The method of obtaining substituted hydrocarbon
(57) Abstract:Usage: in the petrochemical industry, in particular in the processes of obtaining substituted hydrocarbons. The inventive method involves the oxidation reactor C6-C10-aromatic hydrocarbon or lower C2-C6alkane and/or the corresponding alkene oxygen-containing gas in the presence of the oxide catalyst in the diluent. Receive a gaseous product containing the target product and flue gases, comprising unreacted hydrocarbons, which are in contact with the solvent in the scrubber. Almost the entire product is dissolved in a solvent and is removed from the scrubber, and washed exhaust gas is sent to the heater, in which the oxidation catalyst (CT) WITH the conditions, not oxidizing unreacted hydrocarbon. As CT use mixed-oxide copper - manganese or Nickel - Nickel catalyst. The gas stream is depleted in CO, separated from the latter part of the carbon dioxide separator and recycle in the process. 8 C.p. f-crystals, 3 ill., 5 table. The invention is directed to a method and apparatus for hydrocarbon derivatives of hydrocarbon and Keysaney performance while reducing or excluding the danger of explosion or fire in known or new headspace of the reactor system, where petrochemical product is produced from a hydrocarbon and oxygen.Some hydrocarbon derivative gain in the industry by incomplete oxidation of the corresponding hydrocarbon in the vapor phase over a catalyst and in the presence of oxygen-containing gas. For example, cyclic anhydrides get in the industry by a vapor-phase catalytic partial oxidation of aromatic hydrocarbons, such as o-xylene or benzene, or a hydrocarbon, a linear structure, such as n-butane or butene, in the presence of oxygen-containing gas over a vanadium-containing catalyst. Similarly, NITRILES, alkalinity, aldehydes and halogenated hydrocarbons receive an incomplete oxidation of the corresponding alkanes and alkenes in the presence of selected catalysts. As the oxygen-containing gas typically use air because of its low cost and easy availability. The reaction may be conducted in any suitable reactor, such as reactor with a fixed catalyst bed, fluidized bed, moving bed of catalyst, irrigated catalyst layer or a floating layer of catalyst, and it allows you to get the angle is and other partially oxidized by-products. The sequence of the reaction equipment usually consists of a reactor,in which receive the hydrocarbon derivative, scrubbers, in which the hydrocarbon derivative is washed out from the waste gases of the reactor, through water or another solvent for hydrocarbons, and means for further processing the washed flue gases.Previously it was a common to apply the above method based on a single pass, and the conversion of the hydrocarbon to the desired petrochemical product was increased to the limit. This resulted in a low overall efficiency, since the selectivity of transformation in the petrochemical product was below the maximum. Therefore, exhaust gases of the gas contained significant amounts of CO and CO2besides unreacted hydrocarbon. These products are usually burned, so that only received from them the result was the cost of heat. In the later part ways flue gas scrubber recycled, the conversion of hydrocarbons is reduced and the selectivity of conversion of the hydrocarbon to the desired petrochemical product has increased. The remainder of the off-gas removed from the system to prevent the accumulation of CO,CO2Describes how to obtain maleic anhydride, in which raw materials for the reactor includes hydrocarbons WITH4, air, CO, and CO2. In this way maleic anhydride is recovered from the off-gas flow reactor, and the remaining part of the recycle stream. Bhutan stands out from precirculated gas stream by adsorption with temperature change in the reactor and recycle.Also described method with the vapor recirculation for obtaining maleic anhydride by reacting hydrocarbon WITH4linear structure with oxygen in the presence of CO2. In this way, the gas mixture may contain up to 30% vol. carbon dioxide as inert diluent, and contains at least 25 vol.% hydrocarbon WITH4.Recycling part of the exhaust gas from the reactor gas-phase partial oxidation of the hydrocarbon increases capital costs, compared to single-pass methods, because the size of the reactor and associated equipment must be increased to manipulate the increased volume of CO,CO2and nitrogen, resulting in the recycling stage. The problem Wuxi is to provide adequate heat dissipation to prevent overheating of the reactor requires a large gas flows.Another problem associated with gas-phase obtaining petrochemical product by oxidation of hydrocarbons oxygen-containing gas is that, since the reaction is carried out at elevated temperatures, there is always a danger of fire or explosion in the reactor or equipment, or pipelines, related to the reactor. Accordingly, the concentration of reagents in the support system such that the mixture is outside the limits of Flammability. Although nitrogen is used to reduce the Flammability limits of the mixture as the source of oxygen for the reaction using the air Flammability limits for mixtures of hydrocarbon-air are still very wide. Therefore, usually operated reactors gas-phase oxidation of hydrocarbons at low concentrations of hydrocarbon, so that the reaction mixture remained outside the limits of Flammability.Also known is a method of obtaining maleic anhydride by reacting n-butane and air in the presence of a catalyst comprising the oxides of vanadium and phosphorus.The method of this patent involves the stages of selection of maleic anhydride from the waste gases of the reactor gaseous okelani is of relatively pure n-butane from the remaining exhaust gas and recycling the relatively pure n-butane in the commodity system.Described another way to obtain gas-phase maleic anhydride, in which the oxidizing gas using oxygen and an inert gas such as nitrogen, argon, helium or a lower hydrocarbon is introduced into the reactor with n-butane and oxygen, and an inert gas as a diluent to reduce the concentration of oxygen and butane in the reactor below the concentration at which they form a flammable mixture. In the described method, part of the off-gas, containing also butane, carbon monoxide, carbon dioxide and inert gas, recycle. One of the drawbacks of this method is that the recirculated carbon monoxide increases fire and explosion hazards, because carbon monoxide is itself flammable.Closest to the proposed method describes the recirculation method for vapor obtain maleic anhydride by reacting hydrocarbon WITH4linear structure with oxygen in the presence of CO2. According to this method, the gas mixture may contain up to 30% vol. carbon dioxide as inert diluent and contains at least 25 vol.% hydrocarbon WITH4. Thus at most 2% vol. and more preferably the UB> can make the gas mixture in the system ignited.U.S. patent N 4.987.239 describes a method of obtaining anhydrides by reacting hydrocarbons with oxygen-containing gas in the presence of an appropriate catalyst. In this way separate the separator provides recycling a substantial portion of unreacted hydrocarbon and a controlled amount of gaseous, the vast flame tools.Because of the increasing importance attached to security, and energy costs in industry continue to attempt the creation of chemical processes, including oxygen and flammable compounds, less hazardous and more economical in operation. The present invention provides a method that provides these benefits.The proposed method of producing substituted hydrocarbon is gas-phase oxidation WITH6-C10-aromatic hydrocarbon, or lower2-C6-alkane and/or the corresponding alkene oxygen-containing gas in the presence of a catalyst for the oxidation of hydrocarbon and diluent inert gas at elevated temperature in the reactor to obtain a gaseous product, from which the inert gas, by recycling part of the exhaust gases in the line of fresh raw materials, the distinctive feature of which is that the gaseous product is subjected to contact with the solvent in the scrubber, with virtually the entire product is dissolved in a solvent and is removed from the scrubber, and washed exhaust gas enters the Converter containing a catalyst capable of oxidizing carbon monoxide under conditions in which little or not oxidize unreacted hydrocarbons contained in the gas product, such as a mixed oxide of copper and manganese or platinum-Nickel catalyst, optionally deposited on a substrate, for example, silicon oxide or aluminum oxide, to obtain a gas stream depleted in carbon monoxide, a selection from the last part of the carbon dioxide separator and recycling the remaining depleted carbon monoxide gas stream through recycling.Carbon dioxide is usually present in the reaction zone as a diluent, preferably, as a main solvent. Specific derived hydrocarbon derivative depends on what alkanes and/or alkenes interact, from the concrete used in the comprehension of hydrocarbons usually also contains carbon monoxide, carbon dioxide, unreacted hydrocarbon (HC), oxygen, inert gases, if they are introduced into the reactor, and possibly small amounts of other by-products of the reaction. The flow of gaseous product leaving the oxidation reactor, then enter in the tool to highlight the desired derivative, which, for example, may be a condenser or scrubber, in which the flow is brought into contact with liquid solvent that removes from the gas stream, essentially, the entire petrochemical product. Derivative isolated from the means for selecting in liquid form solids. To the stage of selection of petrochemical product or followed her the whole or part of the flow of gaseous product is processed in the Converter of carbon monoxide to convert a number or all of the carbon monoxide in the stream to carbon dioxide. In a preferred execution of the chosen catalyst, which oxidizes carbon monoxide without oxidation present in the stream of unreacted hydrocarbon to any significant degree. Part of the carbon dioxide in further separated from the stream, and the remaining stream is recycled to the reactor for the oxidation of hydrocarbons.In predpochtitel as the main diluent is carbon dioxide. In another preferred application, the concentration of carbon dioxide in all parts of the reaction system is high enough one of carbon dioxide prevented the formation of inflammable mixture in the system. Preferably from the gas stream of carbon dioxide can be distinguished by adsorption; pressure change when carbon dioxide is at least 60% of the gas component flowing into the process.The proposed method will now be described using examples with reference to the accompanying figures, in which: Fig.1 illustrates in a block diagram of a system for obtaining petrochemical product, in accordance with one implementation of the present invention; Fig.2 - in the form of a block diagram of a system for obtaining petrochemical product, in accordance with the second implementation of the invention; Fig.3 - in the form of a block diagram, a modified version of the system depicted in Fig.1.The method of the invention can be used for the production of any petrochemical product, which is produced by gas-phase reaction of a hydrocarbon with oxygen at elevated temperatures. Typical petrochemical production processes, which can be applied and the th or hydrocarbon, a linear structure WITH4with oxygen in the presence of a catalyst based on vanadium oxide. Examples include obtaining maleic anhydride by reacting benzene or saturated or unsaturated hydrocarbon WITH4with oxygen, and obtaining phthalic anhydride by reacting o-xylene or naphthalene with oxygen. Currently, a hydrocarbon, a linear structure WITH4prefer the benzene to produce maleic anhydride, due to the high cost of benzene. To obtain maleic anhydride is most preferred hydrocarbon is n-butane, due to the fact that it is cheaper unsaturated hydrocarbons WITH4the latter are more valuable because of its suitability as monomers. n-butane varieties often contain other hydrocarbons such as ISO-butane, but these impurities are undesirable because they do not interfere with the obtaining of maleic anhydride from n-butane.2. Obtaining unsaturated NITRILES by the interaction of lower alkanes or alkenes with oxygen and ammonia in the presence of an oxide catalyst containing bismuth and molybdenum, or an oxide catalyst containing iron and antimony deposited on the oxide substrate credit is Odom and ammonia to obtain Acrylonitrile or the interaction of ISO-butane or ISO-butylene with oxygen and ammonia in obtaining Methacrylonitrile.3. Obtaining aldehydes by reacting lower alkanes or alkenes with oxygen in the presence of various catalysts on the basis of the halides of the metals or metal oxides. Examples include obtaining acetaldehyde by reacting ethylene with oxygen in the presence of copper chloride and palladium chloride, and receiving acrolein by reacting propylene with oxygen over a molybdenum-bismuth-iron catalyst.From the above examples it is evident that the method of the invention can be used for various petrochemical products within the classes mentioned by interaction of the corresponding hydrocarbons with oxygen. The specific reaction of partial oxidation is carried out in the method of the invention, is not critical to the invention. In General, the method of the invention may include any of the oxidation reaction of hydrocarbons carried out in the vapor phase at elevated temperatures, to obtain any of these petrochemical products, and which includes the interaction of hydrocarbon and oxygen (and, where appropriate, other reagents, such as ammonia, hydrogen chloride or chlorine) in the presence of the catalyst recip as by-products.Specific hydrocarbon or hydrocarbons to be used as reagents in phase oxidation of a hydrocarbon of the method of the invention, will be determined by the specific get petrochemical product. In General, the raw hydrocarbon may be aromatic, aliphatic or cycloaliphatic, he may be saturated or ethyleneamines, a linear or branched structure. Suitable aromatic hydrocarbons include hydrocarbons having up to twelve or more carbon atoms, and suitable aliphatic and cycloaliphatic hydrocarbons include hydrocarbons having two to twelve or more carbon atoms. Preferred aromatic hydrocarbons are hydrocarbons having 6 to 10 carbon atoms, such as benzene, o-xylene and naphthalene, and the preferred aliphatic hydrocarbons are saturated or ethylbenzene hydrocarbons linear structure having 2-6 carbon atoms, such as ethane, ethylene, propane, propylene, n-butane, ISO-butane, n-butylene, ISO-butylene, butadiene and pentane, pentene, hexane and hexene.Sources of oxygen used in the method may be pure oxygen or oxygen-containing gauduchon, oxygen-enriched, mean air contains more oxygen than is usually present in the air. A mixture of the oxygen-inert gas includes a mixture of oxygen, nitrogen, a mixture of oxygen, argon, a mixture of oxygen, carbon dioxide etc., Pure oxygen is preferred because its use avoids the introduction of excess inert gases such as nitrogen and argon, into the system and, further, it is necessary to remove excess quantities of these inert gases from the gaseous product stream to prevent their accumulation in the system.The invention can best be understood on the basis of the accompanying drawings to designate the same or similar equipment in the various drawings used the same number. Auxiliary equipment, including valves, compressors, and heat exchangers that are not necessary for understanding the invention have been eliminated from the drawings to simplify discussion of the invention.With regard to Fig.1, the apparatus of this model includes the reactor incomplete oxidation of hydrocarbons 2 having input means 4 of the raw material and the output 6 of the product. The output 6 of the product associated with the installation of extraction of product, for example, the scrubber 8, which pinborough output washed gas 14, which is connected with the Converter monoxide 16. The Converter 16 unloads oxidized gas through line 18 associated with the separator carbon dioxide 20. The separator 20 is equipped with a line discharging flue gases 22 and is also connected through the recirculation line 24 together with the input of raw material 4. The system depicted in Fig.1, is also equipped with a bypass line 26 controlled by valves 28 and 30, and the bypass line 32 controlled by valve 34.In Fig. 2 depicts a variation of the system shown in Fig.1. This system is essentially the same as the system in Fig.1, however, in the system of Fig. 2, the separator 20 of carbon dioxide Fig.1 has been replaced by the purge line 36, which is controlled by valve 38.In Fig.3 shows another variation of the system of Fig.1.In the version of Fig.3 Converter 16 monoxide and the separator 20 of carbon dioxide have in parallel, and each of these units can be taken as raw material part of the off-gas from the scrubber 8. The Converter 16 receives the exhaust gas scrubber through line 14 and unloads the oxidized gas for recirculation to the reactor 2 through line 40 and 24; and the separator 20 receives exhaust gas scrubber through line 14 and 36 and unloads the smoke provided with a bypass line 26, controlled by valve 28. The flow through the Converter 16, the separator 20, and the loop line 26 can be adjusted to any desired speed.Reactor 2 may be any suitable reactor, but usually it is a design with a fixed, moving, fluidized, irrigated or floating layer of the catalyst. The invention is particularly effective when petrochemical products in the reactor with a fixed catalyst bed due to Nichelino greater heat generation in this type of reactor. Reactor 2 may be provided with heat exchange means to remove heat generated in the reaction, which is exothermic. Specific details of the construction of the respective reactors are well known and do not constitute part of the present invention. Installation 8 allocation of petrochemical product is usually a standard scrubber, i.e., the absorber, usually Packed structure, here shown as provided with means for spraying water or an aqueous or nonaqueous liquid, gas product, coming into this setting from the reactor 2. The Converter 16, and the reactor 2 may be of any suitable design. In preferred versions of the is located downstream of the scrubber petrochemical product, it can be positioned against the flow of gas petrochemical product, or, if desired, it can even be included in the reactor 2.The purpose of the separator 20 carbon dioxide is the removal of carbon dioxide and other inert gases from the system, and this setting may represent any device that will allow you to achieve this result. The separator 20 is typically an adsorber or absorber. In preferred versions of the invention, the separator 20 is a unit for adsorption with pressure variation (PSA) or the installation of adsorption with temperature change (TSA).In the method of the invention, the raw materials comprising the corresponding hydrocarbon, oxygen-containing gas, other reagents, where appropriate, and re-circulating gas flow into the reactor 2 through the input means 4, which may include a single line of input, through which the reactor 2 is introduced a mixture of gaseous reactants and diluents, or it may include several separate lines of input for the separate entry of the reactants into the reactor. Specific input device in most cases will depend on the type of reactor used for the application of the invention. In reactor reactor, and thus injected into the reactor through a single line, whereas in reactor systems fluidized bed of catalyst components are separately introduced into the reactor.You can specify that in order to realize the main advantage of the invention, i.e., oxidation of carbon monoxide to carbon dioxide, the carbon dioxide must be recycled in the system as a diluent. In a preferred execution of the carbon dioxide present in the system as the primary inert diluent, i.e., carbon dioxide is present in the system at the concentrations higher than any other inert gaseous component. Thus, other inert gaseous components such as nitrogen, argon, water vapor and directionspanel compounds, including directionspanel hydrocarbons may be present in the system, but the concentration of each of these other inert components in the system, based on volume less than the concentration of carbon dioxide in the system. Inert gaseous component is a component that does not react under the conditions existing in the system. The concentration of carbon dioxide in the system, preferably, podderjivayutsa. In a preferred implementation, the carbon dioxide is at least 50 vol.%, and in the most preferred version of the carbon dioxide is at least 70 vol.%, of the total amount of gases in the system.In order to start the operation of the method of the invention, carbon dioxide or any other inert gas can be introduced into the system with the raw material, to ensure that the gas mixture is and remains outside the limits of Flammability. Often at the beginning of operation it is convenient to use an inert gas, in addition to carbon dioxide. For example, if the source of oxygen during the initial period of use air, nitrogen component of the air can serve as a diluent as long as the concentration of carbon dioxide reaches the desired level. Then, in a preferred implementation, the air can be gradually replaced with essentially pure oxygen or oxygen-enriched air. Carbon dioxide can be easily maintained in the desired range, adjusting the amount of recycled carbon dioxide.Raw gases entering the reactor 2, in contact with the catalyst and react to form product gases. In the method of the invention can be used lubcke under specific conditions. Suitable catalysts include catalysts based on vanadium oxide to obtain a cyclic anhydrides; multicomponent molybdate catalysts or catalysts containing antimony, to obtain NITRILES; bismuth molybdate for the first stage and mixed molybdenum-tungsten-vanadium catalyst for the second stage of the two-stage process for obtaining unsaturated Karbanovich acids from alkenes; and silver oxide or mixed molten nitrates to obtain alkalisation. These catalysts and their use of standard and well known to experts in the field of production of petrochemical products. Specific catalysts for partial oxidation of hydrocarbons, used in the method of the invention, do not constitute part of the invention.Conditions of incomplete oxidation of hydrocarbons are well known and do not constitute part of the invention. Typically, the oxidation reaction is carried out at a temperature 120-600aboutWith, and typically 150-500aboutC, and at pressures typically in the range of 0.14 to 35.15 ATI, usually in the range of 0.21-24,64 ATI. The reagents usually pass through the reactor with a velocity in the range from 0.15 to 1.5 m/s Volume ratio of oxygen to hydrocarbon raw materials, it is advisable in the range of 0.3:as the main product, and carbon dioxide and carbon monoxide as by-products. In accordance with the above, the flow of the product usually contains unreacted hydrocarbon and oxygen, and may contain small amounts of other by-products, impurity gases and directionspublic hydrocarbons. The product gas stream (see Fig.1-3) leaves the reactor through line 6 and enters the scrubber 8 product. The purpose of the installation of 8 is selected hydrocarbon derived from the exhaust gas reactor for the conversion of hydrocarbons. In the scrubber 8 product gases lead in direct contact with the solvent for the petrochemical product. The solvent dissolves, essentially, the entire petrochemical product from the product gas stream, and the solution leaving the scrubber 8 through line 12. In the future, it is usually processed to highlight petrochemical product. The washed gas stream leaving the scrubber 8 through line 14 and enters the Converter monoxide 16.The purpose of the Converter monoxide 16 is the conversion of carbon monoxide obtained in the oxidation of hydrocarbons, carbon dioxide, to prevent acoplado in carbon dioxide. In the method of the invention can be any catalyst which will promote the oxidation of carbon monoxide to carbon dioxide. The preferred catalysts are those which oxidize carbon monoxide to carbon dioxide under such conditions that a little oxidized or not oxidized hydrocarbons present in the gas stream entering the Converter of carbon monoxide. Among the catalysts suitable for use in the Converter 16 are mixed copper-manganese oxides and catalysts based on noble metals, such as platinum-Nickel catalyst.These compositions can be used as they are, or deposited on an appropriate substrate, such as silicon oxide or aluminum oxide. As will be clear from the following discussion, unreacted hydrocarbon and carbon dioxide leaving the Converter 16, recycle to the reactor 2 so that the method can be optimized. Accordingly, if the carbon monoxide (also with recycle of unreacted hydrocarbon) is not completely removed, as, for example, by conversion to carbon dioxide, the carbon monoxide concentration in the system will increase and eventually reaches the best amount of carbon monoxide, equivalent to the amount produced in the reactor 2 for each pass. Thus, the Converter 16 may be a relatively small reactor.As a rule, from 1 to 20 mol.% hydrocarbon (e.g., 5-20%) entering the reactor 2, is converted into carbon dioxide, and 1 to 20 mol.% hydrocarbon (e.g., 5-20%) is converted into carbon monoxide. Since the amount of carbon monoxide into carbon dioxide in the Converter 16, often essentially equal to the number monoxide produced in the reactor 2, the total amount of carbon dioxide produced in the reaction method is 2-40 mol.%, in relation to the number of hydrocarbon entering the reactor 2. Thus, it is possible to determine that the advantage of the invention lies in the fact that in many cases the concentration of carbon dioxide can be quickly brought to the desired operating level during the beginning of the operation.In some cases, it may not be necessary to pass all the washed gas through the Converter 16 to obtain the desired degree of conversion of carbon monoxide. In such cases, the portion of the washed flue gas in line 14 can be put in the contour around the Converter 16 via line 26, opening the valve 28 is in the washed gas in line 14 is bypassed Converter 16 and the separator 20. In this case, open the valves 28 and 34 and close the valve 30. Thus, the system can be operated so that all or part of the washed gas in line 14 is passed through the reactor 16.After the stage of oxidation of carbon monoxide, the gas stream leaving the Converter 16 through line 18 and into the separator 20. The separator 20 serves the purpose of removal of carbon dioxide and other inert gases found in excess in relation to the quantities desired for recycling. For example, when the source of oxygen used air, carbon dioxide, in excess relative to the amount desired for recycling, nitrogen and argon is removed from the system in the separator 20. To prevent accumulation of nitrogen and argon in the system, when the source of oxygen used air, as a rule, it is necessary to remove essentially all of the nitrogen and argon entering the reactor 2 together with fresh raw materials. This can easily be done by exploiting the separator 20 so that the nitrogen and argon passed through the separator, and the hydrocarbon and some or all of the carbon dioxide was absorbed or adsorbiroval. Nitrogen, argon and the excess carbon dioxide is removed from the separator 20 through laroda recycle to the reactor 2 via line 24. Line 24 may be connected with line 4, as shown in Fig.1-3, or it can be connected directly to the reactor 2.In accordance with the above, the separator 20 may be any means for separation of unreacted hydrocarbon and carbon dioxide from flue gas from Converter 16, but in the preferred implementation, this installation is the EVAP pressure change. Adsorption with pressure variation is a well-known method for separation of components from a mixture of gases by differences in the degree of adsorption on powdered adsorbent held in a stationary layer. Typically, two or more such layers are used in a cyclic process involving adsorption at relatively high pressure and desorption at a relatively low pressure or vacuum. The desired component or components can be obtained at any of these stages. The cycle may contain other stages, in addition to the main stages of adsorption and regeneration, and it typically contains two or more layers of adsorbent, making its turnover through 180aboutout of phase in order to ensure pseudosteady the flow of the desired product. Because standartizaciya under vacuum.In a preferred execution of the invention, essentially pure oxygen is used as oxidant, and carbon dioxide is used as the primary dilution gas. In this case, systems impose very little or not introducing nitrogen, and a gas flow separator 20 consists essentially of unreacted hydrocarbon, carbon dioxide and carbon monoxide. Then the separator 20 is used to remove only small amounts of carbon dioxide from the system, and the remainder of the gas stream entering the separator 20, consisting of carbon dioxide, unreacted hydrocarbon and carbon monoxide, recycle to the reactor 2. In some cases, it may not be necessary to pass all of the carbon dioxide through the separator 20.In such cases, part of the off-gas from the Converter 16 can be unloaded directly into the recirculation line 24 by opening valves 30 and 34, and closing the valve 28. If desired, the system can be operated with open valves 28, 30 and 34 (see Fig.1).In the operation of the method of the invention in accordance with Fig.2, a portion of the exhaust gas stream from Converter 16 is removed from the system through line 36, opening the valve 38, and the remainder of insulinaemia gas, the way this performance is the most convenient, when the oxidant is essentially pure oxygen. In this case, in the gas recycled to the reactor 2 will not be present in significant amounts of nitrogen. As it was with the execution of Fig.1, a portion of the washed gas leaving the scrubber 8, can be put into the outline of the Converter 16 by opening valve 28.When using the method of the invention in the system of Fig.3 part of the off-gas from the scrubber 8 passes through the Converter 16 to oxidize the desired amount of carbon monoxide to carbon dioxide, as part of a flue gas scrubber is sent to the separator 20 to remove the desired amount of carbon dioxide and other inert gases, if any are present, from the system through line 22. The exhaust gas from Converter 16 (line 40) and the stream selected for recirculated from the separator 20 (line 44), mix and return to the reactor 2 via line 24. In some situations it may not be necessary to skip the entire flue gas scrubber through the Converter 16 and the separator 20. In such cases, the portion of the waste stream is recycled directly to the reactor 2 through line 26 and 24 by opening valve 28.Will actenoides to regulate the flow of gases in the system so the system can be fully automated in order to effectively run continuously.When applying the invention several advantages are achieved. For example, the use of the Converter monoxide allows the method to work, not emitting carbon monoxide into the atmosphere; removes excess carbon monoxide from the reaction system, thereby reducing the risk of fire or explosion in the equipment used in the method; and reduces the time required to increase the concentration of carbon dioxide in the system to the desired operating level. The use of carbon dioxide as inert diluent increases the productivity of the reaction system, because of the relatively high heat capacity of carbon dioxide allows the reaction proceeded with a smaller presence of inert gas. Accordingly, the reagents can be introduced into the reactor at a higher flow rate. Other advantages of the method of the invention are its simplicity, ease of operation and low capital and operational investments. Furthermore, the method can operate at a relatively low conversion per pass of raw hydrocarbons in the desired product to achieve sname, in which percentage, ratios and parts, including parts per million (ppm) is given in the calculation amount if not specified.P R I m e R 1. A gas mixture consisting of the components listed in table. 1, the raw material was applied to a half inch reactor of carbon steel containing 2 g of a mixed catalyst is copper oxide-manganese oxide, sold Carus Chemical Company under the trademark Carulite 200. The catalyst bed was held in the reactor volume, is equal to 2.2 cm3. The gas mixture was heated to a temperature of 200aboutWith and filed in the reactor at a specific flow rate equal 67,6 min-1. The results of this experiment are presented in table.1.Table. 1 shows that a 99.16% monoxide hydrocarbon fed to the reactor was turned into carbon dioxide, while the degree of conversion of the hydrocarbon minimal.P R I m m e R 2. The experiment vapor obtaining maleic anhydride was produced in a reactor with a fixed catalyst bed, based on the results obtained in the experiment of example 1. Reactor system similar to the system of Fig.3. Reproducible flow in hydrocarbon reactor component consists of Fresh Raw materials and component Recir is containing a series of fixed catalyst layer of the oxide of vanadium-phosphorus, Converter of carbon monoxide, comprising a fixed catalyst bed consisting of Carulite 200 and EVAP pressure change, adsorption layer containing molecular sieves. Different flow rates and the results of the experiments are presented in table.2.P R I m e R 3. The experiment vapor to obtain Acrylonitrile reproduced in a reactor with a fixed bed of the catalyst on the basis of the results obtained in the experiment similar to the experiment of example 1 is conducted at a temperature of approximately 300aboutC. Reactor system similar to the system of Fig. 2. Reproducible flow in hydrocarbon reactor component consists of Fresh Raw materials and component Recirculating Stream. The reaction was reproduced based on the use of hydrocarbon vapor reactor containing a fixed catalyst layer of bismuth oxide/molybdenum, Converter, carbon, comprising a fixed bed of the catalyst Carulite 200. Different flow rates and the results of the experiments are presented in table.3.Methacrylonitrile can be obtained similarly, using as the hydrocarbon reactant isobutylene.P R I m e R 4. A gas mixture consisting of components, l2O3sold United Catalysis Inc. under oboznachaiut G# 43D. The gas mixture was heated to 150aboutWith and filed in the reactor at a flow rate of 85 cm3/min. the Results of this experiment are presented in table.4.Table.4 shows that 80% vol. carbon monoxide fed to the reactor was turned into carbon dioxide, while the degree of conversion of the hydrocarbon minimal.P R I m e R 5. Experiment two-stage vapor obtaining acrylic acid was produced in a reactor with a fixed catalyst bed, based on the results obtained in the experiment of example 4. The reactor system was similar to the system of Fig.2. Reproducible flow in hydrocarbon reactor component consists of Fresh Raw materials and component Recirculating Stream. The reaction reproduce based on the use of hydrocarbon vapor to the reactor containing the first fixed catalyst bed of bismuth molybdate and the second fixed layer, a molybdenum-tungsten-vanadium catalyst. The system used in this experiment included Converter monoxide containing a fixed bed of catalyst G# 43D. Different flow rates and the results of the experiment is the firmness of the hydrocarbon reactant isobutylene.Table. 5 shows that 80% vol. carbon monoxide fed to the reactor was turned into carbon dioxide at that time, as the degree of conversion of the hydrocarbon minimal.P R I m e R 6. The propylene oxide can be obtained by reaction of propylene in the presence of a catalyst based on molten salts, including sodium nitrate and potassium nitrate, as described in U.S. patent N 4.785.123. In the method of this experiment can be used a catalyst for the oxidation of carbon monoxide used in any of examples 1 or 4.Although the invention has been described with special reference to a particular experiment, this experiment is just an illustrative example of the invention and variations are assumed. For example, the reaction can be performed in the liquid phase or mixed phase, or other conditions that will allow for other petrochemical products. Similarly, if it is desirable, in the invention it is possible to use other catalysts and adsorbents, and other means for gas separation. Also, if desirable, the product gases leaving the system through line 22, can be further processed, for example by cryogenic stages or additional adsorption="ptx2">It is also understood that the invention is not limited to the arrangement of equipment shown on the drawings. In accordance with the above, if it is desired, the Converter 16 monoxide can be placed against the stream separation unit petrochemical product 8. In fact, the separator may even be included in the reactor 2, or mixed with a catalyst for oxidation of hydrocarbons in the form of a single mixed layer of the catalyst, or by itself, in the form of a separate layer. If the separator is included in the reactor 2 in the form of a separate layer, it preferably include a downstream catalyst layer oxidation of hydrocarbons. You can determine that the location of the connecting lines to move liquids for this variant of the invention is different from the location shown on the drawings. 1. The METHOD of OBTAINING SUBSTITUTED HYDROCARBON gas-phase oxidation WITH6- C10-aromatic hydrocarbon or lower WITH2- C6-alkane and/or the corresponding alkene oxygen-containing gas in the presence of a catalyst for the oxidation of hydrocarbon and diluent inert gas at elevated temperature in the reactor to obtain a gaseous product, which verty gas, by recycling part of the exhaust gases in line fresh original products, characterized in that the gaseous product is subjected to contact with the solvent scrubber, almost the entire product is dissolved in a solvent and is removed from the scrubber, and washed exhaust gas enters the Converter containing a catalyst capable of oxidizing carbon monoxide under conditions in which little or not oxidize unreacted hydrocarbons contained in the gas product, such as a mixed oxide of copper and manganese or sinker-Nickel catalyst, optionally deposited on a substrate, such as silicon oxide or aluminum oxide, obtaining a gas stream depleted in carbon monoxide, a selection from the last part of the carbon dioxide separator and recycling the remaining depleted carbon monoxide gas stream through recycling.2. The method according to p. 1, characterized in that an inert gas diluent use carbon dioxide.3. The method according to PP.1 and 2, characterized in that as the oxygen-containing gas is used almost pure oxygen.4. The method according to PP.1 to 3, characterized in that diox xed carbon separated from the gas stream by adsorption with pressure variation.6. The method according to PP.1 to 4, characterized in that the process is conducted in the presence of gaseous ammonia.7. The method according to PP.1 - 6, characterized in that get substituted hydrocarbon selected from the group of maleic anhydride, phthalic anhydride, Aceto or Acrylonitrile, acrolein, acrylic acid, propylene oxide.8. The method according to PP.1 to 7, characterized in that the carbon dioxide is at least 60% of the gas component flowing into the process.9. The method according to p. 1, characterized in that the flow amount of carbon dioxide sufficient to prevent the formation of inflammable mixture.Priority signs:
31.10.91 a way of producing maleic and phthalic anhydrides;
15.10.91 a way of producing other compounds mentioned in paragraphs.1 to 4, and a way of getting under item 6.
FIELD: chemical industry; petrochemical industry; methods (versions) of the ammoxidation of the carboxylic acids in the mixture of nitriles.
SUBSTANCE: the invention is pertaining to the methods (versions) of the ammoxidation or to the method of increasing of the yield of the acetonitrile in the form of the by-product produced in the process of manufacture of acrylonitrile, which provide for injection of the reactants, which contain at least one hydrocarbon selected from the group, which includes propylene and the propane, at least one С1-С4 carboxylic acid, ammonia and the gas containing the molecular oxygen, into the reaction zone containing the catalyst of the ammoxidation, and realization of the reaction of the indicated reactants above the indicated catalyst at the heightened temperature with production of the yield, which contains acrylonitrile, hydrogen cyanide and acetonitrile. The method may additionally include the contact of the effluent of the reaction zone with the liquid of extinguishing, which contains the water and at least one С1-С4 carboxylic acid, and the addition of at least a part of the extinguishing liquid into the reaction zone after the extinguishing liquid contacting the liquid of the reaction zone. The invention allows to increase the yield and, predominantly, the ratio of the by-product - acetonitrile to the acrylonitrile produced in the process of the ammoxidation of the hydrocarbon, such as propylene or propane into acrylonitrile.
EFFECT: the ensures the increased yield and the ratio of the by-product - acetonitrile to the acrylonitrile produced in the process of the ammoxidation of the hydrocarbon, such as propylene or propane into acrylonitrile.
22 cl, 1 tbl, 1 ex
SUBSTANCE: the scope of invention covers economically feasible methods of isolation and purification of valuable nitrogen-containing organic compounds obtained by catalytic ammoxidation of at least one original compound selected from the group consisting of propane, propylene, isobutane and isobutylene in the presence of ammonia with production of gaseous product. The methods described in invention include cooling of gas flow leaving reactor with water-containing liquid coolant; production of water solution containing relevant unsaturated mononitrile, hydrocyanic acid and other organic products; and application of integrated sequence of distillations and phase separations to isolate for recycling useful water-containing liquid and production of desired nitrogen-containing products.
EFFECT: maintenance of effective quantity to inhibit polymerisation.
30 cl, 1 dwg, 3 ex
SUBSTANCE: mixed metal oxide catalyst based on antimonite in a catalytic active oxidation state has the empirical formula: MeaSbbXcQdReOf, where Me is at least one element from the group: Fe, Co, Ni, Sn, U, Cr, Cu, Mn, Ti, Th, Ce, Pr, Sm, or Nd; X is at least one element from the group: V, Mo, or W; Q is at least one element from the group: Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Zr, Hf, Nb, Ta, Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Ge, Pb, As, or Se; R is at least one element from the group: Bi, B, P, or Te; and the indices a, b, c, d, e and f denote atomic ratios: a has a value from 0.1 to 15; b has a value from 1 to 100; c has a value from 0 to 20; d has a value from 0 to 20; e has a value from 0 to 10 and f is a number, taken to fulfill the valency requirements of the metals answering for the oxidation degree they have in the composition of the catalyst. Method of obtaining such a catalyst includes the following stages. At first they are subjected to aqueous suspension of Sb2O3 with HNO3 and with one or more compounds of Me, and voluntarily with one or more compounds from the groups: X, Q or R, for obtaining the first mixture (a). The first mixture is then heated and dried to form a solid product (b). After this the solid product is calcinated forming the catalyst. The particular metal oxide catalyst based on antimonite in the catalytic active oxidation state as per the invention has the empirical formula: Ua'FeaSbbMocBieOf, where the indices a, a', b, c, e and f denote atomic ratios: a has a value from 0.1 to 5; a' has a value from 0.1 to 5; b has a value from 1 to 10; c has a value from 0.001 to 0.2; e has a value from 0.001 to 0.2; and f is a number, taken to fulfill the valency requirements of Sb, U, Fe, Bi, and Mo, answering for the oxidation degree they have in the composition of the catalyst. Method of obtaining such a catalyst includes the following stages. At first they are subjected to aqueous suspension of Sb2O3 with HNO3, oxides or nitrates of bismuth and oxides or nitrates of uranium to form the first mixture (a). The first mixture is then heated under temperature and in a period of time, enough for the induction of the process for the formation of the antimonic oxide crystals and formation of the second mixture (b). An aqueous solution of a ferric compound iss then added to the second mixture for the formation of a third mixture (c). The pH of the third mixture is regulated in the range of 7 - 8.5, a precipitate of a hydrated mixture of oxides in the aqueous phase is formed (d). The precipitate is separated from the aqueous phase (e). An aqueous suspension of precipitate components of hydrated mixed oxides is obtained (f). Molybdate is added to the suspension component of hydrated mixed oxides (g). A suspension of hydrated mixed oxides of Molybdate component in the form of dy particles is formed (h). Later the calcination of the dry particles with the formation of the catalyst is carried out (i).
EFFECT: increase in the activity and selectivity of the catalyst.
30 cl, 2 tbl, 7 ex
SUBSTANCE: 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 %.
EFFECT: reduced process performance due to reduced output of target product and enhanced selectivity of carbon oxide generation at the second process stage.
50 cl, 10 ex
SUBSTANCE: described is mass of metal oxides, intended as catalyst for heterogeneously-catalysed partial oxidation and/or ammoxidation of at least one saturated and/or unsaturated hydrocarbon, of general stechiometry I MO1VaM1 bM2 cM3 dOn (I), were M1= stands for Te; M2=stands for Nb; M3= stands for at least one of elements from group, which includes Pb, Ni, Co, Bi and Pd; a = 0.05 to 0.6, b= 0.01 to 0.5, c= 0.01 to 0.5, d = 0.0005 to 0.5 and n= equals the number determined by valence and number of different from oxygen elements in (I), whose X-ray diffractogragm has diffraction reflexes h, i and k , whose peaks are at diffraction angles (2Θ) 22.2±0.5° (h), 27.3±0.5° (i) and 28.2±0.5° (k), and - diffraction reflex h in the range of X-ray diffractogram is the most intensive and has peak half-width maximal value 0.5°, intensity Pi of diffraction reflex i and intensity Pk fulfill ratio 0.65≤R≤0.85, in which R is determined by formula R=Pi/(Pi+Pk) intensity ratio, and - half-width of diffraction reflex i and diffraction reflex k each constitute ≤1°, and at least one mass of metal oxides (I) represents such, X-ray diffractogram of which does not have diffraction reflex with peak position 2Θ=50.0±0.3°. Described is mass of metal oxides, which contains equal or more than 80 wt % of at least one mass of metal oxides, indicated above, and whose X-ray diffractogram has diffraction reflex with peak 2Θ=50.0±0.3°.Also described are methods of heterogeneously catalysed partial gas phase oxidation or ammoxidation of at least one saturated or unsaturated hydrocarbon, using as catalytic active mass at least one mass of metal oxides, described above. Described is method of obtaining metal oxides mass by mixing sources of its elementary components, calcination of dry mixture at 350-700°C and washing by organic and/or inorganic acid solution.
EFFECT: increasing target product selectivity.
17 cl, 1 tbl, 16 ex, 17 dwg
SUBSTANCE: present invention relates to mixed metal oxide oxidation catalysts and ammonolysis of propane and isobutane, methods of obtaining them and usage. Described is a mixed metal-oxide system, containing molybdenum, vanadium, niobium, antimony, germanium and oxygen or molybdenum, vanadium, tantalum, antimony, germanium and oxygen, with the following stoichiometric ratios of elements: molybdenum to antimony from 1:0.1 to approximately 1:0.5, and molybdenum to germanium from 1:>0.2 to approximately 1:1. Description is given of a catalyst, which is a mixed metal-oxide system, effective in vapour-phase conversion of propane to acrylic acid or acrylonitrile or conversion of isobutane to methacrylic acid or methacrylonitrile. The mixed metal-oxide system has an empirical formula Mo1VaNbbSbcGedOx or Mo1VaTabSbcGedOx, in which a ranges between 0.1 and 0.6, b ranges between 0.02 and 0.12, c ranges between 0.1 and 0.5, d ranges from more than 0.2 to 1, and x depends on the oxidation number of other elements in the mixed metal-oxide system. Described also is a method of obtaining the system described above, involving the following stages: addition into a reaction vessel of precursors Mo, V, Nb or Ta, Ge and Sb in an aqueous solvent to form a reaction medium with initial pH 4 or less, and optional addition of another aqueous solvent into the reaction vessel; sealing the reaction vessel; reaction of the reaction mixture at temperature above 100°C and pressure above atmospheric pressure for a period of time, sufficient for formation of a mixed metal-oxide system; optional cooling of the reaction mixture; and extraction of the mixed metal-oxide system from the reaction mixture. Description is given of a method of converting propane into acrylonitrile and isobutane into methacrylonitrile using the catalyst described above.
EFFECT: simple technology of making catalyst, increased catalyst activity and output of the target product in reactions of oxidative ammonolysis of propane and isobutane.
27 cl, 8 tbl, 50 ex, 1 dwg
SUBSTANCE: invention relates to a method for oxidative ammonolysis in the presence of mixed metal oxide catalysts. The method for oxidative ammonolysis to obtain an unsaturated nitrile involves bringing saturated or unsaturated hydrocarbon or a mixture of saturated or unsaturated hydrocarbon with ammonia and an oxygen-containing gas in the presence of a catalyst composition containing molybdenum, vanadium, antimony, niobium, tellurium, at least one element selected from a group consisting of titanium, tin, germanium, zirconium, hafnium and mixtures thereof, at least one lanthanide selected from a group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium and mixtures thereof. Disclosed is a version of the method for oxidative ammonolysis, where the catalyst contains, in addition to the listed elements, lithium and an element selected from sodium, caesium, rubidium and mixture thereof.
EFFECT: catalysts are characterised by very low content of tellurium in the composition, catalyst compositions are effective in gas-phase conversion of propane to acrylonitrile and isobutane to methacrylonitrile.
25 cl, 2 tbl, 15 ex
SUBSTANCE: invention relates to hydrocarbon oxidation catalysts. Described is a catalyst for oxidising hydrocarbons during gas-phase contact, containing a mixed oxide of molybdenum (Mo), vanadium (V), tellurium (Te) and niobium (Nb), having chemical formula 1: Mo1.0VaTebNbcon, (l) where a, b or c independently denotes atomic molar ratios of vanadium, tellurium or niobium, provided that 0.01≤a≤1, 0.01≤b≤1, 0.01≤c≤1 and n denotes the atomic molar ratio of oxygen, which is determined by valence and atomic molar ratios of vanadium, tellurium and niobium, and tungsten (W) or tungsten oxide bonded to the mixed metal oxide, where the atomic molar ratio of tungsten bonded to the mixed metal oxide and molybdenum contained in the mixed metal oxide ranges from 0.00001:1 to 0.02:1. Described is a method of producing said catalyst involving steps for: preparing a first mixture of molybdenum (Mo) precursor, a vanadium (V) precursor, a tellurium precursor (Te), a niobium precursor (Nb) and acid; obtaining a mixed oxide of molybdenum (Mo), vanadium (V), tellurium (Te) and niobium (Nb) by calcining the first mixture; preparing a second mixture of mixed metal oxide and the tungsten precursor and calcining the second mixture. Described is a method for gas-phase oxidation of hydrocarbons, involving oxidation of hydrocarbons in the presence of the catalyst described above.
EFFECT: high activity and selectivity of the catalyst.
10 cl, 2 tbl, 12 ex
SUBSTANCE: described is a catalyst for oxidising hydrocarbons during gas-phase contact, containing a mixed oxide of molybdenum (Mo), vanadium (V), tellurium (Te) and niobium (Nb), having chemical formula 1: Mo10VaTebNbcOn, (1) where a, b or c independently denotes atomic molar ratios of vanadium, tellurium or niobium, provided that 0.01≤a≤1, 0.01≤b≤1, 0.01≤c≤1 and n denotes the atomic molar ratio of oxygen, which is determined by valence and atomic molar ratios of vanadium, tellurium and niobium, and palladium (Pd) or palladium oxide bonded to the mixed metal oxide, where the atomic molar ratio of palladium bonded to the mixed metal oxide and molybdenum contained in the mixed metal oxide ranges from 0.00001:1 to 0.02:1. Described is a method of producing said catalyst, comprising steps for: preparing a first mixture of a molybdenum (Mo) precursor, a vanadium (V) precursor, a tellurium precursor (Te), a niobium precursor (Nb) and an acid; preparing a mixed oxide of molybdenum (Mo), vanadium (V), tellurium (Te) and niobium (Nb) by calcining the first mixture; preparing a second mixture of mixed metal oxide and a palladium precursor and calcining the second mixture. Described is a method for gas-phase oxidation of hydrocarbons, involving oxidation of hydrocarbons in the presence of the catalyst described above.
EFFECT: high activity and selectivity of the catalyst.
10 cl, 2 tbl, 12 cl
SUBSTANCE: invention relates to a method of producing acrylonitrile from glycerine. The method involves a first step for gas-phase dehydration of glycerine in the presence of a catalyst having Hammett acidity, denoted by H0, less than +2, at temperature ranging from 150°C to 500°C and at pressure and at pressure ranging from 1 to 5 bar, to obtain acrolein; a second step for ammoxidation of acrolein on an ammoxidation catalyst at temperature ranging from 300°C to 550°C and at pressure ranging from 1 to 5 bar, to obtain acrylonitrile; and an intermediate step for partial condensation of water and heavy byproducts obtained at the dehydration step. The invention also relates to acrylonitrile with 14C content of the order 10-10 wt % with respect to total weight of carbon which can be obtained using the method given above.
EFFECT: method enables to optimise the acrolein ammoxidation step by reducing the amount of water and impurities in a stream rich in acrolein.
3 cl, 2 dwg, 1 tbl, 3 ex
FIELD: chemical industry; production of synthesis gas, methanol and acetic acid on its base.
SUBSTANCE: the invention is dealt with the methods of production of synthesis gas, production of methanol and acetic acid on its base. The method of upgrading of the existing installation for production of methanol or methanol/ ammonia provides for simultaneous use of the installation also for production of acetic acid or its derivatives. The existing installation contains a reformer, to which a natural gas or other hydrocarbon and a steam (water), from which a synthesis gas is formed. All the volume of the synthesis gas or its part is processed for separation of carbon dioxide, carbon monoxide and hydrogen. The separated carbon dioxide is fed into an existing circuit of synthesis of methanol for production of methanol or is returned to the inlet of the reformer to increase the share of carbon monoxide in the synthesis gas. The whole volume of the remained synthesis gas and carbon, which has not been fed into the separator of dioxide, may be transformed into methanol in the existing circuit of a synthesis of methanol together with carbon dioxide from the separator and-or carbon dioxide delivered from an external source, and hydrogen from the separator. Then the separated carbon monoxide is subjected to reactions with methanol for production of acetic acid or an intermediate compound of acetic acid according to the routine technology. A part of the acetic acid comes into reaction with oxygen and ethylene with formation of monomer of vinyl acetate. With the help of the new installation for air separation nitrogen is produced for production of additional amount of ammonia by the upgraded initial installation for production of ammonia, where the separated hydrogen interacts with nitrogen with the help of the routine technology. As the finished product contains acetic acid then they in addition install the device for production of a monomer of vinyl acetate using reaction of a part of the acetic acid with ethylene and oxygen. With the purpose of production of the oxygen necessary for production of a monomer of vinyl acetate they additionally install a device for separation of air. At that the amount of nitrogen produced by the device of separation of air corresponds to nitrogen demand for production of additional amount of ammonia. The upgraded installation ensures increased production of additional amount of ammonia as compared with the initial installation for production of methanol. The invention also provides for a method of production of hydrogen and a product chosen from a group consisting of acetic acid, acetic anhydride, methyl formate, methyl acetate and their combinations, from hydrocarbon through methanol and carbon monoxide. For this purpose execute catalytic reforming of hydrocarbon with steam in presence of a relatively small amount of carbon dioxide with formation of the synthesis gas containing hydrogen, carbon monoxide and carbon dioxide, in which synthesis gas is characterized by magnitude of the molar ratio R = ((H2-CO2)/(CO+CO2)) from 2.0 up to 2.9. The reaction mixture contains carbon monoxide, water -up to 20 mass %, a dissolvent and a catalytic system containing at least one halogenated promoter and at least one rhodium compound, iridium compound or their combination. The technical result provides, that reconstruction of operating installations increases their productivity and expands assortment of produced industrial products.
EFFECT: the invention ensures, that reconstruction of operating installations increases their productivity and expands assortment of produced industrial products.
44 cl, 3 ex, 6 dwg
SUBSTANCE: invention concerns improved method of obtaining carboxylic acid and/or complex alcohol ether and carboxylic acid, involving carbonylation of C1-C8 aliphatic alcohol and/or its reactive derivative by carbon monoxide in liquid reaction mix in carbonylation reactor. Liquid reaction mix includes indicated alcohol and/or its reactive derivative, carbonylation catalyst, alkylhalide co-catalyst and optionally water in limited concentration, the catalyst including cobalt, rhodium or iridium coordinated with tridentate ligand, or their mix. Also invention concerns application of carbolylation catalyst including cobalt, rhodium or iridium coordinated with tridentate ligand, or their mix, in carbonylation method of obtaining carboxylic acid and/or complex alcohol ether and carboxylic acid.
EFFECT: enhanced carbonylation speed and selectivity.
36 cl, 6 tbl, 3 ex
SUBSTANCE: method includes carbonylation of the alcohol and/or of its reactive derivative with carbon monooxide in liquid reaction mixture carried out in carbonylation reactor. The said liquid reaction mixture contains the said alcohol and/or its reactive derivative, carbonylation catalyst, alkyl halide cocatalyst whereat the said catalyst includes at least one metal selected from rhodium or iridium coordinated with polydentate ligand whereat the said polydentate ligand has the bite angle at least 145° or forms the "hard" Rh or Ir metal-ligand complex; the said polydentate ligand includes at least two coordination groups; at least two of them independently contain P, N, As or Sb as coordination atoms. The hydrogen/carbon monooxide mole ratio is supported in the range at least 1:100 and/or carbon monooxide directed to carbonylation reactor contains at least 1 mole % of hydrogen; catalyst flexibility range is less 40°. The method is tolerable to hydrogen presence i.e. liquid side-products are formed in small amounts or are not formed at all.
EFFECT: improvement of the method of carboxylic acid and its ester obtaining.
49 cl, 3 tbl, 13 ex
SUBSTANCE: described is a carbonylation method for producing a carbonylation product by bringing carbon monoxide into contact with initial material containing alcohol and/or its reactive derivative, in vapour phase using a heterogeneous heteropolyacid catalyst containing one or more metal cations selected from Cu, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt. The initial material contains 0.5-20 wt % water and water in the initial material is fresh and/or recycled.
EFFECT: increased catalyst activity, increased degree of convertion of methanol into the desired product.
35 cl, 5 ex, 3 tbl
SUBSTANCE: method of producing acetic acid and its ester or anhydride involves bringing methanol and/or its reactive derivative selected from methyl acetate and dimethyl ether into contact with carbon monoxide in the presence of a catalyst at temperature ranging from 250 to 600°C and pressure ranging from 10 to 200 bars, and where content of iodide in the methanol and/or its reactive derivative, carbon monoxide and catalyst is less than 500 parts/million, where the catalyst essentially consists of mordenite which contains skeleton elements in form of silicon, aluminium and one or more of other elements selected from gallium and boron, and in which copper, nickel, iridium, rhodium or cobalt is added through ion exchange or some other method.
EFFECT: high selectivity with respect to the end product and high catalyst stability.
22 cl, 3 tbl, 5 ex
SUBSTANCE: invention relates to an improved method of producing dialkyl ether of naphthalene dicarboxylic acid used in production of different polymer materials such as polyesters or polyamides from a liquid-phase reaction mixture containing low-molecular alcohol, naphthalene dicarboxylic acid, and material which contains polyethylene naphthalate, in mass ratio of alcohol to acid between 1:1 and 10:1, at temperature between 260°C and 370°C and pressure between 5 and 250 absolute atmospheres.
EFFECT: method enables production of highly pure NDC.
6 cl, 2 ex
SUBSTANCE: method relates to production of acetic acid ether (methyl acetate) via carbonylation of dimethyl ether in gas phase in presence of catalyst and may be used in chemical industry. Invention covers catalyst for carbonylation of dimethyl ether that comprises acid cesium salt of phosphor-tungsten heteropoly acid CsxHyPW12O40, where 1.3≤x≤2.2, y=3-x with platinum additive in amount of 0.25-1.0 wt %. Catalyst in prepared on adding cesium soluble salt to mix of solutions of phosphor-tungsten heteropoly acid and platinum-hydrochloric acid, both taken in required ratio, evaporating, drying, tabletting and grinding to required size. Invention covers also production of methyl acetate in presence of above described catalyst.
EFFECT: higher catalytic activity.
5 cl, 9 ex, 1 tbl
SUBSTANCE: invention relates to an improved carbonylation method intended for producing a carbonylation product through reaction of carbon monoxide with raw material which contains alcohol and/or reactive derivative thereof, in vapour phase using a heterogeneous catalyst in form heteropoly acid which undergoes ion exchange with one or more metals selected from a group comprising rhodium, iridium, copper and palladium, and a group IA metal selected from lithium, sodium, potassium and rubidium, or in which these metals are included, where the heteropoly acid has formula H3M12XO40, where M denotes tungsten, molybdenum, chromium, vanadium, tantalum or niobium and X denotes phosphorus or silicon.
EFFECT: method provides high conversion of the methanol reagent and longer service life of the catalyst.
28 cl, 1 tbl
SUBSTANCE: invention relates to an improved method of reducing concentration of aldehyde in the crude stream of a carbonylation process, involving feeding a crude stream containing a carbonylatable agent selected from a group consisting of methanol, methyl acetate, methyl formate and dimethyl ether or mixture thereof, having primary concentration of aldehydes; and reaction thereof in gaseous phase with a deposited catalyst which contains at least one metal from group 8 to 11, in conditions which facilitate reduction of primary concentration of aldehydes to secondary concentration of aldehydes.
EFFECT: method improves degree of reduction of aldehyde.
28 cl, 3 tbl, 3 ex
SUBSTANCE: invention relates to an improved method of producing C1-C3 aliphatic carboxylic acid and/or the corresponding ester, by carbonylating the corresponding C1-C3 aliphatic alcohol and/or an ester or ether derivative thereof with carbon monoxide material containing hydrogen, in the presence of a catalyst containing a zeolite having at least one 8-member ring channel, said 8-member ring channel being connected with a channel formed by a ring with greater than or equal to 8 members, said 8-member ring having a window size of at least 2.5 Å × at least 3.6 Å and at least one Bronsted acid site and that zeolite has a silicon dioxide: X2O3 molar ratio of not less than 5, where X is selected from aluminium, boron, iron, gallium and mixtures thereof with the condition that the zeolite is not mordenite or ferrierite. The catalysts demonstrate considerable carbonylation activity compared to other zeolite catalysts.
EFFECT: improved method of producing C1-C3 aliphatic carboxylic acid.
41 cl, 2 tbl, 18 ex