Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/132—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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/656—Manganese, technetium or rhenium
  • B01J23/6567—Rhenium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals

Definitions

• the invention relates to a process for the preparation of aliphatic alcohols by hydrogenation of aliphatic carboxylic acids or anhydrides or esters thereof or lactones in the presence of a catalyst.
• DE-A-27 15 667 describes a process for the preparation of 1,4-butanediol by hydrogenation of maleic anhydride, maleic acid or fumaric acid, Pd and Re being used as catalyst on a special silicon acetate.
• the reaction temperature is 205 to 230 ° C.
• EP-B-0 417 867 describes catalysts for the hydrogenation of carboxylic acids and their anhydrides to alcohols or esters.
• Pd, Pd / Re, Ag / Pd, Ag / Pd / Re on carbon are used as catalysts.
• the reactions from acetic acid to ethanol and from maleic anhydride to gamma-butyrolactone are described.
• the reaction is carried out at temperatures in the range from 194 to 251 ° C.
• No. 4,214,106 describes a process for the production of ethylene glycol from glycolic acid.
• the reaction is carried out on Pd / Re, Pd / Ag, Ru / Rh, Pd / Au, Re / Ag, Pt / Rh or Pd / Re / Ag as catalysts at a temperature in the range from 145 to 241 ° C.
• the known catalysts do not have sufficiently high activities or selectivities in all applications.
• the object of the present invention is to provide a process for the preparation of aliphatic alcohols by hydrogenation of aliphatic carboxylic acids having at least 3 carbon atoms or anhydrides or esters thereof or lactones in the presence of a catalyst containing Pt and Re in metallic or oxidic form, which has the disadvantages of the known processes avoids.
• the object is achieved according to the invention by using a catalyst which, in addition to Pt and Re in each case in metallic and oxidic form, also has at least one further element from groups 5 to 12 and 14 and the lanthanides of the Periodic Table of the Elements in metallic or oxidic form.
• the invention also relates to such a catalyst and the use thereof for the hydrogenation of aliphatic carboxylic acids or anhydrides or esters thereof or lactones.
• the above-mentioned reaction can be carried out at low temperatures, preferably at most 200 ° C., using the catalyst according to the invention, which leads to a very great reduction in the corrosion problem in the apparatus.
• the catalyst according to the invention or used according to the invention contains or in particular consists of Pt, Re and at least one further element from groups 5 to 12 and 14 and the lanthanides of the periodic table of the elements (IV. Main group, L, II., V., VI. , VII., VIII. Subgroup of the Periodic Table of the Elements) each in metallic or oxidic form, optionally on a support.
• the invention further relates to a catalyst which can be prepared by reducing an aqueous slurry and / or solution of oxides, oxide hydrates, carbonates, nitrates, carboxylates, chelates, sulfates, phosphates and / or halides of Pt, Re and at least one further element from groups 5 to 12 and 14 and the lanthanides of the periodic table of the elements.
• the at least one further element preferably originates from the groups
• the catalyst contains only one further element in metallic or oxidic form.
• the catalyst can be used as a full or supported catalyst.
• all suitable materials can be used as the support material, for example activated carbons, SiO 2 , Al 2 O 3 , TiO 2 , ZrO 2 , clays, such as montmorillonites, zeolites or mixtures thereof.
• the catalyst can be produced in different ways.
• the catalyst can be prepared by reducing an aqueous slurry and / or solution of oxides, oxide hydrates, carbonates, nitrates, carboxylates, chelates, in particular with 1,3-diketo compounds, sulfates, phosphates and / or halides of Pt, Re and at least one other Element from groups 5 to 12 and 14 and the lanthanides of the periodic table of the elements.
• the production can be carried out in such a way that all components are introduced together and are preferably reduced with hydrogen. However, the reduction can also take place one after the other.
• the activation or reduction of the catalyst or the catalyst precursor is preferably carried out at temperatures from 200 to 500 ° C., particularly preferably from 210 to 400 ° C., in particular from 220 to 300 ° C.
• the catalysts are often not present or only to a small extent as intermetallic compounds.
• PtO ⁇ a Re compound such as Re 2 O 7 and at least one further compound of the third component are initially introduced in water and then reduced with hydrogen.
• the catalyst obtained in this way can be used directly for the hydrogenation.
• Supported catalysts can for example are produced in such a way that platinum oxide or platinum oxide hydrate is already on the support, the Pt / support mixture being able to be produced by impregnation or joint precipitation of the platinum oxide or platinum oxide hydrate precursor and support material and subsequent calcination.
• the re-compounds and the further component can additionally be applied by impregnation or precipitation.
• the platinum oxide or platinum oxide hydrate may have already been reduced on the support beforehand.
• the weight ratio of Pt to Re or Pt to the at least one further element is preferably from 100 to 0.01, particularly preferably 50 to 0.05, in particular 10 to 0.1 L.
• Pt is preferably used in the form of the oxide or hydrated oxide before the reduction or activation.
• the Pt component is in the form of PtO 2 .
• Conventional Re compounds can be used as the Re source, preferably Re 2 O 7 .
• the catalysts can be obtained in powder form, in the form of shaped bodies such as extrudates, tablets, pellets or as a fixed bed.
• all aliphatic carboxylic acids or anhydrides or esters thereof or lactones can be hydrogenated to the aliphatic alcohols in the process according to the invention.
• the aliphatic carboxylic acid preferably has at least 3 carbon atoms, particularly preferably at least 4 carbon atoms.
• the number of carbon atoms refers to the individual acid and includes that Carboxyl groups.
• derivatives of carboxylic acid have more carbon atoms.
• the carboxylic acid contains no OH groups adjacent to the carboxyl groups or no hydroxyl groups at all.
• the number of carboxyl groups in the carboxylic acid is not critical. Mono-, di-, tri- or tetracarboxylic acids are usually used, particularly preferably mono- or dicarboxylic acids.
• the number of carbon atoms in the carboxylic acid is also not critical. It preferably has 3 to 30, in particular 4 to 20, especially 4 to 10 carbon atoms.
• the aliphatic radical can be linear or branched. It can have one or more double and / or triple bonds in the framework. Conventional anhydrides or esters can be used in the process according to the invention instead of the free carboxylic acid.
• suitable carboxylic acids are monocarboxylic acids, such as propionic acid, butyric acid, pentanoic acid, hexanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid and octadecanoic acid.
• the monocarboxylic acids can be unsaturated.
• suitable dicarboxylic acids are succinic acid, fumaric acid, maleic acid and adipic acid.
• lactones examples are butyrolactone, methylbutyrolactone or caprolactone.
• the alcohols obtained can be used in many ways, for example as solvents, intermediates or alcohol components for polymers.
• Dicarboxylic acids can be used undiluted in hydrogenation or in solution or suspension.
• Suitable solvents are all substances which are inert under the reaction conditions, such as water, dioxane, tetrahydrofuran, ethylene glycol ether, hydrocarbons such as hexane or alcohols such as methanol, ethanol or the reaction product obtained in the reaction. Water and / or alcohols formed in the reaction are preferably used as solvents.
• butanol is used in the hydrogenation of butyric acid.
• the hydrogenation can be carried out continuously or batchwise.
• the catalysts are arranged, for example, in powder form, in the case of the continuous mode of operation, for example in a fixed bed.
• a product return can be provided for continuous operation.
• the temperature during the hydrogenation is preferably at most 200 ° C.
• the hydrogenation temperatures are preferably in the range from 30 to 200 ° C., particularly preferably 100 to 185 ° C., in particular 120 to 170 ° C.
• the reaction pressure which is generally set using hydrogen, is preferably in the range from 1 to 350 bar.
• the reaction can be carried out in the gas phase, the pressure preferably being 1 to 80 bar.
• the pressure is preferably 20 to 330 bar, particularly preferably 100 to 300 bar.
• the hydrogenation can be carried out in the presence of water.
• Esters thereof in the presence of the catalyst according to the invention can also form lactones by ring closure in addition to aliphatic diols.
• the selectivity with respect to diol or lactone can be controlled by suitable selection of the at least one further element of the catalyst. For example, when using cobalt acetate as the source for the further element, predominantly methylbutyrolactones are formed in the reduction of itaconic acid. When using palladium acetate as the source for the further element, predominantly 2-methylbutanediol is formed.
• Example 3 Analogously to Example 1, itaconic acid was hydrogenated. At 100% conversion, 45.2% 2-methylbutanediol and 47.9% methylbutyrolactone were found in the reaction discharge. The rest consisted mainly of 3-methyltetrahydrofuran, 2-methylbutanol and 3-methylbutanol.
• Example 2 Analogously to Example 2, cobalt acetate was used for the catalyst preparation instead of silver acetate. After hydrogenation as in Example 2, 17.1% of 2-methylbutanediol and 75.6% of methylbutyrolactones were found in the reaction discharge. The rest consisted mainly of 3-methyltetrahydrofuran, 2-methylbutanol and 3-methylbutanol.
• triphenylphosphinogold nitrate was used for the catalyst preparation instead of silver acetate.
• 2-methylbutanediol and 24.4% methylbutyrolactones were found in the reaction discharge.
• the rest consisted mainly of 3-methyltetrahydrofuran, 2-methylbutanol and 3-methylbutanol.
• Example 2 Analogously to Example 2, instead of silver acetate, palladium acetate was used for the catalyst preparation. After hydrogenation as in Example 2, 76.7% of 2-methylbutanediol and 1.8% of methylbutyrolactones were found in the reaction discharge. The rest consisted mainly of 3-methyltetrahydrofuran, 2-methylbutanol and 3-methylbutanol.
• Example 2 Analogously to Example 1, maleic acid was hydrogenated at 140 ° C. With 100% conversion, 70% 1,4-butanediol was found in the discharge. The rest consisted mainly of tetrahydrofuran, gamma-butyrolactone, 4-hydroxybutyraldehyde and butanol.

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

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• 1997
  • 1997-05-16 DE DE19720657A patent/DE19720657A1/de not_active Withdrawn
• 1998
  • 1998-05-12 DE DE59806195T patent/DE59806195D1/de not_active Expired - Lifetime
  • 1998-05-12 WO PCT/EP1998/002777 patent/WO1998052891A1/de not_active Ceased
  • 1998-05-12 US US09/423,876 patent/US6204417B1/en not_active Expired - Lifetime
  • 1998-05-12 ES ES98925581T patent/ES2187029T3/es not_active Expired - Lifetime
  • 1998-05-12 JP JP54989498A patent/JP4138025B2/ja not_active Expired - Fee Related
  • 1998-05-12 CN CN98805932A patent/CN1109009C/zh not_active Expired - Fee Related
  • 1998-05-12 EP EP98925581A patent/EP0983219B1/de not_active Expired - Lifetime

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