The catalyst of low-temperature conversion of carbon monoxide and method thereof

 

(57) Abstract:

The invention relates to a process for the preparation of catalysts used for chemical transformations in the gas phase, and can be used for the conversion of carbon monoxide with water vapor. The proposed catalyst for low-temperature conversion of carbon oxide includes oxides of copper, zinc, modifying compound of the metal and the aluminum oxide containing at least one connection element selected from the group of K, Na, Si, Fe, Ca, Ba, or a mixture thereof in an amount of 0.01 - 2.0 wt.% in terms of the oxide, as well as the modifying compound, the catalyst contains at least one compound of a metal selected from the group Ni, Mn, Cr, Zr, Na, Ti, Mg or a mixture thereof, in an amount of 0.1 - 15 wt.% in terms of the oxide and the catalyst has the following composition, wt.%: CuO 35,0 - 61,0; ZnO 12,0 - 29,0. At least one connection of reactive metal from the group of Ni, Mn, Cr, Zr, Na, Ti, Mg or a mixture of 0.1 to 15.0. The aluminum oxide containing at least one connection element selected from the group: K, Na, Si, Fe, Ca, BA, or a mixture thereof, in an amount of 0.01 - 2.0 wt.% - the rest. Also described is a method of obtaining catalyst for low-temperature conversion of carbon monoxide, comprising a mixture of compounds is the quality of the aluminum hydroxide used hydrated compound of aluminium of the formula Al2ABOUT3mo2Oh, where 1,1 n 2, containing at least one compound of element of group K, Na, Si, Fe, Ca, Ba, or a mixture thereof in an amount of 0.01 - 2 wt. % in terms of oxide, add nitric acid in a quantity of 0.05 - 1.5 moles of HNO3on mol Al2ABOUT3acidic module 0.0 to 1.5, introducing oxygen-containing compounds of copper, zinc, modifying metal link in the quantity necessary to obtain a catalyst of the above composition. Used the method of producing catalyst allows to simplify the technology of its receipt, and the catalyst has a high mechanical strength and catalytic activity. 2 S. and 4 C.p. f-crystals, 2 tab.

The invention relates to a process for the preparation of catalysts used for chemical transformations in the gas phase, and can be used for the conversion of carbon monoxide with water vapor.

There is a method of preparation of the catalyst for carbon monoxide conversion, consisting of the oxides of zinc, chromium, copper oxide additives of aluminum, manganese, titanium, and others, by mixing suspensions of the respective oxides with a solution of chromic anhydride followed by treatment of the catalyst mass by known methods.with. the local is also the method of preparation of the catalyst for carbon monoxide conversion by mixing at room temperature ammonia-carbonate complex copper compound of the metal at pH 12-14, followed by drying the catalyst mass at 110-150oC and pelletizing. As metal joining using zinc oxide. The weight ratio of copper ammonium carbonate complex of the zinc oxide is 1: 0,96. The catalyst to activate the gas-vapor mixture at 160-170oC (and.with. USSR N 184818, IPC B 01 J 23/72, 1965).

A known method of producing a catalyst for the conversion of carbon oxide containing oxides of zinc, copper, chromium, graphite and modifier - skeletal metallic copper. The hallmark of the invention is used as a modifier of "skeletal" copper in a specified ratio with other components.with. USSR N 733721, IPC B 01 J 37/04, 23/76, publ. 1980).

Known catalyst for hydrogen production by steam reforming of carbon monoxide in the presence of the oxide copper-zinc-manganese catalyst containing, wt.%: 30-65 of copper oxide, 18-31 of zinc oxide, 0.1 to 2.7 manganese dioxide 0,08-0,8 carbon and carrier-based alumina rest. The process is carried out at 190-400oC and pressures up to 30 MPa (RF patent N 2050975, IPC601 J 23/72, 01 3/16, 1995).

However, all of the catalysts prepared by known methods, is insufficient activity and mechanical strength.

Closest to the claimed ka is zinc oxide, aluminum hydroxide, water, chromic acid, followed by drying, molding and calcining, the catalyst mass. As starting compounds using aqueous suspension of basic carbonates of copper and zinc or zinc oxide and a suspension of aluminum hydroxide and chromic acid, and the process of mixing are in a closed cycle at a temperature of 100-120oC and the ratio of solid: liquid 1: 2-1: 3 (and.with. USSR N 736433, IPC6B 01 J 37/04, 1995).

The catalyst has the following composition, wt.%:

CuO - 54

ZnO - 11

Cr2O3- 14

Al2O3- 19,6

The disadvantage of this method is not sufficiently high strength, complex technology of preparation of the catalyst, is associated with considerable effort.

The present invention is to develop a catalyst with high mechanical strength while maintaining high activity and method of its preparation.

The problem is solved by using a catalyst of low-temperature conversion of carbon monoxide, comprising the oxides of copper, zinc, modifying compound of the metal and the aluminum oxide containing at least one connection element selected from the group of K, Na, Si, Fe, Ca, Ba, or their mixture in the at least one compound of the metal selected from the group Ni, Mn, Cr, Zr, Na, Ti, Mg (or their mixture) in an amount of 0.1-15 wt.% (in terms of oxide) and the catalyst has the following composition, wt.%:

CuO - 35,0-61,0

Zn0 - 12,0-29,0

At least one connection of reactive metal from the group of Ni, Mn, Cr, Zr, Na, Ti, Mg (or their mixture) is 0.1 to 15.0

The aluminum oxide containing at least one connection element selected from the group:

K, Na, Si, Fe, Ca, Ba (or their mixture) in an amount of 0.01-2.0 wt.% . - Rest

When the content as modifying compounds chromium metal catalyst, preferably has the following composition, wt.%:

CuO - 54,0-61,0

ZnO - 12,0-18,0

Cr2O3- 12,0-15,0

The aluminum oxide containing at least one connection element selected from the group: K, Na, Si, Fe, Ca, Ba (or their mixture) in an amount of 0.01-2.0 wt.% - Rest

When the content of as modifying the connection of the metal manganese catalyst preferably has the following composition, wt.%:

CuO - 54,0-61,0

ZnO - 12,0-14,0

MnO2- 12,0-15,0

The aluminum oxide containing at least one connection element selected from the group: K, Na, Si, Fe, Ca, Ba (or their mixture) in an amount of 0.01-2.0 wt.% - Rest

The catalyst may Saderat account of the method of producing a catalyst for low-temperature conversion of carbon monoxide, comprising a mixture of compounds of copper, zinc, modifying metal joints, aluminum hydroxide, followed by drying, calcination. As aluminum hydroxide use hydrated compound of aluminium of the formula Al2O3nH2O, where 1,1 n 2, containing at least one compound of element of group K, Na, Si, Fe, Ca, Ba (or their mixture) in an amount of 0.01-2 wt.% (in terms of oxide), add nitric acid in a quantity of 0.05-1.5 moles of HNO3on mol Al2O3, (acid module 0,05-1,5), introducing oxygen-containing compounds of copper, zinc, at least, modifying the connection metal selected from the group of Ni, Mn, Cr, Zr, Na, Ti, Mg (or their mixture) in an amount necessary to obtain a catalyst of the following composition, wt.%:

CuO - 35,0-61,0

ZnO - 12,0-29,0

At least one connection of reactive metal from the group of Ni, Mn, Cr, Zr, Na, Ti, Mg or a mixture of 0.1 to 15.0

The aluminum oxide containing at least one connection element selected from the group: K, Na, Si, Fe, Ca, Ba (or their mixture) in an amount of 0.01-2.0 wt.% - Rest

the resulting mixture is stirred, followed by molding by extrusion, drying and calcination.

The catalyst has the shape of a cylinder, spear in one stage, while maintaining high catalytic activity.

The catalyst is prepared as follows:

For the preparation of the catalyst used hydrated compound of aluminum with the gross formula Al2O3nH2O, where 1,1 n 2,0 containing at least one compound of element of group K, Na, Si, Fe, Ca, Ba (or their mixture) in an amount of 0.01-2 wt.% (in terms of oxide), add nitric acid in a quantity of 0.05-1.5 moles of HNO3on mol Al2O3then add the active components in the form of oxygen-containing compounds of copper, zinc, modifying metal compounds, stirred, is then formed by extrusion. Then the catalyst was dried, calcined at a temperature of 450-500oC and restore in a stream of hydrogen containing gas.

Composition and physico-chemical properties of the obtained catalyst is determined as follows:

- the content of Mn, Cr, Cu, Zn, K, Na, Fe, Ca, Si - x-ray fluorescence method;

the crushing strength - on device MP-9S.

Data on the method of preparation of the catalyst and its composition is shown in table 1.

The proposed catalyst was tested in the reaction of carbon monoxide conversion. The test results presented in table 2. The catalyst is characterized by konstantnosti steam:gas - of 0.7:1, volume concentration of N2AND 23.1%, H2- 55,6%, 12,5%, CO29.4%, respectively.

The invention is illustrated by the following examples.

Example 1 (the prototype)

In the reactor 1 with constant stirring continuously injected chromic acid 45% concentration in number 231 ml and 322 g of aluminum hydroxide. The resulting suspension (T:W=1:1,5-2) with constant stirring and the temperature of 100-120oC was incubated for 1.0 to 3 h, and then injected into the synthesis reactor catalyst mass.

In another reactor similar in design to preparing a suspension of a basic carbonate of copper and zinc oxide in bidistillate. In the reactor pour 1,750 l bidistillate load of 750 g of basic copper carbonate and 122 g of zinc oxide. The resulting suspension (T: W=1:2) is heated with constant stirring at a temperature of 80-90oC for 0.5 hours Both suspensions simultaneously drained from both reactors through the lower fittings in the synthesis reactor catalyst mass.

The resulting suspension of catalyst mass is maintained at 120oC for 4 h with constant stirring, then cooled to 40-50oC, add 20 g of graphite, filtered (the content of H2CrO4- 5-10 g/l), dried and calcined at 380 - 500oS="ptx2">

Example 2

The aluminum hydroxide containing Na2O in the amount of 0.03%, then add oxygen-containing compounds of Cu, Cr, Zn in an amount necessary to obtain the catalyst composition CuO - 52%, ZnO - 9,96%, Cr2O3- 12 add nitric acid (acid module is 0.75), the mass is stirred for 30 min, ekstragiruyut, dried at a temperature of 110oC and calcined at a temperature of 450oC for 6 hours.

Examples 3-9

The catalyst is prepared analogously to example 2, only vary the connection of an additional element in the media, the composition of the catalyst and acid module.

As can be seen from the table, used a method of producing catalyst allows to simplify the technology of its receipt, and the catalyst has a high mechanical strength and catalytic activity.

1. The catalyst of low-temperature conversion of carbon monoxide, comprising the oxides of copper, zinc, modifying compound of the metal and the alumina, wherein the alumina contains at least one compound of an element selected from group K, Na, Si, Fe, Ca, Ba, or a mixture thereof in an amount of 0.01 - 2.0 wt.% in terms of the oxide, as well as modifying soedinenii, in an amount of 0.1 - 15 wt.% in terms of the oxide and the catalyst has the following composition, wt.%:

CuO - 35,0 - 61,0

ZnO - 12,0 - 29,0

At least one connection of reactive metal from the group of Ni, Mn, Cr, Na, Ti, Mg or a mixture of 0.1 to 15.0

The aluminum oxide containing at least one connection element selected from the group: K, Na, Si, Fe, Ca, Ba, or a mixture thereof in an amount of 0.01 - 2.0 wt.% - Rest

2. The catalyst p. 1, characterized in that the modifying compound metal catalyst containing Cr and has the following composition, wt.%:

CuO - 54,0 - 61,0

ZnO - 12,0 - 18,0

Cr2O3- 12,0 - 15,0

The aluminum oxide containing at least one connection element selected from the group: K, Na, Si, Fe, Ca, Ba, or a mixture thereof, in an amount of 0.01 - 2.0 wt.% - Rest

3. The catalyst p. 1, characterized in that the modifying compound metal catalyst contains MnO2and has the following composition, wt. %:

CuO - 54,0 - 61,0

ZnO - 12,0 - 14,0

MnO2- 12,0 - 15,0

The aluminum oxide containing at least one connection element selected from the group: K, Na, Si, Fe, Ca, Ba, or a mixture thereof in an amount of 0.01 - 2.0 wt.% - Rest

4. The catalyst p. 1, characterized in that it contains carbon in kolida, comprising a mixture of compounds of copper, zinc, modifying metal joints, aluminum hydroxide, followed by drying, calcination, wherein gidratirovannom compound of aluminium of the formula Al2O3n H2O, where 1,1 n 2, containing at least one compound of element of group K, Na, Si, Fe, Ca, Ba, or a mixture thereof in an amount of 0.01 - 2 wt.% in terms of the oxide add nitric acid in a quantity of 0.05 - 1.5 moles of HNO3on mol Al2O3acidic module is 0.05 to 1.5, introducing oxygen-containing compounds of copper, zinc, at least, modifying the connection metal selected from the group Ni, Mn, Cr, Zr, Na, Ti, Mg or a mixture thereof in an amount necessary to obtain a catalyst of the following composition in terms of oxide, wt.%:

CuO - 35,0 - 61,0

ZnO - 12,0 - 29,0

At least one connection of reactive metal from the group of Ni, Mn, Cr, Zr, Na, Ti, Mg or a mixture of 0.1 to 15.0

The aluminum oxide containing at least one compound of an element from groups: K, Na, Si, Fe, Ca, Ba, or a mixture thereof in an amount of 0.01 - 2.0 wt.% - Rest

the resulting mixture is stirred, followed by molding by extrusion, drying and calcination.

6. The method according to p. 5, characterized in that the catalysate is

 

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