EP1768942A1 - Catalyseur et procede d'hydrogenation de composes carbonyles - Google Patents

Catalyseur et procede d'hydrogenation de composes carbonyles

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Publication number
EP1768942A1
EP1768942A1 EP05759669A EP05759669A EP1768942A1 EP 1768942 A1 EP1768942 A1 EP 1768942A1 EP 05759669 A EP05759669 A EP 05759669A EP 05759669 A EP05759669 A EP 05759669A EP 1768942 A1 EP1768942 A1 EP 1768942A1
Authority
EP
European Patent Office
Prior art keywords
copper
weight
oxidic material
range
proportion
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Withdrawn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
EP05759669A
Other languages
German (de)
English (en)
Inventor
Christophe Houssin
Henrik Junicke
Andrea Haunert
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
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1768942A1 publication Critical patent/EP1768942A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—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
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • C07C29/147—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 carboxylic acids or derivatives thereof
    • C07C29/149—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 carboxylic acids or derivatives thereof 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the present invention relates to a process for the hydrogenation of organic compounds which have at least one carbonyl group, using a catalyst which is distinguished, inter alia, by the fact that it consists of copper oxide, aluminum oxide and iron oxide, and that by adding Iron oxide is a catalyst with high selectivity and high stability. Copper powder, copper flakes or cement can also be added during its manufacture.
  • the present invention likewise relates to the catalyst itself and very generally to the use of lanthanum oxide in the production of catalysts with high selectivity and at the same time high stability.
  • catalytic hydrogenation of carbonyl compounds such as e.g.
  • carboxylic acid esters are carried out almost exclusively in fixed bed reactors.
  • supported catalysts for example copper, nickel or noble metal catalysts, are used as fixed bed catalysts.
  • No. 3,923,694 describes, for example, a catalyst of the copper oxide / zinc oxide / aluminum oxide type.
  • the disadvantage of this catalyst is that it is not mechanically stable enough during the reaction and therefore disintegrates relatively quickly. This results in a loss of activity and a build-up of differential pressure across the reactor due to the disintegrating shaped catalyst bodies. As a result, the system must be shut down prematurely.
  • DE 198 09 418.3 describes a process for the catalytic hydrogenation of a carbonyl compound in the presence of a catalyst which comprises a support which primarily contains titanium dioxide and copper as an active component or a mixture of copper with at least one of the metals selected from the group consisting of zinc, Aluminum, cerium, a noble metal and a metal of subgroup VIII, comprises, the copper surface being a maximum of 10 m a / g.
  • Preferred carrier materials are mixtures of titanium dioxide with aluminum oxide or zirconium oxide or aluminum oxide and zirconium oxide.
  • the catalyst material is deformed with the addition of metallic copper powder or copper flakes.
  • DE-A 195 05 347 describes very generally a process of catalyst tablets with high mechanical strength, a metal powder or a powder of a metal alloy being added to the material to be stripped of tablets.
  • aluminum powder or copper powder or copper flakes is added as the metal powder.
  • a shaped body is obtained with a copper oxide / zinc oxide / aluminum oxide catalyst, which has a poorer lateral compressive strength than a shaped body which was produced without the addition of aluminum powder, and the shaped body according to the invention showed at it Use as a catalyst has poorer conversion activity than catalysts which were produced without the addition of aluminum powder.
  • a hydrogenation catalyst composed of NiO, ZrO2, MoO3 and CuO is also disclosed there, to which Cu powder, inter alia, was added during manufacture. No information is given in this document about selectivity or activity.
  • DE 256 515 describes a process for the production of alcohols from synthetic gas, wherein catalysts based on Cu / Al / Zn are used, which are obtained by grinding and pilling with metallic copper powder or copper flakes.
  • the main focus in the process described is on the preparation of mixtures of C1 to C5 alcohols, a process being chosen in which the reaction reactor in the upper third of the layer contains a catalyst which contains a higher proportion of copper powder or Has copper flakes, and in the lower third contains a catalyst that has a lower proportion of copper powder or copper flakes.
  • An object of the present invention was to provide a process and a catalyst which do not have the disadvantages of the prior art and to provide processes for the catalytic hydrogenation of carbonyl compounds and catalysts, the catalysts having both high mechanical stability and high hydrogenation activity and have selectivity.
  • the present invention relates to a process for the hydrogenation of an organic compound having at least one carbonyl group, in which the organic compound is brought into contact in the presence of hydrogen with a shaped body which can be prepared by a process in which
  • powdered metallic copper, copper flake, powdered cement or graphite or a mixture thereof can be added to the oxidic material, and
  • Iron oxide is understood to mean Fe (III) oxide.
  • the moldings according to the invention are used as solid, impregnated, shell and precipitation catalysts.
  • the catalyst used in the process according to the invention is characterized in that the active component copper, the component aluminum and the component iron are preferably precipitated simultaneously or in succession with a soda solution, then dried, calcined, tableted and again calcined.
  • a copper salt solution, an aluminum salt solution and a solution of an iron salt or a solution containing copper, aluminum and an iron salt is precipitated in parallel or in succession with a soda solution. The precipitated material is then dried and, if necessary, calcined.
  • a copper salt solution and a solution of an iron salt or a solution containing copper salt and at least one salt of iron on a prefabricated aluminum oxide support is present as a powder in an aqueous suspension.
  • the carrier material can also be in the form of balls, strands, grit or tablets.
  • a copper salt solution and a solution of an iron salt or a solution containing copper salt and a salt of iron, preferably with soda solution An aqueous suspension of the carrier material aluminum oxide is used as a template.
  • Precipitated precipitates which result from A) or B) are filtered in a conventional manner and preferably washed free of alkali, as is described, for example, in DE 198 09 418.3.
  • Both the end products from A) as well as from B) are at temperatures of 50 to 15O 0 C, preferably dried at 12O 0 C and subsequently, if necessary, preferably 2 hours at in general from 200 to 600 0 C, particularly at 300 to 500 0 C calcined.
  • all of the Cu (I) and / or Cu (II) salts soluble in the solvents used in the application can be used as starting substances for A) and / or B) -Complexes, analog aluminum salts and salts of iron can be used.
  • Copper nitrate is particularly preferably used for processes according to A) and B).
  • the dried and optionally calcined powder described above is preferably used to form tablets, rings, ring tablets,
  • the composition of the oxidic material is generally such that the proportion of copper oxide in the range from 40 to 90% by weight, the proportion of oxides of iron oxide in the range from 0 to 50% by weight and the proportion of aluminum oxide in the range up to 50% by weight, in each case based on the total weight of the sum of the above-mentioned oxidic components, these three oxides together representing at least 80% by weight of the oxidic material after calcination, cement not being present in the oxidic material is attributed to the above sense.
  • the present invention therefore relates to a method as described above, which is characterized in that the oxidic material
  • the process according to the invention and the catalysts according to the invention are characterized in that the addition of iron during the precipitation leads to a high stability of the shaped body which is used as a catalyst.
  • the oxidic material is powdered copper, copper flake or powdered cement or graphite or a mixture thereof in the range from 1 to 40% by weight, preferably in the range from 2 to 20% by weight and particularly preferably in the range from 3 to 10 % By weight, based in each case on the total weight of the oxidic material.
  • an alumina cement is preferably used as the cement.
  • the alumina cement consists essentially of aluminum oxide and calcium oxide, and particularly preferably it consists of approximately 75 to 85% by weight of aluminum oxide and approximately 15 to 25% by weight of calcium oxide.
  • a cement based on magnesium oxide / aluminum oxide, calcium oxide / silicon oxide and calcium oxide / aluminum oxide / iron oxide can also be used.
  • the oxidic material in a proportion of at most 10% by weight, preferably at most 5% by weight, based on the total weight of the oxidic material, may have at least one further component which is selected from the group consisting of the elements Re, Fe, Ru, Co, Rh, Ir, Ni, Pd and Pt.
  • graphite is added to the oxidic material before it is shaped into the shaped body in addition to the copper powder, the copper flakes or the cement powder or the mixture thereof.
  • Sufficient graphite is preferably added that the shaping into a shaped body can be carried out better.
  • 0.5 to 5% by weight of graphite, based on the total weight of the oxidic material, is added. It does not matter whether graphite is added to the oxidic material before or after or simultaneously with the copper powder, the copper flakes or the cement powder or the mixture thereof.
  • the present invention also relates to a process as described above, which is characterized in that the oxidic material or the mixture resulting from (ii) graphite in a proportion in the range from 0.5 to 5% by weight, based on the total weight of the oxidic material is added.
  • the present invention therefore also relates to a shaped body comprising
  • the shaped body obtained after the shaping is optionally calcined at least once over a period of generally 0.5 to 10 h, preferably 0. 5 to 2 hours.
  • the temperature in this at least one calcination step is all ⁇ common in the range of 200 to 600 0 C, preferably in the range of 250 to 500 0 C and more preferably in the range 270-400 0 C.
  • the shaped body When used as a catalyst in the oxidic form, the shaped body is coated with reducing gases, for example hydrogen, preferably hydrogen / inert gas mixtures, in particular hydrogen / nitrogen mixtures, at temperatures in the range from 100 to 500 ° C., preferably in the range, before being coated with the hydrogenation solution pre-reduced from 150 to 350 0 C and in particular in the range of 180 to 200 0 C.
  • reducing gases for example hydrogen, preferably hydrogen / inert gas mixtures, in particular hydrogen / nitrogen mixtures, at temperatures in the range from 100 to 500 ° C., preferably in the range, before being coated with the hydrogenation solution pre-reduced from 150 to 350 0 C and in particular in the range of 180 to 200 0 C.
  • the molded article according to the invention is activated in a manner known per se by treatment with reducing media before use as a catalyst. Activation takes place either beforehand in a reduction furnace or after installation in the reactor. If the reactor has been activated beforehand in the reduction furnace, it is installed in the reactor and charged directly with the hydrogenation solution under hydrogen pressure.
  • the preferred area of use for the shaped articles produced by the process according to the invention is the hydrogenation of organic compounds having carbonyl groups in a fixed bed.
  • the hydrogenation can be carried out in the gas phase or in the liquid phase.
  • the hydrogenation is preferably carried out in the liquid phase, for example in a trickle or bottoms mode.
  • the liquid starting material containing the carbonyl compound to be hydrogenated is allowed to trickle in the reactor, which is under hydrogen pressure, over the catalyst bed arranged therein, a thin film of liquid forming 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 bubbles.
  • the solution to be hydrogenated is pumped over the catalyst bed in a single pass.
  • a part of the product is continuously drawn off as a product stream after passing through the reactor and, if appropriate, passed through a second reactor as defined above.
  • the other part of the product is fresh along with that The reactant containing carbonyl compound is fed to the reactor again. This procedure is referred to below as the cycle procedure.
  • the cycle mode is preferred. It is further preferred to work in a cycle mode using a main and post-reactor.
  • the process according to the invention is suitable for the hydrogenation of carbonyl compounds, e.g. Aldehydes and ketones, carboxylic acids, carboxylic acid esters or carboxylic acid anhydrides to give the corresponding alcohols, aliphatic and cycloaliphatic saturated and unsaturated carbonyl compounds being preferred.
  • carbonyl compounds e.g. Aldehydes and ketones, carboxylic acids, carboxylic acid esters or carboxylic acid anhydrides to give the corresponding alcohols, aliphatic and cycloaliphatic saturated and unsaturated carbonyl compounds being preferred.
  • aromatic carbonyl compounds undesired by-products can be formed by hydrogenation of the aromatic nucleus.
  • the carbonyl compounds can carry further functional groups such as hydroxyl or amino groups. Unsaturated carbonyl compounds are generally hydrogenated to the corresponding saturated alcohols.
  • carbonyl compounds as used in the context of the invention includes all compounds which have a C nieO group, including carboxylic acids and their
  • 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, as can be obtained, for example, by oxo synthesis from linear or branched olefins with an internal or terminal double bond. Furthermore, oligomeric compounds which also contain more than 30 carbonyl groups can also be hydrogenated.
  • long-chain aliphatic aldehydes are also particularly suitable, as can be obtained, for example, from linear ⁇ -olefins by oxosynthesis.
  • Enalization products such as e.g. 2-ethylhexenal, 2-methyl-pentenal, 2,4-diethyloctenal or 2,4-dimethylheptenal.
  • Preferred hydroxyaldehydes are C 3 -Ci 2 -hydroxyaldehydes, 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 (pentaerythrital), 3-hydroxybutanal (acetaldol), 3-hydroxy-2-ethylhexanal (butylaldol), 3-hydroxy-2-methylpentanal (propienaldol), 2-methylolpropanal, 2,2- Dimethylolpropanal, 3-hydroxy-2-methylbutanal, 3-hydroxypentanal, 2-methylolbutanal, 2,2-dimethylolbutanal, hydroxypivalaldehyde.
  • Hydroxypivalaldehyde (HPA) and dimethylolbutanal (DMB) are particularly preferred.
  • 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, 2,3-butanedione , 4-pentanedione, 2,5-hexanedione and methyl vinyl ketone.
  • carboxylic acids and derivatives thereof preferably those with 1-20 C atoms, can be reacted.
  • carboxylic acids and derivatives thereof preferably those with 1-20 C atoms, can be reacted.
  • 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 , Linoleic acid, linolenic acid, cyclohexane carboxylic 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 -Amino-benzoic acid, oxalic acid, malonic acid, succinic
  • Carboxylic acid esters such as, for example, the CrCi O alkyl esters of the abovementioned carboxylic acids, in particular methyl formate, ethyl acetate, butyric acid butyl ester, phthalic acid, isophthalic acid, terephthalic acid, adipic acid, maleic acid dialkyl esters, such as, for example, the dimethyl ester of these acids, (meth) acrylic acid methyl ester Butyrolactone, caprolactone and polycarboxylic acid esters, such as polyacrylic and polymethacrylic acid esters and their Copolymers and polyesters, such as polymethyl methacrylate, terephthalic acid esters and other engineering plastics, in particular hydrogenolysis, ie the conversion of esters to the corresponding acids and alcohols, being carried out here;
  • Carboxylic anhydrides such as e.g. the anhydrides of the above-mentioned carboxylic acids, in particular acetic anhydride, propionic anhydride, benzoic anhydride and maleic anhydride;
  • Carboxamides e.g. Formamide, acetamide, propionamide, stearamide, terephthalic acid amide.
  • Hydroxycarboxylic acids such as e.g. Lactic, malic, tartaric or citric acid, or amino acids such as e.g. Glycine, alanine, proline and arginine, and peptides are implemented.
  • Saturated or unsaturated carboxylic acids, carboxylic esters, carboxylic anhydrides or lactones or mixtures of two or more thereof are hydrogenated as particularly preferred organic compounds.
  • the present invention also relates to a method as described above, which is characterized in that the organic compound is a carboxylic acid, a carboxylic acid ester, a carboxylic acid anhydride or a lactone.
  • Examples of these compounds include maleic acid, maleic anhydride, succinic acid, succinic anhydride, adipic acid, 6-hydroxycaproic acid, 2-cyclododecylpropionic acid, the esters of the aforementioned acids such as e.g. Methyl, ethyl, propyl or butyl ester.
  • Other examples are ⁇ -butyrolactone and caprolactone.
  • the present invention relates to a process as described above, which is characterized in that the organic compound is adipic acid or an adipic acid ester.
  • the carbonyl compound to be hydrogenated can be fed to the hydrogenation reactor alone or as a mixture with the product of the hydrogenation reaction, this being possible in undiluted form or using an additional solvent.
  • Water, alcohols such as methanol, ethanol and the alcohol which is produced under the reaction conditions are particularly suitable as an additional solvent.
  • Preferred solvents are water, THF and NMP, water is particularly preferred.
  • the hydrogenation is carried out both in the upflow mode or in the downflow mode, wherein in each case preferably in the circulation mode, is generally carried out at a temperature in the range of 50 to 350 0 C, preferably in the range of 70 to 300 0 C, particularly vorzugt in Range from 100 to 27O 0 C and a pressure in the range from 3 to 350 bar, preferably in the range from 5 to 330 bar, particularly preferably in the range from 10 to 300 bar.
  • the catalysts according to the invention are used in processes for the preparation of hexanediol and / or caprolactone, as described in DE 196 07 954, DE 196 07955, DE 19647 348 and DE 19647 349.
  • the present invention therefore relates to the use of Cu-Al catalysts which, through the addition of lanthanum, tungsten, molybdenum, titanium and / or zirconium oxides, in the production of a catalyst for increasing both the mechanical stability as well as the activity and selectivity of the catalyst.
  • the present invention relates to a use as described above, which is characterized in that the catalyst comprises copper as the active component.
  • the lateral compressive strength was determined in the context of the present application using a device of the "Z 2.5 / T 919" type from Zwick (Ulm). Both with the reduced and with the used catalysts, the measurements were carried out under a nitrogen atmosphere in order to obtain a Re -Avoid oxidation of the catalysts. Examples
  • solution 1 A mixture of 12.41 kg of a 19.34% copper nitrate solution and 14.78 kg of an 8.12% aluminum nitrate solution and 1.06 kg of a 37.58% iron nitrate solution x 9H 2 O was prepared in 1.5 I dissolved water (solution 1).
  • Solution 2 contains 60 kg of a 20% anhydrous Na 2 CO 3 .
  • Solution 1 and solution 2 are separate Lei ⁇ obligations, passed into a precipitation vessel provided with a stirrer and containing 10 1 heated to 8O 0 C water. The pH was brought to 6.2 by appropriately adjusting the feed rates of solution 1 and solution 2.
  • the filter cake was calcined for 16 hours at 12O 0 C and then dried for 2 h at 300 0 C.
  • the catalyst powder obtained in this way is precompacted with 1% by weight of graphite.
  • the compact obtained is mixed with 5% by weight of Unicoat copper flakes and then with 2% by weight of graphite and compressed to tablets of 3 mm in diameter and 3 mm in height.
  • the tablets were finally 2 ned hours at 350 0 C calci ⁇ .
  • the catalyst produced in this way has the chemical composition 57% CuO / 28.5% Al 2 O 3 / 9.5% Fe 2 O 3 /5% Cu.
  • the side compressive strength in the oxidic state was 117 N, in the reduced state 50 N, as indicated in Table 1.
  • the total duration of the experiment was 7 days.
  • GC analysis were in the reactor at 190 0 C Esterum accounts of 99.9%, a hexanediol selectivity of 97.5% was detected. After removal, the catalyst was still fully intact and showed high mechanical stability.
  • Table 1 The test results are summarized in Table 1.
  • the comparative catalyst was produced analogously to catalyst 2, but without the addition of the iron nitrate solution, which means: 14.5 kg of a 19.34% copper nitrate solution and 14.5 kg of an 8.12% aluminum nitrate solution (solution 1) are added a soda solution analogous to catalyst 1.
  • the catalyst produced in this way has the chemical composition 66.5% CuO / 28.5% Al 2 O 3 /5% Cu.
  • the side compressive strength in the oxidic and reduced state are listed in Table 1.
  • Example 4 Hydrogenation of dimethyl adipate on a comparative catalyst
  • the total duration of the experiment was 7 days.
  • ester conversions 80.2% each, hexanediol portions of 86.6% were detected by GC analysis. After removal, the catalyst was still fully intact and had high mechanical stability.
  • Table 1 The test results are summarized in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé pour hydrogéner un composé organique comportant au moins un groupe carbonyle. Selon ledit procédé, ce composé organique est mis en contact avec un corps moulé en présence d'hydrogène, lequel corps peut être fabriqué selon un procédé consistant : i) à préparer un matériau oxydé, contenant de l'oxyde de cuivre, de l'oxyde d'aluminium et de l'oxyde de fer, ii) à ajouter à ce matériau oxydé du cuivre métallique pulvérulent, des lamelles de cuivre, du ciment pulvérulent, du graphite ou un mélange de ces derniers puis iii) à façonner le mélange résultant de l'étape (ii) pour obtenir un corps moulé.
EP05759669A 2004-07-09 2005-07-07 Catalyseur et procede d'hydrogenation de composes carbonyles Withdrawn EP1768942A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004033554A DE102004033554A1 (de) 2004-07-09 2004-07-09 Katalysator und Verfahren zur Hydrierung von Carbonylverbindungen
PCT/EP2005/007339 WO2006005506A1 (fr) 2004-07-09 2005-07-07 Catalyseur et procede d'hydrogenation de composes carbonyles

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EP1768942A1 true EP1768942A1 (fr) 2007-04-04

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US (1) US20080071120A1 (fr)
EP (1) EP1768942A1 (fr)
JP (1) JP2008505156A (fr)
KR (1) KR20070038548A (fr)
CN (1) CN1984859B (fr)
CA (1) CA2569246A1 (fr)
DE (1) DE102004033554A1 (fr)
WO (1) WO2006005506A1 (fr)

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DE102005049135A1 (de) * 2005-10-14 2007-04-19 Basf Ag Verfahren zur Hydrierung von Carbonylverbindungen
US7879756B2 (en) * 2007-08-10 2011-02-01 Rentech, Inc. Precipitated iron catalyst for hydrogenation of carbon monoxide
USD570170S1 (en) 2007-10-12 2008-06-03 Staples The Office Superstore Llc Stapler
RU2522761C2 (ru) 2008-11-05 2014-07-20 Басф Се Способ получения n, n-замещенных 3-аминопропан-1-олов
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US20080071120A1 (en) 2008-03-20
WO2006005506A1 (fr) 2006-01-19
CN1984859A (zh) 2007-06-20
CA2569246A1 (fr) 2006-01-19

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