Method of making catalyst support

FIELD: chemistry.

SUBSTANCE: present invention relates to catalysts supports which are used as supports for metal and metal oxide components of catalysts used in different chemical reactions. The invention describes a catalyst support precursor which contains a mixture of alpha aluminium oxide and/or transition aluminium oxide; binder; and a solid sponging agent which expands or releases gas when sufficient heat is supplied. A method of making a catalyst support is described, which involves preparation of the catalyst support precursor described above and water, moulding the obtained precursor into a structure, heating the said structure for a sufficient time and at temperature sufficient for formation of a porous structure as a result of the effect of the sponging agent, and then heating the porous structure for a sufficient time and at temperature sufficient for melting of the porous structure, thereby forming a porous catalyst support. A catalyst preparation method is described, which involves the above described steps for making a porous catalyst support and depositing a catalytically effective amount of silver onto the surface of the support. Described also is a catalyst made using the method described above and a method for oxidising ethylene in the presence of the said catalyst. Described also are catalyst support precursors which contain alpha aluminium oxide and/or transition aluminium oxide, binder, a sponging agent and/or talc or a water-soluble titanium compound, and methods of making the said precursors.

EFFECT: increased bearing strength of the carrier, optimum surface area and porosity, which eliminates diffusion resistance for reagents and gaseous products under reaction conditions.

33 cl, 1 tbl, 14 ex

The technical field to which the invention relates

This invention relates to a carrier of catalysts that are used as carriers of metal and metaloxide components of catalysts used in various chemical reactions. More specifically, the invention relates to a method for producing a catalyst having a carrier of alpha alumina with a low surface area, which is used as a carrier for silver, and the use of such a catalyst in chemical reactions, in particular for the epoxidation of ethylene to ethylene oxide.

Description of the prior art

It is well known that aluminum oxide is used as catalyst carrier for epoxidation of olefins. It in particular is used as a catalyst carrier, including silver, which is used for oxidation of ethylene to ethylene oxide. The material of the carrier is produced by fusing alumina of high purity silicon dioxide or without silicon dioxide. Therefore, the material of the carrier often includes 90 percent or more by weight of alpha alumina and to 6 percent by weight of silicon dioxide. They usually have a high porosity and a high or low surface area, depending on their intended use.

In the known methods projectors, the manufacture of the carrier alpha alumina and/or a transition alumina (precursor of alpha alumina) are thoroughly mixed with temporary and permanent binder. Temporary binder to hold together the components of the precursor of the carrier during processing. Permanent binders which impart mechanical strength to the finished media are inorganic materials having a melting point lower than that of alumina, and cause melting at the contact points of the particles of aluminum oxide. After thorough dry mixing add to the bulk of sufficient water to convert the mass into a paste-like substance. Then the particles of the catalyst carrier is formed by conventional methods such as extrusion at high pressure, tableting, granulation or other methods of forming ceramics. Then the particles are dried and then fired at an elevated temperature.

At the stage of firing temporary binder burn out or thermally decompose to carbon dioxide and water and evaporated. In engineering it is known that catalysts based on ceramic carriers include inert solid carriers, such as alpha alumina. Such media are described in U.S. Patents 3664970; 3804781; 4428863 and 4874739. The U.S. patents which describe the preparation of native aluminum oxide include U.S. Patents 2499675; 2950169 and 3172866. In other patents, such as U.S. Patents 3222129; 3223483 and 3226191, disclosed the preparation of active alumina. Methods of obtaining highly porous aluminum oxides is disclosed in U.S. Patent 3804781; 3856708; 3907512 and 3907982. The native oxide of aluminum with high thermal stability is discussed in U.S. Patents 3987155; 3997476; 4001144; 4022715; 4039481; 4098874 and 4242233. In U.S. Patent 3664970 disclosed media containing mainly aluminum oxide, but which also contains silicon dioxide, magnesium oxide and titanium dioxide. In U.S. Patent 4410453 revealed that the characteristics of the catalyst of silver on aluminum oxide for the oxidation of ethylene to ethylene oxide improves by including oxide or a precursor of zinc oxide, lanthanum, and magnesium. In U.S. Patent 4200552 revealed to the media, which is obtained from α-aluminum oxide and at least one of the compounds SiO₂, TiO₂, ZrO₂, CaO, MgO, B₂O₃, MnO₂or Cr₂O₃as sintering additives. In U.S. Patent 4455392 describes the composition of the carrier of aluminum oxide, which as components of the binder material contains silicon dioxide and magnesium oxide. In U.S. Patent 5100859 disclosed to the media that contains silicate alkaline earth metal, which can be added as a source component or formed in situ by reacting silicon dioxide or compounds forming silicon dioxide, compounds which decompose to the oxide of the alkali earth metal when heated. In U.S. Patent 5512530 describes a method for catalyst carrier, to the which is based on a mixture of alpha alumina, burnt material and titanium dioxide. In U.S. Patent 5380697 disclosed media containing ceramic bundle, which includes 60 wt.% silicon dioxide, 29 wt.% aluminum oxide, 3 wt.% of calcium oxide, 2% of magnesium oxide, 4 wt.% oxides of alkali metals and less than 1 wt.% each of the iron oxide and titanium dioxide. In U.S. Patent 5733840 and U.S. Patent 5929259 described modification of the forming carriers of titanium dioxide. Treatment consisted of impregnating a pre-formed carrier with a solution of oxalate of Titania, bis(ammoniacal)dihydroxide titanium(IV), or a similar organic salts, and then the impregnated carrier was progulivali at a temperature of from about 450 to 700°C. In the patents were disclosed, that if titanium dioxide is added during preparation of media, it can affect the seal structure of the media, which can lead to unacceptable properties. In U.S. Patent 4368144 indicated that improved catalytic characteristics are obtained from the media that contain not more than 0,07% Na. In U.S. Patent 6103916 revealed that the characteristics of the catalyst was improved when the carrier was washed by boiling in clean water until the resistivity of the water was not more than 10000 Ohm·see

One of the problems characteristic of the catalysts deposited on the porous media, is the fact they are not a homogeneous pore structure. In U.S. Patent 4022715 trying to solve the problem by using an organic solution of a pore-forming substance is mixed with the composition of the precursor medium. Now discovered that improved pore structure of the carrier can be formed by using a precursor catalyst carrier which comprises a mixture of alpha alumina and/or a transition alumina; a binder; and or solid pore-forming substance which expands, or allocates gas under the application of sufficient heat, talc and/or water-soluble compounds of titanium. The carrier of the catalyst of this invention has excellent crushing strength, porosity and surface area. The optimal porosity ensures the absence of diffusion braking for the reactants and gaseous products under the reaction conditions. The minimum surface area is important because it provides the structure on which the catalytic component will be applied. The crushing strength is a parameter of the physical integrity of the media. This mechanical strength is important from the point of view of the ability of the catalyst to withstand the operation of loading and unloading, as well as its long life in the industrial reactor. It was found that the new pore-forming substances what about in combination with a binder can significantly change the characteristics of the finished media. The carrier, which has an optimum surface area and porosity, may be insufficient crushing strength and Vice versa. The balance between the different physical characteristics of the media is important.

The INVENTION

The invention provides a precursor of the catalyst carrier, which includes a mixture of alpha alumina and/or a transition alumina; binder and solid pore-forming substance which expands or emit gas when the application of sufficient heat.

The invention also provides a method of obtaining a catalyst carrier, which includes:

a) preparation of the precursor of the catalyst carrier, which includes a mixture of alpha alumina and/or a transition alumina; a binder; a solid pore-forming substance which expands or emit gas when the application of sufficient heat, and water; then

b) molding the obtained precursor structure; then

c) heating the specified structure for a sufficient time and at sufficient temperature to cause the formation of a porous structure as a result of a pore-forming substance, and thereafter

d) heating the porous structure for a sufficient time and at sufficient temperature to t the th to fuse the porous structure and thereby to form a porous catalyst carrier.

The invention also provides a method of producing a catalyst, which includes:

a) preparation of the precursor of the catalyst carrier, which includes a mixture of alpha alumina and/or a transition alumina; a binder; a solid pore-forming substance which expands or allocates gas under the application of sufficient heat, and water; then

b) molding the obtained precursor structure; then

c) heating the specified structure for a sufficient time and at sufficient temperature to cause the formation of a porous structure as a result of a pore-forming substance, then

d) heating the porous structure for a sufficient time and at sufficient temperature to fuse the porous structure, thereby to form a porous catalyst carrier; and then

e) applying a catalytically effective amount of silver on the surface of the catalyst carrier.

The invention also provides a precursor of the catalyst carrier, which includes a mixture of alpha alumina and/or a transition alumina; binder and talc.

The invention also provides a method of obtaining a catalyst carrier, which includes:

a) preparation of the precursor of the media was pushing the congestion, which includes a mixture of alpha alumina and/or a transition alumina; a binder; talc and water; then

b) molding the obtained precursor structure; then

c) heating the specified structure for a sufficient time and at sufficient temperature for the formation of porous structure, and thereafter

d) heating the porous structure for a sufficient time and at sufficient temperature to fuse the porous structure and thereby to form a porous catalyst carrier.

The invention also provides a precursor of the catalyst carrier, which includes a mixture of alpha alumina and/or a transition alumina; binder and water-soluble compounds of titanium.

The invention also provides a method of obtaining a catalyst carrier, which includes:

a) preparation of the precursor of the catalyst carrier, which includes a mixture of alpha alumina and/or a transition alumina; a binder; a water-soluble compounds of titanium and water;

b) molding the obtained precursor structure; then

c) heating the specified structure for a sufficient time and at sufficient temperature for the formation of porous structure, and thereafter

d) heating the porous structure is sufficient time and at sufficient temperature, to fuse the porous structure and thereby to form a porous catalyst carrier.

DETAILED description of the INVENTION

In one embodiment of the invention, the precursor of the catalyst carrier is prepared by obtaining a physical mixture of alpha alumina and/or a transition alumina; binder and solid pore-forming substance which expands or emit gas when the application of sufficient heat. The precursor may include alumina, such as alpha-alumina and/or a transition alumina. The preferred media is prepared from particles of alpha-alumina. The transition aluminium oxide may include aluminum hydroxide such as gibbsite, boehmite, diaspore, Beherit and combinations thereof. Alpha alumina and/or a transition alumina can be present in an amount of about from 80 mass % to 100 mass % of the mass of the finished media. Preferably, it is present in the amount from about 90 mass % to 99 mass % of the mass of the finished carrier, more preferably from about 97 mass % to 99 mass percent by weight of the finished media.

The precursor further includes a binder, which may be a temporary binder, a permanent binder or both. Temporary binders are the cat the key degradable organic compounds, having a medium to high molecular weight. Permanent binders are inorganic materials such as clays, which give mechanical strength to the finished media.

Temporary binder and consumable materials include polyolefin oxides, oils, such as mineral oil, gum, carbon materials such as coke, carbon powder, graphite, cellulose, substituted cellulose, such as methylcellulose, ethylcellulose and karboksimetilcelljuloza, esters of cellulose, stearates, such as the stearates of complex organic esters, for example methyl or telstart, waxes, powdered plastics, such as polyolefins, in particular polyethylene and polypropylene, polystyrene, polycarbonate, sawdust, starch, and flour from the crushed shells of nuts such as shell pecans, cashews, walnuts and hazelnuts, and other similar materials that burn when used temperatures burning. Burnt material are mainly used in order to ensure the safety of patterns in the stages prior to the firing, which mixture may be attached to the particle shape by molding or extrusion, and also to provide the desired porosity of the finished product. In the case of a temporary binder is almost completely removed during firing with getting ready media. For about the especiany preservation of the porous structure after firing media preferably, the carriers of the invention produced with the inclusion of the material of the permanent binder. Permanent binders include inorganic materials such as clay, silica, silicon dioxide with a compound of alkali metal silicates of elements of Group II of the Periodic table of elements and combinations thereof. Suitable clays include, without limitation kaolinite. Handy binder material which can be entered with particles of aluminum oxide is a mixture of boehmite, stable Sol of silicon dioxide and soluble salts of sodium. A binder may be present in the precursor in an amount of about from 0.1 mass % to 15 mass % of the mass of the precursor, preferably approximately from 0.2 mass % to 10 mass % of the mass of the precursor, and more preferably approximately from 0.5 mass % to 5 mass % of the mass of the precursor.

Predecessor, in addition, includes a solid pore-forming substance which expands or emit gas for the purpose of sufficient heat. In one embodiment, a pore-forming substance comprises a composition of the microspheres, which include thermoplastic membranes that encapsulate hydrocarbons. Hydrocarbon extends thermoplastic shell while making a sufficient amount of heat. Such a pore-forming substances is and include gas-tight thermoplastic shell, which can encapsulate the hydrocarbon in liquid form. When heated hydrocarbon passes into the gaseous state, and increases its pressure, at the same time, thermoplastic shell softens, resulting in increased volume of the microspheres. Examples are able to expand the microspheres are Advancell, areas on the basis of Acrylonitrile, manufactured by Sekisui Chemical Co. (Osaka, Japan), and microspheres Expancel.RTM., manufactured by Expancel, Stockviksverken, Sweden. The Expancel microspheres are available in the form of pressurewise and expanding forms. Pressurewise microspheres have a diameter from about 6 to 40 μs, depending on the brand. When heated, these microspheres are expanded from about 20 to 150 microns in diameter. The preferred hydrocarbon inside the shell is isobutane or isopentane. Preferably, the shell was a copolymer of monomers, such as vinylidenechloride, Acrylonitrile, and methyl methacrylate. In another embodiment, a pore-forming substance may be a solid granular chemical pore-forming agent which decomposes when heated, releasing a significant amount of gaseous products of decomposition, leading to the formation of pores. Preferably, the chemical pore-forming substances were solid form hydrazine derivatives, which will be visvobodit the gases such as CO ₂and nitrogen. Examples of chemical pore-forming substances are p-toluensulfonate, benzosulfimide and azodicarbonamide, H₂NCO-N=N-CONH₂. Azodicarbonamide decomposes at 200°C in N₂, CO and CO₂.

A suitable amount of a pore-forming substance to provide the desired porosity may be in the range from about 0.1 mass % to 30 mass % of the total weight of the precursor. Preferably, the amount of pore-forming substances were in the range from about 1 mass % to 20 mass %, and more preferably from about 3 mass % to 15 mass percent by weight of the precursor. The amount of pore-forming substance depends on its type, the type components of alpha alumina and/or a transition alumina, and the nature of porosity, which should characterize the finished product.

After thorough dry mixing of material from alpha alumina and/or a transition alumina, a binder and a pore-forming substance to the mass of the precursor add sufficient amount of water for the formation of a pasty substance. Water and/or water-containing substance is added to subject the processing of the precursor, to give a mixture of plasticity. The plastic mixture is then formed into rebeau form using standard processing methods ceramics, for example tableting or extrusion. The amount of water added to the precursor medium will depend on the method for molding paste. Extrusion may require the addition of large amounts of water to achieve the optimal level of plasticity. When the particles formed using extrusion, it may be desirable to introduce traditional excipients used in the extrusion process, such as lubricant, such as petroleum jelly or mineral oil. The lubricant can be present in the precursor in an amount of about from 0.1 mass % to 10 mass percent by weight of the precursor, preferably about from 0.5 mass % to 5 mass % of the mass of the precursor, and more preferably from about 1 mass % to 3 mass % of the mass of the precursor. The number of components used are to some extent interrelated, and they will depend on a number of factors that apply to used equipment. However, these issues are well known to any expert in the field of extrusion of ceramic materials. For preparation of the catalyst carrier usually uses the stage of kneading of the material of the precursor into the desired shape and size. The particles of the catalyst carrier is then formed from the paste by conventional methods, such as, for example, the R, tableting, extrusion at high pressure, granulation or other methods of forming ceramics. When used for industrial preparation of ethylene oxide carriers preferably be molded in the correct form of pellets, spheres, rings, particles, lumps, pieces, forms a type of wagon wheels, cylinders, trilistniku, chetyrehlistnik and other similar forms with a size convenient for use in reactors with a fixed layer. It is desirable that the particles of the medium could have "equivalent diameters in the range from about 3 mm to 20 mm, and preferably in the range from about 4 mm to 12 mm, which are generally aligned with the inner diameter of the tubular reactor, in which is placed the catalyst. "Equivalent diameter" is the diameter of a sphere having the same outer surface (i.e., not taking into account the surface within the pores of the particles) for three-dimensional relationships, as used particles of the medium. The particles are then dried and then calcined at an elevated temperature. Task stage of drying is to remove water from the molded tablets. Molded precursor of the carrier is dried at a temperature of from about 80°C to 150°C for a time sufficient to remove almost all the water. Then extruded material is calcined under conditions sufficient to remove burnt substances, organic the ski binders and for fusing the particles of alpha alumina in the porous solid mass. The carrier is heated at a temperature which is high enough for sintering the particles of aluminum oxide and receiving structure with the physical properties capable of withstanding the impact of the environment in which it is expected the use of media. Firing temperature and duration should be high enough to turn any of the transition alumina to alpha alumina and to initiate melting at the grain boundary. The regulation of the firing process is important to obtain a carrier having an optimal balance between surface area, porosity and strength. Typically, the temperature of annealing is more than 1000°C, preferably in the range from 1150°C to 1600°C. exposure Times when these maximum temperatures are usually in the range of from about 0 hours to 10 hours, preferably from about 0.1 hours to 10 hours, preferably about from 0.2 hours to 5 hours to form the carrier.

The finished carrier has a volume of aqueous pores in the range of from about 0.2 cm³/g to 0.8 cm³/g, preferably from about 0.25 cm³/g to 0.6 cm³/, it is Preferable that the area of the surface of the medium, measured by BET, was in the range of 0.4-4.0 m²/g, more preferably from about 0.6 to 1.5 m²/, a Suitable value of strength p is sdavlivaya value is about 8 pounds or more, and preferably about 10 pounds or more.

In another embodiment of the invention, the precursor of the catalyst carrier receives the same way as described above except that the mixture comprises the above-described alpha alumina and/or a transition alumina and in similar quantities and talc, instead of or in addition to the component of the permanent binder. Talc may be present in the precursor in an amount of about from 0.1 mass % to 15 mass % of the mass of the precursor, preferably about from 0.5 mass % to 10 mass % of the mass of the precursor, and more preferably from about 1 mass % to 8 mass % of the mass of the precursor. The media is then formed in a manner analogous to that described above.

In another embodiment of the invention, the precursor of the catalyst carrier receives the same way as described above except that the mixture comprises the above-described alpha alumina and/or a transition alumina and in similar quantities and a water-soluble compound of titanium instead of or in addition to the component of the permanent binder. Suitable water-soluble titanium compounds include, without limitation, the oxalate of Titania and bis(ammoniacal)dihydroxide titanium(IV). Water-soluble compound of titanium may be present in the precursor in which Alceste approximately from 0.01 mass % to 10 mass percent by weight of the precursor, preferably from about 0.1 mass % to 8 mass percent by weight of the precursor, and more preferably about from 0.2 mass % to 5 mass percent by weight of the precursor. The media is then formed in a manner analogous to that described above.

In order to obtain a catalyst for oxidation of ethylene to ethylene oxide, formed above the carrier and then put a catalytically effective amount of silver. The catalysts obtained by impregnation of native silver ions, compounds, complexes and/or salts dissolved in a sufficient degree in a suitable solvent for application predecessor of silver compounds to the media. Impregnated carrier is then removed from the solution and deposited compound of silver reduced to metallic silver by firing at high temperature. It is also preferred that the carrier caused or to the deposition of the silver, or simultaneously with the application of silver, or after application of silver corresponding promoters in the form of ions, compounds and/or salts of an alkali metal dissolved in a suitable solvent. Also applied to the media or to the deposition of the silver and/or alkali metal, or simultaneously with applying silver and/or alkali metal, or after applying silver and/or alkali metal suitably the compound of the transition metal, complexes and/or salts dissolved in an appropriate solvent.

Formed above the media impregnorium using impregnation of silver solution, preferably an aqueous solution of silver. The media also impregnorium at the same time or at separate stages of various catalyst promoters. Preferred catalysts prepared in accordance with the invention contain up to about 45% by weight of silver calculated on a metal deposited on the surface and in the pores of porous media. Preferred are silver content, in terms of the metal, from about 1 to 40% of the total weight of the catalyst, while the silver content of from about 8 to 35% are more preferred. The amount of silver supported on a carrier or present on the media, is that amount which is catalytically effective amount of silver, that is the amount that is cost-effectively catalyzes the reaction of ethylene and oxygen with the receipt of ethylene oxide. Used herein, the term "catalytically effective amount of silver," signifies the amount of silver, which provides a significant conversion of ethylene and oxygen to ethylene oxide and the constancy of the selectivity and activity over the lifetime of the catalyst. Suitable connections, sod is readie silver, include, without limitation, the oxalate of silver, silver nitrate, silver oxide, silver carbonate, silver carboxylate, silver citrate, phthalate, silver, silver lactate, propionate, silver butyrate and silver salts of higher fatty acids, and combinations thereof.

This catalyst comprises a catalytically effective amount of silver, a promoting amount of alkali metal, a promoting amount of a transition metal deposited on a porous carrier. Used herein, the term "promoting amount" of a particular component of the catalyst means amount of this component, which effectively provides an improvement of one or more of the catalytic properties of this catalyst compared to a catalyst not containing the specified component. Accurate used concentration, of course, will depend, among other factors, the desired silver content, the nature of the medium, the viscosity of the liquid and the solubility of silver compounds.

In addition to the silver catalyst also contains the promoter of an alkali metal selected from lithium, sodium, potassium, rubidium, cesium or combinations thereof, and cesium is preferred. The amount of alkali metal deposited on a carrier or a catalyst, or is present on the carrier or the catalyst should be promoting. Suppose the equipment, to this number was in the range of from about 10 ppm (parts per million) up to 3000 ppm, more preferably from about 50 ppm to 2000 ppm, and more preferably from about 100 ppm to 1500 ppm, and even more preferably from about 200 ppm to 1000 ppm of the total weight of the catalyst, calculated on the metal.

Preferably, the catalyst also contained the promoter of the transition metal, which includes an element from Groups 4b, 5b, 6b, 7b and 8 of the Periodic table of elements and combinations thereof. Preferably, the transition metal included an element selected from the Group 6b, and 7b of the Periodic table of elements. Preferred transition metals are rhenium, molybdenum and tungsten, and molybdenum and rhenium are preferred. The amount of the promoter of the transition metal supported on a carrier or catalyst or present on the carrier or the catalyst should be promoting. The promoter of the transition metal may be present in amounts of from about 0.1 micromol per gram to 10 micromol per gram, preferably from about 0.2 micromol per gram to 5 micromol per gram, and more preferably from about 0.5 micromol per gram to 4 micromol per gram of total catalyst, calculated on the metal.

The silver solution used for impregna the Finance media may also include an optional solvent or complexing/solubilizing substance known in the art. To solubilize the silver to the desired concentration in the impregnating medium may be used in a variety of solvents or complexing/solubilizing substances. Suitable complexing/solubilizing substances include amines, ammonia or lactic acid. Amines include alkylenediamine and alkanolamine having from 1 to 5 carbon atoms. In one preferred embodiment, the solution includes an aqueous solution of silver oxalate and ethylene diamine. Complexing/solubilizing substance may be present in the impregnating solution in an amount of about from 0.1 to 5.0 moles of Ethylenediamine per mole of silver, preferably from about 0.2 to 4.0 moles, and more preferably from about 0.3 to 3.0 moles of Ethylenediamine per mole of silver.

In the case of using the solvent, it can be water-based or organic-based solvent may be polar or almost or completely non-polar. In General, the solvent should be sufficient solutious ability to solubilize the components of the solution. At the same time, it is preferable to select the solvent excluded the presence of neblagopriyatna the impact on solvated promoters or adverse interaction with solvated by the promoters. The salt concentration of silver in the solution is in the range from about 1% by weight up to the maximum attainable solubility when using a specific combination salt/ solubilizers substance. Usually it is very convenient to use solutions of silver salts containing from about 5% to 45% by weight of silver, and are preferred concentration of silver salts from 10 to 35% by mass.

Impregnation of a selected medium is achieved in the usual way using the excess impregnating solution, the source of the moisture, and so forth. Typically, the material of the carrier is placed in a solution of silver up until a sufficient amount of solution is not absorbed by the media. Preferably, the amount of silver solution used for impregnating porous media, not accounted for a greater amount than is necessary to fill the pore volume of the carrier. Containing silver liquid penetrates into the pores of the medium due to absorption, capillary action and/or vacuum. Can be used single impregnation or the number of stages of impregnation, drying or without drying the intermediate product, depending to some extent on the concentration of silver salts in solution. Methods of impregnation are described in U.S. Patents 4761394, 4766105, 4908343, 5057481, 5187140, 5102848, 5011807, 5099041 and 5407888, the content of which is ZV is camping by reference to them. Can be used in previously known methods of the prior application, the joint application and the subsequent application of different promoters.

Examples of catalytic properties include, in particular, performance (resistance to deviation), selectivity, activity, conversion, stability and output. For any specialist in this field it is obvious that one or more of the individual catalytic properties can be enhanced with the help of "promoting amount", while other catalytic properties can be enhanced or may not be reinforced, or can even be lowered. In addition, it is obvious that different catalytic properties can be enhanced at different operating modes. For example, a catalyst having high selectivity under one set of operating modes that can be used at different set of conditions under which the improvement is manifested in the activity, not in selectivity, and to optimize conditions and results with regard to raw material costs, energy costs, the cost of removing the by-product and other similar costs plant producing ethylene oxide, the operator will be specifically to change operating modes to take advantage of the specific catalytic properties even at the expense of other catalytic properties. To skretny the combination of silver, media, promoter of alkaline metal and promoter of the transition metal of the present invention is to provide improvement in one or more catalytic properties compared with the same combination of silver and the media in the absence of promoters, or in the presence of only one promoter.

After impregnating the carrier impregnated connection predecessor of silver and promoters, calcined or activated in the period of time sufficient to recover containing silver component to metallic silver and to remove solvent and evaporation of decomposition products from containing silver media. The firing is performed by heating the impregnated carrier, preferably at a constant rate to a temperature in the range of from about 200°C to 600°C, preferably from about 230°C to 500°C, and more preferably from about 250°C to 450°C when the reaction pressure in the range from 0.5 to 35 bar, in a period of time sufficient for conversion of contained silver in metallic silver and to decompose all or substantially all present the organic materials and remove them in the form of vapor. Usually, the higher the temperature, the shorter the required period of firing. In the technique for thermal processing impregnated media offers a wide range of periods for which rewane, for example, in U.S. Patent 3563914 offers heated for less than 300 seconds, however, in U.S. Patent 3702259 disclosed heating for 2 to 8 hours at a temperature of from 100°C to 375°C for recovery of silver salts in the catalyst; usually for 0.5 to 8 hours, but it is very important that the recovery time corresponds to the temperature, so that was made almost a full recovery of silver salts in a catalytically active metal. For this purpose, can be used with continuous or step-by-step heating.

Impregnated media stand in an atmosphere comprising inert gas and optionally oxygen-containing oxidizing component. In one embodiment, the oxidizing component is present in amount from about 10 ppm to 5% of the volume of gas. For the purposes of this invention, inert gases believe those gases, which practically do not interact with forming the catalyst components under conditions selected for preparation of the catalyst. These gases include nitrogen, argon, krypton, helium, and combinations thereof, with the preferred inert gas is nitrogen. In a preferred embodiment, the atmosphere comprises oxygen-containing oxidizing component is from about 10 ppm to 1% of the volume of gas. In another preferred embodiment, the atmosphere VK is uchet oxygen-containing oxidizing component is from about 50 ppm to 500 ppm by volume of gas.

Obtaining ethylene oxide

Usually used in industry methods of producing ethylene oxide is carried out by continuous contact of oxygen-containing gas with ethylene in the presence of the present catalysts at a temperature in the range of from about 180°C to 330°C, and preferably from about 200°C to 325°C, more preferably from about 210°C to 270°C at a pressure which may vary from about atmospheric pressure to 30 atmospheres, depending on the mass velocity and the desired performance. However, within the scope of the invention can be used in higher pressure. The time of stay in industrial reactors typically comprise about 0.1 - 5 seconds. Oxygen may be fed to the reaction in the form of oxygen-containing stream such as air or commercial oxygen. The resulting ethylene oxide is separated and recovered from the reaction products using traditional methods. However, for this invention the method of producing ethylene oxide provides for recycling the gas, which consists in the recycling of carbon dioxide at normal concentrations, for example about 0.1 to 15 volume percent. The usual method of oxidation of ethylene to ethylene oxide includes a vapor-phase oxidation of ethylene with molecular oxygen in the presence of a catalyst of the invention in a fixed bed tubular react the RA. Traditional industrial reactors fixed bed to obtain ethylene oxide are many long parallel tubes (in a suitable enclosure) with an external diameter of approximately from 0.7 to 2.7 inches and an inner diameter of from 0.5 to 2.5 inches and a length of 15-45 feet, filled with a catalyst.

It was demonstrated that the catalysts of the invention are particularly selective catalysts for the oxidation of ethylene with molecular oxygen to ethylene oxide. Conditions for carrying out such oxidation reactions in the presence of catalysts of the present invention approximates the conditions described in the prototype. This applies, for example, for the relevant temperatures, pressures, time stays, diluting materials such as nitrogen, carbon dioxide, steam, argon, methane, the presence or absence of inhibiting substances for regulation of the catalytic activity, such as ethylchloride, 1,2-dichloroethane or vinyl chloride, whether to use the operations of the recycling or the use of a serial conversion in different reactors to increase yields of ethylene oxide, and any other special conditions that may be selected methods for producing ethylene oxide. Molecular oxygen is used as the reagent, can be obtained from the traditional is the R sources. As the oxygen supplied can be used relatively pure oxygen, the flow of concentrated oxygen, including oxygen as a principal component, with smaller amounts of one or more diluents, such as nitrogen, argon and so forth, or another oxygen-containing stream such as air. The use of these catalysts in oxidation reactions of ethylene in no way limited to use in those specific conditions for which it is known that their use is effective.

The resulting ethylene oxide is separated and recovered from the reaction products known and used technique in traditional ways. The application of the silver catalysts of the invention in methods for producing ethylene oxide gives a higher total selectivity of the oxidation of ethylene to ethylene oxide at a given conversion of ethylene, how is this achieved in the case of conventional catalysts.

Upon receipt of ethylene oxide introduced a mixture of reagents may contain from 0.5 to 45% ethylene and from 3 to 15% oxygen, and the balance inert materials, including such substances as nitrogen, carbon dioxide, methane, ethane, argon and other similar inert. In a preferred embodiment, the silver catalysts of the invention, ethylene oxide were obtained when the content of oxygen-containing gas is about 95 or more oxygen. Only a portion of the ethylene is usually reacts per pass on the catalyst, and after separation of the desired product of ethylene oxide and removal of the corresponding purified stream and carbon dioxide to prevent the unregulated accumulation inertol and/or by-products, unreacted materials are returned to the oxidation reactor. Only for purposes of illustration, the following conditions are conditions that are often used in modern industrial reactor plant production of nitric oxide. GHSV - 1500-10000; the inlet Pressure is 150 to 400 lb/in². Supplied raw materials: ethylene 1-40%; O₂3-12%; CO₂0.1 to 40%; ethane 0-3%; argon and/or methane and/or nitrogen; the balance, 0.3 to 20 ppmv total dilution chloropiperonyl retarder; the temperature of the refrigerant - 180-315°C.

The following non-limiting examples serve to illustrate the invention.

EXAMPLE 1

Stage 1 was Thoroughly mixed with the following components:

250 grams of alpha aluminum oxide(I)*

250 grams of alpha aluminum oxide(II)**

15 g of Methocel K15M (methylcellulose)

2 g Gum

28.8 g Expancel

25 g Vaseline oil

8 g of 50% Solution of Ti (in the form of bis-ammoniacontaminated titanium)

20 g of Talc

107 g of Water

* Alpha aluminum oxide(I) is a high-purity alpha alumina which has a surface area according to BET 0.7 m²/g and a sodium content less than 0.3%.

**Alpha alumina(II) is a high-purity alpha alumina, which has a surface area according to BET of 11 m²/g and a sodium content less than 0.15 per cent.

All dry ingredients were mixed together in the mixer for dry bulk materials (US Stoneware Model M93120DC). The dry mixture was transferred into a mixer with large shear forces (Lancaster Model 53 OPO). There it was mixed with water and water soluble components, and mixing was carried out for more than 15 minutes.

Stage 2

The plastic mixture was extrudible in hollow cylinders of size 8 mm Killion extruder (Model 43211 11282).

Stage 3

Molded tablets were dried at 120°C for 3 hours, followed by firing under slow and predetermined program diagram. The firing process included heating unfired ceramics in high temperature oven, using oven monitoring and control (Model 1720). Diagram of the firing included rapid linear increase of temperature at a speed of 4°C/min up to 1275°C. the oven Temperature was maintained at this level for 2 hours and then it was lowered at a speed of 6°C/min. This carrier is designated as carrier A. the Test media has shown that it has the following characteristics:

The crushing strength of 27.6 pounds

Water absorption of 30 ml/100 g

Surface area according to BET of 1.3 m²/g

EXAMPLE 2

Thoroughly mixing the following components:

150 grams of alpha aluminum oxide(I)*

150 grams of alpha aluminum oxide(II)***

9 g CM Methocel (methyl cellulose)

1.2 g Gum

2.9 g of Expancel

7.5 g Graphite

15 g Vaseline oil

4.7 grams of 50% Solution of Ti (in the form of bis-ammoniacontaminated titanium)

0.5 g of Boric acid

20 g of Talc

80 g of Water

* Alpha aluminum Oxide(I) is a high-purity alpha alumina which has a surface area according to BET 0.7 m²/g and a sodium content less than 0.3%.

*** Alpha aluminum Oxide(III) is of high-purity alpha alumina which has a surface area according to BET 9 m²/g and a sodium content less than 0.4%.

Mixing, molding and drying of these components was performed as in example 1.

Diagram of the firing included rapid linear increase in temperature at a rate of 3°C/min to 800°C. the oven Temperature was maintained at this level for 30 minutes. The temperature is again linearly increased at a speed of 4°C/min up to 1325°C. Then the temperature of the furnace was maintained at this level for 2 hours and then lowered at a speed of 5°C/min This carrier is designated as the carrier B. the Test media has shown that it has the following characteristics:

The crushing strength 17,6 1b

Water absorption of 33.8 ml/100 g

Surface area according to BET of 1.13 m²/g

EXAMPLE 3

Thoroughly mixing the following components:

250 grams of alpha aluminum oxide(I)*

250 grams of alpha aluminum oxide(II)**

15 g CM Methocel (methyl cellulose)

2 g Gum

4.8 g Expancel

25 g Vaseline oil

0.85 grams of Boric acid

10 g of Talc

115 g of Water

* Alpha aluminum Oxide(I) is a high-purity alpha alumina which has a surface area according to BET 0.7 m²/g and a sodium content less than 0.3%.

** Alpha alumina(II) is a high-purity alpha alumina which has a surface area according to BET of 11 m²/g and a sodium content less than 0.15 per cent.

Mixing, molding and drying of these components was performed in the same way as in example 1. Molded tablets were dried at 120°C for 3 hours, followed by firing under slow and predetermined program diagram. The firing process included heating unfired ceramics in high temperature oven, using oven monitoring and control (Model 1720). Diagram of the firing included rapid linear increase of temperature at a speed of 4°C/min up to 1275°C. the oven Temperature was maintained at this level for 2 hours and then it was lowered at a speed of 5°C/min This carrier is designated as the carrier C. the Test media has shown that it has the following characteristics:

The crushing strength of 36.6 pounds

Water absorption is 25.3 ml/100 g

Surface area according to BET of 1.33 m²/g

EXAMPLE 4

Thoroughly mixing the following components:

250 g of alpha hydroxy is aluminum(I)*

250 grams of alpha aluminum oxide(II)**

15 g CM Methocel (methyl cellulose)

2 g Gum

4.8 g Expancel

7,8 g 50% Solution of Ti (in the form of bis-ammoniacontaminated titanium)

25 g Vaseline oil

10 g of Talc

107 g of Water

* Alpha aluminum Oxide(I) is a high-purity alpha alumina which has a surface area according to BET 0.7 m²/g and a sodium content less than 0.3%.

** Alpha alumina(II) is a high-purity alpha alumina which has a surface area according to BET of 11 m²/g and a sodium content less than 0.15 per cent.

Mixing, molding, drying and firing of these composites was performed as in example 3. This carrier is designated as the carrier D. the Test media has shown that it has the following characteristics:

The crushing strength of 32.9 pounds

Water absorption 26 ml/100 g

Surface area according to BET of 1.12 m²/g

EXAMPLE 5

Thoroughly mixing the following components:

250 grams of alpha aluminum oxide(I)*

250 grams of alpha aluminum oxide(II)**

of 37.5 g of alumina Sol (20% colloidal alumina in water)

15 g K 15M Methocel (methyl cellulose)

2 g Gum

4.8 g Expancel

25 g Vaseline oil

7,8 g 50% Solution of Ti (in the form of bis-ammoniacontaminated titanium)

10 g of Talc

95 g of Water

Mixing, molding and drying of these components was performed in the same way as in example 1, Scheme firing included rapid linear increase of temperature at a speed of 4°C/min up to 1225°C. The oven temperature was maintained at this level for 2 hours and then lowered at a speed of 5°C/min This carrier is designated as the carrier E. the Test media has shown that it has the following characteristics:

The crushing strength of 30.4 pounds

Water absorption is 27.4 ml/100 g

Surface area in RESPONSE to 1,25 m²/g

EXAMPLE 6

Thoroughly mixing the following components:

250 grams of alpha aluminum oxide(I)*

250 grams of alpha aluminum oxide(II)**

15 g CM Methocel (methyl cellulose)

2 g Gum

25 g of Azodicarbonamide

25 g Vaseline oil

7,8 g 50% Solution of Ti (in the form of bis-ammoniacontaminated titanium)

10 g of Talc

107 g of Water

Mixing, molding, drying and firing of these composites was performed in the same way as in example 1. This carrier is designated as the carrier F. the Test media has shown that it has the following characteristics:

The crushing strength to 30.1 pounds

Water absorption of 29.1 ml/100 g

Surface area according to BET of 1.39 m₂/g

EXAMPLE 7

Stage 1 was Thoroughly mixed with the following components:

225 grams of alpha aluminum oxide(I)*

75 g of alpha alumina(Ii)**

9 g CM Methocel (methyl cellulose)

1.2 g Gum

2.8 g Expancel

15 g Vaseline oil

4.7 grams of 50% Solution of Ti (in the form of bis-ammoniacontaminated titanium)

6 g of Talc

80 g of Water

Mixing, molding and drying e the components was performed in the same way as in example 1. Diagram of the firing included rapid linear increase of temperature at a speed of 4°C/min up to 1225°C. the oven Temperature was maintained at this level for 2 hours and then lowered at a speed of 5°C/min This carrier is designated as the carrier of G. the Test media has shown that it has the following characteristics:

The crushing strength of 41.7 pounds

Water absorption of 27.3 ml/100 g

Surface area by BET 1.35 m²/g

EXAMPLE 8

Stage 1. Thoroughly mixing the following components:

250 grams of alpha aluminum oxide(I)*

250 grams of alpha aluminum oxide(II)**

15 g CM Methocel (methyl cellulose)

2 g Gum

4.8 g Expancel

25 g Vaseline oil

1,25 g Hexaferrite ammonium

10 g of Talc

115 g of Water

Mixing, molding and drying of these components was performed in the same way as in example 1. Diagram of the firing included rapid linear increase of temperature at a speed of 4°C/min up to 1275°C. the oven Temperature was maintained at this level for 2 hours and then lowered at a speed of 5°C/min This carrier is designated as the carrier H. the Test media has shown that it has the following characteristics:

The crushing strength of 22.6 pounds

Water absorption of 29.4 ml/100 g

Surface area by BET 1.15 m²/g

EXAMPLE 9

Stage 1. Thoroughly mixing the following components:

250 grams of alpha aluminum oxide(I)*

25 grams of alpha aluminum oxide(II)**

15 g Kl 5 M Methocel (methyl cellulose)

2 g Gum

25 g of mineral oil

7,8 g 50% Solution of Ti (in the form of bis-ammoniacontaminated titanium)

10 g of Talc

115 g of Water

Mixing, molding and drying of these components was performed in the same way as in example 1. Diagram of the firing included rapid linear increase of temperature at a speed of 4°C/min up to 1375°C. the oven Temperature was maintained at this level for 2 hours and then lowered at a speed of 5°C/min This carrier is designated as the carrier I. the Test media has shown that it has the following characteristics:

The crushing strength of 14.4 pounds

Water absorption of 33.3 ml/100 g

Surface area by BET 0,88 m²/g

EXAMPLE 10

Stage 1. Thoroughly mixing the following components:

176 g of alpha alumina(II)**

232 g of Hydrated alumina (Gibsa)

48 g of Boehmite

12 g CM Methocel (methyl cellulose)

2 g Gum

80 g Azodicarbonamide

25 g of Mineral oil

6.2 g of 50% Solution of Ti (in the form of bis-ammoniacontaminated titanium)

16 g of Talc

108 g of Water

Mixing, molding and drying of these components was performed in the same way as in example 1. Diagram of the firing included rapid linear increase of temperature at a speed of 4°C/min up to 1375°C. the oven Temperature was maintained at this level for 2 hours and then lowered at a speed of 5°C/min, This wear is ü designated as media J. The test media has shown that it has the following characteristics:

The crushing strength of 17.4 pounds

Water absorption of 29.6 ml/100g

Surface area according to BET of 1.03 m²/g

EXAMPLE 11

Stage 1. Thoroughly mixing the following components:

250 grams of alpha aluminum oxide(I)*

250 grams of alpha aluminum oxide(IV)****

15 g of Methocel K15M (methylcellulose)

2 g Gum

4.8 g Expancel

25 g Vaseline oil

24 g 34% Colloidal silicon dioxide, suspended in water

0.84 g of Boric acid

10 g of magnesium Stearate

116 g of Water

**** Alpha aluminum Oxide (IV) is a high-purity alpha alumina which has a surface area according to BET of 14 m²/g and a sodium content less than 0.4%.

Mixing, molding and drying of these components was performed in the same way as in example 1. Diagram of the firing included rapid linear increase of temperature at a speed of 4°C/min to 1450°C. the oven Temperature was maintained at this level for 2 hours and then lowered at a speed of 5°C/min This carrier is designated as medium K. the Test media has shown that it has the following characteristics:

The crushing strength of 36.3 pounds

Water absorption of 25.1 ml/100 g

Surface area by BET 0.89 m²/g

EXAMPLE 12

Stage 1. Thoroughly mixing the following components:

1075 grams of alpha aluminum oxide (I)*

105 g of alpha alumina (IV)****

65 g CM Methocel (methyl cellulose)

9 g Gum

124 g of Expancel

110 g Vaseline oil

3.6 g of Boric acid

43 g of magnesium Stearate

516 g of Water

**** Alpha aluminum Oxide (IV) is a high-purity alpha alumina which has a surface area according to BET of 14 m²/g and a sodium content less than 0.4%.

Mixing, molding and drying of these components was performed in the same way as in example 1. Diagram of the firing included rapid linear increase of temperature at a speed of 4°C/min to 1500°C. the oven Temperature was maintained at this level for 2 hours and then lowered at a speed of 5°C/min Test media showed that he has the following characteristics:

The crushing strength of 16.1 pounds

Water absorption of 42.8 ml/100 g

Surface area by BET 1,32 m²/g

EXAMPLE 13

a. Preparation of the starting solution of the complex silver/amine:

The silver solution was prepared using the following components (parts by weight):

The silver oxide - 834 parts

Oxalic acid - 442 parts

Deionized water - 1180 parts

The Ethylenediamine - 508 parts

The silver oxide was mixed with water at room temperature, and then was gradually added oxalic acid. The mixture was stirred for 15 minutes, and during this time the color black suspension of silver oxide was changed to a light brown color OK the Alata silver. The mixture was filtered and the solids washed with 3 liters of deionized water.

The sample was placed in an ice bath and stirred, and at the same time slowly added Ethylenediamine and water (in the form of a mixture of 66%/34%), in order to maintain the reaction temperature is lower than 33°C. After adding all of the mixture of Ethylenediamine/water solution was filtered at room temperature. Clear filtrate was used as the initial solution of silver/amine for the preparation of the catalyst.

b. Adding promoters:

In order to prepare a catalyst containing 11% silver and the appropriate amount of cesium and sulfur, a transparent original solution was diluted with a mixture of 66/34 the Ethylenediamine/water. In addition, to the diluted solution of silver were added to the hydroxide solution Cs and hydrosulphate of ammonia.

c. Impregnation of the catalyst:

The sample carrier in a quantity of 150 g was placed in a vessel, working under pressure, and then created a vacuum of 50 mm was Introduced into a vessel under vacuum, 200 ml of the adjusted solution of silver/promoters. Brought the pressure in the vessel to atmospheric pressure, and its contents were shaken for several minutes. The catalyst was separated from the solution, and then he was ready for firing.

d. Calcination of the catalyst:

Firing the deposited silver was carried out by heating the catalyst up to tempera is URS decomposition of silver salts. This was achieved by heating in a furnace, which had several heating zones with controlled atmosphere. The catalyst was loaded on a moving conveyor belt, which consisted in a furnace at ambient temperature. The temperature is gradually raised as the catalyst passed from one zone to the next zone. The temperature was increased to 400°C as the catalyst passed through seven heating zones. After heating zones belt conveyor and passed through a cooling zone in which the catalyst is gradually cooled to a temperature lower than 100 °C. the Total time in the furnace was 22 minutes. The atmosphere in the furnace was controlled by means of a stream of nitrogen in the different heating zones.

c. The catalyst test:

The catalyst test was performed in a stainless steel pipe, which was heated in a bath of molten salt. The source gas mixture containing 15% ethylene, 7% oxygen and 78% inert, mainly nitrogen and carbon dioxide, used for testing of the catalyst at a pressure of 300 lb/in². The reaction temperature was regulated so as to obtain the standard performance for ethylene oxide 160 kg per hour per m³catalytic Converter.

EXAMPLE 14

Media A-K used for the preparation of catalysts for the oxidation of ethylene to ethylene oxide by the same method, Kotor is shown in example 13. The results of the testing of the catalysts are shown in table 1.

Although the present invention has been specifically shown and described based on preferred embodiments, for normal specialists in this area it is obvious that various changes and modifications can be made without deviating from the essence and scope of the invention. It is assumed that explain the claims covers disclosed an implementation option, the options that have been discussed above and, in addition, all cash equivalents.

1. The precursor of the catalyst carrier, which contains a mixture of alpha alumina and/or a transition alumina; a binder; and a solid pore-forming substance which expands or emit gas when reviewing a sufficient amount of heat.

2. The precursor according to claim 1, in which a pore-forming substance contains a composition of thermoplastic membranes that encapsulate the hydrocarbon, which extends thermoplastic shell at the end of the residual amount of heat.

3. The precursor according to claim 2, in which the shell contain homopolymers or copolymers comprising a material selected from the group consisting of vinylidenechloride, Acrylonitrile, and methyl methacrylate; and the hydrocarbons include isobutane or isopentane.

4. The precursor according to claim 1, in which a pore-forming substance contains granular pore-forming substance which gives off gas when you draw sufficient heat.

5. The precursor according to claim 4, in which the solid pore-forming substance contains a material selected from the group consisting of p-toluensulfonate, benzosulphochloride, and azodicarbonamide, H₂NCO-N=N-CONH₂and their combinations.

6. The precursor according to claim 1, additionally containing water in an amount sufficient to give the mixture the ability to extrusion.

7. The precursor according to claim 1, in which component of alpha alumina and/or a transition alumina contains one or more alpha alumina, and optionally one or more transition alumina.

8. The precursor according to claim 1, in which component of alpha alumina and/or a transition alumina contains one or more transition alumina, and optionally one or more alpha alumina.

9. The precursor according to claim 1, in which the binder contains a material selected from the group consisting of thermally decomposing organic compounds, clays, silica, silicates of elements of Group II of the Periodic table of elements, and combinations thereof.

10. The precursor of claim 1, wherein the mixture further comprises one or more components selected from the group consisting of talc, water-soluble compounds of titanium, lubricants, consumable material, and combinations thereof.

11. The precursor according to claim 1, in which the binder contains a material selected from the group consisting of oxides of polyolefins, oil, gum, carbon, cellulose, substituted cellulose ether cellulose, stearates, waxes, granular polyolefin, polystyrene, polycarbonate, sawdust, flour from crushed walnut shells, boehmite, silica, sodium, and combinations thereof.

12. The method of receiving the catalyst carrier, including:
a) preparation of the precursor of the catalyst carrier, which contains a mixture of alpha alumina and/or a transition alumina; a binder; a solid pore-forming substance which expands or emit gas when reviewing a sufficient amount of heat; and water; then
b) molding the obtained precursor structure; then
c) heating the specified structure for a sufficient time and at sufficient temperature to cause the formation of porous structure in achiev is Tate actions pore-forming substance, and after that
d) heating the porous structure for a sufficient time and at sufficient temperature to fuse the porous structure, thereby to form a porous catalyst carrier.

13. The method according to item 12, in which a pore-forming substance contains a composition of thermoplastic membranes that encapsulate the hydrocarbon, which extends thermoplastic shell while making a sufficient amount of heat.

14. The method according to item 12, in which a pore-forming substance contains granular pore-forming substance which gives off gas when reviewing a sufficient amount of heat.

15. The method according to 14, in which the solid pore-forming substance contains a material selected from the group consisting of p-toluensulfonate, benzosulphochloride, and azodicarbonamide, H₂NCO-N=N-CONH₂and their combinations.

16. The method according to item 12, in which component of alpha alumina and/or a transition alumina contains one or more alpha alumina, and optionally one or more transition alumina.

17. The method according to item 12, in which the binder contains a material selected from the group consisting of thermally decomposing organic compounds, clays, silica, silicates of elements of Group II of the Periodic table of elements, and combinations

18. The method according to item 12, in which stage C), stage d) or stage) and stage d) is carried out in an atmosphere of inert gas, and, optionally, an oxidizing gas.

19. The method of preparation of the catalyst, including:
a) preparation of the precursor of the catalyst carrier, which contains a mixture of alpha alumina and/or a transition alumina; a binder; a solid pore-forming substance which expands or emit gas for the purpose of sufficient heat, and water; then
b) molding the obtained precursor structure; then
c) heating the specified structure for a sufficient time and at sufficient temperature to cause the formation of a porous structure as a result of a pore-forming substance, and after that
d) heating the porous structure for a sufficient time and at sufficient temperature to fuse the porous structure, thereby to form a porous catalyst carrier; and then
e) applying a catalytically effective amount of silver on the surface of the catalyst carrier.

20. The method according to claim 19, in which a pore-forming substance contains a composition of thermoplastic membranes that encapsulate the hydrocarbon, which extends thermoplastic shell for the purpose of sufficient heat.

21. The method according to A19, in which a pore-forming substance contains granular pore-forming substance which gives off gas when you draw sufficient heat.

22. The method according to item 21, in which the solid pore-forming substance contains a material selected from the group consisting of p-toluensulfonate, benzosulphochloride, and azodicarbonamide, H₂NCO-N=N-CONH₂and their combinations.

23. The method according to claim 19, in which the component of alpha alumina and/or a transition alumina contains one or more alpha alumina, and optionally one or more transition alumina.

24. The method according to claim 19, in which the binder contains a material selected from the group consisting of thermally decomposing organic compounds, clays, silica, silicates of elements of Group II of the Periodic table of elements, and combinations thereof.

25. The method according to claim 19, in which stage C), stage d) or stage) and stage d) is carried out in an atmosphere of inert gas, and optionally, an oxidizing gas.

26. The method according to claim 19, further comprising applying a promoting amount of a promoter to the surface of the catalyst carrier containing one or more compounds containing alkali metal, one or more compounds containing a transition metal, one or more components of sulfur, one or more components containing their fluorine, or combinations thereof.

27. The catalyst for the epoxidation of olefins, obtained by the method according to claim 19.

28. The method of oxidation of ethylene to ethylene oxide, comprising vapor-phase oxidation of ethylene with molecular oxygen in a fixed bed tubular reactor in the presence of a catalyst obtained by the method according to claim 19.

29. The method of oxidation of ethylene to ethylene oxide which comprises vapor-phase oxidation of ethylene with molecular oxygen in a fixed bed tubular reactor in the presence of a catalyst obtained by the method according to p.

30. The precursor of the catalyst carrier, which contains:
(i) alpha alumina and/or a transition alumina;
(ii) a binder;
(iii) a pore-forming substance; and
(iv) talc.

31. The method of receiving the catalyst carrier, including:
a) preparation of the precursor of the catalyst carrier, which includes a mixture of alpha alumina and/or a transition alumina; a binder; a pore-forming agents; talc; water; then
b) molding the obtained precursor structure; then
c) heating the specified structure for a sufficient time and at sufficient temperature for the formation of a porous structure, and then
d) heating the porous structure for a sufficient time and at sufficient temperature to which levity porous structure, and thereby to form a porous catalyst carrier.

32. The precursor of the catalyst carrier, which contains:
(i) alpha alumina and/or a transition alumina;
(ii) a binder;
(iii) a pore-forming substance; and
(iv) a water-soluble compound of titanium.

33. The method of receiving the catalyst carrier, including:
a) preparation of the precursor of the catalyst carrier, which includes a mixture of alpha alumina and/or a transition alumina; a binder; a pore-forming agents; water-soluble compounds of titanium; and water;
b) molding the obtained precursor structure; then
c) heating the specified structure for a sufficient time and at sufficient temperature for the formation of a porous structure, and then
d) heating the porous structure for a sufficient time and at sufficient temperature to fuse the porous structure, thereby to form a porous catalyst carrier.