PL104463B1 - METHOD OF MANUFACTURING A CATALYST INTENDED FOR THE PRODUCTION OF ALKYLENE OXIDES - Google Patents

Description

The invention relates to a manufacturing process catalyst intended for the production process of alkylene oxides by oxidation oxygen of the corresponding alkylene oxide.

Ethylene oxide is usually made from ethylene by its oxidation with oxygen, which may be up to supplied in the form of air. Because part of ethics The flax is oxidized to by-products, which I have carbon oxides and water, it is desirable to the consumption of ethylene for these products was as low as possible s. In other words, change should characterize high selectivity, i.e. high efficiency ethylene oxide. The catalyst for this process was increased do not combine two important features, namely high activity and high selectivity transformations under given conditions.

Typically the catalyst used in the preparation of The alkylene oxide contains silver. Many are known such catalysts. According to the patent description No. 73 51: 2 kiatailiiziafcor contains silver particles of a size dice below 10,000 A, but not present in it promoter. * This catalyst, according to the patent specification vice no. 83 211 can be activated by subjecting it heating for 2 to 24 hours at 175-300 ° C followed by treatment with methanol or ethanol. After ta When treated, the selectivity of the catalyst was up to 76.1% conversion of ethylene oxide. In British in the patent description No. 1321 095 it was discussed the catalyst which is obtained by co-operation no silver carbonate with earth metals kaliiczinych, drying to a powder produced so products and embedding them in that form on a carrier made of aluminum. It says that for Jed One of the catalysts thus prepared was obtained selectivity by ethylene oxide 76.6%. We¬ the debt of the German patent specification No. 1,442,770 carbonate silver is combined with the alkaline earth metal and zinc and / or cadmium from an aqueous solution, a then the product in powder form is introduced on the medium, and according to the British description, the patent No. 1,129,190, silver is inserted on the carrier bro in the form of a powder. According to the patent specification Germany, No. 1767 012, is saturated with the solution silver compound, which is then reduced to silver. The promoter in this catalyst is e.g. lit.

It has now surprisingly been found that by selection of promoter combinations in which lithium does not turn off tapping, you can get a catalyst for the process for the production of alkylene oxide above Including the known catalysts for aces catalytic activity and selectivity of transformation, which catalyzes and in terms of its stability wear for a very long period of use.

According to the invention, the method of producing the catalyst blockage intended for the manufacturing process alkylene oxides by oxidation to the appropriate olefiri with oxygen, consisting in the fact that porous, porous, surface-resistant carrier with a specific properties in the range of 0.04 to 10 m2 / g, which means 1044633 104463 4 the combined method of Brunauer, Emmett and Teller, followed by apparent purity of at least 20%, marked mercury absorption method, and the median diameter ranging from 0.3 to 15 microns, that is mercury porometric method, it saturates a solution of a silver compound that decomposes, wherein the solution is alkaline or contains complexing agent and reducing agent, na¬ the solution is steadily evaporated and decomposed silver on silver, and also in the carrier it is the promoter who is characterized by the fact that I both the activating amount and the promoter are used sci (a) copper, gold, cynic, cadmium, mercury, molifade different. ^ nilrfrtflimii nftarfrymi wapULa, magnesium, strontium '"tKibaitfuJ & A V 4fc © compelling amounts of at least one 3o component from the group (to) of sodium, cesium and rutoid. [ Catalyst produced by a method according to naiaakiy containing as promoters at least one metal of group (a) in combination with at least less one metal from group (b) is particularly not useful because of its high selection activity in the conversion of alkylene to alkyl oxide nu, in particular in the transformation of ethylene in the background ethylene or propylene oxide to propylene oxide.

This is confirmed by the following examples.

By the term "activating amounts" is meant amounts that increase activity or benefit no selectivity of the catalyst at any time during its useful life. Thanks to this se¬ Initial laxity may be higher and / or may be that persist for a longer period.

Under the term "alkaline solution" of the compound Decomposable silver is understood as such solution that was added up to 10 times (by volume) the amount of water makes it alkaline. Solution in addition to a silver compound, which may be an oxide, hydrogen silver oxide or salt, contains a nitrogen base pouring as ligand, e.g. pyridine, acetonitrile, amine ne, especially primary or secondary numbers 1-6 carbon atoms, or more preferably ammonia. In chap thus, silver forms a complex compound you. An aqueous solution containing from 3 to 50% by weight of silver. Reducer component The solution may be an amine capable of heating to reduce the silver compound, or maybe it may be an additional compound, for example, formic acid you, alcohol with 1-6 carbon atoms, multi-alcohol hydro-oxygen, nip. ethylene glycol or culkier, or an aldehyde, e.g. formaldehyde. A preferred compound silver is acetate, oxalate, citrate, lactate, carbonate and nitrate. A silver solution can contain promoters, that is, activating amounts do¬ specified additional catalyst components above, or they may be prepared separately solutions to saturate the carrier before or after saturation with silver.

In the catalyst, the silver may be present in half in an amount of 3-µl2% / o of silver or silver metal by weight, preferably from 6 to 12% by weight bra, preferably at least 80% contiguous to the nose it disappears discontinuously in the form of particles whose Equivalent diameter is less than 10,000 amps Preferably 200-10,000 A, especially 4,000-8,000 A.

The term "equivalent diameter" means that 45 50 55 60 65 it tells the diameter of the sphere of the same grade day as a given particle. Silver tends to be accepted thinking rounded shapes, e.g. the hemisphere of the actual diameter is slightly larger than the diameter equivalent. The size of the silver particles can be determined Clean, for example, a method of examination under an electro microscope new.

Determination of the silver content in the catalyst by specifying the size range of the particles in which should be present in the catalyst, you can za¬ blend with another, e.g. the range of the actual surface silver. However, determining the amount of silver based on 0 its mass contained in particles of a given range size would be less helpful as already several large silver particles present in the catalyst outside of the given size range causes a marked increase in the total mass of silver, influencing while slightly on the property of the catalyst.

The carrier in the catalyst may be carbon monoxide nu, silicon carbide, silicon oxide, zirconium oxide nu or a mixture of silicon oxide with aluminum oxide, but alpha-oxide is considered particularly preferred of aluminum in the form of aggregates in which alpha-alumina particles are sticky, under the influence with heating or with a binder, with frequent with e.g. silicon oxide or barium oxide.

In general, the central pore diameters are at the ridge from 0.5 to 5 microns for the catalyst small steaks, e.g. with an effective diameter of 0.4 to 6 mm, and 2 to 10 microns for the catalyst o larger particles, e.g. with an effective diameter of 2— 8 mm. By "effective diameter" is to be understood the diameter of the sphere with the ratio of the volume to the surface proper as for a given particle. Size distribution the pores can be bimodal (that is, exist I have two groups of pores that differ greatly in size bone). In this case, the larger group had will give pores 0.3-15 microns in diameter, preferably 1-15 microns.

Preferably, it is at least half and na even at least 3/4 of the number of pores are medium ce in the range of 0.3-15, preferably 1-15 microns. The proper volume of pores is favorable is 0.15-0.5 cm3 / g, more preferably 0.17- 0.3 cc / g and the ratio of the median pore diameter to the average diameter of the equivalent particle sre-, bra ranges from 5 to 100, preferably from 10 to 80, particularly rs 15-20.

The catalyst according to the invention contains an active ingredient the amount of alkali metal, especially sodium, half potassium or rubidium, and alkaline earth metal, e.g. strontium, calcium or preferably barium.

Activating amount of alkali metal in general it decreases with increasing its atomic weight and by it is believed that increases with the concentration of strontium, calcium ia and / or a bar. Generally per 1,000 silver atoms There are 10-50,000, preferably 10-5,000 atoms lithium, 1-30,000, preferably 1-5,000, e.g. 10-3,000 or 50-1,000 sodium atoms, 1-5,000, preferably 10-500, especially 20 to 200 potassium atoms, 0.01 to 500 k preferably 0.1-10, especially 1-8 rubidium atoms, 0.01-500, preferably 0.05-6, and lighter 0.5-5 atoms say cesium. The amount of alkali metal used for 1,000 silver atoms are generally the higher the5 higher is the olefin partial pressure which may be, for example, from 0.01 to 15 bar absolute.

Activating amounts of copper, gold, magnesium, zinc, cadmium and / or mercury is 1-500 and more preferably 1 to 100 atoms per 1,000 atoms of silver, and of calcium 5 and / or barium 1-1,000, more preferably 1-400, e.g. 1-200 or from 1 to 100 atoms per 1,000 silver atoms.

Activating amounts of molybdenum, woUfratmiu and chr mu is from 0.001 to 10, preferably from 0.01 to 5, particularly 0.1-2 atoms per 1,000 silver atoms. 10 Silver solution described above until saturation the carrier, as mentioned, may contain a dissolution promoters included therein, or it can also be prepared separate solution, preferably aqueous, promo tracks' to saturate the carrier through or after saturation - 15 with a silver solution. Kind of relationship, i¬ who the promoter is used is of no great importance it, as long as it was well soluble. It could be halides, e.g. chlorides, sulfates, nitrates, nitriles, carboxylates and others. You can also use 20 compounds, which include two promotions rice, e.g., potassium dichromate, as well as compounds complex, especially with amines.

The alkali metal can be introduced into the carrier by saturating it with an aqueous solution as much as possible free of inhibitory anions in which the metal the alkaline was dissolved, for example, as the hydroxide salt, carbonate, bicarbonate, nitrate, nitrite, form tate, acetate, oxalate, citrate or lactate. Mo- There are also other compounds of alkaline mealtails, e.g. chlorides.

Gold and cadmium are very beneficial promoters and bar. The catalyst may include one of these or more, especially bar, e.g. in bar / gold combination or bar / cadmium. When they are introduced into the carrier together with silver, they are preferably used in half salt form converted to oxide or metal under conditions reducing the silver compound to silver. It is therefore mentioned as favorable carboxylates, e.g. acetates, oxalates, lactates, nitrates, nitrites. Gold is preferably added to solution with a solvent no; it may be present in solution as chloride gold (I) as a complex with thioxane. 45 It is advisable that the silver be deposited on the medium in a discontinuous manner, with particles. silver should appear on all available the surface of the carrier, that is, inside the pores as well as on external surfaces. Since 50 the presence of silver and other compositions is more preferred nodes inside the pores of the media to introduce the maximum number of particles there, the medium becomes saturated rather, an amount of solution which will be completely dissolved holy absorption in the carrier, leaving no excess measure. Any excess of this solution should be remove before drying the saturated carrier ka. The silver compound is decomposed by heating saturated carrier at 200-400 ° C, preferably rt 200-350 ° C. 60 A temperature in the range of 200-300 ° C is recommended, when decomposition is carried out in the presence of a strong a reducing component, e.g. hydrogen or ethanol amines; in other cases, for silver salt, ta such as carboxylates, e.g. silver acetate, or salt 65 6 silver in combination with carboxylates of other metals decomposition temperature of 300-350 ° C is recommended.

For the production of ethylene oxide or pro-oxide of polyethylene, which consists in oxidation with oxygen, respectively, ethylene or propylene, is preferable a catalyst according to the invention containing silver introduced into the medium by saturating it with a solution of a silver compound that decomposes under heating, being in solution this includes the complexing agent and the ingredient reducing. In addition, most of the catalyst the silver present adheres to the carrier in particles spaced discreetly with dimensions in diameter below t0,000 A, together with (a) 1 to 100 atoms copper, gold, calcium, magnesium, zinc, cadmium and / or mercury and / or (b) 1 to 200 strontium atoms and / or barium for every 1000 silver atoms.

The components (a) and (b) are present in the carrier in given amounts in excess to possibly ingredients present as carrier contaminants ka or binder. In other words, the stated amounts are composition (a) and (b) do not depend on those, if any amounts that are present in the carrier in the form of uncleanness.

The conversion of alkylene to alkylene oxide as present The catalyst loadings according to the invention are carried out conventional method. And so in the case of the process of generating ethylene oxide is carried out under at a pressure of 1 to 35 bar absolute, at a temperature of temperature in the range of 190-270 ° C, preferably 210- —245 ° C. In general, a thinner is also used % by weight, e.g. methane, in a ratio of, for example, 10-50 wt.

Typically 5 to 70% of the ethylene is converted the rest goes back to the trial. Oxygen can deliver in air or commercial form oxygen. Usually, carbon dioxide is also present.

To prevent local deterioration of catalysis tora can be used, for example, ethylene dichloride.

In the process of producing propylene oxide, can to observe an increase in the rate of transformation that increase in the total pressure of the reacting gases, especially this speed increases with increasing pressure particle oxygen. It is also known that the se¬ the laxity of propylene oxidation to propylene oxide flax increases with increasing oxygen pressure ratio to the pressure of propylene. As a favorable ratio molar oxygen to propylene is considered in the range 0.05 to 100, especially in the range 0.1 to 5.

The partial pressure of propylene can be from 0.3 to 50 bar, total pressure 1 to 100 abs. bar, molar ratio of oxygen to propylene in the range of 0.05 ^ 100, oxygen partial pressure from 0.02 to 10 bar, preferably 0.5-5 bar, especially 1-4 bars, supplied in the form of air or commercial oxygen. Thinner or a mixture of diluents, e.g. helium, nitrogen, argon, methane, and carbon dioxide may be present with respect to 30: 1, preferably between 0.5: 1 and 5: 1, to the total number of moles of propylene + oxygen nu.

The temperature is preferably from 200 to 300 ° C, especially 220-280 ° C. Contact time should be sufficient for a conversion from 0.05 to 50%, e.g. from 1 to 20% of propylene, the rest of the propylene as is ready for trial. There may also be two-104463 present 8 Carbon monoxide. To make the katas work better lyser, you can also introduce a modifier, e.g. ethylene dichloride or vinyl chloride.

Carbon dioxide has been found to affect higher selectivity of transformation. It is used in 5 transformation of olefins, especially propylene, in a ratio molar to O 2 in the range 1: 1 to 50: 1, preferably no 2: 1 to 10: 1. Partial pressure of dioxide the carbon is 0.5 to 50 bars, preferably 4-10 bars. Well Propylene oxide can be produced advantageously by contacting propylene and oxygen over the catalyst embolism according to the invention in the presence of a response the concentration of the reaction modifiers causing lowering the oxygen conversion from 20 to 99%, preferably 15 no 30-98%, especially 40-95%. It could be the components of the catalyst or supplied to the property gas during the reaction. Modifiers re¬ stocks include fluorine, chlorine, bromine, iodine, bismuth, sulfur, selenium, tellurium and / or phosphorus. 20 A preferred reaction modifier is chlorine.

Maybe a keel with 1 to 6 carbon atoms, e.g. methyl chloride or tert-butyl chloride, chlorinated diphenyl or polyphenyl, dichloromethane or chloroform, chlorine 25 rated benzene, e.g. chloro- or dichlorobem- nem, vinyl chloride or preferably ethylene chloride flax. They can also be used suitable compounds containing bromine or iodine, and sulfur, selenium, tellurium or phosphorus can be added as 30 volatile organic compounds, oxides or water dorków.

Preferably, sulfur, selenium, tellurium or phosphorus for could appear as components of the catalyst easily retained by the catalytic converter and retained - 35 jace your action. By contrast, halides are easy removed from the catalyst, so it is recommended that leading them, as mentioned above, to the phase gas, preferably continuously during the process reaction. 40 Recommended when the reaction modifier contains chlorine is for it to be added continuously in an amount to have 5-10,000 present, preferably —2,000 ppm by weight of chlorine, based on propylene. These proportions are partially dependent on 45 reaction temperature, molar proportions flax in the reaction mixture, the flow rate in the mixture of gases, pressure and the composition of the directory lighter, but are also partially dependent on the use of this reaction modifier. For example, 50 in general, a 2-12 chlorine feed is required times more in the form of vinyl chloride than twice as chlortou ethylene 0.1-2 times in the form of chloroiben- zem and 0.02-2 times in the form of dichlorobenzene.

Sulfur, selenium, tellurium and phosphorus can be supplied 55 to the catalyst in the form of volatile compounds, e.g. as mercaptans or phosphines, or in un volatile inorganic compounds, for example sulfur oxides ki and tellurium oxides, or may be introduced into the catalyst in the form of a salt. In this case, 60 the catalyst used according to the invention may have less pore size limited. Watch out it is clear that the average pore diameter in the medium is it should be from 1 to 1000 microns, preferably not 1-15 microns, especially 2-10 microns, 65 marked mercury porometric method. Co- The first nasal spray is alfa-tilenelk gliou.

In many cases it has been found that catalysis the track can be conveniently regenerated by remaining for a while under oxidizing conditions e.g. by interrupting the propylene supply. Out the propylene oxide formed in the process is recovered is present in the gaseous product from which it has been isolated it is obtained by a suitable method, for example by extracting water or an organic solvent, such as kim such as propylene glycol or polyol peroxic; or as a condensate from the product here the gaseous can be directed to further re¬ shares, for example with acids or bases. Understandable is that in the process must be observed safeguards red against ignition or explosion.

Example 1 A catalyst was prepared for the oxidation of ethylene to ethylene oxide (meaning catalyst A) as follows: 80 g of silver acetate, analytical grade, dil discharged in 80 ml of ammonia water at c. 0.880 and filtered. For a slide where ana¬ Lysis showed 5.63 moles of silver per liter three, 12 mL of ethanolamine was added. 60 ml of this solution the product was added dropwise to 300 g of carrier while mixing, which was a gramiuilate of aluminum silicon (sold the important company Nionton Co. under the name "ALUNDUM") and from which, after shredding and processing In the haying process, particles with a diameter of 0.42-1 mm were obtained.

The apparent porosity of the carrier was 4-44%, and a porosity with respect to water of 16-20%.

Medium after saturation with silver solution it was heated for 4 hours in a forced oven continuous flow of air, increasing the temperature re from 100 ° C to 280 ° C at a rate of 0.8 ° C / min.

The result was a product containing 8% by weight metallic silver. (Alternatively the carrier saturated with silver solution by pouring over with the measure of the solution which was then decanted or descended).

Example II. A series of catalysts were prepared silver tracks containing additional meta wrong, following example I, but with this rose nica, with a soluble salt of the additional metal dissolved in the silver solution directly not before saturating the media. So prepared catalyst B contained 10 cadmium atoms (added it as acetate) to 1,000 Ag atoms. Kata C lysator contained 10 gold atoms (added as the diolxaininium of gold (I) chloride per 1000 silver atoms bra) and catalyst D contained 10 barium atoms (added as acetate) per 1000 silver atoms. Ka¬ talcum G contained 10 zinc atoms (added as acetate) per 1,000 silver atoms. Catalyst H contained 10 copper atoms (added as formate) per 1,000 silver atoms.

Catalyst E contained 10 barium atoms per 1000 Ag atoms (it was prepared by saturation the price of the carrier described in the aqueous example barium hydroxide solution, heating at 300 ° C for 60 minutes under a CO 2 gas atmosphere to the transition of barium hydroxide to carbonate and then not saturation with silver solution as in example class I). Catalyst I contained 10 ma. Atoms gnesium on 1000 silver atoms (prepared as9 104463 catalyst E, with the difference that the medium is saturated magnesium formate instead of hydroxide bar).

Silver catalyst F containing cadmium plus bar with 10 cadmium and 130 barium atoms for 1000 silver atoms, it was prepared as follows puje: The carrier described in Example 1 was saturated with three has quarters of the amount needed bar used as the hydroxide, which was converted to veg lan bar, as in the case of E. Cal's catalyst the amount of cadmium and a quarter of the amount of barium contained it was in a silver solution as cadmium acetates and barium (as for catalysts B, C and D).

Example III. Catalysts A-F were subjected to tests for catalytic activity followed which way: g of the catalyst was charged to the glass reservoir actuator (inner diameter 8 mm) placed it in a circulating air oven and thermoregulation, then conditioned in increasingly harsher conditions until the catalyst is reached low catalytic properties. Then over the canal A gaseous mixture was passed through the talc consisting of 30% C2H4, 8% O2, 62% N2, and 4 ppm of ethylene chloride at a pressure of 1 bar.

The selectivity and the conversion at 240 ° C were determined and at the hourly space velocity of the gas GHSV = 200 h_1. The gas velocity then changed It was titrated to obtain 5% and 40% oxygen conversion and the selectivity of the reaction was determined with respect to ethylene oxide. The results are presented in Table 1.

Table 1 Kiata- atatior 1 AND B C. T> E. F i G. H. AND Performance at GHSV = 200 h "1 c | s 2 24 23 3 21 60 *) 40 3 79.5 83.8 89 86.0 88 87.6 74 80 78 C = 5 S. 4 81.5, 85.9 90.2 86.7 88.7 90.1 82 *) 83 83 C = 40 1 s 1 78 82.0 - 85.2 86.8 85.9 78 *) 79 78 2 | 5 45 GHSV - Hourly Gas Space Velocity C -% oxygen conversion S - yield in moles tilemtou ethylene per 100 moles of ethylene consumed *) at 230 ° C Example IV. The catalyst was burned up to the oxidation of ethylene or propylene as appropriate ethylene oxide or propylene oxide: 0.175 g of sodium formate was dissolved in 11.85 ml 12.6% i. (w / w) of a warm aqueous water solution barium hydroxide. The carrier was saturated with this solution described in example I. Apparent porosity of the carrier was 50%, the porosity with respect to water %, specific pore volume 0.24 cm / week, approx surface proper 0.36 m2 / g. Out of the overall volume 98% of pores were contained in pores with a diameter 50 55 1-15 microns. The average pore diameter is force of 27 microns.

The saturated carrier was heated in a suction oven with a direct stream of air for 30 minutes at 300 ° C, and then for 60 minutes under a dioxide atmosphere towards carbon at the same temperature.

Cooled media, now containing sodium and bar, saturated with the second solution, i.e. 9 ml 42 wt.% aqueous silver nitrate solution and dried at 110 ° C for 2 hours. Silver salt, ref was induced to metallic silver by passing through the bed within 6 hours a nitrogen stream started containing 0.6% vol. hydrogen followed by 1 hour nitrogen stream containing 10% hydrogen, at 220 ° C. The product obtained was suspended paradises 7.2%. by weight of metallic silver.

EXAMPLE 5 15 g of catalyst, prepared by as described in example IV, was loaded for glass reactor (inner diameter 8 mm), placed in a flow oven air and thermoregulation. Conditioner catalyst used under increasingly stringent conditions, to obtain permanent catalytic properties by the catalyst tics.

Pressure was passed over the catalyst 1 bar gas mixture consisting of 30% ethylene, 62% nitrogen, 8% oxygen and 4 ppm chloride ethylene. The selectivity was determined at 240 ° C and at GHSV = 200 h_1. Feed speed was changed gas so that the oxygen conversion was 5% and 40% and the selectivity of the hundredth conversion was determined to ethylene oxide. The results are shown in table 2.

Table 2 1 Capacity at GHSV = 200 h "1 C. 2.8 S. 89.0 C = 5 S. 88.8 C ^ 40 S. 85.0 65 Example VI. 15 g of catalyst, prepare as described in example IV, was loaded to glass reactor placed in a furnace with a thermal moregulation. Passed over the catalyst a mixture of 30% propylene, 8% oxygen, 62% nitrogen and 500 ppm of dichloromethane at a pressure of 1 bar and the hourly space velocity of the gas GHSV = 200 h "i. At 240 ° C selectively conversion rate with respect to propylene oxide nu was 42% and the oxygen conversion was 10%.

Example VII. Alpha Alumina Granules (described in Example I) ground and sieved well, obtaining particles with a diameter of 0.42-1 mm. Mon. the apparent roughness of the carrier was 40-44%, porosity weight in relation to water 16-20%, weight volume capacity 2.3 g / ccm3, apparent specific weight 3.95 g / cms, specific pore volume 0.19 cm / week, * surface proper 0.17 m2 / g. 100% by volume the trench was in the pores of 1-40 microns, 79% the pores were 1.5-15 microns in diameter, the intestinal pore diameter was 2.5 microns.

The catalysts containing 8% by weight of 104463 were prepared 11 12 silver and 130 barium atoms per thousand atoms say silver ,, and (with the exception of catalyst J, which served as a comparison) metal compound al¬ calcane (as given in Table 3), followed which way: The medium was saturated with three-quarters of the required the amount of barium used as barium hydroxide plus the total amount of alkali metal as you formate. Barium and alkali metal compounds it was carried out in carbon by heating in an air atmosphere at a temperature of 300 ° C for minutes, then under a dioxide atmosphere carbon at 300 ° C for 60 minutes. The other one a fourth amount of barium was added as acetate to a silver solution prepared as follows puje: 80 g of silver acetate, analytical grade discharged in 80 ml of ammonia water (c. wl = 0.880) was filtered and 12 ml was added to the filtrate ethanolamines and barium acetate. 60 ml of the solution thus obtained were added dropwise at mixing up to 300 g of carrier. Saturated medium it was heated for 4 hours in a forced oven with a constant stream of air, raising the temperature from 100 ° C to 280 ° C at a rate of 0.8 ° C / minute.

Catalysts tested for catalytic activity in the following way: g of the catalyst was charged to the glass reservoir an actuator with an inner diameter of 8 mm, placed in a circulating air and thermoregulating oven lation and conditioned as in previous tests clades. Then pass over the catalyst a mixture of £ 0% ethylene, 8% oxygen, 62% nitrogen and 4 ppm of ethylene chloride under pressure 1 bar.

» The selectivity and the conversion at 240 ° C were determined and at GHSV = 200 h-1. The speed of gas was changed, so that the oxygen conversion would be 5% and 40% and the selectivity and conversion were determined ethylene to ethylene oxide. The results are summarized in the table below: GHSV - Hourly Gas Space Velocity C -% oxygen conversion io- After discharging the catalyst after 40 hours J, work, all silver particles in catalyst Q They had diameters in the range of 0.1-1 microns, of which > U- greater than 50%, in the range of 0.2-0.5 microns, what was left found in examinations under an electric microscope throne seat. Similar measurements for catalyst P ru showed that 100% of the particles fell within the range ; as 0.1-1.5 microns, 80% in the range 0.1-1.0 ml- Le- kron, and 60% in the range of 0.4-0.8 microns, lie! 0 Example VIII. The catalysts were prepared : browe 1 and 2 for the oxidation of ethylene to ethylene oxide for len, containing bar as a promoter: on 6 ml of freshly prepared solution, by to dissolve 8 g of silver acetate, pure to ana- ; e-lysis in 8 ml of ammonia water (CW = 0.880), filtering and dissolving 1.2 ml of ethanolamine ) from - and 0.186 g of barium acetate, added dropwise with = using up to 30 g of carrier. For Catalyst 1 used ml medium described in Ex. I. Apparent porosity The 2ó carrier was 24.8%, the pore volume specific zy 0.24 cm3 / g, and the specific surface 0.36 m2 / g. ik Out of the total pore volume, 95% was contained in with diameters of 1 - 15 microns, and 88% in from 2 to 10 microns in diameter.

The average pore diameter was 2.7 microns on on. The carrier for Catalyst 2 was granules alpha alumina sold by the company Verei e- nigte Aluminum-Werke Aktierigesellschaft (VAN), of which also after crushing and sieving u-particles with a diameter of 0.42-1 mm were obtained. Poro- The apparent viability of the carrier was 40%, Water content 26%, specific volume after % equals 0.24 cm3 / g and the specific surface area is 1.0 m2 / g. im Out of the total pore volume, 95% was in with diameters in the range of 0.1-3 microns, 5C a 75% and in pores with diameters in the range 0.4-2.0 it, microns. The average pore diameter was 0.8 % micron. The carrier, after saturation with a solution was placed in the oven for 4 hours, with a constant in 40 air flow and temperature rise from 100 ° C to 300 ° C with a rate of 0.8 ° C / min.

S - yield in moles of ethylene oxide per 100 moles of ethylene consumed Catal blockage "^ J K. L. M. N Q P. Q R S. T. Addition symbol - Rb Cs Cs On On On On On K. K. quantity atoms at 1000 atoms Ag - 4 2 2 69 346 692 70 Table 3 Performance at GHSV = 200 h "i C. 13 13 11 22 23 16 18 16 9.2 21 '19 S. 80 ^ 5 87 87.5 87 80.4 87.5 92.5 92 90.8 89.5 87.5 C = 5 S. 82 " 88.5. 89 85.9 91 93.5 92.7 91 92.5 88.6 C = 40 S. 78 ' 81 81 76.2 80.0 90.6 90.4 90.1 86.0 85.8 35104463 13 Example IX. Catalysts 1 and 2 were subjected to analysis, and then the activity of the catalyst was examined tic in the following way: g of catalyst was charged to the glass reactor with an inner diameter of 13 mm, placed in an air-flow and thermore- gulation. Stirring was passed over the catalyst nine 30% C2H4, 8% O 2, 62% H2 and 4 ppm chloride of ethylene at a pressure of 1 bar and at GHSV = = 200 h_1. The selectivity against ethylene oxide (S), oxygen conversion (C) and active catalytic performance (A) at 240 ° C. Composition of the catalyst and the results of the activity studies are given in tab face 4.

S - olefin oxide yield (in moles on 100 moles of olefins consumed).

C -% oxygen conversion A - olefin consumption rate (in moles per ki¬ catalyst logram per hour).

Table 4 14 Catal blockage 1 2 Pro motor Ba ppm 2,000 2,000 Operation of the catalyst | S. % 86.9 87.0 C. % ¦ 11.6 16.2 A 1 m.Kg "1 h "1 0.19 0.28 Example X. Silver catalysts were prepared browe 3 and 4 for the oxidation of ethylene oxide: 6 ml of a fresh solution were mixed with the carrier. prepared by dissolving 8 g of acetate of silver in 8 ml of ammonia water (CW = 0.880). filtering and dissolving 1.2 ml of ethynolamine, 0.186 g of barium acetate and 0.208 g of sodium acetate. Carriers Catalyst 3 was alpha-oxy granulate aluminum as in ex. I. Porosity in relation to water (which is the same with mercury) was 0.24 cm3 / g, which corresponds to the apparent porosity 40-44% ', a specific surface area 0.36 m2 / g.

Of the total volume of pores, 95% was in half diameters ranging from 1 to 15 microns, and 80% in the pores of 2-10 microns. Average average The pore size was 2JI microns.

The carrier for the catalyst 4 was alpha - VAN alumina, used in the same fragmentation (particle diameter 0.42-1 mm). Mon. apparent carrier roughness was 26%, volume specific pore 0.24 cm3 / g and surface area approx at 1.0 m2 / g. 95% of the total pore volume it was worth in pores with a diameter of 0.1-3 microns, and 75% in the 0.4-20 micron pores. Average The pore diameter was 0.8 microns. Medium, after saturated with the solution, heated for 4 hours in a forced draft oven at increasing the temperature from 100 ° C to 300 ° C with a 'Rate of 0.8 ° C / min. After this, the canal is processed The talismans contained 8% by weight of silver.

Example XI. Catalysts 3 and 4 after analysis was tested for catalytic activity: g of the catalyst was charged to glass reflux 50 55 the actuator (inner diameter 13 mm) is placed in an air-flow and thermo- control. Mixture was passed over the catalyst 30%: C2H4, 8% O2, 62% N2 and 4 ppm chlorine to ethylene at 1 bar and GHSV = = 200 h_1. The selectivity against ethylene oxide (S), oxygen conversion (C) and active catalytic performance (A) at 240 ° C. The results are given in the table below: S = the yield of olefinic oxide in moles per 100 moles of olefins consumed C =% oxygen conversion A = olefin consumption rate in moles per kilogram of catalyst per hour

Table 5 Kata lysis track 3 4 Ba ppm 2000 2000 On ppm 1180 1180 Performance S. % 89.8 90.8 C. % 24 32 ¦ A m.kg-1 0.15 0.29 . Example XII. The procedure was as in the example on day VII, using two catalysts with a high content of sodium in relation to silver, unchanged barium to silver ratio. Received niki: Table 6 The quantity of atoms say Na na 1000 atoms say Ag 2 344 4,688 Performance at GHSV = 200 h "1 C, (%) 12.0 7.0 S.

Claims (5)

Patent claims 1.: A method for the preparation of a catalyst intended for the production of alkylene oxides by oxidation of appropriate olefins with oxygen, consisting in the fact that a porous support resistant to heating with a specific surface area ranging from 0.04 to 10 m2 / g, determined by the Brunauer, Emmett and Teller method, the apparent porosity at least 20%, determined by the mercury absorption method, and the mean pore diameter ranging from 0.3 to 15 microns, determined by the mercury porometric method, is saturated with a solution of a silver compound decomposable, the solution being alkaline or containing a complexing agent and a reducing component, then the solution is evaporated and the silver compound is broken down into silver, and a promoter is introduced into the carrier, characterized in that a promoter is used as a promoter. both activating amounts of copper, gold, zinc, cadmium, mercury, molybdenum, tungsten, chromium, calcium, magnesium, catalyst 18 '19' 20 '' 21 'Add Symbol Na Na K atk number of atoms per 1000 atoms Ag 69 692 70 Table 19 Efficiency at GHSV = 200 h -1 C 11.3 15 10 14 S 83.6 88.6 90.6 88.1 C = 5% S 84.0 89.6 90, 9 89.7 C = 40% S 72.9 85.4 87.1 85.2 | C -% oxygen conversion S - yield of ethylene oxide in moles per 100 moles of ethylene consumed, strontium and / or barium, and activating amounts of at least one component from the group of sodium, potassium, cesium and rubidium. 2. Way according to ziastriz. The method of claim 1, characterized in that the carrier is impregnated with a solution of a silver compound decomposed by heating, the solution containing a complexing agent and a reducing component, then the solution is evaporated and the silver compound is decomposed to form silver particles with a diameter below 10,000 A, adhering to the carrier together with 1 to 100 atoms of copper, gold, calcium, magnesium, zinc, cadmium and / or mercury and / or 1 to 200 atoms of strontium and / or barium per 1000 atoms of silver, the above amounts represent an excess over the content of these ingredients in the possible impurities and / or binder. 3. The method according to p. A method as claimed in claim 1 or 2, characterized in that a solution of a silver compound is used for the impregnation, which contains a complexing agent which also acts as a reducing component and is an amine capable of reducing the silver compound under heating. 4. Way according to history. The process of claim 1 or 2, characterized in that bar and sodium or barium and potassium are used as promoter. 5. A method of producing a catalyst for the production of ethylene oxide or propylene oxide by contacting the catalyst with ethylene or propylene and oxygen, whereby the heat-resistant, porous, shaped carrier is saturated with a solution of the compound decomposable silver and decomposes this compound into silver, and a promoter is introduced into the carrier, characterized in that the promoter is used in amounts activating sodium, cesium, rubidium and / or potassium and in amounts activating magnesium, strontium, calcium and / or more preferably barium.