US20060041167A1 - Microporous catalyst and method for hydrogenating aromatic compounds - Google Patents

Microporous catalyst and method for hydrogenating aromatic compounds Download PDF

Info

Publication number
US20060041167A1
US20060041167A1 US10/519,413 US51941305A US2006041167A1 US 20060041167 A1 US20060041167 A1 US 20060041167A1 US 51941305 A US51941305 A US 51941305A US 2006041167 A1 US2006041167 A1 US 2006041167A1
Authority
US
United States
Prior art keywords
catalyst
support material
metal
hydrogenation
periodic table
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.)
Abandoned
Application number
US10/519,413
Other languages
English (en)
Inventor
Michael Grass
Alfred Kaizik
Wilfried Buschken
Axel Tuchlenski
Dietrich Maschmeyer
Kurt-Alfred Gaudschun
Frank Brocksien
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.)
Evonik Operations GmbH
Original Assignee
Individual
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 Individual filed Critical Individual
Assigned to OXENO OLEFINCHEMIE GMBH reassignment OXENO OLEFINCHEMIE GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BROCKSIEN, FRANK, BUESCHKEN, WILFRIED, GAUDSCHUN, KURT-ALFRED, GRASS, MICHAEL, KAIZIK, ALFRED, MASCHMEYER, DIETRICH, TUCHLENSKI, AXEL
Publication of US20060041167A1 publication Critical patent/US20060041167A1/en
Priority to US12/025,292 priority Critical patent/US8207375B2/en
Assigned to EVONIK OXENO GMBH reassignment EVONIK OXENO GMBH CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: OXENO OLEFINCHEMIE GMBH
Assigned to EVONIK DEGUSSA GMBH reassignment EVONIK DEGUSSA GMBH MERGER (SEE DOCUMENT FOR DETAILS). Assignors: EVONIK OXENO GMBH
Abandoned legal-status Critical Current

Links

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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • 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
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J35/66—Pore distribution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • 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
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the invention relates to the hydrogenation of aromatic compounds, in particular the preparation of alicyclic polycarboxylic acids or their esters by core hydrogenation of the corresponding aromatic polycarboxylic acids or their esters, and also to catalysts suitable therefor.
  • Alicyclic polycarboxylic esters for example the esters of cyclohexane-1,2-dicarboxylic acid, are used as lubricant components and as assistants in metal processing. They also find use as plasticizers for polyolefins and for PVC.
  • esters of phthalic acid are used predominantly, for example the dibutyl, dioctyl, dinonyl or didecyl esters. Since the use of these phthalates has been discussed with increasing controversy in recent times, their use in plastics could be restricted. Alicyclic polycarboxylic esters, some of which have already been described as plasticizers for plastics in the literature, could then be available as suitable substitutes.
  • the most economical route for preparing alicyclic polycarboxylic esters is the core hydrogenation of the corresponding aromatic polycarboxylic esters, for example the abovementioned phthalates.
  • U.S. Pat. No. 3,027,398 discloses the hydrogenation of dimethyl terephthalate over supported Ru catalysts at from 110 to 140° C. and from 35 to 105 bar.
  • DE 28 23 165 discloses the hydrogenation of aromatic carboxylic esters over supported Ni, Ru, Rh and/or Pd catalysts to the corresponding alicyclic carboxylic esters at from 70 to 250° C. and from 30 to 200 bar.
  • a macroporous support having an average pore size of 70 nm and a BET surface area of approx. 30 m 2 /g is used.
  • WO 99/32427 and WO 00/78704 disclose processes for hydrogenating benzenepolycarboxylic esters to the corresponding alicyclic compounds.
  • Supported catalysts are used which comprise a metal of transition group, VIII alone or together with at least one metal of transition group I or VII of the Periodic Table and have macropores.
  • a preferred metal of transition group VIII used is ruthenium.
  • To hydrogenate three different catalyst types are used which differ substantially by their average pore diameter and BET surface areas.
  • Catalyst I average pore. diameter greater than 50 nm and BET surface area less than 30 m 2 /g
  • Catalyst II average pore diameter from 5 to 20 nm and BET surface area greater than 50 m 2 /g
  • Catalyst III average-pore diameter greater than 100 nm and BET surface area less than 15 m 2 /g
  • the pore volume formed by pores of a certain diameter is specified.
  • the support materials used in the preparation of catalyst II have a pore distribution in which from approx. 5 to approx. 50% of the pore volume by macropores (diameter from approx. 50 nm to 10 000 nm) and from approx. 70 to approx. 90% of the pore volume by mesopores (diameter from approx. 2 to 50 nm).
  • the average pore diameter is between approx. 5 and 20 nm.
  • the activity and selectivity of hydrogenation catalysts depends on their surface properties such as pore size, BET surface area or surface concentration of the active metals.
  • the catalysts used for the core hydrogenation of aromatic carboxylic acids or their esters should allow a high reaction rate, only generate a small proportion of by-products and have a long on-stream time.
  • a catalyst In a continuously operated process, a catalyst is exposed to mechanical, thermal and chemical stresses which change the pore size and the BET surface area and thus reduce the activity and selectivity of this catalyst.
  • Aromatic polycarboxylic esters frequently contain small amounts of carboxylic acids, and traces of acid additionally form during the core hydrogenation of esters. Partial esters of polycarboxylic acids or polycarboxylic acids themselves are acidic as a consequence of their structure. Therefore, a hydrogenation catalyst suitable for a continuous process should be resistant to acid even at relatively high temperatures under the hydrogenation conditions.
  • the surface properties of the catalysts are also responsible for their reactivity.
  • the existing catalysts are in need of improvement in this respect.
  • catalysts which comprise at least one metal of the eighth transition group of the Periodic Table and consist of a support material having an average pore diameter of from 2 to 50 nm and a narrow pore distribution having a fine-pored surface structure hydrogenate aromatic carboxylic acids and/or their esters (full or partial esters) in high selectivity and space-time yield without significant side reactions to the corresponding alicyclic polycarboxylic acids or their esters.
  • the present invention therefore provides a catalyst for hydrogenating aromatic compounds to the corresponding alicyclic compounds, said catalyst comprising at least one metal of the eighth transition group of the Periodic Table on or in a support material, wherein the support material has an average pore diameter of from 2 to 50 nm and that over 91% of the total pore volume of the support materials is accounted for by pores having a diameter of less than 50 nm.
  • Catalysts of this type may be used particularly for hydrogenating aromatic compounds.
  • a process for catalytically hydrogenating aromatic compounds using hydrogen-containing gases over a catalyst which comprises at least one metal of the eighth transition group of the Periodic Table on or in a support material, wherein that the support material has an average pore diameter of from 2 to 50 nm and over 91% of the total pore volume of the support materials is accounted for by pores having a diameter of less than 50 nm likewise forms part of the subject matter of the present invention.
  • the catalysts may comprise any metal of the eighth transition group of the Periodic Table.
  • the active metals used are preferably platinum, rhodium, palladium, cobalt, nickel or ruthenium or a mixture of two or more thereof, and ruthenium in particular is used as the active metal.
  • At least one metal of the first and/or seventh transition group of the Periodic Table may additionally be present in the catalysts. Preference is given to using rhenium and/or copper.
  • the content of active metals i.e. the metals of the first and/or seventh and/or eighth transition group of the Periodic Table is generally from 0.1 to 30% by mass.
  • the noble metal content i.e. the metals of the eighth transition group of the Periodic Table and of the fifth or sixth period, e.g. palladium, ruthenium, calculated as the metal, is in the range from 0.1 to 10% by mass, in particular in the range from 0.8 to 5% by mass, very particularly between 1 and 3% by mass.
  • support materials having an average pore diameter which is in the range from 2 to 50 nm are used.
  • the average pore diameter is determined by Hg porosimetry, in particular to DIN 66133.
  • micropores pore diameter less than 2 nm
  • mesopores pore diameter from 2 to 50 nm
  • macropores pore diameter greater than 50 nm
  • the average pore diameter of the support material is between 2 and 50 nm.
  • the average pore diameter is from 5 to 24 nm, more preferably from 10 to 19 nm.
  • the specific surface area of the support (determined by the BET process by nitrogen adsorption, to DIN 66 131 is 1-350 m 2 /g, preferably 1-200 m 2 /g, more preferably 1-100 m 2 /g, in particular 10-90 m 2 /g or 50-80 m 2 /g or 1-40 m 2 /g.
  • the catalysts are prepared using support materials in which over 95%, in particular over 97%, of the total pore volume is accounted for by micro- and mesopores, i.e. pores having a diameter of from 2 to 50 nm.
  • the total pore volume of the catalyst according to the invention is from 0.25 to 0.50 ml/g, in particular from 0.28 to 0.43 ml/g.
  • the carriers used for the preparation of the catalysts according to the invention are solids whose average pore diameter and whose specific surface area are within the abovementioned ranges.
  • the carriers used may be, for example, the following materials: activated carbon, silicon carbide, aluminum oxide, silicon oxide, aluminosilicate, titanium dioxide, zirconium dioxide, magnesium oxide and/or zinc oxide or their mixtures.
  • these support materials may comprise alkali metals, alkaline earth metals and/or sulfur.
  • the starting material used for the preparation of the catalysts according to the invention is preferably a titanium hydroxide (metatitanic acid).
  • Metatitanic acid is obtained as an intermediate in TiO 2 preparation according to the classical sulfate process by digestion of ilmenite with sulfuric acid (cf. Ullmann's Encyklopädie der ischen Chemie, 4th edition, vol. 18 (1979), p. 574 ff).
  • the sulfuric acid-containing metatitanic acid after substantial removal of the sulfuric acid and washing with demineralized water and also partial peptizing with nitric acid, is converted to a titanium dioxide of the anatase type by calcining at from 490 to 530° C.
  • the sulfuric acid may be removed by neutralizing with ammonia or alkali metal hydroxide solutions and subsequent water washing.
  • Another possibility of deacidification involves washing the sulfuric acid-containing metatitanic acid with water-soluble barium salts, for example barium nitrate, barium chloride or barium carbonate, and washing with water.
  • barium salts for example barium nitrate, barium chloride or barium carbonate
  • titanium dioxide is obtained which comprises barium salts and possibly small amounts of sulfuric acid and sulfate.
  • the material obtained in this way is ground to the desired particle sizes and sieved.
  • the calcined TiO 2 powder and/or TiO 2 powder mixtures are homogenized with the addition of water and plasticizing assistant in a mixing apparatus, for example in a kneader or stirrer, and shaped in a shaping apparatus, for example in an extruder or a tableting machine, to give shaped bodies of a desired shape, such as extrudates or tablets.
  • Subsequent drying at 80-120° C. and calcining at 450-550° C. provides the finished TiO 2 support having the pore structure according to the invention.
  • the barium content is between 1.0 and 4.0% by mass.
  • the content of “free” sulfate may be 1.0-5.5% by mass.
  • Free sulfate refers to sulfur, calculated as sulfate of oxidation state 6, which is not present as barium sulfate. Free sulfate may be determined, for example, by titration after oxidative treatment of the catalyst material in aqueous solution, since barium sulfate as a very substantially insoluble salt is not included in the determination.
  • the catalysts according to the invention may be obtained by applying at least one metal of the eighth transition group of the Periodic Table and optionally at least one metal of the first and/or seventh transition group of the Periodic Table to a suitable support. It is also possible to prepare the active metals and the support at the same time, i.e. use an unsupported catalyst.
  • the application may be achieved by saturating the support in aqueous metal solutions, for example aqueous ruthenium salt solutions, by spraying appropriate metal salt solutions onto the support or by other suitable processes.
  • aqueous metal solutions for example aqueous ruthenium salt solutions
  • Useful metal salts of the first, seventh or eighth transition group of the Periodic Table include the nitrates, nitrosyl nitrates, halides, carbonates, carboxylates, acetylacetonates, chloro complexes, nitrito complexes or amine complexes of the appropriate metals, and preference is given to the nitrates and nitrosyl nitrates.
  • the metal salts or metal salt solutions may be applied at the same time or in succession.
  • the supports coated or saturated with metal salt solution are then dried, preferably at temperatures of from 80 to 150° C., and optionally calcined at temperatures of from 200 to 600° C. In the case of separate saturation, the catalyst is dried after each saturation step and optionally calcined as described above.
  • the sequence in which the active components are applied can be chosen freely.
  • the application of the active components, drying and calcining may be effected in one operation, for example by spraying an aqueous metal salt solution onto the support at temperatures over 200° C.
  • the catalysts according to the invention are advantageously brought into a shape which offers a low flow resistance on hydrogenation, for example tablets, cylinders, extrudates or rings.
  • the shaping may be effected when desired at different points in the catalyst preparation.
  • the hydrogenation is, carried out in the liquid phase or in the gas phase.
  • the hydrogenation may be carried out continuously or batchwise over suspended catalysts or catalysts arranged in pieces in a fixed bed.
  • preference is given to a continuous hydrogenation over a catalyst arranged in a fixed bed in which the product/reactant phase is mainly in the liquid state under the reaction conditions.
  • the hydrogenation is carried out continuously over a catalyst arranged in a fixed bed, it is advantageous to convert the catalyst into the active form before the hydrogenation.
  • This may be effected by reducing the catalyst with hydrogen-containing gases by a temperature program.
  • the reduction may optionally be carried out in the presence of a liquid phase which trickles over the catalyst.
  • the liquid phase used may be a solvent or the hydrogenation product.
  • different process variants may be selected. It may be carried out adiabatically, polytropically or virtually isothermally, i.e. with a temperature rise of typically less than 10° C., in one or more stages. In the latter case, all reactors, advantageously tubular reactors, may be operated adiabatically or virtually isothermally, or else one or more may be operated adiabatically and the others virtually isothermally. It is also possible to hydrogenate the aromatic compounds in straight pass or with product recycling.
  • the reactors are preferably operated with high liquid superficial velocities of from 15 to 120, in particular from 25 to 80, m 3 per m 2 of cross section of the empty reactor and hour.
  • the liquid hourly space velocity may assume values between 0.1 and 10 h ⁇ 1 .
  • the hydrogenation may be carried out in the absence or preferably in the presence of a solvent.
  • a solvent are any liquids which form a homogeneous solution with the reactant and product, behave inertly under the hydrogenation conditions and can be easily removed from the product.
  • the solvent may also be a mixture of several solvents and optionally comprise water.
  • straight-chain or cyclic ethers for example tetrahydrofuran or dioxane, and also aliphatic alcohols in which the alkyl radical has from 1 to 13 carbon atoms.
  • Alcohols which can be used with preference are isopropanol, n-butanol, isobutanol, n-pentanol, 2-ethylhexanol, nonanols, technical nonanol mixtures, decanol, technical decanol mixtures and tridecanols.
  • alcohols are used as solvents, it may be advantageous to use that alcohol or that alcohol mixture which would be formed on hydrolysis of the product. This would rule out by-product formation by transesterification.
  • a further preferred solvent is the hydrogenation product itself.
  • the use of a solvent allows the aromatic concentration in the reactor feed to be limited, which allows better temperature control in the reactor. This may have the consequence of minimizing secondary reactions and thus increasing the product yield.
  • the aromatic content in the reactor feed is preferably between 1 and 35%, in particular between 5 and 25%.
  • the desired concentration range may be attained via the circulation ratio (ratio of recycled hydrogenation effluent to reactant).
  • the process according to the invention is carried out within a pressure range of from 3 to 300 bar, in particular between 15 and 200 bar, very particularly between 50 and 200 bar.
  • the hydrogenation temperatures are between 50 and 250° C., in particular between 100 and 200° C.
  • the hydrogenating gases used may be any desired hydrogen-containing gas mixtures which do not contain any damaging amounts of catalyst poisons, for example carbon monoxide or hydrogen sulfide.
  • the use of inert gases is optional, and preference is given to using hydrogen in a purity of greater than 95%, in particular greater than 98%.
  • Inert gas constituents may be, for example, nitrogen or methane.
  • the individual reactors may be charged with fresh hydrogen.
  • feedstock and hydrogenation gas flow in opposite sequence through the reactors. It is advantageous to maintain the hydrogen excess, based on the stoichiometric amount required, below 30%, in particular below 10%, very particularly below 5%.
  • the hydrogenation of octyl, nonyl, decyl or dodecyl phthalates is preferably carried out under the following conditions:
  • the concentration of these phthalates at the entrance of the first reactor is between 1 and 30% by mass, preferably between 2 and 10% by mass, most preferably between 3 and 8% by mass.
  • the concentration of the phthalates is between 0.5 and 20% by mass, in particular between 1 and 10% by mass.
  • the liquid hourly space velocity (LHSV, liters of fresh reactant per liter of catalyst per hour) in the loop reactor is from 0.1 to 5 h ⁇ 1 , in particular from 0.5 to 3 h ⁇ 1 .
  • the superficial velocity in the loop reactor is in the range from 10 to 100 m 3 /m 2 /h, preferably in the range from 20 to 80 m 3 /m 2 /h, most preferably in the range from 40 to 60 m 3 /m 2 /h.
  • the average hydrogenation temperatures in the loop reactor are from 60 to 150° C., in particular from 70 to 120° C.
  • the hydrogenation pressure in the loop reactor is from 25 to 200 bar, in particular from 80 to 110 bar.
  • the concentration of reactant is less than 0.3% by mass, in particular less than 0.1% by mass, very particularly less than 0.05% by mass.
  • the liquid hourly space velocity in the second reactor (liters of nonyl phthalate per liter of catalyst per hour) is from 1 to 20 h ⁇ 1 , in particular from 2 to 10 h ⁇ 1 .
  • the average temperature is between 60 and 150° C., in particular 70 and 120° C.
  • the hydrogenation pressure in the second reactor is from 25 to 200 bar, in particular from 80 to 110 bar.
  • the process according to the invention allows aromatic compounds such as aromatic poly- and/or monocarboxylic acids or their derivatives, in particular their alkyl esters, to be converted to the corresponding alicyclic polycarboxylic acid compounds.
  • Both full esters and partial esters may be hydrogenated.
  • a full ester is a compound in which all acid groups are esterified.
  • Partial esters are compounds having at least one free acid group (or optionally an anhydride group) and at least one ester group.
  • polycarboxylic esters When polycarboxylic esters are used in the process according to the invention, these preferably contain 2, 3 or 4 ester functions.
  • the aromatic compounds or polycarboxylic esters used in the process according to the invention are preferably polycarboxylic acids of benzene, diphenyl, naphthalene and/or anthracene, their anhydrides and/or the corresponding esters.
  • the resulting alicyclic polycarboxylic acids or their derivatives consist of one or more C 6 rings, optionally linked via a C—C bond or fused on.
  • the alcohol component of the carboxylic esters used preferably consists of branched or unbranched alkyl, cycloalkyl, or alkoxyalkyl groups having from 1 to 25 carbon atoms. These may be identical or different within one molecule of a polycarboxylic ester, i.e. they may be identical or different isomers or possess an identical or different number of carbon atoms. It will be appreciated that it is also possible to use isomers with regard to the substitution pattern of the aromatic system in the form of a mixture, for example a mixture of phthalic ester and terephthalic ester.
  • the present invention relates to a process for hydrogenating benzene-1,2-, -1,3-, or -1,4-dicarboxylic esters, and/or benzene-1,2,3-, -1,2,4-, or -1,3,5-tricarboxylic esters, i.e. the isomers of cyclohexane-1,2-, -1,3-, or -1,4-dicarboxylic esters, or of cyclohexane-1,2,3-, -1,3,5-, or -1,2,4-tricarboxylic esters are obtained.
  • Esters of the following aromatic carboxylic acids may be used in the process of the invention: naphthalene-1,2-dicarboxylic acid, naphthalene-1,3-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-1,6-dicarboxylic acid, naphthalene-1,7-dicarboxylic acid, naphthalene-1,8-dicarboxylic acid, phthalic acid (benzene-1,2-dicarboxylic acid), isophthalic acid (benzene-1,3-dicarboxylic acid), terephthalic acid.
  • alkyl, cycloalkyl, or else alkoxyalkyl esters for example, of the abovementioned acids, these radicals each independently including from 1 to 25, in particular from 3 to 15, very particularly from 8 to 13, particularly 9, carbon atoms. These radicals may be linear or branched. If a starting material has more than one ester group, these radicals may be identical or different.
  • Examples of compounds which may be used in the process of the invention as esters of an aromatic polycarboxylic acid are the following: monomethyl terephthalate, dimethyl terephthalate, diethyl terephthalate, di-n-propyl terephthalate, dibutyl terephthalate, diisobutyl terephthalate, di-tert-butyl terephthalate, monoglycol terephthalate, diglycol terephthalate, n-octyl terephthalate, diisooctyl terephthalate, di-2-ethylhexyl terephthalate, di-n-nonyl terephthalate, diisononyl terephthalate, di-n-decyl terephthalate, di-n-undecyl terephthalate, diisodecyl terephthalate, diisododecyl terephthalate, ditride
  • the process according to the invention can in principle also be applied to benzoic acid and its esters.
  • benzoates of diols for example glycol dibenzoate, diethylene glycol benzoate, triethylene glycol dibenzoate and propylene glycol dibenzoate, and also alkyl benzoates.
  • the alcohol component of the alkyl benzoates may consist of from 1 to 25, preferably from 8 to 13, carbon atom(s).
  • the alcohols may be linear or branched.
  • mixtures of two or more polycarboxylic esters may be obtained in the following ways:
  • Aromatic esters are frequently prepared industrially from alcohol mixtures, in particular the full esters by route c).
  • C 6 alcohol mixtures prepared from a pentene or from a mixture of two or more pentenes, by hydroformylation followed by hydrogenation;
  • C 8 alcohol mixtures such as 2-ethylhexanol (2 isomers), prepared by aldol condensation of n-butyraldehyde followed by hydrogenation;
  • C 9 alcohol mixtures prepared from C 4 olefins by dimerization, hydroformylation, and hydrogenation.
  • the starting materials for preparing the C 9 alcohols may be isobutene or a mixture of linear butenes or mixtures of linear butenes and isobutene.
  • the C 4 olefins may be dimerized with the aid of various catalysts, for example protic acids, zeolites, organometallic nickel compounds, or solid nickel catalysts.
  • the C 8 olefin mixtures may be hydroformylated with the aid of rhodium catalysts or cobalt catalysts. There is therefore a wide variety of industrial C 9 alcohol mixtures.
  • alcohol mixtures may be obtained by hydroformylation followed by hydrogenation from olefins or olefin mixtures which arise, for example, in Fischer-Tropsch syntheses, in dehydrogenations of hydrocarbons, in metathesis reactions, in the polygas process, or in other industrial processes.
  • Olefin mixtures with olefins of differing carbon numbers may also be used to prepare alcohol mixtures.
  • any ester mixture prepared from aromatic polycarboxylic acids and the abovementioned alcohol mixtures may be used.
  • Vestinol C (di-n-butyl phthalate) (CAS No. 84-74-2); Vestinol IB (diisobutyl phthalate) (CAS No. 84-69-5); Jayflex DINP (CAS No. 68515-48-0); Jayflex DIDP (CAS No. 68515-49-1); Palatinol 9P (68515-45-7), Vestinol 9 (CAS No. 28553-12-0); TOTM (CAS No. 3319-31-1); Linplast 68-TM, Palatinol N (CAS No. 28553-12-0); Jayflex DHP (CAS No. 68515-50-4); Jayflex DIOP (CAS No. 27554-26-3); Jayflex. UDP (CAS. No.
  • Linplast 68 FP (CAS No. 68648-93-1); Linplast 812 HP (CAS No. 70693-30-0); Palatinol AH (CAS No. 117-81-7); Palatinol 711 (CAS No. 68515-42-4); Palatinol 911 (CAS No. 68515-43-5); Palatinol 11 (CAS No. 3648-20-2); Palatinol Z (CAS No. 26761-40-0); Palatinol DIPP (CAS No. 84777-06-0); Jayflex 77 (CAS No. 71888-89-6); Palatinol 10 P (CAS No. 53306-54-0); Vestinol AH (CAS No. 117-81-7).
  • each isomer used in the core hydrogenation of aromatic polycarboxylic acids or their esters may result in at least two stereoisomeric hydrogenation products.
  • the ratios of the resulting stereoisomers to each other depend on the catalyst used and on the hydrogenation conditions.
  • the invention further provides the use of the alicyclic polycarboxylic esters prepared according to the invention as plasticizers in plastics.
  • Preferred plastics include PVC, homo- and copolymers based on ethylene, propylene, butadiene, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, acrylates, acrylates having alkyl radicals of branched or unbranched alcohols having from one to ten carbon atom(s) bonded to the oxygen atom of the ester group, styrene or acrylonitrile, or homo- or copolymers of cyclic olefins.
  • polyacrylates having the same or different alkyl radicals having from 4 to 8 carbon atoms bonded to the oxygen atom of the ester group, in particular having the n-butyl, n-hexyl, n-octyl, 2-ethylhexyl or isononyl radical, polymethacrylate, polymethyl methacrylate, methyl acrylate-butyl acrylate copolymers, methyl methacrylate-butyl methacrylate copolymers, ethylene-vinyl acetate copolymers, chlorinated polyethylene, nitrile rubber, acrylonitrile-butadiene-styrene copolymers, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, styrene-acrylonitrile copolymers, acrylonitrile-butadiene rubber, styrene-butadiene elastomers, methyl methacrylate-s
  • alicyclic polycarboxylic esters prepared according to the invention may be used for modifying plastic mixtures, for example the mixture of a polyolefin with a polyamide.
  • plastics and the alicyclic polycarboxylic esters prepared according to the invention likewise form part of the subject matter of the present invention.
  • Suitable plastics are the compounds already mentioned.
  • Such mixtures preferably comprise at least 5% by weight, more preferably 20-80% by weight, most preferably 30-70% by weight, of the alicyclic polycarboxylic esters.
  • plastics in particular PVC, which comprise one or more of the alicyclic polycarboxylic esters prepared according to the invention may, for example, be present in the following products or be used for their preparation: casings for electrical equipment, for example kitchen appliances, computer casings, casings and components of phonographic and television equipment, pipes, apparatus, cables, wire sheaths insulating tapes or window profiles, in interior decoration, in vehicle and furniture construction, plastisols, floor coverings, medical products, food packaging, seals, films, composite films, phonographic disks, synthetic leather, toys, packaging containers, adhesive tape films, clothing, coatings and as fibers for fabrics.
  • casings for electrical equipment for example kitchen appliances, computer casings, casings and components of phonographic and television equipment, pipes, apparatus, cables, wire sheaths insulating tapes or window profiles, in interior decoration, in vehicle and furniture construction, plastisols, floor coverings, medical products, food packaging, seals, films, composite films, phonographic disks, synthetic leather
  • alicyclic polycarboxylic esters prepared according to the invention may also be used as a lubricant component, or as a constituent of cooling liquids and metalworking fluids. They may likewise be used as a component in dyes, paints, inks and adhesives.
  • the solid obtained formally contained 91.5% by mass of titanium dioxide, 5.5% by mass of barium sulfate and 3.1% by mass of free sulfate. This solid was ground to give two powder types and the desired particle size fraction was sieved out.
  • One powder consisted of particles having particle sizes of from 1 to 30 ⁇ m, and the other powder of particles having particle sizes of from 20 to 500 ⁇ m. The two different powder types were mixed in a 1/1 ratio.
  • the total pore volume was determined from the sum of the pore volumes of the pores having a pore diameter >7.6 nm (determined by Hg porosimetry) and pores having a pore diameter ⁇ 7.6 nm (determined by the N 2 adsorption method).
  • the Ru solution in nitric acid was diluted with water to a volume corresponding to the pore volume of the support.
  • the Ru solution was applied to the support material by dropwise application or preferably by uniform spraying while circulating the support. After drying at 120° C. under nitrogen, the support coated with ruthenium salt was activated (reduced) in a hydrogen/nitrogen mixture, (ratio 1:9) at 200° C. for over 6 hours.
  • N.B. The catalysts prepared in this way were referred to in the following text by the same capital letters as the parent supports, and the active metal and its contents were reported in subsequent brackets.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US10/519,413 2002-07-19 2003-06-07 Microporous catalyst and method for hydrogenating aromatic compounds Abandoned US20060041167A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/025,292 US8207375B2 (en) 2002-07-19 2008-02-04 Microporous catalyst and method for hydrogenating aromatic compounds

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10232868.4 2002-07-19
DE10232868A DE10232868A1 (de) 2002-07-19 2002-07-19 Feinporiger Katalysator und Verfahren zur Hydrierung von aromatischen Verbindungen
PCT/EP2003/006002 WO2004009526A1 (de) 2002-07-19 2003-06-07 Feinporiger katalysator und verfahren zur hydrierung von aromatischen verbindungen

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/025,292 Division US8207375B2 (en) 2002-07-19 2008-02-04 Microporous catalyst and method for hydrogenating aromatic compounds

Publications (1)

Publication Number Publication Date
US20060041167A1 true US20060041167A1 (en) 2006-02-23

Family

ID=30010232

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/519,413 Abandoned US20060041167A1 (en) 2002-07-19 2003-06-07 Microporous catalyst and method for hydrogenating aromatic compounds
US12/025,292 Active 2026-08-29 US8207375B2 (en) 2002-07-19 2008-02-04 Microporous catalyst and method for hydrogenating aromatic compounds

Family Applications After (1)

Application Number Title Priority Date Filing Date
US12/025,292 Active 2026-08-29 US8207375B2 (en) 2002-07-19 2008-02-04 Microporous catalyst and method for hydrogenating aromatic compounds

Country Status (10)

Country Link
US (2) US20060041167A1 (ja)
EP (1) EP1549603B1 (ja)
JP (1) JP4490264B2 (ja)
CN (1) CN100341838C (ja)
AT (1) ATE457298T1 (ja)
AU (1) AU2003242651A1 (ja)
DE (2) DE10232868A1 (ja)
ES (1) ES2339937T3 (ja)
TW (1) TWI292723B (ja)
WO (1) WO2004009526A1 (ja)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040097773A1 (en) * 2002-08-06 2004-05-20 Oxeno Olefinchemie Gmbh Oligomerization of isobutene in N-butenic hydrocarbon streams
US20060036121A1 (en) * 2002-12-10 2006-02-16 Oxeno Olefinchemie Gmbh Method for producing 1-olefins by catalytically splitting 1-alkoxyalkanes
US20060167151A1 (en) * 2004-12-31 2006-07-27 Oxeno Olefinchemie Gmbh Method for preparing alicyclic carboxylic acids and their esters
US20070003583A1 (en) * 2003-05-09 2007-01-04 Basf Aktiengesellschaft Cosmetic compositions comprising cyclohexanepolycarboxylic acid derivatives
US20070104627A1 (en) * 2004-09-16 2007-05-10 Oxeno Olefinchemie Gmbh Device for carrying out liquid reactions with fine-grained solid catalysts and method for the use thereof
US20080039646A1 (en) * 2004-06-21 2008-02-14 Basf Aktiengesellschaft Cyclohexane Polycarboxylic Acid Derivatives Containing Adjuvants
US20080188601A1 (en) * 2005-06-22 2008-08-07 Oxeno Olefinchemie Gmbh Mixture of Diisononyl Esters of 1,2-Cyclohexanedicarboxylic Acid, Method For the Production Thereof and Use of These Mextures
KR20100116176A (ko) * 2008-01-28 2010-10-29 에보니크 옥세노 게엠베하 테레프탈산의 디이소노닐 에스테르의 혼합물, 이의 제조 방법 및 이의 용도
US20110060169A1 (en) * 2007-08-31 2011-03-10 Evonik Oxeno Gmbh Hydrogenation catalyst and process for preparing alcohols by hydrogenation of carbonyl compounds
US20110152596A1 (en) * 2006-08-29 2011-06-23 Oxeno Olefinchemie Gmbh Catalyst and process for preparing isoolefins
US20110217552A1 (en) * 2008-12-17 2011-09-08 Evonik Degussa Gmbh Process for preparing an aluminium oxide powder having a high alpha-al2o3 content
US8207375B2 (en) 2002-07-19 2012-06-26 Evonik Oxeno Gmbh Microporous catalyst and method for hydrogenating aromatic compounds
US8455701B2 (en) 2009-10-15 2013-06-04 Evonik Oxeno Gmbh Method for producing decanols by means of hydrogenating decenals
US20130150614A1 (en) * 2011-12-12 2013-06-13 Industrial Technology Research Institute Process for hydrogenation of polycarboxylic acids or derivatives therof
US8841492B2 (en) 2010-10-21 2014-09-23 Evonik Degussa Gmbh Method for purification of mixtures comprising MTBE as well as production of isobutene by splitting of mixtures comprising MTBE
US8846994B2 (en) 2009-07-01 2014-09-30 Evonik Degussa Gmbh Method for producing low-odor n-butane
US8859834B2 (en) 2010-07-06 2014-10-14 Evonik Degussa Gmbh Process for the selective hydrogenation of multiply unsaturated hydrocarbons in olefin-containing hydrocarbon mixtures
US8940951B2 (en) 2009-07-01 2015-01-27 Evonik Degussa Gmbh Preparation of isobutene by dissociation of MTBE
US8980784B2 (en) 2011-03-16 2015-03-17 Evonik Degussa Gmbh Silicon-aluminum mixed oxide powder
US9084983B2 (en) 2009-12-15 2015-07-21 Basf Se Catalyst and process for hydrogenating aromatics
US9371255B2 (en) 2011-03-16 2016-06-21 Evonik Degussa Gmbh Mixed oxide compositions and process for preparing isoolefins
WO2017034160A1 (ko) * 2015-08-27 2017-03-02 한화케미칼 주식회사 프탈레이트 화합물의 수소화 방법
US10000440B2 (en) 2015-11-19 2018-06-19 Evonik Degussa Gmbh Influencing the viscosity of N-butene-based ester mixtures by controlled use of ethene in the preparation of the ester precursors

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004063673A1 (de) * 2004-12-31 2006-07-13 Oxeno Olefinchemie Gmbh Verfahren zur kontinuierlichen katalytischen Hydrierung von hydrierbaren Verbindungen an festen, im Festbett angeordneten Katalysatoren mit einem wasserstoffhaltigen Gas
US8372912B2 (en) * 2005-08-12 2013-02-12 Eastman Chemical Company Polyvinyl chloride compositions
US8476476B2 (en) 2008-10-14 2013-07-02 Exxonmobil Chemical Patents Inc. Offgas cleanup in olefin hydroformylation
JP2010126448A (ja) * 2008-11-25 2010-06-10 Showa Denko Kk β，γ−不飽和アルコールの水素化反応による飽和アルコールの製造方法
EP2471743B1 (en) 2009-08-28 2016-11-16 Nanjing University of Technology Mesoporous composite titania and preparing method thereof
US8921590B2 (en) 2009-12-15 2014-12-30 Exxonmobil Chemical Patents Inc. Oligomerisation process
CN102958900B (zh) 2010-09-20 2016-09-28 埃克森美孚化学专利公司 邻苯二甲酸酯的液相氢化方法
KR20130135286A (ko) 2010-12-23 2013-12-10 바스프 에스이 열가소성 엘라스토머 조성물 및 그의 제조 방법
EP2716623A1 (de) 2012-10-05 2014-04-09 Basf Se Verfahren zur Herstellung von Cyclohexanpolycarbonsäure-Derivaten mit geringem Nebenproduktanteil
EP3077453B1 (de) 2013-12-06 2018-03-28 Basf Se Weichmacher-zusammensetzung, die tetrahydrofuranderivate und 1,2-cyclohexandicarbonsäureester enthält
WO2016027217A1 (en) 2014-08-18 2016-02-25 Basf Se Organic semiconductor composition comprising liquid medium
CN106866415A (zh) * 2015-12-12 2017-06-20 中国科学院大连化学物理研究所 一种脂环族羧酸酯的制造方法
PL3424901T3 (pl) 2017-07-05 2021-01-11 Basf Se Uwodornianie związków aromatycznych
KR102506281B1 (ko) * 2017-11-29 2023-03-06 한화솔루션 주식회사 프탈레이트 화합물의 수소화 방법
TWI704132B (zh) * 2019-02-13 2020-09-11 台灣中油股份有限公司 苯多羧酸酯氫化反應形成脂環族多羧酸酯之氫化方法
KR20210133219A (ko) 2019-02-25 2021-11-05 바스프 에스이 벤젠 폴리카르복실산 에스테르의 가공 방법 및 시클로헥산 폴리카르복실산 에스테르를 생성하기 위한 그의 용도

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US38285A (en) * 1863-04-28 Fluosilicic acid
US260113A (en) * 1882-06-27 Albert l
US4018706A (en) * 1975-07-21 1977-04-19 Nippon Shokubai Kagaku Kogyo Co., Ltd. Catalysts for purifying exhaust and waste gases
US4314982A (en) * 1979-06-21 1982-02-09 General Atomic Company Catalytic decomposition of H2 SO4
US4422960A (en) * 1980-02-19 1983-12-27 Chiyoda Chemical Engineering & Construction Co., Ltd. Catalysts for hydrotreatment of heavy hydrocarbon oils containing asphaltenes
US4427576A (en) * 1981-03-13 1984-01-24 Rhone-Poulenc Specialites Chimques Catalyst for oxidation of hydrogen sulfide and/or organosulfur compounds to SO2 and process for preparing the catalyst
US4665274A (en) * 1985-09-11 1987-05-12 Sumitomo Chemical Company, Limited Method for producing cycloolefins
US5137855A (en) * 1988-06-09 1992-08-11 W. R. Grace & Co.-Conn. Catalysts for selective catalytic reduction denox technology
US5242880A (en) * 1992-05-27 1993-09-07 Eastman Kodak Company Photoactive catalyst of barium phosphate or calcium phosphate supported on anatase titanium dioxide
US5258348A (en) * 1989-10-31 1993-11-02 The Dow Chemical Company Supported catalyst for the dehydrogenation of hydrocarbons and method for the preparation of the catalyst
US5558766A (en) * 1991-05-08 1996-09-24 Intevep, S.A. Hydrocracking of feedstocks and catalyst therefor
US5856578A (en) * 1994-05-27 1999-01-05 Norvartis Corporation Process for the preparation of unsaturated amino compounds
US6284917B1 (en) * 1997-12-19 2001-09-04 Basf Aktiengesellschaft Method for hydrogenating benzene polycarboxylic acids or derivatives thereof by using a catalyst containing macropores
US6344568B1 (en) * 1999-02-19 2002-02-05 Nippon Shokubai Co., Ltd. Catalyst for gas phase partial oxidation
US20040097773A1 (en) * 2002-08-06 2004-05-20 Oxeno Olefinchemie Gmbh Oligomerization of isobutene in N-butenic hydrocarbon streams
US6743819B1 (en) * 2003-03-24 2004-06-01 E. I. Du Ponte De Nemours And Company Production of 5-methyl-N-aryl-2-pyrrolidone and 5-methyl-N-cycloalkyl-2-pyrrolidone by reductive amination of levulinic acid with aryl amines
US20060036121A1 (en) * 2002-12-10 2006-02-16 Oxeno Olefinchemie Gmbh Method for producing 1-olefins by catalytically splitting 1-alkoxyalkanes
US20060167151A1 (en) * 2004-12-31 2006-07-27 Oxeno Olefinchemie Gmbh Method for preparing alicyclic carboxylic acids and their esters

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3143647A1 (de) 1981-11-04 1983-05-11 Chemische Werke Hüls AG, 4370 Marl Verfahren zur selektiven hydrierung von mehrfach ungesaettigten kohlenwasserstoffen in kohlenwasserstoff-gemischen
EP0520435A3 (en) * 1991-06-28 1993-05-05 Kyowa Hakko Kogyo Co., Ltd. Dc-89 derivatives
DE4419974C2 (de) * 1994-06-08 1996-10-17 Huels Chemische Werke Ag Verfahren zur Herstellung eines geformten Katalysators auf der Basis von Titandioxid sowie dessen Verwendung
CN1057982C (zh) * 1998-01-14 2000-11-01 中国科学院固体物理研究所 介孔二氧化钛块体及制备方法
DE19927978A1 (de) 1999-06-18 2000-12-21 Basf Ag Ausgewählte Cyclohexan-1,3- und 1,4-dicarbonsäureester
US6589908B1 (en) * 2000-11-28 2003-07-08 Shell Oil Company Method of making alumina having bimodal pore structure, and catalysts made therefrom
DE10146869A1 (de) 2001-09-24 2003-04-24 Oxeno Olefinchemie Gmbh Alicyclische Polycarbonsäureestergemische mit hohem trans-Anteil und Verfahren zu deren Herstellung
DE10146848A1 (de) 2001-09-24 2003-04-24 Oxeno Olefinchemie Gmbh Gemisch alicyclischer Polycarbonsäureester mit hohem cis-Anteil
DE10225565A1 (de) 2002-06-10 2003-12-18 Oxeno Olefinchemie Gmbh Katalysator und Verfahren zur Hydrierung von aromatischen Verbindungen
DE10232868A1 (de) 2002-07-19 2004-02-05 Oxeno Olefinchemie Gmbh Feinporiger Katalysator und Verfahren zur Hydrierung von aromatischen Verbindungen

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US260113A (en) * 1882-06-27 Albert l
US38285A (en) * 1863-04-28 Fluosilicic acid
US4018706A (en) * 1975-07-21 1977-04-19 Nippon Shokubai Kagaku Kogyo Co., Ltd. Catalysts for purifying exhaust and waste gases
US4314982A (en) * 1979-06-21 1982-02-09 General Atomic Company Catalytic decomposition of H2 SO4
US4422960A (en) * 1980-02-19 1983-12-27 Chiyoda Chemical Engineering & Construction Co., Ltd. Catalysts for hydrotreatment of heavy hydrocarbon oils containing asphaltenes
US4427576A (en) * 1981-03-13 1984-01-24 Rhone-Poulenc Specialites Chimques Catalyst for oxidation of hydrogen sulfide and/or organosulfur compounds to SO2 and process for preparing the catalyst
US4665274A (en) * 1985-09-11 1987-05-12 Sumitomo Chemical Company, Limited Method for producing cycloolefins
US5137855A (en) * 1988-06-09 1992-08-11 W. R. Grace & Co.-Conn. Catalysts for selective catalytic reduction denox technology
US5258348A (en) * 1989-10-31 1993-11-02 The Dow Chemical Company Supported catalyst for the dehydrogenation of hydrocarbons and method for the preparation of the catalyst
US5558766A (en) * 1991-05-08 1996-09-24 Intevep, S.A. Hydrocracking of feedstocks and catalyst therefor
US5242880A (en) * 1992-05-27 1993-09-07 Eastman Kodak Company Photoactive catalyst of barium phosphate or calcium phosphate supported on anatase titanium dioxide
US5856578A (en) * 1994-05-27 1999-01-05 Norvartis Corporation Process for the preparation of unsaturated amino compounds
US6284917B1 (en) * 1997-12-19 2001-09-04 Basf Aktiengesellschaft Method for hydrogenating benzene polycarboxylic acids or derivatives thereof by using a catalyst containing macropores
US6344568B1 (en) * 1999-02-19 2002-02-05 Nippon Shokubai Co., Ltd. Catalyst for gas phase partial oxidation
US20040097773A1 (en) * 2002-08-06 2004-05-20 Oxeno Olefinchemie Gmbh Oligomerization of isobutene in N-butenic hydrocarbon streams
US20060036121A1 (en) * 2002-12-10 2006-02-16 Oxeno Olefinchemie Gmbh Method for producing 1-olefins by catalytically splitting 1-alkoxyalkanes
US6743819B1 (en) * 2003-03-24 2004-06-01 E. I. Du Ponte De Nemours And Company Production of 5-methyl-N-aryl-2-pyrrolidone and 5-methyl-N-cycloalkyl-2-pyrrolidone by reductive amination of levulinic acid with aryl amines
US20060167151A1 (en) * 2004-12-31 2006-07-27 Oxeno Olefinchemie Gmbh Method for preparing alicyclic carboxylic acids and their esters

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8207375B2 (en) 2002-07-19 2012-06-26 Evonik Oxeno Gmbh Microporous catalyst and method for hydrogenating aromatic compounds
US20040097773A1 (en) * 2002-08-06 2004-05-20 Oxeno Olefinchemie Gmbh Oligomerization of isobutene in N-butenic hydrocarbon streams
US7161053B2 (en) 2002-08-06 2007-01-09 Oxeno Olefinchemie Gmbh Oligomerization of isobutene in N-butenic hydrocarbon streams
US20060036121A1 (en) * 2002-12-10 2006-02-16 Oxeno Olefinchemie Gmbh Method for producing 1-olefins by catalytically splitting 1-alkoxyalkanes
US7342144B2 (en) 2002-12-10 2008-03-11 Oxeno Olefinchemie Gmbh Method for producing 1-olefins by catalytically splitting 1-alkoxyalkanes
US20070003583A1 (en) * 2003-05-09 2007-01-04 Basf Aktiengesellschaft Cosmetic compositions comprising cyclohexanepolycarboxylic acid derivatives
US20080039646A1 (en) * 2004-06-21 2008-02-14 Basf Aktiengesellschaft Cyclohexane Polycarboxylic Acid Derivatives Containing Adjuvants
US7816553B2 (en) 2004-06-21 2010-10-19 Basf Se Cyclohexane polycarboxylic acid derivatives containing adjuvants
US20070104627A1 (en) * 2004-09-16 2007-05-10 Oxeno Olefinchemie Gmbh Device for carrying out liquid reactions with fine-grained solid catalysts and method for the use thereof
US7569196B2 (en) 2004-09-16 2009-08-04 Oxeno Olefinchemie Gmbh Device for carrying out liquid reactions with fine-grained solid catalysts and method for the use thereof
US7435848B2 (en) 2004-12-31 2008-10-14 Oxeno Olefinchemie Gmbh Method for preparing alicyclic carboxylic acids and their esters
US20060167151A1 (en) * 2004-12-31 2006-07-27 Oxeno Olefinchemie Gmbh Method for preparing alicyclic carboxylic acids and their esters
US20080188601A1 (en) * 2005-06-22 2008-08-07 Oxeno Olefinchemie Gmbh Mixture of Diisononyl Esters of 1,2-Cyclohexanedicarboxylic Acid, Method For the Production Thereof and Use of These Mextures
US7786201B2 (en) * 2005-06-22 2010-08-31 Evonik Oxeno Gmbh Mixture of diisononyl esters of 1,2-cyclohexanedicarboxylic acid, method for the production thereof and use of these mixtures
US20110152596A1 (en) * 2006-08-29 2011-06-23 Oxeno Olefinchemie Gmbh Catalyst and process for preparing isoolefins
US8680356B2 (en) 2006-08-29 2014-03-25 Evonik Oxeno Gmbh Catalyst and process for preparing isoolefins
US20110060169A1 (en) * 2007-08-31 2011-03-10 Evonik Oxeno Gmbh Hydrogenation catalyst and process for preparing alcohols by hydrogenation of carbonyl compounds
US20100305255A1 (en) * 2008-01-28 2010-12-02 Evonik Oxeno Gmbh Mixtures of diisononyl esters of terephthalic acid, method for the production thereof and use thereof
KR20100116176A (ko) * 2008-01-28 2010-10-29 에보니크 옥세노 게엠베하 테레프탈산의 디이소노닐 에스테르의 혼합물, 이의 제조 방법 및 이의 용도
US8329796B2 (en) * 2008-01-28 2012-12-11 Evonik Oxeno Gmbh Mixtures of diisononyl esters of terephthalic acid, method for the production thereof and use thereof
KR101582699B1 (ko) 2008-01-28 2016-01-05 에보니크 데구사 게엠베하 테레프탈산의 디이소노닐 에스테르의 혼합물, 이의 제조 방법 및 이의 용도
US20110217552A1 (en) * 2008-12-17 2011-09-08 Evonik Degussa Gmbh Process for preparing an aluminium oxide powder having a high alpha-al2o3 content
US8834833B2 (en) 2008-12-17 2014-09-16 Evonik Degussa Gmbh Process for preparing an aluminium oxide powder having a high alpha-Al2O3 content
US8846994B2 (en) 2009-07-01 2014-09-30 Evonik Degussa Gmbh Method for producing low-odor n-butane
US8940951B2 (en) 2009-07-01 2015-01-27 Evonik Degussa Gmbh Preparation of isobutene by dissociation of MTBE
US8455701B2 (en) 2009-10-15 2013-06-04 Evonik Oxeno Gmbh Method for producing decanols by means of hydrogenating decenals
US9084983B2 (en) 2009-12-15 2015-07-21 Basf Se Catalyst and process for hydrogenating aromatics
US8859834B2 (en) 2010-07-06 2014-10-14 Evonik Degussa Gmbh Process for the selective hydrogenation of multiply unsaturated hydrocarbons in olefin-containing hydrocarbon mixtures
US8841492B2 (en) 2010-10-21 2014-09-23 Evonik Degussa Gmbh Method for purification of mixtures comprising MTBE as well as production of isobutene by splitting of mixtures comprising MTBE
US8980784B2 (en) 2011-03-16 2015-03-17 Evonik Degussa Gmbh Silicon-aluminum mixed oxide powder
US9371255B2 (en) 2011-03-16 2016-06-21 Evonik Degussa Gmbh Mixed oxide compositions and process for preparing isoolefins
US8722922B2 (en) * 2011-12-12 2014-05-13 Industrial Technology Research Institute Process for hydrogenation of polycarboxylic acids or derivatives therof
US20130150614A1 (en) * 2011-12-12 2013-06-13 Industrial Technology Research Institute Process for hydrogenation of polycarboxylic acids or derivatives therof
WO2017034160A1 (ko) * 2015-08-27 2017-03-02 한화케미칼 주식회사 프탈레이트 화합물의 수소화 방법
US10000440B2 (en) 2015-11-19 2018-06-19 Evonik Degussa Gmbh Influencing the viscosity of N-butene-based ester mixtures by controlled use of ethene in the preparation of the ester precursors

Also Published As

Publication number Publication date
TWI292723B (en) 2008-01-21
US8207375B2 (en) 2012-06-26
CN100341838C (zh) 2007-10-10
JP2005537914A (ja) 2005-12-15
TW200403102A (en) 2004-03-01
ATE457298T1 (de) 2010-02-15
DE10232868A1 (de) 2004-02-05
AU2003242651A1 (en) 2004-02-09
EP1549603B1 (de) 2010-02-10
ES2339937T3 (es) 2010-05-27
DE50312411D1 (de) 2010-03-25
CN1668568A (zh) 2005-09-14
EP1549603A1 (de) 2005-07-06
JP4490264B2 (ja) 2010-06-23
WO2004009526A1 (de) 2004-01-29
US20080146832A1 (en) 2008-06-19

Similar Documents

Publication Publication Date Title
US8207375B2 (en) Microporous catalyst and method for hydrogenating aromatic compounds
US7361714B2 (en) Catalyst and method for hydrogenating aromatic compounds
US7435848B2 (en) Method for preparing alicyclic carboxylic acids and their esters
US7683204B2 (en) Mixture of alicyclic polycarboxylic acid esters having high cis isomer content
US8044229B2 (en) Alicyclic polycarboxylic ester mixtures with a high trans proportion and method for the production thereof
US8586784B2 (en) Method for continuous catalytic hydrogenation
US7632961B2 (en) Method for the production of alicyclic polycarboxylic acid esters from partial esters of aromatic polycarboxylic acids
KR20010033257A (ko) 매크로포어를 함유하는 촉매를 사용하는 벤젠폴리카르복실산 또는 그의 유도체의 수소화 방법
DE10146847A1 (de) Verfahren zur Herstellung von alicyclischen Polycarbonsäureestergemischen mit hohem trans-Anteil

Legal Events

Date Code Title Description
AS Assignment

Owner name: OXENO OLEFINCHEMIE GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GRASS, MICHAEL;KAIZIK, ALFRED;BUESCHKEN, WILFRIED;AND OTHERS;REEL/FRAME:016199/0853

Effective date: 20041124

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

AS Assignment

Owner name: EVONIK OXENO GMBH,GERMANY

Free format text: CHANGE OF NAME;ASSIGNOR:OXENO OLEFINCHEMIE GMBH;REEL/FRAME:024006/0287

Effective date: 20070926

Owner name: EVONIK OXENO GMBH, GERMANY

Free format text: CHANGE OF NAME;ASSIGNOR:OXENO OLEFINCHEMIE GMBH;REEL/FRAME:024006/0287

Effective date: 20070926

AS Assignment

Owner name: EVONIK DEGUSSA GMBH, GERMANY

Free format text: MERGER;ASSIGNOR:EVONIK OXENO GMBH;REEL/FRAME:032335/0453

Effective date: 20130806