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.
FIELD: petrochemical industry; production of zeolite.
SUBSTANCE: the invention offers the method of production of titanium-containing zeolite by: (a) combining a capable to be hydrolyzed silicon compound and a capable to be hydrolyzed titanium compound; (b) adding a basic quaternary ammonium compound in a water medium into the mixture from a stage (a) and a hydrolysis of a reaction mixture at the temperature within the interval from 0 up to 100°C with production of a synthesis sol; and then (c) the synthesis sol aging at the temperature within the interval from 150 up to 190°C and (d) crystallizations of the synthesis sol at this temperature, differing by the fact, that aging duration at the increased temperature at the stage of (c) makes less than 240 minutes. The method ensures production of zeolite with a catalytic activity in reactions of epoxidation of olefins by hydrogen peroxide.
EFFECT: the invention ensures production of zeolite with a catalytic activity in reactions of epoxidation of olefins by hydrogen peroxide.
8 cl, 1 tbl
FIELD: zeolite production processes.
SUBSTANCE: method comprises steps of preparing synthesis gel by combination and hydrolysis of silicon compound capable to be hydrolyzed, titanium compound capable to be hydrolyzed and basic quarternary ammonium compound in aqueous medium taken in quantities providing on conversion to said initial compound value of molar relation Si/Ti equal to or more than 30 and relation N/Si is in range 0.12 - 0.20; then crystallizing synthesis gel at temperature 150 - 220°C for time period less than 3 days.
EFFECT: possibility for producing titanium-containing zeolite with high catalytic activity at process of epoxydation of olefins with use of hydrogen peroxide.
10 cl, 5 ex, 2 tbl
FIELD: industrial organic synthesis.
SUBSTANCE: invention relates to composition suitable for use in reaction zone wherein aniline is brought into contact with nitrobenzene to produce 4-aminodiphenylamine synthesis intermediates, which composition contains zeolite having internal channels with a base introduced therein to take part in above reaction. Dimensions of cross-section of channels is such that a limited reaction transition state is ensured thereby improving selectivity of reaction with regard to desired intermediates. Invention also related to the title process using above defined composition.
EFFECT: improved selectivity of 4-aminodiphenylamine intermediates production.
9 cl, 12 dwg, 7 tbl, 8 ex
FIELD: organic synthesis catalysts.
SUBSTANCE: invention provides novel synthetic porous crystalline material, named MCM-71, method of preparation thereof and its use in organic compounds catalytic conversion processes. This material is characterized by specific radiograph and has unique three-dimensional channel system including generally straight high-elliptic channels, each of which is determined by 10-membered rings of tetrahedrally coordinated atoms crossing with sinusoidal channels, each of which is determined by 8-membered rings of tetrahedrally coordinated atoms.
EFFECT: extended choice of catalytically active zeolite material.
9 cl, 7 dwg, 4 tbl, 4 ex
FIELD: oil refining; preparation of catalysts for refining of oil fractions; preparation of catalysts for benzene hydroisomerization process.
SUBSTANCE: proposed method includes mixing of components: zeolite component-mordenite with binder-aluminum hydroxide, plastification by means of peptizing by acid solution, granulation, application of platinum and reduction of catalyst; components are mixed at mass ratio of from 1:9 to 2:3 in terms of calcined mordenite and aluminum hydroxide; after application of platinum, heat treatment is carried out at two stages at temperature of 100-110°C at first stage and not above 250-300°C at second stage; reduction of catalyst is performed at temperature not below 500°C. Used as aluminum hydroxide is pseudo-boehmite of Catapal A grade. Used as zeolite component is high-modulus mordenite at silicate modulus M=20-30 at its content in catalyst of 20-30%. Used as zeolite component is low-modulus mordenite at silicate modulus M=10 at its content in catalyst not exceeding 10%.
EFFECT: enhanced selectivity of catalyst; considerable reduction of power requirements.
1 tbl, 3 ex
SUBSTANCE: invention relates to the microporous crystalline material of zeolite origine (ITQ-22) which in tempered condition has the empiric formula x (M1/nXO2): y YO2 - z GeO2 : (1 - z) SiO2 where M is H+ or at least one inorganic cation with +n charge; X is at least one chemical element with the oxidation rate +3 chosen preferably from the group that consists of Al, Ga, B, Fe and Cr; Y is at least one chemical element with the oxidation rate +4, different from Si and Ge, and chosen preferably from the group that consists of Ti, Sn and V; x has the value less than 0.2, preferably less than 0.1 and can be equal to zero, y has the value less than 0.1, preferably less than 0.05 and can be equal to zero, z has the value less than 0.8, preferably between 0.005 and 0.5 and can be equal to zero. In accordance with the invention, the material has the typically X-ray diffraction pattern.
EFFECT: invented material can recommended as catalyst in processes which include separation and transformation of organic compounds.
40 cl, 2 dwg, 18 ex
SUBSTANCE: claimed is water solution of hydrogen peroxide, suitable for olefine epoxidation, which includes: I) in total less than 50 wt fraction/mln of alkaline metals, alkaline-earth metals or their combinations irrespective of whether said alkaline or alkaline-earth metals are in catione-active or complex form; II) in total at least 50 wt fraction/mln of amines, which have pkb value less than 4.5, or respective protonated compounds; and III) in total at least 100 wt fraction/mln anions or compounds, which are able to dissociate with anion formation, according to which values in wt fraction/mln are given in terms of hydrogen peroxide weight. Claimed is method of obtaining hydrogen peroxide solution. Claimed is application of water solution of hydrogen peroxide.
EFFECT: economically efficient production of water solution of hydrogen peroxide and improved long-term activity and selectivity of catalyst.
18 cl, 5 ex, 2 tbl
SUBSTANCE: present invention refers to catalyst compositions containing zeolite and inorganic binding agent with particular mechanical characteristics porosity and characteristics, and available as a catalysts in industrial fixed-bed catalytic reactors. There is disclosed composition containing zeolite and inorganic binding agent, where zeolite has crystal structure with holes formed by 12 tetrahedrons, while binding agent is aluminium γ-oxide. Herewith the composition described above is characterised by pore space derived from summing up mesoporous and macroporous components found in the specified catalyst composition, exceeding or equal 0.7 cm3/g, and at least 30% of said pore space volume consist of pores of diameter exceeding 100 nanometres. Additionally there are disclosed method of preparing catalyst composition specified above, method of aromatic hydrocarbon transalkylation involving aromatic hydrocarbon contacting to one or more polyalkylated aromatic hydrocarbon with the said catalyst composition added. Besides, there is disclosed method of preparing monoalkylated aromatic hydrocarbons involving: a) aromatic hydrocarbon contacting to C2-C4- olefin with acid catalyst added in such alkylation conditions, that reaction is enabled, at least partially in liquid phase, b) product separation to fraction containing aromatic hydrocarbon, fraction containing monoalkylated aromatic hydrocarbon, fraction containing polyalkylated aromatic hydrocarbons, and fraction containing heavy aromatic hydrocarbons, c) fraction containing polyalkylated aromatic hydrocarbons contacting to aromatic hydrocarbon with the said catalyst added, in such transalkylation conditions, that reaction is enabled, at least partially in liquid phase.
EFFECT: improved catalyst performance, both concerning its durability and productivity, improved mechanical characteristics of the catalyst, such as crushing strength and abrasion resistance, ensured high yield and high efficiency of transalkylation.
40 cl, 1 tbl, 6 dwg, 4 ex
SUBSTANCE: invention refers to method of isobutylene production by decomposition methyl-tertiary-butyl ether with heterogeneous catalyst at raised temperature and pressure, characterised that catalyst is multi-purpose synthetic zeolite NaX, while process is enables at atmospheric pressure with water vapour with observing the conditions as follows: temperature 200-250°C, volumetric MTBE feed rate 1.0-2.0 h-1. These conditions ensure minimal generation of MTBE decomposition by-products.
EFFECT: MTBE conversion per run is 96-99% with isobutylene selectivity at least 99%.
1 cl, 3 tbl, 9 ex
SUBSTANCE: present invention relates to compositions and methods of reducing adverse effect of metallic contaminants on catalytic cracking. An additive for catalytic cracking is described, which contains a combination of: a) material which traps metals, selected from calcium-containing compound, magnesium-containing compound or their combination, a compound similar to hydrotalcite, a compound which contains silicon dioxide and aluminium oxide, mixed metal oxide or their combination; and b) a highly active catalyst, with percentage content of zeolite at least approximately 1.5 times greater and/or total surface area at least approximately 1.5 times greater, and/or total crystallinity at least approximately 1.5 times greater than that of a bulk catalyst, also used in catalytic cracking. Also described is a circulating available amount of catalyst particles in the method of cracking with a fluidised catalyst, where approximately from 2 to 80 wt % of the said available amount makes up the said additive for catalytic cracking. A method is described for catalytic cracking starting material, involving bringing the said starting material, under catalytic cracking conditions, into contact with a composition, which contains a bulk catalyst and the said additive for catalytic cracking. A method is also described for catalytic cracking starting material in the presence of at least one metal with improved operational characteristics of the bulk catalyst, involving bringing into contact with the said additive for catalytic cracking.
EFFECT: increased conversion of the process, at the same time minimising output of byproducts, such as coke and hydrogen.
42 cl, 3 dwg, 5 tbl, 7 ex
FIELD: polymerization processes and catalysts.
SUBSTANCE: alkylene oxide polymerization is conducted in presence of catalyst based on bimetallic cyanide complex and initiator containing hydroxyl group. Al last part of the catalyst is preliminarily subjected to treatment by ultrasonic and/or electromagnetic emission. Invention discloses both polymerization catalyst treatment method and catalyst itself.
EFFECT: enabled production of polyether-polyols with low unsaturation level and increased activity of catalyst.
10 cl, 3 ex
FIELD: woodworking and resin industries.
SUBSTANCE: invention concerns anthraquinone-based wood delignification catalyst, which can be used in vegetable stock cooking process involving alkaline technologies. Method comprises liquid-phase interaction of anthracene with oxidant in organic solvent followed by crystallization of anthracene. The latter operation is conducted for 1 to 10 min in presence of benzoic acid (consumption 0.01-0.3%) in ultrasonic field generated by ultrasonic emitter at acoustic power 0.6 kW and frequency 22 kHz.
EFFECT: increased catalytic activity of anthraquinone and reduced consumption of catalyst.
3 cl, 4 tbl, 4 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: catalyst preparation method comprises: mixing high-silica Pentasil ZSM-5-type zeolite in ammonium form with distilled water, zinc nitrate, aluminum hydroxide, and boric acid; evaporating resulting mass; molding granules; drying; and treating granules with laser emission at power 40-50 W in three passes across monolayer of catalyst granules at scanning rate 800-1000 mm/min.
EFFECT: increased yield of aromatic hydrocarbons.
1 tbl, 11 ex
FIELD: oxide catalyst preparation methods.
SUBSTANCE: invention relates to preparation of oxide-structure catalysts and provides a method for preparing oxide catalyst characterized by mixing two or more salt precursors of catalyst components followed by melting resulting mixture to achieve homogenous melt, cooling this melt to room temperature and subsequent decomposition of salts and calcination, wherein salt precursors of catalyst components are selected from d-metal nitrates (Ce and Y nitrates), melting of mixture is effected at 90 to 170°C in presence of ammonium nitrate used at ratio (2-10):1 to metal nitrate mixture, and decomposition of the melt into oxides is performed under effect of microwave emission. In a preferred embodiment of invention, microwave emission is used for 0.5-5 min at working frequency 2.45 GHz and power 600-1900 W. A method of preparing oxide catalysts involving introduction of oxide structure carrier into resulting melt at continuous stirring is also described.
EFFECT: enabled preparation of oxide catalysts and spinel-structure catalysts characterized by high degree of uniformity, lack of harmful impurities in catalyst composition, high-developed surface, and high heat resistance.
8 cl, 2 tbl