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WO1999028030A1 - Epoxidation catalyst, its use and epoxidation method in the presence of said catalyst - Google Patents

Epoxidation catalyst, its use and epoxidation method in the presence of said catalyst Download PDF

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Publication number
WO1999028030A1
WO1999028030A1 PCT/EP1998/007528 EP9807528W WO9928030A1 WO 1999028030 A1 WO1999028030 A1 WO 1999028030A1 EP 9807528 W EP9807528 W EP 9807528W WO 9928030 A1 WO9928030 A1 WO 9928030A1
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Prior art keywords
weight
catalyst according
titanium zeolite
catalyst
titanium
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PCT/EP1998/007528
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French (fr)
Inventor
Michel Strebelle
Jean-Pierre Catinat
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Solvay SA
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Solvay SA
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Priority to AU14358/99A priority Critical patent/AU1435899A/en
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    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium

Definitions

  • Epoxidation catalyst and its use epoxidation process in the presence of this catalyst Epoxidation catalyst and its use epoxidation process in the presence of this catalyst
  • the present invention relates to epoxidation catalysts. in particular catalysts based on zeolite titanium It also relates to the use of these catalysts in reactions of epoxidation and methods of epoxidation in the presence of these catalysts II is known to use catalysts based on silica you with titanium in epoxvdation reactions
  • catalysts based on silica you with titanium for example, in patent application EP-A2-0 200 260 we use rmcrospheres based on titanium silicahte with a diameter of about 20 ⁇ m obtained by atomization in epoxvdation reactions
  • This known catalyst gives rise to a deactivation phenomenon Regeneration cycles, implying manipulations, are therefore necessary
  • Regeneration cycles implying manipulations, are therefore necessary
  • these relatively small diameter catalysts are used in epoxidation reactions, they are difficult to isolate from the reaction medium in order to be able to transfer them to a treatment regeneration
  • the present invention aims to remedy to this problem by providing an easy new catalyst separate from the reaction medium epoxidation for the transpo ⁇ er in a regeneration unit
  • Another objective of the invention is to provide a Catalyst of epoxvdation presenting good mechanical strength high catalytic activity and high selectivity
  • Yet another object of the invention is to provide an easily usable catalyst in a fixed or agitated ht
  • titanium zeohte is meant to designate a solid containing silica which has a microporous crystalline structure of the zeohte type and in which several silicon atoms are replaced by titanium atoms
  • the titanium zeolite advantageously has a crystal structure of the ZSM-5, ZSM-1 1 or MCM-41 type. It can also have a crystal structure of the zeohte ⁇ type, free of aluminum.
  • Titanium zeolites of the silicahte type are well suited Those corresponding to the formula xTi ⁇ 2 (lx) Si ⁇ 2 in which x is from 0.0001 to 0.5, preferably from 0.001 to 0.05, are effective materials of this type, known as TS-1, have a microporous crystalline zeolitic structure similar to that of ze te ZSM-5 The properties and the main applications of these compounds are known (B Nota ⁇ , Structure-Activity and Selectivity Relationship in
  • extruded granules is understood to mean grains obtained by extrusion.
  • the granules are obtained by extraditing an extrudable mass containing the titanium zeohte and by cutting the extradate leaving the granular extruder.
  • the extruded granules can have any shape. be full or hollow They can be of round or rectangular section or of another section with a higher external surface. The cylindrical shapes are preferred.
  • the extruded granules of cylindrical shape advantageously have a diameter of at least 0.5 mm, preferably at least 1 mm
  • the diameter is usually at most 5 mm, in particular at most 2 mm
  • Cylindrical shapes usually have a length of at least 1 mm, in particular at least 2 mm
  • the lengths d '' at most 8 mm are common, those at most 4 mm give good results
  • Cylindrical shapes with a diameter of 0.5 to 5 mm, preferably 1 to 2 mm, and a length of 1 to 8 m m, preferably 2 to 4 mm are suitable
  • the content of titanium zeohte in the catalyst according to the invention is generally at least 1% by weight, in particular at least 50% by weight
  • the content of titanium zeolite is most often at most 99 % by weight, in particular at most 98% by weight
  • the catalyst according to the invention generally contains from 1 to 99% by weight, preferably from 50 to 98% by weight, titanium zeolite, the remainder consisting of a matrix. This matrix preferably contains a siliceous material.
  • the catalyst according to the invention can be obtained by a process comprising:
  • step (b) a step of shaping the dough obtained in step (a) by extrusion, in order to obtain an extradate
  • Step (c) a drying step, in order to remove at least part of the water, (d) a calcination step, in order to remove at least a part of the organic residues present, and comprising a granulation step carried out between step (b) of extrusion and step (c) of drying or after step (d) of calcination, in order to obtain extruded granules.
  • Step (a) generally consists in mixing a titanium zeolite powder with water, at least one binder, at least one plasticizer and possibly other additives until a paste of such viscosity is obtained. that it can be used in an extruder.
  • the mixing can be carried out in any mixer or kneader. All the constituents of the mixture can be mixed simultaneously.
  • the mixing is advantageously carried out at room temperature.
  • the particle size of the titanium zeolite powder used in step (a) can vary to a large extent. It is preferably characterized by an average diameter less than or equal to 10 ⁇ m, in particular less than or equal to 5 ⁇ m.
  • the average diameter is generally at least 0.05 ⁇ m, in particular at least 0.1 ⁇ m. Diameters less than 0.05 ⁇ m are also suitable.
  • the plasticizer which can be used in step (a) can be a polysaccharide such as a starch or a cellulose. Celluloses are fine. Mention may be made, as examples of cellulose, of methyl-, carboxymethyl- and hydroxyethylcellulose.
  • the amount of plasticizer used in step (a) can vary to a large extent. Reduced amounts of at least 1% and less than 10% by weight relative to the weight of titanium zeolite used are recommended because they lead to better resistance to attrition compared to higher amounts.
  • the binder that can be used in step (a) can be chosen from silicon derivatives such as siloxanes. We can cite as examples the ethers of methyl- or ethylsiloxane.
  • Polymethylsiloxane-based silicone resins can also be used. Polymethyl / phenylsiloxane type silicone resins are also suitable. It can also be mixtures of different oligomers of the methylsiloxane type.
  • the binder used in step (a) can be in the form of a powder. Alternatively, it may be in the form of an aqueous emulsion. It can also be used in liquid form. Silicone resins based on polymethylsiloxane in the form of a powder and mixtures of different oligomers of the methylsiloxane type in liquid form are preferred because they lead to catalysts of higher mechanical strength.
  • the binder is transformed, in step (d) of calcination. in a material constituting the matrix present in the catalyst according to the invention.
  • the amount of binder used in step (a) can vary to a large extent. It is usually at least 3% by weight, in particular at least 5% by weight, relative to the weight of titanium zeolite used. It is commonly less than 30% by weight, relative to the weight of titanium zeolite used. The amounts of 5 to 20% by weight relative to the weight of titanium zeolite used are particularly suitable because they lead to a better compromise between catalvtic activity and mechanical strength compared to the lower and higher amounts. Lubricants can also be added to the mixture of step (a).
  • They may be paraffin-based compounds, polyvinylpyrrolidone, polyethyleneoxide and polyvinyl alcohol.
  • Porogenic substances can also be added to the mixture of step (a). These substances are removed during step (d) of calcination and thus increase the porosity of the catalyst. Mention may be made, as examples of pore-forming substance, of melamine.
  • the amount of pore-forming substance used is generally at least 5% by weight, in particular at least 6% by weight, relative to the weight of titanium zeolite used. It is usually at most 35% by weight, in particular at most 14% by weight, relative to the weight of titanium zeolite used.
  • the amounts of 6 to 14% by weight relative to the weight of titanium zeolite used are particularly suitable because they lead to better resistance to attrition relative to the higher amounts.
  • Extraction step (b) can be carried out in a piston extruder. As a variant, it can be produced in a screw extruder.
  • the drying step (c) is advantageously carried out at low drying rates to ensure good cohesion of the catalyst. For example, pre-drying at low temperature (for example from room temperature to 90 ° C, possibly in combination with infrared or microwave irradiation) can first be carried out; then the temperature can be slowly increased to reach the final drying temperature. Alternatively, when the water can be removed quickly by adequate ventilation, the temperature can be increased at a higher speed. Temperatures of 100 to 400 ° C may be suitable when the drying time is long enough, for example 10 to 20 hours.
  • the calcination step (d) is generally carried out at a temperature of at most 550 ° C. Temperatures above 550 ° C are not recommended as most titanium zeolites do not withstand such temperatures.
  • the duration of the calcination step (d) must be long enough to be able to remove most of the organic residues from the binder and / or the plasticizer. Typical durations of 60 hrs.
  • the calcination step (d) is preferably carried out under an oxidizing atmosphere, for example in air.
  • the catalyst according to the invention can be used in the synthesis of oxiranes by reaction between an olefinic compound with a peroxide compound.
  • the invention therefore also relates to the use of the catalyst described above in these syntheses.
  • the invention also relates to a process for the manufacture of an oxirane by reaction between an olefinic compound and a peroxide compound in the presence of the catalyst described above.
  • the oxirane is preferably 1,2-epoxy-3-chloropropane or 1,2-epoxypropane.
  • the olefinic compound is preferably allyl chloride or propylene.
  • the peroxide compound can be chosen from those containing active oxygen and capable of carrying out an epoxidation. Hydrogen peroxide and peroxide compounds which can produce hydrogen peroxide under the conditions of the epoxidation reaction are well suited.
  • the peroxide compound is preferably hydrogen peroxide.

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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)
  • Epoxy Compounds (AREA)

Abstract

The invention concerns a catalyst based on titanium zeolite in the form of extruded granules and the use of said catalyst in the synthesis of oxirannes, preferably 1,2-epoxy-3-chloropropane or 1,2-epoxypropane, by reaction between an olefinic compound, preferably allyl chloride or propylene, with a peroxidized compound, preferably hydrogen peroxide. The invention also concerns a method for making an oxiranne, preferably 1,2-epoxy-3-chloropropane or 1,2-epoxypropane, by reaction between an olefinic compound, preferably allyl chloride or propylene, and a peroxidized compound, preferably hydrogen peroxide, in the presence of said catalyst.

Description

Catalyseur d epoxydation son utilisation et procède d'epoxydation en présence de ce catalyseurEpoxidation catalyst and its use epoxidation process in the presence of this catalyst

La présente invention concerne des catalyseurs d epoxydation. en particulier des catalyseurs a base de zeolite au titane Elle concerne également l'utilisation de ces catalyseurs dans des reactions d' epoxydation ainsi que des procèdes d' epoxydation en présence de ces catalyseurs II est connu d'utiliser des catalyseurs a base de silica te au titane dans des reactions d'epoxvdation Par exemple, dans la demande de brevet EP-A2-0 200 260 on utilise des rmcrospheres a base de silicahte au titane de diamètre d environ 20 μm obtenues par atomisation dans des reactions d epoxvdation Ce catalvseur connu donne lieu a un phénomène de desactivation Des cycles de régénération, impliquant des manipulations, sont donc nécessaires Lorsque ces catalyseurs de diamètre relativement faible sont utilises dans des reactions d'epoxydation, ils sont difficiles a isoler du milieu reactionnel pour pouvoir les transférer dans un traitement de régénérationThe present invention relates to epoxidation catalysts. in particular catalysts based on zeolite titanium It also relates to the use of these catalysts in reactions of epoxidation and methods of epoxidation in the presence of these catalysts II is known to use catalysts based on silica you with titanium in epoxvdation reactions For example, in patent application EP-A2-0 200 260 we use rmcrospheres based on titanium silicahte with a diameter of about 20 μm obtained by atomization in epoxvdation reactions This known catalyst gives rise to a deactivation phenomenon Regeneration cycles, implying manipulations, are therefore necessary When these relatively small diameter catalysts are used in epoxidation reactions, they are difficult to isolate from the reaction medium in order to be able to transfer them to a treatment regeneration

La présente invention vise a remédier a ce problème en fournissant un catalyseur nouveau facile a séparer du milieu de reaction d'epoxydation en vue de le transpoπer dans une unité de régénération Un autre objectif de l'invention est de fournir un catalvseur d epoxvdation qui présente une bonne résistance mécanique une activité catalvtique élevée et une sélectivité élevée Encore un autre objectif de l'invention est de fournir un catalyseur facilement utilisable en ht fixe ou agiteThe present invention aims to remedy to this problem by providing an easy new catalyst separate from the reaction medium epoxidation for the transpoπer in a regeneration unit Another objective of the invention is to provide a Catalyst of epoxvdation presenting good mechanical strength high catalytic activity and high selectivity Yet another object of the invention is to provide an easily usable catalyst in a fixed or agitated ht

La présente invention concerne des lors un catalyseur d'epoxydation a base de zeohte au titane qui se présente sous la forme de granules extrudes II a ete constate qu'un tel catalyseur présente simultanément les avantages suivantsThe present invention therefore relates to an epoxidation catalyst based on titanium zeohte which is in the form of extruded granules It has been found that such a catalyst simultaneously has the following advantages

- il est facile a séparer du milieu de reaction d epoxydation en vue de le transporter dans une unité de régénération,- it is easy to separate from the epoxidation reaction medium in order to transport it to a regeneration unit,

- il présente une bonne résistance mécanique, une activité catalvtique élevée et une sélectivité élevée, et- it has good mechanical strength, a high catalvtic activity and a high selectivity, and

- il est facilement utilisable en lit fixe ou agite- it can be easily used in a fixed or agitated bed

Par zeohte au titane on entend designer un solide contenant de la silice qui présente une structure cristalline microporeuse de type zeohte et dans laquelle plusieurs atomes de silicium sont remplaces par des atomes de titane La zeolite au titane présente avantageusement une structure cristalline de type ZSM-5, ZSM-1 1 ou MCM-41 Elle peut aussi présenter une structure cristalline de type zeohte β exempte d'aluminium Elle présente de préférence une bande d'absorption infrarouge a environ 950 - 960 cm~l Les zeolites au titane de type silicahte conviennent bien Celles repondant à la formule xTiθ2(l-x)Siθ2 dans laquelle x est de 0,0001 a 0,5, de préférence de 0,001 à 0,05, sont performantes Des matériaux de ce type, connus sous le nom de TS-1, présentent une structure zeolitique cristalline microporeuse analogue a celle de la zeo te ZSM-5 Les propπetes et les principales applications de ces composes sont connues (B Notaπ, Structure-Activity and Selectivity Relationship inBy titanium zeohte is meant to designate a solid containing silica which has a microporous crystalline structure of the zeohte type and in which several silicon atoms are replaced by titanium atoms The titanium zeolite advantageously has a crystal structure of the ZSM-5, ZSM-1 1 or MCM-41 type. It can also have a crystal structure of the zeohte β type, free of aluminum. It preferably has an infrared absorption band at approximately 950 - 960 cm ~ l Titanium zeolites of the silicahte type are well suited Those corresponding to the formula xTiθ2 (lx) Siθ2 in which x is from 0.0001 to 0.5, preferably from 0.001 to 0.05, are effective materials of this type, known as TS-1, have a microporous crystalline zeolitic structure similar to that of ze te ZSM-5 The properties and the main applications of these compounds are known (B Notaπ, Structure-Activity and Selectivity Relationship in

Heterogeneous Catalysis, R K Grasselli and A W Sleight Editors, Elsevier, 1991, p 243-256) Leur synthèse a ete étudiée notamment par A Van der Poel et J Van Hooff (Applied Catalysis A, 1992, Volume 92, pages 93-11 1) D'autres matériaux de ce type ont une structure analogue a celle de la zéolite bêta ou de la zeohte ZSM- 11Heterogeneous Catalysis, RK Grasselli and AW Sleight Editors, Elsevier, 1991, p 243-256) Their synthesis has been studied in particular by A Van der Poel and J Van Hooff (Applied Catalysis A, 1992, Volume 92, pages 93-11 1) Other materials of this type have a structure similar to that of zeolite beta or zeohte ZSM-11

Par granules extradés on entend designer des grains obtenus par extrusion En particulier les granules sont obtenus en extradant une masse extrudable contenant la zeohte au titane et en coupant l'extradât sortant de l'extradeuse en grains Les granules extradés peuvent avoir une forme quelconque Ils peuvent être pleins ou creux Ils peuvent être de section ronde ou rectangulaire ou encore d'une autre section a surface extérieure plus élevée On préfère les formes cylindriques Les granules extrudes de forme cylindrique ont avantageusement un diamètre d'au moins 0,5 mm, de préférence d'au moins 1 mm Le diamètre est couramment d'au plus 5 mm, en particulier d'au plus 2 mm Les formes cylindriques ont habituellement une longueur d'au moins 1 mm, en particulier d'au moins 2 mm Les longueurs d'au plus 8 mm sont courantes, celles d'au plus 4 mm donnent de bons résultats Les formes cylindriques ayant un diamètre de 0,5 a 5 mm, de préférence de 1 à 2 mm, et une longeur de 1 à 8 mm, de préférence de 2 a 4 mm conviennent bienThe term “extruded granules” is understood to mean grains obtained by extrusion. In particular, the granules are obtained by extraditing an extrudable mass containing the titanium zeohte and by cutting the extradate leaving the granular extruder. The extruded granules can have any shape. be full or hollow They can be of round or rectangular section or of another section with a higher external surface. The cylindrical shapes are preferred. The extruded granules of cylindrical shape advantageously have a diameter of at least 0.5 mm, preferably at least 1 mm The diameter is usually at most 5 mm, in particular at most 2 mm Cylindrical shapes usually have a length of at least 1 mm, in particular at least 2 mm The lengths d '' at most 8 mm are common, those at most 4 mm give good results Cylindrical shapes with a diameter of 0.5 to 5 mm, preferably 1 to 2 mm, and a length of 1 to 8 m m, preferably 2 to 4 mm are suitable

La teneur en zeohte au titane dans le catalyseur selon l'invention est en gênerai d'au moins 1 % en poids, en particulier d'au moins 50 % en poids La teneur en zeolite au titane est le plus souvent d'au plus 99 % en poids, en particulier d'au plus 98 % en poids Le catalyseur selon l'invention contient généralement de 1 a 99 % en poids, de préférence de 50 à 98 % en poids, de zeolite au titane, le restant étant constitué d'une matrice. Cette matrice contient de préférence une matière siliceuse.The content of titanium zeohte in the catalyst according to the invention is generally at least 1% by weight, in particular at least 50% by weight The content of titanium zeolite is most often at most 99 % by weight, in particular at most 98% by weight The catalyst according to the invention generally contains from 1 to 99% by weight, preferably from 50 to 98% by weight, titanium zeolite, the remainder consisting of a matrix. This matrix preferably contains a siliceous material.

Le catalyseur selon l'invention peut être obtenu par un procédé comprenant :The catalyst according to the invention can be obtained by a process comprising:

(a) une étape de malaxage d'un mélange comprenant une poudre de zeolite au titane, de l'eau, au moins un liant, au moins un plastifiant et éventuellement d'autres additifs, pour former une pâte,(a) a step of kneading a mixture comprising a titanium zeolite powder, water, at least one binder, at least one plasticizer and possibly other additives, to form a paste,

(b) une étape de mise en forme de la pâte obtenue dans l'étape (a) par extrasion, pour obtenir un extradât,(b) a step of shaping the dough obtained in step (a) by extrusion, in order to obtain an extradate,

(c) une étape de séchage, afin d'éliminer au moins une partie de l'eau, (d) une étape de calcination, afin d'éliminer au moins une partie des résidus organiques présents, et comprenant une étape de granulation effectuée entre l'étape (b) d' extrasion et l'étape (c) de séchage ou après l'étape (d) de calcination, afin d'obtenir des granules extradés. L'étape (a) consiste généralement à mélanger une poudre de zeolite au titane avec de l'eau, au moins un liant, au moins un plastifiant et éventuellement d'autres additifs jusqu'à l'obtention d'une pâte de viscosité telle que l'on puisse la mettre en oeuvre dans une extrudeuse. Le mélange peut être effectué dans un mélangeur ou un malaxeur quelconque. Tous les constituants du mélange peuvent être mélangés simultanément. Le mélange est avantageusement réalisé à température ambiante.(c) a drying step, in order to remove at least part of the water, (d) a calcination step, in order to remove at least a part of the organic residues present, and comprising a granulation step carried out between step (b) of extrusion and step (c) of drying or after step (d) of calcination, in order to obtain extruded granules. Step (a) generally consists in mixing a titanium zeolite powder with water, at least one binder, at least one plasticizer and possibly other additives until a paste of such viscosity is obtained. that it can be used in an extruder. The mixing can be carried out in any mixer or kneader. All the constituents of the mixture can be mixed simultaneously. The mixing is advantageously carried out at room temperature.

La granulométrie de la poudre de zeolite au titane mise en oeuvre dans l'étape (a) peut varier dans une large mesure . Elle est de préférence caractérisée par un diamètre moyen inférieur ou égal à 10 μm, en particulier inférieur ou égal à 5 μm. Le diamètre moyen est généralement d'au moins 0,05 μm, en particulier d'au moins 0, 1 μm. Des diamètres inférieurs à 0,05 μm conviennent également.The particle size of the titanium zeolite powder used in step (a) can vary to a large extent. It is preferably characterized by an average diameter less than or equal to 10 μm, in particular less than or equal to 5 μm. The average diameter is generally at least 0.05 μm, in particular at least 0.1 μm. Diameters less than 0.05 μm are also suitable.

Le plastifiant utilisable dans l'étape (a) peut être un polysaccharide tel qu'un amidon ou une cellulose. Les celluloses conviennent bien. A titre d'exemples de cellulose on peut citer la méthyl-, carboxyméthyl- et hydroxyéthylcellulose. La quantité de plastifiant mise en oeuvre dans l'étape (a) peut varier dans une large mesure. Des quantités réduites d'au moins 1 % et inférieures à 10 % en poids par rapport au poids de zeolite au titane mis en oeuvre sont recommandées car elles conduisent à une meilleure résistance à l'attrition par rapport aux quantités plus élevées. Le liant utilisable dans l'étape (a) peut être choisi parmi les dérivés du silicium tels que les siloxanes. On peut citer à titre d'exemples les éthers de méthyl- ou éthylsiloxane. Des résines siliconées à base de polyméthylsiloxane peuvent également être utilisées. Des résines siliconées de type polyméthyl/phénylsiloxane conviennent aussi. Il peut également s'agir de mélanges de différents oligomères de type méthylsiloxane. Le liant mis en oeuvre dans l'étape (a) peut être sous la forme d'une poudre. En variante, il peut être sous la forme d'une émulsion aqueuse. Il peut également être utilisé sous forme liquide. Les résines siliconées à base de polyméthylsiloxane sous forme d'une poudre et les mélanges de différents oligomères de type méthylsiloxane sous forme liquide sont préférés car ils conduisent à des catalyseurs de résistance mécanique plus élevée. Le liant est transformé, dans l'étape (d) de calcination. en une matière constituant la matrice présente dans le catalyseur selon l'invention.The plasticizer which can be used in step (a) can be a polysaccharide such as a starch or a cellulose. Celluloses are fine. Mention may be made, as examples of cellulose, of methyl-, carboxymethyl- and hydroxyethylcellulose. The amount of plasticizer used in step (a) can vary to a large extent. Reduced amounts of at least 1% and less than 10% by weight relative to the weight of titanium zeolite used are recommended because they lead to better resistance to attrition compared to higher amounts. The binder that can be used in step (a) can be chosen from silicon derivatives such as siloxanes. We can cite as examples the ethers of methyl- or ethylsiloxane. Polymethylsiloxane-based silicone resins can also be used. Polymethyl / phenylsiloxane type silicone resins are also suitable. It can also be mixtures of different oligomers of the methylsiloxane type. The binder used in step (a) can be in the form of a powder. Alternatively, it may be in the form of an aqueous emulsion. It can also be used in liquid form. Silicone resins based on polymethylsiloxane in the form of a powder and mixtures of different oligomers of the methylsiloxane type in liquid form are preferred because they lead to catalysts of higher mechanical strength. The binder is transformed, in step (d) of calcination. in a material constituting the matrix present in the catalyst according to the invention.

La quantité de liant mise en oeuvre dans l'étape (a) peut varier dans une large mesure. Elle est habituellement d'au moins 3 % en poids, en particulier d'au moins 5 % en poids, par rapport au poids de zeolite au titane mis en oeuvre. Elle est couramment inférieure à 30 % en poids, par rapport au poids de zeolite au titane mis en oeuvre. Les quantités de 5 à 20 % en poids par rapport au poids de zeolite au titane mis en oeuvre conviennent particulièrement bien car elles conduisent à un meilleur compromis entre l'activité catalvtique et la résistance mécanique par rapport aux quantités plus faibles et plus élevées. Des lubrifiants peuvent également être ajoutés dans le mélange de l'étape (a).The amount of binder used in step (a) can vary to a large extent. It is usually at least 3% by weight, in particular at least 5% by weight, relative to the weight of titanium zeolite used. It is commonly less than 30% by weight, relative to the weight of titanium zeolite used. The amounts of 5 to 20% by weight relative to the weight of titanium zeolite used are particularly suitable because they lead to a better compromise between catalvtic activity and mechanical strength compared to the lower and higher amounts. Lubricants can also be added to the mixture of step (a).

Il peut s'agir de composés à base de paraffine, de polyvinylpyrrolidone, de polyéthylèneoxyde et d'alcool polyvinylique.They may be paraffin-based compounds, polyvinylpyrrolidone, polyethyleneoxide and polyvinyl alcohol.

Des substances porogènes peuvent aussi être ajoutées dans le mélange de l'étape (a). Ces substances sont éliminées lors de l'étape (d) de calcination et augmentent ainsi la porosité du catalyseur. On peut citer à titre d'exemples de substance porogène la mélamine. La quantité de substance porogène mise en oeuvre est généralement d'au moins 5 % en poids, en particulier d'au moins 6 % en poids, par rapport au poids de zeolite au titane mis en oeuvre. Elle est habituellement d'au plus 35 % en poids, en particulier d'au plus 14 % en poids, par rapport au poids de zeolite au titane mis en oeuvre. Les quantités de 6 à 14 % en poids par rapport au poids de zeolite au titane mis en oeuvre conviennent particulièrement bien car elles conduisent à une meilleure résistance à l'attrition par rapport aux quantités plus élevées.Porogenic substances can also be added to the mixture of step (a). These substances are removed during step (d) of calcination and thus increase the porosity of the catalyst. Mention may be made, as examples of pore-forming substance, of melamine. The amount of pore-forming substance used is generally at least 5% by weight, in particular at least 6% by weight, relative to the weight of titanium zeolite used. It is usually at most 35% by weight, in particular at most 14% by weight, relative to the weight of titanium zeolite used. The amounts of 6 to 14% by weight relative to the weight of titanium zeolite used are particularly suitable because they lead to better resistance to attrition relative to the higher amounts.

L'étape (b) d'extrasion peut être réalisée dans une extrudeuse à piston. En variante, elle peut être réalisée dans une extrudeuse à vis. L'étape (c) de séchage est avantageusement réalisée à des vitesses faibles de séchage pour assurer une bonne cohésion du catalyseur. Par exemple, un préséchage à basse température (par exemple de la température ambiante à 90 °C, éventuellement en combinaison avec une irradiation infrarouge ou de micro-ondes) peut d'abord être réalisé; ensuite, la température peut être montée lentement pour atteindre la température finale de séchage. En variante, lorsque l'eau peut être évacuée rapidement par une ventilation adéquate, la température peut être augmentée à une vitesse plus élevée. Des températures de 100 à 400 °C peuvent convenir lorsque la durée du séchage est suffisamment longue, par exemple de 10 à 20 h.Extraction step (b) can be carried out in a piston extruder. As a variant, it can be produced in a screw extruder. The drying step (c) is advantageously carried out at low drying rates to ensure good cohesion of the catalyst. For example, pre-drying at low temperature (for example from room temperature to 90 ° C, possibly in combination with infrared or microwave irradiation) can first be carried out; then the temperature can be slowly increased to reach the final drying temperature. Alternatively, when the water can be removed quickly by adequate ventilation, the temperature can be increased at a higher speed. Temperatures of 100 to 400 ° C may be suitable when the drying time is long enough, for example 10 to 20 hours.

L'étape (d) de calcination est généralement effectuée à une température d'au plus 550°C. Des températures qui dépassent 550 °C ne sont pas recommandées car la plupart des zéolites au titane ne résistent pas à de telles températures. La durée de l'étape (d) de calcination doit être suffisamment longue pour pouvoir éliminer la plus grande partie des résidus organiques provenant du liant et/ou du plastifiant. Des durées de 60 h sont typiques. L'étape (d) de calcination est de préférence opérée sous atmosphère oxydante, par exemple sous air.The calcination step (d) is generally carried out at a temperature of at most 550 ° C. Temperatures above 550 ° C are not recommended as most titanium zeolites do not withstand such temperatures. The duration of the calcination step (d) must be long enough to be able to remove most of the organic residues from the binder and / or the plasticizer. Typical durations of 60 hrs. The calcination step (d) is preferably carried out under an oxidizing atmosphere, for example in air.

Le catalyseur selon l'invention peut être utilisé dans la synthèse d'oxirannes par réaction entre un composé oléfinique avec un composé peroxyde. L'invention concerne dès lors également l'utilisation du catalyseur décrit plus haut dans ces synthèses.The catalyst according to the invention can be used in the synthesis of oxiranes by reaction between an olefinic compound with a peroxide compound. The invention therefore also relates to the use of the catalyst described above in these syntheses.

L'invention concerne aussi un procédé de fabrication d'un oxiranne par réaction entre un composé oléfinique et un composé peroxyde en présence du catalyseur décrit plus haut. L'oxiranne est de préférence le l,2-époxy-3- chloropropane ou le 1,2-époxypropane. Le composé oléfinique est de préférence le chlorure d'allyle ou le propylene. Le composé peroxyde peut être choisi parmi ceux contenant de l'oxygène actif et capables d'effectuer une epoxydation. Le peroxyde d'hydrogène et les composés peroxydes qui peuvent produire du peroxyde d'hydrogène dans les conditions de la réaction d'epoxydation conviennent bien. Le composé peroxyde est de préférence le peroxyde d'hydrogène. The invention also relates to a process for the manufacture of an oxirane by reaction between an olefinic compound and a peroxide compound in the presence of the catalyst described above. The oxirane is preferably 1,2-epoxy-3-chloropropane or 1,2-epoxypropane. The olefinic compound is preferably allyl chloride or propylene. The peroxide compound can be chosen from those containing active oxygen and capable of carrying out an epoxidation. Hydrogen peroxide and peroxide compounds which can produce hydrogen peroxide under the conditions of the epoxidation reaction are well suited. The peroxide compound is preferably hydrogen peroxide.

Claims

R E V E N D I C A T I O N S R E V E N D I C A T I O N S 1 - Catalyseur d'epoxydation à base de zeolite au titane caractérisé en ce qu'il se présente sous la forme de granules extradés.1 - Epoxidation catalyst based on titanium zeolite, characterized in that it is in the form of extruded granules. 2 - Catalyseur selon la revendication 1, caractérisé en ce que la zeolite au titane présente une stracture cristalline de type ZSM-5, ZSM-11, MCM-41 ou de type zeolite β exempte d'aluminium.2 - Catalyst according to claim 1, characterized in that the titanium zeolite has a crystalline structure of type ZSM-5, ZSM-11, MCM-41 or of type zeolite β free of aluminum. 3 - Catalyseur selon la revendication 1 ou 2, caractérisé en ce que la zeolite au titane présente une bande d'absorption infrarouge à environ3 - Catalyst according to claim 1 or 2, characterized in that the titanium zeolite has an infrared absorption band at approximately 950 - 960 cm"1.950 - 960 cm " 1 . 4 - Catalyseur selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la zeolite au titane est une silicahte répondant à la formule xTiθ2(l-x)Siθ2 dans laquelle x est de 0,0001 à 0,5, de préférence de 0,001 à 0,05.4 - Catalyst according to any one of claims 1 to 3, characterized in that the titanium zeolite is a silicahte corresponding to the formula xTiθ2 (lx) Siθ2 in which x is from 0.0001 to 0.5, preferably from 0.001 to 0.05. 5 - Catalyseur selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les granules extradés sont cylindriques et ont un diamètre de 0,5 à 5 mm, de préférence de 1 à 2 mm, et une longeur de 1 à 8 mm, de préférence de 2 à 4 mm.5 - Catalyst according to any one of claims 1 to 4, characterized in that the extruded granules are cylindrical and have a diameter of 0.5 to 5 mm, preferably 1 to 2 mm, and a length of 1 to 8 mm, preferably 2 to 4 mm. 6 - Catalyseur selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il contient de 1 à 99 % en poids, de préférence de 50 à 98 % en poids, de zeolite au titane, le restant étant constitué d'une matrice.6 - Catalyst according to any one of claims 1 to 5, characterized in that it contains from 1 to 99% by weight, preferably from 50 to 98% by weight, of titanium zeolite, the remainder consisting of a matrix. 7 - Catalyseur selon l'une quelconque des revendications 1 à 6, caractérisé en ce que les granules extradés sont susceptibles d'être obtenus par un procédé comprenant :7 - Catalyst according to any one of claims 1 to 6, characterized in that the extruded granules are capable of being obtained by a process comprising: (a) une étape de malaxage d'un mélange comprenant une poudre de zeolite au titane, de l'eau, au moins un liant, au moins un plastifiant et éventuellement d'autres additifs, pour former une pâte,(a) a step of kneading a mixture comprising a titanium zeolite powder, water, at least one binder, at least one plasticizer and possibly other additives, to form a paste, (b) une étape de mise en forme de la pâte obtenue dans l'étape (a) par extrasion, pour obtenir un extradât,(b) a step of shaping the dough obtained in step (a) by extrusion, in order to obtain an extradate, (c) une étape de séchage, afin d'éliminer au moins une partie de l'eau, (d) une étape de calcination, afin d'éliminer au moins une partie des résidus organiques présents, et comprenant une étape de granulation effectuée entre l'étape (b) d' extrasion et l'étape (c) de séchage ou après l'étape (d) de calcination, afin d'obtenir des granules extradés.(c) a drying step, in order to remove at least part of the water, (d) a calcination step, in order to remove at least some of the organic residues present, and comprising a granulation step carried out between step (b) extrasion and step (c) drying or after step (d) to calcination, to obtain extrudates granules. 8 - Catalyseur selon la revendication 7, caractérisé en ce que le plastifiant est un polysaccharide, tel qu'un amidon ou une cellulose, de préférence choisie parmi la méthyl-, carboxyméthyl- et hydroxyéthylcellulose, et en ce que le liant est choisi parmi les dérivés du silicium tels que les siloxanes.8 - Catalyst according to claim 7, characterized in that the plasticizer is a polysaccharide, such as a starch or a cellulose, preferably chosen from methyl-, carboxymethyl- and hydroxyethylcellulose, and in that the binder is chosen from silicon derivatives such as siloxanes. 9 - Catalyseur selon la revendication 7 ou 8, caractérisé en ce que la poudre de zeolite au titane mise en oeuvre dans l'étape (a) présente un diamètre moyen inférieur ou égal à 10 μm.9 - Catalyst according to claim 7 or 8, characterized in that the titanium zeolite powder used in step (a) has an average diameter less than or equal to 10 μm. 10 - Catalyseur selon l'une quelconque des revendications 7 à 9, caractérisé en ce que la quantité de plastifiant mise en oeuvre dans l'étape (a) est d'au moins 1 % et inférieure à 10 % en poids par rapport au poids de zeolite au titane mis en oeuvre.10 - Catalyst according to one of Claims 7 to 9, characterized in that the amount of plasticizer implemented in step (a) is at least 1% and less than 10% by weight based on the weight of titanium zeolite used. 11 - Catalyseur selon l'une quelconque des revendications 7 à 10, caractérisé en ce que la quantité de liant mise en oeuvre dans l'étape (a) est de 3 à 70 % en poids, de préférence de 5 à 20 % en poids, par rapport au poids de zeolite au titane mis en oeuvre.11 - Catalyst according to any one of claims 7 to 10, characterized in that the amount of binder used in step (a) is from 3 to 70% by weight, preferably from 5 to 20% by weight , relative to the weight of titanium zeolite used. 12 - Catalyseur selon l'une quelconque des revendications 7 à 11, caractérisé en ce qu'une substance porogène est ajoutée au mélange de l'étape (a) en une quantité de 5 à 35 % en poids par rapport au poids de zeolite au titane mis en oeuvre.12 - Catalyst according to any one of claims 7 to 11, characterized in that a pore-forming substance is added to the mixture of step (a) in an amount of 5 to 35% by weight relative to the weight of zeolite in titanium used. 13 - Utilisation d'un catalyseur à base de zeolite au titane en forme de granules extradés dans la synthèse d'oxirannes, de préférence le l,2-époxy-3- chloropropane ou le 1.2-époxypropane, par réaction entre un composé oléfinique, de préférence le chlorare d'allyle ou le propylene, avec un composé peroxyde, de préférence le peroxyde d'hydrogène.13 - Use of a catalyst based on titanium zeolite in the form of granules extradited in the synthesis of oxiranes, preferably 1,2-epoxy-3-chloropropane or 1,2-epoxypropane, by reaction between an olefinic compound, preferably allyl chlorare or propylene, with a peroxide compound, preferably hydrogen peroxide. 14 - Procédé de fabrication d'un oxiranne, de préférence le l,2-époxy-3- chloropropane ou le 1,2-époxypropane, par réaction entre un composé oléfinique, de préférence le chlorare d'allyle ou le propylene, et un composé peroxyde, de préférence le peroxyde d'hydrogène, en présence d'un catalyseur à base de zeolite au titane en forme de granules extradés 14 - Process for the manufacture of an oxirane, preferably 1,2-epoxy-3-chloropropane or 1,2-epoxypropane, by reaction between an olefinic compound, preferably allyl chlorare or propylene, and a peroxide compound, preferably hydrogen peroxide, in the presence of a titanium zeolite catalyst in the form of extruded granules
PCT/EP1998/007528 1997-11-27 1998-11-18 Epoxidation catalyst, its use and epoxidation method in the presence of said catalyst Ceased WO1999028030A1 (en)

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BE9700963A BE1011578A3 (en) 1997-11-27 1997-11-27 EPOXIDATION CATALYST, ITS USE AND EPOXIDATION PROCESS IN THE PRESENCE OF THIS CATALYST.

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CN100575028C (en) * 2003-02-05 2009-12-30 巴斯福股份公司 The method and apparatus of separating pasty materials
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