WO2025264573A2 - Améliorations apportées et se rapportant à la préparation de catalyseurs - Google Patents

Améliorations apportées et se rapportant à la préparation de catalyseurs

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Publication number
WO2025264573A2
WO2025264573A2 PCT/US2025/033804 US2025033804W WO2025264573A2 WO 2025264573 A2 WO2025264573 A2 WO 2025264573A2 US 2025033804 W US2025033804 W US 2025033804W WO 2025264573 A2 WO2025264573 A2 WO 2025264573A2
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catalyst
hydrotalcite
metal cation
fischer
source
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WO2025264573A3 (fr
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Alyssa LOVE
Stuart L. Soled
Yi Du
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ExxonMobil Technology and Engineering Co
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ExxonMobil Technology and Engineering Co
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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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B01J27/236—Hydroxy carbonates
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • 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
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy

Definitions

  • the present invention concerns a method of preparing a catalyst.
  • the invention also concerns a catalyst made by the method; and a process for producing a Fischer-Tropsch hydrocarbon product comprising the step of contacting the catalyst with synthesis gas.
  • BACKGROUND OF THE INVENTION [0002] Methane is available in large quantities in many areas of the world. Some methane is generated from refinery applications while large amounts of methane, as the principal constituent of natural gas, are found in deposits in various areas. [0003] Methane can be used directly as a gas for heating purposes and the like when the source of methane is relatively close to the end user.
  • Methane is also used as a starting material to produce hydrocarbons.
  • the conversion of methane is normally carried out in a two-step procedure involving reforming the methane to produce hydrogen and carbon monoxide i.e., synthesis gas (syngas), and then converting the syngas to higher hydrocarbons in a Fischer-Tropsch type reaction. Both steps of the process are well-known and can be readily illustrated: the first step by U.S. Pat. Nos. 1,711,036, 1,960,912 and 3,138,438; the second step by U.S. Pat. Nos.
  • 4,523,047 disclose employing a catalyst system comprising zeolite ZSM-45 in combination with tungsten, vanadium, molybdenum, rhodium, nickel, cobalt, chromium, manganese, platinum or lead to produce liquid hydrocarbons from syngas in a Fischer-Tropsch synthesis slurry reactor system.
  • Cobalt-containing catalysts are also well-known in the art for use in Fischer- Tropsch synthesis.
  • Payne et al., U.S. Pat. No. 4,542,122 disclose a catalyst composition comprising cobalt or thoria-promoted cobalt on a titania support for converting syngas to C 10 + linear paraffins and olefins.
  • No.4,544,671 high surface area iron- cobalt spinels which are fully reduced/carburized to selectively convert syngas to alpha- olefins
  • Fiato et al. U.S. Pat. No. 4,544,672 (reduced and carbided unsupported iron-cobalt single phase spinels containing low levels of cobalt to selectively produce low molecular weight olefins)
  • Fiato et al., U.S. Pat. No.4,544,674 alkali promoted iron-cobalt single phase spinels containing low levels of cobalt to selectively produce low molecular weight olefins
  • Soled et al. U.S. Pat.
  • No.4,477,595 describes employing ruthenium catalysts supported on titanium oxide, niobium oxide, vanadium oxide or tantalum oxide to produce C5 to C40 hydrocarbons in a Fischer-Tropsch hydrocarbon synthesis process; and Wachs et al., U.S. Pat. No.4,861,747 describe a catalyst comprising ruthenium supported on a non-crystalline surface-modified oxide containing titania support for producing substantially alcohol free hydrocarbon products having high concentrations of internal olefins in a Fischer-Tropsch hydrocarbon synthesis process.
  • cobalt-ruthenium catalysts for Fischer-Tropsch hydrocarbon synthesis have been described in, e.g., Iglesia et al., U.S. Pat. No.4,738,949 and Iglesia et al., U.S. Pat. No.4,822,824 (cobalt and ruthenium deposited on a titania support).
  • cobalt-ruthenium catalysts for Fischer-Tropsch hydrocarbon synthesis have been described in, e.g., Iglesia et al., U.S. Pat. No.4,738,949 and Iglesia et al., U.S. Pat. No.4,822,824 (cobalt and ruthenium deposited on a titania support).
  • copper promoted iron-manganese catalysts are described in Fiato et al., U.S. Pat. No. 4,618,597 for the conversion of CO/H 2 into alpha-olefins.
  • the iron-manganese spinels are prepared by utilizing an alpha-hydroxy aliphatic carboxylic acid which acts as a solubilizing agent for the iron and manganese salts in aqueous solution.
  • alpha-hydroxy aliphatic carboxylic acid which acts as a solubilizing agent for the iron and manganese salts in aqueous solution.
  • Representative examples of such acids are given as glycolic, malic, glyceric, mandelic, tartaric, lactic acids and mixtures thereof.
  • 4,624,968 disclose a two stage Fischer-Tropsch hydrocarbon synthesis process wherein an iron-based catalyst, e.g., iron/cesium/zinc/potassium, iron/manganese/potassium, iron/cobalt/potassium, is employed in the first stage to selectively produce olefins; and a ruthenium-based catalyst, e.g., ruthenium/titanium oxide, ruthenium/aluminium oxide, ruthenium/niobium oxide, ruthenium/silicon oxide, is employed in the second stage to selectively produce paraffins.
  • an iron-based catalyst e.g., iron/cesium/zinc/potassium, iron/manganese/potassium, iron/cobalt/potassium
  • ruthenium-based catalyst e.g., ruthenium/titanium oxide, ruthenium/aluminium oxide, ruthenium/niobium oxide, rut
  • CuCo2O4 and CoNiO4 show activity and selectivity for biacetyl formation.
  • Van der Riet et al. "Selective Formation of C 3 Hydrocarbons from CO+H2 using Cobalt-Manganese Oxide Catalysts," J. Chem. Soc., Chem. Commun., pp. 798-99 (1986) reports that selective formation of C 3 hydrocarbons is obtained when cobalt-manganese oxide catalysts are employed in hydrocarbon synthesis processes.
  • Clay minerals are composed of layers of metal or non-metal oxides and hydroxides stacked one on top of the other.
  • interlayer cations Na + , Ca 2+ etc.
  • the far less common anionic clays have positively charged metal oxide/hydroxide layers with anions located interstitially. Many of these are based on double hydroxides of such main group metals as Mg and Al and transition metals such as Ni, Co, Cr, Zn, Fe often together with Al.
  • These clays have a structure similar to brucite [Mg(OH)2] in which the divalent ions are octahedrally surrounded by hydroxyl groups with the resulting octahedra sharing edges to form infinite sheets.
  • some of the divalent ion is isomorphously replaced by a trivalent ion, such as Al 3+ .
  • the Mg 2+ , Al 3+ , OH- layers are then positively charged necessitating charge balancing by insertion of anions between the layers.
  • One such clay is hydrotalcite in which the carbonate ion is the interstitial anion.
  • Rhombohedral hydrotalcite has the idealized unit cell formula [Mg 6 Al 2 (OH) 16 ]CO 3 . 4H 2 O.
  • the ratio of Mg/Al in hydrotalcite can vary between 1.7 and 4 and various other divalent and trivalent ions may be substituted for the magnesium and aluminium.
  • the anion, which is carbonate in hydrotalcite can vary in both the naturally occurring and synthetic varieties being replaced by a variety of simple anions such as NO3-, Cl-, OH-, SO4 -2 etc. in naturally occurring varieties and by more complicated pillaring organic, inorganic, and organic-inorganic ion combinations in synthetic varieties.
  • Hydrotalcites containing the large pillaring anions are generally made by substituting a hydrotalcite containing a simple anion by the larger pillaring anion. Substitution techniques which have been used are ion exchange and acid treatment in the presence of the desired replacing anion. Through changes in the size of the pillar used to separate the sheets in the clay structure, the pore size of the clay may be tailored to a particular use. [0016] In U.S. Patent Nos.4,458,026 and 4,476,324 and “Catalytic reactions by thermally activated, synthetic, anionic clay minerals”, J.
  • EP 0536879 A1 describes locating metal oxo species in the anion layer in a hydrotalcite, with such anions as B(OH)4-, [B3O3(OH)4]-, [B3O3(OH)5] 2- , [B 4 O 5 (OH)4] 2- , V 2 O 7 4- V 4 O 12 4- , V 10 O 28 6- , as well as Nb 6 O 19 8- , HNb 6 O 19 7- , H 2 Nb 6 O 19 6- , NbO 4 3- , Ta6O19 8- , HTa6O19 7- ,TaO4 3- , Mo7O24 6- , HW6O21 5- , and Keggin-type ions such as PW11O39 7- and SiW 11 O 39 7- which are stable at a pH above about 6.
  • the present invention is primarily concerned with the Fischer-Tropsch reaction. To this end, the present invention provides an improved catalyst for selectively converting syngas to hydrocarbons. Despite the attempts to enhance the efficiency of Fischer-Tropsch synthesis using state-of-the-art catalysts, a need exists for the development of catalysts which under Fischer-Tropsch conditions selectively produce hydrocarbons, especially high molecular weight paraffins, with a high conversion rate of carbon monoxide and with low methane production. The present invention seeks to mitigate the above-mentioned need in the art.
  • the present invention provides, according to a first aspect, a method of preparing a catalyst comprising the steps of: a) contacting a source of a divalent metal cation Md 2+ and a source of a trivalent metal cation M t 3+ in an aqueous medium in the presence of carbonate anion CO 3 2- at a pH of at least 8.0 to form a mixture; b) maintaining the mixture under conditions suitable to crystallize a hydrotalcite; c) recovering the hydrotalcite; and d) reducing the recovered hydrotalcite by heating in a reducing atmosphere to produce the catalyst.
  • a catalyst made by the method of the first aspect.
  • a process of producing a Fischer-Tropsch hydrocarbon product comprising the step of contacting a catalyst of the second aspect with synthesis gas comprising hydrogen and carbon monoxide under conditions suitable for Fischer-Tropsch synthesis to generate the Fischer-Tropsch hydrocarbon product.
  • the divalent metal cation M d 2+ may be any divalent metal which has catalytic activity in the zero oxidation state, that is, when reduced to the metallic state.
  • the divalent metal cation M d 2+ is selected from the group consisting of Co 2+ , Ni 2+ , Fe 2+ , Cu 2+ , Zn 2+ and mixtures thereof .
  • the divalent metal cation M d 2+ is selected from the group consisting of Co 2+ , Ni 2+ , Cu 2+ , and mixtures thereof.
  • the divalent metal cation Md 2+ is selected from the group consisting of Co 2+ , Ni 2+ , Fe 2+ , Cu 2+ , Zn 2+ , Mg 2+ , Ca 2+ , and mixtures thereof.
  • the trivalent metal cation Mt 3+ is optionally selected from the group consisting of Al 3+ , Mn 3+ , Fe 3+ and mixtures thereof.
  • the trivalent metal cation M t 3+ is optionally selected from the group consisting of Al 3+ , Mn 3+ and mixtures thereof.
  • the trivalent metal cation Mt 3+ is selected from the group consisting of Al 3+ , Mn 3+ , Fe 3+ , Co 3+ , and mixtures thereof.
  • the trivalent metal cation Mt 3+ is Al 3+ .
  • source of a divalent metal cation M d 2+ is a source of Co 2+ and the source of a trivalent metal cation M t 3+ is a source of Al 3+ .
  • the source of aluminium cation is optionally selected from a group consisting of aluminium hydroxide, aluminium trihydroxide, (boehmites and pseudoboehmites), basic aluminium carbonate, aluminium hydroxide-alkali carbonate complex, aluminium aminoacid salt, aluminium alcoholate, water-soluble aluminium salts, and water-soluble aluminate.
  • the source of divalent metal cation M d 2+ is optionally selected from a group consisting of oxides, hydroxides, carbonates and water soluble salts, e.g., cobalt cation is optionally selected from a group consisting of cobalt oxide, cobalt hydroxide, cobalt carbonate and water soluble cobalt salts.
  • the source of the divalent cation M d 2+ and the source of the trivalent metal cation Mt 3+ may both be soluble in water such that the mixture formed in step a) is an aqueous solution.
  • one or both of the source of the divalent cation M d 2+ and the source of the trivalent metal cation Mt 3+ may be insoluble in water such that the mixture formed in step a) is a solid-liquid mixture, for example, a slurry.
  • water-soluble sources of aluminium may include aluminium sulphate, aluminium chloride, aluminium nitrate, aluminium acetate, and alkali aluminates, such as sodium aluminate.
  • water insoluble sources of aluminium are gamma, theta or alpha alumina, alumina oxyhydroxide including boehmite and pseudoboehmite or aluminium trihydroxides, including bayerite and gibbsite. It is possible to form aluminium hydroxide, aluminium hydroxide-alkali carbonate complexes, basic aluminium carbonate or aluminium aminoacids, salts in situ, preceding the described catalyst synthesis.
  • the source of a divalent metal cation M d 2+ and the source of a trivalent metal cation Mt 3+ are contacted in an aqueous medium in the presence of carbonate anion CO3 2- at a pH of at least 8.0, optionally at least 9.5, for example in the range of from 8.0 to 13.0, for example a pH in the range of from 9.5 to 11.0, to form a mixture capable of producing a hydrotalcite when heated in step b).
  • the carbonate anion may originate as a counterion present in the source of a divalent metal cation M d 2+ and/or the source of a trivalent metal cation M t 3+ .
  • a separate source of carbonate anion may be added to the aqueous medium in step a).
  • Such procedure may advantageously be omitted when the carbonate salt of the divalent metal cation Md 2+ and/or the trivalent metal cation Mt 3+ is used, since in those cases the reaction system may contain sufficient carbonate anion.
  • alkaline substances such as an alkali metal hydroxide, for example, sodium hydroxide, and/or an alkali metal carbonate such as sodium carbonate may be added to the aqueous medium.
  • a water-soluble trivalent metal cation Mt 3+ salt e.g., aluminium salt
  • a water-soluble divalent metal cation M d 2+ salt e.g., cobalt, nickel, or copper salt
  • the divalent metal cation Md 2+ and trivalent metal cation M t 3+ are used in stochiometric ratio.
  • the source of a divalent metal cation Md 2+ and a source of a trivalent metal cation Mt 3+ are soluble in water
  • the mixture formed in step a) may therefore be an aqueous solution if the source of a divalent metal cation M d 2+ and the source of a trivalent metal cation M t 3+ are both soluble in water or may be an aqueous suspension or slurry if one or both of those is insoluble in water.
  • step b) the conditions suitable for crystallizing a hydrotalcite will depend on the particular source of a divalent metal cation M 2+ and a source of a trivalent metal c 3+ d ation Mt employed.
  • the temperature is optionally in the range of from about 0 °C to about 300 °C, optionally in the range of from 0 °C to about 200 °C, optionally 100 °C to 200 °C.
  • the duration of step b) will depend on the temperature and on the particular source of a divalent metal cation M d 2+ and source of a trivalent metal cation M t 3+ used, but is optionally in the range of from 1 hour to 48 hours.
  • the resulting hydrotalcite crystallized in step b) optionally has a structure according to formula (I): M 2+ 3+ d aMt b(OH)(2a+2b)(CO3)b/2 (I) wherein M d 2+ is a divalent metal cation; M t 3+ is a trivalent metal cation; and the ratio of a and b is in the range of from about 2.0 : 1.0 to about 4.5 : 1.0, optionally in the range from 2.0 : 1.0 to 4.1 : 1.0, for example in the range from 2.5 : 1.0 to 3.5 : 1.0.
  • Md 2+ is optionally selected from the group consisting of Co 2+ , Ni 2+ , Fe 2+ , Cu 2+ , Zn 2+ and mixtures thereof.
  • Mt 3+ is optionally selected from the group consisting of Al 3+ , Mn 3+ , Fe 3+ and mixtures thereof.
  • the hydrotalcite has the formula M d 2+ 3 M t 3+ 1 (OH) 8 (CO 3 ) 0.5 , e.g., Co3Al1(OH)8(CO3)0.5.
  • copper or nickel can form aluminium containing hydrotalcites with ratios in the same range of from about 2.0 : 1.0 to about 4.5 : 1.0, optionally in the range from 2.0 : 1.0 to 4.1 : 1.0, for example in the range from 2.5 : 1.0 to 3.5 : 1.0 by similar types of reactions as described for cobalt.
  • solutions of water- soluble nickel salts or copper salts such as nickel nitrate or copper nitrate together with water- soluble aluminium compounds may be dissolved in water and precipitated with sodium hydroxide with air present.
  • the water-soluble nickel salts or copper salts may be mixed with sodium hydroxide and sodium carbonate.
  • step c) the hydrotalcite crystallized in step b) may be recovered from the mixture by any suitable means, for example, by known solid-liquid separation means such as filtration or centrifugation, optionally followed by drying to provide the dry hydrotalcite.
  • the hydrotalcite formed can be easily identified with X-ray diffraction.
  • step d) the recovered hydrotalcite is reduced by heating in a reducing atmosphere to produce the catalyst.
  • the catalyst has the formula of any one of formulas (II), (III) or (IV), or is a mixture thereof: M 0 d aM3+ t bO3b/2 (II); M 0 M2+ d a t bOb (III); M 0 d aM0 t b (IV).
  • the catalyst has the formula (II) when only the divalent metal cation M d 2+ is fully reduced and the trivalent metal cation Mt 3+ is not reduced.
  • the catalyst has the formula (III) when the divalent metal cation M d 2+ is fully reduced and the trivalent metal cation Mt 3+ is reduced to become divalent.
  • the catalyst has the formula (IV) when both the divalent M d 2+ and trivalent metal cations M t 3+ are fully reduced.
  • All the first row transition metal hydrotalcites may be reduced in a flowing stream of hydrogen gas at temperatures of at or above about 600 °C.
  • the hydrotalcite may be heated in step d) to a temperature of at least 400 °C, optionally at least 550 °C, for example at or above 600 °C.
  • the heating takes place in a reducing atmosphere, for example, an atmosphere comprising hydrogen.
  • the reducing atmosphere is hydrogen.
  • an intermediate structure may be formed prior to the reduction.
  • references herein to reducing the recovered hydrotalcite by heating in a reducing atmosphere should be understood to include converting the hydrotalcite to an intermediate form having the rock salt structure and then reducing such an intermediate having a rock salt structure by heating in a reducing atmosphere.
  • the inventors have found that the catalyst particles so formed may be smaller than those that would be formed by a calcination of the corresponding carbonates or nitrate precursors (without the presence of the trivalent cation Mt 3 and/or without the hydrotalcite structure) at the same temperature, followed by reduction in a reducing atmosphere, indicating that the presence of trivalent metal cation Mt 3+ may promote increased metal surface area in the resulting catalyst.
  • the concentration of the reduced metal derived from the divalent metal ion Md 2+ may be higher than is generally possible to obtain in catalysts prepared by conventional methods such as impregnation of a support material. Such high metal loadings with small metal particle sizes are desirable as catalysts for Fischer Tropsch synthesis of hydrocarbons.
  • the catalyst made by the method of the invention may have an average particle diameter of no more than 300 ⁇ , optionally no more than 200 ⁇ .
  • the catalyst optionally has an average particle diameter in the range of about 50 ⁇ to 200 ⁇ , optionally in the range of from 80 ⁇ to about 120 ⁇ , optionally in the range of from about 90 ⁇ to about 110 ⁇ , such as about 100 ⁇ .
  • the synthesis gas feed used in typical Fischer-Tropsch processes can comprise a mixture of H2 and CO wherein H2 : CO are present in a ratio of at least about 1.7, preferably at least about 1.75, more preferably 1.75 to 2.5, such as at least about 2.1 and/or about 2.1 or less.
  • Fischer-Tropsch processes can be implemented in a variety of systems such as fixed bed, slurry bed, and multiple channel designs. In various aspects, Fischer-Tropsch processes can be employed in a wide variety of reactors, such as small reactors (e.g.1+ barrel/day) or in very large reactors (e.g. 10,000-50,000 barrels/day or more).
  • Fischer- Tropsch process When the goal of the Fischer- Tropsch process is synthesis of longer chain molecules, such as compounds suitable for use as a naphtha feed, a diesel feed, or other distillate boiling range molecules, some small (C 1 –C 4 ) alkanes, olefins, oxygenates, and/or other hydrocarbonaceous compounds may be incorporated into the tail gas.
  • the primary products from Fischer-Tropsch synthesis can be used directly, and/or can undergo further processing, as desired.
  • a Fischer-Tropsch synthesis process for forming distillate boiling range molecules can generate one or more product streams that can subsequently be dewaxed and/or hydrocracked in order to generate final products, e.g. with desired chain lengths, viscosities, and cold flow properties.
  • Example 2 Preparation of cobalt- and aluminium-containing hydrotalcites
  • a series of cobalt/aluminium hydrotalcites with varying Co/Al ratios and base additions were prepared, as shown in Table 1.
  • the synthesis of Co3Al hydrotalcite i.e.
  • Clause 4 The method of Clause 1, i) wherein M d 2+ is selected from the group consisting of Ca 2+ , Mg 2+ , Co 2+ , Ni 2+ , Fe 2+ , Cu 2+ , Zn 2+ and mixtures thereof; ii) wherein M t 3+ is selected from the group consisting of Co 3+ , Al 3+ , Mn 3+ , Fe 3+ and mixtures thereof; or iii) a combination of i) and ii).
  • Clause 8 The method of any one of Clauses 1 to 7, wherein the hydrotalcite has the formula: Co 3 Al 1 (OH) 8 (CO 3 ) 0.5 ; and the catalyst has the formula: Co 3 Al 1 O 1.5 .
  • Clause 9 The method of any one of Clauses 1 to 8, wherein the source of the divalent cation Md 2+ and the source of the trivalent metal cation Mt 3+ are soluble in water such that the mixture in step a) is an aqueous solution.
  • Clause 15 A process of producing a Fischer-Tropsch hydrocarbon product comprising the step of contacting a catalyst made by a method according to any of Clauses 1 to 13 or a catalyst according to Clause 14 with synthesis gas comprising hydrogen and carbon monoxide under conditions suitable for Fischer-Tropsch synthesis to generate the Fischer- Tropsch hydrocarbon product.
  • Clause 16 A process according to Clause 15 wherein the conditions suitable for Fischer-Tropsch synthesis include a temperature of about 150 °C to about 320 °C and a pressure in the range of from about 100 kPaa to about 10 MPaa.

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Abstract

La présente invention concerne un procédé de préparation d'un catalyseur par préparation d'une hydrotalcite de formule : Md 2+ aMt 3+ b(OH)(2a+2b)(CO3)b/2 ; Md 2+ étant un cation métallique divalent ; Mt 3+ étant un cation métallique trivalent ; et le rapport entre a et b étant dans la plage d'environ 2,0:1,0 à environ 4,5:1,0 ; puis la réduction de l'hydrotalcite par chauffage dans une atmosphère réductrice à une température d'au moins 600 °C pour produire le catalyseur, le catalyseur ayant la formule de l'une quelconque des formules : Md 0 aMt 3+ bO3b/2; Md 0 aMt 2+ bOb ; ou Md 0 aMt 0 b. L'invention concerne également un catalyseur fabriqué par le procédé ; et un procédé de production d'un produit hydrocarboné Fischer-Tropsch comprenant l'étape de mise en contact du catalyseur avec un gaz de synthèse.
PCT/US2025/033804 2024-06-21 2025-06-16 Améliorations apportées et se rapportant à la préparation de catalyseurs Pending WO2025264573A2 (fr)

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