• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Ammonia synthesis processes are disclosed which provide enhanced conversion of hydrogen values to ammonia. In the processes, a purge stream from an ammonia synthesis loop is treated to reduce its ammmonia content to less than about 0.5 volume percent. The purge stream is then contacted at a pressure of at least substantially the superatmospheric synthesis pressure of the ammonia synthesis with the feed side of a separation membrane which exhibits selective permeation of hydrogen as compared to the permeation of each of methane and argon. A total pressure differential is maintained across the membrane to provide a driving force for hydrogen permeation through the membrane. A hydrogen-rich permeating gas is obtained on the permeate exit side of the membrane. The permeating gas is combined with gas passing to the ammonia synthesis reaction zone for conversion to ammonia. For instance, the permeating gas can be combined with synthesis feed gas or directly introduced into the ammonia synthesis loop. A non-permeating gas is removed from the feed side of the separation membrane at substantially the same pressure at which the purge stream is contacted with the separation membrane and provides a valuable source of energy due to its high pressure and combustible gas content.
    公开号:SU1001852A3
    申请号:SU792742250
    申请日:1979-03-19
    公开日:1983-02-28
    发明作者:Перри Эли
    申请人:Монсанто Компани (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD OF SYNTHESIS AAAMIAK
    one
    This invention relates to methods for producing ammonia and relates to the removal of hydrogen from purge gases.
    A known method for the synthesis of ammonia from nitrogen and hydrogen under pressure, in which separate components, for example hydrogen, is made of purge gases using a deep cooling gas stream.
    The disadvantages of this method are the significant costs associated with the use of cold, as well as the production of isolated components with low pressure.
    The closest to the proposed technical essence and the achieved result is the method of ammonia synthesis, which includes compression of the nitric mixture, ammonia accumulation, ammonia extraction, circulation of unreacted nitric mixture, purging, part of these gases, followed by hydrogen separation from them through separation membranes , and the supply of hydrogen in the initial hydrous mixture of J.
    A disadvantage of the known method is that purge gas, which contains ammonia, is fed to the separation membranes, in order to remove hydrogen. 5 Ammonia entering the initial nitric mixture negatively affects the ammonia synthesis process. In addition, methane and argon present in the gas stream are recovered. The presence of these impurities
    10 also reduces the productivity of the process.
    The goal of the invention is an increase in permeability capable of ammonia synthesis. The goal is achieved by
    ) 5 that according to the method of ammonia synthesis, which includes compression of the initial nitrogenous prenatal mixture, ammonia synthesis, release of ammonia, circulation of unreacted aero hydrogen-hydrogen mixture, purge part of these gases, followed by separation of hydrogen from purge gases using separation membranes, supply of separated hydrogen in the initial nitric mixture, the ammonia from the purge gases is removed before their contact with the separation membrane to a content of 0.01-0.5% by volume. Such an amount does not affect the structure of the used membranes, does not destroy it, and allows the use of membranes, the result of IHZ of their permeability to hydrogen. In addition, the release of ammonia from the purge below the specified limits is not economically feasible. Ammonia from the purge gases can be removed by cooling, and then the residual amount of ammonia can be removed by flushing. The gas not permeable through the membrane can be used as fuel or directed to expansion to remove energy, since it is under pressure. Gas that has passed through the membrane and contains hydrogen may be returned to the main cycle of ammonia synthesis. The method is carried out as follows. The initial nitric mixture is fed under pressure of 125-275 atm, 1 to the reactor, where in the presence of, for example, an iron-based catalyst, the ammonia is reacted at 2OO600 ° C. The reaction gases leaving the reactor contain from 10–15 to 25% ammonia, which is condensed and released as a liquid product. Ammonia separators are used to more completely release ammonia. Unreacted nitrogen and hydrogen are recycled. In order to reduce the amount of inert impurities in the nitrogen – nitrogen mixture, a part of the gases is hydrogenated and methane, argon and helium are extracted from them. Regardless of the place of collection, it is necessary to separate the ammonia before contacting the purge gases with the separation of the BELLOW membrane. The concentration of ammonia in the stream in front of the membrane is reduced to 0.01-0.5% by volume. Ammonia is removed from the stream with the aid of cooling, and then using water washing, in a scrubber. The purge gases are in contact with the separation membrane, which is characterized by hydrogen permeability selectivity in comparison with methane and argon permeability. The volume ratio between the permeable and non-permeable gases, as well as their composition, can vary in a wide range. The passed membrane containing hydrogen can be fed into the initial nitrogen-containing mixture 52.44 between the pressure stages, but not directly into the feed line of the initial mixture into the reactor or into the initial mixture for compression in the compressor, Example. The initial mixture of hydrogen and nitrogen in the amount of 65,000 kg / h under a pressure of 28 at and compressed to 70 at and cooled to condense water. The synthesis gas is compressed to 133 atm and introduced into the ammonia synthesis loop. The gas in the ammonia synthesis circuit is compressed for another 6–7 atm and treated in an ammonia separator, which removes about 44,500 kg of ammonia per hour. The gases are preheated to 10 5 -NO C. In the ammonia synthesis reactor, approximately 300,000 kg / h of gas is injected, containing, say: hydrogen, 67; nitrogen 2.2; methane 6.5; argon 3,3 and ammonia 1,2, and the reaction is carried out on a promoted iron catalyst. The reaction gases exit with a temperature of 280 ° C and an ammonia content of about 11.5%. The reaction gases are cooled to 43 ° C, and about 2.1% of the total amount of the exhaust gases is taken off and the rest of the gases are returned. are in the ammonia synthesis circuit. The purge gases are cooled to -23 ° C and about 820 kg of liquid ammonia per hour are removed. The purge gases are then sent to a water scrubber at 25 ° C. After the separation of ammonia, purge gases contain it less than 100 ppm by vol.) And with a pressure of about 136 atm, after being heated to 30 ° C, they are sent to separation membranes, which are made of anisotropic polysulfone. On the membrane, through which passes about 2,700 kg / h of gas with a content, vol.%: Hydrogen 88.7; nitrogen 7.2; methane 2.7; Argon 1.2 and Water 0.2 maintain a pressure drop of about 65 Ata. The unleaded gas has a pressure of about 136 at and contains vol.%: Hydrogen 40.3; nitrogen 38.4; methane 14.1 and argon 7.3. The gas passed through the membrane is introduced into the initial nitric hydrogen mixture after the first compressor prior to the condensation of water. The application of the proposed method of ammonia synthesis on a plant with an average productivity of 37,900 kg / h of ammonia allows to obtain a productivity of 39,800 kg / h, which constitutes an increase in the yield of the final product by 5%. In addition, energy consumption is reduced by 5%. 5100 acquisitions - Formula Ammonia synthesis method, which includes compression of the initial nitric mixture, synthesis of ammonia, release of ammonia, circulation of unreacted nitrogen-hydrogen mixture, purging part of these gases, followed by hydrogen from purge gases using cenaraionic membranes, supplying separated hydrogen to the original membrane, and releasing hydrogen into the original gas from the source gas from the purge gas of hydrogen through centrifugal membranes, supplying the separated hydrogen to the original hydrogen from purging gases using centered ionic membranes 52 ", characterized in that, in order to increase productivity, ammonia from the purge gases is removed before their contact with the separation membrane to a content of 0.01-0.5% by volume. Sources of information taken into account during the examination 1. US Patent No. 3675434, cl. 62-23, pubic. 1972., g, CiieniicaE Bi neenng, 1977, No. 10, p. 76-78 (prototype).
    权利要求:
    Claims (1)
    [1]
    Claim "
    A method for synthesizing ammonia, including compressing an initial nitrogen-hydrogen mixture, synthesizing ammonia, separating ammonia, circulating an unreacted nitrogen-hydrogen mixture, purging part of these grooves, and then emitting hydrogen from the purge gases using cena-iration membranes, supplying the separated hydrogen to the initial nitrogen-hydrogen mixture, which differs in order to increase the productivity, ammonia is removed from the purge gases before their contact with the separation membrane to a content of 0.01-0.5 vol.%.
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    同族专利:
    公开号 | 公开日
    RO79453A|1983-02-01|
    FR2420510A1|1979-10-19|
    DD142327A5|1980-06-18|
    GB2017071B|1982-09-29|
    US4172885A|1979-10-30|
    IT7921113D0|1979-03-19|
    GB2017071A|1979-10-03|
    NL182797C|1988-05-16|
    MX150538A|1984-05-23|
    DE2910742A1|1979-09-27|
    PL214235A1|1980-02-11|
    FR2420510B1|1983-07-18|
    NL7902102A|1979-09-24|
    BE874949A|1979-09-19|
    TR21143A|1983-11-22|
    BR7901687A|1979-10-16|
    JPS5725491B2|1982-05-29|
    CA1107479A|1981-08-25|
    AU514585B2|1981-02-19|
    JPS54157797A|1979-12-12|
    NL182797B|1987-12-16|
    AU4521779A|1979-09-27|
    IT1113314B|1986-01-20|
    IN149407B|1981-11-28|
    PL117802B1|1981-08-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    US3492099A|1964-10-12|1970-01-27|Lummus Co|Parallel gas flow reactor|
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    US3947551A|1974-05-29|1976-03-30|The Benfield Corporation|Ammonia synthesis|
    GB1460681A|1975-02-06|1977-01-06|Petrocarbon Dev Ltd|Treatment of ammonia synthesis purge gas|
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    US4652283A|1983-06-30|1987-03-24|Monsanto Company|Polyphenylene oxide membrane having chemically bonded coating|
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    US4592903A|1983-11-10|1986-06-03|Exxon Research & Engineering Co.|Low severity hydrocarbon steam reforming process|
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    US4527999A|1984-03-23|1985-07-09|Abcor, Inc.|Separation membrane and method of preparing and using same|
    FR2564452B1|1984-05-18|1988-06-10|Rumyantsev Ivan|PROCESS FOR THE PREPARATION OF AMMONIA AND AMMONIA OBTAINED BY SAID PROCESS|
    US4645516A|1985-05-24|1987-02-24|Union Carbide Corporation|Enhanced gas separation process|
    US5055116A|1989-05-22|1991-10-08|Hoechst Celanese Corp.|Gas separation membranes comprising miscible blends of polyimide polymers|
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    US4762535A|1987-06-02|1988-08-09|Air Products And Chemicals, Inc.|Ammonia separation using semipermeable membranes|
    US5096468A|1987-10-19|1992-03-17|W. R. Grace & Co.-Conn.|Cellulose acetate butyrate gas separation membranes|
    US4836833A|1988-02-17|1989-06-06|Air Products And Chemicals, Inc.|Production and recovery of hydrogen and carbon monoxide|
    US4793829A|1988-03-10|1988-12-27|International Permeation, Inc.|Permeation process for separating ammonia from a gas mixture|
    US5000763A|1989-06-14|1991-03-19|The Dow Chemical Company|Process for separating hydrogen from gas mixtures using a semi-permeable membrane consisting predominantly of polycarbonates derived from tetrahalobisphenols|
    US5009678A|1989-10-31|1991-04-23|Union Carbide Industrial Gases Technology Corporation|Process for recovery of ammonia from an ammonia-containing gas mixture|
    US5028307A|1989-12-26|1991-07-02|Rightmyer Donald A|Apparatus for generation of hydrogen and other gases from the decomposition of organic matter|
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    US5114694A|1990-04-02|1992-05-19|C. F. Braun & Co.|Ammonia recovery from purge gas|
    US5034026A|1990-04-20|1991-07-23|The Dow Chemical Company|Polybenzazole polymers containing indan moieties|
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    GR1002482B|1995-12-07|1996-12-03|Γεωργιος Σακελλαροπουλος|New polymer membranes prepared from polysulfone and polyimide blends for the separation of industrial gas mixtures.|
    MXPA01007837A|1999-02-03|2004-08-19|Texaco Development Corp|Utilizing purge gas from ammonia synthesis.|
    NO317382B1|2001-02-16|2004-10-18|Norsk Hydro As|Method for carrying out a catalytic or non-catalytic process|
    JP5373410B2|2009-01-09|2013-12-18|トヨタ自動車株式会社|Ammonia synthesis method|
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    CN104986734B|2015-06-24|2017-03-08|杭州中泰深冷技术股份有限公司|A kind of synthesis ammonia synthesis gas self-loopa cryogenic separation purifier and its purification method|
    IT201800000620A1|2018-01-08|2019-07-08|Nuovo Pignone Tecnologie Srl|AMMONIA PRODUCTION PLANT|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/888,101|US4172885A|1978-03-20|1978-03-20|Process for the recovery of hydrogen from ammonia purge gases|
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