The method of epoxidation using heterogeneous catalytic composition of improved quality

 

(57) Abstract:

The invention relates to an improved method of epoxidation, which uses a titanium-containing catalyst composition. The catalytic composition is obtained by impregnation in the liquid phase silicon-containing solid materials with a titanium halide such as titanium tetrachloride in a hydrocarbon solvent with subsequent calcination. The above-mentioned catalyst, optional, also reacts with water and/or silylium agent. The technical result is the improved performance of the catalyst, increasing the yield of the epoxy compounds. 4 C. and 30 C.p. f-crystals, 3 tables.

This application is a partial continuation of application 08/900794, which was filed on July 25, 1997, which, in turn, is a partial continuation of application 08/851,105, filed may 5, 1997

The scope of the invention

The present invention relates to an improved method of epoxidation, which uses a titanium-containing catalyst composition. Mentioned catalytic composition is obtained by impregnation in the liquid phase silicon-containing solids by the halide totalizator optional also reacts with water and/or silylium agent. Performance of the catalyst is improved by annealing at high temperature (in the preferred embodiment, at a temperature of at least 700o(C) in the practical absence of oxygen.

Background of the invention

Developed many different methods for producing epoxy compounds. One such method involves epoxidation of the olefin in the liquid-phase reaction using an organic hydroperoxide as the oxidant and some dissolved compounds transition metal as a catalyst. Based on the results of previous works in this field of technology concluded that the optimal rate of epoxidation and the selectivity of the epoxy compounds are given as a rule, in case of using metal catalysts which are soluble in the organic reaction medium.

The obvious disadvantage of this method epoxidation, in which the catalyst used is a soluble compound of the metal, is the difficulty associated with the regeneration of the above-mentioned catalyst for reuse in subsequent operations. When other components of the reaction mixture for ASU is absent hydroperoxide and alcohol, derived from unreacted hydroperoxide) have a relative volatility mentioned components can be separated from the non-volatile catalyst by distillation, and the catalyst regenerated in the form of flux residue. The essence of the problem with this method is, however, that the said flux residues can have a tendency to accumulate certain heavy substances, such as acids and polymers, which can have a negative effect on the selectivity of the epoxy compounds or conversion of the olefin in the case of repeated use of the above-mentioned flow. The above-mentioned catalyst may also have a tendency to precipitation from solution in the case of excessive concentration of the above-mentioned flux residue. Consequently, it may be necessary to cycle the flux residue is relatively large volume, which will adversely affect the performance of this method for epoxidation.

Thus, it would be desirable to develop insoluble (heterogeneous) epoxidation catalyst with high activity and selectivity, which could easily be recycled in active Otdelenia or which could be used as the fixed layer, etc.

In U.S. patent 4367342 disclosed method of epoxidation of olefins, in which the olefin is in contact with an organic hydroperoxide in the presence of the insoluble catalyst, which includes an inorganic oxygen compound of titanium. Additional description of such catalysts is shown in UK patent 1332527 and U.S. patents 4021454, 3829392 and 3923843. Unfortunately, the catalysts obtained in accordance with the methods described in the above-mentioned sources do not have optimal activity and selectivity. Attempt incorporating relatively high levels of titanium in the catalyst of this type, with the aim of increasing the activity of the catalyst, also gave negative results.

Therefore, it would be highly desirable to develop alternative methods for the synthesis of heterogeneous titanium-containing catalysts, devoid of the disadvantages of the previously developed methods, as well as secure and simple to obtain materials having higher activity and selectivity in the epoxidation reactions of olefins.

In the United Kingdom patent 1332527 disclose a method of obtaining a catalyst of improved quality, which consists of di is a, essentially nonaqueous compounds of titanium in colorazione hydrocarbon solvent, removing the solvent from the above-mentioned impregnated siliceous solids with subsequent annealing specified impregnated silicon-containing solids. Suitable solvents for this purpose are limited to the oxa - and/or oxazolidone hydrocarbons that are liquid at ambient conditions and include usually from 1 to 12 carbon atoms. Among such solvents include alcohols, ketones, ethers and esters. According to the mentioned patent is the reason that a catalyst comprising silicon dioxide - titanium dioxide obtained by the method in which used kislorodozaschitny hydrocarbon impregnation solvent, has improved properties compared with similar catalysts prepared by other methods, is that such a catalyst has a more uniform distribution of respectivos titanium dioxide.

In a later filed patent application (EP 345856) disclose the receipt of epoxidation catalysts, which are claimed to have higher activity compared to the same kata is different titanium tetrachloride, followed by calcination, hydrolysis and optional sellerbuyer. In the comparative example, it was found that the catalyst is obtained by impregnation of silica with a solution of tetraisopropyldisiloxane in complex with acetylacetone in isopropanol was used as solvent, was 4.5 times lower compared to the activity of the catalyst is obtained by impregnation of titanium tetrachloride in the vapor phase. The meaning of disclosure of the invention is that in the case of the impregnation method in the liquid phase it is impossible to achieve catalytic activity with high selectivity for the epoxy compounds which can be obtained through use of the method of impregnation in the vapor phase.

In the application EP 734764 described improvement of the impregnation method in the liquid phase, unveiled in the United Kingdom patent 1323527, the essence of which is that after impregnation of the silica with a solution of compounds of titanium in oxygen-containing organic solvent and removal of the mentioned impregnating solvent, the said catalyst is washed proryvnym solvent with subsequent calcination. In the preferred embodiment mentioned proryvnym rastia, outstanding activity and selectivity, although the study of comparative examples included in the EP 734764 suggests that this method provides only a very modest improvement in performance of the catalyst. Another practical disadvantage of the above method is that it generates significant amounts of waste solvent, which must either be disposed of or recycled after cleaning. Such removal or cleaning significantly increase the cost of obtaining the above-mentioned catalyst. The next disadvantage is the difficulty of attaining high levels of inclusion of titanium, since the washing process removes significant amounts of titanium, and this effect is exacerbated in the case of a large number of titanium reagent relative to the amount of silicon dioxide. Moreover, the above method does not provide precise control of the final titanium content in the resulting catalyst.

The authors of the present application have discovered a simple and efficient method for the catalytic compositions having activity and selectivity epoxidation at least travnia.

Summary of the invention

The present invention is a method of epoxidation of olefins with the catalyst composition used in the above-mentioned method, receiving method, comprising the following steps:

(a) impregnating an inorganic silicon-containing solid solution of titanium halide in a hydrocarbon solvent that does not contain oxygen, with getting impregnated silicon-containing solids;

(b) annealing mentioned impregnated silicon-containing solids, and mentioned method differs practical with the exception of water until at least the end of stage (a).

Optional-mentioned method of producing the catalyst comprises the additional steps of heating the specified catalyst in the presence of water (which can be done simultaneously with the annealing and/or processing of this catalyst silylium agent. Epoxydiols the catalyst activity can be significantly enhanced by the implementation of the step of annealing at a relatively high temperature (for example, at a temperature of from 500 to 1000o(C) in the practical absence of oxygen. Negative vaseegara annealing a reducing gas, for example carbon monoxide.

Detailed description of the invention

In the method of epoxidation corresponding to the present invention, use of titanium-containing heterogeneous catalyst, obtained in a special way, which was unexpectedly set provides the materials having excellent vibration characteristics epoxidation compared to materials obtained by using other methods of impregnation in the liquid phase. The above-mentioned method of producing catalyst is impregnated inorganic silicon-containing solid solution of titanium halide in a hydrocarbon solvent that does not contain oxygen. Among the solvents suitable for this purpose are hydrocarbons that do not contain atoms of oxygen in the liquid state at ambient temperatures and capable of dissolving a halide of titanium. It would be desirable to find a hydrocarbon solvent, at a temperature of 25oWith can be obtained concentration of the titanium halide component is at least 0.5 wt.%. Uglevodorodnyi solvent in the preferred embodiment, should be relatively volatile, so that it can b is thus, mainly can be used a solvent having a normal boiling point in the range from 25 to 150oC. the hydrocarbons are particularly preferred classes include, but are not limited to, C5-C12aliphatic hydrocarbons (straight chain, branched or cyclic), WITH6-C12aromatic hydrocarbons (including alkyl substituted aromatic hydrocarbons), C1-C10halogenated aliphatic hydrocarbons and C6-C10halogenated aromatic hydrocarbons. In the most preferred embodiment, the above-mentioned solvent does not include other elements in addition to carbon, hydrogen, and (optional) halogen. In the presence of halogen in the above-mentioned solvent, in the preferred embodiment, is chloride.

If necessary, can be used a mixture of hydrocarbons that do not contain oxygen. In a preferred embodiment, the above-mentioned solvent used for impregnation, essentially devoid of water (i.e. anhydrous). Despite the fact that in the mixture with the desired hydrocarbon not containing oxygen, may be present oxygen-containing hydrocarbons such as alcohols, ethers, the amount of solvent in the impregnation process is used only hydrocarbon, not containing oxygen. Examples of suitable hydrocarbon solvents are n-pentane, n-hexane, n-heptane, n-octane, n-nonan, n-decane, neohexane, cyclohexane, cyclopentane, 2-methylbutane, methylpentane, methylcyclohexane, dimethylpentane, methylhexane, dimethylhexane, methylheptane, trimethylpentane, benzene, toluene, xylenes, cumin, ethylbenzene, t-butylbenzoyl, methylene chloride, chloroform, carbon tetrachloride, ethylchloride, dichlorethane, tetrachlorethane, chlorobenzene, dichlorobenzene, trichlorobenzene, benzylchloride, chlorotoluene, etc. as well as their isomers.

Unlike the method described in example I of U.S. patent 4021454, where a mixture of titanium tetrachloride and silicon dioxide in n-heptane, water is added, the method corresponding to the present invention, in preferred embodiments, the implementation of the invention differs essentially, with the exception of the water to at least complete impregnation (i.e., after removal of the mentioned impregnating solvent) and in the preferred embodiment, prior to the completion of the annealing. The expression "essentially" in the context of this invention means that the water is not intentionally added or not paid or, in the case of intentional add it or made the necessary interaction of the above-mentioned titanium halide with the surface of inorganic siliceous solids). The use of reagents and starting materials that contain trace amounts of water, which usually traditionally found in such substances sold on a commercial scale, is within the scope of the present invention. In a preferred embodiment, the hydrocarbon that does not contain oxygen, contains less than 500 ppm (parts per million) of water (in a more preferred embodiment, less than 100 ppm water). As will be described in more details below, before using inorganic siliceous solids highly desirable is its thorough drying.

The number of suitable halides of titanium include titanium compounds having at least one Deputy halogen, in the preferred embodiment, the chloride is attached to the titanium atom. Although most preferred to use the titanium halide is titanium tetrachloride, examples of other halides of titanium, which can be used at the stage of impregnation are tetraploid titanium, tetrabromide titanium, tetraiodide titanium, trichloride titanium, and mixed halides of Ti(III) and Ti(IV). Along with the halide may be present also other substituents, such as alcox the Xia halides.

Despite the fact that the concentration of the titanium halide in the above-mentioned hydrocarbon solvent is not critical, the concentration of the halide of titanium, as a rule, will be in the range from 0.01 mol/l to 1.0 mol/l Concentration of the above-mentioned titanium halide in a hydrocarbon solvent and the used quantity of the solution is preferably adjusted to ensure that the titanium content in the finished catalyst is in the range from 0.1 to 10 wt.% (calculated as Ti, based on the total weight of the above catalyst). On the optimal content of titanium is influenced by a number of factors. The higher the surface area mentioned inorganic silicon-containing solids, the greater the amount of titanium that can be included in the above-mentioned catalyst without loss of activity (measured at constant Ti under conditions of epoxidation) or selectivity. In those cases, when the surface area of the inorganic siliceous solids is within, for example, from 250 to 375 m2/g, it is desirable that the content of titanium in the catalyst ranged from 1 to 5 wt. %. To achieve the necessary content and activity of titanium can b is="ptx2">

To inorganic silicon-containing solid substances suitable for the purposes of the present invention are solid materials, which include a large proportion of silica (silicon dioxide). Particularly preferred for use are amorphous (i.e. non-crystalline) silicon oxides. In General, suitable inorganic siliceous solids additionally have a relatively large surface area relative to their mass. The term that is used in the present description and which is typically used in the art for expression of the interdependence between surface area and mass, is the term "specific surface area". Numerically specific surface area is expressed as square meters per 1 g (m2/g). In General, the aforementioned inorganic silicon-containing solid substance has a specific surface area of at least 1 m2/g, and an average specific surface area in the preferred embodiment ranges from 25 to 1200 m2/,

Among the suitable inorganic siliceous solids are synthetic porous silica, consisting of particles of amorphous silicon dioxide, which their materials are silica gel and precipitated silica. Mentioned silica porous products, because their structure is penetrated by numerous pores, cavities or crevices.

Other suitable inorganic siliceous solids are powdered synthetic silica, consisting of particles of amorphous silicon dioxide, forming a loose, easily destroyed, loosely Packed aggregates. Among the illustrative powdered silica are white soot obtained by burning hydrogen and oxygen with the tetrachloride or silicon tetrafluoride.

Synthetic inorganic oxide materials containing a large portion of silicon dioxide, represent another class of inorganic siliceous solids. Such materials are known as refractory oxides include silica - alumina, silica - magnesia, silica - Zirconia, silica - alumina - boron oxide and silicon dioxide - aluminum oxide - magnesium oxide. Molecular sieves, in particular macroporous or mesoporous molecular sieves such as MCM-41, MCM-48 and M41S, can also be used as Neorganicheskie silicon-containing solid substances include substances, consisting essentially of pure silica, for example materials containing at least 99% of silicon dioxide.

Silicon-containing inorganic solids are well known in this area and was previously used to obtain a titanium-containing heterogeneous catalysts, as described, for example, in U.S. patents 4367342, 4021454, 3829392 and 3923843, the publication of European patent applications 0129814, 0345856 and 0734764, the Japan patent 77-07908 (Chem. Abstracts 98: 135000s), PCT application W094/23834, the German patent 3205648 and work Castillo (Castillo) and others, J. Catalysis 161, pages 524-529 (1996), which are not fully included in this application as references. Any of the above-mentioned silicon-containing inorganic solid substances described in the above reference sources, suitable for use in this invention.

Mentioned inorganic silicon-containing solid material before use is highly desirable to dry. Drying can be carried out, for example, by heating the aforementioned inorganic siliceous solids for several hours at a temperature of from 100 to 700oSince, in the preferred embodiment, at a temperature of at least 200oC. Gotur, exceeding 700oC. To speed up the drying process you can use a vacuum or a stream of dry gas, such as nitrogen.

Can be used any of the traditionally used method of impregnation of porous solids dissolved impregnating agent. For example, the above-mentioned titanium halide may be dissolved in a hydrocarbon solvent and then added to or otherwise connected with the said inorganic silicon-containing solids. These inorganic siliceous solids may also be added to the above-mentioned hydrocarbon solution of titanium halide.

Fit is also the so-called impregnation method with rudimentary humidity," in which, to avoid the formation of the suspension, using the minimum amount of solvent. The resulting mixture before further processing can be maintained with optional stirring or make it dynamic state otherwise. In General, the specified impregnating solution should be brought into contact with the aforementioned inorganic siliceous solids over a period of time sufficient for the teacher, used for impregnation, can then be removed by drying at a moderately elevated temperature (for example, at a temperature of from 50 to 200oS) and/or reduced pressure (for example, at a pressure of 1 mm Hg to 100 mm Hg) before calcination.

Conditions specified stage of solvent removal in the preferred embodiment, are chosen in such a way that before annealing was removed at least 80%, more preferred embodiment, at least 90% mentioned hydrocarbon solvent used for impregnation. Stage drying can be preceded by decantation, filtration or centrifugation to remove any excess impregnating solution. Rinsing mentioned impregnated silicon-containing solids is not required. Thus, one of the desirable embodiments of the present invention is characterized by the absence of such a washing step.

Mentioned impregnated silicon-containing solids prokalyvayutsya by firing at elevated temperatures. The calcination may be carried out in the presence of oxygen (e.g. air) or, in a more preferred embodiment, an inert gas, COA, essentially free from oxygen atmosphere in the annealing process provides usually receive a much more active catalyst than in the case of using oxygen-containing atmosphere, for example air.

In one of the embodiments of the present invention, the first annealing is carried out in essentially devoid of oxygen atmosphere, followed by the introduction of oxygen. In a preferred embodiment, the atmosphere of the calcination contains less than 10,000 ppm mol of oxygen. In a more preferred embodiment, in the above-mentioned atmosphere annealing contains less than 2000 ppm mol of oxygen. In the ideal case, the concentration of oxygen in the process of annealing is less than 500 ppm. Recognized, however, is the difficulty of ensuring a virtually oxygen-free conditions in large-scale industrial operations. The surprise was that the catalysts having epoxydiols activity comparable to epoxygenase activity of the catalysts calcined in the practical absence of oxygen, can be obtained even in the presence of a certain amount of oxygen (for example, up to 25,000 ppm mol) under condition of presence is also a reducing gas. A particularly effective gas-Voss what I typically do not as obtained in a similar way catalysts have a lower activity (possibly due to water formation in the conditions of annealing). The optimum quantity of a reducing gas will naturally vary depending on a number of factors, including the concentration of oxygen in the atmosphere of the annealing and the nature of a reducing gas, however, in the structure mentioned atmosphere annealing is sufficient, as a rule, are the levels of a reducing gas in the range from 0.1 to 10 mol %. In one of the embodiments of the present invention, the calcination is carried out in an atmosphere consisting of oxygen, a reducing gas (in the preferred embodiment, the carbon monoxide) and optionally one or more inert gases (e.g. nitrogen, helium, argon, carbon dioxide).

The above-mentioned catalyst in the process of annealing can be used as the fixed layer with the gas flow passing through the said layer of catalyst. The important point increase epoxygenase the activity of the catalyst is performing annealing at a temperature of at least 500oC. In a more preferred embodiment, the specified temperature annealing is, is livania, component of from about 0.1 to 24 hours

The above-mentioned catalyst may react with water after and/or during calcination. This reaction can be carried out, for example, by contacting the catalyst with steam at an elevated temperature (in the preferred embodiment, when the temperature is above 100oSince, in the preferred embodiment at a temperature ranging from 150 to 650oC) for from about 0.1 to 6 hours, the Reaction with water, it is desirable to reduce the residual amount of the halide in the above-mentioned catalyst derived from a halide of titanium, and to increase the density of the above-mentioned catalyst for hydroxyl groups.

The specified catalyst may also be processed organic silylium agent at elevated temperature. Similarobama, as a rule, increases the selectivity of the epoxy compounds. Similarobama in the preferred embodiment, is carried out after calcination and in the preferred embodiment, after calcination and reaction with water. Description of suitable methods sililirovanie suitable for use in the present invention, is shown in U.S. patent 3829392 and 3923843 (included in the full objeetilii, organosilane and organosilazane.

Can be used organosilane containing from one to three organic substituents which include, for example, chlorotrimethylsilane, dichlorodimethylsilane, nitratenitrogen, chlorotriethylsilane, chlorodimethylvinylsilane, etc. among the preferred organochlorosilanes similarbuy agents include Tetra-substituted silanes having from 1 to 3 halogensubstituted selected from among chlorine, bromine and iodine, while the other substituents are methyl, ethyl or a combination thereof.

Organosilazane represented by the formula where R is a group independently represent gidrolabilna group (preferred option - C1-C4alkyl or hydrogen. Particularly preferred for use are hexadecylamine disilane, for example, hexamethyldisilazane.

Processing mentioned silylium agent can be carried out either in the liquid phase (for example, when the above catalyst is treated silylium agent in liquid form, either independently or in the form of a solution in an appropriate solvent (e.g., hydrocarbon), or in the vapor phase (for example, when mentioned si is doctitle variant within 80-450oSince, moreover, preference is usually given somewhat higher temperatures (e.g. temperatures in the range from 300 to 425o(C) in cases where silylium agent is organohalogens, and slightly lower temperatures (e.g. temperatures in the range from 80 to 300o(C) in the case organosilazane. Mentioned similarobama may be performed periodically, semi-continuous or continuous.

The length of time required for the reaction mentioned cilleruelo agent with the surface of the above-mentioned catalyst depends, in part, on the applied temperature and the agent. At lower temperatures is required, as a rule, the longer the response time. In General, suitable intervals from 0.1 to 48 hours

The amount used cilleruelo agent may vary within wide limits. The appropriate number cilleruelo agent can be from about 1 wt.% (based on the total weight of the catalytic composition) to about 75 wt. %, with preference generally given to amounts of from 2 to 50 wt.%. The catalyst may be subjected to a single or multiple processing mentioned silylium Aoba, is usually from about 0.1 to 10 wt.% (in the preferred embodiment, from 1 to 5% titanium, usually in the form of titanium oxide in the preferred embodiment, a high degree of oxidation), which in the preferred modalities of the implementation of the present invention are balanced, predominantly or exclusively silica (silicon dioxide). In cases where the above-mentioned catalyst is subjected to siciliani, in its composition, as a rule, also includes from 1 to 4 wt.% carbon in the form of organic silyl groups. The composition of the above-mentioned catalyst may also contain relatively small amounts of halide (for example, up to approximately 5000 ppm). Desirable distinctive feature of the present invention lies in the fact that with its help it is possible to obtain highly active and selective catalytic compositions containing relatively large amounts of titanium (e.g., 1 wt.% and more). This advantage was completely unexpected, taking into account the preceding description of the ways in which it was stated that to minimize sintering of titanium and maximize the effectiveness of the catalyst in the process of impregnation in the liquid phase must ispasakojo specific surface area and can be characterized as including an inorganic oxygen compound of silicon in chemical combination with an inorganic oxygen compound of titanium (for example, oxide or hydroxide).

Mentioned catalyst composition may optionally include a neutral substance and/or promoters of the catalyst, especially those that are relatively chemically inert to the reagents and products of the epoxidation. The composition of the above-mentioned catalysts may include minor amounts of promoters, such as alkali metals (e.g. sodium, potassium) or alkaline earth metals (such as barium, calcium, magnesium), in the form of oxides or hydroxides. Appropriate, as a rule, are the levels of alkaline and/or alkaline earth metal is from 0.01 to 5 wt.%, on the basis of the total mass of the aforementioned catalytic composition.

Mentioned catalytic compositions can be used in any suitable physical form, for example in the form of powder flocculent particles, granules, beads or pellets. Inorganic silicon-containing solid substance can exist in a similar form before impregnation or by annealing or alternatively turn after impregnation and/or calcination from one form into another physical form by conventional methods, for example extrusion, granulation, grinding, etc.

Particularly preferred olefinic reactants are acyclic alkenes, comprising from 3 to 10 carbon atoms, for example, propylene, butene, Panten, hexene, hapten, octene, nonen, the mission and their isomers. Preference is also given to the unsaturated olefin compounds, substituted hydroxyl group or halogen group, such as allylchloride or allyl alcohol. Preferred organic hydroperoxides are the hydroperoxides of hydrocarbons having from 3 to 20 carbon atoms. Especially preferred are secondary and tertiary hydroperoxides, comprising from 3 to 15 carbon atoms, in particular secondary hydroperoxides of alkyl, where mentioned hydroperoxidase the group is on a carbon atom attached directly to an aromatic ring, such as ethylbenzene hydroperoxide. Examples of other organic hydroperoxides suitable for use include hydroperoxide, t-butyl, hydroperoxide, t-amyl, hydroperoxide of cyclohexyl and the hydroperoxide cumene.

the plays, the preferred molar ratio is, however, from 1:1 to 20:1.

The above epoxidation reaction is carried out in the liquid phase in solvents or diluents which are liquid at the temperature and pressure of the reaction and, as such, are inert in respect of these reagents and derived products.

In industrial practice, the most economical is used as the hydrocarbon solvent used to obtain the aforementioned organic hydroperoxide reagent. For example, in the case of cumene ethylbenzene preference is given to using ethylbenzene as epoxidised solvent. The above reaction is carried out at moderate temperatures and pressures. The concentration of hydroperoxide is usually from about 1 to 50 wt.% the reaction mixture to effect the epoxidation (including olefin). A suitable reaction temperature ranges from 0 to 200oSince, however, in the preferred embodiment, it ranges from 25 to 150oC.

The reaction in the preferred embodiment, is carried out at atmospheric pressure, l is outa the reaction mixture may, for example, be maintained essentially in negators state or in the form of a two-phase (gas/liquid) system. Mentioned catalyst composition, of course, is heterogeneous and, thus, is present in the form of a solid vase in the epoxidation process corresponding to the present invention. Typical pressure ranges from 1 atmosphere to 100 atmospheres.

Epoxidation may be carried out using a reactor of any conventional configuration known in the art for the reaction of olefin and an organic hydroperoxide in the presence of the insoluble catalyst. Can be used as a continuous or periodic process. For example, the catalyst may be used in the form of a stationary layer or suspension, provided the abstraction of heat resulting from the exothermic reaction of epoxidation.

Description catalytic reactor with a porous layer suitable for use in the present method, described in EP 323663. When carrying out the epoxidation in the required volume of the resulting mixture of products was separated and the resulting products (epoxysilane and alcohol, poluchennoi distillation, selective extraction, filtration, etc., Reactive solvent, catalyst composition and any unreacted amount of olefin or organic hydroperoxide are recirculated for further use.

EXAMPLES

Example 1-a

This example shows getting a catalyst in accordance with the present invention.

The dried sample of silicon dioxide Grace V-432 (30 g) having a specific surface area of 320 m2/g and a pore volume of 1.1 ml/g, was introduced into a 500 ml 3-necked round bottom flask equipped with condenser, an inlet for inert gas scrubber, which was an aqueous solution of sodium carbonate. After that, in the above-mentioned flask in an atmosphere of dry inert gas was added to the solution, which included 51 grams of heptane and 2.1 ml (3.6 g; 0.019 mol) of titanium tetrachloride. The resulting mixture using an oil bath was heated to a temperature of distillation for 2 hours then the oil bath temperature was raised to 150oWith and the solvent drove by blowing the bulb with an inert gas. The oil bath temperature was raised to 200oC and kept at this temperature for 2 h

The obtained solid ve is dnow acid, formed in the process of increasing the temperature, washed with aqueous sodium carbonate. After that, the obtained product was progulivali in the presence of air flow at a temperature of 800oC for 2 hours Quartz reactor was cooled to a temperature of 400oAnd its contents were treated with steam at mentioned temperature using an inert gas as a carrier. Through a layer of catalyst missed 4.5 g (0.25 mol) of water. After cooling the quartz reactor to a temperature of 200oWith the obtained catalyst was treated with a stream of inert gas, which in the form of steam were hexamethyldisilazane. Through the catalyst missed, in General, 3.0 g hexamethyldisilazane. Subsequently, the reactor was cooled to ambient temperature by a flow of inert gas to obtain the final catalytic composition.

Example 1-

Was repeated procedure of example 1, except that the purge water vapor was carried out at a temperature of 500oWith using air as the carrier gas.

Example 1-

Was repeated procedure of example 1, except that the purge water vapor was carried out at a temperature of 600oWith ispolzovaniem, the calcination of the above-mentioned catalyst was carried out at a temperature of 600oC.

Example 1-E

Was repeated procedure of example 1, except that the calcination of the above-mentioned catalyst was carried out at a temperature of 700oC.

Example 1-F

Was repeated procedure of example 1, except that the calcination of the above-mentioned catalyst was carried out at a temperature of 900oC.

Example 1-G

Was repeated procedure of example 1, except stage blowdown water vapor.

Example 1-H

Was repeated procedure of example 1, except stage sililirovanie.

Example 1-I (comparative)

Was repeated procedure of example 1, except that as a solvent for impregnation instead of heptane was used anhydrous isopropanol.

Comparative example 2

This example demonstrates how to compare obtaining a catalyst with the use of alcohol as an impregnating solvent and alkoxide of titanium as titanium source.

Get solution containing 137 g of isopropanol and 13.8 g of diisopropoxide bis(acetylacetonate) titanium.

The mentioned solution to the catalyst 2, which have different titanium content as shown in table. I) in a round bottom flask and mix thoroughly. Subsequently the solvent is removed by rotary evaporator bath temperature reaches 85oC. After drying, the resulting material is calcined at a temperature of 800o(The rate of temperature rise of 5oC/min) in air for 6 h

A portion of the calcined product (78 g) contribute in a tubular glass reactor (outer diameter of 1.25 inches (31.75 mm); length 30 inches (762 mm)) with a pocket for a thermocouple, a 500 ml 3-necked round-bottomed flask, a heating casing, inlet for inert gas scrubber, which is water. The reactor is heated using a furnace with 3 zones of heating in a stream of nitrogen (300-600 cm3/min). Output power adjust so that the temperature in each of the three zones were maintained at 190-200oC. In the flask add hexamethyldisilazane (5.7 g). Subsequently the flask is heated by means of a heating enclosure to a temperature of distillation. Pair hexamethyldisilazane using an inert purge gas through the catalyst bed. After 1 h the whole hexamethyldisilazane is consumed. The rate mentioned layer within 5 hours After this the device with a flow of inert gas is cooled to the ambient temperature.

Example 3

To determine the operating characteristics of the above-mentioned catalysts obtained in example 1 and comparative example 2 was carried out periodic epoxidation of 1-octene using ethylbenzene hydroperoxide. Used the following method: a mixture containing 17.0 g of 1-octene, 10 g of a solution of ethylbenzene hydroperoxide (obtained by oxidation of ethylbenzene with oxygen) in benzene and 1.0 g nonane (internal standard), were made in 4-necked round bottom flask equipped with a condenser, a thermocouple, a stirrer and a hole for sampling. After heating mentioned mixture to a temperature of 80oWith added catalyst (0.5 g). The temperature of the mixture for 30 min was maintained at a level of 80oC.

The results of periodic epoxidation using catalysts obtained as described earlier, are summarized in table. I. Conversion and selectivity determined using gas chromatographic analysis of the initial reaction mixture and reaction product. These results show that under the same loads on the titanium activity and selectivity of Ethan in the hydrocarbon, higher than the corresponding figures of the catalyst obtained by liquid phase impregnation of silica with a solution of titanium alkoxide in alcohol.

Example 4-

The dried sample of silicon dioxide (30 g) were introduced into a 500 ml 3-necked round bottom flask equipped with condenser, an inlet for inert gas scrubber, which was an aqueous solution of sodium carbonate. After that the flask in an atmosphere of dry inert gas was added to the solution, which included 51 grams of heptane and 2.1 ml (3.6 g; 0.019 mole) of TiCl4. After thorough mixing of the contents of the flask temperature mentioned oil bath was raised to 150oWith and the solvent drove through purging said system with an inert gas. Then the oil bath temperature was further increased to 200oC and kept at this temperature for 2 h

The obtained dried impregnated silica was transferred to a quartz reactor and heated to a temperature of 850oWith overlooked through said reactor a stream of air. HCl formed in the process of increasing the temperature, washed with aqueous sodium carbonate.

After SUP>And the catalyst was treated with steam, using an inert gas as a carrier. Through a layer of catalyst missed, in General, 4.5 g (0.25 mol) of water. After that, the reactor was cooled to a temperature of 200oAnd the catalyst was treated with a stream of inert gas, which in the form of steam were hexamethyldisilazane (HMDS). Through the catalyst missed, in General, 3.0 g HMDS. Subsequently, the reactor was cooled by a flow of inert gas.

Example 4-

Was repeated example 4, except that the calcination was carried out at a temperature of 850oC for 30 min using a flow of helium.

Example 4-

Was repeated example 4, except that the calcination was carried out using a flow of helium and the temperature in the process of roasting was increased to 900oWith subsequent decrease for 1.5 h to 600oC.

Example 4-D

Was repeated example 4, except that as an impregnating solvent hexane was used.

Example 5

Using the method periodic epoxidation described in example 3, compared the catalytic properties of the materials, which were obtained in examples 4-A-4-D. Received financial p is moved in the case when the ignition instead of the oxygen-containing atmosphere (example 4-A) is carried out in an inert atmosphere (examples 4-B-4-D). Negative impact on the selectivity of the epoxy compounds was not observed.

Example 6

Characteristics of the catalyst 4 were tested in the epoxidation reaction of propylene with a fixed catalyst bed. The reactor was loaded 25 g of the catalyst. The reaction mixture (12 moles of propylene per mole of ethylbenzene hydroperoxide in ethylbenzene) in the reactor was filed with an average hourly velocity of the fluid 8 h-1and at a pressure of 885 lb-ft2(62,226 kg/cm2). The concentration of ethylbenzene hydroperoxide in ethylbenzene was 35 wt.%. Through 266 h average temperature of the layer was 78oC; conversion of cumene ethylbenzene and selectivity to propylene oxide was 98% and 99%, respectively.

Example 7

Characteristics of the catalyst 4 was tested under the same conditions as in example 6. Through 261 h average temperature of the layer was 73oC; conversion of cumene ethylbenzene and selectivity to propylene oxide was 99% and 98%, respectively.

Example 8-a

The dried sample of silicon dioxide (103 g) westerlies for discharge of the gas and the scrubber, which was an aqueous solution of sodium hydroxide. After that, in the above-mentioned flask in an atmosphere of dry inert gas was added to the solution, which consisted of 143 g of n-heptane (99+%; <50 ppm water) and 7.4 ml of titanium tetrachloride (IV) (12.8 g; 0,067 mol). The resulting mixture was thoroughly mixed using a vortex mixer. The solvent was removed with a rotary evaporator at a temperature of 80oC and a pressure of 5-10 mbar.

Portion obtained in this way dried impregnated silica was made in a tubular quartz reactor (inner diameter of 1 inch (25.4 mm); length 16 inches (406.4 mm)) with a pocket for a thermocouple, a 500 ml 3-necked round-bottomed flask, a heating casing, inlet for inert gas scrubber (which was an aqueous solution of sodium hydroxide). Layer impregnated silica was heated to a temperature of 850oWith a stream of dry nitrogen (purity 99.999% availability, 400 cm3/min). After maintaining the temperature of the layer at the level of 850oC for 30 min the power supply for the furnace was stopped and the catalyst bed was cooled to a temperature of 400oC.

After that, in the above-mentioned 3-necked round bottom flask was added water (5.0 g) and the contents SUP>/min). Water was distilled through a layer of catalyst for 30 min; round bottom flask was heated using a jet air dryer to ensure that all residual water out of the flask and to drive through the catalyst bed. The temperature mentioned layer was additionally supported at the level of 400oC for 2 h, after which the tubular reactor was stood to cool to room temperature.

Received likewise steamed catalyst (35 g) were introduced into a 500 ml 3-necked round bottom flask together with 70 g of heptane (<50 ppm water) and 4.4 g hexamethyldisilazane. The flask was equipped with condenser, thermometer and inlet for inert gas. After that, the flask using an oil bath having a temperature of 115oC, was heated to a temperature distillation (98o(C) in an inert atmosphere and maintained at a temperature of distillation for 4 hours After cooling in an atmosphere of inert gas obtained by catalytic composition was collected by filtration, washed with 100 ml of heptane, and then dried in a flask in a stream of inert gas at a temperature of from 180 to 200oC for 2 h

Example 8-

The catalytic composition were obtained using the same method, episodically instead of nitrogen in the air flow.

Example 8-

The catalytic composition were obtained using the same method described in example 8, except that the steps of annealing and blowing water vapor was carried out using nitrogen containing 2000 ppm mol of oxygen.

Example 8-D

The catalytic composition were obtained using the same method described in example 8, except that the steps of annealing and blowing water vapor was carried out using nitrogen containing 4 mol % of carbon monoxide.

Example 8-E

The catalytic composition were obtained using the same method described in example 8, except that the steps of annealing and blowing water vapor was carried out using nitrogen containing 6000 ppm mol of oxygen and 4 mol % of carbon monoxide.

Example 8-F

The catalytic composition were obtained using the same method described in example 8, except that the steps of annealing and blowing water vapor was carried out using nitrogen containing 1 mol % of hydrogen.

Example 8-G

The catalytic composition were obtained using the same method, the description of the cat is whether using nitrogen, containing 4 mol % hydrogen and 0.5 mol % of oxygen.

Example 8-o

The catalytic composition were obtained using the same method described in example 8, except that the calcination was carried out at a temperature of 500oC for 30 minutes

Example 8-I

The catalytic composition were obtained using the same method described in example 8, except that the calcination was carried out at a temperature of 400oC for 30 minutes

Example 8-J

The catalytic composition were obtained using the same method described in example 8, except that the calcination was carried out at a temperature of 300oC for 30 minutes

Example 9

Catalytic compositions obtained in examples 8-A-8-J, checked through periodic epoxidation of 1-octene using the following method. The original reaction solution was obtained by mixing 170 g of 1-octene, 100 g of the solution of ethylbenzene hydroperoxide (obtained by oxidation of ethylbenzene with oxygen) in benzene and 10 g nonane (internal standard). 3-necked 100 ml round bottom flask equipped with a condenser, thermocouple, mesalc what of it 28 g portion of the above-mentioned initial reaction solution. The solution in the flask was heated to a temperature 58-59oWith, mixing it with stirrers, rotating with a frequency of 700 rpm After that the flask was added 0.5 g portion of the catalytic composition under test. The temperature of the reaction mixture within the first 10 min was controlled with 1-minute intervals, in the next - to 5-minute intervals. The temperature of the reaction mixture ranged usually within 60-63oC. After 30 min after adding the aforementioned catalytic composition selected 3 ml sample of the reaction mixture. Samples as the original reaction mixture, and the obtained product was analyzed by means of gas chromatography to determine the concentration of hydroperoxide and epoxyoctane. To calculate the conversion and selectivity of the epoxy compounds relative to the spent hydroperoxide.

The results of the epoxidation presented in table. III. It was found that the composition of the atmosphere, which was carried out by the annealing, significantly influenced the activity of the catalyst. A consequence of the presence in the process of annealing in example 8 With even a small amount of oxygen was getting less active catalyst (cf experience 9-With experience 9-a). what I for example, carbon monoxide is also present in the process of annealing (see the experience of the 9th). It was found that another important factor affecting the activity of the catalyst is the temperature of calcination. In that case, when the temperature was reduced from 850oWith up to 500oWith the conversion of cumene ethylbenzene decreased by more than half (cf. the experience of 9-and experience 9-N). At lower temperature annealing below 500oWith a further decline in catalyst activity.

1. The method of epoxidation, comprising contacting the organic hydroperoxide with an olefin in the presence of a catalytic composition obtained by the process comprising the steps of: (a) impregnation of inorganic siliceous solids with a solution of titanium halide in a hydrocarbon solvent that does not contain oxygen, and (b) annealing mentioned impregnated silicon-containing solids to obtain a catalytic composition, and the above-mentioned method differs practical with the exception of water until at least the end of stage (a).

2. The way epoxidation under item 1, where the said titanium halide is titanium tetrachloride.

3. The way epoxides Ogorodnik solvent, not containing oxygen, inorganic siliceous solid with the subsequent removal of the mentioned hydrocarbon solvent.

4. The way epoxidation under item 1 where the above-mentioned inorganic siliceous solid is silica.

5. The way epoxidation under item 1 where the above-mentioned hydrocarbon solvent that does not contain oxygen, selected from the group which consists of5-C12aliphatic hydrocarbon, C6-C12aromatic hydrocarbon, C1-C10halogenated aliphatic hydrocarbon, C6-C10halogenated aromatic hydrocarbons, and mixtures thereof.

6. The way epoxidation under item 1, where the said method for the catalytic composition comprises after step (b), an additional step of heating the aforementioned catalyst composition in the presence of water.

7. The way epoxidation under item 1, where the water is essentially eliminated before the end of the phase (b).

8. The way epoxidation under item 1, where the said method for the catalytic composition comprises after step (b) further processing step mentioned catalytic composition siliconwave includes after step (b) additional steps of heating the aforementioned catalyst composition in the presence of water and processing mentioned catalytic composition silylium agent.

10. The way epoxidation under item 1, where the step of annealing (b) is carried out at a temperature of at least 500oC.

11. The way epoxidation under item 1 where the above-mentioned organic hydroperoxide is ethylbenzene hydroperoxide.

12. The way epoxidation under item 1, where the said olefin is a C3-C10acyclic alkene.

13. The way epoxidation under item 1, where step (b) is carried out in an atmosphere essentially devoid of oxygen.

14. The way epoxidation under item 1, where step (b) is carried out in an atmosphere including oxygen and the gas-reducing agent.

15. The method of epoxidation, including the contacting of the ethylbenzene hydroperoxide with propylene in the presence of a catalytically effective amount of a catalytic composition obtained by the process comprising the steps of: (a) formation of a mixture by combining a solution of titanium tetrachloride in a hydrocarbon solvent selected from the group which consists of C5-C12aliphatic hydrocarbon, C6-C12aromatic hydrocarbon, C1-C10halogenated aliphatic hydrocarbon, C6-C10halogenated aromatic hydrocarbon is getting impregnated silicon dioxide; (c) annealing the mentioned impregnated silica at a temperature of from 700 to 1000oWith obtaining calcined catalyst precursor; (d) heating the aforementioned calcined catalyst precursor in the presence of water and (e) processing mentioned calcined catalyst precursor silylium agent, and the above-mentioned method differs, essentially, with the exception of water prior to completion of step (C).

16. The way epoxidation under item 15, where the step (C) is carried out in an atmosphere essentially devoid of oxygen.

17. The way epoxidation under item 15, where the step (C) is carried out in an atmosphere including oxygen and the gas-reducing agent.

18. The way epoxidation under item 15, where mentioned similarbuy agent selected from the group including organosilane, organosilicones, organosilazane and mixtures thereof.

19. The way epoxidation under item 15, where the content of Ti in the above catalytic composition is from 1 to 5% (wt.).

20. The way epoxidation under item 15, where the above-mentioned method for the catalytic composition includes before step (a), an additional step of drying the silica.

21. The method for the catalytic composition, clitena in a hydrocarbon solvent, not containing oxygen; (b) annealing mentioned impregnated siliceous solids with obtaining a calcined catalyst precursor and at least one of steps (C) or (d): (c) heating the aforementioned calcined catalyst precursor in the presence of water; or (d) processing mentioned calcined catalyst precursor silylium agent, and the above-mentioned method differs, essentially, with the exception of water until at least the end of stage (a).

22. The method according to p. 21, where the step (b) is carried out in an atmosphere essentially devoid of oxygen.

23. The method according to p. 21, where the said titanium halide is titanium tetrachloride.

24. The method according to p. 21, where the impregnation of (a) is carried out by combining a solution of a titanium halide in a hydrocarbon solvent that does not contain oxygen, inorganic siliceous solid with the subsequent removal of the mentioned hydrocarbon solvent.

25. The method according to p. 21, where it is mentioned inorganic siliceous solid is silica.

26. The method according to p. 21, which are both steps (C) and (d).

27. The method according to p. 21, where EB is the sphere, including oxygen and the gas-reducing agent.

29. The method according to p. 21, where the step (b) is carried out at a temperature of at least 500oC.

30. The method for the catalytic composition, comprising the steps of: (a) formation of a mixture by combining a solution of titanium tetrachloride in a hydrocarbon solvent selected from the group which consists of C5-C16aliphatic hydrocarbon, C6-C12aromatic hydrocarbon, C1-C10halogenated aliphatic hydrocarbon, C6-C10halogenated aromatic hydrocarbons and mixtures thereof with silicon dioxide; (b) deleting the hydrocarbon solvent from the mixture obtained with getting impregnated silica; (c) annealing the mentioned impregnated silica at a temperature of from 700 to 1000oWith obtaining calcined catalyst precursor; (d) heating the aforementioned calcined catalyst precursor in the presence of water and (e) processing mentioned calcined catalyst precursor silylium agent, and the above-mentioned method differs, essentially, with the exception of water prior to completion of step (C).

31. The method according to p. 30, where this is keys in the atmosphere, including oxygen and the gas-reducing agent.

33. The method according to p. 30 where the above-mentioned gas-reducing agent is carbon monoxide.

34. The method according to p. 30 comprising before step (a), an additional step of drying the silica.

Priority points

05.05.1997 - PP.1-34;

25.07.1997 - PP.1-34 (clarification of signs);

15.04.1998 - PP.1-34 (clarification of signs).

 

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