The method of preparation of the catalyst deposited on activated carbon, and the catalyst obtained in this way

 

(57) Abstract:

Group of inventions relates to catalysts, evenly distributed on the surface of activated carbon. The method of obtaining deposited on activated carbon catalyst includes mixing the liquid thermosetting resin as preobrazuemogo substance and forming the catalyst substance, curing preobrazuemogo substances if necessary, carbonation preobrazuemogo substances and activation of coal from getting deposited on activated carbon catalyst. Put evenly on activated carbon catalyst can be in the form of coatings on the basis of powder or solid products and has mounted thereon the electrodes for passing an electric current. Is achieved by simplifying and improving the efficiency of the method of producing the catalyst, and the improvement of the obtained catalyst. 2 C. and 10 C.p. f-crystals.

The invention relates to a method for producing a catalyst uniformly distributed on the basis of activated charcoal. Preferably the substance forming the metal catalyst, is mixed with a substance forming the activated carbon, which is then applied in the form of pokryto coating of activated carbon, containing dispersed therein a catalyst.

In many chemical reactions as catalysts for use metals, such as transition metals, including precious and base metals. Typically, the catalysts increase the rate of chemical reactions that leads to higher performance of the industrial process. Some catalysts are also used for the reaction for the desired route, i.e., in the presence of catalysts the formation of certain substances are more energetically favorable than the other.

Typically, the cost of the catalyst is high, therefore, it is necessary to reach the maximum use of a given amount of catalyst. This is carried out by maximizing the surface area of the catalyst, i.e., by increasing its dispersion. The catalysts used in the form of liquids or solids. Although solid catalysts can be used in the form of powders, typically, they are applied to the substrate with a large surface area. In these cases, the properties of bases are of great importance.

As the basis for metal catalysts, for example, noble metals, use activeelement in various petrochemical processes. Typically, these catalysts are obtained by dispersing fine particles of the noble metal on the pre-obtained activated carbon (method initial wetting).

Method initial wetting is the dispersion of the powder activated carbon in a solution of metal salt. When this powder activated carbon is impregnated with a solution. The powder is filtered, dried and heated to the temperature required for decomposition of the salt to the desired shape of the catalyst metal or metal oxide. Usually requires repetition of the procedure of impregnation to produce the desired amount of catalyst on charcoal. Surface properties of powder activated carbon has a very large impact on the resulting distribution of the metal catalyst. To obtain good distribution of the metal on charcoal should be carefully controlled oxygen content and pH of surface coal powder. The use of multiple stages in this way leads to a very high value put on activated carbon catalyst.

Another way to get deposited on activated carbon catalysts Saket coal. In this way, the surface chemistry of coal affects the choice of forming the catalyst substances. For most of the required catalysts often impossible to find the original substance. As examples of metal catalysts that cannot easily precipitated from the vapor can cause alkaline earth metals, chromium, manganese, copper, etc. as compounds of these metals have a low vapor pressure. Other metals, such as platinum, palladium and cobalt, it is difficult to check due to the fact that volatile compounds of these metals is rapidly decomposed in the vapor phase. In addition, many of the available volatile compounds are highly toxic. Finally, this method requires sophisticated, expensive equipment for deposition.

In U.S. patent 3886093 described a method of producing catalyst deposited on activated carbon, comprising the combination of preobrazuemogo substances forming the catalyst substance in a soluble form, carbonation preobrazuemogo substances and activation of coal from getting deposited on activated carbon catalyst, and thus obtained catalyst powder of activated charcoal coated with a catalytic substance. The specified method Aligator substance in a soluble form (solution, containing a salt of the transition metal), carbonation preobrazuemogo substances and activation of coal from getting deposited on activated carbon catalyst. The result is a powder of activated carbon containing active metal centers.

The disadvantages of this method is the need to work with solutions, precipitation and drying. The disadvantage of the obtained catalyst is that it has the form of a powder, which, as a rule, difficult to use and requires further drawing it on the canvas. In addition, this catalyst is unsuitable in cases when the required heating with an electric current.

The objective of the invention is to provide a simple and economical method of producing catalyst on charcoal, evenly on it and distributed with the desired shape, and the catalyst obtained in this way.

This task is solved in that in the method of producing catalyst deposited on activated carbon, comprising the combination of preobrazuemogo substances forming the catalyst substance in a soluble form, carbonation preobrazuemogo substances and activation of coal polucau thermosetting resin, the catalyst is distributed on the particles of activated carbon uniformly and applied in the form of a coating on an inorganic basis or molded into a monolithic product.

As forming the catalyst substance is possible to use a transition metal, alkali metal, alkaline earth metal or combinations thereof.

The metal catalyst may be selected from the group comprising Pt, Pd, Rh, Ag, Au, Fe, Co, Cr, Ni, Mn, Cu, Li, Mg, Ba or combinations thereof, preferably Pt.

As forming the catalyst substance can be used chloroplatinate ammonium.

Combined preobrazuyas substance and forming the catalyst material can be applied in the form of a coating on an inorganic basis.

As inorganic bases can be used honeycomb. The advantage of the framework in the form of honeycombs is that it is a ready-reactor for carrying out a continuous process stream.

The inorganic base may be a ceramic, glass, glass-ceramic, metal or combinations thereof. In particular, the inorganic base can be made from cordierite.

As thermosetting resin can be used phenolic resin.

After ), and/or after the stage of combining preobrazuem substance and forming the catalyst substance can be formed into a monolithic product.

This task is solved in that the catalyst deposited on activated carbon and is obtained by combining preobrazuemogo substances forming the catalyst substance in a soluble form, carbonization preobrazuemogo substances and activation of coal from getting deposited on activated carbon catalyst, as preobrazuemogo substance use liquid thermosetting resin, the catalyst is distributed on the particles of activated carbon uniformly and applied in the form of a coating on an inorganic basis or molded into a monolithic product.

The catalyst may have mounted thereon the electrodes to pass through it of an electric current.

The catalytic reactor in the form of honeycombs can also be equipped with electrodes and heat to achieve a specific temperature required for this reaction.

In the General case the method comprises contacting forming a catalyst substance forming activated carbon substance with subsequent carbonization preobrazuemogo substances and

This one-step method has several advantages over more traditional methods of obtaining deposited on charcoal catalysts. For example, the catalyst is a finely dispersed metal on highly porous activated carbon and is obtained in one stage, i.e. by pre-contact forming the catalyst substance with Preobrazhensk substance. Single-stage process proposed by the invention is more economical than the known methods, because there is no stage or stage of deposition of the catalyst on charcoal.

Activated carbon and the catalyst may be in the form of fine powder, granules or solid products. The carbon can be deposited on the particles, flakes, plates inorganic substances such as clay, mica, or any other inorganic powder or inorganic fibers, such as alumina, mullite, glass, glass ceramics, SiC, Si3N4and so the Coal can be applied on a molded base, for example in the form of a pipe, foam or mesh materials. The preferred form of carbon products or bases coated with coal is a multi-cell structure, such as honeycomb.

You are the synthesis, the contamination, such as automobile exhaust gases, etc.

Forming a catalyst substance, as a rule, is a combination of a catalytically active metal, such as organic or inorganic salts, which upon heating decomposes to metal or metal oxide. As the inorganic compounds can be, for example, oxides, salts such as chlorides, nitrates, carbonates, sulfates, ammonium complex salt, etc. as organic compounds can be used, for example, ORGANOMETALLIC compounds of the corresponding type.

Typical catalytically active metals are transition, alkali, alkaline earth metals or combinations thereof. Preferably the catalytically active metals are Pt, Pd, Rh, Ag, Au, Fe, Co, Cr, Ni, Mn, Cu, Li, Mg, Ba, Mo, Ru, Os, Ir or combinations thereof. As only some possible examples of catalytically active metals, non-exhaustive list can be the oxides of V, Co, Cu, Ni or Fe for the conversion of oxides of nitrogen and sulfur, noble metals, Cu, Zn, Co, Ni, Mn, Cr, Fe for various chemical reactions, etc.

One particularly effectively used catalyst is platinum. Usually in this case the m ammonium (NH4)2PtCl4.

Under Preobrazhensk understand the substance containing carbon, which is converted by heating coal with a continuous structure. Preobrazhensk can be any liquid or turn into a liquid carbon-containing substance. As examples of suitable preobrazuemyh substances can result in a thermoplastic resin (for example, polyvinylidene, polyvinyl chloride, polyvinyl alcohol, etc.,), solutions of sugar, furfuryl alcohol, and coal tar pitch.

Preferred preobrazilsya substances with low viscosity (e.g., thermoset resins), especially if preobrazuyas substance and the catalyst are in contact with the base, because the low viscosity promotes deeper penetration preobrazuemogo substances into the porous base. The most preferred phenolic resins because of their low viscosity, high carbon content, high degree of crosslinking during curing in comparison with other Preobrazhenski substances, and low rates. Among particularly well suited for this purpose resins can be called phenol-rezol (N 43290) and plife manufactured by Occidental Chemical Co., Niagara Falls, N. Y.

Preobrazuyas liquid ispolzuya substances.

Preobrazuyas substance and forming the catalyst substance is combined by mixing them with each other with formation of a solution or emulsion.

After mixing preobrazuemogo and forming the catalyst substances subjected to the treatment for carbonization preobrazuemogo matter and activated carbon, if necessary, activate the catalyst, and transfer of activated carbon in the desired physical form.

In accordance with the preferred method of implementation interact preobrazuemogo substance and forming the catalyst substance with the appropriate inorganic porous monolithic Foundation with the formation on the substrate surface coverage of preobrazuemogo substance and the catalyst.

The base has an external surface with leaving inside pores. The coating penetrates into and distributed in the pores of the support, coating their surface.

The most preferred form a solid Foundation has the ability to pass a flow of the working fluid, i.e., has a system of connecting with each other then, passing from outside to inside, and/or channels passing from one end of the monolith to the other for the passage through them of the fluid flow, vhodyashih durability and to withstand heat treatment at temperatures necessary for formation of a coating of activated charcoal.

It is desirable that the total content of the open pores in the base was at least 10%, preferably more than 25%, most preferably more than 40%. In most cases, the desired degree of porosity of 45% to 55%. Preferably, the pores in the base material formed of an open pore system, in which pores are connected and/or intersect with other pores with the formation of three-dimensional porous systems within the bed.

Among suitable for use as the basis of porous materials include ceramics, glass ceramics, glass and combinations thereof. Under these combinations involve physical or chemical combinations, for example mixtures, compounds, or composites.

Some materials, especially suitable for use in this invention (although it is clear that the invention is not restricted by them), made of cordierite, mullite, clay, talc, zircon, Zirconia, zirconates, zirconium spinel, magnesium silicates, spinel, alumina, silica, silicates, borides, silicates, such as porcelain, lithium aluminosilicates, alimokrane oxides, feldspar, mnia or mixtures thereof. It is preferable to use cordierite, as its coefficient of thermal expansion comparable to the coefficient of thermal expansion of the coal, which increases the strength of the element that contains activated charcoal. Some typical ceramic materials for the foundations described in the literature (U.S. Pat. USA N 4127961 and N 3885977). Suitable metallic materials are any metals or alloys or intermetallic compounds, which provide reliable performance patterns, it is desirable that they do not soften at temperatures up to 600oC. the Most suitable alloys for the most part consisting of a metal of the iron group (i.e., Fe, Ni and Co), as containing carbon (for example, of steel, especially stainless steel or high temperature), and not containing carbon. The most typical of the alloys of the latter type for high temperature use are alloys consisting only of a metal of the iron group (preferably iron) and aluminum. Especially preferred Fe, Al and Cr. For example, particularly suitable powders Fe5-20Al-5-40Cr, and Fe7-10Al10-20Cr with other possible additives. Some typical compositions of metal powders to form the basis described in the literature (U.S. Pat. USA N 3885977 and 4992233. is composed of metal powders of Fe and Al with possible addition of Sn, Cu and Cr. In Europe. application N 0488716 described porous agglomerated elements containing 5-40 wt.% Cr, 2-30 wt.% Al, 0-5 wt.% special metal, 0-4 wt.% the additive oxide of rare earth metal, the rest is metal group iron and inevitable impurities, with the preferred metal of the iron group is iron. If the oxide of rare earth metal, special metal is at least one from a group comprising Y, lanthanides, Zr, Hf, Ti, Si, alkaline earth metals, B, Cu and Sn. In the absence of oxide of rare earth metal special metal is at least one from a group comprising Y, lanthanides, Zr, Hf, Ti, Si and B with possible addition of alkaline earth metals, Cu and Sn.

The base preferably is a cell or a matrix of thin walls forming a multitude of open cells extending from one end of the honeycomb to the other.

As examples of honeycombs obtained by the proposed method, while not limiting the scope of invention, it is possible to specify a cell with about 172 cells/cm2(1100 cells/inch2), about 94 cells/cm2(600 cells/inch2), about 62 cells/cm2(400 cells/inch2), about 47 cells/cm2(300 cells/inch2/cm2(16 cells/inch2), or about 1.5 cells/cm2(9 cells/inch2).

The thickness of the walls (partitions) in most cases is usually from 0.1 to 1.3 mm (4 to 50 miles), although the invention is not limited to these intervals. External dimensions and shape of the product depend on the application and is not limited by the above parameters. For example, can be used, and other combinations of density and cell wall thickness.

As the basis for the application of activated carbon is the most suitable honeycomb cordierite.

Communication carried out by any method that ensures close contact preobrazuemogo substance and the catalyst with an inorganic base. As examples of such methods can lead dive bases in solution preobrazuemogo substance and the catalyst (or in the corresponding liquid) or direct plating solution preobrazuemogo substance and the catalyst (or liquid) on the canvas.

Possible number of coal (and catalyst) formed on the basis depends on the number preobrazuemogo substances (as well as forming the catalyst substance) held by the Foundation. This quantity can be ovalization substance) with intermediate drying basics after each contact. In addition, the number of retained basis preobrazuemogo substances is possible in the case of the porous framework be adjusted by simply changing the total porosity of the base (for example, with the increase in porosity increases the number of retained basis preobrazuemogo substances (and forming the catalyst substance) and, consequently, the number of produced coal and metal catalyst)).

Next, the base with Preobrazhensk substance (and catalyst) is subjected to heat treatment to convert preobrazuemogo substances in a continuous layer of coal (carbonization). Then received at the base with a layer of coal (and catalyst) is subjected to heat treatment with the implementation of the activated coal and receiving structures containing activated carbon with dispersed therein a catalyst.

If Preobrazhensk substance is a thermosetting resin, it utverjdayut before activating, and often before carbonization. Curing is usually carried out by heating the substrate with a coating to a temperature of from 100 to 200oC for from 0.5 to 5.0 hours typically, curing is carried out in air at atmospheric pressure. Some of preobrazuemyh substances (e.g. who, islanova catalyst, at room temperature.

Carbonation is a thermal decomposition of carbon-containing substances, which are substances with low molecular weight (for example, carbon dioxide, water and so on) and forms a hardened mass of coal with a residual porosity.

This conversion or carbonization of the cured preobrazuemogo substances are usually by heating the basics to a temperature of 600-1000oC for 1-10 hours in a reducing or inert atmosphere (nitrogen, argon, and so on).

After curing and carbonization preobrazuemogo substances the base surface of the obtained structure is entirely covered with a layer without any gaps coal containing dispersed catalyst. This carbon coating is fixed in the pores of the substrate and therefore is firmly connected with it. The outer surface of the carbon coating is a continuous coating of carbon-carbon bonds.

As noted above, if the basis for a system of interpenetrating then, the inside is formed of interconnected carbon surface, which allows to obtain a carbon coating with greater adhesion. Continuous coal-ion capacity despite the relatively low content of carbon, and high strength and high temperature operation. Can be obtained structures containing not more than 50%, often not more than 30% of coal from the total mass of the base and the coal.

Activation is carried out for a substantial increase in the volume and diameter of micropores formed during carbonization and the formation of new pores. Activation creates a large surface area, which in turn gives the structure a high adsorption capacity. The activation is carried out by known methods, for example by treatment patterns oxidants, such as steam, carbon dioxide, chloride of a metal (e.g. zinc chloride), phosphoric acid or potassium sulfide at high temperatures (for example from 600 to 1000oC).

In the above structure, the layer of activated carbon has a high resistance to chipping and flaking, has high strength and temperature resistance compared to carbon coatings obtained by immersing the base in a suspension of activated carbon in a binder. In addition, these charcoal design exhibit higher adsorption properties than the design with extruded coal or structure with a floor, manufacture the integration of coal, perform joint processing preobrazuemogo substance and forming the catalyst substance with the formation of a powder, beads, granules or solid products. In this case, the carbon is applied on the porous inorganic base. However, treatment of the catalyst, deposited on charcoal, similar to the processing bases coated with activated carbon. For example, forming the catalyst substance is mixed with Preobrazhensk substance in sufficient quantity to obtain the specific content of the metal catalyst (typically from 0.1 to 10 wt.%). Then preobrazuyas substance several times subjected to heat treatment for curing, if necessary, preobrazuemogo substances with subsequent transformation into a layer of continuous carbon coating by carbonization.

The resulting catalyst on charcoal gives the form of powder, beads, granules or solid products at the stage of curing or carbonization. Powders can be obtained by grinding the cured or carbonized material or by spray drying of a solution of the substances that make up the coal and catalyst, at a temperature of curing preobrazuemogo substances (if conduct curing). Then begin by casting preobrazuemogo and forming the catalyst substances in the form of careful curing, the carbonization and activation form. Beads and granules can be obtained from the monolith using a grinding or casting solution or emulsion of the original substances in small forms.

Carbonized catalyst in the carbon-containing material to activate one of the above methods to obtain large surface area of the coal and create streaming access of reagents to the surface of a metal catalyst.

The catalyst deposited on activated carbon in powder form, granules, beads or solid coal products, has a number of advantages, characteristic of the coated activated carbon framework, namely the high dispersion of the catalyst, high adsorption capacity, large pore volume and a large area of the active surface. The special advantage that distinguishes this method of preparation of the catalyst on charcoal from other methods, is its efficiency, subject to obtaining highly dispersed catalysts in a one-step process. Other methods, such as the method of initial wetting or vapor deposition, require special attention to surface chemistry of coal and repeated application of the catalyst, and therefore are extremely dmer phenolic resin, with a platinum compound in the form of a salt, such as (NH4)2PtCl4in amount, for example, from 0.5 to 5 wt.% metal Pt from the amount of coal produced after activation, and apply the mixture on the basis of, for example, cordierite in the form of a honeycomb. It is established that the size of crystallites of platinum and the degree of its dispersion on charcoal can be adjusted by changing the temperature of carbonization and activation, as can be seen from the examples below.

In another most preferred embodiment, the mixed compounds of transition metals such as Fe, Cu, Ni, Cr in the form of soluble salts such as chlorides, with Preobrazhensk substance, for example a phenolic resin, and is applied as a coating on the basis of, for example honeycomb cordierite.

During operations carbonization and activation conditions of firing various metal compounds are transformed into metals or oxides of metals according to their thermodynamic equilibrium. Under restoration conditions during carbonization, only metals with high oxidation potentials, such as chromium, to form oxides, metals with low oxidation potentials are highlighted in the metallic form. In a mild oxidative conditions the asset is IDA, whereas metals with weak potentials of oxidation, such as platinum and copper, are obtained in the form of metal crystallites. The invention is not limited to catalysts, which are formed directly on the stages of carbonization and activation. The oxidation state and chemical form of the metal catalyst can be changed by appropriate processing after the stage of activation. The metal oxides can be restored by heat treatment in the presence of hydrogen without any violation of the structure of activated carbon. Metals can be converted into oxides without appreciable oxidation of the coal media exposure in air at a temperature below 400oC. If necessary, obtain a different chemical forms of the catalyst, such as sulfide, it is possible to use the heat treatment in the atmosphere containing H2S, for the conversion of metals from oxides of metals in the fine particles of catalyst metal sulfide without any noticeable effect on the structure of coal.

The carbonization can be carried out in an inert or reducing atmosphere at temperatures from 500 to 1000oC for 1-10 hours, preferably from 700 to 900oC. Activation is performed at a tempo of the original substances.

In another embodiment, the base with a coating of activated carbon and catalyst can be installed electrodes. Preferably this is carried out by the method described in EP-A-0684071.

The preferred basis is a basis in the form of a honeycomb, the most preferred honeycomb cordierite.

In this embodiment used the conductive properties of the coal. When electric current passes through the coal latter is heated to a certain temperature-dependent resistance element and the applied voltage. The design element can be used such resistance values and voltage, which allow heating element to the desired temperature.

Such elements, provided with electrical contacts for heating to the required temperature, coated, containing uniformly dispersed catalyst may serve as reactors continuous action for certain reactions. For this reaction to prepare the basis of activated carbon containing the desired catalyst dispersed in charcoal. Such an element having the electrodes are heated to the optimum reaction temperature. Reagents miss soprovojdavshie means is positioned so that so that they can conduct electric current through the structure or, in particular, through the coal with a uniform heating of coal. The actual location of the conductive means depends on the type of device and the shape of the structure, and the invention is not limited to any specific types of conductive means, if only the electric current caused uniform heating patterns without local overheating.

Typically, conductive means should have a resistivity of at least about 0.001 OSM, but it usually takes at least 0,01 MSM, most typically not less than 0.1 Omsm. To solve problems of the present invention, the specific resistance can be from 0.10 to 25 ASM.

For this invention the resistivity of the product is described by the formula:

< / BR>
where is the resistivity, Ohm cm

R - resistance, Ohm,

A - the area of the conductive surface, cm2,

L is the distance between the two running surfaces, see

Requirements for voltage and current vary depending on the application, and the resistivity can be changed in accordance with this equation. For example, if you want to heat the product is and must be chosen so that so nowhere in the product was not local overheating above 350oC. If the element is heated in an inert or directionspanel atmosphere, for example nitrogen, the voltage and current must be such that nowhere in the item no local overheating above 1000oC.

Some of the most preferred conductive materials are metals such as copper, silver, aluminum, zinc, Nickel, lead, tin and their alloys, while preferred is copper because of its high conductivity and minimum resistance, as well as cheapness.

Conductive device, as a rule, is a strip of conductive material or electrode, or a coating of conductive material on a monolithic structure. In this invention, the term "conductive coating" refers to the coating on the structure of activated carbon and, therefore, different from the carbon coating of the structure.

When the electrode can be set by the clamping device, such as a spring. In addition, you can install on the structure of a strip of electrically conductive metal using a conductive adhesive such as silver-containing epoxides, such as E-p is the initial resistance, that allows to avoid local overheating.

One particularly viable option is to install metal conductors on the opposite surface of the product. Under imply the opposite surfaces in accordance with the shape of the product so that the transmission between the electric current leads to uniform heating of coal.

The preferred form of the monolith are cells, such as cells, covered with coal obtained from preobrazuemogo substances, of rectangular form with a conductive coating on two opposite sides.

Conductive coatings are within the monolithic structure and cover the walls of the cells into at some length. The penetration depth of coverage may be different, but it should be sufficient for uniform distribution of current passing through the product.

Other possible forms of products and variants coatings can be honeycomb rectangular or cylindrical profile with a conductive coating in the form of stripes along the closed sides, or in the form of rings around the sides at the open ends or open ends, or one contact is on the whole external surface of the nurses, but do not limit the scope of the invention. They depend on the application and factors such as cost, size, temperature, etc. it is Necessary to provide low resistance and high mechanical strength of the structure.

The conductive coating can be applied to any suitable known method, for example by connecting ratowanie, arc spraying, flame spraying, plasma spraying, ultrasonic welding, nakruchivaniem etc.

The invention is not limited to any coating thickness. The thickness is determined by the nature of the covered surface and the metal used for coating. The coating should have a thickness sufficient to ensure a low resistance passing current, and to be durable, i.e., resistant to oxidation and corrosion, and have good mechanical strength. However, the thickness of the coating should not be so large that it peeled off or was crumbling, and it should not be prohibitively expensive.

One of the most acceptable ways of applying electrically conductive coating on the first stage consists of giving a smooth surface, coated with activated carbon. This is usually carried out by grinding covered activated carbon surface is a smooth coating of activated carbon is applied conductive coating. Described below are some practical methods of applying the conductive coating.

One method consists in preparing a mixture for coating consisting of metallic copper powder and a glass Frit, a mass ratio of copper and Frits is from 10:1 to 2:1, usually from 6:1 to 2: 1. For example, a typical composition of copper and Frits have a composition of 70 wt.% copper and 30 wt.% Frit or 84 wt.% copper and 16 wt.% the Frits. Then the coating is subjected to firing.

An acceptable method is also arc spraying. It is produced by passing two metal wires through the feeding device and the gun arc spraying. Electric current creates an electric arc between the wires. The arc creates a zone of high heat, which melted wires, and a jet of compressed air napisy molten metal on an appropriate basis with the formation of a solid coating.

Another method is the preparation of solder, such as silver, Nickel or other suitable electrically conductive coating, and applying the above described methods, including ultrasonic welding.

The invention is illustrated below by examples, not ogran

Platinum salt (NH4)2PtCl4manufactured by Englehard specialty chemicals Newark, N. J., was dissolved in deionized water to obtain a 33% aqueous solution. As the phenolic resin used phenol-rezol resin (N 43290) manufactured by Occidental Chemical Co., Niagara Falls, N. Y., About 7.5 g of the solution of a platinum salt was added under stirring phenolic resin. Then the mixture was applied on the basis of porous cordierite honeycomb containing 62 cells/cm2(400 cells/inch2) immersion for 1 minute, followed by purification of the channels from the excess resin by blowing compressed air. Samples were heated from room temperature to a temperature of about 150oC at a rate of 25oC per hour for drying and curing of the resin. Covered utverzhdenii resin cellular basis for further heated in nitrogen atmosphere at 500oC at 150oC per hour and held at this temperature for about 1 hour. Then the design was heated to 900oC and kept for 6 hours for carbonizing the resin. Next cell element coated with carbonized resin, activated with steam at 800oC for 1 hour under nitrogen content in about 30 mole fractions of steam. Activated in this way the sample was cooled to room temperature-programmed desorption (TPD) and the method of x-ray diffraction. Method TPD shows that the crystallite size of Pt is about 100 . By x-ray diffraction determined that the platinum crystallites do not contain or contain little PtO or PtO2. It is assumed that such a well-dispersed platinum can be a highly active catalyst for various chemical reactions.

Temperature-programmed reduction (TPR) and temperature programmed desorption (TPD) is a well - known methods for determining the dispersion of the catalyst. The sample containing the catalyst of the coal is first heated in argon to 300oC with the speed of blowing argon 30 cm3/min to remove any adsorbed particles. The sample was then heated to 380oC in a stream of hydrogen (30 cm3/min) for recovery of metals. Next, the sample is cooled to room temperature and passed over it a stream of hydrogen for its adsorption. Adsorbed hydrogen is desorbed by heating the sample and measure the amount of hydrogen produced at different temperatures. A measured quantity of hydrogen used to calculate the area of the active surface of the metal platinum, and from this value and the known amount of catalyst in the sample expect dispersement by electron transmission microscopy (ETM). The average crystallite size calculated from the results of TPR, correlates well with the crystallite size measured using ETM. ETM is a method of electronic microscopy, allowing you to see the details when the degree of increase of over 1 million that enables direct measurement of the dispersed particles.

Example 2.

Repeated operations of example 1, but the activation was carried out in CO2if 900oC for 2 hours. From the results of TPV established that the size of crystallites of platinum is about 170 . By x-ray diffraction revealed the presence of Pt crystallites, not containing or containing little PtO or PtO2preferably, as catalytically active platinum in the form of metal rather than oxide. The results show that platinum is obtained in the form of metal, is preferable for catalysis.

Example 3.

Repeated operations of example 2, but the activation of coal was carried out at 700oC for 2 hours in CO2. The size of the crystallites of platinum in this sample was about 25 . In this case, the dispersion is much higher than in examples 1 and 2.

The above examples clearly illustrate the possibility of regulating the dispersion of the square is persnaly 20 catalysts, the resulting embryonic method.

Example 4.

Received solutions of the chlorides of iron, Nickel, copper and chromium containing about 2 parts of a suitable metal 5 to 10 parts of water. The solution of metal chloride was mixed with the same volume of phenolic resin, which produces about 98 parts of activated charcoal. The resulting mixture of metal chloride and resin was utverjdali at 150oC and carbonizable at 700-900oC. Samples activated in CO2if 900oC for 1 hour. By x-ray diffraction found that carbonated mixture of resins and salts of Fe, Ni and Cu containing metal of zero oxidation degree (no metal salts or compounds formed during carbonization). Chromium forms in coal phase Cr2O3not containing nonvalence metal. Carbonized at 900oC samples activated for about 1.5 hours at 900oC and examined by x-ray diffraction. Chromium and iron were formed oxides, and Nickel were present in the form of NiO and metallic Nickel. Copper was present only in the form of metal. The results show that the chemical state of the metal in the activated carbon depends on processing conditions and therefore the via the process, you can obtain a catalyst in metallic or oxidized form.

One of the many areas of use in the present invention products is the decomposition of ozone. It is established that the ozone produced during the operation of laser printers and photocopiers, creates in offices concentrations hazardous to human health. Adsorption and decomposition of ozone, followed by separation of oxygen in the environment using a layer of activated charcoal. The problem with using a layer of activated charcoal is that cooling of the internal working parts of printers and copiers fan must overcome a large resistance caused by the pressure drop, when pumping sufficient for cooling air quantity. The solution to this problem is the use of activated carbon in a honeycomb structure. Disadvantages molded activated carbon discussed above. Products proposed in this invention, have high performance characteristics when the decomposition of ozone.

The following examples show that the proposed cellular elements containing catalyst activated carbon is well applicable for times>(200 cells/inch2) with cells of square cross section with dimensions of 0.3 mm (12 miles) covered profenofos phenolic resin manufactured by Occidental Chemical Co., Niagara Falls, N. Y. Then the resin was utverjdali, carbonizable in nitrogen at 900oC and activated in CO2at the same temperature. The resulting coal had a surface area of about 753 m2/g measured by the BET method by adsorption of N2. Then in cell element with a diameter of 2.54 cm (1 inch) and a length of 2.54 cm (1 inch) determined the adsorption of ozone at a flow rate of air 15,24 m/min (50 ft/min and ozone concentration of 0.60 million hours (ppm) of ozone. Found that adsorption capacity was 92%. Content of the coal sample was 21 wt.% of the mass of the cell element.

Example 6.

A sample of cordierite containing about 59 cells/cm2(380 cells/inch2) with cells of triangular section was coated, was utverjdali it was carbonizable and activated as in example 5. This sample was tested for the adsorption of ozone in the air stream velocity of about 50 ft/min and ozone concentration approximately 0.63 million hours (ppm). In this case, the adsorption capacity was approximately 86%. Content of the coal sample to 19.8%.

High adsorption methods for coal. As a rule, charcoal on the basis of the applied catalysts to increase the adsorption capacity and duration of service.

Below are examples of the application on the cellular elements of the various oxides of transition metals as catalysts, using single-stage method proposed in this invention.

Example 7.

Dissolve 5.6 g Mn(NO3)24H2O in 30 g of distilled water. Then this solution was added to 187,5 g profenofos phenolic resin. The mixture of the resin and the solution was applied to the cell element of cordierite. The resin was utverjdali and carbonizable at 900oC in nitrogen and activated at 900oC for 2 hours to obtain cell element with the applied in situ catalyst. Cell element cordierite contained 62 cells/cm2(400 cells/inch2) with a wall thickness of 0.15 mm (6 miles). Tests on the adsorption of ozone was carried out at the ozone in the air about 1 million hours (mass.), when the air speed of 120 ft/min 36 m/min, the Efficiency of decomposition of ozone was 100%.

Example 8.

Repeated operation of example 7 to a solution of 8 g of CuSO435 r water. The solution was added to 250 g of the solution of phenolic resin as in example 7. Honeycomb is listed and activated, as before, obtaining cell element containing precipitated CuO. In the test conditions, similar to that shown in example 7, the efficiency of decomposition of ozone was 100%.

Example 9.

Repeated operation of example 8 with MnSO4instead of CuSO4obtaining MnO deposited on the cell element. In the test conditions, similar to that shown in example 7, the efficiency of decomposition of ozone was 100%.

Example 10. A solution of 8.8 g of Fe(NO3)39H2O and 5.6 g of Mn(NO3)24H2O was added to 187,5 g profenofos phenolic resin. This solution was coated cell element made of cordierite, utverjdali, carbonizable and activated item as described previously, when 900oC. In the test conditions, similar to that shown in example 7, the efficiency of decomposition of ozone was 100%.

Example 11.

In some applications of the catalysts obtained in the present invention may take the coal in the form of powder, granules, capsules or solid products. The following example illustrates the method of obtaining a Nickel catalyst deposited on a carbon powder.

Samples of Nickel deposited on the powder and the Lee 1.85 g NiCl26H2O in 5 ml of water and add this solution to 100 ml of profenofos phenolic resin. The samples were utverjdali at 150oC, carbonizable at 600-800oC. Then the samples were activated by CO2when 700-900oC. Each of the samples obtained in the form of a granular powder by grinding utverzhdenii resin to a particle size less than 100 mesh before carbonization.

One part utverzhdenii resin was carbonizable at 900oC for 6 hours and were examined by the method ETM. The average particle size of the Nickel on the microphotographs amounted to 500 . Using x-ray diffraction determined that Nickel is present in the form of metallic Nickel.

Another sample containing Nickel utverzhdenii resin was carbonizable at 700oC for 6 hours. This sample had an average particle size of 250-350 and, in addition, significantly crystallized substrate coal. The particle size of the Nickel dropped as carbonization and activation were carried out in milder conditions, which shows the ability to control the particle size by optimizing the heat treatment of the material.

The third sample was carbonizable at 600oC for 2 hours and activated at 800oC 1 hour, got the coal, containing 1. The method of preparation of the catalyst deposited on activated carbon, comprising the combination of preobrazuemogo substances forming the catalyst substance in a soluble form, carbonation preobrazuemogo substances and activation of coal from getting deposited on activated carbon catalyst, characterized in that as a carbonaceous substance use liquid thermosetting resin, the catalyst is distributed on the particles of activated carbon uniformly and applied in the form of a coating on an inorganic basis or molded into a monolithic product.

2. The method according to p. 1, characterized in that forming the catalyst substance use transition metal, alkali metal, alkaline earth metal or combinations thereof.

3. The method according to p. 2, characterized in that the metal catalyst is chosen from the group comprising Pt, Pd, Rh, Ag, Au, Fe, Co, Cr, Ni, Mn, Cu, Li, Mg, Ba or combinations thereof, preferably Pt.

4. The method according to p. 3, characterized in that forming the catalyst substance use chloroplatinate ammonium.

5. The method according to any of paragraphs.1 to 4, characterized in that the combined preobrazuyas substance and forming the catalyst substance is applied in the form of a coating is sportsouth honeycomb.

7. The method according to p. 5 or 6, characterized in that the inorganic base is a ceramic, glass, glass-ceramic, metal or combinations thereof.

8. The method according to p. 7, wherein the inorganic base is made of cordierite.

9. The method according to any of paragraphs.1 to 8, wherein as thermosetting resin used phenolic resin.

10. The method according to any of paragraphs.1 to 9, characterized in that after the stage of curing preobrazuyas substance and forming the catalyst substance grind into powder and/or after the stage of combining preobrazuem substance and forming the catalyst substance formed into the shape of solid products.

11. The catalyst deposited on activated carbon obtained by combining preobrazuemogo substances forming the catalyst substance in a soluble form, carbonization preobrazuemogo substances and activation of coal from getting deposited on activated carbon catalyst, characterized in that as preobrazuemogo substance use liquid thermosetting resin, the catalyst is distributed on the particles of activated carbon uniformly and applied in the form of a coating on an inorganic basis or otherelectronic to pass through it of an electric current.

 

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