WO2017098385A1 - Procédés de production de gaz de synthèse à partir de dioxyde de carbone - Google Patents
Procédés de production de gaz de synthèse à partir de dioxyde de carbone Download PDFInfo
- Publication number
- WO2017098385A1 WO2017098385A1 PCT/IB2016/057280 IB2016057280W WO2017098385A1 WO 2017098385 A1 WO2017098385 A1 WO 2017098385A1 IB 2016057280 W IB2016057280 W IB 2016057280W WO 2017098385 A1 WO2017098385 A1 WO 2017098385A1
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- WIPO (PCT)
- Prior art keywords
- syngas
- feed stream
- stream
- carbon dioxide
- temperature
- Prior art date
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Classifications
-
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
-
- 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
- C01B2203/06—Integration with other chemical processes
- C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
-
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
Definitions
- the disclosed subject matter relates to methods for producing syngas from carbon dioxide.
- Syngas also known as synthesis gas, is primarily a mixture of carbon monoxide (CO) and hydrogen (H 2 ), and can also contain carbon dioxide (C0 2 ) and/or water (H 2 0).
- Syngas can be a feedstock for producing higher hydrocarbons, such as fuels, for example in a Fischer- Tropsch process.
- Syngas can also be used to produce various chemicals, including olefins, methanol, ethylene glycol, and aldehydes, for example by oxo-synthesis (also known as hydroformylation) and carbonylation reactions.
- the composition of the syngas, and particularly the stoichiometric ratio of H 2 and C0 2 in the syngas can be important in determining which materials are produced.
- Syngas can be produced from hydrocarbons, for example by methane steam reforming.
- carbon dioxide can be converted to syngas.
- Certain methods for producing syngas from carbon dioxide are known in the art.
- U.S. Patent No. 8,551,434 discloses a process for hydrogenating C0 2 to form syngas. The reaction is carried out adiabatically in the presence of a non-zinc catalyst and within a reactor containing nickel or iron components.
- International Patent Publication No. WO2015/069840 discloses a process for generating syngas from C0 2 in an adiabatic metal reactor using a metal oxide catalyst.
- the disclosed subject matter provides novel methods for producing syngas from carbon dioxide.
- an exemplary method of producing syngas from carbon dioxide (C0 2 ) includes heating a feed stream including hydrogen (H 2 ) and C0 2 to a temperature from about 800°C to about 900°C to generate a heated feed stream and feeding the heated feed stream to an adiabatic reactor containing a Catofin catalyst to generate a product stream including syngas.
- H 2 and C0 2 can be present in the feed stream in a molar ratio (H 2 /C0 2 ) of less than about 2 or less than about 1.
- the feed stream can contain H 2 and C0 2 in a molar ratio (H 2 /C0 2 ) of about 0.67.
- the feed stream can be heated to a temperature of about 830°C.
- the Catofin catalyst can include chromium supported on alumina.
- the product stream can contain syngas having H 2 and CO in a molar ratio (H 2 /CO) of less than about 2 or less than about 1.
- the product stream can have a temperature from about 600°C to about 700°C. In particular embodiments, the product stream can have a temperature of about 660°C.
- C0 2 conversion can be from about 35% to about 40%.
- the produced syngas can be used to generate olefins. Alternatively or additionally, the produced syngas can be used in an oxo-synthesis reaction. Alternatively or additionally, the produced syngas can be used in a carbonylation reaction.
- an exemplary method of producing syngas includes heating a feed stream including H 2 and C0 2 to a temperature from about 800°C to about 900°C to generate a heated feed stream, feeding the heated feed stream to an adiabatic reactor containing a Catofin catalyst, and removing a product stream including syngas from the reactor.
- the product stream can have a temperature from about 600°C to about 700°C.
- the syngas can include H 2 and CO in a molar ratio (H 2 /CO) of about 1.
- FIG. 1 depicts a method for producing syngas from carbon dioxide according to one exemplary embodiment of the disclosed subject matter.
- the presently disclosed subject matter provides novel methods for producing syngas from carbon dioxide.
- 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.
- FIG. 1 is a schematic representation of a method for hydrogenating carbon dioxide to form syngas according to a non-limiting embodiment of the disclosed subject matter.
- the method 100 can include heating a feed stream including hydrogen (H 2 ) and carbon dioxide (C0 2 ) 101.
- feed stream as used herein can refer to a single feed stream or multiple feed streams, which can be combined before or during the hydrogenation reaction.
- the feed stream can be a single mixture of H 2 or C0 2 .
- multiple feed streams containing H 2 and/or C0 2 can be provided.
- the C0 2 in the feed stream can originate from various sources.
- the C0 2 can be sourced from other chemical processes, e.g., as a waste product, and/or unconverted C0 2 can be recovered from the product stream and recycled to the feed stream.
- the H 2 in the feed stream can also originate from various sources, for example from gaseous streams from other chemical processes.
- the flow rate of the feed stream can be from about 500 cc/min to about 4000 cc/min, from about 1000 cc/min to about 3000 cc/min, or about 2000 cc/min.
- the flow rate of H 2 in the feed stream can be from about 100 cc/min to about 1500 cc/min, from about 500 cc/min to about 1200 cc/min, or about 800 cc/min.
- the flow rate of C0 2 in the feed stream can be from about 400 cc/min to about 2000 cc/min, from about 800 cc/min to about 1600 cc/min, or about 1200 cc/min.
- the flow rate of the feed stream can depend on the space velocity of the hydrogenation reaction.
- the space velocity of the hydrogenation reaction can be from about 2800 to about 3500 h "1 .
- the feed stream can include H 2 and C0 2 in a particular ratio.
- the molar ratio of H 2 to C0 2 (H 2 /C0 2 ) in the feed stream can be less than about 5, less than about 3, less than about 2, or less than about 1.
- the feed stream can contain H 2 and C0 2 in a molar ratio (H 2 /C0 2 ) of about 0.67.
- the method 100 can further include providing the heated feed stream to an adiabatic reactor 102.
- the feed stream can be heated to a temperature from about 500°C to about 1200°C, from about 700°C to about 1000°C, or from about 800°C to about 900°C.
- the feed stream is heated to a temperature of about 830°C.
- the feed stream can be preheated prior to entering the reactor.
- the feed stream can be heated as it enters the reactor.
- the feed stream can be provided at atmospheric pressure. Alternatively, the feed stream can be pressurized, e.g., to from about 1 bar to about 26 bar.
- the reactor can be a fixed bed reactor.
- the reactor can be a quartz reactor having a diameter of about 1 inch to about 4 inches.
- the dimensions and structure of the reactor can vary depending on the capacity of the reactor. The capacity of the reactor can be determined by the reaction rate, the stoichiometric quantities of the reactants and/or the feed flow rate.
- the reactor can be operated under adiabatic conditions.
- a catalyst can be loaded into the reactor.
- Catalysts for use in the presently disclosed subject matter can include a Catofin® catalyst (Clariant, Cr/Al 2 0 3 ).
- the catalyst can include about 16 wt-% chromium (Cr) supported on alumina (A1 2 0 3 ).
- catalyst loading can be from about 100 mL to about 800 mL, from about 300 mL to about 600 mL, or from about 400 mL to about 500 mL. In particular embodiments, catalyst loading is about 426 mL.
- the contact time for contacting the feed stream with the catalyst can depend on a number of factors including, but not limited to, the temperature, the pressure, the amount of catalyst, and the flowrate of reactants, i.e., C0 2 and H 2 , in the feed stream.
- the feed stream can contact the catalyst for from about 1 second to about 10 seconds.
- the method 100 can further include removing a product stream including syngas from the reactor 103.
- the reactor is operated adiabatically such that the temperature of the product stream when it exits the reactor is less than the temperature of the feed stream.
- the product stream can have a temperature from about 300°C to about 1000°C, from about 500°C to about 800°C, or from about 600°C to about 700°C.
- the product stream can have a temperature of about 660°C.
- the product stream can be formed by the hydrogenation of C0 2 in the feed stream.
- C0 2 and H 2 in the feed stream can react to form carbon monoxide (CO) and water (H 2 0) in a reverse water gas shift reaction.
- CO carbon monoxide
- H 2 0 water
- the reverse water gas shift reaction is illustrated by:
- the reverse water gas shift reaction is equilibrium-driven, and can be performed under conditions resulting in only partial conversion of C0 2 and H 2 .
- the hydrogenation of C0 2 by the reverse water gas shift reaction can result in a product stream containing C0 2 and H 2 , as well as CO and H 2 0.
- H 2 0 can be separated from the product stream, e.g., by condensation.
- C0 2 conversion can be from about 10% to about 65%>, from about 20% to about 55%, from about 30% to about 45%, or from about 35% to about 40%).
- the amount of C0 2 in the product stream can be from about 25 mol-% to about 65 mol-%, from about 35 mol-% to about 55 mol-%, or from about 40 mol-% to about 50 mol- %. In certain embodiments, the amount of C0 2 in the product stream is about 45 mol-%.
- the amount of H 2 in the product stream can be from about 10 mol-% to about 50 mol-%, from about 20 mol-% to about 40 mol-%, or from about 25 mol-% to about 35 mol-%.
- the amount of H 2 in the product stream is about 27 mol-%.
- the amount of CO in the product stream can be from about 5 mol-% to about 45 mol-%, from about 15 mol-%) to about 35 mol-%, or from about 20 mol-% to about 30 mol-%. In certain embodiments, the amount of CO in the product stream is about 27 mol-%.
- the ratio of H 2 and CO in the product stream can be manipulated by varying process conditions, e.g., reaction conditions, catalyst type or amount, or the ratio of H 2 to C0 2 in the feed stream. Although it is possible to adjust the H 2 to CO ratio in the syngas of the product stream after the hydrogenation reaction, e.g., by a subsequent reverse water gas shift reaction or by mixing the syngas with another gaseous stream, it can be desirable to generate a product stream which contains a suitable H 2 to CO ratio for a downstream use.
- the product stream can contain H 2 and CO in a molar ratio (H 2 /CO) of less than about 3, less than about 2, or less than about 1.5.
- the product stream can contain H 2 and CO in a molar ratio (H 2 /CO) of about 1.
- the method can include separating at least some C0 2 from the CO and H 2 in the product stream to produce purified syngas.
- unconverted C0 2 in the product stream can be recovered and recycled to the feed stream.
- C0 2 can be separated by a process including absorption by an amine.
- the syngas produced by the presently disclosed methods can be suitable for use in oxo-synthesis reactions, e.g., to produce aldehydes.
- the syngas can be suitable for use in carbonylation reactions, e.g., to produce ketones, aldehydes, and/or organic acids.
- the syngas can be suitable for olefins synthesis, e.g., by using a Fischer-Tropsch process or via an alcohol intermediary, such as methanol or ethanol.
- the methods of the presently disclosed subject matter provide advantages over certain existing technologies for producing syngas from carbon dioxide. Exemplary advantages include improved syngas composition for downstream processes, as well as increased catalyst stability and carbon dioxide conversion.
- Example 1 Hydrogenation of CO? over a Catofin catalyst
- carbon dioxide (C0 2 ) was hydrogenated in the presence of hydrogen (H 2 ) to produce syngas.
- the hydrogenation of carbon dioxide (C0 2 ) was performed in a quartz reactor under adiabatic conditions. For the top of the reactor, the temperature distribution was: 829°C, 798°C, 753°C, 723°C, 702°C, and 66FC.
- the reactor was loaded with an industrial Catofin catalyst.
- the catalyst loading was 426 mL.
- the flow rate of H 2 was 803 cc/min and the flow rate of C0 2 was 1200 cc/min.
- Table 1 displays the composition of the syngas after 80 and more days on stream, as well as the conversion of C0 2 .
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Abstract
La présente invention concerne des procédés de production de gaz de synthèse à partir de dioxyde de carbone. Les procédés peuvent comprendre le chauffage d'un courant d'alimentation comprenant de l'hydrogène (H2) et du dioxyde de carbone (CO2) à une température d'environ 800 °C à environ 900 °C pour générer un courant d'alimentation chauffé. Les procédés peuvent comprendre en outre l'alimentation du courant d'alimentation chauffée dans un réacteur adiabatique contenant un catalyseur Catofin pour générer un courant de produit comprenant un gaz de synthèse.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US201562264245P | 2015-12-07 | 2015-12-07 | |
US62/264,245 | 2015-12-07 |
Publications (1)
Publication Number | Publication Date |
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WO2017098385A1 true WO2017098385A1 (fr) | 2017-06-15 |
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PCT/IB2016/057280 WO2017098385A1 (fr) | 2015-12-07 | 2016-12-01 | Procédés de production de gaz de synthèse à partir de dioxyde de carbone |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113501491A (zh) * | 2021-07-20 | 2021-10-15 | 广东博大新能源科技有限公司 | 一种二氧化碳低温常压转化获得合成气的方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5140049A (en) * | 1985-10-25 | 1992-08-18 | Exxon Research And Engineering Co. | Method for producing olefins from H2 and CO2 using an iron carbide based catalyst |
WO2014003817A1 (fr) * | 2012-06-29 | 2014-01-03 | Saudi Basic Industries Corporation | Procédé de formation d'un mélange de gaz de synthèse |
WO2015069840A1 (fr) * | 2013-11-11 | 2015-05-14 | Saudi Basic Industries Corporation | Procédé pour l'hydrogénation du co2 dans des réacteurs métalliques adiabatiques |
-
2016
- 2016-12-01 WO PCT/IB2016/057280 patent/WO2017098385A1/fr active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5140049A (en) * | 1985-10-25 | 1992-08-18 | Exxon Research And Engineering Co. | Method for producing olefins from H2 and CO2 using an iron carbide based catalyst |
WO2014003817A1 (fr) * | 2012-06-29 | 2014-01-03 | Saudi Basic Industries Corporation | Procédé de formation d'un mélange de gaz de synthèse |
WO2015069840A1 (fr) * | 2013-11-11 | 2015-05-14 | Saudi Basic Industries Corporation | Procédé pour l'hydrogénation du co2 dans des réacteurs métalliques adiabatiques |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113501491A (zh) * | 2021-07-20 | 2021-10-15 | 广东博大新能源科技有限公司 | 一种二氧化碳低温常压转化获得合成气的方法 |
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