CN104069716B - Solvent for removing CO2 and sulfides in acidic airflow, and application thereof - Google Patents
Solvent for removing CO2 and sulfides in acidic airflow, and application thereof Download PDFInfo
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- CN104069716B CN104069716B CN201410333175.4A CN201410333175A CN104069716B CN 104069716 B CN104069716 B CN 104069716B CN 201410333175 A CN201410333175 A CN 201410333175A CN 104069716 B CN104069716 B CN 104069716B
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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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
- 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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Abstract
The invention discloses a solvent for removing CO2 and sulfides in an acidic airflow, and application thereof, and aims to provide a solvent capable of removing CO2 and the sulfides in high removal rate. The solvent comprises the following components in percentage by weight: 20-60% of an amine compound, 1-10% of an activating agent, and the balance of water, wherein the activating agent comprises tetramethylene sulfone and diethylene glycol, and the amine compound is N-methyldiethanolamine. The solvent provided by the invention can remove CO2 and the sulfides from acidic gas, adopts the amine compound as a main absorbent, is supplemented with the activating agent consisting of tetramethylene sulfone and diethylene glycol, and can improve the removal rate of the CO2 and the sulfides through mutual synergy. Compared with a conventional desulfurization method, the solvent can effectively remove acidic substances such as H2S, CO2, COS and mercaptans, so that the treatment processes are reduced, and a higher economic value is provided. Meanwhile, the solvent further has the advantages of being renewable, low in cost and good in effect, can realize cyclic utilization, and has an important significance of reducing treatment cost of the acidic gas.
Description
Technical field
The present invention relates to field of gas purification, especially gas take off CO2And sulfide field, specially one kind is from sour gas
CO is removed in stream2And the solvent of sulfide and its application, this solvent can be used for natural gas, synthesis gas, refinery gas, liquefied petroleum gas
Take off CO Deng acid gas stream2And sulfide.
Background technology
CO is usually contained in industrial gases2、H2The objectionable impurities such as S and COS, various mercaptan, thioether, further with front,
These carbon dioxide and sulfide impurities must be removed clean.Up to the present, it is applied to the technology of gas sweetening decarburization
Under, hundreds of, be most commonly that acid gas stream and organic solvent（Or the aqueous solution of organic solvent）Gas cleaning plant connects
Touch, by organic solvent（Or the aqueous solution of organic solvent）To the CO in gas2, sulfide removed, had a large amount of literary compositions
Offer and carried out corresponding report.In general, take off CO for gas2And the purifying solvent of sulfide mainly has physical solvent, change
Learn two kinds of solvent.
Physical solvent relies primarily on Physical Absorption, typical physical solvent have sulfolane and it derivant, linear,
NMP（N-Methyl pyrrolidone）, the mixture of N- alkyl pyrrolidone, methanol and polyvinyl alcohol dialkyl ether.And chemical solution
Agent is then based on chemical reaction, makes sour gas generate the compound easily removed, thus reaching removing CO2, the purpose of sulfide.Lift
For example, industrial the most frequently used chemical agent is hydramine, because the salt generating easily decomposes or easily by steam stripping, amine
Therefore can recycle.Remove the reasonable amine of acid ingredient mainly to include from air-flow：Ethanolamine（MEA）, diethanolamine
（DEA）, triethanolamine（TEA）, diisopropanolamine (DIPA)（DIPA）, aminoethoxy ethanol（AEE）, methyl diethanolamine（MDEA）With
And with the addition of the MDEA of various activators.
For chemical field, how to improve CO in acid gas stream further2And the removing depth of sulfide, always
The focus of people's research.
Content of the invention
The goal of the invention of the present invention is：For above-mentioned problem, provide a kind of removing CO from acid gas stream2And
The solvent of sulfide and its application.The solvent of the present invention can be used in removing CO from sour gas2, sulfide, it is with compound
Amine, as main absorbent, is aided with sulfolane and the activator of diethylene glycol composition simultaneously, by the mutual coordinated between component,
CO can be effectively improved2With sulfide removal efficiency.Compared with traditional sulfur method, energy deep removal H of the present invention2S、CO2、
The acidic materials such as COS, mercaptan, thus decreasing treatment process, thus have higher economic worth.Meanwhile, the present invention's is molten
Agent also has renewable, low cost and other advantages, significant for the processing cost reducing sour gas.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of removing CO from acid gas stream2And the solvent of sulfide, including the component of following percentage by weight：
Serotonin 20～60%；
Activator 1～10%；
Water surplus；
Described activator is made up of sulfolane and diethylene glycol；
Described serotonin is N methyldiethanol amine.
In described activator, the weight of sulfolane and diethylene glycol is than for 1：10~10:1.
The percentage by weight of described serotonin is 30～50%.
The percentage by weight of described N methyldiethanol amine is 35～45%.
Also include additive, described additive is one or more of corrosion inhibitor, defoamer, antisludging agent.
Component including following percentage by weight：
Serotonin 20～60%；
Activator 1～10%；
Additive 0.01～5%；
Water surplus.
Aforementioned removing CO from acid gas stream2And the application of the solvent of sulfide, comprise the steps：Solvent and sour gas
Stream counter current contacting, removes the CO in acid gas stream2And sulfide.
Aforementioned removing CO from acid gas stream2And the application of the solvent of sulfide, comprise the steps：Solvent is divided into many
Stock, is made solvent be carried out multiple counter current contacting from top to bottom with acid gas stream, removes the CO in acid gas stream2And sulfide.
Aforementioned removing CO from acid gas stream2And the application of the solvent of sulfide, comprise the steps：
（1）Remove impurity：By solvent and acid gas stream counter current contacting, remove the CO in acid gas stream2And sulfide, must remove respectively
Air-flow after miscellaneous and the solvent of rich sour gas；
（2）Solvent reclamation：The solvent of rich sour gas is reduced pressure, foreign gas therein is overflowed, and obtains regenerated solvent,
Remove impurity will be carried out in regenerated solvent return to step 1.
In described step 2, first the solvent of rich sour gas is carried out flash distillation, the solvent of the rich sour gas after flash distillation is again
Carry out decompression regeneration, obtain regenerated solvent, remove impurity will be carried out in regenerated solvent return to step 1.
In described step 1, the solvent of rich sour gas reclaims energy therein using turbine mode.
The present invention provides a kind of removing CO from acid gas stream2And the solvent of sulfide and its application.The solvent of the present invention
Can be used in removing CO from sour gas2, sulfide (include H2S and organic sulfur), can be used for natural gas, synthesis gas, refinery
The sour gas such as air-liquid liquefied oil gas.By the contact with air-flow for this solvent, remove the CO in acid gas stream2And sulfide.This
The solvent of invention, using serotonin as main absorbent, is aided with sulfolane and the activator of diethylene glycol composition simultaneously, divides it by group
Between mutual coordinated, CO can be effectively improved2With sulfide removal efficiency.By contrast experiment as can be seen that independent adopt
MDEA, or adopt MDEA+ sulfolane, or adopt MDEA+ diethylene glycol, the effect of this three is far away from the solvent of the present invention.
This is due to having preferable synergism between the component of the present invention, by organic cooperation of component, achieves and is significantly better than
The effect of conventional amine method.Contrast experiment in embodiment proves, more conventional amine method is compared, and is had higher using the solvent of the present invention
CO2With sulfide removal efficiency, postprocessing working procedures can be effectively reduced.For chemical field, the minimizing for the treatment of process, meaning
Taste the reduction of production cost, and the minimizing of consumption of raw materials, and this also reduce further the probability of pollutant generation, has
Significantly economic benefit and social benefit.
Meanwhile, the solvent of the present invention is renewable and recycles, and has the advantages that use cost is low, effect on environment is little,
Significant for the processing cost reducing sour gas.The using method of solvent of the present invention is simple, can be connect using adverse current
Tactile mode, that is,：Make the CO in air-flow2It is removed by contacting with solvent of the present invention with sulfide.Absorption process can be adopted
With once absorbing, may also be employed repeatedly being carried out continuously, the latter can use the solvent of multiply to press temperature successively from bottom of towe to tower top
The order reducing carries out gas-to-liquid contact.
CO after solvent and acid gas stream counter current contacting, in acid gas stream2And sulfide is removed, obtain the gas after remove impurity
Body, simultaneously solvent become the solvent of rich sour gas.The solvent liquid of rich sour gas passes through decompression and realizes regeneration, and it can pass through
Choke valve is realizing.The energy containing in rich acid gas solvent can be reclaimed by turbine.Meanwhile, in decompression regeneration
Before, also can adopt one or many flash distillation, remove acid gas.
There is between instant component good synergism, CO2And the removal efficiency of sulfide is significantly higher than conventional amine method,
Postprocessing working procedures can be effectively reduced, significant for the process cycle and processing cost reducing sour gas.
Specific embodiment
All features disclosed in this specification, or disclosed all methods or during step, except mutually exclusive
Feature and/or step beyond, all can combine by any way.
Any feature disclosed in this specification, unless specifically stated otherwise, all can be equivalent or there is similar purpose by other
Alternative features are replaced.I.e., unless specifically stated otherwise, each feature is a series of equivalent or one of similar characteristics example
?.
Embodiment 1
Weigh 44kg MDEA respectively（N methyldiethanol amine）, 5kg sulfolane, 4kg diethylene glycol, 47kg water, mixing is all
Even, obtain final product solvent.
Embodiment 2
（1）Prepare solvent
Weigh 38kgMDEA respectively（N methyldiethanol amine）, 6kg sulfolane, 3kg diethylene glycol, 53kg water, mix homogeneously,
Obtain final product solvent.
（2）Measure
Configuration unstripped gas, contains 5% CO in unstripped gas2, 1% H2S.The unstripped gas preparing enters and absorbs tower bottom, and with
The solution counter current contacting that tower top enters, the acid gas in unstripped gas is absorbed, and purified gas from tower top out, enters gas-liquid and divides
Reclaim from device and be vented after the drop of entrained with.
After measured, in purified gas, CO2Content is 47ppmv, H2S content is 3ppmv, and organic sulfur removal rate is
82.9%.
Embodiment 3
（1）Prepare solvent
Weigh 30kgMDEA, 5kg sulfolane, 5kg diethylene glycol, 55kg water, mix homogeneously respectively, obtain final product solvent.
（2）Measure
Configuration unstripped gas, contains 5% CO in unstripped gas2, 1% H2S.The unstripped gas preparing enters and absorbs tower bottom, and with
The solution counter current contacting that tower top enters, the acid gas in unstripped gas is absorbed, and purified gas from tower top out, enters gas-liquid and divides
Reclaim from device and be vented after the drop of entrained with.
After measured, in purified gas, CO2Content is 50ppmv, H2S content is 3ppmv, and organic sulfur removal rate is
82.6%.
Embodiment 4
（1）Prepare solvent
Weigh 47kgMDEA, 3kg sulfolane, 2kg diethylene glycol, 48kg water, mix homogeneously respectively, obtain final product solvent.
（2）Measure
Configuration unstripped gas, contains 5% CO in unstripped gas2, 1% H2S.The unstripped gas preparing enters and absorbs tower bottom, and with
The solution counter current contacting that tower top enters, the acid gas in unstripped gas is absorbed, and purified gas from tower top out, enters gas-liquid and divides
Reclaim from device and be vented after the drop of entrained with.
After measured, in purified gas, CO2Content is 45ppmv, H2S content is 3ppmv, and organic sulfur removal rate is
83.50%.
Embodiment 5
（1）Prepare solvent
Weigh 55kgMDEA respectively（N methyldiethanol amine）, 3kg sulfolane, 1kg diethylene glycol, 41kg water, mix homogeneously,
Obtain final product solvent.
（2）Measure
Configuration unstripped gas, contains 5% CO in unstripped gas2, 1% H2S.The unstripped gas preparing enters and absorbs tower bottom, and with
The solution counter current contacting that tower top enters, the acid gas in unstripped gas is absorbed, and purified gas from tower top out, enters gas-liquid and divides
Reclaim from device and be vented after the drop of entrained with.
After measured, in purified gas, CO2Content is 44ppmv, H2S content is 3ppmv, and organic sulfur removal rate is
83.10%.
Contrast experiment
Assay device is directly tested to the operating characteristics of concrete absorbent.Test absorption tower internal diameter be
40mm, built-in Φ 25 rustless steel rectangular saddle ring, regenerator internal diameter 50mm, built-in Φ 25 rustless steel rectangular saddle ring, regeneration tower bottom equipped with
Reboiler.
The unstripped gas preparing（5% CO is contained in this unstripped gas2, 1% H2S）Enter and absorb tower bottom, and enter with tower top
Solution counter current contacting, the acid gas in unstripped gas absorbed, and purified gas from tower top out, enters gas-liquid separator and reclaims
It is vented after the drop of entrained with.
The rich acid gas solvent absorbing acid gas leads to regenerator top from absorbing tower bottom, and in regenerator with
The steam counter-flow rising contacts and obtains regeneration.Regenerate the lean solution obtaining and send into the absorption of absorption tower jacking row after cooling.From again
Raw tower top gas out enters regeneration Gas Cooler, the vapor in gas is reclaimed, is vented after regeneration gas is separated.
On the premise of unstripped gas is certain, the operating characteristics of different lyosoption agent is tested, test result such as table 1
Shown.
The operating characteristics of the different lyosoption of table 1
In table 1：MDEA50% refers to the water of MDEA, 50%wt that this solvent contains 50%wt；MDEA47%+ sulfolane 5% refers to
This solvent contains the sulfolane of MDEA, 5%wt of 47%wt and the water of 48%wt；MDEA47%+ diethylene glycol 5% refers to that this solvent contains
The diethylene glycol of MDEA, 5%wt of 47%wt and the water of 48%wt；MDEA44%+ sulfolane 5%+ diethylene glycol 4% is the embodiment of the present invention 1
The solvent of preparation.The determination data of table 1 shows：The solvent of the present invention is to CO2There is significantly higher removal efficiency with sulfide.
The invention is not limited in aforesaid specific embodiment.The present invention expands to and any discloses in this manual
New feature or any new combination, and the arbitrary new method of disclosure or the step of process or any new combination.
Claims (9)
1. one kind removes CO from acid gas stream2And the solvent of sulfide is it is characterised in that this solvent is used for from acid gas stream
Remove CO2And sulfide, including the component of following percentage by weight：
Serotonin 20～60%；
Activator 1～10%；
Water surplus；
Described activator is made up of sulfolane and diethylene glycol；
Described serotonin is N methyldiethanol amine；
In described activator, the weight of sulfolane and diethylene glycol is than for 1：10~10:1.
2. remove CO according to claim 1 from acid gas stream2And the solvent of sulfide is it is characterised in that described serotonin
Percentage by weight be 30～50%.
3. remove CO according to claim 1 from acid gas stream2And the solvent of sulfide is it is characterised in that described N- methyl
The percentage by weight of diethanolamine is 35～45%.
4. remove CO according to any one of claim 1-3 from acid gas stream2And the solvent of sulfide is it is characterised in that go back
Including additive, described additive is one or more of corrosion inhibitor, defoamer, antisludging agent.
5. remove CO according to claim 4 from acid gas stream2And the solvent of sulfide is it is characterised in that include weighing as follows
The component of amount percentage ratio：
Serotonin 20～60%；
Activator 1～10%；
Additive 0.01～5%；
Water surplus.
6. remove CO according to any one of claim 1-5 from acid gas stream2And the application of the solvent of sulfide, its feature
It is, comprise the steps：Solvent and acid gas stream counter current contacting, remove the CO in acid gas stream2And sulfide.
7. remove CO according to any one of claim 1-5 from acid gas stream2And the application of the solvent of sulfide, its feature
It is, comprise the steps：Solvent is divided into multiply, makes solvent carry out multiple counter current contacting with acid gas stream from top to bottom, go
Except the CO in acid gas stream2And sulfide.
8. remove CO according to any one of claim 1-5 from acid gas stream2And the application of the solvent of sulfide, its feature
It is, comprise the steps：
（1）Remove impurity：By solvent and acid gas stream counter current contacting, remove the CO in acid gas stream2And sulfide, after obtaining remove impurity respectively
Air-flow and rich sour gas solvent；
（2）Solvent reclamation：The solvent of rich sour gas is reduced pressure, foreign gas therein is overflowed, and obtains regenerated solvent, will again
Carry out remove impurity in raw solvent return to step 1.
9. remove CO according to claim 8 from acid gas stream2And the application of the solvent of sulfide is it is characterised in that described
In step 2, first the solvent of rich sour gas is carried out flash distillation, the solvent of the rich sour gas after flash distillation carries out reducing pressure again again
Raw, obtain regenerated solvent, remove impurity will be carried out in regenerated solvent return to step 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410333175.4A CN104069716B (en) | 2014-07-14 | 2014-07-14 | Solvent for removing CO2 and sulfides in acidic airflow, and application thereof |
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| CN104069716B true CN104069716B (en) | 2017-02-15 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109420409B (en) * | 2017-08-22 | 2021-08-06 | 中国石油化工股份有限公司 | Selective removal of H-containing compounds from gas streams2S and CO2And method for absorbing acid gas |
| WO2023125006A1 (en) * | 2021-12-27 | 2023-07-06 | 中国石油天然气股份有限公司 | Method and system for removing acid gas from ethylene cracking gas |
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| CN1546207A (en) * | 2003-12-09 | 2004-11-17 | 南化集团研究院 | Method for separating carbon dioxide dissolvent from gas mixture |
| CN1615173A (en) * | 2002-01-14 | 2005-05-11 | 国际壳牌研究有限公司 | Process for removing carbon dioxide from gas mixtures |
| CN101600488A (en) * | 2007-01-19 | 2009-12-09 | 道达尔公司 | Be used for the method that purifying contains the admixture of gas of sour gas |
| CN101822932A (en) * | 2010-06-12 | 2010-09-08 | 中国石油集团工程设计有限责任公司 | Composite decarbonization solvent for eliminating carbon dioxide in natural gases |
| WO2011121633A1 (en) * | 2010-03-29 | 2011-10-06 | 株式会社 東芝 | Acidic gas absorbent, acidic gas removal device, and acidic gas removal method |
| CN102284229A (en) * | 2011-06-02 | 2011-12-21 | 大连理工大学 | Composite decarbonization solution for capturing carbon dioxide in mixed gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100518892C (en) * | 2007-06-07 | 2009-07-29 | 华东理工大学 | Method and device for removing hydrogen sulphide from mixture gas containing low-concentration hydrogen sulphide |
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- 2014-07-14 CN CN201410333175.4A patent/CN104069716B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1615173A (en) * | 2002-01-14 | 2005-05-11 | 国际壳牌研究有限公司 | Process for removing carbon dioxide from gas mixtures |
| CN1546207A (en) * | 2003-12-09 | 2004-11-17 | 南化集团研究院 | Method for separating carbon dioxide dissolvent from gas mixture |
| CN101600488A (en) * | 2007-01-19 | 2009-12-09 | 道达尔公司 | Be used for the method that purifying contains the admixture of gas of sour gas |
| WO2011121633A1 (en) * | 2010-03-29 | 2011-10-06 | 株式会社 東芝 | Acidic gas absorbent, acidic gas removal device, and acidic gas removal method |
| CN101822932A (en) * | 2010-06-12 | 2010-09-08 | 中国石油集团工程设计有限责任公司 | Composite decarbonization solvent for eliminating carbon dioxide in natural gases |
| CN102284229A (en) * | 2011-06-02 | 2011-12-21 | 大连理工大学 | Composite decarbonization solution for capturing carbon dioxide in mixed gas |
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