Ethylene oxide production catalyst

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to a method of preparing ethylene oxide production catalyst containing silver deposited on alumina carrier originally having sodium and silicate ions on its surface. Carrier is preliminarily treated with aqueous solution of lithium salt at temperature below 100°C, after which at least 25% sodium ions are removed and replaced with up to 10 mln-1 lithium ions. Carrier is dried and then silver and promoters are precipitated on the pretreated and dried carrier.

EFFECT: achieved stability of catalyst.

7 cl, 11 tbl, 17 ex

 

The technical field to which the invention relates.

The present invention relates to silver catalysts for the oxidation of ethylene to ethylene oxide and, in particular, to receive the substrates or carriers of catalysts with improved properties, making the catalysts, which include the above-mentioned carriers, have increased usefulness.

Description of the prior art.

Among the methods for producing ethylene oxide is the oxidation of ethylene in the vapor phase with molecular oxygen using a solid catalyst, which includes silver on a carrier, for example, aluminum oxide. Many researchers have made efforts to improve the efficiency and productivity of a silver catalyst to obtain ethylene oxide. In U.S. patent No. 5051395 presents the analysis of such efforts previously undertaken by numerous researchers.

In U.S. patent No. 3962136, 4010115 and 4012425 describes the use of alkali metals such as cesium, as promoters to improve silver catalysts for production of ethylene oxide.

Among the many preceding information in this field includes information of U.S. patent No. 4007135 (see also the patent of great Britain No. 1491447)which describes the various silver catalysts for production of oxides of the ethyl is a and propylene, which include promoting amounts of copper, gold, magnesium, zinc, cadmium, mercury, strontium, calcium, niobium, tantalum, molybdenum, tungsten, chromium, vanadium and/or preferably barium in excess of any amount present in a fixed form in a pre-molded carrier in the form of impurities or binder (column 2, lines 1-15), a silver catalyst to obtain propylene oxide containing a promoting amount of at least one promoter selected from the group comprising lithium, potassium, sodium, rubidium, cesium, copper, gold, magnesium, zinc, cadmium, strontium, calcium, niobium, tantalum, molybdenum, tungsten, chromium, vanadium and barium in excess of any amount present in a fixed form in a pre-molded carrier in the form of impurities or binder (column 2, lines 16-34), and silver catalysts for production of ethylene oxide or propylene oxide, containing (a) a promoting amount of sodium, cesium, rubidium and/or potassium, and (b) magnesium, strontium, calcium and/or preferably barium in promoting amount (column 3, lines 5-8).

In U.S. patent No. 5057481 and related U.S. patent No. 4908343 it comes to silver catalysts for production of ethylene oxide, which include cesium and oxygen-containing anion of an element from groups 3b-7b.

In U.S. patent No. 3888889 describing the tsya catalysts, suitable for the oxidation of propylene to propylene oxide, which include atomic silver modified compound of element of group 5b and 6b. Despite the mention of using media, the examples are not given. The use of cesium is not mentioned.

In Europatent No. 0266015 and U.S. patent No. 4766105 considered a silver catalyst on a substrate, promoted with rhenium, and includes an extensive list of possible copromotion.

In U.S. patent No. 5102848 considered catalysts suitable for the production of ethylene oxide, which include media, impregnated with silver, on which there is at least one cationic promoter, for example, cesium, and promoter containing (i) a sulfate anion, (ii) the anion of fluorine and (iii) oxygen-containing anion of an element from groups 3b-6b, inclusive, of the Periodic table of elements.

In U.S. patent No. 5486628 describes a silver catalyst promoted with alkali metal, rhenium and rare-earth or lantanoides component.

In U.S. patent No. 5011807 is considered the catalyst for the receipt of ethylene oxide, containing silver, alkali metal, transition metal and sulfur on the media aluminum oxide.

The media, the most widely used in the past to obtain silver catalysts for production of ethylene oxide, were solid reorganizes the e materials for example, compounds based on aluminum oxide, silicon dioxide, titanium dioxide or combinations thereof. The carrier, which was given special preference is alpha-alumina, which may contain silicon dioxide.

In various patents focusing on pre-processing such media to improve their usefulness. In U.S. patent No. 5102848, for example, shows repeated flushing of alpha-alumina with deionized water having a temperature of 90°With, before deposition of the catalyst components. According to the same patent, the media was also washed with a solution of HF having a temperature of 25°C. In both cases is not stated, and has not been demonstrated the effect of washing medium on the stability of the catalyst.

In later U.S. patent No. 6103916 also shows multiple flushing media from the alpha alumina with water having a temperature of 90°With, before deposition of the catalytic components in the manufacture of a catalyst to obtain ethylene oxide.

The prior art discloses that the presence of sodium or lithium has a significant influence on the characteristics of a silver catalyst. The claims of the various patents, however, do not agree on the impact of these two alkali metals.

Known level is ehniki contradictory regarding the effect of sodium on the catalytic properties of silver catalyst. In several patents, for example, reveals the importance of the presence of a minimum number of Na on the surface of the carrier:

1. In U.S. patent No. 4740493 approved (see paragraph 1 and paragraph 5 of the claims)that the carrier must have at least 50 million-1soluble sodium ion.

2. In the first paragraph of the claims of U.S. patent No. 4414135 approved the advantage of the catalyst, which in addition to the Cs is at least 1000 million-1Na.

3. In the first paragraph claims Europatent No. 0247414 B2 disclosed a necessary condition for the presence of media, which includes at least from 0.08% to 2% of sodium. Moreover, it is specified that, along with K, or Cs in the composition of the impregnating solution of silver must be Na.

In contrast, in the claims of the following patents disclose the importance of reducing the number of surface sodium:

1. In U.S. patent No. 43681-44 argues that the best characteristics are obtained from the media, which can include not more than 0.07% Na.

2. In applications WO 00/15333, WO 00/15334, WO 00/15335 revealed improvement of the properties of the medium by reducing the concentration of dissociable compounds, in particular, sodium and silicon dioxide, with boiling deionized water. In the above-mentioned applications is disclosed that preference is given to decrease the concentration is Na tion and silicon dioxide on at least 5%.

In the method of removing Na preferred, the media repeatedly immersed in boiling water.

3. In U.S. patent No. 6103916 and Europatent No. 0937498 A1 States that the characteristics of the catalyst are improved in the case when the carrier is washed by boiling in clean water until the resistivity of the water does not reach values in excess of 10,000 Ohms·see

Li has repeatedly mentioned as an example of an alkali metal, which can be added to improve the selectivity of the catalyst. He was mentioned along with Na, K, Rb and Cs, and Cs was presented as the preferred alkali metal promoter. In a few cases, however, Li was added to Cs as copromotor, see, for example, U.S. patent No. 4272443, patent # US 4278562, U.S. patent No. 4212772 and Europatent No. 0384312 B1.

In Europatent No. 0624398 B1 discloses the addition of Li to the impregnating solution of silver together with other promoters: Cs, W and Na (example 2).

A few patents indicates that Li and Na have similar effect on the characteristics of the catalyst are:

1. In U.S. patent No. 4916243 discloses the use of combinations of Cs salt and salts of any other alkali metal.

2. In U.S. patent No. 4820675 discloses the use of combinations of Cs salt and salts of any other alkali metal. Adding Li to Cs was supplemented by the addition of Na, column and experiment 7-28, column 25.

3. U.S. patent No. 4212772 indicates that Na and Li are equivalent with respect to their impact on the lifetime and selectivity of the catalyst and their mixtures in any ratio, have a positive impact, column 2, line 49.

4. In applications WO 00/15333, WO 00/15334, WO 00/15335 revealed improvement of the carrier by removing "dissociable compounds" from its surface. These dissociable compounds include compounds of sodium, cesium and lithium.

Processing media Li before applying known and disclosed in the following documents:

1. In U.S. patent No. 5705661 revealed that the media is pre-processed by impregnation of Li and Cs, provided that the finished catalyst will contain at least 100 million-1Li. Pre-processing consisted of impregnation of the carrier with an aqueous solution containing carbonates as Li and Cs, with subsequent drying.

2. In Europatent No. 0716884 B1 reveals the advantage of the pre-preliminary deposition of the additive of at least one alkali metal, Li, or Cs. Preliminary preliminary deposition of the additive includes a vacuum impregnation medium for 3 min with subsequent drying medium at a temperature of up to 1000°C. the Number of pre-additive ranges from 10 million-1up to 5,000 million-1.

3. In U.S. patent No. 3563913 and No. 3563914 describe pre-impregnated alpha-alumina compound of lithium, such as lithium hydroxide, followed by drying before impregnation with silver.

4. In the application WO 00/15333 proposed leaching and ion exchange, along with several other ways to reduce the concentration of dissociable compounds, in particular, silicates. The hydroxide solutions of tetraethylammonium, ammonium acetate, lithium carbonate and barium acetate are mentioned as examples of washing and ion-exchange solutions. Examples showing the processing of the Li, not shown, and in the disclosure of the invention not mentioned or even suggested the possibility of using lithium salts as an alternative reagents.

In applications WO 00/15333, WO 00/15334, WO 00/15335 revealed that dissociable compounds that must be removed from the surface of the media, particularly the silicates are dissolved in the same solution in which is dissolved and Na. Thus, the determination of the dissolution rate Na is a direct determination of the solubility of other ions (WO 00/15335, page 4, line 1).

Summary of the invention

Despite the multitude of sometimes contradictory information pertaining to the known prior art, it was found that in the case of pre-treatment of the carriers with the removal of the surface of sodium and part of the substitute for his lithium, receive catalysts with improved performance, mainly with high resistance. This is completely different from the provisions of the known prior art, in which the influence of Na and Li is considered as two different problems.

Detailed description of the invention

The concentration of Na on the surface of the carrier may be higher or lower concentrations in the underlying layers. The number of surface Na may depend on the composition of the core material of the carrier, and the composition of the binder material and parameters of the annealing medium. Because of the active particles of silver are deposited only on the surface of the carrier, the chemistry of the surface influences the function of silver and has a profound impact on the characteristics of the catalyst.

We have found that the final characteristics of the catalyst to obtain ethylene oxide significantly improved in the case when Na ions on the surface of the media are partly replaced by Li ions at the stage of preliminary processing.

Replacement of sodium by lithium provides a surface containing Li ions and fully or partially devoid of sodium. The overall goal of this process is to remove at least 25% of the surface of sodium and in at least partial replacement of its lithium. Preference is given to removing at least 50% of the surface of sodium and naibors the e preferred to remove at least 90% of the sodium from the surface and partial replacement of his Li (up to 10 million -1in the acceptable variant 1 million-1up to 10 million-1).

An additional distinctive feature of this invention is to regulate the number of connections of silicon removed from the surface, i.e. in contrast to the prior art an essential condition is that the removal of sodium is not accompanied by a similar dissolution and removal of silicon. Silicon is added as a binder material, and its removal reduces the strength of the media. We have found that the removal of silicates does not improve the catalytic performance.

Silica and silicates are important components of the composition of the media. The carrier consists essentially of aluminum oxide, silicon dioxide and/or particles of aluminium silicate, which is shaped in the form of granules and which prokalyvayutsya at high temperature. Silicon dioxide or a silicate is added to the binder material that holds these particles in the final pellet form. Thus, it is assumed that the surface of the carrier are compounds of silicon, and a distinctive feature of the present invention is that pre-processing of the media should not lead to a significant removal of this binding material, i.e. the removal and replacement of sodium should not be associated with comparable removing connection is on the silicon.

The number of silicon compounds in the composition of the medium may vary within wide limits depending on the manufacturing method.

We found no Association between the rate of removal of surface sodium and rate of removal of silicates, in contrast to the information from the prior art. In fact, we have found that, in the case of prolonged washing at high temperatures, the ratio of deleted quantities Si/Na increases, and it does not have a fixed value, as stated in the prior art. We have found that this ratio can be reduced by lowering the processing temperature Li, i.e. at a lower temperature processing Li is removed only the minimum amount of silicates. The consequence is a lower ratio of deleted quantities Si/Na in solution. Thus, according to the present invention is mandatory implementation of the auxiliary pre-treatment at a temperature lower than 100°C, preferably lower than 80°and most preferably the temperature of the auxiliary pre-treatment should be lower than 70°C. According to the present invention, it is expedient that the processing of the media was carried out so that the mass ratio of Si/Na in the remote material was what the Eney than about 5.0, and preferably it is less than approximately 2.0. This is in contrast to technological operations prior art, where the ratio of Si/Na in the remote material often exceed 10.

The consequence of applying clean water to remove surface sodium is the removal of a significant part of the surface of the silicon. When using pure water setpoint removal of Na is achieved only in the case when the water is boiling or close to it. When this temperature is also removed a significant amount of silicates. On the other hand, when pure water is used at a temperature significantly lower than 100°With removal of sodium is rather limited and does not reach the set value even after repeated washing for several hours. Thus, processing of the media only with water is not effective at obtaining improved media.

The surface concentration of Na ions on the media, not subjected to the processing is the essential aim of treatment in accordance with the present invention. The concentration is determined by the manufacturer of the media by the test method acid leaching. The standardized method, acid leaching the sample carrier in a short period of time subject to leaching in the 30% solution and is now acid. The concentration of sodium, potassium, calcium and silicon in the final solution is determined by atomic absorption spectrophotometry (Varian AA-110) in the air-acetylene flame at a wavelength of 589 nm, respectively, and the 766.5 nm. According to an alternative variant, the quantitative determination is carried out by extraction of the solution in the spectrophotometer with induction plasma (spectral analysis of electro-optical photometer with induction plasma). Wavelengths for simultaneous determination of Al, Si, Na and K, respectively 394,40 nm, 212,41 nm, 589,59 nm and 766,46 nm.

The purpose of the present invention is to remove at least 25% of the surface concentration of Na, preferably at least 50% and most preferably at least 90% of the sodium and replacement remote sodium lithium in an amount up to 10 million-1, preferably in an amount of 5 million-1up to 10 million-1.

The amount of sodium removed from the surface, determined by analysis of the solution used for pre-processing.

Pre-treatment of the carrier can be any effective means. Presented below for illustrative purposes, the methods are acceptable means to achieve the goal of pre-processing:

1. The heat carrier in the solution, which includes the ol lithium. Processing by heating continues until the solution used for processing, not achieved the desired sodium concentration.

2. The mixing of the carrier in the solution, which includes a lithium salt, at room temperature or at elevated temperature. Mixing continues until the solution used for processing, not achieved the desired sodium concentration.

3. The pumping of the solution of lithium on the surface of media to be processed at room temperature or at elevated temperature.

4. Vacuum impregnation of the support with a solution of lithium with subsequent washing of the carrier water.

As a rule, I prefer the combination of two or more of the above methods in the course of one treatment.

The suitability of a solvent for pre-treatment depends on its ability as used to dissolve lithium salts, and the dissolution remove sodium ions without excessive simultaneous removal of silicate anions. For the implementation of pre-treatment is suitable conventional solvents such as water, alcohol or a mixture thereof.

It is important that the surface of the carrier remained of the remnant of the lithium counterion of the salt anion, which can affect the functioning of the catalyst. Examples of suitable with the lei lithium chloride are, the carbonate, nitrate, formate and lithium hydroxide. A suitable solution for the implementation of pre-treatment is an aqueous solution of lithium salts (from 0.001 to 1.0 N. N.). Preference is given to application of 0.005 N. of 0.5 n solution of lithium salts; the most preferred application of 0.01 N. - 0.1 G. of the lithium salt solution.

We have found that for optimum catalytic characteristics of Li should be replaced only part of the deleted Na. Thus, the preferred replacement Li not more than 50% removed Na (per mol). The most preferred replacement Li not more than 25% of the deleted Na. Typically, the finished catalyst contains less than 10 million-1Li.

After pre-processing of lithium carrier is dried to remove solvent from the pores of the carrier in preparation for impregnation with a solution of silver. An important condition, however, is rinsing the treated media (before or after stage drying) pure solvent before using it to obtain a catalyst.

By the end of the pre-treatment solution of Li in the pores of the medium is a solution containing both lithium and sodium, as well as other compounds which were removed from the surface of the carrier. A consequence of the drying medium is the deposition of these materials and surface contamination. T is thus, flushing media pure solvent after processing Li reduces the level of surface contamination and enhanced performance. For the final rinse instead of the pure solvent can be used a weak solution of Li.

Processing in order to remove sodium, according to the present invention differs from the different treatments with the purpose of the preliminary injection of additives or pre-impregnation, as described, for example in Europatent No. 0716884. In previous methods, the lithium admixture is added and precipitated on the surface of the carrier in addition to surface Na. According to the present invention is mandatory replacement and removal of sodium.

The drying medium may be carried out in vacuum or at atmospheric pressure. The carrier is dried at a temperature lower than 400°S; preferably at a temperature lower than 200°C. the Medium is most preferably heated to a temperature of 0-50°above the boiling point of the solvent to evaporate all of the solvent in the pores.

The present invention is preferred because it provides the following unique advantages:

1. The removal efficiency of sodium:

The removal of sodium according to the present invention is more efficient than in the washing water in the well known is the level of technology.

2. Given the removal of sodium:

The present invention is set to the predetermined level of removal of sodium. This specified level proportional to the surface concentration, as indicated by the results of the test method for acid leaching. In this regard, different carriers will have different target levels of removal of sodium. Water used in the prior art, has a limited ability to remove sodium and will not be able to delete a specified number of operations.

3. Adjustable deposition of lithium:

The prior art discloses the processing of media lithium without simultaneous removal of sodium. The consequence is an excessive amount of both alkali metals on the surface of the medium which will prevent the deposition of silver and adversely affect the durability of the catalyst. The present invention avoids this serious deficiency by removing sodium from the pores simultaneously with the deposition of lithium.

4. Removing unbound alkali metals:

In several versions prior art, when the media was treated with Li as a pre-additive, it is not washed after treatment. When drying Li salt and sodium, present in the solution inside the pores, was deposited on the surface. This large number of nespas is the R salts will interfere with the operation of the catalyst. The present invention is proposed stage rinse after pre-treatment with lithium to remove most of the unbound ions. Unbound are those ions that are not associated with a specific site on the surface of the carrier, and if they remain in the pores, this leads to the precipitation of salts on the surface.

5. Prevent the removal of silicates:

The present invention prevents excessive removal of silicon compounds simultaneously with the removal of Na. Silicates are necessary to ensure the strength of the media and their removal does not improve the catalytic performance.

6. Lower temperature drying:

The prior art discloses that the temperature of the drying medium can reach 1000°preference is given to temperatures of up to 600°C. Such a high temperature drying can cause the movement of sodium ions from subsurface layers to the surface, resulting a bad catalytic quality. The present invention discloses the advantage of much lower temperature drying to prevent the movement of sodium.

7. Check the resistance of the catalyst

The present invention represented by comparative examples, proving the claimed improved performance, in particular, the persistence of the pre-processed n is sites.

The catalysts corresponding to the present invention are more stable performance and higher selectivity upon receipt of ethylene oxide. As will be shown in the examples, the resistance of these catalysts is superior to the resistance of the catalysts to which the lithium components were added at the stage of impregnation of the silver catalysts produced using the media not exposed to processing, media processed only water, or carriers, which were subjected to preliminary processing lithium without simultaneous removal of sodium.

The preferred carriers are carriers containing mainly alpha-alumina, in particular, the media containing up to about 15% (wt.) silicon dioxide. Particularly preferred carriers have a porosity of about 0.1-1.0 cm3/g, preferably about 0.2-0.7 cm3/, Preferred carriers also have a relatively low surface area, i.e. about 0.2-2.0 m2/g, preferably 0.4 to 1.6 m2/g and most preferably 0.5 to 1.3 m2/t, according to the definition by the method of brunauer-Emmett-teller (BET). See J. Am. Chem. Soc. 60, 3098-16 (1938). The porosity is determined by the method of mercury porometry; see Drake (Drake) and Ritter (Ritter), Ind. Eng. Chem., Anal. Ed., 17, 787 (1945). The distribution of pores and pore diameters determine what about the results of measurement of surface area and apparent porosity.

The media, for their use in industrial production of ethylene oxide, it is desirable to give a geometrically correct form of pellets, beads, rings, etc. it is Desirable that the carrier particles have equivalent diameters in the range 3-12 mm and preferably in the range of 4-10 mm, which is generally comparable with the internal diameter of the tubes, which places the catalyst. The equivalent diameter is the diameter of the ball, having the same relation to the outer surface (i.e. neglecting the surface of the pores of the particles) to the extent that the particles of the used media.

Preferred catalysts obtained in accordance with the present invention contain up to about 30% (wt.) silver (in terms of metal)deposited on the surface and in the pores of a porous refractory carrier. The silver content in excess of 20% of the total mass of the catalyst, effectively, however, as a consequence, the catalysts become too expensive. The preferred content of silver (in terms of metal)of about 5-20% by weight of the total catalyst, and particular preference is given to silver content, comprising 8-15%.

In the composition of the catalyst corresponding to the present invention, along with silver, are the promoters, in particular, the critical number promotor component on the basis of the e alkali metal. The number of promoter-based alkali metal, in terms of alkali metal, does not exceed 3000 million-1by weight of the catalyst; preferably the catalyst contains 400-1500 million-1more preferably 500-1200 million-1the alkali metal by weight of the catalyst. Preferably the alkali metal is cesium, although can also be applied lithium, potassium, rubidium and mixtures thereof.

The optional option practical implementation of the present invention is the use of sulfur as a promoting component of the catalyst. Sulfur can be added to the solution used for impregnation of the catalyst carrier in the form of sulphate, for example, cesium sulfate, ammonium sulfate, etc. In U.S. patent No. 4766105 describes the use of sulfur-containing promoting agents, for example, in column 10, lines 53-60, and this disclosure of the invention included in the present description by reference. In the case of the use of sulfur preference is given its quantity (in terms of elementary) in the range from 5 million-1(wt.) up to 300 million-1(wt.), by weight of the catalyst.

The catalyst may also contain a fluorine-containing promoter in the amount (in terms of elemental fluorine) 10-300 million-1(wt.) by weight of the catalyst. Can be used ammonium fluoride, fluoride of an alkali metal etc.

Preferably silver add the carrier by immersing the carrier in an impregnation solution of silver/amine or the method of initial moisture. The liquid containing the silver penetrates into the pores of the carrier under the action of force absorption, capillary forces and/or vacuum. May be disposable or reusable impregnation with intermediate drying or without it, depending, in part, on the concentration of silver salts in solution. To obtain a catalyst with silver content within the preferred range, suitable impregnating solutions contain, as a rule, from 5% (wt.) up to 50% (wt.) silver, in terms of metal. Specific applicable concentration depends, among other factors, from the desired silver content, the nature of the medium, the viscosity of the liquid and the solubility of silver compounds.

Impregnation pre-treated carrier is performed in a traditional way. The media is kept in a solution of silver up until the entire solution is not absorbed by the media. Most preferably the dry pre-treated carrier is placed in a vacuum, and then introducing the solution of silver. Vacuum discharge only after all the granules media are covered by the solution, or when the liquid level is sufficient to cover the applicable number of media. Because of this, all the pores of the carrier are filled with an impregnating solution.

Impregnating solution, as already mentioned, is a RAS is a thief silver/amine; preferably such, as fully described in U.S. patent No. 3702259, disclosure of which is incorporated into this description by reference.

After impregnation any excess impregnating solution is separated and the carrier impregnated with silver and promoters, calcined or activated. In the most preferred embodiment, the practical implementation of the invention, the calcination is carried out, as described in state-owned U.S. patent No. 5504052, issued April 2, 1996, and at the same time pending application No. 08/587,281, filed January 16, 1996, the disclosure of which is incorporated into this description by reference. The calcination carried out by heating the impregnated carrier, preferably gradually, to a temperature in the range 200-500°C for a period of time sufficient to convert the contained salts of silver in metallic silver and to decompose organic materials and their disposal in the form of volatile components.

Impregnated carrier optional kept in an inert atmosphere at temperatures above 300°With throughout the entire process. Without binding themselves to theoretical calculations, we can assume that at temperatures of 300°and above the oxygen in large quantities absorbed amount of silver, where he provides tricatel the impact on the characteristics of the catalyst.

Inert atmospheres, optionally used in accordance with the present invention, are the atmosphere, practically free from oxygen.

An alternative method of annealing consists of heating the catalyst in a stream of air at a temperature not exceeding 300°S, preferably not exceeding 270°C.

The catalysts obtained in accordance with the present invention have improved characteristics, in particular, resistance to obtain ethylene oxide by oxidation of ethylene in the vapor phase with molecular oxygen. Typical conditions such processes include the reaction temperature in the range from about 150°With up to 400°typically from about 200°to 300°and pressure of the reaction in the range from 0.5 bar to 35 bar (0,05-3.5 MPa). The initial mixture of the reagents contain from 0.5% to 20% of ethylene and from about 3 to 15% oxygen, the remainder are relatively inert materials, including substances such as nitrogen, carbon dioxide, methane, ethane, argon, etc. in a single pass over the catalyst enters the reaction, as a rule, only part of the ethylene, and after separation of the desired ethylene oxide and removal of the respective purge flows and carbon dioxide to prevent the uncontrolled accumulation of inert substances and by-products, neproreagirovavshimi the materials are returned to the reactor for oxidation.

The following examples illustrate the invention.

Example 1

A. Obtaining a concentrated solution of the complex silver/amine:

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

The silver oxide - 834 parts

Oxalic acid - 442 parts

Deionized water - 2808 parts

The Ethylenediamine - 415 parts

The silver oxide was mixed with water at room temperature, followed by gradual addition of oxalic acid. The mixture was stirred for 15 min and at this stage the suspension of silver oxide black acquired gray-brown color of silver oxalate. The mixture was filtered and the solids washed with 3 l of deionized water.

The sample was placed in an ice bath and stirred while gradually adding Ethylenediamine and water (in the form of a mixture of 66%/34%) to maintain the reaction temperature is lower than 33°C. After complete addition, the whole mixture of Ethylenediamine and water, the solution was filtered at room temperature. Clear filtrate was used as a concentrated solution of silver/amine to obtain a catalyst.

b. Adding promoters:

Transparent concentrated solution was diluted with mixture of Ethylenediamine/water (66/34). In addition to diluted solution of silver hydroxide was added Cs and hydrosulfate am one for the preparation of the catalyst, containing 11% silver, 40 million-1sulfur and 800 million-1cesium.

C. the Impregnation of the catalyst:

150 g sample of the medium was placed in an apparatus for working under pressure with subsequent evacuation of the latter to a residual pressure of 50 mm Hg to 200 ml of a solution of silver/promoters with the adjusted composition was made in insulated flask. The pressure in the apparatus was raised to atmospheric and the contents of which were within a few minutes. The catalyst was separated from the solution. The catalyst was ready for roasting.

d. The calcination of the catalyst:

The annealing and deposition of silver induced by heating the catalyst to a temperature of decomposition of silver salts. This was achieved by heating in a furnace having multiple heating zones, in a controlled gas environment. The catalyst was loaded on the conveyor belt, which consisted in a furnace at ambient temperature. The temperature, as you move the catalyst from one zone to the next, gradually increased. The temperature was increased to 400°as catalyst were seven heating zones. After heating zones of the conveyor is passed through a cooling zone, where the catalyst was gradually cooled to a temperature lower than 100°C. the Total residence time in the furnace was 22 minutes

C. the catalyst Test:

The catalyst and is having experienced in the stainless steel tube which was heated in a bath of molten salts. A gas mixture containing 15% ethylene, 7% oxygen and 78% inert gas, mainly nitrogen and carbon dioxide was passed through the catalyst at a pressure of 300 pounds per square inch (206,7 MPa). The reaction temperature pre-set in order to achieve the performance of ethylene oxide 160 kg·h-1·m-3of the catalyst. After about a week of working with such low productivity the reaction temperature was increased to increase the productivity of ethylene oxide to 330 kg·h-1·m-3catalytic Converter.

Used catalysts represented catalysts with low sodium, made mainly of alpha-aluminum oxide and having the following characteristics:

Table 1
MediaMoisture absorption (ml/g)Surface analysis (m-1): (test method for acid leaching)
sodiumpotassium
And31,18141
In31,65749
30,489 5
Dthe 33.44612
F33,67814

Example 2

This example shows the lack of correlation between the dissolution rate of the surface of the sodium and the rate of dissolution of silicates:

Stage 1. The sample carrier And a weight of 300 g was placed in an apparatus for working under pressure with subsequent evacuation of the latter to a residual pressure of 50 mm Hg In the flask under vacuum, made 1500 ml of 0.02 n solution of lithium carbonate in water. When you are finished adding all of the solution pressure in the apparatus was increased to atmospheric and the contents of the flask were heated. The duration of pre-treatment at this stage was 15 minutes

Stage 2. The solution was removed and the flask was added 1500 ml of boiling a 0.02 n solution of lithium carbonate in water. Boiling the mixture was resumed and continued for 15 minutes This step was repeated twice.

Stage 3. After removal of the solution of lithium at the end of the last cycle, the media was added to 1500 ml of deionized water and boiling the mixture was resumed. Washing with water was repeated one more time.

Six samples of the liquid were weighed and analyzed for the content of soluble salts to determine the number of remote Na and Si (table 2):

Table 2
Cycle No.Salts that are removed from the media (m-1)The ratio of remote Si/Na
SiNa
1373,3110,03,4
2378,257,66,6
3383,744,28,7
4194,515,012,9
557,84,512,9
642,02,516,5

The above results show no relationship between the removal of Na and Si from the media.

Example 3

Repeated operations of example 2, with the difference that the treatment was applied only deionized water. The duration of boiling increased in order to compensate for the limited ability of clean water to remove a specified number Na. The analysis of the collected solutions were as follows (table 3):

Table 3
Cycle No.Salts that are removed from the media (m-1)The ratio remotely the Si/Na
SiNa
121,610,82
221,75,793,76
3of 19.03a 3.94,91
440,5of 5.058,02
523,952,1511,14
628,12,1413,16
719,341,2815,16

This example also demonstrates the lack of correlation between rd Na and silicates. It also shows that water does not provide delete the appropriate number of sodium without the simultaneous removal of a large number of silicates.

Example 4

This example is intended to illustrate that to remove a specified number Na, the number of remote silicates can be regulated by the temperature regulation processing.

Stage 1. 300 g of the sample carrier And having a surface concentration of Na 81 million-1, was placed in the apparatus for working under pressure with subsequent evacuation of the latter to a residual pressure of 50 mm Hg In the flask under vacuum, made 1500 ml of a solution of lithium chloride (0,02 N. p is the target of LiCl in water). When you are finished adding all of the solution pressure in the apparatus was increased to atmospheric and the contents of the flask was stirred at room temperature for 15 minutes the Solution was weighed and analyzed.

Stage 2. The solution was removed and the flask was added 1500 ml of fresh solution of LiCl. Stirring was resumed and continued at room temperature for 15 minutes the Solution was weighed and analyzed. The number of Na and Si extracted on the last two stages, summarized and used to calculate the total amounts that have been deleted from the media. Stage 2 was repeated as many times as needed to achieve a given level of Na removal (80 million-1Na).

Stage 3. After finishing the Li carrier was washed with deionized water at room temperature.

Stage 4, 5, 6: the same operations stages 1-3 were repeated at a temperature of 45°, 65°C to 85°and 100°C. After these treatments, the carriers were washed with deionized water at room temperature. The summarized results are presented in Table 4.

Table 4
ExampleThe solution used to remove NaTreatment temperature (°)Total time* (h)Remote of Na (m -1)Remote number Si (m-1)The ratio of Si/Na
4Awater1001661,89225,3of 3.64
4b0,02-N. LiCl253,561,81,80,03
4C0,02-N. LiCl451,75to 80.859,20,11
4d0,02-N. LiCl650,7580,7617,730,22
4th0,02-N. LiCl850,7582,4332,960,4
4f0,02-N. LiCl1000,2582,5045,480,55
*Total time (h)required to remove a given quantity Na (80 million-1).

As can be seen from the results of Table 4, the use of only water was relatively ineffective for removing Na, even with an excess of time contacting and led to excessive removal of Si.

Example 5

This example is intended to demonstrate that the destruction of a large number of silicates negatively affects the durability of the carrier. Present from bretania is designed to remove a minimum number of silicates and preserving the physical characteristics of the medium:

Stage 1: 300 g medium And processed in a manner similar to Example 2. At low temperature the water has a very low ability to dissolve the surface ions. Thus, in this example, used boiling deionized water. Water was removed every 15 min and replaced with a fresh portion of deionized water. Even at a temperature of 100°water has a limited ability to remove sodium to the specified level. After twenty cycles deleted quantity of sodium and silicon dioxide were respectively 74 million-1and 454 million-1.

Stage 2. 300 g of the carrier And processed in a manner similar to the above in stage 1. Instead of deionized water was applied a solution of lithium chloride (0,02 BC). At this stage, the operation was carried out at a temperature of 45°and at this low temperature, a solution of lithium was effective enough relative to the removal of sodium. After seven cycles deleted quantity of sodium and silicon were respectively 81 million-1and 9 million-1.

Stage 3. The processed media from stages 1 and 2 of this example were tested for crushing strength (hardness). The test was performed using an instrument CHATILLON (model UTSM). The table below shows that washing with deionized water was lowered strength of the medium due to excessive del the surface of silicates. In contrast, treatment of Li has no negative effects on the strength of the medium (table 5):

Table 5
MediaRemote number Na (m-1)Remote number Si (m-1)The crushing strength (lbs)
The sample is not exposed to processing0022
Water-washed7445418,9
Media treated with LiCl81921,4

Stage 4: the Processed media stages 1 and 2 of this example was tested for abrasion. The method used for testing the abrasion meets the ASTM (American society for testing materials) D-4058-81: "Standard test method for ATTRITION AND ABRASION OF CATALYSTS AND CATALYST CARRIERS" ("Standard method of testing CATALYSTS AND CATALYSTS CARRIERS, WEAR AND ABRASIVE WEAR")

The test results show that after the standard 30 min test loss from abrasion is higher after washing with deionized water. This indicates that the washing water decreases the strength of the carrier due to excessive removal of surface silicate. In ioproject this, processing Li has no negative effects on the strength of the medium (table 6):

Table 6
MediaRemote number Na (m-1)Remote number Si (m-1)Loss from abrasion, %
The sample is not exposed to processing008,6
Water-washed7445410,2
Media treated with LiCl8198,4

Example 6

The purpose of this example is to demonstrate the effectiveness of procedures for the handling of Li relative to the removal of surface Na without excessive removal of silicates. Such efficiency has provided the possibility of processing at room temperature, which also helped to reduce the ratio of Si/Na:

Stage 1. The sample carrier And a weight of 300 g was placed in an apparatus for working under pressure with subsequent evacuation of the latter to a residual pressure of 50 mm Hg In the flask under vacuum, made 1500 ml of a solution of lithium salts. When you are finished adding all of the solution pressure in the apparatus was increased to atmospheric and the contents of the flask was stirred at room is the temperature within 15 minutes The solution was weighed and analyzed.

Stage 2. The solution was removed and the flask was added 1500 ml of fresh solution of Li. Stirring was resumed and continued at room temperature for 15 minutes the Solution was weighed and analyzed. The number of Na and Si extracted on the last two stages, summarized and used to calculate the total amounts that have been deleted from the media.

Stage 2 was repeated as many times as needed to achieve a given level of Na removal.

Stage 3. After removal of the solution of the last cycle to the medium was added 1500 ml of deionized water and was further stirred at room temperature for 15 min in order to ensure that the solution in the pores free from salts extracted. This aqueous solution was also analyzed for salt content.

The experiment was repeated using various lithium salts, as shown in Table 7:

Table 7
ExampleThe solution used to remove NaTreatment temperature (°)Total time* (h)Remote number Na (m-1)Remote number Si (m-1)The ratio of Si/Na
6A (comparative water1001661,89225,3of 3.64
6b0,02-N. Li2CO3253,558,620,03
6s0,02-N. LiCl253,561,81,80,03
6d0,02-N. LiNO3253,555,21,70,03

It is obvious that the ratio of remote Si/Na is significantly lower at low temperature and remove Si minimized.

Example 7

The sample carrier And a weight of 300 g was impregnated under vacuum using 1500 ml of 0.01 n solution of lithium carbonate in water as in Example 2. After that, the media and the liquid was transferred into an addition funnel with a shirt and ensured the circulation of the solution of lithium through the layer of the device. The flow of solvent is continuously fed into the upper part of the funnel at a rate of about 15 l/h Stream of solvent with the same speed were taken through the lower part of the funnel and the solution level inside the funnel maintained at a height of approximately 1 inch (25 mm) above the level of the media. The shirt provides circulation of the hot liquid to maintain the temperature at the level of 85-90°C. After 1 h, the solution was decanted and with whom Bireli for analysis.

After that, the same pattern of media was treated with hot deionized water for washing solution remaining in the pores of the carrier at the completion of processing of Li. Circulation of hot water (90° (C) in the funnel supported in the same manner as in the processing phase Li. At the end of the additional hours the water was decanted and collected for analysis. The treated carrier was dried by placing it in an oven at a temperature of 150°at 10 o'clock

Analysis of the solution Li showed that the first merged solution Li was removed from the surface of the carrier 65 million-1of sodium. The results of the second analysis of the solution showed that it contained as Li and Na, and that the total amount of sodium removed during pre-processing, has reached 75 million-1.

Example 8 (comparative)

The sample carrier And a weight of 300 g was treated with deionized water, just as was done in Example 7. The total number of remote sodium 19.5 million-1.

Example 9

The sample carrier In a weight of 300 g was treated at a temperature of 65°From 0.02 N. solution of lithium hydroxide in water. The procedure was identical to the procedure shown in Example 4d. After that the processed media was twice washed with 1500 ml of deionized water at room temperature. The duration of each wash cycle, the water was 30 min, and at the end of the carrier was dried at te is the temperature of 150° C.

Example 10

The sample carrier With a weight of 300 g was treated at a temperature of 65°From 0.02 N. solution of lithium hydroxide in water. The procedure was identical to the procedure shown in Example 4d. After that the processed media was twice washed with 1500 ml of deionized water at room temperature. The duration of each wash cycle, the water was 30 min, and at the end of the carrier was dried at a temperature of 150°C.

Example 11

The sample carrier D weight of 300 g was treated at a temperature of 65°From 0.02 N. solution of lithium nitrate in water. The procedure was identical to the procedure shown in Example 4d. After that the processed media was twice washed with 1500 ml of deionized water at room temperature. The duration of each wash cycle, the water was 30 min, and at the end of the carrier was dried at a temperature of 150°C.

The solutions collected in Examples 9-11, were analyzed for the presence of Na and Si to determine the number of remote salts. The results are summarized in Table 8:

Table 8
ExampleMediaSalts that are removed from the carrier, mn-1The ratio of remote Si/Na
SiNa
In42590,54,5
10661956,9
11D781340,6

Example 12

Example 12A: Example 6 was repeated using media and 0.1 G. of a solution of LiCl in water; the treatment was carried out at room temperature. The number of remote Na amounted to 91 million-1.

Example 12b: Example 6 was repeated using media And and 0.02 n solution of HNO3in water at a temperature of 45°C. the Number of remote Na amounted to 79 million-1.

Surface treated media, 12A and 12b, analyzed by means of x-ray photoelectron spectroscopy (XPS). For comparison also analyzed the surface of the carrier (carrier A), not exposed to processing.

Conditions analysis
DeviceScanning XPS spectroscopy Quantum 2000 (Physical Electronics)
The x-ray sourceMonochromatic, A1α
The area under analysis1.4mm×0.2 mm
The exit angle of radiation45 degrees
Neutralization of the charge of electron and ion fluxes Low

Results

Table 9
The atomic concentration (atomic %)
MediaProcessingThe number of remote NaSurface concentration (XPS)
NaSi
The media Andnot processed01,73,4
The carrier 12A0.1 N. the solution of LiCl at a temperature of 25°911,02,25
The carrier 12bof 0.02 N. the solution LiNO3at a temperature of 45°790,83,4

This example, based on the results of x-ray photoelectron spectroscopy shows that pre-treatment of Li has been effectively remove a specified number of Na without changing the surface concentration of Si.

Examples 13-15

Samples are processed media was used to obtain a silver catalyst on a substrate for the epoxidation of ethylene. Thus, to obtain the catalyst, carried out under the exact details of the process of Example 1, used 150 g samples of the following media. After calcination the catalyst was tested with high performance (330 kg SW·m-3·h-1) to determine their relative stability (table 10):

Table 10
Example No.MediaThe sample was selected through
100 h200 h300 h400 h500 h600 h
13 comparativeAnd (raw)80,880,780,179,579,4
144C80,180,1an 80.2an 80.280,080,1
154fan 80.2an 80.2an 80.280,080,080,0

It is evident that the catalysts that use raw media, less hours than catalysts made with the media treated according to the present invention.

Example 16

Repeating Example 2, with the difference that it only includes two loop Li without washing water is th at the end of processing.

Analysis of dry processed media (media 16) showed that the solutions were removed 129 million-1sodium and that dry media included 57 million-1Li.

Samples of the carrier 16 with the weight of 150 g was used to obtain the Ag catalyst in accordance with the exact details of the process of Example 1. After calcination the catalyst was tested with high performance (330 kg SW·m-3·h-1) to determine its relative stability. Table 11 summarizes the test results and compared with the results of Example 15. In the latter case, the carrier was washed with water after treatment Li.

Table 11
Example No.MediaLi (m-1in the catalystThe sample was selected through
100 h200 h300 h400 h500 h600 h
164C2980,880,579,578,5
154f3,5an 80.2an 80.2an 80.280,080,0 80,0

This example shows that to obtain a higher stability characteristics of the catalyst need only a limited amount of Li. A consequence of the higher concentration of Li was getting lower catalyst stability. Therefore, a prerequisite, after pre-treatment media is the removal of Li in the pores, leaving only a limited number of Li on the surface of the carrier, i.e. up to 10 million-1Li.

Example 17

The sample carrier And a weight of 300 g was impregnated under vacuum using 1500 ml of 0.02 n solution of lithium carbonate in water as in Example 2. After that, the media and the liquid was transferred into an addition funnel with a shirt and ensured the circulation of the solution of lithium through the layer of the device. The flow of solvent is continuously fed into the upper part of the funnel at a rate of about 15 l/h Stream of solvent with the same speed were taken through the lower part of the funnel and the solution level inside the funnel maintained at a height of approximately 1 inch (25 mm) above the level of the media. The shirt provides circulation of fluid (25° (C) to maintain its temperature below room temperature. After 2 h, the solution was decanted and collected for analysis.

After that, the same pattern of media was twice treated with deionized water for washing down the astora, remaining in the pores of the carrier at the completion of processing of Li. The circulation of water at room temperature in the funnel supported in the same manner as in the processing phase Li. The treated carrier was dried by placing it in an oven at a temperature of 150°at 10 o'clock the Dried carrier was analyzed for the content of Li.

Analysis of the solution Li showed that the first merged solution Li was removed from the surface of the carrier 40 million-1sodium and 12 million-1of silicon. The results of the analysis of dry media showed that it contained 5.2 million-1Li.

1. The method of producing catalyst to obtain ethylene oxide, which includes silver on a carrier of alumina, a source having on its surface ions such as sodium and silicate involving pre-treatment of the carrier in an aqueous solution of lithium salt at a temperature lower than 100°With removal of at least 25% of the sodium ions with the replacement of up to 10 million-1lithium ions, drying the carrier, followed by deposition of silver and promoters on the surface of the pretreated and dried media.

2. The method according to claim 1, in which the carrier is treated with an aqueous solution of lithium salt at a temperature lower than 80°C.

3. The method according to claim 1, in which the carrier is treated with an aqueous solution of lithium salt at a temperature lower than 70°C.

4. The method according to claim 1, in which education is otany carrier is washed with water before using it upon receipt of the catalyst.

5. The method according to claim 1, wherein when removing sodium ions removal Si support below the level that would have a negative effect on the structural characteristics of the media.

6. The method according to claim 5, in which the weight ratio of remote Si/Na is 5.0 or less.

7. The catalyst for obtaining ethylene oxide obtained by the method according to claim 1.



 

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The invention relates to the field of chemical technology

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