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WO2025110346A1 - Système de conversion de dioxyde de carbone ayant un rendement en combustible liquide amélioré à l'aide de zéolite, et réacteur de conversion de dioxyde de carbone associé - Google Patents

Système de conversion de dioxyde de carbone ayant un rendement en combustible liquide amélioré à l'aide de zéolite, et réacteur de conversion de dioxyde de carbone associé Download PDF

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Publication number
WO2025110346A1
WO2025110346A1 PCT/KR2024/001168 KR2024001168W WO2025110346A1 WO 2025110346 A1 WO2025110346 A1 WO 2025110346A1 KR 2024001168 W KR2024001168 W KR 2024001168W WO 2025110346 A1 WO2025110346 A1 WO 2025110346A1
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carbon dioxide
catalyst
zeolite
catalyst section
reactor
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Korean (ko)
Inventor
권기욱
김우영
유수진
오진호
송창열
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GS Caltex Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen

Definitions

  • the present invention relates to a carbon dioxide conversion system and a carbon dioxide conversion reactor thereof, which utilize zeolite to improve the yield of liquid fuel, and more particularly, to a carbon dioxide conversion system and a carbon dioxide conversion reactor therefor, which utilize silicoaluminophosphate (SAPO-34) zeolite to improve the yield of naphtha and gasoline produced by the hydrogenation reaction of carbon dioxide.
  • SAPO-34 silicoaluminophosphate
  • the flue gas discharged from the oil refining process contains an excessive amount of carbon dioxide, it can be utilized to produce chemicals such as olefin and paraffin, effectively reducing carbon dioxide.
  • the optimal condition for carbon dioxide conversion is a H 2 /CO 2 molar ratio of 3, but since the H 2 /CO 2 molar ratio in the flue gas is less than 2, it is difficult to convert carbon dioxide.
  • the carbon dioxide conversion rate can be improved by additionally supplying hydrogen to the flue gas in the oil refining process, but additionally supplying hydrogen at the current high price of hydrogen is not efficient in terms of process cost.
  • the present invention is intended to solve the problems of the prior art, and to improve the yield of liquid fuel by utilizing SAPO-34, which is widely known as a Si-P-Al zeolite catalyst for carbon dioxide hydrogenation reaction.
  • the present invention provides a reactor including a carbon dioxide hydrogenation reaction catalyst and a zeolite catalyst as dual beds within one reactor.
  • a system for converting carbon dioxide with improved liquid fuel yield utilizing the zeolite of the present invention may include a first catalyst section including an Fe-based catalyst and converting carbon dioxide to produce a reaction product; and a second catalyst section including a zeolite and producing a liquid fuel from the reaction product.
  • the above first catalyst section and second catalyst section can be operated as a single process including a dual bed in one reactor.
  • the above liquid fuel may have a carbon number of C 5 to C 12 .
  • the above Fe-based catalyst may be a compound represented by the following [chemical formula 1].
  • the above M includes at least one selected from rare earth metals including Ce, La, and Pr,
  • composition ratios of a, b, c, d, and e above is 1.
  • the above Fe-based catalyst may have a pore volume of 0.17 to 0.21 cm 3 /g in BET analysis.
  • the above Fe-based catalyst can have a S BET of 80 to 200 m 2 /g.
  • the above zeolite may include a Si-Al zeolite, a Si-P-Al zeolite, or a mixture thereof.
  • the above Si-P-Al zeolite may be a silicaluminophosphate-34 (SAPO-34) zeolite.
  • the pore size of the above SAPO-34 can be 1 to 5 ⁇ .
  • the Acidity of the above SAPO-34 can be 1 to 1.5 mmol/g cat .
  • the (Si+P)/Al ratio of the above SAPO-34 can be 0.6 to 0.65.
  • the pressure of the first catalyst section and the second catalyst section can be 1 to 50 bar.
  • the temperature of the first catalyst part and the second catalyst part can be 100 to 1000°C.
  • the H 2 /CO 2 molar ratio of the gas flowing into the first catalyst section and the second catalyst section may be 1 to 3.
  • the GHSV Gas Hourly Space Velocity of the first catalyst part and the second catalyst part may be 1,000 to 10,000 mL/g ⁇ h.
  • the yield of the above C 5 to C 12 can be 20 to 30%.
  • the carbon dioxide conversion reactor of the present invention comprises: a columnar body; an inlet formed in a first direction through which gas is introduced from the outside into the columnar body; an outlet formed in a direction opposite to the first direction; and a furnace for applying heat to the columnar body; wherein the interior of the columnar body is connected to the inlet and the outlet, and comprises a first catalyst section for converting carbon dioxide to produce a reaction product; and a second catalyst section for producing a liquid fuel from the reaction product; the rear ends of the first catalyst section and the second catalyst section may include silica gel for absorbing and removing moisture; and glass wool for blocking heat energy emission.
  • the above first direction may be from top to bottom.
  • the above first catalyst part may include an Fe-based catalyst of a carbon dioxide conversion system with improved liquid fuel yield utilizing the zeolite.
  • the above second catalyst part may include a zeolite of a carbon dioxide conversion system with improved liquid fuel yield by utilizing the zeolite.
  • the molar ratio of H 2 /CO 2 of the gas introduced from the outside may be 1 to 3.
  • the internal pressure of the above columnar body can be 1 to 50 bar.
  • the internal temperature of the above columnar body can be 100 to 1000°C.
  • the GHSV (Gas Hourly Space Velocity) of the above columnar body can be 1,000 to 10,000 mL/g ⁇ h.
  • the above liquid fuel may have a carbon number of C 5 to C 12 .
  • the yield of the above C 5 to C 12 can be 20 to 30%.
  • a carbon dioxide conversion system and a carbon dioxide conversion reactor thereof with improved liquid fuel yield utilizing the zeolite of the present invention utilize SAPO-34 zeolite in a carbon dioxide hydrogenation reaction, thereby oligomerizing base fractions (C 2 to C 4 ) produced by reverse water gas shift reaction (RWGS) and Fischer-Tropsch synthesis reaction, and cracking long-chain hydrocarbons (C 13+ ) to improve the yields of naphtha and gasoline (C 5 to C 12 ).
  • RWGS reverse water gas shift reaction
  • C 13+ Fischer-Tropsch synthesis reaction
  • Figure 1 is a schematic diagram showing a reactor for carbon dioxide conversion according to one embodiment of the present invention.
  • Figure 2 shows a TEM image of an Fe-based catalyst according to the CeO 2 content of the present invention.
  • Figure 3 shows the XRD results of the Fe-based catalyst according to the CeO 2 content of the present invention.
  • Figure 4 shows the results of H 2 -TPR, CO 2 -TPD, and CO-TPD analyses of the Fe-based catalyst according to the CeO 2 content of the present invention.
  • Figure 5 shows the results of H 2 -TPR, CO 2 -TPD, and CO-TPD analyses of an Fe-based catalyst according to the type of rare earth metal of the present invention.
  • Figure 6 shows the reaction activity according to the use of zeolite of the present invention.
  • Figure 7 shows the hydrocarbon distribution of a liquid product according to the zeolite of the present invention.
  • Figure 8 shows the carbon distribution of the liquid product according to the use of zeolite of the present invention.
  • a part such as a film (layer), region or component is located “on,” “above,” “upper,” “below,” “lower,” or “below” another part, this includes not only cases where one part is in contact with another part, but also cases where another part exists between the two parts.
  • numerical ranges used herein include lower and upper limits and all values within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of upper and lower limits of numerical ranges defined in different shapes.
  • Hydrogenation is a reaction in which a hydrogen molecule is added to a compound with an unsaturated functional group, such as a double bond or triple bond, under a metal catalyst to obtain a product.
  • an unsaturated compound, hydrogen, and a catalyst are required.
  • the reaction proceeds at various temperatures and pressures.
  • the hydrogenation reaction of carbon dioxide is as follows.
  • Cobalt-based and iron-based catalysts are mainly used. Iron-based catalysts are relatively inexpensive, have a wide range of reactor operating conditions, and produce a large proportion of higher products such as branched hydrocarbons and lower olefins, so they are widely used.
  • FeCuKAl catalysts which are conventionally known as Fe-based catalysts
  • carbon dioxide conversion was relatively low. Therefore, in the present invention, a rare earth metal was applied as a cocatalyst that facilitates carbon dioxide adsorption and desorption to the FeCuKAl catalyst.
  • Rare earth metals refer to 15 elements, from Lanthnum with atomic number 57 to Lutetium with atomic number 71. These elements are chemically very stable, do not change state even in dry air, and have the characteristic of conducting heat well. Also, since they can maximize the performance of devices even in small quantities, they are widely used in information technology (IT) electronic products such as liquid crystal displays (LCDs), light-emitting diodes (LEDs), and smartphones, as well as military supplies such as missile control devices and fighter jets. In addition, they are applied in various fields as core elements such as fluorescent substances, catalysts, abrasives, and alloying elements.
  • IT information technology
  • cerium (Ce) the most abundant element among rare earth metal elements, is a highly electropositive and chemically reactive metal that is easily oxidized to cerium(IV) oxide (CeO 2 ) in the air.
  • cerium oxide is highly hydrophobic, a characteristic unique to rare earth metals, so it adsorbs organic compounds well, and due to this characteristic, it is utilized as various catalysts.
  • CeO 2 forms oxygen vacancies at the interface, which not only has a higher oxygen storage capacity but also greatly increases the rate of redox reactions.
  • the Fe-based catalyst introducing a rare earth metal according to the present invention hydrogenates carbon dioxide contained in an externally introduced gas to produce a reaction product including a base fraction (C 2 to C 4 ) and a long-chain hydrocarbon (C 13+ ).
  • the Fe-based catalyst includes a rare earth metal and Fe, and can be used without limitation on type as long as it can convert carbon dioxide into a hydrocarbon compound. As an example, it may be a compound represented by the following [Chemical Formula 1], but is not limited thereto.
  • the above M includes at least one selected from rare earth metals including Ce, La, and Pr,
  • composition ratios of a, b, c, d, and e above is 1.
  • the molar ratio of H2 / CO2 in the exhaust gas required for the hydrogenation reaction of carbon dioxide is 3, and the reaction pressure also requires 30 to 40 bar.
  • the hydrogenation reaction activity of carbon dioxide at this time is the maximum carbon dioxide conversion rate of 40% and C5 + yield of 20% according to the values reported so far.
  • Zeolite refers to natural and synthetic silicate minerals. Due to the porous structure of zeolite in which cavities large enough to adsorb molecules exist regularly inside the crystal, zeolites exhibit excellent interfacial activity and have excellent catalytic properties.
  • the catalytic properties of zeolites vary depending on the structure of zeolite, the nature and structural position of cations, the Si/Al content ratio, and the presence of active metal elements.
  • the catalytic properties of zeolites are utilized in the fields of petroleum refining and petrochemicals, and when long-chain hydrocarbons and light olefins are supplied as reactants, the carbon chain can be controlled through cracking and oligomerization to improve the yield of naphtha and gasoline.
  • Si-Al zeolites composed of Si-Al were widely used as catalysts.
  • Si-Al zeolites have the disadvantages of producing a lot of CH4 as a by-product during the cracking process due to strong acid sites, causing a decrease in catalytic activity due to coke, and forming more aromatic hydrocarbons than linear hydrocarbons due to the large pore size (5-6 ⁇ ).
  • Si-P-Al zeolites which are widely known as MTO (Methanol to Olefin) catalysts
  • MTO Methanol to Olefin
  • the Si-P-Al zeolite may be, as an example, preferably silicon aluminophosphate (silicoaluminophosphate-34, SAPO-34), but is not limited thereto.
  • SAPO-34 is a molecular sieve with a unique shape structure and pore structure, appropriate acid properties, and excellent stability under various operating conditions. Unlike Si-Al zeolites, SAPO-34 is a molecular sieve in which the P element exists between Si-Al, and is characterized by a three-dimensional configuration of pores measuring 3.8 x 3.8 ⁇ in size to form a unique framework (Chabazite type, CHA). Due to the nest having a diameter of 7.5 x 8.2 ⁇ in the middle of the three-dimensional channel, it has the advantage of suppressing the production of aromatic compounds and heavy olefins, thereby increasing the yield of light olefins (C 2 to C 4 ). In addition, since the strength of the acid site is weaker than that of conventional zeolites, it can relatively suppress the production of by-products such as coke and CH 4 .
  • the present invention aims to improve the yield of naphtha and gasoline (C 5 to C 12 ), which are liquid fuels, through carbon dioxide conversion by applying Si-P-Al zeolite as a dual bed to an Fe-based catalyst.
  • the present invention relates to a carbon dioxide conversion system with improved liquid fuel yield utilizing zeolite, comprising: a first catalyst section including an Fe-based catalyst and converting carbon dioxide to produce a reaction product; and a second catalyst section including zeolite and producing a liquid fuel from the reaction product.
  • the above first catalyst section and second catalyst section are operated as a single process including a dual bed in one reactor.
  • the above first catalyst section comprises an Fe-based catalyst, which hydrogenates carbon dioxide contained in an externally introduced gas to produce a reaction product comprising a base fraction (C 2 to C 4 ) and a long-chain hydrocarbon (C 13+ ).
  • the Fe-based catalyst comprises a rare earth metal and Fe, and any catalyst capable of converting carbon dioxide into a hydrocarbon compound may be used without limitation on type.
  • the catalyst may preferably be a compound represented by the following [Chemical Formula 1], but is not limited thereto.
  • the above M includes at least one selected from rare earth metals including Ce, La, and Pr,
  • composition ratios of a, b, c, d, and e above is 1.
  • the Fe-based catalyst represented by the above [chemical formula 1] has a pore volume of 0.17 to 0.21 cm 3 /g in BET analysis and an S BET of 80 to 200 m 2 /g and 95 to 100 m 2 /g.
  • the second catalyst part includes zeolite, and increases the carbon number by oligomerizing the base oil (C 2 to C 4 ) generated in the first catalyst part, and cracks long-chain hydrocarbons (C 13+ ) into molecules having a smaller carbon number, thereby improving the yield of liquid fuel (C 5 to C 12 ).
  • the zeolite includes Si-Al zeolite, Si-P-Al zeolite, or a mixture thereof, and as an example, preferably, it may be silicon aluminophosphate (silicoaluminophosphate-34, SAPO-34).
  • the pore size of the above SAPO-34 may be 1 to 5 ⁇ , the Acidity may be 1 to 1.5 mmol/g cat , and the (Si+P)/Al ratio may be 0.6 to 0.65.
  • the pressure of the first catalyst section and the second catalyst section is 1 to 50 bar, and the temperature is 100 to 1000°C, preferably 20 bar and 300°C, but is not limited thereto. If the pressure and temperature inside the column-shaped body are too low, the conversion reaction of carbon dioxide is insufficient, resulting in a small amount of reaction product produced, and if the pressure and temperature of the reactor are too high, there is a problem that energy efficiency is reduced.
  • the H 2 /CO 2 molar ratio of the gas flowing into the first catalyst section and the second catalyst section is 1 to 3, preferably 1.5 to 2, but is not limited thereto.
  • the GHSV Global Hourly Space Velocity
  • the GHSV Global Hourly Space Velocity of the first catalyst part and the second catalyst part is 1,000 to 10,000 mL/g ⁇ h, preferably 3,000 to 8,000 mL/g ⁇ h, more preferably 6,000 to 7,000 mL/g ⁇ h, but is not limited thereto.
  • Figure 1 is a schematic diagram showing a reactor for carbon dioxide conversion according to one embodiment of the present invention.
  • a columnar body ; an inlet formed in a first direction through which gas is introduced from the outside into the columnar body; an outlet formed in a direction opposite to the first direction; and a furnace for applying heat to the columnar body; wherein the interior of the columnar body is connected to the inlet and the outlet, and includes a first catalyst section which converts carbon dioxide to generate a reaction product; and a second catalyst section which generates liquid fuel from the reaction product; and the rear ends of the first catalyst section and the second catalyst section include silica gel which absorbs and removes moisture; and glass wool which blocks heat energy emission.
  • the above first direction is not particularly limited, and is preferably from the top to the bottom of the reactor.
  • the first catalyst section includes an Fe-based catalyst to hydrogenate carbon dioxide to produce a reaction product including a base oil (C 2 to C 4 ) and a long-chain hydrocarbon (C 13+ ).
  • the Fe-based catalyst includes a rare earth metal and Fe, and any catalyst capable of converting carbon dioxide into a hydrocarbon compound may be used without limitation on type. As an example, it may be a compound represented by the following [Chemical Formula 1], but is not limited thereto.
  • the above M includes at least one selected from rare earth metals including Ce, La, and Pr,
  • composition ratios of a, b, c, d, and e above is 1.
  • the Fe-based catalyst represented by the above [chemical formula 1] has a pore volume of 0.17 to 0.21 cm 3 /g in BET analysis and an S BET of 80 to 200 m 2 /g and 95 to 100 m 2 /g.
  • the reaction product generated in the first catalyst unit is supplied to the second catalyst unit.
  • the second catalyst unit includes zeolite to oligomerize the base oil (C 2 to C 4 ) generated in the first catalyst unit to increase the carbon number, and crack long-chain hydrocarbons (C 13+ ) to decompose them into molecules having a smaller carbon number, thereby improving the yield of liquid fuel (C 5 to C 12 ).
  • the zeolite includes Si-Al zeolite, Si-P-Al zeolite or a mixture thereof, and as an example, preferably, it may be silicon aluminophosphate (silicoaluminophosphate-34, SAPO-34).
  • the pore size of the above SAPO-34 may be 1 to 5 ⁇ , the Acidity may be 1 to 1.5 mmol/g cat , and the (Si+P)/Al ratio may be 0.6 to 0.65.
  • the first catalyst section and the rear section of the first catalyst section include silica gel and glass wool.
  • the silica gel removes moisture generated in the process reaction, and the glass wool prevents the release of heat energy of the reverse water gas shift reaction and the Fischer-Tropsch synthesis reaction.
  • the gas introduced from the outside contains carbon dioxide and hydrogen, and the molar ratio of H 2 /CO 2 is 1 to 3, preferably 1.5 to 2.
  • the internal pressure of the columnar body is 1 to 50 bar, and the temperature is 100 to 1000°C, preferably 20 bar and 300°C, but is not limited thereto. If the pressure and temperature inside the columnar body are too low, the conversion reaction of carbon dioxide is insufficient, resulting in a small amount of reaction product produced, and if the pressure and temperature of the reactor are too high, there is a problem that energy efficiency is reduced.
  • the GHSV Global Hourly Space Velocity
  • the GHSV Global Hourly Space Velocity of the columnar body is 1,000 to 10,000 mL/g ⁇ h, preferably 3,000 to 8,000 mL/g ⁇ h, more preferably 6,000 to 7,000 mL/g ⁇ h, but is not limited thereto.
  • the liquid fuel produced in the second catalyst section is most preferably a hydrocarbon compound having a carbon number of C 5 to C 12 , and is delivered to the outside of the reactor or to another process through an outlet formed in the column-shaped body in a direction opposite to the first direction.
  • the present invention introduces the characteristics of CeO 2 into an Fe-based catalyst for the purpose of increasing the oxygen vacancy of the catalyst. Accordingly, the influence of the content of CeO 2 in the Fe-based catalyst was confirmed.
  • Figure 2 shows TEM images of Fe-based catalysts according to the CeO 2 content of the present invention.
  • (a) is CeO 2 10 wt%
  • (b) is CeO 2 20 wt%
  • (c) is CeO 2 50 wt%
  • (d) is CeO 2 100 wt%.
  • CeO 2 (111), (200), (220), (311) planes were confirmed.
  • the average particle size was measured to be 89 nm for 10 wt% CeO 2 , 250 nm for 20 wt% CeO 2 , 410 nm for 50 wt% CeO 2 , and over 500 nm for 100 wt% CeO 2.
  • CeO 2 lattice d-spacing value was calculated through the TEM image, it could be seen that as the CeO 2 content increased, many CeO2 (111) and (220) planes were formed.
  • the particles were clumped into round spherical shapes by CeO 2 , and it could be seen that as the CeO 2 content increased, the metal mixed particles clumped by CeO 2 gradually grew larger.
  • the crystal growth state differs significantly depending on the electronic state of Ce, and is generally divided into Rod (110), Cube (100), and Octahedral (111) forms.
  • Rod is formed when it is between Ce3 + and Ce4 +
  • Cube is formed a lot when it is Ce3 +
  • Octahedral is formed when it is Ce4 +.
  • CeO 2 addition amount Catalyst name catalyst S BET (m 2 /g) t-plot micropore area (m 2 /g) pore volume (cm 3 /g) Pore size (nm) CeO 2 0 wt% FeCuKeAl Fe 0.38 Cu 0.04 K 0.09 Al 0.49 158 0 0.15 3.4 CeO 2 10 wt% FeCuK10CeAl Fe 0.37 Cu 0.04 K 0.09 Ce 0.02 Al 0.48 99 0 0.1 4.1 CeO 2 20 wt% FeCuK20CeAl Fe 0.37 Cu 0.04 K 0.09 Ce 0.03 Al 0.47 98.6 0 0.19 5.6 CeO 2 50 wt% FeCuK50CeAl Fe 0.35 Cu 0.04 K 0.09 Ce 0.08 Al 0.45 30 3.4 0.08 8.6 CeO 2 100 wt% FeCuKCeO 2 Fe 0.5 Cu 0.06 K 0.14 Ce 0.26 9.3 2.6 0.06 21
  • Fig. 3 shows the XRD results of the Fe-based catalyst according to the CeO 2 content of the present invention.
  • the XRD analysis according to the CeO 2 content in the Fe-based catalyst was confirmed.
  • a peak corresponding to CeO 2 was confirmed at 33.3 °
  • a peak corresponding to Fe 2 O 3 was confirmed at 35.9 °
  • a phenomenon in which the Fe 2 O 3 peak shifted to a low angle was observed. It can be presumed that this was due to substitution by electron transfer between Fe and another transition metal.
  • FIG. 4 shows the results of H 2 -TPR, CO 2 -TPD, and CO-TPD analyses of the Fe-based catalyst according to the CeO 2 content of the present invention.
  • thermal decomposition analysis H 2 -TPR, CO, and CO 2 -TPD
  • H 2 consumed by reduction gradually increased as the CeO 2 content increased, and in particular, reduction was observed at high temperature. Since reduction is performed at 350 °C as a pretreatment in the actual CO 2 hydrogenation reaction, the FeCuK20CeAl catalyst has the largest reduction amount in the actual reaction.
  • Table 3 is a table showing the evaluation of reaction activity according to the CeO 2 content of the Fe-based catalyst. Yield indicates the yield according to the conversion of CO+CO2.
  • CeO 2 addition amount Catalyst name X CO+CO2 (%) X CO2 (%) Yield (%) CH 4 C 2 ⁇ 4 C 5 ⁇ 12 C 13+ CeO 2 0 wt% FeCuKeAl 24.9 18.1 1.4 4.0 11.8 7.7 CeO 2 3 wt% FeCuK3CeAl 26.5 18.4 1.6 4.4 12.9 7.6 CeO 2 10 wt% FeCuK10CeAl 28 18.3 1.5 6.0 13.0 4.0 CeO 2 20 wt% FeCuK20CeAl 36.8 25.9 1.5 10.6 18.0 6.0 CeO 2 30 wt% FeCuK30CeAl 30.4 16.7 3.1 7.3 13.0 3.2 CeO 2 50 wt% FeCuK50CeAl 29 15.5 2.8 7.0 14.5 4.7 CeO 2 100 wt% FeCuKCeO 2 29.4 16.8 1.2 5.8 15.3 7.1
  • the present invention confirmed the same oxygen vacancy effect by adding a rare earth metal along with Ce to an Fe-based catalyst, and also added La and Pr to confirm the catalytic activity.
  • [Table 4] is a table showing a comparison of the reaction activity evaluation according to the type of rare earth metal of the Fe-based catalyst. Yield indicates the yield according to the conversion of CO+ CO2 .
  • FIG. 5 shows the results of H 2 -TPR, CO 2 -TPD, and CO-TPD analyses of the Fe-based catalyst according to the type of rare earth metal of the present invention. While La exists as La 2 O 3 oxide, Pr exists as Pr 6+ or Pr 5+ , so relatively many reducing sites can be expected. However, in reality, due to the high oxidation number, the number of sites adjacent to Al and Fe increases, so the number of sites for CO or CO 2 to be adsorbed is relatively reduced, resulting in a lower adsorption amount than Ce in CO 2 -TPD and CO-TPD.
  • the present invention compares SAPO-34, a Si-P-Al zeolite, with ZSM-5, the most widely used conventional Si-Al zeolite.
  • the average pore size of SAPO-34 is 3.8 ⁇ , and the average pore size of ZSM-5 is 5.5 ⁇ .
  • the reaction activity was evaluated when only an Fe-based catalyst (FeCuK20CeAl) was used and when an Fe-based catalyst and zeolite (SAPO-34 or ZSM-5) were used as a dual bed.
  • the reaction conditions were as follows.
  • Figure 7 shows the hydrocarbon distribution of the liquid product according to the zeolite of the present invention.
  • the hydrocarbon distribution of the liquid product (C 4 ⁇ C 10 ) was analyzed by Reformulyzer.
  • (a) is Fe-based catalyst + ZSM-5
  • (b) is Fe-based catalyst + SAPO-34.
  • (a) shows 17% of the produced aromatic compound, while (b) shows 4.2%, which is significantly less than ZSM-5. This is thought to be because the aromatic compound was not formed during the oligomerization process due to the pore specificity of SAPO-34.
  • Figure 8 shows the carbon distribution of the liquid product according to the utilization of zeolite of the present invention.
  • (a) is when only an Fe-based catalyst is used, and
  • (b) is when an Fe-based catalyst and SAPO-34 are used as a dual bed.
  • the specific gravity of C 5 ⁇ C 12 in the liquid product of (a) is 74.6%, and the specific gravity of C 5 ⁇ C 12 in the liquid product of (b) is 81.5%, confirming that the specific gravity of C 5 ⁇ C 12 in the liquid product increased by about 7% compared to (a).

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Abstract

La présente invention concerne un système de conversion de dioxyde de carbone présentant un rendement en combustible liquide amélioré à l'aide de zéolite, et un réacteur de conversion de dioxyde de carbone associé, et, plus particulièrement, un système de conversion de dioxyde de carbone et un réacteur de conversion de dioxyde de carbone associé, le système utilisant de la zéolite silicoaluminophosphate-34 (SAPO-34) de façon à avoir un rendement amélioré en naphta et en essence, qui sont produits par hydrogénation de dioxyde de carbone.
PCT/KR2024/001168 2023-11-20 2024-01-25 Système de conversion de dioxyde de carbone ayant un rendement en combustible liquide amélioré à l'aide de zéolite, et réacteur de conversion de dioxyde de carbone associé Pending WO2025110346A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000063014A (ko) * 1999-03-24 2000-10-25 바이벨 베 연료 합성법
KR20190136978A (ko) * 2018-05-30 2019-12-10 한국화학연구원 에너지 효율적인 이산화탄소의 전환 시스템 및 방법
US20220213394A1 (en) * 2021-01-07 2022-07-07 Chevron U.S.A. Inc. Processes for catalyzed ring-opening of cycloparaffins
KR20230004857A (ko) * 2020-05-04 2023-01-06 인피니움 테크놀로지, 엘엘씨 이산화탄소와 수소로부터 액체연료를 직접 생산하기 위한 개선된 촉매 및 공정
KR20230129189A (ko) * 2021-02-05 2023-09-06 인피니움 테크놀로지, 엘엘씨 Co₂와 h₂로부터 액체연료를 직접 생산하는 효율적인2단계 공정

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100903439B1 (ko) 2007-10-15 2009-06-18 한국화학연구원 천연가스로부터 경질탄화수소의 직접 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000063014A (ko) * 1999-03-24 2000-10-25 바이벨 베 연료 합성법
KR20190136978A (ko) * 2018-05-30 2019-12-10 한국화학연구원 에너지 효율적인 이산화탄소의 전환 시스템 및 방법
KR20230004857A (ko) * 2020-05-04 2023-01-06 인피니움 테크놀로지, 엘엘씨 이산화탄소와 수소로부터 액체연료를 직접 생산하기 위한 개선된 촉매 및 공정
US20220213394A1 (en) * 2021-01-07 2022-07-07 Chevron U.S.A. Inc. Processes for catalyzed ring-opening of cycloparaffins
KR20230129189A (ko) * 2021-02-05 2023-09-06 인피니움 테크놀로지, 엘엘씨 Co₂와 h₂로부터 액체연료를 직접 생산하는 효율적인2단계 공정

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