Catalytic epoxidation of olefins.

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

C = C + -C -O-O

Olefin group Hydroperoxide group Oxirane group

CC + - C - OH

hydroxyl

reacted with an organic hydroperoxide compound.

The usefulness of oxirane compounds is known. Many of these compounds are commercial products, especially olefin oxides such as ethylene or propylene oxide. As described, for example, in US Pat. Nos. 2,815,343, 2,871,219 and 2,987,498, propylene oxide can be converted into 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, glycerin can also be prepared from the oxirane compound formed using allyl alcohol as the starting material.

Of particular interest is the reaction of propylene with ethylbenzene hydroperoxide according to the following reaction equation:

H₂C = CH-CH₃ +

> H₂C CH-CH₃

Propylene oxide Mcthylphenylcarbinol

In this case, styrene can be obtained as a valuable by-product.

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 heteropolyacids used in dissolved form which contain transition metals such as chromium, molybdenum or tungsten. The US-PS 33 50 422 and 33 51 635 describe the use of solutions of eo compounds of the transition metals (V, Mo, W, Ti, Nb, Ta, Re, Se, Zr, Te and U). However, these known catalysts are generally effective only if they are homogeneously dissolved in the reaction mixture.

According to DE-PS 12 51298 olefins are epoxidized with organic hydroperoxides in the presence of a catalyst comprising a compound of a metal of IV. To VI. Subgroup of the Periodic Table and a compound of a metal of the VII. Or VIII. Nebengruppi; of the periodic table. It is generally stated that the reaction can proceed in a homogeneous or heterogeneous phase and the catalyst can be present in solution, in suspension or on support materials, such as asbestos, activated carbon, alumina or silica gel. The subject of DE-OS 15 18 644 is a process for the epoxidation of olefinic compounds by means of organic hydroperoxides which at -20 to 15O⁰C in the presence of a compound of a metal of IV. To VI. Subgroup of the periodic table is carried out as a catalyst, the reactants are not suddenly reacted with each other, but slowly combined in small portions, eg. B. by dropping. It is only generally stated that the catalyst is supported on support material.

Rialia may be present, and as in DE-PS 12 51 298 soluble catalysts are clearly preferred.

DE-PS 12 51 298 does not teach, from which must be a practically useful heterogeneous epoxidation catalyst. Such a catalyst should not only be completely insoluble in the reaction mixture, but also have high activity.

Heterogeneous catalysts have the advantage that they are easily separated from the reaction products.

It has surprisingly been found that the catalysts specified below, which contain titanium in chemical combination with silica and / or inorganic solid silicates, have high activity as epoxidation catalysts and a high degree of conversion of the hydroperoxide used and a high selectivity towards the formation of the desired oxirane compounds guarantee. The selectivity is defined by the molar ratio of the oxirane compound to the hydroperoxide. Heterogeneous catalysts containing titanium in chemical association with silica and / or inorganic solid silicates are not mentioned in the above references. It is very surprising that the latter catalysts have a high activity, because it was found (see Table X) that the inorganic titanium compounds TiO₂, Bi₂Ti₂O₇, MgTiO₃, SrTiO₃ and CaTiO₃ and a physical mixture of SiO₂ and TiO₂ are inactive as epoxidation catalysts.

The invention thus provides a process for the preparation of oxirane compounds by reacting an optionally substituted by a hydroxyl group or a halogen atom alkene having 3 to 40 carbon atoms, mesityl oxide, methyl-j3, ^ '- dimethyl acrylate or cyclohexene, optionally by a hydroxyl group , an aldehyde group or a 4-cyano group is substituted with a hydrocarbon hydroperoxide having 3 to 20 C-atoms at temperatures from 0 to 200⁰C in a heterogeneous system in the presence of a titanium catalyst which is essentially insoluble in the reaction mixture, optionally on a support material, which is characterized in that the catalyst consists of a chemical compound of silicon dioxide and / or inorganic solid silicates having a specific surface area of ​​from 25 to 800 m²/ g, and titanium in a catalyst based amount of 0.2 to 50 weight percent in terms of titanium dioxide, and optionally up to 10 weight percent of the oxides or hydroxides of boron, zinc, niobium, tin, zirconium, Tantalum, chromium, molybdenum, tungsten, rhenium, uranium, bismuth and the rare earth metals (atomic numbers from 57 to 71) and to which promoters are optionally added, the content of the silicon in the silicate, expressed as silica, at least 50 weight percent.

In the context of the invention, preference is given to catalysts in which the content of silicon in the silicate, expressed as silicon dioxide, is at least 75 percent by weight, in particular at least 90 percent by weight.

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 Maferialien contained in the hydroperoxide solution used. In addition, the preferred solvents are mononuclear aromatics, benzene, toluene, chlorobenzene, bromobenzene or o-dichlorobenzene, and alkanes, such as octane, decane or benzene

However, an excess of the olefinic compound used together with the solvent which has been introduced together with the hydroperoxide can also serve as solvent so that no further solvents need be added. The total content of the solvent may be up to 20 mol / mol of hydroperoxide.

The reaction generally proceeds at moderate temperatures and under moderate pressures.

Temperatures of 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. Pressures of 1 to 98 bar are generally sufficient, atmospheric pressure is appropriate.

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 combination of titanium with solid inorganic silicon dioxide-containing compounds, ie silica and / or silicates. The titanium becomes tetravalent during the reaction and is preferably combined with the inorganic solid siliceous compounds in this oxidation state. The proportion of titanium in the catalyst can be varied in the range of 0.2 to 50 weight percent in terms of titanium dioxide.

Relatively dense, tightly packed, porous masses of aggregated or bound together

Particles of amorphous silica, such as silica gel or precipitated silica, are suitable for example for catalysts in the process of the invention. The production and the properties of these products are z. In the book »The Colloid Chemistry of

b5 Silica and Silicates ", Cornell University Press, New York (1955), Chapter VI, by RG Her, and in US Pat. No. 2,657,149. Silica gel commercial products containing at least 99% silica

exist and have a specific surface area of ​​25 to 700 m²/ g and a pore 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 nuberverförmige Siliziumdioxidsorten consisting of particles of amorphous silica. These particles are flakes in the form of open-packed, easily separable, loosely bound aggregates. An example of powdered Srliciumdioxidsorten is fumed silica in airgel form, which is obtained by combustion of hydrogen and oxygen with silicon tetrachloride or tetrafluoride. Airgel silica is commercially available in the form of several products. Generally, most suitable are airgel silica grades consisting of at least 99% silica and a specific surface area of ​​50 to 400 m²/ g and have a particle size of 0.007 to 0.05 μ.

Further examples of erfindungsgv.-suitably suitable inorganic solid silicon dioxide-containing compounds are known under the name "molecular sieves" crystalline aluminosilicates and naturally occurring crystalline mineral silicates such as asbestos minerals, eg. As serpentine (crystal water-containing magnesium silicate), clay minerals, z. Hectorite (magnesium lithium silicate), kaolins, bentonites and mica minerals, e.g. B. Phlogopite (potassium magnesium aluminum silicate) or vermiculite (magnesium silicate containing water of crystallization). However, preferred are synthetic amorphous inorganic solid silica-containing compounds, especially those consisting essentially of substantially pure silica, e.g. B. at least 95% of silica consist.

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 into oxides. To carry out the conversion into oxides, it may be advantageous to pretreat the originally prepared catalyst prior to its use. The proportions of the promoter or promoters are not critical, but usually at most 10 percent by weight, in terms of metal and based on the catalyst support, is required. The incorporation of promoters is particularly useful when inorganic solid silica-containing compounds having strong acid sites are used, e.g. B. at a Eigenacidität of below -3. The generally by the value pK_a expressed natural acidity is determined by titration of the material in question with a suitable base in the presence of an indicator dye, such. B. in US-PS 28 68 688 is described

For the preparation of the catalysts used in the invention kiinn man z. For example, a mixture of silica and titanium dioxide and / or a silicate calcine. It is also possible, for example, to drop a mixture of titanium tetrachloride and silicon tetrachloride into water, which is dissolved¹age>^p Evaporate and dry the residue obtained. The catalyst can also be prepared by the methods described in U.S. Patent Nos. 3,166,542, 2,120,959, or 3,174,120 by reacting the hydroxyl groups on the surface of the inorganic solid silica-containing compound with a titanium salt. According to a weaker process, a pyrogenic

50

55

60

A catalyst in airgel form, in particular a fumed titania-silica, 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 can be pretreated. Such pretreatment is preferred for achieving higher activity.⁷or treatment, the catalyst is generally advantageously heated 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 method is the most appropriate in each case. B. the catalyst initially contains titanium in the form of its tetrachloride, it is useful to convert the chlorine atoms present in the catalyst into oxidic groups, since the chlorine atoms are likely to affect the epoxidation reaction by formation of HCl. The conversion can be carried out in the rule with advantage 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 may be employed in the process of the invention in any suitable physical form, e.g. As a powder, flakes, grains or pellets.

The titanium-SiO 2 catalysts described above may additionally contain up to 10% by weight of the oxides or hydroxides of boron, zinc, niobium, tin, zirconium, tantalum, chromium, molybdenum, tungsten, rhenium, uranium, bismuth and the rare earth metals ( Atom numbers from 57 to 71).

Suitable hydrocarbon hydroperoxide compounds are compounds having from 3 to 20 carbon atoms, especially in the form of a secondary or tertiary alkyl or aralkyl radical, such as tert-butyl, tert-pentyl, cyclopentyl, 1-phenylethyl-1 - And 2-phenylpropyl-2-restes or the various Tetralinylresie, which are formed by cleavage of a hydrogen atom from the aliphatic side chain of a tetralin molecule. The hydroperoxide having the 1-phenylethyl-l-residue is also known as ethylbenzene hydroperoxide and the compound having the 2-phenylpropyl-2-residue as cumyl hydroperoxide tert-butyl hydroperoxide and aralkyl hydroperoxides whose hydroperoxy group is linked to a carbon atom bonded directly to an aromatic ring is, such as ethylbenzene hydroperoxio, are preferably used.

The hydrocarbon hydroperoxide is usually used in the form of solutions having a hydroperoxide content of 5 to 70 percent by weight, since such solutions are readily preparable by oxidation of the hydrocarbon in question

In the context of the invention, preference is given to using alkenes having 3 to 40 C atoms which are substituted by a hydroxyl group or a chlorine atom, such as allyl alcohol, crotyl alcohol and allyl chloride.

The examples illustrate the invention.

example 1

.There are five suitable catalysts for the process according to the invention (catalyst Ai, A2, A3, B, C)

and three other comparative catalysts (catalyst D, E, F) prepared and tested.

Preparation of a Titanium on Silica

Catalyst (catalyst Ai) from pyrogenic

Silica and titanium tetrachloride

A mixture of 5 g of a commercially available pyrogenic silicon diuxide having a specific surface area of ​​390 m²/ g and 1700 ml of n-heptane is dried by heating under reflux for 19 hours in a glass reactor equipped to trap the azeotropic boiling water / heptane mixture with a Dean-Stark trap. After cooling the mixture to about 25 ° C, a sample of 0.47 g (2.5 mmol) of tantalum 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 mmoles of HCl (1 equivalent, based on TiCU) are released, 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 hours at a temperature of 97 ° C, the hydrogen chloride evolution stops. The reaction mixture is then evaporated under reduced pressure at elevated temperature, and the residue obtained is overnight under a pressure of 239.94 mbar at 12O⁰C dried. The titanium content of the obtained product is 0.4% by weight.

The catalyst A₂ is prepared in the same manner as the catalyst Ai, but a TiCU content of 4.68 g is 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 Ai, but titanium trichloride is used instead of titanium tetrachloride. The proportion of titanium trichloride is 3.62 g (0.023 mol). The addition of water is started when about 0.023 moles of hydrogen chloride (1 equivalent, based on T1CI3) are released. 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 silicon tetrachloride

A mixture of 25 g of a commercially available fumed titanium dioxide having a specific surface area of ​​50 m²/ g and a grain size of 15 to 40 ηιμ, and 1700 mi n-heptane is heated for 19 hours under reflux in a glass reactor, which is equipped to capture the azeotropic boiling water / heptane mixture with a Dean-Stark trap , After cooling the mixture to room temperature, a sample of 7.84 g (0.046 mol) of silicon tetrachloride in 25 ml of anhydrous n-heptane is fed to the reactor and the reaction mixture is brought to about 97⁰C heated until about 0.046 mol of hydrogen chloride are released. The hydrogen chloride is expelled through a stream of dry nitrogen and passed into a stripping apparatus containing a dilute alkali solution. To initiate the evolution of further hydrogen chloride, about 10 ml of water is added in about 0.5 ml aliquots after a reaction time of about 20

15

Hours at a temperature of 97⁰C stops the hydrogen chloride evolution. The reaction mixture is then reduced to about 100 under reduced pressure⁰C. and the resulting residue is stirred at 120.degree. C. under a pressure of 239.94 mbar for 16 hours⁰C dried. The silicon content of the obtained product is 3.2% by weight.

Preparation of a silica-titania

Catalyst (catalyst C) of fumed silica and pyrogenic titanium dioxide

3 pyrogenic silica (S1O2, type X) and 1 g of pyrogenic titanium dioxide (TiO₂, Type Y) are thoroughly mixed and then heated to 700 in an oven for 24 hours⁰C heated. The product obtained is ground to a powder.

Titanium dioxide catalyst without silicon (catalyst D)

This catalyst is the aforementioned pyrogenic titanium dioxide (TiO₂Y).

Silica catalyst without titanium (catalyst E)

This catalyst is the aforementioned fumed silica (SiO₂X).

Physical mixture of fumed silica and titania (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 now each 1 g of the aforementioned catalysts are treated in a 100 ml glass reactor with 36.5 g octene-1 and 4.5 g tert-butyl hydroperoxide, in the case of catalysts A₂ and A3 also 2.1 g of nonane can be added as a diluent. Table 1 shows the reaction conditions, the degree of hydroperoxide conversion and the yield of octene-1-oxide.

Table I

<p><tgroup cols="7"><tbody><row><entry> 45 </entry><entry>Cata- capacitor</entry><entry>Reaction time</entry><entry>4</entry><entry>Temperature</entry><entry>Hydroperoxide conversion degree</entry><entry>Epoxide selectivity</entry></row><row><entry></entry><entry></entry><entry>H</entry><entry>1</entry><entry>C</entry><entry>%</entry><entry>%</entry></row><row><entry> 50 </entry><entry>A,</entry><entry>2,25</entry><entry>107</entry><entry>82,3</entry><entry>97,3</entry></row><row><entry></entry><entry>A₂</entry><entry>21</entry><entry>107</entry><entry>86</entry><entry>90</entry></row><row><entry></entry><entry>A₃</entry><entry>10</entry><entry>106</entry><entry>64,7</entry><entry>93,8</entry></row><row><entry> 55 </entry><entry>B</entry><entry>18</entry><entry>109</entry><entry>33,1</entry><entry>81</entry></row><row><entry></entry><entry>C</entry><entry>20</entry><entry>110</entry><entry>85</entry><entry>91</entry></row><row><entry></entry><entry>D</entry><entry>24</entry><entry>110</entry><entry>90</entry><entry>0</entry></row><row><entry></entry><entry>e</entry><entry>110</entry><entry>37,8</entry><entry>10,3</entry></row><row><entry> 60 </entry><entry>F</entry><entry>110</entry><entry>39</entry><entry>0</entry></row></tbody></tgroup></p>

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.

Step Example! 2

Four catalysts which can be used in a process according to the invention (catalysts A, B), C j, di) are prepared and tested as well as two further comparative catalysts (catalyst Ei, Fi).

Production of an approximately equimolar amount of

Containing titanium dioxide and silica

Catalyst (catalyst A) of SiCU and TiCU

A mixture of 32.86 g of silicon tetrachloride (commercial product, semiconductor grade) and 27.96 g of titanium tetrachloride is heated at temperatures of 25 to 40⁰C was added dropwise to 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 wt .-%.

Preparation of a titanium-on-silica catalyst (catalyst Bj) from SiCU and TiCU

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 Ci) from SiCU and TiCU

This catalyst is prepared by a process similar to that used to prepare catalyst A. A mass 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 Di) from TiCU

This catalyst is prepared by a process similar to that used to prepare 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 E₁) made of TiCU

A sample of 43 g of titanium tetrachloride is added dropwise within 500 ml of deionized water within 15 minutes. 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 No Titanium-Containing Silica Catalyst (Catalyst Fi)

25 ml of a commercially available silicon tetrachloride (semiconductor grade) are added dropwise within 20 minutes in 500 ml cntionisieiK ^ water. The resulting mixture is evaporated on a steam bath under reduced pressure and the resulting silica residue is left at 120 overnight⁰C and dried at a pressure of 180 Torr. Analysis shows that the silica product contains less than 0.0035 wt% titanium

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

Table II

<p><tgroup cols="5"><tbody><row><entry>catalytically</entry><entry>Tem</entry><entry>reaction</entry><entry>hydro-</entry><entry>epoxide</entry></row><row><entry>sator</entry><entry>temperature</entry><entry>TION</entry><entry>peroxide-</entry><entry>Selekli-</entry></row><row><entry></entry><entry></entry><entry>daucr</entry><entry>conversion</entry><entry>tivity</entry></row><row><entry></entry><entry></entry><entry></entry><entry>Degree</entry><entry></entry></row><row><entry></entry><entry> C </entry><entry>H</entry><entry>%</entry><entry>%</entry></row></tbody></tgroup></p>

111 106 105 103 113 107

4,5

2,5

21 20

73,8

61,3

73,1

84 92,2 87,2 88 9,2 27

Example 3

Two catalysts are prepared by using substantially the same procedure used in the preparation of catalysts Ai and A2 of Example 1. However, in place of the silica, other inorganic silica-containing solid materials are used. The catalysts are also tested in the same manner as the catalysts A2 and A3 of Example 1. Table III shows the reaction conditions and the results.

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 azeotrope-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 .- ° / o Si).

Table III

<p><tgroup cols="5"><tbody><row><entry>catalytically</entry><entry>Tem</entry><entry>reak</entry><entry>hydro-</entry><entry>epoxide</entry></row><row><entry>sator</entry><entry>temperature</entry><entry>TION</entry><entry>peroxide-</entry><entry>selective</entry></row><row><entry></entry><entry></entry><entry>duration</entry><entry>conversion</entry><entry>tivity</entry></row><row><entry></entry><entry></entry><entry></entry><entry>Degree</entry><entry></entry></row><row><entry></entry><entry>C "</entry><entry>H</entry><entry>%</entry><entry>%</entry></row></tbody></tgroup></p>

103 110

3 3

I !,

78 72,3

77 87,5

4

Four catalysts are prepared using substantially the same procedure used in the preparation of catalysts Ai, A2 and A3 of Example 1. It will, however

li I:

other metals except titanium incorporated in the catalysts. The catalysts are prepared in the same way as the catalysts A₂ and A₃ tested by Example 1. Table IV shows the reaction conditions and results.

Preparation of a Titanium / Zirconium on Silica Catalyst (Catalyst A5)

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 proceed as described.

Preparation of 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 NbCl₅ and 1.7 g of TiCl₄ prepared with 25 g of the aforementioned azeotrope-dried fumed silica, wherein substantially the same method is used, which was carried out in the preparation of the catalyst A5.

Preparation of a Titanium / Boron on Silica Catalyst (Catalyst C₂)

This catalyst (titanium content = 1.6 wt .-%, boron content = 0.2 wt .-%) 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, wherein substantially the same procedure used in the preparation of catalysts A5 and B₃ was carried out.

Preparation of a Titanium / Tin on Silica Catalyst (Catalyst D₂)

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 abovementioned azeotrope-dried fumed silica, essentially the same procedure used in the preparation of catalysts A5, B₃ and C₂ was carried out.

<p><tgroup cols="7"><tbody><row><entry>table</entry><entry>IV</entry><entry>Temperature</entry><entry>Reaction time</entry><entry>0,5</entry><entry>Hydroperoxide conversion degree</entry><entry>Epoxide selectivity</entry></row><row><entry>Cata- capacitor</entry><entry>C</entry><entry>H</entry><entry>0,5</entry><entry>%</entry><entry>%</entry></row><row><entry></entry><entry>106</entry><entry>17</entry><entry>77</entry><entry>91</entry></row><row><entry>A₅</entry><entry>110</entry><entry>4,5</entry><entry>69</entry><entry>86</entry></row><row><entry>B₃</entry><entry>105</entry><entry></entry><entry>99</entry><entry>79</entry></row><row><entry>C₂</entry><entry>106</entry><entry>75</entry><entry>85</entry></row><row><entry>D₂</entry><entry></entry><entry></entry></row></tbody></tgroup></p>

calcined before use. The catalysts are then tested by adding samples of the catalysts (0.5 g in the case of catalysts A₆, B₄ and D₃; 1 g in the case of the catalysts C₃, E₂ and F₂) with 1-octene (42 g in the case of the catalysts Ae, B₄ and C₃; 30 g in the case of the catalyst D₃; 36.5 g in the case of catalysts E₂ and F₂) and tertiary butyl hydroperoxide (5.5 g in the case of the catalysts Ae, B₄ and C₃; 4 g in the case of the catalyst D₃; 4.5 g in the case of catalysts E₂ and F₂) in a 100 ml glass reactor. In the case of the catalyst D₃ 16 g of η-hexane are also added to the reaction mixture as a diluent. Table V shows the reaction conditions and the results.

Preparation of Tuan on silica catalyst (Catalyst Ab)

20 g of a commercially available silica gel (silica gel Z; specific surface = 340 m²/ g, pore volume = 1, 15 cc / g) for 2 hours to 500⁰C was preheated, are treated at 25 ° C with a solution of 2 ml of titanium tetrachloride in 26 ml of 1.72 N hydrochloric acid. The impregnated silica gel is pre-dried on a steam bath and then at 25⁰C treated with 15 ml of 8 η-nitric acid. The liquid components are then evaporated on a steam bath. The residue obtained is 15O for 3 hours⁰C and then 800 for 2 hours⁰C calcined. The product obtained has a titanium content of 4.4% by weight.

Preparation of a Titanium on Silica Catalyst (Catalyst B₄)

20 g silica gel Z with a solution of 1 ml of titanium tetrachloride in 24 ml of 1.72 η hydrochloric acid and about

1 ml 5Ogewichts per cent aqueous hydrogen peroxide treated. The impregnated silica gel is applied to a steam bath at 150⁰C dried and then

2 For hours at 500⁰C calcined. The product obtained has a titanium content of 2.2% by weight.

15 cis ρ 11_ I 5

There are six catalysts (catalysts Ae, B₄, C₃, D₃, E₂, F₂) These catalysts are made

Preparation of a titanium-on-magnesium silicate catalyst (Catalyst C₃)

20 g of a commercially available magnesium silicate gel (10.2% by weight of Mg, 35.6% by weight of Si, pore volume = 1.1 cc / g) are mixed with a solution of 1 ml of titanium tetrachloride, 4 ml of 16 μm. Nitric acid, ImI 50gew.% Aqueous hydrogen peroxide and 10 ml of water. The impregnated magnesium silicate gei becomes i50⁼C and then for 2 hours at 500⁰C calcined The product obtained has a titanium content of 2.8% by weight.

Preparation of a Titanium / MDidynw on Silica Catalyst (Catalyst D₃)

20 g of silica gel Z are treated 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% aqueous hydrogen peroxide Mixture is evaporated on a steam bath, at 150⁰C and then calcined for 2 hours at 500 ° C. The product obtained has a titanium content of 4.4

JIf II

Wt .-% and a "Didym" content of 4.3 wt .-% Table V on.

Preparation of a Titanium / Molybdenum Silica Catalyst (Catalyst E2)

20 g of silica gel Z are treated with a solution of 1.73 g of titanium tetrachloride and 0.441 g of ammonium paramolybdate [(NH₄hMon₇O₂-I-4H₂O] in 20 ml of 9 η-nitric acid and 4 ml 50gew.% Aqueous hydrogen peroxide. The impregnated silica gel is at 15O⁰C and then for 2 hours at 500⁰C calcined. The product obtained has a titanium content of 2.2% by weight and a molybdenum content of 1.2% by weight.

<p><tgroup cols="5"><tbody><row><entry>catalytically</entry><entry>reaction</entry><entry>Tem</entry><entry>hydro-</entry><entry>epoxide</entry></row><row><entry>sator</entry><entry>Lions</entry><entry>temperature</entry><entry>peroxide-</entry><entry>selective</entry></row><row><entry></entry><entry>duration</entry><entry></entry><entry>conversion</entry><entry>tivity</entry></row><row><entry></entry><entry></entry><entry></entry><entry>Degree</entry><entry></entry></row><row><entry></entry><entry>H</entry><entry>C</entry><entry>%</entry><entry>%</entry></row></tbody></tgroup></p>

A₆

C₃ D₃ e₂ F,

4 1 1 3/4

107 107 110 88 105 104

56,7

62,2

91,2

86

83,4

91,6

83

83

Preparation of a Titanium-Molybdenum »Didym« on Silica Catalyst (Catalyst F₂) Example! 6

20 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-mentioned didymine nitrate in 20 ml of 4N nitric acid and 4 ml of 50% by weight aqueous hydrogen peroxide. The impregnated silica gel is at 150⁰C and then for 2 hours at 500⁰C calcined. 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.

Table VI

Using a titanium on silica

Catalyst for the epoxidation of various olefinic compounds

The olefinic compounds are each in a glass reactor in the presence of titanium-on-silica catalysts according to the from Table VI

In the experiments 1 to 11, the catalyst used is a fumed silica which contains 0.3% by weight of titanium and was prepared by flame hydrolysis of SiCU and TiCU. In experiments 12 and 13 is

in each case the catalyst A₂ used by Example 1

<p><tgroup cols="9"><tbody><row><entry>Olefin</entry><entry>Ole</entry><entry>Kata</entry><entry>hydroperoxide</entry><entry>dilution</entry><entry>Tem</entry><entry>reak</entry><entry>hydro-</entry><entry>epoxide</entry></row><row><entry>search</entry><entry>fin</entry><entry>lysa</entry><entry></entry><entry>medium</entry><entry>pera</entry><entry>TION</entry><entry>peröxid-</entry><entry>selective</entry></row><row><entry></entry><entry></entry><entry>gate</entry><entry></entry><entry></entry><entry>door</entry><entry>duration</entry><entry>Umwand-</entry><entry>tivitäl</entry></row><row><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry>development degree</entry><entry></entry></row><row><entry></entry><entry>G</entry><entry>G</entry><entry>G</entry><entry></entry><entry>t</entry><entry>H</entry><entry>%</entry><entry>%</entry></row></tbody></tgroup></p>

Octene-1 octene-1 octene-1 isobutene

52,5 1

36,5 1

73 2

6 1

Ethylbenzene (3.1 g) ethylbenzene (18 g) 110 17

Cyclohexene 40

Cyclohexene 28

4-cyanocyclohexene 20

Cyclohexenol 5

1,2,5,6-tetrahydro-50-benzaldehyde

Mesityl oxide methyl-Λ / '-dimethylacrylai

Allyl chloride allyl alcohol

50 25

18,5 29

1 1

0,5 2

0,5

1 1

Cumene (7 g) t-Butyl (9 g) t-Butyl (4.5 g)

t-Butyl (4.5 g) cyclohexene (15) t-butyl (2.3 g) t -butyl! - (69 g)

t-butyl (4.5 g)

t-butyl (4.5 g) t-butyl (4.5 g)

t -butyl- (4.6 g) t -butyl- (4.5 g)

Cumene (1 g) Nonane (2.1 g) o-Dichlorobenzene (20 ml)

«Dichlorobenzene (40 ml)

110 110 112

85

85

110

110

105

105 110

110 98

3 1

3,5 20

2,2

99 84,3 76,8 44,8

43,2 94 90 84

59

68,7

55

49 32

82 72,3 99 86,8

98,5 95 96,5 85

36

52,6 87

74 71

Example 7

Epoxidation of propylene with

Ethylbenzene hydroperoxide in the presence of a

Titanium-on-silica catalyst

This catalyst is prepared as follows: 60 g of a commercially available silica gel (specific surface area = 340 m²/G; Pore ​​volume

1.5 g of titanium tetrachloride in 68 ml of 4 N nitric acid and 4 ml of 50% by weight hydrogen peroxide. The impregnated silica gel is dried at 100 ° C. and then calcined at 800 ° C. for 2 hours Analysis of the resulting titania-silica product gives a titanium content of 2.18%. The epoxidation of propylene with Äthylbenzolhy-

droperoxide 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 treated with one of 6 moles of propylene per mole of ethylbenzene hydroperoxide, which is in Ethylbenzene is dissolved, existing reaction mixture charged. The residence time of the mixture in the reactor is about 24 minutes, and the temperatures shown in Table VIl and a pressure of about 42 bar (gauge) are set in the reactor. The reaction conditions and the results of the analysis of the product mixture after each reaction time are shown in Table VI seen.

Table VII

Example 8

Test duration, h

(total)

Tem hydro- propylene oxide

peroxide peroxide selectivity

Degree of conversion Use of catalysts containing titanium and

other metals on non-siliceous

Carriers included (comparative experiment)

Several catalysts containing various metals, such as titanium, as well as supports containing silica-free materials are tested for their suitability for epoxidation of octene-1 with tert-butyl hydroperoxide. The reaction conditions and results are shown in Table VIII. The catalysts used in Experiments I to VII are prepared by reacting a metal halide with either pyrogenic alumina having a specific surface area of ​​100 m²/ g or Mg (OH) Cl with a specific surface area of ​​about 20 mVg or zirconia with a specific surface area of ​​169 m²each method used is similar to that used in the preparation of the catalyst Ai. The catalyst used in the experiment VIU contains 2.5% by weight of cobalt and 9.5% by weight.

<p><tgroup cols="19"><tbody><row><entry></entry><entry>100</entry><entry>Table VIII</entry><entry>raw materials</entry><entry>76,8</entry><entry>metal</entry><entry>84,0</entry><entry> 25 </entry><entry>Molybdenum and Alumimurnoxic</entry><entry>, In verse</entry><entry>i IX</entry><entry>becomes</entry><entry>1 as a carrier (</entry><entry>commercial</entry><entry>nonane</entry><entry>Tem</entry><entry>reaction</entry><entry>hydro-</entry><entry>epoxide</entry></row><row><entry>44</entry><entry>110</entry><entry>Ver</entry><entry>Catalyst-</entry><entry>89,0</entry><entry>share in</entry><entry>85,0</entry><entry></entry><entry>product)</entry><entry>the epoxidation of</entry><entry>when</entry><entry>pera</entry><entry>Lions</entry><entry>peroxide-</entry><entry>selective</entry></row><row><entry>83</entry><entry>110</entry><entry>search</entry><entry>manufacturing</entry><entry>85,2</entry><entry>Catalyst-</entry><entry>83,0</entry><entry></entry><entry>Octene-1</entry><entry>with tert-butyl hydroperoxide without catalyst</entry><entry>Dilute</entry><entry>door</entry><entry>duration</entry><entry>Umwand-</entry><entry>tivity</entry></row><row><entry>310</entry><entry>114</entry><entry></entry><entry></entry><entry>87,6</entry><entry>carrier</entry><entry>86,5</entry><entry></entry><entry>carried out.</entry><entry>-voltage</entry><entry></entry><entry></entry><entry>development degree</entry><entry></entry></row><row><entry>379</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry>Octene-1</entry><entry></entry><entry>medium</entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry></entry><entry></entry><entry></entry><entry>Ge \ v .-%</entry><entry>Kata</entry><entry></entry><entry></entry><entry>2</entry><entry>C</entry><entry>H</entry><entry>%</entry><entry>%</entry></row><row><entry></entry><entry>TiCl₄ (Ig) and</entry><entry></entry><entry>1.2% Ti</entry><entry>lyst</entry><entry></entry><entry>tert</entry><entry>2,1</entry><entry>110</entry><entry>23</entry><entry>69</entry><entry>13</entry></row><row><entry>I</entry><entry>al₂O₃ (25 g)</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry>butyl</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry>TiCl₄ (5 g) and</entry><entry></entry><entry>4.4% Ti</entry><entry></entry><entry></entry><entry>hydro-</entry><entry>2,1</entry><entry>110</entry><entry>23</entry><entry>74</entry><entry>13</entry></row><row><entry>II</entry><entry>al₂O₃ (25 g)</entry><entry></entry><entry></entry><entry></entry><entry>G</entry><entry>peroxide</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry>TiCl₄ (4.7 g) and</entry><entry></entry><entry>3.5% Ti</entry><entry>G</entry><entry>36,5</entry><entry></entry><entry>2,1</entry><entry>111</entry><entry>5</entry><entry>24</entry><entry>18</entry></row><row><entry>III</entry><entry>ZrO₂ (25 g)</entry><entry></entry><entry></entry><entry>1</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry>TiCl₄ (2.3 g) and</entry><entry></entry><entry>2.9% Ti</entry><entry></entry><entry>36,5</entry><entry>9,5</entry><entry>2,1</entry><entry>110</entry><entry>4,5</entry><entry>60,2</entry><entry>6</entry></row><row><entry>IV</entry><entry>Mg (OH) Cl (12.7 g)</entry><entry></entry><entry></entry><entry>1</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry>NbCl₅ (3.8 g) and</entry><entry></entry><entry>5% Nb</entry><entry></entry><entry>36,5</entry><entry>4,5</entry><entry>0</entry><entry>110</entry><entry>22</entry><entry>55</entry><entry>7</entry></row><row><entry>V</entry><entry>al₂O₃ (25 g)</entry><entry></entry><entry></entry><entry>1</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry>TaCl₅ (5 g) and</entry><entry></entry><entry>5% Ta</entry><entry></entry><entry>36,5</entry><entry>4,5</entry><entry>0</entry><entry>110</entry><entry>23</entry><entry>63</entry><entry>0</entry></row><row><entry>VI</entry><entry>al₂O₃ (25 g)</entry><entry></entry><entry></entry><entry>1</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry>ZrCl₄ (2.9 g) and</entry><entry></entry><entry>2.5% Zr</entry><entry></entry><entry>36,5</entry><entry>4,5</entry><entry>2,1</entry><entry>110</entry><entry>U</entry><entry>45</entry><entry>1</entry></row><row><entry>VII</entry><entry>al₂O₃ (25 g)</entry><entry></entry><entry></entry><entry>1</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry>Co and Mo with Al₂O₃</entry><entry></entry><entry>2.5% CoI 9.5% Mo /</entry><entry></entry><entry>36,5</entry><entry>4,5</entry><entry>0</entry><entry>110</entry><entry>2</entry><entry>70,2</entry><entry>21</entry></row><row><entry>VIII</entry><entry>none</entry><entry></entry><entry>-</entry><entry>1</entry><entry></entry><entry></entry><entry>2.1</entry><entry>110</entry><entry>20</entry><entry>17</entry><entry>13</entry></row><row><entry>IX</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry>36,5</entry><entry>4,5</entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry>1</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry></entry><entry>42</entry><entry>4,5</entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry>1</entry><entry>36,5</entry><entry></entry></row><row><entry></entry><entry>0</entry><entry>5,5</entry></row><row><entry></entry><entry></entry><entry>4,5</entry></row><row><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry></entry></row><row><entry></entry></row><row><entry></entry></row><row><entry></entry></row></tbody></tgroup></p>

Example 9

Use of catalysts containing other metals

as titanium-on-silica as a carrier

(Comparative Experiment)

Several catalysts consisting of metals other than titanium and silica supported will be tested for their suitability for the epoxidation of octene-1 with tert-butyl hydroperoxide. Table IX shows the reaction conditions and results. The catalysts used in experiments X to XII are prepared by reacting a metal halide with SiO₂, Type X, using a method similar to that used in the

130 215/24

Preparation of the catalyst Ai of Example 1 procedure is similar. The catalysts used in experiments XIII 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 the impregnated silica gel at 150⁰C and then calcined for 2 hours at 500 ° C. In experiment XX, a catalyst is used which is obtained by treating 20 g of a commercially available magnesium silicate gel (10.2% by weight of magnesium, 35.6% by weight). Silicon) having a pore volume of about 1.1 cc / g with a solution of 0.1 g of chromium trioxide in 25 ml of water, drying the impregnated magnesium silicate gel at 150⁰C and calibration of the dried gel at 500⁰C is made 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 (H₂WHERE₄), 45 ml of 25% by weight ammonium hydroxide and 5 ml of 50% by weight aqueous hydrogen peroxide, and the impregnated silica at 150⁰C dried and then bsi 800 for 2 hours⁰C is calcined. To prepare the catalyst used in experiment XXII, 10 g of commercially available fumed silica are mixed with a solution of 1 g of rhenic acid (HReO₄) in 30 ml of water and then at 200⁰C dried.

Table IX

<p><tgroup cols="11"><tbody><row><entry>Ver</entry><entry>catalyst</entry><entry>The kata</entry><entry>kata-</entry><entry>Octene-1</entry><entry>tert</entry><entry>nonane</entry><entry>Tem</entry><entry>reak</entry><entry>hydro-</entry><entry>epoxide</entry></row><row><entry>search</entry><entry>made of</entry><entry>lyst</entry><entry>lysa-</entry><entry></entry><entry>butyl</entry><entry>as an alternative</entry><entry>pera</entry><entry>TION</entry><entry>peroxide-</entry><entry>Selek</entry></row><row><entry></entry><entry></entry><entry>be in favor</entry><entry>gate-</entry><entry></entry><entry>hydro-</entry><entry>thin</entry><entry>door</entry><entry>duration</entry><entry>Umwand-</entry><entry>tivity</entry></row><row><entry></entry><entry></entry><entry>leibter</entry><entry>amount</entry><entry></entry><entry>by-</entry><entry>nungs-</entry><entry></entry><entry></entry><entry>lungs-</entry><entry></entry></row><row><entry></entry><entry></entry><entry>metal</entry><entry></entry><entry></entry><entry>oxide</entry><entry>medium</entry><entry></entry><entry></entry><entry>Degree</entry><entry></entry></row><row><entry></entry><entry></entry><entry>proportion of</entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry></entry><entry>Wt .-%</entry><entry>G</entry><entry>G</entry><entry>G</entry><entry>G</entry><entry>C</entry><entry>H</entry><entry>%</entry><entry>%</entry></row></tbody></tgroup></p>

X WCI₆ (2.3 g) and SiO₃ (25 g)

XI NbCl₅ (3.8 g) and SiO₂ (25 g)

XII TaCl₅ (3 g) and SiO₂ (25 g)

XIII NbCl₅ (0.9 g) and SiCl₄ (36.7 g)

XIV NbCl₅ (0.08 g) and SiCI₄ (36.7 g)

XV WCI₆ (0.65 g) and SiCl₄ (36.9 g)

XVI WCI₆ (0.07 g) and SiCl₄ (36.7 g)

XVII TaCl₅ (0.6 g) and SiCl₄ (36.7 g)

XVIII TaCl₅(0.06 g) and SiCl₄ (36.6 g)

XIX CrO₃ and SiO₂

XX CrO₃ and MgO-SiO₂ XX) H₂WHERE₄ and SiO₂ XXII HReO₄ and SiO₂

3.8 (W) 5 (Nb) 5 (Ta) 1.4 (Nb) 0.2 (Nb) 1.5 (W) 0.3 (W) 3.1 (Ta)

0.26 (Ta) I

1,3 (Cr) 1

0.5 (Cr) 1

2.9 (W) 1

6.9 (Re) 1

36,5 36,5 36,5 36,5 36,5 36,5 36,5 36,5 36,5

4,5 4,5 4,5 4,5 4,5 4,5 4,5 4,5 4,5

7,5 4,5 5,5 4,5

2,1 2,1 2,1 2,1 2,1 2,1 2,1 2,1 2,1

0 0 0 0

105 108 110 110 103 110 110

110 HO 110 105

IS 13

6V₂

7 21 70 70

108 20 111 20

3S, 6

60

40

50

39,7

29

34

53,6

45,4

76 39 26,2 100

25,2

1 32

19,8 10 14

7 14,4

15

18

37,2

B ic ρ i L-1 ι U

Use of various metal compounds

without siliceous material

(Comparative Experiment)

In a series of experiments, various metal compounds on their suitability as heterogeneous catalysts in the Ερυ.ικίιιτιιημ ve · i "&gt;₍ ten-1 with terl.-Bui&gt; lhydroperoxid tested. In each experiment, a sample of 1 g of the respective metal compound is treated with proportions of 36.5 to 42 g of octene-1 and proportions of 4.5 to 5.5 g of tert-butyl hydroperoxide. Table X shows the reaction conditions and the results.

Table X

<p><tgroup cols="8"><tbody><row><entry>Ver</entry><entry>catalyst</entry><entry>Nonane as</entry><entry>reaction</entry><entry>20</entry><entry>temperature</entry><entry>hydro-</entry><entry>epoxide</entry></row><row><entry>search</entry><entry></entry><entry>dilution</entry><entry>duration</entry><entry>18</entry><entry></entry><entry>peroxide-</entry><entry>selectivity</entry></row><row><entry></entry><entry></entry><entry>medium</entry><entry></entry><entry>21</entry><entry></entry><entry>Umwand-</entry><entry></entry></row><row><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry></entry><entry>development degree</entry><entry></entry></row><row><entry></entry><entry></entry><entry>G</entry><entry> ii </entry><entry>4</entry><entry>C</entry><entry>%</entry><entry>%</entry></row><row><entry>1</entry><entry>TiO₂ (Commercial product)</entry><entry>2,1</entry><entry>12</entry><entry>110</entry><entry>50</entry><entry>0</entry></row><row><entry>2</entry><entry>TiO₂ (Commercial product)</entry><entry>2,1</entry><entry>16</entry><entry>110</entry><entry>40</entry><entry>0</entry></row><row><entry>3</entry><entry>TiO₂ (Hydrolysed)</entry><entry>2,1</entry><entry>16</entry><entry>113</entry><entry>73,1</entry><entry>9,2</entry></row><row><entry></entry><entry>TiCl₄ v. Example HE</entry><entry></entry><entry>20</entry><entry></entry><entry></entry><entry></entry></row><row><entry>4</entry><entry>Bi₂Ti₂O₇</entry><entry>0</entry><entry>2</entry><entry>110</entry><entry>48</entry><entry>6</entry></row><row><entry>5</entry><entry>MgTiO₃</entry><entry>2,1</entry><entry>2</entry><entry>116</entry><entry>28</entry><entry>1</entry></row><row><entry>6</entry><entry>SrTiO₃</entry><entry>2,1</entry><entry>2</entry><entry>111</entry><entry>35</entry><entry>1</entry></row><row><entry>7</entry><entry>CaTiO₃</entry><entry>2,1</entry><entry>4,5</entry><entry>110</entry><entry>28</entry><entry>1</entry></row><row><entry>8</entry><entry>ZrO₂</entry><entry>2,1</entry><entry>4,5</entry><entry>107</entry><entry>76,7</entry><entry> 5 </entry></row><row><entry>9</entry><entry>(NH₄J₄ZrF₆</entry><entry>0</entry><entry>0,5</entry><entry>110</entry><entry>24</entry><entry>0</entry></row><row><entry>10</entry><entry>ZrB₂</entry><entry>0</entry><entry>1,5</entry><entry>110</entry><entry>85</entry><entry>0</entry></row><row><entry>11</entry><entry>CaZrO₃</entry><entry>0</entry><entry>112</entry><entry>110</entry><entry>10</entry><entry>0</entry></row><row><entry>12</entry><entry>Nb₂O₅</entry><entry>0</entry><entry>22</entry><entry>115</entry><entry>9</entry><entry>0</entry></row><row><entry>13</entry><entry>Ta₂O₅</entry><entry>0</entry><entry>4</entry><entry>110</entry><entry>11</entry><entry> 5 </entry></row><row><entry>14</entry><entry>CrO₃</entry><entry>0</entry><entry>22</entry><entry>108</entry><entry>99</entry><entry>22</entry></row><row><entry>15</entry><entry>CrCl₃</entry><entry>0</entry><entry>3</entry><entry>96</entry><entry>98</entry><entry>0</entry></row><row><entry>16</entry><entry>WC</entry><entry>2,1</entry><entry>20</entry><entry>116</entry><entry>56</entry><entry>5</entry></row><row><entry>17</entry><entry>WHERE₃</entry><entry>0</entry><entry>111</entry><entry> 85 </entry><entry>8</entry></row><row><entry>18</entry><entry>re₂O₇</entry><entry>0</entry><entry>110</entry><entry>100</entry><entry>0</entry></row><row><entry>19</entry><entry>TeO₂</entry><entry>0</entry><entry>110</entry><entry>33</entry><entry>7</entry></row><row><entry>20</entry><entry>SeO₂</entry><entry>0</entry><entry>110</entry><entry>97</entry><entry>0</entry></row><row><entry>21</entry><entry>UO₂</entry><entry>0</entry><entry>110</entry><entry>55</entry><entry>5</entry></row></tbody></tgroup></p>

Example 11

Three catalysts (catalyst R, S, T) are prepared and tested by adding in each case a sample of «1 g of the respective catalyst in a 100 ml glass reactor for 90 minutes at 125 ° C. with 17 g each of octene-1 , 25 g of ethylbenzene hydroperoxide (as a 14.2 weight% solution in ethylbenzene) and 8 g of nonane. 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% SiO₂ and 1.2% Al₂O₃), which has a pKa of -5, a specific surface area of ​​300 mVg and a pore volume of 0.75 cc / g and is mainly present as Al silicate, is treated with a solution of 10 ml of titanium tetrachloride in 144 ml 4 η Nitric acid and 18 ml of 50% by weight aqueous hydrogen peroxide. The impregnated silica / alumina is at 15O⁰C and then calcined at 800 ° C for 2 hours. The product obtained has a titanium content of 2.2% by weight.

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

20 g of the silica-alumina used to prepare the catalyst R are treated 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 50% by weight aqueous hydrogen peroxide. The impregnated silica-alumina is dried at 160 ° C and then calcined at 800 ° C for 2 hours. The product obtained has a titanium content of 2.2% by weight and a magnesium content of 1.1% by weight. It has a pKa of 3.3.

Preparation of a Titanium / Calcium Silica / Alumina Catalyst (Catalyst T)

20 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 4 N nitric acid and

1 treated with 50% by weight aqueous hydrogen peroxide. The impregnated silica-alumina is dried at 160 ° C and then

2 Calcined at 800 ° C for hours. The product obtained has a titanium content of 2.2% by weight, a calcium content of 1.8% by weight and a pKa of 1.5.

<p><tgroup cols="6"><tbody><row><entry>LU β% • ft i * &amp;, </entry><entry>20 15 21 Table XI</entry><entry>503</entry><entry> 22 </entry><entry>Epoxide selectivity</entry><entry>*</entry></row><row><entry>j "</entry><entry>Catalyst search</entry><entry>Hydroperoxide conversion degree</entry><entry>29,1 72,7 66,3</entry><entry></entry></row><row><entry> I </entry><entry>R 2.2 wt.% Ti on SiO 2₂ · AI₂O₃ S 2.2 wt% Ti / 1.1 wt% Mg on SiO 2₂ Al₂O₃ T 2.2% by weight of Ti / 1, 8% by weight of Ca on SiO 2₂ Al₂O₃</entry><entry>74,1 80,9 93,3</entry><entry></entry><entry></entry></row><row><entry> I </entry><entry></entry><entry></entry><entry></entry></row><row><entry> ι 5 η ki I </entry><entry></entry><entry></entry><entry></entry></row><row><entry>f ί '</entry><entry></entry><entry></entry><entry></entry></row><row><entry> j </entry><entry></entry><entry></entry><entry></entry></row><row><entry> Ij:</entry><entry></entry><entry></entry></row><row><entry></entry><entry></entry><entry></entry></row><row><entry>J</entry><entry></entry><entry></entry></row><row><entry></entry><entry></entry></row></tbody></tgroup></p>