
US11001542B2 (en) | 2017-05-23 | 2021-05-11 | Lummus Technology Llc | Integration of oxidative coupling of methane processes |
US10836689B2 (en) | 2017-07-07 | 2020-11-17 | Lummus Technology Llc | Systems and methods for the oxidative coupling of methane |
US11505755B2 (en) | 2017-07-20 | 2022-11-22 | Proteum Energy, Llc | Method and system for converting associated gas |
US10870810B2 (en) * | 2017-07-20 | 2020-12-22 | Proteum Energy, Llc | Method and system for converting associated gas |
US10329215B2 (en) | 2017-10-24 | 2019-06-25 | Sabic Global Technologies, B.V. | Process for converting a natural gas feedstock with inert content to chemical intermediates |
US20190193027A1 (en) * | 2017-10-26 | 2019-06-27 | Marc Privitera | Mobile Extraction Array with brine constituent separation, purification and concentration |
US11085124B2 (en) * | 2018-03-20 | 2021-08-10 | Kabushiki Kaisha Toshiba | Electrochemical reaction device |
CN112973584A (en) * | 2021-02-07 | 2021-06-18 | 中国科学院过程工程研究所 | Fluidized bed reaction device and application thereof |
Also Published As
Publication number | Publication date |
---|---|
WO2016160563A1 (en) | 2016-10-06 |
US20200172452A1 (en) | 2020-06-04 |
CA2975743A1 (en) | 2016-10-06 |
US11186529B2 (en) | 2021-11-30 |
CA2975743C (en) | 2023-11-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11186529B2 (en) | Advanced oxidative coupling of methane | |
US11001543B2 (en) | Separation methods and systems for oxidative coupling of methane | |
US10960343B2 (en) | Methods and systems for performing chemical separations | |
KR101887843B1 (en) | System and Method for Generating Power and Enhanced Oil Recovery | |
KR101788346B1 (en) | Apparatus & process for treating natural gas | |
AU2010298708B2 (en) | Maintaining low carbon monoxide levels in product carbon dioxide | |
GB2591188A (en) | Separations with ionic liquid solvents | |
US20110308388A1 (en) | Absorption method for recovering gas contaminants at high purity | |
WO2019005716A1 (en) | Process for gas separation by solvent or absorbent | |
CN104031681A (en) | Method for recovering ethylene and hydrogen from refinery dry gases by combining cold oil absorption and pressure swing adsorption (PSA) | |
AU2010328581B2 (en) | Maintaining lowered CO in a CO2 product stream in a process for treating synthesis gas | |
JP4758711B2 (en) | Pretreatment method for gas hydrate production | |
CN112969677A (en) | Process for recovering ethylene from dry gas | |
EP2627434A2 (en) | Capturing carbon dioxide from high pressure streams |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: SILURIA TECHNOLOGIES, INC., CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DUGGAL, SUCHIA;RADAELLI, GUIDO;MCCORMICK, JAROD;AND OTHERS;SIGNING DATES FROM 20151001 TO 20151005;REEL/FRAME:036886/0183 |
|
STCV | Information on status: appeal procedure |
Free format text: NOTICE OF APPEAL FILED |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |