How hydrocyclone of olefins to olefin oxides by using a catalyst based on oxidized gold

 

(57) Abstract:

This invention relates to a method of hydrocyclone olefins with getting oxides of olefins having three or more carbon atoms, such as propylene oxide, and a catalyst for oxidation of olefins and method of its production. How hydrocyclone olefins comprises contacting the olefin with oxygen in the reaction conditions in the presence of hydrogen and of a catalyst containing oxidized gold on such a carrier, preferably a carrier having a many types of coordination sphere of titanium, such as titanium, grafted on titanosilicate, with more than 30 mass% of gold, based on the total amount of gold present in the catalyst, is oxidized gold. The olefin oxides are used alkoxysilane alcohols with obtaining polyester polyols, and also as intermediate products in the production of alkalophile and alkanolamines. The technical result is an increase in the selectivity with respect to the olefin oxide with good conversion of the olefin, as well as increased service life of the catalyst. 4 N. and 33 C.p. f-crystals, 5 PL.

This invention relates to a method and to catalystic as propylene oxide.

Oxides of olefins, such as propylene oxide, are used alkoxysilane alcohols with obtaining polyester polyols, which are widely used in the manufacture of polyurethanes and synthetic elastomers. The olefin oxides are also important intermediate products in the production of alkalophile, such as propylene glycol, and alkanolamines, such as isopropanolamine, which are used as solvents and surfactants.

The propylene oxide commercially get through widely known chlorohydrin method, in which propylene interacts with the aqueous solution of chlorine with a mixture of propylenglykol. Chlorhydrin dihydrochloride excess alkali with obtaining propylene oxide. The disadvantage of this method is the formation of the dilute salt stream (see K. Weissermel and H. J. Agra, Industrial Organic Chemistry, 2nd ed., VCH Publishers. Inc., New York, NY/ 1993, pp. 264-265).

Another well-known way of getting olefin oxides based on the transfer of the oxygen atom of the organic hydroperoxide or peroxycarbonates acid to the olefin. In the first stage of this journey, oxylene source of peroxide, such as isobutane, ethylbenzene or acetaldehyd algebrabased or peracetic acid. Peroxide is used to epoxidation of olefin, usually in the presence of a catalyst based on a transition metal, including titanium, vanadium, molybdenum and other compounds or complexes of metals. Along with obtaining the olefin oxide, this method is undesirable formation of equimolar quantities of by-product, for example alcohol, such as tert-butanol or methylphenylcarbinol, or acids, such as acetic acid. By-products, such as tert-butanol and acetic acid, must be regenerated or their cost must be factored into the market price. Other by-products must be further converted to products having a commercial value; for example, methylphenylcarbinol should be digidrirovanny obtaining styrene. (Industrial Organic Chemistry, ibid., pp. 265-269).

Recently reported on the direct oxidation of olefins, such as propylene, oxygen in the presence of hydrogen and catalyst to obtain olefin oxides, such as propylene oxide, as shown in EP-A1-0709360. Indicates that the catalyst consists of ultra-fine particles of metallic gold deposited on titanium dioxide, preferably the crystalline phase of anatase. The disadvantage is a short time, LM is Yunosti relative to the olefin oxide and a high degree of water formation.

There are other ways of hydrocyclone, for example as described in international patent publications WO 98/00413 and WO 98/00415, where the olefin, such as propylene, reacts with oxygen in the presence of hydrogen and of a catalyst containing gold, deposited on titanosilicate media, or gold, supported on a carrier containing disordered phase titanium dispersed on silica. In international patent publication WO 98/00414 described a similar way, where the catalyst contains gold and the promoting metal, such as metal of group I, group II, or rare earth metal of the lanthanide deposited on a titanium containing media. The catalysts of these links have a longer life time and better efficiency of hydrogen at a comparable selectivity to olefin in comparison with the catalyst according to EP-A1-0709360. The catalyst WO 98/00414 also has a higher activity than the catalyst according to EP-A1-0709360. However, there is still a need to increase the activity, lifetime and hydrogen efficiency of the catalysts.

This invention relates to a new method of hydrocyclone with obtaining the olefin oxide directly from the olefin and oxygen in presslondon in the presence of hydrogen and in the presence of a catalyst under conditions sufficient to obtain the corresponding olefin oxide. The particular catalyst used in the method according to this invention, includes oxidized gold deposited on a titanium containing media. The term "oxidized gold means that the gold is in the form of a non-metallic gold, i.e. gold is in one or more States with a positive oxidation state greater than 0. To determine whether oxidized gold can be used any modern analytical method (for example, rentgenofotoelektronnoj spectroscopy) or the combination of analytical methods.

The new method according to this invention is used to obtain the olefin oxide directly from oxygen and olefin having three or more carbon atoms. Unexpectedly, the method according to this invention at high temperatures and for an extended period of time gives the olefin oxide with high activity and selectivity. According to the method of this invention, the products of partial or complete oxidation, such as acrolein and carbon dioxide, are formed in small quantities. It is important that the method according to this invention can be carried out at higher temperatures than described peraturan has the advantage of that gives additional source of steam due to the heat produced. Therefore, the method according to this invention can be included in the General scheme of the enterprise, where the heat produced by the steam, is used in additional processes, for example, separation of olefin oxides from the water, and the water is a by-product gidrokhimicheskogo process. Even more importantly, in the preferred embodiments of the method according to this invention, the effectiveness of hydrogen, calculated as the molar ratio of water to the obtained olefin oxide is significantly improved compared with the methods previously known in this field. In preferred embodiments, for example, the molar ratio of water to olefin oxide is lower than about 10:1, can be achieved over an extended period of time at high operating temperatures. Even more importantly, in the preferred embodiments of the method achieves the improvement of the conversion of the olefin with a small decontamination during a period of at least about 100 hours Most importantly, the method can be carried out using small amounts of gold compared to the methods described previously in this area.

In another aspect, Noah on such media. As noted here previously, oxidized gold represents a non-metallic gold, i.e. gold is characterized by one or more oxidation States higher than 0.

The new composition of this invention can be effectively used in the above method hydrocyclone, where olefin having three or more carbon atoms, is converted to the corresponding olefin oxide. In preferred embodiments, in addition to activity and high selectivity to olefin oxide, a new catalyst according to this invention allows to use hydrogen more efficiently and has a significantly longer service life compared with the catalysts known in this field. In addition, the catalyst according to this invention achieves this high level of performance at operating temperatures that are higher than those used in previously known methods. Work at higher temperatures allows to have an additional source of steam for conduct related or subsequent processes. As an additional advantage, the catalyst according to this invention can operate at a lower load of gold compared with the previously known method is th catalyst has very desirable properties to effect the oxidation of propylene and higher olefins to their corresponding olefin oxides.

In one preferred embodiment, the catalyst according to this invention can be easily obtained by the methods of impregnation, which greatly simplify the commercial getting compared to previously known methods of getting in this area, including drawing deposition. Method of treatment has the advantage that avoids manipulation of large amounts of gold-bearing fluids and the need for careful control of pH.

A new way of hydrocyclone this invention involves contacting the olefin containing three or more carbon atoms, with oxygen in the presence of hydrogen and catalyst for epoxidation in process conditions sufficient to obtain the corresponding olefin oxide. Optionally, the method can be used diluent. The relative molar amounts of olefin, oxygen, hydrogen, and optional diluent can be any that are sufficient to obtain the desired olefin oxide. In the preferred embodiment of this invention, the olefin is a C3-12olefin, and it is converted into the corresponding oxide WITH3-12the olefin. In another preferred embodiment, used is In the most preferred embodiment, olefin is a propylene and an olefin oxide is a propylene oxide.

A new catalyst that is used in the epoxidation process according to this invention, contains oxidized gold dispersed on titanium containing media. Oxidized gold is characterized in that it has a positive oxidation state or combination of positive oxidation States higher than 0. In other words, oxidized gold is a metallic gold. The person skilled in the art will understand that the metallic gold (or elemental gold) has an oxidation number of 0.

In the preferred embodiment, such a carrier containing titanium, grafted on titanosilicate, as detailed here below. In another preferred embodiment of such a carrier containing titanium dispersed on a carrier obtained by a method comprising dispersing titanium containing monomer, dimer, polymer, or a mixture thereof on the media. In another preferred embodiment of such a carrier containing titanium dispersed on silica obtained by a method comprising dispersing the monomer titanium oxide-silicon dimer, polymer clay is a s possible the presence of oxidized gold put on the amount of titanium dioxide.

In another preferred embodiment, the catalyst further comprises a promoting metal, which is defined as any metal or metal ion, which enhances the action of the catalyst. More preferably, the promoting metal selected from silver, elements of group I, group II, lanthanide and rare earth actinide elements of the Periodic table, as described in the CRC Handbook of Chemistry and Physics, 75thed., CRC Press, 1994. In another preferred embodiment of such a media receiving method comprising dispersing a mixture containing the alkoxide promoting metal and an alkoxide of titanium, silicon dioxide.

In the method according to this invention can be used any olefins containing three or more carbon atoms, or a mixture of such olefins. Suitable are monoolefinic, which are compounds containing two or more olefinic communication, such as diene. The olefin can be a simple hydrocarbons containing only carbon and hydrogen atoms; or alternatively, the olefin may be substituted on any carbon atoms of the inert Deputy. The term "inert", as used here, denotes replace the local substituents include, but not limited to, the group of halogen, simple ester, complex ester, alcohol, and an aromatic group; preferably chlorine, a simple C1-12essential, complex C1-12ethereal and C1-12alcohol and C1-12 aromatic group. Non-limiting examples of olefins which are suitable in the method according to this invention include propylene, 1-butene, 2-butene, 2-methylpropene, 1-penten, 2-penten, 2-methyl-1-butene, 2-methyl-2-butene, 1-hexene, 2-hexene, 3-hexene and, similarly, the various isomers of methylpentene, ethylbutane, Heptene, methylhexane, ethylpentane, propylbetaine, octene, including, preferably, 1-octene, and other higher analogues; as well as butadiene, cyclopentadiene, Dicyclopentadiene, styrene, -methylsterol, divinylbenzene, allyl alcohol, allyl ether, arelatively ether, allylmalonate, ZIOC scientists, Olivenza, allergenicity ether, arylpropionic ether and allylanisole. Preferably the olefin is an unsubstituted or substituted C3-12olefin, more preferably represents an unsubstituted or substituted C3-8olefin. Most preferably, the olefin is a propylene. Many of the previously mentioned olefins are commercially available; others moonsamy olefins can vary widely, provided in the process receive the corresponding olefin oxide. Typically, the amount of olefin depends on the specific characteristics of the method, including, for example, the device of the reactor, particularly of the olefin and the issues of economy and safety. Professionals in this field know how to determine the appropriate level concentrations of olefins for the specific characteristics of the method. In the light of the present description, the amount of olefin is usually more than 1, preferably more than 10 and more preferably more than 20 molar percent, relative to the total molar number of the olefin, oxygen, hydrogen, and optional diluent. Generally, the amount of olefin is less than 99, preferably less than 85, and more preferably less than 70 molar percent, relative to the total molar number of the olefin, oxygen, hydrogen, and optional diluent.

In the method according to this invention also requires the participation of oxygen. Any source of oxygen is acceptable, including air or substantially pure molecular oxygen. Other sources of oxygen may be acceptable, including ozone and oxides of nitrogen such as nitrous oxide. Molecular oxygen is preferably what is sufficient to obtain the desired olefin oxide. Typically, the number of moles of oxygen per mole of olefin used on the input stream, is less than 1. Preferably the amount of oxygen is more than 0.01, more preferably more than 1 and most preferably more than 5 molar percent, relative to the total molar number of the olefin, oxygen, hydrogen, and optional diluent. Preferably the amount of oxygen is less than 30, more preferably less than 25 and most preferably less than 20 mole percent, relative to the total molar number of the olefin, oxygen, hydrogen, and optional diluent. The oxygen concentration of more than about 20 mole percent can get into the area of the fire to a mixture of the olefin-hydrogen-oxygen.

In the method according to this invention is also necessary hydrogen. In the absence of hydrogen the catalyst is greatly reduced. In the method according to this invention can be used hydrogen of any origin, including, for example, molecular hydrogen, obtained by dehydration of hydrocarbons and alcohols. In an alternate embodiment according to this invention, hydrogen can be produced in situ in the reactor for the oxidation of olefins, e.g. by dehydrogenation alkantpan to obtain complex catalyst-hydride or complex catalyst is hydrogen, who can provide the necessary for the process of hydrogen.

The method can be used any number of hydrogen provided that number is sufficient to obtain the olefin oxide. Suitable amounts of hydrogen are usually more than 0.01, preferably more than 0.1, and more preferably more than 3 molar percent, relative to the total molar number of the olefin, oxygen, hydrogen, and optional diluent. Suitable amounts of hydrogen are usually less than 50, preferably less than 30 and more preferably less than 20 mole percent, relative to the total molar number of the olefin, oxygen, hydrogen, and optional diluent.

In addition to the above reagents may be desirable to use together with reagents diluent, although its use is not mandatory. Since the process according to this invention is exothermic, the diluent is convenient to use as a means of removal and dissipation of the heat. In addition, the diluent provides in the extended area of concentration mode, in which the reagents will not be able to fire. The diluent can be any gas's actions will depend on the way which process takes place. For example, if the process is carried out in the gas phase, then suitable gaseous diluent include, but are not limited to, helium, nitrogen, argon, methane, carbon dioxide, steam, and mixtures thereof. Most of these gases are essentially inert with respect to the method according to this invention. If the process is carried out in the liquid phase, then the diluent can be any liquid that is resistant to oxidation and thermally stable. Examples of suitable liquid diluents include aliphatic alcohols, preferably C1-10aliphatic alcohols, such as methanol and tert-butanol; chlorinated aliphatic alcohols, preferably chlorinated C1-10the alkanols, such as chloropropanol; chlorinated hydrocarbons, preferably chlorinated C1-10hydrocarbons, such as dichloroethane, and chlorinated benzenes, including chlorobenzene and dichlorobenzene; aromatic hydrocarbons, preferably C6-15aromatic hydrocarbons, such as benzene, toluene and Kilani; ethers, preferably2-20ethers, including tetrahydrofuran and dioxane; and liquid polyethers, polyesters, and polyalcohol.

If the diluent done more than 15 molar percent, relative to the total molar number of the olefin, oxygen, hydrogen, and optional diluent. If a diluent is used in the gas phase, the amount of diluent is typically less than 90, preferably less than 80 and more preferably less than 70 molar percent, relative to the total molar number of the olefin, oxygen, hydrogen, and optional diluent. If you are using liquid diluent (or solvent) in the liquid phase, the amount of liquid diluent (or solvent) is usually more than 0 and more preferably 5 mass%, relative to the total molar number of the olefin, oxygen, hydrogen, and optional diluent. When a liquid diluent is used in the liquid phase, the amount of liquid diluent is typically less than 99 and preferably less than 95 mass%, relative to the total molar number of the olefin and diluent.

The concentration of olefin, oxygen, hydrogen and diluent described herein above, are determined appropriately device of the reactor and process parameters described herein. Specialists in this field will understand that the concentration differing from those described herein may be suitable for use with other reslut in gidroksilaminom the method according to this invention, contains gold on titanium containing medium and is characterized by the fact that gold is present in the form of oxidized gold, or, in other words, in the form of a non-metallic gold. Oxidized gold is defined as any(s) type(s) of gold, having(s) oxidation state or combination of oxidation States greater than 0. Can be used any modern analytical method that determines the degree of oxidation of the gold or its relative amount, including, for example, rentgenofotoelektronnoj spectroscopy (RFS). Data RFU can be obtained on the device Kratos Axis 165 of the RFU or the device PHI 5400 RFU, using the characteristics and conditions mentioned herein below, or any similar device. In some embodiments of the catalyst, in particular, where there are organic ligands, x-rays can cause the recovery of parts of oxidized gold. Given this fact, the percentage of oxidized gold as measured by the RFU may be lower than the actual percentage content of the catalyst. In addition to the RFU, to analyze the presence or absence of metallic gold particles can be used in high-performance (high-resolution) transmission electron microscopy (VE-TEM). Dlya permission “from point to point” 2 or more resolution. Scattering by Mie (Mie Acattering) measured the diffusion reflective spectrometer in the UV-visible region (UV-VIS DRS), for example, DRS model UV-RS, scanning the area of 525 nm, can also be used to analyze the presence or absence of metallic gold. When the catalyst is essentially white or lightly colored, in the field of scattering on Mi essentially not observed peaks above background levels, or, for the most part, you can observe the very weak peaks. These observations are consistent with the absence or low presence of metallic gold. Elemental analysis for gold can confirm the presence of gold and, indirectly, oxidized gold, if other methods do not detect the presence of particles of metallic gold. Preferably the oxidation state of gold varies from more than 0 to about +3. On the contrary, metallic gold has an oxidation number of 0.

Usually oxidized gold is more than 30 percent by weight of the total gold content. Preferably oxidized gold is more than 50 percent and more preferably greater than 70 percent, relative to the total gold content. In one of the most preferred embodiments, Catalunya gold is oxidized. In other preferred embodiments, the catalyst includes more than 95 weight percent of oxidized gold.

If there is metallic gold, there is no limit on the absolute number or the size of the particles; however, the usual and preferred amounts of the oxidized gold relative to metallic gold were specified here above.

Usually, the average particle size of the metal gold, if present, is less than 150 nm, more typically less than 50 nm, as measured using a VE-TEM. In the preferred embodiment essentially metallic gold is not present, which, as it turns out, was correlated with better efficiency for hydrogen (low molar ratio of water to olefin oxide) in the process of hydrocyclone. When the catalyst essentially contains no metal gold and the media is white, the catalyst is usually white or slightly colored.

Load media gold can be in any amount that provides an active catalyst in the method according to this invention. Usually, the load of gold more than about of 0.001 weight percent (10 parts per million), preferably greater than 0.005 and more preferably more sustained fashion than less than 10 and more preferably less than 5,0 mass percent, relative to the total weight of the catalyst. In one preferred embodiment of the method mainly carried out at a load of gold is less than 0.5 mass%, more preferably less than 0.1 mass percent.

Such a medium may take many forms. Preferably the titanium on the carrier exists in the form of essentially non-metallic titanium. The media itself can be any substance, for example, to which titanium can be attached, including amorphous or crystalline silicates, such as silicalite or MSM-41; aluminium oxides; metroselect, such as aluminosilicate and titanosilicates; silicates of metals promoters, such as the silicates of elements of groups I and II, and lanthanide and actinide elements; and other refractory oxides and similar materials media. Still other such media that are appropriate for gidrokhimicheskogo the method according to this invention include porous crystalline titanosilicates, known in the art, such as TS-1, TS-2, Ti-beta, Ti-MCM-41 and Ti-MCM-48, and stoichiometric and non-stoichiometric titanates promoting metals. The titanates promoting metals can also be crystal is nudnyh metals. Preferably titanates metal promoters selected from magnesium titanate, calcium titanate, barium titanate, strontium titanate, sodium titanate, potassium titanate and titanate erbium, lutetium, thorium, and uranium. As an additional alternative, non-crystalline and crystalline titanium oxides, including anatase, rutile and brugidou phase of titanium dioxide, may be acceptable for use as a titanium containing media.

Such media may be crystalline, quasicrystalline or amorphous, and may include regular or irregular arrangement of unbound or interconnected micropores and/or mesopores. As it is used here, the term "micropore" refers to the pore diameter (or critical dimension, as in the case of non-circular perpendicular cross-section), in the range of 4 to 20, whereas the term "mesopores" refers to the pore diameter or critical dimension, in the range of more than 20 to 500.

In cases where titanium is attached to the carrier, the load on the titanium can be any, which gives increased activity of the catalyst in the method according to this invention. Typically, the titanium content is bol is the load on the titanium is less than 20 mass% and preferably less than 10 mass percent relative to the mass media.

In one preferred embodiment, such a carrier has multiple (two or more) types of coordination sphere of titanium, which leads to a variety of types of titanium. The coordination environment refers to the number of links and geometry relations with titanium. In the case of titanosilicates types of coordination environments may include a frame and nececery titanium. For clarification, crystalline titanosilicate has a three-dimensional structure, known as "the cage" constructed of tetrahedra SiO4where each oxygen atom forms a bridge between two silicon atoms. Frame titanium is defined as the titanium atom, which replaced the frame silicon atom. On the contrary, nececery Titan is defined as the atom/ion titanium, which is attached to the frame usually through an oxygen bridge. There are no restrictions on the way nececery titanium attached to the frame. Any type of binding, varying from very weak interactions (weak Coulomb interaction) to a fully coordinated (attached or grafted) links is acceptable. Thus, it can be considered done, dispersed and grafted model. A full description of suitable interaction is ozinger, and J. Weitkamp, eds., VCH Veriagsgesellschaft mbH, Weinheim, Germany, 1997, pp. 264-286. On the other hand, titanium is preferred media, whether framed or nececery titanium, has no restrictions in coordination at a specific site until such time as there are many areas of coordination. Coordination, such as tetrahedral, trigonal-bipyramidal, square pyramidal, octahedral and distorted variations are acceptable. The condition of many types of coordination may also be satisfied when there are two or more variations of the same coordination, for example, two different types of tetrahedral coordination, as determined using the analytical methods described below. Non-limiting examples of media containing nececery and, optionally, frame titanium include titanium dioxide (or other discrete titanium containing composition), occluded in the material medium, such as a framework silicate or metroselect (for example, titanosilicate); titanium, is applied in the form of ions or ion clusters on material media, such as frame refractory oxide or metroselect (for example, titanosilicate); and titanium, preferably nececery titanium grafted on frame struckby modified titanosilicate, which is the most preferred of such media in the method according to this invention. This modified titanosilicate contains quasi-crystalline product with the MFI structure, as determined using x-ray diffraction (XRD), and has many kinds of titanium, as defined, for example, DRL and/or US-VIS DRS. At least one kind of titanium is, apparently, titanium frame; at least one other type of titanium, apparently, is grafted titanium, although this assumption is in any case does not limit the composition or method according to this invention.

The atomic ratio of silicon to titanium (Si:Ti) in titanosilicates media can be any ratio that provides active and selective epoxidation catalyst in the method according to this invention. As a rule, pre-emptive atomic ratio of Si:Ti is equal to or greater than about 5:1, preferably equal to or greater than about 10:1. As a rule, pre-emptive atomic ratio of Si:Ti equal to or less than about 500:1, preferably equal to or less than about 100:1.

Synthesis of new modified titanosilicates in some aspects is similar to the receiving TS-1, which apisai more kinds of titanium. As with similar schemes, the reaction mixture comprises water, a source of titanium, a source of silica and template reagent in the form of amino compounds or Quaternary ammonium compounds. Almost all sources of silica are suitable, including tetrachlorozincate, preferably tetraethylorthosilicate, or common fine or deposited silicon oxides, but it is preferable that the silicon oxide does not contain sodium ions. The source of titanium is any hydrolyzable compound of titanium, preferably selected from Tetra(alkoxides) titanium, more preferably Tetra(ethoxide) titanium, Tetra(n-butoxide) titanium or Tetra(isopropoxide) titanium; and from tetrachloride titanium, preferably titanium tetrachloride; and from oxyhalogenation titanium, such as titanium oxychloride. Another source of titanium and silicon oxide can be mixed titanium and silicon compounds, such as titanium or titanium dioxide deposited on silicon dioxide, or sagely silicon dioxide and titanium dioxide. Trialkylamine represents preferably three(C1-15alkyl)amine, such as triethylamine, Tripropylamine and three(n-butyl)amine. Quaternary ammonium compounds may be hydroxide(propyl)ammonium, hydroxide, Tetra(n-butyl)ammonium and the corresponding halides and the like. In the reaction mixture the molar ratio of silicon to titanium can be in the range from 1:1 to 1000:1, preferably from 10:1 to 200:1 and more preferably from 20:1 to 150:1. The molar ratio of water and silicon may be in the range of from 15:1 to 500:1, preferably from 20:1 to 200:1 and more preferably from 30:1 to 100:1. The molar ratio of reagent - link amine or Quaternary ammonium and silicon can be in the range from 0.1:1 to 4:1 and preferably from 0.4:1 to 1.0:1. In preferred methods of synthesis of the silicon source and the titanium source are mixed and the resulting mixture is cooled to a temperature of between 0 and-6S, preferably-4C. The cooled mixture was then quickly added, usually without stirring, cooled in a similar way, the solution containing the reagent. The temperature of the resulting reaction mixture then increase and the reaction allowed to proceed at hydrothermal conditions, more specifically in an autoclave at a temperature between 110 and 2200With under autogenous pressure for a time ranging from 1 day to 10 days. Alternatively, the synthesis can be conducted at atmospheric pressure and at a lower temperature, preferably between 70 and 110S, is nnow mixture ultracentrifuging with obtaining a solid product, which can be washed and dried, for example, by freeze drying, to obtain a new titanosilicate product. In another suitable method of separation of the reaction mixture is centrifuged and the liquid obtained by centrifugation, is heated at a temperature in the range from 50 to 110S for releasing fluid from volatile compounds, such as alcohol and amine. The resulting liquid is treated with acid, such as nitric or hydrochloric acid (from 0.01 to 5.0 M) and the precipitate discarded. The fluid is then re-centrifuged to collect new titanosilicate product. In the third method of separation of aqueous suspension of new titanosilicate product can be processed inorganic acid to achieve a pH between 7 and 9; and then treated with acid, the mixture is centrifuged to collect titanosilicates product. The fourth method of allocating includes centrifugation of the reaction mixture to collect solid crystalline substance, which is then washed with acid, for example, from 0.01 to 5.0 M nitric or hydrochloric acid. Flushing, which can be repeated, usually carried out at temperatures between 23 and 90. The solid product collected by any of the recovery methods, usually dried in air at a temperature of between 480 and S within 2 to 12 h to obtain a new modified titanosilicates media according to this invention.

New titanosilicate obtained as described herein above, has an orthorhombic structure MFI-type, as was shown by the powder x-ray. Unlike some known materials TS-1 new titanosilicate contains many kinds of titanium, as shown, for example, using the RFU. One peak RFU is about 460 eV, this titanium refers to nizkolegirovannaja or mind frame titanium. The second peak RFU is about 458 eV and indicates vysokolegirovannye, nececery type titanium. As it seems, the second type is not crystalline titanium dioxide, since it is usually x-ray analysis shows the presence of a volume of titanium dioxide in the material. Alternative types of titanium or a coordination environment can be analyzed using UV-VIS ORS. In this method, one peak is at about 255 nm and indicates the frame or nizkolegirovannyh titanium. At least one peak is more than about 270 nm and indicates vysokolegirovannye nececery titanium. The second type titanium is supposed to be a form of titanium, which is grafted on the frame MFI; however, this assumption should not restrict in any way the invention. Assetscash and nearcash kinds of titanium can vary from 95 mole percent of the frame to about 95 mole percent Nekrassova titanium. May also be present other kinds of titanium frame and/or Nekrassova type. The average size of the crystals of the new substance is usually in the range from 20 nanometers (nm) to 1 micrometer (μm).

Another preferred type of such media includes disordered phase dispergirovannogo titanium on the material of the carrier, preferably silica. Disordered phase titanium does not have an ordered, periodic crystallinity and can be distinguished from ordered (crystalline) phase, such as crystalline titanium dioxide, using one or more modern analytical methods, such as VE-TEM, x-ray and Raman spectroscopy. UV-VIS DRS and edge x-ray absorption spectroscopy structure (XANES) at the edge of the absorption bands of titanium It can also be used to distinguish the disordered phase from an ordered or crystalline phase. Preferred media containing disordered phase titanium described in international patent publication WO 98/00415. More preferably disordered phase titanium also includes a variety of coordination environments of titanium, as defined, for example, with P the carrier is impregnated with a titanium compound at a temperature between 0 and 50 ° C, when the ambient pressure over time within from 30 minutes to 24 hours non-limiting examples of suitable titanium compounds include titanium alkoxides, such as isopropoxide titanium, propoxy titanium, atoxic titanium and piperonyl titanium, titanium sulfate, oxysulfate titanium, titanium halides, preferably chloride titanium; titanium carboxylates, preferably the titanium oxalate and titaniumalloy; and technoorganic halides, such as dichloride of dicyclopentadienyliron and other technoorganic dichloride. A mixture of alkoxides of titanium and alkoxides of metals promoters, preferably alkoxides of alkaline earth metals such as barium alkoxide may also be used. A mixture of alkoxides of titanium and alkoxides of metals promoters, dissolved in a solvent such as alcohol, may be commercially available, for example, by Gelest, Inc., and can be deposited on silicon dioxide. For mixed alkoxides number of alkoxides of titanium and promoters in the solution can vary; thus, atomic or mass ratio of promoter and titanium may vary, if desired. Alternatively, the mixed complexes of titanium-promoting metal, such as Li promoter and titanium are constant and the ratio of promoter and titanium is not changed.

Other titanium compounds, which are suitable for receiving the disordered phase titanium include inorganic and organic titanium containing monomers, dimers and polymers, and polymers based on carbon containing functional groups, such as alkoxides, communicating with titanium ions; they are commercially available, for example, by Gelest, Inc. Non-limiting examples of suitable such polymers based on carbon include poly(dibutyltin) and poly(octile-glycol-titanate).

Preferably compounds of titanium, which are suitable for receiving the disordered phase titanium include inorganic and organic titanium and silicon-containing monomers, dimers and polymers, more preferably containing titanium and silicon dioxide monomers, dimers and polymers. Such substances are widely known in the field of engineering. Organic monomers, dimers and polymers containing titanium, can be any compound, characterized by a main chain containing Si, Ti and the group -(CR2)z- where the groups -(CR2)z- form a bridging connection connecting the Si atoms, Ti atoms or atoms of Si and Ti (e.g.,- Si- (CR2)z-Si, -Ti-(CR2)z-Ti - and-Si- (CRis selected from the groups alkyl, aryl, alkoxy and halogen, preferably groups1-20alkyl, C6-20aryl, C1-20alkoxy and chlorine. Attached to the Si atoms and Ti are organic groups which preferably have the form of lower alkyl and/or CNS groups and/or aryl and/or aryloxy. Similarly, titanosilicates polymer can be any polymer, characterized by a main chain containing atoms of Si, Ti and O. the Oxygen atoms form bridges between adjacent Si atoms, Ti atoms and atoms of Si and Ti (e.g.,- Si-O-Si, -Ti-O-Ti and Si-O-Ti-). The atoms of Si and Ti is attached organic groups, which preferably have the form of lower alkyl and/or CNS groups and/or aryl and/or aryloxy. Titanosilicates polymer may be a linear structure, a branched or cross-linked, and titanium partially cross-linked to silicon through communication-Si-O-Ti-O-Si. Titanosilicate polymers, such as described in US 5759945, are particularly suitable. Of such polymers, such as titanosilicate may be commercially available, for example, by Gelest, Inc. Mixed Ti and Si-containing polymers having as-O-, and -(CR2)zgroups in the main chain, may also be suitable DL is alleny the following formula:

(R1)xTi[O-Si(R2)3-y(R3)y]4-x

where R1, R2and R3each independently selected from the group comprising groups alkyl, alkoxy, aryl, aryloxy and halogen; preferably from groups C1-20alkyl, C1-20alkoxy, C6-20aryl, C6-20aryloxy and chlorine; x is an integer from 0 to 3; y is an integer from 0 to 3. Similarly, the preferred titanium containing dimers and polymers can be represented by the formula shown further here, except that the3can also be selected from the following groups:

[O-Si(R2)3-y(R3)y] and [O-Ti(R2)3-y(R3)y]

where R2, R3and u can have any definition of the above. It should be noted that R3represents the repeating group. If R3repeats once, the formula represents a dimer; if R3repeated two or more times, then the formula is a polymer. Non-limiting examples of suitable such monomers include tetrakis(trimethylsiloxy)titanium, tetrakis(triethylsilane) titanium, tetrakis(triethoxysilane)titanium, tetrakis[Tris(tert-butoxy)siloxy]titanium and things like iltifat.

Other titanium containing compounds that can be suitably impregnated on the carrier with the formation of the disordered phase of titanium include titanium-silsesquioxane complexes described M. Crocker et at. in Chemical Communications, 1997, pp. 2411-2412, and M. Crocker et al. in the patent OS 5750741. In addition, mixtures of any of the above titanium containing compounds, complexes, monomers, dimers and polymers can also be successfully impregnated on a carrier and can be even more preferable to obtain many of the coordination environment of Titan.

The connection of titanium may be applied in pure form from the gas phase or from a solvent in any media.

When using the solvent, it can be anything that dissolves the compound of titanium, including, for example, aliphatic alcohols, aliphatic and aromatic hydrocarbons and water, if necessary. After contacting the original data carrier with a solution containing compound of titanium, the carrier is dried at a temperature of from 0 to 150C, preferably from 50 to 150 C, in vacuum or in a stream of air or inert gas, such as nitrogen, argon or helium. After that, the media can be used without annealing or posleduyushego or helium, at a temperature of from 100 to 1000C, preferably from 100 to 800C.

Any combination or mixture of such carriers described herein above, can be used in the catalyst according to this invention.

Such carriers may be of any form suitable as catalytic particles, such as beads, plates, spheres, honeycombs, monoliths, extrudates and films. Optional, such media can be extruded with the second media associated with him or printed on the second medium for bonding with the catalyst particles and/or improve the strength of the catalyst or resistance to friction. For example, it may be desirable to obtain a thin film of such media on the second carrier that has the form of a bead, plate or die. The second carrier is usually inert in the way, and does not need to contain titanium. Suitable secondary carriers include carbon and any refractory oxide, such as silicon oxide, aluminum oxide, alumosilicate; ceramics, including ceramic carbides and nitrides, as well as any metal media. Usually, the number of the second carrier ranges from 0 to 95 weight percent of atnasio gold on titanium containing media, if only the catalyst shows activity in the process of hydrocyclone according to this invention. Non-limiting examples of suitable methods include obtaining a coating deposition, impregnation, spray drying, ion exchange, deposition from the vapor phase and the interaction of solids with solids. Coating deposition and impregnation are to some degree preferred. In the implementation of the receiving conditions are usually chosen so as to minimize the recovery of oxidized gold to metallic gold. By way of applying the deposition of such media is typically in contact with the solution containing the compound of gold at a temperature and pH sufficient to place the connection oxidized gold to the media. Reaction conditions can vary as a function of several parameters, such as the specific nature of the gold compounds, the concentration of gold compounds in solution, the nature and concentration of other types of ions, such as chloride ions and sodium silicate; specific media, pH, temperature, specific reason and time of contact. By way of impregnation of the carrier is wetted with a solution, suspension or colloid, staroste, as it is desirable. Here you can also vary the conditions of impregnation depending on, for example, particular compounds of gold, its concentration in solution or suspension, the particular carrier and the temperature of the impregnation. The media can be processed by multiple impregnations, if desirable.

Temperature application methods by precipitation and impregnation (or ion-exchange method, if used) is typically in the range from ambient temperature to be taken equal to 21 to 100C, but other temperatures may be found suitable. Any connection gold can be used to obtain a solution or suspension of gold for methods of coating deposition and impregnation or ion-exchange method, if it is used. Non-limiting examples of suitable gold compounds include solitonopodobnogo acid, chloraurate sodium, chloraurate potassium gold cyanide, qualitativeand, acetate, gold, trichloride diethylamin-eurynomos acid, alkylhalogenide gold, preferably alkylchloride gold and aurate alkali metals, such as Aurat lithium Aurat sodium, Aurat potassium, Aurat rubidium and Aurat cesium. Zolotodolinskaya compounds may also be used. Suitable R is, for example, methanol, ethanol and isopropanol), ethers, ketones, and aliphatic and aromatic hydrocarbons. A mixture of water and organic solvents are also acceptable for use. Usually, in the case of both molarity of a solution of a soluble gold compounds is in the range from 0.0001 M to the saturation point of soluble gold compounds, preferably from 0.0005 to 0.5 M When using an aqueous solution containing salts of oxidized gold, the pH of the solution can be increased to any value between 5 and 14, preferably using a base selected from, for example, carbonates, borates, carboxylates, hydroxides, silicates and mixtures thereof. Optionally, the solution may contain cationic and/or anionic additive to positively stabilize the oxidized species of gold, including, for example, some metal ions-promoters (e.g., Li+MD+2and La+3), as well as the halides, sulfates, phosphates, carbonates, borates and carboxylates, such as acetates, lactates, citrates, maleate, cinnamate and mixtures thereof.

For illustrative purposes, shows the synthesis of coating deposition, which is suitable for obtaining the preferred catalytic compositions containing oxidized salads illustration and is not meant to limit the methods of synthesis which can be used to obtain the catalyst according to this invention. Such a carrier is in contact with an aqueous solution of a soluble gold compounds, for example zolotoporfirovoe acid. the pH is usually adjusted to 5-14 any suitable base, such as sodium hydroxide, sodium carbonate, sodium silicate, sodium acetate, potassium carbonate, cesium hydroxide, lithium carbonate, cesium carbonate, rubidium carbonate or a mixture thereof. The pH value is selected to facilitate and preferably optimization of the interaction between ions of gold with the carrier. a pH of more than 7 and less than 14 is preferred. The mixture is stirred in air at a temperature of between 20 and 80 ° C for a time ranging from 1 to 24 hours At the end of this period the solid products was separated, washed with water, and the water optionally contains one or more salts of the promoting metals. Then the solid products are dried at a temperature of between 20 and 120C.

As another illustration shows the synthesis of impregnation, which is suitable for obtaining the preferred catalytic compositions containing oxidized gold on titanium containing media, with many kinds of titanium. And again, consider, Thu is Sitel may be impregnated with an aqueous solution of a soluble gold compounds, for example zolotoporfirovoe acid. the pH is usually adjusted to 5-14 any suitable base, as described above with respect to coating deposition. The pH value greater than 7 and less than 14 is preferred. Alternatively, the impregnating solution can be obtained by using an organic solvent, such as alcohol, or a mixture of water with an organic solvent. The connection of the gold and/or other salt used is not necessarily completely dissolved in the solvent; can be used with suspension. Then the solid is dried in air at a temperature of between 20 and 120C to remove solvent.

Newly synthesized catalyst can be used without further processing. Optional, newly synthesized catalyst may be calcined in air or heated in an inert atmosphere, such as nitrogen. The temperature of annealing/heat depends on the specific sample, but can vary from 100 to 8000C, preferably from 120 to S. Preferably, the temperature is chosen such as to minimize the recovery of oxidized gold to metallic gold. Alternatively, the newly synthesized catalyst may be conditioned before the COI is, including inert gas, such as helium, and, optionally, one or more compounds selected from hydrocarbons (e.g., oxidized olefin, hydrogen and oxygen at a temperature between about ambient adopted equal to 21 and 600C.

Optionally, the catalyst according to this invention may contain the promoting metal or a combination of the promoting metals. Any metal or metal ion, or a combination thereof, which improve the productivity of the catalyst in the oxidation process of this invention can be used as the promoting metal. Factors contributing to improved performance include, but are not limited to, increasing the conversion of the olefin, the increase of selectivity to olefin oxide, the reduced formation of water and increase the service life of the catalyst. Usually the valence promoting (their) ion(s) of metal(s) ranges from +1 to +7, but can also be particles of metals. Non-limiting examples of suitable promoting metals include the metals of groups I-XII of the periodic table and rare earth lanthanides and actinides, as stated in the CRC Handbook of Chemistry and Physics, 75thed., CRC Press, 1994. Preferably the promoting metal is erelli, magnesium, calcium, strontium and barium; lanthanide rare earth metals including cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; and actinide metals, in particular thorium and uranium. More preferably, the promoting metal selected from silver, magnesium, calcium, barium, erbium, lutetium, lithium, sodium, potassium, rubidium, cesium, and combinations thereof. Preferably the promoting metal eliminates palladium and, more preferably, the promoting metal eliminates the metals of group VIII, especially iron, cobalt, Nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum. As used here, the word "exclude" means that the total concentration of the metals of group VIII of less than 0.01 mass percent, preferably less 0.005 mass%, relative to the total amount of catalyst.

If you use one or more of the promoting metals, the total amount of the promoting(s) of metal(s) is usually more than 0.001, preferably more than 0.01 mass%, relative to the total amount of catalyst. The total number of promoting(s) of metal(s) is usually less than 20, preferably less than 15 mass% of the GDP) is to be applied(s) of such carrier concurrently with titanium or alternatively, in a separate step either before or after the titanium. If you are promoting(s) metal(s) may be applied(s) of such carrier concurrently with gold, or, alternatively, in a separate step either before or after deposition of the gold. For discussion purposes, the word "application" includes all methods of deposition by precipitation, ion exchange and impregnation. Alternatively, the promoting metal may be deposited on the preceding form of catalyst prior to addition of titanium or after it is added to or concurrent with the Titan. Usually the promoting metal is applied from aqueous or organic solution or suspension containing the salt of the promoting metal and, optionally, other additives that contribute to the stabilization of the oxidized particles of gold, as described previously. Can be used any salt promoting metal; for example, halides of metals such as fluorides, chlorides and bromides; nitrates, borates, silicates, sulfates, phosphates, carbonates, and carboxylates, in particular acetates, oxalate, cinnamate, lactates, maleate, the citrates. Can be used mixtures of the above salts. When using an organic solvent, it can be any solvent from eticheskie hydrocarbons. Usually the media interacts with the solution of the promoting metal in conditions that are similar to those used when contacting the carrier with a solution of gold. Once applied the promoting metal, rinsing is optional; and if washed, the washing liquid preferably contains a salt of the desired promoting metal. Then annealed in air or heating in an inert gas or air conditioning in the oxidation reactor can optionally be carried out in a manner similar to that previously described for the deposition of gold; however, the process conditions of any treatment carried out after the synthesis of the catalyst, preferably selected in such a way as to minimize the recovery of oxidized gold to metallic gold.

The method according to this invention can be carried out in any standard reactor designs suitable for processes in gaseous or liquid phase. These devices are broadly include the batch reactor, the reactor fixed bed reactor with a transport layer, a reactor with a moving bed reactor fluidized bed reactor with jet stream in a layer, a shell and tube reactor, and protein, hydrogen and oxygen can be brought in contact together. Alternatively, the process may be conducted in stages, with the first catalyst reacts with oxygen, and then the oxidized catalyst is in contact with a mixture of propylene and hydrogen. Preferably the process is carried out in the gas phase, and the reactor has a constructive possibility of heat transfer for the purpose of removal of the heat. Preferred reactors intended for these purposes, include a reactor with a fixed bed, shell and tube reactor, a reactor with a fluidized bed and a reactor with a moving bed, and the batch reactor, the containing many catalytic layers connected in parallel and used in an alternative way.

Conditions for the oxidation process described herein may change significantly during the transition from the regime of non-mode Flammability. It is convenient, however, to know the conditions that allow us to distinguish non-flammable and flammable mixture of olefin, hydrogen and oxygen. Respectively, may be constructed or taken into account the state diagram for the composition, which for any data the temperature and pressure of the process shows the region participated. More preferably the reaction mixture, defined earlier, apparently, are outside mode Flammability, when the process is carried out at the preferred temperatures and pressures defined below. However, the mode Flammability possible, in accordance with the design specialist in this field.

Usually the process is carried out at a temperature which is greater than the ambient temperature is adopted equal to 21, preferably higher than 70, more preferably above 130C. Usually the process is carried out at a temperature below 300, preferably below S. Typically, the pressure ranges from about atmospheric to 400 psig (2758 kPa), preferably from 100 psig (690 kPa) to 300 psig (2069 kPa).

In flow reactors, the residence time of the reactants and the molar ratio of the reactants and catalyst is defined as the volumetric rate. For the process in the gas phase volumetric rate of gas per hour (GHSV) for olefin can vary in a wide range, but usually it is more than 10 ml of olefin per ml catalyst per hour (h-1), preferably more than 100 h-1and more preferably more than 1000 h-1. Biteline less than 20000 h-1. Also for the process in the gas phase total volume srednica gas flow rate (GHSV) for the input flow can be varied in a wide range, but usually it is more than 10 ml of gas per ml of catalyst per hour (h-1), preferably more than 100 h-1and more preferably more than 1000 h-1. Usually GHSV input flow is less than 50000 h-1preferably less than 35000 h-1and more preferably less than 20000 h-1. Similarly, for the process in the liquid phase mass srednica feed rate (WHSV) of olefinic component can vary in a wide range, but usually it is more than 0.01 g of the olefin on g catalyst per hour (h-1), preferably more than 0.05 h-1and more preferably more than 0.1 h-1. Typically, the WHSV of the olefin is less than 100 h-1preferably less than 50 h-1and more preferably less than 20 h-1. Gas and mass velocity per hour of components oxygen, hydrogen and diluent can be determined by the rate of olefin, taking into account the desired relative molar ratio.

When the olefin having at least three carbon atoms, in contact with the oxygen in prison output. The preferred olefin oxide is propylene oxide.

Conversion of olefin in the method of this invention can vary depending on the specific conditions of the method used, including the specific olefin, temperature, pressure, molar ratio and catalyst. For the purposes of this invention, the term "conversion" refers to the number of mole percent of the olefin, which interacts with the formation of products. Usually achieved conversion of the olefin of more than 0.25 mole percent. Preferably the conversion of the olefin is greater than 1.0 mole percent, more preferably more than 1.5 mole percent and most preferably greater than 2.0 mole percent.

The selectivity to olefin oxide may vary depending on the specific conditions used. For the purposes of this invention, the term "selectivity" is defined as the amount in mole percent of unreacted olefin, which forms a specific product, preferably the olefin oxide. In the method according to this invention have the olefin oxides with unexpectedly high selectivity. Typically, the selectivity to olefin oxide more than 70, more preferably 80 or more the guide of propylene oxide per kilogram of catalyst per hour (g PO/kg cat-h) depends on the specific catalyst and the process conditions, such as temperature, pressure and flow rate. Performance is usually more than 30 g PO/kg cat-h, more preferably 50 g PO/kg cat-h, and more preferably more than 100 g PO/kg cat-h

The efficiency of hydrogen in the method according to this invention is favorably high. More specifically, the molar ratio of water: olefin oxide is typically more than about 1:1, but less than about 30:1 and preferably less than about 10:1.

In preferred embodiments, the catalyst of this invention gives evidence of his superior long life. The term "life" as it is used here, refers to the time specified from the start of the oxidation process to the moment when the catalyst after regeneration is so lost activity that it becomes useless as a catalyst, in particular useless for commercial use. As proof long life is that the catalyst remains active for a long service life with low decontamination. Usually in the reactor with a fixed bed is achieved duration of work more than 40 hours without deactivation of the catalyst. Preferably can be postign the catalyst according to this invention operates 400 h with a small decontamination. The preferred length between regenerations will depend on the reactor design and can vary from minutes to reactors with the transport layer up to several months for a reactor with a fixed bed.

When its activity is reduced to an unacceptably low level, in preferred embodiments, the catalyst according to this invention can be easily regenerated. Any method of regeneration of the catalyst, known generally specialists in this field can be used for the catalysts according to this invention, provided that the reactivated catalyst with respect to the described here is oxidation. One suitable regeneration method includes heating the deactivated catalyst at a temperature of from 150 to 500 ° C in an atmosphere of a regeneration gas containing oxygen, hydrogen, hydrogen, or mixtures thereof, and, optionally, an inert gas. The preferred regeneration temperature is between 200 and 400C. The amount of oxygen, hydrogen and/or water in the regeneration gas may be any, such that effectively regenerates the catalyst. Preferably oxygen, hydrogen or water is from 2 to 100 mole percent of the regeneration gas. The approach which the gas is recovered, can vary from as short as 2 min, before long, such as several hours, for example, 20 h at low temperature regeneration.

The invention will be further clarified by considering the following examples, which are intended only for examples of using the present invention. Other embodiments of the invention will become clear to experts in this area from consideration of this specification or practice of the invention, as described here. If not stated otherwise, all percentages are given in mole percent.

X-ray photoelectron spectra presented in the examples, is usually received on the device Kratos Axis 165 or PHI 5400 XPS. Usually the operating parameters of the device Kratos Axis were the following: the x-ray source, Monochromatic A1 Ka (210 watt, 14 kV, 15 mA; Analyzer Pass Energy of 80 eV (the investigated range), 20 or 40 eV (range, high resolution); the spread Angle, 90; lenses, hybrid; Aperture, the slot (310 mm) for samples on carbon tape and a diameter of 2 mm for samples on Al-holder; Aperture, 50; Analyzed area (16-84 interest unit level), 600 (x) x 220 (y), uncalibrated, 1.5 mm in diameter, and conditions Flood Gun current thread carrier, 2.0 a; the balance of the charge of 3.25 In; the 15 kV, 15 mA; Analyzer Pass Energy, 89 eV (the investigated range), 17,8 eV (range, high resolution); the spread Angle, 45; lenses, 3:1 zoom, Aperture, slot (103 mm) (31 mm of the analyzed area); Aperture, 50; Flood Gun is not used. Samples were obtained either by spreading powdered sample on a double-sided conductive carbon tape, or by pressing the powdered sample into blind holes (3 mm diameter) in an aluminum sample holders. Spectra were recorded in the areas spectra of the Si(2p) and Au(4f). The spectrum of the Si(2p) was used to calibrate the energy scale of the binding for calculation of surface electric charge that is induced in the analysis process. Gold volume gives line 4f at 84,0 and 87.7 eV with theoretical intensity ratio 7:2 and 5:2 spin-orbit doublet of 4:3.

Example 1

Crystals titanosilicate nanometer size were obtained using tetraethylorthosilicate (TEOS), n-piperonyl titanium hydroxide of tetrapropylammonium (TRON), in an aqueous reaction mixture containing the following molar composition: 1,0 SiO2; 0,015 Tio2; 35 H2O; 0,33 TRA. With vigorous stirring into a solution TRAON (20 mass%) was added to a solution containing TEOS and isopropanol was slowly added a solution of Tetra(n-piperonyl) titanium in dry isopropyl alcohol (ratio 1:5). A clear solution was stirred for 1 h, then was slowly added to a chilled deionized water. The reaction mixture was stirred in a sealed autoclave under stirring at C under autogenous pressure for 4 days. The crystalline solid product was isolated by centrifugation at 2000 rpm for 3 hours, the Crystalline solid product washed twice with hydrochloric acid (0.1 M), washed with deionized water and dried at 70 C for 2 h and Then the solid product was annealed at C in air for 8 hours Product titanosilicate containing orthorhombic crystals with an average size of 100 nm, as measured by THOSE with structure type MFI, as determined using the x-ray powder. The presence of titanium dioxide was not detected. The atomic ratio of Si:Ti equal to 90:1, Ti-RAF shows two peaks of titanium, 460 and 458 eV, interpreted as 81 percent of low coordination (frame) and 19 percent of high coordination (grafted) titanium, respectively.

When mixing of the upper layer was added solitonopodobnogo acid (HAuCl4·3H2d, 0,171 g) in deionized water (171 ml). The obtained yellow solution was heated on a water bath until S (pH 2,4). The pH value was brought the th, and the measured pH value was $ 8,97. In the solution under stirring was added magnesium nitrate (0,236 g), after which the pH of the solution after 5 min was equal to 8.6. The stirring was stopped, and the beaker containing the solution was placed in a cold water bath for 20 minutes Measured at 24C pH of the solution was equal 9,12. Thus obtained titanosilicate (5 g) was added to the gold solution under intensive stirring of the upper layer. The suspension was stirred for 2 h; measured pH was equal to 8,29.

The solid products were filtered and washed with deionized water (185 ml). Then the solid products were progulivali as follows: heated in a stream of air at a temperature of from room temperature up to 110S for 30 min and kept at 110S for 12 hours, heated from 110 to 700C for 5 h and kept at 7000C for 10 h to obtain a catalyst according to the invention.

The catalyst having a weak pink color around the edges of particles, essentially does not contain any metal of gold, as determined using a VE-TEM. A small peak was observed using scattering on Mi. Gold presents essentially in the form of oxidized gold, as determined using the RFU, in conjunction with VE-TEM. The data of elemental analysis, mass is prohibited by neutron activation analysis (NAA).

The catalyst was tested in hydrocyclone propylene to propylene oxide in the following manner. The catalyst (2 g) were loaded into the flow reactor continuous fixed bed [0.5 inch (12.5 mm) diameter x 12 inches (30 cm) length)] and activated as follows. At 140 C, the catalyst was heated in a helium atmosphere for 5 h, then heated in a stream of propylene and hydrogen for 10 min, then added oxygen. The composition of the stream at the entrance consists of 10 percent hydrogen, 10 percent oxygen and 20 percent propylene, the rest is helium. Propylene, oxygen and helium was used in the form of net flows; hydrogen was mixed with helium in a mixture with a ratio of 20 N2, 80 (V/V). After reaching the constant speed of the propylene oxide product was received within 1 h, the temperature was raised at intervals of 150With up to working. The working pressure was atmospheric. The products were analyzed simultaneously using either gas chromatography (column Chrompack Poraplot S, 25 m), or mass spectrometry.

When 1860C and residence time (reactor) 1,74 (GHSV 2069 h-1and after 68 h in the flow of the catalyst gave a conversion of propylene 1.5 percent, the selectivity towards propylene oxide (PO) 90 percent, prosvetili of titanosilicate nanometer size received, using tetraethylorthosilicate, n-piperonyl titanium compound hydroxide of tetrapropylammonium (TRON) in an aqueous reaction mixture containing a molar composition of the following composition: 1,0 SiCO2; 0,025 TiO2; 36 H2O; 0,235 TRAIN. The reaction mixture was obtained using the initial mixing of tetraethylorthosilicate and n-butoxyaniline in stainless steel tanks in the atmosphere of inert gas, after which they were heated to 80C for 3 hours the mixture and the solution TRAON (40 mass%) was cooled in an ice bath to 50C. With vigorous stirring to a mixture of alkoxides was slowly added a solution TRON with the preparation of a gel. The gel was added chilled deionized water and the gel was heated to room temperature. The gel was kept for 10 h and then loaded into a stainless steel autoclave, which was heated at 160S and a pressure of 300 psig (2068 kPa) for 6 days. After this time, the autoclave was cooled and the contents were centrifuged at 2000 rpm for 3 hours to obtain a translucent white solid product. The solid product was discarded and the fluid from the centrifugation was heated at 80 ° C for 5 h to remove from the liquid ethanol, ostatic is based acid (2M). Formed suspension. The suspension was centrifuged at 2000 rpm for 30 min to obtain white quasi-crystalline solid product. The solid product was dried at 80 ° C for 12 h, then was progulivali at 5500C in air for 8 h with getting titanosilicates media. The product had the appearance of thick plates of irregular shape with an average size of 80 nm, as observed using VE-TEM. Powder x-ray showed orthorhombic structure type MFI. Bulk titanium dioxide was not detected by XRD. The atomic ratio of Si:Ti was 46:1. Ti-RAF showed two peaks of titanium at 460 and 458 eV, interpretirovany as 61 percent titanium low coordination (frame) and 39 percent titanium high coordination (grafted), respectively.

When mixing of the upper layer in deionized water (171 ml) was added solitonopodobnogo acid (0,171 g). Transparent yellow solution having a pH of 2.4, was heated on a water bath to 70 ° C. the pH was brought to 8.6 with sodium carbonate solution (0,5 N.). The solution became colorless. The solution was stirred for 75 min at 70C. The measured pH was 9,03. When adding magnesium nitrate (0,236 g) the pH was changed to 8.64 after 5 minutes the Stirring was stopped and the glass, when remesiana upper layer obtained titanosilicate (5 g) was added to the solution and the resulting mixture was stirred for 2 hours Whenever necessary to maintain pH equal to 8 was added sodium carbonate (0.5 in BC). After 2 h, the measured pH was 8,54 when S. The solid products were filtered and washed with deionized water (185 ml). Solid products were progulivali in accordance with the following procedure: heated in air from room temperature up to 110S for 30 min and kept at 110S for 12 h, then was heated from 110 to 700C for 5 h and kept at 700C for 10 hours to obtain a catalyst according to the invention.

The catalyst had a white color, is not essentially contained metal gold, which was confirmed using a VE-TEM. Was not observed scattering by Mi. Gold was essentially presented in the form of oxidized gold, which was confirmed using the RFU. Elemental analysis by weight: 0,015% AI, 47 percent Si, 1.35 percent Ti, 0,46% Na, and 0.14 percent of CBMs, which was confirmed using NAA.

The catalyst (2 g) was evaluated by gidrookislov propylene to propylene oxide by the method described in example 1. At a temperature of 1920With time and stay 1,71 (GHSV 2105 h-1and after 450 h in the stream, the catalyst gave a conversion of propylene of 1.5%, the selectivity for RO 92 percent, and the performance of 37 g R is="ptx2">

When mixing of the upper layer in deionized water (171 ml) was added solitonopodobnogo acid (0,171 g). Transparent yellow solution was heated on a water bath until S, pH was equal 2,36. the pH was brought to 8.63 sodium carbonate (0.5 in BC). The solution became colorless. The solution was stirred for 80 min at C. The measured pH was equal cent to 8.85. When adding magnesium nitrate (0,237 g) pH changed to 8.64 after 5 min at 71,7 C. the Stirring was stopped and the glass of the solution was kept in a cold water bath for 20 min. Measured at S the pH of the solution was 9,13. When mixing of the upper layer was added titanosilicate (5 g) of example 1 and stirring was continued for 2 hours the pH was equal of 8.37 at 20C. The solid products were filtered and washed with deionized water (185 ml). Solid products were progulivali the method described in example 2, to obtain the catalyst according to this invention. The catalyst was only slightly colored, which pointed to the fact that gold was being oxidized. The catalyst (2 g) was evaluated in hydrocyclone propylene to propylene oxide as described in example 1. When S and time 1,83 (GHSV 1967 h-1and after 21 hours in the stream of the catalyst gave conversione water:RO 3,15:1, and 0.44% RO at the output of the reactor with very little deactivation. At the peak of activity (6 h in the thread), this catalyst showed conversion, equal to 2.6 percent, the selectivity 88.5 percent, productivity, equal to 61 g PO/kg cat-h, the molar ratio of water:RO, equal to 3.7:1, and the mass percentage of RHO at the exit of the reactor 0,54.

Example 4

When mixing of the upper layer in deionized water (171 ml) was added solitonopodobnogo acid (0,171 g). Transparent yellow solution was heated on a water bath to 70 C, pH equal 2,37. the pH was brought to 8.67 aqueous solution of rubidium carbonate (1 BC). The solution became colorless. The solution was stirred for 2 h at S. the pH was equal to 9.1. When adding magnesium nitrate (0,116 g) pH changed to 8,94 after 5 min at 66,1 C. the Stirring was stopped and the glass of solution was placed in a cold water bath for 20 minutes At 17,9 With pH brought to 9,54 solution of rubidium carbonate. When mixing of the upper layer was added titanosilicate (5 g) of example 2. The mixture was stirred for 2 hours Measured pH value was equal to 8.2 at 21,8 C. the Solid products were filtered and washed with deionized water (100 ml). Solid products were progulivali as described in example 2, with receipt shall now Si, 1.22% Ti, 1.6 percent Rb, 0.010 percent, 0,0028% Na. The catalyst had only weak staining, which showed that gold was being oxidized.

The catalyst (2 g) was evaluated by gidrookislov propylene to propylene oxide. At 180C and time of 1.76 (GHSV 2045 h-1and after 120 h in the flow of the catalyst gave a conversion of propylene, 2.5%, while the selectivity for RHO, equal to 91 percent, the performance of 60 g PO/kg cat-h, the molar ratio of water:RO equal 4,0,1, and the mass percentage of RHO at the reactor outlet of 0.53 with a very small decontamination.

The above catalyst (3 g) was evaluated in hydrocyclone propylene to propylene oxide in the reactor under pressure at 230 pounds per square inch (psia) (1586 kPa) supply and 20 percent of propylene, 7.5 percent oxygen and 7.5 percent hydrogen in helium. When 190S and time 2,33 with and after 15 h in the flow of the substance gave a conversion of propylene, equal to 1.8 percent, while RO selectivity equal to 92 percent, and productivity 270 g PO/kg cat-h

Example 5

When mixing of the upper layer in deionized water (85.5 ml) was added solitonopodobnogo acid (0,088 g). Transparent yellow solution was heated on the maintain. The mixture was stirred for 80 min at 69,5 C. pH was equal 9,13. The stirring was stopped and the glass of solution was placed in a bath of cold water. When 23,30With the pH of the solution was equal 9,43. When the upper stirring was added titanosilicate (2.5 g) of example 1 and the resulting mixture was stirred for 2 hours the PH was falling, so I added dropwise addition of the solution of rubidium carbonate, has established a pH value of about 8. The final pH value was 8,31 when S. The solid products were filtered and washed with deionized water (90 ml). Solid products were progulivali in accordance with the method of example 2 to obtain a catalyst according to this invention. Oxidized gold amounted to 46 mass% relative to the total content of gold, which was confirmed using the RFU.

The catalyst (2 g) was evaluated by gidrookislov propylene to propylene oxide as described in example 1. At 180C and time of 1.76 (GHSV 2045 h-1), and after 120 h in the flow of the material was achieved 2.2 percent conversion of propylene at RO selectivity of 90%, the performance of 53 g PO/kg cat-h, molar ratio water:RO, equal to 6.6:1, and 0.46 mass% RO at the reactor outlet.

Note the g) and deionized water (171 ml), additionally diluted with deionized water (other 153.9 ml). Clear light yellow solution was heated on a water bath to 72.7 (pH 2,79). the pH was brought to 8.68 aqueous solution of rubidium carbonate (1 BC). The solution became colorless. The solution was stirred for 80 min at 75,7 C. pH was changed to 8.78. When adding magnesium nitrate (0,141 g) pH changed to 8.47 after 5 min at C. The stirring was stopped, and the beaker containing the solution was placed in a cold water bath for 20 minutes At 24,3 With the pH value was $ 9,18. When mixing of the upper layer was added titanosilicate (3 g) of example 1 and the mixture was stirred for 2 hours, the pH Value was lowered, so I added an additional solution of rubidium carbonate to maintain the pH at about 8. After 2 h the measured pH value was $ 8,03 when 20,7 C. the Solid products were filtered and washed with deionized water (90 ml). Solid products were progulivali in accordance with the method of example 2 to obtain a catalyst according to this invention. Elemental analysis, mass, using NAA was as follows: 0,011% AI, 47 percent Si, 1.12 percent Ti, 0,93% Rb, 0,090% MD, 0,0052% Na. The catalyst had only a weak shade which showed that gold was on creatures is written in example 1. At 200C and time 1,69 (GHSV 2130 h-1), and after 120 h in the flow of the catalyst gave a conversion of propylene, equal to 1.8%, the selectivity for RHO, equal to 89 percent, the performance of 42 g PO/kg cat-h, the molar ratio of water:RO of 3.8:1, and 0.39 weight percent RO at the reactor outlet.

Example 7

14-liter stainless steel container with lid was purged for 15 minutes with dry nitrogen. The container was placed Tetra(ethyl)orthosilicate (11,276 g). Under intensive stirring silicate was added piperonyl titanium (236,4 g). The resulting solution was heated to 91P, continuously stirring while blowing nitrogen, and kept at this temperature for a total time of heating 2 hours the Solution is then cooled to 1.90C in an ice bath for 2 hours an Aqueous solution of hydroxide of tetrapropylammonium (9874 g, 40 mass percent TRON) having a low alkali content (less than 20 million-1Na), was placed in a container made of polypropylene with a volume of 16 gpm (60,6 l). Under stirring into a solution TRON was added deionized water (5814 g). The container was placed in an ice bath. The solution TRAIN also was pumped through the outer outlet tube with a diameter of 1/4 inch (0.6 cm) stainless steel, immersed in a bath of dry ice-azet the target was cooled to-4C. Cold alkoxide solution was pumped into a container with a volume of 16 gpm (60,6 l) at a speed of 150 ml/min. After adding about half of the alkoxide solution. the temperature of the mixture slowly grew, reaching-2C. Finally, with stirring, to the mixture was added deionized water (5432 g). The temperature of the resulting mixture was 8,2 C. the Mixture was stirred for 18 h at room temperature.

Then spent hydrothermal synthesis in an autoclave of stainless steel with stirring at 200 rpm, the Autoclave was heated up to 160S and held at this temperature for 4 days. Then the reactor was cooled to room temperature and the product was drained from the reactor. The product contained a large organic layer, which was separated from the remainder of the mixture. pH of the aqueous liquid milky white brought up to approximately 8.7 nitric acid (1,5 BC) and the product was recovered by centrifugation at 3000 rpm/min, the Solid was again dispersible in deionized water and centrifuged. The obtained solid substance was dried at 110S for 12 h, after which he progulivali in an air-oven. The substance was heated to C for 5 h, then for 5 h was heated at S. Powder x-ray diffraction analysis showed that on.

An aqueous solution of cesium hydroxide (0,296 g, 50% by weight) was added to deionized water (19,85 g). the pH of the resulting solution was 12,6. The trihydrate of sodium acetate (0,128 g) was dissolved in s under stirring. the pH of the solution was changed to 12.5. The trihydrate of tetrachloroaurate hydrogen (0.008 g) was added to the solution and dissolved with stirring. the pH of the solution remained unchanged. Titanosilicates medium (5 g, 2 mm particles) obtained above was placed in a 250 ml round bottom flask. The flask was attached to a rotary evaporator and was pumped up to 30 mm Hg. Titanosilicate was heated in vacuum at 80 ° C for 1 h, then cooled to room temperature. Titanosilicate slowly impregnated with a solution of gold (7,63 g) in vacuum and kept at room temperature for 2 hours Finally, the impregnated substance was heated at 80 ° C in vacuum for 2,3 hours the Catalyst was very weak staining, which showed that gold was being oxidized.

The catalyst (2 g) was loaded into the continuous flow reactor of stainless steel with a diameter of 0.5 inch (12.5 mm) with a fixed layer. The catalyst was heated at 140 C in a stream of helium for 4 h, then in a stream of propylene and hydrogen for about 10 min and, finally, in pathelem in a ratio of 20:80 by volume of the mixture. The composition of the stream at the entrance consisted of 10 percent hydrogen, 10 percent oxygen and 20 percent propylene, the rest is helium. The working pressure was maintained at 10 psig (69 kPa). The products were analyzed using simultaneous (online) gas chromatography (Chromopack Poraplot S column, 25 m) and/or mass spectrometry. When 190S and time 1,72 with through 58 h in the flow of the catalyst gave a conversion of propylene of 3.5 percent, the selectivity to propylene oxide of 92.6 percent, productivity by propylene oxide 80 g/kg cat-h and the molar ratio of water:RO equal to 4.5:1. The same harakteristika observed in 82 hours.

Example 8

Under stirring in deionized water (79,45 g) was added potassium hydroxide (0.27 g). The trihydrate of sodium acetate (1,43 g) was dissolved in the above solution with stirring. The trihydrate of tetrachloroaurate hydrogen (0.08 g) was added to the solution and dissolved under stirring with education after 30 minutes a clear solution having a pH of 12.3. Medium (40 g) containing titanosilicate in example 7, was associated with 18 mass% of silicon oxide in 1/8-inch (0,32 cm) extrudates were placed in a 500 ml round bottom flask. The flask was connected with a rotary was isperdal to room temperature and kept at room temperature for 30 minutes Titanosilicate slowly impregnated with a solution containing gold (38,24 g), in vacuum and kept at room temperature for 2 hours Impregnated substance was heated at 80 ° C in vacuum for 2.25 hours to obtain a catalyst according to this invention. The catalyst had only a weak coloration, showing that the gold contained in it, was essentially oxidized.

The catalyst (20 g) was evaluated in hydrocyclone propylene to propylene oxide by the method described in example 7, except that the WHSV was 11.3 h-1and the pressure was equal to 215 pounds per square inch (1482 kPa). The products were analyzed using simultaneous mass spectrometry. When 160S after 20 h in the flow of the catalyst gave a conversion of propylene, equal to 1.45 percent, the selectivity to propylene oxide, equal to 97 percent, and the molar ratio of water:RO, equal to 6.2:1. After 70 h in the stream, the conversion of propylene was 1.25 percent, the selectivity to propylene oxide was equal to 96 percent, and the molar ratio of water:RO was equal to 8.1:1.

Example 9

Crystalline titanium silicate (3 g) obtained as in example 7, was progulivali when C in air for 4 h and cooled to room temperature. Prepared ethanol solution, coloroption acid (0.015 g in 10 g of ethanol). The resulting solution used for impregnation of titanium silicate by wet impregnation until the initial moisture content. The impregnated silica was dried in air to obtain a catalyst containing oxidized gold on titanium containing media. The catalyst had a white color, indicating a catalytic content of oxidized gold. Metallic gold was not detected using the VE-TEM or RFU. Oxidized gold was not detected by the RFU. It should be noted that the loading of gold was very low and the signal RFU for oxidized gold was usually weak.

The catalyst (2 g) was evaluated by gidrookislov propylene to propylene oxide using the following input flow: propylene (35 percent), hydrogen (10 percent), oxygen (10 percent), other - helium; and according to the method described in example 1. At a pressure of 15 psi (103 kPa), total flow rate of 200 NCM3and 200C conversion of propylene was 2.3%, with a selectivity of 88% relative to propylene oxide.

Example 10

Crystalline titanium silicate (15 g) obtained as in example 7, was caliciviral in air up to 6000C for 8 h and cooled to room temperature. Preparing the local solution, containing solitonopodobnogo acid (0.06 g in 5 g of methanol). The resulting solution used for impregnation of titanium silicate until the initial moisture content. The impregnated silica was then dried in a vacuum oven for 30 min and then was heated in an oven at 60C for 1 h to obtain a catalyst containing gold on titanium containing media. Re-TEM showed a small amount of gold particles. Scattering in the Mie showed a weak band of metallic gold. As determined using the RFU, 40 mass% of the total gold content were oxidized.

The catalyst (3.0 g) was evaluated by gidrookislov propylene to propylene oxide in the manner similar to example 1. The flow at the entrance contained propylene (35 percent), hydrogen (10 percent), oxygen (10 percent), the rest is helium. The process conditions were: 225 psig (1551 kPa) with a total flow of 500 normal cubic centimeters per minute (MNC3). When the temperature IS conversion of propylene was 1.5% with a selectivity to propylene oxide 99% and the molar ratio of water: RO was 3.2:1.

Example 11

Tetraethylorthosilicate (50 g) was cooled to temperatures below 5 ° C in an ice bath and at first adny (below 5 ° C) solution of tetrapropylammonium hydroxide (TRON, 43,9 g; 40% in water) and water (43,5 g) with such speed, that did not appear visible solid phase. After adding a solution TRAIN the mixture is hydrolyzed at room temperature for gyrorotor shaker (gyrotary shaker) within 24 hours Gidralizovanny the suspension is then heated at C for 64 hours After crystallization, the suspension was centrifuged at 16400 rpm for 2 h and the solid phase was isolated by decanting the liquid. The solid phase was again dispersible in fresh water and the suspension was centrifuged as described above. This washing process was repeated 3 times. The obtained purified suspension was dried by freezing to obtain a powder, which was identified using XRD as titanosilicate structure of the MFI. The size of the crystals was in the middle 46-60 nm. RAF showed peaks at 460 and 458 eV, related to the frame and grafted titanium, respectively.

When mixing of the upper layer in deionized water (68,5 ml) was added solitonopodobnogo acid (0,069 g). The obtained transparent yellow solution was heated on a water bath to 70 C (pH 2,30). the pH was brought to 8.60 using an aqueous solution of sodium carbonate (0.5 in BC). The solution became colorless. The mixture was stirred for 80 min at 73,8 C. pH was equal 9,10. To Rast is ATEM stirring was stopped and the glass of solution was placed in a cold water bath for approximately 20 minutes When 20,1 With the pH of the solution was equal 9,26. When mixing of the upper layer was added titanosilicate (2.0 g) and the resulting mixture was stirred for 2 h pH fell, therefore, to maintain a pH of about 8 was added an additional amount of sodium carbonate solution. The final pH value was by 8.22 when 21,1 C. the Solid products were filtered and washed with deionized water (90 ml). Solid products were progulivali in accordance with the method of example 2 to obtain a catalyst according to this invention. The catalyst had only a weak coloration which indicates that the contained gold was essentially oxidized.

The catalyst was evaluated in hydrocyclone propylene to propylene oxide by the method described in example 1, except that the temperature of the process was 180C, the pressure was 10 psi (69 kPa), and the time was 1,76 (GHSV, 2,045 h-1). In these working conditions, the catalyst gave a conversion of propylene of 2.0 percent, the selectivity to propylene oxide of 89.9 percent, the molar ratio of N2About:RO of 4.7:1 and performance on propylene oxide 54 g/kg cat-h

Example 12

The catalyst according to example 4 was evaluated by gidrookislov 1-butene to 1-butenolide. Hydra 8% oxygen, 8% hydrogen and the rest is helium. When S, atmospheric pressure and the General flow of 150 cm/min initial conversion of 1-butene was 0.7%, the selectivity for 1-butenolide 86 percent. After 20 h in the flow conversion was 0.3%, the selectivity towards 1-butenolide 85 percent.

Example 13

The catalyst (2 g) containing oxidized gold on titanosilicate the extrudates size 1/8 " (0,32 cm) containing 8% silica bundles was evaluated by gidrookislov butadiene. Gold was besieged by the method of planting-deposition as follows. Applying the mixing of the upper layer to deionized water (of 9.55 kg) was added solitonopodobnogo acid (9,48 g). Transparent yellow solution was heated to 73S (pH 2,39). the pH was brought to 8.67 using an aqueous solution of rubidium carbonate (1 BC). The solution became colorless. The mixture was stirred for 2 h at 72,1 C. pH was equal 8,96. To the solution was added to the uranyl nitrate magnesium (6,15 g). After stirring for 5 min the pH was equal to € 8.74 when 71,9 C. Then, the stirring was stopped and the solution was cooled for 12 h with constant agitation. When 22,8 With the pH of the solution was equal 9,16. LV bring the extrudate (280 g) and the resulting mixture was stirred for 8 hours The final pH value was of 7.96 when 27,2 C. the Solid products were filtered and washed with 500 ml of a solution of rubidium carbonate at pH of 9.4. Solid products were progulivali blower in the furnace by heating from room temperature up to 110S for 30 min, followed by maintaining for 4 h at this temperature, then was heated to 700C for 5 h, and then kept for 5 h at 700C, obtaining a catalyst according to this invention.

The catalyst was evaluated by gidrookislov butadiene manner similar to that described in example 1. The flow at the entrance contained 1,3-butadiene (20 percent), oxygen (10 percent), hydrogen (10 percent); propane as an internal standard (4,2 molar percent), the rest is helium. Education monoxide 1,3-butadiene was confirmed using gas chromatography. As a major side product was observed carbon dioxide.

The catalyst was tested at a temperature of layer 280S approximately 6 h in the flow at lower temperatures, then 12 h was purged with helium at 140 ° C. Process conditions and results are presented in table 1.

Example 14

A mixture of barium alkoxides and titanium (Gelest, Inc., Tullytown, PA; DBATI50, 12,51 g 0.5 M solution, content is oru was added silica gel (PQ HP321, 30,2 g), which was progulivali at 300C, was added to the solution and the resulting mixture was stirred over night. The solvent was removed under 35S in vacuum for 1 h the Solid residue was dried at 110S for 5 h, progulivali at a temperature of from 110S to 600C in air for 5 h and kept at 600C for 4 hours to obtain titanium containing substrate.

Solitonopodobnogo acid (0,1514 g) was dissolved in water (320 ml). The solution was heated to 70 C and the pH was brought to 8.0 with sodium carbonate. Then the solution was cooled to room temperature. Such media (6,29 g) was added to the gold solution. the pH of the solution was lowered; to maintain pH 7.5) was added sodium carbonate. The mixture was stirred for 1 h, the Solid products were filtered, washed with water (100 ml at pH 7.5) and filtered. The washed solids were dried at 110S for 5 h, then was progulivali in air at a temperature of from 110 to C for 5 h, and then kept at C for 4 h with obtaining a catalyst according to the invention. Elemental analysis: 940 million-1AI; 0.97 percent Ti; 1290 million-1Na; 2.40% VA; mass, which is determined using NAA.

The catalyst contained several gold particles with a size of 3.5 nm. Using x-ray SPE is contained gold particles, which were less than 1 nm. About 30 mass percent of the gold was oxidized, as measured by the RFU.

The catalyst was evaluated by gidrookislov propylene to propylene oxide by the method described in example 1, using for analysis of on-line mass spectrometry. The process ran for about 4 hours at 150C; then the catalyst was regenerated at C in a mixture of oxygen (20 volume percent) and water (1 volume percent), the rest is helium. After the first regeneration process hydrocyclone was carried out at 150 C for about 5 h and then the catalyst was regenerated a second time at 450C in a mixture of water, oxygen, and helium. After the second regeneration, the catalyst was evaluated according to the method of hydrocyclone at 150 results are shown in table.2.

Example 15

Titanosilicates polymer, described as a copolymer of detoxification-utilitate (Gelest, Inc. Tullytown, PA; PSITI-019, 22,43 g containing of 19.1-19.6 percent silicone and 2.1-2.3 percent titanium) was dissolved in isopropanol (150 ml). Silica gel (PQ HP 321; 20,3 g, which was annealed at 300C) was added to the solution and the mixture was stirred over night. The solvent was removed under 35S in vacuum on a rotary evaporator. The solid residue was heated to 100C in vacuum and kept the s 5 h, and then progulivali at 600C for 4 hours to obtain titanium containing substrate.

Solitonopodobnogo acid (0,1503 g) was dissolved in water (350 ml). The solution was heated to 70 C; pH was brought to 8.0 with sodium carbonate and the solution was cooled to room temperature. Such media (6,03 g) was added to the gold solution. the pH of the solution was lowered; to maintain pH 7.5) was added sodium carbonate. The mixture was stirred for 1 h, the Solid products were filtered, washed with water (100 ml, pH 7.5) and again filtered. The solid products were dried at 110S for 5 h, and then was progulivali in air at a temperature of from 110S to C for 5 h, and then kept at C for 4 hours Solid products were removed from the furnace, and then again placed in the oven at 300C and was heated for 1 h to S, then kept at C for 2 h with obtaining a catalyst according to the invention. Elemental analysis: 610 million-1AI; 1.50 percent Ti; 4700 million-1Na, mass. The catalyst contained gold particles with a size of 3.5 nm. Using EDS on VE-TEM, it was found that, along with gold particles of 3.5 nm, the catalyst also contained gold particles that were less than 1 nm. Oxidized gold was 40 mass percent relative to obseg is and propylene oxide according to the method, described in example 1. The process ran for about 4 hours at 150C; then the catalyst was regenerated at C in a mixture of oxygen (20 volume percent) and water (1 volume percent), the rest is helium. After the first regeneration process hydrocyclone was carried out at 150 C for about 5 h, and then the catalyst was regenerated a second time at 450C in a mixture of water, oxygen, and helium. After the second regeneration, the catalyst was evaluated according to the method of hydrocyclone at 150 results are shown in table.3.

Example 16

Solitonopodobnogo acid (0,1513 g) and barium nitrate (0,3037 g) was dissolved in water (350 ml). The resulting solution was heated to 70 C; pH was brought to 7.0 with sodium carbonate; and the solution was cooled to room temperature. Added to the gold solution and barium titanium containing media (6,05 g), identical to those used in example 15. the pH of the solution was lowered; to maintain pH 7.0) was added sodium carbonate. The mixture was stirred for 1 h, the Solid products were filtered, washed with water (100 ml, pH 7.5) and again filtered. The solid products were dried at 110S for 5 h, then was progulivali in air at a temperature of from 110 to C for 5 h and then kept at C for 4 hours Solid products were removed from the obtaining of the catalyst according to the invention. Elemental analysis: 3200 million-1AI; 1.47% Ti; 1550 million-1Na, 1,95% VA. Oxidized gold was 42 mass% relative to the total gold content, as measured by the RFU. Re-TEM showed that some metal particles of gold were average size of 5.0 nm and many particles of about 1.5 nm.

The catalyst was evaluated by gidrookislov propylene to propylene oxide by the method described in example 1. The process ran for about 4 hours at 150C; then the catalyst was regenerated at C in a mixture of oxygen (20 volume percent) and water (1 volume percent), the rest is helium. After the first regeneration process hydrocyclone was carried out at 150 for about 4 hours and then the catalyst was regenerated a second time at 450C in a mixture of water, oxygen, and helium. After the second regeneration, the catalyst was evaluated according to the method of hydrocyclone at 150 results are shown in table.4.

Example 17

Such media were prepared using silicone powder (silica gel PQ-HP-420; 50.0 g), which was dried at 300C. After cooling to room temperature, the silica gel powder was transferred into the air in a 2-liter flask of a rotary evaporator. Powder silica gel, Ostrov(trimethylsiloxy)titanium (Gelest, 2,60 g) in isopropyl alcohol (300,0 g) and the resulting solution was transferred into a funnel to add and have sealed. To the powder of silica gel in a vacuum solution was added tetrakis(trimethylsiloxy)titanium and the mixture was kept under vacuum for another 5 minutes Then through the flask missed nitrogen for about 16 hours was Applied vacuum to remove solvent at 40 ° C for 1 h, then at 85C for 1 h Selected solid products were progulivali in air in a muffle furnace at a temperature of from room temperature up to 800C for 5 h, then kept at 800C for 5 h and cooled to room temperature to obtain titanium containing substrate according to this invention.

Solitonopodobnogo acid (0,150 g), lithium nitrate (0,160 g) and magnesium nitrate (0,30 g) was dissolved in deionized water (350 g). The resulting solution was heated to 70C, bringing the pH to 7.8 by adding dropwise an aqueous solution of lithium carbonate (0.10 M). The resulting solution was cooled to room temperature; the pH was raised to 8.3. Then the solution was added titanium containing medium (5.0 g). The flask was which on a rotating shaker for 90 min, while the pH was brought to 7.5 with an aqueous solution of lithium carbonate (0.5 M). The solid products were filtered, using a funnel Bubnov washed with methanol (80,0 ml). Filtration was continued for 30 minutes the Solid products were placed in a vacuum oven at 60C for 3 hours to obtain catalyst according to this invention. The catalyst, from white to pale blue in color, not progulivali, and used after vacuum drying. Elemental analysis, by weight, was as follows: 0,037% AU, 0.56% Ti, 0.017% Na 0.23% MD, according to the NAA. RAF showed 66 weight percent of oxidized gold. Ti-RAF showed 92 percent nizkolegirovannaja and 8 percent vysokomehanizirovannogo titanium.

The catalyst (2.0 g) was evaluated by gidrookislov propylene to propylene oxide using conditions and results shown in the table.5.

Example 18

Titanium containing medium (30 g), prepared as described in example 7, was progulivali in air at C for 8 h and cooled to room temperature. Got a solution containing solitonopodobnogo acid (0.035 g) and sodium acetate (0.5 g) in methanol (35 g). The sample was dried in vacuum at room temperature until free-flowing condition, and then heated in a vacuum to 100C for 2 hours to obtain a catalyst according to this invention.

The catalyst (30 g) was evaluated by gidrookislov propylene was 210 psi (1448 kPa); and temperature membrane reactor was 160S. It had been the conversion of propylene at 3.2 percent with a selectivity to propylene oxide in 96 percent.

Example 19

Tetraethylorthosilicate (50 g) was cooled below 5 ° C in an ice bath and with stirring was added Tetra(ataxic) titanium (IV) (1,37 g). To this cooled mixture was added a cold (less than 5C) hydroxide solution of tetrapropylammonium (TRAN and 43.9 g; 40% in water) and water (43,5 g). Then add about 15 drops of the mixture TRON/water with stirring, and the solution was slightly Motel. The remaining mixture TRON/water is then quickly added to a mixture of TEOS/Ti with vigorous stirring for 5 min, and shortly thereafter, the solution was transparent, indicating that the visible absence of the solid phase products. Stirring is continued until such time as the temperature of the mixture did not become room temperature, and then the mixture is hydrolyzed at room temperature for gyrorotor a shaker for 24 hours Gidralizovanny the suspension is then heated at C for 64 hours After crystallization, the suspension was centrifuged at 16400 rpm for 2 h and the solid phase was isolated by decandia fluid. Phase solid product was again dispersible in the Yu purified suspension was dried by freezing to produce powder, which identified using XRD as titanosilicate structure of the MFI. The size of the crystals was in the middle 46-60 nm. RAF showed peaks at 460 and 458 eV, related to the frame and legirovannom titanium, respectively.

1. The method of producing oxide olefin comprising contacting the olefin containing at least three carbon atoms with oxygen in the presence of hydrogen and, optionally, a diluent and in the presence of a catalyst containing oxidized gold on titanium containing media, with more than 30 wt.% all the gold in the calculation of the total amount of gold present in the catalyst, is oxidized gold.

2. The method according to p. 1, characterized in that the olefin is a C3-12-monoolefins or diolefins.

3. The method according to p. 1 or 2, characterized in that the gold deposited on the carrier in an amount greater than about 0.001 and less than 20 wt.%, in relation to the total weight of the catalyst.

4. The method according to any of paragraphs.1-3, characterized in that more than 70 wt.% all the gold in the calculation of the total amount of gold present in the catalyst, is oxidized gold.

5. The method according to any of paragraphs.1-4, characterized in that the titanium containing media contains titanosilicate is about 500:1.

6. The method according to p. 5, characterized in that titanosilicate has a crystal structure of the MFI type.

7. The method according to any of paragraphs.1-4, characterized in that the titanium containing carrier containing titanium dispersed on silica.

8. The method according to any of paragraphs.1-7, characterized in that the titanium containing media contains many types of the coordination environment of Titan.

9. The method according to any of paragraphs.1-4, 7 or 8, characterized in that the titanium containing medium obtained by (a) dispersing titansiloxanes complex or a mixture of these complexes on silica; (b) dispersing a mixture of a titanium alkoxide and alkoxide of the metal-promoter on the carrier silicon oxide and subsequent annealing of the specified media; (c) dispersion titanosilicates monomer, dimer, polymer or mixtures thereof on a carrier of silica and subsequent annealing specified media, where titanosilicates monomer represented by the formula

(R1)xTi[O-Si(R2)3-(R3)y]4-x,

where R1, R2and R3each independently selected from the groups alkyl, alkoxy, aryl, aryloxy and halogen;

x is an integer Naghdi titanosilicates dimer and polymer represented by the formula, shown above, except that R3can also be repetitive element, selected from the following residues:

[O-Ti(R2)3-y(R3)y] and [O-Si(R2)3-y(R3)y],

where R2, R3and u have any value specified above;

or (d) dispersion of titanium containing polymer on a carrier of silica and subsequent annealing specified media, where such polymer is an organic titanium containing polymer containing a main chain made of titanium, silicon and group -(CR2)z- where z is an integer in the range of 1 to 20, and each R is independently selected from alkyl, aryl, alkoxy or halogen.

10. The method according to any of paragraphs.1-4, characterized in that the titanium containing carrier selected from titanium oxide, titanates metals promoters and titanium dispersed on the silicates of metals promoters.

11. The method according to any of paragraphs.1-10, characterized in that the titanium loaded on the carrier in a quantity greater than 0.02 wt.%, and less than about 20 wt.%, relative to the mass media.

12. The method according to any of paragraphs.1-11, characterized in that the catalyst is connected to the second nositele">

13. The method according to any of paragraphs.1-11, characterized in that the catalyst has the form of a bead, pellet, sphere, honeycomb, monolith, extrudate or film, or under item 12, characterized in that the catalyst is deposited on the second carrier that has the form of a bead, pellet, sphere, honeycomb, monolith, extrudate or film.

14. The method according to any of paragraphs.1-13, characterized in that the catalyst additionally contains at least one promoter selected from silver, elements of group 1, group 2, the lanthanide rare earth and actinide elements and their combinations.

15. The method according to any of paragraphs.1-14, characterized in that the promoter is selected from silver, magnesium, calcium, barium, lithium, sodium, potassium, rubidium, cesium, erbium, lutetium, and combinations thereof.

16. The method according to any of paragraphs.1-15, characterized in that the method is carried out at temperatures above 20 and below 300°C., at a pressure of from atmospheric to 400 psig (2758 kPa) and not necessarily in the gas phase at a volumetric hourly rate of feed olefin is greater than 10 h-1and less than 50000 h-1.

17. The method according to any of paragraphs.1-16, characterized in that the gas phase propylene in contact with oxygen in the presence of hydrogen, and optional diluent, qatn inch (2758 kPa) and average hourly volumetric feed rate of the olefin is greater than 10 h-1and less than 50000 h-1with the receipt of propylene oxide.

18. Catalytic composition for obtaining the olefin oxide containing oxidized gold on such media, where the total amount of gold is greater than 0.001 and less than 20 wt.%, in relation to the total weight of the catalytic composition, and where more than 30 wt.% all the gold in the calculation of the total amount of gold present in the catalyst, is oxidized gold.

19. The composition according to p. 18, in which there is no oxidized gold on bulk titanium dioxide.

20. The composition according to p. 18 or 19, characterized in that more than 70 wt.% gold present in the catalyst, is an oxidized gold.

21. The composition according to p. 18 or 19, characterized in that if there are particles of gold, these particles have an average size less than 1 nm.

22. Composition according to any one of paragraphs.18-21, wherein the catalyst additionally contains at least one promoter selected from silver, elements of group 1, group 2, the lanthanide rare earth and actinide elements and their combinations.

23. Composition according to any one of paragraphs.18 to 22, characterized in that the total concentrat the

24. Composition according to any one of paragraphs.18-23, wherein the titanium containing media is titanosilicate, where, optionally, titanosilicate has the crystal structure of the MFI type and the atomic ratio of silicon to titanium in the range from 1:1 to 500:1.

25. Composition according to any one of paragraphs.18-23, wherein the titanium containing carrier containing titanium dispersed on silica.

26. Composition according to any one of paragraphs.18-25, characterized in that the medium contains many types of the coordination environment of Titan.

27. Composition according to any one of paragraphs.18-23, 25 or 26, characterized in that the medium is obtained by (a) dispersing titansiloxanes complex or combination titansiloxanes complexes on the media of silicon dioxide; (b) dispersing a mixture of a titanium alkoxide and alkoxide of the metal-promoter on the carrier of silicon dioxide and subsequent calcination of the carrier; (c) dispersion licenselanguage monomer, dimer or polymer on a carrier of silica and subsequent calcination of the carrier, where titanosilicates monomer represented by the following formula:

(R1)xTi[O-Si(R2)3-(R3)y

x is an integer in the range of 0 to 3;

y is an integer in the range of 0 to 3;

and where titanosilicates dimer and polymer can be represented by the formula shown above, except that R3can also be repetitive element, selected from the following residues:

[O-Si(R2)3-y(R3)y] and [O-Ti(R2)3-y(R3)y],

where R2, R3and u can have any value above

or (d) dispersion of titanium containing polymer on a carrier of silica and subsequent calcination of the carrier, where such polymer contains the main chain of titanium, silicon and group -(CR2)z- where z is an integer in the range of 1 to 20, and each R is independently selected from alkyl, aryl, alkoxy or halogen.

28. Composition according to any one of paragraphs.18-23, wherein the titanium containing carrier selected from titanium oxide, titanates metals promoters and titanium dispersed on the silicates of metals promoters.

29. Composition according to any one of paragraphs. 18-28, characterized in that the load of the media Titan who notice according to any one of paragraphs. 18-28, wherein the composition is extruded together with the second media associated with him or applied thereto, where the second carrier is selected from silica, alumina, aluminosilicates, magnesium oxide, titanium dioxide, carbon and mixtures thereof.

31. Composition according to any one of paragraphs.18-30, characterized in that the catalyst has the form of a bead, pellet, sphere, honeycomb, monolith, extrudate or film, or p. 30, where the catalyst is deposited on the second carrier that has the form of a bead, pellet, sphere, honeycomb, monolith, extrudate or film.

32. Composition according to any one of paragraphs.18-31, characterized in that the catalyst obtained by the method comprising the dispersion to such carrier by impregnation or deposition by precipitation of an aqueous solution of gold, having a pH between 7 and 14, and/or organic solution, and one or both of the solution containing the compound of gold, including oxidized gold, and, optionally, the dispersion in such media, one or more anionic additives selected from halides, phosphates, sulfates, borates, carbonates and carboxylates of metals promoters and mixtures thereof, moreover, the dispersion by impregnation or coating deposition wire is nosily dried in air at a temperature of from 20 to 120C; and then the dried composition can be optionally calcined in air or heated in an inert atmosphere at a temperature of from 120 to S.

33. The method of producing catalyst according to p. 18, comprising dispersing by impregnation or deposition deposition of gold compounds containing oxidized gold, titanium containing medium, and the dispersion by impregnation or coating deposition is carried out at a temperature of from 20 to 80C; and, after dispersion by impregnation or coating deposition, the resulting composition is dried in air at a temperature of from 20 to 120C; and then dried composition can be optionally calcined in air or heated in an inert atmosphere at a temperature of from 120 to S.

34. The method according to p. 33, characterized in that one or more anionic additives dispersed in a carrier or combination of promoter (s) and anion(-s) additives (additives) dispersed in the carrier.

35. Composition of media suitable for use in the process of producing olefin oxide comprising titanium containing media, characterized by many types of the coordination environment of Titan.

36. The composition according to p. 35, wherein the titanium containing noscapine on p. 35, characterized in that the medium is received by a process comprising dispersing licenselanguage monomer, dimer or polymer on a carrier of silica and subsequent calcination of the carrier, where titansiloxanes monomer represented by the following formula:

(R1)xTi[O-Si(R2)3-(R3)y]4-x,

where R1, R2and R3each independently selected from the groups alkyl, alkoxy, aryl, aryloxy and halogen;

x is an integer in the range of 0 to 3;

y is an integer in the range of 0 to 3;

and where titanosilicates dimer and polymer can be represented by the formula shown above, except that R3can also be repetitive element, selected from the following residues:

[O-Si(R2)3-y(R3)y] and [O-Ti(R2)3-y(R3)y],

where R2, R3and u can have any of the values specified above.

 

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