The method of preparation of the catalyst for oxychlorination process of ethylene into 1,2-dichloroethane

 

(57) Abstract:

The invention relates to catalytic chemistry, in particular to catalysts for the synthesis of dichloroethane oxychloination ethylene. The described 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 containing metal ion Me2+and/or Me3+the aluminum oxide with a ratio of Al3+and Me2+and/or Me3+within 200 : 1 to 20 : 1, followed by drying at a temperature that provides a complete crystallization of the active component in less than 30 minutes Application of active component on a carrier and drying is carried out in a rotating drum with variable speed and is equipped with a device for the introduction of the impregnating solution and the heating element for drying. The technical result - the development of user-friendly hardware design method of producing catalyst for the oxychlorination process of ethylene into 1,2-dichloroethane and the resulting acceleration of the processes of impregnation and drying, with high catalyst activity and durability, reducing energy consumption and waste. 8 C.p. f-crystals, 1 table.

The invention relates to a spacecraft

1,2-Dichloroethane is a starting compound for the production of vinyl chloride is the most important of monometr in the production of polyvinyl chloride and vinyl copolymers.

1,2-Dichloroethane in an industrial environment is produced by interaction of ethylene, hydrogen chloride and oxygen in the fluidized bed of catalyst.

The catalysts for the oxychlorination process of ethylene into 1,2-dichloroethane are a carrier coated with a active ingredient, as a rule, compounds of copper (II).

Known catalyst comprising a chloride of copper deposited on the oxide alumomagnesium media (U.S. Patent N 4451683, class C 07 C 17/02, 1984), and part of the magnesium oxide is in the form of compounds with aluminum oxide. The composition of this catalyst corresponds to the following content, wt.%:

The active ingredient is a compound of copper (in terms of copper) - 1-15

Media - Rest

moreover, the molar ratio of MgO: Al2O3= (0,2-2,5):1 (in terms of ion Al ratio3+Mg2+= (0,2-2,5):1).

Alumomagnesium media is prepared by precipitation by mixing solutions of sodium aluminate and magnesium nitrate. The precipitate is washed, preparing a suspension (7% of the solid phase) and dried Raspletin what are the active component, for example, copper chloride, and dried at 130oC.

The main disadvantage of the synthesis of 1,2-dichloroethane using a catalyst (U.S. Patent N 4451683, class C 07 C 17/02, 1984) is a high temperature reaction oxychlorination process - 240-250oC. Useful conversion of ethylene into 1,2-dichloroethane, proven in our conditions (220oC) is 86%. The disadvantages of this method (U.S. Patent N 4451683) preparation of the catalyst is the use of a special node spray drying, significant energy consumption for spray drying low concentrated (7%) suspensions, as well as a large number of diluted wastewater and wash water.

The closest solution is the catalyst for ethylene oxychlorination process and the method of its preparation (Patent RF N 2115472, IPC6B 01 J 27/122, 21/04, 37/02; C 07 C 19/045, 1998). Application of copper compounds and subsequent crystallization on the alumina carrier is carried out in the apparatus with a stirrer, a first solution of chloride of copper concentration of 350 g/l when the agitator. After impregnation the catalyst is dried for 3 minutes with stirring, then raise the temperature to 140oC for 15 minutes without turning off the stirrer.

The disadvantage of the method of obtaining this catalyst the two is almost impossible for the machine with agitator. With increasing crystallization time more than 30 minutes, the catalyst activity decreases.

The purpose of this solution is the development of user-friendly hardware design method of producing catalyst for the oxychlorination process of ethylene into 1,2-dichloroethane and the resulting acceleration of the processes of impregnation and drying, with high catalyst activity and durability, reducing energy consumption and waste.

The problem is solved by the method of preparation of the catalyst for oxychlorination process of ethylene to 1,2-dichloroethane. The method comprises applying the active component is a compound of copper on alumina carrier containing metal ion Me2+and/or Me3+the aluminum oxide with a ratio of Al3+and Me2+and/or Me3+within 200:1 to 20:1, followed by drying at a temperature that provides a complete crystallization of the active component in less than 30 minutes. The application of active component on a carrier and drying is carried out in a rotating drum with variable speed and is equipped with a device for the introduction of the impregnating solution and the heating element for drying.

For the preparation of the catalyst using alumina media in jus the mechanical abrasion resistance of not less than 85% when the content of metal ion in terms of the metal oxide of 0.05 - 1,0%.

Application of copper compounds is performed by sputtering to content in the catalyst based on copper 3,5 - 5,5% capacity through a nozzle with compressed air.

Application of copper compounds is conducted by spraying with speed 1-9 l/HR per 1 kg of catalyst.

For the preparation of the catalyst using alumina carrier with a metal ion is introduced into a rotating drum, and the mechanical strength of the carrier resistance is 85-90%.

The device for the introduction of the impregnating solution is set in the moving mass media motionless.

The rotating drum is made with the possibility of changing the angle of inclination.

thermocouple is installed in the moving mass media motionless.

Drying is carried out in a vacuum.

In accordance with the proposed method, the catalyst is prepared as follows.

For the preparation of the catalyst used termoaktivirovannye the aluminum hydroxide of the desired fractions, obtained, for example, patent RF N 2064435. You can use thermoactivation aluminum hydroxide obtained and other known methods.

Termoaktivirovannye aluminum hydroxide peasausages drums at a temperature of 50-100oC, prepare a solution of metal salt in the apparatus, heated to 50-100oC. Then, heat treatment (700-800oC) easily form solid solutions of ions Me2+and/or Me3+in the aluminum oxide.

The resulting alumina carrier mainly has the form-Al2O3and meets the following requirements:

Specific surface area of 140 to 250 m2/g

Vaccum - 0,3 - 0,45 cm3/g

Mechanical abrasion is Not less than 85%

The content of the metal oxide is 0.05 to 1.0%

When applying especially large quantities of copper compounds drying is conducted in a rotating apparatus with the creation of the vacuum. Irritation contributes to the acceleration of the crystallization, which takes place at a lower temperature, and drying time is reduced, thereby increasing the activity of the catalyst.

The drum speed is regulated depending on the volume of the load carrier and the amount of deposited copper compounds, the greater the amount of impregnating solution, the higher the rotation speed, in order to intensify the processes of application of compounds of copper and its crystallization.

As Me2+use calcium, barium, zinc, stron is+ the media is in the range from 200 : 1 to 20:1.

As compounds of copper using a water-soluble copper compounds: salts (chlorides, nitrates, and so on) or complexes of copper (e.g., ammonia).

The catalytic properties of the sample in the reaction of ethylene oxychlorination process to determine the flow type reactor, representing a quartz tube with a diameter of 42 mm and a length of 1500 mm with electric heating and a pocket for thermocouples. The amount of catalyst in the reactor 850 mm Source components are fed in a molar ratio of ethylene : hydrogen chloride: air = 1,07:2:0,7; contact time 10 C. Analysis of gas mixtures before and after reaction, and condensation spend chromatography.

The table presents data for the conversion of ethylene to 1,2-dichloroethane in the reaction oxychlorination process depending on the conditions of its preparation.

The following examples illustrate the proposed solution.

Example 1 (the prototype). Technical hydrate of alumina, activated by a rapid thermal treatment at 350oC for 5 s, is subjected to hydration with an aqueous solution of cerium nitrate at a temperature of 80oC for 2 h to 100 kg of activated technical hydrate of alumina (soteriological, dried at 110oC and calcined at 750oC for 2 h to 100 kg received media represents a solid solution of cerium ions in the aluminum oxide with a ratio of Al3+to Ce3+= 200:1, placed in the machine with agitator, external heating, include a mixer, coating type 90 l of a solution of chloride of copper concentration of 350 g/L. After impregnation the catalyst is dried for 3 min at 90oC when the stirrer, raise the temperature to 140oC for 57 minutes

The composition of the obtained catalyst, wt.%:

Chloride copper (in terms of copper) - 4,5

Solid solution of ions Ce3+the oxide of aluminum (Al ratio3+: Ce3+= 200:1) - Rest

Example 2. Technical hydrate of alumina, activated by a rapid heat treatment at 800oC for 1 s, is subjected to hydration with an aqueous solution of copper chloride at a temperature of 60oC for 3 hours to 100 kg technical activated alumina hydrate (alumina content of about 85 wt.%) add 250 l of an aqueous solution of copper chloride concentration of 22.5 g/l Precipitate is filtered off, dried at 110oC and annealed at 800oC for 0.5 h

The resulting carrier load into the rotating drum volume is odigna in the layer of the device, spray the required amount of the active component. After impregnation is dried 5 minutes at 60oC when rotating the catalyst bed, then raise the temperature to 140oC for 21 min, crystallization of the active ingredient takes place in full during this time.

Example 3. Reactive aluminum hydroxide of the General formula Al2O3nH2O, where 0.5 n0,92, is subjected to hydration with an aqueous solution of magnesium nitrate at a temperature of 95oC for 0.5 h to 100 kg technical activated alumina hydrate (alumina content of about 85 wt. %) add 250 l of an aqueous solution of magnesium nitrate concentration of 5 g/L. Precipitate is filtered off, dried at 110oC and calcined at 700oC for 3 hours.

The resulting carrier load in a rotating drum with a volume of 1 m3. The apparatus is put into rotation at an angle of 10oto the horizon and through the nozzle, mounted in a fixed position in the layer of the device, spray the required amount of the active component. After impregnation is dried 5 minutes at 60oC when rotating the catalyst bed, then raise the temperature to 140oC for 20 min, the crystallization of the active ingredient takes place in full aimer 4. Reactive aluminum hydroxide (see example 3) is subjected to hydration with an aqueous solution of manganese chloride at a temperature of 80oC for 2 h to 100 kg technical activated alumina hydrate (alumina content of about 85 wt.%) add 250 l of an aqueous solution of manganese chloride concentration of 9.3 g/l Precipitate is filtered off, dried at 110oC and calcined at 750oC for 2 hours Then to 100 kg received media represents a solid solution of manganese ions in alumina ratio Al3+: Mn2+=90:1, spray add 0.3 l of a solution of chloride of copper concentration of 350 g/l in a rotating drum with a speed of 9 l/HR per 1 kg of catalyst. After impregnation the catalyst is dried for 5 minutes at 60oC, then raise the temperature to 120oC for 17 minutes under vacuum (5-7 mm RT.cent.). 22 minutes pass complete crystallization of the active component.

Example 5. Reactive aluminum hydroxide is subjected to hydration with an aqueous solution of gallium nitrate at a temperature of 70oC for 2.5 h to 100 kg of activated aluminum hydroxide (alumina content of about 85 wt.%) add 250 l of an aqueous solution of gallium nitrate concentrate kg received media represents a solid solution of gallium ions in the aluminum oxide with a ratio of Al3+: Ga3+=150:1, evaporated in a rotary drum type 30 l of a solution of chloride of copper concentration of 430 g/l at a rate of 1 l/HR per 1 kg of catalyst. After impregnation the catalyst is dried for 7 minutes at 70oC and stirring, and then raise the temperature to 130oC in 21 minutes. Thus there is a complete crystallization of the active ingredient. Next, the catalyst is maintained at a specified temperature for 2 hours.

Example 6. Reactive aluminum hydroxide is subjected to hydration mixed aqueous solution of salts of magnesium nitrate and cerium nitrate, at a temperature of 70oC for 2.5 h to 100 kg of chemically activated aluminum hydroxide (alumina content of about 85 wt.%) add 250 l of a mixed aqueous solution of magnesium nitrate (concentration 25 g/l) and nitrate (cerium concentration of 55 g/l). The precipitate is filtered off, dried at 110oC and calcined at 700oC for 3 hours to 100 kg received carrier is placed in a rotating drum, capacity add a solution of chloride of copper concentrations 265 g/l After impregnation the catalyst is dried 5 minutes at 80oC, then raise the temperature the ID of the aluminum is subjected to hydration in a rotating drum in a solution of magnesium nitrate.

From the above examples that the use for the preparation of the catalyst of the rotating drum in which are drying and impregnation of the active component in the moving layer of the device without mechanical movement of the stirrer, as in the prototype (example 1), leads to the production of active catalysts with high strength.

In the prototype upon receipt of the same catalyst time of crystallization of the active component is 60 minutes, which leads to a decrease in catalyst activity. The inputs for production of the catalyst according to the proposed method reduced by 30% since thermocouple is installed in the moving layer of the device, and therefore the energy loss is minimal.

1. The method of preparation of the catalyst for oxychlorination process of ethylene into 1,2-dichloroethane, including the application of the active component is a compound of copper on alumina carrier containing metal ion IU2+and/or IU3+the aluminum oxide with a ratio of Al3+and IU2+and/or IU3+within 200:1 to 20:1, followed by drying at a temperature that provides a complete crystallization of the active component in less than 30 min, characterized in that the deposition of the active component on the carrier and with the internal solution and a heating element for drying.

2. The method according to p. 1, characterized in that for the preparation of catalyst using alumina media mostly in the form-Al2O3with a specific surface area of from 140 to 250 m2/g, with a capacity of 0.3 - 0.45 cm3/g, with mechanical abrasion resistance of not less than 85% when the content of metal ion in terms of oxide of 0.05 to 1.0%.

3. The method according to PP.1 and 2, characterized in that the application of copper compounds is performed by sputtering to content in the catalyst based on copper 3,5 - 5,5% capacity through a nozzle with compressed air.

4. The method according to PP.1 to 3, characterized in that the application of copper compounds is performed by sputtering at a rate of 1 to 9 l/h per 1 kg of catalyst.

5. The method according to PP.1 to 4, characterized in that use alumina carrier with a metal ion is introduced into a rotating drum, and the mechanical strength of the carrier resistance is 85 - 90%.

6. The method according to p. 1, characterized in that the device for the introduction of the impregnating solution is set in the moving mass media motionless.

7. The method according to p. 1, characterized in that the rotating drum is made with the possibility of changing the angle of inclination.

8. The method according to p. 1, characterized in that h is decomposing the, that drying is carried out in vacuum.

 

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