GB2192347A - Removing H2S and CO2 from a gas mixture - Google Patents

Removing H2S and CO2 from a gas mixture Download PDF

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Publication number
GB2192347A
GB2192347A GB08616508A GB8616508A GB2192347A GB 2192347 A GB2192347 A GB 2192347A GB 08616508 A GB08616508 A GB 08616508A GB 8616508 A GB8616508 A GB 8616508A GB 2192347 A GB2192347 A GB 2192347A
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GB
United Kingdom
Prior art keywords
gas mixture
absorbent
contacting
pressure
partly
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB08616508A
Other versions
GB2192347B (en
GB8616508D0 (en
Inventor
Martin Maersk Suenson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Priority to GB8616508A priority Critical patent/GB2192347B/en
Publication of GB8616508D0 publication Critical patent/GB8616508D0/en
Priority to NL8701225A priority patent/NL194362C/en
Priority to CA000538120A priority patent/CA1296160C/en
Priority to CN87104539A priority patent/CN1016166B/en
Priority to IN473/MAS/87A priority patent/IN169707B/en
Priority to AU75007/87A priority patent/AU590866B2/en
Priority to DE19873721789 priority patent/DE3721789A1/en
Priority to DK337487A priority patent/DK170394B1/en
Priority to NO872756A priority patent/NO166920C/en
Publication of GB2192347A publication Critical patent/GB2192347A/en
Application granted granted Critical
Publication of GB2192347B publication Critical patent/GB2192347B/en
Expired legal-status Critical Current

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Classifications

    • 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
    • B01D53/1468—Removing hydrogen sulfide
    • 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
    • B01D53/1406—Multiple stage absorption
    • 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
    • B01D53/52—Hydrogen sulfide
    • B01D53/526—Mixtures of hydrogen sulfide and carbon dioxide
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)
  • Filtering Of Dispersed Particles In Gases (AREA)

Description

GB2192347A 1
SPECIFICATION
Removing H2S and C02 from a gas mixture containing H2S and C02 The present invention relates to removing H2S and C02 from a gas mixture including H2S and 5 C02, in particular to removing these sour components from a gas mixture containing hydrcarbons and between 10 and 50% by volume C02, and only a small amount of H2S, wherein for example the volume ratio of H2S to C02 is between 10-6 and 0. 1. Examples of such a gas mixture are natural gas..
It is an object of the present invention to provide a flexible process for deep H2S removal and 10 bulk C02 removal.
To this end the process for removing H2S and C02 from a gas mixture including H2S and C02 according to the invention comprises the steps of. a) contacting the gas mixture a first contacting zone with an aqueous reactant solution containing an effective amount of an oxidizing reactant to produce a partly purified gas mixture 15 and an aqueous solution comprising sulphur and reduced reactant, passing the partly purified gas mixture to a second contacting zone; and b) contacting the partly purified gas mixture in the second contacting zone with a liquid and regeneratable absorbent to produce a purified gas mixture and loaded absorbent.
Sulphur obtained in step a) can be removed from the aqueous solution produced in step a) 20 before or after regenerating at least part of the reduced reactant by oxidizing the reactant.
The partly purified gas mixture is passed without further treating or converting to the second contacting zone, although the partly purified gas mixture may be heated or cooled if required.
In. a suitable embodiment the aqueous reactant solution comprises a coordination of Fe(I11) with an organic acid, for example nitfliotriacetic acid (NTA), or ethylene- diamine tetra acetic acid 25 (EDTA).
In a preferred embodiment the aqueous reactant solution comprises an ammonium form of a coordination complex of Fe(I11) with NTA, and an ammonium form of a coordination complex of Fe(I1) with NTA. The aqueous reactant solution may further comprise aqueous ammonia. The pH of the solution is suitably between 5 and 8.5, and the molar ratio of the coordination complex 30 of Fe(I11) with NTA to the ammonium form of a coordination complex of Fe(I1) with NTA in the solution is suitably between 0.2 and 6. The aqueous reactant solution comprises about 2-15 mol of an ammonium form of a coordination complex of Fe(I11) with NTA per mol H2S to be removed.
The partly purified gas mixture comprises C02 which will be removed in step b) by means of 35 the liquid and regeneratable absorbent. To remove C02 from the loaded absorbent obtained in step b), the loaded absorbent is flashed at least once by releasing the pressure to a level below the partial pressure of CO, at the prevailing temperature. If it is required to remove co-absorbed hydrocarbons this step may be preceded by flashing the loaded absorbent at.least once by releasing the pressure to a level between.the pressure prevailing at dontacting in step b) and the 40 partial pressure of C02 Pt the prevaffing temperaturd.
In a further suitable embodiment the liquid and regeneratable absorbent is an aqueous solution of an amine, for example a tertiairy amine, such as methyl diethanolamine (MIDEA).
The liquid and regeneratable absorbent may further comprise a physical solvent for example sulfolane. 45 The liquid and regeneratable absorbent comprises suitably an aqueous solution of 10-60% by mass MDEA and 15-55% by mass sulfolane.
The invention wili now be elucidated in more detail with reference to the Figure showing schematically the apparatus for carrying out the process according to the invention.
The apparatus comprises a first contacting zone 1, a sulphur recovery zone 3, a first regenera- 50 tion zone 5, a second contacting zone 6, a first flash vessel 8 and a second flash vessel 9.
To the first contacting zone 1 is connected a sour gas supply conduit 10. The first contacting zone 1 is connected to the sulphur recovery zone 3 by conduit 12, and to the second contacting zone 6 by conduit 14. The sulphur recovery zone 3 is provided witha sulphur outlet 15, and the zone 3 is connected to the first regeneration zone 5 by conduit 16. To the first 55 regeneration zone 5 is connected an oxidant supply conduit 17 and a spent gas outlet 19, and the first regeneration zone 5 is connected to the first contacting zone 1 by conduit 20.
The second contacting zone 6 has a purified gas outlet 21, and the zone 6 is connected to the first flash vessel 8 by conduit 22 which is provided with pressure relief valve 23. The first flash vessel 8 has a gas outlet 25, and is connected by conduit 26 provided with pressure relief 60 valve 27 to the second flash vessel 9. The second flash vessel 9 has a gas outlet 30, and is connected to the second zone 6 by conduit 31.
EXAMPLE
A hydrocarbon-containing sour gas mixture including 15% by volume C02 and 250 ppmv 65 2 GB2192347A 2 (parts per million by volume) H2S is supplied to the first contacting zone 1 via the sour gas supply conduit 10. In the first contacting zone 1 the sour gas mixture is contacted with an aqueous reactant solution containing 0.65 mol/1 of an ammonium form of a coordination com plex of Feffil) with NTA to produce a partly purified gas mixture, which contains 12% by volume C02 and 2ppmv H.S, and an aqueous solution comprising sulphur and reduced reactant compris- 5 ing an additional amount of an ammonium form of a coordination complex of Fe(I1) with NTA.
The aqueous solution comprising sulphur and reduced reactant is passed through conduit 12 to the sulphur removal zone 3 from which sulphur is removed through conduit 15, and the substantially sulphur free aqueous solution is passed through conduit 16 to the first regeneration zone 5 where at least Part of the reduced reactant is oxidized by contacting the aqueous 10 solution with air supplied through the oxidant supply conduit 17. The regenerated aqueous reactant solution is passed to the first contacting zone 1 through conduit 20 and spent air is removed from the first regeneration zone 5 through spent gas outlet 19.
The partly purified gas mixture is passed, without being treated, through conduit 14 to the second contacting zone 6 where it is contacted with a liquid and regeneratable absorbent in the 15 form of an aqueous solution containing 30% by mass MDEA under conditions to remove C02 from the partly purified gas mixture to produce a purified gas mixture and loaded absorbent. The purified gas mixture, which contains 1% by volume C02 and 1.5 ppmv H2S, is removed from the second contacting zone 7 through purified gas outlet 21, and the loaded absorbent is passed through conduit 22 to the first flash vessel 8. In the first flash vessel 8 co-absorbed hydrocar- 20 bons are -removed by flashing the loaded absorbent by releasing the pressure to a level between the pressure prevailing in the second contacting zone 6 and the partial pressure of CO. at the prevailing temperature. The desorbed hydrocarbon-containing gas mixture, which is substantially free of CO., is removed from the first flash vessel 8 through gas outlet 25. The partly loaded absorbent obtained in the first flash vessel 8 is passed through conduit 26 to the second flash 25 vessel 9. In the second flash vessel 9 C02 is removed from the partly loaded absorbent by 1 releasing the pressure to a level below the partial pressure of C02 at the prevailing temperature, to obtain a regenerated absorbent, which is supplied to the second contacting zone 6 through conduit 31. The desorbed C02, which is substantially free of H2S, is removed from the second flash vessel 9 through gas outlet 30. 30 The first contact zone 1 and the first regeneration zone 5 may be columns suitable for counter-currently contacting gas and liquid, or columns suitable for co- currently contacting gas and liquid.

Claims (8)

CLAIMS 35
1. Process for removing H2S and C02 from cl gas mixture including H2S and C02 comprising the steps of a) contacting the gas mixture in a first contacting zone with an aqueous reactant solution containing an effective amount of an oxidizing reactant to produce a. partly purified gas mixture and an aqueous solution comprising sulphur and reduced reactant, passing the partly purified gas 40 mixture to a second contacting zone; and b) contacting the partly purified gas mixture in the second contacting zone with a liquid and regeneratable absorbent to produce a purified gas mixture and loaded absorbent.
2. Process as claimed in claim 1, wherein the aqueous reactant solution comprises a coordi nation complex of Fe(I11) with a suitable organic acid. 45
3. Process as claimed in claim 1, wherein the aqueous reactant solution comprises an ammonium form of a coordination complex of Fe(J11) with nitrflotriacetic acid, and an ammonium form of a coordination complex of Fe(I1) with nitrilotriacetic acid.
4. Process as claimed in any one of the claims 1-3, wherein the liquid and regeneratable absorbent is an aqueous solution of a tertiairy amine. 50
5. Process as claimed in claim 4, wherein the tertiary amine is methyl diethanolamine.
6. Process as claimed in any one of the claims 1-5, wherein the loaded absorbent is flashed in at least one step by releasing the pressure to a level below the partial pressure Of C02 at the prevailing temperature to obtain a regenerated absorbent for use in step b).
7. Process as claimed in any one of the claims 1-5, wherein the loaded absorbent is flashed 55 - in at least one step by releasing the pressure a level between the pressure prevailing at contacting in step b) and the partial pressure of C02 at the prevailing temperature to obtain a partly loaded absorbent, and wherein the partly loaded absorbent is flashed in at least one step by releasing the pressure to a level below the partial pressure of C02 at the prevailing tempera- ture to obtain a regenerated absorbent for use in step b). 60
8. Process for removing H,S and C02 from a gas mixture including H2S and C02 as claimed in claim 1 substantially as described hereinbefore with reference to the drawing.
Printed for Her Majesty's Stationery Office by Burgess & Son (Abingdon) Ltd. Dd 8991685, 1988. Published at The Patent Office, 25 Southampton Buildings, London, WC2A 1AY, from which copies may be obtained.
GB8616508A 1986-07-07 1986-07-07 Removing hydrogen sulphide and carbon dioxide from a gas mixture containing hydrogen sulphide and carbon dioxide. Expired GB2192347B (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
GB8616508A GB2192347B (en) 1986-07-07 1986-07-07 Removing hydrogen sulphide and carbon dioxide from a gas mixture containing hydrogen sulphide and carbon dioxide.
NL8701225A NL194362C (en) 1986-07-07 1987-05-22 Method for removing H # 2S and CO # 2 from a gas mixture containing H # 2S and CO # 2.
CA000538120A CA1296160C (en) 1986-07-07 1987-05-27 Removing h s and co_ from a gas mixture containing h s and co_
CN87104539A CN1016166B (en) 1986-07-07 1987-06-30 Method for removing hydrogen sulfide and carbon dioxide from mixed gas containing hydrogen sulfide and carbon dioxide
IN473/MAS/87A IN169707B (en) 1986-07-07 1987-07-01
AU75007/87A AU590866B2 (en) 1986-07-07 1987-07-01 Removing h2s and co2 from a gas mixture containing h2s and co2
DE19873721789 DE3721789A1 (en) 1986-07-07 1987-07-01 METHOD FOR REMOVING H (DOWN ARROW) 2 (DOWN ARROW) S AND CO (DOWN ARROW) 2 (DOWN ARROW) FROM AN H (DOWN ARROW) 2 (DOWN ARROW) S AND CO (DOWN ARROW) 2 (DOWN ARROW) CONTAINING GAS MIXTURE
DK337487A DK170394B1 (en) 1986-07-07 1987-07-01 Process for removing H2S and CO2 from a gas mixture containing H2S and CO2
NO872756A NO166920C (en) 1986-07-07 1987-07-01 PROCEDURE FOR AA REMOVE H2S AND CO2 FROM A GAS MIXTURE.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB8616508A GB2192347B (en) 1986-07-07 1986-07-07 Removing hydrogen sulphide and carbon dioxide from a gas mixture containing hydrogen sulphide and carbon dioxide.

Publications (3)

Publication Number Publication Date
GB8616508D0 GB8616508D0 (en) 1986-08-13
GB2192347A true GB2192347A (en) 1988-01-13
GB2192347B GB2192347B (en) 1989-12-13

Family

ID=10600677

Family Applications (1)

Application Number Title Priority Date Filing Date
GB8616508A Expired GB2192347B (en) 1986-07-07 1986-07-07 Removing hydrogen sulphide and carbon dioxide from a gas mixture containing hydrogen sulphide and carbon dioxide.

Country Status (9)

Country Link
CN (1) CN1016166B (en)
AU (1) AU590866B2 (en)
CA (1) CA1296160C (en)
DE (1) DE3721789A1 (en)
DK (1) DK170394B1 (en)
GB (1) GB2192347B (en)
IN (1) IN169707B (en)
NL (1) NL194362C (en)
NO (1) NO166920C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0279667A2 (en) * 1987-02-19 1988-08-24 The Dow Chemical Company Process for the removal of hydrogen sulfide and optionally carbon dioxide from gaseous streams

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4014018A1 (en) * 1990-05-01 1991-11-07 Metallgesellschaft Ag Gas purificn. using recyclable scrubber soln. - esp. for desulphurisation of fuel gas
GB9606685D0 (en) * 1996-03-29 1996-06-05 Boc Group Plc Gas separation
DE102008052612A1 (en) * 2008-10-21 2010-04-22 Uhde Gmbh Wash solution for gas scrubbing with amines in aqueous ammonia solution and use
CN102350174A (en) * 2011-07-11 2012-02-15 中国石油化工集团公司 Method for selective removal of H2S by dynamic wave scrubber
CN104667714A (en) * 2013-12-03 2015-06-03 中国科学院过程工程研究所 Device and method for deep removal of acid gas in industrial mixed gas
CN110218596B (en) * 2019-05-30 2020-09-29 中石化石油机械股份有限公司研究院 Deacidifying technological process of natural gas

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4091073A (en) * 1975-08-29 1978-05-23 Shell Oil Company Process for the removal of H2 S and CO2 from gaseous streams
US4359450A (en) * 1981-05-26 1982-11-16 Shell Oil Company Process for the removal of acid gases from gaseous streams
US4409199A (en) * 1981-12-14 1983-10-11 Shell Oil Company Removal of H2 S and COS

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0279667A2 (en) * 1987-02-19 1988-08-24 The Dow Chemical Company Process for the removal of hydrogen sulfide and optionally carbon dioxide from gaseous streams
EP0279667A3 (en) * 1987-02-19 1989-04-05 The Dow Chemical Company Process and composition for the removal of hydrogen sulfide and/or carbon dioxide from gaseous streams

Also Published As

Publication number Publication date
GB2192347B (en) 1989-12-13
NL194362C (en) 2002-02-04
CN1016166B (en) 1992-04-08
AU7500787A (en) 1988-01-14
NO872756L (en) 1988-01-08
NL194362B (en) 2001-10-01
AU590866B2 (en) 1989-11-16
CN87104539A (en) 1988-02-17
DK337487A (en) 1988-01-08
NO872756D0 (en) 1987-07-01
NO166920C (en) 1991-09-18
GB8616508D0 (en) 1986-08-13
DK170394B1 (en) 1995-08-21
IN169707B (en) 1991-12-14
CA1296160C (en) 1992-02-25
DK337487D0 (en) 1987-07-01
NO166920B (en) 1991-06-10
DE3721789A1 (en) 1988-01-21
NL8701225A (en) 1988-02-01

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PCNP Patent ceased through non-payment of renewal fee

Effective date: 20050707