CN104415643A - Method for selectively removing H2S from gas flow containing CO2 - Google Patents

Method for selectively removing H2S from gas flow containing CO2 Download PDF

Info

Publication number
CN104415643A
CN104415643A CN201310363785.4A CN201310363785A CN104415643A CN 104415643 A CN104415643 A CN 104415643A CN 201310363785 A CN201310363785 A CN 201310363785A CN 104415643 A CN104415643 A CN 104415643A
Authority
CN
China
Prior art keywords
amine liquid
order
gas
absorption
level
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.)
Pending
Application number
CN201310363785.4A
Other languages
Chinese (zh)
Inventor
毛松柏
朱道平
周志斌
杨绪甲
余勇
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.)
China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
Original Assignee
China Petroleum and Chemical Corp
Research Institute of Nanjing Chemical Industry Group Co Ltd
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 China Petroleum and Chemical Corp, Research Institute of Nanjing Chemical Industry Group Co Ltd filed Critical China Petroleum and Chemical Corp
Priority to CN201310363785.4A priority Critical patent/CN104415643A/en
Publication of CN104415643A publication Critical patent/CN104415643A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Landscapes

  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention provides a method for selectively removing H2S from an acidic gas containing CO2. A two-stage absorption technology is employed for increasing the concentration of H2S in a regenerated acidic gas, wherein amine solution in each absorption stage is individually regenerated. The acidic gas, which is higher in H2S concentration and is generated after amine solution regeneration after the first absorption stage, can be directly fed to a subsequent treatment process. The acidic gas, which is generated after the amine solution regeneration after the second absorption stage, is compressed and then is fed back to a raw material gas in the first absorption stage.

Description

A kind of from containing CO 2air-flow in selectively removing H 2the method of S
Technical field
The invention belongs to gas separation technique field, being specifically related to a kind of from containing CO 2admixture of gas in selectively removing H 2s technique.
Background technology
Usually containing a certain amount of H in the industrial gasses such as natural gas, synthesis gas, refinery gas 2s, before further processing and utilization, needs H wherein 2s is removed to quite low level.
For containing a large amount of H 2the gas of S, the employing alkanolamine aqueous solution absorbs H wherein usually 2s, then regenerates under suitable conditions, then the sour gas born is usually by CLAUS explained hereafter sulphur.
But nearly all gas is containing H 2while S, also can with a large amount of CO 2.H is absorbed at the employing alkanolamine aqueous solution 2during S, certainty also can simultaneously stability CO 2.As CO in unstripped gas 2/ H 2when the ratio of S acquires a certain degree, this simultaneously stability will cause CO in the sour gas born again 2too high, thus affect the operation of CLAUS device.Therefore, must develop from containing CO 2sour gas in remove H selectively 2the technology of S.
Optionally one of the Main Means improving desulfurization adopts novel high selective solvent, as:
US4,405,585 propose to realize selectively removing H with sterically hindered amine aqueous solution 2s;
US4,895,670 proposition sterically hindered amines and sterically hindered amino acid whose mixed liquor carry out selectively removing H 2s;
WO93/10883 proposition sterically hindered amines carrys out the H in enrichment lean gas 2s is to meet the requirement of Claus device;
The metal sulfonate of CN200680029581.5 proposition hindered amine, metal phosphinate hydrochlorate, metal phosphate, metal sulfate, metal aminosulfonate, metal phosphoramidate or metal carboxylate carry out selectively removing H 2s.
The another kind of optionally Main Means improving desulfurization is improving technique flow process, as:
DE2003113438 proposes absorbing the amine liquid of acid gas through multistage flash evaporation, parses part CO wherein 2, thus containing higher H in the acid gas produced when making amine liquid regenerate 2s.
The acid gas that US2008/0019899 proposes to produce when being regenerated by amine liquid is partly refluxed to absorption operation, makes H in the amine liquid of absorption step 2the ratio of S improves, thus H in the acid gas produced when improving the regeneration of amine liquid 2the concentration of S.
Pu Guang purification plant then adopts cascade EDFA technology, namely utilizes and absorbs temperature to amine absorption H 2s and CO 2impact, return absorption step again by after the amine liquid cooling but in absorption process, suppress CO with lower amine liquid temp 2absorption.
Summary of the invention
The object of the invention is to propose a kind of improvement from containing CO 2air-flow in selectively removing H 2the method of S.
The technique that the present invention adopts two-stage to absorb is to improve H in regeneration acid gas 2the concentration of S, the amine liquid in every grade of absorption regenerates separately, in first order absorption step, the H of the overwhelming majority in gas 2s is absorbed, and only has a small amount of CO 2absorbed, the acid gas produced after the amine liquid regeneration after the first order absorbs directly can be sent to follow-up CLAUS unit, in second level absorption step, mainly removes the H of minute quantity 2s, with the requirement making the gas after process can meet rear operation, the acid gas produced after the amine liquid regeneration after the second level absorbs returns in the unstripped gas of the first order after compression.
It can be conventional methyl diethanolamine (MDEA) solution that the first order and the second level absorb the selective desulfurization amine liquid adopted, also can be diisopropanolamine (DIPA) (DIPA) and various sterically hindered amines etc., they can be used alone, also can compositely use, or add different activator etc., in a word, those skilled in the art can adopt the aqueous alkanolamine of different formulations neatly according to processed material characteristic, its using method is known by those skilled in the art.. two-stage absorbs the amine liquid adopted can be identical, also can be different.
Can according to the component of unstripped gas and rear operation to the requirement of acid gas, H in adjustment two-stage absorption step flexibly 2the ratio that S absorbs.
Anyly comprise H simultaneously 2s and CO 2gas can process according to the present invention.Source of the gas is not crucial for purposes of the invention, comprises such as natural gas, synthesis gas and various refinery gas.
Absorption equipment of the present invention can be conventional plate column, also can be to improve selectively removing H 2the equipment of S comprises hypergravity machine, dynamic wave scrubber etc.Preferential use improves selectively removing H 2the equipment of S.
The present invention can be regenerated amine liquid by heating and steam stripped mode.Concrete regeneration is that the art personnel are known.
Advantage of the present invention is: H in the sour gas born again 2the content of S is higher than conventional method.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the inventive method embodiment selective desulfurization.
In figure: 1-5-gas line, 21-first order absorber, 31-second level absorber, 22-first order regenerator, 32-second level regenerator, 23,33-lean solution cooler, 24,34-lean pump, 25,35-solution heat exchanger, 26,36-reboiler, 27,37-acid gas cooler, 28,38-separator.
Detailed description of the invention
The invention will be further described below by way of embodiments and drawings, but it does not limit the scope of the invention.
Embodiment:
As shown in Figure 1, unstripped gas regenerates after acid gas mixes through pipeline 1 and the second level and enters in first order absorber 21 the present embodiment method, wherein the H of the overwhelming majority 2s and a small amount of CO 2by amine absorption, enter second level absorber 31 from first order absorber 21 gas out through pipeline 2, in second level absorber 31, most H in gas 2s and part CO 2by amine absorption, reach gas operation after pipeline 3 is sent to that purification requires.
From the first order absorber 21 amine liquid (rich solution) absorbing acid gas out, in solution heat exchanger 25, carry out heat exchange with lean solution, after recovery section heat, enter in first order regenerator 22, separate sucking-off sulfide wherein and CO 2.Cool from first order regenerator 22 regeneration acid gas out through acid gas cooler 27, then through moisture trap 28 reclaim go after condensate liquid after operation.
From the first order regenerator 22 good solution of regeneration (lean solution) out, through solution heat exchanger 25 and rich solution heat exchange, then after pressurizeing through solution pump 24, being cooled by lean solution cooler 23, enter first order absorber 21 and recycle.
From the second level absorber 31 amine liquid (rich solution) absorbing acid gas out, in solution heat exchanger 35, carry out heat exchange with lean solution, after recovery section heat, enter in second level regenerator 32, separate sucking-off sulfide wherein and CO 2.Cool through acid gas cooler 37 from second level regenerator 32 regeneration acid gas out, then reclaim after condensate liquid through moisture trap 38 and mixed with unstripped gas by pipeline 5.
From the second level regenerator 32 good solution of regeneration (lean solution) out, through solution heat exchanger 35 and rich solution heat exchange, then after pressurizeing through solution pump 34, being cooled by lean solution cooler 33, enter second level absorber 31 and recycle.
Adopt above-mentioned technological process, to certain coal based synthetic gas (4.0MPa, temperature normal temperature, H 2s0.6%vt, CO 231.0%vt) carry out desulfurization, first order absorber is 6 blocks of column plates, and second level absorber is 10 blocks of column plates, with the MDEA aqueous solution of 50%wt for absorbent, and purified gas H 2s < 20 × 10 -6, H in regeneration gas 2s > 12% vt.

Claims (5)

1. one kind from containing CO 2air-flow in selectively removing H 2the method of S, is characterized in that the technique that it adopts two-stage to absorb regenerates H in acid gas to improve 2the concentration of S, the amine liquid in every grade of absorption regenerates separately, and wherein, the acid gas produced after the amine liquid regeneration after the first order absorbs directly is sent to follow-up treatment process, and the acid gas produced after the amine liquid regeneration after the absorption of the second level returns in the unstripped gas of the first order after compression.
2. method according to claim 1, it is characterized in that the first order and the second level absorb the selective desulfurization amine liquid adopted is one or more composite uses in methyl diethanolamine MDEA solution, diisopropanolamine (DIPA) DIPA, various sterically hindered amines.
3. method according to claim 1 and 2, is characterized in that adding different activators in described amine liquid.
4. method according to claim 1 and 2, is characterized in that the first order and the second level absorb the amine liquid phase adopted same.
5. method according to claim 1 and 2, is characterized in that the first order and the second level absorb the amine liquid adopted different.
CN201310363785.4A 2013-08-20 2013-08-20 Method for selectively removing H2S from gas flow containing CO2 Pending CN104415643A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310363785.4A CN104415643A (en) 2013-08-20 2013-08-20 Method for selectively removing H2S from gas flow containing CO2

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310363785.4A CN104415643A (en) 2013-08-20 2013-08-20 Method for selectively removing H2S from gas flow containing CO2

Publications (1)

Publication Number Publication Date
CN104415643A true CN104415643A (en) 2015-03-18

Family

ID=52966424

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310363785.4A Pending CN104415643A (en) 2013-08-20 2013-08-20 Method for selectively removing H2S from gas flow containing CO2

Country Status (1)

Country Link
CN (1) CN104415643A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110052119A (en) * 2019-03-26 2019-07-26 昆明理工大学 Organic solvent absorbs hydrogen sulfide and the method for the utilization of resources in concentrate commercial acid gas
CN112246071A (en) * 2020-09-29 2021-01-22 中国船舶重工集团公司第七一一研究所 Torch gas compression and desulfurization integrated process and system thereof
CN113528206A (en) * 2020-04-13 2021-10-22 中国石油天然气股份有限公司 Desulfurization system and method

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1554467A (en) * 2003-12-26 2004-12-15 南化集团研究院 Removing sulfide from CO2 enriched gas by complex iron method
WO2005075056A1 (en) * 2004-01-20 2005-08-18 Fluor Technologies Corporation Methods and configurations for acid gas enrichment
CN1891328A (en) * 2006-05-10 2007-01-10 杨皓 Low concentration adsorbable contituent variable-pressure adsorption and separation method
CN1962032A (en) * 2005-11-09 2007-05-16 南化集团研究院 Solvent and method for simultaneous removal of hydrogen sulphide and carbon dioxide
CN101143286A (en) * 2006-09-15 2008-03-19 南化集团研究院 Method for removing COS from acid airflow
CN101676018A (en) * 2008-09-19 2010-03-24 南化集团研究院 Method for selectively removing COS from acid gas flow
CN101745289A (en) * 2008-12-12 2010-06-23 南化集团研究院 Method for selectively removing H2S from gas mixture containing CO2

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1554467A (en) * 2003-12-26 2004-12-15 南化集团研究院 Removing sulfide from CO2 enriched gas by complex iron method
WO2005075056A1 (en) * 2004-01-20 2005-08-18 Fluor Technologies Corporation Methods and configurations for acid gas enrichment
CN1962032A (en) * 2005-11-09 2007-05-16 南化集团研究院 Solvent and method for simultaneous removal of hydrogen sulphide and carbon dioxide
CN1891328A (en) * 2006-05-10 2007-01-10 杨皓 Low concentration adsorbable contituent variable-pressure adsorption and separation method
CN101143286A (en) * 2006-09-15 2008-03-19 南化集团研究院 Method for removing COS from acid airflow
CN101676018A (en) * 2008-09-19 2010-03-24 南化集团研究院 Method for selectively removing COS from acid gas flow
CN101745289A (en) * 2008-12-12 2010-06-23 南化集团研究院 Method for selectively removing H2S from gas mixture containing CO2

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王开岳: "《天然气净化工艺：脱硫脱碳、脱水、硫磺回收及尾气处理》", 31 July 2005, 石油工业出版社 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110052119A (en) * 2019-03-26 2019-07-26 昆明理工大学 Organic solvent absorbs hydrogen sulfide and the method for the utilization of resources in concentrate commercial acid gas
CN113528206A (en) * 2020-04-13 2021-10-22 中国石油天然气股份有限公司 Desulfurization system and method
CN112246071A (en) * 2020-09-29 2021-01-22 中国船舶重工集团公司第七一一研究所 Torch gas compression and desulfurization integrated process and system thereof

Similar Documents

Publication Publication Date Title
CN101835524B (en) Removal of carbon dioxide from a feed gas
EP2164608B1 (en) Method for recovering a gaseous component from a gas stream
US9902914B2 (en) Configurations and methods for processing high pressure acid gases with zero emissions
AU2011205517B2 (en) Water wash method and system for a carbon dioxide capture process
CN104548874A (en) Deacidification process and system for gas mixtures containing acid gases
CN101213010B (en) Method and apparatus for energy reduction in acid gas capture processes
AU2014200271B2 (en) Integrated carbon dioxide removal and ammonia-soda process
JP2012525253A (en) Absorbent that self-concentrates to separate acidic gases
JP4216152B2 (en) Desulfurization decarboxylation method and apparatus
CN101745289B (en) Method for selectively removing H2S from gas mixture containing CO2
KR20110085983A (en) Reabsorber for ammonia stripper offgas
CN107073388B (en) Regeneration method of energy-saving solvent for carbon dioxide capture
US20130008310A1 (en) Alcohol-based gas stripping process
CN105214445A (en) A kind of amine absorbent for removing sulfur dioxide in gaseous mixture
CN104338418A (en) Ammonia stripper for a carbon capture system for reduction of energy consumption
EP3645672B1 (en) Process for gas separation by solvent or absorbent
CN106311149A (en) Absorbent used for natural gas decarburization
CN104415643A (en) Method for selectively removing H2S from gas flow containing CO2
KR102037878B1 (en) Carbon Dioxide Absorbent And Method for Absorbing Carbon Dioxide Using the Same
CN104772021B (en) Polyalcohol ethylenediamine solution traps CO in industrial gas2Method
CN105344205A (en) Absorber for selectively removing H2S from CO2-containing mixing gas
CN107376586A (en) A kind of effective ways of coal-fired flue gas desulfurization decarburization
US20160008755A1 (en) Method and device for the treatment of a gas stream, in particular for the treatment of a natural gas stream
JP2014100623A (en) Amine recovery method, amine separation apparatus and acid gas separation and recovery apparatus
KR20160046592A (en) Energy savings type- LNG Feed gas pre-processing apparatus

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20150318