The method of obtaining alumina catalyst of training materials for the hydrofining of petroleum fractions

 

(57) Abstract:

Describes the method of obtaining alumina catalyst of training materials for the hydrofining of petroleum fractions by impregnation of the carrier - aluminium oxide, calcined at a temperature of not lower than 800C, aqueous solutions of salts of active ingredients, followed by drying and calcining, provided that as the carrier is alumina, having in its composition 2-5 wt.% -aluminium oxide, 73-85 wt.% -aluminium oxide and 25-10% by weight -of aluminium oxide is formed in the form of geometric solids having a size of 8 to 20 mm and the ratio of volume to surface area of 1.0 to 2.5 mm3/mm2drying the impregnated carrier in the temperature range of 40-120C is the speed of rise in temperature of 10-15C/h Technical result - obtaining catalyst, the use of which, together with the traditional Ecumenical or aluminoborosilicate Hydrotreating catalysts when they are layered loading will significantly increase the activity and prolong mainegenealogy period catalytic systems in reactions hydrodesulphurization unit in the processing of heavy petroleum fractions and raw materials containing unsaturated compound and mechanical impurities. 2 t is I a catalyst for hydrofining of crude oil.

One of the reserves to increase the yield of distillate products by refining is the inclusion of the so-called non-conforming raw materials, in particular products of secondary origin containing in its structure a significant amount of unsaturated hydrocarbons, mechanical and other impurities. The processing of such raw materials to the Hydrotreating unit leads to a sharp decrease of the service life of traditional catalysts [B. K. Nefedov, E. D. Radchenko, R. R. Aliev, Catalysts processes deep oil processing. M: Chemistry, 1992, -s.].

In this regard, in recent years, leading catalyst firms refining instead of inert ceramic media, downloadable usually above and below the main catalyst layer, proposed a number of Ecumenical and aluminoborosilicate catalysts of type KF-542 (Akzo Nobel);-514, 544, NS-814, NS-844 (Criterion Catalyst); TK-709 (Haldor Topsoe) [Oil and Gas Journal, 1993, V. 93, N 40, p.35-56], used as components of the layered charge along with the basic catalysts (catalyst system).

The disadvantage of the above catalysts is relatively rapid deactivation of catalytic systems when they are used in the Hydrotreating process among the species and solids.

The closest solution to the technical essence and the achieved effect is a method of obtaining a catalyst of the protective layer TC-711 (oil Refining and petrochemistry" 1996, N3, C. 18-20.), which consists in impregnating granules of aluminum oxide, calcined at a temperature of not lower than 800oC, aqueous solutions of the active components.

One of the major drawbacks of this method is to obtain a catalyst with a low level of activity in the hydrodesulphurization unit in the processing of heavy oil fractions containing unsaturated hydrocarbons and solids that do not always produce products that meet the modern requirements to their quality. In addition, obtained in this way the catalyst is characterized by relatively low meregenerasikan period due to the increase of the pressure drop in the reactor when it is used in catalytic systems. The pressure drop is usually observed in the processing of such raw materials due to the intensive coking upper catalyst layer (crust formation).

The aim of the invention is to obtain a catalyst, the use of which, together with traditional aluminum is sustained fashion to increase the activity and prolong mainegenealogy period catalytic systems in reactions hydrodesulphurization unit in the processing of heavy petroleum fractions and raw materials containing unsaturated compounds and mechanical mixtures.

This goal is achieved by producing the alumina catalyst of training materials for the hydrofining of petroleum fractions by impregnation of the carrier - aluminium oxide, calcined at a temperature of not lower than 800oC aqueous solutions of salts of active ingredients, followed by drying and calcining, provided that as the carrier is aluminum oxide having a composition of 2 to 5 wt.% -aluminium oxide, 73-85 wt.% -aluminium oxide and 25-10% by weight -of aluminium oxide is formed in the form of geometric solids having a size of 8 to 20 mm and the ratio of volume to surface area of 1.0 - 2.5 mm3/mm2; drying the impregnated carrier in the temperature range 40 - 120oC is speed of temperature rise 10-15oC/hour.

The hallmark of the invention is that as the carrier is alumina, having in its composition 2-5 wt. % of aluminum oxide, 73-85 wt. % of aluminum oxide and 25-10% by weight -of aluminium oxide is formed in the form of geometric solids, having the size of 8 - 20 mm and the ratio of volume to surface area of 1.0 - 2.5 mm3/mm2drying the impregnated carrier use as a carrier of aluminum oxide of a given composition (and respectively - structure) results in broad porous catalyst, characterized by the presence of hydrogenating and gidroobesserivaniya functions with a relatively low content of surface acid sites. This in turn provides, firstly, the protection of basic catalyst layer from mechanical impurities contained in raw materials and, secondly, significantly reduces the formation of cocaethlyene in the processing of raw materials with high content of unsaturated hydrocarbons. The combination of these characteristics allows using the proposed pre-catalyst Hydrotreating as weighted raw materials and raw materials containing unsaturated compounds and impurities for a long period of time with high bulk velocity without loss of activity and increase of the differential pressure hydrotreater unit.

Certain ratios of geometric shapes and sizes of the granules of the catalyst allow for loading of catalyst to achieve the optimum ratio of the bulk density and hydrodynamic resistance of the catalyst layer, which has a significant impact on the flow of raw materials processed and retains high activity of the data granules of the medium together with other parameters of the formulas of the present invention results in a catalyst with the highest strength, making it suitable for use as the top layer and the substrate under the main catalyst bed.

All this makes it possible to use an object of the present invention in the form of protective active layer in the preparation of catalytic systems for deep hydrodesulphurization unit weighted feedstock containing unsaturated hydrocarbons.

In known methods for producing catalysts for Hydrotreating processes of oil fractions the application of the described technology 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.

Prepare the impregnating solution. For this, 500 ml of water, heated to 40oC, dissolved with continuous stirring, 120 g of paramolybdate ammonium, the resulting solution add 4 ml of orthophosphoric acid and 125 g of Nickel nitrate. Next, 0.5 kg of aluminum oxide, formed in the form of a cylinder with a height of 20 mm and a diameter of 12 mm, containing 2 wt.% -aluminium oxide, 73 wt. % alumina and 25 wt.% -aluminum oxide, load capacity for impregnation. Required specialsa carrying out heat treatment, the molded pellets of aluminum hydroxide at a temperature of 850oC. media Loaded pour impregnating solution so that the level in the tank was 2-3 cm above the upper level of the media. The duration of the impregnation at a temperature of 20oC is 0.5 hours. Impregnated carrier provalivajut in air at room temperature for 6 hours, then aged in an oven at a temperature of 120oC for 6 hours, and the rate of rise of temperature in the range of 40-120oC is 15oC/hour. The resulting drying, the product is calcined at a temperature of 400oC for 3 hours. In obtained in example 1, the sample of catalyst contained 3.2 wt.% MoO3and 1.1 wt.% NiO

Samples of the catalysts according to examples 2-6 are prepared in the same sequence and using the same impregnating solution, as in example 1. Upon receipt of the sample of catalyst according to example 2 instead of the nitrate Nickel nitrate used cobalt. During the synthesis of the sample according to example 3 instead of Nickel nitrate used Nickel acetate, to obtain a sample according to example 4 is used only solution of Nickel nitrate. Other features of the synthesis of the catalysts of examples 1 to 6 shown in table 1. The samples of the examples is the result. Example 7 - prototype obtained in accordance with the note to obtain catalyst TK - 711.

Synthesized according to examples 1-7 of the catalysts was determined by mechanical crushing strength, bulk density and spent catalytic tests.

To determine the bulk density using measuring cylinders with a capacity of 500 cm3. Measuring cylinder weighing not exposed. The catalyst volume defined by shaking, weighed separately. When shaken, the cylinder is filled selected from the average sample pellets of catalyst portions 10-15 pellets. Volume to 500 cm3occupied by the granules, assessed visually with an error of 5.0 cm3. For the test arithmetic mean of two determinations, if the difference between them does not exceed 0.05 g/cm3.

Mechanical crushing strength is determined on procamera PC-2-1.0.

When carrying out catalytic tests in the quality of raw material used mixed diesel fraction 180 - 360oC with a sulfur content of 1.6 wt%, of unsaturated hydrocarbons 10 wt.%, mechanical impurities 1.2 wt.%

The tests were carried out at pilot plant with a total volume of the reactor 30 MPa, the volumetric feed rate to 5 h-1.

Catalytic tests of the invention were carried out in the composition of the catalytic system. In the preparation of the catalytic system as aluminoborosilicate catalyst used catalyst TH-70 (TU 38.1011111-96). The activation of the catalytic system was performed according to OST 38.01130 straight-run diesel fuel with a sulfur content of 1.3 wt.%.

The catalytic activity of the system was assessed by the sulfur content in the hydrogenation product and pressure drop in the reactor after 100 and 500 hours of catalytic systems.

A list of the catalytic systems used to estimate object of the present invention, and the results are shown in table 2.

It is seen that the catalytic system comprises a catalyst samples made in accordance with the formula of the invention (N 1-4) are far superior in activity in reactions hydrodesulphurization unit, and lower pressure drop as a catalytic system containing the prototype (N7) or traditionally used ceramic balls (N8), or without any protective layer (N9), and samples of the catalyst made by supraterritoriality oil fractions by impregnation of the carrier - aluminium oxide, calcined at a temperature of not lower than 800oWith aqueous solutions of salts of active ingredients, followed by drying and calcining, characterized in that as the carrier uses aluminum oxide, having in its composition 2 to 5 wt. % of aluminum oxide, 73 - 85% -aluminium oxide and 10 to 25 wt.% -of aluminium oxide is formed in the form of geometric solids, having the size of 8 - 20 mm and the ratio of volume to surface area of 1.0 to 2.5 mm3/mm2, drying the impregnated carrier in the temperature range 40 - 120oWith lead with the speed of temperature rise of 10 - 15oS/h

 

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