Method of conversion of carbon oxides

FIELD: chemistry.

SUBSTANCE: invention relates to catalyst, suitable to application in reactions of conversion of carbon oxides, in form of granules, formed by pressing reduced and passivated catalyst powder, and claimed powder contains copper in the interval 10-80 wt %, zinc oxide in the interval 20-90 wt %, aluminium oxide in the interval 5-60 wt % and, optionally, one or several oxide promoter compounds, selected from compounds of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare-earth elements, in quantity in the interval 0.01-10 wt %. Said granules have average crush strength in horizontal direction after production ≥6.5 kg, ratio of values of average crush strength in horizontal direction after reduction and after production ≥0.5:1 and area of copper surface over 60 m2/g Cu. Invention also relates to method of claimed catalyst production and to method of conversion of carbon oxides in presence of claimed catalyst.

EFFECT: catalyst has high strength of granules and high activity as a result of increased area of copper surface, which makes it possible to apply reactors of smaller size and increase process productivity.

15 cl, 9 ex

 

This invention relates to reactions of carbon monoxide conversion, such as the reaction of the conversion of water gas and methanol synthesis, and copper-containing catalysts suitable for use in such reactions.

The processes of conversion of carbon monoxide plays an important role in the processing of synthesis gas by the reaction of conversion of water gas and in the production of alcohols, such as methanol. These reactions are presented below.

CO+H2O→CO2+H2

CO+2H2→CH3OH

CO2+3H2→CH3OH+H2O

Catalysts for such reactions are usually obtained by molding in the form of granules of small discrete particles of a homogeneous mixture of copper oxide and one or more other oxide materials, usually consisting of zinc oxide, which are not recovered when the reaction conditions conversion. A homogeneous mixture is usually obtained by precipitation of copper compounds and compounds into other oxide materials, and/or precipitation of copper compounds in the presence of other oxide materials, or turn them in compounds, with subsequent firing to turn precipitated copper compounds and, optionally, other components in the oxides. Accordingly, the oxide powder is formed into pellets. In order to form the active catalyst, the pellets are exposed to rebuild the nutrient conditions, to restore the copper oxide in said pellets to metallic copper. The recovery phase is usually performed in the reactor, which should be the process of conversion of carbon monoxide: generally, the catalyst precursor, in which the copper is present in the form of copper oxide, is loaded into the reactor and the recovery is carried out by passing through it a suitable gas mixture. Recovery of copper oxide is exothermic, and this stage of recovery in-situ is often performed for an extended period of time using flows of dilute hydrogen in order to avoid damage to the catalyst. Such extended initial procedures are difficult to manage and they can be expensive to run.

Due to such technologies deposition/annealing/restore catalysts typically have a surface area of copper more than 20 m2per gram of copper, often more than 40 m2per gram of copper. Commercially available catalysts for the conversion of carbon monoxide typically have a surface area of copper of approximately 50 m2/g per gram of copper. The surface area of copper can be measured by the decomposition of nitrous oxide, for example, as described in Evans et al. in Applied Catalysis 1983, 7, 75-83 and, in particular, appropriate technology described in EP 0202824.

Because the activity of cat is Satarov associated with the surface area of copper, it is desirable to obtain catalysts with increased surface area of copper.

US 4863894 describes a method of making a catalyst, comprising the formation of a composition containing a homogeneous mixture of discrete particles of copper and zinc and/or magnesium and, optionally, at least one element X selected from aluminum, vanadium, chromium, titanium, zirconium, thorium, uranium, molybdenum, tungsten, manganese, silicon, and rare earth elements, and exposure of the composition to the influence of reducing conditions in such a way that the copper compounds in it into the copper, with copper compounds in a homogeneous mixture is recovered to metallic copper without heating the specified homogeneous mixture to a temperature above 250°C. Direct recovery of the compositions of precipitated catalyst precursor leads to the formation of catalysts with the magnitude of the surface area of copper >70 m2per gram of copper.

However, the surface area of copper is not the only criterion that must be taken into account catalysts for the conversion of carbon oxides. In particular, the strength and stability of the catalyst in terms of activity and selectivity. The average crushing strength in the horizontal direction (MHCS) is a method widely used is in the production of catalysts for measuring the strength of the granules of the catalyst. MHCS is measured as established for the pellets to ensure that their strength is sufficient to be subjected to stresses applied during loading of the catalyst, and to provide guidance in terms of strength during operation. The catalysts obtained by the method according to US 4863894 not have a high stability strength required in modern processes of conversion of carbon oxides, and is currently still used for oxide catalysts.

We now have developed catalysts with increased surface area of copper, which overcome the disadvantages of the prior catalysts.

Accordingly, this invention provides a method of converting carbon oxides, which comprises the reaction interaction process gas containing carbon monoxide, which contains hydrogen and/or water vapor and contains at least one component of the hydrogen and carbon monoxide, in the presence of a catalyst containing molded elements, formed from a powder recovered and passivated catalyst, and powder that contains copper in the range of 10-80 wt.%, zinc oxide in the range of 20-90 wt.%, the aluminum oxide in the range of 5-60 wt.% and, optionally, one or more oxide promoting compounds selected from compounds of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare earth elements, in a quantity in the range of 0.01-10 wt.%, these molded elements have a ratio of average strength crush strength in the horizontal direction after the re-restoration and post production ≥0.5 and the surface area of copper of more than 60 m2/g Cu.

The invention also provides a catalyst suitable for use in the reactions of carbon monoxide conversion, in the form of molded elements, formed from a powder recovered and passivated catalyst, and powder that contains copper in the range of 10-80 wt.%, zinc oxide in the range of 20-90 wt.%, the aluminum oxide in the range of 5-60 wt.% and, optionally, one or more oxide promoting compounds selected from compounds of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare earth elements, in a quantity in the range of 0.01-10 wt.%, these molded elements have a ratio of average strength crush strength in the horizontal direction after the re-restoration and post production ≥0.5 and the surface area of copper of more than 60 m2/g Cu.

The invention also provides a method of manufacturing a catalyst containing the following stages:

(i) forming, in an aqueous medium, the composition containing a homogeneous mixture of discrete particles of copper, zinc, aluminum and, optionally, one or more compounds selected from compounds of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare earth elements,

(ii) recovering and drying the composition to form a catalyst precursor,

(iii) placing the dried composition of the catalyst precursor effects of reducing conditions in such a way that the copper compounds in it turn into copper,

(iv) the passivation of surfaces restored copper, and

(v) forming restored and passivated composition,

characterized in that before recovery of copper compounds homogeneous mixture is subjected to at the stage of drying at a temperature in the range of 180-240°C.

Stage of drying, which does not convert compounds of copper, copper oxide, provides the catalyst precursor, capable of forming molded elements of high strength, which supports high surface area copper during recovery. Stage passivation creates a protective layer on the surface of the recovered copper and enables secure molding the recovered composition. In this invention the volumetric conversion of copper to copper oxide, for example, by firing the composition is very undesirable, because it results in catalysts with smaller Majesty the us surface area of copper and accordingly, low activity.

The catalyst according to this invention is particularly applicable because it provides faster commissioning, than conventional oxide catalysts, gives a higher activity due to its increased surface area of copper, which, in turn, gives the potential use of reactors of smaller size and/or increased performance and provides high strength pellets, which provides a number of advantages, including the production of new forms, which provide reduced pressure drop in the processes of the conversion.

The content of copper (expressed in per Cu atoms) of the active catalyst is typically in the range of 10-80%, preferably 15-70%by weight. Within this interval, the copper content in the range of 50-70 wt.% generally applicable for the synthesis of methanol, whereas for the reaction conversion of the copper content is usually somewhat lower and is, in particular, in the range of 15-50 wt.%. In the catalyst according to this invention, the copper will be oxidized form in the passivated layer and in the elemental form below this layer. Preferably the catalyst immediately after manufacture <50% (based on atoms), more preferably <40% (calculated on the atoms) of copper is in the oxidized form.

In addition to the metal is worked copper, the catalyst may contain one or more other metals having catalytic activity: when the process is a synthesis of alcohol, examples of such other metals are cobalt, palladium, rhodium or ruthenium. May not necessarily be metallic silver. Other catalytically active metals, if present, are usually present in relatively low proportions; the proportion of such other catalytically active metals is typically 1-10 atoms of these metals on 100 atoms of copper.

Copper-containing catalysts are experiencing the problem, namely, that when heated above about 250°C, the copper atoms tend to mutual agglomeration, leading to reduction of the area of the copper surface after a certain period of time at an elevated temperature with a corresponding decrease of activity. In order to alleviate this drawback, the catalyst contains at least one additional material, including zinc compounds, and, optionally, one or more promoting compounds selected from compounds of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare earth elements. The catalyst content of the zinc oxide may be in the range of 20-90 wt.%, and one or more oxide promoting compounds, if present, may be present in the amount of online is rule 0.01 to 10 wt.%. Compounds of magnesium are preferred, and the catalyst preferably contains magnesium in an amount of 1-5 wt.%, in the calculation of the MgO. Promoting connections are not restored to the metal in the process and are usually present in the catalyst in the form of one or more oxides.

Aluminum in the form of aluminum oxide, which may be partially gidratirovannym aluminum oxide, is also present in the catalyst. The amount of aluminum oxide may be in the range of 5-60 wt.% (based on Al2O3). The aluminum oxide can be included directly or formed from aluminum compounds, which decomposes to the oxide or hydrated oxide.

The preferred composition of the catalyst precursor contains, before recovery, the dry residue containing mixed carbonates, including hydroxycarbonate, metals, Cu and Zn, aluminum oxide or gidratirovannym aluminum oxide, dispersed therein, and, optionally, containing compounds of one or more metals of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si, or rare earth elements, in particular compounds of Mg, as a promoter. The catalyst preferably contains 30 to 70 wt.% copper (calculated as CuO). The mass ratio of Cu:Zn (calculated as CuO:ZnO) may be 1:1 or more, but preferably is in the Arvale from 2:1 to 3.5:1 by weight catalysts for alcohol synthesis, and in the range of from 1.4:1 to 2.0:1 catalysts for the conversion of water gas.

Especially preferred compositions of the catalysts suitable for methanol synthesis, have a molar ratio of Cu:Zn:Mg:Al at intervals 16,5-19,5:5,5-8,5:1,0:2,5-6,5. Especially preferred compositions of the catalysts suitable for the reaction of conversion of water gas, have a molar ratio of Cu:Zn:Mg:Al at intervals of 10-15:6-10:1:6-12.

As stated above, copper-containing catalysts are usually prepared by forming a homogeneous mixture of particles of compounds of copper and zinc, calcining the mixture, often in oxygen-containing atmosphere, usually air, to convert these compounds into oxides, followed by granulating and then restore. Firing is generally carried out at temperatures above 275°C and is usually carried out at temperatures in the range from 300 to 500°C.

In this invention, in order to obtain large values of the surface area of copper, stage firing is omitted, and a homogeneous mixture is subjected to reducing conditions in such a way that the copper compounds in it turn into copper without the original single stage heat for the conversion of copper to copper oxide. On the contrary, the drying is carefully controlled to ensure that water is removed as completely as possible, without causing decomposition of the copper in the copper oxide.

The value of area of the surface is copper catalysts obtained in accordance with this invention, is ≥60 m2/g Cu, preferably ≥70 m2/g Cu, more preferably ≥75 m2/g Cu, most preferably ≥80 m2/g Cu. As mentioned above, the surface area of copper can easily be determined by applying reactive frontal chromatography, as described in EP-A-202824. A particularly suitable method is the following. The formed elements of the catalyst is crushed and sieved to particle size of 0.6 to 1.00 mm, About 2.0 g of the ground material is weighed into a glass tube and heated to 30°C (restored and passivated samples) or 68°C (for oxide samples) and purge with helium for 2 minutes. Then the catalyst restore it by heating in a stream of 5% vol. H2in helium, at 4°C/min up to 230°C and subsequent keeping at this temperature for 30 minutes. The catalyst was then cooled to 68°C in a helium atmosphere. Through the reduced catalyst is then passed to 2.5% vol. N2O in helium. Selected gases was passed through a gas chromatograph and determined the allocation of N2. Its value can be calculated surface area of the copper catalyst.

The ratio of tensile crushing the formed elements of the catalyst according to this invention is the ratio of the average coloring strength and crush strength in the horizontal direction (in kilograms) restored molded element to the average crushing strength in the horizontal direction (in kilograms) of the molded element, catalyst after fabrication. In the catalyst according to this invention, this ratio is ≥0,500:1, preferably ≥0,600:1, more preferably ≥0,650:1, most preferably ≥0,700:1 and particularly preferably ≥0,750:1. The measurement of this ratio requires the measurement of crushing strength of the molded catalyst elements after fabrication, i.e. molded elements, formed from the restored and passivated powder, and re-restored molded elements, i.e. molded elements after copper passivated layer was re-converted to elemental copper by exposure to the influence of a stream of reducing gas. Accordingly, the strength of the formed elements of the catalyst after manufacturing can be measured on recovered and passivated catalyst in air, whereas the renewed strength of the catalyst, it is desirable to measure in an inert atmosphere to prevent the exothermic oxidation of the molded element. The crushing strength of the catalyst after manufacture, expressed as the average crushing strength in the horizontal direction, is preferably ≥6.5 kg, more preferably ≥10,0 kg, most preferably ≥12.0 kg, so that the catalyst possesses rises the th strength for loading into the reactor for the process of conversion of carbon oxides. The average crushing strength in the horizontal direction (MHCS) can be determined by conventional techniques. A suitable method for molded items after fabrication is the following method. The crushing strength of the molded items are measured on cylindrical pellets with a diameter in the range of 5-6 mm when using calibrated machines CT5 to determine the strength of the granules. Strength pellet crush strength is measured in the horizontal (i.e. radial) plane. Used a load cell 50, the speed when determining the crushing strength is 2.5 mm/min Tested at least 20 pellets, and determined the average value. For measuring the crushing strength of the recovered granules oxidized or restored and passivated granules must be initially processed at the stage of recovery. This can be achieved by placing the granules in the vessel, the air purge with nitrogen and the subsequent exposure of the granules to impact 2% H2nitrogen and heated to 90°C for 2 hours, then to 120°C for an additional 2 hours, then to 180°C for an additional 5 hours and then up to 235°C for an additional 7 hours, keeping at 235°C for 3 hours, followed by heating to 240°C for updat the additional 1 hour and subsequent curing at 240°C for 3 hours before cooling in the presence of a reducing gas and a purge with nitrogen for storage. The recovered pellets tested in inert (i.e. not containing O2the atmosphere during use of the machine CT5 placed in the glove box.

Because there is no stage firing before restoring, then a homogeneous mixture before recovery is not formed, since the porosity inside the granules, due to the decomposition of, for example, hydroxycarbonate compounds, during which allocated water and/or carbon dioxide, can lead to low mechanical strength, thereby reducing the process time.

A homogeneous mixture can be obtained by wet processing of oxides, for example, through joint reaction interaction of copper oxide, zinc oxide and ammonia in the aquatic environment, such as water, or by mixing a soluble metal compounds. A more simple way, it is obtained by decomposition of metal nitrates and alkaline precipitating reagent in aqueous medium, such as water, for example as described in GB-A-1010871, GB-A-1159535, GB-A-1296212 and GB-A-1405012. The reaction conditions of interaction and subsequent processing of the resulting suspension can be selected to obtain certain crystalline compounds, for example, the type of manasseite, rosasite, aurichalcite or malachite. A suitable procedure involves the joint precipitation of soluble metal salts precipitating real Tom, such as ammonium or alkali metal hydroxide, carbonate or bicarbonate. The order in which the mixed reagents, can be optimized in accordance with known principles, for example, using single-stage co-deposition, as in GB-A-1159035, or two-phase co-deposition, as in GB-A-1296212 and GB-A-1405012. Preferably all of the divalent oxide components are introduced through such co-deposition.

In a preferred embodiment, insoluble compounds of copper and one or more other insoluble metal compounds are precipitated by combining an aqueous solution of one or more soluble metal compounds, such as nitrate, sulfate, acetate, chloride of a metal or the like, and an aqueous solution of alkali carbonate as the precipitating reagent, such as sodium carbonate or potassium. Can also be non-carbonate precipitating reagents such as hydroxides of alkali metals or ammonium hydroxide.

Accordingly, a homogeneous mixture of discrete particles can be formed by combining aqueous solutions of soluble compounds of copper, zinc and, optionally, one or more of the promoting metal compounds selected from compounds of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si, or rare earth elements, with an aqueous solution of alkaline carb the Nata as a precipitating reagent in the presence of aluminum oxide or hydrated oxide of aluminum or degradable to them aluminum compounds. In a preferred embodiment, the aluminum oxide or aluminum hydroxide dispersed in the form of a colloidal solution, is used as a source of aluminum oxide. Such aluminum oxide or aluminum hydroxide dispersed in the form of a colloidal solution, are commercially available or can be prepared by the known methods. Their use in obtaining copper catalysts are described, for example, in US4535071. When combining a solution of the compound of the metal and solution precipitating reagent alkaline carbonate reacts with soluble compound of the metal, forming insoluble metal carbonate, including hydroxycarbonate metal. Aging the precipitated material may be in the form of periodic or semi-continuous process, in accordance with which the aqueous suspension of precipitated material is maintained at elevated temperatures in one or more stirred tanks during the selected time periods. Suspension of the compounds in the liquid can be maintained by simple stirring, vigorous mixing, depending on the tendency of particles to settle. Optionally, the solution may be a polymer, to prevent subsidence. Alternatively, the deposited material may be subjected to aging in the reactor with pulsed flow, as the description is but in our application WO2008/047166, which are incorporated herein by reference.

After such mixing, the homogeneous mixture to extract the desired manner, for example by separation of mother solutions using known methods such as filtration, decanting or centrifugation, and washed to remove soluble salts. Especially, when the present compounds of alkali metals, alkaline metal preferably should be reduced to less than 0.2 wt.%, preferably less than 0.1 wt.%, more preferably less than 0.05 wt.% in the calculation of the corresponding oxide of the alkali metal to the dried material.

After each washing, the material is dried to form a powder of the catalyst precursor in the process, including the stage performed at a maximum temperature in the range of 180-240°C. Drying may therefore include heating the wet mixture into separate steps or in a continuous manner over an extended period of time, until it reaches the maximum temperature. Preferably stage of drying is performed using two or more separate stages of drying, which remove the water in several stages. Stage drying can be accomplished by the use of conventional equipment for drying, such as that used for oxide catalysts. One in which the version of the implementation drying includes the initial stage of heating the homogeneous wet mixture to a temperature in the range of 90-150°C, preferably 100-125°C in air or in inert gas in the furnace, drum dryer or similar equipment before drying at 180-240°C. In an alternative embodiment, the initial stage of drying is performed while applying the spray dryer, which also acts so that the formed agglomerates homogeneous mixture, is particularly suitable for compression molding into pellets. To facilitate spray drying, the washed material is preferably dispersing in water. The content of the solid residue in the source material for spray dryers can be more than 15 wt.%, however, preferably is ≥20 wt.%. Conventional spray equipment may be used when the inlet temperature in the range of 150-300°C and the outlet temperature in the range of 100-200°C. In the conditions when the inlet temperature above 240°C, the feed rate should be adjusted so that copper compounds are essentially not subjected to thermal decomposition. Preferred are agglomerates, spray dried, with an average particle size (when determining the fractions of screening, i.e. average particle size) in the range of 10-300 μm (microns), especially 100-250 microns.

Initial drying by oven or spray drying, preferably reduces containing the s of water in the catalyst precursor to < 20 wt.%, preferably <15 wt.%, more preferably ≤10 wt.%.

In any case, whether the process is single-stage drying, or a number of separate stages of drying, a homogeneous mixture is subjected to a stage of drying where it is heated to a temperature in the range of 180-240°C. Without intending to be limited by theory, believe that drying at these temperatures removes hemosorption and physically adsorbed water from the catalyst precursor, and that this gives the catalyst precursor increased strength. The time during which the mixture is maintained at a temperature in this range depends on the selected temperature, with longer periods of time desired for lower temperatures in this range, and shorter periods of time, are desired for higher temperatures. The maximum drying temperature 210-240°C is therefore preferred. Desirable are the drying times range from 2 to 8, preferably from 2 to 6 hours. Stage drying can be performed in air or in an inert gas, such as nitrogen or argon, in a furnace, drum dryer or other conventional drying equipment. As described above, the phase of drying does not make copper compounds, for example hydroxycarbonate compounds of copper, the copper oxide. After drying, the precursor is utilizator preferably stored in an atmosphere of dry air or dry inert gas, to prevent re-adsorption of atmospheric moisture.

Recovery of copper compounds may be conveniently achieved by exposure of the dried catalyst precursor effects gas containing hydrogen and/or carbon monoxide at atmospheric or increased pressure. Recovery is performed preferably at the lowest temperature at which it will occur. Accordingly, there can be used conventional methods of reduction with hydrogen, using a diluted stream of hydrogen, for example, 2% H2in N2and the catalyst precursor is slowly heated until then, until the start of the recovery. Found that usually the recovery begins at about 80°C and sufficiently completed at 200°C or even 150°C.

In this invention, the authors observed that the recovery of the precursor catalyst containing a carbonate of copper compounds, such as hydroxycarbonate copper (malachite) and/or zinc-containing malachite, can be performed at high concentrations of hydrogen in the stream of reducing gas for the whole stage of recovery without the problems commonly observed in the recovery of materials containing copper oxide. Therefore, in the preferred embodiment, recovery of the catalyst precursor, sod is rasih materials on the basis of hydroxycarbonate copper, performed by exposure of the dried catalyst precursor effect flow of hydrogen containing gas, containing >50% vol. hydrogen, more preferably >75% vol. hydrogen, particularly preferably >90% vol. of hydrogen. If desirable, it can be used even essentially pure hydrogen.

Recovery can be controlled with the use of conventional methods. For example, recovery can be performed for the precursor catalyst containing hydroxycarbonate copper, up until no more will be allocated to water and carbon dioxide. Recovery usually converts at least 50% of the recovered compounds, for example, carbonates of copper, the metal, but preferably continues until until >95% recoverable connections will not be converted into metal. Zinc and promoting connections during the recovery phase is converted mainly to their respective oxides.

In a particularly preferred method, the recovery is performed by means of fluidization of the powder precursor in a stream of reducing gas, in a suitable tank. The tank can be with external cooling and/or reducing gas may be subjected to heat in order to regulate the temperature of the recovered material, and condensive the ü and to remove the water from the reducing gas. Dried the reducing gas is desirable in the case of recycle to the fluidized bed material. This method is particularly suitable method for the rapid recovery of the catalyst precursor in the shortest possible time.

In restored condition, due to the large surface area, copper can rapid and exothermic to react with oxygen and moisture present in the air, and so it must be passivated for forming and storing. The composition is considered to be passivated if it is stable with respect to air, especially air at a temperature >50°C. This can be determined by thermogravimetric analysis (TGA), which is controlled by changing the mass of the material when it is heated. When oxidation occurs, the weight of the catalyst increases. Preferably, the passivated catalyst does not show a significant increase in weight when it is heated in air at 20°C/min until the temperature reached at least 80°C, preferably at least 90°C.

Passivation can be accomplished by the application of diluted oxygen and/or carbon dioxide, or powder catalyst precursor may be covered kislorodopronitsaemaya material. Passivation can be achieved by applying mixtures of inert gas/air, neprimerna nitrogen/air, in accordance with which the air concentration slowly increases over a certain period of time in order to form a thin layer of metal oxide on the surfaces of copper. Typically the oxygen is introduced in the application of air with a flow rate sufficient to maintain the temperature of the catalyst precursor between 10 and 100°C, preferably between 10 and 50°C, particularly preferably at 20-40°C, during passivation. For example, the recovered material may be subjected to a flow of inert gas, for example nitrogen, and air, is added at a content of 0.1 vol.%. It gently increases for some period of time up to 0.5% vol. oxygen, then up to 1 vol.%, then up to 2 vol.%, 5% vol. and up until the oxygen content is equal to its content in the air. Alternatively, the recovered composition of the catalyst can be passivated using a gas mixture containing carbon dioxide and oxygen in the ratio of CO2:O2≥2:1 to form a thin surface layer of metal carbonate, such as hydroxycarbonate metal.

In a preferred method, the passivation is performed by the fluidization of the powder recovered precursor in an inert gas, such as nitrogen, and the subsequent filing of gases containing oxygen and/is whether carbon dioxide, such as air or mixture of air and carbon dioxide at low concentrations. The tank can be with external cooling and/or passivating gas may be subjected to heat in order to regulate the temperature passivemode material.

If desired, the reservoir of fluidization can be used for both stages of recovery and passivation, as it eliminates the risk of exposing the recovered precursor to oxygen during storage.

Restored and passivated powder catalyst precursor can be further processed to obtain a molded elements, in particular, the following stages:

(i) Pre-compaction and granulation restored and passivated powder so that the molded elements were granules.

(ii) Combining the recovered and passivated powder with one or more binders and optionally with one or more powder materials and shaking to form spherical agglomerates or granules.

(iii) Converting the recovered and passivated powder in suspension (preferably non-aqueous), mixing/grinding in a disc mill and extrusion to form extrudates.

(iv) conversion of the Finance in suspension as described above, mixing/grinding in a disc mill and extrusion, with the formation of complex shaped structures, such as a monolithic structure or plate catalyst with secondary structure.

(v) Applying restored and passivated powder in an inert or, equally, the catalytically active native deposition of thin layers or similar processes.

All processes can be used binders and additives conventional in this type of technology. Also there are numerous other possibilities for additional processing.

Preliminary compaction and granulation of the powder is the most suitable for the preparation of molded elements according to this invention. Granules may be conventional cylindrical pellets with flat ends. Cylindrical pellets processes for the conversion of carbon monoxide respectively have a diameter in the range of 2.5-10 mm, preferably 3-10 mm, and the size ratio (length/diameter) in the range of 0.5 to 2.0. Alternatively, the formed elements of this invention can be in the form of rings or shamrocks. In a preferred embodiment, the molded element has the shape of a cylinder with hemispherical ends, with two or more grooves along its length. In one such variation is made, the ing the catalyst has the shape of a cylinder, having a length C and diameter D, and the outer surface of the element has two or more grooves, elongated along its length, the said cylinder has hemispherical ends of lengths A and B, so (A+B+C)/D is in the range from 0.50 to 2.00, and (A+B)/C is in the range from 0.40 to 5.00. A and B preferably are the same. C is preferably in the range from 1 to 25 mm, D is preferably in the range from 4 to 40 mm, more preferably from 4 to 10 mm and most preferably there are 4 grooves located at the same distance from one another in the direction of the circumference of the cylinder. Alternatively or in addition, the molded elements can have one or more through holes running along their length. Such cylindrical catalysts with hemispherical ends have improved ability to fill and/or lower pressure drop compared to conventional forms without grooves or without holes. Such adaptation of the catalyst of the usual cylindrical shape with flat ends became possible due to the improved strength properties of the powder recovered and passivated catalyst precursor.

Granules, in particular of cylindrical pellets with a flat or hemispherical ends, as described above, preferably are made at densities is of renul in the range of from 1.4 to 2.5 g/cm 3, more preferably from 1.8 to 2.4 g/cm3. The density of the granules can be easily determined by calculating the volume of the sizes of the granules and the measurement of its mass. When the density is increased, the volume of voids in the molded elements is reduced, which, in turn, reduces the penetration of the reaction gases inside the element and out of it. Therefore, densities >2.5 g/cm3the reactivity of the catalyst may be less than optimal, despite the large surface area of copper recovered and passivated powder. For densities <1.4 g/cm3strength crush strength may be insufficient for long-term use in modern processes of conversion of carbon monoxide.

Surface area by BET restored and passivated catalyst, when it is determining the absorption of nitrogen is preferably >80 m2/g, more preferably >90 m2/g; and a pore volume, measured using the desorption branch at 0.99, and is preferably >0.15 cm3/g, more preferably >0.2 cm3/year

The invention includes a method of converting carbon oxides, which comprises the reaction interaction process gas containing carbon monoxide, which contains hydrogen and/or water vapor and contains at least one component is UNT of hydrogen and carbon monoxide, in the presence of a catalyst. The catalyst may be activated in situ by exposure to its effects flow of reducing gas, preferably containing hydrogen to transform the layer passivated copper again in elementary copper. Accordingly, the invention preferably involves the following stages (i) activating the catalyst by bringing the specified catalyst in contact with a stream of reducing gas and (ii) the reaction of the interaction process gas containing carbon monoxide, which contains hydrogen and/or water vapor and contains at least one component of the hydrogen and carbon monoxide, in the presence of a catalyst to form a product flow. Since the bulk copper is already in the metallic form, this stage of activation may be performed faster and with less formation of water as a by-product to be disposed of than in the case of conventional catalysts containing copper oxide. Activation can be accomplished by the use of hydrogen-containing gas, including synthesis gas containing hydrogen and oxides of carbon, at temperatures above 80°C and at pressures in the range of 1-50 barg. pressure (0.1-5 MPa). In addition, the maximum temperature recovery is preferably from 150 to 200°C.

And the finding provides processes using the catalyst, in particular:

A. Synthesis of methanol, in which a gas mixture containing carbon monoxide, hydrogen and optionally carbon dioxide, is passed through the catalyst at a temperature in the range of 200-320°C, a pressure in the range of 20-250 (2-25 MPa), preferably 30-120, bar abs. pressure (3-12 MPa) and time flow rate in the range of 500-20000 h-1. The process can be carried out in a single circulation or recirculation, and may include cooling by surface indirect heat exchange contact with the reaction gas, or by units of the catalyst layer and the gas cooling between layers by injection of a cooling gas or by means of indirect heat exchange. For this process, the catalyst preferably contains copper, zinc oxide and magnesium oxide, together with the aluminum oxide.

B. Modified methanol synthesis, in which the catalyst also contains free alumina with a surface area of 50-300 m2g-1so that the product of synthesis is relatively enriched dimethyl ether. Temperature, pressure, time and flow rate are the same as for methanol synthesis, however, the synthesis gas contains hydrogen and carbon monoxide in a molar ratio of less than 2.

C. Modified methanol synthesis, in which the catalyst also contains alkali metal UB is not content in the range from 0.2 to 0.7 wt.%, in particular potassium, added on a separate stage to the homogeneous mixture so that the product of the synthesis contains higher alcohols containing from 2 to 5 carbon atoms), usually in addition to methanol. The process conditions in General similar conditions B, however, are preferred over high pressure and temperature, and lower hourly flow rate at the set interval.

D. Low-temperature reaction conversion, in which a gas containing carbon monoxide (preferably 4% in volume per dry gas) and water vapor (molar ratio of water vapor to the total dry gas is usually in the range of from 0.3 to 1.5), is passed through the catalyst in a fixed bed adiabatic conditions at a temperature in the range from 200 to 300°C and at a pressure in the range of 15-50 bar abs. pressure (1.5 to 5 MPa). Typically, the gas inlet is a product of "high-temperature reaction of conversion", in which the content of carbon monoxide is reduced by the reaction of interaction of iron-chromium catalyst at a temperature in the range 400 to 500°C, and then cooled by indirect heat exchange. The content of carbon monoxide output is usually in the range from 0.1 to 1.0%, mainly at 0.5% in volume ratio calculated on a dry gas.

E. Createmirror the second reaction conversion, in which a gas containing carbon monoxide and water vapor, is served at a pressure in the range of 15-50 bar abs. pressure (1.5 to 5 MPa) to the catalyst at the inlet temperature typically in the range from 200 to 240°C, although the temperature at the input can be as high as 280°C and the outlet temperature is typically up to 300°C, but can be as high as 360°C. These conditions are more stringent than those in D, so it is expected that the new catalyst is particularly advantageous.

F. Low-temperature reaction conversion and heat transfer, in which the reaction interaction in the catalyst layer is in contact with the heat exchange surfaces. Coolant is usually water at such pressure that there is a partial or full boil. A suitable pressure is from 15 to 50 bar abs. pressure (1.5 to 5 MPa), and the resulting steam can be used, for example, to drive a turbine or to provide process steam for the reaction conversion, or for the previous stage, which generates the source water gas for conversion. Water can be in tubes surrounded by the catalyst, or Vice versa. Discusses two private mode of carrying out this type of conversion process:

(i) Lowering the temperature profile, for example, when the interval of the input 240 is about 350°C (preferably from 240 to 310°C) in a typical reduction of up to 50°C (preferably from 10 to 30°C) between input and output. This provides improved heat recovery in the upper reaches, as the source gas that is produced at high temperature can be cooled to a lower temperature than in the conventional process. It also provides an equally low content of carbon monoxide at the outlet, as in conventional low-temperature reaction conversion;

(ii) Increasing the temperature profile, for example, when the inlet temperature in the range of 100 to 240°C, increasing to a maximum of 240 to 350°C, with subsequent lowering of the temperature profile as in (i) above. This profile is suitable for the reaction of conversion of gas obtained by partial oxidation of coal or raw materials on the basis of heavy hydrocarbons, with subsequent treatments at ambient temperature or below, to remove carbon dust and sulfur compounds. Hot water when the heat brings the raw gas to a temperature at which the reaction conversion occurs rapidly. In such a process zone at the entrance to the catalyst bed of the reaction conversion can be a preheating zone in which the loaded inert granules, for example, of alpha-aluminum oxide. In any such conversion may be desirable to protect the catalyst from poisoning, such as sulfur or chlorine, and for that upstream can be placed protective layer rashodov the catalyst or zinc oxide or padmalochan aluminum oxide.

Processes involving heat transfer, described, furthermore, in EP-A-157480. Providing heat also helps to regulate the temperature of the catalyst during reductive activation and also by responding to any reduction in temperature below the condensation temperature of water vapor, makes practical the use of chloride of protective material, such as podslushannyy aluminum oxide, in the input zone above the catalyst.

Alternatively, for the synthesis of alcohol, instead of applying a fixed catalyst layer, the catalyst may be suspended in the liquid. Despite the fact that, in principle, the particles obtained above methods of preparation of the catalyst, suitable for use in a fixed bed, can also be used in suspension in a liquid, it is preferable to use mobile connections in powder form or in any form of fine particles agglomerated to the extent insufficient for what is necessary in the process fixed bed.

The invention will now be additionally described by reference to the examples below.

The surface area of copper and an average crushing strength in the horizontal direction was measured by using the methods described above. The crushing strength was measured by the ü when using a desktop automatic tester mechanical strength CT5 (made Engineering Systems (Nottn) Ltd).

X-ray diffractometry (XRD) was performed using advanced diffractometer Bruker AXS D8-mode parallel rays using Cu Ka radiation, filtered Nickel, and LaB6 standard profile line.

Shrinkage of the pellets was measured manually using a caliper with digital display. Granules before recovery and after him physically measured to determine volume changes. The recovered pellets were tested in a glove box in an inert (i.e. not containing O2) atmosphere. Experienced 20-50 pellets and determine the average.

EXAMPLE 1. Preparation of catalyst

The powder catalyst precursor was prepared at a molar ratio of Cu:Zn:Mg:Al average of 17.5:6,5:1:4 deposition at 60-75°C and a pH of more than 6.0 homogeneous mixture of the solutions of the nitrates of copper, zinc and magnesium in the presence of Zola aluminum hydroxide dispersed in the form of a colloidal solution, using potassium carbonate as the precipitating reagent. When the coprecipitation was completed, the suspension is kept at 65°C until there was no color transition from blue to green. The suspension was then filtered and washed until such time as the levels of alkali metals did not reach the minimum level (<500 million-1).

The precipitate on the filter then is was spencervale to obtain a suspension of 35 wt.% and then dried by spraying, to form agglomerates with a diameter of about 10-50 microns.

Powder, spray dried, and then subjected to processing at the stage of drying by heating it to 210-240°C and maintain at this temperature for 6 hours. X-ray diffraction analysis (XRD) confirmed the presence of hydroxycarbonate copper and showed no formation of copper oxide during the stage of drying. The material of the catalyst precursor was then cooled to 60-80°C in a dry nitrogen.

The catalyst precursor was restored by exposure exposure to hydrogen-containing gas, containing >90% H2initially at about 80°C, during restoration, performed at a maximum temperature of 160°C. the recovery Process continued up until no longer stood out water and carbon dioxide when measured with conventional detectors. The calculations showed that >95% copper turned into elemental form. The recovered catalyst material was then cooled to 20 to 40°C in a dry nitrogen.

The recovered catalyst material was then passivatable at 20-40°C with the use of mixtures of nitrogen/air, which was initially adjusted to provide the oxygen content of 0.1 vol.%, and then gradually increase the oxygen content up to 1% vol. oxygen and then to higher values, while passivating g is C not become 100% air. The rate of increase of the oxygen content was regulated by temperature monitoring.

The passivated powder catalyst was mixed with a small amount of graphite and shaped in the form of cylindrical pellets using conventional equipment for granulation in the air. The granules had a diameter of 5.4 mm in length 3,2 mm

For comparison, a comparative catalysts having the same molar ratio of Cu:Zn:Mg:Al, was prepared by the same deposition process and was spray dried using the same method, spray drying, however, instead of a stage of high-temperature drying powders, spray dried, subjected to firing at (I) 295°C or (II) 500°C, at which copper compounds are turned into copper oxide. The resulting oxide powder was again mixed with a small amount of graphite and shaped in the form of cylindrical pellets with a diameter of 5.4 mm and a length of 3.2 mm

The magnitude of the surface area of the copper granules was determined reactive frontal chromatography, as described above. In each case, the surface area was measured on crushed and sieved granules. The results were as follows:

SampleThe surface area of copper, m2/g Cu
Comparative mA is Arial I (fired at 295°C) 40,0
Comparative material II (annealed at 500°C)38,8
Example 189,6

The results show that the magnitude of the surface area of the copper recovered and passivated catalyst in accordance with this invention exceed those that take place in cases where the preparation includes a step of firing.

The average crushing strength in the horizontal direction (MHCS) were determined for the pellets immediately after production and after recovery in order to simulate the strength in situ.

Granular hydrated materialA raft of granules, g/cm3MHCS granules after manufacture manufacture (kg)MHCS was established granules (kg)The ratio of MHCS (after restitution:after fabrication)
Comparative catalyst I1,9712,22,40,197:1
Comparative catalyst II1,978,4 2,60,310:1
Example 1a2,0417,214,30,831:1

The results show that there can be achieved a very high resistance to crushing, and that at a comparable density granules, made from a powder precursor obtained at the stage of firing, is significantly reduced after recovery compared with the granules according to this invention.

EXAMPLE 2

The preparation of the catalyst of example 1 was repeated using sodium carbonate as the precipitating reagent instead of potassium carbonate.

The source material for the spray dryer had a solids content of residue 37 wt.%.

The settings of the spray dryer were as follows:

Inlet temperature: 350°C

Outlet temperature: 110°C

Discharge pressure: 40 bar (4 MPa)

The residual moisture content in the powder after spray drying was 4.7%, but the particles had a free fluidity. 92 wt.% the particles had a particle size of 53-250 µm (microns) when 62.3 wt.% particles having a particle size in the range of 100-180 microns.

The product, spray dried, subjected to the same stage of drying, restoration and passivation, as in example 1. ostanovlennyi and passivated powder was again shaped in the form of cylindrical pellets with a diameter of 5.4 mm and a length of 3.2 mm, when the density of the pellets roughly 2.0. The surface area of copper was measured for these pellets using the above method.

SampleThe surface area of copper, m2/g Cu
Example 283,0

Also, we studied the range of densities of the granules. The average crushing strength in the horizontal direction (MHCS) were determined for the pellets immediately after production and after re-restore to simulate the strength in situ. The results were as follows:

SampleThe density of the granules, g/cm3MHCS after production, kgMHCS after re-restore kgThe ratio of MHCS
Example 2a1,737,56,50,867:1
Example 2b1,768,06,60,825:1
Example 2c 2,0015,913,50,849:1
Example 2dto 2.0618,214,90,819:1
Example 2e2,2523,416,30,697:1

Compared to this, the usual copper oxide catalyst having a molar ratio of Cu:Zn:Mg:Al and prepared using the same sodium precipitating reagent, gave MHCS after recovery of oxide pellets approximately 2.5 kg (at a density of granules of 1.97).

EXAMPLE 3

Repeated the preparation of the catalyst of example 1.

The source material for the spray dryer had a content of the solid residue 20-25 wt.%.

The settings of the spray dryer were as follows:

Inlet temperature: 290-300°C

Outlet temperature: 114-120°C

Discharge pressure: 18-20 bar (1,8-2,0 MPa)

The content of residual moisture in the powder, spray dried, was 8-10%. 95 wt.% the particles had a particle size of 63-250 µm (microns) in 62,8 wt.% particles having a particle size in the range of 150-210 μm.

The product, spray dried, subjected to the same stage of drying restoration and passivation, as in example 1. Restored and passivated powder was again shaped in the form of cylindrical pellets with a diameter of 5.4 mm and a length of 3.2 mm, with a density of pellets roughly 2.0.

The surface area of copper was measured using the above method.

SampleThe surface area of copper, m2/g Cu
Example 380,1

Also, we studied the range of densities of the granules. The average crushing strength in the horizontal direction (MHCS) were determined for the pellets immediately after production and after re-restore to simulate the strength in situ. The results were as follows.

SampleThe density of the granules (g/ml)MHCS after the fabrication of (kg)MHCS after re-recover (kg)The ratio of solution MHCSShrinkage after restitution (vol.%)
Example 3a1,738,86,90,784:111,2
Example 3b1,9414,610,30,705:19,9
Example 3c2,1017,710,70,604:1the 10.1

The properties of the granules after fabrication (crushed and screened), measured using the absorption of nitrogen were as follows:

SampleSurface area by BET (m2/g)Pore volume (cm3g-1)
Example 3a95,70,30
Example 3b94,00,27
Example 3c91,50,24

EXAMPLE 4: Test - methanol synthesis

The sample pellets from examples 1 to 3 were crushed and 2 ml (0.50 g) fragments in the range of sieves 0.6-1.0 mm were loaded into a microreactor and restored to activate the catalyst in the gas mixture 2% vol. H2/N2to 240°C. the Gas for methanol synthesis when status is ve, in volume %, 6,0 CO, 9,2 CO2, 67,0 H2and 17.8 N2was passed through the catalyst at a pressure of 50 barg. pressure (MPa), a temperature of 225°C, and time flow rate 40000 h-1. The methanol output was measured in the mode of "on-line" using a combination of systems, IR and gas chromatography. Then for accelerated testing on the service life of the pressure and the temperature was increased to values above normal operating conditions; these values are supported for 144 h, and then decreased to their original levels that are again measured the methanol content in the output.

The relative activity of the catalysts of Examples 1a, 2c and 3b, each of which had a density of granules roughly 2.0 below. Activity is shown in comparison with its value for standard oxide (i.e. fully restored in situ) a catalyst having the same molar ratio of Cu:Zn:Mg:Al, tested under the same conditions. Measurements were conducted with 17 hours on-line and 144 hours on-line. The results were as follows:

CatalystThe on-line timeRelative activity
Example 1a171,46
Use the 2c 171,29
Example 3b171,33

Standard171,00
Example 1a1441,52
Example 2c1441,24
Example 3b1441,42
Standard1441,00

The results show high activity and reduced the degree of deactivation of the catalysts according to this invention in comparison with a standard oxide catalysts with the same molar ratio of Cu:Zn:Mg:Al.

EXAMPLE 5

The method of example 1 was repeated, except that the washed homogeneous mixture was dried in a drying pan with stirrer at 110°C for 6 hours in a drying Cabinet with a fixed air instead of spray drying, before drying at 210-240°C. the Dried powder was recovered and was passivatable in accordance with the method of Example 1. Then restored and assidiously powder was again shaped in the form of cylindrical pellets with a diameter of 5.4 mm and a length of 3.2 mm and a density of roughly 2.0. The surface area of copper was measured using the above method.

SampleThe surface area of the Cu (m2/g Cu)
Example 584,4

We studied the range of densities of the granules. The average crushing strength in the horizontal direction was measured as described above.

SampleThe density of the granules, g/cm3MHCS after production, kgMHCS after repeated restitution, kgThe ratio of MHCS
Example 5a1,717,78,31,078:1
Example 5b1,9514.4V12,20,847:1

The residual strength of these catalysts after recovery was very high compared to the standard oxide catalysts (restored in-situ). Relative activity for example 5b, measured with the aid the receiving test, described in example 4, compared to the standard oxide (restored in-situ) the catalyst at 144 hours, was 1,73. Thus, the activity of the catalyst according to this invention is significantly higher than in the case of a standard catalyst.

EXAMPLE 6 (comparative)

The catalyst was prepared in accordance with example 1 of US 4863894 (at a molar ratio of Cu:Zn:Al, constituting 59,8:25,6:14,5). The washed material was dried at 110°C, but without the stage of drying at 180-240°C, and then restored using a mixture of 5% H2+ 95% N2in volume. The recovered powder was passivatable and was molded in the same manner as in example 1. We studied the range of densities of the granules. The average crushing strength in the horizontal direction (MHCS) were measured for granules after manufacture and for granules after re-restore to simulate the strength in situ.

SampleA raft of granules (g/ml)MHCS after production-ing (kg)MHCS after re-restore-recovery (kg)The ratio of solution MHCSShrinkage after restore-recovery (% vol.)
Comparative example 6a1,70 8,11,70,210:116,2
Comparative example 6b1,8311,43,70,325:119,2
Comparative example 6c1,8812,3the 3.80,309:119,0

Although granular material was originally durable, value for re recovery show a significant loss of strength, which gives the ratio of the strength of a lot less than 0,500:1, and the shrinkage in excess of its value for the conventional oxide catalysts and catalysts according to this invention. High value of shrinkage is undesirable for catalysts because it is wasteful in relation to the volume of the reactor.

The catalyst (example 6c) tested in accordance with test method shown in example 4. The relative activity of the catalyst was decreased to 0.97 for 144 hours.

EXAMPLE 7:

Test - low-temperature conversion of water gas

Activity towards the conversion of water gas for example 1a and a conventional oxide catalyst with the eat same molar ratio of Cu:Zn:Mg:Al was determined by grinding granulated material and loading of approximately 0.5 g of the fraction of material with a size of 0.6-1.0 mm in a laboratory reactor. The catalyst was restored before the test through a mixture of 2% H2/N2at a temperature of from 150 to 220°C and then cooled to the desired operating temperature. The reactor was operated using the standard gas composition for low temperature conversion (LTS), is presented below:

ComponentCOCO2H2N2H2O
vol.%to 2.6710,6736,6716,6733,33

The process was carried out at 27 barg. pressure of 2.7 MPa and in the temperature range from 205 to 250°C. the Hourly space velocity ranged from 20000 to 80000 h-1.

Manufactured gas was analyzed with the use of infrared analysis, and the condensate was collected and analyzed by gas chromatography to determine the conversion of CO. The conversion was determined for each catalyst as a function of time on-line and temperature. Conversion after 1 week was 41% for example 1a against the conversion of 37% for the comparative oxide catalyst (restored in-situ), indicating took the group activity. When used conditions, the catalyst according to this invention showed a higher selectivity than the oxide catalyst. It was formed less methanol, i.e. the catalyst was more selective, and this was seen in relation to other reaction products, such as propionic acid, the content of which has been reduced by about 20 wt.% compared to oxide catalyst. Based on the profile conversion, the catalyst of this invention also showed improved resistance to sintering, i.e. the slower the loss of activity than the oxide catalyst.

EXAMPLE 8:

The preparation of the catalyst; the influence of the shape and density of the granules

Repeated the preparation of the catalyst of example 1. The material supplied to the spray dryer had a content of the solid residue 30-35 wt.%. The settings of the spray dryer were as follows:

Inlet temperature: 280-300°C

Outlet temperature: 110-120°C

Discharge pressure: 18-20 bar (1,8-2,0 MPa)

The content of residual moisture in the powder, spray dried, was <5%. 95 wt.% the particles had a size of 63-250 µm (microns). The product, spray dried, subjected to the same drying, restoration and passivation, as in example 1.

Restored and passivated powder was molded in the form:

a) 4-lobed/grooved cilindric the ski granules with exactly hemispherical ends of a diameter of 6.0 mm and a total length of 4.0 mm at a density of pellets is approximately equal to 1.82 g/cm 3. The height of the upper and lower hemispheres was 1.5 mm,

b) 4-lobed/grooved cylindrical pellets with exactly hemispherical ends of a diameter of 6.0 mm and a total length of 4.0 mm at a density of granules about 2,02 g/cm3. The height of the upper and lower hemispheres was 1.0 mm, and

c) 4-lobed/grooved cylindrical pellets with exactly the hemispherical ends with a diameter of 5.0 mm and a total length of 4.0 mm at a density of granules of about 1.83 g/cm3. The height of the upper and lower hemispheres was 0.5 mm.

The surface area of copper was measured using the above method.

ExampleThe density of the granules, g/cm3The surface area of copper, m2/g Cu
Example 8a1,8275,8
Example 8b2,0273,7
Example 8c1,83to 78.3

The average crushing strength in the horizontal direction (MHCS) were determined for the pellets immediately after production and after re-restore to simulate the strength in situ. The results were following the I.

SampleA raft of granules (g/ml)MHCS after production-ing (kg)MHCS after re-restore-recovery (kg)The ratio of MHCSShrinkage after restore-recovery (% vol.)
Example 8a1,827,04,00,571:18,9
Example 8b2,028,14,60,568:1the 9.7
Example 8c1,8312,19,10,752:19,6

The properties of the granules after fabrication (crushed and screened), measured using the absorption of nitrogen were as follows:

td align="center"> 107,1
SampleSurface area by BET (m2/g)Pore volume (cm3g-1)
Example 8a0,26
Example 8bto 114.40,29
Example 8c91,50,25

The results show that the number of specific molded pellets of the catalyst can be manufactured with sufficient strength and surface area for large-scale industrial applications.

EXAMPLE 9:

Test - low-temperature conversion of water gas

The catalysts were prepared in accordance with the method of Example 1, in which stage leaching was controlled for the influence on the residual content of K2O.

Products, spray dried, subjected to the same drying, restoration and passivation, as in example 1. Restored and passivated powders were molded in the form of cylindrical pellets with a diameter of 5.4 mm and a length of 3.6 mm, and the density of the granules is from about 1.8 to 2.0 g/cm3.

Activity and selectivity for the conversion of water gas these catalysts and conventional oxide catalyst with the same molar ratio of Cu:Zn:Mg:Al was determined using the method and apparatus of Example 6. Results after 1 week were as follows:

the Rymer The content of alkali metal, m-1Conversion, %The selectivity ratio
Example 9a38051,11,22
Example 9b31051,11,14
Example 9c1154a 38.52,20
Example 9d157130,52,41
Comparative oxide catalyst34037,01,00

The results show that the catalysts according to this invention having a low (<500 million-1the content of alkali metal, are more active and have higher selectivity than conventional oxide catalyst, and that the increase of the content of alkali metal to ≥1000 million-1can give comparable activity with a significant improvement in selectivity. Accordingly, the content of the alkali metal is between 0.1 wt.% and 02 wt.% can provide better selectivity of the conversion of water gas.

1. The catalyst suitable for use in reactions for the conversion of carbon oxides in the form of granules, formed by pressing the powder recovered and passivated catalyst, and powder that contains copper in the range of 10-80 wt.%, zinc oxide in the range of 20-90 wt.%, the aluminum oxide in the range of 5-60 wt.% and, optionally, one or more oxide promoting compounds selected from compounds of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare earth elements, in a quantity in the range of 0.01-10 wt.%, and these granules have an average crushing strength in the horizontal direction after fabrication ≥6.5 kg, the ratio of the average crushing strength in the horizontal direction after the restoration and post production at ≥0.5:1 and a surface area of copper of more than 60 m2/g Cu.

2. The catalyst according to claim 1, containing magnesium in the amount of 1-5 wt.%, in the calculation of the MgO.

3. The catalyst according to claim 1, in which the mass ratio of Cu:Zn per oxide is 1:1 or higher.

4. The catalyst according to claim 1, in which the ratio of strength crush strength is ≥0,600:1, preferably ≥0,650:1, more preferably ≥0,700:1, particularly preferably ≥0,750:1.

5. The catalyst according to claim 1, in which the average crushing strength in the horizontal direction of the catalyst after manufacturing status is made by ≥10,0 kg preferably ≥12,0 kg

6. The catalyst according to claim 1, in which the surface area of copper is ≥70 m2/g Cu, preferably ≥75 m2/g Cu, more preferably ≥80 m2/year

7. The catalyst according to claim 1, in which the granules have a density in the range of from 1.4 to 2.5 g/cm3preferably from 1.8 to 2.4 g/cm3.

8. A method of manufacturing a catalyst according to claim 1, comprising the following stages:
(i) forming in an aqueous medium of the composition containing a homogeneous mixture of discrete particles of copper, zinc, aluminum and, optionally, one or more of the promoting metal compounds selected from compounds of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare earth elements,
(ii) recovering and drying the composition with the formation of the catalyst precursor,
(iii) placing the dried composition of the catalyst precursor effects of reducing conditions in such a way that the copper compounds in it turn into copper,
(iv) the passivation of surfaces restored copper, and
(v) forming restored and passivated composition in the form of pellets by extrusion,
characterized in that before recovery of copper compounds homogeneous mixture is subjected to drying at a temperature in the range of 180-240°C.

9. The method according to claim 8, in which a homogeneous mixture of discrete particles formed by joint precipitation through the your combining aqueous solutions of soluble compounds of metals from copper compounds, zinc and, optionally, one or more of the promoting metal compounds selected from compounds of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare earth elements, with an aqueous solution of alkali carbonate as the precipitating reagent in the presence of alumina or hydrated alumina.

10. The method according to claim 9, in which the source of alumina or hydrated alumina is dispersed in the form of a colloidal solution of aluminum oxide or aluminum hydroxide.

11. The method according to claim 8, in which the drying is performed in two or more stages, and one step includes heating the homogenous mixture to a temperature in the range of 90-150°C, preferably 100-125°C in air or in an inert gas to reduce the moisture content to <20 wt.%, preferably <15 wt.%, more preferably ≤10 wt.%, before drying at 180-240°C.

12. The method according to claim 11, in which the drying is performed in two or more stages, including the stage of drying the homogeneous mixture spray before drying at 180-240°C.

13. The method according to item 12, in which the spray drying produces a spray dried powder with an average particle size (average particle size) in the range from 10 to 300 μm (microns).

14. The method according to claim 8, in which the recovery is performed using a hydrogen-containing gas having a hydrogen concentration ≥50 vol.%, preference is sustained fashion ≥75 vol.%, more preferably ≥90%vol.

15. A method of converting carbon oxides, which comprises the reaction interaction containing carbon monoxide process gas that contains hydrogen and/or water vapor and contains carbon monoxide, in the presence of a catalyst according to any one of claims 1 to 7 or of the catalyst prepared by the method according to any of PP-14.



 

Same patents:

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

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.

1 tbl, 1 dwg

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: process engineering.

SUBSTANCE: invention relates to production of metal-carbon-bearing bodies. Said bodies include ferromagnetic metal particles encapsulated with graphite carbon plies. This method comprises impregnation of cellulose, cellulose-like or carbohydrate boy or bodies produced by hydrothermal treatment with aqueous solution of at least one metal compound. Said metal or metals are selected from ferromagnetic metals or alloys. Then, impregnated bodies are subjected to thermal carbonisation by heating said bodies in inert atmosphere deprived, practically of oxygen at temperature over about 700°C. Now, the portion of at least one metal compound is reduced to appropriate metal or metal alloy.

EFFECT: production of catalytically active bodies.

15 cl, 8 dwg, 5 ex

Catalysts // 2517700

FIELD: chemistry.

SUBSTANCE: invention relates to catalysis. Described are methods of preparing a catalyst precursor, the first preparation step of which involves impregnating catalyst support particles with an organic cobalt compound in an impregnating liquid to form an impregnated intermediate product, calcining the impregnated intermediate product at calcination temperature not higher than 400°C to obtain a calcined intermediate product; and the second preparation step of which involves impregnating the calcined intermediate product from the first step with an inorganic cobalt salt in an impregnating liquid to form an impregnated support and calcining the impregnated support to obtain a catalyst precursor, wherein neither of the inorganic cobalt salts used at the second preparation step is used at the first preparation step. Described is synthesis of hydrocarbons in the presence of catalysts obtained using said method.

EFFECT: high catalyst activity.

20 cl, 5 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: invention relates to field of catalysis. Described is method of obtaining metal oxide on substrate, suitable for application as precursor for catalyst or sorbent, which includes the following stages: (i) impregnation of substrate material with metal nitrate solution in solvent, (ii) keeping impregnated material in gas mixture, containing nitrogen oxide, at temperature within the range to remove solvent from impregnated material with simultaneous drying and stabilisation of metal nitrate on substrate, with obtaining dispersed on substrate metal nitrate and (iii) calcination of dispersed on substrate metal nitrate to realise its decomposition and formation of metal oxide on substrate, where calcinations is performed in gas mixture, which consists of one or several inert gases and nitrogen oxide, and concentration of nitrogen oxide in gas mixture is within the range 0.001-15 vol.%.

EFFECT: increased catalytic activity of obtained products.

12 cl, 4 dwg, 11 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: described is a catalyst for selective oxidation of carbon monoxide in a mixture with ammonia, containing 0.7-1.2 wt % gold, 0.8-5.0 wt % Fe3+ and a crystalline theta-modification of aluminium oxide (θ-Al2O3) - the balance. Described are methods of producing said catalyst.

EFFECT: obtaining a catalyst with high activity and selectivity in oxidation of CO while reducing activity in ammonia conversion.

3 cl, 1 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: described is a catalyst for selective oxidation of carbon monoxide in a mixture with ammonia, containing 0.5-1.0 wt % gold, 1.0-5.0 wt % ruthenium and aluminium oxide - the balance. Described is a method of preparing said catalyst.

EFFECT: high selectivity in oxidising CO in a mixture with ammonia while reducing ammonia conversion.

3 cl, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to method of obtaining SCR-active zeolite catalyst and to catalyst, obtained thereof. Described is method of obtaining said catalyst, characterised by the fact that Fe-ion-exchange zeolite is first subjected to exposure to reducing hydrocarbon atmosphere for first thermal processing (3) in the range from 300 to 600°C, which reduces degree of oxidation of Fe ions and/or increases dispersion of Fe ions in zeolite, after that, reduced zeolite is subjected to exposure of oxidising atmosphere for second thermal processing (4) in the range from 300 to 600°C, which removes hydrocarbon residues and/or carbon residues in oxidation manner, and zeolite is burnt (2) in the course of first and second thermal processing (3 and 4) with obtaining catalyst. Described is SCR-active catalyst with burnt catalytic composition, which includes Fe-ion exchange zeolite, where Fe ions are present mainly with oxidation degree less than +3 and/or with high dispersion in zeolite, characterised by the fact that conversion of Fe ions into ions with higher degree of oxidation +3 and/or reduction of their dispersion is blocked.

EFFECT: increased catalytic activity with respect to selective reduction of nitrogen oxides in low-temperature range lower than 300°C.

19 cl, 2 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of obtaining block catalysts, catalysts of purification of exhaust gases (EG) of combustion engines (CE). Described is method of preparing catalyst for CE EG purification, in which for application of intermediate coating and active phase used is water suspension, which includes aluminium hydroxide - boehmite (AlOOH), reducing disaccharide and soluble salts of Ce, Zr, Y, La in form of nitric acid salts in proportion required for formation in coating of tetragonal phase Zr0.5Ce0,5O2, stable in temperature range 500-1000°C and ratio in coating (Me2O3+ZrO2+CeO2):γ-Al2O3-1:1, where - Me - Y, La, as well as one or several inorganic salts of platinum group metals, with thermal processing of coating being carried out simultaneously with reduction at temperature 550-1000°C. Obtained is catalyst for purification of exhaust gases of combustion engine with composition in wt %: Al2O3 - 6,0-7,0, (Me2O3+ZrO2+CeO2), where - Me - Y, La, - 6.0-7.0, including content of Me2O3, where - Me - Y, La,- 0.35-0.5 wt %. Active phase, in terms of platinum group metals is 0.07-0.08 wt %. Block carrier constitutes the remaining part to 100 wt %. Specific surface of coating after TP: 500°C - 100-120 m2/g, 800°C - 80-100 m2/g, 1000°C - 60-70 m2/g, 1200°C - 5-10 m2/g.

EFFECT: simplification of technology due to reduction of number of technological stages, time of their realisation, obtaining highly active and thermally stable catalyst.

5 cl, 1 tbl, 4 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of preparing a catalyst for hydroskimming organooxygen products of processing plant biomass. Described is a method of preparing a catalyst for hydroskimming organooxygen products of processing plant biomass, which is a composite containing nickel or a combination thereof with copper, which involves combined decomposition of transition metal compounds with a stabilising additive while heating to temperature of 300-350°C on air, followed by reduction with hydrogen, wherein the transition metal compounds used are nickel and copper carbonates, or hydroxides or a combination thereof, the stabilising additive used is ethyl silicate or powdered silicon dioxide SiO2; after decomposition, a molybdenum and/or phosphorus compound is added to the composite.

EFFECT: catalysts obtained using said method have high stability in media with high acidity and high water content.

2 cl, 4 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts. Described are methods of producing a cobalt Fischer-Tropsch synthesis catalyst, which involve preparation of a granular support from starting material - oxides of group III and IV metals, mixing the latter with modifying additives, followed by calcining, saturation with cobalt compounds, followed by calcining and activation of the catalyst in a current of a hydrogen-containing gas during Fischer-Tropsch synthesis.

EFFECT: low power consumption of the Fischer-Tropsch synthesis process.

2 cl, 11 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: method of producing a Fischer-Tropsch synthesis catalyst, involving calcining material: nitrate, oxonitrate, hydroxide or oxohydroxide of aluminium, zirconium, silicon or titanium, at temperature of 400-800°C, grinding particles to size of not more than 0.5 mm, granulating, calcining the granules at temperature of 400-800°C, saturating with a solution of cobalt compounds in amount of 20-30 wt % and promoters selected from: Re, Ru, followed by calcination at temperature of 270-450°C, grinding the granules to particle size of not more than 0.5 mm, mixing with a zeolite selected from: ZSM-5, Y, β, content of which ranges from 30 to 70% of the mass of the ready catalyst, granulating the obtained mixture together with boehmite, the mass of which ranges from 10 to 20% of the mass of the mixture, and calcining at temperature of 400-600°C, ion exchange of the granules with soluble compounds of palladium or Fe, Co, Ni, with content thereof of 0.5-8.0% of the mass of the ready catalyst, in a suspension of granules and a solution of said metal compounds at temperature of 60-80°C for 1-3 hours, drying the suspension at temperature of 80-150°C and calcining the residue at temperature of 300-500°C, activating the catalyst with hydrogen at 250-500°C in a fixed bed Fischer-Tropsch synthesis reactor while passing hydrogen with volume rate of 3000 h-1 at atmospheric pressure.

EFFECT: low cost of the catalyst, high stability of the catalyst.

1 tbl, 48 ex

FIELD: chemistry.

SUBSTANCE: metal-oxide catalytic electrode represents a 2-15 mcm thick porous nano-structured layer of composite, consisting of: catalyst - monocrystalline particles ruthenium and antimony-doped tin dioxide, with the average diameter about 30 nm, on which chemically applied are particles of a catalytic metal of a platinum group with the average diameter 3 nm, as well as 10-30% of a hydrophobisator, preferably polytetrafluoroethylene, and 10-20% of a ion-conducting additive, preferably sulphonated fluoropolymer. A suspension of an active composite mass is prepared by dispersion of a metal-oxide catalyst, hydrophobising and ion-conducting additives in a mixture of water, isopropyl alcohol and glycerol in a ratio of 0.4:0.2:0.4, respectively, after which it is applied on a gas-diffusion layer in any way and thermally processed at 120°C.

EFFECT: increased power of a fuel cell with such electrode.

2 cl, 3 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: described is a bead cracking catalyst which contains 10-35 wt % fine zeolite ReHY, 30-80 wt % kaolin and 60-5 wt % aluminium oxide, the source of which is a mixture of components of thermally activated aluminium oxide and basic aluminium chloride in weight ratio of 1:(0.25-0.95). Described is a method of producing said catalyst.

EFFECT: high catalytic activity.

2 cl, 1 tbl, 5 ex

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