SU1696460A1 - Method of processing petroleum stock - Google Patents

Abstract

The invention relates to petrochemistry, in particular to the processing of crude oil, the purpose of which is to increase the degree of purification of raw materials from sulfur. The processing is carried out by hydrotreating in the presence of an alumino-cobalt-molybdenum or alum-nickel-molybdenum catalyst at elevated temperature and pressure. The catalyst used is a spent catalyst for the process of adsorptive purification of hydrogen-containing reforming gas from hydrogen sulfide at 20-120 ° C and containing 0.5-4.0% sulfur. The degree of desulfurization increases to 99.4 rel.% When refining gasoline and to 51.1 rel.% When refining diesel fuel. 1 tab. fe

Description

The invention relates to a method for hydrotreating petroleum feedstock and can be used in the petrochemical industry.

There is a method of refining crude oil by hydrotreatment on catalysts containing metals of the VI and VIII groups, in which the catalysts are first contacted with a mixture of hydrogen-containing gas (HBG) and hydrogen sulfide at a concentration of 5–10% by volume, a pressure of 0.1–3.5 MPa and temperature of 150-370 ° C. Then sulfur-containing raw materials are fed to the catalyst.

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The disadvantage of this method is the low activity of hydrotreating catalysts due to the reduction of part of the metal oxides to metals, which are more difficult to convert to sulfides.

There is a known method for the processing of petroleum distillates, in which the catalyst is heated in a VSG medium with elemental sulfur, which is loaded over the catalyst bed. The heating is performed stepwise at first to 140 ° C and at a pressure of 0.5-1.7 MPa, then a shutter speed of 2.0-2.5 hours is made, the temperature is raised to 180-200 ° C and the catalyst is kept at this temperature at a pressure of 2 , 0-2,5 MPa 2-3 hours. Then raw materials 2 are fed to the catalyst.

The disadvantages of this method are the difficulty in controlling the sulfidiro process.

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Because of the simultaneous loading of a large amount of sulfur, the possibility of rapid interaction of sulfur with a catalyst, the need to open hydrotreating reactors to overload the catalyst and to load sulfur after each regeneration.

The closest to the invention is a method of refining petroleum feedstock in which the hydrotreating catalysts used in the pre-sulfidation stage are treated with a sulfur-containing feedstock in the presence of hydrogen or a feed with the addition of various sulfur compounds, disulfide, carbon disulfide, mercaptans. Optimum temperatures of sulphurization are 260-300 ° C, pressure 0.2-2.0 MPa. Then hydrotreated 3.

The disadvantage of this method is the lack of activity of hydrotreating catalysts due to the coking of the feedstock. Thus, when hydrotreating diesel fuel with an initial sulfur content of 0.88 wt.% On an alumino-cobalt-molybdenum (ACM) catalyst under the conditions of a known method, the residual sulfur content in the hydrogenation product is 0.53 May. %, which corresponds to the degree of desulfurization of 39.8 rel.%.

The aim of the invention is to increase the degree of purification of raw materials from sulfur.

This goal is achieved by a method of refining petroleum feedstock by hydrotreatment at elevated temperatures and pressures using spent AKM or alum-nickel-molybdenum (AHM) catalyst during adsorption purification of VSH reforming from hydrogen sulfide at 20-120 ° C and containing 0.5-4.0 wt. % sulfur.

The specified temperature range corresponds to the operating parameters of the circulating VSG of industrial catalytic reforming units.

Example 1. 30 cm3 industrial AKM catalyst of the following composition, wt.%: CoO 4.5; MOOS 14.0; y-A120z - the rest, after unloading the pilot reformer from the adsorber, it is loaded into the reactor of the pilot hydrotreating unit. The sulfur content of the catalyst is 2.2% by weight. The adsorption of hydrogen sulfide from VSH reforming is carried out at 45 ° C.

The catalyst is dried and reduced with hydrogen (hydrogen consumption 20 l / h) while slowly raising the temperature to 150 ° C (7.5 h). Then it is sulphided by high-sulfur straight race gasoline containing 0.1 wt.% Sulfur, when the temperature rises from 150 to 300 ° C for 12 hours, at a pressure of 3.0 MPa, gasoline feed rate 150 nl / h and hydrogen supply 38 l / h

Hydrotreating subjected to prongon

high-sulfur gasoline with an initial sulfur content of 0.1 wt.%. Hydrotreating conditions: temperature 340 ° С, pressure 3.0 MPa, hydrogen supply 76 l / h, feed rate 150 ml / h, test duration 24 hours.

The residual sulfur content of the hydrogenate obtained in this example is 0.0006 May. % that corresponds

5 degrees of desulfurization 99.4 Rel. %

EXAMPLE 2: For hydrotreatment, an AKM catalyst is used after unloading from the canister a pilot reforming unit with a sulfur content of 0.5 May. % Adsorption

0 hydrogen sulfide from VSH reforming is carried out at 20 ° C. Drying, reduction, and serification of the catalyst are carried out as in Example 1. A diesel is subjected to hydrotreatment.

5 fuel with an initial sulfur content of 0.08 May. % The hydrotreating conditions are similar to example 1.

The residual sulfur content in the hydrogenation product obtained in this example is 0.49% by weight, which corresponds to a desulfurization degree of 44.3 rel.%.

Example 3. Use 30 cm3 of an industrial ANM catalyst of the following composition, wt.%: N104.5; MoO 18; y-AYuZ

5 - the rest, after unloading from the adsorber pilot plant reformer with a sulfur content of 4.0 wt.%. The adsorption of hydrogen sulfide from VSH reforming is carried out at 120 ° C. Drying, Restoration and Aging

0 catalyst is carried out as in example 1.

Diesel fuel with an initial sulfur content of 0.88 wt.% Is hydrotreated. Hydrotreating conditions are similar to Example 1.

5 The residual sulfur content in the hydrogenation product obtained in this example is equal to 0.43 wt.%, Which corresponds to the degree of desulfurization of 51.1 rel.%.

Example 4 (the famous method). 30 cm3

0 freshly rolled industrial AKM catalyst is loaded into the reactor of the pilot hydrotreatment unit, dried and reduced with hydrogen while slowly raising the temperature to 150 ° С (7.5 h). Then

5, the catalyst is sulfided by high-sulfur straight race gasoline containing 0.1 wt.% Sulfur when the temperature rises from 150 to 300 ° C for. 12 h, at a pressure of 2.0 MPa, gasoline feed rate 150 ml / h, hydrogen supply 38 l / h.

Diesel fuel with an initial sulfur content of 0.88 wt.% Is hydrotreated. Hydrotreating conditions are similar to Example 1.

The residual sulfur content in the hydrosonate obtained in this example is 0.53 wt.%, Which corresponds to a degree of desulfurization of 39.8 wt.%.

Example 5 (for comparison). For hydrotreatment, an AKM catalyst is used after discharging a pilot reformer with a sulfur content of 0.3 wt.% From the adsorber. The adsorption of hydrogen sulfide and VSH reforming is carried out at 15 ° C. The remaining conditions are similar to those described in example 2.

The residual sulfur content in the hydrosonate obtained in this example is equal to 0.54 wt.%, Which corresponds to the degree of desulfurization of 38.6 rel.%.

Example 6 (for comparison), For hydrotreatment, an ACM catalyst is used after discharging a pilot reformer with a sulfur content of 4.2% by weight from the canister. The adsorption of hydrogen sulfide from VSH reforming is carried out at 130 ° C. The remaining conditions are similar to those described in example 2.

The residual sulfur content in the hydrosonate obtained in this example is equal to 0.43 wt.%, Which corresponds to the degree of desulfurization 51.1 rel.%.

The conditions of the process and the results obtained are shown in the table.

An example (known method). The experiment was carried out according to Example 4, only hydrotreating was subjected to high-sulfur gasoline with an initial sulfur content of 0.1% by weight.

Residual sulfur content in hydro-. obtained in this example is equal to

0

0.01 wt.%, Which corresponds to the degree of desalination 90.4 rel.%.

Try (known method). The experiment was carried out according to Example 4, except that the AHM catalyst described in Example 3 was used as 5 Hydrotreating catalyst.

The residual sulfur content in the hydrosonate obtained in the example is 0.50 wt.%, Which corresponds to the degree of desulfurization of 43.1 rel.%.

The results are summarized in the table.

As can be seen from the table, the degree of desulfurization increases from 90.4 to 99.4 rel.% When refining gasoline and from 43.1 to 51.1 rel.% When refining diesel fuel. In this case, hydrotreating catalysts on which sulfur was adsorbed on less than 0.5 wt.% (Example 5) do not offer advantages over the known method. At the same time, an increase in the content of adsorbed sulfur in excess of 4% does not lead to further improvement in performance (Example 6). In addition, such a high content of adsorbed sulfur is achieved only after skipping hydrogen sulphide in the adsorber of circulating GAS.

Claims (1)

The invention The method of refining petroleum feedstock by hydrotreatment in the presence of an aluminum-cobalt-molybdenum or alum-nickel-molybdenum catalyst at elevated temperatures and pressures, is different from the fact that, in order to increase the degree of purification of the raw material from sulfur, the catalyst used hydrogen-containing reforming gas from hydrogen sulfide at a temperature of 20-120 ° C and and containing 0.5-4.0% sulfur. 0 five