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WO2018141646A1 - Catalyseurs de méthanation au nickel dopés par le fer et le manganèse - Google Patents

Catalyseurs de méthanation au nickel dopés par le fer et le manganèse Download PDF

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Publication number
WO2018141646A1
WO2018141646A1 PCT/EP2018/051993 EP2018051993W WO2018141646A1 WO 2018141646 A1 WO2018141646 A1 WO 2018141646A1 EP 2018051993 W EP2018051993 W EP 2018051993W WO 2018141646 A1 WO2018141646 A1 WO 2018141646A1
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Prior art keywords
catalyst
precipitate
solution
methanation
carbon dioxide
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PCT/EP2018/051993
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German (de)
English (en)
Inventor
Klaus Koehler
Oliver THOMYS
Kai-Olaf Hinrichsen
Franz KOSCHANY
Thomas Burger
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Clariant Produkte (Deutschland) Gmbh
Wacker Chemie Ag
Technische Universität München
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Publication of WO2018141646A1 publication Critical patent/WO2018141646A1/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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/745—Iron
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B01J37/06—Washing
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • 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
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
    • 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
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/0445—Preparation; Activation
    • 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
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/745—Iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/889—Manganese, technetium or rhenium

Definitions

  • the energy supply through the so-called renewable energy photovoltaic and wind energy suffers from the problem of weather and daytime dependent fluctuations in electricity production.
  • a way has to be found to intercept weather and time-dependent fluctuations in electricity production.
  • One potential method of chemically storing the energy is the power-to-gas process, which uses excess electricity to split water into hydrogen and oxygen by electrolysis. Hydrogen in which the energy is stored after the electrolysis of water can itself be stored only with great effort or transported to the consumer. After the power-to-gas process, the hydrogen is therefore converted in a further step with carbon dioxide, which acts in the atmosphere as a greenhouse gas harmful to the climate, in the methanation reaction to methane and water.
  • Methane can be easily stored in existing infrastructures, which have capacities for storage in the range of several months, can be transported almost lossless over longer distances and can be reconverted in times of energy demand.
  • the methanation reaction which is associated with high energy release and usually catalyzes, forms the heart of the process.
  • the high exothermicity of the reaction (-165 kJ / mol) gives rise to two direct problems.
  • the thermodynamic equilibrium limits the maximum achievable methane yield at high temperatures.
  • a high level of purity is necessary for the feeding of methane into the natural gas network.
  • there is a demand for high catalyst activity and selectivity so that higher yields of methane can be achieved at industrially applied reaction pressures at low temperatures.
  • catalysts which contain not only an active metal, but are promotiert. It is known from the literature that a promotion with iron or manganese can have a positive influence on the catalyst performance.
  • a doping of nickel-based methanation catalysts with manganese is described, for example, in CN 103464163 A, CN 103752315 A, CN 102600860 A, CN 102553610 A, CN 102527405 A, CN 102513124 A, CN 102463120 A and CN 1024631 19 A and by Zhao et al. , Journal of Natural Gas Chemistry (2012), 21 (2), 170-177.
  • a doping of nickel-based methanation catalysts with iron is described, for example, in CN 104399482 A, CN 104399466 A, CN 104209127 A, CN 102872874 A, CN 101703933 A, CN 101537357 A and WO 2007025691 A1 and by Pandey et al., Journal of Industrial and Engineering Chemistry (2016), 33, 99-107 and Gao et al., RSC Advances (2015), 5 (29), 22759-22776.
  • CN 103706366 A describes a catalyst comprising 15 to 55% an active component, 1 to 6% of a 1. catalytic promoter, 3 to 15% of a second catalytic promoter and, moreover, a catalytic support, wherein the active component is nickel oxide, the catalytic support is Al 2 O 3 , the 1.
  • the catalytic promoter is one selected from lanthanum oxide, cerium oxide or samarium oxide
  • the second catalytic promoter is at least one of magnesium oxide, manganese oxide, iron oxide and zirconium oxide.
  • the production method comprises the steps of dissolving a reducing agent in water to obtain a reducing solution, mixing in nickel nitrate, aluminum nitrate, the 1. Metal salt and the 2nd metal salt in water to obtain a raw material solution, and adding the reducing mixture to the raw material solution with uniform stirring to obtain a 1.
  • the metal salt is one selected from lanthanum nitrate, cerium nitrate and samarium nitrate
  • the second metal salt is at least one selected from magnesium nitrate, manganese nitrate, iron nitrate and zirconium nitrate
  • the alkali solution is an aqueous solution of sodium carbonate, sodium hydroxide, potassium carbonate, ammonium carbonate, urea or NH 3 * H 2 0 is.
  • the catalyst may be mixed with a binder (calcium aluminate), a lubricant (graphite) and water and then pressed in particulate form.
  • the catalyst is suitable for methanating coal gas at high temperature and high pressure to produce synthetic natural gas.
  • CN 104028270 A discloses a methanation catalyst comprising 5 to 60 wt .-% of a catalytically active NiO component, based on the total weight of the catalyst and otherwise Al 2 0 3 , which also 1 to 25 wt .-%, based on the total weight of Catalyst, may participate in participating component M, wherein the co-acting component M is selected from one or more oxides of the metals Ce, Ca, Co, La, Sm, Zr, Ba, Mn, Fe, Mo, Ti and Cu.
  • the document also provides a method of preparing the methanation catalyst which comprises admixing the precursor of the catalytically active component, precursor of the co-acting component M, and a catalyst support according to the proportion in the methanation catalyst composition of an organic fuel and thoroughly mixing and drying to form a gel-like product, carrying out a combustion reaction, cleaning and drying to obtain the final product.
  • CN 101745401 discloses a supported sulfur-resistant methanation catalyst characterized by comprising a main metal M as the active component, a second metal M1 as an excipient and S as a support material, wherein the weight ratio between M1, M and S is between 0.01 to 39 : 1 to 30: 0.01 to 90, M is one or more of Mo, W and / or V, the second metal M1 is one or more of Fe, Co, Ni, Cr, Mn, La, Y or / and Ce and the support S is Zr0 2 , Al 2 0 3 , MgO or Ti0 2 .
  • the supported sulfur-resistant methanation catalyst is prepared by a sol-gel method. It is an object of the invention to provide a methanation catalyst for the methanation of carbon monoxide and / or carbon dioxide, which has a high selectivity compared to the catalysts of the prior art improved activity and stability.
  • a catalyst for the methanation of carbon monoxide and / or carbon dioxide comprising aluminum oxide and a Ni active composition, and Fe and Mn, characterized in that the molar Ni / Fe ratio in the catalyst is 5.0 to 10.0, preferably 5.3 to 7.0 and more preferably 5.4 to 5.7.
  • the stability of the catalyst in the sense of the application means the property of the catalyst to deactivate as little as possible under reaction conditions and to maintain the high selectivity / activity as far as possible.
  • the alumina need not be stoichiometric Al 2 O 3, but may be a non-stoichiometric alumina.
  • the molar Ni / Mn ratio in the catalyst is 5.0 to 32.0, preferably 9.0 to 11.0, more preferably 10 to 10.6, or else 27 to 34, preferably 28 to 32 is.
  • catalysts having a Ni / Mn and Ni / Fe ratio (each in this order) 9.3 to 9.8 and 6.6 to 7.1; 29 to 30 and 6.6 to 7.1; 9.5 to 10.1 and 5.1 to 5.9; and 26 to 27 and 4.9 to 5.9.
  • the catalysts having the following Ni / Mn and Ni / Fe ratios (each in that order): 9.4 and 6.8; 29.5 and 6.9; 9.8 and 5.6; as well as 26.5 and 5.4.
  • the promoters Fe and Mn may be contained completely or partially in the Ni active material.
  • the catalyst may contain further promoters in addition to Mn and Fe, but it may also contain exclusively the promoters Mn and Fe.
  • the oxidation states of Al, Ni and the promoters can vary depending on the treatment of the catalyst.
  • Al, Ni and the promoters are typically present as metal cations (eg Al 3+ , Ni 2+ , Mn 2+ , Mn 3+ , Mn 4+ , Fe 2+ , Fe 3+ ).
  • the catalyst of the present invention may contain other components in addition to alumina (i.e., Al xx of x ⁇ 1.5) Ni, Fe, and Mn (as well as the oxygen anions necessary for charge balance), but may be composed solely of alumina Ni, Fe, and Mn.
  • the catalyst does not contain any of the elements selected from Ta, In, Cu, Ce, Cr, Bi, P, Sb, Sn, B, Si, Ti, Zr, Co, Rh, Ru, Ag, Ir, Pd and Pt.
  • the catalyst does not contain a noble metal.
  • the atomic Al / Ni ratio may be between 0.5 and 1.5, preferably between 0.8 and 1.2, more preferably the Al / Ni ratio is approximately 1.
  • the catalysts according to the invention can advantageously have crystallites in the Ni active composition with a diameter of less than 20 nm, preferably less than 10 nm.
  • the Ni active composition may also consist wholly or substantially of crystallites having a diameter of less than 20 nm, preferably less than 10 nm.
  • the Ni active material is preferably in a metallic state.
  • the C0 2 absorption capacity of the catalysts at 35 ° C may be greater than 200 ⁇ / g and is preferably in the range between 200 to 400 ⁇ / g, more preferably, between 250 to 300 ⁇ / g.
  • the BET surface area of the catalyst according to the invention is preferably greater than 100 m 2 / g, preferably greater than 200 m 2 / g, in particular in the range between 200 and 400 m 2 / g and in particular in the range between 200 and 300 m 2 / g.
  • the specific metal surface area (Swiet) of the catalyst according to the invention may be greater than 5 m 2 / g, preferably greater than 10 m 2 / g, or between 5 and 25 m 2 / g, preferably between 10 and 20 m 2 / g, or in the range between 6 and 9 m 2 / g.
  • the invention relates to a process for the preparation of a methanation catalyst, comprising the steps:
  • step d) calcining the dried precipitate from step c).
  • the solution from step a) is an aqueous solution and Al, Ni, Mn and Fe are present dissolved in the aqueous solution as ionic compounds.
  • Al is preferably dissolved as aluminum nitrate, aluminum trichloride or aluminum sulfate.
  • Mn is preferably present in the oxidation state II or IV and is dissolved as manganese nitrate, manganese acetate, manganese dichloride, manganese sulfate or in the oxidation state VII as a permanganate ion.
  • Ni is preferably dissolved as nickel nitrate, nickel dichloride, nickel sulfate, nickel acetate or nickel carbonate.
  • Fe is preferably in the oxidation state II or III and is dissolved as iron nitrate, iron or trichloride, iron acetate, iron sulfate or iron hydroxide.
  • Al, Ni, Mn and Fe are in dissolved form as ionic compounds in the aqueous solution and have the same anion, which may be, for example, nitrate.
  • the coprecipitation is carried out by adding the solution containing Al, Ni, Mn and Fe to a basic solution or by adding a basic solution to the solution which contains Al, Ni, Mn and Fe.
  • the solution containing Al, Ni, Mn and Fe and the basic solution are simultaneously added to a vessel which may already contain a solvent such as water and is mixed therein.
  • the basic solution has a pH greater than 7, preferably in the range from 8 to 10, and preferably contains an alkali hydroxide and / or an alkali carbonate.
  • the basic solution is an aqueous solution of sodium hydroxide and sodium carbonate.
  • the coprecipitation is preferably carried out under temperature control, so that the temperature of the solution is approximately room temperature or, for example, 30 ° C.
  • the precipitate in the solution is aged for at least 30 minutes, preferably for more than 1 hour, more preferably for longer than 12 hours.
  • the aging preferably takes place in that the precipitate is left in the solution (mother liquor) with stirring at approximately room temperature.
  • the precipitate obtained by the coprecipitation is isolated, for example by filtering.
  • the filtering can be done in a suitable manner, for example by a filter press.
  • the isolated precipitate is preferably washed, for example with distilled water, until a neutral pH is reached.
  • the isolated precipitate can be dried, for example at elevated temperature in air.
  • the drying takes place at a temperature between 70 ° C and 90 ° C for a period longer than 4 hours, preferably longer than 12 hours.
  • the isolated precipitate is calcined, this can be done in air at a temperature between 300 ° C to 600 ° C, preferably at 400 ° C to 500 ° C and in a period of 3 hours to 10 hours, preferably 5 to 7 hours.
  • the catalyst according to the invention is intended to be used in particular in the methanation of carbon monoxide and / or carbon dioxide.
  • the methanation of carbon dioxide can be represented by the following reaction equation:
  • the methanation of carbon monoxide can be represented by the following reaction equation:
  • the reaction gas containing carbon dioxide and / or carbon monoxide or a mixture of both is contacted with the catalyst at a temperature higher than 200 ° C.
  • FIG. 1 activity / stability diagram of the samples described.
  • the determination of the composition of the calcined catalysts was carried out by means of inductively coupled plasma optical emission spectroscopy (ICP-OES). 50 mg of catalyst were dissolved in 50 ml of 1 molar phosphoric acid (VWR, pA) at 60 ° C. To dissolve any brownstone formed, 50 mg Na 2 S0 3 (Sigma Aldrich, pA) was added to the solution. After cooling, the solutions were diluted 1/10 and filtered by 0.1 ⁇ filters (Pall). The calibration solutions were prepared at 1, 10 and 50 mg I -1 (Merck). Determination of metal concentrations was performed using an Agilent 700 ICP-OES. Determination of the specific surface
  • the specific surface area of the catalysts was determined by N 2 -BET analysis on a NOVA 4000e (Quantachrome). For this purpose, 100 mg of catalyst were degassed for 3 hours at 120 ° C and then absorbed adsorption and Desorptionsiso- therme in the p / p 0 range of 0.007 to 1. To determine the BET surface area, the data points in the p / p 0 range of 0.007 to 0.28 were used.
  • the catalysts were prepared by coprecipitation and the atomic ratio of nickel and aluminum was adjusted to 1.
  • iron (III) nitrate was added to the salt solution of nickel and aluminum nitrate during catalyst synthesis.
  • manganese nitrate and iron (III) nitrate were added to the salt solution of nickel and aluminum nitrate during the catalyst synthesis.
  • the purity of all the chemicals used was pa Water was purified by a Millipore filter system and the degree of purity was verified by means of conductivity measurements. The synthesis was carried out in a double-walled, 3 l stirred tank.
  • the double jacket which was filled with water, controlled the temperature of the synthesis batch to 30 ° C via a thermostat, and two flow breakers provided for improved mixing.
  • a KPG stirrer with 150 revolutions min -1 was used.
  • the dosage of the mixture of dissolved nitrates was 2.5 ml min -1 .
  • the controlled addition of the precipitating reagent was used to maintain the pH.
  • T 7 5 As a measure of the activity was representative temperature T 7 5, i determined, which is necessary in order to achieve a CC conversion of 75% during the measuring step S-curve 1.
  • T 7 5 the temperature in the specified range was gradually increased by 25 ° C. Therefore, the lower T 7 5, i, the higher the activity of the catalyst.
  • the temperature T 7 5.2 was determined representative, which is necessary to achieve a CC conversion of 75% during the measuring step S-curve. 2
  • the temperature in the specified range was gradually increased by 25 ° C.

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  • Catalysts (AREA)

Abstract

L'invention concerne un catalyseur de méthanation de monoxyde de carbone et/ou de dioxyde de carbone, comprenant de l'oxyde d'aluminium, une masse active de Ni ainsi que du Fe et du Mn. Ce catalyseur est caractérisé en ce que le rapport molaire Ni/Fe dans ledit catalyseur est compris entre 5,0 et 10,0, de préférence entre 5,3 et 7,0 et de préférence encore entre 5,4 et 5,7. Ce catalyseur présente de préférence un rapport molaire Ni/Mn compris entre 5,0 et 32,0, de préférence entre 9,0 et 10,0. Ce catalyseur est caractérisé par une activité et une stabilité améliorées. L'invention concerne également un procédé de fabrication d'un catalyseur selon l'invention, comprenant les étapes suivantes : a) coprécipitation à partir d'une solution contenant les éléments Al, Ni, Mn et Fe sous forme dissoute de manière à obtenir un précipité, b) isolement du précipité obtenu à l'étape a), c) séchage du précipité isolé obtenu à l'étape b) et d) calcination du précipité séché obtenu à l'étape c).
PCT/EP2018/051993 2017-01-31 2018-01-26 Catalyseurs de méthanation au nickel dopés par le fer et le manganèse WO2018141646A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109759061A (zh) * 2019-01-03 2019-05-17 浙江工业大学 一种γ-Fe2O3晶型的FeAl氧化物及其制备方法
CN113101930A (zh) * 2021-03-12 2021-07-13 中南大学 珊瑚状形貌的铁酸铜类芬顿催化剂的制备及其在垃圾渗滤液类芬顿催化氧化中的用途
CN115672331A (zh) * 2021-07-23 2023-02-03 国家能源投资集团有限责任公司 甲烷化催化剂及其制备方法和应用

Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007025691A1 (fr) 2005-09-02 2007-03-08 Haldor Topsøe A/S Procede et catalyseur pour l'hydrogenation d'oxydes de carbone
WO2008110331A1 (fr) 2007-03-13 2008-09-18 Umicore Ag & Co. Kg Oxydes de nickel dopés par un métal comme catalyseurs pour la méthanation du monoxyde de carbone
CN101537357A (zh) 2009-04-28 2009-09-23 中国科学院山西煤炭化学研究所 一种合成气制甲烷催化剂及制备方法和应用
CN101703933A (zh) 2009-11-06 2010-05-12 山西大学 一种双金属甲烷化催化剂及其制备方法
CN101745401A (zh) 2009-12-07 2010-06-23 中国科学院山西煤炭化学研究所 一种负载型耐硫甲烷化催化剂及制备方法和应用
CN102091629A (zh) 2009-12-09 2011-06-15 中国科学院兰州化学物理研究所 二氧化碳甲烷化催化剂
CN102259003A (zh) 2011-05-31 2011-11-30 武汉科林精细化工有限公司 一种焦炉气甲烷化催化剂及其制备方法
CN102463119A (zh) 2010-11-05 2012-05-23 中国石油化工股份有限公司 一种甲烷化催化剂及其制备方法
CN102463120A (zh) 2010-11-05 2012-05-23 中国石油化工股份有限公司 一种含镍和锰的催化剂及其制备方法和应用
CN102513124A (zh) 2011-12-15 2012-06-27 大连凯特利催化工程技术有限公司 一种用于焦炉煤气甲烷化的催化剂及其制备方法
CN102527405A (zh) 2012-02-15 2012-07-04 华东理工大学 一种高温合成气完全甲烷化催化剂及其制备方法
CN102553610A (zh) 2010-12-30 2012-07-11 中国科学院大连化学物理研究所 一种用于合成气制甲烷并联产油品的催化剂、其制备和应用方法
CN102600860A (zh) 2012-02-15 2012-07-25 华东理工大学 适用于中低温合成气完全甲烷化的催化剂及其制备方法
CN102872874A (zh) 2012-09-19 2013-01-16 太原理工大学 一种用于浆态床甲烷化负载型镍基催化剂及其制法和应用
CN103464163A (zh) 2013-08-27 2013-12-25 中国华能集团清洁能源技术研究院有限公司 无机铵盐燃烧法制备甲烷化催化剂的方法
CN103480375A (zh) 2013-09-29 2014-01-01 福州大学 一种一氧化碳甲烷化催化剂及其制备方法
CN103706366A (zh) 2013-12-18 2014-04-09 中国海洋石油总公司 一种新型甲烷化催化剂及其制备方法
CN103752315A (zh) 2014-01-15 2014-04-30 易高环保能源研究院有限公司 一种金属相载体负载型催化剂及其制备方法和用途
CN104028270A (zh) 2014-06-10 2014-09-10 中国华能集团清洁能源技术研究院有限公司 一种甲烷化催化剂及其制备方法
CN104043454A (zh) 2014-06-10 2014-09-17 中国华能集团清洁能源技术研究院有限公司 一种新型纳米复合甲烷化催化剂及其制备方法
CN104209127A (zh) 2013-06-05 2014-12-17 中国石油天然气股份有限公司 一种镍铁双金属甲烷化催化剂及其制备和应用
CN104399482A (zh) 2014-11-13 2015-03-11 大连理工大学 用于甲烷化的含铁天然矿石负载镍催化剂及其制备方法
CN104399466A (zh) 2014-11-13 2015-03-11 大连理工大学 一种含铁天然矿石负载镍的甲烷化催化剂及其制备方法
CN104888783A (zh) 2014-03-03 2015-09-09 中国石油化工股份有限公司 一种甲烷化催化剂及其制备方法和应用
CN106268858A (zh) * 2016-07-16 2017-01-04 中国科学院山西煤炭化学研究所 一种高性能二氧化碳加氢甲烷化的催化剂及制法和应用

Patent Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007025691A1 (fr) 2005-09-02 2007-03-08 Haldor Topsøe A/S Procede et catalyseur pour l'hydrogenation d'oxydes de carbone
WO2008110331A1 (fr) 2007-03-13 2008-09-18 Umicore Ag & Co. Kg Oxydes de nickel dopés par un métal comme catalyseurs pour la méthanation du monoxyde de carbone
CN101537357A (zh) 2009-04-28 2009-09-23 中国科学院山西煤炭化学研究所 一种合成气制甲烷催化剂及制备方法和应用
CN101703933A (zh) 2009-11-06 2010-05-12 山西大学 一种双金属甲烷化催化剂及其制备方法
CN101745401A (zh) 2009-12-07 2010-06-23 中国科学院山西煤炭化学研究所 一种负载型耐硫甲烷化催化剂及制备方法和应用
CN102091629A (zh) 2009-12-09 2011-06-15 中国科学院兰州化学物理研究所 二氧化碳甲烷化催化剂
CN102463119A (zh) 2010-11-05 2012-05-23 中国石油化工股份有限公司 一种甲烷化催化剂及其制备方法
CN102463120A (zh) 2010-11-05 2012-05-23 中国石油化工股份有限公司 一种含镍和锰的催化剂及其制备方法和应用
CN102553610A (zh) 2010-12-30 2012-07-11 中国科学院大连化学物理研究所 一种用于合成气制甲烷并联产油品的催化剂、其制备和应用方法
CN102259003A (zh) 2011-05-31 2011-11-30 武汉科林精细化工有限公司 一种焦炉气甲烷化催化剂及其制备方法
CN102513124A (zh) 2011-12-15 2012-06-27 大连凯特利催化工程技术有限公司 一种用于焦炉煤气甲烷化的催化剂及其制备方法
CN102600860A (zh) 2012-02-15 2012-07-25 华东理工大学 适用于中低温合成气完全甲烷化的催化剂及其制备方法
CN102527405A (zh) 2012-02-15 2012-07-04 华东理工大学 一种高温合成气完全甲烷化催化剂及其制备方法
CN102872874A (zh) 2012-09-19 2013-01-16 太原理工大学 一种用于浆态床甲烷化负载型镍基催化剂及其制法和应用
CN104209127A (zh) 2013-06-05 2014-12-17 中国石油天然气股份有限公司 一种镍铁双金属甲烷化催化剂及其制备和应用
CN103464163A (zh) 2013-08-27 2013-12-25 中国华能集团清洁能源技术研究院有限公司 无机铵盐燃烧法制备甲烷化催化剂的方法
CN103480375A (zh) 2013-09-29 2014-01-01 福州大学 一种一氧化碳甲烷化催化剂及其制备方法
CN103706366A (zh) 2013-12-18 2014-04-09 中国海洋石油总公司 一种新型甲烷化催化剂及其制备方法
CN103752315A (zh) 2014-01-15 2014-04-30 易高环保能源研究院有限公司 一种金属相载体负载型催化剂及其制备方法和用途
CN104888783A (zh) 2014-03-03 2015-09-09 中国石油化工股份有限公司 一种甲烷化催化剂及其制备方法和应用
CN104028270A (zh) 2014-06-10 2014-09-10 中国华能集团清洁能源技术研究院有限公司 一种甲烷化催化剂及其制备方法
CN104043454A (zh) 2014-06-10 2014-09-17 中国华能集团清洁能源技术研究院有限公司 一种新型纳米复合甲烷化催化剂及其制备方法
CN104399482A (zh) 2014-11-13 2015-03-11 大连理工大学 用于甲烷化的含铁天然矿石负载镍催化剂及其制备方法
CN104399466A (zh) 2014-11-13 2015-03-11 大连理工大学 一种含铁天然矿石负载镍的甲烷化催化剂及其制备方法
CN106268858A (zh) * 2016-07-16 2017-01-04 中国科学院山西煤炭化学研究所 一种高性能二氧化碳加氢甲烷化的催化剂及制法和应用

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
ANMIN ZHAO ET AL: "Ni/Al2O3 catalysts for syngas methanation: Effect of Mn promoter", JOURNAL OF NATURAL GAS CHEMISTRY., vol. 21, no. 2, 1 March 2012 (2012-03-01), US, CN, pages 170 - 177, XP055480082, ISSN: 1003-9953, DOI: 10.1016/S1003-9953(11)60350-2 *
GAO ET AL., RSC ADVANCES, vol. 5, no. 29, 2015, pages 22759 - 22776
PANDEY ET AL., JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY, vol. 33, 2016, pages 99 - 107
SUNHWAN HWANG ET AL: "Methanation of Carbon Dioxide Over Mesoporous Nickel-M-Alumina (M = Fe, Zr, Ni, Y, and Mg) Xerogel Catalysts: Effect of Second Metal", CATALYSIS LETTERS, KLUWER ACADEMIC PUBLISHERS-PLENUM PUBLISHERS, NE, vol. 142, no. 7, 18 May 2012 (2012-05-18), pages 860 - 868, XP035079940, ISSN: 1572-879X, DOI: 10.1007/S10562-012-0842-0 *
SUNHWAN HWANG ET AL: "Methanation of carbon dioxide over mesoporous Ni-Fe-Al2O3 catalysts prepared by a coprecipitation method: Effect of precipitation agent", JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY, vol. 19, no. 6, 1 November 2013 (2013-11-01), KOREA, pages 2016 - 2021, XP055480070, ISSN: 1226-086X, DOI: 10.1016/j.jiec.2013.03.015 *
WAN AZELEE WAN ABU BAKAR ET AL: "Nickel Oxide Based Supported Catalysts for the In-situ Reactions of Methanation and Desulfurization in the Removal of Sour Gases from Simulated Natural Gas", CATALYSIS LETTERS, KLUWER ACADEMIC PUBLISHERS-PLENUM PUBLISHERS, NE, vol. 128, no. 1-2, 11 November 2008 (2008-11-11), pages 127 - 136, XP019671959, ISSN: 1572-879X *
ZHAO ET AL., JOURNAL OF NATURAL GAS CHEMISTRY, vol. 21, no. 2, 2012, pages 170 - 177

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109759061A (zh) * 2019-01-03 2019-05-17 浙江工业大学 一种γ-Fe2O3晶型的FeAl氧化物及其制备方法
CN109759061B (zh) * 2019-01-03 2021-08-10 浙江工业大学 一种γ-Fe2O3晶型的FeAl氧化物及其制备方法
CN113101930A (zh) * 2021-03-12 2021-07-13 中南大学 珊瑚状形貌的铁酸铜类芬顿催化剂的制备及其在垃圾渗滤液类芬顿催化氧化中的用途
CN115672331A (zh) * 2021-07-23 2023-02-03 国家能源投资集团有限责任公司 甲烷化催化剂及其制备方法和应用

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