Method of purification of liquid hydrocarbons from sulfur compounds

 

(57) Abstract:

The invention relates to petrochemistry and oil refining and can be used in the processes hydrodesulphurization unit of hydrocarbon fractions. Cleaning liquid hydrocarbons is carried out in the presence of hydrogen in aluminium oxide-platinum catalyst, pre-activated with hydrogen at 80 - 300oC and high pressure. This method allows to obtain a hydrocarbon feedstock with a high degree of purification from sulfur compounds.

The invention relates to methods for cleaning hydrocarbons from sulfur compounds and can be used for desulfurization paraffinic, olefinic and aromatic hydrocarbons.

Known method of hydrodesulfurization and hydrogenation distillate hydrocarbon complex bimetallic catalyst consisting of various catalytic zones. In the composition of the catalyst 1 zone comprises active components containing precious metals such as cobalt, Nickel, molybdenum, tungsten. Catalyst 2 zone contains the active component of the platinum group metal. Moreover, it is interesting to note that purification from sulfur occurs mainly in the first reaction zone, and platinum katalia diesel fuel in two stages, using the first stage lookbetteronline catalyst, and the second stage catalyst platinum source. The disadvantage of this method is the use of advanced secondary treatment and use of high temperatures [2].

There is a method of Hydrotreating sulfur kerosene to improve his raketoopasnyh characteristics [3]. The method consists in the treatment of this fraction with hydrogen at the maximum allowable for this catalyst temperature ( < 400oC) a catalyst comprising an inorganic carrier containing aluminum oxide, 0.1 to 1.5 wt.% halogen component, a platinum component, a rhodium and tin component. The disadvantage of this method is the necessity of using high temperatures.

The closest in technical essence and the achieved effect is a method of desulfurization of crude benzene, light and heavy oil and shale oils and other hydrocarbons [4]. The method consists in passing the vapors of these hydrocarbons in a stream of hydrogen at atmospheric pressure and a temperature of 300-350oC over a catalyst selected from the group of Nickel deposited on alumina, platinum or palavered removed by ordinary methods.

To obtain hydrocarbons with a high degree of Hydrotreating at lower temperatures, we propose a method of purification of liquid hydrocarbons from sulphur at 80-300oC on aluminium oxide-platinum catalyst, pre-activated with hydrogen. As aluminium oxide-platinum catalyst used aluminium oxide-platinum catalyst for isomerization.

Distinctive features of the invention are the use of aluminium oxide-platinum catalyst, pre-activated with hydrogen, and the process of purification at 80-300oC.

When comparing essential features of the invention with those prototypes and analogues, it is possible to draw a conclusion on the conformity of the proposed technical solution the criteria of "novelty" and "inventive step", since the use of pre-activated hydrogen aluminium oxide-platinum catalyst isomerization in the process hydrodesulphurization unit is not known. Pre-activation of the catalyst allows to achieve a desired degree of purification of hydrocarbons from sulfur compounds. It is the activation of known industrial catalyst allows the process of hydrodesulfurization at lower temperature is feasible in industry, as evidenced by the following examples.

Example 1. Testing is carried out at a flow setting of continuous operation. Before carrying out the process of conducting the preliminary preparation of the catalyst, which are as follows: charged to the reactor known industrial aluminium oxide-platinum catalyst (TU 3810173-77. Catalyst FE-62 is a platinum uniformly distributed on the external and internal surfaces of the extrudates fluorinated activity of aluminum oxide. Mass fraction of platinum 0,550,03; mass fraction of fluorine 3,50,5; mass fraction of iron, not more than 0.02; mass fraction of sodium, not more than 0.01; the bulk density of the catalyst, calcined at 550oC 0,650,05 kg/l; the ratio of the strength of the catalyst is not less than 0.97 kg/mm; the diameter of the extrudates 2,80,2 mm). The reactor is heated to activate the catalyst with hydrogen at atmospheric pressure, after which install in the reactor specified temperature and pressure and do not stop the flow of hydrogen into the reactor served raw. The reaction product is purified from sulfur-containing impurities of the hydrocarbon fraction is removed from the reactor in the collection and analyzed for total sulfur content (GOST 19121-73). The process of cleaning hydrocarbons from sulfur compounds conduct is mperature in the reactor 80oC, hydrogen pressure of 10 ATM.. Purified hydrocarbon fraction is directed to a collection, then taken and analyzed for total sulfur content, which is 0.0001 wt.%. The degree of purification from sulfur compounds thus equals 98,33%. As hydrocarbon use fraction C5-C7 c tKip.60-100oC.

Example 2. Experience in the conditions of example 1, but the temperature in the reactor support 150oC. the Content of total sulfur in the treated hydrocarbon fraction is missing. The degree of desulfurization is 100%.

Example 3. The experience is conducted under the conditions of example 1, but the temperature in the reactor support 200oC. the Content of total sulfur in the treated hydrocarbon fraction is missing. The degree of desulfurization is 100%.

Example 4. The experience is conducted under the conditions of example 1, but the temperature in the reactor support 250oC. the Content of total sulfur in the treated hydrocarbon fraction is missing. The degree of desulfurization is 100%.

Example 5. The experience is conducted under the conditions of example 1, but the temperature in the reactor support 300oC. the Content of total sulfur in the treated hydrocarbon fraction is missing. The degree of desulfurization is 100%.

Example 6. Experience conducting condition in which one faction is 0,00005 wt.%. The degree of desulfurization is 99.7%. As hydrocarbon use fraction C5-C7with tKip.30-90oC.

Example 7 the Experience carried out in the conditions of example 6, but the temperature in the reactor support 150oC. the Content of total sulphur and unsaturated in the treated hydrocarbon fraction is missing. The degree of desulfurization is 100%.

Example 8. The experience is conducted under the conditions of example 6, but the temperature in the reactor support 200oC. the Content of total sulfur in the treated hydrocarbon fraction is missing. The degree of desulfurization is 100%.

Example 9. The experience is conducted under the conditions of example 6, but the temperature in the reactor support 250oC. the Content of total sulfur in the treated hydrocarbon fraction is missing. The degree of desulfurization is 100%.

Example 10. The experience is conducted under the conditions of example 6, but the temperature in the reactor support 300oC. the Content of total sulfur in the treated hydrocarbon fraction is missing. The degree of desulfurization is 100%.

These examples show that the optimal conditions for the desulfurization process are a temperature of 80-300oC and a pressure of 10-15 bar. The invention allows to reduce energy consumption and the related compounds.

Method of purification of liquid hydrocarbons from sulfur compounds at elevated temperature in the presence of hydrogen, the catalyst containing platinum, wherein the cleaning is performed at 80 - 300oWith aluminium oxide-platinum catalyst, pre-activated with hydrogen.

 

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