Method of sweetening kerosene fractions

 

(57) Abstract:

The invention relates to a method of sweetening kerosene fractions and can be used in the refining industry. The demercaptanization of kerosene fractions is carried out by heating up to 150-250oWith a mixture containing feedstock and hydrocarbon gas (containing 4-20 wt. % H2), in the ratio 5: 50 nm3/m3of raw materials. Then this mixture is contacted at a pressure of 0.1-0.5 MPa with a catalyst containing the oxides of metals of the 6th and 8th groups of the Periodic system of elements. To feed, the catalyst was pretreated for 12-48 h in a solution containing 0.5 to 1.0 wt. % of polysulfides in the oil fraction at a temperature of 150-250oC, a pressure of 0.1-0.3 MPa and the flow of hydrocarbon gas (containing 4-20 wt. % H2) not less than 10 nm3/m3kerosene fractions. The invention solves the problem of simplifying the technology of purification of kerosene fractions from mercaptans.

The invention relates to a method of sweetening straight-run kerosene fractions and can be used in the oil industry.

In kerosene fractions present to 0,010% (100 ppm) or more mercaptans. Known spoilerroom air in the presence of podnasadochnyh solutions phtalocyanines catalysts, followed by the separation of the catalyst solution from purified raw materials the process Merox" [Sittig M. the oxidation of hydrocarbons. - M. : Chemistry, 1970. - 300 S. ] .

The main disadvantage of this method is the formation of stable emulsions oil fraction with alkaline solutions.

Known methods for removal of petroleum products from mercaptans (demercaptanization) by transferring mercaptans aqueous solutions of alkalis in mercaptide with subsequent oxidation of mercaptans oxygen to disulfides in the presence of catalysts, and by treating them with solutions of sodium hypochlorite, hydrogen peroxide, organic peroxides, nagkakamali and dimethylsulfoxide [Shigeru UAE. The chemistry of organic sulfur compounds. - M. : Chemistry, 1975. - c. 98-103, 512] .

Known [U.S. Pat. RF 2145972, class C 10 G 27/20, 1998 ] the method of purification of petroleum distillates from mercaptans by oxidative treatment in the reactor with a fixed bed catalyst containing metalphthalocyanine on a solid medium in the presence of an alkaline agent. Next, the spent alkaline agent is separated from the purified fractions, concentrate and recycle to the reactor at the stage of cleaning.

Known [U.S. Pat. RF 2106387, class C 10 G 27/04, 1996 ] method demercaptanization of petroleum distillates by the aqueous carbon fiber fabric. The catalyst periodically through 50-200 hours impregnated with an aqueous solution of sodium hydroxide.

A disadvantage of known methods is the complexity of their implementation, requiring the creation of a special multi-stage industrial installations.

The closest in technical essence and the achieved result of the present invention is a method of sweetening kerosene fractions [and. C. 1664814, USSR, class C 10 G 45/02, 1989] by heating the feedstock and hydrogen, contact Gutseriev mixture at a temperature of 300-350oC and a pressure of 1-5 MPa.

The disadvantage of the method adopted for the prototype, is the necessity of using high-pressure equipment, which complicates the process of sweetening kerosene fractions at most refineries.

The aim of the invention is to simplify the technology of purification of kerosene fractions from mercaptans.

This goal is achieved by way of sweetening kerosene fractions by heating to a temperature of 150-250oWith a mixture containing feedstock and hydrocarbon gas (containing 4-20 wt. % H2), in the ratio 5: 50 nm3/m3allow 6 and 8 groups of the Periodic system of elements. To feed, the catalyst was pretreated within 12-48 hours with a solution containing 0.5 to 1.0 wt. % of polysulfides in the oil fraction at a temperature of 150-250oC, a pressure of 0.1-0.3 MPa and the flow of hydrocarbon gas (containing 4-20 wt. % H2) not less than 10 nm3/m3kerosene fraction.

The main feature of the proposed method of sweetening kerosene fractions is contacting heated to a temperature of 150-250oWith the mixture comprising the feedstock and the hydrocarbon gas containing 4-20 wt. % H2in the ratio 5: 50 nm3/m3raw material, at a pressure of 0.1-0.5 MPa with a catalyst containing the oxides of metals of the 6th and 8th groups of the periodic system of elements, and to implement the sweetening catalyst pretreated with a solution containing 0.5 to 1.0 wt. % of polysulfides in the oil fraction at a temperature of 150-250oC, a pressure of 0.1-0.3 MPa and the flow of hydrocarbon gas (containing 4-20 wt. % H2) not less than 10 nm3/m3kerosene fraction.

Specified distinctive feature of the proposed solution defines its novelty and inventive step in comparison with the known level of those is the shaft of the technical solutions according to the methods allows to make a conclusion about the absence of these signs, similar to the essential distinctive features of the claimed process, i.e. the compliance of the proposed method to the requirements of inventive step.

The method is as follows. Gutseriev mixture consisting of straight-run kerosene fraction and a hydrocarbon gas containing 4-20 wt. % H2in the ratio 5: 50 nm3/m3raw material is heated to a temperature of 150-250oC and sent to the reactor where it comes into contact at a pressure of 0.1-0.5 MPa with a catalyst containing the oxides of metals of the 6th and 8th groups of the Periodic system of elements. Prior to the implementation of the sweetening catalyst pretreated within 12-48 hours with a solution containing 0.5 to 1.0 wt. % of polysulfides in the oil fraction at a temperature of 150-250oC, a pressure of 0.1-0.3 MPa and the flow of hydrocarbon gas (containing 4-20 wt. % H2) not less than 10 nm3/m3kerosene fraction.

The proposed method is simple to implement and can be easily implemented in refineries.

The advantages of the proposed method are illustrated by the following examples.

Example 1

In a reactor loaded allocability catalyst KGM-70 (TU-301-MESI the catalyst is treated for 48 hours with a solution, containing 0.5 wt. % of polysulfides in the oil fraction at a temperature of 150oC, a pressure of 0.3 MPa and the flow of hydrocarbon gas (containing 20 wt. % H2) 10 nm3/m3kerosene fraction.

Straight-run kerosene fraction 150-240o(The content of mercaptans 79 ppm) is mixed with a hydrocarbon gas containing 20 wt. % H2in the ratio of 5 nm3/m3raw material is heated to a temperature of 150oC and sent to the reactor where it comes into contact at a pressure of 0.5 MPa with a catalyst.

After separation of the hydrocarbon gas and stabilization of purified kerosene fraction content of mercaptans in her 18 ppm (degree of purification from mercaptans 77%).

Example 2

In a reactor loaded allocability catalyst TH-70 (TU-38.101-1111-87, contains Soo - 4.5 wt. % Moo3of 14.5 wt. %, the rest aluminum oxide).

Before filing Gutseriev mixture, the catalyst is treated for 12 hours with a solution containing 1.0 wt. % of polysulfides in the oil fraction at a temperature of 250oC, a pressure of 0.1 MPa and a flow of hydrocarbon gas (containing 4 wt. % H2) not less than 50 nm3/m3kerosene fraction.

Straight-run kerosene fraction with the raw material is heated to a temperature of 250oC and sent to the reactor where it comes into contact at a pressure of 0.1 MPa with a catalyst.

After separation of the hydrocarbon gas and stabilization of purified kerosene fraction content of mercaptans in her 9 ppm (degree of purification from mercaptans 88%).

Example 3

In a reactor loaded aluminumalloy catalyst OD-17 (TU-38.4011010 contains NiO - 4.6 wt. % Moo3- 12 wt. %, P2ABOUT5- 3.6 wt. %, the rest aluminum oxide).

Before filing Gutseriev mixture, the catalyst is treated for 24 hours with a solution containing 0.75 wt. % of polysulfides in the oil fraction at a temperature of 210oC, a pressure of 0.3 MPa and the flow of hydrocarbon gas (containing 18 wt. % H2) not less than 20 nm3/m3kerosene fraction.

Straight-run kerosene fraction according to example 1 is mixed with a hydrocarbon gas containing 18 wt. % H2in the ratio of 10 nm3/m3raw material is heated to a temperature of 210oC and sent to the reactor where it comes into contact at a pressure of 0.3 MPa with a catalyst.

After separation of the hydrocarbon gas and stabilization of purified kerosene fraction content of mercaptans in it is according to example 1 are heated to a temperature of 300oWith and in contact with a preheated 450oWith hydrogen, taken in the amount of 800 nm3/m3raw material, at a pressure of 1.3 MPa without a catalytic Converter.

After separation of the hydrogen and stabilization of purified kerosene fraction content of mercaptans in 24 ppm (degree of purification from mercaptans 70%).

Thus, during the process of sweetening kerosene fractions according to the proposed method obtained free from mercaptans (purification 71-88%) kerosene fraction in the conditions of (pressure of not more than 0.5 MPa, a temperature not exceeding 250o(C) allowing the use of equipment distillation unit, i.e., without the construction of special facilities or capacity installations hydrotreatment units.

Method of sweetening kerosene fractions by heating the feedstock and hydrogen, contact Gutseriev mixture at elevated temperature and pressure, characterized in that the kerosene fraction is mixed with a hydrocarbon gas containing 4-20 wt. % H2in the ratio 5: 50 nm3/m3raw material is heated to a temperature of 150-250oC and at pressures of 0.1-0.5 MPa in contact with a catalyst containing the oxides of metals of the 6th and 8th groups of the Periodic system the functions, within 12-48 hours at a temperature of 150-250oC, a pressure of 0.1-0.3 MPa and the flow of hydrocarbon gas containing 4-20 wt. % H2not less than 10 nm3/m3kerosene fractions.

 

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