RU2062146C1 - Method to produce catalyst for heavy petroleum fractions hydraulic purification - Google Patents

Abstract

FIELD: oil refinery. SUBSTANCE: catalyst for heavy petroleum fractions hydraulic purification has composition: MoO₃ - 16 - 21 % mass, Nio (CoO) - 5 -7 % mass, Al₂O₃ - balance. It is produced by impregnation of carrier ( aluminum oxide with given distribution of pores) with solutions of salts of molybdenum and nickel (cobalt), drying and calcination of extrudates. Method is distinguished by the fact, that for production catalyst with increased activity to remove sulfur by hydraulic action extrudates of aluminum oxide are subjected to impregnation, that are produced by moulding, drying and calcining of mixture of aluminum hydroxide with residual oil with at least 1 % mass of sulfur and taken in amount of 3 - % mass in respect to aluminum hydroxide weight and characterized by total volume of pores of 0.4 - 0.5 cm₃/g under condition that share of pores with radius of 10000 - 15000 A is equal to 20 - 25 %, crushing strength index is no less than 1.3 kg/mm. Example: 100 g of aluminum hydroxide is mixed with 5 g of residual oil with sulfur share of 1.0 % mass and is peptized with 18 % solution of nitric acid, moulded in the form of extrudates of 2 mm diameter, dried for 5 hours under temperature of 20 C, calcined under temperature 600 C and as result of it carrier is produced with 0.6 cm₃/g volume of pores, share of pores with diameter of 10000 - 15000 A equal to 25% and strength - 1.3 kg/mm. Produced carrier is impregnated with solutions of ammonium paramolybdate and nitrate of nickel with share of MoO₃ equal to 21 % mass and NiO - 7 % mass. EFFECT: simplified process. 1 tbl

Description

 The invention relates to the field of oil refining and petrochemistry, in particular to methods for producing a catalyst for hydrotreating oil fractions.

 Known methods for producing catalysts for hydrodesulfurization of oil fractions do not allow to obtain an effective catalyst for the implementation of the hydrotreating process of high sulfur heavy oil fractions characterized by elevated boiling points and the presence of tar-asphaltene compounds. Nevertheless, the development of such processes is necessary, in particular, for hydrotreating vacuum gas oil in order to obtain low-sulfur cracking feedstock, as well as hydrofining oil distillates.

 To date, in the implementation of such processes, hydrotreating catalysts of middle distillate fractions are used, which does not allow to obtain a product with a fairly low sulfur content.

 Known, for example, is a method for producing alumina-nickel-molybdenum impregnation catalysts for hydrofining oil fractions obtained on the basis of alumina modified with zeolite-containing components [1] Such catalysts are characterized by low strength characteristics and insufficient hydrotreatment of heavy oil fractions.

 There is also known a method for producing an aluminum-nickel-molybdenum catalyst for hydrotreating hydrocarbons by impregnating a carrier pretreated with fluorosilicic acid [2] This production method is very complicated technologically, in addition, the operation of the catalyst obtained by this method is accompanied by increased corrosion wear of the process equipment.

и >60% пор диаметром 20-60

, растворами соединений никеля и молибдена [3]
Однако использование при гидроочистки тяжелых нефтяных фракций такого катализатора не позволяет получить продукт требуемого качества в течение длительного времени.The closest solution to the technical nature and the achieved result is a method for producing a hydrodesulfurization catalyst by saturating a support Y-A1203 having> 75% pores with a diameter of 30-100

and> 60% of pores with a diameter of 20-60

, solutions of compounds of nickel and molybdenum [3]
However, the use of such a catalyst in hydrotreating heavy oil fractions does not allow a product of the required quality to be obtained for a long time.

 The aim of the alleged invention is to develop a method for producing a highly effective catalyst for hydrotreating heavy oil fractions.

cоставляет 20-25% индекс прочности на раскалывание не менее 1,3 кг/мм.This goal is achieved by implementing the method of producing a catalyst for hydrotreating heavy oil fractions containing MoO ₃ - 16-21% wt. NiO (CoO) 5-7% wt. Al ₂ O _{3 the} rest, by impregnating the alumina support with a predetermined pore distribution, solutions of molybdenum and nickel (cobalt) salts, drying and calcining the extrudates, provided that the alumina extrudates obtained by molding, drying and calcining the aluminum hydroxide mixture are fuel oil containing sulfur not less than 1.0% wt. taken in an amount of 3-5% wt. by weight of aluminum hydroxide, and characterized by a total pore volume of 0.3-0.6 cm ³ / g, provided that the proportion of pores with a radius of 10000-15000

makes up a 20-25% index of splitting strength of at least 1.3 kg / mm.

составляет 20-25% индекс прочности на раскалывание не менее 1,3 кг/мм.A distinctive feature of the proposed method for the preparation of a catalyst for hydrotreating petroleum fractions is that during the synthesis of the catalyst, aluminum oxide extrudates obtained by molding, drying and calcining a mixture of aluminum hydroxide with fuel oil containing at least 1.0 wt% sulfur are subjected to impregnation. taken in an amount of 3-5% wt. by weight of aluminum hydroxide, and characterized by a total pore volume of 0.3-0.6 cm ³ / g, provided that the proportion of pores with a radius of 10000-15000

constitutes 20-25% an index of breaking strength of at least 1.3 kg / mm.

 The introduction of aluminum hydroxide in the cake before the stage of extruding the carrier of fuel oil in a predetermined quantity results in a carrier with an optimal pore distribution, total pore volume and strength. In the synthesis of a carrier based on aluminum oxide without the use of fuel oil, optimum performance was not achieved.

в заданном количестве увеличивает доступ сырья к активным центрам катализатора, что повышает его активность. Чрезмерное увеличение доли транспортных пор приводит к снижению прочности носителя.An increase in the total volume due to an increase in pore diameter leads to a decrease in inactive spinel structures during the preparation of the catalyst; the presence of transport pores in the catalyst [4] with a pore radius of 10,000-15,000

in a given amount increases the access of raw materials to the active centers of the catalyst, which increases its activity. Excessive increase in the proportion of transport pores leads to a decrease in the strength of the carrier.

 The requirement for sulfur content in fuel oil is determined by the need to create optimal conditions for subsequent sulfidation of the catalyst at the stage of calcination of the carrier.

 The use of other oil fractions instead of fuel oil does not allow to obtain the desired results.

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

The proposed method is illustrated by the following examples:
Example 1.

25% прочностью 1,3 кг/мм. Полученный носитель пропитывают растворами парамолибдата аммония и азотнокислого никеля с содержанием Мо0₃ 21% мас. и NiO 7% мас.100 g of aluminum hydroxide is mixed with 5 g of fuel oil with a sulfur content of 1.0% wt. peptized with a solution of 18% nitric acid, molded in the form of extrudates with a diameter of 2.0 mm, dried for 5 hours at a temperature of 20 ^o C, 6 hours at a temperature of 100 ^o C, calcined at a temperature of 600 ^o C. The result is a carrier with a pore volume of 0, 6 cm ³ / g, fraction of pores with a diameter of 10000-15000

25% strength 1.3 kg / mm. The resulting carrier is impregnated with solutions of ammonium paramolybdate and nickel nitrate with a content of Mo 0 _{3 of} 21% wt. and NiO 7% wt.

 Catalytic tests are carried out for the obtained catalyst. During the catalytic tests, vacuum gas oil with a sulfur content of 0.84% wt. Was used as a raw material. The catalytic activity of the sample was evaluated by the degree of conversion of sulfur-containing compounds.

The results are shown in the table. The same table shows the parameters for the preparation of the catalysts according to examples 2 to 7 and the results of their tests. The sequence of operations when performing examples 2 to 7 is similar to example 1. All catalytic tests were carried out with the same technological parameters (partial pressure of hydrogen 30 ati, volumetric feed rate of 3 hours ^-1 , temperature 360 ^o C).

 It can be seen from the data in the table that the introduction of aluminum hydroxide into the cake before the stage of its formation of fuel oil with a given sulfur content and in the indicated amounts leads to an increase in pore volume without reducing the strength of the catalyst, and also creates an optimal pore radius distribution, which increases the activity of the catalyst. TTT1

Claims (1)

 A method of obtaining a catalyst for hydrotreating heavy oil fractions containing, by weight. MoO ₃ 16 21
NiO or CoO 5 7
Al ₂ O ₃ Else
by impregnating an alumina support with a predetermined pore distribution, solutions of molybdenum and nickel or cobalt salts, drying and calcining the extrudates, characterized in that the alumina extrudates are obtained by molding, drying and calcining a mixture of aluminum hydroxide with fuel oil containing sulfur no less than 1.0 wt. taken in an amount of 3-5 wt. by weight of aluminum hydroxide, and characterized by a total pore volume of 0.4-0.6 cm ³ / g, provided that the proportion of pores with a radius of 10000-

constitutes 20-25% an index of breaking strength of at least 1.3 kg / mm.

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