• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 引用文献
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  • 优先权
    • 专利摘要:
    Catalytic process for the production of sulphur from an acid gas containing H2S, in which a part of H2S is catalytically oxidized in order to form an effluent containing H2S and SO2 in a molar ratio of 2:1 and a given quantity of sulphur. The effluent is then contacted with a CLAUS catalyst to form a further quantity of sulphur. Said process involves: an oxidation reactor with a fixed bed an indirect gas/gas heat exchanger deoxygenation reactor having a fixed bed a catalyst conversion battery a thermal incinerator.
    公开号:SU1291025A3
    申请号:SU823478231
    申请日:1982-08-18
    公开日:1987-02-15
    发明作者:Вуатрен Робер
    申请人:Сосьете Насьональ Елф Акитэн (Продюксьон) (Фирма)；
    IPC主号:
    专利说明:

    ,
    .1129
    This invention relates to catalytic processes for the production of sulfur from acid gas containing hydrogen sulphide up to 20% by volume.
    The aim of the invention is to simplify the process of oxidation of hydrogen sulfide by allowing it to be carried out before.
    The method according to the invention consists in that hydrogen sulfide-containing gas is oxidized with atmospheric oxygen at a temperature of up to 700 ° C to obtain a gas mixture with a HjS: SOn ratio of 2: 1 in the presence of a catalyst deposited on an alkali refractory oxide in an amount of 3 - 12% and a compound of the metal selected from the group consisting of iron, copper, zinc, cadmium, chromium, molybdenum, tungsten, cobalt, nickel, bismuth, or a mixture of compounds of one of these metals with palladium, platinum, iridium and rhodium, in quantity be 0.02-0.09 wt.%. The resulting reaction mixture is further cooled with the elimination of elemental sulfur, and the remaining gas mixture is processed according to the Claus method.
    The catalyst carrier having a specific surface area of at least 5, in particular 120-800 m Ug, is selected from the group consisting of silicon dioxide, titanium oxides, zirconium, mordenite, fujazite zeolite, felerite, alumina.
    Oxides, salts of mineral or organic acids, for example, sulfa, are used as metal compounds.
    you, nitrates, phosphates, acetates.
    The contact time of the gas reaction
    Wednesday 10 s.
    with a catalyst it is 0.5 When the content of hydrogen sulfide in the gas mixture after oxidation is less than 2 vol.%.
    The Claus process is carried out at a temperature below the sulfur dew point (in the range of 80-160 ° C), and sulfur obtained during the reaction of H S with SO. deposited on the catalyst. Ø catalyst periodically regenerated by purging with oxygen-free gas with a temperature of 200-400 C.
    If the content of H S in the gas mixture is higher than 2 vol.%, Then the Claus process is carried out at a temperature of about 10–40 ° C.
    2
    by this
    Example 1 A method is carried out on a pilot plant comprising the following elements: a fixed bed oxidation reactor containing 600 kg of the proposed catalyst
    } 0
    15
    ,,
    0
    25
    thirty
    35
    40
    t
    50
    55
    a pipeline for supplying a mixture of acid gas and air and a pipeline for discharging oxidation effluent; an indirect gas / gas heat exchanger, one of the heat exchange circuits, is mounted in series on the sour gas and air mixture supply line, the other circuit is in series with the oxidation effluent output line; a fixed bed reduction reactor containing 1200 kg of antioxidant catalyst in the form of balls with a diameter of 4-5 mm, consisting of activated alumina impregnated with ferrous sulfate (4 wt.% iron based on the weight of the calcined catalyst); the reactor inlet is connected to the outlet pipe of the oxidation effluent through the corresponding circuit of the heat exchanger; a catalytic converter system containing two catalytic converters and a sulfur condenser cooled with water vapor, each of the converters containing 1800 kg of one CLAUS catalyst consisting of activated alumina in the form of balls 4-6 mm in diameter, the converters and the sulfur condenser are installed in such a way that the outlet of the reduction reactor is connected in turn with the input of one or another converter, and the latter are connected in series through a sulfur condenser; a furnace, the input of which is connected to the output of the catshitic transformation group.
    As an oxidation catalyst, a catalyst obtained by impregnation of balls with a diameter of 4–6 mm from silica with a specific surface area of 240 iron sulphate is used; this catalyst contains 5% by weight of iron relative to the weight of the calcined catalyst,
    The acid gas produced is coal gasification product and has the following composition, vol.%: 1.5; CO 5 91.5; 7
    Air at a rate of 35.7 and the resulting gas mixture are added to the acid gas at a flow rate of 1000 (standard condition).
    preheated to 250 ° C by passing through a heat exchanger, then introduced into the oxidation reactor. The contact time of the gas mixture with the oxidation catalyst is 2 s (standard condition), and the temperature inside the catalytic layer is 315 ° C.
    The oxidation reactor effluent contains hydrogen sulphide and sulfur dioxide in a molar ratio of hydrogen sulfide to sulfur dioxide 2: 1, as well as 10 vol, h per million of free oxygen and vaporous sulfur, the amount of which corresponds to the degree of conversion of hydrogen sulfide into sulfur equal to 40% .
    The effluent — at 315 ° C — goes to a heat exchanger, where part of its heat is used to preheat the oxygen-gas-air mixture. The cooled effluent then passes through a reduction reactor, where it is freed from residual oxygen. The contact time of the reduction catalyst with the cooled effluent. with.
    The reaction mixture containing hydrogen sulfide, sulfur dioxide and sulfur vapor coming from the reduction reactor is passed through a converter operating in regeneration mode, which would blow the catalyst filled with sulfur contained in the converter, and this blowing at 300 ° C and the contact time gas / / catalyst "6 p. The gas containing sulfur leaves the regeneration converter, then passes through a sulfur condenser cooled by water vapor, where it is cooled before and freed from the sulfur it contained as a result of condensation. The cooled gas, which contained hydrogen sulfide and sulfur dioxide, as well as a small amount of sulfur vapor, is passed through a catalytic converter operating in the Claus reaction mode, system. Catalytic converters, operating at ISO C, with the gas / catalyst contact time sulfur as a result of the reaction of hydrogen sulfide and sulfur dioxide, and this sulfur is deposited on the catalyst.
    Residual gases leaving the converter in the Claus reaction mode are directed to thermal ashing, and the smoke resulting from ozo. Laziness, containing a small amount of sulfur dioxide as the only sulfur compound, is emitted into the atmosphere through a chimney.
    Residual gases leaving the group of catalytic converters contain no more than 936 ob.h. per million of the total amount of sulfur, namely HjS, SOj, bubbly or vaporous sulfur, which corresponds to a total conversion of hydrogen sulfide to sulfur of 93.5%.
    Examples of the method are presented in table. one. .
    PRI mme R 2. In an installation similar to that used in Example 1, a series of tests on the treatment of acid gas of the following composition were carried out,% by volume: H, 14; CO 80; 6
    As oxidation catalyst, 600 kg of catalyst are used, different in each 3 tests, which are prepared by impregnating silica balls 4-6 mm in diameter (130 surface area) with an aqueous solution of one or more metal compounds selected from the group Fe, Cu, Zn, Cd, Cr, Mo, W, Co, Ni, Bi, Pt, Ir and Rli, followed by drying the impregnated balls at 110 ° C and calcining at 460 ° C.
    The characteristics of the antioxidant catalyst in the reduction reactor and the catalyst K. 1AUS present in each converter of the catalytic conversion battery, as well as the amounts of these catalysts, are as described in Example 1.
    35.0 air are added to the acid gas coming from the races (1000 run (standard conditions) and the resulting gaseous mixture is preheated to 200 ° C, passed through a heat exchanger, then into the oxidation reactor. The contact time of the gas mixture with the oxidation catalyst is 2 s ( standard conditions), the temperature in the catalyst bed is 700 ° C for each test.
    The effluent of the short-circuit oxidation reactor is fed to the reduction reactor, then to the catalytic conversion battery, and then to the furnace for calcination under operating conditions corresponding to those described in Example 1.
    In tab. 2 shows examples of the method.
    5 1291025
    The proposed catalyst allows to operate at temperatures up to 700 ° C without a significant decrease in its activity and thereby simplifies the stage.
    oxidation of H.S due to elimination after cooling to this stage to reduce the process temperature.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    10 a compound of a metal selected from the group consisting of iron, copper, zinc, cadmium, chromium, molybdenum, tungsten, cobalt, nickel, bismuth, or a mixture of compounds of one of these metals
    The method of obtaining sulfur from sulfur dioxide-containing gas, including oxidation of the latter with oxygen-containing gas to obtain a gas mixture with a ratio of H SrSOj equal to 2: 1, t5 fishing with a metal compound from the group, at a higher temperature in the presence of pags, platinum, catalyst iridium deposited in co-and rhodium, taken in an amount of 0.02- 3-12 wt.% per non-alkaline 0.09 wt.% in terms of metal,
    refractory oxide, cooling of the oxidation products with separation of the obtained elemental sulfur and subsequent processing of the remaining gas
    5 mixtures according to the Claus method, characterized in that, in order to simplify the oxidation process due to the possibility of carrying it up to, a catalyst is used as a catalyst
    0 a compound of a metal selected from the group consisting of iron, copper, zinc, cadmium, chromium, molybdenum, tungsten, cobalt, nickel, bismuth, or a mixture of a compound of one of these metals with a compound of a metal from the group including pagsadium, platinum, iridium and rhodium, taken in the amount of 0.02-0.09 wt% in terms of metal,
    Spreadsheets
    Editor L. Veselovska
    Compiled by L. Temirova
    Tehred M. Khodanych Proofreader t.Kolb
    Order 7921/60 Circulation 456 Subscription
    VNISh State Committee of the USSR
    for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab, 4/5
    Production and printing company, Uzhgorod, ul, Proektna, 4
    Taldnia2
    类似技术:
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    同族专利:
    公开号 | 公开日
    IT1153716B|1987-01-14|
    DK370482A|1983-02-20|
    FR2511663B1|1985-02-15|
    DE3230553C2|1997-04-24|
    DE3230553A1|1983-03-31|
    JPS5836906A|1983-03-04|
    CA1208885A|1986-08-05|
    US4479928A|1984-10-30|
    GB2105315A|1983-03-23|
    FR2511663A1|1983-02-25|
    IT8222893D0|1982-08-19|
    UA5551A1|1994-12-28|
    GB2105315B|1985-06-12|
    NL8203223A|1983-03-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    US2083895A|1933-12-21|1937-06-15|Sulco Lab Inc|Catalytic process for the conversion of sulphur compounds|
    US2083894A|1933-12-21|1937-06-15|Sulco Lab Inc|Process for the treatment of sulphur compounds|
    US2697064A|1953-07-13|1954-12-14|Universal Oil Prod Co|Desulfurization and reforming of hydrocarbon fractions|
    FR72408E|1957-10-23|1960-04-13|Fr D Oxycatalyse Oxy France So|Process for the desulfurization of gases and the recovery of elemental sulfur contained in the sulfur compounds they contain|
    GB1340067A|1970-08-26|1973-12-05|British Gas Corp|Recovery of sulphur from gases|
    FR2190517B1|1972-06-29|1975-08-29|Rhone Progil|
    US4141962A|1973-04-09|1979-02-27|Rhone-Progil|Catalysts for treating gases containing sulphur compounds|
    FR2242145B1|1973-08-30|1977-09-09|Rhone Progil|
    FR2277877B1|1974-07-11|1976-12-24|Aquitaine Petrole|
    US4012486A|1975-07-02|1977-03-15|Shell Development Company|Process for reducing the total sulfur content of Claus off-gases|
    DE2531930A1|1975-07-17|1977-01-20|Metallgesellschaft Ag|PROCESS FOR THE RECOVERY OF ELEMENTARY SULFUR FROM GASES RICH IN CARBON DIOXIDE, SULFUR COMPOUNDS AND POLLUTIONS|
    US4171347A|1975-08-18|1979-10-16|Union Oil Company Of California|Catalytic incineration of hydrogen sulfide from gas streams|
    FR2327960B1|1975-10-17|1980-05-30|Elf Aquitaine|
    US4192857A|1975-10-17|1980-03-11|Societe Nationale Elf Aquitaine |Sulphur production|
    FR2456543B1|1979-05-15|1984-02-10|Inst Francais Du Petrole|
    FR2481254B1|1980-04-23|1984-02-17|Elf Aquitaine|
    FR2494255B1|1980-11-17|1984-12-14|Elf Aquitaine|DE3143400A1|1981-11-02|1983-06-01|Mobil Oil Corp., 10017 New York, N.Y.|METHOD FOR REDUCING THE SULFUR CONTENT IN GAS FLOWS WITH ELEMENTAL SULFUR|
    FR2540092B1|1983-01-31|1986-02-21|Elf Aquitaine|CATALYTIC PROCESS FOR THE PRODUCTION OF SULFUR FROM A H2S-CONTAINING GAS|
    JPS61219704A|1985-03-25|1986-09-30|Babcock Hitachi Kk|Sulfur recovering device|
    DE3529665A1|1985-08-20|1987-02-26|Metallgesellschaft Ag|METHOD FOR REMOVING SULDURATE FROM EXHAUST GASES|
    DE3535815A1|1985-10-08|1987-04-09|Metallgesellschaft Ag|METHOD FOR PURIFYING HYDROGEN SULFUR AND EXHAUST GAS SULFUR DIOXIDE|
    FR2589082B1|1985-10-25|1989-12-01|Elf Aquitaine|PROCESS FOR REMOVAL OF SULFUR COMPOUNDS CONTAINED IN A WASTE GAS, PARTICULARLY FROM A CLAUS SULFUR FACTORY, WITH RECOVERY OF SUCH SULFUR COMPOUNDS|
    FR2589141B1|1985-10-25|1987-12-11|Elf Aquitaine|PROCESS FOR REMOVAL OF SULFUR COMPOUNDS CONTAINED IN A WASTE GAS, PARTICULARLY FROM A CLAUS SULFUR FACTORY, WITH RECOVERY OF SUCH SULFUR COMPOUNDS|
    US5185140A|1985-10-25|1993-02-09|Elf Aquitaine Production|Process for removing sulphur compounds from a residual gas|
    FR2589140B1|1985-10-25|1991-02-22|Elf Aquitaine|CATALYTIC PROCESS FOR THE PRODUCTION OF SULFUR FROM AN ACID GAS CONTAINING H2S|
    US4849203A|1987-12-07|1989-07-18|Amoco Corporation|Sulfur recovery plant and process using oxygen|
    US4798716A|1986-04-29|1989-01-17|Amoco Corporation|Sulfur recovery plant and process using oxygen|
    CA1307652C|1986-05-13|1992-09-22|Iron Otto Simek|Mte sulphur recovery process|
    US5004588A|1988-01-15|1991-04-02|Chevron Research & Technology Company|Process for removal of hydrogen sulfide from gaseous stream|
    KR970001270B1|1993-08-09|1997-02-05|조말수|Process for removing h2s|
    FR2727101B1|1994-11-17|1996-12-20|Elf Aquitaine|PROCESS FOR OXIDIZING SULFUR DIRECTLY BY CATALYTIC H2S CONTAINED IN LOW CONCENTRATION IN A GAS AND CATALYST FOR CARRYING OUT THIS PROCESS|
    NL1002524C2|1996-03-04|1997-09-05|Gastec Nv|Catalyst for the selective oxidation of sulfur compounds to elemental sulfur, process for the preparation of such a catalyst and method for the selective oxidation of sulfur compounds elemental sulfur.|
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    CN101519192B|2009-03-27|2011-02-09|成都赛普瑞兴科技有限公司|Low temperature Claus sulfur recovery process and device therefor|
    CN106391135A|2016-09-27|2017-02-15|长春东狮科贸实业有限公司|Special catalyst for removing hydrogen sulfide through selective catalytic oxidation and preparation method for special catalyst|
    US11253816B2|2019-05-10|2022-02-22|Saudi Arabian Oil Company|Direct oxidation of hydrogen sulfide in a hydroprocessing recycle gas stream with hydrogen purification|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8115900A|FR2511663B1|1981-08-19|1981-08-19|
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