The preparation method of catalyst for hydrotreating petroleum distillates

 

(57) Abstract:

The invention relates to catalytic chemistry, and in particular to methods of preparation of the catalyst for Hydrotreating a petroleum distillate from the sulfur compounds. Preparation includes obtaining suspensions of cobalt molybdate or Nickel containing 0.005-0.02 g-atom of iron per 1 g-atom of cobalt or Nickel, obtained by adding to the solution paramolybdate ammonium 1.5 to 20.0% hydrogen peroxide solution of nitrate of iron, then nitrate of cobalt or Nickel and mixing the resulting suspension of cobalt molybdate or Nickel with aluminum hydroxide with subsequent filtering, shaping, drying and calcination. The technical result - obtaining a catalyst with increased activity. table 1.

The invention relates to catalytic chemistry, and in particular to methods of preparation of the catalyst for Hydrotreating a petroleum distillate from the sulfur compounds.

There are several ways to obtain a catalyst for Hydrotreating petroleum distillates, closest to the technical essence and the achieved effect. Thus, known methods of obtaining a Hydrotreating catalyst comprising a mixture of compounds of molybdenum hydroxide al the compounds of cobalt or Nickel (U.S. Patent 3980522, CL 01 J 37/04, published. 1976 ) and the method of producing catalyst for Hydrotreating petroleum distillates by mixing compounds of molybdenum and cobalt with a suspension of aluminium hydroxide, evaporation of the slurry, extruding and calcining (U.S. Patent 4094820, CL 01 J 37/04, published. 1978).

The method of producing catalyst for Hydrotreating petroleum distillates (U.S. Patent 4094820, CL 01 J 37/04, published. 1978) is the closest to the technical essence and the achieved effect.

The disadvantage of these methods is to obtain a catalyst with a low level of activity, and with the increasing content of active components in the catalysts obtained in this way, you are unable to significantly increase their activity. So, when the Hydrotreating gasoline on the catalysts prepared according to U.S. patent 4094820 (CL 01 J 37/04, published. 1978), with increase in the content of molybdenum oxide in the catalyst from 11.6 to 15.0 wt.%, the sulfur content of the hydrotreated gasoline decreases from 2.3 only to 1.9 ppm. Further increase in the content of active components in the catalyst obtained by this method, practically does not increase its activity in the Hydrotreating of petroleum distillates.

The aim of the invention is the camping due to the method of producing a catalyst for Hydrotreating petroleum distillates, comprising a mixture of compounds of cobalt or Nickel and molybdenum with a suspension of aluminium hydroxide, followed by filtering, shaping, drying and calcination, characterized in that compounds of cobalt or Nickel and molybdenum using a suspension of cobalt molybdate or Nickel containing 0.005-0.02 g-atom of iron per 1 g-atom of cobalt or Nickel, obtained by dissolving paramolybdate ammonium 1.5 to 20.0% hydrogen peroxide solution, followed by introduction into the solution of nitrate of iron and then nitrate of cobalt or Nickel.

The hallmark of the invention is that as compounds of cobalt or Nickel and molybdenum use suspension molybdate Nickel or cobalt containing 0.005-0.02 g-atom of iron per 1 g-atom of cobalt or Nickel, obtained by dissolving paramolybdate ammonium 1.5-20% aqueous solution of hydrogen peroxide, followed by the introduction of iron nitrate and then nitrate of cobalt or of Nickel nitrate.

The modification of the suspension molybdate Nickel or cobalt iron ions can improve gidroobesserivaniya activity Hydrotreating catalyst, apparently due to the higher dispersion of obrazuyushcheisya not only at low, but at high concentrations of active ingredients.

In known methods for producing catalyst for Hydrotreating petroleum distillates application described reception is not known. Therefore, this solution meets the criteria of "novelty" and "significant difference".

The proposed method is illustrated by the following examples.

Example 1. In 51 ml of 1.5% hydrogen peroxide solution, dissolve 17 g of paramolybdate ammonium make 0.09 g of iron nitrate Fe(NO3)3N2O (atomic ratio of iron to cobalt in the solution of 0.005:1.0 in). In the resulting solution make 16 g of cobalt nitrate Co(NO3)36N2O. the resulting suspension of cobalt molybdate contribute 356 g of aluminium hydroxide (Al content2ABOUT3- 20 wt. %) and homogenized by intensive stirring for 1 h at 70oC. the Suspension is filtered. The resulting paste is formed into pellets with a diameter of 1.5 mm, dried for 4 h at 90-120oC and calcined at 500oWith over 8 hours

The resulting catalyst has the following characteristics.

The composition of the catalyst: the Moo3to 15.0 wt.%; Soo - 4.3 wt.%; Fe2ABOUT3- a 0.035 wt.%.

When the Hydrotreating of disallowance raw materials 4,0 h-1the effective reaction rate constant hydrodesulphurization unit was 25.

Using techniques described in example 1, the prepared catalyst samples 2, 3 and 4 when using different concentrations of hydrogen peroxide and with the addition of various quantities of nitrate of iron. A sample of catalyst 2 was synthesized using Nickel nitrate.

For comparison was prepared in a 5 sample of the catalyst in an analog (U.S. Patent 4094820, CL 01 J 37/04, published. 1978).

Example 5. 80 g of molybdenum oxide (IV) is suspended in 200 ml of water and heated to 90oC. Then, 65 g of a powder of cobalt carbonate is gradually mixed with the obtained suspension. The mixture is heated at 100oC for 2.5 h, diluted with water to 500 ml and contribute aluminium hydroxide. The catalyst mass is evaporated to a pasty state, formed by extrusion, dried and calcined by raising temperature at 45oS/h to 650oC and then maintained at 720oC for 1 h

The resulting catalyst has the following characteristics.

The composition of the catalyst: the Moo3to 15.0 wt.%; Soo - 5.0 wt.%; Fe203of 0.01 wt.%.

When the Hydrotreating of diesel fractions containing 0.9 Fiktivna the reaction rate constant hydrodesulphurization unit was 12.

For comparison was prepared in sample 6, upon receipt of which has been changed the order of the input of nitrate of iron.

Example 6. In 51 ml of 1.0% hydrogen peroxide solution, dissolve 17 g of paramolybdate ammonium make 16 g of cobalt nitrate Co(NO3)36N2O. To the resulting solution make 0.09 g of iron nitrate Fe(NO3)3N2O (atomic ratio of iron to cobalt in solution of 0.05:1.0 in). In the resulting suspension of cobalt molybdate enter 356 g of aluminium hydroxide (Al content2ABOUT3- 20 wt. %) and homogenized by intensive stirring for 1 h at 70oC. the Suspension is filtered. The resulting paste is formed into pellets with a diameter of 1.5 mm, dried for 4 h at 90-120oC and calcined at 500oWith over 8 hours

The resulting catalyst has the following characteristics.

The composition of the catalyst: the Moo3to 15.0 wt.%; Soo - 4.2 wt.%; Fe2ABOUT3- 0,034 wt.%.

When the Hydrotreating diesel fraction, containing 0.9 wt.% sulfur, when 340oWith, the partial hydrogen pressure of 3.5 MPa and space velocity of the raw material 4,0 h-1the effective reaction rate constant hydrodesulphurization unit was 14.

Comparative data with the data in example 1, shown in the table.

The data in the table confirm that the Hydrotreating catalyst obtained by the proposed method outperforms activity in the hydrodesulphurization unit oil distillate with a catalyst obtained by a known method. Thus, the reaction rate constant hydrodesulphurization unit on the catalyst obtained by a known method (example 5), in 2-2,5 times lower than the rate constant for the catalysts obtained by the proposed method (examples 1-3). Example 6 illustrates that changing the order of input of iron nitrate (nitrate of iron in example 6 was introduced after the introduction of nitrate of cobalt, and in examples 1-3 to make nitrates of cobalt or Nickel) is practically not observed to increase the activity of the catalyst in the Hydrotreating compared to the prototype.

A method of producing a catalyst for Hydrotreating petroleum distillates, comprising a mixture of compounds of cobalt or Nickel and molybdenum to aluminum hydroxide, filtering, shaping, drying and calcination, characterized in that compounds of cobalt or Nickel and molybdenum use suspension molybdate Nickel or cobalt containing 0.005-0.02 g-atom of iron per 1 g-atom of cobalt or nicein the introduction of iron nitrate and then nitrate of cobalt or of Nickel nitrate.

 

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