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Continuous method of manufacturing geometrical moulded products from catalyst k Invention relates to field of catalysis. Described is method of manufacturing geometrical moulded products from catalyst K, in which active mass represents multi-element oxide, which contains Mo element, Bi and/or V elements, as well as one or several elements from series Co, Ni, Fe, Cu and alkali metals, in which highly dispersed mixture is obtained by means of sources of different elements, said mixture is coarsened to powder by pressing, and moulded product V is formed from said coarser powder by agglomeration; said products are divided into undamaged moulded products V+ and damaged moulded products V-, undamaged moulded products V+ are made into moulded products from catalyst K, and damaged moulded products V- are crushed and returned into production of highly dispersed mixture. |
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Method of filling longitudinal section of contact pipe Invention relates to a method of filling a longitudinal section of a contact pipe with a homogeneous part of a solid catalyst bed. The method of filling a longitudinal section of a contact pipe with a homogeneous part of a solid catalyst bed, the active mass of which is at least one multielement oxide which contains a) elements Mo, Fe and Bi, or, b) elements Mo and V, or c) element V, and additionally P and/or Sb, or the active mass of which contains elementary silver on an oxide support-article, and which consists of only one type Si, or a homogenised mixture of various types Si of catalytically active moulded articles of a defined geometrical shape or catalytically active moulded articles and inert moulded articles of a defined geometrical shape, wherein the median of the maximum longitudinal dimensions Ls i of the articles of a defined geometrical shape of type Si is characterised by the value Ds i, at least within one type Si of moulded articles of a defined geometrical shape, the following set of conditions M is satisfied, such that 40 to 70% of the total number of moulded articles of a defined geometrical shape belonging to S1, have a maximum longitudinal dimension Ls i, for which the inequality 0.98·Ds i≤Ls i≤1.02·DS i holds, at least 10% of the total number of moulded articles of a defined geometrical shape belonging to Si have a maximum longitudinal dimension Ls i, for which the inequality 0.94·Ds i≤Ls i<0.98·Ds i holds, at least 10% of the total number of moulded articles of a defined geometrical shape belonging to S1 have a maximum longitudinal dimension Ls i for which the inequality 1.02·Ds i<Ls i≤1.10·Ds i holds, less than 5% of the total number of moulded articles of a defined geometrical shape belonging to Si have a maximum longitudinal dimension Ls i for which the inequality 0.94·Ds i>Ls i holds, and less than 5% of the total number of moulded articles of a defined geometrical shape belonging to Si have a maximum longitudinal dimension Ls i for which the inequality 1.10·Ds i<Ls i holds, wherein the sum of all moulded articles of a defined geometrical shape belonging to Si is 100%; described also is a method of loading a contact pipe with a solid catalyst bed, a shell-and-tube reactor, a method for oxidation of an organic compound and a method for synthesis of separate organic compounds. |
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Catalyst and method of producing unsaturated aldehyde unsaturated carboxylic acid Invention relates to production of catalyst for producing unsaturated aldehyde and unsaturated carboxyl acid. Proposed method comprises applying catalyst powder coating on inert substrate to produce applied catalyst wherein inert substrate features ring shape and has outer periphery bent in longitudinal direction of substrate. Note here that catalyst is produced in atmosphere of granulating chamber at application of coating to ensure absolute humidity of 0.01 and higher. Catalyst thus produced is used for gas-phase oxidation of propylene, isobutylene, tert-butyl alcohol or methyl-tert-butyl ether to produce appropriate unsaturated aldehyde, or for gas-phase oxidation of said aldehyde to produce carboxylic acid. |
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Invention relates to a method of regenerating a catalyst layer and a method of producing acrolein and/or acrylic acid via heterogeneously catalysed partial gas-phase oxidation of propylene. The method of regenerating a catalyst layer which is deactivated during heterogeneously catalysed partial dehydrogenation of a hydrocarbon involves passing a regenerating gas through a layer of deactivated catalyst for a period of time t, said gas being at high temperature and containing molecular oxygen and an inert gas but not containing a hydrocarbon, under the condition that during the regeneration process total content GA of carbon oxides in the regenerating gas passed through the catalyst layer at the outlet of the catalyst layer within a period of time t at least periodically exceeds total content GE of carbon oxides in the regenerating gas passed through the catalyst layer at the inlet of the catalyst layer, wherein the corresponding content values are expressed as a percentage of the volume (vol. %) of the regenerating gas and wherein the difference ΔG=GA-GE before the end of the regeneration process passes through a maximum ΔGmax, where: a) 0.2 vol. % ≤ ΔGmax≤ to 5 vol. %, and b) content of molecular oxygen in the regenerating gas to be passed through the catalyst layer expressed in vol. % of the regenerating gas, for a period of time t before the end of the regeneration process, is increased at least thrice, wherein the increase in content of molecular oxygen each time is at least 2 vol. %. In the method of producing acrolein and/or acrylic acid, the catalyst layer is regenerated using the disclosed regeneration method from time to time. |
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Method to produce acrolein or acrylic acid or their mixture from propane In the first reaction zone A at least two gaseous supply flows are supplied, containing propane, at least one of which contains fresh propane, to produce a reaction gas A; - in the reaction zone A the reaction gas A passes through at least one layer of catalyst, in which, by means of partial heterogeneous-catalysed dehydration of propane, molecular hydrogen and propylene are produced; - molecular oxygen is supplied into the reaction zone A, which oxidises in the reaction zone A at least a part of molecular hydrogen contained in the reaction gas A to water vapour - the gas-product A is taken from the reaction zone A, containing propylene, propane, molecular hydrogen and water vapour; B) water vapour contained in the gas-product A, if necessary, fully or partially by means of direct and/or indirect cooling, is separated in the first zone of separation I by the method of condensation with preservation of the gas-product A*; C) in the reaction zone B, by supply of molecular oxygen, the gas-product A or the gas-product A* is used to supply at least into one oxidisation reactor with the reaction gas B, comprising propane, propylene and molecular hydrogen, and propylene contained in it is exposed to heterogeneous-catalysed partial oxidation in the gas phase to produce acrolein or acrylic acid or their mixture as a target product, and also the gas-product B containing non-converted propane; D) from the reaction zone B the gas-product B is released, and the target product contained in it is separated in the second separation zone II, besides, the residual gas containing propane remains; E) whenever necessary, a part of the residual gas is returned having the composition of the residual gas, as a supply flow containing propane, into the reaction zone A; F) in the zone of separation III propane contained in the residual gas that has not been returned into the reaction zone A, from which earlier, if required, water vapour contained in it has been removed, possibly, by condensation and/or using a separating membrane, molecular hydrogen contained in it has been fully or partially removed, is separated by means of absorption in an organic dissolvent (absorbent) with production of absorbate containing propane; and G) in the separation zone IV propane is separated from absorbate and returned into the reaction zone A in the form of a supply flow containing propane, besides, in the reaction zone A enough amount of molecular hydrogen is oxidised to water vapour so that this hydrogen amount oxidised in the reaction zone A to the water vapour makes from 30 to 70 mol% of molecular hydrogen amount produced in the reaction zone A, and for values of the working pressure P in each case identified at the inlet to an appropriate area, in different zones of the method under the invention the following ratios are in effect: Preaction zone A>Pseparation zone I>Preaction zone B>Pseparation zone II>Pseparation zone III>Pseparation zone IV>Preaction zone A. |
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Invention relates to an improved method of producing at least one product from acrolein and acrylic acid via partial oxidation of propylene, where a) purified propane is converted at the first reaction step in the presence and/or absence of molecular oxygen, at least one dehydrogenation from a group comprising homogeneous dehydrogenation, heterogeneous catalytic dehydrogenation, homogeneous oxydehydrogenation and heterogeneous catalytic oxydehydrogenation, wherein a gaseous mixture 1 is obtained, which contains unconverted propane and the formed propylene, and b) optional separation from the total amount or partial amount of the gaseous mixture 1 of a partial amount of components other than propane and propylene contained therein, e.g., hydrogen, carbon monoxide, water vapour and/or optional conversion thereof to other compounds, e.g., water and carbon dioxide, and where a gaseous mixture 1' is obtained, which contains propane and propylene, and on at least one of the following reaction steps, c) the gaseous mixture 1 or gaseous mixture 1' or a mixture from the formed gaseous mixture 1' and the remaining gaseous mixture 1 as a component of a gaseous mixture 2 are subjected to heterogeneous catalytic gas-phase partial oxidation of propylene contained in gaseous mixture 1 and/or gaseous mixture 1', wherein a gaseous mixture 3 is obtained, which contains at least one product, d) on at least one separation step, the product is separated from gaseous mixture 3 and from the remaining residual gas, at least propane is returned to the first reaction step, where purified propane is obtained from crude propane which contains ≥90 wt % propane, ≤99 wt % propane and propylene, ≥100 ppm hydrocarbons, having 2 carbon atoms, and ≥100 ppm hydrocarbons, having 4 carbon atoms, under the condition that crude propane is fed into the fractionation column and purified propane is obtained higher than the feeding point under the condition that content of hydrocarbons having 2 carbon atoms, in wt %, in terms of the contained propane, in the purified propane is more than 100% of the corresponding content in crude propane and content of hydrocarbons having 4 carbon atoms, in wt %, in terms of content of propane, in the purified propane is at most 50% of the corresponding content in crude propane. |
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Invention relates to an improved method for long-term heterogeneous catalytic partial gas-phase oxidation of an organic starting compound selected from propylene, isobutene, acrolein, methacrolein, propane or isobutane, to the desired organic compound, where the starting gaseous reaction mixture, containing the organic starting compound and molecular oxygen, is first passed through a freshly loaded sold catalyst layer which is filled with separation into two temperature zones A and B, lying in space one behind the other, temperature TA of which is such that the difference ΔTBA between temperature TB of zone B and temperature TA of zone A, which is calculated by taking the greater of the two values as the minuend, is greater than 0°C, such that the starting reaction mixture of gases successively flows through temperature zones A, B, first through A and then B, where temperature zone A extends until conversion of the organic starting compound UA = 15-85 mol %, and in temperature zone B conversion of the organic starting compound increases to a value UB ≥ 90 mol %, and as the operating life increases, temperature of zones A, B is changed in order to compensate for deterioration of quality of the solid catalyst layer, where as the duration of operation increases, temperature of that temperature zone which initially had a lower value, is raised, and the difference ΔTBA between temperature values of both zones is lowered, such that when calculating the difference, temperature of that zone which was initially the higher value, remains as the minuend. |
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Invention relates to an improved method for heterogeneous catalytic gas-phase partial oxidation of at least one initial organic compound selected from propylene, isobutene, acrolein, methacrolein, propane or isobutane with molecular oxygen on a fixed catalyst bed freshly put into a reaction space, in which, for partial oxidation, a reaction gaseous mixture containing at least one initial organic compound and molecular oxygen is passed through the fixed catalyst bed, and reaction heat is removed via indirect heat exchange with a liquid heat carrier directed outside the reaction space, and as the quality of the fixed catalyst bed falls with operation time, not all, but part of the fixed catalyst bed is replaced with part of a replacement fixed catalyst bed in order to restore the quality of the fixed catalyst bed, where the specific volume activity of the replacement part of the fixed catalyst bed is lower than that of the replaced part of the fixed catalyst bed in its fresh state. |
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Method involves: a) heterogeneously catalysed vapour-phase partial oxidation of a starting organic compound selected from propylene, propane, isobutylene, isobutane, acrolein or methacrolein with molecular oxygen in a parallel-functioning system of oxidation reactors containing catalysts, which results in formation of two gas streams respectively containing the desired compound and respectively formed in one of two systems of oxidation reactors, and b) subsequent extraction of the desired product from two streams of the obtained gas to form at least one stream of crude desired product according to which c) before extraction of two from two streams, the obtained gas is mixed with each other into a mixed stream. In case of change in selectivity of formation of the desired product and/or by-products during operation the entire amount or partial amount of catalyst is replaced in parallel with fresh catalyst not in all parallel-functioning systems of oxidation reactors in which end products contained in the mixed stream are formed. |
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Method of producing acrylic acid from propane According to the method: A) at least two initial gas streams containing propane, which form the reaction gas A, are fed into a reaction zone A, where one of said gas streams contains fresh propane; the reaction gas A is passed through at least one catalyst layer in reaction zone A in which partial heterogeneously catalysed dehydrogenation of propane results in formation of molecular hydrogen and propylene; molecular oxygen is fed into reaction zone A and oxidises molecular hydrogen in the reaction gas A to water vapour, and a gaseous product A is collected from reaction zone A, said product containing molecular hydrogen, water vapour, propylene and propane; B) the gaseous product A collected from the reaction zone A, while feeding molecular oxygen, is used in reaction zone B to supply at least one oxidation reactor with reaction gas B which contains molecular hydrogen, water vapour, propane, propylene and molecular oxygen, and propylene contained in reaction gas B undergoes two-step heterogeneously catalysed partial gas-phase oxidation in reaction zone B to obtain a gaseous product B containing acrylic acid as the end product, unconverted propane, molecular hydrogen, water vapour and carbon dioxide as by-products, as well as other secondary components with boiling point lower or higher the boiling point of water; C) gaseous product B is output from the reaction zone B and acrylic acid, water and secondary components with boiling point higher than that of water contained therein are separated in a first separation zone I through fractional condensation or absorption, wherein the residual gas I contains unconverted propane, carbon dioxide, molecular hydrogen, secondary components with boiling point lower than that of water, as well as, if necessary, propylene and molecular oxygen not converted in reaction zone B; D) residual gas I undergoes further treatment by washing carbon dioxide contained therein, separation of a partial amount of residual gas I, as well as, if necessary, separation of molecular hydrogen contained in the residual gas I using a separating membrane; E) after further treatment, unconverted propane-containing residual gas I is returned to reaction zone A as at least one of at least two propane-containing initial streams, where in reaction zone A, a certain amount (M) of molecular hydrogen is oxidised to water vapour, which makes up at least 35 mol % but not more than 65 mol % of the total amount of molecular hydrogen produced in reaction zone A and, if necessary, fed into said reaction zone A. |
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Invention relates to a method of conducting a continuous process of producing acrolein, acrylic acid or mixture thereof from propane in a stable operating mode, according to which: A) propane in a first reaction zone A undergoes heterogeneously catalysed dehydrogenation in the presence of molecular oxygen to obtain a gaseous mixture of products A containing propane and propylene, B) the gaseous mixture of products A, if needed, is fed into a first separation zone A in which a portion or more of components different from propane and propylene is separated therefrom and a gaseous mixture of products A' containing propane and propylene remaining after separation is obtained, C) the gaseous mixture of products A or gaseous mixture of products A' is fed into at least one oxidation reactor of the second reaction zone B, in which propylene contained therein undergoes partial selective heterogeneously catalysed gas-phase oxidation with molecular oxygen to obtain a gaseous mixture of products B, which contains acrolein, acrylic acid or mixture thereof as the desired product, unconverted propane, excess molecular oxygen and, if needed, unconverted propylene, D) in the second separation zone B, the desired product contained therein is separated from the gaseous mixture of products B, and at least a portion of the remaining gas containing propane, molecular oxygen and, if needed, unconverted propylene is returned to the reaction zone A as circulation gas 1 containing molecular oxygen, E) fresh propane is fed into at least one continuous flow process zone selected from a group comprising reaction zone A, separation zone A, reaction zone B and separation zone B, where the said fresh propane is fed at a rate characterised by a given stationary value when realising the process in a stable operating mode, and F) content of molecular oxygen in the gaseous mixture of products B is continuously determined and said value is compared with the desired stationary value needed to realise the process in stable operating mode, characterised by that if at a certain moment in time, content of molecular oxygen in the gaseous mixture of products B exceeds the given desired stationary value, fresh propane is fed into the process right away at feed rate higher than its stationary value, and if at a certain moment in time, content of molecular oxygen in the gaseous mixture of products B is lower than the corresponding given desired stationary value, fresh propane is fed into the process right away at feed rate lower than its stationary value. |
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Method of producing acrolein, acrylic acid or mixture thereof from propane According to method A) an input stream of the reaction gaseous mixture A is fed into the input of the first reaction zone A, where the input stream is obtained by merging at least four different gaseous initial streams 1, 2, 3 and 4, where the gaseous initial streams 1 and 2 contain propane, gaseous initial stream 4 is molecular hydrogen and gaseous initial stream 3 is fresh propane, the input stream of the reaction gaseous mixture A is passed at least through one catalyst layer of the first reaction zone A on which, if needed, when feeding other gaseous streams, as a result of heterogeneous catalytic partial dehydrogenation of propane, a stream of products of gaseous mixture A forms, which contains propane and propylene, the stream of products of gaseous mixture A comes out of the first reaction zone A through the corresponding outlet, while splitting said stream into two partial streams 1 and 2 of products of the gaseous mixture A with identical composition, and the partial stream 1 of products of the gaseous mixture A is returned to the first reaction zone A as the gaseous initial stream 1, the partial stream 2 of products of the gaseous mixture A, if needed, is directed to the first separation zone A, in which a portion or more of components contained therein, which are different from propane and propylene, are separated, as a result of which a stream of products of gaseous mixture A' which contains propane and propylene, B) partial stream 2 of products of the gaseous mixture A or a stream of products of gaseous mixture A' is used in a second reaction zone B for supplying at least one oxidation reactor, in which propylene contained in the partial stream 2 of products of gaseous mixture A or in the stream of products of gaseous mixture A' undergoes selective heterogeneously catalysed partial gas-phase oxidation with molecular oxygen to obtain a stream of products of a gaseous mixture B, which contains acrolein, acrylic acid or mixture thereof as the desired product, unconverted propane and, if needed, unconverted propylene, as well as molecular oxygen, the stream of products of gaseous mixture B comes out of reaction zone B, the desired product contained in separation zone B is separated in said separation zone B and at least a portion of residual gas formed after separation and containing unconverted propane, molecular oxygen and, if needed, unconverted propylene, is returned to reaction zone A as gaseous initial stream 2. Gaseous initial streams 2, 3 and 4 as well as, if needed, additional gaseous initial streams different from the gaseous initial stream 1, are merged into a gaseous stream of the working mixture, after which, using this gaseous stream of the working mixture as the working stream, a jet pump is activated, said pump having a nozzle, a mixing section, a diffuser and a suction inlet. Movement of the working stream which is throttled through the nozzle, the mixing section and the diffuser to the input of the first reaction zone A, as well as the suction effect of the suction inlet takes place in the direction of outlet of the stream of products of gaseous mixture A from the first reaction zone A. The pressure drop created in the suction nozzle with splitting of the stream of products of the gaseous mixture A into two partial streams 1 and 2 results in suction of the partial stream 1 of products of the gaseous mixture A, its movement through the diffuser with simultaneous mixture with the working stream on the mixing section and inlet of the formed reaction stream of gaseous mixture A at its inlet point into the first reaction zone A, characterised by that a gaseous initial mixed stream is formed first by merging in random sequence gaseous initial streams 2 and 3, as well as, if needed, additional gaseous initial streams different from gaseous initial streams 1 and 4, and only after that the gaseous initial stream 4 is added to the formed gaseous initial mixed stream to obtain a gaseous mixed working stream. |
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Present invention relates to a carrier with a catalytic coating, production method thereof, use thereof in processes with heterogeneous catalysts, as well as a reactor containing the said catalyst layer. Described is a carrier with a catalytic coating, having at least one porous and cavity-containing catalyst layer, where the cavity consists of random voids with size greater than 5 mcm in at least two dimensions or with cross-sectional area of at least 10 mcm2. Described is a method of producing the said carrier, comprising a) preparing a carrier substrate, b) if needed, depositing an adhesion improving layer, c) spraying a suspension with at least 30% content of solid substance containing a catalytically active substance with average diameter of at least 5 mcm and/or precursor thereof and, if needed, an additional component of a catalytically active layer, and d) if needed, repeating step c) once or more. Described is a rector with a surface intended for coating, having at least one carrier with a catalytic coating described above. Described is use of the carrier in a method for catalytic oxidation of aliphatic compounds, in a method for oxidation of xylene and/or naphthalene to phthalic acid, in a method for oxidative coupling of acetic acid and ethane to form vinyl acetate using oxygen, in a method for catalytic hydrogenation of organic compounds and in a method for converting synthetic gas. |
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Initial mixture 2 of the reaction gas which contains propylene and molecular oxygen, as well as molecular nitrogen and propane as inert gases - diluents, in which molar ratio of molecular oxygen to propylene O2:C3H6≥1, at high temperature is passed through a fixed catalyst bed, the active mass of which is at least one polymetallic oxide containing Mo, Fe and Bi, in which the initial mixture 2 of the reaction gas, per total volume, contains 7-9 vol. % propylene, 9.8-15.5 vol. % molecular oxygen, 10.5-15.5 vol. % propane and 40-60 vol. % molecular nitrogen, provided that the molar ratio V1 of propane contained in the initial mixture 2 of the reaction gas to propylene contained in the initial mixture 2 of the reaction gas is between 1.5 and 2.2, molar ratio V2 of molecular nitrogen contained in the initial mixture 2 of the reaction gas to molecular oxygen contained in the initial mixture 2 of the reaction gas is between 3.5 and 4.5, and molar ratio V3 of molecular oxygen contained in the initial mixture 2 of the reaction gas to propylene contained in the initial mixture 2 of the reaction gas is between 1.4 and 2.14. |
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Method for synthesis of acrolein through oxidation of propylene involves a step for dehydrating glycerine to acrolein in the presence of a propylene-containing gas. The propylene-containing gas is a reaction gas taken from the step for oxidising propylene to acrolein or a gas mixture which is fed into a propylene oxidation reactor. |
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Method of producing acrylic acid Invention relates to an improved method of producing acrylic acid from propylene, involving a first step where propylene is oxidised to acrolein and a second step where acrolein is oxidised to acrylic acid, as well as a step for dehydrating glycerin to acrolein in the presence of a propylene-containing gas. The said step for dehydrating glycerin is carried out before catalytic oxidation of propylene to acrolein in the presence of the supplied propylene-containing gas, or after catalytic oxidation of propylene to acrolein in the presence of a gaseous mixture coming out after oxidation of propylene to acrolein. |
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Mixed oxide catalysts for catalytic olefin oxidation in gas phase and method for preparing thereof Invention refers to mixed oxide catalysts for catalytic oxidation of olefins and methylated aromatic compounds in gas phase, to a method for preparing such catalysts and a method for making aldehydes and carboxylic acids. There are described mixed oxide catalysts of general formula I (Mo12BiaCb(Co+Ni)cDdEeFfGgHh)Ox (I), where C means iron, D means P, E means at least one of elements of the group including Li, K, Na, Rb, Cs, F means Mn, G means at least one of elements of the group including Sm, Gd, La, H means at least one of elements of the group including Si, Al, and a means a number 0 to 5.0, b means a number 0.5 to 5.0, c means a number 2 to 15, d means a number 0.01 to 5.0, e means a number 0.001 to 2, f means a number 0.001 to 5, g means a number 0 to 1.5, h means a number 0 to 800, and h means a number determined by the valence and concentration of the elements differing from oxygen. There is described a method for preparing a catalysts of formula (1), where solutions of the compounds found in mixed oxide catalysts of formula of I metals are mixed; cosediment are prepared; a formed solid substance is recovered, dried, baked and if necessary processed to shape as required. There is also described a method for making aldehydes and acids by air or oxygen oxidation of olefins or methylated aromatic compounds in the inert gas, steam or end reaction gas medium at higher temperatures with using described catalyst of general formula (1). |
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Method of obtaining acrolein or acrylic acid or mixture thereof from propane In accordance with the method A) at least two propane-containing gas supply streams are fed into the first reaction zone A, where at least one of the said streams contains fresh propane, and propane fed into this reaction zone undergoes heterogeneous catalytic dehydrogenation with a fixed bed catalyst, obtaining a propane- and propylene-containing gaseous mixture of products A, B) which is extracted from reaction zone A, in the first separation zone, A is separated from at least a portion of components contained in it, which are different from propane and propylene, and the remaining gaseous mixture of products A' which contains propane and propylene C) is used in the second reaction zone B for supplying at least one oxidation reactor, and propylene contained in the gaseous mixture of products A' in at least one oxidation reactor undergoes heterogeneous catalytic two-step gas-phase partial oxidation with molecular oxygen to acrylic acid or a mixture of acrolein and acrylic acid as an end product, as well as to an excess molecular oxygen-containing gaseous mixture of products B, D) which is extracted from the reaction zone B, in the second separation zone B, the end product contained in it is extracted through absorption or fractional condensation, and at least a portion of the remaining residual gas which contains unconverted propane, molecular oxygen, and also if necessary, unconverted propylene are recycled into the reaction zone A as at least one of two propane-containing supply streams, where the said recycling into the reaction zone A is done along the path of the heterogeneous catalysed dehydrogation of propane in that reaction zone such that, at the point for feeding the recycled gas into reaction zone A at least 5 mol % of propane has already undergone dehydrogenation, where the said propane is fed into this reaction zone with other supply streams, where molar ratio of the propylene contained in the reaction gaseous mixture to molecular hydrogen contained in the said mixture within the reaction zone A does not exceed 10. |
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Invention relates to an improved method of continuous, heterogeneous, catalytic, partial gas-phase oxidation of at least one organic compound selected from a group comprising propene, acrolein, isobutene, methacrolein, isobutene and propane, in an oxidation reactor loaded with a gas mixture which, along with at least one compound to undergo partial oxidation and molecular oxygen as an oxidation agent, includes at least one diluent gas which is essentially inert in conditions of heterogeneous, catalytic, gas-phase partial oxidation, where the source of oxygen and inert gas for the loaded gas mixture is air which is compressed in a compressor beforehand from a low initial pressure value to a high final pressure value, where before entering the compressor, the air undergoes at least one mechanical separation procedure through which particles of solid substance dispersed in the air can be separated. |
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Method of producing acrolein through heterogeneously catalysed oxidation of propene in gaseous phase Present invention relates to a method of producing acrolein through heterogeneously catalysed partial oxidation of propene in a gaseous phase and a catalyst for producing acrolein. A method is described for producing acrolein through heterogeneously catalysed partial oxidation in a gaseous phase, in which the initial gaseous reaction mixture, which contains propene, molecular oxygen and at least one inert gas, where molecular oxygen and propene are in molar ratio of O2:C3H6≥1, as well as carbon dioxide and saturated hydrocarbons together in total amount of at most 15 mol %, is passed through a fixed catalyst bed at high temperature while loading the fixed catalyst bed with propene contained in the gaseous reaction mixture at a rate ≥120 nl/l·h, where the catalysts are in form of annular solid catalysts, the active mass of which is at least one multimetal oxide of general formula I, Mo12WaCobFecBidSieKfOn (I), where a ≥1 to ≤3, b ≥3 to ≤8, c ≥1 to ≤4, d ≥0.5 to ≤1.5, e ≥0 to ≤10, f ≥0 to ≤0.2 and n is a number which is determined by valency and number of elements in formula I which are not oxygen, so that conversion of propene in a single passage is ≥90 mol % and associated selectivity of formation of acrolein is ≥80 mol %. The following mass ratios are also satisfied in the mass of multimetal oxides I: Co/Fe=2 to 3.5 and Co/Mo=0.5 to 0.7. Also described is an annular, solid catalyst, active mass of which is a multimetal oxide of general formula I, under the condition that, the following molar ratios are also satisfied in the mass of multimetal oxide I: Co/Fe=2 to 3.5 and Co/Mo=0.5 to 0.7. |
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Method of producing (meth)acrylic acid or (meth)acrolein Invention relates to improvement of the method of producing (meth)acrylic acid or (meth)acrolein through gas-phase catalytic oxidation of at least one oxidisable substance, chosen from propylene, propane, isobutylene and (meth)acrolein, molecular oxygen or a gas, which contains molecular oxygen, using a multitubular reactor, with such a structure that, there are several reaction tubes, with one (or several) catalytic layer (catalytic layers) in the direction of the axis of the tube, and a coolant can flow outside the said reaction tubes so as to regulate temperature of reaction, in which temperature of the said reaction of gas-phase catalytic oxidation is increased by varying temperature of the coolant at the inlet for regulating temperature of the reaction, while (1) temperature of coolant at the inlet for regulating temperature of the reaction is varied by not more than 2°C for each variation as such, and (2) when variation is done continuously, the time interval from the variation operation, directly preceding the present, is not more than 10 minutes, and, in addition, the difference between the maximum value of peak temperature of reaction of the catalyst layer of the reaction tube and temperature of the coolant at the inlet for regulating temperature of reaction is not less than 20°C. |
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Method of producing (met)acrolein and/or (met)acrylic acid Invention relates to an improved method of producing (met)acrolein and/or (met)acrylic acid through heterogeneous catalytic partial oxidation in gaseous phase, in which a fresh fixed-bed catalyst at 100-600°C in a reactor is loaded with a mixture of loading gas, which along with at least, one C3/C4 organic precursor compound subject to partial oxidation and oxidation with molecular oxygen, contains at least one gas-diluent. The process is carried out after establishing content of the mixture of loading gas at constant conversion of organic precursor compound and at constant content of the mixture of loading gas initially in the input period for 3-10 days with load of 40-80% of higher final load, and then at higher filling load of the catalyst with a mixture of loading gas. In the input period, maximum deviation of conversion of organic precursor compound from arithmetic time-averaged and maximum deviation of the volume ratio of one component of the mixture loading gas, oxidising agent, organic precursor compound and gas-diluent, from the arithmetic time-averaged volume ratio of the corresponding component of the mixture of loading gas should not exceed ±10% of the corresponding arithmetic mean value. |
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Present invention relates to an improved method of monitoring and/or controlling the process of producing (meth)acrolein and/or (meth)acrylic acid through partial oxidation in a gas of C3- and/or C4- precursor compounds in the presence of heterogeneous catalyst in form of particles, in a reactor with two or more vertical thermo-plates, placed parallel each other, forming gaps between them. A heterogeneous catalyst in form of particles is put in the gaps. The gaseous reaction mixture is passed through the gaps. The controlled and/monitored value chosen is one or several temperature values, which are measured in one or several gaps, in one or several points of measurement, which are distributed along the height of each gap. |
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Present invention relates to an improved method of producing at least one product of partial oxidation and/or ammoxidation of a hydrocarbon, chosen from a group containing acrolein, acrylic acid, methacrolen, methacrylic acid, acrylonitrile and methacrylonitrile. At least one saturated hydrocarbon is subjected to heterogeneous catalysed dehydrogenation in a gas phase, obtaining a gas mixture, containing at least one partially dehydrogenated hydrocarbon. Components of the gas mixture except saturated hydrocarbon and partially dehydrogenated hydrocarbon are left in the mixture. Alternatively, the extra gas mixture obtained is partially or completely separated, and the gas mixture and/or extra gas mixture are used for obtaining another gas mixture, containing molecular oxygen and/or molecular oxygen and ammonia. This gas mixture is subjected to at least single heterogeneous catalysed partial oxidation and/or ammoxidation of at least one partially dehydrogenated hydrocarbon contained in the gas mixture and/or extra gas mixture. The gas mixture, extra gas mixture and/or the other gas mixture, before at least one partial heterogeneous catalysed oxidation and/or ammoxidation, are subjected to at least a single mechanical separation, aimed at separating particles of solid substance contained in the above mentioned gas mixtures. |
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Method of recovering (meth)acrolein or (meth)acrylic acid and installation intended for this purpose Invention relates to improved method of recovering (meth)acrolein or (meth)acrylic acid, including stage of cooling of gaseous reaction mixture containing (meth)acrolein or (meth)acrylic acid obtained by reaction of catalytic oxidation in vapour phase of one or both reagents selected from (A) propane, propylene or isobutylene and (B) (meth)acrolein, with molecular oxygen or gas, containing molecular oxygen, to temperature 140-250°C; contacting of said gaseous reaction mixture with solvent, whose temperature is 20-50°C, in recovery installation for recovering (meth)acrolein or (meth)acrylic acid in solvent, where said recovery installation contains contact zone, where gaseous reaction mixture contacts with solvent, having transversal section of round form and many devices of gaseous reaction mixture supply for supplying gaseous reaction mixture into contact zone, devices of gaseous reaction mixture supply are installed in contact zone at the same height directed towards contact zone centre, gaseous reaction mixture is supplied to contact zone from devices of gaseous reaction mixture supply and is subjected to collision straight in one point of contact zone, and recovery installation does not have device which prevents direct collision of gaseous mixture supplied from devices of gaseous reaction mixture supply. Invention also relates to recovery installation for recovering (meth)acrolein or (meth)acrylic acid. |
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Method of obtaining (meth)acrylic acid or (meth)acrolein Invention relates to improved method of obtaining (meth)acrylic acid or (meth)acrolein, which includes process of catalytic gas-phase oxidation for obtaining (met)acrylic acid or (meth)acrolein by supplying propylene, propane or isobutylene and gas, containing molecular oxygen, into reactor, filled with catalyst, which contains composition of metal oxides, including Mo, where gas, containing molecular oxygen, is continuously supplied from outside on catalyst both during installation operation, and during stoppage of catalytic gas-phase oxidation process. |
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Present invention pertains to the method of prolonged heterogeneous catalysed partial oxidation of propene to acrolein in gaseous phase. The initial reaction gaseous mixture, containing propene, molecular oxygen and at least one inert gas-diluting agent, is passed through a fixed catalyst bed at high temperature. The catalysts are such that, their active mass contains at least, one multi-metal oxide, which contains molybdenum and/or tungsten, as well as at least, one of the elements bismuth, tellurium, antimony, tin, and copper. The temperature of the catalyst bed is increased for a period of time. Partial oxidation in gaseous phase is interrupted at least, once in a calendar year, and at 250-550°C temperature of the fixed catalyst bed a gas mixture, containing molecular oxygen, inert gas and, if necessary, water vapour, is passed through the fixed catalyst bed. |
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Method of producing (met)acrylic acid or (met)acrolein Present invention pertains to improvement of the method of producing (met)acrylic acid or (met)acrolein using a multi-pipe reactor with a fixed bed. The reactor has several pipes, with at least one catalyst bed in the direction of the axis of the pipe. A heat carrier can regulate temperature outside the flow of the reaction pipe. In the reaction pipes, there is gas-phase catalytic oxidation of at least one type of oxidisable substance, propylene, propane, isobutylene and (met)acrolein by molecular oxygen or a gas, containing molecular oxygen. At the beginning of the process, the difference between the coolant temperature and the peak temperature of the catalyst is set in the interval 20-80°C, and during the process, peak temperature T(°C) of the catalyst in the direction of the axis of the pipe satisfies equation 1, given below: (equation 1), where L, T0, X and X0 stand for length of the reaction pipe, peak temperature of the catalyst in the direction of the axis of the pipe at the beginning of the process, the length up to the position which gives the peak temperature T at the input of the reaction pipe, and the length to the position which gives the peak temperature T0 at the input of the reaction pipe, respectively. |
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Method of obtaining, at least, one product of partial oxidation and/or ammoxidising of propylene Present invention pertains to perfection of the method of obtaining at least, one product of partial oxidation and/or ammoxidising of propylene, chosen from a group, comprising propylene oxide, acrolein, acrylic acid and acrylonitrile. The starting material is raw propane. a) At the first stage, raw propane, in the presence and/or absence of oxygen, is subjected to homogenous and/or heterogeneous catalysed dehydrogenation and/or oxydehydrogenation. Gas mixture 1, containing propane and propylene is obtained. b) If necessary, a certain quantity of the other components in gas mixture 1, obtained in the first stage, besides propane and propylene, such as hydrogen and carbon monoxide is separated and/or converted to other compounds, such as water and carbon dioxide. From gas mixture 1, gas mixture 1' is obtained, containing propane and propylene, as well as other compounds, besides oxygen, propane and propylene. c) At the third stage, gas mixture 1 and/or gas mixture 1' as a component, containing molecular oxygen, of gas mixture 2, is subjected to heterogeneous catalysed partial gas-phase oxidation and/or propylene, contained in gas mixture 1 and/or gas mixture 1', undergoes partial gas-phase ammoxidising. Content of butane-1 in gas mixture 2 is ≤1 vol.%. The method increases output of desired products and efficiency of the process. |
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Method of obtaining at least one product of partial propylene oxidation and/or ammoxidation Invention concerns improved method of obtaining at least one product of partial propylene oxidation and/or ammoxidation, propylene selected out of group including propyleneoxide, acrolein, acrylic acid and acrylnitryl, where source substance is propane. Method involves a) at the first stage, homogeneous and/or heterogeneous catalysed dehydration and/or oxydehydration of raw propane in the presence and/or in the absence of oxygen, to obtain gas mix containing propane and propylene; and b) if required, separation of part gas mix 1 obtained at the first stage and its components other than propane and propylene, such as hydrogen, carbon monoxide, or transformation of this part in the other compounds, such as water, carbon dioxide, so that gas mix 1' containing propane and propylene and compounds other than oxygen, propane and propylene is obtained from gas mix 1; and at least one more stage c) heterogeneous catalysed ammoxidation and/or partial gas phase ammoxidation of propylene containing in gas mix 1 and/or gas mix 1' in gas mix 1 or gas mix 1' containing molecular oxygen of gas mix 2, where total C4-hydrocarbon content in gas mix 2 is < 3 volume %. |
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Method of catalytic oxidation in vapour phase implemented in multiple-tubular reactor Invention concerns improved method of catalytic oxidation in vapour phase which supplies effective removing of reactionary heat, excludes hot spot formation, and supplies effective receipt of base product. Method of catalytic oxidation is disclosed in the vapour phase (a) of propylene, propane or isobutene by the instrumentality of molecular oxygen for receiving (meth)acrolein, and/or oxidation (b) of (meth)acrolein by molecular oxygen for receiving (meth)acryl acid, by the instrumentality of multiple-tubular reactor, contained: cylindrical reactor vessel, outfitted by initial material supply inlet hole and discharge hole for product, variety of reactor coolant pipes, located around the cylindrical reactor vessel and used for insertion the heat carrier into cylindrical reactor vessel or for removing the heat carrier from it, circulator for connection of variety loop pipeline to each other, variety of reaction tube, mounted by the instrumentality of tube reactor lattices, with catalyst. Also multiple-tubular reactor contains: variety of partitions, located lengthways of reaction tubes and used for changing heat carrier direction, inserted into reactor vessel. According to this heat carrier coolant flow is analysed and there are defined zones in reactor which have heat-transfer coefficient of heat carrier less than 1000 W/(m2·K); also reaction of catalytic oxidation is averted in the vapour phase in mentioned zones of reactor and reaction of catalytic oxidation is implemented in the vapour phase in reactor. |
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Method for preparing acrolein or acrylic acid or their mixture from propane Invention relates to an improved method for synthesis of acrolein or acrylic acid or their mixture. Method involves at step (A) propane is subjected for partial heterogenous catalyzed dehydrogenation in gaseous phase to form a gaseous mixture A of product comprising molecular hydrogen, propylene, unconverted propane and components distinct from propane and propene, and then from a gaseous mixture of product from step (A) distinct from propane and propylene at least partial amount of molecular hydrogen is isolated and a mixture obtained after this isolation is used as a gaseous mixture A' at the second step (B) for loading at least into one oxidation reactor and in at least one oxidation reaction propylene is subjected for selective heterogenous catalyzed gas-phase partial oxidation with molecular oxygen to yield as the end product of gaseous mixture B containing acrolein or acrylic acid, or their mixture, and the third (C) wherein in limits of partial oxidation of propylene at step (B) of gaseous mixture B acrolein or acrylic acid or their mixtures as the end product are separated and at least unconverted propane containing in gaseous mixture at step (B) is recovered to the dehydrogenation step (A) wherein in limits of partial oxidation of propylene at step (B) molecular nitrogen is used as additional diluting gas. Method provides significant decreasing of by-side products. |
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Invention relates to catalytic oxidation of organic substances in vapor phase in reaction tubes of multitube reactor of heat-exchange type with an immobile catalyst layer, and to a method for synthesis of (meth)acrolein or (meth)acrylic acid in these reactors. Method for catalytic oxidation in vapor phase for preparing the reaction product is carried out in multitube reactor with a great number of reaction tubes by feeding the parent gaseous raw and oxygen-containing gas into reaction tubes filled with a solid catalyst. Method involves measurement and regulation of pressure loss in reaction tubes after filing a catalyst by such manner that pressure loss in corresponding tubes will be in limits ±20% of average pressure loss value of reaction tubes. If necessary, inert substance is filled into inlet part of reaction tubes or removal of filled catalyst and repeated filling catalyst for reaction tube showing pressure loss value less an average pressure loss for reaction tube or a reaction tube showing pressure loss value above an average pressure loss value. Method for synthesis of (meth)acrolein or (meth)acrylic acid is carried out in indicated multitube reactor by feeding propane, propylene or isobutylene and molecular oxygen into reaction tubes filled with a catalyst with regulation pressure loss values as said above. For regulation of filling an inert substance is used. Also, method involves prediction of reaction states into reaction tubes by measurement of temperature of catalytic layer of reaction tubes or by imitation analysis of liquid state of a heat-carrier circulating on the outside of reaction tubes with heat of material into reaction tubes. Then method involves assay of conditions in filling catalyst into tubes in correspondence with prognosis results and heterogeneity of reaction states among reaction tubes is removed. Invention provides enhancing yield of the end product and increasing the catalyst life work based on retaining its mechanical strength by prevention its grinding during charge and removal of decomposed catalyst from reaction tubes. |
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The invention provides, that the multitubular reactor consists of the set of the reaction tubes containing the placed in them catalyst, and the housing supplied with the reaction tubes located inside it, in which the heat-carrier passing in the inter-tubular space is introduced. The reaction tubes are selected from the tubes having the equal nominal outer diameter and the wall thickness. The tolerance of the outer diameter is selected from ±0.62 % and the tolerance of the wall thickness - from ±19 % up to -0 %. The tolerance of the outer diameter - from ±0,56 % and the tolerance of the wall thickness - from ±17 % up to -0 %. The method of the catalytic oxidation in the vapor-phase consists in the usage of the multitubular reactor, circulation of the heat carrier in the reaction tubes inter-tube space and feeding of the source gas into the reaction tubes filled with the catalyst, for production of the gaseous product of the reaction, including the determination of the performance specification on the catalyst packing into the reactionary tubes. The multitubular reactor additionally includes the deflectors connected with the reaction tubes through the positions of the joints, for the change of the directions of the passage of the heat-carrier medium introduced into the housing. It is possible to use the heat-exchange reactor with the immovable layer of the catalytic agent additionally containing the set of the reaction tubes, in the inter-tube space of which the heat carrier is passing. The specification is determined by means of provision in one of the reaction tube of at least two catalytic layers with the different specifications of packaging of the catalyst and the change of the lengths of the reaction zones of the reaction tube for relocation of the places of the maximal temperatures of the catalytic layer along the reaction tube or formation of the layer containing the thinning agent in the reaction tube disposed in the places of the joints for determination of the specification on the catalyst packaging to provide the control of the reaction temperature in the places of joints. The version of realization the method of the catalytic oxidation use oxidation of propylene, propane or isobutylene and-or (metha) acrolein by the catalytic oxidation in the vapor phase with the help of the gas containing the molecular oxygen, for production of the (metha)acrolein and-or the(metha)acrylic acid including the packaging of the Mo-Bi catalyst and-or Sb-Mo catalyst in the reaction tubes so, that activity is increasing from the inlet of the process gas into the reaction tubes up to the outlet of the process gas from the reaction tubes and ensures the possibility for the heat-transfer medium and the process gas to pass through as the counter current. The multitubular reactor used in the method contains: the cylindrical housing, the set of the annular tubes, the circulation device, the set of the reaction tubes limited by the set of the of tube plates of the reactor and containing the catalyst, and the set of the deflectors. According to the method of the start-up of the shell-and-tube reactor having the circulating system of the heat-exchange medium, which is the solid substance at the room temperature, the heating of reaction tubes takes place by introduction of the gas with the temperature from 100 up to 400°С into the inter-tube space of the reaction tubes and circulation of the heated heat carrier. The shell-and-tube reactor has the reaction tubes and the inlet and the outlet for the liquid passing in the inter-tube space of the reaction tubes for withdrawal of the heat formed inside the reaction tubes. Due to the method of the catalytic oxidation the invention ensures prevention of formation of the local overheating and the clogging of the reaction tubes, the increased outlet of the gaseous product of the reaction and the increased service life of the catalyst and also the stable operation of the multi-tube reactor for the long time. |
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Method for preparing acrolein and/or acrylic acid Invention relates to a method for synthesis of acrolein and/or acrylic acid from propane and/or propene. Method involves the following steps: (a) isolating propane and/or propene from gaseous mixture A containing propane and/or propene by their absorption with adsorbent; (b) isolating propane and/or propene from adsorbent to form gas B containing propane and/or propene, and (c) using gas B obtained in stage (b) for oxidation of propane and/or propene to acrolein and/or acrylic acid wherein the heterogeneous catalytic dehydrogenation of propane without feeding oxygen is not carried out. Method shows economy and maximal exploitation period of used catalyst without its regeneration. |
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Method for production of (meth)acrolein and (meth)acrlic acid compounds Claimed method includes feeding of raw gas mixture through pipeline from raw material mixer into oxidation reactor and catalytic oxidation of raw mixture in vapor phase to produce (meth)acrolein or (meth)acrylic acid. Said pipeline is heated and/or maintained in heated state and temperature of gas mixture fed into oxidation reactor is by 5-250C higher then condensation temperature of raw gas mixture. |
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Method for preparing acrylic acid Invention relates to the improved method for preparing acrylic acid and selective oxidation of propylene to acrolein. Method involves carrying out reaction of propylene with oxygen in the first zone reaction with the first catalyst corresponding to the following formula: AaBbCcCadFeeBifMo12Ox wherein A means Li, Na, K, Rb and Cs and their mixtures also; B means Mg, Sr, Mn, Ni, Co and Zn and their mixtures also; C means Ce, Cr, Al, Sb, P, Ge, Sn, Cu, V and W and their mixtures also wherein a = 0.01-1.0; b and e = 1.0-10; c = 0-5.0 but preferably 0.05-5.0; d and f = 0.05-5.0; x represents a number determined by valence of other presenting elements. Reaction is carried out at enhanced temperature providing preparing acrylic acid and acrolein and the following addition of acrolein from the first reaction zone to the second reaction zone containing the second catalyst used for conversion of acrolein to acrylic acid. Method provides high conversion of propylene to acrylic acid and acrolein. |
Another patent 2551185.