The preparation method of catalyst for ethylene oxychlorination process

 

(57) Abstract:

Use: preparation of catalyst for the oxychlorination process of ethylene containing chloride copper (2) acidsolution media. The inventive microspheres technical three-hydrate of aluminium is subjected to heat treatment in a suspended layer of gaseous fluid is flue gas obtained by burning bessonnitsa of the heating gas at 750 to 1000 deg. C for 4-6 hours, in chess furnace with a nozzle of baked molded pellets, made of solid inert material with the specified resulting aluminum trihydrate is passed through the nozzle upward co-current. Then the carrier is impregnated with an aqueous solution of copper chloride and dried the resulting catalyst precursor.

The invention relates to the preparation of the catalyst of ethylene oxychlorination process containing chloride copper (II) on active aluminum oxide.

There is a method of preparation of the catalyst of ethylene oxychlorination process, in accordance with which is mixed dowolny chloride copper (II) with a water suspension of the three-hydrate of alumina, peptizer mixture by adding a solution of hydrate of oxide of ammonium and sodium in the preparation of a gel, the floor is washed, subjected to spray-dried and calcined at a temperature of 300-500 deg. C obtaining microspherical catalyst /1/.

This method results in a catalyst with low activity.

More active catalysts are impregnated industrial prepared microspheres of aluminum oxide dowolnym chloride copper (II) with subsequent drying and calcining the impregnated carrier. Such technology with minor variations described in /2/-/5/.

In particular, it is noted that the best properties is characterized by a catalyst containing about 5% of the chloride of copper /per copper/ characterized by the following particle size distribution:

90-95% less than 80 μm

40-50% less than 45 microns

15-30% less than 30 microns

3-10% less than 20 microns

1-5% more than 200 microns.

Similar granulometric composition provides gazodinamichesky optimal turbulent fluidized bed. The resulting catalyst is characterized by relatively high activity. However, this method cannot provide a sufficiently durable to abrasion and active catalysts /4/-/5/.

In another modification of the same method, the impregnation of Wesnoth, the same technical result /6/.

Closest to the claimed method of preparation of the catalyst involves special training oxindolimine media before impregnation, which consists of the following: porous microspheres of aluminum oxide is heated in the fluidized bed formed by air, nitrogen, or oxygen to a temperature of 250-500°. C for 1-5 hours, cooled air in the fluidized bed to a temperature less than 50 degrees. C, impregnated microspheres with a solution of chloride of copper (II), which is injected in the amount of 0.7 to 0.9 of the volume of the pores of the support /solution contains 16-40 g CuCl2/ 100 ml water/ after impregnation of the particles that remain in the fluid state, is heated with a rate of 5-30 degrees. C per hour to a temperature not higher than 180 deg. C, for example, up to 140 deg. C and kept at this temperature for 0.5 to 15 hours. /7/

The catalyst is characterized by the following parameters: specific surface area /S on BET/ 140-200 sq. m/g, pore volume of 0.38-0.45 ml/g, average pore 3,4-3,5 nm, the content of chloride of copper 3-7 wt. In accordance with the examples get the catalyst in the form of microspheres with an average diameter of 40 μm, containing copper chloride in an amount of 5% by weight based on copper. Testing this katalysator4:O2- 2:1,0,2:0.8, the conversion of ethylene was: 99.8% of the selectivity of the formation of dichloroethane to 98.5% conversion of HCl was 99,1% selectivity education dichloroethane 99.7% of

This method, however, is very difficult: it is necessary at all stages of preparation of the catalyst precisely controlled conditions of all stages of the technology of preparation of the catalyst, humidity, etc. parameters, which are difficult to manage efficiently. In the event of absence of suitable sredstv control the play received good results very difficult.

In accordance with the invention proposes a method of preparation of the catalyst of ethylene oxychlorination process containing chloride copper (II) on acidsolution media, in accordance with which the microspheric technical trihydrate of aluminum is subjected to heat treatment at a temperature of 750-800 deg. C for 4-6 hours, which is carried out in a shaft furnace with a nozzle of baked molded pellets, made of solid inert material with the specified resulting aluminum trihydrate is passed through the nozzle upward co-current, generated flue gas obtained by burning bessonnitsa heating gas, with posledney catalyst" used in this description only to separate the prepared catalyst from the true catalytically active form, which is formed spontaneously in conditions catalyzed reaction/.

General features of the process in accordance with image and prototype /7/ are the same /the preparation of the catalyst of ethylene oxychlorination process containing chloride copper (II) on acidsolution the medium, the presence of heat treatment operations microspherical predecessor media in suspended layer of gaseous fluid with subsequent impregnation with an aqueous solution of copper chloride and drying the obtained catalyst precursor.

Unlike the prototype as microspherical predecessor media use technical trihydrate of aluminum, heat treatment which is carried out at a temperature of 750-800 deg C for 4-6 hours in a shaft furnace with a nozzle of baked molded pellets, made of solid inert material with the specified resulting aluminum trihydrate is passed through the nozzle upward co-current, generated flue gas obtained by burning bessonnitsa heating gas.

The claimed method is simple, does not require sportivnie catalysts for ethylene oxychlorination process. As a technical three-hydrate of aluminium is recommended to use technical alumina marks RG 0 or DG-1 /GOST 6912-74/. As the material annealed molded pellets, made from an inert material, it is possible to use granules of various forms /cylindrical, spherical and so on/ and heat-resistant materials such as mullite, corundum, aluminum oxide, calcined at a temperature of 1160-1460 deg C, etc., Microspheres made from industrial alumina in a stream of flue gases pass upward flow through the shaft furnace, loaded the specified nozzle. To provide the required residence time of the beads in the shaft furnace distinguish them from the stream of gas leaving the furnace, catch the dust collector of any known construction /cyclones, centrifugal dust separator and so on/ and return to the furnace in the flue gas stream. In this case, the linear velocity of the stream of flue gas and microspheres predecessor catalyst carrier, designed for the living section, exceed the drift rate of these particles is /usually it lies in the range of 3-5 m/s /, and the time consumption of processed microspherical particles should not exceed 1/3 of the volume of the nozzle. Under such conditions, the nozzle performs two functions is s, and the function of the nozzle, providing close to porshneva the flow of the microspheres through the shaft furnace and the resulting factor is equal to the processing time for all particles of the precursor medium. The latter fact highlights another new technical result compared with prototype: in General if a fluidized bed is equal to the residence time of the carrier at the stage of thermal training can only be achieved with periodic registration process, in accordance with the invention it can be provided not only periodic, but also in a continuous process of thermal treatment, which is especially promises advantages in large-tonnage production of the catalyst.

Examples

These and other advantages of the method in accordance with the invention is illustrated below by examples.

Shaft furnace at a height of 10 m and a diameter of 0.8 m load fired at 140-1450 deg. C granules of aluminum oxide. The pellets are molded in the form of a cylinder the size /diameter approximately equal to the height/ 12-15 mm. After loading shaft furnace is heated flue gases obtained from the combustion of bessonnitsa natural gas to a temperature 77525 deg. Then in the thread d is 0 kg/h. The flow of three-hydrate of aluminum and flue gases pass through the said shaft furnace with a linear speed of 4 m/s in the calculation of the living section of the furnace. On leaving the furnace, the particles of the catalyst precursor is separated from the gas flow in the battery three-stage cyclone and returned to the entrance of the furnace. After 4-6 hours begin by selecting a thermally-prepared particles of the catalyst carrier, which is carried out at the outlet of the cyclone. Exhaust media continuously replace power technical three-hydrate of aluminum.

The resulting carrier is cooled and impregnated with an aqueous solution of copper chloride (II) / 20 g of CuCl2/ 100 ml H20/ 5% CuCl2/Al2O3and dried 4 hours at a temperature of 120 deg. C.

The resulting catalyst has the following fractional composition /content of the particles of/ in

less than 30 μm 4

less than 40 microns 9

less than 50 μm 65

less than 80 microns 89.

The catalyst test is as follows: the initial reagents ethylene, hydrogen chloride, and air in the ratio of C2H4:HCl:O21,02-1,08:2: 0,55-0,8 through the drying system, cleaning impurities and dosing served in the lower part of the reactor, representing a quartz tube with a diameter of 42 mm and is built in the form of a filter SCHOTT, ensure uniform distribution of the gas supply section of the reactor. The upper part of the reactor is made for extended trapping carried away by the gas flow of the catalyst particles. To measure and control the temperature of the reactor is equipped with a movable thermocouple, for measuring and controlling pressure mercury manometer.

In the reactor load 840 ml of catalyst. The reactor is heated to a temperature of 220 deg. C when the air supply to maintain the catalyst in a fluidized bed. After reaching this temperature the supply air change power source reagents, taken in the above ratio. The amount of power that corresponds to the conditional contact time of 16 C. the atmospheric Pressure. During the experience visually monitor the condition of the fluidized bed in the reactor. The amount of unreacted hydrogen chloride is determined by titration. Other reaction products chromatography. According to the analysis calculates the catalytic properties of a sample of the catalyst, which is presented below.

Conversion of HCl, 98,8

Conversion of C2H4, 97,6

The efficiency of the use of C2H4, 91,5

Burning, 4,6.

For comparison, in the same conditions ispyisail characterized by the following fractional composition, /particle content/

less than 30 microns 20

less than 40 microns 38

less than 50 μm 60

less than 80 microns 92.

Catalytic properties of a sample of the catalyst, is presented below.

Conversion of HCl, 96,7

Conversion of C2H4, 94,6

The efficiency of the use of C2H4, 88,0

Burning, 2,9

The data provided in addition to the above advantages of the technology of preparation of the catalyst illustrate the obtained catalyst activity and selectivity large compared to the prototype.

The examples illustrate the invention but do not limit its essence is expressed in the following claims.

The preparation method of catalyst for the oxychlorination process of ethylene containing chloride copper (II) on acidsolution media, including 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, characterized in that as microspherical predecessor media use technical trihydrate of aluminum and termicheskoe, made of solid inert material, thus resulting aluminum trihydrate is passed through the nozzle upward co-current, generated flue gas obtained by burning bessonnitsa the heating gas.

 

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