CN87104539A - From the gas mixture that contains hydrogen sulfide and carbonic acid gas, remove the method for hydrogen sulfide and carbonic acid gas - Google Patents

From the gas mixture that contains hydrogen sulfide and carbonic acid gas, remove the method for hydrogen sulfide and carbonic acid gas Download PDF

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Publication number
CN87104539A
CN87104539A CN87104539.7A CN87104539A CN87104539A CN 87104539 A CN87104539 A CN 87104539A CN 87104539 A CN87104539 A CN 87104539A CN 87104539 A CN87104539 A CN 87104539A
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China
Prior art keywords
gas mixture
aqueous solution
contactor
remove
nta
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Withdrawn
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CN87104539.7A
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Chinese (zh)
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CN1016166B (en
Inventor
马丁·马尔斯克·孙森
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Shell USA Inc
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Shell Oil Co
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Publication date
Application filed by Shell Oil Co filed Critical Shell Oil Co
Publication of CN87104539A publication Critical patent/CN87104539A/en
Publication of CN1016166B publication Critical patent/CN1016166B/en
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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
    • B01D53/1456—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)

Abstract

From containing H 2S and CO 2Remove H in the mixed gas 2S and CO 2Method comprise that gas mixture contacts with the oxidation agent reactant aqueous solution that contains significant quantity in first contactor (1), to obtain the mixed gas that part purifies and to contain sulphur and reactant reduction aqueous solution.Part purifies mixed gas and contacts with reproducible stripping liquid in second contactor (6), to be purified mixed gas and saturable absorber.

Description

The present invention relates to from containing H 2S and CO 2Gas mixture in remove H 2S and CO 2Method, the method for particularly from the gas mixture that contains hydro carbons, removing these acidic components.Contain 10～50%(volume in the gas mixture) CO 2With a spot of H 2S, for example H wherein 2S is for CO 2Volume ratio between 10 to 0.1.Sweet natural gas is an example of this acidic mixed gas.
The purpose of this invention is to provide a kind of concentration and remove H 2S and remove CO in a large number 2Flexible way.
In order to reach this purpose, of the present invention from containing H 2S and CO 2Gas mixture in remove H 2S and CO 2Method comprise following two steps:
A) gas mixture is contacted at first contactor with a kind of aqueous solution that contains the oxidation agent of significant quantity, obtaining the gas mixture that part purifies and the aqueous solution of a kind of sulfur-bearing and reducing agents, and will partly purify gas mixture and feed second contactor,
B) make part purify gas mixture and contact with a kind of reproducible stripping liquid, purify gas mixture and saturable absorber to produce at second contactor.
By the oxidation of reagent, make before or after the partial reduction reagent regeneration at least, can from the aqueous solution that step a) obtains, remove the sulphur that generates in the step a).
Though part purifies gas mixture and need not further to handle or transform to enter second contactor, if desired, can heat or cool off partly purifying gas mixture.
In a suitable embodiment, reactant aqueous solution contains organic acid [for example a nitrilotriacetic acid(NTA) (NTA) or ethylenediamine tetraacetic acid (EDTA) (EDTA)] and Fe(III) co-ordination complex.
At one preferably in the embodiment, reactant aqueous solution contains the Fe(III) with ammonium formula title complex and NTA and the Fe(II of NTA) ammonium formula title complex.Reactant aqueous solution and can contain ammoniacal liquor.The suitable pH value of solution between 5 to 8.5, Fe(III in the solution) and the ammonium formula title complex of NTA to NTA and Fe(II) the optimum mol ratio of ammonium formula title complex between 0.2 to 6.Whenever remove one mole of H 2The S reactant aqueous solution to comprise about 2～15 moles with the Fe(III) the ammonium formula title complex of NTA.
Part purifies CO contained in the gas mixture 2To in step b), be removed by means of reproducible stripping liquid.In order to remove CO the saturable absorber that obtains from step b) 2, this saturable absorber will carry out flash distillation once at least, and flash evaporation is to being lower than CO under the temperature commonly used with pressure release 2The level of dividing potential drop.Remove the hydrocarbon that is absorbed simultaneously if desired, saturable absorber will carry out flash distillation once at least before this step, and flash evaporation is to use CO under pressure and the temperature commonly used always when step b) contacts with pressure release 2Between the dividing potential drop.
In a more suitable embodiment, reproducible stripping liquid is a kind of aqueous solution of amine, for example the tertiary amine of weevil base diethanolamine (MDEA) class.
Reproducible stripping liquid also can comprise for example tetramethylene sulfone of a kind of physical solvent.
This reproducible stripping liquid should contain 10～60%(weight) the MDEA aqueous solution 15～55%(weight) tetramethylene sulfone and 5～35%(weight) water.
Equipment flowsheet below with reference to the inventive method is done comparatively detailed explanation to the present invention.
Equipment has: first contactor, 1. sulfur recovery devices, 3, the first revivifier 5, the second contactors, 6, the first flashers 8 and second flashers 9.Sour gas service 10 is connected with first contactor 1, and first contactor links to each other with sulfur recovery device 3 by pipeline 12, is connected with second contactor 6 by pipeline 14.Sulfur recovery device 3 is provided with sulphur relief outlet 15, and links to each other with first revivifier 5 by pipeline 16.First revivifier 5 is connected to oxygenant service 17 and exhaust pipe 19.By pipeline 20, first revivifier 5 is linked to each other with first contactor 1.
Second contactor 6 is equipped with the outlet conduit 21 of purified gas, and by pipeline 22 this contactor 6 is linked to each other with first flasher 8, and reducing valve 23 is housed on pipeline 22.First flasher 8 is equipped with vapor pipe 25, and links to each other with second flasher 9 by the pipeline 26 that reducing valve 27 is housed.Second flasher 9 is equipped with vapor pipe 30, and links to each other with second contactor 6 by pipeline 31.
Embodiment
Contain the 15%(volume) CO 2With 250ppmv(1,000,000/, by volume) the hydrocarbonaceous acidic mixed gas of H S enters in first contactor 1 by sour gas service 10.
In first contactor, acidic mixed gas contains 0.65 mole of Fe(III with every liter) contact with the reactant aqueous solution of the ammonium formula title complex of NTA.To obtain containing the 12%CO(volume) and 2ppmvH 2The part of S purifies gas mixture, and the Fe(II that comprises sulphur and additional content) with the aqueous solution of the reduction reaction agent of the ammonium formula title complex of NTA.The aqueous solution of sulfur-bearing and reduction reaction agent enters devulcanizer 3 by pipeline 12, by pipeline 15 sulphur is discharged from devulcanizer 3.The aqueous solution that is substantially free of sulphur enters first revivifier 5 through piping 16, contacts with the aqueous solution by the air of sending into from oxygenant service 17 there, has at least the partial reduction reagent to obtain oxidation.The regenerative response agent aqueous solution enters first contactor 1 by pipeline 20, and off-air is discharged from first revivifier 5 by exhaust pipe 19.
Do not have processed part to purify gas mixture and enter second contactor 6, contact with reproducible stripping liquid [for containing 30%(weight) MDEA aqueous solution form] there, removing CO the gas mixture from partly purifying by pipeline 14 2Condition under to be purified gas mixture and saturated absorption agent.Contain the 1%(volume) CO 2With 1.5ppmv H 2The purification gas mixture of S is discharged from second contactor 7 by purified gas vent pipe 21, and saturable absorber enters first flasher 8 by pipeline 22.In first flasher 8, by the flash distillation of saturable absorber, removing the hydrocarbon that got off by coabsorption, the method for flash distillation is with pressure release CO under the pressure of second contactor 6 and the normal temperature 2Level between the dividing potential drop.Remove and, be substantially free of CO 2The hydrocarbonaceous gas mixture, by vapor pipe 25, discharge from first flasher 8.The absorption agent of the fractional saturation that obtains in first flasher 8 enters second flasher 9 by pipeline 26.In second flasher 9 by with pressure release to being lower than CO under the normal temperature 2Dividing potential drop, remove the CO in the fractional saturation absorption agent 2, to obtain absorbent regeneration.By pipeline 31 absorbent regeneration is supplied with second contactor 6.Remove the H that is substantially free of that gets off 2The CO of S 2Discharge from second flasher 9 by vapor pipe 30.
First contactor 1 and first revivifier 5 can be to help that gas contacts with liquid countercurrent or and the various tower contactor of stream contact.

Claims (8)

1, from containing H 2S and CO 2Gas mixture in remove H 2S and CO 2Method, this method comprises following two steps:
A) gas mixture is contacted in first contactor with the reactant aqueous solution of the oxidation agent that contains significant quantity,, will purify gas mixture and feed second contactor to obtain the aqueous solution that part purifies gas mixture and sulfur-bearing and reduction reaction agent;
B) make part purify gas mixture and in second contactor, contact, purify gas mixture and saturable absorber to produce with reproducible stripping liquid.
2, method according to claim 1, reactant aqueous solution wherein contain a kind of suitable organic acid and Fe(III) compound.
3, method according to claim 1, reactant aqueous solution wherein contain nitrilotriacetic acid(NTA) and F(III) ammonium formula compound and nitrilotriacetic acid(NTA) and F(III) ammonium formula compound and also F(II of nitrilotriacetic acid(NTA)) ammonium formula compound.
4, according to each requires described method in the claim 1-3 item, reproducible stripping liquid wherein is the tertiary amine aqueous solution.
5, method according to claim 4, tertiary amine wherein are methyldiethanolamine.
6, require described method according in the claim 1-5 item each, wherein saturable absorber carries out single flash at least, and to obtain the absorbent regeneration that the guiding principle step b) is used, flash evaporation is to be discharged in the future to be lower than CO under the temperature commonly used 2Dividing potential drop.
7, require described method according in the claim 1-5 item each, wherein saturable absorber will carry out single flash at least, to obtain the fractional saturation absorption agent; The method of flash distillation is, with pressure release to CO under the wirking pressure of step b) contact and temperature commonly used 2Between the dividing potential drop; Wherein the fractional saturation absorption agent will carry out single flash at least, is pressure release to be dripped to be lower than use CO under the temperature always to obtain for the absorbent regeneration flash evaporation that step b) is used 2Dividing potential drop.
8, according to claim 1 from containing H 2S and CO 2Remove H in the gas mixture 2S and CO 2Method, be with reference to the method described in the last texts and pictures basically.
CN87104539A 1986-07-07 1987-06-30 Removing h2s and co2 from gas mixture containing h2o and co2 Expired CN1016166B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8616508 1986-07-07
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.

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CN87104539A true CN87104539A (en) 1988-02-17
CN1016166B CN1016166B (en) 1992-04-08

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CN87104539A Expired CN1016166B (en) 1986-07-07 1987-06-30 Removing h2s and co2 from gas mixture containing h2o and co2

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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 (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1090044C (en) * 1996-03-29 2002-09-04 英国氧气集团有限公司 Gas seperation
CN102186561A (en) * 2008-10-21 2011-09-14 犹德有限公司 Washing solution for gas scrubbing, containing amines in an aqueous ammonia solution and use thereof
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
CN110218596A (en) * 2019-05-30 2019-09-10 中石化石油机械股份有限公司研究院 A kind of deacidifying process process of natural gas

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ223528A (en) * 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
DE4014018A1 (en) * 1990-05-01 1991-11-07 Metallgesellschaft Ag Gas purificn. using recyclable scrubber soln. - esp. for desulphurisation of fuel 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 (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1090044C (en) * 1996-03-29 2002-09-04 英国氧气集团有限公司 Gas seperation
CN102186561A (en) * 2008-10-21 2011-09-14 犹德有限公司 Washing solution for gas scrubbing, containing amines in an aqueous ammonia solution and use thereof
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
CN110218596A (en) * 2019-05-30 2019-09-10 中石化石油机械股份有限公司研究院 A kind of deacidifying process process of natural 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

Also Published As

Publication number Publication date
NO166920C (en) 1991-09-18
DK337487A (en) 1988-01-08
NO166920B (en) 1991-06-10
NL8701225A (en) 1988-02-01
NO872756D0 (en) 1987-07-01
AU590866B2 (en) 1989-11-16
NO872756L (en) 1988-01-08
GB8616508D0 (en) 1986-08-13
GB2192347A (en) 1988-01-13
DK337487D0 (en) 1987-07-01
NL194362B (en) 2001-10-01
AU7500787A (en) 1988-01-14
IN169707B (en) 1991-12-14
DE3721789A1 (en) 1988-01-21
CA1296160C (en) 1992-02-25
DK170394B1 (en) 1995-08-21
GB2192347B (en) 1989-12-13
CN1016166B (en) 1992-04-08
NL194362C (en) 2002-02-04

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