Method of producing granular titanium-containing zeolite

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing moulded titanium-containing zeolite. Powdered titanium-containing zeolite is moulded with binding material in form of a basic salt of aluminium 5,6-oxynitrate. The granules undergo drying at room temperature and at temperature 100-150°C, and are annealed at temperature 250-350°C.

EFFECT: high strength of zeolite granules and low power consumption.

5 ex

 

The invention relates to a method for producing a granulated high-strength titanium containing zeolite.

It is known that zeolites with MFI structure containing titanium, are used as catalysts in reactions of direct oxidation by hydrogen peroxide of substrates such as aromatic hydrocarbons (US 7038093, SS 37/00, publ. 02.05.2006), olefins (EP 0100119, C07D 301/12, C07D 303/04, publ. 08.02.1984), nitrogen-containing compounds (US 4918194, C07D 295/22, SS 87/02, publ. 17.04.1990; US 5320819, COIB 21/20, publ. 14.06.1994), and reactions maximiliane carbonylic compounds (US 4794198, SS 131/04, publ. 27.12.1988). However, the main constraint to industrial implementation of these processes is the small particle size titanium containing catalyst, greatly complicating the stage of its separation from the reaction mass. To remedy this allows the formation of a titanium containing zeolite particles in the desired size.

The known method (EN 2332409, C07D 301/12, B01J 29/89, B01J 37/04, publ. 27.08.2008) obtaining a molded titanium containing zeolite, which consists in the synthesis of titanium containing zeolite having the x-ray structure type MWW, and his subsequent molding. The resulting zeolite is mixed with a binder component, which is used as silicasol, a substance that promotes extrusion (methylcellulose), blowing agent (polystyrene Vara is this and water); a lot plastificator, and after achieving uniformity ekstragiruyut, receiving the granules of 1-2 mm; they are then dried at a temperature of 90-130°C for 3-5 hours and calcined at temperatures from 450 to 500°C for 3-7 hours.

This method has several disadvantages.

1. Granules of zeolite have low mechanical strength (resistance to lateral pressure is only 2 to N). This leads to the destruction of the granules in the process of operation, which contaminates the process flow and requires additional equipment to remove small particles of catalyst, carry out the reaction mass.

2. Such granular catalyst with x-ray structure type MWW, in the oxidation of olefins by hydrogen peroxide is characterized by a low yield of the target products in comparison with zeolite having a MFI structure.

In another method (EN 2353580, SW 39/02, publ. 27.04.2009) for granulated titanium containing zeolite spend a mixture of the prepared zeolite with a binder, a pore-forming substance, a substance that increases the viscosity of the moldable mass, in the presence of alcohol or water. Use preferably titanium containing zeolites with MFI-, MEL or MFI/MEL-structures, as a binder used aluminum oxide (25-45% wt.), the pore-forming - polystyrene (25-55% wt.), pastoor the respective additive cellulose or polyvinyl alcohol. The mixture is plastificator, ekstragiruyut, dried and calcined (at a temperature of from 400 to 800°C).

The disadvantage of this method is the use of a large amount of a binder Al2About3this inevitably leads to reduction of the proportion of the active component and increase the acidity of the resulting catalyst, which is undesirable in the oxidation processes, as well as the use of high temperatures on the stage of calcination, resulting in the destruction of the catalytic centers titanium containing zeolite and increase energy costs for the production of granulate.

The closest in technical essence and the achieved result of the present invention is the method described in the patent application "Process for obtaining molded silicalite titanium, which is chosen for the prototype. (EP 1268058, B01J 29/04, C07D 301/12, SS 249/04, publ. 02.01.2003).

According to this method, the process of obtaining the catalyst for the epoxidation includes the prior receipt of titanium containing zeolite and its formation, consisting of a mixture of zeolite powder with a binder of aluminum oxide, silicon oxide, hydrolyzable silicon compounds and partial or complete products of their hydrolysis, compounds of boron, phosphorus-containing compounds, clay minerals and their mixtures is pasteurisation; the molded mass to obtain granules; drying and calcination at a temperature of 500-750°C.

However, this method of obtaining granulated titanium containing catalyst has the following disadvantages.

1. The low mechanical strength of the granules (average value of the lateral compressive strength of pellets 23 H (~2.3 kg/cm2)).

2. The use of a large amount of binding of the component.

3. The high temperature stage of calcination.

The task of the invention is to improve the technology of granulated titanium containing zeolite in the form of a molded product when the expansion of raw materials.

The technical result is an increase in strength of granular titanium containing zeolite while reducing energy costs.

This technical result is achieved in that in the method of obtaining titanium containing zeolite in the form of a molded product, comprising a mixture of titanium containing zeolite with a binder, mixing, molding granules, drying and calcination, it is proposed to use as a binder in the formation of granules basic salt of 5,6-oxynitride aluminum and to carry out drying the granules at a temperature of 100-150°C and calcination at a temperature of 250-350°C. This allows to obtain granules of titanium containing zeolite after stage ignition with mechanical the th strength of at least 60 kg/cm 2.

The method is as follows.

Mix titanium containing zeolite of the MFI type and binder, taken in an amount of 10-25% by weight. calculated on the dry zeolite. The mixture is stirred for 15-20 minutes, then add water to it and stirring is continued for another 30-40 minutes until pliable, well-moldable mass. The resulting paste ekstragiruyut through the die plate screw granulator. The obtained extrudates - cylinders with a diameter of 2-5 mm and a length of 5-8 mm, dried in air at room temperature for 2-3 hours, and then subjected to heat treatment at a temperature of 100-150°C for 2-3 hours. After removing most of the water at the stage of drying the granules are subjected to calcination at a temperature of 250-350°C for 4-5 hours.

The essence of the invention is illustrated by the following examples.

Example 1.

208 g of tetraethylorthosilicate placed in a 3-liter reactor, add with stirring 8.5 g of tetraethylorthosilicate and the resulting mixture is cooled to approximately 1-2°C. Then with stirring at this temperature for about 5 h add a solution comprising 364,5 g of Tetra-n-propylaminoethyl (TPA-HE concentration of 40 wt.%) and 257 grams of deionized water. To complete the hydrolysis and distillation of the formed ethanol the reaction mixture is heated initially to approx the positive 80°C, and then incubated for approximately 3 hours at a maximum of 95°C.

Next, the resulting Sol was placed in an autoclave, mounted on the rocking chair, reciprocating motion with a speed of 2-1when the amplitude of 0.05 m, and maintained at a temperature of 170°C for 40 hours, continuing the stirring. After cooling, the resulting suspension of the obtained solid by centrifugation separated from strong mother liquor, washed with water to pH 7-8, dried for 12 hours at 120°C under vacuum (20 mm Hg), and then calcined at 550°C for 6 hours in a muffle furnace.

In example 1 get powdered titanium containing zeolite.

Example 2.

In a reactor equipped with a jacket for heating, place 100 g svezheosazhdennoi washed wet aluminum hydroxide (the content of Al(Oh)3in the pulp 18% wt.) and gradually added under stirring of 18.2 g of 40%nitric acid, maintaining the pH level 4-6, to complete the transition formed the basic salt of 5,6-oxynitride aluminum in the solution. To accelerate the interaction of the acid with the hydroxide precipitate reactor is heated to a temperature of 50°C.

The resulting solution was concentrated by evaporation at 105°C to constant mass.

In example 2, we can get a basic salt of 5,6-oxynitride aluminum.

In examples 4 and 5 were used to face acetoxysilane (TU 6-052-708-76) and glass liquid sodium (GOST 13078-81).

Example 3.

35 g of a powder of titanium containing zeolite with the spatial structure of the MFI obtained according to example 1, is mixed with 5.9 g (16,8%) basic salt of 5,6-oxynitride aluminum, obtained according to example 2. The mixture of powders is stirred for 10 minutes, and then portions add up 29.6 g of water and continue stirring for another 30 minutes.

The resulting mass is loaded into the extruder and forced through a die plate having holes with a diameter of 4.5 mm, obtain cylindrical pellets.

Thus obtained granulated titanium containing zeolite is dried in air at room temperature for 2 hours, and then sent to a convection dryer. The temperature in the dryer is maintained in the range of 100-120°C (temperature rise operate at a speed of 5°C/min). Then the samples are subjected to calcination at a temperature of 320°C for 5 hours.

The mechanical strength of 71.7 kg/cm2. Giprostoymost samples is 99.6% at the time of definition 8 o'clock abrasion Resistance (weight loss) is 98.2%.

Example 4.

30 g of a powder of titanium containing zeolite with the spatial structure of the MFI obtained according to example 1, is mixed with 8.8 g with water-alcohol emulsion of tetraethoxysilane (18,3% wt. in the calculation of the powder titanium containing zeolite). The mixture is stirred for 15 minutes and then add Aut 8 g of water and 1.5 g of carboxymethyl cellulose and continue stirring for another 30 minutes.

The resulting mass is loaded into the extruder and forced through a die plate having holes with a diameter of 4.5 mm, obtain cylindrical pellets.

Drying and calcination is conducted as in example 3.

Mechanical strength - 62.9 kg/cm2. Giprostoymost samples is 99% at the time of definition 8 o'clock abrasion Resistance (weight loss) - 98%.

Example 5.

20 g of a powder of titanium containing zeolite with the spatial structure of the MFI obtained according to example 1, is mixed with 3.6 g (18%) aqueous solution of liquid sodium glass (silicate modulus of 2.8; the density of a solution of 1.24 g/cm3). The mixture is stirred for 5 minutes, then add 10 g of water and 1 g of carboxymethyl cellulose and continue stirring for another 20 minutes.

The resulting mass is loaded into the extruder and forced through a die plate having holes with a diameter of 4.5 mm, obtain cylindrical pellets.

Thus obtained granulated titanium containing zeolite is dried in air at room temperature for 2 hours, then the samples are placed in a container with a solution of ammonium sulfate and incubated for 24 hours with slow stirring. Next, the granules of titanium containing zeolite is washed with water until neutral. Drying and calcination is conducted as in example 3.

Mechanical PR is durability - 65,3 kg/cm2. Giprostoymost samples was 97% at the time of definition 8 o'clock abrasion Resistance (weight loss) - 96%.

When using a binder in the amount of less than 10% there is a sharp decrease of the strength characteristics of samples of granular titanium containing zeolite, which is associated with the physical lack of binder. Thus, the mechanical strength of the samples obtained using 5% binder, depending on the applied component is 10-19 kg/cm2. Abrasion resistance is also reduced to 55-61%. When the content of the binder component in a mixture of more than 25% of the strength of samples increases, however, the use of such granular zeolites as catalysts of oxidation processes is impossible due to low catalytic performance (activity, selectivity, and others).

The optimum temperature at the stage of drying 100-120°C. Lower temperatures will not allow you to remove the water from the micropores of granulated titanium containing zeolite, and the rise of the temperature over 120°inappropriate and will lead to additional expenditure of energy.

When the temperature of annealing of less than 250°C. the binder component does not form stable relationships with particles of titanium containing zeolite, which does not allow to obtain samples with high mechanical strength. Thus, the mechanical strength of the samples, obtained at a temperature of calcination 230°C, depending on the applied binder is 25-28 kg/cm2. In addition, at low temperature calcination may occur incomplete removal of components, improving the rheological properties of the moldable mass, which, in turn, adversely affects the catalytic characteristics of granular titanium containing zeolite. Increasing the temperature of annealing above 350°C leads to increased energy consumption while maintaining mechanical and catalytic properties of the catalyst.

A method of obtaining a granulated titanium containing zeolite, comprising mixing powdered titanium containing zeolite with a binder, mixing, molding granules, the granules drying and calcination, wherein the binder in forming pellets using a basic salt of 5,6-xinitrc aluminum in amounts of 10-25 wt.% calculated on the dry zeolite, and the resulting granules titanium containing zeolite is dried first in air at room temperature for 2-3 h, and then at a temperature of 100-150°C for 2-3 h and calcined 4-5 h at 250-350°C.



 

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