The method of producing catalyst for hydrofining of petroleum fractions

 

(57) Abstract:

The method of producing catalyst for hydrofining petroleum fractions containing oxides of molybdenum in the amount of 14-21 wt.%, oxides of cobalt or Nickel in amounts of 4 to 8 wt.%, oxides of phosphorus in the number ve 3-6 wt.% on a porous solid acid carrier, characterized in that when receiving carrier aluminium hydroxide peptizer by a mixture of nitric and phosphoric acids, taken in the ratio of 1:0.2 to 1:0.5 to mass fractions, molded in the form of extrudates, dried at a temperature of 100-120oC for 3-5 hours at a speed of temperature rise 20-30oC/h and calcined at a temperature of 400-700oC 4 hours, the impregnated carrier is carried out in two stages with intermediate drying at tempera - ture 100-120oC for 4 hours at a speed of temperature rise 20-25oC/h under the condition that the solution of salts of molybdenum, used- ' on the first impregnation stage, has a pH of 3.0 to 6.0.

The invention relates to the refining and petrochemical industries, in particular to methods of producing catalysts hydrofining petroleum fractions.

Known methods for producing catalysts for hydrodesulphurization unit oil fractions do not allow to synthesize kata is abode high-sulphur crude oil without reconstruction of existing facilities or performance.

Known, for example, a method of obtaining aluminoborosilicate catalyst for hydrofining of petroleum fractions by extruding material containing compounds of cobalt, molybdenum and aluminum hydroxide with bemani or pseudoboehmite structure [1]

The use of such catalyst in the Hydrotreating process high-sulphur diesel fractions is not possible to obtain low-sulfur diesel fuel.

When the hydrodesulphurization unit of hydrocarbons containing sulfur and nitrogen is used, the catalyst obtained by the preparation of extruded Al203containing material containing 2-6% NiO, 19-21,5% of Moo3and 2-6% R [2] This technology also does not allow to obtain a catalyst of high activity in reactions Hydrotreating of hydrocarbons.

The closest solution to the technical essence and the achieved result is a method of producing catalyst for conversion of hydrocarbons (hydrodesulphurization unit, hydrometallisation, hydrogencitrate and others) by impregnation of a carrier with a specific surface area of 10-400 m2/g and a pore volume of 0.15-1.5 cm3/g (Al2O3) stable (5-50)% aqueous solution of one or more compounds of al-10% of one or more components of group VIII (Ni, Co or their mixture in the form of nitrates, oxides and carbonates) [3]

However, the catalyst obtained has described activity is insufficient for processing high-sulphur raw in a long time.

The aim of the invention is to develop a method of producing catalyst for hydrofining of petroleum fractions in terms of existing hydrotreatment units.

This goal is achieved by a method of producing catalyst for hydrofining petroleum fractions containing oxides of molybdenum in the amount of 14-21 wt. oxides of cobalt or Nickel in amounts of 4-8 wt. oxides of phosphorus in the amount of 2-6 wt. on a porous solid acid carrier, characterized in that when receiving carrier aluminium hydroxide peptizer by a mixture of nitric and phosphoric acids, taken in the ratio of 1:0.2 to 1:0.5 to mass fractions, molded in the form of extrudates, dried at a temperature of 100-120oC for 3-5 hours at a speed of temperature rise 20-30oC/h, calcined at a temperature of 400-700oC 4 hours, the impregnated carrier is carried out in two stages with intermediate drying at a temperature of 100-120oC for 4 hours, at a speed of temperature rise 20-25oC/hour at Telsim sign the proposed method to obtain the catalyst for hydrofining petroleum fractions, when receiving carrier aluminium hydroxide peptizer by a mixture of nitric and phosphoric acids, taken in the ratio of 1:0.5 to>2-1:0,5 mass fractions, molded in the form of extrudates, dried at a temperature of 100-120oC for 3-5 hours at a speed of temperature rise 20-30oC/h and calcined at a temperature of 400-700oC 4 hours, the impregnated carrier is carried out in two stages with intermediate drying at a temperature of 100-120oC for 4 hours at a speed of temperature rise 20-25oC/h under the condition that the solutions of salts of molybdenum, used in the first impregnation stage, has a pH of 3.0 to 6.0.

Peptidase aluminium hydroxide with a mixture of phosphoric and nitric acids in predetermined ratios and the subsequent heat treatment to create the preconditions for receiving media with the textural characteristics, allowing for its use to various Hydrotreating petroleum fractions.

The two-stage impregnation of the carrier with solutions of salts of active metals allows you to choose for each solution the optimum value of pH, determined by the pH value. Stage intermediate drying can fix applied during the impregnation of molybdenum compounds on the surface of the aluminum oxide is ins pH, mounted to a solution of salts of molybdenum, is determined by the fact that at different pH values anions of molybdenum in the solution in a different form. It is found experimentally that the maximum activity in reactions hydrodesulphurization unit have heptamolybdate. In this state, ions of molybdenum are found in aqueous solutions at pH values of 3.0 to 6.0.

In known methods for producing catalysts hydrofining petroleum fractions the application of the described technology is unknown. Therefore, this solution meets the criteria of "novelty" and "significant difference".

The proposed method is illustrated by the following examples.

Example 1.

100 g of aluminium hydroxide is mixed with 25 ml of a mixture of phosphate (18%) and nitric acid (18%), taken in the ratio 1:0,2, moulded in the form of extrudates with a diameter of 2.0 mm and dried at a temperature of 100oC 3 hours. The speed of temperature rise of 20oC/hour. The obtained extrudates prokalyvayutsya at a temperature of 400oC for 4 hours. The resulting carrier is impregnated with an aqueous solution having a pH of 3.0 and containing paramolybdate ammonium in an amount necessary for the content in the finished product 21 wt. ACS isoC/hour. The obtained semi-product is impregnated with a solution containing Nickel nitrate in an amount necessary for the content in the finished product 8 wt. oxides of Nickel, dried at a temperature of 120oC for 4 hours and made red-hot at a temperature of 400oC for 3 hours.

For the obtained catalyst determine the mechanical strength, and spend the catalytic tests. When carrying out catalytic testing of a sample of the catalyst obtained in example 1, the raw material used gasoline fraction (raw material 1, table 1). The catalytic activity of the sample was evaluated by the reduction of sulfur and nitrogen stable hydrogenation product compared to the feedstock. When testing samples of catalysts on diesel fraction and a vacuum gasoil activity of samples was evaluated by the decrease in the content of sulfur and aromatic compounds in the hydrogenation product.

Process parameters for obtaining catalysts corresponding to examples 1-5 are given in table. 2. The quality of the raw materials used in the testing of catalysts are given in table.1. The test results in table.3.

The sequence of operations during execution of examples 2-5 is similar to example 1.

The method of producing catalyst for hydrofining petroleum fractions containing oxides of molybdenum in the amount of 14 to 21 wt. oxides of cobalt or Nickel in amounts of 4 to 8 wt. oxides of phosphorus in the amount of 2 to 6 wt. on a porous solid acid carrier, characterized in that when receiving carrier aluminium hydroxide peptizer by a mixture of nitric and phosphoric acids, taken in the ratio of 1: 0.2 to 1:0.5 to mass fractions, molded in the form of extrudates, dried at 100 120oC for 3 to 5 h at a speed of temperature rise 20 30oC/h and calcined at 400 700oC 4 h, the impregnation of the support is carried out in two stages with intermediate drying at 100 120oC for 4 h at a speed of temperature rise 20 25oC/h under the condition that the solution of salts of molybdenum, used in the first impregnation stage, has a pH of 3.0 to 6.0.

 

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