A method of obtaining a zeolite catalyst

 

(57) Abstract:

The invention relates to heterogeneous catalysis of redox and acid-base processes and can be used in refining and petrochemical industries, as well as in analytical chemistry and organic synthesis. In addition, the invention can find application in medicine, the treatment of sewage and industrial waters and other processes. The aim of the invention is to increase the catalytic activity of the catalyst, the reduction in water consumption and wastewater. The goal achieved by a method of obtaining a zeolite catalyst by treating the zeolite in the chamber of the electrolytic cell, in which the treatment is carried out at a voltage of 50 To 100 V for 2 to 3 h, and as the aqueous phase taken from 0 to 0.2%, the solution of the background electrolyte. 1 C. p. F.-ly, 1 table.

The invention relates to heterogeneous catalysis of redox and acid-base processes and can be used in refineries, petrochemical and organic synthesis during aromatization of paraffin and olefin hydrocarbons, and mixtures thereof, in the hydrofining gasoline fractions.

The centre is Asa or water molecules in ion cation.

The formation of hydroxyl groups occurs by replacement of the sodium cations in the zeolite framework on the proton is called decationization.

A method of obtaining zeolite catalyst by treating the zeolite in an aqueous phase through NH4form, which is obtained directly by the exchange of sodium ions in the zeolite to ammonium ion and solutions of various ammonium salts. Then NH4-form of the zeolite is heated to a temperature of 450 to 500oC in vacuum or in air for removal of ammonium. To achieve a high degree of decationization treatment is carried out repeatedly, combining with intermediate annealing at 450 500oC. the Degree of exchange of sodium reaches 80 to 99% (Minachev H. M. and I. Isakov, I. the Preparation, activation and regeneration of zeolite catalysts. Analyte. review, ser. Refining, M. Tsniiteneftehim, 1971).

The disadvantages of this method are multi-stage processes, high consumption of the ammonium salts, the formation of significant quantities of wastewater containing anions of acids. This method is implemented in industry.

The closest in technical essence to the present invention is a method of obtaining a zeolite catalyst dictionaraoke Na DCM spend 25% solution of hydrochloric acid at 60oC for 2 hours After that zeolite thoroughly washed with distilled water to a reaction of the chloride ions. Dried, formed with the addition of 20% aluminum hydroxide and fractionary. Just before experience the catalyst is activated by blowing air at 550oC for 14 h (Minachev H. M. and I. Isakov, I. the Preparation, activation and regeneration of zeolite catalysts. Analyte. review, ser. Refining, M. Tsniineftekhim, 1971).

The disadvantages of this method are the high corrosiveness of the solution, and therefore the establishment of wastewater with a high degree of acidity, containing anions of acids.

The problem to which this invention is directed, is to develop a method of producing zeolite catalyst having a high catalytic activity, with a low consumption of water and wastewater.

The problem is solved by the proposed method obtain a zeolite catalyst by treating the zeolite in an aqueous phase in the diaphragm electrolyzer to achieve the minimum content of Na2O. In an advantageous embodiment of the method the aqueous phase is taken in the form of 0.01 to 0.2% aqueous solution of neutral, El is DSTV GOZ, VNIIM/ loaded into the chamber of the electrolyzer banochnogo type. Previously there was pouring water or an aqueous solution of indifferent electrolyte. As electrodes for use of ORT /titanium anodes coated with ruthenium oxide/. The current source rectifier ICA. After turning on the current in the anode space of the pH of the solution is reduced, and the cathode is increased. The treatment is carried out at a voltage of 50 to 120 In during 1,0 3,0 h until reaching the minimum value Na2O. After treatment, the zeolite is filtered, dried, molded, activate air at 500 550oC, analyzed by sodium by flame photometry. Catalytic activity test in the aromatization reaction of ethylene. As the target product take exit liquid catalyst consisting of 95 to 98% of aromatic hydrocarbons. The reaction is carried out in a flow microcatalytic reactor (volume of catalyst 1 cm3), the feed rate of ethylene 7.5 ml/min, T 500oC.

As a result of leaking water electrolysis in the anode space is intense acidification of the solution to pH less than 2, and cathode - alkalization to pH over 9.0 in. Secondary camera in case it is used the pH is lowered to about 4.0 to 4.5. The intensity of the electrolysis is determined by the processing time, the difference potentiate ions from the channels of the zeolite. So there is a modification of the acid-base properties of the zeolite by ion exchange of sodium and aluminum in the crystal structure, the cations contained or formed on the electrode space or secondary camera. The concentration of sodium cations in the cathode chamber can significantly reduce the amount of wash water and dispose of alkaline solution Catolica in the process.

Used to obtain catalysts zeolites CVM and NaY differ silicate module SiO2/Al2O3, structure and reactivity of the crystalline framework. For the CVM module is 25 to 50, for NaY module is equal to 2 4.

A new set of claimed essential features allows along with high catalytic activity of the obtained catalyst to significantly reduce the water consumption and the production of effluent.

The analysis selected in the search process known solutions showed that in science and technology there is no object, similar to the declared essential features and possessing high catalytic activity at low water consumption and wastewater, which allows to make a conclusion on compliance of the proposed facility cryo object of the criterion of "industrial applicability" presented concrete examples of implementation of the method.

Example 1 (according to the method of the prototype). Decationization zeolite DCM is carried out by processing 25% aqueous solution of hydrochloric acid for 2 hours at a temperature of 60oC. After treatment, the zeolite is washed with distilled water and analyzed by flame photometry on the content of sodium ions. The residual content of Na2O in the zeolite 0.04% of the Catalytic tests were carried out in flowing microcatalytic reactor with a capacity of 1 cm3. The zeolite is dried, formed with the addition of 10 wt. aluminum hydroxide, crushed, selected fraction 0,2 0,1 mm. Before you experience the catalyst was activated by blowing air at 500oC for 5 h In the quality of the target product of the process of aromatization of ethylene was taken out of liquid catalyst. The maximum yield of the catalyst was observed at 2 to 3 hours of reactor operation. The feed rate of ethylene 7.5 ml/min, the temperature in the reactor 500oC.

Example 2 (present method). A portion of the zeolite DCM 4 g is placed in a chamber pot, fill the pot with 0.2% aqueous electrolyte solution /ammonium chloride/. Include a current source, a potential difference of 50 C. processing time of 2.0 h, the pH of the analyte of 2.5. After treatment, the zeolite is formed and activated by calcination in a stream >. Catalytic tests carried out analogously to example 1.

Examples 3 to 14. The process is carried out analogously to example 3, changing the type of zeolite, voltage, treatment time, concentration and nature of the background electrolyte. The data obtained in examples 1 to 14, are summarized in table.

As can be seen from the table, the optimal voltage for the process 50 120 depending on the concentration of indifferent electrolyte. At high voltages there is intense boiling of the solution due to the significant flow of current through the electrolyzer. Lower voltage is not allowed to obtain active catalyst due to the large residual content of sodium ions in the zeolite.

From the table it is seen that the proposed method allows

to get more active the catalyst, the increase in activity 15%

to exclude the consumption of washing water and, consequently, reduce the production of effluent;

significantly reduce the consumption of reagents used.

1. A method of obtaining a zeolite catalyst by treating the zeolite in an aqueous phase, followed by forming and activation annealing, characterized in that the processing of the aqueous phase are in the pot until the aqueous phase is taken as 0.01 to 0,2% solution of indifferent electrolyte.

 

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