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WO2018141648A1 - Catalyseurs de méthanation au nickel dopés par le fer - Google Patents

Catalyseurs de méthanation au nickel dopés par le fer Download PDF

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Publication number
WO2018141648A1
WO2018141648A1 PCT/EP2018/051995 EP2018051995W WO2018141648A1 WO 2018141648 A1 WO2018141648 A1 WO 2018141648A1 EP 2018051995 W EP2018051995 W EP 2018051995W WO 2018141648 A1 WO2018141648 A1 WO 2018141648A1
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Prior art keywords
catalyst
precipitate
solution
methanation
iron
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PCT/EP2018/051995
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German (de)
English (en)
Inventor
Klaus Koehler
Oliver THOMYS
Kai-Olaf Hinrichsen
Franz KOSCHANY
Thomas Burger
Original Assignee
Clariant Produkte (Deutschland) Gmbh
Wacker Chemie Ag
Technische Universität Muenchen
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Publication of WO2018141648A1 publication Critical patent/WO2018141648A1/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
    • B01J23/745—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
    • 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
    • B01J23/70—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
    • 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
    • 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
    • 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

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 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 purity of 95% is necessary in Germany. This results in the demand for a high catalyst activity, so that at industrially applied reaction pressures at low temperatures higher yields of methane can be achieved.
  • 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 iron is described, for example, in CN 104399482 A, CN 104399466 A, CN 104209127 A, CN 102872874 A, CN 101703933 A, CN 101537357 A, WO 2007025691 A1, CN 103706366 A, CN 104028270 A and CN 101745401 A. 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 104399482 A and CN 104399466 A disclose a natural ore loaded iron containing nickel catalyst for methanization and the production thereof.
  • Nickel oxide makes up 2 to 15% by weight of the catalyst.
  • the calcination temperature of the carrier, the calcination temperature of the catalyst, the reduction temperature of the catalyst and the like made a bimetallic iron-nickel methanation catalyst.
  • the catalyst thus prepared is characterized by a low nickel loading capacity, high activity, good stability, high strength and the like.
  • CN 104209127 A relates to a bimetallic nickel / iron methanation catalyst and the preparation and use thereof.
  • the alumina carrier In a ratio of 0.7 to 1 ml of soluble salt solution to 1 g of alumina carrier, the alumina carrier is immersed in the prepared soluble salt solution.
  • the carrier In a ratio of 0.7 to 1 ml of a soluble nickel salt solution to 1 g of the additive-containing carrier, the carrier is immersed in the nickel salt solution to obtain a nickel-containing carrier.
  • the nickel-containing carrier In a ratio of 0.7 to 1 ml of an iron salt solution to 1 g of the nickel-containing carrier the nickel-containing carrier is dipped in the iron salt solution to be subsequently dried and calcined to obtain a catalyst containing 2.5 to 10% by weight of nickel oxide, 2.5 to 10% by weight of iron oxide, 0.01 to 5 wt .-% of an additive, wherein the additive is at least one element selected from lanthanum, cerium, barium, and magnesium.
  • the catalyst thus prepared exhibits a greatly increased activity in cryogenic methanation, has reduced costs and improves methane selectivity and stability.
  • CN 102872874 A relates to a nickel-based loaded catalyst used for the methylation in a suspension, a production process and the use thereof.
  • the nickel-based loaded catalyst consists of 10 to 40% by weight of NiO, 56 to 90% by weight of a carrier and 0 to 4% by weight of an adjuvant.
  • the nickel-based loaded catalyst is prepared by the steps of preparing a soluble salt solution with 0.5 to 1.3 g / ml nickel nitrate and the excipient; adding a catalyst carrier and a soluble organic fuel to the salt solution in tandem; impregnation for 6 to 24 hours with stirring; heating the solution, for concentration, in a water bath at a temperature of 60 to 90 ° C, after impregnation or heating to directly ignite the solution at a temperature of 300 to 700 ° C; isolating the post-combustion powder, grinding and granulating the powder, and reducing for 2 to 6 hours with a reducing gas in a fixed bed reactor at a temperature of 500 to 700 ° C.
  • CN 101537357 A relates to a methanation catalyst produced from synthetic gas.
  • the methanation catalyst comprises the following components: 1 to 20% iron oxide, 1 to 30% cobalt oxide, 1 to 30% nickel oxide, 0 to 10% of a rare earth oxide, 0 to 10% molybdenum oxide, and 50 to 97% silicon carbide support.
  • the preparation of the methanation catalyst comprises the silicon carbide material, which is chemically stable and has good thermal conductivity, as a catalyst support for producing a methanation catalyst by synthetic gas.
  • WO 2007025691 A1 relates to a process for the hydrogenation of carbon oxides comprising contacting a gas mixture containing carbon oxides and hydrogen with a catalyst comprising a bimetallic iron-nickel or iron-cobalt alloy as an active catalyst material, applied to an oxidic support.
  • the support preferably has a surface area> 20 m 2 / g.
  • CN 103706366 A describes a catalyst comprising 15 to 55% of 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.
  • a metal salt of at least one selected from magnesium nitrate, manganese nitrate, iron nitrate and zirconium nitrate, the alkali metal 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 the methanation of 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 making the methanation catalyst which comprises mixing the precursor of the catalytically active component, the precursor of the co-acting component M and a catalyst support according to the proportion in the methanation catalyst composition, adding an organic fuel and the 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 which is characterized in that it comprises a main metal M as active component, a second metal M1 as auxiliary and S as support material, the weight ratio between M1, M and S being between 0 Where 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 and / or Ce and the support S Zr0 2 , Al 2 0 3 , MgO or Ti0 2 .
  • the supported sulfur-resistant methanation catalyst is prepared by a sol-gel method.
  • a catalyst for the methanation of carbon monoxide and / or carbon dioxide comprising aluminum oxide and a Ni active composition which contains Fe, characterized in that the molar Ni / Fe ratio in the catalyst is 4.0 to 25.0, preferably 5.0 to 10.0, and more preferably 5.0 to 6.0.
  • 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 / Fe ratio may be in the range of 4.5 to 8.0, preferably in the range of 5.0 to 7.0, most preferably in the range of 5.3 to 5.5.
  • the promoter Fe may be contained completely or partially in the Ni active material.
  • the catalyst may contain other promoters in addition to Fe, but it may also contain exclusively the promoter 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+, Fe 2+, Fe 3+). After calcination, eg in air, high oxidation states or the maximum oxidation states can be achieved. Becomes the catalyst is reduced at temperatures above room temperature, for example under reaction conditions with hydrogen, AI, Ni and the promoters can assume lower oxidation states or occur partially or completely in the oxidation state 0. The charge balance to the metal cations is carried out by negatively charged oxygen atoms (0 2 ⁇ ).
  • the catalyst according to the invention may contain other components besides aluminum oxide (AlO x with x ⁇ 1.5) Ni and Fe (as well as the oxygen anions necessary for charge equalization), but it may also consist exclusively of aluminum oxide, Ni and Fe.
  • the Ni active material in addition to Fe may contain further promoters, but it may also contain only the promoter Fe.
  • the catalyst does not contain any of the elements selected from Ta, In, Cu, Ce, Cr, Bi, Mn, P, B, Sb, Sn, Si, Ti, Zr, Co, Rh, Ru, Ag, Ir, Pd and Pt ,
  • the catalyst does not contain a noble metal.
  • the catalyst does not contain Mn.
  • 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 material may also consist entirely or substantially of crystallites with 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 150 ⁇ / g and is preferably in the range between 150 to 250 ⁇ / g, more preferably, between 180 to 210 ⁇ / g.
  • the BET surface area (SBET) of the catalyst according to the invention may be greater than 100 m 2 / g, preferably greater than 200 m 2 / g, or in the range between 200 and
  • 400 m 2 / g preferably in the range between 200 and 300 m 2 / g and in particular in the range between 200 and 250 m 2 / g.
  • the specific metal surface area (Swiet) of the catalyst according to the invention is preferably greater than 5 m 2 / g, preferably greater than 10 m 2 / g, or in the range between 5 and 25 m 2 / g, preferably in the range between 10 and 20 m 2 / g, or in the range between 9 and 12 m 2 / g. Furthermore, 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 and Fe are present dissolved in the aqueous solution as ionic compounds.
  • Al is preferably dissolved as aluminum nitrate, aluminum trichloride or aluminum sulfate.
  • 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 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 and Fe to a basic solution or by adding a basic solution to the proposed solution containing Al, Ni and Fe.
  • the solution containing Al, Ni 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 of 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 preferably more preferably for at least 30 minutes, preferably longer than 1 hour aged for more than 12 hours.
  • the aging is preferably carried out by stirring the precipitate at approximately room temperature in the solution (mother liquor).
  • 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 400 ° C to 500 ° C and in a period of 3 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: 4H 2 + C0 2 -> CH 4 + 2H 2 0
  • 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.
  • the figures show the catalytic behavior of the iron-doped catalysts Fe2, Fe4, Fe7 and Fe10 before and after aging.
  • Figure 1 Catalytic test results for Fe2 (example).
  • FIG. 3 Catalytic test results for Fe7 (example).
  • FIG. 4 Catalytic test results for Fe10 (comparative example).
  • FIG. 5 Normalized WTY (CH4) as a function of the aging time for Fe711 in comparison to Nill at an aging temperature of 450 ° C.
  • FIG. 6 Normalized WTY (CH4) as a function of the aging time for Fe711 in comparison to Nill at an aging temperature of 350 ° C.
  • 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.
  • 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. chemisorption
  • the equilibration time for the adsorption was set to 10 min with otherwise unchanged parameters. Before the absorption of the chemisorption data, any kinetic inhibition of CO 2 chemisorption under these conditions was experimentally excluded. Metal surfaces and CC uptake capacities were extrapolated to a pressure of 0 mmHg according to the extrapolation method.
  • 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 (II) nitrate was added to the salt solution of nickel and aluminum nitrate during catalyst synthesis.
  • the purity of all chemicals used was pa Water was purified by a Millipore filter system and the degree of purity verified by conductivity measurements.
  • the synthesis was carried out in a double-walled, 3 l stirred tank. The water-filled double jacket allowed the temperature of the synthesis approach to 30 ° C via a thermostat, two baffles provided for an improved mixing. For stirring, a KPG stirrer with 150 revolutions min.
  • the precipitation reagent was a mixture of 0.5M NaOH and 0.5 M Na 2 C0 3 solutions of equal volume, for the metering of which a titrator was used. With constant stirring, the suspension was aged overnight in the mother liquor, the precipitate was then filtered off and washed with H 2 0 until the filtrate had a neutral pH. After drying at 80 ° C in a drying oven overnight, the dried precipitate (precursor) was heated at a heating rate of 5 K min -1 to 450 ° C and calcined for 6 hours under synthetic air. Activity and stability measurement
  • Table 1 Parameters of the measurement steps for determining the activity and stability profile
  • the temperature in the specified range was gradually increased by 25 ° C and each determines the activity.
  • a comparison of the two S-curves before and after 32 hours of aging at 500 ° C gives an insight into the stability of the systems in terms of high temperatures.
  • the temperature T 7 5, i was determined, which is necessary in order to achieve a C0 2 conversion of 75% during the measuring step S-curve 1.
  • 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 which is necessary in order to achieve a C0 2 conversion of 75% during the measuring step S-curve 2, was determined representatively.
  • the temperature in the specified range was gradually increased by 25 ° C.
  • FIGS. 1 to 4 show that the promotion of a Ni / AlO x catalyst with iron, with a Ni / Fe ratio in the catalyst of 4.0 to 25.0, leads to a significant increase in the catalyst stability.
  • 50 mg of the calcined catalyst was mixed with 450 mg Fe-free SiC (ESK) and placed in a quartz glass-coated tube reactor (4 mm ID).
  • the catalyst bed was fixed with quartz wool plugs and positioned in the isothermal zone of a furnace.
  • the catalyst temperature would be measured via a thermocouple in the catalyst bed.
  • the catalyst was contacted with a heating rate of 2 K min-1 in 5% H2 in Ar with 50 min- NL 1 to 485 5 C. and reduced there for 5 h.
  • the aging time was 2 h in the initial deactivation treatment and 4 h in all further treatments.
  • the catalyst bed was cooled to 230 ° C before the catalyst activity was re-determined under the above conditions to follow the catalyst deactivation in the kinetic regime under conditions free of product or equilibrium limitations. These cycles were repeated to obtain catalysts aged for 0, 6, 40 and 72 hours. The aged catalysts were transferred under Ar atmosphere to a glovebox, from which further characterization studies were prepared.

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Abstract

Catalyseur de méthanation de monoxyde de carbone et/ou de dioxyde de carbone, comprenant de l'oxyde d'aluminium, une masse active de Ni et du Fe, caractérisé en ce que le rapport molaire Ni/Fe dans ledit catalyseur est compris entre 4,0 et 25,0, de préférence entre 5,0 et 10,0 et de préférence encore entre 6,5 et 7,5. 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 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/EP2018/051995 2017-01-31 2018-01-26 Catalyseurs de méthanation au nickel dopés par le fer WO2018141648A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112517036A (zh) * 2019-09-17 2021-03-19 中国石油天然气股份有限公司 合成气甲烷化催化剂及其制备方法
CN114870846A (zh) * 2022-06-06 2022-08-09 华南农业大学 一种二氧化碳甲烷化催化剂及其制备方法与应用

Citations (16)

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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
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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
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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
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
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