EP1261423A1 - Method for catalytic hydrogenation on rhenium-containing active carbon carrier catalysts - Google Patents

Method for catalytic hydrogenation on rhenium-containing active carbon carrier catalysts

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Publication number
EP1261423A1
EP1261423A1 EP01909811A EP01909811A EP1261423A1 EP 1261423 A1 EP1261423 A1 EP 1261423A1 EP 01909811 A EP01909811 A EP 01909811A EP 01909811 A EP01909811 A EP 01909811A EP 1261423 A1 EP1261423 A1 EP 1261423A1
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EP
European Patent Office
Prior art keywords
activated carbon
acid
weight ratio
catalyst
platinum
Prior art date
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Application number
EP01909811A
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German (de)
French (fr)
Inventor
Rolf-Hartmuth Fischer
Rolf Pinkos
Stephan Andreas Schunk
Joachim Wulff-Döring
Frank Stein
Thomas NÖBEL
Sylvia Huber
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BASF SE
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BASF SE
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Classifications

    • 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
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/177—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of a carboxy group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6567—Rhenium
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered

Definitions

  • the invention relates to a process for the hydrogenation of compounds containing carbonyl groups on Re-containing, partially non-oxidatively pretreated activated carbon supported catalysts, for the production of alcohols while avoiding the formation of ethers, or for the production of ethers and lactones, the production of the desired product being controlled selectively can be.
  • the industrial production of alcohols is often based on starting materials containing carbonyl groups, such as aldehydes, ketones, carboxylic acids, carboxylic anhydrides and esters, which are hydrogenated with hydrogen.
  • the production of ethers and lactones is often based on carboxylic acids, esters or anhydrides thereof, lactones or mixtures thereof.
  • EP-A-0 848 991 describes a catalyst containing palladium, silver, rhenium and iron which, for example, can hydrogenate maleic acid or its ester to give butanediol.
  • a selectivity to butanediol of 89.5% is achieved.
  • the hydrogenation success is diminished by the fact that the byproduct is ether tetrahydrofuran (THF) with 5.6%.
  • THF ether tetrahydrofuran
  • n-butanol is formed as a further by-product.
  • 5,698,749 describes catalysts which contain an element from Group VIII and at least rhenium, tungsten or molybdenum on an oxidatively pretreated carbon support.
  • Pd / Re / C or Pd / Re / Ag / C catalysts are described.
  • hydrogenation of aqueous maleic acid in turn produces, in addition to butanediol, THF.
  • Butane diol is obtained with up to 92.8% selectivity.
  • THF is still 1.6%
  • the other by-product n-butanol is 4.6%.
  • US 5,478,952 relates to the hydrogenation of maleic acid on an Ru / Re activated carbon catalyst to form THF and gamma-butyrolactone as main products. - 3 -
  • EP-A-0 276 012 relates to the hydrogenation of maleic acid to gamma-butyrolactone and butanediol over P ⁇ VRe / TiO 2 catalysts.
  • the object is achieved according to the invention by a process for the catalytic flydration of carbonyl compounds on a catalyst which contains rhenium on activated carbon, the catalyst being rhenium (calculated as metal) in a weight ratio to activated carbon of 0.0001 to 0.5 platinum (calculated as metal) in a weight ratio to activated carbon of 0.0001 to 0.5 and optionally at least one further metal selected from Zn, Cu, Ag, Au, Mi, Fe, Ru, Mn, Cr, Mo, W and V used in a weight ratio to the activated carbon of 0 to 0.25, for the production of alcohols, the activated carbon has not been pretreated oxidatively, or for the preparation of ethers and lactones, starting from carboxylic acids, esters or anhydrides thereof, lactones or their mixtures and the Hydrogenation is carried out at a maximum hydrogen pressure of 25 bar and the activated carbon can be pretreated non-oxidatively.
  • carbonyl compounds can be catalytically hydrogenated to the corresponding alcohols without ether formation at low temperatures (preferably below 140 ° C.) by using at least rhenium or rhenium / platinum on non-oxidatively treated carbon supports such as activated carbon for the hydrogenation. Without ether formation, this means that the ether formation should have a maximum of 0.5% of the hydrogenation products.
  • the ether content is preferably below 0.2%, particularly preferably below 0.1%.
  • a non-oxidative treatment of the carbon support material with mineral acids or bases can furthermore be regarded as advantageous compared to an oxidative treatment with ENT or peroxides, since an oxidative pretreatment of activated carbons with H 2 O or peroxides is an expensive pretreatment process, which increases the catalyst production costs considerably.
  • oxidative pretreatment with ENT nitrous gases are generated which have to be removed in complex exhaust gas cleaning processes (DeNOX).
  • DeNOX complex exhaust gas cleaning processes
  • Another disadvantage of the oxidative pretreatment is the loss of material due to the oxidative pretreatment.
  • the carbon-containing carrier materials partially dissolve in the oxidizing agents and moldings can even completely disintegrate at the appropriate temperature.
  • the commercially available activated carbons are generally suitable as activated carbons. Preference is given to using those which contain little chlorine and sulfur and whose proportion of micropores is as small as possible in relation to the proportion of mesopore and macropores.
  • the non-oxidative treatment of the activated carbons can be carried out by treatment with solvents such as water or alcohols.
  • the carbon carrier can also be conditioned by non-oxidative treatment with mineral acids such as HC1, H 3 PO 4 , H 2 SO 4, HBr or HF.
  • Organic acids such as formic acid or acetic acid can also be used for the pretreatment of the carrier material / 64338
  • Coal carriers that have been pretreated with solutions of bases such as NH 4 OH, NaOH or KOH also have a positive effect on the catalytic performance.
  • the active carbon can be treated with the non-oxidizing agent before or during the application of the platinum and rhenium component or other catalyst components.
  • catalysts are used in which the activated carbon carrier is first pretreated non-oxidatively and then oxidatively. In a further particular embodiment, catalysts are used in which the activated carbon carrier is first pretreated oxidatively and then non-oxidatively.
  • the activated carbon carrier is stirred in the pretreatment agent at elevated temperature (50 to 90 ° C.).
  • Both concentrated and diluted pretreatment agents (acids, alkalis) can be used as pretreatment agents.
  • Concentrated pretreatment agents are preferably used (conc. HC1, conc. NaOH, semi-conc. H 3 PO).
  • the treatment time is usually between one and 48 hours, preferably between 5 and 30 hours.
  • the carbon carrier is washed with water to purify interfering ions. Aftertreatment at elevated temperature in water (between one and 48 hours, preferably between 5 and 30 hours) can follow.
  • the pH test (boil 5g of charcoal in dist. H 2 0 20 minutes, filter solution, let cool under nitrogen, measure at pH 20 ° C) reveals a more acidic surface than the starting material basic pretreatment agent ensures a more basic surface.
  • the rhenium component used is usually (NH 4 ) ReO 4 , Re O 7 , ReO, ReCl 3 , ReCl 5 , Re (CO) 5 Cl, Re (CO) 5 Br or Re 2 (CO) ) 0 , without this list is meant exclusively.
  • Re O 7 is preferably used.
  • platinum is also applied to the catalyst.
  • the platinum can e.g. Platinum powder, oxide, hydrated oxide, nitrate, platinum (II) - or - (IV) - chloride, platinum (IV) -hydrochloric acid, platinum (II) - or - (IV) -bromide, platinum (II) -iodide, ice or trans-platinum (II) diamine chloride, ice or trans platinum (IV) diamine chloride, platinum (II) diamine nitrite, platinum (II) ethylenediamine chloride, platinum (II) - Tetramine chloride or chloride hydrate, platinum (II) tetramine nitrate, platinum (II) ethylenediamine chloride, platinum (0) tetrakis (triphenylphosphine), ice or trans-platinum (II) bis (triethylphosphine) ) chloride, ice or trans platinum (I
  • Platinum (IV) bis (triphenylphosphine) oxide platinum (II) (- 2,2'-6 ', 2 "-terpyridine) chloride dihydrate, cis-platinum-bis- (acetonitrile) dichloride, cis- Platinum bis (benzonitrile) dichloride, platinum (II) acetylacetonate, platinum (II) -lc, 5c-cyclooctadiene chloride or - bromide, platinum nitrosyl nitrate, preferably as platinum oxide or nitrate, particularly preferably as platinum nitrate, without this list being meant exclusively.
  • Rhenium (calculated as metal) can be applied in a weight ratio to activated carbon of 0.0001 to 0.5, preferably 0.001 to 0.2, particularly preferably from 0.01 to 0.15. The same conditions apply to platinum.
  • the weight ratio of rhenium to platinum (calculated as metals) is in a range from 0.01 to 100. Preferably 0.05 to 50, particularly preferably 0.1 to 10.
  • the catalyst There may be other elements on the catalyst. Examples include Zn, Cu, Ag, Au, Ni, Fe, Ru, Mn, Cr, Mo W and V. These elements modify the catalyst essentially with regard to activity and selectivity (hydrogenolysis products) but are not essential.
  • Their weight ratio to Re can be 0 to 100, preferably 0.5 to 30, particularly preferably 0.1 to 5.
  • the active components Re and Pt can be applied by impregnation in one or more steps with an aqueous, alcoholic or other organic solvent solution of the respective dissolved salts, impregnation with a solution of dissolved oxidic or metallic colloid of the active components, equilibrium adsorption in one or more Steps of the salts dissolved in aqueous or alcoholic solution or equilibrium adsorption of dissolved metallic or oxidic colloid on the pretreated activated carbon.
  • the active components can be applied to the activated carbon either simultaneously or in succession. There is a drying step between the individual impregnation and equilibrium adsorption steps to remove the solvent.
  • the active components are preferably applied in one step by impregnation with an aqueous salt solution or an aqueous oxidic colloid.
  • the impregnated catalyst is dried.
  • the drying temperature is 30-350 ° C, preferably 40-280 ° C, particularly preferably 50-150 ° C.
  • the catalysts are usually activated before they are used. This activation can be done by applying a reducing gas atmosphere to the catalyst. Activation with the aid of hydrogen is preferably used.
  • the activation temperature is usually 100-500 ° C., preferably 130-400 ° C., particularly preferably 150-350 ° C.
  • Alternative reduction methods are the reduction of the metallic components by bringing them into contact with a liquid reducing agent such as hydrazine, formaldehyde or sodium formate.
  • the liquid reducing agents are usually brought into contact at temperatures between 10 and 100 ° C. Contacting at temperatures between 20 to 80 ° C. is particularly preferred. - 8th -
  • the hydrogenation for the production of alcohols is usually carried out at 50-250 ° C., preferably at 60-220 ° C., particularly preferably at 70-190 ° C., very particularly preferably at 80-140 ° C. Hydrogenation is usually carried out at a reaction pressure between 3 and 330 bar, preferably 20 and 300 bar.
  • the pressure range of the hydrogenation in the liquid phase in the fixed bed at more than 150 bar, preferably 150-300 bar, in the fixed bed in the gas phase 3 to 100 bar and in suspension 10-90 bar is preferred.
  • Suitable starting materials for the hydrogenation for the production of alcohols are in general carbonyl compounds which can additionally contain double or triple C-C bonds.
  • aldehydes are propionaldehyde, butyraldehyde, crotonaldehyde, ethylhexanal, nonanal and glucose.
  • carboxylic acids are succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, hydroxycaproic acid, octanedioic acid, dodecanedioic acid, 2-cyclododecylpropionic acid and saturated or unsaturated fatty acids.
  • esters are esters of the aforementioned acids, e.g.
  • Anhydrides such as succinic anhydride or maleic anhydride can also be used.
  • Preferred starting materials are succinic acid, maleic acid, adipic acid, 2-cyclododecylpropionic acid, succinic anhydride, maleic anhydride and the esters of these acids and gamma-butyrolactone.
  • ethers and lactones can be prepared by catalytically in particular C 4 -C 5 dicarboxylic acids, dicarboxylic esters and anhydrides, in particular to the corresponding cyclic ethers and lactones as further valuable components at low hydrogen pressures ( ⁇ 25 bar, preferably ⁇ 20 bar ) can be hydrogenated by using at least rhenium and platinum on carbon supports such as activated carbons for the hydrogenation. So far, only gamma-butyrolactone (GBL) has been obtained at similarly low pressures. Another considerable disadvantage has hitherto been incomplete acid conversion at such low pressures. These disadvantages are now eliminated.
  • the hydrogenation is preferably carried out at 50 to 250 ° C, preferably at 60 to 240 ° C, particularly preferably at 70 to 235 ° C.
  • the cyclic ethers and lactones obtained in the process according to the invention are used, for example, as solvents and intermediates. Treatment of the carbon support material can also be carried out to produce ethers and lactones, but is not absolutely necessary.
  • Suitable starting materials for the hydrogenation for the production of ethers and lactones are generally suitable carbonyl compounds which additionally have double or double carbon atoms
  • Esters of the abovementioned acids for example as methyl, ethyl, propyl or butyl esters, can also be mentioned, and lactones, for example ⁇ -butyrolactone, ⁇ -valerolactone or caprolactone, can also be used.
  • Anhydrides such as succinic anhydride or maleic anhydride can also be used.
  • Preferred educts are succinic acid, maleic acid,
  • Adipic acid succinic anhydride, maleic anhydride and the esters thereof
  • Acids and ⁇ -butyrolactone Acids and ⁇ -butyrolactone.
  • the compounds to be hydrogenated can be hydrogenated in bulk or in solution.
  • suitable solvents are the hydrogenation product itself, or substances which are inert under the reaction conditions, such as alcohols such as methanol, ethanol, propanol or butanol, are also ethers such as THF or Ethylene glycol ether suitable.
  • a preferred solvent is water, especially in the hydrogenation of carboxylic acids.
  • the hydrogenation can be carried out in the gas or liquid phase, in one or more stages. In the liquid phase, both the suspension and the fixed bed procedure are possible. In exothermic reactions, the heat can be dissipated by external coolants (e.g. tube reactor). Boiling cooling in the reactor is also possible, especially if hydrogenation is carried out without recycling the product. A cooler in the return flow is recommended for product return.
  • external coolants e.g. tube reactor
  • the alcohols obtained in the process according to the invention are e.g. as
  • BG 09® activated carbon
  • 30% maleic acid solution after a total of 78 h of test time at approximately 122 ° C. reaction temperature, approximately 88.92% butanediol and 10.77% n-butanol, 0.3% propanol and no THF were found in the discharge.
  • Example 5 Example 5:
  • 30% maleic acid solution after a total of 78 h of test time at a reaction temperature of approximately 131 ° C., approximately 91.4% butanediol and 8.26% n-butanol, 0.32% propanol and no THF were found in the discharge.
  • Catalysts produced by non-oxidative pretreatment of the activated carbon were able to hydrogenate maleic acid to the target product 1,4-butanediol at a lower temperature than the known catalysts.
  • the proportion of ether by-product could be greatly reduced.
  • activated carbon (Epibon from Lurgi) were pretreated with phosphoric acid and dried at 120 ° C. 9.81 g of Pt (NO 3 ) 2 were impregnated as an aqueous solution onto 50 g of the coal pretreated in this way.
  • the soaked activated carbon was 18 h dried at 110 ° C, then reduced in a nitrogen / hydrogen stream for 4 h at 300 ° C and ambient pressure and passivated at room temperature in a nitrogen / air stream. 5 g of Re O 7 were then impregnated onto the passivated catalyst and dried at 110 ° C. for 18 hours.
  • the catalyst obtained in this way was activated in a nitrogen / hydrogen stream for 4 h at 300 ° C. and ambient pressure and passivated at room temperature in a nitrogen / air stream.
  • the reduced catalyst contains 3% Pt and 3% Re. 25 ml of the activated / passivated catalyst were then introduced into a 25 ml reactor.
  • the hydrogenation was carried out in trickle mode, without product return.
  • the reaction pressure was 20 bar, about 180 NL hydrogen / h were introduced.
  • an LHSV of 0.1 h "1 and at a reactor temperature of 235 ° C the hydrogenation output after a total of 3 test hours showed approximately 73.5% THF, 1.3% GBL, 0% BDO , 25.0% alcohols (n-butanol + n-propanol).
  • the acid conversion was 95.3%.
  • an LHSV of 0.2 h "1 under otherwise identical reaction conditions, a hydrogenation discharge with approx. 36.5% THF, 42.7% GBL, 0.90% BDO and 19.8% alcohols (n-butanol + n-propanol). The acid conversion was 95.1%.
  • activated carbon (Epibon from Lurgi) were pretreated with phosphoric acid and dried at 120 ° C.
  • 2.5 g of PdCl were impregnated as an aqueous solution onto 50 g of the coal pretreated in this way.
  • the impregnated activated carbon was dried at 110 ° C. for 18 h, then reduced in a nitrogen / hydrogen stream for 4 h at 300 ° C. and ambient pressure and passivated at room temperature in a nitrogen / air stream.
  • 5 g of Re 2 O 7 were then impregnated onto the passivated catalyst and dried at 100 ° C. for 18 hours.
  • the catalyst obtained in this way was activated in a nitrogen / hydrogen stream for 4 h at 300 ° C. and ambient pressure and passivated at room temperature in a nitrogen / air stream.
  • the reduced one Catalyst contains 3% Pd and 3% Re. 25 ml of the activated / passivated catalyst were then introduced into a 25 ml reactor.
  • the hydrogenation was carried out in trickle mode, without product return.
  • the reaction pressure was 20 bar, about 100 NL hydrogen / h were introduced.
  • an LHSV of 0.1 h "1 and a reactor temperature of 235 ° C the hydrogenation output after a total of 3 test hours showed approximately 65.2% THF, 11.9% GBL, 0% BDO and 22.9% alcohols (n-butanol + n-propanol)
  • the acid conversion was 98.5%.

Abstract

The invention relates to a method for producing alcohols by catalytic hydrogenation of carbonyl compounds on a catalyst containing rhenium on active carbon. According to said method, rhenium is used as a catalyst (calculated as a metal) in a weight ratio to active carbon of 0.0001 -0.5, platinum (calculated as a metal) in a weight ratio to active carbon of 0.0001 0.5 and optionally at least one other metal selected from Zn, Cu, Ag, Au, Ni, Fe, Ru, Mn, Cr, Mo, W and V in a weight ratio to active carbon of 0 0.25. The active carbon is not non-oxidatively pre-treated. It is also possible to produce ethers and lactones if the water pressure does not exceed a maximum of 25 bars during treatment. The active carbon in the catalyst can also be non-oxidatively pre-treated

Description

Verfahren zur katalytischen Hydrierung an rheniumhaltigen Aktivkohle-Trägerkatalysatoren Process for the catalytic hydrogenation on rhenium-containing activated carbon supported catalysts
Die Erfindung betrifft ein Verfahren zur Hydrierung von Carbonylgruppen enthaltenden Verbindungen an Re-haltigen, teilweise nichtoxidativ vorbehandelten Aktivkohle-Trägerkatalysatoren, zur Herstellung von Alkoholen unter Vermeidung der Bildung von Ethern, oder zur Herstellung von Ethern und Lactonen, wobei die Herstellung des gewünschten Produktes selektiv gesteuert werden kann.The invention relates to a process for the hydrogenation of compounds containing carbonyl groups on Re-containing, partially non-oxidatively pretreated activated carbon supported catalysts, for the production of alcohols while avoiding the formation of ethers, or for the production of ethers and lactones, the production of the desired product being controlled selectively can be.
Bei der industriellen Herstellung von Alkoholen geht man häufig von Carbonylgruppen enthaltenden Edukten wie Aldehyden, Ketonen, Carbonsäuren, Carbonsäureanhydriden und Estern aus, die mit Wasserstoff hydriert werden. Zur Herstellung von Ethern und Lactonen geht man häufig von Carbonsäuren, Estern oder Anhydriden davon, Lactonen oder deren Gemischen aus.The industrial production of alcohols is often based on starting materials containing carbonyl groups, such as aldehydes, ketones, carboxylic acids, carboxylic anhydrides and esters, which are hydrogenated with hydrogen. The production of ethers and lactones is often based on carboxylic acids, esters or anhydrides thereof, lactones or mixtures thereof.
In der jüngeren Vergangenheit wurden dabei unter Verwendung von oxidativ vorbehandelten Aktivkohleträgern besonders aktive Katalysatoren gefunden. In EP-A-0 848 991 ist ein Palladium, Silber, Rhenium und Eisen enthaltender Katalysator beschrieben, der z.B. Maleinsäure oder deren Ester zu Butandiol hydrieren kann. Bei der Hydrierung von Maleinsäure bei 100 bis 162°C wird eine Selektivität zu Butandiol von 89,5 % erreicht. Der Hydriererfolg wird dadurch geschmälert, daß als Nebenprodukt der Ether Tetrahydrofuran (THF) mit 5,6% entsteht. Daneben entsteht noch als weiteres Nebenprodukt n-Butanol mit 4 %. In US 5,698,749 sind Katalysatoren beschrieben, die ein Element der Gruppe VIII und mindestens noch Rhenium, Wolfram oder Molybdän auf einem oxidativ vorbehandelten Kohleträger enthalten. Insbesondere werden Pd/Re/C- bzw. Pd/Re/Ag/C- Katalysatoren beschrieben. Mit diesen Katalysatoren entsteht bei der Hydrierung von wäßriger Maleinsäure wiederum neben Butandiol THF. Dabei wird Butandiol mit bis zu 92,8 % Selektivität erhalten. THF entsteht jedoch immer noch zu 1,6 %, das weitere Nebenprodukt n-Butanol zu 4,6 %.In the recent past, particularly active catalysts have been found using oxidatively pretreated activated carbon carriers. EP-A-0 848 991 describes a catalyst containing palladium, silver, rhenium and iron which, for example, can hydrogenate maleic acid or its ester to give butanediol. When hydrogenating maleic acid at 100 to 162 ° C, a selectivity to butanediol of 89.5% is achieved. The hydrogenation success is diminished by the fact that the byproduct is ether tetrahydrofuran (THF) with 5.6%. In addition, 4% of n-butanol is formed as a further by-product. No. 5,698,749 describes catalysts which contain an element from Group VIII and at least rhenium, tungsten or molybdenum on an oxidatively pretreated carbon support. In particular, Pd / Re / C or Pd / Re / Ag / C catalysts are described. With these catalysts, hydrogenation of aqueous maleic acid in turn produces, in addition to butanediol, THF. Butane diol is obtained with up to 92.8% selectivity. However, THF is still 1.6%, the other by-product n-butanol is 4.6%.
Die Tendenz der Hydriermetalle Rhenium bzw. Platin, bei der Hydrierung von Maleinsäure-Derivaten THF und damit Ether zu bilden, ist bekannt (siehe z.B. A.F. Timofeev et al., Prikl. Khim. (Leningrad) 1981 , 54 (2), 335-8, Chemical Abstracts 95: 80602 X. Der gleiche Effekt wird auch in GB-A-1 551 741 unter Verwendung von geträgerten Pd/Re-, Pt/Re- oder Pt/Pd/Re-Katalysatoren beschrieben.The tendency of the hydrogenation metals rhenium or platinum to form THF and thus ethers in the hydrogenation of maleic acid derivatives is known (see, for example, AF Timofeev et al., Prikl. Khim. (Leningrad) 1981, 54 (2), 335- 8, Chemical Abstracts 95: 80602 X. The same effect is also described in GB-A-1 551 741 using supported Pd / Re, Pt / Re or Pt / Pd / Re catalysts.
H.S. Broadbent et al. beschrieben in J. Org. Chem. 24, 1847-1854 (1959) die Bernsteinsäurehydrierung an nicht geträgertem metallischem Re, bei der erhebliche Mengen an THF gebildet werden.H. S. Broadbent et al. described in J. Org. Chem. 24, 1847-1854 (1959) the succinic acid hydrogenation on unsupported metallic Re, in which considerable amounts of THF are formed.
Die Vermeidung von Ethern als Nebenprodukt ist bei technischen Hydrierprozessen zur Herstellung von Alkoholen jedoch wünschenswert, da deren Bildung die Wirtschaftlichkeit des Verfahrens vermindert. Ferner sind die Ether mitunter schwer vom gewünschten Produkt abzutrennen. Darüber hinaus verursachen die Ether erhebliche Entsorgungskosten. THF ist beispielsweise nur schwer biologisch abbaubar und darf daher bereits in kleinen Mengen nicht mehr in eine Kläranlage eingebracht werden.Avoiding ethers as a by-product is desirable in industrial hydrogenation processes for the production of alcohols, however, since their formation reduces the economics of the process. Furthermore, the ethers are sometimes difficult to separate from the desired product. In addition, the ethers cause considerable disposal costs. For example, THF is difficult to biodegrade and must therefore no longer be introduced into a sewage treatment plant in small quantities.
US 5,478,952 betrifft die Hydrierung von Maleinsäure an einem Ru/Re- Aktivkohlekatalysator zur Bildung von THF und gamma-Butyrolacton als Hauptprodukten. - 3 -US 5,478,952 relates to the hydrogenation of maleic acid on an Ru / Re activated carbon catalyst to form THF and gamma-butyrolactone as main products. - 3 -
EP-A-0 276 012 betrifft die Hydrierung von Maleinsäure zu gamma-Butyrolacton und Butandiol an PαVRe/TiO2-Katalysatoren.EP-A-0 276 012 relates to the hydrogenation of maleic acid to gamma-butyrolactone and butanediol over PαVRe / TiO 2 catalysts.
Aufgrund der hohen Korrosivität von Säurelösungen bei hohen Temperaturen und Drücken ist es wünschenswert, die Hydrierung bei niedrigen Temperaturen durchzuführen.Due to the high corrosiveness of acid solutions at high temperatures and pressures, it is desirable to carry out the hydrogenation at low temperatures.
Aufgabe der vorliegenden Erfindung ist die Bereitstellung von Rhenium- Katalysatoren, mit denen man mit hoher Gesamtselektivität Carbonylver- bindungen wahlweise zu Alkoholen hydrieren kann, ohne Ether zu bilden, oder selektiv zu Ethern und Lactonen hydrieren kann.It is an object of the present invention to provide rhenium catalysts which can be used to selectively hydrogenate carbonyl compounds to alcohols with high overall selectivity without forming ether, or to selectively hydrogenate to ethers and lactones.
Die Aufgabe wird erfindungsgemäß gelöst durch ein Verfahren zur katalytischen Flydrierung von Carbonylverbindungen an einem Katalysator, der Rhenium auf Aktivkohle enthält, wobei man als Katalysator Rhenium (als Metall gerechnet) in einem Gewichts- Verhältnis zur Aktivkohle von 0,0001 bis 0,5, Platin (als Metall gerechnet) in einem Gewichtsverhältnis zur Aktivkohle von 0,0001 bis 0,5 und gegebenfalls mindestens ein weiteres Metall, ausgewählt aus Zn, Cu, Ag, Au, Mi, Fe, Ru, Mn, Cr, Mo, W und V in einem Gewichtsverhältnis zur Aktivkohle von 0 bis 0,25 einsetzt, zur Herstellung von Alkoholen, wobei die Aktivkohle nichtoxidativ vorbehandelt ist, oder zur Flerstellung von Ethern und Lactonen, wobei von Carbonsäuren, Estern oder Anhydriden davon, Lactonen oder deren Gemischen ausgegangen wird und die Hydrierung bei einem Wasserstoffdruck von maximal 25 bar durchgeführt wird und die Aktivkohle nichtoxidativ vorbehandelt sein kann.The object is achieved according to the invention by a process for the catalytic flydration of carbonyl compounds on a catalyst which contains rhenium on activated carbon, the catalyst being rhenium (calculated as metal) in a weight ratio to activated carbon of 0.0001 to 0.5 platinum (calculated as metal) in a weight ratio to activated carbon of 0.0001 to 0.5 and optionally at least one further metal selected from Zn, Cu, Ag, Au, Mi, Fe, Ru, Mn, Cr, Mo, W and V used in a weight ratio to the activated carbon of 0 to 0.25, for the production of alcohols, the activated carbon has not been pretreated oxidatively, or for the preparation of ethers and lactones, starting from carboxylic acids, esters or anhydrides thereof, lactones or their mixtures and the Hydrogenation is carried out at a maximum hydrogen pressure of 25 bar and the activated carbon can be pretreated non-oxidatively.
Es wurde gefunden, daß man Carbonylverbindungen katalytisch zu den entsprechenden Alkoholen ohne Etherbildung bei niedrigen Temperaturen (bevorzugt unter 140°C) hydrieren kann, indem man mindestens Rhenium oder Rhenium/Platin auf nichtoxidativ behandelten Kohlenstoff-Trägern wie Aktivkohlen zur Hydrierung einsetzt. Dabei heißt ohne Etherbildung, daß die Etherbildung höchstens 0,5 % Anteil an den Hydrierprodukten haben soll. Bevorzugt liegt der Etheranteil unter 0,2 %, besonders bevorzugt unter 0,1 %.It has been found that carbonyl compounds can be catalytically hydrogenated to the corresponding alcohols without ether formation at low temperatures (preferably below 140 ° C.) by using at least rhenium or rhenium / platinum on non-oxidatively treated carbon supports such as activated carbon for the hydrogenation. Without ether formation, this means that the ether formation should have a maximum of 0.5% of the hydrogenation products. The ether content is preferably below 0.2%, particularly preferably below 0.1%.
Bei niedrigen Drücken ist die Herstellung von Ethern und Lactonen, in der Regel im Gemisch, möglich. Über den Wasserstoffdruck kann die Umsetzung in Richtung der gewünschten Produkte gesteuert werden, wobei bei höheren Drücken überwiegend Alkohole und bei niedrigen Drücken überwiegend Ether und Lactone gebildet werden. Dabei können Ether als Hauptprodukte entstehen.At low pressures, the production of ethers and lactones, usually in a mixture, is possible. The reaction in the direction of the desired products can be controlled via the hydrogen pressure, alcohols being formed predominantly at higher pressures and ether and lactones predominantly being formed at low pressures. Thereby, ethers can be the main products.
Eine nichtoxidative Behandlung des Kohlenstoffträgermaterials mit Mineralsäuren oder Basen ist einer oxidativen Behandlung mit HNO oder Peroxiden gegenüber weiterhin als vorteilhaft zu bewerten, da eine oxidative Vorbehandlung von Aktivkohlen mit H2O oder Peroxiden einen teuren Vorbehandlungsprozeß darstellt, der die Katalysatorfertigungskosten erheblich in die Höhe treibt. Bei der oxidativen Vorbehandlung mit HNO entstehen nitrose Gase, die in aufwendigen Abgasreinigungsverfahren (DeNOX) entfernt werden müssen. Ein weiterer Nachteil der oxidativen Vorbehandlung liegt in dem Materialverlust an Trägermaterial durch die oxidative Vorbehandlung. Die kohlenstoffhaltigen Trägermaterialien lösen sich zum Teil in den Oxidationsmitteln auf und Formkörper können bei entsprechender Temperatur sogar komplett zerfallen.A non-oxidative treatment of the carbon support material with mineral acids or bases can furthermore be regarded as advantageous compared to an oxidative treatment with ENT or peroxides, since an oxidative pretreatment of activated carbons with H 2 O or peroxides is an expensive pretreatment process, which increases the catalyst production costs considerably. During the oxidative pretreatment with ENT, nitrous gases are generated which have to be removed in complex exhaust gas cleaning processes (DeNOX). Another disadvantage of the oxidative pretreatment is the loss of material due to the oxidative pretreatment. The carbon-containing carrier materials partially dissolve in the oxidizing agents and moldings can even completely disintegrate at the appropriate temperature.
Als Aktivkohlen kommen im allgemeinen die handelsüblichen Aktivkohlen in Frage. Bevorzugt werden solche eingesetzt, die wenig Chlor und Schwefel enthalten und deren Mikroporenanteil im Verhältnis zum Meso- und Makroporenanteil möglichst gering ist. Die nichtoxidative Behandlung der Aktivkohlen kann im einfachsten Fall durch Behandlung mit Lösungsmitteln wie Wasser oder Alkoholen vorgenommen werden. Der Kohleträger kann auch durch nichtoxidative Behandlung mit Mineralsäuren wie HC1, H3PO4, H2SO4, HBr oder HF konditioniert werden. Auch organische Säuren wie Ameisensäure oder Essigsäure können für die Vorbehandlung des Trägermateriales verwendet /64338The commercially available activated carbons are generally suitable as activated carbons. Preference is given to using those which contain little chlorine and sulfur and whose proportion of micropores is as small as possible in relation to the proportion of mesopore and macropores. In the simplest case, the non-oxidative treatment of the activated carbons can be carried out by treatment with solvents such as water or alcohols. The carbon carrier can also be conditioned by non-oxidative treatment with mineral acids such as HC1, H 3 PO 4 , H 2 SO 4, HBr or HF. Organic acids such as formic acid or acetic acid can also be used for the pretreatment of the carrier material / 64338
- 5 -- 5 -
werden. Einen ebenfalls positiven Effekt auf die katalytische Performance haben Kohleträger, die mit Lösungen von Basen wie NH4OH, NaOH oder KOH vorbehandelt wurden.become. Coal carriers that have been pretreated with solutions of bases such as NH 4 OH, NaOH or KOH also have a positive effect on the catalytic performance.
Die Behandlung der Aktivkohle mit dem nichtoxidativ wirkenden Agens kann vor oder auch während der Aufbringung der Platin- und Rheniumkomponente bzw. weiterer Katalysatorkomponenten erfolgen.The active carbon can be treated with the non-oxidizing agent before or during the application of the platinum and rhenium component or other catalyst components.
In einer weiteren besonderen Ausführungsform werden solche Katalysatoren verwendet, bei denen der Aktivkohleträger zuerst nichtoxidativ und dann oxidativ vorbehandelt wird. In einer weiteren besonderen Ausführungsform werden solche Katalysatoren verwendet, bei denen der Aktivkohleträger zuerst oxidativ und dann nichtoxidativ vorbhandelt wird.In a further particular embodiment, catalysts are used in which the activated carbon carrier is first pretreated non-oxidatively and then oxidatively. In a further particular embodiment, catalysts are used in which the activated carbon carrier is first pretreated oxidatively and then non-oxidatively.
Bei einer bevorzugten nichtoxidativen Vorbehandlung wird der Aktivkohleträger bei erhöhter Temperatur (50 bis 90°C) im Vorbehandlungsmittel gerührt. Als Vorbehandlungsmittel können dabei sowohl konzentrierte, als auch verdünnte Vorbehandlungsmittel (Säuren, Laugen) verwendet werden. Bevorzugt werden konzentrierte Vorbehandlungsmittel verwendet (konz. HC1, konz. NaOH, halbkonz. H3PO ). Die Behandlungszeit liegt in der Regel zwischen einer und 48 Stunden, bevorzugt zwischen 5 und 30 h. Nach der Behandlung wird der Kohlenstoffträger zur Reinigung von störenden Ionen mit Wasser gewaschen. Es kann sich eine Nachbehandlung bei erhöhter Temperatur in Wasser (zwischen einer und 48 Stunden, bevorzugt zwischen 5 und 30 Stunden) anschließen.In a preferred non-oxidative pretreatment, the activated carbon carrier is stirred in the pretreatment agent at elevated temperature (50 to 90 ° C.). Both concentrated and diluted pretreatment agents (acids, alkalis) can be used as pretreatment agents. Concentrated pretreatment agents are preferably used (conc. HC1, conc. NaOH, semi-conc. H 3 PO). The treatment time is usually between one and 48 hours, preferably between 5 and 30 hours. After the treatment, the carbon carrier is washed with water to purify interfering ions. Aftertreatment at elevated temperature in water (between one and 48 hours, preferably between 5 and 30 hours) can follow.
Bei der Verwendung von sauren Vorbehandlungsmitteln wird beim pH-Test (5g Kohleträger in dest. H20 20 Minuten kochen, Lösung filtrieren, unter Stickstoff erkalten lassen, bei 20°C pH messen) eine saurere Oberfläche als beim Ausgangsmaterial festgestellt, die Verwendung von basischen Vorbehandlungs- mittein sorgt für eine basischere Oberfläche. Als Rheniumkomponente wird üblicherweise (NH4)ReO4, Re O7, ReO , ReCl3, ReCl5, Re(CO)5Cl, Re(CO)5Br oder Re2(CO))0 verwendet, ohne daß diese Aufzählung ausschließlich gemeint ist. Bevorzugt wird Re O7 eingesetzt.If acidic pretreatment agents are used, the pH test (boil 5g of charcoal in dist. H 2 0 20 minutes, filter solution, let cool under nitrogen, measure at pH 20 ° C) reveals a more acidic surface than the starting material basic pretreatment agent ensures a more basic surface. The rhenium component used is usually (NH 4 ) ReO 4 , Re O 7 , ReO, ReCl 3 , ReCl 5 , Re (CO) 5 Cl, Re (CO) 5 Br or Re 2 (CO) ) 0 , without this list is meant exclusively. Re O 7 is preferably used.
Es wird neben Rhenium noch Platin auf den Katalysator aufgebracht. Das Platin kann als z.B. Platinpulver, Oxid, Oxidhydrat, Nitrat, Platin(II)- oder -(IV)- chlorid, Platin(IV)-chlorwasserstoffsäure, Platin(II)- oder -(IV)-Bromid, Platin(II)-jodid, eis- bzw. trans-Platin(II)-diamin-chlorid, eis- bzw. trans- Platin(IV)-diamin-chlorid, Platin(II)diamin-nitrit, Platin(II)-ethylendiamin- chlorid, Platin(II)-tetraminchlorid bzw. -chlorid-Hydrat, Platin(II)-tetraminnitrat, Platin(II)-ethylendiamin-chlorid, Platin(0)-tetrakis-(triphenylphosphin), eis- bzw. trans-Platin(II)-bis-(triethylphosphin)-chlorid, eis- bzw. trans-Platin(II)-bis- (triethylphosphin)oxalat, cis-Platin(II)-bis-(triphenylphosphin)-chlorid,In addition to rhenium, platinum is also applied to the catalyst. The platinum can e.g. Platinum powder, oxide, hydrated oxide, nitrate, platinum (II) - or - (IV) - chloride, platinum (IV) -hydrochloric acid, platinum (II) - or - (IV) -bromide, platinum (II) -iodide, ice or trans-platinum (II) diamine chloride, ice or trans platinum (IV) diamine chloride, platinum (II) diamine nitrite, platinum (II) ethylenediamine chloride, platinum (II) - Tetramine chloride or chloride hydrate, platinum (II) tetramine nitrate, platinum (II) ethylenediamine chloride, platinum (0) tetrakis (triphenylphosphine), ice or trans-platinum (II) bis (triethylphosphine) ) chloride, ice or trans platinum (II) bis (triethylphosphine) oxalate, cis platinum (II) bis (triphenylphosphine) chloride,
Platin(IV)-bis-(triphenylphosphin)-oxid, Platin(II)(-2,2'-6',2"-terpyridin)chlorid- Dihydrat, cis-Platin-bis-(acetonitril)-dichlorid, cis-Platin-bis-(benzonitril)- dichlorid, Platin(II)-acetylacetonat, Platin(II)-lc,5c-cyclooctadien-chlorid bzw. - bromid, Platinnitrosylnitrat, bevorzugt als Platinoxid oder -nitrat, besonders bevorzugt als Platinnitrat aufgebracht werden, ohne daß diese Aufzählung ausschließlich gemeint ist.Platinum (IV) bis (triphenylphosphine) oxide, platinum (II) (- 2,2'-6 ', 2 "-terpyridine) chloride dihydrate, cis-platinum-bis- (acetonitrile) dichloride, cis- Platinum bis (benzonitrile) dichloride, platinum (II) acetylacetonate, platinum (II) -lc, 5c-cyclooctadiene chloride or - bromide, platinum nitrosyl nitrate, preferably as platinum oxide or nitrate, particularly preferably as platinum nitrate, without this list being meant exclusively.
Rhenium (als Metall gerechnet) kann in einem Gewichts- Verhältnis zur Aktivkohle von 0,0001 bis 0,5 bevorzugt 0,001 bis 0,2, besonders bevorzugt von 0,01 bis 0,15 aufgebracht sein. Für Platin gelten die gleichen Verhältnisse. Das Gewichtsverhältnis von Rhenium zu Platin (als Metalle gerechnet) liegt in einem Bereich von 0,01 - 100. Bevorzugt 0,05 bis 50, besonders bevorzugt 0,1 bis 10.Rhenium (calculated as metal) can be applied in a weight ratio to activated carbon of 0.0001 to 0.5, preferably 0.001 to 0.2, particularly preferably from 0.01 to 0.15. The same conditions apply to platinum. The weight ratio of rhenium to platinum (calculated as metals) is in a range from 0.01 to 100. Preferably 0.05 to 50, particularly preferably 0.1 to 10.
Es können auf dem Katalysator noch weitere Elemente vorhanden sein. Beispielhaft seien Zn, Cu, Ag, Au, Ni, Fe, Ru, Mn, Cr, Mo W und V genannt. Diese Elemente modifizieren den Katalysator im wesentlichen bzgl. Aktivität und Selektivität (Hydrogenolyseprodukte) sind aber nicht essentiell. Ihr Gewichtsverhältnis zu Re kann 0 bis 100, bevorzugt 0,5 bis 30, besonders bevorzugt 0,1 bis 5 betragen. -7-There may be other elements on the catalyst. Examples include Zn, Cu, Ag, Au, Ni, Fe, Ru, Mn, Cr, Mo W and V. These elements modify the catalyst essentially with regard to activity and selectivity (hydrogenolysis products) but are not essential. Their weight ratio to Re can be 0 to 100, preferably 0.5 to 30, particularly preferably 0.1 to 5. -7-
Die Aufbringung der Aktivkomponenten Re und Pt kann durch Imprägnierung in einem oder mehreren Schritten mit einer wäßrigen, alkoholischen oder mit anderen organischen Lösungsmitteln hergestellten Lösung der jeweiligen gelösten Salze, Imprägnierung mit einer Lösung von gelöstem oxidischen oder metallischen Kolloid der Aktivkomponenten, Gleichgewichtsadsorption in einem oder mehreren Schritten der in wäßriger oder alkoholischer Lösung gelösten Salze oder Gleichgewichtsadsorption von gelöstem metallischem oder oxidischem Kolloid an der vorbehandelten Aktivkohle vorgenommen werden. Bei diesen Verfahren können die Aktivkomponenten entweder gleichzeitig oder nacheinander auf die Aktivkohle aufgebracht werden. Zwischen den einzelnen Imprägnierungs- und Gleichgewichtsadsorptionsschritten liegt jeweils ein Trocknungsschritt zur Entfernung des Lösungsmittels. Bevorzugt geschieht die Aufbringung der Aktivkomponenten durch Imprägnierung mit einer wäßrigen Salzlösung oder einem wäßrigen oxidischen Kolloid in einem Schritt.The active components Re and Pt can be applied by impregnation in one or more steps with an aqueous, alcoholic or other organic solvent solution of the respective dissolved salts, impregnation with a solution of dissolved oxidic or metallic colloid of the active components, equilibrium adsorption in one or more Steps of the salts dissolved in aqueous or alcoholic solution or equilibrium adsorption of dissolved metallic or oxidic colloid on the pretreated activated carbon. In these processes, the active components can be applied to the activated carbon either simultaneously or in succession. There is a drying step between the individual impregnation and equilibrium adsorption steps to remove the solvent. The active components are preferably applied in one step by impregnation with an aqueous salt solution or an aqueous oxidic colloid.
Zur Entfernung des Lösungsmittels nach dem Imprägnierungs- oder Gleichgewichtsadsorptionsschritt erfolgt eine Trocknung des imprägnierten Katalysators. Die Trocknungstemperatur liegt dabei bei 30 - 350 °C, bevorzugt 40 - 280°C, besonders bevorzugt 50 - 150°C.To remove the solvent after the impregnation or equilibrium adsorption step, the impregnated catalyst is dried. The drying temperature is 30-350 ° C, preferably 40-280 ° C, particularly preferably 50-150 ° C.
Die Katalysatoren werden üblicherweise vor ihrem Einsatz aktiviert. Diese Aktivierung kann durch Anwendung einer reduzierend wirkenden Gasatmosphäre auf den Katalysator geschehen. Bevorzugt wird eine Aktivierung mit Hilfe von Wasserstoff angewendet. Die Aktivierungstemperatur liegt dabei üblicherweise bei 100 - 500°C, bevorzugt 130 - 400°C, besonders bevorzugt 150 - 350°C. Alternative Reduktionsmethoden sind die Reduktion der metallischen Komponenten durch in Kontaktbringen mit einem flüssigen Reduktionsmittel wie Hydrazin, Formaldehyd oder Natriumforrniat. Dabei werden die flüssigen Reduktionsmittel üblicherweise bei Temperaturen zwischen 10 und 100°C in Kontakt gebracht. Besonders bevorzugt ist das Inkontaktbringen bei Temperaturen zwischen 20 bis 80°C. - 8 -The catalysts are usually activated before they are used. This activation can be done by applying a reducing gas atmosphere to the catalyst. Activation with the aid of hydrogen is preferably used. The activation temperature is usually 100-500 ° C., preferably 130-400 ° C., particularly preferably 150-350 ° C. Alternative reduction methods are the reduction of the metallic components by bringing them into contact with a liquid reducing agent such as hydrazine, formaldehyde or sodium formate. The liquid reducing agents are usually brought into contact at temperatures between 10 and 100 ° C. Contacting at temperatures between 20 to 80 ° C. is particularly preferred. - 8th -
Die Hydrierung zur Herstellung von Alkoholen wird üblicherweise bei 50 - 250°C, bevorzugt bei 60 - 220°C, besonders bevorzugt bei 70 - 190°C, ganz besonders bevorzugt bei 80 - 140°C durchgeführt. Dabei wird üblicherweise bei einem Reaktionsdruck zwischen 3 und 330 bar, bevorzugt 20 und 300 bar hydriert. Dabei wird der Druckbereich der Hydrierung in der Flüssigphase im Festbett bei über 150 bar, vorzugsweise 150 - 300 bar, im Festbett in der Gasphase 3 bis 100 bar und in Suspension 10 - 90 bar bevorzugt.The hydrogenation for the production of alcohols is usually carried out at 50-250 ° C., preferably at 60-220 ° C., particularly preferably at 70-190 ° C., very particularly preferably at 80-140 ° C. Hydrogenation is usually carried out at a reaction pressure between 3 and 330 bar, preferably 20 and 300 bar. The pressure range of the hydrogenation in the liquid phase in the fixed bed at more than 150 bar, preferably 150-300 bar, in the fixed bed in the gas phase 3 to 100 bar and in suspension 10-90 bar is preferred.
Als Ausgangsstoffe für die Hydrierung zur Herstellung von Alkoholen sind im allgemeinen Carbonylverbindungen geeignet, die zusätzlich C-C-Doppel- oder Dreifachbindungen enthalten können. Beispiel für Aldehyde sind Propionaldehyd, Butyraldehyde, Crotonaldehyd, Ethylhexanal, Nonanal und Glucose. Beispiele für Carbonsäuren sind Bernsteinsäure, Fumarsäure, Maleinsäure, Glutarsäure, Adipinsäure, Hydroxycapronsäure, Octandisäure, Dodecandisäure, 2- Cyclododecylpropionsäure und gesättigte oder ungesättigte Fettsäuren. Als Ester sind Ester der vorgenannten Säuren, z.B. als Methyl-, Ethyl-, Propyl- oder Butylester zu nennen, ferner sind Lactone, z.B. gamma-Butyrolacton,, delta- Valerolacton oder Caprolacton einsetzbar. Außerdem können Anhydride wie Bernsteinsäureanhydrid oder Maleinsäureanhydrid verwendet werden. Bevorzugte Ausgangsstoffe sind Bernsteinsäure, Maleinsäure, Adipinsäure, 2- Cyclododecylpropionsäure, Bernsteinsäureanhydrid, Maleinsäureanhydrid sowie die Ester dieser Säuren und gamma-Butyrolacton.Suitable starting materials for the hydrogenation for the production of alcohols are in general carbonyl compounds which can additionally contain double or triple C-C bonds. Examples of aldehydes are propionaldehyde, butyraldehyde, crotonaldehyde, ethylhexanal, nonanal and glucose. Examples of carboxylic acids are succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, hydroxycaproic acid, octanedioic acid, dodecanedioic acid, 2-cyclododecylpropionic acid and saturated or unsaturated fatty acids. As esters are esters of the aforementioned acids, e.g. Mention may be made of methyl, ethyl, propyl or butyl esters, lactones, e.g. gamma-butyrolactone, delta-valerolactone or caprolactone can be used. Anhydrides such as succinic anhydride or maleic anhydride can also be used. Preferred starting materials are succinic acid, maleic acid, adipic acid, 2-cyclododecylpropionic acid, succinic anhydride, maleic anhydride and the esters of these acids and gamma-butyrolactone.
Es wurde nun Herstellung von Ethern und Lactonen gefunden, daß man insbesondere C4-C5-Dicarbonsäuren, -dicarbonsäureester und -anhydride katalytisch vornehmlich zu den entsprechenden cyclischen Ethern und Lactonen als weitere Wertkomponenten bei niedrigen Wasserstoffdrücken (< 25 bar, vorzugsweise < 20 bar) hydrieren kann, indem man mindestens Rhenium und Platin auf Kohlenstoff- Trägern wie Aktivkohlen zur Hydrierung einsetzt. Bislang wurde bei ähnlich niedrigen Drücken ausschließlich gamma-Butyrolacton (GBL) erhalten. Ein weiterer erheblicher Nachteil bestand bislang in einem unvollständigen Säureumsatz bei derart niedrigen Drücken. Diese Nachteile sind nunmehr behoben.It has now been found that ethers and lactones can be prepared by catalytically in particular C 4 -C 5 dicarboxylic acids, dicarboxylic esters and anhydrides, in particular to the corresponding cyclic ethers and lactones as further valuable components at low hydrogen pressures (<25 bar, preferably <20 bar ) can be hydrogenated by using at least rhenium and platinum on carbon supports such as activated carbons for the hydrogenation. So far, only gamma-butyrolactone (GBL) has been obtained at similarly low pressures. Another considerable disadvantage has hitherto been incomplete acid conversion at such low pressures. These disadvantages are now eliminated.
Die Hydrierung wird vorzugsweise bei 50 bis 250°C, bevorzugt bei 60 bis 240°C, besonders bevorzugt bei 70 bis 235°C durchgeführt.The hydrogenation is preferably carried out at 50 to 250 ° C, preferably at 60 to 240 ° C, particularly preferably at 70 to 235 ° C.
Die im erfindungsgemäßen Verfahren erhaltenen cyclischen Ether und Lactone werden zum Beispiel als Lösungsmittel und Zwischenprodukte eingesetzt. Eine Behandlung des Kohlenstoffträgermaterials kann auch zur Herstellung von Ethern und Lactonen durchgeführt werden, ist aber nicht zwingend erforderlich.The cyclic ethers and lactones obtained in the process according to the invention are used, for example, as solvents and intermediates. Treatment of the carbon support material can also be carried out to produce ethers and lactones, but is not absolutely necessary.
Als Edukte für die Hydrierung zur Herstellung von Ethern und Lactonen sind im allgemeinen Carbonylverbindungen geeignet, die zusätzlich C-C-Doppel- oderSuitable starting materials for the hydrogenation for the production of ethers and lactones are generally suitable carbonyl compounds which additionally have double or double carbon atoms
Dreifachbindungen enthalten können. Beispiele für Carbonsäuren sindTriple bonds can contain. Examples of carboxylic acids are
Bersteinsäure, Fumarsäure, Maleinsäure, Glutarsäure, Adipinsäure,Succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid,
Hydroxycapronsäure. Als Ester sind Ester der vorgenannten Säuren, zum Beispiel als Methyl-, Ethyl-, Propyl- oder Butylester zu nennen, ferner sind Lactone, zum Beispiel γ-Butyrolacton, δ-Valerolacton oder Caprolacton einsetzbar. Außerdem können Anhydride wie Bernsteinsäureanhydrid oder Maleinsäureanhydrid verwendet werden. Bevorzugte Edukte sind Bernsteinsäure, Maleinsäure,Hydroxycaproic. Esters of the abovementioned acids, for example as methyl, ethyl, propyl or butyl esters, can also be mentioned, and lactones, for example γ-butyrolactone, δ-valerolactone or caprolactone, can also be used. Anhydrides such as succinic anhydride or maleic anhydride can also be used. Preferred educts are succinic acid, maleic acid,
Adipinsäure, Bernsteinsäureanhydrid, Maleinsäureanhydrid sowie die Ester dieserAdipic acid, succinic anhydride, maleic anhydride and the esters thereof
Säuren und γ-Butyrolacton. Insbesondere werden Maleinsäure, Fumarsäure, Bernsteinsäure oder Ester oder Anhydride davon, oder gamma-Butyrolacton zuAcids and γ-butyrolactone. In particular, maleic acid, fumaric acid, succinic acid or esters or anhydrides thereof, or gamma-butyrolactone
THF und gamma-Butyrolacton hydriert.THF and gamma-butyrolactone hydrogenated.
Die zu hydrierenden Verbindungen können in Substanz oder in Lösung hydriert werden. Als Lösungsmittel bietet sich z.B. das Hydrierprodukt selbst an, oder es werden unter den Reaktionsbedingungen inerte Stoffe eingesetzt wie Alkohole wie Methanol, Ethanol, Propanol oder Butanol, ferner sind Ether wie THF oder Ethylenglycolether geeignet. Ein bevorzugtes Lösungsmittel ist Wasser, insbesondere bei der Hydrierung von Carbonsäuren.The compounds to be hydrogenated can be hydrogenated in bulk or in solution. Examples of suitable solvents are the hydrogenation product itself, or substances which are inert under the reaction conditions, such as alcohols such as methanol, ethanol, propanol or butanol, are also ethers such as THF or Ethylene glycol ether suitable. A preferred solvent is water, especially in the hydrogenation of carboxylic acids.
Die Hydrierung kann in der Gas- oder Flüssigphase, ein- oder mehrstufig ausgeübt werden. In der Flüssigphase ist sowohl die Suspensions- als auch die Festbettfahrweise möglich. Bei exothermen Reaktionen kann die Wärme durch außenliegende Kühlmittel abgeführt werden (z.B. Röhrenreaktor). Ferner ist Siedekühlung im Reaktor möglich, vor allem wenn ohne Produktrückführung hydriert werden. Bei Produktrückführung bietet sich ein Kühler im Rückführstrom an.The hydrogenation can be carried out in the gas or liquid phase, in one or more stages. In the liquid phase, both the suspension and the fixed bed procedure are possible. In exothermic reactions, the heat can be dissipated by external coolants (e.g. tube reactor). Boiling cooling in the reactor is also possible, especially if hydrogenation is carried out without recycling the product. A cooler in the return flow is recommended for product return.
Die im erfindungsgemäßen Verfahren erhaltenen Alkohole werden z.B. alsThe alcohols obtained in the process according to the invention are e.g. as
Lösemittel und Zwischenprodukte eingesetzt. Diole wie Butandiol finden alsSolvents and intermediates used. Find diols such as butanediol as
Diolkomponente in Polyestern Verwendung. 2-Cyclododecylpropan-l-ol ist ein gesuchter Moschus-RiechstoffDiol component in polyesters use. 2-Cyclododecylpropan-l-ol is a sought-after musk fragrance
Das erfindungsgemäße Verfahren wird anhand der nachstehenden Beispiele näher erläutert. Die angegebenen Gehalte der einzelnen Komponenten in den Hydrierausträgen sind gaschromatographisch ermittelt worden. Sie sind, wenn nicht anderes angegeben, lösungsmittelfrei gerechnet.The process according to the invention is explained in more detail with the aid of the examples below. The specified contents of the individual components in the hydrogenation discharges have been determined by gas chromatography. Unless otherwise stated, they are calculated without solvents.
BeispieleExamples
Herstellung von AlkoholenManufacture of alcohols
Beispiel 1 (Vergleich):Example 1 (comparison):
Es wurden 20 g Aktivkohle (Epibon Spezial®, von Lurgi) oxidativ mit 95 %20 g of activated carbon (Epibon Spezial®, from Lurgi) were oxidatively at 95%
H?S04 vorbehandelt und mit 5 g Re2O7 sowie 15 g Platinnitratlösung (= 2,5 g PtO2) getränkt und getrocknet. Danach wurde wie folgt weiter vorgegangen: BeiH? S0 4 pretreated and impregnated with 5 g Re 2 O 7 and 15 g platinum nitrate solution (= 2.5 g PtO 2 ) and dried. After that, the procedure was as follows: At
30 %-iger Maleinsäurelösung wurde nach insgesamt 78 h Versuchszeit bei ca. 155°C Reaktionstemperatur im Austrag ca. 94 % Butandiol und 5,26 % n- Butanol, 0,31 % Propanol, 0,3 % Methanol und 0,3 % THF gefunden.30% maleic acid solution was obtained after a total of 78 hours of testing at approx. 155 ° C reaction temperature in the discharge about 94% butanediol and 5.26% n-butanol, 0.31% propanol, 0.3% methanol and 0.3% THF found.
Beispiel 2 (Vergleich):Example 2 (comparison):
Analog Beispiel 1 wurden 20 g Aktivkohle (BG 09®, von Jacobi) oxidativ mit 44 % H2SO4 vorbehandelt und mit 5 g Re2O7 sowie 15 g Platinnitratlösung (= 2,5 g PtO2) getränkt und getrocknet. Danach wurde wie in Beispiel 1 weiter vorgegangen. Bei 30 %-iger Maleinsäurelösung wurde nach insgesamt 78 h Versuchszeit bei ca. 141°C Reaktionstemperatur im Austrag ca. 76,63 % Butandiol und 20,53 % n-Butanol, 1 ,84 % Propanol, 0,52 % Methanol und 0,49 % THF gefunden.Analogously to Example 1, 20 g of activated carbon (BG 09®, from Jacobi) were pretreated oxidatively with 44% H 2 SO 4 and impregnated with 5 g of Re 2 O 7 and 15 g of platinum nitrate solution (= 2.5 g of PtO2) and dried. Then the procedure was as in Example 1. In the case of a 30% maleic acid solution, after a total of 78 h of test time at a reaction temperature of approx. 141 ° C., about 76.63% butanediol and 20.53% n-butanol, 1, 84% propanol, 0.52% methanol and 0 were discharged , 49% THF found.
Beispiel 3:Example 3:
Analog Beispiel 1 wurden 20 g Aktivkohle (BG 09®, von Jacobi) nichtoxidativ mit IM NaOH nichtoxidativ vorbehandelt und mit 5 g Re2O sowie 15 g Platinnitratlösung (= 2,5 g PtO ) getränkt und getrocknet. Danach wurde wie in Beispiel 1 weiter vorgegangen. Bei 30 %-iger Maleinsäurelösung wurde nach insgesamt 78 h Versuchszeit bei ca. 122°C Reaktionstemperatur im Austrag ca. 88,92 % Butandiol und 10,77 % n-Butanol, 0,3 % Propanol und kein THF gefunden.Analogously to Example 1, 20 g of activated carbon (BG 09®, from Jacobi) were pretreated non-oxidatively with IM NaOH and impregnated with 5 g Re 2 O and 15 g platinum nitrate solution (= 2.5 g PtO) and dried. Then the procedure was as in Example 1. In the case of 30% maleic acid solution, after a total of 78 h of test time at approximately 122 ° C. reaction temperature, approximately 88.92% butanediol and 10.77% n-butanol, 0.3% propanol and no THF were found in the discharge.
Beispiel 4:Example 4:
Analog Beispiel 1 wurden 20 g Aktivkohle (BG 09® von Jacobi) nichtoxidativ mit konzentrierter HC1 nichtoxidativ vorbehandelt und mit 5 g Re2O sowie 15 g Platinnitratlösung (= 2,5 g PtO2) getränkt und getrocknet. Danach wurde wie in Beispiel 1 weiter vorgegangen. Bei 30 %-iger Maleinsäurelösung wurde nach insgesamt 78 h Versuchszeit bei ca. 114°C Reaktionstemperatur im Austrag ca. 92,13 % Butandiol und 7,87 % n-Butanol und kein THF gefunden. Beispiel 5:Analogously to Example 1, 20 g of activated carbon (BG 09® from Jacobi) were pretreated non-oxidatively with concentrated HC1 and were impregnated with 5 g Re 2 O and 15 g platinum nitrate solution (= 2.5 g PtO 2 ) and dried. Then the procedure was as in Example 1. In the case of 30% maleic acid solution, after a total of 78 h of test time at about 114 ° C. reaction temperature, about 92.13% butanediol and 7.87% n-butanol and no THF were found in the discharge. Example 5:
Analog Beispiel 1 wurden 20 g Aktivkohle (BG 09® von Jacobi) nichtoxidativ mit Wasserdampf und anschließend 5 %-iger HC1 nichtoxidativ vorbehandelt und mit 5 g Re2O7 sowie 15 g Platinnitratlösung (= 2,5 g PtO2) getränkt und getrocknet. Danach wurde wie in Beispiel 1 weiter vorgegangen. Bei 30 %-iger Maleinsäurelösung wurde nach insgesamt 78 h Versuchszeit bei ca. 131°C Reaktionstemperatur im Austrag ca. 91,4 % Butandiol und 8,26 % n-Butanol, 0,32 % Propanol und kein THF gefunden.Analogously to Example 1, 20 g of activated carbon (BG 09® from Jacobi) were pretreated non-oxidatively with steam and then 5% HC1 non-oxidatively and soaked with 5 g of Re 2 O 7 and 15 g of platinum nitrate solution (= 2.5 g of PtO 2 ) and dried , Then the procedure was as in Example 1. In the case of 30% maleic acid solution, after a total of 78 h of test time at a reaction temperature of approximately 131 ° C., approximately 91.4% butanediol and 8.26% n-butanol, 0.32% propanol and no THF were found in the discharge.
Beispiel 6:Example 6:
Analog Beispiel 1 wurden 20 g Aktivkohle (BG 09® von Jacobi) nichtoxidativ mit 44 % H3PO4 nichtoxidativ vorbehandelt und mit 5 g Re O sowie 15 g Platinnitratlösung (= 2,5 g PtO2) getränkt und getrocknet. Danach wurde wie in Beispiel 1 weiter vorgegangen. Bei 30 %-iger Maleinsäurelösung wurde nach insgesamt 78 h Versuchszeit bei ca. 107°C Reaktionstemperatur im Austrag ca. 93,36 % Butandiol und 5,86 % n-Butanol, 0,21 % Methanol und kein THF gefunden.Analogously to Example 1, 20 g of activated carbon (BG 09® from Jacobi) were pretreated non-oxidatively with 44% H 3 PO 4 and were impregnated with 5 g Re O and 15 g platinum nitrate solution (= 2.5 g PtO 2 ) and dried. Then the procedure was as in Example 1. In the case of a 30% maleic acid solution, after a total of 78 h of test time at a reaction temperature of about 107 ° C., about 93.36% butanediol and 5.86% n-butanol, 0.21% methanol and no THF were found in the discharge.
Durch nichtoxidative Vorbehandlung der Aktivkohle hergestellte Katalysatoren waren in der Lage, bei niedrigerer Temperatur Maleinsäure zum Zielprodukt 1 ,4- Butandiol zu hydrieren, als die bekannten Katalysatoren. Zudem konnte der Anteil an Ether-Nebenprodukt stark vermindert werden.Catalysts produced by non-oxidative pretreatment of the activated carbon were able to hydrogenate maleic acid to the target product 1,4-butanediol at a lower temperature than the known catalysts. In addition, the proportion of ether by-product could be greatly reduced.
Herstellung von Ethern und LactonenManufacture of ethers and lactones
Beispiel 1 :Example 1 :
60 g Aktivkohle (Epibon von Lurgi) wurden mit Phosphorsäure vorbehandelt und bei 120°C getrocknet. Auf 50 g der so vorbehandelten Kohle wurden 9,81 g Pt(NO3)2 als wässrige Lösung aufgetränkt. Die getränkte Aktivkohle wurde 18 h bei 1 10°C getrocknet, im Anschluß im Stickstoff/Wasserstoffstrom 4 h bei 300°C und Umgebungsdruck reduziert und bei Raumtemperatur im Stickstoff/Luftstrom passiviert. Anschließend wurden 5 g Re O7 auf den passivierten Katalysator aufgetränkt und bei 110°C 18 h getrocknet. Der so gewonnene Katalysator wurde im Stickstoff/Wasserstoffstrom 4 h bei 300°C und Umgebungsdruck aktiviert und bei Raumtemperatur im Stickstoff/Luftstrom passiviert. Der reduzierte Katalysator enthält 3 % Pt und 3 % Re. Vom aktivierten/passivierten Katalysator wurden anschließend 25 ml in einen 25 ml fassenden Reaktor eingefüllt.60 g of activated carbon (Epibon from Lurgi) were pretreated with phosphoric acid and dried at 120 ° C. 9.81 g of Pt (NO 3 ) 2 were impregnated as an aqueous solution onto 50 g of the coal pretreated in this way. The soaked activated carbon was 18 h dried at 110 ° C, then reduced in a nitrogen / hydrogen stream for 4 h at 300 ° C and ambient pressure and passivated at room temperature in a nitrogen / air stream. 5 g of Re O 7 were then impregnated onto the passivated catalyst and dried at 110 ° C. for 18 hours. The catalyst obtained in this way was activated in a nitrogen / hydrogen stream for 4 h at 300 ° C. and ambient pressure and passivated at room temperature in a nitrogen / air stream. The reduced catalyst contains 3% Pt and 3% Re. 25 ml of the activated / passivated catalyst were then introduced into a 25 ml reactor.
Die Hydierung erfolgte in Rieselfahrweise, ohne Produktrückführung. Der Reaktionsdruck lag bei 20 bar, es wurden ca. 180 NL Wasserstoff/h eingeleitet. Bei einer Maleinsäurekonzentration von 30 % (Wasser), eine LHSV von 0,1 h"1 und bei 235°C Reaktortemperatur fanden sich im Hydrieraustrag nach insgesamt 3 Versuchsstunden ca. 73,5 % THF, 1,3 % GBL, 0 % BDO, 25,0 % Alkohole (n- Butanol + n-Propanol). Der Säureumsatz betrug 95,3 %. Bei einer LHSV von 0,2 h"1 wurde unter sonst identischen Reaktionsbedingungen nach 17,5 h Versuchsdauer ein Hydrieraustrag mit ca. 36,5 % THF, 42,7 % GBL, 0,90 % BDO und 19,8 % Alkohole (n-Butanol + n-Propanol) erhalten. Der Säureumsatz betrug 95,1 %.The hydrogenation was carried out in trickle mode, without product return. The reaction pressure was 20 bar, about 180 NL hydrogen / h were introduced. With a maleic acid concentration of 30% (water), an LHSV of 0.1 h "1 and at a reactor temperature of 235 ° C, the hydrogenation output after a total of 3 test hours showed approximately 73.5% THF, 1.3% GBL, 0% BDO , 25.0% alcohols (n-butanol + n-propanol). The acid conversion was 95.3%. With an LHSV of 0.2 h "1 , under otherwise identical reaction conditions, a hydrogenation discharge with approx. 36.5% THF, 42.7% GBL, 0.90% BDO and 19.8% alcohols (n-butanol + n-propanol). The acid conversion was 95.1%.
Beispiel 2 (Referenz):Example 2 (reference):
60 g Aktivkohle (Epibon von Lurgi) wurden mit Phosphorsäure vorbehandelt und bei 120°C getrocknet. Auf 50 g der so vorbehandelten Kohle wurden 2,5 g PdCl als wässrige Lösung aufgetränkt. Die getränkte Aktivkohle wurde 18 h bei 110°C getrocknet, im Anschluß im Stickstoff/Wasserstoffstrom 4 h bei 300°C und Umgebungsdruck reduziert und bei Raumtemperatur im Stickstoff/Luftstrom passiviert. Anschließend wurden 5 g Re2O7 auf den passivierten Katalysator aufgetränkt und bei 100°C 18 h getrocknet. Der so gewonnene Katalysator wurde im Stickstoff/Wasserstoffstrom 4 h bei 300°C und Umgebungsdruck aktiviert und bei Raumtemperatur im Stickstoff/Luftstrom passiviert. Der reduzierte Katalysator enthält 3 % Pd und 3 % Re. Vom aktivierten/passivierten Katalysator wurden anschließend 25 ml in einen 25 ml fassendenReaktor eingefüllt.60 g of activated carbon (Epibon from Lurgi) were pretreated with phosphoric acid and dried at 120 ° C. 2.5 g of PdCl were impregnated as an aqueous solution onto 50 g of the coal pretreated in this way. The impregnated activated carbon was dried at 110 ° C. for 18 h, then reduced in a nitrogen / hydrogen stream for 4 h at 300 ° C. and ambient pressure and passivated at room temperature in a nitrogen / air stream. 5 g of Re 2 O 7 were then impregnated onto the passivated catalyst and dried at 100 ° C. for 18 hours. The catalyst obtained in this way was activated in a nitrogen / hydrogen stream for 4 h at 300 ° C. and ambient pressure and passivated at room temperature in a nitrogen / air stream. The reduced one Catalyst contains 3% Pd and 3% Re. 25 ml of the activated / passivated catalyst were then introduced into a 25 ml reactor.
Die Hydrierung erfolgte in Rieselfahrweise, ohne Produktrückführung. Der Reaktionsdruck lag bei 20 bar, es wurden ca. 100 NL Wasserstoff/h eingeleitet. Bei einer Maleinsäurekonzentration von 30 % (Wasser), einer LHSV von 0,1 h"1 und bei 235°C Reaktortemperatur fanden sich im Hydrieraustrag nach insgesamt 3 Versuchsstunden ca. 65,2 % THF, 11,9 % GBL, 0 % BDO und 22,9 % Alkohole (n-Butanol + n-Propanol). Der Säureumsatz betrug 98,5 %.The hydrogenation was carried out in trickle mode, without product return. The reaction pressure was 20 bar, about 100 NL hydrogen / h were introduced. With a maleic acid concentration of 30% (water), an LHSV of 0.1 h "1 and a reactor temperature of 235 ° C, the hydrogenation output after a total of 3 test hours showed approximately 65.2% THF, 11.9% GBL, 0% BDO and 22.9% alcohols (n-butanol + n-propanol) The acid conversion was 98.5%.
Bei Verwendung von Pt/Re-Katalysatoren auf Aktivkohleträgermaterialien ist es möglich, bei niedrigen Wasserstoffdrücken Maleinsäure mit höheren Selektivitäten überwiegend zum Zielprodukt Tetrahydrofuran und zu geringen Anteilen gamma-Butyrolacton als weiteres Wertprodukt bei gleichzeitig hohen Säureumsätzen zu hydrieren als vergleichbare Pd/Re-Aktivkohlekatalysatoren. When using Pt / Re catalysts on activated carbon support materials, it is possible to hydrogenate maleic acid with higher selectivities at low hydrogen pressures predominantly to the target product tetrahydrofuran and to small proportions of gamma-butyrolactone as a further product of value with high acid conversions than comparable Pd / Re activated carbon catalysts.

Claims

Patentansprüche claims
1. Verfahren zur katalytischen Hydrierung von Carbonylverbindungen an einem Katalysator, der Rhenium auf Aktivkohle enthält, dadurch gekennzeichnet, daß man als Katalysator Rhenium (als Metall gerechnet) in einem Gewichts- Verhältnis zur Aktivkohle von 0,0001 bis 0,5, Platin (als Metall gerechnet) in einem Gewichtsverhältnis zur Aktivkohle von 0,0001 bis 0,5 und gegebenfalls mindestens ein weiteres Metall, ausgewählt aus Zn, Cu, Ag, Au, Ni, Fe, Ru, Mn, Cr, Mo, W und V in einem Gewichtsverhältnis zur Aktivkohle von 0 bis1. A process for the catalytic hydrogenation of carbonyl compounds on a catalyst which contains rhenium on activated carbon, characterized in that rhenium (calculated as metal) as catalyst in a weight ratio to activated carbon of 0.0001 to 0.5, platinum (as Metal calculated) in a weight ratio to activated carbon of 0.0001 to 0.5 and optionally at least one further metal, selected from Zn, Cu, Ag, Au, Ni, Fe, Ru, Mn, Cr, Mo, W and V in one Weight ratio to activated carbon from 0 to
0,25 einsetzt, zur Herstellung von Alkoholen, wobei die Aktivkohle nichtoxidativ vorbehandelt ist, oder zur Herstellung von Ethern und Lactonen, wobei von Carbonsäuren, Estern oder Anhydriden davon, Lactonen oder deren Gemischen ausgegangen wird und die Hydrierung bei einem Wasserstoffdruck von maximal 25 bar durchgeführt wird, und die Aktivkohle nichtoxidativ vorbehandelt sein kann.0.25 is used for the production of alcohols, in which the activated carbon has not been pretreated by oxidation, or for the production of ethers and lactones, starting from carboxylic acids, esters or anhydrides thereof, lactones or mixtures thereof and hydrogenation at a hydrogen pressure of at most 25 bar is carried out, and the activated carbon can be non-oxidatively pretreated.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Aktivkohle mit Wasser, Alkoholen, nicht oxidierenden Mineralsäuren oder nicht oxidierenden organischen Säuren oder Basen vorbehandelt ist.2. The method according to claim 1, characterized in that the activated carbon is pretreated with water, alcohols, non-oxidizing mineral acids or non-oxidizing organic acids or bases.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Vorbehandlung der Aktivkohle mit HC1, H3PO , Ameisensäure, Essigsäure, NH4OH, NaOH oder KOH durchgeführt wird.3. The method according to claim 1 or 2, characterized in that the pretreatment of the activated carbon with HC1, H 3 PO, formic acid, acetic acid, NH 4 OH, NaOH or KOH is carried out.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Aktivkohle vor oder nach der nichtoxidativen Vorbehandlung zusätzlich oxidativ vorbehandelt wurde.4. The method according to any one of claims 1 to 3, characterized in that the activated carbon was additionally oxidatively pretreated before or after the non-oxidative pretreatment.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Carbonylverbindung zur Herstellung von Alkoholen ausgewählt ist aus Aldehyden, Carbonsäuren oder Estern oder Anhydriden davon, oder Lactonen. 5. The method according to any one of claims 1 to 4, characterized in that the carbonyl compound for the production of alcohols is selected from aldehydes, carboxylic acids or esters or anhydrides thereof, or lactones.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Carbonylverbindung ausgewählt ist aus Maleinsäure, Fumarsäure, Bernsteinsäure oder Estern oder Anhydriden davon, oder gamma-Butyrolacton, und zu 1 ,4-Butandiol hydriert wird.6. The method according to claim 5, characterized in that the carbonyl compound is selected from maleic acid, fumaric acid, succinic acid or esters or anhydrides thereof, or gamma-butyrolactone, and is hydrogenated to 1,4-butanediol.
7. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Carbonylverbindung ausgewählt ist aus Adipinsäure, 6-Hydroxycapronsäure oder Estern davon, oder Caprolacton, und zu 1 ,6-Hexandiol hydriert wird.7. The method according to claim 5, characterized in that the carbonyl compound is selected from adipic acid, 6-hydroxycaproic acid or esters thereof, or caprolactone, and is hydrogenated to 1, 6-hexanediol.
8. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Carbonylverbindung 2-Cyclododecylpropionsäure oder ein Ester davon ist, und zu 2-Cyclododecylpropan-l-ol hydriert wird.8. The method according to claim 5, characterized in that the carbonyl compound is 2-cyclododecylpropionic acid or an ester thereof, and is hydrogenated to 2-cyclododecylpropan-l-ol.
9. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Hydrierung in der Flüssigphase an fest angeordneten Katalysatoren zur Herstellung von Alkoholen bei einem Druck im Bereich von 150 bis 300 bar und einer Temperatur im Bereich von 60 bis 220°C und zur Herstellung von Ethern und Lactonen bei einer Temperatur im Bereich von 180 bis 235°C durchgeführt wird.9. The method according to any one of claims 1 to 4, characterized in that the hydrogenation in the liquid phase on fixed catalysts for the production of alcohols at a pressure in the range from 150 to 300 bar and a temperature in the range from 60 to 220 ° C and for the production of ethers and lactones at a temperature in the range of 180 to 235 ° C.
10. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Carbonylverbindung ausgewählt ist aus Maleinsäure, Fumarsäure, Bernsteinsäure oder Estern oder Anhydriden davon, oder gamma- Butyrolacton, und zu Tetrahydrofuran und gamma-Butyrulacton hydiert wird.10. The method according to any one of claims 1 to 4, characterized in that the carbonyl compound is selected from maleic acid, fumaric acid, succinic acid or esters or anhydrides thereof, or gamma-butyrolactone, and is hydrogenated to tetrahydrofuran and gamma-butyrulactone.
1 1. Katalysator aus Rhenium (als Metall gerechnet) in einem Gewichts-Verhältnis zur Aktivkohle von 0,0001 bis 0,5, Platin (als Metall gerechnet) in einem Gewichts-Verhältnis zur Aktivkohle von 0,0001 bis 0,5 und gegebenfalls mindestens einem weiteren Metall ausgewählt aus Zn, Cu, Ag, Au, Ni, Fe, Ru,1 1. Catalyst made of rhenium (calculated as metal) in a weight ratio to activated carbon of 0.0001 to 0.5, platinum (calculated as metal) in a weight ratio to activated carbon from 0.0001 to 0.5 and if necessary at least one further metal selected from Zn, Cu, Ag, Au, Ni, Fe, Ru,
Mn, Cr, Mo, W, V (als Metall gerechnet) in einem Gewichts-Verhältnis zur Aktivkohle von 0 bis 0,25 aus nichtoxidativ vorbehandelter Aktivkohle als Träger.Mn, Cr, Mo, W, V (calculated as metal) in a weight ratio to Activated carbon from 0 to 0.25 from non-oxidatively pretreated activated carbon as a carrier.
12. Katalysator nach Anspruch 11, in dem die Aktivkohle vor oder nach der nichtoxidativen Vorbehandlung zusätzlich oxidativ vorbehandelt wurde.12. Catalyst according to claim 11, in which the activated carbon was additionally oxidatively pretreated before or after the nonoxidative pretreatment.
13. Verwendung eines Katalysators gemäß Anspruch 1 1 oder 12 bei der kataly- tischen Hydrierung von Carbonylverbindungen. 13. Use of a catalyst according to claim 1 1 or 12 in the catalytic hydrogenation of carbonyl compounds.
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