The way to fix nitrogen
(57) Abstract:The method used to fix nitrogen and receiving nitrogen-containing compounds. The method of fixation of nitrogen is that gases containing nitrogen, in contact with the catalyst at atmospheric pressure and low temperatures. As catalysts carbonyl complexes of transition metals, in particular platinum group, in the form of solid products, solutions or suspensions with neutral, acidic or alkaline environment. In the composition of gases containing nitrogen may be reducing agents and/or oxidizing agents. The end products are ammonia or nitrogen oxides. 3 C.p. f-crystals. The method relates to the field of inorganic chemistry.As is known, molecular nitrogen under normal conditions, is chemically inert. Therefore, translating it into a bound state requires mild conditions - high temperatures and high pressure, as is the case when obtaining ammonia from nitrogen and hydrogen. This process is energy intensive and requires the use of special expensive equipment. Therefore, the development of ways of linking molecular nitrogen under mild conditions is an important task that you are trying to solve with pomoshyu ammonia from hydrogen and nitrogen at low temperatures and pressures in the presence of compounds of molybdenum, containing metallographie communication .The disadvantage of this method is the low yield of the final product (0.4%) and the performance of 0.1% per hour.The proposed method is based on the high activity of CO molecules included in carbonyl complexes of transition metals, in particular platinum group metals.Thus, for reactions (1, 2, 3)
< / BR>there is a high thermodynamic possibility of leakage. However, reaction (1, 2, 3) under mild conditions (room temperature and atmospheric pressure) does not occur because of the high values of activation energy.At the same time, the CO molecule included in the carbonyl complexes, significantly activated and able to join in the reduction reaction of which with the free CO molecules does not occur.Thus, the reaction in solution
2CuII+ CO + H2O = 2CuI+ CO2+ 2H+(4)
does not leak. But in the presence of salts of palladium (II) forming a CO carbonyl complexes, reaction (4) easily proceeds under mild conditions .The essence of the proposed method lies in the fact that the gas mixture containing nitrogen comes into contact with the catalyst - carbonyl complexes of transition meta is to and in the oxidized form (NO,N2O), which is primarily determined by the composition of the gas mixture in contact with the catalyst.The process proceeds under mild conditions at atmospheric pressure and temperatures from room temperature up to 200 - 300oC.The catalyst may be in dry form, in the form of aqueous or aqueous-organic pulp, as well as in the form of a solution. The original liquid phase can be acidic, alkaline or neutral.Example 1. 700 mg of carbonyl plate [Pt(CO2]nrasulovna in 150 ml of 0.1 n hydrochloric acid solution. Through this pulp at t = 60oC and atmospheric pressure with stirring missed a mixture of CO + air in a volume ratio of 1:2 at a rate of 10 ml/min for 30 minutesIn the exhaust gas was discovered 8.5 mg of N2O.Per reaction
CO + N2+ O2= N2O + CO2< / BR>the output of the associated nitrogen is 20%.Example 2. 35 mg of carbonyl platinum [Pt(CO)2]nwas dissolved in 50 ml of NaOH solution. Through this solution at t=20oC, atmospheric pressure and stirring missed a mixture of CO + air in a volume ratio of 1:2 at a rate of 10 ml/min for 30 minutesThe solution was found associated oxidized nitrogen 5.1 mg the data of nitrogen is 12.3%
Example 3. 60 mg of rhodium, 40 mg of ruthenium and 12 mg of iridium in the form of its carbonyl-chloride-Rh2(CO)2Cl2Ir2(CO)2Cl2, Ru(CO)2Cl2dissolved in 35 ml of liquid, consisting of 5 ml of H2O and 30 ml of methanol and pH 9. Through this solution at 30oC, atmospheric pressure and stirring missed a mixture of CO+H2in a volume ratio of 1:1 for 1.3 hours at a rate of 10 ml/min Exhaust gas absorbed solution of hydrochloric acid. Was obtained bound nitrogen in the calculation of the ammonium chloride 9 mg
For the reaction
3CO+N2+3H2O=2NH3+3CO2< / BR>the output of the associated nitrogen is 1.4%.Example 4. 500 mg of carbonyl composition Pt7Pd2(CO)15in the form of crystals were placed in a boat in a tubular furnace. At t= 200oC and atmospheric pressure over a catalyst missed a gas mixture of CO, N2and water vapor in a volume ratio of 3:1:2 at a rate of 10 ml/min for 2 hIn the exhaust gas was detected 12 mg of ammonia.Per reaction
3CO+N2+3H2O=2NH3+3CO2< / BR>the output of the associated nitrogen was of 4.75%.As seen from the above examples, the carbonyl complexes of transition CLASS="ptx2">Literature.1. Shilov, A. E. USP, 1974, T. 43, S. 863
2. Patent Germany N 956674, 1957.3. Spitsyn, C. I., I. Fedoseev Century, Ponomarev, A. L., Elesin A. I. J. neorg. chemistry, 1978, T. 26, vol. 2, S. 454. 1. The method of fixation of nitrogen by contact with gases containing nitrogen with a catalyst, wherein the catalyst used carbonyl complexes of transition metals.2. The method according to p. 1, characterized in that the nitrogen is part of the gases containing the reducing agents and/or oxidizing agents.3. The method according to p. 1, characterized in that the catalyst may be dry mixed with the liquid phase or in solution.4. The method according to p. 3, characterized in that the used water or water-organic solutions with acidic, alkaline or neutral media.
FIELD: industrial organic synthesis.
SUBSTANCE: invention provides a method for preparing improved oxirane hydroformylation catalyst, improved oxirane hydroformylation catalyst, and single-stage process for production of 1,3-diol in presence of such catalyst. Preparation of catalyst comprises preparing complex A by contacting ruthenium(0) compound with di-tertiary phosphine ligand and preparing complex B via redox reaction of complex A with cobalt(0) carbonyl compound. Single-stage 1,3-diol production process involves reaction of oxirane with synthesis gas under hydroformylation conditions in inert solvent in presence of aforesaid catalyst, where recovery of product is preferably accomplished through separation of product-rich phase.
EFFECT: reduced number of stages to a single one or increased yield of 1,3-diol without by-products and preserved catalytic activity after catalyst regeneration operation.
10 cl, 3 dwg, 6 tbl, 21 ex
FIELD: industrial organic synthesis.
SUBSTANCE: invention relates to improved method for preparing 1,3-dioles comprising (i) bringing into contact oxirane, carbon monoxide, and hydrogen at 30 to 150°C and pressure 3 to 25 MPa in essentially water-immiscible solvent in presence of effective amount of homogenous bimetallic hydroformylation cobalt carbonyl-containing catalyst and cocatalyst based on metal selected from ruthenium group and which is bound to phosphine ligand optionally in presence of promoter, wherein molar ratio of ligand to this cocatalyst metal atom is within a range of 0.2:1.0 to 0.4:1.0, under reaction conditions effective to obtain reaction products mixture containing aliphatic 1,3-diol; (ii) adding aqueous solution to reaction product mixture obtained and extracting major part of aliphatic 1,3-diol into said aqueous solution at temperature below 100°C to form aqueous phase containing aliphatic 1,3-diol in higher concentration that that of aliphatic 1,3-diol in reaction product mixture and organic phase containing at least part of bimetallic hydroformylation catalyst; (iii) separating aqueous phase from processing phase; and (iv) optionally recycling at least part of catalyst-containing organic phase to stage (i). Invention also relates to catalyst composition for hydroformylation of ethylene oxide into aliphatic 1,3-propanediol, which composition is obtained via a method comprising (i) preparation of complex A by bringing cocatalyst ruthenium-group metal compound into contact with phosphine ligand at ligand-to-cocatalyst metal atom from 0.2:1.0 to 0.4:1.0; (ii) preparation of complex B by subjecting complex A to redox reaction with cobalt carbonyl.
EFFECT: enabled less costly single-step hydroformylation process.
8 cl, 2 dwg, 4 tbl, 52 ex
SUBSTANCE: invention relates to polymerisation catalyst components and use thereof. Described are olefin polymerisation catalyst components, which are essentially spherically shaped, containing Mg, Ti and a halogen as basic components and containing an electron donor compound of formula (I) RaCR1(OR4)-CR2R3(OR5) (I), in which Ra is a metal group or is condensed with R4 to form a ring, R1, R2 and R3 independently denote hydrogen or C1-C20 hydrocarbon groups, possibly containing heteroatoms, R4 and R5 denote methyl or R6CO-groups, in which R6 is a C1-C20-alkyl group, or may be bonded with Ra and R3, respectively, to form a ring; provided that when Ra and R4 form a ring, R5 is methyl. Described also is an olefin CH2=CHR polymerisation catalyst in which R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms, which includes a product of a reaction between: (a) catalyst components described above, (b) an alkylaluminium compound; described also is use of thereof in polymerisation.
EFFECT: described catalyst enables to obtain polymers having a narrow molecular weight distribution and high apparent density.
8 cl, 2 tbl, 8 ex
SUBSTANCE: invention relates to an integrated method, in which pure iron carbonyl powder is prepared by decomposition of pure iron pentacarbonyl in a plant A, and carbon monoxide (CO) liberated during decomposition of iron pentacarbonyl is used in plant A for further preparation of iron carbonyl powder from iron or is fed into a connected plant B for preparation of synthesis gas or is fed into a connected plant C for preparation of hydrocarbons from synthesis gas. The iron carbonyl powder prepared in plant A is used as catalyst or catalyst component in the connected plant C for preparation of hydrocarbons from synthesis gas from plant B, and spent catalyst obtained in plant C is used as additional iron source for preparation iron carbonyl powder in plant A.
EFFECT: use of the disclosed method enables to avoid wastes such as salts or waste water.
11 cl, 4 dwg
SUBSTANCE: invention relates to the catalyst for accelerating the curing of novolac resins modified by propargilgalogenidom comprising as an organic nickel compound a 0.01-0.5 mol % solution of 2-ethylhexanoate nickel in a ketone solvent.
EFFECT: invention reduces heat capacity while maintaining low curing temperature, and its storage stability in air.
1 tbl, 2 dwg
SUBSTANCE: invention relates to the ruthenium complexes of formulas (1a), (1b), (1c) or (1d): [Ru Hal2 L CO S] (1a); [Ru2 Hal4 L2 (CO)2 ] (1b); [Ru2 Hal4 L2 CO] (1c); [Ru Hal2 L (CO)2 ] (1d). In these formulas Hal represents a halogen ligand, L is a substituted or an unsubstituted paracyclophane ligand of the formula (2):
where X1 X2 represent bonding groups including linear, branched, or cyclic structures where the link is formed via 2, 3 or 4 carbon atoms, each group Y1 Y2 Y3 Y4 independently from each other is selected from the group including an unsubstituted C1-C20 alkyl, replaced by C1-C20 alkyl, an unsubstituted C3-C10cycloalkyl, substituted C3-C10 cycloalkyl, unsubstituted C6-C20 aryl, substituted C6-C20 aryl, unsubstituted C5-C20 heteroaryl and substituted C5-C20 heteroaryl; or Y1 Y2 and/or Y3 Y4 are connected so that the ring structure is formed, that includes the phosphorus atom, each of the groups Z1, Z2 and Z3 is the same or different, and they are selected from the group consisting of unsubstituted branched C1-C30 alkyl, substituted branched C1-C30 alkyl, unsubstituted linear C1-C30alkyl, substituted linear C1-C30 alkyl, unsubstituted C6-C20 aryl, substituted C6-C20 aryl, benzyl, substituted benzyl, halogen, hydroxyl, -O-(C1-C30 alkyl), -OSi(C1-C30 alkyl), -OCH2Ph, carbonyl, carboxyl, anhydride, methacrylate, epoxide, vinyl, nitrile, sulfate, sulfonyl, mercapto group, sulfide, amino group, amine, imine, amide and imide; a, b, C, d, e and f represent integers of 0 or 1 and a+b+c+d+e+f = from 0 to 6, CO represents a carbonyl ligand; and S represents a ligand solvent. Also methods of producing such complexes are proposed.
EFFECT: ruthenium complexes of the formula are useful in a variety of chemical reactions, such as those of isomerization, hydrogenation, hydrogen transfer, hydrogenation, hydroformylation or carbonylation.
16 cl, 8 ex
SUBSTANCE: invention relates to the method of producing alkyl ethers of 4-biphenylcarboxylic acid where R = Me, Et, Prn, which are used as starting compounds for the preparation of medicaments and thermotropic polymers. The essence of the method consists in the interaction of biphenyl with carbon tetrachloride and alcohols (MeOH, EtOH, PrnOH) in the presence of a catalyst selected from the series Fe(acac)3, Fe(OAc)2, Fe(OAc)2*4H2O, FeCl2 and Fe2(CO)9, at 130-150°C for 4-10 hours at a molar ratio of [Fe]: [biphenyl]:[CCl4]:[ROH]=5-20:100:100-2000:100-2000. The following ratios of the catalyst and the reagents [Fe]:[biphenyl]:[CCl4]:[RON]=10:100:1000:1000, at a temperature of 130°C for 8 hours at a temperature of 130°C and a reaction time of 8 hours, the yield of methyl 4-biphenylcarboxylic acid is 41%, ethyl 4-biphenylcarboxylic acid - 14%, propyl ether - 90%.
EFFECT: method improvement.
1 tbl, 22 ex
SUBSTANCE: essence of the method consists in the interaction of anisole with carbon tetrachloride and alcohols (MeOH, EtOH, PrnOH, BunOH) in the presence of a catalyst selected from the series FeBr3, FeCl3*6H2O, Fe2CO9, FeCl3(harmless), FeCl2, FeBr2, Fe(acac)3, FeCl2*4H2O, Fe(OAc)2, Fe(OAc)2*4H2O at 130°C for 4-8 hours at a molar ratio of [Fe]:[anisole]:[CCl4]:[ROH]=1-10:100:100-1000:100-1000. The following ratios of catalyst and reagents are optimal for the reaction: [Fe]:[anisole]:[CCl4]:[ROH]=10:100:1000:1000 at a temperature of 130°C for 6 hours. At a temperature of 130°C and the reaction time of 6 hours, the yield of methyl ethers of ortho- and para-methoxybenzic acid is 15% and 46%, ethyl - 32% and 68%, propyl - 23% and 78%, and butyl - 12% and 82%.
EFFECT: increasing the yield.
1 tbl, 27 ex
FIELD: cleaning exhaust gases from nitrogen oxides in industrial plants by means of selective catalytic cleaning with the use of ammonia.
SUBSTANCE: proposed method includes reduction of nitrogen oxides by ammonia on catalyst in presence of hydrogen. Before delivery to catalyst, exhaust gases are mixed with purge gases from the ammonia synthesis cycle. Content of hydrogen in mixture is maintained below low limit of ignition. Purge gases are enriched with ammonia by mixing them with ammonia synthesis gases.
EFFECT: reduced consumption of ammonia; enhanced mixing of exhaust gases with ammonia; reduced emissions of ammonia into atmosphere; reduced power requirements.
SUBSTANCE: invention relates to a special perovskite type compound, a catalyst which contains such a compound, a method of decomposing dinitrogen monoxide (N2O), a device for producing nitric acid and a method of producing nitric acid. The invention also relates to use of the said perovskite type compound in decomposing N2O. The invention describes the device used in the method of producing nitric acid at the ammonia oxidation step, which includes a perovskite type compound for decomposing dinitrogen monoxide having general formula (1). There is an ammonia oxidation catalyst, one or more separating gauzes and a perovskite type compound along the gas stream containing the product. The invention describes a method of producing nitric acid using the said device. Described also is a catalyst for use in the said device, which has a cellular support and a perovskite type compound of general formula (1). The invention also describes a method of decomposing dinitrogen monoxide for use in the device described above, which involves bringing dinitrogen monoxide into contact with the perovskite type compound of general formula (1) and using the said perovskite compound to decompose dinitrogen monoxide for use in the device described above.
EFFECT: decomposition of N2O in the gas containing the product formed during oxidation of ammonia when producing nitric acid.
14 cl, 5 ex, 16 tbl, 1 dwg
FIELD: production of disodic phosphate by neutralization of phosphoric acid by soda for obtaining neutralized disodic phosphate solution after cooling.
SUBSTANCE: phosphoric acid is first neutralized by disodic phosphate solution to ratio Na2O/P2O5 = 0.6-0.7 at temperature of 80°C and then with soda at temperature of 70-75°C at liberation of disodic phosphate by cooling the neutralized solution to 35°C at rate of 4-4.5 deg/h. Proposed method makes it possible to increase productivity of process by 1.15-1.5 times and to reduce amount of coolant by 1.5-2 times. Proposed method provides for reduction of expenses for packaging, storage, transportation and use by 1.3 times.
EFFECT: reduction of expenses for packaging, storage, transportation and use.
FIELD: heat power and chemical industries, applicable in production of ammonia.
SUBSTANCE: in the method for steam generation at production of ammonia from hydrocarbon gases, saturation of the hydrocarbon gas after desulfurization and/or process air fed to the secondary reforming is effected due to the use of the flue gas of a tube furnace at a temperature of 160 to 580C, preferably within 220 to 480C, by means of water recirculation.
EFFECT: reduced consumption of energy due to reduction of the total amount of generated steam, reduced consumption of feed water, and recovered gases dissolved in the process condensate.
4 cl, 1 dwg
FIELD: heat power and chemical industries, applicable in production of ammonia.
SUBSTANCE: in the method for steam generation at production of ammonia from hydrocarbon gases the mean-pressure steam used for the process of steam reforming and/or for the compressor drives is subjected to humidification by injection of the process condensate or feed water, and the obtained humidified steam is overheated by the heat of the flue gas in a unit of the heat-using equipment of the reforming tube furnace.
EFFECT: reduced consumption of energy due to reduction of the amount of generated steam and reduced of the amount of generated steam and reduced consumption of feed water; provided additional cleaning of the process condensate and recovering of gases dissolved in it in the process of steam humidification in the mass transfer device.
2 cl, 1 dwg
FIELD: inorganic synthesis catalysts.
SUBSTANCE: invention provides ammonia synthesis catalyst containing ruthenium as active ingredient supported by boron nitride and/or silicon nitride. Catalyst can be promoted by one ore more metals selected from alkali, alkali-earth metal, or rare-earth metals. Ammonia synthesis process in presence of claimed catalyst is also described.
EFFECT: increased temperature resistance of catalyst under industrial ammonia synthesis conditions.
4 cl, 6 ex
FIELD: chemical industry; production of ammonia.
SUBSTANCE: the invention is pertaining to the process of synthesis of ammonia, in particular to improvement of the process of cleanout synthesis of the gas added into the catalytic reactor for substitution of the reacted synthesis gas. The method of synthesis of ammonia provides for compression of the synthesis gas containing hydrogen and nitrogen in a many-stage centrifugal compressor. On the first stage of this compressor the synthesis gas is compressed up to the pressure making from approximately 800 up to 900 pounds per a square inch - (56-63)·105 Pa, withdraw from this stage and cool, and also dehydrate by a contact to a liquid ammonia in a dehydrator. Then the cooled and dehydrated synthesis gas is fed back in the compressor and bring it on the second stage. The installation for realization of this process contains a centrifugal compressor supplied with the synthesis gas outlet, that connects the synthesis gas discharge outlet from the first stage of the compressor with the synthesis gas inlet in the dehydrator, and also an intermediate inlet of the synthesis gas connecting by a hydraulic link the inlet of the second stage of the compressor with the synthesis gas discharge (outlet) from the dehydrator. Due to the intermediate cooling and a dehydration the compressor rate is lowered, and due to favorable effect of the dehydrator on the last two stages of the compressor a significant saving of the consumed power is also achieved. The additional saving of the consumed power is possible due to decreased need of chill in the closed contour of the synthesis process.
EFFECT: the invention ensures a significant saving of the consumed power for the synthesis process in the installation.
13 cl, 1 dwg
FIELD: industrial inorganic synthesis.
SUBSTANCE: process comprises passing nitrogen and hydrogen-containing synthesis gas stream through three stacked catalyst beds, wherein catalyst is based on iron with magnetite as principal constituent, which is reduced during the process until catalytically active form of alpha-iron is produced. Above-mentioned synthesis gas stream is obtained by combining stream directly supplied onto first catalyst bed with another stream, which is preheated via indirect heat exchange with products exiting first and second catalyst beds, whereupon product is recovered. Method is characterized by that gas under treatment is passed through middle catalyst bed at volume flow rate between 0.65 and 2.00 value of volume flow rate, at which gas under treatment is passed through upper catalyst bed, volume ratio of middle catalyst bed to upper catalyst bed lying preferably between 0.5 and 1.5.
EFFECT: increased yield of product.
2 cl, 1 dwg, 1 tbl
FIELD: inorganic synthesis catalysts.
SUBSTANCE: ammonia synthesis catalyst includes, as catalytically active metal, ruthenium deposited on magnesium oxide having specific surface area at least 40 m2/g, while concentration of ruthenium ranges between 3 and 20 wt % and content of promoter between 0.2 and 0.5 mole per 1 mole ruthenium, said promoter being selected from alkali metals, alkali-earth metals, lanthanides, and mixtures thereof. Regeneration of catalytic components from catalyst comprises following steps: (i) washing-out of promoters from catalyst thereby forming promoter-depleted catalyst and obtaining solution enriched with dissolved promoter hydroxides; (ii) dissolution of magnesium oxide from promoter-depleted catalyst in acidic solvent wherein ruthenium is insoluble and thereby obtaining residual ruthenium metal in solution enriched with dissolved magnesium compound; and (iii) regeneration of residual ruthenium metal from solution enriched with dissolved magnesium compound via liquid-solids separation to form indicated solution enriched with dissolved magnesium compound and ruthenium metal.
EFFECT: increased catalyst activity.
6 cl, 6 ex