Method of making ball zeolite catalyst

 

(57) Abstract:

The invention relates to catalytic chemistry, in particular the preparation of pelletized zeolite-containing catalyst for the processes in the petrochemical, refining, organic synthesis. Increasing the strength of the spherical granules of zeolite-containing catalysts, as well as obtaining high output faction narrow particle size distribution in a wide range of sizes of the granules is achieved in that the binder used aluminum hydroxide in the amount of 20 to 40 wt.%, forming granules of the required size are by extrusion with a simultaneous sharp, followed by wilting to a moisture content of not more than 90% of the original moisture content of the molding material and the rolling of the pellets on the disc activatel with simultaneous dusting. In the molding composition may optionally enter recur in the amount of 1-15 wt.% the number of dry molding material; as reture use waste ground after rolling and sieving of the granules. 2 C.p. f-crystals, 1 table.

The invention relates to catalytic chemistry, in particular the preparation of pelletized zeolite-containing catalyst for the processes in the petrochemical, refining, organizes the ranks of the processes with stationary, and with a moving catalyst bed.

From the prior art there are known various methods of cooking the ball, including zeolite, catalyst. So, for example, ballpoint zeolite-containing catalyst formed from pseudonaja containing aluminum hydroxide and zeolite (pH 4-6), by passing droplets of pseudosasa first through a layer of hydrocarbon oil fraction, and then through an ammonia solution (method a liquid molding with external melirovanie) /1, 2/. Such methods of forming have several disadvantages, namely a long aging process of Almohades, leading to the frequency of the molding process, a large amount of wastewater containing ammonia, the low mechanical strength of the beads of zeolite-containing catalyst, which does not allow to use it in many processes.

There is also known a method of liquid forming with the inner melirovanie /3/. This method of molding involves the use of oil as the dispersion medium, which leads to the need for operation periodic regeneration oil as pollution and waste. This technology requires the use of additional AG is E. In this way forming the mechanical strength of the ball zeolite catalysts obtained are slightly higher compared with the method of liquid forming external melirovanie, however, this strength of the catalyst for use in many processes is insufficient.

Known methods for producing spherical granules of zeolite-containing catalysts methods okutyvaya. So, for example, zeolite, crushed to a grain size <0.25 mm, mixed with bentonite same grit and embryos from pre-granulated material is crushed to a size of 0.3-0.9 mm; the mixture is moistened continuously imposed on the rotating plate granulator and simultaneously moisturize her ode /4/. The disadvantages of these methods is again the low mechanical strength of the resulting balls in the case of cooking them on the basis of vysokoglinozemistykh zeolites.

Closest to the invention to the technical essence is a method of preparation of spherical granules of zeolite catalysts with balling /5/. Zeolite is mixed in the dry state with an inorganic binder and aglomerated in viriom mixer with the addition of water, and then the granules are stabilized by adding powder on zeolite-containing catalyst of existing in the presence of zeolite ZSM-5 and hydrated aluminium hydroxide (dried and ground) with p. p. p. (loss on ignition) 14% wt. according to the method described in the prototype.

Example 1 (prototype). In a vortex mixer mixed in a dry state 1 kg of zeolite with structure of ZSM-5 (air-dried) with 0.5 kg of hydrated aluminium hydroxide (HPA), with p. p. p. 14 wt.

After 5 minutes in the mixer serves the water sprayed in the form of a mist and obtain granules having humidity (110oC) 34 wt. Granules pripudrivayut zeolite powder with hydrated aluminum hydroxide and roll 10 min to retrieve balls. The resulting beads are dried at room temperature, sieved fraction of the desired size (2.5-3 mm) and calcined for 6 h at 550oC. the resulting beads have a strength of 3 kg/bulb. The yield of the target fraction is 30 wt.

This method has the following disadvantages:

low yield of spherical granules with a size less than or equal to 3 mm (this way with a good solution to get a sphere with a size of 4-6 mm);

the crushing strength of the obtained balls after annealing is (for the balls about 2.5 mm in size) 2-3 kg/bulb.

Although methods okutyvaya and seaming are more waste-free and environmentally friendly in comparison with methods Jew who, ball catalysts 2-3 mm in size on the basis of vysokoglinozemistykh zeolites suitable for industrial use.

The invention solves the problem of increasing the strength of spherical granules of zeolite-containing catalysts and to obtain high output faction narrow particle size distribution in a wide range of sizes of granules.

The essence of the proposed method lies in the manufacture of ball zeolite catalysts by preparing the masses for moulding consisting of a zeolite powder, 20-40 wt. the binder, which is used as the aluminum hydroxide with the addition of up to 15% (by weight total dry) rature (or without it) and water, followed by wet forming granules of the required diameter by extrusion with simultaneous cutting them so that the diameter of the granules was equal to the length, wilting them in one way or another in the conditions that lead to uniform distribution of moisture on the diameter and length of the pellets to a moisture content of not more than 90% of the original moisture content of the molding material and rolling the dried granules on the disc activatel with simultaneous dusting returm. Subsequent drying and calcining the spherical granules is carried out by any isdi after disc activates and sieving the dried catalyst, milled in a hammer, ball, disc or planetary mill.

Aluminum hydroxide is used as a binder instead of clay, because the clay contains impurities of oxides of other elements (e.g., iron and others), which may be parasitic activity in the process in which is used the resulting catalyst. It is known that the more binders are added, the greater strength is obtained catalyst. However, in the proposed method, the amount of binder is limited to 20 to 40 wt. since the introduction of a larger amount of the binder (catalytically inert) leads to a sharp decline in the catalyst activity.

The original humidity weight La molding by extrusion depends on such factors as the size and morphology of the zeolite crystals, the chemical composition of zeolites, including the degree of ion exchange, the type and quality of the binder, the type of extruder, etc., and can range 28-40 wt.

Use reture in the preparation of ball catalysts allows to avoid losses of zeolite and binder and to make a virtually waste-free technology. Adding more than 15% retur leads to deterioration of the strength characteristics of the floor is) to increase the strength of the resulting ultimately balls (compared with the methods of liquid moulding and wet seaming of powders), and secondly, significantly narrow the particle size distribution of spherical granules and cook the balls almost any required size, and varying the diameter used in extrusion dies.

Dusting granules by returm during okutyvaya on plate activatel prevents sticking of beads and education spheres agglomerates larger.

Wilting to a moisture content of not more than 90% of the source is made to prevent sticking of the granules and obtain a semi-product having optimum properties for seaming. For various types of zeolites, and even (if different morphology, crystal size and their chemical composition) for the same type of zeolite, can be very different not only to the original moisture content of the molding material, but the rest of humidity to which you want to podvalivat mass before rolling up. So if you have a large number of different types of zeolites virtually impossible to define a universal lower limit of residual moisture, which must be podvalivat catalyst pellet. However, for all types of zeolites, the upper limit of residual moisture before sealing should be no more than 90 wt. from Exodus is the current conditions, leading to uniform distribution of moisture on the diameter and length of the pellets, for example, by dusting dry powder Remora or exposure in the so-called "climate chamber", because the slow loss of granules moisture, or some other way.

Examples 2-9 illustrate the proposed method.

Example 2. In the mixer with Z-shaped blades 1 kg of powder of zeolite ZSM-5 is mixed with 0.5 kg of dry, milled hydrated aluminium hydroxide, having a loss on ignition (p. PP) 14 wt. and stirred for 15 min, then gradually with continued stirring, poured 0.8 l of water in which dissolved 5 ml of concentrated HNO3. Stirring is continued until the formation of the plastic mass. The resulting mass is transferred into an extruder and formed with a simultaneous sharp extrudates with a diameter of 3 mm and a length of 3 mm Obtained granules pripudrivayut dry mixture of zeolite and binder of the same composition, transferred to a high-speed disc activatel and doused to retrieve balls. The resulting beads are dried at room temperature in air, sieved fraction of 2.5 to 3 mm and calcined at 550oC for 3 h the resulting beads have the strength . what differentiates itself here the fact that in the preparation of the masses for forming in the mixer before adding water fall asleep yet 0,2 kg rature (milled in a ball mill dry residue after sieving beads obtained according to example 2), and dusting in both cases are powder reture. The resulting beads have a crushing strength of 18 kg/bulb. The yield of the target fraction is 87 wt.

Example 4. In the mixer with Z-shaped blades 1 kg of powder of zeolite ZSM-11 mixed with 0.5 kg of dry, milled pereosazhdeniya aluminium hydroxide (PGA) having a loss on ignition (p. PP) 14 wt. and stirred for 15 min, then gradually with continued stirring, poured 0,73 l of water. Stirring is continued until the formation of the plastic mass. The resulting mass is transferred into the extruder and molded simultaneously cutting the extrudates with a diameter of 2 mm and a length of 2 mm Obtained granules pripudrivayut dry mixture of zeolite and binder of the same composition, transferred to a high-speed disc activatel and doused to retrieve balls. The resulting beads are dried at 110oC for 5 h, sieved fraction of 1.8-2 mm and calcined at 550oC for 3 h the resulting beads have the strength razdavlivanija when preparing the masses for forming into a mixer, before adding water fall asleep yet 0,2 kg rature (milled in a ball mill dry residue after sieving beads obtained in example 4), and dusting in both cases are powder reture. The resulting beads have a crushing strength of 18 kg/bulb. The yield of the target fraction is 85 wt.

Example 6. In the mixer with Z-shaped blades 1 kg of powder of zeolite ZSM-48 is mixed with 0,95 kg autoclaved aluminium hydroxide (AH), with p. p. p. 70 wt. and stirred for 15 min, then gradually with continued stirring, poured 0,12 l of water. Stirring is continued until the formation of the plastic mass. The resulting mass is transferred into an extruder and formed with a simultaneous sharp extrudates with a diameter of 3 mm and a length of 3 mm Obtained granules pripudrivayut dry mixture of zeolite and binder of the same composition, transferred to a high-speed disc activatel and doused to retrieve balls. The resulting beads are dried at room temperature in air, sieved fraction 3.5-4 mm and calcined at 550oC for 3 hours, the Obtained balls have a crushing strength of 27 kg/bulb. The yield of the target fraction is 92 wt.

Example 7. Similar to example 6. About rature (milled in a ball mill dry residue after sieving balls obtained according to example 6), and dusting in both cases are powder reture. The resulting beads have a crushing strength of 21 kg/bulb. The yield of the target fraction is 90 wt.

Example 8. In the mixer with Z-shaped blades 1 kg powder galleriessilicone with the structure type ZSM-5 is mixed with 0.5 kg of dry, milled hydrated aluminium hydroxide, having a loss on ignition (p. PP) 14 wt. and stirred for 15 min, then gradually with continued stirring, poured 0.8 l of water. Stirring is continued until the formation of the plastic mass. The resulting mass is transferred into an extruder and formed with a simultaneous sharp extrudates with a diameter of 1.5 mm and a length of 1.5-1.8 mm. Obtained granules incubated at room temperature for 10 h under conditions practically prevents moisture loss (so-called "climate chamber") to a moisture content comprising 90 wt. from the source, transferred to a high-speed disc activatel and doused with simultaneous dry dusting original zeolite to retrieve balls. The resulting beads are dried at 110oC for 4 h, sieved fraction of 1.5-2 mm and calcined at 550oC for 3 h the resulting beads have p the example 8. Characterized in that in the preparation of the masses for forming in the mixer before adding water fall asleep yet 0,2 kg rature (milled in a ball mill dry residue after sieving beads obtained in example 8), and dusting are powder reture. The resulting beads have a crushing strength of 22 kg/bulb. The yield of the target fraction is 87 wt.

Thus, as seen from the above examples and tables, the use of the proposed method in comparison with the prototype allows

significantly increase the yield of the target fraction of balls;

to obtain a high yield of fractions narrow particle size distribution in a wide range of sizes;

significantly increase the strength of the resulting balls crush strength (almost an order of magnitude).

All the above suggests that the proposed method can find wide industrial use for ball zeolite catalysts.

1. Method of making ball zeolite catalyst comprising preparing a molding material by mixing the zeolite with an inorganic binder, the introduction of water into the molding composition, molding the pellets, followed by dusting, zacatin the aluminum in the amount of 20 to 40 wt. forming granules are by extrusion with a simultaneous sharp, subsequent uniform wilting granules to a moisture content of not more than 90% of the original moisture content of the molding material and the rolling of the pellets with simultaneous dusting returm.

2. The method according to p. 1, wherein the molding composition additionally impose recur in quantities of 1 to 15 wt. the number of dry molding material.

3. The method according to p. 2, characterized in that as reture use waste ground after rolling and sieving of the granules.

 

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