CN101455932A - Absorbing agent capable of removing sulfide from acid gas flow and method thereof - Google Patents
Absorbing agent capable of removing sulfide from acid gas flow and method thereof Download PDFInfo
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- CN101455932A CN101455932A CNA2007101911882A CN200710191188A CN101455932A CN 101455932 A CN101455932 A CN 101455932A CN A2007101911882 A CNA2007101911882 A CN A2007101911882A CN 200710191188 A CN200710191188 A CN 200710191188A CN 101455932 A CN101455932 A CN 101455932A
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- absorbent
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- acid gas
- air current
- formyl
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Abstract
The invention belongs to the technical field of gas purification, and relates to an absorbent and a method for removing sulfide from acid air current. The acid air current comprises natural gas, synthesis gas, refinery gas, liquefied petroleum gas and the like. The absorbent comprises the following components by weight percentage: 15 to 55 percent of serotonin solution and 5 to 11.5 percent of activating agent. If the acid air current is contacted with the absorbent, the sulfides of H2S, COS, thiol and the like can be deeply removed from the air current, thereby reducing a post-treatment procedure.
Description
Technical field:
The invention belongs to the gas purification technique field, be specifically related to from acid gas stream, remove the absorbent and the method for sulfide.This acid gas stream comprises natural gas, synthesis gas, refinery gas, liquefied petroleum gas etc.
Background technology:
Usually contain H in the industrial gasses
2S, CO
2With objectionable impurities such as COS, various mercaptan, thioethers, before further utilizing, they must removed totally, up to the present, the technology that is applied to the decarburization of qi exhaustion sulphur is descended hundreds of.Modal is that acid gas stream contacts in gas cleaning plant with organic solvent (or aqueous solution of organic solvent).A large amount of patent documentations have been arranged in these processes.Generally speaking, two kinds of different gas purification solvents are roughly arranged.
First kind is physical solvent, and what lean on is Physical Absorption.Typical physical solvent has the mixture of sulfolane and its derivative, straight chain acid amides, NMP (N-methyl pyrrolidone), N-alkyl pyrrolidone, relevant pyrrolidones, methyl alcohol and polyvinyl alcohol dialkyl ether.
Another kind is a chemical solvent.Based on chemical reaction, make sour gas generate the compound of easily removing.For instance, industrial the most frequently used chemical solvent is a hydramine, because the salt that generates decomposes easily or carried by steam gas easily, therefore amine can recycle.From air-flow, remove the MDEA that the reasonable amine of acid ingredient has monoethanolamine (MEA), diethanol amine (DEA), triethanolamine (TEA), diisopropanolamine (DIPA) (DIPA), amido ethoxy ethanol (AEE), methyl diethanolamine (MDEA) and added various activators.
Usually, above-mentioned solvent is to removing H
2S and CO
2Have higher efficient, but then there are many difficulties in organic sulfur.Physical solvent can be with organic sulfur removal to very low level, but this process is inappropriate, because these physical solvents can absorb other linear paraffin, regeneration deals with very expensive.In the chemical solvent, various hydramine are not high to the percent hydrolysis of COS, and only rely on physical dissolution to remove mercaptan to sulfur alcohol compound, because the solubility of mercaptan in aqueous alkanolamine is very little, therefore, removal effect extreme difference to organic sulfur, after the amine method is handled, to adopt catalyzing hydrolysis or alkali cleaning, catalytic oxidation desulfurization alcohol toward contact, again through the fixed bed fine desulfurization process by dry, cause that the desulfurization general steps is various, main-process stream is tediously long, thereby equipment is many, the investment big, wastage in bulk or weight index height.
Therefore, there is Many researchers that organic sulfide removal has been proposed suggestion, comprises:
US3,716,620 propose to add iodine in amine aqueous solution removes H
2S and mercaptan.
US4,808,765 propose to remove H in the unstripped gas with MDEA and diisopropanolamine (DIPA) (DIPA) mixed solution
2S and COS.
US5,589,149 propose to remove mercaptan in the unstripped gas with the mixed solution of amine aqueous solution and polyethylene glycol alkyl ether.
DE19933301 proposes to remove H with MDEA and piperazine
2S and mercaptan.
DE19947845 proposes to remove H with MDEA and piperazine
2S and COS.
Said method all fails in amine aqueous solution organic sulfur to be removed simultaneously, thereby also need increase other desulfurizer.
The objective of the invention is to, adopt a kind of novel solution, it is compared with traditional sulfur method, can deep removal H
2S, COS, mercaptan, thioether sulfides, thus treatment process reduced, make method of the present invention more economical.
Summary of the invention:
The present invention adopts a kind of varies aqueous solution to make absorbent; comprise the varies solution of percentage by weight 15-55% and the activator of percentage by weight 5-11.5%; varies solution is made up of methyl diethanolamine MDEA and diisopropanolamine (DIPA) DIPA, and activator is made up of formyl-morpholine and hydroxyethyl piperazine or is made up of formyl-morpholine and piperazine.
Absorbent of the present invention and method thereof can be removed most H from air-flow
2S and most mercaptan, thus postprocessing working procedures reduced, make method of the present invention more economical.
MDEA and DIPA are 2-3:1 in the varies solution.
Activator is made up of formyl-morpholine and hydroxyethyl piperazine or is made up of formyl-morpholine and piperazine.Wherein the ratio of formyl-morpholine and hydroxyethyl piperazine or piperazine is 1-3:1.
In the absorbent varies aqueous solution used in the present invention, also can comprise as corrosion inhibitor, defoamer and antisludging agent, perhaps the additive of similar components.Typically, the concentration range of these additives is 0.01%～2% (wt), and the use of these additives is that present technique field personnel are known.
Method of removing sulfide of the present invention is that the sulfide in the air-flow is removed by contacting with absorbent of the present invention.
Adopt the employed device of solvent removal mercaptan of the present invention can with habituation use identical.Sulfide in the air-flow was removed by contacting with the mixed amine aqueous solution of the present invention.
Absorption process can one-time-reach-place, also can continuous several times carry out.Can use the solution of multiply to carry out the gas-liquid contact among the latter from the order that reduces successively by temperature to cat head at the bottom of the tower.
The rich solution that has absorbed acid gas is realized regeneration by decompression, can realize by choke valve.The energy that rich solution contains can reclaim by turbine.
Flash tank can be adopted when removing acid gas, also repeatedly flash distillation can be carried out.Rich solution passes through and further regenerates the back and then be recycled to absorption step after the flash distillation.
Any known equipment in this area may be used to absorb, regenerate and other step.
The specific embodiment:
Below the invention will be further described by embodiment, its objective is in order to understand content of the present invention better, but it does not limit protection scope of the present invention.
Embodiment:
Operating characteristics to concrete absorbent on an experimental rig is directly measured.The absorption tower internal diameter 20mm of test usefulness, interior dress φ 3 * 3 stainless steel θ ring, regenerator internal diameter 50mm, interior dress φ 6 * 6 * 1 porcelain Raschig ring, reboiler is equipped with in the regenerator bottom.
The unstripped gas for preparing (contains H
2S 5%, CO
28%, COS 138 * 10
-6, methyl mercaptan 57 * 10
-6, ethyl mercaptan 32 * 10
-6, 1-propanethiol 8 * 10
-6, 2-propanethiol 9 * 10
-6) entering the solution counter current contacting that absorption tower bottom and cat head enter, the acid gas in the gas is absorbed, and purified gas comes out to enter gas-liquid separator from cat head and reclaims emptying after institute's droplets entrained.
The rich solution that has absorbed acid gas leads to the regenerator top at the bottom of the absorption tower, contact and obtain regeneration with the steam counter-flow of rising in regenerator.Lean solution after the regeneration is sent into absorption tower jacking row and is absorbed after cooling.The gas that comes out from regeneration overhead enters the regeneration gas cooler with the recovery of the water vapour the gas, and regeneration gas is emptying after separating.
At gas flow one regularly, the operating characteristics of different absorbents sees Table one.
Table one: the operating characteristics of different composite absorbers
Table one data show uses absorbent composition of the present invention, and its removal efficiency to total sulfur can obviously improve.
Claims (6)
1. absorbent of from acid gas stream, removing sulfide; it is characterized in that absorbent is the aqueous solution; comprise the varies solution of percentage by weight 15-55% and the activator of percentage by weight 5-11.5%; varies solution is made up of methyl diethanolamine MDEA and diisopropanolamine (DIPA) DIPA, and activator is made up of formyl-morpholine and hydroxyethyl piperazine or is made up of formyl-morpholine and piperazine.
2. absorbent according to claim 1 is characterized in that the weight ratio of MDEA and DIPA is 2-3:1 in the varies.
3. absorbent according to claim 1, the weight ratio that it is characterized in that formyl-morpholine and hydroxyethyl piperazine is 1-3:1.
4. absorbent according to claim 5, the weight ratio that it is characterized in that formyl-morpholine and piperazine is 1-3:1.
5. absorbent according to claim 1 is characterized in that adding in the absorbent corrosion inhibitor, defoamer and antisludging agent.
6. a method of removing sulfide from acid gas stream is characterized in that making the sulfide in the air-flow to be removed by contacting with the described absorbent of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101911882A CN101455932A (en) | 2007-12-11 | 2007-12-11 | Absorbing agent capable of removing sulfide from acid gas flow and method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101911882A CN101455932A (en) | 2007-12-11 | 2007-12-11 | Absorbing agent capable of removing sulfide from acid gas flow and method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101455932A true CN101455932A (en) | 2009-06-17 |
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ID=40767227
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101911882A Pending CN101455932A (en) | 2007-12-11 | 2007-12-11 | Absorbing agent capable of removing sulfide from acid gas flow and method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844035A (en) * | 2010-06-28 | 2010-09-29 | 四川省精细化工研究设计院 | High-efficient desulfurizing agent for removing hydrogen sulfide and organic mercaptan from mixed gas |
| CN102051244A (en) * | 2009-10-28 | 2011-05-11 | 中国石油化工股份有限公司 | High-efficiency purification desulfurizer for high-acid oil and gas |
| CN102580473A (en) * | 2012-03-20 | 2012-07-18 | 中国石油化工股份有限公司 | Absorbent for selectively removing H2S and organic sulfur |
| CN103272472A (en) * | 2013-06-18 | 2013-09-04 | 上海电力学院 | Flue gas desulfurization synergist for wet desulfurization system, and preparation method and application thereof |
| CN103814013A (en) * | 2011-07-28 | 2014-05-21 | 陶氏环球技术有限责任公司 | Aminopyridine derivatives for removal of hydrogen sulfide from gas mixture |
| CN104334252A (en) * | 2012-05-25 | 2015-02-04 | 道达尔公司 | Process for purifying gas mixtures containing acid gases |
| CN105344205A (en) * | 2014-08-20 | 2016-02-24 | 中国石油化工股份有限公司 | Absorber for selectively removing H2S from CO2-containing mixing gas |
| CN105879602A (en) * | 2016-05-25 | 2016-08-24 | 郝天臻 | Desulfurization solvent for treating sulfur-containing tail gas and treatment process |
| CN106540516A (en) * | 2015-09-18 | 2017-03-29 | 中国石油化工股份有限公司 | The Special desulfurizing agent of mercaptan is removed in a kind of natural gas |
| CN107684803A (en) * | 2016-08-05 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of organic amine absorbing liquid for removing air-flow middle acid substance |
-
2007
- 2007-12-11 CN CNA2007101911882A patent/CN101455932A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051244A (en) * | 2009-10-28 | 2011-05-11 | 中国石油化工股份有限公司 | High-efficiency purification desulfurizer for high-acid oil and gas |
| CN102051244B (en) * | 2009-10-28 | 2014-04-02 | 中国石油化工股份有限公司 | High-efficiency purification desulfurizer for high-acid oil and gas |
| CN101844035A (en) * | 2010-06-28 | 2010-09-29 | 四川省精细化工研究设计院 | High-efficient desulfurizing agent for removing hydrogen sulfide and organic mercaptan from mixed gas |
| CN103814013B (en) * | 2011-07-28 | 2016-06-01 | 陶氏环球技术有限责任公司 | For removing the aminopyrazole derivatives of hydrogen sulfide from gaseous mixture |
| CN103814013A (en) * | 2011-07-28 | 2014-05-21 | 陶氏环球技术有限责任公司 | Aminopyridine derivatives for removal of hydrogen sulfide from gas mixture |
| CN102580473A (en) * | 2012-03-20 | 2012-07-18 | 中国石油化工股份有限公司 | Absorbent for selectively removing H2S and organic sulfur |
| CN104334252A (en) * | 2012-05-25 | 2015-02-04 | 道达尔公司 | Process for purifying gas mixtures containing acid gases |
| CN103272472B (en) * | 2013-06-18 | 2015-06-17 | 上海电力学院 | Flue gas desulfurization synergist for wet desulfurization system, and preparation method and application thereof |
| CN103272472A (en) * | 2013-06-18 | 2013-09-04 | 上海电力学院 | Flue gas desulfurization synergist for wet desulfurization system, and preparation method and application thereof |
| CN105344205A (en) * | 2014-08-20 | 2016-02-24 | 中国石油化工股份有限公司 | Absorber for selectively removing H2S from CO2-containing mixing gas |
| CN106540516A (en) * | 2015-09-18 | 2017-03-29 | 中国石油化工股份有限公司 | The Special desulfurizing agent of mercaptan is removed in a kind of natural gas |
| CN105879602A (en) * | 2016-05-25 | 2016-08-24 | 郝天臻 | Desulfurization solvent for treating sulfur-containing tail gas and treatment process |
| CN107684803A (en) * | 2016-08-05 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of organic amine absorbing liquid for removing air-flow middle acid substance |
| CN107684803B (en) * | 2016-08-05 | 2021-12-10 | 中国石油化工股份有限公司 | Organic amine absorption liquid for removing acidic substances in gas flow |
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Application publication date: 20090617 |