Method of preparing deep hydrocarbon oxidation palladium catalyst

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation of catalyst comprises applying palladium compound onto silica cloth and heat treatment. Palladium compound is applied by circulation of toluene or aqueous palladium acetate solution through fixed carrier bed until palladium content achieved 0.01 to 0.5%. Palladium is introduced into cloth in dozed mode at velocity preferably between 0.1 and 5.9 mg Pd/h per 1 g catalyst. Heat treatment includes drying at temperature not higher than 150oC under nitrogen or in air and calcination in air or nitrogen-hydrogen mixture flow at temperature not higher than 450oC. Original silica cloth can be modified with 0.6 to 6.5% alumina. Palladium is uniformly distributed in silica cloth and has particle size preferably no larger than 15 Å. Invention can be used in treatment of industrial gas emissions and automobile exhaust to remove hydrocarbons.

EFFECT: deepened oxidation of hydrocarbons.

5 cl, 1 tbl, 4 ex

 

The invention relates to the production of catalysts and can be used in the treatment of industrial gas emissions and emissions from hydrocarbons.

A known method of producing catalyst for the oxidation of organic compounds and carbon monoxide (RF Patent No. 2046654, IPC6B 01 J 37/02, 23/44, 1995), including the impregnation of the carrier - γ-alumina with a solution of palladium salt, drying and restoration, characterized in that as a palladium salt used di-acetate palladium.

The disadvantage of this method is that the catalyst is prepared by impregnation of moisture content by mechanical mixing of the carrier and preservative solutions. Unfavorable mode of impregnation is the cause of uneven distribution of the active phase on the height of the layer of the medium, and the intensity of mixing required for uniform distribution of the active ingredient in the granules of the media limit to avoid abrasion. Another disadvantage is the use of the known method of recovering palladium formate, sodium, followed by washing until neutral wash water, which is connected with the problem of disposing of large quantities of wastewater.

There is a method of preparation of the catalyst for purification of gas emissions from motor vehicles and industry (RF Patent is 2046653, IPC6B 01 J 37/02, 23/44, 1995) by applying to the media by the method of circulation of toluene solution of palladium acetate. As media use γ, λ, θ, δ, χ - aluminum oxide or with additions of cobalt, lanthanum, cerium, followed by heat treatment.

The main disadvantage of the catalysts obtained in this method is the traditional ball shape and not enough high activity in the reaction of deep oxidation of hydrocarbons related to the size of the granules of the catalyst and its porous structure.

A known method of manufacturing impregnating textile catalyst on the substrate of the optical fibers (Patent RF № 2134613, IPC6B 01 J 37/02, 23/80, 1999), which includes the following steps: degreasing with annealing for 30 min at 350°in a muffle furnace, the impregnation compound of the active component by dipping the material into the solution, followed by drying in a drying and heat treatment.

In this way the preparation of the catalyst on a substrate of glass used different equipment depending on the stage, and the stage of deposition of the active component is carried out by dipping in an ordinary public baths, which are used for processing of fabrics in light industry. But when the catalyst solutions of the active components, usually regulatel is pour in the bath because in addition to the loss of active components, it is difficult to create acceptable conditions for environmental protection.

In addition, when using media with fine pores, it is difficult to enter the modifying compound and the active components of the catalyst. By dipping into the impregnating solution is not strong adhesion of the active components with the surface of the carrier.

The closest technical solution is the catalyst and the process for oxidation of hydrocarbons (RF Patent No. 2069584, IPC6B 01 J 23/38, 23/70, 1996) on a woven or non-woven media, including SiO2in the mass introduced alloying metals selected from the group of Pt, Pd, Rh, Zr, Ag, Au, Fe, Cr, Co, Ni, Mn, Pb, si in an amount of 0.0001 to 1.0% by weight of the carrier.

The disadvantage of the catalyst is the complexity of the implementation stage of alloying medium. A significant disadvantage is not sufficiently high activity and resistance to sintering of palladium chloride added to the mixture, followed by heat treatment at a temperature of 1350°when the glass is melted.

In addition to the above, the use of palladium chloride as a precursor of the active component does not allow to obtain highly dispersed active component of the catalyst.

The problem solved by the present invention is to develop an efficient way to obtain visicoach the main catalyst using a carrier based on silica fabric, leading to strong pinning of the active component in the pores of the media.

The problem is solved using the method of producing a catalyst for deep oxidation of hydrocarbons, including the application of compounds of palladium on a carrier, representing a silica fabric, and heat treatment. The application of the palladium compounds is carried out by circulation toluene or an aqueous solution of palladium acetate through the stationary layer of the device before the content of palladium in the catalyst is 0.01-0.5 wt.% followed by heat treatment at a temperature of not more than 450°C.

Preferably the heat treatment is carried out as follows: dried at a temperature not exceeding 150°With nitrogen and calcined in a stream of air or nitric mixture at a temperature of not more than 450°C.

The source of silica fabric can be modified aluminum oxide in the amount of 0.5 to 6.5 wt.%.

Palladium efficiently distributed in the silica fabric and has a particle size of preferably not more than 15 Å.

To obtain a catalyst on a silica fabrics, containing palladium in an amount of 0.1-0.5 wt.%, speed dosed introduction of palladium is preferably 0.1 to 5.0 mg Pd/g catalyst·h

In the present method is proposed for introduction intercalation of active components in the fine structure of silica fabric used is with a method of impregnation of the active component through an intensive circulation of the solutions of the active component through the stationary layer of fabric. When circulation of the solution with the active ingredient through silica fabric gradual promotion - intercalation of the active component into the pores of the carrier and secure it in the object structure.

For the preparation of the catalyst used simple equipment. The resulting catalyst after heat treatment, the impregnated silica fabrics include palladium, which has a particle size of not more than 15 Å

To more firmly secure the active component in silica fabrics modify its aluminum oxide by known methods, for example by impregnation oxynitride aluminum with a subsequent heat treatment and fixing of aluminium oxide in the pores of the silica cloth.

The proposed method significantly reduces, virtually eliminates loss of palladium in the prevention of mechanical abrasion of the catalyst. In addition, the inventive method of preparation of the catalyst is characterized by the absence of wastewater. The hallmark of the invention is a process for the impregnation of silica fabrics using the circulation of working fluid through the stationary layer of fabric. At this stage impregnation with a solution of palladium compounds is carried out at a metered introduction of palladium with a speed of 0.1-5.0 mg Pd/g catalyst·h earlier in the circulating solvent.

The particle size of the Pallady is in a highly dispersed active component of catalysts, prepared using palladium acetate, 5 times less in comparison with the known coarse active component of the ball catalyst SPF-0,5, in the way that palladium deposited from acidic solution of palladium chloride.

In the case of the use of catalysts on conventional granular media is problematic to make a sufficiently strong media the optimal form of high geometric surface, good gas permeability. These specific properties of the media, representing the silica cloth.

Operational properties of the catalyst, the carrier is silica fabric, namely, their high strength and low hydraulic resistance, have significant advantages compared with the traditional form of the used catalysts, in particular for deep oxidation of hydrocarbons and CO in the converters of automobile exhaust.

The application of the present invention allows to obtain the above-mentioned process of the active catalysts with high dispersion of palladium and, as a consequence, low total content of the precious metal.

The catalysts obtained by the proposed method were tested for activity in the reaction of deep oxidation of n-butane. For measure of catalytic activity is Rinata the reaction rate of the full oxidation of butane at 400° And volume concentration of butane 0.2 percent.

The content of palladium in the catalyst is determined on the quartz spectrograph SP-30.

The present invention is illustrated by the following examples.

Example 1.

The catalyst is prepared in the pilot impregnating-circulation installation. 153,45 g media - silica fabric is placed in propitiating and provide circulation through the fixed layer of the device 500 ml of toluene for 15 minutes Then spend the dosed introduction of 94.5 ml of toluene solution of palladium acetate with a concentration of 3.25 g/l with a speed of 2.0 mg Pd/g CT·h to the circulating solvent. The impregnation is carried out to complete discoloration impregnating solution. Then the solution is drained and the catalyst is subjected to heat treatment, dried 2 h at 150°With nitrogen and restore in nitric mixture at 450 4 hours

Mass fraction of palladium in the catalyst is 0.15 wt.%.

Example 2.

Similar to example 1 with the difference that as the carrier use a modified silica fabric containing 3.6% Al2About3prepared by impregnation with a solution of oxynitride aluminium concentration of 28.7 g/l Al with step heat treatment in air flow: 110°3 h, 250°C - 2 h, 450° - 2 hours

Mass fraction of palladium in the catalyst - 0.13 wt.%.

Example 3.

Similar to example 1 with the difference that it is the quality of the precursor of the active component using an aqueous solution of palladium acetate in sodium acetate, and as the solvent used water, with silica fabric modified to 6.5 wt.% Al2About3obtained as described in example 2 method.

After application of the active component heat treatment carried out analogously to example 1 with the difference that the dried catalyst in the air.

Mass fraction of palladium in the catalyst is 0.15 wt.%.

Example 4.

Similar to example 1 with the difference in the amount of active component applied with the speed of dispensing of 0.1 mg Pd/g CT·h, and silica fabric contains additional 0.5% Al2About3.

Example 5.

Similar to example 1 with the difference that as the precursor of the active component using an aqueous solution of palladium acetate.

Mass fraction of palladium in the catalyst is 0.5 wt.%.

The rate of dispensing of palladium is 5 mg Pd/g CT·'clock of the following examples and tables, it follows that the catalyst obtained by the proposed method has high activity in the deep oxidation of hydrocarbons.

1. A method of producing a catalyst for deep oxidation of hydrocarbons, including the application of compounds of palladium on a carrier, representing a silica fabric, heat treatment, characterized in that the deposition of palladium compounds is carried out by circulation toluene or water what about the solution of palladium acetate through the stationary layer of the device before the content of palladium in the catalyst is 0.01-0.5 wt.% followed by drying at a temperature not exceeding 150° With nitrogen, air and calcination in a stream of air or nitric mixture at a temperature of not more than 450°C.

2. The method according to claim 1, characterized in that the heat treatment is carried out as follows: dried at a temperature not exceeding 150°With nitrogen and calcined in a stream of air or nitric mixture at a temperature of 450°C.

3. The method according to claim 1, wherein the source of silica fabric additionally modify the aluminum oxide in the amount of 0.5 to 6.5 wt.%.

4. The method according to claim 1, characterized in that palladium is efficiently distributed in the silica fabric and has a particle size of not more than 15.

5. The method according to claim 1, characterized in that to obtain a catalyst on a silica fabrics, containing palladium in an amount of 0.1-0.5 wt.%, speed dosed introduction palladium is 0.1-5.0 mg Pd/g catalyst · h



 

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