• 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:
    A process for removing hydrogen sulfide from a gaseous stream in a contact zone by contacting the gaseous stream with an aqueous alkaline scrubbing solution containing a polyvalent metal chelate at a pH of 7 to 10, wherein the polyvalent metal chelate is: in one embodiment, all or substantially all in the reduced or lower valence state in a contact zone and is oxidized to the oxidized or higher valence state in an oxidation zone, so as to convert hydrosulfide and/or sulfide and salts present in the contact zone to sulfur; and in a second embodiment, the aqueous alkaline solution contacting the gaseous stream is a mixture containing higher and lower valence polyvalent metal chelates.
    公开号:SU1679970A3
    申请号:SU874202504
    申请日:1987-04-30
    公开日:1991-09-23
    发明作者:С.Джеффри Геинс；Д.Маерс Джон
    申请人:Дзе Дау Кемикал Компани (Фирма)；
    IPC主号:
    专利说明:

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    This invention relates to processes for the purification of gas from hydrogen sulfide by catalytic oxidation thereof to elemental sulfur.
    The purpose of the invention is to reduce the loss of the absorption solution,
    Example 1: Gas washing in a scrubber containing gas hydrogen sulfide is carried out continuously. The aqueous-alkaline solution contains iron complexed with N-hydroxyethyl-ethylenediamine-tri-acetic acid (HEDTUC) and has a pH of 8.0-8.5, which is regulated by the addition of sodium hydroxide. The process is fully automated using a computerized control system and continuously carried out 24 hours a day, 7 days a week for several months to obtain the following data. The flow rates of the process streams (gas and liquid) are continuously measured and recorded. Regulate the temperature of the water-alkaline scrubber solution using the heat exchanger integrated in the line at a level of about 40 ° C. Containing hydrogen sulfide gas entering the contact zone, and the exhaust gas from the contact zone is analyzed according to standard methods for the content of hydrogen sulfide using an in-line flame photometric analyzer. Samples of a water-alkaline scrubber solution are removed periodically from the process for laboratory analysis according to the following indicators: total iron is determined by atomic absorption analysis; iron (111) is determined by a conventional thiocyanate photometric method; the chelate concentration is determined by the liquid
    Vj yu
    YU VI O
     WITH
    by chromatographic method. In-line bag filters are used to continuously remove crystalline sulfur from the aqueous scrubber (gas wash) solution before transferring the scrubber solution to the contact zone. The amount of sulfur produced in the process is determined.
    The total concentration of chelated iron in the aqueous scrubber solution is adjusted to provide a significant molar excess relative to the sulfide in the contact zone for a series of experiments to study the effect of the concentration of iron (III) on the decomposition of the chelate. The concentration of iron (III) is adjusted at various levels. in each experiment by adjusting the conditions in the oxidation zone, i.e. air flow rate and solution retention time in the oxidation zone. Essentially all absorbed sulfide is oxidized to crystalline sulfur in the oxidized zone and the excess iron (III) leaving the oxidizing zone is adjusted to the required level. Samples of the process solution are analyzed for free sulphide using a pre-calibrated specifically sulphide-ion electrode. The decomposition of the chelating agent is determined for each experiment and calculated as the mass (in pounds) of the chelating agent lost per pound of the mass of sulfur produced. The concentration of iron (III) is calculated as the molar ratio of iron (III) fed to the contact zone, the stoichiometric amount of iron (111) required relative to the hydrogen sulfide fed to the contact zone.
    Examples 2-13. Analogously to example 1, a series of experiments are carried out, the results of which are presented in Table 1. These results show that the decomposition of the chelate is reduced to either a low level or an acceptable level, provided that the total amount of iron (II) chelate fed to the contact zone exceeds five times the amount of iron (III) fed to the contact zone. When stoichiometric amount is present or
    more iron (III) chelate (required for the conversion of hydrogen sulfide, hydrosulfide and / or sulfide present in the contact zone) and the ratio Fe (II) / Fe (lll) decreases below five times the amount of iron chelate (111), the loss of chelate can become so significant that the process becomes uneconomical compared with competitive technological processes.
    Examples 14-19. The second series of experiments was carried out using the same process as in Examples 1-8, except that iron chelated with ethylenediaminetetraacetic acid (EDTA) was used instead of Re-HEDTUC. The results are shown in Table 2. The same relationship between the decomposition of the chelate and the concentration of iron (II) and iron (III) ions is shown,
    Examples 20-21. The third series of experiments (Table 3) was carried out using the same process as in the previous examples, but with the exception of using iron complexed with nitrile triacetic acid (NTUC), instead of Fe-EDTA or Fe-HEDUC.
    The loss of the absorption solution in comparison with the known method is reduced by 50%.
    权利要求:
    Claims (2)
    [1]
    1. A method for purifying gas from hydrogen sulphide, including washing it with a water-alkaline solution containing a mixture of iron (I) and (III) chelated with polyamino-carboxylic acid, and the subsequent regeneration of the resulting solution with an oxygen-containing gas, characterized in that absorption solution, washing is carried out with a solution containing iron chelate () is 5 times more than iron (III4) chelate.
    [2]
    2. A method according to claim 1, wherein it is assumed that N-hydroxyethyl-ethylenediamine-tri-acetic acid, or ethylenediamine-tetraacetic acid, or nitrile-tri-acetic acid is taken as the polyamino carboxylic acid.
    Table 1
    Table 2
    Table 3
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1679970A3|1991-09-23|Process for removing ydrogen sulfide from gas
    DE2532175C3|1979-06-21|Process for separating sulfur oxides from exhaust gases
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    US6872371B2|2005-03-29|Method and apparatus for NOx and SO2 removal
    US4133650A|1979-01-09|Removing sulfur dioxide from exhaust air
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    US4957716A|1990-09-18|Method for removal of SO2 and NOx from combustion gases by metal chelation and thermal reduction
    US4400361A|1983-08-23|Method of removing H2 S from a gas stream utilizing boron-vanadium and iron complexes
    US4731232A|1988-03-15|Process for the purification of industrial gases or waste gases
    CA1100291A|1981-05-05|Method and apparatus for removing sulfur and nitrogencompounds from a gas mixture
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    US5200161A|1993-04-06|Process for the separation of hydrogen cyanide from gases and waste gases
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    US4944929A|1990-07-31|Process for the removal of nitrogen oxide from flue gases
    KR102143932B1|2020-08-12|Absorption composition for removing NOx and SOx simultaneously
    KR800000279B1|1980-04-10|Exhaust gas scrubbing process
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    同族专利:
    公开号 | 公开日
    EP0244249B1|1995-09-20|
    DK225387A|1987-11-02|
    AU7219987A|1987-11-05|
    AU605764B2|1991-01-24|
    NO871807D0|1987-04-30|
    CA1288087C|1991-08-27|
    NZ220088A|1990-10-26|
    NO871807L|1987-11-02|
    US4774071A|1988-09-27|
    NO168231C|1992-01-29|
    CN87103152A|1987-12-23|
    PH23589A|1989-09-11|
    CN1008071B|1990-05-23|
    EP0244249A3|1989-02-22|
    DK225387D0|1987-05-01|
    NO168231B|1991-10-21|
    JPS62269729A|1987-11-24|
    EP0244249A2|1987-11-04|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB999800A|1962-03-13|1965-07-28|Humphreys & Glasgow Ltd|Purification of gases|
    US4091073A|1975-08-29|1978-05-23|Shell Oil Company|Process for the removal of H2 S and CO2 from gaseous streams|
    US4076621A|1976-03-15|1978-02-28|Air Resources, Inc.|Chelate oxidation of hydrogen sulfide in sour water|
    US4388293A|1981-11-24|1983-06-14|Shell Oil Company|H2 S Removal|
    US4455287A|1982-03-15|1984-06-19|Ari Technologies, Inc.|Method of stabilizing chelated polyvalent metal solutions|
    US4532118A|1984-03-29|1985-07-30|Kimura Chemical Plants Co., Ltd.|Process for removal of hydrogen sulfide from gases|
    IN166496B|1984-12-24|1990-05-19|Shell Int Research|
    IN168471B|1985-08-23|1991-04-13|Shell Int Research|
    US4664902A|1985-08-23|1987-05-12|Shell Oil Company|Recovery of sulfur from a solid sulfur-containing solution of solubilized iron chelate of nitrilotriacetic acid|US4889701A|1982-01-04|1989-12-26|Mobil Oil Corporation|Process for oxidizing multivalent metals|
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    US5149460A|1985-08-23|1992-09-22|Shell Oil Company|Composition for H2 S removal|
    NZ223528A|1987-02-19|1991-08-27|Dow Chemical Co|Process and scrubbing solution for removal of h 2 s and/or co 2 from gas streams|
    US4789530A|1987-12-09|1988-12-06|Phillips Petroleum Company|Absorption of hydrogen sulfide with an alkali metal ethylenediaminetetraacetate and/or alkali metal nitrilotriacetate|
    US4830838A|1988-11-01|1989-05-16|The Dow Chemical Company|Removal of hydrogen sulfide from fluid streams with minimum production of solids|
    US5026503A|1989-07-21|1991-06-25|Amoco Corporation|Composition and method for removing hydrogen sulfide from gas streams|
    US5407646A|1989-12-05|1995-04-18|The University Of Toronto Innovations Foundation|Dual impeller method and apparatus for effecting chemical conversion|
    DE4117382A1|1991-05-28|1992-12-03|Metallgesellschaft Ag|METHOD FOR REGULATING THE PH VALUE OF AN ACID WASHING LIQUID|
    DE4130132A1|1991-09-07|1993-03-11|Michael Wolter|Hydrogen sulphide absorption from gas with high carbon di:oxide content - in ferric amino-carboxylate soln. stabilised with alkali hydrogen carbonate to avoid oxidative decomposition of amino-carboxylate|
    CA2100294C|1992-07-27|2003-08-19|David Frederick Bowman|Process of removing hydrogen sulphide from a gas mixture|
    US5549789A|1992-08-28|1996-08-27|The United States Of America As Represented By The Secretary Of Agriculture|Oxidation of lignin and polysaccharides mediated by polyoxometalate treatment of wood pulp|
    NL9401036A|1994-06-23|1996-02-01|Tno|Anaerobic removal of sulfur compounds from wastewater.|
    US5543122A|1994-11-09|1996-08-06|The Dow Chemical Company|Process for the removal of h2 S from non-condensible gas streams and from steam|
    US5958360A|1997-02-07|1999-09-28|Gas Research Institute|Absorber for liquid redox processes|
    GB2369310A|2000-09-29|2002-05-29|Fluid Technologies|Removal of contaminants from gas stream using acidic scrubber and oxidation|
    US8034231B2|2008-02-20|2011-10-11|Baker Hughes Incorporated|Method for reducing hydrogen sulfide evolution from asphalt|
    WO2015005296A1|2013-07-12|2015-01-15|株式会社Ihi|Exhaust gas purification device and co2 recovery system|
    US9783458B2|2014-01-31|2017-10-10|Innophos, Inc.|Hydrogen sulfide scavenger|
    EP3121251B1|2014-03-17|2019-05-08|Kuraray Co., Ltd.|Removal of sulphur-containing compounds|
    CN104437085B|2014-12-26|2017-01-25|中南大学|Liquid phase efficient reduction method for regeneration denitration iron base chelating agent|
    CN106395756B|2016-08-31|2018-08-31|华陆工程科技有限责任公司|It is a kind of to handle containing ammonia, carbonyl sulfur, hydrogen sulfide sour gas, and carry out the novel process of sulphur recovery|
    CN109622038A|2018-12-14|2019-04-16|长春东狮科贸实业有限公司|It is a kind of for removing the suppression salt desulphurization catalyst of hydrogen sulfide|
    CN112275048A|2020-10-15|2021-01-29|吉林建筑大学|Purification and treatment device for atmospheric pollution|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/857,863|US4774071A|1986-05-01|1986-05-01|Process and composition for the removal of hydrogen sulfide from gaseous streams|
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