The method of obtaining aromatic hydrocarbons

 

Usage: petrochemistry. Essence: conducting the contacting in a reactor paraffin hydrocarbons with a catalyst based on high ZSM-5 at 350-380oWith separation of the products of the contacting liquid and gaseous products, followed by complete combustion of gaseous products in the presence of the catalyst for complete oxidation of light hydrocarbons and adding to the original paraffin hydrocarbons formed during the combustion of a mixture of carbon dioxide and water vapor in the amount of 2.0 to 20.0 wt.%. As a catalyst based on zeolite using a catalyst containing 53,28-59,69 wt.% high zeolite ZSM-5 with a residual content of Na2O not more than 0.1 wt.% and the ratio of SiO2/Al2O3=39, of 35.5-37.5 wt.% Al2About3, 2.5 to 4.5 wt.% In2O3, 2.0 to 4.0 wt.% Zn, 0.2 to 0.5 wt.% Re, 0.01 to 0.02 wt.% Nd, 0.1 to 0.2 wt. %. When this first reactor is served at 450-480oWith sulfur-containing light paraffin hydrocarbons With3-C4with a sulfur content of 0.15-0.25 wt.% in an amount to provide a ratio of rhenium in the zeolite catalyst and sulfur in the sulfur-containing paraffin hydrocarbons of about 1:25. Effect: increase the yield of aromatic hydrocarbons, the

The invention relates to the catalytic conversion of hydrocarbons and can be used to produce high octane motor fuel.

There is a method of processing a light hydrocarbon feedstock in the presence of high zeolite with additions of si, Zn or CR at 300-700oC. the Method consists of passing a mixture of hydrocarbons containing C1-C10such as light naphtha through high-silica zeolite (JP 59-152337, 1984).

The disadvantage of this method is the formation of compounds of carbon (coke deposits) on the catalyst, which significantly reduces its activity.

A method of obtaining aromatic hydrocarbons by contacting the paraffin hydrocarbons With3-C11with the catalyst on the basis of high zeolite ZSM-5 (SiO2/Al2O320-100) and metals group 11b (Zn) alone or in combination with metals of group VIB (Cr) and/or group 1B (si) in an amount of 0.01-5% metal.

The process occurs at 380-580oWith and includes the separation of the products of the contacting liquid and gaseous products (DD 251710, class B 01 J 29/28, 1986).

The disadvantage of this method is the low yield of the target product, as well as high is skim the technical nature with the claimed invention is a method for aromatic hydrocarbons by contacting the paraffin hydrocarbons With3-C11with the catalyst on the basis of high zeolite ZSM-5 at 380-580oWith, including the separation of the products of the contacting liquid and gaseous products, while the gaseous products are subjected to complete combustion in prisutstvie catalyst for complete oxidation of light hydrocarbons (e.g., vanadium catalysts V2O3/MoO3in the form of granules, copper in the form of plates, mesh, granules of copper oxide and others), and the resulting mixture of carbon dioxide and water vapor is added to the original paraffin hydrocarbons in the amount of 2.0 to 20.0 wt.%.

The operating temperature of the catalyst support due to combustion of gaseous side products of the reaction. As a catalyst in the method using a catalyst containing high-silica zeolite ZSM-5 having a ratio of SiO2/Al2O3- 39 (to 57.0 wt.%), Al2About3of 36.5% In2About3- 3.5% Zn - 3% (EN 2030376, 10.03.1995).

According to the method, the yield of aromatic hydrocarbons (C6-C9to 40 hour work is 57%, the duration of the working period is 400 h, which currently does not meet the requirements of the petrochemical industry.

Technical problem statement the working cycle.

This object is achieved in that in a method of producing aromatic hydrocarbons by contacting in a reactor paraffin hydrocarbons with a catalyst based on vysokokremnezemnstogo zeolite ZSM-5 at 350-580oWith, including the separation of the products of the contacting liquid and gaseous products, followed by complete combustion of gaseous products in the presence of the catalyst for complete oxidation of light hydrocarbons, adding to the original paraffin hydrocarbons formed during the combustion of a mixture of carbon dioxide and water vapor in the amount of 2.0 to 20.0 wt.%, first, in the reactor serves at 450-480oWith sulfur-containing light paraffin hydrocarbons With3-C4with a sulfur content of 0.15-0.25 wt.%. As the catalyst on the basis of high zeolite using a catalyst containing 53,28-59,69 wt.% high zeolite ZSM-5 with the ratio of SiO2/Al2O3=39 and a residual content of Na2O not more than 0.1 wt. per cent, of 35.5-37.5 wt.% aluminum oxide (Al2About3), 2.5 to 4.5 wt.% In2O3, 2.0 to 4.0 wt.% Zn, 0.2 to 0.5 wt.% Re, 0.01 to 0.02 wt. % Nd, 0.1 to 0.2 wt.% To, and the amount of added sulfur-containing light hydrocarbons regulate the condition that the ratio of rhenium in the catalysis of the Colo 1:25.

As the original paraffin hydrocarbons using paraffin hydrocarbons3-C4or C5-C11or2-C5.

The process is carried out on standard equipment using an adiabatic reactor.

Used in the method according to the invention the catalyst on the basis of high zeolite ZSM-5 of the above composition obtained by methods based on ion exchange is the replacement of alkali metal ions ammonium ions and including the subsequent processing of ammonium forms of promoting additives (metals) used in the form of various compounds (oxides, salts), including rare earth metals, the formation of granules with a binder, calcination and activation.

Use as promoters additives neodymium (Nd) and rhenium (Re), together with other additives (Zn, Al2About3In2O3To) increases the period of stable activity of the catalyst, which, in turn, increases the efficiency of the method of producing aromatic hydrocarbons.

Below is a specific example illustrating the method of producing catalyst based on zeolite ZSM-5 of the above composition.

Example 1.

4)2SO41 EQ. Na2O in the zeolite. In the prepared solution with stirring download 1245, high zeolite in sodium form, the resulting suspension is heated to 50-60oC and maintained at this temperature for 2 hours, the Suspension of the zeolite is drained on a suction filter and after extraction of the mother liquor is washed in 12,45 l condensate (per 1 kg of dry matter). The resulting pellet is discharged from the suction filter and subjected to subsequent processing (cation exchange) to a residual content of Na2Of the zeolite is not more than 0.1%. After washing the pellet and conducting cation-exchange with ammonium sulfate spend processing of zeolite powder in a solution of 6.8 l of 0.5 n solution of Zn (CH3COOH)2. The treatment is carried out for 2 h at a temperature of 60oIn the resulting suspension is added a suspension of orthosilicate Nd (7Nd2O39SiO3and solutions of acetates Re (10%) and (15%) in amounts corresponding content in the catalyst of 0.2-0.5% Re, 0.01 to 0.02% and 0.1 Nd K. After that, the suspension of the zeolite is filtered and sent to the granulation. Zeolite granularit with a binder in the following ratio of components: zeolite 60 wt. % (1245 g), Althe binder. The procedure for preparation of the masses for molding: in the mixer load estimated number of cakes (1245 g), Al2About3757 g2About3to 72.6 g and are peptization mass with addition of NGO3to pH 3. The mass is stirred until homogeneous and evaporated to the desired granulating humidity (40-48%).

Ready to moldable mass plastificator on rollers and is then formed on the screw granulator. Granules provalivajut on the air for 20 h and then dried in a chamber dryer for 10 hours Obtained granules are calcined in an electric furnace at a temperature of 500-550oWith over 6 hours the Temperature is raised to the desired speeds of no more than 150oWith in hours the catalyst has the following composition: (wt.%) vysokorentabelnoy zeolite ZSM-5 (with a ratio of SiO2/Al2About3- 39) 57,0; Al2About337,19;2About33,5; Zn 3,0; Re 0,2; Nd 0,01; 0,1.

Then spend processing (activation) of the catalyst with a gas mixture of, for example, contains, wt%: carbon monoxide 5; carbon dioxide 6; water vapor 15; 15 hydrogen; oxygen 5; nitrogen else if 500oC for 6 hours After completion of the gas treatment catalyst pellet purge air and cool air flow to the e bags, inserted into the barrel.

The catalyst prepared in this way preserves stable activity in the reaction of transformation of broad fraction of light hydrocarbons during 240 h, and in making gasoline for 480 hours Indicators control catalyst prepared in accordance with the method prototype is 100 and 280 h, respectively. Evaluation of the stability of the catalyst was carried out on the yield of aromatic hydrocarbons.

An additional effect is achieved due to the fact that the working temperature of the catalyst support due to combustion of gaseous side products, but not at the expense of the energy supply from the outside.

As catalysts for complete oxidation in the method according to the invention using known catalysts V2O5/MoO3in the form of granules, copper in the form of plates, mesh, granules of copper oxide and others.

As the light sulfur-containing raw material used is light hydrocarbon feedstock With3-C4paraffin with sulfur content of 0.15-0.25 wt.%.

The method according to the invention is that when the catalytic conversion of paraffin hydrocarbons (C3-C11in the process of aromatization reaction along with aromatic Pleven6that can be used to heat the catalyst instead of the main gas. In this case the presence of the oxidation catalyst leads to the formation of flue gases (carbon dioxide, water vapor), which by passing them through a zeolite catalyst together with the original paraffin hydrocarbons lead to a reduction of coke deposition on the catalyst.

Adding a gas mixture of carbon dioxide with water vapor in the amount of 2.0 to 20.0% is the most effective, as when adding a smaller amount on the catalyst surface remains strong acid centers on which active processes coking. Thus, adding the mixture of gases is less than 2.0% not achieved full alignment spectrum acidity of the catalyst surface due to lack of oxide and carbon dioxide.

The increase in the content of the gas mixture more than 20,0% leads to a qualitative change of surface acid sites of the catalyst due to their damping water vapor, nitric oxide and carbon dioxide. The result is dramatically reduced catalytic activity of the catalyst. In both cases, the yield of the target products (aromatic hydrocarbons) lower than in the known method, which is confirmed by e the gas to paraffin hydrocarbons according to below table.

Below is a specific example of the method according to the invention.

Example 2.

In the process of obtaining aromatic hydrocarbons using the catalyst in the amount of 4 kg, containing 57,0% high zeolite ZSM-5 with a residual content of Na2O not more than 0.1 wt.%, with a ratio of SiO2/Al2O3= 39, Al2O3- 37,19%2O3- A 3.5% Zn - 3%, Re - 0,2%, Nd - 0.01 Percent To - 0.1 Percent.

A portion of catalyst (100 g) containing 0.2 g (0,0027 mol) of rhenium are placed in a reactor and in a stream of air heated to a temperature of 450oC. Then the reactor instead of the air is nitrogen with a bulk velocity of 10 h-1. After two hours of Stripping with nitrogen in the reactor is fed a stable natural gasoline (sulfur-containing paraffin hydrocarbons)3-With a sulphur content of 0.2 wt.% with a bulk velocity of 50 h-1at a temperature of 450oC. Through a bed of the catalyst miss this volume of raw materials, through to the layer was omitted 0,0067 mole of sulfur (about 1065 g gasoline fraction). When this is achieved, the ratio of rhenium and sulfur at about 1:25.

Then the reactor was supplied raw materials (a mixture of paraffin hydrocarbons of the following composition, %: isobutane - 30, n-butane - 43, I-pentane - 11, n-pentane - 16 when the temperature is of telesfora complete oxidation (as a catalyst for complete oxidation was used vanadium catalysts V2O5/Moo3in the form of granules). Side of gaseous products at 550oWith a bulk velocity of 250 h-1subjected to full oxidation (weight of catalyst for complete oxidation was 400 g) prior to the formation of carbon dioxide and water vapor.

The mixture of carbon dioxide and water vapor mixed with the raw material in the preheater raw materials at 200oWith the amount of 15% to a mixture of paraffin hydrocarbons. The resulting mixture was fed into the reactor flavoring.

As a result of aromatization reaction the yield of aromatic hydrocarbons (C6-C9after passing for 40 hours (40 hour) was 66% (in the prototype, in similar conditions, the yield of aromatic hydrocarbons amounted to 57%).

The duration of the working period (to reduce the yield of the target products by 30% in comparison with the initial activity) amounted to 460 h (in the prototype, the duration was 400 h).

The composition can produce at the outlet of the reactor: aromatic hydrocarbons (C6-C9)-66%, aliphatic hydrocarbons - 8.4%, and gas - 24% (including hydrogen - 2,5%, methane - 4,0%, With2- 7,5%, With3+C4- 19%), coke 1,6%.

Similar results were obtained when using as the catalyst Ihad aromatic hydrocarbons.

Claims

The method of obtaining aromatic hydrocarbons by contacting in a reactor paraffin hydrocarbons with a catalyst based on high ZSM-5 at 350-380oWith, including the separation of the products of the contacting liquid and gaseous products, followed by complete combustion of gaseous products in the presence of the catalyst for complete oxidation of light hydrocarbons and adding to the original paraffin hydrocarbons formed during the combustion of a mixture of carbon dioxide and water vapor in the amount of 2.0 to 20.0 wt. percent, wherein the first reactor is served at 450-480oWith sulfur-containing light paraffin hydrocarbons With3-C4with a sulfur content of 0.15-0.25. % of catalyst based on zeolite using a catalyst containing 53,28-59,69 wt.% high zeolite ZSM-5 with a residual content of Na2O not more than 0.1 wt.% and the ratio of SiO2/Al2O3=39, of 35.5-37.5 wt. % Al2O3, 2.5 to 4.5 wt.% In2O3, 2.0 to 4.0 wt.% Zn, 0.2 to 0.5 wt.% Re, 0.01 to 0.02 wt.% Nd, 0.1 to 0.2 wt.% For, with the added sulfur-containing paraffin hydrocarbons injected in an amount to provide a ratio of rhenium in the zeolite catalyst and the silver is

 

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