Titanium containing zeolite, a process for its production (options), the method of epoxidation of olefins and dcetermine ammonium compound to obtain a titanium containing zeolite

 

(57) Abstract:

Describes titanium containing zeolite with structure isomorphic to the structure of beta zeolite containing silicon atoms and titanium and containing no aluminum atoms in the zeolite lattice, and having a composition corresponding to the General formula SiO2: TiO2where is the value in the range from 0.01 to 0.25. Also describes how to obtain it (options), the method of epoxidation of olefins and dcetermine ammonium compound to obtain a titanium containing zeolite. The technical result - obtaining simple ways (options) molecular sieves, catalysts, selective catalytic epoxidation of olefins using hydrogen peroxide. 5 S. and 19 C.p. f-crystals, 4 tab., 3 Il.

The invention relates to a method of selective oxidation of olefins with obtaining products containing epoxy functional groups. Primarily, the present invention relates to processes in which the sources of active oxygen, such as organic gidroperekisi or hydrogen peroxide, react with the ethylene-unsaturated substance in the presence of a catalyst based on a zeolite with a relatively large pore volume, containing titanium, with images of Adamu of silicon and titanium, but, practically does not contain a lattice of aluminum.

Currently, a large number of methods for producing epoxides. One such method consists in the reaction of liquid-phase epoxidation of olefins using as oxidizing agent for organic gidroperekisi, and as a catalyst, some of the soluble compounds of the transition metal. Although this approach is implemented on an industrial scale and, as a rule, provides high selectivity to epoxide, has at least two characteristics that limit the flexibility of the process and increase the cost of production. Thus, the use of organic gidroperekisi leads to side to obtain alcohol, forming from the gidroperekisi during epoxidation, for every equivalent of epoxide formed about 1 equivalent of such a by-product. If the market for such alcohol is not present, then this by-product must be subjected to additional chemical transformations (which causes additional production costs) to return hydropeaking oxidant, or should be implemented by way of getting another connection that suitelipitor for its further use in the process. In this regard, there is a great need in creating insoluble (heterogeneous) epoxidation catalyst with high activity and selectivity of action when used with this oxidant like hydrogen peroxide, which in the course of the reaction does not form an organic by-product. In the ideal case, such a catalyst should in its active form it is easy to stand out from the reaction mixture resulting from the epoxidation by filtration or similar methods, or must exist the possibility of its application in the form of a fixed layer, etc.

Recently in the proceedings of the Polytechnic University of Valencia was reported for the synthesis of cranioleuca titanium, isomorphous beta zeolite (see Camblor with TCS. in J. Chem. Soc. Chem. Commun. C. 589-590 (1992), Camblor with TCS. in Zeolites 13, S. 82-87 (1993) and ES 2037596 (published 6/16/98). It was found that such aluminum-containing substances catalyze the oxidation of alkanes to alcohols, ketones, etc., using, etc. when used as the oxidant hydrogen peroxide. However, this type of cranioleuca titanium unmodified) (fully protonated) form is a poor catalyst for the reaction of obtaining epoxides NGOs have established the fact, that titanium containing zeolites, characterized by the fact that their matrix structure isomorphous beta zeolite and consists of atoms of Si and Ti, but practically does not contain a matrix of aluminum, can be obtained by two different methods of synthesis. In one such method uses a combination of stages of dealumination and implementation of titanium, while the other used compounds benzyl-substituted ammonium. Such molecular sieves to selectively catalyze the epoxidation of olefins using organic gidroperekisi or predecessor of hydrogen peroxide.

The invention is explained using the drawings.

In Fig. 1 shows x-ray diffraction pattern of a sample of titanium containing molecular sieve prepared according to the method of example 1. In Fig. 2 shows x-ray diffraction pattern of a sample of titanium containing molecular sieves prepared using methods according to example 2. In Fig. 3 presents a range of13C-NMR of benzyl-substituted derivative of ammonia in different environments.

In accordance with the method of epoxidation of the present invention the olefin in contact with organic hydropredict or lane is the presence of a catalytically effective amount of titanium containing molecular sieves. Titanium containing molecular sieve suitable for use in the present process is characterized by the matrix structure, isomorphic beta zeolite. The atoms of Si and Ti are present in a matrix structure (usually in the form of oxides). Matrix molecular sieve substantially does not contain aluminum (Al) however, it was found that the presence of significant quantities of aluminum has a negative impact on molecular sieves as catalysts for epoxidation, if the protons associated with aluminium substituted ammonium, alkali metal or alkaline earth cations of the metal. In the context provided above, the term "practically free" refers to a matrix structure molecular sieve containing less than 1000 h/million Al. Preferably, in a matrix structure was attended by less than 500 h/million Al. Most preferably, this number was less than 100 hours per million Molar ratio of Si to Al (Si:Al), preferably, is at least 750, more preferably at least 1000, but it can have a value of more than 3000.

Zeolite beta is characterized by the openings of the pores of the 12-membered ring and three-dimensional interconnected channel system, this matrix structure is, The Zeolites 8,446 (1986) and in the work of Treacy with TCS. in Nature, 332,249 (1988). Thus, the catalyst according to the present invention has a structure that is fundamentally different from the structures of other titanium containing molecular sieves reported in the literature (for example, a catalyst TS-1, described in U.S. patent N 4410501, which has a MFI structure, catalyst TS-2, described Reddy with TCS. in Appl. Cat 58, 11 (1990), which has the structure of ZSM-11 fully-oxide-silicon Ti/ZSM-48, described Serrano al. in J. Chem. Commun 745 (1990).

According to preferred variants of execution of the invention titanium containing molecular sieves have a relatively large pores (average sized 6 angstroms or more) and are characterized by zeolite-like structure consisting of Si and smaller amounts of Ti. Usually it is desirable for them the value of crystallinity of more than 75%.

The method of synthesis described in the above references, capable of crystallinity in excess of 95%. Preferably, the molar ratio of Ti:Si was 1:to 99.9 to 20:80, and particularly preferred ratios are in the range of 1:99 to 15:85. Preferably, when the titanium containing molecular sieve has a titanium content is 1-10 wt.%.

PR is>in which Y has a value in the range of 0,01-0,25 (preferably 0,02-0,20).

Preferred methods of synthesis of practically free from Al titanium containing molecular sieves, which are the subject of this application, include the use of compounds benzyl-substituted ammonium. Without specific theoretical considerations it can be assumed that the compounds benzyl-substituted ammonium functions template governing the formation of the desired structural skeleton of zeolite beta from reagents that are sources Si and Ti. They also provide the target product, acting as a buffer, or structural-regulating agent. Used in the text of the description, the term "template" does not imply that the compounds benzyl-substituted ammonium participate effectively in a matrix arrangement. The use of compounds benzyl-substituted ammonium to obtain catalysts of the present invention is advantageous in that such a method provides for obtaining molecular sieves, which are less acidic, contain fewer out-of frame Ti (for example, anatase) and contain fewer defects than the molecular sieve produced by the method of dealumination/Vnedrenie is able to properly function as a template for these purposes, such compounds of tetraalkylammonium, as salt tetraethyl ammonium, traditionally used as templates in the synthesis of other titanium containing molecular sieves, are not able to provide vysokokritichnyh products of high purity. Without any theoretical reasoning, we can assume that the critical (templates) used type is associated with the absence of such syntheses any aluminum compounds. It is assumed that beta-structure is unstable kinetic phase, which crystallizes only in very specific conditions. The assumption is not consistent with the relative ease of obtaining a molecular sieve having MFI structure (e.g., TS-1, ZSM-5, silicates) using matrix-regulatory methods, such substances may crystallize when using a large number of matrices.

Suitable compounds benzyl-substituted ammonium include Quaternary ammonium compounds containing at least one nitrogen atom, substituted benzyl group, Preferred is a case where each nitrogen has only one benzyl group and other groups attached to the nitrogen atom, preferably, are of one to date have been unsuccessful).

Preferred compounds benzyl-substituted ammonium used as templates in the synthesis of free from Al titanium containing zeolites having the structure of the beta include dichloride compounds containing two nitrogen atom in the same molecule, and each nitrogen atom has four hydrocarbon substituent, one of which represents a benzyl group. Such nitrogen atoms are linked by an organic fragment with normal aliphatic, branched, cyclic, aromatic or mixed alifaticheskii-aromatic nature. Preferably, the nitrogen atoms are separated from each other, at least two, but not more than sixteen carbon atoms. According to a particularly preferred embodiment, this template is a compound 4,4-trimethylene-bis(N-benzyl-N-methylpiperidine) corresponding to the structure

< / BR>
in which X preferably represents halogen (such as Br) or hydroxyl (OH).

In accordance with one method in which compounds benzyl-substituted ammonium can be used as a template matrix for the synthesis of molecular sieves, which are the subject of the present invention, solubilizers in acidic conditions. Used in the context of the present description, the term "capable of hydrolysis" refers to a compound that can act as a source of SiO2or TiO2for the structure of crystalline titanium containing molecular sieves in the reaction with water. Although this hydrolysis reaction can be carried out in any order, it is preferable to carry out the reaction capable of hydrolysis of the silicon compound with water before hydrolysis able to join him titanium.

As capable of hydrolysis of the silicon compound can be any compound that functions as a source of SiO2(silicon oxide), including, for example, amorphous silica or white carbon, or, more preferably, such tetraalkoxysilane as tetraethylorthosilicate, etc. Suitable, capable of hydrolysis of the titanium compounds are such compounds that serve as sources of TiO2(titanium oxide), for example, a titanium halide (e.g. TiCl4) or, more preferably, the titanium alkylate, as tetrabutyl titanium, etc.

Incomplete hydrolysis of the above reagents catalyzed by such acid catalyst such as mineral or organic whale. Incomplete hydrolysis can be carried out in any solvent capable of dissolving the formed partial hydrolysate. In accordance with a particularly preferred as the solvent for the hydrolysis reaction are water and/or an aliphatic alcohol, as ethanol or isopropanol. The temperature of the hydrolysis is selected in such a way as to provide a partial hydrolysis and not excessive hydrolysis, as a result of leaking excessive hydrolysis can form insoluble forms SiO2and/or TiO2. For such purposes, as a rule, suitable temperature in the range of 0-50oC. the Water is in contact with the above reagents in the course of time (typically, 0.5 to 12 hours) required for the formation of soluble partial hydrolyzate, which is characterized by the absence of precipitated silica and titanium. Although the exact structure of the soluble partial hydrolyzate is unknown, it is assumed that it includes an elongated frame of atoms of Si and Ti, are related to each other bridging oxygen atoms, and this structure contains a sufficient number of non-oxygen substituents associated with the atoms of Si and Ti, such as alkoxygroup, etc. providing restoretask amount of benzyl-substituted ammonium, effective for the implementation of additional hydrolysis, resulting in the formation of solid amorphous gel SiO2-TiO2. In the system there must be a sufficient amount of benzyl-substituted ammonium in order to neutralize the acid and make the hydrolysis alkaline environment. Usually specified gel is separated from the hydrolytic environment and it is possible to allocate any such suitable means as filtration, centrifugation, decantation, etc., For reasons not fully understood, as it was established, the use of benzyl-substituted ammonium, and not other types of bases, for example ammonia, ensures the successful receipt of the crystal free from Al, titanium containing molecular sieve having the structure of zeolite beta. Hydrolysis of soluble partial hydrolysate leads to the formation of amorphous solid gel SiO2-TiO2. This gel can be used directly as a matrix for impregnating, or, if desired, can be separated from the remaining liquid components (for example from the solvent by drying, filtration or other methods.

Solid gel is brought into contact with a solution of benzyl-substituted ammonium in creant, when the template is mainly contained in the pores of the gel. The total amount of benzyl-substituted ammonium stages of hydrolysis and impregnation, preferably, 50% (more preferably 20%) of the amount needed to fill the available pore volume of the gel. At the same time, it is preferable that the amount of solvent (which preferably is a polar compound, such as water and/or alcohol) was sufficient for dissolving benzyl-substituted ammonium, but not excessive in order to lead to the formation of a suspension of the gel in the specified solvent (e.g capable of free flowing and pumping the suspension of the gel in a liquid solvent). For these purposes, can be used technique wet impregnation. The contacting of the solid gel and benzyl-substituted ammonium is carried out within such time and at such temperature that ensure the implementation of the matrix-template in the pores of the gel (usually, this time of 0.25 to 24 hours at a temperature of 0-50oC). Then the impregnated gel is heated at a temperature of 120-160oC (more preferably, at 130-140oC) in a period of time which is effective to obtain the desired titanium containing mobs impregnated gel during heating not stirred.

The relative ratios of the various reagents upon receipt impregnated gel can change at will, but so was beneficial effect on the elemental composition of the final titanium containing molecular sieves. The composition of the impregnated gel in terms of molar ratios, in the case where the benzyl-substituted ammonium is dcetermine connection, can be the following:

DiO2/TiO25-20, preferably 10-100

X-/SiO20,002-1, preferably, from 0.05 to 0.6

H2O/SiO2of 0.1-10, preferably 1-5

M+/SiO20-0,5, preferably about 0

DQ2+/SiO2of 0.005 to 2.0, preferably of 0.025 to 1.0

where M+represents a metal cation, Na+or K+preferably, when the alkali metal cations are absent), DQ2+represents dictionay part dicatating ammonium compounds, and X-represents an anion associated with dicerorhinus connection ammonium (preferably Br2or OH-).

According to an alternative approach, titanium containing molecular sieve according to the present invention can be obtained using joint the mixture, preferably, in solution, capable of hydrolysis of a silicon compound capable of hydrolysis of compounds and titanium compounds benzyl-substituted ammonium and hydrothermal processing said mixture at a temperature of 100-200oC (more preferably, at 120-180oC) over time, which is effective for the formation of crystalline titanium containing molecular sieves. Most preferably such hydrothermal processing in the aquatic environment (which, in addition to water, may contain such miscible with water, an organic solvent, such as alcohol) in such circumstances that provide the hydrolysis of compounds of silicon and titanium. If desired, the hydrolysis can kataliziruetsa base. For such purposes can be any of the previously described capable of hydrolysis of silicon compounds, titanium compounds, benzyl-substituted ammonium. In those cases, when the compounds benzyl-substituted ammonium is used dcetermine connection, the preferred molar ratio of components in the source, the reagents can beat the following:

SiO2/TiO2- 5-2000

X-/SiO2- 0,1-2,0

H2O/SiO2- 20-200

DQ2+/SiO>+is a dication associated with dicerorhinus connection ammonium. A suitable method of obtaining the above-mentioned mixture may be given by the following: first, carry out a partial hydrolysis able to it first silicon compound is carried out by reaction of the compounds with water containing part of the compounds benzyl-substituted ammonium (hydroxide form). Then the obtained product of the incomplete hydrolysis combined with capable of hydrolysis of a compound of titanium (and, optionally, with an additional amount capable of hydrolysis of silicon compounds). Then add the remainder of the compounds benzyl-substituted ammonium with the formation of the gel precursor. Any volatile by-products that are formed as a result of hydrolysis (as, for example alcohols formed in the case, when capable of hydrolysis of the silicon compound is tetrachlorosilane, or when capable of hydrolysis of a compound of titanium is tetraalkyl titanium), if so desired, can be removed by any appropriate means, for example by distillation or evaporation prior to hydrothermal treatment. This hydrothermal treatment is best carried out in an autoclave or Finance titanium containing molecular sieve crystalline, precipitated form. Usually, the best results are achieved when the duration of hydrothermal treatment for about fourteen days. Such crystals, which usually contain a matrix pattern of benzyl-substituted ammonium compounds, can be separated from the mother liquor by such suitable means as filtration, decantation, centrifugation, then washed such a suitable liquid medium, such as water, and dried.

The crystalline product obtained by the described methods that includes a matrix pattern of compounds benzyl-substituted ammonium, if desired, may be subjected to calcination air at temperatures above 400oC removal of matrix-template still present in the pores of the molecular sieve.

Another method of obtaining the above-described titanium containing molecular sieves is that the zeolite-beta dialuminium and the resulting lattice vacancies are filled with titanium atoms. This method is relatively fast and provides a high output active catalyst, in comparison with hydrothermal methods requiring 1 week or more in one load and giving the lower exit of the catalyst and (for example HCl, H2SO4, HNO3or leaching them, or reaction with chelating agents and hydrothermal or steam treatment (possibly in conjunction with acid etching). In this regard, you can refer to the extensive list of publications describing methods dealuminated zeolite described in U.S. patent N 4576805, (excerpt from column 8, line 62 to line 27 in column (9) and article Sherzer Obtain and charakterisierung aluminum-deficient zeolites" ACS Symp. fez 248, 157-200 (1984). In a particularly preferred method is treatment of the zeolite-beta mineral acid such as nitric acid (preferably having a concentration 2-13 M, most preferably concentrated nitric acid) at a temperature of 25-150oC during the period of time from 5 minutes to 24 hours. Can be used and other mineral and carboxylic acids, as specified in the patent UK N 1061847, in published European patent N 488867, article Kraushaar with TCS. in Catalysis Letters 1. , 81-84 (1988), in Chinese patent N 1059701 (Chem. Abst. 117; 114655), in the published European patent N 95304 and Chinese patent N 1048835 (Chem. Abst. 115: 52861). Preferably implement the suspension of beta-zeolite or contactyou the TEI nitric acid 1 wt. part of the zeolite-beta). This operation dealumination can be repeated multiple times to implement a more complete removal of Al. Appropriate ways of dealumination of this type is described in detail in the work forces with al. in Microporous Materials 1, 237-245 (1993) and in the published European patent N 488867. Next delaminating material can be treated with a source of titanium. So, for example dealuminated zeolite beta can be processed in such a volatile source of titanium, as TiCl4in a nitrogen atmosphere, for 1-24 hours at elevated temperature (preferably 250-750oC). Such liquid-phase source (titanium, (NH4)2TiF6(aq.) or TiF4(aq.) can also be used for introduction of the Ti atoms in the lattice vacancies dealuminated zeolite-beta. For these purposes, also suitable such solid sources of titanium, which is able to evaporate at moderate temperatures, such as alkylates, Tirana (for example, Ti (OMe)4. Ways titanium zeolite material after synthesis is described, for example in U.S. patent N 4576805, U.S. patent N 4828812, as well as in article Kraushaar with TCS. in Catal. Lett. 1, 81- 84 (1988). Further, it is desirable to carry out the processing of titanium containing molecular sieves such salt ammonium: nitrate montou form (such as hydrogen or proton form) or to remove excess aluminum in the lattice. Successful operations are also drying and/or calcination.

Titanium containing molecular sieves of the present invention are characterized in addition to the extremely low content of Al low acidity. However, to improve the technical characteristics of some titanium containing molecular sieves obtained as described above, successful operation is the contacting of the catalyst with ammonia, alkaline and/or alkaline earth metal, without any theoretical reasoning, we can assume that this improvement can be attributed to the neutralization of some related acid metal centers present in the titanium containing molecular sieve. The preferred method of implementation of this modification is dissolving ammonium compounds, alkali or alkaline earth metal in water or other suitable liquid medium, then carry out a stage of intensive contacting the resulting solution with a molecular sieve. This method preferably is carried out at a temperature high enough to make partial (approximately, at least 25%) or complete exchange of, or substitution by ammonia alkaline or Selo what I period of time (for example 24 hours). For these purposes it is usually sufficient to use a temperature in the range of 25-150oC. the concentration of ammonium compounds, alkali or alkaline earth metals can vary, generally they are of 0.001-5M. The optimum concentration can be easily installed method of the conventional experiment. After the desired cation-exchange, excess liquid may be separated from the titanium containing molecular sieves by filtration, decantation, centrifugation, or other suitable methods, and the resulting modified titanium containing molecular sieve (if desired), washed with water or other suitable liquid and then dried and/or calcined prior to use in epoxidation reaction of the present invention. If you use ammonium compounds, it is preferable to avoid the stage of calcination, in order to minimize any deprotonirovaniem catalyst.

The particular form of ammonium compounds, alkali or alkaline earth metal selected for the specified use, is not critical, but preferably, such compounds are water-soluble material, and preferably is sodium, potassium hydroxide, barium hydroxide, calcium hydroxide), carbonates of ammonium, alkali or alkaline earth metal (e.g. sodium carbonate, potassium carbonate), bicarbonates of ammonium, alkali or alkaline earth metal (e.g. sodium bicarbonate, potassium bicarbonate, nitrate, ammonium, alkali or alkaline earth metal (such as sodium nitrate, potassium nitrate, ammonium halides, alkali or alkaline earth metals (such as potassium chloride, sodium bromide, sodium chloride), sulphate of ammonium, alkali or alkaline earth metal (such as sodium sulfate, potassium sulfate, ammonium carboxylates, alkaline or alkaline earth metals (e.g. sodium acetate), and like compounds and mixtures thereof. The counterion for ammonium compounds, alkali or alkaline earth metal should be chosen in such a way that it does not impact adversely on the desired activity of the titanium containing molecular sieve and its crystal structure. For example, it was found that under certain conditions the use of pyrophosphates of alkali metals can deactivate or poison the catalyst on the basis of the molecular sieve.

In coatedsteel, titanium containing molecular sieve receive in situ during epoxidation resulting from the use of unmodified titanium containing molecular sieve in combination with the compound of ammonium, alkali or alkaline earth metal belonging to the above-described type, or with a buffer consisting of ammonium carboxylates, alkali or alkaline earth metals, etc., for example, the reaction medium in which the olefin is in contact with hydrogen peroxide, may contain a buffer system NaOAc/HOAc (preferably in a concentration of 0.1-5M) in a suitable solvent such as alcohol (for example methanol). On the other hand, you can use the connection of an alkali metal, such as, for example sodium acetate. Periodic processes, ammonium compounds, alkali or alkaline earth metal, can, for example, be added as such to initiate epoxidation, while in continuous processes (as, for example, in cases of using reactor CSTR), these compounds can be combined with one of the flows of raw materials containing one of the other reaction components, such as oxidizing gas.

The acidity of the surface of the titanium containing molecular sieves may, with other eacli with chlorotrimethylsilane etc.

The amount of catalyst used for the epoxidation of olefin is not critical, but it should be sufficient to complete the reaction for almost acceptable period of time. The optimum amount of catalyst will depend on Rada of factors including the reaction temperature, the reactivity of the olefin and its concentration, the concentration of oxidizing agent, the type and concentration of organic solvent, and the catalyst activity. However, as a rule, when periodic epoxydecane, the amount of the catalyst is 0.001 to 10 g per mol of olefin. In systems with a fixed bed of catalyst, the optimum amount of catalyst depends on the flow of reagents through the fixed layer (typically comprising 1-100 moles of oxidizing agent per kg of catalyst per hour) Typically, the total concentration of titanium in the epoxidation reaction mixture is 10-10000 h/million

Such a catalyst may be used in powdered, granulated, microspheric, solid, extruded, or in any other suitable form. It may be preferable to use a filler (gel) or a substrate in combination with a titanium containing molecular sieve. Namesecure for zeolite catalysts in General. For example, the catalyst may be deposited on the titanium oxide by applying the methods described in U.S. patent N 5354875.

Examples of fillers and substrates (which, preferably, are not acidic in nature) can be silicon oxide, aluminum oxide, type silica-alumina, silica-titanium oxide, silicon oxide-thorium oxide, silica-magnesia, silica-Zirconia, silica-oxide of beryllium, as well as a four-part composition based on silica and other refractory oxides. Can also be used such clay as montmorillonite, kaolins, bentonites, halloysite, dickite, nacrite and anxiety. The ratio between the titanium containing molecular sieve and a filler or substrate may be in the range 99:1-1:99, preferably 5: 95-80: 20. Consider the catalyst may be impregnated or mixed with such noble metals like Pt, Pd, etc.

Olefin exposed epoxydecane according to the method of the present invention may be any organic compound containing at least one ethylenevinylalcohol group (i.e., carbon-carbon double bond) and may be the olefin cyclizes the Teal). Preferably, the olefin is aliphatic in nature and contains 2-30 carbon atoms (i.e., olefin C2-C30. Particularly successful is the use of lightweight (low-boiling) monoolefins C2-C10. In the molecule of the olefin may contain more than one carbon-carbon double bond, thus can be used dieny, triene and other polyunsaturated substrates. The double bond in the olefin may be a terminal or inside a molecule, or form part of a cyclic structure (as it occurs for example in cyclohexane). Other examples of suitable substrates include unsaturated fatty acids or their derivatives, such as esters of glycerides, as well as oligomeric or polymeric unsaturated compounds as polybutadiene. Epoxydecane can also be benzyl and olefins, styrene, although it should be borne in mind that the epoxides some styrene olefins, such as styrene, may enter into subsequent isomerization reactions in the conditions of the present invention with the formation of aldehydes, etc.

The olefin may contain other substituents other than hydrocarbon, for example a halide, carboxylate, ether, hydroxyl, Tilney">

Examples of olefins suitable for use in the method of the present invention can serve as ethylene, propylene, butenes, for example, 1,2-butene, 2,3-butene, isobutylene, butadiene, pentane, isopropane, 1-Gakuen, 3-hexene, 1-hepten, 1-octene, Diisobutylene, 1 none, 1-tetradecene, pentamycin, camphene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecane, 1-Gelderen, 1-heptadecene, 1 octadecan, 1-nonadecane, 1 achozen, trimers and tetramer propylene styrene (and other vinylaromatic substrates), polybutadiene, polyisoprene, cyclopentene, cyclohexene, cycloheptene, zilactin, cyclooctadiene, cyclododecene, cyclododecatriene, Dicyclopentadiene, methylenecyclopropane, methylenecyclobutane, methyltriclosan, vinylcyclohexane, vinylcyclohexane, metallic-ketone, allyl chloride, allyl bromide, acrylic acid, methacrylic acid, crotonic acid, vinilkosmo acid, methallyl-chloride, dichlorobutane, allyl alcohol, allyl-carbonate, allyl-acetate, alkylacrylate and methacrylates, diallyl-maleate, diallyl-phthalate, such unsaturated triglycerides as soybean oil and such unsaturated acids as oleic acid, linolenic acid, linoleic acid, erucic acid, palmarola acid, and ricinoleic KIS is aniu may be a mixture of olefins and the resulting mixture of epoxides can be used either in a mixed form, or be subjected to separation into individual components.

The method of the present invention is particularly useful for the epoxidation of olefins, C2-C30that meet the General structure

< / BR>
in which R1, R2, R3and R4can have identical or different meanings and they are chosen from the group consisting of hydrogen and Akilov C1-C20.

As the oxidizing agent in the process of the present invention can be used a source of hydrogen peroxide, for example, the hydrogen peroxide (H2O2), organic Gidropress, or a compound capable of reaction conditions epoxidation to form or select the peroxide or organic hydropeaking. It was found that often epoxidation proceeds more easily (i.e. with higher speeds, with higher selectivity for epoxide) when used as an oxidizing agent for organic gidroperekisi, although the causes of the established fact, to date, unclear. This result was completely unexpected in light of recent reports (HOU al. J. Catalysis, 149 195-205 (1994), which States that other free from aluminum titanium containing ZSM and that such inactivity is not associated with a relatively small pore size TS-1, but rather connected with the volume of the mass of organic hydroperoxides in the formation of their complexes with the active centers of Ti.

The ratio between the amount of oxidizing agent and the amount of olefin is not critical, but it is best to use a molar ratio of oxidizing agent: olefin in the range of 100:1-1:100 in the case where the olefin contains one ethylenevinylalcohol group. The molar ratio between the number ethanobotany groups in the olefin and the amount of oxidizing agent is preferably selected from the range of 1:10-10:1. Theoretically, to oxidize one equivalent of monounsaturated olefin requires one equivalent of the oxidizing agent, however, sometimes, to improve the selectivity of the reaction of the epoxide, it is desirable to use an excess of one of the reagents,

Although hydrogen peroxide suitable for use as the oxidizing agent, can be obtained from any suitable source, the advantage of the method of the present invention is the fact that the hydrogen peroxide can be obtained by contacting such secondary alcohol as alpha-methyl-benzyl alcohol, isopropyl alcohol, 2-butanol or cyclohexanol with Molinaro alcohol and hydrogen peroxide (and/or predecessor hydrogen peroxide). Typically, such oxidizing the mixture will also contain ketones such as acetophenone, acetone or cyclohexanone corresponding secondary alcohol (i.e., having the same carbon skeleton), a small amount of water and varying amounts of other forms of active oxygen, for example, organic hydroperoxides. To obtain hydrogen peroxide can also be used oxidation by molecular oxygen of anthrahydroquinone, alkyl substituted anthrahydroquinone, or water-soluble anthrahydroquinone compounds. The hydrogen peroxide can be formed in situ immediately prior to or simultaneously with epoxydecane, as for example described in the published European patent N 526945 Japanese Kokai N4-352771, the report Ferrini with TCS. /"Catalytic oxidation of alkanes using titanium silicate in the presence formed in situ. hydrogen peroxide DSMC conference on selective oxidation in the petrochemical industry, September 16-18, 1992, S. 205-213, and in published European patent N 469662.

As organic hydroperoxides suitable for use as the oxidizing agent in the method of epoxidation of the present invention, can be any organic is Vlada secondary and tertiary gidroperekisi, due to the high instability of the primary hydroperoxides and safety reasons. Organic Gidropress preferably has the following General structure

< / BR>
where R1, R2and R3can have identical or different meanings and they are chosen from the group consisting of hydrogen, Akilov C1-C10(for example methyl, ethyl, tert-butyl) and allow C6-C12(for example, phenyl, alkyl substituted, phenyl, provided that not more than one of the radicals R1, R2or R3represent hydrogen. Examples of organic hydroperoxides can serve tert-butyl of gidroperekisi, tert-amyl hydroperoxide, Gidropress has been studied, Gidropress ethylbenzene, Gidropress of cyclohexyl, Gidropress methyl-cyclohexyl, Gidropress of tetralin, Gidropress isobutylbenzene, Gidropress naphthalene, etc., May also be used mixtures of organic hydroperoxides.

If it is desirable, in the epoxidation process of the present invention can further be used a solvent to dissolve the reagents, other than titanium containing molecular sieves in order to provide better temperature control of the reaction or blogwriter can be 1-99 wt.% of the total number of the reaction mixture of epoxydecane and preferably, the solvent is chosen so that it was a liquid at the reaction temperature of the epoxidation.

As a rule, preferred to use are organic compounds with boiling points at atmospheric pressure 25-300oC. an Excess of the olefin may serve as a solvent or diluent. Examples of suitable solvents may include ketones (for example acetone, methyl ethyl ketone, acetophenone), ethers (for example tetrahydrofuran, butyl ether), NITRILES (for example acetonitrile), aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, and alcohols (e.g. methanol, ethanol, isopropyl alcohol, tert.butyl alcohol, alpha-methyl, benzyl alcohol, cyclohexanol, triptoreline). It was found that the use of polar, but subcoordinator solvent, such as triptorelin, increases the activity and selectivity of the catalyst, especially in the case where the oxidant is an organic Gidropress as the state. An important practical advantage of the present invention is the fact that the process may be implemented practically using the Yes as in the use of these solvents in the application of other titanium containing molecular sieves, as TS-1 as catalyst, are achieved poor results. This flexibility of the process minimizes the problems that have to be considered in other cases, when there are attempts to highlight the epoxy product from the epoxidation reaction mixture. For example, quantitative separation of methanol from such relatively lightweight epoxide as propylene oxide, hampered with close values of the boiling points. Can be used several types of solvents. Water can also be used as solvent or diluent, it has been unexpectedly found that the method according to the invention is implemented with minimal hydrolysis even in cases, when the epoxidation reaction mixture has a significant amount of water. Thus, to implement the method of the present invention can be used as two-phase and single-phase reaction system.

The reaction temperature is not critical, but it should be sufficient to achieve significant conversion of the olefin to the epoxide for a reasonably short period of time. It is reasonable to carry out the reaction to achieve the highest possible degree of conversion of oxidizing agents is at least 95%, this must be accompanied by significant selectively. Among the various factors influencing the optimum reaction temperature, it is possible to note the activity of the catalyst, the reactivity of the olefin and the oxidizing agent, the concentration of the reagent and the type of solvent, but generally, this temperature lies in the range of 0-150oC (more preferably, 25-120oC). Generally, suitable, depending on the above factors, can serve as the reaction times from 1 minute to 48 hours (more preferably, from 10 minutes to 8 hours). Although there may be pressure above atmospheric, preferably, (especially in the case where the boiling point of the olefin is lower than the temperature of the epoxidation reaction) to carry out the reaction at atmospheric pressure or at elevated pressure (typically 1-100 ATM). Usually, it is desirable to create in the epoxidation reactor sufficient pressure to maintain the components of the reaction in the liquid phase. For example, carrying out the epoxidation reaction at high pressure increases solubility of such gaseous reagents as propylene, solvent and hydrogen peroxide.

The way nastojashem reaction vessels or equipment of the appropriate type, for example, reactors, fixed bed, moving bed, fluidized bed, the reactor peremestivsheesya emulsion or CSTR reactor when using single-phase or two-phase systems. Known methods of implementation of the epoxidation reactions of olefins under conditions of catalysis by metals, using an oxidizing agent on the basis of active oxygen

also, can be used for this case. For example, the reagents can be combined all at once or enter in the reaction sequence. For example, the oxidizing agent may be introduced into the reaction zone parts. The oxidizing agent can also be formed in situ in the same reactor zone, where the epoxidation reaction. After carrying out the epoxidation reaction to the desired degree of conversion, epoxy product can be separated or select from the reaction mixture using appropriate techniques, such as fractional distillation, extractive distillation, extraction system liquid-liquid, crystallization, etc., After separation from the epoxidation reaction mixture by any of the methods, for example by filtration, the regenerated catalyst can economically be used for subsequent epoxy the epoxidation zone in the form of a stream practically, does not contain a catalyst, since the latter is held in the epoxidation zone. In some embodiments of the present invention, providing for the receipt of epoxide in the continuous variant, it may be desirable to periodically or continuously regenerate the whole amount or the part used titanium containing molecular sieve catalyst in order to maintain optimum activity and selectivity. Appropriate regeneration methods include, for example, treatment of the catalyst with a solvent, the calcination of the catalyst, and/or the contacting of the catalyst with the compound ammonium, alkali or alkaline earth metal. Any amount of unreacted olefin or oxidizing agent can be subjected to the same separation and recycling. On the other hand, unreacted oxidizing agent (particularly, in the case when it is present in concentrations too low for economical regeneration) may be subjected to thermal or chemical decomposition of the peroxide content chain of connection. In those embodiments, the performance of the present method, when the oxidizing agent is a peroxide mixture epoxidation also contains a secondary alcohol and a ketone, corresponding to such a secondary alcohol. After separation of the epoxide from the secondary alcohol and the corresponding ketone, the latter can be subjected to reverse conversion of the secondary alcohol by hydrogenation. For example, the ketone can react with hydrogen in the presence of such a hydrogenation catalyst based on a transition metal, as Nickel of Renee, chromite, copper, ruthenium, or palladium deposited catalyst. The hydrogenation reaction of this type is well known to specialists. The secondary alcohol can be subjected to dehydration using known methods, with the formation of such securities alkenyl products, such as styrene.

Described in the text of titanium containing molecular sieve, in addition to its use as a valuable catalyst for the epoxidation may also find use as an ion exchanger selective adsorbent separator, or catalysts other processes conversion of hydrocarbons, such as cracking, selective reforming, hydrogenation, dehydrogenation, oligomerization, alkylation, isomerization, dehydration, hydroxylation of olefins or aromatic compounds, oxidation of alkanes, reforming, disproportion reactions in which previously used silicalite titanium (also referred to as titanium silicates). Examples of applications of this type are as follows:

a/ way to obtain ketone-oxime, which is in the reaction of ketone such as cyclohexanone with ammonia and hydrogen peroxide in the liquid phase at a temperature of 25-150oC, in the presence of a catalytically effective amount of titanium containing molecular sieves. Reaction of this type is well known from the literature and appropriate conditions for the exercise of such synthetic transformations in the presence of titanium - silicalite catalyst is described, for example in U.S. patent N 4745221, article, Raffia with TCS. Cyclohexanone Ammoximation: A. Breakthroagh in the b. Caprolactam production process in the book "New approaches to selective oxidation" as amended, senti other S. 43-52 (1990), in the article by Raffia with al, "a New process of obtaining cyclohexasiloxane" la eh: mica and L. Industria 72, S. 598-603, 1990), U.S. patent N 4894478, U.S. patent N 5041652, U.S. patent N 4794198, in the article by Ride with TCS. "Maximilianii cyclohexanone on titanosilicate molecular sieves," J. Hol. Cat. 69, 383-392 (1991), in European patent publication N 496385, in published European patent N 384390 and U.S. patent N 4968842.

b/ the Way of the oxidation of paraffin compounds (i.e., Nasima hydrogen in the presence of a catalytically effective amount of titanium containing molecular sieves. Reactions of this type are well known from the literature and the appropriate conditions for the implementation of such a synthesis reaction in the presence of silicalite titanium is described, for example, article Huibrecht with TCS. Nature 345, 240(1990), article Clerici. Appl. Catal. 68, 249(1991) article Tatsumi with TCS. in J. Chem. Soc. Chem. Comm. 476 (1990), Huybrechts with TCS. in Catalysis Zetters 8 237-244 (1991).

in the Way hydroxylation of aromatic hydrocarbons (such as phenol), which consists in the reaction of aromatic compounds at a temperature of 50-150oC with hydrogen peroxide in the presence of a catalytically effective amount of titanium-containing molecular sieves with the formation of phenolic compounds such as cresol). Reactions of this type are well known from the literature and the appropriate conditions for the implementation of such a synthesis reaction in the presence of silicalite titanium is described, for example in U.S. patent N 4396783, article Romano al. "Selective oxidation in the presence of silicalite Ti ". La Chimica L' Industrim 72, 610-616 (1990) article Reddy with TCS. Appl. Catalysis 58, 11-14 (1990).

g/ Method of isomerization of aryl-substituted epoxide to the corresponding beta-phenyl aldehyde, which consists in contacting the aryl-substituted epoxide with a catalytically effective amount of titanosoderzhashchie).

n/ a Method of oxidation vinylbenzene connection to the corresponding beta-phenyl aldehyde, which consists in the reaction vinylbenzene compounds with hydrogen peroxide at a temperature of 20-150oC in the presence of a titanium containing molecular sieves. Cm. for example, U.S. patent N 4609765.

e/ a Method for the synthesis of N,N-dialkyl hydroxylamine, which consists in the reaction of the corresponding secondary dialkylamino with hydrogen peroxide in the presence of a titanium containing molecular sieves. Cm. for example, U.S. patent N 4918194.

W/ the Way of the oxidation of aliphatic alcohol, which consists in the reaction of aliphatic alcohol with hydrogen peroxide in the presence of a titanium containing molecular sieve at a temperature of 25-150oC with the formation of the corresponding ketone or aldehyde corresponding to the specified aliphatic alcohol. Cm. for example, U.S. patent N 4480135.

C/ Way of synthesis monoalkyl ether glycol, which consists in the reaction of olefins, aliphatic alcohol and hydrogen peroxide, in the presence of a titanium containing molecular sieve at a temperature of 25-150oC. Cm. for example, U.S. patent N 4476327.

Based on the above, the person skilled in the art can easily appreciate the significant paths with the in order to adapt the invention to different applications and conditions.

The following additional examples illustrate the method of the present invention and does not limit the invention.

Example 1.

This example illustrates the obtaining of such molecular sieves, practically free from lattice aluminum and having a lattice structure is isomorphic to the structure of zeolite beta and the connections of the benzyl-substituted ammonium is used as the matrix-template.

Matrix-template 4,4'-trimethylene-bis(N-benzyl-N-methylpiperidine)-dihydroxide, was prepared as follows: to 800 ml of ethyl acetate was added 25 g (0,105 mole) 4,4'-trimethylene-bis-(1-methylpiperidine). Then to the resulting solution was bury in a stream of nitrogen to 36.8 g (0,215 mole) benzyl bromide. Soon formed a white precipitate and the resulting mixture was stirred overnight in a stream of nitrogen. The solid precipitate was isolated, washed with ethyl acetate and then subjected to resuspending from pentane. After precipitation for the second time and washing with pentane, the resulting product was dried in vacuum at 30oC for 48 hours. The output of the dibromide was close to calician 300 g anyone-exchange resin BioRad Ag I-X8. The target connection dicatating ammonium received in the form of almost colorless aqueous solution after low-temperature removal of water to the concentration of the solution.

To 30 g (0,144 mole) of tetraethylorthosilicate was bury 0,72 g 0.05 M aqueous solution of HCl. The resulting clear solution was stirred for two hours at room temperature in a weak stream of nitrogen. After this was added 30 ml absolute ethanol and then bury 1,53 g (0,045 mol) of a solution of Tetra. n-butyl titanium in 20 ml of isopropanol. Next, bury 2 g of 1.27 N solution trimethylene-bis(benzyl-methylpiperidine)dihydroxide. The resulting solution was dried at 110oC during the night with the formation of 23.3 g of dry white powder. In the UV spectrum of the diffuse reflection of the dried gel is characterized by two strong absorption bands in the region 216 and 235 nm.

An additional part (17 g) of the above solution matrix template was combined with 4 g of double-distilled deionized water. Using the method of wet impregnation, the resulting diluted solution of the matrix-template bury to the dried gel.

The amount of solution was slightly greater than that required for the initial uvlazhneniya the following:

0,144 Si : 0,045 Ti : 0,012 DQ : 0,24 OH : 0,973 H2O

Si/Ti = 32, DQ/Si = 0,084, OH/Si = 0,167, H2O/Si = 6,8

DQ = dictiona the connection part dicatating ammonium. The resulting suspension was placed in futureready Teflon Parr reactor and heated in a static condition within 8 days at 135oC (it was found that shorter heating leads to the formation of partially amorphous products). After that, the solid was isolated, washed with water and then dried at 110oC during the night. X-ray analysis of the powder confirmed that the dried titanium containing molecular sieve has the structure of beta zeolite and contains redetection contamination from other phases such as ZSM-12. In accordance with the data of TGA analysis, it was found that at 800oC observed weight loss of 26.1%, associated with loss of matrix-template, which corresponds to 3.3 molecules in the matrix pattern on a 64 atom of Ti. DSC analysis showed one ectothermy (up to 700oC) with center at 432oC and start at 382oC. In accordance with literature data / van-der Waal with TCS. J. Chem. Soc. Chem. Comm. 1241-1242 (1994) ocenography-boric zeolite beta contains substantial amounts of coke after calcinations at 400oC, and for udalennaya. In contrast, the titanium containing zeolite beta obtained in accordance with the present invention can be sintered at 550oC for 8 hours in an atmosphere of dry air with complete removal of the total number of matrix-template (as evidenced by the data of elemental analysis). Data of x-ray analysis of the calcined substance (Fig. 1) evidence of the preservation and crystallinity.

Elemental analysis of the calcined substance showed the presence of 32% Si, 2.0 Ti<100 h/million Al, 0.025% Of Na (Si/Ti=27.3 Si/Al 3500). The calcined substance has a volume of micropores 0,269 ml/g (N2the measurement according to BET), which is in good agreement with the value 0,266 ml/g obtained for fully silicon-containing zeolite beta. Adsorption of toluene was 230 mg/g, compared to 170 mg/g for the H-Al/beta, which confirms the more hydrophobic nature of the first sample. Data OTHER UV spectroscopy revealed a strong absorption in the region 216 nm and a second smaller peak at 232 nm. A small peak in the region of 330 nm, present in the spectrum indicates a small degree of contamination Anatsui. In the IR spectrum of the calcined molecular sieve there is a moderately strong resonance at 953 cm-1that was attributed to perturbation of the cell SiO4in re calendula) molecular sieves showed matrix-based pattern dicatating ammonium remains intact inside the lattice frame during hydrothermal synthesis13C MASS-NMR spectrum of the synthesized molecular sieve, shown in Fig. 3 under the index A, and13C-MASS-NMR spectrum of 4,4'-trimethylene-bis(benzyl-methylpiperidine)-dibromide (B in Fig. 3) and13C MASS-NMR spectrum dibromide in solution d6-acetone (C in Fig. 3) provided additional confirmation of the presence of compounds dicatating ammonium. In the spectrum of13C MASS NMR calcined molecular sieve is a strip Q3 (-101 h/million) intensity of which is higher than 2.5 times than the strip Q4 (-110 h/million), which is similar to the ratio observed for TS-1 (MF 1) silicalite titanium. This indicates the fact that the molecular sieve of the present invention does not contain a significantly larger number of defect centers silanol (SiOH) than TS-1. SEM analysis of the synthesized molecular sieve showed the presence of a homogeneous, small (submicron) particles of spherical morphology and gave no evidence of the presence of amorphous material.

It was found that the calcined titanium containing molecular sieve having the structure of zeolite beta obtained in accordance with the described above hydrogen or organic peroxides, as the peroxide tert-butyl. The results obtained are presented in table. I and II. For example, when using 1-hexene as a substrate at 60oC in the presence of 50% H2O2(the ratio of olefin: H2O2= 3.3V) in the environment of methanol through the hour was achieved by conversion of 27%, the selectivity of 37% (calculated as H2O2) epoxide and 12% selectivity for methyl esters. After 3 hours was observed conversion of 71% with a selectivity to epoxide 17% and the selectivity for methyl ether glycol 110 (ratio of epoxide/glycols = 3,2). When using non-neitralizovannom Ti-Al/ (i.e., beta-zeolite, containing in the structure matrix atoms of Si, Ti and Al in a similar situation, on the contrary, there is almost 100% selectivity for products disclosure cycle. To determine the influence of water, the reaction solution is first dried over magnesium sulfate. In conditions similar to those described above, it was found that after 1 hour the conversion of H2O2was 40% while the selectivity to epoxide 40% and a selectivity of side products disclosure of the cycle only 4% (the ratio of epoxide/glycols = 10).

Even better results were obtained when using as the oxidizing agent gidroperekisi tert.butyl (90 - as olefin in the 90oC it was found that after 1 hour the conversion of the state amounted to 78% with a selectivity to epoxide 68% and selectivity to glycol of less than 1%. For comparison it should be noted that in similar conditions (reaction time 1.5 hours) use is not subjected to the neutralization of Ti-Al/ leads to the conversion of the state's 58%, the selectivity to epoxide only 38% and selectivity to glycol 61%.

Example 2.

This example demonstrates an alternative method of obtaining titanium containing molecular sieve according to the present invention.

The calcined zeolite-beta (5 g, onteko, 41-89-001) having a ratio of SiO2: Al2O3equal to 24, were added 500 ml 13N nitric acid solution. The resulting suspension was heated at 80oC for four hours, with stirring. Suspended solids were isolated by filtration and was twice subjected to the above-described processing fresh portions 13N nitric acid. After separating by filtration, the solids were washed with deionized water and dried at 95oC during the night with the formation of dealuminated zeolite beta with a molar ratio Si/Al 940.

Dealuminated beta zeolite was loaded in a quartz tube. Obrazec was heated at 400oC, then heated at 600oC and the flow rate of nitrogen was increased to 300 cm3/min. After the establishment of the temperature value 600oC the sample was processed within eight hours of titanium tetrachloride by blowing nitrogen through a heated (40oC) a solution of TiCl4. After this processing using TiCl4stopped and through the sample for one hour at 600oC continued flowing nitrogen. Next, the sample was cooled to room temperature overnight in a stream of nitrogen. Chilled neck was treated with 1M aqueous solution of ammonium nitrate at 80oC for four hours. The sample was isolated by filtration, well washed with water, dried at 95oC and then progulivali at 550oC for 6 hours to obtain titanium containing molecular sieve having a very low content of aluminum. The data of Raman spectroscopy, as well as29Si and27Al MASS NMR also confirmed that there was almost complete dealumination and that titanium was incorporated into the structure of the zeolite. Range of x-ray powder diffraction titanium containing molecular sieve is shown in Fig. 2 and systematized in table. III. Elemental analysis showed that the molecular sieve soderquist the catalyst for the epoxidation of 1-hexene hydrogen peroxide using the following conditions: 60oC, 12.2 g of methanol (solvent), to 16.5 mmole of 1-hexene, 4.5 mmole of hydrogen peroxide, 0.10 g of catalyst.

The results of this assessment are presented in table. IV. Example 2-A shows that a good selectivity for epoxide can be achieved without modification of the catalyst metal cations of Group IA or group IIA that (as expected) is associated with an extremely low content in the catalyst is aluminum. The activity of such a catalyst is sufficiently high, 90% conversion of hydrogen peroxide is achieved in one hour. When washing the catalyst with 0.5% solution of sodium acetate (example 2-B) is not much lower initial reaction rate, as measured by the conversion of hydrogen peroxide for improved selectivity. Example 2-C shows the fact that the titanium containing molecular sieve is subjected to processing with sodium acetate, also provides obtaining satisfactory results, the replacement of methanol by the alpha methylbenzylamine alcohol as solvent in the epoxidation. In contrast, the activity using alpha-methyl benzyl alcohol as solvent (example 2-D)

Example 3.

The following example illustrates alternativnaya as matrix-template connection dicatating ammonium.

A solution of 4,4'-trimethylene-bis-(N-benzyl-N-methylpiperidine)dihydroxide was prepared according to the method of example 1 from 30 g of the corresponding dibromide. Tetraethylorthosilicate (30 g, 144 mole was subjected to partial hydrolysis by adding dropwise 50 ml of 0.49 N (hydroxide) aqueous solution of the matrix-template. To this homogeneous solution was added tetrabutyl titanium (1,74, 0,00511 mod 5 g (0,024 mmole) of tetraethylorthosilicate. To the resulting turbid fluid was added to the remaining solution of the matrix-template (from 0,0517 mol). After stirring at room temperature for two hours ethanol, obrazovavsheisya during hydrolysis was removed by evaporation and the precursor gel was allowed to age overnight. The gel precursor has the following composition:

TiO2:10 matrix-template: 33 SiO2:800 H2O

Transparent precursor gel was loaded into Teflon lined reactor and heated with shaking for 9 days at 135oC. the resulting crystalline solid was given a spectrum x-rays, characteristic of beta-structure matrix. After annealing, molecular sieve showed two bands in the spectrum of UV /VIS at 233 nm and 214 nm with the intensity/P> Epoxidation of 1-hexene using hydrogen peroxide and calcined molecular sieve at 60oC led after 1 hour, 44% conversion, the selectivity of 45.3% in the calculation of the hydrogen peroxide. Organic reaction products consisted of 73.8% of the oxide of Helena-1 and 26.2% glycol ethers. In the sample taken after six hours of reaction time was set to 100% conversion and 31% selectivity based on hydrogen peroxide. The resulting organic products represented oxide, hexene-1 (42 wt.%) and glycol ethers (58 wt.%).

1. Titanium containing zeolite with structure isomorphic to the structure of beta zeolite containing silicon atoms and titanium and containing no aluminum atoms in the zeolite lattice, and having a composition corresponding to the General formula SiO2: TiO2where is the value in the range from 0.01 to 0.25.

2. Titanium containing zeolite under item 1, characterized in that it contains in the lattice of the zeolite is less than 100 ppm of aluminum atoms.

3. Titanium containing zeolite under item 1, characterized in that it has a characteristic spectrum of x-ray diffraction according to Fig.1.

4. Titanium containing zeolite under item 1, 2 or 3, characterized in that it further contains the m, it contains titanium in the range of 1 to 10 wt.%.

6. The method of obtaining titanium containing zeolite with structure isomorphic to the structure of beta zeolite containing silicon atoms and titanium and containing no aluminum atoms in the zeolite lattice, and having a composition corresponding to the General formula SiO2: TiO2where is the value in the range from 0.01 to 0.25, namely, that

a) carry out the reaction capable of hydrolysis of compounds of silicon and titanium compounds with water in an acid environment with formation of solubilizing partial hydrolyzate, not containing precipitated silicon dioxide and titanium dioxide; b) contacting the solubilized partial hydrolyzate with dicerorhinus ammonium compounds, in which each nitrogen atom bears one benzyl Deputy, taken in an amount effective to catalyze additional hydrolysis with formation of a solid amorphous SiO2- TiO2gel; C) contacting the solid amorphous SiO2- TiO2gel with a solution of the specified dicatating ammonium compounds in the environment of the solvent with the formation of the impregnated gel and g) the obtained gel is heated at 120 - 160oC for a time sufficient for the formation of the th ammonium compounds in stages (b) and (C) approximately 50% of the quantities necessary to fill the pore volume of the solid amorphous SiO2- TiO2- gel.

8. The method according to PP.6, 7, consists in the fact that the solvent is taken in a quantity sufficient to dissolve dicatating ammonium compounds, in which each nitrogen atom bears one benzyl Deputy without the formation of slurry impregnated gel in the specified solvent.

9. The method according to PP.6 to 8, which consists in the fact that the impregnated gel has a composition corresponding to the following molar ratios

SiO2/TiO2- 5 - 200

X-/SiO2- 0,002 - 1

H2O/SiO2the 0.1 - 10

M+/SiO2is less than or equal to 0.5

Q2+- 0,005 - 2

where M+is a cation of an alkali metal;

X-anion dicatating ammonium compounds, in which each nitrogen atom bears one benzyl Deputy;

Q2+- dication specified dicatating ammonium compound.

10. A method of obtaining a crystalline titanium containing zeolite with structure isomorphic to the structure of beta zeolite containing silicon atoms and titanium and containing no aluminum atoms in the zeolite lattice, and having a composition corresponding to about mesh capable of hydrolytic silicon compound, compounds of titanium and dicatating ammonium compounds, in which each nitrogen atom bears one benzyl Deputy, and the hydrothermal treatment of the mixture at a temperature of 100 - 200oC for a time sufficient to form a crystalline titanium containing zeolite.

11. The method according to p. 1, which is capable of hydrolysis of the silicon compound and dcetermine ammonium compound taken in a molar ratio of 0.03 to 2.0.

12. The method according to PP.10, 11, which consists in the fact that they use is capable of hydrolysis of a compound of titanium, which represents a Tetra-n-butyl titanium.

13. The method according to PP.6 - 12, which is capable of hydrolysis of the silicon compound is subjected to partial hydrolysis prior to the merger with capable of hydrolysis of a compound of titanium.

14. The method according to PP.6 - 13, which consists in the fact that they use is capable of hydrolysis of the silicon compound, representing tetrachlorosilane and tetraethoxy titanium.

15. The method according to PP.6 - 14, which consists in the fact that the obtained crystalline catasterismi zeolite is subjected to calcination.

16. The method of epoxidation of olefins by kontaktierung amount of crystalline titanium containing zeolite in the course of time and at a temperature sufficient for the selective formation of the epoxide of the olefin, characterized in that use crystalline titanium containing zeolite with structure isomorphic to the structure of beta zeolite containing silicon atoms and titanium and containing no aluminum atoms in the zeolite lattice, and having a composition corresponding to the General formula SiO2: TiO2where y has a value in the range from 0.01 to 0.25.

17. The method according to p. 16, characterized in that the olefin representing2- C10-monoolefins.

18. The method according to p. 17, characterized in that the olefin selected from the group ethylene, propylene, butene-1, butene-2, isobutylene, penten-1, penten 2 cyclopentene, hexene-1, cyclohexene, vinylcyclohexane, allyl alcohol, hepten-1, octene-1, 1,3-butadiene.

19. The method according to PP.16 to 18, characterized in that use organic Gidropress having the structural formula

< / BR>
where R1, R2, R3have the same or different values and they are chosen from the group consisting of C1- C10of alkyl, C6- C12aryl and hydrogen, provided that not more than one radical of R1, R2or R3represents hydrogen.

20. The way trichosis fact, what olefin and organic Gidropress take in a molar ratio of(10 : 1) - (1 : 10).

22. The method according to PP.16 to 21, characterized in that use organic Gidropress selected from the group consisting of tert.butylhydroperoxide, tert. AMYLPEROXY, gidroperekisi cumene, gidroperekisi ethylbenzene and gidroperekisi of cyclohexyl.

23. The method according to PP.16 to 22, characterized in that the crystalline titanium containing zeolite is used as the fixed layer or in suspension.

24. Dcetermine ammonium compound of the formula

< / BR>
in which X represents halogen or hydroxyl.

Priority points:

23.12.93 on PP.1 - 5, 10 - 18, 20.

26.10.94 on PP.6 - 9, 19, 21 - 24.

 

Same patents:

The invention relates to 4-amino-1-piperidinecarbonitrile formula (I):

< / BR>
where R1and R2each independently of one another denote H, A, Ph, Ph-ALK, CO-A, CO-Het, or known of the chemistry of protective peptides for amino group;

R1and R2together also denote alkylene with 4-5 C atoms, and one or two CH2- groups may be replaced by-O-, -S-, -CO-, -NH-, -NA - and/or N-CH2-Ph and, if necessary, the benzene ring may be precondensation so that the formed dihydroindole, tetrahydropyrimidines, tetrahydroisoquinolinium or dehydrobenzperidol the rest;

R3and R4each independently of one another denote H, A, Gal, -X-R5, CN, NO2, CF3CH2-CF3, SOn-R7or SO2-NR5R6;

R5denotes H, A, CF3CH2-CF3Ph, Ph-alk, C5-C7- cycloalkyl or C5-C7-cycloalkyl-alk;

R6denotes H or A, or

R5and R6together also denote alkylene with 4-5 C atoms, and one CH2group can be replaced by-O-, -S-, -NH-or-N-CH2-Ph;

R7denotes A or Romani;

Gal denotes F, Cl, Br or I;

Ph denotes unsubstituted or one-or two-, or three times substituted by A, OA, Gal, CF3, NH2, NHA or NA2phenyl;

Het denotes a saturated or unsaturated five - or six-membered heterocyclic residue with 1 to 4 atoms of nitrogen, oxygen and/or sulfur; and

"n" represents 1 or 2;

and their physiologically acceptable salts

The invention relates to chemical technology and can be used in the processes of selection vinylcyclohexane and alkalinities compounds from mixtures and/or purification by distillation, as well as during storage and transportation

The invention relates to a method for inhibiting the polymerization of unsaturated hydrocarbons on the basis of 2,2',6,6'-tetramethyl-4-oxopiperidin-1-oxyl

The invention relates to derivatives of 3-(piperidinyl-1)-chroman-5,7-diol and 1-(4-hydroxyphenyl)-2-(piperidinyl-1)alkanol General formula I or their pharmaceutically acceptable salts accession acid, in which (a) R2and R5taken individually and R1, R2, R3and R4independently represent hydrogen, (C1-C6)-alkyl, halogen, HE or or7and R5represents methyl; or (b) R2and R5taken together form a ring chroman-4-ol, a R1, R3and R4each independently represent hydrogen, (C1-C6)-alkyl, halogen, HE or or7; R7represents methyl; and R6represents a substituted piperidinyl or 8-azabicyclo[3,2,1]octenidine derived; provided that (a) if R2and R5taken separately, at least one of R1, R2, R3and R4is not hydrogen; and (b) if R2and R5taken together, at least one of R1, R3and R4is not hydrogen, with the property that the NMDA antagonist

The invention relates to derivatives of piperidine derivatives, process for their preparation, containing their pharmaceutical compositions and their use in medicine

The invention relates to an improved process for the preparation of TRANS-cyclohexanediol-1.2 and its alkyl derivatives, which are used in the chemical industry

The invention relates to the preparation of heterogeneous catalysts used in the processes of oxidative chlorination of hydrocarbons
The invention relates to methods of producing catalysts for the polymerization of butadiene and may find application in the production of CIS-1,4-polybutadiene in the synthetic rubber industry
The invention relates to the production of catalysts, in particular to a method for the catalytic hydrogenation of benzene and alkylaromatic hydrocarbons in the raw mixes with the mixture of sulfur-containing compounds that can be used in the petrochemical industry, for example in processes of dearomatization diesel fuel
The invention relates to the production of a solution based on iridium, as well as to use it as a catalyst

The invention relates to catalytic chemistry, in particular the production of complex cobalt containing catalyst for the polymerization of butadiene-1,3

The invention relates to an improved process for the preparation of similarcanadian, which is the industrial catalysts for isomerization of dehydrolinalool in citral is the most important natural terpenoid, which is widely used in perfumery, cosmetics and in the production of vitamins a and E
The invention relates to the production of a solution based on iridium, and also to its use as a catalyst

The invention relates to catalytic chemistry, in particular to the preparation of catalysts for Hydrotreating of crude oil, and can be used in the refining industry
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