EP0909214A1 - Catalyseur pour la deshydrogenation du cyclohexanol, procede de production et utilisation dudit catalyseur - Google Patents

Catalyseur pour la deshydrogenation du cyclohexanol, procede de production et utilisation dudit catalyseur

Info

Publication number
EP0909214A1
EP0909214A1 EP97927189A EP97927189A EP0909214A1 EP 0909214 A1 EP0909214 A1 EP 0909214A1 EP 97927189 A EP97927189 A EP 97927189A EP 97927189 A EP97927189 A EP 97927189A EP 0909214 A1 EP0909214 A1 EP 0909214A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
copper
cyclohexanol
aluminum oxide
bet surface
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97927189A
Other languages
German (de)
English (en)
Inventor
Daniel Heineke
Ruprecht Meissner
Michael Hesse
Robert MÄRKL
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 EP0909214A1 publication Critical patent/EP0909214A1/fr
Withdrawn legal-status Critical Current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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to an improved catalyst consisting of ⁇ -aluminum oxide as a support material and copper as an active component, which is characterized in that the BET surface area (measured according to DIN 66131) of the aluminum oxide 10 is not less than 30 m 2 / g.
  • the invention further relates to a process for the preparation of the catalyst according to the invention and its use in the dehydrogenation of cyclohexanol to cyclohexanone and the use of ⁇ -aluminum oxide with a BET surface area (measured according to DIN 66131) of the aluminum oxide of not less than 30 m 2 / g for the production of a catalyst.
  • Cyclohexanone is produced as an important precursor for polyamide 6 and - 6.6 0 on an industrial scale mainly by catalytic dehydrogenation of cyclohexanol.
  • the high-temperature variant cyclohexanol is dehydrated at temperatures from 320 to 420 ° C
  • the low-temperature variant is carried out in a temperature range from 220 to 260 ° C.
  • a disadvantage of dehydrogenation at high temperatures is low selectivity to cyclohexanol, since considerable secondary reactions such as dehydration of the cyclohexanol to cyclohexene or dimerizations such as the formation of cyclohexenylcyclohexanone occur at the high temperatures.
  • the formation of the by-products requires extensive work-up and affects the economics of the process. 5
  • Catalysts based on copper are primarily used for the dehydrogenation of cyclohexanol at lower temperatures. These catalysts allow the reaction temperature to be reduced to approximately 240 to 280 ° C. and thus enable higher cyclohexanone selectivities. However, the sales due to the equilibrium at the comparatively lower temperature are generally not very high.
  • One class of these low-temperature catalysts contains compositions which consist of copper and a ceramic support, which can be SiO or Al 2 O 3 or a mixture of these oxides.
  • the copper content of these catalysts can be up to 50% by weight.
  • these catalysts can contain small amounts of alkali metals as promoters.
  • the copper catalysts in question are usually produced in such a way that the copper active component is applied either to a prefabricated support by precipitation of a copper salt or by impregnation with a suitable copper salt solution or the components from which the catalyst is composed, be felled together.
  • Another possibility for the production of copper catalysts is the dry mixing of the components and the subsequent calcination.
  • the acidity can be reduced by adding alkali or alkaline earth metals (see, for example, Appl. Cat. A: General Vol. 83, No. 2 (1992), pp. 201-11), but this measure simultaneously leads to a decrease in activity
  • the advantage of higher activity of copper catalysts compared to high-temperature catalysts therefore goes through a
  • catalysts described in A 103 (1994) 233-42 are not suitable for large-scale use, since the catalysts are in the form of a powder. Compression into shaped bodies such as tablets is made difficult by the poor tabletting ability. In addition, the low hardness of the moldings produced in this way means that the reactor has little resistance to abrasion, combined with an increasing pressure loss as the reaction time progresses. This means that large-scale use is generally not possible.
  • the object on which the present invention is based was therefore to provide a catalyst which does not have the aforementioned disadvantages.
  • the catalyst should have a long service life and dehydrate cyclohexanol in high yield and high selectivity to cyclohexanone at comparatively low reaction temperatures. Constant adjustment of the reaction temperature should also be avoided.
  • the catalyst should be able to be processed into molded articles, in particular tablets, strands, rings, cylinders, without great effort and, owing to good hardness and abrasion resistance, should also be able to be used.
  • an improved catalyst consisting of ⁇ -aluminum oxide as support material and copper as active component has been found, the BET surface area (measured according to DIN 66131) of the aluminum oxide being not less than 30 m 2 / g.
  • the catalyst according to the invention is produced by applying the active components copper to an ⁇ -Al 0 3 support in a manner known per se, such as impregnation, precipitation, dry mixing or electroless copper plating, the ⁇ -Al 2 0 3 support according to the invention being a BET Surface area of not less than 30 m 2 / g.
  • An ⁇ -Al 2 O 3 with a BET surface area in the range from 50 to 300 m 2 / g is preferably used, particularly preferably from 100 to 250 m 2 / g.
  • high-surface area ⁇ -Al 2 0 3 is commercially available (for example, obtainable from Alcoa).
  • the carrier When impregnating, the carrier is generally impregnated with an aqueous solution of copper salts, preferably with the nitrates, sulfates, acetates or chlorides of copper, and the impregnated carrier is then dried and calcined.
  • a precipitant which leads to the formation of a poorly soluble copper compound is usually added to an aqueous solution of a copper salt (see above) in the presence of the carrier.
  • the copper is preferably used for the precipitation
  • the carrier When mixing dry, the carrier is usually mixed with the desired copper salt and then calcined.
  • a further preferred embodiment consists in the production of the catalyst by electroless deposition (copper plating) in the presence of the high-surface area ⁇ -aluminum oxide used according to the invention (see also Appl. Catal. A 103 (1994) 233-242).
  • the carrier is usually "inoculated" with a noble metal such as platinum, rhodium, iridium, gold or palladium, preferably palladium, i.e. crystallization-triggering centers are formed.
  • a noble metal such as platinum, rhodium, iridium, gold or palladium, preferably palladium, i.e. crystallization-triggering centers are formed.
  • the complexed copper is deposited on the carrier with a reducing agent.
  • a strong complexing agent such as ethylenediaminotetraacetate, the alkali metal salts of which are added, such as the tetrasodium salt, ethylenediamine or phenathroline, are preferably added.
  • the reduction is then generally carried out using a reducing agent which is able to separate copper (0) from copper salt solutions, such as formaldehyde or sodium formate.
  • the electroless deposition produces particularly small Cu particles.
  • Their size which can be determined with the aid of X-ray diffraction, is generally less than 50 nm, preferably less than 20 nm.
  • the powder or the corresponding shaped body obtained is calcined at a temperature in the range from 250 to 450 ° C. for one to 24 hours in air or an inert gas atmosphere, advantageously in nitrogen. Shaped articles can be produced before or after the calcination process.
  • the catalyst powder obtained from the electroless deposition and by the other processes listed above is preferably, generally with admixture of tabletting aids, to shaped articles such as tablets, strands, rings, wagon wheels, stars, monoliths, spheres, grit or extrudates, preferably tablets , pressed.
  • tabletting aids you can Use commonly used tableting aids. Examples include graphite, magnesium stearate, methyl cellulose (such as Walocel®), Cu powder or mixtures thereof.
  • the Cu content of the catalyst is usually chosen in the range from 0.01 to 50% by weight, preferably from 2 to 30% by weight, particularly preferably from 5 to 20% by weight, based on the total weight of the catalyst composition.
  • the BET surface area (measured according to DIN 66131) of the catalyst is generally not less than 30 m 2 / g, preferably in the range from 50 to 300 m 2 / g, particularly preferably in the range from 100 to 250 m 2 / g.
  • the dehydrogenation of cyclohexanol to cyclohexanone is generally carried out in the gas phase at temperatures from 180 to 400 ° C., preferably from 200 to 350 ° C., particularly preferably from 220 to 260 ° C.
  • the pressure is generally selected in the range from 50 kPa to 5 MPa, in particular one works under atmospheric pressure.
  • a mixture of cyclohexanol and cyclohexanone is generally used as the starting material for the reaction. Of course, you can also use pure cyclohexanone.
  • the mixture to be used usually consists of 50 to 100, preferably 60 to 99, in particular 96% by weight of cyclohexanol and 50 to 0, preferably 40 to 1, in particular 4% by weight, cyclohexanone.
  • Cyclohexanone and cyclohexanol are usually obtained by oxidation of cyclohexane and subsequent concentration of the cyclohexanol by removal of cyclohexanone and other low-boiling components by distillation.
  • the catalyst is reduced with hydrogen before the actual reaction.
  • the procedure is generally such that a hydrogen stream diluted with inert gas, preferably nitrogen, is passed over the catalyst at a certain temperature, preferably in the range from 120 to 300.degree.
  • the proportion of hydrogen in the reducing gas is then usually increased continuously until there is no significant change in temperature.
  • the starting material is passed over the catalyst in gaseous form, the LHSV (Liquid Hourly Space Velocity) preferably being from 0.1 to 100 h -1 , particularly preferably from 0.1 to 20 h -1 .
  • the starting material can be mixed with an inert gas such as nitrogen or with steam.
  • the product of the dehydration can be used as usual (see for example DE-A 1,296,625 and DE-A 1,443,462) are processed and further processed.
  • the hydrogen is separated from the reaction mixture leaving the reaction zone and added to the gas mixture entering the reaction zone. Furthermore, it is advantageous to circulate the reaction mixture until the desired conversion is reached.
  • the catalyst of the invention can because of its high
  • the catalyst according to the invention is characterized by good tablettability, sufficient hardness, high conversions at low operating temperatures, high selectivities to cyclohexanol and a good service life.
  • Pd-Sol polyvinylpyrrolidone
  • the suspension was heated to 70 ° C. and the pH was kept in the range from 12 to 12.5 by adding further NaOH (consumption of NaOH about 45 400 ml). The suspension was then stirred for a further 30 minutes after the temperature had reached 70 ° C. and then cooled to room temperature. The suspension was filtered off and washed with water until the water had a neutral pH (the filtrate had a light blue color). The washed solid was then dried at 110 ° C. under nitrogen for 16 h and then calcined at 300 ° C. for 2 h.
  • the catalyst produced in this way contained 16.5% by weight of copper and 0.046% by weight of sodium, based on the total weight of the gray-black catalyst.
  • the side pressure of the tablets was 53 N, the standard deviation 16 N (measured with a device from Frank, type no. 81557).
  • the catalyst tests were carried out in a tubular reactor with a diameter of 5 cm and a length of 60 cm. 200 ml of the catalyst were installed in each case and activated before the reaction with hydrogen. The catalyst was activated at 120 ° C. with 150 1 N 2 / h and 1.5 1 H 2 / h before the educt was applied. When the temperature rose more than 10 ° C, the hydrogen flow was stopped. The temperature was then gradually increased by 20 ° C to 240 ° C, the amount of hydrogen was kept constant. The catalyst was then activated at 240 ° C. with 150 1 H 2 / h and 7.5 1 H 2 / h.
  • Example 2 The test was carried out as described in Example 1, with the difference that a commercial Cu catalyst (catalyst CU 5 940 from Procatalyse) was used for the dehydrogenation.
  • a commercial Cu catalyst catalyst CU 5 940 from Procatalyse
  • the catalyst according to the invention already shows a conversion close to equilibrium at> 230 ° C. and at the same time very high selectivity> 99%. At this temperature, no noticeable
  • the temperatures in the comparative example are approximately 40 ° C. above the temperatures of the example according to the invention.
  • the selectivities in the example according to the invention are optimal. This was due to the use of aluminum oxide with a BET surface area of not less than

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

Catalyseur contenant en tant que matériau de support un α-oxyde d'aluminium et en tant que composant actif, du cuivre. La surface BET (déterminée conformément à la norme DIN 66131) de l'oxyde d'aluminium est égale ou supérieure à 30 m2/g. L'invention concerne également un procédé de production de ce catalyseur et l'utilisation de ce dernier pour la déshydrogénation du cyclohexanol en cyclohexanone. L'invention porte en outre sur l'utilisation d'α-oxyde d'aluminium dont la surface BET (selon DIN 66131) est égale ou supérieure à 30 m2/g, pour la production d'un catalyseur.
EP97927189A 1996-07-02 1997-06-17 Catalyseur pour la deshydrogenation du cyclohexanol, procede de production et utilisation dudit catalyseur Withdrawn EP0909214A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19626587 1996-07-02
DE19626587A DE19626587A1 (de) 1996-07-02 1996-07-02 Katalysator zur Dehydrierung von Cyclohexanol
PCT/EP1997/003135 WO1998000233A1 (fr) 1996-07-02 1997-06-17 Catalyseur pour la deshydrogenation du cyclohexanol, procede de production et utilisation dudit catalyseur

Publications (1)

Publication Number Publication Date
EP0909214A1 true EP0909214A1 (fr) 1999-04-21

Family

ID=7798698

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97927189A Withdrawn EP0909214A1 (fr) 1996-07-02 1997-06-17 Catalyseur pour la deshydrogenation du cyclohexanol, procede de production et utilisation dudit catalyseur

Country Status (15)

Country Link
EP (1) EP0909214A1 (fr)
JP (1) JP2000513269A (fr)
KR (1) KR20000022369A (fr)
CN (1) CN1094785C (fr)
AU (1) AU3176497A (fr)
BR (1) BR9710017A (fr)
CA (1) CA2258549A1 (fr)
CZ (1) CZ425498A3 (fr)
DE (1) DE19626587A1 (fr)
NO (1) NO986155L (fr)
PL (1) PL330957A1 (fr)
RU (1) RU2190468C2 (fr)
SK (1) SK172198A3 (fr)
TW (1) TW460327B (fr)
WO (1) WO1998000233A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6573409B1 (en) 1999-07-02 2003-06-03 The Nutrasweet Company Process for the preparation of 3,3-dimethylbutanal
KR100409083B1 (ko) * 2001-03-12 2003-12-11 주식회사 엘지화학 올레핀 제조용 탄화수소의 수증기 분해 촉매
KR100431898B1 (ko) * 2001-08-04 2004-05-17 애경유화 주식회사 카르보닐기 함유 화합물의 수소화 또는 사이클로알콜의탈수소화 반응에 유용한 구리-실리카 촉매 및 이의 제조방법
CN100360228C (zh) * 2005-05-31 2008-01-09 中国石油化工股份有限公司 一种醇脱氢制酮催化剂及其制备方法
CN102500420B (zh) * 2011-11-30 2014-03-05 大丰海嘉诺药业有限公司 一种醇气相脱氢催化剂及其制备方法和应用
RU2546122C1 (ru) * 2013-10-10 2015-04-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования (Российский химико-технологический университет им. Д.И. Менделеева) Катализатор для дегидрирования циклогексанола в циклогексанон

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU522853A1 (ru) * 1974-12-13 1976-07-30 Институт физико-органической химии АН Белорусской ССР Катализатор дл дегидрировани циклогексанола
JPS5620541A (en) * 1979-07-30 1981-02-26 Mitsubishi Chem Ind Ltd Preparation of cyclohexanone
US4472593A (en) * 1981-10-16 1984-09-18 Shell Oil Company Conversion of isopropyl alcohol to acetone
US5202511A (en) * 1989-08-16 1993-04-13 The Dow Chemical Company Catalyst diluent for oxychlorination process
CN1056067A (zh) * 1990-04-29 1991-11-13 王炳炎 多组分环己醇脱氢催化剂

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9800233A1 *

Also Published As

Publication number Publication date
NO986155D0 (no) 1998-12-28
CN1094785C (zh) 2002-11-27
NO986155L (no) 1998-12-28
BR9710017A (pt) 1999-08-10
JP2000513269A (ja) 2000-10-10
PL330957A1 (en) 1999-06-21
AU3176497A (en) 1998-01-21
SK172198A3 (en) 1999-04-13
CA2258549A1 (fr) 1998-01-08
RU2190468C2 (ru) 2002-10-10
DE19626587A1 (de) 1998-01-08
CN1224371A (zh) 1999-07-28
KR20000022369A (ko) 2000-04-25
TW460327B (en) 2001-10-21
WO1998000233A1 (fr) 1998-01-08
CZ425498A3 (cs) 1999-11-17

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