The method of purification of products of catalytic reforming from olefinic hydrocarbons

 

(57) Abstract:

The invention relates to the field of oil and can be used in the process of cleaning catalytic reforming products from olefin hydrocarbons. The products of the reforming hydronaut on platypodinae mono-, bi - or polymetallic catalyst in the presence of hydrogen at elevated temperature and pressure. The catalyst periodically during mezhregionalnogo period and before the regeneration process flow of liquid hydrocarbons, which are used or monocyclic aromatic hydrocarbons, or a mixture thereof, or the reforming catalysate, or hydrotreated gasoline fraction, possibly in the presence of hydrogen, in the amount of 2-10 m3/m3catalyst at a temperature of 20 - 180oC, a pressure of 0.1 to 3.0 MPa. The result is restored to the initial activity of the catalyst in mainegenealogy period, after the regeneration, the degree of hydrogenation of olefins is reduced by 4% compared to 15%, which increases the life of the catalyst. 1 C.p. f-crystals, 2 tab.

The invention relates to the field of oil and can be used in the process of cleaning catalytic reforming products from all the political hydrocarbons of high quality by catalytic reforming of gasoline fractions with subsequent liquid-phase extraction it is necessary to clear the products of reforming from olefinic hydrocarbons. One of the methods of cleaning products reformer from olefinic hydrocarbons is their selective hydrogenation in the gas-vapor stream on Latinoamerica catalysts at a temperature of 150-250oC and high pressure.

Known methods of cleaning products reformer from olefinic hydrocarbons and their hydrogenation on aluminium oxide-platinum monometallic catalyst with a platinum content of 0.10 to 0.15 wt.% [2] and combined loading aluminium oxide-platinum monometallic catalysts [3], providing selective hydrogenation of olefins at a temperature of 160-220oC and high pressure.

The disadvantages of these methods are reducing the degree of hydrogenation of olefins from 98% for the fresh catalyst to 80% after 12 months of operation and reduced the degree of hydrogenation of the olefins to 75% after regeneration.

Closest to the present invention is a method of cleaning products reformer from olefinic hydrocarbons with a more stable polymetallic catalyst, one of the metal which is platinum [1], providing selective hydrogenation of olefins at a temperature of 160-220oC and high pressure.

The known method has the following is exploitatie;

reducing the degree of hydrogenation of the olefins to 82% after regeneration;

after the second and subsequent regeneration does not provide the required degree of hydrogenation of olefins, which leads to a forced reduction in the stiffness of the reforming process with a corresponding decrease in production of aromatic hydrocarbons and eventually requires replacement of the catalyst.

The invention is directed to solution of the problem - maintaining high activity and selectivity in mainegenealogy period, the increase in life Latinoamerica catalysts cleaning products reformer from olefinic hydrocarbons.

Problem solving mediated new technical result consists in the periodic processing of the catalyst a stream of liquid hydrocarbons, possibly in the presence of hydrogen, which ensures the maintenance of the initial activity of the catalyst in mainegenealogy period and reducing the loss of its activity during regeneration.

Cleaning products reformer from olefinic hydrocarbons is carried out by selective hydrogenation of the latter in the presence of hydrogen at elevated pressure and temperature on platypodinae catalyst.

3/m3catalyst at a temperature of 20-180oC and a pressure of 0.1 to 3.0 MPa.

Example 1. When the catalytic reforming of hydrotreated gasoline fraction, wikipeida within 68 - 105oC, obtain a catalyst of the following composition, wt.%:

Unsaturated hydrocarbon - 1,2 (bromine number 2.50 g Br/100 g)

Aromatic hydrocarbons, including - 42,5

Benzene - 16,6

Toluene - 22,5

Ethylbenzene and xylenes - 3,4

Saturated hydrocarbons - 56,3

Extracted from the reactor industrial installations after 10 months. operation in the process of cleaning products reformer from olefinic hydrocarbons polymetallic catalyst G-01 content, wt.%: platinum 0,10, rhenium 0,025, cadmium, 0,10, antimony 0,005 on active aluminum oxide. THE 38.101998-84, loaded into the reactor pilot plant in the amount of 50 cm3.

Spend processing of the catalyst with hydrogen-containing feed gas (SU) and catalyzate at a temperature of 180oC and a pressure of 3.0 MPa. At the same time the volume ratio of SIVs to ASS="ptx2">

Cleaning products reformer from olefinic hydrocarbons is carried out at a temperature of 170oC, a pressure of 1.5 MPa, flow rate of raw material 10 h-1and circulation of hydrogen containing gas 1.2 thousand nm3/m3of raw materials.

The resulting hydrogenation product contains of 42.3 wt.% aromatic hydrocarbons and has a bromine number of 0.06 (table. 1).

Example 2. Polymetallic catalyst specified in example 1 is loaded into the reactor pilot plant in the amount of 50 cm3.

Spend processing catalyst feed everything and catalyst at a temperature of 130oC and a pressure of 1.6 MPa. At the same time the volume ratio of SIVs and catalyzate 1.2 thousand nm3/m3. Serving the liquid phase in the amount of 4 m3/m3a catalyst.

Cleaning products reformer, whose composition is given in example 1 is carried out in the conditions of example 1.

The resulting hydrogenation product contains 42,2 wt.% aromatic hydrocarbons and has a bromine number of 0.06 (table. 1).

Examples 3-6. Polymetallic catalyst specified in example 1 is loaded into the reactor pilot plant in the amount of 50 cm3.

Spend processing catalyst supply of liquid hydrocarbons, specified the matrix given in example 1, carried out under the conditions of example 1.

Example 7 (the prototype). Polymetallic catalyst specified in example 1 is loaded into the reactor pilot plant in the amount of 50 cm3.

Cleaning products reformer, whose composition is given in example 1 is carried out in the conditions of example 1 without pre-treatment of the catalyst.

The resulting hydrogenation product contains 42,4 wt.% aromatic hydrocarbons and has a bromine number of 0.33 (table. 1).

Thus, cleaning products reformer by a known method leads to a significant reduction in catalyst activity during mezhregionalnogo period.

Example 8 (comparison). Fresh polymetallic catalyst G-01 is loaded into the reactor pilot plant in the amount of 50 cm3.

Cleaning products reformer, whose composition is given in example 1 is carried out in the conditions of example 1.

The resulting hydrogenation product contains 42,2 wt.% aromatic hydrocarbons and has a bromine number of 0.06 (table. 1).

Thus, treatment of the catalyst under the conditions of examples 1 to 6 allows you to restore its initial activity while maintaining high selectivity.

Example 9. Polymetallics who W ill result processing feed everything and catalyzate in the conditions of example 2.

The catalyst is subjected to regeneration by the filing of a nitrogen-air mixture with the oxygen concentration of 2 wt.% at a temperature of 300oC and a pressure of 1.0 MPa, which corresponds to conditions regeneration in an industrial setting. Regeneration of the catalyst is carried out to achieve the concentration of CO2at the exit of the reactor is less than 0.1 wt.%.

Regenerate the catalyst by feeding a hydrogen-containing gas at a temperature of 170oC and a pressure of 1.5 MPa for 8 hours

Cleaning products reformer, whose composition is given in example 1 is carried out in the conditions of example 1. You get a hydrogenation product containing 42,3 wt. % of aromatic hydrocarbons and having a bromine number of 0.15 (table. 1).

Thus, the activity of the treated catalyst during regeneration is reduced by 4%.

Example 10 (the prototype). Polymetallic catalyst specified in example 1 is loaded into the reactor pilot plant in the amount of 50 cm3.

The catalyst without pre-treatment is subjected to regeneration and subsequent recovery in the conditions of example 9.

Cleaning products reformer, whose composition is given in example 1 is carried out in the conditions of example 1. You get a>Thus, cleaning products reformer by a known method leads to reduced activity of the catalyst during regeneration by 15%.

Example 11. Aluminium oxide-platinum catalyst for selective hydrogenation of olefins AP-15 content of 0.15 wt.% platinum on active aluminum oxide, THE 38.101283-80, extracted from the reactor industrial plants after 12 months. operation in the process of cleaning products reformer from olefinic hydrocarbons, are loaded into the reactor pilot plant in the amount of 50 cm3.

Spend processing catalyst feed was catalyzate reforming in a volume ratio of 1.2 thousand nm3All 1 m3catalyzate at a temperature of 130oC and a pressure of 1.6 MPa. Serving the liquid phase in the amount of 4 m3/m3a catalyst.

Cleaning products reformer, whose composition is given in example 1 is carried out in the conditions of example 1. You get a hydrogenation product containing 42,3 wt.% aromatic hydrocarbons and having a bromine number of 0.05 (table. 2).

Example 12 (similar). Aluminium oxide-platinum catalyst specified in example 11, is loaded into the reactor pilot plant in the amount of 50 cm3.

Cleaning products reformer, the composition of which PR is t hydrogenation product, containing 42,4 wt.% aromatic hydrocarbons and having a bromine number of 0.50 (table. 2).

Thus, cleaning products reformer in accordance with similar leads to a significant reduction in catalyst activity during mezhregionalnogo period.

Example 13 (for comparison). Fresh aluminium oxide-platinum catalyst AP-15 is loaded into the reactor pilot plant in the amount of 50 cm3.

Cleaning products reformer, whose composition is given in example 1 is carried out in the conditions of example 1. You get a hydrogenation product containing 42,3 wt.% aromatic hydrocarbons and having a bromine number of 0.05 (table. 2).

Thus, the processing of aluminium oxide-platinum catalyst under the conditions of example 11 (proposed method) restores its initial activity.

Example 14. Aluminium oxide-platinum catalyst specified in example 11, is loaded into the reactor pilot plant in the amount of 50 cm3and carry out the processing in the conditions of example 5.

Spend the regeneration and recovery of the catalyst under the conditions of example 9.

Cleaning products reformer, whose composition is given in example 1 is carried out in the conditions of example 1.

Received hydro is the way, the activity of the catalyst during regeneration after processing is reduced by 4%.

Example 15 (analog). Aluminium oxide-platinum catalyst specified in example 11, is loaded into the reactor pilot plant in the amount of 50 cm3.

The catalyst without pre-treatment is subjected to the regeneration and restoration in the conditions of example 9.

Cleaning products reformer, whose composition is given in example 1 is carried out in the conditions of example 1.

The resulting hydrogenation product contains 42,4 wt.% aromatic hydrocarbons and has a bromine number to 0.63 (table. 2).

Thus, cleaning products reformer in accordance with the analog results in decreased activity of the catalyst during regeneration by 23%.

From the test results it is seen that the cleaning products reformer from olefinic hydrocarbons by the proposed method (examples 1-6, 11) maintains the initial activity Latinoamerica catalysts in mainegenealogy period and decrease their activity during regeneration (examples 9, 14) 4% vs. 15%, thus increasing the life of the catalysts.

The optimum temperature and pressure selected on the basis of the reformer. The processing temperatures of the catalyst is selected from the condition of finding hydrocarbons used in the processing, in the liquid phase, which limits the maximum temperature 180oC. With increasing temperature and increasing the concentration of aromatic hydrocarbons in the liquid phase is required to apply a smaller quantity to restore the initial activity of the catalyst, so it is impractical to carry out the treatment of the catalyst at a temperature below 20oC.

1. The method of cleaning products reformer from olefinic hydrocarbons by selective hydrogenation of the latter at elevated temperature and pressure in the presence of hydrogen at platypodinae catalyst, wherein the hydrogenation is carried out in the presence of mono-, bi - or polymetallic platypodinae the catalyst and the catalyst is periodically during mezhregionalnogo period and before the regeneration process flow of liquid hydrocarbons, possibly in the presence of hydrogen, in the amount of 2 - 10 m3/m3catalyst at a temperature of 20 - 180oC, a pressure of 0.1 to 3.0 MPa.

2. The method according to p. 1, characterized in that a hydrocarbon is used or catalysate reforming, or monoc the

 

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