WO2002068119A1 - Shaped copper and chromium containing catalyst for use in hydrogenation and dehydrogenation reactions - Google Patents

Shaped copper and chromium containing catalyst for use in hydrogenation and dehydrogenation reactions Download PDF

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Publication number
WO2002068119A1
WO2002068119A1 PCT/EP2002/000211 EP0200211W WO02068119A1 WO 2002068119 A1 WO2002068119 A1 WO 2002068119A1 EP 0200211 W EP0200211 W EP 0200211W WO 02068119 A1 WO02068119 A1 WO 02068119A1
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WIPO (PCT)
Prior art keywords
catalyst according
catalyst
acid
hydrogenation
hydrogenolysis
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PCT/EP2002/000211
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German (de)
French (fr)
Inventor
Guido Stochniol
Inge Beul
Kurt-Alfred Gaudschun
Daniel Ostgard
Peter Panster
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Degussa Ag
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Application filed by Degussa Ag filed Critical Degussa Ag
Priority to EP02710001A priority Critical patent/EP1361921A1/en
Priority to JP2002567467A priority patent/JP2004518533A/en
Publication of WO2002068119A1 publication Critical patent/WO2002068119A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0063—Granulating
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/868—Chromium copper and chromium
    • 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
    • B01J35/60—
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a shaped copper catalyst, a process for its production and its use.
  • Cu catalysts and their use in hydrogenation and dehydrogenation reactions are known. Cr or Zn is frequently mentioned as a second important component, Cr generally being a component with a high mass fraction.
  • These Cu-containing systems are used industrially in various reactions. These include, for example, the hydrogenation of aldehydes in the production of oxo alcohols . Hydrogenolysis of fatty acid methyl esters, the hydrogenation of fatty acids to fatty alcohols, the reductive amination and the dehydrogenation of alcohols to aldehydes or ketones. The synthesis of methanol from synthesis gas with Cu-containing catalysts is also known.
  • precipitation is precipitated from an aqueous solution of Cu (II) and Mn (II) salts by adding alkalis, which is filtered off and thermally treated to produce the catalyst.
  • US Patent 5,008,235 describes a process for hydrogenating a starting material to the corresponding alcohol with the aid of a catalyst consisting of Cu, Al and a metal from the group Mg, Zn, Ti, Zr, Sn, Ni, 0, or a mixture of these elements.
  • This catalyst is produced by means of a precipitation reaction.
  • EP 0 522 669 describes a process for producing a catalyst by co-precipitation of the components two aqueous solutions in which an alkaline third solution serves as the precipitation medium.
  • EP 0 790 074 AI describes the use of sulfate salts and aluminum hydroxide as starting materials for the precipitation reaction.
  • the powder mixtures produced by this precipitation reaction and tempering are generally shaped by extrusion using oxidic binder phases, such as pseudoboehmite or alpha-hydroxyböhmite.
  • the invention relates to a shaped catalyst consisting of Cu and at least one of the components listed: Al, Si, Ti, Zr, Cr, Zn, Fe, Mn, Ni, Co, V, W, Mo, Ru, Ag, Re, Alkali, alkaline earth elements, lanthanum and lanthanides, which can be present in whole or in part in oxidic form, with the proviso that this catalyst is produced by mixing the constituents and build-up granulation, if appropriate with organic additives, whereby further shaping processes, such as extrusion or tableting, are possible are.
  • Catalyst production is possible in devices with the appropriate mixing and agglomerating or granulating properties, these include, for example, intensive mixers, cone mixers with a rotating screw, granulating plates, granulating drums, Fluid bed granulator, granulation using an avalanche effect, granulating plate.
  • the elements can be used as salts, such as nitrates, sulfates, their oxides, hydroxides, oxalates, carbonates, acetates, citrates or mixtures thereof.
  • the catalyst can have a pore volume between 0.20 and 1.2 ml / g, preferably between 0.20 and 0.90 ml / g.
  • the proportion of pores with a pore diameter of more than 20 n can be greater than 20 ml / g.
  • the pore distribution can be bimodal.
  • the pore volume is determined using the mercury porosimetry method according to DIN 66133.
  • the total metal content of the catalyst can be at least 5% by weight, preferably between 10-60% by weight, in particular between 25-50% by weight.
  • the metals of the catalyst can be in different oxidation states, and individual metals can be in more than one oxidation state.
  • the Cu content can be 1-60% by weight, preferably 15-40% by weight.
  • the catalyst can have a Cu: Cr ratio of (5-15): (0.05-3), preferably 10: 1.
  • the constituents of the catalyst can also be mixed oxides, for example, but without limitation, spinel structures such as CuCr 2 0 4 , perovskites such as LaMn0 3 or silicates such as NaSi0 3 .
  • the elements AI, Si can be used in oxidic or non-oxide form.
  • Examples of the oxidic form are: precipitated silica, pyrogenic SiO 2, fibrous SiO 2 .
  • the Si0 2 can be used in amorphous, crystalline or partially crystalline form.
  • AI can be used as a pure oxide, pseudoboehmite, boehmite (alpha-aluminum oxide monohydrate), aluminum hydroxide such as bayerite or gibbsite.
  • mixed systems made of AI and Si can be used, such as in the form of
  • Aluminum silicates or natural clays are included. These include, for example, montmorrillonite, kaolin, sepiolite and the like. a. as well as mixtures thereof. It is also possible to use natural or synthetic zeolites and pyrogenic mixed oxides.
  • the catalyst can be prepared without a precipitation reaction of an aqueous solution and without a filtration step.
  • the drying of the catalyst can be carried out at 100-200 ° C., preferably at 105-130 ° C. in air or an inert gas such as nitrogen or argon or a mixture of these gases.
  • the calcination can be carried out at 300-800 ° C., preferably at 450-700 ° C., in air or an inert gas such as nitrogen or argon or under steam or a mixture of these gases.
  • the specific surface area of the catalyst can be between 15-200 m 2 / g.
  • the advantages of the catalyst according to the invention result from the significantly lower production costs, because instead of the many time-intensive individual steps such as precipitation, filtration, mixing, compacting and extrusion, only one mixing and shaping step is used.
  • X-ray diffraction analyzes depending on the constituents of the catalyst and the oxidation states of the constituents, different crystal structures, such as spinel phases, oxidic copper can be identified.
  • Mn in addition to Cr Cu-Mn mixed oxides can be found.
  • Ba in addition to Cr BaCr0 4 can also be found, for example.
  • the catalyst may be activated by liquid or gas phase reduction.
  • the reduction can take place in the actual process reactor or in special reduction vessels.
  • the metallic phases can be stabilized by partial oxidation, so that the catalyst can be handled in air without any problems.
  • the metallic phases can be stabilized by an inert solvent, such as paraffin, waxes or high-boiling aromatic-free gasoline, so that the catalyst can be handled in air without problems as long as it remains covered with the inert phase.
  • an inert solvent such as paraffin, waxes or high-boiling aromatic-free gasoline
  • the starting material or starting material mixture to be reacted can be the reducing agent itself.
  • the partial oxide layer Before starting a hydrogenation process or hydrogenolysis, the partial oxide layer can be removed by treatment with hydrogen.
  • the catalyst according to the invention is suitable for the hydrogenation of carbonyl compounds, such as aldehydes and ketones to the corresponding alcohols.
  • carbonyl compounds such as aldehydes and ketones to the corresponding alcohols.
  • the carbonyl compounds can have further functional groups such as hydroxyl or amino groups.
  • Unsaturated carbonyl compounds are generally added the corresponding saturated
  • Aromatic carbonyl compounds can hydrogenate the aromatic nucleus.
  • the catalyst according to the invention can be used for the hydrogenation of aldehydes, hydroxyaldehydes, ketones, acids, esters, anhydrides, lactones, sugars and aromatic nitro compounds.
  • aldeydes formaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde, 2,2-dimethylpropionaldehyde,
  • Preferred aldehydes are branched and unbranched saturated and / or unsaturated C 2 -C 40 aldehydes, which are synthesized, for example, in a hydrofromylation reaction. These include, for example, 2-methylpentenal, 2-ethylhexenal, isomers of nonanal, 2,4-diethyloctenal, 2,4-dimethylheptenal or isomers of tridecanal.
  • Typical hydroxy aldehydes are products of an aldol reaction of aldehydes or ketones with themselves or with formaldehyde. Examples of this without being restrictive are 3-hydroxypropanal, dimethyolethanal, trimethyloethanal, 3-hydroxybutanal, 3-hydroxy-2-ethylhexanal, 3-hydroxy-2-methylbutanal, 3-hydroxypentanal, 2-methylobutanal, hydroxypivalinaldehyde.
  • the ketones include C 2 -C 4 o-ketones such as, for example, acetone, butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, cyclohexanone, isophorone, methylisobutyl ketone, mesityl oxide, acetophenone, propiophenone, benzophenone, benzallactone, Dibenzallactone, benzalacetophenone, 2,3-butanedione, 2, 4-pentanedione, 2, 5-hexanedione and
  • Methyl vinyl ketone oligomers or polymers such as acetophenone resin or polyketone are also possible.
  • the carboxylic acids and their derivatives include compounds with 1-40 C atoms, such as formic acid,
  • Cyclohexanoic acid benzoic acid, phenylacetic acid, o-toluic acid, m-toluic acid, p-toluic acid, o-chlorobenzoic acid, p-chlorobenzoic acid, p-nitrobenzoic acid, salicylic acid, p-hydroxybenzoic acid, anthranilic acid, p-aminobenzoic acid, oxalic acid, malonic acid, malonic acid, malonic acid Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isphthalic acid, terephthalic acid.
  • Carboxylic acid halides are understood to mean chlorides or bromides of the abovementioned compounds.
  • carboxylic acid esters which can be counted are, for example, C 1 -C 8 -alkyl esters of the abovementioned carboxylic acids, such as methyl formate, ethyl acetate, butyric acid butyl ester, dimethyl terephthalate, Dimethyl adipate, dimethyl maleate, acrylic acid ester, methacrylic acid ester, butyrlactone, caprolactone and polycarboxylic acid esters, such as, for example, polyacrylic and polymethycrylic acid esters and their copolymers and polyesters, such as, for example, polymethacrylate,
  • the esters also include fatty acid esters, for example fatty acid methyl esters and fatty acid wax esters.
  • Carboxylic anhydrides are, for example, anhydrides of the above-mentioned carboxylic acids, in particular acetic anhydride, propynic anhydride, bezoic anhydride and maleic anhydride.
  • Carboxamides are, for example, formamide, acetamide, propionic acid amide, terephthalic acid amide.
  • the preferred hydroxycarboxylic acids are lactic acid,
  • the catalyst according to the invention can be used as the dehydrogenation catalyst for the dehydrogenation of saturated and unsaturated primary, secondary, tertiary alcohols and aromatic alcohols, such as, for example, 1-propanol, iso-propanol, 1-butanol, 2-butanol, iso-butanol, isomers of hexanol and cyclo-hexanol, isomers of dodecanol and cyclo-dodecanol.
  • saturated and unsaturated primary, secondary, tertiary alcohols and aromatic alcohols such as, for example, 1-propanol, iso-propanol, 1-butanol, 2-butanol, iso-butanol, isomers of hexanol and cyclo-hexanol, isomers of dodecanol and cyclo-dodecanol.
  • the catalyst according to the invention can also be used for the hydrogenation of aromatic nitro compounds.
  • aromatic nitro compounds include, for example, nitrobenzene and alkylated aromatic nitro compounds, which can also contain hydroxyl groups.
  • the production of methanol from carbon monoxide and hydrogen with the catalyst according to the invention can be used in the low pressure process at 100 to 250 bar or in the medium pressure process at 40 to 100 bar and generally at temperatures of 200 to 300 ° C.
  • the ratio of the formal-kinetic constants of wax ester formation to wax ester degradation can be greater than 2.
  • the catalyst can be used in the gas or liquid phase.
  • the production process according to the invention not only leads to the production of Cu-containing catalysts in a more environmentally friendly manner because it is only slightly water-polluting and significantly faster, but improvements in various processes could also be found compared to known production processes and known catalysts.
  • the catalysts according to the invention show improved dehydrogenation activity.
  • the fatty acid methyl ester reaction in addition to good hydrogenolysis behavior, a very good ratio of build-up to breakdown reaction of long-chain wax esters is found, so that shorter residence times can be achieved during the process control.
  • a Cu-containing catalyst of high activity and selectivity can be produced without carrying out a precipitation reaction which is normally characterized by a high wastewater load containing heavy metals.
  • the starting components can be produced by the simultaneous intensive mixing and agglomeration without going through a precipitation reaction.
  • the spherical particles created by the build-up agglomeration can be used directly as a catalyst after drying and calcining.
  • the reduction of the catalyst in a hydrogen stream is necessary as a step for activation.
  • the structural agglomeration carried out in this way represents a possibility for direct shaping of the catalyst.
  • the size of the agglomerates formed can be controlled via the dwell time, rotational speeds of the rotating components and adjustment of the moisture.
  • At least one other of the elements from the group AI, Si, Ti, Zr, Cr, Zn, Fe, Mn, Ni, Co, V, W, Mo, Ru, Ag, Re, alkali metal, alkaline earth metal elements, lanthanum and lanthanides be used to produce the catalyst.
  • the metals of the catalyst can come in different
  • Oxidation levels exist, whereby individual metals can exist in more than one oxidation level.
  • the catalyst can have a total metal content of at least 5% by weight, typically have between 10-60% by weight, preferably between 25-50% by weight.
  • both catalysts with high and low proportions of a second element such as Al, Si, Ti, Zr, Cr, Zn, Fe, Mn, Ni, Co, V, W, Mo, Ru, Re, alkali, alkaline earth elements, Lanthanum and lanthanides can be used.
  • a second element such as Al, Si, Ti, Zr, Cr, Zn, Fe, Mn, Ni, Co, V, W, Mo, Ru, Re, alkali, alkaline earth elements, Lanthanum and lanthanides
  • Cr is present as a further catalyst component, comparatively small amounts can also be used without adversely affecting the activity, selectivity or aging behavior.
  • a catalyst with a low Cr content is used, a Cu: Cr ratio of (5-15): (0.05-3), preferably 10: 1, has a particularly advantageous effect.
  • the oxides, oxide hydroxides, carbonates, basic carbonates, nitrates, sulfates, acetates, citrates or other salts of the particular compound can be used as starting substances.
  • NH 3 can also be used as an aqueous solution or as (NH) 2 CO 3 .
  • Other ammoniacal starting substances, such as (NH) 2 Cr 2 0 7 or Cu (NH 3 ) 4 C0 3 are also suitable.
  • AI and Si can be used in oxidic or non-oxide form.
  • Examples of the oxidic form can be: precipitated silica, pyrogenic Si0 2 , fibrous Si0 2 .
  • the Si0 2 can be used in amorphous, crystalline or partially crystalline form. Silicon oil and silica sol can also be used.
  • AI can be used as a pure oxide, pseudoboehmite, boehmite (alpha-aluminum oxide monohydrate), aluminum hydroxide such as bayerite or gibbsite.
  • mixed systems made of Al and Si such as those contained in the form of aluminosilicates or natural clays, can be used.
  • aluminosilicates or natural clays which includes for example montmorrillonite, kaolin, sepiolite and others as well as mixtures thereof.
  • Elements of the alkali or alkaline earth group can be introduced in the form of their silicates.
  • the addition of water can be used to adjust the moisture required for building agglomeration and pelleting.
  • the amount of water required can be determined by the properties of the starting substances used in each case.
  • the amount of water added can be between 20 and 45 parts by weight.
  • an additional additional shaping can be carried out.
  • these include, for example, extrusion via screw extruders, die presses, "Hutt” shaping or tableting.
  • Organic additives such as waxes, wax emulsions, oils, plasticizers or methyl celluloses, but also polyethylene oxide, polyethylene glycols, can be used for extrusion and tabletting.
  • the use of graphite can be advantageous for tableting.
  • the amount of organic additives to be used can be 0.1-30% by weight, preferably between 1-10% by weight. After shaping, it may be necessary to dry the particles according to the invention for several hours. Drying can be carried out in a temperature range of 100-200 ° C, preferably 105-130 ° C.
  • the final step can be the calcination, which can be carried out at 300-800 ° C., preferably at 450-700 ° C.
  • specific internal surfaces BET
  • the pore volume can be between 0.20 and 1.2 ml / g of catalyst, a pore volume between 0.20 and 0.90 ml / g is preferred.
  • the proportion of pores with a pore diameter of more than 20 n can be greater than 20 ml / g of catalyst.
  • the pore distribution can be monomodal or bimodal. If you carry out X-ray examinations, depending on the type of components and in
  • a partial or complete reduction in the gas or liquid phase may be required to activate the catalyst for dehydrogenation reactions, hydrogenation reactions or hydrogenolysis.
  • solvents such as hydrocarbons such as paraffins, ethers such as dioxane, alcohols and esters can be used.
  • the activating agent can thus be the starting material solution itself.
  • the reduction in the liquid phase using an ester can be carried out according to GB 385625 for a copper-chromium catalyst.
  • the catalyst can be reduced at a temperature between 120-160 ° C by adding hydrogen to an inert gas, usually nitrogen.
  • the amount of hydrogen can usually be 1-5 vol .-%. It must be avoided that the catalyst or the reactor is damaged by the released Exothermic is coming. Hydrogen is therefore initially added in small quantities. After the initial exotherm has subsided, the temperature can be increased to 180-250 ° C and the hydrogen flow and pressure slowly increased.
  • the heat of reduction in the reduction of copper oxide is 86 kJ / mol. Depending on the size of the amount of catalyst in the reactor, it may therefore take from a few hours to a few days for the reduction process to be completed.
  • the catalyst is kept in a stream of hydrogen for a few hours. Only then can the necessary conditions for hydrogenation or hydrogenolysis be set and the actual reaction started.
  • Alcohol dehydrogenation reactions found an increased activity of the catalyst.
  • kWA kinetic constant of wax ester hydrogenolysis to alcohols
  • kWE kinetic constant of wax ester formation
  • granules are produced with the addition of 20 g of organic shaping aids, which, however, are processed in a single-screw extruder into extrudates with a diameter of 4 mm before drying.
  • the extrudates are dried and calcined as under 1.
  • Components start to form granules after a short time.
  • the granules are processed into extrudates and heat treated as described in Example K2.
  • Catalyst example (K6) 450 g of precipitated silica, 50 g of pyrogenic silica, 160 g of Cu hydroxide carbonate (55% by weight of Cu), 530 g of Cu tetramine carbonate solution (14% by weight of Cu), 62 g are placed in an Eirich mixer Ba acetate, 30 g Cr0 3 , deionized water mixed for about 30 minutes, the components starting to form granules after a short time. The granules are heat-treated as described in Example K2.
  • a commercially available catalyst with a Cu content of 33% by weight is selected, which is produced without direct granulation according to the invention.
  • a commercially available catalyst with a Cu content of 22% by weight is selected as the comparative catalyst, which is produced without direct granulation according to the invention.
  • Experimental example VB1 hydrogenolysis of fatty acid methyl ester
  • the tests are carried out batchwise in a stirred tank autoclave.
  • the catalyst lying in a basket is first activated with hydrogen.
  • the test temperature is 200 ° C and the hydrogen pressure is 285 bar.
  • the analysis is carried out using gas chromatography.
  • the total amount of ester is analyzed at the end of the reaction time, and the saponification number (VZ) in mg (KOH) / g of starting material is also determined.
  • VZ saponification number
  • the ratio of the kinetic constants is determined according to formula (I).
  • the experiments are carried out batchwise in a stirred tank reactor.
  • the catalyst is housed in a basket.
  • the educt (2700 g) is in the Brought reactor and the temperature increased to 230 ° C.
  • the stirrer speed is set at 800 rpm and a zero point is set by taking a sample.
  • the course of the reaction is monitored via the released hydrogen and with the aid of gas chromatography.

Abstract

The invention relates to a shaped catalyst, consisting of Cu and at least one of the components: Al, Si, Ti, Zr, Cr, Zn, Fe, Mn, Ni, Co, V, W, Mo, Ru, Ag, Re, alkali elements, alkaline earth elements, lanthane and lanthanides that are completely or partially present in oxidic form, with the proviso that said catalyst is produced by mixing the components and granulation. Other shaping methods such as extrusion or pelleting may also be used. The elements may be used in the form of their salts such as nitrates, sulfates, their oxides, hydroxides, oxalates, carbonates, acetates, citrates or mixtures thereof. The catalyst can be used for hydrogenation or dehydrogenation.

Description

GEFORMTER KUPFER- UND CHROMHALTIGER KATALYSATOR FÜR HYDRIER- UND D EHYDRI ERREAKT I ONEN MOLDED COPPER AND CHROME-CONTAINING CATALYST FOR HYDRATING AND D EHYDRI REREACT I ONES
Die Erfindung betrifft einen geformten Kupfer-Katalysator, ein Verfahren zu seiner Herstellung sowie seine Verwendung.The invention relates to a shaped copper catalyst, a process for its production and its use.
Cu-Katalysatoren und ihre Verwendung in Hydrier- und Dehydrierreaktionen sind bekannt. Als zweiter wichtiger Bestandteil wird häufig Cr oder Zn genannt, wobei sich Cr in der Regel als Komponente mit hohem Masseanteil auszeichnet. Diese Cu-haltigen Systeme werden industriell in verschiedenartigen Reaktionen eingesetzt. Hierzu zählen beispielsweise die Hydrierung von Aldehyden bei der Herstellung von Oxoalkoholen, die. Hydrogenolyse von Fettsäuremethylestern, die Hydrierung von Fettsäuren zu Fettalkoholen, die reduktive Aminierung und die Dehydrierung von Alkoholen zu Aldehyden oder Ketonen. Weiterhin ist die Synthese von Methanol aus Synthesegas mit Cu-haltigen Katalysatoren bekannt.Cu catalysts and their use in hydrogenation and dehydrogenation reactions are known. Cr or Zn is frequently mentioned as a second important component, Cr generally being a component with a high mass fraction. These Cu-containing systems are used industrially in various reactions. These include, for example, the hydrogenation of aldehydes in the production of oxo alcohols . Hydrogenolysis of fatty acid methyl esters, the hydrogenation of fatty acids to fatty alcohols, the reductive amination and the dehydrogenation of alcohols to aldehydes or ketones. The synthesis of methanol from synthesis gas with Cu-containing catalysts is also known.
Es ist bekannt die Hauptkomponenten des Katalysators durch Fällungsreaktion aus wässrigen Lösungen ihrer Salze zu gewinnen. So wird gemäß US 5,243,095 die Aktivkomponente des Katalysators durch Fällung des Nitratsalzes erhalten.It is known to obtain the main components of the catalyst by precipitation reaction from aqueous solutions of their salts. According to US Pat. No. 5,243,095, the active component of the catalyst is obtained by precipitation of the nitrate salt.
Gemäß DE 40 28 295 wird aus einer wässrigen Lösung von Cu(II)- und Mn (II) -Salzen durch Zugabe von Alkalien Niederschlag gefällt, der abfiltriert und zur Katalysatorherstellung thermisch behandelt wird.According to DE 40 28 295, precipitation is precipitated from an aqueous solution of Cu (II) and Mn (II) salts by adding alkalis, which is filtered off and thermally treated to produce the catalyst.
US Patent 5,008,235 beschreibt einen Prozeß zur Hydrierung eines Eduktes zum entsprechenden Alkohol mit Hilfe eines Katalysators, bestehend aus Cu, AI und einem Metall der Gruppe Mg, Zn, Ti, Zr, Sn, Ni, 0, beziehungsweise einer Mischung dieser Elemente. Dieser Katalysators wird mittels Fällungsreaktion hergestellt.US Patent 5,008,235 describes a process for hydrogenating a starting material to the corresponding alcohol with the aid of a catalyst consisting of Cu, Al and a metal from the group Mg, Zn, Ti, Zr, Sn, Ni, 0, or a mixture of these elements. This catalyst is produced by means of a precipitation reaction.
EP 0 522 669 beschreibt ein Verfahren zur Herstellung eines Katalysators durch gemeinsame Fällung der Komponenten aus zwei wässrigen Lösungen, bei der eine alkalisch gestellte dritte Lösung als Fällungsmedium dient.EP 0 522 669 describes a process for producing a catalyst by co-precipitation of the components two aqueous solutions in which an alkaline third solution serves as the precipitation medium.
EP 0 790 074 AI beschreibt die Verwendung von Sulfatsalzen und Aluminiumhydroxid als Ausgangsmaterialien zur Fällungsreaktion.EP 0 790 074 AI describes the use of sulfate salts and aluminum hydroxide as starting materials for the precipitation reaction.
Die Formgebung der durch diese Fällungsreaktion und Temperung hergestellten Pulvermischungen erfolgt in der Regel durch Extrusion mittels oxidischer Binderphasen, wie Pseudoböhmit oder alpha-Hydroxyböhmit .The powder mixtures produced by this precipitation reaction and tempering are generally shaped by extrusion using oxidic binder phases, such as pseudoboehmite or alpha-hydroxyböhmite.
Es ist bekannt, direkt oxidische Materialien einzusetzen, die nach Homogenisierung zu pastenartigen Substanzen verarbeitet, extrudiert und abschließend getrocknet und calciniert werden. So beschreibt beispielsweise WO US 6,049,008 eine derartige Herstellroute unter Verwendung von Kupferoxid, Calciumsilikat, Tonerde und Wasser. Teilweise sollen organische Zusätze den Extrusionvorgang erleichtern.It is known to directly use oxidic materials which, after homogenization, are processed into paste-like substances, extruded and finally dried and calcined. For example, WO US 6,049,008 describes such a production route using copper oxide, calcium silicate, alumina and water. In some cases, organic additives should make the extrusion process easier.
Gegenstand der Erfindung ist ein geformter Katalysator, bestehend aus Cu und mindestens einem der aufgeführten Komponenten: AI, Si, Ti, Zr, Cr, Zn, Fe, Mn, Ni, Co, V, W, Mo, Ru, Ag, Re, Alkali-, Erdalkalielemente, Lanthan und Lanthaniden, die ganz oder eilweise in oxidischer Form vorliegen können mit der Maßgabe, daß dieser Katalysator durch Mischung der Bestandteile und Aufbaugranulation gegebenenfalls mit organischen Zusätzen hergestellt wird, wobei weitere Formgebungsverfahren, wie zum Beispiel Extrusion oder Tablettierung, möglich sind.The invention relates to a shaped catalyst consisting of Cu and at least one of the components listed: Al, Si, Ti, Zr, Cr, Zn, Fe, Mn, Ni, Co, V, W, Mo, Ru, Ag, Re, Alkali, alkaline earth elements, lanthanum and lanthanides, which can be present in whole or in part in oxidic form, with the proviso that this catalyst is produced by mixing the constituents and build-up granulation, if appropriate with organic additives, whereby further shaping processes, such as extrusion or tableting, are possible are.
Die Herstellung der erfindungsgemäßenThe preparation of the invention
Katalysatorherstellung ist in Geräten mit entsprechenden Misch- und Agglomerier- beziehungsweise Granuliereigenschaften möglich, dazu zählen beispielsweise Intensivmischer, Konusmischer mit UmlaufSchnecke, Granulierteller, Granuliertrommel, Wirbelschichtgranulierer, Granulation unter Ausnutzung eines Lawinene fekts, Granulierteller.Catalyst production is possible in devices with the appropriate mixing and agglomerating or granulating properties, these include, for example, intensive mixers, cone mixers with a rotating screw, granulating plates, granulating drums, Fluid bed granulator, granulation using an avalanche effect, granulating plate.
Weitere Formgebungsverfahren wie zum Beispiel Extrusion oder Tablettierung sind möglich.Other shaping processes such as extrusion or tableting are possible.
Die Elemente können als Salze, wie Nitraten, Sulfaten ihren Oxiden, Hydroxiden, Oxalaten, Carbonaten, Acetaten, Citraten oder Mischungen hieraus, eingesetzt werden.The elements can be used as salts, such as nitrates, sulfates, their oxides, hydroxides, oxalates, carbonates, acetates, citrates or mixtures thereof.
Der Katalysator kann ein Porenvolumen zwischen 0,20 und 1,2 ml/g, bevorzugt zwischen 0,20 und 0,90 ml/g aufweisen.The catalyst can have a pore volume between 0.20 and 1.2 ml / g, preferably between 0.20 and 0.90 ml / g.
Der Anteil an Poren mit einem Porendurchmesser über 20 n kann größer als 20 ml/g betragen.The proportion of pores with a pore diameter of more than 20 n can be greater than 20 ml / g.
Die Porenverteilung kann bimodal sein kann. Das Porenvolumen wird mittels der Methode der Quecksilberporosimetrie nach DIN 66133 ermittelt.The pore distribution can be bimodal. The pore volume is determined using the mercury porosimetry method according to DIN 66133.
Der Gesamtmetallgehalt des Katalysators kann mindestens 5 Gew.-%, bevorzugt zwischen 10 - 60 Gew.-%, insbesondere zwischen 25 - 50 Gew.-% betragen.The total metal content of the catalyst can be at least 5% by weight, preferably between 10-60% by weight, in particular between 25-50% by weight.
Die Metalle des Katalysators können in unterschiedlichen Oxidationsstufen vorliegen, wobei einzelne Metalle in mehr als einer Oxidationsstufe vorliegen können.The metals of the catalyst can be in different oxidation states, and individual metals can be in more than one oxidation state.
Der Cu-Gehalt kann von 1 - 60 Gew.-%, bevorzugt 15 - 40 Gew.-% betragen.The Cu content can be 1-60% by weight, preferably 15-40% by weight.
Bei der bei der Verwendung von Cr kann der Katalysator ein Cu:Cr Verhältnis von (5 - 15) : (0,05 - 3), bevorzugt 10 : 1 aufweisen.When using Cr, the catalyst can have a Cu: Cr ratio of (5-15): (0.05-3), preferably 10: 1.
Die Bestandteile des Katalysators können auch Mischoxide sein, so zum Beispiel, jedoch ohne einzuschränken, Spinellstrukturen, wie CuCr204, Perowskite wie LaMn03 oder Silikate wie NaSi03. Die Elemente AI, Si können in oxidischer oder nicht oxidscher Form verwendet werden können.The constituents of the catalyst can also be mixed oxides, for example, but without limitation, spinel structures such as CuCr 2 0 4 , perovskites such as LaMn0 3 or silicates such as NaSi0 3 . The elements AI, Si can be used in oxidic or non-oxide form.
Als Beispiele der oxidischen Form können sein, ohne damit einzuschränken: Fällungskieselsäure, pyrogenes Si0, faseriges Si02. Das Si02 kann in amorpher, kristalliner oder teilweise kristalliner Form eingesetzt werden. AI kann als reines Oxid, Pseudoböhmit, Böhmit (alpha-Aluminiumoxid- Monohydrat) , Aluminiumhydroxid wie Bayerit oder Gibbsit eingesetzt werden. Daneben sind Mischsysteme aus AI und Si einsetzbar wie sie beispielsweise in Form vonExamples of the oxidic form, without being restricted thereby, are: precipitated silica, pyrogenic SiO 2, fibrous SiO 2 . The Si0 2 can be used in amorphous, crystalline or partially crystalline form. AI can be used as a pure oxide, pseudoboehmite, boehmite (alpha-aluminum oxide monohydrate), aluminum hydroxide such as bayerite or gibbsite. In addition, mixed systems made of AI and Si can be used, such as in the form of
Alumosilikaten oder natürlichen Tonerden enthalten sind. Hierzu zählen beispielsweise Montmorrillonit, Kaolin, Sepiolit u. a. sowie Mischungen hieraus. Weiterhin ist der Einsatz von natürlichen oder synthetischen Zeoliten und pyrogenen Mischoxiden möglich.Aluminum silicates or natural clays are included. These include, for example, montmorrillonite, kaolin, sepiolite and the like. a. as well as mixtures thereof. It is also possible to use natural or synthetic zeolites and pyrogenic mixed oxides.
Die Herstellung des Katalysators kann ohne Fällungsreaktion einer wäßrigen Lösung und ohne Filtrationsschritt durchgeführt werden.The catalyst can be prepared without a precipitation reaction of an aqueous solution and without a filtration step.
Die Trocknung des Katalysators kann bei 100 - 200 °C, bevorzugt bei 105 - 130 °C an Luft oder einem Inertgas wie Stickstoff oder Argon oder einem Gemisch dieser Gase durchgeführt werden.The drying of the catalyst can be carried out at 100-200 ° C., preferably at 105-130 ° C. in air or an inert gas such as nitrogen or argon or a mixture of these gases.
Die Kalzinierung kann bei 300 - 800 °C, bevorzugt bei 450 - 700 °C, an Luft oder einem Inertgas wie Stickstoff oder Argon oder unter Wasserdampf oder einem Gemisch dieser Gase durchgeführt werden.The calcination can be carried out at 300-800 ° C., preferably at 450-700 ° C., in air or an inert gas such as nitrogen or argon or under steam or a mixture of these gases.
Die spezifische Oberfläche des Katalysators (BET) kann zwischen 15 - 200 m2/g liegen.The specific surface area of the catalyst (BET) can be between 15-200 m 2 / g.
Die Vorteile des erfindungsgemäßen Katalysators ergeben sich aus den deutlich günstigeren Herstellkosten, weil anstelle der vielen Zeitintensiven Einzelschritte wie Fällung, Filwation, Mischen, Kompaktieren und Extrusion lediglich ein Misch- und Formgebungsschritt angewandt wird. Bei Röntgenbeugungsanalysen können je nach den Bestandteilen des Katalysators und den Oxidationsstufen der Bestandteile verschiedene Kristallstrukturen, wie Spinellphasen, oxidisches Kupfer erkennbar sein. Bei der Verwendung von Mn neben Cr können Cu-Mn-Mischoxide gefunden werden. Bei der Verwendung von Ba neben Cr kann beispielsweise auch BaCr04 gefunden werden.The advantages of the catalyst according to the invention result from the significantly lower production costs, because instead of the many time-intensive individual steps such as precipitation, filtration, mixing, compacting and extrusion, only one mixing and shaping step is used. In X-ray diffraction analyzes, depending on the constituents of the catalyst and the oxidation states of the constituents, different crystal structures, such as spinel phases, oxidic copper can be identified. When using Mn in addition to Cr, Cu-Mn mixed oxides can be found. When using Ba in addition to Cr, BaCr0 4 can also be found, for example.
Für den Einsatz in Dehydrier- Hydrierprozessen oder Hydrogenolysen kann eine Aktivierung des Katalysators durch Flüssig- oder Gasphasenreduktion vorausgehen. Die Reduktion kann im eigentlichen Prozessreaktor oder in speziellen Reduktionsbehältern erfolgen.For use in dehydrogenation-hydrogenation processes or hydrogenolysis, the catalyst may be activated by liquid or gas phase reduction. The reduction can take place in the actual process reactor or in special reduction vessels.
Nach der Reduktion in der Gasphase kann eine Stabilisierung der metallischen Phasen durch partielle Oxidation erfolgen, sodaß der Katalysator problemlos an Luft gehandhabt werden kann.After the reduction in the gas phase, the metallic phases can be stabilized by partial oxidation, so that the catalyst can be handled in air without any problems.
Nach der Reduktion in der Gasphase kann eine Stabilisierung der metallischen Phasen durch ein inertes Lösemittel, wie Paraffin, Wachse oder hochsiedendes aromatenfreies Benzin, erfolgen, sodaß der Katalysator problemlos an Luft gehandhabt werden kann, solange er mit der Inertphase bedeckt bleibt.After the reduction in the gas phase, the metallic phases can be stabilized by an inert solvent, such as paraffin, waxes or high-boiling aromatic-free gasoline, so that the catalyst can be handled in air without problems as long as it remains covered with the inert phase.
Bei der Verwendung einer Flüssigphase zur Aktivierung kann das umzusetzende Edukt oder Eduktgemisch das Reduktionsmittel selbst sein.When using a liquid phase for activation, the starting material or starting material mixture to be reacted can be the reducing agent itself.
Vor dem Start eines Hydrierprozesses oder einer Hydrogenolyse kann die partielle Oxidschicht durch Behandlung mit Wasserstoff entfernt werden.Before starting a hydrogenation process or hydrogenolysis, the partial oxide layer can be removed by treatment with hydrogen.
Bei der Verwendung eines inertisierenden Mittels kann dieses vom Katalysator freigewaschen werden. AlsIf an inerting agent is used, it can be washed free of the catalyst. As
Waschmittel können verschiedenartige organische Medien, wie Alkohole, Ether, Aldehyde, Ketone oder Kohlenwasserstoffe eingesetzt werden. Der erfindungsgemäße Katalysator eignet sich zur Hydrierung von Carbonylverbindungen, wie zum Beispiel Aldehyden und Ketonen zu den entsprechenden Alkoholen. Der Begriff „Carbonlyverbindungen" umfaßt im Sinne dieser Erfindung alle Verbindungen die eine C=0-Gruppe besitzen, einschließlich Carbonsäuren und deren Derivate wie beispielsweise Carbonsäureamide. Die Carbonylverbindungen können weitere funktioneile Gruppen wie Hydroxy- oder Aminogruppen haben. Ungesättigte Carbonylverbindungen werden in der Regel zu den entsprechenden gesättigtenVarious types of organic media such as alcohols, ethers, aldehydes, ketones or hydrocarbons can be used. The catalyst according to the invention is suitable for the hydrogenation of carbonyl compounds, such as aldehydes and ketones to the corresponding alcohols. For the purposes of this invention, the term “carbonly compounds” encompasses all compounds which have a C = 0 group, including carboxylic acids and their derivatives such as, for example, carboxamides. The carbonyl compounds can have further functional groups such as hydroxyl or amino groups. Unsaturated carbonyl compounds are generally added the corresponding saturated
Alkoholen hydriert. Bei aromatischen Carbonyl erbindung kann es zur Hydrierung des aromatischen Kerns kommen.Alcohols hydrogenated. Aromatic carbonyl compounds can hydrogenate the aromatic nucleus.
Der erfindungsgemäße Katalysator kann zur Hydrierung von Aldehyden, Hydroxyaldehyden, Ketonen, Säuren, Ester, Anhydride, Lactone, Zucker und aromatischen Nitroverbindungen eingesetzt werden.The catalyst according to the invention can be used for the hydrogenation of aldehydes, hydroxyaldehydes, ketones, acids, esters, anhydrides, lactones, sugars and aromatic nitro compounds.
Als Beispiele für Aldeyde können genannt werden: Formaldehyd, Propionaldehyd, n-Butyraldehyd, iso- Butyraldehyd, Valeraldehyd, 2-Methylbutyraldehyd, 3- Methylbutyraldehyd, 2,2 Dimethylpropionaldehyd,The following may be mentioned as examples of aldeydes: formaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde, 2,2-dimethylpropionaldehyde,
Capronaldehyd, 2-Methylvaleraldehyd, 3- Methylvaleraldehyd, 4- Methylvaleraldehyd, 2-Ethylbutyraldehyd, 2-2 Dimethylbutyraldehyd, 3, 3-Dimethylbutyraldehyd, Caprylaldehyd, Caprinaldehyd, Glutardialdehyd.Capronaldehyde, 2-methylvaleraldehyde, 3-methylvaleraldehyde, 4-methylvaleraldehyde, 2-ethylbutyraldehyde, 2-2 dimethylbutyraldehyde, 3, 3-dimethylbutyraldehyde, caprylaldehyde, caprinaldehyde, glutardialdehyde.
Bevorzugte Aldehyde sind verzweigte und unverzweigte gesättigte und/oder ungesättigte C2-C40-Aldehyde, die beispielsweise in einer Hydrofromylierungsreaktion synthetisiert werden. Dazu zählen beispielsweise, 2- Methylpentenal, 2-Ethylhexenal, Isomere des Nonanals, 2,4- Diethyloctenal, 2,4 Dimethylheptenal oder Isomere des Tridecanals.Preferred aldehydes are branched and unbranched saturated and / or unsaturated C 2 -C 40 aldehydes, which are synthesized, for example, in a hydrofromylation reaction. These include, for example, 2-methylpentenal, 2-ethylhexenal, isomers of nonanal, 2,4-diethyloctenal, 2,4-dimethylheptenal or isomers of tridecanal.
Typische Hydroxyaldehyde sind Produkte einer Aldolreaktion von Aldehyden oder Ketonen mit sich selbst oder auch mit Formaldehyd. Beispiele hierfür, ohne einschränkend zu sein, sind 3-Hydroxypropanal, Diemthyolethanal, Trimethyloethanal, 3-Hydroxybutanal, 3-Hydroxy-2- ethylhexanal, 3-Hydroxy-2-methylbutanal, 3-Hydroxypentanal, 2-Methylobutanal, Hydroxypivalinaldehyd.Typical hydroxy aldehydes are products of an aldol reaction of aldehydes or ketones with themselves or with formaldehyde. Examples of this without being restrictive are 3-hydroxypropanal, dimethyolethanal, trimethyloethanal, 3-hydroxybutanal, 3-hydroxy-2-ethylhexanal, 3-hydroxy-2-methylbutanal, 3-hydroxypentanal, 2-methylobutanal, hydroxypivalinaldehyde.
Zu den Ketonen zählen C2-C4o-Ketone wie beispielsweise Aceton, Butanon, 2-Pentanon, 3-Pentanon, 2-Hexanon, 3- Hexanon, Cyclohexanon, Isophoron, Methylisobutylketon, Mesityloxid, Acetophenon, Propiophenon, Benzophenon, Benzallacton, Dibenzallacton, Benzalacetophenon, 2,3- Butandion, 2, 4-Pentandion, 2, 5-Hexandion undThe ketones include C 2 -C 4 o-ketones such as, for example, acetone, butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, cyclohexanone, isophorone, methylisobutyl ketone, mesityl oxide, acetophenone, propiophenone, benzophenone, benzallactone, Dibenzallactone, benzalacetophenone, 2,3-butanedione, 2, 4-pentanedione, 2, 5-hexanedione and
Methylvinylketon. Darüberhinaus sind auch Oligomere oder Polymere möglich wie beispielsweise Acetophenonharz oder Polyketon.Methyl vinyl ketone. In addition, oligomers or polymers such as acetophenone resin or polyketone are also possible.
Zu den Carbonsäuren und deren Derivate zählen Verbindungen mit 1-40 C-Atomen wie beispielsweise Ameisensäure,The carboxylic acids and their derivatives include compounds with 1-40 C atoms, such as formic acid,
Essigsäure, Propionsäure, Buttersäure, Isobuttersäure, Acrylsäure, Methacrylsäure, n-Valeriansäure, Trimethylessigsäure, Capronsäure, Cyprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, Ölsäure, Eladinsäure, Lonolsäure, Linolensäure,Acetic acid, propionic acid, butyric acid, isobutyric acid, acrylic acid, methacrylic acid, n-valeric acid, trimethylacetic acid, caproic acid, cyprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, eladic acid, lonolic acid, linolenic acid,
Cyclohexansäure, Benzoesäure, Phenylessigsäure, o- Toluylsäure, m-Toluylsäure, p-Toluylsäure, o- Chlorbenzoesäure, p-Chlorbenzoesäure, p-Nitrobenzoesäure, Salicylsäure, p-Hydroxybenzoesäure, Anthranilsäure, p- Aminobenzoesäure, Oxalsäure, Malonsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure, Sebacinsäure, Maleinsäure, Fumarsäure, Phthalsäure, Isphthalsäure, Terephthalsäure.Cyclohexanoic acid, benzoic acid, phenylacetic acid, o-toluic acid, m-toluic acid, p-toluic acid, o-chlorobenzoic acid, p-chlorobenzoic acid, p-nitrobenzoic acid, salicylic acid, p-hydroxybenzoic acid, anthranilic acid, p-aminobenzoic acid, oxalic acid, malonic acid, malonic acid, malonic acid Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isphthalic acid, terephthalic acid.
Unter Carbonsäurhalogenide sind Chloride oder Bromide der oben genannten Verbindungen zu verstehen.Carboxylic acid halides are understood to mean chlorides or bromides of the abovementioned compounds.
Als Beispiele für Carbonsäureester können beispielsweise Cι-Cιo-Alkylester der oben genannten Carbonsäuren gezählt werden wie Methylformiat, Essigester, Buttersäurebutlyester, Terephtahlsäuredimethylester, Adipinsäuredimethylester, Maleinsäuredimethylester, Acrylsäureester, Methacrylsäureester, Butyrlacton, Caprolacton und Polycarbonsäureester, wie zum Beispiel Polyacryl- und Polymethycrylsäureester und deren Copolymere und Polyester, wie zum Beispiel Polymethacrylat,Examples of carboxylic acid esters which can be counted are, for example, C 1 -C 8 -alkyl esters of the abovementioned carboxylic acids, such as methyl formate, ethyl acetate, butyric acid butyl ester, dimethyl terephthalate, Dimethyl adipate, dimethyl maleate, acrylic acid ester, methacrylic acid ester, butyrlactone, caprolactone and polycarboxylic acid esters, such as, for example, polyacrylic and polymethycrylic acid esters and their copolymers and polyesters, such as, for example, polymethacrylate,
Terephthalsäureester und andere technische Kunststoffe. Zu den Estern zählen auch Fettsäureester beispielsweise Fettsäuremethyleseter und Fettsäurewachsester.Terephthalic acid esters and other engineering plastics. The esters also include fatty acid esters, for example fatty acid methyl esters and fatty acid wax esters.
Carbonsäureanhydride sind beispielsweise Anhydride der oben genannten Carbonsäuren, insbesondere Essigsäureanhydrid, Propinsäureanhydrid, Bezoesäureanhydrid und Maleinsäureanhydrid.Carboxylic anhydrides are, for example, anhydrides of the above-mentioned carboxylic acids, in particular acetic anhydride, propynic anhydride, bezoic anhydride and maleic anhydride.
Carbonsäureamide sind beispielsweise Formamid, Acetamid, Propionsäureamid, Terephthalsäureamid.Carboxamides are, for example, formamide, acetamide, propionic acid amide, terephthalic acid amide.
Als bevorzugte Hydroxycarbonsäuren sind Milchsäure,The preferred hydroxycarboxylic acids are lactic acid,
Äpfelsäure, Weinsäure, Zitronensäure oder Aminosäuren zu nennen.Malic acid, tartaric acid, citric acid or amino acids.
Als Dehydrierungskatalysator kann der erfindungsgemäße Katalysator zur Dehydrierung von gesättigten und ungesättigten primären, sekundären, tertiären Alkoholen sowie aromatischen Alkoholen eingesetzt werden, wie beispielsweise 1-Propanol, iso-Propanol, 1-Butanol, 2- Butanol, iso-Butanol, Isomere des Hexanols und cyclo- Hexanols, Isomere des Dodekanols und cyclo-Dodekanols.The catalyst according to the invention can be used as the dehydrogenation catalyst for the dehydrogenation of saturated and unsaturated primary, secondary, tertiary alcohols and aromatic alcohols, such as, for example, 1-propanol, iso-propanol, 1-butanol, 2-butanol, iso-butanol, isomers of hexanol and cyclo-hexanol, isomers of dodecanol and cyclo-dodecanol.
Der erfindungsgemäße Katalysator kann auch zur Hydrierung von aromatischen Nitroverbindungen eingesetzt werden. Hierzu zählen beispielsweise Nitrobenzol und alkylierte aromatische Nitroverbindungen, die auch Hydroxygruppen enthalten können.The catalyst according to the invention can also be used for the hydrogenation of aromatic nitro compounds. These include, for example, nitrobenzene and alkylated aromatic nitro compounds, which can also contain hydroxyl groups.
Weiterhin ist ein Einsatz des erfindungsgemäßenAnother use of the invention
Katalysators zur Herstellung von Methanol aus Kohlenmonoxid und Wasserstoff möglich. ω r > I-1 o Cπ o Cπ O cπ trCatalyst for the production of methanol from carbon monoxide and hydrogen possible. ω r> I- 1 o Cπ o Cπ O cπ tr
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Die Herstellung von Methanol aus Kohlenmonoxid und Wasserstoff mit dem erfindungsgemäßen Katalysator kann im Niederdruckverfahren bei 100 bis 250 bar oder im Mitteldruckverfahren bei 40 bis 100 bar und allgemein bei Temperaturen von 200 bis 300 °C eingesetzt werden.The production of methanol from carbon monoxide and hydrogen with the catalyst according to the invention can be used in the low pressure process at 100 to 250 bar or in the medium pressure process at 40 to 100 bar and generally at temperatures of 200 to 300 ° C.
Bei der Hydrogenolyse von Fettsäuremethylestern kann das Verhältnis der formalkinetischen Konstanten von Wachesterbildung zu Wachsesterabbau größer als 2 sein.In the hydrogenolysis of fatty acid methyl esters, the ratio of the formal-kinetic constants of wax ester formation to wax ester degradation can be greater than 2.
Der Katalysator kann in der Gas- oder Flüssigphase eingesetzt werden.The catalyst can be used in the gas or liquid phase.
Bei der erfindungsgemäßen Katalysatorherstellung wurde überraschenderweise gefunden, daß das erfindungsgemäße Herstellverfahren nicht nur umweltfreundlicher, weil nur geringfügig wasserbelastend und deutlich schneller zur Herstellung von Cu-haltigen Katalysatoren führt, sondern auch gegenüber bekannten Herstellungsverfahren und bekannten Katalysatoren Verbesserungen bei verschiedenen Prozessen festgestellt werden konnte.In the catalyst production according to the invention, it was surprisingly found that the production process according to the invention not only leads to the production of Cu-containing catalysts in a more environmentally friendly manner because it is only slightly water-polluting and significantly faster, but improvements in various processes could also be found compared to known production processes and known catalysts.
So ist beispielsweise im Falle der Alkoholdehydrierungsreaktionen neben einer. gutenFor example, in the case of alcohol dehydrogenation reactions, one is . good
Selektivität vor allem eine sehr hohe Aktivität des Katalysators gewünscht.Selectivity above all a very high activity of the catalyst is desired.
Bei der Hydrogenolyse von Fettsäuremethylestern ist neben der Aktivität eine geringe Bildung von intermediären Zwischenprodukten (Wachsestern) beziehungsweise deren rasche Hydrogenolyse zu den Alkoholen von Bedeutung.In the hydrogenolysis of fatty acid methyl esters, in addition to the activity, low formation of intermediate intermediates (wax esters) or their rapid hydrogenolysis to the alcohols is important.
Die erfindungsgemäßen Katalysatoren zeigen im ersten Fall eine verbesserte Dehydrieraktivität. Im Fall der Fettsäuremethylesterreaktion wird neben einem guten Hydrogenolyseverhalten vor allem ein sehr gutes Verhältnis von Aufbau- zu Abbaureaktion von langkettigen Wachsestern gefunden, sodaß kürzere Verweilzeiten während der Prozessführung erreicht werden können. Überraschenderweise wird gefunden, daß ein Cu-haltiger Katalysator von hoher Aktivität und Selektivität hergestellt werden kann, ohne eine Fällungsreaktion durchzuführen, die normalerweise durch eine hohe schwermetallhaltige Abwasserfracht gekennzeichnet ist. Gemäß Erfindung können die Ausgangskomponenten durch die gleichzeitige intensive Mischung und Agglomeration hergestellt werden, ohne über eine Fällungsreaktion zu gehen. Die dabei durch die Aufbauagglomeration entstehenden sphärischen Partikel können nach Trocknung und Calcinierung direkt als Katalysators eingesetzt werden.In the first case, the catalysts according to the invention show improved dehydrogenation activity. In the case of the fatty acid methyl ester reaction, in addition to good hydrogenolysis behavior, a very good ratio of build-up to breakdown reaction of long-chain wax esters is found, so that shorter residence times can be achieved during the process control. Surprisingly, it is found that a Cu-containing catalyst of high activity and selectivity can be produced without carrying out a precipitation reaction which is normally characterized by a high wastewater load containing heavy metals. According to the invention, the starting components can be produced by the simultaneous intensive mixing and agglomeration without going through a precipitation reaction. The spherical particles created by the build-up agglomeration can be used directly as a catalyst after drying and calcining.
Für Hydrierreaktionen oder Hydrogenolysen ist die Reduktion des Katalysators in einem Wasserstoffström als Schritt zur Aktivierung nötig. Die hierbei durchgeführte Aufbauagglomeration stellt somit neben der Homogenisierung der Einzelkomponenten eine Möglichkeit zur direkten Formgebung des Katalysators dar. Die Größe der dabei entstehenden Agglomerate kann über die Verweilzeit, Umdrehungsgeschwindigkeiten der umlaufenden Bauteile und Einstellung der Feuchte gesteuert werden.For hydrogenation reactions or hydrogenolysis, the reduction of the catalyst in a hydrogen stream is necessary as a step for activation. In addition to homogenizing the individual components, the structural agglomeration carried out in this way represents a possibility for direct shaping of the catalyst. The size of the agglomerates formed can be controlled via the dwell time, rotational speeds of the rotating components and adjustment of the moisture.
Für dieses Herstellverfahren können alle geeigneten Mischersysteme, die eine gleichzeitige Pelletierung oder Aufbaugranulation beziehungsweise Agglomeration der Eduktsubstanzen ermöglichen eingesetzt werden.All suitable mixer systems which enable simultaneous pelleting or build-up granulation or agglomeration of the starting substances can be used for this production process.
Neben Cu kann mindestens ein weiteres der Elemente der Gruppe AI, Si, Ti, Zr, Cr, Zn, Fe, Mn, Ni, Co, V, W, Mo, Ru, Ag, Re, Alkali-, Erdalkalielemente, Lanthan und Lanthaniden zur Herstellung des Katalysators eingesetzt werden.In addition to Cu, at least one other of the elements from the group AI, Si, Ti, Zr, Cr, Zn, Fe, Mn, Ni, Co, V, W, Mo, Ru, Ag, Re, alkali metal, alkaline earth metal elements, lanthanum and lanthanides be used to produce the catalyst.
Die Metalle des Katalysators können in unterschiedlichenThe metals of the catalyst can come in different
Oxidationsstufen vorliegen, wobei einzelne Metalle in mehr als einer Oxidationsstufe vorliegen kann. Der Katalysator kann einen Gesamtmetallgehalt von mindestens 5 Gew.-%, typischer Weise zwischen 10 - 60 Gew.-%, bevorzugt zwischen 25 - 50 Gew.-% aufweisen.Oxidation levels exist, whereby individual metals can exist in more than one oxidation level. The catalyst can have a total metal content of at least 5% by weight, typically have between 10-60% by weight, preferably between 25-50% by weight.
Gemäß Erfindung können sowohl Katalysatoren mit hohen als auch niedrigen Anteilen eines Zweitelementes, wie AI, Si, Ti, Zr, Cr, Zn, Fe, Mn, Ni, Co, V, W, Mo, Ru, Re, Alkali-, Erdalkalielemente, Lanthan und Lanthaniden verwendet werden. Liegt beispielsweise Cr als weiterer Katalysatorbestandteil vor, so können auch vergleichsweise geringe Mengen eingesetzt werden, ohne die Aktivität, Selektivität oder das Alterungsverhalten negativ zu beeinflussen. Wird ein Katalysator mit niedrigem Cr-Gehalt eingesetzt, so wirkt sich ein Cu:Cr Verhältnis von (5 - 15): (0,05 - 3), bevorzugt 10:1, besonders vorteilhaft aus.According to the invention, both catalysts with high and low proportions of a second element, such as Al, Si, Ti, Zr, Cr, Zn, Fe, Mn, Ni, Co, V, W, Mo, Ru, Re, alkali, alkaline earth elements, Lanthanum and lanthanides can be used. For example, if Cr is present as a further catalyst component, comparatively small amounts can also be used without adversely affecting the activity, selectivity or aging behavior. If a catalyst with a low Cr content is used, a Cu: Cr ratio of (5-15): (0.05-3), preferably 10: 1, has a particularly advantageous effect.
Als Ausgangssubstanzen können die Oxide, Oxidhydroxide Carbonate, basische Carbonate, Nitrate, Sulfate, Acetate, Citrate oder andere Salze der jeweiligen Verbindung eingesetzt werden. Ebenfalls kann NH3 als wäßrige Lösung oder als (NH)2C03 verwendet werden. Außerdem sind weitere ammoniakalische Ausgangsubstanzen, wie (NH)2Cr207 oder Cu(NH3)4C03, geeignet.The oxides, oxide hydroxides, carbonates, basic carbonates, nitrates, sulfates, acetates, citrates or other salts of the particular compound can be used as starting substances. NH 3 can also be used as an aqueous solution or as (NH) 2 CO 3 . Other ammoniacal starting substances, such as (NH) 2 Cr 2 0 7 or Cu (NH 3 ) 4 C0 3 , are also suitable.
AI und Si können in oxidischer oder nicht oxidscher Form verwendet werden.AI and Si can be used in oxidic or non-oxide form.
Als Beispiele der oxidischen Form können sein: Fällungkieselsäure, pyrogenes Si02, faseriges Si02. Das Si02 kann in amorpher, kristalliner oder teilweise kristalliner Form eingesetzt werden. Weiterhin kann Silikanöl und Kieselsol eingesetzt werden.Examples of the oxidic form can be: precipitated silica, pyrogenic Si0 2 , fibrous Si0 2 . The Si0 2 can be used in amorphous, crystalline or partially crystalline form. Silicon oil and silica sol can also be used.
AI kann als reines Oxid, Pseudoböhmit, Böhmit (alpha- Aluminiumoxid-Monohydrat) , Aluminiumhydroxid wie Bayerit oder Gibbsit eingesetzt werden.AI can be used as a pure oxide, pseudoboehmite, boehmite (alpha-aluminum oxide monohydrate), aluminum hydroxide such as bayerite or gibbsite.
Daneben sind Mischsysteme aus AI und Si wie sie beispielsweise in Form von Alumosilikaten oder natürlichen Tonerden enthalten sind, einsetzbar. Hierzu zählen beispielsweise Montmorrillonit, Kaolin, Sepiolit u. a. sowie Mischungen hieraus.In addition, mixed systems made of Al and Si, such as those contained in the form of aluminosilicates or natural clays, can be used. Which includes for example montmorrillonite, kaolin, sepiolite and others as well as mixtures thereof.
Weiterhin ist der Einsatz von natürlichen oder synthetischen Zeoliten und pyrogenen Mischoxiden möglich.It is also possible to use natural or synthetic zeolites and pyrogenic mixed oxides.
Elemente der Alkali- oder Erdalkaligruppe können in Form ihrer Silikate eingebracht werden.Elements of the alkali or alkaline earth group can be introduced in the form of their silicates.
Zur Einstellung der zur Aufbauagglomeration und Pelletierung nötigen Feuchte kann durch die Zugabe von Wasser erfolgen. Die nötige Wassermenge kann durch die Eigenschaften der jeweils verwendeten Ausgangssubstanzen bestimmt werden. Die zugegebene Wassermenge kann zwischen 20 und 45 Gewichtsanteilen betragen.The addition of water can be used to adjust the moisture required for building agglomeration and pelleting. The amount of water required can be determined by the properties of the starting substances used in each case. The amount of water added can be between 20 and 45 parts by weight.
Nach dem Pelletierungsschritt kann eine zusätzliche weitere Formgebung durchgeführt werden. Hierzu zählen die beispielsweise die Extrusion über Schneckenextruder, Matrizenpressen, Formgebung nach „Hutt" oder aber die Tablettierung.After the pelleting step, an additional additional shaping can be carried out. These include, for example, extrusion via screw extruders, die presses, "Hutt" shaping or tableting.
Zur Extrusion und Tablettierung können organische Zusätze, wie Wachse, Wachsemulsionen, Öle, Plastifizierer oder Methylcellulosen aber auch Polyethylenoxid, Polyethlenglykole, eingesetzt werden.Organic additives such as waxes, wax emulsions, oils, plasticizers or methyl celluloses, but also polyethylene oxide, polyethylene glycols, can be used for extrusion and tabletting.
Bei der Tablettierung kann die Verwendung von Graphit vorteilhaft sein. Die einzusetzende Menge der organischen Zusätze kann 0,1 - 30 Gew.-%, vorzugsweise zwischen 1 - 10 Gew.-% betragen. Nach der Formgebung kann eine mehrstündige Trocknung der erfindungsgemäßen Partikel nötig sein. Die Trocknung kann in einem Temperaturbereich von 100 - 200 °C, bevorzugt bei 105 - 130 °C durchgeführt werden.The use of graphite can be advantageous for tableting. The amount of organic additives to be used can be 0.1-30% by weight, preferably between 1-10% by weight. After shaping, it may be necessary to dry the particles according to the invention for several hours. Drying can be carried out in a temperature range of 100-200 ° C, preferably 105-130 ° C.
Zum Abschluß der eigentlichen Katalysatorherstellung kann sich als letzter Schritt die Calcinierung anschließen, die bei 300 - 800 °C, bevorzugt bei 450 - 700 °C ausgeführt werden kann. Je nach Art der Ausgangsstoffe und der thermischen Behandlung können spezifische innere Oberflächen (BET) zwischen 15 - 200 m2/g beobachtet werden. Das Porenvolumen kann zwischen 0,20 und 1,2 ml/g Katalysator liegen, bevorzugt wird ein Porenvolumen zwischen 0,20 und 0,90 ml/g. Der Anteil an Poren mit einem Porendurchmesser von mehr als 20 n kann größer sein als 20 ml/g Katalysator. Die Porenverteilung kann monomodal oder bimodal auftreten. Führt man röntgenographische Untersuchungen durch, so lassen sich, je nach Art der Bestandteile sowie inAt the end of the actual catalyst preparation, the final step can be the calcination, which can be carried out at 300-800 ° C., preferably at 450-700 ° C. Depending on the type of raw materials and the thermal treatment, specific internal surfaces (BET) between 15 - 200 m 2 / g can be observed. The pore volume can be between 0.20 and 1.2 ml / g of catalyst, a pore volume between 0.20 and 0.90 ml / g is preferred. The proportion of pores with a pore diameter of more than 20 n can be greater than 20 ml / g of catalyst. The pore distribution can be monomodal or bimodal. If you carry out X-ray examinations, depending on the type of components and in
Abhängigkeit der sich ausbildenden Oxidationsstufen und thermischen Behandlungen, unterschiedliche Strukturen indizieren. So können beispielsweise folgende Phasen beobachtet werden: Kupferoxide, Spinellstrukturen, bei Verwendung von Mn neben Cr können entsprechende Mischoxide gefunden werden. Eine Indizierung von BaCr0 ist bei gleichzeitiger Verwendung von Ba und Cr möglich, ohne hiermit eine Einschränkung zu geben.Depending on the oxidation levels and thermal treatments that develop, different structures are indicated. For example, the following phases can be observed: copper oxides, spinel structures; when Mn is used in addition to Cr, corresponding mixed oxides can be found. BaCr0 can be indexed when Ba and Cr are used at the same time without giving any restrictions.
Zur Aktivierung des Katalysators für Dehydrierreaktionen, Hydrierreaktionen oder Hydrogenolysen kann eine partielle oder vollständige Reduktion in der Gas- oder Flüssigphase erforderlich sein. Bei einer Reduktion in der Flüssigphase kann beispielsweise Lösemittel Kohlenwasserstoffe, wie Paraffine, Ether wie Dioxan, Alkohole und Ester eingesetzt werden. Das Aktivierungsmittel kann somit die Eduktlösung selbst sein. Die Reduktion in der Flüssigphase mittels eines Esters kann gemäß GB 385625 für einen Kupfer-Chrom- Katalysator durchgeführt werden.A partial or complete reduction in the gas or liquid phase may be required to activate the catalyst for dehydrogenation reactions, hydrogenation reactions or hydrogenolysis. In the case of a reduction in the liquid phase, solvents such as hydrocarbons such as paraffins, ethers such as dioxane, alcohols and esters can be used. The activating agent can thus be the starting material solution itself. The reduction in the liquid phase using an ester can be carried out according to GB 385625 for a copper-chromium catalyst.
Bevorzugt wird eine Reduktion in der Gasphase. Hierbei kann der Katalysator bei einer Temperatur zwischen 120 - 160 °C durch Zugabe von Wasserstoff zu einem Inertgas, normalerweise Stickstoff, reduziert werden. Die Wasserstoffmenge kann in der Regel 1 - 5 Vol.-% betragen. Dabei muß vermieden werden, daß es zu einer Schädigung des Katalysators oder des Reaktors durch die freiwerdende Exothermie kommt. Die Zugabe von Wasserstoff erfolgt daher zunächst in geringen Mengen. Nach Abklingen der Anfangsexothermie kann die Temperatur auf 180 - 250°C und der Wasserstoffström sowie der Druck langsam erhöht werden. Die Reduktionswärme bei der Reduktion von Kupferoxid beträgt 86 kJ/mol. Je nach Größe der Katalysatormenge im Reaktor kann es daher von einigen Stunden bis zu einigen Tagen dauern, bis der Reduktionsprozeß abgeschlossen ist.A reduction in the gas phase is preferred. The catalyst can be reduced at a temperature between 120-160 ° C by adding hydrogen to an inert gas, usually nitrogen. The amount of hydrogen can usually be 1-5 vol .-%. It must be avoided that the catalyst or the reactor is damaged by the released Exothermic is coming. Hydrogen is therefore initially added in small quantities. After the initial exotherm has subsided, the temperature can be increased to 180-250 ° C and the hydrogen flow and pressure slowly increased. The heat of reduction in the reduction of copper oxide is 86 kJ / mol. Depending on the size of the amount of catalyst in the reactor, it may therefore take from a few hours to a few days for the reduction process to be completed.
Nach Abklingen der ersten Reduktionswärme wird der Katalysator für einige Stunden im Wasserstoffstrom gehalten. Erst dann können die notwendigen Bedingungen zur Hydrierung oder Hydrogenolysen eingestellt und mit der eigentlichen Reaktion begonnen werden.After the first heat of reduction has subsided, the catalyst is kept in a stream of hydrogen for a few hours. Only then can the necessary conditions for hydrogenation or hydrogenolysis be set and the actual reaction started.
Neben den Vorteilen der erfindungsgemäßen deutlich umweltschonenderen sowie schnelleren und somit kostengünstigen Herstellroute, die zu hochaktiven und selektiven Katalysatoren führt, wird bei der Herstellung des erfindungsgemäßen Katalysators überraschenderweise gefunden, daß das erfindungsgemäße Herstellverfahren gegenüber bekannten Verfahren zur Herstellung von Katalysatoren eine verbesserte Prozessführungen mitsichbringt.In addition to the advantages of the significantly more environmentally friendly and faster and therefore less expensive production route according to the invention, which leads to highly active and selective catalysts, it is surprisingly found in the production of the catalyst according to the invention that the production process according to the invention brings improved process control compared to known processes for the production of catalysts.
So wird beispielsweise im Falle derFor example, in the case of
Alkoholdehydrierungsreaktionen eine gesteigerte Aktivität des Katalysators gefunden.Alcohol dehydrogenation reactions found an increased activity of the catalyst.
Bei Hydrogenolysen von Fettsäuremethylestern wird neben sehr guten Hydriereigenschaften eine geringe Bildung von intermediären Zwischenprodukten (Wachsestern) beziehungsweise deren rasche Hydrogenolyse zu den Alkoholen gefunden, sodaß kürzere Verweilzeiten während derIn hydrogenolysis of fatty acid methyl esters, in addition to very good hydrogenation properties, there is little formation of intermediate intermediates (wax esters) or their rapid hydrogenolysis to the alcohols, so that shorter residence times during the
Prozessführung erreicht werden können. Dieses Verhältnis definiert sich aus der kinetischen Konstante der intermediär gebildeten Wachsester zur kinetischen Konstante der Abbaureaktion gemäß: V = kWA / kWE ( I )Litigation can be achieved. This ratio is defined from the kinetic constant of the intermediate wax esters to the kinetic constant of the degradation reaction according to: V = kWA / kWE (I)
mitWith
kWA= kinetische Konstante der Wachsesterhydrogenolyse zu AlkoholenkWA = kinetic constant of wax ester hydrogenolysis to alcohols
kWE = kinetische Konstante der Wachsesterbildung undkWE = kinetic constant of wax ester formation and
Beispiele:Examples:
Katalysatorbeispiel (Kl) :Catalyst example (Kl):
In einem Eirich-Mischer werden 860 g Böhmit, 800 g Cu- Hydroxidcarbonat (55 Gew.-% Cu) , 120g Ba-Acetat, 100g Cr03, 700g NHHC03, mit 250g entsalztem Wasser ca. 30 Minuten vermischt, wobei die Komponenten nach kurzer Zeit anfangen späherische Granulate zu bilden. Die Granulation wird fortgesetzt bis Partikel von 3 - 5 mm Durchmesser erhalten werden. Die Granulate werden bei 120 °C für 8h getrocknet und bei 650 °C für 10 h calciniert.In an Eirich mixer, 860 g of boehmite, 800 g of copper hydroxide carbonate (55 wt .-% Cu), 120g Ba acetate, 100g Cr0 3, 700g 3 NHHC0 mixed with 250g of deionized water for about 30 minutes, wherein the components after a short time, spherical granules begin to form. The granulation is continued until particles of 3-5 mm in diameter are obtained. The granules are dried at 120 ° C. for 8 hours and calcined at 650 ° C. for 10 hours.
Katalysatorbeispiel (K2) :Catalyst example (K2):
Gemäß Katalysatorbeispiel Kl werden Granulate mit dem Zusatz von 20 g organischen Formgebungshilfsmitteln hergestellt, die vor der Trocknung jedoch in einem Einschneckenextruder zu Extrudaten mit 4 mm Durchmesser verarbeitet werden. Die Extrudate werden wie unter 1 getrocknet und calciniert.According to catalyst example C1, granules are produced with the addition of 20 g of organic shaping aids, which, however, are processed in a single-screw extruder into extrudates with a diameter of 4 mm before drying. The extrudates are dried and calcined as under 1.
Katalysatorbeispiel (K3) :Catalyst example (K3):
Gemäß Katalysatorbeispiel K2 werden Extrudate mit 4 mm Durchmesser mit vorhergehender Granulation hergestellt, das Böhmit stammt jedoch von einem anderen Hersteller.According to catalyst example K2, extrudates with a diameter of 4 mm are produced with previous granulation, but the boehmite comes from another manufacturer.
Katalysatorbeispiel (K4) :Catalyst example (K4):
In einem Eirich-Mischer werden 500 g Fällungskieselsäure, 160 g Cu-Hydroxidcarbonat (55 Gew.-% Cu) , 530 g Cu- Tetramincarbonatlösung (14 Gew.-% Cu) , 160g Ba-Acetat, 32g Cr03, mit 400g entsalztem Wasser ca. 30 Minuten vermischt, wobei die Komponenten nach kurzer Zeit anfangen Granulate zu bilden. Die Granulate werden zu Extrudaten weiterverarbeitet und temperaturbehandelt wie unter K2 beschrieben.In an Eirich mixer, 500 g of precipitated silica, 160 g of Cu hydroxide carbonate (55% by weight of Cu), 530 g of Cu tetramine carbonate solution (14% by weight of Cu), 160 g of Ba acetate, 32 g of CrO 3 , are desalted with 400 g Water mixed for approx. 30 minutes, the components begin to form granules after a short time. The granules are processed into extrudates and heat treated as described under K2.
Katalysatorbeispiel (K5) :Catalyst example (K5):
In einem Eirich-Mischer werden 500 g Fällungskieselsäure, 160 g Kupferhydroxidcarbonat (55 Gew.-% Cu) , 530 g Kupfer- Tetramincarbonatlösung (14 Gew.-% Cu) , 62 g Barium-Acetat, 30 g Cr03, 50 g organische Formgebungshilfsmittel mit 300g entsalztem Wasser ca. 30 Minuten vermischt, wobei dieIn an Eirich mixer, 500 g of precipitated silica, 160 g of copper hydroxide carbonate (55% by weight of Cu), 530 g of copper tetramine carbonate solution (14% by weight of Cu), 62 g of barium acetate, 30 g of CrO 3 , 50 g of organic Shaping aid mixed with 300g of demineralized water for about 30 minutes, the
Komponenten nach kurzer Zeit anfangen Granulate zu bilden. Die Granulate werden zu Extrudaten weiterverarbeitet und temperaturbehandelt wie in Beispiel K2 beschrieben.Components start to form granules after a short time. The granules are processed into extrudates and heat treated as described in Example K2.
Katalysatorbeispiel (K6) : In einem Eirich-Mischer werden 450 g Fällungskieselsäure, 50 g pyrogene Kieselsäure, 160 g Cu-Hydroxidcarbonat (55 Gew.-% Cu) , 530 g Cu-Tetramincarbonatlösung (14 Gew.-% Cu) , 62 g Ba-Acetat, 30 g Cr03, entsalztem Wasser ca. 30 Minuten vermischt, wobei die Komponenten nach kurzer Zeit anfangen Granulate zu bilden. Die Granulate werden temperaturbehandelt wie in Beispiel K2 beschrieben.Catalyst example (K6): 450 g of precipitated silica, 50 g of pyrogenic silica, 160 g of Cu hydroxide carbonate (55% by weight of Cu), 530 g of Cu tetramine carbonate solution (14% by weight of Cu), 62 g are placed in an Eirich mixer Ba acetate, 30 g Cr0 3 , deionized water mixed for about 30 minutes, the components starting to form granules after a short time. The granules are heat-treated as described in Example K2.
Katalysatorbeispiel (VK1) :Catalyst example (VK1):
Als Vergleichskatalysator wird ein handelsüblicher Katalysator mit einem Cu-Anteil von 33 Gew.-% ausgewählt, der ohne erfindungsgemäße direkte Aufbaugranulation hergestellt wird.As a comparative catalyst, a commercially available catalyst with a Cu content of 33% by weight is selected, which is produced without direct granulation according to the invention.
Katalysatorbeispiel (VK2) :Catalyst example (VK2):
Als Vergleichskatalysator wird ein handelsüblicher Katalysator mit einem Cu-Anteil von 22 Gew.-% ausgewählt, der ohne erfindungsgemäße direkte Aufbaugranulation hergestellt wird.A commercially available catalyst with a Cu content of 22% by weight is selected as the comparative catalyst, which is produced without direct granulation according to the invention.
Versuchsbeispiel VB1: Hydrogenolyse von Fettsäuremethylester Die Versuche werden diskontinuierlich in einem Rührkesselautoklav durchgeführt. Der in einem Korb liegende Katalysator wird zunächst mit Wasserstoff aktiviert. Die Versuchstemperatur beträgt 200 °C und der Wasserstoffdruck 285 bar. Die Analytik wird mittels Gaschromatographie durchgeführt. Für die Esterhydrieraktivität wird die Gesamtestermenge am Ende der Reaktionszeit analysiert, außerdem wird die Verseifungszahl (VZ) in mg (KOH) /g Edukt bestimmt. Zur Bestimmung des Abbauverhaltens von intermediär gebildeten Wachsestern wird das Verhältnis der kinetischen Konstanten gemäß Formel (I) bestimmt.Experimental example VB1: hydrogenolysis of fatty acid methyl ester The tests are carried out batchwise in a stirred tank autoclave. The catalyst lying in a basket is first activated with hydrogen. The test temperature is 200 ° C and the hydrogen pressure is 285 bar. The analysis is carried out using gas chromatography. For the ester hydrogenation activity, the total amount of ester is analyzed at the end of the reaction time, and the saponification number (VZ) in mg (KOH) / g of starting material is also determined. To determine the degradation behavior of intermediate wax esters, the ratio of the kinetic constants is determined according to formula (I).
Folgende Ergebnisse werden erzielt:The following results are achieved:
Tabelle 1: Ergebnisse zu Versuchsbeispiel 2: Hydrogenolyse von FettsäuremethylesterTable 1: Results of experimental example 2: hydrogenolysis of fatty acid methyl ester
Figure imgf000019_0001
Figure imgf000019_0001
i) V-Wert gemäß Formel (I)i) V value according to formula (I)
2) VZ = Verseifungszahl2) VZ = saponification number
Versuchsbeispiel VB2: Dehydrierung eines sekundären AlkoholsExperimental example VB2: dehydration of a secondary alcohol
Die Versuche werden diskontinuierlich in einem Rührkesselreaktor durchgeführt. Der Katalysator ist in einem Korb untergebracht. Das Edukt (2700 g) wird in den Reaktor gebracht und die Temperatur auf 230 °C erhöht. Die Rührergeschwindigkeit wird auf 800 U/min festgelegt und mit einer Probennahme ein Nullpunkt gesetzt. Der Reaktionsverlauf wird über den freigesetzten Wasserstoff und mit Hilfe der Gaschromatographie verfolgt. The experiments are carried out batchwise in a stirred tank reactor. The catalyst is housed in a basket. The educt (2700 g) is in the Brought reactor and the temperature increased to 230 ° C. The stirrer speed is set at 800 rpm and a zero point is set by taking a sample. The course of the reaction is monitored via the released hydrogen and with the aid of gas chromatography.
Folgende Ergebnisse werden erzielt:The following results are achieved:
Tabelle 2: Ergebnisse zu Versuchsbeispiel 1 Alkoholdehydrierung in der FlüssigphaseTable 2: Results of experimental example 1 alcohol dehydrogenation in the liquid phase
Figure imgf000021_0001
Figure imgf000021_0001

Claims

Patentansprüche claims
1. Geformter Katalysator, bestehend aus Cu und mindestens einem der aufgeführten Komponenten: AI, Si, Ti, Zr, Cr, Zn, Fe, Mn, Ni, Co, V, W, Mo, Ru, Ag, Re, Alkali-, Erdalkalielemente, Lanthan und Lanthaniden, die ganz oder teilweise in oxidischer Form vorliegen können mit der Maßgabe, daß dieser Katalysator durch Mischung der Bestandteile und Aufbaugranulation gegebenenfalls mit organischen Zusätzen hergestellt wird, wobei weitere Formgebungsverfahren möglich sind.1. Shaped catalyst consisting of Cu and at least one of the listed components: Al, Si, Ti, Zr, Cr, Zn, Fe, Mn, Ni, Co, V, W, Mo, Ru, Ag, Re, alkali, Alkaline earth elements, lanthanum and lanthanides, which may be present in whole or in part in oxidic form, with the proviso that this catalyst is prepared by mixing the constituents and build-up granulation, if appropriate with organic additives, further shaping processes being possible.
2. Katalysator gemäß Anspruch 1, dadurch gekennzeichnet, daß das Porenvolumen zwischen 0,20 und 1,2 ml/g Katalysator liegt.2. Catalyst according to claim 1, characterized in that the pore volume is between 0.20 and 1.2 ml / g catalyst.
3. Katalysator gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Anteil an Poren mit einem3. Catalyst according to claim 1 or 2, characterized in that the proportion of pores with a
Porendurchmesser über 20 nm größer als 20 ml/g beträgt.Pore diameter over 20 nm is greater than 20 ml / g.
4. Katalysator gemäß Anspruch 1-3, dadurch gekennzeichnet, daß die Porenverteilung bimodal sein kann.4. Catalyst according to claims 1-3, characterized in that the pore distribution can be bimodal.
5. Katalysator gemäß Anspruch 1-4, dadurch gekennzeichnet, daß der einen Gesamtmetallgehalt von mindestens 5 Gew.-5. Catalyst according to claims 1-4, characterized in that the total metal content of at least 5 wt.
% aufweist.% having.
6. Katalysator gemäß Anspruch 1-5, dadurch gekennzeichnet, daß dessen Metalle in unterschiedlichen Oxidationsstufen vorliegen, wobei einzelne Metalle in mehr als einer Oxidationsstufe vorliegen können.6. Catalyst according to claims 1-5, characterized in that its metals are present in different oxidation states, wherein individual metals can be present in more than one oxidation state.
7. Katalysator gemäß Anspruch 1-6, dadurch gekennzeichnet, daß er einen Cu-Gehalt von 1 - 60 Gew.-% aufweist.7. Catalyst according to claims 1-6, characterized in that it has a Cu content of 1-60% by weight.
8. Katalysator gemäß Anspruch 1-7, dadurch gekennzeichnet, daß er bei der Verwendung von Cr ein Cu:Cr Verhältnis von (5 - 15): (0,05 - 3), bevorzugt 10:1 aufweist. 8. Catalyst according to claims 1-7, characterized in that when using Cr it has a Cu: Cr ratio of (5-15): (0.05 - 3), preferably 10: 1.
9. Katalysator gemäß Anspruch 1-8, dadurch gekennzeichnet, daß seine Bestandteile auch Mischoxide sind.9. A catalyst according to claims 1-8, characterized in that its components are also mixed oxides.
10. Katalysator gemäß Anspruch 1-9, dadurch gekennzeichnet, daß die Elemente AI, Si in oxidischer oder nicht oxidscher Form verwendet werden.10. Catalyst according to claims 1-9, characterized in that the elements AI, Si are used in oxidic or non-oxide form.
11. Katalysator gemäß Anspruch 1-10, dadurch gekennzeichnet, daß der Herstellprozeß ohne Fällungsreaktion einer wässrigen Lösung und ohne Filtrationsschritt durchgeführt wird.11. A catalyst according to claims 1-10, characterized in that the manufacturing process is carried out without a precipitation reaction of an aqueous solution and without a filtration step.
12. Katalysator gemäß Anspruch 1-11, dadurch gekennzeichnet, daß bei 100-200 °C, bevorzugt bei 105- 130 °C, an Luft oder einem Inertgas, wie Stickstoff oder Argon oder einem Gemisch daraus, getrocknet wird.12. A catalyst according to claims 1-11, characterized in that at 100-200 ° C, preferably at 105-130 ° C, in air or an inert gas, such as nitrogen or argon or a mixture thereof, is dried.
13. Katalysator gemäß Anspruch 1-12, dadurch gekennzeichnet, daß bei 300-800 °C, bevorzugt bei 450- 700 °C, an Luft oder einem Inertgas, wie Stickstoff oder Argon oder unter Wasserdampf oder einem Gemisch daraus, calciniert wird.13. A catalyst according to claims 1-12, characterized in that at 300-800 ° C, preferably at 450-700 ° C, in air or an inert gas such as nitrogen or argon or under steam or a mixture thereof, calcined.
14. Katalysator gemäß Anspruch 1-13, dadurch gekennzeichnet, daß die spezifische Oberfläche des Katalysators (BET) zwischen 15 - 200 m2/g liegt.14. A catalyst according to claims 1-13, characterized in that the specific surface area of the catalyst (BET) is between 15-200 m 2 / g.
15. Katalysator gemäß Anspruch 1-14, dadurch gekennzeichnet, daß bei Röntgenbeugungsanalysen je nach den Bestandteilen des Katalysators und den Oxidationsstufen der Bestandteile verschiedene Kristallstrukturen erkennbar sein können, wie Spinellphasen, oxidisches Kupfer, bei Verwendung von Mn neben Cr können Cu-Mn-Mischoxide gefunden werden, bei Verwendung von Ba neben Cr beispielsweise auch BaCr04 u.a..15. Catalyst according to claims 1-14, characterized in that in X-ray diffraction analyzes, depending on the constituents of the catalyst and the oxidation states of the constituents, different crystal structures can be recognizable, such as spinel phases, oxidic copper, when using Mn besides Cr can Cu-Mn mixed oxides can be found when using Ba in addition to Cr, for example also BaCr0 4 and others.
16. Katalysator gemäß Anspruch 1-15, dadurch gekennzeichnet, daß für den Einsatz in Dehydrier- Hydrierprozessen oder Hydrogenolysen eine Aktivierung des Katalysators durch Flüssig- oder Gasphasenreduktion vorausgehen kann.16. A catalyst according to claims 1-15, characterized in that for use in dehydrogenation Hydrogenation processes or hydrogenolysis can precede activation of the catalyst by liquid or gas phase reduction.
17. Katalysator gemäß Anspruch 1-16, dadurch gekennzeichnet, daß nach Reduktion in der Gasphase eine Stabilisierung der metallischen Phasen durch partielle Oxidation erfolgen kann, sodaß der Katalysator problemlos an Luft gehandhabt werden kann.17. A catalyst according to claims 1-16, characterized in that after reduction in the gas phase, the metallic phases can be stabilized by partial oxidation, so that the catalyst can be handled in air without any problems.
18. Katalysator gemäß Anspruch 1-17, dadurch gekennzeichnet, daß nach Reduktion in der Gasphase eine Stabilisierung der metallischen Phasen durch ein inertes Lösemittel wie Paraffin, Wachse hochsiedendes aromatenfreies Benzin erfolgt, so daß der Katalysator problemlos an Luft gehandhabt werden kann, solange er mit der Inertphase bedeckt bleibt.18. A catalyst according to claims 1-17, characterized in that after reduction in the gas phase, the metallic phases are stabilized by an inert solvent such as paraffin, waxes and high-boiling aromatics-free gasoline, so that the catalyst can be handled in air without any problem as long as it is with the inert phase remains covered.
19. Katalysator gemäß Anspruch 1-18, dadurch gekennzeichnet, daß bei Verwendung einer Flüssigphase zur Aktivierung das umzusetzende Edukt oder Eduktgemisch das Reduktionsmittel selbst ist.19. A catalyst according to claims 1-18, characterized in that when using a liquid phase for activation, the starting material or starting material mixture to be reacted is the reducing agent itself.
20. Katalysator gemäß Anspruch 1-19, dadurch gekennzeichnet, daß vor Start eines Hydrierprozesses oder einer Hydrogenolyse die partielle Oxidschicht durch Behandlung mit Wasserstoff entfernt wird, beziehungsweise bei Verwendung eines inertisierenden Mittels dieses vom Katalysator freigewaschen wird.20. A catalyst according to claims 1-19, characterized in that before the start of a hydrogenation process or hydrogenolysis the partial oxide layer is removed by treatment with hydrogen, or when an inerting agent is used, the latter is washed free of the catalyst.
21. Katalysator gemäß Anspruch 1-20, eingesetzt in Hydrierungen von Aldehyden.21. A catalyst according to claims 1-20, used in hydrogenations of aldehydes.
2-2. Katalysator gemäß Anspruch 1-20, eingesetzt in Hydrierungen von Ketonen.2-2. Catalyst according to claims 1-20, used in hydrogenations of ketones.
23. Katalysator gemäß Anspruch 1-20, eingesetzt in23. A catalyst according to claims 1-20, used in
Hydrierungen von aromatischen Nitroverbindungen. Hydrogenation of aromatic nitro compounds.
24. Katalysator gemäß Anspruch 1-20, eingesetzt in24. A catalyst according to claims 1-20, used in
Hydrogenolysen von Carbonsäureestern, zu den jeweiligen Alkoholen.Hydrogenolysis of carboxylic acid esters to the respective alcohols.
25. Katalysator gemäß Anspruch 1-20 dadurch gekennzeichnet, daß bei Hydrogenolysen von Fettsäuremethylestern das Verhältnis der formalkinetischen Konstanten von Wachesterbildung zu Wachsesterabbau größer als 2 ist.25. Catalyst according to claims 1-20, characterized in that the ratio of the formal-kinetic constants of wax ester formation to wax ester degradation is greater than 2 in the hydrogenolysis of fatty acid methyl esters.
26. Katalysator gemäß Anspruch 1-20, eingesetzt in Hydrierungen von Fettsäuren zu Fettalkoholen.26. Catalyst according to claims 1-20, used in hydrogenations of fatty acids to fatty alcohols.
27. Katalysator gemäß Anspruch 1-20, eingesetzt in Hydrierungen von Ketonen.27. A catalyst according to claims 1-20, used in hydrogenations of ketones.
28. Katalysator gemäß Anspruch 1-20, eingesetzt zu Dehydrierungen von Alkoholen.28. A catalyst according to claims 1-20, used for dehydrogenation of alcohols.
29. Katalysator gemäß Anspruch 1-20, eingesetzt zur Synthese von Methanol aus Kohlenmonoxid und29. A catalyst according to claims 1-20, used for the synthesis of methanol from carbon monoxide and
Wasserstoff.Hydrogen.
30. Katalysator gemäß Anspruch 1-20, eingesetzt in Verfahren gemäß Anspruch 21-28 in der Gas- oder Flüssigphase. 30. Catalyst according to claims 1-20, used in processes according to claims 21-28 in the gas or liquid phase.
PCT/EP2002/000211 2001-02-23 2002-01-11 Shaped copper and chromium containing catalyst for use in hydrogenation and dehydrogenation reactions WO2002068119A1 (en)

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DE10108842A DE10108842A1 (en) 2001-02-23 2001-02-23 Molded copper catalyst

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WO2007030298A1 (en) * 2005-09-02 2007-03-15 Sud-Chemie Inc. Catalytically inactive heat generator and improved dehydrogenation process
WO2009051767A1 (en) 2007-10-16 2009-04-23 Sud-Chemie Inc. Improved endothermic hydrocarbon conversion process
US7781368B2 (en) 2006-02-14 2010-08-24 Basf Se Adsorption composition and method of removing CO from streams
US8022264B2 (en) 2006-06-21 2011-09-20 Basf Se Adsorption composition and method of removing CO from streams
GB2482887A (en) * 2010-08-18 2012-02-22 Johnson Matthey Plc Catalyst and process for hydrogenation of aldehydes
US8236264B2 (en) 2006-12-01 2012-08-07 Basf Se Adsorption composition and process for removing CO from material streams
CN102850181A (en) * 2011-06-30 2013-01-02 中国石油化工股份有限公司 Preparation method of higher alcohol
US8637723B2 (en) 2010-09-09 2014-01-28 Guido Henze Process for the activation of a copper-, zinc- and zirconium oxide-comprising adsorption composition
US8637724B2 (en) 2010-09-09 2014-01-28 Basf Se Process for the regeneration of a copper, zinc and zirconium oxide-comprising adsorption composition
US8680350B2 (en) 2006-07-17 2014-03-25 Basf Se Process for hydrogenating unsaturated hydrocarbons in the presence of catalysts containing copper and zinc
WO2015138664A1 (en) 2014-03-14 2015-09-17 Clariant Corporation Improved dehydrogenation process with heat generating material
US9963644B2 (en) 2013-12-12 2018-05-08 Evonik Degussa Gmbh Cleaning of liquid hydrocarbon streams by means of copper-containing sorbents
CN108659963A (en) * 2018-05-25 2018-10-16 未名生物能源有限公司 A method of producing biodiesel by raw material of grease inferior

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WO2007030298A1 (en) * 2005-09-02 2007-03-15 Sud-Chemie Inc. Catalytically inactive heat generator and improved dehydrogenation process
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US8680350B2 (en) 2006-07-17 2014-03-25 Basf Se Process for hydrogenating unsaturated hydrocarbons in the presence of catalysts containing copper and zinc
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GB2482887A (en) * 2010-08-18 2012-02-22 Johnson Matthey Plc Catalyst and process for hydrogenation of aldehydes
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CN102850181A (en) * 2011-06-30 2013-01-02 中国石油化工股份有限公司 Preparation method of higher alcohol
US9963644B2 (en) 2013-12-12 2018-05-08 Evonik Degussa Gmbh Cleaning of liquid hydrocarbon streams by means of copper-containing sorbents
WO2015138664A1 (en) 2014-03-14 2015-09-17 Clariant Corporation Improved dehydrogenation process with heat generating material
US9725380B2 (en) 2014-03-14 2017-08-08 Clariant Corporation Dehydrogenation process with heat generating material
CN108659963A (en) * 2018-05-25 2018-10-16 未名生物能源有限公司 A method of producing biodiesel by raw material of grease inferior
CN108659963B (en) * 2018-05-25 2021-09-21 未名生物能源有限公司 Method for producing biodiesel by using inferior grease as raw material

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