The method of hydrotreating a hydrocarbon fractions and a catalyst for hydrotreating hydrocarbon fractions

 

(57) Abstract:

Use: preparation of hydrocarbons. Essence: carry out the hydrotreatment of hydrocarbon fraction at elevated temperature in the presence of hydrogen in aluminium oxide-platinum catalyst, the activated hydrogen. Used Hydrotreating catalyst is a spent catalyst isomerization of hydrocarbons, treated with an inert gas at 190-200oAnd a mixture of inert gas with oxygen content in the mixture of oxygen up to 8 wt.% when 200-470oWith stepwise increasing temperature. The temperature rise during the processing of the catalyst may occur with a speed of 5-15oWith/including Technical result: increased degree of cleaning hydrocarbon fractions from unsaturated and aromatic hydrocarbons and sulfur compounds. 2 S. and 1 C.p. f-crystals.

The invention relates to the field of petrochemicals, and particularly to a method of Hydrotreating a liquid hydrocarbon fractions.

A known method of purification of products of catalytic reforming from olefinic hydrocarbons by hydrogenation at a temperature of 150-250oC and a pressure of 0.5 to 1.5 MPa in the presence of a catalyst containing a mixture of two aluminium oxide-platinum contacts with code aims only to remove olefins and is not used for treatment of unsaturated and aromatic hydrocarbons and sulfur compounds.

Closest to the present invention is a method of purification of liquid hydrocarbons from sulfur compounds at a temperature of 80-300oWith aluminium oxide-platinum catalyst, pre-activated hydrogen (RF Patent 2111232, IPC C 07 C 7/163, publ. 20.05.98).

The disadvantage of this method is that liquid hydrocarbons are purified only from sulfur compounds.

A known catalyst for hydrofining petroleum fractions containing oxides of molybdenum, cobalt or Nickel and phosphorus on the carrier aluminium hydroxide (RF Patent 2074769, IPC601 J 21/04, With 10 G 45/08, publ. 10.03.97). Upon receipt of the carrier aluminium hydroxide peptizer by a mixture of nitric and phosphoric acids, is then formed in the form of extrudates, dried and calcined. The process of obtaining such a catalyst requires complex technological design and obtained in the described way catalyst does not allow clearance sufficiently from aromatic hydrocarbons.

A known catalyst for Hydrotreating catalytic reforming products from olefin hydrocarbons containing a mixture of two aluminium oxide-platinum contact with a platinum concentration of 0.1 to 0.15 wt.% and 0.3-0.7 wt.% respectively (A. C. the USSR co from olefinic hydrocarbons and is not used for treatment of unsaturated and aromatic hydrocarbons and sulfur compounds.

Closest to the proposed catalyst is aluminium oxide-platinum catalyst for hydrotreatment of liquid hydrocarbons from sulfur compounds (RF Patent 2111232, IPC C 07 C 7/163, publ. 20.05.98). The catalyst before Hydrotreating process activate hydrogen.

The described catalyst allows you to clean hydrocarbon fraction to a sufficient extent only from sulfur compounds, clearing of unsaturated and aromatic hydrocarbons such catalyst could be carried out.

The objective of the invention is to increase the degree of purification of hydrocarbon fractions from unsaturated and aromatic hydrocarbons and sulfur compounds.

To solve this problem is proposed a method of Hydrotreating a hydrocarbon fractions at elevated temperature in the presence of hydrogen in aluminium oxide-platinum catalyst, activated hydrogen, the catalyst used exhaust aluminium oxide-platinum catalyst for the isomerization of hydrocarbons, treated with an inert gas at a temperature of 190-200oAnd a mixture of inert gas with oxygen content in the mixture of oxygen up to 8 wt. % at a temperature of 200-470oWith stepwise increasing temperature.

oAnd a mixture of inert gas with oxygen content in the mixture of oxygen up to 8 wt.% when the temperature 200-470oWith the three-step temperature increase.

Carrying out Hydrotreating process to extract aluminium oxide-platinum-catalyzed isomerization of hydrocarbons, previous treatment with an inert gas and a mixture of inert gas with oxygen and subsequent activation by hydrogen, allows not only to use for a new purpose the spent catalyst is sent for recycling, but to get this catalyst cleaner products, i.e. to carry out the hydrotreatment from unsaturated and aromatic hydrocarbons and sulfur compounds with high selectivity. The surface of the catalyst is changed in comparison with fresh, which changes the properties of the catalyst.

The proposed mode of processing spent catalyst allows to obtain the catalyst required for the process of Hydrotreating a dispersion of platinum and transfer platinum in form, active in the Hydrotreating, which leads to increased selectivity purification by hydrogenation of hydrocarbon fractions from unsaturated and aroma, space velocity of the raw material 0,7-3,0 h-1the temperature of 80-300oWith a volume ratio of raw material and hydrogen is 1:100-500, aluminium oxide-platinum catalyst. Before carrying out of the process exhaust aluminium oxide-platinum catalyst (TU 38.10173-88 "aluminium oxide-platinum Catalyst high temperature isomerization PI-62 M) containing 0,550,5 wt.% platinum is loaded into the reactor and spend processing an inert gas at a pressure of 0.1-1.0 MPa and a temperature of 190-200oTo the lack of hydrocarbons in the exhaust gas, after which the inert gas type oxygen at a rate of 0.2 to 0.4 vol.% per hour up to 8 vol.%, increasing the temperature up to 290-300oWith speeds of 5-15oWith in the hour, and treated with the catalyst within 20-45 h to lack of moisture. Determine the oxygen content and temperature at the inlet and outlet of the reactor and the carbon dioxide content at the reactor outlet. After aligning them raise the temperature to 370-390oWith speeds of 5-15oWith in the hour and treated with the catalyst at this temperature to equalize the oxygen content and temperature at the inlet and outlet of the reactor and the establishment of the minimum-standing carbon dioxide at the outlet of the reactor. Then raise the temperature to 440-470oWith the speed of the Yes and temperature before and after the reactor and the establishment of the minimum-standing carbon dioxide at the outlet of the reactor, then stop the flow of oxygen in the inert gas reduces the temperature of the catalyst speeds of 5-15oWith an hour to 300-350oAnd restore the catalyst with hydrogen at a volumetric flow of hydrogen-containing gas 450-600 nm/m3catalyst, the pressure in the reactor of 0.1 to 1.0 MPa with a gradual rise in temperature speeds of 20-50oWith an hour to 370-430oWith and maintain the catalyst at this temperature for 7-10 hours. After that is installed in the reactor specified temperature and pressure and, without stopping the flow of hydrogen into the reactor, start feeding the hydrocarbon fraction. The hydrogenation product from the reactor serves for cooling in the fridge and in a cooled receiver.

The composition of the reaction products determined by gas-liquid chromatography, the bromine number of standard bromate-bromanil method, the total sulfur - according to GOST 19121-73.

The invention is illustrated 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. Exhaust aluminium oxide-platinum catalyst that meets the requirements of THE 38.10173-88 "aluminium oxide-platinum Catalyst, high-temperature isomerizate what atom - nitrogen at a pressure of 1.0 MPa and a temperature of 190oTo the lack of hydrocarbons in the exhaust gas, after which the inert gas type oxygen at a rate of 0.2 vol.% per hour up to 5% vol. and this mixture is treated with the surface of the catalyst within 45 hours, raising the temperature to 290oWith a speed of 5oWith an hour and soaking at this temperature until no moisture. Determine the oxygen content and temperature at the inlet and outlet of the reactor and the carbon dioxide content at the reactor outlet. After aligning them raise the temperature to 380oWith a speed of 5oWith in the hour and treated with the catalyst at this temperature to equalize the oxygen content and temperature at the inlet and outlet of the reactor and the establishment of the minimum-standing carbon dioxide at the outlet of the reactor. Then raise the temperature to 450oWith a speed of 5oWith in the hour and treated with the catalyst at this temperature to equalize the oxygen content and temperature before and after the reactor and the establishment of the minimum-standing carbon dioxide at the outlet of the reactor, and then stop the flow of oxygen in the inert gas reduces the temperature of the catalyst at a speed of 5oIn net assets3catalyst, the reactor pressure 1.0 MPa, with a gradual temperature rise rate of 20oWith an hour to 430oWith and maintain the catalyst at this temperature for 10 hours.

After that is installed in the reactor specified temperature and pressure and, without stopping the flow of hydrogen into the reactor, served raw material fraction C5-C7hydrocarbons with initial boiling point 63oWith the end of the boil - 75oC. the feedstock contains serosoderjaschei compounds of 0.03 wt.%, aromatic hydrocarbons - 2.9 wt.%, bromine number is 0.3 g Br/100 g

The hydrotreatment is carried out under the following conditions: a pressure of 1.5 MPa, the volumetric feed rate is 0.7 h-1temperature - 300oWith that, the volumetric ratio of the feedstock and hydrogen is 1:500. The hydrogenation product from the reactor serves for cooling in the refrigerator and cooled receiver, then select and analyze.

The degree of purification of total sulfur is 100%; aromatic hydrocarbons - 100%; unsaturated hydrocarbons - 99,94%.

Example 2

The experience carried out as described in example 1, but exhaust aluminium oxide-platinum catalyst for the isomerization of hydrocarbons is treated with nitrogen at a temperature of 198oWith, then a mixture of nitrogen from the fish processing 15oWith an hour on the first level up to 300oSince, in the second stage to 390oWith the third stage - to 470oWith it, recover hydrogen at a volumetric flow of hydrogen-containing gas 600 nm3/m3catalyst, the reactor pressure 1.0 MPa, with a gradual rise of temperature at 50oWith up to 370oWith and maintain the catalyst at this temperature for 7 hours

The Hydrotreating is carried out at a pressure of 1.0 MPa, a temperature of 80oC, space velocity of the raw material to 3.0 h-1, a volume ratio of raw material and hydrogen is 1: 100.

The degree of purification of total sulfur is 98,33%; aromatic hydrocarbons - 71,43%; unsaturated hydrocarbons to 90.0%.

Example 3

The experience carried out as described in example 1, but the Hydrotreating is carried out at a pressure of 1.5 MPa, a temperature of 250oC, space velocity of the raw material - 1,0 h-1, a volume ratio of raw material to the hydrogen - 1:450.

The Hydrotreating serves fraction C5hydrocarbons with initial boiling point 27oWith the end of the boil - 52oC. the feedstock contains serosoderjaschei compounds 0,065 wt. % of aromatic hydrocarbons - 3.1 wt.%, bromine number is 0.37 g Br/100 g

The degree of purification in General seen from the above examples, purification of hydrocarbon fractions by hydrogenation of the proposed aluminium oxide-platinum catalyst produces purer products, i.e. allows the Hydrotreating from unsaturated and aromatic hydrocarbons and sulfur compounds with high selectivity.

1. The method of Hydrotreating hydrocarbon fraction at elevated temperature in the presence of hydrogen in aluminium oxide-platinum catalyst, activated hydrogen, characterized in that as aluminium oxide-platinum catalyst used exhaust catalyst for isomerization of hydrocarbons, treated with an inert gas at 190-200C and a mixture of inert gas with oxygen content in the mixture of oxygen up to 8 wt.% at 200-S with stepwise increasing temperature.

2. Aluminium oxide-platinum catalyst for Hydrotreating hydrocarbon fractions, activated hydrogen, characterized in that the catalyst is an exhaust aluminium oxide-platinum catalyst for the isomerization of hydrocarbons, treated with an inert gas at 190-200C and a mixture of inert gas with oxygen content in the mixture of oxygen up to 8 wt.% at 200-S with a three-stage temperature increase.

3. The catalyst p. 2, characterized in that t

 

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