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WO2002068119A1 - Catalyseur moule contenant du cuivre et du chrome et destine a des reactions d'hydrogenation et de deshydrogenation - Google Patents

Catalyseur moule contenant du cuivre et du chrome et destine a des reactions d'hydrogenation et de deshydrogenation 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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WO
WIPO (PCT)
Prior art keywords
catalyst according
catalyst
acid
hydrogenation
hydrogenolysis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2002/000211
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German (de)
English (en)
Inventor
Guido Stochniol
Inge Beul
Kurt-Alfred Gaudschun
Daniel Ostgard
Peter Panster
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Evonik Operations GmbH
Original Assignee
Degussa GmbH
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Priority to JP2002567467A priority Critical patent/JP2004518533A/ja
Priority to EP02710001A priority patent/EP1361921A1/fr
Publication of WO2002068119A1 publication Critical patent/WO2002068119A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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.

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

Abstract

L'invention concerne un catalyseur moulé composé de cuivre et d'au moins un composant parmi: Al, Si, Ti, Zr, Cr, Zn, Fe, Mn, Ni, Co, V, W, Mo, Ru, Ag, Re, éléments alcalins, éléments alcalino-terreux, lanthane et lanthanides pouvant se présenter entièrement ou partiellement sous forme oxydée sachant que ce catalyseur est obtenu par mélange des constituants et de granulation. D'autres procédés de façonnement comme, par exemple, l'extrusion ou la mise en comprimés sont possibles. Les éléments peuvent être utilisés à partir de leurs sels comme les nitrates, les sulfates de leurs oxyddes, les hydroxides, oxalates, carbonates, acétates, citrates ou leurs mélanges. Le catalyseur peut être utilisé pour l'hydrogénation ou la déshydrogénation.
PCT/EP2002/000211 2001-02-23 2002-01-11 Catalyseur moule contenant du cuivre et du chrome et destine a des reactions d'hydrogenation et de deshydrogenation Ceased WO2002068119A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2002567467A JP2004518533A (ja) 2001-02-23 2002-01-11 水素化反応および脱水素化反応のための形成された銅含有およびクロム含有の成形された触媒
EP02710001A EP1361921A1 (fr) 2001-02-23 2002-01-11 Catalyseur moule contenant du cuivre et du chrome et destine a des reactions d'hydrogenation et de deshydrogenation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10108842A DE10108842A1 (de) 2001-02-23 2001-02-23 Geformter Kupfer-Katalysator
DE10108842.6 2001-02-23

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WO2002068119A1 true WO2002068119A1 (fr) 2002-09-06

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WO2007030298A1 (fr) * 2005-09-02 2007-03-15 Sud-Chemie Inc. Generateur thermique catalytiquement inactif et processus de deshydrogenation ameliore
WO2009051767A1 (fr) 2007-10-16 2009-04-23 Sud-Chemie Inc. Procédé amélioré de conversion endothermique d'hydrocarbures
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 (zh) * 2011-06-30 2013-01-02 中国石油化工股份有限公司 一种高碳醇的制备方法
US8637724B2 (en) 2010-09-09 2014-01-28 Basf Se Process for the regeneration of a copper, zinc and zirconium oxide-comprising adsorption composition
US8637723B2 (en) 2010-09-09 2014-01-28 Guido Henze Process for the activation 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 (fr) 2014-03-14 2015-09-17 Clariant Corporation Procédé de déshydrogénation amélioré au moyen d'une matière thermogène
US9963644B2 (en) 2013-12-12 2018-05-08 Evonik Degussa Gmbh Cleaning of liquid hydrocarbon streams by means of copper-containing sorbents
CN108659963A (zh) * 2018-05-25 2018-10-16 未名生物能源有限公司 一种以劣质油脂为原料生产生物柴油的方法

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JP7099493B2 (ja) * 2020-07-06 2022-07-12 日本ゼオン株式会社 シクロペンタノンの製造方法

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US2649420A (en) * 1948-12-08 1953-08-18 Celanese Corp Preparation of barium-chromiumcopper-silica-containing catalyst
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US3883445A (en) * 1971-07-07 1975-05-13 Monsanto Co Shrinkage resistant auto exhaust catalysts
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US4982020A (en) * 1986-07-23 1991-01-01 Henkel Kommanditgesellschaft Auf Aktien Process for direct hydrogenation of glyceride oils

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US7622623B2 (en) 2005-09-02 2009-11-24 Sud-Chemie Inc. Catalytically inactive heat generator and improved dehydrogenation process
US7973207B2 (en) 2005-09-02 2011-07-05 Sud-Chemie Inc. Endothermic hydrocarbon conversion process
RU2428250C2 (ru) * 2005-09-02 2011-09-10 Зюд-Кеми Инк. Каталитически неактивный тепловой генератор и усовершенствованный процесс дегидрирования
WO2007030298A1 (fr) * 2005-09-02 2007-03-15 Sud-Chemie Inc. Generateur thermique catalytiquement inactif et processus de deshydrogenation ameliore
US7781368B2 (en) 2006-02-14 2010-08-24 Basf Se Adsorption composition and method of removing CO from streams
US7884048B2 (en) 2006-02-14 2011-02-08 Basf Se Adsorption composition and process for removal of CO from material streams
US8022264B2 (en) 2006-06-21 2011-09-20 Basf Se Adsorption composition and method of removing CO from streams
US8680350B2 (en) 2006-07-17 2014-03-25 Basf Se Process for hydrogenating unsaturated hydrocarbons in the presence of catalysts containing copper and zinc
US8236264B2 (en) 2006-12-01 2012-08-07 Basf Se Adsorption composition and process for removing CO from material streams
WO2009051767A1 (fr) 2007-10-16 2009-04-23 Sud-Chemie Inc. Procédé amélioré de conversion endothermique d'hydrocarbures
GB2482887A (en) * 2010-08-18 2012-02-22 Johnson Matthey Plc Catalyst and process for hydrogenation of aldehydes
US9199220B2 (en) 2010-09-09 2015-12-01 Basf Se Process for the activation of a copper-, zinc- and zirconium oxide-comprising adsorption composition
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
US9931613B2 (en) 2010-09-09 2018-04-03 Basf Se Process for the regeneration of a copper, zinc and zirconium oxide-comprising adsorption composition
CN102850181A (zh) * 2011-06-30 2013-01-02 中国石油化工股份有限公司 一种高碳醇的制备方法
US9963644B2 (en) 2013-12-12 2018-05-08 Evonik Degussa Gmbh Cleaning of liquid hydrocarbon streams by means of copper-containing sorbents
WO2015138664A1 (fr) 2014-03-14 2015-09-17 Clariant Corporation Procédé de déshydrogénation amélioré au moyen d'une matière thermogène
US9725380B2 (en) 2014-03-14 2017-08-08 Clariant Corporation Dehydrogenation process with heat generating material
CN108659963A (zh) * 2018-05-25 2018-10-16 未名生物能源有限公司 一种以劣质油脂为原料生产生物柴油的方法
CN108659963B (zh) * 2018-05-25 2021-09-21 未名生物能源有限公司 一种以劣质油脂为原料生产生物柴油的方法

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JP2004518533A (ja) 2004-06-24

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