WO2006079850A1 - Catalyseur et procédé de fabrication - Google Patents

Catalyseur et procédé de fabrication Download PDF

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Publication number
WO2006079850A1
WO2006079850A1 PCT/GB2006/050020 GB2006050020W WO2006079850A1 WO 2006079850 A1 WO2006079850 A1 WO 2006079850A1 GB 2006050020 W GB2006050020 W GB 2006050020W WO 2006079850 A1 WO2006079850 A1 WO 2006079850A1
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metal
catalyst
monolith
cobalt
nickel
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PCT/GB2006/050020
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English (en)
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Cornelis Martinus Lok
Jill Turner
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Johnson Matthey Plc
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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • 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
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • 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
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • 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
    • B01J35/392—Metal surface area
    • 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
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g

Definitions

  • the present invention relates to a metal-containing catalyst in the physical form of a monolith and to a novel method of preparing such a catalyst.
  • Metal catalysts such catalysts containing nickel, copper or cobalt in their elemental or an oxidic form, are commercially useful catalysts for a number of reactions, for example hydrogenation reactions. They have been made by a variety of methods such as precipitation of an insoluble metal salt, or impregnation of a support with a soluble metal salt in each case usually followed by conversion to the elemental metal which is the active form of the catalyst in hydrogenation reactions.
  • the catalysts may be supplied in the form of small particles, e.g. up to about 100 ⁇ m in diameter for use in slurry-phase reactions.
  • supported metal catalysts may be supplied as larger particles, e.g. tablets, granules or extruded pellets up to about 10mm in dimension, for use in fixed or trickle-bed reactions.
  • Nijhuis et al (Catalysis Today 66 (2001) 157 - 165) describe the hydrogenation of ⁇ -methyl styrene using a monolithic catalyst made by impregnation of a solution of nickel nitrate and urea onto an alumina-washcoated monolith.
  • EP-A-0233642 describes the hydrogenation of organic compounds using a monolith-supported catalyst which comprises a washcoated monolith substrate which is impregnated with a catalyst metal selected from Pd, Pt, Ni, Cu, Ag and mixtures of two or more of these metals.
  • a monolithic catalyst and its use for the hydrogenation of animal and vegetable oils is described in US-A-4584139.
  • the catalyst comprises a Raney-metal surface alloy which is integral with and derived from a nickel alloy monolithic mesh structure.
  • US-A-4163750 relates to the catalytic hydrogenation of edible oils using a supported catalyst metal selected from Fe, Co, Ni, and platinum group metals deposited on the outer surfaces of a support which may be a honeycomb or so-called cross-flow support.
  • a structured monolith catalyst comprising a metal compound deposited on a support, said catalyst support being in the form of a structured monolith having a plurality of channels extending through the monolith, each channel having a surface comprising said metal compound, wherein the metal is selected from the group consisting of nickel, copper and cobalt and wherein, when the metal is nickel, the nickel surface area of the catalyst per gram of nickel following reduction in hydrogen at 425 0 C when measured by hydrogen chemisorption at 35 0 C is > 80 m 2 g "1 more preferably > 100 m 2 g "1 , especially > 120 m 2 g "1 , and wherein, when the metal is copper, the copper surface area of the catalyst per gram of copper following reduction in hydrogen at 230 0 C when measured by nitrous oxide chemisorption at 68 0 C is > 60 m 2 g "1 more preferably > 80 m 2 g "1 , especially > 100 m 2 g "1 and and wherein, when the metal is nickel, the nickel
  • the metal surface area of the catalyst per gram of metal when measured by hydrogen chemisorption is described, in "Physical and Chemical Aspects of Adsorbents and Catalysts", edited by B. G. Linsen, Academic Press, 1970 London and New York, page 494 and 495, is a measure of the surface area of the reduced, i.e. elemental metal in the catalyst.
  • the detailed methods for metal surface area determination are given below.
  • Hydrogen chemisorption at 35 and 150 0 C is used for nickel and cobalt respectively, whilst nitrous oxide decomposition is used to determine metallic copper surface areas as described by Evans et al (Applied Catalysis 7 (1983) 75 - 83).
  • the catalysts may, of course, be reduced for use under different conditions; the specified reduction conditions are given in order to define the metal surface areas claimed.
  • the catalyst comprises from 1 - 20% by weight of metal (measured as oxide). More preferably the metal content of the catalyst (i.e. the total catalyst, including the monolith core and any wash-coated support) is from 1 - 15%, most preferably from 3 - 10% by weight.
  • Metal in this context refers to the catalytic metal, i.e. the copper, cobalt or nickel metal, and not to any metallic monolith support that may be present.
  • a method of preparing a catalyst comprising a metal compound deposited on a support, wherein the metal is selected from the group consisting of nickel, copper and cobalt nickel, said catalyst being in the form of a structured monolith having a plurality of channels each channel having a surface comprising said metal compound, the method comprising the steps of :-
  • Monolithic structured catalysts are known in the art and are well described by Kapteijn et al in CAT-TECH June 1999 VoI 3 No 1.
  • structured monolith and structured monolith catalyst we mean the materials described in that article, i.e. a block having channels incorporated therein, within which a chemical reaction may take place which is catalysed by the active component of the monolith catalyst.
  • the channels are preferably of uniform shape and cross-section, although foams and sponge structures which have irregularly shaped channels, which may interconnect, are included in the invention.
  • the channels preferably run linearly through the monolith in the same direction and are preferably parallel with each other. In "cross-flow" monolith structures, channels are provided which run in more than one direction, often perpendicular with one another.
  • the channels may have a cross-section which is round, square, rectangular or other polygonal shape such as hexagonal or octagonal.
  • the monolith may be of any convenient size and more than one monolith may be employed in a single reactor. In many applications, the monolith is of a size and shape to fill the reactor. Monolith catalysts are sometimes referred to as "honeycomb" catalysts.
  • the catalyst support material may be selected from a variety of known supports such as ceramic materials or carbon.
  • Preferred ceramic supports include transition alumina, especially gamma or delta aluminas, alpha alumina, silica, silica-alumina, kieselguhr, titania, zirconia, ceria, magnesia, including coated supports such as titania- or zirconia-coated silicas or aluminas
  • the support material is preferably a porous material.
  • the monolith structure may be formed from the catalyst support e.g. by extruding the support material in the shape of the desired monolith. It is more preferred, however, to use as a monolith substrate an inert monolith-shaped core structure formed from e.g.
  • a preferred method of forming a layer of catalyst support material on a monolith core is washcoating, in which the monolith core is dipped into a solution of the catalyst support in a soluble form or a suspension of solid catalyst support particles and then removed and dried.
  • the catalyst support forms a layer over the surface of the monolith core material rather than being entirely deposited within the pores of the monolith core. It is further preferred that at least a portion of the catalyst support material is located within the pores of a porous monolith core material in order to increase the mechanical bonding between the catalyst support and the monolith core.
  • the metal ammine carbonate complex solution may be formed by first dissolving ammonium carbonate or carbamate in an ammonia solution (aqueous ammonium hydroxide) using about 200 - 400 g per litre of aqueous ammonia solution containing about 30 - 33% ammonia. Then a basic metal carbonate is dissolved in the ammonium carbonate/ammonia solution.
  • the amount of basic metal carbonate used depends upon the amount of metal desired to be in the final catalyst although it is usual to dissolve the metal carbonate in an amount approaching the saturation point in order to produce as high a loading of metal in the catalyst in a single impregnation as is practicable.
  • the pH of the solution is preferably in the range from 8 - 12.
  • the metal comprises nickel and/or cobalt and/or copper. More preferably the metal consists essentially of one of nickel or cobalt or copper. By "consists essentially of we mean that the metal consists of either nickel or cobalt or copper with the exception of certain impurities normally found in commercial samples of nickel or cobalt or copper. These impurities are typically present at concentrations of less than 1 % and do not affect the essential function of the catalyst.
  • the metal preferably comprises nickel and/or cobalt. Most preferably the metal consists essentially of either nickel or cobalt.
  • the catalyst support monolith should be immersed in the metal ammine carbonate solution for sufficient time to displace air from the surface of the support and channels of the monolith. Normally the monolith should remain in the solution for more than 60 seconds.
  • the monolith may thereafter be removed from the solution, excess solution being removed from the monolith, e.g. by wiping or blowing with air, and dried. In the drying process it is recommended to dry with the monolith channels running in a horizontal position, preferably with rotation of the monolith to minimise the movement of solution within the monolith which may result in an uneven distribution of the metal complex solution.
  • the monolith and associated metal ammine carbonate complex solution are then heated to a temperature sufficient to decompose said metal ammine carbonate complex to form and deposit an insoluble metal compound on the surface and within the pores of the support.
  • the temperature is preferably in excess of 50 0 C and is preferably in the range from 60 0 C to 120 0 C, more preferably from 80 to 110 0 C.
  • the nature of the insoluble metal compound varies depending on the conditions of heating, the identity of the metal and the time of heating. Normally the insoluble compound comprises a basic metal carbonate and/or hydroxy-carbonate, and/or metal oxides and/or metal hydroxides.
  • the metal ammine carbonate and monolith may be heated together whilst the monolith remains immersed in the liquid. In this case the metal ammine carbonate complex is decomposed and deposited onto the walls, including into the pores, of the catalyst support material.
  • the metal is cobalt
  • This oxidation may be achieved by allowing the solution to stand in contact with air, optionally with stirring/agitation, for a few hours or several days. Alternatively air may be bubbled through the solution.
  • the solution may be chemically oxidised by adding a peroxide solution or alternative oxidant to the cobalt ammine carbonate solution.
  • the composition of the insoluble cobalt compound resulting from the decomposition of the cobalt ammine complex is readily reducible to cobalt metal of high surface area.
  • cobalt species which is precipitated from the solution of complex e.g. a cobalt ammine carbonate complex, comprising Co(III) species contains a greater amount of Co 3 O 4 and less cobalt carbonate, cobalt hydroxycarbonate or ammonia than is deposited from the decomposition of a freshly made solution containing more Co(II) and less Co(III).
  • the precipitated cobalt compound contains a higher proportion of Co oxides than would be precipitated from a non-oxidised solution, so that calcination to convert the precipitated carbonates to oxides may be unnecessary.
  • the oxidation of the complex is sufficient for a preferred form of the method of making cobalt-containing catalysts of the invention when the redox potential is between O V and -20OmV, more preferably from -50 to -150 mV, and most preferably about - 10OmV, e.g. from -90 to -130 mV.
  • the preferred oxidation procedures for solutions of a cobalt ammine carbonate complex are fully described in WO05/107942.
  • the monolith loaded with deposited insoluble metal compound formed by decomposition of the metal ammine carbonate complex may, optionally, be calcined to form a dispersed metal oxide supported on the monolith.
  • the monolith catalyst may be useful for certain reactions, especially oxidation reactions.
  • the calcination conditions which may be used are variable depending upon the nature of the metal, the support and the form of the catalyst which is desired. For nickel, copper or cobalt catalysts calcination should be carried out for at least one hour at a temperature of from 200 - 600 0 C, preferably from 250 - 400 0 C. Normally the calcination process is continued for between 2 and 8 hours.
  • the dried monolith loaded with the deposited insoluble metal compound(s) formed by decomposition of the metal ammine carbonate complex is reduced in hydrogen, optionally after a calcination step as described above.
  • the reduction conditions to be used depend primarily on the identity of metal and the likelihood and desirability of a reaction between the metal and the catalyst support, to form e.g. metal aluminates or metal silicates in the case of alumina and silica supports respectively. If too high a reduction temperature is selected then there is a possibility that the dispersed metal may sinter leading to a reduction in metal surface area.
  • a reduction temperature in the range 250 to 550 0 C, particularly in the range 300 to 450 0 C are suitable.
  • a temperature in the range 150-400 0 C, particularly 200-300 0 C is preferred.
  • the hydrogen containing gas may be pure hydrogen, or hydrogen mixed with an inert gas such as argon, helium or nitrogen.
  • the reduction of the catalyst may be effected in situ in the reactor in which the catalyst is to be used.
  • the catalyst may be reduced ex-situ and then protected from oxidation of the reduced metal surface by passivation with e.g. an oxygen, CO 2 and/or nitrogen-containing gas or by storing in a protective atmosphere.
  • the monolith-supported catalysts of the invention are useful in a variety of chemical reactions as indicated in the literature referred to above.
  • the catalysts in their reduced form may be used for hydrogenation reactions, for example the hydrogenation of oils and fats, fatty acids, nitriles, aldehydes, unsaturated hydrocarbons, such as the C 5 - Ci 2 hydrocarbons normally present in pyrolysis gasoline ("Pygas”), including aromatics such as styrene and methyl styrene, and other organic species.
  • the cobalt catalysts of the invention and/or made by the process of the invention may additionally be useful in the Fischer-Tropsch synthesis of hydrocarbons.
  • the well-known Fischer-Tropsch synthesis converts a mixture of carbon monoxide and hydrogen, typically a synthesis gas having a hydrogen: carbon monoxide ratio in the range 1.7-2.5:1 to hydrocarbons.
  • the catalysts of the present invention are of particular utility because of their high metal surface areas.
  • the metal surface areas are measured using a standard procedure and instrumentation supplied by Micromeritics.
  • the procedure includes reduction of the sample in situ and differs depending on the metal to be measured.
  • sample Approximately 0.2 to 0.5 g of sample is used for the analysis.
  • the weight used to calculate the metallic surface area is that obtained after reduction.
  • the sample is degassed and dried by heating to 140 0 C at 10°C/min in a vacuum and holding at 140 0 C for 5 mins.
  • the pretreated sample is then reduced by changing the flowing gas to hydrogen and heating the sample from
  • a sample (1 - 2 g) of catalyst is crushed and sieved to a particle size of 0.6 - 1.0 mm, placed in a reactor tube and purged with flowing helium (100 ml/min) at 68 0 C for 2 minutes.
  • the temperature is increased at 8 0 C /min to 230 0 C under a flowing gas mixture of 5%v/v H 2 in helium (100 ml/min) and held at that temperature for 3 hours to effect reduction of the copper compounds to copper metal.
  • the catalyst is then cooled to 68 0 C under helium.
  • a gas mixture of 2.5% v/v N 2 O in helium is passed over the catalyst at a rate of 68 ml/min and the volume of N 2 evolved is measured.
  • the copper surface area per gram of catalyst is then calculated from the following equation:
  • a cordierite monolith, 1cm in diameter and having 400 channels per square inch to which an alumina washcoat had been pre-applied was dried at 105 °C for 2 hours and allowed to cool under dry conditions.
  • the monolith contained 140 kg of AI 2 O 3 per m 3 of monolith.
  • a solution of nickel ammine carbonate solution containing about 10 wt% of nickel was made as follows:- 25Og of ammonium carbonate chip was slowly dissolved in 1000ml of (33% w/v NH 3 ) ammonia solution. Then 30Og of nickel basic carbonate was added to the solution in 5Og aliquots and allowed to dissolve. Slow addition of the nickel compound is necessary to avoid excessive heat generation. The resultant liquor was filtered to remove any particulate matter.
  • a 10cm portion of the dried monolith was slowly immersed in a into the nickel ammine carbonate solution whilst being maintained in a vertical position and ensuring that all air was displaced from the channels. After two minutes immersion, the monolith was lifted out, drained of excess solution and the channels cleared using an air jet before drying at 105 0 C for 2 hours.
  • a series of six dipped monoliths was made by repeating the dipping and drying procedure a number of times shown in the Table 1.
  • the finished monoliths were calcined at up to 280 0 C (temperature ramp rate of 5 0 C per minute) for 4 hours.
  • the catalyst surface area was measured using a conventional BET method. The catalyst was reduced in hydrogen at 425 0 C and the nickel metal surface area was measured by hydrogen chemisorption at 35°C. The results are shown in Table 1.
  • a nickel catalyst containing 6 wt% of Ni (42.3 kg Ni per m 3 of monolith) was made from a 25.4 mm diameter x 150mm length alumina washcoated monolith using the method of Example 1 (3 successive immersion / drying steps).
  • the catalyst was used in the hydrogenation of a model Pygas liquid mixture comprising isoprene (3.1%), trans-1 ,3-pentadiene (0.9%), cis-1 ,3- pentadiene (0.5%), n-octane (34.4%), toluene (32.0%), styrene (24.0%) and dicyclopentadiene (5.2%).
  • the reaction was carried out in a batch recycle reactor. The catalyst was charged into the reactor and the reactor system purged with nitrogen.
  • a solution of 50Og Ni(NO 3 ) 2 .6H 2 O and 217g urea was prepared in 15Og of demineralised water.
  • the alumina washcoated monoliths (as used in Example 1) were dipped three times in the nickel/urea solution. After each dip the channels were cleared with compressed air then dried overnight at 80 0 C. The external surfaces were not dried. A fourth dip was not possible because the solution became unstable and gel-like, eventually solidifying. The monoliths were finally calcined at 280 0 C for 2 hours. The monolith properties were measured as described in Example 1 and the results are shown in Table 2. Table 2
  • Example 3 was repeated but using a solution comprising 35Og Ni(NO 3 ) 2 .6H 2 O, 15Og AI(NO 3 ) 3 .9H 2 O and 217g urea in 15Og of demineralised water.
  • the cordierite monolith core was not pre-coated with alumina.
  • the monolith was dipped in order to co-deposit the aluminium and nickel salts on the core, i.e. in order to avoid a separate alumina wash-coating step.
  • Table 3 The results are shown in Table 3.
  • a cobalt hexammine solution containing approximately 14 -15% w/w Co was made by dissolving 5 634g of ammonium carbonate chip in 1880ml of (30% w/v NH 3 ) ammonia solution. Then 528g of cobalt basic carbonate was added to the solution in 5Og aliquots and allowed to dissolve. The slow addition of the cobalt compound avoids excessive heat building up in the solution. The resultant liquor was filtered to remove any particulate matter. The redox potential of the solution was measured as -293 mV. 0
  • An alumina wash-coated cordierite monolith of dimensions 1" (25 mm) diameter, 6" (150mm) length & 400 cpsi was used as the catalyst support after drying at 105 0 C for 2 hours.
  • a 100 ml measuring cylinder was filled with the cobalt hexammine solution.
  • the pre-dried monolith was placed in a wire holder, maintaining a vertical position throughout the dipping procedure.
  • the 5 monolith was slowly lowered into the cobalt solution until completely immersed, ensuring all air was displaced from the channels.
  • a total immersion time of two minutes was employed after which the monolith was slowly lifted out. Following initial draining of the monolith the channels were cleared of all remaining solution using a jet of compressed air.
  • the external walls were cleared of excess solution by gently rolling over filter paper.
  • the impregnated monolith was 0 dried in a horizontal position at 105 0 C for a minimum of 2 hours.
  • Example 5 The preparation of a cobalt-containing monolith was carried out as described in Example 5, except that the prepared solution of cobalt ammine carbonate complex was stored in a plastic container and statically oxidised by means of regular ingress of oxygen and agitation (by shaking) until the redox potential was -5OmV. After this oxidation procedure it was used to prepare a monolith using the dipping and drying procedure of Example 5. Half of the dried monolith was calcined at 280 0 C for 4 hours at a ramp rate of 5°C. The cobalt metal surface area results are shown in Table 5.
  • a cobalt ammine carbonate solution was prepared as described in Example 5 but using 1056g cobalt basic carbonate (i.e. twice as much as in Example 5), added in aliquots over 10 hours, whilst continually stirring the solution, to dissolve. Slow addition was used to prevent any heat build up during dissolution of the cobalt powder. The final solution was stirred continually for a further 16 hours with air access before filtering to remove any undissolved cobalt carbonate. Filtration took 48 hours because the solution was very viscous.
  • Example 6 The dipping and drying procedure described in Example 5 was followed, although the solution was more viscous than the solution of Example 5 with the result that the channels of the monolith were difficult to clear before drying. Some crystal growth was observed to occur on the external surface of the monolith.
  • Table 6 The properties of the resulting catalyst were measured and are shown in Table 6. This example shows that monolith catalysts containing a relatively high loading of cobalt may be prepared using the method of the invention.

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Abstract

La présente invention décrit et revendique un catalyseur à support monolithique qui comprend du cuivre, du nickel ou du cobalt ayant une grande surface métallique, conjointement avec un procédé pour la préparation d’un tel catalyseur monolithique. Le procédé est basé sur l’imprégnation du monolithe et du support d’un complexe de carbonate de métal-amine, suivie par la décomposition du carbonate de métal-amine par chauffage.
PCT/GB2006/050020 2005-01-28 2006-01-26 Catalyseur et procédé de fabrication WO2006079850A1 (fr)

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EP2210664A1 (fr) * 2007-10-26 2010-07-28 Asahi Kasei Chemicals Corporation Article chargé de particules composites, procédé de production de l'article chargé de particules composites, et procédé de production de composé à l'aide de l'article chargé de particules composites en tant que catalyseur de synthèse chimique
WO2010089265A2 (fr) 2009-02-09 2010-08-12 Basf Se Catalyseurs d'hydrogénation, préparation et utilisation
WO2010089346A2 (fr) 2009-02-09 2010-08-12 Basf Se Procédé d'amélioration de l'activité catalytique de catalyseurs monolithiques
WO2010089266A2 (fr) 2009-02-09 2010-08-12 Basf Se Procédé pour améliorer l'activité catalytique de catalyseurs monolithiques
WO2010128137A3 (fr) * 2009-05-07 2011-05-26 Shell Internationale Research Maatschappij B.V. Améliorations concernant l'hydrogénation de composés aromatiques et d'autres composés organiques insaturés
US8778831B2 (en) 2008-03-27 2014-07-15 Umicore Ag & Co. Kg Base metal and base metal modified diesel oxidation catalysts
US9403151B2 (en) 2009-01-30 2016-08-02 Umicore Ag & Co. Kg Basic exchange for enhanced redox OS materials for emission control applications
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EP2210664A4 (fr) * 2007-10-26 2011-12-21 Asahi Kasei Chemicals Corp Article chargé de particules composites, procédé de production de l'article chargé de particules composites, et procédé de production de composé à l'aide de l'article chargé de particules composites en tant que catalyseur de synthèse chimique
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US9403151B2 (en) 2009-01-30 2016-08-02 Umicore Ag & Co. Kg Basic exchange for enhanced redox OS materials for emission control applications
WO2010089265A2 (fr) 2009-02-09 2010-08-12 Basf Se Catalyseurs d'hydrogénation, préparation et utilisation
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WO2010089266A2 (fr) 2009-02-09 2010-08-12 Basf Se Procédé pour améliorer l'activité catalytique de catalyseurs monolithiques
WO2010089346A2 (fr) 2009-02-09 2010-08-12 Basf Se Procédé d'amélioration de l'activité catalytique de catalyseurs monolithiques
WO2010128137A3 (fr) * 2009-05-07 2011-05-26 Shell Internationale Research Maatschappij B.V. Améliorations concernant l'hydrogénation de composés aromatiques et d'autres composés organiques insaturés
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US9567276B2 (en) 2014-12-23 2017-02-14 Evonik Degussa Gmbh Chromium-free hydrogenation of hydroformylation mixtures

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