The catalyst for oxychlorination process of ethylene into 1,2-dichloroethane and method thereof

 

(57) Abstract:

Group of inventions relates to catalytic chemistry, in particular to catalysts for the synthesis of dichloroethane oxychloination of ethylene to 1,2-dichloroethane. The catalyst for oxychlorination process of ethylene into 1,2-dichloroethane includes chloride, divalent copper, and aluminium oxide formed during the heat treatment resulting aluminum compounds of the formula Al2ABOUT3mo2Oh, where n=0.3 to 1.5, the layered structure together with the chloride of divalent copper. Used layered compound of the formula Al2ABOUT3mo2Oh, where n=0.3 to 1.5, is amorphous, poorly crystalsound or partially crystalline structure. The catalyst may additionally contain at least one connection element selected from the group of potassium, sodium, magnesium, boron, silicon, cerium, zirconium, or their mixture in an amount of 0.05-2.0 wt.%, the catalyst has the following composition, wt.% (in terms of element): chloride divalent copper 3,5-8,0; at least one connection element selected from the group of potassium, sodium, magnesium, boron, silicon, cerium, zirconium, or a mixture of 0.05 to 2.0; aluminium oxide - rest. The catalyst has a value of specific surface area 120-250 m2/g, pore volume is aratan includes a mixture of aluminum hydroxide with bivalent copper chloride, followed by drying and heat treatment, moreover, as the aluminum hydroxide is used as a compound of aluminium of the formula Al2ABOUT3mo2Oh, where n=0.3 to 1.5, the layered structure in the form of granules microspheric form, after drying the wet catalyst conduct its heat treatment at a temperature not exceeding 660oC. Used the aluminum hydroxide of the formula Al2ABOUT3mo2Oh, where n= 0.3 to 1.5, is amorphous, poorly crystalsound or partially crystalline structure. For the preparation of the catalyst used, the aluminum hydroxide in the form of compounds of formula Al2ABOUT3mo2Oh, where n=0,3-1,5, additionally containing at least one compound of an element selected from the group of: potassium, sodium, magnesium, boron, silicon, cerium, zirconium, or their mixture in an amount of 0.05-2.0 wt.% in terms of the item or provide a mixture of aluminum hydroxide in the form of compounds of formula Al2ABOUT3mo2Oh, where n=0.3 to 1.5, with chloride of divalent copper simultaneously, at least one additional connection element selected from the group of potassium, sodium, magnesium, boron, silicon, cerium, zirconium, or their mixture in an amount of 0.05-2.0 wt. % in terms of element. The proposed catalyst composition has a high mechanical strength, imee catalytic chemistry, in particular, the catalysts for the synthesis of dichloroethane oxychloination ethylene. 1,2-dichloroethane is a starting compound for the production of vinyl chloride is the most important monomer in the production of polyvinyl chloride and vinyl copolymers.

It is known that oxidative chlorination of hydrocarbons, particularly ethylene, is carried out in the presence of tigernach salt catalysts, when salt (usually CuCl2KCl) is applied by impregnation on devices such as alumina, silica gel, synthetic and natural silicates, clay, etc.

As the media usually use aluminum oxide in the form of microspherical particles with a size of from 20 to 200 μm, which receive the spray drying of a suspension of aluminum hydroxide with subsequent annealing and receiving media, have formed a crystalline structure (gamma-Al2O3, theta, Delta and others), which cause impregnation of the active components of the catalyst. For fixing these components on the media carry out heat treatment. The properties of the medium are determined by the important parameters of the applied catalyst for ethylene oxychlorination process, such as bulk density, durability, fracc the Torah ethylene oxychlorination process (Patent RF 2080922, IPC6B 01 J 27/122, 1997), containing the chloride of copper (II) oxide-aluminum carrier, which includes heat treatment microspherical predecessor media in suspended layer of gaseous fluid, followed by impregnating it with an aqueous solution of copper chloride and drying the obtained catalyst precursor, as microspherical predecessor media use technical trihydrate of aluminum and thermal processing is conducted at 750-1000oC for 4-6 h in a shaft furnace with a nozzle of baked molded pellets, made of solid inert material from the microspheric of three-hydrate of aluminium is formed a mixture of high-temperature crystalline phases of aluminum oxide.

The disadvantage is the complexity of the method of preparation of the catalyst, the catalyst does not have a sufficiently high strength and activity.

Known catalyst for oxychlorination process of ethylene into 1,2-dichloroethane and the method of its preparation (RF Patent 2115472, IPC6B 01 J 27/122, 21/04, 37/02, C 07 C 19/045, 1998), including the 3.5-5.5 wt.% compounds of copper, calculated on copper and alumina carrier containing metal ion, the carrier is a solid solution of ions meta is x 200S 20:1.

As Me2+and/or Me3+the media contains CE3+, Ga3+, Mg2+, MP2+, C2+.

The method of preparation of the catalyst for oxychlorination process of ethylene into 1,2-dichloroethane comprises applying the active component is a compound of copper on alumina carrier, which is a solid solution of metal ions Me2+and/or Me3+the aluminum oxide with a ratio of Al3+and Me2+and/or Me3+within 200S 20:1, and the application of copper compounds on the carrier lead plating solution and heat-treated under conditions that ensure complete crystallization of the component in less than 30 min, and the process is carried out at a ratio of components providing the following content in the catalyst, wt.%:

The connection of copper in terms of copper - 3,5-5,5

Media - Rest

The disadvantages of this invention are complex method of its preparation, insufficient mechanical strength.

A known method of preparation of microspherical catalyst for oxychlorination process hydrocarbons (RF Patent 2139761, IPC 6 B 01 J 37/04, 1999), which includes obtaining aluminum hydroxide and the introduction of the active component, the aluminum hydroxide is produced by mixing panyam the resulting suspension for 1-3 h, filtering and washing the precipitate to a residual content of Na2O less than 1.5% and the introduction of the active component is carried out by mixing the obtained precipitate with chloride of copper and magnesium chloride, spray drying at a temperature of gases at the outlet of the dryer 130-200oWith additional annealing the resulting catalyst at 600-660oC for 2-4 h

The disadvantages are the complexity of the method of preparation of the catalyst and low level.

The closest method for producing a catalyst composition and achieve catalytic properties is the method of preparation of microspherical catalyst for oxychlorination process hydrocarbons (RF Patent 2131298, IPC6B 01 J 37/04, 1999), which includes obtaining aluminum hydroxide by precipitation from sodium aluminate hydrochloric or nitric acid and the introduction of metal chlorides, aluminum hydroxide is precipitated at pH 9.0 to 10.5 and 20-75oC, washed to a residual content of Na2O less than 4.5%, is mixed with chlorine copper, or with a mixture of chloride of copper and magnesium chloride, or with a mixture of chloride of copper, potassium chloride and magnesium chloride, and the resulting suspension is subjected to spray drying at ASS="ptx2">

The disadvantages are the complexity of the method of preparation of the catalyst, low mechanical strength and low level.

The present invention is to develop a catalyst having high strength while maintaining high activity, and simplification of the method of its production.

The problem is solved at the expense of the catalyst for oxychlorination process of ethylene into 1,2-dichloroethane, including chloride, divalent copper, aluminium oxide, the catalyst formed during the heat treatment resulting aluminum compounds of the formula Al2ABOUT3mo2Oh, where n=0.3 to 1.5, the layered structure together with the chloride of divalent copper.

Used layered compound of the formula Al2ABOUT3mo2Oh, where n=0.3 to 1.5, is amorphous, poorly crystalsound or partially crystalline structure.

The catalyst additionally contains at least one compound of an element selected from the group of: potassium, sodium, magnesium, boron, silicon, cerium, zirconium, or their mixture in an amount of 0.05-2.0 wt.%, and the catalyst has the following composition, wt.% (in terms of element):

Chloride ferrous copper - 3,5-8,0

At least one of co,0

Alumina - Rest

The catalyst has a value of specific surface area 120-250 m2/g, pore volume of 0.2-0.4 cm3/g and a particle size of 20-100 microns.

The problem is solved by the method of producing a catalyst for oxychlorination process of ethylene into 1,2-dichloroethane, which comprises mixing aluminum hydroxide with bivalent copper chloride, followed by drying and heat treatment, where the aluminum hydroxide is used as a compound of aluminium of the formula Al2ABOUT3mo2Oh, where n=0.3 to 1.5, the layered structure in the form of granules microspheric form, after drying the wet catalyst conduct its heat treatment at a temperature not exceeding 660oC.

Used the aluminum hydroxide of the formula Al2ABOUT3mo2Oh, where n=0.3 to 1.5, is amorphous, poorly crystalsound or partially crystalline structure.

For the preparation of the catalyst used, the aluminum hydroxide in the form of compounds of formula Al2ABOUT3mo2Oh, where n=0,3-1,5, additionally containing at least one compound of an element selected from the group of: potassium, sodium, magnesium, boron, silicon, cerium, zirconium, or their mixture in an amount of 0.05-2.0 wt. % calculated on the item or about the om divalent copper simultaneously with at least one additional connecting element, selected from the group of potassium, sodium, magnesium, boron, silicon, cerium, zirconium, or their mixture in an amount of 0.05-2.0 wt.% in terms of the element.

Under the connection Al2ABOUT3mo2Oh, where n=0,3-1,5, x-ray amorphous layered structure is understood in this connection, x-ray analysis does not detect any lines, characteristic of any crystalline phase. This compound has high reactivity, which becomes possible intercalation compounds of the catalyst components in the interlayer space between alyumogidroksidnykh packages, accompanied by a shift alyumogidroksidnykh packages relative to each other. As a result of intercalation compounds of copper and additional connection elements, these compounds not only are uniformly distributed in the aluminum oxide, but also chemically bound with the compound of aluminium. Further, when the heat treatment is thermodispersion compounds of the catalyst components, leading to the formation of highly dispersed x-ray amorphous phases catalyst components, is strongly related to the structure of aluminum oxide. The formation of the grains of the catalyst occurs as the way the types of structure formation - crystallization or condensation, provide the most durable structure. This explains the high mechanical strength of the resulting grains of the catalyst. The transformation of hydroxides to oxides governed by the laws of the morphological Genesis, in fact, this means that the lattice of the aluminum oxide is based on a lattice of aluminum hydroxide, the proposed solution is based on the connection of Al2ABOUT3mo2Oh, where n= 0.3 to 1.5.

As is well known, x-ray amorphous state of the catalyst components is preferred for increased catalyst activity. However, the drawback of such structures is their low stability at elevated temperatures, which consists in sintering of fine particles with the formation of large crystallites, resulting in sharply reduced catalytic activity. In the proposed catalyst stability x-ray amorphous structure of the copper compounds provide additional compounds of elements from the group of magnesium, boron, silicon, cerium, zirconium, or their mixture in an amount of 0.05-2.0 wt.% in terms of the element.

Thus, the proposed solution is the formation of the catalyst during the heat treatment of closetoyou structure or partly crystalline structure, together with a compound of copper and an additional connection elements. This forms a high strength catalyst in which the active component is in the x-ray amorphous state, which allows to significantly improve the catalyst activity.

In the closest known solution (Patent RF 2131298, 01 J 37/04, 1999) for the preparation of the catalyst used aluminum hydroxide svezheosazhdennoi formula Al(Oh)3that represents a crystal phase - bayerite (Zisco C. A., Karnaukhov, A. P., Tarasov, D. C. Physico-chemical bases of synthesis of oxide catalysts. - Novosibirsk, "Nauka", 1978. - 60 C.-65), and when mixed with a compound of copper formed suspension, which is then subjected to spray drying to obtain resulting granules with a subsequent heat treatment.

In the drying of the suspension occurs coagulation formation. The strength of coagulation structures significantly lower crystallization, because van der Waals forces bind between a particle through a thin residual layer of liquid medium.

The heat treatment of the dried catalyst is the formation of crystalline phases of aluminum oxide and chloride m is

The catalyst is prepared as follows.

For the preparation of the catalyst is used as a compound of aluminum layered x-ray amorphous structure of the formula Al2ABOUT3mo2Oh, where n=0.3 to 1.5. This compound can be obtained by any known means, for example, by the rapid dehydration of hydrargillite. As the copper compounds used ul22H2O. Compound of aluminum is mixed at an elevated temperature with a solution of CuCl2and, if necessary, with additional connection elements, and some additional connection elements may already be contained in the layered compound of aluminum. The obtained catalyst mass is stirred for 1 h, then dried and calcined at a temperature of not more than 660oC.

The proposed method allows to significantly simplify the technology for producing catalyst for the oxychlorination process of ethylene to 1,2-dichloroethane in comparison with existing methods by eliminating the stage of preparation of the media.

Specific surface area determined by BET method, the volume of pore - water adsorption, particle size - sieve method.

The abrasion resistance is determined by the fraction of total mass loss during abrasion katalizatorkiado.hu, the speed of which is stable.

Determination of the activity of the catalyst is carried out at the installation volume of catalyst 840 cm3. The reactor is a quartz tube with a diameter of 42 mm with electric heating. Gas is fed into the catalytic zone through the porous plate (filter SCHOTT), located in the lower part of the reactor. Measuring the temperature of the layer is held suspended by a thermocouple in the middle part of the catalyst layer. In the reactor establish a controlled flow of gaseous reagents: air, hydrogen chloride, ethylene. The reaction temperature is 220oC.

The composition of the obtained catalyst are presented in table 1, and its physico-chemical and catalytic properties are presented in table 2.

The invention is illustrated by the following examples.

Example 1

The compound of aluminium of the formula Al2ABOUT3mo2(N=0,7) x-ray amorphous structure in the form of microspherical powder with a particle size of from 20 to 100 μm in the amount of 400 g load in the mixer, pour the solution containing the calculated amount of CuCl2and KCl, and implement the mixture for 1 hour, followed by drying of the catalyst. Dried rolled the Yat analogously to example 1, only differs in the structure of the aluminum compounds, composition and number of connections of additional elements.

Example 9 (prototype)

At room temperature, mix 10 DM318% hydrochloric acid, 60 DM3the sodium aluminate solution containing 290 g of Al2ABOUT3/DM3and 250 g of NaOH/DM3and receive a suspension of aluminum hydroxide with a pH of 10. The suspension is stirred for one hour, the precipitate is filtered and washed on the filter 120 DM3of distilled water. The filtered and washed precipitate of aluminum hydroxide is stirred with 0.5 kg CuCl22H2Oh, dilute the resulting suspension with water to the desired consistency, in particular, to the content of aluminum hydroxide in terms of Al2ABOUT3wt.%, put the suspension was spray-dried in a stream of hot flue gases when the temperature of the gases at the outlet of the dryer 150oC. the Dried product is calcined for 3 h at 250oWith and receive 2.7 kg microspherical catalyst containing 8 wt.% copper.

As seen from the examples, the catalyst of the proposed structure has high mechanical strength, has a high activity and is obtained by a simplified ti chloride divalent copper, aluminum oxide, characterized in that the catalyst formed during the heat treatment resulting aluminum compounds of the formula Al2ABOUT3mo2Oh, where n= 0.3 to 1.5, the layered structure together with the chloride of divalent copper.

2. The catalyst p. 1, characterized in that the connection of the layered structure of the formula Al2ABOUT3mo2Oh, where n= 0.3 to 1.5, is amorphous, poorly crystalsound or partially crystalline structure.

3. The catalyst p. 1, characterized in that it contains additionally at least one compound of an element selected from the group of: potassium, sodium, magnesium, boron, silicon, cerium, zirconium, or their mixture in an amount of 0.05-2.0 wt. %, the catalyst has the following composition, wt. % (in terms of element):

Chloride ferrous copper - 3,5-8,0

At least one connection element selected from the group of potassium, sodium, magnesium, boron, silicon, cerium, zirconium, or a mixture - 0,05-2,0

Alumina - Rest

4. The catalyst p. 1, characterized in that it has a value of specific surface area 120-250 m2/g and a pore volume of 0.2-0.4 cm3/,

5. The catalyst p. 1, characterized in that it has a particle size of 20-100 microns.

6. The way the floor is lorida divalent copper with subsequent drying and heat treatment, characterized in that aluminum hydroxide is used as a compound of aluminium of the formula Al2ABOUT3mo2Oh, where n= 0.3 to 1.5, the layered structure in the form of granules microspheric form, after drying the wet catalyst conduct its heat treatment at a temperature not exceeding 660oC.

7. The method according to p. 6, characterized in that the aluminum hydroxide of the formula Al2ABOUT3mo2Oh, where n= 0.3 to 1.5, is amorphous, poorly crystalsound or partially crystalline structure.

8. The method according to p. 6, characterized in that for the preparation of the catalyst used, the aluminum hydroxide in the form of compounds of formula Al2ABOUT3mo2Oh, where n= 0,3-1,5, additionally containing at least one compound of an element selected from the group of: potassium, sodium, magnesium, boron, silicon, cerium, zirconium, or their mixture in an amount of 0.05-2.0 wt. % in terms of element.

9. The method according to p. 6, characterized in that the mixture of aluminum hydroxide in the form of compounds of formula Al2ABOUT3mo2Oh, where n= 0.3 to 1.5, with chloride of divalent copper is carried out simultaneously with at least one additional connection element selected from the group of potassium, sodium, magnesium, boron, silicon, cerium, circa the

 

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