The preparation method of catalyst for hydrotreating petroleum products

 

(57) Abstract:

The invention relates to the refining, in particular to methods for preparing catalysts for use in hydrogenation processes in the Hydrotreating of petroleum fractions. The technical result is to increase the efficiency of manufacture of the catalyst with simultaneous improvement of physical-mechanical and technological characteristics. In the method, based on the preparation of the original mixture, which includes natural aluminosilicate, the formation of granules, the implementation of their heat treatment and impregnation with solutions of salts of hydrogenating metals, according to the invention, in the preparation of the initial mixture powder of natural aluminosilicate, preferably of Tripoli, in the amount of 10-30% by weight is mixed with aluminum hydroxide, and the annealing prepared mixture of aluminum hydroxide and natural silicate is carried out at a temperature of from 200 to 700oC. 8 C. p. F.-ly, 2 tab.

The invention relates to the refining, in particular to methods for preparing catalysts for use in hydrogenation processes in the Hydrotreating of petroleum fractions, the benefits of which use the main bearer of soosazhdenie silica gel and alumets of alumosilicates (U.S. patent N 4028273, CL 252-432, 1973). In the preparation of the basic carrier original mix aluminol and silicasol in such proportions as to obtain the carrier of Al2O3SiO2(1,5 30) 1. The resulting carrier is dried at 100-215oC. Alumosilicate mixed with 5-50 wt. inorganic oxide (ZrO2, But2or B2O3). The obtained dry mixture is impregnated with a solution of boron compounds and phosphates so that the phosphate content of boron was 13-35% of the Carrier is dried and impregnated with a solution of salts of Nickel and molybdenum. Then again dried and calcined at 700-1200oC.

The disadvantages of this method is that the preparation of a carrier

alumosilicates through aluminol and silicasol complicated by the use of dilute solutions of salts, acids, additional filtration and leaching; required treatment and recycling of wastewater.

Known method of preparing a catalyst for Hydrotreating petroleum fractions by impregnation at a pH of 1.5 to 3.5 pre-calcined alumina with a solution of salts of Nickel and molybdenum in the presence of phosphoric acid, followed by drying and calcination of the obtained catalyst mass. At the same time as aluminum oxide using hydroxy and 350-500oC for 15-180 min with subsequent hydration of the amorphous product at pH 5.0-5.5 and a temperature of 75-90oC, plasticization in an autoclave at 140-300oC for 3-6 h, molding, drying and calcination (RF patent N 2026111, class B 01 J 37/16, 27/19, 1995).

A disadvantage of this known method include its complexity, a lot of stages and, consequently, the high cost of the preparation of aluminum oxide of catalonias.

Known method of preparing a catalyst for Hydrotreating petroleum products (patent UK N 1528982, CL 1 E, 5 E, 1978), which contains hexagonal disulfide metal of group VIA of the Periodic table of chemical elements deposited on a refractory carrier of compounds with a layered structure, which may include natural or synthetic clay (kaolin, talc, pyrophyllite, montmorillonite and mica (floorit, Muscovite, Margarit). In a preferred embodiment, the carrier is formed by montmorillonite with empirical formula:

(2,4-3,0)SiO2Al2O3) (0,2-0,6)AB xH2O,

moreover, the layered lattice contain silica, alumina and B; And a cation selected from the group consisting of hydrogen ions, alkali and alkaline earth metals; is laineste 50% of the Activity of the catalyst increases by activator in particular, oxide or sulfide of a metal of the iron group, particularly cobalt. The catalyst is produced by impregnation of catalonias solution compounds decompose with the formation of hexagonal metal disulfide, for example, thiomolybdate ammonium thermally decompose with the formation of trisulde molybdenum, which in turn can be converted into molybdenum disulfide and hydrogen sulfide in the presence of hydrogen at 50-290oC and activated by heating in hydrogen at 325-400oC. the Activator is added by impregnation of the carrier with a solution of salts of cobalt, Nickel or iron, for example, iron nitrate. The carrier impregnated with a solution of the activator, followed by drying and thermal decomposition is carried out before application of the metal sulfide.

This is a known catalyst based on montmorillonite, although characterized by a smaller surface area than, for example, in the case of media from graphitized carbon, however, has a relatively high activity and selectivity in the hydrogenation compared with the known catalysts based on alumina, on the level of characteristics of known catalysts on the basis of graphite, and at the same time, has satisfied the bat is known as a material with good coking properties, which, as you know, leads by heating puttying then. The decrease in porosity is not possible to provide good mechanical properties (strength) of the catalyst without affecting the selectivity and activity.

The objective of the invention to provide a method for preparing a catalyst for Hydrotreating, do not have the disadvantages inherent in the above-mentioned known methods. Achievable technical result is reduced cost of manufacture of the catalyst with simultaneous improvement of physical-mechanical and technological characteristics, in particular, strength and activity.

This result is achieved in that in the preparation method of catalyst for Hydrotreating of petroleum products, which are prepared in the initial mixture, which includes the natural aluminosilicate, shut the mixture shuts liquid is formed into granules, carry out the heat treatment of the obtained granules comprising drying and calcination, impregnation obtained pre-calcined alumina with solutions of salts of hydrogenating metals and final heat treatment, according to the invention, when forming the initial mixture powder of natural silicate in the amount of 10-30% from m the Oia and natural silicate is carried out at a temperature of from 200 to 700oC.

Preferably as a natural aluminosilicate use loose weakly cemented tongaporutu breed based on opal Tripoli.

Preferably also natural aluminosilicate used in the form of powder with particle size less than 200 microns.

If the produced catalyst is designed to remove oil, as shuts the fluid is preferably used an aqueous solution of phosphoric acid, the amount of which is determined from the conditions for obtaining 2-10% of the phosphorus in the calcined product, and if produced, the catalyst is designed for purification of diesel fuel, as shuts liquid use water.

In addition, the pre-impregnation of the calcined alumina is preferably carried out with aqueous solutions of salts of hydrogenating metals with pH from 2 to 10, and the impregnation is carried out in two stages, separated additionally introduced cycle intermediate heat treatment, the annealing phase of the intermediate processing is carried out at a temperature from 200 to 500oC during the time interval from 2 to 10 o'clock

Finally, the annealing in the final heat treatment of the granules SS="ptx2">

The achievement of the technical result of the invention is the whole set of essential features. The features that distinguish the invention from its closest analogue, are the composition and physical characteristics of the original mixture, the conditions of heat treatment of the granules prepared catalyst mixture. The achievement of the technical result is proved as follows.

Corresponding to the invention the modification of the initial mixture, consisting in the replacement of the component of the main carrier at substantially cheaper component (the cost of natural aluminosilicate more than 100 times less than the cost of aluminum hydroxide), can be carried out without deterioration, and in some cases, and the improvement of the main physical-mechanical and technological characteristics of the catalyst, subject to the above processing conditions, composition and parameters of the used materials. In particular, it was found that the Hydrotreating catalyst obtained using the corresponding the invention, a method has higher catalytic activity and mechanical strength compared with what is provided by traditional known similar way Tripoli - friable, poorly cemented temporada rock, consisting mainly of opal, which is an amorphous gel of silicic acid, contains small quantities of components, which, in particular, serve as sintering additives, resulting in a hardening without deterioration of properties due to reduction of the surface caused by sintering.

In addition, in the production of catalysts are of great importance sorption characteristics of kataloogidele, and used the aluminosilicate is a good sorbent is characterized by a specific surface area of up to 250 m/g, and ensure effective absorption of the impregnating solutions active in the catalysis of components.

Activation of phosphoric acid in the above proportions improves the adsorption characteristics of aluminosilicate due to the formation of oxysalts, and also improves the strength characteristics due to the formation of aluminum phosphate.

Studies have shown that when the Hydrotreating of diesel fuel is have both macropores and micropores of the catalyst Hydrotreating. Micropores, obviously, overgrown formed by activation with phosphoric acid phosphate of aluminum. Therefore actionable peers. Therefore, in this case, the main advantage of the new method is associated with significantly higher efficiency.

Provided by the invention is the possibility of using natural silicate in the composition of the initial mixture in an amount up to 30 wt. with a corresponding significant reduction in cost, allows the use of the catalyst for purification of heavy residues, which ensures an increase in the depth of oil processing in General. At the same time use in this situation, the existing catalysts, taking into account their cost, it would be unprofitable.

When the Hydrotreating of vacuum gas oil, as research has shown, is of greater significance macropores. The aluminosilicate has pores sufficiently large size so that the total effect of the impurities of aluminum silicate and phosphoric acid allows a great activity of the obtained catalyst Hydrotreating.

Quantitative characteristics of the modes of implementation of the claimed method are defined as follows. The minimum value of the temperature T and duration t on ignition is determined by when the desired strength of the catalyst. The maximum value for T on the e specifically that the temperature value, from which the reduced specific surface area and decreases the activity of the catalyst.

As for the maximum value of the interval of annealing, it is determined by economic considerations is the length of time, a further increase which was not feasible due to costs.

Specific values of T and t within the specified boundary values are determined for each individual case, taking into account specifically selected ratio of aluminum hydroxide, aluminum silicate and phosphoric acid, the ratio of Al2O3/SiO2in the aluminosilicate, etc.

The invention is illustrated below with specific examples of the preparation of the catalyst Hydrotreating.

500 g of aluminum hydroxide was mixed with 100 g of natural aluminosilicate and loaded into the mixing machine. There was added 180 ml of 10% phosphoric acid, and the whole mixture was stirred for 1 h the resulting mass was extrudible. The extrudate was dried in an oven to a temperature of 180oC and then progulivali in the temperature range 200-700oC for 24 h Obtained granules were filled with a solution of paramolybdate ammonium concentration of 15-20% (based on 1.5 volume rest is stirred during the day and progulivali for 3 h at 500oC.

The pellets were cooled, placed in a solution of Nickel nitrate (can also be used a solution of cobalt nitrate) concentration of 10% at the rate of 1.5 volume of solution to 1 volume of the granules, and kept in the solution for 4 h Then was carried out by drying and calcination at 500oC for 3 h

Testing of the catalyst was carried out under the following conditions: a pressure of 0.4 MPa, the volumetric feed rate 3 h-1the rate of circulation of the hydrogen-containing gas 500, raw diesel fuel with a sulfur content of 1.9% and vacuum gasoil Arlan oil with a sulfur content of 3.2%

The temperature was varied from 350 to 390oC in increments of 10oC. the catalyst Activity was determined by the formula

< / BR>
where Cnthe sulphur content in raw materials, wt.

Ctothe sulfur content in product, wt.

For comparison, by the same method and with impregnating solutions of the same concentrations were prepared Hydrotreating catalysts on the basis of pure aluminum hydroxide and aluminum hydroxide with the addition of phosphoric acid.

Data on the activity of the catalysts obtained according to the invention, and a known manner (Radchenko D. E. Nefedov B. K. found in table. 1 (diesel) and in table. 2 (vacuum gasoil).

As follows from the data table. 1, the addition of phosphoric acid to pure aluminum hydroxide (line 2) practically does not change the properties of the catalyst on the basis of pure aluminum hydroxide (line 1). Supplement natural aluminosilicate (line 3) has not resulted in significant changes in the properties of the comparison catalysts (lines 1 and 2). Additional activation of the acid (line 4) is also weakly altered properties compared to previous versions.

Thus, the obtained results show that the addition of natural aluminosilicate when relevant to the invention the composition of the processed mixture and processing modes without deterioration of the catalyst gives a real effect, as a kind of cost-cutting thinner. As mentioned above, the cost of aluminum hydroxide is greater than the cost of natural aluminosilicate almost 100 times.

In the case of Hydrotreating of vacuum gas oil additive only phosphoric acid to aluminum hydroxide weakly increases the activity of the catalyst compared with a catalyst based on pure aluminum hydroxide (line 2 of the table. 2 compared with the line 1 table. 1).

Similarly, d is compared with manufactured on the basis of pure aluminum hydroxide and based on pure aluminum hydroxide with the addition of phosphoric acid (line 3).

At the same time, the addition of phosphoric acid and natural aluminosilicate to aluminum hydroxide in the proportions provided by the invention, leads to a noticeable increase in the activity of the catalyst compared with the previous cases (line 4).

Thus, in the case of Hydrotreating of vacuum gas oil using the catalyst obtained according to the invention, the decreasing value due to the additive nature of the silicate, as well as increased activity compared to conventional known methods.

1. The preparation method of catalyst for Hydrotreating of petroleum products, which are prepared in the initial mixture, which includes the natural aluminosilicate, shut the mixture shuts liquid is formed into granules, carry out the heat treatment of the obtained granules comprising drying and calcination, impregnation obtained pre-calcined alumina with solutions of salts of hydrogenating metals and final heat treatment, characterized in that in the preparation of the initial mixture powder of natural aluminosilicate in an amount of 10 to 30% by weight is mixed with aluminum hydroxide, the use of the.

2. The method according to p. 1, characterized in that as a natural aluminosilicate use loose labiekartosanu tongaporutu breed based on opal Tripoli.

3. The method according to p. 1 or 2, characterized in that the natural aluminosilicate used in the form of powder with particle size less than 200 microns.

4. The method according to PP.1 to 3, characterized in that when the purpose of the catalyst for purification of oil as shuts the fluid using an aqueous solution of phosphoric acid, the amount of which is determined from the conditions for obtaining 2 10% phosphorus in the calcined product.

5. The method according to PP.1 to 3, characterized in that when the purpose of the catalyst for purification of diesel fuel as shuts liquid use water.

6. The method according to PP. 1 to 5, characterized in that the impregnation of the pre-calcined alumina carried out with aqueous solutions of salts of hydrogenating metals from pH 2 to 10.

7. The method according to PP.1 to 6, characterized in that the pre-impregnation of the calcined alumina is carried out in two stages, separated additionally introduced cycle intermediate heat treatment.

8. The method according to p. 7, characterized in that the annealing at the stage that the intermediate annealing during final heat treatment of the catalyst pellets of the mixture is carried out at 200 500oC for 2 to 10 hours

 

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