The method of producing olefination direct oxidation of olefins, the catalyst composition for this process and the method of regeneration

 

(57) Abstract:

The invention relates to a method of producing olefination, in particular propylene oxide, direct oxidation of olefins, in particular propylene, oxygen in the presence of hydrogen, and optional diluent and in the presence of a catalyst containing gold, at least one promoting metal selected from the group consisting of metals of Group 1, Group 2, rare earth lanthanoide actinoid metals and metals of the Periodic table of elements, and such media, and the contacting is carried out at a temperature higher than the 20oC and lower than 250oWith, and to a catalytic composition for this process and the method of regeneration. Suitable carrier materials include titanium dioxide, titanosilicates, and titanates metals promoters, titanium dispersed on silica, and silicates of metals-promoters. The technical result is the high selectivity for refinanced with simultaneous cost-effective conversion of the olefin. 5 C. and 73 C.p. f-crystals, 21 PL.

The invention is carried out with the support of the government of the United States Grand 70NANB5H1143, awarded by the National Institute of Standards and Technology. Pravitelstvo claims the benefit of provisional application U.S. 60/021013, filed July 1, 1996, the provisional application 60/026590, filed September 20, 1996, and preliminary applications 60/026591, filed September 20, 1996 This application is part of a continuing application of U.S. 08/679605 filed July 11, 1996, which claims the benefit of provisional application U.S. 60/021013, filed July 1, 1996

The present invention relates to a method and catalyst for the direct oxidation of olefins, such as propylene, oxygen refinanced, such as propylene oxide.

Refinanced, such as propylene oxide, are used to alkoxysilane alcohols with getting polyether polyols, such as polypropyleneglycol, which are widely used in the manufacture of polyurethanes and synthetic elastomers. Refinanced are also important intermediate compounds in the production of alkalophile, such as propylene glycol and dipropyleneglycol, and alkanolamines, such as isopropanolamine, which are used as solvents and surfactants.

Industrial production of propylene oxide implement well-known chlorhydrins way, in accordance with which propylene interacts with the aqueous solution of chlorine with receipt what dostatkom process is the obtaining of salt flow low concentration (see K. Weissermel and H. J. Arpe, Industrial Organic Chemistry, 2nded., VCH Publishers, Ink., New York, NY, 1993, p.264-265).

Another well known method of obtaining olefination includes the transfer of the oxygen atom of the organic gidroperekisi or nadarbazevi acid to the olefin. In the first stage of this method of oxidation generator peroxide, such as isobutane or acetaldehyde, smokecloud oxygen with obtaining peroxide, such as tert-butylhydroperoxide or peracetic acid. This connection is used for the epoxidation of olefins, typically in the presence of a catalyst based on a transition metal, including titanium, vanadium, molybdenum and other heavy metal compounds or complexes. Together with olefination this process is disadvantageous due to the fact that are formed in equimolar quantities of by-product, for example alcohol, such as tert-butanol, or acids, such as acetic acid, whose value on the market is limited (Industrial Organic Chemistry, ibid, p. 265-269).

Although in the manufacturing method of direct oxidation of ethylene with molecular oxygen to ethylene oxide is carried out in the presence of a silver catalyst, it is known that similar direct oxidation of propylene containing low by-products C1-3(Industrial Organic Chemistry, ibid, p. 264). In some patents, such as U.S. patents 4007135 and 4845253, disclosed the use of a silver catalyst promoted with metal for oxidation of propylene with oxygen in propylene oxide. Metal-promoters disclosed, gold, beryllium, magnesium, calcium, barium, strontium and rare earth lanthanides. These promoted silver catalysts also exhibit low selectivity towards refinanced.

Alternative EP-A1-0709360 discloses a method of oxidation of unsaturated hydrocarbons such as propylene, oxygen in the presence of hydrogen and catalyst to obtain epoxide such as propylene oxide. As a catalytic composition reveals the gold deposited on titanium dioxide, preferably in the anatase crystalline phase of titanium dioxide, optionally immobilized on a carrier, such as silicon dioxide or aluminum oxide. The catalyst is characterized by a lower selectivity towards refinanced and less efficient consumption of hydrogen during operation at elevated temperatures. In addition, the catalyst has a short operating period.

PCT publication WO-A1-96/02323 raskryvay is xida. The catalyst is silicalite titanium or vanadium containing at least one platinum group metal and optional additional metal selected from gold, iron, cobalt, Nickel, rhenium, and silver. The process is characterized by low productivity refinanced.

From the above it follows that in the chemical industry there remains a need for an efficient direct method of obtaining propylene oxide and higher olefination by the reaction of oxygen with C3and higher olefins. Disclosure of such method, in which a high selectivity for refinanced attained with the cost-effective conversion of olefin, represents a significant achievement compared with the prior art. From the point of view of the commercial viability of this method also requires that the catalyst had a long service life.

U.S. patents 4839327 and 4937219 are additional prior art disclosing a composition comprising gold particles having a size of less than approximately immobilized on the oxide of alkaline-earth metal or titanium dioxide, or a composite oxide of titanium dioxide with oxide of alkaline-earth metal. Getting t omposition oxide, followed by calcination to obtain a metallic gold with a particle size of less what about nothing is said Here about the way to get refinanced.

The present invention relates to a new method of obtaining refinanced directly from the olefin and oxygen. The method involves contacting the olefin containing at least three carbon atoms with oxygen in the presence of hydrogen and a catalyst under conditions sufficient to obtain the corresponding refinanced. In the method of the present invention uses a unique catalyst containing gold, at least one metal promoter such media.

The new method according to the present invention is used to obtain refinanced directly from oxygen and olefins containing three or more carbon atoms. Unexpectedly it was found that the method according to the present invention ensures refinanced with significantly high selectivity. The products of complete or partial combustion, such as acrolein and carbon dioxide, which is found in large quantities in many ways prior art, the method according to the present invention receive smaller amounts. It is important that the proposed method can be carried out at high temperature, the Operation at higher temperatures mainly provides couples received from the selected heat. Accordingly, the method according to the present invention can be integrated in a common unit in which the heat supplied by the steam, used for holding additional processes, such as the Department of refinanced from the water. Because the water in this process is obtained as a by-product, an additional advantage of this method is the high efficiency of hydrogen determined by the molar ratio of water to refinanced. Most advantageously, the method in the preferred embodiments of the implementation shows good conversion of the olefin.

In accordance with another aspect of the present invention discloses a unique catalyst composition containing gold, at least one promoting metal (metal-promoter) of such media. The metal-promoter selected from Group 1, Group 2, rare earth lanthanoid metals and actinoid metals and their combinations. Impose the following condition. The composition of the present invention does not contain gold titanate metal-promoter Group 2.

The new composition of the present invention can be effectively used in the above direct oxidation of an olefin containing Toko selective on refinanced, he follows a long service life. An additional advantage is that the catalyst is easily regenerated by partial or complete. Consequently, this unique structure has highly desirable properties for catalysis direct oxidation of propylene and higher olefins to their corresponding refinanced.

The new method according to the present invention comprises the contacting of the olefin containing three or more carbon atoms, with oxygen in the presence of hydrogen and catalyst for the epoxidation under conditions sufficient to obtain the corresponding refinanced. In accordance with one preferred embodiment of a diluent is used, as described in detail below. Can be used any relative molar number of the olefin, oxygen, hydrogen, and optional diluent sufficient to retrieve the target refinanced. In the preferred embodiment of the invention used by the olefin is a C3-12olefin, and his turn in the appropriate3-12refinanced. In accordance with the preferred embodiment the olefin is a C3-8olefin, and it turned into sootvetstvuschie a propylene and olefination is propylene oxide.

The new catalyst, which is used in the method according to the present invention, contains gold, at least one metal promoter such media. In the preferred embodiment of the method, the metal-promoter selected from metals of Group 1, Group 2, the rare earth lanthanides, and actinides of the Periodic table of the elements according to the CRC Handbook of Chemistry and Physics, 75-oe edition, CRC Press, 1994-1995. You can also use combinations of the above metals.

In the method according to the present invention can be any olefin containing three or more carbon atoms. Preferred monoolefinic, but can also be used compounds containing two or more olefins, such as diene. The olefin may be a simple hydrocarbon containing only atoms of carbon and hydrogen, or alternatively, the olefin may be substituted at any carbon atom with an inert substituent. The term "inert" as used in the description means that the Deputy essentially inactive in the method according to the present invention. Suitable inert substituents include, but are not limited to, halides, ethers, esters, alcohols, and aromatic groups, preferably chlorine,1-12PR is new, which are suitable for the method according to the present invention include propylene, 1-butene, 2-butene, 2-methylpropene, 1-penten, 2-penten, 2-methyl-1-butene, 2-methyl-2-butene, 1-hexene, 2-hexene, 3-hexene, and similarly, the various isomers of methylpentene, ethylbutane, Heptene, methylhexane, ethylpentane, propylbetaine, octenol, including preferably 1-octene and other higher analogues, as well as butadiene, cyclopentadiene, Dicyclopentadiene, styrene, -methylsterol, divinylbenzene, allylchloride, allyl alcohol, allyl simple ether, arelatively simple ether, allylmalonate, ZIOC scientists, Olivenza, allergenicity simple ether, arylpropionic simple ether and allylanisole. Preferably, the olefin is an unsubstituted or substituted C3-12olefin, more preferably unsubstituted or substituted C3-8olefin. More preferably, the olefin is a propylene. Many of these olefins are commercially available; others can be obtained by methods known to experts in this field.

The amount of olefin used in the method may vary within wide limits, provided that they receive the appropriate refinanced. Generally, the amount of olefin depends on the spiral is agenia and security. Professionals in this field know how to determine the acceptable range of concentrations of the olefin with the specific characteristics of the method. Usually in a molar ratio of olefin is used in excess relative to the oxygen, since this condition increases productivity by refinanced. In light of the above, the amount of olefin is typically greater than about 1, preferably greater than about 10 and more preferably greater than about 20 mol.% relative to the total moles of olefin, oxygen, hydrogen, and optional diluent. Generally, the amount of olefin is less than about 99, preferably less than about 85, and more preferably less than about 70 mol.% relative to the total molar content of olefin, oxygen, hydrogen, and optional diluent.

For implementing the method of the present invention is also necessary oxygen. Acceptable is any source of oxygen, including air, and, essentially, pure molecular oxygen. You can also use other sources of oxygen, including ozone and oxides of nitrogen such as nitrous oxide. Molecular oxygen is preferred. The applied amount of oxygen may vary Isle of moles of oxygen per mole of olefin is less than 1. Under these conditions, the selectivity for refinanced increases while the selectivity for products of combustion, such as carbon dioxide, is reduced to a minimum. Preferably, the amount of oxygen is higher than approximately to 0.01, more preferably higher than about 1, and most preferably higher than about 5 mol.% relative to the total moles of olefin, hydrogen, oxygen, and optional diluent. Preferably, the amount of oxygen is less than about 30, more preferably less than 25 and most preferably less than 20 mol.% relative to the total moles of olefin, hydrogen, oxygen, and optional diluent. At concentrations above about 20 mol.% the oxygen concentration may be in the range of Flammability for olefin-hydrogen-oxygen mixtures.

In the method according to the present invention is also necessary hydrogen. In the absence of hydrogen the catalyst is significantly reduced. In the method according to the present invention can use any source of hydrogen, including, for example, molecular hydrogen obtained from dehydrogenization alkanes and alcohols. In an alternate embodiment of the hydrogen generating system is tan, or alcohols, such as Isobutanol. Alternatively, hydrogen can be used for formation of the catalyst-hydride complex or the catalyst-hydrogen complex, which can supply the necessary hydrogen in the way.

The method can be used any number of hydrogen provided that this amount is enough to get refinanced. Suitable amounts of hydrogen are usually higher than approximately to 0.01, preferably higher than about 0.1, and more preferably higher than about 3 mol.% relative to the total molar content of olefin, hydrogen, oxygen, and optional diluent. Suitable amounts of hydrogen are usually less than about 50, preferably less than about 30 and more preferably less than about 20 mol.% relative to the total molar content of olefin, hydrogen, oxygen, and optional diluent.

In addition to the above reagents may be desirable to use in the reaction mixture of the diluent, although its use is optional. Since the method according to the present invention is exothermic, the diluent is advantageously provides a means of removal, russaian the reagents are non-flammable. The diluent can be any gas or liquid that do not inhibit the way. The specific choice of solvent will depend on the conditions under which the method. For example, if the method is carried out in the gas phase, then a suitable gaseous diluents include, but are not limited to, helium, nitrogen, argon, methane, carbon dioxide, water vapor and mixtures thereof. Most of these gases are essentially inert relative to the method according to the present invention. Carbon dioxide and water vapor can be optional inert, but can have a beneficial promoting effect. If the method is carried out in the liquid phase, then the diluent can be any stable to oxidation and thermally stable liquid. Acceptable liquid diluents include chlorinated aromatic compounds, preferably chlorinated benzenes, such as chlorobenzene and dichlorobenzene; chlorinated aliphatic alcohols, preferably C1-10chlorinated alkanols, such as chloropropanol and liquid polyethers, polyesters, and polyalcohol.

If used, the amount of diluent is typically greater than about 0, preferably greater than about 0.1 and Bo is Yes, hydrogen, and optional diluent. The amount of diluent is typically less than about 90, preferably less than about 80, and more preferably less than about 70 mol.% relative to the total molar content of olefin, oxygen, hydrogen, and diluent.

The concentration of olefin, oxygen, hydrogen and diluent disclosed above, respectively, based on the reactor design and the parameters of the method disclosed in the description. For specialists in this area it is obvious that in other various embodiments, the technical implementation of the method is possible using other concentrations that differ from those disclosed in the description.

The unique catalyst which is advantageously used in the method according to the present invention, contains gold, at least one metal promoter such media. Gold may be in the form of discrete gold particles and/or multimodal particle-gold - metal-promoter. Gold can be in the zero valence or positive valence in the range of from higher than 0 to +3, as determined by x-ray absorption spectroscopy or x-ray electron spectroscopy. Usually approximately as determined by transmission electron microscopy (FACT). On the surface of the carrier can be dispersed gold particles and/or particles of gold - metal-promoter smaller. Preferably, the average particle size of gold is greater than approximately more preferably more than about and most preferably greater than about Preferably, the average particle size of gold is less than approximately more preferably less than about and most preferably less than about

Such a medium may take many forms. As determined by the methods of x-ray electron spectroscopy and x-ray absorption spectroscopy of titanium is mostly in a positive oxidation state. More preferably, the titanium exists in the oxidation state of about +2 or higher, most preferably in the oxidation state of about +3 to about +4. Non-limiting examples of such carriers which can suitably be used in the catalyst of the present invention, include those described below. Following such media not containing the desired metal(s) promoter(s) shall be subjected to the processing for the introduction of the metal(s)-produced no additional metal(s) promoter(s), want to add to the media.

A. Titanium dioxide.

As such media can be used amorphous and crystalline titanium dioxide. The crystalline phase include anatase, rutile and brookite. Included in this category are the composites containing titanium dioxide deposited on silicon dioxide.

b. The promoter - metal titanates.

As the catalyst carrier can also be used stoichiometric and non-stoichiometric compounds, including promoter - metal titanates. The promoter - metal titanates can be crystalline or amorphous. Non-limiting examples include the titanates of the metals of Groups 1, 2 and metals, lanthanides, and actinides. Preferably, the promoter is a titanate of a metal selected from the group consisting of magnesium titanate, calcium titanate, barium titanate, strontium titanate, sodium titanate, potassium titanate and titanate erbium, lutetium, thorium, and uranium.

C. Titanosilicates.

As the carrier can also be used crystalline and amorphous titanosilicates, preferably those that are porous. Titanosilicates have a frame structure formed of SiO4

The pore size (or critical dimension), the size distribution of pores and the surface area of the porous titanosilicate can be obtained from measurements of adsorption isotherms and pore size. Usually the measurements are carried out on the powder titanosilicate using as adsorbate nitrogen at 77 K or argobar get from the amount of adsorption of long having a diameter ranging from about to about Similarly, the measurement of the volume of mesopores is obtained from the amount of adsorption of pores having a diameter ranging from higher than about to about In the form of adsorption isotherms possible qualitative identification of the type of porosity, for example microporous or macroporous. In addition, increased porosity may be correlated with increased surface area. The pore size (or critical dimension) can be identified from the data, using the equations given in the work of Charles N. Satterfield, "Heterogeneous Catalysis in Practice, McGraw-Hill Book Company, New York, 1980, pp.106-114 entered into the description by reference.

In addition, porous crystalline titanosilicates can be identified by x-ray diffraction (XRD) or by comparing the XRD diagrams of the investigated material with previously published standard, or by analyzing the XRD diagram of the single crystal to determine the frame structure and, when the presence of pores, their geometry and size.

Non-limiting examples of porous titanosilicates, which can be used in the method according to the present invention include porous amorphous titanosilicates; porous layered titanosilicates; crystalline high performance embedded the ETA), titanosilicate ZSM-12 (Ti-ZSM-12) and titanosilicate ZSM-48 (Ti-ZSM-48), and mesoporous titanosilicates, such as Ti-MCM-41.

The porous structure of TS-1 includes two connecting cylindrical 10-ring pores with a diameter of about 10-ring pore is formed in the sum of ten tetrahedra (SiO44-and TiO44-). Titanium silicalite and its characteristic XRD pattern is shown in U.S. patent 4410501 included in the description by reference. TS-1 can be commercially obtained, but it can also be synthesized by methods described in U.S. patent 4410501. Other methods are described in the following works (introduced in the description as reference): A. Tuel, Zeolites, 1996, 16, 108-117; S. Gontier, A. Tuel, Zeolites, 1996, 16, 184-195; A. Tuel and Y. Ben Taarit, Zeolites, 1993, 13, 357-364; A. Tuel and Y. Ben Taarit, C. Naccache, Zeolites, 1993, 13, 454-461; A. Tuel and Y. Ben Taarit, Zeolites, 1994, 14, 272-281 and A. Tuel and Y. Ben Taarit, Microporous Materials, 1993, 1, 179-189.

The porous structure of TS-2 includes one three-dimensional 10-ring of microporous system. TS-2 can be synthesized by the methods described in the following sources (included in description as references): J. Sudhakar Reddy, R. Kumar, Zeolites, 1992, 12, 95-100; J. Sudhakar Reddy, R. Kumar, Journal of Catalysis, 1991, 130, 440-446 and A. Tuel and Y. Ben Taarit, Applied Catal. A. General, 1993, 102, 69-77.

The porous structure of Ti-beta includes two svyazyvayuschaya the following sources, included in the description as reference: PCT patent publication WO 94/02245 (1994); M. A. Camblor, A. Corma, J. H. Perez-Pariente, Zeolites, 1993, 13, 82-87 and M. S. Rigutto, R. de Ruiter, J. P. M. Niederer and N. van Bekkum, Stud. Surf. Sci. Cat. 1994, 84, 2245-2251.

The porous structure of Ti-ZSM-12 includes one one-dimensional 12-ring channel system size according to S. Gontier and A. Tuel, ibid, included as a reference.

The porous structure of Ti-ZSM-48 includes a one-dimensional 10-ring channel system size according to R. Szostak, Handbook of Molecular Sieves, Chapman & Hall, New York, 1992, p.551-553. Other sources, describe the preparation and properties of Ti-ZSM-48 include C. B. Dartt, C. B. Khouw, H. X. Li, M. E. Davis, Microporous Materials, 1994, 2, 425-437 and A. Tuel and Y. Ben Taarit, Zeolites, 1996, 15, 164-170. The above materials are included in the description as references.

Ti-MCM-41 is a hexagonal phase, is isomorphic to the aluminosilicate MCM-41. The channels of mcm-41 is one-dimensional with a diameter in the range from about Ti-MCM-41 can be obtained in accordance with the following materials are included in the description by reference: S. Gontier, A. Tuel, Zeolites, 1996, 15, 601-610 and M. D. Alba, Z. Luan, J. Klinowski, J. Phys. Chem., 1996, 100, 2178-2182.

The atomic ratio of silicon to titanium (Si/Ti) in titanosilicate can be any that provides active and selective epoxidation catalyst in spectitle equal to or greater than about 10:1. Usually it is desirable that the atomic ratio Si/Ti was equal to or less than about 200:1, preferably equal to or less than about 100:1. It should be noted that the atomic ratio Si/Ti, defined here, refers to the total relation, which includes the content of titanium in the lattice and excess titanium in the lattice. At high relations Si/Ti, for example, about 100:1 or more, there may be a small excess titanium in the lattice, and the total ratio, essentially corresponds to the relation in the lattice.

In one preferred embodiment of the present invention, the titanium silicate is essentially free from crystalline titanium dioxide that is present, for example, in the form of excess titanium dioxide in the lattice, or as an added substrate or media. To detect the presence of crystalline titanium dioxide can be used Raman spectroscopy. The anatase phase of titanium dioxide manifests in the Raman spectrum of strong sharp characteristic peak at about 147 cm-1. The rutile phase of titanium dioxide exhibits peaks at about 448 cm-1and approximately 612 cm-1. Bruketa phase, which usually exists only in the form of a natural mineral that shows characteristic is and at 147 cm-1. In the preferred embodiment of the invention Raman peaks, essentially missing for the phases of anatase, rutile and brookite titanium dioxide. When the catalyst is, in essence, does not show defined peaks at the above wavelengths, this means that the crystalline form of titanium dioxide there is less than about 0.02 wt. % of catalyst. Range Ramana can be obtained in any suitable laser Raman spectrometer, equipped, for example, laser argon ion laser having a stripe excitation at 514.5 nm, 532 nm and/or 785 nm, and having a laser power of about 90-100 mW, measured on the sample.

d. Titanium dispersed on silica.

Another acceptable carrier of the catalyst according to the present invention includes titanium dispersed on silica. Such media may be commercially obtained or alternatively can be obtained by methods described below. The preferred form of such media are described in concurrently pending application U.S. _ __ (notification attorney-A), filed concurrently in the name of Howard W. Clark, Joseph J. Maj, Robert G. Bowman, Simon R. Bare, and George E. Hartwell, which is included in the description by reference.

In the above you is adokenai phase. The term "essentially" means that more than about 80 wt. % titanium is in the disordered phase. Preferably, more than about 85 wt. %, even more preferably more than about 90 wt.% and most preferably more than about 95 wt. % titanium is in the disordered phase. This means that typically less than about 20 wt. %, preferably less than about 15 wt. %, even more preferably less than about 10 wt. % and most preferably less than about 5 wt. % of titanium in the media exists in the ordered crystalline form, especially crystalline titanium dioxide. Thus, in his usual form, media, essentially, contains no crystalline titanium dioxide in its most preferred form, essentially, contains no crystalline titanium dioxide. In another preferred embodiment of the invention gold particles preferably associated with disordered titanium phase than with any crystalline phase of titanium dioxide, which may be present. HR-TEM and analysis of energy dissipation by x-rays (EDX) can be used to give an idea about the relationship between gold particles and titanium.

Ions of titanium in neporyadochen links with other ions of titanium in small domains of two-dimensional single-layer mesh. Regardless of the actual topology, the disordered phase does not show an ordered periodic crystallinity. In another aspect of the present invention titanium ions preferentially occupy the nodes, essentially, four - or five-coordinate or strain changes, in contrast to the octahedral coordination. In a broad sense, however, the disordered phase titanium is not limited to any particular topology or coordination.

Disordered titanium phase can be distinguished from bulk crystalline titanium dioxide using the method of transmission electron microscopy, high-resolution (HR) and/or a method of Raman spectroscopy, as described below. In addition, disordered phase does not show a specific pattern of x-ray diffraction (XRD). The x-ray diffraction, however, is less sensitive for the detection of crystalline titanium dioxide. Accordingly, the absence of XRD-pattern characteristics of bulk crystalline phases of titanium dioxide is not convincing evidence that these phases are not present in the media. UV spectroscopy and spectroscopy in the visible part of the spectrum of the diffuse reflectance (UV-VIS DRS) are the and crystalline titanium dioxide. Usually to identify disordered phase may be any of the methods HR-TEM, Raman spectroscopy or UV-VIS DRS. To identify the disordered phase, it is preferable to use two or more of these methods. Furthermore, in addition to the HR-TEM, Raman spectroscopy and/or UV-VIS DRS methods of analysis to identify the disordered phase can be applied x-ray absorption spectroscopy at near-edge structure (XANES) at the titanium K-edge. It should be noted that the methods of spectroscopy of L2-edge and L3-edge titanium XANES K-edge of oxygen XANES can provide additional data that are consistent with the above methods and the differences between the disordered phase and a crystalline titanium dioxide.

To get a picture of a catalyst or carrier in the present invention can be applied to any transmission electron microscope high resolution. The expression "high resolution" involves the resolution on the level of atomic lattices. Accordingly, the resolution from point to point of the device should be at least or better. The preferred catalyst or the carrier of this type do not exhibit essentially distinct ordered paintings, izobrajenia titanium, give the image planes of the crystal lattice, separated by about for anatase and about for rutile.

Raman spectroscopy, as described above in paragraph (C), is also sensitive to the presence of crystalline titanium dioxide. In the media described in the description essentially, there are no peaks in the Raman spectrum for phases of anatase, rutile and brookite titanium dioxide.

Range of UV-VIS DRS of the carrier of this type can be obtained on any device designed for this purpose, such as DRS spectrometer Model UV-3101PC, allowing scanning in the range of 200-800 nm. The range includes the convolution of the bands caused by charge transfer from oxygen to titanium in the region of about 300 nm, Mie scattering of gold particles in the range of about 525 nm and other bands attributed to scattering by particles of gold or absorption of organic substances detected in the samples of the used catalyst. Decomposition of the spectrum into its individual components can be performed by non-linear alignment by the method of least squares. The scope of the charge transfer is particularly useful, and its preliminary analysis revealed S. Klein with al., Journal of Catalysis, 163, 489-491 (1996). Fresh catalyst or the carrier containing auparavant. On the contrary, the catalyst or the carrier containing crystalline titanium dioxide, find the band charge transfer at about 315 nm or longer wavelengths. For example, a pure phase of anatase and rutile titanium dioxide show a peak at 359 and 395 nm, respectively.

Range XANES K-edge titanium is also used to distinguish disordered titanium phase and phases of anatase and rutile titanium dioxide. Measurement of the XANES spectrum is described below. And anatase, and retelny Titan show three peaks in the spectrum of the Ti K-edge XANES. When the device operates in the transmission mode and calibrated internal metal titanium standard, in which the zero energy is set when 4966,0 eV (anatase and rutile each show three peaks at about +2,9, +5.9 and +8.3 eV. In anatase and rutile distorted octahedral coordination of titanium. In contrast, disordered titanium phase of the present invention shows essentially a single peak at about +4,61,2 eV, preferably at +4,60,3 eV. Apparently, the coordination of titanium in the disordered phase is approaching a four - or five-fold coordination.

The carrier may be any silicon dioxide, provided that it is acceptable for the active catalytic who hydroxylamino surface. Non-limiting examples of suitable silica include pulverized silicon dioxide, silica gel, precipitated silica, precipitated silica, silicalite and mixtures thereof. Preferably, the surface area of the silica is higher than approximately 15 m2/g, more preferably above about 20 m2/g and most preferably above about 25 m2/, More preferably, the surface area of the silica is less than about 800 m2/g, most preferably less than about 600 m2/,

Download titanium on the silicon dioxide can be anything that increases the activity of the catalyst in the method according to the present invention. Typically, the loading of titanium is higher than about 0.02 wt.%, preferably above about 0.1 wt. % relative to the weight of silicon dioxide. Typically, the loading of titanium is less than about 20 wt. % and preferably less than about 10 wt. % relative to the weight of silicon dioxide.

The method of deposition of titanium ions on the silicon dioxide is essential to obtain a disordered titanium phase described above. Description get used here, see S. Srinivasan with al., Journal of Catalysis, 131, 260-275 (1991) and R. Castillo with SOT is to see a titanium compound, which interacts with the hydroxyl groups on the surface of the silicon dioxide. Typically, the solution containing the reactive compound of titanium is in contact with the silicon dioxide under mild conditions such as at a temperature in the range of from about 0oWith up to about 50oWith, at about atmospheric pressure for a time from about 30 minutes to about 24 hours. Non-limiting examples of suitable reactive titanium compounds include titanium alcoholate, such as isopropyl titanium, propilot titanium, titanium ethylate and butyl titanium; titanium sulfate, oxysulfate titanium, titanium halides, preferably chloride titanium; titanium carboxylates, preferably the titanium oxalate, and technoorganic halides, such as dicyclopentadienyltitanium, and other organotitanate. Preferably use a titanium alcoholate. The solvent can be any, which dissolves the reactive compound of titanium, for example aliphatic alcohols, aliphatic and aromatic hydrocarbons, and water, where necessary. After contacting the carrier with a solution containing the reactive compound of titanium, the carrier is dried at a temperature in the interval is, in vacuum or in a stream of air or inert gas, such as nitrogen, argon or helium. After that, the media can be used without annealing or further processing. Alternatively, after drying medium can be ignited in air or in an inert gas, such as nitrogen or helium, at a temperature of from about 100oWith up to approximately 800oC, preferably from about 100oWith up to about 650oC.

An alternative method of deposition of titanium is vapor. Volatile compounds of titanium, such as titanium chloride, propilot titanium or isopropyl titanium, can be passed through the media of silicon dioxide in a stream of inert gas, such as nitrogen, argon or helium. The connection of titanium can be heated to volatilization or evaporation in a stream of inert gas. The media of silicon dioxide can be heated in the process. After this media can be used without annealing or further processing. Alternatively, the carrier may be calcined in air or in an inert gas, such as nitrogen or helium, at a temperature of from about 100oWith up to approximately 800oC, preferably from about 100oWith up to about 650oC.

that is, Titanium, dispersed n is briteney includes titanium, dispersed in the promoter metallosindikat. Can be used stoichiometric or non-stoichiometric compositions containing promotor metroselect. May be any amorphous or crystalline silicate of the metal-promoter. Preferred silicates of metals such promoters include silicates of metals of Group 1, Group 2, lanthanoide rare earth metals and actinoid metals, and combinations thereof. Non-limiting examples of preferred silicates promoter metals include magnesium silicate, calcium silicate, barium silicate, silicate erbium and lutetium silicate. Titanium can be dispersed in the silicate promoter-metal manner similar to that described in section (d) above. To identify dispersed titanium phase it is possible to use analytical methods that are described in section (d) above.

f. The mixture of media.

In the catalyst according to the present invention can be applied to any combination or mixture of the carriers a to e described above.

Download gold on titanium containing media (a-f) can be any that provides improved catalyst of the present invention. Typically, the loading of gold is higher than about 0.01 wt. % relative, preferably above approximately 0.05 wt. %. Typically, the loading of gold is less than about 20 wt. %. Preferably, the loading of gold is less than about 10.0 wt. %, more preferably less than about 5.0 wt. %.

The gold component may be deposited or applied to the carrier by any known technique in a way that ensures the active and selective epoxidation catalyst in the method according to the present invention. Non-limiting examples of known methods of deposition include impregnation, ion exchange, and sediment deposition. The preferred deposition method is disclosed S. Tsubota, M. Haruta, T. Kobayashi, A. Ueda, Y. Nakahara, "Obtaining highly dispersed gold on titanium and magnesium oxide in the Preparation of Catalysts, V. G. Poncelet, P. A. Jacobs, P. Grange, B. Delmon, Elsevier Science Publishers B. V., Amsterdam, 1991, p. 695ff included in the description by reference. This method comprises contacting the carrier with an aqueous solution of a soluble gold compounds at a temperature and pH sufficient to precipitate gold compounds on the carrier. Can also be used non-aqueous solutions. After that, in the preferred method according to the present invention, which differs from the above-mentioned references, the composite gold/media is not washed or slightly washed predpochitayut at a temperature sufficient to restore gold to essentially metallic gold with an average particle size in the range from about to about

In the case of aqueous solutions can be used any water-soluble gold compounds such as gold(3)chloride-hydrogen acid, chloraurate sodium, chloraurate potassium gold cyanide, qualitativeand and trichloride diethylaminotoluene(3) acid.

Usually both molarity soluble gold compounds varies from about 0.001 M to the saturation point of soluble gold compounds, preferably from about 0.005 M to about 0.5 M. the pH of an aqueous solution of gold govern in the range of from about 5 to about 11, preferably from about 6 to about 9, any suitable base, such as hydroxides or carbonates of a metal of Group 1, preferably sodium hydroxide, sodium carbonate, potassium carbonate, cesium hydroxide and cesium carbonate. To the solution add the required amount of media or, conversely, if necessary, re-adjust the pH. After that, the mixture is stirred in air at a temperature in the range from about 20oWith up to approximately 80oWith the passage of time from about 1 hour to about 24 hours. At the end of this period the e metal salts of promoters, preferably at a pH in the range of from about 5 to about 11. Then the solid is dried in air at a temperature of from about 80oWith up to approximately 120oC. the Solid is then calcined in air or in a reducing atmosphere such as hydrogen or heated in the atmosphere of inert gas, such as nitrogen, at a temperature ranging from approximately 250oWith up to approximately 800oWith the passage of time from about 1 hour to 24 hours.

Used in the method according to the present invention, the catalyst requires at least one metal promoter. As the metal promoter may be any metal ion having a valence of from +1 to +7, which increases the productivity of the catalyst in the oxidation method of the present invention. Factors that cause an increase in the productivity of the catalyst include increased conversion of olefin, increased selectivity for refinanced, reduced water outlet and extended service life of the catalyst. Limitiruyuschie examples of suitable metal-promoter include the metals of Groups 1 To 12 of the Periodic table of elements, and rare earth lanthanides and actinides, as stated in the CRC Handbook of Chemistry and Physics, 75-oe ed., CRC Press, 1994. Predpochtitel is try, potassium, rubidium and cesium; from metals of Group 2, which includes beryllium, magnesium, calcium, strontium and barium; of lanthanoid rare earth metals including cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; actinoid metals, especially thorium and uranium. More preferably, the metal-promoter is magnesium, calcium, barium, erbium, lutetium, lithium, potassium, rubidium, cesium, or a combination of both.

In another preferred embodiment of the invention, the metal-promoter excludes palladium and even more preferably the metal-promoter eliminates the metal of Group VIII, namely iron, cobalt, Nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum. Used in the description of the term "exclude" means that the total concentration of metal (metals) of Group VIII is less than 0.01 wt. %, preferably less than about 0.005 wt. per cent, of the total catalyst composition.

The full amount of metal(metals)-promoter deposited on the carrier, as a rule, is more than about 0.01 wt. %, preferably more than about 0.10 wt. % and more preferably more than approximately 0.15 wt. % relative to the total weight of the catalyst. The total number of edocfile less than about 15 wt. % and more preferably less than about 10 wt. % relative to the total weight of the catalyst. Specialists in this field will be obvious that when using metal-promoter titanate or silicate mass percentage of the metal promoter may be much higher, for example as high as about 80 wt. %.

If necessary, the promoting metal (metals) may be deposited on such carrier concurrently with gold or, alternatively, in a separate stage of the deposition, either before or after deposition of gold. Alternatively, the metal promoter may be deposited to form the catalyst precursor prior to the addition of titanium or after adding it, or simultaneously with the titanium. Typically, the metal-promoter precipitated from aqueous or organic solution containing a soluble salt of the metal-promoter. You can use any salt of the metal-promoter with the corresponding solubility, for example, are suitable nitrates, carboxylates and galley metals, preferably nitrates. In the case of the use of an organic solvent may be any of many known organic solvents, including, for example, alcohols, esters, ketones, and aliphatic and aromatic from the those used when contacting the carrier with a solution of gold. After deposition of the metal-promoter making the rinsing is optional and if it is done excessively, can cause leaching of the catalyst at least part of the metal-promoter. Then carry out the calcination in air or in a reducing atmosphere or heated in an inert gas in accordance with the method similar to that described above for the deposition of gold.

Optionally, the catalyst according to the present invention can be extruded, connected with/or printed on the second medium, such as silicon dioxide, aluminum oxide, aluminum silicate, magnesium oxide, titanium dioxide, carbon or mixtures thereof. The second medium can improve the physical properties of the catalyst, such as strength or resistance against abrasion, or to bind together the particles of catalyst. Generally, the amount of the second medium is from about 0 wt. % to about 95 wt.% on the combined weight of the catalyst and the second carrier. It should be noted that although the catalyst of the present invention may be physically mixed or extruded with titanium dioxide or associated with titanium dioxide as the second carrier, in predpochtitelno contains no crystalline titanium dioxide, as pointed out above. If titanium dioxide is used as the second carrier, you must bear in mind that his presence may hinder the analytical identification of the catalyst. In this case, especially the analysis of the catalyst should be carried out in the absence of the second medium.

The method according to the present invention can be carried out in any standard reactor designs suitable for gas-phase or liquid-phase process. These designs are widely include reactors periodic operation with fixed bed, moving layer, fluidized bed, moving bed, casing and tubular reactors with a layer with jet stream of fluid, as well as the design of the reactor with continuous flow and intermittent flow and swing reactors. Preferably, the method is carried out in the gas phase and the reactor is designed with heat transfer elements of the heat. Preferred reactors are designed for these purposes include reactors, fluidized bed and moving bed, and swinging reactors, designed from a variety of catalytic layers connected in parallel and used in an alternative way.

e and non-Flammability. It is necessary, however, to distinguish the conditions that exist between non-flammable and flammable mixtures of olefin, hydrogen and oxygen. Respectively, may be constructed or taken into account the phase diagram, which for any given temperature and pressure method, you can define ranges of Flammability and non-for compositions of the reagents, including the diluent, if used. It is believed that the preferred mixture of the reactants, as defined above, are beyond the mode of ignition, when the method is carried out at the preferred temperatures and pressures specified in the description below. However, experts in this field it is obvious that it is possible to conduct the method in the mode of ignition.

Typically, the method is carried out at a temperature that is higher than about ambient, taken equal to 20oC, preferably above about 70oC, more preferably above about 120oC. Typically, the method is carried out at a temperature of less than approximately 250oWith, preferably less than about 225oC, more preferably less than about 200oC. Preferably, the pressure ranges from about at the CLASS="ptx2">

In flow reactors, the residence time of the reactants and the molar ratio of the reactants to the catalyst will be determined by the bulk velocity. In the case of gas-phase method average hourly feed rate (GHSV) of gaseous olefin can vary widely, but typically is greater than about 10 ml of the olefin to 1 ml of catalyst per hour (h-1), more preferably about 100 h-1and more preferably more than about 1000 hours-1. Usually GHSV of olefin is less than about 50000 hours-1, preferably less than about 35000 h-1and more preferably less than about 20000 h-1. Similarly, in the case of liquid-phase method average hourly feed rate (WHSV) of olefinic component may vary within a wide range, but typically is greater than about 0.01 grams of olefin per 1 g of catalyst per hour (h-1), more preferably approximately 0.05 h-1and more preferably more than about 0.1 h-1. Usually WHSV of olefin is 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 raw material oxygen, hydrogen and rolary ratios.

When contacting the olefin containing at least three carbon atoms with oxygen in the presence of hydrogen and catalyst, described above, receive the appropriate refinanced (epoxide) with a good yield. The most preferable received olefination is propylene oxide.

Conversion of olefin in the method according to the present invention may vary depending on the particular applicable conditions of the method, including the specific olefin, temperature, pressure, molar ratio and the shape of the catalyst. Used in the description of the term "conversion" is defined as the molar percentage of olefin, reacting with the formation of products. Typically, the conversion increases with increasing temperature and pressure and decreases with increasing flow rate. Typically, the conversion of the olefin is higher than about 0.1 mol. %, preferably above about 0.2 mol. % and more preferably above about 1.5 mol. %.

Similarly, the selectivity for refinanced may vary depending on the particular applicable conditions. Used in the description, the term "selectivity" is defined as the molar percentage of the reacted olefin which forms Conques the temperature and increase with increase in flow rate. The method according to the present invention ensures olefination with unexpectedly high selectivity. Normal selectivity for refinanced in the present method, above about 80 mol. %, preferably above about 90 mol. % and more preferably above about 94 mol. %. Even at 165oWith selectivity for propylene oxide surprisingly high, ranging from about 85 to 95 mol. %.

Mainly, the efficiency of hydrogen in the method according to the present invention is satisfactory. A number of additional hydrogen can be burned directly with the formation water. Accordingly, it is desirable to provide a lower molar ratio of water to refinanced. In the method according to the present invention the molar ratio of water to refinanced is usually above about 2:1 but less than about 15:1 and preferably less than about 10:1 and more preferably less than about 7:1.

The catalyst of the present invention demonstrates a long service life. As used in the description, the term "service life" means the time measured from the beginning of the oxidation process to the moment at which the catalyst after regeneration loses sufficient activity and becomes the Kaa service the catalyst remains active for long periods of time with minor decontamination. Usually in a reactor with a fixed layer is achieved duration of work without deactivation of the catalyst is higher than approximately 125 hours. The preferred length between regenerations will depend on the reactor design and can vary from a few minutes for reactors with moving a layer up to several months for reactors with a fixed layer. Additional evidence of its longevity is that the catalyst according to the present invention can be regenerated for multiple cycles without significant loss of catalytic activity or selectivity.

When the activity is reduced to an unacceptably low level, the catalyst according to the present invention can be easily regenerated. Regeneration of the catalysts of the present invention may be any known in the chemical technology way, provided that the regenerated catalyst to the oxidation process described in this invention. One of the ways regeneration includes heating the deactivated catalyst at a temperature of from about 150oWith up to approximately 500oWith a regeneration gas containing hydrogen and/or oxygen and, neosapien 400oC. the Amount of hydrogen and/or oxygen in the regeneration gas may be any that provides effective regeneration of the catalyst. Preferably, the hydrogen and/or oxygen is from about 2 to about 100 mol. % gas for regeneration. Suitable inert gases are chemically inactive and include, for example, nitrogen, helium and argon. The time during which the regeneration of the catalyst may vary from about 2 minutes to several hours, for example about 20 hours at low temperature regeneration. In an alternate embodiment of the gas for regeneration is useful to add water in an amount preferably from about 0.01 to about 100 mol. %.

The invention is additionally illustrated by the following examples, which are illustrative only. Other embodiments of the invention will be obvious to specialists in this area when considering the present description, or the practice of the present invention disclosed in the description. Unless specifically stated, all percentages are given on a molar basis.

Getting silicalite titanium TS-1 with Si/Ti = 100.

In a 4-liter glass stainless steel give tetraethylorthosilicate (Fisher TEO is obyavlaemyi to TEOS weight of n-butyl titanium, defined by difference, was 14,07, Get a transparent yellow solution. The solution is heated and stirred in a nitrogen atmosphere for about 3 hours. The temperature change from the 50oWith up to 130oC. the Solution is then cooled in an ice bath.

In a plastic bottle measure a 40% (wt.) a solution of hydroxide of tetrapropylammonium (TRON, 710,75 g), close it with a cap and placed in an ice bath. To a chilled solution of TEOS with vigorous stirring overhead stirrer is added dropwise TRAIN. After adding half of TRON the TEOS solution was Motel and began to thicken. Within five minutes the solution was completely frozen. At this point add the rest of TRON, destroy gel with a spatula and resume mixing. Add deionized water (354 g) and the solution warmed to room temperature. After 5 hours, the solid was largely dissolved, and add an additional amount of deionized water (708 g). Stirring is continued throughout the night, getting transparent yellow synthetic gel that does not contain solids.

Synthetic gel poured into a stainless steel autoclave with a volume there are 3,785 liters (1 gallon) and sealed. The autoclave is heated to 120assessment of the reaction, the autoclave is cooled and extracted a milky-white suspension. The solid is extracted, washed, centrifuged and re-suspended in deionized water. The solid is filtered off, dried at room temperature and slowly heated to 550oC and calcined in air for 8 hours. The solid is identified as having a MFI structure, as determined by XRD. In the Raman spectrum did not reveal any crystalline titanium dioxide. By x-ray fluorescence (XRF) found that the atomic ratio Si/Ti is equal to 100. Output silicalite titanium 106,

Example 1. Obtaining catalyst for epoxidation.

Silicalite titanium TS-1 (10,042 g) with the atomic ratio Si/Ti = 100, obtained in accordance with the above described method, is added to aqueous solution of gold(3)hydrochloric acid HAuCl43H2O (0,4829 g in 50 ml water). The addition of sodium carbonate establish a pH in the range 7-8. Add magnesium nitrate, Mg(NO3)26N2O (1,97 g) when more sodium carbonate, up until the pH becomes 7-8. The total amount used of sodium carbonate is of 0.62, the Mixture is stirred over night. The solid product is filtered and the filter cake washed three times with 150 ml of water. Wet filtrowanie and then calcined in air at 400oC for 5 hours, obtaining the epoxidation catalyst containing gold on TS-1. By neutron activation analysis (NAA) determine the composition of the catalyst: Au 1,07%, Si 41,0%, Ti of 0.77%, Mg of 0.21% and Na 0,31% (mass percent). According to THE average particle size of gold is equal to

Example 2. The oxidation of propylene to propylene oxide.

The epoxidation catalyst from Example 1 experience in the direct oxidation of propylene to propylene oxide. The catalyst (5 cm3) load in a continuous flow reactor with a fixed bed of 10 cm3through which flow streams of helium, oxygen, hydrogen and propylene. The total flow rate of 150 cm3/min (or GHSV 1800 h-1). The composition of the flow of raw materials includes 5,0% hydrogen, 10.5% oxygen and 53,6% propylene, the rest is helium. Propylene, oxygen and helium served as the pure streams of hydrogen in a mixture with helium in a ratio of 20 N2/80 Not (./vol.). The pressure in the atmospheric reactor, the temperature in the reactor from the 50oWith up to 165oC. the Products analyzed, using built-in gas chromatograph (column ChrompakTMPoraplotTMS, 25 m). The results are shown in Table 1.

The data show that the composition comprising gold and the magician is Lena. The activity increases with increasing temperature and at 110oWith the conversion of propylene reaches of 0.20%. The maximum selectivity for propylene oxide reaches above 99%.

Getting silicalite titanium TS-1 with Si/Ti = 27.

A 3-liter flask Erlenmeyer measure tetraethylorthosilicate (Fisher TEOS, 1250 g) and rinsed with gaseous nitrogen for 30 minutes. From the syringe into the TEOS introduce n-butyl titanium (DuPont, Ti(O-n-Bu)4, a 51.2 g) with vigorous stirring. The flask placed in a water bath at 50oC, stirred for 1 hour and then allowed to stand for about 60 hours under a layer of nitrogen. a 40% (wt. ) solution of hydroxide of tetrapropylammonium (the Sachem TRAON, 1069,7 g) is added to deionized water (540 g) in 2-liter beaker and cooled in an ice bath. TEOS is also cooled in an ice bath. When two solutions are cooled to a temperature below 10oWith the TEOS solution is transferred into a 4 liter beaker of stainless steel, equipped with overhead stirrer. The solution TRAN added dropwise from a dropping funnel. Adding complete after 5 hours and get transparent yellow synthetic gel.

Synthetic gel poured into a stainless steel autoclave with a volume there are 3,785 liters (1 gallon) and sealed. The autoclave is heated to 100oWith the t continuously stirred. At the end of the reaction, the autoclave is cooled and extracted a milky-white suspension. The solid is extracted, washed, centrifuged and re-suspended in deionized water. The washing was repeated three times until the pH of wash water is below a pH of 9. The solid is dried at 65oWith during the night and get white bread, which are crushed before the sieve size 20 mesh. The solid is heated to 500oC for 8 hours and then calcined in air at 500oC for 2 hours. The solid is identified by XRD method in the presence of MFI structure. In the spectrum of the detected Raman titanium dioxide in the anatase phase (about 50% of the total mass of the titanium). Method XRF found that the atomic ratio Si/Ti is equal to 27. Output 175,5,

Examples 3(a) and 3(b). Obtaining catalysts and their evaluation in the oxidation of propylene to propylene oxide.

Get two catalyst. Gold(3)hydrochloric acid is dissolved in water (50 g). TS-1 with Si/Ti=27, obtained above, is added to the solution with stirring. For sample 3(a) add the sodium carbonate. For sample 3(b) add the sodium carbonate and nitrate of erbium. The mixture is stirred for one hour. To each mixture is added sodium carbonate to pH regulation in dicebant sodium. The mixture is stirred over night. The solid is filtered off from each sample and three times washed with water (150 cm3for leaching). The solid is dried in air at 110oC for 1 hour, slightly crushed to loosen large particles, and then calcined in air at 120oC for 3 hours. Then the solid is heated to 400oC for 8 hours and maintained at 400oC for 5 hours. Then the solid is cooled to 350oC for 1 hour and then to room temperature, obtaining a catalyst containing gold, deposited on TS-1. For each catalyst specify the number of reagents.

Example 3(a): gold(3)hydrochloric acid 0,217 g; TS-1 10,040 g; sodium carbonate 0,218,

Example 3(b): gold(3)hydrochloric acid 0,134 g; TS-1 - 5,054 g; erbium nitrate 1,048 g; sodium carbonate 0,596,

The average size of the gold particles in the catalyst 3(a) equal and catalyst 3(b) For both catalysts loading of gold is approximately 0.7 wt. %. Download erbium defined XRF method, 6.5 wt. %. THE analysis showed mixed particles of gold-erbium and gold particles and erbium deposited on the surface of silicon dioxide.

Both catalyst to catalyze the direct oxidation of propylene to propylene oxide. When comparing Example 3 with Example 3(b) under identical conditions, the method can be seen that the catalyst with an erbium promoter exhibits a higher conversion at almost the same selectivity. In Example 3(b) conversion reaches of 0.44% at a selectivity for propylene oxide 96,7%.

Example 4. Evaluation of the regenerated catalysts.

Used catalysts of Examples 3(a) and 3(b) are removed from the reactor, placed in an air thermostat at 400oC and stirred every 30 minutes for a total of 2 hours, receiving the regenerated catalysts, which have in the oxidation of propylene to propylene oxide, as shown in Table 3, Examples 3(a)-1 and 3(b)-1. Catalysts regenerate the second time at 220oWith in a mixture of 10% oxygen with helium and then cooled to a temperature of 130oWith, where they are evaluated in the oxidation process, as shown in Table 3, Examples 3(a)-2 and 3(b)-2. Catalysts regenerate third time at 250oC in an atmosphere of helium with 10% oxygen and then cooled to a temperature of 130oWith, where they are evaluated in the oxidation process, as showing a mixture of oxygen and helium, evaluated in the oxidation process, as shown in Table 3, Example 3(b)-4.

As can be seen from Table 3, the catalysts regenerated up to four times, continue to show significant activity with high selectivity for propylene oxide.

Example 5. Receiving catalyst and process for the epoxidation.

Following the procedure of Example 1 and using reagents in the amounts indicated in Table 4, get three catalyst (a, b, C), containing gold on TS-1 (Si/Ti = 27).

Catalysts a, b and C estimate in the direct oxidation of propylene according to the method of Example 2. The results are presented in Table 5.

As can be seen from Table 5, at constant temperature, pressure, and flow rate, while increasing the loading of gold also increases the conversion of propylene. Also with the increase in the process pressure significantly increases the conversion of propylene. Under these conditions, the process selectivity remains approximately constant when the value is higher than about 90%.

Examples 6 (a-j).

Get 10 catalysts: in water (500,0 cm3) dissolved gold(3)hydrochloric acid (1,4526 g). The solution is divided into 10 portions 50 cm3each. The carrier of TS-1 (Ti/Si=31) selolwane the suspension is stirred at room temperature for about 30 minutes To each mixture, add salt promoting metal in the amount indicated in Table 6, and the mixture is stirred for 1 hour.

Add sodium carbonate to a pH of 7.6, and the mixture is stirred for 1 hour. If necessary, to bring the pH to 7.6 add sodium carbonate. The mixture is stirred over night and then leave for the weekend at room temperature. The mixture is filtered, the filtered substance was washed with water, dried in air at 120oWith, calcined in air for 8 hours to 400oWith and incubated for 5 hours at 400oC. Each catalyst (5 cm3) experience in the oxidation of propylene with a flow rate of 150 cm3/min, 30% propylene, 10% oxygen, 10% hydrogen, the rest is helium. The results are shown in Tables 7 and 8.

From Tables 7 and 8 shows that the catalysts containing gold and metals of the Groups 2 or rare earth lanthanides, applied to TS-1, are active catalysts for the oxidation of propylene to propylene oxide.

Examples 7(a-d).

Get five catalysts according to the following procedure: in the water (500,0 cm3) dissolved gold(3)hydrochloric acid (1,4539 g). Portions of a solution of gold by 50 cm3used for each sample, catalyst The resulting suspension is stirred at room temperature for 1 hour. the pH of the solution was adjusted to 7.6 one of the following carbonate salts: (a) lithium carbonate; (b) potassium carbonate; (C) rubidium carbonate, and (d) cesium carbonate. The mixture is stirred for 1 hour and then, if necessary, to raise the pH to 7.6 add carbonate salt. The mixture is stirred over night at room temperature. The mixture is filtered and the filtered substance was washed with water (150 cm3). The wet solid is dried in air at 120oC and then calcined in an air oven to 400oWith 8 hours and maintained at 400oWith 5 hours. Each of the catalysts (5 cm3) experience in the oxidation of propylene stream containing 30% propylene, 10% oxygen, 10% hydrogen, the rest is helium at a flow rate of 150 cm3/min. and the Results are presented in Tables 9 and 10.

From Tables 9 and 10, it is seen that the catalyst containing gold and not necessarily the promoting metal of Group 1, deposited on a porous titanosilicate, is an active catalyst for the oxidation of propylene with oxygen in propylene oxide.

Comparative experiment 1 (CE 1).

The catalyst was prepared according to the method of Example 7, except that h is of atalla. Testing of the catalyst in the oxidation of propylene is carried out in accordance with Example 7, the results obtained are presented in Tables 9 and 10. From the comparison of Examples 6 (a-j) and example 7 (a-d) with Comparative experiment 1, one can conclude that the presence of the promoting metal in the catalyst increases the selectivity for propylene oxide and essentially reduces the receiving water. In some cases, the conversion also increases. The gold concentration in the comparative experiment is equal to 1.28 wt. %. From the comparison it is necessary that promoted metal catalysts according to Examples 6 (a-j) and 7 (a-d) the amount of gold less. Accordingly, the application of the promoting metals in these examples leads to a more efficient use of gold.

In the following Example 8 was recorded range XANES K-edge titanium. Spectrum data XANES K-edge titanium collect on a radial line HA National synchrotron light source (NSLS). As a monochromator is used NSLS flat crystal monochromator bumerangue-type Si (111) crystals. For focusing the beam in the horizontal and vertical directions using reflectors, obtaining a beam size of approximately 1 mm x 1 mm in the focal position inside the experts is t with the energy of the electrons 2,583 GeV thread-rays in the range of 100-300 mA. Higher harmonics of the beam was deflected by the detuning of the second Si(111) monochromator crystals up to 75% of the maximum intensity, the intensity of the incident beam was recorded ion chamber, which is connected to the beam tube and which was continuously purged with helium. X-ray absorption spectrum was recorded as fluorescently range using the in situ cell Lytle, nitrogen purged. Do not use any fluorescent filter, although the Soller slits were in place. Camera with sample was placed near the end of the beam tube in order to minimize the absorption of air and scattering at relatively low energy K-edge titanium (4,996 Kev). All catalyst samples were measured using the cell in situ Lytle with a catalytic powders, pressed into a self-sustaining plate diameter 25.4 mm (1 inch) (typical parameters used: 0.3 to 0.4 g catalyst 3500 kg over 5 minutes).

The device operates in the mode of transmission. For calibration of the energy used titanium foil. The first maximum of the first derivative of the K-edges of the metal titanium was installed when 4966,0 eV. The energy dimension of the sample is carried out relative to a calibration point 4966,0 eV which is taken for Ozzy heated to 500oWith in a mixture of 20% oxygen in helium. By placing thermocouple in the cell Lytle believe that the actual temperature of the catalyst may be lower by more than 50oWith the set point. After treatment, the cell is rinsed with clean helium to minimize the absorption of x-ray radiation with oxygen.

Example 8.

Media containing titanium dispersed on silica produced in accordance with the method described by S. Srinivasan with TCS. in Journal of Catalysis, 131, 260-275 (1991), except that the composite titanium-silicon dioxide does not heat up to temperatures above 200oC. Use silica Cabosil. Neutron activation analysis (NAA) media shows the content of titanium 2,84% and silicon 44%. The surface area of the carrier is equal to 300 m2/, Methods of spectral analysis of the Raman and XANES K-edge titanium found that the media does not show crystalline phases of titanium dioxide. XANES K-edge titanium shows the presence of a single peak at +4.8 eV relative to the inner metal titanium standard set at 4966 eV. Gold precipitated on the carrier as follows: gold(3)hydrochloric acid (0.04 g) dissolved in water (100 ml). the pH of the solution was adjusted to 7.5 at 80otemperature and add the magnesium nitrate (0.1 g). The mixture is stirred over night at room temperature. The solid is filtered and washed once with water. The solid is calcined in air by heating to 400oC for 8 hours and aged there for 3 hours. Then the solid is cooled to room temperature.

The composition of the catalyst according to NAA ( wt. %): Ti 2,86; Si 45,0; Au 0,25; 0,54 Mg and Na 0,33. HR-TEM indicates the lack of an ordered structure of the crystalline titanium dioxide. In the spectrum of the Raman missing peaks for crystalline titanium dioxide. According to the HR-TEM average particle size of gold is

The catalyst (1 g) is loaded into the flow reactor continuous fixed bed volume of 10 cm3that serves helium, oxygen, hydrogen and propylene. The composition of the flow of raw materials: polypropylene 30%, hydrogen, 7% oxygen, 7%, the rest is helium. The molar ratio of propylene/hydrogen equal to 4.2; the ratio of propylene/oxygen equal to 4.2; the ratio of hydrogen/oxygen is 1.0. Propylene, oxygen and helium are used as pure streams; the hydrogen is mixed with helium in the mixture 20N2/Ne (about. /about.). The total flow 2400 cm3/hour. The atmospheric pressure; the temperature of the reactor 135oC. the Products analyzed, using built-in ECENA 20 hours, the catalyst shows the conversion of propylene to 2%, with 92% selectivity for propylene oxide. The maximum conversion is equal to 3.3%, while 92% selectivity for propylene oxide; as by-products are detected only carbon dioxide and water. Within 20 hours, the catalyst produces more than of 0.58 mmol/g cat.-hour with a peak at 1.0 mmol/g cat. -hours. The concentration of propylene oxide at the outlet is higher than 0.6%, with a peak at 1% for 20 hours.

Example 9.

Sealed in a fume hood in hexane (20,8 g) dissolved titanium ethylate [1,14 g, Ti(O-Et)4(about 20 wt. % Ti in ethanol) from Aldrich]. The resulting solution is added to the silicon dioxide (11.1 g, 40/60 mesh, Cabot Cab-O-Sil EH5 pulverized silicon dioxide). Silicon dioxide is pre-moistened and dried at 110oC and calcined at 500oC. the Mixture is shaken and let stand for 10 minutes. The solvent and volatile components are removed at the rotary evaporator at room temperature for 1 hour in vacuum. Then the residue is heated to 100oWith vacuum, rotating at 100oWith about 1 hour and cooled to room temperature to obtain the carrier of the present invention.

The gold solution is get, dissolving gold(3)hydrochloric acid (0,1040 g) in water (400 cm3) and heating to 70oC. add the ri 70oC. Re-adjusted the pH to 7.5 with sodium carbonate. The mixture is stirred for 1 hour at 70oWith maintaining pH 7.5, and then cooled to room temperature. The solid is filtered. The solid is added to water (200 cm3) at pH 7.5 (Na2CO3) and stirred for 5 minutes.

The solid is filtered, dried at room temperature for 1 hour by passing air through a solid substance on a porous filter. The product is calcined in air in the temperature range from room temperature to 100oC for 1 hour, incubated at 100oC for 1 hour, then heated to 400oC for 8 hours and maintained at 400o4 hours, obtaining a catalyst according to the present invention.

Defined by NAA ( wt. %) the catalyst had the following composition: Au 0,106; Na of 0.48; Ti 1,96; Si 43,2; magnesium is not found. Not detected crystalline titanium dioxide in the Raman spectrum (excitation at 532 nm) and HR-TEM. The average particle size of gold is In the spectrum of UV-VIS DRS (fresh catalyst) found peak at 309,9 nm. In the spectrum of the Ti K-edge XANES contains single peak at +4,70 eV.

Test catalyst (2,01 g, 7.5 cm3in the oxidation of propylene with oxygen. Palatalization rinsed with a mixture of oxygen (10%) with helium until the disappearance of propylene in the mass spectrum. Then the catalyst was heated from 140oWith up to 350oC for 45 minutes in a mixture of oxygen and helium at a flow rate of 150 cm3/min, then maintained at 350oC for 2 hours. The catalyst is cooled to 120oWith in the gas mixture. The regenerated catalyst was tested in the oxidation process. The results are shown in Table 3. The catalyst to regenerate the second time in the following way. The catalyst was rinsed with a mixture of oxygen (10%) with helium before disappearing in the mass spectrum of propylene. The catalyst was heated from 120oWith up to 350o1 hour in a mixture of oxygen with helium and at a flow rate of 150 cm3/min, then heated to 370oC for about 15 minutes and kept at this temperature for 1 hour. The catalyst is cooled to 350oWith a mixture of oxygen with helium and maintained at 350oWith 4 hours. The catalyst is cooled to 120oWith a mixture of oxygen with helium and then repeat the test in the oxidation process. The results are shown in Table 11.

From Table 11 it is seen that the catalyst according to Example 8, containing gold and sodium on the carrier obtained with titanium ethylate, is an active catalyst for the direct oxidation of propylene to propylene oxide.

the water (400 cm3) and heating to 70oC. the Addition of sodium carbonate bring the pH to 7.5. Quickly add media (5,035 g) according to Example 9 and thoroughly stirred at 70oC. the pH is again adjusted to 7.5 by adding sodium carbonate. To the solution add magnesium nitrate (0.50 g) and the pH was adjusted with sodium carbonate. The mixture was stirred at 70o1 hour, maintaining the value, pH 7.5, and then cooled to room temperature. The solid is filtered. The solid is added to water (200 cm3) at pH 7.5 (Na2CO3) and stirred for 5 minutes. The solid is filtered, dried at room temperature for 1 hour by passing air through a solid substance on a porous filter. The material calcined in air at a temperature of from room temperature to 100oC for 1 hour, incubated at 100o1 hour, then heated for 8 hours to 400oC and maintained at 400o4 hours, obtaining a catalyst according to the present invention.

The composition defined by NAA, the following ( wt. %): Au 0,207; 0,53 Mg; Na 0,17; Ti 1,94; Si 42,0. In the Raman spectrum is not detected crystalline titanium dioxide (excitation at 532 nm). In UV-VIS DRS spectrum (fresh catalyst) is present peak at 306,4 nm. Ti K-edge XANES shows only the I of propylene with oxygen. The results are shown in Table 12. The catalyst regenerate twice as described in Example 9 and re-experience in the oxidation process. The results are given in Table 12.

As can be seen from Table 12, the catalyst according to Example 10, containing gold, sodium, and magnesium on the media received from ethylate titanium has a high selectivity for propylene oxide, a good conversion of propylene and high efficiency of hydrogen.

Example 11.

Media get in accordance with Example 9 with the difference that instead of ateleta titanium, dissolved in hexane, applied isopropyl titanium (1,34 g) dissolved in isopropanol (24,0 g). Gold precipitated on a carrier as in Example 9 with the difference that the gold(3)hydrochloric acid (0,1050 g) apply with the carrier (5,045 g).

The composition defined by NAA, the following ( wt. %): Au 0,098; Na 0,43; Ti 1,89; Si 42,0; Mg is not detected. Not detected crystalline titanium dioxide in the Raman spectrum (excitation at 532 nm) and HR-TEM. The average particle size of gold is In the spectrum of UV-VIS DRS (fresh catalyst) has a peak at 301,5 nm. In the spectrum of the Ti K-edge XANES has a peak at +4,42 eV.

Experience the catalyst (2.0 g, 7.5 cm3in the process of oxidation prop the comfort analogously to Example 9 and re-experience in the oxidation process. The results are shown in Table 13.

The data show that the catalyst according to Example 11, containing gold and sodium on the media received from isopropylate titanium has excellent selectivity for propylene oxide, provides a good conversion of propylene and an excellent efficiency of hydrogen.

Example 12.

Gold precipitated on the carrier according to Example 11 (5,045 g) in accordance with the procedure described in Example 10. Gold(3)hydrochloric acid (0,1044 g) is used for solution of gold, and to the mixture nitrate magnesium (0,49 g).

The composition defined NAA, the following ( wt. %): Au 0,210; 0,48 Mg; Na Of 0.14; Ti 1,85; Si 41,2. Not detected crystalline titanium dioxide in the Raman spectrum (excitation at 532 nm). In the spectrum of DRS (fresh catalyst) has a peak at 298,1 nm. In the Ti K-edge XANES has a peak at +of 4.66 eV.

Test catalyst (2.00 g, 7.5 cm3) in the oxidation of propylene with oxygen. The results obtained are presented in Table 14. Used catalyst twice regenerate in a manner analogous to Example 9, and re-experiencing in the oxidation process. The results are shown in Table 14.

The data show that the catalyst initial selectivity for propylene oxide, provides good conversion of propylene and high efficiency of hydrogen.

Example 13(A-E).

Get five catalysts, using a carrier of titanium dioxide (anatase) and the reagents in the amounts listed in Table 15. Gold(3)hydrochloric acid is dissolved in water (100 g). Add titanium dioxide (Degussa P25) and stirred. Add the promoters and mix. Add sodium carbonate to a pH of 7.0 and 7.6. The mixture is stirred over night. The solid is filtered and washed three times with water and dried at 120oWith during the night. Samples calcined in air at 120-400oC for 4 hours and maintained at 400oWith 5 hours.

Conduct testing of catalysts in the oxidation of propylene with oxygen in propylene oxide. The results obtained are presented in Table 16.

The catalysts recovered four times according to the method described below, and after each regeneration re-experiencing in the oxidation process with the results shown in Table 16.

Regeneration 1. The catalysts are heated to 300oWith a mixture of oxygen (20%) with helium. If 300oC for 30 minutes over a catalyst miss a mixture of hydrogen (20%) with helium to produce water. Catheterization heated at a rate of 10oWith/h to 300oWith a mixture of oxygen (10%) with helium maintained at 300oWith over the weekend, then cooled to 80oC. Raw material serves at 80oC.

Regeneration 3. The catalysts are heated at 50oWith/h to 300oWith a mixture of oxygen (10%) with helium maintained at 300oWith overnight, then cooled to 80oC. Raw material serves at 80oC.

Regeneration 4. The catalysts are heated to 350oWith a mixture of oxygen (10%) with helium and cooled to 80oC. the Catalysts purge helium mixture containing oxygen (10%) and water (2%), with 80oC. Then the water stops and served raw materials at 80oC.

Regeneration 5. The catalysts are heated to 350oWith in helium containing oxygen (10%) and water (2%) and then cooled to 80oC. the water Flow stops and served raw materials at 80oC.

Table 16 shows that the catalyst obtained from the gold on the media containing titanium dioxide and metal-promoter Group 2 or rare earth metal, is an active and selective catalyst for the direct oxidation of propylene to propylene oxide. The catalyst may be regenerated many times.

Example 14.

The following brazolot (1,501 g) in water (1 l). To a solution of gold (150 ml) was added with stirring titanium dioxide (10 g, Degussa P25). The promoting metal indicated in Table 17, was dissolved in water (50 ml) and added to a mixture of gold with titanium dioxide with stirring. The mixture is titrated to pH 7.5 with sodium carbonate and stirred for 2 hours. The solid is filtered and washed three times with water (100 ml). The sample And dried at 110oWith in the furnace. The samples and dried at 60oWith on the air. Samples calcined in a small tube furnace in an atmosphere of gases shown in Table 17. The temperature during annealing was increased from room temperature up to 400oC for 8 hours, and the samples were kept at 400oWith 5 hours.

The catalysts tested in oxidation of propylene with oxygen in propylene oxide. The results of the tests are presented in Table 18.

Table 18 shows that the catalyst containing gold on the media of titanium dioxide and metal-promoter Group 2 and obtained by annealing in an atmosphere of oxygen or hydrogen, is an active and selective catalyst for the direct oxidation of propylene to propylene oxide.

Comparative experiment 2.

Get the catalyst, as in Example 14, with the difference that do not add publice 17. Testing of the catalyst is carried out in the oxidation of propylene with oxygen in propylene oxide. The results are shown in Table 18. When comparing Example 14 Comparative experiment 2 found that the catalyst of gold on titanium dioxide, containing a metal promoter, essentially, more active and selective than catalyst obtained in the same manner but without the metal-promoter.

Example 15.

Used a sample of catalyst (10 cm3) Of example 14C recovered at 230oAnd then again experience in the oxidation of propylene at 80oC and a pressure of 98 psia (0,689 MPa). The results are shown in Table 19. The catalyst to regenerate the second time by heating in a mixture of oxygen (10%), water (1%), the rest is helium, up to 230oC, and then cooled to 110oC. oxygen and water ceased, the catalyst was rinsed with helium to remove water. The catalyst is cooled to 80oWith helium. A stream containing propylene (28%), oxygen (7%), the rest is helium, is passed over the catalyst as long as the threads will not become stable. Then the composition of the flow change on stream containing propylene (28%), oxygen (7%), hydrogen (7%), the rest is helium, and the catalyst again ispitivanja catalyst, containing gold on the media of titanium dioxide and magnesium, achieves good activity and high selectivity for propylene oxide.

Example 16.

The sample of silicon dioxide (49,67 g) [PQ CS1040-E, 1/16"extrudates], calcined to 300oWith nitrogen impregnated in an airtight Boxing isopropylate titanium (4,62 g) in isopropanol (44 g). The impregnated material was kept at room temperature for 1 hour in a flask in Boxing. Then the flask attached to a rotary evaporator and the solvent and volatile components are removed at room temperature in vacuum. The residue is heated in vacuum up to 50oC and maintained for 1 hour, then up to 80oC and maintained for 1 hour, and finally 100oC and maintained under vacuum for 2 hours. The material, the medium containing the titanium dispersed on silica, cooled to room temperature.

A solution of gold(3)hydrochloric acid (0.40 g) in water (1000 ml) heated to 60oC, pH adjusted to 8.0 with sodium carbonate and the solution is cooled to room temperature. Titanium containing medium (25 g) is added to the gold solution and stirred overnight on a rotary evaporator at atmospheric pressure. The resulting catalyst was washed with water (300 ml) at pH 8 and dried at 110

The catalyst (25 cm3, 10,45 g) experience in the oxidation of propylene with oxygen in the reactor with downward flow. When tested under pressure and 20-fold regeneration of the catalyst remained active. After using three samples of the catalyst is analyzed by NAA method; samples taken from different points of the catalyst layer (the top point at the entrance to the reactor, as shown in Table 20.

As can be seen from Table 20, the catalyst maintains a stable structure after 20 cycles, regardless of the position in the catalyst bed.

During the first ten cycles the catalyst is used at different temperatures, flow rates and pressures and regenerate at 350-400oC. Then the catalyst was tested for ten cycles at 120oWith according to the following scheme regeneration and testing. The catalyst is blown ABOUT2(7%) in helium to the disappearance of propylene in the mass spectrum. Consumption is 2000 cm3/min at a pressure of 1379 kPa (200 psi). Water (0,44%) served in the flow of the pump. The catalyst is heated in a mixture of oxygen (7%), water (0,44%) and helium up to 400oWith approximately 28 minutes (at a speed of approximately 600oWith/hour), aged at 400oWith 30 minutes, then cooled as quickly as possible to 1203/min at a pressure of 1379 kPa (200 psi). Next, the flow is replaced by a mixture of propylene (30%), oxygen (7%), hydrogen (7%) and helium (the rest). The sample for gas chromatography are selected on the "peak" of obtaining propylene oxide (about 5 min after the filing of the H2and after 60 minutes, and at night for some cases of regenerations. During all test cycles the catalyst retains activity and selectivity, which is confirmed by the data of Table 21 for cycles 11-20.

1. The method of producing olefination, including the contacting of the olefin having at least three carbon atoms with oxygen in the presence of hydrogen, and optional diluent and in the presence of a catalyst containing gold, at least one promoting metal selected from the group consisting of metals of Group 1, Group 2, rare earth lanthanoide actinoid metals and metals of the Periodic Table of Elements, and such media, and the contacting is carried out at a temperature higher than the 20oC and lower than 250oC.

2. The method according to p. 1 where the olefin is a C3-12olefin.

3. The method according to p. 2, where the olefin is a propylene.

Divinylbenzene, allylchloride, allyl alcohol, dialiawah simple ether, allylation ether, allylmalonate ZIOC scientists allylbenzene, allylanisole simple ether, arylpropionic simple ether and allylanisole.

5. The method according to p. 1 where the olefin is used in quantities of more than 1 mol. % and less than 99 mol. % relative to the amount of moles of olefin, oxygen, hydrogen, and optional diluent.

6. The method according to p. 1, where the oxygen is used in the amount of more than 0.01 mol. % and less than 30 mol. % relative to the amount of moles of olefin, oxygen, hydrogen, and optional diluent.

7. Way but p. 1, where the hydrogen is used in the amount of more than 0.01 mol. % and less than 50 mol. % relative to the amount of moles of olefin, oxygen, hydrogen, and optional diluent.

8. The method according to p. 1, in which use thinner.

9. The method according to p. 8, where the method is carried out in the vapor phase, the diluent is chosen from helium, nitrogen, argon, methane, carbon dioxide, water vapor and mixtures thereof; and when the method is carried out in the liquid phase, the diluent is chosen from chlorinated benzenes,1-10aliphatic alcohols, chlorinated WITH1-10alkanols and liquid polyether, police is. % and less than 90 mol. % relative to the amount of moles of olefin, oxygen, hydrogen, and optional diluent.

11. The method according to p. 1, where gold has an average particle size or more.

12. The method according to p. 11, where the average particle size of gold is higher than and less than

13. The method according to p. 1 where the gold is loaded onto the carrier in the amount of more than 0.01 wt. % and less than 20 wt. %.

14. The method according to p. 1, where the promoting metal selected from the group consisting of metals of Group 1, Group 2, lanthanoid rare-earth metals, actinoid metals and mixtures thereof.

15. The method according to p. 1, where the promoting metal selected from the group consisting of potassium, rubidium, cesium, magnesium, calcium, barium, erbium, lutetium, and mixtures thereof.

16. The method according to p. 1, where the promoting metal is loaded on the carrier when the load is higher than about 0.01 wt. % and less than about 20 wt. % relative to the weight of the catalyst.

17. The method according to p. 1, where the titanium is in the form of titanium dioxide or titanium dioxide deposited on silicon dioxide.

18. The method according to p. 17, where titanium dioxide is an anatase or rutile.

19. The method according to p. 1, where the titanium is in the form of titanosilicate.

20. Spotsa microporous or mesoporous titanosilicates, having pores in the range of

22. The method according to p. 21, where titanosilicate is a TS-1, TS-2, Ti-beta, Ti-ZSM-12, Ti-ZSM-48 or Ti-MCM-41.

23. The method according to p. 1, where the titanium is in the form of a mixture of titanium dioxide and porous titanosilicate.

24. The method according to p. 1, where the titanium is in the form of titanosilicate essentially free of titanium dioxide.

25. The method according to p. 24, where, as determined by the method of Raman spectroscopy, titanosilicate essentially free from crystalline titanium dioxide, so that the spectrum of the Raman media essentially shows no peaks at about 147 cm-1, 155 cm-1, 448 cm-1and 612 cm-1.

26. The method according to p. 1, where the titanium is in the form of titanate promoting metal.

27. The method according to p. 26 titanate promoting metal is a magnesium titanate, calcium titanate, barium titanate, strontium titanate, sodium titanate, potassium titanate, erbium titanate, titanate lutetium, titanate thorium or uranium titanate.

28. The method according to p. 1, where the titanium is in the form of titanium dispersed on silica.

29. The method according to p. 28, where the titanium dispersed on silica, essentially free from crystalline titanium dioxide, as Eden is where HR-TEM image basically shows the crystallographic plane separated by about or around

31. The method according to p. 28, where the titanium dispersed on silica, essentially free from crystalline titanium dioxide, as identified by the method of Raman spectroscopy.

32. The method according to p. 31, where the spectrum of the Raman essentially shows no peaks at about 147 cm-1, 155 cm-1, 448 cm-1and 612 cm-1.

33. The method according to p. 28, where identified as diffuse reflection in the ultraviolet - visible parts of the spectrum (UV-VIS DRS) titanium is in the disordered phase.

34. The method according to p. 33, where the UV-VIS DRS spectrum of the fresh catalyst shows the band at 310 nm or lower wavelengths.

35. The method according to p. 29 or 31, as identified by x-ray absorption spectroscopy at near-edge structure K-edge titanium (Ti K-edge XANES) titanium is in the disordered phase.

36. The method according to p. 35, where in the XANES spectrum of the Ti K-edge measured relative to the internal metal titanium standard, for which the zero energy is set at 4966,0 eV, essentially there is only one peak at +4.6 eV to 1.2 eV.

37. The method according to p. 1, where the titanium is in the form of titanium dispersed on silica promos titanium dioxide, the titanosilicates, titanate metal promoters, titanium dispersed on silica, and titanium dispersed on silicates of metals promoters.

39. The method according to p. 1, where the method is carried out at a temperature higher than the 20oC and lower than 250oC.

40. The method according to p. 1, where the method is carried out at a pressure from atmospheric to 2758 kPa (400 psig).

41. The method according to p. 1, where the method is carried out in gas phase at an average hourly rate of gas supply of the olefin of more than 1000 h-1and less than 20000 h-1.

42. The method according to p. 1, where the method is carried out in the liquid phase at an average hourly feed rate of the raw material olefin is more than 0.1 h-1and less than 20 h-1.

43. The method according to p. 1, where the reactor is selected from a reactor with a moving layer, moving bed, fluidized bed, continuous flow type, periodic actions layer with jet stream of fluid, casing and tubular and swing type.

44. The method according to p. 1, where the conversion of the olefin is more than 0.2 mol. % and the selectivity for refinanced is more than 90 mol. %

45. The method of obtaining propylene oxide, comprising contacting propylene with oxygen in the gas phase in prismera particles of at least one promoting metal, selected from metals of Group 1, Group 2, the rare earth lanthanides and actinoid metals of the Periodic Table, such media; and the contacting is carried out at a temperature higher than the 20oWith and lower than 250oC.

46. The method according to p. 45, where the propylene is more than 20 mol. % and less than 70 mol. %.

47. The method according to p. 45, where the amount of oxygen is more than 0.01 mol. % and less than 20 mol. % relative to the amount of moles of propylene, oxygen, hydrogen, and optional diluent.

48. The method according to p. 45, where the amount of hydrogen is more than 0.01 mol. % and less than 50 mol. % relative to the amount of moles of propylene, oxygen, hydrogen, and optional diluent.

49. The method according to p. 45, where the amount of diluent is more than 15 mol. % and less than 70 mol. % relative to the amount of moles of propylene, oxygen, hydrogen, and optional diluent.

50. The method according to p. 45, where the conversion of propylene is more than 0.2 mol. % and the selectivity for propylene oxide is more than 90 mol. %.

51. Catalyst composition containing gold, at least one promoting metal selected from the group consisting of metals of Group 1, Group 2, rare-earth loslave, that the composition does not include palladium and provided that the composition does not contain gold titanates promoting metals Group 2.

52. The composition according to p. 51, where the gold is present as particles having an average size of from or more than before or less.

53. The composition according to p. 51, where gold is present in the amount of more than 0.01% wt. and less than 20% wt.

54. The composition according to p. 51, where the promoting metal is potassium, rubidium, cesium, magnesium, calcium, barium, erbium, lutetium, or mixtures thereof.

55. The composition according to p. 51, where the titanium is in the form of titanium dioxide or titanium dioxide deposited on silicon dioxide.

56. The composition according to p. 55, where the titanium dioxide is in the form of anatase.

57. The composition according to p. 51, where the titanium is in the form of titanosilicate.

58. The composition but p. 57, where titanosilicate is a porous titanosilicate having a pore size

59. The composition according to p. 58, where the porous titanosilicate is a TS-1, TS-2, Ti-beta, Ti-ZSM-12, Ti-ZSM-48 or Ti-MCM-41.

60. The composition according to p. 57, where titanosilicate essentially free of titanium dioxide.

61. The composition according to p. 60, where titanosilicate essentially free from crystalline titanium dioxide, as determined by spectral analysis of the Raman sci-1.

62. The composition according to p. 51, where the titanium is in the form of titanium dispersed on silica.

63. The composition according to p. 62, where, as identified by transmission electron microscopy, high-resolution (HR), titanium dispersed on silica, essentially free of crystalline titanium dioxide.

64. The composition according to p. 63, where the HR-TEM image basically shows the crystallographic plane, separated by about or around

65. The composition according to p. 62, where, as determined by Raman spectroscopy, titanium dispersed on silica, essentially free of crystalline titanium dioxide.

66. The composition according to p. 65, where in the spectrum of the Raman media essentially no peaks at about 147 cm-1, 155 cm-1, 448 cm-1and 612 cm-1.

67. The composition according to p. 62, where, as defined by the diffuse reflection in the ultraviolet - visible parts of the spectrum (UV-VIS DRS), titanium is in the disordered phase.

68. The composition according to p. 67, where the UV-VIS DRS spectrum of the fresh catalyst shows the band at 310 nm or lower wavelengths.

69. The composition according to p. 63 and 65, where the disordered phase identified by x-ray absorption spectrum of the Ti K-edge, measured with respect to the inner metal titanium standard, for which the zero energy is set when 4966,0 eV, there is essentially a single peak at +4.6 eV to 1.2 eV.

71. The composition according to p. 51, which does not contain a metal of Group VIII.

72. The composition according to p. 51, obtained by the process comprising (a) contacting such media with a solution of the compound of gold and a solution of at least one salt of the promoting metal, where the promoting metal selected from Group 1, Group 2, rare earth lanthanoid and actinoid metals of the Periodic Table of Elements, and the contacting is carried out at a temperature in the range from 20 to 80oC, then (b) adjusting the pH of the resulting mixture in the range of from 5 to 11, to obtain a composite gold-promoting metal carrier, (C) optionally washing of the composite is not more than 100 ml of wash liquid per gram of the composite and (d) calcination of the composite in air or in a reducing atmosphere, or heating in an inert atmosphere at a temperature of from 250 to 800oC.

73. The regeneration method of composition p. 51, comprising heating the deactivated catalyst at temperatures in the range from 15 the gas.

74. The way the regeneration of p. 73, where the concentration of hydrogen and/or oxygen in the regeneration gas is changed from 2 to 100 mol. %.

75. The way the regeneration of p. 73, where the regeneration gas, water is added.

76. The regeneration method of composition p. 51, comprising heating the deactivated catalyst at a temperature of from 150 to 500oIn the presence of water.

77. The method according to p. 1 or the composition according to p. 51, which used only one promoting metal in the amount of more than 0.1 wt. % relative to the total weight of the catalytic composition.

78. The method according to p. 1 or the composition according to p. 51, where the promoting metal(s) contains sodium in an amount of more than 0.1 wt. % relative to the total weight of the catalytic composition.

Priority points and features:

01.07.1996 - PP. 1-78;

11.07.1996 - PP. 1-78 (varieties of signs);

20.09.1996 - PP. 1-78 (varieties of signs).

 

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