Monolith catalyst and application thereof

FIELD: chemistry.

SUBSTANCE: invention relates to the application of a catalyst, which contains a monolith and a layer of the catalyst, for the dehydrogenation of alkanes to alkenes or aromatisation in dehydrogenation. The monolith consists of a catalytically inert material with BET surface area <10 m2/g, with the catalyst layer, applied on the monolith, containing platinum and tin and/or rhenium and if necessary other metals on an oxide carrier material, the catalyst layer thickness constitutes from 5 to 500 microns. In addition, the hour volume rate of gas supply constitutes from 500 to 2000 h-1. The invention also relates to methods of the dehydrogenation of alkanes to alkenes and aromatisation in dehydrogenation with the application of the catalyst described above.

EFFECT: claimed application of the catalyst provides high conversions, volume productivity and selectivity.

14 cl, 13 tbl, 25 ex

 

The invention relates to a solid catalyst and to its use for petrochemical transformation, such as dehydrogenation, aromatization, reforming and combustion.

In many petrochemical reactions (e.g., dehydrogenation, aromatization, reforming and combustion) use the applied catalysts of noble metals. The use of such catalysts is very expensive due to high costs of precious metals. In addition, unfavorable distribution of precious metals and longest path of diffusion in conventional catalysts lead to a small use of precious metals.

U.S. patent 4788371 describes a method of dehydrogenation with water vapor capable of dehydrogenation of hydrocarbons in the gas phase, combined with oxidative heating of the intermediate connections, and use the same catalyst for selective oxidation of hydrogen and dehydrogenation with water vapor. Here, the hydrogen may be introduced by simultaneous submission. The used catalyst contains a noble metal of group VIII, alkaline metal and another metal selected from the group consisting of In, Ga, In, Ge, Sn and Pb, on an inorganic oxide support such as alumina. The process can be conducted in one or several stages in fixed or moving bed.

International �avca WO 94/29021 describes the catalyst, which contains a carrier composed mainly of a mixed oxide of magnesium and aluminum Mg(Al)O and also a noble metal of group VIII, preferably platinum, a metal of group IVA, preferably tin, and possibly an alkali metal, preferably cesium. The catalyst used in the dehydrogenation of hydrocarbons, which can be carried out in the presence of oxygen.

U.S. patent 5733518 describe a method of selective oxidation of hydrogen with oxygen in the presence of hydrocarbons, such as n-butane over a catalyst comprising a phosphate, germanium, tin, lead, arsenic, antimony or bismuth, preferably tin. The combustion of hydrogen generates at least one reaction zone, the reaction heat required for the endothermic dehydrogenation.

European application EP-A-0838534 describes a catalyst for hydrogenation without water vapor alkanes, in particular of isobutene, in the presence of oxygen. The used catalyst contains a platinum group metal deposited on a carrier containing tin oxide/zirconium oxide and having a tin content of at least 10%. The oxygen content in the stream fed to the dehydrogenation, is calculated so that the amount of heat produced by the combustion reaction of hydrogen and oxygen, was equal to the amount of heat required for dehydrogenation.

International�native application WO 96/33151 describes a method for the dehydrogenation of alkanes with 2-5 carbon atoms in the absence of oxygen over a dehydrogenation catalyst, containing Cr, Mo, Ga, Zn, or a metal from group VIII, with simultaneous oxidation of the resulting hydrogen recovered over a metal oxide, e.g. oxide of Bi, In, Sb, Zn, Ti, Pb or Te. The dehydrogenation you need to stop at regular intervals to re-oxidize the recovered oxide by the oxygen source. U.S. patent 5430209 describes the process in which a stage and stage dehydrogenation oxidation is carried out sequentially, and the associated catalysts are physically separated from each other. The catalysts used for selective oxidation of hydrogen, represent the oxides of Bi, Sb and Te, and their mixed oxides.

Finally, international application WO 96/33150 describes a method in which alkane with 2-5 carbon atoms dehydrogenase over the dehydrogenation catalyst in the first stage, the gas, the exhaust from the stage of dehydrogenation, mixed with oxygen and the second stage is passed over an oxidation catalyst, preferably, Bi2O3to selectively oxidize the generated hydrogen to water, and in the third stage, the gas, the exhaust from the second stage, again passed over the dehydrogenation catalyst.

It is known that aromatic hydrocarbons can be obtained by catalytic aromatization through dehydrogenation of hydrocarbons with an open circuit (see, for example, Catalysis VI,p. 535-542, ed. by R. N. Emmet, Reinhold Publishing Co., New York, 1958).

U.S. patent US 3449461 describes the aromatization by dehydrogenation of paraffins with 6-20 carbon atoms with an open circuit in aromatic hydrocarbons, including o-xylene, using sulfur catalyst which contains a noble metal such as palladium or platinum.

The patent application U.S. 2004/0044261 describes selective method of obtaining p-xylene by conversion isoalkanes or alkenes from 8 carbon atoms over a catalyst which contains molecular sieve coated with a noble metal of transition group VIII.

German application DE-A 19727021 describes a method of producing aromatic compounds with 8 carbon atoms from butenes by dehydrogenation of mixtures of vinyl hydrocarbons with 8 carbon atoms derived di-Marisela technical factions €4 over a catalyst which contains at least one element of the platinum group in amphoteric ceramic media. The main reaction product is ethylbenzene, and optionally also formed o-xylene.

The object of the present invention is to create a method for the dehydrogenation of hydrocarbons, which guarantees a high conversion rate, volumetric productivity and selectivity.

This task reach with the help of a catalyst comprising a monolith composed of catalyticconverter material with low surface area by BET, and a catalyst layer which is deposited on the monolith and comprises, on an oxide carrier material, at least one noble metal selected from the group consisting of noble metals of group VIII of the periodic table of the elements, optionally tin and/or rhenium, and optionally other metals, where the thickness of the catalyst layer is 5 to 500 microns.

The invention provides a fixed bed catalysts with significantly reduced requirement for the number of noble metal and improved performance. At the same time, the depth of penetration of the catalyst is limited by the value from 5 to 500 μm, preferably from 5 to 250 μm, more preferably from 25 to 250 μm, and particularly from 50 to 250 μm. The depth of penetration of the catalyst is limited by the thickness of the catalyst layer deposited on the monolith.

The catalyst layer on the monolith contains at least a ceramic oxide as a catalyst and at least one noble metal selected from the transition elements of group VIII of the periodic table of elements, particularly palladium, platinum or rhodium, may, rhenium and/or tin. The substrate comprise one or more ceramic oxides of elements of main group of the second, third and fourth groups, and third auxiliary groups chetvertoi groups (subgroup IVB) elements and lanthanides, particularly, MgO, Cao, Al2O3, SiO2, ZrO2, TiO2La2O3and CE2O3. In a particularly preferred embodiment of the invention, the catalyst carrier contains SiO2and ZrO2in particular, a mixed oxide of SiO2and ZrO2.

In addition to the noble metals side of the subgroups of group VIII, it is possible to use other elements; in particular, rhenium and/or tin, which serve as supplements to the side elements of subgroup VIII of the group. Another part is the addition or doping or compounds of elements of main and auxiliary groups of the third group (IIIA or IIIB) or basic compounds, such as oxides of alkali, alkaline earth or rare earth metals or their compounds which can be converted to the corresponding oxides at temperatures above 400C. Simultaneous doping of many of the above elements or their compounds. Suitable examples are compounds of potassium and lanthanum. In addition, the catalyst may be mixed with sulfur, tellurium, arsenic, antimony or selenium, which in many cases cause an increase in selectivity is possible by partial "poisoning" (retarders).

The catalyst bed contains at least one noble metal of group VIII of the periodic�coy table of elements (Ru, Rh, Pd, Os, Ir, Pt). The preferred noble metal is platinum. The catalyst may, optionally, contain tin and/or rhenium, preferably tin.

In a preferred embodiment of the invention, the catalyst layer contains platinum and tin.

In addition, the catalyst layer can be alloyed with other metals. In a preferred embodiment of the invention, the catalyst layer contains one or more metal side of a subgroup of the third group (IIIB) of the periodic table of elements, including lanthanides (Sc, Y, La, CE, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), and preference is given to cerium and lanthanum, special preference to lanthanum.

In another preferred embodiment of the invention, the catalyst layer contains platinum, tin and lanthanum.

In addition, the catalyst may contain metals selected from the metals of main group I and II group of the periodic table of elements. In a preferred embodiment of the invention, the layer of catalyst comprises potassium and/or cesium. In a specific embodiment of the invention, the catalyst layer contains platinum, tin, lanthanum and an alkaline metal selected from the group consisting of potassium and cesium.

The catalyst layer containing the oxide carrier material and at least one noble metal of group VIII of periodicheskaia elements tin and/or rhenium and, if appropriate, other metals deposited on the monolith by coating in the wet state of the catalytically active material. For this purpose, otherwise it is also possible to first apply a layer of a catalyst consisting of an oxide carrier material, a monolith by coating in the wet state and to impregnate this layer in the next stage of the process one or more different solutions containing the metals.

The catalysts according to the invention is used in particular, for the dehydrogenation of alkanes to alkenes, such as propane to propylene or n-butane to butenes (1 - and 2-butenes), for flavoring in dehydrogenation and catalytic combustion of hydrogen with oxygen.

Monoliths

Suitable monolithic structures are either metal or ceramics. Preferably, they consist of single blocks with small (0.5-4 mm) parallel channels. Preferably, use one solid piece or Corning Incorporated, either NGK or Denso.

The most common material for monolithic structures is a cordierite (a ceramic material comprising magnesium oxide, dioxide of silicon and of aluminum oxide in the ratio of 2:5:2). Other materials, whose monolithic structures are commercially available, are metals, mullite (mixed silica and alumina�, the ratio 2:3) and silicon carbide. These materials have, like cordierite, low specific surface Brunauer, Emmett and Teller (BET) (e.g., cordierite, usually 0.7 m2/g). Low surface area according to BET in the context of this invention is a surface area by BET<10 m2/g

Preferably, the invention uses monolithic piece made of cordierite.

Ceramic monolithic units are available with densities of cells 25-1600 cpsi (cells per square inch, which is equal to the cell size 5-0,6 mm). When using higher cell densities, the geometric surface area is increased and, thus, the catalyst can be used more effectively. Discomfort higher cell densities are somewhat more difficult manufacturing process, more difficult application in the wet state and a higher pressure drop in the reactor. However, the pressure drop remains very low for monoliths with a high density of cells (usually a ratio below 10) compared to the reactor with a porous layer, due to the direct channels in the monolith.

Preferably, the density of cells of the monolithic elements used in the present invention, range from 100 to 1200 cpsi, most preferably, from 300 to 600 cpsi.

Ceramic monolithic elements can be obtained put�m of a mixture of talc, clay and component, giving the aluminum oxide and dioxide silicon, mixing the mixture to form a molding composition, casting the mixture, drying of raw and heated at a temperature of from 1200 to 1500S to form ceramics containing primarily cordierite and having a low coefficient of thermal expansion. Generally speaking, pasta with suitable rheological properties and composition can be extruded into a monolithic carrier. The paste usually consists of a mixture of ceramic powders of appropriate size, inorganic and/or organic additives, solvent (water), chemical plasticizer (acid) to find the pH, and the permanent binder (colloidal solution or Sol). Supplements can be a plasticizer, or a surface-active substance to match the viscosity of the paste, or a temporary binder, which can later be burned. Sometimes add glass or carbon fibers to increase the mechanical strength of the monolith. Permanent binder should improve the integrity of the monolith.

Cordierite monoliths can be produced from a load consisting of talc, kaolin, calcined kaolin and alumina which collectively provide a chemical compound of SiO2from 45 to 55, Al2O332 to 40 and MgO from 12 to 15 wt%. Talc is a mate�ial, consisting mainly of water magnesium silicate, Mg3Si4O10(OH)2. Depending on the source and purity of talc, it may also be associated with other minerals such as tremolite (CaMg3(5SiO3)4), serpentine (3MgO×2SiO2×2H2O), anthophyllite (Mg7(OH)2(Si4O11)2), magnesite (MgCO3), mica and chlorite.

Can also be used for extrusion production of monoliths made of other materials, such as SiC, B4C, Si3N4, BN, AlN, Al2O3, ZrO2, mullite, titanate Al, ZrB2, Stallone, perovskite, carbon and TiO2.

In extrusion, in addition to the quality of a die and the nature and properties of materials used for the manufacture of molding compounds, also are important additional additives, pH, water content and strength are used in extrusion, relative to the properties of monolithic products. Additives used in extrusion, represent, for example, cellulose, CaCl2, glycol, diethyleneglycol, alcohols, waxes, paraffin, acid and heat-resistant inorganic fibers. In addition to water, may also be used other solvents such as ketones, alcohols and ethers. The addition of additives can lead to improved properties of monoliths, such as the production of micro-cracks, which increases the mustache�ascioti to thermal shock, the best porosity and absorption capacity, and increased mechanical strength or low thermal expansion.

The application procedure is wet

According to the present invention, the bare monolithic structure coated with a layer of a catalyst containing one or more ceramic oxides, or a layer of catalyst comprising a catalytically active metals and optionally other elements (promoters), already deposited on a ceramic oxide carrier material, where the coating produced according to the procedure applying in the wet state.

The macroporous structure of ceramic monoliths facilitates the fixing of the applied wet layer. The method, which produce the application in the wet state, can be divided into two methods: a macroporous carrier can be (partially) filled with material deposited in a wet state, with high surface area, or applied when wet can be placed as a layer in the pores of the ceramic medium. Filling of the pores leads to the strong interaction between the monolith and applied in the wet state, when a large portion of the coating layer is actually fixed inside the pores of the carrier, instead only to join the outer surface of the channels of the monolith. This type of coating Provo�it using a solution (or Sol) of the material, be placed, either with the use of a solution containing a very small colloidal particles. The lack of coverage by filling the pores is that the amount of coating that can be applied is limited, because at one stage the pores will be completely filled, and the coating in the wet state becomes unreachable.

Preferably, the catalyst or the catalyst layer is applied on the monolithic wall. Applying a layer on a monolithic wall has the advantages that the possible higher load, and that diffusion in thicker walls does not affect the reaction. This type of coating is carried out by coating with a suspension of particles of size similar to macropores in the monolithic walls, for example, cordierite (typically 5 μm). The principle that therapies of the coating of the suspension next. The monolith is placed in a liquid containing suspended particles. The pores in the wall is a liquid, the precipitated particles on the walls of the monolith, because these particles cannot enter into the pores, leaving a layer of deposited particles.

Get the solution or suspension for coating in the wet state, in which are immersed for a short time dried monolith (dip). Preferably, dipped in a Sol or a suspension of pre-dried and evacuated monolithic detail. Monolith at�Aleut from the liquid, and most of the liquid off, and the residue gently blow with compressed air. Most often, this is done with the use of "air scraper", thin slits for blowing off compressed air, because this method simultaneously clear the entire number of channels. Then the monolith was dried in a horizontal position in a continuous rotation around its axis, to prevent the force of gravity did not cause uneven distribution when applied in the wet state. Finally, the coating is fixed on the monolith stage perforation at high temperature. Download received by drawing in the wet state, is usually 5-10% of the mass. for most methods. If you want download above, you need to repeat the application procedure. This can be done after calcination, or the monolith can be dipped again after drying.

To obtain a layer of a catalyst, the monolith may be coated with a suitable Zola wet application. This Sol can be obtained by hydrolytic. One method of obtaining Zola represents the hydrolysis of a suitable alkoxide. Hydrolysis of metal alkoxide is usually accelerated by the presence of acid or base. During aging Zola, is in the process of polycondensation, leading to cross-linking and the formation of compounds like polymer.

In one of the embodiments of the us�Mr sage of the invention, monolithic structure coated with a wet coating using aluminum oxide in the form of Zola Al. In addition to the hydrolysis of the alkoxide mentioned above, the Sol of aluminum oxide can be obtained from other of his predecessors, such as pseudo-boehmite AlO(OH)×xH2O or hydrolysis of AlCl3.

Additives, such as urea or organic amines, such as hexane-trenchermen, can be added to solu to improve the quality of aluminum oxide. In addition, additives can affect the stability of the sols.

Maybe cations such as La, Mg, Zr, Si, which inhibit the transition of active aluminum oxide in an inert α-phase can be included in the Sol to stabilize the applied wet aluminium oxide from after sintering heat treatment.

In another embodiment of the present invention, a monolithic structure is produced by applying a wet silicon dioxide using Sol Si. Sol Si can be obtained by hydrolysis of tetraalkoxysilane (TAOS), tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) and tetrapropoxide (TPOS). Due to the fact that TAOS is usually not miscible with water, alcohols are often added as co-solvents, to obtain a homogeneous Sol.

Other oxides can be deposited in wet condition similarly. When used�isout in the deposition of wet mixed sols, the layer of mixed oxides can be formed on the surface of the monolith.

Silicon dioxide can be easily applied using a commercial colloidal solutions of silicon dioxide, for example, type Ludox AS. Liquid glass can be added to increase the integrity of the coating of silicon dioxide. Colloidal solutions of silicon dioxide can also be used as a permanent binder for the coating of zeolites and other materials, such as titanium dioxide and dioxide Zirconia or polymer catalyst. The coating in the wet state can be carried out similarly to the procedures described above for the application of wet alumina.

Also you can cover with a wet application of metal monoliths with the previous oxidation. In the first case, the adhesion of the applied wet layer is better.

Instead of Zola can be used the suspension to obtain a layer of a catalyst layer or a catalyst. This may increase the amount of oxide deposited each time. In addition, to obtain a monolithic catalysts when applied in the wet state can be used optimized catalyst powders. Often with the purpose of improving the coating it is necessary to grind in a ball mill for a period to�isit the size of the solid particles to a certain size.

In a preferred embodiment of the invention, the particle size of the oxide carrier material reduces the grind to a medium size from 1 to 40 μm, preferably from 5 to 20 μm. This average particle size is defined as comprising 90% of the particles.

The active ingredient, which is usually a metal side subgroups of group VIII, is usually applied application predecessor in the form of a suitable metal salt. Instead of impregnation, the active ingredient may also be applied by other methods, for example, by spraying the precursor in the form of a metal salt on the carrier. Suitable precursors in the form of metal salts are, for example, nitrates, acetates and chlorides of the respective metals; it is also possible to use hydroxides or complex anions of the metals used. Preference is given to the use of platinum in the form of H2PtCl6or Pt(NO3)2. Suitable solvents for the precursors in the form of metal salts include both water and organic solvents. Particularly useful solvents are water and lower alcohols such as methanol and ethanol.

To cause the alkali and alkaline earth metals are preferably used, the use of aqueous solutions of compounds that can be converted to the corresponding oxides by calcination. P�Rhodesia compounds are, for example, the hydroxides, carbonates, oxalates, acetates or basic carbonates of alkali and alkaline earth metals. If the catalyst doped with metals of main and minor subgroups of group III, is often used hydroxides, carbonates, nitrates, acetates, formiate or oxalates, which can be converted into a suitable oxides by calcination, for example, La(OH)3La3(CO3)2La(NO3)3, lanthanum acetate, lanthanum formate or oxalate of lanthanum.

In one preferred embodiment of the present invention, conduct a post-impregnation of the active components after the application of wet and calcining the honeycomb monolith as follows:

Raw material, i.e. the material(s) media and - if necessary - stable binder for coating in the wet state, is mixed in a suitable vessel, tanks, etc. and mix or stir in suspendirovanie water. The resulting suspension was diluted to the desired solids content and adjusted to a specific pH with the use of certain acids and bases. Then the suspension circulates continuously through the existing mill to reduce the particle size to the average size from 1 to 40 μm, preferably from 5 to 20 μm; the distribution of particle size can be controlled by Autonomous laser �fraccia. Prepared slurry was used for coating.

The application may be made, for example, manually by using a manual nozzle for the process air direction. Correct total solids content for the coating can be determined in a preliminary procedure to achieve a certain load of wet deposition in g/inch3or g/L.

Details immerse in length, preferably 80-90%, but not completely, in the slurry, and - after taking them out - turn so that the suspension is flowed through the cell. The ultimate load applied in the wet state is determined by using a pneumatic gun to distribute the slurry across the channel and blow out excess slurry. Stage of the coating can be repeated to achieve the full target download the application in the wet state. Samples are dried after each stage of deposition at a temperature of from 100 to 200°C, preferably at 120-140°C and calcined at a temperature of 400-750°C, preferably 550-650°C before the next stage.

The thickness of the layer determines the given full amount applied in the wet state of the coating that comes from the density of the deposited wet ingredients and distribution of their particle size. Depending on the rheology of suspensions total quantity of pumps�CSOs in the wet state of the coating should be applied in more than one stage of application.

For impregnation of the active components water absorption is determined using a representative prototype. The active components are dissolved in the desired concentration in water, and part is dipped into the solution for a certain amount of time, mostly a few seconds, then excess water is blown by the air nozzle. These stages of impregnation is repeated as often as required by the method.

After each stage of the impregnation prototypes can be dried and calcined, as described above.

In another embodiment, the active components are already impregnert in material (s) media and/or added to the suspension before or after milling. The full regulation of the content of solids or pH were performed as described above. The stage of applying can be repeated to achieve the full specified load applied in the wet state of the coating. Prototypes can be dried after each stage of the coating at a temperature of 100-200°C, preferably at 120-140°C and calcined at a temperature of 400-750°C, preferably 500-650°C before the next stage.

The penetration depth (dWC) can be determined from the load applied in the wet state of the coating (WCL), the density of the applied wet coating (ρWC) and geometric surface area (GSA)of the monolith:

dWC=WCL/ρWCGSA

The density of the applied wet coating (ρWC) can be determined from the densities of the final monolithic catalyst (ρCathal.) and substrate (ρsubstr.), and the load applied in the wet state of the coating and the specific weight (SW: the total weight of the catalyst relative to its volume) monolithic catalyst:

ρWC=WCLSW/ρKatalandzatop(SWWC)/ρCIbCtpat

The density of the monolithic catalyst and substrate can be determined by density measurements using mercury or helium.

Catalysts for aromatization by dehydrogenation and dehydrogenation, which is applied as a layer on the monoliths

To obtain a catalyst suitable for �romatically during dehydrogenation and dehydrogenation, can be used the so-called amphoteric ceramic oxide, i.e., in particular the oxides of titanium and zirconium, or mixtures thereof; also suitable are the compounds that can be converted into these oxides by calcination. They can be obtained by known methods, for example by the Sol-gel process, precipitation of salts, dehydration of the corresponding acids, dry mixing, suspendirovanie or spray drying.

Suitable ceramic oxide media are all modifications of zirconium oxide and titanium oxide. However, it was found that to obtain catalysts on the basis of ZrO2preferably, when the ratio of monoclinic ZrO2detected by diffraction of x-rays more than 90%. Monoclinic ZrO2characterized by x-ray diffraction pattern of two strong signals in the two-theta range of about 28.2 and 31.5.

The main alloying compound can be produced in the course of obtaining, for example, coprecipitation, or later, for example, impregnava of ceramic oxide compound of alkali metal or alkaline earth metal or compound of the element side of a subgroup of the third group or the rare earth metal compound.

The content of alkali metal or alkaline earth metal, metal main or side GE�uppy group III, rare-earth metal or zinc is usually up to 20 wt.%, preferably between 0.1 and 15 wt.%, more preferably between 0.1 and 10 wt%. As the source of alkali and alkaline earth metal is usually used compounds that can be converted to the corresponding oxides by calcination. Suitable examples are hydroxides, carbonates, oxalates, acetates, nitrates or mixed bicarbonates of alkali and alkaline earth metals.

When the ceramic carrier optionally doped metal or main side of a subgroup of the third group, the source material in this case must also be compounds which can be converted to the corresponding oxides by calcination. When used, for example, lanthanum, suitable compounds of lanthanum containing organic anions, such as lanthanum acetate, lanthanum formate or oxalate of lanthanum.

The components of the noble metal can be deposited in various ways. For example, a ceramic carrier material of the catalyst layer or a catalyst on the monolith may be generally impregnated or sprayed with a solution of corresponding compound of the noble metal or rhenium or tin. Suitable metal salt to obtain such solutions are, for example, nitrates, halides, formate, oxalates, AC�Tata precious metal. It is also possible to use the complex anions or acids of these complex anions, such as H2PtCl6. Particularly suitable compounds for preparing the catalysts according to the invention, as observed, are PdCl2, Pd(OAc)2, Pd(NO3)2and Pt(NO3)2.

Can also be used sols noble metals with one or more components in which the active ingredient is present in the already partially or fully restored condition.

When using noble metal sols, they are obtained in advance in a conventional manner, for example, the recovery of the metal salt or mixture of many metal salts in the presence of a stabilizer such as polyvinylpyrrolidone, and then his application, or application or spraying of the ceramic material of the carrier of the catalyst layer or a catalyst. The methods of production are disclosed in German patent application 19500366.7.

The content in the catalyst of the side elements of the subgroup of group VIII and possibly rhenium or tin, for example, be from 0.005 to 5 wt.%, preferably from 0.01 to 2 wt.%, more preferably from 0.05 to 1.5 wt%. When in addition use rhenium or tin, their relation to the component of the noble metal can be, for example, from 0.1:1 to 20:1, preferably from 1:1 to 10:1.

�retarding additives used (conventional concept of partial poisoning of the catalyst), if you want to be a compound of sulphur, tellurium, arsenic or selenium. The addition of carbon monoxide during catalyst operation is also possible. It was found that the use of sulfur particularly preferably, it is convenient to use in the form of sulphide of ammonium (NH4)2S. the Molar ratio of noble metal to slow down the connection can be from 1:0 to 1:10, preferably from 1:1 to 1:0,05.

The material of the catalyst typically has a surface area according to BET of up to 500 m2/g, typically from 2 to 300 m2/g, more preferably from 5 to 300 m2/g. pore Volume is generally between 0.1 and 1 ml/g, preferably from 0.15 to 0.6 ml/g, more preferably from 0.2 to 0.4 ml/g Average pore diameter of the mesopores determined by the analysis of the penetration of Hg, is usually between 8 and 60 nm, preferably between 10 and 40 nm. The proportion of pores having a width greater than 20 nm, varies typically between 0 and 90%; it was found that it is preferable to use the media with the fraction of macropores (i.e., pores of a width exceeding 20 nm) more than 10%.

One example of aromatization by dehydrogenation, which can be used catalysts according to the invention, represents the aromatization by dehydrogenation of 3,4 - or 2,3-dimethylhexane in o-xylene.

In one embodiment, the catalyst material forming the layer ka�of Aligator on the monolith, has a bimodal distribution of pore radius and contains

a) from 10 to 99.9% wt. Zirconia and

b) 0 to 60 wt%. aluminum oxide, silicon oxide and/or titanium oxide and

b) from 0.1 to 30 wt.%, at least one element of main group I or group II element side of the subgroups of group III, including cerium and lanthanum, side noble metal of subgroup VIII of the periodic table of the elements, and optionally tin,

provided that the sum of the percentages by weight is 100. This material is particularly suitable catalyst for dehydrogenation of alkanes to alkenes and aromatization by dehydrogenation, for example, 3,4 - or 2,3-dimethylhexane in o-xylene.

The material of the catalyst forming the catalyst layer on the monolith, preferably contains

a) from 10 to 99.9% wt., more preferably from 20 to 98 wt.%, particularly preferably from 30 to 95 wt%. zirconium dioxide, from which 50 to 100 wt.%, preferably from 60 to 99 wt.%, particularly preferably from 70 to 98 wt%. are monoclinic and/or tetragonal modification, and

b) from 0.1 to 60 wt.%, preferably, 0.1 to 50 wt.%, particularly preferably, from 1 to 40 wt.%, in particular, from 5 to 30 wt%. aluminum oxide, silicon dioxide and/or titanium dioxide in the form of rutile or anatase, and

b) from 0.1 to 10 wt.%, preferably from 0 to 8 wt%, especially preferably 0.1 to 5 wt.%, at least one element selected from main group I or II group of the side and the subgroups III and VIII groups of the periodic table of the elements cerium, lanthanum and/or tin,

where the sum of the percentages by weight is 100.

In one particularly preferred embodiment, component b) comprises 0.1 to 30 wt.%, preferably 0.5 to 25 wt.%, particularly preferably 1-20 wt%. of silicon dioxide.

The catalyst material preferably consists of a composition, the composition of which is indicated above.

The material of the catalyst forming the catalyst layer on the monolith contains from 70 to 100%, preferably from 75 to 98%, especially preferably from 80 to 95% over 20 nm, preferably between 40 and 5000 nm.

To obtain the material of the catalyst forming the catalyst layer on the monolith, can be used predecessors of okido zirconium, titanium, lanthanum, cerium, silicon and aluminum (forming media), which can be converted by calcination to the oxides. They can be obtained by known methods, for example, a Sol-gel process, precipitation of salts, dehydration of the corresponding acids, dry mixing, suspendirovanie or spray drying. For example, a mixed oxide of ZrO2×xAl2O3×xcho2can be prepared initially accessed�m-enriched water to zirconium oxide of the General formula ZrO 2×xH2O during the deposition of a suitable precursor containing zirconium. Suitable precursors of zirconium represent, for example, Zr(NO3)4, ZrOCl2or ZrCL4. The deposition is carried out by adding a base, such as NaOH, Na2CO3and NH3it is described for example in European application EP-a-849224.

To obtain the mixed oxide ZrO2×xcho2the Zr precursor obtained as described above, may be mixed with Si-containing precursor. Well suited as precursors of SiO2are, for example, water-containing sols SiO2such as Ludox®. These two components can be mixed, for example, simple mechanical mixing or by spray drying in a scrubber with spray.

When using mixed oxides may affect the pore structure in the desired direction. The particle sizes for the different precursors affect the pore structure. Thus, for example, macropores in the microstructure can be generated by using an Al2O3having low loss at burning and a certain distribution of particle size. Aluminum oxide, which was found to be preferred for this purpose is a Puralox (Al2O3with the loss the burning of about 3%).

To obtain the mixed oxide ZrO2 2×Al2O3the mixture of powders of SiOZrO2obtained as described above, can be mixed with a precursor containing Al. This can be carried out, for example, a simple mechanical blending in the mixer. However, the mixed oxide ZrO2×xcho2×Al2O3can also be obtained in a single step by dry mixing the individual predecessors.

Another possible way of manufacturing a carrier having a specific distribution of pore radius for the above catalysts in the target method, is to add in the course of obtaining polymers that can be partially or completely removed by calcination so as to form pores in certain intervals of pore radius. The mixing of polymers and precursors of oxides can be carried out, for example, simple mechanical mixing or by spray drying in a scrubber with spray.

It was found that the use of PVP (polyvinylpyrrolidone) is especially preferable for the production of media with bimodal distribution of pore radius. If PVP is added during the production stage to one or more precursors of the oxides of the elements Zr, Ti, La, CE, Al or Si, after annealing are formed macropores in the range from 200 to 5000 nm. Another advantage of using PVP is Thu� the carrier can be formed more easily. Thus, extrudates having good mechanical properties, can be produced from freshly precipitated, water-containing ZrO2×xH2O, which was previously dried at 120°C, with the addition of PVP and formic acid, even without other precursors of oxides.

Mixed oxide catalyst carriers usually have a higher surface area by BET after calcination than pure media of ZrO2. Surface area according to BET of the mixed oxide supports are typically in the range from 40 to 300 m2/g, preferably from 50 to 200 m2/g, particularly preferably from 60 to 150 m2/g. pore Volume of the catalysts used according to the present invention, is usually from 0.1 to 0.8 ml/g, preferably from 0.2 to 0.6 ml/g Average pore diameter of the catalysts according to the present invention, may be determined by Hg-parametria, is from 5 to 30 nm, preferably from 8 to 25 nm. In addition, preferably, from 10 to 80% of space volume has been compiled by then >40 nm.

Calcination of the mixed oxide supports is preferably carried out after application of the active components and is carried out at a temperature of from 400 to 750°C, preferably from 500 to 700°C, particularly preferably from 550 to 650°C. the temperature of the perforations should generally be at least as �e high, as the temperature of the dehydrogenation reaction.

The material of the catalyst has a bimodal distribution of pore radius. The pores lie in the range, mainly to 20 nm and in the range from 40 to 5000 nm. Relative to the pore volume, the pores constitute at least 70%. The proportion of pores less than 20 nm, is typically about 20 to 60%, while the proportion of pores in the range from 40 to 5000 nm is usually similar from 20 to 60%.

The doping of the mixed oxides of the basic compound can be carried out either when they are received, for example, coprecipitation, or then, for example, application of a mixed oxide compound of alkali metal or alkaline earth metal compound, or coupling element side of the subgroups of group III or rare earth metal compound. Particularly suitable alloying additives are K, Cs and La.

The application component, active in dehydrogenation, which is a side noble metal of subgroup VIII of the group, usually carried out by application with a suitable precursor in the form of a metal salt which can be converted into the corresponding metal oxide by calcination. Alternatively, the application, the component is active in the dehydrogenation can also be applied to other methods, for example, by spraying the precursor in the form of a metal salt on the n�Sitel. Suitable precursors in the form of metal salts are, for example, nitrates, acetates and chlorides of the respective metals, or complex anions of the metals used. Preference is given to the use of platinum in the form of H2PtCl6or Pt(NO3)2. Solvents that can be used to predecessors in the form of a metal salt, which are water and organic solvents. Particularly suitable solvents are lower alcohols such as methanol and ethanol.

Other suitable precursors when using noble metals as a component active in the dehydrogenation, sols are suitable noble metals that can be received by one of known methods, for example, the recovery of the metal salt reducing agent in the presence of a stabilizer such as PVP. The method of obtaining comprehensively described, for example, in German application DE-A 19500366.

As precursors of the alkali metal and alkaline earth metal is usually used compounds that can be converted to the corresponding oxides by calcination, Examples of suitable precursors are hydroxides, carbonates, oxalates, acetates or mixed bicarbonates of alkali and alkaline earth metals.

If mixed occidential additionally or exclusively alloyed metal or main side of a subgroup of the group III, source material in this case must also be compounds which can be converted to the corresponding oxides by calcination. If you use lanthanum, suitable starting compounds are, for example, oxycarbonate lanthanum, La(OH)3La2(CO3)3La(NO3)Wor lanthanum compounds containing organic anions, for example, lanthanum acetate, lanthanum formate or oxalate of lanthanum.

The dehydrogenation catalysts, which are applied as layers on the monoliths

Other suitable materials of the dehydrogenation catalysts generally contain a metal oxide selected from the group consisting of zirconium dioxide, zinc oxide, aluminum oxide, silicon dioxide, titanium dioxide, magnesium oxide, lanthanum oxide, cerium oxide and mixtures thereof, as a ceramic carrier material. Preferred carriers are zirconium dioxide and/or silicon dioxide; specific preference is given to mixtures of zirconium dioxide and silicon dioxide.

Active material composition of the dehydrogenation catalyst usually contains one or more noble metals side of the subgroups of group VIII, preferably platinum and/or palladium, particularly preferably platinum. In addition, the dehydrogenation catalyst may further contain one or more �elements of main group I and/or II groups, preferably, potassium and/or cesium. The dehydrogenation catalyst may further contain one or more side elements of the subgroup of group III including the lanthanides and actinides, preferably lanthanum and/or cerium. Finally, the dehydrogenation catalyst may also contain tin, preferably tin contains.

In a preferred embodiment of the invention, the dehydrogenation catalyst contains at least one element side of the subgroups of group VIII, at least one element of main group I and/or II) at least one element side of the subgroups of group III including the lanthanides and the actinides, and tin.

To obtain the carrier material of the dehydrogenation catalyst, applied in the wet state on a monolith in the form of a layer, it is possible to use precursors of oxides of zirconium, silicon, aluminum, titanium, magnesium, lanthanum or cerium, which can be converted into oxides by calcination. They can be produced by known methods, for example by the Sol-gel process, precipitation of salts, dehydration of the corresponding acids, dry mixing, suspendirovanie or spray drying. To obtain the mixed oxide ZrO2×SiO2containing zirconium precursor obtained above, can be mixed with containing silicon precursor. Well coming�their predecessors SiO 2represent, for example, water-containing sols SiO2such as Ludox™ or methoxyphenylalanine methylpolysiloxanes, such as SILRES® MSE 100. These two components can be mixed, for example, simple mechanical mixing or by spray drying in the dryer with a spray.

Materials ceramic carriers of the catalyst for dehydrogenation catalysts, which are applied in the wet state in the form of layers on the monoliths according to the present invention usually have a high surface area by BET after calcination. Surface area by BET is usually over 40 m2/g, preferably more than 50 m2/g, particularly preferably greater than 70 m2/g. the Volume of pores of the dehydrogenation catalysts used according to the present invention, is usually from 0.2 to 0.6 ml/g, preferably from 0.25 to 0.5 ml/g Average pore diameter of the dehydrogenation catalysts used according to the present invention, may be determined by the Hg parametria, is from 3 to 30 nm, preferably from 4 to 25 nm.

In addition, the material of the dehydrogenation catalyst according to the present invention have a bimodal distribution of pore radius. The pores have a size in the range up to 20 nm and in the range from 40 to 5000 nm. These pores together constitute at least 70% of the total space �the PR of the dehydrogenation catalyst. The proportion of pores less than 20 nm is usually in the range from 20 to 60%, while the proportion of pores in the range from 40 to 5000 nm is usually similar from 20 to 60%.

Active in dehydrogenation component, which is a side noble metal of subgroup VIII of the group, usually applied application a suitable precursor in the form of a metal salt.

Instead of impregnating the component active in the dehydrogenation may also be applied by other methods, for example, by spraying the precursor in the form of a metal salt on the carrier. Suitable precursors in the form of metal salts are, for example, nitrates, acetates and chlorides of the respective metals; it is also possible to use the complex anions of these metals. Preference is given to the use of platinum in the form of H2PtCl6or Pt(NO3)2. Suitable solvents for the precursors in the form of a metal salt include both water and organic solvents. Particularly preferred solvents are water and lower alcohols such as methanol and ethanol.

For the deposition of alkali and alkaline earth metals preferably used aqueous solutions of compounds that can be converted to the corresponding oxides by calcination. Suitable compounds are, for example, hydroxides, carbonates, oxalates, �zetty or basic carbonates of alkali and alkaline earth metals. If the catalyst doped with metals or main side of a subgroup of group III, is often used hydroxides, carbonates, nitrates, acetates, formiate or oxalates, which can be converted to the corresponding oxides by calcination, for example, La(OH)3La2(CO3)3La(NO3)3, lanthanum acetate, lanthanum formate or oxalate of lanthanum.

When you use precious metals as components, active in dehydrogenation, suitable precursors also include an appropriate noble metal sols, which can be received by one of known methods, for example, the recovery of the metal salt by using a reducing agent in the presence of a stabilizer such as PVP. The method of obtaining comprehensively described, for example, in German application DE-A 19500366.

The amount of noble metal that is present as a component active in the dehydrogenation, the dehydrogenation catalysts used according to the present invention, is from 0 to 5 wt.%, preferably from 0.05 to 1 wt.%, particularly preferably, from 0.05 to 0.5% of the mass.

Other active components of the composition can be applied either during manufacture of the carrier, for example, coprecipitation, or later, for example, application of appropriate media connections-PR�destinygame. Used, the precursor compounds are generally compounds that can be converted to the corresponding oxides by calcination. Suitable precursors are, for example, hydroxides, carbonates, oxalates, acetates, chlorides or mixed carbonates of the respective metals.

In preferred embodiments of the invention, the active composition further contains the following additional components:

- at least one element of main group I or II group, preferably cesium and/or potassium in an amount of from 0 to 20 wt.%, preferably from 0.1 to 15 wt.%, particularly preferably, from 0.1 to 10 wt%.;

- at least one element side of the subgroups of group III including the lanthanides and actinides, preferably lanthanum and/or cerium, in an amount of from 0 to 20 wt.%, preferably from 0.1 to 15 wt.%, particularly preferably, from 0.2 to 10 wt%.;

- tin in an amount of from 0 to 10 wt%.

The dehydrogenation catalyst preferably contains no halogen.

Calcination of the catalyst carriers impregnated consider a solution of a metal salt, usually carried out at a temperature from 400 to 750°C, preferably from 500 to 700°C, particularly preferably from 550 to 650°C for a period from 0.5 to 6 hours.

The catalyst for the combustion of hydrogen

The preferred catalyst, to�which catalyzes the combustion of hydrogen, contains side noble metal of subgroup VIII and/or group I of the periodic table and/or tin. Especially preferred are catalysts containing platinum, possibly in combination with tin. As materials of the carrier for these catalysts can be used metal oxides selected from the group consisting of zirconium dioxide, zinc oxide, aluminum oxide, silicon dioxide, titanium dioxide, magnesium oxide, lanthanum oxide, cerium oxide, zeolites and mixtures thereof. Preferred carriers from oxides of metals are zirconium dioxide, magnesium oxide, silicon dioxide, zinc oxide and aluminum oxide, or mixtures thereof.

Hydrogen, the catalyst can be used for selective oxidation of hydrogen to supply heat for dehydrogenation as described above. In another embodiment of the process, the catalyst combustion of hydrogen can also be used as a purifying catalyst to selectively remove oxygen from streams containing hydrocarbons.

Catalytic dehydrogenation

The dehydrogenation can be carried out as oxidative or non-oxidative dehydrogenation. Non-oxidative dehydrogenation can be carried out autothermal or autothermal. The dehydrogenation can be carried out izotermicheskii or adiabatically.

�okisliteljno the catalytic dehydrogenation of alkanes, preferably, spend autothermal. In this case, oxygen is additionally mixed into the reaction gas mixture of the dehydrogenation in at least one reaction zone and the hydrogen and/or hydrocarbon present in the reaction gas mixture is burned, at least partially, that produces at least part of the heat of dehydrogenation required in at least one reaction zone directly in the reaction gas mixture.

In a preferred embodiment of the catalyst according to the invention is used for dehydrogenation of propane to propylene or dehydrogenation of butane to butene.

One feature of the nonoxidative method compared to an oxidative method is, at least in the intermediate formation of hydrogen, which is manifested in the presence of hydrogen in the gaseous dehydrogenation product. Oxidative dehydrogenation of free hydrogen is not found in the gaseous dehydrogenation product.

A suitable form of reactor is a tubular reactor with a fixed bed or a shell and tube reactor. In these reactors, the catalyst (dehydrogenation catalyst and, if appropriate, specific oxidation catalyst) is in the form of a fixed bed in a reaction tube or in a bundle of reaction tubes. Conventional internal� diameters of the reaction tubes is from about 10 to 15 cm. A typical shell-and-tube reactor dehydrogenation contains from about 300 to 1000 reaction tubes. The internal temperature in the reaction tubes usually varies in the range from 300 to 1200°C, preferably in the range from 500 to 1000°C. the Operating pressure is usually from 0.5 to 8 bar, frequently from 1 to 2 bar when using low dilution steam, or even from 3 to 8 bar when using high vapor dilution (corresponding to the active process of steam reforming (STAR process) or the Linde process) for the dehydrogenation of propane or butane of Phillips Petroleum Co. Regular hourly volumetric gas flow rate (GHSV) is 500 to 2000 h-1regarding the choice of hydrocarbon. The geometry of the catalyst can, for example, be spherical or cylindrical (hollow or solid). It is also possible to operate the multiple tubular reactors or reactors of the tube bundle with fixed bed next to each other, of which at least one is alternately in a state of regeneration.

Non-oxidative catalytic autothermal dehydrogenation can also be carried out under heterogeneous catalysis in a fluidized bed, according to the Snamprogetti process/Yarsintez-FBD. Accordingly, the two fluidized bed operate in parallel, one of which is usually in a state of regeneration. Working giving�the amount is usually 1 to 2 bar, the dehydrogenation temperature is usually from 550 to 600°C. the Heat required for dehydrogenation, may be introduced into the reaction system prior to heating the dehydrogenation catalyst to the reaction temperature. Adding a parallel stream containing oxygen, eliminates heater to generate heat directly in the reactor system by burning hydrogen and/or hydrocarbons in the presence of oxygen. If this is acceptable, you can add an additional stream containing hydrogen.

Nonoxidative autothermal dehydrogenation is preferably carried out in a plate reactor. This reactor contains one or more successive catalyst layers. The number of catalyst beds may be from 1 to 20, preferably from 1 to 6, more preferably from 1 to 4, especially from 1 to 3. Layers of the catalyst preferably is blown radially or along the axis of the reaction gas. Typically, such a plate reactor is exploited by using a fixed bed of catalyst. In the simplest case, the fixed catalyst layers are arranged along an axis in a shaft reactor or in the annular gaps of concentric cylindrical grids. Mine reactor corresponds to one plate. Carrying out the dehydrogenation in a single shaft reactor corresponds to one and� embodiment of the invention. In another preferred embodiment, the dehydrogenation is carried out in plate reactor having a catalyst layer 3.

Usually the amount of gaseous oxygen that is added to the reaction gas mixture is chosen so that the required for dehydrogenation alkane (e.g., propane and/or n-butane) the amount of heat generated by the combustion of hydrogen present in reaction gas mixture, and any hydrocarbons present in the reaction gas mixture and/or of carbon present in the form of coke. Usually the total quantity of oxygen relative to the total number alkane is from 0.001 to 0.5 mol/mol, preferably from 0.005 to 0.25 mol/mol, more preferably from 0.01 to 0.25 mol/mol. Oxygen can be used either in the form of pure oxygen or as oxygen-containing gas that contains an inert gas. To prevent the loss of higher alkanes and alkenes at work (see below), may be preferable when the content of oxygen in oxygen-containing gas is high, and is at least 50% vol., preferably at least 80% vol., more preferably at least 90% by vol.. Especially preferred oxygen-containing gas is oxygen technical purity of the contents O2 approximately 99% by vol. In addition, a method in which the oxygen-containing gas supplied air.

Hydrogen is combusted to produce heat is the hydrogen formed in the catalytic dehydrogenation alkane, and any hydrogen is optionally added to the reaction gas mixture as gaseous hydrogen. The number of the presence of hydrogen should preferably be such that the molar ratio between N2/O2in the reaction gas mixture immediately after the oxygen ranged from 1 to 10 mol/mol, preferably from 2 to 6 moles/mole. In multistage reactors, this applies to each intermediate feed gas containing oxygen and hydrogen.

The hydrogen is burned catalytically. A commonly used dehydrogenation catalyst also catalyzes the combustion of hydrocarbons and of hydrogen with oxygen, so that, in principle, not required no special oxidation catalyst, in addition. In one embodiment of the invention, the operation is performed in the presence of one or more oxidation catalysts which selectively catalyze the combustion of hydrogen with oxygen in the presence of hydrocarbons. The combustion of these hydrocarbons with oxygen to give CO, CO2and water, therefore, occurs only in a small step�no. The dehydrogenation catalyst and the oxidation catalyst is preferably present in different reaction zones.

When the reaction is conducted in more than one stage, the oxidation catalyst may be present in only one, in more than one or in all reaction zones.

Preference is given to placement of a catalyst which selectively catalyzes the oxidation of hydrogen at points where there is a higher oxygen partial pressure than at other points in the reactor, especially near the point of feed of oxygen-containing gas. Gaseous oxygen and/or hydrogen can be fed at one or more points in the reactor.

In one embodiment of the method according to the invention, there is an intermediate flow of oxygen-containing gas and hydrogen above each plate of the reactor. In another embodiment, the method according to the invention, oxygen-containing gas and the hydrogen serves above each plate, except for the first plate. In one embodiment of the invention, a special layer of oxidation catalyst is present below along the flow of each point of filing and is accompanied by a layer of the dehydrogenation catalyst. In another embodiment of the invention, there is no specific oxidation catalyst. The dehydrogenation temperature is generally from 400 to 1100°C; the pressure in the last layer of catalysis�ora disc reactor is generally from 0.2 to 5 bar absolute, preferably from 1 to 3 bar absolute. GHSV (hourly space velocity of feed gas) is typically from 500 to 2000 h-1and when working with high load even up to 100000 h-1preferably from 4000 to 16000 h-1.

Catalytic aromatization by dehydrogenation

Aromatization by dehydrogenation is usually carried out at temperatures of from 300 to 800°C, preferably from 400 to 700°C, more preferably from 450 to 650°C and at pressures from 100 mbar to 100 bar, preferably from 1 to 30 bar, more preferably from 1 to 10 bar, LHSV (hourly volumetric velocity of the fluid) from 0.01 to 100 h-1preferably from 0.1 to 20 h-1. In addition to a mixture of hydrocarbons may contain diluents, such as CO2N2, inert gases or steam. Similarly, it is possible to add, if required, hydrogen at a volume ratio of hydrogen to hydrocarbons (gaseous) may be from 0.1 to 100, preferably from 0.1 to 20. Add hydrogen, or can be used the one that formed during dehydrogenation and, if suitable, recyclezone to remove the carbon that builds up on the catalyst surface, increasing the reaction time.

In addition to the permanent (continuous) the addition of a gas which prevents the deposition of coke during the reaction, there is a possibility of periodic regeneration to�of telesfora the hydrogen or the air above it. The regeneration takes place at temperatures in the range from 300 to 900°C, preferably from 400 to 800°C with the free oxidizing agent, preferably air or mixtures of air and nitrogen, and/or in a reducing atmosphere, preferably hydrogen. Regeneration can be conducted at atmospheric pressure, reduced pressure, or above atmospheric. Suitable pressures are, for example, from 500 mbar to 100 bar.

The invention is further illustrated by the following examples

Examples

Examples 1-12

The preparation of catalysts dehydrogenation/aromatization according to the invention, a method And

Method And describes the post-impregnation of the active components after the application of wet and calcining the honeycomb monolith.

Getting suspensions for application in wet conditions

To obtain suspensions for application in wet condition use with spray-dried powder of zirconium dioxide BASF SE D9-89. 17000 g of this powder was dispersed in 15000 ml of water and mixed with 1200 g of SILRES® MSE 100. The resulting suspension with a theoretical total solids content of 52% has a pH of from 3.2 to 3.8. This the resulting suspension is milled in a continuously operating mill for about 1 h to achieve the final particle size of 11.5 microns in average with an acceptable range of +/-1,5 μm for 90% of the particles. Distributed�e particle size control repeatedly during the process offline laser diffraction. Willing suspension has a pH of from 3.2 to 3.8. The resulting suspension is used for coating.

The process of applying wet

This slurry was then appropriately diluted for application to a ceramic substrate with full solids content of about 50% with a deviation of +/-1%. The coating was carried out through a process with a directional air blowing. Correct total solids content for the coating must be determined in a preliminary procedure to achieve a given load applied in the wet state of the coating in g/inch3or g/L.

Use one solid piece of cordierite 400 cpsi (cells per square inch) from Corning Incorporated. To prototype these parts are immersed for 80-90% in the suspension; after taking their turn, and the suspension flows through the cell. Download of the applied wet coating of reach by using a pneumatic gun to distribute the slurry across the channel and to blow an excessive amount of suspension. Under cover again, to eventually achieve a specific end-load applied in the wet state of the coating 4.5 g/inch3. Samples are dried after each stage of the coating at a temperature of from about 120 to 140°C for 15 minutes with frequent reversal balloon�flux and calcined at 560°C for 3 h before the next stage.

Impregnation of the active components

The active components are applied in two stages by absorption of water from solutions of the materials of his predecessors. First, determine the water absorption on a representative sample and calculate the concentration based on the absorption.

214,9 g (IEA)2Pt(OH)6in the form of a solution concentration gained 17.22% in IEA (IEA = monoethanolamine) and 82 g of KOH dissolved in 8000 g of water, yielding a pale yellow solution with a pH of about 12. The coated components are immersed into the solution while soaking 15 seconds. When the parts are removed from the solution, gently blow air above the nozzle, and dried in reversing the air stream at a temperature of from 120 to 140°C for another 15 minutes. Calcination takes place in a furnace or device for continuous firing at 560°C for about 3 h.

To obtain a second solution for impregnation CsNO3, SnCl2×N2About and La(NO3)3dissolved in 6750 g of water, whereas the same water absorption for wet impregnation. The parts are immersed and removed from the solution after 15 seconds, freely purged moderate air flow. These parts are dried in reversing the air stream at a temperature of from 120 to 140°C for another 15 minutes. Calcination takes place in a furnace or device for continuous firing at 560°C for about 3 h.

table 1 below shows an overview of the properties of the produced catalysts. The penetration depth (dWC) was determined from the load applied in the wet state of the coating (WCL), the density of the applied wet coating (ρWC) and geometric surface area (GSA) of the monolith:

dWC=WCL/ρWCGSAd

The density of the applied wet coating (ρWC) was determined from the densities of the final monolithic catalyst (katalysator) and cordierite substrate (substrate), and the load applied in the wet state of the coating and the specific weight (SW: the total weight of the catalyst relative to its volume) monolithic catalyst:

ρWC=WCLSW/ρKatalandzatop(SWWC)/ρCIbCtpat

The density of the monolithic catalyst and substrate was determined by density measurements using mercury or helium.

Table 1
PR.Downld. the nanos. in VL. comp. p-TIA [g/l]Destiny. weight [g/l]Downld. Pt [g/l]The elemental composition [% wt.]The penetration depth [µm]
PtSnToCsLaZrSi
13206522,00,310,880,060,211,22913153
23206231,50,240,560,160,262,73211 148
33206231,40,220,510,180,242,63112148
43206231,30,210,550,150,252,53012148
53206231,70,270,530,170,232,42713148
63206231,50,240,510,17 0,242,52913148
73206231,60,250,570,150,212,32514148
83206231,90,310,450,150,212,43012148
93206231,90,30,530,160,162,62813148
103006380,9 0,140,480,190,231,33013143
112906022,00,340,440,20,232,553112135
122807170,50,0640,260,130,191,92215138

Example 13

The preparation of catalysts dehydrogenation/aromatization according to the invention by method B

Method B differs only slightly from the method And the fact that the active components are generally impregnated into the carrier material and milled to form a slurry prior to application on a monolithic substrate.

Getting suspensions for application in wet and impregnation of the act�VNOM components

6220 g of Zirconia D9-89 impregnert to 131.4 g of the Pt salt solution used in examples 1 through 12, and 23 g KOH dissolved in 1730 g of water. This impregnated Zirconia then impregnert a solution of 45 g SnCWW, 35 g CsNOs and 237 g of La(NO3)3dissolved in 3270 g of water containing 13 g of HCl (37%). The resulting suspension is milled at pH 3.6 in a continuously operating mill for about 1 h in order to achieve the final particle size of 10.5 μm on average (with a standard deviation of +/-1,5 μm for 90% of the particles). The distribution of particle size control several times during the process offline laser diffraction. Willing suspension has a pH from 3.6 to 4. The resulting suspension is used for coating.

The process of applying wet

Application is carried out as described above in 3 separate stages, followed by drying at a temperature of about 130°C and calcining at 590°C after each stage of the coating.

Table 2 below shows an overview of the properties produced in example of catalyst. The depth of penetration was determined as described in examples 1 through 12.

Table 2
PR.Downld. the nanos. in VL. comp. POC-TIA [g/l]Destiny. weight [HL] Downld. Pt [g/l]Elemental composition [% wt.]The penetration depth[µm]
PtSnToCsLaZrSi
132706970,80,110,220,090,171,12415133

Comparative example 1

Obtaining extrudates of catalysts for dehydrogenation/aromatization

The catalyst was produced in the form of extrudate according to example 4 of German application DE 19937107. Download Pt in this catalyst was 4.0 g/L.

Dehydrogenation of propane on a laboratory scale

Examples 14 to 19 and comparative examples 2 to 5

General procedure

The reactor consists of a chamber made of steel 1.4841 surrounded by insulating material and casing from external pressure, made of steel 1.4541. This reactor is designed for an adiabatic method. With�m casing pressure is supporting the supply of heat via the heating circuit, to compensate for heat loss from the chamber. The camera has an internal diameter of 20 mm. This chamber is filled with catalyst. Above the adiabatic region, in the upper third (above in the course relative to the catalyst), pre-heater with a copper jacket.

Propane, nitrogen, hydrogen and air is dosed out in the reactor in gaseous form by means of mass flow controllers (Brooks). The air was added separately through the tube 8 cm higher in the course of the catalyst layer. Water moved from the reservoir through the pump for HPLC in the evaporator of a steel pipe, and the vapor being made by heating in the reactor.

The exhaust gases introduced through the pressure regulator and filter in the water separator, cooled to 10°C. Below the separator, the waste gas is passed through the regulator outlet pressure at about 1.3 bar (abs.) in working online gas chromatograph (NR, from Agilent) for analysis and determination of conversion and selectively.

For carrying out dehydrogenation of propane, the catalyst was installed in the middle of the adiabatic section of the reactor. The catalysts according to the invention represented in each case round cells with cell bars with a length of 101.6 mm and a diameter of 15 mm. In the case of the catalysts of comparison, set 1.5 mm extrudates with 20 ml. Above and below the catalyst layer value�Wali inert material (steatite spheres from 2-3 mm).

For the first activation, the catalyst was reduced by hydrogen flow (12 l in n. o./h) at 450°C and 3 bar (abs.) within 45 minutes. During the dehydrogenation temperature of the preheater was set at 450°C and the reaction pressure was 1.5 bar (abs). The dehydrogenation was carried out autothermal, i.e. with simultaneous combustion of hydrogen to provide heat required for the dehydrogenation. Length dehydrogenation cycle was 12 h.

Between cycles of dehydrogenation, the catalyst was regenerated by burning off coke and subsequent reduction with hydrogen. Coke is burned in advance of when the heater temperature of 450°C and a pressure of 3 bar (abs.) depleted air (a mixture of nitrogen/air, air flow 15 l when n. o./h) with an oxygen content of 1% by vol. Thereafter, the air content was gradually increased to 100% (the air flow of 80 l with n. o./h) and the temperature increased to 550°C. the reduction with hydrogen was carried out at 450°C, 3 bar (abs.) and with a hydrogen flow of 12 l at n. o./p.m.

Table 3 below shows the results of the autothermal dehydrogenation of propane at boot time (hour volumetric gas velocity, GHSV) of 2000 l (n. o.) (propane)/l (catalyst)/h. the composition of the feed gas mixture was 41,0% vol. propane, 41,0% vol water, 5,1% vol. hydrogen, 10.3% of vol. nitrogen and 2.6% vol. oxygen. The values indicated performance�control an average of three cycles of dehydrogenation with fresh catalyst. From this it becomes clear that the catalysts according to the invention (examples 8, 12 and 13) achieve significantly higher performance relative to propylene Pt than the extrudates of catalyst on the previous technology. This is true for catalysts produced according to the method A (examples 1 through 12) and method B (example 13).

Table 3
The catalyst in exampleFormConversion [%]Selectivity [%]Vol. production capacity [kgpropyl/kgPt/h]
8cell1797295
12cell1196831
13cell1097486
sravnitel. 1layer1896159

propane(n.)/lcatalyst/h and the feed composition of 42.6% vol. propane, 42.6% of vol. water, 4,2% vol. hydrogen, 8,5% vol. nitrogen and 2.1% by vol. oxygen. These values represent averages from three cycles of the catalyst, formed more than 35 cycles. From this it becomes clear that the catalyst according to the invention (example 10), even after a long period of time and with different loadings and achieves significantly higher performance relative to propylene Pt than the extrudates of catalyst on preceding technologies.

Table 4
The catalyst in exampleFormGHSV h-1Conversion [%]Selectivity [%]Vol. production capacity [kgpropyl./kgPt/h]
10cell20001398525
will compare. 1layer2000159913
10cell40001198910
will compare. 1layer40001399235
10cell600010981209
will compare. 1layer60001098283

Dehydrogenation of propane to the pilot scale installation

Test dehydrogenation of propane was performed in the adiabatic reactor of stainless steel (steel 1.4841, inner diameter 36 mm, length 4 m), which consists of 3 layers of catalyst is about 90 cm long each, depending on the type of catalyst. The temperature inside the catalyst layer was controlled by two 14-point thermocouples (internal diam. 6 mm) inserted through the middle of the catalyst layer, one top and one bottom. The reaction medium consists of a mixture of propane, hydrogen, steam and pure�of O 2. O2and steam was injected into the mixture in three separate points of dispensing, one for each catalyst. The distance between the feeding points and the catalyst layers was varied, but usually it was between 554 and 150 mm. in addition, the flow velocity Of2slightly changed during the dehydrogenation cycle, while the feed speed of the other components were maintained constant. Before entering into the reactor a mixture of hydrogen and propane pre-heated by passing through a separate heat pump water heater 520, 525, 530, 580°C.

When the test was conducted with the catalyst in the form of extrudate, used 3 mm extrudate catalyst of comparative example 1. When the test was performed with a monolithic catalyst, used catalyst from example 11. Just put together 6 monoliths (34 mm di am. 15 cm length) to form a single layer. In the center of each monolith was then drilled a 6 mm hole along the axis direction, which ensured the possibility of installation of thermocouples. The perimeters of the top and bottom of the monolith was used to compact the fiberglass to prevent bypass flow. In each case the gap between the two catalyst layers filled with a layer of steatite.

The testing activity was carried out continuously, alternating cycles of dehydrogenation and regeneration (approximately 0 hours each). After each cycle of the dehydrogenation reactor is purged with N2. The regeneration procedure was started at a pressure of 4.5 bar with dilute mixture of air for 240 min., and then clean air for 8 hours. At the end of the regeneration cycle was performed 6 cycles of pressure increase and decrease (alternating between pressure of 0.5 and 4 bar every 10 min) to remove residual traces of coke on the surface. After purging the reactor with N2he restored the catalyst, starting with diluted H2within 30 minutes, then pure H2for 30 min at 500°C. Then the reaction mixture is again introduced into the reactor for the next cycle of dehydrogenation.

Conversion and selectivity are given for each cycle are averaged values on this cycle. The volumetric flow rate defined as the rate of flow of propane divided by the volume of the catalyst, where the amount of catalyst is determined as the volume of the layer, the catalyst employed, including the volume of voids.

Example 20

Only 18 monoliths of example 11 with a total weight of 1448 g (2.30 l) uniformly distributed in three layers. Each layer consisted of 6 monoliths, and the content of Pt was 2.0 g Pt /liter of reactor volume. 6360 g/h of propane (GHSVC3=1400 lC3/lcat./h) and 75 g/h H2filed in the reactor in the form of the reaction mixture with O2and H2O (steam) supplied to each feeding point. Couples filed with the UK�the rate of 1000 g/h of each feeding point, while the rate of O2varied over the cycle in accordance with table 5 below:

170
Table 5
The dehydrogenation time (min)O2O2O2
1st point of the feed (g/h)2nd feeding point (g/h)3 point of feed (g/h)
25000
26303030
27804040
281356050
292108560
3025011075
31280 12580
6934013185
10734013486
14434013787
18234014088
22034014389
25834014790
29534015192
33334015594
37134016096
409340165100
446340105
484340175110
522330185120
560325195120
598320200132
635315205137

The average conversion rate of propane and the selectivity to propylene cycle is 35% and 95%, respectively, with a volumetric capacity of 420 kgof propylene./kgPt/h.

Example 21

All conditions remained the same as in example 20, but with 8600 g/h of propane and feed About2in table 6 below:

Table 6
The dehydrogenation time (min)O2O2O2
1st point of the feed (g/h)2nd feeding point (MS) 3 point of feed (g/h)
10000
13250135105
16275150111
54278161121
92280163123
129283164123
167285164124
205287165124
243288165124
280289166124
318 290166124
356291167124
394292167125
431293168125
469294168125
507295168125
545295168126
583295170126
620295170126

The average conversion rate of propane and the selectivity to propylene cycle were 28% and 95%, respectively, with a volumetric capacity of 446 kg (propylene)/kg(Pt)/h.

Comparative example 6

Just 3,27 kg (2,49 l) of 3 mm extrudates were evenly distributed in three layers. Each slo� consisted of 1090 g of catalyst (830 ml). Download Pt was 4.0 gPt/l of reactor volume. 6360 g/h propane (GHSVC3=1300 lC3/lcat./h) and 75 g/h of N2introduced into the reactor as the reaction mixture with O2and H2O supplied to each feeding point. Steam was applied at a rate of 1000 g/h of each feeding point, while the Oz speed was varied over the cycle, according to the table 7 below:

280
Table 7
The dehydrogenation time (min)O2O2O2
1st point of the feed (g/h)2nd feeding point (g/h)3 point of feed (g/h)
323516040
625019555
4426019765
8226520067
11920569
15726921071
19527121273
23327321475
27027521680
30827621885
34627722087
38427822289
42127922491
45928022693
49728022895
53523095
57328023095
61028023095

The average conversion rate of propane and the selectivity to propylene cycle is 35% and 95%, respectively, with a volumetric capacity of 210 kg (propylene)/kg (Pt)/h.

Comparative example 7

All conditions remained the same as in comparative example 7, but with 8600 g/h of propane and submission of O2in table 8 below:

221
The dehydrogenation time (min)O2O2O2
1st point of the feed (g/h)2nd feeding point (g/h)3 point of feed (g/h)
324515550
626019065
44270 19275
8227519577
11927720079
15727920581
19528120783
23328320985
27028521190
30828621395
34628721597
38428821799
421289219101
459290103
497290223105
535292225107
573292225107
610292225107

The average conversion rate of propane and the selectivity to propylene cycle amounts to 29% and 96%, respectively, with a volumetric capacity of 242 kg (propylene)/kg (Pt)/h.

Dehydrogenation of n-butane on a laboratory scale Example 22 and comparative example 8

The dehydrogenation of n-butane was carried out in an electrically heated tubular reactor (steel 1.4841, inner diameter 18 mm), n-butane, nitrogen, hydrogen and air is dosed out in the reactor in gaseous form by means of mass flow controllers. The air was added separately in 10 cm up above in the course of the catalyst layer. Water moved from the reservoir through the pump for HPLC in the evaporator of a steel pipe, and the vapor was directed into the reactor.

The exhaust gases introduced through the pressure regulator in a water separator, cooled�th to 10°C. Below along the flow of the separator, the waste gas is passed into a working online gas chromatograph (µGC, from Varian) to analyze and determine conversion and selectively.

In order to carry out the dehydrogenation of n-butane, the catalyst was installed in the middle of the isothermal section of the reactor. In the case of the catalyst according to the invention, installed round cells with cell rod with a length of 101.6 mm and a diameter of 15 mm. In the case of the comparative catalyst, was established round cells with cell rod with a length of 101.6 mm and a diameter of 15 mm. In the case of the comparative catalyst, was established 20 ml of 1.5 mm extrudate. Above and below along the flow of the catalyst layer was injected inert material (steatite spheres of 2-3 mm).

For the first activation, the catalyst was reduced with hydrogen flow of 10 l (n. u.)/h at 500°C and 2.5 bar (abs.) within 30 minutes. During the dehydrogenation temperature in the reactor furnace was set to 570°C. the pressure in the reactor was 1.5 bar (abs). Length dehydrogenation cycle was 12 h. the Dehydrogenation was performed at boot time (hour volumetric flow rate, GHSV) of 500 l (n. o.) (n-butane)/l (catalyst)/h with the following composition of the supplied gas mixture: 41,4% vol. n-butane, 16,6% vol. water, 18.6% of vol. hydrogen, or 18.7% vol. nitrogen and 4.7% vol. oxygen.

Between cycles the catalyst was regenerated you�iganie coke and then by reduction with hydrogen at a pressure of 2.5 bar (abs). Cox was previously scorched depleted air (nitrogen/air mixture, the air flow of 5 l (n. u.)/h) with oxygen content of 4% vol. when the temperature in the furnace at 400°C. thereafter, the air content was gradually increased to 100% (the air flow 33 l (n. u.)/h) and the temperature increased to 500°C. during recovery more than 30 minutes the temperature was 500°C, and the hydrogen flow was 10 l (n. u.)/p.m.

Table 9 below shows the mean values of three cycles of catalysts formed by an at least 20 cycles. Also in the case of the dehydrogenation of butane, it is clear that the catalyst according to the invention from example 8, with similar conversion and selectivity reaches a substantially higher relative to platinum performance for propylene than the extrudates of catalyst on preceding technologies.

Table 9
The catalyst in exampleFormConversion [%]Selectivity [%]Vol. production capacity [kgbutene/kgPt/with]
comparative 1layer4095120
8cell3896230

Example 23

Dehydrogenation of n-butane in the pilot scale installation

The reactor consists of a steel chamber, made of steel 1.4841, which is surrounded by insulating material and casing protection from external pressure, made of steel 1.4541. The reactor is designed for an adiabatic method. Casing protection from the pressure itself is supporting the supply of heat via a heating cuff to compensate for heat loss from the chamber. The camera has an internal diameter of 52.5 mm and a length of 2.25 m. the Chamber was filled with catalyst. Above in the course relative to the adiabatic reactor has a steel pre-heater engaged in the supply of heat by heating the cuff.

n-butane, nitrogen, hydrogen, oxygen, and air is dosed out in the reactor in gaseous form through the mass flow controllers. Oxygen dehydrogenation added separately through the tube 25 cm above the catalyst layer. Water was similarly applied to steel pipe of the evaporator in liquid form through the mass flow controllers, and water vapor, which formed, was sent into the reactor in a heated form.

The exhaust gases introduced through the pressure regulator and filter in the water separator, cooling�established to 10°C. Below, in the course of the separator, the waste gas sent to working online gas chromatograph (NR, from Agilent) for analysis and determination of conversion and selectively.

For carrying out dehydrogenation of n-butane, the catalyst was placed in three layers in the adiabatic section of the reactor, each separated from each other by a layer of inert steatite rings, height × outer diameter × inner diameter = 5×3×2 mm). The full amount of the catalyst was 1 l; it was divided into three layers of catalyst having the same volume. In the case of the catalyst according to the invention installed honeycomb cores 5 cm in diameter and specified lengths. In the case of the comparative catalyst used 3.0 mm extrudate.

For the first activation, the catalyst was reduced with hydrogen flow of 200 l (n. u.)/h at 500°C and 2.5 bar (abs.) within 45 minutes. During dehydrogenation heater temperature was set to 450°C, and the reaction pressure was 2,25 bar (abs). The dehydrogenation was carried out autothermal, i.e. with simultaneous combustion of hydrogen to provide the necessary heat of dehydrogenation. Length dehydrogenation cycle was 12 h.

The dehydrogenation was performed at boot time (hour volumetric flow rate, GHSV) 650 l (n. o.) (n-butane)/l (catalyst)/h (1.7 kg/h of n-butane) and with the following composition of the supplied gas mixture: 35% of�of Yemen. n-butane, 41% vol. water, 16% vol. hydrogen, 2.7% of vol. nitrogen and 5.3% vol. oxygen. Oxygen was fed in portions above the layer of catalyst: 40% above the first layer in the flow direction, 35% above the second layer and 25% above the third layer. During the dehydrogenation temperature of the heater was set to 470°C. When the duration of the dehydrogenation cycle of 12 h, the reaction pressure was 1.5 bar (abs.).

Between cycles of dehydrogenation, the catalyst was regenerated by burning the coke, and then reduced with hydrogen. Cox pre-burned at the temperature of the preheater 450°C and a pressure of 4.8 bar (abs.) depleted air with an oxygen content of 1% by vol. (a mixture of nitrogen/air, air flow 250 l (n. u.)/h). Thereafter, the air content was gradually increased to 100% (the air flow 1500 l (n. u.)/h) and the temperature increased to 500°C. the reduction with hydrogen was carried out at 500°C, 2.5 bar (abs.) and a hydrogen flow of 200 l (n. u.)/p.m.

Table 10 below shows the mean values of three cycles formed catalysts. When the dehydrogenation of butane in the scale of the pilot plant also becomes clear that the catalyst according to the invention (PDR7927), with similar conversion and selectivity, reaches significantly higher, relative to Pt, performance butene than bulk catalysts according to the previous technology.

Table 10
The catalyst in exampleFormConversion [%]Selectivity [%]Vol. production capacity [kgbutene/kgPt/h]
comparative 1layer4095158
examples 2-9cell4195398

Examples 24 and 25

Aromatization by dehydrogenation was carried out in a heated electricity tubular reactor (steel 1.4841, internal diameter 21 mm). 20 ml of the extrudate catalyst of comparative example 1 or 12 ml of catalyst from example 1 were installed in the reactor and activated with hydrogen at 400°C for 1 h. the Raw materials are dosed into the reactor, represent hydrogen, water and the fraction With8with approximately 95% of the mass. predecessors of o-xylene, preferably, 3,4 - and 2,3-dimethylhexane-2 ("DMH" for short). Hydrogen is dosed out in the reactor in gaseous form through a mass flow controller. Water and the fraction With8direction�the drug from the reservoir by means of pumps for HPLC in steel tubular evaporator, and gas mixture, which was formed, was passed into the reactor in a heated form. Aromatization by dehydrogenation was carried out at a furnace temperature of 400°C, a pressure of 1 bar (abs.), 14 g/h of organic components, the relationship H2O/DMH 16/1 mol/mol and N2/DMH 3/1 mol/mol.

Table 11 below shows the average results of aromatization for more than 4 hours time. Similarly flavoring in o-xylene, it is clear that the catalyst according to the invention (PDR6936), with a similar conversion, reaches significantly higher, relative to Pt, performance on o-xylene than the extrudates of catalyst on preceding technologies.

Table 11
The catalyst in exampleFormConversion DMH [%]The selectivity to xyleneThe ratio of o-xylene (m-xylene + p-xylene)Vol. production capacity [kgo-xylene/kgPt/h]
1cell50191758
sravnitel. 1 layer5438937

Example 25

A catalyst for selective oxidation of hydrogen with oxygen in the presence of hydrocarbons

The procedure of impregnation on capacity for Pt/Sn on the carrier of alpha-Al2O3

2-4 mm spheres of alpha-alumina from Axens (aluminium oxide Spheralite 512) was used as the carrier material. The impregnation procedure was as follows:

i to determine the initial moisture content of the material of aluminum oxide which is subject to application,

a) 10 g of the carrier material of alumina was placed in a plastic vial.

(b) was Added to the material of deionized water (DI) is 10% more of the total weight of the carrier

c) Mixing the water and the media. When he reached the initial moisture content, the material of the carrier komkali.

(d) For the sample of aluminum oxide 10 g were added 4 g of water. The weight percentage of water to be added to the carrier, identified in 40% of the mass.

ii Determined the number of Pt nitrate solution necessary to obtain the desired level Pt. To 50 g of the carrier material of aluminum oxide, 0.52 g of Pt nitrate solution with the concentration of nitrate Pt is 13.46% was diluted to 20 ml and added.

iii This liquid was poured into the dry powder. These two components were mixed� to obtain a homogeneous mixture.

iv the Mixture was dried at 75°C for 16 hours.

v Desirable amount of SnCl2×2H2O it was necessary to calculate and dissolved in DI water. To 50 g of the carrier material of aluminum oxide, 0,046 g of solid tin chloride was dissolved in 20 ml of water was added.

vi the Mixture was dried at 75°C for 16 hours.

vii Calcination was carried out at 540°C for 2 hours.

The application procedure is in a wet state Pt/Sn-Frit on a monolithic substrate

The application procedure is in a wet state was as follows:

i Grind or reduce the size of the particles of Frit.

(a) Received a suspension with a solids content of 35%, using a Pt/Sn on a carrier of aluminum oxide and DI water.

(b) This slurry was placed in a ceramic ball in mini-mill.

c) This ball mill was placed on the drum of the firm's US Stoneware, and the speed control set at the speed of about 107 rpm.

g) Milling was performed for about 9 hours until 90% of particles become less than 10 microns.

ii the Suspension is unloaded into a container for storage.

ii Cut the cores out of a piece of material Corning, block untreated substrate 400 cpsi/6,5 mil. These rods are 16mm in diameter and 100 mm length. The full amount was 324 ml.

iv Suspension was mixed until uniform. Then the vessel was loaded into a cylinder that was slightly larger in diameter than the rod. Rod �oguzeli in suspension and removed after 5 seconds. Excess suspension was shaking with the rod, and the channel is purged clean.

v the Mixture was dried at a temperature of from 75 to 90°C for 16 hours.

vi Stage 4 and 5 were repeated until the dried applied wet coating did not reach values between 0.16 and 0.17 g/ml.

vii Calcination was carried out at 540°C for 2 hours.

viii the Mass of the rod was determined at the temperature of the rod above 150°C. When weighing the rod in a warm condition can be determined the correct weight load applied in the wet state of the coating. When the rod cools, it absorbs water, which leads to incorrect loading applied in the wet state of the coating.

Characteristics of the catalyst are given in table 12 below. The depth of penetration was determined as described in examples 1 through 12.

Table 12
ExampleDownload applied. in humid. status. coating[g/l]Destiny. weight [g/l]Download Pt [g/l]Elemental composition [% wt.]The depth penetrated.[µm]
PtSnAl
251664850,160,0330.031 inch3264

Comparative example 9

Getting the bulk of the catalyst for selective combustion Exhaust gas with hydrogen

The catalyst received in international application WO 2005097715, example A.

Example 26 and comparative example 10

The removal of oxygen by catalytic combustion with hydrogen at laboratory scale

Selective catalytic incineration O2conducted in an electrically heated tubular reactor (steel 1.4841, inner diameter 18 mm). n-butane, butadiene-1,3, nitrogen, hydrogen and air is dosed out in the reactor in gaseous form through the mass flow controllers (Bronckhorst). Water moved from the reservoir through the pump for HPLC in steel tubular evaporator, and the vapor was directed into the reactor.

The exhaust gases introduced through the pressure regulator in a water separator, cooled to 10°C. Below the separator, the waste gas is passed into a working online gas chromatograph (µGC, from Varian) to analyze and determine conversion and selectively.

For the implementation of the removal of O2the catalyst was installed in the middle of isothermal sections react�RA. In the case of the catalyst according to the invention, installed round cells with cell rod with a length of 101.6 mm and a diameter of 15 mm. In the case of the comparative catalyst, was established 20 ml of 1.5 mm extrudate. Above and below the catalyst layer had a layer of inert material (steatite spheres of 2-3 mm).

During the combustion of O2, the temperature of the reactor furnace was set to 300°C. the reaction Pressure was 1.5 bar (abs.). The burning of O2was performed under flow fraction C420 l (n. o.)C4/h and the following composition of the gas mixture supplied: 11.6% of vol. n-butane, 9.8% of butadiene-1,3, of which 23.5% vol. water, 6,2% vol. hydrogen, 47.0% of vol. nitrogen and 1.9% by vol. oxygen.

Table 13 below shows the results of catalytic deoxygenation after 2 days of the process. In the selective combustion of O2with hydrogen, it is clear that the catalyst according to the invention, with a substantially higher relative to Pt loading of oxygen (WHSV, hour weight gas flow rate) reaches the conversion of O2similar to that of the bulk catalyst according to the preceding technology.

Table 13
The catalyst in exampleFormWHSV O2[kgO2/kgPt /h]Conversion of O2The selectivity of the combustion of N2
25cell118199,790
comparative 9layer9199,790

1. The use of a catalyst comprising a monolith composed of a catalytically inert material with a surface area by BET <10 m2/g, and the catalyst layer, which is applied to the monolith and comprises the material of the oxide carrier, platinum and tin and/or rhenium, and optionally other metals, where the thickness of the catalyst layer is 5 to 500 microns, and where the hourly volumetric gas flow rate is from 500 to 16000 h-1for dehydrogenation of alkanes to alkenes or aromatization by dehydrogenation.

2. The use according to claim 1, wherein the catalyst layer contains a metal from the side of a subgroup of the third group of the periodic table of elements, including lanthanides, and/or alkali metal or alkaline earth metal.

3. The use according to claim 1 or 2, where the catalyst contains at least one element selected from the group consisting of tin and lanthanum.

5. The use according to claim 1 or 2, which comprises a monolith of cordierite.

6. The use according to claim 1 or 2 for dehydrogenation of propane to propylene or n-butane to butenes.

7. Method dehydrogenation of alkanes to alkenes, including interaction in the reaction zone of the reaction gas mixture containing hydrocarbon, with a catalyst as defined in any one of claims.1-5, where the dehydrogenation is carried out in the form of oxidative or non-oxidative dehydrogenation.

8. A method according to claim 7, where the dehydrogenation is carried out in the form of non-oxidative dehydrogenation.

9. A method according to claim 8, wherein the non-oxidative dehydrogenation is carried out autothermal.

10. A method according to claim 9, where the autothermal dehydrogenation is performed in the disc reactor.

11. A method according to claim 9 or 10, where the catalyst also catalyzes the combustion of hydrocarbons and hydrogen present in the reaction mixture.

12. Method of aromatization by dehydrogenation, including interaction in the reaction zone of the gas reaction mixture containing hydrocarbon, with a catalyst as defined in any one of claims.1-5, where the aromatization by dehydrogenation is carried out at a temperature of from 300 to 800°C.

13. A method according to claim 12, where the reaction gas mixture�, containing hydrocarbons add hydrogen.

14. A method according to claim 13, wherein the volumetric ratio of hydrogen to hydrocarbon is from 0.1 to 100.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a method of aromatising non-aromatic hydrocarbons contained in a hydrogenated fraction of a C6-C8 pyrolysis condensate. The method involves reaction of starting material with a metal-containing zeolite aromatisation catalyst at high temperature, and is characterised by that the starting material is a hydrogenated fraction of a C6-C8 pyrolysis condensate containing not less than 70 wt % aromatic hydrocarbons and 8-30 wt % non-aromatic hydrocarbons. The aromatisation catalyst used is a zeolite having entrance window diameter 5.1-7.3Ǻ, having molar ratio of silicon to aluminium equal to 25-140, modified with metals selected from: zinc, gallium, silver, rhodium, platinum, rare-earth elements, as well as combinations thereof.

EFFECT: invention increases output of the end product - benzene and reduces output of light hydrocarbon fractions when processing pyrolysis condensate.

7 cl, 42 ex, 4 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to method of producing aromatic hydrocarbon compounds from light hydrocarbons by catalytic reaction of ring formation and to catalyst to this end. Zeolite-containing compacted catalyst, to be used in method of producing aromatic hydrocarbon compounds from light hydrocarbons by catalytic reaction of ring formation, wherein zeolite contained in zeolite-containing compacted catalyst meets the following requirements: (a) zeolite represents that with average diametre of pores varying from 5 to 6.5 Å; (b) zeolite features diametre of primary particle varying from 0.02 to 0.25 mcm; and (c) zeolite comprises at least one metal element selected from the group consisting of metals from IB-group of periodic system in the form of appropriate cations, and wherein zeolite-containing compacted catalyst comprises at least one element selected from the group made up of elements that belong in IB, IIB, IIIB, VIII groups of periodic system.

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FIELD: chemistry.

SUBSTANCE: invention relates to technology of making nanostructured metal-carbon composite materials and can be used in heterogeneous and electrocatalysis. The metal-carbon nanocomposite contains metallic nanoparticles of alloys of Pt with a metal selected from Ru, Re, Rh, uniformly dispersed in the carbon matrix structure. The matrix is made from polyacrylonitrole which is pyrolysed through exposure to infrared light with intensity which corresponds to temperature of 650-1100°C. Total amount of metal equals 0.1-20% of the mass of the composite. The method of making a metal-carbon composite is based on reducing the said metals from solutions of their salts. A combined solution of metal salts, one of which is platinum and the other is either Ru or Re or Rh in an amide or sulfoxide solvent is added to polyacrylonitrile solution in the same solvent and undergoes pyrolysis while exposed to infrared light with intensity which corresponds to temperature of 650-1100°C.

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3 cl, 3 dwg, 11 ex, 3 tbl

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention relates to processes for hydrocarbon feedstock conversion into aromatic hydrocarbons, in particular to light hydrocarbon aromatization process catalysts, to catalyst preparation processes, and aromatic hydrocarbon production processes. A composite light hydrocarbon aromatization process catalyst is described, which contains acidic microporous component with pore size at least 5 Å and oxide component exhibiting dehydrogenation activity and selected from aluminum hydroxide and/or oxide having transportation pore size at least 20 nm, said oxide component having been treated with promoter element compounds. Described are this catalyst preparation method and aromatic compound production process in presence of above-described catalyst.

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11 cl, 1 tbl, 23 ex

The invention relates to the field of preparation of the catalyst used in the production of aromatic hydrocarbons

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3 cl, 1 tbl, 7 ex

FIELD: chemistry.

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EFFECT: obtaining a catalyst with a uniform composition, high mechanical strength, catalytic activity, selectivity and stability in processes of hydrogenating paraffin hydrocarbons into corresponding olefin hydrocarbons.

4 cl, 1 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of alkylaromatic hydrocarbon dehydration, which includes: contact of vapour reagent flow, containing alkylaromatic hydrocarbon and water vapour and having first weight ratio of vapour to alkylaromatic hydrocarbon, with dehydration catalyst with formation of vapour-phase output flow, which contains hydrocarbon product, water vapour and alkylaromatic hydrocarbon, which did not react; supply of, at least, part of output flow into separator for separation of hydrocarbon product from alkylaromatic hydrocarbon, which did not react, removed from separator in form of bottom and main fractions respectively; utilisation of heat of first part f said main fraction by indirect heat-exchange with mixture, containing alkylaromatic hydrocarbon and water, for at least, partial condensation of said part and formation of azeotropic evaporation product, which contains vapour of alkylaromatic comound and water vapour, having second ratio of vapour to alkylaromatic hydrocarbon; and combination of azeotropic evaporation product with additional alkylaromatic hydrocarbon and additional vapour, together or separately, with formation of vapour reagent flow.

EFFECT: application of claimed method makes it possible to use heat of upper separator distillate more effectively.

12 cl, 5 dwg

FIELD: chemistry.

SUBSTANCE: described is method of catalyst preparation, which consists in impregnation of product of thermochemical activation of hydrargillite by active components under microwave radiation with operating frequency 2.46 GHz and power 180-900 Wt for 3-30 min with the following drying in electromagnetic field of ultrahigh-frequency range and incineration at temperature from 600 to 800°C.

EFFECT: increase of method productivity, high mechanical strength and thermal stability of catalyst, increase of catalytic properties.

2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: dehydration catalyst represents aluminium oxide carrier, modified with silicon oxide, on which active component chrome oxide and promoter potassium oxide are distributed. Silicon oxide is fixed on aluminium oxide in form of silicon oxide structures Si(OSi)n(O-)4-n, where n is from 1 to 4, in which silicon in spectrum NMR MAS 29Si is characterised by presence of lines with chemical shifts from -95 to -105 ppm (line Q3) and from -107 to -124 ppm (line Q4) with ratio of integral intensities Q3/Q4 from 0.5 to 1.5, with chrome in active component being characterized in UV-Vis-spectrum of diffuse reflection by band of absorption of d-d electronic transition of octahedral Cr(III) cation with wave number from 16500 to 17000 cm-1. Catalyst has specific surface value from 10 to 250 m2/g, volume of pores not less than 0.15 cm3/g, and its composition is formed in the following ratio, wt %: chrome oxide - 8-20, potassium oxide- 0.1-5, silicon oxide - 0.1-5, aluminium oxide carrier - the remaining part.

EFFECT: claimed catalyst of paraffin hydrocarbons possesses high activity, selectivity and thermal stability.

3 cl, 2 dwg, 1 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: invention relates to processes of paraffin dehydration. A method for the regulation of temperatures in a dehydration reactor includes the supply of a catalyst into the dehydration reactor in such a way that the catalyst flows downwards via the reactor, supply of the flow, enriched with paraffins, into the dehydration reactor in such a way that the flow passes upwards via the reactor with the formation of a technological flow, which contains the catalyst and dehydrated hydrocarbons, as well as a certain amount of non-converted paraffins, separation of a vapour phase from the technological flow with the formation of a flow of products, supplying the flow of products into a cooling unit with the formation of a cooled flow of products and the supply of a part of the cooled flow of products into the technological flow.

EFFECT: invention provides the effective and economical dehydration process with the prevention of undesirable side reactions.

10 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of carrying out reactions of dehydration with further absorption purification of gases, with the absorption gas purification followed by a stage of pressure release in a reservoir of high pressure flash evaporation, provided by mass-exchange elements, with the said stage being carried out with the application of combustible gas, flowing through the mass-exchange elements towards gravity direction, which passes through the high-pressure flash evaporation reservoir in a counterflow with respect to a solvent, subjected to pressure release, so that the absorbed hydrocarbons are absorbed by combustible gas. Combustible gas is represented by fuel gas, used for heating the dehydration reactor and which, for instance, is natural gas. To increase the process efficiency the flow of carbohydrates, separated from acid-forming gases, can be returned back into a channel of technological gas before absorption purification of gases.

EFFECT: method provides a possibility of an improved separation of carbon dioxide and hydrocarbons in the process of removal of acid-forming gases.

13 cl, 2 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of propane dehydrogenation, which includes passing of a preliminarily heated initial propane flow into a dehydrogenation reactor, mixing and interaction of the initial propane flow with a non-metallic fluidised catalyst, which contains zirconium oxide, in the dehydrogenation reactor, which represents a reactor of fast fluidisation with formation of a flow of a propylene-containing product. The catalyst is in the reactor with the average time of presence from 15 to 45 minutes; passing of a waste catalyst into a catalyst regeneration unit with formation of a flow of a regenerated catalyst; and passing the flow of the regenerated catalyst into the dehydrogenation reactor.

EFFECT: application of the claimed method makes it possible to increase the passing capability of the system.

8 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to a mesoporous carbon-supported copper-based catalyst, a method for production and use thereof in catalytic dehydrogenation of a compound with a C2-C12 alkyl chain to convert said compound to a compound with a corresponding alkenyl chain. The catalyst contains mesoporous carbon, a copper component and an auxiliary element supported on said mesoporous carbon. One or more auxiliary elements (in form of oxides) are selected from a group consisting of V2O5, Li2O, MgO, CaO, Ga2O3, ZnO, Al2O3, CeO2, La2O3, SnO2 and K2O. The amount of the copper component (calculated as CuO) is 2-20 wt % based on the total weight of the catalyst. The amount of the auxiliary element (calculated as said oxide) is 0-3 wt %. The amount of the mesoporous carbon is 77.1-98 wt % based on the total weight of the catalyst. The method of producing the catalyst involves: (1) a step of contacting a copper component precursor, auxiliary element precursor and mesoporous carbon in a given ratio to form an intermediate product and (2) a step of calcining the intermediate product to obtain the mesoporous carbon-supported copper-based catalyst.

EFFECT: catalyst is cheap, environmentally safe and has high thermal stability and caking resistance with considerably high and relatively stable catalytic activity.

19 cl, 47 ex

FIELD: chemistry.

SUBSTANCE: described is a method of producing C3-C5 olefin hydrocarbons via dehydrogenation of corresponding C3-C5 paraffin hydrocarbons or mixtures thereof in the presence of a catalyst which contains chromium oxide, zinc oxide, aluminium oxide and additionally a aluminium-magnesium spinel and at least tin oxide in amount of 0.1-3.0 wt %. Before the regeneration step, reaction products are removed from the catalyst by first passing C1-C5 hydrocarbons or mixtures thereof and then nitrogen through the catalyst. The catalyst contains chromium oxide, zinc oxide, aluminium oxide, aluminium-magnesium spinel and tin oxide, with the following ratio of components in terms of oxides, wt %: Cr2O3 - 10.0-30.0, ZnO - 10.0-40.0, SnO2 - 0.1-3.0, MgO - 1.0-25.0, Al2O3 - the balance. The catalyst can further contain a manganese compound in amount of 0.05-5.0 wt %.

EFFECT: high efficiency of the process of producing olefin hydrocarbons.

3 cl, 1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: catalyst is characterised by the following content of components: 30-70 wt % (Mo5-12Sb>6.0-15Bi0.2-3M10.1-10M20.05-0.5M30.01-2On) and 70-30 wt % SiO2, where M1 is one or more elements selected from Co, Ni, Fe, Cr, Cu; M2 is one or more elements selected from Na, K, Cs, Mg, Ce, La, M3 is an element selected from P, B, n is a number defined by the valence and number of elements other than oxygen. The invention also relates to a method of producing butadiene-1,3 using said catalyst.

EFFECT: catalyst enables to achieve high butadiene selectivity in oxidative dehydrogenation of n-butenes and provides high output of butadiene.

3 cl, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing light olefins, which comprises: (a) passing oxygen-containing feedstock into a reactor for converting oxygen-containing compounds to olefins, such that the oxygen-containing feedstock comes into contact with a molecular sieve-based catalyst and is converted to light olefins, which come out of said reactor in the form of an effluent stream; (b) dividing the effluent stream into a first stream of light olefins and a first stream containing C4 or heavier hydrocarbons separate from the first stream; (c) selective hydrogenation and subsequent cracking of the first stream containing C4 or heavier hydrocarbons to obtain a first effluent stream of cracking gases containing light olefins; (d) separate cracking of the hydrocarbon stream to obtain a second effluent stream of cracking gases containing light olefins; (e) combined fractionation of he first and second effluent streams of cracking gases to obtain a second stream containing light olefins, separate from the second stream containing C4 or heavier hydrocarbons; (f) combined treatment of the first and second streams containing light olefins to remove acidic gases and obtain a treated stream; (g) dividing the treated stream into an ethylene product stream, a propylene product stream and a stream containing C4 hydrocarbons; and (h) optional selective hydrogenation of the stream containing C4 hydrocarbons, and subsequent fraction of the optionally selectively hydrogenated stream to separate a 2-butene stream from the first 1-butene stream. The invention also relates to a method of extracting 1-butene from a stream of C4 hydrocarbons, which uses the method described above.

EFFECT: method is an improved process of obtaining light olefins through smart combination of an apparatus for converting oxygen-containing compounds to olefin with a hydrocarbon pyrolysis apparatus.

17 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: pyrolysis of methylene chloride is carried out on a catalyst with a carbonisation degree in the range of 2.6-5.2 wt %, which is obtained during 60-150 minutes of a reactor work, after which in order to support the obtained degree of carbonisation a catalyst is constantly discharged into a regenerator, excessive carbon is removed by burning with air at a temperature of 550°C. After that it is returned into the reactor, providing constant circulation of the carbonised catalyst from the reactor of pyrolysis into the regenerator and back.

EFFECT: application of the method makes it possible to increase selectivity of the process of obtaining lower olefins due to increase of the catalyst selectivity, applied in the process of methylene chloride pyrolysis.

2 ex, 2 tbl

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