WO2004050233A1 - Process for the preparation of epoxidation catalysts - Google Patents

Process for the preparation of epoxidation catalysts Download PDF

Info

Publication number
WO2004050233A1
WO2004050233A1 PCT/EP2003/050875 EP0350875W WO2004050233A1 WO 2004050233 A1 WO2004050233 A1 WO 2004050233A1 EP 0350875 W EP0350875 W EP 0350875W WO 2004050233 A1 WO2004050233 A1 WO 2004050233A1
Authority
WO
WIPO (PCT)
Prior art keywords
carrier
process according
silicon containing
catalyst
preparation
Prior art date
Application number
PCT/EP2003/050875
Other languages
French (fr)
Other versions
WO2004050233A8 (en
Inventor
Johannes Petrus Van Der Linden
Eduardus Petrus Simon Schouten
Original Assignee
Shell Internationale Research Maatschappij B.V.
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 Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to MXPA05005699A priority Critical patent/MXPA05005699A/en
Priority to EP03796044A priority patent/EP1567261A1/en
Priority to CA002508043A priority patent/CA2508043A1/en
Priority to BR0316825-5A priority patent/BR0316825A/en
Priority to JP2004556324A priority patent/JP2006507932A/en
Priority to AU2003298312A priority patent/AU2003298312A1/en
Publication of WO2004050233A1 publication Critical patent/WO2004050233A1/en
Publication of WO2004050233A8 publication Critical patent/WO2004050233A8/en

Links

Classifications

    • 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
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0209—Impregnation involving a reaction between the support and a fluid

Definitions

  • the present invention relates to the preparation of an epoxidation catalyst and to the process of preparing alkylene oxide with the help of such catalyst.
  • An epoxidation catalyst is understood to be a catalyst which catalyses the manufacture of an epoxy group containing compound.
  • a well known process comprises contacting a hydroperoxide and alkene with a heterogeneous epoxidation catalyst and withdrawing a product stream comprising alkylene oxide and an alcohol.
  • Catalysts for the manufacture of an epoxy group containing compound are well known.
  • EP-A-345856 describes the preparation of such catalyst comprising titanium in chemical combination with a solid silica and/or inorganic silicate.
  • the preparation comprises (a) impregnating a silicium compound with a stream of gaseous titanium tetrachloride preferably comprising an inert gas, (b) calcining the obtained reaction product of step (a) , and (c) hydrolysis of the product of step (b) .
  • the stream of inert gas also has the function of a carrier for the gaseous titanium tetrachloride. For such use, the gas is to be present in a relatively large amount .
  • the present invention relates to a process for the preparation of an epoxidation catalyst, which process comprises impregnating a silicon containing carrier with a gas stream consisting of titanium halide.
  • a catalyst of improved selectivity was obtained even though the carrier had been in contact with the same amount of titanium halide.
  • the catalyst of the present invention is obtained by impregnating a silicon containing carrier.
  • any silicon containing carrier is suitable for use in the preparation process according to the present invention.
  • silicon containing carriers comprise zeolites.
  • the silicon containing carrier is a silica carrier.
  • Silica carriers will substantially consist of silicon dioxide. However, limited amounts of further compounds such as contaminants can be present as well. It is known that contaminants can influence the performance of the final catalyst.
  • the silica carrier for use in the present invention preferably contains at most 1200 ppm of sodium, more specifically at most 1000 ppm of sodium. Further, the silica carrier preferably comprises at most 500 ppm of aluminium, at most 500 ppm of calcium, at most 200 ppm of potassium, at most 100 ppm of magnesium and at most 100 ppm of iron. The amounts are based on amount of carrier.
  • the silica carrier preferably is a silica gel.
  • the silica gel carrier for use in the present invention can in principle be any carrier derived from a silicon containing gel.
  • silica gels are a solid, amorphous form of hydrous silicon dioxide distinguished from other hydrous silicon dioxides by their micro- porosity and hydroxylated surface.
  • Silica gels usually contain three-dimensional networks of aggregated silica particles of colloidal dimensions. They are typically prepared by acidifying an aqueous sodium silicate solution to a pH of less than 11 by combining it with a strong mineral acid. The acidification causes the formation of monosilicilic acid (Si (OH) ), which polymerizes into particles with internal siloxane linkages and external silanol groups.
  • Si (OH) monosilicilic acid
  • silica gel carrier would be silica support V432 and DAVICAT P-732, which are commercially available from Grace Davison.
  • Silica gel carriers for use in the present invention preferably have a weight average particle size of at most 2 millimetres. Particle sizes which were found to be especially suitable were weight average particle, sizes of from 0.2 to 1.8 mm, more specifically of from 0.4 to 1.6 mm, most specifically of from 0.6 to 1.4 mm.
  • the silicon containing carrier preferably has a low water content when contacted with the titanium halide.
  • a low water content can be achieved in any way known to someone skilled in the art.
  • a preferred way comprises drying the silicon containing carrier before impregnating the silicon containing carrier with the gas stream consisting of titanium halide.
  • a suitable drying method comprises subjecting the silicon containing carrier to a temperature of from 200 to 700 °C. Surprisingly it has been found that drying under specific circumstances gives a further improved catalyst.
  • the preferred drying conditions comprise drying the carrier at a temperature of from more than 200 to 300 °C. The drying is preferably carried out during of from 1 to 8 hours, preferably in the presence of an inert gas such as nitrogen.
  • the preferred method has been described in more detail in co- pending patent application claiming priority of European application 02258294.4.
  • Hydrolysis comprises treating the carrier with water or steam.
  • the hydrolysis is carried out with steam.
  • the hydrolysis treatment may comprise a washing treatment using an aqueous solution of a mineral acid, an aqueous solution of an ammonium salt or a combination thereof. Any water which might still be present after the hydrolysis, is preferably removed before treating the carrier further. Water is preferably removed by drying.
  • the calcination is carried out at a relatively high temperature.
  • a preferred calcination treatment comprises (a) calcining a silica gel carrier at a temperature of at least 400 °C, (b) hydrolysing the calcined silica gel carrier, (c) impregnating the hydrolysed carrier obtained in step (b) with a titanium-containing impregnating agent, and (d) calcining the impregnated carrier.
  • the calcination of step (a) is carried out at a temperature of from 450 to 800 °C, more preferably of from 500 to 700 °C.
  • the silica gel carrier for use in the present invention preferably has a surface area of at most 1000 m2/gram, more preferably at most 800 m2/gram, most preferably at most 500 m2/gram.
  • Titanium halides which can be used in the process according to the present invention comprise tri- and tetra-substituted titanium complexes which have of from 1 to 4 halide substituents with the remainder of the substituents, if any, being alkoxide or amino groups.
  • the titanium halide can be either a single titanium halide compound or can be a mixture of titanium halide compounds.
  • the titanium halide comprises at least 50 %wt of titanium tetrachloride, more specifically at least 70 %wt of titanium tetrachloride.
  • the gas stream consists of titanium tetrachloride.
  • the present invention comprises impregnating the carrier with gas consisting of titanium halide.
  • catalyst having higher selectivity for the desired alkylene oxide could be obtained if the silicon containing carrier was impregnated with gas consisting of titanium halide.
  • the preparation according to the present invention is carried out in the absence of a carrier gas. Without wishing to be bound to any theory, it is thought that the carrier gas interferes with the impregnation. However, limited amounts of further gaseous compounds are allowed to be present during the contact between the silicon containing carrier and the gaseous titanium halide.
  • the gas in contact with the carrier during impregnation preferably consists for at least 70 %wt of titanium halide, more specifically at least 80 %wt, more specifically at least 90 %wt, most specifically at least 95 %wt.
  • Gaseous titanium halide can be prepared in any way known to someone skilled in the art.
  • a simple and easy way comprises heating a vessel containing titanium halide to such temperature that the gaseous titanium halide is obtained.
  • the impregnated carrier will be calcined and subsequently hydrolysed before being used as a catalyst. It is believed that calcination removes hydrogen halide, more specifically hydrogen chloride which is formed upon reaction of titanium halide and silicon compounds present on the surface of the silicon containing carrier.
  • the optional calcination of the impregnated carrier generally comprises subjecting the impregnated carrier to a temperature of at least 500 °C, more specifically at least 600 °C. Preferably, the calcination is carried out at a temperature of at least 650 °C. From a practical point of view, it is preferred that the calcination temperature applied is at most 1000 °C.
  • Hydrolysis of the impregnated and calcined carrier can remove Ti-halide bonds.
  • the hydrolysis of the impregnated carrier will generally somewhat more severe than the optional hydrolysis of the carrier before impregnation. Accordingly, this hydrolysis of the impregnated carrier is suitably carried out with steam at a temperature in the range of from 150 to 400 °C.
  • the hydrolysed impregnated carrier is subsequently silylated for instance by contacting the hydrolysed impregnated carrier with a silylating agent, preferably at a temperature of between 100 and 425 °C.
  • Suitable silylating agents include organosilanes like tetra-substituted silanes with C]_-C3 hydrocarbyl substituents.
  • a very suitable silylating agent is hexamethyldisilazane. Examples of specific suitable silylating methods and silylating agents are, for instance, described in US-A-3, 829, 392 and US-3,923,843 which are referred to in US-A-6, Oil, 162, and in EP-A-734764.
  • titanium as metallic titanium
  • the amount of titanium will normally be in the range of from 0.1 to 10% by weight, suitably of from 1 to 5% by weight, based on total weight of the catalyst.
  • titanium or a titanium compound, such as a salt or an oxide is the only metal and/or metal compound present.
  • alkylene oxides such as propylene oxide
  • a hydroperoxide such as hydrogen peroxide or an organic hydroperoxide as the source of oxygen.
  • the hydroperoxide can be hydrogen peroxide or any organic hydroperoxide such as tert-butyl hydroperoxide, cumene hydroperoxide and ethylbenzene hydroperoxide.
  • the alkene will generally be propene which gives as alkylene oxide, propylene oxide.
  • the catalyst prepared according to the present invention has been found to give especially good results in such process.
  • the present invention further relates to a process for the preparation of alkylene oxide which process comprises contacting a hydroperoxide and alkene with a heterogeneous epoxidation catalyst and withdrawing a product stream comprising alkylene oxide and an alcohol and/or water, in which process the catalyst has been prepared according to the present invention.
  • a specific organic hydroperoxide is ethylbenzene hydroperoxide, in which case the alcohol obtained is 1-phenyl ethanol.
  • the 1-phenylethanol usually is converted further by dehydration to obtain styrene.
  • Another method for producing propylene oxide is the co-production of propylene oxide and methyl tert-butyl ether ( TBE) starting from isobutane and propene.
  • a further method comprises the manufacture of propylene oxide with the help of cumene.
  • cu ene is reacted with oxygen or air to form cumene hydroperoxide.
  • Cumene hydroperoxide thus obtained is reacted with propene in the presence of an epoxidation catalyst to yield propylene oxide and 2-phenyl propanol.
  • the latter can be converted into cumene with the help of a heterogeneous catalyst and hydrogen. Suitable processes are described for example in WO 02/48126.
  • the conditions for the epoxidation reaction according to the present invention are those conventionally applied.
  • typical reaction conditions include temperatures of 50 to 140 °C, suitably 75 to 125 °C, and pressures up to 80 bar with the reaction medium being in the liquid phase.
  • the silica gel carrier used in the examples had a surface area of 300 2/g and a weight average particle size of about 1 mm. Substantially all particles had a particle size between 0.6 and 1.4 mm.
  • the dried silica gel carrier was contacted with a gas stream containing titaniumtetrachloride.
  • the gas stream was obtained by heating titaniumtetrachloride to 200 °C with the help of an electrical heating system. Different gas streams were obtained by adding different amounts of nitrogen. At the end of each experiment, each silica carrier had been in contact with the same amount of titaniumtetrachloride.
  • the impregnated catalysts thus obtained were calcined at 600 °C during 7 hours.
  • the calcined catalysts were subsequently contacted with steam at 325 °C during 6 hours.
  • the steam flow consisted of 3 grams of water per hour and 8 Nl of nitrogen per hour.
  • the catalysts were silylated at 185 °C during 2 hours by being contacted with 18 grams of hexamethyldisilazane per hour in a nitrogen flow of 1.4 Nl per hour.
  • the catalysts obtained were analysed for the amount of titanium deposited on the carrier.
  • the selectivity of the catalysts was tested in a continuous epoxidation bench scale unit containing a number of vessels on automatic weight balances containing respectively the ethylbenzene hydroperoxide and propene feed streams, two high pressure pumps, a fixed bed reactor, a third pump for pumping a recycle stream over the reactor, means to maintain the reactor continuously at temperatures between 60 and 120 °C, a stripper to remove light boiling components like propene, a cooler and a vessel for receiving the product.
  • the feeds were supplied to the reactor via the two high pressure pumps and mixed together before entering the reactor.
  • the reactor was operated liquid full at
  • the feed consisted of 40 %wt of propene, 20 %wt of ethylbenzene hydroperoxide and 40 %wt of ethylbenzene.
  • the results obtained are given in Table 1.
  • the selectivity is the molar ratio of propylene oxide formed to ethylbenzene hydroperoxide converted.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Epoxy Compounds (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Process for the preparation of an epoxidation catalyst, which process comprises impregnating a silicon containing carrier with a gas stream consisting of titanium halide, and process for the preparation of alkylene oxide with the help of such catalyst.

Description

PROCESS FOR THE PREPARATION OF EPOXIDATION CATALYSTS
The present invention relates to the preparation of an epoxidation catalyst and to the process of preparing alkylene oxide with the help of such catalyst. Background of the Invention An epoxidation catalyst is understood to be a catalyst which catalyses the manufacture of an epoxy group containing compound. A well known process comprises contacting a hydroperoxide and alkene with a heterogeneous epoxidation catalyst and withdrawing a product stream comprising alkylene oxide and an alcohol. Catalysts for the manufacture of an epoxy group containing compound, are well known. EP-A-345856 describes the preparation of such catalyst comprising titanium in chemical combination with a solid silica and/or inorganic silicate. The preparation comprises (a) impregnating a silicium compound with a stream of gaseous titanium tetrachloride preferably comprising an inert gas, (b) calcining the obtained reaction product of step (a) , and (c) hydrolysis of the product of step (b) . The stream of inert gas also has the function of a carrier for the gaseous titanium tetrachloride. For such use, the gas is to be present in a relatively large amount .
There is a continuous interest in improving the selectivity of epoxidation processes in general, and more specifically of processes for the preparation of alkylene oxide. We found a simple and attractive way to achieve this. Summary of the Invention
The present invention relates to a process for the preparation of an epoxidation catalyst, which process comprises impregnating a silicon containing carrier with a gas stream consisting of titanium halide.
A catalyst of improved selectivity was obtained even though the carrier had been in contact with the same amount of titanium halide. Detailed description of the invention The catalyst of the present invention is obtained by impregnating a silicon containing carrier. In principle, any silicon containing carrier is suitable for use in the preparation process according to the present invention. Examples of silicon containing carriers comprise zeolites. Preferably, the silicon containing carrier is a silica carrier.
Silica carriers will substantially consist of silicon dioxide. However, limited amounts of further compounds such as contaminants can be present as well. It is known that contaminants can influence the performance of the final catalyst. The silica carrier for use in the present invention preferably contains at most 1200 ppm of sodium, more specifically at most 1000 ppm of sodium. Further, the silica carrier preferably comprises at most 500 ppm of aluminium, at most 500 ppm of calcium, at most 200 ppm of potassium, at most 100 ppm of magnesium and at most 100 ppm of iron. The amounts are based on amount of carrier.
The silica carrier preferably is a silica gel. The silica gel carrier for use in the present invention can in principle be any carrier derived from a silicon containing gel. In general, silica gels are a solid, amorphous form of hydrous silicon dioxide distinguished from other hydrous silicon dioxides by their micro- porosity and hydroxylated surface. Silica gels usually contain three-dimensional networks of aggregated silica particles of colloidal dimensions. They are typically prepared by acidifying an aqueous sodium silicate solution to a pH of less than 11 by combining it with a strong mineral acid. The acidification causes the formation of monosilicilic acid (Si (OH) ), which polymerizes into particles with internal siloxane linkages and external silanol groups. At a certain pH the polymer particles aggregate, thereby forming chains and ultimately gel networks. Silicate concentration, temperature, pH and the addition of coagulants affect gelling time and final gel characteristics such as density, strength, hardness, surface area and pore volume. The resulting hydrogel is typically washed free of electrolytes, dried and activated. A suitable silica gel carrier would be silica support V432 and DAVICAT P-732, which are commercially available from Grace Davison.
Silica gel carriers for use in the present invention preferably have a weight average particle size of at most 2 millimetres. Particle sizes which were found to be especially suitable were weight average particle, sizes of from 0.2 to 1.8 mm, more specifically of from 0.4 to 1.6 mm, most specifically of from 0.6 to 1.4 mm.
The silicon containing carrier preferably has a low water content when contacted with the titanium halide. A low water content can be achieved in any way known to someone skilled in the art. A preferred way comprises drying the silicon containing carrier before impregnating the silicon containing carrier with the gas stream consisting of titanium halide. A suitable drying method comprises subjecting the silicon containing carrier to a temperature of from 200 to 700 °C. Surprisingly it has been found that drying under specific circumstances gives a further improved catalyst. The preferred drying conditions comprise drying the carrier at a temperature of from more than 200 to 300 °C. The drying is preferably carried out during of from 1 to 8 hours, preferably in the presence of an inert gas such as nitrogen. The preferred method has been described in more detail in co- pending patent application claiming priority of European application 02258294.4.
A further improvement was observed if the silicon containing carrier had been subjected to a pretreatment comprising calcining the silicon containing carrier and subsequently hydrolysing the carrier obtained. Hydrolysis comprises treating the carrier with water or steam. Preferably, the hydrolysis is carried out with steam. Alternatively, the hydrolysis treatment may comprise a washing treatment using an aqueous solution of a mineral acid, an aqueous solution of an ammonium salt or a combination thereof. Any water which might still be present after the hydrolysis, is preferably removed before treating the carrier further. Water is preferably removed by drying. Preferably, the calcination is carried out at a relatively high temperature. A preferred calcination treatment comprises (a) calcining a silica gel carrier at a temperature of at least 400 °C, (b) hydrolysing the calcined silica gel carrier, (c) impregnating the hydrolysed carrier obtained in step (b) with a titanium-containing impregnating agent, and (d) calcining the impregnated carrier. Preferably, the calcination of step (a) is carried out at a temperature of from 450 to 800 °C, more preferably of from 500 to 700 °C.
The silica gel carrier for use in the present invention preferably has a surface area of at most 1000 m2/gram, more preferably at most 800 m2/gram, most preferably at most 500 m2/gram.
Titanium halides which can be used in the process according to the present invention comprise tri- and tetra-substituted titanium complexes which have of from 1 to 4 halide substituents with the remainder of the substituents, if any, being alkoxide or amino groups. The titanium halide can be either a single titanium halide compound or can be a mixture of titanium halide compounds. Preferably, the titanium halide comprises at least 50 %wt of titanium tetrachloride, more specifically at least 70 %wt of titanium tetrachloride. Most preferably, the gas stream consists of titanium tetrachloride.
The present invention comprises impregnating the carrier with gas consisting of titanium halide.
Surprisingly, it was found that catalyst having higher selectivity for the desired alkylene oxide could be obtained if the silicon containing carrier was impregnated with gas consisting of titanium halide. The preparation according to the present invention is carried out in the absence of a carrier gas. Without wishing to be bound to any theory, it is thought that the carrier gas interferes with the impregnation. However, limited amounts of further gaseous compounds are allowed to be present during the contact between the silicon containing carrier and the gaseous titanium halide. The gas in contact with the carrier during impregnation preferably consists for at least 70 %wt of titanium halide, more specifically at least 80 %wt, more specifically at least 90 %wt, most specifically at least 95 %wt.
Gaseous titanium halide can be prepared in any way known to someone skilled in the art. A simple and easy way comprises heating a vessel containing titanium halide to such temperature that the gaseous titanium halide is obtained.
Generally, the impregnated carrier will be calcined and subsequently hydrolysed before being used as a catalyst. It is believed that calcination removes hydrogen halide, more specifically hydrogen chloride which is formed upon reaction of titanium halide and silicon compounds present on the surface of the silicon containing carrier. The optional calcination of the impregnated carrier generally comprises subjecting the impregnated carrier to a temperature of at least 500 °C, more specifically at least 600 °C. Preferably, the calcination is carried out at a temperature of at least 650 °C. From a practical point of view, it is preferred that the calcination temperature applied is at most 1000 °C.
Hydrolysis of the impregnated and calcined carrier can remove Ti-halide bonds. The hydrolysis of the impregnated carrier will generally somewhat more severe than the optional hydrolysis of the carrier before impregnation. Accordingly, this hydrolysis of the impregnated carrier is suitably carried out with steam at a temperature in the range of from 150 to 400 °C.
Preferably, the hydrolysed impregnated carrier is subsequently silylated for instance by contacting the hydrolysed impregnated carrier with a silylating agent, preferably at a temperature of between 100 and 425 °C. Suitable silylating agents include organosilanes like tetra-substituted silanes with C]_-C3 hydrocarbyl substituents. A very suitable silylating agent is hexamethyldisilazane. Examples of specific suitable silylating methods and silylating agents are, for instance, described in US-A-3, 829, 392 and US-3,923,843 which are referred to in US-A-6, Oil, 162, and in EP-A-734764.
The amount of titanium (as metallic titanium) will normally be in the range of from 0.1 to 10% by weight, suitably of from 1 to 5% by weight, based on total weight of the catalyst. Preferably, titanium or a titanium compound, such as a salt or an oxide, is the only metal and/or metal compound present.
As mentioned above, it is well known in the art to produce alkylene oxides, such as propylene oxide, by epoxidation of the corresponding olefin using a hydroperoxide such as hydrogen peroxide or an organic hydroperoxide as the source of oxygen. The hydroperoxide can be hydrogen peroxide or any organic hydroperoxide such as tert-butyl hydroperoxide, cumene hydroperoxide and ethylbenzene hydroperoxide. The alkene will generally be propene which gives as alkylene oxide, propylene oxide. The catalyst prepared according to the present invention has been found to give especially good results in such process. Therefore, the present invention further relates to a process for the preparation of alkylene oxide which process comprises contacting a hydroperoxide and alkene with a heterogeneous epoxidation catalyst and withdrawing a product stream comprising alkylene oxide and an alcohol and/or water, in which process the catalyst has been prepared according to the present invention. A specific organic hydroperoxide is ethylbenzene hydroperoxide, in which case the alcohol obtained is 1-phenyl ethanol. The 1-phenylethanol usually is converted further by dehydration to obtain styrene. Another method for producing propylene oxide is the co-production of propylene oxide and methyl tert-butyl ether ( TBE) starting from isobutane and propene. This process is well known in the art and involves similar reaction steps as the styrene/propylene oxide production process described in the previous paragraph. In the epoxidation step tert-butyl hydroperoxide is reacted with propene forming propylene oxide and tert-butanol. Tert- butanol is subsequently etherified into MTBE.
A further method comprises the manufacture of propylene oxide with the help of cumene. In this process, cu ene is reacted with oxygen or air to form cumene hydroperoxide. Cumene hydroperoxide thus obtained is reacted with propene in the presence of an epoxidation catalyst to yield propylene oxide and 2-phenyl propanol. The latter can be converted into cumene with the help of a heterogeneous catalyst and hydrogen. Suitable processes are described for example in WO 02/48126.
The conditions for the epoxidation reaction according to the present invention are those conventionally applied. For propene epoxidation reactions with the help of ethylbenzene hydroperoxide, typical reaction conditions include temperatures of 50 to 140 °C, suitably 75 to 125 °C, and pressures up to 80 bar with the reaction medium being in the liquid phase. The invention is further illustrated by the following
Examples . Examples
The silica gel carrier used in the examples had a surface area of 300 2/g and a weight average particle size of about 1 mm. Substantially all particles had a particle size between 0.6 and 1.4 mm.
75 grams of silica gel carrier was dried at 250 °C during 2 hours.
The dried silica gel carrier was contacted with a gas stream containing titaniumtetrachloride. The gas stream was obtained by heating titaniumtetrachloride to 200 °C with the help of an electrical heating system. Different gas streams were obtained by adding different amounts of nitrogen. At the end of each experiment, each silica carrier had been in contact with the same amount of titaniumtetrachloride.
The impregnated catalysts thus obtained were calcined at 600 °C during 7 hours. The calcined catalysts were subsequently contacted with steam at 325 °C during 6 hours. The steam flow consisted of 3 grams of water per hour and 8 Nl of nitrogen per hour. Finally, the catalysts were silylated at 185 °C during 2 hours by being contacted with 18 grams of hexamethyldisilazane per hour in a nitrogen flow of 1.4 Nl per hour.
The catalysts obtained were analysed for the amount of titanium deposited on the carrier.
The selectivity of the catalysts was tested in a continuous epoxidation bench scale unit containing a number of vessels on automatic weight balances containing respectively the ethylbenzene hydroperoxide and propene feed streams, two high pressure pumps, a fixed bed reactor, a third pump for pumping a recycle stream over the reactor, means to maintain the reactor continuously at temperatures between 60 and 120 °C, a stripper to remove light boiling components like propene, a cooler and a vessel for receiving the product.
The feeds were supplied to the reactor via the two high pressure pumps and mixed together before entering the reactor. The reactor was operated liquid full at
40 bara pressure and 90 CC. A large recycle stream was maintained over the reactor to have isothermal operation of the reactor bed and to ensure that the catalyst to be re-activated is contacted with epoxidation reaction product. The feed was mixed with the recycle stream prior to introduction into the reactor.
The feed consisted of 40 %wt of propene, 20 %wt of ethylbenzene hydroperoxide and 40 %wt of ethylbenzene. The results obtained are given in Table 1. The selectivity is the molar ratio of propylene oxide formed to ethylbenzene hydroperoxide converted. Example 2
Further catalysts were prepared in a way similar to the one described in Example 1. However, the impregnated catalysts were calcined for 6 hours {instead of 7 hours) while the steam flow during the subsequent hydrolysis contained 5 grams of water per hour (instead of 3 grams of water per hour) . The results of these experiments are shown in Table 2.
TABLE 1
Figure imgf000012_0001
TABLE 2
to
I
Figure imgf000013_0001

Claims

C L A I M S
1. Process for the preparation of an epoxidation catalyst, which process comprises impregnating a silicon containing carrier with a gas stream consisting of titanium halide.
2. Process according to claim 1, in which process the silicon containing carrier is a silica gel.
3. Process according to any one of the preceding claims, in which process the gas stream consists of titanium tetrachloride .
4. Process according to any one of the preceding claims, in which process the silicon containing carrier comprises at most 1200 ppm of sodium, based on amount of carrier.
5. Process according to any one of the preceding claims, which process comprises drying the silicon containing carrier before impregnation.
6. Process according to any one of the preceding claims in which process the impregnated carrier is calcined and subsequently hydrolysed.
7. Process according to claim 6, in which process the hydrolysed impregnated carrier is subsequently contacted with a silylating agent.
8. Process for the preparation of alkylene oxide which process comprises contacting a hydroperoxide and alkene with a heterogeneous epoxidation catalyst and withdrawing a product stream comprising alkylene oxide and an alcohol and/or water, in which process the catalyst has been prepared by a process according to any one of the preceding claims.
9. Process according to claim 8, in which process the alkene is propene and the alkylene oxide is propylene oxide.
10. Process according to claim 9, in which process the organic hydroperoxide is ethylbenzene hydroperoxide and in which the alcohol is 1-phenyl ethanol.
11. Process according to claim 10, which process further comprises dehydration of 1-phenylethanol to obtain styrene.
PCT/EP2003/050875 2002-12-02 2003-11-24 Process for the preparation of epoxidation catalysts WO2004050233A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
MXPA05005699A MXPA05005699A (en) 2002-12-02 2003-11-24 Process for the preparation of epoxidation catalysts.
EP03796044A EP1567261A1 (en) 2002-12-02 2003-11-24 Process for the preparation of epoxidation catalysts
CA002508043A CA2508043A1 (en) 2002-12-02 2003-11-24 Process for the preparation of epoxidation catalysts
BR0316825-5A BR0316825A (en) 2002-12-02 2003-11-24 Processes for the preparation of an epoxidation catalyst and alkylene oxide
JP2004556324A JP2006507932A (en) 2002-12-02 2003-11-24 Method for preparing epoxidation catalyst
AU2003298312A AU2003298312A1 (en) 2002-12-02 2003-11-24 Process for the preparation of epoxidation catalysts

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP02258296 2002-12-02
EP02258296.9 2002-12-02

Publications (2)

Publication Number Publication Date
WO2004050233A1 true WO2004050233A1 (en) 2004-06-17
WO2004050233A8 WO2004050233A8 (en) 2004-08-05

Family

ID=32405785

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/050875 WO2004050233A1 (en) 2002-12-02 2003-11-24 Process for the preparation of epoxidation catalysts

Country Status (8)

Country Link
EP (1) EP1567261A1 (en)
JP (1) JP2006507932A (en)
CN (1) CN1720097A (en)
AU (1) AU2003298312A1 (en)
BR (1) BR0316825A (en)
CA (1) CA2508043A1 (en)
MX (1) MXPA05005699A (en)
WO (1) WO2004050233A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7763564B2 (en) 2006-05-02 2010-07-27 Shell Oil Company Titanium catalyst, its preparation and its use in epoxidation reactions
WO2012010491A1 (en) 2010-07-19 2012-01-26 Shell Internationale Research Maatschappij B.V. Epoxidation process
WO2017080962A1 (en) 2015-11-09 2017-05-18 Shell Internationale Research Maatschappij B.V. Catalyst preparation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2859946A1 (en) * 2013-10-11 2015-04-15 Repsol, S.A. Process for regenerating heterogeneous epoxidation catalysts and their use to catalyze epoxidation reactions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0345856A1 (en) * 1988-06-08 1989-12-13 Shell Internationale Researchmaatschappij B.V. A process for the preparation of an oxirane compound
EP0525503A1 (en) * 1991-07-16 1993-02-03 Neste Oy Method for preparing heterogeneous catalysts of desired metal content
WO1995007305A1 (en) * 1993-09-10 1995-03-16 Neste Oy Catalyst for polymerization of ethylene
US6383966B1 (en) * 1999-09-28 2002-05-07 Arco Chemical Technology, L.P. Method for making a heterogeneous epoxidation catalyst

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2704159B1 (en) * 1993-04-22 1995-06-09 Atochem Elf Sa Solid catalyst based on particulate silica, comprising titanium, Method for obtaining, and use in the epoxidation of olefins.
BR9809020A (en) * 1997-05-05 2000-08-01 Arco Chem Tech Epoxidation process using improved heterogeneous catalyst composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0345856A1 (en) * 1988-06-08 1989-12-13 Shell Internationale Researchmaatschappij B.V. A process for the preparation of an oxirane compound
EP0525503A1 (en) * 1991-07-16 1993-02-03 Neste Oy Method for preparing heterogeneous catalysts of desired metal content
WO1995007305A1 (en) * 1993-09-10 1995-03-16 Neste Oy Catalyst for polymerization of ethylene
US6383966B1 (en) * 1999-09-28 2002-05-07 Arco Chemical Technology, L.P. Method for making a heterogeneous epoxidation catalyst

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7763564B2 (en) 2006-05-02 2010-07-27 Shell Oil Company Titanium catalyst, its preparation and its use in epoxidation reactions
WO2012010491A1 (en) 2010-07-19 2012-01-26 Shell Internationale Research Maatschappij B.V. Epoxidation process
US8664412B2 (en) 2010-07-19 2014-03-04 Shell Oil Company Epoxidation process
WO2017080962A1 (en) 2015-11-09 2017-05-18 Shell Internationale Research Maatschappij B.V. Catalyst preparation

Also Published As

Publication number Publication date
JP2006507932A (en) 2006-03-09
MXPA05005699A (en) 2005-07-26
EP1567261A1 (en) 2005-08-31
AU2003298312A1 (en) 2004-06-23
CN1720097A (en) 2006-01-11
BR0316825A (en) 2005-10-18
CA2508043A1 (en) 2004-06-17
WO2004050233A8 (en) 2004-08-05

Similar Documents

Publication Publication Date Title
US7763564B2 (en) Titanium catalyst, its preparation and its use in epoxidation reactions
JP3658790B2 (en) Catalyst and method for producing oxirane compound
WO2017080962A1 (en) Catalyst preparation
US7713906B2 (en) Catalyst composition, process for its preparation and use thereof
NO138883B (en) PROCEDURE FOR THE PREPARATION OF OXIRANIUM COMPOUNDS
WO2005002723A1 (en) Catalyst preparation
US20150182959A1 (en) Relating to epoxidation catalysts
US8664412B2 (en) Epoxidation process
EP1572362B1 (en) Process for preparing an epoxidation catalyst and process for preparing epoxides
KR20030077603A (en) Process for production of titanium-containing silicon oxide catalysts
US7125819B2 (en) Catalyst preparation
EP1567261A1 (en) Process for the preparation of epoxidation catalysts
KR20030080226A (en) Method for preparing a titanium-containing silicon oxide catalyst

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
D17 Declaration under article 17(2)a
WR Later publication of a revised version of an international search report
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: PA/a/2005/005699

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2508043

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2004556324

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 20038A4860X

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2003796044

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2003796044

Country of ref document: EP

ENP Entry into the national phase

Ref document number: PI0316825

Country of ref document: BR

WWW Wipo information: withdrawn in national office

Ref document number: 2003796044

Country of ref document: EP