EP2776164A1 - Procédé de préparation d'un catalyseur de méthanisation et procédé de méthanisation d'un gaz de synthèse - Google Patents

Procédé de préparation d'un catalyseur de méthanisation et procédé de méthanisation d'un gaz de synthèse

Info

Publication number
EP2776164A1
EP2776164A1 EP12847684.3A EP12847684A EP2776164A1 EP 2776164 A1 EP2776164 A1 EP 2776164A1 EP 12847684 A EP12847684 A EP 12847684A EP 2776164 A1 EP2776164 A1 EP 2776164A1
Authority
EP
European Patent Office
Prior art keywords
range
temperature
catalyst
methanation
metal salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12847684.3A
Other languages
German (de)
English (en)
Other versions
EP2776164A4 (fr
Inventor
Claudia Querner
Andrian Milanov
Stephan Schunk
Andreas Strasser
Guido WASSERSCHAFF
Thomas ROUSSIÈRE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP12847684.3A priority Critical patent/EP2776164A4/fr
Publication of EP2776164A1 publication Critical patent/EP2776164A1/fr
Publication of EP2776164A4 publication Critical patent/EP2776164A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • 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
    • B01J23/005—Spinels
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • B01J23/78—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 alkali- or alkaline earth metals
    • 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
    • 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
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B01J35/67—Pore distribution monomodal
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J37/0081—Preparation by melting
    • 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
    • B01J37/04—Mixing
    • 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
    • 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

Definitions

  • the invention relates to a process for the preparation of a methanation catalyst and to a process for the methanation of CO and / or CO 2 -containing gas streams, preferably at high temperatures.
  • hydrotalcite-containing starting material is brought into contact with a meltable metal salt, preferably containing nickel nitrate, intimately mixed and subjected a.) To a thermal treatment step and b.) To a calcination step.
  • SNG Substituted Natural Gas
  • 3,912,775 describes the preparation of a precipitate with the composition NieAl.sub.2 (OH) .sub.16 CO.sub.3.times.H.sub.2O.sub.2, which is obtained by the precipitation of nickel nitrate and aluminum nitrate from aqueous solution using sodium carbonate solution.
  • the precipitation may also be carried out in the presence of a carrier component.
  • the precipitate is dried at a temperature in the range of 80 to 180 ° C and calcined at a temperature in the range of 300 to 550 ° C.
  • Characteristic for the production process is that the temperature increase between the drying process and the calcining process takes place by applying a temperature gradient by means of a controlled heating rate.
  • naphtha and water vapor are used as starting materials which, at a temperature in the range of 270 ° C. and 460 ° C. and a pressure in the range from 15.8 to 29.6 bar, come into contact with the active composition to be brought.
  • the efficiency of nickel-containing catalysts for the methanation can be increased in accordance with US Pat. No. 3,865,753 by additionally adding magnesium species to the aluminum-containing synthesis system.
  • a nickel-containing magnesium aluminate is obtained as the active composition, which has a high activity and stability with respect to the methanation.
  • the divalent metals (magnesium and nickel) and the trivalent aluminum be at least in a 1: 1 molar ratio, with a preferred molar ratio between M 2 + and M 3 + in a range of 2.5 : 1 to 3: 1.
  • the increased activity of the catalyst is also explained by the fact that - after drying, calcination and reduction - a magnesium spinel forms during the reaction.
  • US 3,988,262 discloses an improved catalyst obtained by depositing the nickel-containing component on the aluminum-containing support in the presence of zirconia.
  • the catalyst according to the invention has a nickel oxide content of 15 to 40 wt .-%, wherein at least a large part of the nickel oxide is reduced to nickel before the start of the methanation.
  • the thermal stability of the methanation catalysts can be further increased in that the catalyst has a certain proportion of molybdenum oxide.
  • a molybdenum content which has 0.25 to 8% by weight of molybdenum or molybdenum oxide has proved to be advantageous.
  • EP 2 308 594 A2 discloses a nickel-containing catalyst for the production of synthesis gas from methane, water and carbon dioxide with a ratio in the range of 1, 0/1, 0-2.0 / 0.3-0.6.
  • the improved stability of the catalyst is achieved by adding Ce and / or Zr.
  • a synthesis using magnesium aluminum hydrotalcite as a starting material is also disclosed.
  • An impregnation process is disclosed in which hydrotalcite as carrier is impregnated with an aqueous nickel nitrate solution, the water subsequently being removed in a vacuum evaporator at 70 ° C.
  • EP 2 308 594 A2 discloses an example in which the catalytic studies for the production of synthesis gas were carried out at 10 atm.
  • EP 031 472 A2 discloses and claims a methane production catalyst prepared with thermally decomposable salts of nickel, cobalt and magnesium which are fixed on a carrier. The support is converted by thermal treatment in the metal oxides.
  • DE 29 52 683 discloses a methanation catalyst containing Co and Ni species as active components.
  • support materials are aluminum oxides or mixed oxides of alumina and silica or silica, wherein the catalytic properties of the catalyst is improved by the addition of magnesium-containing salts to the synthesis mixture.
  • the thermal treatment of the catalyst precursor material the formation of a spinel-containing phase is reported.
  • the catalysts are used for methanation reactions, which are carried out at temperatures below 500 ° C and where the pressure is in the range of atmospheric pressure.
  • One of the objects on which the invention is based is to provide an improved process and an improved catalyst for the methanation of CO and / or CO 2 -containing synthesis gas.
  • a catalyst material should be provided here whose thermal and mechanical resistance is superior to the materials known from the prior art.
  • Methane formation by the reaction of carbon monoxide and / or carbon dioxide with hydrogen is a highly exothermic process. In the presence of a suitable catalyst, the reaction usually proceeds to equilibration.
  • Catalytic methane formation is carried out under adiabatic process conditions. The increase in temperature within the reactor associated with the adiabatic process is determined, among other things, by the composition of the gas, the temperature of the gas supplied and the working pressure. Typically, the temperature rise in carrying out the methanation is in a range of 200 to 500 ° C.
  • the temperature of the gas supplied to the reactor is chosen so that the effectiveness of the catalyst can be used with a high degree of conversion.
  • the supplied gas must already be preheated to a suitable inlet temperature.
  • methane formation within the catalyst bed is limited to a narrow reaction zone. The local area of the reaction zone depends on the operating time of the methanation process. At the beginning of the methanation process, methane formation first extends to the area of the catalyst bed which is close to the educt gas feed. With increasing operating time and progressive deactivation of the catalyst within the reaction zone, this then shifts in the gas flow direction from the inlet region to the outlet region of the catalyst bed.
  • the input temperature and the process parameters should be chosen so that the formation of Ni (CO) 4 is prevented.
  • an inlet temperature of greater than 250 ° C is required.
  • the methanation of C02-containing educt gas can also be carried out at lower inlet temperatures, for example at a temperature of 200 ° C. or even below 200 ° C.
  • the implementation of the methanization with educt gas, which has a lower inlet temperature, is also possible in conjunction with nickel-free catalysts. Due to the mode of operation mentioned herein, that part of the catalyst bed that is near the reactor exit is exposed to a higher thermal load than that part of the catalyst bed that is near the reactor inlet. Here, the higher thermal stress of the catalyst material, which is located in the catalyst bed in the vicinity of the reactor outlet before it is used for methanation. To limit the thermal load of the catalyst, the temperature of the
  • the operating parameters are set in such a way that the temperature of the product mixture at the reactor outlet does not exceed an upper temperature limit. This can be achieved, for example, by diluting the educt stream with a certain proportion of product stream (recycle). Due to the dilution, the CO or CO 2 content in the educt current is reduced and the temperature increase caused by the exotherm is limited. It should be noted that all temperature data, which are referred to in the context of the present disclosure in relation to the methanation process according to the invention, always refer to the temperature of the reaction chamber-side obtained gas mixture, unless otherwise specified.
  • the objects mentioned here, as well as other objects which are not mentioned here, are achieved by providing a process for the preparation of a catalyst for the methanation of CO and / or CO 2 -containing synthesis gases.
  • the method relates to the impregnation of a starting material with a meltable metal salt, the production method comprising the following steps:
  • the method is characterized in that the calcining according to the process steps (iv) and (vi) is carried out using a defined heating rate and / or cooling rate, wherein the heating and / or cooling rate preferably in the range of 0.01 to 10 ° C per minute, more preferred is a range of 0.1 to 5 ° C per minute.
  • the molding step (v) is followed by a screening step.
  • the metal salt fraction used in (i) contains a nickel salt, preferably nickel nitrate hexahydrate.
  • the hydrotalcite-containing starting material preferably has defined proportions of magnesium and aluminum, preferably at least 10 mol% of magnesium and at least 10 mol% of aluminum.
  • the subject of the invention also relates to a catalyst for the methanation of CO and / or CO 2 -containing synthesis gas, this catalyst being obtainable by the following steps.
  • cryogenic calcination of the mixture at a temperature ⁇ 500 ° C, preferably at a temperature in the range of 250 to 500 ° C, the time for the cryogenic calcination preferably being in the range of 0.1 to 24 hours, preferably smaller 2 hours, in the case of a continuous process, the preferred calcination time is ⁇ 1 hour.
  • the preferred calcination time is ⁇ 1 hour.
  • Characteristic of the catalyst according to the invention is that the nickel is very highly dispersed on the carrier oxide and that the carrier oxide consists of or contains very small particles of MgA C. This results in catalysts with an improved property profile, which manifests itself both in improved sintering stability at high temperatures and improved coking behavior.
  • the production method according to the invention has advantages over those production methods which are based on precipitation methods.
  • the process according to the invention does not give rise to any significant amounts of process water or the process according to the invention can also be carried out in a manner in which no process water is produced at all.
  • precipitation reagents can also be saved.
  • the problems associated with precipitation reagents, which is the result of contamination, can be prevented.
  • the synthesis of the catalysts according to the invention it should also be emphasized that an extremely energy-efficient and environmentally friendly process is provided due to the largely anhydrous production process.
  • the amount of water used is preferably 100 100%, more preferably -i 90%, more preferably 70 70%, more preferably ⁇ 50%, still more preferably ⁇ 40% , more preferably ⁇ 30%, and more preferably ⁇ 20% of the total pore volume of the carrier.
  • the catalyst can be prepared without the addition of water, since the water necessary for the synthesis in this case is supplied solely by the water of hydration of the salt.
  • the type of mixing and the resulting compound of hydrotalcite-containing starting materials with the molten metal salt according to the method of the invention is extremely effective in terms of the application and incorporation of active components into the framework structure.
  • Catalysts are obtained which have nickel crystallites at temperatures up to 1000 ° C. which are less than 100 nm, preferably less than or equal to 70 nm and particularly preferably less than or equal to 40 nm, and which have high resistance to sintering and coking processes ,
  • the present nanostructuring of the material is particularly advantageous in terms of its catalytic properties.
  • the material of the invention over the prior art has proven to be an advantageous catalyst, which is particularly suitable for the methanation of CO and / or CO 2 -containing synthesis gases.
  • the catalyst support comprises a magnesium spinel in intimate contact with a mixed oxide phase of nickel and magnesium.
  • Characteristic of this catalyst or catalyst precursor according to the invention is that both the nickel-containing and the spinel-containing phase have very small crystallite sizes.
  • the average crystallite size is ⁇ 100 nm, preferably the average crystallite size is ⁇ 70 nm, more preferably the average crystallite size is ⁇ 40 nm.
  • FIG. 1 An exemplary representation of a typical diffractogram (5-80 ° 2 ⁇ ) of a catalyst according to the invention is shown in FIG. It is not excluded that the catalyst material according to the invention or the catalyst precursor material also contains small amounts of Ni spinel phase and possibly also NiO. However, if a Ni spinel phase is present in the precursor material of the present invention, then it is believed that it will convert at the high pressures and high temperatures of the catalyst use of the present invention.
  • all active metals can be applied to hydrotalcite or to hydrotalcite-containing starting material which is in the temperature range of 30 ° C to 250 ° C as a metal salt melt and in which the resulting catalysts have a catalytic activity as a methanation catalyst.
  • promoters may be added to the metal salt melt and / or, in addition to the hydrotalcite-containing starting material, further carrier oxides, pore-forming agents or binders may be added to the synthesis system.
  • metal salts which do not decompose during the melting process or in which the decomposition is kinetically strongly inhibited.
  • metal salts include nitrates, nitrites, halides, chlorates, bromates, iodates, sulfates, sulfites.
  • Particularly preferred are nitrates, nitrites or molten salts containing nitrates and nitrites.
  • the addition of certain additives to the melts - such as urea, ethylene glycol - is included.
  • the meltable metal salts may include, for example, Na, K, Ca, Mg, Sr, Ba, Al, La, Y, Mo, W, Nb, Zr, Ti, Fe, Co, Ni, Cu, a platinum metal, and / or Ce contain.
  • Suitable anionic species are, in particular, nitrogen-containing anions, such as nitrates and nitrites. In principle, however, it is also possible to use other anions such as halogens, sulfates and sulfites and other inorganic and organic anions known to the person skilled in the art.
  • the metal salts contain at least one nickel-containing or cobalt-containing component, preferably nickel nitrate or cobalt nitrate hydrate such as hexahydrate. Particularly preferred is nickel nitrate hexahydrate.
  • hydrotalcite-containing starting material in the sense of the present disclosure means that the material used contains as essential constituent at least one hydrotalcite-like compound and may optionally contain oxidic aggregate and / or minor constituents.
  • the proportion of hydrotalcite-like compound and the oxidic aggregate is greater than 50 wt .-%, preferably greater than 70 wt .-% and especially preferably greater than 90 wt .-%.
  • the hydrotalcite-containing starting material may also have minor constituents, for example consisting of metal salts, which serve, for example, to adjust the metal concentration of trivalent to divalent metal salt.
  • Such secondary constituents of metal salts are less than or equal to 10% by weight, preferably less than or equal to 5% by weight.
  • Hydrotalcite-like compounds are composed of polycations
  • divalent metals for example, metals from the group of Mg, Zn, Cu, Ni, Co, Mn, Ca and / or Fe
  • trivalent metals for example, metals from the group AI, Fe, Co, Mn, La, Ce and / or Cr be used.
  • the hydrotalcite-like compound is hydrotalcite.
  • the hydrotalcites used for the process according to the invention comprise magnesium as bivalent metal and aluminum as trivalent metal.
  • the metals of the hydrotalcites used consist predominantly of magnesium and aluminum.
  • the oxidic aggregate may also be mixtures, these preferably containing aluminum-containing compounds.
  • aluminum-containing oxidic additives include gibbsite, boehmite or pseudoboehmite.
  • Typical contents of such aluminas, hydroxides or oxide hydrates may be between 30 and 95 percent by weight calculated on the basis of alumina. This corresponds to a molar proportion of aluminum based on total metal of 26 to 84 mol%. Particularly preferred are ranges of 50 to 80 weight percent calculated based on alumina. This corresponds to a molar proportion of aluminum based on total metal of 44 to 70 mol%. Most preferred is a range of from 60 to 75 weight percent based on alumina. This corresponds to a molar proportion of aluminum based on total metal of 53 to 66 mol%.
  • hydrotalcite-like compounds and the oxidic aggregate have a very thorough mixing. The same applies to minor constituents, if they should be contained in the hydrotalcite-containing starting material.
  • Such mixing can be carried out, for example, by a physical mixing of hydrotalcite-like and aluminum hydroxide-containing powders.
  • a physical mixing of hydrotalcite-like and aluminum hydroxide-containing powders For example, be carried out by powder mixing in suitable technical equipment such as mixers.
  • suitable technical equipment such as mixers.
  • Such mixing methods are known to the person skilled in the art.
  • Another possibility is to mix the hydrotalcite-like and the aluminum hydroxide-containing powders in suitable dispersants.
  • suitable dispersants for example, water, alcohols, such as methanol, ethanol, propanol, butanol, ethylene glycol and / or butanediol, and ketones, such as acetone or methyl ethyl ketone, can be used as the dispersing agent.
  • the dispersants are present as mixtures and contain surface-active agents such as surfactants.
  • surfactants examples include polyethylene glycols, mersolates, carboxylates, long chain ammonium compounds such as CTAB.
  • Another possibility of intimate mixing is the direct synthesis of a mixture of hydrotalcite-like and aluminum hydroxide-containing mixtures by precipitation reactions. Such methods can be carried out, inter alia, as described in DE 195 03 522 A1 on the basis of the hydrolysis of water-sensitive precursors, which allows a large number of possible compositions.
  • Other alternative processes for the preparation of mixtures of hydrotalcite-containing and aluminum hydroxide-containing mixtures can also be carried out on the basis of precipitation reactions from aqueous media.
  • Carbonate-containing precipitants may be used here, for example, or carbon dioxide-containing gas generators may be used. be applied under pressure to suitable precursor solutions of metal salts or hydroxides.
  • hydrotalcite-containing starting materials used in the invention are products of the company Sasol, which are commercially available under the trade name Pural MG (Pural MG 5 to Pural MG 70 are commercially available, wherein Pural MG 70 is a Mg-Al hydrotalcite without aluminum hydroxide admixture ) to be expelled.
  • Pural MG Physical MG 5 to Pural MG 70 are commercially available, wherein Pural MG 70 is a Mg-Al hydrotalcite without aluminum hydroxide admixture ) to be expelled.
  • the intimate mixing of magnesium and aluminum-containing hydrotalcites with other carbonates, hydroxides or hydroxycarbonates is also included within the scope of the invention.
  • Hydrotalcites or hydrotalcite-like compounds of particular purity are preferably used for the process according to the invention.
  • the process for preparing these hydrotalcite-like compounds which are particularly preferably used in the process according to the invention is described by J.P. van Berge et al. disclosed in DE 195 03 522 A1.
  • the hydrotalcites or hydrotalcite-like compounds are formed by the hydrolysis of metal alcoholates with water and subsequent drying of the precipitated hydrolysis products.
  • the metal alkoxides are formed by reacting mono-, di- and / or trivalent alcohols with one or more divalent metals and / or one or more trivalent metals.
  • the water used for the hydrolysis preferably contains water-soluble anions selected from the group consisting of hydroxide anions, organic anions, in particular alcoholates, alkyl ether sulfates, aryl ether sulfates and / or glycol ether sulfates and / or inorganic anions, in particular carbonate, bicarbonate, chloride, nitrate, sulfate and / or polyoxometalanions.
  • the counterion used is preferably ammonium.
  • hydrotalcite-containing materials which are particularly suitable as starting materials for the preparation of the catalyst and which have been prepared by hydrolysis of metal alcoholates, are materials which are sold by the company Sasol under the trade name Pural MG5, Pural
  • MG20, Pural MG30, Pural MG50 and Pural MG70 can be sourced. It is the indication of the manufacturer, whereby the numerical value in the product name refers to the percentage weight content of MgO. In order to obtain a total weight of 100%, the proportion by weight of MgO must be supplemented with the content of Al2O3. It should be noted that the information given here is given based on the oxides, the samples also containing hydroxide groups and water. It is possible that the samples may also contain other anions, such as carbonate anions. It is also possible to obtain materials which have other MgO-to-A Os ratios.
  • a particularly preferred hydrotalcite-containing starting material Pural MG30 for example, consists of a mixture of hydrotalcite (ie, a component having a composition of Mg6Al2 (OH) i8 * 4H 2 0 or Mg6Al2 (OH) i6C03 * 4H 2 0) and boehmite, wherein the mixture has an overall AOS / MgO ratio close to seventy to thirty percent by weight.
  • hydrotalcite ie, a component having a composition of Mg6Al2 (OH) i8 * 4H 2 0 or Mg6Al2 (OH) i6C03 * 4H 2 0
  • boehmite wherein the mixture has an overall AOS / MgO ratio close to seventy to thirty percent by weight.
  • hydrotalcite which is particularly preferred according to the preparation process according to the invention as a constituent of the hydrotalcite-containing starting material
  • other metal hydroxides or hydroxycarbonates are particularly preferred.
  • Particularly preferred are those which can be prepared by the same synthesis method as hydrotalcites and hydrotalcite-like compounds.
  • the hydrotalcite-containing starting material has a preferred Al / Mg ratio.
  • the preferred alumina / magnesia ratio (ie, the A Os / MgO ratio) is in a range of 0.5 to 20 by weight Base, with an alumina / magnesia ratio of 1 to 10 on a weight basis being more preferred.
  • the preferred Al / Mg ratio is in a range of 1.5 to 2.5 on a molar basis, with an Al / Mg ratio of 1.7 to 2.3 on a molar basis being more preferred.
  • the preferred hydrotalcite-containing starting material should preferably be convertible in significant proportions, more preferably almost completely, to a material having spinel or spinel-related structures or phase mixtures of such structures.
  • NiO content is about 55 - 73.5 wt .-%.
  • the XRD results indicate that in the mixed oxide phase Ni x Mg (i -X ) 0, magnesium species are depleted.
  • the Mg species are incorporated in Ni spinel as a substitute for Ni species.
  • a possible explanatory approach, which is not intended to limit the invention, would be that even at high temperatures some of the aluminum will be present further than alumina hydrate. Under reductive conditions at high temperatures, a precipitate tion of the metallic nickel from the mixed oxide phase Ni x Mg (i -X ) 0 take place, in which case the liberated magnesium reacts with the Aluminiumoxihydrat to magnesium-aluminum spinel.
  • the molar ratio of metal species in the hydrotalcite-containing starting material MHT and metal species in the molten salt Ms is always greater than 1.
  • the molar ratio MHT / MS is in a range of 15 to 1.5 and more preferably in a range of 10 to 3.
  • the use of a preferred ratio is important to the conditions for good mixing of the components and a homogeneous coating to ensure the hydrotalcite and thus ensure the nano-structuring, in particular the high dispersion and fineness of the nickel or the mixed oxide of Ni and Mg and the fineness of the Mg spinel, the material according to the invention.
  • the powdered hydrotalcite-containing material is heated prior to contacting with the refractory metal salt and, when brought into contact with the metal salt, has a temperature in the range of 30 to 250 ° C, preferably the temperature is in the range of 50 ° C to 140 ° C.
  • the temperature required to melt the metal salt depends on the properties of the particular metal salt or metal salt mixture used.
  • the metal salts which are particularly suitable for the process according to the invention have a melting point in the range from 30 to 250.degree.
  • the hydrotalcite-containing starting material is brought into contact with the metal salt melt.
  • the metal salts In order to prevent the solidification of the metal salt melt during the contacting and the mixing with the hydrotalcite, it is advantageous to preheat the metal salts to a temperature which is at least 10 ° C., preferably 20 ° C., above the temperature of the melting point of the salts or salt mixture used lies.
  • the water of crystallization of the hydrotalcite and the metal salt melt is subject to evaporation.
  • the evaporation depends on the temperature, the gas exchange, the gas atmosphere and the time of the process.
  • Complete evaporation of the water of crystallization may be undesirable, since thereafter decomposition of the salt or hydrotalcite may occur before the mixture is homogenized.
  • the solidification of an area in the melt which has not yet been intimately mixed with the hydrotalcite-containing material impairs the homogeneity of the distribution of the metal species on the solid hydrotalcate-containing starting material.
  • the time for the contacting should be as short as possible, ie preferably less than or equal to 30 minutes.
  • the gas atmosphere should contain a certain amount of water in order to suppress the decomposition of metal salt or the hydrotalcite-containing starting material during the mixing.
  • the content of water vapor may here be, for example, in a range of 0 to 10 vol .-%.
  • hydrotalcite-containing starting material It is advantageous to heat the hydrotalcite-containing starting material to a temperature which corresponds approximately to the temperature of the molten salt before it is brought into contact with the molten salt, in order to prevent uncontrolled solidification of the molten salt.
  • the process step of contacting the hydrotalcate-containing starting material with the metal salt is not subject to any limitation. In the following, however, several embodiments of the contacting are listed, which are advantageous.
  • the hydrotalcite-containing starting material can first be combined with the powdered metal salt at a temperature below the melting point of the salt and mixed before it is melted.
  • the combination of substances takes place initially in the cold.
  • the combination and mixing can be done in several steps or in a single step.
  • the pulverulent hydrotalcite-containing starting material is initially introduced into a receiver and the metal salt melt is added while the solid is agitated.
  • the melt can be added in portions to the hydrotalcite in several steps or in a single step.
  • the hydrotalcite-containing starting material is first coated with the metal salt before it is then melted.
  • the hydrotalcite-containing starting material can first be suspended in water and combined with a metal salt-containing solution. The mixture of the hydrotalcite-containing starting material and the metal salt-containing solution forms a suspension which can be dried, for example by spray-drying.
  • the components brought into contact with each other must be mixed and homogenized by means of mechanical mixing elements.
  • a mixer for example, powder mixer, tumbler, kneader, etc. can be used.
  • the person skilled in the art should be familiar with the appropriate technical means for mixing.
  • the time duration is> 2 minutes, more preferred is a time duration> 10 minutes, and even more preferred is a time duration> 30 minutes.
  • the mixing according to step (ii) and the thermal treatment according to step (iii) are carried out simultaneously. During the mixing process, it is preferable that the material to be mixed is heated to prevent solidification or solidification of the molten salt.
  • the heating of the material is preferably carried out using a controlled heating rate.
  • the heating rate is less than 20 ° C / min, preferably less than 10 ° C / min, and more preferably less than 5 ° C / min.
  • the material obtained after the low-temperature calcination may be present as a finely divided powder or as a coarse-grained bulk material.
  • a shaping process may be necessary. As a shaping step, for example, division, grinding, tableting or extrusion can be performed.
  • the material calcined at low temperature is subjected to a molding process to obtain a molded material.
  • This shaping process may include one or more of the following steps:
  • the shaping process consists of an extrusion process.
  • the melt-impregnated catalyst mass is processed, for example, with additives with an extruder to the desired moldings.
  • the process step of the low-temperature calcination step (iv) does not have to take place.
  • the process can be carried out in a manner in which the calcination takes place only after the extrusion in the form of a high-temperature calcination step. Generally precalcination is performed prior to extrusion.
  • the molded material is always subjected to a high-temperature calcination process.
  • the target temperature in the high-temperature calcination is in the range of greater than or equal to 500 ° C, preferably in the range of 500 to 1000 ° C.
  • the duration of the high-temperature calcination, ie the temperature of the sample at the target temperature, is in the range of 0.1 to 24 h.
  • High temperature calcination may be carried out in the presence of an oxygen-containing atmosphere, preferably air.
  • the heating of the sample to the target temperature is preferably carried out using a controlled heating rate, preferably the heating rate is less than 20 minutes and more preferably less than 10 ° C / min.
  • the preparation of the catalyst according to the invention it may be preferred that at least individual substeps of the preparation process are carried out in a continuous manner. It is particularly preferred, for example, to carry out the low-temperature calcination in a continuously operated rotary kiln.
  • the calcined catalyst may be exposed to a reductive gas atmosphere while heating, in order to reduce at least part of the metal species, preferably of the nickel.
  • This thermal treatment is preferably carried out under a reductive gas atmosphere in the same reactor in which the catalytic process is carried out.
  • the invention relates to a catalyst for catalyzing heterogeneous reactions, preferably the reaction of methane, carbon dioxide and water to synthesis gas comprising at least the three phases nickel-magnesium mixed oxide, magnesium spinel and aluminum oxide hydroxide and characterized in that the nickel-magnesium mixed oxide has an average crystallite size of ⁇ 100 nm, preferably ⁇ 70 nm, more preferably ⁇ 40 nm, and the magnesium spinel phase has an average crystallite size of ⁇ 100 nm, preferably ⁇ 70 nm preferably ⁇ 40 nm, the proportions of nickel in the range of 7 to 28 mol%, of magnesium in the range of 8 to 26 mol%, of aluminum in the range of 50 to 70 mol% and the BET surface area in the range of 10 - 200 m 2 / g.
  • the catalyst according to the invention which has a nickel content in the range from 6 to 30 mol% and a magnesium content in the range from 8 to 38 mol%, preferably in the range from 23 to 35 mol%.
  • the aluminum content is preferably in the range of 50-70 mol%.
  • the catalyst according to the invention is characterized in that its physicochemical properties selected from the group of phase composition according to XRD, BET surface area, average pore diameter and / or ramming weight have preferred values.
  • a particularly preferred embodiment of the catalyst has a BET surface area whose value is in the range from 10 to 200 m 2 / g, preferably from 15 to 150 m 2 / g, more preferably from 20 to 100 m 2 / g, even more preferably from 30 to 80 m 2 / g, more preferably from 30 to 78 m 2 / g and especially preferably from 30 to 76 m 2 / g.
  • the BET specific surface area was determined according to DIN 66131.
  • a preferred embodiment of the catalyst also has a characteristic ramming weight which is preferably ⁇ 1500 g / L, more preferably ⁇ 1350 g / L, and still more preferably ⁇ 1 100 g / L.
  • the determination of the characteristic ramming weight was carried out by means of a ramming volume STAV 2003 from JEL. For the measurement, a 0.5-1.0 mm split fraction of the catalyst was used.
  • Another and essential aspect of the invention relates to a process for methanation, preferably high-temperature methanization, which is characterized by the features set forth in claims 7 to 14 features.
  • the preparation of the catalyst according to the invention is carried out according to one of claims 1 to 4 or the methanation catalyst according to the invention can be prepared according to claims 5 to 6.
  • the methanation process according to the invention can be carried out over a temperature range from 300.degree. C. to 900.degree. It is preferred to carry out the methanation method according to the invention in a temperature range above 500 ° C, more preferably, the implementation of the method in a temperature range of 500 ° C to 800 ° C, even more preferred is a temperature range of 600 ° C 750 ° C.
  • the high thermal stability of the catalyst material in carrying out the methanation process according to the invention in comparison to carrying out the process with a catalyst material which is known from the prior art. Due to the high thermal stability of the catalyst according to the invention Its deactivation is relatively low even under high temperature load. By means of the method according to the invention, the service life of the catalyst can be significantly extended, which leads to an improvement in the economy of the process. In addition to the improved thermal stability of the catalyst, the catalyst of the invention also has a higher mechanical hardness over comparable prior art catalysts. Due to the increased mechanical stability of the inventive method can be made at high process pressures. The process pressures can be in a range of 10 to 50 bar, usually between 20 and 30 bar, for example 25 bar.
  • the coking tendency is low in connection with the process according to the invention, which is conducive to obtaining the high activity.
  • a preferred embodiment of the process according to the invention relates to the methanation of synthesis gas which has a h / CO ratio in the range from 2.5 to 4, more preferably in the range from 3 to 3.5.
  • the synthesis gas is provided, for example, from a coal gasification (for example Lurgi process).
  • this synthesis gas originating from the coal gasification is first purified before the methanization. For example, the sulfur-containing components and much of the CO2 are removed prior to performing the methanation.
  • the Lurgi process is characterized by the fact that a relatively high proportion of methane is already present in the synthesis gas.
  • the dry synthesis gas contains the following main components in the following typical concentrations in volume fractions: -35 vol% CH 4 , ⁇ 45 vol% H2 and -15 vol% CO, secondary components may be: in particular CO2, but also nitrogen or higher hydrocarbons , for example ethane.
  • the reaction starting temperature is limited by reducing the CO content in the synthesis gas by recycling part of the product stream in order to limit the exothermicity of the overall reaction.
  • the catalyst is thus treated according to Lurgi process with a synthesis gas of the following composition: CH 4 content in the range of 36 to 42 vol .-%, H 2 content in the range of 35 to 45 vol .-%, CO content in the range of 9 to 12 vol.%, H 2 O content in the range of 8 to 12 vol.% and CO 2 in the range of 0 to 3 vol.%.
  • the recycle stream and directly the purified synthesis gas from the coal gasification which was previously subjected to the usual purification steps used.
  • the synthesis gas may also contain other components - such as nitrogen, argon - that do not participate themselves in the methanation reaction.
  • the sulfur content of the synthesis gas should be as low as possible to avoid poisoning of the nickel centers by sulfidation.
  • the inventive method is operated in a driving manner, the GHSV in the range of 500 to 50,000 r 1, preferably in a range from 1,000 to 15,000 r 1, and particularly preferably is in a range of 1000 to 5000 hr. 1
  • the use of the catalyst according to the invention in the form of shaped bodies is also advantageous, in particular, with regard to carrying out the methanation reaction, since it is possible by means of the shaped body to achieve a lower pressure drop within the reactor than by means of a bulk material catalyst.
  • a particular suitability of the catalyst material in connection with the use in methanation reactions is also based on the high mechanical stability of the material.
  • shaped bodies With regard to shaped bodies, they have a nearly identical shape and have a certain minimum extension in each direction of the three spatial axes, the extent in each direction of a spatial axis being greater than 2 mm.
  • the masterbatch was heated to 80 ° C in the rotary kiln and held there for 1 hour at 80 ° C with the rotary tube and the premix therein moved at two revolutions per minute and an air flow of 150 L / h was passed through the rotary tube ,
  • the amount by weight of the premix obtained after cooling was 886 g.
  • the sample obtained in the premix was subjected to cryogenic calcination.
  • the sample was placed in a quartz glass flask, this mounted in a rotary kiln and heated therein at a heating rate of 5 ° C / min to a target temperature of 425 ° C and heated at 425 ° C for one hour.
  • the quartz flask was moved at a rotation frequency of 12 revolutions per minute while simultaneously passing air through the piston at a flow rate of 1 L / min.
  • the sample obtained in the low-temperature calcination was mixed with graphite powder and pressed by means of a stamp press into tablets.
  • the graphite powder serves as a lubricant, and instead of the graphite, it would also be possible to use stearic acid or magnesium stearate.
  • the tablets produced by means of the press used here had a diameter of 4.75 mm and a thickness of about 4-5 mm.
  • the lateral compressive strength of the tablets was 60-70 N.
  • the tablets were comminuted with a screen mill and forced through a sieve to obtain a split fraction of ⁇ 1.6 mm.
  • the precompacted material was again tableted, yielding tablets with a diameter of 4.75 mm and a thickness of 3-4 mm.
  • the tablets had a lateral compressive strength of 130-150 N.
  • the thus-obtained sample material was calcined in a muffle furnace while passing air at 850 ° C for one hour and then cooled to room temperature.
  • the sample material positioned in the muffle furnace was heated from room temperature to 850 ° C using a heating rate of 5 ° C / min.
  • the air which was passed through the furnace during the heating phase, the calcination and the cooling phase had a flow rate of 6 L / min.
  • the calcined sample material was subjected to chemical and physical characterization. In the elemental analysis, the following composition was found: 21 wt .-% NiO, 53 wt .-% Al 2 0 3 and 23 wt .-% MgO, wherein the information refers to the oxides.
  • magnesium spinel (MgA 0 4 ) or MgNiO 2 were detected as phases.
  • the mean crystallite size of the phases was determined using the reflections. The result was that the spinel particles had a crystallite size of 9.0 nm and the mixed oxide particles had a crystallite size of 16.5 nm.
  • the sample material was characterized by nitrogen sorption and Hg porosimetry.
  • the sample material had a BET surface area of 67 m 2 / g.
  • the sample material had a Hg
  • the sample material had a monomodal pore structure. On average, the pores of the sample material had a pore diameter of about 15 nm.
  • a further catalyst M2 was prepared analogously to M1, this was calcined at a temperature of 950 ° C. In the elemental analysis, the following composition was found: 21 wt .-% NiO, 53 wt .-% Al 2 0 3 and 23 wt .-% MgO, the information on refers to the oxides.
  • magnesium spinel (MgA C) or MgNiO 2 were detected as phases (see FIG. 1). Using the Scherrer equation, the mean crystallite size of the phases was determined using the reflections. The result was that the spinel particles had a crystallite size of 14 nm and the mixed oxide particles had a crystallite size of 13 nm.
  • the sample material was characterized by nitrogen sorption and Hg porosimetry.
  • the sample material had a BET surface area of 58 m2 / g.
  • the sample material had a Hg pore volume of 0.41 mL / g and a pore surface area of 48 m 2 / g, with the sample material having a monomodal pore structure.
  • the pores of the sample material had a pore diameter of about 34 nm.
  • the solution of the metal nitrate salts and the soda solution were simultaneously dropped into the aqueous hydrotalcite dispersion container.
  • the template with the aqueous hydrotalcite dispersion was heated to 48 ° C and the dispersion with a stirrer durmischt.
  • the pH of the aqueous dispersion was controlled and the addition of the soda solution was controlled to maintain the pH in the receiver at 8.0.
  • a total of 3.5 L soda solution had been used as the precipitation reagent.
  • the suspension obtained by the precipitation process was stirred for a further 15 minutes and then the precipitate was filtered off with suction by means of a suction filter.
  • the filter cake was washed with deionized water, at the same time the nitrate content of the filtrate was determined.
  • the temperature of the water used for washing was 20 ° C.
  • the washing process was stopped as soon as nitrate ions could no longer be detected in the filtrate (the nitrate content was thus below the detection limit of 10 ppm).
  • an amount of water of 350 L was needed.
  • the washed filter cake was then dried at 120 ° C for a period of 16 h in a drying oven.
  • the dried solid was heated for 5 h at 700 ° C in a muffle furnace.
  • the muffle furnace and the solid contained therein were heated to 700 ° C at a controlled heating rate, and during heating, an air stream was passed through the muffle furnace at a flow rate of 20 L / min.
  • the solid obtained in this calcination was mixed with 3% by weight of graphite powder and the mixture was compressed to tablets with a stamping press.
  • the tablets obtained had a diameter of 4.75 mm and a thickness of about 2 mm.
  • the tablets were comminuted with a sifting mill and forced through a sieve with a mesh size of 1 mm to obtain a split fraction with particles smaller than 1 mm.
  • the fracture fraction obtained after precompacting was mixed with 10% by weight of Puralox (Bohmite from Sasol) and 3% by weight of graphite, intimately mixed and subjected to tableting.
  • the resulting tablets had a diameter of 4.75 mm and a thickness of about 3 to 4 mm.
  • the lateral compressive strength of the tablets was 100 N.
  • the composition of the tablets or the calcined samples was determined, which has a Ni content of 29.8 wt .-%, an Al content of 21, 1 wt .-%, an Mg content of 4.7 Wt .-% and a carbon content of 3.1 wt .-% had.
  • the samples showed an ignition loss of 7.3% by weight.
  • the oxides the following composition was determined for the calcined precipitate: 41% by weight NiO, 43% by weight Al 2 O 3 , 8.4% by weight MgO and 3.3% by weight C.
  • the XRD analysis of the calcined sample identified nickel oxide (NiO) and nickel spinel (Ni-AI2O4).
  • the nickel oxide particles had an average crystallite size of 5.0 nm, which was determined from an analysis of the respective reflections using the Scherrer equation.
  • the sample material had a BET surface area of 165 m 2 / g.
  • the sorption test was carried out with nitrogen.
  • a pore volume of 0.33 mL / g was determined.
  • the sample material showed a bimodal pore structure: the majority of the pores had a mean pore diameter of 6 nm and the small part of the pores a mean pore diameter of 30 nm. On average, a pore diameter of 11 nm was determined.
  • a calculation of the surface area of the sample material based on the Hg analysis revealed a surface area of 123 m 2 / g.
  • the catalysts Example M1, Example M2 and Comparative Example VM1 were sequentially exposed to the process conditions of CO methanation in a pilot reactor to produce synthetic natural gas to further characterize the performance characteristics of the catalysts in terms of CO methanation.
  • the experimental reactor was equipped with a equipped with 50 ml_ of the respective catalyst sample before the individual tests (ie example M1, example M2 or comparative example VM1). When filled, the catalyst samples were in the form of tablets.
  • the catalyst built into the tube reactor and the test stand Comparative Example VM1 was first subjected to activation.
  • the catalyst VM1 was heated in the presence of a stream of nitrogen to 280 ° C and then exposed for 16 h a reductive atmosphere by the nitrogen stream 5 vol .-% Hb were admixed.
  • the catalysts according to the invention, Example M1 and Example M2 were not activated but were incorporated and started directly in the oxidic form. It should be mentioned as an advantage that a start-up of the method according to the invention is also possible without activation of the catalysts.
  • the methanation reaction was started, with the catalyst exposed to a feed gas stream preheated to 280 ° C.
  • the feed gas stream had a flow rate of 1202 NL / h and comprised the six components hydrogen, CO, CO2, CH4, N2 and H2O, which were composed of the respective individual volume flows in the following ratio: 468 NL / h hydrogen, 132 NL / h CO , 12 NL / h C0 2 , 456 NL / h CH 4 , 24 NL / h N 2 and 1 10 NL / h H 2 0.
  • the catalyst of the invention (Example M1) showed a CO conversion of 93% and the comparative example (VM1) showed a CO conversion of 88%.
  • the CO conversion of Example M1 was 5% higher than that achieved with Comparative Example VM1.
  • the catalyst according to the invention (Example M1) was able to provide the high conversion over a period of more than 1200 h, whereas the catalyst from Comparative Example VM1 already showed a significant loss of activity after approximately 300 h, which led to the discontinuation of the experiment.
  • the catalyst from Example M1 also had a significantly higher mechanical resistance than the catalyst from Comparison Example VM1.
  • Example M1 The catalysts of Example M1, Example M2 and Comparative Example VM1 were removed from the reaction tube after the completion of the methanation test and subjected to characterization.
  • the samples were the expansion catalyst Example M1, the expansion catalyst Example M2 and the expansion catalyst Comparative Example VM1.
  • the catalyst of the invention showed a higher CO conversion of 95%.
  • the CO conversion achieved on the catalyst of Example M2 was 2% higher than that achieved with the catalyst of Example M1.
  • the catalyst according to the invention was able to deliver the high conversion over a period of more than 480 h, whereas the catalyst from Comparative Example VM1 already showed a significant loss of activity after approximately 300 h, which led to the discontinuation of the experiment.
  • the catalyst from Example M2 also had a higher mechanical resistance than the catalyst from Example M1 with a lateral compressive strength of 168 N.
  • Table 1 shows the composition of the educt gas before it was contacted with the catalyst and the product gas obtained after contacting with the inventive catalyst Example M1.
  • the data for the individual components refer to% by volume.
  • the duration of the catalyzed experiment was 1200 h.
  • Table 2.A shows the reactant and product gas composition of the methanation test of the comparative catalyst (Comparative Example VM1) over a test period of 300 h. After this time, a decline in turnover was observed, i. H and CO content in the product stream increased and the CH content decreased. The details of the individual components are given in% by volume.
  • Table 2.B shows the composition of the educt gas before it was contacted with the catalyst and the product gas obtained after contacting with the inventive catalyst Example M2.
  • the data for the individual components refer to% by volume.
  • the duration of the catalysis experiment was 480 h.
  • Table 3 shows a summary of the parameters determined by XRD, nitrogen sorption, and Hg porosimetry analysis of expanded catalyst Example 1 (after 1200 h of testing) and maturing catalyst VM1 (after 300 h of testing).
  • the Scherrer equation was used to estimate the crystallite size.
  • the XRD analyzes were performed on a Bruker / AXS D8 Advance Series 2 using CuK alpha source (0.154nm wavelength at 40kV and 40mA). The measurements were made over the measuring range: 5-80 ° (2Theta), 0.02 ° steps with 4.8 seconds / step.
  • the structural analysis software TOPAS (Bruker AXS) was used to determine the mean crystallite sizes of the individual phases.
  • Figure 4 shows a plot of the powder diffractogram plotted on catalyst sample Example M2 after high temperature calcination.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un catalyseur pour mettre en œuvre des réactions de méthanisation. La préparation du catalyseur repose sur la mise en contact d'une substance de départ contenant de l'hydrotalcite avec un sel métallique fusible. Les composés mis en contact subissent un mélange de l'intérieur et sont traités thermiquement de sorte que la fraction sel métallique est mise en fusion, puis soumise à une étape de calcination à basse température et à haute température. La masse en fusion de sel métallique contient au moins un métal qui est choisi dans le groupe comprenant K, La, Fe, Co, Ni, Cu et/ou Ce, de préférence Ni. De préférence, la masse en fusion de sel métallique comprend/contient du nitrate de nickel hexahydraté. La substance de départ contenant de l'hydrotalcite est de préférence de l'hydrotalcite ou un composé analogue à hydrotalcite, la substance de départ contenant de l'hydrotalcite comprenant de préférence du magnésium et de l'aluminium comme espèces métalliques. Le catalyseur selon l'invention est employé de préférence pour la mise en œuvre de réactions de méthanisation à pression élevée (10 à 50 bar) et haute température.
EP12847684.3A 2011-11-08 2012-11-07 Procédé de préparation d'un catalyseur de méthanisation et procédé de méthanisation d'un gaz de synthèse Withdrawn EP2776164A4 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12847684.3A EP2776164A4 (fr) 2011-11-08 2012-11-07 Procédé de préparation d'un catalyseur de méthanisation et procédé de méthanisation d'un gaz de synthèse

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11188238 2011-11-08
PCT/IB2012/056208 WO2013068931A1 (fr) 2011-11-08 2012-11-07 Procédé de préparation d'un catalyseur de méthanisation et procédé de méthanisation d'un gaz de synthèse
EP12847684.3A EP2776164A4 (fr) 2011-11-08 2012-11-07 Procédé de préparation d'un catalyseur de méthanisation et procédé de méthanisation d'un gaz de synthèse

Publications (2)

Publication Number Publication Date
EP2776164A1 true EP2776164A1 (fr) 2014-09-17
EP2776164A4 EP2776164A4 (fr) 2015-08-19

Family

ID=48288611

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12847684.3A Withdrawn EP2776164A4 (fr) 2011-11-08 2012-11-07 Procédé de préparation d'un catalyseur de méthanisation et procédé de méthanisation d'un gaz de synthèse

Country Status (8)

Country Link
EP (1) EP2776164A4 (fr)
JP (1) JP6125518B2 (fr)
KR (1) KR20140097308A (fr)
CN (1) CN104039452B (fr)
CA (1) CA2854914A1 (fr)
RU (1) RU2014123057A (fr)
WO (1) WO2013068931A1 (fr)
ZA (1) ZA201404092B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021152614A1 (fr) * 2020-01-31 2021-08-05 Institute Of Chemical Technology Catalyseur permettant la réaction de méthanation du co2 ayant une activité et une stabilité à long terme élevées et son procédé

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2776157B1 (fr) * 2011-11-08 2021-01-06 Basf Se Procédé de fabrication d'un catalyseur de reformage et reformage de méthane
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
CN105817219B (zh) * 2015-01-04 2018-10-16 神华集团有限责任公司 一种甲烷化催化剂及其制备方法和应用
WO2018219992A1 (fr) 2017-06-02 2018-12-06 Basf Se Procédé d'hydrogénation de dioxyde de carbone en présence d'un catalyseur contenant du nickel et des spinelles de magnésium
CN114250357B (zh) * 2020-09-22 2023-07-25 中冶长天国际工程有限责任公司 高氢低碳烧结料层结构、烧结系统及方法
CN113368851A (zh) * 2021-06-09 2021-09-10 中国科学院青岛生物能源与过程研究所 一种制备氧化物负载金属的方法及应用
KR102619167B1 (ko) * 2022-02-25 2023-12-27 포항공과대학교 산학협력단 열안정성이 향상된 메탄 개질 반응용 촉매 제조방법 및 그 촉매

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL302476A (fr) * 1962-12-29
DE2231317A1 (de) * 1972-06-27 1974-01-10 Basf Ag Katalysator und dessen verwendung zur herstellung von methan
DE2314804C3 (de) * 1973-03-24 1982-01-21 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur Erzeugung methanhaltiger Gase aus Kohlenwasserstoffen
US4217295A (en) * 1975-07-16 1980-08-12 Nl Industries, Inc. Process of catalytic methanation
CA1078878A (fr) * 1975-07-16 1980-06-03 Nl Industries Procede catalytique de preparation du methane
DE2729921C3 (de) * 1977-07-02 1985-01-03 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur Erzeugung eines mit Erdgas austauschbaren Gases
DE2952683A1 (de) * 1979-12-29 1981-07-02 Ruhrchemie Ag, 4200 Oberhausen Methanisierungskatalysator und verfahren zu seiner herstellung
GB2222963B (en) * 1988-09-23 1992-01-02 British Gas Plc Catalysts
US5399537A (en) * 1992-12-21 1995-03-21 Amoco Corporation Method for preparing synthesis gas using nickel catalysts
EP1013603A1 (fr) * 1998-12-22 2000-06-28 Haldor Topsoe A/S Procédé de reformage à la vapeur catalytique d'une charge d'hydrocarbures
DE60011868T2 (de) * 1999-10-01 2005-08-25 Bp Corporation North America Inc., Warrenville Verfahren zur Herstellung von Synthesegas unter Verwendung von aus Hydrotalcit abgeleiteten Nickelkatalisatoren
FR2809030B1 (fr) * 2000-05-22 2002-08-16 Univ Pasteur Catalyseur pour la gazeification de la biomasse en lit fluidise, procede d'obtention et utilisations d'un tel catalyseur
KR100398058B1 (ko) * 2001-05-18 2003-09-19 주식회사 경동도시가스 수식된 θ-알루미나에 담지되어 이루어진 니켈계 개질촉매및 이를 이용한 천연가스로부터 합성가스의 제조방법
JP4488178B2 (ja) * 2004-02-26 2010-06-23 戸田工業株式会社 メタン化触媒及びその製造方法、並びに該メタン化触媒を用いた一酸化炭素をメタン化する方法
KR100892033B1 (ko) * 2007-10-08 2009-04-07 한국에너지기술연구원 고표면적 스핀넬 구조의 나노크기 결정을 가지는ｙＭｇＯ(1-ｙ)Ａｌ₂Ｏ₃에 나노크기로 담지된 니켈계개질촉매 및 이를 이용한 수증기-이산화탄소 복합개질에의한 천연가스로부터 합성가스의 제조방법
EP2226308B1 (fr) * 2007-12-28 2018-10-17 Toda Kogyo Corp. Article poreux moulé, son procédé de fabrication, support de catalyseur et catalyseur
KR100991263B1 (ko) * 2008-08-01 2010-11-01 현대중공업 주식회사 천연가스를 수증기와 이산화탄소로 동시에 개질하는 혼합개질 반응용 니켈계 촉매

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021152614A1 (fr) * 2020-01-31 2021-08-05 Institute Of Chemical Technology Catalyseur permettant la réaction de méthanation du co2 ayant une activité et une stabilité à long terme élevées et son procédé
GB2605087A (en) * 2020-01-31 2022-09-21 Institute Of Chemical Tech Catalyst for Co2 methanation reaction having high activity and long term stability and process thereof
GB2605087B (en) * 2020-01-31 2024-05-22 Institute Of Chemical Tech Catalyst for Co2 methanation reaction having high activity and long term stability and process thereof

Also Published As

Publication number Publication date
JP2015502247A (ja) 2015-01-22
CN104039452A (zh) 2014-09-10
RU2014123057A (ru) 2015-12-20
CN104039452B (zh) 2017-03-08
EP2776164A4 (fr) 2015-08-19
KR20140097308A (ko) 2014-08-06
ZA201404092B (en) 2016-06-29
CA2854914A1 (fr) 2013-05-16
JP6125518B2 (ja) 2017-05-10
WO2013068931A1 (fr) 2013-05-16

Similar Documents

Publication Publication Date Title
US8916491B2 (en) Process for producing a methanation catalyst and a process for the methanation of synthesis gas
EP2776164A1 (fr) Procédé de préparation d'un catalyseur de méthanisation et procédé de méthanisation d'un gaz de synthèse
US9259712B2 (en) Process for producing a reforming catalyst and the reforming of methane
EP2776157B1 (fr) Procédé de fabrication d'un catalyseur de reformage et reformage de méthane
EP3116826B1 (fr) Catalysezr contenant de l'yttrium pour la hydrogenation de dioxid de carbone, hydrogenation de dioxid de carbone a haute temperature et/ou reformage et procede pour la hydrogenation de dioxid de carbone et/ou reformage
WO2013118078A1 (fr) Catalyseur contenant de l'hexaaluminate pour le reformage d'hydrocarbures et procédé de reformage
EP2886514A1 (fr) Procédé de reformage de mélanges à partir d'hydrocarbures et de dioxyde de carbone
DE60015345T2 (de) Verfahren zur herstellung von quasi-kristallinen boehmiten
DE112012000702T5 (de) Katalysatoren
US10987660B2 (en) Hexaaluminate-comprising catalyst for the reforming of hydrocarbons and a reforming process
DE112012002361T5 (de) Wassergas-Shift-Katalysator
WO2012171933A1 (fr) Catalyseur oxyde mixte contenant du cobalt et du molybdène, ainsi que sa production et son utilisation comme catalyseur de conversion du gaz à l'eau
DE112013000754T5 (de) Behandlung eines Katalysatorträgers
DE4303715A1 (de) Chromfreier Katalysator auf Basis Eisenoxid zur Konvertierung von Kohlenmonoxid
DE102008004135B4 (de) Katalysatorpulver
WO2018219992A1 (fr) Procédé d'hydrogénation de dioxyde de carbone en présence d'un catalyseur contenant du nickel et des spinelles de magnésium
WO2024056606A1 (fr) Procédé de reformage de nh3
KR20170057168A (ko) 알코올 합성용 촉매, 이의 제조방법 및 그의 용도
DE1667121A1 (de) Verfahren zur Umbildung von Kohlenwasserstoffen mit Dampf

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140610

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RA4 Supplementary search report drawn up and despatched (corrected)

Effective date: 20150716

RIC1 Information provided on ipc code assigned before grant

Ipc: B01J 37/04 20060101ALI20150710BHEP

Ipc: B01J 23/02 20060101ALI20150710BHEP

Ipc: B01J 37/00 20060101ALI20150710BHEP

Ipc: B01J 23/00 20060101ALI20150710BHEP

Ipc: B01J 37/08 20060101ALI20150710BHEP

Ipc: B01J 35/00 20060101ALI20150710BHEP

Ipc: B01J 23/70 20060101ALI20150710BHEP

Ipc: B01J 23/78 20060101ALI20150710BHEP

Ipc: B01J 37/16 20060101ALI20150710BHEP

Ipc: B01J 27/236 20060101ALI20150710BHEP

Ipc: C10L 3/08 20060101AFI20150710BHEP

Ipc: B01J 35/10 20060101ALI20150710BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20171222