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WO2007042456A1 - Procede pour hydrater des composes de carbonyle - Google Patents

Procede pour hydrater des composes de carbonyle Download PDF

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Publication number
WO2007042456A1
WO2007042456A1 PCT/EP2006/067078 EP2006067078W WO2007042456A1 WO 2007042456 A1 WO2007042456 A1 WO 2007042456A1 EP 2006067078 W EP2006067078 W EP 2006067078W WO 2007042456 A1 WO2007042456 A1 WO 2007042456A1
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Prior art keywords
diameter
copper
catalyst
height
acid
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PCT/EP2006/067078
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German (de)
English (en)
Inventor
Thorsten Johann
Steffen Maas
Stephan Schlitter
Tilman Sirch
Michael Koch
Stefan Rittinger
Michael Steiniger
Hermann Petersen
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BASF SE
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BASF SE
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—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
    • B01J23/005—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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain 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
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • 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
    • B01J35/19—Catalysts containing parts with different compositions
    • 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 invention relates to a process for the catalytic hydrogenation of carbonyl compounds in the presence of copper-containing catalyst moldings having in oxidic form a specific surface area of 50 to 150 m 2 / g, preferably 70 to 130, particularly preferably 80 to 1 10 m 2 / g and wholly or partially contain crystals with spinel structure and copper in the form of copper oxide and the copper oxide-containing catalyst shaped body in which the diameter d, the height h, the wall thickness w or the cell diameter r z of the shaped body ⁇ 5 mm, with the restriction of in the case of tablets in the form of symmetrical tablets, the diameter d and the height h are ⁇ 4 mm.
  • the catalytic hydrogenation of carbonyl compounds is carried out in industrial processes almost exclusively in fixed bed reactors.
  • catalysts in addition to catalysts of the Raney type especially supported catalysts, such as copper, nickel or noble metal catalysts are used.
  • DE-A 30 27 890 describes a process for the preparation of propanediols to hydrogenation catalysts which have a specific surface area of 50 to 150m 2 / g, wholly or partially contain crystals of spinel structure and copper in the form of copper oxide and have been obtained by Copper and aluminum in a ratio of 0.15 to 3 atoms of copper to an atom of aluminum from their compounds in the presence of carbonates at a pH of 4.5 to 9 drops and dries the precipitate thus obtained and at a temperature of Calcined 300 to 800 0 C.
  • the hydrogenation catalysts can be used as tablets or strand.
  • the object is achieved by a process for the catalytic hydrogenation of carbonyl compounds or a mixture of two or more carbonyl compounds in the presence of copper-containing catalyst moldings which in oxidic form have a specific surface area of 50 to 150 m 2 / g, preferably 70 to 130 m 2 / g, more preferably 80 to 1 10 m 2 / g, which have wholly or partially crystals with spinel structure and copper in the form of copper oxide. They are obtainable by a precipitation, which may include a subsequent stirring phase at settings different from the precipitation parameters, such as increased pH value.
  • the precipitate in a ratio of 0.25 to 3 atoms to an atom of aluminum from their compounds in the presence of carbonates at a pH of 4.5 to 9 during precipitation and subsequent stirring phase. It follows, a drying of the precipitate, an at least simple calcination at 200 to 650 ° C, preferably at 300 to 500 ° C, more preferably at 300 to 450 ° C and shaping with subsequent optional calcination at 300 to 600 ° C, in particular at 400 to 600 ° C, characterized in that the diameter d, the height h, the wall thickness w or the cell diameter r z of the shaped body ⁇ 5 mm, with the restriction that in the case of shaped bodies in the form of symmetrical tablets of the diameter d and the height is h ⁇ 4mm.
  • the diameter d, the height h, the wall thickness w or the cell diameter r z of the shaped bodies are preferably not smaller than 1.5 mm, particularly preferably not smaller than 1 mm.
  • Copper / aluminum / OH / CO 3 mixed crystals have a defined and measurable crystal lattice.
  • the crystals are preferably present in a layer structure.
  • the individual lattice sites are occupied by copper and aluminum and the radicals CO3, OH and H2O, with additional additives, usually in an amount of 0 to 10, in particular 0 to 5 wt .-%, based on the total catalyst, lattice sites can prove.
  • Suitable additives are suitably chromium, calcium, cobalt or magnesium, which in the form of their carbonates, hydroxides or oxides as lattice points be installed or occupy defects; if appropriate, the additives can also be present in amorphous or crystalline form in a mixture with the mixed crystals according to the invention.
  • calcined catalyst suitably consist of up to 90 wt .-%, in particular 1 to 80 wt .-% of the catalyst of crystals of the spinel type.
  • structure of the spinel type reference is made to Ullmanns Encyklopadie der ischen Chemie, Volume 6, pages 242 to 244.
  • the structure may correspond to the natural or synthetic pure spinel as well as the reddish, blue, black, greenish blue, yellow-green, green, emerald green, pink or ruby spinels, the spinel-like sapphire or the alexandrite-like spinel.
  • the catalyst components of the invention are in a ratio of 0.25 to 3, in particular 0.5 to 3 atoms of copper per atom of aluminum.
  • the catalyst has a specific surface area of 50 to 150 m 2 / g, preferably 70 to 130 m 2 / g, particularly preferably 80 to 1 10 m 2 / g.
  • the catalysts may have a pore volume of from 0.3 to 6, preferably from 0.3 to 1 cm 3 / g.
  • the precipitation is expediently carried out from an aqueous solution of the copper salts and aluminum salts and optionally the additives with carbonates and optionally hydroxides.
  • suitable salts are the acetates, chlorides, sulfates, bicarbonates, hydrogen sulfates and, in particular, nitrates of copper, aluminum and the additional metals.
  • the carbonate radicals in the catalyst can be added to the precipitation bath in the form of corresponding carbonates of copper, aluminum or additional metal, or expediently in the form of additional alkali metal carbonates or alkali bicarbonates, for example the potassium or sodium salts, which adjust the pH according to the invention.
  • the catalyst used according to the invention is advantageously prepared by means of two aqueous solutions, solution 1 containing the nitrates of copper, aluminum and optionally additional metal.
  • the solution 2 consists of an aqueous sodium carbonate solution. It is expedient to use 0.1 to 3 molar solutions of the metal compounds and 0.1 to 3 molar carbonate solutions or bicarbonate solutions. In the case of using a mixture of carbonates and hydroxides, usually alkali metal hydroxides, the carbonate content is expediently from 25 to 95% by weight of the mixture.
  • the precipitation is advantageously carried out at a temperature of 5 to 90, preferably 20 to 90 ° C. Preferably, both solutions are passed into a heated to the precipitation temperature stirred tank.
  • the precipitation can be carried out in one stage, generally at a pH of 5 to 9, in particular 5.5 to 8.5.
  • the overflow is stirred at a pH which has been increased by up to 3 pH units in the subsequent stirring phase (second precipitation) compared with the first precipitation.
  • the resulting precipitate is then filtered off appropriately and washed with water. salt-free, eg nitrate-free, washed.
  • salt removal from the precipitate is washing with very dilute, for example, adjusted to pH 10 sodium hydroxide solution, expedient to pH values in the wash water between 7.8 and 9.5 before filtration can be achieved.
  • nitrates are used, it is also possible to remove the nitrate from the precipitate with 0.1 to 1, preferably 0.2 to 0.3,% by weight aqueous CO 2 solution; in this case, a proportion of 5 to 20 wt .-% of the precipitated copper in solution.
  • the washed precipitate is then desirably dried, calcined at least once at 200 to 650 ° C, preferably at 300 to 500 ° C, more preferably at 300 to 450 ° C, optionally granulated and then deformed. After the deformation, additional calcination may optionally be carried out. However, it is also possible to calcine only after the deformation at 300 to 600 ° C, especially at 400 to 600 ° C.
  • the catalytic converter is brought into the desired shape.
  • the catalysts usually require the development of their special properties after filtration and drying of this special temperature treatment to develop their full activity and mechanical stability, recrystallization occurs; it forms copper oxide and crystals of spinel structure, which can be checked by X-ray structure analysis.
  • the catalyst generally shrinks upon calcination.
  • the specific surface according to the invention forms.
  • the catalyst contains Na 2 O or other alkali metal oxides in amounts greater than 0.3% by weight, based on the catalyst, higher temperatures, e.g. 610 to 750 ° C, appropriate. In the case of aluminum-poorer catalysts, calcination temperatures between 300 and 600 ° C. are expedient.
  • the above-described dried powder is used to produce the shaped catalyst bodies according to the invention with the aid of a suitable pressing tool to give moldings having a diameter d, a height h, a wall thickness w or a cell diameter r z ⁇ (smaller than) 5 mm, preferably ⁇ ( less than or equal to) 4mm, deformed, with the restriction that when deformed into symmetrical tablets, the diameter d and the height of these tablets is h ⁇ (less than) 4mm, preferably diameter and height ⁇ (less than) 3mm.
  • the diameter d, the height h, the wall thickness w or the cell diameter r z of the shaped bodies are preferably not smaller than 1, 5 mm, particularly preferably not smaller than 1 mm.
  • Suitable moldings are all customary catalyst bodies which can be produced by means of compression or deformation tools known per se, such as, for example, tablets, ring tablets, strands, rods or honeycomb bodies.
  • As a deformation aid graphite, stearic acid, Mg stearate, copper powder or other substances are used for the deformation process.
  • Supporting the shaping suitable substances preferably in a proportion of 2-4 wt .-%, based on the weight of the dried powder added.
  • the shaped catalyst bodies can be symmetrical, ie height h and diameter d are the same, or be asymmetrical, that is, height h and diameter d assume different values.
  • Ring tablets with a wall thickness w ⁇ (less than or equal to 4 mm) are particularly preferred; symmetrical catalyst tablets in which diameter d and height h are 3 mm are particularly preferred in the method according to the invention.
  • the wall thickness w of the ring tablets are preferably not smaller than 1, 5 mm, more preferably not smaller than 1 mm.
  • the present invention also relates to a copper-containing shaped catalyst body which in oxidic form having a specific surface area of 50 to 150 m 2 / g, preferably 70 to 130 m 2 / g, particularly preferably 80 to 1 10 m 2 / g, the Wholly or in part, crystals of spinel structure and copper in the form of copper oxide, which is obtainable by two-step precipitation of copper and aluminum in the ratio of 0.25 to 3 atoms of copper to one atom of aluminum from their nitrate compounds in the presence of carbonates at a pH Value of 4.5 to 9, drying of the precipitate, at least simple calcination and shaping, characterized in that the diameter d, the height h, the wall thickness w or the ZeII- diameter r z of the moldings ⁇ 5 mm, with the Restriction that for shaped articles in the form of symmetrical tablets the diameter d and the height h ⁇ 4mm.
  • the moldings of the invention are annealed at 300 to 600 ° C, in particular at 400 to 600 0 C.
  • the maxima in the pore radius distribution of the catalysts of the invention are between 1 and 1000 nm, preferably the distribution is bimodal with maxima between 10 and 60 nm and 60 and 800 nm.
  • the specific surface of the catalyst tablet is determined by the BET method by N 2 adsorption, in particular according to DIN 66 131.
  • the determination of the average pore diameter and the pore size distribution was carried out by Hg
  • Porosity in particular DIN 66 133 on a 1 10 Micromeritics Autopore 4 9500 at a contact angle of 140 °.
  • the fracture hardness of samples is determined by placing the sample under a stamp with a defined area and then moving the stamp against the sample until it breaks.
  • the pressure exerted on the sample by the punch, which is necessary to achieve the breakage, is called breakage hardness.
  • the lateral compressive strength was determined in the context of the present application with a device of the type "BZ 2.5 / T-S1 S" Twick (Ulm).
  • Activating the annealed catalyst occurs either before or after incorporation into the reactor.
  • the catalyst is to be used in its reduced form, it is incorporated into the reactor and charged directly under hydrogen pressure with the hydrogenation solution.
  • the catalyst before charging with the hydrogenation with reducing gases, for example hydrogen, preferably hydrogen inert gas mixtures, in particular hydrogen / nitrogen mixtures at temperatures of 100 to 300, preferably from 150 to 250, in particular from 180 to 240 ° C. prereduced. Preference is given to using a mixture with a hydrogen content of 1 to 100% by volume.
  • the preferred field of use of the catalyst moldings produced according to the invention is hydrogenation in a fixed bed.
  • the embodiment in the form of a fluidized-bed reaction with catalyst material in an up-and-down motion is likewise possible.
  • the hydrogenation can be carried out in the gas phase or in the liquid phase.
  • the hydrogenation is carried out in the liquid phase, for example in trickle or sump mode.
  • the liquid starting material containing the carbonyl compound to be hydrogenated is allowed to trickle over the catalyst bed arranged in the reactor, which is under hydrogen pressure, forming a thin liquid film on the catalyst.
  • hydrogen gas is introduced into the reactor flooded with the liquid reaction mixture, the hydrogen passing through the catalyst bed in ascending gas beads.
  • the solution to be hydrogenated is pumped in a straight pass over the catalyst bed.
  • a portion of the product is withdrawn continuously after passing through the reactor as a product stream and optionally passed through a second reactor as defined above.
  • the other part of the product is recycled to the reactor together with fresh reactant containing the carbonyl compound. This procedure is referred to in the following as Kreislauffahrweise.
  • the circulation mode of operation is preferred. It is further preferred to work in a circulation mode using a main reactor and a secondary reactor.
  • the process according to the invention is suitable for the hydrogenation of carbonyl compounds such as, for example, aldehydes and ketones to give the corresponding alcohols, alipathic and cycloaliphatic saturated and unsaturated carbonyl compounds being preferred.
  • carbonyl compounds may carry other functional groups such as hydroxy or amino groups. Unsaturated carbonyl compounds are usually hydrogenated to the corresponding saturated alcohols.
  • mixtures of two or more than two carbonyl compounds can be hydrogenated together.
  • the single carbonyl compound to be hydrogenated may contain more than one carbonyl group.
  • the process according to the invention is preferably used for the hydrogenation of aliphatic aldehydes, hydroxyaldehydes, ketones, acids, esters, anhydrides, lactones and sugars.
  • Preferred aliphatic aldehydes are branched and unbranched saturated and / or unsaturated aliphatic C 2 -C 30 -aldehydes, such as are obtainable, for example, by oxo-synthesis from linear or branched olefins with internal or terminal double bond. Furthermore, it is also possible to hydrogenate oligomeric compounds which also contain more than 30 carbonyl groups.
  • long-chain aliphatic aldehydes are particularly suitable, as can be obtained, for example, by oxo-synthesis from linear ⁇ -olefins.
  • enolization products e.g. 2-ethylhexenal, 2-propyl heptenal, 2-methylpentenal, 2,4-diethyloctenal or 2,4-dimethylheptenal.
  • Preferred hydroxyaldehydes are C 3 -C 12 -hydroxy aldehydes, such as are obtainable, for example, by aldol reaction from aliphatic and cycloaliphatic aldehydes and ketones with themselves or formaldehyde.
  • Examples are 3-hydroxypropanal, Dimethylolethanal, trimethylolethanal (pentaerythritol), 3-hydroxybutanal (acetaldol), 3-hydroxy-2-ethylhexanal (butylaldol), 3-hydroxy-2-methylpentanal (propienaldol), 2-methylolpropanal, 2,2-dimethylolpropanal, 3-hydroxy 2-methylbutanal, 3-hydroxy pentanal, 2-methylol butanal, 2,2-dimethylol butanal, hydroxypivalaldehyde.
  • Particularly preferred are hydroxypivalaldehyde (HPA) and dimethylolbutanal (DMB).
  • ketones are acetone, butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, cyclohexanone, isophorone, methyl isobutyl ketone, mesityl oxide, acetophenone, propiophenone, benzophenone, benzalacetone, dibenzalacetone, benzalacetophenone, 2,3-butanedione, 2 , 4-pentanedione, 2,5-hexanedione and methyl vinyl ketone.
  • carboxylic acids and derivatives thereof preferably those having 1 to 20 carbon atoms can be reacted.
  • carboxylic acids and derivatives thereof preferably those having 1 to 20 carbon atoms can be reacted.
  • the following are to be mentioned:
  • Carboxylic acids e.g. Formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, n-valeric acid, trimethylacetic acid ("pivalic acid”), caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, methacrylic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid , Cyclohexanecarboxylic acid, benzoic acid, phenylacetic acid, o-toluic acid, m-toluic acid, p-toluic acid, o-chlorobenzoic acid, p-chlorobenzoic acid, o-nitrobenzoic acid, p-nitrobenzoic acid, salicylic acid, p-hydroxybenzoic acid, anthranilic acid, p-aminobenzo
  • Carboxylic acid halides e.g. the chlorides or bromides of the abovementioned carboxylic acids, in particular acetyl chloride or bromide, stearyl chloride or bromide and benzoyl chloride or bromide, which are in particular dehalogenated;
  • Carboxylic esters e.g. the C1-C10-alkyl esters of the abovementioned carboxylic acids, in particular methyl formate, ethyl acetate, butyl butyrate, terephthalic acid dimethyl ester, dimethyl adipate, dimethyl maleate, (meth) acrylic acid methyl ester, butyrolactone, caprolactone and polycarboxylic acid esters, such as e.g. Polyacrylic and polymethacrylic acid esters and their copolymers and polyesters, such as e.g. Polymethylmethacrylat, terephthalic acid esters and other engineering plastics, in particular hydrogenolyses, ie the implementation of esters to the corresponding acids and alcohols are carried out;
  • Carboxylic acid anhydrides such as the anhydrides of the above carboxylic acids, especially acetic anhydride, propionic anhydride, benzoic anhydride and maleic anhydride;
  • Carboxylic acid amides e.g. Formamide, acetamide, propionamide, stearamide, terephthalic acid amide.
  • hydroxycarboxylic acids e.g. Lactic, malic, tartaric or citric acid
  • amino acids e.g. Glycine, alanine, proline and arginine, and peptides are reacted.
  • the process according to the invention is particularly preferably used for the hydrogenation of aldehydes and hydroxyaldehydes.
  • the carbonyl compound to be hydrogenated may be supplied to the hydrogenation reactor alone or as a mixture with the product of the hydrogenation reaction, which may be done neat or using additional solvent.
  • additional solvent In particular, water, alcohols such as methanol, ethanol and the alcohol which is formed under the reaction conditions are suitable as additional solvents.
  • Preferred solvents are water, THF, NMP, and ethers, e.g. Dimethyl, diethyl ether, MTBE, particularly preferred is water.
  • Suitable tertiary amines are mentioned by way of example in DE-A 25 07 461.
  • Preferred tertiary amines are tri-n-C 1 -C 4 -alkylamines and trimethylamine, triethylamine, tri-n-propylamine and tri-n-butylamine are particularly preferred.
  • the hydrogenation in both the bottoms and in trickle in each case preferably operated in circulation mode and the trickle is preferred, is generally carried out at a temperature of 50 to 250 ° C, preferably at 70 to 200 ° C, particularly preferably at 100 to 140 ° C and a pressure of 15 to 250 bar, preferably 20 to 200 bar, particularly preferably 25 to 100 bar by.
  • the catalyst loading is preferably 0.1 to 1 kg of starting material / I of catalyst / hour, more preferably 0.2 to 0.6 kg / l / h.
  • Starting materials were a 20% strength by weight sodium carbonate solution and an aqueous solution I which contained 2.67% by weight Al and 5% by weight Cu in the form of their nitrates.
  • solution I and soda solution were metered into a precipitation vessel at 80 ° C. in such a way that a pH of 5.6 was established.
  • the precipitation mixture was transferred to a larger stirred tank and adjusted at 80 ° C with sodium carbonate solution to a pH of 7.9.
  • the suspension was then passed to a filter press.
  • the powder diffractometry according to Figure 1 (Fig. 1) was made with a Bruker AXS D 5000.
  • the mixture was then filtered and washed with water nitrate-free.
  • the filter paste was suspended in water and dried in a spray tower with hot air at 130-150 ° C outlet temperature. This is followed by a calcination at a temperature of 375 - 390 ° C and again a powder diffractogram (Bruker AXS D 5000) was made.
  • the powder with 3 wt .-% graphite was tabletted as an aid to tablets with 5 x 5 mm.
  • This comparison catalyst A according to DE-A 30 27 890 consisted of 55% by weight of CuO and 45% by weight of Al 2 O 3 and had a specific surface area (BET) of 95 m 2 / g, a Hg pore volume of 0.44 ml / g at a vibrating weight of 952 g / l.
  • BET specific surface area
  • Catalyst B was prepared according to Catalyst A but compressed to 3x3 mm tablets.
  • the catalyst according to the invention consists of 55% CuO and 45% by weight Al 2 O 3, has a specific surface area (BET) of 95 m 2 / g, an Hg porosity of 0.38 ml / g with a shaking weight of 1042 g / l ,
  • catalyst A or B 150 ml of catalyst A or B were in a tubular reactor at 190 ° C by passing a mixture of 5 vol.% Hydrogen and 95 vol.% Nitrogen (total volume 50 Nl / h) depressurized for 24 h.
  • catalyst B according to the invention is superior to comparative catalyst A in terms of conversion (activity).
  • the pore radius distribution of the catalysts used is between 1 and 1000 nm, preferably bimodal between 10 and 60 and 60 and 800 nm. The ignition loss in both catalysts at 900 ° C ⁇ 8%.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne un procédé pour réaliser une hydratation catalytique de composés de carbonyle ou d'un mélange d'au moins deux composés de carbonyle, en la présence de corps moulés catalytiques contenant du cuivre qui sous la forme d'oxyde ont une surface spécifique de 50 à 150 m<SUP>2</SUP>/g, et qui sous la forme d'oxyde comprennent en intégralité ou en partie des cristaux ayant une structure de spinelle et présentant du cuivre sous la forme d'oxyde de cuivre. L'invention se caractérise en ce que le diamètre d, la hauteur h, l'épaisseur de paroi w ou le diamètre cellulaire r<SUB>2</SUB> des corps moulés est = 5 mm, à la condition que le diamètre d et la hauteur h soit = 4 mm lorsqu'il s'agit de corps moulés se présentant sous la forme de pastilles symétriques.
PCT/EP2006/067078 2005-10-14 2006-10-05 Procede pour hydrater des composes de carbonyle Ceased WO2007042456A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200510049135 DE102005049135A1 (de) 2005-10-14 2005-10-14 Verfahren zur Hydrierung von Carbonylverbindungen
DE102005049135.9 2005-10-14

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WO2007042456A1 true WO2007042456A1 (fr) 2007-04-19

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PCT/EP2006/067078 Ceased WO2007042456A1 (fr) 2005-10-14 2006-10-05 Procede pour hydrater des composes de carbonyle

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WO2011141470A1 (fr) 2010-05-12 2011-11-17 Basf Se Procédé de production de néopentylglycol
US8853465B2 (en) 2010-05-12 2014-10-07 Basf Se Process for preparing neopentyl glycol
EP3603801B1 (fr) 2017-03-28 2022-01-05 Korea Kumho Petrochemical Co., Ltd. Methode de préparation d'un alcool par hydrogénation d'un cétone au milieu d'un catalyseur à base d'un oxide métallique
CN118059945A (zh) * 2024-04-08 2024-05-24 深圳阳辰节能科技有限公司 一种高效燃煤催化剂及其制备方法

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DE102012019123B4 (de) * 2012-09-28 2021-10-21 Clariant International Ltd. Hydrierkatalysator und Verfahren zu dessen Herstellung durch die Verwendung von unkalziniertem Ausgangsmaterial
DE102014004413A1 (de) 2014-03-26 2015-10-01 Clariant International Ltd. Hydrierkatalysator und Verfahren zu dessen Herstellung

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WO2006005505A1 (fr) * 2004-07-09 2006-01-19 Basf Aktiengesellschaft Corps moule catalytique et procede d'hydrogenation de composes carbonyles
WO2006005506A1 (fr) * 2004-07-09 2006-01-19 Basf Aktiengesellschaft Catalyseur et procede d'hydrogenation de composes carbonyles

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US4308176A (en) * 1980-03-28 1981-12-29 Norsk Hydro A.S. Catalyst and method for producing said catalyst
DE3027890A1 (de) * 1980-07-23 1982-03-04 Basf Ag, 6700 Ludwigshafen Hydrierkatalysatoren fuer die herstellung von propandiolen und verfahren zur herstellung von propandiolen mit solchen katalysatoren
DE19730939A1 (de) * 1997-07-18 1999-01-21 Basf Ag Verfahren zur Hydrierung von Carbonylverbindungen
DE10313702A1 (de) * 2003-03-27 2004-10-07 Basf Ag Katalysator und Verfahren zur Hydrierung von Carbonylverbindungen
WO2006005505A1 (fr) * 2004-07-09 2006-01-19 Basf Aktiengesellschaft Corps moule catalytique et procede d'hydrogenation de composes carbonyles
WO2006005506A1 (fr) * 2004-07-09 2006-01-19 Basf Aktiengesellschaft Catalyseur et procede d'hydrogenation de composes carbonyles

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011141470A1 (fr) 2010-05-12 2011-11-17 Basf Se Procédé de production de néopentylglycol
US8853465B2 (en) 2010-05-12 2014-10-07 Basf Se Process for preparing neopentyl glycol
EP3603801B1 (fr) 2017-03-28 2022-01-05 Korea Kumho Petrochemical Co., Ltd. Methode de préparation d'un alcool par hydrogénation d'un cétone au milieu d'un catalyseur à base d'un oxide métallique
EP3603801B2 (fr) † 2017-03-28 2025-07-23 Korea Kumho Petrochemical Co., Ltd. Methode de préparation d'un alcool par hydrogénation d'un cétone au milieu d'un catalyseur à base d'un oxide métallique
CN118059945A (zh) * 2024-04-08 2024-05-24 深圳阳辰节能科技有限公司 一种高效燃煤催化剂及其制备方法

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