Invented by Suchia Duggal, Guido Radaelli, Jarod McCormick, Andrew Aronson, Joel Cizeron, CB&I Technology Inc

The market for Advanced Oxidative Coupling of Methane (AOCM) is expected to grow significantly in the coming years. AOCM is a process that converts methane, the primary component of natural gas, into ethylene, a key building block for the chemical industry. This process has the potential to revolutionize the way we produce ethylene, as it is a more efficient and environmentally friendly alternative to traditional methods. The global demand for ethylene is expected to continue to grow, driven by the increasing demand for plastics, packaging materials, and other chemical products. According to a report by Grand View Research, the global ethylene market size was valued at USD 163.5 billion in 2019 and is expected to grow at a compound annual growth rate (CAGR) of 4.2% from 2020 to 2027. The AOCM process has several advantages over traditional methods of producing ethylene. Firstly, it is a more environmentally friendly process, as it produces fewer greenhouse gas emissions compared to traditional methods. Secondly, it is a more efficient process, as it converts methane into ethylene with a higher yield and selectivity. Finally, it is a more cost-effective process, as it requires less energy and fewer raw materials compared to traditional methods. The AOCM market is still in its early stages, but several companies are already investing in this technology. For example, ExxonMobil has developed a proprietary catalyst for AOCM and has been testing the technology in a pilot plant in Texas. In addition, several research institutions and universities are also working on developing new catalysts and improving the efficiency of the AOCM process. The AOCM market is expected to grow significantly in the coming years, driven by the increasing demand for ethylene and the need for more environmentally friendly and cost-effective production methods. However, there are still several challenges that need to be addressed, such as the development of more efficient catalysts and the optimization of the AOCM process. In conclusion, the market for Advanced Oxidative Coupling of Methane is expected to grow significantly in the coming years, driven by the increasing demand for ethylene and the need for more environmentally friendly and cost-effective production methods. While there are still several challenges that need to be addressed, the potential benefits of this technology make it a promising alternative to traditional methods of producing ethylene.

The CB&I Technology Inc invention works as follows

The present disclosure reveals a method to generate higher hydrocarbon(s), from a stream consisting of compounds with two or more Carbon atoms (C2+). It involves introducing methane as well as an oxidant (e.g. O2) into an OCM (oxidative coupling methane) reactor. This reactor has been retrofitted into an ETL (ethylene-to-liquids) reactor. The OCM reactor reacts methane with the oxygenant to produce a first stream containing the C2+ compounds. The first product stream can be directed to the pressure swing adsorption unit (PSA), which recovers at most a portion the C2+ compound from the first stream. This will produce a second stream that contains at least the amount of C2+ compounds. The second product stream can be then directed to the ETL reactor. From the ETL reactor’s C2+ compounds, the higher hydrocarbon(s), can be produced.

Background for Advanced Oxidative Coupling of Methane

Fractionation technology is used extensively in modern refining and Petrochemical industries to separate and produce various desired compounds from crude oil. Fractionation technology can be energy-intensive and expensive to set up and maintain. Cryogenic distillation is a method that separates and recovers hydrocarbon products from various industries. It has been used for more than 100 years. There is still a need for other methods and systems for the separation of hydrocarbon products, especially for OCM (oxidative coupling methane) processes.

Aspects of this disclosure include methods for recovering olefins in a stream that contains a mix of hydrocarbons using techniques that use adsorbents. Systems and methods are available that enable separation, pre-separation and purification of hydrocarbons. These include olefins and ethylene, propylene and methane from multicomponent streams of hydrocarbons. In certain cases, the hydrocarbon stream may also be used as the feed to an OCM or ETL reactor. In some cases, the OCM reactor’s effluent can be the feed to the ETL reactor. Sometimes, an adsorbent-based separation can be used to pre-treat and purify existing hydrocarbon streams. This is followed by the use of the ETL feed as the PSA tail gas or refinery offgases.

The present disclosure provides a number of improvements to OCM and ETL processes such as, but not limited to, a separation process and preseparation process for recovering desired or predetermined parts from an OCM reactor effluent. CO2 recovery and capture methods, enhanced heat recovery techniques to use the OCM reaction heat more effectively, and techniques and technologies that further reduce the OCM process’s carbon footprint.

An aspect to the present disclosure provides a means of generating higher hydrocarbons from a stream consisting of compounds with two or more Carbon atoms (C2+). This involves introducing methane as well as an oxidant (e.g. O2) into an OCM (oxidative coupling methane) reactor. The reactor has been retrofitted into an ETL (ethylene-to-liquids) system. The OCM reactor reacts methane with the oxygenant to produce a first stream containing the C2+ compounds. The first product stream can be directed to the pressure swing adsorption unit (PSA), which recovers at most a portion the C2+ compound from the first stream. This will produce a second stream that contains at least the amount of C2+ compounds. The second product stream can be then directed to the ETL reactor. From the ETL reactor’s C2+ compounds, the higher hydrocarbon(s), can be produced.

In some cases, the product stream can be directed to intermediate units prior to the PSA. For example, a PBC (post-bed cracking) unit that produces alkenes from the alkanes. You can include the alkenes in the first product stream. This can then be directed towards the PSA.

In one aspect, the present disclosure provides a means of generating higher hydrocarbons from streams comprising compounds having two or more carbonatoms (C2+). This involves: (a) inserting methane and an oxygenant into an OCM reactor. The OCM reactor reacts with methane to produce a first product stream; (b) directing that first product stream into a pressure swing-adsorption (PSA), unit that recovers at most a portion the C2+ compound from the ETL reactor; and (d).

In some embodiments, this method also includes: (e) recovering hydrogen and (iii) carbon dioxide (CO2) from a PSA unit and recycling it to the OCM nuclear reactor; (f), directing at most a portion into a methanation device that reacts the hydrogen with the CO and/or the CO2 to create methane; (g) directing methanation product streams into the OCM nuclear reactor.

In some embodiments, the method also includes recovering C2 or C3 compounds from a second product stream and directing those C2 or C3 compounds to an OCM reactor. Some embodiments include a PBC (post-bed cracking) unit.

In another aspect, this disclosure describes a method of generating compounds having two or more carbon-atoms (C2+ compound). It involves: (a) directing oxygen [O2] and methane [CH4] into an oxidative coupled of methane reactor that reacts the O2 (OCM process) to produce a product stream that contains (i) C2+ substances including ethylene (C2H4); (b) directing the OCM reactor’s product stream into a separations unit that uses a refrigerant, which includes methane from product stream, to enriching the C2+.

In some embodiments, product streams are directed through one or more units into the separations systems.

In some embodiments, this method also includes separating methane out of the product stream to be used in the refrigeration unit. Some embodiments further include directing CO or CO2 from the productstream to a methanation reaction that produces methane. The method may also include directing at most a portion the methane from the methanation production stream to the OCM reactor. The method may also include separating the product stream into an ethylene product stream that contains ethylene, and (ii), a C3+ productstream comprising compounds with three or greater carbon atoms (C3+ compound). The method may also include directing the ethane from a product stream to an OCM reactor. Some embodiments further include compressing the product stream before directing it into the separations.

In another aspect, this disclosure provides a method of generating compounds having two or more carbon-atoms (C2+ compound). It involves: (a) directing oxygen [O2] and methane [CH4] into an oxidative coupled of methane reactor that reacts the O2 (OCM) process to produce a product stream that includes (i) C2+ substances including ethylene (C2H4); (ii) carbon monoxide/carbon dioxide (CO2); (b) a complexation cata complexation that forms the ethylene in the product streams, enriching the C2+ compounds with the product stream to enrich the C2+.

In some embodiments, the product streams are directed through one or more additional units to the separations system. The method may also include using the complexation unit for the removal of one or more impurities in the product stream. These impurities can be selected from the group consisting CO2, sulfur compounds and acetylenes. The complexation catalyst may include one or more metals from the group consisting silver and copper. The method may also include directing CO or CO2 from the productstream to a methanation reaction that produces methane. The method may also include directing methane from the methanation stream to the OCM reactor. The method may also include the separation of the product stream into an ethylene product stream that contains ethylene, and (ii), a C3+ productstream comprising compounds with three or greater carbon atoms (C3+ compound). The method may also include directing the ethane from a product stream to an OCM reactor. Some embodiments further include compressing the product stream before directing it into the separations.

In another aspect, this disclosure describes a method of generating compounds with two- or more carbon atoms. It includes: (a) directing oxygen and methane into an OCM reactor that reacts O2 and CH4 in an OCM reaction to produce a product stream that contains (i), C2+ compounds including C2H4 and (ii), carbon dioxide and carbon dioxide. (b) directing the OCM reactor’s product stream into a CO2 separation system to separate CO2 from the CO2 and to extract CO2 at a cryogenic or low-temperature of CO2 that has an operating temperature that is less than the boiling point of methane but not exceeding the boiling point of carbon dioxide.

In some cases, the product stream is directed through one or more additional units into the separations systems. Some embodiments use an amine-based absoprtion method to sorb or solvent separate CO2. Some embodiments employ a Benfield process for solvent separation or sorbent of CO2. Some embodiments use diethanolamine as a solvent or sorbent for CO2 separation. Glycol dimethylether is sometimes used as a solvent or sorbent for CO2 separation in some instances. Some embodiments use propylene carbonate as a solvent or sorbent for CO2 separation. Sulfinol is sometimes used as a solvent or sorbent for CO2 separation in some embodiments.

Some embodiments use a zeolite as a solvent or sorbent for CO2 separation. Some embodiments use active carbon as a solvent or sorbent for CO2 separation. The CO2 separation system may include a membrane CO2 separation device. Some embodiments use a polymeric membrane for the separation of CO2. Some embodiments use a metallic membrane for the membrane separation. Some embodiments use a ceramic membrane for CO2 membrane separation. Some embodiments use a hybrid membrane that supports a solvent or absorbent for the membrane separation of CO2. Some embodiments use a poly-ionic liquid membrane for CO2 membrane separation. Some embodiments use a supported ionic fluid membrane for CO2 membrane separation. Some embodiments use a polyetherimide membrane for the membrane separation of CO2.

In some embodiments, this method also includes directing the CO2 from a product stream to a reactor that reacts the CO2 and produces a methanation product streams comprising methane. The method may also include directing methane from the methanation product streams to the OCM reactor. The method may also include the separation of the product stream into an ethylene product stream that contains ethylene, and (ii), a C3+ productstream comprising compounds with three or greater carbon atoms (C3+ compound). The method may also include directing the ethane from product stream to OCM reactor. Some embodiments further include compressing the product stream before directing it into the separations unit.

In another aspect, this disclosure provides a method of generating compounds having two or more carbon-atoms (C2+ compound). It includes: (a) directing water in an electrolysis device that electrolyzes water to produce oxygen (O2) and hydrogen (H2);(b) directing O2 from an electrolysis reactor and methane to an OCM reactor that reacts O2 and CH4 to create CH4; (c) directing at most a portion the CO and/or the CO2 into the OCM reactor to the OCM; and/or the CO2 to generates to yielding the CO2 to produce CH4 to the OCM; and/or the OCM reactor; and/or the CO2 to make CH4 to the OCM.

In some embodiments, an alkaline water electrolysis is included in the electrolysis unit. The electrolysis unit may also include a proton exchange membrane system. In some embodiments, an electrolysis unit includes a steam electrolysis device.

In another aspect, this disclosure describes a method of generating compounds having two or more carbon-atoms (C2+ compound). It includes: (a) directing oxygen [O2] and methane [CH4] into an OCM reactor that reacts O2 and CH4 in an OCM reaction to produce a product stream that contains (i) C2+ substances including ethylene (C2H4); (b) directing product stream from OCM reactor into a separations unit that uses a CO2+ compound to enrich the C2+; and (c) to the OCM].

In some embodiments, product streams are directed through one or more units into the separations systems.

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