The method of obtaining 1,3-butadiene and the catalyst to obtain
(57) Abstract:Use: petrochemical industry. The inventive product-1,3-butadiene (BD) and the catalyst to obtain it from reactive oxygen. It contains, by weight. percent: molybdenum oxide 8,4 - 24,30; the oxide of the alkali metal 0,16 - 1,43; media - the rest. The media consists of MgO, Al2O3and/or alumomagnesium spinel, the mass ratio of MgO/Al2O30,38 - 0,79, surface area 25-184,3 m2/, the Catalyst further comprises of 0.58 - 0.85 wt.%. Conditions of oxidative dehydrogenation of butane: 550 - 650°C, 7 - 210 KPa and other conditions that ensure the selectivity DB not less than 40 wt.%. 2 S. and 2 C.p. f-crystals, 10 PL. The invention relates to the oxidation of aliphatic hydrocarbons such as monoolefins and alkanes, in order to obtain more highly unsaturated aliphatic hydrocarbons.Unsaturated aliphatic hydrocarbons, such as monoolefinic and diolefine, are used as monomers or comonomers in obtaining plastics based on polyolefin.There is a method of oxidative dehydrogenation of hydrocarbons of the paraffin series, such as butane, in the presence of a catalyst, soderjaschii silicon. The process is conducted at 500-650aboutWith the pressure 7-210 kPa and other conditions for obtaining a reaction mixture containing 1,3-butadiene with a selectivity of at least 40 M If the butane interacts with the catalyst, the products contain butenes and BUTADIENES. However, the selectivity and the volume yield of butadiene remains below the desired level. In addition, the original content of the hydrocarbon and oxygen is undesirable for security reasons. And finally, the media is based on magnesium oxide does not have sufficient toughness and abrasion resistance required for use in the fluidized bed reactor, or reactors, moving bed.In one embodiment, the invention relates to a method for producing unsaturated aliphatic hydrocarbons, which includes the interaction of aliphatic hydrocarbon having at least three carbon atoms, with a catalyst of the invention, which will be described below. When the reaction conditions of the proposed method is more unsaturated aliphatic hydrocarbons, such as diolefin formed with a selectivity of at least about 40 M%
Mainly aliphatic hydrocarbons may be any of aliphatic hydrocarbons. The proposed method showed high selectivity and high productivity of more highly unsaturated aliphatic hydrocarbons, in particular diolefins. The proposed method showed low selectivity and low yield undesirable products of deep oxidation, such as the monoxide, and carbon dioxide. In addition, using the proposed method butadiene can be obtained directly from Bhutan with a high degree of selectivity and productivity and at the same time with a low degree of selectivity for products of deep oxidation. For the purposes of the invention "productivity" is defined as grams of target product, obtained on 1 g of catalyst per 1 hourUnsaturated aliphatic hydrocarbons, such as monoolefinic or diolefine, are used as monomers or comonomers in obtaining polyolefins. Butadiene can also be used as an intermediate connection upon receipt of styrene.In another embodiment, the invention relates to a solid heterogeneous catalytic composition containing an active oxygen atom with the specified catalyst may be used in a specified way to obtain unsaturated aliphatic hydrocarbons. This is in concentration, approximately 0.1-5 wt. by weight of the combined oxides of magnesium and molybdenum. The catalyst may contain an oxide of vanadium.In yet another embodiment, the invention relates to catalytic compositions of molybdate containing reactive oxygen. This composition comprises a carrier comprising magnesium oxide and at least one aluminum oxide selected from the group consisting of Al2O3and magnesium aluminate (MgAl2O4). The specified media has a mass ratio of MgO/Al2O3in the range of 0.30 to 4.0 and a surface area of at least about 25 m2/, This catalytic composition also contains a catalytic component consisting mainly of molybdenum oxide, magnesium oxide and an activating amount of a promoter of an alkali metal. The catalyst may contain an oxide of vanadium. In the preferred implementation of the invention, the resistance to abrasion, as defined below, is less than 5 wt. for 1 hThe catalytic composition of the invention is used in a specified way oxidation of aliphatic hydrocarbons in the more unsaturated aliphatic hydrocarbons. In the preferred his performance catalytic composition oblad the invention can be used in the fluidized bed reactor and the reactor moving bed, such as reactor with a rising layer of the catalyst.Aliphatic hydrocarbons, which can be used in the proposed method, include alkanes and olefins, which have three or more carbon atoms.Alternative alkanes can be characterized as a hydrocarbon of the paraffin series. These connections are known in the art as saturated hydrocarbons. As mentioned, alkanes contain at least three carbon atoms and can be straight or branched chain. Usually alkanes containing up to 20 carbon atoms. Examples of suitable alkanes can serve as n-butane, n-pentane, n-hexane, n-heptane, n-octane, n-nonan, n-decane, n-dodecane and more saturated homologues, as well as isobutane, isopentane, neopentane and, in addition, an extensive hexane, heptane, octane, nonanes, decanes, dodecane and more branched homologues. Some alicyclic hydrocarbons are suitable reactants and therefore also used in the proposed method. Examples of aliphatic hydrocarbons can be CYCLOBUTANE, cyclopentane, cyclohexane, Cycloheptane, cyclooctane, Methylcyclopentane, methylcyclohexane, and other alkyl-substituted cycloalkanes. Preferably the AK aliphatic hydrocarbons, containing at least one unsaturated double bond. As mentioned above, the olefins contain at least three carbon atoms, and typically up to 20 carbon atoms. The location of the double bond is not critical; therefore, it can be at the end or within the carbon chain. Preferably, however, to the olefin had normal or linear and not branched structure. For example, 1-butene is preferable than isobutylene. Examples of suitable olefins include 1-butene, 2-butene, 1-penten, 2-penten, 3-penten, 1-hexene, 2-hexene, 3-hexene and, in addition, 1-hepten, 1-octene, 1 ion, 1-mission and their isomers, where the unsaturation is in any other position of the carbon chain.The proposed method can also be used olefins containing more than one double bond, such as 1,3-hexadien and isoprene, which become more unsaturated hydrocarbons. Some of aliphatic olefins, such as cyclohexene and vinylcyclohexane, are also suitable source materials and therefore may also be included in the invention. The preferred olefin is monoolefins. More preferred is 1 - or 2-butene. Alkynes, however, are not the pods are typical of suitable for the proposed method of hydrocarbons, however, these examples should not limit other options. Suitable for the proposed method can be and other aliphatic hydrocarbons, known to specialists.Preferred alkanes are normal paraffins, which can be represented by the following General formula:
CH3-(CH2)n-CH3where n is an integer from 1 to 8. More preferably, if n is an integer from 2 to 6. Most preferably, if n is 2, and alkanol is n-butane.Optional aliphatic hydrocarbon reagent may be diluted directionspanel gas, such as nitrogen, helium, argon, methane, carbon dioxide, or steam. Because the type of diluent is chosen mainly for reasons of economic order, the preferred diluent can be considered as nitrogen. The amount of diluent (if used) can vary within wide limits, depending on the structure of the reactor and the reactivity of solid oxidizer. The content of hydrocarbon in the mixture of the hydrocarbon diluent is typically 1-100 M Preferred content of hydrocarbon in the mixture is 10-100 M% and most preferred 4 least part of the oxygen which is active. This means that the catalyst is present in an active form of oxygen and that this active form of oxygen capable of oxidizing aliphatic hydrocarbons. Thus, in one embodiment of the invention the catalyst is a solid oxidizer. After active oxygen is removed from the reactor, the catalyst is depleted. In addition, the catalyst may form some time carbon remains on the surface. Depleted and poisoned catalyst can be restored by using a gaseous source of oxygen. Thus, for the implementation of the catalytic process of the invention it is necessary to aliphatic hydrocarbon add oxygen.Oxygen is normally supplied from the gas source equipped with a continuous flow of oxygen. In this way, you can use any source of oxygen, such as pure elemental oxygen, air or nitrous oxide. The preferred source of oxygen is air (gas). Optional gaseous elemental oxygen can be diluted directionspanel gas, such as nitrogen, helium, argon, or carbon dioxide. The preferred diluent is nitrogen. If you use n siteline 50 M% is More preferable, if the oxygen content in the mixture is in the range of 0.5-30 M% Most preferred oxygen content in the mixture is 1-20 M%
The amount of oxygen used in the proposed catalytic method should be sufficient for complete oxidation of a solid heterogeneous catalyst and sufficient to remove carbon residue from the surface of the catalyst. Preferably, if the regeneration of the catalyst is carried out separately from the oxidation of aliphatic hydrocarbons.Alternatively, you can supply aliphatic hydrocarbon together with a small amount of gaseous elemental oxygen. The purpose of this filing is to remove carbon residue from the surface of the catalyst, recovering to some extent reactive oxygen catalyst and the removal of any hydrogen formed during the reaction. The oxygen concentration of the aliphatic hydrocarbon and the feed is dictated only by considerations of explosion of this mixture. Preferably, if the oxygen concentration is below the limit of detonation.The solid heterogeneous catalyst used in the invention mainly contains magnesium oxide, OK is to, however, MgO is preferred. Similarly as molybdenum oxide can be used any acceptable source, such as MoO3, (NH4)6Mo7O24MoO4. The molybdenum oxide can also be obtained from the preceding molybdenum compounds such as molybdenum carbonyl, for example, Mo(CO)6. A preferred source of a mixture of molybdenum is (NH4)6Mo7O24-- and forms of alumina, such as benski alumina, aqueous, colloidal alumina, stoichiometric Al(OH)3and alkoxides of aluminum, as will be shown below. Suitable sources of aluminum oxide are also aluminate and magnesium hydroxide magnesium aluminate. In the proposed method, magnesium oxide plays a dual role: first, it acts as a carrier for the catalytic component, which neutralizes the acidity of aluminum oxide and other residual acid sites. It is extremely desirable that the catalyst was essential, as the basicity increases the desorption of olefinic products. As magnesium oxide can be used any acceptable source, but it is preferable MgO. The oxide of molybdenum makes a significant contribution and activity of the catalyst, in particular the EN is in oxidation state +6. As the oxide of molybdenum can be used by any acceptable source, such as MoO3, (NH4)6Mo7O24MoO4. The molybdenum oxide can also be obtained from the molybdenum precursor, such as molybdenum carbonyl, such as Mo(CO)6. A preferred source of molybdenum oxide is heptamolybdate ammonium represented by the formula (NH4)6Mo7O24-,- and-alumina and benski alumina. The mass ratio of magnesium oxide to aluminum oxide (MgO/Al2O3) is a critical parameter and is described in more detail below. The temperature of calcination is usually in the range 400-1200aboutWith, preferably in the range 450-900aboutS, and most preferably in the range of 500-700aboutC. the Calcination is carried out in a period of time sufficient for the formation of a fused and cured composite material, which acts as a carrier for the catalytic components. Typically, the calcination is conducted at least about 0.5 hours During the calcination part of aluminum oxide and magnesium oxide can be chemically mixed, forming a phase spinel (MgAl2O4), which is a homogeneous mixture between before the IRS magnesium add colloidal alumina and the resulting mixture is dried under conditions sufficient to obtain the media from magnesium oxide and aluminum oxide. Colloidal alumina is an acidified aqueous suspension of hydrated aluminum oxide in which the surface area of the particles is so much greater than their size, these particles are not deposited under the action of gravity. The number of the specified colloidal suspension of aluminum oxide added to the magnesium oxide should be such that the final mass ratio of magnesium oxide to aluminum oxide was within certain limits which will be defined below. The pH value of the mixture of colloidal aluminum oxide and magnesium oxide is about 9. The mixture is then dried using one of the standard methods, such as curing and evaporation, spray drying, drying in a stream of hot air, drying drum, etc., One of the preferred methods is artificial and evaporation of the mixture over the hot stove or equivalent means for heating in order to obtain a more dense gel and eventually solid mass which is then milled and sieved to obtain particles of desired sizes. Temperature-keeping and evaporation can be any temperature which is compatible with the solvent system is 0aboutC. the Preferred temperature is the temperature of 50-90aboutS, and most preferred 60-80aboutC. the Time required for curing depends on the amount of gel and it should be sufficient to obtain a solid refractory mass.In conditions of industrial production of the above-described mixture of magnesium oxide and colloidal aluminum oxide preferably osasivat by spraying. For these purposes may be used in any device for drying spray, which is typically used in the fluidized bed reactor. As example can serve as a device for spraying Niro Atomizer S-12, 5-R/N. the Specified device has means for regulating the temperature at the inlet and outlet. Usually crushed particles obtained by spray drying, have a spherical shape with a diameter of from about 10-250 microns and a good yield.The powder obtained after drying by keeping the spray, calicivirus in order to obtain a composite carrier comprising mainly of oxides of magnesium and aluminum, not necessarily of the spinel phase of magnesium aluminate. The calcination is conducted under conditions sufficient for alloying of aluminum oxide and an oxide which contain the calcination at 350-900aboutS, and most preferred is a temperature of 500-700aboutC. Typically, the period of calcination depends on the number kellnerweg material and is at least about 0.5 hoursComponent carrier of the invention can have any mass ratio of magnesium oxide to aluminum oxide, provided that the resulting carrier has a sufficient hardness and basicity. It should be noted that although the spinel phase is present as a separate composition MgAl2O4however , the mass ratio of MgO/Al2O3can be calculated. Basically, the mass ratio of MgO/Al2O3is within 0.1-9,0; however, it is preferable mass ratio of 0.3 to 4.0, and more preferred is 0.3 to 2.0. The most preferred ratio is 0,38-0,80. If the value of the mass relations below the specified lower preferred limit, it means too low content of magnesium oxide, and therefore, the catalyst can have too much acidity. If the value of the mass relationship above the upper preferred limit, it means too high content of magnesium oxide, and therefore, the catalyst may be too low shock Vya the second surface area, Generally, surface area is at least about 25 m2/, Preferred its value is at least about 35 m2/g, and more preferable at least 50 m2/, Even more preferably, if the surface area ranges from 50-250 m2/g, and most preferably 80-170 m2/, Specialists are well aware that too small a surface area corresponds to the low catalytic activity, while the large surface area usually corresponds to high catalytic activity. The catalytic composition of the invention has a large surface area and high catalytic activity.After receiving the media on it put the catalytic elements of the oxide of molybdenum, alkali metal promoter and optionally an oxide of vanadium. If the ratio MgO/Al2O3is within the allowable values specified above, the additional addition of magnesium oxide is not necessary. Usually the required amount of the oxide of molybdenum or molybdenum compounds predecessor, such as heptamolybdate ammonium or carbonyl ammonium, dissolved in a solvent to obtain a solution. Prada. Then the solution is subjected to interaction with the composite carrier manufactured as described above, and the resulting suspension is dried to remove solvent. If this solution is water, then drying is carried out in a furnace at 70-120aboutC. Then, the dried slurry is subjected to calcination for the formation of the catalytically active composition containing aluminum oxide, magnesium oxide and molybdenum oxide. Basically, the calcination is carried out at 300-900aboutC for 0.5-24 hours a Preferred temperature of calcination is 500-800aboutWith, and more preferred 550-650aboutC. Alternative drained suspension described above can, without prior calcination, directly used in the catalytic process of the invention. Since molybdenum precursor can be converted into molybdenum oxide at 300aboutWith or so, and the catalytic layer is heated to a temperature exceeding 300aboutSince then dried composition will be transformed in situ into a catalytically active mixture of oxides of magnesium and molybdenum.Mixed oxide catalyst composition, typically shows one or more diffraction peaks at Eli and aluminum oxide. Elemental analysis of the calcined solid of the composition reveals the following composition, wt. Moo33-50; MgO 90-10, balanced aluminum oxide. The preferred composition is the following composition, wt. MoO310-30; MgO 60-20, and more preferred of Moo312-25; MgO 40-25.The above-described catalyst on the carrier you want to add an activating quantity of at least one promoter of the alkali metal. The promoter serves to improve the selectivity and productivity of unsaturated products, such as diolefins, in the proposed method. Specified by the promoter are usually compounds of lithium, sodium, potassium, rubidium, cesium or fractions having sufficient basicity to improve the selectivity for the more highly unsaturated compounds of the invention. Suitable promoter compounds are alkali oxides, hydroxides and carbonates. Suitable are compounds which, when heated, decompose into oxide, such as acetates and oxalates of alkali metals. Can also be used salts of alkali metals, however, halide and silicates of alkali metals to use are undesirable because of their low basicity. Preferred is actualname are oxide or hydroxide of potassium or cesium. The most preferred promoter is an oxide or hydroxide of potassium.The amount of alkali metal promoter is a critical parameter for the performance of the catalyst. Usually acceptable is any number of specified promoter, sufficient to increase the selectivity and the volumetric output of unsaturated products, such as diolefin, in the proposed method. Typically, the amount of alkali metal promoter ranges from 0.1 to 5 wt. with respect to the total mass of the oxides of magnesium and molybdenum. The preferred amount specified promoter, such as a hydroxide of an alkali metal, is 0.2-2 wt. by weight of oxides of magnesium and molybdenum, and a more preferred amount is 0.5 to 1.5 wt. If the number specified promoter below the lower limit of the preferred values, the selectivity for diolefines will be lower, as in this case, increasing the selectivity for products of deep oxidation. If the number of promoter exceeds the upper limit of the preferred values, in this case also there is a decrease in selectivity for diolefines.Usually, the amount of alkali metal promoter, R is I and molybdenum. The preferred amount specified promoter, calculated on the basis of a hydroxide of alkaline metal is 0.1-2 wt. from the total mass of the oxides of aluminum, magnesium and molybdenum, and a more preferred amount of 0.3-1.5 wt. If the number specified promoter below the lower limit of the preferred values, then there is a more low selectivity for diolefines, and the selectivity for products of deep oxidation increases. If the number specified promoter exceeds the upper limit of the preferred values, in this case also there is a decrease in selectivity and productivity for diolefines.Alkali metal promoter may be added to the catalyst on the basis of molybdate using standard methods. For example, the promoter may be applied using well-known specialists impregnation technique, described for example Charles N. Satterfield in the work of Heterogeneous Catalysis in Practice, McGraw-Hill Book Company, New York, 1980, pp. 82-83, which is introduced in the present description by reference. In the specified technique, molybdenum-impregnated carrier is dipped in a solution of alkali metal promoter, such as a methanol solution of the oxide or hydroxide of an alkali metal. Then the excess of solvent and calicivirus at 550-650aboutC. Alternative specified carrier impregnated with alkali metal promoter with moisturizing techniques so that the pores were filled with a solution of alkali metal oxide or hydroxide of alkaline metal, but the solution should not be in excess. Thus obtained impregnated media is also dried in an oven to remove solvent. In yet another alternative embodiment, the molybdenum compound may be impregnated with the same solution as the connection of an alkali metal.Optional catalyst of the molybdate of the invention may contain an activator that promotes the activity of the catalyst at any given temperature. Preferably, if the activator is not greatly reduces the selectivity to diolefins and monoolefins. It is preferable that the activator was given the opportunity to conduct the reaction at a lower temperature, while maintaining high selectivity and high productivity diolefines. Suitable activators for the introduction of the catalyst can serve as vanadium oxide, preferably V2O5. The catalyst can be added any number of vanadium oxide, provided that this activity catanzarite activator (if used) in the range 0.05-10 wt. with respect to the total mass of the catalyst. The preferred concentration of the activator concentration is from 0.1-5 wt. and more preferred of 0.15-1.5 wt. The specified activator can be introduced into a carrier and a suspension of molybdenum oxide to calcification or it can be drawn on whether aluminum oxide-magnesium-molybdenum using the technique of impregnation described above.Preferred industrial reactor, used in the invention is a reactor with a movable layer, for example with a rising layer of catalyst. In such reactors catalytic particles is subjected to constant collisions with other catalytic particles and with the walls of the reactor. These forces gradually reduce the size of the catalyst to small dust particles, which are lost in the reaction products; thus, the service life of the catalyst is very limited. Therefore, the catalyst must be manufactured in a form that could withstand impact forces and erosion. Catalyst for oxidation of butane containing magnesium molybdate deposited on magnesia, does not have sufficient abrasion resistance required for industrial production. Front of the catalyst of the invention on the basis of the l, as described above, has sufficient abrasion resistance required for use in industrial production.It is obvious that the wear of the catalyst containing magnesium molybdate deposited on magnesia, is directly linked to high sensible sintering of magnesium oxide and strong intermolecular bonds. The sintering temperature is much more than the normal temperature of calcination and the normal operating temperature of the proposed method that the particles do not have the ability to manage and communicate with one another. One of the ways of hardening catalyst containing magnesium molybdate, is the introduction of a catalyst carrier component. Preferably, the specified component had a large surface area and high abrasion resistance and consisted of a composite material containing magnesium oxide and aluminum oxide and optional phase aluminasilica spinel, as described above. Obviously, the alumina provides the catalyst hardness, whereas magnesium oxide and/or magnesium aluminate reduce the natural acidity of aluminum oxide. However, the above theory should not limit the disclosure of the invention. According to the government of the catalyst of the invention is the size of its particles. In the prototypes is usually considered the use of a catalyst with spheroidal particles of small size, which is suitable for reactors fixed bed and moving fluidized bed. These particles typically have a diameter of 20-200 μm, and preferably 80-120 microns. The author of an invention, it was found that ductile (i.e., having a form approaching a spherical) particle size 200-1700 microns provide the best performance in reactors with a movable layer. Preferably, if the particles have a size of 500-1200 μm, and more preferably 600-1000 microns. Larger particles of the invention find less "sliianie" and therefore give a smoother low-speed flow. Thus, larger particles give a smaller pressure drop in the sections of the reactor with a dense layer and a less intense collision of particles with the walls and have the ability to better differentiate the residence time of the gas and the residence time of the catalyst in the reactor.The proposed method can be carried out in any suitable reactor, for example in a batch reactor, the steps in the reactor continuous fixed bed catalyst in a slurry reactor, the reactor of pcev the EOS continuous action, such as the reactor, a continuous fixed bed catalyst or reactor with a rising thickened layer of the catalyst described below type.The reactor with a rising thickened layer of the catalyst contains a vertical vessel with a relatively low ratio of diameter to length. The catalyst is continuously loaded into the lower part of the reactor with a bottom-up layer. In addition, in the lower part of the said reactor at the same time is a stream of aliphatic hydrocarbon in the vapor phase or the liquid phase. Preferably, if the alkane is supplied in a vapor phase, pre-mixed with an inert gas diluent, and optionally with a small amount of oxygen. The feed stream moves through the reactor up, reacting with the catalyst. When interacting with the catalyst, the feedstock is converted into a mixture of products, such as monoolefins, diolefins more highly unsaturated olefins cracking products, products of deep oxidation, such as the monoxide and dioxide, and products of deep cracking, such as benzene and furan, if the raw material was Bhutan. The flow of products present in the reactor with a rising layer, divide the standard alkanes returned to the reactor for further oxidation.The technology used in reactors with a rising layer of catalyst is suitable for the invention, because it eliminates the danger of using a mixture of alkane and/or olefin and elemental oxygen and increases the selectivity for diolefines, especially at high temperatures, used in this way. On the contrary when using raw materials containing alkane and oxygen, at high temperature and high molar ratio of oxygen/alkane has a tendency to the formation of products of deep oxidation, such as the monoxide, and carbon dioxide. In addition, increases the risk of reaction with the rapidly increasing speed.The operation of the reactor with a rising layer of catalyst can be simulated using the method of alternating pulses. For example, the pulse stream of hydrocarbon feedstock is passed through the catalyst bed, where the raw material is oxidized, forming the target products of olefins. Then through a layer of catalyst is passed to pulse the flow of inert gas for cleaning layer from the residual alkanes and alkenes. After purification through a layer of catalyst flow pulse flow oxygen-containing raw materials for catalyst regeneration. And finally, through a repeat. This procedure is used in the embodiments of the invention.Aliphatic hydrocarbon interacts with the catalyst at any operating temperature, which contributes to the activation of the oxidation process of the invention and increasing the yield of the desired unsaturated products. Such temperature is typically the temperature of 400-700aboutC. the Preferred temperature is 500-650aboutWith, and a more preferred temperature 530-600aboutC. If the temperature is below the specified lower limit of the preferred range, the conversion reagent may be reduced. If the temperature exceeds the upper value of the specified range, while there is a decrease in selectivity and productivity diolefines products.Similarly aliphatic hydrocarbon interacts with the catalyst at any operating pressure, which contributes to the activation process of the invention and increasing the yield of the desired unsaturated products. Typically, the partial pressure of the reagent is adjusted so that the specified reagent were in a gaseous state at a given operating temperature. Preferably, if the partial pressure of aliphatic hydrocarbon is in the sight of the equipment, if the partial pressure is within 1-30 psig (7-207 kPa). Finally, the preferred partial pressure is the pressure within 3-15 psig (21-104 kPa).If the method of the invention is carried out in a reactor for the continuous process described below, the flow rate of the reactants may vary. Basically, the proposed method aliphatic hydrocarbon fed into the reactor at any operating speed of the flow, which contributes to the activation of the oxidation process of the invention and to increase the yield and selectivity to unsaturated products. The flow rate is expressed as a volumetric hourly rate of gas (GHSV) and is given in units of volume of gaseous feedstock containing aliphatic hydrocarbon, the whole volume of the reactor for 1 hour or just h-1. Usually these values vary in the range of 100-20000 h-1. It should be noted that the volumetric rate regulates the residence time of the reactants in the reactor. For example, in a reactor with a rising layer of the catalyst, the preferred residence time of the gas in the reactor is less than 10, more preferably less than 5 and most preferably less than 1 secondIn the case of using the ohms the spent catalyst is removed from the upper part of the reactor and transferred to the second reactor for regeneration. The regeneration is carried out by using the reaction of interaction with oxygen. Usually in the lower part of the second reactor serves pre-heated oxygen source, similar to that described above. The spent catalyst interacts with the specified source of oxygen at any temperature, pressure, and flow rate of the oxygen source that are sufficient for regeneration of the catalyst. The parameters of this process should be, however, regulated, to prevent unmanaged reactions or excessive heat. Preferably, if the temperature varies in the range of 500-700aboutS, and more preferably in the range 550-650aboutC. the Preferred pressure ranges from pressure below atmospheric to 100 psig (690 KPa), and more preferred 2-50 psig (14-345 kPa). The flow rate of the oxygen source depends on the heat transfer properties of a particular reactor. For example, if too high flow rates can cause excessive temperature rise, which could lead to uncontrolled reactions.When interacting aliphatic hydrocarbon with the catalyst of the invention, the oxidation alifaticescoe with the formation of water as a by-product. The resultant organic products are mainly unsaturated hydrocarbons, such as monoolefinic and diolefine. These unsaturated products usually contain the same number of carbon atoms as the reagent aliphatic hydrocarbon. Therefore, these products are not products of cracking, as the latter contain fewer carbon atoms than the original hydrocarbon. Mostly unsaturated products have a higher degree of unsaturation than the reagent hydrocarbon. For example, alkanes, such as butane, can lose two hydrogen atoms, forming monoolefinic, such as 1-butene, TRANS-2-butene and CIS-2-butene. In turn, monoolefins, such as the above butenes can lose two hydrogen atoms, forming 1,3-butadiene.Preferred diolefine products can be represented by the General formula:
CH2= CH-CH= CH-(CH2)m-N, where m is an integer from 0 to 6. Preferably, if m is from 0 to 2. The preferred value of m is 0 and preferred unsaturated product is 1,3-butadiene. Can be also formed isomers of the above formula, where the unsaturation may occur in any position of the carbon is saturated variants of the General formula can be formed by further oxidation, which gives more than two ethylene double bonds. However, alkanes are not formed in significant amounts.Along with alkenes product stream may contain various side products. For example, if a saturated alkanol is n-butane, can produce small amounts of the product of cracking, such as propylene and ethylene, and heavier fractions, such as benzene and furan, and in addition, the products of deep oxidation, such as the monoxide, and carbon dioxide. However, it has been unexpectedly discovered that these by-products, especially the products of deep oxidation, with the proposed method of the invention are formed in much smaller quantities.For the purposes of the invention, "conversion" is defined as the percentage (in moles) reacting aliphatic hydrocarbon loss from the original thread in the reaction. The conversion can vary widely depending on the reagents, the shape of the catalyst and the reaction conditions such as temperature, pressure, flow rate and the residence time of the catalyst in the reactor. Within the preferred temperature range with increasing temperature conversion typically increases. Within predpochtitel is. Typically, the conversion of aliphatic hydrocarbon is at least about 10%, Preferably, if the conversion is at least about 20%, more preferably at least about 40% and most preferably at least about 50 M%
Similarly, for the purposes of the invention, "selectivity" is defined as the percentage (in moles) was converted to carbon, which forms a specific product. Typically, the selectivity varies widely depending on the reagents, the shape of the catalyst and reaction conditions. As a rule, in the proposed method achieves high selectivity to diolefins. Within the preferred temperature range, with increasing temperature the selectivity tends to decrease. Within the preferred range of the volumetric flow rate with increasing volumetric flow rate selectivity to alkanes usually increases. Preferably, if the total selectivity to all alkenes is at least about 50M%, more preferably at least 60 M% even more preferably at least 70% and most preferably at least about 80 M% generally, the selectivity for diolefines is at%, more preferably at least about 60 M% most preferably at least about 70 M%
The concept of simultaneously high conversion and high selectivity can be defined as the output. For the purposes of the invention, the term "output" means the amount of product formed as a result of conversion and selectivity in a single passage through the reactor. For example, in the implementation of the proposed method when the conversion of 0.65 or 65 M% and selectivity to diolefins of 0.75 or 75% yield of diolefin is 0.49 or 49% As a rule, in the proposed method achieved the output diolefines at least about 8%, Preferably, if the output diolefin is at least about 18%, more preferably at least about 28 M% and most preferably at least 35 M% usually in the oxidation of butane full output WITH4-olefin is at least about 25%, Preferably, if the oxidation of butane full output WITH4-olefin is at least about 30%, more preferably at least about 35% and most preferably at least about 40 M%
The speed at which the proposed method formed the target product can be defined by the concept of volume of output. In the invention, the term "volumetric output" is defined as the output target is kratom the transmission with the appropriate selectivity, the hourly volumetric flow rate of gas and the concentration of aliphatic hydrocarbons in the feedstock, where the conversion, selectivity and concentration are expressed in decatizing shares. Preferably, if the volume output diolefin is at least about 30% for 1 hour, more preferably at least about 120% for 1 h, and more preferably at least about 200% in 1 hAnother measure of the speed at producing the target product is "efficiency", defined as grams of educated target product per gram of catalyst per hour (g/g cat.-h). In the proposed method, the preferred productivity butadiene is at least about 0.2 g/g cat.-h, more preferred productivity is at least about 0.4 g/g cat.-h, and the most preferred productivity is at least about 0.5 g/g cat.-including Preferred productivity With full-olefins in the proposed method, at least approximately 0.3 g/g cat.-h; preferred productivity is at least about 0.4 g/g cat.-h; and the most preferred productivity is at least about 0.9 g/g cat.-hThe test strongly what is needed is a simple test of strength, wear small samples of the catalyst. This procedure is a test of strength crush strength, because the increased crushing strength is an indicator of high strength, wear. The crushing strength can be determined using any of the standard installation, which are typically used for this purpose, for example an Instron Model 1125. Usually in this case, a catalyst, which first screened for the selection of the granules with the size of 8 mesh (2.36-mm), and then these granules calicivirus at 600aboutC for 2 h, and then determine the crushing strength. The crushing strength of the preferred catalysts of the invention is at least about 5 lbs (2270 g), preferably at least about 10 lbs (4540 g); and more preferably at least about 15 pounds (6810 g).The actual abrasion of the preferred catalyst of the invention can be determined using a standard installation, which is typically used for this purpose. Suitable instruments for testing contain vertical stainless steel pipe with a diameter of 1/2 inch (13 mm) and a length of about 30 inches (760 mm), which is connected through the I-valve with a vertical column of same dia is Anna vertical column at the inlet of the cyclone and to the said vertical pipe at the outlet of the cyclone, thus forming a circulation circuit in which the separation of gas and solid phase, after which the solids are returned to a vertical pipe. Typically, the subject material is loaded into the system and subjected to fluidization by introducing gas into the I-valve with a flow rate of 0.11-1,01 with-1. Entrained powder moving in the upward gas flow and after separation under the force of gravity returns to the cyclone recovery system. Usually full time testing samples takes about 15 hours Then determine the number of fine particles formed per unit time and the rate of abrasion is calculated by comparison with the initial coarse-grained fraction. The preferred measure of abrasion of the catalyst of the invention is approximately less than 5 wt. for 1 h (wt.h-1); and more preferably approximately less than 1 wt.h-1.The invention is illustrated in detail with specific examples, which, however, does not limit the possible variations in its implementation. All percentages are given in M% carbon, if it is not specifically mentioned.P R I m e R 1 (a-b). The manufacture of the catalyst. a) a Powder of magnesium oxide (17 g, Magox Premium Grade MDI suspension was gradually added 20 wt. colloidal alumina (200 g, Nyacol) in order to obtain a viscous mixture containing, by weight. MgO 30; Al2O370. Then he added 52 g of water to obtain controlled rheological properties. The resulting mixture was stirred and was gilotinirovaniya on a hot plate with stirring at 70aboutC for 2 h to obtain a white solid. This substance is crushed, and then heated for 4 h at 600aboutWith and illnerova another 4 h when 600aboutWith, resulting in a received composite carrier-based spinel, having a mass ratio of MgO/Al2O3of 0.43 and a surface area of 169 m2/year x-Ray spectrum of media gives the diraction pattern of crystalline MgO and spinel and aluminum oxide. The media was tested on the device Instron Model 1125 and estimated an average crushing strength, which was 15 pounds (6810) ,b) Spinel composite media made in accordance with the procedure of example 1A except that used 44 g of powder of magnesium oxide, 280 g of colloidal alumina and 249 g of deionized water. The resulting composite media had a mass ratio of MoO/Al2O30,78 and power which may correspond to crystalline MgO, as well as spinel and aluminum oxide. Spinel composite media (20 g) was soaked to the initial stage of humidity through 20,44 g of a solution containing, by weight. heptamolybdate ammonium 35,25; cesium hydroxide of 1.85. Impregnated with the solution was dried for 2 h at 125aboutFrom heated at 600aboutC for 4 h and was caliciviral at 600aboutWith another 3 hours the catalyst (EI) contained, by weight. MoO322,4; Cs2O 1,20, and had a surface area of 122 m2/,P R I m m e R 2. The oxidation of butane. The catalyst (EI) obtained in accordance with the description in example IB was used for the oxidation of butane as follows: approximately 15 cm3the catalyst was loaded into the chamber (18 mm external. diameter x 7.6 cm length) Vycor reactor. The temperature of the reactor was determined using the pocket thermocouple stainless steel (1/8 inch (3.2 mm) EXT. diameter), embedded in the sample catalyst. The flow of raw materials containing butane about 10-20. and helium about 90-80. was passed through the catalyst at approximately 10-30 C. Then the flow of raw materials stopped and through the catalyst for 1 min and at the same speed missed the stream for cleaning, containing pure helium. Then the stream for cleaning stopped and rolled through the Goy stream of helium for cleaning within 1 minutes This cycle was repeated and the combined products were collected for analysis and polyvinylidenechloride plastic camera SaranThe analysis was performed on a gas chromatograph Carle designed for analysis1-C5-alkanes, alkenes and alkadienes, as well as permanent gases, such as N2O2, CO, CO2H2and heavy products, including furan, benzene and C6connection. Isobutane was mixed with the feedstock or products as standard. "Unknown" were obtained from the difference between the carbon balance and 100% Results and process conditions are presented in table.1.As can be seen from the table.1, which is activated cesium catalyst containing magnesium molybdate and put on aluminasilica spinel composite, catalyzes the oxidation of butane to butadiene and butene with a high selectivity.P R I m e R 3. The manufacture of the catalyst. Aluminasilica spinel composite media produced in accordance with example 1B. Spinel composite (20 g) was soaked to the initial moisture with the help of 19.49 g of a solution containing, by weight. the cesium hydroxide 1,66; ammonium Vanadate 1,39; heptamolybdate ammonium 27,22. The impregnated carrier was dried at 1 is the first in the catalyst (OH) contained wt. MoO317,44; V2O50,85; Cs2O 1,43, and had a surface area after calcination 122 m2/,P R I m e R 4 (a-b). The oxidation of butane. The catalyst obtained in accordance with the description in example 3 (OH), used in the oxidation of Bhutan, conducted in accordance with the description in example 2. Process conditions and results are presented in table.1. From table.1 shows that activated cesium catalyst containing magnesium molybdate and vanadium oxide and deposited on aluminasilica spinel composite, catalyze the oxidation of butane to butadiene and butene with a high degree of selectivity.P R I m e R 5. The manufacture of media. Powder magnesium oxide (600 g) was dispersible in deionized water (5733 g) using a disperser with a high shearing force. To the resulting suspension at low shear force was gradually added colloidal alumina (7000 g, 20 wt.). Thus obtained mixture was spray dried using a spray gun with a nozzle having a hole diameter of 2 mm, under a pressure of 40 psi (276 kPa). The inlet temperature of the injector was 300aboutC, and the output 120aboutC. Obtained by spray drying powder white CW for 2 h, resulting in a received composite carrier having a surface area of 184,3 m2/g and the mass ratio of MgO/Al2O30,43. X-ray spectrum of media showed the reflective pattern, which may correspond to crystalline MgO and spinel and aluminum oxide. The calcination part of the powder for 4 h at 800aboutWith only slightly reduced surface area to 143,2 m2/, Media, obtained by calcination of the powder at 600aboutWith, had an average particle size of about 60 microns. The study of particles with a scanning electron microscope showed the presence of spheroidal particles having excellent characteristics of fluidity. In addition, the media was tested for abrasion in the circuit, as described, resulting in a figure of strength, wear received equal to 0.28 wt.h-1. From the comparison it is seen that this media is clearly superior to the commercial fluidized catalyst cracking (FCC) on the basis of aluminum oxide, which is commonly used in reactors with mobile layer and the resistance to abrasion which is 0.99 wt. h-1.Examples of catalysts (b-d). Media based is that these carriers contain a sufficient amount of MgO to obtain a composition with 40, 44 and 30 wt. MgO; and moreover they were not subjected to calcination. Then the medium was subjected to pressing at 5 Kropotov per square inch (35 MPa) in isostatic press with chopping up a 20-80 mesh (850-180 μm) and calcination at 600aboutC for 5 hours To 50 g of each medium was added to the solution containing, by weight. heptamolybdate ammonium 33,23;2CO30,62; peroxide 2.5 to 30 wt. the peroxide solution, neutralized to pH 9 with ammonium hydroxide. Saturated media (E-5-b-d) were dried for 18 h at 110aboutWith and illnerova for 3 h at 600aboutWith, resulting in the obtained catalysts. The amount of solution added to each medium are given in table.2.P R I m e R 6. The oxidation of butane. The catalysts obtained in accordance with the description in example 5 (E-5b-E-5d) was used for the oxidation of butane by the method described in example 2. Conditions of the method and the results are shown in table. 2. As can be seen from the table.2, activated potassium catalysts containing magnesium molybdate and plotted on a composite of aluminasilica spinel, catalyze the oxidation of butane to butadiene and butene with a high degree of selectivity.P R I m e R 7. The manufacture of the catalyst. Preds pH 9) from an aqueous solution of salts of magnesium and aluminum by adding NaOH and Na2CO3. The precursor spinel was caliciviral at 600aboutC for 3 h, resulting in a received aluminasilica spinel (MgAl2O4). The obtained spinel impregnated to the initial stage of humidity using 1.75 M aqueous solution of acetotartrate magnesium (37 wt.).Impregnated spinel was caliciviral for 3 h at 600aboutFrom the resulting received spinel composite containing, in addition, 17,1 wt. MgO and having a mass ratio of MgO/Al2O30,69. Then the composite (16.3 g) was soaked to the initial stage of humidity by using an aqueous solution (17,53 g) heptamolybdate ammonium (26.5 wt.), and then caliciviral for 4 h at 600aboutC. Then the material was saturated methanol solution (8.5 g) of cesium hydroxide (to 0.63 wt.) and again caliciviral for 3 h at 600aboutC. the resulting catalyst (E7) contained, by weight. Moo318,8; Cs2O to 0.25, and had a surface area of 115 m2/,P R I m e R 8 (a-b). The oxidation of butane. The catalyst of example 7(E7) used in the oxidation of Bhutan, conducted in accordance with the description in example 2. The results are presented in table.3.As can be seen from the table.3, activated cesium catalyst containing m is some degree of selectivity.Comparative example 1 (a-b). In accordance with the description in example 7 was obtained composition with the only exception that the catalyst was impregnated with cesium hydroxide. The resulting composition was used in the oxidation of Bhutan, conducted in accordance with the description in example 2. The results are presented in table. 3. From the comparison of example 8 and comparative example 1 shows that the catalyst of the invention containing a small amount of cesium promoter, has a higher selectivity to butadiene and butene and less selectivity to products of deep oxidation than a similar catalyst containing cesium promoter.P R I m e R 9 (a-e). The manufacture of the catalyst. An aqueous solution (1184 g) containing 71,5 wt. uranyl nitrate magnesium, were added to the porous alumina balls (to 713.3 g; VOP, 700 μm). The resulting suspension was dried at 150aboutC for 18 h and was caliciviral by heating to 460aboutC for 4 h, keeping at 460aboutC for 2 h, another two-hour heat up to 540aboutAnd keeping at 540aboutC for 3 h in air flow. Then the dried alumina balls were added 1186,9 g of a solution of magnesium nitrate, and then repeated the PI ratio MgO/Al2O30.38 and surface area of 101 m2/year Samples (35 g) of the composite was soaked with a solution containing heptamolybdate ammonium and potassium carbonate, as shown in the table.4. The concentration of heptamolybdate ammonium in each solution was different, while the concentration of potassium carbonate was approximately the same. Impregnated composites were caliciviral at 600aboutC for 4 h, resulting in a received molybdate activated potassium catalysts (e a-e), plotted on aluminasilica spinel composite and described in table.4.P R I m e R 10 (a-e). The oxidation of butane. Catalysts (e a-e) obtained in example 9 was used in the oxidation of butane in accordance with the description given in example 2, the results of which are presented in table.4. From table. 4 shows that activated potassium molybdate catalyst deposited on aluminasilica spinel composite, catalyze the oxidation of butane to butenes and butadiene with a high degree of selectivity. In addition, it was found that the selectivity to C4the olefins decreases when the concentration of molybdate falls below 11 wt.P R I m e R 11. The manufacture of the catalyst. Balls of aluminum oxide (4.09 g; UOP-SAB16), it is each solution, containing 1,15 g MgO in the form of uranyl nitrate magnesium.Between each addition of solution impregnated alumina was caliciviral for 2 h at 600aboutWith, resulting in a received composite carrier having a mass ratio of MgO/Al2O30,75. To the sample (6.42 per g) media was added a solution of 9.2 ml) containing heptamolybdate ammonium (11,8 g)2CO3(0,228 g) and NH4VO3(0,60 g) per 100 ml of solution, after which the media was illnerova and received the catalyst (E-11) containing, by weight. Moo3A 12.03; V2O50,58;2About 0,16, and having a surface area of 34 m2/,P R I m e R 12. The oxidation of butane. The catalyst (5,65 g) of example 11 (E-11) were loaded into the reactor with a porous layer as described in example 2. Then at 600aboutAnd GSV 1200 h-1through the reactor missed pulse flows: a mixture of helium and about 20. Bhutan for 5 s and then 60 seconds, respectively, helium, air, and helium. Then the cycle was repeated and got the following results: conversion of butane 45.2% of the selectivity of 58.3% for butadiene, to 20.6% for butene; 78,9% and 78.9 per cent for the total butenes; 6,4% for products of deep oxidation (CO2and WITH); to 8.0% for the cracking products and 6.8% for unknown products is4-hydrocarbons and butadiene greater than the magnitude of productivity, adopted for the standard method, 0.2 g/g cat.-hP R I m e p 13. Obtaining a catalyst. Alumina balls (to 713.3 g; UOP-MS-P-27) with a particle diameter of 500-1000 μm used in the production of composite media containing aluminasilica spinel, the method described in example 2. The obtained composite media had a mass ratio of MgO/Al2O30.38 and surface area of 106 m2/year / Sample (686 g) of the composite was soaked 728 g of a solution containing, by weight. heptamolybdate ammonium 22,5; potassium carbonate 0,66. The impregnated composite was caliciviral for 4 h at 600aboutFrom the resulting received a catalytic composition (E-13) containing, by weight. Moo318,4;2About 0,45.P R I m e R 14. The oxidation of butane. The catalyst obtained in accordance with example 13, used in a laboratory reactor with a rising layer of catalyst. Raw tank fluidized bed of catalyst (with a capacity of 3500 ml) connected to its lower part through a long tube, called "catalytic pipe. The specified vertical pipe is connected through valve "J" with a vertical chamber reactor with a length of 2 m and dim. The catalyst recovered in cyclones, returned to the top of the tank for feeding catalyst. Gaseous feedstock stream containing about. nitrogen 10; butane, 6.9 and balanced helium, pre-heated in the heating chamber, with only 4 mm in diameter, thereby minimizing the residence time, and hence thermal cracking of butane. Chamber for pre-heating was connected to the system at the connection catalytic pipe and valve "J", and gaseous raw stream has podpisala with a speed of 500 cm3/min. and Then the catalyst was heated to 650aboutWith in camera raw, served in the chamber of the reactor with a velocity of 200 cm3/min. and the Temperature of the reactor chamber was about 580aboutC. the residence Time of the gas in the reactor was 1.6 C. In the described procedures were obtained the following results: conversion of butane 23,3% selectivity, butadiene 61,9; butenes 22,1; products of deep oxidation (CO2and WITH) 5,1; C2-3-the cracking products 7,7; methane 1,0; unknown to 2.1. Productivity was about 0.43 g C4/g cat.-h and 0.32 g of butadiene g cat.-'clock From the above results show that productivity4-carbon and butadiene exceeds productivity, etc is used in the reactor with a rising layer of the catalyst, described in example 14, together with the gaseous feedstock stream containing about 67. butane and balanced nitrogen and helium. The gas flow rate was 1000 cm3/min, and the gas retention time in the reactor was about 0,82 C. the Catalyst was applied at a rate of about 455 cm3/min, the residence time of the catalyst in the reactor was about 3.1 C. the Average temperature in a vertical tube was 584aboutC. as a result received the following data: conversion of butane 17,1; selectivity, butadiene 39,1; butane 2.4; products of deep oxidation of CO and CO2) 2,5; the cracking products, including2-C3products 10,6; methane 1,6; isobutane 0,5; unidentified products of 1.8. The productivity of combined butadiene and butenova products amounted to 0.94 g C4/g cat.-h, and the yield of butadiene was 0.49 g of butadiene/g cat.-hours of these results shows that the productivity of hydrocarbons and butadiene exceeds productivity adopted for the standard method (0.2 g/g cat.-h).P R I m e R s 16-20 (a-b).a) preparing the catalysts activated by cesium 16-20. Have received lots of molybdate catalysts doped with cesium, in accordance with the following procedure, p is ω, g: catalyst 1 0,16; catalyst 2 0,23; catalyst 3 0,29; catalyst 4 0,53; and the catalyst 5 0,76.(NH4)6Mo7O24). The obtained products were analyzed by gas chromatography using a multicolumn Carle gas chromatograph, equipped with a column with a diameter of 1/8" (3.2 mm) with the following content: (1) 2,70% carbowax (Carbowax 1540) on Porasil Porasil (21" (530 mm), 80/100 mesh. (180/150 μm)); Tmax175about(2) 3,0% Carbowax 1540 on Porasil (4'(1220 mm) 60/80 mesh. (250/180 μm)), Tmax150aboutWith; (3) 27,5% 2(HEH) on Chromosorb PAW (17", (5180 mm) 45/60 mesh. (328/250 μm), Tmax150aboutWith; (4) Porapak Q 9'(2745 mm), 50/80 mesh. (292/180 μm), Tmax250aboutC; (5) molecular sieve h (9'(2745 mm), 45/60 (328/60 µm) mesh. Tmax300aboutC; (6) molecular sieve 5A (3'(914 mm), 80/100 mesh. (180/150 μm)), Tmax300aboutC; (7) 28%DC 200/500 on Chromosorb PAW 3,5' (1068 mm) 60/80 mesh. (250/180 μm)), Tmax175aboutC. the results Obtained are presented in table. 5. The data show that in the presence of doped cesium catalyst containing magnesium molybdate, butane is oxidized predominantly butadiene and butenes.With R a n t I l n m s p R I m m e R 2. Made a composition as described above for the manufacture of catalysts 16-20, I, wt. MoO322; MgO 78. As already indicated, this composition did not contain cesium. Then the above composition was used as catalyst in the oxidation of butane by the method described in examples 16-20 (b). The results obtained are presented in table. 6.From the comparison of the results of comparative example 2 (GHSV 336 h-1and results of examples 16-20 shows that the presence of cesium in the catalyst significantly improves the selectivity of heavy products, such as furan and benzene, and particularly to the products of deep oxidation, such as carbon monoxide, is reduced accordingly. However, comparing the results of comparative example 2 (GHSV 336 h-1with the results of examples 16-20 showed that the presence of cesium in the catalyst reduces the conversion of butane.P R I m e R s 21-25. a) preparing catalysts 21-25 activated by alkali. Series doped alkali catalysts containing magnesium molybdate, received in accordance with the following procedure, with the amount of alkali metal hydroxide 40 g of a methanol solution was varied as follows: the catalyst 6, CON 0,049 g; catalyst 7, CON 0,098 g; catalyst 8, CON of 0.133 g; catalyst 9, CON 0,320 g; and produce the scientists, the solution was added to magnesium (300 g; CE Basic Industries, Madox Premium magnesia to obtain a suspension. The suspension was dried for 18 h at 70aboutC and for 2 h at 30aboutIn order to obtain a solid mixture. The resulting mixture was ground and passed through a sieve to obtain particles of a size of 20-120 mesh. (850-122 μm). The sieved particles were caliciviral by slowly heating for 5 hours to a temperature of 600aboutC, and then held at this temperature for another 2 hours, Calcined solid product was cooled to room temperature and was received magnesium molybdate containing, by weight. Moo322; MgO 78. The methanol solution was obtained by adding the appropriate quantity of alkali metal hydroxide, as described above, 40 g of a methanol solution. The magnesium molybdate at 15 min was immersed in a methanol solution. The resulting mixture was filtered and the filtered solid was dried in air at room temperature for 4 h, and then in an oven at 120aboutC for 16 hours the Dried solid product was caliciviral by heating for 5 h to 600aboutC, and then held at this temperature for another 2 h, resulting in a received activated alkaline metal catalyst containing magnesium molybdate. The percentage del the Directors 21-25. The above catalysts 21-25, doped potassium and sodium were used in the oxidation of butane by the method described in examples 16-20 b. The results are presented in table.7. The data obtained showed that in the presence of a catalyst containing magnesium molybdate and doped with ions of potassium and sodium, predominantly butane is oxidized in butadiene and butane. In addition, from the comparison of the results of examples 21 to 25 and comparative example 2 (GHSV 336 h-1) shows that when using catalysts doped with potassium and sodium (catalysts 21-25), achieved a significantly higher selectivity to butadiene and butane than when using non-alloy catalysis - tori containing magnesium molybdate. While the selectivity to products of deep oxidation when using doped alkali catalysts is greatly reduced.P R I m e R s 26 and 27. a) preparing an activated potassium catalysts 26 and 27. Received two solution containing (NH4)6Mo7O24H2O (35 g), and potassium carbonate in 125 g of an aqueous solution. The first solution contained 0,63 g (catalyst 26) of potassium carbonate, and the second solution contained 1.44 g (esia and the mixture was drained and illnerova, as described in the examples of the preparation of catalysts 16-20, resulting received doped potassium catalysts containing magnesium molybdate.b) Oxidation of butane using catalysts 26 and 27. Catalysts 26 and 27 used in the oxidation of butane (examples 26 and 27, respectively) according to the procedure described in examples 16-20. The results obtained under different conditions, are presented in table.8. The data table.8 show that in the presence of a catalyst containing molybdate and magnesium-doped potassium carbonate, predominantly butane is oxidized in butadiene and butane. These data also show that increasing the reaction temperature from 550 to 570aboutWith the conversion of butane increases, whereas the selectivity to butenes and butadiene decreases. In addition, the results show that at lower gas flow from 600 up to 336 h-1the conversion of butane is increased, and the selectivity to butane and butadiene falls. From the comparison of examples 26 and 27 shows that the catalyst containing higher amounts (wt. ) potassium, gives a lower conversion of butane and higher selectivity to butenes and BUTADIENES. From the comparison of examples 27(a) and 27(C) comparative Et to BUTADIENES and lower selectivity to heavy products and to the products of deep oxidation, than the catalyst not containing ions of alkali metals.P R I m e R 28. a) preparing doped potassium Catalyst 28. Ammonium Vanadate NH4VO3(2.55 g; of 0.022 M) was added to 100 ml of water and the resulting mixture was heated to 60aboutIn order to accelerate the dissolution, after which the temperature of the solution was raised to about 97aboutC and stirring was added (NH4)6Mo7O24H2O (18.5 g; 0,015 M). The resulting solution was heated up until its volume is reduced to 70 ml, and then added magnesia (34 g; 0.85 M) and received a thick paste. Then this thick paste was added 50 ml of water and was given a homogeneous kremoobraznoy mixture. This mixture was poured into a quartz crucible during the night was dried in air, then for 2 h, dried at 110aboutWith and illnerova at 600aboutC for 2 h, resulting in the obtained calcined solid material containing, by weight. V2O54; MoO330; MgO 65. Then of 8.2 ml of a methanol solution containing sodium hydroxide (1 g KOH/100 ml), diluted incremental amount of methanol to volume 16 ml. and then diluted solution of one drop was added to the resulting higher cal is Uchenie 30 min, and then for 1 h and dried in an oven at 100aboutC. the resulting solid contained vanadium oxide, magnesium oxide, molybdenum oxide and about 1 wt. potassium, calculated as potassium hydroxide.b) Oxidation of butane using catalyst 28. The catalyst 28, obtained above, was used in the oxidation of Bhutan, conducted in accordance with the procedure described in examples 16-20. The results are presented in table.9.The results show that in the presence of a catalyst containing magnesium molybdate, vanadium oxide and potassium ions, butane is oxidized predominantly butadiene and butenes.With R a n t I l n m s p R I m e R 3. The material for the comparative example was obtained in accordance with the description in example 28 except that the catalyst was not impregnated with potassium hydroxide. The resulting material contained, by weight. V2O54; 30 MoO; MgO 66. This material is then used in the oxidation of butane in accordance with the procedure described in examples 16-20. The results obtained are presented in table.9. From the comparison of comparative example 3 with example 28 shows that the presence of the potassium catalyst promoter contributes to a significant increase in selectivity for the bout the production of activated potassium catalyst 29. (NH4)6Mo7O244H2O (13.5 g; of 0.11 M) was dissolved in 120 ml of water, and the resulting mixture was heated to 60aboutWith for a solution. Then gradually and intensively stirring for 5 min the solution was added magnesium oxide (39 g), resulting in the obtained homogeneous suspension. This suspension during the night was dried at 110aboutWith the purpose of obtaining the sintered material, which was then caliciviral in air at 600aboutC for 2 h and the result has been a mixture of magnesium oxide and molybdenum oxide. This powdery oxide mixture was condensed by pressing in a Carver press with a force of 20,000 pounds (9000 kg) and received 1 tablet per 1/8" of 28.6 mm, This tablet was crushed into several pieces and saturated methanol solution of potassium hydroxide containing 1 g of KOH in 100 ml of methanol. Dosage of potassium hydroxide was reached 0.5. Impregnated with potassium hydroxide catalyst containing magnesium molybdate, dried in air for 2 h, and then another 2 hours in an oven at 110aboutC.b) Oxidation of butane using the catalyst 29. Impregnated with potassium hydroxide catalyst containing magnesium molybdate (catalyst 29; 7,15 g), obtained as described above, zagrai its results are presented in table.10.The results showed that in the presence of doped potassium catalyst containing magnesium molybdate, butane is oxidized predominantly butadiene and butenes. In addition, it was found that at constant temperature and volume hourly flow rate of gas volume flow of butadiene increases significantly with increasing percentage of butane in raw materials. Under these same conditions, the conversion of butane and the selectivity to butadiene are maintained at a high level. Similar conclusions can also be made relative to the volumetric flow rate and selectivity sum4products (butadiene and butenes). 1. The method of obtaining 1,3-butadiene through the oxidative dehydrogenation of butane in the presence of a catalyst comprising the oxides of magnesium and molybdenum and the media on the basis of aluminum oxide, at 500 650oAnd 7 210 KPa and other conditions for obtaining a reaction mixture containing 1,3-butadiene with a selectivity of at least 40 mol. characterized in that, to improve the performance of the process, using a catalyst reactive with oxygen, optionally containing an oxide of an alkali metal and containing a carrier with a surface area 25,0 184,3 m2/g SOS 3 0,38 0,79 when the next content, wt.Molybdenum oxide 8,40 24,30
The oxide of the alkali metal 0,16 1,43
The media and the Rest
2. The method according to p. 1, wherein the used catalyst, optionally containing 0,58 0,85 wt. the vanadium pentoxide and the process is carried out at 500 650oWith, 10,5 210,0 KPa, space velocity of Bhutan 400 4000 h-1and other conditions for obtaining a reaction mixture containing butadiene with a selectivity of at least 50 mol.3. The catalyst for obtaining 1,3-butadiene, comprising the oxides of magnesium and molybdenum and the media on the basis of aluminum oxide, characterized in that, to improve the activity and stability of the catalyst, it is additionally contains an alkali metal oxide and contains a carrier with a surface area 25,0 184,3 m2/g consisting of magnesium oxide and aluminum and/or alumomagnesium spinel, having a mass ratio of MgO / Al2O30,38 0,79, and has the ability to deliver active oxygen when the next content, wt.Molybdenum oxide 8,4 24,3
The oxide of the alkali metal 0,16 1,43
The media and the Rest
4. The catalyst p. 3, characterized in that, to increase active
FIELD: petrochemical process catalysts.
SUBSTANCE: catalyst constitutes cements formed during heat treatment and depicted by general formula MeO·nAl2O3, where Me is at least one group IIA element and n is number from 1.0 to 6.0, containing modifying component selected from at least one oxide of magnesium, strontium, copper, zinc, indium, chromium, manganese, and strengthening additive: boron and/or phosphorus oxide. The following proportions of components are used, wt %: MeO 10.0-40.0, modifying component 1.0-5.0, boron and/or phosphorus oxide 0.5-5.0, and alumina - the balance. Catalyst is prepared by dry mixing of one group IIA element compounds, aluminum compounds, and strengthening additive followed by mechanochemical treatment on vibromill, molding of catalyst paste, drying, and calcination at 600-1200°C. Modifying additive is incorporated into catalyst by impregnation and succeeding calcination. Method of pyrolysis of hydrocarbon feedstock producing C2-C4-olefins is also described.
EFFECT: increased yield of lower olefins.
3 cl, 2 tbl, 18 ex
FIELD: industrial organic synthesis catalysts.
SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at median pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:0.3:(0.014-0.038):(0.047-0.119):(0.05-0.1):(0.007-0.014):(0.0292-0.054).
EFFECT: increased mechanical strength and wear resistance of catalyst.
FIELD: reduction-oxidation catalysts.
SUBSTANCE: invention relates to catalysts for deep oxidation of carbon monoxide that can be used to treat industrial emission gases and motor transport exhaust gases. Aluminum-based oxidation catalyst contains 1.3-5.1% of rare-earth and/or alkali-earth element and represents ultradisperse powder.
EFFECT: increased catalytic activity.
FIELD: fuel combustion catalysts.
SUBSTANCE: invention provides catalyst containing active aluminum oxide, magnesium oxide, at least one platinum-group precious metal, and also at least one material capable of accumulating nitrogen oxides, said magnesium oxide forming homogenous mixed oxide with aluminum oxide in concentration ranging form about 1 to about 40 wt % based on total weight of mixed oxide. The use of catalyst is also disclosed.
EFFECT: increased heat resistance of catalyst and accelerated conversion of nitrogen oxides.
24 cl, 14 dwg, 3 tbl, 8 ex
FIELD: petrochemical process catalyst.
SUBSTANCE: invention, in particular, relates to precursors of catalysts used in production of hydrocarbons from synthesis gas. Preparation of catalyst precursor involves contacting crude catalyst carrier, which is partly soluble in aqueous acid solution and/or in neutral aqueous solution, with modifying component of general formula Me(OR)x, wherein Me is selected from Si, Zr, Ti, Cu, Zn, Mn, Ba, Co, Ni, Na, K, Ca, Sn, Cr, Fe, Li, Ti, Mg, Sr, Ga, Sb, V, Hf, Th, Ce, Ge, U, Nb, Ta, and W; R represents alkyl or alkoxy group; and x is integer from 1 to 5. Therefore, modifying component is introduced into catalyst carrier or deposited onto surface thereof to form protected modified catalyst carrier, which is less soluble and more inert in aqueous acid solution and/or in neutral aqueous solution than crude carrier. Resulting catalyst carrier is then subjected to heat treatment at temperature lower than 100° C so that calcination of the carrier does not take place. Non-calcined protected modified catalyst carrier is mixed with aqueous solution of cobalt, which is active component of catalyst or its precursor, to form slurry. Which is exposed to subatmospheric pressure to facilitate impregnation of the catalyst carrier with cobalt or its precursor. Impregnated carrier is then dried at subatmospheric pressure and finally calcined.
EFFECT: enhanced selectivity and activity of catalyst in Fischer-Tropsch synthesis and eliminated need to perform calcination step after contact of crude Carrier with modifying component and drying.
16 cl, 5 dwg, 1 tbl, 6 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: invention relates to chemistry of heterogeneous catalysts and is directed to production of high-octane gasoline component via alkylation of isobutane with butane-butylene fraction on heterogeneous catalysts. Solid catalyst represents porous superacid based on zirconium and/or hafnium metallosilicates promoted with salts of double- or triple-charged metal cations with double-charged anions and depicted by general formula (EO2·aSiO2)·b(McXd) wherein E = Zr and/or Hf, a=17-34; b=0.5 when c=1 and d=1, M= Ni2+, Zn2+, or ZrO2+, X=SO4 2- or ZrF6 2-; or b=0.1666 when c=2 and d=3, M=Sc3+, Y3+, or Ga3+ and X= SO4 2-, parameter "a" being allowed to deviate from indicated value to larger or lesser side by 20% and parameter "b" by 5%. High-octane gasoline component is produced as indicated above at temperature 348 to 375 K, pressure 1.7 to 2.5 MPa, isobutane-to-butenes molar ratio 10-15, and volume feed supply velocity between 6.4 and 8.5 g/mL catalyst/h. Catalyst can optionally be regenerated.
EFFECT: enhanced conversion, yield of alkylate, productivity, and prolonged catalyst lifetime.
7 cl, 4 tbl, 11 ex
SUBSTANCE: aqueous suspension containing earth metal salt, powdered metal chloride and powdered transition metal oxide is made; aqueous suspension is made by dispersing in water the earth metal salt chosen from the group including barium and/or calcium and probably strontium or their combination. Water is added in powdered metal chloride, where powdered metal chloride is chosen from the group including Sn, Mg, Na, Li, Ba. Further powdered transition metal oxide is added being titanium oxide, to water; then plastic binder is added to until paste is formed; paste is dried up paste to powder; powder is heated up at raising temperature following preset temperature profile. Heated powder is baked to produce perovskite catalyst. Suspension contains mixed Ba and/or Ca and/or Sr (0.95mole) + TiO2 + metal chloride chosen from the group Sn, Mg, Na, Li, Ba in amount 0.05 mole.
EFFECT: simplified technology of catalyst producing.
19 cl, 14 ex, 2 tbl, 8 dwg
SUBSTANCE: invention refers to catalyst preparation of the low temperature conversion of carbon oxide with water vapour including: mixing of the components containing copper and zinc; mechanic activation during passing-through of the gas mix containing ammonia, carbon dioxide and water vapour; additional activation with pass of water vapour containing the additives of alkali metals carbonates and calcium aluminate at mass ratio (on oxide basis): CuO:ZnO:CaAl2O4:Me2O-(42-60):(24-42):(13-15):(1-3), where Me-K, Rb, Cs; 4) pellets moulding and calcination.
EFFECT: enhancing of catalyst selectivity and durability at retaining of its high activity.
1 tbl, 11 ex
SUBSTANCE: described is catalyst for isomerisation of xylols, which includes in wt %: zeolite ZSM-5 - 10-35, calcium 0.05-1.0, calculated per zeolite, sodium 0.05-0.12, calculated per zeolite, aluminium oxide - the remaining part. Also described is method of preparing said catalyst, which includes mixing of aluminium hydroxide with zeolite ZSM-5, processing of obtained mixture with water solutions of calcium and, possibly, sodium compounds, with following forming and burning of obtained extrudates.
EFFECT: ensuring of xylol isomerisation until equilibrium composition of isomer is achieved, reduction of xylol loss at isomerisation temperature 400-460°C, increase of level of ethyl benzene, n-Nona and cumene conversion.
3 cl, 1 tbl, 9 ex
SUBSTANCE: catalysts for preparation of biofuel by reesterification of vegetable oil with alcohol represent composition based on hexaaluminate (MAl12O19) having magnetoplumbite or β-Al2O3 whereat: M - Ba or Sr, or La, or having spinel structure (MR2O4) whereat: M - Ca or Sr, or Ba, whereat R contains Y or La, or composition based on MgO+R2O3+solid solution R2-xMgxO3 with hexagonal structure whereat R contains Y or La, x=0.05÷0.12. The method for catalysts preparation includes precipitation of mixed solution of M and Al nitrates whereat M contains Ba or Sr, or La at constant values of pH 7.5-8.0 and temperature with water solution of NH4HCO3, or precipitation of mixed solution of M and R whereat M = Ca or Sr, or Ba, R contains Y or La at constant values pH equal to 9.9÷11.9 and temperature with water solution of KOH, or precipitation mixed solution of Mg and R nitrates at constant values of pH equal to 9.0-9.5 and temperature with water solution of KOH followed with stages of filtration, washing, drying and calcination. The method of biofuel preparation involves the reesterification of vegetable oil with alcohol implemented in the presence of the catalyst described above.
EFFECT: high level of the vegetable oil conversion.
13 cl, 1 tbl, 18 ex
FIELD: organic synthesis catalysts.
SUBSTANCE: invention, in particular, concerns preparation of catalyst soluble in reaction medium, which is efficient in reactions of epoxidation of olefins by organic hydroperoxides. Preparation of catalyst comprises providing water-ammonia solution of ammonium molybdate, bringing it into reaction with C2-C8-alkanediol, and distilling away aqueous ammonia and excess diol followed by modifying resulting catalyst with nitrogen-containing organic compound, which is introduced into catalyst in aliphatic C3-C4-alcohol solution at molar ratio of nitrogen-containing organic compound to molybdenum compound (1-10):1. Nitrogen-containing organic compound is selected from diamines of general formula R1NHR2NHR3, where R1 is phenyl, C6-cycloalkyl, naphthyl, or diphenylamine, R2 is C1-C2-alkylene, C6-C8-arylene, or -C(=NH)-, and R3 is isopropyl, phenyl, naphthyl or diphenylamine; aminophenols of general formula R4R5R6N, where R4 is hydroxynaphthyl or 4-hydroxy-3,5-di-tert-butylbenzyl, R5 is hydrogen, C1-C2-alkyl, or phenyl, and R6 is methyl or 4-hydroxy-3,5-di-tert-butylbenzyl; and stable nitroxyl radical 2,2,6,6-tetramethylpyperidine-1-oxyl. Method allows: preparation of molybdenum-containing catalyst showing high activity and selectivity in reaction of hydroperoxide epoxidation of olefins, including low-reactive ones, e.g. propylene; simplification of technology due to use of commercially available organic nitrogen-containing compounds, so that additional synthesis stages can be avoided; and use of ammonium molybdate obtained during regeneration of molybdenum-containing epoxidation catalyst.
EFFECT: increased catalyst preparation efficiency and increased activity and selectivity of catalyst.
2 cl, 2 tbl, 18 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention proposes method for epoxydation of olefins with ethyl benzene hydroperoxide in the presence of molybdenum-containing catalyst and nitrogen-containing compound. Derivatives of quinolines or Mannich base or their mixtures are used as nitrogen-containing compound and the mole ratio molybdenum : nitrogen-containing compound is maintained = 1:(0.05-0.4). Invention provides enhancing conversion and selectivity of the epoxydation process of olefins with organic hydroperoxides.
EFFECT: improved method for epoxydation.
3 cl, 15 ex
FIELD: petrochemical processes and catalysts.
SUBSTANCE: invention relates to supported olefin metathesis catalyst and to a olefin metathesis process using the latter. Catalyst is essentially composed of transition metal or oxide thereof, or a mixture of such metals, or oxides thereof deposited on high-purity silicon dioxide containing less than: 150 ppm magnesium, 900 ppm calcium, 900 ppm sodium, 200 ppm aluminum, and 40 ppm iron. When pure 1-butene comes into interaction with this catalyst under metathesis reaction conditions, reaction proceeds with 2-hexene formation selectivity at least 55 wt %. Use of catalyst according to invention in olefin metathesis process minimizes double bond isomerization reactions.
EFFECT: increased olefin metathesis selectivity regarding specific products.
17 cl, 2 tbl, 2 ex
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: oxidation is performed at 20-60°C with hydrogen peroxide aqueous solution in presence of molybdenum-containing catalyst, in particular molybdenum bis-alkylsulfoxide peroxo complexes.
EFFECT: increased yield of sulfoxides, oxidation selectivity, and oxidation rate.
2 tbl, 6 ex
FIELD: petrochemical industry; natural gas industry; manufacture of the three-dimensional catalytic nets braided in two or more layers.
SUBSTANCE: the invention is pertaining to the catalytic nets braided in two or more layers and used for the gaseous reactions. The nets are braided in two or more layers from the noble metals wire, the meshes of the separate layers are connected to each other by the interlinking threads filaments. The filling threads are inserted between the layers. The catalytic nets allow to increase activity and productivity and to use the smaller amount of the noble metal.
EFFECT: the invention ensures, that the catalytic nets allow to increase activity and productivity and to use the smaller amount of the noble metal.
15 cl, 2 dwg, 2 ex
FIELD: technological processes; chemistry.
SUBSTANCE: method involves reaction of raw material containing organic component with a catalyst composition. Processing method is selected out of alkylation, acylation, hydrotreatment, demetallisation, catalytic deparaffinisation, Fischer-Tropsch process and cracking. Catalyst composition includes mainly mesoporous silicon dioxide structure containing at least 97 vol.% of pores with size in the interval from ca. 15 Å to ca. 300 Å, and at least ca. 0.01 cm3/g of micropores. Mesoporous structure features at least one catalytically and/or chemically active heteroatom in amount of at least ca. 0.02 mass %, selected out of a group including Al, Ti, V, Cr, Zn, Fe, Sn, Mo, Ga, Ni, Co, In, Zr, Mn, Cu, Mg, Pd, Ru, Pt, W and their combinations. The catalyst composition radiograph has one 0.3° to ca. 3.5° peak at 2θ.
EFFECT: highly efficient method of organic compound processing in the presence of catalyst composition without zeolite.
20 cl, 31 ex, 17 tbl, 22 dwg
SUBSTANCE: catalytic composition contains compounds of formula: Mo1VaSbbNbcMdOx, in which Mo represents molybdenum, V stands for vanadium, Sb stands for antimony, Nb stands for niobium, M represents gallium, a constitutes from 0.01 to 1, b constitutes from 0.01 to 1, c constitutes from 0.01 to 1, d constitutes from 0.01 to 1, and x is determined by requirements of valency of other present elements.
EFFECT: increase of alkane conversion degree, increase of selectivity of catalytic composition in one stage process of alkane transformation into unsaturated carbonic acid.
9 cl, 1 tbl, 12 ex