Patent Grant
11001543
The modern refining and petrochemical industry may make extensive use of fractionation technology to produce and separate various desirable compounds from crude oil. The conventional fractionation technology may be energy intensive and costly to install and operate. Cryogenic distillation has been used to separate and recover hydrocarbon products in various refining and petrochemical industries.
Recognized herein is a need for non-cryogenic separation methods and systems, such as 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., pressure swing adsorption 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 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 unit that employs a CO2 separation unit to separate the CO2 from the product stream and 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, (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, (iv) metal-organic framework-based separation, or (v) antisublimation separation of CO2.
In some embodiments of aspects provided herein, the product stream is directed into the separations unit through one or more additional units. In some embodiments of aspects provided herein, the sorbent or solvent separation of CO2 employs an amine based absorption unit. In some embodiments of aspects provided herein, the sorbent or solvent separation of CO2 employs a Benfield process. In some embodiments of aspects provided herein, the sorbent or solvent separation of CO2 employs diethanolamine. In some embodiments of aspects provided herein, the sorbent or solvent separation of CO2 employs glycol dimethylether. In some embodiments of aspects provided herein, the sorbent or solvent separation of CO2 employs propylene carbonate. In some embodiments of aspects provided herein, the sorbent or solvent separation of CO2 employs Sulfinol. In some embodiments of aspects provided herein, the sorbent or solvent separation of CO2 employs a zeolite. In some embodiments of aspects provided herein, the sorbent or solvent separation of CO2 employs active carbon. In some embodiments of aspects provided herein, the CO2 separation unit comprises a membrane CO2 separation unit. In some embodiments of aspects provided herein, the membrane separation of CO2 employs a polymeric membrane. In some embodiments of aspects provided herein, the membrane separation of CO2 employs a metallic membrane. In some embodiments of aspects provided herein, the membrane separation of CO2 employs a ceramic membrane. In some embodiments of aspects provided herein, the membrane separation of CO2 employs a hybrid membrane comprising a membrane supporting a solvent or sorbent. In some embodiments of aspects provided herein, the membrane separation of CO2 employs a poly ionic liquid membrane. In some embodiments of aspects provided herein, the membrane separation of CO2 employs a supported ionic liquid membrane. In some embodiments of aspects provided herein, the membrane separation of CO2 employs a polyetherimide membrane. In some embodiments of aspects provided herein, the membrane separation of CO2 employs an amorphous fluoropolymer based membrane. In some embodiments of aspects provided herein, 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 of aspects provided herein, the method further comprises directing the methane in the methanation product stream to the OCM reactor. In some embodiments of aspects provided herein, 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 of aspects provided herein, the method further comprises directing ethane from the product stream to the OCM reactor. In some embodiments of aspects provided herein, the method further comprises, prior to directing the product stream into the separations unit, compressing the product stream. In some embodiments of aspects provided herein, the CO2 separation unit employs the sorbent or solvent separation of CO2. In some embodiments of aspects provided herein, the CO2 separation unit employs the membrane separation of CO2. In some embodiments of aspects provided herein, the CO2 separation unit employs the 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 of aspects provided herein, the CO2 separation unit employs the metal-organic framework-based separation. In some embodiments of aspects provided herein, the CO2 separation unit employs the antisublimation separation of CO2.
Another aspect of 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 first CO2 separation unit that separates at least some of the CO2 from the product stream to produce an enriched stream comprising (i) the C2+ compounds and (ii) at least some of the CO2; (c) directing the enriched stream to a cryogenic separations unit that separates the C2H4 from the C2+ compounds to produce an ethylene stream comprising (i) the C2H4 and (ii) the CO2; and (d) directing the ethylene stream to a second CO2 separation unit that separates the CO2 from the ethylene stream to produce an ethylene product stream.
In some embodiments of aspects provided herein, the enriched stream contains at most about 2.0 mol % CO2. In some embodiments of aspects provided herein, the enriched stream contains at most about 1.0 mol % CO2. In some embodiments of aspects provided herein, the enriched stream contains at most about 0.5 mol % CO2. In some embodiments of aspects provided herein, the first CO2 separation unit comprises a membrane, a pressure swing absorption (PSA) unit, an amine unit, or any combination thereof. In some embodiments of aspects provided herein, the second CO2 separation unit comprises a membrane, a pressure swing absorption (PSA) unit, an amine unit, or any combination thereof. In some embodiments of aspects provided herein, the cryogenic separations unit comprises a de-methanizer.
Another aspect of 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 unit that selectively separates olefins from the paraffins.
In some embodiments of aspects provided herein, the separations unit selectively separates ethylene from paraffins. In some embodiments of aspects provided herein, the separations unit comprises an absorber stripper unit employing pi-complexation. In some embodiments of aspects provided herein, the separations unit comprises a membrane unit including a membrane contactor employing pi-complexation. In some embodiments of aspects provided herein, the separations unit comprises a pressure swing adsorption (PSA) unit comprising a sorbent having dispersed metal ions that are capable of complexing with the olefins. In some embodiments of aspects provided herein, the PSA unit comprises a sorbent selected from a zeolite, a molecular sieve sorbent, a carbon molecular sieve, an activated carbon, a carbon nanotube, and a polymeric resin. In some embodiments of aspects provided herein, the method further comprises using an oxidizing agent to regenerate stabilize the pi-complex. In some embodiments of aspects provided herein, the oxidizing agent comprises HNO3 or KMnO4. In some embodiments of aspects provided herein, the separations unit comprises (i) a pressure swing adsorption (PSA) unit, (ii) a temperature swing adsorption (TSA) unit, or (iii) a membrane unit employing a metal-organic framework (MOF), and the olefins separated in (b) comprise ethylene.
Another aspect of 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) C1 compounds including un-reacted CH4; and (b) directing the product stream into a separations unit that separates the C2+ compounds from the C1 compounds, which separations unit does not contain a de-methanizer.
In some embodiments of aspects provided herein, the separations unit contains a distillation column and an oil absorber. In some embodiments of aspects provided herein, the distillation column does not condense methane.
Another aspect of 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) C1 compounds including un-reacted CH4; (b) directing the product stream into a pre-separations unit that produces (i) a bottoms stream comprising the C2+ compounds and (ii) an overhead stream comprising the C1 compounds and at least some of the C2+ compounds; and (c) directing the overhead stream into an oil absorber that removes the at least some of the C2+ compounds to produce a C1 stream.
In some embodiments of aspects provided herein, the OCM process is integrated with a methanol to olefins (MTO) unit, a steam cracker, or a metathesis process. In some embodiments of aspects provided herein, the pre-separation unit does not include a de-methanizer. In some embodiments of aspects provided herein, the pre-separation unit does not condense methane. In some embodiments of aspects provided herein, the overhead stream comprises at least about 10% C2+ compounds. In some embodiments of aspects provided herein, the overhead stream comprises at least about 5% C2+ compounds. In some embodiments of aspects provided herein, the overhead stream comprises at least about 1% C2+ compounds. In some embodiments of aspects provided herein, the overhead stream comprises at least about 0.1% C2+ compounds.
Another aspect of 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) C1 compounds including un-reacted CH4; and (b) directing the product stream into a separations unit containing a metal organic framework (MOF) that produces (i) a bottoms stream comprising the C2+ compounds and (ii) an overhead stream comprising the C1 compounds.
In some embodiments of aspects provided herein, the method further comprises (c) directing the overhead stream to a methanation unit for converting carbon dioxide (CO2) and/or carbon monoxide (CO) into methane (CH4); and (d) directing the CH4 into the OCM reactor. In some embodiments of aspects provided herein, the method further comprises (e) directing the bottoms stream to a second separations unit containing a metal organic framework (MOF) that separates olefins from paraffins. In some embodiments of aspects provided herein, the separations unit comprises a pressure swing absorber (PSA) that contains the MOF. In some embodiments of aspects provided herein, the separations unit comprises a temperature swing absorber (TSA) that contains the MOF. In some embodiments of aspects provided herein, the C1 compounds include hydrogen (H2).
Another aspect of 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 having a catalytic section and a cracking section to produce an OCM product stream, which catalytic section reacts the O2 and CH4 to yield ethylene (C2H4), ethane (C2H6) and heat, which cracking section uses the heat to convert C2H6 into C2H4, and which product stream comprises (i) C2+ compounds including ethylene (C2H4) and ethane (C2H6) and (ii) C1 compounds including un-reacted CH4; (b) directing the product stream into a separations unit containing a metal organic framework (MOF) that produces (i) a first stream comprising the C2H4, (ii) a second stream comprising the C2H6 and (iii) a third stream comprising the C1 compounds; (c) directing the second stream into the cracking section; and (d) directing the third stream into the catalytic section.
In some embodiments of aspects provided herein, the third stream is directed to a methanation unit prior to directing to the catalytic section, which methanation unit converts carbon dioxide (CO2) and/or carbon monoxide (CO) into methane (CH4). In some embodiments of aspects provided herein, the separations unit comprises a pressure swing absorber (PSA) that contains the MOF. In some embodiments of aspects provided herein, the separations unit comprises a temperature swing absorber (TSA) that contains the MOF. In some embodiments of aspects provided herein, the C1 compounds include hydrogen (H2).
Another aspect of the present disclosure provides a system for generating compounds with two or more carbon atoms (C2+ compounds), comprising: (a) an oxidative coupling of methane (OCM) reactor configured to receive oxygen (O2) and methane (CH4) and react 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) a separations unit fluidically coupled to the OCM reactor and configured to receive the product stream from the OCM reactor, wherein the separations unit comprises a CO2 separation unit to separate the CO2 from the product stream, and 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, (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, (iv) metal-organic framework-based separation, or (v) antisublimation separation of CO2.
In some embodiments of aspects provided herein, the separations unit comprises one or more additional units, and the product stream is directed into the separations unit through the one or more additional units. In some embodiments of aspects provided herein, the sorbent or solvent separation of CO2 employs an amine based absorption unit. In some embodiments of aspects provided herein, the sorbent or solvent separation of CO2 employs a Benfield process. In some embodiments of aspects provided herein, the sorbent or solvent separation of CO2 employs diethanolamine. In some embodiments of aspects provided herein, the sorbent or solvent separation of CO2 employs glycol dimethylether. In some embodiments of aspects provided herein, the sorbent or solvent separation of CO2 employs propylene carbonate. In some embodiments of aspects provided herein, the sorbent or solvent separation of CO2 employs Sulfinol. In some embodiments of aspects provided herein, the sorbent or solvent separation of CO2 employs a zeolite. In some embodiments of aspects provided herein, the sorbent or solvent separation of CO2 employs active carbon. In some embodiments of aspects provided herein, the CO2 separation unit comprises a membrane CO2 separation unit. In some embodiments of aspects provided herein, the membrane separation of CO2 employs a polymeric membrane. In some embodiments of aspects provided herein, the membrane separation of CO2 employs a metallic membrane. In some embodiments of aspects provided herein, the membrane separation of CO2 employs a ceramic membrane. In some embodiments of aspects provided herein, the membrane separation of CO2 employs a hybrid membrane comprising a membrane supporting a solvent or sorbent. In some embodiments of aspects provided herein, the membrane separation of CO2 employs a poly ionic liquid membrane. In some embodiments of aspects provided herein, the membrane separation of CO2 employs a supported ionic liquid membrane. In some embodiments of aspects provided herein, the membrane separation of CO2 employs a polyetherimide membrane. In some embodiments of aspects provided herein, the membrane separation of CO2 employs an amorphous fluoropolymer based membrane. In some embodiments of aspects provided herein, the system further comprises a methanation reactor that is configured to receive the CO2 from the product stream and react the CO2 to yield a methanation product stream comprising methane. In some embodiments of aspects provided herein, the methane in the methanation product stream is directed to the OCM reactor. In some embodiments of aspects provided herein, the product stream is further separated 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 of aspects provided herein, ethane is directed from the product stream to the OCM reactor. In some embodiments of aspects provided herein, the product stream is compressed, prior to being directed into the separations unit. In some embodiments of aspects provided herein, the CO2 separation unit employs the sorbent or solvent separation of CO2. In some embodiments of aspects provided herein, the CO2 separation unit employs the membrane separation of CO2. In some embodiments of aspects provided herein, the CO2 separation unit employs the 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 of aspects provided herein, the CO2 separation unit employs the metal-organic framework-based separation. In some embodiments of aspects provided herein, the CO2 separation unit employs the antisublimation separation of CO2.
Another aspect of the present disclosure provides a system for generating compounds with two or more carbon atoms (C2+ compounds), comprising: an oxidative coupling of methane (OCM) reactor configured to receive oxygen (O2) and methane (CH4) and react 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); a first CO2 separation unit fluidically coupled to the OCM reactor and configured to receive the product steam from the OCM reactor, wherein the first CO2 separation unit separates at least some of the CO2 from the product stream to produce an enriched stream comprising (i) the C2+ compounds and (ii) at least some of the CO2; a cryogenic separations unit fluidically coupled to the first CO2 separation unit and configured to receive the enriched stream from the first CO2 separation unit, wherein the cryogenic separations unit separates the C2H4 from the C2+ compounds to produce an ethylene stream comprising (i) the C2H4 and (ii) the CO2; and a second CO2 separation unit fluidically coupled to the cryogenic separations unit and configured to receive the ethylene stream from the cryogenic separations unit, wherein the second CO2 separation unit separates the CO2 from the ethylene stream to produce an ethylene product stream.
In some embodiments of aspects provided herein, the enriched stream contains at most about 2.0 mol % CO2. In some embodiments of aspects provided herein, the enriched stream contains at most about 1.0 mol % CO2. In some embodiments of aspects provided herein, the enriched stream contains at most about 0.5 mol % CO2. In some embodiments of aspects provided herein, the first CO2 separation unit comprises a membrane, a pressure swing absorption (PSA) unit, an amine unit, or any combination thereof. In some embodiments of aspects provided herein, the second CO2 separation unit comprises a membrane, a pressure swing absorption (PSA) unit, an amine unit, or any combination thereof. In some embodiments of aspects provided herein, the cryogenic separations unit comprises a de-methanizer.
Another aspect of the present disclosure provides a system for generating compounds with two or more Carbon atoms (C2+ compounds), comprising: an oxidative coupling of methane (OCM) reactor configured to receive oxygen (O2) and methane (CH4) and react 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 a separations unit fluidically coupled to the OCM reactor and configured to receive the product stream from the OCM reactor, wherein the separations unit selectively separates olefins from the paraffins.
In some embodiments of aspects provided herein, the separations unit selectively separates ethylene from paraffins. In some embodiments of aspects provided herein, the separations unit comprises an absorber unit employing pi-complexation. In some embodiments of aspects provided herein, the separations unit comprises a membrane unit including a membrane contactor employing pi-complexation. In some embodiments of aspects provided herein, the separations unit comprises a pressure swing adsorption (PSA) unit comprising a sorbent having dispersed metal ions that are capable of complexing with the olefins. In some embodiments of aspects provided herein, the PSA unit comprises a sorbent selected from a zeolite, a molecular sieve sorbent, a carbon molecular sieve, an activated carbon, a carbon nanotube, and a polymeric resin. In some embodiments of aspects provided herein, the system further comprises an oxidizing agent used to regenerate and/or stabilize the pi-complex. In some embodiments of aspects provided herein, the oxidizing agent comprises HNO3 or KMnO4. In some embodiments of aspects provided herein, the separations unit comprises (i) a pressure swing adsorption (PSA) unit, (ii) a temperature swing adsorption (TSA) unit, or (iii) a membrane system employing a metal-organic framework (MOF), and the olefins separated comprise ethylene.
Another aspect of the present disclosure provides a system for generating compounds with two or more carbon atoms (C2+ compounds), comprising: an oxidative coupling of methane (OCM) reactor configured to receive oxygen (O2) and methane (CH4) and react the O2 and CH4 in an OCM process to yield a product stream comprising (i) C2+ compounds including ethylene (C2H4) and (ii) C1 compounds including un-reacted CH4; and a separations unit fluidically coupled to the OCM reactor and configured to receive the product stream from the OCM reactor, wherein the separations unit separates the C2+ compounds from the C1 compounds, and wherein the separations unit does not contain a de-methanizer.
In some embodiments of aspects provided herein, the separations unit contains a distillation column and an oil absorber. In some embodiments of aspects provided herein, the distillation column does not condense methane.
Another aspect of the present disclosure provides a system for generating compounds with two or more carbon atoms (C2+ compounds), comprising: an oxidative coupling of methane (OCM) reactor configured to receive oxygen (O2) and methane (CH4) and react the O2 and CH4 in an OCM process to yield a product stream comprising (i) C2+ compounds including ethylene (C2H4) and (ii) C1 compounds including un-reacted CH4; a pre-separations unit fluidically coupled to the OCM reactor and configured to receive the product stream from the OCM reactor, wherein the pre-separations unit produces (i) a bottoms stream comprising the C2+ compounds and (ii) an overhead stream comprising the C1 compounds and at least some of the C2+ compounds; and an oil absorber fluidically coupled to the pre-separations unit and configured to receive the overhead stream from the pre-separations unit, wherein the oil absorber removes the at least some of the C2+ compounds to produce a C1 stream.
In some embodiments of aspects provided herein, the OCM process is integrated with a methanol to olefins (MTO) unit, a steam cracker, or a metathesis process. In some embodiments of aspects provided herein, the pre-separation unit does not include a de-methanizer. In some embodiments of aspects provided herein, the pre-separation unit does not condense methane. In some embodiments of aspects provided herein, the overhead stream comprises at least about 10% C2+ compounds. In some embodiments of aspects provided herein, the overhead stream comprises at least about 5% C2+ compounds. In some embodiments of aspects provided herein, the overhead stream comprises at least about 1% C2+ compounds. In some embodiments of aspects provided herein, the overhead stream comprises at least about 0.1% C2+ compounds.
Another aspect of the present disclosure provides a system for generating compounds with two or more carbon atoms (C2+ compounds), comprising: an oxidative coupling of methane (OCM) reactor configured to receive oxygen (O2) and methane (CH4) and react the O2 and CH4 in an OCM process to yield a product stream comprising (i) C2+ compounds including ethylene (C2H4) and (ii) C1 compounds including un-reacted CH4; and a separations unit fluidically coupled to the OCM reactor and configured to receive the product stream from the OCM reactor, wherein the separations unit contains a metal organic framework (MOF) that produces (i) a bottoms stream comprising the C2+ compounds and (ii) an overhead stream comprising the C1 compounds.
In some embodiments of aspects provided herein, the system further comprises a methanation unit fluidically coupled to the separations unit and configured receive the overhead stream from the separations unit, wherein the methanation unit converts carbon dioxide (CO2) and/or carbon monoxide (CO) into methane (CH4), and wherein the CH4 is directed into the OCM reactor. In some embodiments of aspects provided herein, the system further comprises a second separations unit fluidically coupled to the separations unit and configured receive the bottoms stream from the separations unit, wherein the second separations unit contains a metal organic framework (MOF) that separates olefins from paraffins. In some embodiments of aspects provided herein, the separations unit comprises a pressure swing absorber (PSA) that contains the MOF. In some embodiments of aspects provided herein, the separations unit comprises a temperature swing absorber (TSA) that contains the MOF. In some embodiments of aspects provided herein, the C1 compounds include hydrogen (H2).
Another aspect of the present disclosure provides a system for generating compounds with two or more carbon atoms (C2+ compounds), comprising: an oxidative coupling of methane (OCM) reactor configured to receive oxygen (O2) and methane (CH4) and react the O2 and CH4 to produce an OCM product stream, the OCM reactor having a catalytic section and a cracking section, which catalytic section reacts the O2 and CH4 to yield ethylene (C2H4), ethane (C2H6) and heat, which cracking section uses the heat to convert C2H6 into C2H4, and which product stream comprises (i) C2+ compounds including ethylene (C2H4) and ethane (C2H6) and (ii) C1 compounds including un-reacted CH4; and a separations unit fluidically coupled to the OCM reactor and configured to receive the product stream from the OCM reactor, wherein the separations unit contains a metal organic framework (MOF) that produces (i) a first stream comprising the C2H4, (ii) a second stream comprising the C2H6 and (iii) a third stream comprising the C1 compounds, and wherein the second stream and the third stream are directed into the cracking section and the catalytic section respectively.
In some embodiments of aspects provided herein, the third stream is directed to a methanation unit prior to directing to the catalytic section, which methanation unit converts carbon dioxide (CO2) and/or carbon monoxide (CO) into methane (CH4). In some embodiments of aspects provided herein, the separations unit comprises a pressure swing absorber (PSA) that contains the MOF. In some embodiments of aspects provided herein, the separations unit comprises a temperature swing absorber (TSA) that contains the MOF. In some embodiments of aspects provided herein, the C1 compounds include hydrogen (H2).
Another aspect of the present disclosure provides a non-transitory computer-readable medium comprising machine-executable code that, upon execution by one or more computer processors, implements any of the methods above or elsewhere herein.
Another aspect of the present disclosure provides a system comprising one or more computer processors and a non-transitory computer-readable medium coupled thereto. The non-transitory computer-readable medium comprises machine-executable code that, upon execution by the one or more computer processors, implements any of the methods above or elsewhere herein.
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:
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.
The term “unit,” as used herein, generally refers to a unit operation. A unit operation may be one or more basic steps in a process. A unit may have one or more sub-units (or sub-systems). Unit operations may involve a physical change or chemical transformation, such as separation, crystallization, evaporation, filtration, polymerization, isomerization, and other reactions. A unit may include one or more individual components. For example, a separations unit may include one or more separations columns or an amine unit may include one or more amine columns.
Separations
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.
Auto Refrigeration
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 %, 90 mol %, or more. 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.
Mixed Refrigeration
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
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
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, or a PSA system with metal ions dispersed on the sorbent. For good adsorption, the cations can be spread (e.g., with high dispersion) on solid substrates with a high surface area. There are at least three types of metal complexation sorbents that can be used in the methods and systems described herein (i.e., monolayer or near monolayer salts supported on porous substrates, ion-exchange zeolites, and ion-exchange resins). For bulk separation, the monolayer salts on porous substrates and ion-exchange resins can be more suitable in some cases. Ion-exchange zeolites are usually more suitable for olefin recovery or purification. Substrates for supporting salts may include Y-Alumina (porous), silica gel, activated carbon, TiO2, and a number of zeolites. The metal ion can be Ag+ or Cu+ ion.
Membrane contactors using a silver nitrate solution or a copper salt solution can be used to separate the olefins from the OCM effluent stream. The contactor can include the salt solution in a membrane module or unit. Many such modules or units can be put together in a contactor system where the salt solution is circulated. Such membrane contactors can result in substantial olefin recovery from a feed containing a mixture of olefins and paraffins (e.g., propane and/or propylene). The process described herein can be used to separate ethylene from the OCM effluent containing methane and ethane, resulting in elimination of whole, or part of the cryogenic recovery system in a typical OCM system.
As described herein, OCM process can be integrated with a Permylene membrane system to recover or separate the bulk of ethylene. In some cases, Permylene membranes can be used to separate olefins from paraffins. The Permylene process can use a flat sheet composite structure based on chitosan material and silver cations as facilitating agents. Chitosan can be produced by the deacetylation of chitin, which is the structural element in the exoskeleton of crustaceans. Chitosan can act as the active layer of the Permylene membrane. In contact with an aqueous solution containing silver ions, a hydrogel can be formed and the silver ions can form metal complexes with the olefins. The olefin molecules can be transported across the membrane under the influence of the olefin partial pressure differential between the feed and permeate sides of the membrane and can be released on the low pressure permeate side. Gases without a carbon-carbon double bond are rejected.
In some instances, an oxidizing agent can be used to either stabilize or improve the formation of the desired metal complex with olefin, and/or to regenerate or destabilize the undesired complexes formed. For example, in a copper based system, adding nitric acid can improve the stability of formation of the metal-olefin complex.
Membranes
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.
Pressure Swing Adsorption (PSA) and Adsorption Technology
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.
Pressure Swing Adsorption (PSA)
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
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
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 4A zeolite is one such example. For example, a three-bed system can be used to recover olefins from a stream containing 80-85% olefins and 10-15% paraffins, using a 4A type zeolite at elevated temperatures (e.g., the Petrofin process). Pi complexation sorbents, such as AgNO3/SiO2, can give excellent results as compared to 4A 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).
Separations, such as of ethylene and propylene, can be conducted using an amorphous fluoropolymer based membrane. Facilitated transport using silver ions can selectively transport ethylene and/or propylene. The membrane can be a part of a membrane contactor system. The feed to the system can be of a low to moderate olefin concentration. The feed to the system can contain other hydrocarbons, including, but not limited to, methane, ethane, propane, butane, butenes, C5 components and higher hydrocarbons. The feed can also contain CO2, CO, H2, and inert components, such as nitrogen.
CO2 Separation
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.
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
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.
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 can separate 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, but are not limited to, polymeric membranes based on or comprising polyamides, poly semicarbazides, polycarbonates, polyarylates, polyaniline, poly(phenylen oxide), polysulfones, polypyrrolones, or combinations thereof. 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/or 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
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.
As shown in
As shown in
The first (bulk) CO2 separations system can be a membrane or a PSA system, an amine removal system, or any other solvent based CO2 removal system as described herein. The final CO2 removal step can be a caustic tower, a membrane based system, a PSA based system, or any other CO2 removal system as described herein. The ethylene product CO2 removal system 580 can be followed by further drying and/or purification steps.
One advantage of the two step process described herein can be energy saving that arise from decreasing the gas volumes being processed for the final CO2 removal step. If CO2 removal is done entirely upstream of the demethanizer, the energy consumption is much greater than described in
The concentration of CO2 going into the de-methanizer (following the first CO2 removal unit) can be any suitable amount (i.e., such that CO2 doesn't freeze in the de-methanizer). In some embodiments, the concentration of CO2 going into the de-methanizer is about 0.1 mol %, about 0.2 mol %, about 0.3 mol %, about 0.4 mol %, about 0.5 mol %, about 0.6 mol %, about 0.7 mol %, about 0.8 mol %, about 0.9 mol %, about 1.0 mol %, about 1.2 mol %, about 1.4 mol %, about 1.6 mol %, about 1.8 mol %, about 2.0 mol %, about 2.2 mol %, about 2.4 mol %, about 2.6 mol %, about 2.8 mol %, about 3.0 mol %, about 3.5 mol %, about 4.0 mol %, or about 5.0 mol %. In some cases, the concentration of CO2 going into the de-methanizer is at least about 0.1 mol %, at least about 0.2 mol %, at least about 0.3 mol %, at least about 0.4 mol %, at least about 0.5 mol %, at least about 0.6 mol %, at least about 0.7 mol %, at least about 0.8 mol %, at least about 0.9 mol %, at least about 1.0 mol %, at least about 1.2 mol %, at least about 1.4 mol %, at least about 1.6 mol %, at least about 1.8 mol %, at least about 2.0 mol %, at least about 2.2 mol %, at least about 2.4 mol %, at least about 2.6 mol %, at least about 2.8 mol %, at least about 3.0 mol %, at least about 3.5 mol %, at least about 4.0 mol %, or at least about 5.0 mol %. In some cases, the concentration of CO2 going into the de-methanizer is at most about 0.1 mol %, at most about 0.2 mol %, at most about 0.3 mol %, at most about 0.4 mol %, at most about 0.5 mol %, at most about 0.6 mol %, at most about 0.7 mol %, at most about 0.8 mol %, at most about 0.9 mol %, at most about 1.0 mol %, at most about 1.2 mol %, at most about 1.4 mol %, at most about 1.6 mol %, at most about 1.8 mol %, at most about 2.0 mol %, at most about 2.2 mol %, at most about 2.4 mol %, at most about 2.6 mol %, at most about 2.8 mol %, at most about 3.0 mol %, at most about 3.5 mol %, at most about 4.0 mol %, or at most about 5.0 mol %. In some cases, the concentration of CO2 going into the de-methanizer is between any of the two values described above, for example, between about 0.5 mol % and about 2.0 mol %.
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 at least about 1 wt %, 5 wt %, 10 wt %, 15 wt %, 20 wt %, 25 wt %, 30 wt %, 35 wt %, or more amine and/or polyol. In some cases, 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.
CO2 Anti-Sublimation
Carbon capture (e.g., CO2 capture) can be used to reduce greenhouse gas (GHG) emissions. For example, carbon can be captured from stationary fired sources (e.g., flue gas emissions from fired equipment in power plants and industry). CO2 capture technologies may be cost prohibitive. The cost of disposing CO2 can be divided into: separation (for example, the cost range for CO2 separation from flue gas using amine absorption is $30-$50 per ton of CO2); compression (for example, CO2 is compressed typically to 2000 psi for pipeline delivery and compression costs can range from $8-$10 per ton of CO2); pipelines (for example, CO2 pipelining costs can range from $0.7 to $4 per ton CO2 per 100 km); and injection (for example, compressed CO2 injection to geological reservoirs on land can cost from $2-$8 per ton CO2.
The separation of process CO2 from the OCM process can be simpler and less expensive than a CO2 capture from a flue gas system. Flue gas CO2 capture may have inherent challenges, which are absent from the OCM system CO2: low pressure (for example, the typical flue gas pressures are at or about atmospheric pressure, and therefore involve high volumes that can need to be compressed and treated, resulting in bigger and hence more expensive equipment); high temperature (for example, flue gases can exit a furnace or heater at a high temperature); oxygen content (for example, oxygen can cause corrosion problems); NOx and fly ash content (for example, this can cause degradation in certain systems); and CO2 concentration (for example, in flue gases CO2 concentration can range from 10%-15%; in OCM CO2 concentrations can be 95% and higher post amine system or 4-6% at OCM outlet).
To integrate well with OCM, a CO2 separation process can be: less energy and capital intensive than current designs (e.g., amine system); scalable downwards and upwards; capable of reliable and continuous operation; able to take advantage of high CO2 concentrations and convert to high purity CO2, which can be used as a feedstock for other operations.
CO2 anti-sublimation can be used to remove CO2 (e.g., from flue gas). CO2 anti-sublimation can use an SO2 removal unit followed by a water cooling step. The water can be eventually removed, for example first as liquid then below the triple point as ice. Dry flue gas can be further cooled until CO2 precipitates. The process can employ anti-sublimating CO2 on a low temperature surface, thus transforming the carbon dioxide from its gaseous phase to a solid phase frosted on a cold surface. Anti-sublimation can allow CO2 capture at a pressure slightly higher than atmospheric. CO2 anti-sublimation can be used with a flue gas system (flue gas composition, e.g., in mol %: CO2 15%, H2O 13%, N2 70% and O2 3%) at various temperatures (e.g., about 51° C.).
The triple point of CO2 is −56.4° C. and 5.11 atm. For 100% pure CO2 at a pressure P′ (where P′ is less than 5.11 atm) the frosting temperature can be given by T′=(P′−15.6)*(22.1/4.11). Accordingly, for a pressure of 4.5 atm, T=−59.6° C.
The sublimation temperature of a substance within a gas mixture can depend on its partial pressure (its corresponding concentration within the mixture). Table 1 shows frosting temperatures at different exemplary CO2 concentrations.
For use in an OCM process, a CO2 anti-sublimation unit may encounter higher pressure of OCM effluent (e.g., feed to CO2 capture system), lower CO2 concentration, and higher hydrocarbon content (e.g., methane, ethane, ethylene). Lower CO2 concentration can be addressed by a recycle.
Process Configurations
Electrolysis to Generate Oxygen and Hydrogen for OCM Process
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.
Different Quench Media for the OCM Reaction
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.
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.
Heat Recovery
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).
Organic Rankine 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.
Thermoelectric Power Generation
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 Publication No. US 2015/0210610, which is entirely incorporated herein by reference. ETL systems are described in, for example, U.S. Patent Publication No. 2015/0232395, which is entirely incorporated herein by reference.
An OCM system, such as that shown in
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.
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 it-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.,
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.
Retrofits for OCM
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 may include addition of, or debottlenecking of, the existing fractionation towers for the entire flow addition for the revamp. However, as shown in
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
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.
ETL Systems
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 Publication No. 2015/0232395, which is entirely incorporated herein by reference.
In some cases, 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.
Retrofit Applications for Midstream and Refining
Systems, such as those of
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.
Refining
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.
As shown in
Metal-Organic Frameworks (MOFs) for Hydrocarbon Separation
The separation section of OCM unit can employ cryogenic distillation systems. In some cases, the distillation section can be partially or completely replaced by efficient advanced separation technologies that operate at higher/room temperatures, such as membranes or PSA. This can result in energy savings.
Among the materials used for membranes and adsorption beds, metal-organic frameworks (MOFs) can be highly beneficial. MOFs can comprise metal ions and organic linkers. MOFs can be highly porous sponge-like materials. The choice of metal ion and linker can define the structure and hence the properties of MOFs. MOFs can exhibit advantages of both organic and inorganic moieties. They can be more advantageous than zeolites due to higher surface areas and higher flexibility in pore sizes (e.g., based on their synthesis). They can be better than typical membranes for separation since they can be more robust, more mechanically and thermally stable, and can avoid issues such as carrier poisoning or reduction of complexing agents.
The process effluent from OCM can comprise light gases, such as methane, hydrogen, carbon dioxide, ethylene, ethane, acetylene, propane, propene and C4+ compounds. MOFs can be used to separate C2+ compound streams from the bulk CH4 and H2 in effluent. MOFs can also be used to recover ethylene from a mixed stream of C2 compounds, C3 compounds and C4+ compounds, remove CO2, and recover hydrogen for further processing.
Different combinations of MOFs can be synthesized to provide different separation properties. MOFs can be useful in hydrocarbon separation due to their capability of separating component gases by mechanisms such as molecular sieving, characteristic gate opening pressures for different penetrant molecules or other changes in the structure of the MOFs due to adsorbent/adsorbate interactions. Without being limited by theory, adsorption selectivity can arise from interactions using it-complexation between the double bond in ethylene molecules and partial positive charges of co-ordinatively unsaturated metal ions (e.g., Cu(II)). MOFs such as HKUST-1 can be used to separate ethylene from ethane. Other MOFs capable of separating ethylene over ethane include Ag+ based MOFs, Co2(2,5-dihydroxyterephthalate, or “dhtp”), and Mg2(dhtp). MOFs such as ZIF-7, ZIF-8, and ZIF-4 can be used for selective adsorption of paraffins (e.g., ethane) over ethylene due to the gate-opening effect or the breathing behavior of the MOF. ZIF-8 can adsorb alkanes (e.g., methane) over alkenes (e.g., ethylene). The selectivity of this separation can be controlled by adjusting the hydration level of the MOF. MOFs such as ZIF-67, SBMOF-1, SBMOF-2, Cu-TDPAT, USTA-33a, ZJU-61, USTA-33, USTA-10a can be used for selective separation of methane from other hydrocarbons such as C2 compounds. The MOF M2(dobdc) can be used to effectively separate acetylene, ethylene, ethane, and methane collectively or individually from their mixtures. The M2(dobdc) can be in the meta form M2(m-dobdc) or the para form M2(p-dobdc). The metal can be any suitable metal such as iron (Fe), nickel (Ni) or cobalt (Co). Further information on these MOFs can be found in PCT Publication No. WO 2015/066693A1, which is incorporated herein by reference in its entirety. IRMOFs, such as MOF-5, can be used for separation of hydrogen from hydrogen/methane and hydrogen/C2 mixtures. RPM3-Zn can be used to separate C1-C4 paraffins. MOFs such as UTSA-100, SIF SIX, ZJU-5 can be utilized for acetylene removal from the olefins stream where back-end acetylene removal is used rather than acetylene hydrogenation. MOFs such as M-(dobdc) can be modified with amines to selectively remove CO2. Several MOFs such as ZIF-68-70, 78, 79, 81 82, MOF-11, MOF-508b, PCN-60, 61, MIL-100, MIL-101, ZIF-8, SNU-9, MIL-102(Cr), MIL-53(Cr) have been studied for removal of CO2 from methane and nitrogen and can be utilized for, e.g., a front end CO2 removal system. MOFs such as M2(dobpdc) can be used to remove CO2 from other gases and can be used for CO2 removal front or back of the OCM process described herein. MOFs such as Fe-BTTri can be used for CO removal from various components such as CO2, N2, CH4 and can be used for back end CO removal in the OCM unit.
MOFs can be used in the adsorbent beds of PSA/TSA system or as a part of membrane based applications. As part of membrane systems, they can be incorporated in thin film membranes or mixed matrix membranes (MMMs). With MMMs, MOFs have shown improved gas separation qualities, with increased permeability and selectivity using MMMs. Mixed matrix membranes can combine the advantages of easy and cheap fabrication of polymer membranes with the improved gas separation properties of different MOFs.
For an OCM process, MOFs can be utilized for separation of various light hydrocarbons. In
In
In
In summary, different MOFs can be utilized for their specific selectivities and adsorption capabilities, for example in MMMs or adsorbent beds as PSA systems for hydrocarbon separation of the OCM effluent. MOFs can be very advantageous for their on-purpose synthesis and high surface areas (highest surface area/gram compared to any other material). MOFs in combination with other separation systems (such as polymeric membranes, zeolites, and cryogenic distillation) can be used in novel process schemes to produce OCM product (e.g., ethylene).
Separations Systems Using an Oil Absorption Tower
Another aspect of the present disclosure provides a method and system for separating the OCM reactor product mixture using an oil absorption system along with distillation. The oil absorption system may include (a) an oil absorption and stripper system and/or (b) an oil absorption system preceded by a pre-separation column to do a bulk separation between C1 and C2 compounds. This system can eliminate the need of a demethanizer, thereby reducing the overall energy consumption and capex by eliminating the need for C2 or C1 refrigeration.
As shown in
In some cases, the feed to the separation system can be the product from either an OCM reactor as discussed above, an OCM process integrated with a Methanol to Olefins (MTO) unit, an OCM process integrated with a steam cracker, or an OCM process integrated with a dimerization and metathesis unit for example.
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, now U.S. Pat. No. 9,334,204, 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.
This application is a continuation of U.S. patent application Ser. No. 15/272,205, filed Sep. 21, 2016, which claims priority to U.S. Provisional Patent Application No. 62/242,777, filed Oct. 16, 2015, and U.S. Provisional Patent Application No. 62/304,877, filed Mar. 7, 2016, each of which is entirely incorporated herein by reference for all purposes.
This invention was made with government support under grant numbers DE-EE0005769 awarded by the United States Department of Energy (DOE). The government has certain rights in the invention.
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| Number | Date | Country | |
|---|---|---|---|
| 20200048165 A1 | Feb 2020 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62304877 | Mar 2016 | US | |
| 62242777 | Oct 2015 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15272205 | Sep 2016 | US |
| Child | 16357012 | US |
