METHOD FOR OXIDATIVE COUPLING OF METHANE TO GENERATE HYDROCARBON COMPOUNDS CONTAINING AT LEAST TWO C

专利摘要:
method for the oxidative coupling of methane to generate hydrocarbon compounds containing at least two carbon atoms The present disclosure provides for petrochemical and natural gas processing systems including oxidative coupling of methane reactor systems that integrate process inputs and outputs for cooperative use different inputs and outputs of the various systems in the production of higher hydrocarbons from natural gas and other hydrocarbon feedstocks.
公开号:BR112015000393B1
申请号:R112015000393-1
申请日:2013-07-09
公开日:2021-08-31
发明作者:Rahul Iyer；Alex Tkachenko；Sam Weinberger；Erik C. Scher；Guido Radaelli；Hatem Harraz
申请人:Lummus Technology Llc；
IPC主号:

专利说明:

CROSS REFERENCE
[0001] This application claims the benefit of US Provisional Patent Application No. 61/773,669, filed March 6, 2013 and US Provisional Patent Application No. 61/669,523, filed July 9, 2012, each of which are incorporated herein by reference in their entirety. FUNDAMENTALS
[0002] There is a petrochemical processing infrastructure throughout the world. This infrastructure is deployed on virtually every continent, serves industries of a wide scope, and employs a wide variety of different implementations of similar or very different technologies.
[0003] As a major constituent to this infrastructure, the gas industry itself involves various components of exploration, recovery, processing and conversion technologies in transforming natural gas into useful products. In the United States alone, the gas industry involves hundreds of thousands of processing and fractionation facilities. These facilities typically include all the process equipment necessary for processing and separating natural gas into its constituent and valuable components, as well as the necessary gas delivery infrastructure and storage and distribution infrastructure for a wide range of different products, including products liquids.
[0004] Additional processing, conversion and/or marketing of these products may also involve additional infrastructure. For example, converting ethane from gas to higher value chemicals, eg olefins, involves substantial infrastructure in the form of steam cracking devices and their associated infrastructure. Likewise, in other geographic areas, production of olefins depends on the conversion of by-products, refining oil or naphtha, through alternative cracking operations to produce ethylene and other olefins.
[0005] As will be estimated, the capital costs associated with each of the types of facilities described above can range from tens of millions of dollars to hundreds of millions of dollars each. Furthermore, there are inputs and outputs of these facilities, in terms of energy and materials, which have additional costs associated with them, both financial and otherwise, that could be further optimized in terms of cost and efficiency. Furthermore, because different facilities tend to be optimized for the particularities (eg products, processing conditions) of the market in which they exist, they tend to be operated inflexibly, in some cases without the flexibility or option to optimize your particular market, for example, a particular oil or gas environment. ABSTRACT
[0006] The present disclosure provides systems and methods for reacting methane in an oxidative process methane coupling ("OCM") to produce products comprising hydrocarbon compounds with two or more carbon atoms (also "C2+ compounds" herein) and separate products into streams for use in various downstream processes. OCM systems and disclosure methods can be integrated into various hydrocarbon processes. The present disclosure provides integrated processing facilities for producing higher hydrocarbons from natural gas and other hydrocarbon feedstocks.
[0007] In some examples, processing facilities or systems include an integrated OCM reactor system that provides various components of your OCM product, or other outputs, as an input to various systems in the processing facility, including, for example, refineries, extraction systems, fractionation systems and the like. Alternatively or additionally, integrated OCM reactor systems are provided which comprise various product streams or outputs from different units or systems in these processing facilities.
[0008] The existing processing infrastructure can be advantageously leveraged for new processing methods and systems without spending significant capital resources on retreading this infrastructure, in some cases taking advantage of the different inputs and outputs of these facilities to create greater value from them or similar infrastructure, raw materials, and/or process flows.
[0009] In one aspect, a method for oxidative coupling of methane to produce hydrocarbon compounds containing at least two carbon atoms (C2+ compounds) comprises (a) directing a feed stream comprising methane from a hydrocarbon processing in a coupling reactor methane oxidative (OCM), where the OCM reactor is configured to generate C2+ compounds from methane, and where hydrocarbon processing is a non-OCM process; running one or more OCM reactions in the OCM reactor using methane to produce a product stream composed of one or more C2+ compounds; and separating the product stream into at least a first stream and a second stream, where the first stream has a lower C2+ concentration than the second stream, and wherein the second stream has a higher C2+ concentration than the product flow.
[0010] In some embodiments, the hydrocarbon processing is an oil refinery, a natural gas liquids process or a cracking. In some embodiments, at least a portion of the first stream is directed to the OCM reactor.
[0011] In some cases, a concentration of C2+ compounds in the second stream is less than about 90%. In some embodiments, concentration of C2+ compounds in the second stream is less than about 80%. In some cases, the concentration of C2+ compounds in the second stream is less than about 70%. In some embodiments, concentration of C2+ compounds in the second stream is less than about 60%. In some cases, the first stream has a concentration of C2+ compounds that is less than about 50%.
[0012] In some cases, the product stream is separated into a maximum of three separation units. In some embodiments, the product flow is separated into a maximum of two separation units.
[0013] In some cases, the separation is with the aid of adsorption by pressure variation. Alternatively, or in addition to, separation takes place with the aid of cryogenic separation. Alternatively, or in addition to, separation takes place with the aid of temperature change adsorption.
[0014] In another aspect, a method for oxidative coupling of methane to generate hydrocarbon compounds containing at least two carbon atoms (C2+ compounds) comprises (a) directing a feed stream comprising methane into a methane reactor oxidative coupling (OCM), where the OCM reactor is configured to generate C2+ methane compounds; (b) performing one or more OCM reactions in the OCM reactor using methane to produce a product stream composed of one or more C2+ compounds; (c) separate the product stream into at least a first stream and a second stream, where the first stream has a lower C2+ concentration than the second stream, and where the second stream has a higher C2+ concentration than the that the product flow; and (d) driving the second stream into a hydrocarbon processing, where the hydrocarbon processing is a non-OCM process.
[0015] In some embodiments, the hydrocarbon processing is an oil refinery, a natural gas liquids process or a cracking. In some embodiments, the product stream is separated into a maximum of three separation units.
[0016] In some cases, a concentration of C2+ compounds in the second stream is within about 20% of the concentration of C2+ compounds in a portion of the hydrocarbon processing into which the second stream is directed. In some embodiments, a concentration of C2+ compounds in the second stream is within about 5% of the concentration of C2+ compounds in a portion of the hydrocarbon processing into which the second stream is directed.
[0017] In some cases, the separation is with the aid of adsorption by pressure variation. In some modalities, separation takes place with the aid of cryogenic separation. In some embodiments, the feed flow is directed into the OCM reactor with the aid of a pumping system.
[0018] In another aspect, an oxidative coupling of the methane system (OCM) is composed of (a) a non-OCM hydrocarbon processing that provides a feed stream composed of methane; (b) a OCM reactor fluidly coupled to the processing of non-OCM hydrocarbons, where the OCM reactor (i) takes the input feed stream and (ii) generates, from methane, a product stream consisting of compounds of C2+ and non-C2+ impurities; and (c) at least one separations unit downstream and fluidly coupled to the OCM reactor, wherein at least one separation unit (i) receives as input the product flow, and (ii) separates the C2+ compounds from at least a subset of the non-C2+ impurities.
[0019] In some cases, the processing of non-CMO hydrocarbons is an oil refinery, a natural gas liquids process or a cracking. In some embodiments, the system still comprises a non-OCM hydrocarbon processing downstream of at least one separation unit. In some embodiments, the at least one separation unit is composed of a pressure variation adsorption unit. In some embodiments, at least one separation unit one is composed of a cryogenic separation unit.
[0020] In some embodiments, non-C2+ impurities comprise one or more of nitrogen (N2), oxygen (O2), water (H2O), argon (Ar), carbon monoxide (CO), carbon dioxide (CO2) and methane (CH4).
[0021] In another aspect, an oxidative coupling of the methane system (OCM) is composed of (a) an OCM reactor that (i) takes as input a feed stream composed of methane, and (ii) generates, from from methane, a product stream consisting of non-C2+ impurity compounds; (b) at least one separations unit downstream of and fluidly coupled to the OCM reactor, wherein the at least one separations unit (i) accepts the product flow as input and (ii) separates the C2+ compounds from at least a subset of the non-C2+ impurities in a process stream, comprising at least a subset of the C2+ compounds; and (c) a downstream non-OCM hydrocarbon processing fluidly coupled to at least one separations unit, wherein the non-OCM hydrocarbon process inputs the process flow for use in one or more non-OCM processes .
[0022] In some embodiments, the processing of non-CMO hydrocarbons is an oil refinery, a natural gas liquids process or a cracking. In some embodiments, the system still comprises a non-OCM hydrocarbon processing downstream of at least one separation unit. In some embodiments, the at least one separation unit is composed of a pressure variation adsorption unit.
[0023] In some cases, at least one separation unit one is composed of a cryogenic separation unit.
[0024] In another aspect, a method for integrating a methane process oxidative coupling (OCM) with a hydrocarbon processing comprises (a) directing a feed stream composed of methane into a methane reactor oxidative coupling (OCM), where the OCM reactor is configured to generate C2+ methane compounds; (b) performing one or more OCM reactions in the OCM reactor using methane to produce a product stream composed of one or more C2+ compounds; (c) separate the product stream into at least a first stream and a second stream, where the first stream has a lower C2+ concentration than the second stream, and where the second stream has a higher C2+ concentration than the that the product flow; and (d) driving the second stream in a process stream of a hydrocarbon processing at a time when the concentration of C2+ compounds in the process stream is at most about 10% different from the concentration of C2+ compounds in the second stream .
In some cases, the point at which the second stream enters hydrocarbon processing has a concentration of C2+ compounds that is at most about 5% different from the concentration of the one or more C2+ compounds in the second stream. In some embodiments, the concentration of C2+ compounds in the second stream is greater than the concentration of C2+ compounds at the point where the second stream enters hydrocarbon processing.
[0026] In some embodiments, the hydrocarbon processing is an oil refinery, a natural gas liquids (NGL) process or a cracking. In some embodiments, the product stream still comprises non-C2+ impurities. In some embodiments, the second stream has a lower concentration than the first stream of non-C2+ impurities. In some embodiments, in (d), the second stream is directed to the process stream at a point where the concentration of C2+ compounds is at most about 10% less than the concentration of C2+ compounds in the second stream.
[0027] In another aspect, a method of concentrating hydrocarbons having at least two carbon atoms (C2+) comprises (a) introducing a fluid composed of one or more C2+ compounds and non-C2+ impurities into a container at a first pressure, where the container comprises an adsorbent medium, in which after introducing the liquid into the container, the fluid is brought into contact with the adsorbent medium; (b) change the pressure in the container to a second pressure to release (i) at least a subset of the one or more C2+ compounds or (ii) the non-C2+ impurities from the adsorbent medium, thereby separating at least the subset of the one or more C2+ compounds from non-C2+ impurities; and (c) recovering at least the subset of the one or more C2+ compounds.
[0028] In some embodiments, the one or more C2+ compounds are hydrocarbons with between two and five carbon atoms. In some embodiments, the C2+ compounds comprise ethylene. In some modalities, the adsorbent medium is selected from the group consisting of activated carbon, silica gel, alumina and zeolite. In some modalities, the second pressure is greater than the first pressure. In some modalities, the second pressure is less than the first pressure.
[0029] In another aspect, a method for recovering hydrocarbons having two or more carbon atoms (C2+) from a methane process oxidative coupling (OCM) comprises (a) directing a feed stream comprising methane to a reactor oxidative coupling of methane (OCM), where the OCM reactor is configured to generate C2+ methane compounds; (b) performing one or more OCM reactions in the OCM reactor using methane to produce a product stream composed of one or more C2+ compounds; (c) subjecting the product stream to pressure swing adsorption (PSA) to generate at least a first stream and a second stream, where the first stream has a lower C2+ concentration than the second stream.
[0030] In some cases, the method still comprises, between (b) and (c), drying the product stream. In some modalities, subjecting the product stream to PSA separates C2+ from methane and impurities. In some cases, the first stream is composed of methane and impurities.
[0031] In some embodiments, the method further comprises, after (c), separating the impurities from the methane. In some embodiments, the method further comprises returning at least a portion of the methane to the CMO reactor. In some embodiments, impurities include argon (Ar), hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), nitrogen (N2) or any combination of these. In some embodiments, at least 95% of the impurities are removed in the PSA.
[0032] In another aspect, a method for recovering hydrocarbons having two or more carbon atoms (C2+) from a methane process oxidative coupling (OCM) comprises (a) providing, from an OCM reactor, a product stream comprising C2+ compounds, impurities and methane; (b) separating the product stream to provide at least (i) a first stream enriched in impurities, (ii) a second stream enriched in methane and (iii) a third stream enriched in C2+ compounds; and (c) cooling the third stream to condense the C2+ compounds.
[0033] In some cases, said first stream has an impurity content of at least about 70%. In some embodiments, the second stream has a methane content of at least about 70%. In some embodiments, the third stream has a C2+ content of at least about 70%. In some embodiments, impurities include argon (Ar), hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), nitrogen (N2) or any combination of these.
[0034] In some embodiments, the third stream mass flow rate is less than 30% of the product flow mass flow rate. In some embodiments, the method further comprises flowing the second stream into the reactor. In some embodiments, the method further comprises flowing the third stream to a hydrocarbon processing. In some embodiments, the method further comprises flowing a feed stream comprising methane from a hydrocarbon process into the OCM reactor. In some embodiments, the third stream is cooled in a cryogenic separation unit.
[0035] In another aspect, a method for integrating a methane process oxidative coupling (OCM) with a hydrocarbon processing comprises (a) providing, from an OCM reactor, a product stream consisting of hydrocarbon compounds comprising two or more carbon atoms (C2+) and methane; (b) separating the product stream into a first stream enriched in methane and a second stream enriched in C2+ compounds; and (c) combustion of methane in the first stream to provide energy for use in a hydrocarbon processing.
[0036] In some cases, the burning methane is directed through a heat exchanger that is coupled to a process stream from the hydrocarbon processing. In some embodiments, the hydrocarbon processing is an oil refinery, a natural gas liquids (NGL) process, or a cracking.
[0037] In another aspect, the invention provides natural gas processing systems comprising a OCM reactor system comprising at least a first reactor vessel with at least one first OCM catalyst disposed therein. The systems also comprise one or more of an extraction systems for separating at least one hydrocarbon compound from at least one non-hydrocarbon compound and a fractionation system for separating at least two different hydrocarbon compounds. The systems further comprise an interconnected duct, the fluidly interconnected duct connecting one or more of an inlet or an outlet of the OCM reactor system to one or more of an inlet or outlet of the one or more extraction systems and the fractionation system .
[0038] In another aspect, provided that there are natural gas processing systems and methods, comprising a OCM reactor system comprising at least a first container having at least a first OCM catalyst disposed therein. The system also comprises an extraction system for separating at least one non-hydrocarbon compound from at least one hydrocarbon compound and a fractionation system for separating at least two different hydrocarbon compounds. Also included is an interconnected duct, the fluidly interconnected duct connecting one or more of an inlet or an outlet of the OCM reactor system to one or more of an inlet or an outlet of one or more of the fractionation system and the fractionation system. extraction.
[0039] Also provided herein are methods and systems for producing hydrocarbon compounds. The methods comprise contacting methane and air/oxygen with a OCM catalyst under OCM reaction conditions in a first reactor system to produce a OCM product, the OCM product comprising two or more different hydrocarbon compounds; The OCM product produced in the contact step is then transferred to a fractionation system fluidly coupled to the first reactor system. At least one hydrocarbon compound in the OCM product is then separated from at least one other hydrocarbon compound in the OCM product in the fractionation system.
[0040] Another aspect provides methods and systems for the production of hydrocarbon compounds, comprising contacting methane and air/oxygen with a OCM catalyst under OCM reaction conditions in a first reactor system to produce a OCM product , the OCM product comprising one or more hydrocarbon compounds and at least one non-hydrocarbon compound. The OCM product produced in the contact phase is transferred to an extraction system fluidly coupled to the first reactor system. At least one hydrocarbon compound in the product is OCM is separated from at least one hydrocarbon compound or non-hydrocarbon compound in the OCM product.
Also provided herein are integrated hydrocarbon processing systems that include both a steam cracking device configured to convert one or more saturated hydrocarbons to one or more unsaturated hydrocarbons, and a CMO reactor system configured to convert methane to ethylene. These two systems are both fluidly connected at their outlets to the inlet of an integrated hydrocarbon fractionation system such that C2+ containing streams from each of the steam cracking devices and OCM reactor system are passed to the fractionation system.
[0042] Another aspect provides methods for producing one or more desired hydrocarbon compounds, comprising directing a first hydrocarbon feedstock comprising saturated hydrocarbons to a steam cracking device to produce a stream containing unsaturated hydrocarbon. These methods also include directing a second hydrocarbon feedstock comprising methane to a CMO reactor system to produce an ethylene-containing stream. The resulting streams, for example, the stream containing unsaturated hydrocarbon and the stream containing ethylene are then both routed to an integrated fractionation system, e.g., a common integrated fractionation system, to produce one or more desired hydrocarbon product streams .
[0043] Another aspect provides methods and systems for producing hydrocarbon compounds, comprising contacting methane and air/oxygen with a OCM catalyst under OCM reaction conditions in a first reactor system to produce a OCM product , the OCM product comprising one or more different hydrocarbon compounds. The OCM product produced in the contacting step is then transferred to an integrated oligomerization system to produce one or more higher hydrocarbon compounds from the one or more hydrocarbon compounds in the OCM product. The one or more higher hydrocarbons produced in the oligomerization system are then transferred to a fluid fractionation system coupled to the separation system to separate at least one hydrocarbon compound in the OCM product from at least one higher hydrocarbon.
[0044] In another aspect, natural gas processing systems and methods comprise a CMO reactor system for processing natural gas to produce a CMO product, the CMO reactor system including a thermally thermal energy extraction system coupled to the OCM reactor system to draw thermal energy from the OCM reactor system. The system also includes a natural gas fractionation unit for separating one or more hydrocarbon components in one or more of natural gas or the product of CMO from at least one other hydrocarbon product in the natural gas or product of CMO. Also included are heat exchangers thermally coupled to each of the thermal energy extraction system and the fractionation unit, to transmit the thermal energy from the thermal energy extraction system to the fractionation unit to heat the natural gas or product of OCM in the fractionation unit to separate the one or more hydrocarbon components in natural gas or OCM product from at least one other hydrocarbon product in natural gas or OCM product.
[0045] In another aspect, natural gas processing systems and methods comprise an extraction system for separating methane from NGLs into natural gas, the extraction system having a methane-rich effluent outlet, and further comprising a reactor system of OCM comprising a flowable inlet coupled to the methane rich effluent outlet of the extraction system. The system also includes a thermal energy removal system to remove thermal energy from the OCM reactor system, and a heat exchanger thermally coupled to each thermal energy removal system and a fluid connection between the methane-rich effluent outlet and the inlet of the OCM reactor, to heat the methane-rich effluent from the extraction system to over 400°C.
[0046] In another aspect, natural gas processing systems and methods comprise a OCM reactor system, a steam generator thermally connected to the OCM reactor, to generate thermal energy steam produced by the OCM reactor, and a generator electrically coupled to the steam generator to generate electricity from the steam produced by the steam generator.
[0047] In another aspect, methods and systems for collecting CO2 comprise, in a OCM reactor system, contacting methane and air/oxygen with a OCM catalyst under OCM reaction conditions to produce a product stream composed of one or more hydrocarbon compounds and CO2, separating CO2 from the one or more hydrocarbon compounds in the product stream in an extraction system integrated with the OCM reactor system, and collecting the separate CO2 from the product stream.
[0048] Additional aspects and advantages of the present disclosure will become apparent to those skilled in the art from the following detailed description, where only illustrative embodiments of the present disclosure are shown and described. As it will be carried out, the present disclosure is capable of other and different modalities, and its various details are capable of modification in several obvious respects, all without departing from the disclosure. In this sense, the description and drawings should be considered as illustrative in nature and not restrictive. INCORPORATION BY REFERENCE
[0049] All publications, patents and patent applications mentioned in this specification are incorporated herein by reference as if each individual publication, patent or patent application were specifically and individually indicated to be incorporated by reference. BRIEF DESCRIPTION OF THE FIGURES
[0050] The new features of the invention are set out with particularity in the appended claims. A better understanding of the characteristics and advantages of the present invention will be obtained by referring to the following detailed description which sets out illustrative embodiments, in which the principles of the invention are used, and the accompanying drawings or figures (also "Fig." and "Figs" in this document), of which:
[0051] Figure 1 provides a schematic illustration of the products of a methane process oxidative coupling (OCM) being integrated with a hydrocarbon process;
[0052] Figure 2 provides a schematic illustration of methane for a CMO process being provided by a hydrocarbon process;
[0053] Figure 3 provides a schematic illustration of the methane for a OCM process being provided by a hydrocarbon processing and the products of an OCM process being integrated with the hydrocarbon processing;
[0054] Figure 4 provides a schematic illustration of heat from a OCM process being integrated with a hydrocarbon process;
[0055] Figure 5 provides a schematic illustration of an OCM process having a separations module comprising a dryer and a nitrogen recovery unit;
[0056] Figure 6 provides a schematic illustration of an OCM process having a separations module comprising a bed of C2+ and/or pressure change adsorbent;
[0057] Figure 7 provides a schematic illustration of an example of a refinery;
[0058] Figure 8 provides a schematic illustration of an example of a gas plant;
[0059] Figure 9 provides a schematic illustration of an example of the integration of a OCM process with a refinery;
[0060] Figure 10 provides a schematic illustration of an example of the integration of a OCM process with a gas plant;
[0061] Figure 11 provides a schematic illustration of an example of integration of an oxidative dehydrogenation of ethane to ethylene or propane to propylene (ODH) process with a refinery;
[0062] Figure 12 provides a schematic illustration of an example of a recovery unit for aromatic compounds;
[0063] Figure 13 provides a schematic illustration of an example of integration of an ODH and ethylene to liquid process (ETL) with a refinery;
[0064] Figure 14 schematically illustrates an example of a natural gas installation;
[0065] Figure 15 schematically illustrates an example of the operations of the main unit of a steam cracking installation;
[0066] Figure 16 presents a block diagram showing the points where the inputs and outputs of a CMO reactor system can integrate a conventional natural gas processing system or installation;
[0067] Figure 17 presents a schematic illustration of a CMO adiabatic reactor system integrated at a prime location in a natural gas processing facility;
[0068] Figure 18 provides a schematic illustration of a CMO adiabatic reactor system integrated at a second location in a natural gas processing facility;
[0069] Figure 19 provides a schematic illustration of a CMO adiabatic reactor system and cryogenic separation system integrated in a steam cracking plant; and
[0070] Figure 20 provides a schematic illustration of the integration of thermal energy systems from an OCM reactor system into thermal management processes for other processing systems within a natural gas processing facility. DETAILED DESCRIPTION
[0071] Although various 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. Countless variations, alterations, 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 can be used.
[0072] The term "C2+," as used herein, generally refers to a compound consisting of two or more carbon atoms. C2+ compounds include, without limitation, alkanes, alkenes, alkynes, aldehydes, ketones, aromatic esters and carboxylic acids containing two or more carbon atoms. Ethane, ethene, ethine, propane, propene and propyne are examples of C2+ compounds.
[0073] The term "the term non-C2+ impurities," as used herein, generally refers to material that does not include C2+ compounds. Nitrogen (N2), oxygen (O2), water (H2O), argon (Ar), hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2) and methane (CH4) are examples of non-C2+ impurities .
[0074] The term "natural gas processing unit" as used herein generally refers to a facility that takes one or more of natural gas or NGLs and produces more than one product from these inputs.
[0075] The term "methane conversion", as used herein, generally refers to the percentage or fraction of methane introduced into the reaction that is converted to a product other than methane.
[0076] The term "C2+ selectivity," as used herein, generally refers to the percentage of all carbon that contains methane reaction oxidative coupling (OCM) products that are desired or otherwise preferred C2+ products, by example, ethane, ethylene, propane, propylene etc. Although primarily stated as C2+ selectivity, it will be estimated that selectivity can be indicated in terms of any of the desired products, eg only C2, or only C2 and C3.
[0077] The term "C2+ yield," as used herein, generally refers to the amount of carbon that is incorporated into a C2+ product as a percentage of the amount of carbon introduced into a reactor in the form of methane. This can usually be calculated as the product of conversion and selectivity divided by the number of carbon atoms in the desired product. C2+ yield is normally additive to the yield of components other than C2+ included in the identified C2+ components, eg ethane yield + ethylene yield + propane yield + propylene yield etc.)
[0078] The term "OCM process," as used herein, generally refers to a process that employs or substantially employs an oxidative coupling reaction of methane (OCM).
[0079] The term "Non-OCM process", as used herein, generally refers to a process that does not or substantially does not employ an oxidative coupling reaction of methane. Examples of processes that may be non-OCM processes include non-OCM hydrocarbon processing, such as an oil refinery, a natural gas liquids process, or a cracking.
[0080] The term "substantially equivalent", as used herein in the context of methane concentration, generally means that the methane concentration is within about 80%.70%, 60%, 50%, 40%, 30%, 20%, 10% or 5% of the methane concentration normally passed to an existing cracking train of a gas plant or cracking plant. Integration of OCM with Hydrocarbon Processing
[0081] The present disclosure provides for the integration of oxidative coupling of methane ("OCM") and, optionally or additionally, oxidative dehydrogenation of ethane to ethylene or propane processes to propylene ("ODH") processes and systems in existing natural gas and other petrochemical processes and facilities to take advantage of raw material flexibility, energy efficiency and flexibility to better define the product resulting from such processes. In particular, by providing an integrated OCM process with other processes one can take advantage of the complementarity of OCM processes with these other gas or petrochemical processes to improve one or all of raw material flexibility, product range flexibility, energy efficiency and other advantageous process parameters. While this integration provides benefits to a variety of different processes and systems, for illustration installation it is described in more detail with respect to integration into existing hydrocarbon processes (eg NGL natural gas processes, olefin production processes a from ethane, ethane/propane, and/or naphtha, as well as petroleum refining).
[0082] A CMO process can take as input methane and generate as product (or output) one or more hydrocarbons, such as C2+ compounds, as well as the heat of the exothermic reaction. The OCM process can be facilitated by a catalyst. An example of OCM process is as follows: 2CH4 +O2 > C2H4 + 2H2O.
[0083] Reference will now be made to figures, where as numerals always refer to similar parts, it will be appreciated that figures and features are not necessarily drawn to scale.
[0084] Incoming methane (CH4) can be supplied from various sources, and the product(s) from the CMO process can be directed to various downstream processes. An OCM process can be integrated with hydrocarbon processing in any number of ways. Figure 1 shows an example of an OCM integration process with a hydrocarbon processing 100. Hydrocarbon processing can take any raw material 102 and convert it into one or more products 104 using any number of operations (eg, 106 and 108), such as refinery, NGL fractionation, ethane cracking or other hydrocarbon processing operations. In some cases, in OCM processes, methane (eg, from a geological, biological, or industrial hydrocarbon source) 110 is fed into a CMO 112 process (eg, a OCM reactor) to produce compounds of C2+. C2+ compounds can be integrated with hydrocarbon processing. In some cases, C2+ compounds can be enriched and/or purified in a separations module 114, for example, to at least approximately match the composition of a stream in hydrocarbon processing having C2+ compounds 108.
[0085] Figure 2 shows another example of integration with a hydrocarbon processing. In this case, methane is supplied from a hydrocarbon processing stream having methane 106. Methane can be converted to C2+ compounds in process 112 and, in some cases, separated in process 114 to provide a product stream having C2+ compounds 200 .
[0086] Another example is shown in Figure 3. Here, methane is supplied from a hydrocarbon processing stream with methane 106, converted to C2+ compounds in process 112, optionally separated in process 114 and integrated with a hydrocarbon processing stream 108 having C2+ compounds.
[0087] A OCM process can be an exothermic process, producing heat that can be employed for use in various processes. In some cases, the OCM process is integrated with respect to energy, in some cases in addition to the integration of material flows. Figure 4 shows an example where heat 400 is transferred from a reactor of OCM 112 to a part of the hydrocarbon processing that requires heat 106. In some cases, methane is also removed from the hydrocarbon processing and/or C2+ compounds are fed for the processing of hydrocarbons. The removal or excess of methane can be combusted to provide energy for the processing of hydrocarbons.
[0088] Provided in this document are various types of hydrocarbon processing that can be integrated with an OCM process and examples of separations (eg in rough cut separations) that can be performed. Integrated Catalytic Systems
[0089] In some embodiments, existing gas or petrochemical processing facilities or systems are integrated with new processes and systems to produce a synergistic and highly valuable overall process. In some cases, additional value-added catalytic reaction processes are integrated into existing conventional gas or petrochemical processing facilities or systems to take one or more outputs from those facilities and systems and/or provide one or more inputs to these facilities and systems, to take advantage of the efficiency advantages derived from combining these processes in addition to those individual processes. In some cases, these integrated catalytic reactor systems typically (1) take one or more end-product or intermediate streams from the processes performed at these facilities to catalytically convert those end-product or intermediate streams into higher-value or more easily managed materials, (2) contribute one or more of the final or intermediate product streams to be processed within one or more different processing units within these facilities, and/or (3) contribute and/or use thermal energy required by or produced by these systems processing.
[0090] The resulting integrated processing facilities can have greatly enhanced efficiency and profitability, both in terms of the products produced depending on the raw material consumed, the types of raw materials used, the types of products produced, as well as the energy requirements for the functioning of these facilities. Consequently, the environmental impact of these facilities can be substantially reduced, both in terms of waste reduction and reduction of externally generated energy consumption.
[0091] In some cases, integrated reactor systems for carrying out catalytic exothermic reactions can be used to convert natural gas components to higher value components, such as for the conversion of higher methane and ethane alkanes, olefins and the like . Examples of such reactions include exothermic catalytic reactions for eg the oxidative coupling of methane (OCM) as well as the oxidative dehydrogenation (ODH) of eg ethane, propane and other hydrocarbons.
[0092] The oxidative coupling of methane ("OCM") with ethylene may involve the following reaction: 2CH4+O2 C2H4 + 2H2O (see, for example, Zhang, Q., Journal of Natural Gas Chem, 12:81, 2003; Olah, G. "Hydrocarbon Chemistry", Ed. 2, John Wiley & Sons (2003)). This reaction is exothermic (ΔH =-67 kcal/mole) and has usually been shown to occur at very high temperatures (>700°C). Although the detailed reaction mechanism may not be fully characterized, and without being bound by theory, experimental evidence suggests that free radical chemistry may be involved (Lunsford, J. Chem. Soc, Chem. Comm., 1991; H. Lunsford, Angew. Chem., Int. Ed. Engl., 34:970, 1995). In the reaction, methane (CH4) can be activated on the catalyst surface, forming methyl radicals, which then bond in the gas phase to form ethane (C2H6), followed by dehydrogenation to ethylene (C2H4). Various catalysts have demonstrated activity for OCM, including various forms of iron oxide and vanadium oxides, molybdenum, cobalt, platinum, rhodium, lithium, zirconium, gold, silver, manganese, cerium, magnesium, lanthanum, sodium, zinc and their combinations (eg, V2O5, MoO3, Co3O4, Pt-Rh, Li/ZrO2, Ag-Au, Au/Co3O4, Co/Mn, CeO2, MgO, La2O3, Mn3O4, Na2WO4, MnO, ZnO) on various supports. Some doping elements may also be useful in combination with the above catalysts.
[0093] Since the OCM reaction was first reported over thirty years ago, it has been the target of intense scientific and commercial interest. In some cases, fundamental limitations of the conventional approach to C-H bond activation seem to limit the yield of this attractive reaction under practical operating conditions. Specifically, numerous publications from industrial and academic laboratories have consistently demonstrated performance characteristic of high selectivity at low methane conversion, or low selectivity at high conversion (J.A. Labinger, Cat. Lett., 1:371, 1988). Limited by this conversion/selectivity threshold, some OCM catalysts do not exceed 20-25% combined yield of C2 (ie, ethane and ethylene). In some cases, such high conversions and selectivities are at extremely high temperatures (>800C), low pressures and low gas hourly space velocity. New systems and catalysts have been developed, however, that can operate in low temperature environments with greater yield/selectivity (see, for example, U.S. Published U.S. Patent Applications Nos. 2012/0041246 and 2013/0023709.
[0094] Although primarily described in terms of integrating a OCM reactor system, additional reactor systems can likewise be integrated, such as ODH reactor systems. In some cases, oxidative dehydrogenation (ODH) of light alkanes offers an attractive route for alkenes since, like the OCM reaction, the reaction is exothermic and avoids the thermodynamic restrictions of non-oxidative routes, forming water as a by-product. Furthermore, carbon deposition during ODH can be drastically reduced, leading to stable catalytic activity. However, the yield of alkenes obtained by ODH can be limited in most catalysts by burning alkene to CO and CO2 (eg from COx).
[0095] In one aspect, the present disclosure provides modular CMO reactor systems that can be configured to "plug" into something, and in some aspects are integrated into existing natural gas processing facilities. As such, a gas processing plant can take natural gas and produce pipeline-ready natural gas, as well as NGLs, or it can take NGLs and fractionate them to produce two or more different resulting NGL products. In some cases, the specific configuration and type of processing plant will depend on the material taken and the resulting products produced, and may include, in many cases, for example, NGL extraction plants, fractionators, straddle plants and the like, that meet the aforementioned criteria.
[0096] In some aspects, processing facilities include one or more of an extraction unit and a fractionation unit, and optionally one or more additional processing units (eg without extensive custom retrofitting of such facilities). In addition, integrated OCM reactor systems can be integrated and configured to take one or more effluent streams from different processing units within these facilities as a feed stream to the OCM reactor system, contribute one or more streams of effluents to one or more different processing units within these facilities as a feed stream to these units, use thermal energy produced elsewhere in the facility to carry out the OCM reaction, and/or contribute thermal energy to other systems and units elsewhere places, in the processing facility.
[0097] As used herein, an OCM reactor system typically includes one or more reactor vessels that contain an appropriate OCM catalyst material, typically together with additional system components. A variety of OCM catalysts have been previously described, such as, for example, in U.S. Patent No. 5,712,217; U.S. Patent No. 6,403,523 and U.S. Patent No. 6,576,803, which are fully incorporated into the addendum by reference. Although these catalysts have been shown to catalyze an OCM reaction, for most of these catalysts the reactions are carried out under conditions that are less practical or economical, ie at very high temperatures and/or pressures (eg, greater than 800 °C ). Some catalysts yield conversion and selectivity that allow economical methane conversion under practical operating conditions. Examples of such catalysts are described in, for example, U.S. Patent Application No. 2012/0041246 and U.S. Patent Publication No. 2013/0023709, which are fully incorporated herein by reference.
[0098] Products produced from these catalytic reactions typically include CO, CO2, H2, H2O, C2+ hydrocarbons such as ethylene, ethane and higher alkanes and alkenes. In some embodiments, OCM reactor systems operate to convert methane, for example, the methane component of natural gas, into desired higher hydrocarbon products (ethane, ethylene, propane, propylene, butanes, pentanes, etc.) collectively referred to as high-yielding C2+ compounds. In particular, the progress of the OCM reaction is generally discussed in terms of methane conversion, C2+ selectivity and C2+ yield.
[0099] In some cases, OCM reactor systems typically provide a methane conversion of at least 10% per process pass in a single integrated reactor system (for example, isothermal reactor single system or adiabatic reactor multistage integrated system ), with a C2+ selectivity of at least 50%, at reactor inlet temperatures between 400 and 600 °C and reactor inlet pressures of between about 103 kPa (15 pounds per square inch gauge (psig)) and about 1034 kPa (150 psig). In some cases the single pass conversion is 10% or greater with a selectivity of 60% or more and in some cases a conversion of 15% or more with a selectivity of 50% or greater or even a selectivity of 60 % or more. Likewise, in some cases, reactor inlet pressures are between about 930 kPa (135 psig) and about 103 kPa (15 psig), in some cases, about less than 827 kPa (120 psig), about of less than 689 kPa (100 psig), less than about 620 kPa (90 psig), less than about 586 kPa (85 psig), or less than about 551 kPa (80 psig) or even less than about 482 kPa (70 psig). In some cases, the reactor inlet pressure is between about 207 kPa (30 psig) to 689 kPa (100 psig), or even between about 207 kPa (30 psig) and one of about 620, or 586, or 551 kPa (90, or 85 or 80 psig), for example, when achieving the selectivities and conversions described above. In some cases, catalysts employed within these reactor systems are capable of providing the described conversion and selectivity under the described reactor temperature and pressure conditions. In some cases, reactor inlet or feed temperatures typically substantially correspond to the minimum "start up" or start reaction for the catalyst or system. In other words, the feed gases can be contacted with the catalyst at a temperature at which the OCM reaction is able to start after introduction to the reactor. Because the OCM reaction is exothermic, once start-up is achieved, heat from the reaction can be expected by keeping the reaction at proper catalytic temperatures and even generating excess heat.
[0100] In some embodiments, OCM reactors and reactor systems, when performing the OCM reaction, operate at pressures of between about 103 kPa (15 psig) and about 861 kPa (125 psig) at the temperatures described above, when provide the conversion and selectivity described above and in some cases at pressures less than 689 kPa (100 psig), for example, between about 103 kPa (15 psig) and about 689 kPa (100 psig) or even less than about 620 kPa (90 psig).
[0101] Examples of catalyst materials are described in, for example, U.S. Patent Publication No. 2012/0041246 and U.S. Patent Publication No. 2013/0023709, which are fully incorporated into the addendum by reference. Catalysts can include bulk catalyst materials, for example, having relatively undefined morphology, or, in some cases, the catalyst material is composed, at least in part, of nanowires containing catalytic materials. In any event, the catalysts used in accordance with the present disclosure can be specifically employed under the full range of reaction conditions described above, or in any narrower described range of conditions. Likewise, catalyst materials can be supplied in a variety of different larger scale forms and formulations, for example as mixtures of materials with different catalytic activities, mixtures of catalysts and relatively inert materials or diluent, incorporated into extrudates, pellets , or monolithic shapes or something like that. Ranges of exemplary catalyst forms and formulations are described, for example, in U.S. Patent Publication No. 13/901,319, filed May 23, 2013, the entire disclosure of which the addendum is incorporated by reference in its entirety for all purposes.
[0102] Reactor vessels used to carry out the OCM reaction in the OCM reactor systems of the invention may include one or more discrete reactor vessels each containing OCM catalyst material fluidly coupled to a methane source and an oxidant source as further discussed elsewhere in this document. Methane-containing feed gas can be contacted with the catalyzing material under conditions suitable for the initiation and progression of the reaction within the reactor to catalyze the conversion of methane to ethylene and other products.
[0103] For example, the OCM reactor system can comprise one or more phase reactor vessels operating under isothermal or adiabatic conditions, for carrying out OCM reactions. For adiabatic reactor systems, reactor systems can include one, two, three, four, five or more phased reactor vessels arranged in series, which are fluidly connected such that the effluent or "product gas" of a reactor is directed, at least in part, to the input of a subsequent reactor. Such prepared serial reactors can provide higher yields for the entire process, allowing for the catalytic conversion of previously unreacted methane. These adiabatic reactors are generally characterized by the lack of an integrated thermal control system used to maintain little or no temperature gradient across the reactor. Without an integrated temperature control system, the exothermic nature of the OCM reaction can result in a temperature gradient across the reactor indicative of the progress of the reaction, where the inlet temperature can range from about 400°C to about 600° C, while the outlet temperature ranges from about 700°C to about 900°C. Typically, such temperature gradients can range from about 100°C to about 500°C. In some cases, adiabatic reactors are prepared, with intermediate cooling systems to go through a more complete catalytic reaction without generating extreme temperatures, for example, above 900 °C.
[0104] In operation, methane-containing gas feed can be introduced into the inlet side of a reactor vessel, eg the first reactor in a phase reactor system. Within this reactor, methane can be converted to C2+ hydrocarbons as well as other products as discussed above. At least a portion of the product gas stream can be cooled to a suitable temperature and introduced into a subsequent reactor stage for further catalytic reaction. In some cases, effluent from a previous reactor, which in some cases may include unreacted methane, can provide at least part of the methane source to a subsequent reactor. An antioxidant source and a methane source, separate from unreacted methane from the first reactor stage, can normally also be coupled at the inlet of each subsequent reactor.
[0105] In some cases, reactor systems may include one or more 'isothermal' reactors, which maintain a relatively low temperature gradient across the entire length or depth of the global reactor bed, for example, between the inlet gas and output or gas product, through the inclusion of integrated temperature control elements, such as cooling systems that contact the heat exchange surfaces in the reactor to remove excess heat and maintain a flat or insignificant temperature gradient between the input and output of the reactor. Typically, such reactors use molten salt or other cooling systems that operate at temperatures below 593°C. As with adiabatic systems, isothermal reactor systems can include one, two, three, ten or more reactors that can be configured in series or orientation. Reactor systems for performing these catalytic reactions are also described in U.S. Patent Publication No. 13/900,898, filed May 23, 2013, the full disclosure of which is incorporated into the addendum by reference in its entirety for all purposes.
[0106] OCM reactor systems also typically include thermal control systems that are configured to maintain a desired thermal profile or temperature across the overall reactor system, or individual reactor vessels. In the context of adiabatic reactor systems, thermal control systems can include, for example, heat exchangers, arranged upstream, downstream or between serial reactors within the global system, in order to maintain the desired temperature profile through a or more reactors. In the context of reactors, carrying out exothermic reactions, such as OCM, such thermal control systems also optionally include control systems to modulate reactant flow, for example, the feeding of gas containing methane and oxidant, into reactor vessels in response feedback of temperature information in order to modulate reactions to achieve reactor thermal profiles within the desired temperature ranges. These systems are also described in U.S. Patent Publication No. 13/900,898, previously incorporated into the addendum by reference.
[0107] For isothermal reactors, such thermal control systems may include the foregoing, as well as integrated heat exchange components, such as integrated heat exchangers incorporated in the reactors, such as tube/pump reactor heat exchangers, where a Empty space is provided around a reactor vessel or through which one or more reactor vessels or tubes pass. A heat exchange medium can be passed through the vacuum to remove heat from individual reactor tubes. Heat exchange medium can then be routed to an external heat exchanger to cool the medium before recirculation into the reactor.
[0108] In some cases, products from OCM reactor systems integrated into processing facilities are transferred to additional process components for the production of higher hydrocarbons, eg C3+ hydrocarbons from the products of the OCM reaction. In particular, C2+ hydrocarbons derived from the OCM reaction process, and which optionally include the extraction processes described above or are upstream of such extraction processes, are subject to further processing for conversion to C2+ hydrocarbons, such as ethylene, in even higher hydrocarbons such as C3+ hydrocarbons, NGLs, cyclic hydrocarbons or linear and branched alkanes, aromatic compounds. In some cases, although generally worded in terms of OCM reactor system effluent, effluent from individual reactor steps can be routed to further process steps, including, for example, demethanization, where separate C2+ compounds are routed to a different process, while the methane-rich fluxes are passed through subsequent reactor stages. As a result, processing efficiency and equilibrium reaction can be favorably controlled over several stages.
[0109] For ease of discussion, these additional processes are generally referred to in this document as "oligomerization" processes, although this term encompasses a variety of different types of reaction. Likewise, processing units or systems for carrying out these reactions are generally referred to in this document as "oligomerization systems" or "units", although such terminology includes a variety of different reactions for converting high hydrocarbons from C2 hydrocarbons. for example, ethane and ethylene. Examples of such reactions include, for example; directed oligomerization of ethylene optionally followed by hydrogenation to form narrow distribution of linear or branched alkanes, such as butanes, hexanes, octanes, decanes, dodecanes, tetradecanes, etc., undirected oligomerization of ethylene optionally followed by hydrogenation for wide form distributions of alkanes linear or branched such as hydrocarbons within the C4-C16+ range, dimerization of ethylenes to butenes followed by dimerization to i-octanes, undirected oligomerization of ethylene optionally followed by hydrogenation to form a mixture of aromatic compounds, alkanes, alkenes, which is nominally a gasoline blendstock, undirected oligomerization of ethylene optionally followed by hydrogenation to form a blend of cyclic and branched chain, unbranched alkanes, which is nominally a blendstock of jet or diesel fuel, undirected oligomerization of ethylene to form distributions est eites of aromatics, such as benzene, toluene, and xylenes (collectively, "BTX"), or benzene, toluene, ethyl-benzene, xylene ("BTEX"), for use as a chemical feedstock. In general, many of these oligomerization processes involve catalytic reactions and reactor systems converting C2+ hydrocarbons to higher hydrocarbons. The nature and configuration of reactor oligomerization and catalyst system may depend on the specific type of product desired. In some embodiments, the oligomerization reaction takes place over a heterogeneous catalyst in a fixed bed reactor (adiabatic or isothermal) although methods and processes for homogeneous catalysts are suitable, and these can be used in combination such as a heterogeneous process for dimerization of ethylenes in butenes and homogeneous process for butenes in octenes. A variety of these additional conversion processes that can be integrated into the processes described in this document are described in, for example, US Provisional Patent Application No. 61/734,865, filed December 7, 2012, the full disclosure of which is by this medium incorporates the addendum by reference in its entirety for all intents and purposes.
[0110] In some cases, outputs from additional processes, eg oligomerization processes, may be routed through the integrated unit operations of a gas processing facility, cracking facility or other processing facility. For example, separation processes can be equally applicable to oligomerization products as they are CMO products and cracking products. In addition, oligomerization products can be routed into upstream unit processes, including the cracking device itself, for further cracking of LAOs or other higher hydrocarbons to form the most diverse of products.
[0111] For ease of discussion, in addition to one or more reactor vessels and associated piping and conduits, the phrase "OCM reactor system" also typically includes those elements that allow for ready-to-use integration of a OCM process into a pipeline. processing or existing gas plant. As such, such OCM reactor systems can include heat exchangers for both raising the temperature of the feed gases to reach temperatures suitable for catalysis, as well as cooled product gases to meet the temperature requirements of later process steps. Likewise, such reactor systems may include compressors, pumps and the like, to apply adequate pressures to supply gas feeds or recycle streams to reactor systems and/or product streams to other processing units, for example , separation or fractionation units. separations
[0112] Higher hydrocarbons (C2+) produced in a OCM reactor can be integrated with (eg fed into) a hydrocarbon processing as described in this document. In some cases, integration with hydrocarbon processing may use hydrocarbon processing separations equipment, thereby eliminating or reducing the amount of separations equipment that is required to add a OCM component to an existing hydrocarbon process. However, in some cases separations are performed over the OCM product stream prior to feeding the hydrocarbon processing. Separations can achieve any number of objectives, including but not limited to matching the composition of the OCM product stream to the hydrocarbon processing stream into which it is being integrated and/or reducing the volume of the stream (eg partially enriching C2+). Processes and systems for carrying out the described methods are also provided in this document.
[0113] Some separation processes to recover C2+ compounds from OCM product streams include the use of cryogenic separations as described in US Patent Application No. 13/739,954 ("PROCESS FOR SEPARATING HYDROCARBON COMPOUNDS"), which is incorporated herein document by reference in full for all purposes. However, cryogenic separations can be expensive due to high energy requirements so the present disclosure provides methods to perform an initial "raw cut" separation to remove impurities and inert compounds, thus concentrating the C2+ flux and effectively reducing the amount of gas entering the cryogenic separation unit per unit of desired product, thus reducing the cost of cryogenic separation. Such coarse-cut separation can be beneficial when the oxygen source for the OCM reaction is air.
[0114] Separations can be performed in a separations module comprising any number of individual pieces of equipment (unit operations) working together to achieve a separation. In some cases, the separations module has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or more pieces of equipment. Separation units can be eliminated in series, parallel or both (for example, some located in series and others located in parallel).
[0115] In one aspect, a method for recovering hydrocarbons having two or more carbon atoms (C2+) from an oxidative coupling of methane (OCM) comprises providing an OCM product stream comprising C2+ hydrocarbons, impurities and non- reacted. In some cases, the OCM product stream is provided by performing an OCM reaction. Any suitable amount of methane can be converted to C2+ hydrocarbons (eg at least 1%, at least 3%, at least 5%, at least 10% or at least 20%).
[0116] The method may then include performing a separation that provides a first stream comprising the impurities and/or inert components, provides a second stream enriched with methane, and provides a third stream enriched in C2+ hydrocarbons. The three streams can be provided by performing a separation. In some cases, the separation includes pressure variation adsorption. The method may include temperature change adsorption (TSA), refrigeration, pressurization and/or vacuum pumping the third stream to condense the C2+ hydrocarbons. In one example, the method includes TSA, refrigeration, pressurization, vacuum pumping and then cooling the third stream to condense the C2+ hydrocarbons.
[0117] In some cases, the second stream is fluid in a CMO reactor, thus recycling unreacted methane. In some cases, the second stream is flared or used as fuel in a hydrocarbon process. As described in this document, the heat generated by the OCM reactor can be integrated with any appropriate part of hydrocarbon processing. In some cases, the third stream (comprising C2+ hydrocarbons) is fluid in a hydrocarbon process.
[0118] The first stream can include any suitably large proportion of impurities and/or inert components (ie, reducing the amount of material in a cryogenic separation unit). In some cases, about 60%, about 70%, about 80%, about 90%, or about 95% of the impurities and/or inert components leaving the OCM reactor are separated for the first stream. In some cases, at least about 60%, at least about 70%, at least about 80%, at least about 90%, or at least 95% of the impurities and/or inert components that come out of the OCM reactor are separated into the first stream. In some cases, impurities and/or inert components are derived from air. Impurities and/or inert components can be any compound, but in some cases include argon (Ar), hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), water (H2O), nitrogen (N2 ) or any combination thereof.
[0119] The raw cut separation described here can reduce the volumetric flow rate of the third stream compared to the volumetric flow rate of the OCM product stream. In some modalities, the volumetric flow of the third flow is about 5%, about 10%, about 15%, about 20%, about 30%, about 35%, about 40%, about 45% , or about 50% of the volumetric flow rate of OCM product at a constant temperature and pressure. In some cases, the volumetric flow of the third flow is at most about 5%, at most about 10%, at most about 15%, at most about 20%, at most about 30%, at most about about 35%, at most about 40%, at most about 45%, or at most about 50% of the volumetric flow rate of the OCM product stream at a constant temperature and pressure.
[0120] Figure 5 provides an example of a process for performing separations (eg prior to integration with a hydrocarbon processing. In some cases, methane (eg natural gas) 502 is heated 504 and injected into an OCM reactor 506. An oxygen source (eg air) 508 can also be heated 510 and injected into the OCM reactor In some cases, natural gas and air are heated in the same heater.
[0121] In some cases, the products produced in the OCM reactor (eg C2+ hydrocarbons) are separated from the OCM reactor effluent through chemical absorption. An example of chemical absorption is possible by contacting the reactor off-gas mixed with an aqueous or organic solution containing metal ions (such as copper and silver) capable of binding with the olefins contained in the reactor effluent. The olefins contained in the solution can then be stripped in a conveniently designed operating unit (eg a packed or tray column) by reducing pressure and/or increasing temperature.
[0122] Products produced in the CMO reactor (for example, C2+ hydrocarbons) as well as impurities, inert components (for example, argon, nitrogen, water) and unreacted methane can be fed into a separations module, consisting of one or more unit operations, as depicted on the dotted edge 512. In some cases, the separations module reduces the downstream compression of the third stream by about 40%, about 50%, about 60%, about 70%, about 80%, or about 90% when compared to cryogenic separation. In some embodiments, the separation module reduces the compression downstream of the third stream by at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%. The separation module can eliminate amine units and/or cryogenic separation units. The cryogenic separation unit can be replaced with a smaller refrigeration unit in some cases.
[0123] In some cases, the separations module comprises a dryer 514 and a nitrogen recovery unit 516. As shown here, the products from the OCM reactor can be initially fed into a dryer 514 in which the water 535 is removed. Any adequate amount of water can be removed, including at least 80%, at least 90%, at least 95%, at least 99% or at least 99.9%.
[0124] After dryer 514, the remaining components can be fed into a nitrogen recovery unit (NRU) 516. The NRU can be any type of unit operation. In some cases, NRU is a pressure variation adsorption unit (PSA). NRU generally separates 518 hydrocarbons (eg methane and higher hydrocarbons) from other gases as impurities and inert 520 components. Inert components and impurities include, but are not limited to argon (Ar), hydrogen (H2), carbon monoxide ( CO), carbon dioxide (CO2) and nitrogen (N2). In some cases, impurities and inert components include some unreacted methanes (CH4). The NRU 516 generally removes most impurities and inert components 520, however some of the inert components and impurities can be removed elsewhere in the process (eg in flow 535). In some cases, NRU removes about 60%, about 70%, about 80%, about 90%, about 95%, about 97%, about 99%, or about 99.5% of impurities and inert components (eg when comparing mass flow rate 520 with flow 535). In some embodiments, NRU removes at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97%, at least about 99% or at least about 99.5% impurities and inert components.
[0125] The 518 hydrocarbon stream from NRU 516 can be fed into one or more 522 compressors. Compressors are generally smaller and/or require less energy than would be required in the absence of the 512 separations module (ie, because of the majority impurities and inert components). In some cases, compressors are about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, or about 80% of the size that it would be necessary in the absence of the separations module. In some cases, compressors are less than 10%, less than 20%, less than about 30%, less than about 40%, less than 50%, less than about 60%, less than about 70% , or less than about 80% of the size as would be required in the absence of the separations module. In some cases compressors are between 10% and 60% of the size, as would be required in the absence of the separations module. In some cases, compressors are about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, or about 80% of the energy that would be needed in the absence of the separations module. In some cases, compressors are less than 10%, less than 20%, less than about 30%, less than about 40%, less than 50%, less than about 60%, less than about 70% , or less than about 80% of the energy as would be required in the absence of the separations module.
[0126] The compressed hydrocarbon stream 524 can be fed to a refrigeration unit 526. The refrigeration unit can lower the temperature of the compressed hydrocarbons such that one or more hydrocarbons are condensed. In some cases, the temperature is lowered in stages such that a series of various hydrocarbons are condensed according to their boiling points. For example, hydrocarbons with three or more carbons can be condensed first 528 (eg at a temperature below -42°C). The temperature can be reduced further, such that ethane (C2H6) condenses 530. In some cases, the temperature is lowered (in one or more steps) such that ethylene (C2H4) condenses 532 (eg, to less than -103°C).
[0127] In some cases, unreacted methane 533 is returned to the reactor of OCM 506, either directly or through a heater 504. Impurities and inert components can be removed from any part of the process, including from the 535 refrigeration unit.
[0128] The refrigeration unit is generally smaller and/or requires less energy than would be needed in the absence of the 512 separations module (i.e., due to most impurities and inert components). In some cases, the refrigeration unit is about 10%, 20%, about 30%, about 40%, about 50%, about 60%, about 70%, or about 80% of the size as would be required in the absence of the separations module. In some cases, the refrigeration unit is less than 10%, less than 20%, less than about 30%, less than about 40%, less than about 50%, less than about 60%, less than about 70%, or less than about 80% of the size as would be required in the absence of the separations module. In some cases, the refrigeration unit is between about 10% and 60% of the size as would be required in the absence of the separations module. In some cases, the refrigeration unit requires about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, or about 80% of the energy as would be required in the absence of the separations module. In some cases, the refrigeration unit requires less than 10%, less than 20%, less than about 30%, less than about 40%, less than about 50%, less than about 60%, less than about 70%, or less than about 80% of the energy as would be required in the absence of the separations module.
[0129] The addition of a bed of C2+ (eg separation or concentration bed) to the separations module 512 shown in Figure 5 can reduce the size and/or energy required in a cryogenic and/or separation unit. refrigeration. The C2+ bed can be any unit that increases the concentration of C2+ compounds (eg, a pressure change adsorption unit (PSA), a temperature shift adsorption unit (TSA), a membrane separator, a lean oil adsorption unit, silver adsorption unit (Ag) and the like). The present disclosure provides the use of pressure swing adsorption (PSA) to concentrate hydrocarbons having greater than or equal to two carbon atoms (C2+), in some cases between two and five carbons (C2-5).
[0130] In one aspect, a method of concentrating hydrocarbons having between two and five carbons (C2-5) comprises introducing a fluid (eg OCM product stream) comprising C2+ compounds, in some cases C2-5 compounds , inside a container with a first pressure. The container may contain an adsorbent medium.
[0131] The adsorbent medium can be any medium suitable for carrying out PSA. In some cases, the medium is a molecular sieve. The medium can be a microporous material that can selectively adsorb gases and/or liquid. In some cases they are synthetic zeolites such as crystalline metal aluminosilicates. The medium can have any suitable pore size, including about 1 angstrom, about 2 angstroms, about 3 angstroms, about 4 angstroms, about 5 angstroms, about 6 angstroms, about 7 angstroms, about 8 angstroms , about 9 angstroms, or about 10 angstroms. In some cases, the medium has a pore size of at most about 1 angstrom, at most about 2 angstroms, at most about 3 angstroms, at most, about 4 angstroms, at most about 5 angstroms, at most about 6 angstroms, at most about 7 angstroms, at most about 8 angstroms, at most about 9 angstroms, or at most about 10 angstroms. In some cases, the medium has a pore size of at least about 1 angstrom, at least about 2 angstroms, at least about 3 angstroms, at least about 4 angstroms, at least about 5 angstroms, at least about of 6 angstroms, at least about 7 angstroms, at least about 8 angstroms, at least about 9 angstroms, or at least about 10 angstroms.
[0132] In other cases, the adsorbent can be properly designed to chemically bond with selected components of the reactor effluent. For example, the adsorbent can contain specific metals (such as copper or silver) that can bind with the olefins in the reactor effluent.
[0133] Then the pressure in the vessel is changed to a second pressure. The first pressure can be greater than the second pressure or the second pressure can be greater than the first pressure. The method may also include cycling through two or more pressures, or changing the pressure accordingly such that C2+ compounds (eg, C2-5) are separated. In one example, the pressure can be increased with the aid of a compressor. In one example, the pressure can be lowered with the aid of a pump.
[0134] For example, pressure can be increased to generate a motive force that drives C2+ compounds into the adsorbent medium. The pressure can be reduced to desorb C2+ compounds from the adsorbent medium. PSA can function to preferentially adsorb or desorb one or more species over other species. For example, the adsorbent medium can be selected such that, with a change in pressure, C2+ compounds are adsorbed onto or desorbed from the adsorbent medium, while other species such as non-C2+ compounds (eg, N2, O2, H2O ), do not adsorb onto or desorb from the adsorbent medium.
[0135] In some examples, a product stream from an OCM reactor is directed to a PSA unit at a first pressure (P1). Then, the pressure is changed from the first pressure to a second pressure (P2) to selectively separate C2+ compounds in the product stream from non-C2+ compounds. The pressure can be selected such that the ratio between the first and second pressure (P2/P1) is at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 1000, 10,000 or 100,000.
[0136] Next, C2+ compounds are recovered from the container. The C2+ compounds can encompass ethane, ethylene, propane, propylene, butane, or higher carbon hydrocarbons or any combination thereof. In some examples, the C2+ compounds are C2-5 compounds.
[0137] In one aspect, a method for recovering hydrocarbons having two or more carbon atoms (C2+) from a methane process oxidative coupling (OCM) comprises drying a product gas from an OCM reactor, performing an adsorption by variation pressure (PSA) to separate C2+ from methane and impurities, separating methane from impurities and returning the methane to the CMO reactor.
[0138] An example of a process is shown in Figure 6, where equal numbered elements represent equal flows of equipment and/or material compared to Figure 5, the separations module can include a bed of C2+ 602. The bed of C2+ it can be a separation and/or concentration bed. In some cases, the C2+ bed is a pressure swing adsorption unit (PSA).
[0139] In some cases, the C2+ bed recovers a high percentage of the C2+ compounds that are produced in the reactor of OCM 506. For example, the C2+ bed can recover about 75%, about 80%, about 85% , about 90%, about 95%, about 97%, about 99%, about 95.5%, or about 99.9% of the C2+ compounds that are produced in the OCM reactor. In some cases, the C2+ bed recovers at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 97%, at least about 99%, at least about 95.5%, or at least about 99.9% of the C2+ compounds that are produced in the OCM reactor.
[0140] In some cases, the C2+ bed recovers the C2+ compounds in high concentration. For example, flux enriched in C2+ compounds may comprise about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90% , or approximately 95% C2+ compounds by mass. In some cases, the flux enriched in C2+ compounds may include at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, or at least about 95% C2+ compounds by mass.
[0141] The stream comprising the recovered compounds of C2+ 604 can be fed to a compressor 522 and refrigeration unit 526 for fractionation as described in this document. The stream depleted in C2+ 606 compounds can be fed to the Nitrogen Recovery Unit (NRU) as described in this document. As shown in Figure 6, NRU 516 can recover unreacted methane and feed it to a 608 compressor. The compressor can increase the pressure to any suitable pressure (for example, the reactor pressure of OCM 506). In some cases, the compressor increases the pressure by about 69 to 138 kPa (10 to 20 pounds per square inch (psi)). The compacted methane can be recycled to the 506 CMO reactor.
[0142] Inclusion of a bed of C2+ 602 in the separations module 512 can further reduce the size and/or reduce the energy requirements of the refrigeration unit 526 (ie, the refrigeration unit, shown in Figure 6, may be smaller and/or requires less energy than the refrigeration unit as shown in Figure 5). The greatest reduction in refrigeration size and/or energy requirement may be the result of removing unreacted methane from the enriched C2+ 604 stream and/or removing most (eg, at least 80%, at least 90%, or at least 95%) of the impurities and/or inert compounds from the enriched stream C2+ 604.
[0143] In some cases, the refrigeration unit is about 0.5%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 10%, about 12%, about 15%, or about 20% of the size as would be required in the absence of the separations module. In some cases, the refrigeration unit is less than about 0.5%, less than about 1%, less than about 2%, less than about 3%, less than about 4%, less than about 5% , less than about 6%, less than about 7%, less than about 8%, less than about 10%, less than about 12%, less than about 15%, or less than about 20% the size as would be required in the absence of the separations module. In some cases, the refrigeration unit is between about 2% and 5% of the size as would be required in the absence of the separations module.
[0144] In some cases, the refrigeration unit is about 0.5%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 10%, about 12%, about 15%, or about 20% of the energy as would be required in the absence of the separations module. In some cases, the refrigeration unit requires less than about 0.5%, less than about 1%, less than about 2%, less than about 3%, less than about 4%, less than about 5% , less than about 6%, less than about 7%, less than about 8%, less than about 10%, less than about 12%, less than about 15%, or less than about 20% of energy as would be required in the absence of the separations module.
[0145] In some cases, separation does not result in a completely purified product stream. The composition of the OCM product stream can be adjusted using the separations described in this document. In some cases, the OCM product stream is adjusted to more closely match the composition of the hydrocarbon processing stream into which the OCM product stream is integrated.
[0146] In one aspect, a method for integrating a methane process oxidative coupling (OCM) with a hydrocarbon processing comprises performing an OCM reaction in a feed stream comprising methane to produce a product stream consisting of C2+ compounds , performing a separation on the product stream to produce an enriched stream and flowing the enriched stream to a hydrocarbon processing. Hydrocarbon processing can be, without limitation, an oil refinery, a natural gas liquids (NGL) process or a cracking.
[0147] In some cases, enriched flux does not include purified C2+ compounds. That is, the concentration of C2+ compounds can be about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80% , or about 90% by mass. In some cases, the concentration of C2+ compounds is less than 10%, less than 20%, less than about 30%, less than about 40%, less than about 50%, about 60%, less than about 70%, less than about 80%, or less than about 90% by mass.
[0148] The enriched flux can be relatively more enriched in C2+ compounds than the OCM product flux. In some cases, the ratio of the concentration of C2+ compounds in the enriched stream to the OCM product stream is about 1.1, about 1.3, about 1.5, about 2, about 3, about 3.5, about 4, about 4.5, about 5, about 6, about 8, about 10, about 15, about 20, or about 50. In some cases, the ratio of concentration of C2+ compounds in the enriched stream for the OCM product stream is at least about 1.1, at least about 1.3, at least about 1.5, at least about 2, at least about 3 at least about 3.5, at least about 4, at least about 4.5, at least about 5, at least about 6, at least about 8, at least about 10, at least about of 15, at least about 20, or at least about 50.
[0149] Raw cut separation can be used to roughly match the OCM product stream composition to the hydrocarbon stream composition in which it is integrated. Performing rough cut separation can mean that hydrocarbon processing operating parameters do not need to be adjusted when being integrated with OCM. The OCM product stream can include various C2+ compounds, impurities, inert components and unreacted methane, the concentration of any combination of which can roughly match the concentration of the hydrocarbon stream into which the OCM product stream is integrated. In some cases, one or more of the concentrations correspond to about 0.5%, about 1%, about 2%, about 5%, about 7%, about 10%, about 15%, 20%, about 30%, about 40%, or about 50%. In some cases, one or more of the concentrations are combined to within a maximum of 0.5%, within a maximum of 1%, within a maximum 2%, within a maximum 5%, within a maximum of 7%, within maximum 10%, within maximum 15%, within maximum 20%, within maximum 30%, within maximum 40% or within maximum 50%.
[0150] In some cases, the OCM reaction is carried out at an inlet temperature between 400 °C and 600 °C. The method can also include flowing enriched stream in a hydrocarbon process such as an oil refinery, a natural gas liquids (NGL) process, or a cracking.
[0151] In one aspect, a method for integrating a methane process oxidative coupling (OCM) with a hydrocarbon processing comprises performing an OCM reaction in a feed stream composed of methane to produce a product stream comprising C2+ compounds , performing a separation in the product stream to enrich C2+ compounds, thus producing an enriched stream; and flowing the enriched stream in a hydrocarbon processing at a point in the hydrocarbon processing where the concentration of C2+ compounds approximately corresponds to the concentration of C2+ compounds in the enriched stream. In some cases, hydrocarbon processing is an oil refinery, a natural gas liquids (NGL) process or a cracking.
[0152] In one aspect, a method for integrating a methane process oxidative coupling (OCM) with a hydrocarbon processing comprises performing an OCM reaction in a feed stream composed of methane to produce a product stream consisting of compounds of C2+ and impurities, performing a separation in the product stream to deplete the impurities, thus producing a depleted impurity stream; and flowing the depleted impurity stream in a hydrocarbon processing at a point in the hydrocarbon processing where the impurity concentration is less than 10% different than the impurity concentration in the depleted impurity stream. In some cases, hydrocarbon processing is an oil refinery, a natural gas liquids (NGL) process or a cracking. Integration with a Refinery
[0153] An oil refinery or petroleum refinery is an industrial process plant where crude oil is processed and refined into more useful products such as petroleum naphtha, gasoline, diesel fuel, asphalt base, heating oil, kerosene and liquefied petroleum gas. Oil refineries are typically large, sprawling industrial complexes with extensive piping running alongside them, carrying fluid flows between large chemical processing units. In many ways, oil refineries make much of the technology of, and can be thought of as, types of chemical plants. Crude oil feedstock was typically processed by an oil production plant. There is usually an oil depot (tank farm) at or near an oil refinery for the storage of incoming crude oil feedstock as well as bulk liquid products.
[0154] The OCM process can be integrated with an oil refinery in any suitable way, such as designing any flow with methane, flowing C2+ compounds to the refinery at any flow location having or that can accept C2+ compounds , and/or heat transfer between the CMO process and the oil refinery.
[0155] In some cases, the refinery produces "off-gas" comprising methane that can be converted to C2+ compounds in a CMO process. In some cases, off-gas is burned either inside furnaces or in other systems of a processing facility, for example, for heat generation, or it can be burned for any purpose other than disposal (burning) in the refinery of oil. Integrating an oil refinery with a CMO process provides a way for the oil refinery to recover the additional value of its crude oil feedstock, recovering values from what is normally considered a waste gas or low-value component, for example, the fuel gas.
[0156] Figure 7 shows a schematic drawing of an oil refinery. Additional details can be found in "Petroleum Refining in Nontechnical Language, 4th Edition" by William Leffler, published November 13, 2008, which is incorporated herein by reference in its entirety. As shown, crude oil 700 can be split between a flash tank 702 and a visbreaker 704. The flash tank can feed the visbreaker and a catalytic cracking unit (CCU) 706. The visbreaker can reduce the amount of oil waste produced in crude oil distillation and increase the yield of middle distillates (eg, thermally cracking large hydrocarbon molecules by heating in an oven to reduce viscosity and produce small amounts of light hydrocarbons). The CCU can convert high molecular weight hydrocarbon fractions (eg molecular weight from about 200 to 600 grams/mole) to gasoline, olefinic gases and other lower molecular weight products. In some cases, the CCU is a fluid catalytic cracking device accepting material having an initial boiling point of 340°C or higher. A portion of the CCU material can be fed with an alkylation unit 708. In some cases, the alkylation unit converts isobutene and low molecular weight alkenes (eg, propene and butene) in the presence of an acid catalyst strong. The refinery can also produce 730 waste fuel.
[0157] Material entering the 710 distillation unit may be oil 700 or its derivatives. High molecular weight compounds from a 710 distillation unit can also be fed into the CCU. Medium boiling compounds can be taken out in various fractions to be converted to distillate 712 fuel and 714 jet fuel, for example. In some cases, fractions are treated with hydrogen 716 (eg to remove sulfur). Figure 7 shows two hydrotractors 716 (ie, one for 712 distillate fuel and one for 714 jet fuel), but any numbers are possible. Compounds boiling at a lower temperature in the distillation column can be fed to a splitter 716 which splits the input stream between a 718 reformer and a 720 isomerizer. In some cases, the reformer, also known as a catalytic reformer, converts naphtha typically having low octane in high octane liquid products called reformates, a component of 722 gasoline. In some cases, the isomerizer converts linear molecules to this higher octane branched molecules for mixing with gasoline or feeding the alkylation units.
[0158] Gases from the 710 distillation unit(s) can be fed into a 724 gas plant. The gas plant can produce, among other things, sulfur 726 and fuel gas 728.
[0159] Figure 8 shows a schematic drawing of a representative 724 gas plant. Gas 800 can be fed into an 802 compressor, followed by an 804 phase separator. The phases of the phase separator can be divided between an 806 and an absorber an 808 debutanizer. Some material from the debutanizer can be returned to the absorbent 806 and some can be placed in an 810 depropanizer. The depropanizer can produce a fraction of propane 812 and flow the butanes into an deisobutanizer 814. The deisobutanizer can split the flow. butane of which enters iso-butane 816 and n-butane 818 fractions. Absorber 806 can also flow lower molecular weight gases (C2-) to a sponge absorber 820. In some embodiments, C2-822 gases are integrated with a CMO or ODH process as described in this document.
[0160] Figure 9 shows an example of the integration of a OCM 900 process with a refinery gas plant 724. Methane can be drawn from 902 geological and/or biological sources (eg natural gas) and/or from the 904 gas plant or other appropriate part of the refinery. In some cases, the OCM 906 product is fed into the 724 gas plant where it can be separated into one or more fractions. In some cases, separations are performed before the OCM product is fluid to the gas plant (not shown). In some cases, carbon dioxide from the 908 gas plant is used in enhanced oil recovery (EOR). Figure 10 shows an example of the integration of a OCM process with the gas plant in more detail where as numbered elements are the same as those described in Figures 8 and 9.
[0161] In some embodiments, OCM, ODH, and/or ethylene-to-liquid ("ETL") processes described herein are integrated with a refinery. Figure 11 shows additional examples of such integration with the 724 gas plant. Propane 1100 can be taken from the gas plant and fed through an ODH 1102 process to produce propylene. The 1104 propylene can be separated from the 1106 unreacted propane in a 1108 separator. The 1106 unreacted propane stream can alternatively be fed back to the 1102 ODH reactor. The 1106 unreacted propane stream can alternatively be used as a diluent for the ETL reactor (not shown). Some of the 1110 propylenes can be fed to the alkylation unit 708. In some cases, an ETL reactor (not shown) can produce butane (eg, iso-butane, n-butane or a combination thereof) that can be fed to the unit. of alkylation 708. In some cases, the amount of propylene fed into the alkylation unit is greater than would be the case in the absence of integration of OCM, ODH and/or ETL. Alternatively, if the OCM effluent undergoes separations instead of a gas plant as described above, the hydrogen that is separated can be fed into the 716 hydrotreatment units.
[0162] In some cases, ETL, ODH/OCM processes produce gases (eg products, co-products, unreacted gases, and/or gases introduced from the air used as a source of oxygen). These gases can be separated in the gas plant. As shown in Figure 11, hydrogen (H2) from the 1112 gas plant can be fed into one or more 716 hydrotreating units. In some cases, hydrogen is a greater amount of hydrogen than would be present in the absence of OCM integration , ODH and/or ETL.
[0163] As described in this document, refineries can produce a mixture of aromatic hydrocarbons, commonly known as BTX. Figure 12 shows an example of an aromatics recovery unit, which is a process for recovering BTX from a refinery. Hydrocarbons having BTX 1200 (eg straight-run gasoline and/or reformats) can be fed into a first separations unit 1202 which removes hydrocarbons that are lighter than benzene (ie, have a lower molecular weight and/or more low boiling point) 1204. The remaining material can be fed into a second separations unit 1206 which removes hydrocarbons that are heavier than toluene (ie has a higher molecular weight and/or higher boiling point) 1208. The remaining material from the second separations unit (eg, known as a "heartcut" and comprising aromatics concentrate) can be fed into a 1210 aromatics recovery unit. The 1210 aromatics recovery unit can separate the heartcut into BTX 1212 and refined 1214. In some cases, refined is a gasoline blending component.
[0164] In some embodiments, the ethylene-to-liquid ("ETL"), or OCM and ETL, and/or ODH and ETL processes described herein are integrated with a refinery (eg, a refinery with a compound recovery unit aromatics). Figure 13 shows a refinery with a 1300 aromatics recovery unit for the production of BTX 1302 (with refined co-product 1304 which is for example suitable for blending with gasoline). In some embodiments, the aromatics recovery unit is supplemented with hydrocarbons from integrated OCM, ODH and/or ETL processes.
[0165] As shown in Figure 13, 1306 ethane can be taken from the 724 gas plant and converted to ethylene in an ODH 1308 reactor. A 1310 separations module can separate ethylene from unreacted 1312 ethane. additional 1320 is provided to the 1310 separations module. Ethylene can be fed into an ethylene-to-liquid (ETL) 1314 process for conversion to higher molecular weight hydrocarbons (C2+). Higher molecular weight hydrocarbons can be transferred to an ETL 1316 separations unit where propane and 1318 butane are optionally returned to the gas plant or an alkylation unit. Other fractions from the ETL separations unit can be blended with 722 gasoline or fed into the 1300 aromatics recovery unit.
[0166] Exothermic reactions can occur in one or more of the OCM, ODH and ETL units. Reaction heat can be recovered to produce steam, a portion of which can be used to supply heat to or to generate energy for the OCM, ODH and ETL units themselves. The remaining part of the steam can be fed to the refinery plant or can be used to generate energy that is exported outside the battery limits of the OCM, ODH and ETL units.
[0167] The various figures showing the integration with a refinery are illustrative and not limiting. Additional modalities can easily be generated by combining the examples shown in figures 7 to 13. In some cases, thermal energy and/or electricity are integrated with the refinery (eg heat from an exothermic OCM reaction can be transferred anywhere in the refinery that requires heat). Integration with Natural Gas Processing
[0168] Compared to crude oil, natural gas is currently relatively abundant in supply, especially in accessible and available places such as in North America. When viewed at the national level, gas reserves within the United States are currently among the largest in the world, providing not only a valuable natural resource, but also providing the potential for greater energy independence for the country. Exploitation of these reserves, however, can pose challenges different from those faced and managed by the oil industry. In some cases, large-scale transport of natural gas is typically carried out by pipeline, which can create costly infrastructure requirements. Long-distance pipelines often require consistent and predictable qualities of gas to function economically and safely. For example, the energy density and vapor pressure of the gas being moved over a long distance is generally required to stay within a predetermined specification. As a result, the gas industry has resorted to building processing facilities near gas fields in which raw natural gas containing impurities such as CO2, N2, water, regulated compounds such as heavy metals and valuable components including C1, C2, C3, C4, and C5+ are separated into more manageable gases and liquids that can, for example, be transported by less costly and more suitable means, for example, common transport pipeline, rail, truck etc.
[0169] These facilities normally receive natural gas, which is, depending on the source of the gas, usually composed of a mixture of different amounts of methane, high hydrocarbons (eg C2+), water vapor, hydrogen sulfide (H2S), carbon dioxide, helium, nitrogen and other compounds.
[0170] Natural gas processing typically involves separating the various impurities, higher hydrocarbons and fluids from the gas, to produce what is commonly known as "duct quality" dry natural gas. Main transport pipelines often impose restrictions on the composition of natural gas that is allowed in the pipeline. Which means that, before natural gas can be transported, it must be treated properly to meet pipeline requirements. The ethane, propane, butane, pentane and other higher hydrocarbons that are removed from this natural gas are generally known as "natural gas liquids" (NGLs). NGLs can be valuable by-products of natural gas processing and therefore are typically also recovered at these facilities. NGLs can include ethane, propane, butane, isobutane and natural gasoline. These NGLs are generally sold separately from pipeline ready gas and can have a variety of different uses; including supplying raw materials to oil refineries or petrochemical plants and as energy sources, while other separate components are used in other applications, for example, to increase oil recovery.
[0171] While some of the necessary treatments may be performed at or near the gas well (field processing), as noted in this document, the complete processing of natural gas typically takes place in one or more processing plants that are usually located within the region of natural gas production. The extracted natural gas can be transported to these processing plants through a network of collection pipelines, which are generally small-diameter, low-pressure pipes. A complex collection system can include thousands of miles of pipe, linking the processing plant to more than 100 wells in the area.
[0172] In addition to processing done at the wellhead and centralized processing plants, some additional processing is also sometimes performed at “straddle extraction plants.” These plants are typically located in main pipeline systems. that reaches these straddle extraction plants is normally already of pipeline quality, in some cases there may still be small amounts of NGLs or other impurities, which can be extracted from the straddle plants.
[0173] The practice of processing natural gas to pipeline quality dry gas can be quite complex, but generally involves four main processes to remove the various impurities: oil and condensate removal, water removal, glycol dehydration and dehydration solid desiccant. In addition to these four processes, heaters and purifiers are often installed, usually at or near the wellhead. Purifiers are mainly used to remove sand and other impurities from large particles. Heaters can ensure that the gas temperature does not drop too low (eg such that unwanted water condensation occurs). With natural gas that contains even low amounts of water, natural gas hydrates can have a tendency to form when temperatures drop. These are typically solid or semi-solid compounds, resembling ice-like crystals, and their accumulation can impede the passage of natural gas through valves and collection systems. To reduce the occurrence of hydrates, small natural gas-fired heating units are normally installed along the collection tube, wherever hydrates can form.
[0174] As noted here, natural gas coming directly from a well can contain many natural gas liquids that are usually removed. Most NGLs are removed to meet the most commonly performed pipeline specifications, often referred to as required extraction. When natural gas liquids (NGLs) have sufficiently high economic values as separate products, it can become economical to extract more than the minimum amount of NGLs contained in the gas stream, a scenario that is often referred to as discretionary extraction. Removal of liquids from natural gas generally takes place in a relatively centralized processing plant and uses techniques similar to those used to dehydrate natural gas. Generally, there are two basic steps for treating natural gas liquids in the natural gas stream. First, liquids are extracted from natural gas. Second, these natural gas liquids are separated into their base or purer components. Integration with NGL Extraction
[0175] The NGLs can initially be extracted from the natural gas stream. In typical gas processing, there are two principle techniques for removing NGLs from the natural gas stream: the absorption method and the cryogenic expansion process, also known as a cryogenic extraction or separation process. According to the Gas Processors Association, these two processes currently represent around 90% of total natural gas liquid production.
[0176] In NGL absorption, an absorbent oil that has an affinity for NGL is usually used in the same way as glycol (which has an affinity for water when used in the dehydration process). Before the absorbent oil has collected any NGL, it is often called "lean" absorption oil. In some cases, as natural gas is passed through an absorption tower, it is brought into contact with the absorption oil, which absorbs, or sucks up, a high proportion of NGLs. "Rich" absorption oil, now containing NGLs, can exit the absorption tower through its bottom. It is now typically a mixture of absorptive oil, propane, butanes, pentanes and other heavier hydrocarbons. Rich oil can be fed into lean oil stills, where the mixture can be heated to a temperature above the boiling point of NGLs but lower than that of the oil. Generally this process allows the recovery of about 75% of butanes and from 85 to 90% of the heavier pentanes and hydrocarbons from the natural gas stream.
[0177] The basic absorption process described above can be modified to improve its effectiveness, or to target the extraction of specific NGLs, for example. In the chilled oil absorption method, where lean oil is cooled through refrigeration, propane recovery can be greater than 90% in some cases, and about 40% of the ethane can be extracted from the natural gas stream in some cases . Extraction of other, heavier, NGLs can be close to 100% using this process (eg at least 90%, at least 95%, at least 99% or at least 99.9%).
[0178] Cryogenic extraction processes can also be used to extract NGLs from natural gas and are more commonly used today. While absorption methods can extract almost all heavier NGLs (eg at least 95%), lighter hydrocarbons such as ethane are often more difficult to recover from the natural gas stream. In some cases, it is economical to simply let NGLs lighter into the natural gas stream. However, if it is economical to extract ethane and other lighter hydrocarbons, cryogenic processes can be used for high recovery rates. In some cases, cryogenic processes include dropping the temperature of the gas stream around minus 120 degrees Fahrenheit (about minus 84 degrees Celsius). In some cases, the condensed NGLs are then transported to subsequent processes while the gas components (eg methane and nitrogen and other gases) are removed in the form of a gas.
[0179] In some cases, the extraction systems used in this document operate both to separate non-hydrocarbon compounds, eg CO2, N2, and water, from hydrocarbon compounds, eg NGLs, but also function to demethanize the gas flow (eg separating methane from higher hydrocarbons and NGLs). As such, extraction units can separate one or more non-hydrocarbon compounds from one or more hydrocarbon compounds, or, when functioning as a demethanization unit, can separate at least one hydrocarbon component, i.e. methane, from at least one. minus one other hydrocarbon component, i.e. C2+ compounds.
[0180] There may be a number of different ways to cool the gas to these temperatures, but the turbo expansion process is generally more effective. In this process, external refrigerants can be used to cool the natural gas flow. Then an expansion turbine can be used to rapidly expand the cooled gases, which can drop the temperature significantly. This rapid temperature drop can condense ethane and other hydrocarbons in the gas stream, leaving methane in its gaseous state. This process can allow recovery of about 90% to 95% of the ethane originally in the gas stream. In addition, the expansion turbine is generally capable of converting the energy released when the natural gas stream is expanded to recompress the gaseous methane effluents, saving energy costs associated with ethane extraction.
[0181] Extracting NGLs from the natural gas stream can produce cleaner, purer natural gas, as well as allow for a more complete extraction of the valuable hydrocarbons that are the NGLs themselves (when compared to non-extraction of NGLs). Integration with Natural Gas Liquid Fractionation
[0182] Once hydrocarbons, eg ethane and NGLs have been removed from the natural gas stream, they are typically broken down into their basic components which may each have a separate value. The process that is commonly used to accomplish this task is called fractionation. Fractionation processes typically operate based on the different boiling points of different hydrocarbons in the NGL stream. In some cases, fractionation is carried out in the same facility as the previous gas processing steps, eg dehydration, deacidification and extraction/demethanization, while in other cases, fractionation takes place in separate facilities to which the composite NGLs are delivered.
[0183] The entire slicing process can be divided into steps, starting with removing the lighter NGLs from the stream. The fractionating operation can take place in stages where different hydrocarbons are boiled off one by one, where the name of a particular fractionator reflects its function, as it is conventionally named after the hydrocarbon that is boiled out. In this sense, the process generally includes, in order, a de-ethanizer, which separates the ethane from the remaining NGL stream, a de-propanizer; which separates the propane from the remaining NGL stream and a debutanizer, which boils the butanes out. In some cases, the remaining stream then contains mostly the heavier pentanes and hydrocarbons in the NGL stream. The separated butanes are also normally passed through a butane splitter or deisobutanizer, which can separate iso and normal butanes. In some cases, the fractionation system, whether referred to in its entirety or in relation to individual fractionation units, for example, a depropranizer, normally operates to separate at least one hydrocarbon component, such as propane, from at least one other component of different hydrocarbon such as butane, pentane etc. In some cases, the separation is not completely complete. For example, the deethanizer can remove 100% less ethane in the remaining NGL stream. Likewise, subsequent individual fractionation units may remove less than 100% of their respective compounds. In general, these fractionation steps can remove a substantial amount, and most of the compound to which they are directed, from the remainder of the NGL flux, for example, more than 50%, more than 60%, more than 75% and even more than 90% or 95%.
[0184] Figure 14 provides a schematic illustration of the processes and systems of major components in a typical natural gas processing facility. As shown in this example, raw gas from the gas well or other source 1402, which may have been treated in the well or other facility or intermediate processing unit to remove water and other condensate, for example, in step 1404, is transported to a facility processing. Raw gas inlet 1406 is then treated in a step/acid gas removal unit 1408, to remove any hydrogen sulfide or other corrosive gases 1410. Removed sulfur compounds or "acid gas" can be subjected to further processing, for example , in sulfur plant 1412 and further processing to produce elemental sulfur and tail gas, which can be further processed and/or incinerated.
[0185] The deacidified gas 1414 is then passed through a dehydration unit 1416 to further remove water and then passed through one or more additional purification units 1418, for example, for the removal of other impurities such as mercury. The purified natural gas is then passed to a 1420 extraction unit, which can be a cryogenic extractor comprising a 1420a turbo cryogenic expansion unit and a 1420b cryogenic nitrogen rejection unit, for methane separation into a rich methane stream 1422a and nitrogen 1422b from the NGL stream 1424. The resulting methane-rich component is then passed on as pipeline-ready natural gas, eg, transferred to the sales pipeline for the market, or as discussed in more detail in this document, can be submitted to subsequent treatment. As noted in this document, the extraction system 1420 can optionally include a lean oil extraction unit in place of a cryogenic extraction unit.
[0186] The resulting demethanized NGL containing product 1424, including ethane and other higher hydrocarbons (generally referred to in this document as C2+ components), is then passed through a 1426 fractionating train which typically includes a 1428 deethanizer unit which boils off the hydrocarbons of C2 1430 and passes the remaining fluids or "bottoms" 1432 to a depropanizer unit 1434. The depropanizer unit, in turn, boils out the C3 gases 1436, and passes the remaining bottoms 1438 to a debutanizer unit 1440, which boils off butanes 1442, leaving pentanes and higher order hydrocarbons in stream 1444. Each of the higher hydrocarbon streams 1430, 1436, 1442 and 1444 then can be subjected to further processing, for example, through sweetening units or splitters. butane. Integration with Steam Cracking
[0187] As described in this document, other significant petrochemical processing may revolve around the production of olefins and other higher hydrocarbons from natural gas, or petroleum distillates such as naphtha. In particular, saturated hydrocarbons can be transformed or converted to unsaturated hydrocarbons through a process called steam cracking. In steam cracking, a hydrocarbon gaseous or liquid feed such as naphtha, diesel, liquefied petroleum ("LPG"), or ethane can be diluted with steam and briefly heated in an oven without the presence of oxygen. Normally, the reaction temperature is very high, around 850°C or more, but the reaction can only take place briefly. In modern cracking furnaces, residence time is reduced to milliseconds to improve throughput, resulting in gas velocities faster than the speed of sound. In some cases, after the cracking temperature has been reached, the gas is rapidly quenched to stop the reaction in a transfer line heat exchanger or within a quench pipeline using quench oil. The resulting products are then further processed into separate high value separate products, such as olefins, from unwanted by-products and unreacted feed gases.
[0188] In some cases, many of the processes incorporated in conventional steam cracking facilities follow the same underlying principles of operation as systems used in NGL processing or other processing facilities. For example, many separations systems, such as depropanizer and/or desethanizer systems and C2 splitters, are typically included within cracking facilities to separate unreacted components such as methane and ethane or unwanted by-products from the olefin streams that emanate from the cracking.
[0189] Figure 15 shows a schematic illustration of an example of a steam cracking process and system. As shown, a gas feed 1502, such as naphtha or ethane from an NGL processing facility described above, is delivered along with a steam feed (not shown) to the furnace of the cracking device 1504. Following the cracking , the product is then quenched in refrigeration, for example, in transfer line exchanger 1506. The resulting product gas is then passed through compression and treatment steps (1508 and 1510), which may include, for example, compression of multi-stage gas, with each stage followed by cooling and removal of liquid hydrocarbons and water, as well as gas treatment to remove acidic gas components, eg, H2S and CO2, as well as dehydration to remove water, before being transferred to cryogenic section (cold box) 1511 for primed cooling and condensation of various components in order to remove CO and hydrogen at outlet 1514. then sent to the 1512 demethanizer to separate C1 1516 compounds, such as methane, from higher hydrocarbons, eg C2+ compounds in flow 1518. After demethanizing, the rich flow of C2+ 1518 is then passed through further fractionation steps, for example, deethaneizer 1522, to separate the C2 components from higher hydrocarbons in stream 1528, an acetylene reactor 1524, to convert acetylene in the rich stream from C2 to ethylene and ethane, and C2 splitter 1526 to separate ethylene from any residual ethane . The rich ethylene stream 1530 is then recovered as a product, while the residual ethane recovered from the C2 splitter is recycled through the cracker kiln 1504 into the recycle stream 1532. OCM Gas Processing Integration
[0190] OCM reactor processes and systems can be integrated into existing natural gas or other petrochemical processing facilities at one or more of a number of different specific points in those facilities, and with respect to a number of different inputs and outputs either from one or both of the OCM system and the unit processes of the global processing facility. In particular, OCM reactor systems can be integrated into conventional processing plants as one or two of a feed stream producer to one or more processing units within the processing facility, and/or as a stream consumer of product from one or more processing units within the processing facility.
[0191] In some cases, integration includes a variety of different types of integration, including, for example, integration of processes through fluid or gas coupling within a process flow. Fluid integration or fluid coupling or connection generally refers to a persistent fluid connection or fluid coupling between two systems within a total system or installation. Such persistent fluid communication usually refers to a network of interconnected ducts, coupling one system to another. Such interconnected pipelines may also include additional elements between two systems, such as control elements, for example, heat exchangers, pumps, valves, compressors, turboexpanders, sensors, as well as other fluids or systems for transport and/or storage of gas, for example, pipes, collectors, storage containers and the like, but they are generally entirely closed systems, distinguishing two systems where materials are transported from one another by means of any non-integrated component, for example, transport by rail car or truck, or systems not co-located in the same facility or immediately adjacent facilities. As used herein, fluid connection and/or fluid coupling includes complete fluid coupling, for example, where all effluent from a given point such as an outlet of a reactor, is directed to the inlet of another unit with which the reactor is connected with fluidity. Also included within such fluid connections or couplings are partial connections, for example, where only a portion of the effluent from a given first unit is routed to a second fluidly connected unit. Furthermore, stated in terms of fluid connections, such connections include connections to transport one or both of liquids and gases.
[0192] In some cases, integration refers to the thermal or energy integration of, for example, a CMO reactor system, into the energy infrastructure of a facility. Such integration may also include spatial integration of an OCM reactor system within the physical processing plant, for example, "within battery limits" (IBL), or it may be otherwise integrated but outside battery limits ( OBL) of the installation.
[0193] Figure 16 schematically illustrates a number of integration points of a CMO reactor system in the general process path of a natural gas processing facility shown in Figure 14. In particular, as shown in this example, an input of OCM, schematically identified as block 1602, is shown integrated in and fluidly coupled at various points in the process flow where the output or product from a specific processing unit is fed into the input of an OCM reactor system. For example, as shown, the OCM reactor is shown optionally with fluidity coupled to the output of, for example, dehydration unit 1416 or purification unit 1418 extraction unit 1420b desethanization unit 1428.
[0194] Alternatively or additionally, the output of the OCM reactor, illustrated schematically as block 1604, is shown integrated, eg fluidly connected, with various points in the process flow, where the OCM reactor product flows are fed into various processing units in the global facility. By way of example, the output of OCM 1604 may optionally be fluidly coupled to the input of extraction unit 1420, fractionating train 1426, e.g., fractionating units 1428, 1434 or 1440, or more processing units (not shown ). Integration with OCM Gas Feed
[0195] In some embodiments, a OCM reactor system is connected downstream of one or more processing units in a gas processing facility through which product streams from the processing unit are fed into the input stream of the gas system. CMO reactor. In particular, processing units that include one or more outlets, which contain methane and/or rich methane streams, can provide a gas feed to the CMO reactor system for converting methane to higher hydrocarbons. Likewise, OCM system outputs can often provide feed streams to and leverage the infrastructure of a number of systems in conventional processing units used to separate, modify and purify hydrocarbon mixtures.
[0196] In some cases, a CMO reactor system is provided integrated into an existing processing facility to occupy at least a portion of the natural gas ready for clean and dry pipeline for the conversion of the methane contained in the gas to higher hydrocarbons , instead of passing part of the dry gas through the extraction and fractionation units. In some cases, the inlet to the OCM reactor system may be fluidly coupled to acid gas removal unit 1408, dehydration unit 1416, or, as shown, additional purification unit 1418. As noted, this fluid connection may include one or more heat exchangers, pumps, compressors, or the like to present the dry gas to the OCM reactor system under conditions suitable for initiation of the OCM catalytic reaction, for example, inlet temperatures between 450°C and 600°C and pressures of 1 atmosphere or greater and preferably from about 103 kPa (15 pounds per square inch gauge (psig)) to about 1034 kPa (150 psig), 103 kPa (15 psig) to about 861 kPa (125 psig), or less than 689 kPa (100 psig), or from about 103 kPa (15 psig) to about 689 kPa (100 psig).
[0197] Alternatively or additionally, the OCM reactor system can be fluidly coupled with one or more output 1420 extraction unit(s) to route methane rich effluents from the 1420 extraction unit into the reactor system from OCM for conversion of methane to ethylene and other hydrocarbons, which can be passed through the extraction unit to separate ethylene and other C2+ components from gas components, eg CO, CO2, N2 and unreacted methane. In some cases, these and other outputs from conventional processing facilities are beneficially exploited. For example, in some cases, CO2 recovered from CMO reactor products and separated in the extraction unit can be transported via pipeline or truck, used on site or otherwise beneficially used in enhanced oil recovery (EOR). Likewise, N2 from the OCM reactor product and separated in the extraction unit is optionally recovered and transported via pipeline or truck, used on site, or otherwise beneficially used in, for example, enhanced oil recovery (EOR). Likewise, H2O from the OCM reactor product that is separated in OCM extraction or other purification units can be recovered and transported via pipeline or truck, used on site or otherwise beneficially used, for example, as a hydraulic fracturing.
[0198] In some cases, ethane rich streams from the 1426 fractionation train, for example, ethane rich effluent from deethaniser unit 1428, which may include small amounts of methane not previously removed, can be cycled in the CMO reactor, alone or in combination with one or more rich methane streams to convert any residual methane in the CMO reactor into higher hydrocarbons. Furthermore, as an intermediate in the OCM process, under the same OCM reaction conditions, the ethane present in the OCM feed can be reacted and converted to ethylene in the OCM reactor.
[0199] Rich ethane streams from the dethanizer can likewise be routed to ethane conversion systems. Such ethane conversion systems include, for example, steam cracking units that convert ethane to ethylene via non-oxidative dehydrogenation. In some cases, ethane may be routed to additional reactor systems containing catalysts for the oxidative dehydrogenation ("ODH") of ethane in the presence of an oxygen source, for the production of ethylene. Catalysts and systems for performing ODH reactions are described in, for example, Cavani, et al, Catalysis Today (2007), Vol. 127 (1-4), 113-131, the entire disclosure of which is incorporated in the addendum by reference. in full for all purposes. Again, the output streams from any of these systems can be further recycled or routed as needed to other processing units within the facility. Integration with the OCM Product
[0200] In some embodiments, the OCM reactor system is provided upstream of one or more processing units in the gas processing facility, so that product flows from the OCM reactor system, known as "Product flows of OCM" or "OCM product gases" can be further treated by different processing units within the facility.
[0201] For example, a CMO reactor system product stream, which generally includes C2+ hydrocarbons, as well as potentially CO, CO2, N2 and unreacted methane and other products, is passed through extraction unit 1420, such as a two-stage cryogenic extraction unit 1420a and 1420b, to separate ethylene, ethane and other C3 to C5+ hydrocarbons from nitrogen, CO and CO2 components, as well as any residual methane and other gas components. An example of a cryogenic extraction system for processing CMO product streams is described in US Patent Application No. 13/739,954, filed January 11, 2013, incorporated herein by reference, in its entirety for all effects. Briefly, cryogenic extraction systems typically include at least first and second separation units (eg 1420a and 1420b separation units), where the first unit (1420a) reduces the temperature of the inlet gases, eg NGL containing natural gas , or a CMO product gas. For discussion purposes, the separations system is described in terms of a CMO product gas. The first separations unit within a cryogenic separations system normally functions as a demethanizer, as lowering the temperature liquefies the C2+ components to result in a bottom portion that is rich in C2+, while the remaining gas component mainly comprises Methane components and N 2 is removed from the top of the unit. This methane-containing component is then passed through the second separations unit (1420b) which functions as a nitrogen rejection unit by liquefying the methane component and venting the nitrogen component.
[0202] Likewise, the OCM reactor system can also be supplied fluidly coupled to a lean oil extraction unit for separating the lighter hydrocarbon components from the other gas components.
[0203] In some cases, an OCM reactor system product stream, or optional system oligomerization, is optionally routed through the fractionation system, or one or more individual fractionation units of a conventional gas processing facility, to separate heavier hydrocarbons eg C3, C4 or C5+ and NGLs from lighter hydrocarbons eg ethane and ethylene. In such processes, ethane can be pulled in as a product or, as noted elsewhere in this document, redirected back to the OCM reactor system or to an ethane conversion process, for example, as described above. In some cases, the OCM product may be routed through a full length fractionation system, for example, multi-phase fractionation units, or it may be routed through any individual or any subset of fractionation units in the fractionation system global, eg only one de-ethanizer or only one de-ethanizer and/or de-propanizer etc.
[0204] In some cases, CMO reactor system integrations in an upstream or downstream configuration to one or more processing units within a gas processing facility are not mutually exclusive, as in many cases, the reactor A CMO will have inputs and provide outputs for several different processing units in the processing facility and in some cases will have inputs and provide outputs for a single processing unit, for example, a cryogenic extraction unit or a fractionation unit.
[0205] Figure 17 schematically illustrates an example of an integrated CMO reactor system in a conventional gas processing facility. In particular, a prepared OCM adiabatic reactor system 1702 coupled to the outlet of the purification unit 1418 of a gas plant is shown. As shown, a clean, dry gas stream 1720 from purification unit 1418, which may be a part or all of the output of purification unit 1418 at any given time, is routed to the input of the first reactor 1704 of a reactor system. of 1702 phase adiabatic OCM. The 1722 product stream from the 1704 reactor is then at least partially then introduced into the inlet of the 1706 reactor, which the 1724 product stream is at least partially introduced into the 1708 reactor inlet. illustrated as a 1702 adiabatic reactor three-phase system, it will be estimated that two three, four or more phases can be employed in an adiabatic system. Such adiabatic phase systems are described in U.S. Provisional Patent Application No. 13/900,898, filed May 23, 2013 and incorporated into the addendum by reference in its entirety for all purposes.
[0206] As shown, additional clean and dry gas from purification unit 1418 can also be introduced into subsequent reactors 1706 and 1708 in addition to the product stream from the previous reactor, eg product streams 1722 and 1724, respectively, as shown by the dashed arrows 1728 and 1730, to provide an additional source of methane for these subsequent reactors.
[0207] In addition to taking a portion of the product stream from the facility's 1418 purification unit(s), the OCM product stream from the global OCM reactor system, for example, is shown as the 1726 effluent stream from the 1708 reactor , may also undergo subsequent processing in the additional processing units of the gas processing facility.
[0208] In particular, as shown in figure 17, the output of the reactor system of OCM 1702 is fluidly coupled with the input of the extraction unit 1420 such that the product stream of OCM 1726 is introduced into the extraction unit 1420 to separate the higher hydrocarbons, eg C2+ components, in stream 1424, from any residual methane and nitrogen within the 1726 CMO product gas stream, eg in cryogenic demethanization unit 1420a. These higher hydrocarbons, optionally, are then routed to fractionating train 1426, e.g., units 1428, 1434 and 1440, for separating various different C2+ constituents from the demethanised product stream 1424. The fractionating unit is also referred to herein as a C2+ fractionation unit. The methane and nitrogen containing components are then optionally routed through the nitrogen rejection unit, eg the 1420b unit, to separate the nitrogen from the methane, methane which, optionally, can then be re-introduced into the OCM reactor system 1702 (not shown). As noted above, the cryogenic demethanizing unit, the entire cryogenic system 1420 or a similar separations unit can be positioned to receive effluent gas from individual reactor phases, eg, phases 1704 and 1706, as opposed to just receiving the gas of final CMO reactor system product (stream 1726), in order to grab C2+ compounds from streams 1722 and 1724, respectively, while passing methane to subsequent reactor steps for conversion. The resulting streams containing C2+ would then be routed for further processing, eg in fractionation train 1426. As noted, this would allow for efficiency in terms of reducing phase-to-phase C2+ product losses as well as improving reaction efficiency. based on the displacement of equilibria, for example, of a relatively higher concentration of reactant in each of the subsequent phases.
[0209] Figure 18 schematically illustrates an example of coupling the reactor system of OCM 1702 with the extraction unit 1420 and, particularly, the cryogenic separation unit 1420b and the fractionation system, for example, through the de-ethanizer 1428. In In particular, as shown, the 1820 methane-rich gas effluent stream from the cryogenic extraction unit 1420b is presented as a feed gas entering the inlet of reactor 1704. As noted above, the product gas from the first stage reactor is, at least partially fed into subsequent reactors 1706 and 1708, along with optional additional methane-containing gas streams 1822 and 1824 from the output of cryogenic extraction unit 1420b. The product gas stream 1726 from the OCM reactor system 1702 is then fed into the fractionating train 1426 in order to separate the various constituent products C2+. As shown, OCM optionally passes through optional oligomerization unit 1832 to convert C2+ hydrocarbons, eg ethylene, to high hydrocarbons, eg C3+ hydrocarbons, which are then transferred to the fractionation system for separation of different hydrocarbons high. Optionally, the output of the oligomerization unit 1832 can be transferred to the fractionation system at various points, including, but not limited to, the input or output of units 1428, 1434, 1440.
[0210] Alternatively, or in addition, the product stream from the OCM reactor system is fed back through the extraction units 1420, as shown by the dashed line 1826 of the reactor outlet 1708, in order to separate any residual methane and/ or nitrogen from desired CMO products, eg C2+ products, as described above.
[0211] Alternatively, or in addition, the product stream from the oligomerization system is fed back through 1420 extraction units in order to separate any residual methane and/or nitrogen from the desired oligomerization products, e.g., C2+ products, as per described above. OCM - Cracking Device Integration
[0212] As with the natural gas processing facilities described above, substantial value can be derived from integrating CMO reactor systems into existing cracking device facilities such as ethane or naphtha cracking devices. Figure 19 provides a schematic illustration of the integration of an OCM system into a cracking device installation. As shown in the simplified schematic of Figure 15, a typical cracking unit, for example a naphtha cracking device, includes the cracking furnace 1504 and closely associated quenching/quenching systems 1506. The C2+ product gases from the device Crackers are then passed through suitable treatment and compression systems 1508 and 1510, respectively, before routing to a cold box and 1512 demethanizer to separate any residual methane and hydrogen present in the cracking device effluent. The 1518 C2+ flow is then routed through a separation or fractionation system that typically includes a 1522 deethaneizer to separate the C2 components from the high hydrocarbons, eg, C3+, a 1524 acetylene converter that converts any acetylene produced during operation. of cracking in ethylene and a 1526 C2 divider to separate the ethylene (flow 1530) from the ethane (flow 1532) in the product gas, which is recycled back to the cracking furnace 1504.
[0213] In some cases, a CMO reactor system is integrated into a more conventional cracking facility to provide a number of benefits, including raw material flexibility, product range selectivity and energy efficiency.
[0214] An illustration of this integration is schematically shown in Figure 19 for example. As shown, a 1702 OCM reactor system again includes one, two, three or more OCM reactors, such as adiabatic phase reactors, 1704, 1706 and 1708, or one, two three or more isothermal serial or parallel reactors ( not shown). In contrast to certain integrations within gas processing facilities within a cracking device process, the OCM reactor system may not share raw materials with the underlying facility. In particular, as mentioned above, the CMO reactor uses methane and natural gas as its main feedstock, for example, in feed gas stream 1902, while the cracking device feedstock (stream 1502) will generally consist of ethane from NGLs, LPG or naphtha. However, by providing an alternative source of ethylene, while relying on many of the same unit operations for its production, an integrated OCM reactor system within a cracking facility provides significant raw material flexibility advantages. In particular, adverse fluctuations in the prices of raw materials and/or availability of naphtha or ethane from NGLs can be mitigated substantially, in whole or in part through the partial or substantial transition of a facility from a cracking facility fueled by naphtha or ethane to a methane-powered CMO installation. In some cases, the methane feed to OCM may come from methane produced from the steam cracking process which is normally combusted to produce energy for the endothermic cracking process.
[0215] As shown, a 1902 methane-containing gas feed typically including an oxidizing gas component, eg air or enriched air, is delivered to the 1702 OCM reactor system and brought into contact with the OCM catalyst contained therein under the OCM reaction conditions as described in this document. As shown, the 1726 OCM product gas, for example, including ethylene, methane, ethane and nitrogen, as well as other gases such as CO and CO2, is passed through a heat exchanger and compressor (not shown) before being passed in a 1906 cryogenic separation unit (including, for example, cryogenic separation units 1420a and 1420b in Figure 14) for the separation of nitrogen, CO and CO2 and removal of at least some of the residual methane present in the CMO gas. The C2+ rich stream from the separation unit (1908 stream), containing ethylene, ethane, C3+ hydrocarbons as well as additional residual methane is then transferred to the processing units downstream of the cracking device with which it is fluid integrated, for example , connected through a fluid coupling or connection. In particular, these product effluents from the cryogenic separation unit 1906 can be routed into, for example, cold box 1511 and demethanizer 1512 for the separation of any residual methane as well as any remaining hydrogen, CO and CO2. For this integration, the rejection of methane in the demethanizer portion of the cryogenic unit associated with the CMO reactor, eg cryogenic demethanizing unit 1420a, preferably can be adapted to yield methane/C2+ concentrations that are approximately equivalent to these concentrations for which the demethanizer cracking device, e.g., demethanizer 1512, is configured to address. As a result of reliance on the demethanizing capability of the existing cracking device, the cryogenic separation unit associated with the OCM reactor, for example the 1906 cryounit, is unloaded and can be supplied with a correspondingly reduced capacity, generating significant savings in capital. In some cases, a similar approach can be used in implementing the gas processing facility described above. In particular and with reference to Figure 17, an additional demethanization operation can be included in stream 1726 in order to be substantially equivalent to the CMO output methane content with the operating methane load of the facility's existing extraction unit, for example, unit 1420. In both the cracking device and gas processing implementation, this results in a substantial reduction in capital expenditure, which allows lower cost operations to integrate existing higher cost separations operations.
[0216] The C2+ products can then be routed to the cracking device's fractionation train, for example, deethaneizer 1522, acetylene reactor 1524 and C2 splitter 1526, to recover ethylene and recycle ethane back into the device's oven of cracking 1504.
[0217] In addition to providing raw material flexibility for a cracking device installation, an integrated OCM reactor system can also provide flexibility in the selection of product ranges, allowing for a relaxation in the operational severity of the cracking process. In particular, the ratio of ethylene to co-products, eg propylene etc., in a cracking process is a function of the cracking severity, which may be a function of the reaction conditions. Because the greatest demand is usually for ethylene, cracking devices tend to be operated to maximize ethylene production and minimize co-products, typically with an ethylene to propylene ratio of, say, greater than 2, using the raw material of naphtha. However, by complementing ethylene production through the use of the integrated OCM reactor system, one can adjust the severity of the cracking process, for example, to an ethylene to propylene ratio of less than 2, less than or equal to about 1.5, less than or equal to 1.25, less than or equal to 1, or less, using the naphtha feedstock to produce a greater amount of co-products as may be economically prudent given current market conditions. Product range optimization can be particularly useful in a naphtha cracking device environment where co-product production is more significant than in an ethane cracking environment where no significant co-product is generally produced.
[0218] In some cases, a cracking device installation is completed using an integrated OCM reactor system in the amount of more than about 5% of the ethylene produced on a weight to weight basis, greater than about 10 % of ethylene produced, on a weight-to-weight basis. In some cases, a cracking device installation is supplemented using an integrated OCM reactor system in the amount of at least 20%, at least about 30% and in some cases greater than about 40% or even 50%. In some embodiments, at least 2%, at least 5%, at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% of the ethylene produced by the integrated plant is produced directly from the reactor part of CMO.
[0219] In some embodiments, the contribution of the CMO integrated system, calculated on a weight-to-weight basis when including as ethylene produced from CMO the total ethylene produced from CMO reactor feedstock (ie, including both the ethylene produced directly from the OCM reaction, as well as the cracked ethylene from ethane that is produced by the OCM reactors) is between 10% and about 50%, between about 20% and about 50%, between about from 30% to about 50%, or from about 40% to about 50%.
[0220] In some embodiments, to additionally provide more product flexibility, the OCM effluent can be routed, optionally, forming an ethylene oligomerization unit (adiabatic or isothermal reactors described above) that is intended to output a closed range of aromatic hydrocarbons, eg benzene, toluene and xylene (BTX) or benzene, toluene, ethylbenzene and xylenes (BTEX), for a portion of the OCM outflow stream. In conjunction with the operational flexibility described above, this configuration can specifically provide the ability to change the gravity of the cracking units in combination with the OCM unit and optional ethylene oligomerization unit to output the desired combination of ethylene, propylene, olefins of C4 and C5 and provide additional flexibility in selecting product ranges from the global system to produce greater amounts of high value aromatics. Energy Integration
[0221] Heat, electricity, mechanical work or any other form of energy can be transferred between processes described in this document (eg, OCM, ODH) and hydrocarbon or other processes (eg, non-OCM processes such as refineries , natural gas processing facilities, cracking devices). Energy can be transferred to the OCM process or the OCM process at any appropriate time and in an appropriate manner (eg using a heat exchanger).
[0222] In addition to integration of OCM reactor feeds and products into conventional hydrocarbon processing facilities, eg natural gas processing facilities, refineries, cracking devices etc., or their component units or systems, also here presented is the energetic integration of the CMO process into existing systems. In particular, by exploiting the thermal energy produced in the highly exothermic CMO reaction, one can augment the thermal systems of an existing installation, eg heaters and boilers to potentially reduce the overall energy that is required to be generated separately for control. of the processing units at the facility.
[0223] As noted above, OCM is a strongly exothermic reaction that, in some circumstances, operates at temperatures between about 400° C and 950° C, depending on the reactor process and system used and in any case, at temperatures of reactor feed input between about 400°C and 600°C. Therefore, initiation of the OCM reaction tends to require an initial input of thermal energy to raise the reactants and catalysts for proper reaction initiation, or "temperature of boot". Once started, the exothermic nature of the reaction usually produces enough thermal energy to sustain the reaction. In addition, as the OCM catalytic process tends to generate thermal energy, it may be necessary to draw thermal energy from one or more of the reactor systems and/or product gas flows in order to efficiently manage the catalytic reaction and steps subsequent processing. In some cases, this excess thermal energy can be used as one or both of a thermal source and another energy source for other installation operations. In some configurations, general reaction temperatures can range from start-up temperatures between 400°C to 600°C, to maximum reactor outlet temperatures of more than 950°C, depending on whether the reactor system is operated in a configuration isothermal or adiabatic.
[0224] In some cases and with reference to, for example, a natural gas fractionation facility, thermal energy created by the OCM reaction can be removed from OCM product gas streams, or in the case of isothermal reactor systems , other heat exchange means, for heating the different components of the fractionation unit, e.g. In other words, rather than separately generating thermal energy to move the process aspects of a processing facility, the OCM reactor system provides some or all of this thermal energy. This provides additional value of the OCM reactor system in addition to the generation of highly valuable hydrocarbon products.
[0225] For example, referring to the process illustrated in Figure 20, OCM product gas streams, for example, intermediate OCM product streams 1722 and/or 1724, and/or OCM end product stream 1726, they can be passed through one or more heat exchangers, e.g., 2002 and 2004 heat exchangers, to reduce the temperature of the OCM gas product to temperatures suitable for introduction into subsequent reactors 1706 and 1708, respectively. Likewise, the OCM 1726 product gas stream can be passed through the 2006 heat exchanger to reduce the stream temperature to levels suitable for subsequent processing steps. Steam, water or any other means of heat exchange that runs through heat exchangers, 2002, 2004 and/or 2006 are routed through one or more of 1428 de-ethanizer, 1434 de-propanizer and/or 1440 de-butenizer to supply used thermal energy to boil the components in the fractionation process. This thermal energy can be used alone or to supplement the existing boiling capacity of a processing facility and reduce the amount of energy required for that boiling capacity.
[0226] In addition, thermal energy removed from the reactor system of OCM or product streams can also be used to heat other process streams in the facility. For example, in addition to being used to heat the feed stream of the OCM reactor system to suitable catalytic temperatures, the thermal energy from the OCM product streams or reactor systems can be used to heat the cooled NGL streams after cryogenic extraction from those NGL of natural gas flow or OCM reactor gas outlet. This is illustrated schematically in Figure 20.
[0227] In some cases, using heat transfer between the cooled NGL stream from the cryogenic extractor, one is simultaneously heating the NGL stream and cooling the heat exchange medium that is used to cool the OCM product streams.
[0228] Alternatively, or in addition, thermal energy removed from the OCM system can be converted to electrical energy. For example, product gases, or in the case of isothermal reactors, a heat exchange medium that is carrying heat away from a reactor itself, can be passed through a heat exchanger to create steam, which is used to move the turbine of an electric generator. Then, the resulting electrical energy can be used to increase the energy used to run additional systems in the facility, such as lighting, office systems, pumps and other control systems. In such cases, the electrical generation system constitutes a processing unit, for the integration of energy from the CMO reactors in the processing plant. In particular, thermal energy from the CMO reactor system is transmitted to the electric generator to generate electricity from steam, which electrical energy is in turn transmitted to one or more different processing units within the plant, or to other operations within the plant, even back to the grid.
[0229] As mentioned above, with respect to feed and product integration of OCM reactor systems in a gas processing facility or system, OCM reactor systems can have multipoint integration in a system in terms of feed, product, thermal energy and electrical energy and can, in some cases, be integrated with most or all of the above aspects. For example, feed to the OCM reactor can be derived from effluent from an extraction unit, while the product from the OCM reactor system can be fed to the global facility's extraction unit. Thermal energy derived from the OCM exothermic reactor system can simultaneously be used to increase the boiling capacity used to operate the fractionation systems and/or heat the feed gases used in the OCM reactor system. Excess steam generation, moreover, from the OCM exothermic reactor system can simultaneously be utilized in the generation of electricity using a conventional electric steam generator system. Any combination of multipoint integration can be practiced.
[0230] As with the NGL processing facilities described above, energy conservation and reuse may be applicable to cracking device facilities for the purpose of "on purpose" steam generation, eg for driving turbines, boilers, compressors etc. In particular, the heat generated by OCM reactor systems can be used to supplement or replace boilers normally used in cracking device operations. Likewise, refrigerant streams or heat exchange media can be circulated through heat exchangers in the OCM reactor system to cool effluents from that system. Furthermore, heat energy can again be converted to electrical energy as described above.
[0231] In some cases, integrated systems can be used in the generation and collection of carbon dioxide for use in still other natural gas processes. In particular, bulk carbon dioxide has found recycling uses in the oil and gas industry in, for example, improved oil recovery ("EOR") processes. In EOR processes, CO2 is injected into oil reservoirs to displace oil from the porous rock as well as provide reduced viscosity.
[0232] Carbon dioxide (CO2) generated as a by-product of a OCM reaction can be separated in an extraction process. Rather than being discarded, however, the CO2 can be collected for use. The collected CO2 can be stored on-site at the facility or it can be transported to a location where it will be used, such as an oil field. Such transport may involve a truck, train or transport pipeline, depending on the amount of CO2 involved. In addition to using a 'waste' product from the global system for a useful purpose, the beneficial use of CO2 can also provide gas facility operators with carbon credits for sale or exchange with other greenhouse gas producers. These credits can provide additional value to operators of OCM integrated systems installations described here.
[0233] Using Unreacted Methane as a Fuel in Hydrocarbon Processing
[0234] OCM reactions are generally not run with complete conversion (eg not all methane entering the OCM reactor is converted to C2+ hydrocarbons). Unreacted methane can be recycled back to the OCM reactor in some cases (eg after a separation). Another use for the unreacted methane disclosed in this document is to burn the methane in a hydrocarbon process (i.e., to provide energy).
[0235] In one aspect, a method for integrating a methane process oxidative coupling (OCM) with a hydrocarbon processing comprises providing an OCM product stream comprising C2+ hydrocarbons and unreacted methane, performing a separation that provides an enriched first stream in methane and provides a second stream enriched in C2+ hydrocarbons and combusts the first stream to provide energy for hydrocarbon processing. Hydrocarbon processing can be, without limitation, an oil refinery, a natural gas liquids (NGL) process or a cracking.
[0236] It should be understood from the foregoing that, although particular implementations have been illustrated and described, several modifications may be introduced and are contemplated in this document. Nor is the invention intended to 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 preferred embodiments herein are not intended to be construed in a limiting sense. Furthermore, it is to be understood that all aspects of the invention are not limited to the specific embodiments, configurations or relative proportions set forth herein which are dependent upon a variety of conditions and variables. Various modifications in the form and detail of the embodiments of the invention will be apparent to those skilled in the art. It is, therefore, anticipated that the invention will also encompass any such modifications, variations and 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 are covered.

权利要求:
Claims (23)
[0001]
1. Method for the oxidative coupling of methane to generate hydrocarbon compounds containing at least two carbon atoms (C2+ compounds), the method characterized in that it comprises: (a) directing a feed stream comprising methane from a process from hydrocarbons to a methane oxidative coupling (OCM) reactor at an inlet temperature between 400°C and 600°C, where the OCM reactor is operated under adiabatic conditions without an integrated thermal control system used to maintain little or no temperature gradient in the OCM reactor, wherein the OCM reactor is configured to carry out one or more OCM reactions to generate a reactor effluent comprising C2+ compounds from said methane, wherein said OCM reactor comprises a nanostructured catalyst that catalyzes one or more OCM reactions, wherein said hydrocarbon process is a non-OCM process, wherein during the one or more OCM reactions, the OCM reactor has a profile positive temperature across the OCM reactor, wherein the positive temperature profile includes a first feed stream temperature and a second reactor effluent temperature, and wherein the second temperature is greater than the first temperature; (b) performing one or more OCM reactions in the OCM reactor using said methane to produce a reactor effluent comprising one or more C2+ compounds; (c) separating the reactor effluent into at least a first stream and a second stream, wherein the first stream has a lower C2+ concentration than said second stream, and wherein said second stream has a higher C2+ concentration than said product stream; and (d) directing said second stream to said hydrocarbon process.
[0002]
2. Method according to claim 1, characterized in that the hydrocarbon process is an oil refinery, a natural gas liquids process, or a cracking.
[0003]
3. Method according to claim 1, characterized in that at least a portion of said first stream is directed to said OCM reactor.
[0004]
4. Method according to claim 1, characterized in that a concentration of C2+ compounds in said second stream is less than 90%.
[0005]
5. Method according to claim 4, characterized in that said first stream has a concentration of C2+ compounds that is less than 50%.
[0006]
6. Method according to claim 1, characterized in that said reactor effluent is separated into at most three separation units.
[0007]
7. Method according to claim 6, characterized in that said reactor effluent is separated into at most two separation units.
[0008]
8. Method according to claim 1, characterized in that said separation is with the aid of pressure balance adsorption.
[0009]
9. Method according to claim 1, characterized in that said separation is with the aid of cryogenic separation.
[0010]
10. Method according to claim 1, characterized in that said first stream and said second stream are directed to said hydrocarbon process.
[0011]
11. Method according to claim 1, characterized in that a concentration of C2+ compounds in said second stream is within 20% of a concentration of C2+ compounds in a portion of said hydrocarbon process for which the second stream is targeted.
[0012]
12. Method according to claim 1, characterized in that said reactor effluent also comprises non-C2+ impurities.
[0013]
13. Method according to claim 12, characterized in that said non-C2+ impurities comprise one or more nitrogen (N2), water (H2O), argon (Ar), carbon monoxide (CO), carbon dioxide (CO2) and methane (CH4).
[0014]
14. Method according to claim 12, characterized in that said second stream has a lower concentration of said non-C2+ impurities than said first stream.
[0015]
15. Method according to claim 1, characterized in that said one or more C2+ compounds are hydrocarbons having between two and five carbon atoms.
[0016]
16. Method according to claim 1, characterized in that the C2+ compounds comprise ethylene.
[0017]
17. The method of claim 1, characterized in that a second stream mass flow rate is less than 30% of a mass flow rate of a portion of said hydrocarbon process for which the second current is directed.
[0018]
18. Method according to claim 1, characterized in that said separation is with the aid of a lean oil extraction system.
[0019]
19. Method according to claim 1, characterized in that said separation comprises: (i) introducing said reactor effluent comprising the one or more C2+ compounds and non-C2+ impurities into a vessel at a first pressure, in that the vessel comprises an adsorbent medium, wherein upon introduction of said reactor effluent into said vessel, said reactor effluent is brought into contact with said adsorbent medium; (ii) changing the pressure in the vessel to a second pressure to release (i) at least a subset of said one or more C2+ compounds or (ii) said non-C2+ impurities from said adsorbent medium, thereby separating said at least the subset of said one or more C2+ compounds from said non-C2+ impurities; and (iii) recovering said at least a subset of said one or more C2+ compounds in said second stream.
[0020]
20. Method according to claim 1, characterized in that said separation is with the help of one or more of a de-ethanization unit, a de-propanization unit and a de-butanization unit.
[0021]
21. Method according to claim 1, characterized in that the OCM reactor has a pressure of less than 150psig and in which the one or more OCM reactions have a methane conversion of at least 10% in a single process pass and a C2+ selectivity of at least 50%.
[0022]
22. Method according to claim 16, characterized in that it further comprises, after (b) and before (c), the transfer of reactor effluent to an oligomerization system to produce one or more higher hydrocarbon compounds from the C2+ compounds in the reactor effluent.
[0023]
23. Method according to claim 1, characterized in that said separation is carried out using at least a portion of thermal energy generated in said one or more OCM reactions.

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法律状态:
2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-11-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-03-31| B25A| Requested transfer of rights approved|Owner name: LUMMUS TECHNOLOGY LLC (US) |

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2021-04-20| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-07-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-31| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/07/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201261669523P| true| 2012-07-09|2012-07-09|

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US61/669,523|2012-07-09|

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US201361773669P| true| 2013-03-06|2013-03-06|

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US61/773,669|2013-03-06|

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PCT/US2013/049742|WO2014011646A1|2012-07-09|2013-07-09|Natural gas processing and systems|

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