Production of cu/zn/al-catalysts via formate route

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing Cu/Zn/Al catalysts, to a catalyst produced using this method, as well as to its use in methanol synthesis, methanol reforming and for low-temperature conversion of carbon monoxide. A method is described for preparing Cu/Zn/Al catalysts, involving preparation of a first aqueous solution which contains at least copper formate and zinc formate, preparation of a second solution which contains a precipitation agent, wherein the first and/or second solution contains an aluminium hydroxide sol/gel mixture, combining both solutions, separating the obtained precipitate from the aqueous phase which forms waste water, washing the precipitate until an alkali content, based on a catalyst which calcined at 600°C, of not less than 500 parts per million is attained, and drying. A catalyst prepared using this method is described, and its use in methanol synthesis, methanol reforming and conversion of carbon monoxide.

EFFECT: simpler technology of producing catalyst and increased activity of the catalyst.

32 cl, 5 tbl, 8 ex

 

The invention relates to a method for Cu/Zn/Al catalysts, the catalyst, which can be obtained by this method and also to its use for the synthesis of methanol and reforming of methanol and for low-temperature conversion of carbon monoxide.

Cu/Zn/Al catalysts, which catalyze the conversion of CO, CO2and H2in methanol, known for a long time. The atomic ratio of copper and zinc can these known catalysts to change, and usually the copper is present in excess. In addition, part of the zinc component may be replaced by calcium, magnesium and/or manganese. Aluminum oxide, used as an " oven " substance, can also be partially replaced by chromium oxide.

So, for example, from the document DE 1 965 007 known catalyst for low-temperature methanol synthesis. To obtain a first catalyst from a solution of suitable salts of zinc and copper by adding carbonates of alkali metals are planted corresponding basic carbonate. It is separated from the aqueous phase, dried and calcined to obtain the corresponding oxides. Then the oxides of zinc and copper is mixed with aluminum oxide, and obtained a suspension of the oxides, which contains not more than 20% of the solid phase. It then homogenized, and the homogenization takes so much to dispersed oxides were not deposited in t the value of 2 hours. After homogenization, the mixture is dried, tabletirujut and calcined. To convert the oxide form of the catalyst additionally restore the flow of hydrogen.

From the document DE 2 302 658 A known way to obtain a catalyst precursor, which can be used for methanol synthesis. To obtain a catalyst precursor first get the first precipitate, which contains divalent metal, for example zinc and trivalent metal such as aluminum in the form of any compound which can be decomposed thermally to the corresponding oxides. Suitable compounds are, for example, carbonates or bicarbonates. Next, get a second precipitate, which contains copper compounds which can be thermally decompose to oxides. Both sediment mix. This is immediately followed by the usual steps of drying and calcination, to obtain from the metal compounds are oxides and, if possible, to cause the formation of spinel structure. Then the solid phase tabletirujut. In order to convert the precursor into the active catalyst tablets restore the flow of hydrogen.

In the document DE 2 056 612 describes a method of producing methanol, in which the reaction takes place on the catalyst containing zinc, copper and aluminum. The catalyst refers to a series of mixed crystals of the formula (CuxZny)Al2/sub> (OH)16× CO3× 4H2O, in which x and y can take numerical values from 0.5 to 5.5, and the sum of x and y is equal to 6. Connection with mixed crystals precipitated from an aqueous solution that contains a salt of copper, zinc and aluminum, adding alkali carbonate, alkali bicarbonate or mixtures thereof. The atomic ratio of the sum of divalent metals copper and zinc to trivalent aluminum in a series of mixed crystals and constantly is 6:2. To obtain copper, zinc and aluminum in the form of appropriate salts, preferably nitrates, dissolved in water, and, moreover, in the proportion that corresponds to the desired composition of the catalyst. This solution is heated to a temperature of from 50 to 100°C, preferably from 70 to 100°C, and processed with the proper heated aqueous solution of a precipitant, for example, a carbonate of an alkali metal. Resulting precipitate is filtered off, washed and dried. The dried compound calcined at temperatures in the range from 200 to 500°C for 12-24 hours. The calcined product formed into tablets and then by restoring the flow of hydrogen is transferred to the active form of the catalyst.

In the document US 4,279,781 described catalyst for methanol synthesis, which includes the oxide of copper and zinc, and the metal oxide for thermal stabilization, for example, aluminum oxide. The ratio of copper oxide to about the sid of zinc based on the weight of the metal is from 2:1 to 3.5:1. Obtaining catalyst occurs through the total precipitation of the dissolved salts of zinc, copper and aluminum, for example, nitrates. This ensures thorough mixing of the catalyst components. To obtain the active form of the catalyst precursor restore the flow of hydrogen.

From the document EP 0 125 689 A2-known catalyst for methanol synthesis, which as catalytically active substances contains copper oxide and zinc oxide, and as the " oven " of a substance is aluminum oxide. The catalyst is different in a certain pore radius, and the proportion of pores with a diameter from 20 to 75 D (mesopores) is at least 20%, and the proportion of pores with a diameter of more than 75 D (macropores) is at most 80%. The desired distribution of the pore radius can be assured, however, that upon receipt of the catalyst used colloidal dispersed oxide or aluminum hydroxide. For these catalysts, the catalytically active components, copper oxide and zinc oxide are precipitated from aqueous solutions of the corresponding salts, such as nitrates, sulfates, chlorides, acetates, using alkaline substances in the presence of dispersed colloidal oxide or hydroxide of aluminum. Product deposition can then be dried, calcined, pressed into the molded product and, if necessary, in the becoming.

From the document EP 0 152 809 A2-known catalyst for synthesis of methanol and an alcohol mixture containing higher alcohols, which in the form of an oxide precursor contains copper oxide and zinc oxide, which by restoring at least part of the copper oxide can be converted into the catalytically active components, and aluminum oxide as " oven " substance and at least one alkali carbonate or alkali oxide. The proportion of pores with a diameter from 14 to 7.5 nm in oxide precursor is from 20 to 70% of full volume. The alkali content is from 13 to 130×10-6gram-atoms of alkali metal per gram of the oxide precursor. Component aluminum oxide were received from dispersed colloidal aluminum hydroxide. For the preparation of the catalyst is usually used solutions of nitrates of copper and zinc and the deposition is conducted preferably in an aqueous solution of K2CO3. The concentration of the solution is preferably from 5 to 20 wt.%. Instead of nitrates can also come from the corresponding formate or acetates of the metals. The deposition can be carried out using a solution of bicarbonate of potassium. The deposition may be performed periodically or continuously. Preferably the deposition is carried out by the continuous connection of a solution of nitrate of copper and zinc containing colloi the material dispersed aluminum hydroxide, with a water solution of K2CO3. Immediately after deposition of the washed precipitate is calcined catalyst and alkalinized by treating a solution of the compound of the alkali metal. Podslushannyy the catalyst precursor after drying pressed a manner that is itself known, with the formation of the molded body, and can be added to the lubricant as graphite. In order to convert the catalyst precursor into the active form, it is reactivated by hydrogen.

From the document WO 03/053569 A1 is known a catalyst for methanol synthesis, which contains copper oxide and zinc oxide as catalytically active substances, and alumina as the " oven " substance. For the preparation of the catalyst from a solution that contains salts of Cu and Zn, and part of the Al salt with a solution of alkali carbonate or alkali aluminate is precipitated by the appropriate hydroxocobalamin or hydroxides. Or a solution of salts of Cu and Zn, or a solution of alkali carbonate or alkali aluminate contains the Sol of aluminum hydroxide. The precipitate is separated from the solution in which the precipitation, washed, dried and optionally calcined. Upon receipt of the catalyst preferably extend from the nitrates of copper and zinc, which are deposited preferably sodium carbonate or sodium aluminate.

In the document JP 2001-144779 described honey is about-zinc catalyst for the reaction of carbon monoxide and water to obtain carbon dioxide and water, given the fact that the solution containing the copper formate and formate, zinc, mixed with an aqueous solution of alkaline material. The resulting precipitate is then filtered, washed, dried and calcined. The calcined solid Usacheva the addition of water and applied to the surface of the substrate with a honeycomb structure. As a binder can be applied Sol of aluminum oxide or Sol of zirconium oxide. They can be added into a suspension of calcined precipitate. While aluminum oxide is distributed in the catalyst is not uniform, but is only between the catalyst particles. Thus, his task is only to act as a binder between containing copper and zinc particles of the catalyst and the substrate with a honeycomb structure, and it is not an active component of the catalyst.

To obtain Cu/Zn/Al catalysts for methanol synthesis in a technically implemented the way they are used mainly nitrates of zinc and copper because of its good solubility in water. When the precipitation accumulates waste water that contains large amounts of sodium nitrate. When discharged into surface waters, it would have led to excessive concentration of fertilizer. Therefore, prior to discharge to surface water content of water-soluble nitrogen accumulated in the receiving catalysts for methanol synthesis, otruba is these waters should be significantly reduced.

Therefore, the object of the invention is to develop a method of obtaining a Cu/Zn/Al catalysts, which, on the one hand, helps to visibly reduce the content of salt in the waste water, in particular, nitrates, alkali metal, and which, on the other hand, provides catalysts for methanol synthesis, the activity of which is at least comparable to the activity of the catalyst obtained from the nitrate of the metal.

This problem is solved by a method with the distinctive signs of paragraph 1 of the claims. An advantageous form of implementation of the method are the object of dependent claims.

In the process for Cu/Zn/Al catalysts according to the invention will first receive a first aqueous solution containing at least copper formate and formate zinc. Next, get the second solution, which contains the precipitator. Under the precipitator is understood to mean a reagent which directly or indirectly produces ions, for example, hydroxyl ions and/or carbonate ions, which can precipitate metals, particularly copper, zinc and aluminum. The first solution and/or the second solution contains the Sol/gel mixture of aluminum hydroxide. Under the Sol of aluminum hydroxide is understood finely dispersed distribution of aluminum hydroxide in water, in which were already polyacid formed by condensation of aluminum hydroxide, however, in vodnochas the naked eye can not see any particles, so the solution is transparent. Under the gel of aluminum hydroxide is the dispersion of aluminum hydroxide in water, and formed large agglomerates of PolicyKit, so that even the naked eye can distinguish particles, for example, as the turbidity of the aqueous phase.

At the stage of deposition of the first solution and the second solution are combined, and the obtained residue. The precipitate was separated from the aqueous phase and the aqueous phase forms the waste water, which is carried out for processing.

The precipitate is washed until the concentration of alkali is less than 500 parts per million per calcined at 600°C the catalyst. Then the precipitate is dried, optionally calcined and grind.

In the method according to the invention the waste water containing nitrates, is not formed. Through the use of copper formate and formate zinc as water-soluble salts of copper and zinc in waste water contains formatnya ions, which can be recycled more simple way. Through the use of formate load of wastewater organic material remains relatively low. This is an advantage compared with the use of higher carboxylic acids, such as acetic acid, as they are due to the higher number of links C-H increase the load of wastewater organics. Another advantage is the Econ is mikeski best obtaining formic acid, which is necessary to obtain formate, copper and zinc, so that the method according to the invention is advantageous also from an economic point of view.

For the method according to the invention it is essential that at least part of the aluminum into the solution, which is the deposition, in the form of a Sol of aluminum hydroxide, and the other part is like a gel of aluminum hydroxide. If you refuse to add the Sol/gel mixture of aluminum hydroxide in the solution of metal salts decreases the product yield in weight per unit time (GZA, [kg methanol/{kg of catalyst × h}]).

The residue after the separation of thoroughly washed, so that the content of alkali, calculated on calcined at 600°C the oxide catalyst, fell to values less than 500 ppm, preferably less than 400 ppm, in particular, to values in the interval from 100 to 300 parts per million of Accumulated during this wash water can be combined with containing formate waste water and, if necessary, revise. After washing, drying and optionally annealing the oxide form of the catalyst is still detects the residual content of formate less than 5 wt.%, preferably from 0.5 to 4 wt.%, in particular, preferably 1-2 wt.%. The content of the formate can be defined, for example, oxidative titration or quantitative chromatographic analysis, for example, HPLC.

In addition to fo is Miata copper and zinc formate, the first aqueous solution may also contain conventional promoters, such as calcium, magnesium, manganese, cerium, lanthanum and ruthenium or palladium. In addition to these promoters can also be used by other promoters. Promoters are introduced preferably in the form of their formate, preferably in the first aqueous solution. Their share in oxide form of the catalyst, calculated on an oxide, is preferably less than 10 wt.%, in particular less than 5 wt.%. If the promoters are noble metals, such as ruthenium or palladium, they are preferably contained in amounts of less than 1 wt.%.

As already mentioned, in the method according to the invention the first and/or second solution contains the Sol/gel mixture of aluminum hydroxide. As the initial product for the Sol/gel mixture of aluminum hydroxide may, for example, to use the product commercially available. However, the Sol/gel mixture of aluminum hydroxide can also get the fact that a dilute solution of an aluminum salt add a little ammonium hydroxide, and heating are avoided, to prevent turning in Angelov V. coarse. According to another variant, it is possible to solution of alkali aluminate add a small amount of acid, forming a Sol/gel aluminum hydroxide. Predpochtitel is but the Sol/gel aluminum hydroxide is contained in the first aqueous solution. The products formed from the Sol/gel of aluminum hydroxide on the following stages are used as the substrate, and " oven " substance. Not bound by this theory, the inventors suggest that during heating of the Sol/gel mixture of aluminum hydroxide is formed three-dimensional mesh, in free volumes which are crystals of copper within the active components obtained after recovery. Because this is complicated further intergrowth of crystals of copper in the synthesis of methanol, which increases the stability of the catalyst and its service life in industrial processes.

It is believed that the zinc oxide, firstly, has a strong influence on the formation of the active components, and secondly, partly due to its needle-like structure contributes to the stability of the catalyst. In addition, the zinc oxide acts as a trap for toxic substances reacting with sulfur compounds, which can accidentally swallow.

Present in known cases, as promoters of the oxides of calcium, magnesium, manganese, cerium and lanthanum are also stabilizirawe.

The first solution that contains a mixture of different metal salts, preferably receive the fact that

- receive an aqueous solution of copper formate, completely dissolving the copper salt by adding formic acid,

- get the same dispersion or solution of zinc salt,

- receive an aqueous solution of an aluminum salt, and

- solution of copper formate, dispersion or solution of salt of zinc and a solution of an aluminum salt bridge.

If Cu/Zn/Al catalyst should be modified by the promoters, they can be administered, for example, in the first solution. Promoters may be added in the form of suitable salts, such as carbonates, oxides or hydroxides. By themselves, these salts can be added at any point in time, i.e. in a solution of copper formate, in a dispersion or a solution of zinc salts, or after connection of a solution of copper formate and dispersion or solution of zinc salts. Especially dear promoters, as the noble metals, are added to the suspension, preferably at a later stage of the process, for example, before spray drying, or napylyaetsya micronized dry powder after spray drying.

Upon receipt of a solution of copper formate and zinc is preferably added so much of formic acid to the calculation on the amount of salt used copper and zinc, with regard to stoichiometry, formic acid was in excess of at least 10 mol%, preferably from 10 to 20 mol%, particularly preferably from 14 to 16 mol%. The pH of a solution of copper formate after addition of formic acid is preferably less than 3, preferably less than 2.5.

In the main the compulsory implementation of the solution or dispersion of the zinc salts are combined with a solution of copper formate. After connection of a solution or dispersion of copper formate and zinc salts such as copper and zinc are in solution in the form of formate. The resulting solution preferably has a pH in the range from 3.0 to 4.0, particularly preferably from 3.5 to 3.7. Then to a solution of copper with zinc add a solution of an aluminum salt.

The solution of an aluminum salt is preferably introduced into the copper-zinc solution in several parts. At least the first part of the solution of an aluminum salt get to at least a first portion of an aluminum salt was dissolved in water by adding formic acid.

Upon receipt of the first part of the solution of an aluminum salt are preferably so that, for example, is first dissolved in water, sodium aluminate, and then add as much of formic acid so that the pH was less than 5, preferably from 4.5 to 2, in particular from 4 to 3. Preferably add enough formic acid to obtain a clear solution.

Next, the second part of the solution of an aluminum salt get preferably those that dissolve in water the second part of the aluminium salts. In this second part of the solution of an aluminum salt of formic acid is added. For the preparation of the first solution, which contains a mixture of all metal salts prior to deposition, in this case, in an aqueous copper-zinc solution preference is sustained fashion enter the first part of the solution of an aluminum salt and the second part of the solution of an aluminum salt, preferably separated by time.

The second part of the solution of an aluminum salt get, for example, the fact that NaAlO2dissolve in water. The pH of an aqueous solution NaAlO2is, depending on the excess of alkali in the source material, from 11 to 14, preferably from 12 to 13.

The proportion of the first and second parts of a solution of an aluminum salt can be calculated content of aluminum in the range from 0:100 to 100:0, preferably from 1:99 to 99:1, particularly preferably from 30:70 to 70:30, and in particular, preferably selected about 50:50.

Obtaining solutions of aluminium salts is carried out preferably at temperatures below 40°C, particularly preferably below 30°C. This temperature is also not exceeded, when the solution of an aluminum salt is introduced into the copper-zinc solution, or a solution of copper formate or dispersion, or a solution of zinc salts. This suppresses the formation of coarse polymeric aluminum compounds. Under coarse polymeric aluminum compounds are defined as complex hydroxocobalamine aluminum, which form a distinct eye particles, falling relatively quickly. Therefore, to obtain solutions is preferably in the boiler, which is equipped with appropriate cooling device.

Aluminum salts suitable for use in the method of solenoidality, are, for example, di - and reformat aluminum hydrate Al(NO3)3or NaAlO2. Solutions of aluminium salts are preferably the concentration of aluminum in the range of from about 0.4 to about 1.1 mol/l, particularly preferably from about 0.9 to 1.1 mol/l While the upper values of these intervals are determined by the limits of solubility of salts of aluminum, while the lower bounds are derived from economic considerations.

As copper salts, preferably applied such salts, the anions of which are oxides, hydroxides and carbonate or received by the recovery of derivatives and that in the first solution or in oxide form of the catalyst is no longer to be detected individually among distinct elements. Preferably, the copper salt is selected from CuO, Cu(OH)2and Cu(OH)2×

ISSS3.

As zinc salts preferably selects the connection of zinc, the anion of which in the first solution or in oxide catalyst precursor is no longer detected as interfering with, preferably as a distinct element. Preferably as a salt of zinc is selected ZnO.

The concentration of the solution of copper formate is preferably selected so that upon connection of a solution of copper formate and a solution or dispersion of zinc salts, the concentration of copper ostanavlivalas is in the range of from about 0.1 to about 0.5, in particular, preferably from 0.3 to about 0.5 mol/L. the Upper value is determined by the boundary of the solubility of salts of copper, and the lower bound is derived from economic considerations, since the processing of dilute solutions leads to increased amounts of, for example, that affect the determination of the size of the device that implements the method according to the invention.

The concentration of the zinc salts are preferably selected so that upon connection of a solution of copper formate and the solution or suspension zinc salts zinc concentration preferably lying in the range of from about 0.1 to about 0.2 mol/l, preferably from about 0.15 to about 0.2 mol/L. There is also the upper bound is obtained from the solubility of the zinc salts and the lower bound - economic reasons.

The solution of an aluminum salt is preferably introduced into the copper-zinc solution. The pH of the first solution, which preferably contains the full amount of Cu, Zn and Al, while preferably set to a value in the range from 4.0 to 5.0, particularly preferably from 4.2 to 4.4.

As a precipitator is preferably applied to the base of the alkali metals. As bases alkali metal used preferably carbonates of alkali metals, carbonates of alkali metals or aluminates of alkali metals. As the alkali metal preferably used sodium. If, for example, as the precipitator is used a solution of soda, the soda concentration of the solution is preferably from 80 g/l to 200 g/l, preferably from 170 to 180 g/L.

According to another form of implementation of the method according to the invention as a precipitant used hydrogen peroxide. Hydrogen peroxide is introduced into the first solution or dispersion that contains copper, zinc and aluminum in the form of formate or gidroksiapatitov. Due to the hydrogen peroxide formate is oxidized to carbonate, which precipitates rolled metals in the form of their hydroxocobalamin, carbonates or hydroxides. In the oxidation of formate anions initially formed the anions bicarbonate, then with increasing pH, the carbonate anions. Used anions metals are deposited sequentially in a series of Al-Cu-Zn as hydroxocobalamin. Thus, it is possible to abandon the use of carbonate-bearing alkaline solution. In addition to hydrogen peroxide, can also be used other suitable oxidizing agents such as ozone.

To obtain the oxide precursors of catalysts, first connect the first and second solution, and get the precipitate. The deposition is preferably carried out so that during deposition, the pH value was maintained in the range from 3.5 to 7.5, preferably from 6.0 to 7.0 in particular, preferably 6,5 ± 0,1.

Te is the temperature during the precipitation held preferably in the range of from 25 to 95°C, in particular, preferably from 50 to 75°C.

After mixing the precipitate formed is preferably subjected to maturation. This can, for example, to translate the suspension is formed by mixing the first and second solution in the tank maturation, in which the suspension can be rotated, for example, a suitable stirrer.

The maturation is carried out preferably within a period from 10 minutes to 10 hours, particularly preferably from 1 to 5 hours.

When ripe, the suspension is preferably maintained at an elevated temperature, and maturation occurs, in particular, at temperatures over 60°C, particularly preferably in the range of from 65 to 80°C.

The connection of the first and second solutions is preferably carried out so that the solution injected simultaneously into the mixing tank and mix there. This tank is rough mixing, for example, by means of a suitable stirrer.

However, it is preferable that the deposition was carried out as a continuous deposition. It requires to have the appropriate dimensions of the mixing tank, which is continuously served the first and the second solution and the resulting mixture is continuously divert. Preferably the volume of the mixing tank is chosen so as to achieve a continuous supply of the first and second solutions in the MCA is sustained fashion tank and continuous removal of the mixture, moreover, the residence time of the mixture is preferably from about 0.1 seconds to 10 minutes, particularly preferably from about 1 to 120 seconds, particularly preferably from 1 to 20 seconds.

The residence time of the mixture in the mixing tank is strongly dependent on the size of the mixing tank, and flow rate. The respective sizes of the mixing tank and the velocity of the inlet and outlet solutions or suspensions may be selected by the technician.

After deposition and held when necessary stage of ripening of the precipitate was separated from the aqueous phase, which can be applied by conventional methods, for example, filtration. The precipitate is then washed and dried. Preferably after drying, the precipitate is calcined. The calcination is carried out, depending on the method used, at temperatures of preferably from 140°C to 1000°C, particularly preferably from 170°C to 350°C for at least 0.1 second, preferably at least 4 minutes, particularly preferably from 20 minutes to 8 hours, particularly preferably from 30 minutes to 4 hours. Depending on the chosen conditions of annealing remaining in the sediment on the filter formate during calcination to remove essentially all of the oxidation in air or by intramolecular redox reaction in an inert gas. At last lyrics by the tea Cu(HCO 2)2× H2O in all probability first decomposes to H2and CuC2O2. Then the copper oxalate reacts to the formation of the CO2and elemental copper. The calcination may be conducted in conventional devices. In industrial production because of better heat transfer are used as pulse reactors, and reactors with a fluidized bed of catalyst is preferred from the point of view of a rotary kiln. Pulsation dryer makes possible very short drying times, in the region of less than 1 second, typically in the range from 0.1 seconds to 4 minutes, and can be applied very high temperatures up to 1000°C.

The calcined powder can, if necessary, grind them and then with the usual tools to process, for example, into tablets or extrudates. However, you can also cosmocity powder, grind them to a very small grain size and apply the obtained suspension on a suitable substrate, for example, honeycomb. You can use the usual methods. Thus a suitable grain size is set to the average grain size D50ranged from 10 nm to 10 μm, particularly preferably from 100 nm to 5 μm. The average grain size can be determined, for example, a laser diffraction. Suitable catalysts can be obtained, for example, grain size, where mn is the significance of D 50is in the range of about 2-3 microns.

A particular advantage of the method according to the invention is that accumulated after separation of the sludge waste water containing formate, can be treated with relatively simple means. For this purpose, containing formate waste water is preferably subjected to oxidation processing, and formatnya ions oxidize in aqueous solution, depending on pH, mainly to carbonate, hydrocarbonate, carbon dioxide and water. The content of the formate, for example, in the form of sodium formiate, in the waste water is in the technical implementation of the method according to the invention in the range from 0.2 to 1.5 mol/l, particularly preferably from 0.8 to 1.0 mol/l, but may also be present in higher or lower concentrations of formate. By oxidative treatment of wastewater can reduce the concentration of formate to values less than 0.1 mol/l, preferably from 0.01 to 0.075 mol/l, particularly preferably from 0.02 to 0.04 mol/L. This corresponds to a reduction of formate contained in the waste water, more than 95%.

According to a preferred form of implementation for the oxidation process containing formate waste water add hydrogen peroxide. Hydrogen peroxide in containing formate waste water to relax the Ute preferably in the form of a solution, the concentration of hydrogen peroxide which lies in the range of from about 9 to 20 mol/l (up to about 60 wt.%). For the case, when should observe the specific rules of transportation, the concentration of the used hydrogen peroxide solution can be increased to more than 90 wt.%. Preferably the hydrogen peroxide is added in excess, and the quantity added in the calculation contained in the waste water formate is selected in the range from 160 to 200 mol%, particularly preferably from 160 to 170 mol%. In addition to hydrogen peroxide, may also be used by other oxidants, such as ozone or sodium hypochlorite solution. When choosing oxidant plays a role, for example, cost and legislation on the environment. Depending on the legal restrictions and additional purification steps are not required to oxidize all the number formatnya ions. A significant decrease in the concentration formatnya ions chemical oxidation treatment may be already sufficient, and processed in such a way that waste water can be directed, for example, on the degree of biological clarification.

Treatment with hydrogen peroxide containing formate waste water is conducted preferably at 20-95°C, particularly preferably at 50-80°C in the pH range of 4-8, cha is in the surrounding area, preferably from 5.0 to 6.5.

According to one form of implementation of the method according to the invention oxidation treatment containing formate waste water is already before separating the precipitate. This can, for example, after the stage of maturation to add to the suspension a suitable quantity of hydrogen peroxide, and separating the precipitate only after significant oxidative cleavage formatnya ions. In alternate sequence of process steps can be performed adding hydrogen peroxide solution to the solution of formate containing Cu, Zn, Al, and precipitator (carbonate ions) are obtained by oxidation of formiate ions.

Oxidative treatment of waste water by addition of a suitable oxidant, such as hydrogen peroxide, is very simple to carry out technically, and it also allows you to process waste water, which contains a relatively high concentration formatnya ions. However, it is also possible to oxidation treatment was conducted exclusively biological treatment containing formate waste water. When waste water containing formate, can optionally be diluted to a suitable concentration.

Oxidative treatment containing formate waste water is preferably so that the concentration of formate is the waste water after the oxidation treatment was less than 0.1 wt.%.

If you compare the Cu/Zn/Al catalyst obtained by the use of formate, with catalysts, which were obtained on the basis of nitrates, the catalyst obtained by the method according to the invention, is better or comparable activity and comparable selectivity. Also long-term stability of the catalyst obtained by the use of formate, determined at 250°C in the test for methanol synthesis, is slightly better or at least comparable with the stability of the catalyst, which was derived from the nitrates of the metals. Therefore, an object of the invention is the catalyst, which can be obtained as described above.

The catalyst according to the invention in its oxide form contains less than 5 wt.%, preferably from 0.5 to 4 wt.%, in particular, preferably from 1 to 2 wt.% formate, calculated as formic acid. By annealing under mild conditions can preserve the structure of formate, which, according to common in catalysis rule "key and lock" can play an important role in achieving high activity. During annealing in gentle conditions at approximately 170°C for 4 minutes to form a catalyst, which has a very high activity at 250°C.

The catalyst according to the invention has a high volume of mesopores. The share of mesopores is the radius of 3.75 to 7.0 nm is preferably more than 30%, preferably from 30 to 80% of the total pore volume. Full pore volume includes the volume of pores with a radius of 3.75 to 7500 nm. Pore volume can be determined by indentation method of mercury. Preferably, the total volume of pores defined for tablets 6×4 mm, 100 mm3/g -700 mm3/g, preferably 250 mm3/g - 450 mm3/year

The content of copper, calculated as CuO, and is referred to the weight of the oxide form of the catalyst, taking into account the loss on ignition at 600°C, is selected preferably between 55 and 69 wt.%, in particular, preferably 60 and 63 wt.%.

The content of zinc, calculated as ZnO and related to the weight of the oxide form of the catalyst, taking into account the loss on ignition at 600°C is selected preferably between 20 and 33 wt.%, in particular, preferably between 25 and 31 wt.%.

The content of aluminum, calculated as Al2O3and referred to the weight of the oxide form of the catalyst, preferably selected between 5 and 20 wt.%, in particular, preferably between 8 and 11 wt.%.

Percentage data for copper, zinc and aluminum are calculated on the catalyst, progulivavshimisya three hours at 600°C.

In addition, the catalyst according to the invention is in oxide form, the content of alkali ions, in particular sodium ions, preferably less than 500 ppm, particularly preferably less than 300 ppm, in which lastnosti, from 100 parts per million to 300 parts per million

In its oxide form of the catalyst according to the invention has a specific surface area of preferably more than 90 m2/g, particularly preferably more than 100

m2/year

The catalyst according to the invention may be made as a molded body of arbitrary form. For example, it can be executed in the form of rings, molded bodies with 3-20 holes, tablets with smooth or wavy outer surface or as honeycomb. The size of the molded body corresponds to the normal values. To obtain molds pressed powdered catalyst, optionally with the addition of lubricants, as graphite, for example, into tablets, for example, 6×4 mm

Before use, the catalyst is transferred from the oxide form to the active form. For this purpose, the copper oxide at least partially reduced to elemental copper. In addition, the oxide form of the catalyst according to the invention preferably restores the flow of hydrogen. Activation can be performed directly in the synthesis reactor, and preferably it is carried out in that first carry out the restoration of using an inert gas, such as nitrogen, containing a small amount of hydrogen. The first nitrogen usually contains roughly 2.0% vol. H2. During this temperature increase, for example, from 100 to 235°C for 16 h the century Then the hydrogen content increases, and, for example, recovery of lead with 2.0 vol.% H2(the rest of N2) for 3 hours in the temperature range from 235 to 270°C. the Completion of the recovery processing can be carried out with 99.9%H2for about 3 hours at a temperature of from 270°C to 300°C. Typically, the catalyst is activated at the volume rate of from about 3000 to 4000 litres of reducing gas per hour per liter of catalyst.

In restored condition, the size of the crystals of copper is preferably about 4-12 nm, preferably 5-7 nm.

The catalyst according to the invention is suitable in particular for use in methanol synthesis. Therefore, an object of the invention is the use of the above catalyst for methanol synthesis from CO, CO2and H2. The synthesis is usually carried out at a temperature of from about 200 to 320°C, preferably from 210°C to 280°C at a pressure of from about 40 to 150 bar, preferably from about 60 to 100 bar, and at a volume rate of from about 2000 to 22000, preferably from 8000 to 12000 liters of synthesis gas per hour per liter of catalyst, and the synthesis gas may contain from about 5 to 25, preferably from 6 to 12% vol. CO, from about 4 to about 10.% CO210 to 30 vol.% N2plus CH4(inert gases) and how the rest of H2.

Further, the catalyst according to the invention on the walks for use in the reforming of methanol, as well as in the low-temperature conversion of carbon monoxide to carbon dioxide. The last reaction, also called low-temperature shift (LTS), takes place at temperatures in the range of from about 175 to 250°C, preferably from 205 to 215°C and the relations vapor/gas in the range of from about 0.4 to 1.5 (norm. l/standards. l). A typical raw gas mixture contains about 3% vol. CO., 17% vol. CO2, 2% vol. N2and 78% H2conducted through the reactor with a volume rate of from about 2000 to 12,000 liters of dry gas (i.e. without water) per liter of catalyst per hour. With good catalysts for flow rate 11200 h-1and the ratio of steam to gas approximately 1.5 attained the degree of conversion of CO from 70 to 85%.

Hereinafter the invention is explained more examples.

Example

(a) obtaining a solution of copper

5054 g of a suspension of Cu(OH)2× ISSS3(Cu content: 27.7 wt.%, which corresponds to 1400 g of Cu) was dispersed in 10-liter beaker and portions mixed with 85%formic acid (D=1,1856 g/cm3), just 2,399 ml until there is no further allocation of CO2. The solution of copper has a pH of 2.35 and a temperature of 55°C.

(b) Obtaining a solution of Cu/Zn (predecessor of the first solution)

A 5-liter beaker from 781 g of ZnO and 4000 ml of H2O get the dispersion of ZnO. The suspension is combined with a solution of copper obtained according to (a). the ongoing ri dispersion portions add the following 890 ml of formic acid and 33.6 liters of demineralized water. Blue, first slightly cloudy solution is stirred until then, until it becomes completely transparent.

(c) Obtaining sodium carbonate solution (second solution)

Get 24000 ml Na2CO3that has a concentration of approximately

180 grams of CO3/100 ml, and the solution is heated to 70°C.

(d) obtaining the solution of the first aluminum

In 5-quart mixer, equipped with a cooling device, which is 2193 ml of soft water, add 246,7 g NaAlO2. The solution is heated to the temperature of maximum 30°C and then added in several portions 350 ml of formic acid. Milky white solution pH is about 4.0.

(e) obtaining the solution II aluminum

In a mixer equipped with a cooling device, which is 2,193 ml water, added in several portions 246,7 g NaAlO2. Thus ensure that the solution temperature did not exceed 30°C. the Mixture is stirred until then, until you get a clear solution.

(f) Deposition

The solution obtained according to (b), is transferred to the first storage tank to the mixing device. Then the solution I aluminum, obtained according to (d), is injected into the tank and there stirred at room temperature until such time as the United solutions will not be fully transparent. If necessary, you can add water to eliminate the opalescence of the solution. Before n is commenced at the beginning of the deposition solution is heated to 70°C. About 30 minutes before the start of the deposition obtained according to (e) solution II aluminum transfer tank, and produces milk, pale blue suspension.

Second accumulating tank fill obtained according to (c) with a solution of Na2CO3and heated to 70°C.

The solutions contained in the first and second tanks, simultaneously served in a mixing device, and after keeping for about 20 to spend out in the overflow tank. The speed of injection is set so that the pH during the precipitation is 6.5±0,1. From the mixing device, the mixture flows into the overflow tank. From the overflow tank the suspension obtained is held in the tank for maturation, where it is maintained under stirring at about 65°C. the Precipitation ends after about 35 minutes. Then the installation was washed with about 600 ml of softened water and the temperature in the tank to maturity increased to 70°C. Upon completion of the washing process, the suspension is incubated under stirring. The beginning of the maturation process is determined by the end of the washing process. Used in the examples, the duration of ripening are shown in table 2.

At the end of ripening, the suspension is filtered, washed with softened water up until the residual content of sodium in the sediment on the filter will not fall to less than 350 parts per million, and the obtained solid is dried in countercurrent by spray drying using a one-component nozzle. As of the filing install a suspension with a solids content of 30 wt.%. The hot gas temperature at the entrance is about 330-350°C, product temperature at the exit of 110-120°C. the Dried powder is then calcined 50 minutes at about 320°C or in a porcelain Cup shelf in the oven, or working intermittently laboratory rotary tube furnace.

(g) Processing waste water

Collected by filtration and washing waste water is treated with hydrogen peroxide, and with the help of sulfuric acid pH kept at the level of from 5 to 6.5, and the temperature of the waste water held at 70°C. the concentration of formate in the waste water set at the values from 2.8 wt.% up to 0.09 wt.%. The selectivity, defined as the number of moles reacted formate, related to the number of moles of the used hydrogen peroxide is approximately 60%.

Comparative example

(a) obtaining a solution of nitrate of copper/zinc

To 9,79 kg of a solution of nitrate of copper, which contains 1400 g of copper add 781,25 g of zinc oxide. Then add 2077 g of nitric acid (58%) and the mixture is stirred until then, while the solid phase is completely dissolved.

(b) obtaining a solution of aluminium nitrate

In 1.5 liters of fully softened water dissolve 246,7 g Na2AlO2. Then add 1365 g of nitric acid (58%) peremeshivayte until until the solution is clear. The resulting solution of aluminium nitrate are added to a solution of nitrate of copper and zinc and a solution of Cu/Zn/Al is heated to 60°C.

(c) Obtaining Zola aluminum

In 1.5 liters of fully softened water for 30 minutes under stirring to dissolve 246,7 g Na2AlO2. The resulting solution was added to a solution of Cu/Zn/Al and the mixture is heated to 60°C.

(d) Deposition

In the first accumulating tank mixing devices pour the mixture obtained according to (c). In the second accumulating tank mixing devices pour 25 l of an aqueous solution that contains 172 g Na2CO3per liter. Two solutions are simultaneously pumped into the mixing tank and from there the mixture is sent to the tank for curing.

After the deposition of the mixing tank is washed completely softened water, the temperature in the tank maturation increase to 70°C and the precipitate bear from 1 to 4 hours. On maturity, the suspension is filtered, washed with demineralized water up until the residual content of sodium in the sediment on the filter will not be less than 350 ppm, and the resulting solid phase is dried by spray drying with the use of one-component nozzles in a counter. The inlet temperature of the hot gas is 330-350°C, product temperature at the exit of 110-120°C. Then the dried powder p is kaliwat 50 minutes at about 320°C or in a porcelain Cup shelf in the oven, or running in periodic mode laboratory rotary tube furnace.

Implemented examples of deposition, and the following conditions of annealing are summarized in tables 2a and 2b. In these tables shows chemical compositions and physical parameters of the obtained precursors of oxide catalysts.

Determination of physical parameters was carried out as follows:

Determination of the size of the crystals of Cu:

The size of the crystals of Cu determined by x-ray powder diffraction (XRD). Reflex Cu (III) was measured in the range ~43,3° (2θ). The width and the integral intensity of the reflex is calculated in function of pseudovoigt. The size of the crystal Cu is calculated using sherrer based on the calculated half-width.

To prepare for x-ray determination of the crystal size of the oxide catalysts restore as follows:

2-5 g tablets 6×4 mm is heated in a tubular reactor with a regenerating gas (98% N2, 2% H2from room temperature to the maximum temperature at a heating rate of 2°C/min Catalysts that were obtained from formate is heated to the maximum temperature of 80-120°C. the Catalysts that were obtained with the use of nitrates, first warm during the night at 175°C. Then within less than 2 hours the set maximum temperature: (a) 180°C for catalysts, received formatnum/carbonate by; (b) 240°C obtained for nitrate/carbonate by. While keeping the maximum temperature of the hydrogen content in pampering gas increase at the end to 100% within one hour and the sample was then restore another 3 hours.

Determination of specific surface

The BET surface for powder oxide catalyst, as well as for tablets size 6 4mm determined by single-point method of nitrogen adsorption according to DIN 66132.

Determination of loss on ignition

If you need to determine the loss on ignition for tablets, their first grind into powder. The analyzed sample is weighed in a weighed porcelain crucible, which was heated for 3 hours at 600°C in a muffle furnace and then cooled in a desiccator to room temperature. The crucible was heated for 3 hours in a muffle furnace to 600°C and then cooled in a desiccator to room temperature. The cooled crucible was again weighed and the difference was determined by loss on ignition at 600°C.

Determination of the strength of lateral compression

The strength of lateral compression was determined according to DIN EN 1094-5, edition 1995-09, fire-resistant products designed for insulation - part 5: Determination of tensile-compression molded in a cold state. The determination was carried out is as a standard device, as Schleuninger 6-D or ERWEKA TBH MD 310 according to the instructions of the manufacturer of the device.

For a representative amount of sample in 100 tablets in the test for resistance to punching shear was determined by the pressure applied to the cylindrical shell, and using the device of the statistical program calculated the mean value, standard deviation, and minimum and maximum hardness. The distribution of tablets hardness (N) was presented in graphic form.

Determination of pore volume

Pore volume for powder oxide catalysts, as well as tablets 6×4 mm is determined by the indentation method mercury, following the standard DIN 66133.

Determination of formate

Approximately 10-20 g of the calcined powder of the catalyst is introduced into a 300-ml flask it-Meier (25+x) ml H2SO4(25%) and dissolved by heating to about 70°C. the Number of x ml of H2SO4(25%) is determined from the minimum necessary additional quantity of sulfuric acid required to achieve complete dissolution of the sample. The flask was filled with distilled water to about 100 ml by the Addition of from about 2.5 to 25 ml of NaOH (30%) sets the value of pH 8-10. Then the solution is heated for at least another 5 minutes at 70°C. then add 20 ml KMPO4(0.2 n) and Rast is the PR heat to light boil for at least 30 minutes The hot solution acidified with H2SO4(25-50 ml) and add 20 ml of oxalic acid (0.2 n)to recover the manganese dioxide and excess KMnO4to Mn2+. Add a solution of oxalic acid must exactly match the number of regenerative equivalents of oxidizing equivalents of permanganate solution. Finally, a clear solution is titrated with 0.2 n KMnO4, until a light pink color.

Calculation:

Each spent ml of 0.2 n solution of KMnO4corresponding to 4.5 mg formate. The percentage in the sample formate is obtained from:

[% formate] = [(spent ml of 0.2 n solution of KMnO4) × (4.5 mg formate/ml 0.2 n solution of KMnO4) × 100)/(weight of the amount of sample in mg]

The method gives reliable results for concentrations of formate in the titrated solution from 0.08 to 0.5 wt.% errors < +8%. These errors in the application of 0.02 N. the permanganate solution can be reduced to +/-2%. Because of the dependence of accuracy of the method depends on the concentration of formate, which is unknown, may need to take a portion corresponding to the expected value, so that after receiving the first result to repeat the titration with a revised linkage, which will give the total concentration of formate in the titrated solution in the above range.

The content of formate in the mod is scah of examples 3 and 5 are listed in table 1.

Table 1
The content of formate in the calcined catalysts (value "as is" = not classified GV)
ExampleThe content of the formate
31,3%
51,1%

The physical properties of the obtained catalysts are shown in table 2. This table 2a relates to powder catalysts, whereas the values from table 2b are catalysts that have been molded pressed into pellets with dimensions of 6×4 mm

Table 2b
Physical data of the tablets obtained from catalysts
No.UD. stand-here3
(m2/g)
SDF
(H)5
The size of the crystals Cu
(E)
PV6
R=3.75 to 7500 nm
(mm3/g)
PV7
R=3.75 to 7 nm
(mm3/g)
PV7/PV6
()
PV7(sample)/ (standard)
%
080,3155,075,0268,882,830,8100
193,0159,867,8256,7128,350,0155,0
299,0157,063,4283,9136,047,9164,3
3115,0157,962,7425,2159,037,4USD 192.1
4104,0176,350,9340,2140,641,3169,9
5 111,0159,159,9435,8at 149.534,3180,6
699,0185,156,6281,1150,853,6of 182.2
791,0213,967,3277,192,5the 33.4111,8
899,0202,755,4286,7102,935,9124,3
5: Resistance to lateral compression
6,7: pore volume determined by the method of indentation Hg at 2000 bar

Test activity for methanol

Oxidized tablets divided into four parts, one fraction with sizes ranging from 2.5 to 3.5 mm filled tubular reactor and after activation were subjected to standardized test Akti the activity with periodic temperature changes. When assessing the weight output per unit of time ((GZA), kg(methanol)/(kg of catalyst) × h)) was determined as the average value for each period of constant temperature. In the test reaction system consisting of 6-16 separate pipes in one of the test tubes as standard was introduced catalyst C79-7 company SÜd-Chemie AG, Munich, Germany, and GZA defined for the other samples was determined in each case in relation to the value for the standard. This method is advantageous because minor fluctuations, for example, in the composition of the synthesis gas for all samples are the same, and therefore the results of different experiments can be compared with each other.

By-products were determined using gas-chromatographic examination of samples of condensate that each time I added an internal standard. The installed values are also relative to the values obtained for the standard.

The test results on the activity for methanol are given in table 3.

Table 3
The relative weight output per unit of time in the calculation of the standard catalyst
No.GZASide products which you onlyA byproduct of the ethanol
250°C230°C210°C250°C250°C230°C210°C250°C250°C230°C210°C250°C
0100,01100,02100,03100,04100,01100,02100,03100,04100,01100,02100,03100,04
192,2186,2282,6393,048918628731084972993984
296,0194,2293,5397,6497193286311149619126831044
3103596691799899595611579789859661637938
410651026967102810151046 120710981115118623571098
5102,4196,9297,13101,04103189295311441021892613994
699,2199,02100,9399,14113192278310941071722343944
796,4978,910 92,2111029111101091110391941010711
8103,59100,510102,011109998101171111991281011911

1. A method of obtaining a Cu/Zn/Al catalysts, characterized in that
receive a first aqueous solution that contains at least copper formate and formate, zinc,
receive a second solution which contains precipitator,
and the first solution and/or the second solution contains the Sol/gel mixture of aluminum hydroxide,
at the stage of deposition of the first solution and the second solution are combined, and the obtained precipitate,
the precipitate was separated from the aqueous phase, forming an elaborate water and
the precipitate is washed until then, until the alkali content,based on calcined at 600°C the catalyst, will not be less than 500 hours/million, and
then the precipitate is dried.

2. The method according to claim 1, characterized in that the first solution is produced by
obtain an aqueous solution of copper formate, in which the dissolved salt of copper residue by adding formic acid,
obtain a water dispersion or solution of zinc salts,
obtain an aqueous solution of an aluminum salt, and
connection of a solution of copper formate, dispersion or solution of salt of zinc and a solution of an aluminum salt.

3. The method according to claim 2, where the solution of copper formate has a pH value below 3, preferably below 2.5.

4. The method according to claim 2, where the solution or dispersion of the zinc salts are combined with a solution of copper formate with the formation of copper-zinc solution, and the obtained copper-zinc solution has a pH in the range from 3.0 to 4.0, preferably from 3.5 to 3.7, and copper-zinc solution was added a solution of an aluminum salt.

5. The method according to claim 4, where the solution of an aluminum salt is added in several partial solutions, and at least a first portion of a solution of an aluminum salt get so that at least the first part of the aluminium salts dissolved in water by adding formic acid.

6. The method according to claim 4, where the second part of the solution of an aluminum salt get so that the second part of an aluminum salt is dissolved in water and to obtain a first solution, the first part of the solution of an aluminum salt and the second part of p is the target of an aluminum salt is added to copper-zinc solution, preferably separated by time.

7. The method according to claim 2, characterized in that an aqueous solution of an aluminum salt, the first part of the solution of an aluminum salt and/or the second part of the solution of an aluminum salt before deposition is heated to a temperature maximum 40°C, in particular a maximum of 30°C.

8. The method according to claim 1, where, during the stage of deposition pH maintained within the range from 3.5 to 7.5, preferably from 6.0 to 7.0, particularly preferably 6,5±0,1.

9. The method according to claim 1, characterized in that the salt of copper selected from Cu(OH)2and Cu(OH)2·CuCO3.

10. The method according to claim 1, characterized in that as the zinc salts selected ZnO.

11. The method according to claim 1, where the precipitant is an alkaline base, preferably alkali carbonate.

12. The method according to claim 1, where the precipitator is hydrogen peroxide.

13. The method according to claim 1, characterized in that the sediment after deposition is subjected to maturation.

14. The method according to item 13, characterized in that the maturation is carried out in a period of from 10 min to 10 h, preferably from 1 to 5 hours

15. The method according to item 13, characterized in that the ripening is carried out at temperatures above 60°C, in particular in the range from 65 to 80°C.

16. The method according to claim 1, characterized in that stage of deposition is conducted as a continuous deposition.

17. The method according to claim 1, characterized in that the first solution contains copper and zinc in a ratio selected from 1:99 to 99:1.

18. Ways who according to claim 1, characterized in that the precipitate after drying, calcined.

19. The method according to p, where sludge calcined at temperatures in the range 140-1000°C, preferably 170-350°C. for at least 0.1, preferably from 20 minutes to 8 hours, particularly preferably from 30 minutes to 4 hours

20. The method according to claim 1, characterized in that the waste water contains formatnya ions and the fact that the containing formate waste water is subjected to oxidation processing, and formatnya ions are oxidized mainly to carbonate, hydrocarbonate, carbon dioxide and water.

21. The method according to claim 20, characterized in that the oxidation treatment in containing formate waste water is added to hydrogen peroxide.

22. The method according to claim 20, characterized in that the oxidizing treatment containing formate waste water is performed before separating the precipitate.

23. The method according to claim 20, characterized in that the oxidizing treatment is carried out by biological treatment containing formate waste water.

24. The catalyst obtained by the method according to one of claims 1 to 23, with the content of the formate, based on the oxidic catalyst, less than 5%, preferably 0.5 to 4%, particularly preferably 1-2%.

25. The catalyst according to paragraph 24, wherein the proportion of mesopores with a radius of 3.75-7,0 nm is more than 30% of the total pore volume.

26. The catalyst according to paragraph 24, characterized t is m, the copper content, calculated on the copper oxide and related to the weight of the oxide catalyst, choose between 55 and 69 wt.%.

27. The catalyst according to paragraph 24, wherein the content of zinc, calculated on zinc oxide and related to the weight of the oxide catalyst is chosen between 20 and 33 wt.%.

28. The catalyst according to paragraph 24, wherein the content of aluminum, calculated on alumina and referred to the weight of the oxide catalyst is chosen between 5 and 20 wt.%.

29. The catalyst according to paragraph 24, wherein the oxide catalyst has a content of alkali ions is less than 500 hours/million

30. The use of the catalyst according to one of PP-29 for methanol synthesis.

31. The use of the catalyst according to one of PP-29 for reforming of methanol.

32. The use of the catalyst according to one of PP-29 for low-temperature conversion of carbon monoxide to carbon dioxide.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention pertains to the method of methanol obtaining from a concentrated mixture of hydrogen and carbon oxides with the following components in vol %: H2 - 62.0-78.5; Ar - 0.02-0.07; N2 - 0.05-2.2; CH4 - 1.0-3.5; CO - 10.4-29.5; CO2 - 3.2-10.7. The methanol is obtained by concentrating it in a copper containing catalyst at high temperature and pressure in two stages. The gas mixture from the reformer is divided into two streams in volume ratios of 100 : (1-50), one of which is in direct contact with the catalyst in the flow reactor at the first stage, at temperature of 200-285°C, pressure of 5-15 MPa and volume rate of 800-2000 h-1. The other stream is mixed with a cycled gas in volume ratio of 10 : (10-100) and with volume rate of 2500-10000 h-1. This stream is then channelled to the second stage, with separation of methanol and water on each stage in corresponding devices.

EFFECT: increased production of methanol and increased efficiency of the process.

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FIELD: chemistry.

SUBSTANCE: method includes contact of gas mixture containing carbon oxides and hydrogen ballasted down with nitrogen with copper-containing catalyst under heating, pressure and definite rate velocity of feeding into reactor. Reactor unit consists of two adiabatic-type reactors connected with a pipeline; the original gas mixture containing CO - 10-15 % v/v, CO2 - 0.3-5.0 % v/v, H2 - 15-40 % v/v, N2 -40.0-74.7 % v/v and volumetric ratio H2/(CO+CO2) equal to 1.00-2.91, at 200-260°C and pressure 3.5-5.0 MPa with rate velocity 2000-5000 h-1 is fed into the first reactor with larger main part of unconverted gas fed to circulation and produced at the outlet of the second reactor cooled to 15-20°C and further purified to remove methanol in tower washer and compressed; then the reaction mixture from the first reactor is fed into the second reactor along with the rest minor part of circulating gas indicated above as quench - cold circulation gas fed into the pipeline between the two rectors.

EFFECT: method allows increasing methanol yield, efficiency of the process and reducing energy consumption.

4 cl, 3 tbl, 1 dwg, 1 exsid1190496

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at high pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:(0.7-1.1):(0.086-0.157):(0.05-0.15):(0.125-0.2):(0.018-0.029):(0.04-0.075).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at low pressure and provides a wear-resistant catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, and boron and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3 = 1:0.3:(0.15-0.2):(0.1-0.025):(0.25-0.3):(0.08-0.1).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at median pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:0.3:(0.014-0.038):(0.047-0.119):(0.05-0.1):(0.007-0.014):(0.0292-0.054).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

The invention relates to a method of producing methanol from natural gas

The invention relates to a method for producing methanol, which finds application in the field of organic synthesis

The invention relates to methods for nizkoatomnye linear alcohols from synthesis gas at pressures not exceeding 100 atmospheres in the presence of a catalyst

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry and can be used for producing hydrogen and methane. The device has a case 1, a reactor for vapour conversion of hydrocarbon fuel 2, with a burner 3 inside it, a reactor for vapour conversion of carbon monoxide 4, a reactor for selective methanation 5 or reactor for selective methanation 5 and a reactor for selective oxidation of carbon monoxide 6, vapour generator 7, stream distributor 8 with channels for carrying reformate and products of combustion of hydrocarbon fuel, two heat-insulation units 9 and 10, fitted in line with the reactor for vapour conversion of hydrocarbon fuel 2 and vapour generator 7 with formation of annular channels between them for carrying heat to the reformate. Heat-insulation units 9 and 10 are fitted on both sides of the vapour generator 7, which is made in form of a screw conveyor and is installed in line with the reactor for vapour conversion of hydrocarbon fuel 2. Between the inner surface of the case 1 and the outer surface of the heat insulation unit 10, adjacent to the vapour generator 7, there is a heat exchanger 11, made in form of two coaxial pipes 23 and 24, separated from each other by at least one longitudinal baffle 25, fitted with a gap from the bottom end of the pipes. The reactor for vapour conversion of carbon monoxide, reactor for selective methanation 5 or reactor for selective methanation and reactor for selective oxidation of carbon monoxide 6 are joined on the height, and catalysts for these reactors are separated from each other by inert filling material or separating grids 14. The reactor for vapour conversion of hydrocarbon fuel is joined to the vapour generator 7 by pipes 15. In the bottom part of the annular gap between the outer surface of the vapour generator and the inner surface of the heat-insulating unit there is a collector 16 for collecting reformate coming out of the reactor for vapour conversion of hydrocarbon fuel, joined by pipes 17 with each pipe 12 of the reactor for vapour conversion of carbon monoxide 4. The device also has a flame control sensor 18, water and natural gas mixer 19, connecting pipe for inlet and outlet of reagents 20, heat insulation 21, ignition plug 22, thermocouple for monitoring temperature of structural components of the device. Temperature conditions for vapour conversion of hydrocarbon fuel and vapour conversion of carbon monoxide are regulated using the burner by varying flow of hydrocarbon fuel and excess air factor. Temperature conditions during fine purification of hydrogen-bearing gas from carbon monoxide are regulated by using air, which is further transferred to the burner, as heat carrier.

EFFECT: invention increases efficiency of the process.

2 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry and can be used for producing hydrogen and methane. The device has a case 1, a reactor for vapour conversion of hydrocarbon fuel 2, with a burner 3 inside it, a reactor for vapour conversion of carbon monoxide 4, a reactor for selective methanation 5 or reactor for selective methanation 5 and a reactor for selective oxidation of carbon monoxide 6, vapour generator 7, stream distributor 8 with channels for carrying reformate and products of combustion of hydrocarbon fuel, two heat-insulation units 9 and 10, fitted in line with the reactor for vapour conversion of hydrocarbon fuel 2 and vapour generator 7 with formation of annular channels between them for carrying heat to the reformate. Heat-insulation units 9 and 10 are fitted on both sides of the vapour generator 7, which is made in form of a screw conveyor and is installed in line with the reactor for vapour conversion of hydrocarbon fuel 2. Between the inner surface of the case 1 and the outer surface of the heat insulation unit 10, adjacent to the vapour generator 7, there is a heat exchanger 11, made in form of two coaxial pipes 23 and 24, separated from each other by at least one longitudinal baffle 25, fitted with a gap from the bottom end of the pipes. The reactor for vapour conversion of carbon monoxide, reactor for selective methanation 5 or reactor for selective methanation and reactor for selective oxidation of carbon monoxide 6 are joined on the height, and catalysts for these reactors are separated from each other by inert filling material or separating grids 14. The reactor for vapour conversion of hydrocarbon fuel is joined to the vapour generator 7 by pipes 15. In the bottom part of the annular gap between the outer surface of the vapour generator and the inner surface of the heat-insulating unit there is a collector 16 for collecting reformate coming out of the reactor for vapour conversion of hydrocarbon fuel, joined by pipes 17 with each pipe 12 of the reactor for vapour conversion of carbon monoxide 4. The device also has a flame control sensor 18, water and natural gas mixer 19, connecting pipe for inlet and outlet of reagents 20, heat insulation 21, ignition plug 22, thermocouple for monitoring temperature of structural components of the device. Temperature conditions for vapour conversion of hydrocarbon fuel and vapour conversion of carbon monoxide are regulated using the burner by varying flow of hydrocarbon fuel and excess air factor. Temperature conditions during fine purification of hydrogen-bearing gas from carbon monoxide are regulated by using air, which is further transferred to the burner, as heat carrier.

EFFECT: invention increases efficiency of the process.

2 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry and can be used for producing hydrogen and methane. The device has a case 1, a reactor for vapour conversion of hydrocarbon fuel 2, with a burner 3 inside it, a reactor for vapour conversion of carbon monoxide 4, a reactor for selective methanation 5 or reactor for selective methanation 5 and a reactor for selective oxidation of carbon monoxide 6, vapour generator 7, stream distributor 8 with channels for carrying reformate and products of combustion of hydrocarbon fuel, two heat-insulation units 9 and 10, fitted in line with the reactor for vapour conversion of hydrocarbon fuel 2 and vapour generator 7 with formation of annular channels between them for carrying heat to the reformate. Heat-insulation units 9 and 10 are fitted on both sides of the vapour generator 7, which is made in form of a screw conveyor and is installed in line with the reactor for vapour conversion of hydrocarbon fuel 2. Between the inner surface of the case 1 and the outer surface of the heat insulation unit 10, adjacent to the vapour generator 7, there is a heat exchanger 11, made in form of two coaxial pipes 23 and 24, separated from each other by at least one longitudinal baffle 25, fitted with a gap from the bottom end of the pipes. The reactor for vapour conversion of carbon monoxide, reactor for selective methanation 5 or reactor for selective methanation and reactor for selective oxidation of carbon monoxide 6 are joined on the height, and catalysts for these reactors are separated from each other by inert filling material or separating grids 14. The reactor for vapour conversion of hydrocarbon fuel is joined to the vapour generator 7 by pipes 15. In the bottom part of the annular gap between the outer surface of the vapour generator and the inner surface of the heat-insulating unit there is a collector 16 for collecting reformate coming out of the reactor for vapour conversion of hydrocarbon fuel, joined by pipes 17 with each pipe 12 of the reactor for vapour conversion of carbon monoxide 4. The device also has a flame control sensor 18, water and natural gas mixer 19, connecting pipe for inlet and outlet of reagents 20, heat insulation 21, ignition plug 22, thermocouple for monitoring temperature of structural components of the device. Temperature conditions for vapour conversion of hydrocarbon fuel and vapour conversion of carbon monoxide are regulated using the burner by varying flow of hydrocarbon fuel and excess air factor. Temperature conditions during fine purification of hydrogen-bearing gas from carbon monoxide are regulated by using air, which is further transferred to the burner, as heat carrier.

EFFECT: invention increases efficiency of the process.

2 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to hydrogen power engineering, and more specifically to a hydro-reaction composition for producing hydrogen. The hydro-reaction composition for producing hydrogen contains, wt %: aluminium powder 10 to 30, sodium water glass or its aqueous solutions 90 to 70.

EFFECT: invention allows for changing hydrogen output in a wide range, thus controlling the process.

7 ex

FIELD: chemistry.

SUBSTANCE: invention refers to the field of inorganic synthesis and can be used at preparation of hydrogen and crystalline aluminium hydroxide in the form of boehmite which can be used in different branches of industry. The method involves the suspending of pulverised aluminium in water with adding of no more than 0.1 M of catalyst - alkali metal hydroxide. The reactor is pressurised with saturated water vapours, the obtained aluminium suspension is sprayed to the high-pressure reactor. After that but before boehmite removal from the reactor the suspension is allowed for implementing of aluminium complete oxidation and boehmite crystallisation Then the mixture of water vapours and hydrogen is removed from the reactor and boehmite is unloaded to the receiver For providing of process continuity at least one additional reactor is used; during suspension spraying in one of reactors at least in one of the others the aluminium oxidation is completed and crystallisation and withdrawal of boehmite are carried out.

EFFECT: invention allows obtaining of chemically pure crystalline boehmite

2 cl, 3 dwg, 4 tbl

,

FIELD: chemistry.

SUBSTANCE: invention refers to the field of chemistry, namely to the methods for hydrogen preparation from hydrocarbon and/or organic raw materials. The method for hydrogen preparation includes periodic interchange of the following stages: a) hydrogen preparation by mixing the raw materials vapours with water vapour and pass of the obtained mixture through at least one mixed fixed bed consisting of particles of the catalyst for vapour hydrocarbon conversion and particles of carbon dioxide chemisorbent and b) periodic chemisorbent regeneration at elevated temperature in the flow of regenerating gas with removal of desorbing carbon dioxide in the regenerating gas flow. In the stage of chemisorbent regeneration the regenerating gas is the mix of the air with ignitable substance capable of catalytic oxidising with air oxygen liberating the heat to the catalyst particles. The temperature of the regenerating gas flow at the input to the layer of catalyst and chemisorbent particles is maintained lower than the onset temperature of the catalytic oxidising of the ignitable substance, and the flow regenerating gas is passed through the bed of catalyst particles and chemisorbent in the direction contrary to the direction of the flow of starting materials vapours fed together with water vapour. The starting materials are either light gaseous paraffins (particularly methane) as well as mixtures thereof (particularly natural gas) or light alcohols (particularly methanol or ethanol); the ignitable substance is either starting materials vapours or hydrogen.

EFFECT: invention allows hydrogen obtaining with minimal admixtures of carbon oxides.

7 cl, 1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention refers to the field of chemistry, namely to the methods for hydrogen preparation from hydrocarbon and/or organic raw materials. The method for hydrogen preparation includes periodic interchange of the following stages: a) hydrogen preparation by mixing the raw materials vapours with water vapour and pass of the obtained mixture through at least one mixed fixed bed consisting of particles of the catalyst for vapour hydrocarbon conversion and particles of carbon dioxide chemisorbent and b) periodic chemisorbent regeneration at elevated temperature in the flow of regenerating gas with removal of desorbing carbon dioxide in the regenerating gas flow. In the stage of chemisorbent regeneration the regenerating gas is the mix of the air with ignitable substance capable of catalytic oxidising with air oxygen liberating the heat to the catalyst particles. The temperature of the regenerating gas flow at the input to the layer of catalyst and chemisorbent particles is maintained lower than the onset temperature of the catalytic oxidising of the ignitable substance, and the flow regenerating gas is passed through the bed of catalyst particles and chemisorbent in the direction contrary to the direction of the flow of starting materials vapours fed together with water vapour. The starting materials are either light gaseous paraffins (particularly methane) as well as mixtures thereof (particularly natural gas) or light alcohols (particularly methanol or ethanol); the ignitable substance is either starting materials vapours or hydrogen.

EFFECT: invention allows hydrogen obtaining with minimal admixtures of carbon oxides.

7 cl, 1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: methane or natural gas is mixed with air, the mixture is forcibly ignited and methane is oxidised with atmospheric oxygen in a combustion chamber. Methane is completely oxidised in the combustion chamber. From the products of the oxidation process and atmospheric nitrogen, carbon dioxide is separated, and then mixed with methane again. Complete carbon dioxide conversion of methane is carried out in a reaction chamber, obtaining synthetic gas. The device comprises a combustion chamber 2, for methane or natural gas with atmospheric oxygen, and a mixer 4. The combustion chamber contains an ignition device and is made in form of a flow chamber, the outlet of which is attached to the mixer through an anti-slippage frame 3. Pipes 5 and 6, carrying methane and air respectively, are connected to the mixer. The outlet of the combustion chamber is connected to a heat exchanger 8 for cooling oxidation products and heating air, which is fed into the combustion chamber. The heat exchanger is provided with a socket piece for outlet of oxidation products. The device is also provided with a system 11, for releasing carbon dioxide, carbon dioxide and methane mixer 13 and a carbon dioxide conversion chamber 15, put in the combustion chamber The carbon dioxide conversion chamber is made in form of a flow reactor with walls of heat resistant material.

EFFECT: obtaining concentrated synthetic gas with high output, using air as an oxidising agent, reduced soot output, possibility of regulating content of synthetic gas.

12 cl, 1 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: present invention refers to the production of catalyst for hydrocarbon conversion. The said catalyst includes nickel, titanium, boron, manganese, lanthanum and aluminium oxides with following components content, wt %: nickel oxide - 8.5-24.5; titanium oxide - 0.05-2.1; boron oxide - 0.1-3.0; manganese oxide - 0.01-2.8; lanthanum oxide - 0.1-5.0; aluminium oxide constitutes the remaining percentage. The method of catalyst obtaining consists of following stages: 1) preparation of the batch mixture including alumina, titanium oxide, boric acid, manganese oxide, lanthanum oxide; 2) addition of the binder including paraffin, wax and oleinic acid; 3) moulding of the carrier pellets by slip casting at excessive pressure 0.4-2 MPa and temperature 70-80°; 4) air-seasoning and two-stage calcination of the obtained carrier whereat the first stage is carried out in ceramic forms in alumina bed at temperature 1100-1200°C during 4-8 hrs, then the temperature is increased during 1 hour up to 1350-1420°C, and the calcination is carried out at this temperature during 2-4 hrs; 5) carrier impregnation with nickel and aluminium and/or lanthanum nitrates; 6) drying and calcination of catalyst mass at 400-500°C.

EFFECT: preparation of catalyst with enhanced activity and mechanical reliability, decreasing of catalyst bed hydraulic resistance

7 cl, 1 tbl, 19 ex

FIELD: treatment facilities.

SUBSTANCE: invention may be used for cleaning hydrogen-rich gas mixtures from carbon oxide. The process is divided into two stages, i.e at temperature no less than 90°C and pressure no less than 1 atm. At the first stage cleaning is performed by selective oxidation of carbon oxide by oxygen and/or air. At the second stage cleaning is performed by selective methanation of carbon oxide. According to the other version of invention, selective methanation may be conducted first, and selective oxidation of the residual carbon oxide may be conducted at the end. Copper and cerium oxide system is used as an active component of selective oxidation catalyst, whereas nickel and cerium oxide system is used an active component of selective methanation catalyst.

EFFECT: invention allows for improving effectiveness of hydrogenous gas mixtures cleaning from carbon oxide.

22 cl, 1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry and can be used for producing hydrogen and methane. The device has a case 1, a reactor for vapour conversion of hydrocarbon fuel 2, with a burner 3 inside it, a reactor for vapour conversion of carbon monoxide 4, a reactor for selective methanation 5 or reactor for selective methanation 5 and a reactor for selective oxidation of carbon monoxide 6, vapour generator 7, stream distributor 8 with channels for carrying reformate and products of combustion of hydrocarbon fuel, two heat-insulation units 9 and 10, fitted in line with the reactor for vapour conversion of hydrocarbon fuel 2 and vapour generator 7 with formation of annular channels between them for carrying heat to the reformate. Heat-insulation units 9 and 10 are fitted on both sides of the vapour generator 7, which is made in form of a screw conveyor and is installed in line with the reactor for vapour conversion of hydrocarbon fuel 2. Between the inner surface of the case 1 and the outer surface of the heat insulation unit 10, adjacent to the vapour generator 7, there is a heat exchanger 11, made in form of two coaxial pipes 23 and 24, separated from each other by at least one longitudinal baffle 25, fitted with a gap from the bottom end of the pipes. The reactor for vapour conversion of carbon monoxide, reactor for selective methanation 5 or reactor for selective methanation and reactor for selective oxidation of carbon monoxide 6 are joined on the height, and catalysts for these reactors are separated from each other by inert filling material or separating grids 14. The reactor for vapour conversion of hydrocarbon fuel is joined to the vapour generator 7 by pipes 15. In the bottom part of the annular gap between the outer surface of the vapour generator and the inner surface of the heat-insulating unit there is a collector 16 for collecting reformate coming out of the reactor for vapour conversion of hydrocarbon fuel, joined by pipes 17 with each pipe 12 of the reactor for vapour conversion of carbon monoxide 4. The device also has a flame control sensor 18, water and natural gas mixer 19, connecting pipe for inlet and outlet of reagents 20, heat insulation 21, ignition plug 22, thermocouple for monitoring temperature of structural components of the device. Temperature conditions for vapour conversion of hydrocarbon fuel and vapour conversion of carbon monoxide are regulated using the burner by varying flow of hydrocarbon fuel and excess air factor. Temperature conditions during fine purification of hydrogen-bearing gas from carbon monoxide are regulated by using air, which is further transferred to the burner, as heat carrier.

EFFECT: invention increases efficiency of the process.

2 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry and can be used for producing hydrogen and methane. The device has a case 1, a reactor for vapour conversion of hydrocarbon fuel 2, with a burner 3 inside it, a reactor for vapour conversion of carbon monoxide 4, a reactor for selective methanation 5 or reactor for selective methanation 5 and a reactor for selective oxidation of carbon monoxide 6, vapour generator 7, stream distributor 8 with channels for carrying reformate and products of combustion of hydrocarbon fuel, two heat-insulation units 9 and 10, fitted in line with the reactor for vapour conversion of hydrocarbon fuel 2 and vapour generator 7 with formation of annular channels between them for carrying heat to the reformate. Heat-insulation units 9 and 10 are fitted on both sides of the vapour generator 7, which is made in form of a screw conveyor and is installed in line with the reactor for vapour conversion of hydrocarbon fuel 2. Between the inner surface of the case 1 and the outer surface of the heat insulation unit 10, adjacent to the vapour generator 7, there is a heat exchanger 11, made in form of two coaxial pipes 23 and 24, separated from each other by at least one longitudinal baffle 25, fitted with a gap from the bottom end of the pipes. The reactor for vapour conversion of carbon monoxide, reactor for selective methanation 5 or reactor for selective methanation and reactor for selective oxidation of carbon monoxide 6 are joined on the height, and catalysts for these reactors are separated from each other by inert filling material or separating grids 14. The reactor for vapour conversion of hydrocarbon fuel is joined to the vapour generator 7 by pipes 15. In the bottom part of the annular gap between the outer surface of the vapour generator and the inner surface of the heat-insulating unit there is a collector 16 for collecting reformate coming out of the reactor for vapour conversion of hydrocarbon fuel, joined by pipes 17 with each pipe 12 of the reactor for vapour conversion of carbon monoxide 4. The device also has a flame control sensor 18, water and natural gas mixer 19, connecting pipe for inlet and outlet of reagents 20, heat insulation 21, ignition plug 22, thermocouple for monitoring temperature of structural components of the device. Temperature conditions for vapour conversion of hydrocarbon fuel and vapour conversion of carbon monoxide are regulated using the burner by varying flow of hydrocarbon fuel and excess air factor. Temperature conditions during fine purification of hydrogen-bearing gas from carbon monoxide are regulated by using air, which is further transferred to the burner, as heat carrier.

EFFECT: invention increases efficiency of the process.

2 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry and can be used for producing hydrogen and methane. The device has a case 1, a reactor for vapour conversion of hydrocarbon fuel 2, with a burner 3 inside it, a reactor for vapour conversion of carbon monoxide 4, a reactor for selective methanation 5 or reactor for selective methanation 5 and a reactor for selective oxidation of carbon monoxide 6, vapour generator 7, stream distributor 8 with channels for carrying reformate and products of combustion of hydrocarbon fuel, two heat-insulation units 9 and 10, fitted in line with the reactor for vapour conversion of hydrocarbon fuel 2 and vapour generator 7 with formation of annular channels between them for carrying heat to the reformate. Heat-insulation units 9 and 10 are fitted on both sides of the vapour generator 7, which is made in form of a screw conveyor and is installed in line with the reactor for vapour conversion of hydrocarbon fuel 2. Between the inner surface of the case 1 and the outer surface of the heat insulation unit 10, adjacent to the vapour generator 7, there is a heat exchanger 11, made in form of two coaxial pipes 23 and 24, separated from each other by at least one longitudinal baffle 25, fitted with a gap from the bottom end of the pipes. The reactor for vapour conversion of carbon monoxide, reactor for selective methanation 5 or reactor for selective methanation and reactor for selective oxidation of carbon monoxide 6 are joined on the height, and catalysts for these reactors are separated from each other by inert filling material or separating grids 14. The reactor for vapour conversion of hydrocarbon fuel is joined to the vapour generator 7 by pipes 15. In the bottom part of the annular gap between the outer surface of the vapour generator and the inner surface of the heat-insulating unit there is a collector 16 for collecting reformate coming out of the reactor for vapour conversion of hydrocarbon fuel, joined by pipes 17 with each pipe 12 of the reactor for vapour conversion of carbon monoxide 4. The device also has a flame control sensor 18, water and natural gas mixer 19, connecting pipe for inlet and outlet of reagents 20, heat insulation 21, ignition plug 22, thermocouple for monitoring temperature of structural components of the device. Temperature conditions for vapour conversion of hydrocarbon fuel and vapour conversion of carbon monoxide are regulated using the burner by varying flow of hydrocarbon fuel and excess air factor. Temperature conditions during fine purification of hydrogen-bearing gas from carbon monoxide are regulated by using air, which is further transferred to the burner, as heat carrier.

EFFECT: invention increases efficiency of the process.

2 cl, 4 dwg

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