Catalytic epoxidation of olefins.

© Beginning of patent period: March 15, 1972 Longest possible duration:

© Issued on: lO.November 1972 © Inventor:

© dependence:

© Pamphlets considered to delineate the prior art:

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Olefinic compounds are known to be converted to the corresponding oxirane compounds by equating them to the equation

-C-OH

Oxirane group Hydroxyl group ^ C = cX + -COOH-sI

Olefin group hydroperoxide group with an organic hydroperoxide compound.

The hydroxyl compound obtained after the reaction according to the above equation can be converted back to the hydroperoxide compound. When a carbon atom bearing at least one hydrogen atom adjacent to the carbon atom linked to the hydroxyl group is present, regeneration is usually carried out with the greatest advantage by dehydration, hydrogenation and oxidation according to the following reaction scheme:

H OH II -cc-

Η HII

-e> -ccCC- + O "

-CCOOH

The first two stages corresponding to the above scheme can often be performed simultaneously.

When the olefin compound intermediate product according to the above reaction scheme is a salable product, the hydrogenation and oxidation step can be dispensed with. If the hydroxyl compound is salable, one may even omit the dehydration step.

Hydroperoxides are known to be prepared by an oxidation reaction according to the following equation:

RH + O -5 * ROOH

In this equation, R represents an optionally substituted monovalent hydrocarbon radical.

It will be appreciated that the last stage of the regeneration scheme explained above is also represented by the above equation.

The radical R is preferably a C₃_₁₍₎Hydrocarbon radical, in particular a corresponding non-substituted hydrocarbon radical, especially a secondary or tertiary C₃__lgAlkyl or aralkyl radical. Most preferred as R radicals are the tertiary alkyl radicals and secondary or tertiary aralkyl radicals, such as the tert. Butyl, tert-pentyl, cyclopentyl, 1-phenylethyl-l- and 2-phenylpropyl-2-group, as well as the most diverse Tetralinylreste, which are formed by cleavage of a hydrogen atom from the aliphatic side chain of a tetralin molecule.

Aralkyl hydroperoxides in which a hydroperoxide group is linked to that C atom of an alkyl side chain which is bonded directly to the aromatic ring, such as 1-phenylethyl-1-hydroperoxide or 2-phenylpropyl-2-hydroperoxide, are often referred to as the corresponding hydrocarbons , eg as ethylbenzene hydroperoxide or cumene hydroperoxide. This notation is also used hereinafter. It will be appreciated that when ethylbenzene hydroperoxide is used as the corresponding hydroxyl compound, 1-phenylethanol-1 (referred to as methylphenylcarbinol) which can be dehydrated to styrene, and 2-phenylpropanol-2 (referred to as dimethylphenylcarbinol) is obtained as the corresponding hydroxyl compound when using cumene hydroperoxide , which can be dehydrated to ct-methylstyrene. Both styrene and α-methylstyrene are of course technically valuable products, which are thus preferably used and / or sold as such, wherein the regeneration zn ethylbenzene or cumene is dispensed with.

Suitable tertiary amylenes as isoprene precursors can be obtained by dehydration of the by using tert. -Pentyl hydroperoxide formed alcohol.

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By hydrocarbon is meant hereinafter the compound RH defined above, although R, as mentioned, may also mean a substituted hydrocarbon radical.

The organic hydroperoxide used as starting material may be diluted or concentrated or

be used in purified or unpurified form. Solutions of from 5 to 70% by weight of the hydroperoxide in the corresponding hydrocarbon can, as is generally known, be readily prepared by oxidation of the hydrocarbon in question. Isolation of the hydroperoxides is more difficult the more the volatility of the hydrocarbons decreases, and the use of the solutions as such may then be preferable. Suitable processes for the oxidation of the hydrocarbons considered here are known.

The solutions of hydroperoxides in the ent speaking hydrocarbons obtained by one of the known oxidation processes generally contain some of the alcohol formed by reduction of the hydroperoxide, and this alcohol may also be partially oxidized to the corresponding ketone. A solution of ethylbenzene hydroperoxide in ethylbenzene thus generally also contains methylphenylcarbinol and methyl phenyl ketone. After reaction with an olefinic compound, methyl phenyl ketone can be converted to methylphenyl carbinol by hydrogenation, and the total amount of methylphenyl carbinol finally obtained can be converted to styrene and optionally further to ethylbenzene.

In principle, any organic compound having at least one olefinic double bond can be reacted with a hydroperoxide in the manner described above. It is possible to use acyclic, monocyclic, bicyclic or polycyclic as well as monoolefinic, diolefinic or polyolefinic compounds. If more than one olefinically unsaturated bond is present in the molecule, these bonds may be conjugated or non-conjugated.

Preference is given to olefinic compounds having 2 to 60 carbon atoms. Although substituents, which are preferably to be relatively stable, can be present, acyclic monoolefins having 2 to 10 C atoms, such as ethylene, propylene, isobutene, hexene-3, octene-1 or decene-1, are particularly preferred. An example of a suitable diolefin is butadiene. If substituents are present, these can, for example, halogen atoms or from oxygen, sulfur or Nitrogen be hydrogen and / or carbon atoms existing groups. Especially preferred are olefinically unsaturated alcohols and halogen-substituted olefinically unsaturated

Hydrocarbons, such as allyl alcohol, crotyl alcohol or allyl chloride.

The usefulness of oxirane compounds is known. Many of these compounds are commercial products, in particular olefin oxides, such as ethylene oxide or propylene oxide. For example, as described in U.S. Pat. Nos. 2,815,343, No. 2,871,219 and No. 2,987,498, propylene oxide can be converted to valuable polymeric products by polymerization or copolymerization. There is also an economic interest in epichlorohydrin, which is derived from allyl chloride and can be converted to glycerine. Of course, glycerol may also be prepared from the oxirane compound formed using allyl alcohol as the starting material.

Ethylene oxide is known to be widely prepared by reacting ethylene with molecular oxygen in the presence of a silver-containing catalyst. A further production method for ethylene oxide is the addition of hypochlorous acid to the double bond and subsequent elimination of hydrogen chloride. The latter method is also very suitable for the production of propylene oxide. However, the above-described reaction of propylene with a hydroperoxide is a promising further preparation route. Of particular interest is the epoxidation of propylene with ethylbenzene hydroperoxide according to the following reaction equation.

CH.

CH.

HC = CH-CH + 2 3

CO-OH, / hn₂c • CH-CH.

C-OH ./H

propylene oxide

methylphenyl

It has already been mentioned that in this case styrene can be obtained as a valuable by-product. The invention relates to a novel, compared to the above-described known method improved process in which in principle an olefinic compound is converted by means of an organic hydroperoxide to an oxirane compound. The improvement is based on the use of a specific type of catalyst. There are already a wide variety of catalysts known for the methods considered here. For example, US Pat. No. 2,754,325 describes the use of hetero-50 polyacids in solution containing transition metals such as chromium, molybdenum or tungsten. The United States Patents

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Nos. 3,350,422 and 3,351,635 describe the use of solutions of transition metal compounds (V, Mo, W, Ti, Nb, Ta, Re, Se, Zr, Te and U.) However, these known catalysts are generally effective only when homogeneously dispersed in the reaction mixture.

The object of the invention is to provide a novel process for the preparation of oxirane compounds by reacting 5 olefinic compounds with hydroperoxides available, which is carried out in the presence of heterogeneous, substantially insoluble in the reaction mixture and thus easily separable from the reaction products catalysts.

The invention thus provides a process for the epoxidation of olefinic compounds by means of hydroperoxides, which is characterized in that the reaction is carried out using a heterogeneous SylO stems in the liquid phase and in the presence of a catalyst substantially insoluble in the reaction mixture, consisting of SiO₂ and / or inorganic solid silicates in chemical association with titanium in a catalyst based amount of at least 0.1% by weight expressed as titanium dioxide.

Surprisingly, it was found that the catalyst combination used in the process has a high activity and ensures high degrees of conversion of the hydroperoxides used and high selectivities of the oxirane compounds formed. The selectivities are defined by the molar ratios of the oxirane compounds to the hydroperoxides.

The reaction is generally carried out in the liquid phase using solvents and / or diluents which are liquid at the reaction temperature and under the appropriate pressure and substantially inert to both the starting materials and the reaction products.

The presence of reactive materials, such as water, is expediently avoided. A substantial proportion of the solvent may consist of those materials contained in the hydroperoxide solution used. Also preferably used as solvents are mononuclear aromatics, such as benzene, toluene, chlorobenzene, bromobenzene or o-dichlorobenzene, and alkanes, such as octane, decane or dodecane. However, it is also possible for an excess of the olefinic compound used together with the solvent which has been introduced together with the hydroperoxide to serve as solvent, so that no further solvents need be added. In most cases, however, additional solvent is used. The total content of the solvent can be up to 20 mol / mol of hydroperoxide.

The reaction generally proceeds at moderate temperatures and under moderate pressures. Temperatures of 0 to 20 ° C, in particular from 25 to 200 ° C, are preferred. The exact pressure is not critical; it only has to be sufficient to keep the reaction mixture in a liquid state. Atmospheric pressure may be sufficient; Pressures of 1 to 100 atmospheres are generally sufficient.

After completion of the reaction, the liquid mixture containing the desired products can be easily separated from the solid catalyst. Subsequently, the liquid mixture may be worked up by any conventional method, such as by fractional distillation, selective extraction or filtration. The solvent, the catalyst and optionally present unreacted olefin or hydroperoxide can be recycled for further processing. The process of the invention may be advantageously carried out in the presence of a catalyst which is in the form of a slurry, a fluidized bed or a fluidized bed. For the industrial scale, however, the use of a catalyst fixed bed is preferable. The process of the invention may be carried out batchwise, but also semi-continuously or continuously. The liquid containing the starting materials can then be passed through the catalyst bed so that the effluent from the reaction zone is completely or practically free of catalyst.

The catalyst used in the process of the invention contains, as mentioned, a chemical compound of titanium with solid inorganic silicon dioxide-containing compounds, ie silicon dioxide and / or silicates. The titanium turns into the tetravalent state during the reaction and is preferably combined with the inorganic solid silica-containing compounds in this oxidation state. The proportion of titanium in the catalyst can be varied, as a rule the amounts already mentioned of at least 0.1% by weight of titanium, expressed as titanium dioxide, are sufficient. Titanium contents of 0.2 to 50% by weight are preferred. However, it is also possible to use higher titanium proportions.

Inorganic solid silicates suitable according to the invention contain at least 50% by weight, preferably at least 75% by weight, in particular at least 90% by weight, as SiO₂ expressed silicon. The inorganic solid silicates also have a relatively high specific surface area, preferably a specific surface area of ​​at least 1 m²/G. Materials with specific surface areas from 25 to 800 m²/ g are particularly preferred.

Relatively dense, closely packed, porous masses consisting of coagulated or bonded particles of amorphous silica, such as silica gel or precipitated silica, are useful in the process of the invention, for example. The production and the properties of these products are z. For example, in The Colloid Chemistry of Silica and Silicates, Cornell University Press, New York (1955), Chapter VI, by RG Iler and in the US Pat. No. 2,657,149. Silica gel merchandising products consisting of at least 99% silica and a specific surface area of ​​25 to 700 m²/ g and a pore5

No. 302983 volume of 0.3 to 1.3 cm³/ g are generally most suitable as catalyst components for the process of the invention.

However, also suitable are powdery types of silica which consist of particles of amorphous silicon dioxide. These particles are flakes in the form of open-packed, easily separable, loosely-bound aggregates. An example of fumed silica grades is fumed silica in airgel form obtained by combustion of hydrogen and oxygen with silicon tetrachloride or tetrafluoride. Airgel silica is commercially available in the form of several products. Generally best suited are airgel silica grades consisting of at least 99% silica and a specific surface area of ​​50 to 400 m^z/ g and have a particle size of 0.007 to 0.05 μ,

Further examples of inorganic solid silicates which are suitable according to the invention are the crystalline aluminosilicates known as molecular sieves and naturally occurring crystalline mineral silicates, such as asbestos minerals, eg serpentine (magnesium silicate containing water of crystallization), clay minerals, eg hectorite (magnesium lithium silicate), kaolins, bentonites and mica minerals, eg Phlogopite (potassium magnesium aluminum silicate) or vermiculite (magnesium silicate containing water of crystallization). However, preferred are syn15 thetische amorphous inorganic solid silica-containing compounds, especially those which consist mainly of substantially pure silica, for example, at least 95% of silicon dioxide.

It may be expedient to incorporate promoters into the catalysts used according to the invention, in particular alkaline earth compounds, such as magnesium, calcium, strontium or barium compounds. Preference is given to the oxides and compounds which are readily convertible to oxides; to carry out the conversion into oxides, it may be advantageous to pretreat the originally prepared catalyst before use. The proportions of the promoter or promoters are not critical, as a rule however, at most 10 parts by weight, in terms of metal, and based on the catalyst support is required. The incorporation of promoters is particularly useful when inorganic solid silicon dioxide-containing compounds are used with strongly acidic sites, eg at a Eigenacidität of below -3. The generally by the value pK_a expressed intrinsic acidity is determined by titration of the subject material with a suitable base in the presence of an indicator dye, as described, for example, in U.S. Pat. No. 2,868,688.

The catalysts used according to the invention can be prepared by conventional processes, such as by mixing the dry components and subsequent calcination, cogelation, co-precipitation, impregnation or ion exchange. For example, one may cogelate a mixture of a titanium salt and a silica sol, dry the resulting gel and finally mill to a suitable grain size. However, you can also sludge the cogel and spray-dry it. However, the catalyst may also be prepared by the methods described in U.S. Patent Nos. 3,116,542, 3,270,459 or 3,274,120, by reacting the hydroxyl groups on the surface of the inorganic solid silica-containing compound 35 with a titanium salt. According to another method, a pyrogenic catalyst in airgel form, in particular a pyrogenic titanium dioxide silica, can be prepared by combustion of hydrogen and oxygen with a mixture of silicon tetrahalide and a titanium halide.

Prior to use in the process of the invention, the aforementioned catalysts may be pretreated. Such pretreatment is preferably used to achieve higher activity. For pretreatment, the catalyst can be heated, as a rule, advantageously in an atmosphere of a non-reducing gas, such as nitrogen, argon or carbon dioxide, or a gas containing free oxygen, such as air. However, in general it also depends on the type in which the titanium component is chemically bonded, which pretreatment process is the most appropriate. In many cases, Titan45 compounds must be converted into the oxide, for example when the catalyst initially contains titanium in the form of its tetrachloride or in the form of a mixture of tetrakismethylpropylaminotitanium and KCl. The conversion can be carried out with advantage in general by heating the catalyst in a non-reducing atmosphere, in particular at temperatures of 350 to 800 ° C, for 1 to 18 hours.

The catalyst can be employed in the process of the invention in any suitable physical form, for example as powders, flakes, granules or pellets.

The catalyst used in the process of the invention may further contain other components that are inert to the starting materials and reaction products. In combination with the aforementioned catalysts, other materials can be used in the process of the invention, the catalyzing effect on the Epoxidydationsreaktion is known, provided that the catalyst activity by these

Combination is not lowered. The titanium SiC described above₂In general, catalysts may additionally contain up to 10% by weight of the oxides or hydroxides of boron, zinc, niobium, tantalum, chromium, molybdenum, tungsten, rhenium, uranium, bismuth and the rare earth metals (atomic numbers from 57 to 71).

The examples illustrate the invention.

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EXAMPLE 1 Five catalysts suitable for the process according to the invention (catalyst A,

A₂, A ^, B, Q and three other comparative catalysts (catalyst D, E, F) prepared and tested.

Preparation of a titanium-on-silica catalyst (catalyst AJ of fumed silica and titanium tetrachloride.

A mixture of 25 g of a commercially available fumed silica having a specific surface area of ​​390 m²/ g and 1700 ml of n-heptane are dried by heating at reflux for 19 hours in a glass reactor equipped to trap the azeotropic boiling water / heptane mixture with a DeanStark trap. After cooling the mixture to about 25 ° C, a sample of 0.47 g (2.5 mmol) of titanium tetrachloride is fed to the reactor, and the reaction mixture is heated to 97 ° C to evolve hydrogen chloride. The hydrogen chloride is expelled through a stream of dry nitrogen and passed into a stripping apparatus containing a dilute alkali solution. After about 2.5 mmol HCl (1 equivalent, based on TiCl₄) are added, about 10 ml of water are added in portions of about 0.5 ml to release more hydrogen chloride. After a reaction time of about 16 h at a temperature of 97 ° C, the hydrogen chloride evolution stops. The reaction mixture is then concentrated under reduced pressure at elevated temperature and the residue obtained is dried overnight at 180 ° C. under a pressure of 180 torr. The titanium content of the product obtained is 0.4% by weight.

The catalyst A₂ is carried out in the same way as the catalyst Α_χ However, it becomes a TiCl₄Proportion of 4.68 g used. The product obtained has a titanium content of 4% by weight.

The catalyst A₃ is prepared by a similar method to that used to prepare the catalyst, but titanium trichloride is used instead of titanium tetrachloride. The proportion of titanium trichloride is 3.62 g (0_;023 The addition of water is started when about 0.023 moles of hydrogen chloride (1 equivalent, based on TiCip are liberated.) The product obtained has a titanium content of 4.2% by weight.

Preparation of a silicon-on-titanium dioxide catalyst (catalyst B) of pyrogenic titanium dioxide and Sili ciumtetra chloride.

A mixture of 25 g of a commercially available fumed titanium dioxide having a specific surface area of ​​50 m²g and a grain size of 15 to 40 mg, and 1700 ml of n-heptane is refluxed for 19 hours in a glass reactor equipped to trap the azeotropic boiling water / heptane mixture with a 30 Dean-Stark trap, heated. N_acAfter cooling the mixture to room temperature, a sample of 7.84 g (0.046 mole) of silicon tetrachloride in 25 ml of anhydrous n-heptane is fed to the reactor and the reaction mixture is heated to about 97 ° C until about 0.046 mole of hydrogen chloride is liberated , The hydrogen chloride is expelled through a stream of dry nitrogen and passed into a stripping apparatus containing a dilute alkali solution. In order to initiate the evolution of further hydrogen chloride, about 10 ml of water are added in about 0.5 ml aliquots. After a reaction time of about 20 h at a temperature of 97 ° C, the evolution of hydrogen chloride stops. The reaction mixture is then evaporated under reduced pressure at about 100 ° C, and the resulting residue is dried at 120 ° C for 16 hours under a pressure of 180 Torr. The silicon content of the product obtained is

3.2 wt.

Preparation of a Silica Titanium Dioxide Catalyst (Fumed Silica Catalyst Q and Fumed Titanium Dioxide.

pyrogenic silica (SiO₂ Type X) and 1 g of pyrogenic titanium dioxide (TiO₂ Type Ύ) are thoroughly mixed and then heated in an oven at 700 ° C for 24 hours. The resulting product is ground to a powder.

Titanium dioxide catalyst without silicon (catalyst D).

This catalyst is the aforementioned pyrogenic titanium dioxide (TiO₂T).

Silica catalyst without titanium (catalyst E).

This catalyst is the aforementioned fumed silica (SiO 2)₂X).

Physical mixture of fumed silica and titanium dioxide (Catalyst F).

This catalyst is a 0.75 g fumed silica (SiO₂X) and 0, 25 g of pyrogenic titanium dioxide (TiO₂Y) existing physical mixture.

In a series of experiments are now each 1 g of the aforementioned catalysts in a 100 ml glass reactor with 36.5 g octene-1 and 4.5 g tert. Butyl hydroperoxide treated, wherein in the case of the catalysts A₂ and A₃ 2.1 g of nonane can also be added as diluent. Table 1 shows the reaction conditions, the degree of hydroperoxide conversion and the yield of octene-1-oxide.

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Table I

<td>catalyst</td><td>reaction time H</td><td>temperature ° C</td><td>Hydroperoxyd- degree of conversion %</td><td>epoxy selectivity %</td>

<td>Λ</td><td>4</td><td>107</td><td>82.3</td><td>97.3</td>

<td>a₂</td><td>1</td><td>107</td><td>86</td><td>90</td>

<td>A,</td><td>2.25</td><td>106</td><td>64.7</td><td>93.8</td>

<td>B</td><td>21</td><td>109</td><td>33.1</td><td>81</td>

<td>C</td><td>10</td><td>110</td><td>85</td><td>91</td>

<td>D</td><td>18</td><td>110</td><td>90</td><td>0</td>

<td>e</td><td>20</td><td>110</td><td>37.8</td><td>10.3</td>

<td>F</td><td>24</td><td>110</td><td>39</td><td>0</td>

After completion of the reaction in the presence of the catalyst A₂ This catalyst is separated from the reaction mixture by filtration. Colorimetric analysis of the reaction mixture indicates the presence of less than 0.00004% titanium in the solution.

Example 2: Four catalysts which can be used in a process according to the invention (catalysts Α, B, C_x, D *) and tested as well as two other comparative catalysts (catalyst E *, F).

Preparation of an approximately Equimolar Share of Titanium Dioxide and Silica-Containing Catalyst (Catalyst A) from SiCl * and TiCl *.

A mixture of 32.86 g of silicon tetrachloride (commercial product, semiconductor grade) and 27.96 g of titanium tetrachloride is added dropwise at temperatures of 25 to 40 ° C in 550 ml of deionized water. The resulting mixture is evaporated on a steam bath under reduced pressure and the resulting residue is dried overnight at 150 ° C. The product obtained has a titanium content of 48.6% by weight.

Preparation of a titanium-on-silica catalyst (catalyst B *) from SiCl * and TiCl *.

This catalyst is prepared by a process similar to that used to prepare catalyst A. A composition containing 3.9% by weight of titanium is prepared using as starting material a mixture of 25 ml of silicon tetrachloride and 2.8 g of titanium tetrachloride, which is treated with 500 ml of deionized water.

Preparation of a titanium-on-silica catalyst (Catalyst C) from SiCl * and TiCl₄,

This catalyst is prepared by a process similar to that used to prepare catalyst A. A composition containing 1.9% by weight of titanium is prepared by treating a mixture of 36.5 g of silicon tetrachloride and 0.82 g of titanium tetrachloride with 500 ml of deionized water.

Preparation of a titanium-on-silica catalyst (catalyst D *) from TiCl *.

This catalyst is prepared by a method similar to that used to prepare the catalyst A. A composition containing 0.3% by weight of titanium is prepared by treating a mixture of 36.5 g of silicon tetrachloride and 0.08 g of titanium tetrachloride with 500 ml of deionized water.

Preparation of a Titanium Dioxide Catalyst Not Containing Silicon (Catalyst Ep Made of TiCl₄·

A sample of 43 g of titanium tetrachloride is added dropwise within 15 min in 500 ml of deionized water. The resulting mixture is evaporated on a steam bath and the titanium dioxide residue is dried for 20 hours at 120 ° C under a pressure of 180 Torr. This catalyst contains 60% by weight of titanium. Preparation of a Titanium-Containing Silica Catalyst (Catalyst F *).

ml of a commercially available silicon tetrachloride (semiconductor grade) are added dropwise within 20 min in 500 ml of deionized water. The resulting mixture is evaporated on a steam bath under reduced pressure and the resulting silica residue is heated at 120 ° C overnight and at

Dried pressure of 180 Torr. The analysis indicates that the silica product contains less than 0.0035 wt% titanium.

In a series of experiments now samples of each 1 g of the aforementioned catalysts in a 100 ml glass reactor with each 36.5 g octene-1 and 4.5 g tert. Butyl hydroperoxide in each 2.1 g of nonane treated as a diluent. Table II shows the reaction conditions and the results.

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Table II

<td>catalyst</td><td>temperature ° C</td><td>reaction time H</td><td>Hydroperoxyd- ümwandlungsgrad %</td><td>epoxy selectivity %</td>

<td>A</td><td>111</td><td>4.5</td><td>61</td><td>84</td>

<td>Βχ</td><td>106</td><td>2.5</td><td>73.8</td><td>92.2</td>

<td>c_x</td><td>105</td><td>3</td><td>75</td><td>87.2</td>

<td>B&gt; x</td><td>103</td><td>5</td><td>61.3</td><td>88</td>

<td></td><td>113</td><td>21</td><td>73.1</td><td>9.2</td>

<td>^Fr</td><td>107</td><td>20</td><td>35</td><td>27</td>

Example 3: Two catalysts are prepared by using substantially the same procedure used in the preparation of catalysts Α_χ and A₂ of Example 1 was carried out. However, in place of the silica, other inorganic silica-containing solid materials are used. The catalysts are also tested in the same way as the catalysts A.₂ and A_G of Example 1. From Table III, the reaction conditions and the results are apparent.

Preparation of a titanium-on-clay catalyst (catalyst A₄).

This catalyst (titanium content = 4.4% by weight) is prepared from 4.68 g of titanium tetrachloride and 25 g of a commercially available azeotropically dried clay.

Preparation of a titanium-on-magnesium silicate catalyst (Catalyst B₂).

This catalyst (titanium content - 3.7 wt .-%) is from 4.6 g of titanium tetrachloride and 25 g of azeotropically dried, commercially available magnesium silicate gel (10.2 wt -.% Mg and 35, 6 wt -.% Si).

Table III

<td>catalyst</td><td>temperature ° C</td><td>reaction time H</td><td>Hydroperoxide conversion%</td><td>epoxy selectivity %</td>

<td>^A4</td><td>103</td><td>3</td><td>78</td><td>77</td>

<td>^BS</td><td>110</td><td>3</td><td>72.3</td><td>87.5</td>

Example 4: Four catalysts are prepared using essentially the same procedure used in the preparation of catalysts Ap A₂ and A_G of Example 1 was carried out. However, metals other than titanium are incorporated into the catalysts. The catalysts are prepared in the same way as the catalysts A_G and A_G tested by Example 1. Table IV shows the reaction conditions and results.

Preparation of a titanium / zirconium on silica catalyst (catalyst Af.

This catalyst (titanium content = 2.9% by weight zirconium content = 0.5% by weight) is prepared from 1.3 g of zirconium tetrachloride and 1.7 g of titanium tetrachloride with 25 g of azeotropically dried, commercially available fumed silica. First, the SiO₂ added only the zirconium tetrachloride, and after the release of 1 equivalent of HCl, based on ZrCl used₄, the titanium tetrachloride is added. Then continue as described.

Preparation of a titanium / niobium on silica catalyst (Catalyst B₃).

This catalyst (titanium content = 3.3% by weight, niobium content = 0.4% by weight) is prepared from 1.4 g of NbCl 2 and 1.7 g of TiCl 2₄ prepared with 25 g of the aforementioned azeotrope-dried fumed silica, wherein substantially the same method is used, which in the preparation of the catalyst A_G was carried out.

Preparation of a Titanium / Boron on Silica Catalyst (Catalyst Cp.

This catalyst (titanium content = 1.6% by weight, boron content = 0.2% by weight) is prepared from 3.4 g of boron trichloride and 2.4 g of titanium tetrachloride with 25 g of the aforementioned azeotropically dried fumed silica, essentially the same procedure is used in the preparation of the catalysts

A and B was performed.

3

Preparation of a Titanium / Tin on Silica Catalyst (Catalyst Dp.

This catalyst (titanium content = 2.4% by weight, tin content = 1.1% by weight) is prepared from 2.4 g of titanium tetrachloride and 0.45 g of tin tetrachloride with 25 g of the aforementioned azeotrope-dried fumed silica, essentially the same procedure which is used in the preparation of catalysts A_G, B₃ and C₂ was carried out.

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Table IV

<td>catalyst</td><td>temperature ° C</td><td>reaction time H</td><td>Hydroperoxide conversion%</td><td>EpoxydSelektivität %</td>

<td>A</td><td>106</td><td>0.5</td><td>77</td><td>91</td>

<td>b₃</td><td>110</td><td>0.5</td><td>69</td><td>86</td>

<td>c₂</td><td>105</td><td>17</td><td>99</td><td>79</td>

<td>^D2</td><td>106</td><td>4.5</td><td>75</td><td>85</td>

Example 5: Six catalysts (catalysts A_G, B₄, C₃, D₃, E₂, Made Fp. These catalysts are calcined before use. The catalysts are then tested by adding samples of the catalysts (0.5 g in the case of catalysts A_G, B₄ and D₃; 1 g in the case of the catalysts C_3&gt;e₂ and Fp with 1-octene (42 g in the case of catalysts A_G, B₄ and C₃; 30g in the case of the catalyst D₃; 36.5 g in the case of catalysts E₂ and Fp and tert. Butyl hydroperoxide (5.5 g in the case of catalysts A_G, B₄ and C₃; 4 g in the case of the catalyst D₃; 4.5 g in the case of the catalysts Ε_χ and Fp are treated in a 100 ml glass reactor. In the case of the catalyst D₃ 16 g of n-hexane are also added as diluent to the reaction mixture. Table V shows the reaction conditions and the results.

Preparation of a Titanium on Silica Catalyst (Catalyst A_G).

g of a commercially available silica gel (silica gel Z; specific surface = 340 m²/ g, pore volume = 1.15 cm³/ g), which has been preheated to 500 ° C for 2 h, are treated at 25 ° C with a solution of 2 ml of titanium tetrachloride in 26 ml of l, 72n hydrochloric acid. The impregnated silica gel is pre-dried on a steam bath and then treated at 25 ° G with 15 ml of 8N nitric acid. The liquid components are then evaporated on a steam bath. The residue obtained is dried at 150 ° C. for 3 hours and then calcined at 800 ° C. for 2 hours. The product obtained has a titanium content of 4.4% by weight.

Preparation of a Titanium on Silica Catalyst (Catalyst B₄).

g of silica gel Z are mixed with a solution of 1 ml of titanium tetra chloride in 24 ml of l, 72n hydrochloric acid and about 1 ml of 50 wt. treated with% aqueous hydrogen peroxide. The impregnated silica gel is dried on a steam bath at 150 ° C and then calcined at 500 ° C for 2 h. The product obtained has a titanium content of 2.2% by weight.

Preparation of a titanium-on-magnesium silicate catalyst (Catalyst CJ.

g of a commercially available magnesium silicate gel (10.2% by weight of Mg, 35.6% by weight of Si, pore volume = 1.1 cm 3 / g) are mixed with a solution of 1 ml of titanium tetrachloride and 4 ml of 16N nitric acid , 1 ml 50 wt. % aqueous hydrogen peroxide and 10 ml of water. The impregnated magnesium silicate gel is dried at 150 ° C and then calcined at 500 ° C for 2 h. The product obtained has a titanium content of 2.8% by weight.

Preparation of a titanium / didym on silica catalyst (catalyst DJ.

g of silica gel Z are mixed with a solution of 2 ml of titanium tetrachloride, 2.63 g of didymnitrate (commercially available Didym, ie a complex mixture of rare earth metals), 26 ml of l, 72n hydrochloric acid and 5 ml of 50 wt. treated with% aqueous hydrogen peroxide. The resulting mixture is evaporated on a steam bath, dried at 150 ° C and then calcined at 500 ° C for 2 h. The product obtained has a titanium content of 4.4% by weight and a Didym content of 4.3% by weight.

Preparation of a Titanium / Molybdenum Silica Catalyst (Catalyst Ep.

g of silica gel Z are treated with a solution of 1.73 g of titanium tetrachloride and 0.441 g of ammonium paramolybdate [(ΝΗ₄)₆ΜορΖ&gt;₂₄ , 4 H₂O] in 20 ml of 9N nitric acid and 4 ml of 50 wt .-% aqueous hydrogen peroxide. The impregnated silica gel is dried at 150 ° C and then calcined at 500 ° C for 2 h. The product obtained has a titanium content of 2.2% by weight and a molybdenum content of 1.2% by weight.

Preparation of a Titanium-Molybdenum Didym on Silica Catalyst (Catalyst F).

g of silica gel Z are treated with a solution of 1.73 g of titanium tetrachloride, 0.883 g of ammonium paramolybdate and 1.75 g of the above didymnitrate in 20 ml of 4N nitric acid and 4 ml of 50% by weight aqueous hydrogen peroxide. The impregnated silica gel is dried at 150 ° C and then calcined at 500 ° C for 2 h. The product obtained has a titanium content of 2.2% by weight, a molybdenum content of 2.4% by weight and a Didym content of 2.9% by weight.

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Table V

<td>catalyst</td><td>reaction time H</td><td>temperature ° C</td><td>Hydroperoxide conversion%</td><td>epoxy selectivity %</td>

<td>A</td><td>1</td><td>107</td><td>56.5</td><td>91.2</td>

<td>^B4</td><td>1</td><td>107</td><td>62.2</td><td>86</td>

<td>c₃</td><td>4</td><td>110</td><td>40</td><td>83.4</td>

<td rowspan="2">^Ds e₂</td><td>1</td><td>88</td><td>11</td><td>91.6</td>

<td>1</td><td>105</td><td>90</td><td>83</td>

<td>^p2</td><td>3.4</td><td>104</td><td>89</td><td>83</td>

Example 6: Use of a titanium on silica catalyst to epoxidize various olefinic compounds.

The olefinic compounds are each epoxidized in a glass reactor in the presence of titanium-on-Sili5 ciumdioxyd catalysts according to the apparent from Table VI reaction conditions. In experiments 1 to 11, the catalyst used is a fumed silica containing 0.3% by weight of titanium and by flame hydrolysis of SiCl₄ and TiCl₄ was produced. In experiments 12 and 13, the catalyst A is used in each case_z used by Example 1.

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Table VI

<td>epoxy selectivity %</td><td>CO CO W U3 ¢ 0 CQ CQ * 05 «5 00 * IO« 3 US &lt;»CQ * C ~ otc-05co050505oow iraooc-c</td>

<td>Hydroperoxide conversion%</td><td>M 00 00 CQ c- 05 xjl co τί co 'S «o -sf &lt;5 58 i5 2 £? φοοε-'Φ ^^03030010 co in Tf co</td>

<td>reaction time H</td><td>in CQ C-OCOi-ICOCQCOO ") CO * O CO * CO 1-) CQ oil</td>

<td>temperature ° C</td><td>ooocQinuooouo looooo 3rHrQ ^ OOOOr-lr-! 2 2 2 2 ° γΗγΗγ-ΙγΗ γΗρ-ΙγΗ γ-ιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιι</td>

<td>dilution medium</td><td>γ- &lt;«- &lt; oo NN jj 3 rl ff &lt;p fZ? SbObßbO'SS 'SS 5 7 7 I ¹ '3' 1 ii 1 £ oo ofi E ci ο ο ο O fr ΰ G ~ 8 ~ S 2 · o 53 3 Ο ii : &lt;UZ Ο O</td>

<td>Peroxide G</td><td>g H * «_ W | r. "³- 7 ^ 7. ^W, 2 co * 3 c- fr «fr * ** fr« * * § 2 fr^N for S fr fr * fr * fr * &gt;&gt; G 3 3 3 Τί ^ϊ_* 3 3 \ S 3 s- / 3/3 3 3 X'-S '-' co ^ ra '-' pa '-' ^ '-' ca '-' ca »« m »» : &lt;υΛΛΛυΛΛΛ fr fr fr</td>

<td>catalyst G</td><td>IO LO r-lr-iCNr-irHrHoCNr-l i-! Ο Ή r-1</td>

<td>olefin G</td><td>in U3 * 5 CQ CO * C0CQO00C5U3O OW 00 05 in CO C-&gt; Per CQ CQ U3 in CQ&gt; -! CQ</td>

<td>olefin</td><td>1 , * V « ό O -Ö _ «_ g &amp; £ g * &lt;a Ö 5 'S rH r-ί rH GG) G) HG) fl) XJ 2 22 5 3 3 3 O 'S «3' S in 5 fr fr fr fr 2 2 • 4) ω 4) 3 7 {7) n ^u Ti «3 &lt;B 'S» 33&gt; S&gt;. 43 Q-&gt; -W -S 3 UUX 2 CQ T3 τίSi 4) 4) cd - ü ο ο o&gt; s&gt;. 14). »». S ä «=! e Γ2 r! ο ο o 2 υ υ -φ Yes u · -i cs 2 2 G &lt;&lt;</td>

<td>attempt</td><td>rHCQCO \ tcmtOC-0OO5 O ll CQ CO rH rM rl rl</td>

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Example 7: Epoxidation of propylene with ethylbenzene hydroperoxide in the presence of a titanium-on-silica catalyst.

This catalyst is prepared as follows.

g of a commercially available silica gel (specific surface = 340 m²/G; Pore ​​volume = 1.15 cm³/ g) with a solution of 5.18 g of titanium tetrachloride in 68 ml of 4N nitric acid and 4 ml of 50 wt. - Treated% hydrogen peroxide. The impregnated silica gel is dried at 100 ° C and then calcined at 800 ° C for 2 h. Analysis of the titanium dioxide-silica product obtained gives a titanium content of 2.18%.

The epoxidation of propylene with ethylbenzene hydroperoxide is carried out in a tubular reactor (diameter = 12.7 mm, length = 1.83 m) in which the catalyst is arranged in the form of a fixed bed. The reactor is continuously charged with a reaction mixture consisting of 6 moles of propylene per mole of ethylbenzene hydroperoxide dissolved in ethylbenzene. The residence time of the mixture in the reactor is about 24 minutes, and it will be in the reactor apparent from Table VII temperatures and a pressure of about 42 kg / cm² (Overpressure). The reaction conditions and the results of the analysis of the product mixture after each indicated reaction time are shown in Table VII.

Table VII

<td>Test duration h (total)</td><td>temperature ° C</td><td>Hydroperoxyd- degree of conversion %</td><td>Propylenoxyd- selectivity %</td>

<td>44</td><td>100</td><td>76.8</td><td>84.0</td>

<td>83</td><td>110</td><td>89.0</td><td>85.0</td>

<td>310</td><td>110</td><td>85.2</td><td>83.0</td>

<td>379</td><td>114</td><td>87.6</td><td>86.5</td>

EXAMPLE 8 Use of Catalysts Containing Titanium and Other Metals on Non-Silica-Dioxide-Containing Carrier (Comparative Experiment)

There are several catalysts containing various metals, such as titanium, and as a carrier silicon dioxide-free materials, for their suitability for epoxidation of octene-1 with tert. Butyl hydroperoxide tested. The reaction conditions and the results are shown in Table VIII. The catalysts used in Experiments I to VII are prepared by reacting a metal halide with either fumed alumina having a specific surface area of ​​100 m²/ g or Mg (OH) Cl with a specific surface area of ​​about 20 m²/ g or zirconium dioxide with a specific surface area of ​​169 m²/ g, each using a method similar to that used in the preparation of the catalyst A ^. The catalyst used in Experiment VIII contains 2.5% by weight of cobalt and 9.5% by weight of molybdenum and aluminum oxide as carrier (commercial product). In Experiment IX, the epoxidation of octene-1 with tert. Butyl hydroperoxide carried out without a catalyst.

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Table VIII

<td>epoxy selectivity %</td><td>ri il CQ ft</td>

<td>»2 00 κ ob 2 § o gj 3 Ο- Ό 0 c 22 * 4 Ό&gt; &gt; · £ x E □</td><td>CM CM O ^ TfQlßCOUOOC " toc-oiSio "O5fc-w</td>

<td>ΰ 23 rt Ό C Joe oi</td><td>eat COCOlß ^ CMCOrHCMQ Ol Ol CM CM rH CM</td>

<td>a rt SLU e ° 4) H</td><td>ooi-ioooooö</td>

<td>Nonane as a diluent G</td><td>ri rH rH rH W «H CM * CM * CM * CM Ο O CM O CM</td>

<td>tert. -Butylhydroperoxyd G</td><td>LQkßkßkßlßkßtßrtDiß □) xj «« ψ rt * * * ί * uo M *</td>

<td>Octene-1 G</td><td>1/3 tss ate {Ο to to to «Ο« O CM &lt;0 COCOCOCOCOCQCO ^⁴⁰³</td>

<td>catalyst G</td><td>rMKiHrHrHrrtrH'-IO</td>

<td>Metal content at Catalyst carrier wt. -Io</td><td>Η PPP § PN Ö 2 tf · $ 1 Oil is eaten ri TjT ei cm 5a Eat CM CM oil</td>

<td>Aiisgangsmaterialien Catalyst Preparation</td><td>Ό Ό Ό Ό Ό §§§§§§§ Έ © © © © © © © © © © © c- co c- oo ⁰⁵ &lt; ri iq u3 ß CM CM CM CM CM CM i U3 i i CM i i i i i i * -&gt; Ol CM CM W CM CM CM * S '-' • w '' w '»* -' -r- _ V-, g G 2 σΧ G's: σ'ο σΐ § "2 ~ iS- o's:! .1 H &lt;Pn P 2 § &lt;h &lt;n &lt;u λ</td>

<td>attempt</td><td>~ 5 &gt;&gt; £££ *</td>

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Example 9: Use of catalysts containing metals other than titanium on silica as support (comparative experiment).

There are several catalysts, which are made of metals other than titanium and silica as support be tested for their suitability for the epoxidation of octene-1 with tert-butyl hydroperoxide. Table IX 5 shows the reaction conditions and the results. The catalysts used in Experiments X through XII are prepared by reacting a metal halide with SiO, Type X, using a procedure similar to that used in the preparation of Catalyst A, Example 1. The catalysts used in experiments XII to XVIII are prepared by co-hydrolysis of a metal halide and silicon tetrachloride, using a procedure similar to that described in Example 2. The catalyst for experiment XIX is prepared by treating 50 g of a commercially available silica gel (specific surface area = 750 m²/ g) with a solution of 0.625 g of chromium trioxide in 20 ml of water, drying of the impregnated silica gel at 150 ° C and then calcination for 2 hours at 500 ° C prepared. In experiment XX, a catalyst is used which is prepared by treating 20 g of a commercially available magnesium silicate gel (10.2% by weight of magnesium, 35.6% by weight of silicon), the pore volume of about 1.1 cm³/ g, with a solution of 0.1 g of chromium trioxide in 25 ml of water, drying of the impregnated magnesium silicate gel at 15O ° C and calcination of the dried gel at 500 ° C is prepared overnight. The catalyst used in experiment XXI is prepared by mixing 10 g of a commercially available fumed silica (specific surface area = 200 m²/ g) with a solution of 0.308 g of tungstic acid (H, WO₄), 45 ml 25 wt. -% ammonium hydroxide and 5 ml 50 wt. 20% hydrogen peroxide are treated and the impregnated silica is dried at 50 ° C and then calcined at 800 ° C for 2 h. To prepare the catalyst used in experiment XXII, 10 g of commercially available fumed silica with a solution of 1 g of rhenic acid (HReO₄) in 30 ml of water and then dried at 200 ° C.

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<td>epoxy Selectivity 7 »</td><td>CM 00 CM U3 ri CM iß © © C "Iß 00 Γ- O CM CO rl il rl ι-1 rM ti CO</td>

<td>Ό¹ 2 &gt;&gt; 8P X BO 8 § o oc Ό ·&gt; XE P</td><td>© C- &lt;O CM co © © © © © © co © © © © © Q3 © rf in CO, CM, C- CO CM O</td>

<td>reaction time H</td><td>CM tl 00 co CO c- Γ-l © © O tl xf tf rl rH ri CM C- CM CM</td>

<td>temperature ° c</td><td>io 00 Ο O CO © © 00 rd © © © o o tl i- (© ri rl © ti rl rt O ι-l rl ri tl ii tl tl ri tl rl ti ti</td>

<td>Nonane as a diluent G</td><td>rl t-1 r-I «-1 rl rl rl t-1 r-1 CM CM CM CM CM CM CM CM CM © © © ©</td>

<td>tert. Butyl hydroperoxide g</td><td>m in io io io io io i Tp TjT xf xf -φ xf χ £ xf 'Φf IO xf</td>

<td>Octene-1 G</td><td>misleading to td td © to to co cd cd to cm cm to CO CO CO CO CO CO CO CO CO 'Φ co</td>

<td>Catalyst- amount G</td><td>r-ι Γ-l Ti rl ι-H tl Wri rl τΊ fl</td>

<td>the metal incorporated in the catalyst, Wt.</td><td>to 00 xfCMlßCOflCMCOiss ©© CO W i fl © Ri © 'C0 O ti O CM ©</td>

<td>Catalyst made from</td><td>ooooooooo ccccccccc O 'Sö'DÖ'S &amp;' Sbiö'Sö'Sb'Sb'SJ'SS ^ 'SöSi'SÖ®'®®® ⁰³co oo © e-oe-Soioc-coc ^ oco _N OQ 2 CM ß co '' co © © to © to © © © © © © © Ο ^ww⁰⁴ SS * «α t, Ό to § § § s,, σγ gy gy §y cv «y sy 2- s ι £ w Zw Hw Zw Zw 5w £ w Hw Hw (JUXX</td>

<td>attempt /</td><td>Ξ&gt;&gt; 5 5 £ x SS xxxxxxxxx xxxx</td>

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Example 10: Use of Various Metal Compounds Without Silicon Dioxide-Containing Material (Comparative Experiment)

In a series of experiments, various metal compounds are tested for their suitability as heterogeneous catalysts in the epoxidation of octene-1 with tert-butyl hydroperoxide. In each experiment, a Pro5 be of 1 g of the respective metal compound in proportions of 36.5 to 42 g octene-1 and proportions of 4.5 to 5, 5 g tert. Butyl hydroperoxide treated. Table X shows the reaction conditions and the results.

Table X

<td>attempt</td><td>catalyst</td><td>Nonane as thinners voltage medium G</td><td>reaction duration H</td><td>temperature- ture ° C</td><td>Hydroperoxide conversion%</td><td>epoxy selective tivity %</td>

<td>1</td><td>TiO₂ (Commercial product)</td><td>2.1</td><td>20</td><td>110</td><td>50</td><td>0</td>

<td>2</td><td>TiO₂ (Commercial product)</td><td>2.1</td><td>18</td><td>110</td><td>40</td><td>0</td>

<td>3</td><td>TiO₂ (hydrolyzed TiCl₄ v. Example II E</td><td>2.1</td><td>21</td><td>113</td><td>73.1</td><td>9.2</td>

<td>4</td><td>Bi Ti O 2 2 7</td><td>0</td><td>4</td><td>110</td><td>48</td><td>6</td>

<td>5</td><td>MgTiO₃</td><td>2.1</td><td>12</td><td>116</td><td>28</td><td>1</td>

<td>6</td><td>SrTiO₃</td><td>2.1</td><td>16</td><td>111</td><td>35</td><td>1</td>

<td>7</td><td>CaTiO₃</td><td>2.1</td><td>16</td><td>110</td><td>28</td><td>1</td>

<td>8th</td><td>ZrO₂</td><td>2.1</td><td>20</td><td>107</td><td>76.7</td><td>5</td>

<td>9</td><td>(NH₄)₄^zrh₆</td><td>0</td><td>2</td><td>110</td><td>24</td><td>0</td>

<td>10</td><td>Zrß₂</td><td>0</td><td>2</td><td>110</td><td>85</td><td>0</td>

<td>11</td><td>CaZrO_G</td><td>0</td><td>2</td><td>110</td><td>10</td><td>0</td>

<td>12</td><td>Nb O 2 5</td><td>0</td><td>4.5</td><td>115</td><td>9</td><td>0</td>

<td>13</td><td>^Ta2 °₅</td><td>0</td><td>4.5</td><td>110</td><td>11</td><td>5</td>

<td>14</td><td>CrO₃</td><td>0</td><td>0.5</td><td>108</td><td>99</td><td>22</td>

<td>15</td><td>CrCl₃</td><td>0</td><td>1.5</td><td>96</td><td>98</td><td>0</td>

<td>16</td><td>WC</td><td>2.1</td><td>112</td><td>116</td><td>56</td><td>5</td>

<td>17</td><td>Where 3</td><td>0</td><td>22</td><td>111</td><td>85</td><td>8th</td>

<td>18</td><td>Re O 2 7</td><td>0</td><td>4</td><td>110</td><td>100</td><td>0</td>

<td>19</td><td>TeO 2</td><td>0</td><td>22</td><td>110</td><td>33</td><td>7</td>

<td>20</td><td>Se0_O2</td><td>0</td><td>3</td><td>110</td><td>97</td><td>0</td>

<td>21</td><td>uo 2</td><td>0</td><td>20</td><td>110</td><td>55</td><td>5</td>

Example 11: Three catalysts (catalyst R, S, T) are prepared and tested by adding 10 g of a sample of 1 g of the respective catalyst in a 100 ml glass reactor for 90 min at 125 ° C with 17 g octene each -1, 25 g of ethylbenzene hydroperoxide (as a 14.2% strength by weight solution in ethylbenzene) and 8 g of nonene. The results are shown in Table XI.

Preparation of a titanium-on-silica / alumina catalyst (catalyst R).

210 g of a commercially available silica-alumina (97, 6% SiO 2 and 1.2% Al₂O₃), the 15 a pK_aValue of -5, a specific surface of 300 m²/ g and a pore volume of 0.75 cm³/ g and is present mainly as Al-silicate, with a solution of 10 ml of titanium tetrachloride in 144 ml of 4N nitric acid and 18 ml of 50 wt. treated with% aqueous hydrogen peroxide. The impregnated silica / alumina is dried at 150 ° C and then calcined at 800 ° C for 2 h. The product obtained has a titanium content of 2.2% by weight.

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Preparation of a Titanium / Magnesium on Silica / Alumina Catalyst (Catalyst S).

g of the silica used for the preparation of the catalyst R alumina are with a

Mixture of 1 ml of titanium tetrachloride, 2.31 g of magnesium nitrate hexahydrate, 19 ml of 4N nitric acid and 1 ml of wt. treated with% aqueous hydrogen peroxide. The impregnated silica-alumina is dried at 160 ° C and then calcined at 800 ° C for 2 h. The product obtained has a titanium content of 2.2% by weight and a magnesium content of 1.1% by weight. It owns a pK_aValue of 3.3.

Preparation of a titanium / calcium-silica / alumina catalyst (catalyst Ί).

g of the silica-alumina used to prepare the catalysts R and S are mixed with a mixture of 1 ml of titanium tetrachloride, 2.12 g of calcium nitrate tetrahydrate, 19 ml of 4N nitric acid and 1 ml of 50 wt. treated with% aqueous hydrogen peroxide. The impregnated silica-alumina is dried at 160 ° C and then calcined at 800 ° C for 2 h. The product obtained has a titanium content of 2.2% by weight, a calcium content of 1.8% by weight and a pK_aValue of 1.5.

Table XI

<td>attempt</td><td>catalyst</td><td>Hydroperoxide conversion degree%</td><td>epoxy selectivity %</td>

<td>R</td><td>2.2% by weight of Ti on SiO 2₂ , A1₂O₃</td><td>74.1</td><td>29.1</td>

<td>S</td><td>2.2% by weight of Ti / 1.1% by weight Mg on SiO ". Al O, 2 2 3</td><td>80.9</td><td>72.7</td>

<td>T</td><td>2, 2% by weight of Ti / 1.8% by weight Ca on SiO 2₂ , A1₂O₃</td><td>93.3</td><td>66.3</td>