Catalytic composition for carbonylation
(57) Abstract:The carbonylation catalyst used for the carbonylation of methanol to acetic acid, acetic anhydride, or both, contains a polymeric carrier (substrate) having a lateral pyrrolidinone groups, which are particles of rhodium. Other polymeric carriers, capable of withstanding the temperature of the carbonylation of at least 150oC, are considered for the carbonylation reaction in which it is assumed the content of rhodium in the reaction medium than 500 parts per million 7 C.p. f-crystals, 1 table. The invention relates to a new catalyst that is used for carbonylation of methanol to acetic acid carbonylation of methyl acetate to acetic anhydride, or both. The invention also relates to a method for carbonylation of lower alcohols, esters or ethers to carboxylic acids, anhydrides, acids, or both in the presence registeruser catalyst.Among the modern methods of synthesizing acetic acid is one of the most used industrial methods is catalyzed by a rhodium carbonylation of methanol with carbon monoxide (U.S. patent 3769329 issued Pay the catalyst may be used dissolved or otherwise dispersed in a liquid medium, or deposited on a solid support (substrate). In the industrial production of the catalyst is used in a homogeneous reaction system, in which the rhodium catalyst dissolved in the reaction solvent, which is usually acetic acid. Homogeneous catalytic system also includes galogensoderjasimi promoter catalyst represented idestam the stands. The reaction is carried out under continuous bubbling gaseous carbon monoxide through the liquid reaction medium.In the patent Polika indicates that the liquid reaction medium may include any solvent compatible with the catalyst system, and which may contain, for example, pure alcohol, which is reactive, and mix it with the final product of the desired carboxylic acid and/or esters of these two compounds. The preferred solvent and liquid reaction medium of this method is the most desired carboxylic acid, e.g. acetic acid, when methanol carbanilide to obtain acetic acid.In the patent Polika also describes that the addition of water increases the reaction rate of carbonylation of the alcohol to the carboxylic sour is indicated at Polika and others, uses 14 - 15 wt.% water in the reaction medium. It is characterized as "wet" method carbonylation. Unfortunately, regenerative acetic acid in water or substantially anhydrous form of such significant amounts of water involves significant energy consumption at the stage of distillation and/or additional stages of purification, such as by solvent extraction, and also requires a large amount of equipment cleaning method compared with that used for the purification of carboxylic acids containing much smaller amounts of water. Thus, while the performance of the reactor by acetic acid is highly effective at high concentrations of water in the reactor, the performance is usually limited by the ability to remove water from the product acetic acid.Improvement in abounding ways Monsanto carbonylation of alcohol to carboxylic acid having one carbon atom more than the alcohol, in the presence of a rhodium catalyst developed by Hoechst Celanese and considered jointly designed the U.S. patent N 5001259, issued March 19, 1991, and N 5026908, issued on 25 June 1991, and in a pending application U.S. N 61 the th environment, containing methyl acetate, methylguanosine, especially methyliodide, and rhodium is present in a catalytically effective concentration.The invention is mainly that the catalytic stability and performance of the carbonylation reactor can be maintained at a surprisingly high level, even at low water concentrations, i.e. below 14 wt.%, and even at 10 wt.% and significantly less in the reaction medium (despite the General industry practice to maintain the concentration of water at approximately 14 - 15 wt.%). The way Hoechst Celanese characterized as "dry" method carbonylation and provides significantly better performance in comparison with the wet method, since the performance of the reactor is maintained at the level of abounding fashion, and at the same time regenerative dry acid product is much easier (i.e. less energy consumption, less equipment, less use of rhodium) due to the low water content. These results are achieved while maintaining in the reaction medium, along with a catalytically effective amount of rhodium at least a limited concentration of water, methyl acetate and under the conditions, the organic iodide. Ion iodide is present in the form of simple salts, and lithium iodide is preferred. Concentrations of acetate and iodide salts are important parameters affecting the rate of carbonylation of methanol upon receipt of acetic acid, especially at low concentrations of water in the reactor. When using relatively high concentrations of acetate and iodide salts get an amazing level of catalytic stability and performance of the reactor, even when the liquid reaction medium contains water in concentrations up to about 0.1 wt.%, such a low that, generally speaking, it can be defined as "the limited concentration of water. Additionally, the reaction medium improves the stability of the rhodium catalyst, i.e., resistance to deposition of the catalyst, especially during the production stage-regenerating method, where distillation to extract the product acetic acid is committed to the removal of the catalyst by carbon monoxide, which is supported in the reactor environment is a ligand with a stabilizing effect with respect to the rhodium. U.S. patent N 5001259 and 5026908 and pending application U.S. N 615846 are presented as links.Despite the speed of production of acetic acid, this method has still some drawbacks. For example, because the water content in the reaction mixture decreases, the instability and, thus, the precipitation of the rhodium catalyst is increased. Accordingly, the number liiiiiive stabilizer, which should be added increases. It was further established that the product is acetic acid, which is formed, contains tiny amounts of impurities that can degrade the quality of the product acetic acid, as determined by time permanganate. Subsequent purification of the product acetic acid helps to remove impurities, but such processes only add additional costs to the method and products.As an alternative used the serial homogeneous catalytic systems, attempts have been made to use for carbonylation of methanol to acetic acid heterogeneous rhodium catalyst. The advantages of this catalytic system is easy separation of rhodium from the reaction products, as well as the desire to prevent settling or falling of rhodium from realizando system, as a result of the homogeneous catalytic system. Reducing the loss of rhodium catalyst by deposition and/or is and whether such attempts were very successful, and it is unknown whether any industrial application that uses heterogeneous catalytic system catalyzed by the rhodium carbonyliron of methanol to acetic acid.Examples of the use of heterogeneous catalysts include European patent 277824 published on 10 August 1988 and transferred to the firm Reily Jar and Chemical Corp., which describes the carbonylation of methanol to acetic acid using a rhodium deposited on a heterogeneous polymeric carrier (substrate), which contains salt(4 - and 2-vinylpyridine)type copolymers. In particular, Reilex - copolymers made in accordance with this patent are preferred and include a pyridine ring, attached directly at 2 - or 4-positions to the main chain of the polymer, which, in turn, made a small amount of divinylbenzene. For the reaction, probably copolymer or N-oxide copolymer quaternized alkylhalogenide, such as methyliodide, and subjected to reaction with rhodium salt. In the European patent 277824 describes more than 6-fold increase in catalytic activity compared to the described and calculated values for homogeneous way Monsanto. Orascom patent shows roughly comparable activity when using a heterogeneous catalyst in relation to the wet method Monsanto but 6-fold increases, as expected, was not reproduced.Early attempts to obtain a heterogeneous catalyst for catalyzed by rhodium carbonylation of methanol to acetic acid include such as work Jarrell and gates, Journal of Catalysis, 40, 255 - 267, 1975, where as the carrier of rhodium for both liquid-phase and gas-phase reactions is a styrene-divinylbenzene containing diphenylphosphino group. Similarly, the work of Weber, Chats Drenar, Journal of Molecukar Catalysis, 3, 1977/78, 1 - 9, also describes bifunctional polymer for rhodium catalyzed carbonylation reaction of methanol. The polymer was slightly cross-linked polystyrene containing attached rhodium complexes, and also contains the attached group, similar to pentachlorothiophenol, which serve both for coordination compounds of rhodium with the polymer, and for oxidative addition to rhodium at a stage similar to stage comprising rhodium and a soluble promoter in the reaction in solution. Seemed that the associated promoter sets so strong coordination bond with rhodium that the problems of separation, corrosion and loss of expensive rhodium can be facilitated. However, it was set"ptx2">In the work of Drago and others, Jnorg. Chem., 20, 641 - 644, 1981 describes the possibility of applying rhodium compounds on ion resin, such as Dowex 1-XB, Bio-Rex 9 or possible a copolymer of styrene and 4-vinylpyridine) - derivatives, alkilirovanny methyliodide. This article does not include experimental results of the use of the catalyst based on the proposed polyvinylpyridine derived. Based on the above examples it is concluded that their ion media rhodium catalyst is approximately equivalent catalytic activity of the homogeneous complex, and that the leaching of the catalyst can be minimized by appropriate choice of solvent and the high ratio of resin with rhodium. All of these tests are only used low temperature (120oC and below) and a pressure of 80 lb/inch2. In addition, it was assumed that doubling the amount of catalyst on the carrier (and thus, the present rhodium) will give a corresponding doubling of the reaction rate, and effective way to carry out the reaction can be achieved by maintaining a high concentration of catalyst, in particular, in a flow system.In a recently issued U.S. patent N 4328125 Drago other, anal/inch2up to 160 lb/in2in one example, the carbonylation of methanol with heterogeneous rhodium catalyst. These conditions, and in particular, low temperatures, are entirely unsuitable for any industrial use in the production of acetic acid and, especially, far from the conditions of the way Monsanto temperature, which varies in the range of about 170 - 200oC. the reaction rate is so low compared to homogeneous way, that in order to have a hope of getting industrial products, will require large reactors with increased cost, big time and end low outputs in terms of volume and time. These average conditions Drago and others, however, are required for most ionoobmennyh resins, which are unstable, for example, when supported elevated temperatures above 130oC and approximately 170oC. Thus, in order to be commercially viable, the stabilizer must be stable under the conditions of the carbonylation at least at 170oC and does not form significant amounts of the degradation products at least for about 6 months. In the patent it is concluded that large con the reaction in the method, preferably performed at these low temperatures less corrosive conditions than methods that use traditional homogeneous catalysts. Although the patent Drago and others mentioned in the same moment polyvinylpyridine as such, but examples of their production and use. Instead, the examples are limited to one example associated with polystyrene pyridine and commercially available aminoaldehyde resins identified as Amfer-lite IR A-400 and Doex I-XB, which are used as catalysts gereformeerde olefins.There are additional examples of the use of polymeric carriers for rhodium catalysts used in carbonyliron of methanol to acetic acid. Patent USSR N 1108088 uses a complex of rhodium with polyethylene oxide and alkylhalogenide promoter for the manufacture of acetic acid by carbonyliron methanol. In the work of yuan and others, Chinese Journal of Polymer Jcience, T. 7, No. 3, 1989, S. 219 methanol carbanilide to acetic acid in the complexation of rhodium with etilenvinilatsetata copolymers of 2-vinylpyridine) - derivatives and methyl acrylate. Rhodium also forms complexes with other polymeric substrates for hydroformylation of the olefin to the Alda is a fibrous substrate.U.S. patent N 4667053 considers carbonylation of olefins to ethers using a heterogeneous palladium-copper catalyst on the polymer carrier, which can include polyvinylpyrrolidone, polyvinylpyridine and pyridine copolymers with styrene.Despite the fact that catalyzed by rhodium carbonylation of methanol to acetic acid offers a variety of heterogeneous catalytic systems, it is currently unknown that somewhere there are some industrial reactors using such technology. One reason for this is that, as was established, heterogeneous catalytic systems are relatively unstable. Known polymeric catalytic systems have problems of chemical, thermal and physical stability in the industrial environment the implementation of the carbonylation reaction.Elevated levels of rhodium are known to provide high catalytic activity and high productivity of the reactor upon receipt of acetic acid, and the levels of rhodium to 1000 parts per million are described in the above General purpose of the U.S. patent N 5001259 and N 5026908. However, the application of the x arguments for limiting levels of rhodium in the reactor. For example, an increased amount of rhodium leads to the problem of sedimentation, although the concentration of water in the reactor refers to the low concentrations, the problem of deposition at levels rhodium 500 parts per million and above are significantly more pronounced. In dry conditions a significant number jednoosobowego stabilizer, usually 10% or higher, is required to control the deposition of rhodium. In some way elevated levels of rhodium also lead to problems of sedimentation, and even if such problems can be alleviated, the increased output of the reactor can not be adapted to the flow going down, where the water must be removed from the product acetic acid. Heterogeneous systems are described in European patent 277824 above, only involving the use of levels of rhodium below 500 parts per million relative to the reaction system. It is known that when carbonyliron of acetate to obtain acetic anhydride are used, the levels of the rhodium catalyst is significantly higher than 1000 parts per million However, for the stabilization of a homogeneous rhodium catalyst requires more than 10% of the stabilizer, which is usually the monodentate phosphine ligand type. Usually neobhodimosti, as well as the cost of cleaning.Thus, the main aim of the invention is a method catalyzed by rhodium carbonylation of methanol to acetic acid carbonylation of methyl acetate to acetic anhydride or the joint production, in which (way) reactivity of the catalyst can be significantly improved without the need for significant levels of stabilizing salts, and which may still be overall performance.It is now established that the carbonylation of alcohols, esters, ethers to acids, anhydrides, or both can be successfully carried out using the polymer carrier (substrate) of the catalyst, which is securely connected with the rhodium catalyst. Polymer carrier (substrate) can be liquid, solid, homogeneous or heterogeneous with respect to the reaction medium. Polymeric carriers are able to provide a stable concentration of rhodium in amounts of more than 500 parts per million in the reaction medium and thus to link the rhodium that in conditions of low water carbonylation number iodide stabilizer can be significantly reduced. The specific catalyst contains equipment catalyst is slightly crosslinked polyvinylpyrrolidone, which is filled with rhodium salt or in the reactor, or as a pre-obtained material.When using polymeric catalyst of the invention in dry conditions, as set out in previous U.S. patent N 5001259, industrial way will realize the advantages of lower energy consumption, smaller working equipment and low output of by-products (i.e., organic iodides, CARBONYLS and unsaturated organics). The polymeric catalyst of the invention holds firmly rhodium on a carrier (substrate), and thus lower losses of rhodium lead to less consumption of rhodium. At the same time, since the polymer carrier can firmly rhodium, a higher content of rhodium can be effective, greatly improving the performance of the reactor.At that time, as the preferred catalyst uses polyvinylpyrrolidones media (substrate), the invention in its broadest aspect is suitable for use rhodium catalysts on polymer carrier for low water carbonylation of methanol to acetic acid, where the polymeric carrier (substrate) contains any atom that has a lone pair of electrons and can clicks the effect carbonylation. Thus, any polymer carrier (substrate), which contains a nitrogen atom, phosphorus or sulfur in its main chain, and, more preferably, in the side groups, and has adequate thermal and chemical resistance to the industrial implementation of the carbonyl can be used for low water carbonylation and presumably will give all of the above advantages.The invention relates primarily to improved polymeric catalyst for the carbonylation of methanol or methyl acetate to obtain acetic acid, as well as in anhydrous conditions to obtain acetic anhydride, or with the joint receipt of acetic acid and acetic anhydride. The catalyst of the invention contains a polymeric carrier (substrate), which has numerous sections, each of which may be connected in any way with alkylation and particles of rhodium. Polymer carrier (substrate) may be liquid or solid and either soluble or insoluble in the reaction medium. Thus, the polymeric carrier (substrate) can be homogeneous liquid reaction medium or contains heterogeneous particles or in the form of a liquid, such as Ki-resistant and heat-resistant under normal working conditions carbonyl in particular, when the supported temperature 150oC and above and, preferably, with 175 - 225oC. For industrial applications, the polymer must be stable at the above elevated temperatures for at least 6 months and most preferably at least 1 year. Polymer carrier (substrate) must be able to effectively bind enough of rhodium with providing more than 500 parts per million of rhodium in the reaction medium and/or enough to bind rhodium to reduce the amount used odesolver stabilizer in dry conditions to less than 10 wt.%, in a time when content is provided rhodium 300 to 500 parts per millionPreferred polymeric carrier is insoluble polymer having side pyrrolidinone groups, which are particles of rhodium. The most preferred catalyst is polyvinylpyrrolidone, which is stitched and filled with rhodium as described above. Stitching can be done using caustic catalyst, as described in U.S. patent N 2938017, or when using a cross-linking agent, such as described in German patent N 2059484. These links are provided here for comparison. This predprodej. Both the reaction is easily carried out by standard methods and using known components for such reactions. For example, it is preferable to simply add the amount of insoluble polymer in the form of powder or beads, to the fact that the opposite is homogeneous environment for the carbonylation reaction of methanol. This environment carbonylation reaction include methanol and/or methyl acetate, acetic acid and a small amount of water in the pressure vessel simultaneously with the compound of rhodium and iodide promoter. The preferred promoter receipt of acetic acid and derivatives is methyliodide. Triiodide rhodium and rhodium acetate is selected compounds of rhodium, although known and are available other appropriate connections.In addition to polyvinylpyrrolidone polymers, as described above, as a catalyst carrier metal rhodium can be used with other polymers, which found, in particular, the use of heterogeneous carbonylation of methanol to acetic acid, acetic anhydride or the joint production of these materials with high content of rhodium, i.e., > 500 parts per million, and/or milovidnyh conditions studied is 4, and which are available under the trademark Reillex om Riley Jar and Chemical Corporarion of Jndiana Indiana Polis. Further, polymer systems that contain any of the group of phosphorus, sulfur or nitrogen, which can form complexes with alkylhalogenide, such as methyliodide and rhodium salt may be used as the polymer carrier heterogeneous catalyst and found use in the desired carbonyliron. in particular, in dry conditions carbonylation. These groups are preferably contained in the side chains to the main chain of the polymer, but can be part of the main circuit. In this respect, using any suitable polymer which can form a complex with alkylhalogenide and rhodium, and which is soluble (homogeneous) or insoluble (heterogeneous) in the reaction mixture when the insolubility comes from the molecular weight, crosslinking chemical, thermal or radiation means or some other means or methods. In addition, such polymers should be stable at elevated temperatures, which is industrial carbonylation reaction, as described previously. Another important characteristic is the fact that the polymeric carrier is a metal rhodium plated with required conditions of concentration to ensure a favorable catalytic activity. Examples of other polymeric carriers include polymeric carriers, which contain diaryl - or dialkylphosphinate, alkyl - or arylsulfonyl and sulfoxidov in the side chain to the heat-resistant vinyl main chain.As noted above, polymeric carriers used in the invention may be heterogeneous, but such catalysts may also be soluble or homogeneous in the reaction medium carbonylation. So, polymeric carriers, which are in the liquid state, can be used as carriers of the catalyst in the carbonylation reactions of the invention. Such liquid polymers usually do not have a high degree of crosslinking or have low molecular weight. Although homogeneous polymeric catalysts do not have the advantages of heterogeneous media, because the release of the rhodium catalyst from the reaction medium by physical means can not be easily achieved, polymeric media given the large number of available sites connections will be able to bind a sufficient amount of rhodium to provide a much larger content of rhodium in the reaction medium compared to currently used systems. Thus, it is expected that when erogeny systems homogeneous polymer systems must withstand long-term operating conditions of the carbonylation reaction, including maintaining the temperature above 150oC. in Addition to the requirement that such polymers should be stable at elevated temperatures for sufficient periods of time, no other requirements with respect to the polymer carrier, except that such polymers must be able to connect or form a complex or other type of interfacing with alkylidene promoter and catalyst particles of rhodium. It is assumed that these homogeneous polymeric catalysts can be used either wet or dry carbonylation reactions. It is assumed that similar heterogeneous system is homogeneous polymeric carriers provide the content of rhodium in the reaction medium than 500 parts per million and/or dry carbonyliron reduce the number ideologi stabilizer, which you must enter to stabilize the rhodium particles.Rhodium carbonylation catalyst on the polymer carrier of the invention can be used for carbonylation of methanol under standard conditions water carbonylation, as is done in practice in industry in accordance with U.S. patent N 3769329 in the name of the girl and other CatalystsThe use of water-intensive technology with polymeric catalyst has some advantages listed above. Again, these advantages include the fact that small amounts of water greatly reduces the amount of equipment, energy consumption and, accordingly, the value provided in the separation of the product from the reaction of water. Moreover, due to the fact that the polymeric carrier binds rhodium with polymer matrix, rhodium is not deposited and flaking on the reactor, as in the homogeneous system. In this regard, the number limiting stabilizer, which is used in dry way to prevent deposition of rhodium, can be significantly reduced or completely eliminated. With regard to the stability of the polymer for binding to the rhodium catalyst, the content of rhodium can be increased, and, thus, increased catalytic activity in the reactor. In addition, when using heterogeneous polymeric catalyst, recycling and regenerative catalyst is easily accomplished using known technology Department, such as simple filtration of the solid catalyst from the liquid reagents or decantation of the liquid catalyst from reaction the present invention, requires a liquid reaction medium, which may include any compatible solvent, such as pure alcohols or supplied alcohol mixture and/or the desired carboxylic acid and/or esters of these two compounds. The preferred solvent and liquid reaction medium for shallow way carbonylation contain the product carboxylic acid. So, for carbonylation of methanol to acetic acid is the preferred solvent is acetic acid.In the production of carboxylic acids by dry method provided the concentration of water is less than 14 wt.%, most preferably, 1 to 6 wt. %, relative to the liquid reaction medium. The concentration of water is less than 1 wt.% is used, in particular, to obtain anhydride and co-production anhydride and acid.In accordance with shallow way carbonyl mainly used in the present invention, the desired reaction rate are obtained even at low concentrations of water when introduced into the reaction medium of ester, which corresponds carbonyliron alcohol, and acid reaction product of the carbonylation. Optional can be entered dopey, such as methyliodide or other organic iodide. So, when carbonyliron of methanol to acetic acid complex ester is methyl acetate, and an additional iodide promoter is an iodide salt, and lithiated is preferred. Usually this is considered an important concentration of iodide ions in the catalytic system, but not cation, United with iodide, and that at a given molar concentration of iodide nature of the cation is not as important as the effect of the concentration of iodide. Can be used any iodide salt of a metal iodide or any salt of any organic cation provided that the salt is sufficiently soluble in the reaction medium to provide the necessary content of iodide, didney salt may be a Quaternary salt of an organic cation or iodide salt of an inorganic cation. Preferably, it is an iodide salt of a representative group consisting of metals of Group Ia and Group IIa of the periodic system of elements, as it is given in "Handbook of Chemistry and Physics" published by CRC Press, Cleveland, Ohio, 1975-76 (56th edition). In particular, are the iodides of alkali metals, preferably is lithium iodide.At that time, as the l is IU, this component can be removed in a polymeric catalytic system of the invention. However, a number of additional iodide ion can be used for additional promotion of the carbonylation reaction. So, for this purpose can be used, the concentration of iodide salt, such as LiJ, from 0 to less than 10 wt.%. Alternatively, the catalyst of the invention can be added to the previous dry homogeneous system to ensure a more stable areas of the rhodium catalyst. In this case, it may take up to 20 mass. % LiJ or other iodide salts to stabilize and promotion dissolved rhodium like any other shallow homogeneous system, as described in U.S. Patent N 5001259.The carbonylation reaction may be carried out with the direct participation of the supplied alcohol, ether complex and simple ether, which is in the liquid phase, with gaseous carbon monoxide, bubbling fluidised bed through a liquid reaction medium containing dispersed therein rhodium catalyst, a halide-containing promoter, alkyl(complex)ether and any additional promoter soluble iodide salt in terms of temperature is galogensoderjasimi promoting component will contain methyliodide (forming a complex with a polymer carrier), and alkyl ester will contain the acetate. The acetate is present in quantities of 0.5 to 30, preferably 1 to 5 wt.%, and methyliodide is present in quantities of 5 to 20, and preferably 10 to 16 wt.%. The rhodium catalyst is present in amounts of 200 to 5000 parts per million In the previous shallow homogeneous system, the concentration of rhodium were, preferably, 400 to 600 parts per million, although in practice the concentration of rhodium supported below 500 parts per million using polymeric catalyst can be provided to the concentration of rhodium above 500 parts per million, higher than 900 parts per million or even 100 - 5000 parts per million, since the deposition of the rhodium is not a significant problem, as for the old stable homogeneous system. The high content of rhodium significantly improves space-time outputs.The typical reaction temperature of the carbonylation approximately 150 - 250oC, and the preferred range is 175 - 220oC. the Partial pressure of carbon monoxide in the reactor may vary within wide limits, but is usually 2,03 - 50,66 bar (2 to 50 MPa).The polymeric catalyst of the invention is not only used, when used as the sole catalyst emery the catalyst is a solid, or, in other words, is present as a heterogeneous phase in the reaction medium, the catalyst may be used in combination with known homogeneous catalyst to further increase the content of rhodium and performance of the reactor. It can be used in such a mixed system in conditions of low water carbonylation with the addition of a small amount of iodide salt, such as lithium iodide, to stabilize the homogeneous catalyst. Additionally, the polymeric catalyst may be a heterogeneous mixture of polymeric catalyst and homogeneous polymeric catalyst. In this case, the rhodium will be firmly connected with the polymeric catalyst is either insoluble or soluble form, so we need a little, if not no amount of additional iodide salt stabilizer.For purposes of illustration, the invention should now be made by reference to the following examples, which are aimed at individual examples of the production and application of polymeric catalyst of the invention. The examples are only illustrative and do not limit the invention shown here are specific options.Example 1. In this Prime,4 g of acetic acid, 75,4 g under the conditions. to 20.0 g of water and 0,7011 g [Rh (acetate)2]2equivalent to 46.3% rhodium or 0,3246 g of rhodium metal is loaded into the autoclave Hastel-loy C under stirring and heated to 190oC for 2 h and Then the polymeric catalyst was filtered from the liquid reagents. In the filtrate 0,001845 g unabsorbed rhodium. The rhodium content in the polymer is determined by the absorption of metal and is of 1.062% by weight of the polymer.Example 2. Carbonylation is carried out in dry conditions in a 1-liter Hastelloy C autoclave for comparison of the reaction rate between the non-stabilized Rh system, Li-stabilized system and polymer-coordination of Rh-catalyst described in example 1. In all the experiments in this example, the initial water concentration in the reactor is equal to 2%, speed stirrer 1500 rpm./min and the temperature in the reactor 190oC. Critical parameter in the experiments in the autoclave is that it requires a high speed stirrer to prevent the reactor from the beginning of the mass transfer CO., limited at higher space-time yields. This phenomenon is specific for laboratory autoclaves and does not apply to well-designed industrial reactors is I determine the relative kinetic activity of each catalytic system. In each case used 200 g of a solution consisting of 38 g under the conditions, 54 g of methyl acetate, 4 g of water specified concentrations of Rh (as RhJ3given the concentrations of Rh-vinylpyrrolidone and 20.2 g LiJ for comparative experiments, which contained LiJ. The solution is added acetic acid to obtain a total mass of 200 g In each case of the space-time yield of the catalyst is determined by the absorption CO.The autoclave is sealed, opressively gaseous CO to 28.6 bar (400 lb/in2), and the pressure is monitored for 15 min, after which the autoclave is slowly vented from CO to 11.35 bar (150 lb/in2) and then heated to 190oC. Immediately after reaching the desired temperature the autoclave additionally opressively to 28.6 bar (400 lb/in2), and starts stirring (1500 rpm./min). The reaction rate is determined by controlling the number of absorbed CO depending on time. For this specific 1-liter reaction using 200 g of the catalyst solution scheme requires temperature control in the reactor, using cooling coils containing silicone oil, for removal of heat of reaction and maintain the isothermal reaction temperature 190oC deprivated in the table.After the reaction, the polymer-coordination catalyst is separated from the solution by filtration, and is determined by the remaining dissolved Rh to illustrate the high degree of Association between the polymer and the active Rh-part. This high level of Association between the polymer and the Rh component allows the use of high Rh concentration without the problems of deposition and shedding Rh inherent in the known methods.Example 3. For acetic anhydride is used heterogeneous rhodium catalyst from example 1 or produced in situ by reaction of accession, for example, RhJ3with cross-linked polyvinylpyrrolidone and methyliodide (MeJ), methyl acetate (MeAc) and acetic acid (HAc). In a 300 ml Hastelloy C autoclave loads of 4.46 g of crosslinked polyvinylpyrrolidone, 0,2237 g RhJ3, 55,73 g HAc, 27,12 g MeAc and 19,60 g MeJ. In the reactor does not contain any amount of water, and is not added to limiited. The mixture is heated to <190C under pressure of CO, then starts mixing, and pressure in the reactor is brought to 28.6 bar (400 lb/in2). The reaction temperature is maintained at 190oC with an accuracy of 1oC. is Determined by the initial absorption of CO, and calculated space-time output speed of receiving AC
FIELD: waste water treatment.
SUBSTANCE: invention relates to biological waste water treatment methods that can be used at enterprises of power, petroleum processing, petrochemical, chemical, paper-and-pulp, food processing, and other industries as well as for treatment of household sewage. Biocatalytic waste water treatment is performed by oxidation in air tanks or on biofilters in presence of catalytically acting substance and activated sludge. In case of air tanks, catalytically acting substance consists of one (multifunctional) or three (one multifunctional and two selective) heterogeneous catalysts for oxidation of inorganic and/or organic compounds and containing active component: variable-valence metal oxides and/or hydroxides, or spinels, and, additionally, modifying additive, in particular organic bases and/or heteropolyacids, active component being deposited on polymer carrier (polyethylene or polypropylene). Content of active component is 15-20% and that of modifying additive 0.5-20%. For oxidation of organic, sulfur, and nitrogen compounds, multifunctional catalyst is used containing active component consisting of variable-valence metal oxides and hydroxides. For nitrification process (ammonium nitrogen oxidation), selective catalyst is used containing active component consisting of variable-valence metal spinels and oxides. In case of denitrification process (reducing nitrites and nitrates into molecular nitrogen), selective catalyst is used containing active component consisting of variable-valence metal spinels and hydroxides. Oxidation process is accomplished at catalyst-to-water ratio 1:75 at consumption of air not higher than 9.0 m3/m3. Invention also discloses biocatalytic treatment of waste waters via oxidation on biofilters in presence of activated sludge and catalytically acting substance consisting of active component (15-50%): one or several variable-valence metal compounds, flux (50-10%): silicon-containing compound, modifying additive (0.5-20%): carbon-containing material, and carrier: clay.
EFFECT: increased productivity and reduced power consumption on existing treatment plants, reduced investment and operational expenses, and deepened waste water treatment.
8 cl, 5 tbl, 10 ex
FIELD: textile, paper and chemical industries; protection of environment in production of bleachers, biocides and components of oxidizing processes.
SUBSTANCE: proposed catalyst contains one or more metals of platinum group used as active component, one or more polyolefines and activated carbon carrier. It is preferably, that polyolefines have molecular mass above 400 and are selected from ethylene homopolymers and ethylene copolymers with alpha-olefines, propylene homopolymers and propylene copolymers with alpha olefines, butadiene homopolymers and copolymers with styrene and other olefines, isoprene homopolymers and copolymers with other olefines, ethylene-propylene copolymers, ethylene-propylene diolefine three-component copolymers, thermoplastic elastomers obtained from butadiene and/or isoprene and styrene block-copolymers, both hydrogenized and non-hydrogenized. Hydrogen peroxide is produced in presence of said catalyst from hydrogen and oxygen in reaction solvent containing halogenated and/or acid promoter. Proposed catalyst makes it possible to increase degree of conversion and selectivity of process, to obtain aqueous H2O2 solutions at content of acids and/or salts at level of trace amount.
EFFECT: enhanced efficiency.
48 cl, 1 tbl,18 ex
FIELD: chemical industry; methods of preparation of the platinum hydrophobic catalyst used for separation of the isotopes of hydrogen and water.
SUBSTANCE: the invention is pertaining to the methods of preparation of the platinum hydrophobic catalyst used for separation of the isotopes of hydrogen in the columns of the isotope exchange of hydrogen with water. According to the offered method platinum is deposited at the room temperature from the solution of hexachloroplatinum acid H2PtCl6·6H2O in the mixed solvent (the mixture of acetone and mesityl oxide containing 10÷90 vol. of % of mesityl) on the hydrophobic spherical granules of the copolymer of styrene with divinylbenzene (DVB), in which the contents of paradivinylbenzene is no more than 15 mass %, the total contents of the all forms of DVB makes 10-70 mass %, and the mean size of the pores in the granules of the carrier is no less than 300 Å. After ageingin the impregnating solution the carrier is dried and restored with the help of hydrogen. The prepared catalyst possesses the high catalytic activity (the exchange constant кe ˜ 10÷20 s-1), stability (no less than three years), radiation resistance (up to the dose of the irradiation - 100 Mrad). At that the quantity of platinum makes 0.4-1.0 mass %, and the size of the spherical granules lays in the interval of 0.5÷1.0 mm.
EFFECT: the invention ensures, that the prepared catalyst possesses the high catalytic activity (the exchange constant кe ˜ 10÷20 s-1), stability (no less than three years), radiation resistance (up to the dose of the irradiation - 100 Mrad).
4 cl, 10 ex, 6 tbl, 2 dwg
FIELD: chemical industry; other industries; production of the vanadium catalysts for oxidation of sulfur dioxide and sulfur trioxide.
SUBSTANCE: the invention is pertaining to production of the vanadium catalysts for oxidation of sulfur dioxide and sulfur trioxide used in production of the sulfuric acid by the contact method, in particular, to the fusion mixture for production of the catalyst. The technical problem of the present invention is improvement of the operational properties of the catalyst of the conversion of SO2 into SO3, namely - improvement of the strength of the extruded calcined granules of the ready catalyst without deterioration of its catalytic activity at the expense of decrease of the minimal working humidity of the contact mass at extrusion. The fusion mixture for preparation of the catalyst of conversion of SO2 into SO3 includes vanadium oxides and oxides of the alkali metals (K, Na, Rb, Cs), sulfur, polyethyleneoxide, silicon dioxide in the form of the natural and-or synthetic silica. The contents in it of the polyethyleneoxide is within the limits from 0.005 up to 0.195 mass %, in terms of the dry substance.
EFFECT: the invention ensures the improved operational properties of the catalyst of the conversion of sulfur dioxide into sulfur trioxide and the improved strength of the extruded calcined granules of the ready catalyst without deterioration of its catalytic activity.
10 ex, 1 tbl, 1 dwg
FIELD: organic synthesis catalysts.
SUBSTANCE: invention relates to synthesis of C7+-aldehydes from C6+-olefins, carbon monoxide, and hydrogen via hydroformylation reaction and to preparation of catalyst used in this reaction. Olefin hydroformylation catalyst contains complex compound of rhodium with polymeric nitrogen-containing ligand including phosphorus-containing fragments. Each of these fragments contains organic radicals, at least one of which is linked to nitrogen atom of polymeric nitrogen-containing ligand and phosphorus atom is in the form of Ph(III). Catalyst preparation consists in that nitrogen-containing polymer is subjected to reaction in organic solvent with Ph(III) compound including organic radicals, of which at least one radical includes group -C(O)OH. Thus obtained product is then subjected to reaction with rhodium compound and organic solvent is removed.
EFFECT: increased and preserved specific activity and regioselectivity of recycled catalyst and reduced pressure in aldehyde production process.
11 cl, 1 tbl, 8 ex
FIELD: technological processes.
SUBSTANCE: invention is related to methods for preparation of catalyst for dehydration of cyclohexanol in cyclohexanone, which contains copper introduced into solid carrier as active component. It is described the method of preparing catalyst for dehydration of cyclohexanol into cyclohexanone by application of active component - copper from water solution of its salt, which is water solution of its ammonia-carbonate complex, and copper is applied on carrier at thermal decomposition of ammonia-carbonate complex at the temperature of 55-350°C.
EFFECT: simplification of method for catalyst preparation for dehydration of cyclohexanol into cyclohexanone with preservation of produced catalyst quality.
2 cl, 1 tbl, 6 ex
SUBSTANCE: invention refers to making heat-resistant sulphocation catalysts. There is disclosed method for making heat-resistant sulphocation catalysts containing aromatic rings chemically combined with solid polymer base, at least two groups -SO2OH, by sulphonation of aromatic rings of polymer base followed by desulfonation at higher temperature of those aromatic rings having only one group -SO2OH whereat heat-resistant polymer base is sulphonated, while aromatic rings are sulphonated in two or more stages with gradually increasing sulphonation hardness. The first stage involves soft sulphonation with aqueous sulphuric acid solution concentrated 95 wt % and more at temperature 90°C and less, preferentially 70°C and less. The last stage implies sulphonation with aqueous sulphuric acid solution concentrated 90 wt % and more or with oleum with SO3 concentrated 1 to 30 wt % higher than chemically combined in acid. The catalyst is sequentially washed by dissolved sulphuric acid solution, then by water. Thereafter it contacts at temperature 150 to 200°C with an inert solvent not containing groups neutralising -SO3OH groups and introduced in amount required to remove groups -SO2OH from the aromatic rings containing one group -SO2OH only.
EFFECT: making heat-resistant catalyst of required dimension and/or shape.
8 cl, 1 tbl, 5 ex
SUBSTANCE: invention relates to organic chemistry, more specifically to a method of producing sulfoxides through catalytic oxidation of thioethers in the presence of hydrogen peroxide, distinguished by that, the catalyst is in form of zinc compounds such as: zinc salts Zn(NO3)2·6H2O or Zn(CH3COO)2·2H2O, zinc complex compound Zn(salen), coordination polymers based on complex zinc compounds such as homochiral microporous coordination polymers with composition: [Zn2BDC·(L-Lac)·DMF]·(DMF)x, where: BDC - dianion of terephthalic acid, L-Lac - dianion of lactic acid, DMF - dimethylformamide; [Zn2camph2bipy]·3DMF·H2O, where H2camph - (+)-camphoric acid, biry -4,4'-bipyridyl; [Zn2(bpdc)(R-man)(dmf)]·4DMF·H2O, where: H2bpdc - 4,4'-biphenyldicarboxylic acid, R-man - R- mandelic acid; [Zn2camph2bpe]·5DMP-H2O, where: bpe - trans-bis(4-pyridyl)ethylene.
EFFECT: method is designed for producing sulfoxides with high conversion and selectivity, which are widely used in synthesis of organic compounds, including biologically active compounds.
1 cl, 4 ex, 4 tbl
SUBSTANCE: invention relates to a method of photoactivation of a photocatalyst by irradiating a composition containing the said catalyst. The method of using a photolatent catalyst (a) in which a composition containing said catalyst is irradiated before subsequent treatment is characterised by that, the photolatent catalyst is: (a1) a compound selected from a group consisting of a photolatent acid, an aromatic iodonium salt or oxime-based photolatent acid; (a2) a photolatent base compound. Also described is a substrate on which a coating made from the composition is deposited in accordance with the above described method. Also described is a method of using photolatent catalyst (a), in which a composition containing said catalyst is irradiated before subsequent treatment, characterised by that subsequent treatment is preparation of foam material and the composition contains polyol and isocyanate components and photolatent base (a2) as photolatent catalyst.
EFFECT: provision for solidification of the system.
13 cl, 10 tbl, 16 ex
SUBSTANCE: invention relates to curing agents used in epoxide composite materials for acid curing. Disclosed is a method of producing a curing agent by reacting epoxide compounds with anhydrous orthophosphoric acid in molar ratio 3:1-9:1 mole of epoxide groups per mole of acid, in which a reactive solvent is added to both the epoxide compound and acid, where he said solvent is selected from ketones, dimethyl formamide or dimethyl sulphoxide, in amount of 0.2-0.5 pts.wt per 1 pts.wt of reagents. The acid solution is then heated to temperature 50-70°C and the epoxide compound is proportionally added. The orthophosphoric acid used is obtained by reacting aqueous sulphuric acid solution with phosphorus pentoxide, and the epoxide compounds used are selected from phenylglycidal or butylglycidal ether, epichlorohydrin, diane epoxide oligomers or mixtures thereof with aliphatic epoxide oligomers.
EFFECT: method enables to obtain a curing agent which increases the degree of cure and improves physical and mechanical properties of coatings, while preserving their processing properties (working life and stability) regardless of storage time before application onto an article.
1 cl, 2 tbl, 15 ex
FIELD: chemistry of metalloorganic compounds, chemical industry.
SUBSTANCE: invention relates to preparing compounds of tetrapyrazinoporphyrazine order, namely, to cobalt octasulfooctaphenyltetrapyrazinoporphyrazine of the formula:
that can be used as a catalyst in oxidation reactions of sulfur-containing compounds, in particular, cysteine and thioureas, and diethylamine also being both in acid and neutral media.
EFFECT: valuable properties of compound.
2 cl, 2 dwg, 4 ex
FIELD: chemistry, pharmacology.
SUBSTANCE: present invention relates to method for production of indolo-pyrrolo-carbazole derivative according to formula (I) , or its pharmaceutically acceptable salt, that have antitumour activity. Invention also relates to method for production of indole compound according to formula (XII) , or its pharmaceutically acceptable salt, where R1 is protective hydroxy-group, distinguished by conducting interreaction between compound with formula (XIII) , or its pharmaceutically acceptable salt, where R1 is definitely above, Ra and Rb are either separately C1-C7-alkyl, or together form C3-C6-alkylene group, and hydrogen gas at 1 to 5 atmospheres, in presence of hydrogenation catalyst (applied as novel catalyst as well), which consist of rhodium compound, metal compound, and optionally amine, in inert solvent at room temperature; the rhodium compound being 1 to 10% rhodium on carbon, aluminium oxide, calcium carbonate, or barium sulphate, and metal compound being nickel (II), iron (II), iron (III), cobalt (II), or cobalt (III). Method is also submitted for production of bis-indole compound by formula (VIII) , or its pharmaceutically acceptable salt, where R1 is protective hydroxy-group, Y is hydrogen, C1-C7-alkyl, phenyl, benzyloxymethyl, or C7-C12-aralkyl, consisting in reaction of indole compound by formula (XII), or its pharmaceutically acceptable salt, where R1 is protective hydroxy-group, with ethylmagnesium chloride, or butylmagnesium chloride, or magnesium compound by formula (X) RdMgRd, where Rd is butyl, in inert solvent, followed by conducting interreaction between product obtained and maleimide compound by formula (IX) , where X is halogen, and Y as above, in inert solvent.
EFFECT: improved method for indolo-pyrrolo-carbazole production.
15 cl, 68 ex, 12 tbl
SUBSTANCE: method involves catalytic telomerisation of butadiene with diethylamine in the presence of a catalyst based on cationic complexes of palladium (II) of general formula [(acac)Pd(L)2]BF4 (where acac is an acetylacetonate ligand, L=PPh3, P'Pr3, P"Bu3 P(p-Tol)3 or (L)2=diphosphine ligands, selected from bis(diphenylphosphino)methane(dppm), bis(diphenylphosphino)propane(dppp), bis(diphenylphosphino)butane(dppb), bis(diphenylphosphino)ferrocene(dppf)). The process is carried out in a substrate medium, specifically diethylamine and butadiene, at temperature of 50-90°C. The method enables to obtain N,N-diethylocta-2,7-diene-1-amine with selectivity of 99.9% from the overall mixture of reaction products with high process output which reaches 4180 g of product per 1 g Pd. The catalysts used are more readily available compared to those previously used for the process.
EFFECT: improved method.
1 tbl, 1 ex