EP1044196A2 - Verfahren zur selektiven oxidation von organischen verbindungen - Google Patents

Verfahren zur selektiven oxidation von organischen verbindungen

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Publication number
EP1044196A2
EP1044196A2 EP98958553A EP98958553A EP1044196A2 EP 1044196 A2 EP1044196 A2 EP 1044196A2 EP 98958553 A EP98958553 A EP 98958553A EP 98958553 A EP98958553 A EP 98958553A EP 1044196 A2 EP1044196 A2 EP 1044196A2
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EP
European Patent Office
Prior art keywords
catalyst
group
carbon atoms
hydrogen peroxide
integer
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.)
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EP98958553A
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English (en)
French (fr)
Inventor
Michael Brian D'amore
Stephan Schwarz
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication of EP1044196A2 publication Critical patent/EP1044196A2/de
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/72—Epoxidation

Definitions

  • the invention generally relates to a process for oxidizing organic compounds.
  • the invention relates to a process utilizing hydrogen peroxide to oxidize an oxidizable organic substrate in the presence of a silica- modified titania/silica-containing catalyst and to a preparation of a catalyst using a copolymer of diethoxysilane and ethyl titanate.
  • Catalytic oxidation processes are important routes to many commercial chemicals.
  • numerous commercial processes for the epoxidation of olefins have been disclosed in the art.
  • One such process involves the reaction of an organic hydroperoxide with an olefin in the presence of catalytic amounts of certain soluble transition metal compounds (e.g., molybdenum, tungsten, or vanadium napthenates).
  • certain soluble transition metal compounds e.g., molybdenum, tungsten, or vanadium napthenates.
  • U.S. Patent No. 3,923,843 claims a process for the epoxidation of an olefinically unsaturated compound comprising reacting the compound in the liquid phase with an organic hydroperoxide in the presence of a catalyst comprising an inorganic siliceous compound in chemical combination with an oxide or hydroxide of titanium.
  • the catalyst is treated with an organic silylating agent before use.
  • the epoxide selectivity is increased from about 3% to about 15% when comparing the untreated catalyst to the silylated form.
  • the activity for both types of catalyst is about the same.
  • Hydrogen peroxide is often employed as an oxidizing agent for the production of organic chemicals.
  • a wide variety of organic compounds may be oxidized utilizing hydrogen peroxide, for example, olefins can be oxidized to epoxides (oxiranes) using this reagent.
  • titanosilicates have been reported to be useful as oxidation catalysts.
  • the catalytic oxidation of alkanes and alkenes by titanium silicates is disclosed in C. B. Khouw et al., "Studies on the Catalytic Oxidation of Alkanes and Alkenes by Titanium Silicates", Journal of Catalysis 149, 195-205 ( 1994).
  • Such catalysts are used for the selective oxidation of n-octane using organic hydroperoxides as the oxidants at temperatures below 100°C. The absence of water is deemed critical for catalytic activity.
  • the invention provides a process for oxidizing organic compounds comprising: contacting, in a zone of reaction, an oxidizable organic compound with hydrogen peroxide in the presence of a catalytically effective amount of an insoluble catalyst comprising silicon oxide and an oxide of at least one hydrogen peroxide-activating metal, which catalyst is treated with a silylating agent, and wherein the activity of the treated catalyst is increased by a factor of at least two compared to the untreated catalyst.
  • the organic compound is selected from the group consisting of:
  • the invention also provides a process for the preparation of a molecular sieve catalyst comprising synthesizing a catalyst comprising oxides of silicon and titanium by contacting the catalyst with a copolymer of diethoxysilane and ethyl titanate to form a molecular sieve catalyst.
  • Hydrogen peroxide-activating metals include, for example, silver, cobalt, cerium, manganese, iron, copper, molybdenum, tungsten, vanadium, titanium, chromium and mixtures thereof.
  • Metallosilicates containing the above metals can be prepared in a similar manner to that described in R. Neumann et al., "Metal Oxide (Ti ⁇ 2, M0O3, WO3) Substituted Silicate Xerogels as Catalysts for the Oxidation of Hydrocarbons with Hydrogen Peroxide", Journal of Catalysis, 166, pp. 206-217 (1997).
  • a presently preferred metal is tetrahedrally coordinated titanium.
  • Metallosilicates which can contain tetrahedrally coordinated titanium include the following molecular sieve structures: silicalite- 1 (TS-1), silicalite-2 (TS-2), zeolite-beta, silicon analogs of ZSM-48 and MCM-41. (See R. Murugavel and H. W. Roesky, "Titanosilicates: Recent Developments in Synthesis and Use as Oxidation Catalysts", Angew. Chem. Int. Ed. Engl., 36, No. 5, pp. 477-479 (1997) for a discussion of titanosilicates, their synthesis, and use as oxidation catalysts).
  • crystalline titanium silicalite is used as the catalyst.
  • porous crystalline titanium silicalite (TS-1) which corresponds to the foimula, xTiO2(l-x)SiO2, where x is between about 0.0005 and about 0.04 has been disclosed in U.S. Patent No. 4,410,501 the contents of which are incorporated herein by reference.
  • TS-1 has been shown to catalyze numerous reactions including the following selective oxidations; aromatic hydroxylations, alkane oxidations and aikene epoxidations.
  • the oxidation reactions are perfoimed using dilute (40% or less) aqueous hydrogen peroxide.
  • the reactions are typically run at 100°C or less and at atmospheric pressure.
  • molecular sieve catalysts prepared by the process of this invention include materials having MFI, MEL, M41S, MOR and BEA type structures.
  • Materials having an M41S structure are described in A. Corma, Chem. Rev., 97, 2373 to 2419 (1997), particularly at page 2386.
  • the other molecular sieve structures are described in W. M. Meier et al., "Atlas of Zeolite Structure Types", 4 th ed., published in Zeolites, 17, Nos. 1/2 (1996).
  • Si ⁇ 2 is between 0.0005:1 and 0.5:1 can also be the catalyst in the above-named oxidation reactions.
  • This material is commercially available or it can be prepared by the procedure disclosed in D. C. M. Dutoit et al., "Titania-Silica Mixed Oxides", Journal of Catalysis, 164, pp. 433-439 (1996).
  • activities are improved by modifying the catalyst with a coating using a silylating agent.
  • coating of the oxidation catalyst can be accomplished by a variety of techniques.
  • a sample of the catalyst can be exposed to the ambient atmosphere and immersed in tetraethylorthosilicate (TEOS) for 2 hours; the sample is then filtered and dried at room temperature overnight; (the sample is then heated in flowing nitrogen at 550°C for 3 hours).
  • TEOS tetraethylorthosilicate
  • the preceding treatment can be performed with one or more compounds containing at least one element selected from silicon, aluminum, boron and phosphorus, to deposit substantially, on the external surfaces of the oxidation catalyst, at least 0.05 weight % of the element.
  • Silicon compounds are the presently preferred coating agents used for silylation.
  • suitable silylating agents include organosilanes, organosilylamines, and organosilazanes.
  • suitable silanes include chlorotrimethylsilane ((C ⁇ SiCl), dichlorodimethylsilane ((CH 3 ) 2 SiCl2), bromochlorodimethylsilane ((CH 3 ) 2 SiBrCl), chlorofriethylsilane ((C 2 H 5 ) 3 SiCl) and chlorodimethylphenylsilane ((CH3) 2 Si(C6H 5 )Cl).
  • silazanes examples include 1 ,2-diethyldisilazane (C2H 5 SiH2NHSiH2C2H5), 1 , 1 ,2,2-tetramethyldisilazane ((CH 3 ) 2 SiHNHSiH(CH 3 ) 2 ), 1,1,1 ,2,2,2-hexamethyldisilazane ((CH 3 ) 3 SiNHSi(CH 3 ) 3 ), 1,1 ,2,2-tetraethyldisilazane (C 2 H5)2SiHNHSiH(C 2 H 5 )2 and 1 ,2-diisopropyldisilazane ((CH 3 )2CHSiH2NHSiH 2 CH(CH3) 2 ).
  • the silylation of the oxidation catalyst may be done in various ways including that described above.
  • the catalyst particles may be mixed with a liquid silylating agent at temperatures from about room temperature to about 450°C.
  • the catalyst particles may be heated from about 100°C to about 450°C and then contacted with a stream of hot silylating agent vapor.
  • the silylation may be carried out as a batch, semi-continuous or continuous process.
  • the time required for the silylating agent to react with the catalyst surface is dependent on the temperature and agent used. Lower temperatures require longer reaction times. Typically, times of from about OJ to about 48 hours are suitable.
  • silylating agent used, for practical reasons it is believed that it can vary from about 1% to about 1000% by weight of the entire catalyst composition.
  • the silylating agent can be applied to the catalyst either in one or a series of treatments.
  • Olefins useful in the process of this invention may be any organic compound having at least one ethylenically unsaturated functional group (i.e., a carbon-carbon double bond) and may be a cyclic, branched, or straight chain olefin.
  • the olefin is reacted with hydrogen peroxide to produce an epoxide (oxirane).
  • the olefin may contain aryl groups such as phenyl.
  • the olefin is an aliphatic compound containing from 2 to 20 carbon atoms. Multiple double bonds may be present in the olefin, e.g., dienes, trienes, and other polyunsaturated substrates.
  • the double bond may be in a terminal or internal position of the olefin or may form part of a cyclic structure as in cyclohexene.
  • suitable organic compounds include unsaturated fatty acids or esters and oligomeric or polymeric unsaturated compounds such as polybutadiene.
  • the olefin may optionally contain functional groups such as halide, carboxylic acid, ether, hydroxy, thio, nitro, cyano, ketone, acyl, ester, amino, and anhydride.
  • Prefeired olefins include ethylene, propylene, butenes, butadiene, pentenes, isoprene, and hexenes.
  • Mixtures of olefins may be epoxidized and the resulting mixtures of epoxides may be used in mixed form or separated into the component epoxides.
  • Cyclic ketones useful in the process of this invention include cyclopentanone, cyclohexanone.
  • the cyclic ketone is reacted with the in-situ generated hydrogen peroxide to produce lactones.
  • cyclopentanone is converted to valerolactone and cyclohexanone is converted to caprolactone.
  • ammonia cyclohexanone is converted to cyclohexanone oxime.
  • Alicyclic hydrocarbons of the foimula R 8 R 9 CH 2 , wherein R 8 and R 9 together form a link selected from the group consisting of (-CH 2 -) p , wherein p is an integer from 4 to 11 useful in the process of this invention include cyclohexane and cyclododecane.
  • Alicyclic hydrocarbons of the formula R 8 R 9 CH2 are reacted with hydrogen peroxide to produce ketones and alcohols. For example, cyclohexane is converted to a mixture of cyclohexanol and cyclohexanone and cyclododecane is converted to a mixture of cyclododecanol and cyclododecanone.
  • Aliphatic hydrocarbons of the formula C q H2 q+ 2 > wherein q is an integer from 1 to 20 useful in the process of this invention include hexane and heptane. Aliphatic hydrocarbons of the formula CqH 2 q + 2 are reacted with hydrogen peroxide to produce alcohols and ketones.
  • Alcohols according to the formula R ⁇ R 1 iCHOH, wherein R 10 and R 1 ⁇ * are as defined above include 2-butanol, cyclohexanol, and cyclododecanol. These alcohols are oxidized to 2-butanone, cyclohexanone, and cyclododecanone, respectively.
  • oximes can be prepared by
  • n is an integer from 2 to 9
  • the reaction may also be conducted in organic solvents.
  • organic solvents are hydrocarbons such as hexane, benzene, methylene chloride, acetonitrile, lower aliphatic alcohols, ketones and dioxane, dimethylformamide and dimethylsulfoxide and mixtures thereof.
  • the solvents which are used are ones in which the substrate and products of the reaction are highly soluble.
  • the reaction is typically conducted at temperatures of from about 0°C to about 200°C, preferably from about 25°C to about 150°C.
  • the reaction pressure is typically from about 1 atmosphere to about 100 atmospheres.
  • the oxidation products are recovered from the product mixtures by conventional techniques such as fractional distillation, extraction, and crystallization.
  • Titanium isopropoxide (28.4 g) and isopropyl alcohol (IPA, 30 mL) were mixed and acetylacetone (10.01 g) in IPA (10 mL) was added.
  • IPA isopropyl alcohol
  • the resulting solution was heated to reflux for one hour and then cooled.
  • the IPA was removed under vacuum and the resultant solid was redissolved in IPA to make up 100 mL.
  • the solution was 1 molar in Ti.
  • the sol-gel was extracted with supercritical CO2 at 40°C at 3500 psig (24.2 MPa) for 5 hours.
  • the resulting fluffy yellow powder was calcined as follows: 400°C for 1 hour in N 2 followed by 600°C for 5 hours in air.
  • Catalyst A was x-ray amorphous.
  • Catalyst A The procedure for the preparation of Catalyst A was followed except that the gel mixture was aged for 90 hours.
  • toluene 7.96 g
  • Catalyst B2 To Catalyst A (1.02 g) was added a mixture of 1.05 g BSTFA (1.05 g) and toluene (7.87 g). The slurry mixture was stirred for two hours at room temperature, filtered, the solids washed with toluene, and air dried. Preparation of Catalyst C
  • a homogeneous slurry of 50% aqueous NaOH solution (9.066 g), fumed Si ⁇ 2 (20 g) and H2O (98 g) was prepared. The slurry was stirred for 1/2 hour. A solution of dodecytrimethylammoniumbromide (51.39 g) in H2O (74.5 g) was added and the mixture was stirred for 1 hour, resulting in a translucent gel. This gel was digested in a Teflon® bottle at 100°C for 5 days. The material was calcined in air as follows: 5°C/min to 250°C; 2°C/min to 550°C; and held at temperature for 4 hours. It was then cooled.
  • the resultant solid had the x-ray pattern of molecular sieve MCM-41.
  • the calcined dry MCM-41 (3.5 g) was treated with 0.427 g of TYZOR
  • Catalyst C (0.482 g) was added a mixture of BSTFA (1.08 g) and toluene (8.97 g). The slurry mixture was stirred for two hours at room temperature, filtered, the solids washed with toluene, and air dried.
  • Catalyst E 0.527 g was added a mixture of BSTFA (1.04 g) and toluene (8.94 g). The mixture was stirred for two hours at room temperature, filtered, the solids washed with toluene, and air dried.
  • Preparation of Catalyst G To titanosilicalite (0J23 g; prepared in a manner similar to that described in U.S. Patent No. 4,410,501 and having Ti:SiO 2 weight ratio of 1.9%) was added BSTFA (0.486 g) and toluene (3.96 g). After stirring at room temperature for two hours, the solids were filtered, washed with toluene, and air dried.
  • Cetyltrimethylammoniumbromide (6.44 g) was dissolved in tetramethyl- ammoniumhydroxide (26.98 g).
  • the PSITI-019 precursor (20.0 g) was added dropwise with strong agitation. The mixture was stirred at 25 °C for 3 days and 17 hours. The products were filtered and washed with distilled H 2 O (1 L). The dried white solids were calcined by heating in air at l°C/min to 550°C, which was maintained for 4 hours before cooling. Long range mesoporous order was demonstrated by an XRD peak at
  • Cetyltrimethylammoniumbromide (3.22 g) was dissolved in dilute HC1 made by combining 36.6 g cone. HC1 and 148.5 g H2O.
  • Tetraethylorthosilicate (15.4 g) was added to the PSITI-019 precursor (4.61 g). 40% aqueous tetrapropylammoniumhydroxide (19.34 g, TPAOH) solution was dripped into the clear alkoxide mixture while stirring vigorously at 25°C. After less than 15 minutes, the mixture gelled into a hard brittle mass. This was broken up and dispersed by the addition of the rest of the TPAOH. Almost all of the solids were dissolved during stirring and addition of H 2 O (140.5 g) over a period of about 1 hour. The final clear solution was filtered into a Teflon® bottle, which was sealed and placed into an oven at 100°C. The synthesis was stopped after 5 days and 18 hours. The filtered, washed, and dried material was calcined at 520°C for 10 hours.
  • TPAOH aqueous tetrapropylammoniumhydroxide
  • Tetrahedral Ti was present as shown by a single UVNisible spectral band at 206 nm. The infrared band at 971 cm -1 was further evidence of Ti framework incorporation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP98958553A 1997-11-24 1998-11-12 Verfahren zur selektiven oxidation von organischen verbindungen Withdrawn EP1044196A2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US6642997P 1997-11-24 1997-11-24
US66429P 1997-11-24
PCT/US1998/024176 WO1999026936A2 (en) 1997-11-24 1998-11-12 Process for the selective oxidation of organic compounds

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DE19918431A1 (de) 1999-04-23 2000-10-26 Bayer Ag Verfahren zur Herstellung eines Katalysators zur selektiven Oxidation von Kohlenwasserstoffen
DE19954322A1 (de) * 1999-11-10 2001-05-17 Basf Ag Oxid und Verfahren zu dessen Herstellung
DE19959525A1 (de) * 1999-12-09 2001-06-13 Bayer Ag Katalysatoren auf Basis Edelmetall- und Titan-haltiger, organisch-anorganisch Hybridmaterialien zur selektiven Oxidation von Kohlenwasserstoffen
DE10023717A1 (de) * 2000-05-17 2001-11-22 Bayer Ag Formkörper, Verfahren zu dessen Herstellung und Verwendung dieser Formkörper zur selektiven Oxidation von Kohlenwasserstoffen
JP2002145872A (ja) * 2000-11-01 2002-05-22 Maruzen Petrochem Co Ltd エポキシ化合物の製造方法
FR2824565B1 (fr) * 2001-05-09 2003-07-04 Solvay Procede de desulfuration d'un melange d'hydrocarbures
EP1488853A4 (de) * 2002-03-04 2011-11-02 Sumitomo Chemical Co Verfahren zur verbesserung von kristallinem titansilicatkatalysator mit mww-struktur
JP2004285055A (ja) * 2003-03-06 2004-10-14 Sumitomo Chem Co Ltd プロピレンオキサイドの製造方法
CN102766032B (zh) * 2011-05-05 2014-10-01 中国石油化工股份有限公司 一种环己烷氧化的方法

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JP2001524475A (ja) 2001-12-04
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