WO1994008932A1 - Procede pour la decomposition par voie catalytique de peroxydes d'hydrogene organiques - Google Patents

Procede pour la decomposition par voie catalytique de peroxydes d'hydrogene organiques Download PDF

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Publication number
WO1994008932A1
WO1994008932A1 PCT/NL1993/000199 NL9300199W WO9408932A1 WO 1994008932 A1 WO1994008932 A1 WO 1994008932A1 NL 9300199 W NL9300199 W NL 9300199W WO 9408932 A1 WO9408932 A1 WO 9408932A1
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Prior art keywords
catalyst
decomposition
apo
metal
molecular sieve
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PCT/NL1993/000199
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English (en)
Inventor
Roger Arthur Sheldon
Ji Dong Chen
Jihad Dakka
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Technische Universiteit Delft
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.)
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Publication date
Application filed by Technische Universiteit Delft filed Critical Technische Universiteit Delft
Priority to EP93924212A priority Critical patent/EP0665827A1/fr
Priority to AU53776/94A priority patent/AU5377694A/en
Publication of WO1994008932A1 publication Critical patent/WO1994008932A1/fr

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    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the invention relates to a method for the catalyzed
  • Organic hydroperoxides are important intermediates in the preperation of, in particular, alcohols, ketones and acids, which in turn are frequently used as starting materials for organic synthesis processes.
  • Chhp cyclohexylhydroperoxide
  • cyclohexanol (Chol) are prepared through catalyzed decomposition. Chon can be converted to adipic acid, which is a reagent in the preparation of nylon 6.6. According to another industrial
  • Chhp Chon is converted with hydroxylamine to form Chon-oxime, which, via a Beckmann transformation, yields ⁇ -caprolactam, which is polymerized to nylon 6.
  • the decomposition of Chhp takes place under the catalytic action of metals, in particular transition metals such as cobalt, according to a mechanism known under the name of Haber-Weiss mechanism.
  • metals in particular transition metals such as cobalt
  • the catalytically active metals are used as an organic salt, for instance cobalt octoate, or in the form of a complex, but the catalysis involved is always a homogeneous catalysis, which means that the catalyst is present in dissolved condition, either in the organic liquid phase in which the decomposition occurs, or in an aqueous phase which is in contact therewith.
  • the catalytically active metals are used as an organic salt, for instance cobalt octoate, or in the form of a complex, but the catalysis involved is always a homogeneous catalysis, which means that the catalyst is present in dissolved condition, either in the organic liquid phase in which the decomposition occurs, or in an aqueous phase which is in contact therewith.
  • the decomposition of Chhp using a homogeneous catalyst has a number of important disadvantages.
  • the fact is it is inevitable that through lixiviation important quantities of catalyst are lost, ending up partly in the desired product and partly in waste streams. It is difficult to recover the catalyst therefrom, so that, on the one hand, fresh catalyst must always be added and, on the other, the environment is undesirably affected with metal waste coming from the lost catalyst.
  • the selectivity in the known decomposition of Chhp with a homogeneous catalyst is rather unfavorable in the sense that, in addition to the desired Chon, approximately twice that amount of Chol is obtained, which must' subsequently be converted to Chon by dehydrogenation.
  • EP-A-0 096 798 discloses the preparation of Chon and Chol by treating Chhp with a catalyst consisting of cobalt oxide
  • This catalyst possesses a slight stability, so that important quantities of the
  • the object of the invention is to prevent the above-described loss of catalyst and thereby to avoid the environment being burdened with metal waste.
  • hydroperoxides utilizing a heterogeneous catalyst which is composed of a three-dimensional microporous structure, a so-called molecular sieve, comprising aluminum, silicon and/or phosphorus oxides and a metal (Me) catalyst incorporated into the lattice.
  • a heterogeneous catalyst which is composed of a three-dimensional microporous structure, a so-called molecular sieve, comprising aluminum, silicon and/or phosphorus oxides and a metal (Me) catalyst incorporated into the lattice.
  • EP-A-0 203 632 describes a catalyst where aluminum and boron are incorporated into the lattice of zeolite crystals. This is an acid catalyst which is used in carrying out a specific acid catalysis. The fact is it has been found to effect a selective decomposition of cumene hydroperoxide in phenol and acetone.
  • the catalytic metal component (Me) of the present invention is the catalytic metal component (Me) of the present invention.
  • heterogeneous catalyst appears to remain inseparably bonded to the molecular sieve functioning as support, so that no metal (Me) is released into the reaction medium and also no metal (Me) is lost when the catalyst, for instance through filtration, is separated from the reaction medium and is subsequently
  • heterogeneous catalysts to be used in accordance with the invention are composed of a molecular sieve in which
  • molecular sieves are inorganic crystalline solid substances which are provided with fine holes or cavities where reactions can take place.
  • Examples of molecular sieves to be used in accordance with the invention include aluminophosphates (APGs), aluminophospho-silicates (SAPOs), aluminosilicates (zeolites) and silicalites (based exclusively on silica).
  • such molecular sieves which are eligible for use in accordance with the invention can conveniently be designated as Me-APOs, Me-SAPOs, Me-zeolites arid Me-silicalites.
  • the preparation can thus be carried out that first an aqueous paste is formed which contains the selected starting materials in the desired relative
  • Suitable starting materials include hydrated
  • the selected metal (Me) typically a suitable Me-salt
  • a so-called template which is a compound which determines the positions where later the holes or cavities of the molecular sieve are formed.
  • the metal (Me) then appears to be incorporated into the crystal lattice and occupy positions there which would otherwise be occupied by aluminum or silicon for instance.
  • the ultimate heterogeneous catalyst is then obtained by calcination, whereby the organic template material is burnt from the holes or cavities.
  • the catalytic metal (Me) is selected from the transition metals from the groups IV A (Ti, etc.), V A (V, etc.), VI A (Cr, etc.), VII A (Mn, etc.) and VIII A (Fe, Co, Ni, etc.) of the Periodic System and the rare earth metals such as Ce, La, etc.
  • the metals involved are redox metals or metals which can occur in different valence states and in fact the same metals (Me) are eligible as can also be used in the homogeneous
  • the holes or cavities in the molecular sieve should have a minimum size to allow the reaction medium and the reaction components present therein to penetrate.
  • the minimum size is therefore mainly determined by the nature of the hydroperoxide to be decomposed, for instance Chhp, and the medium in which it is dissolved, for instance cyciohexane.
  • larger holes or cavities may be present as well, but unduly large cavities, for instance of a size three or more times larger than the specified minimum size are less desirable, because they do not favor the efficient operation of the system.
  • the desired size of the holes or cavities can be controlled in known manner, in particular by the choice of the template.
  • templates are organic cavity-forming or cavity-filling compounds, for instance tri-alkylamines and tetra-alkylammonium salts, the size of the compounds used, for instance the length of the alkyl chains, being determinative of the final size of the holes or cavities.
  • the actual holes or cavities are formed when the template is burnt away by an a final calcination.
  • the heterogeneous catalysts for use according to the invention are redox catalysts, which are different from acid catalysts, and are catalytically active in such a manner that, through decomposition of the hydroperoxide, reaction products are formed which can be situated along the redox line, such as the ketone and the alcohol which correspond with that hydroperoxide.
  • Organic hydroperoxides which can be decomposed in accordance with the present method can be represented by the general formula ROOH, wherein R represents a primary, a secondary or a tertiary alkyl, alkenyl, alkynyl, cycloalkyl or aralkyl group, while the aromatic core may optionally be substituted by, for instance, alkyl, chlorine, etc.
  • R represents a primary, a secondary or a tertiary alkyl, alkenyl, alkynyl, cycloalkyl or aralkyl group
  • the aromatic core may optionally be substituted by, for instance, alkyl, chlorine, etc.
  • the following compounds can be mentioned: cyclohexylhydroperoxide, cyclododecylhydroperoxide, ethylbenzenelriydroperoxide,
  • the starting-point is a 2-5% solution of the hydroperoxide to be decomposed in a suitable solvent, preferably in the hydrocarbon from which the hydroperoxide is made.
  • a suitable solvent preferably in the hydrocarbon from which the hydroperoxide is made.
  • heterogeneous catalyst is added, whilst the amount of catalyst can vary within wide limits. It is for instance possible to add an amount of catalyst such that the molar ratio of hydroperoxide to catalytic metal (Me) is in the range of 5/1 to 450/1. For practical use on an industrial scale, such hydroperoxide to catalytic metal (Me) ratio is preferably selected in the range of 10/1 to 250/1.
  • the decomposition is then carried out by stirring the reaction mixture at increased temperature, for instance at a temperature of 50-80°C. These reaction conditions are known to a person of ordinary skill or can easily be determined.
  • heterogeneous catalyst is separated from the reaction mixture.
  • conventional techniques can be used, such as filtration or centrifugation.
  • conversions of almost 100% can be achieved. This points to a high catalytic activity.
  • the fact that even at molar ratios of hydroperoxide to catalytic metal (Me) of about 400/1 still a very reasonable conversion of about 50% could be observed is a further indication of a high catalytic activity.
  • a favorable selectivity can be achieved.
  • Chon/Chol ratios of between approximately 50/50 and 90/10 were determined, as mentioned hereinabove.
  • the catalyst separated from the reaction mixture can be washed and reactivated.
  • the reactivation is typically carried out by calcining the catalyst for some time. Then the catalyst can be used again. It appears to possess a high stability and even an increase of the catalytic activity could be observed. This constitutes supplementary evidence that the catalytically active metal (Me) is retained completely and that working in accordance with the invention prevents the environment from being damaged by the lost catalyst.
  • the viscous gel was placed in a teflon-coated 50 ml
  • the autoclave was cooled with an air stream and the Cr-APO-5 crystals were recovered by stirring the contents of the autoclave for a few minutes in 300 ml demineralized water to allow the crystals to settle and decanting the supernatant liquid. This procedure was repeated a number of times until a clear liquid was obtained. Then 150 ml ethanol was used to wash the crystals twice. Then the crystals were filtered off and dried for 4 h at 120°C.
  • the calcination was carried out by heating the crystals to 480°C with a temperature increase of 60°C/hour and maintaining them at 480°C for 5 h.
  • the molar composition of the Cr-APO-5 obtained is as
  • the Cr-APO-5 composition and structure were determined by the following techniques and by comparison with examples from the literature:
  • DRS diffuse reflection spectra
  • - elemental analysis of the calcined Me-APOs was performed by the use of inductively coupled plasma-atomic emission spectrometry (ICP-AES, Perkin-Elmer Plasma-II); the sample to be analyzed was pretreated as follows: 150 mg of the calcined Me-APO was weighed out in a plastics bottle and 6 ml of an acid solution prepared by diluting 1 ml concentrated H 2 SO 4 with 4 ml water and 1 ml 40% HF was added to the bottle; the bottle was closed and stored for 4-6 h at 60°C; then the bottle was cooled with ice and 8 ml 2.5% H 3 BO 3 was added; finally it was filled up with water to 100 ml.
  • ICP-AES inductively coupled plasma-atomic emission spectrometry
  • Co-APO-5 was prepared similarly to Cr-APO-5, but instead of Cr 3 (OH) 2 (CH 3 COO) 7 an equimolar amount of CoSO 4 .7H 2 O (Janssen) was used.
  • the composition and structure were determined by the above-mentioned techniques.
  • MN-APO-5 was also prepared similarly to Cr-APO-5, but instead of Cr 3 (OH) 2 (CH 3 COO) 7 an equimolar amount of
  • diisopropylamine was dropwise added to the mixture with stirring. A gel was obtained, which was stirred for 2 h at a temperature between 0 and 5°C.
  • the viscous blue gel was charged to a teflon-coated 50 ml autoclave and heated in an oven at 175°C for 2 days under
  • V-APO-11 composition and structure were determined by the techniques mentioned at the end of preparation 1.
  • V-APO-5 was prepared in the same manner as V-APO-11, except that as template triethanolamine was used instead of
  • V-APO-5 was carried out in the same manner as for V-APO-11.
  • a solution (B) was prepared, consisting of 22.05 g Na 2 SiO 3 in 14.5 g H 2 O .
  • a solution (C) was prepared of 12.22 g NaCl, 0.66 g
  • the solutions (A) and (B) were slowly introduced into solution (C) with a supply pump, with stirring and under a nitrogen stream.
  • the supply rate was regulated such that the pH of the mixture was kept within the range 10-10.5.
  • the supply time was 20 minutes. Although some gel precipitation was observed, the solution was stirred for another 30 minutes. Then the solution was homogenized for 1 h.
  • the solution was then transferred into an autoclave of stainless steel which was provided with a teflon coating.
  • the H-form ir the crystals was subjected to ion exchange with (NH 4 ) 2 CO 3 and Lhen calcined for 3 h at 470°C.
  • composition and structure of the product obtained were confirmed on the basis of XRD spectra and by comparison with examples from the literature.
  • Figures presenting the XRD of the product prepared and of an example from the literature for comparison are annexed.
  • the product prepared possesses the so-called pentasil structure.
  • Example 1
  • This example describes the catalytic decomposition of cyclohexylhydroperoxide (Chhp) utilizing heterogeneous catalysts according to the invention.
  • the reaction was carried in a 50 ml flask which was provided with a condensor and a magnetic agitator. 3.08 g of a Chhp-solution in cyclohexane (883 mmol Chhp/kg cyclohexane), 10 ml cyclohexane and an amount of heterogeneous catalyst corresponding with 0.028 mmol catalytic metal (Me) were incroduced into the flask. Then the flask was heated with circulating water of 70°C and stirred for 5 h. The reaction mixture was then cooled, whereafter the catalyst was separated by centrifugation.
  • chromatography analysis This was carried out under the following conditions: column 10 m ⁇ 0.53 mm, CP WAX 52 CB, film thickness 2.04 ⁇ m, ratio 65; temperature program 80°C, 0 min; 5°C/min; 140°C, 0 min.
  • the sample to be analyzed was prepared as follows: to 10 ml of a triphenylphosphine solution in 1,2-dichioroethane (24g/l) 15 ⁇ l hexadecane (internal standard) was added. 20 ⁇ l of the sample to be examined was added to 0.3 ml of the solution thus prepared. The solution thus obtained was agitated for a few seconds. Then 0.5 ⁇ l of this solution was analyzed directly by GC .
  • the conversion percentage was determined by titration of Chhp: to 35 ml chloroform/acetic acid (1:2 v/v) 3.0 g of the sample to be examined was added and then 2.5 ml of an aqueous KI solution (65 g/100 ml). The solution thus obtained was set in the dark for 0.5 h. After addition of 50 ml demineralized water, the solution was titrated with a 0.1 N solution of sodium thiosulfate until the brown-yellow color disappeared. A control sample containing no Chhp was analyzed as well.
  • reaction solution was also examined for traces of catalytic metal (Me) originating from the heterogeneous catalyst used. This examination was carried out through molecular spectrography. No traces of Me in the ppb range could be
  • Example 2 Two of the heterogeneous catalysts used in Example 1 were recirculated, a first time without being reactivated, and

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

L'invention se rapporte à une amélioration apportée à la décomposition par voie catalytique de peroxydes d'hydrogène organiques. Cette amélioration consiste à utiliser un catalyseur hétérogène qui est composé d'une structure microporeuse tridimensionnelle, à savoir un tamis moléculaire, contenant de l'aluminium, du silicium et/ou des oxydes de phosphore et un métal (Me) catalytique incorporé dans la structure en treillis du tamis. Un tel catalyseur n'entraîne substantiellement aucune perte lors de l'utilisation, de sorte qu'une économie considérable est réalisée et, en plus, toute nuisance à l'environnement par la production de déchets métalliques est évitée.
PCT/NL1993/000199 1992-10-09 1993-10-08 Procede pour la decomposition par voie catalytique de peroxydes d'hydrogene organiques WO1994008932A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP93924212A EP0665827A1 (fr) 1992-10-09 1993-10-08 Procede pour la decomposition par voie catalytique de peroxydes d'hydrogene organiques
AU53776/94A AU5377694A (en) 1992-10-09 1993-10-08 Method for the catalyzed decomposition of organic hydroperoxides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL9201756 1992-10-09
NL9201756A NL9201756A (nl) 1992-10-09 1992-10-09 Werkwijze voor de gekatalyseerde ontleding van organische hydroperoxiden.

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WO1994008932A1 true WO1994008932A1 (fr) 1994-04-28

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2744719A1 (fr) * 1996-02-09 1997-08-14 Rhone Poulenc Fibres Procede de decomposition catalytique des hydroperoxydes organiques
WO1997036910A1 (fr) * 1996-04-02 1997-10-09 Exxon Chemical Patents Inc. Production catalytique d'arylalkyl-hydroperoxydes par des agregats polynyucleaires de metaux de transition
WO1998034894A2 (fr) * 1997-02-11 1998-08-13 E.I. Du Pont De Nemours And Company Procede de decomposition d'hydroperoxydes
WO2000024698A1 (fr) * 1998-10-27 2000-05-04 Basf Aktiengesellschaft Procede de decomposition catalytique d'hydroperoxydes
FR2823745A1 (fr) * 2001-04-20 2002-10-25 Rhodia Polyamide Intermediates Procede de decomposition catalytique des hydroperoxydes organiques
JP2008510002A (ja) * 2004-08-17 2008-04-03 ソルティア・インコーポレーテッド シクロアルカン類の酸化およびシクロアルキルヒドロパーオキシドの分解のための触媒
US7417003B2 (en) 2006-12-29 2008-08-26 Uop Llc Solid acid catalyst and process for decomposition of cumene hydroperoxide
CN104525183A (zh) * 2014-12-08 2015-04-22 太原理工大学 一种负载铬基的介孔催化剂及其制备方法和应用
US9708238B2 (en) 2012-07-26 2017-07-18 Rhodia Operations Cycloalkane oxidation catalysts and method to produce alcohols and ketones

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0096798A1 (fr) * 1982-06-11 1983-12-28 BASF Aktiengesellschaft Procédé de préparation de cyclohexanol et de cyclohexanone
EP0203632A2 (fr) * 1985-04-23 1986-12-03 ENICHEM SYNTHESIS S.p.A. Catalyseur pour la décomposition sélective de l'hydroperoxyde de cumène et procédé de préparation
EP0492807A2 (fr) * 1990-12-27 1992-07-01 Texaco Chemical Company Procédé de préparation de phénol/acétone à partir d'hydroperoxyde de cumène

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0096798A1 (fr) * 1982-06-11 1983-12-28 BASF Aktiengesellschaft Procédé de préparation de cyclohexanol et de cyclohexanone
EP0203632A2 (fr) * 1985-04-23 1986-12-03 ENICHEM SYNTHESIS S.p.A. Catalyseur pour la décomposition sélective de l'hydroperoxyde de cumène et procédé de préparation
EP0492807A2 (fr) * 1990-12-27 1992-07-01 Texaco Chemical Company Procédé de préparation de phénol/acétone à partir d'hydroperoxyde de cumène

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2744719A1 (fr) * 1996-02-09 1997-08-14 Rhone Poulenc Fibres Procede de decomposition catalytique des hydroperoxydes organiques
WO1997036910A1 (fr) * 1996-04-02 1997-10-09 Exxon Chemical Patents Inc. Production catalytique d'arylalkyl-hydroperoxydes par des agregats polynyucleaires de metaux de transition
EA002422B1 (ru) * 1997-02-11 2002-04-25 Е.И.Дюпон Де Немур Энд Компани Способ разложения гидропероксида
WO1998034894A3 (fr) * 1997-02-11 1999-01-21 Du Pont Procede de decomposition d'hydroperoxydes
US6284927B1 (en) 1997-02-11 2001-09-04 E. I. Du Pont Nemours And Company Hydroperoxide decomposition process
WO1998034894A2 (fr) * 1997-02-11 1998-08-13 E.I. Du Pont De Nemours And Company Procede de decomposition d'hydroperoxydes
WO2000024698A1 (fr) * 1998-10-27 2000-05-04 Basf Aktiengesellschaft Procede de decomposition catalytique d'hydroperoxydes
FR2823745A1 (fr) * 2001-04-20 2002-10-25 Rhodia Polyamide Intermediates Procede de decomposition catalytique des hydroperoxydes organiques
WO2002085826A2 (fr) * 2001-04-20 2002-10-31 Rhodia Polyamide Intermediates Procede de decomposition catalytique des hydroperoxydes organiques
WO2002085826A3 (fr) * 2001-04-20 2003-11-06 Rhodia Polyamide Intermediates Procede de decomposition catalytique des hydroperoxydes organiques
JP2008510002A (ja) * 2004-08-17 2008-04-03 ソルティア・インコーポレーテッド シクロアルカン類の酸化およびシクロアルキルヒドロパーオキシドの分解のための触媒
US7417003B2 (en) 2006-12-29 2008-08-26 Uop Llc Solid acid catalyst and process for decomposition of cumene hydroperoxide
US9708238B2 (en) 2012-07-26 2017-07-18 Rhodia Operations Cycloalkane oxidation catalysts and method to produce alcohols and ketones
CN104525183A (zh) * 2014-12-08 2015-04-22 太原理工大学 一种负载铬基的介孔催化剂及其制备方法和应用
CN104525183B (zh) * 2014-12-08 2016-08-17 太原理工大学 一种负载铬基的介孔催化剂及其制备方法和应用

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EP0665827A1 (fr) 1995-08-09
AU5377694A (en) 1994-05-09
NL9201756A (nl) 1994-05-02

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