RU2011122471A - METHOD FOR CLEANING GAS MIXTURES CONTAINING MERCAPTANES AND OTHER ACIDIC GASES - Google Patents

METHOD FOR CLEANING GAS MIXTURES CONTAINING MERCAPTANES AND OTHER ACIDIC GASES Download PDF

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RU2011122471A
RU2011122471A RU2011122471/05A RU2011122471A RU2011122471A RU 2011122471 A RU2011122471 A RU 2011122471A RU 2011122471/05 A RU2011122471/05 A RU 2011122471/05A RU 2011122471 A RU2011122471 A RU 2011122471A RU 2011122471 A RU2011122471 A RU 2011122471A
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gas mixture
ethoxylated polyethyleneimine
hydrogen
ppm
carbon
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RU2518626C2 (en
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Катрин ВЮ
Жан-Патрик БОНН
Дидье АНГЛЕРО
Жорж Фреми
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Тоталь С.А.
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/308—Carbonoxysulfide COS
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/06—Polluted air
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Abstract

1. Способ очистки газовой смеси, содержащей меркаптаны и другие кислые газы, включающий этап приведения в контакт указанной газовой смеси с поглощающим раствором, содержащим алканоламин, этоксилированный полиэтиленимин и воду, причем средняя молекулярная масса этоксилированного полиэтиленимина составляет от 500 до 10г/моль.2. Способ по п.1, в котором указанная газовая смесь является природным газом.3. Способ по п.1 или 2, в котором газовая смесь содержит метилмеркаптан и/или этилмеркаптан, и возможно один или несколько газов, выбранных из сероводорода, диоксида углерода и карбонилсульфида.4. Способ по п.1, в котором алканоламин выбран из моноэтаноламина, диэтаноламина, триэтаноламина, диизопропаноламина, метилдиэтаноламина, активированного метилдиэтаноламина, стерически затрудненных аминов и их смесей.5. Способ по п.1, в котором средняя молекулярная масса этоксилированного полиэтиленимина составляет от 500 до 10г/моль.6. Способ по п.1, в котором этоксилированный полиэтиленимин содержит от 50 до 60% углерода, от 9 до 11% водорода, от 1 до 33% азота и от 1 до 40% кислорода, предпочтительно содержит от 50 до 60% углерода, от 9 до 11% водорода, от 1 до 15% азота и от 10 до 40% кислорода, причем количества выражены в массе.7. Способ по п.5, в котором этоксилированный полиэтиленимин содержит от 50 до 60% углерода, от 9 до 11% водорода, от 1 до 33% азота и от 1 до 40% кислорода, предпочтительно содержит от 50 до 60% углерода, от 9 до 11% водорода, от 1 до 15% азота и от 10 до 40% кислорода, причем количества выражены в массе.8. Способ по п.1, в котором поглощающий раствор содержит:- от 20 до 60 мас.% диэтаноламина, предпочтительно от 30 до 50%, в идеале примерно 40%;- от 20 до 70 мас.% воды, пред1. A method for purifying a gas mixture containing mercaptans and other acidic gases, comprising the step of contacting said gas mixture with an absorbing solution containing alkanolamine, ethoxylated polyethyleneimine and water, the average molecular weight of ethoxylated polyethyleneimine being from 500 to 10 g / mol. The method of claim 1, wherein said gas mixture is natural gas. The method according to claim 1 or 2, in which the gas mixture contains methyl mercaptan and / or ethyl mercaptan, and optionally one or more gases selected from hydrogen sulfide, carbon dioxide and carbonyl sulfide. The method of claim 1, wherein the alkanolamine is selected from monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, methyldiethanolamine, activated methyldiethanolamine, hindered amines, and mixtures thereof. The process according to claim 1, wherein the average molecular weight of the ethoxylated polyethyleneimine is 500 to 10 g / mol. The method according to claim 1, in which the ethoxylated polyethyleneimine contains from 50 to 60% carbon, from 9 to 11% hydrogen, from 1 to 33% nitrogen and from 1 to 40% oxygen, preferably contains from 50 to 60% carbon, from 9 up to 11% hydrogen, from 1 to 15% nitrogen and from 10 to 40% oxygen, and the amounts are expressed in mass. 7. The method according to claim 5, in which the ethoxylated polyethyleneimine contains from 50 to 60% carbon, from 9 to 11% hydrogen, from 1 to 33% nitrogen and from 1 to 40% oxygen, preferably contains from 50 to 60% carbon, from 9 up to 11% hydrogen, from 1 to 15% nitrogen and from 10 to 40% oxygen, and the amounts are expressed in mass. 8. The method according to claim 1, in which the absorption solution contains: from 20 to 60 wt.% Diethanolamine, preferably from 30 to 50%, ideally about 40%; - from 20 to 70 wt.% Water, before

Claims (19)

1. Способ очистки газовой смеси, содержащей меркаптаны и другие кислые газы, включающий этап приведения в контакт указанной газовой смеси с поглощающим раствором, содержащим алканоламин, этоксилированный полиэтиленимин и воду, причем средняя молекулярная масса этоксилированного полиэтиленимина составляет от 500 до 106 г/моль.1. A method for purifying a gas mixture containing mercaptans and other acid gases, comprising the step of bringing said gas mixture into contact with an absorbing solution containing alkanolamine, ethoxylated polyethyleneimine and water, wherein the average molecular weight of ethoxylated polyethyleneimine is from 500 to 10 6 g / mol. 2. Способ по п.1, в котором указанная газовая смесь является природным газом.2. The method according to claim 1, wherein said gas mixture is natural gas. 3. Способ по п.1 или 2, в котором газовая смесь содержит метилмеркаптан и/или этилмеркаптан, и возможно один или несколько газов, выбранных из сероводорода, диоксида углерода и карбонилсульфида.3. The method according to claim 1 or 2, in which the gas mixture contains methyl mercaptan and / or ethyl mercaptan, and possibly one or more gases selected from hydrogen sulfide, carbon dioxide and carbonyl sulfide. 4. Способ по п.1, в котором алканоламин выбран из моноэтаноламина, диэтаноламина, триэтаноламина, диизопропаноламина, метилдиэтаноламина, активированного метилдиэтаноламина, стерически затрудненных аминов и их смесей.4. The method according to claim 1, wherein the alkanolamine is selected from monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, methyldiethanolamine, activated methyldiethanolamine, sterically hindered amines and mixtures thereof. 5. Способ по п.1, в котором средняя молекулярная масса этоксилированного полиэтиленимина составляет от 500 до 105 г/моль.5. The method according to claim 1, in which the average molecular weight of ethoxylated polyethyleneimine is from 500 to 10 5 g / mol. 6. Способ по п.1, в котором этоксилированный полиэтиленимин содержит от 50 до 60% углерода, от 9 до 11% водорода, от 1 до 33% азота и от 1 до 40% кислорода, предпочтительно содержит от 50 до 60% углерода, от 9 до 11% водорода, от 1 до 15% азота и от 10 до 40% кислорода, причем количества выражены в массе.6. The method according to claim 1, in which ethoxylated polyethyleneimine contains from 50 to 60% carbon, from 9 to 11% hydrogen, from 1 to 33% nitrogen and from 1 to 40% oxygen, preferably contains from 50 to 60% carbon, from 9 to 11% hydrogen, from 1 to 15% nitrogen and from 10 to 40% oxygen, and the amounts are expressed in mass. 7. Способ по п.5, в котором этоксилированный полиэтиленимин содержит от 50 до 60% углерода, от 9 до 11% водорода, от 1 до 33% азота и от 1 до 40% кислорода, предпочтительно содержит от 50 до 60% углерода, от 9 до 11% водорода, от 1 до 15% азота и от 10 до 40% кислорода, причем количества выражены в массе.7. The method according to claim 5, in which ethoxylated polyethyleneimine contains from 50 to 60% carbon, from 9 to 11% hydrogen, from 1 to 33% nitrogen and from 1 to 40% oxygen, preferably contains from 50 to 60% carbon, from 9 to 11% hydrogen, from 1 to 15% nitrogen and from 10 to 40% oxygen, and the amounts are expressed in mass. 8. Способ по п.1, в котором поглощающий раствор содержит:8. The method according to claim 1, in which the absorbing solution contains: - от 20 до 60 мас.% диэтаноламина, предпочтительно от 30 до 50%, в идеале примерно 40%;- from 20 to 60 wt.% diethanolamine, preferably from 30 to 50%, ideally about 40%; - от 20 до 70 мас.% воды, предпочтительно от 30 до 60%, в идеале от 40 до 50% и- from 20 to 70 wt.% water, preferably from 30 to 60%, ideally from 40 to 50%, and - от 5 до 40 мас.% этоксилированного полиэтиленимина, предпочтительно от 5 до 30%, в идеале от 10 до 20%.- from 5 to 40 wt.% ethoxylated polyethyleneimine, preferably from 5 to 30%, ideally from 10 to 20%. 9. Способ по п.1, в котором приведение в контакт газовой смеси с поглощающим раствором проводят в абсорбционной колонне при температуре, составляющей от примерно 40 до примерно 100°С, предпочтительно от примерно 50 до примерно 90°С.9. The method according to claim 1, in which bringing the gas mixture into contact with the absorbing solution is carried out in an absorption column at a temperature of from about 40 to about 100 ° C, preferably from about 50 to about 90 ° C. 10. Способ очистки по п.1, в котором приведение в контакт газовой смеси с поглощающим раствором проводят при скорости подачи газовой смеси, составляющей от 0,23·106 Нм3/сут до 56·106 Нм3/сут и при расходе поглощающего раствора от 800 до 100000 м3/сут.10. The cleaning method according to claim 1, in which bringing the gas mixture into contact with the absorbing solution is carried out at a gas mixture supply rate of 0.23 · 10 6 Nm 3 / day to 56 · 10 6 Nm 3 / day and at a flow rate absorbing solution from 800 to 100,000 m 3 / day. 11. Способ очистки по п.9, в котором приведение в контакт газовой смеси с поглощающим раствором проводят при скорости подачи газовой смеси, составляющей от 0,23·106 Нм3/сут до 56·106 Нм3/сут и при расходе поглощающего раствора от 800 до 100000 м3/сут.11. The cleaning method according to claim 9, in which bringing the gas mixture into contact with the absorbing solution is carried out at a gas mixture supply rate of 0.23 · 10 6 Nm 3 / day to 56 · 10 6 Nm 3 / day and at a flow rate absorbing solution from 800 to 100,000 m 3 / day. 12. Способ по п.1, содержащий дополнительно этап регенерации поглощающего раствора насыщенного меркаптанами и другими кислыми газами, предпочтительно при давлении регенерации, составляющем от 0 до 20 бар, в частности от 1 до 2 бар, и предпочтительно при температуре от 100 до 140°С.12. The method according to claim 1, further comprising the step of regenerating the absorbing solution saturated with mercaptans and other acid gases, preferably at a regeneration pressure of 0 to 20 bar, in particular 1 to 2 bar, and preferably at a temperature of from 100 to 140 ° FROM. 13. Способ по п.1, в котором концентрация меркаптанов, содержащихся в газовой смеси, снижается до значения ниже примерно 5 млн.д., и/или концентрация сероводорода, содержащегося в газовой смеси, снижается до значения ниже примерно 4 млн.д., и/или концентрация диоксида углерода, содержащегося в газовой смеси, снижается до значения ниже примерно 50 млн.д., и/или концентрация карбонилсульфида, содержащегося в газовой смеси, снижается до значения ниже примерно 1 млн.д.13. The method according to claim 1, in which the concentration of mercaptans contained in the gas mixture is reduced to below about 5 ppm, and / or the concentration of hydrogen sulfide contained in the gas mixture is reduced to below about 4 ppm. and / or the concentration of carbon dioxide contained in the gas mixture decreases to below about 50 ppm, and / or the concentration of carbonyl sulfide contained in the gas mixture decreases to below about 1 ppm. 14. Способ по п.3, в котором концентрация меркаптанов, содержащихся в газовой смеси, снижается до значения ниже примерно 5 млн.д., и/или концентрация сероводорода, содержащегося в газовой смеси, снижается до значения ниже примерно 4 млн.д., и/или концентрация диоксида углерода, содержащегося в газовой смеси, снижается до значения ниже примерно 50 млн.д., и/или концентрация карбонилсульфида, содержащегося в газовой смеси, снижается до значения ниже примерно 1 млн.д.14. The method according to claim 3, in which the concentration of mercaptans contained in the gas mixture is reduced to below about 5 ppm, and / or the concentration of hydrogen sulfide contained in the gas mixture is reduced to below below 4 ppm. and / or the concentration of carbon dioxide contained in the gas mixture decreases to below about 50 ppm, and / or the concentration of carbonyl sulfide contained in the gas mixture decreases to below about 1 ppm. 15. Композиция, содержащая:15. A composition comprising: - алканоламин,- alkanolamine, - воду и- water and - этоксилированный полиэтиленимин,- ethoxylated polyethyleneimine, в которой средняя молекулярная масса этоксилированного полиэтиленимина составляет от 500 до 106 г/моль.in which the average molecular weight of ethoxylated polyethyleneimine is from 500 to 10 6 g / mol. 16. Композиция по п.15, содержащая:16. The composition according to clause 15, containing: - от 20 до 60 мас.% алканоламина, предпочтительно от 30 до 50%, в идеале примерно 40%,- from 20 to 60 wt.% alkanolamine, preferably from 30 to 50%, ideally about 40%, - от 20 до 70 мас.% воды, предпочтительно от 30 до 60%, в идеале от 40 до 50% и- from 20 to 70 wt.% water, preferably from 30 to 60%, ideally from 40 to 50%, and - от 5 до 40 мас.% этоксилированного полиэтиленимина, предпочтительно от 5 до 30%, в идеале от 10 до 20%.- from 5 to 40 wt.% ethoxylated polyethyleneimine, preferably from 5 to 30%, ideally from 10 to 20%. 17. Композиция по п.15 или 16, в которой алканоламин выбран из моноэтаноламина, диэтаноламина, триэтаноламина, диизопропаноламина, метилдиэтаноламина, активированного метилдиэтаноламина, стерически затрудненных аминов и их смесей.17. The composition of claim 15 or 16, wherein the alkanolamine is selected from monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, methyldiethanolamine, activated methyldiethanolamine, sterically hindered amines and mixtures thereof. 18. Композиция по п.15, в которой этоксилированный полиэтиленимин является таким, как описан в п.5.18. The composition of claim 15, wherein the ethoxylated polyethyleneimine is as described in claim 5. 19. Композиция по п.15, в которой этоксилированный полиэтиленимин является таким, как описан в п.6. 19. The composition of claim 15, wherein the ethoxylated polyethyleneimine is as described in claim 6.
RU2011122471/05A 2008-11-04 2009-11-03 Method of purifying gas mixtures, containing mercaptans and other acidic gases RU2518626C2 (en)

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FR0806128A FR2937887B1 (en) 2008-11-04 2008-11-04 PROCESS FOR THE PURIFICATION OF GASEOUS MIXTURES CONTAINING MERCAPTANS AND OTHER ACIDIC GASES
FR0806128 2008-11-04
PCT/IB2009/054881 WO2010052643A1 (en) 2008-11-04 2009-11-03 Method for purifying gaseous mixtures containing mercaptans and other acid gases

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