Method of producing olefin oxide, method of using olefin oxide and catalytic composition

FIELD: chemistry.

SUBSTANCE: present invention relates to methods of producing a catalytic composition, to the method of producing olefin oxide and method of producing 1,2-diol or 1.2-diol ether. Described is a method of producing a catalytic composition, involving deposition of silver on a carrier and deposition of a promoter - alkali metal on the carrier. The alkali metal contains potassium in amount of at least 10 mcmol/g and lithium in amount of at least 1 mcmol/g in terms of mass of catalytic composition. The alkali metal is deposited on the carrier before depositing silver, at the same time or after depositing silver on the carrier. Described is a method of producing a catalytic composition, involving use of potassium as a promoter in amount of at least 10 mcmol/g and sodium in amount of at least 5 mcmol/g in terms of mass of the catalytic composition. Description is given of a method of producing olefin oxide by reacting olefin, which has at least three carbon atoms, with oxygen in the presence of a catalytic composition, obtained using the method described above. This invention also pertains to the method of producing 1,2-diol or 1,2-diol ether using olefin oxide, obtained using the said method.

EFFECT: increased selectivity and stability of the catalytic composition.

20 cl, 5 tbl, 37 ex

The technical field to which the invention relates.

The invention relates to a method of producing refinanced interaction of the olefin having at least three carbon atoms with oxygen in the presence of a catalytic composition containing silver and promoter deposited on the carrier. The invention also relates to a method of applying such refinanced to obtain 1,2-diol and ester 1,2-diol. In addition, this invention relates to a catalytic composition containing silver and promoter deposited on the carrier.

Background of invention

The olefins can be oxidized to the corresponding refinanced direct oxidation using molecular oxygen as oxidant. The catalysts used in the oxidation, contain silver as a catalytically active metal supported on a carrier. Most of these catalysts contains a porous inert support or carrier, such as alpha-alumina, which caused silver and promoters.

In the oxidation of olefins characteristics of the catalyst can be estimated on the basis of selectivity, activity and stability. Selectivity represents the percentage of olefin in the flow of power, giving the desired refinanced. During aging of the catalyst interest to icesto the reacted olefin is usually reduced, and to maintain a constant level of gain refinanced the reaction temperature is increased. However, this adversely affects the selectivity of transformation to the desired refinanced. Since the reactor equipment can withstand temperatures only up to a certain level, it is necessary to stop the reaction when the temperature reaches an unacceptable level. Thus, the longer the selectivity can be maintained at a high level and the oxidation can be carried out at an acceptable temperature, the longer the catalyst loading can be contained in the reactor and the more product is obtained. Relatively small improvements in the preservation of selectivity for long periods of time potentially give great gains in the efficiency of the method.

Many studies have been done to improve and optimise the performance of the catalyst in the oxidation of ethylene on industrial installations for the production of ethylene oxide. However, so far not found commercially reasonable manner similar to the direct oxidation mostly higher olefins, in particular propylene.

US-A-3962136 considers the use of catalytic compositions for the oxidation of ethylene to ethylene oxide, where the catalytic composition consists essentially of silver and certain amounts of alkali metal deposited on newpenny media.

US-A-4833261 considers the method of producing ethylene oxide by the interaction of ethylene with oxygen-containing gas in the presence of a catalytic composition containing silver, the promoter is an alkali metal and the promoter is rhenium deposited on a refractory carrier. The alkali metal is preferably potassium, rubidium or cesium or mixtures thereof. Contains a long list of combinations of alkali metals.

US-A-4168247 considers the use in the oxidation of olefins catalyst, which contains a promoting amount of sodium together with at least one of potassium, rubidium or cesium.

US-A-5625084 and US-A-5770746 consider the direct oxidation of propylene to propylene oxide in the presence of a catalyst containing silver deposited on a carbonate of alkaline earth metal and containing a potassium salt with potassium cation and nitrogen oxyanions or her predecessor. In addition, the catalyst may contain a promoting amount of a molybdenum promoter. In these documents there are no descriptions regarding alkali metal other than potassium.

US-A-5698719 considers the oxidation of propylene using a catalyst containing silver, deposited on calcium carbonate, and, in addition, containing potassium nitrate.

US-A-5387751 considers the direct oxidation of olefins, such as ethylene and propylene, in the presence of sulfur is dosoderzhashchego catalyst and in the presence of nitrate or nitridebased substances. In the long list of preferred options identified elements that may be present in the catalyst. The list contains alkali metals, alkaline earth metals and transition metals.

According to US-A-5770746 and US-A-5625084 it is known that catalysts and reaction conditions that are best suited for obtaining ethylene oxide, do not give comparable results in the direct oxidation of higher olefins such as propylene. According to US-A-5698719 problem with the catalytic oxidation of propylene in the vapor phase with molecular oxygen in comparison with the oxidation of ethylene is usually poor selectivity achieved at an acceptable level of transformation.

Thus, it is known that catalysts and reaction conditions that are most suitable for obtaining ethylene oxide, often do not give comparable results in the direct oxidation of higher olefins such as propylene. Thus, it would be most desirable to create methods for producing propylene oxide by direct oxidation in the vapor phase with a higher yield and selectivity than is achievable at the present time.

Refinanced are valuable starting materials for producing 1,2-diols or ester of 1,2-diols. In many cases, refinanced have properties that make them less suitable for transportation over long distances. This is ricine transportation olefination often avoid by turning olefination immediately after their receipt in the corresponding 1,2-diols or esters of 1,2-diols, which are better suited for transportation.

Brief description of the invention

The present invention provides a catalytic composition comprising silver, the promoter is an alkali metal and a carrier, in which the promoter is an alkali metal contains potassium in an amount not less than 5 mmol/g with respect to the weight of the catalytic composition, and not less than 10 mmol/g of an alkali metal selected from the group consisting of lithium and sodium and mixtures thereof.

The present invention also encompasses a method of producing refinanced, including the interaction of the olefin having at least three carbon atoms with oxygen in the presence of a catalytic composition containing silver, the promoter is an alkali metal and a carrier, in which the promoter is an alkali metal contains potassium in an amount not less than 5 mmol/g with respect to the weight of the catalytic composition, and not less than 1 mmol/g of an alkali metal selected from the group consisting of lithium and sodium and mixtures thereof.

Also provided are a method for producing 1,2-diol or ether 1,2-diol, where the method comprises the transformation of refinanced in 1,2-diol or ether 1,2-diol, in which refinanced get in the way described above.

Detailed description of the invention

In accordance with this invention in the oxidation of higher olefins with oxygen improved characteristic is erotici catalyst can be achieved using a silver catalyst on the carrier, which additionally contains some combination of the promoters of the type of alkali metal. This, in particular, occurs when the oxidation is carried out in the additional presence of nitrate or nitridebased substances. The term "improved performance of the catalyst" means that there is an improvement, at least one of the properties of the catalyst (catalysts) include the catalytic activity, selectivity, characteristic changes in activity or selectivity in time, efficiency (i.e. resistance to off), the degree of transformation and performance. Therefore, the present invention provides a method of producing refinanced, which includes the interaction of the olefin having at least three carbon atoms with oxygen in the presence of a catalytic composition containing silver, the promoter is an alkali metal and a carrier, in which the promoter is an alkali metal contains potassium and advanced lithium or sodium.

The present invention also provides a method for producing 1,2-diol or ether 1,2-diol, including the transformation of refinanced in the corresponding 1,2-diol or ether 1,2-diol, in which refinanced get method according to this invention.

The material of the catalyst carrier can be any material suitable for the application is utilizator and having the necessary physical and chemical properties, to withstand a chemical process such as oxidation. For example, carriers may be selected from materials based on carbon, magnesium oxide, zirconium dioxide, preparation of (fuller's earth, diatomaceous earth, and synthetic and natural zeolites. Preferred media contain carbonate of alkaline earth metal, particularly magnesium carbonate, and especially calcium carbonate. Other preferred carriers are alumina, silica, titanium dioxide)-containing compounds, and combinations thereof, such as alumina-silica-containing compounds, in particular, alpha alumina-containing compounds.

Typically, the carrier is a porous carrier, preferably having a specific surface area of 0.01 m²/g to 50 m²/g, more preferably 0.03 to 40 m²/g and, most preferably, from 0.05 m²/g to 30 m²/g as measured by BET method, and an apparent porosity of from 0.05 ml/g to 3 ml/g, preferably 0.07 to 2,50 ml/g and, more preferably, from 0.1 ml/g to 2 ml/g, as determined by the traditional method of water absorption. BET method, as it is here referred to, is described in detail in the work S.Brunauer, P.Y.Emmet and E.Teller, J. Am. Soc., 60, 309-316 (1938).

Of particular interest are alpha-alumina, which have a specific surface area of 0.1 m²/g to 25 m²/g, preferably 0.2 to 15 m²/g and, more preferably, at,3 m ²/g to 10 m²/g as measured by BET method, and which have an apparent porosity of from 0.1 ml/g to 0.6 ml/g and, preferably, from 0.1 ml/g to 0.55 ml/g, as determined by the traditional method of water absorption. Preferably, these alpha-alumina have relatively uniform pore size. Some examples of such alpha-alumina supply company NorPro under the trademark ALUNDUM and firm Südchemie.

Also of particular interest are the carbonates of alkaline earth metals, particularly calcium carbonate and magnesium carbonate, which have a specific surface area of 1 m²/g to 20 m²/g, preferably 2-18 m²/g and, more preferably, from 3 m²/g to 15 m²/g as measured by BET method, and which have an apparent porosity of from 0.05 ml/g to 2 ml/g, preferably 0.07 to 1.7 ml/g and, more preferably, from 0.1 ml/g to 1.5 ml/g, as determined by the traditional method of water absorption. The media containing carbonate of alkaline earth metal, are of particular interest, as they provide catalysts which have improved the characteristics of the activity in time. The media containing the carbonate of the alkali earth metal associated with silver is preferred. Associated with silver medium containing a carbonate of alkaline earth metal, characterized by high relative area is updated on the surface and a minimum compressive strength 22 N (5 lb) and contains 80-99 wt.% carbonate of alkaline earth metal and 1-20 wt.% silver, more preferably, 85-97 wt.% carbonate of alkaline earth metal and 3-15 wt.% silver, and most preferably 90-95% wt. carbonate of alkaline earth metal and 5-10 wt.% silver. Associated with silver medium containing a carbonate of alkaline earth metal, can be obtained by blending industrial powder carbonate, alkaline earth metal complex is a silver-oxalylamino having a concentration of silver from 15 to 33 wt.%, preferably, from 27 to 33 wt.%, in such quantities that the final ratio of silver:(a carbonate of alkaline earth metal) is from about 1:5 to 1:100, preferably from 1:6 to 1:30, more preferably from 1:8 to 1:10, for example, 1:9. After mixing the above components in the mixture can be added to organic extrusion additive such as starch, and, optionally, burnable material, so that there is a 90 to 100 mass parts (parts by weight) of calcium carbonate, mixed with 1-2 parts by weight of the extrusion additives. Can then be introduced with sufficient water, usually 35-45 parts by weight of a solution of silver to make the extrudable composition and the resulting composition can be mixed to homogeneity and extraterrest. The paste can then be extruded. One way of extrusion may be pushing the paste through a die plate from 0.5 mm to 5 cm, in castnet is, from 1 mm to 5 mm Extrudate may then be annealed in the temperature range from 180°C to 870°C, in particular from 200°C to 750°C for 1-12 hours the resulting extrudate can also be first dried for a period of time from 1 h to 18 h in the temperature range, for example, from 10°C to 500°C, in particular from 50°C to 200°C., especially from 80°C to 120°C, and then annealed. An example of a program annealing of the catalyst may be the following: 0.1 to 10 h linear change, as, for example, a linear change in the course of 1 h, 200°C to 250°C, holding for 1 h, then 4 h ramp to 500°C. and aging for 5 hours Obtained catalyst carrier has good mechanical properties, in particular, the crushing strength, and is suitable for preparation of catalysts of this invention used for the oxidation of olefins.

Regardless of the material used media, it can be molded into particles, chunks, pieces, etc. Preferably, for use in a tubular reactor with a fixed bed they are formed in a rounded shape, for example, in the form of spheres, pellets, cylinders, rings or tablets, which typically have dimensions in the range from 2 mm to 2 cm, the Term "shaped" ("shaped") is used interchangeably with the term "formed" ("molded").

The amount of silver that can be supported on a carrier, can be vybranou wide limits. A suitable amount of silver is in the range from 0.5 wt.% up to 60 wt.%, preferably, 0.7 to 58 wt.%, and, more preferably, from 1 wt.% up to 55 wt.%, in relation to the weight of the catalytic composition.

In accordance with this invention, the catalyst contains as promoters alkali metals in combination of potassium and sodium or lithium. The combination of potassium and lithium is preferred compared to a combination of potassium and sodium. However, more preferred is a combination of potassium with lithium and sodium. Other alkali metals may be present or may not be present. Unexpectedly it was found that the additional presence of rubidium or, especially, cesium is useful. Acceptable combinations are the following: potassium, lithium and rubidium, potassium, sodium and rubidium, potassium, lithium and cesium, potassium, sodium and cesium, potassium, lithium, sodium, and rubidium, potassium, lithium, sodium, rubidium and cesium, and, in particular, potassium, lithium, sodium, and cesium.

The amount of potassium is usually not less than 5 mmol/g, preferably not less than 10 μmol/g, and typically, the largest 10 mmol/g or may be the biggest 1 mmol/g with respect to the weight of the catalytic composition. If the carrier is alpha-alumina, preferably, the amount of potassium is not less than 5 mmol/g, preferably not less than 10 μmol/g, and no matter what my big 0.5 mmol/g, preferably, the biggest of 0.2 mmol/g, in the same respect. If the carrier is a carbonate of alkaline earth metal, usually calcium carbonate, preferably, the amount of potassium is not less than 10 μmol/g, in particular not less than 50 μmol/g, and the largest independently 10 mmol/g, in particular, the largest 5 mmol/g, in the same respect.

The total amount of sodium and lithium is usually not less than 1 µmol/g and usually the largest 10 mmol/g with respect to the weight of the catalytic composition. If the carrier is alpha-alumina, preferably, the total amount of sodium and lithium is not less than 1 mmol/g, more preferably not less than 5 mmol/g, and the largest independently of 0.5 mmol/g, more preferably, at most 0.1 mmol/g, in the same respect. If the carrier is a carbonate of alkaline earth metal, usually calcium carbonate or magnesium, preferably, the total amount of sodium and lithium is not less than 5 mmol/g, particularly not less than 10 μmol/g, and the largest independently 10 mmol/g, in particular, the largest 5 mmol/g, in the same respect.

If sodium and literaturae promoters both are applied to the medium, the molar ratio of sodium:lithium is usually in the range from 0.01 to 100, more usually in the range of from 0.1 to 10.

The total number of rubidium and cesium is usually not less than the 0.01 µmol/g and usually the biggest 1 mmol/g with respect to the weight of the catalytic composition. If the carrier is alpha-alumina, preferably, the total number of rubidium is not less than 0.01 μmol/g, in particular not less than 0.1 mmol/g, and the largest independently of 0.1 mmol/g, in particular, the biggest of 0.05 mmol/g, in the same respect. If the carrier is a carbonate of alkaline earth metal, usually calcium carbonate, preferably, the total number of rubidium and cesium is not less than 0.1 mmol/g, particularly not less than 1 mmol/g, and the largest independently 1 mmol/g, in particular, the highest at 0.2 mmol/g, in the same respect.

If the rubidium - and cesium-bearing promoters both are applied to the medium, the molar ratio of rubidium:cesium is usually in the range from 0.01 to 100, more usually in the range of from 0.1 to 10.

Specialist in the art will note that the amount of alkali metal promoters, as defined, are not necessarily shared by the quantities of these metals present in the catalytic composition. Number, as defined here, are the quantities that enter in the catalyst, for example, by impregnation with suitable solutions of compounds of alkali metals, such as salts or complexes of alkali metals. These amounts do not include amounts of alkali metals, which are blocked in the media, for example, calcination, or not extracted in suitable Rast is oritel, such as water or a lower alcohol, or amine, or mixtures thereof, and therefore do not provide the promoting activity. Specialist in the art will also note that the media can be a source of alkali metal promoter, which can be used for impregnation of the carrier. I.e., the carrier may contain alkali metals that can be extracted with a suitable solvent, thereby obtaining a sealing solution, from which the alkali metal ions are precipitated or presidida to the media.

The catalysts can be obtained in accordance with methods such as the method known from US-A-3962136 and WO-00/15333.

In a suitable method of producing the catalyst carrier is impregnated with the liquid composition of silver, potassium, sodium and/or lithium and, if desired, other compounds, for example, rubidium and/or cesium, and then dried by heating at a temperature in the range from 150°C to 500°C, preferably from 200°C to 450°C over a period of time from 1 min to 24 h, preferably from 2 minutes to 2 hours, more preferably 2-30 min, in an atmosphere of air, inert gas, such as nitrogen or argon or water vapor. Usually there are the reducing agents to effect the recovery of silver compounds to metallic silver. For example, can be used reducing atmosphere, such as bogorods the holding gas, or the reducing agent may be present in one or more impregnating liquids, for example, the oxalate. If desired, the impregnation time can be carried out in more than one stage of impregnation and drying. For example, the silver impregnation can be carried out in more than one stage, and impregnation by the promoters may be conducted in one or more separate stages before impregnation with silver, after impregnation with silver or between different stages of impregnation of silver. The liquid composition is usually the solution in a more typical case, an aqueous solution. The compounds used for the impregnation, can be independently selected from, for example, inorganic and organic salts, hydroxides and complex compounds. They are used in such quantities that the catalyst is obtained the desired composition.

This invention is used for oxidation of any olefin that has at least three carbon atoms. Typically, the number of carbon atoms is the most 10, more typically no more than 5. Most preferably, the number of carbon atoms is 3.

In addition to the presence of olefinic linkages (i.e. part of the >C=C<), the olefin may contain other olefinic bond or any other type of unsaturation, for example, in the form of aryl groups, e.g. phenyl groups. Thus, the olefin may be sopryazheny is or non-conjugate diene or paired or unpaired vinylaromatic connection, for example, 1,3-butadiene, 1,7-octadiene, styrene or 1, 5cyclooctadiene.

In a preferred embodiment, the olefin contains simple olefinic bond, but other than that he is a saturated hydrocarbon. It can be linear, branched or cyclic. Only an alkyl group can be attached to the olefinic communication as 1-hexene, or two alkyl groups can be attached to olefinic link as 2-methyl-octene-1 or pentene-2. It is also possible that three or four alkyl groups attached to olefinic linkages. Two alkyl groups may be joined together by a chemical bond, so that together with the olefinic bond they form a ring structure, such as in cyclohexane. In these preferred embodiments, the hydrogen atom attached to the olefinic linkages in places that are not busy alkyl group. Particularly preferably, when the olefinic link attached single alkyl group.

The most preferred olefins having at least 3 carbon atoms are 1-penten, 1-butene, and especially propylene.

Specialist in the art will note that in accordance with the geometrical structure of molecules olefin can give a mixture of olefination, for example, refinanced in more than one isomeric form.

Typically, the method of the present invention done by the is as a gas-phase method, which is the way in which gaseous reactants interact under the influence of the solid catalyst. Often the reagents and any other components that are fed into the process, mixed with the formation of the reaction mixture, which then interacts with the catalyst. The ratio between the amounts of reagents and other components, if they exist, and other reaction conditions are not the subject of this invention, and they can be selected within wide limits. So, usually a mixture of interacting with the catalyst, is gaseous, the concentration of quantities of reagents and other components, if any, are defined below as the volume fraction of the mixture in gaseous form.

The concentration of the olefin may in an appropriate case, be not less than 0.1 vol.%, preferably not less than 0.5 vol.%, and concentration may in an appropriate case, to make the most 60 vol.%, preferably, the biggest 50 vol.%. Preferably, the concentration of the olefin is in the range from 1 vol.% up to 40 vol.%. If the olefin is propylene, 1-butene or 1-penten, its concentration preferably is in the range from 1 vol.% up to 30 vol.%, in particular, from 2 vol.% up to 15%vol.

The oxygen concentration may in an appropriate case, be not less than 2 vol.%, usually not less than 4 vol.%, and in practice, the concentration is often the largest 20% vol. preferably, the big 15 vol.%. If the olefin is propylene, 1-butene or 1-penten, preferably, the oxygen concentration is in the range from 6% vol. up to 15 vol.%, preferably, from 8% vol. up to 15 vol.%. The source of oxygen may be air, but is preferably used oxygen-containing gas, which can be obtained by separation from air.

As the regulator of the catalyst, improving the selectivity in the reaction mixture may be introduced organic chloride compounds. Examples of such organic chloride compounds are alkylchloride and alkenylamine. Preferred organic chloride compounds are methyl chloride, vinyl chloride, 1,2-dichloroethane and, especially, ethylchloride. In the case of propylene concentration of organic chloride should be at least 20 hours per million by volume, more preferably not less than 50 hours per million by volume, and concentration may be the biggest 2000 hours/million by volume, in particular, the biggest 1500 hours/million by volume, where h/million by volume calculated as the molar amount of chlorine atoms in the total number of the reaction mixture.

Characteristics of the catalyst can be improved by introducing into the reaction mixture nitrate or nitridebased connection. Nitrate - or nitridebased connection is the connection that is capable in the conditions under which it wsimages is there with catalyst, enter on the catalyst nitrate or nitrite ions. Usually nitrate or nitrite ions have a tendency to disappear from the catalyst during the process, in this case, they must be replenished. As a result, preferably the nitrate - or nitridebased compound in the reaction mixture is continuously or periodically, at least at times, when the need arises. For the initial stage of the method can be simply enter the nitrate - or nitridebased connection or nitrate or nitrite ions in the catalyst at the stage of preparation of the catalyst. The preferred nitrate or nitridebased compounds are nitric oxide, nitrogen dioxide and/or dinitrogen tetroxide. Alternatively, it may be hydrazine, hydroxylamine, ammonia, nitromethane, nitropropane or other nitrogen-containing compounds. Preferably there is used a mixture of nitrogen oxides, which may be referred to the General formula NO_xin which x is a number in the range from 1 to 2, expressing srednemotornoy atomic ratio of oxygen and nitrogen to nitrogen oxides in the mixture.

For the oxidation of propylene nitrate or nitridebased the connection may in an appropriate case, be used in a concentration of at least 10 hours per million by volume, typically at least 50 hours per million by volume, and concentration may be eligible with the my big 500 hours per million by volume, in particular, the largest 300 hours per million by volume. If the catalyst used for the oxidation of propylene, there is rubidium and/or cesium nitrate or nitridebased compound preferably used in a concentration of at least 10 hours per million by volume, in particular at least 20 hours per million by volume, and the concentration is usually the largest 200 hours per million by volume, more typically no more than 150 hours per million by volume, preferably not more than 80 hours per million by volume, in particular, not more than 50 hours per million by volume, in the same respect.

Carbon dioxide may be present or not be present in the mixture. Carbon dioxide can reduce the activity and selectivity of the catalyst and, thus, the output of refinanced. Carbon dioxide may typically be present in the largest concentration of 35 vol.%, in particular, the largest 20%vol.

In addition, in the mixture can be inert compounds, for example, nitrogen or argon. In a separate embodiment of the present invention, it is preferable to have the methane present in the mixture, as methane can improve the heat dissipation of the reaction without detrimental effect on the selectivity and conversion.

The method can preferably be carried out at a temperature of not lower than 150°C., in particular above 120°C. Preferably, the temperature is the biggest 320°C., more preferably is, the largest 300°C. the Method can preferably be carried out at a pressure of not less than 50 kPa (0.5 brisb (i.e. bar overpressure)), more preferably not less than 100 kPa (1 brisb). Preferably, the pressure is the greatest 10 MPa (100 brisb), more preferably, at most 5 MPa (50 brisb).

In the General case, it is preferable to operate at high oxygen concentrations. However, in practice, in order to stay out of the ignition of the mixture of reagents and any other components present in it, the oxygen concentration should be reduced as the concentration of the olefin increases. The actual safe working conditions vary along with the composition of the gas from the individual installation conditions, such as temperature and pressure.

When implementing the method in the form of a gas-phase process using a reactor with a fixed layer of the hourly average gas flow rate SSPG (GHSV) may preferably be not less than 1000 N./(l·h), in particular at least 2000 N./(l·h). SCSP may, preferably, be the biggest 15000 N./(l·h), in particular, the biggest 10000 N./(l·h). The term "SSPG" ("GHSV") represents the hourly average gas flow rate, which is the volumetric flow rate of the injected gas, which here is defined in normal conditions (i.e. the ri 0°C and an absolute pressure of 1 bar), divided by the volume of the catalyst layer.

The product of the method of the present invention is refinanced you can turn or not to turn in the corresponding 1,2-diol or a simple ester 1,2-diol. Transformation into a 1,2-diol or ethers, 1,2-diol may include, for example, the interaction of refinanced with water using a suitable acid or alkaline catalyst. For example, to obtain predominantly 1,2-diol, and not esters 1,2-diol, refinanced can interact with a tenfold excess of water in the liquid-phase reaction in the presence of an acid catalyst, for example, 0.5 to 1.0 wt.% sulphuric acid relative to the total reaction mixture, at a temperature of 50-70°C at 100 kPa (1 bar absolute) or in gas-phase reactions in 130-240°C and 2-4 MPa (20-40 bar), preferably in the absence of catalyst. If the proportion of water decreases, the proportion of esters 1,2-diol in the reaction mixture increases. Thus obtained esters of 1,2-diol can be fluids, triavir, tetraethyl and subsequent esters. Alternatively, the esters of 1,2-diol can be obtained by transformation of refinanced with alcohol, in particular, a primary alcohol, such as methanol or ethanol, with the substitution of at least part of the water with alcohol.

1,2-diols and ethers, 1,2-diol can be used in a wide range of industrial applications, e.g. in the areas of food, beverages, tobacco, cosmetics, thermoplastic polymers, cured polymer systems, detergents, coolants, etc.

If not otherwise specified, low molecular weight organic compounds mentioned herein are in an appropriate case, the largest 20 carbon atoms, typically the most 10 carbon atoms, in a more typical case, most 6 carbon atoms. It is assumed that organic compounds are compounds that contain carbon atoms and hydrogen atoms in their molecules. As defined here, the intervals for numbers of carbon atoms (i.e. carbon numbers include the numbers for certain limits of the intervals. The number of carbon atoms, as defined here, includes the carbon atoms are all carbon main chain, and the carbon atoms of the ramifications, if any are available.

The invention will now be illustrated by the following non-limiting examples.

An example of a

Getting cerebrovasculature mother liquor

Cerebrohepatorenal mother liquor receive the following procedure: 415 g of sodium hydroxide reactive varieties dissolved in 2340 ml deionized water, and the temperature is brought to 50°C. 1699 g of silver nitrate high purity "Spectropure" dissolved in 2100 ml of deionized water, and the temperature is brought to 50°C. a Solution of hydro is sid sodium is added slowly to the silver nitrate solution with stirring while maintaining the solution temperature of 50°C. This mixture is stirred for 15 minutes, then reduce the temperature to 40°C. Remove the water from the sludge formed during mixing, and measuring the conductivity of the water which contains sodium ions and nitrate. To a solution of silver again add fresh deionized water in an amount equal to the remote number. The solution is stirred for 15 min at 40°C. the Procedure is repeated up until the conductivity of the remote water will not be less than 90 µs/see Then add 1500 ml of fresh deionized water.

Portions of approximately 100 g add 630 g of dihydrate of oxalic acid of high purity. The temperature of the support at 40°C, and the pH is maintained at the level above 7.8. Remove the water from this mixture, so it is very concentrated silver-containing suspension. A slurry of silver oxalate is cooled to 30°C. Then, 699 g of 92 wt.% Ethylenediamine (8% deionized water) is injected into the slurry while maintaining the temperature below 30°C. the resulting solution contains approximately 27-33 wt.% silver.

The example In

Callicarpenal media used in the catalysts of this invention, was prepared as follows: 100 parts by weight (parts by weight) of calcium carbonate is mixed with 2 parts by weight of organic extrusion additives, such as starch. Add 45 parts by weight of a solution of silver obtained as showing the but in example a, and the resulting composition mixed to homogeneity and extraterrest. The resulting paste is forced through a 3 mm die plate. The resulting extrudate is dried until the morning at 110°C and then annealed as follows: for 5 h linear rise of temperature up to 500°C and holding for 5 hours

Examples 1-18

(Examples 1-16 - for comparison; examples 17 and 18 in accordance with this invention)

The catalysts obtained by impregnation of the pores of the molded porous media, which is alpha-alumina, obtained from the firm of Norton Chemical Process Products Corporation, which has a surface area by BET method 0.8 m²/g and an apparent porosity or water absorption of 0.4 ml/year Impregnation spend a single stage impregnation using solutions obtained from silver nitrate and nitrates or hydroxides of alkali metals, with the application of the method known from US-A-4833261, illustrative option 1. Impregnated alpha-alumina is dried and heated at 250°C for 5 min. Workpiece is crushed and sieved to a particle size of 12-20 mesh. The content of silver is 14 wt.% in relation to the weight of the catalytic composition, the content of alkali metals indicated in table I.

Samples (5 g) thus obtained particles 12-20 mesh loaded into a microreactor for the characterization of the catalyst in the oxidation of propylene. Conditions the experience is of amenta are as follows. The composition of the injected gas (power): 8% vol. oxygen, 5% vol. propylene, 100 parts by weight of/million NO_x, 150 parts by weight per million of ethylchloride, relative to the total volume or weight, respectively, of gas. The rest of the gaseous feed is nitrogen. The gas is fed at 9 N./H. the Temperature indicated in table I, the pressure is 350 kPa (3.5 brisb).

Results characterization of the catalyst, namely, selectivity and operating speed, at the time when the stable selectivity shown in table I. the Selectivity is expressed as mol.% the obtained propylene oxide with respect to spent propylene. Operating speed is the speed of obtaining propylene oxide per unit mass of catalyst (kg/(kg·h)).

In table I the results show that all alkali metals, with the exception of potassium, an adverse effect on the selectivity and/or operating speed of the catalyst as compared with the case where the alkali metal is not introduced (compare examples 3, 4 and 10-15 with examples 1 and 2). The positive effect of potassium is useful for all tested concentrations (compare example 1 with examples 5-9). However, it is seen that higher concentrations of 18 µmol/g potassium does not provide any additional improvement of the characteristics of the catalyst (compare examples 7 and 9 with example 6) Add 13 µmol/g of cesium to 18 µmol/g of potassium does not improve the characteristics of the catalyst (compare example 16 example 6).

In example 17 according to the present invention can be seen that the improved performance of the catalyst can be achieved with the introduction of lithium and potassium, even when the concentration of potassium, when additional improvements can be seen with the introduction of larger quantities of potassium (compare example 17 example 7). In example 18 (according to the present invention) can see the same effects for the introduction of sodium and potassium (compare example 18 with examples 6 and 7).

Examples 19-22

(examples 19 and 20 for comparison; examples 21 and 22 according to the present invention)

Repeat the techniques described for examples 1-18, with the following differences:

alpha-alumina has a surface area by BET method 2.0 m²/g instead of 0.8 m²/g and a water absorption of 0.4 ml/g;

before impregnation, the carrier is washed by immersing the carrier into three servings of boiling deionized water (300 g per 100 g of carrier) in each portion 15 min followed by drying in an oven with ventilation at 150°C for 18 h;

the amount of silver is 24 wt.% instead of 12 wt.% in relation to the weight of the catalytic composition;

half the silver is introduced into the carrier by a separate impregnation stage, prior to impregnation with the rest of the silver and alkali metal;

in the microreactor instead of samples of 5 g load samples 10 g; and

- gas supply function is 12% vol. oxygen and 8% vol. propylene instead of 8% vol. and 5 vol.%, respectively.

Details of the experimental conditions and the results of the characterization of the catalyst are given in table II.

In examples 21 and 22 according to the present invention can be seen that the improved performance of the catalyst can be obtained by adding lithium and sodium to potassium even when the concentration of potassium, when additional improvements can be seen with the introduction of larger quantities of potassium (compare with examples 19 and 20).

Examples 23-28 (according to the invention)

Repeat the techniques described for examples 1-18, with the following differences:

alpha-alumina has a surface area by BET method 2.0 m²/g instead of 0.8 m²/g and an apparent porosity of 0.4 ml/g, a water absorption;

before impregnation, the carrier is washed by immersing the carrier into three servings of boiling deionized water (300 g per 100 g of carrier) in each portion 15 min followed by drying in an oven with ventilation at 150°C for 18 h;

the amount of silver is 23 wt.% instead of 12 wt.% in relation to the weight of the catalytic composition;

half the silver is introduced into the carrier by a separate impregnation stage, prior to impregnation with the rest of the silver and alkali metal;

in the microreactor instead of samples of 5 g load samples of 15 g; and

- razoobrazny the e food contains 12% vol. oxygen and 8% vol. propylene instead of 8% vol. and 5 vol.%, respectively.

Details of the experimental conditions and the results of the characterization of the catalyst are given in table III.

In examples 24, 25, 27 and 28 according to the present invention can be seen that the improved performance of the catalyst can be obtained by adding rubidium or cesium to potassium, lithium and sodium (compare with examples 23 and 26 according to the invention). The improvement may be in selectivity and/or operating speed.

Examples 29 and 30

(example 29 for comparison; example 30 according to the present invention )

Repeat the techniques described for examples 1-18, with the difference that the characteristics of the catalyst are determined during a 10-day period of time.

Details of experimental conditions and results are given in table IV.

When comparing example 30 according to the invention from example 29 can be seen that for a long period of time characteristics of the catalyst according to the invention are more stable than the comparative catalyst.

Examples 31-37

(examples 31-34 - for comparison; examples 35-37 according to the present invention)

Repeat the techniques described for examples 1-18, with the following differences:

porous carrier is calcium carbonate;

- Koli is estvo silver introduced in the media, is 26 wt.% instead of 12 wt.% in relation to the weight of the catalytic composition;

half the silver is introduced into the carrier by a separate impregnation stage, prior to impregnation with the rest of the silver and alkali metal;

in the microreactor instead of samples of 5 g load catalyst samples of different weights; and

- gas supply contains 12% vol. oxygen and 8% vol. propylene instead of 8% vol. and 5 vol.%, accordingly, unless otherwise indicated.

Details of the experimental conditions and the results of the characterization of the catalyst, namely, selectivity and operating speed, time after 2 days of testing are given in table V.

In examples 35-37 according to the present invention can be seen that the improved performance of the catalyst can be obtained by adding lithium and sodium to potassium even when the concentration of potassium, when additional improvements can be seen with the introduction of larger quantities of potassium (compare with examples 31-34).

This application provides a detailed description of private variants of the present invention, as described above. It is clear that all the equivalent features are intended to be included in the contents of this patent of invention.

1. The method for the catalytic composition, including:
besieged is e silver on the carrier and
the deposition promoter is an alkali metal on a carrier,
with the indicated promoter - alkali metal contains potassium in the amount of at least 10 μmol/g per weight of the catalytic composition, and lithium in the amount of at least 1 μmol/g per weight of the catalytic composition, and the promoter is an alkali metal precipitated on the carrier before the deposition of silver on the carrier simultaneously with the deposition of silver on the carrier or after the deposition of silver on the carrier.

2. The method according to claim 1, in which potassium is precipitated in the amount of at least 32 µmol/g per weight of the catalytic composition.

3. The method according to claim 1, in which lithium is precipitated in the amount of at least 5 μmol/g per weight of the catalytic composition.

4. The method according to claim 1 which further includes the deposition of sodium in the amount of at least 5 μmol/g per weight of the catalytic composition, prior to the deposition of silver, simultaneously with the deposition of silver or after deposition of silver on the carrier.

5. The method according to claim 4, in which the lithium and sodium is precipitated on the carrier in a molar ratio in the range from 0.01 to 100.

6. The method according to claim 4, in which the lithium and sodium is precipitated on the carrier in a molar ratio in the range from 0.1 to 10.

7. The method according to claim 1, wherein the medium contains alpha-alumina having a specific surface area is in BET from 0.1 to 25 m ²/g and an apparent porosity as measured by the absorption of water, from 0.1 to 1.2 ml/year

8. The method according to claim 1, in which the carrier has associated with silver calcium carbonate, having a compressive strength of at least 22 N.

9. The method according to claim 1, in which the carrier has associated with silver calcium carbonate, in which the mass ratio of silver: the calcium carbonate is from 1:5 to 1:100.

10. The method according to claim 1, in which the carrier has associated with silver calcium carbonate, specific surface area which is from 1 to 20 m²/year

11. The method according to claim 1, in which the carrier has associated with silver calcium carbonate, apparent porosity which ranges from 0.05 to 2 ml/year

12. The method according to claim 1, wherein the medium contains at least 95% alpha-alumina.

13. The method for the catalytic composition, including:
deposition of silver on the carrier and
the deposition promoter is an alkali metal on a carrier,
with the indicated promoter - alkali metal contains potassium in the amount of at least 10 μmol/g per weight of the catalytic composition, and sodium in the amount of at least 5 μmol/g per weight of the catalytic composition, and the promoter is an alkali metal precipitated on the carrier before the deposition of silver on the carrier simultaneously with the deposition of silver on the carrier or the settlement of the e deposition of silver on the carrier.

14. The method according to item 13, in which the precipitated sodium in the amount of at least 10 μmol/g per weight of the catalytic composition.

15. The method according to item 13, in which the precipitated sodium in the amount of at least 32 µmol/g per weight of the catalytic composition.

16. The method according to item 15, in which potassium is precipitated in the amount of at least 32 µmol/g per weight of the catalytic composition.

17. The method of producing refinanced, which includes the interaction of the olefin having at least 3 carbon atoms with oxygen in the presence of a catalytic composition obtained by a method including:
deposition of silver on the carrier and
the deposition promoter is an alkali metal on a carrier,
with the indicated promoter - alkali metal contains potassium in the amount of at least 10 μmol/g per weight of the catalytic composition, and lithium in the amount of at least 1 μmol/g per weight of the catalytic composition, and the promoter is an alkali metal precipitated on the carrier before the deposition of silver on the carrier simultaneously with the deposition of silver on the carrier or after the deposition of silver on the carrier.

18. The method according to 17, which, in addition, is carried out in the presence of nitrate or nitridebased connection.

19. The method according to 17, in which the olefin comprises propylene.

20. The way polucheniya,2-diol or a simple ester 1,2-diol, including
getting refinanced, which includes the interaction of the olefin having at least 3 carbon atoms, by reaction with oxygen in the presence of a catalytic composition obtained by a method including:
deposition of silver on the carrier and
the deposition promoter is an alkali metal on a carrier,
with the indicated promoter - alkali metal contains potassium in the amount of at least 10 μmol/g per weight of the catalytic composition, and lithium in the amount of at least 1 μmol/g per weight of the catalytic composition, and the promoter is an alkali metal precipitated on the carrier before the deposition of silver on the carrier simultaneously with the deposition of silver on the carrier or after the deposition of silver on the carrier and
turning refinanced in 1,2-diol or a simple ester 1,2-diol.