The preparation method of catalyst for redox processes

 

(57) Abstract:

The invention relates to a process for preparation of the catalyst for redox processes. According to the invention the method comprises dry mixing the starting components, formation, hydrothermal and thermal treatment of the granules, and prior to forming by extruding the catalyst mass plastificator aqueous solution of boric acid or boric acid and surface-active substances (surfactants), or boric acid and ammonia, or boric acid, ammonia and surfactants at a given ratio of components and the ratio of solid : liquid (T:W), in addition, depending on the plasticizer spend the crop has wilted or dried extrudates in the specified mode, and the final heat treatment of the granules is carried out at 40-650oC. the use of surfactants, water-soluble nonionic surfactants containing the hydrophilic group-HE or-COOH, or Cho, or-NH2. The method allows to obtain a catalyst with high characteristics: reduced by 19 - 44% bulk density, increased 1.2 - 3 times the porosity, increased by 6 - 81% activity increase 2 to 3 times the performance of the process, to reduce on is whether the exclusion of the use of certain kinds of materials. 4 C.p. f-crystals, 3 tables.

The invention relates to a process for the preparation of cement-containing catalysts based on copper and Nickel for redox processes and can be used in chemical, petrochemical and metallurgical industries, in particular, in the processes of conversion of carbon monoxide, synthesis of alcohols WITH1-C4the decomposition of methanol, hydrogenation of fatty acid esters, deep oxidation, for example, aromatic hydrocarbons, ketones, purification of process gases from carbon monoxide, oxygen, and sulfur compounds, industrial waste gases from organic impurities, the exhaust gases of internal combustion engines and other processes.

In the development of production of catalysts can be traced to two trends: first, the increase in unit capacity installations preparation of catalysts, the second expansion of the range of commercial catalysts. The contradiction of these trends can be resolved by creating a generic and flexible technology that allows you to get on the same installation of several catalysts. Studies have shown that in some cases the replacement method of forming catalyst, such as tabletting is widely used contact. It is known that at the stage of forming laid or are developed and fixed such important characteristics of the catalyst activity, selectivity, porosity, specific surface area, mechanical strength, bulk density, degree of use of a unit volume of catalyst and other Molding by extrusion best provides the catalyst for listed properties.

From literature is known processes for the preparation of mixed type catalysts based on metal oxides, formed by extrusion of a paste-like mass. A number of studies devoted to obtaining molded oxide and aluminum hydroxide. Getting plastic materials (pastes) hydroxide and aluminum oxide by treatment with acid processing method, widely used in the manufacture of granular active alumina. Analysis of the known sources showed that the mineral acid, in particular boric acid may be used in some cases as a plasticizer, increasing the dispersion system, in others as a structural promoter, preventing the sintering of the particles of the material and thereby increase their resistance. Sometimes in the known methods together with barnabo as peptization, to some extent, improves the rheological properties of the material, or as a reagent precipitator. Surfactants used as builders for the development of porosity or get bidisperse patterns then. Research practice has shown that the selection of the surface-active substances, which, acting as a plasticizer and stabilizing agent in the molding process, did not weaken the properties of the catalysts is a problem that can be solved only in the course of experimental determination. This also applies to their optimal concentrations.

In catalyst production attempts have been made to create new or get the already known catalytic systems in a different form in the form of extrudates having a set of properties needed for successful use in industrial environments.

So, there is a method of cooking medicinklinik catalyst for carbon monoxide conversion by mixing the starting components, their annealing at 400oC for 6 h, added to the calcined mixture 3 9 wt. chromate zinc, moistening the mixture with distilled water to a moisture content of 25 - 35% and plasticization her in the 25oC for 0.5 h followed by molding and drying is dinani, comprising mixing the starting components with magnesia binder and an aqueous solution of high molecular weight colloid polyvinyl alcohol or hydroxypropylcellulose when the mass ratio of MgO PVA (2-5) 1, the resulting mass is molded, dried at 120oC for 1 h and calcined at 380oC, carrying a temperature rise rate of 20 to 30oC/h

Obtained by the above methods, the contacts have a low porosity is 35 to 50% and the mechanical strength of up to 1.0-1.2 kg/mm granules, low activity, due to the large number of input additives reducing the proportion of active component. In addition, the removal of the pellet weight plasticizer, such as polyvinyl alcohol, requires the creation of an oxidizing environment and high temperature.

Also known is a method of obtaining absorber for cleaning gases from sulfur compounds comprising the mixture within 2 h of oxides of zinc and magnesium with an aqueous solution of high molecular weight colloid, which is used as polyacrylamide, with respect to the magnesium oxide is 1:(6) is 300), then the resulting mass is formed, the extrudates are dried at 120oC for 1 h layer is not more than 7 cm with constant air circulation, temper ora significantly limits the possibility of its application.

The closest to the essential features is a method for preparing a catalyst for redox processes, including mixing the dry method the basic Nickel carbonate and/or dual core carbonate salts of copper and zinc aluminates of calcium and iron, molding, which includes two to three-fold compaction of the mass in the mill, the grinding compacted plates to grain and pressing it in the form or tablets, hydrothermal processing of pellets in the aquatic environment at a temperature of between 15 and 20oC to 70 100oC at a heating speed of 0.25 to 1oC/min and aged for 1 to 4 hours, a heat treatment (drying) granules 100 120oC.

Method tabletting (pressing) used in this method is time-consuming, multistage and continuous process that requires the use of manual labour, a considerable amount of electricity and additional equipment, which quickly wears out and fails. For the implementation of the tabletting necessary to conduct repeated transactions seals dry mass of catalyst in the mill, which ultimately reduces the performance of the production unit is raised, which reduce the mechanical strength. In addition, the introduction of the catalyst mass of graphite (up to 2 to 3.5 wt.) as the solid lubricant reduces the concentration of active components and stabilizers.

Hydrothermal processing, which is the main stage where the heterogeneous ion exchange is the formation of the phase composition of the catalyst, this method must be implemented in strict regulation and control of the rate of temperature rise of not more than 0.25 to 1oC/min

The temperature of the heat treatment (drying) 100 120oC, are chosen from considerations prevent decomposition of the resulting heterogeneous ion exchange occurring during the TRP complex salt with the atomic distribution of copper, zinc and aluminum and sufficient only to dry the catalyst in a laboratory or workshop conditions small experimental batches were insufficient for effective drying of commercial batches of catalyst.

The catalyst obtained in this way has a high bulk density of 1.6 to 1.8 kg/l (tablet 6x4) and 1.3 1.5 kg/l (ring 15 x 7 x 10) and a relatively low porosity in activated condition 42 of 46% (tablet) and 52 58% (ring) result of the method of its production.

The aim of the invention is to remedy these disadvantages.

In accordance with the purpose of the task was to create such a preparation method of catalyst for redox processes, which would provide the catalyst was extruded in the form of improved properties, in particular reduced bulk density and increased porosity and consequently increased the activity and efficiency of the catalyst in the growth rate per unit volume of catalyst. The invention is also improving the performance of the method and the possibility of resource and energy saving in the production of the catalyst.

The preparation method of catalyst for redox processes should include a dry mixture of basic Nickel carbonate and/or dual core carbonate salts of copper and zinc with calcium aluminates, molding, hydrothermal and thermal treatment of the granules.

The task is solved in that before forming the catalyst mass by extruding implement plasticization using as a plasticizer of an aqueous solution of boric acid or boric acid is the following ratio of components: boric acid ammonium surfactant, equal in wt. (0,1 3) (1,8 4,7) (0,01 - 0,05), and the solid liquid ratio equal to 1 (0,18 0,23), and using the plasticizer that does not contain ammonia, after extrusion spend the crop has wilted granules in air or air-humid environment, and the use of a plasticizer containing ammonia, after extrusion are drying the pellets in a stream of air, their final heat treatment is carried out in the temperature range 40 650oC.

In order to better implement the method and optimum rheological properties of the catalyst mass as surface-active substances are used water-soluble neionogennye surfactant containing a hydrophilic group-HE or-COOH, or Cho, or-NH2.

In addition, to optimize the preparation of extrudates and increase their strength characteristics of the crop has wilted granules in air is carried out at ambient temperature for 49 96 hours

Also to improve the performance stage of the crop has wilted granules in the air-humid environment is carried out at a temperature of 40 60oC for 8 to 24 hours

The performance stage is significantly increased if the drying of the pellets is carried out the first mass with the set of optimal rheological properties (plasticity, viscosity limits the fluidity and thereby ensure its formemost according to the invention before forming by extruding implement plasticization by adding in obtained after mixing the dry weight of the plasticizer. The plasticizer in this case is an aqueous solution of boric acid or boric acid and surfactant, or boric acid and ammonia, or boric acid, ammonia and surfactants with the proposed ratio of components.

Boric acid as a plasticizer, the proposed method is also used in a new capacity as a moderator of the setting of the aluminates of calcium, which is extremely important for this catalytic system. In the result of the impact of extended time during which the plasticized mass retains its rheological properties, for 1.5 to 2 h, which has an impact on the effectiveness of the overall process. So, when using as aluminates of calcium taluma having a predominant content of monoaluminate calcium Al2O3and quick-setting 127Al2O3, plasticized mass is capable of rapidly (within 20 to 30 minutes) to lose its formability, which prevents its further use.

2. The choice is due, primarily, to the fact that surfactant, showing its primary properties, namely the reduction of surface tension, uniform wetting of the material, preventing the adhesion of the dispersed particles, etc. should not degrade the properties of the catalyst, in particular not to reduce its activity or selectivity. Observed with the introduction of surfactants to improve formemost caused by increasing the strength of the adsorbed hydrated membranes on the surface of the particulate moldable mass. The effectiveness of the action entirely depends on the nature and concentration of surfactant. Reinforcing the action of the surfactant due to the formation of a strong coagulation and condensation links in places of contact of the particles of material due to adsorption modification of their surface.

Ammonia, which is a component of the plasticizer improves the rheological properties of the moldable mass. But the mechanism of its effect in this case is that the ammonia is not only dissolves due to the complexation of water-insoluble basic carbonate salt, but, as it turned out, translates them into the melt. However, in order to gage the molding, according to the proposed invention, low concentrations of ammonia, allowing to achieve only a superficial "melting" of the salt crystals, which beneficially affects the fluidity within moldable mass. Fused salt crystals after molding mass cocrystallized provide the mechanical strength of the extrudates, equal to 0.4 to 0.8 kg/mm o granules, while their mechanical strength when using a plasticizer that does not contain ammonia, 0.15 0.25 kg/mm o granules. This difference was maintained throughout the process and is at the end of Mach 3.3 kg/mm o granules and 2.1 kg/mm o granules, respectively.

Rheological properties of the catalyst mass and, consequently, its formability can be adjusted also by changing the humidity of the material. The proposed solid liquid ratio (T W) equal to 1 (0,18 0,23), allows to achieve the best results and to optimize the molding process.

Since the mechanical strength of the extrudates, component 0,15 0,25 kg/mm o granules, is insufficient to prevent their destruction at the promotion of the granules of the catalyst in the process, spend their crop has wilted. When the crop has wilted happens what about in air at ambient temperature for 48 to 96 h, that gives the opportunity to optimize the process and reduce energy consumption 40 60oC for 8 to 24 hours, resulting in improved process performance by reducing the amount of catalyst that are in process at a time.

The mechanical strength of the extrudates, component 0,4 0,8 kg/mm o granules (using plasticizer containing ammonia) allows directly drying the pellets in a stream of air, as in this case, the strength of granules is provided by cocrystallization basic carbonate salts. This results in reduced time technological stage, during which the strength of the extrudates (crop has wilted 24 to 96 h, drying 8 10 h). To reduce the duration of the drying granules up to 1 to 3 hours, and thereby increasing the performance of this stage according to the invention is proposed to carry out at a temperature of 80 120oC.

Replacement method of molding provides obtain granules with a more porous structure and a lower bulk density, as well as less intensive mechanical stress during extrusion (as opposed to compression) less change the structure of the material, in particular krueperi the awn granules increases with decrease in the ratio of solid liquid (T W), i.e. if you increase the amount of fluid, and in the lengthening of the hydrocarbon radical of a surfactant included in the composition of the plasticizer.

It should be noted that the introduction of fluid (plasticizer) in dry mixture of the catalyst components "launches" the mechanism of heterogeneous ion exchange already at the stage of plasticization, which takes place both in the Z-mixer, and the granules until they are dry crop has wilted or dried, which gives the possibility in the future on the stage hydrothermal processing does not comply with a soft and strictly controlled heating mode water environment between 15 and 20oC with a speed of 0.25 to 1oC/min Therefore, the proposed method stage TRP carried out at a temperature from 50oC (without waiting for pre-cooling of the working fluid) and the system is heated with greater speed, for example 1,3 - 1,5oC/min. this circumstance allows to improve the performance stage, to reduce energy consumption and reduce waste heat.

Depending on the desired properties, conditions for activation and use of the catalyst in each specific process in the proposed method provides the possibility of obtaining a catalyst with specified characterise temperature 40 650oC. Varying the heat treatment conditions may be adjusted in a specified direction porosity, specific surface area, strength and bulk density of the catalyst. Different degree of "depth" heat treatment can also be specified to change the phase composition of the catalyst. The effect of partial sintering, which is accompanied by heat treatment of the pellets at high temperatures 600 650oC), also directed changes the strength and porous structure of the catalyst, destroying the delicate pores and promoting the specific content of macropores, necessary for a number of processes in organic synthesis. It should also be noted that the possibility of carrying out heat treatment of the catalyst at low temperature (40 to 90oC) allows you to save electricity and steam, as this operation can be performed using exhaust steam.

Thus, the optimal combination of different plasticizers, techniques and conditions of the stages of the plasticizing, extruding, wilting or drying, hydrothermal and thermal treatment allowed in the proposed way to achieve a necessary and controlled set of properties of the catalyst for a wide range of technological processes.

The energy efficiency is also at the stage of hydrothermal and thermal treatment of the catalyst due to the optimization of these stages.

In addition to reducing (or eliminating) the use of certain types of expensive and scarce equipment, the ability resource is manifested in the fact that there is no need in graphite, in production for some processes the catalyst with a high content of active components (Nickel and copper), thanks to greater use per unit volume of the catalyst, due to the increased volume activity.

The bulk density of the catalyst, PR is Isadora increased 1.2 to 3 times, the catalyst is in the activated condition 1.3 1.4 times.

The development of the proposed technology catalyst with high catalytic performance, makes a significant contribution to improving the efficiency of a number of technological processes in various industries. For example, the process of conversion of carbon monoxide with water vapor ammonia should be noted that the decrease in the bulk density of the catalyst only 15% saves about 20 tons of catalyst per 1 Converter ammonia plant with a capacity of 1360 tons/day. At lower due to the high activity of the catalyst in Congaz concentration WITH 0.1% of the amount of purge gases is reduced by 10% and the performance of the ammonia increases by 0.7 1% i.e. 7 to 10 tons of ammonia per day.

Hence it becomes clear how much value the efficiency of the catalyst to improve the economic performance of the process. Along with this it should be emphasized extensive use of molded megynkelly catalysts on the basis of aluminates of calcium in the processes of environmental catalyst for solving environmental problems.

Example 1. Cooked the 50oC and dissolved under stirring for 15 20 min 29 g of boric acid, then the solution is cooled to ambient temperature. The ready solution of the plasticizer with the concentration of H3BO30.1 wt. dispense in a homogeneous catalyst mixture.

In the Z-mixer download 98 kg dried and disaggregated dual core carbonate salts of copper and zinc (composition in terms of oxides, wt. CiO 57,0; ZnO 43,0), 30 kg of calcium aluminates. The mixture was thoroughly stirred until a homogenous mixture for 30 min, after which the dry mixture is moistened with the solution prepared plasticizer (29 l), the ratio of the solid liquid (T W) is 1 to 0.23. The mixture continued to stir for another 8 to 10 minutes to obtain a plastic mass. Then plasticized mass ekstragiruyut to screw formulatea. The extrudates coming onto the baking sheets, put the crop has wilted in air at ambient temperature ( 20oC) for 48 hours Then provyalennuyu extrudates loaded in a perforated basket, placed in a tank with condensate having a temperature environment ( 20oC), heated to 90oC for 1 h (heating rate of 1.16oC/min, then kept at this pace the zines stream of air at a temperature of 180oC for 6 h

The resulting catalyst has the following chemical composition (in terms of oxides) wt. the copper oxide 40,0; zinc oxide 30,0; aluminates of calcium else; bulk density of the catalyst is 1.05 to 1.25 kg/DM3; mechanical durability (index, tensile splitting strength, which is determined on acute 0.1 mm "knife" semi-automatic device design Vniineftehim) 1.5 to 1.9 kg/mm o granules; total porosity 28 36% of the total porosity of the activated catalyst 60 72%

The catalyst was tested in the process of conversion of carbon monoxide with water vapor with overheating (change to 8 h): 225 200 260 320 400 200 - 225oC when the following shifts: 3 1 1 1 1 1 1 (shifts), respectively.

The test is carried out in a flow reactor with a volume of 400 cm3the catalyst straws with a diameter of 5 mm, a length of 4 to 15 mm test Conditions: volumetric rate of gas flow 6000 h-1the pressure of 2.8 MPa, the ratio of the vapor/gas is 0.6, the composition of the source gas, about. 2 5; H254 56; CO216 20; CH4+ Ar no more than 1.0; N2the rest of it. About the activity of the catalyst is judged by the residual CO content in Congaz.

Testing of the catalyst in the methanol synthesis process is carried out in a flow reactor with a volume of 5 cm3: atur 250oC, the pressure 8,0 25 MPa, flow rate of gas 40000 h-1the composition of the source gas, about. FROM 16 TO 18; CO26 8; N250 57; CH4+ Ar no more than 1.0; N2the rest of it. The catalyst activity is the performance of the process, i.e. the removal volume of methanol, 1 h per unit volume or unit mass of the catalyst.

Testing of the catalyst in the synthesis of butyl alcohols is carried out in a flow type reactor with a volume of 100 cm3the catalyst fractions 2 to 3 mm, at a temperature of 190 to 230oC, space velocity of the raw material 2 5 h-1the pressure of 28.0 MPa. Raw material is a mixture of products of propylene hydroformylation obtained in the industrial reactor. About the activity of the catalyst is judged by the performance of the process, i.e., the amount of butyl alcohol obtained in 1 h per unit volume of catalyst.

Testing of the catalyst in the decomposition of methanol is carried out in a flow type reactor with a volume of 0.5 cm3the catalyst fraction 0,4 0,63 mm, at temperatures of 200, 250, 270, 300, 350 and 400oC, space velocity of the raw material mixture consisting of about 20. helium and about 80. vapors CH3HE - 5500 h-1, a pressure of 0.1 MPa. About the activity of the catalyst in this process is judged by the degree of radloactively catalyst, as well as the conditions and the results of his tests are presented in table.1, 2 and 3, respectively.

The method of preparation of the catalyst according to the invention are presented in examples 1 to 9, prototype method in example 10, in examples 11 and 12 ways using techniques ed. St. N 926822 and 874134 respectively.

Example 2. The method is carried out as in example 1, but with the difference that for the preparation of plasticizer in 28, 42 l condensate dissolved 580 g of boric acid and 2.9 g of triethylene glycol. The ready solution of the plasticizer with the ratio of boric acid triethylene glycol, equal to 2,0 0,01, dispense in a homogeneous catalyst mixture. The obtained extrudates provalivajut on trays at 40oC in the air-humid environment for 24 h, and the final heat treatment of the catalyst is carried out at 550oC for 5 h

The bulk density of the catalyst is 0.85 1.05 kg/DM3, mechanical strength index of tensile splitting strength of 0.8 to 1.2 kg/mm granules, the total porosity 54 62 total porosity of the activated catalyst 56 64 (PL.2).

The results of the testing of the catalyst in the processes of conversion of carbon monoxide with water vapor, methanol synthesis and butyl alcohols, methanol decomposition predanie plasticizer in 28,84 l condensate dissolved in 145 g of boric acid and 14.5 g of ethylene glycol. The ready solution of the plasticizer with the ratio of boric acid ethylene glycol, 0.5 to 0.05, is metered into the catalyst mixture. The obtained extrudates provalivajut in the air damp conditions at a temperature of 60oC for 8 h, the final heat treatment of the catalyst is carried out at 650oC for 5 h

The bulk density of the catalyst is 0.9 1,10 kg/DM3index of tensile splitting strength of 0.9 to 1.3 kg/mm o granules, the total porosity 50 58 total porosity of the activated catalyst 52 60

The test results of the catalyst are presented in table.3.

Example 4. The method is carried out as in example 1, but with the difference that for the preparation of plasticizer in 28,83 l condensate dissolve 29 g of boric acid and 145 g 8% polyacrylamide gel. The ready solution of the plasticizer with the ratio of boric acid polyacrylamide, 0.1 0.04) was metered into a homogeneous catalyst mixture. The obtained extrudates provalivajut in air at ambient temperature ( 20oC) for 96 h, the final heat treatment of the catalyst is carried out in soft conditions, this is still wet granules after stage TRP drums with open lids set in a room with CLASS="ptx2">

The bulk density of the catalyst is 1,20 1,40 kg/DM3index of tensile splitting strength of 1.5 to 2.1 kg/mm o granules, the total porosity 24 34% of the total porosity of the activated catalyst 60 70%

The test results of the catalyst are presented in table.3.

Example 5. The method is carried out as in example 1, but with the difference that for the preparation of plasticizer in the reactor with a stirrer and a steam jacket filled 21,26 l condensate is heated to a temperature of 50oC and dissolved with stirring, 24 g of boric acid, then the solution is cooled to 20oC and poured 3.0 l 25% ammonia water (2,721 kg of ammonia water containing 680,2 g of ammonia) and stirred. The ready solution of the plasticizer with the ratio of boric acid ammonia 0.1 2,83, dispense in a homogeneous catalyst mixture.

In the Z-mixer download 98 kg dried and disaggregated basic carbonate salts of copper and zinc (composition in terms of oxides, wt. CuO 57,0; ZnO 43,0) and 30 kg of taluma, mix thoroughly until a homogenous mixture for 30 min, then the mixture hydrate prepared by the plasticizer, the ratio of the solid liquid (T W) is 1 0,187, stirred for another 7 to 10 minutes to get plastinochnoy dryer, where at first the tape dried active ventilation at ambient temperature and the second is dried at a temperature of 80oC for 3 hours and Then the catalyst is loaded in a perforated basket, placed in the capacity of a condensate having a temperature natural cooling from the previous cycle, but not above the 50oC, heated to 90oC for half an hour (heating rate of 1.33oC/min) and maintained at this temperature for 2 hours Total time TRP is 2.5 hours the pellets thermoablative in baskets stream of air at a temperature of 140oC for 8 h

The composition of the obtained catalyst (in terms of oxides, wt. the copper oxide 40,0; zinc oxide 30,0; Calum else. The bulk density of the catalyst is 1,20 1,40 kg/DM3mechanical durability (index of tensile splitting strength) of 1.6 to 2.8 kg/mm o granules, the total porosity of 22 to 30% of the total porosity of the activated catalyst 58 68%

The test results of the catalyst are presented in table.3.

Example 6. The method is carried out as in example 5, but with the difference that for the preparation of plasticizer in 17,75 l condensate dissolved 690 g of boric acid, 23 g of glycerin, add 5.0 litres of 25% ammonia water (4,535 kg solution aerin, equal 3,0 4,7 0,01, dispense in a homogeneous catalyst mixture. The ratio of the solid liquid (T W) is 1 0,18.

The resulting extrudates are dried at the second ribbon belt drier at a temperature of 100oC for 2 h

The bulk density of the catalyst is 1,25 1,50 kg/DM3index of tensile splitting strength of 1.6 3.3 kg/mm o granules, the total porosity of 20 to 28% of the total porosity of the activated catalyst 56 66%

The test results of the catalyst are presented in table.3.

Example 7. The method is carried out as in example 5, but with the difference that for the preparation of plasticizer in 23,16 l condensate dissolved 25 g of boric acid, 2.5 g of xylitol, add 2.0 l 25% ammonia water (1,814 kg of a solution containing 453,5 g NH3). The ready solution of the plasticizer with the ratio of boric acid ammonia xylitol equal to 0,01 0,1 1,8, dispense in a homogeneous catalyst mixture. The ratio of the solid liquid (T W) is 1 of € 0.195. The extrudates are dried at a temperature of 120oC for 1 h Final heat treatment of the granules is carried out at a temperature of 270oC for 3 h

The bulk density of the catalyst is 1.05 to 1.25 kg/DM3index tensile rascal is Aligator presented in table.3.

Example 8. The method is carried out as in example 5, but with the difference that for the preparation of the plasticizer in each holding 21.25 l condensate dissolved 24 g of boric acid and 2.4 g of tartaric acid, add 3.0 l 25% ammonia water (2,721 kg ammonia solution containing 680,2 g NH3). The ready solution of the plasticizer with the ratio of boric acid ammonia tartaric acid 0.1 2,83 0,01, dispense in a homogeneous catalyst mixture. The ratio of the solid liquid (T W) is 1 0,187.

In the Z-mixer download 98 kg dual core carbonate salts of copper and zinc, 3.5 kg of basic Nickel carbonate and 28 kg of alumina (ALUMIN - high-alumina cement aluminothermic production). The extrudates are dried at a temperature of 80oC for 3 h

After stage TRP catalyst thermoablative 400oC for 8 h

The composition of the obtained catalyst, wt. the copper oxide 40,0; zinc oxide 30,0; Nickel oxide 2,0; ALUMIN else.

The bulk density of the catalyst is 0.95 1.15 kg/DM3index of tensile splitting strength of 0.85 1.6 kg/mm o granules, the total porosity 58 66% of the total porosity of the activated catalyst 60 68%

The test results of the catalyst are presented in table atora (example 8) in each holding 21.25 l condensate dissolved 24 g of boric acid, 2.4 g of glucose and add 3.0 l 25% ammonia water. The ready solution of the plasticizer ratio of boric acid, ammonia, glucose, 0.1 2,83 0,01, dispense in a homogeneous catalyst mixture. The ratio of the solid liquid (T W) is 1 0,187.

In the Z-mixer load (example 1) 98 kg dual core carbonate salts of copper and zinc and 30 kg of calcium aluminates.

In forming plasticized mass screw formulatea extrudates using a cutting device to cut into pieces with a length of 3 to 5 mm and rolled on the plate granulator in the balls with a diameter of 3 to 5 mm

The composition of the obtained catalyst, wt. the copper oxide 40,0; zinc oxide 30,0; aluminates of calcium else.

The bulk density of the catalyst is 1.25 to 1.45 g/DM3index of tensile splitting strength of 1.6 2.8 kg/mm o granules, the total porosity of 22 to 30% of the total porosity of the activated catalyst 58 68%

The test results of the catalyst are presented in table.3.

Example 10 (the prototype). In the Z-mixer download 98,0 kg dual core carbonate salts of copper and zinc (composition in terms of oxides, wt. CiO 57,0, ZnO 43,0), 30.0 kg of calcium aluminates and 3.5 kg of graphite. The mass is thoroughly mixed to one of the m received the tablet is subjected to hydrothermal treatment, for which they are loaded into the container, pour 80 l of water and carry out the hydrothermal treatment program is heated from 20 to 90oC for 1 h 10 min, i.e., the heating rate is 1oC/min, and then maintained at this temperature for 1 h 50 min Total time TRP is 3 hours and Then the catalyst pellet is dried at 120oC for 5 h

The composition of the obtained catalyst (in terms of oxides), wt. the copper oxide 40,0; zinc oxide 30,0; aluminates of calcium else. The bulk density of the catalyst is 1,60 1,80 kg/DM3, mechanical strength, determined by crushing the ends tablets 80 130 MPa (800 1300 kg/cm2), the index of tensile splitting strength of 2.0 to 2.5 kg/mm o granules, the total porosity 18-24% of the total porosity of the activated catalyst 46 - 52%

The test results of the catalyst according to the method prototype is presented in table.3.

Example 11 (comparative, using a receiving method according to ed. St. N 926822).

The method is carried out as in example 4, but with the difference that, as a plasticizer use zinc chromate (3 kg chromate zinc, i.e., 3% by weight calcined at 900oC catalyst).

In the Z-mixer download 93,5 kg dual core carbon is min, then the obtained dry mixture is moistened 29 l condensate. The ratio of the solid liquid (T W) is 1 to 0.23. After stage TRP granules thermoablative at 140oC for 8 h

The composition of the obtained catalyst (in terms of oxides), wt. the copper oxide 38,2; zinc oxide 30,1; chromium oxide 1,7; aluminates of calcium else.

The bulk density of the catalyst of 1.1 to 1.3 kg/DM3index of tensile splitting strength of 0.4 to 0.8 kg/mm o granules, the total porosity of 30 to 40% of the total porosity of the activated catalyst 60 70%

The test results of the catalyst are presented in table.3.

Example 12 (comparative, using a receiving method according to ed. St. N 874134).

The method is carried out as in example 4, but with the difference that as the plasticizer used 0,08 aqueous solution of polyacrylamide (290 g 8% polyacrylamide gel on 28,710 l condensate).

In the Z-mixer download source components for the preparation of the catalyst in the composition and quantity as in example 1. After thorough mixing in a homogeneous catalyst mixture is metered 29 l prepared plasticizer. The ratio of solid liquid (T W) is 1 to 0.23. Otherwise, the process is carried out n is 1.0 to 1.5 kg/mm o granules, the total porosity of 24 - 34% of the total porosity of the activated catalyst 60 72%

The test results of the catalyst are presented in table.3.

From the data given in table.2, it is seen that the catalyst according to examples 2, 3 and 8 is sharply reduced bulk density, it is mainly a consequence of the conditions of the heat treatment of the catalyst at a temperature of from 400oC) due to the removal of volatile H2And CO2. From specified causes depends on the reduction of its mechanical strength and an increase in the total porosity. It is known that "working" the porosity of the catalyst is manifested in its activated state, so for comparison, in adequate conditions important characteristics of this catalyst was subjected to an activation current is converted gas at a pressure of 0.1 MPa, a temperature of 250oC and flow rate of 500 h-1.

From the data table. 3 characterizing the activity of the catalyst in various processes (activity expressed through the main indicator of a particular process), it is seen that the catalyst is particularly affected as used plasticizers (example 4), a high temperature heat treatment (examples 2 and 3), and the chemical composition of catalyst (example 8) and the size of his gnosti catalyst in the process of conversion of carbon monoxide (at low temperatures, examples 4 and 12), as activation of the catalyst in the above-mentioned conditions in a reducing environment PAA does not fade and prevents the access of reactants to the active centers. The catalyst according to example 8, having in its composition of Nickel is in the process of conversion of carbon monoxide parallel reaction of hydrogenation of carbon monoxide to methane, which slightly increases the activity indicators. In the process of methanol synthesis the presence of Nickel in the catalyst dramatically reduces its activity (process performance), as in this case, Nickel is a poison, and Vice versa, in the synthesis reaction of butyl alcohols in the presence of Nickel in the catalyst improves the performance of the process. The use of fine particles of catalyst granules (beads with a diameter of 3 to 5 mm instead of straws with a diameter of 5 mm and 14 to 15 mm) increases the activity of the catalyst in the process of conversion of carbon monoxide (example 9).

Thus, the present invention allows

to organize continuous large-capacity technology of preparation of extruded catalyst for a wide range of processes;

to obtain a catalyst with high characteristics: reduced by 19 44% bulk density, Uwe times the capacity of a production line;

reduce by 30 to 40% of energy consumption;

to increase the saving process of the preparation of the catalyst by reducing the units of the equipment, reduce or eliminate the use of certain types of materials.

1. The preparation method of catalyst for redox processes, including dry blending the basic Nickel carbonate and/or dual core carbonate salts of copper and zinc with calcium aluminates, molding, hydrothermal and thermal treatment of the granules, characterized in that before forming mass by extruding implement plasticization using as a plasticizer of an aqueous solution of boric acid or boric acid and surface-active substances (surfactants), or boric acid and ammonia, or boric acid, ammonia and surfactants at the following mass ratio of components: boric acid ammonium surfactant of 0.1-3 from 1.8 to 4.7 0.01 to 0.05 and the ratio of T W 1 0,18-0,23, and using the plasticizer that does not contain ammonia, after extrusion spend the crop has wilted granules in air or air-humid environment, when using a plasticizer containing ammonia, after extrusion are drying the pellets in a stream of air , the as surface-active substances are used water-soluble, neionogennye surfactant containing hydrophilic groups,- OH, or-COOH, or CHO, or-NH2.

3. The method according to PP. 1 and 2, characterized in that the crop has wilted granules in air is carried out at ambient temperature for 48 - 96 hours

4. The method according to PP. 1 and 2, characterized in that the crop has wilted granules in the air-humid environment is carried out at 40 to 60oC for 8 to 24 hours

5. The method according to PP.1 and 2, characterized in that the drying of the granules is carried out at 80 120oC for 1 to 3 h

 

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FIELD: chemistry.

SUBSTANCE: invention relates to a homogeneous catalyst based on tetra-4-(4'-carboxyphenylsulphanium)-5-cobalt nitrophtalocyanine(II) of tetrasodium salt of formula .

EFFECT: invention allows to produce a compound having a high catalytic activity in the oxidation of sodium diethyldithiocarbamate.

4 dwg, 1 tbl, 2 ex

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