Method for the production of ammonia
(57) Abstract:Sobranie relates to the production of ammonia from gaseous and liquid hydrocarbons and can be used in the chemical and petrochemical industries. Method for the production of ammonia includes a two-stage catalytic conversion of hydrocarbons under pressure with steam and air compressed by a compressor driven by a gas turbine, the conversion of carbon monoxide with obtaining nitric mixture, purification from carbon oxides, the selection of the purified gas mixture of hydrogen, a mixture of the latter with a gas stream enriched in nitrogen to the stoichiometric ratio of hydrogen to nitrogen is 3 : 1, flow derived nitric mixture for the synthesis of ammonia, in order to reduce energy consumption before the release of hydrogen gas mixture is divided into flows in a volume ratio(0,42 - 0,63) : (0,58 - 0,37), however, the selection of hydrogen lead from the second stream and separate the hydrogen is mixed with the first stream with obtaining nitric mixture of stoichiometric composition, and the remaining after the separation of the hydrogen fraction is served on a turbine with a pressure equal to 95 - 98% of the partial pressure of the mixture. The cost of the low-potential is(0,67 - 0,425) Gcal/t NH3. 1 Il., table 4. The invention relates to the production of ammonia from gaseous and liquid hydrocarbons and can be used in the chemical and petrochemical industries.The aim of the invention is the reduction of energy consumption.To achieve this goal in the method of producing ammonia, comprising a two-stage catalytic conversion of hydrocarbons under pressure with steam and air compressed by a compressor driven by a gas turbine, the conversion of carbon monoxide with obtaining a mixture of nitric, cleaned from oxides of carbon, separation of the purified gas mixture of hydrogen, a mixture of the latter with a gas stream enriched in nitrogen, up to the stoichiometric ratio of hydrogen to nitrogen is 3:1, flow derived nitric mixture for the synthesis of ammonia, according to the present invention, before the release of hydrogen gas mixture is divided into flows in a volume ratio(0,42-0,63):(0,58-0,37), however, the selection of hydrogen lead from the second stream and separate the hydrogen is mixed with the first stream with obtaining nitric mixture of stoichiometric composition, and the remaining after the separation of the hydrogen fraction is served on Turbin to reduce energy consumption.This is due to the following:
1. Replacing the separation process converted and purge gases to the process of separation of the hydrogen gas in the presence of intermetallic compounds or by passing them through a diffusion membrane, while maintaining the pressure of the liberated hydrogen and waste fractions.2. Separation of nitric mixture after stage mahanirvana into two streams, one of which komprimiert to pressure synthesis, and from the second emit hydrogen, mix it before komprimirovannom with the first stream and the waste fraction under pressure is directed to the combustion gazoturbogeneratorov unit.3. The bonding emitted from the converted and the purge gas intermetallic compounds of hydrogen until the pressure synthesis.In the drawing given technological scheme of the proposed method of production of ammonia and hydrogen. It includes mixer hydrocarbons with water vapor 1, the heat exchanger 2, the Converter tubular primary reformer 3, mine deconverter secondary reformer 4, the apparatus teplooborudovanie 5, CO conversion stage 6, stage washing from CO27, the stage of mahanirvana 8, the intermetallic compression ammonia synthesis 12, hedebrant 13, the circulation compressor 14, a separator 15, the separator of hydrogen from the purge gas ammonia synthesis 16, the process air compressor 17, the air compressor to the combustion 18, the combustion chamber gazoturbogeneratorov unit 19, the gas turbine 20, the unit teplooborudovanie for gas turbine 21.Compressed hydrocarbon raw materials in the mixer 1 is mixed with steam and after heating in the heat exchanger 2 by the heat converted gas after the secondary reformer is served in a tubular Converter 3, where in the reaction tubes at the Nickel catalyst through indirect heat exchange with the converted gas stream after the air shaft reforming is the process of steam reforming at 621-749aboutTo the residual methane 25-44% about. The converted gas after the Converter 3 is fed in mine deconverter 4. This also serves heated to 700-900aboutWith process air. In mine deconverter 4 the process air dikonversi hydrocarbons at 1100aboutRatio (H2+CO)/N21,37-2,0. The converted gas is sent to the Converter tube 3, which gives off heat to cover the endothermic effect of the steam reforming process.
aboutWith converted gas sequentially passes through the stages of conversion of carbon monoxide 6, shaded from carbon dioxide 7 and stage mahanirvana residues co and CO28. All of these stages is rational utilization of secondary heat resources in the process of exothermic reactions to produce process energy and steam. Cleaned from oxide and dioxide nitric mixture with a ratio of N2/N2= 1,33-1,91 divided into two streams in relation to(0,42-0,63):(0,68-0,37). The first stream is sent to the Department of synthesis and of the second flow produce hydrogen in the hydrogen separator 9 under the pressure of one of the known methods and mix it with the first stream in the mixer 10, with the formation of nitric mixture with a ratio of N2/N2=2,9-3,0 and remaining after the separation of the hydrogen-enriched nitrogen fraction under pressure is directed to the combustion in the chamber of the gas turbine 19.Nitric mixture komprimiert in the compressor 11 to the pressure of the synthesis, mixed with the circulating gas and sent to the ammonia synthesis column of 12.The mixture is proektnym turn holocoenic 13, is divided into two streams. One of the threads is sent to the circulating gas compressor 14, and the second purge gases ammonia synthesis) - separator of hydrogen from the purge gas ammonia synthesis 16.Purge gases after separation of the hydrogen gas containing methane, hydrogen, argon and nitrogen, under pressure mixed with a second stream enriched in nitrogen fractions after hydrogen separator 9 and is directed to the combustion in the combustion chamber 19 of the gas turbine unit 20. This also serves compressed in the compressor 18 for combustion air. Gas turbine unit is used to drive the compressor fuel air 18 and the process air compressor 17, after which the process air is heated to 700-900aboutWith the unit teplooborudovanie 21 and is directed to the process of mine dikonversi the Converter 4.P R I m e R 1. Hydrocarbons in the number 54405,6 m3/h with the composition, vol.%: CO2- 0,03; N2- 4,2; N2- 6,98; Ar - 0,03; CH4- 82,2; C2H6- 4,47; C3H8- 1,36; C4H10- 0,49; C5H12- 0,24 komprimiert to 4.3 MPa, is mixed with steam in the mixer 1, is heated in heat exchanger 2 to 450aboutWith and served in a tubular reactor 3, where the reactions the e secondary shaft reforming is the process of steam reforming at 721aboutWith up to a content of residual methane in the mixture 28,08%. In mine Converter 4 receives the converted gas after the primary reformer and 107870 m3/h of air, heated to 800aboutC. Process air reforming of hydrocarbons occurs at 1010aboutWith the pressure of 3.69 MPa and the ratio (H2+CO)/N2=1,84.377606 m3/h converted gas having a composition, vol.% : CO2- 4,53; CO - 9,41; N2- 33,60; N2- 23,31; Ar - 0,28; CH4- 0.24, N2On - 28,63, out of the annulus of the tubular reactor at 580aboutWith the heating source progresterone mixture in the heat exchanger 2.Next, the converted gas is sequentially sent to the stage of conversion of carbon monoxide, flashing of carbon dioxide and stage mahanirvana from the remnants of co and CO2.< / BR>After the stage of mahanirvana drained nitric mixture of the following composition, about. %: H2- 62,95; N2- 35,59; Ar - 0,42; CH4- 1,04 when the pressure 2,99 MPa, a temperature of 40aboutWith divided into two streams. The first thread in the amount of 125483 m3/h to send kompremirovannyj, and from the second stream, which is 92401 m3/h, allocate 49441 m3/h of hydrogen, mix it with the first stream, naprawcze after the separation of the hydrogen-enriched nitrogen fraction, under pressure, equal 2,8 (95%) - 2,87 (98%) MPa, is directed to the combustion in the combustion chamber of the gas turbine unit.P R I m e R s 1-5 are shown in table. The table shows that in the proposed method in contrast to the known costs of low-grade heat to the hydrogen gas is reduced by dividing the flow of nitric mixture after stage mahanirvana against(0,42-0,63)/(0,58-0,37).The total energy savings in the proposed method, including the energy consumption for kompremirovannyj, heated process air and energy on the production of hydrogen, as compared with the method of the prototype is 0,473-0,688 Gcal/NH3.Limits to reduce power consumption caused by the temperature of the reformed gas at the outlet of the annulus of the tubular Converter. Temperature below 540aboutWith causes irrational change of the constructive and technological parameters (increase in the length of the reaction tubes and the height of the apparatus, increasing the resistance of the pressure drop, which will lead to an increase in the intensity), and at a temperature of 800aboutWith a two-step conversion of methane is practically replaced by a single-stage shaft conversion. WAY Prom with water vapor and air, compressed by a compressor driven by a gas turbine, the conversion of carbon monoxide with obtaining nitric mixture, purification from carbon oxides, the selection of the purified gas mixture of hydrogen, a mixture of the latter with a gas stream enriched in nitrogen to the stoichiometric ratio of hydrogen to nitrogen is 3 :1, flow derived nitric mixture for the synthesis of ammonia, characterized in that, to reduce energy consumption, before the release of hydrogen gas mixture is divided into flows in a volume ratio(0,42 - 0,63) : (0,58 - 0,37), however, the selection of hydrogen lead from the second stream and separate the hydrogen is mixed with the first stream with obtaining nitric mixture of stoichiometric composition, and the remaining after the separation of the hydrogen fraction is served on a turbine with a pressure equal to 95 - 98% of the partial pressure of the mixture.
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
FIELD: petrochemical industry; methods of the synthesis of ammonia from the nitrogen and hydrogen mixture produced from the natural gases.
SUBSTANCE: the invention is pertaining to the field of petrochemical industry, in particular, to the method of the synthesis of ammonia from the nitrogen and hydrogen mixture produced from the natural gases. The method of the catalytic synthesis of ammonia from the mixture of nitrogen and hydrogen provides, that the natural gas together with the oxygen-enriched gas containing at least 70 % of oxygen is subjected to the autothermal reforming at temperature from 900 up to 1200°C and the pressure from 40 up to 100 bar at the presence of the catalyzer of cracking, producing the unstripped synthesis gas containing in terms of the dry state 55-75 vol.% of H2, 15-30 vol.% of C and 5-30 vol.% CO2. At that the volumetric ratio of H2: CO makes from 1.6 : 1 up to 4 : 1. The unstripped synthesis gas is removed from the furnace of the autothermal reforming, cooled and subjected to the catalytic conversion producing the converted synthesis gas containing in terms of the dry state at least 55 vol.% of H2 and no more than 8 vol.% of CO. The converted synthesis gas is subjected to the multistage treatment for extraction ofCO2, CO and CH4. At that they realize the contact of the synthesis gas with the liquid nitrogen and using at least one stage of the absorption treatment produce the mixture of nitrogen and hydrogen, which is routed to the catalytic synthesizing of ammonia. At that at least a part of the synthesized ammonia may be transformed into carbamide by interaction with carbon dioxide. The realization of the method allows to solve the problem of the ammonia synthesis efficiency.
EFFECT: the invention ensures solution of the problem of the ammonia synthesis efficiency.
8 cl, 1 ex, 2 tbl, 2 dwg
FIELD: chemical industry; installations and the methods of production of the synthesis-gas from the natural gas.
SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the installation and the method for simultaneous production from the natural gas of the methanol synthesis-gas, the ammoniac synthesis-gas, carbon monoxide and carbon dioxide. The installation consists of the in-series connected to each other assembly units and includes: the first reactor (A), in which at feeding of oxygen realize the transformation of the natural gas into the synthesis gas consisting of carbon monoxide, carbon dioxide, hydrogen and the steam; the second reactor (B), in which exercise the regular transformation of carbon monoxide into carbon dioxide; if necessary the compressor (C) using which the formed gases may be contracted; absorbing apparatus D, which serves for absorption of carbon dioxide and production of he mixture of monoxide with hydrogen used for synthesizing methanol; the refrigerating separator E, in which at feeding of the liquid nitrogen receive the ammoniac synthesis gas and simultaneously produces carbon monoxide, argon and methane. The invention allows to increase profitability of the installation due to production at one installation of several products.
EFFECT: the invention ensures the increased profitability of the installation due to production at one installation of several products.
15 cl, 1 dwg, 1 tbl
FIELD: inorganic synthesis catalysts.
SUBSTANCE: ammonia synthesis catalyst is based on ruthenium on carrier of inoxidizable pure polycrystalline graphite having specific BET surface above 10 m2/g, said graphite being characterized by diffraction pattern comprising only diffraction lines typical of crystalline graphite in absence of corresponding bands of amorphous carbon and which graphite being activated with at least one element selected from barium, cesium, and potassium and formed as pellets with minimal dimensions 2x2 mm (diameter x height). Catalyst is prepared by impregnating above-defined catalyst with aqueous potassium ruthenate solution, removing water, drying, reduction to ruthenium metal in hydrogen flow, cooling in nitrogen flow, water flushing-mediated removal of potassium, impregnation with aqueous solution of BaNO3 and/or CsOH, and/or KOH followed by removal of water and pelletizing of catalyst.
EFFECT: increased activity of catalyst even when charging ruthenium in amount considerably below known amounts and increased resistance of catalyst to methane formation.
12 cl, 1 tbl
FIELD: chemical industry; methods and devices for production of ammonia from the synthesis gas.
SUBSTANCE: the invention is pertaining to the method and installation for production of ammonia from the synthesis gas. The method of production of ammonia provides for the catalytic reaction of the synthesis gas contracted in the appropriate compressor having several stages, each of which has the inlet and the outlet for the synthesis gas. The synthesis gas is purified by the liquid ammonia from contained in it water and carbon dioxide. At that at purification of the synthesis gas use the gas-liquid mixer, which is connected on the one hand to the outlet of the first stage of the compressor, or to the outlet of the intermediate stage of the compressor, and on the other hand - with the inlet of the second stage located behind the first stage, or with the inlet of the intermediate stage of the compressor, and has the section of the certain length with diminishing cross-section. Into the mixer in the axial direction feed in the forward flow the stream of the synthesis gas taken from the first stage of the compressor, or from the intermediate stage and the stream of the liquid ammonia, essentially the dehydrated synthesis gas is separated from the mixture flow coming out of the mixer and guide it into the second stage of the compressor, which is located behind the first stage or behind the intermediate stage. The technical result of the invention consists in the rise of the conversion outlet and in the decrease of the power inputs.
EFFECT: the invention ensures the increased conversion outlet and the decreased power inputs.
10 cl, 2 dwg