Catalyst to obtain a vinyl acetate, a method thereof, a method of producing vinyl acetate and method for producing a carrier for catalyst for the synthesis of vinyl acetate

 

(57) Abstract:

Describes a catalyst to obtain a vinyl acetate in the fluidized bed, characterized in that it is a catalyst corresponding to the formula Pd-M-A where M is barium, gold, lanthanum, niobium, cerium, zinc, lead, calcium, strontium, antimony, or mixtures thereof; A represents at least one alkaline metal containing material impregnation in pre-cooked practically inert carrier in the form of microspherical particles in which the size of at least 50% of the particles are less than 10-4m (10 μm). Also described method thereof, and methods for producing vinyl acetate and media for synthesis catalyst and a carrier for catalyst for the synthesis of vinyl acetate. The technical result is to simplify the process and obtain a catalyst having high efficiency and adequate resistance to abrasion. 5 C. and 30 C.p. f-crystals, 2 tab.

The scope of the invention

This patent application is a continuation-in-part patent application of U.S. 200130, filed February 22, 1994

The present invention relates to a method for producing a fluidized bed of palladium-promoted catalyst for ispolzovat the invention relates to new media fluidized bed and use media to obtain a palladium-promoted fluidized catalyst, used to obtain vinyl acetate.

Getting vinyl acetate joint interaction of ethylene, acetic acid and oxygen in the gas phase in the presence of a catalyst is known. Typically, the catalysts used in the form of a fixed layer and is applied to the material of the porous media as silicon dioxide or aluminum oxide.

Early examples of such catalysts show that palladium and gold more or less evenly distributed throughout the media (see, for example, to U.S. patent 3275680, 3743607 and 3950400 and the United Kingdom patent 1333449 and patent of the Republic of South Africa 687990). Later it turned out that this is a flaw, because it is found that the material in the inner part of the carrier does not contribute to the reaction, as the reaction reagents are not able in substantial amounts to diffuse into the media. To resolve this problem have been developed new methods of making catalysts, to obtain a catalyst in which activetestsuite components are concentrated in the outer shell material of the carrier. For example, in the description of the patent in the UK 1500167 offered catalysts in which at least 90% of palladium and the radius of this particle. In addition, in the description of the patent in the UK 1283737 States that the degree of penetration into the porous carrier can be adjusted prior to processing the porous carrier with an alkaline solution, for example sodium carbonate or sodium hydroxide. Another solution to this problem in order to obtain particularly active catalysts proposed in the description of the U.S. patent 4048096, and other methods of making the catalyst-impregnated membrane are available in the descriptions to the U.S. patent 4087622 and 5185308. Each of these patents relates to the obtaining of the fixed catalyst layer used to obtain vinyl acetate. However, in the description of the U.S. patent 3950400 also States that its proposed catalyst can be used in the reactor with a fluidized bed. Moreover, in the description of the patent in the UK 1266623 features, as stated in this description, a fluidized bed of catalyst to obtain vinyl acetate, which contains palladium promoted with various alkali, alkaline earth and other metals.

From an economic perspective, it would be best to get the vinyl acetate in the course of the process in the fluidized bed, as well as the process in n is that the design of the reactor fluidized bed easier design novotrubnogo reactor with fixed bed, the ability to extend the service life of the catalyst due to the absence of hot spots, which are usual for a reactor with a fixed bed, the possibility of continuous addition of fresh portions of the catalyst that allows you to maintain maximum performance and virtually eliminate the need for operations of replacement of the catalyst, and the ability to achieve improved performance, because without prejudice to the security of the oxygen can be introduced into the reactor at higher concentrations without the risk of a flammable mixture.

Prior to the development of the method according to the present invention attempt to obtain a palladium-promoted catalyst in the form of a fluidized bed did not lead to the formation of a catalyst having the desired properties, which would allow to develop a cost-effective way of getting in the fluidized bed vinyl acetate. The method according to the present invention enables to solve the problems associated with known prior art technology, and to obtain a catalyst which has high efficiency and adequate resistance to abrasion, so that it can be used to obtain vinyl acetate.

Brief sloganeering catalyst, which is a palladium-metal-promoter-alkaline metal, for use when obtaining vinyl acetate.

Another objective of the present invention is the creation of new media for use in preparation of a fluidized bed of palladium-metal-alkali metal-promoted catalyst suitable for use in obtaining in the fluidized bed vinyl acetate.

In addition, another purpose of this invention is to provide a new method of obtaining media used in the preparation of vinyl acetate catalyst.

Additional objectives and advantages of the present invention partially set forth in the following description and partly obvious from this description, or become apparent from the practical implementation of the present invention. These objectives and advantages of the present invention can be achieved and implemented through techniques and combinations that are specified in the attached claims.

To achieve the above objectives of the present invention in the method of preparation of fluid bed vinyl acetate catalyst, corresponding to the following formula Pd-M-A, where M denotes a bar least one of the alkali metals or their mixture, provided by impregnation of pre-cooked microspherical particles of the medium in which the size of at least 50% of the particles are selected in such a way that they are less than 100 microns, the solution containing free from halide salt of palladium, M, and at least one alkali metal, and drying the impregnated catalyst. Practically inert carrier in the form of particles generally consists of microspherical particles of a material selected from the group including aluminum oxide, silicon dioxide, zirconium dioxide or mixtures thereof.

In accordance with another variant of implementation of the present invention the method is carried out using an aqueous solution that contains no or substantially not containing any organic solvent.

In a preferred embodiment of the present invention the metal salt of the alkali metal separately impregnated carrier, preferably followed by impregnation of the material of the carrier with a solution which contains a salt of palladium and the element M.

In another embodiment, the present invention is impregnated carrier is heated in a reducing conditions, receiving on the surface of the carrier precipitate of palladium and M. This reconstruction is another preferred implementation of the present invention, the catalyst is dried at a temperature below 80oC, preferably between about 60 to 70oC.

In one of preferred embodiments of the present invention the particle size (particle diameter) is practically inert material of the carrier is chosen so that these dimensions are at least 50% of the particles were less than about 60 microns. In a more preferred embodiment, the dimensions of at least 75% of the particles are less than 100 microns, in a particularly preferred embodiment, the dimensions of at least 80% of the particles should be less than 100 microns. Finally, the preferred media is practically not contain sodium.

In another embodiment, the present invention carrier for the preparation of vinyl acetate catalyst is a mixture of virtually inert microspherical particles, the specific pore volume ranging from 0.2 to 0.7 ml/g, specific surface area is in the range from 100 to 200 m2/g and a size of at least 50% of these particles is less than 100 microns.

In a preferred variant implementation of the invention, the dimensions of at least 75% of the particles are less than 100 microns, especially preferably at least 85% must be less than 100 microns.

Even odnoetapnoe a microspherical inert particles, preferably of silicon dioxide, zirconium dioxide, aluminium oxide or mixtures thereof, and the specific volume of the pores ranges from 0.2 to 0.7 ml/g, specific surface area equal to from 100 to 200 m2/g obtained from a mixture of from 80 to 20% Zola inert carrier and from 20 to 80% dried inert particles.

In the preferred embodiment of this aspect of the present invention, the specific pore volume of inert particles is in the range from 0.3 to 0.65 ml/g, particularly preferably from 0.4 to 0.55 ml/g

In another preferred embodiment of the present invention, the specific surface area of the particles is in the range from 110 to 195 m2/g, particularly preferably from 120 to 195 m2/,

In yet another additional embodiment of the present invention, the material of the carrier of the microspherical particles of silicon dioxide is obtained by mixing from 20 to 80% Sol of silicon dioxide and from 80 to 20% of Aerosil silica spray drying this mixture at elevated temperature from 125 to 280oC, preferably from 130 to 240oC, and calcining mentioned spray dried particles is preferably at a temperature of from 550 to 700oC, more preferably from 630 is th acetate catalyst can be obtained by way which provides mixing from 80 to 20 weight. % aqueous Zola, representing almost inert microspherical particles, and from 20 to 80 wt.% solid practically inert material in the form of particles to obtain water mix, spray drying specified water mixture and calcining the above-mentioned particles to form the above practically inert carrier.

In the catalyst according to the present invention, palladium, M and alkaline metal contained in the following weight percentages: from 0.1 to 5.0 wt.% palladium, preferably from 0.2 to 4.0 wt.%, most preferably from about 0.3 to about 1.0 wt.%; from more than 0 to 10 wt.% alkali metal, preferably from 1.0 to 8.0 wt.%, most preferably from 0.1 to 5.0 weight. %; from more than 0 to about 5.0 wt.% component M, preferably from 0.1 to about 4.0 wt.%, most preferably from 0.1 to 3.0 wt.%.

Detailed description of the invention

Below is a detailed description of the preferred variant implementation of the invention, embodiments of which are shown only for illustrative purposes.

Test reactor

The catalysts were tested in a reactor with a fluidized bed laboratory by weight of the R in combination with a diluent in a volume of 30 ml. Typically, the catalyst was injected into the reactor in an amount such that the during the evaluation of each of the catalysts containing metallic palladium was 0,093, the Total volume of 30 ml was achieved by mixing activitiesthese catalyst with a sufficient amount of spherical inert particles of silicon dioxide prior to loading them into the test reactor. This reactor was equipped with two inlet openings for the source material. In the course of some experiments that study the ethylene, acetic acid and oxygen was introduced into the reactor through the bottom hole, and through the Central inlet was filed only nitrogen. During other tests through a Central inlet for the starting material was additionally applied to the oxygen. A Central hole was provided by 2.5 inches (63.5 mm) above the bottom of the hole for the intake of the source material.

In a reactor maintained excess pressure at the level of 115 pounds per square inch (8.1 kg/cm2and all lines leading to the reactor and the exhaust from him, were equipped with heaters to maintain the temperature of 150-155oC, allowing to prevent the condensation of liquid raw materials or products. As correctly from 135 to 190oC.

The exhaust from the reactor, the gas stream is continuously analyzed during the process by gas chromatography a Hewlett Packard model 5890 equipped with detectors as TCD and FID. Oxygen, nitrogen, ethylene and carbon dioxide were separated in g-mole / tube sheet column in parallel with 10% carbowax 20M on Chromosorb WAW 80/100 and 23% SP2700 on 80/100 Chromosorb PAW and quantitatively determined using TCD. The vinyl acetate and acetic acid were separated in the column 80/120 carbopack with 4% carbowax 20M and quantitatively determined using FID.

Preparation of media

Microspherical particles of silicon dioxide are two types were prepared and used as a carrier in the practical implementation of the present invention. Before using sifted all media and in all catalytic preparations used particles of the carrier the following size distribution:

5% of the particles less than 105 microns, but more than 88 microns

70% of the particles less than 88 microns, but more than 44 microns

25% of particles less than 44 microns.

It must be borne in mind that the above distribution of particle size is not the limiting condition and that depending on the size of the reactor and the operating conditions in this distribution, you can make different variations.

l Company) with silicon dioxide DeGussa Aerosil(company DeGussa Chemical Company). In the dried media source 80% of silicon dioxide was Sol, and the source of 20% of silicon dioxide was Aerosil. Dried spray microspherical particles were caliciviral in air at a temperature of 640oC for 4 h

Silicon dioxide Aerosilis a trademark of fume silica company DeGussa. This material is characterized by a high specific surface area (~200 m2/g), almost no micropores, a homogeneous distribution of particle sizes in the nanometer range (110-9m) and absence of sodium. Fume silica, properties which are comparable with the properties of Aerosilcan other companies; in the method of preparation of the carrier 1 it can also be used instead of the product Aerosil.

Due to the large average particle size of the silica in the ash Nalco 1060 (60 millimicron) in this field of technology is particularly advantageous to apply the Sol of silica Nalco 1060. Such larger particles of silicon dioxide are packaged less efficiently than particles Zola smaller (~30 millimicron as a product of Nalco 2327) and give the finished media with high specific pore volume of 1 instead of Zola silicon dioxide 1060 can use other sols of silica with similar large average particle size (~40-80 millimicron).

The carrier 2

The number of carriers of the microspherical particles (carriers 2A-2D), containing the product of KA-160 (firm Sud Chemie), were prepared as follows.

Media 2A: 75% SiO2of KA-160 25% SiO2from Zola.

750 g of the product of KA-160 to grind so that the particles are sifted through a sieve with mesh size of 35 mesh (0.50 mm) and washed to remove all soluble impurities, in particular chlorine ions. Further, this solid silica was mixed with 694,4 g Zola silicon dioxide Snotex - N-30 (Nissan Chemical) (36 wt.% solid particles) and 556 g of distilled water. This mixture is milled overnight in a vibratory mill. Then a homogeneous suspension was spray dried to obtain microspherical particles suitable for use in a reactor with a fluidized bed. Next microspherical particles of the medium was caliciviral at a temperature of 640oC for 4 h

Media feature KA-160 is to create a significant portion of the porous structure inside the microspherical particles. The carrier for the fixed layer, KA-160, produced by the company Sud Chemie; it has properties, which with advantage can be used in the preparation of vinyl acetate catalyst. Advantages of coporatist or her absence and significant porosity (~of 0.57 ml/g) in mesoporous range. Also available with other carriers for the catalysts of the fixed layer with properties specific surface area and specific pore volume, which are similar to the product of KA-160 (small microporosity or her absence, the specific volume of mesopores ~1.5 to 0.25 ml/g and specific surface area of 80-200 m2/g). In the preparation method of the carrier 2 instead of KA-160 can be used such media.

Media 2B: 65% SiO2from the product of KA-160 and 35% SiO2from Zola.

This medium is prepared exactly the same as the carrier 2A, except that when used 227,5 g of KA-160, 408,3 g of the product Snotex-N-30 (30 wt.% solid particles) and 64 g of distilled water.

The carrier 2C: 50% SiO2from the product of KA-160 and 50% SiO2from Zola.

This medium is prepared exactly the same as the carrier 2A, except that when used 175 g of KA-160 and 583,3 g of the product Snotex-N-30 (30 wt.% solid particles).

Media 2D: 75% SiO2from the product of KA-160 and 25% SiO2from Zola.

This medium is prepared exactly the same as the carrier 2A, except that when used 262 g of KA-160, 210 g of the product Nalco 2327 (40% solids) (company Nalco Chemical Company) and 219 gap above, can be used in accordance with the method of the present invention for the preparation of fluidized catalyst to obtain a vinyl acetate monomer. When used in the preparation of fluidized catalysts by impregnation activetestsuite metals such media showed unexpectedly improved physical properties for vinyl acetate catalysts of the present invention in comparison with any technically currently available media. Selected analytical data for all media are summarized in the following table 1.

Preparation of catalyst

Used the usual method of preparation is outlined below.

Typically, the carrier of the microspherical particles impregnated with a solution (or solutions) of active metals by the method of initial moisture content. Does not contain halides compounds of active metals, palladium, element M (e.g., gold) and potassium acetate can be dissolved in appropriate proportions in an acceptable solvent with subsequent impregnation their spherical particles of the medium. Usually it is desirable that all activetestsuite metals that you want to use the spine adequate to which is required to fill the pore volume of the carrier. In some examples, the desired promoter may be insoluble in the same solvent in which other soluble metal compounds, which are intended for use. In such cases, the carrier can be impregnated with a solution containing some metal components, with subsequent impregnation with a second solution containing the other components. It is acceptable for such use solvents include water and volatile organic solvents, in particular, carboxylic acids with four or fewer carbon atoms, alcohols, ethers, esters and aromatic compounds. After drying the wet catalyst can be used to obtain vinyl acetate or you can first restore using methods known to any person skilled in the technical field.

Usually in the presence of acetic acid and heating the catalyst to high temperatures (~ 100oC) the catalyst darkens to black and loses activity. In addition, when a solution of palladium acetate (together with other acetates of metals or without them) is heated to too high teehnieal to greenish and the formation of black sludge. Usually a temperature of 60oC is safe for work, but for dissolving palladium acetate for short periods of time the temperature can be maintained at the level of ~80oC.

Example 1

The catalyst of the following composition: 0.75% wt. Pd, 0.32 wt.% Au and 2.88 weight. % Prepared by dissolving palladium acetate in the solution Zolotarenko reagent acetic acid, described in U.S. patent 4933204, and then impregnated with this solution microspherical particles of carrier 2A, identified above. The solid material was dried at a temperature of 60oC in a rotary evaporator, and then Pd and Au were recovered aqueous solution of hydrazine (without a hydroxide of alkaline metal). The solid material was washed to remove hydrazine, dried and impregnated with potassium acetate. A portion of the catalyst 12,67 g (16,7 ml) for testing were placed in the reactor. The results of the test of this catalyst in the reactor under different conditions are summarized in the following table 2. These results show that in the case of 10.55% of O2and 14,31% HOAc at a temperature 164,9oC conversion was 18.2%, and the selectivity of 83%.

Example 2

The catalyst of this example, which contained 1.07 wt.% pulled the patent UK 1266623, except that the medium was the same as used in experiment example 1. For testing in the reactor was placed a portion of the catalyst 8,68 g (11.3 ml). The results of the test of this catalyst under different conditions are summarized in the following table 2. Its application in the case of 7% oxygen and 10% acetic acid at a temperature of 159oC allows you to achieve the conversion of ethylene to 8.1% and the selectivity in respect of the vinyl acetate - 84.4 per cent.

Example 3

Repeating the procedure of example 2 to obtain a catalyst containing 1.01 wt.% palladium, 0.38 wt.% gold and 2,60% wt. potassium. However, used identified above the carrier 1. For testing in the reactor was placed a portion of the catalyst of 9.2 g (10,6 oz). The results of the test of this catalyst under different conditions are summarized in the following table 2. The use of this catalyst in the manner described in example 2, was it possible to achieve the conversion of ethylene to 8.6% and the selectivity in respect of the vinyl acetate - 85,3%. Operational properties of the catalyst of examples 2 and 3 are very close, but the catalyst prepared on the carrier 1, it has, as it turned out, a slightly higher activity. Because the compositions of these two catalysts are almost identical, since ivali in accordance with the description of U.S. patent 3950400, except that in this case used the carrier 1 of the microspherical particles (fluidized bed), which is described above. The catalyst contained 0.82 wt.% palladium, 0.40 wt.% gold, 0.13 wt.% barium and 2,69% wt. potassium. At a temperature of 60oC in vacuum was carefully removed with acetic acid (via rotary evaporator). Color solids remained yellowish-brown. A portion of the catalyst 11,57 g (13.4 ml) was placed in the reactor for testing. The results of the test of this catalyst in the reactor, are presented in table 2, showed that he has a high activity and selectivity. Using 7% oxygen and 14% of acetic acid was achieved conversion of ethylene to 12.5% with a selectivity 87,2%.

Example 5

The catalyst, which contained 0.81 wt.% palladium, 0.34 wt.% gold and 2,71 weight. % potassium were prepared by dissolving palladium acetate (PdAc) and potassium acetate (KAc) in acetic acid, followed by addition of acetate gold and impregnation of the carrier 1 is obtained by the solution. Acetic acid was removed in a vacuum at a temperature of 60oC. At this stage, the solid material is retained yellowish-brown color. The process of preparing this catalyst is similar to that described in example 1, excluding the R downloaded portion of 11.75 g (13,2 ml) of the catalyst. The test results of such a catalyst in various conditions are shown in table 2. The catalyst gave a conversion of 9.2% with a selectivity in relation to vinyl acetate of 87.8%.

Example 6

The catalyst, which contained 0.77 wt.% palladium, 0.40 wt.% gold and 2.2 weight. % potassium, prepared as described in example 5. Then the solid was subjected to restore hydrazinehydrate, washed with water to remove hydrazine and added additional potassium acetate. To test the reactor was loaded of 14.25 g (17.6 ml) of the catalyst. There were obtained excellent results, shown in table 2. This catalyst was possible to achieve results similar to the results of the experiment of example 5, i.e. conversion 10,17% with a selectivity of 85.7%.

Various catalysts were prepared on the media type silica with Pd/M/K, where M denotes not gold. The estimated class materials included M = barium, lanthanum, antimony, lead, cerium, niobium, calcium, zinc and strontium. These different metals is illustrated in the following examples.

Example 7

The catalyst prepared with low palladium content, which is common in type catalysts Bayer, 0.88 wt.% palladium, but it's usually been luila acetic acid. This catalyst contained 2.9 wt.% potassium. A portion of this catalyst 15,52 g (21,0 ml) for testing were placed in the reactor. The results of the tests are summarized in the following table 2, in various conditions showed the possibility of achieving the conversion of ethylene, approaching 10%, with 81% selectivity in relation to vinyl acetate. Exposure at elevated temperature (100oC) led to some deactivation of the catalyst, while acetic acid was still present.

Example 8

Using water as the sole solvent to prepare a catalyst, which contained 0.41 wt.% palladium, 0.49 wt.% barium and 2.2 weight. % potassium. A mixture of palladium acetate with potassium acetate and barium acetate dissolved in distilled water to a degree which is sufficient for the possibility of using water as the sole solvent. For testing in the reactor was placed a portion 24,77 g (30,0 ml) of the catalyst. Testing of the spent catalyst in the reactor under various conditions that are specified in the following table 2, which gave a 10% conversion rate of ethylene in selectivity in relation to BA 85%.

The use of water as the impregnating solvent instead of acetic acid-reducing the Yu corrosion, than acetic acid. All this leads to the reduction of expenses for carrying out of the way with water. In addition, water is not a reducing agent for palladium. When the exposure of the catalyst prepared using acetic acid in a furnace at a temperature of 100oC it's getting dark, getting almost black in color, while a similar catalyst prepared with water, retains its yellowish-brown in color and still has excellent catalytic performance. Finally the water is softer solvent with respect to any undesirable effects on the media.

Example 9

Pre-cooked microspherical particles of the carrier was impregnated with a solution of palladium acetate, potassium acetate and antimony acetate. The wet solid material was dried at a temperature of 60oC in vacuum. No prior recovery of the catalyst is not produced. The finished catalyst contained 0.81 wt.% palladium, 0.70 wt.% antimony and 2.9 wt.% potassium. A portion of the 10,95 g (of 12.8 ml) of the catalyst for testing were placed in the reactor. Tests, the results of which are summarized in table 2, the reactor was allowed to reach a conversion of ethylene of about 17% to 89% of the congestion, containing antimony, resulted in a significant decrease in catalytic activity. Tested the catalyst consisted of 0.71 wt.% palladium, 0.71 wt.% barium, 0.71 wt.% antimony and 2.6 wt.% potassium. To test the reactor was loaded portion 10,95 g (13.5 ml) of the catalyst. As shown by the results of the tests are summarized in the following table 2, the estimated concentrations of antimony and barium showed no synergistic action.

Examples 11 and 12

A mixture of palladium acetate, lanthanum acetate and potassium acetate were quite soluble in acetic acid. In the experiment of example 11 was used carrier 1, as in the experiment example 12 carrier 2A. This solution was impregnated pre-prepared media and materials were dried under vacuum, resulting in an excellent catalysts, as indicated in the following table 2. The catalysts of examples 11 and 12 were characterized, respectively, in the following composition (in weight percent): 0,77 palladium, 0,70 lanthanum, potassium of 2.7; 0,80 palladium, 0.57 lanthanum, 3,1 potassium. In the experiment of example 11 to test the reactor was loaded portion 10,95 g (13,0 ml) of the catalyst. In example 12 to test the reactor was loaded portion of the 10,95 g (15.0 ml) of the catalyst. In was still very good.

Example 13

A mixture of palladium acetate with lanthanum acetate and potassium acetate was dissolved in water rather than in acetic acid to obtain a catalyst which consisted of the following composition: 0.15 wt.% palladium, 0.34 wt.% lanthanum, 1.4 weight. % potassium. For testing in the reactor was placed a portion of 25.2 g (30,0 ml) of the catalyst. If you consider the low palladium content, 8% conversion of ethylene, as shown in table 2, it turns out pretty good.

Example 14

Niobium oxalate, used as a source of niobium, is not soluble in acetic acid. For this reason, pre-impregnation of the support 1 of niobium oxalate produced with the use of its aqueous solution. After drying media this last was soaked with a solution in acetic acid palladium acetate and potassium acetate. For testing in the reactor was placed a portion 11,04 g (14,0 ml) of the catalyst. The finished catalyst contained 0.81 wt.% palladium, 0.64 wt.% niobium and 3.1 wt.% potassium. Operational characteristics of the reactor were adequate at ~ 9% conversion and 84% selectivity, but this catalyst, as it turned out, lost activity faster than expected.

Examples 15 and 16

Calcium as a promoter was added VI the same weight percentage, as the barium in example 7. In each case used the carrier 2A. In example 15 for testing in the reactor was placed a portion 10,95 g (15,8 ml) of the catalyst. In example 16 for testing in the reactor was placed a portion 10,95 g (15,4 ml) of the catalyst. As can be seen from the results, summarized in table 2, none of the catalysts was not effective, but at a lower calcium content achieved higher conversion and higher selectivity. To improve the catalytic performance properties can also more regulation of calcium.

Examples 17 and 18

In accordance with the General procedure described above, was used to promoted with cerium catalyst (example 17) and promoted with zinc catalyst (example 18), and these metals was dissolved in acetic acid and drying produced at a temperature of 60oC in vacuum. In each case used the carrier 2A. The finished catalyst contained: example 17 - 0.80 wt.% palladium, 0.69 wt.% cerium, 2.8 wt.% potassium; case 18 - 0.81 wt.% palladium, 0.33 wt.% zinc and 2.9 wt.% potassium. In example 17 in the reactor for testing was placed a portion of the catalyst 10,96 g (15.6 ml). In example 18 was loaded portion 10,96 g (15.6 ml) of the catalyst. Testing of these catalysts prodenia promoter and restorative treatment. Cerium, in particular, showed very good initial activity.

Examples 19 and 20

The catalysts of examples 19 and 20 were prepared using the same carrier and in accordance with almost the same procedure as in the above examples 17 and 18, except that instead of cerium and zinc used lead and strontium. The finished catalyst of example 19 was included in the weight percent 0,81 palladium, 0,70 lead and 2.9 potassium. The finished catalyst of example 20 contained in the weight percent 0,80 palladium, 0.68 strontium and potassium of 2.7. In example 19 to test the reactor was loaded portion of the catalyst 11,71 g (13,2 ml). In example 20 was used portion of the catalyst 10,95 g (15,4 ml). As shown in table 2, promoted lead the catalyst was lost, as it turned out, the activity faster than expected, while promoted strontium catalyst showed low activity and poor selectivity.

1. The catalyst intended for producing vinyl acetate in the fluidized bed, characterized in that it is a catalyst corresponding to the formula Pd-M-A where M denotes barium, gold, lanthanum, niobium, cerium, zinc, lead, calcium, strontium, antimony or what about cooked almost inert carrier in the form of microspherical particles, in which the size of at least 50% of the particles are less than 10-4m (100 μm).

2. The catalyst p. 1, characterized in that the size of at least 75% of the microspherical particles of the carrier is less than 10-4m (100 μm).

3. Catalyst under item 1 or 2, characterized in that practically inert microspherical particles of the medium are selected from the group including silicon dioxide, zirconium dioxide, aluminum oxide and mixtures thereof.

4. The catalyst p. 3, characterized in that as an almost inert microspherical particles using silicon dioxide.

5. The catalyst PP.1-4, characterized in that as M using antimony.

6. The catalyst PP.1-4, characterized in that as M using gold in the absence of barium.

7. The catalyst PP.1-6, characterized in that the carrier is a mixture of virtually inert microspherical particles with a specific pore volume of 0.2 to 0.7 ml/g and a specific surface area of from 100 to 200 m2/g, and the sizes of at least 50% of these particles are less than 10-4m (100 μm).

8. The catalyst according to p. 7, wherein the specific pore volume is from 0.3 to 0.65 ml/g, UD is m (100 μm).

9. The catalyst PP. 1-8, characterized in that practically inert carrier obtained by mixing 80 to 20 wt.% water Zola, including almost inert microspherical particles, and from 20 to 80 wt.% solid practically inert material in the form of particles with formation water mixture, followed by spray drying specified water mixture, and calcining the above-mentioned particles to provide the above is practically inert carrier.

10. The catalyst p. 9, characterized in that the aqueous Sol is a Sol dioxide with a particle size of silicon dioxide from about 410-8to 810-8m (40-80 μm).

11. The catalyst PP.9-10, characterized in that the solid is practically inert material in the form of a particle is a silica with a small mikroporistogo or her absence, the specific volume of mesopores from about 1.5 to 0.25 ml/g and a specific surface area of from 80 to 200 m2/,

12. The catalyst PP.9-11, characterized in that the aqueous mixture is subjected to spray drying at 125-280oC, preferably 130-240oC.

13. The catalyst PP.9-12, characterized in that the spray dried particles, for example, is audica fact, that contains palladium in an amount of 0.1-5.0 wt.%, preferably 0.2 to 4.0 wt.% and most preferably 0.3 to 1.0 wt.%.

15. The catalyst PP. 1-14, characterized in that the alkali metal in an amount of not more than 10 wt.%, preferably in an amount of 0.1 to 8.0 wt.% and most preferably in an amount of 0.1-5.0 wt.%.

16. The catalyst PP.1-15, characterized in that it contains the component M in the amount of not more than 5.0 wt.%, preferably in an amount of 0.1 to 4.0 wt.% and most preferably in an amount of 0.1 to 3.0 wt.%.

17. The method of obtaining characterized in PP.1-16 catalyst aimed to produce vinyl acetate in the fluidized bed, comprising the impregnation of pre-cooked practically inert microspherical particles of the medium is practically free from organic solvent with an aqueous solution containing free from halides of a metal salt of palladium, the component M, as described above, and at least one alkali metal, followed by drying the impregnated microspherical particles of the medium.

18. The method of obtaining characterized in PP.1-16 catalyst aimed to produce vinyl acetate in the fluidized bed, including propeto least 50% of the particles less than 100 microns, the solution containing free from halides of a metal salt of palladium, the component M, as described above, and at least one alkali metal, followed by drying the impregnated pre-prepared media.

19. The method according to p. 17 or 18, where microspherical particles of the material of the carrier separately impregnated with an alkaline metal before drying media.

20. The method according to p. 19, where microspherical particles of the carrier is impregnated with an alkaline metal after impregnation of the carrier with a solution which contains free from halide salts of palladium and component M

21. The method according to PP.17-20 which further includes drying the catalyst at temperatures up to approximately 80oC.

22. The method according to PP.17-21, where the solution containing free from halide salt of palladium, the component M and at least one alkali metal is an aqueous solution containing no organic solvent.

23. The method of producing vinyl acetate, including the joint interaction of ethylene, acetic acid and oxygen in the gas phase in the presence of a fluidized bed of the catalyst obtained by the PP.17-22 or described in paras.1-16.

is lucetta in the fluidized bed and is characterized in PP. 1-16, or for use in the method according to PP.17-22, comprising a mixture of from 80 to 20 wt.% water Zola, including almost inert microspherical particles, and from 20 to 80 wt.% solid inert material in the form of particles with formation water mix, spray drying specified water mixture and calcining the above-mentioned particles with obtaining virtually inert carrier.

25. The method according to p. 24, where practically inert particles of water Zola is chosen from the group that includes silicon dioxide, zirconium dioxide, aluminum oxide and mixtures thereof.

26. The method according to p. 25, where practically inert particles of water Zola are silicon dioxide.

27. The method according to p. 26 where water Sol is a colloidal solution of silicon dioxide with a particle size of silicon dioxide from about 410-8to 810-8m (40-80 μm).

28. The method according to PP.26 and 27, where almost solid inert material in the form of a particle is a silica with a small mikroporistogo or her absence, the specific volume of mesopores from about 1.5 to 0.25 ml/g specific surface area of from 80 to 200 m2/,

29. The method according to PP. 24-28, where virtually inert solid is which is less than 10-4m (100 μm).

30. The method according to p. 29, where the size of at least 85% of the microspherical particles of the carrier is less than 10-4m (100 μm).

31. The method according to PP. 24-30, where almost solid inert carrier is a mixture of virtually inert microspherical particles, the specific pore volume ranging from 0.2 to 0.7 ml/g, specific surface area is from 100 to 200 m2/g and a size of at least 50% of these particles is less than 10-4m (100 μm).

32. The method according to p. 31, where the specific pore volume is 0.3 to 0.65 ml/g, preferably from 0.4 to 0.5 ml/g

33. The method according to PP.24-32, where virtually inert solid carrier has a specific surface area equal to from 110 to 195 m2/g, preferably from 120 to 195 m2/,

34. The method according to PP.24-33, where water mixture is subjected to spray drying at a temperature of from 125 to 280oC, preferably from 130 to 240oC.

35. The method according to PP.24-34, where the spray dried particles are subjected to calcination at a temperature of from 550 to 700oC, preferably from 630 to 660oC.

Priority points:

22.02.94 - PP.3, 4, 6 and 17;

20.01.95 - PP.1, 2, 5, 7-16 and 18-35.

 

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