The preparation method of catalyst for hydrofining of crude oil

 

(57) Abstract:

The preparation method of catalyst for hydrofining oil stock comprising introducing into the alumina carrier of the active hydrogenating compounds, photobrush promoters and a pore-forming components, molding, drying and calcination before and after the introduction of all or part of the active hydrogenating compounds differs in that as photobrush promoters use aluminosilicate compounds of amorphous and crystalline structure and/or mixtures thereof in the amount of 20-70 wt.% from the General mass media, as aluminosilicate compounds crystal structure using the type zeolites , ZSM-5, the active hydrogenating compounds contribute from aqueous solutions of compounds of tungsten and/or molybdenum, Nickel or cobalt, having a pH of 2-6. The technical result is to obtain a catalyst that allows the hydrofining processes heavy oil fractions under conditions relevant technological parameters of operation of the domestic units for hydrotreatment of diesel fractions. table 1.

The invention relates to the refining, Neftekhimiya and chemistry, in particular to methods Aligator for Hydrotreating petroleum fractions, includes treatment of aluminosilicate media boric acid, salts of Nickel and molybdenum, drying and subsequent calcination of granulated catalyst at 500-550oC for 4-8 h, as silica-alumina carrier, a mixture of crystalline zeolite type CVM and of aluminum hydroxide with different structural characteristics in a specific mass ratio of the components [U.S. Pat. RF 2067023, bull. 27 from 27.09.96]. The disadvantage of this method is low kekirawa the ability of the resulting catalyst, which is explained by a suboptimal way to the introduction of the hydrogenating catalyst components (compounds of Nickel and molybdenum).

Also known preparation method of catalyst for hydrodewaxing oil fractions, including the application of hydrogenating components of Nickel and tungsten on a carrier which is a mixture of aluminum oxide and high zeolite [U.S. Pat. RF 2004321, bull. 45-46 from 15.12.93]. The disadvantage of this method is the impossibility of operation of the resulting catalyst in the processes of hydrofining of diesel fractions due to the rapid poisoning of the acid sites of the decomposition products contained in diesel fractions ser is of processing.

Closest to the proposed technical solution to the technical essence and the achieved effect is a method for preparing a catalyst for mild hydrocracking of crude oil, including the introduction in alumina porous carrier of the active hydrogenating component compounds of molybdenum and Nickel and/or cobalt, photobrush promoters, a pore-forming components, molding, drying and calcining, provided that razobratsya promoters bring in the media to the active components, and a pore-forming components contribute after making active components [RF Patent 2124400, bull. 1 from 10.01.99].

The disadvantage of this method is low kekirawa activity of the obtained catalyst at pressures below 50 MPa, i.e. in most existing installations hydrofining of diesel fractions and vacuum gasoil.

The aim of the present invention to provide a catalyst that allows the hydrofining processes heavy oil fractions under conditions relevant technological parameters of operation of the domestic units for hydrotreatment of diesel fractions.

This objective is achieved in that the hydrated carrier of the active hydrogenating compounds, photobrush promoters and a pore-forming components, molding, drying and calcination, provided that the drying and calcination is carried out before and after the introduction of all or part of the active hydrogenating compounds. As photobrush promoters and a pore-forming components used aluminosilicate compounds of amorphous and crystalline structure and/or mixtures thereof in the amount of 20-70 wt.% from the total mass of the carrier. As aluminosilicate compounds crystal structure using the zeolite type Y, ZSM-5. Active hydrogenating compounds contribute from aqueous solutions of compounds of tungsten and/or molybdenum, Nickel or cobalt, having a pH of 2-6.

The hallmark of the invention is that the drying and calcination is carried out before and after the introduction of all or part of the active hydrogenating compounds; as photobrush promoters and a pore-forming components used aluminosilicate compounds of amorphous and crystalline structure and/or mixtures thereof in the amount of 20-70 wt.% from the General mass media; as aluminosilicate compounds crystal structure using the zeolite type Y, ZSM-5; active hydrogenating compounds contribute from aqueous solutions with the Nations drying and calcination before and after introduction of the catalyst of all or part of the active hydrogenating component provides a carrier with the textural characteristics, necessary for optimal distribution of the active hydrogenating component on the carrier surface. Use as photobrush promoters and preobrazuemyh components aluminosilicate compounds of amorphous and crystalline structures, namely zeolite type Y, ZSM-5 allows due to the peculiarities of the structure and the geometric size of the input window to organize selective adsorption to hydrocarbons of various classes depending on the spatial location, shape and size of the molecule, which allows the reaction of selective hydrocracking of high molecular compounds. Making active hydrogenating compounds from aqueous solutions of compounds of tungsten and/or molybdenum, Nickel or cobalt leads to optimal dispersion hydrogenating component that increases the activity of the catalyst.

Thus, the present invention meets the criteria of "novelty" and "significant differences".

The following are specific examples of implementation of the proposed method.

Example 1.

stage 1

In the mixer load 250 g pellet of aluminum hydroxide mainly pseudoboehmite patterns with combustion loss parmout by extrusion into pellets through a die plate with a diameter of 3.0 mm These granules are maintained at a temperature of 20-22oC for 24 h, then dried at a temperature of 120oC for 4 h, and calcined at 550oC for 12 h Obtained granules have a diameter of from 2.1 to 2.3 mm, the strength is 2.8 kg/mm, water absorption is 0.52 ml of N2O 1,

stage 2

To make active hydrogenating compounds prepared aqueous solution as follows: 60 g of parabolicamara ammonium dissolved in a mixture of 100 ml of water and 50 ml of hydrogen peroxide with stirring for 1.5 h and heated to a temperature of 60oWith the addition of phosphoric acid to obtain a true sustainable solution at pH 2. Powder Nickel nitrate in the amount of 24 g was dissolved in 60 ml of water and added to a solution of parabolicamara ammonia under stirring at a temperature of 60oTo obtain a solution with pH value of 3. Before impregnation of the granules of the solution is brought to pH 4.

The calcined granules in the amount of 85 g pour the prepared solution taken in a volume of 65 ml, and mix thoroughly to a uniform distribution and the complete absorption of the solution.

The impregnated granules are maintained at a temperature of 18-22oC for 6 h, dried at temperature is contained WO3at 18.1 wt.%, NiO - 2.1 wt.%. Strength it is 2.3 kg/mm

The catalytic activity of the catalyst of example 1 was determined in the pilot installation in the hydrofining process of atmospheric gas oil with the following characteristics:

Density, g/cm3- 0,870

Fractional composition, oWITH:

N. K. - 280

10% boils at - 312

50% boils at - 339

Output fractions up to 360oWITH, % - 75

TemperatureoWith, not above:

turbidity - +9

pour - +3

Contents:

Sulfur, wt.% - 1,2

Aromatic hydrocarbons, wt.% - 23,0

Test conditions:

The hydrogen pressure, MPa - 40

The volumetric feed rate, h-1- 2

The temperature in the catalyst bed,oC - 360

The catalyst activity is assessed by the following indicators:

the increase in the output of FR. up to 360o(Kekirawa activity);

- reduction of sulfur content in FR. up to 360o(Obestsenivaya activity);

the decrease in the content of aromatic hydrocarbons in FR. up to 360o(Dearomatizing activity).

As a result of tests of the catalyst of example 1 is detected that the release of FR. up to 360oWith 87%, the sulfur content in this fracc the adiya

In the kneading machine was loaded to 90 g powder alumosilicate mainly pseudoboehmite patterns with SPT=32% and 61 g of a powder of zeolite ZSM-5 was mixed and added portions of water in the amount of 100 ml with intermediate and final mixing until a homogeneous mass. In the resulting mass make 60 ml of an aqueous solution of parabolicamara ammonium obtained as follows: 30 g of parabolicamara ammonium dissolved in a mixture of 50 ml of water and 25 ml of hydrogen peroxide with stirring for 1.5 hours at a temperature of 60oC.

The resulting mass is molded by extrusion through a die plate with a diameter of 3 mm, maintained at a temperature of 20-22oC for 24 h, dried at a temperature of 120oC for 4 h, and calcined at a temperature of 550oC for 12 h

The resulting granules have a diameter of from 2.2 to 2.4 mm, the strength is 1.8 kg/mm of diameter, water absorption of 0.57 ml of N2O 1,

stage 2

For depositing Nickel oxide prepared aqueous solution of Nickel nitrate: 11 g of Nickel nitrate dissolved in 60 ml of water and pH 3.8 pour 100 g obtained in the first stage, the intermediate product, mix thoroughly to a uniform distribution and the complete absorption of the solution. The impregnated granules is more at a temperature of 550oWith over 8 hours

The resulting catalyst contained WO3- 17.9 wt.%, NiO - 2.1 wt.%. Strength is 1.8 kg/mm

The catalytic activity is determined by the conditions of example 1. The output FR. up to 360oWith 90% of the sulfur content in this fraction was 0.2%, the content of aromatic hydrocarbons - 15%.

Example 3.

stage 1

Granules media is prepared analogously to example 1, except that instead of zeolite powder using the powder obtained by grinding chips aluminosilicate cracking catalyst containing 10% of zeolite type Y and 90% amorphous aluminosilicate.

The resulting granules have a diameter of from 2.2 to 2.4 mm, the strength of 2.5 kg/mm, the absorption 0,63 mm H2O 1,

stage 2

To make active hydrogenating components prepare an aqueous solution as in example 1, except that instead of parabolicamara ammonium use paramolybdate ammonium instead of nitrate Nickel nitrate cobalt.

The resulting catalyst contained the Moo3to 12.2 wt.%, Soo - 2.8 wt.%. Strength is 2.2 kg/mm Catalytic activity under the conditions of example 1: output FR. up to 360o- 91%, a sulfur content of 0.2%, the content of aromatic hydrocarbons 1-3.

Comparative data on the preparation conditions and properties of the catalyst according to the proposed method and the method according to the prior art (example 11) are given in the table.

As can be seen from the data presented, the catalyst samples prepared according to examples 1-7, process parameters, corresponding to the formula of the invention have high mechanical strength and activity. The yield of the target fraction FR.180-360oC is 87-92 wt.% (raw output of this fraction is 75 wt.%). The sulfur content in FR.180-360oFor samples with catalyst according to examples 1-4, which as hydrogenating components include compounds of Nickel and tungsten, is reduced from 1.2 to 0.2 wt.%, aromatic hydrocarbons - 23,0 15-18 wt.%. A sample of catalyst (example 4), containing compounds of Nickel and molybdenum, shows high activity in reactions of cracking (exit FR.180-360oC) and in reactions hydrodesulphurization unit (the sulfur content in FR.180-360oWith 0.2 wt. %), the content of aromatic hydrocarbons is not changed. A sample of catalyst according to example 5, which consists of hydrogenating components only compounds of Nickel, has only cretinously functions, but dostane Nickel, molybdenum and tungsten, exhibit high activity in reactions of hydrocracking and hydrogenation of sulfur compounds and aromatic hydrocarbons.

Beyond the proposed technical solution (examples 8-10) does not allow to achieve the desired result. Namely, in examples 8 and 10, it turns out the low strength of the catalyst, which does not allow to use it in an industrial environment. The catalyst according to example 9 does not have the required activity in reactions hydrofining.

Use during hydrofining heavy fractions of the type of atmospheric gas oil catalyst for prototype (example 11) does not allow to increase the yield of the target fraction of the required quality.

Thus, the described method compared with the method of the prototype allows to obtain a set of catalysts with high mechanical strength and high catalytic activity in the reactions of hydrocracking, hydrodesulphurization unit and hydrogenation of aromatic hydrocarbons in the processing of heavy petroleum fractions with technological parameters corresponding to the potential of the domestic hydrotreatment units.

The preparation method of catalyst for hydroalcohol obrazuyuscikh promoters and a pore-forming components, molding, drying and calcination before and after the introduction of all or part of the active hydrogenating compounds, characterized in that as photobrush promoters use aluminosilicate compounds of amorphous and crystalline structure and/or mixtures thereof in the amount of 20-70 wt.% from the General mass media, as aluminosilicate compounds crystal structure using the type zeolites , ZSM-5, the active hydrogenating compounds contribute from aqueous solutions of compounds of tungsten and/or molybdenum, Nickel or cobalt, having a pH of 2-6.

 

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