Methanol synthesis method

FIELD: chemistry.

SUBSTANCE: invention relates to a methanol synthesis method, which includes the following steps: (i) conducting a reaction, in a reaction loop, of a process gas containing hydrogen, carbon dioxide and carbon monoxide over a catalyst to obtain a product gas, (ii) condensing methanol, water and secondary oxygenates from the product gas, (iii) returning unreacted gases into the reaction loop, where the catalyst includes pellets obtained by pressing from a reclaimed and passivated powdered catalyst, where said powder contains copper in the range of 15-70 wt %, zinc oxide, wherein the weight ratio Cu:Zn with respect to the oxide is in the range of 2:1 to 3.5:1, aluminium oxide in the range of 5-60 wt %, and optionally one or more oxide promoting compounds selected from Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare-earth elements, in the range of 0.01-10 wt %, wherein the catalyst is obtained by carrying out steps which include: (i) preparing, in an aqueous medium, a composition containing a homogeneous mixture of separate particles of copper, zinc, aluminium and optionally one or more promoting compounds of metals selected from Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare-earth elements, (ii) separating and drying the composition to form a catalyst precursor, (iii) exposing the dried catalyst precursor composition to reducing conditions so that copper compounds contained therein are reduced to copper, (iv) passivating the surface of the reduced copper, and (v) forming a reduced and passivated composition, where, before reducing the copper compounds, the homogeneous mixture is treated at the drying step at temperature in the range of 180-240°C.

EFFECT: when carrying out the disclosed method, total content of secondary oxygenates in the condensate is not more than 500 ppm.

12 cl, 7 tbl, 5 ex

 

The present invention relates to a method of methanol synthesis.

The methanol synthesis is of great importance for the industry. Methanol is normally synthesized in the reaction loop over containing copper catalyst from the synthesis gas comprising carbon monoxide and carbon dioxide. These reactions are shown below.

CO + 2H2→ SN3HE

CO2+ 3H2→ SN3HE + H2About

Unreacted gases are recycled in the circuit which can be purged to prevent the accumulation of inert components.

Catalysts for these reactions are usually made by giving the form of tablets small discrete particles formed from a homogeneous mixture of copper oxide and one or more other materials in the form of oxide, typically consisting of zinc oxide, which is not restored under the conditions of the reaction conversion. A homogeneous mixture is obtained by precipitation of copper compounds and compounds capable of turning into other materials in the form of oxides, and/or precipitation of copper compounds in the presence of other materials in the form of oxides or capable of turning them in connection with subsequent calcination in order to convert the precipitated copper compounds and, as necessary, other components in the oxides. Thus, tablets are usually made from poroshkoobraz�s oxides. To obtain an active catalyst, the tablets are subjected to redox conditions with the aim of restoring copper oxide in these pills to metallic copper. Stage of recovery is usually carried out in the reactor, to obtain a methanol synthesis process: that is usually a precursor of a catalyst in which copper is present in the form of copper oxide was charged into the reactor and carry out recovery by passing through an appropriate mixture of gases. Recovery of copper oxide is an exothermic process, and stage of recovery is often carried out in situ in a long time, applying streams of dilute hydrogen to avoid the destruction of the catalyst. This long start-up procedure is difficult to control and may require large operating costs.

Through these methods, the deposition/firing/ restore are usually catalysts, characterized by the surface area of copper of more than 20 m2per gram of copper, often more than 40 m2per gram of copper. Commercially available catalysts for the reaction of conversion of carbon monoxide typically have a surface area of copper of about 50 m2/g copper. The surface area of copper can be measured by the method of decomposition of nitric oxide, for example, as described in Evans and others in "Applied Catalysis", 1983, 7, 7 to 83, a particularly suitable method is described in ER.

Since the activity of the catalysts is related to the surface area of copper, it is desirable to obtain catalysts with a greater surface area of copper.

In US 4863894 described production method of the catalyst comprising a composition containing a homogeneous mixture of separate particles of compounds 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 the influence on this song redox conditions so that the contained copper compounds turned into copper, this is contained in a homogeneous mixture of copper compounds are restored to metallic copper without heating the specified homogeneous mixture to a temperature exceeding 250°C. Direct the restoration of the compositions of precipitated precursors of the catalyst allows to obtain catalysts with surface area of copper >70 m2per gram of copper.

However, the surface area of copper is not the only parameter of catalysts for conversion of carbon oxides, which need to be taken into account. In particular, are also of great importance to the strength and stability of the catalyst, both one and the other from the point of view of its activity and the CE�aktivnosti. The catalysts obtained by the method described in US 4863894 not have high stability needed for modern processes of conversion of carbon oxides, and today are still used for the oxide catalysts.

The inventors have unexpectedly discovered that the method using the catalyst of some form, formed from restored and passivated powder catalyst, can provide higher selectivity of the formation of methanol than the conventional catalysts.

Therefore, the present invention provides a method of synthesis of methanol, comprising the following stages:

(i) carry out the reaction of process gas containing hydrogen, carbon dioxide and carbon monoxide over a catalyst comprising shaped units derived from restored and passivated powder catalyst, and powder that contains copper in the range 10-80% by weight., zinc oxide in the range 20-90% by weight., the alumina in the range 5-60% by weight. and, optionally, one or more oxide promiting compounds selected from compounds of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare earths in the range 0.01-10% wt., with getting gas product, and

(ii) condensation of methanol, water and byproducts generated oxygenates, wherein the total content Pabon�x oxygenates in the condensate does not exceed 500 parts per million.

It should be understood that in General the content side of oxygenates does not include the amount of condensed water or methanol (product). The total content side of oxygenates can be easily determined using conventional techniques such as gas chromatography using known standards. The total content side of oxygenates can be a total measured concentration of organic oxygenates, however, convenient to consider it as an amount expressed in weight parts per million quantities of ethanol, 2-propanol, 1-propanol, methyl ethyl ketone, 2-butanol, 2-methylpropan-1-ol and 1-butanol in the extracted condensate. Taking into account that the total content side of oxygenates in the process is < 500 ppm, using the present invention, it is possible to obtain the total content side of oxygenates less than 400 ppm, preferably less than 300 parts per million.

Ethanol is the most significant side oxygenate. The ethanol content in the condensate preferably is ≤ 300 ppm, preferably ≤ 250 parts per million.

The relative degree of purity condensate also can be regarded as a convenient measure of the selectivity of the process. The relative degree of purity can be determined by measuring the total content of side oxygen�tov for catalyst, containing the same molar ratio of Cu, Zn, Al and other ingredients, cooked by restoring the molded blocks formed from an oxide precursor of the catalyst, as opposed to molded blocks formed from restored and passivated precursor obtained as described herein. The relative degree of purity of the condensate in the method of the present invention can be expressed as a percentage of the total content side of oxygenates in the condensate, obtained by the method of the present invention, to the same content, obtained by the method of an oxide catalyst using a catalyst of the same composition. The relative degree of purity of the condensate of the method of the present invention is ≤ 75%, preferably ≤ 50%, i.e. the method of the present invention allows to obtain a ≤ 75%, preferably ≤ 50% the number of side oxygenates in the condensate compared to the equivalent "method with an oxide catalyst."

Thus, the present invention includes a method of synthesis of methanol, comprising the following stages:

(i) implementation in the reaction loop response of the process gas containing hydrogen, carbon dioxide and carbon monoxide over a catalyst comprising shaped units derived from restored�about and passivated powder catalyst, and powder that contains copper in the range 10-80% by weight., zinc oxide in the range 20-90% by weight., the alumina in the range 5-60% by weight. and, optionally, one or more oxide promiting compounds selected from compounds of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare earths in the range 0.01-10% wt., with getting gas product, and

(ii) condensation of methanol, water and byproducts generated oxygenates, the relative degree of purity of the condensate is ≤ 75%, preferably ≤ 50%.

The method of the present invention is particularly useful, because it opens the possibility of faster start-up than conventional methods with an oxide catalyst, provides a higher activity and improved selectivity for methanol production, which is a significant advantage for modern large-scale installations, since it contributes to increased productivity and reduced waste.

The content of copper (calculated as Cu atoms) in the active catalyst generally corresponds to the range 10-80%, preferably 15-70% by weight. In this range, the copper content of 50-70% by weight. especially suitable for methanol synthesis. In this copper catalyst is present in the oxidized form in pestiviruses layer and in the elemental form under the ice. Preferably, in the catalyst after production of the present�em < 50% (in terms of atoms), more preferably, < 40% (in terms of atoms) of copper in the oxidized form.

In addition to copper metal, the catalyst may contain one or more other metals having catalytic activity for the synthesis of alcohols examples of such other metals may serve as cobalt, palladium, rhodium or ruthenium. Optional, may be present metallic silver. Other catalytically active metals, if present, are usually present in relatively smaller amounts; the percentage of such other catalytically active metals, usually between 1-10 atoms of metals per 100 atoms of copper.

Containing copper catalysts peculiar to the problem consists in the fact that when heated above 250°C, the copper atoms tend to be sintered with each other, which leads to decrease of the area of the copper surface after some time of use at elevated temperatures and, as a consequence, the decline in activity. To partially address this shortcoming, the catalyst contains at least one additional material, including zinc compounds and optionally one or more oxidic promiting compounds selected from compounds of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare earth elements. In this catalyst, the content of zinc oxide may lie in diapazone-90% wt., and one or more oxide promiting connections, if any, may be present in amounts in the range 0.01-10% by weight. Magnesium compounds are preferred, and this catalyst preferably contains magnesium in an amount of 1-5% by weight., in terms of MgO. Promiting the connection is not restored to the metal in terms of the process and are usually present in the catalyst in the form of one or more oxides.

Aluminum in the form of aluminum oxide, including partially hydrated aluminum oxide, is also present in the catalyst. The amount of aluminum oxide may be in the range 5-60% by weight. (in terms of Al2O3). Aluminum oxide can be added directly or formed from aluminum compounds which decompose to oxide or hydrated oxide.

The preferred composition of the catalyst precursor includes, before reconstruction, solid substance containing mixed carbonates, including hydroxycarbonate, metals - Cu and Zn, in which is dispersed aluminum oxide or hydrated oxide of aluminum, and optionally containing one or more compounds of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare earth elements, in particular, compounds of Mg, as the promoter. This catalyst preferably contains 30-70% by weight. copper (in terms of CuO). Weight ratio of Cu:Zn (Peres�those for CuO:ZnO) may be 1:1 or more, but preferably lies in the range from 2:1 to 3.5:1 by weight catalysts for the synthesis of alcohols.

A particularly preferred catalyst composition suitable for methanol synthesis, characterized by the ratio of Cu:Zn:Mg:Al in the range 16,5-19,5:5,5-8,5:1,0:2,5-6,5.

As described above, containing copper catalysts traditionally produced by preparing a homogeneous mixture of particles of compounds of copper and zinc, firing this mixture, often in the oxygen atmosphere, usually air, in order to convert these compounds into oxides, and subsequent tabletting and recovery. Roasting is usually carried out at temperatures above 275°C, typically at a temperature in the range from 300 to 500°C.

Preferably, the catalyst used in the present invention, produced in the following stages:

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

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

(iii) impact on the dried precursor composition of the catalyst redox conditions so that the contained copper compounds recovered to the copper,

(iv) passivateobject restored copper, and

(v) forming restored and passivated composition,

where, before recovering copper compounds, homogeneous mixture is treated in the drying step at a temperature in the range 180-240°C.

In accordance with the present invention, to achieve high catalyst activity, stage firing and exclude the dried homogenous mixture is subjected to the reducing conditions to convert the contained copper compounds in copper without preliminary heating stage to convert the copper to copper oxide. Instead, the drying process is carefully controlled, making sure to keep the water as much as possible, was given without causing decomposition of copper to copper oxide.

The surface area of copper in these catalysts is preferably ≥ 60 m2/g Cu, preferably ≥ 70 m2/g Cu, more preferably ≥ 75 m2/g Cu, most preferably ≥ 80 m2/g Cu. As indicated above, the surface area of the copper can be easily determined by means of the reactive frontal chromatography, as described in EP-A-202824. Particularly suitable method is the following; molded catalyst blocks milled and sieved, obtaining a particle size of 0.6 to 1.00 mm. to About 2.0 g of the ground material is weighed in a glass of TRU�ku and heated to 30°C (for restored and passivated samples) or 68°C (for oxide samples) and purged for 2 min with helium. Then the catalyst was reduced by heating in a stream of 5% vol. N2in helium by heating 4°C/min to 230°C, and then maintained at this temperature for 30 min. the catalyst was Then cooled to 68°C in a helium atmosphere. Using this recovered catalyst is then passed to 2.5%. N2O in helium. The separated gas is passed through a gas chromatograph and measure the excretion of N2. Based on these data, one can calculate the surface area of copper for a given catalyst.

The coefficient of crushing strength catalyst molded blocks, which is the ratio of the average horizontal crushing strength (in kilograms) restored molded block to the medial-lateral crushing strength (in kilograms) molded catalyst unit after manufacture, is preferably ≥ 0,500:1, preferably ≥ 0,600:1, more preferably ≥ 0,650:1, most preferably ≥ 0,700:1, especially, ≥ and 0.750:1. To measure this relationship it is necessary to measure the crushing strength of a molded catalyst blocks after production, that is molded blocks obtained from restored and passivated powder and molded restored blocks, that is, molded blocks, in which the copper passivation layer has already been overcome�Radovan to elemental copper as a result of exposure to the reducing gas stream. Consequently, the strength of the molded catalyst blocks after production can be measured on restored and passivated catalyst in air, whereas the strength of the re-reduced catalyst is preferably measured in an inert atmosphere to prevent the exothermic oxidation of this block. The crushing strength of the catalyst after production, expressed as the average horizontal the crushing strength preferably is ≥ 6.5 kg, more preferably ≥ 10.0 kg, most preferably ≥ 12,0 kg, then the catalyst has sufficient strength for loading in the reactor the conversion of carbon oxides. Average horizontal the crushing strength can be measured using traditional methods. Suitable for molded blocks after fabrication method is the following. The crushing strength of molded blocks measured on cylindrical tablets using a calibrated machine to determine the strength of preformed material ST5. Strength tablets crush is measured in the horizontal (radial) plane. Use torque wrench (item 50 kg and speed of crushing of 2.5 mm/min To measure the use of at least 20 tablets and calculate the average value. To measure p�echnosti crush is restored pills oxide or restored and passivated pills should first be subjected to recovery. This can be accomplished by placing these tablets in the tank, blowing air with nitrogen and the subsequent effects on tablets 2% N2in nitrogen when heated to 90°C for 2 hours, then to 120°C for 2 hours, then to 180°C for 5 hours and up to 235°C for 7 hours, standing at 235°C for 3 hours, heating to 240°C for 1 hour and kept at 240°C for 3 hours and then cooling in the presence of the reducing gas and purging with nitrogen during storage. Measurement of tensile strength restored tablets is carried out in an inert (oxygen free) atmosphere using a machine ST5, located in a glove box.

Since the stage of firing before restoring missing, shaping a homogeneous mixture before recovery is also not hold, as the internal porosity of the tablets resulting from the decomposition of, for example, hydroxycarbonate, during which emits water and/or carbon dioxide, can cause low mechanical strength and, consequently, reduction of service life.

A homogeneous mixture can be obtained by wet processing of oxides, for example, by the reaction of copper oxide and zinc oxide and ammonia in an aqueous medium, such as water, or by mixing soluble compounds�s metals. Easier to make it through the decomposition of metal nitrates and alkaline precipitating substance in an 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 and the subsequent processing of the resulting suspension can be adjusted to obtain certain crystalline compounds, for example, the type of manasseite, rosasite, aurichalcite or malachite. Suitable for this method include joint deposition of soluble salts of the metals using a precipitating agent such as a hydroxide, carbonate or bicarbonate of ammonium or alkali metal. The order of mixing of reagents can be selected in accordance with known principles, for example, using one-step co-deposition described in GB-A-1159036 or two-phase co-deposition described in GB-A-1296212 and GB-A-1405012. Preferably, all of the divalent oxide components injected by such co-deposition.

In a preferred embodiment of the invention, the insoluble copper compounds 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, etc. of metal, and an aqueous solution of the precipitating carbonate of alkaline metal�and, such as sodium carbonate or potassium. There also may be non-carbonates precipitating substances such as hydroxides of alkali metals or ammonium hydroxide. Consequently, a homogeneous mixture of individual particles can be obtained by combining aqueous solutions of soluble compounds of copper, zinc and optionally one or more compounds promiting metals selected from compounds of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare earth elements, with an aqueous solution of precipitating alkali metal carbonate in the presence of aluminum oxide or hydrated aluminum oxide or degradable them to aluminum compounds. In a preferred embodiment of the invention, as the source of aluminum using a colloidal dispersion of aluminum oxide or aluminum hydroxide. Such aluminum oxide or aluminum hydroxide in the form of colloidal dispersions are commercially available or can be obtained by known methods. Their use in the manufacture of copper catalysts is described, for example, in US4535071. After combining the solution of the metal compound with a solution of the precipitating substances alkali metal carbonate reacts with soluble compound of the metal with the formation of insoluble metal carbonate, including, hydroxycarbonate metal. Maintaining besieged m�of the material can be carried out in batch or semi-continuous mode, wherein the aqueous suspension of precipitated material is maintained at an elevated temperature in one or several tanks with agitator for a predetermined period of time. The suspension of the compounds in the liquid can only be stirred, the intensity of mixing depends on the tendency of the particles to the deposition. If you want to prevent deposition in the solution may be a polymer. Alternatively, the dopant material can be maintained in the reactor with pulsating flow, as described in the application by the same authors WO2008/047166, incorporated herein by reference.

After this mixing, the homogeneous mixture is preferably separated, for example, by separating the stock solution, using known methods such as filtration, decanting or centrifugation, and washed to remove soluble salts. Especially if there are compounds of alkali metals, the alkali content is preferably reduced to less than 0.2% wt., preferably, less than 0.1% wt., more preferably, less than 0.05% by weight. in terms of the corresponding oxide of the alkali metal in the dried material.

After washing, the material can be dried for the purpose of obtaining a powder of the catalyst precursor. In one of the embodiments of the invention, the dryer includes a step, carried out by PR� maximum temperature in the range 180-240°C. Therefore, drying may include heating the wet mixture in the course of individual stages or continuously for a long period, until it reaches the maximum temperature. Preferably, the drying stage consists of two or more separate stages of drying in which water is removed in several steps. The drying step can be carried out using conventional equipment for drying, such as equipment used for oxide catalysts. In one embodiment of the invention comprises primary drying stage of heating of a moist homogeneous mixture to a temperature in the range of 90-150°C, preferably 100-125°C in air or in an inert gas atmosphere in a drying oven, drum dryer or similar equipment. In an alternative embodiment, the initial stage of drying is carried out using a spray dryer, in which agglomerates are formed of a homogeneous mixture that is particularly suitable for the case of compression molding of tablets. To facilitate spray drying, the washed material is preferably dispersed in water. The solid content of the raw material in a spray dryer may exceed 15% wt., however, preferably is ≥ 20% weight. Perhaps the use of conventional spray equipment�ia with inlet temperature in the range of 150-300°C and the outlet temperature in the range of 100-200°C. In those cases, when the inlet temperature exceeds 240°C, the feed rate of the raw material should be adjusted so that the copper compounds are essentially not subjected to thermal decomposition. Preferably, the receiving subjected to spray-dried agglomerates with an average size (determined by sieve fractions, i.e. weighted mean particle size in the range of 10-300 μm (microns), particularly preferably 100-250 μm.

During primary drying, in a drying oven or a spray dryer, the water content of the catalyst precursor preferably is reduced to < 20% by weight., preferably < 15% by weight., more preferably ≤ 10 wt%.

As in single-stage drying and during drying for a number of distinct stages homogeneous mixture preferably is subjected to drying, in which it is heated to a temperature in the range 180-240°C. Without intending to be limited by theoretical explanation is believed that the drying at this temperature allows to remove from the catalyst precursor as hemosorbtion and physically adsorbed water and what it means for obtaining a precursor of a catalyst with increased strength. The time during which the mixture was kept at a temperature within this range depends on the selected temperature, a longer period is desirable at lower temperatures of this range, � shorter - at a higher temperature. It is desirable that the drying time ranged from 2 to 8 hours, preferably from 2 to 6 hours. Stage of drying may be effected in air or in an inert gas atmosphere, such as nitrogen or argon, in a drying oven, drum dryer, or similar hardware. As indicated above, during the drying phase, copper compounds, such as carbonate of copper, is not converted to copper oxide. After drying the catalyst precursor, preferably stored in an atmosphere of dried air or dry inert gas to avoid re-adsorption of water from the atmosphere.

Recovery of copper compounds is convenient to carry out by exposure of the dried catalyst precursor containing hydrogen and/or carbon monoxide gas at atmospheric or elevated pressures. Preferably, the recovery is carried out at the lowest temperature at which it is possible. So, you can use the usual methods of reduction with hydrogen, i.e. the use of the diluted stream of hydrogen, for example, 2% H2in N2at a slow heating of the catalyst precursor until then, until the recovery starts. Typically, recovery begins at about 80°C and was largely completed by 200°C or even 150°C.

In accordance with the present invention it was discovered that covestone precursor of the catalyst, containing carbonates of copper, such as hydroxycarbonate copper (malachite) and/or zinc malachite, can be carried out at high concentration of hydrogen in the reducing gas stream to the recovery phase took place in full, without usually observed when you restore containing zinc oxide materials problems. Therefore, in a preferred embodiment of the invention, recovery of the catalyst precursor containing hydroxycarbonate copper, is carried out by exposure of the dried catalyst precursor hydrogen-rich gas streams containing > 50%. hydrogen, more preferably, > 75%. hydrogen, especially > 90%. hydrogen. If necessary, can be used even essentially pure hydrogen.

Recovery can be accomplished as long while from the precursor catalyst no longer stand out as water and carbon dioxide. As a result, usually develops in at least 50% of the recovered compounds such as copper carbonate, recovering to the metal, however, it is preferable to carry out the recovery until > 95% recoverable compounds not converted into metal. Zinc and promiting connections in the reconstruction phase is transformed mainly into the corresponding oxides.

In the restored �condition, due to the large surface area, copper can quickly enter into exothermic reaction with oxygen and moisture present in the air, so it is necessary to passivate before shaping and storage. The composition is considered to be passivated if it is stable to air, particularly, to air with a temperature of > 50°C. This can be determined using thermogravimetric analysis, in which we are observing the weight change of a material when heated. When oxidation occurs, the weight of the catalyst increases. It is desirable that the weight of the passivated catalyst was not changed when heated in air at 20°C/min until until the temperature reaches at least 80°C, preferably at least 90°C.

Passivation can be carried out using a dilute oxygen and/or carbon dioxide, or powdered catalyst precursor may be deposited protivogololednye protective material. Passivation can be carried out using mixtures of inert gas/air, such as a mixture of nitrogen/air, thereby the concentration of the air can slowly increase to the copper surface formed a thin layer of metal oxide. Usually, oxygen is injected using an air flow rate sufficient to maintain the temperature of the catalyst precursor in� the passivation level is from 10 to 100°C, preferably, from 10 to 50°C, especially from 20 to 40°C. for Example, the recovered material can be influenced by a stream of inert gas, e.g. nitrogen, and add 0,1% vol. air. This number is gradually, over a period of time, increased to 0.5%. oxygen, then 1% vol., then 2% by volume; 5% vol. etc until until the oxygen content does not become equal to its content in the air. Alternatively, the composition of the reduced catalyst to passivate using a mixture of gases containing carbon dioxide and oxygen in the ratio2:O2≥ 2:1, so that the surface formed a thin layer of metal carbonate, such as hydroxycarbonate metal.

Restored and passivated powder of the catalyst precursor can then be subjected to additional processing for the purpose of producing molded blocks, among others, the following stages:

(i) pre-compaction and tabletting restored and passivated powder so that the molded blocks were a pill,

(ii) the connection is restored and passivated powder with one or more binders and optionally one or more additional powders and processed in the rotary drum to obtain spherical agglomerates and�and granules,

(iii) the transfer is restored and passivated powder in the slurry (preferably non-aqueous), powder/grinding in a disc mill and extrusion with obtaining extrudates,

(iv) a transfer to the slurry, as described above, the plasticization/grinding in a disc mill and extrusion with obtaining products of complex shape, such as a monolithic structure or plate, with a secondary structure or without it,

(v) applying restored and passivated powder in an inert or, similarly, on the catalytically active substrate through protravnogo priming or the like.

In all cases, can be used binders and additives commonly used in this field. Also there are numerous other options for additional processing.

Pre-compaction and tabletting powder is most suitable for producing molded blocks. The tablet may be a conventional cylindrical tablet with flat ends. Cylindrical tablets for processes of conversion of carbon monoxide in a suitable case have a diameter in the range of 2.5-15 mm, preferably 3-10 mm, and the dimensions (length/diameter) in the range of 0.5-2.0. Alternatively, the molded block may be in the form of rings or trehdolchatye elements. In a preferred embodiment of osushestvlyaetsya, the block has the shape of a domed cylinder with two or more grooves running along its length. In one of such embodiments of the invention, the catalyst has the shape of a cylinder with a length C and diameter D, wherein on the outer surface of the unit also includes two or more recesses along its length, and the specified cylinder has domed ends of lengths A and b, so the value of (A+b+C)/D is in the range from 0.50 to 2.00, and the value of (A+b)/C is in the range from 0.40 to 5.00. A and b are preferably equal. With preferably corresponds to the range from 1 to 25 mm, D preferably corresponds to a range from 4 to 40 mm, more preferably from 4 to 10 mm, most preferably 4 notches evenly spaced around the circumference of the cylinder. Alternatively or additionally, the molded blocks can have one or more through holes. This cylindrical, with high domed end, the catalysts peculiar to an improved stacking and/or a lower pressure drop compared to conventional forms without notches or without holes. Such an improvement of the traditional cylindrical shape of the catalyst with flat ends made possible thanks to the increase of the strength characteristics of the restored and passivated powder of the catalyst precursor.

Tablets, sabenacommissie tablets with flat or domed ends, as described above, preferably is made so that the density of the tablets is in the range from 1.4 to 2.5 g/cm3more preferably from 1.8 to 2.4 g/cm3. The density of the tablet can easily be determined by calculating the volume based on the dimensions of the tablet and measure its weight. As we increase the density of free volume in the molded block is reduced, which, in turn, leads to a decrease in the permeability of the unit for entry and exit of reacting gases. Consequently, for values of the density of > 2.5 g/cm3the reactivity of the catalyst may be less than optimal, despite the high surface area copper restored and passivated powder. For values of density < 1.4 g/cm3the crushing strength may be insufficient for long-term use in the modern processes of conversion of carbon monoxide.

Specific surface area by BET (Brunauer-Emmett-teller) of the catalyst, determined by the absorption of nitrogen, is preferably > 80 m2/g, more preferably > 90 m2/g; a pore volume, determined using the desorption branch at 0,99 is preferably > 0.15 cm3/g, more preferably > 0.2 cm3/g.

The catalyst may be placed in a conventional methanol synthesis reactor, such as reactor with the motionless�th layer of the catalyst, although the size of the Converter can be reduced, since the method of the present invention allows to obtain a higher yield of methanol due to the higher activity and selectivity of the catalyst.

The catalyst may be activated in situ by the impact of the flow of reducing gas, preferably containing hydrogen, to convert the layer passivated copper again to elemental copper. Thus, the invention preferably involves the following stages: (i) the activation containing the catalyst shaped units formed from a restored and passivated powder catalyst, and powder that contains copper in the range 10-80% by weight., zinc oxide in the range 20-90% by weight., the alumina in the range 5-60% by weight. and, optionally, one or more oxide promiting compounds selected from compounds of Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si and rare earths in the range 0.01-10% wt., through the implementation of contact of said catalyst with a reducing gas stream and (ii) passing through the reduced catalyst process gas containing hydrogen, carbon dioxide and carbon monoxide, with the formation of flow of the product. Since the bulk of the copper is already present in the metallic form, the stage of activation can be osushestvlenie and with less water and by-products, to remove, compared to conventional containing zinc oxide catalysts. Activation can be accomplished using hydrogen gas, including a synthesis gas containing hydrogen and carbon oxides at a temperature of 80°C and a pressure in the range 1-50 bar. Similarly, maximum temperature recovery, preferably ranges from 150 to 200°C.

Typically, the methanol synthesis reaction is carried out in the circuit while the unreacted gases, after removal of the condensation and optionally after one or more additional stages of the synthesis of methanol, mixed with fresh gas containing hydrogen and oxides of carbon, in the desired ratio and recycled to the methanol synthesis reactor.

From any such circuit can be produced a flow of purge gas to prevent unwanted accumulation of inert/directionsparking gases. If necessary, this purge gas can also be obtained from methanol, or may be extracted hydrogen is used to regulate the stoichiometric ratio in the raw gas or to produce energy. The present invention provides a method of synthesis of methanol using the catalyst, in particular:

A. Synthesis of methanol, during which the mixture of gases containing carbon monoxide, hydrogen and neo�satalino, carbon dioxide, is passed over the catalyst at a temperature in the range of 200-320°C, a pressure in the range of 20-250, especially 30-120 bar abs. and a space velocity in the range 500-20000 h-1. This process can be arranged for single-pass or recirculating principle and may include cooling surfaces through indirect heat exchange contact with the reacting gases, or by dividing the catalyst layer and gas cooling between layers by introducing more cold gas or by indirect heat exchange. The catalyst for this process preferably comprises copper, zinc oxide and magnesium oxide with aluminum oxide.

V. Modified methanol synthesis in which the catalyst also contains free aluminum oxide with a specific surface area of 50-300 m2g-1and as a result the product of the synthesis is relatively enriched in dimethyl ether. The values of temperature, pressure and space velocity is similar to that given for the synthesis of methanol, however, the reactive gas contains hydrogen and carbon monoxide in a molar ratio less than 2.

In both cases, the methanol synthesis may be part of the process of multiple synthesis, during which the formed gas after the removal of condensate is served in one or more subsequent reactors for methanol synthesis, in which m�can be the same or different catalyst for methanol synthesis.

The composition of the reacting gas in the circuit is preferably characterized by the ratio RH 2> 2PWITH+ 3PCO2however, an excess of hydrogen that reacts with the oxides of carbon in accordance with the following equations of the reactions:

CO + 2H2→ SN3HE

CO2+ 3H2→ SN3HE + H2About

The stoichiometric number, R, defined as R=(H2-CO2)/(CO+CO2), for a reacting gas in the loop with catalyst is preferably ≥ 3, more preferably ≥4, most preferably ≥ 5.

The invention is further described with reference to the following examples.

The surface area of copper and the average horizontal the crushing strength was measured using the methods described above. The crushing strength was measured using a desktop automatic mechanical dynamometer ST5 (manufacturing Systems Engineering (Nottingham) Ltd).

Shrinkage of the tablets was measured manually using a caliper with a digital readout. Pills before and after restoration were subjected to physical measurements to determine volume changes. Restored the tablets was investigated in a glove box in an inert (oxygen-free) atmosphere. Researched 20-50 tablets and calculated the average value.

Example 1. Cooking �of utilizator

Prepared powdery catalyst precursor with a molar ratio Cu:Zn:Mg:Al 17,5:6,5:1:4 by deposition at 60-75°C and a pH of more than 6.0 a homogeneous mixture of solutions of nitrates of copper, zinc and magnesium in the presence of colloidal dispersion Sol of aluminum hydroxide using as precipitating substances potassium carbonate. After co-deposition of the suspension was maintained at 65°C until the color changes from blue to green. Then the suspension was filtered and washed until a minimum alkali content (< 500 ppm).

The obtained filter cake is then re-suspended with obtaining a suspension of 35% wt./weight., which was subjected to spray drying with the formation of agglomerates of about 10-50 microns in diameter.

With spray-dried powder is then subjected to drying by heating the powder up to 210-240°C and kept at this temperature for 6 hours. Data of x-ray diffraction analysis confirmed the presence of hydroxycarbonate copper and lack of education of dioxide of copper during the drying phase. This material is a precursor of the catalyst is then cooled to 60-80°C in a dry nitrogen atmosphere.

The precursor of the catalyst was restored by exposure to hydrogen-containing gas containing > 90% N2first , at about 80°C, maximum temperature recovery amounted to�sludge 160°C. The recovery process continued until, until no longer produced water and carbon dioxide that was fixed by using appropriate sensors. Calculations found that > 95% copper moved into elemental form. The recovered catalyst material is then cooled to 20-40°C in a dry nitrogen atmosphere.

Then restored the material of the catalyst was passivatable at 20-40 ° C, using a mixture of nitrogen/air, the composition of which is regulated so that the first oxygen content was 0.1% by volume; then gradually increased to 1%. oxygen and then higher concentrations, up to use as a passivation gas 100% air. The rate of increase of the oxygen content was adjusted based on the temperature control.

Passivated powdered catalyst is mixed with a small amount of graphite and subjected to molding to obtain a cylindrical tablets using conventional equipment for tableting. Tablet was 5.4 mm in diameter and 3.2 mm in length.

For comparison, prepared comparative catalysts with the same molar ratio of Cu:Zn:Mg:Al, using the same methods of deposition and spray drying, but instead the stage of high-temperature drying dried spray-dried powders were subjected to calcination at (I) 295º or (II 500º, wherein the copper compounds are turned into copper oxide. The obtained oxide powders was mixed with a small amount of graphite and subjected to molding to obtain a cylindrical tablets of 5.4 mm in diameter and 3.2 mm in length.

The surface area of copper for these tablets was determined using reactive frontal chromatography as described above. In each case, to measure the surface area used milled and sieved pills. Got the following results:

SampleThe surface area of copper, m2/g Cu
Comparative material I (firing at 295°C)40,0
Comparative material II (calcination at 500°C)38,8
Example 1to 89.6

These results show that the surface area of copper for restored and passivated catalyst corresponding to the present invention, is superior to a similar magnitude to those of the catalysts, the receipt of which includes the phase of firing.

Average horizontal the crushing strength (MARPS) was determined for tablets after production, and after the restoration for the purpose of modeling strength of the catalyst at that location.

Preformed materialThe density of the tablets, g/cm3MARPS tablets after production, kgMARPS restored tablets kgThe ratio of MARPS (restored, after production)
Comparative catalyst I1,9712,22,40,197:1
Comparative catalyst II1,978,42,60,310:1
Example 1A2,0417,214,30,831:1

These results show what can be achieved is very large, the crushing strength and that is comparable to the density of the tablets made from powdered precursor obtained by using the stage of firing, unexpectedly showed less strength after recovery than those that were manufactured by the method of the present invention.

Example 2

Prepared catalyst �reamer 1.

In raw materials spray dryer the solids content amounted to 20-35% by weight.

Settings spray dryer were as follows:

Inlet temperature: 280-300°C

Outlet temperature: 110-120°C

Pump pressure: 18-20 bar

Residual moisture of the dried spray dried powder amounted to < 5-10%. 95% of the weight. the particles had a size 63-250 µm (micron).

Dried spray-dried product was subjected to the same procedure of drying, restoration and passivation, as in example 1. Restored and passivated powder was given in the form:

a) cylindrical tablets with a diameter of 5.4 mm, a length of 3.2 mm and a density of 1.73;

(b) cylindrical tablets with a high domed end and 4 shares/recesses with a diameter of 6.0 mm, a total length of 4.0 mm and a density of 1.82 g/cm3. The height of the dome at the top and bottom equal to 1.5 mm;

(C) cylindrical tablets with a high domed end and 4 shares/recesses with a diameter of 5.0 mm, a total length of 4.0 mm and a density of 1.83 g/cm3. The height of the dome at the top and bottom equal to 0.5 mm.

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

SampleThe surface area of copper, m2/g Cu
Example 2A0,1
Example 2b75,8
Example 2C78,3

For material 2A also explored some range of values of the density of the tablets. Identified MARPS for tablets after production and after restoring to simulate the strength of the catalyst at that location. Got the following results:

SampleThe density of the tablets, g/mlMARPS tablets after production, kgMARPS restored tablets kgThe ratio of MARPSShrinkage during the recovery, % vol./about.
Example 2A1,738,86,90,784:111,2
Example 2A'1,9414,610,30,705:19,9
Example 2A”2,1017,710,7 0,604:110,1
Example 2bof 1.827,04,00,571:18,9
Example 2C1,8312,19,10,752:19,6

Example 3. Test activity

Samples of the tablets of examples 1 and 2 milled, 2 ml (0.50 g) fragments in the range of sieve fractions of 0.6-1.0 mm were loaded into the micro-reactor and restored with the aim of producing a catalyst in a gaseous mixture of 2%. N2/N2at temperatures up to 240°C. the Synthesis gas for synthesis of methanol containing (in % by vol./about.) 6,0, 9,2 CO2that 67,0 N2and 17.8 N2(R=3,8), is passed over the catalyst at a pressure of 50 bar, 225°C and a space velocity of 40,000 h-1. The methanol content at the outlet was measured in real time using a combination of infrared and gas chromatographs. Then, for conducting accelerated tests on the service life of the pressure and the temperature increased to above normal operating conditions values; these conditions were supported by 144 h, and then the rates decreased to the initial levels at which measured again the content of the meta�Ola output.

The relative activity of the catalysts of examples 1A and 2A' (in both cases, the density of the tablets was approximately 2,0) below. Summarizes the activity relative to the activity of standard oxide catalyst (calcined catalyst based on copper oxide, which is fully restored at the point of use) with the same molar ratio of Cu:Zn:Mg:Al, the test of which was conducted under the same conditions. Measurements were performed after 17 hours in real-time and 144 hours in real time. The following results are obtained:

CatalystTime measurement in real-timeRelative activity
Example 1A171,46
Example 2A'171,33
Standard171,00
Example 1A144of 1.52
Example 2A'1441,42
Standard�th 1441,00

These results show that the catalyst used in the method of the present invention, compared to the standard oxide catalyst with the same molar ratio of Cu:Zn:Mg:Al has a higher activity and a lower rate of deactivation.

Example 4 (comparative)

The catalyst prepared in accordance with Example 1 of US patent 4863894 (with molar ratio Cu:Zn:Al 59,8:25,6:14,5). The washed material was dried at 110°C, but without a drying step at 180-240°C, then restored with a mixture of 5% H2+ 95% N2in terms of volume. The recovered powder was passivatable and gave it the same shape as in Example 1. Investigated the range of values of the density of the tablets. MARPS measured for tablets after production for tablets and after re-restoring to simulate the strength of the catalyst at that location.

SampleThe density of the tablets, g/mlMARPS tablets after production, kgMARPS restored tablets kgThe ratio of MARPSShrinkage during the recovery, % vol./about.
Will compare. 4A 1,708,11,70,210:1the 16.2
Will compare. 4b1,8311,43,70,325:119,2
Compare 4C1,8812,33,80,309:119,0

Although initially preformed material was solid, the data to be re-restored material indicate a significant loss of strength and a large shrinkage. High shrinkage of catalyst is undesirable because it is irrational from the point of view of use of the reactor volume.

The catalyst of Example 4 was tested in accordance with test method described in Example 3. The relative activity of this catalyst to 144 hour fell to 0.97.

Example 5. Test selectivity

Capacitive reactor with constant stirring was used to measure kinetic parameters and characteristics of the deactivation of catalysts for methanol synthesis Examples 1 and 2 and comparative oxide catalyst with the same molar ratio of Cu:Zn:Mg:Al. Gas analysis �was held by the real-time using a combination of infrared and gas chromatographs. Used the following composition of the raw gas (% vol./vol.):

WITH6
CO26
N279
N29
R = 6,08

Just the reactor was loaded with approximately 5 g of the catalyst tablets.

The test lasted from 1 to 8 weeks with one loading of the catalyst with the purpose of obtaining information about the activity, stability and selectivity of the catalyst. Initial operating conditions were: 225°C (498 K), 65 bar, mass flow rate of 80,000 l/h/kg, space time of the reactor (W/F - weight/flow rate) 0,110×10-4g cat./g·mol raw material/h. After an initial period spent accelerated deactivation at elevated temperatures. The temperature changed cyclically to collect real-time comparative data over time.

The condensate exiting the flow reactor was collected and analyzed. Analysis was performed by gas chromatography, using as a reference calibrated standards. The content of contaminating impurities�th in the condensate is given below.

Example 1AExample 2AExample 2bExample 2CStandard oxide material
The content of impurities in the condensate, parts per million
Ethanol170,7212,5227,4154,1378,8
2-propanol11,3a 33.321,99,037,8
1-propanol44,956,946,914,0102,5
Methyl ethyl ketone4,35,6BUT5,08,1
2-butano� 24,7to 61.449,127,982,3
2-methylpropan-1-ol11,617,9of 15.3BUT33,2
1-butanol10,116,110,7BUT22,9
Total277,6403,6371,3210,0665,6
The proportion of the standard catalyst, %41,760,455,8of 31.5-
BUT - not found

These data suggest that the catalyst provides a more selective methanol synthesis than conventional catalyst based on oxide. In all cases, the total content of by-products for the pre-reduced catalyst < 405 ppm, and the content of ethanol < 250 parts per m�of lion.

1. The method of synthesis of methanol, comprising the following stages:
(i) holding in the reaction loop response of the process gas containing hydrogen, carbon dioxide and carbon monoxide over a catalyst, to obtain a gas product,
(ii) condensation of methanol, water and by-oxygenates formed from the gas-product,
(iii) returning the unreacted gases in the reaction loop,
where the catalyst includes tablets, obtained by pressing of restored and passivated powder catalyst, where powder that contains copper in the range of 15-70% by weight., zinc oxide, and the weight ratio of Cu:Zn based oxide is in the range from 2:1 to 3.5:1, alumina in the range 5-60% by weight. and, optionally, one or more oxide promiting compounds selected from compounds of Mg, Cr, Mn, V, Ti, Zr, TA, Mo, W, Si and rare earths in the range 0.01-10% wt., moreover, the catalyst obtained by carrying out stages, including:
(i) preparation in aqueous medium of the composition containing a homogeneous mixture of separate particles of compounds of copper, zinc, aluminum and, optionally, one or more promiting compounds of metals selected from Mg, Cr, Mn, V, Ti, Zr, TA, Mo, W, Si and rare earth elements,
(ii) separating and drying the composition to form a catalyst precursor,
(iii) Vosges�of redox conditions on the dried composition of the catalyst precursor, so that the contained copper compounds recovered to the copper,
(iv) passivation of surfaces restored copper, and
(v) forming restored and passivated composition,
where, before recovering copper compounds, homogeneous mixture is treated in the drying step at a temperature in the range 180-240°C,
and where the total content side of oxygenates in the condensate does not exceed 500 parts per million.

2. A method according to claim 1, wherein the total content of oxygenates is the amount expressed in weight parts per million quantities of ethanol, 2-propanol, 1-propanol, methyl ethyl ketone, 2-butanol, 2-methylpropan-1-ol and 1-butanol in the extracted condensate.

3. A method according to claim 1, wherein the total content side of oxygenates is less than 400 ppm, preferably less than 300 parts per million.

4. A method according to claim 1, wherein the ethanol content in the condensate is ≤ 300 ppm, preferably ≤ 250 parts per million.

5. A method according to claim 1, wherein the relative degree of purity of the condensate is ≤ 75%, preferably ≤ 50%.

6. A method according to claim 1, wherein the catalyst contains magnesium in an amount of 1-5% by weight. in terms of MgO.

7. A method according to claim 1, wherein the source of aluminum oxide or hydrated aluminum oxide in the catalyst is colloidal Mgr�rsia of aluminum oxide or aluminum hydroxide.

8. A method according to claim 1, in which these molded blocks of a catalyst characterized by the ratio of the average horizontal crushing strength after recovery and after production ≥ 0,5:1 and the surface area of copper of more than 60 m2/g Cu.

9. A method according to claim 1, wherein the catalyst has the form of cylindrical pellets with flat ends, rings or trehdolchatye element or dome-shaped cylinder with two or more grooves running along its length, optionally with one or more through-holes.

10. A method according to claim 1, wherein the density of the tablet is from 1.4 to 2.5 g/cm3.

11. A method according to claim 1, wherein the methanol synthesis process is carried out at a temperature in the range of 200-320°C.

12. A method according to claim 1, wherein the stoichiometric number, R, defined as R=(H2-CO2)/(CO+CO2), for a reacting gas in the loop with catalyst, is ≥ 3, preferably ≥ 4, most preferably ≥ 5.



 

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10 cl, 3 dwg, 2 tbl, 2 ex

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FIELD: chemistry.

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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: 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

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