Naphtha reforming catalyst and catalytic reforming of naphtha

FIELD: chemistry.

SUBSTANCE: present invention refers to naphtha reforming catalyst. There is disclosed a catalyst effective in naphtha reforming involving particles of heat-resistant inorganic oxide carrier containing dispersed bivalent tin, platinum group metal and rhenium and optionally halogen, characterised that tin uniformly coats the catalyst, and platinum group metal uniformly coats the catalyst; tin is impregnated into the carrier with using tin chelate resulted from reaction of chelating agent representing amino acid and bivalent tin salts. There is also disclosed catalytic reforming of naphtha as feed stock, wherein feed stock contacts with said catalyst in reforming environment involving temperature 315°C-600°C, pressure 100 KPa - 7 MPa (abs.), liquid hourly space velocity 0.1-20 h-1, and molar ratio of hydrogen to naphtha feed stock 1-20.

EFFECT: new naphtha reforming catalyst and new catalytic reforming of naphtha.

10 cl, 2 dwg, 1 tbl, 6 ex

 

The technical field to which the invention relates.

The present invention relates to a catalyst for reforming of naphtha. The catalyst includes the use of chelating ligand to obtain a chelate complex of tin. The invention also relates to a method of reforming catalyst, which provides increased selectivity to gasoline and aromatic products.

Prior art

Catalytic reforming involves many competing processes or sequences of reactions. They include dehydrogenation of cyclohexanes to aromatic compounds, dehydroisomerization of alkylcyclopentanes to aromatic compounds, dehydrocyclization acyclic hydrocarbons to aromatics, hydrocracking of paraffins to light products boiling outside the range of gasoline, dealkylation of alkyl benzenes and isomerization of paraffins. Some of the reactions occurring during reforming, such as hydrocracking, which gives light gaseous paraffins, cause a negative effect on the yield of products boiling in the range of gasoline. Improvements in catalytic reforming process thus aim at increasing the contribution of reactions leading to a higher yield of gasoline fraction with a given octane number.

Criticismwagner is that the catalyst had the ability to fulfill their nominal functions and effectively initially and satisfactorily over long periods of time. The parameters commonly used in the prior art to determine how well the individual catalyst performs its intended function in a separate reactions involving hydrocarbons, are activity, selectivity and stability. When carrying out reforming these parameters are defined as follows:

(1) Activity is a measure of the ability of the catalyst to convert hydrocarbon reactants into products at a rigidly specified level, with a level of rigidity, the combination of a reaction conditions: temperature, pressure, time of contact and the partial pressure of hydrogen. The activity is usually characterized as the octane number of pentane and heavier flow ("C5+") products for a given consumption of raw materials on tightly specified level, or conversely as the temperature required to achieve a given octane number.

(2) Selectivity refers to the percentage of output petrochemical aromatic compounds or5+ components of gasoline on specified raw materials with a certain level of activity.

(3) Stability refers to the rate of change in activity or selectivity per unit time is or recycled raw materials. The stability of the activity, in General, measured as the rate of change of the working temperature per unit of time or raw materials to achieve a desired octane number of the C5+ product, with a lower rate of temperature change corresponding to the best stability activity as catalytic reforming units typically operate with a relatively constant ostanovit number of the product. The stability of the selectivity is measured as the rate of decrease of the output With5+ product or aromatic compounds per unit of time or materials.

Programs to improve the performance of reforming catalysts are stimulated by changes in the composition of gasoline, after large-scale abandonment lead antitelomerase additive to reduce harmful vehicle emissions. The improvement of gasoline, for example, catalytic reforming, should work with greater efficiency and flexibility to meet these changing requirements. The selectivity of the catalyst becomes more important than ever to align components of gasoline to these requirements, when excluding losses less valuable products. The main problem faced by professionals working in this field of technology, therefore, is the development of more selective catalysts while maintaining an effective activity and stability of the catalyst.

The reforming catalysts containing tin as a modifier of the platinum group (or group VIII), together with additional third metal promoter, such as rhenium, indium, gallium, iridium, etc. are well known in the prior art. US 6153090 open way catalytic reforming catalyst, comprising at least one metal of group VIII, at least one additional element selected from the group consisting of germanium, tin, lead, rhenium, gallium, indium, thallium, in which the element of the promoter is added in the form of metal-organic carboxylate compounds containing at least one ORGANOMETALLIC bond, such as acetate anti.

It is also known that chelating ligands can be used for impregnation of the carrier metal. For example, US 4719196 disclose the receipt of the catalyst application solution containing ethylenediaminetetraacetic acid (EDTA), a noble metal and ammonia. US 5482910 disclose a method of obtaining a catalyst with the use of a mixed solution containing EDTA, noble metal, and a metal promoter, such as alkaline earth metal. US 6015485 and US 6291394 disclose a method of processing an existing catalyst EDTA to create a bimodal structure with mesopores of aluminum oxide with two different the sizes of the crystallites.

Accordingly, the inventors have developed a method of producing catalysts, which involves the use of a chelate complex of divalent tin to tin impregnation. The method includes obtaining a solution of tin containing chelate ligand, for example EDTA. This solution is heated and then used for impregnation of refractory oxide carrier such as alumina. Before, during or after chelation impregnation another solution can be applied for impregnation of platinum group metals and any other desired metal promoters, such as rhenium. Preferably, the impregnation chelate tin perform under alkaline conditions, while the other components impregnation is performed in acidic conditions. After impregnation, calcination and restore get the desired catalyst.

A brief statement of the substance of the invention

The present invention relates to an improved method of reforming naphtha, the catalyst for implementing the method of reforming naphtha, and method for producing a catalyst for reforming of naphtha. Accordingly, one aspect of the invention is a method of producing catalyst for reforming of naphtha, comprising: a) obtaining a first aqueous solution containing a chelating agent and a compound of divalent tin; (b) heating the specified first solution flows, is from 5 minutes to 5 hours at a temperature of 40°C-100°C; (C) obtaining a second aqueous solution containing a compound of an element of the platinum group and the compound of rhenium; (e) the impregnation of a solid refractory oxide carrier a first solution to obtain the first impregnated solid carrier; (g) impregnation of the specified first impregnated solid carrier indicated by the second solution to obtain a second impregnated solid carrier; (h) calcining the second impregnated solid carrier at a temperature of 300°C-850°C for from 10 minutes to 18 hours to obtain a calcined catalyst and (i) recovering the calcined catalyst at a temperature of 300°C-850°C for from 10 minutes to 18 hours in a reducing atmosphere, thus obtaining the specified catalyst suitable for reforming naphtha.

The invention also relates to a method of catalytic reforming of naphtha as feedstock, which includes the contact of the raw material in the reforming conditions with a catalyst comprising particles of inorganic oxide carrier with a printed on it divalent tin, platinum group metal and rhenium; catalyst, characterized in that the tin deposited on the carrier by impregnation of a chelate complex of tin and a uniform distribution on the support.

In addition, the invention relates to a catalyst effective in the reforming of naphtha, including cha is based heat-resistant inorganic oxide carrier, printed on it divalent tin in an amount of 0.01-5 wt.% the element platinum in an amount of 0.01-2 wt.% element, and rhenium in an amount of 0.05-5 wt.% on the item. The catalyst is characterized by the fact that tin is distributed uniformly, and the platinum group metal is distributed uniformly; tin deposited on the carrier by impregnation using chelate complex of tin.

Brief description of drawings

Figure 1 is a graph of the dependence of the yield of liquid With5+ products from the lifetime of the catalyst for various catalysts with tin, applied in various ways.

Figure 2 is a plot of the average temperature of the reactor block, the activity of the catalyst, from the lifetime of the catalyst to the various ways of applying the tin.

A detailed description of the invention

The catalyst of the present invention is particularly useful as a catalyst for conversion of hydrocarbons. The catalyst is particularly suitable for catalytic reforming feedstock range of gasoline, and can also be used, among other things, to dehydrocyclization, isomerization of aliphatic and aromatic compounds, dehydrogenation, hydrocracking, disproportionation, dealkylation, alkylation, transaminirovania and oligomerization. In the preferred catalytic FPIC shall be reforming hydrocarbons and rich hydrogen gas is preheated and loaded into the reforming zone, contains consistently usually from two to five reactors. Suitable means of heating are between reactors to compensate for the total heat loss due to the endothermic reaction in each reactor. The reactants may be contacted with the catalyst in a separate reactor or in an upward, downward or radial flow, with the preferred radial flow. The catalyst is in the system with a fixed layer or preferably in the system moving bed continuous catalyst regeneration. Alternative approaches to the reactivation of the deactivated catalyst is well known qualified specialists in the art and include preregistration operation, in which the entire set is disconnect for catalyst regeneration and reactivation or disable operation of the reactor, in which a separate reactor is isolated from the system regenerate and reactivit, while the other reactors remain in operation.

The reforming conditions used in the method of reforming the present invention include a pressure selected within the range of 100 KPa To 7 MPa (abs). Particularly good results are obtained at low pressure, i.e. at a pressure of 350-2500 KPa (abs). The temperature of the reformer is in the range of from 315° to 600°C., and preferably from 425° to 565°C. As is well known, to unificirovannykh specialists in the field of reforming, the initial selection of the temperature within this broad range is carried out, primarily on the basis of the desired octane of the product of reforming taking into account the characteristics of the feedstock and catalyst. Usually the temperature is then slowly increase during operation to compensate for the inevitable deactivation to ensure a constant octane product. Enter enough hydrogen to achieve a content of 1 to 20 moles of hydrogen per mole of hydrocarbon feedstock fed to the reforming zone, with very good results obtained with the application of 2-10 moles of hydrogen per mole of hydrocarbon feedstock. Similarly, the hourly space velocity of fluid (LHSV)used in reforming, selected in the range 0.1 to 20 h-1with the preferred value in the range 1-5 h-1.

The hydrocarbon feedstock fed to the system reforming, preferably represents a naphtha comprising naphthenes, and paraffins boiling in the range of gasoline. The preferred feedstock is naphtha, consisting mainly of naphthenes and paraffins, although in many cases, the aromatic compounds will also be present. This preferred class includes gasoline straight race gas gasolines, synthetic gasolines, and the like Naphtha with a boiling range gasoline fraction as recognize the aqueous raw material can be completely wikipedi gasoline, with an initial boiling point (ASTM D-86 from 40° to 80°C and a final boiling point within the range of from 160° to 220°C., or may be a selected fraction of naphtha, which, in General, will be more high-boiling fraction, usually referred to as a heavy naphtha -- for example, a naphtha boiling in the range of 100°-200°C. If the reformer is directed to receive one or more of benzene, toluene and xylenes, the boiling range may be primarily or substantially within the range of 60°-150°C.

As indicated, the present invention relates to a method for producing the catalyst. The catalyst includes a solid carrier of heat-resistant oxide coated on the tin, at least one metal of the platinum group and optionally a metal modifier, such as rhenium. The carrier can be any of a variety of well-known carriers in the prior art, including aluminum oxide, silicon dioxide/aluminum oxide, silicon dioxide, titanium dioxide, Zirconia, and zeolites. Oxides of aluminum, which can be used as the carrier include gamma-alumina, theta-alumina, Delta-alumina and alpha alumina, preferably gamma - and theta-alumina. Among the oxides of aluminum included oxides of aluminum, which contain modifiers such as tin, zirconium, and titanium phosphate. Zeolites, to the which can be applied, include faujasite, beta-zeolite, L-zeolite, ZSM-5, ZSM-8, ZSM-11, ZSM-12 and ZSM-35. The media can be molded in any desired form, for example, spheres, tablets, bars, extrudates, powders, granules, etc. and they can be used with any specific size.

One method of obtaining spherical carrier of aluminum oxide is a well known method drops in oil, which is described in US 2620314. The way a drop in oil involves the formation of an aluminum Hydrosol by any of the methods employed in the prior art and preferably by the reaction of aluminum metal with hydrochloric acid; combining the Hydrosol with a suitable generouse agent; and puncturing the mixture in an oil bath with a high temperature. Droplets of the mixture remain in the oil bath until they harden and form hydrogel spheres. The spheres are then continuously removed from the oil bath and typically subjected to specific aging treatment and drying in an oil and ammoniacal solution to further improve their physical characteristics. Then we get old and melirovanie sphere washed and dried at a relatively low temperature of 80°-260°C. and then calcined at a temperature of 455°-705°C for 1-20 hours. This treatment leads to the conversion of the hydrogel to the corresponding transparent gamma aluminum oxide If necessary theta-alumina, the hydrogel spheres calcined at a temperature of 950°-1100°C.

An alternative form of carrier is a cylindrical extrudate, preferably obtained by mixing the alumina powder with water and suitable peptization, for example HCl, to education extrudable mass. The amount of added water for the education of the masses is usually sufficient to achieve weight loss on ignition (LOI) at 500°C 45-65 wt.%, preferably 55 wt.%. The share of added acid is usually sufficient to ensure 2-7 wt.% the alumina powder without volatile components used in the mixture, preferably 3-4 wt.%. The resulting mass ekstragiruyut through the die plate of the appropriate size for receiving the extrudate particles. Then these particles are dried at a temperature of 260°-427°C for 0.1 to 5 hours to obtain particles of the extrudate. Preferably heat-resistant inorganic oxide includes mostly pure alumina with an apparent bulk density of 0.6 to 1 g/cm3and surface area 150-280 m2/g (preferably 185-235 m2/g with a pore volume of 0.3-0.8 cm3/g).

The metal of group IVA (IUPAC 14) is an essential component of the catalyst of the present invention. From metals of group IVA (IUPAC 14), germanium and tin is preferable, and tin are particularly preferable. This component can prisutstvovat is how the metal, as a chemical compound such as the oxide, sulfide, halide, oxychloride, etc. or as a physical or chemical combination with the porous material of the carrier and/or other components of the catalytic composite. Preferably, the main part of the metal of group IVA (IUPAC 14) is in the final catalyst in oxidation States higher than the elemental metal. The metal of group IVA (IUPAC 14) optimally used in a quantity sufficient to achieve the final content in the catalytic composite from 0.01 to 5 wt.% metal, calculated on the element, with the best results obtained with 0.1 to 0.5 wt.% metal.

The metal or metals of group IVA (IUPAC 14) is applied on the desired media in the following way. First get a water solution of the chelating ligand and at least one soluble, degradable compounds metal promoter to obtain a chelate complex of a metal promoter. Preferably the compound of the metal is a compound of tin. More preferably the compound of the tin salt is tin. Examples of suitable tin salts or water-soluble compounds of tin include, without limitation bromide tin (II)chloride tin (II)fluoride, tin (II)iodide, tin (II)sulfate, tin (II)tartrate, tin (II)oxalate, tin (II)acetate, tin (II) and similar compounds. The use of salts of tin in the form of chloride compounds, for example, chlorine is IDA divalent or tetravalent tin especially preferably because this facilitates the inclusion and tin and at least a minor quantity of the halogen on one stage. Highly preferred is a salt of divalent tin, with two additional degrees of oxidation.

Chelating ligands, which can be used in the method of the present invention include amino acids, which after decomposition do not leave extremely harmful components on the media, such as sulfur. Specific examples of these amino acids include ethylenediaminetetraacetic acid ("EDTA"), nitrilotriacetic acid, N-methyliminodiacetic acid, iminodiethanol acid, glycine, alanine, sarcosine, α-aminobutyric acid, N,N-dimethylglycine, α,β-diaminopropionic, aspartate, glutamate, histidine, and methionine.

The solution of the chelate complex of a metal, which is preferably a solution of the chelate complex tin, heated for from 5 minutes to 5 hours at a temperature of 40°-100°C or up to its boiling point. The ratio of the chelating ligand to metal salt varies from 1 to 8 and preferably from 1.5 to 4.

The solution of the chelate complex of a metal described above may also contain a basic compound selected from the group consisting of ammonium hydroxide and Quaternary ammonium compounds with the formula NR1R2R3R4+X-where R1, R 2, R3, R4are each separately methyl, ethyl, propyl, butyl or t-butyl and X is a hydroxy-group. The purpose of adding one or more of these basic compounds is to regulate the pH of the solution to changes in the distribution of metals. Next, the metal distribution IVA (IUPAC 14) may differ from the distribution of platinum group metal or other metal promoter. In the present invention preferably tin, and platinum components group were uniformly distributed in the catalyst.

The solution of the chelate complex of a metal used for the deposition of metal on the carrier by known means in the prior art. Examples of these funds include aerosol and evaporative impregnation. Aerosol treatment includes spraying a small amount of the mixed solution on the carrier in motion. After spraying the moistened carrier can be moved to another machine for drying or final stages. One particular way of evaporative impregnation includes rotary dryer with steam jacket. In this way the carrier is dipped in the solution impregnation, which is placed in the dryer and the medium is stirred by rotation of the dryer. Evaporation of the solution in contact with peremeshivajutsa carrier is accelerated by the application of p is RA in the jacket of the dryer. The impregnated carrier is then dried at 60°-300°C and then calcined at a temperature of 300°-850°C for 30 minutes to 18 hours, to obtain a calcined catalyst. Finally, the calcined catalyst is restored by heating the catalyst in a reducing atmosphere, preferably in a dry hydrogen at a temperature of 300°-850°C for from 30 minutes to 18 hours.

In one implementation of the invention refractory oxide carrier is first impregnated with a chelate complex of tin and then impregnated with the platinum group component. In another implementation of the invention chelate complex tin impregnated after the platinum group component. You should note that the stage of impregnation can also be combined, thus effectively functioning as a co-impregnation. Preferably, when at least 80 wt.% component of the platinum group deposited by impregnation on the media, and then immediately can be started impregnation chelate complex of tin. Alternatively, when two different impregnation, then the carrier may be dried and/or calcined between the required procedures in the conditions of drying and calcination, as listed below. Preferably, the annealing after the first separate impregnation should be enough to turn the tin oxide in connection olo is A.

An essential component of the catalyst is distributed platinum group component. This platinum group component may be part of the final catalytic composite as a compound such as oxide, sulfide, halide, oxyhalide, etc. in chemical combination with one or more other ingredients of the composite or metal. It is preferable that basically all of this component was present in the elemental state and was homogeneously distributed in the material of the carrier. This component may be present in the final composite catalyst in any amount which is catalytically effective, but preferred a relatively small number. Of the platinum group metals, which can be distributed on the desired media, the preferred metals are rhodium, palladium, platinum, and most of all preferred platinum. Platinum is usually 0.01 to 2 wt.% the final catalytic composite, calculated on the element. Very good results are obtained when the catalyst contains 0.05-1 wt.% platinum.

This platinum group component may be incorporated in the catalyst composition in any suitable manner such as coprecipitation or joint melirovanie, ion exchange or impregnation to create a uniformly deposited platinum component is enta on the material media. The preferred method of preparation of the catalyst involves the use of a soluble, decomposable compound of platinum for impregnation of the material medium. For example, this component can be added to the carrier by mixing the latter with an aqueous solution chloroplatinic acid. Other water-soluble compounds of platinum may be employed in impregnation solutions and include ammonium of chloroplatinate, bromopurine acid, platinum dichloride, hydrate tetrachloride platinum dichloride dichlorocarbanilide, dinitrodiphenylamine, etc. the Use of chloride of platinum compounds, for example chloroplatinic acid is preferable because it facilitates the inclusion and platinum component and at least a small amount of halide component in a single stage. Best results are obtained in the preferred impregnation stage, if the platinum compound gives a complex anions containing platinum in acidic aqueous solutions. Salt, or the like acid is also typically added to a solution impregnation, in order to further facilitate the occurrence of the halide component and distribution of the metallic component. In addition, usually prefer to impregnate the material of the carrier after annealing to minimize the risk of washout of valuable platinum compounds; however, in some cases, it may be a field is but to impregnate the material of the carrier, when he is in generowania condition.

Rhenium is a metal promoter and a catalyst. Platinum and rhenium final catalytic composite can be deposited on a refractory inorganic oxide carrier in any way, which leads to a preferably homogeneous distribution of these components, such as coprecipitation, joint melirovanie, joint extrusion, ion exchange or impregnation. Alternatively, a heterogeneous distribution, such as surface treatment, are included in the scope of claims of the present invention. The preferred method for the catalytic composite involves the use of a soluble decomposable compounds of the platinum and rhenium for impregnation of the heat-resistant inorganic oxide of relatively uniform manner. For example, platinum and rhenium can be added to the heat-resistant inorganic oxide, mixing the latter with an aqueous solution chloroplatinic acid and then with a solution of rhenium acid. Other water-soluble compounds or complexes of platinum and rhenium can be applied in the impregnation solutions. Typical decomposable compounds of rhenium, which can be used include ammonium perrhenate, perrenate sodium, perrenate potassium, potassium rhenium oxychloride, hexachloroiridate (IV) potassium, chloride, rhenium, dirani heptaoxide and such connection is of high value. The use of aqueous solution of rhenium acid is preferred impregnated with rhenium.

As mentioned previously, can be applied to any procedure for the application of platinum and rhenium on a heat-resistant inorganic oxide, while she gives a relatively uniform distribution of these components. Accordingly, when applied stage impregnation, platinum and rhenium can be applied using a separate impregnation solutions or, preferably, one solution impregnation, comprising decomposable compound of platinum and rhenium. Regardless of the application of one or various solutions impregnation, also add salt, nitric acid or a similar acid to the solution or solution impregnation, in order to further facilitate uniform distribution of the platinum and rhenium on a heat-resistant inorganic oxide. Additionally, usually prefer to impregnate the heat-resistant inorganic oxide after calcination, to minimize the risk of washout of valuable compounds of platinum and rhenium; however, in some cases, it may be useful to impregnate the heat-resistant inorganic oxide, when it is in generowania state, in the form of plastic masses or dried state. If there are two separate solution impregnation, for the deposition of platinum and rhenium on a heat-resistant inorganic oxide can be applied separate from the adiya's of oxidation and reduction between the use of the individual solutions impregnation. Additionally, the stage of adjustment of the content of Halogens can be applied between the use of the individual solutions impregnation. Such phase halogenation will facilitate the introduction of catalytic components and halogen in the heat-resistant inorganic oxide.

It may be desirable to apply the methods US 5482910 for use chelating agents to activate the platinum group and/or rhenium in the form of a dual component, or co-impregnation compounds of the platinum group and/or rhenium together with chelate complex of tin or without complex.

Regardless of its exact structure of the dispersion of platinum and rhenium should be sufficient that the content of platinum was, by element, from 0.01 to 2 wt.% the final catalytic composite. Additionally, should be sufficient rhenium to the content item, from 0.01 to 5 wt.% the final composite.

In addition to the catalytic components described above, the catalyst may be added other components. For example, a metal modifier selected from the group consisting of germanium, lead, indium, gallium, iridium, lanthanum, cerium, phosphorus, cobalt, Nickel, iron and mixtures thereof can be added to the catalyst.

An additional step in the method of the present invention includes halogenoalkane, which is preferably oxychloination, restored the second catalyst, described above. If this stage is desired, the catalyst was placed in a reactor and a gaseous stream containing halogen which is preferably chloride or chlorine is passed over the catalyst with a flow rate of 0.9 kg/h to 18,1 kg/h at a temperature of 300°-850°C for 10 minutes - 12 hours. The gaseous stream may be a stream of hydrogen chloride/chlorine, stream water/HCl, water flow/Cl2or a stream of chlorine. The purpose of this phase is to ensure optimal dispersion of the metals of group VIII and of the presence of some quantity of a halide, preferably chloride, in the final catalyst. Halogen content of the final catalyst should be such that it contains enough of halogen, by element, from 0.1 to 10 wt.% the final composite. Additionally, the catalytic composite may be subjected to pre-acarnania. Additional sulfur component may be incorporated into the catalyst by any known method.

EXAMPLE 1

Relatively many catalyst compositions include adding tin to modify the metal catalyst and an acid function. For example, in the case of spherical media, aluminum oxide, tin is added to the Sol of aluminum oxide which, because of the very high acidity, provides very good conditions for uniform distribution of the tin. When the media use the extrudate, tin can be implemented by adding the corresponding salts of tin (usually an aqueous solution of SnCl4) to a plastic mass prior to extrusion or impregnated extrudate. The addition of tin in the plastic mass usually leads to the deposition of tin due to the buffer action of the aluminum oxide in a solution with a pH of 4-5 and the formation of flakes tin containing agglomerated tin. Finely dispersed and almost homogeneous tin can be obtained by impregnation of the support with a solution of SnCl4but to prevent the tin deposition typically requires a high concentration of acid (10-12 wt.% HCl, for example), which makes this procedure impregnation undesirable from a commercial point of view, which includes loss of aluminum oxide and practical problems of corrosion. Initially it was found that only divalent tin Sn2+forms solutions are stable complex with EDTA at a temperature of 40°-90°C, whereas, on the contrary, tetravalent tin Sn4+deposited under any conditions. For comparison, the distribution of tin+4 on a carrier obtained by impregnation of tin in the presence of 12% HCl was not quite homogeneous with a high concentration on the surface in the analysis of scanning electron microscopy (SEM). In other words, tin+4 could not be dissolved with EDTA and cannot be properly distributed on the media kata is Isadora in the formation of sediment. To determine how tin+4 is included in the catalyst, it is impregnated with and without EDTA, but with a high concentration of HCl. The authors observed how uniformly tin+4 is included in the catalyst in an acidic environment. However, tin+4 concentrated near the surface and may not be uniformly distributed on the carrier. In fact, a rough calculation shows that nearly 66% tin+4 is located on the surface of the first half of 400 µm catalyst particles.

EXAMPLE 2

A comparative study performed with the method of the US 3994832 to characterize the final catalyst and to determine the profiles of tin on the catalyst particles, applying this method of processing media aluminum oxide EDTA to all impregnations metals.

The material of the catalyst carrier is treated with a chelating agent in accordance with the way US 3994832, dissolution of 6.17 grams of EDTA in 5 cubic centimeters of concentrated ammonium hydroxide and dilute solution up to 500 cubic centimeters of water. Approximately 500 cubic centimeters of spheres with a diameter of 1/16 inch gamma alumina is then immersed in the solution contained in a rotary dryer with steam jacket. Sphere is stirred solution within1/2hours at room temperature, after which direct the steam in the jacket of the dryer, and the solution evaporated to dryness in contact with paramashiva the feasible areas.

About 100 cubic centimeters spheres of aluminum oxide impregnated chelating agent impregnated with the General solution of chloride of divalent tin and chloroplatinic acid. The solution impregnation is prepared by dissolution of 0.37 grams of chloride pentahydrate divalent tin in 2 cubic centimeters of concentrated hydrochloric acid and 20 cubic centimeters of water. Then add 18,8 cubic centimeters chloroplatinic acid (10 milligrams of platinum per cubic centimeter) and the final solution was diluted to 100 cubic centimeters of water. Saturated chelating agent sphere stirred solution impregnation within1/2hours at room temperature in a rotary dryer with steam jacket. Then direct the steam in the jacket of the dryer, and the solution evaporated to dryness in contact with the mixed spheres of aluminum oxide. The dried spheres are then heated to 392°F in air and after1/2hours at the same temperature, heated up to 1000°F in air and maintained at 1000°F for 21/2hours. The sphere is then treated with a stream of substantially pure hydrogen for 1 hour at 1050°F to obtain the reduced forms of the catalyst. The final catalyst contains the 0.375 wt.% platinum and 0.25 wt.% tin, calculated on the metal.

Profiles of the content of tin in the catalyst particles is seraut using scanning electron microscopy (SEM). Data SEM show that in all cases tin impregnated way 832 patent, is not uniformly distributed on media tablets. Data SEM show that divalent tin is not homogeneous with high concentration on the surface of the first half of 400 µm catalyst particles.

EXAMPLE 3

Tin is added to the media in the forming stage, called extrusion, or preferably by joint extrusion. 2500 g of alumina powder (commercially available under the trade names Catapal b and/or Versal 250) placed in the mixer. The solution was prepared with the use of 60.8 g of nitric acid (67.5% of HNO3), 220 g of deionized water, and then adding 5,91 g tartrate tin and stirring the solution. The solution is added to the alumina powder in a blender and mix to obtain a plastic mass suitable for extrusion. Plastic mass ekstragiruyut through the plate matrix to form extrudate particles. The extrudate particles are dried in a conveyor kiln operating in the first zone at 370°C for 15 minutes and the second zone at 620°C for 30 minutes.

The extrudate particles are placed in a rotary evaporator and heated to 60°C. a Solution containing deionized water, hydrochloric acid, chloroplatinic acid and rhenium acid, add in a rotary evaporator and raise the the temperature value to 100°C, the medium is stirred for 5 hours. Then the impregnated carrier is heated to a temperature of 525°C in dry air. On reaching this temperature flow stream of air containing HCl and Cl2through the catalyst for 6 hours. Finally, the catalyst is reactivated by passing pure hydrogen over the catalyst at a temperature of 510°C for 2.5 hours.

Analysis of the catalyst showed that it contains 0.25 wt.% Pt and 0.25 wt.% Re and 0.1 wt.% Sn. Platinum, rhenium and tin are uniformly distributed along the carrier. This catalyst is designated as catalyst A.

EXAMPLE 4

Spherical carrier of aluminum oxide is prepared in a known manner droplets in oil, according to US 3929683. Tin is introduced into the carrier by mixing the precursor component tin with a Hydrosol of alumina and then heliroute Hydrosol. Then the catalyst particles are dried at 600°C for 2 hours.

This carrier is placed in a rotary evaporator and heated at 60°C. the Solution containing deionized water, hydrochloric acid, chloroplatinic acid and rhenium acid is added to a rotary evaporator and raise the temperature to 100°C., and the medium is stirred for 5 hours. Then the impregnated carrier is heated to a temperature of 525°C in dry air. On reaching this temperature flow stream of air containing HCl and Cl2through the catalyst for 6 hours. Finally, the catalyst is reactivated by passing pure hydrogen over the catalyst at a temperature of 510°C for 2.5 hours.

Analysis of the catalyst showed that it contains 0.25 wt.% Pt and 0.25 wt.% Re and 0.3 wt.% Sn. Platinum, rhenium and tin are uniformly distributed along the carrier. This catalyst is designated as catalyst C.

EXAMPLE 5

A solution of tin-EDTA is prepared by placing in a flask 300 g of deionized water, 1.42 g of ammonium hydroxide (concentration of 29.6% NH4OH) and 0.88 g of EDTA and stirring to dissolve the EDTA. Then 0,3392 g of tin chloride (SnCl2·2H2O) is added under stirring to the solution and heated to 60°C. for dissolution.

The second solution is produced by adding 300 g of deionized water 14,21 g of hydrochloric acid (37.6% of HCl) and 17,48 ml chloroplatinic acid (a solution of N2PtCl6with Pt concentration of 27.6 mg/ml). Then add 14,65 ml rhenium acid (solution HReO4with the concentration of Re is 32.8 mg/ml).

178,92 g of the extrudates of the gamma alumina is placed in a rotary evaporator and heated to 60°C. a Solution of tin-EDTA is added to the gamma alumina in a rotary evaporator and raise the temperature to 100°C. and the medium is stirred for 5 hours.

Then in a rotary evaporator add the second solution. The second solution is evaporated for 5 hours. Then the impregnated carrier is heated to a temperature of 525°C in dry air. what about reaching this temperature flow stream of air, containing HCl and Cl2through the catalyst for 6 hours. Finally, the catalyst is reactivated by passing pure hydrogen over the catalyst at a temperature of 510°C for 2.5 hours.

Analysis of the catalyst showed that it contains 0.25 wt.% Pt and 0.25 wt.% Re and 0.1 wt.% Sn. Platinum, rhenium and tin are uniformly distributed along the carrier. This catalyst is designated as catalyst C.

EXAMPLE 6

Check the ability of the catalysts a, b, C with a uniform and homogeneous distribution of metals for catalytic reforming pilot plant using naphtha as typical of the raw materials available in the Western United States, as follows. The process conditions selected to achieve the research octane number (RONC) 100. The pressure of 1379 KPa (200 lb/in2), the molar ratio of hydrogen to hydrocarbon of 1.5 hour and the volumetric rate of fluid 2.5 h-1. The lifetime of the catalyst is measured by the prevailing industrial standards using the barrel of raw material per cubic foot of catalyst, or BPCF, as shown in figure 1 and figure 2. First, figure 1 is a plot of output With5+ liquid products from the lifetime of the catalyst. Second, figure 2 is a plot of average temperature of the reactor block, the corresponding activity of the catalyst from the time life is utilizator. The results of this test are summarized in the table below, indicating equivalent to the initial activity and output at 12,5 BPCF.

Table
CatalystActivity, °CYield, wt.%
And515of 83.4
In52683,9
51484,3

The data indicate that the catalyst has better output and activity.

1. The catalyst is effective for reforming naphtha comprising particles of a refractory inorganic oxide carrier with distributed by media divalent tin, platinum group metal and rhenium, and optionally by halogen, characterized in that the tin is uniformly distributed in the media and the platinum group metal is uniformly distributed on the carrier; tin distributed on the carrier impregnated with the use of chelate complex of tin formed by the interaction of chelating agent representing the amino acid and the salt of divalent tin.

2. It is talization according to claim 1, in which a chelate is a chelating agent selected from the group consisting of ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-methyliminodiacetic acid, iminodiacetic acid, glycine, alanine, sarcosine, α-aminoadamantane acid, N,N-dimethylglycine, α,β-diaminopropionic, aspartate, glutamate, histidine and methionine.

3. The catalyst according to claims 1 and 2, in which the chelating agent is ethylenediaminetetraacetic acid.

4. The catalyst according to claims 1 and 2, which comprises 0.1 to 10 wt.% of halogen, calculated on an element.

5. The catalyst according to claims 1 and 2, in which the carrier is alumina.

6. The catalyst according to claims 1 and 2, in which the divalent tin is present in an amount of 0.01-5 wt.% in terms of the element.

7. The catalyst according to claims 1 and 2, in which the platinum group metal is platinum, which is present in an amount of 0.01-2 wt.% in terms of the element.

8. The catalyst according to claims 1 and 2, in which the rhenium is present in an amount of 0.05-5 wt.% in terms of the element.

9. The catalyst according to claim 2, in which the ratio of the chelating agent and compounds of divalent tin is from 1 to 8.

10. Way catalytic reforming of naphtha as feedstock, wherein the feedstock is in contact at reforming conditions with a catalyst according to claims 1 to 9, and the reforming conditions include temperature-600°C, pressure 100 kPa to 7 MPa (abs), clock volumetric liquid velocity of 0.1-20 h-1and the molar ratio of hydrogen to the raw material in the form of naphtha 1-20.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention refers to noble-metal catalyst, to method for making and application thereof. There is disclosed method for making noble-metal catalyst for hydrocarbon conversion, involving the stages as follows: a) preparation of the carrier containing zeolite, chosen from zeolites with medium and large pores and acid sites, at temperature within 423 to 1173 K and optional carrier modification; b) deposition of noble metal chosen from platinum, palladium, ruthenium, rhodium, iridium and their mixtures and combinations, by gas-phase deposition including evaporation of noble metal precursor chosen from β-diketonates and metallocenes, and interaction with the carrier, and c) heat treatment in oxidising or reducing environments. There is disclosed application of noble-metal catalyst produced by the method described above, in ring opening, isomerisation, alkylation, hydrocarbon reforming, dry reforming, hydrogenation and dehydrogenation, and preferentially, in ring opening of naphthenic molecules. Additionally, there is disclosed method for making medium diesel fuel distillate by introducing raw medium distillate into the reactor wherein it reacts at temperature 283-673 K and under pressure 10-200 bar with hydrogen with added noble-metal catalyst produced as described above until ring opening of naphthenes with two or more rings completed to produce isoparaffins, n-paraffins and mononaphthenes within medium distillate.

EFFECT: production of catalyst with improved selectivity for hydrocarbon conversion.

16 cl, 5 tbl, 20 ex

FIELD: chemistry.

SUBSTANCE: process proposed for catalytic reforming of petroleum naphtha in presence of hydrogenous gas is carried out in three stages in system of several series-connected reactors over platinic catalysts at increased pressure and temperature; on first stage cycloalkanes and alkanes aromatization is effected by contacting the hydrocarbon components with aluminium-platinum-rhenium catalyst at mass rate of crude material feed 4 to 8 hour-1, relative to catalyst weight, and temperature 460-480°C; on second stage arenes, cycloalkanes, and alkanes hydro-isomerisation is effected over zirconium-sulphate catalyst, containing platinum, at mass rate of feed minimum 8 hour-1, relative to catalyst weight, and temperature 150-200°C; and on third stage cycloalkanes aromatization is effected again over aluminium-platinum-rhenium catalyst also at mass rate of feed minimum 8 hour-1, relative to catalyst weight, and temperature 360-400°C; the reforming reactors system input pressure being 1.5 MPa, and the hydrogenous gas is fed to the system entrance in quantity, corresponding hydrogen to raw material molar proportion minimum 8.

EFFECT: production of high-octane component with lowered aromatic hydrocarbons level, and increase in manufacture efficiency of modern pollution-free fuel.

5 ex, 1 tbl

FIELD: CHEMISTRY.

SUBSTANCE: zeolite catalyst for process of conversion of straight-run gasoline to high-octane number component is described. The said catalyst contains high-silica zeolite with SiO2/Al2O3=60 and residual content of Na2О of 0.02 wt.% maximum, metal-modified, Pt, Ni, Zn or Fe metals being in nanopowder form. Content of the said metals in the catalyst is 1.5 wt.% maximum. Method to manufacture zeolite catalyst for conversion of straight-run gasoline to high-octane number component is described. The said method implies metal modification of zeolite, Pt, Ni, Zn or Fe metals being added to zeolite as nanopowders, produced by electric explosion of metal wire in argon, by dry pebble mixing in air at room temperature. Method to convert straight-run gasoline using the said catalyst is also described.

EFFECT: increase in catalyst activity and gasoline octane number, accompanied by increase in yield.

4 cl, 3 tbl, 4 ex

FIELD: petroleum processing and catalysts.

SUBSTANCE: invention relates to bismuth- and phosphorus-containing catalyst carriers, petroleum reforming catalysts prepared on these carriers, to methods for preparing both carriers and catalysts, and to petroleum reforming process using these catalysts. Described are catalyst carrier containing γ-alumina particles wherein bismuth and phosphorus are distributed essentially uniformly in catalytically efficient concentrations and a method for preparation thereof comprising (a) preparing solution containing bismuth precursor and solution containing phosphorus precursor; (b) preparing γ-alumina/alumina sol mixture; (c) mixing mixture of step (b) with solutions prepared in step (a) to produce carrier precursor containing essentially uniformly distributed phosphorus and bismuth; (d) molding; and (e) drying and calcination. Invention also describes petroleum reforming catalyst containing above-defined carrier and catalytically efficient amount of platinum, chlorine, and optionally rhenium; method of preparation thereof; and petroleum reforming process after hydrofining, which involves contacting petroleum with above-defined catalyst in presence of hydrogen at elevated temperature and pressure.

EFFECT: reduced catalyst coking velocity and achieved high stable activity of catalyst.

25 cl, 6 dwg, 4 tbl, 10 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: long gasoline fraction is divided into two streams, one of them being subjected to reforming process on industrial Pt-eryonite-containing catalyst SG-3P at 475-480°C, pressure 1.5-2.0 MPa, and volumetric feedstock flow rate 2.8-4.2 h-1, and the other being processed on platinum-rhenium catalyst KP-108 at 500-520°C, pressure 1.5-2.0 MPa, and volumetric feedstock flow rate 1.2-1.7 h-1. Before processing of the second stream, it is supplemented with 5-25% of the first-stream reforming product containing at least 8% of methylcyclopentane hydrocarbons.

EFFECT: simplified technology and increased octane number of reforming process.

2 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: straight-run gasoline fractions are subjected to preliminary dehydration followed by reforming of resulting product in a system consisting of several in series arranged reactors. Dehydration and reforming operations are conducted on industrial Pt-eryonite catalyst (SG-3P) pretreated for 10-12 h with nitrogen at 100-130°C and then with hydrogen or hydrogen-containing gas while gradually raising temperature from 120°C to 480°C for 12 h and subsequent ageing at 480°C during 2-4 h. Dehydration temperature is 410-450°C and temperature of reforming in all reforming reactors is 475-490°C.

EFFECT: increased yield and octane number of reforming product.

2 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: catalytic reforming carried out at temperature in the reforming zone entry not higher than 485°C is supplemented by sulfidizing accomplished by introducing sulfur-containing compounds by doses each constituting 0.001-0.02% sulfur of the weight of catalyst, intervals between doses being not less than 1/2 one dose introduction time and at summary amounts of added sulfur 0.02-0.2% sulfur of the weight of catalyst during additional sulfidizing period. Additional sulfidizing is performed one or several times over the service cycle lasting hundreds or thousands hours. One sulfur dose addition time ranges from 0.5 to 1.5 h.

EFFECT: increased yield of reforming catalysate.

3 cl, 1 tbl, 7 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: catalytic reforming of gasoline fractions is accomplished in a system constituted by several in series connected reactors at elevated pressure and hydrogen-containing gas circulation, wherein temperature of gas at first reactor inlet ranges from 380 to 470°C and in the other reactors 470-540°C. Reforming catalyst comprises alumina-supported platinum, fluorine, and optionally rhenium. In the first reactor, catalyst additionally contains 0.02 to 1.5% of fluorine.

EFFECT: increased yield and improved quality of product.

2 cl, 7 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: catalyst for reforming of benzene fractions contains carrier represents compound: xAl2O3·yZrO2·zTiO2 with molar values of coefficients: x=(9.2-9.7)·10-1; y=(8.1-49.0)·10-3; z=(0.63-6.3)·10-3 and also platinum, rhenium and/or iridium and chlorine with following weight ratio of components: platinum 0.1-1.0; rhenium and/or iridium 0.1-1.0; chlorine 0.5-2.5; carrier to 100.

EFFECT: high activity and stability at high volume speed of raw material feeding and low pressure.

2 cl, 1 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: catalyst contains silver, applied on profiled carrier with geometric configuration in form of hollow cylinder, in which ratio of length to outer diameter lies within interval from 0.3 to 2, and inner diameter constitutes up to 30% of outer diameter of said profiled carrier with assumption that when carrier contains more than one channel, inner diameter is considered to be the diameter of one channel with area of transverse section equal to the sum of areas of transverse sections of all channels. Described is method which includes obtaining profiled carrier with geometric configuration in form of hollow cylinder described above, and application of silver on profiled carrier. Described is method of obtaining ethylene oxide which includes: contacting under suitable epoxidation conditions of raw material flow, containing ethylene and oxygen, with described above catalyst. Also described is method of obtaining ethylene glycol, ethylene glycol ester, or 1,2-alkanolamine, which includes using ethylene oxide obtained by described above method and its conversion to ethylene glycol, ethylene glycol ester or 1,2-alaknolamine.

EFFECT: increase of initial activity and stable activity.

18 cl, 4 tbl, 4 ex, 3 dwg

FIELD: petroleum processing catalysts.

SUBSTANCE: catalyst containing platinum, rhenium, antimony, and chlorine on alumina are prepared by impregnation of carrier with aqueous solution of compounds of indicated elements, antimony being deposited as first or second component. Once antimony or platinum-antimony combination, or rhenium-antimony combination deposited, catalyst is dried at 130°C and then calcined in air flow at 500°C. Reduction of catalyst is performed at 300-600°C and pressure 0.1-4.0 MPa for 4 to 49 h. After deposition of antimony or two elements (platinum-antimony or rhenium-antimony) and drying-calcination procedures, second and third or only third element are deposited followed by drying and calcination. Final reduction of catalyst is accomplished in pilot plant reactor within circulating hydrogen medium at pressure 0.3-4.0 MPa and temperature up to 600°C for a period of time 12 to 48 h.

EFFECT: enhanced aromatization and isomerization activities of catalyst and also its stability.

2 cl, 1 tbl, 8 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides gasoline fraction reforming catalyst containing 0.1-0.5% platinum, 0.1-0.4% rhenium, halogen (chorine, 0.7-1.5%, or chorine and fluorine, 0.05-0.1%), and carrier: surface compound of dehydrated aluminum monosulfatozirconate of general formula Al2O3·[ZrO(SO4)]x with weight stoichiometric coefficient x = 0.45·10-2 - 9.7·10-2 and real density 3.3±0.01 g/cm3. Catalyst preparation process comprises preparation of carrier by mixing (i) aluminum hydroxide, from which iron and sodium impurities were washed out (to 0.02%) and which has pseudoboehemite structure, with (ii) aqueous solution of monosulfatozirconic acid HZrO(SO4)OH containing organic components (formic, acetic, oxalic, and citric acids) followed by drying, molding, and calcination. Carrier is treated in two steps: first at temperature no higher than and then at temperature not below 70°C.

EFFECT: enabled production of reforming gasolines with octane number not below 97 points (research method) with yield not less than 86% and increased activity and selectivity of catalyst.

4 cl, 2 tbl, 13 ex

FIELD: methods of preparation of catalysts for reforming of gasoline fractions in oil producing and petrochemical industries for production of high-octane motor fuels, aromatic hydrocarbons and commercial hydrogen.

SUBSTANCE: proposed method includes vacuum treatment of carrier, recirculation through aqueous solution of hydrochloric and acetic acids under vacuum, recirculation of impregnating solution; solutions of chloro-platinous and rhenium acids are introduced into impregnating solution at constant rate, after which solution is subjected to drying and calcination; treatment of carrier with impregnating solution is carried out at three stages: at first and second stages, temperature of circulating impregnating solution does not exceed 30°C and at third stage its temperature is not below 70°C.

EFFECT: enhanced activity, selectivity and stability of catalyst; reduced usage of metals; reduction of wastes and losses of platinum and rhenium.

10 cl, 2 dwg, 1 tbl, 8 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: catalytic reforming carried out at temperature in the reforming zone entry not higher than 485°C is supplemented by sulfidizing accomplished by introducing sulfur-containing compounds by doses each constituting 0.001-0.02% sulfur of the weight of catalyst, intervals between doses being not less than 1/2 one dose introduction time and at summary amounts of added sulfur 0.02-0.2% sulfur of the weight of catalyst during additional sulfidizing period. Additional sulfidizing is performed one or several times over the service cycle lasting hundreds or thousands hours. One sulfur dose addition time ranges from 0.5 to 1.5 h.

EFFECT: increased yield of reforming catalysate.

3 cl, 1 tbl, 7 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides reforming catalyst containing Pt and Re on oxide carrier, in particular Al2O3, wherein content of Na, Fe, and Ti oxides are limited to 5 (Na2O), 20 (Fe2O3), and 2000 ppm (TiO2) and Pt is present in catalyst in reduced metallic state and in the form of platinum chloride at Pt/PtCl2 molar ratio between 9:1 and 1:1. Contents of components, wt %: Pt 0.13-0.29, PtCl2 0.18-0.04, Re 0.26-0.56, and Al2O3 99.43-99.11. Preparation of catalyst comprises impregnation of alumina with common solution containing H2PtCl6, NH4ReO4, AcOH, and HCl followed by drying and calcination involving simultaneous reduction of 50-90% platinum within the temperature range 150-550оС, while temperature was raised from 160 to 280оС during 30-60 min, these calcination conditions resulting in creation of reductive atmosphere owing to fast decomposition of ammonium acetate formed during preparation of indicated common solution.

EFFECT: increased catalytic activity.

2 cl, 1 tbl, 3 ex

The invention relates to the refining and petrochemical industries

The invention relates to the field of petrochemical, refining, or rather to the catalysts used in the refining

The invention relates to the production of catalysts, in particular latinoreview catalyst for reforming of gasoline fractions

FIELD: chemistry.

SUBSTANCE: present invention refers to catalytic system and to the method of reduction of nitrogen oxides emissions using the said system. The described catalytic system for NOx reduction contains: the catalyst containing the metal oxide substrate, catalytic metal oxide which is gallium oxide or silver oxide or both of them and initiating metal chosen from the group consisting of silver, cobalt, molybdenum, wolfram, indium, bismuth and their mixtures, gas flow containing the organic reducing agent and sulfur-containing substance. The described catalytic system for NOx reduction contains: the catalyst consisting of (i) the metal oxide substrate, containing aluminium oxide, (ii) catalytic metal oxide which is gallium oxide or silver oxide or both of them in quantity 1-31 mole %; and (iii) initiating metal or their combination selected from the group consisting of silver, cobalt, molybdenum, wolfram, indium, bismuth, indium and wolfram, silver and cobalt, indium and molybdenum, indium and silver, bismuth and silver, bismuth and indium and molybdenum and indium in quantity 1-31 mole %, gas flow containing (A) water in quantity 1-15 mole %; (B) gaseous oxygen in quantity 1-15 mole %; and (C) organic reducing agent selected from the group consisting of alcanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates and their combinations; and sulfur oxide; where at the specified organic reducing agent and NOx are present in approximate molar ratio carbon to NOx from 0.5:1 to 24:1. The described method of NOx reducing includes the stages of gaseous mixture containing NOx, organic reducing agent and sulfur-containing substance inflow and of said gaseous mixture contact with specified catalyst. The described method of NOx reduction includes: inflow of gaseous mixture containing (A) NOx, (B) water in quantity 1-15 mole %; (C) oxygen in approximate quantity 1-15 mole %; (D) organic reducing agent selected from the group consisting of alcanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates and their combinations and (E) sulfur oxide; and contact of said gaseous mixture with catalyst described above and containing the specified components in the defined molar ratio.

EFFECT: improved action of the catalyst.

35 cl, 10 tbl, 84 ex

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