RU2298578C1 - Heavy crude oil feed hydrogenation processing - Google Patents

Abstract

FIELD: petroleum processing.

SUBSTANCE: heavy crude oil feed is subjected to two-stage hydrogen treatment at elevated temperature and pressure in presence of oxide catalyst in the first stage and oxide zeolite-containing catalyst in the second stage, whereupon gasoline fraction, diesel fraction and upgraded residue are recovered from the catalytic reaction product. Diesel fraction is combined with starting feedstock in amount ranging from 2 to 45 wt %. Volume ratio of first-stage catalyst to second-stage catalyst varies between 1:1 and 1:3.

EFFECT: increased quality of target products.

3 cl, 3 ex

Description

The invention relates to the field of oil refining, specifically to a method for the hydrogenation processing of heavy oil feedstocks.

A known method of hydrogenation refinement of heavy diesel distillates (with K.K. = 400 ° C), providing fuel distillates containing about 0.1 wt.% Sulfur. The process is carried out at a temperature of 345-370 ° C, a pressure of 3.8-4.0 MPa on nickel-molybdenum catalysts. ("Oil refining and petrochemicals", No. 1, 1999, p. 11).

The disadvantage of this method is the possibility of its use only for raw materials with an end of boiling not higher than 400-410 ° C, which narrows the scope of its practical use.

There is also known a method for catalytic hydrocracking of crude oil at a temperature of 360-445 ° C and a pressure of 5.7-6.1 MPa with the release of gasoline, middle distillate fractions and residue from the hydrogenate. The output of the middle distillate fraction (component of diesel fuel) is 35-38 wt.% ("Refining and petrochemicals", No. 11, 1999, p. 28)

However, this method does not allow the production of commercial diesel fuel, and the high sulfur content in the residue does not allow using it as a high-quality raw material for other oil refining processes.

A known method of hydrogenation processing of a fraction boiling in the range of 250-500 ° C, which is carried out at a temperature of 360-425 ° C, a pressure of 4-6 MPa in the presence of aluminum-nickel-molybdenum or aluminum-cobalt-molybdenum catalyst in the first stage and at a temperature 350-415 ° C in the presence of aluminum-nickel-molybdenum zeolite-containing catalyst in the second stage. Gasoline and diesel fractions and the residue, which can be used as raw materials for catalytic cracking, hydrocracking, oil production, etc., are isolated from the obtained hydrogenate.

(RF patent No. 2205200, С10G 65/12, 2003). Closest to the claimed is a method for the hydrogenation processing of heavy petroleum feedstocks (vacuum distillates, deasphalting agents, mixtures thereof), which consists in a two-stage treatment of the feedstock with hydrogen at a temperature of 350-430 ° C, a pressure of 5-20 MPa, a volumetric feed rate of 0.1- 5.0 hour ^-1 in the presence of a catalyst containing elements of groups VI and VIII on alumina in the first stage and at a temperature of 350-430 ° C, a pressure of 5-20 MPa, a volumetric feed rate of 0.1-5.0 hours ^-1, in the presence of a catalyst comprising the elements of VI and VIII RUPP, type Y zeolite to alumina in the second step and subsequent isolation of fractions srednedistillatnyh processing products, and the balance comprising base oil. (RF patent No. 2135549, C10G 65/12, 1999).

The disadvantage of this method is the insufficient yield of high-quality fuel distillates.

The objective of the invention is to develop a method that allows for the hydrogenation processing of heavy petroleum feedstocks to increase yield and improve the quality of fuel distillates and residue while expanding raw materials without complicating the process flowchart.

To solve this problem, a method for the hydrogenation processing of heavy oil feedstock is proposed, which consists in a two-stage treatment of the feedstock with hydrogen at elevated temperature and pressure in the presence of an oxide catalyst in the first stage and in the second stage in the presence of an oxide zeolite-containing catalyst, followed by separation of gasoline and diesel fractions from the processed products and ennobled residue, in which according to the invention a diesel fraction in an amount of 2-45% wt. return to mixing with the feedstock and the ratio of the volumes of the catalysts of the first and second stages is from 1: 1 to 1: 3.

Oxide catalysts containing Group VI and VIII metal oxides and zeolite-containing oxide catalysts containing the above oxides and zeolites such as zeolite X, high-silica zeolites, for example, ICS, are used.

Preferably, the first stage is carried out at a temperature of 340-420 ° C, a pressure of 14-20 MPa, a volumetric feed rate of 0.5-3.0 h ^-1 on a wide-porous alumina-cobalt, a nickel-molybdenum catalyst and the second stage is carried out at a temperature of 360 -420 ° C, a pressure of 14-20 MPa, a volumetric feed rate of 0.3-2.0 hour ^-1 on an aluminum-nickel-molybdenum zeolite-containing catalyst.

The differences of the proposed method consist in the partial return of the separated diesel fraction to mixing with the feedstock and the ratio of the volumes of the catalysts of the first and second stages.

These differences make it possible to obtain a total of up to 65 wt.% Fuel distillates, including up to 50 wt.% Diesel distillate. The quality of the resulting fuel distillates meets modern requirements: diesel fuel contains less than 0.035 wt.% And 0.005 wt.% Sulfur, depending on the process conditions, the enriched residue contains less than 0.5 wt.% Sulfur and can be used as raw material for the catalytic cracking process.

When implementing the method, the placement of the catalysts of both stages can be carried out in a single reaction apparatus (in the form of two consecutive layers), or in two successive reaction apparatuses. Both stages of the process are carried out in a general hydrogen circuit.

The proposed method allows at the first stage to reduce the sulfur content by at least 40 wt.% And heavy metals (vanadium and nickel) by at least 50 wt.%, Which provides favorable conditions for the operation of the second stage catalyst.

The essence of the proposed method is illustrated by the following examples.

Example 1

Western Siberian oil is: sulfur content - 2.5 wt.%, Vanadium content - 60 ppm, nickel content - 30 ppm is subjected to hydrogenation in two stages. The first stage is carried out on a catalyst containing 3 wt.% Cobalt oxide and 10 wt.% Nickel oxide on wide-pore alumina at a temperature of 420 ° C, a pressure of 20 MPa, a feed volumetric rate of 0.5 hour ^-1 . The resulting product is subjected to processing in the second stage, which is carried out on a catalyst containing 5 wt.% Nickel oxide, 15 wt.% Molybdenum oxide and 5 wt.% Type X zeolite on alumina at a temperature of 390 ° C, a pressure of 20 MPa, space velocity feedstock 0.5 hour ^-1 . The catalysts of the first and second stages are taken in a ratio of 1: 1 and placed in one apparatus. The processing products obtained in the second stage are subjected to rectification with the release of 10 wt.% Gasoline distillate NK-160 ° C, 45 wt.% Diesel distillate 160-350 ° C and the residue boiling above 350 ° C. Diesel distillate in an amount of 22.5 wt.% Return to mixing with fuel oil.

After the first stage, the vanadium content decreased to 15 ppm, the nickel content to 5 ppm.

The resulting gasoline distillate contains 0.01 wt.% Sulfur, diesel distillate contains 0.035 wt.% Sulfur, the remainder is 0.2 wt.% Sulfur.

Example 2

Vacuum distillate of West Siberian oil, fraction 350-550 ° С: sulfur content - 1.6 wt.%, Vanadium content - 10 ppm, nickel content - 5 ppm subjected to hydrogenation in two stages. The first stage is carried out on a catalyst containing 2.5 wt.% Nickel oxide and 5 wt.% Molybdenum oxide on wide-pore alumina at a temperature of 340 ° C, a pressure of 14 MPa, a feed volumetric rate of 3.0 h ^-1 . The product obtained in the first stage is subjected to processing in the second stage, which is carried out on a catalyst containing 4 wt.% Nickel oxide, 17 wt.% Molybdenum oxide, 10 wt.% SVK zeolite on alumina at a temperature of 360 ° C, a pressure of 14 MPa, volumetric feed rate of 1.0 hour ^-1 .

The catalysts of the first and second stages are taken in a ratio of 1: 3 and placed in two sequentially arranged apparatuses.

The products obtained in the second stage are subjected to rectification with the release of 15 wt.% Gasoline distillate NK-180 ° C, 50 wt.% Diesel distillate 180-350 ° C and a residue above 350 ° C. Diesel distillate in an amount of 45 wt.% Return to mixing with the original vacuum distillate.

After the first stage, the content of vanadium decreased to 2 ppm, and nickel to 1.5 ppm.

The resulting gasoline distillate contains 0.03 wt.% Sulfur, diesel distillate contains 0.005 wt.% Sulfur, the remainder is less than 0.1 wt.% Sulfur.

Example 3

Vacuum distillate of eastern sulphurous oils - fraction 350-570 ° С, sulfur content 2.1 wt.%, Vanadium content 14 ppm, nickel content 8 ppm subjected to hydrogenation processing in two stages. The first stage is carried out on a catalyst containing 2 wt.% Nickel oxide and 10 wt.% Molybdenum oxide on wide-pore alumina at a temperature of 380 ° C, a pressure of 17 MPa, a bulk feed rate of 1.5 h ^-1 . The product obtained in the first stage is subjected to hydroprocessing in the second stage, which is carried out on a catalyst containing 7 wt.% Nickel oxide, 19 wt.% Molybdenum oxide and 10% by weight of CBK zeolite on alumina at a temperature of 420 ° C, a pressure of 17 MPa, volumetric feed rate 0.75 hour ^-1 .

The catalysts of the first and second stages are taken in a ratio of 1: 2 and placed in two sequentially located apparatuses.

The product obtained in the second stage is subjected to rectification with the release of 12 wt.% Gasoline distillate NK-160 ° C, 48 wt.% Diesel distillate 160-360 ° C and a residue above 360 ° C.

Diesel distillate in an amount of 2 wt.% Is returned to mixing with the original vacuum distillate.

After the first stage, the vanadium content decreased to 4 ppm, the nickel content to 2.5 ppm.

The resulting gasoline distillate contains 0.02 wt.% Sulfur, diesel distillate contains 0.035 wt.% Sulfur, the remainder is 0.15 wt.% Sulfur.

The proposed method can be carried out using oxide and zeolite-containing catalysts of a different composition in the framework of the above with similar results.

The above examples confirm that the proposed method allows the processing of heavy sulfur vacuum distillates having a boiling end of 550 ° C and above, and fuel oil containing a significant amount of heavy metal salts, to increase the production of high-quality fuel distillates that meet modern requirements, and in addition, to obtain ennobled residue that can be used as feedstock for catalytic cracking.

Claims (3)

1. The method of hydrogenation processing of heavy petroleum feedstock, which consists in a two-stage treatment of the feedstock with hydrogen at elevated temperature and pressure in the presence of an oxide catalyst in the first stage and in the second stage in the presence of an oxide zeolite-containing catalyst, followed by separation of gasoline and diesel fractions from the processed products, and ennobled residue, characterized in that the diesel fraction in an amount of 2-45 wt.% return to mixing with the feedstock and the ratio of volumes rolled congestion of the first and second stages is from 1: 1 to 1: 3. 2. The method according to claim 1, characterized in that the first stage is carried out at a temperature of 340-420 ° C, a pressure of 14-20 MPa, a volumetric feed rate of 0.5-3.0 h ^-1 on wide-porous alumina-cobalt-nickel molybdenum catalyst. 3. The method according to claim 1, characterized in that the second stage is carried out at a temperature of 360-420 ° C, a pressure of 14-20 MPa, a bulk feed rate of 0.3-2.0 h ^-1 on aluminum-nickel-molybdenum zeolite-containing the catalyst.