A method of producing a catalyst for hydrotreatment of crude oil

 

(57) Abstract:

The invention relates to the refining catalysts, in particular catalysts for Hydrotreating of crude oil. The method is intended for the production of catalyst for Hydrotreating of crude oil with increased activity in the hydrogenolysis reaction of nitrogen-containing compounds in the oil. The method consists in the introduction of the aluminum hydroxide active components from a solution containing compounds of molybdenum, phosphorus and cobalt or Nickel, prepared at the beginning of paramolybdate ammonia, phosphoric acid and hydrogen peroxide at a ratio of Mo : P not more than 2.5 g-EQ./g-EQ and H2O2: Mo is not more than 0.4 mol/g-EQ, followed by the introduction in the resulting solution of proximaldistal ammonium composition [P2Mo5O23-x(O2)x] (NH4)6where x = 1 or 2, nitrate of cobalt or Nickel, while maintaining the pH of the solution is 1.0 to 2.6 when the common ratio in the solution in terms of g-EQ. Ni(Co) Mo : P= (0,8-1,8) : (1,1:2,5) : 1. 2 table.

The invention relates to the refining and petrochemical industries, in particular to methods of producing catalysts for Hydrotreating of crude oil.

A method of obtaining a catalyst is ammonium solution, followed by drying and calcining (SU, auth. St. N 1397077, class B 01 J 37/02, 1988).

There is also known a method of preparation of Hydrotreating catalyst by introducing a solution of ammonium molybdate in the presence of boric acid and hydrogen peroxide and ammonia solution of Nickel nitrate, followed by drying and calcining (SU, ed. St. N 1734818, class B 01 J 37/02, 1992).

The disadvantage of this method is the low activity of the resulting catalyst in the Hydrotreating of nitrogen-containing medium and heavy distillate fractions. This is a consequence of the formation on the surface of the medium coarse oxide phases of molybdenum and Nickel, which are then in the transition to working sulfide phase eternauta only partially, thereby reducing the efficiency of the active components.

In addition, the use of media in the oxide form leads to a decrease in specific surface area due to the closure fine pore crystalline oxide phase, and also makes it almost impossible to adjust the distribution of pore size.

The closest solution to the technical essence and the achieved effect is a method of producing catalyst for Hydrotreating petroleum fractions by introducing the carrier of the active components of the treatment of RA, or phosphoric acid, 2) nitrate cobalt, 3) zirconium bearing compounds, followed by ripening at ambient temperature, drying at 120oC during the night and annealing for 4 h at 500oC (FR, application, N 2688149, class B 01 J 37/02, 1992).

The disadvantage of this method is to obtain a catalyst with low diasterous activity in Hydrotreating processes of middle and heavy distillate fractions.

The disadvantage of this method is its complexity in the introduction active components by nabryzgivaniya impregnating solution for pellets calcined carrier, then it is necessary to conduct virtually unregulated stage of ripening at ambient temperature.

In addition, the inclusion in the resource base catalyst zirconium bearing liquid product firms Magnesium Electron Ltd unknown composition limits the production of the catalyst used in this method.

The objective of the proposed technical solution is to obtain a catalyst with increased activity against the hydrogenolysis of C-N bonds in the composition of the nitrogen-containing aromatic compounds that are prevalent in the middle * of the Hydrotreating catalyst is injected into the carrier solution, containing compounds of molybdenum and cobalt, or Nickel, followed by drying and calcining, as compounds of molybdenum use proximaldistal ammonium composition [P2Mo5O23-x(O2)x] (NH4)6(x=1,2) with a total value in the solution in terms of g-equivalents of Ni(Co) Mo:P=(0,8-1,8):(1,1-2,5):1 and pH of 1.0 to 2.6.

Phosphomolybdenum paracomplex are formed in the process of preparing an impregnating solution as a result of interaction of paramolybdate ammonium, hydrogen peroxide and phosphoric acid at a ratio of Mo:P<2.5 g-EQ/g-EQ and H2O2: Mo<0.4 mol/g-EQ (Volnov And. And. Paracomplex chromium, molybdenum, tungsten, M., Nauka, 1989, S. 56-80).

Comparative analysis of the prototype shows that the proposed solution differs from the prototype in that the impregnating solution proposed composition contains molybdenum in the composition of heteropolyanions, in which he coordinated with phosphate groups, and Nickel (cobalt) nitric acid in such a ratio in which the surface of the carrier are formed fine and legkovosstanovimymi and easy usernames active phase, which creates favorable conditions for interaction aktivnih optimum pH, what contributes to maintaining the high specific surface of the catalyst, which is very important to ensure deep diazotoluene of crude oil.

The method of preparation of the catalyst according to the proposed technical solution is as follows.

The preparation of the impregnating solution.

In water heated to a temperature of 50 - 60oC, dissolved paramolybdate ammonium, then add 30% hydrogen peroxide solution and stirred for 20 to 30 minutes, then make 85% phosphoric acid and stirred for 20 - 30 minutes In the resulting solution of proximaldistal ammonium 3 - 4 portions contribute Nickel (cobalt) nitric acid with continuous stirring, after making the last portion is stirred for 15 to 20 minutes until dissolved. Thus prepared solution is injected into the aluminum hydroxide, homogenized mass within 1 to 2 h at 70 - 85oC, filter, form, dried 4 h at 120oC and calcined at 480 - 500oC for 6 - 8 hours

The catalytic activity is determined in the Hydrotreating process of straight-run diesel fuel (fraction 180 - 360oC) at pilot plant with a reactor volume of 50 cm3at 380oC, hydrogen pressure of 20 ATM, the volume is 120 ppm.

Below are examples of the implementation of the proposed technical solutions.

Example 1. In 58 ml heated to a temperature of 53oWith water dissolve 22.1 g of paramolybdate ammonium, then make a 4.9 ml of 30% hydrogen peroxide solution and 8.4 g of 85% phosphoric acid. In the resulting solution of proximaldistal ammonium enter 23.3 g of cobalt nitrate and stirred until complete dissolution. The solution has a pH of 2.6.

Thus prepared solution is injected in 500 g of aluminum hydroxide (PPPoC = 80 wt.%) and homogenized for 1 h at 70oC. the Suspension is filtered, and the resulting paste with a pH of 5.2 molded into pellets with a diameter of 2.0 mm, dried at 120oC for 4 h, and calcined at 500oC for 6 h

The catalyst composition, wt.%:

MoO3- 14,1

CoO - 4,5

P2O5- 4,0

Al2O3- The rest.

The catalyst activity was evaluated by the residual content of sulfur and nitrogen in the hydrogenation product after 2 h after stable mode.

The sulfur content of 0.045 wt.%

The nitrogen content of 9 ppm.

Example 2 - 7. Perform all operations as in example 1, but with different ratios of components.

Information about golitely). For comparison was prepared alumnirelations the catalyst according to the method described in the prototype.

Data on the chemical composition and the activity of the catalyst are given in table. 2.

Consideration of the results of determination of the activity of catalysts prepared by the proposed method showed high activity in the process of gidrogenizirovanii diesel fuel with high activity in the process of hydrodesulphurization unit compared with the catalyst of the prototype. The strength of the catalyst according to the proposed technical solution is not inferior to the strength of the catalyst of the prototype, and the specific surface is much superior.

A method of producing a catalyst for hydrotreatment of crude oil is injected into the carrier of the active components from a solution containing compounds of molybdenum, phosphorus and cobalt or Nickel, followed by drying and calcining, wherein the first solution is prepared from paramolybdate ammonia, phosphoric acid and hydrogen peroxide at a ratio of Mo R not more than 2.5 g-EQ. /g-EQ. and H2ABOUT2Mo is not more than 0.4 mol/g-EQ. then, the resulting solution of proximaldistal ammonium composition

[P2Mo

 

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