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WO2025220721A1 - Procédé de génération d'hydrocarbures et dispositif de génération d'hydrocarbures - Google Patents

Procédé de génération d'hydrocarbures et dispositif de génération d'hydrocarbures

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Publication number
WO2025220721A1
WO2025220721A1 PCT/JP2025/015052 JP2025015052W WO2025220721A1 WO 2025220721 A1 WO2025220721 A1 WO 2025220721A1 JP 2025015052 W JP2025015052 W JP 2025015052W WO 2025220721 A1 WO2025220721 A1 WO 2025220721A1
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WIPO (PCT)
Prior art keywords
synthesis reaction
reaction
hydrocarbon
catalyst
hydrocarbon production
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PCT/JP2025/015052
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English (en)
Japanese (ja)
Inventor
崇 鈴木
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Sumitomo Heavy Industries Ltd
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Sumitomo Heavy Industries Ltd
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Publication of WO2025220721A1 publication Critical patent/WO2025220721A1/fr
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/06—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen in the presence of organic compounds, e.g. hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/14—Aliphatic saturated hydrocarbons with five to fifteen carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/22—Aliphatic saturated hydrocarbons with more than fifteen carbon atoms
    • 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

Definitions

  • the present invention relates to a hydrocarbon production method and hydrocarbon production apparatus using the Fischer-Tropsch synthesis reaction (hereinafter also referred to as the "FT synthesis reaction"). More specifically, the present invention relates to a hydrocarbon production method and hydrocarbon production apparatus that uses the FT synthesis reaction to obtain saturated hydrocarbons having a specific carbon number.
  • FT synthesis reaction the Fischer-Tropsch synthesis reaction
  • the FT synthesis reaction is a reaction in which a mixed gas of carbon monoxide and hydrogen is reacted in the presence of a catalyst to produce a hydrocarbon mixture.
  • Patent Document 1 describes a synthesis gas production method that can reduce operating costs in the upgrading reaction step and make the equipment more compact in a process for producing liquid hydrocarbons from natural gas, as well as a synthesis gas production method that can increase the raw material consumption rate by incorporating purge gas from the hydrogen separation step back into the process and reusing it as a raw material.
  • the objective of the present invention is to provide technology related to a hydrocarbon production method and hydrocarbon production apparatus that can reduce the facilities and equipment that make up a plant and more easily produce hydrocarbons with a specific carbon number on-site.
  • the hydrocarbon production method of the present invention which solves the above-mentioned problems, includes an FT synthesis reaction step of supplying a feedstock gas into a reaction vessel containing a reaction catalyst and carrying out a Fischer-Tropsch synthesis reaction, and a saturated hydrocarbon recovery step of selectively recovering saturated hydrocarbons having a carbon number of 16 or less, wherein the FT synthesis reaction step is carried out under conditions such that the value of the chain growth probability ( ⁇ ) in the Fischer-Tropsch synthesis reaction is 0.85 or less.
  • the present invention by proceeding with the FT synthesis reaction so as to satisfy a specific chain growth probability value, it is possible to select to a certain extent the number of carbon atoms in the resulting hydrocarbons (saturated hydrocarbons), and further, by selectively recovering saturated hydrocarbons having a specific carbon number, it is possible to simply produce saturated hydrocarbons that are useful as SAF.
  • the saturated hydrocarbon recovery step includes a reflux step of refluxing the saturated hydrocarbons obtained in the FT synthesis reaction step, and the reflux step is carried out at a temperature of 110°C or higher and 230°C or lower.
  • a jet fuel (SAF) fraction having about 8 to 16 carbon atoms can be selectively obtained.
  • the FT synthesis reaction step is carried out at a reaction temperature of 200°C or higher and 270°C or lower. According to the present invention, the CO and CO2 conversion rates are increased, and productivity can be improved.
  • the FT synthesis reaction step is carried out at a reaction pressure of 0.5 MPa.G or more and 3 MPa.G or less. According to the present invention, chain growth can be promoted.
  • one embodiment of the method for producing saturated hydrocarbons according to the present invention is characterized in that the reaction catalyst used in the FT synthesis reaction step contains at least one element selected from yttrium, cerium, lanthanum, praseodymium, neodymium, holmium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, and copper. According to the present invention, it is possible to increase the amounts of carbon monoxide and carbon dioxide adsorbed on the catalyst surface and also to increase the number of reaction active sites.
  • the reaction catalyst contains at least one selected from the group consisting of cobalt, ruthenium, and iron. According to the present invention, a fraction of saturated hydrocarbons (fraction equivalent to SAF) having a carbon number sufficient for use in diesel, jet fuel (SAF), kerosene, etc. can be efficiently obtained.
  • the value of the chain growth probability ( ⁇ ) is 0.72 to 0.78. According to the present invention, the efficiency of producing the SAF-equivalent fraction can be increased.
  • the present invention provides an apparatus for producing saturated hydrocarbons, which comprises an FT synthesis reaction section in which a raw material gas is supplied into a reaction vessel having a reaction catalyst and a Fischer-Tropsch synthesis reaction is carried out, and a saturated hydrocarbon recovery section in which saturated hydrocarbons having a carbon number of 16 or less are selectively recovered, and the FT synthesis reaction section is operated under conditions in which the value of the chain growth probability ( ⁇ ) in the Fischer-Tropsch synthesis reaction is 0.85 or less.
  • the present invention by proceeding with the FT synthesis reaction so as to satisfy a specific chain growth probability value, it is possible to select to a certain extent the number of carbon atoms in the resulting hydrocarbons (saturated hydrocarbons), and further, by selectively recovering saturated hydrocarbons having a specific carbon number, it is possible to simply produce saturated hydrocarbons that are useful as SAF.
  • the saturated hydrocarbon recovery section includes a reflux section for refluxing the saturated hydrocarbons obtained in the FT synthesis reaction section, and the reflux section is maintained at a temperature of 110°C or higher and 230°C or lower.
  • a jet fuel (SAF) fraction having about 8 to 16 carbon atoms can be selectively obtained.
  • the present invention provides technology related to a hydrocarbon production method and hydrocarbon production apparatus that can reduce the facilities and equipment that make up a plant and more easily produce hydrocarbons with a specific carbon number on-site.
  • FIG. 1 is a schematic diagram illustrating a catalyst surface reaction in an FT synthesis reaction.
  • FIG. 1 is a schematic diagram illustrating the chain propagation probability and the distribution of hydrocarbon (crude product) composition obtained by the FT synthesis reaction.
  • 1 is a schematic illustration of a hydrocarbon production apparatus according to an embodiment of the present invention.
  • the FT synthesis reaction is a reaction in which synthesis gas (a mixed gas of carbon monoxide (CO) and hydrogen (H 2 )) is brought into contact with a catalyst, gradually increasing the number of methylene groups (—CH 2 —) according to the following formula 1, and producing hydrocarbons with a wide range of carbon numbers, from methane (C 1 ) to wax (C 30+ ).
  • synthesis gas a mixed gas of carbon monoxide (CO) and hydrogen (H 2 )
  • the types of hydrocarbons produced follow the ASF distribution based on the Anderson-Schulz-Flory (hereinafter referred to as "ASF") law. It is known that the composition of the produced hydrocarbons is correlated with the value of the chain propagation probability ( ⁇ ) in the FT synthesis reaction as shown in Equation 2.
  • Wn is the weight fraction of hydrocarbon products consisting of n carbon atoms in all hydrocarbons
  • ⁇ is the chain growth probability.
  • FIG. 2 shows the relationship between the chain propagation probability ( ⁇ ) and the composition of hydrocarbons (crude product composition) produced by the FT synthesis reaction.
  • ⁇ chain propagation probability
  • hydrocarbons produced by the FT synthesis reaction contain multiple hydrocarbon compositions regardless of the value of the chain growth probability ( ⁇ ). Therefore, it is difficult to obtain only hydrocarbons with a specific composition or only hydrocarbons suitable for a specific application using a conventional FT synthesis reaction.
  • step 1 For example, to obtain jet fuel, it was necessary to separate the wax component from the product (step 1), upgrade the wax component (hydrocracking and hydrotreating) (step 2), and then distill the liquid hydrocarbons obtained in step 1 and the hydrocracked and hydrotreated liquid hydrocarbons obtained in step 2 to obtain a jet fuel fraction with carbon numbers of 9 to 15 ( C9 to C15 ) (step 3). This required equipment to perform steps 1 to 3.
  • the Fischer-Tropsch synthesis reaction is carried out under conditions in which the value of the chain propagation probability ( ⁇ ) falls within a specific range, and saturated hydrocarbons having 8 to 16 carbon atoms are selectively recovered, thereby easily obtaining useful saturated hydrocarbons that can be used for SAF and the like.
  • the hydrocarbon production method in this embodiment comprises the following steps: That is, the hydrocarbon production method in this embodiment includes an FT synthesis reaction step of supplying a raw material gas into a reaction vessel containing a reaction catalyst and carrying out a Fischer-Tropsch synthesis reaction, and a saturated hydrocarbon recovery step of selectively recovering saturated hydrocarbons having 8 to 16 carbon atoms.
  • the FT synthesis reaction step is carried out under conditions in which the chain propagation probability ( ⁇ ) in the Fischer-Tropsch synthesis reaction is 0.65 to 0.85.
  • the hydrocarbon production method of this embodiment includes an FT synthesis reaction step in which a raw material gas is supplied into a reaction vessel containing a reaction catalyst to carry out a Fischer-Tropsch synthesis reaction.
  • the feed gas is a raw material for producing hydrocarbons by the FT synthesis reaction.
  • the feed gas consists of a mixed gas of carbon monoxide (CO) and hydrogen (H 2 ).
  • the feed gas may contain carbon dioxide (CO 2 ).
  • the rate of the FT synthesis reaction depends on the hydrogen partial pressure, a certain level of H2 partial pressure is required, and the partial pressure ratio (molar ratio) of hydrogen to the total of (carbon monoxide + carbon dioxide) in the raw material gas is appropriately 0.6 to 2.7, preferably 0.8 to 2.5, and more preferably 1 to 2.3.
  • the ratio of carbon monoxide to carbon dioxide can be varied depending on the purpose; the ratio of carbon dioxide is increased for the purpose of carbon recycling, and the ratio of carbon monoxide is increased to increase the conversion rate to hydrocarbons.
  • carbon dioxide may be 100%, and carbon monoxide may not be used.
  • the ratio of carbon dioxide to carbon monoxide is not particularly limited, but the ratio of carbon dioxide to the total amount of carbon monoxide and carbon dioxide must be 1% by volume or more, preferably 10% by volume or more, more preferably 30% by volume or more, and even more preferably 40% by volume or more. Furthermore, as other components, substances other than the above-mentioned hydrogen, carbon monoxide, and carbon dioxide may be mixed into the raw material gas, as long as they do not interfere with the FT synthesis reaction.
  • the reaction vessel into which the raw material gas is introduced and the catalyst placed in the reaction vessel may be any catalyst that can cause the FT synthesis reaction step in this embodiment to proceed so that the value of the chain growth probability ( ⁇ ) satisfies a specific range, and specific examples will be given in the description of the hydrocarbon production apparatus that produces hydrocarbons based on the hydrocarbon production method of this embodiment (the hydrocarbon production apparatus of this embodiment).
  • the conditions (reaction temperature, reaction pressure) for allowing the FT synthesis reaction to proceed in the FT synthesis reaction step may be any conditions as long as they allow the reaction to proceed so that the value of the chain growth probability ( ⁇ ) satisfies a specific range, and specific examples will be described later together with the explanation of the hydrocarbon production apparatus of this embodiment.
  • the technical significance of carrying out the FT synthesis reaction under conditions in which the value of the chain growth probability ( ⁇ ) is 0.65 to 0.85 in the FT synthesis reaction step in the hydrocarbon production method of this embodiment will be described.
  • the FT synthesis reaction is a type of polymerization reaction, and it is generally difficult to maintain a constant degree of polymerization (n number), resulting in a wide range of products, from C1 to C100+ .
  • the carbon number distribution of the produced hydrocarbons follows the ASF distribution law and can be expressed by the chain propagation probability ( ⁇ ) in this distribution law, and it is known that with industrial catalysts, the value of the chain propagation probability ( ⁇ ) is approximately 0.85 to 0.95.
  • the catalyst/dispersion medium ratio was 25 (w/w)% for a silica-supported cobalt catalyst (Na-Co/ SiO2 catalyst) containing 2/5 parts by weight of sodium as a cocatalyst relative to the Co content (25 wt%).
  • the FT reaction was performed at a reaction temperature of 220°C, a pressure of 950 kPa, G (9.5 kg/ cm2 , G), and a mixed gas ( H2 /CO ratio 1/2 (0.5)) flow rate (volume (vg)) relative to the catalyst volume (vc) was supplied at a rate ranging from 500 to 750 per hour (vg/vc ⁇ h -1 ).
  • the one-pass conversion rate once-through conversion
  • the chain propagation probability ( ⁇ ) was 0.9.
  • the horizontal axis represents the carbon number
  • the vertical axis represents the weight distribution of hydrocarbons. As shown in FIG.
  • the catalyst/dispersion medium ratio for a silica-supported cobalt catalyst (Ce-Co/ SiO2 catalyst) containing cerium as a promoter at 1/20 weight part relative to the Co content (10 weight%) was 3 (w/w)%.
  • the FT reaction was performed at a reaction temperature of 230°C, a pressure of 600 kPa, G (6 kg/ cm2 , G), and a flow rate (volume (vg)) of the mixed gas ( H2 /CO ratio 2/1 (2.0)) relative to the catalyst volume (vc) was supplied in the range of 1,100 to 1,500 (vg/vc ⁇ h -1 ) per hour.
  • the one-pass conversion rate was 50 to 58%, and the chain propagation probability ( ⁇ ) was 0.75. 4
  • the horizontal axis represents the carbon number and the vertical axis represents the weight distribution of hydrocarbons, as in Fig. 3. It goes without saying that the above conditions are merely an example and are not limited to these.
  • the chain propagation probability ( ⁇ ) value suitable for obtaining saturated hydrocarbons having a carbon number (8 to 16 carbon atoms) particularly useful as SAF is preferably 0.65 to 0.85, more preferably 0.70 to 0.80, and most preferably 0.72 to 0.78. If the value is outside this range, the production efficiency of the SAF-equivalent fraction will decrease.
  • the hydrocarbon production method of this embodiment also includes a saturated hydrocarbon recovery step of selectively recovering saturated hydrocarbons having 8 to 16 carbon atoms from the hydrocarbons obtained in the above-described FT synthesis reaction step.
  • the hydrocarbons introduced into the saturated hydrocarbon recovery step are mainly those having a carbon number of 20 or less. Therefore, the saturated hydrocarbon recovery step may be any step that can effectively separate and recover saturated hydrocarbons having a carbon number of 8 to 16 from the saturated hydrocarbon recovery step.
  • An example of the saturated hydrocarbon recovery step in this embodiment includes a reflux step in which the saturated hydrocarbons obtained in the FT synthesis reaction step are refluxed.
  • the temperature range suitable for obtaining the SAF-equivalent fraction is preferably 110°C or higher and 230°C or lower, more preferably 150°C or higher and 230°C or lower, and most preferably 170°C or higher and 220°C or lower.
  • naphtha which is lighter than the SAF-equivalent fraction, will be recovered as the main component.
  • the difference between the total hydrocarbons introduced into the saturated hydrocarbon recovery step (the fraction obtained in the FT synthesis reaction step) will be small.
  • the hydrocarbon production apparatus in this embodiment is an apparatus for producing hydrocarbons based on the hydrocarbon production method described above, and includes an FT synthesis reaction section in which a raw material gas is supplied into a reaction vessel containing a reaction catalyst to carry out an FT synthesis reaction, and a saturated hydrocarbon recovery section that selectively recovers saturated hydrocarbons having a carbon number of 8 to 16.
  • the saturated hydrocarbon recovery section may include one that includes a reflux section that refluxes the saturated hydrocarbons obtained in the FT synthesis reaction section.
  • the hydrocarbon production apparatus in this embodiment may include a reflux unit, which corresponds to the reflux section in the saturated hydrocarbon recovery section, installed downstream of the upflow where components including unreacted gases from the FT synthesis reaction section are vented upward at the FT reaction temperature, a cooling unit installed downstream of which a fraction collector is further installed in series downstream.
  • the reflux unit is maintained at a predetermined temperature and is filled with a plate-like structure and a hollow ring.
  • FIG. 5 shows a schematic illustration of a hydrocarbon production system 100 according to an embodiment of the present invention. Referring to FIG. 5, the hydrocarbon production device 100 in this embodiment will be described.
  • the hydrocarbon production system 100 includes an FT reactor 10 as an FT synthesis reaction section, a reflux unit 20 as a saturated hydrocarbon recovery section, a cooling unit 30, and a fraction collector 40.
  • FT reactor 10 as an FT synthesis reaction section
  • reflux unit 20 as a saturated hydrocarbon recovery section
  • cooling unit 30 as a cooling unit
  • fraction collector 40 a fraction collector
  • the FT synthesis reaction section is for carrying out the above-mentioned FT synthesis reaction step, and supplies a raw material gas into a reaction vessel (FT reactor 10 in this embodiment) containing a reaction catalyst to carry out the FT synthesis reaction.
  • FT reactor 10 for the FT synthesis reaction section in this embodiment is a slurry bubble column reactor (SBCR) 10. This is for capturing the hydrocarbon vapor containing the SAF fraction rising from the top of the reactor.
  • SBCR slurry bubble column reactor
  • reaction types such as a circulating fluidized bed (CFB) reactor, a fluidized bed reactor, or a fixed bed reactor can be used.
  • a powdered reaction catalyst (hereinafter referred to as "FT catalyst 16") and a hydrocarbon that is liquid near the reaction temperature are placed in the FT reactor 10 as a dispersion medium, and the feed gas is introduced from below a sparger (gas dispersion section) 12 installed at the bottom of the FT reactor 10.
  • the hydrocarbon placed together with the FT catalyst 16 during the reaction preferably has a carbon number of 12 to 50, more preferably 15 to 40, and most preferably 15 to 30. If the carbon number is less than this, the vapor pressure near the reaction temperature will be too high, and if it exceeds this range, the hydrocarbon will need to be preheated before being placed, reducing operability.
  • the dispersion medium in the FT reactor 10 is replaced by hydrocarbons (FT oil) synthesized in the FT synthesis reaction.
  • the slurry bed in the FT reactor 10 is maintained at a temperature of 200° C. or more and 270° C. or less, and at a pressure of 0.5 MPa.G or more and 3 MPa.G or less.
  • the reaction temperature is preferably 200°C or higher and 270°C or lower, more preferably 210°C or higher and 240°C or lower, and even more preferably 220°C or higher and 240°C or lower. Below this temperature, the CO and CO2 conversion rates are low, resulting in low productivity.
  • the reaction pressure is preferably 0.5 MPa ⁇ G or more and 3 MPa ⁇ G or less, more preferably 0.5 MPa ⁇ G or more and 2 MPa ⁇ G or less, and most preferably 0.6 MPa ⁇ G or more and 1.5 MPa ⁇ G or less.
  • This pressure range chain growth tends to be difficult to proceed, and there is a risk of a decrease in the SAF yield.
  • chain growth saturates, and the unit consumption increases due to compression, making the technical significance of this method diminished.
  • ⁇ Agitation mechanism The feed gas disperses as bubbles in the hydrocarbons and moves upward, creating an upward flow of liquid hydrocarbons.
  • the upward flow and buoyancy force disperse the FT catalyst 16 within the bubble column of the FT reactor 10.
  • the FT reactor 10 can also be provided with a stirring mechanism 14. It is also preferable to provide the stirring mechanism 14 with stirring blades 15 to forcibly disperse the FT catalyst 16.
  • the provision of stirring blades 15 increases the contact efficiency of the feed gas (gas), dispersion medium (liquid), and FT catalyst 16 (solid), allowing the height of the reaction column of the FT reactor 10 to be reduced, thereby saving space in the plant.
  • the FT catalyst 16 in this embodiment may be any catalyst that functions as a catalyst for the FT synthesis reaction, and examples thereof include a main catalyst, a catalyst carrier, and an auxiliary catalyst.
  • the main catalyst in the FT catalyst 16 is a metal catalyst selected from cobalt, ruthenium, and iron. Iron is inexpensive but has relatively low catalytic activity, while ruthenium is a precious metal with high catalytic activity but is extremely expensive.
  • the products of the FT synthesis reaction using an iron-based catalyst are characterized by a high naphtha content and also contain oxygen-containing compounds. For this reason, cobalt is most preferably used as the main catalyst to obtain a fraction of saturated hydrocarbons (fraction equivalent to SAF) having the carbon number used in diesel, jet fuel (SAF), kerosene, etc.
  • the amount of the main catalyst is preferably 5% by weight or more and 25% by weight or less, more preferably 7.5% by weight or more and 20% by weight or less, and even more preferably 8% by weight or more and 15% by weight or less, calculated as metal based on the weight of the FT catalyst 16. If the amount is less than this range, the activity in the FT synthesis reaction tends to be insufficient, whereas if the amount exceeds this range, the activity in the FT synthesis reaction saturates, and there is little technical significance, particularly in terms of cost.
  • the catalyst support used in the FT catalyst 16 is a support containing at least one of silica (SiO 2 ), alumina (Al 2 O 3 ), and zeolite (aluminosilicate). Of these, it is preferable to use silica. Silica is chemically stable and therefore does not affect the main catalyst or auxiliary catalyst. This allows the chemical properties of the main catalyst and auxiliary catalyst to be fully exhibited. Furthermore, because of its large specific surface area, it has high contact efficiency with the raw material gas (substrate), allowing the FT synthesis reaction to proceed efficiently. The true density (true specific gravity) of the catalyst support increases in the order of alumina > zeolite > silica.
  • silica is considered to be the catalyst support with the best operability in this embodiment.
  • the FT catalyst 16 may contain an auxiliary catalyst in addition to the main catalyst.
  • the auxiliary catalyst is characterized by containing at least one rare earth element selected from the group consisting of yttrium, cerium, lanthanum, praseodymium, neodymium, and holmium, at least one alkali metal selected from the group consisting of sodium, potassium, rubidium, and cesium, at least one alkaline earth metal selected from the group consisting of beryllium, magnesium, calcium, strontium, and barium, and copper.
  • yttrium, cerium, lanthanum, praseodymium, neodymium, holmium, and copper are preferred, yttrium, cerium, lanthanum, praseodymium, neodymium, and holmium are more preferred, and yttrium is most preferred.
  • the addition of the auxiliary catalyst is thought to increase the amount of carbon monoxide and carbon dioxide adsorbed on the catalyst surface, as well as increase the number of reactive active sites.
  • charge transfer occurs between the main catalyst (such as cobalt) and copper, slightly lowering the oxidation number of the main catalyst ( ⁇ -).
  • reaction frequency (turnover frequency)
  • TOF turnover frequency
  • the amount of auxiliary catalyst is preferably 1/30 to 1/3 of the weight of the main catalyst (such as cobalt), and more preferably 1/20 to 1/5.
  • the FT catalyst 16 contained in the FT reactor 10 may be in the form of a fine powder.
  • the particle shape of the FT catalyst 16 is preferably crushed, ellipsoidal, spherical, cylindrical, or the like, and it is also preferable to use a combination of these shapes.
  • the particle size (longest part of the across length) of the FT catalyst 16 in this embodiment is preferably 0.07 mm or more and 1 mm or less, more preferably 0.07 mm or more and 0.7 mm or less, and even more preferably 0.08 mm or more and 0.17 mm or less.
  • the specific surface area (SA) of the FT catalyst 16 is preferably 100 m 2 /g or more, more preferably 200 m 2 /g or more, and most preferably 300 m 2 /g or more. There is no particular upper limit to the specific surface area of the FT catalyst 16, but the substantial upper limit is 500 m 2 /g. Furthermore, if the specific surface area is below this lower limit range, the active metals related to the main catalyst and the like described above cannot be sufficiently supported in the FT catalyst 16.
  • Equation 3 is a general chemical reaction formula, and includes the case where the FT synthesis reaction shown in formula 1 and the reverse water gas shift reaction shown in formula 4 occur in parallel.
  • Equation 3 is also a chemical reaction equation combining Equations 1 and 4.
  • FT reactor 10 In the FT synthesis reaction section (FT reactor 10), by conducting the FT synthesis reaction so that the chain propagation probability ( ⁇ ) value falls within the above-mentioned range (0.65 to 0.85), the production of hydrocarbons with a large carbon number (particularly 20 or more carbon atoms) is suppressed, and hydrocarbons (FT oil) are produced in which the weight distribution of hydrocarbons with a carbon number of 8 to 16 (SAF-equivalent fraction) is greater than the weight distribution of hydrocarbons with a carbon number of 17 or more.
  • ⁇ chain propagation probability
  • the hydrocarbons (fractions) produced in the FT synthesis reaction section are introduced into the saturated hydrocarbon recovery section, which serves to advance the saturated hydrocarbon recovery step described above and selectively recover saturated hydrocarbons having 8 to 16 carbon atoms.
  • the saturated hydrocarbon recovery section in this embodiment may be one equipped with a reflux section for refluxing the saturated hydrocarbons obtained in the FT synthesis reaction section.
  • the reflux unit 20 corresponds to a reflux section.
  • the reflux unit 20 is installed downstream of the FT reactor 10 and serves to selectively obtain hydrocarbons having 8 to 16 carbon atoms (a fraction corresponding to SAF). It may be installed directly above the FT reactor 10 as shown in Figure 5, or it may be installed next to the FT reactor 10 via an insulated conduit from the top of the FT reactor 10.
  • the conduit is desirably maintained (insulated) at a temperature suitable for the reflux unit 20 by heaters A to D.
  • the tower height of the reflux unit 20 can be reduced.
  • metal and/or ceramic Raschig rings can be packed in place of the plates.
  • the reflux unit 20 is preferably maintained at a temperature between 110°C and 230°C, more preferably between 150°C and 230°C, and most preferably between 170°C and 220°C. Below this temperature range, naphtha, which is lighter than the SAF-equivalent fraction, becomes the main component. Furthermore, above this temperature range, there is little difference between the fraction in the FT reactor 10 and the fraction in the FT reactor 10.
  • the cooling unit 30 has a role of cooling and condensing the fraction corresponding to SAF sent from the reflux unit 20 and collecting the fraction in a fraction collector 40 installed downstream of the cooling unit 30 .
  • the cooling pipes inside the cooling unit 30 may be straight pipes as shown in Fig. 5, or may be spiral pipes, ball-shaped pipes, etc. Also, cooling fins may be attached to the cooling pipes.
  • the cooling temperature in the cooling unit 30 is preferably 20° C. or higher and 40° C. or lower, more preferably 20° C. or higher and 35° C. or lower, and most preferably 25° C. or higher and 35° C. or lower. Below this temperature range, the viscosity of the hydrocarbons increases in the cooling unit 30, reducing the recovery efficiency. On the other hand, above this temperature range, the cut range of the hydrocarbons becomes broad.
  • the fraction collector 40 serves to receive and recover the fraction corresponding to the SAF that has passed through the cooling unit 30 .
  • a solenoid valve 42 may be installed below the fraction collector 40, and the liquid height of the SAF-equivalent fraction may be monitored with a level meter. When a certain amount is reached, the liquid may be stored in a product tank via the solenoid valve 42.
  • the reaction conditions in the FT synthesis reaction step were a silica-supported cobalt catalyst (Ce-Co/ SiO2 catalyst) containing cerium as an auxiliary catalyst at 1/20 weight part relative to the Co content (10 weight%), with a catalyst to dispersion medium ratio of 3 (w/w)%.
  • the FT reaction was carried out at a reaction temperature of 230°C, a pressure of 600 kPa, G (6 kg/ cm2 , G), and a flow rate (volume (vg)) of a mixed gas ( H2 /CO ratio 2/1 (2.0)) relative to the catalyst volume (vc) in the range of 1,100 to 1,500 (vg/vc ⁇ h -1 ) per hour.
  • the single-pass conversion rate was 50 to 58%, and the chain growth probability ( ⁇ ) was 0.75.
  • saturated hydrocarbons having a carbon number of 16 or less could be selectively recovered.
  • saturated hydrocarbons having a carbon number (8 to 16) useful as SAF could be easily produced. It goes without saying that the above conditions are merely an example and are not limited to the above conditions.
  • hydrocarbon production method and hydrocarbon production apparatus of this embodiment it is possible to produce an SAF-equivalent fraction without the steps of separating solids including wax and catalyst, upgrading the wax, and distilling.
  • This makes it possible to produce SAF on-site, more specifically, at a CO2 capture site or hydrogen production site adjacent to an airport, and contributes to the spread of carbon-neutral fuels.
  • the above-described embodiment shows an example of a hydrocarbon production method and hydrocarbon production device.
  • the hydrocarbon production method and hydrocarbon production device according to the present invention are not limited to the above-described embodiment, and the hydrocarbon production method and hydrocarbon production device according to the above-described embodiment may be modified within the scope of the gist of the claims.
  • the reflux temperature in the reflux step (reflux section) of the saturated hydrocarbon recovery step (saturated hydrocarbon recovery section) is set to 110°C or higher and 230°C or lower.
  • This temperature range is suitable for obtaining fractions useful as SAF, but by setting the temperature range to, for example, 70°C or higher but lower than 110°C, it is also possible to use the temperature range to obtain saturated hydrocarbons useful for other applications, such as volatile oil fractions (gasoline precursors) and naphtha fractions.
  • the hydrocarbon production method and hydrocarbon production apparatus of the present invention can be used as a technology that can easily and on-site produce hydrocarbons (saturated hydrocarbons) with a specific carbon number. They are particularly suitable for use in the production of kerosene and SAF.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'une technologie relative à un procédé de génération d'hydrocarbure et à un dispositif de génération d'hydrocarbure grâce auxquels il sera possible de réduire les installations et l'équipement constituant une installation et d'obtenir une génération sur site plus facile d'un hydrocarbure ayant un nombre de carbone spécifique.　Afin de résoudre le problème mentionné ci-dessus, la présente invention concerne : un procédé de génération d'hydrocarbures comprenant une étape de réaction de synthèse FT dans laquelle une matière première gazeuse est introduite dans une cuve de réaction comprenant un catalyseur de réaction et une réaction de synthèse Fischer-Tropsch est effectuée, et une étape de récupération d'hydrocarbures saturés dans laquelle un hydrocarbure saturé ayant 8 à 16 atomes de carbone est récupéré sélectivement, l'étape de réaction de synthèse FT étant effectuée dans des conditions dans lesquelles la valeur de la probabilité de croissance de chaîne (α) dans la réaction de synthèse Fischer-Tropsch est de 0,65 à 0,85 ; et un dispositif de génération d'hydrocarbures basé sur le procédé de génération d'hydrocarbures.　La présente invention permet de générer facilement un hydrocarbure saturé qui est utile en tant que SAF.
PCT/JP2025/015052 2024-04-18 2025-04-17 Procédé de génération d'hydrocarbures et dispositif de génération d'hydrocarbures Pending WO2025220721A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004519419A (ja) * 2000-07-24 2004-07-02 シェブロン ユー．エス．エー． インコーポレイテッド 留出燃料及び／又は潤滑油ベースオイル範囲の炭化水素のフィッシャー−トロプシュ合成を最適化する方法
JP2004237254A (ja) * 2003-02-07 2004-08-26 Nippon Oil Corp フィッシャー・トロプシュ合成用触媒および炭化水素の製造法
JP2007529593A (ja) * 2004-03-16 2007-10-25 コンパクトジーティーエル パブリック リミテッド カンパニー 天然ガスのより長鎖の炭化水素への転換
US20080229654A1 (en) * 2005-08-29 2008-09-25 David Bradin Fuel Composition
WO2010119972A1 (fr) * 2009-04-14 2010-10-21 Ｇｇｉジャパン株式会社 Système et procédé de production de carburant btl
JP2015077575A (ja) * 2013-10-18 2015-04-23 岩谷産業株式会社 炭化水素合成触媒、それを用いた炭化水素製造装置、炭化水素製造方法
JP2022540531A (ja) * 2019-01-30 2022-09-16 グリーンフィールド・グローバル・インコーポレイテッド 合成ジェット燃料を製造する方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004519419A (ja) * 2000-07-24 2004-07-02 シェブロン ユー．エス．エー． インコーポレイテッド 留出燃料及び／又は潤滑油ベースオイル範囲の炭化水素のフィッシャー−トロプシュ合成を最適化する方法
JP2004237254A (ja) * 2003-02-07 2004-08-26 Nippon Oil Corp フィッシャー・トロプシュ合成用触媒および炭化水素の製造法
JP2007529593A (ja) * 2004-03-16 2007-10-25 コンパクトジーティーエル パブリック リミテッド カンパニー 天然ガスのより長鎖の炭化水素への転換
US20080229654A1 (en) * 2005-08-29 2008-09-25 David Bradin Fuel Composition
WO2010119972A1 (fr) * 2009-04-14 2010-10-21 Ｇｇｉジャパン株式会社 Système et procédé de production de carburant btl
JP2015077575A (ja) * 2013-10-18 2015-04-23 岩谷産業株式会社 炭化水素合成触媒、それを用いた炭化水素製造装置、炭化水素製造方法
JP2022540531A (ja) * 2019-01-30 2022-09-16 グリーンフィールド・グローバル・インコーポレイテッド 合成ジェット燃料を製造する方法

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