The catalyst in the form of extrudate

 

(57) Abstract:

Describes the catalyst in the form of astrodata consisting of inert binder selected from the class bumitaw or pseudoboehmite and a catalytically active part of SiO2/Al2O3gel, which is the product of the method lies in the (a) preparation of an aqueous solution of tetraalkylammonium hydroxide (TAA-OH), soluble aluminum compounds, the precursor of Al2O3during the hydrolysis, and the silicon compound, the precursor of SiO2during the hydrolysis, taken in amounts corresponding to the following molar ratios: SiO2: Al2O3= from 30:1 to 500:1, TAA-HE:SiO2= from 0.05:1 to 0.2:1, H2O:SiO2= from 5: 1 to 40:1; b) heating the resulting solution to implement in the reaction mixture to hydrolysis and gelation to obtain mixture (A) having a viscosity in the range from 0.01 to 100 Pas; and including d) drying the resulting extrudate; (e) calcining the dried extrudate in an oxidizing atmosphere; characterized in that it is the product of the method lies in V) adding to the said mixture (A) binder in a ratio by weight to the above-mentioned mixture (A) in the range from 0.05 to 0.5 s later added the AI and heated at 40 90°C obtained in stage (C) mixture to obtain a homogeneous paste which is then extruded. The technical result - the creation of a more simple method of obtaining a catalyst with good mechanical strength and greater activity. 9 C.p. f-crystals, 1 Il., table 4.

The present invention relates to a catalyst in extruded form, which is obtained by mixing a high-viscosity Sol obtained by hydrolysis and polycondensation of silicates and aluminates, with an inert binder.

The invention also relates to the use of such catalyst in the ways of oligomerization of olefins.

Known SiO2/Al2O3the gels are amorphous in nature, exhibiting catalytic activity. For example, in EP 160145 is considered a method of alkylation of aromatic hydrocarbons, which uses a catalyst consisting of SiO2/Al2O3gel amorphous nature, having pores with a diameter usually in the range from 50 to 500 at a ratio of SiO2:Al2O3usually in the range from 1:1 to 10:1.

M. P. C. Menton and j.Davids in the Journal of Cafalysis 60, 156-166 (1979) describe a method for the synthesis of amorphous SiO2/Al2O3- supported catalysts having a specific pore volume, i.e. the e l e C amorphous according to x-ray analysis, with the molar ratio of SiO2/Al2O3from 30: 1 to 500:1, with a specific surface area in the range from 500 to 1000 m2/g, a total pore volume from 0.3 to 0.6 ml/g, containing no pores with a diameter of over 30

This SiO2/Al2O3the gel obtained as follows:

(a) preparing an aqueous solution of tetraalkylammonium hydroxide (TAA-OH), soluble aluminum compounds, the precursor of Al2O3during the hydrolysis, and the silicon compound, the precursor of SiO2during the hydrolysis, in the following molar ratios:

- SiO2:Al2O3= from 30:1 to 500:1;

- TAA-OH:SiO2= from 0.05:1 to 0.2:1;

- H2O:SiO2= from 5: 1 to 40:1;

(C) the resulting solution is heated to the flow of the hydrolysis and gelation;

(c) the resulting gel is dried;

(d) the dried gel is calcined first in an inert atmosphere and then in an oxidizing atmosphere.

Received SiO2/Al2O3gel is catalytically active in the method of converting hydrocarbons.

Of course, there was a problem playing SiO2/Al2O3gel, discussed in the above patent, svyazannyi without loss of high catalytic performance.

Specialists known methods for producing extruded products having a sufficiently high values of mechanical strength, without changing their catalytic properties. For example, the catalyst may be ground to obtain a powder composed of particles of appropriate size, which are then mixed with a thickener.

Another way to get is to mix the powder SiO2/Al2O3gel a second powder of metal oxide in the presence of a thickening agent.

All of these methods give extrudates having a good mechanical strength, and unchanged catalytic characteristics.

In EP 550922 is considered extruded catalyst, which is obtained in accordance with known methods and consists of:

the catalytically active part representing SiO2/Al2)3gel is discussed in EP 340868;

- inert binder, representing Al2O3belonging to the class of boehmite or pseudoboehmite.

This catalyst shows good mechanical strength and a greater activity than the original SiO2/Al2ABOUT3-gel.

The specified catalyst obtained is ilkenny so, to have the powder with an average particle diameter of less than 50 microns, with an inert binder in the presence of a thickener containing a mineral or organic acid, to obtain a homogeneous paste which is then extruded with a small cylindrical pellets of a catalyst which is subjected to ripening, drying at 100-120oC and annealed in air at a temperature of from 500 to 600oC.

It has been unexpectedly found that the addition of boehmite or pseudoboehmite during the stage of receiving SiO2/Al2ABOUT3gel, which is preceded by the stages of drying and calcination, the result is a catalyst that is more active than the previously described gel and extruded catalyst discussed in EP 550922, based on SiO2/Al2ABOUT3gel and a binder selected from boehmite or pseudoboehmite.

In addition, the catalyst according to the present invention requires fewer stages of synthesis than is required to obtain extruded catalyst according to EP 550922: in particular, the stage of grinding the dried calcined gel is no longer necessary, and the stages of drying and calcination are performed only once on the extruded catalyst.

bound binder and a catalytically active part of SiO2/Al2O3gel, which is obtained by the fact that

(a) preparing an aqueous solution of tetraalkylammonium hydroxide (TAA-OH), soluble aluminum compounds as the precursor of Al2O3during the hydrolysis, and the silicon compound, the precursor of SiO2during the hydrolysis, in the following molar ratios:

- SiO2:Al2O3= from 30: 1 to 500:1;

- TAA-OH: SiO2= from 0.05:1 to 0.2:1;

- H2O: SiO2= from 5: 1 to 40:1;

(b) heat the resulting solution to implement in the reaction mixture to hydrolysis and gelation to obtain mixture (A) having a viscosity in the range from 0.01 to 100 Pas;

(C) add the specified mixture of (a) a binder selected from the class bumitaw or pseudoboehmite, in the ratio, by weight, to the above-mentioned mixture (A) in the range of 0.05 to 0.5; and then a mineral or organic acid in a quantity ranging from 0.5 to 8 g per 100 g binder;

(g) are mixed and heated at a temperature in the range from 40 to 90oC obtained in stage (C) mixture to obtain a homogeneous paste, which is then subjected to extrusion;

(d) obtained is dried extrudate;

(e) calcined dried extrudate in an oxidizing atmosphere.

The composition of the mixture from stage (b) and Priya in the range of 60 to 100oC for a time ranging from 15 minutes to 2 hours. Achieving a viscosity of from 0.01 to 100 Pas is at this stage is crucial. More viscous or less viscous products are unsuitable for processing in subsequent stages.

On stage (in) binder is preferably in the form of a powder with an average particle diameter of less than 50 microns.

In accordance with a preferred variant of the present invention, at the stage (C) is also added plasticizer. The plasticizer may be, for example, methylcellulose, stearine, glycerine. The plasticizer is added in the interval between adding the binder and the addition of mineral or organic acids.

At stage (d) mechanical mixing and the heat causes the evaporation of the solvent to obtain a homogeneous paste, which is of such a consistency that is typically considered suitable for extrusion. Retrieved cylindrical catalyst pellet sizes, which can vary depending on the requirements of the application, then the granules are subjected to aging at a temperature in the range from 20 to 40oC.

At stage (d) the catalyst is dried in a heating Cabinet at 100-120oC, and then on stage has a higher catalytic activity, than pure SiO2/Al2O3gel, and the SiO2/Al2O3gel, linked by a well-known method using a boehmite or pseudoboehmite.

This catalyst is suitable for use on an industrial scale, because he has an axial tensile strength (tensile strength at break in the range from 25 to 280 kg/cm2, a bimodal distribution of porosity and specific surface area in the range from 400 to 600 m2/,

The catalyst of the present invention can be, respectively, used in such conventional acid catalyzed chemical reactions like alkylation, isomerization and oligomerization.

In particular, it is very effective in the reaction of oligomerization of light olefins, particularly propylene, to obtain the hydrocarbon fractions showing exceptionally good properties as gasoline and jet fuel.

This oligomerization, respectively, is carried out at a temperature in the range from 100 to 250oC at a pressure of from 10 to 70 bar.

The following experimental examples are provided to better illustrate the invention.

An EXAMPLE of EPR-N. Propylamine (TPA-OH) at 13.3 per cent by weight; then added 389 g of demineralized water. The resulting solution was heated at 60oC until complete dissolution of the aluminum compounds; then, with stirring, is added 306 g tetraethylsilane.

The resulting mixture has the following molar ratios:

- SiO2:Al2O3= 50;

- TRA-HE: SiO2= 0,09;

- H2O:SiO2= 21.

The temperature is maintained at 60-65oC to obtain a mixture (A) with a viscosity 0,011 Pas.

800 g of This mixture after 20 hours of aging at room temperature is loaded into the mixer and then added 80 g of pseudoboehmite VERSAL 150 (manufactured by Za Roche) and 13 g of methylcellulose (Mefhocel 64625, the company Fluka). After about 1 hour of stirring is added 1.6 g of glacial acetic acid, and the temperature of the jacket of the mixer is increased to approximately 50-60oC. Stirring is continued until the mixture is hot, to obtain a homogeneous paste with the proper consistency for extrusion.

After extrusion the resulting extrudate of aging (aging) at room temperature until the morning, ripe extrudate is dried at 100oC for 5 hours, and the dried extrudate podvergalas strength 249 kg/cm2and specific surface 608 m2/,

EXAMPLE 2. (Preparation of the catalyst).

The mixture (A) is obtained similarly to obtain mixture (A) in example 1.

This mixture in an amount of 500 g, is loaded into the mixer and then the mixer is added 115 g of pseudoboehmite VERSAL 150 (firm Za Roche) and 19 g of methylcellulose (Mefhocel 64625, the company Fluka). After about 1 hour of stirring is added 0.6 g of glacial acetic acid, and the temperature of the jacket of the mixer is raised to about 50-60oC. Mixing is continued until the mixture is hot, to obtain a homogeneous paste with the proper consistency for extrusion.

After extrusion the resulting extrudate of aging (aging) until the morning when the room temperature is ripe extrudate is dried at 100oC for 5 hours, and the dried extrudate is exposed to 8-hour calcination at 550oC in air. It turns out the catalyst with a mechanical axial strength of 278 kg/cm2and a specific surface area of 500 m2/,

EXAMPLE 3. (Obtaining catalyst).

The technique is similar to the technique of example 2, without the addition of methylcellulose and using 2.3 g of glacial acetic acid.

It turns out cataler 4. (Obtaining catalyst).

The technique is similar to the method of example 3 using 5 g of glacial acetic acid dissolved in 10 ml of water.

It turns out the catalyst with a mechanical axial strength 99 kg/cm2and a specific surface area of 500 m2/,

EXAMPLE 5. (Obtaining catalyst/analogue).

Alumiiniumripplagesid in the amount of 12 g is added to 205 g hydroxide Tatra-ad-Propylamine (TPA-OH) when 13,35% by weight; then added 389 g of demineralized water. The resulting solution was heated at 60oC until complete dissolution of the aluminum compounds; then, with stirring, is added 306 g tetraethylsilane.

The resulting mixture has the following molar ratios:

- SiO2:Al2O3= 50;

- TRA-HE:SiO2= 0,09;

- H2O:SiO2= 21.

The temperature is maintained at 60-65oC for 60 minutes. The obtained gel is subjected to aging (aging) at room temperature for 10 hours, then dried for 3 hours in a rotary evaporator the rotavapor in the air stream, then in a heating Cabinet at 100oC. After 8-hour calcination at 550oC is obtained SiO2/Al2O3gel with appropriate 100 g of This SiO2/Al2O3gel is crushed in a rotary ball mill to obtain a powder with an average particle size distributions in the range from 10 to 200 μm. Such a powder is added to 100 g of industrial pseudoboehmite (CATAPAL IN firms Vista Chemical Company). Both powder are mechanically mixed in the mixer for 10 minutes.

Separately, prepare a 1% by weight aqueous solution of methylcellulose, and 130 g of this solution is then acidified with 2 g of glacial acetic acid (99.8 per cent by weight).

The acidified aqueous solution of methyl cellulose is then added to the powder mixture and the mixing continued until a homogeneous paste.

Thus obtained paste is extruded, and the extrudate is then subjected to aging (aging) at room temperature. Mature extrudate is dried at 100oC for 5 hours and made red-hot at 550oC for 8 hours in the air.

In the resulting catalyst, which has a mechanical axial strength of 87 kg/cm2and the specific surface 482 m2/,

EXAMPLE 6. Oligomerization of propylene.

Extruded catalyst obtained as described in example 1, ispitivanja cylindrical pellet;

- the size of the catalyst: the mean diameter of approximately 2.7 mm, the average length of approximately 5 mm;

- reactor type: reactor fixed bed;

- the size of the reactor: inside diameter: 25.4 mm length - 700 mm;

- the initial reaction mixture: a mixture of propene:propane = 70:30;

the reaction temperature: 120oC;

- reactor pressure: 35 bar;

the feed rate under normal conditions: 1 and 1.76 g of polypropylene per 1 g of the active phase in an hour.

Obtained in these tests results are given in table. 1, in which the JVI (time flow) is the total time of the test.

EXAMPLE 7.

The catalyst obtained according to example 3 is tested in the reaction of oligomerization of propylene in conditions analogous to example 6, except for the temperature and speed of submission:

the reaction temperature in the range from 120 to 160oC;

the feed rate under normal conditions: 1.85 g of polypropylene per 1 g of the active phase in an hour.

Obtained from these tests results are given in table. 2.

EXAMPLE 8.

The catalyst obtained according to example 4 is tested in the reaction of oligomerization of propylene in conditions similar to the conditions of example 6, is s, obtained from these tests are given in table. 3.

The product obtained in the conditions described in the table. 3, the first line contains the fraction suitable for use as gasoline (boiling point in the range from 60 to 170oC), and the fraction suitable for use as fuel in jet engines (the boiling point in the range from 175 to 300oC).

Curve acceleration of the specified product listed on the drawing.

EXAMPLE 9. (Comparative example).

The catalyst obtained in accordance with example 5, is tested in the reaction of oligomerization of propylene in the following operating conditions:

- form catalyst extruded cylindrical pellet;

- the size of the catalyst: the mean diameter of approximately 2.7 mm, the average length of approximately 5 mm;

- reactor type: reactor fixed bed;

- the size of the reactor: inside diameter: 25.4 mm length - 700 mm;

- the initial reaction mixture: a mixture of propene:propane = 70:30;

- reactor pressure: 38 bar;

the feed rate under normal conditions: from 1.8 to 3.1 g of polypropylene per 1 g of the active phase in an hour.

Obtained from these tests results are given in table. 4.

2/Al2O3gel, which is the product of the method lies in the (a) preparation of an aqueous solution of tetraalkylammonium hydroxide (TAA-OH), soluble aluminum compounds, the precursor of Al2O3during the hydrolysis and the silicon compound, the precursor of SiO2during the hydrolysis, taken in amounts corresponding to the following molar ratios:

SiO2: Al2O3= from 30 : 1 to 500 :1;

TAA-HE : SiO2= from 0.05 : 1 to 0.2 : 1;

H2O : SiO2= from 5 : 1 to 40 : 1,

b) heating the resulting solution to implement in the reaction mixture to hydrolysis and gelation to obtain mixture (A), and comprising; d) drying the resulting extrudate; (e) calcining the dried extrudate in an oxidizing atmosphere, characterized in that it is the product of the method lies in V) adding to the said mixture (A) having a viscosity in the range from 0.01 to 100 PA with a binder in a ratio by weight to the above-mentioned mixture (A) in the range of 0.05 to 0.5; and then a mineral or organic acid in a quantity ranging from 0.5 to 8 g per 100 g binder; d) stirring and heating at 40 - 90oC obtained in stage (C) mixture to p is that stage (b) carry out 60 - 100oC for 15 min - 2 h

3. The catalyst p. 1, characterized in that in stage (b) binder is used in powder form with an average particle diameter of less than 50 microns.

4. The catalyst p. 1, characterized in that in stage (b) in the time interval between the addition of the binder and adding a mineral or organic acid type plasticizer.

5. The catalyst p. 4, characterized in that the plasticizer is selected from methylcellulose, stearin and glycerin.

6. The catalyst p. 1, characterized in that the drying stage (d) is carried out at 100 - 120oC.

7. The catalyst p. 1, characterized in that the calcination stage (e) is carried out at 500 - 600oC.

8. The catalyst p. 1 used in the reactions catalyzed by acid.

9. The catalyst p. 8 used in the reaction of oligomerization of light olefins performed at 100 - 250oC and at a pressure of 10 - 70 bar.

10. The catalyst p. 9 used in the reaction of oligomerization of propylene.

 

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