WO2017077421A1 - Procédé et système de production de gaz de synthèse à partir de dioxyde de carbone et d'hydrogène - Google Patents

Procédé et système de production de gaz de synthèse à partir de dioxyde de carbone et d'hydrogène Download PDF

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Publication number
WO2017077421A1
WO2017077421A1 PCT/IB2016/056418 IB2016056418W WO2017077421A1 WO 2017077421 A1 WO2017077421 A1 WO 2017077421A1 IB 2016056418 W IB2016056418 W IB 2016056418W WO 2017077421 A1 WO2017077421 A1 WO 2017077421A1
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Prior art keywords
stream
transferring
feed
fired heater
certain embodiments
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PCT/IB2016/056418
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English (en)
Inventor
Mubarik Ali BASHIR
Awais Ahmed
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Sabic Global Technologies B.V.
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Application filed by Sabic Global Technologies B.V. filed Critical Sabic Global Technologies B.V.
Publication of WO2017077421A1 publication Critical patent/WO2017077421A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0495—Composition of the impurity the impurity being water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0816—Heating by flames
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Definitions

  • the presently disclosed subject matter relates to methods for generating synthesis gas (syngas) from carbon dioxide and hydrogen.
  • Syngas is a mixture of carbon monoxide (CO) and hydrogen (H 2 ), which can also contain other gas components, such as water (H 2 0), carbon dioxide (C0 2 ), methane (CH 4 ) and/or nitrogen (N 2 ).
  • Syngas can be used in the production of synthetic fuel or as feedstock for a number of chemical reactions, including Fischer-Tropsch synthesis to create higher hydrocarbons, methanol synthesis, olefin synthesis, oxo synthesis (also known as hydroformylation), and carbonylation reactions.
  • the presently disclosed subject matter relates to systems and methods for generating syngas from carbon dioxide (C0 2 ) and hydrogen (H 2 ).
  • methods for producing syngas in a reverse water gas shift (RWGS) reaction are provided.
  • a feed stream containing C0 2 and H 2 is heated in the convection section of a fired heater to produce a heated feed stream.
  • the method can further include preheating the feed stream in a heat exchanger prior to transfer to the convection section of a fired heater.
  • the temperature of the heated feed stream is from about 200°C to 800°C, from about 300°C to about 700°C, or from about 350°C to about 650°C.
  • the heated feed stream is fed to catalyst tubes disposed within the radiant section of a fired heater.
  • the method includes contacting the heated feed stream with a catalyst to produce an effluent stream including shift reaction products.
  • the effluent stream includes CO, H 2 , and unconverted C0 2 .
  • the effluent stream has a temperature of about 500°C to about 1400°C, from about 700°C to about 1200°C, from about 800°C to about 1000°C, or from about 850°C to about 900°C.
  • the method further includes reducing the temperature of the effluent stream in a waste heat recovery unit.
  • the method can include transferring the effluent stream to a boiler.
  • the method includes transferring heat from the effluent stream to the boiler feed water to produce steam.
  • the method further includes transferring the steam to one or more coil arrangements in the fired heater to produce superheated steam.
  • the method can include transferring the effluent stream to a product cooler.
  • the temperature of the effluent stream is reduced to from about 15°C to about 75°C, from about 30°C to about 60°C, or from about 40°C to about 50°C.
  • the method further includes transferring the cooled effluent stream to one or more separators.
  • the method includes separating water from the cooled effluent stream to produce a product stream.
  • the method further includes separating C0 2 from the product stream to produce a syngas stream.
  • recovered C0 2 is recycled back into the RWGS reaction.
  • the presently disclosed subject matter further provides a system for producing syngas from a reverse water gas shift (RWGS) reaction.
  • the system includes a fired heater containing a radiant section and a convection section.
  • the radiant section includes catalyst tubes.
  • the convection section includes one or more coil arrangements.
  • the system includes a fired heater coupled to one or more feed lines configured to transfer hydrocarbons to a burner for combustion.
  • the combustion reaction heats the radiant section to a temperature from about 750°C to about 1300°C, from about 900°C to about 1200°C, or from about 1000°C to about 1100°C.
  • flue gas from the combustion reaction heats the convection section of the fired heater.
  • coil arrangements within the convection section are used to heat C0 2 and H 2 feedstock.
  • coil arrangements within the convection section are used to heat air for the combustion reaction.
  • coil arrangements within the convection section are used to superheat steam.
  • the system further includes a feed line for transferring C0 2 and H 2 from a coil arrangement within the convection section to catalyst tubes within the radiant section of the fired heater.
  • the system further includes a waste heat recovery unit coupled to the effluent stream exiting the fired heater.
  • the waste heat recovery unit includes a boiler and product cooler.
  • the boiler is configured to transfer heat from the effluent stream to water to produce saturated steam.
  • the product cooler includes one or more heat exchangers in series for reducing the temperature of the effluent stream.
  • the system further includes one or more product separators.
  • the system includes a water separator for condensing water from the effluent stream to produce a product stream.
  • the system further includes a C0 2 recovery unit for recovering C0 2 from the product stream to produce a purified syngas stream.
  • a C0 2 recycle line is coupled to the C0 2 recovery unit for transferring recovered C0 2 to the product feed line.
  • FIG. 1 is a schematic diagram depicting an exemplary system in accordance with a non-limiting embodiment of the disclosed subject matter.
  • FIG. 2 is a schematic diagram depicting an exemplary method in accordance with a non-limiting embodiment of the disclosed subject matter.
  • the presently disclosed subject matter provides systems and methods for generating syngas from C0 2 and H 2 .
  • the presently disclosed subject matter provides systems and methods for integrating heat recovery into the production of syngas from C0 2 and H 2 .
  • the term “about” or “approximately” means within an acceptable error range for the particular value as determined by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system. For example, "about” can mean a range of up to 20%, up to 10%, up to 5%), and or up to 1% of a given value.
  • the term "coupled” refers to the connection of a system component to another system component by applicable means known in the art.
  • the type of coupling used to connect two or more system components can depend on the scale and operability of the system.
  • coupling of two or more components of a system can include one or more joints, valves, transfer lines or sealing elements.
  • joints include threaded joints, soldered joints, welded joints, compression joints and mechanical joints.
  • fittings include coupling fittings, reducing coupling fittings, union fittings, tee fittings, cross fittings and flange fittings.
  • Non-limiting examples of valves include gate valves, globe valves, ball valves, butterfly valves, and check valves.
  • Syngas can be prepared by the reaction of carbon dioxide (C0 2 ) with hydrogen (H 2 ). C0 2 and H 2 can react to form carbon monoxide (CO) and water (H 2 0) through a reverse water gas shift (RWGS) reaction. This process can be described as hydrogenation of C0 2 .
  • the RWGS reaction is reversible and endothermic and is illustrated by Formula 1 : (1) C0 2 + H 2 ⁇ ⁇ CO + H 2 0
  • FIG. 1 is a schematic diagram of an exemplary system according to the disclosed subject matter.
  • the system 100 can comprise a fired heater 101 including one or more coil arrangements 132, 133, 134.
  • the system 100 can further comprise a waste heat recovery unit, including a boiler 150 and a product cooler 170.
  • the system 100 can further comprise product separators 180, 181 for removing H 2 0 and unconverted carbon dioxide from the product stream. 1. Fired Heaters
  • the system includes a fired heater 130.
  • the fired heater can alternatively be termed a "furnace.”
  • the fired heater includes a radiant section and a convection section.
  • the fired heater can be any type suitable for heating the chemical reaction of C0 2 and H 2 to a high temperature, for example to a temperature from about 750°C to about 1300°C.
  • the heater can be constructed from any suitable material, including but not limited to metals, such as steel or copper, carbon fiber, polymers, concrete, ceramic, glass, or a combination thereof.
  • the radiant section there is a radiant section within the fired heater 130.
  • catalyst tubes 131 are disposed within the radiant section.
  • the catalyst tubes can be made of any suitable material and have any suitable thickness for the transfer of heat from the radiant section to the interior of the catalyst tubes.
  • the catalyst tubes can also include extended surfaces, i.e., fins, to increase heat transfer.
  • the radiant section is coupled to a transfer line 107 for transferring C0 2 and H 2 to the catalyst tubes 131.
  • the radiant section is coupled to one or more feed lines 103, 104.
  • the one or more feed lines are configured to transfer hydrocarbons to a burner for combustion.
  • the radiant section is heated via the combustion of hydrocarbons to a temperature from about 750°C to about 1300°C, from about 900°C to about 1200°C, or from about 1000°C to about 1100°C.
  • the combustion reaction can create a flue gas for heating the fired heater.
  • Flue gas can alternatively be termed "exhaust.”
  • the flue gas travels from the radiant section to the convection section of the fired heater 130.
  • the flow of flue gas within the fired heater is induced by one or fans 135, 136.
  • the flue gas exits the fired heater through a stack 137.
  • the flue gas when exiting the fired heater, has a temperature from about 100°C to about 300°C, from about 130°C to about 250°C, or from about 150°C to about 210°C.
  • the flue gas has a temperature of less than 180°C when it exits the fired heater.
  • the convection section includes one or more coil arrangements 132, 133, 134.
  • one or more coil arrangements 133 are used to heat feedstock containing C0 2 and H 2 .
  • one or more coil arrangements 134 are used to preheat air for the combustion reaction.
  • one or more coil arrangements 132 are used to superheat steam.
  • a coil arrangement for superheating steam 132 is disposed closer to the burner than a coil arrangement for heating feedstock 133.
  • a coil arrangement for heating feedstock 133 is disposed closer to the burner than a coil arrangement for preheating air for the combustion reaction 134.
  • the system 100 can further include one or more feed lines 106 coupled to the fired heater 130 for transferring C0 2 and H 2 feedstock to the fired heater.
  • one or more feed lines are coupled to a heat exchanger 160 for preheating the feedstock.
  • the heat exchanger(s) for use in the presently disclosed subject matter can be any type suitable for heating gaseous or liquid streams known to one of ordinary skill in the art.
  • such heat exchangers include shell and tube heat exchangers, plate heat exchangers, plate and shell heat exchangers, adiabatic wheel heat exchangers, and plate fin heat exchangers.
  • a feed line containing C0 2 and H 2 105 is coupled to a heat exchanger 160.
  • the feed line 105 is also coupled to a mixer 120 for mixing H 2 feedstock 101 and C0 2 feedstock 102.
  • the system 100 further includes an effluent stream 108 coupled to the fired heater 130.
  • heat from the effluent stream is recovered in a waste heat recovery unit.
  • the waste heat recovery unit includes a boiler 150 and a product cooler 170.
  • the waste heat recovery unit further includes one or more heat exchangers 160 for preheating a feed line containing C0 2 and H 2 .
  • the effluent stream 108 is coupled to a boiler 150 for producing steam.
  • the boiler is coupled to a water feed line 153 for transferring feed water to the boiler 150.
  • the water feed line 153 is further coupled to a heat exchanger 151 for preheating feed water prior to the boiler.
  • the heat exchanger 151 is coupled to the transfer line carrying the effluent stream from the boiler 109 for transferring heat from the effluent stream 109 to the boiler feed water 153.
  • the effluent stream 109 coupled to the heat exchanger 151 for preheating the boiler feed water 153 is further coupled to an effluent- feed heat exchanger 160 via a transfer line 110.
  • the effluent-feed heat exchanger is adapted to heat a feed line 105 containing C0 2 and H 2 by transferring heat from the effluent stream in the transfer line 110 to the feed line 105.
  • the boiler 150 is coupled to a steam transfer line 154 for transferring steam from the boiler to a coil arrangement 132 disposed within the fired heater 130.
  • a second steam transfer line 155 is coupled to the coil arrangement 132 for removing steam from the fired heater 155.
  • the system further includes a product cooler 170 coupled to the effluent-feed heat exchanger 160, e.g., via a transfer line 111.
  • the product cooler can contain one or more heat exchangers in series 171, 172 which reduce the temperature of the effluent stream.
  • the product cooler 170 includes a heat exchanger 171 coupled to a deaerator feed line.
  • the deaerator feed line is coupled to a deaerator for removing air from the boiler feed water 153.
  • the presently disclosed system 100 can further include a product separation unit, including a water separator 180 and a C0 2 recovery unit 181.
  • the product separation unit is coupled to the waste heat recovery unit, e.g., via a transfer line 112.
  • the water separator 180 may be a condenser adapted to remove water from the cooled effluent stream. Water from the water separator 180 is removed from the system 100 via a waste water transfer line 113.
  • the water separator 180 is coupled to a transfer line 114 for transferring a product stream containing CO, H 2 , and unconverted C0 2 to a C0 2 recovery unit 181.
  • the C0 2 recovery unit includes a separator for removing unconverted C0 2 from the product stream 114 and producing a purified syngas stream 115.
  • the C0 2 recovery unit is adapted to separate unconverted C0 2 via an acid gas removal process.
  • the acid gas removal process can be, but is not limited to, one of the following: acid gas removal with methyl diethanolamine (MDEA), the Benfield Process, and the Recitsol® process.
  • the product separation unit further includes a C0 2 recycle line 116 coupled to the C0 2 recovery unit.
  • the C0 2 recycle line is coupled to a product feed line 105.
  • the C0 2 recycle line can be coupled to one or more compressors 190 for pressurizing C0 2 .
  • FIG. 2 is a schematic representation of an exemplary method in accordance with a non-limiting embodiment of the disclosed subject matter.
  • an exemplary method 200 can include providing a system 100, as described above for producing syngas from H 2 and C0 2 through the reverse water gas shift (RWGS) reaction.
  • RWGS reverse water gas shift
  • the method 200 can include heating a first feed stream, containing C0 2 and H 2 , to a first temperature , e.g., via a heat exchanger 201.
  • the method can further include heating the first feed stream in the convection section of a fired heater to produce a second feed stream at a second, higher temperature 202.
  • the method can further include transferring the second feed stream to catalyst tubes disposed within the radiant section of a fired heater 203.
  • the method can further include contacting C0 2 and H 2 in the second feed stream with a catalyst to form an effluent stream containing shift reaction products 204.
  • the method can further include feeding the effluent stream through a waste heat recovery unit to the temperature 205.
  • the method can further include separating water from the shift reaction products to produce a product stream comprising CO, H 2 , and unconverted C0 2 206.
  • the method can further include recovering unconverted C0 2 from the product stream to create a syngas stream 207.
  • the method can further include recycling unconverted C0 2 into the first feed stream 208.
  • the C0 2 used in the methods of the presently disclosed subject matter can originate from various sources.
  • the C0 2 can come from a waste gas stream, e.g., from a plant on the same site. Recycling C0 2 as starting material in the methods of the presently disclosed subject matter can contribute to reducing the amount of C0 2 emitted to the atmosphere.
  • the C0 2 used within the feedstream can also, at least partly, originate from the effluent gas or product of the disclosed methods and be recycled back to the feedstream.
  • the H 2 used in the methods of the presently disclosed subject matter can originate from various sources, including gaseous streams coming from other chemical processes, e.g., ethane cracking, methanol synthesis, or conversion of CH 4 to aromatics. In certain embodiments, H 2 can also be sourced through water splitting using renewable energy.
  • the method can include pressurizing a feed stream containing C0 2 and H 2 to a pressure of about 2 bar to about 100 bar, from about 5 bar to about 70 bar, or from about 10 bar to about 40 bar.
  • the method can further include heating the feed stream via a heat exchanger to a temperature from about 80°C to about 200°C, from about 100°C to about 180°C, or from about 120°C to about 160°C.
  • the method further includes transferring the preheated feed stream to a fired heater to produce a heated feed stream.
  • the heated feed stream is transferred to a coil arrangement disposed within the convection section of a fired heater.
  • the heated feed stream has a temperature from about 200°C to 800°C, from about 300°C to about 700°C, or from about 350°C to about 650°C.
  • the method further includes transferring the heated feed stream to catalyst tubes.
  • the catalyst tubes are disposed within the radiant section of a fired heater.
  • the method further includes contacting the heated feed stream containing C0 2 and H 2 with a catalyst within the catalyst tubes to form shift reaction products via the RWGS reaction.
  • the composition of the feed stream suitable for use with the presently disclosed methods can include various proportions of C0 2 and H 2 .
  • the feed stream can include H 2 and C0 2 in a molar ratio (H 2 :C0 2 ) between about 5:1 and about 1:2, e.g., about 5:1, 4:1, 3:1, 2.8:1, 2.6:1, 2.5:1, 2.4:1, 2.3:1, 2.2:1, 2.1:1, 2:1, 1.9:1, 1.8:1, 1.7:1, 1.6:1, 1.5:1, 1.4:1, 1.3:1, 1.2:1, 1.1:1, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, or 1:2.
  • the reaction temperature can be understood to be the temperature of the catalyst tubes within the fired heater.
  • the reaction temperature can influence the RWGS reaction, including conversion of C0 2 and H 2 , the ratio of H 2 :CO in the product mixture, and the overall yield.
  • the reaction temperature can be from about 750°C to about 1300°C, from about 900°C to about 1200°C, or from about 1000°C to about 1100°C.
  • the contact time for contacting the heated feed stream with the catalyst can depend on a number of factors, including but not limited to, the temperature, the pressure and the amount of catalyst and reactants, e.g., H 2 and C0 2 , within the heated feed stream.
  • the catalysts to be used in the methods of the disclosed subject matter can be any catalyst suitable for hydrogenation of carbon dioxide known to one of ordinary skill in the art.
  • catalyst compositions suitable for catalyzing hydrogenation of carbon dioxide include metal oxides, carbides, hydroxides or combinations thereof.
  • Non-limiting examples of suitable metals include oxides of chromium (Cr), copper (Cu), manganese (Mn), potassium (K), palladium (Pd), cobalt (Co), cerium (Ce), tungsten (W), platinum (Pt), sodium (Na) and cesium (Cs).
  • the catalysts compositions can further include an inert carrier or support material.
  • Suitable supports can be any support materials, which exhibit good stability at the reaction conditions of the disclosed methods, and are known by one of ordinary skill in the art.
  • the support material can include aluminium oxide (alumina), magnesia, silica, titania, zirconia and mixtures or combinations thereof.
  • the catalyst compositions of the present disclosure further include one or more promoters.
  • Non-limiting examples of suitable promoters include lanthanides, alkaline earth metals and combinations thereof.
  • the method can include combusting hydrocarbons to produce a flue gas to increase the temperature of the fired heater.
  • natural gas and air are provided to a burner for combustion.
  • the air is heated in the convection section of the fired heater prior to combustion.
  • the air is heated to a temperature from about 150°C to about 500°C, from about 200°C to about 400°C, or from about 250°C to about 350°C.
  • the air is heated to a temperature greater than 250°C prior to combustion.
  • the method further includes inducing the flow of flue gas within the fired heater using one or more fans.
  • the method can further include transferring an effluent stream containing the shift reaction products to a waste heat recovery unit to reduce the effluent stream temperature.
  • the effluent stream has a temperature of about 500°C to about 1400°C, from about 700°C to about 1200°C, from about 800°C to about 1000°C, or from about 850°C to about 900°C.
  • the effluent stream can contain CO, H 2 , unconverted C0 2 , and water.
  • the method can include transferring the effluent stream to a boiler and/or a product cooler comprising one or more heat exchangers.
  • the method includes transferring the effluent stream to a boiler for producing steam.
  • feed water is also transferred to the boiler.
  • the feed water is transferred to a deaerator prior to transfer to the boiler.
  • the effluent stream is used to preheat the feed water before the feed water is transferred to the boiler.
  • the temperature of the effluent stream after exiting the boiler is from about 80°C to about 220°C, from about 100°C to about 200°C, from about 120°C to about 180°C, or from about 140°C to about 160°C. In particular embodiments, the temperature of the effluent stream after exiting the boiler is less than 150°C.
  • the method further includes transferring the steam from the boiler to the fired heater.
  • the steam exiting the boiler is saturated.
  • the steam is transferred to a coil arrangement disposed within the convection section of the fired heater.
  • the steam transferred to the fired heater is superheated to a temperature from about 350°C to about 750°C, from about 450°C to about 650°C, from about 500°C to about 600°C, or from about 500°C to about 550°C.
  • the pressure of the steam exiting the fired heated is from about 800 barg to about 1400 barg, from about 1000 barg to about 1200 barg, or from about 1100 barg to about 1150 barg.
  • the method further includes transferring the effluent stream to one or more heat exchangers for heating the feed stream containing C0 2 and H 2 .
  • the feed stream is heated to a temperature from about 80°C to about 200°C, from about 100°C to about 180°C, or from about 120°C to about 160°C.
  • the method includes transferring the effluent stream to a product cooler comprising one or more heat exchangers.
  • the method further includes transferring heat from the effluent stream to the boiler feed water, e.g., via a heat exchanger, prior to transferring the boiler feed water to a deaerator.
  • the effluent stream is cooled to a temperature from about 15°C to about 75°C, from about 30°C to about 60°C, or from about 40°C to about 50°C.
  • the effluent stream is cooled to a temperature of less than 45°C.
  • the method includes separating water from the shift reaction products in the cooled effluent stream to produce a product stream comprising CO, H 2 , and unconverted C0 2 .
  • the method includes condensing water from the cooled effluent stream to produce a waste water stream and a product stream.
  • the method further includes separating unconverted C0 2 from the product stream to produce a purified syngas stream.
  • the RWGS can be performed to relatively high conversion. That is, the amount of C0 2 present in the product stream can be relatively low.
  • the product mixture can include less than about 25% C0 2 , by mole or less than about 20% C0 2 , by mole.
  • the product mixture can include about 24%, 23%, 22%, 21%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8% by mole.
  • the syngas stream can include H 2 and CO in a molar ratio (H 2 :CO) of about 0.5: 1 to about 5: 1.
  • the product mixture can include H 2 and CO in a molar ratio (H 2 :CO) of about 1 : 1 to about 3 : 1, e.g., about 1 : 1, 1.1 : 1, 1.2: 1, 1.3 : 1, 1.4: 1, 1.5: 1, 1.6: 1, 1.7: 1, 1.8: 1, 1.9: 1, 2: 1, 2.1 : 1, 2.2: 1, 2.3 : 1, 2.4: 1, 2.5: 1, 2.6: 1, 2.7: 1, 2.8: 1, 2.9: 1, or 3 : 1.
  • unconverted C0 2 is recovered from the syngas stream by an acid gas removal process, which can be, but is not limited to acid gas removal with methyl diethanolamine (MDEA), the Benfield Process, or the Recitsol® process.
  • the method further includes recycling recovered C0 2 to the feed stream containing C0 2 and H 2 , i.e., recycling it to the RWGS reaction.
  • the recovered C0 2 is pressurized to a pressure from 2 bar to about 100 bar, from about 5 bar to about 70 bar, or from about 10 bar to about 40 bar, prior to being recycled.

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  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne des procédés et des systèmes de préparation de gaz de synthèse à partir de dioxyde de carbone (CO2) et d'hydrogène (H2). Les procédés comprennent la production de gaz de synthèse à partir de CO2 et H2 à l'aide d'une réaction de décalage eau-gaz inverse (RWGS). Les systèmes comprennent un appareil de chauffage à combustible, un ou plusieurs agencements de bobines, un ou plusieurs échangeurs de chaleur, une unité de récupération de chaleur perdue comprenant une chaudière et dispositif de refroidissement de produit, et un ou plusieurs séparateurs de produit.
PCT/IB2016/056418 2015-11-03 2016-10-25 Procédé et système de production de gaz de synthèse à partir de dioxyde de carbone et d'hydrogène WO2017077421A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11964872B2 (en) 2018-12-03 2024-04-23 Shell Usa, Inc. Process and reactor for converting carbon dioxide into carbon monoxide

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2657598A1 (de) * 1976-12-18 1978-06-22 Krupp Koppers Gmbh Verfahren zur erzeugung eines kohlenmonoxydreichen gases
EP0291857A2 (fr) * 1987-05-18 1988-11-23 Air Products And Chemicals, Inc. Méthode de production d'oxyde de carbone
FR2825995A1 (fr) * 2001-06-15 2002-12-20 Inst Francais Du Petrole Installation et procede de production de gaz de synthese comprenant un reacteur de vaporeformage et un reacteur de conversion du co2 chauffe par un gaz chaud
US7863341B2 (en) 2005-07-20 2011-01-04 Shell Oil Company Preparation of syngas
FR2963932A1 (fr) * 2010-12-23 2012-02-24 Commissariat Energie Atomique Procede de recyclage ameliore du co2 par reaction inverse du gaz a l'eau (rwgs)
US8288446B2 (en) 2007-06-25 2012-10-16 Saudi Basic Industries Corporation Catalytic hydrogenation of carbon dioxide into syngas mixture
US8551434B1 (en) 2012-06-29 2013-10-08 Saudi Basic Industries Corporation Method of forming a syngas mixture

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2657598A1 (de) * 1976-12-18 1978-06-22 Krupp Koppers Gmbh Verfahren zur erzeugung eines kohlenmonoxydreichen gases
EP0291857A2 (fr) * 1987-05-18 1988-11-23 Air Products And Chemicals, Inc. Méthode de production d'oxyde de carbone
FR2825995A1 (fr) * 2001-06-15 2002-12-20 Inst Francais Du Petrole Installation et procede de production de gaz de synthese comprenant un reacteur de vaporeformage et un reacteur de conversion du co2 chauffe par un gaz chaud
US7863341B2 (en) 2005-07-20 2011-01-04 Shell Oil Company Preparation of syngas
US8288446B2 (en) 2007-06-25 2012-10-16 Saudi Basic Industries Corporation Catalytic hydrogenation of carbon dioxide into syngas mixture
FR2963932A1 (fr) * 2010-12-23 2012-02-24 Commissariat Energie Atomique Procede de recyclage ameliore du co2 par reaction inverse du gaz a l'eau (rwgs)
US8551434B1 (en) 2012-06-29 2013-10-08 Saudi Basic Industries Corporation Method of forming a syngas mixture

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11964872B2 (en) 2018-12-03 2024-04-23 Shell Usa, Inc. Process and reactor for converting carbon dioxide into carbon monoxide

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