Method of hydroxidation using catalyst produced from gold cluster complex

FIELD: process engineering.

SUBSTANCE: invention relates to olefin hydroxidation catalysts. Proposed catalytic composition for production of olefin oxide by olefin hydroxidation comprises gold nanoparticles deposited on particles of nanoporous titanosilicate carrier. Note here that said catalyst is obtained by method including deposition of cluster complex gold-ligand on nanoporous titanosilicate carrier at minus 100°C to 300°C to produce catalyst precursor, and heating at not over 50-800°C and/or chemical treatment of catalyst precursor for 15 min to 5 h to form catalyst. Invention covers also the method of producing olefin oxide comprising bringing olefin with, at least, three carbon atoms in contact with oxygen in the presence of hydrogen and catalyst with above described composition. Note here that said contact is realized at 160°C and lower that 300°C and pressure varying from atmospheric pressure to 3549 kPa (500 psi). It covers also catalyst precursor composition including cluster complex ligand-gold deposited on particles of nanoporous titanosilicate carrier.

EFFECT: high catalytic activity, longer life and higher efficiency.

16 cl, 15 tbl, 19 dwg, 24 ex

This application sets the priority of the provisional application U.S. No. 60/859738, filed November 17, 2006 and are included in this description by reference.

The LEVEL of TECHNOLOGY

This invention relates to an improved method and catalyst for hydrocyclone olefins, such as propylene, oxygen in the presence of hydrogen with oxides of olefins, such as propylene oxide.

Oxides of olefins, such as propylene oxide, are used to alkoxysilane alcohols with the formation of polyether 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 such alkalophile as propylene glycol, and such alkanolamines as isopropanolamine applicable as solvents and surfactants.

Direct oxidation of olefins having three or more carbon atoms (C3+olefins), oxygen has been the subject of industrial interest for several decades. Much effort has been focused on the direct oxidation of propylene with oxygen in the propylene oxide. This method sought to replace indirect multistage production methods, common in practice, and which includes well-known methods using chlorhydrin and organic is about hydroperoxide in the case of obtaining propylene oxide. It is known that silver catalysts can catalyze the direct oxidation of propylene with oxygen in the propylene oxide with a selectivity of not more than about 70 mol.%. Unfortunately, in the way that generates significant quantities of by-products of incomplete oxidation, including acrolein, acetone and propionic aldehyde, and the products of complete oxidation, namely monoxide and carbon dioxide.

In the past ten years has received many patents that revealed a direct hydrocyclone olefins having three or more carbon atoms, with oxygen in the presence of hydrogen with oxides of olefins. Disclosed are catalysts of hydrocyclone containing gold, silver and precious metals such as palladium and platinum, and, optionally, one or more of these promoters, as alkali, alkaline earth and rare earth metals, besieged on such such media as titanium dioxide or titanosilicate zeolite. Many patents great attention was especially paid to the gold or gold in combination with silver and/or other noble metal (for example, a bimetallic catalyst with palladium), some patents as catalytically active species revealed oxidized gold, whereas in other patents disclosed a metallic gold with a particle size of more than 1 on the home is RA (nm) and less than about 100 nm. It should be noted group of patents which disclosed hydrocyclone C3+olefins using catalysts containing gold, silver, and/or a noble metal deposited on the titanium containing media, including the following: EP-A1-0709360, WO 98/00413, WO 98/00414, WO 98/00415, U.S. patent No. 6255499, WO 03/062196, WO 96/02323, WO 97/25143 and WO 97/47386. In the above methods of the prior art catalysts obtained by impregnation of one or more solutions of soluble salts of gold, silver and/or one or more noble metals and soluble salts of one or more promoters or deposition of these solutions. In the above methods hydrocyclone prior indicates high selectivity to the formation of a C3+olefin oxides, particularly propylenoxide. The resulting selectivity to propylene oxide is more than 90 mol.%; and, in addition, it is also reported about the selectivity to propylene oxide of more than 95 mol.%.

Despite the progress made, before the method hydrocyclone will be able to replace existing methods of production of olefin oxides, it is necessary to overcome several problems. First, it is necessary to increase the efficiency of hydrogen. Hydrogen is a necessary reagent upon receipt of the olefin oxide. For each mol of the obtained olefin oxide in the way hydrocyclone the olefins formed a stoichiometric equivalent of water. Additional amounts of water may also be formed by one or more undesirable side reactions, for example, in the direct oxidation of hydrogen by oxygen. The efficiency of hydrogen can be determined by measuring the molar ratio of water to olefin oxide, such as water to propylene oxide (N₂About/TO), in the product flow. The desired ratio of 1/1; but in practice, at any given point in time of the process is usually observed a higher ratio. In addition, when using conventional catalysts of the prior art the formation of water and the molar ratio of water to olefin over time is unacceptable increase. Although control over the molar ratio of water to olefin oxide in various intervals of the process is informative, the best indicator of the overall efficiency of hydrogen is the total molar ratio of water to olefin oxide. For the purposes of this invention, the term "cumulative molar ratio water/olefin oxide" means the average molar ratio of water to olefin oxide, obtained during the total time of experience, preferably averaged from measurements of the concentrations of water and the olefin oxide in the product flow, taken at least every three hours, preferably at least every two hours is, more preferably, every hour. In the methods of the prior over time the cumulative molar ratio water/olefin oxide increases and often exceeds the value of about 10/1, which is unacceptably high.

Secondly, the methods of the prior art carried out usually at a temperature in the range from about 70°to about 170°C. Outside the specified temperature range and even in this range, depending on the catalyst, the methods of the prior detect to low selectivity to olefin oxides and increased selectivity to undesirable products of incomplete oxidation (they are, for example, propionic aldehyde, acetone, acrolein), the products of complete oxidation (namely carbon monoxide and carbon dioxide), the products of hydrogenation (e.g., propane) and water. In addition, the catalysts of the prior art have a tendency to rapid deactivation with increasing temperature. In the work at elevated temperatures, for example at 160°C or higher, desired stable activity and selectivity, because, if necessary, in subsequent installations can be used by-product in the form of hot steam (water vapor). Derived from the integrated heat can be beneficial to the General economy and control is the exercise by the installation.

Thirdly, in determining the total saving methods hydrocyclone should take into account the amount of the catalyst of gold, silver and precious metal. Gold, silver and precious metals are known to be expensive, so any reduction in the amounts required for the catalyst hydrocyclone, will give additional benefit.

Fourthly, and most importantly, the catalysts hydrocyclone prior show reduced activity over time and reach a low level of activity within a few days. At this time the process hydrocyclone should be stopped and the catalyst to be regenerated. In this area there is a need to stabilize the activity of the catalyst to work for an extended period of time in order to increase the intervals between regenerations of the catalyst and to improve its overall service life. The term "service life of the catalyst used in this description, refers to the time measured from the beginning of the process hydrocyclone to the point in time at which the catalyst after one or more regenerations loses sufficient activity that makes use of a catalyst is unacceptable, especially from a commercial point of view.

The authors note that T. Alexander Nijhuis et al. in Industrial Engineering and Chemical Research, 38 (1999), 84-891 reveal the catalyst, containing gold particles on the outer surface titanosilicates media designed for hydrocyclone propylene with oxygen in the presence of hydrogen with the formation of propylene oxide. The catalyst was prepared by traditional methods of deposition-the planting of an aqueous solution of chloride of gold (III).

In addition, several references T. V. Choudhary, et al., Journal of Catalysis, 207, 247-255 (2002), discloses catalysts on titanium dioxide, containing as the carrier of the gold nanoparticles obtained from cluster complexes gold-phosphine ligand. In WO 2005/030382 revealed heterogeneous catalyst containing gold particles in the environment of media, such as alumina-coated titanium dioxide, in which gold particles are physically deposited from the vapor phase with the ratio of the penetration depth in the range from about 1×10^-9to about 0.1. In these references are not mentioned ways of hydrocyclone.

The INVENTION

This invention relates to a method of producing olefin oxide directly from the olefin and oxygen in the presence of hydrogen hydrocyclones. The method involves contacting the olefin having three or more carbon atoms, with oxygen in the presence of hydrogen and in the presence of a catalyst of hydrocyclone in process conditions sufficient to obtain the corresponding olefin oxide. COI is litovany in the method according to this invention the catalyst hydrocyclone contains nanoparticles of gold, deposited on the nanoporous particles of such carrier, and the catalyst obtained by the process, including deposition cluster complex gold-ligand on nanoporous titanium containing media under conditions sufficient for the formation of the catalyst precursor, and subsequent heating and/or chemical treatment of the catalyst precursor under conditions sufficient for the formation of catalyst hydrocyclone.

The new method according to this invention is applicable to obtain the olefin oxide directly from an olefin having three or more carbon atoms, and oxygen in the presence of hydrogen. Advantages of the method according to this invention are disclosed hereinafter; however, this disclosure does not impose any restrictions on the method that is defined in the claims. As a first advantage, the method according to this invention is usually achieved steady catalyst activity over a long period of time, approximately more than 25 days, and preferably more than about 30 days. Long time experience advantageously increases the intervals between regenerations of the catalyst and increases the service life of the catalyst. In addition, in preferred embodiments of the method according to this invention advantageously is formed of the olefin oxide with a selectivity of more than about 90 mol.% and preferably is m ore than about 93 mol.% for a long time of experience. Other oxidation products may include carbon dioxide, acrolein, acetone, acetaldehyde and propionic aldehyde, which, as noted hereinafter, are obtained in reasonable quantities, if any, are obtained. Compared with the methods of the prior art, the method according to this invention can be carried out at elevated temperatures without significant reduction in selectivity to olefin oxide and the increase of by-products of incomplete oxidation. While in practice the methods of the prior art typically operate at a temperature from about 70°to about 170°C., the method according to this invention works in practice at a temperature of from about 160°to about 300°C., thus providing increased temperature flexibility. As a by-product of the method of the invention is water, work at elevated temperatures, if necessary, can provide a greater amount of water vapor. Accordingly, the method according to this invention may be combined and implemented in a General setting, in which heat is extracted from water vapor, is used to control additional processes, such as separation of the olefin oxide from the by-product water. Compared with the methods of the prior art, the method according to this invention shows increased the current efficiency of hydrogen, measured by the cumulative molar ratio of water/olefin oxide. In the method according to the invention cumulative molar ratio water/olefin oxide, less than or equal to about 8/1 and preferably less than about 6/1, can be achieved during the whole time of the experience. The method according to this invention in comparison with the methods of the prior art can be advantageously carried out under reduced gold content of such media without reducing the catalytic activity. To achieve economic benefits can be used in the content (loading) of gold from 10 am/million (ppm) to about 20000 hours per million and preferably from about 50 hours per million to about 1000 hours/million

In accordance with a second aspect, this invention relates to a new catalytic compositions containing gold nanoparticles deposited on the nanoporous particles of such carrier, and the catalyst was prepared by the process comprising the deposition cluster complex gold-ligand on nanoporous titanium containing media under conditions sufficient for the formation of the catalyst precursor, and subsequent heating and/or chemical treatment of the catalyst precursor under conditions sufficient for the formation of the catalytic composition.

In accordance with a third aspect, this invention relates to a CSP is trained receipt of the above catalytic composition according to this invention, the method includes the deposition of the cluster complex the gold-ligand on nanoporous titanium containing media under conditions sufficient for the formation of the composition of the catalyst precursor, and subsequent heating and/or chemical treatment composition of the catalyst precursor under conditions sufficient for the formation of a catalytic composition containing gold nanoparticles deposited on the nanoporous particles of such media.

In accordance with a fourth aspect, this invention relates to the composition of the catalyst precursor containing the cluster complex the gold-ligand deposited on the nanoporous particles titanosilicates media.

The composition of the catalyst precursor according to this invention is advantageously used to obtain a catalytic composition according to this invention, which itself can be advantageously used in the above method hydrocyclone in which olefin having three or more carbon atoms directly and selectively turn with oxygen in the presence of hydrogen in the corresponding olefin oxide.

Description of the DRAWINGS

Figure 1 shows the graphical dependence of the conversion of propylene of time and the graphical dependence of the selectivity to propylene oxide in the way Yes the resultant invention, shown in example 1, in which propylene is oxidized by oxygen in the presence of hydrogen and in the presence of a catalyst in one of the variants of the present invention obtained from cluster compounds Au₉the ligand.

Figure 2 shows the graphical dependence of the cumulative molar ratio of water to propylene oxide from time to time for the method shown in example 1.

Figure 3 shows the graphical dependence of the conversion of propylene of time and the graphical dependence of the selectivity to propylene oxide in the method according to this invention shown in example 2, using the catalyst according to this invention, obtained from cluster compounds Au₉the ligand.

Figure 4 shows the graphical dependence of the cumulative molar ratio of water to propylene oxide in the manner shown in example 2.

Figure 5 shows the graphical dependence of the conversion of propylene of time and the graphical dependence of the selectivity to propylene oxide in the method according to this invention shown in example 3, using the catalyst according to this invention, obtained from the cluster complex gold brand Nanogold® - ligand.

Figure 6 shows the graphical dependence of the cumulative molar ratio of water to propylene oxide from time to time in the way that pok is sannam in example 3.

Figure 7 shows the graphical dependence of the cumulative molar ratio of water to propylene oxide in the method shown in example 4, in which the propylene reacts with oxygen in the presence of hydrogen and of a catalyst obtained from a mixed cluster complex Pt-Au₆.

Figure 8 shows the graphical dependence of the conversion of propylene of time and the graphical dependence of the selectivity to propylene oxide in the method according to this invention shown in example 5, using the catalyst according to this invention, obtained from the cluster complex Au brand Positively Charged Nanoprobes - ligand.

Figure 9 shows the graphical dependence of the cumulative molar ratio of water to propylene oxide in the manner shown in example 5.

Figure 10 shows the graphical dependence of the conversion of propylene of time and the graphical dependence of the selectivity to propylene oxide in the method according to this invention shown in example 6, using the catalyst according to this invention, obtained from the cluster complex Au brand Negatively Charged Nanoprobes - ligand.

Figure 11 shows the graphical dependence of the cumulative molar ratio of water to propylene oxide in the manner shown in example 6.

Figure 12 shows graficas the th dependence of the conversion of propylene of time and the graphical dependence of the selectivity to propylene oxide in the method according to this invention, shown in example 7, using the catalyst according to this invention, obtained from the cluster complex Au₅₅the ligand.

Figure 13 shows the graphical dependence of the cumulative molar ratio of water to propylene oxide in the manner shown in example 7.

Figure 14 shows the graphical dependence of the conversion of propylene of time and the graphical dependence of the selectivity to propylene oxide in the method according to this invention shown in example 8, using the catalyst according to this invention, obtained from the cluster complex Au brand Nanogold® - ligand.

Figure 15 shows the graphical dependence of the cumulative molar ratio of water to propylene oxide in the method shown in example 8.

Figure 16 shows the graphical dependence of the conversion of propylene of time and the graphical dependence of the selectivity to propylene oxide in the comparative method using a catalyst containing hartlot acid, which is described in comparative experiment 1.

Figure 17 shows the graphical dependence of the cumulative molar ratio of water to propylene oxide in a comparative way, as shown in comparative experiment 1.

Figure 18 shows the graphical dependence of the conversion of propylene is and from time to time and the graphical dependence of the selectivity to propylene oxide in a comparative way with the use of a catalyst, containing hartlot acid, which is described in comparative experiment 2.

Figure 19 shows the graphical dependence of the cumulative molar ratio of water to propylene oxide in a comparative way, as shown in comparative experiment 2.

DETAILED description of the INVENTION

A new way of hydrocyclone according to this invention comprises the contacting of the olefin having three or more carbon atoms, with oxygen in the presence of hydrogen and catalyst hydrocyclone under conditions sufficient to obtain the corresponding olefin oxide. Reagents containing olefin, oxygen and hydrogen, may be optionally submitted with one or more diluents, which will be disclosed below. The relative molar amounts of olefin, oxygen, hydrogen, and optional diluent can be any quantities that are sufficient to obtain the desired olefin oxide. In the preferred embodiment of this invention, the olefin is a C_3-12the olefin, and his turn in the appropriate_3-12the olefin oxide. In a more preferred embodiment, the olefin is a C_3-8the olefin, and his turn in the appropriate_3-8the olefin oxide. In the most preferred embodiment, the olefin is propylene and olefin oxide is propylenes the house.

Used in the method according to this invention the catalyst hydrocyclone contains gold nanoparticles deposited on the nanoporous particles of such carrier, and the catalyst obtained by the process, including deposition cluster complex gold-ligand on nanoporous titanium containing media under conditions sufficient for the formation of the catalyst precursor, and subsequent heating and/or chemical treatment of the catalyst precursor under conditions sufficient for the formation of the catalyst.

For the purposes of this invention the term "gold nanoparticles" refers broadly to the gold particles, having a diameter (or largest size in the case of nonspherical particles) in the range of from more than about 0.6 nm to less than about 50 nm, preferably from more than about 0.7 nm to less than about 10 nm.

For the purposes of this invention, the expression "such carrier" refers to any solid substance, in which titanium is an integral component of the frame structure of solids, or in which the titanium grafted on a frame structure of a solid substance, or where there is a combination of frame structure and grafted titanium. The term "nanoporous"related to such media, refers to the presence of channels, pores and/or cavities within the frame structure of the tours media; moreover, these channels, pores or cavities have a diameter (or largest dimension) from about 0.2 nm to about 50 nm. On distribution channels, pores and/or cavities not imposed any restrictions, and they may be regularly or randomly distributed in a solid timber frame structure. Feeds themselves may have one, two or three dimensions.

Used in this description, the term "ligand" refers to any organic or inorganic neutral molecule or charged ion, which is associated with one or more metal atoms, in this case gold or any other metal present in the catalyst, such as silver or precious metals such as palladium or platinum. Used in this description, the term "ligand" includes the term in the singular and plural and, therefore, may include the cluster complex containing only one ligand, or the cluster complex containing two or more ligands, which may be the same or different.

Used in this description, the term "complex" means a coordination compound formed by combining one or more electronmobility molecules and/or ions (ligand) with one or more elektrosnabzhenie atoms or ions (e.g. metal). In this case electrondoped is authorized(and) atom(s) or ion(s) is(are) gold or combination of gold and silver, or combination of gold and noble metal, or a combination of gold, silver and precious metal, which will be explained later. This statement does not mean that all atoms of gold or other metal cluster complex are elektrosnabzhenie. Some of the gold atoms and/or other metal can be elektrosnabzhenie and associated with one or more ligands, while other gold atoms and/or other metal may not be elektrosnabzhenie and may be associated with other metal atoms, but not with ligands.

Used in this description, the term "cluster" refers to a collection or group of atoms of gold, containing a set of two or more atoms of gold.

In one preferred embodiment, the cluster complex the gold-ligand has a diameter (or largest dimension) larger than the pore size of nanoporous titanium containing media. This preferred option essentially guarantees the absence of receipt of the cluster complex the gold-ligand and, therefore, gold nanoparticles in the pores or channels, or cavities nanoporous titanium containing media, and so essentially they remain on the outer surface of the media.

In another preferred embodiment, the cluster complex the gold-ligand cluster includes complex gold-ligand, it is in store one or more ligands, selected from the group consisting of amines, Iminov, amides, imides, phosphines, thiols, Filatov and mixtures thereof. In another preferred embodiment, the cluster complex the gold-ligand cluster includes complex gold-organophosphorus ligand, more preferably - cluster complex gold-organophosphine ligand.

In another preferred variant of such media includes nanoporous titanosilicate, more preferably nanoporous titanosilicate crystallographic MFI structure. Titanosilicate MFI structure has a maximum pore size of about 0.54±0,04 nm. In a more preferred embodiment, in which the nanoporous titanosilicate has a MFI structure, the cluster complex the gold-ligand preferably has a diameter (or largest dimension) of more than about of 0.54 nm (5.4 angstroms).

In still another preferred embodiment, the catalyst hydrocyclone further includes a promoter, defined as any elemental metal or metal ion, increased activity of the catalyst, which is explained in detail in the future. More preferably, the promoter is selected from silver, elements of the 1st group, 2nd group, lanthanide rare earth elements and actinide elements of the Periodic table, their salts and/or other compounds, and mixtures thereof, referenced in: CRC Hndbook of Chemistry and Physics, 75th ed. CRC Press, 1994.

In accordance with another aspect of this invention relates to the composition of the catalyst precursor containing the cluster complex the gold-ligand deposited on the nanoporous particles titanosilicates media.

In the method according to this invention can be used any olefin containing three or more carbon atoms, or a mixture of such olefins. Suitable are monoolefinic, which are compounds containing two or more ethylene communication, such as diene. The olefin can be a simple hydrocarbon containing only atoms of carbon and hydrogen, or alternatively, the olefin may be substituted at any of the carbon atoms of the inert Deputy. Used in this description, the term "inert" requires that the Deputy in the method according to this invention was essentially chemically inactive. Suitable inert substituents include, but are not limited to halides, simple, ether, ester, alcohol, or aromatic group, preferably chlorine, With_1-12simple broadcast_1-12ester and C_1-12alcohol group and_6-12aromatic group. Non-restrictive examples of olefins suitable for 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-GE the Saint, 3-hexene and, similarly, the various isomers of methylpentene, ethylbutane, Heptene, methylhexane, ethylpentane, propylbetaine, octene, including preferably 1-octene, and other higher analogues of these compounds, and butadiene, cyclopentadiene, Dicyclopentadiene, styrene, α-methylsterols, divinylbenzene, allyl alcohol, simple allyl ether, simple arelatively ether, allylmalonate, ZIOC scientists, Olivenza, simple allergenicity ether, simple arylpropionic ether and allylanisole. The olefin is preferably unsubstituted or substituted C_3-12the olefin, more preferably, unsubstituted or substituted C_3-8the olefin. Most preferably, the olefin is propylene. Many of the above olefins are commercially available, others can be obtained by chemical methods known to experts in this field.

The amount of olefin used may vary within a wide range, provided that the method produces the corresponding olefin oxide. Generally, the amount of olefin is dependent upon individual ways, including, for example, the design of the reactor, the olefin and economic considerations and safety. Professionals in this field know how to determine a suitable range of concentrations of the olefin-specific way. In light of this description, to the number of olefin is usually more than about 1 mol.%, preferably more than about 5 mol.% and, more preferably, more than about 10 mol.% in calculating the total number of moles of olefin, oxygen, hydrogen, and optional diluent. Generally, the amount of olefin is less than about 99 mol.% and, preferably, less than about 80 mol.% and, more preferably, less than about 60 mol.% in calculating the total number of moles of olefin, oxygen, hydrogen, and optional diluent.

For the method according to the invention is also necessary oxygen. Accept any source of oxygen, including air or substantially pure molecular oxygen. Can be other suitable sources of oxygen, including ozone and nitrogen oxides, such as oxides of trivalent nitrogen. The preferred molecular oxygen. The amount of oxygen used may vary within a wide range, provided that it is sufficient to obtain the desired olefin oxide. The amount of oxygen is preferably more than about 0,01 mol.%, more preferably, more than about 1 mol.% and, most preferably, more than about 5 mol.% in calculating the total number of moles of olefin, hydrogen, oxygen, and optional diluent. The amount of oxygen is preferably less than about 30 mol.%, more preferably, less than about 25 mol.% and, most preferably, less sample is about 20 mol.% in calculating the total number of moles of olefin, hydrogen, oxygen, and optional diluent. The oxygen concentration of more than about 20 mol.% may be in the range of Flammability of mixtures of olefin-hydrogen-oxygen.

For the method according to this invention is also necessary hydrogen. In the absence of hydrogen, the catalyst activity is greatly reduced. In the method according to this invention may be made by any source of hydrogen, including, for example, molecular hydrogen obtained from the dehydrogenation of hydrocarbons and alcohols. In an alternative embodiment of this invention, the hydrogen can be generated in situ in the reactor oxidation of the olefin, for example, in the dehydrogenation of alkanes, such as propane or isobutane, or alcohols, such as Isobutanol. Alternatively, hydrogen can be used to generate the catalyst-hydride complex or the catalyst-hydrogen complex, which can provide for how the necessary hydrogen. Trace amount of hydrogen in the air is too small to provide the required amount of hydrogen for the method according to this invention. An additional source of hydrogen must be filed in the manner or generated in the in situ method.

The method can be used any number of hydrogen provided that it is sufficient to obtain the olefin oxide. The appropriate number is odorata are usually more about 0,01 mol.%, preferably, more than about 0.1 mol.% and, more preferably, more than about 3 mol.% in calculating the total number of moles of olefin, hydrogen, oxygen, and optional diluent. Suitable amounts of hydrogen are usually less than about 50 mol.%, preferably, less than about 30 mol.% and, more preferably, less than about 20 mol.% in calculating the total number of moles of olefin, hydrogen, oxygen, and optional diluent.

In addition to the above reagents may be desirable to use a diluent, although its use is optional. Since the method according to this invention is exothermic, the diluent is advantageously provides a means for removal and dispersion formed of heat. In addition, the diluent provides an extended range of concentrations in which the reagents are non-flammable. The diluent can be any gas or liquid that do not inhibit the method according to this invention. The choice of solvent will depend on the circumstances in which the conduct process. For example, if the process is carried out in the gas phase, then a suitable gaseous diluents include, but without limitation, helium, nitrogen, argon, methane, carbon dioxide, water vapor and mixtures thereof. If the process is carried out in the liquid phase, then the diluent can be any resistant oxide the structure and heat-resistant liquid. Examples of suitable liquid diluents include aliphatic alcohols, preferably_1-10aliphatic alcohols, such as methanol and tert-butanol; chlorinated aliphatic alcohols, preferably_1-10chlorinated alkanols, such as chloropropanol; chlorinated hydrocarbons, preferably_1-10chlorinated hydrocarbons such as dichloroethane, and chlorinated benzenes, including chlorobenzene and dichlorobenzene; aromatic hydrocarbons, preferably_6-15aromatic hydrocarbons, such as benzene, toluene and xylene; ethers, preferably_2-20ethers including tetrahydrofuran and dioxane; and liquid polyethers, polyesters and polyols.

If a diluent is used in the gas phase, the amount of diluent is usually more than about 0 mol.%, preferably, more than about 0.1 mol.% and, more preferably, more than about 15 mol.% in calculating the total number of moles of olefin, oxygen, hydrogen, and diluent. If a diluent is used in the gas phase, the amount of diluent is typically less than about 90 mol.%, preferably, less than about 80 mol.% and, more preferably, less than about 70 mol.% in calculating the total number of moles of olefin, oxygen, hydrogen, and diluent. If you are using liquid rabbanites is (or solvent) in the liquid phase, the amount of liquid diluent (or solvent) is usually more than about 0 wt.% and, preferably, more than about 5 wt.% calculated on the total weight of the olefin and diluent. If you use a liquid diluent in the liquid phase, the amount of liquid diluent is usually less than about 99 wt.% and, preferably, less than about 95 wt.% in calculating the total number of moles of olefin and diluent.

Above the concentration of olefin, oxygen, hydrogen and diluent accordingly depend on the reactor design and parameters of the method disclosed in this description. Specialists in this field it is clear that in various hardware implementations of the method can be appropriately used different concentrations than those disclosed in this specification.

Advantageously used in the method of hydrocyclone according to this invention, the catalyst contains gold nanoparticles deposited on the nanoporous particles of such media. Gold is predominantly present in the form of a metallic gold (elemental or gold with zero valence). In this context, the term "primarily" means more than about 80%, preferably more than about 85% and, more preferably, more than about 90 wt.% metallic gold. Oxidized gold may be present in any oxide is hinnon state from more than 0 up to +3 or in the form of variations in the transition state during the catalytic cycle hydrocyclone or in stable form. To determine the degree(s) oxidation of gold can be used in any analytical technique that is capable of measuring the degree of oxidation and/or their relative amounts, such as photoelectron spectroscopy (XPS, XPS) or Mie scattering, measured on a UV spectrometer diffuse reflectance in the visible region (UV-VIS DRS). RES may be preferred and can be performed on the instrument for RES Kratos Axis 165 or instrument for RES PHI 5400 or any equivalents.

For visualization of the gold particles in the catalytic composition in its fresh or used the form, but also in the composition of the catalyst precursor can be advantageously used transmission electron spectroscopy, high-resolution (PAZUR, HRTEM). For this purpose, can be used in any transmission electron microscope high resolution, with permission from point to point 2Å or higher resolution. Statistics count PES are typically used to determine, depending on the preferences of the average or median particle size. ("Average particle size" is calculated by dividing the sum of the sizes of all particles in the sample by the number of particles in the sample. "Median particle size" is the size for which 50% of particles are smaller and 50% of the particles are larger.) As with ylki, discussing the statistics of counting PES, see: A. K. Dayte, et al., Catalysis Today, 111 (2000), 59-67, included in this description by reference. The catalytic composition of this invention typically includes a distribution of diameter gold nanoparticles (or the largest size in the case of nonspherical particles) in the range of from more than about 0.6 nm and preferably from more than about 0.7 nm to typically less than about 50 nm, preferably, less than about 20 nm, more preferably less than about 10 nm, even more preferably less than about 8 nm, which is measured PASUR. In one preferred embodiment, the median particle size of the gold fresh catalyst, measured PASUR, is in the range from about 0.8 nm to less than about 8,0 nm. The gold nanoparticles is not limited to a specific morphology. Can be any shape, including, for example, the bilayers, rafts, hemispheres, spheres, flattened shape (e.g. flat areas), cubooctahedrons and their truncated versions.

To provide information about the average or median particle size of gold in any form of the catalyst (fresh or used) or catalyst precursor may optionally be applied x-ray absorption spectroscopy microstructure (RASM, XAFS) with synchrotron x-ray source (e.g. the R, Advanced Photon Source, Argonne National Laboratory or the National Synchrotron Light Source, Brookhaven National Laboratory, USA). The technique depends on the dimension of the coordination number (or the number of neighboring atoms of gold), which is then correlated with the size of the gold particles. RSM can also give information about the average oxidation state of gold.

In preferred embodiments of the catalyst according to this invention, where the carrier has a pore size between 0.2 nm and 1 nm gold nanoparticles placed essentially on the external or outer surface of the nanoporous particles of such media. In this invention, the term "outer surface" of nanoporous titanium containing carrier includes an outer surface or shell surrounding the particles or agglomerates media. The outer surface includes all the relief forms, as well as surface cracks, the width of which more depth. In contrast to the "external surface", the term "internal or deep surface" includes wall all pores, channels, cavities and cracks, the depth of which is greater than width. In reference to the gold nanoparticles, which in preferred embodiments according to this invention is essentially placed on the outer surface of the carrier, the term "essentially" means that more than about 90% and preferably more than about 95% of the gold nanoparticles placed on the outer surface of the carrier. For the NGOs, less than about 10% and preferably less than about 5% of the gold nanoparticles is present on the inner surface of such media.

The size and placement of the gold nanoparticles can be observed by transmission electron microscopy (TEM) or scanning transmission electron microscopy (SPEM), preferably tomography method transmission electron microscopy (TEM tomography). The imaging method of the EMP provides for the determination of three-dimensional structures by electron microscopy. Sample PAM looks at different angles of rotation, such as when 0°, 15°, 20°, 40° and so on; and from the resulting compilation of images of the person skilled in the art can determine where a particle of gold on the external surface or on the inner wall. Tomography method PAM can be carried out using a FEI Tecnai-12 (FEI COMPANY™, series No. D250)operating at 120 kV. The microscope is usually provided with a subject table CAMPUS© and fully regulated by the computer. Computer software for tomography brand FEI can be used to control the education of the image and the registration conditions during the collection of inclined rows. The alignment of the inclined rows and reconstruction of 3-D volume can be implemented using computer software Inspect 3D© (FEI COMPANY™). For visualization and manipulirua the Oia 3-D volume can be used computer software Amira© (version 3.1.1, FEI COMPANY™).

For TEM measurements and TEM tomography presents the following publications are included in this description by reference:

Willams, D.B. and Carter, C. C., Transmission Electron products microcopy I-Basics, Chapter 1, Plenum Press, New York,1996;FEI company, Advanced THE Tecnai software for easy acquisition, reconstruction and visualization; Flannery, B.P., Deckmean, H.W., Robergy, W.G., and D'amico, K.L., Science1987,237, 1439; Hoppe, W. and Hegerl, R., Three-dimensional structure determination by electron microscopy (nonperiodic specimens), in Hawkes, P.W. (Ed.), Computer Processing of Electron Microscope Images, Springer, Berlin, Heidelberg, New York,1980;Frank, J.. Three-dimensional Electron Microscopy of Macromolecular Assemblies, Academic Press, San Diego,1996;Midgley, P.A. and Weyland, M, "3D Electron Microscopy in the Physical Sciences: the Development of Z-contrast and EFTEM tomography," Ultramicroscopy, 2003,96,413-431.

The method according to this invention in comparison with the methods of the prior art provides best practice process with low loads of gold on the catalyst. Typically, the loading of gold is more than about 10 hours per million), preferably, more than about 50 PM/m and, more preferably, more than about 100 hours/million calculated on the total weight of the catalytic composition. Typically, the loading of gold is less than about 20000 hours per million, preferably less than about 5000 hours/million, more preferably less than about 1000 hours/million calculated on the total weight of the catalytic composition.

"Such media may be any solid substance in which the titanium is integral to the component frame structure of solids, or in which the titanium grafted or deposited on the structure of solids, or where there is a combination of frame structure and grafted or precipitated titanium. The term "nanoporous", when he describes such media, refers to the presence of channels, pores and/or cavities within the frame structure of the carrier width (or largest dimension) in the range from about 0.2 nm to about 50 nm. Such porous structures have micropores in the form of pores of a width not exceeding approximately 2 nm, mesopores in the form of pore width in the range from about 2 nm to 50 nm. The greater the void space between particles or particles inside width of more than 50 nm is not included in the term "nanoporous". As mentioned above, distribution channels, pores and/or cavities may be regular or chaotic; and pores and/or channels may have one, two or three dimensions. Such media may be crystalline, quasicrystalline or amorphous. In such media the titanium exists essentially in the form of a non-metallic titanium.

The distribution width of the pores in such media can be determined from adsorption isotherms using, for example, gaseous nitrogen at a temperature of the boiling point of nitrogen at atmospheric ambient pressure. The specific surface of the carrier can be ODA is divided by adsorption of gas on BET (equation of brunauer, Emmett and teller). For a more complete discussion of such methods is given in ASTM D 3663-78 and IUPAC, K. S. W. Sing, et. al., "Reporting Physisorption Data for Gas/Solid Systems with special Reference to the Determination of Surface Area and Porosity, Pure & Applied Chemistry, Vol. 57, No.4 (1985), pp. 603-619, included in this description by reference. Usually nanoporous titanium containing the carrier has a specific surface area of more than about 5 m²/g, preferably more than about 50 m²/g, more preferably more than about 150 m²/g determined by BET method.

Suitable carrier materials include, but without limitation, such such amorphous and crystalline silicas, as silicalite or MCM-41, alumina, metroselect, such as silicates and, preferably, titanosilicates, silicates metal promoter, such as the silicates of elements of the 1st and 2nd group and lanthanide and actinide elements, and other refractory oxides or traditional materials for media.

Suitable as a carrier can be stoichiometric or non-stoichiometric metal titanates-promoter crystalline or amorphous nature, having a specific surface of more than about 5 m²/g, non-restrictive examples of which include the titanates of metals of the 1st group, 2nd group and lanthanide and actinide metals. A titanate of a metal promoter is suitably selected from groups who, consisting of magnesium titanate, calcium titanate, barium titanate, strontium titanate, sodium titanate, potassium titanate, lithium titanate, titanate cesium, rubidium titanate and titanate erbium, lutetium, thorium, and uranium. As an additional suitable media can be used amorphous or crystalline titanium dioxide, including anatase, rutelinae and brugidou phase of titanium dioxide having a specific surface of more than about 5 m²/year

Preferred of such carriers are disclosed in WO 98/00413, WO 98/00414, WO 98/00415 and in U.S. patent No. 6255499 B1, included in this description by reference.

In cases where titanium is attached to the media or in media, download titanium can be any load, which makes it possible to obtain an active catalyst in the method according to this invention. Typically, the loading of titanium is more than about 0.02 wt.%, preferably, more than about 0.1 wt.% in the calculation of the mass media, including any binder, which was mentioned before. Typically, the loading of titanium is less than about 35 wt.% and, preferably, less than about 10 wt.% in the calculation of the mass media, including any binder. It is clear that in cases where titanium is a stoichiometric component of the carrier, as, for example, titanates, metal-promoter, mass is oncentrate titanium in the media can be more than 35 wt.%.

In a more preferred embodiment, the carrier includes a nanoporous titanosilicate, even more preferably titanosilicate zeolite. Even more preferred of such media includes nanoporous titanosilicate selected from the TS-1, TS-2, beta-Ti, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15 and Ti-SBA-3. The most preferred titanosilicate includes quasi-crystalline titanosilicate having MFI structure, which is orthorhombic structure at room temperature (21°C), as determined by x-ray diffraction (XRD) (XRD). Such a vehicle and method thereof are disclosed in U.S. patent No. 6255499 included in this description by reference.

The atomic ratio of silicon to titanium (Si:Ti) preferred titanosilicates media can be any ratio that provides the catalyst for an active and selective hydrocyclone in the method according to this invention. Usually best atomic ratio of Si:Ti is approximately 5:1 or greater, preferably, equal to about 50:1 or more. Usually best atomic ratio of Si:Ti equal to about 1000:1 or less, preferably, is approximately 300:1 or less.

In the catalyst according to this invention can be used in any combination or mixture of the above titanium containing media.

Such media may be given any shape, suitably is for catalyst particles, for example, it may be in the form of beads, granules, spheres, honeycombs, monoliths, extrudates and films. Such media, optional, can be extruded with the secondary media associated with him or may be on the order of the joint linking catalyst particles and/or increase the strength of the catalyst or resistance to abrasion. It may be desirable, for example, thin films of such carrier to the secondary carrier, which gives the form of beads, pellets or extrudate. Suitable secondary carriers include carbon and any refractory oxide, such as silicon dioxide, titanium dioxide, aluminum oxide, aluminosilicates and magnesium oxide; ceramics, including ceramic carbides and nitrides, as well as any metal carrier. The number of secondary carrier is usually from about 0 to about 95 wt.% calculated on the total weight of the catalyst (gold and titanium containing carrier and a secondary carrier under the following condition. When the binder or the secondary carrier is titanium dioxide, the total amount of titanium dioxide is usually not more than 35 wt.% calculated on the total weight of the catalyst including the secondary carrier. Unless specified otherwise, any binder, is added to the titanium containing media, physically mixed with it, EC is trueromance with it or incorporated in it, should be considered a component of such media.

Particles of nanoporous titanium containing media containing any binder, preferably have a diameter (or largest dimension) of more than approximately 50 nm and less than about 2 microns (μm). More preferably, the particles of nanoporous titanium containing media, including binder, have a diameter (or largest dimension) of more than approximately 50 nm and less than about 1 μm.

Catalyst hydrocyclone according to this invention at the present time is preferably obtained by a process comprising the deposition cluster complex gold-ligand on nanoporous titanium containing media under conditions sufficient to obtain a catalyst precursor, and subsequent heating and/or chemical treatment of the catalyst precursor under conditions sufficient for the formation of catalytic compositions for hydrocyclone according to this invention. In preferred embodiments according to this invention preferably uses the cluster complex the gold-ligand, which has a diameter (or largest dimension) is greater than the pore size of such nanoporous media. This cluster complex essentially has no access to the pores, channels or cavities of the carrier; and therefore, in such preferred embodiments, the cluster complex, there is associated with the external surface of the carrier. Cluster complexes gold-ligand have several advantages in comparison with the colloidal suspensions of the prior art, used in obtaining catalysts hydrocyclone. First, cluster complexes gold-ligand tend to become isolated solid particles of relatively pure and monodisperse form. As with other sustainable connections with the cluster complexes gold-lingand you can go without a lot of effort to prevent contact with oxygen and/or water. The inventors recommend, however, specific preferred methods listed below.

Typical clusters of gold found in the cluster complex the gold-ligand, contain 2, preferably more than about 4 and more preferably, more than about 5 atoms of gold. Typical clusters contain less than about 10,000, preferably less than about 500 atoms of gold. Cluster complexes gold-ligand containing the following number of gold atoms, are particularly preferred for the cluster complex the gold-ligand, which is deposited on the titanium containing carrier: Au₃Au₄Au₅Au₆Au₇Au₈Au₉Au₁₀Au₁₁Au₁₂Au₁₃Au₂₀Au₅₅and Au₁₀₁. Currently, more preferably Au₅₅. Because the number of gold atoms in the cluster increases, when receiving exactly monodisperse clusters can be difficult. Therefore, the number of atoms of gold are expected to be some changes. For clusters containing 20 or more gold atoms, the number of gold atoms can be expected to change by ±10%; for example Au₂₀Au₅₅and Au₁₀₁better be defined as: Au_(20±2)Au_(55±5)and Au_(101±10).

The cluster complex the gold-ligand, optionally, can contain any number of atoms of another metal, which can be found in the mixed cluster complexes gold-silver or gold is a noble metal, noble metal selected from ruthenium, rhodium, palladium, osmium, iridium and/or platinum; preferably in cluster complexes gold-silver, gold-palladium and/or gold-platinum-ligand. Although the noble metal may be present, however it may contribute to the increased degree of hydrogenation of the olefin, for example, increased formation of propane from propylene. Accordingly, when there is a noble metal like palladium or platinum, the catalyst is advantageous to add the silver (i.e. Au/Ag/noble metal) to reduce the hydrogenation. In preferred embodiments according to this invention the cluster complex the gold-ligand eliminates noble metal selected from ruthenium, rhodium, palladium, osmium, iridium, platinum and mixtures thereof.

the data the invention is not limited by the bonds of the atoms in the cluster of gold. The gold atoms can be linked to each other directly through communication Au-Au; or, alternatively, a single gold atom can be bonded to another atom of gold intermediate atom, such as oxygen or sulphur, as in the Au-O-Au; or the gold atom can be associated with an atom of another metal, such as silver or noble metal directly (for example, Au-Ag or Au-Pd) or intermediate atom, which is specified above.

Non-restrictive examples of ligands suitable for cluster complex gold-ligand include organophosphorus ligands, such as organophosphinates, organophosphinates, organophosphites and organophosphine ligands, as well as thiolate [for example, -S(CH₂)₁₁(CH₃)], thiols [HS(CH₂)₁₁(CH₃)], amines (e.g., primary and secondary amines and aminoalcohols), imine, amides (for example, palmitoylated), imides (for example, maleimido, succinimido, phthalimido), carbon monoxide, and a halide (F, Cl, Br, I) and their mixtures. The preferred ligand is an organophosphorus ligand, more preferred variants which include triorganotin, such as triarylphosphine, trialkylphosphine, alkyldiphenylamine and dialkylacrylamide, more preferably, those in which each alkyl is C_1-20the alkyl and each aryl is_6-20the aryl. Neogranicen the s examples of cluster complexes gold-ligand, suitable for use in this invention include:

in which Ph is phenyl and Me is stands; and cluster compounds and complexes of gold-ligand, commercially available from companies including Strem Chemicals and Nanoprobes, Incorporated, including cluster complexes gold-ligand installed catalog number Nanoprobes 2010, 2022, 2023. Suitable permissive varieties mixed cluster complexes gold is a noble metal-ligand include:

where "Ph" is phenyl. Can also be suitably used a mixture of any of the above cluster complexes gold-ligand, including cluster complexes only gold, gold-silver-, gold-precious metal - and gold-a precious metal-silver-ligand. Phosphine ligands in the above formula can be replaced by any other equivalent triorganotin ligand, such as tri(tolyl)phosphine or bis(diphenylphosphino)methane. In addition, in the above preferred formulae of any of the anions can be replaced by an equivalent anion. More preferred the cluster complex the gold-ligand is a cluster complex gold brand Nanogold® - ligand, with an average the size of the gold particles of approximately 1.4 nm, which can be purchased from Nanoprobes, Incorporated.

Before deposition on the carrier of the cluster complex the gold-ligand may be analyzed, for example, infrared spectroscopy and/or spectroscopy nuclear magnetic resonance (NMR) solution (e.g., NMR¹H,¹³With or³¹R) for characteristics of the ligand(s) and complex. Cluster complexes gold-ligand, including mixed cluster complexes of gold is a noble metal-ligand can be purchased from commercial sources or, alternatively, synthesized by the methods disclosed in this region. The following publications describe the synthesis of cluster complexes gold-ligand and their characteristics, and all publications included in this description by reference.

Nesmeyanov, A.N., et ah,Journal of Organometallic Chemistry1980,201,343-349; Briant, C.E., et al., J.Chem. Soc, Chem Commun.1981,201; Briant, C.E., et al,Journal of Organometallic Chemistry1983,254,C18-C20; Van der Velden, J.W.A., et al,Inorganic Chemistry1983,22,1913-1918; Schmid, G., et al,Polyhedron1988,7, 605-608; Ito, L.N., et al,Inorg. Chem.1989,28,2026-2028; Ito, L.N., et al,Inorg. Chem.1989,28,3696-3701; Schmid, G.,Inorganic Syntheses1990,27,214-18; Ramamoorthy, V., et. al,J. Am. Chem. Soc.1992,114,1526-1527; Laguna, A., et al,Organometallics1992,11,2759-2760; Rapoport, D. H., et al,J. Phys. Chem. B.1997,101,4175-4183; Warner, M.G., et al,Chem. Mater.2000,12,3316-3320; K. Nunokawa, et al.Bulletin of the Chemical Society of Japan2003,76,1601-1602-years; Negishi, Y., et al,J. Am. Chem. Soc.2004,126,6518-6519; and Shichibu, Y., et al,J. Am. Chem. Soc.2005,127,13464-13465.

On the method of deposition of the cluster complex the gold-ligand on such media has no limitations until such time as the catalyst is active in the way hydrocyclone according to this invention. Non-restrictive examples of suitable deposition methods include impregnation, deposition-planting, spray drying, ion exchange reaction in the solid phase and drying by freezing. It is preferable to treatment, including, if desired, the wetting of the carrier until the initial moisture or until a greater or lesser humidity solution, suspension or colloid containing the cluster complex the gold-ligand. Conditions of impregnation may vary depending on the specific cluster complex gold-ligand, its concentration in solution or suspension, and specifically from the media. If necessary, the carrier may be processed by multiple impregnations.

Typically, the temperature of deposition is in the range from a temperature below about ambient temperature (taken as about -100°C.) to about 300°C. Suitable solvents include, but without limitation, water and organic solvents, after which the include alcohols (for example, methanol, ethanol, isopropanol, butanol), esters, ketones (e.g. acetone), aliphatic and aromatic hydrocarbons and kalogeropoulou (e.g., methylene chloride) and alkalophile, such as ethylene glycol and diethylene glycol. Suitably also used a mixture of water and organic solvents. If you are using the solution, the concentration of the cluster complex the gold-ligand is typically in the range from approximately 0,M to the point of its saturation, preferably from about 0,M to about 0.5m. The solution optionally may contain cationic and/or anionic additives, including, for example, ions of the metal-promoter (e.g., Li⁺, Na⁺, K⁺, Rb⁺Cs⁺, Mg²⁺Ca²⁺, Sr²⁺, Ba²⁺La³⁺and Sm³⁺), which will be mentioned hereinafter and anionic species such as halides, sulfates, phosphates, carbonates, borates, nitrates and carboxylates, such as acetates, lactates, citrates, maleate, cinnamate and mixtures thereof. The deposition is usually carried out at ambient pressure in air atmosphere. After completion of the deposition can be selected by traditional methods, the composition of the catalyst precursor. To extract the catalyst precursor solution after deposition can be filtered, centrifuged or dementiava; or to extract the por is destinia catalyst, the solvent can be evaporated or distilled. The resulting composition of the catalyst precursor can be dried at room temperature, if necessary, and can be stored for future use. To reduce the moisture is preferably stored in the refrigerator in an air atmosphere.

The composition of the catalyst precursor containing the cluster complex the gold-ligand deposited on the nanoporous particles of such media can be described as any modern analytical method. To establish the chemical composition of the catalyst precursor can be used, for example, neutron activation analysis (NAA, NAA) or x-ray fluorescence (XRF, XRF). To visualize the clusters still attached ligands can be used SPM (STM). To determine the oxidation state of the gold can be used RES (XPS). For the determination of gold or other metals at low concentrations can also be applied spectroscopy of the electron energy losses of high-resolution (SAPEUR, HREELS).

The catalyst precursor is then heated and/or chemically treated under conditions sufficient for the formation of the catalyst according to this invention. One suitable method is to heat in an inert atmosphere. Inert atmosphere include nitrogen, helium, neon, argon and the such noble gases, and thinners, including methane, carbon dioxide, water vapor and aliphatic hydrocarbons, such as propane. The alternative, is also suitable and may be preferred heating with simultaneous chemical treatment, such as annealing in an oxidizing atmosphere or heating in a reducing environment, which will be revealed in the future. The heating temperature depends on specifically incorporated ligand, but may be in the range of from more than about 50°C., preferably from more than about 100°C. to about 800°C., more preferably from about 120°to about 500°C. For the preferred cluster complexes with phosphine ligands, the preferred heating temperature is in the range from about 120°to about 400°C.

Properly can also be used in chemical processing with heating or without heating. Chemical treatment includes contacting the composition of the catalyst precursor with chemically active product, for example, with a reducing agent or oxidizing agent. Non-restrictive examples of suitable oxidants include essentially pure oxygen, air, ozone, nitrogen oxides, hydrogen peroxide and mixtures thereof. The oxidizer, optionally, may be diluted with an inert gas, which was mentioned before. The preferred oxidizer is such or a mixture of oxygen and inert(s) strip(s), such as helium. Non-restrictive examples of suitable reducing agents include hydrogen, alkenes (preferably_1-10alkenes, such as propylene), sodium borohydride, DIBORANE, formaldehyde, sodium nitrite, oxalic acid, carbon monoxide, hydrogen peroxide and mixtures thereof. The authors note that hydrogen peroxide can act either as an oxidant or a reductant. The preferred reducing agent is a hydrogen, optionally diluted with an inert gas. If an oxidizing agent or a reducing agent is used an inert gaseous diluent, the concentration of oxidant or reductant in the diluent may suitably be in the range of from about 1% to about 99 vol.%. The composition of the precursor, as an optional operation, can be washed with hydrogen peroxide or can interact in solution or suspension with sodium borohydride. The catalyst precursor alternative can be turned into a catalyst according to this invention by heating in an atmosphere of hydrogen or oxygen in situ in the reactor hydrocyclone before hydrocyclone. The preferred treatment involves heating the catalyst in situ in an atmosphere of hydrogen or hydrogen diluted with an inert gas, more preferably, at a temperature in the range of about 200º is up to about 300OC.

Heat and/or chemical treatment is carried out in a period of time sufficient for the formation of catalyst hydrocyclone according to this invention. Usually a sufficient period of time from about 15 minutes to about 5 hours. Depending on the specific conditions of heat and/or chemical treatment and temperature relationship of the gold-ligand may or may not be broken. To confirm that the composition of the precursor during heating and/or chemical treatment removes the ligand, can be applied x-ray fluorescence (XRF); however, removal of the ligand is not a requirement to obtain an active catalyst hydrocyclone according to this invention.

The composition of the catalyst and catalyst precursor according to this invention optionally can include a promoter or combination of promoters. As a promoter may be used any of the elemental metal, metal ion, or combination thereof, which enhance the efficiency of the catalyst in the oxidation method according to this invention. Factors contributing to increased efficiency include, but without limitation, an increased degree of conversion of the olefin, increased selectivity to olefin oxide, reduced water production, increased service life of the catalyst and reduced molar ratio of water to olefin oxide is, preferably H₂ABOUT/. Usually the valence of the ion(s) of the promoter is in the range from +1 to +7, but can also be present metal species (zero valence). Non-restrictive examples of suitable promoters include metals 1-12 groups of the Periodic table of elements, and rare earth lanthanides and actinides, which are mentioned in the CRC Handbook of Chemistry and Physics, 75th ed., CRC Press, 1994. The promoter is preferably selected from silver, metals of the 1st group comprising lithium, sodium, potassium, rubidium and cesium; metals of the 2nd group comprising beryllium, magnesium, calcium, strontium and barium; rare earth lanthanides, including lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; and actinide metals, in particular of thorium and uranium. The promoter is preferably selected from silver, magnesium, calcium, strontium, barium, erbium, lutetium, lithium, sodium, potassium, rubidium, cesium, and combinations thereof.

If you are using one or more promoters, the total number of promoter(s) is usually more about about 0.001 wt.% and, preferably, more than about 0.005 wt.% calculated on the total weight of the catalyst. The total number of promoter(s) typically is less than about 20 wt.% and preferably less than about 15 wt.% calculated on the total of Massalfassar.

The promoter(s) may be precipitated(s) of such carrier concurrently with the cluster complex the gold-ligand or, alternatively, on a separate stage, or before the deposition or after the deposition of the cluster complex the gold-ligand. If such media should be made during the preparation of the catalyst, the promoter(s) may be precipitated(s) the material is not Ti-carrier simultaneously with the titanium source or, alternatively, on a separate stage, or before the deposition or after deposition of the titanium source. Typically, the promoter(s) precipitated from aqueous or organic solution or suspension containing one or more salts of the metal-promoter and, optionally, other additives. Can be used any salt of the promoter; for example, a halide promoter, such as the fluorides, chlorides and bromides; nitrates, borates, silicates, sulfates, phosphates, hydroxides, carbonates, bicarbonates and carboxylates, in particular acetates, oxalates, cinnamate, lactates, maleate, the citrates. Can be used mixtures of the above salts. If you are using an organic solvent, it can be any of many known organic solvents, including, for example, alcohols, esters, ketones, and aliphatic and aromatic hydrocarbons. Typically the carrier is in contact with the salt solution of a promotion the RA in terms which are similar to those used for contacting the carrier with a solution of the cluster complex the gold-ligand. After deposition of the promoter(s), optional, carry out the washing; and if it is done, wash liquid preferably contains a salt of the desired promoters. After this can be carried out heating the impregnated promoter of the carrier in an inert gas or heat and/or chemical treatment with reducing agent or oxidizing agent in a manner similar to that previously described for processing after the deposition of the cluster complex the gold-ligand.

The method according to this invention can be carried out in a reactor of any conventional design for processes in the gas or liquid phase. Such designs are widely include the batch reactor, the reactor fixed bed reactor with a moving bed reactor fluidized bed reactor with a moving bed reactor with a layer of nozzles with jet stream of fluid and shelf, and the tubular reactor, and the reactor design of continuous operation with intermittent flow and swing reactor. Olefin, hydrogen and oxygen can communicate together. Alternatively, the method can be carried out Paladino, the first catalyst is introduced into contact with oxygen and then the oxidized catalyst is introduced into contact with a mixture of PR is Elena and hydrogen. The method preferably is carried out in the gas phase and in the design of the reactor provides heat removal of the heat generated. Preferred reactors designed for these purposes include reactors fixed bed, shelving and tubular, fluidized bed and moving bed and the reactor, consisting of a set of catalytic layers connected in parallel and are used interchangeably.

Conditions of the open method of oxidation may vary significantly depending on the non-or Flammability used mixtures. However, it is advisable to recognize that the conditions for non-flammable and flammable mixtures of olefin, hydrogen and oxygen are different. Respectively, may be made or taken into account chart of the composition, which for any given temperature and pressure process shows flammable and nonflammable range of compositions of the reagents, including the diluent, if used. It is assumed that the preferred mixture of the above reagents are outside the Flammability, when the method operates at the preferred temperatures and pressures listed below. However, a possible process in the mode of Flammability, which was developed by experts in this field.

The method is usually carried out when the temperature is more than about 160°C. preferably more than about 180°C. generally carried out at a temperature less than about 300°C., preferably less than about 280°C. the Pressure is typically in the range of from about atmospheric to about 500 psig (3549 kPa), preferably from about 100 psi (690 kPa) to about 300 psig (2170 kPa).

In flow reactors, the residence time of the reactants and the molar ratio of the reactants to the catalyst is usually determined by the bulk velocity. For the process in the gas phase average hourly feed rate of the olefin (GHSV) may vary within a wide range, but is usually more than about 10 ml of olefin per ml catalyst per hour (h^-1), preferably more than about 100 h^-1and, more preferably, more than about 1000 h^-1. GHSV of olefin is usually less than about 50000 h^-1preferably, less than about 35000 h^-1and, more preferably, less than about 20000 h^-1. For the process in the gas phase total average hourly rate of flow of the feedstock containing olefin, oxygen, hydrogen, and optional diluent may vary within a wide range, but is usually more than about 10 ml of gas per ml of catalyst per hour (h^-1), preferably more than about 100 h^-1and, more preferably, more than about 1000 h^-1. GHSV flow source is about raw materials, containing olefin, oxygen, hydrogen, and optional diluent, typically less than about 50000 h^-1preferably, less than about 35000 h^-1and, more preferably, less than about 20000 h^-1. Similar to the process in the liquid phase average hourly feed rate (WHSV), in this case, the olefin component may vary within a wide range, but is usually more than about 0.01 g of the olefin on g catalyst per hour (h^-1), preferably more than approximately 0.05 h^-1and, more preferably, more than about 0.1 h^-1. WHSV of olefin is usually less than about 100 h^-1preferably, less than about 50 h^-1and, more preferably, less than about 20 h^-1. Average hourly rate of gas supply and oxygen, hydrogen and diluent can be determined from the flow rate of the olefin with taking into account the desired relative molar relationship.

When the olefin having at least three carbon atoms, is introduced into contact with oxygen in the presence of hydrogen and the above-mentioned catalyst, receive the corresponding olefin oxide (epoxide) with high selectivity and productivity. The preferred olefin oxide is propylene oxide.

The degree of conversion of the olefin in the method according to this invention may vary depending on oncrete used process conditions, includes separate olefin, temperature, pressure, molar ratio of reactants and the shape of the catalyst. In this invention, the term "degree of transformation (conversion)" is defined as the molar concentration of the olefin, which interacts with the formation of the products. Usually the degree of conversion of the olefin of more than about 1.0 mol.%. The degree of conversion of the olefin is preferably more than about 1.5 mol.%, more preferably more than about a 2.0 mol.%.

The selectivity to olefin oxide may vary depending on the specific conditions used in the process. In this invention, the term "selectivity" is defined as the molar concentration of the reacting olefin, which forms a separate product, preferably the olefin oxide. In preferred variants of the method according to this invention, in which the cluster complex the gold-ligand eliminates noble metal oxides olefins with unexpectedly high selectivity. The selectivity to olefin oxide is usually more than about 80, preferably more than about 85, and more preferably, more than about 90 mol.%.

The performance of the catalyst, measured in grams of propylene oxide per kilogram of catalyst per hour (g/kg cat.-h)used depends on the specific catalyst and the process conditions, such as t mperature, the pressure and feed rate of the feedstock. Performance is usually more than about 200 g/kg cat.-hour, preferably more than about 250 g/kg cat.-hour and, more preferably, more than about 300 g/kg cat.-hour.

The efficiency of hydrogen is predominantly higher than in the methods of the prior art. Accordingly, the cumulative molar ratio water/propylene oxide in the product flow, averaged over the total time of experience is low. More specifically, the cumulative molar ratio water/olefin oxide is usually more than about 1:1 but less than about 8:1 and preferably less than about 6:1.

The catalyst of this invention shows evidence of increased service life of the catalyst. Used in this description, the term "lifetime" refers to the time measured from the beginning of the oxidation process to the moment at which the catalyst after one or more regenerations loses sufficient activity that makes use of a catalyst is unacceptable, especially from a commercial point of view. As evidence of its long life, the catalyst remains active for a longer time intervals with stable activity and low deactivation compared with catalysts hydrocyclone precede the level. Typically, the operating time of the catalyst is more than approximately 25 days, preferably more than about 30 days, can be achieved in the reactor with a fixed bed. In more preferred embodiments, the catalyst according to this invention worked over time to about 40 days with minor decontamination.

When its activity is reduced to an unacceptably low level, in preferred embodiments, the catalyst according to this invention can be regenerated. For catalyst according to this invention can be generally used with any method for regenerating catalyst, known to specialists in this field, provided that the catalyst to regenerate disclosed in this description of how hydrocyclone. One suitable regeneration method includes heating the deactivated catalyst at a temperature of from about 150 º C to about 500º in the atmosphere regeneration gas containing oxygen, hydrogen, water, ozone or a mixture thereof and, optionally, an inert gas installed before. The preferred regeneration temperature is in the range from approximately 200ºC to about 400ºC. Oxygen, hydrogen or water preferably ranges from about 2 to about 100 mol.% the regeneration gas. Regeneration time depends on the used regenerating agent; but typically may be in the range of the t more than about two minutes to about 20 hours.

The invention will be further explained when considering the following examples, which are intended only to illustrate the use of the invention. For specialists in this field will be obvious other variants of the invention from a consideration of this specification or practice of the invention disclosed in this description. Unless otherwise indicated, all percentages are given in mol.%.

To establish compositions of the catalyst precursor and catalyst used, the following analytical methods.

Elemental analysis: concentrations of Au, Ti, Si and metal-promoter determined by neutron activation analysis (NAA, NAA) and the concentration of P determined by x-ray fluorescence (XRF, XRF).

Sample preparation for TEM (TEM): the catalyst particles (14/30 mesh U.S.: 1410/595 μm) was crushed and was dispersively on Cu grid for TEM lattice carbon media purchased from T. Pella (for example, catalog number 01883).

Instrumentation for analytical TEM: to image the nanoparticles of metal on nanoporous media methods in conventional TEM and dark field used gun for field emission (JEOL 2010F No. series EAT 138714-25). TEM was performed at an accelerating voltage of 200 Kev.

Conventional TEM images were recorded using multicamera Gatan digital camera (Model MSC794). Caught also the picture is ment annular dark field with a high angle using computer software Gatan Digiscan with image size 512×512 or 1024×1024 pixels.

General method for the synthesis of crystalline titanosilicate catalyst carrier

Crystals of nanometric size (the largest size of ~500 nm) titanosilicates media synthesize using tetraethylorthosilicate (TEOC) (TEOS), n-butoxide titanium hydroxide of tetrapropylammonium (GTPA, TPAOH) in an aqueous reaction mixture having the molar composition: 1,0 Si:0,0067 Ti:25 H₂O:0,1 TPA. In purged with nitrogen 50-liter bottle add TEOS (20,11 kg). Separately purged with nitrogen vessel in the mixing container add TEOS (1,84 kg) and piperonyl Ti (239,5 g). Then in the container, the mixture is poured into a 50-l bottle containing TEOS. The bottle seal and intensively mixed by shaking. In the second 50-liter bottles of deionized water (41,79 kg) is mixed with GTP (to 8.57 kg). A mixture of GTP/N₂About seal and intensively stirred. The resulting solution of GTP/N₂About placed overnight in a refrigerator and keep cold by placing on ice until further use.

A mixture of piperonyl Ti/TEOS add loading in vacuum purged with nitrogen, the reactor jacket, provides temperature-5ºC. The cooled solution of GTP/N₂About served by the pump into the reactor for about 65 minutes at a stirring speed of 150 rpm After migration is complete, the reactor is heated to 60 to 65 º C (approximately 20 minutes). Found the the temperature value is maintained for 4.5 hours. The temperature was raised to 160º with a maximum heating rate (about 50 minutes) and maintained for 96 hours. Then the reactor is cooled to -20 ° C to extract the crystals titanosilicate.

Crystals titanosilicate removed by flocculation. Using a 1.0m solution of HNO₃the pH of the solution of the above product synthesis adjusted to pH 8.0±0,2 by slow addition of the acid with vigorous stirring while controlling the pH. After adjusting the pH of the suspension is centrifuged at a speed of about 300-600 rpm Suspension with pH adjusted filtered through a cloth filter into a plastic centrifuge bag to retrieve the crystals. The mother liquor recycle and put in a centrifuge bags many times before removing approximately 96% of the total solids content. Then through solid filter residue miss fresh deionized water to flush excess of GTP and unreacted precursor. The wet solid filter residue is distributed in fresh deionized water. After distribution of the crystals in suspension immediately and continuously stirred at room temperature. The obtained solid matter of the above extract by centrifugation and subsequent removal of wet solids and drying in air atmosphere at 80 ° C. The obtained solid is astitsy crushed and sieved to highlight faction 14/30 mesh (U.S. 1410/595 μm). The substance calcined in a muffle furnace in air atmosphere as follows: temperature rise from room temperature up to 550º speeds of 2,5 º C/min, followed by exposure at 550º for 10 hours and subsequent cooling to room temperature. This technique is carried out in a static form, i.e. in the oven intentionally does not serve the air flow. The product contains nanoporous titanosilicate material with the MFI structure, specific DRL. Titanosilicates the product shows the mass ratio of Si:Ti equal to 150:1, a certain NAA.

Example 1

Sample nanoporous titanosilicate media obtained, as mentioned above, dried for 1 hour at 110 º C. Prepare an aqueous solution of sodium acetate (NaOAc) mixing water (75 g) and NaOAc (0,737 g). A solution of NaOAc (70,01 g) is added dropwise into the flask containing titanosilicate media (100,00 g), with shaking while adding. The flask is transferred into a vacuum oven and placed under vacuum at room temperature for 30 minutes, followed by two cycles of shaking and applying vacuum at room temperature for 30 minutes. The sample was then heated in a vacuum to 70 º C (±5 º C, temperature rise for 25 minutes) and incubated for 1 hour. The heating is switched off, the sample is cooled to room temperature and maintained under vacuum during the night. coumou furnace blown off with nitrogen and extract the sample. Substance re-sieved to highlight faction 14/30 mesh (U.S. 1410/595 μm) and placed in a flask.

Part of the saturated NaOAc titanosilicates carrier is dried in an oven at 110 º C for 1 hour. Prepare a solution of a gold cluster-ligand mixing Au₉(PPh₃)₈(NO₃)₃(0,0040 g) with acetone (2,873 g) and methanol (to 0.900 g). The solution cluster gold-ligand (0,738 g) are added to saturated NaOAc/titanosilicates media (1.10 g). Sample cover and allow to stand for 50 minutes, then transferred into a vacuum oven, and then heated in vacuum at 100 º C for 30 minutes. The sample was then cooled to room temperature and kept under vacuum overnight to obtain the composition of the catalyst precursor. Elemental analysis: 267±5 PM/million Au; 1690±90 hours/million Na; 4770±90 hours/million Ti; 43±1% Si; 31±5 PM/million R.

The composition of the catalyst precursor is treated with the formation of the catalyst according to this invention, which have in hydrocyclone propylene to propylene oxide in the following manner. The composition of the catalyst precursor (0.5 g) is loaded into the flow reactor continuous fixed bed & condition as follows for the formation of the catalyst according to this invention. Start feeding a stream of 10% vol. hydrogen in helium. The reactor is heated from room temperature D. the 250º with a speed of 120 ºC/h, maintained at 250º for 1 hour and then cooled to 100ºC. Then, the reactor serves helium heated to 160º, and incubated for 1 hour. After that, the temperature was lowered to 140º and then injected feedstock comprising propylene, oxygen and hydrogen (30% propylene, 10% oxygen, 10% hydrogen, helium else, the volumetric rate of 250 cm³/min, a pressure of 100 psi (690 kPa)). Evaluation of the catalyst is carried out while maintaining the temperature at 140º within 8 hours, raise the temperature to 160º for 8 hours and subsequent increase in temperature to about 240º. The products analyzed by gas chromatography on-line. The results are shown in table 1 and graphically in figures 1 and 2. Measuring the degree of conversion of propylene, the selectivity to propylene oxide and cumulative molar ratio of water to propylene oxide is conducted approximately every hour during the total time of the experience. Measurements shown in the table and in the figure represent the values registered about every 12 and 24 hours (or twice a day) from the start of the experiment.

1. PP - propylene, the propylene oxide 2. Load: 30% propylene, 10% oxygen, 10% hydrogen, the remainder: helium; space velocity: 250 cm 3rpm, 100 psi (690 kPa)

Elemental analysis of the spent catalyst shows the following composition: 230±5 PM/million Au; 1670±90 hours/million Na; 4670±90 hours/million Ti; 42±1% Si; 5±2 hours/million R.

The results show essentially equal selectivity to propylene oxide, equal to about 89 mole% when the process temperature is higher 230º time and experience about 41 days. Cumulative molar ratio of N₂About/ON slowly increases from 4.3 to about 5.2 in the course of the same period of 41 days. The degree of transformation shows an initial increase and peak, and then steady but slow decline in values.

Example 2

Part titanosilicates carrier obtained as described above is dried in an oven at 110 º C for 1 hour. Prepare an aqueous solution of cesium acetate (CsOAc) mixing water (to 4.979 g) and CsOAc (0,052 g). The solution CsOAc (1.54 g) is added dropwise to titanosilicates media (2.20 g). The sample is transferred into a vacuum oven and heated in a vacuum to 70 º C and incubated for 1 hour. Turn off heat; the sample allow to cool to room temperature and maintained under vacuum during the night. Then vacuum furnace blown off with nitrogen and the sample is removed and placed in a flask.

Part impregnated CsOAc titanosilicates carrier is dried in an oven at 110 º C for 1 cha is and. Prepare a solution of a gold cluster-ligand mixing Au₉(PPh₃)₈(NO₃)₃(0,0040 g) with acetone (2,873 g) and methanol (to 0.900 g). The resulting solution cluster gold-ligand (0,742 g) are added to CsOAc/titanosilicates media (1.10 g). The sample is covered and incubated for 50 minutes. The sample was then transferred into a vacuum oven, and then heated in vacuum at 100 º C for 30 minutes. The sample was then cooled to room temperature and kept under vacuum overnight to obtain the composition of the catalyst precursor. Elemental analysis: 233±5 PM/million Au; 4340±90 hours/million Cs; 4720±90 hours/million Ti; 41±1% Si; and 24±3 hours/million R. Then the composition of the catalyst precursor condition in the reactor hydrocyclone propylene to obtain a catalytic composition according to this invention, which is experienced in hydrocyclone propylene; both air-conditioning and hydrocyclone carried out according to the method of example 1. The results are shown in table 2 and graphically in figures 3 and 4.

Table 2 Hydrocyclone propylene using Au/Cs/TC catalyst1,2
1. PP - propylene, the propylene oxide 2. Load: 30% propylene, 10% oxygen, 10% hydrogen, the remainder: helium; space velocity: 250 cm3rpm, 100 psi (690 kPa)

Elemental analysis of the spent catalyst shows the following composition: 230±5 PM/million Au; 4220±90 hours/million Cs; 4790±90 hours/million Ti; 41±1% Si; P is not detected. PAM spent catalyst shows gold nanoparticles with median size of 4.4 nm.

The results show essentially equal selectivity to propylene oxide, equal to about 91 mol.% when the process temperature is higher 220º and over time experience about 41 days. Cumulative molar ratio of N₂On/AT only slowly increases from 3.8 to about 4.4 for the same period of 41 days. The degree of transformation shows an initial increase and peak, and then steady but slow decline in values.

Example 3

Part impregnated CsOAc titanosilicates carrier obtained by the method of example 2, dried in an oven at 110 º C for 1 hour. Prepare for a solution cluster gold shaking cluster complex Au brand Nanogold® - ligand (30 nmol; gold particles with a size of 1.4 nm, Nanoprobes, Incorporated, catalog No. 2010) with cold methanol (0,81 g). The solution is placed in the fridge for 5 minutes and then the entire volume of solution added to COAc/titanosilicates media (1.2 g). The sample is covered and kept in the refrigerator for 1 hour. The sample is transferred into a vacuum oven, maintained at room temperature for 1 hour, heated to 105º for about 30 minutes, incubated at 105º for 60 minutes, cooled to room temperature and then remain over night in vacuum to obtain the composition of the catalyst precursor in this invention. Elemental analysis: 286±5 PM/million Au; 4380±90 hours/million Cs; 4870±90 hours/million Ti; 42±1% Si and 15±3 hours/million R. Then the composition of the catalyst precursor condition in the reactor for formation of the catalytic compositions according to this invention, which is experienced in hydrocyclone propylene; both air-conditioning and hydrocyclone carried out by the method of example 1. The results are shown in table 3 and figures 5 and 6.

Table 3 Hydrocyclone propylene using Au/Cs/Ti catalyst1,2
1. PP - propylene, the propylene oxide 2. Load: 30% propylene, 10% oxygen, 10% hydrogen, the remainder: helium; about the roadways speed: 250 cm 3rpm, 100 psi (690 kPa)

Elemental analysis of the spent catalyst shows the following composition: 278±5 PM/million Au; 4250±90 hours/million Cs; 4450±90 hours/million Ti; 40±1% Si; 12±3 hours/million R. PAM spent catalyst shows gold nanoparticles with median size of 2.3 nm.

The results show high selectivity to propylene oxide constituting more than 95% or close to this value when the process temperature above 200ºC during the time of the experience about 25 days. After about the first four days the degree of conversion is supported when set to approximately 2% by regulating the reaction temperature. Cumulative molar ratio of N₂On/remains at the value less than 4 in the period longer than 20 days.

Example 4

The cluster complex the gold is a noble metal - ligand (PPh₃)Pt(AuPPh₃)₆(NO₃)₂get in line with the literature method, which is disclosed in: Mueting, A.M., et al., Inorganic Syntheses (1992), 29, 279-98. The cluster complex (5.0 mg) is dissolved in methylenechloride (10 g) in a glass vial, to which is added the crystalline titanosilicate (1,00 g)containing sodium acetate (about 1.35 wt.%). Crystalline titanosilicate similar to the above titanosilicate used in example 1. The solid is manually circling in solution, etc is what at this time the cluster compound is adsorbed on titanosilicate. With solids drained of excess solution of methylene chloride and produce the composition of the catalyst precursor on the drying plate. The composition of the precursor is dried in air atmosphere for 4 hours, then in a vacuum oven at 70 º C for 1 hour. Solid (0.50 g) is loaded into a tubular reactor (316 SS; the diameter of the outer surface of 0.25 inch) and dried under a stream is Not at 160º for 1 hour to form a catalyst according to this invention. After cooling to 140º the catalyst was tested in hydrocyclone propylene according to the method of example 1, except that the pressure value is preferable 94 psi (648 kPa)and 100 psi (690 kPa). The results are shown in table 4 and in figure 7.

Table 4 Hydrocyclone propylene using cluster complex Pt/Au1,2
1. PP - propylene, the propylene oxide 2. Load: 30% propylene, 10% oxygen, 10% hydrogen, the remainder: helium; space velocity: 250 cm3/min, 94 psi (648 kPa)

Data show that the catalyst obtained from a mixed cluster complex Au-Pt-phosphine ligand, gives after the start of the experiment, the degree of conversion of propylene of from 9 to about 10% during the time of the experience up to 69.9 hours. The selectivity to propylene oxide is changed and does not exceed 10%; the main product is propane. It is significant that after the start of the experiment the cumulative molar ratio of N₂On/remains stable and is in the range from 6 to 7 during the time of the experience, equal to 69.9 hours.

Example 5

Part impregnated CsOAc titanosilicates carrier obtained by the method of example 2, dried in an oven at 136º for 1 hour. Prepare for a solution cluster of gold by mixing the cluster complex Au brand Positively Charged Nanogold® - ligand (30 nmol; gold particles with a size of 1.4 nm, containing several primary amino groups in the molecule; Nanoprobes, Incorporated, catalog No. 2022) with cold methanol (1,403 g). Then a solution of 0.77 g) are added to CsOAc/titanosilicates media (1.10 g). The sample is covered and incubated at room temperature for 30 minutes. The sample is transferred into a vacuum furnace, heated to 100ºC, incubated at 100ºC for 60 minutes, cooled to room temperature and then remain over night in vacuum to obtain the composition of the catalyst precursor in this izobreteniya the composition of the catalyst precursor condition in the reactor for formation of the catalytic compositions according to this invention, experienced in hydrocyclone propylene; both air-conditioning and hydrocyclone carried out according to the method of example 1. The results are shown in table 5 and figures 8 and 9.

Table 5 Hydrocyclone propylene using cluster complex Au1,2
1. PP - propylene, the propylene oxide 2. Load: 30% propylene, 10% oxygen, 10% hydrogen, the remainder: helium; space velocity: 250 cm3rpm, 100 psi (690 kPa)

Example 6

Repeating example 5, except that instead of the cluster complex Au brand Positively Charged Nanogold®-ligand used the cluster complex brand Negatively Charged Nanogold® - ligand (30 nmol; gold particles with a size of 1.4 nm, containing many carboxyl groups in the molecule; Nanoprobes, Incorporated, catalog No. 2023). The results are shown in table 6 and figures 10 and 11.

Table 6 Hydrocyclone propylene using cluster complex Au1,2
1. PP - propylene, the propylene oxide 2. Load: 30% propylene, 10% oxygen, 10% hydrogen, the remainder: helium; space velocity: 250 cm3rpm, 100 psi (690 kPa)

Example 7

Part impregnated CsOAc titanosilicates carrier obtained by the method of example 2, dried in an oven at 136º for 1 hour. Prepare for a solution cluster of gold by mixing Au₅₅[P(C₆H₅)₃]₁₂Cl₆(0,0040 g; Strem Chemicals, Incorporated) with chloroform (4,616 g). Then the solution (1,420 g) are added to CsOAc/titanosilicates media (1.20 g). The sample is covered and incubated at room temperature for 50 minutes. The sample is transferred into a vacuum furnace, heated to 100ºC, incubated at 100ºC for 30 minutes, cooled to room temperature and then aged in vacuum overnight to obtain the composition of the catalyst precursor in this invention. The composition of the catalyst precursor condition in the reactor for formation of the catalytic compositions according to this invention, which is experienced in hydrocyclone propylene; both air-conditioning and hydrocyclone carried out according to the method of example 1. The results are shown in table 7 and in figures 12 and 13.

Table 7 Hydrocyclone propylene using cluster complex Au551,2
1. PP - propylene, the propylene oxide 2. Load: 30% propylene, 10% oxygen, 10% hydrogen, the remainder: helium; space velocity: 250 cm3rpm, 100 psi (690 kPa)

Example 8

Part impregnated CsOAc titanosilicates carrier obtained by the method of example 2, dried in an oven at 136º for 1 hour. Prepare an aqueous solution of barium acetate by mixing water (4,704 g) and barium acetate (0,0131 g). A solution of barium acetate (0,387 g) are added to CsOAc/titanosilicates media (0.55 g). The sample is transferred into a vacuum oven and heated in a vacuum to 70 º C and incubated for 1 hour. The heating is shut off and the sample cooled to room temperature and maintained under vacuum during the night. Part of CsOAc/acetate barium/titanosilicates carrier is dried in an oven at 136º for 1 hour. Prepare for a solution cluster of gold by mixing the cluster complex Au brand Nanogold® - ligand (30 nmol; gold particles with a size of 1.4 nm, Nanoprobes, Incorporated, catalog No. 2010) with cold methanol (2,185 g). Then the solution (0.375 g) EXT the keys to CsOAc/acetate barium/titanosilicates media (0.55 g). The sample is covered and kept in the refrigerator for 50 minutes. The sample is transferred into a vacuum furnace, heated to 100ºC, incubated at 100ºC for 60 minutes, cooled to room temperature and then aged in vacuum overnight to obtain the composition of the catalyst precursor in this invention. Then the composition of the catalyst precursor in this invention condition in the reactor for formation of the catalytic compositions according to this invention, which is experienced in hydrocyclone propylene; both air-conditioning and hydrocyclone carried out according to the method of example 1. The results are shown in table 8 and in figures 14 and 15.

Table 8 Hydrocyclone propylene using the cluster complex Au1,2
1. PP - propylene, the propylene oxide 2. Load: 30% propylene, 10% oxygen, 10% hydrogen, the remainder: helium; space velocity: 250 cm3rpm, 100 psi (690 kPa)

Examples 9-16

Get a number of catalysts in the following way. Part titanosilicates media obtained as the decrees of ALOS above, dried in an oven at 136º for 1 hour. Prepare an aqueous solution of alkali metal salt by mixing water (5 g) and salts of alkaline metal as follows: example 9: the lithium acetate, LiOAc, 0,018 g; example 10: sodium acetate, NaOAc, 0,0224 g; example 11: potassium acetate, KOAc, 0,0271 g; example 12: rubidium acetate, RbOAc, 0,0390 g; example 13: carbonate, cesium, Cs₂CO₃, 0,0440 g; example 14: formate, cesium, CsOCH(O)0,048 g; example 15: cesium bicarbonate, CsHCO₃, 0,054 g; and example 16: cesium oxalate, 0,048, an Aqueous solution of alkali metal salt is added to titanosilicates media for impregnation and obtain humidity 70% wt. The sample is transferred into a vacuum oven and kept in a vacuum at room temperature for 30 minutes, heated in a vacuum to 70 º C and then kept in a vacuum at 70 º C for 1 hour. The heating is shut off and the sample allow to cool to room temperature and maintained under vacuum during the night. Part of the impregnated salt of an alkali metal titanosilicates carrier is dried in an oven at 136º for 1 hour. Prepare for a solution cluster of gold by mixing the cluster complex Au brand Nanogold® - ligand (Nanoprobes, Incorporated, catalog No. 2010; gold particles with a size of 1.4 nm; 60 nmol for examples 9-12; 30 nmol for examples 13-16) with cold methanol (2,173 g). Then a solution of 0.36-0.39 g) are added to saturated salt of an alkali metal titanosilicate the media (0.56 g). The sample is covered and kept in the refrigerator for about 90 minutes. Then it is transferred into a vacuum furnace, heated to 100ºC, incubated at 100ºC for 30 minutes, cooled to room temperature and then aged in vacuum overnight to obtain the composition of the catalyst precursor in this invention. Then the composition of the catalyst precursor in this invention condition in the reactor for formation of the catalytic compositions according to this invention, which is experienced in hydrocyclone propylene; both air-conditioning and hydrocyclone carried out by the method of example 1. The results for each catalyst are shown in tables 9 and 10.

Table 9 Hydrocyclone propylene using cluster Au and various promoters1,2
1. PP - propylene, the propylene oxide 2. Load: 30% propylene, 10% oxygen, 10% hydrogen, the remainder: helium; space velocity: 250 cm3rpm, 100 psi (690 kPa)

Table 10</> Hydrocyclone propylene using cluster Au and various promoters1,2
1. PP - propylene, the propylene oxide 2. Load: 30% propylene, 10% oxygen, 10% hydrogen, the remainder: helium; space velocity: 250 cm3rpm, 100 psi (690 kPa)

Example 17

Part titanosilicates media obtained as mentioned above, dried in an oven at 136º for 1 hour. Prepare an aqueous solution of cesium chloride (CsCl) mixing water (5,022 g) and CsCl (0,0454 g). A solution of CsCl (1,053 g) are added to titanosilicates media (1.50 g). The sample is transferred into a vacuum oven, kept in a vacuum at room temperature for 30 minutes, heated in a vacuum to 70 º C and then kept in a vacuum at 70 º C for 1 hour. Turn off the heat and the sample allow to cool to room temperature and maintained under vacuum during the night. Part CsCl/titanosilicates carrier is dried in an oven at 136º for 1 hour. Prepare for a solution cluster of gold by mixing the cluster complex Au brand Nanogold® - ligand (30 nmol; gold particles with a size of 1.4 nm; Nanoprobes, Incorporated, catalog No. 2010) with cold methanol (2,155 g). Then R is the target (0,373 g) are added to CsCl/titanosilicates media (0.55 g). The sample is covered and kept in the refrigerator for about 60 minutes. Then it is transferred into a vacuum furnace, heated to 100ºC, incubated at 100ºC for 30 minutes, cooled to room temperature and then aged in vacuum overnight to obtain the composition of the catalyst precursor in this invention. Then the composition of the catalyst precursor condition in the reactor for formation of the catalytic compositions according to this invention, which is experienced in hydrocyclone propylene; both air-conditioning and hydrocyclone carried out by the method of example 1, the obtained results are shown in table 11.

Table 11 Hydrocyclone propylene using cluster Au and various promoters1,2
1. PP - propylene, the propylene oxide 2. Load: 30% propylene, 10% oxygen, 10% hydrogen, the remainder: helium; space velocity: 250 cm3rpm, 100 psi (690 kPa)

Example 18

Repeating example 17, except that instead of the solution of cesium chloride of example 17 with water (5,001 g) smesi the Ute caesium chloride (0,0228 g) and cesium acetate (0,0261 g) and a part of the obtained aqueous solution of CsCl/CsOAc (at 1,047 g) impregnated with titanosilicates media. The results are shown in table 11.

Example 19

Repeating example 17, except that instead of the solution of cesium chloride of example 17 prepare the solution by mixing water (35,013 g) and trifenatate cesium (Fluka, 6M, 0,304 ml) and the resulting solution trifenatate cesium (1,395 g) impregnated with titanosilicates media (2.00 g). The results are shown in table 11.

Example 20

Repeating example 17, except that instead of the solution of cesium chloride prepared solution containing cesium acetate and triptorelin cesium, and precipitated on titanosilicate in accordance with the following method. An aqueous solution of triptoreline cesium prepared by mixing water (35,013 g) and trifenatate cesium (Fluka, 6M, 0,304 ml). An aqueous solution of cesium acetate is prepared by mixing water (17,500 g) and cesium acetate (0,1830 g). The combined solution of cesium acetate and trifenatate cesium prepared by mixing 2.5 ml of a solution of triptoreline cesium with 2.5 ml of a solution of cesium acetate. Then the combined solution (1,397 g) precipitated on titanosilicate (2.00 g) and essentially unchanged continue the procedure according to example 17. The results are shown in table 11.

Example 21

Part impregnated CsOAc titanosilicates carrier obtained by the method of example 2, annealed at 500º for 1 hour. Prepare for a solution cluster gold mix is m Au ₅₅[P(C₆H₅)₃]₁₂Cl₆(0,0040 g; Strem Chemicals, Incorporated) with chloroform (4,616 g). Then the solution (1,442 g) are added to the calcined carrier (1.20 g). The sample is covered and incubated at room temperature for about 50 minutes. The sample is transferred into a vacuum furnace, heated to 100ºC, incubated at 100ºC for 30 minutes, cooled to room temperature and then aged in vacuum overnight to obtain the composition of the catalyst precursor in this invention. Then the composition of the catalyst precursor condition in the reactor for formation of the catalytic compositions according to this invention, which is experienced in hydrocyclone propylene; both air-conditioning and hydrocyclone carried out according to the method of example 1. The results are shown in table 12.

Comparative experience 1

Catalyst hydrocyclone prior is obtained from Hartley acid and evaluated hydrocyclone propylene with oxygen in the presence of hydrogen under conditions of isothermal process. Part titanosilicates carrier obtained by the method of example 1, dried in an oven at 110 º C for 1 hour. An aqueous solution prepared by mixing water (5,01 g), sodium acetate (0,098 d) and three-hydrate sour tetrachloroaurate(III) (0,022 g HAuCl₄·3H₂O). The gold solution (0,772 g) are added to titanosilicates media (1.10 g). The sample is transferred into a vacuum furnace, heated to 70 º C and then kept in a vacuum at 70°C for 1 hour. Heat is shut off and the sample allow to cool to room temperature and maintained under vacuum during the night. The sample was then tested in hydrocyclone propylene, following the method of example 1. The reactor temperature was raised to 160°C and maintained at this level during the experiment. The results are shown in table 13 and figures 16 and 17.

Table 12 Hydrocyclone propylene using cluster Au551,2
1. PP - propylene, the propylene oxide 2. Load: 30% propylene, 10% oxygen, 10% hydrogen, the remainder: helium; space velocity: 250 cm3rpm, 100 psi (690 kPa)

Table 13 Hydrocyclone propylene using Hartley acid1,2
1. PP - propylene, the propylene oxide 2. Load: 30% propylene, 10% oxygen, 10% hydrogen, the remainder: helium; space velocity: 250 cm3rpm, 100 psi (690 kPa)

When comparing table 13 and figures 16 and 17 with the previous tables and figures, representing the invention, it is seen that the catalyst of the prior decreases more rapidly and the cumulative ratio of water/increases more rapidly in comparison with the catalysts according to this invention.

Comparative experience 2

Catalyst hydrocyclone prior is obtained from Hartley acid and evaluated hydrocyclone propylene with oxygen in the presence of hydrogen with the use of temperature control to operate at essentially constant degree of conversion of propylene. Part titanosilicates carrier obtained by the method of example 1, dried in an oven at 110 º C for 1 hour. An aqueous solution prepared by mixing water (5,00 g), sodium acetate (0,098 d) and three-hydrate sour tetrachloroaurate(III) (0,022 g). Solution (1.40 g) are added to titanosilicates media (2.00 g). The sample is transferred into a vacuum furnace, heated to 70 º C and then kept in a vacuum at 70 º C for 1 hour. The heating is shut off and the sample allow to cool to room temperature and remove the more in vacuum over night. The sample was then tested in hydrocyclone propylene, following the method of example 1. To maintain a degree of conversion of propylene in the range of about 1.5 to 2.1% in different time intervals increase the temperature of the reactor. The results are shown in table 14 and figures 18 and 19.

Table 14 Hydrocyclone propylene using Hartley acid1,2
1. PP - propylene, the propylene oxide 2. Load: 30% propylene, 10% oxygen, 10% hydrogen, the remainder: helium; space velocity: 250 cm3rpm, 100 psi (690 kPa)

When comparing table 14 and figures 18 and 19 with the previous tables and figures, representing the invention, it is seen that the catalyst of the prior decreases more rapidly and the cumulative ratio of water/increases more rapidly in comparison with the catalysts according to this invention.

Examples 22-24

Three mixed metallocluster catalyst was prepared as follows. The solution of the cluster complex is prepared by mixing methylene chloride (15 ml) with a mixture of metallic sternum complex: example 22 - 16 mg of Pt(AuPPh₃)₈(NO₃)₂; example 23 15 mg Pt(AuPPh₃)₈Ag(NO₃)₃; example 24 - 14 mg Pt(AuPPh₃)₇Ag₂(NO₃)₃. To a solution of the cluster complex at strong shaking add part saturated NaOAc titanosilicates carrier obtained by the method of example 4 (2.00 g), and drain the excess liquid. The sample is dried in a fume hood for 1 hour, then dried in vacuum at 70 º C for 1 hour. The precursor of the catalyst was tested in hydrocyclone propylene, following the method of example 1, the results shown in table 15.

Table 15 Hydrocyclone propylene using mixed Au-metallocluster
1. PP - propylene, the propylene oxide 2. Load: 30% propylene, 10% oxygen, 10% hydrogen, the remainder: helium; space velocity: 250 cm3rpm, 100 psi (690 kPa)

1. Catalytic composition for obtaining the olefin oxide by hydrocyclones olefins containing gold nanoparticles deposited on the nanoporous particles titanosilicates media, and catalizatorului way including deposition cluster complex gold-ligand on nanoporous titanosilicate media at a temperature of from about -100°C. to about 300°C for the formation of the catalyst precursor and subsequent heating at a temperature of more than approximately 50°C. to approximately 800°C and/or chemical treatment of the catalyst precursor from about 15 minutes to about 5 hours to form the catalyst.

2. The composition according to claim 1, in which more than 80% of gold are metallic gold.

3. The composition according to claim 1, in which the gold nanoparticles have a median particle size in the range from 0.8 nm to less than 8 nm.

4. The composition according to claim 1, in which more than 90% of the gold nanoparticles placed on the outer surface of the nanoporous particles titanosilicates carrier, where the carrier has a pore size between 0.2 nm and 1 nm.

5. The composition according to claim 1, in which the gold loaded on the carrier in the amount of more than 10 h/m and less than 20000 hours/million calculated on the total weight of the catalyst.

6. The composition according to any one of claims 1 to 5, in which the nanoporous titanium containing the carrier has a surface area of more than 50 m²/year

7. The composition according to claim 1, in which the nanoporous titanium containing media is a nanoporous titanosilicate selected from the group consisting of TS-1, TS-2, Ti-beta, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15 and Ti-SBA-3.

9. The composition according to claim 7, in which the loading of titanium is more than 0.02 wt.% and less than 35 wt.% the mass titanosilicates media and any binder.

10. The composition according to claim 1, in which the ligand is selected from organophosphorus compounds, Filatov, thiols, amines, Iminov, amides, imides, carbon monoxide, halides and mixtures thereof.

11. The composition according to claim 1, in which the cluster of gold selected from the group consisting of Au₃Au₄Au₅Au₆Au₇Au₈Au₉, AI₁₀Au₁₁Au₁₂Au₁₃Au_(20±2)Au_(55±5)Au_(101±10)and mixtures thereof, and the cluster, optionally, further comprises silver.

12. The composition according to claim 1, in which the cluster complex the gold-ligand further comprises a noble metal selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum and mixtures thereof, and, optionally, further comprises silver.

13. The method of producing oxide olefin comprising contacting the olefin having at least three carbon atoms with oxygen in the presence of hydrogen and in the presence of a catalyst having the composition according to claim 1, where the contacting is carried out at a temperature of 160°C and 300°C and pressure the AI from atmospheric to 500 psig (3549 kPa) for the formation of olefin oxide.

14. The method according to item 13, in which the olefin is selected from C_3-12monoolefins or diolefins, propylene, butadiene, cyclopentadiene, Dicyclopentadiene, styrene, α-methylstyrene, divinylbenzene, allyl alcohol, simple dialiawah ether, simple allylation ether, allylmalonate ZIOC scientists allylbenzene, simple allylanisole ether, simple arylpropionic ether, allylanisole and mixtures thereof.

15. The composition of the catalyst precursor to a catalytic composition for obtaining the olefin oxide by hydrocyclones olefins, containing the cluster complex the gold-ligand deposited on the nanoporous particles titanosilicates media.

16. The composition of the catalyst precursor according to item 15, in which the cluster complex the gold-ligand has a diameter (or largest dimension) over (0,54±0,04) nm.