EP1341610A1 - Catalyseur poreux adapte a l'hydrogenation d'anhydride de l'acide maleique pour former du tetrahydrofurane - Google Patents

Catalyseur poreux adapte a l'hydrogenation d'anhydride de l'acide maleique pour former du tetrahydrofurane

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Publication number
EP1341610A1
EP1341610A1 EP01989587A EP01989587A EP1341610A1 EP 1341610 A1 EP1341610 A1 EP 1341610A1 EP 01989587 A EP01989587 A EP 01989587A EP 01989587 A EP01989587 A EP 01989587A EP 1341610 A1 EP1341610 A1 EP 1341610A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
hydrogenation
oxide
diameter
pore volume
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP01989587A
Other languages
German (de)
English (en)
Inventor
Holger Borchert
Stephan Schlitter
Markus Rösch
Rolf-Hartmuth Fischer
Ralf-Thomas Rahn
Alexander Weck
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP1341610A1 publication Critical patent/EP1341610A1/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—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
    • B01J35/60—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
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C07D307/08—Preparation of tetrahydrofuran
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
    • 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
    • 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)

Definitions

  • the present invention relates to a process for the preparation of optionally alkyl-substituted ⁇ -butyrolactone and tetrahydrofuran by catalytic hydrogenation in the gas phase of substrates which are selected from the group consisting of maleic acid and succinic acid and derivatives of these acids.
  • substrates which are selected from the group consisting of maleic acid and succinic acid and derivatives of these acids.
  • this includes esters and anhydrides, which, like the acids, can have one or more alkyl substituents.
  • a catalyst is used which has a certain porosity.
  • GBL and THF are maleic acid itself, succinic acid and its anhydride and the esters of these acids. If GBL and THF are to be produced which have alkyl substituents, it is advisable to use the corresponding alkyl-substituted species of the abovementioned acids, esters and anhydrides.
  • US Pat. No. 3,065,243 discloses a process in which copper chromite serves as a catalyst. According to the description and examples, considerable amounts of succinic anhydride (BSA) are formed in this reaction procedure, which must be circulated. As is known, process engineering problems often arise due to the crystallization of the BSA or the resulting succinic acid with subsequent blockage of pipelines.
  • BSA succinic anhydride
  • the disclosure of further copper chromite catalysts for the hydrogenation of MA is found, for example, in the publications US 3,580,930, US 4,006,165, EP-A 638 565 and WO 99/38856. According to the disclosure, high yields of GBL can be achieved with the catalysts described there. THF is only formed in traces. However, it is often the case that higher amounts of THF are desired for several reasons.
  • the catalysts used according to this patent correspond to the general formula CuiZnbAlcMdO x , in which M is at least one element which is selected from the group consisting of groups IIA and IIIA, VA, VIII, Ag, Au, groups IIIB to VIIB and lanthanides and actinides of the Periodic Table of the Elements; b is a number between 0.001 and 500, c a number between 0.001 and 500 and d a number from 0 to ⁇ 200 and x corresponds to the number of oxygen atoms that are necessary according to the valence criteria.
  • the catalysts according to this patent need not contain chromium, chromium-containing catalysts are described in all examples. According to these examples, a maximum THF yield of 96% is obtained, and the hydrogenation is carried out at pressures of 20 to 40 bar.
  • a two-stage catalyst system for the hydrogenation of MA is described in US Pat. No. 5,149,836.
  • the catalyst for the first stage is chrome-free, the catalyst for the second stage is based on Cu-Zn-Cr oxides.
  • a catalyst composed exclusively of Cu and Al oxides for the MA gas phase hydrogenation to GBL is disclosed in WO 97/24346. You can also find here the same disadvantages as in the publications described in the previous paragraph, namely only subordinate or trace formation of THF.
  • the use of a catalyst with basically the same composition as described in WO 97/24346, namely based on Cu-Al oxides, is also disclosed in JP 2 233 631.
  • the aim of this invention is to carry out the hydrogenation of MA so that the main products are THF and 1,4-butanediol in addition to little or no amounts of GBL.
  • This is then achieved by using the catalysts based on mixed Cu-Al oxides and by observing certain reaction conditions.
  • Typical mixtures obtained with this process contain approx. 15 to 20 mol% of 1,4-butanediol and 60 to 80 mol% of THF, the amount of THF even being able to be increased to over 99 mol% according to an example.
  • This is achieved by using GBL as a solvent, in a multiple excess. If, on the other hand, work is carried out without a solvent, the THF yields drop considerably, increasing by 75%.
  • EP-A 0 404 408 discloses a catalyst for MA hydrogenation, the structure of which is fundamentally different from the catalysts in the references mentioned above.
  • the catalytically active material essentially corresponds to the material that is disclosed in the above-cited US 5,072,009.
  • the material is then applied to a substantially inert, at least partially porous support having an outer surface.
  • the catalytically active material adheres to the outer surface of the support.
  • GBL is the preferred product alongside large amounts of BSA as a by-product. It is stated in the description that when using the same active material in the form of a full catalyst as disclosed in US Pat. No.
  • Catalysts based on copper oxide with a certain porosity and their use as hydrogenation catalysts are known per se.
  • No. 5,155,086 discloses powdered catalysts containing copper oxide, zinc oxide and aluminum oxide, in which at least 40% of the total pore volume is taken up by pores with diameters of 120 to 1000 ⁇ .
  • Such catalysts are suitable for the hydrogenation of carboxylic acids and carboxylic acid esters to alcohols and of ketones and aldehydes to alcohol. The hydrogenation of MSA to THF is not described.
  • EP-A 604 792 describes catalysts which contain 100 parts by weight of copper oxide, 40 to 130 parts by weight of zinc oxide, 2 to 50 parts by weight of aluminum oxide and 1 to 40 parts by weight of sodium oxide and a total surface area of 50 to 100 m 2 / g (according to BET) have, with 75 to 95% of the total surface of pores with radii of 9 to 1000 nm and the remaining total surface of pores, the radius of which is ⁇ 9 nm, is formed.
  • Catalysts of this type are used for the hydrogenation of organic compounds, in particular for the hydrogenation of saturated and unsaturated aldehydes, Ketones, carboxylic acids or carboxylic acid esters to saturated alcohols. The hydrogenation of MSA to THF is not described.
  • WO 97/34694 discloses copper oxide / aluminum oxide hydrogenation catalysts which can be present as an extrudate or in tablet form.
  • the extrudates have pore volumes of 0.15 to 0.6 ml / g and bimodal pore radius distributions with maxima around 100 ⁇ and 1000 to 2000 ⁇ , the tablets have pore volumes from 0.2 to 0.6 ml / g and bimodal pore radius distributions with maxima um 100 ⁇ and 500 to 2000 ⁇ .
  • the hydrogenation of MSA to THF is also not mentioned here.
  • the catalysts used according to the invention differ from the catalysts which are described in the prior art. They contain copper oxide and at least one further metal or a compound, preferably an oxide thereof, from the group consisting of Al, Si, Zn, La, Ce, the elements of groups IIIA to VIIIA and groups IA and IIA. Furthermore, the catalysts as solids have a pore volume of ⁇ 0.01 ml / g for pore diameters> 50 nm and a ratio of the pore volume of macropores with a diameter> 50 nm to the total pore volume for pores with a diameter> 4 nm of> 10% ,
  • the catalysts of the invention make it possible to carry out the hydrogenation of C 4 dicarboxylic acids and / or their derivatives in such a way that THF is formed as the main product, in yields of well over 90%, very often close to 100%.
  • C 4 -dicarboxylic acid and its derivatives are understood to mean maleic acid or succinic acid, which may have one or more C 1 -C 18 -alkyl substituents, and the anhydrides and esters of these optionally alkyl-substituted acids.
  • An example of such an acid is citraconic acid.
  • MSA is preferably used as the starting material to be hydrogenated.
  • the THF produced can also have one or more alkyl substituents, depending on the starting material used.
  • a substituted THF is hereinafter referred to as a THF derivative.
  • the catalysts of the invention contain copper oxide as the base material, which is mixed with at least one further metal or a compound thereof, preferably an oxide.
  • a metal is used which is selected from the group consisting of Al, Si, Zn, La, Ce, the elements of groups IIIA to VIIIA and groups IA and IIA or a compound thereof, preferably an oxide.
  • Silicon dioxide, zinc oxide, aluminum oxide, zirconium oxide and / or titanium dioxide is preferably used. Chromium-free systems based on copper oxide / aluminum oxide and copper oxide / zinc oxide / aluminum oxide are particularly preferred.
  • the copper oxide content in the catalysts according to the invention is at values of 10 10% by weight, preferably ⁇ 25% by weight.
  • the catalysts according to the invention must have certain properties with regard to the porosity.
  • the catalysts present as shaped bodies have a pore volume of ⁇ 0.01 ml / g for pore diameters> 50 nm, preferably of ⁇ 0.025 ml / g for pore diameters> 100 nm and in particular ⁇ 0.05 ml / g for pore diameters> 200 nm. These values were determined by mercury intrusion according to DIN 66133. The data were evaluated in the pore diameter range from 4 nm to 300 ⁇ m.
  • the ratio in the molded body of the pore volume of macropores with a diameter> 50 nm to the total pore volume for pores with a diameter> 4 nm should be> 10%. It is preferred if this ratio is at values of> 20%, in particular at values of> 30%.
  • the catalyst mass is produced using methods known to the person skilled in the art. Processes in which the copper oxide is finely divided and intimately mixed with the other constituents are preferred. This can preferably be achieved by precipitation reactions. Copper compounds dissolved in a solvent are precipitated with a precipitant in the presence of further metal compounds which are soluble or suspended in the solvent, filtered off, washed, dried and optionally calcined.
  • the corresponding metal carbonates and / or hydroxides can be precipitated in aqueous solution, filtered off, washed, dried and optionally calcined.
  • the metal carbonates or hydroxides are, for example, by dissolving the corresponding metal salts in water and addition of soda solution available.
  • nitrates, sulfates, chlorides, acetates and / or oxalates are used as metal salts.
  • the catalysts according to the invention are in the form of moldings which are known to the person skilled in the art.
  • suitable moldings include tablets, rings, spheres and extrudates. These moldings are obtained by processes known per se, for example extrusion, tableting or by agglomeration processes.
  • the porosity that the catalysts according to the invention must have in order to achieve the desired hydrogenation activity can be achieved by certain measures during production. These include, for example, the addition of pore formers, additives, the choice of a suitable particle size distribution and porosity of the catalyst powder, suitable process parameters for the deformation of the starting materials or a combination of the measures mentioned above.
  • Suitable pore formers are, for example, carboxylic acids such as oxalic acid, stearic acid and palmitic acid, carbohydrates and modified carbohydrates such as starch and methyl cellulose. Powdered activated carbons, graphite, ammonium salts and nitrates are also suitable. These materials can be removed again after shaping, for example by thermal treatment of the shaped catalyst body.
  • Metal oxides, metal carbides and metal nitrides are suitable as additives for adjusting the porosity that remain permanently in the catalyst.
  • a suitable particle size distribution and porosity of the catalyst powder can be e.g. by thermal pretreatment of a suspension containing catalyst powder.
  • a higher macroporosity can be achieved, for example, by low energy input during the rolling process or reduced compression pressures when tableting.
  • the use of precalcined starting materials and the use of pore formers are preferred.
  • the catalysts according to the invention can also be applied, for example, by applying the active component be produced on a carrier of appropriate porosity.
  • the application can be done by watering.
  • catalysts according to the invention can be obtained by molding a heterogeneous mixture of active component or precursor compounds thereof with a carrier component or precursor compounds thereof.
  • the catalysts used can also contain an auxiliary in an amount of 0 to 10% by weight.
  • auxiliary are understood to be organic and inorganic substances which contribute to improved processing during catalyst production and / or to an increase in the mechanical strength of the shaped catalyst bodies. Such aids are known to the person skilled in the art; Examples include graphite, stearic acid, silica gel and copper powder.
  • the catalyst is subjected to activation, generally hydrogen pretreatment, before use in the reaction.
  • activation generally hydrogen pretreatment
  • the catalyst according to the invention has a sufficient service life.
  • the activity and / or selectivity of the catalyst should nevertheless decrease in the course of its operating time, it can be regenerated by measures known to the person skilled in the art.
  • This includes reductive treatment of the catalyst in a hydrogen stream at elevated temperature. If necessary, the reductive treatment can be preceded by an oxidative treatment. In this case, a molecular mixture containing gas, for example air, flows through the catalyst bed at elevated temperature.
  • a suitable solvent for example methanol, THF or GBL
  • Reactors in which the catalyst is arranged as a fixed bed are generally suitable for carrying out the reaction. Tube-bundle reactors are preferred in order to dissipate the heat released during the reaction cheaply.
  • the starting material preferably MA
  • the starting material is evaporated and passed through the reactor with a gas stream containing hydrogen.
  • the supply of other gaseous components such as water vapor or carbon monoxide, can have a favorable effect on the selectivity, activity or long-term stability.
  • the concentration of the starting material is preferably between 0.2 and 2% by volume. at much higher educt concentrations, particularly when using MA, condenses out in the reactor and coats the catalyst with a liquid film. Much lower concentrations would reduce the space-time yield.
  • the temperature of the reaction is from 150 to 400 ° C, preferably 200 to 300 ° C. Higher temperatures favor the formation of by-products, lower temperatures lead to an unnecessary loss of activity of the catalyst.
  • the pressure is from 0.5 to 100, preferably 1 to 50, in particular ⁇ 20 bar.
  • the GHSV is set so that a complete educt conversion is achieved. This simplifies the processing of the product mixture and saves the return of unreacted starting material.
  • the GHSV is set to values of 10 to 50,000 h "1 , preferably 100 to 10,000 h " 1 .
  • the product mixture can be separated by methods known to those skilled in the art. At least part of the unreacted hydrogen is preferably circulated and thus used again in the hydrogenation.
  • Example 1 1.9 kg of the precipitate from Example 1 are mixed intensively with 100 g of ammonium nitrate and 60 g of graphite and tabletted into tablets of 3 mm in diameter and height. The tablets are calcined at 500 ° C for two hours.
  • the catalyst was subjected to a hydrogen pretreatment.
  • the reactor was first flushed with 200 ⁇ l / h nitrogen at atmospheric pressure and at the same time heated to a temperature in the catalyst bed of 180 ° C. within one hour.
  • the nitrogen volume flow was then increased to 950 hl / h and an additional 50 ⁇ l / h of hydrogen were fed in.
  • a slight increase in temperature in the catalyst bed to about 250 ° C. in the hot spot was observed.
  • the hot spot travels through the reactor from the reactor entrance to the end of the reactor.
  • the nitrogen volume flow was reduced to 900 Nl / h and the amount of hydrogen flow increased to 100 Nl / h.
  • the nitrogen volume flow was gradually switched off, the hydrogen flow was gradually increased to 600 Nl / h.

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

Abstract

La présente invention concerne un catalyseur d'hydrogénation qui est particulièrement adapté à l'hydrogénation d'anhydride de l'acide maléique et de ses dérivés pour former du tétrahydrofurane (THF) ou ses dérivés. Ce catalyseur d'hydrogénation contient de l'oxyde de cuivre et au moins un autre métal ou un composé de celui-ci, de préférence un oxyde, du groupe comprenant Al, Si, Zn, La, Ce, les éléments des groupes IIIA à VIIIA et des groupes IA et IIA, avec un volume de pores ≥ 0,01 ml/g pour des diamètres de pores > 50 nm et un rapport entre le volume de pores pour des macropores présentant un diamètre > 50 nm et le volume de pores total pour des pores présentant un diamètre > 4 nm > 10 %.
EP01989587A 2000-12-11 2001-12-07 Catalyseur poreux adapte a l'hydrogenation d'anhydride de l'acide maleique pour former du tetrahydrofurane Ceased EP1341610A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10061553A DE10061553A1 (de) 2000-12-11 2000-12-11 Poröser Katalysator für die Hydrierung von Maleinsäureanhydrid zu Tetrahydrofuran
DE10061553 2000-12-11
PCT/EP2001/014392 WO2002047818A1 (fr) 2000-12-11 2001-12-07 Catalyseur poreux adapte a l'hydrogenation d'anhydride de l'acide maleique pour former du tetrahydrofurane

Publications (1)

Publication Number Publication Date
EP1341610A1 true EP1341610A1 (fr) 2003-09-10

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EP01989587A Ceased EP1341610A1 (fr) 2000-12-11 2001-12-07 Catalyseur poreux adapte a l'hydrogenation d'anhydride de l'acide maleique pour former du tetrahydrofurane

Country Status (8)

Country Link
US (1) US6888011B2 (fr)
EP (1) EP1341610A1 (fr)
JP (1) JP4149808B2 (fr)
KR (1) KR100809133B1 (fr)
CN (1) CN1308080C (fr)
DE (1) DE10061553A1 (fr)
MY (1) MY126658A (fr)
WO (1) WO2002047818A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10124962A1 (de) * 2001-05-21 2002-12-05 Basf Ag Katalysatoren für die Reinigung von Ethylen
DE10313702A1 (de) † 2003-03-27 2004-10-07 Basf Ag Katalysator und Verfahren zur Hydrierung von Carbonylverbindungen
GB0325526D0 (en) 2003-10-31 2003-12-03 Davy Process Techn Ltd Process
US7659227B2 (en) 2006-05-22 2010-02-09 University Of Notre Dame Du Lac Catalysts for hydrogen production
CN101547733B (zh) 2006-12-01 2014-01-22 巴斯夫欧洲公司 吸附组合物和从料流中除去co的方法
CN102617518B (zh) * 2011-01-27 2014-10-01 中科合成油技术有限公司 顺酐气相加氢一步法制备四氢呋喃
DE102012019123B4 (de) 2012-09-28 2021-10-21 Clariant International Ltd. Hydrierkatalysator und Verfahren zu dessen Herstellung durch die Verwendung von unkalziniertem Ausgangsmaterial
CN103724300B (zh) * 2013-12-18 2016-01-13 江苏大学 一种顺酐加氢与乙醇脱氢耦合制备四氢呋喃的方法
DE102014004413A1 (de) * 2014-03-26 2015-10-01 Clariant International Ltd. Hydrierkatalysator und Verfahren zu dessen Herstellung
CN106268835B (zh) * 2015-06-08 2018-09-25 中国石油化工股份有限公司 一种顺丁烯二酸酐加氢制γ-丁内酯的催化剂及其制备方法
FR3061036B1 (fr) * 2016-12-23 2021-07-02 Ifp Energies Now Solide porteur d'oxygene macroporeux a matrice ceramique d'oxydes, son procede de preparation et son utilisation pour un procede d'oxydo-reduction en boucle chimique
FR3061037B1 (fr) * 2016-12-23 2021-07-02 Ifp Energies Now Solide porteur d'oxygene a base de tectosilicates, son procede de preparation et son utilisation pour un procede d'oxydo-reduction en boucle chimique
CN115007159B (zh) * 2022-06-07 2023-10-13 中国科学院大连化学物理研究所 一种具有磁性的负载型镍催化剂及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5395990A (en) * 1993-12-02 1995-03-07 Eastman Chemical Company Process for the production of alcohols and diols
WO2001044148A1 (fr) * 1999-12-13 2001-06-21 Davy Process Technology Ltd Procede permettant de produire a la fois des diols aliphatiques et des ethers cycliques

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3065243A (en) 1962-11-20 Reduction of dicarboxylic acid esters
DE1668348A1 (de) 1966-12-29 1972-03-30 Kao Corp Verfahren zur Herstellung von gamma-Butyrolacton
US4006165A (en) 1973-08-03 1977-02-01 Deutsche Texaco Aktiengesellschaft Process for converting maleic anhydride to γ-butyrolactone
US5072009A (en) 1987-12-23 1991-12-10 The Standard Oil Company Vapor-phase hydrogenation of maleic anhydride to tetrahydrofuran and gamma-butyrolactone
US5155086A (en) 1989-09-12 1992-10-13 Engelhard Corporation Hydrogenation catalyst, process for preparing and process of using said catalyst
JPH0669163A (ja) * 1991-05-19 1994-03-11 Ulvac Japan Ltd エッチング装置
US5149836A (en) 1991-07-25 1992-09-22 Isp Investments Inc. Process for the production of gamma butyrolactone THF in predetermined amounts
US5122495A (en) 1991-10-02 1992-06-16 Isp Investments Inc. Activated catalyst for the vapor phase hydrogenation of maleic anhydride to gamma-butyrolactone in high conversion and high selectivity
DE4244273A1 (de) 1992-12-28 1994-06-30 Hoechst Ag Kupferkatalysator
DE4301469A1 (de) * 1993-01-21 1994-07-28 Basf Ag Katalysatoren mit hochdisperser Verteilung der Aktivkomponente
DE4326692A1 (de) 1993-08-10 1995-02-16 Akzo Nobel Nv Verfahren zur Herstellung von gamma-Butyrolacton
DE4403187C1 (de) 1994-02-02 1995-09-28 Degussa Geformter Kupfer-Katalysator für die selektive Hydrierung von Furfural zu Furfurylalkohol
IT1273320B (it) 1994-02-22 1997-07-08 Alusuisse Italia Spa Procedimento per la produzione di gamma-butirrolattone
DE19546612A1 (de) * 1995-12-13 1997-06-19 Basf Ag Verfahren zur Reduktion von NOx aus Abgasen
TW341568B (en) 1995-12-27 1998-10-01 Akzo Nobel Nv Process for manufacturing Gamma-butyrolactone and its use
EP2165760A3 (fr) * 1996-03-21 2010-05-12 Basf Catalysts Llc Catalyseur à base d'oxydes mixtes de cuivre et d'aluminium, sa préparation et ses utilisations
IT1298096B1 (it) 1998-01-09 1999-12-20 Lonza Spa Procedimento per la produzione di gamma-butirrolattone
IT1298535B1 (it) 1998-02-02 2000-01-12 Lonza Spa Procedimento per la produzione di gamma-butirrolattone

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5395990A (en) * 1993-12-02 1995-03-07 Eastman Chemical Company Process for the production of alcohols and diols
WO2001044148A1 (fr) * 1999-12-13 2001-06-21 Davy Process Technology Ltd Procede permettant de produire a la fois des diols aliphatiques et des ethers cycliques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO0247818A1 *

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KR20030061428A (ko) 2003-07-18
MY126658A (en) 2006-10-31
KR100809133B1 (ko) 2008-02-29
US6888011B2 (en) 2005-05-03
DE10061553A1 (de) 2002-06-13
WO2002047818A1 (fr) 2002-06-20
CN1308080C (zh) 2007-04-04
US20040030163A1 (en) 2004-02-12
CN1568228A (zh) 2005-01-19
JP4149808B2 (ja) 2008-09-17

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