EP3122453A1 - Catalyseur d'hydrogénation et son procédé de fabrication - Google Patents

Catalyseur d'hydrogénation et son procédé de fabrication

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Publication number
EP3122453A1
EP3122453A1 EP15711489.3A EP15711489A EP3122453A1 EP 3122453 A1 EP3122453 A1 EP 3122453A1 EP 15711489 A EP15711489 A EP 15711489A EP 3122453 A1 EP3122453 A1 EP 3122453A1
Authority
EP
European Patent Office
Prior art keywords
copper
carbonate
range
solution
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15711489.3A
Other languages
German (de)
English (en)
Inventor
Martin Paulus
Frank Grossmann
Karl-Heinz STADLER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant International Ltd
Original Assignee
Clariant International Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Clariant International Ltd filed Critical Clariant International Ltd
Publication of EP3122453A1 publication Critical patent/EP3122453A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • 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
    • B01J23/80—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 zinc, cadmium or mercury
    • 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
    • B01J35/30—
    • B01J35/391—
    • B01J35/392—
    • B01J35/60—
    • B01J35/633—
    • B01J35/635—
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/04—Mixing
    • 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
    • B01J37/08—Heat treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the invention relates to a process for the preparation of a Cu-Zn catalyst molded body via a carbonate-containing precursor, as well as the catalysts obtainable by this process.
  • Catalyst is suitable for the hydrogenation of organic
  • Dicarboxylic anhydrides such as maleic anhydride (MSA) or esters of diacids to di-alcohols, such as butanediol.
  • MSA maleic anhydride
  • esters of diacids to di-alcohols such as butanediol.
  • Carbonyl compounds in particular of carboxylic acids or
  • Ni, Cu, Co or noble metal-containing catalysts are used. These can be used as unsupported catalysts (e.g., Raney catalysts) or as supported catalysts.
  • Patent DE 43 45 265 and DE 43 35 360 describe shaped Raney catalysts based on Ni, Co, Cu and Fe. These are used for the hydrogenation of organic compounds.
  • the disadvantage of these catalysts is the addition of metal powder as a binder, wherein the added metal powder is less catalytically active compared to the Raney metal.
  • the preparation of shaped Raney catalysts without the addition of binders is described in EP 880 996. These catalysts are used for the hydrogenation of nitriles.
  • a metal-aluminum alloy present as a powder is mixed with a high molecular weight polymer and optionally promoters and then shaped into shaped bodies.
  • the moldings are calcined at temperatures up to 850 ° C, resulting in the controlled decomposition of the polymer and the formation of a fixed bed catalyst with sufficient
  • the core of the catalyst continues to consist of the used
  • Metal-aluminum alloy serves as a support for the activated outer layer of the catalyst. This leaves a significant portion of the relatively expensive alloys unused.
  • US 4,666,879 describes an extruded copper chromite-alumina catalyst prepared by mixing 40 to 82 weight percent copper chromite and 18 to 60 weight percent alumina.
  • the AI2O3 is typically used in the form of pseudoboehmite or hydroxy boehmite.
  • the extruded catalyst after calcination is for liquid and gas phase hydrogenation and hydrogenolysis of various
  • Catalysts are typically between 125 and 225 m 2 / g.
  • US Pat. No. 4,762,817 describes a catalyst for the hydrogenation of aldehydes which consists essentially of a mixture of copper and zinc oxide.
  • An improvement in selectivity could be achieved by impregnation with alkali metals such as sodium, potassium, lithium or cesium, in combination with a transition metal such as nickel, cobalt or mixtures thereof.
  • the catalyst contains copper, aluminum and another metal such as magnesium, zinc, titanium, zirconium, tin, nickel, cobalt or mixtures thereof and is subjected to reduction prior to its use.
  • the temperature during the reduction is increased stepwise to a final temperature of 150 ° C to 250 ° C.
  • Aldehydes to alcohols with Cu and Ni-containing catalysts Aldehydes to alcohols with Cu and Ni-containing catalysts.
  • the first stage of the hydrogenation is carried out with a granular, alkaline copper catalyst.
  • the second stage of the hydrogenation is carried out with a granular, alkaline copper catalyst.
  • a supported nickel-containing catalyst is used, the support material having acidic centers of a certain acid strength.
  • a copper chromite catalyst consisting of a mixture containing about 20 to 80% by weight of copper chromite and about 20 to 80% by weight of an extrudable inorganic binder.
  • the catalyst has a specific surface area of about 20 to 225 m 2 / g, and the total pore volume of the pores in the catalyst is 0.35 to 1 cm-Vg.
  • this document describes a method of making a shaped copper chromite catalyst by forming an extrudable mixture, extruding the mixture, and calcining the extrudate.
  • the catalysts are used for the hydrogenation of aldehydes, ketones, carboxylic acids and
  • a hydrogenation catalyst comprising oxides of a first metal, copper or zinc, and a second metal, chromium, molybdenum, tungsten or vanadium, and optionally an oxide of a promoter, such as manganese, barium, zinc, nickel, Cobalt, cadmium or iron.
  • the hydrogenation catalyst is present as a powder whose mean particle diameter is about 6 to 20 ⁇ , and whose surface is about 20 to 70 m ⁇ / g.
  • the catalysts are prepared by precipitation of the metal salts with a base.
  • Hydrogenation catalysts are used for the hydrogenation of aldehydes, ketones, carboxylic acids and carboxylic acid esters.
  • WO 92/04119 describes copper-manganese catalysts for the hydrogenation of fatty acids and their esters.
  • an aqueous solution of Cu (II) and Mn (II) salts is mixed with sodium hydroxide solution, whereby a precipitate of Cu and Mn hydroxide is formed.
  • This precipitate is then calcined as a powder or in tableted form.
  • the resulting catalysts have a BET surface area of about 3 to 45 m ⁇ / g.
  • WO 02/47818 describes Cu-oxide-containing catalysts for the hydrogenation of maleic anhydride and its derivatives.
  • Pore formers are used in particular graphite and ammonium nitrate, which are added to the catalyst powder before tableting.
  • the catalysts in whose production only graphite was used as a pore-forming agent, had a pore volume of less than 0.2 cm-Vg.
  • WO 97/34694 describes copper oxide / alumina hydrogenation catalysts obtained by precipitation of aqueous solutions of Copper nitrate and sodium aluminate be prepared with sodium carbonate. The material obtained is calcined after drying at about 400 ° C to 700 ° C, and then with the addition of
  • the tablets have a pore volume of 0.2 to 0.6 ml / g and a bimodal pore radius distribution with a first maximum at about 10 nm and a second maximum at about 50 to at most 200 nm.
  • the conversion of a catalytically conducted reaction is determined inter alia by the activity of a catalyst, which in turn is influenced inter alia by the size of the so-called “metal surface” of the catalyst.
  • Metal surface is generally understood as the accessible surface of the active component of the catalyst.
  • the catalyst is generally before the actual use by reduction of an oxidic precursor of the active component in the catalytically active
  • a high Cu metal surface is associated with high activity. As a rule, temperature treatments always lead to a more or less pronounced sintering of the
  • Sintering reduces the accessible surface area of the active component of the catalyst. Since the reduction of the catalyst usually takes place at elevated temperature, a suitable temperature control must be observed in order to keep the sintering effects as low as possible.
  • the invention relates to a process for producing a tabletted shaped catalyst body, comprising the following steps:
  • Metal carbonate mixture having a carbonate content in the range of 2.7 to 14.0 wt .-%, preferably in the range of 3.0 to 12.5 wt .-%, particularly preferably in the range of 3.2 to 12.0 wt. %, more preferably in the range of 5.0 to 8.0 wt .-% and
  • step (b) tableting the thermally obtained in step (a)
  • Precipitate 2 is a copper carbonate-containing precipitate, obtainable by combining a solution C with a solution D,
  • Precipitate 3 is a zinc carbonate-containing precipitate, obtainable by combining a solution E with a solution F,
  • Precipitate 4 is a precipitate containing at least one metal carbonate other than copper carbonate and zinc carbonate, obtainable by combining at least one solution G with at least one solution H;
  • Solution A is obtainable by adding a copper compound, a zinc compound and optionally one or more others
  • Metal compounds in a solvent, in particular water, optionally with the aid of an acid or base, are dissolved,
  • Solvent especially water, is dissolved
  • Solution C is obtainable by dissolving a copper compound in a solvent, especially water, optionally with the aid of an acid or base,
  • - Solution E is obtainable by adding a zinc compound in a solvent, in particular water, optionally under
  • - Solution G is obtainable by dissolving a metal compound, which is not a copper or zinc compound, in a solvent, in particular water, optionally with the aid of an acid or base.
  • the carbonate content, in particular of the metal carbonate mixture is preferably determined according to DIN ISO 10693.
  • the invention relates to Cu-Zn catalysts which can be prepared by the inventive method.
  • the invention relates to the use of
  • Cu-Zn catalysts according to the invention for the hydrogenation of organic compounds, in particular of compounds containing a carbonyl function are particularly useful for the hydrogenation of organic compounds, in particular of compounds containing a carbonyl function.
  • the process according to the invention for producing a tabletted shaped catalyst body comprises the following steps:
  • Metal carbonate mixture having a carbonate content, determined by DIN ISO 10693, in the range of 2.7 to 14.0 wt .-%, preferably in the range of 3.0 to 12.5 wt .-%, particularly preferably in the range of 3.2 to 12.0 wt .-%, more preferably in the range of 5.0 to 8.0 wt .-% and
  • step (b) tableting the thermally obtained in step (a)
  • the metal carbonate mixture becomes
  • Solution A is prepared by adding a copper compound, a
  • Zinc compound and optionally one or more others
  • Metal compounds that are not copper or zinc compounds are dissolved in a container in a suitable solvent.
  • a copper compound, a zinc compound, and optionally one or more other metal compounds which are not copper or zinc compounds may be dissolved in a plurality of containers and the solutions obtainable therefrom combined into a solution A.
  • Solution B is prepared by adding a
  • Carbonate compound is dissolved in a suitable solvent.
  • Precipitate 1 is a copper carbonate-containing, zinc carbonate-containing and optionally one of copper carbonate and
  • the metal carbonate mixture is prepared by mixing a precipitate 2, a
  • Precipitate 3 and optionally one or more
  • Precipitates 4 wherein the precipitates are dried prior to mixing and / or after mixing by heating to a temperature in the range of 75 ° C to 130 ° C.
  • Precipitate 2 is a copper carbonate-containing precipitate and is prepared by combining a solution C with a solution D.
  • Precipitate 3 is a zinc carbonate-containing
  • Precipitate 4 is a precipitate containing at least one metal carbonate other than copper carbonate and zinc carbonate, and is prepared by combining at least one solution G with at least one solution H.
  • Solution C is prepared by dissolving a copper compound in a suitable solvent.
  • Solution E is prepared by dissolving a zinc compound in a suitable solvent.
  • Solution G is prepared by adding a metal compound, the no copper or zinc compound is dissolved in a solvent.
  • the formulation solution in the sense of the present invention includes both solutions and suspensions and slurries, with solutions being preferred.
  • the solvent is water.
  • An acid or base may be added to the water to help dissolve the compounds.
  • the water may have a neutral pH of about 7, an acidic pH of about 0 to less than 7, or a basic pH of greater than about 7 to about 14.
  • a pH value suitable for dissolving the compounds is chosen as a function of the compound to be dissolved.
  • the water has a pH in the range of 4 to 10, preferably 5 to 9.
  • copper compounds and zinc compounds it is possible in principle to use both copper and zinc in metallic form and preferably all compounds of copper and zinc which are readily soluble in water, acids or alkalis, in particular the salts of the metals mentioned, especially their nitrates, carbonates, oxides, hydroxides,
  • Hydrocarbonates whose halides, such as chlorides, bromides, and / or iodides, and / or their sulfates are used.
  • oxides of metals such as copper oxide and / or zinc oxide to
  • aqueous solutions Preparation of the aqueous solutions are used, then these are preferably partially or completely dissolved by adding a suitable mineral acid.
  • the copper in copper oxide may be in one or more different oxidation states, such as
  • the mineral acid is preferably selected from HNO3, HCl, H2SO4 and mixtures thereof. If the metals themselves, ie copper and / or zinc, for the preparation of the aqueous solution (s),
  • Suspension (s) or slurry (s) are used, then these are preferably partially or completely dissolved by adding suitable acids or alkalis.
  • suitable acids or alkalis The dissolution of the metals can be carried out, for example, in inorganic acids or alkalis.
  • Preferred copper compounds are copper oxide (CU2O and / or CuO), copper nitrate, copper chloride, copper carbonate,
  • Copper acetate and copper sulfate, in particular copper nitrate are particularly useful in the following processes: Copper acetate and copper sulfate, in particular copper nitrate.
  • copper metal can be dissolved in oxidizing acids such as nitric acid (HNO3).
  • HNO3 nitric acid
  • Preferred zinc compounds are zinc nitrate, zinc sulfate,
  • Zinc chloride, zinc carbonate, zinc hydroxide, zinc sulfite, zinc acetate and zinc phosphate are dissolved.
  • acids such as hydrochloric acid (HCl) or nitric acid (HN0 3 ), or in alkalis, such as sodium hydroxide solution (NaOH) or potassium hydroxide solution (KOH), are dissolved.
  • Zinc compounds are, are preferably selected from
  • Particularly preferred metal compounds are the compounds of aluminum, manganese, cerium and zirconium and mixtures thereof.
  • Very particularly preferred metal compounds are the compounds of zirconium and aluminum.
  • Zinc compound may also include such metal compounds containing in addition to the metals mentioned copper and / or zinc.
  • metal compounds other than copper or zinc compounds may also be metal compound compounds such as
  • Metal complex compounds which in addition to one or more of the above-mentioned metals copper and / or zinc
  • metal compounds that are not copper or zinc compounds are substantially free of copper and zinc compounds.
  • transition metal compounds in principle all in water, Acids or alkalis readily soluble compounds of aluminum, silicon, titanium, manganese, nickel, chromium, iron, cobalt, molybdenum, calcium, barium, cerium and / or zirconium, especially the salts of these metals are used.
  • the transition metals may also be used in metallic form.
  • the transition metals may also be used in metallic form.
  • the carbonate-containing solutions B, D, F and H are prepared by dissolving a carbonate compound in a suitable solvent.
  • the solvent is water.
  • An acid or base may be added to the water to dissolve the
  • the water may have a neutral pH of about 7, an acidic pH of about 5 to less than 7, or a basic pH of greater than about 7 to about 13.
  • the water used to dissolve the carbonate has a pH in the range of 5 to 11, more preferably in the range of 6 to 9, and in particular has a neutral pH of about 7.
  • Solutions B, D, F and G may be the same or different from each other.
  • the solutions may have the same or different concentrations of one or more different carbonates and / or be present at the same or different pH values.
  • the carbonate compound is preferably selected from the
  • alkali metal carbonates such as lithium, sodium, potassium, rubidium or cesium carbonate
  • alkaline earth carbonates such as magnesium, calcium, strontium or barium carbonate
  • Hydrogen carbonates or any mixtures of carbonates and bicarbonates can be used.
  • Preferred alkali metal carbonates are sodium and potassium carbonate, especially sodium carbonate.
  • Preferred alkali metal bicarbonates are sodium and potassium bicarbonate, in particular
  • Sodium bicarbonate Particularly preferred is the use of sodium carbonate and / or sodium bicarbonate.
  • a precipitate is formed.
  • a metal-containing solution such as solution A, solution C, solution E, or solution G
  • a carbonate-containing solution such as solution B, solution D, solution F, or solution H
  • a precipitate 1 is formed.
  • a precipitate 2 is formed.
  • a precipitate 3 is formed by combining a solution G and a solution H a
  • combining may be accomplished by using the above-mentioned solution pairs (such as solution A and
  • Solution B Solution B; Solution C and solution D; Solution E and solution F; or
  • Solution G and solution H are simultaneously added to a common container, such as a precipitation container.
  • the two solutions are preferably introduced continuously into the reaction volume of a precipitation mixer.
  • the combining can also be carried out by adding a solution of the respective solution pair (such as solution A or solution B) to the associated other solution of the present invention, for example in a container such as a precipitation container
  • the carbonate-containing solutions B, D, F and H are preferably heated to a temperature of 20 ° C or more, such as a temperature in the range of 50 ° C to 90 ° C, especially about 80 ° C, before combining, heated and stirred.
  • metal-containing solution such as solution A
  • carbonate-containing solution such as solution B
  • Solution E and solution F; or solution G and solution H) forms a precipitate in the mixture (hereinafter also referred to as
  • precipitate-containing solution mixture The combining of the solutions is usually carried out in a stirred container.
  • the container is preferably equipped with a slanted blade stirrer,
  • the precipitate-containing solution mixture is preferably maintained at a temperature of 20 ° C or more, and more preferably at a temperature in the range of 50 ° C to 90 ° C, preferably at about 80 ° C.
  • the precipitate-containing solution mixture is at a temperature in the range of 50 ° C to 90 ° C, preferably at a temperature of about 80 ° C for at least 30 minutes, preferably 1 to 36 hours, in particular about 2 hours. held to the If necessary, to complete precipitation or to increase the crystallinity of the precipitate by aging.
  • the pH of the precipitate-containing solution mixture is usually kept constant by methods known to the person skilled in the art.
  • the metered addition rate of solutions can be chosen so that a certain pH in the
  • the pH of the precipitate-containing solution mixture is in the range of 5.0 to 8.5, more preferably in the range of 6.0 to 7.5, preferably about 6.8.
  • the precipitate (ie precipitation 1, precipitation 2,
  • Precipitate 3, precipitate 4, etc. is preferably separated by filtration.
  • the precipitate may be separated by decanting or centrifuging.
  • the separated precipitate may be subjected to one or more washes. It can the
  • the separated precipitate may be slurried by filtration, decanting or centrifuging in a container and then re-slurried with a
  • Filter press a centrifuge or a decanter to be separated from the liquid phase. This process is usually one or more times until reaching a specific one
  • the conductivity of the filtrate performed usually correlates with the concentration of sodium ions.
  • the conductivity of the filtrate of the last washing operation is preferably 0.5 mS / cm or less, more preferably 0.2 mS / cm or less.
  • the conductivity is determined according to DIN 38404, Part 8.
  • the separated and optionally washed precipitate is then subjected to drying.
  • the drying takes place by heating the precipitate to a temperature in the range of 75 ° C to 130 ° C, preferably in a range of 90 ° C to 120 ° C.
  • the drying can be done for example by spray drying.
  • a suspension having a solids content of 10 to 40% by weight is prepared from the separated precipitate, such as a filter cake, with water. This suspension will
  • the temperature in the spray dryer during drying is preferably in a range of 75 ° C to 130 ° C, in particular in a range of 90 ° C to 120 ° C.
  • the characteristic for the drying outlet temperature is preferably in the range of 90 ° C to 120 ° C and is usually by
  • Solids content of the suspension (and thus the amount of water that must be evaporated) or controlled temperature in the spray dryer.
  • the treatment of the material with the spray dryer results in particular in a dry powder.
  • precipitates 2, 3 and 4 obtained as described above are first separated, optionally washed and subjected to drying by heating to a temperature in the range of 75 ° C to 130 ° C. The separation, optionally washing and drying is carried out as described above. Subsequently, the mixing of a precipitate 2, a precipitate 3 and
  • the mixing can be carried out, for example, with the aid of a bar or propeller stirrer.
  • the separated precipitates may be mixed prior to drying. These are the received precipitates 2, 3 and 4, first, as described above, separated, optionally washed and with the aid of a
  • the metal carbonate mixture (i) or (ii) preferably has (after drying by heating to a temperature in the range of 75 ° C to 130 ° C) a carbonate content of up to 20 wt .-%, preferably in the range of 10 to 18 wt. -% on.
  • the carbonates contained in the metal carbonate mixture are in the case of copper carbonate
  • the metal carbonate mixture (i) or (ii) is subjected to a thermal treatment in a step (a) until a carbonate content, determined in accordance with DIN ISO 10693, in the range of 2.7 to 14.0% by weight, preferably in the range of 3 , 0 to 12.5 wt%, more preferably in the range of 3.2 to 12.0 wt%, even more preferably in the range of 5.0 to 8.0 wt%.
  • the temperature during the thermal treatment is the same.
  • the thermal treatment can be carried out under air or inert gas, such as argon or nitrogen, under oxygen or
  • the thermal treatment may be discontinuous, e.g. in a rack oven or
  • the duration of the thermal treatment is preferably from 5 minutes to 10 hours, preferably from 1 hour to 6 hours, in particular from 1.5 hours to 5 hours.
  • the thermal treatment is preferably from 5 minutes to 10 hours, preferably from 1 hour to 6 hours, in particular from 1.5 hours to 5 hours.
  • treated metal carbonate mixture preferably has 5 wt .-% or less, preferably 0.1 to 4.0 wt .-%, in particular 0.5 to 3.0 wt .-% of aluminum, based on the total weight of the thermally treated metal carbonate mixture.
  • the tableting is preferably carried out with a tablet press, such as a Korsch tablet press.
  • a tablet press such as a Korsch tablet press.
  • tabletting tablets with a diameter of about 1 to 10 mm, preferably from 1.5 to 8 mm and particularly preferably from 3 to 5 mm and a height of about 1 to 10 mm, preferably from 1.5 to 8 mm and particularly preferably from 3 to 5 mm are obtained.
  • tablets having a lateral compressive strength, measured according to DIN EN 1094-5, of 40 to 250 N, preferably 50 to 160 N, particularly preferably 60 to 120 N prepared.
  • the tablets produced by the tabletting have a diameter in the range of 3 to 5 mm, a height in the range of 3 to 5 mm and a
  • the tabletting is preferably carried out with the addition of
  • Lubricants such as graphite, oils or stearates, preferably graphite.
  • the obtained in step (a) is thermal
  • step (b) the treated metal carbonate mixture with lubricants, in particular graphite, mixed, optionally compacted and / or granulated and then tabletted in step (b).
  • lubricants in particular graphite
  • the treated metal carbonate mixture with lubricants, in particular graphite mixed, optionally compacted and / or granulated and then tabletted in step (b).
  • the lubricants in particular graphite
  • Lubricant before tabletting in an amount in the range of 0.1 to 5 wt .-%, based on the total weight of the
  • Lubricant in an amount in the range of 0.5 to 5 wt .-%, particularly preferably in an amount in the range of 1 to 4 wt .-%, added based on the total weight of the mass to be tableted.
  • the shaped catalyst body is prepared by tableting a mixture of oxidic material and carbonate-containing material.
  • the oxide material includes oxides of the metals used herein and / or
  • Transition metals such as copper oxide, zinc oxide, aluminum oxide,
  • Each metal and / or transition metal can independently in
  • the carbonate-containing material includes carbonates of the metals used herein and / or
  • Transition metals such as copper carbonate, aluminum carbonate,
  • various components such as oxides and / or carbonates also come from different manufacturing processes or have been prepared by various production routes or be, for example, commercially available raw materials.
  • tabletted shaped catalyst bodies produced as follows:
  • a copper compound, a zinc compound and optionally one or more other metal compounds which are not copper or zinc compounds are dissolved in water to obtain a solution A.
  • a carbonate compound is dissolved in water to obtain a solution B.
  • Solution A and solution B are absorbed Formation of a precipitate 1 united.
  • solution A and solution B are combined by adding a volume flow of solution A to a
  • solution B is metered.
  • the precipitate 1 formed is separated, if necessary and dried by heating to a temperature of 75 ° C to 130 ° C, whereby a metal carbonate mixture (i) is obtained.
  • the obtained metal carbonate mixture (i) becomes a
  • thermally treated metal carbonate mixture is determined according to DIN ISO 10693 and is based on the total weight of the thermally treated metal carbonate mixture, preferably 2.7 to 14.0 wt .-%.
  • the thermally treated metal carbonate mixture is then tableted to obtain a
  • tabletted shaped catalyst body obtained in step (b) is reduced in a step (c).
  • the reduction is preferably carried out by heating the
  • the reducing atmosphere is hydrogen.
  • the reduction is carried out for example at a temperature in the range of 150 ° C to 450 ° C, in particular in the range of 180 ° C to 250 ° C, preferably in the range of 190 ° C to 210 ° C, more preferably at about 200 ° C.
  • the reduction takes place, for example, depending on the amount of catalyst to be reduced over a period of 1 hour (for
  • 500 g) to 10 days for example, 60 tons
  • Catalyst quantities on a production scale are preferably reduced over a period of 3 to 8 days.
  • the reduction is carried out at a temperature in the range of 190 ° C to 210 °.
  • the shaped catalyst bodies are stabilized wet or dry after the reduction.
  • the moldings are covered with liquid in order to avoid contact with oxygen as much as possible. Suitable liquids
  • organic liquids and water preferably organic liquids.
  • Preferred organic liquids are those which have a vapor pressure of 0.5 hPa or less at 20 ° C.
  • suitable organic liquids are iso-decanol, fatty alcohols, such as. B. Nafol® the company Sasol, hexadecane, 2-ethyl-hexanol, propylene glycol and mixtures thereof, in particular iso-decanol.
  • the reduction reactor is a mixture of oxygen or an oxygen-containing gas
  • an inert gas such as argon or
  • Mixture is preferably increased from about 0.04% by volume to about 21% by volume.
  • a mixture of air and inert gas can be metered in, wherein the ratio of air to inert gas is initially about 0.2% by volume of air to 99.8% by volume of inert gas. The ratio of air to inert gas is then gradually increased (e.g., continuously or stepwise) until, for example, 100% by volume of air is metered in (which corresponds to an oxygen concentration of about 21% by volume).
  • the reactor temperature is preferably 100 ° C or less, more preferably 20 ° C to 70 ° C, and particularly preferably 30 ° C to 50 ° C.
  • the catalyst is "transportable" and can be used for
  • step (c) In the event that the catalyst user performs step (c) in-situ in the reactor, stabilization is eliminated.
  • the shaped catalyst bodies according to the invention or the shaped catalyst bodies obtainable by the process according to the invention contain, after the reduction, Cu (0) (that is copper in the
  • Oxidation level 0 in particular in a proportion of 5 to 70
  • the tabletted shaped catalyst body obtainable by the process according to the invention preferably has a pore volume in the
  • Range of 0.1 to 0.6 cmVg preferably in the range of 0.13 to 0.40 cm Vg, more preferably in the range of 0.15 to 0.25 cmVg on.
  • the reduced shaped catalyst body obtainable by the process according to the invention preferably has a pore volume in the
  • Range of 0.20 to 0.80 cmVg preferably in the range of 0.22 to 0.70 cmVg, more preferably in the range of 0.25 to 0.35 cmVg.
  • Catalyst molding is to be determined, the measurement of the catalyst molding is preferably carried out in dry-stabilized form.
  • Catalyst body according to the invention in reduced form before, and in dry stabilized form has a pore volume in the range of 0.20 to 0.80 cmVg, preferably in the range of 0.22 to 0.70 cmVg, more preferably in the range of 0.25 to 0 , 35 cmVg up.
  • the catalyst molding obtainable by the process according to the invention before the reduction has a carbonate content in the range of 2.7 to 14.0 wt .-%, preferably in the range of 3.0 to 12.5 wt .-%, particularly preferably in the range from 3.2 to 12.0 wt .-%, more preferably in the range of 5.0 to 8.0 wt .-%, based on the total weight of the shaped catalyst body.
  • the present invention relates
  • the invention relates to a tabletted CuZn catalyst shaped body which, in reduced and stabilized form, has a pore volume, measured by Hg intrusion method according to DIN 66133, in the range from 0.20 to 0.80 cmVg, preferably from 0.22 to 0.70 cmVg, particularly preferably from 0.25 to 0.35 cmVg.
  • the present invention relates to a tabletted Cu-Zn-containing shaped catalyst body, its Cu metal surface in reduced form has a value in the range of 19 m ⁇ / g to 30 m ⁇ / g, preferably in the range of 21 m ⁇ / g to 28 m ⁇ / g, based on the total weight of the shaped catalyst body.
  • the Cu metal surface area of the catalysts is determined by the principle of N20 pulse chemisorption, as described, for example, in GC Chinchen, CM Hay, HD Vandervell, KC Waugh, "The Measurement of Copper Surface Areas by Reactive Frontal Chromatography", Journal of Catalysis , Volume 103, Issue 1, January 1987, pages 79-86.
  • the Cu metal surface results from the formed amount of 2, which can be determined by a thermal conductivity detector.
  • the tabletted Cu-Zn-containing shaped catalyst body has a carbonate content in the range from 3.0 to 12.5% by weight and a reduced-metal Cu metal surface in the range from 19 m.sup.2 / g to 30 m.sup.2 / g on.
  • the tabletted Cu-Zn-containing shaped catalyst body has a carbonate content in the range of 5.0 to 8.0 wt .-% and a Cu metal surface in reduced form in the range of 21 m ⁇ / g to 28 m ⁇ / g.
  • the shaped catalyst bodies according to the invention are suitable for use in numerous reactions. Possible reactions include synthesis gas reactions, methanol syntheses, Fischer-Tropsch syntheses, pyridine synthesis, ester hydrogenolysis,
  • esters in particular fatty acid esters
  • Alcohol to the ketone dehydrogenation of alkanes (e.g., ethylbenzene or propane) to alkenes (e.g., styrene or propylene), dehydrogenation of cycloalkanes to aromatics, dehydrogenation of diols (e.g.
  • alkanes e.g., ethylbenzene or propane
  • alkenes e.g., styrene or propylene
  • dehydrogenation of cycloalkanes to aromatics dehydrogenation of diols (e.g.
  • Butanediol hydrogenation of an aldehyde, hydrogenation of an amide, hydrogenation of a fatty acid (eg by esterification and subsequent hydrogenolysis), selective hydrogenation of a fat, selective hydrogenation of an oil, hydrogenation of a nitroaromatic hydrocarbon, hydrogenation of a ketone, hydrogenation of
  • Hydrogenation of carbonyl compounds in particular for the hydrogenation of aldehydes, ketones, carboxylic acids and / or their esters or di-carboxylic acids and / or their di-esters, very particularly preferably for the hydrogenation of fatty acid esters, in particular
  • Fatty acid alkyl esters preferably fatty acid methyl esters or maleic acid esters used.
  • the catalyst according to the invention is suitable for the bottom phase hydrogenation of carboxylic acids, preferably of fatty acids or fatty acid mixtures having 5 to 24 C atoms and / or their
  • esters optionally mixed with alcohols in the
  • the fatty acids or fatty acid mixtures can be esterified in situ with alcohols present in the reaction mixture.
  • Preferred alcohols present in the reaction mixture are fatty alcohols or mixtures of
  • Figure 1 shows the dependence of the Cu metal surface (in m ⁇ / g sample) of the reduced catalysts as a function of the carbonate content (in wt% carbonate) of the unreduced catalysts.
  • Residual glow loss is determined according to DIN EN 196-2.
  • Pore volume and pore radius distribution are through
  • Carbonate content is determined according to DIN ISO 10693.
  • Cu metal surface is determined by N20 pulse chemisorption.
  • the uncalcined material is produced by precipitating the metal nitrates with sodium carbonate to give their carbonates, then the precipitate is filtered off, washed and spray-dried.
  • Solution 1 is prepared by dissolving 675 g of ZnO in 1636 g of HNO 3 (65%) and then adding 1020 g of Cu (NO 3) 2-3 H 2 O and 10 L of deionized water.
  • Solution 2 is prepared from 1333 g of Na2CC> 3 and 10 L of deionized water. The two solutions are heated to 70 ° C and stirred. These are then metered into a precipitation tank. The pH in the precipitation tank is 6.8. The volume flows of solution 1 and 2 are adjusted so that this pH established. Once the two solutions are used up, the precipitate formed is filtered off and washed with water. The filter cake is then resuspended in about 5 L of water and spray dried. The resulting dried but still
  • uncalcined powdery material is the starting material for the further preparations.
  • the carbonate content of the uncalcined powdered material determined according to DIN ISO 10693, is 16.4% by weight.
  • Carbonate content of catalyst 1, determined according to DIN ISO 10693, is 16.1% by weight.
  • Catalyst 2 is prepared by thermally treating uncalcined material (prepared as described in Reference Example 1) for 0.5 h at 280 ° C.
  • the carbonate content of this thermally treated powder determined according to DIN ISO 10693, is 15.4% by weight.
  • 100 g of this thermally treated powder are mixed with 2 g of graphite and tabletted into moldings having a diameter of about 3 mm and a height of about 3 mm.
  • the carbonate content of catalyst 2, determined according to DIN ISO 10693, is 15.1% by weight.
  • Catalyst 3 is prepared by thermally treating uncalcined material (prepared as described in Reference Example 1) for 1.0 h at 280 ° C.
  • the carbonate content of this thermally treated powder determined according to DIN ISO 10693, is 12.3% by weight.
  • 100 g of this thermally treated powder are mixed with 2 g of graphite and tabletted into moldings having a diameter of about 3 mm and a height of about 3 mm.
  • the carbonate content of catalyst 3, determined according to DIN ISO 10693, is 12.1% by weight.
  • Example 4 (Preparation of Catalyst 4)
  • Catalyst 4 is prepared by thermally treating uncalcined material (prepared as described in Reference Example 1) for 1.5 hours at 280 ° C.
  • the carbonate content of this thermally treated powder determined according to DIN ISO 10693, is 7.7% by weight.
  • 100 g of this thermally treated powder are mixed with 2 g of graphite and tabletted into moldings having a diameter of about 3 mm and a height of about 3 mm.
  • the carbonate content of catalyst 4, determined according to DIN ISO 10693, is 7.5% by weight.
  • Catalyst 5 is prepared by thermally treating uncalcined material (prepared as described in Reference Example 1) for 3 hours at 280 ° C.
  • the carbonate content of this thermally treated powder determined according to DIN ISO 10693, is 5.7% by weight.
  • 100 g of this thermally treated powder are mixed with 2 g of graphite and tabletted into moldings having a diameter of about 3 mm and a height of about 3 mm.
  • the carbonate content of catalyst 5, determined according to DIN ISO 10693, is 5.6 wt .-%.
  • Catalyst 6 is prepared by thermally treating uncalcined material (prepared as described in Reference Example 1) for 4.5 hours at 280 ° C.
  • the carbonate content of this thermally treated powder determined according to DIN ISO 10693, is 3.2% by weight.
  • 100 g of this thermally treated powder are mixed with 2 g of graphite and molded bodies with a diameter of about 3 mm and a height of about 3 mm.
  • Carbonate content of catalyst 6, determined according to DIN ISO 10693, is 3.1% by weight.
  • Catalyst 7 is prepared by thermally treating uncalcined material (prepared as described in Reference Example 1) for 6 hours at 280 ° C.
  • the carbonate content of this thermally treated powder determined according to DIN ISO 10693, is 2.2 wt .-%.
  • 100 g of this thermally treated powder are mixed with 2 g of graphite and tabletted into moldings having a diameter of about 3 mm and a height of about 3 mm.
  • the carbonate content of catalyst 7, determined according to DIN ISO 10693, is 2.2% by weight.
  • Calcined material is prepared by calcining uncalcined material (prepared as described in Reference Example 1) in a convection oven at 325 ° C for 2 hours.
  • the carbonate content of the calcined material determined according to DIN ISO 10693, is 4.9 wt .-%.
  • Catalyst 8 is prepared by adding 15 g of the uncalcined material (prepared as described in Reference Example 1) to 85 g of the 325 ° C calcined powder (prepared as in
  • a comparative catalyst is a catalyst containing 26 wt .-% Cu and 53 wt .-% Zn.
  • the carbonate content, determined according to DIN ISO 10693, is 2.5% by weight.
  • the comparative catalyst is in the form of tablets having a diameter of about 3 mm and a height of about 3 mm and has a pore volume of 210 mm-Vg and a Cu-metal surface of 12.8 m ⁇ / g.
  • the activity of the catalysts is investigated with respect to the hydrogenation of fatty acid methyl ester (FAME).
  • FAME fatty acid methyl ester
  • an electrically heated fixed bed reactor with a reactor volume of 25 ml is used.
  • Catalysts are given as values for the conversions to C12-methyl ester at 180 ° C. It can be clearly seen the improved activity of the catalysts of the invention compared to
  • the Cu metal surface of the catalysts is determined by the principle of N2O decomposition:
  • the sample is reduced in a reduction furnace TRACE GC ULTRA (Fa. Brechbühler) for 16 h at 240 ° C with hydrogen (forming gas 5% H2 in He).
  • the sample is then transferred to Thermo Electron's TPDRO 1100 Series, purged with He, and N20 pulse chemisorption started.
  • the Cu metal surface results from the amount of 2 formed in He, which is determined by a thermal conductivity detector.
  • Table 2 shows the values for the carbonate content of
  • Catalysts vary depending on the duration of the thermal treatment.
  • the carbonate content correlates with the Cu metal surface of the reduced catalysts. In a range from 3.1 to 12.1% by weight of carbonate, the result is a relatively high
  • Profitability in particular an increase in sales to the target product is achieved.

Abstract

L'invention concerne un procédé de fabrication d'un corps moulé catalytique Cu-Zn pour l'hydrogénation de composés organiques qui comprennent une fonction carbonyle. Le corps moulé catalytique est en particulier approprié pour l'hydrogénation des aldéhydes, des cétones ainsi que des acides carboxyliques et/ou leurs esters, en particulier des acides gras ou leurs esters, comme les esters méthyliques d'acides gras, pour donner les alcools correspondants, pour l'hydrogénation des anhydrides d'acide dicarboxylique comme l'anhydride d'acide maléique (MSA) ou leurs esters de diacides, pour donner des dialcools, comme le butanediol. En outre, l'invention concerne des catalyseurs Cu-Zn pouvant être obtenus par le procédé de fabrication.
EP15711489.3A 2014-03-26 2015-03-19 Catalyseur d'hydrogénation et son procédé de fabrication Withdrawn EP3122453A1 (fr)

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PCT/EP2015/055758 WO2015144548A1 (fr) 2014-03-26 2015-03-19 Catalyseur d'hydrogénation et son procédé de fabrication

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CN106083777B (zh) * 2016-08-18 2019-01-01 广西驰胜农业科技有限公司 一种从油茶壳中制备糠醛的方法
EP3320971A1 (fr) 2016-11-15 2018-05-16 Basf Se Catalyseur méchaniquement stable pour l'hydrogénation de composés carbonylés et son procédé de fabrication
DE102016225171A1 (de) * 2016-12-15 2018-06-21 Clariant International Ltd Tablettierter Katalysator für die Methanolsynthese mit erhöhter mechanischer Stabilität
EP3345890A1 (fr) 2017-01-05 2018-07-11 Lanxess Deutschland GmbH Procédé de production de n-méthyle-p-toluidine pour son utilisation en tant qu'additif dans le kérosène
CN111318282B (zh) * 2018-12-13 2023-11-07 中国石油化工股份有限公司 一种铜基催化剂及其制备方法和其在制备羟基酮化合物中的应用
DE102019131569A1 (de) * 2019-11-22 2021-05-27 Clariant International Ltd Chromfreier wasser- und saeurestabiler katalysator fuer hydrierungen
CN113058608B (zh) * 2020-01-02 2023-01-13 万华化学集团股份有限公司 一种用于αα-二甲基苄醇氢解制异丙苯的催化剂及其制备方法
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DE102014004413A1 (de) 2015-10-01
US10226760B2 (en) 2019-03-12
MY175612A (en) 2020-07-01
WO2015144548A1 (fr) 2015-10-01
PH12016501666A1 (en) 2016-10-03
GB2543162A (en) 2017-04-12
US20170113209A1 (en) 2017-04-27

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