Method of refining gasoline distillates

 

(57) Abstract:

The proposed method is intended for refining gasoline distillates containing, along with the sulphur compounds, unsaturated and aromatic hydrocarbons, and can be used in the petrochemical and chemical industry.

We propose a method of refining gasoline distillates, including a preliminary contacting the source of crude oil with aluminum oxide at a temperature of 50 - 160oWith that taken in an amount of 5 to 30% vol. of the total load hydrogenation catalysts, and the subsequent two-stage hydrogenation in the presence of alumina-cobalt-molybdenum catalyst at a temperature of 200 - 280oWith the first stage and at a temperature of 260 -380oWith the second stage, the hydrogenation is carried out at a pressure of 3 to 5 MPa and space velocity of the raw material of 0.5 to 3.0 HR-1at each stage. 1 C. p. F.-ly.

The method is intended for refining gasoline distillates containing unsaturated and aromatic hydrocarbons, and can be used in the petrochemical and chemical industry.

There is a method of refining vysokoperedelnyh gasoline often is. the process is carried out at a temperature of 350 380oC, a pressure of 3 to 4 MPa, the space velocity of the raw material of 0.5 to 4.0 h-1[1] the method can reduce the sulfur content from 0.36% to 0.003 - 0,010% by weight. iodine value between 80 and 0.5 to 1.5 g of iodine per 100 g of product.

However, the process of gentrification is accompanied by large heat so that the temperature Gutseriev mixture at the inlet of the reactor is maintained at level 240 260oWith, at the outlet of the reactor the temperature of the mixture rises to 400 420oC. the Disadvantage of this method is the difficulty of thermal regulation, as well as increasing kokoulina in the heat exchanger and heating equipment.

Also there is a method of hydrofining vysokoperedelnyh gasoline, such as light fractions of the process of coking of tar mixed with straight-run gasoline, which significantly simplifies the process and reduces the sulfur content of from 0.3 to 0.4% wt. to 0.01 to 0.03 wt.%. and to reduce the iodine number of from 130 to 180 1 2 g iodine per 100 g of product. The process is conducted at a temperature of 330 370oC, a pressure of 3 to 5 MPa, the space velocity of the raw material 1 5 h-1[2] the Disadvantage of this method is the need to use scarce straight-run gasoline fractions. Among the disadvantages is luol, xylenes and others) if beautification is subjected aromatyzovanyy products of pyrolysis gasoline or coke production facilities in order to obtain individual aromatic hydrocarbons.

Closest to the claimed method is hydrofining gasoline fraction of the pyrolysis condensate fraction, characterized by an iodine number 44,5 -48,3 g of iodine per 100 g of product and a sulfur content of 0.02 to 0.04 wt.%

According to this method, the finishing is carried out by two-stage hydrogenation.

On the first stage of the process is carried out at a temperature of 70 150oWith the pressure of 4 MPa. As the palladium catalyst used for the oxide-aluminum carrier.

At the second stage of the process is carried out at a temperature of 350 380oC, a pressure of 4 MPa. As the catalyst used industrial alumina-cobalt-molybdenum contact. The total volumetric feed rate on both levels is 0.7 h-1[3] the method can reduce the sulfur content in the product to 0,0026% wt. and iodine number of up to 0.09 iodine per 100 g of product. The resulting hydrogenation product is raw material for the separation from it of individual aromatic hydrocarbons (benzene, toluene the impossibility of using sulfur gasoline fractions (due to the increased sensitivity of palladium catalyst to sulfur compounds), and, on the other hand,

the need to implement the process in the form of two independent stages with separate circulation system, gas (which is also dictated by the high requirements on the content of hydrogen sulfide in the circulating gas for 1 stage of the process). However, even if all these requirements residual sulfur content in the hydrogenation product is not reduced less than 0,002% wt. Due to the existing restrictions on this indicator (not more than 0.005% wt.) it is necessary to use more efficient technologies.

Proposed by the authors aims at eliminating the above drawbacks.

Applying the method of refining gasoline distillates, including two-stage hydrogenation of crude oil in the presence of catalysts at elevated temperature and pressure under which the original oil feedstock pre-contact with the alumina at a temperature of 50 -160oWith that taken in an amount of 5 to 30% vol. of the total load hydrogenation catalysts and hydrogenation is carried out in the presence of alumina-cobalt-molybdenum catalyst at a temperature of 200 to 280oWith the first stage and at a temperature of 260 380oC in the second stage of the process.

Gidrirovanie the IOM method is the original oil - fraction hydrocarbons containing aromatic compounds along with unsaturated hydrocarbons and sulfur compounds, is subjected to three-stage hydrogenation treatment. In the first stage at a temperature of 50 to 160oC and flow rate 5,0 3,0 h-1oil feedstock in contact with the aluminum oxide, resulting in its purification from mechanical particles and resinous compounds adsorbed on the surface of aluminum oxide. This operation can significantly reduce coke deposits in the heat exchanger and heating equipment. In the second stage at a temperature of 200 to 280oWith a milder hydrogenation of the feedstock in the presence of AKM-catalyst for the removal of unsaturated hydrocarbons. The latter are becoming almost completely, while the hydrogenolysis of sulfur compounds occurs only to a minor extent.

In the third stage, carry out the final cleaning of the raw material from sulfur compounds. This stage is carried out at a temperature of 260 380oAlso in the presence of AKM-catalyst. Depth conversion of sulfur compounds reaches 90% or more. The volumetric feed rate with the same path, and between the reactors II and III stage of the process to produce additional heating of raw materials to ensure the necessary degree of transformation of sulfur compounds.

The implementation of this method allows very deeply cleanse raw materials from unsaturated hydrocarbons and sulfur. In the case of upgrading a technical mixture of aromatic hydrocarbons is achieved by obtaining a product containing no unsaturated hydrocarbons, sulfur content is reduced to below 5 ppm.

The inventive method is illustrated by the following examples.

Example 1.

Beautification is subjected to the benzene-toluene fraction containing 70,5% benzene, or 21.0% of toluene (the rest of the hydrocarbons of other types), characterized by the concentration of sulfur compounds 2700 ppm iodine number 24 g of iodine per 100 g of product.

At the first stage in the presence of preformed gamma-alumina in an amount of 5% vol. of the total load hydrogenation catalysts are sorption Gutseriev mixture from mechanical impurities and coke particles at a temperature of 160oC, space velocity of the raw material 30 h-1and a pressure of 3 MPa.

In the second stage in the presence of evagorou, that provides a lower iodine number of up to 2 g of iodine per 100 g of product; the sulfur content is reduced to 2500 ppm. Conditions of the second stage: the pressure of 5 MPa, the volumetric feed rate of 0.5 h-1.

At the third stage in the presence of alumina-cobalt-molybdenum catalyst at a temperature of 380oTo carry out the hydrogenation of sulfur compounds to their residual content of less than 5 ppm (iodine number less than 0.5 g of iodine per 100 g of product).

Conditions of the third stage, the pressure of 3 MPa, the volumetric feed rate to 3 h-1.

The resulting hydrogenation product containing 69% benzene and 20% toluene, directed to the selection of individual aromatic hydrocarbons.

Example 2.

Beautification is subjected benzatropine fraction containing 68% of benzene and 23% of toluene (the rest of the hydrocarbons of other types), characterized by the concentration of sulfur compounds 1500 ppm, iodine number 18 g of iodine per 100 g of product.

At the first stage in the presence of preformed gamma-alumina in the amount of 15% vol. of the total loading of catalyst for hydrogenation are sorption Gutseriev mixture from mechanical impurities and coke particles at a temperature of 50oWith that surround Abdenago catalyst at a temperature of 280oC carry out the hydrogenation of unsaturated hydrocarbons, which results in lower iodine number of up to 1.5 g of iodine per 100 g of product; the sulfur content is reduced to 1150 ppm. Conditions of the second stage: pressure 4 MPa, the volumetric feed rate 3 h-1.

At the third stage in the presence of alumina-cobalt-molybdenum catalyst at a temperature of 320oTo carry out the hydrogenation of sulfur compounds to their residual content of less than 5 ppm (iodine number less than 0.3 g of iodine per 100 g of product).

Conditions of the third stage: pressure 4 MPa, the volumetric feed rate of 0.5 h-1.

The resulting hydrogenation product containing 66% of benzene and 21% of toluene, directed to the selection of individual aromatic hydrocarbons.

Example 3.

Beautification is subjected to a benzene-toluene-xylene fraction containing 60% benzene, 13% toluene, 10% of xylenes (the rest of the hydrocarbons of other types), characterized by the concentration of sulfur compounds 100 ppm iodine number of 15 g of iodine per 100 g of product.

At the first stage in the presence of preformed gamma-alumina in the amount of 30% vol. of the total loading of catalyst for hydrogenation are sorption Gutseriev mixture from IU is pressure - 5 MPa. In the second stage in the presence of alumina-cobalt-molybdenum catalyst at a temperature of 240oC carry out the hydrogenation of unsaturated hydrocarbons, which results in lower iodine number of up to 1.4 g of iodine per 100 g of product; the sulfur content is reduced to 900 ppm. Conditions of the second stage: the pressure to 3 MPa, the volumetric feed rate of 1.5 h-1.

At the third stage in the presence of alumina-cobalt-molybdenum catalyst at a temperature of 260oTo carry out the hydrogenation of sulfur compounds to their residual content of less than 5 ppm (iodine number less than 0.5 g of iodine per 100 g of product).

Conditions of the third stage: the pressure of 5 MPa, the volumetric feed rate of 1.5 h-1.

The resulting hydrogenation product containing 58.5% benzene, 12% of toluene and 9% of xylenes, directed to the selection of individual aromatic hydrocarbons.

The results indicate that the selected ranges provide deep desulfurization of the feedstock (to less than 5 ppm) while maintaining the main mass of the aromatic hydrocarbons. At the same time there is a profound transformation of unsaturated hydrocarbons (iodine value of 0.3, 0.5 g of iodine per 100 g), which indicates that high with the expectation of two-stage hydrogenation of crude oil in the presence of catalysts at elevated temperature and pressure, characterized in that the source of the oil raw material pre-contact with the aluminum oxide at 50 160oWith taken 5,0 30,0 about. of the total load hydrogenation catalysts and hydrogenation is carried out in the presence of allocability-molybdenum catalyst at 200 280oWith the first stage and at 260 380oWith the second stage of the process.

2. The method according to p. 1, characterized in that the hydrogenation is carried out at a pressure of 3.0 to 5.0 MPa and space velocity of the raw material of 0.5 to 3.0 HR-1.

 

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