CN1171659C - Solvent for selectively removing sulfide from CO2-contained gas mixture - Google Patents
Solvent for selectively removing sulfide from CO2-contained gas mixture Download PDFInfo
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- CN1171659C CN1171659C CNB011272597A CN01127259A CN1171659C CN 1171659 C CN1171659 C CN 1171659C CN B011272597 A CNB011272597 A CN B011272597A CN 01127259 A CN01127259 A CN 01127259A CN 1171659 C CN1171659 C CN 1171659C
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- solution
- sterically hindered
- selectively removing
- hindered amines
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- 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
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- 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
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Abstract
The present invention provides a solvent for selectively eliminating sulfides from the gas mixture of CO2, which belongs to the gas treatment field. The present invention provides an improved solution for selectively eliminating the sulfides from the gas mixture; steric hindrance amine (I) and N-methyl diethanolamine (II) are used as main absorbent for H2S. The solution of the present invention has the following obvious characteristics of high selectivity to the H2S, large absorption capacity to the H2S, rapid speed rate of absorption and desorption, low regeneration consumption of the solution and low cost of the solvent.
Description
Technical field: the invention belongs to gas separation technique field, be specifically related to a kind of from containing CO
2Gaseous mixture in the solvent of selectively removing sulfide.
Background technology: the desulfurization of amine method has been to remove H from industrial gas such as Sweet natural gas, refinery gas, synthetic gas since early 1930s is realized industrialization always
2The main method of S.In decades, amine method technology constantly develops, and has obtained rapid progress, has formed multiple alternative amine method desulfurization solvent, as Monoethanolamine MEA BASF, diethanolamine, diethyl Propanolamine and methyldiethanolamine (MDEA) etc.Wherein, the most general with methyldiethanolamine and various improvement methyldiethanolamine, as: US4,537,753 propose to remove CO in the Sweet natural gas with MDEA solution
2And H
2S; US4,397,660 propose with MDEA-sulfolane solution treatment process air-flow; DE3,411,532 propose to remove CO in the gas with the solution that contains MDEA-MEA and glycol (glycol ether)
2And H
2S.But along with the increasingly stringent of energy-intensive aggravation and environmental requirement, more and more higher to the requirement of selective desulfurization, these conventional sweetening agents can not adapt to requirement gradually.
US4,405,585 propose to realize selectively removing H with sterically hindered amine aqueous solution
2S.
US4,892,674 propose to non-space bulky amine solution (as MDEA) in, to add sterically hindered amine salt with (or) sterically hindered amino acid improves the selectivity of solution.
US4,895,670 propose to come selectively removing H2S with sterically hindered amines and sterically hindered amino acid whose mixed solution.
WO93/10883 proposes to come H in the enrichment lean gas with sterically hindered amines
2S is to satisfy the requirement of Claus device.
All there are shortcomings such as solvent is difficult for obtaining, price is more expensive in aforesaid method.
Summary of the invention: the present invention is a kind of novel solutions that contains sterically hindered amines (I) and N methyldiethanol amine (II), is used for from containing CO
2Gaseous mixture in selectively removing sulfide, using this solution than using separately MDEA solution has higher selectivity and acid gas load.
The present invention is achieved like this:
1, the aqueous solution with sterically hindered amines (I) and N methyldiethanol amine (II) is absorption agent.Strength of solution is 10～70% (wt), but is preferably 15～30% (wt).
2, component (I) can be a kind of single sterically hindered amines, also can be the mixture of several sterically hindered amines.
3, the sterically hindered amines of indication of the present invention is to have one or more alcamine compounds with non-linear carbochain of sterically hindered structure on nitrogen-atoms, has following structure:
Or
Wherein, R
1, R
2, R
3, R
5, R
6For containing the straight chained alkyl of 0～3 carbon atom, R
4, R
7Be straight chained alkyl or the alkoxyl group that contains 1～4 carbon atom.Its typical case is represented as:
TERTIARY BUTYL AMINE base ethanol (TBX) (teriarybutylaminoethanol)
TERTIARY BUTYL AMINE base oxethyl ethanol (teriarybutylaminoethoxyethanol),
2-amino-2-methyl-1-propanol (AMX) (2-amino-2-methyl-1-propanol),
(1-methyl isophthalic acid-second Propylamino) ethoxy ethanol ((1-methyl-1-ethylpropylamino) ethoxyethanol),
2-isopropylamine base-1-propyl alcohol (2-isopropylamino-1-propanol),
3-TERTIARY BUTYL AMINE base-just-butanols (3-teriarybutylamino-n-butanol),
2-(2-TERTIARY BUTYL AMINE base) propoxy-ethanol (2-(2-teriarybutylamino) propoxyethanol) etc.
4, component (II) is 0.5～4: 4.5～1 with the mol proportioning of component (I), but is preferably 1～2: 2～3.
Description of drawings:
Accompanying drawing 1 is that laboratory rapid determination absorption liquid is from containing CO
2Gaseous mixture in the optionally device of selectively removing sulfide; Accompanying drawing 2 is that the different absorption liquids of forming are to H
2The selectivity of S and receptivity.In the accompanying drawing 1, the 1-absorption tube; The 2-under meter; The 3-surge flask; The 4-gas mixture; The 5-thermostatic bath; The 6-absorption liquid; The 7-purified gas; A-gasometry thief hole.In the accompanying drawing 2, represents MDEA; ● expression 1.0M MDEA+1.5M AMX; △ represents 1.5MMDEA+1.0M TBX; * expression 1.0M MDEA+1.5M TBX.
Embodiment:
Below in conjunction with accompanying drawing and embodiment the present invention is described in detail:
Embodiment one:
On accompanying drawing one shown device, estimate amine liquid to H
2The selectivity of S.Its flow process is: gas mixture 4 enters in the absorption tube 1 that liquid to be evaluated is housed through surge flask 3 after metering, and bubbling absorbs, absorption temperature after after a while, is carried out sampling analysis to emptying end gas by thermostatic bath 5 controls, close source of the gas then, the rich solution of getting after the absorption carries out liquid phase analysis.H in unstripped gas and the liquid phase
2S adopts iodimetry,iodometry, H in the purified gas
2S adopts mercurimetry, and the gas phase acid gas adopts Ovshinsky instrument analytical method, and the liquid phase acid gas adopts gas evolution method, and organic amine concentration adopts chromatography.
Judgement criteria is:
(1) selectivity S
In the formula: l represents to absorb back rich solution liquid phase,
G represents the tail gas gas phase,
[H
2S] and [CO
2] concentration that analyzes of expression.
This value is big more, shows that absorption liquid is to H in the gas mixture
2The selectivity of S is big more.
(2) the acid gas load refers to the H that every mol organic amine is absorbed here
2S (mol), ideal solution still should have higher selectivity under higher acid gas load.
(3) receptivity refers to absorb when reaching balance, the H that every mol organic amine is absorbed
2S (mol), this value is big more, then can reduce the solution circulated amount, thereby reduces the regeneration energy consumption.
Test conditions is: unstripped gas contains H
2S1%, CO
210%, N
289%, absorption temperature is 40 ℃, and solution amount is 100ml, and soak time is 20min.Test-results sees Table one.
Table one, selectivity test-results
| Numbering | Solution composition (mol/L) | Selectivity | |||
| Always | MDEA | AMX | TBX | ||
| 1 | 2.5 | 2.5 | 0 | 0 | 60 |
| 2 | 2.5 | 1.5 | 1.0 | 0 | 112 |
| 3 | 2.5 | 1.5 | 0 | 1.0 | 416 |
| 4 | 2.5 | 1.0 | 1.5 | 0 | 159 |
| 5 | 2.5 | 1.0 | 0 | 1.5 | 560 |
Embodiment two:
Soak time is 80min, and other is with embodiment one, and test-results is seen accompanying drawing 2.
Embodiment three:
Absorb to saturated, absorption temperature is 40 ℃, 50 ℃, and other is with embodiment one, and test-results sees Table two.
The comparison of table two, receptivity
| Sequence number | Solution composition | Absorption temperature ℃ | H 2When the S approximate equilibrium absorbs in the solution | |
| H 2S mol/mol amine | CO
2Mol/ | |||
| 1 | 1.0M MDEA+1.5M TBX | 40 | 0.157 | 0.392 |
| 2 | MDEA | 40 | 0.086 | 0.247 |
| 3 | 1.0M MDEA+1.5M TBX | 50 | 0.178 | 0.347 |
| 4 | MDEA | 50 | 0.092 | 0.175 |
Claims (4)
1, a kind of from carbonated gaseous mixture the solution of selectively removing sulfide, the aqueous solution with N methyldiethanol amine and sterically hindered amines is the absorption agent of sulfide, described sterically hindered amines is characterized in that having one or more alcamine compounds with non-linear carbochain of sterically hindered structure on nitrogen-atoms, have following structure:
Or
Wherein, R
1, R
2, R
3, R
5, R
6For containing the straight chained alkyl of 0～3 carbon atom, R
4, R
7Be straight chained alkyl or the alkoxyl group that contains 1～4 carbon atom; Total amine concentration is 10～70% (wt) in the solution, and the mol ratio of N methyldiethanol amine and sterically hindered amines is 0.5～4: 4.5～1.
2, according to claim 1 described from carbonated gaseous mixture the solution of selectively removing sulfide, it is characterized in that total amine concentration is 15～30% (wt) in the solution.
3, according to claim 1 described from carbonated gaseous mixture the solution of selectively removing sulfide, it is characterized in that the mol ratio of N methyldiethanol amine and sterically hindered amines is 1～2: 2～3 in the solution.
4, according to claim 1 described from carbonated gaseous mixture the solution of selectively removing sulfide, it is characterized in that sterically hindered amines can be a kind of single sterically hindered amines, also can be the mixture of several sterically hindered amines.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011272597A CN1171659C (en) | 2001-09-26 | 2001-09-26 | Solvent for selectively removing sulfide from CO2-contained gas mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011272597A CN1171659C (en) | 2001-09-26 | 2001-09-26 | Solvent for selectively removing sulfide from CO2-contained gas mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1356157A CN1356157A (en) | 2002-07-03 |
| CN1171659C true CN1171659C (en) | 2004-10-20 |
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ID=4667237
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011272597A Expired - Fee Related CN1171659C (en) | 2001-09-26 | 2001-09-26 | Solvent for selectively removing sulfide from CO2-contained gas mixture |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100384513C (en) * | 2004-12-17 | 2008-04-30 | 南化集团研究院 | Method for preventing corrosion of equipment for recovering carbon dioxide from ethanolamine |
| CN100352536C (en) * | 2004-12-17 | 2007-12-05 | 南化集团研究院 | Method for degrading solvent in system of restraning cholamine to recovery carbon dioxide |
| CN100421768C (en) * | 2005-07-12 | 2008-10-01 | 南京理工大学 | Composite solution for membrane contactor to absorb acid gas |
| CN100427178C (en) * | 2005-11-09 | 2008-10-22 | 南化集团研究院 | Solvent and method for simultaneous removal of hydrogen sulphide and carbon dioxide |
| US20130243677A1 (en) * | 2012-03-14 | 2013-09-19 | Exxonmobil Research And Engineering Company | Amine treating process for selective acid gas separation |
| EP2854993B1 (en) * | 2012-05-31 | 2018-12-26 | Shell International Research Maatschappij B.V. | A method of improving a process for the selective absorption of hydrogen sulfide |
| JP6491090B2 (en) | 2012-05-31 | 2019-03-27 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイＳｈｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌｅ Ｒｅｓｅａｒｃｈ Ｍａａｔｓｃｈａｐｐｉｊ Ｂｅｓｌｏｔｅｎ Ｖｅｎｎｏｏｔｓｈａｐ | Absorbent composition for selective absorption of hydrogen sulfide |
| CN104629700B (en) * | 2015-02-03 | 2018-05-01 | 成都理工大学 | A kind of sulfur elimination for being used to produce water oil well and water-producing gas well |
| KR20180058723A (en) * | 2015-09-29 | 2018-06-01 | 바스프 에스이 | Selective removal of hydrogen sulphide |
| CN109513312A (en) * | 2017-09-18 | 2019-03-26 | 中国石化扬子石油化工有限公司 | A method of utilizing hydrogen sulfide in anhydrous desulfurization solvent removing gaseous mixture |
| CN110385022B (en) * | 2018-04-19 | 2022-07-15 | 中国石油化工股份有限公司 | Desulfurizing agent and application thereof, and method for light hydrocarbon desulfurization processing |
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