WO2001005499A1 - Catalyseurs de deshydrogenation a base d'oxyde de zinc - Google Patents

Catalyseurs de deshydrogenation a base d'oxyde de zinc Download PDF

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Publication number
WO2001005499A1
WO2001005499A1 PCT/EP2000/006376 EP0006376W WO0105499A1 WO 2001005499 A1 WO2001005499 A1 WO 2001005499A1 EP 0006376 W EP0006376 W EP 0006376W WO 0105499 A1 WO0105499 A1 WO 0105499A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
catalysts
particularly preferably
dehydrogenation
sodium
Prior art date
Application number
PCT/EP2000/006376
Other languages
German (de)
English (en)
Inventor
Bernd Pennemann
Andreas Schulze-Tilling
Jörg Dietrich JENTSCH
Heinz Peter Meier
Original Assignee
Bayer Aktiengesellschaft
MEIER-REITER, Erika
Meier, Petra
NADALINI, Ute
Meier, Jutta
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 Bayer Aktiengesellschaft, MEIER-REITER, Erika, Meier, Petra, NADALINI, Ute, Meier, Jutta filed Critical Bayer Aktiengesellschaft
Priority to EP00951346A priority Critical patent/EP1202799A1/fr
Priority to AU64321/00A priority patent/AU6432100A/en
Priority to KR1020027000762A priority patent/KR20020013968A/ko
Priority to JP2001510578A priority patent/JP2003504194A/ja
Publication of WO2001005499A1 publication Critical patent/WO2001005499A1/fr
Priority to HK03100686.6A priority patent/HK1048613A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
    • 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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • 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
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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

Definitions

  • the present invention relates to dehydrogenation catalysts based on zinc oxide as an active component and their use in the dehydrogenation of secondary alcohols to the corresponding ketones.
  • DE-A-19626587 discloses a process for the preparation of cyclohexanone by dehydrogenation over a catalyst containing Cu as the active component and Al 2 O 3 as the carrier. Such catalysts generally allow lower reaction temperatures than those without copper.
  • EP-A-0204 046 describes a process for the preparation of cyclohexanone in which a catalyst consisting of copper, zinc oxide and an alkali metal compound, preferably sodium carbonate, is used for the dehydrogenation.
  • a catalyst consisting of copper, zinc oxide and an alkali metal compound, preferably sodium carbonate.
  • the selectivities of such catalysts are often low, but this is due to suitable ones
  • the reaction temperature is regularly associated with a significantly accelerated aging of the catalysts due to sintering of the copper, which leads to uneconomically short lifetimes for the catalysts used in this way.
  • DE-A-1443462 describes catalysts for the dehydrogenation of cyclohexanol which are prepared by precipitation of zinc salt solution with basic precipitation agents. No information is given on the Na content of the catalysts.
  • DE-A-19609954 describes a process for the dehydrogenation of secondary ones
  • Alcohols known at elevated temperature in the gas phase As a catalyst a mixture of zinc oxide and calcium carbonate is used. The catalyst is obtained by precipitating zinc and calcium nitrate with sodium carbonate, filtering off, washing free of nitrates and drying the filter cake. The product is then calcined and pressed into shaped articles.
  • a selectivity that enables the economical use of this method is only obtained when the in the
  • Dianon is an undesirable by-product in all known processes of the prior art.
  • the object of the present invention was therefore to find a catalyst for a process in which secondary ketones, preferably cyclohexanone, can be obtained with high selectivities and high conversions.
  • the catalyst should have a sufficient service life.
  • secondary alcohols are dehydrated in the presence of a catalyst which consists of zinc oxide with 0.1 to 0.6% by weight sodium, at elevated temperature in the gas phase.
  • cycloaliphatic alcohols and secondary aliphatic alcohols, preferably cyclohexanol can be used as alcohols.
  • Catalysts which contain 0.1 to 3, preferably 0.1 to 0.6% sodium are preferred.
  • Catalysts with 0.15 to 0.4% sodium are particularly preferred.
  • the specific BET surface area is preferably between 5 and 30 m 2 / g, particularly preferably 8 to 20 m 2 / g.
  • a catalyst according to the invention can be obtained by precipitation of a sparingly soluble zinc compound from water-soluble zinc compounds with a base and subsequent processing of the precipitate in a manner familiar to the person skilled in the art.
  • a preparation according to the invention consists, for example, in using aqueous sodium carbonate solution and adding zinc sulfate.
  • the precipitate is filtered off, washed, dried and then not calcined above 650 ° C.
  • the product obtained is optionally ground up and pressed to give shaped articles, for example by mixing it with a tabletting aid and tableting on a tablet machine.
  • aqueous zinc salt solutions For example, zinc sulfate, zinc nitrate, zinc chloride or zinc acetate can be used as zinc salts. Zinc sulfate and zinc chloride are preferred.
  • water-soluble sodium salts such as sodium hydroxide, sodium hydrogen carbonate or sodium carbonates can be used for the precipitation, sodium carbonate and sodium hydroxide being preferred.
  • One of the two salts preferably the base
  • a preparation is described, for example, in DE-A-3900243.
  • the temperature is usually selected in the range from 20 to 90 ° C., preferably from 50 to
  • both salt solutions are metered into a vessel at the same time, the addition being controlled in such a way that a constant pH value is established in the vessel.
  • a pH value during the precipitation of 6 to 9 is preferred.
  • the precipitate is filtered off, washed and dried. The washing is preferably carried out in a continuous manner in such a way that still in the calcined catalyst precursor
  • washable sodium particularly preferably 0.15 to 0.4% washable sodium are contained.
  • the amount of sodium which can be washed out is determined by determining the Na content before and after washing the catalyst precursor with 100 l of distilled water per kg of catalyst precursor. When washing the catalyst precursor, care should be taken to completely wash out the anion of the zinc salt used, since these can adversely affect the selectivity of the catalyst according to the invention.
  • the amount of sodium is added to the processed powder in a targeted manner, for example by pasting the precipitated product obtained with the base solution, for example a sodium carbonate solution, and then drying it.
  • the concentration of the solution is chosen so that the catalyst has the sodium content according to the invention.
  • the washing step is particularly important since it is possible to influence the sodium content of the catalyst, which is easily accessible to those skilled in the art, for example, through elemental analysis.
  • the powder obtained can optionally be pre-calcined, preferably in a spray dryer.
  • the powder is then subjected to a shaping step and the product is calcined, the calcining conditions and, in particular, the temperature being selected such that the resulting catalyst has a BET specific internal surface area of at least 5 and at most 30 m 2 / g, particularly preferably 8 up to 20 m 2 / g.
  • the higher the calcination temperatures and / or the longer the calcification times the smaller the specific surface area. If necessary, the order of shaping and calcining can also be reversed.
  • calcination is carried out, the product obtained is mixed with 0.1 to 5% by weight, preferably 1 to 5% by weight, particularly preferably 2 to 5% by weight of auxiliaries, and the product obtained is pressed to give shaped articles , such as tablets, asterisks, rings, split, wagon wheels, balls, preferably tablets.
  • Graphite is preferred as a tabletting aid, synthetic graphite being particularly preferred because of its higher purity, as one should avoid contamination of the catalyst at all during the processing steps. In general, care should be taken not to allow any metal oxides which the person skilled in the art is aware of to have acidic properties to get into the catalyst. This includes, for example, activated aluminum oxide. They are calcined Tablets so that the BET specific internal surface area of at least 5 and at most 30 m 2 / g, particularly preferably 8 to 20 m 2 / g, is achieved. Catalysts whose lateral compressive strength is 20 to 500 N, particularly preferably 40 to 100 N, are particularly preferred. These compressive strengths can be set by customary measures in the field of tableting, for example setting the stamp pressure and measuring, for example, on an Instron Mini 44, stamp diameter 8 mm.
  • the alcohol can be evaporated in an evaporator and passed through a heated flow tube which contains a catalyst bed.
  • the amount of alcohol added per unit of time is preferably chosen to be 0.5 to 3, particularly preferably 1 to 2 kg of cyclohexanol per liter of catalyst bed and hour, for other alcohols according to their molecular weight in relation to cyclohexanol.
  • a method is particularly preferred in which the product obtained from the cyclohexane oxidation and subsequent purification, a mixture of cyclohexanol and cyclohexanone, is used.
  • the reaction temperature is preferably between 200 to 500 ° C, particularly preferably 300 to 450 ° C, without being unacceptable
  • the temperature is selected so that a conversion of the secondary alcohol of preferably 60% to 90%, particularly preferably 65% to 80%, is obtained. This results in the particularly preferred range of the reaction temperature of 300 to 450 ° C.
  • the product obtained is usually condensed from
  • the catalyst according to the invention has a high selectivity with a long service life and sufficiently high activity.
  • Cyclohexanone produced according to the invention is an important precursor for polyamide 6 and polyamide -6.6.
  • the mixture is stirred for 30 minutes and then left to stand for 30 minutes, the supernatant solution is suctioned off, the suspension is distributed over three suction filters, filtered off and washed with a total of 72 l of distilled water.
  • the filter cake is spread over several trays and dried in a convection oven at 125 ° C overnight. 3570 grams of product are obtained, which are then heated in a standing oven to 400 ° C. and for one
  • the product obtained is ground, mixed with 4% by weight, based on the total solids, of a synthetic graphite (average particle diameter 44 ⁇ m) and compressed in a tablet machine to give tablets of 5 mm in diameter and 3 mm in height.
  • the tablets are annealed in a laboratory oven at 500 ° C for 4 h.
  • the catalyst has a side fracture hardness of
  • a zinc salt solution which consists of zinc sulfate and zinc chloride in a molar ratio of 1: 2.
  • a solution of sodium carbonate and sodium hydroxide in a molar ratio of 40:60 is used as the base. Both solutions are dosed into the container at the same time, the pumping speeds being regulated so that a pH of 8 is established. The product obtained is filtered. Then you wash on Nutsche. Otherwise the procedure is as in Example 1.
  • the finished catalyst has a Na content of 0.39%, a side fracture hardness of 45 N and a BET specific surface area of 9 m 2 / g.
  • Example 2 The procedure is as in Example 2, but the catalyst tablets are not calcined at the end of the preparation. This resulted in a specific BET surface area of 64 m 2 / g. The sodium content of the catalyst was 0.39% and its side hardness was 48 N.
  • Shaped bodies are produced as in Example 2.
  • the resulting catalyst has a sodium content of 0.022%, a side fracture hardness of 35 N and a BET specific internal surface area of 10 m 2 / g.
  • the catalysts obtained were tested in a flow tube of 55 mm in inner diameter and in length.
  • the reaction tube is heated electrically, the volume of the catalyst bed is in each case 2 l. 3 kg of a mixture of 94% cyclohexanol and 6% cyclohexanone per hour are fed to the reactor via an evaporator.
  • the catalysts are run over a period of about 7 to 10 days and the reaction temperature is gradually raised to such an extent that the product contains a cyclohexanone content of 73-75%. Then the dianone content of the product, determined by gas chromatography, and the necessary reaction temperature were used to assess the catalysts. In the catalyst according to Example 3, the conversion was not raised above 63%; Comparable measured values from Example 1 and Example 2 are given.

Landscapes

  • 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)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne des catalyseurs de déshydrogénation à base d'oxyde de zinc en tant que composants actifs ayant une teneur en sodium et une surface spécifique déterminées. L'invention concerne également leur utilisation dans la déshydrogénation d'alcools secondaires pour obtenir les cétones correspondantes.
PCT/EP2000/006376 1999-07-19 2000-07-06 Catalyseurs de deshydrogenation a base d'oxyde de zinc WO2001005499A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP00951346A EP1202799A1 (fr) 1999-07-19 2000-07-06 Catalyseurs de deshydrogenation a base d'oxyde de zinc
AU64321/00A AU6432100A (en) 1999-07-19 2000-07-06 Zinc oxide-based dehydrogenating catalysts
KR1020027000762A KR20020013968A (ko) 1999-07-19 2000-07-06 산화아연 기재 탈수소화 촉매
JP2001510578A JP2003504194A (ja) 1999-07-19 2000-07-06 酸化亜鉛をベースにした脱水素触媒
HK03100686.6A HK1048613A1 (zh) 1999-07-19 2003-01-27 基於氧化鋅的脫氫催化劑

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19933079.4 1999-07-19
DE19933079A DE19933079A1 (de) 1999-07-19 1999-07-19 Dehydrierkatalysatoren

Publications (1)

Publication Number Publication Date
WO2001005499A1 true WO2001005499A1 (fr) 2001-01-25

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ID=7914824

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/006376 WO2001005499A1 (fr) 1999-07-19 2000-07-06 Catalyseurs de deshydrogenation a base d'oxyde de zinc

Country Status (9)

Country Link
EP (1) EP1202799A1 (fr)
JP (1) JP2003504194A (fr)
KR (1) KR20020013968A (fr)
CN (1) CN1361718A (fr)
AU (1) AU6432100A (fr)
DE (1) DE19933079A1 (fr)
HK (1) HK1048613A1 (fr)
WO (1) WO2001005499A1 (fr)
ZA (1) ZA200200015B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8747804B2 (en) 2008-07-18 2014-06-10 Basf Se Modified zinc oxide particles

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007022922A (ja) * 2005-07-12 2007-02-01 Tonen Chem Corp カルボニル化合物の製造法
JP6627219B2 (ja) * 2015-01-05 2020-01-08 株式会社Ihi オレフィンの製造方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1211629B (de) * 1962-08-14 1966-03-03 Basf Ag Verfahren zum Dehydrieren von Cyclohexanol
DE1443462A1 (de) * 1962-12-18 1969-08-14 Basf Ag Verfahren zum Dehydrieren von primaeren oder sekundaeren Alkoholen
US4551556A (en) * 1983-05-02 1985-11-05 Toa Nenryo Kogyo Kabushiki Kaisha Process for producing carbonyl compounds
EP0204046A2 (fr) * 1985-05-31 1986-12-10 Industrial Technology Research Institute Procédé et catalyseur pour la conversion de cyclohexanol en cyclohexanone
US4764498A (en) * 1982-01-09 1988-08-16 Bayer Aktiengesellschaft Silica-containing shaped articles and a process for their preparation
US4918239A (en) * 1988-12-27 1990-04-17 National Science Council Method of producing cyclohexanone from cyclohexanol through oxidative dehydrogenation
US5041682A (en) * 1985-04-16 1991-08-20 Basf Aktiengesellschaft Working up reaction mixtures containing cyclohexanol cyclohexanone and cyclohexyl hydroperoxide
JPH04164816A (ja) * 1990-10-30 1992-06-10 Mitsubishi Materials Corp 液中合成法による針状酸化亜鉛粉末の製造方法
JPH04164813A (ja) * 1990-10-30 1992-06-10 Mitsubishi Materials Corp 酸化亜鉛粉末の製造方法
US5254516A (en) * 1992-03-26 1993-10-19 Research Triangle Institute Fluidizable zinc titanate materials with high chemical reactivity and attrition resistance
DE19609954A1 (de) * 1996-03-14 1997-09-18 Basf Ag Verfahren zur Dehydrierung von sekundären cyclischen Alkoholen

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1543933A (fr) * 1966-11-28 1968-10-31 Inst Francais Du Petrole Procédé et catalyseur de fabrication de cétones cycliques, par déshydrogénationcatalytique d'alcools cycliques

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1211629B (de) * 1962-08-14 1966-03-03 Basf Ag Verfahren zum Dehydrieren von Cyclohexanol
DE1443462A1 (de) * 1962-12-18 1969-08-14 Basf Ag Verfahren zum Dehydrieren von primaeren oder sekundaeren Alkoholen
US4764498A (en) * 1982-01-09 1988-08-16 Bayer Aktiengesellschaft Silica-containing shaped articles and a process for their preparation
US4551556A (en) * 1983-05-02 1985-11-05 Toa Nenryo Kogyo Kabushiki Kaisha Process for producing carbonyl compounds
US5041682A (en) * 1985-04-16 1991-08-20 Basf Aktiengesellschaft Working up reaction mixtures containing cyclohexanol cyclohexanone and cyclohexyl hydroperoxide
EP0204046A2 (fr) * 1985-05-31 1986-12-10 Industrial Technology Research Institute Procédé et catalyseur pour la conversion de cyclohexanol en cyclohexanone
US4670605A (en) * 1985-05-31 1987-06-02 Industrial Technology Research Institute Process and catalyst for the conversion of cyclohexanol to cyclohexanone
US4918239A (en) * 1988-12-27 1990-04-17 National Science Council Method of producing cyclohexanone from cyclohexanol through oxidative dehydrogenation
JPH04164816A (ja) * 1990-10-30 1992-06-10 Mitsubishi Materials Corp 液中合成法による針状酸化亜鉛粉末の製造方法
JPH04164813A (ja) * 1990-10-30 1992-06-10 Mitsubishi Materials Corp 酸化亜鉛粉末の製造方法
US5254516A (en) * 1992-03-26 1993-10-19 Research Triangle Institute Fluidizable zinc titanate materials with high chemical reactivity and attrition resistance
DE19609954A1 (de) * 1996-03-14 1997-09-18 Basf Ag Verfahren zur Dehydrierung von sekundären cyclischen Alkoholen

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 1992-245635, XP002151063 *
DATABASE WPI Derwent World Patents Index; AN 1992-245638, XP002151062 *
PATENT ABSTRACTS OF JAPAN vol. 016, no. 461 (C - 0988) 25 September 1992 (1992-09-25) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8747804B2 (en) 2008-07-18 2014-06-10 Basf Se Modified zinc oxide particles

Also Published As

Publication number Publication date
ZA200200015B (en) 2003-01-02
AU6432100A (en) 2001-02-05
JP2003504194A (ja) 2003-02-04
KR20020013968A (ko) 2002-02-21
EP1202799A1 (fr) 2002-05-08
DE19933079A1 (de) 2001-01-25
CN1361718A (zh) 2002-07-31
HK1048613A1 (zh) 2003-04-11

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