Copper-zinc-aluminum catalyst preparation process (options)

FIELD: various-destination catalysts.

SUBSTANCE: invention relates to production of copper-zinc-aluminum catalysts appropriate for low-temperature steam conversion of carbon monoxide, low-temperature methanol synthesis, and hydrogenation-dehydrogenation of various organic compounds. Catalyst preparation process comprises preparing ammonia-carbonate solutions of copper and zinc, treating aluminum-containing raw material with ammonia-carbonate solution of zinc, mixing thus treated or its mixture with untreated aluminum-containing raw material with copper and zinc compounds, holding resulting suspension in reactor at elevated temperature and stirring, separating formed catalyst mass from solution, drying, calcination, and granulation. Specifically, treatment of aluminum-containing raw material with ammonia-carbonate solution of zinc is carried out at 75-90°C and is followed by ageing at stirring until ammonia-carbonate solution of zinc is decomposed and mixing of copper, zinc, and aluminum-containing raw material is conducted in dosed manner while maintaining reactor temperature 75-90°C and specified copper-to-zinc ratio in liquid phase of suspension. Moreover, zinc compounds are introduced into reactor in the form of ammonia-carbonate solution or oxide, or basic carbonate and copper compound in the form of ammonia-carbonate solution so that copper-to-zinc atomic ratio in finished catalyst is (0.55-2.2):1 and atomic content of aluminum ranges from 2.6 to 10.6.

EFFECT: simplified catalyst preparation technology, avoided noxious effluents and gas emissions, and assured preparation of high-activity, stable, and strong catalysts.

3 cl, 1 tbl, 16 ex

 

The present invention relates to the production of medicinklinik catalysts, which are used for low-temperature conversion of carbon monoxide with water vapor, for low-temperature methanol synthesis, for processes gidrirovanii and dehydrogenation of various organic compounds, for example, for the dehydrogenation of cyclohexanol to cyclohexanone in the manufacture of caprolactam, for gas purification from impurities of sulfur, carbon monoxide, oxygen and other

There is a method of cooking medicinklinik catalyst comprising preparing a solution of nitric acid aluminum by dissolving its hydroxide in nitric acid solution, with the excess against the stoichiometry of the dissolution of zinc oxide in excess nitric acid contained in the solution of nitric acid aluminum, cooking solution of nitric acid copper by dissolving metallic copper in nitric acid solution, feeding the formed nitrous gases in the absorber to absorb, obtaining a working solution by mixing appropriate quantities of the prepared solutions of nitric acid salts of copper, zinc, aluminum, cooking precipitating agent is sodium carbonate solution by dissolving the solid salt in water, sedimentation (one - or two-stage) insoluble compounds of copper, zinc, aluminium when C is data of temperature and pH, by simultaneous or staged injection into the reactor precipitator mixed nitric acid solution of copper, zinc, aluminum, and sodium carbonate solution. Precipitated catalyst mass is stirred, cooled to 40-45°C, filtered off from the mother liquor and washed on the filter with water temperature 40-45°prior to the absence in the wash water with sodium nitrate. The mother liquor and the washing water sent for treatment, and the washed catalyst mass is dried at 150°and then calcined at a temperature of 280-400°to contain the carbonate ion is not more than 7 wt.% (CO2). The calcined mass tabletirujut.

In this way we obtain a catalyst for low-temperature methanol synthesis. (Declarative patent of Ukraine # 51460, B 01 J 37/03, 23/80, 2002).

The disadvantage of this method is the formation of large quantities of wash water contaminated with sodium nitrate and require special treatment, as well as the need for careful maintenance of the preset mode in the deposition process, especially pH, in the narrow interval (6,5-6,9). In the Pets irreproducibility of the properties of the deposited mass and, accordingly, the finished catalyst. Nitric acid used for the preparation of nitric acid solutions, has a strong chemical aggressiveness, and when dissolved in it, the metal is worked copper evolution of nitrogen oxides, which also need to be recycled.

Also known preparation method medicinklinik catalyst for methanol synthesis by thermal decomposition of ammonium carbonate complexes of copper and zinc at a temperature of 60-100°in the presence of aluminum hydroxide. This method involves the preparation of ammonium carbonate solutions of copper and zinc, the mixture prepared solutions and introducing the resulting mixture is hydrated, gel-like aluminum oxide - Al2O3·N2O extract the resulting suspension at a temperature of 75.5-99°to the decomposition of ammonium carbonate complexes of copper and zinc with the formation of basic carbonates, the separation of catalyst mass on the filter and calcining it at 280°, pressing the calcined powder into tablets (U.S. Patent No. 4279781, 502-343, 1981).

This cooking method is different from the above comparative simplicity and absence of harmful emissions, but has several disadvantages.

Thus, the joint decomposition of ammonium carbonate complexes of copper and zinc from mixed solution does not provide them with enough full coprecipitation and obtain a catalyst mass of homogeneous crystal structure: the rate of decomposition of the zinc complex 3-4 times higher than that of the complex of copper.

Closest to the proposed image the structure to the technical essence is a way of cooking medicinklinik catalyst, including preparation of ammonium carbonate solutions of copper and zinc, mixing solutions of ammonium carbonate complexes of copper and zinc, processing of aluminum hydroxide ammonium carbonate solution of zinc, a mixture of ammonium carbonate solution of copper and zinc with suspension svezheosazhdennoi aluminum hydroxide, untreated or treated with ammonium carbonate solution of zinc or mixtures thereof with getting suspended reaction mixture, the flow in the continuous mode of the reaction mixture in the reactor containing the liquid medium, which represents an ammonium carbonate solution of copper and zinc, while maintaining the reactor temperature 84-96°With continuous bubbling WITH2and maintaining the total concentration of copper and zinc at the level of 100-120 g/l

Suspended catalyst mass partially pumped to the filter and the separated precipitate is dried at 105°C, calcined at 300°and the powder is pressed into tablets (RF Patent No. 1774556, B 01 J 37/04, 23/80, 1995).

The disadvantages of this method of preparation of the catalyst are:

- education zincaluminum predecessor (stabilizer) with spinel structure does not provide the accepted conditions of processing of aluminum hydroxide ammonium carbonate solution of zinc at a temperature of 65-70°without proper exposure and monitoring article is singing its decomposition: zincaluminum spinel (ZnAl 2O4) zinc is in the form of cation (Zn2+);

- uniformity of crystal structure of the deposited catalyst weight when fed through the reactor the reaction mixture at a certain speed and maintaining the total concentration of copper and zinc at the level of 100-120 g/l will not provide no control over the amount of deposited mass and a specified ratio of copper to zinc in the liquid phase of the reactor, so as ammonium carbonate solution of zinc is less stable and will settle much faster.

- use as raw material svezheosazhdennoi aluminum hydroxide significantly complicates the technology of preparation of the catalyst: getting hydroxide by precipitation from nitrate salts requires thorough washing from nitrate ions.

The technical result, which aims invention is to provide a simple and economical cooking techniques medicinklinik catalysts that have no harmful wastewater and gas emissions and providing a highly active, stable and mechanically strong catalyst.

The technical result is achieved in the first embodiment of the method of preparation of the catalyst, including the production of ammonium carbonate solutions of copper and zinc, the processing of aluminium-containing raw material ammonium carbonate solution of zinc, the mixture treated aluminum is containing raw material and mix it with raw aluminium-containing raw materials and compounds copper and zinc, maintaining in the reactor resulting suspension at elevated temperature and stirring, separating the resulting catalyst mass from the solution, drying, and calcining the pellet, according to the invention the processing of aluminium-containing raw material ammonium carbonate solution of zinc is carried out at a temperature of 75-90°and extract with stirring until the decomposition of the ammonium carbonate solution zinc, and a mixture of compounds of copper, zinc and aluminium-containing raw material is carried out gradually, keeping the temperature in the reactor 75-90°and a specified ratio of copper to zinc in the liquid phase of the resulting suspension, with zinc compounds injected into the reactor in the form of ammonium-carbonate solution or oxide, or basic carbonate, and copper - ammonium-carbonate solution, and the atomic ratio of copper to zinc in the catalyst is obtained (0,55-2,2):1 at atomic content of aluminium from 2.6 to 10.6.

According to the second variant of the method of preparation of the catalyst, including the production of ammonium carbonate solutions of copper and zinc, a mixture of aluminium-containing raw materials and compounds copper and zinc, maintaining in the reactor resulting suspension at elevated temperature and stirring, separating the resulting catalyst mass from the solution, drying, calcining and granulation, mixing with the joining of copper, zinc and aluminium-containing raw material is carried out gradually, keeping the temperature in the reactor 75-90°and a specified ratio of copper to zinc in the liquid phase of the suspension, while zinc compounds injected into the reactor in the form of an ammonium carbonate solution or oxide or basic carbonate, and copper - ammonium-carbonate solution, and the atomic ratio of copper to zinc in the catalyst is obtained (0,55-2,2):1 at atomic content of aluminium from 2.6 to 10.6.

As in the first and second embodiments of the method as aluminium-containing raw material using hydroxide or oxide aluminum compounds having predominantly crystalline structure up to 100 Å or the past mechanochemical activation.

Distinctive features of the variants of the method according to the present invention consist in the fact that in the first embodiment, the processing of aluminium-containing raw material ammonium carbonate solution of zinc is carried out at a temperature of 75-90°and extract with stirring until the decomposition of the ammonium carbonate solution zinc, and a mixture of compounds of copper, zinc and aluminium-containing raw material is carried out gradually, keeping the temperature in the reactor 75-90°and a specified ratio of copper to zinc in the liquid phase of the suspension, while zinc compounds injected into the reactor in the form of an ammonium carbonate solution or OK the IDA or basic carbonate, and the connection of copper - ammonium-carbonate solution, and the atomic ratio of copper to zinc in the catalyst is obtained (0,55-2,2):1 at atomic content of aluminium from 2.6 to 10.6, and the second variant carry out a mixture of compounds of copper, zinc and aluminium-containing raw material is metered under the same conditions as in the first variant of the method.

Additional distinctive features for both the first and second variants of the method lies in the fact that as aluminium-containing raw material using hydroxide or oxide aluminum compounds having predominantly crystalline structure up to 100 Å or the past mechanochemical activation.

The present invention meets the condition of patentability - novelty, as in the prior art failed to find technical solutions, the essential features which would coincide with all the features available in the independent claims.

Also the present invention meets the condition of patentability - inventive step, because the prior art has failed to find technical solutions, the hallmarks of which was provided by the same technical problems, the solution of which the invention is directed.

The invention is illustrated negativeand the mi examples.

For the preparation of catalysts in the following examples, used ammonium carbonate solutions of copper and zinc obtained by the dissolution of their oxides in solutions of ammonium carbonate with a given ratio of NH3and CO2. For the preparation of solutions can be used also basic salts of copper and zinc, or a metal. In a prepared solutions, the concentration of copper or zinc was 100-120 g/l and the mass ratio of Cu(Zn):NH3:CO2= 1:1,25:0,8.

Example 1

In the decomposition reactor is injected 0,325 l aqueous suspension containing of 18.9 g of aluminum hydroxide with the structure of boehmite (AlOOH) and the size of crystals 80-100 Åis heated to 80-85°and add 0,11 l ammonium carbonate solution of zinc containing (in grams): Zn - 10,5; NH3- 13,2; CO2is 8.5. The reactor is maintained at a temperature of 80-85°and With vigorous stirring until the decomposition of the ammonium carbonate solution zinc. Then injected into the reactor 0,56 l mixed ammonium-carbonate solution of copper and zinc containing (in grams): Cu - 28, Zn - 28,8, NH3- 71,8, CO2- 46,5, dosing it so that the ratio of copper to zinc in the liquid phase of the reactor was at 2.1 to 2.2. At the end of prilipanie solution, the suspension in the reactor is stirred for equalization of concentrations and terazosine residues of ammonium-Carbo is atnah salts to the content of NH 3in a solution of 2-3 g/L. the Resulting catalyst mass is filtered, dried and calcined at a temperature of 280-290°to volatile in prokalavaemy mass - 8-15 wt.%, and then the resulting powder was pressed into tablets.

In the prepared catalyst ratio of Cu:Zn=0,71, and the atomic content of Al - 7,62.

Example 2

In the reactor pour 0,325 l aqueous suspension containing 24 g of technical aluminum hydroxide - AL(OH)3held mechanochemical activation in a bead mill (30 min), heat it up to 85-90°and add 0,11 l ammonium carbonate solution of zinc containing (in grams): Zn - 10,5; NH3- 13,2; CO2is 8.5. The contents of the reactor is maintained at a specified temperature until the completion of the decomposition of the ammonium carbonate solution of zinc, and then injected into the reactor 49 g of zinc oxide and begin to dose of 0.28 l ammonium carbonate solution of copper, maintaining the copper concentration in the liquid phase of 2.0-2.5 g/L. Next, the catalyst is prepared as in example 1.

Example 3

In the reactor pour 0,325 l aqueous suspension containing 16 g of active alumina - γ Al2About3, heated to 75°and add 0,11 l ammonium carbonate solution of zinc containing (in grams): Zn - 10,5; NH3- 13,2; CO2- 8.5 and incubated under stirring until the decomposition of the ammonium carbonate solution qi is ka, then poured into the reactor 0,28 l ammonium carbonate solution of copper and begin to dose and 68.5 g of basic zinc carbonate - 0,9 ZnCO30,1 Zn(OH)2maintaining in the reactor a temperature of 75°and the ratio of Cu:Zn in the liquid phase at 0.75. Further preparation as in example 1.

Example 4

In the reactor pour 0,325 l aqueous suspension containing of 18.9 g of boehmite, heated to 87-88°and add 0,11 l ammonium carbonate solution zinc content of the reactor is maintained at a specified temperature and stirring until the decomposition of the ammonium carbonate solution of zinc, then poured into the reactor 0,28 l ammonium carbonate solution of copper and immediately begin to dose 0,393 l ammonium carbonate solution zinc, maintaining in the reactor set temperature and the ratio of Cu:Zn in the liquid phase of the suspension at 0.75. The resulting suspension of catalyst mass is thoroughly mixed, and then the preparation as in example 1.

Example 5

In the reactor pour 0,325 l aqueous suspension containing of 18.9 g of boehmite, heated to 75°add 0,11 l ammonium carbonate solution zinc. The suspension is incubated at a given temperature until the completion of the decomposition of the ammonium carbonate solution of zinc, then pour into the reactor 0,28 l ammonium carbonate solution of copper and begin to dose zinc oxide, maintaining in the reactor is acceptable temperature and the ratio of Cu:Zn in the liquid phase at the level of 0.71. Further preparation as in example 1.

Example 6

In the decomposition reactor is injected 0,325 l aqueous suspension containing of 18.9 g of aluminum hydroxide with the structure of boehmite (AlOOH), heated to 75°and pour 0,06 l ammonium carbonate solution of zinc containing (in grams): Zn - 5,7, NH3- 7,2, CO2- 4,6. The content of the reactor is maintained at a temperature of 75-80°and With vigorous stirring until the contents of NH3in the liquid phase close to 1 g/L. Then, to maintain the temperature in the reactor is metered 0,61 l ammonium carbonate solution of copper and zinc containing (in grams): Cu - 28, Zn - 33,6, NH3- 77,8, CO2- 50,4 with speed, providing the concentration of copper and zinc in the liquid phase of the suspension, the corresponding Cu:Zn=2.3 to 2.4. Next, the catalyst is prepared as in example 1.

The prepared catalyst has a composition corresponding to the ratio of Cu:Zn=0,71, and the atomic content of the aluminum - 7,62.

Example 7

In the reactor pour 0,325 l aqueous suspension containing 9.5 g of boehmite - AlOOH and 12 g of technical aluminum hydroxide, and heated to 90°C. the suspension is poured 0,11 l ammonium carbonate solution of zinc and under stirring survive until the end of the decomposition of the ammonium carbonate solution of zinc, and then begin to dispense a mixture of ammonium carbonate solutions of copper and zinc to maintain the right temperature and the ratio of the group of Cu:Zn in the liquid phase, equal to 2.1-2.5. At the end of the dosing solutions slurry catalyst mass is thoroughly mixed and then the preparation as in example 1.

Example 8

In the reactor enter 0,325 l aqueous suspension containing of 18.9 g of aluminum hydroxide with the structure of boehmite (AlOOH), heated under vigorous stirring to 88-90°and begin to enter the reactor 0.67 l ammonium carbonate solution of copper, zinc, containing (in grams): Cu - 28, Zn - 39,3, NH3- 85, CO2- 55, dosing him with speed, providing the ratio of Cu:Zn in the liquid phase of the suspension at 2.5. Next, the preparation and composition of the catalyst as in example 1.

Example 9

In the reactor enter 0,325 l aqueous suspension containing of 18.9 g of boehmite (AlOOH), heated to 85-88°pour 0,28 l ammonium carbonate solution of copper containing (in grams): Cu - 28 MN3- 35,5, CO2- 23,1, and with vigorous stirring immediately begin to dose of 0.39 l ammonium carbonate solution of zinc containing (in grams): Zn - 39,3, NH3- 49,5, CO2- 31,9, with speed, providing in the liquid phase of the suspension ratio of Cu:Zn=2,5. Next, the preparation and composition of the catalyst as in example 1.

Example 10

In the reactor, enter 0 l water suspension containing of 18.9 g of aluminum hydroxide with the structure of boehmite, heated to 80-85°pour 0,28 l ammonium carbonate solution of copper, containing the th (in grams):Cu - 28, NH3- 35,5, CO2- 23,1, add 0.1 solution of ammonium carbonate containing (in grams): NH3- 14.5 and CO2to 9.5, and with vigorous stirring start to dose 49 g of zinc oxide (ZnO), maintaining the speed of the feed in the liquid phase slurry reactor, the ratio of Cu:Zn=0,71-0,75. Next, the preparation and composition of the catalyst as in example 1.

Example 11

In the decomposition reactor is injected 0,325 l aqueous suspensions containing (in grams) of 18.9 g of boehmite (AlOOH), heated up to 77-80°pour 0,28 l prepared ammonium carbonate solution of copper, add 0.1 l of a solution of ammonium carbonate containing (in grams): NH3- 14,5, CO2to 9.5, and with vigorous stirring metered 59.3 g of powder of the basic zinc carbonate. Next, the preparation and composition of the catalyst as in example 10.

Example 12

In the reactor enter 0,325 l aqueous suspension containing 16 g of active alumina (γ Al2O3), is heated to a temperature of 85-88°pour 0,28 l prepared ammonium carbonate solution of copper, add 0.1 l of a solution of ammonium carbonate containing (in grams): NH3- 14,5, CO2to 9.5, and with vigorous stirring start to dose 49 g of zinc oxide (ZnO). Next, the preparation and composition of the catalyst as in example 10.

Example 13

In the reactor enter 0,325 l aqueous suspension containing 24.5 g swages the terms of aluminum hydroxide - Al(OH)3, heated to 75-80°pour 0,28 prepared with ammonium carbonate solution of copper, add 0.1 l of a solution of ammonium carbonate containing (in grams): NH3- 14,5, CO2to 9.5, and when mixing the metered ZnO, maintaining in the liquid phase ratio of Cu:Zn level of 0.71 to 0.75. Next, the preparation and composition of the catalyst as in example 10.

Example 14

In the reactor enter 0,325 l aqueous suspension containing 24 g of technical aluminum hydroxide - Al(OH)3held mechanochemical processing biserni mill for 30 minutes, heat the suspension to 85-90°pour 0,28 l prepared ammonium carbonate solution of copper, add 0.1 l of a solution of ammonium carbonate containing (in grams) NH3- 14,5, CO2to 9.5, and with vigorous stirring metered ZnO as in example 13. Next, the preparation and composition of the catalyst as in example 10.

Example 15

In the decomposition reactor is injected with 0.2 l of water suspension containing 5.9 g of aluminum hydroxide with the structure of boehmite (AlOOH) with the size of the crystals 80-100 Å, heated to 75-80°, pour 25 g of zinc oxide (ZnO) and dosed 0,44 l ammonium carbonate solution of copper containing (in grams): Cu - 44, NH3- 55,8, CO2- 36,3. The resulting suspension is incubated under vigorous stirring until the decomposition of ammonium carbonate solutions of copper and the Inca (the content of NH 3in the liquid phase of the suspension 2-3 g/l). Further, the preparation of the catalyst as in example 1.

In the prepared catalyst ratio of Cu:Zn=2,2, and the atomic content of aluminum (Al) is 2.6.

Example 16

In the decomposition reactor is injected 0,42 l aqueous suspension containing 12.5 g of aluminum hydroxide with the structure of boehmite (AlOOH), heated to 85-90°pour 0.2 l ammonium carbonate solution of copper containing (in grams): Cu - 20, NH3- 25,3, CO2is 16.5. In the resulting suspension under vigorous stirring dose of 0.36 l ammonium carbonate solution of zinc containing (in grams): Zn - 36, NH3of 45.4, CO2- 29,3, with speed, providing the ratio of Cu:Zn in the liquid phase of the suspension at the level of 3.0-3.5. Further, the preparation of the catalyst as in example 1. In the prepared catalyst ratio of Cu:Zn=0,55, and the atomic content of aluminum (Al) to 10.6.

Suggested method of preparation of a catalyst based on copper, zinc and aluminum allow you to gain the following benefits:

so the processing of aluminium-containing raw material ammonium carbonate solution of zinc at a temperature of 75-90°followed by its decomposition leads to the formation of cations of zinc (Zn2+), is able to interact with aluminium-containing raw material with the formation of highly dispersed thermally stable zincaluminum connection with W analnoe structure (ZnAl 2O4)provides for the formation of the catalyst crystalline, stable medicinova compounds responsible for its catalytic properties;

dosed introduction the main components of the catalyst in the reactor decay caused by the fact that ammonium carbonate solutions of copper and zinc have different resistance to decomposition: the constant volatility of the zinc solution 3-4 times higher than for a similar solution of copper. Therefore, their joint decomposition leads to the enrichment of the resulting solid products of decomposition compounds zinc: catalyst weight is heterogeneous, without proper co-precipitation of copper with zinc. Maintaining in the liquid phase of the reactor specified ratio between copper and zinc by dispensing components taking into account the different decomposition rates of their ammonium carbonate solutions and chemical composition of the catalyst allows to form the catalyst mass with homogeneous phase and crystal-chemical composition, which determines the high catalytic properties of the finished catalyst;

- with the introduction into the reactor of zinc compounds in the solid state in the form of oxide (carbonate) is unexpected positive effect creates a self-regulating process of decomposition education: ammonium carbonate dissolve the copper is decomposed and released the products of decomposition of NH 3and CO2interact with the zinc oxide with the formation of ammonium-carbonate solution, decomposing in conjunction with ammonium carbonate solution of copper, forms a more uniform medicinebuy structure deposited on the aluminium-containing raw materials. Released during this NH3and CO2dissolve the next portion of the oxide (carbonate) zinc. In this way, the introduction of zinc compounds, along with obtaining a homogeneous finely dispersed catalyst mass, responsible for the high catalytic properties of the finished catalyst, is simplified and reduced the price cooking technology: reduced consumption, ammonium salts and reduces the duration of operation of decomposition;

- use as aluminium-containing raw material is prepared, manufactured, hydroxides and oxides of aluminum with a fine crystalline structure and, accordingly, sufficient reactive allows to obtain catalysts with high catalytic properties, including thermal stability and stability in the work, to simplify and reduce the cost of technology by eliminating the process of getting svezheosazhdennoi aluminum hydroxide with contaminated water.

Characterization of the catalytic properties of the samples of the catalysts obtained in accordance with the variants of the proposed method, a CR is entered in the table.

Table

Characterization of catalysts
ExampleThe properties of the catalysts, the process
The conversion FROM water vapor
Atomic relations of Cu:Zn and Al contentActivity-the degree of transformation WITH at 180°,%Thermostability of activity after overheating at 350°With (4 hours)
1.0.71 and a 7.6298,196,1
2.0.71 and a 7.6298,396,8
3.0.71 and a 7.6298,596,7
4.0.71 and a 7.6298,897,2

95,1
5.0.71 and a 7.6298,196,9
6.0.71 and a 7.6297,995,8
7.0.71 and a 7.6297,496,1
8.0.71 and a 7.6297,2
9.0.71 and a 7.6297,3for 95.3
10.0.71 and a 7.6298,396,6
11.0.71 and a 7.6298,596,5
12.0.71 and a 7.6298,396,7
13.0.71 and a 7.62of 98.296,6
14.0.71 and a 7.6298,196,4
The placeholder1,85 and 6,6395, (12x)94,5
The methanol synthesis
ExampleAtomic relations of Cu:Zn and Al contentActivity-performance, cm3the raw methanol at 220°C and 50 MPaThermostability of activity after overheating at 370°With (4 hours)Selectivity-the obsession of CH 3HE in methanol raw, % wt
15.the 2.2 and 2.62,11,6598,1
The placeholder1,85 and 6.51,951,5-
The dehydrogenation of cyclohexanol to cyclohexanoneXX)
ExampleAtomic relations of Cu:Zn and Al contentThe activity degree of conversion of cyclohexanol (total), %Thermostability of activity after overheating at 350°Selectivity-conversion of cyclohexanol to the target product
To overheatingAfter overheating
16.0,55 and 10.6of 58.957,899,699,3
x)Activity is the rate constant of the reaction conversion (first order) at 225°C. For the catalysts according to examples 1-14 - within 15-16.
XX)- On activity, thermal stability and selectivity of the catalyst is at ur is beyond the best known analogues.

From the table it follows that medicinecabinet catalysts prepared in accordance with the invention (examples 1-16), have a high activity, stability, selectivity with sufficient mechanical strength.

1. The method of preparation medicinklinik catalyst, including the production of ammonium carbonate solutions of copper and zinc, the processing of aluminium-containing raw material ammonium carbonate solution of zinc, a mixture of processed aluminium-containing materials or mixtures thereof with raw aluminium-containing raw materials and compounds copper and zinc, maintaining in the reactor resulting suspension at elevated temperature and stirring, separating the resulting catalyst mass from the solution, drying, calcining and granulation, characterized in that the processing of aluminium-containing raw material ammonium carbonate solution of zinc is carried out at a temperature of 75-90°and extract with stirring until the decomposition of the ammonium carbonate solution of zinc and the mixture of compounds of copper, zinc and aluminium-containing raw material is carried out gradually, keeping the temperature in the reactor 75-90°and a specified ratio of copper to zinc in the liquid phase of the resulting suspension, with zinc compounds injected into the reactor in the form of ammonium carbonate solution, or the CID, or basic carbonate, and copper - ammonium-carbonate solution, and the atomic ratio of copper to zinc in the catalyst is obtained (0,55-2,2):1 at atomic content of aluminium from 2.6 to 10.6.

2. The method of preparation medicinklinik catalyst, including the production of ammonium carbonate solutions of copper and zinc, a mixture of aluminium-containing raw materials and compounds copper and zinc, maintaining in the reactor resulting suspension at elevated temperature and stirring, separating the resulting catalyst mass from the solution, drying, calcining and granulation, characterized in that the mixture of compounds of copper, zinc and aluminium-containing raw material is carried out gradually, keeping the temperature in the reactor 75-90°and a specified ratio of copper to zinc in the liquid phase of the suspension, and the connection of zinc injected into the reactor in the form of an ammonium carbonate solution or oxide or basic carbonate, and copper - ammonium-carbonate solution, and the atomic ratio of copper to zinc in the catalyst is obtained (0,55-2,2):1 at atomic content of aluminium from 2.6 to 10.6.

3. The method according to claim 1 or 2, characterized in that as aluminium-containing raw material using hydroxide or oxide aluminum compounds having predominantly crystalline structure up to 100Å or p is Osadchii mechanochemical activation.



 

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5 ex

FIELD: polymerization catalysts.

SUBSTANCE: catalyst preparation involves interaction of rare-earth element compound, conjugated diene, and diisobutylaluminum hydride followed by ageing of reaction mixture for 10-30 min, adding tetraisobutyl-dialumoxane and alkylaluminum hydroxide at molar ratio 1:(2-20):(3-12):(6-12):(1.5-3), respectively, and ageing resulting mixture for 10-15 h. Diene utilized is in the process is pyperilene or isoprene and rare-earth element compound is rare-earth element carboxylate or alcoholate. Catalyst can, in particular, find use in production of cis-1,4-polydienes.

EFFECT: achieved preparation of high-efficiency catalyst enabling production of highly stereospecific polybutadiene or butadiene/isoprene or butadiene/pyperilene copolymers at narrower molecular mass distribution.

4 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: method of preparing catalyst based on high-silica zeolite comprises calcination of zeolite and treating it with ammonium salt solutions at 160-200°C followed by mixing with binder, drying, and calcination. High-silica zeolite utilized is ZSM-5 zeolite, which is treated with aqueous ammonium solutions until degree of Na+ cation substitution above 99% is attained.

EFFECT: increased catalytic activity and selectivity in benzene-ethylene alkylation process.

1 tbl, 6 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: method of preparing catalyst based on high-silica zeolite comprises calcination of zeolite and treating it with ammonium salt solutions at 120-150°C followed by mixing with binder, drying, and calcination. High-silica zeolite utilized is ZSM-5 zeolite, which is treated with aqueous ammonium solutions at equivalent ratio NH4+:Na+ = (1.5-2.9):1.0 to degree of Na+ cation substitution above 99%.

EFFECT: increased catalytic activity and selectivity in benzene-ethylene alkylation process.

1 tbl, 7 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: preparation of catalyst comprises depositing active components on γ-alumina carrier at stirring, carrier being preliminarily treated with concentrated NaOH solution. Active components are deposited consecutively in three steps. In the first step, preliminarily prepared chitosan in acetic acid solution with KCl solution is deposited for 60-65 min; in the second step, sodium tetrachloropaladate(II) trihydrate Na2PdCl4·3H2O solution is deposited for 60-65 min; and, in the third step, hydrazine hydrate solution as reducing agent is added for 180-240 min. After each step, resulting suspension is filtered off, washed, and dried at 293-303K for 1-2 h in vacuum. Catalyst can be used in chemical industry and in processing of industrial and household wastes.

EFFECT: enhanced nitrate hydrogenation efficiency.

6 cl, 1 dwg, 6 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to improved method of preparing double metal cyanide catalysts for synthesis of polyether-polyols via polyaddition alkylene oxides to starting compounds possessing active hydrogen atoms. Method comprises following steps: (i) mixing one or several solutions of water-soluble salts of Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(IV), Sr(II), W(VI), Cu(II), or Cr(III) with solution of water-soluble cyanide ions-containing salt or acid of Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV), or V(V) with the aid of mixing nozzle, preferably jet disperser; (ii) isolation of catalyst from resulting dispersion; (iii) washing; and (iv) drying.

EFFECT: increased catalytic activity, reduced particle size, and narrowed size distribution of particles in polyether-polyols production process.

8 cl, 5 dwg, 9 ex

FIELD: alternate fuels.

SUBSTANCE: invention relates to a method for production of hydrogen via steam conversion of carbon monoxide and to relevant catalysts and can find used in different fields of national economy. Catalyst phase of copper-zinc-zirconium hydroxocarbonate of general formula (CuxZryZn1-x-2y)(CO3)2(OH)6 with hydrozinkite and/or aurichalcite structure, or of general formula (CuxZryZn1-x-2y)(CO3) (OH)2 with roasite structure, or containing heat treatment product thereof with general formula CuxZryZn1-x-2yO with vurcite structure, where x is number not higher than 0.7 and y number from 0.01 to 0.33. Also, method of conversion of O and H2O-containing gas mixture involving passage of reaction mixture through aforesaid catalyst bed at 150-400°C.

EFFECT: enabled preparation of heat-resistant catalyst efficiently functioning within temperature range 150 to 400°C.

4 cl, 3 dwg, 1 tbl, 7 ex

FIELD: production of catalysts on base of compounds of copper, zinc and aluminum for low-temperature conversion of carbon oxide with water steam; chemical, and petrochemical industries; production of ammonia and hydrogen.

SUBSTANCE: proposed method consists in mixing the solution of ammonia-carbonate complex of copper with solution of ammonia-carbonate complex of zinc and with oxide or hydroxide of aluminum; suspension thus obtained is heated to 40-50°C, then it is subjected to stirring continued for 1-2 h, after which temperature is raised to 85-97°C and purge gas is introduced, for example nitrogen or carbon dioxide and suspension is mixed at solid-to-liquid ratio of 1:(2.0-4.0); sediment is removed; mixture is dried, calcined and liquid stabilizing additives are introduced into calcined mass at solid-to-liquid ratio of 1: (0.2-1.0) and 1-1.5 mass-% of graphite is added; mixture is stirred, granulated and pelletized. Used as stabilizing additives are chromic, nitric or oxalic acids, or their salts, or carbamide.

EFFECT: enhanced activity and thermal stability.

2 cl, 1 tbl, 20 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at high pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:(0.7-1.1):(0.086-0.157):(0.05-0.15):(0.125-0.2):(0.018-0.029):(0.04-0.075).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at low pressure and provides a wear-resistant catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, and boron and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3 = 1:0.3:(0.15-0.2):(0.1-0.025):(0.25-0.3):(0.08-0.1).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at median pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:0.3:(0.014-0.038):(0.047-0.119):(0.05-0.1):(0.007-0.014):(0.0292-0.054).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

The invention relates to a process for the preparation of catalysts based on copper compounds and zinc for low-temperature conversion of carbon monoxide with water vapor and can be used in the chemical and petrochemical industry, for example, in the production of ammonia and hydrogen, the synthesis of methanol and other industries

The invention relates to a method for preparing CdS photocatalyst for hydrogen production and to a method of obtaining hydrogen from water by photochemical reaction with its application

The invention relates to a method for producing ester of formic acid or methanol and the catalyst of this method

FIELD: reduction-oxidation catalysts.

SUBSTANCE: invention relates to catalysts for deep oxidation of carbon monoxide that can be used to treat industrial emission gases and motor transport exhaust gases. Aluminum-based oxidation catalyst contains 1.3-5.1% of rare-earth and/or alkali-earth element and represents ultradisperse powder.

EFFECT: increased catalytic activity.

4 ex

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