Composition based on gold and reducible oxide, method of production and application as catalyst, in particular in carbon monoxide oxidation

FIELD: chemistry.

SUBSTANCE: invention relates to composition based on gold and reducible oxide, method of its production and its application as catalyst, in particular in carbon monoxide oxidation. Described is composition based on gold on carrier based on reducible oxide, as such composition contains titanium or iron (III) oxide, content of halogen in composition, expressed by molar ratio halogen/gold, constitutes not more than 0.05, content of gold in it constitutes not more than 1%, gold is in form of particles with size not more than 10nm, and composition is subjected to reducing processing. Described is method of composition production, which contains following stages: bringing in contact compound based on reducible titanium or iron (III) oxide and compound based on gold halogenated and, in case of necessity, compound based on silver, with formation of suspension of said compounds, pH of obtained medium being set not lower than 8; separation of solid substance from reaction medium; washing solid substance with alkaline solution; in addition method includes reducing processing after mentioned above washing stage. Described is method of carbon monoxide oxidation, method of air purification and method of cigarette smoke purification using described above composition as catalyst.

EFFECT: elaboration of catalysts, efficient at low temperatures and/or high hour volume rates.

16 cl, 12 tbl, 15 ex

 

The present invention concerns a composition based on gold and recoverable oxide, method of its production and its use as a catalyst, in particular, the oxidation of carbon monoxide.

Known catalysts based on gold, which are used, in particular, in the processes of CO oxidation. In addition, a certain number of the above-mentioned oxidation process proceeds at relatively low temperatures, for example less than 250°With, in particular, in the reactions of conversion of water gas (water gas shift). Even attempts to oxidize CO at room temperature, for example, in methods of air purification and/or in harsh environments, such as very high hourly flow rate (Czos) (vvh), as in the case of, for example, cleaning cigarette smoke.

The catalysts available at present and which can be used, from an economic standpoint, it does not have characteristics sufficient to satisfy the aforementioned need.

The subject of the invention is the development of catalysts that are effective at low temperatures and/or high Czos.

For this purpose, the composition according to the invention is a composition of gold-based on the media based on at least one recoverable oxide, and it differs in that the halogen content in it, expressed in molar relation is the group of halogen/gold is not more than 0.05 and the fact that gold is present in the form of particles not larger than 10 nm, and the fact that it is subjected to recovery processing, thus avoiding the compositions of the media in which the only recoverable oxide or only recovered oxides represent a cerium oxide, a cerium oxide in combination with zirconium oxide, cerium oxide in combination with oxide of praseodymium, cerium oxide in combination with titanium oxide or tin oxide in an atomic ratio Ti/Ce or Sn/Ce less than 50%.

The invention also concerns the method of obtaining the above-mentioned composition, which, according to the first implementation variant, characterized in that it contains the following stages:

- bring into contact a compound based on at least one recoverable oxide and connection-based halide gold, forming a suspension of the above compounds, at this pH, thus obtained, are set not lower than 8;

- separate the solid from the reaction medium;

- washed solid alkaline solution;

the method includes, in addition, reductive treatment either before or after the above stage of leaching.

The invention also concerns the method according to the second implementation variant, which is characterized in that it includes the following stages:

- osajda is t gold on the connection-based, at least one recoverable oxide;

- washed solid is obtained on the previous stage, an alkaline solution having a pH of at least 10;

the method includes, in addition, reductive treatment either before or after the above stage of leaching.

The compositions according to the invention is effective at low temperatures, at high Czos and, in addition, have a low gold content.

Other characteristics, details and advantages of the invention more fully apparent when reading the description that follows, as well as various specific examples, which are not restrictive and are intended for illustration purposes only.

Periodic system of the elements, referenced herein, represents the system, published in the "Supplement au Bulletin de la Societe Chimique de France, No. 1 (January 1966).

Under rare earth element mean the elements of the group formed by yttrium and the elements of the Periodic system of the elements with atomic numbers from 57 to 71 inclusive.

Under the specific surface mean the BET specific surface determined by nitrogen adsorption according to ASTM D 3663-78 based on the method of brunauer-Emmett-teller described in the periodical "The Journal of the American Chemical Society",60, 309 (1938).

As indicated above, the composition according to the invention contains gold and recoverable oxide. Recoverable oxide forms of the media.

The term "holder" shall be construed in a broad sense to denote, in the composition according to the invention, the component or components that are predominant in the composition, with the marked element is present mainly on the surface of the above-mentioned components. For simplicity, in the sequel of the description will be talking about the media and caused phase, but will understand that it would not be out of the scope of protection of the present invention in the case in which the item is described as belonging to the put phase will be present in the media, for example, when he was introduced to him during the receiving of the media.

Under the restored oxide imply a metal oxide, which may be located in multiple oxidation States.

Note that the metal, which is part of the carrier is in the form, which consists essentially or only oxide of the above metal. By "consists essentially of" in this description to mean that the amorphous material type, for example, hydroxide or oxyhydroxide are present only in trace quantities.

Defining as any amorphous product, x-ray diffraction pattern which contains no diffraction bands indicating the phase of the oxide, or x-ray diffraction pattern which is EET halogen, indicating the phase of the oxide, but width half max will allow one to calculate using Debye-Scherer a crystallite size less than 2 nm, must be understood in the framework of the present invention, the terms: "amorphous substances are present only in trace quantities", the fact that the comparison of x-ray diffraction pattern of pure metal oxide with the diffraction pattern of the oxide of the same metal, but contains the substances, does not show detectable differences and, in particular, shows no Halogens.

As a recovering oxides that are suitable for use within the present invention, there can be mentioned oxides of transition metals and oxides of rare earth elements. Under transition metals involve elements of IIIA-IIB group of the Periodic system of elements.

More specifically, there can be mentioned oxides of titanium, manganese, iron, copper, cobalt or tin. Thus, the carrier may be preferably based on at least one of these oxides.

As described above, the scope of patent protection of the present invention does not include several special media. Such special media are media based on cerium oxide, cerium oxide and zirconium oxide, cerium oxide and praseodymium oxide, cerium oxide in combination with titanium oxide or tin oxide is in an atomic ratio Ti/Ce or Sn/Ce less than 50%, the extent to which these oxides are only recoverable oxides present in the media. Therefore, note that the medium on the basis of the above oxides, but containing, in addition, other recoverable oxide, such as manganese oxide, is not excluded from the present invention.

The compound used as the carrier, must have, in addition, a sufficiently high specific surface to provide a dispersion of gold on its surface suitable for gold could have a sufficiently high catalytic activity.

Finally, the composition according to the invention should be subjected to recovery processing. Under restoration processing means the processing, which is carried out under such conditions that the media (recoverable oxide) and the applied phase (gold) both are restored. The fact that the composition is subjected to such processing, can be expressed in the presence of oxygen in the media, that is, that the amount of oxygen in the oxide, forming the carrier, less than stoichiometric. This lack of oxygen can be, for example, identified by the method of x-ray diffraction or the analysis method XPE (XPS).

It should be noted that the composition according to the invention can containing the ü gold, in addition, at least one other element selected from silver, platinum, palladium and copper. In this case, the other or these other metal elements may be present, for example, in an amount not more than 400%, more particularly not more than 120%, in particular comprising from 5% to 50% relative to gold, these quantities are expressed in mol.% metal(s) item(s)/gold. The compositions of the specified type, in the case of use at high CIOs can achieve their maximum efficiency even faster.

The content of gold or gold and the above metal element in the composition are not critical, they correspond to the contents of the most commonly used catalysts in order to obtain catalytic activity. As an example, the above-mentioned content is less than 5%, in particular not more than 1%. More specifically, it can be no more than 0, 5% or even not greater than 0.25%. Content greater than 5% usually are not attractive from an economic point of view. These content expressed in mass percent gold, in certain cases, with the metal element, relative to the oxide (or oxides), which form the media.

The composition according to the invention has two other specific characteristics.

The first represents the content of halogen. Over oncrete, the halogen may be bromine or chlorine. Referred to the content that is expressed by the molar ratio of halogen/gold is not more than 0.05. More specifically, it is not more than 0.04, and more specifically does not exceed 0.025.

The halogen can be estimated using the following method. The amount of catalyst required for the analysis, is evaporated in the flame of an oxygen-hydrogen burner (a mixture of N2/About2approximately at 2000°). The resulting steam trap in an aqueous solution containing hydrogen peroxide. When the processing by the flame of a hydrogen-oxygen burner get a solid precipitate, it is transformed into a suspension in water, which were collected gaseous products of combustion (water + N2About2), then filtered. Then the collected filtrate analyzed by ion chromatography and calculate the content of halogen, given the appropriate dilution factor. Finally, calculate the content of halogen in the catalyst, taking into account the mass of catalyst used in the analysis.

Another characteristic is the size of the gold particles present in the composition. The said particles have a size of not more than 10 nm. Preferably, it is less than 3 nm.

Here and for the present description generally referred to the size determined on the basis of analysis is and spectra of x-ray scattering of the composition, using the width (I) at half-height of the diffraction peak of gold. The particle size is inversely proportional to (1/I) the amount referred width I. Note that the x-ray diffraction analysis does not allow you to detect the phase corresponding to the gold particles, the size of which is less than 3 nm, or to detect gold if the gold content is less than 0.25%. In both cases you can then use PAM method.

Now will be described a method of obtaining a composition according to the invention.

This method can be carried out according to the first variant implementation.

In the above-mentioned first embodiment, the first stage of the method consists in bringing into contact connections on the basis of the recoverable oxide and compounds on the basis of the halide of gold and, in certain cases, compounds based on platinum, palladium or copper. Referred to the bringing into contact is carried out, forming a suspension, which is usually water suspension.

Above the original suspension can be obtained on the basis of the preliminary dispersion medium on the basis of the recoverable oxide of the type described above, obtained by the mentioned dispersion medium in the liquid phase and mixed with a solution or dispersion of gold compounds. As the connections of the specified type, you can use chlorinated or brominated soybean is inane gold, for example hartlot acid HAuCl4or its salts, such as NaAuCl4which are the most common.

In the case of a composition also containing silver, platinum, palladium or copper, can be selected as compounds of these elements inorganic salts, such as nitrates, sulphates or chlorides.

You can also use salts of organic acids and, in particular, salts of saturated aliphatic carboxylic acids or salts hydroxycarbonic acids. As examples we can mention the formate, the acetate, propionate, oxalates or citrates. Can be called, at last, in particular, for platinum hydroxide terminplan(II).

In further description of the method will mention only the connection-based halide gold, but the person skilled in the art it is clear that the description applies also to the case in which to apply the connection silver, platinum, palladium or copper, such as described above.

The original suspension can be obtained, for example, by introducing into the dispersion medium solution or dispersion of compound of gold.

According to one particular characteristic of the method, the pH of the suspension, thus obtained, is brought to a value no lower than 8, more specifically, not less than 8.5, and more particularly, not lower than 9.

Preferably maintain the pH at a value not lower than 8 is about the formation of the suspension, during the bringing into contact of the connection based on the recoverable oxide and compounds of halogen gold concomitant introduction connections basic character. For example, when you operate by introducing a dispersion medium solution or dispersion of the compounds of gold, add at the same time the connection of the main character. The flow connection of the main character can be adjusted to maintain the pH at a constant value, i.e. the value of deviating in larger or smaller by 0.3 pH units relative to a fixed size.

As compounds of the main character can be used, in particular, products such as hydroxide or carbonate. You can call hydroxides of alkaline or alkaline earth metals and ammonium hydroxide. You can also use a secondary, tertiary or Quaternary amines. You can also mention the urea. The connection of the main character used usually in the form of a solution.

According to a variant of the method can be applied to the dispersion medium and the solution or dispersion of the compounds of gold, which were both previously brought to a pH of at least 8 so that there is no need to bring them in contact to add the connection to the main character.

The bringing into contact of the compound based on cerium oxide and connect the tion on the basis of the halide of gold carried out usually at room temperature, but this can be done by heating, for example at a temperature of at least 60°C.

The suspension formed during the first stage of the method, the support is usually under stirring for several minutes.

In the second stage separates the solid from the reaction medium by any known method.

The solid, thus obtained, is then washed with an alkaline solution. Preferably, the aforementioned alkaline solution has a pH of at least 8, more specifically at least 9. The alkaline solution may be based on the same connections of the main character as compounds that were mentioned above.

Mentioned rinsing may be carried out in any suitable way, for example, using the technique of flushing piston flow or re-dispersion. In this latter case, the solid is re-dispersed in an alkaline solution, then, usually after keeping under stirring, separating the solid from the liquid medium.

If necessary, washing with an alkaline solution can be repeated several times. In known cases, it may be followed by rinsing with water.

After washing the obtained solid substance is usually dry. Drying can be carried out in any suitable way, for example by air or by lyophilization.

The method according to the invention includes, in addition, reductive treatment. This restorative treatment can take place either before washing with an alkaline solution, which has just been described or mentioned after washing. In this latter case, referred to restorative treatment can also be carried out before washing with water or after it, in the event of such wash water, and before or after drying. The above treatment is carried out in such a way that all the element of gold is in the degree of oxidation, the lower its degree of oxidation before processing, and the above-mentioned oxidation before processing is usually equal to 3. The oxidation state of gold can be determined by methods known to the expert, for example by reduction with programmable temperature change (VAC) or by the method of x-ray electron spectroscopy (RECs).

You can consider different types of restorative treatment.

First, it is possible to carry out chemical recovery, contacting the product with a reducing agent such as ferrous ions, titration, ions of tin(II), oxalic acid, citric acid, hydrogen peroxide, hydrides, such as NaBH4, hydrazine (NH2-NH2), formaldehyde in aqueous solution (H2CO), phosphorus restore the ate, including tetrakis(hydroxymethyl)phosphorylated or NaH2PO2. This processing can be carried out, suspending the product in an aqueous medium containing a reducing agent, or on the product in the reaction medium after the deposition of gold.

You can also restore under the action of ultraviolet rays; and in this case, processing can be carried out in solution or suspension of the product or in the powder.

This treatment can be performed before or after the stage of washing described above.

In addition, the recovery processing can be carried out gas by using the reducing gas, which may be selected from hydrogen, carbon monoxide or hydrocarbons, with the said gas may be used in any concentration. Clearly, you can use hydrogen diluted in argon. In the case of restoration processing in accordance with this latter type, it is carried out after the above stage of leaching.

In this case, processing is carried out at a temperature which is not higher than 200°C, preferably not higher than 180°C. the duration of the treatment can be, in particular, from 0.5 to 6 hours.

At the end of restorative treatment is not usually required to produce firing. About the NACO such firing is not excluded, preferably, at low temperature, i.e. not more than 250°s With a duration of no more than 4 hours, and for example, in the air. In the case of restorative treatment chemical of the type described above, the implementation of such firing may be useful.

The method according to the invention can also be implemented according to the second variant of implementation, which will now be described.

The first stage is the deposition of gold and, in certain cases, silver, platinum, palladium or copper connection on the basis of the recoverable oxide by impregnation or ion exchange.

The method of deposition impregnation are well known. Preferably, use a dry impregnation. Dry impregnation is added to the impregnated product, here based media recoverable oxide, the volume of the solution of the compound of gold, which is equal to the pore volume impregnated solids.

The connection of the gold is here the connection of the same type that the connection that was described above for the first variant implementation.

Deposition using ion exchange is also a known manner. Here, too, can use the same connection type of gold that and before that. In the second stage of the method, the product obtained in the previous phase, then washed with an alkaline solution, the pH of which is equal to, m is Nisha least 10, preferably at least 11. Mentioned rinsing can be carried out in the same manner and with the same connections of the main character as described for the method according to the first variant implementation.

At the same time, in this second variant of realization can be applied reductive treatment and drying in the same manner as the method that was described above.

Finally, it should be noted that it is also possible, in case of receiving structure on the basis of another metal element, in addition to gold, to besiege the media first mentioned metallic element, for example, impregnation, then, in the second place, to start deposition of gold by following the methods that have just been described.

The compositions according to the invention, such as obtained by the method described above, are in the form of powders, but, in certain cases, they can be molded to be in the form of granules, beads, cylinders, extruded or cellular material of variable size. They can also be used in catalytic systems comprising a coating (wash coat) on the basis of the above compounds on the carrier, for example, a monolithic type of metal or ceramics. The coating can contain, for example, aluminum oxide. It should be noted that the deposition of gold can also be carried out to the media, to Oromo pre-given form, above.

The compositions according to the invention, such as described above or obtained by the method detailed above, can be used more specifically as catalysts in the ways of carrying out the oxidation of carbon monoxide.

Quite specifically, they are effective for methods of this type that are carried out at low temperatures, implying thereby a temperature above 250°C. They are effective even at room temperature. Under room temperature here and throughout the description implies, if not otherwise stated to the contrary, the temperature not exceeding 35°more specifically, in the range from 10°to 25°C. Finally, they can also be effective in the high castle, which, for example, can go up to 1500000 cm3/gcat/PM

In addition, the compositions according to the invention can be applied for the oxidation of carbon monoxide at lower temperatures, i.e. below 0°With, for example, in the interval from -10°0°and for the purification of gas or environment with very low CO content, for example not more than 1000 ppm, and at extremely high CIOs that can go up to 30000000 cm3/gcat/PM

Thus, in the example of use in the methods of carrying out the oxidation of carbon monoxide, they can be applied for treatment of smoke si is Aretha, in the reaction gas reforming with water (CO + H2About → CO2+ H2), in particular at a temperature below 100°or when processing the gaseous products of reforming at temperatures below 150°processing type PROC (preferential oxidation of CO in the presence of hydrogen).

In the particular case of cleaning cigarette smoke catalytic composition may be in powder form. It can also be subjected to the appropriate molding, for example, it can be put into the form of granules or flakes. In the case of the powder grain size distribution of the composition may be in the range from 1 to 200 microns. In the case of granules, the above size can be in the range from 700 to 1500 μm, for bead size can be in the range of 200 to 700 μm and in the range from 100 to 1500 μm for scales.

The catalytic composition may be introduced by mixing or by bonding with the fiber forming cigarette filter (e.g., cellulose acetate) during manufacture of the filter, in particular, in the case of filters, called "Double filter" ("Dual filter") or "Triple filter" ("Triple filter"). The catalytic composition may be deposited on the inner side of the paper surrounding the rope, forming a filter ("tipping paper") in the case of a filter of the type "Invoice filter ("filter Patch"). The catalytic composition could also be introduced into the cavity of the filter Volume filter ("Cavity filter").

In the beam of the use of the catalytic composition according to the invention in a filter for cigarettes, you can perform the restoration processing part, once entered in the filter. In this case, the recovery processing is carried out according to the methods that were described above.

The amount of the catalytic composition is not critical. It is limited, in particular, the dimensions of the filter and loss of load resulting from the presence of the composition in the filter. Usually it is not more than 350 mg per cigarette, preferably, it ranges from 20 to 100 mg per cigarette.

Thus, the invention concerns a filter for cigarettes, which contains a composition, such as described before it or obtained by the method detailed above.

Here, note that the term "cigarette" should be considered in a broad sense to include any product that is intended for Smoking, and tobacco, wrapped in a tube, for example on a base of paper or tobacco. Therefore, here this term also applies to cigars and cigarillos.

Finally, the compositions according to the invention can also be used in the purification treatment of air in case of air containing at least one connection type monoxide, ethylene, aldehyde, amine, mercaptan, ozone, and usually the type of volatile organic compounds or atmospheric pollutants, such as fatty acids, hydrocarbons, in chastest the aromatic hydrocarbons, and oxides of nitrogen (for oxidation of NO to NO2), and type of malodorous compounds. More specifically, as the compounds specified varieties can be called ethanthiol, valeric acid and trimethylamine. The above treatment is carried out by contacting the treated air to the composition, such as described before, or obtained by the method detailed above. The compositions according to the invention allow the processing at room temperature.

Now we will provide an example.

In the above examples, the results for CO oxidation. These results were obtained by testing the catalytic oxidation of CO, which is described below.

Catalytic feel a connection in the form of flakes from 125 to 250 μm, which is obtained by pelletizing, grinding and sieving the powder catalytic compounds. The catalytic compound is placed in a reactor on sintered glass, which performs the role of physical media powder.

In this test through the catalyst miss a synthetic mixture containing from 1 to 10 vol.% CO, 10 vol.% CO2, 10% vol. About2, 1,8% vol. H2In N2. The gaseous mixture is continuously circulated through a quartz reactor containing from 25 to 200 mg of catalytic compounds, with a flow rate of 30 l/h

When the mass of catalytic compounds less is 200 mg, add silicon carbide SiC, so that the sum of the masses of catalytic compounds and SiC would be equal to 200 mg of silicon Carbide SiC inert to the oxidation of CO and plays here the role of diluent in order to ensure uniformity of the catalytic layer.

The conversion FROM the initially measured at room temperature (T = 20°in the examples) and only mentioned when the conversion is incomplete at this temperature, the temperature increase through the furnace from room temperature to 300°With a speed of 10°C/min. to measure the conversion of CO in the CO2gases at the outlet of the reactor was analyzed by the method of IR-spectroscopy with an interval of about 10 seconds.

When the conversion FROM at room temperature is incomplete, the results are expressed by the temperature proconvertin (T50%), the temperature at which 50% of the CO present in the gas stream become CO2.

In the examples below, the catalytic compounds were evaluated for the oxidation of CO in CO2in the following conditions.

Conditions: 3% CO - CIOs = 1500000 cm3/gcat/h
Conditions: 3% CO - CIOs = 300000 cm3/gcat/h
Gaseous mixture:3% vol. CO, 10 vol.% CO2, 10% vol. About2, 1,8% vol. H2In N2
Total consumption: 30 l/h
The mass of the catalyst:100 mg
CIOs:300000 cm3/gcat/h
Conditions: 3% CO - CIOs = 600000 cm3/gcat/h
Gaseous mixture:3% vol. CO, 10 vol.% CO2, 10% vol. About2, 1,8% vol. H2In N2
Total consumption:30 l/h
The mass of the catalyst:50 mg
CIOs:600000 cm3/gcat/h
Conditions: 3% CO - CIOs = 900000 cm3/gcat/h
Gaseous mixture:3% vol. CO, 10 vol.% CO2, 10% vol. About2, 1,8% vol. H2In N2
Total consumption:30 l/h
The mass of the catalyst:33 mg
CIOs:900000 cm3/gcat/h
Conditions D: 3% CO - CIOs = 1200000 cm3/gcat/h
Gaseous mixture:3% vol. CO, 10 vol.% CO2, 10% vol. About2, 1,8% vol. H2In N2
Total consumption:30 l/h
The mass of the catalyst:25 mg
CIOs:1200000 cm3/gcat/h
Gaseous mixture:3% vol. CO, 10 vol.% CO2, 10% vol. About2, 1,8% vol. H2In N2
Total consumption:30 l/h
The mass of the catalyst:20 mg
CIOs:1500000 cm3/gcat/h
Conditions F: 3% CO - CIOs = 100000 cm3/gcat/h
Gaseous mixture:3% vol. CO, 10 vol.% CO2, 10% vol. About2, 1,8% vol. H2In N2
Total consumption:12 l/h
The mass of the catalyst:120 mg
CIOs:150000 cm3/gcat/h

EXAMPLE 1

In 250 ml of water was dispersed with stirring 40 g of powder of titanium oxide with a surface of 75 m2/, Then the pH of the suspension was adjusted to 9 by adding a solution of 1 M Na2CO3.

At the same time, 0.8 g HAuCl4·3H2O (Sigma-Aldrich) dissolved in 250 ml of water.

Then the gold solution is added dropwise within one hour to a suspension of titanium oxide. While adding the gold solution the pH of the suspension is maintained within the range of 8.7 to 9.3 by adding a solution of 1 M Na2CO3. The resulting suspension is incubated under stirring for 20 minutes before filter in the vacuum.

The precipitate is again dispersed in a solution of Na2CO3with a pH of 9, the volume of which is equivalent to the volume of uterine fluids removed during the first stage of filtration. The suspension support with stirring for 20 minutes. This procedure alkaline rinse, repeat 2 more times. The precipitate in the end again dispersed in water volume equivalent to the volume of uterine fluids removed during the filtration, then is filtered in a vacuum.

The washed precipitate lyophilizer, then restore 2 hours at 170°With a gaseous mixture composed of 10 vol.% molecular hydrogen diluted in argon.

The analyses carried out on the catalyst, produce results that are presented in table 1, following.

EXAMPLE 2

The catalyst obtained according to the same Protocol as that described in example 1, except that the powder of titanium oxide has a surface 105 m2/g and that the washed precipitate is dried for 2 hours in air at 100°instead liofilizirovanny before processing diluted with hydrogen.

The analyses carried out on the catalyst, produce results that are presented in table 1, following.

EXAMPLE 3, COMPARATIVE

The catalyst was prepared according to the same Protocol as that described in example 1, for which the conclusion of the addition, that the dried product is not treated with diluted hydrogen.

The analyses carried out on the catalyst, produce results that are presented in table 1, following.

EXAMPLE 4

In 250 ml of water was dispersed with stirring 40 g of powder of titanium oxide with the surface 105 m2/, Then the pH of the suspension was adjusted to 9 by adding a solution of 1 M NaOH.

At the same time, 0.8 g HAuCl4·3H2O (Sigma-Aldrich) dissolved in 250 ml of water. The solution is heated to 70°With, then its pH was adjusted to pH 9 by adding a solution of 1 M NaOH.

Then the gold solution is added dropwise within 30 minutes to a suspension of titanium oxide. The resulting suspension was kept at 70°under stirring for 1 hour before filtering under vacuum.

The precipitate is again dispersed in NaOH solution to pH 9, the volume of which is equivalent to the volume of uterine fluids removed during the first stage of filtration. The suspension is incubated under stirring for 20 minutes. This procedure alkaline rinse, repeat 1 more time. The precipitate in the end again dispersed in water volume equivalent to the volume of uterine fluids removed during the filtration, then is filtered in a vacuum.

The washed precipitate lyophilizer, then restore 2 hours at 170°With a gaseous mixture composed of 10 vol.% molecular bodoro is a, diluted with argon.

The analyses carried out on the catalyst, produce results that are presented in table 1, following.

EXAMPLE 5

Now give an example of the preparation of the catalyst in the form of granules.

In column placed 21 g of granulated titanium oxide (TiO2) with a specific surface area of 90 m2/, Mentioned column connect using a circulation system with the reactor (1)containing 125 g of water.

At the same time in the reactor (2)containing 125 g of water, dissolve 0.4 g HAuCl4·3H2O. the Solution of gold in the reactor (2), heated to 70°and bring its pH to 9 using a solution of 1 M Na2CO3.

The solution contained in the reactor (1), is forced to circulate through a column containing granulated TiO2with a capacity of 10 ml/min. Through the circulation between the reactor (1) and a column reactor (1) is heated to 70°and bring its pH to 9 using a solution of 1 M Na2CO3.

The gold solution is injected under stirring in a reactor (1) within 30 minutes. In the reactor (1) maintain pH 9 using a solution of 1 M Na2CO3. Solution support under stirring for 1 hour after addition of the solution of gold.

Stop the circulation between the reactor (1) and column.

The mother liquor is extracted, then replace with 250 g of water (pH is brought to 9 1 M Na2COsub> 3at room temperature). Restore circulation between the reactor (1) and the column for 10 minutes. The described operation is repeated twice before the last rinse 250 g of water.

The granules are separated from the leaching solution, then lyophilizer. Then restore 2 hours at 170°With a gaseous mixture composed of 10 vol.% molecular hydrogen diluted in argon.

The analyses carried out on the catalyst, produce results that are presented in table 1, following.

The following two examples relate to the chemical recovery processingin situi.e. in the reaction medium after the stage of deposition of gold in aqueous solution.

EXAMPLE 6

In the reactor (1)containing 125 g of water was dispersed under stirring 21 g of powder of titanium oxide with a surface of 75 m2/year

At the same time in the reactor (2)containing 125 g of water under stirring to dissolve 0.4 g HAuCl4·3H2O (Sigma-Aldrich).

Both reactor is heated to 70°and, in addition, the pH was adjusted to 9 using a solution of 1 M Na2CO3.

Then the gold solution is added dropwise within 30 minutes to the reactor (1). During the addition of the gold solution, the pH of the reactor (1) support equal to 9, if necessary, by adding a solution of 1 M Na2CO3. The resulting suspension support under stirring at 70°C for 30 min is t after addition of a solution of gold.

In the reactor (1) for several minutes added dropwise 0.32g TGFH (THPC) (chloride, tetrakis(hydroxymethyl)phosphonium 80%aqueous solution, Aldrich), pre-diluted in 5 ml of water. The amount used TGFH corresponds to a molar ratio TGFH/Au, is equal to 1.35. After the addition of the reactor (1) is capable of 30 minutes under stirring at 70°C. Then, after cooling, the resulting suspension is centrifuged (10 minutes at 4500 rpm).

The precipitate is again dispersed in a solution of Na2CO3c pH 9, the volume of which is equivalent to the volume of uterine fluids removed during the first centrifugation. Before the new centrifugation, the suspension support with stirring for 10 minutes. The described procedure is repeated two more times. The precipitate in the end again dispersed in water volume equivalent to the volume of uterine fluids removed during the first centrifugation.

The washed precipitate is dried overnight at 80°C, then calcined 2 hours at 200°s on the air.

The analyses carried out on the catalyst, produce results that are presented in table 1, following.

EXAMPLE 7

In column placed 21 g of granulated titanium oxide (TiO2) with a specific surface area of 90 m2/, Mentioned column connected through a system of qi is in the course of circulation reactor (1), containing 125 g of water.

At the same time in the reactor (2)containing 125 g of water, dissolve 0.4 g HAuCl4·3H2O. the Solution of gold in the reactor (2), heated to 70°and bring its pH to 9 using a solution of 1 M Na2CO3.

The solution contained in the reactor (1), is forced to circulate through a column containing granulated TiO2with a capacity of 10 ml/min. Through the circulation between the reactor (1) and a column reactor (1) is heated to 70°and bring its pH to 9 using a solution of 1 M Na2CO3.

The gold solution is injected under stirring in a reactor (1) within 30 minutes. In the reactor (1) maintain pH 9 using a solution of 1 M Na2CO3. Solution support under stirring for 1 hour after addition of the solution of gold.

In the reactor (1) for several minutes added dropwise 0.32g TGFH (THPC) (chloride, tetrakis(hydroxymethyl)phosphonium 80%aqueous solution, Aldrich), pre-diluted in 5 ml of water. The amount used TGFH corresponds to a molar ratio TGFH/Au, is equal to 1.35.

After the addition of the reactor (1) is capable of 30 minutes under stirring at 70°With, then stops the circulation between the reactor (1) and column.

The mother liquor is extracted, then replace with 250 g of water (pH is brought to 9 1 M Na2CO3at room is temperature). Restore circulation between the reactor (1) and the column for 10 minutes. The described operation is repeated twice before the last rinse 250 g of water.

The granules are separated from the leaching solution, and then dried at 80°C overnight and finally calcined in air at 200°within 2 hours.

The analyses carried out on the catalyst, produce results that are presented in table 1, following.

EXAMPLE 8

In 250 ml of water was dispersed with stirring 40 g of powder of iron oxide (Fe2O3surface 225 m2/, Then the pH of the suspension was adjusted to 9 by adding a solution of 1 M Na2CO3.

At the same time, 0.8 g HAuCl4·3H2O (Sigma-Aldrich) dissolved in 250 ml of water.

Then the gold solution is added dropwise within one hour to a suspension of iron oxide. While adding the gold solution the pH of the suspension support equal to 9 by adding a solution of 1 M Na2CO3. The resulting suspension is incubated for 20 minutes with stirring before filter in the vacuum.

The precipitate is again dispersed in a solution of Na2CO3with a pH of 9, the volume of which is equivalent to the volume of uterine fluids removed during the first stage of filtration. The suspension support with stirring for 20 minutes. This procedure alkaline rinse, repeat 2 more times. The precipitate in the once all again dispersed in water volume, equivalent volume of uterine fluids removed during the filtration, then is filtered in a vacuum.

The washed precipitate lyophilizer, then restore 2 hours at 170°With a gaseous mixture composed of 10 vol.% molecular hydrogen diluted in argon.

The analyses carried out on the catalyst, produce results that are presented in table 1, following.

Table 1
ExampleThe particle size of Au (nm)The Au content (%)Cl/Au (molar)
1<30,650,034
2<30,640,034
3<30,650,034
4<30,650,034
5<30,650,008
6<31,000,006
7<30,800,007
8<30,800,007

In table 2, following, give the results obtained with the catalysts of examples for the conversion of CO (3% vol. WITH).

Table 2
Conditions
ExampleABCDEF
1100% at Tto100% at Tto100% at Tto100% at Tto100% at Tto-
2100% at Tto-----
350% at 42°-----
4100% at Tto100% at Tto100% at Tto50% at 44°--
5---100% at Tto100% at Tto-
6---100% at Tto-
7----100% at Tto-
8----- 40% at 46°

Tto:room temperature = 20°C.

It is seen that the catalyst of example 3 convert only 50%, and is at a temperature of more than 35°whereas the catalyst of example 1 oxidize CO in the CO2100% at room temperature when CIOs, reaching at least to 1,500,000 cm3/gcat/PM

Now give the results for the oxidation of small amounts of CO in the CO2using the test described above. The oxidation reaction is carried out at low temperature, -10°With, in the following conditions:

Conditions I: 50./million CO - CIOs = 6000000 cm3/gcat/h
Condition G: 50./million CO - CIOs = 900000 cm3/gcat/h
Gaseous mixture:50./million, 20% vol. About2in N2
Total consumption:30 l/h
The mass of the catalyst:33 mg
CIOs:900000 cm3/gcat/h
Conditions N: 50./million CO - CIOs = 3000000 cm3/gcat/h
Gaseous mixture:50./million, 20% vol. About2in N2
Total consumption:30 l/h
The mass of the catalyst:10 mg
CIOs:3000000 cm3/gcat/h
Gaseous mixture:50./million, 20% vol. About2in N2
Total consumption:30 l/h
The mass of the catalyst:5 mg
CIOs:6000000 cm3/gcat/h

In table 3, following, give the results obtained with the catalyst of example 1 for the conversion of about 50./million WITH at low temperature.

Table 3
Example 1Conditions
GHI
T = -10°CONV.(CO) = 100%CONV.(CO) = 60%CONV.(CO) = 35%
T = 0°CONV.(CO) = 100%CONV.(CO) = 90%-
T = 10°CONV.(CO) = 100%CONV.(CO) = 100%CONV.(CO) = 90%

Now give the results for the oxidation of small amounts of CO in the CO2at very high Czos, using the following test.

Two gas bag volume 30 l connect respectively with the inlet and outlet of the pump using rubber tubing with an inner diameter of 8 mm rubber tube m is waiting for the pump outlet and the gas bag is placed catalytic compound in the form of flakes from 125 to 250 μm, obtained by pelletizing, grinding and sieving the powder catalytic compounds. Catalytic compound immobilized using two swabs of quartz wool. At that time, before the gas bag is connected to the output of the pump is empty, the bag is connected with its input, creating an atmosphere containing about 100./million of CO in the air. At t=0 run the pump with a capacity of 50 l/min and the contents of the gas bag is connected to the input is transferred through the catalytic layer in an initially empty gas bag. Then measure the CO content in the gas bag by means of the reaction tube Drager for. This test is carried out at room temperature under the following conditions:

Conditions J: 100.million CO - CIOs = 10000000 cm3/gcat/h
Gaseous mixture:100.million, 20% vol. About2in N2
Total consumption:50 l/min
The mass of the catalyst:300 mg
CIOs:10000000 cm3/gcat/h
Conditions K: 100.million CO - CIOs = 15000000 cm3/gcat/h
Gaseous mixture:100.million, 20% vol. About2in N2
Total consumption:50 l/min
The mass of the catalyst:200 mg
CIOs:15000000 cm3/gcat/h
Conditions L: 100.million CO - CIOs = 30000000 cm3/gcat/h
Gaseous mixture:100.million, 20% vol. About2in N2
Total consumption:50 l/min
The mass of the catalyst:100 mg
CIOs:30000000 cm3/gcat/h

In table 4, following, give the results obtained with the catalyst of example 1 for the conversion of 100 rpm./million WITH at room temperature.

Table 4
Example 1Conditions
JKL
T = 28°CONV.(CO) = 35 ± 5%CONV.(CO) = 50 ± 5%CONV.(CO) = 65 ± 5%

The results of tables 3 and 4 show that the catalyst according to the invention is able to oxidize CO in the CO2at low concentrations and at very high Czos.

The following example refers to the conversion of ozone (O3) oxygen (O2in the reaction stage is possible. This result was obtained through the catalytic test, which is described below.

In the above test have closed polymer membrane displacement 5.3 l, provided with several holes, enabling the introduction of ozone, the introduction of the catalyst and sampling of the gas phase.

Use an ozone generator, which regulate in order to create a gas stream containing 125 g/m3ozone in the air. Vials for gas volume of 100 ml, fill up the gas flow, then the aforementioned ampoules for gas using a gas syringe taken 17 ml, which then Inuktitut in a closed shell, in order to create an atmosphere containing about 200./million of ozone in the air.

In the second place, in the shell, using the device, eliminating any contact of the shell with the external atmosphere, administered 200 mg of catalytic compounds in powder form. The reference time is determined by the introduction of the catalyst into the shell. The gas phase homogenized using a recirculating pump, the performance of which was 13.5 l/min

The disappearance of the ozone present in the shell in time keep using reaction tubes Dreger (Draeger) for ozone.

Conversion of molecules (M)subject to oxidation, ozone, calculated as follows, by concentration, determination is pushed through the reaction tubes Dreger (Draeger).

CONV.(M) = [conc.M(t)-conc.M(t=0)]/conc.M(t=0)

EXAMPLE 9

In the test described above, using the catalyst of example 1. In table 5, following the results obtained at room temperature for the conversion of 200 rpm./million of ozone.

Table 5
Time (min)CONV. About3
00
580
10100

The data show that about 200./million of ozone is decomposed to oxygen in less than 10 minutes at room temperature.

EXAMPLE 10

Now give an example of the preparation of the catalyst in the form of pellets, containing, in addition to gold and silver.

Impregnated with 40 g of granulated titanium oxide (TiO2) with a specific surface area of 90 m2/g of 25.8 ml of an aqueous solution of 6,7·10-2M AgNO3. Then the paste is dried in an oven overnight at 120°S, then 2 hours and calcined in air at 500°C.

Then proceed according to example 5, to the deposition of gold on 21 g of the granules obtained in this way.

The analyses carried out on the catalyst, produce results that are presented in table 6, following.

Table 6
ExampleThe particle size of Au (nm)The Au content (%)The Ag content (%)Cl/Au (molar)Ag/Au (molar)
10<30,650,40,0081,13

In table 7, following, give the results obtained with the catalysts of examples for the conversion of 3% vol. WITH.

Table 7
ExampleConditions
DE
5100% at Tto100% at Tto
CONV. maximum at t=90CONV. maximum at t=120 s
10100% at Tto100% at Tto
CONV. maximum at t=0 sCONV. maximum at t=0 s

Tto: room temperature = 20°C.

It is seen that the catalyst of example 10 has a feature to reach their maximum level of CO conversion faster than the catalyst of example 5.

The examples below relate to the oxidation of various volatile organic compounds (VOCS) (COV), such as acetaldehyde (CH3SNO), methanol (CH3IT), ethanthiol (CH3CH SH), valeric acid (CH3(CH2)3CO2N) and trimethylamine ((CH3)3N). These results were obtained through catalytic oxidation test, which is described above.

In the above test have closed polymer membrane displacement 5.3 l, provided with several holes, enabling the introduction of ozone, the introduction of the catalyst and sampling of the gas phase.

First, in a closed envelope by means of a syringe injected volume of the molecules of the liquid. The injected volumes of 2.5, 2, 3,5, 5 and 6 µl respectively for acetaldehyde, methanol, ethanthiol, valerianic acid and trimethylamine (50%aqueous solution). At room temperature (T = 20-30° (C) all of the injected fluid to evaporate in the shell with creating an atmosphere containing about 200./million molecules that are subject to oxidation in the air.

In the second place, in the shell, using the device, eliminating any contact of the shell with the external atmosphere, administered 200 mg of catalytic compounds in powder form. The reference time is determined by the introduction of the catalyst into the shell. The gas phase homogenized using a recirculating pump, the performance of which was 13.5 l/min

To ensure the continuation of the oxidation reaction, the gas phase is withdrawn from the membrane through the membrane is an early separation element and then analyzed by gas chromatography. On the chromatograph Hewlett Packard Micro GC HP M200, thanks to the device for sampling, which is supplied with the analyzer, analyze H2O, CO, CO2CH3CHO, CH3OH and CH3CH2SH. Valeric acid (CH3(CH2)3CO2N) and trimethylamine ((CH3)3N) analyze the chromatograph Varian 3200, using a syringe for sampling of the gas phase from the closed shell. The gas phase to analyze the introduction of the catalyst, and then after administration at regular intervals, components from several minutes to several hours according to the test.

Conversion of molecules (M)subject to oxidation, calculated as follows by using areas of chromatograms:

CONV.(M) = [areaM(t)-areaM(t=0)]/areaM(t=0).

For each study oxidizable molecules in the same conditions hold for the idle experience without catalyst, which does not see any changes in the concentration of oxidized molecules in the course of time.

EXAMPLE 11

In the test, which was described above, using the catalyst of example 1.

In table 8, following, give the results obtained at room temperature for the conversion of 200 rpm./million acetaldehyde.

Table 8
Time (min)the OHB. CH3SNO
00
865
2386
3895
53100

The data show that about 200./million acetaldehyde fully converted in less than 1 hour of reaction.

Chromatographic analysis allows to confirm that the resulting amount of CO2and H2Oh well correspond to the reaction of complete oxidation, which leads to the removal of acetaldehyde according to:

CH3SNO + 5/2O2→ 2SD2+ 2H2About

EXAMPLE 12

In the test, which was described above, using the catalyst of example 1.

In table 9, following, give the results obtained at room temperature for the conversion of 200 rpm./million methanol.

Table 9
Time (min)CONV. CH3HE
00
1138
3648
7455
18267
115791

The data show that about 200./million methanol converted more than 90% over 20 hours of reaction.

Chrome is tographically analysis allows to confirm, that the resulting amount of CO2and H2Oh well correspond to the reaction of complete oxidation, which leads to the removal of methanol under:

CH3HE + 3/2O2→ CO2+ 2H2About

EXAMPLE 13

In the test, which was described above, using the catalyst of example 1.

In table 10, the following, give the results obtained at room temperature for the conversion of 200 rpm./million ethanthiol.

Table 10
Time (min)CONV. CH3CH2SH
00
1062
2575
5590
8594
11596

The data show that about 200./million ethanthiol converted more than 70% after 1 hour of reaction.

Analysis of the gas phase through the tube Dreger (Draeger) for sulfur dioxide (SO2at t=50 minutes shows that the shell is more than 100 rpm./million SO2. The changing concentrations of CO2N2Oh and the presence of SO2allows to attribute the disappearance of ethanthiol partial oxidation.

EXAMPLE 14

In the test, which was described above, the use of catalysis is the PR of example 1.

In table 11, the following, give the results obtained at room temperature for the conversion of valerianic acid.

Table 11
The injection box 200.millionTime (min)Concentration
CH3(CH2)3CO2NCH3(CH2)3CO2N (./million)
1ththe injection box0200
1113
270
2ththe injection box540
6444
8020
963

The data show that when each of the injection 200 rpm./million valerianic acid converted in less than 60 minutes.

The gas phase analysis shows that in total about 400./million valerianic acid converted and formed about 200./million CO2and 1000 rpm./million N2O. the Changing concentrations of CO2N2Oh and valerianic acid allows to attribute the disappearance of valerianic acid partial oxidation.

EXAMPLE 15

In the test, which was described above, using the catalyst of example 1.

In table 12, the following, give the results obtained at room temperature for the conversion of 200 rpm./million trimethylamine.

Table 12
Time (min)CONV. (CH3)3N
00
674
2182
4883
9090

The data show that about 200./million trimethylamine converted more than 80% after 30 minutes of reaction.

The gas phase analysis shows that similarly formed about 50./million CO2and 1000 rpm./million N2O. the Changing concentrations of CO2N2Oh and trimethylamine allows to attribute the disappearance of trimethylamine partial oxidation.

1. The composition of the gold-based on the media based on the recoverable oxide, characterized in that as recoverable oxide composition contains titanium oxide or iron oxide (III), the content of halogen in the composition expressed by the molar ratio of halogen/gold is not more than 0.05, the gold content in it is not more than 1%, gold is in the form of particles of the size of the ROM is not more than 10 nm and a composition subjected to recovery processing.

2. The composition according to claim 1, characterized in that the halogen content in it is not more than 0.04, and more specifically, does not exceed 0.025.

3. The composition according to claim 1 or 2, characterized in that the gold is in the form of particles not larger than 3 nm.

4. The composition according to claim 1 or 2, wherein halogen represents chlorine.

5. The composition according to claim 1 or 2, characterized in that the gold content in it is not more than 0.5%, more specifically, not greater than 0.25%.

6. The composition according to claim 1 or 2, characterized in that it further comprises another metal element represents silver.

7. The composition according to claim 6, characterized in that the above-mentioned other metal element is present in an amount of not more than 400%, more specifically in the range from 5 to 50% relative to gold.

8. A method of obtaining a composition according to one of claims 1 to 7, characterized in that it comprises the following stages:

the bringing into contact of the connection based on the recovered titanium oxide or iron oxide (III) and compounds of halogen gold and, if necessary, based compounds silver with formation of a suspension of the above listed compounds, while the pH of the resulting environment is set not lower than 8;

the separation of solids from the reaction medium;

washing the solids with an alkaline solution

when this method is engages, in addition, the recovery processing after the above stage of leaching.

9. The method according to claim 8, characterized in that the pH of the medium formed in obtaining suspensions of compounds based on renewable oxide and compounds on the basis of the halide of gold and, if necessary, the connection on the basis of silver, supported at the level of values, at least 8 adding connection of the main character.

10. The method according to claim 8 or 9, characterized in that the obtained solid is washed with an alkaline solution having a pH of at least 8, preferably at least 9.

11. The method according to claim 8, characterized in that the reduction treatment is carried out using a reducing gas at a temperature not exceeding 200°C, preferably not higher than 180°C.

12. The method of claim 8, designed to obtain a composition according to claim 6 or 7, characterized in that the connection on the basis of the halide of gold is brought into contact with the connection on the basis of the above recoverable oxide, pre-impregnated with oxide of silver.

13. The method of oxidation of carbon monoxide, characterized in that the catalyst used, the composition according to one of claims 1 to 7 or a composition obtained by the method according to one of p-12.

14. The method according to item 13, characterized in that it is used to clean cigarette smoke, Rea is the conversion of water gas, when processing gases of the reformer.

15. The way to clean air, containing at least one connection type monoxide, ethylene, aldehyde, amine, mercaptan, ozone, type volatile organic compounds or atmospheric pollutants and type compounds with unpleasant smell, characterized in that the air is introduced into contact with the composition according to one of claims 1 to 7 or a composition obtained by the method according to one of p-12.

16. Filter for cigarette, characterized in that it contains a composition according to one of claims 1 to 7 or a composition obtained by the method according to one of p-12.



 

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18 cl, 5 dwg, 3 tbl

FIELD: chemistry.

SUBSTANCE: way of syngas cleaning includes: introduction of the flow of initial syngas, into the feed zone of the distillation column, flow expansion of the liquid remainder from the distillation column by means of a dilator of liquids with the extraction of work for forming the flow of the cooled waste liquid, the rectification of vapour from the feed zone for forming the upper flow of vapour with the decreased content of nitrogen and inert gases, cooling of the upper vapour flow in the indirect heat exchange with the flow of the cooled waste liquid for forming the of partially condensed upper flow and flow of the partially heated waste liquid, separation of the partially condensed upper flow into the flow of condensate and the flow of the purified vapour of syngas with the decreased content of nitrogen and inert gases and the irrigation of distillation column by the flow of condensate. By the first variant the method of production of ammonia includes reforming of hydrocarbon for forming syngas, cooling the flow of initial syngas, expansion of the cooled flow of initial syngas, introduction of the extended flow of initial syngas in the feed zone in the distillation column, flow expansion of liquid remainders from the distillation column with the aid of the dilator of liquid forming the flow of cooled waste liquid, according to the first variant the method of the production of ammonia includes reforming of hydrocarbon for forming syngas, cooling of a stream initial syngas, expansion of the cooled stream initial syngas, introduction of the extended flow of initial syngas in the feed zone in the distillation column, flow expansion of liquid remainders from the distillation column with the aid of the dilator of liquid for forming the flow of the cooled waste liquid, the rectification of vapour from the feed zone in the distillation column for forming the upper flow of vapour with the decreased content of nitrogen and inert gases, cooling the upper flow of vapour in the indirect heat exchange with the flow of the cooled waste liquid for forming of partially condensed upper flow and flow of the partially heated waste liquid, the separation of the partially condensed upper flow into the flow of condensate and the flow of purified vapour of syngas with the decreased content of nitrogen and inert gases, the irrigation the distillation column by the flow of condensate, heating the flow of the purified vapour of syngas in the heat exchanger with the cross-section flow, heating the flow of partially heated waste liquid in the heat exchanger with a cross-section flow, the supply of the flow of the purified vapour of syngas from the heat exchanger with the cross-section flow into the outline of synthesis of ammonia. According to the second variant the method of the production of ammonia includes the reforming hydrocarbon with excess air for forming the flow of initial syngas, removal of nitrogen and inert gases from the flow of the syngas by distillation, thus provide cooling with the aid of the expansion of the liquid by means of the dilator-generator, and the upper flow partially condense the waste flow, cooled by means of expansion of the liquid remainder from the distillation column, and the supply of syngas with the decreased content of nitrogen and inert gases from distillation into the contour of the synthesis of ammonia at which the liquid remainders expand by means of the dilator of liquid with the extraction of work.

EFFECT: invention makes it possible to improve industrial and economic characteristics.

18 cl, 5 dwg, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to dehydrogenation or reforming of alcohols, in particular to a method of dehydrogenation of the primary alcohol, such as methanol or ethanol, for obtaining hydrogen, in particular for use in a fuel element with the purpose of obtaining electrical energy. In the method of dehydrogenation a catalyst containing copper is used, which includes a metallic carrier. To solve the given challenge the method includes bringing to contact of the initial raw mixture of the gases containing alcohol, with the catalyst of reforming in order to obtain a mixture of products of reforming, containing hydrogen, and the catalyst for reforming the contains a metallic spongy carrier and a coating on copper, at least, partially covering surface of the given metal spongy carrier where the given metal spongy carrier is obtained by means of the method including the leaching of aluminium from an alloy, containing aluminium and the main metal.

EFFECT: increased activity in the gas-phase reforming of primary spirits and increased stability.

129 cl, 13 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention relates to dehydrogenation or reforming of alcohols, in particular to a method of dehydrogenation of the primary alcohol, such as methanol or ethanol, for obtaining hydrogen, in particular for use in a fuel element with the purpose of obtaining electrical energy. In the method of dehydrogenation a catalyst containing copper is used, which includes a metallic carrier. To solve the given challenge the method includes bringing to contact of the initial raw mixture of the gases containing alcohol, with the catalyst of reforming in order to obtain a mixture of products of reforming, containing hydrogen, and the catalyst for reforming the contains a metallic spongy carrier and a coating on copper, at least, partially covering surface of the given metal spongy carrier where the given metal spongy carrier is obtained by means of the method including the leaching of aluminium from an alloy, containing aluminium and the main metal.

EFFECT: increased activity in the gas-phase reforming of primary spirits and increased stability.

129 cl, 13 tbl, 13 ex

FIELD: gas.

SUBSTANCE: synthesis gas producing method includes partial oxidation of the first portion of hydrocarbon in partial oxidation reactor, wherein the first flow leaving the reactor is obtained, cooled up to the temperature of 650° to 1000°C, and supplied to the reforming heat-exchanger. Then the second portion of hydrocarbon with steam passes through catalyst space in the reforming heat-exchanger, and the second flow leaving the reactor is generated, discharged from catalyst space, and mixed with the first flow leaving the reactor. Mixture passes through catalyst space in indirect heat exchange therewith, and mixture is cooled and catalyst space is heated, and after that the cooled mixture is taken from the reforming heat-exchanger. Modernising procedure of synthesis gas producing method includes partial oxidation reaction stage, whereat the first hydrocarbon flow is turned into the first flow leaving the reactor, heat recovery stage, whereat the first flow leaving the reactor is cooled, and steam is generated with the help of recovered heat, and outlet flow treatment stage, at which cooled flow leaving the reactor is received, and synthesis gas is produced with increased hydrogen content. It also includes the cooling stage of the first flow leaving the reactor up to the temperature of 650° to 1000°C, the stage at which the first cooled flow leaving the reactor is discharged into the reforming heat-exchanger, stage at which the second portion of hydrocarbon with steam passes through catalyst space in the reforming heat-exchanger, and the second flow leaving the reactor is generated, stage at which the second flow leaving the reactor is discharged from catalyst space and mixes with the first flow leaving the reactor, stage at which mixture passes through catalyst space in indirect heat exchange therewith, and mixture is cooled and catalyst space is heated, and stage at which cooled mixture is supplied from the reforming heat-exchanger to heat recovering stage.

EFFECT: allow to increase in capacity as to hydrogen.

21 cl, 2 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: hydroreactive mixture contains industrial aluminium ACD-1 powder and aluminium nanopowder with particle size of 70÷120 nm, as well as an activating additive in form of granular sodium hydroxide with the following ratio of components, in wt %: industrial ACD-1 powder 67÷79, aluminium nanopowder 30÷14, sodium hydroxide 3÷7.

EFFECT: faster heat release.

1 tbl

FIELD: chemistry.

SUBSTANCE: invention pertains to synthesising gas, containing carbon oxide and hydrogen, and reduction of concentration of carbon dioxide, method of obtaining dimethyl ether, as well as furnace for gas synthesis. The gas synthesis method involves reforming a gas through incomplete combustion of a hydrocarbon in space over a catalyst layer in a furnace. Temperature at the output of the catalyst layer is 1100-1300°C, and concentration of carbon dioxide in the gas synthesis is not more than 10% vol. Time for keeping the gas over the catalyst layer is 2 seconds or more. Dimethyl ether is obtained from the gas synthesis. The gas synthesis furnace allows for effusion of raw material containing, at least, hydrocarbon and oxidant, coming from a burner at the upper part of the furnace, incomplete combustion of the hydrocarbon in the space above the catalyst layer inside the furnace and synthesis of gas, containing carbon oxide and hydrogen in the catalyst layer. In the first alternative of the structure of the furnace, the space over the layer of catalyst satisfies conditions (1) and (2): (1) L≥D/2×cotanθ1 and (2) the time for keeping the gas in the space is 2 seconds or more, where L is the height of the space over the catalyst layer, D is the inner diameter of the furnace, θ1 is ½ the apical angle of the profile of the cone shaped width of the effusion stream into the furnace from the burner, and has values lying in the interval 6.5°≤θ1≤9°. In the second alternative of the structure of the furnace, the above mentioned space above the layer of catalyst satisfies the following conditions (1), (2) and (4): (1) L≥D/2×cotanθ1 and (2) the time the gas spends in the space is 2 seconds or more, and (4) L≥10d, where L is the height of the space over the catalyst layer, D is the inner diameter of the furnace, θ1 is ½ the apical angle of the profile of the cone shaped width of the effusion stream into the furnace from the burner, and lies in the interval 6,5°≤θ1≤9°, and d is the minimum diameter of a circle, encompassing all openings of the burner, through which the gas flows out.

EFFECT: synthesis of gas, which does not contain hydrocarbons, and with low concentration of carbon dioxide.

13 cl, 14 dwg, 7 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the field of catalysis and organic chemistry, in particular, to method of intensification of catalytic reactions under action of SHF (HF) radiation with essential reduction of energy consumption, which can be used when producing devices for hydrogen storage based on reversible reactions of hydration-dehydration of aromatic compounds. Method of hydrogen storage is based on carrying out reversible catalytic reactions of hydration-dehydration of organic substrate by heating it for absorption and releasing hydrogen using heterogeneous catalyst. As organic substrate, aromatic polycyclic hydrocarbons or aromatic oligomers are used. Heterogeneous catalyst includes carbonic or oxide carrier and active metal applied on it, chosen from the line Pt, Pd, Ni in amount of 0.1 to 15 weight %. Stage of hydrogen absorption and its release from organic substrate is carried out under action of SHF or HF radiation on the said heterogeneous catalyst.

EFFECT: increased rate of hydration and dehydration reactions.

5 cl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalyst for obtaining synthesis-gas, which contains carbon monoxide and hydrogen as main components, from raw material, containing hydrocarbon gas, which has 1 to 5 atoms of carbon in each molecule, such as natural gas, and oxygen; as well as to method obtaining synthesis-gas using such catalyst. Catalyst for synthesis-gas production, which contains metal of group VIII applied on carrier is described. Carrier contains the first component, second component and third component. The first component represents oxide of ,at least, alkaline earth metal chosen from the group of magnesium, calcium, strontium and barium. The second component represents oxide of, at least, an element chosen from the group of scandium, iridium and lantanoids. The third component is zirconium dioxide or substance containing zirconium dioxide as main component and has property of hard electrolyte, molar ratio of the second and first components being within the range of 0.02 to 0.40, and that of the third and first components within the range of 0.04 to 1.5. Method of production of synthesis-gas in presence of the above catalyst is also described.

EFFECT: essential reduction of reaction equipment size and improvement of equipment energy efficiency.

17 cl, 2 tbl, 24 ex

FIELD: technological processes.

SUBSTANCE: inventions may be used for preparation of shielded arc atmospheres, which contain nitrogen with hydrogen or nitrogen with hydrogen and carbon oxide that are used in glass, metallurgical, machine building industries. The first variant of shielded arc atmosphere preparation includes conversion of hydrocarbon gas, steam conversion of carbon oxide, cooling of conversion products with separation of condensed moisture and final purification of gas mixture from carbon dioxide and moisture at adsorption plants. Conversion of hydrocarbon gas is carried out in three stages: the first stage is carried out in free volume of device for oxidation of hydrocarbon gas with air; the second stage is carried out in volume of device that is filled with granular fire-resistant material for performance of steam and carbon-dioxide conversion of remaining hydrocarbon gas; the third stage is carried out in volume of device, which is filled with heat-resistant metal rings for saturation of gas flow with moisture and performance of steam conversion of carbon oxide. The second variant of shielded arc atmosphere includes conversion of hydrocarbon gas, steam conversion of carbon oxide, cooling of conversion products with separation of condensed moisture and final purification of gas mixture from carbon dioxide and moisture at adsorption plants. At that catalytic conversion of carbon oxide is regulated by amount of water vapors condensate, which is supplied into volume of device that is filled with heat-resistant metal rings for saturation of gas flow with moisture. The third variant of shielded arc atmosphere includes conversion of hydrocarbon gas, steam conversion of carbon oxide, cooling of conversion products with separation of condensed moisture and final purification of gas mixture from carbon dioxide and moisture at adsorption plants. At that part of hydrocarbon gas conversion products is sent to cooling device, bypassing device of steam conversion of carbon oxide, and further to adsorption purification unit in order to maintain preset content of carbon oxide in shielded arc atmosphere.

EFFECT: inventions allow to intensify the process and to prepare shielded arc atmosphere of triple composition.

4 cl

FIELD: chemistry.

SUBSTANCE: way of syngas cleaning includes: introduction of the flow of initial syngas, into the feed zone of the distillation column, flow expansion of the liquid remainder from the distillation column by means of a dilator of liquids with the extraction of work for forming the flow of the cooled waste liquid, the rectification of vapour from the feed zone for forming the upper flow of vapour with the decreased content of nitrogen and inert gases, cooling of the upper vapour flow in the indirect heat exchange with the flow of the cooled waste liquid for forming the of partially condensed upper flow and flow of the partially heated waste liquid, separation of the partially condensed upper flow into the flow of condensate and the flow of the purified vapour of syngas with the decreased content of nitrogen and inert gases and the irrigation of distillation column by the flow of condensate. By the first variant the method of production of ammonia includes reforming of hydrocarbon for forming syngas, cooling the flow of initial syngas, expansion of the cooled flow of initial syngas, introduction of the extended flow of initial syngas in the feed zone in the distillation column, flow expansion of liquid remainders from the distillation column with the aid of the dilator of liquid forming the flow of cooled waste liquid, according to the first variant the method of the production of ammonia includes reforming of hydrocarbon for forming syngas, cooling of a stream initial syngas, expansion of the cooled stream initial syngas, introduction of the extended flow of initial syngas in the feed zone in the distillation column, flow expansion of liquid remainders from the distillation column with the aid of the dilator of liquid for forming the flow of the cooled waste liquid, the rectification of vapour from the feed zone in the distillation column for forming the upper flow of vapour with the decreased content of nitrogen and inert gases, cooling the upper flow of vapour in the indirect heat exchange with the flow of the cooled waste liquid for forming of partially condensed upper flow and flow of the partially heated waste liquid, the separation of the partially condensed upper flow into the flow of condensate and the flow of purified vapour of syngas with the decreased content of nitrogen and inert gases, the irrigation the distillation column by the flow of condensate, heating the flow of the purified vapour of syngas in the heat exchanger with the cross-section flow, heating the flow of partially heated waste liquid in the heat exchanger with a cross-section flow, the supply of the flow of the purified vapour of syngas from the heat exchanger with the cross-section flow into the outline of synthesis of ammonia. According to the second variant the method of the production of ammonia includes the reforming hydrocarbon with excess air for forming the flow of initial syngas, removal of nitrogen and inert gases from the flow of the syngas by distillation, thus provide cooling with the aid of the expansion of the liquid by means of the dilator-generator, and the upper flow partially condense the waste flow, cooled by means of expansion of the liquid remainder from the distillation column, and the supply of syngas with the decreased content of nitrogen and inert gases from distillation into the contour of the synthesis of ammonia at which the liquid remainders expand by means of the dilator of liquid with the extraction of work.

EFFECT: invention makes it possible to improve industrial and economic characteristics.

18 cl, 5 dwg, 3 tbl

FIELD: chemistry.

SUBSTANCE: way of syngas cleaning includes: introduction of the flow of initial syngas, into the feed zone of the distillation column, flow expansion of the liquid remainder from the distillation column by means of a dilator of liquids with the extraction of work for forming the flow of the cooled waste liquid, the rectification of vapour from the feed zone for forming the upper flow of vapour with the decreased content of nitrogen and inert gases, cooling of the upper vapour flow in the indirect heat exchange with the flow of the cooled waste liquid for forming the of partially condensed upper flow and flow of the partially heated waste liquid, separation of the partially condensed upper flow into the flow of condensate and the flow of the purified vapour of syngas with the decreased content of nitrogen and inert gases and the irrigation of distillation column by the flow of condensate. By the first variant the method of production of ammonia includes reforming of hydrocarbon for forming syngas, cooling the flow of initial syngas, expansion of the cooled flow of initial syngas, introduction of the extended flow of initial syngas in the feed zone in the distillation column, flow expansion of liquid remainders from the distillation column with the aid of the dilator of liquid forming the flow of cooled waste liquid, according to the first variant the method of the production of ammonia includes reforming of hydrocarbon for forming syngas, cooling of a stream initial syngas, expansion of the cooled stream initial syngas, introduction of the extended flow of initial syngas in the feed zone in the distillation column, flow expansion of liquid remainders from the distillation column with the aid of the dilator of liquid for forming the flow of the cooled waste liquid, the rectification of vapour from the feed zone in the distillation column for forming the upper flow of vapour with the decreased content of nitrogen and inert gases, cooling the upper flow of vapour in the indirect heat exchange with the flow of the cooled waste liquid for forming of partially condensed upper flow and flow of the partially heated waste liquid, the separation of the partially condensed upper flow into the flow of condensate and the flow of purified vapour of syngas with the decreased content of nitrogen and inert gases, the irrigation the distillation column by the flow of condensate, heating the flow of the purified vapour of syngas in the heat exchanger with the cross-section flow, heating the flow of partially heated waste liquid in the heat exchanger with a cross-section flow, the supply of the flow of the purified vapour of syngas from the heat exchanger with the cross-section flow into the outline of synthesis of ammonia. According to the second variant the method of the production of ammonia includes the reforming hydrocarbon with excess air for forming the flow of initial syngas, removal of nitrogen and inert gases from the flow of the syngas by distillation, thus provide cooling with the aid of the expansion of the liquid by means of the dilator-generator, and the upper flow partially condense the waste flow, cooled by means of expansion of the liquid remainder from the distillation column, and the supply of syngas with the decreased content of nitrogen and inert gases from distillation into the contour of the synthesis of ammonia at which the liquid remainders expand by means of the dilator of liquid with the extraction of work.

EFFECT: invention makes it possible to improve industrial and economic characteristics.

18 cl, 5 dwg, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to dehydrogenation or reforming of alcohols, in particular to a method of dehydrogenation of the primary alcohol, such as methanol or ethanol, for obtaining hydrogen, in particular for use in a fuel element with the purpose of obtaining electrical energy. In the method of dehydrogenation a catalyst containing copper is used, which includes a metallic carrier. To solve the given challenge the method includes bringing to contact of the initial raw mixture of the gases containing alcohol, with the catalyst of reforming in order to obtain a mixture of products of reforming, containing hydrogen, and the catalyst for reforming the contains a metallic spongy carrier and a coating on copper, at least, partially covering surface of the given metal spongy carrier where the given metal spongy carrier is obtained by means of the method including the leaching of aluminium from an alloy, containing aluminium and the main metal.

EFFECT: increased activity in the gas-phase reforming of primary spirits and increased stability.

129 cl, 13 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention relates to dehydrogenation or reforming of alcohols, in particular to a method of dehydrogenation of the primary alcohol, such as methanol or ethanol, for obtaining hydrogen, in particular for use in a fuel element with the purpose of obtaining electrical energy. In the method of dehydrogenation a catalyst containing copper is used, which includes a metallic carrier. To solve the given challenge the method includes bringing to contact of the initial raw mixture of the gases containing alcohol, with the catalyst of reforming in order to obtain a mixture of products of reforming, containing hydrogen, and the catalyst for reforming the contains a metallic spongy carrier and a coating on copper, at least, partially covering surface of the given metal spongy carrier where the given metal spongy carrier is obtained by means of the method including the leaching of aluminium from an alloy, containing aluminium and the main metal.

EFFECT: increased activity in the gas-phase reforming of primary spirits and increased stability.

129 cl, 13 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention is referred to the area of hydrocarbons preparation by catalytical hydrodeoxygenation of products of fast pyrolysis of a biomass and working out of the catalyst for this process. The catalyst of oxygen-organic products hydrodeoxygenation of fast pyrolysis of lignocellulose biomasses, containing either precious metal in amount of no more 5.0 wt % or containing nickel, or copper; either iron, or their combination in a non-sulphide restored shape in amount of not more than 40 wt % and transitive metals in a non-sulphide shape in amount of not more than 40 wt %, carrying agent - the rest, is described. Three variants of the catalyst preparation method, providing application of transition metals on the carrying agent by a method of impregnation of the carrying agent solutions of metal compounds are described, or simultaneous sedimentation of hydroxides or carbonates of transition metals in the presence of the stabilising carrier, or the catalyst is formed by joint alloying/decomposition of crystalline hydrate nitrates of transition metals together with stabilising components of zirconium nitrate type. The process of oxygen-organic products hydrodeoxygenation of a biomass fast pyrolysis is performed using the above described catalyst in one stage at pressure of hydrogen less than 3.0 MPa, temperature 250-320°C.

EFFECT: increase stability in processing processes of oxygen-containing organic raw materials with the low content of sulphur, and also soft conditions of process realisation.

10 cl, 12 ex, 2 tbl

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