CN101766947B - Composite absorber for catching CO2 gas of membrane contactor - Google Patents
Composite absorber for catching CO2 gas of membrane contactor Download PDFInfo
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- CN101766947B CN101766947B CN2010101219802A CN201010121980A CN101766947B CN 101766947 B CN101766947 B CN 101766947B CN 2010101219802 A CN2010101219802 A CN 2010101219802A CN 201010121980 A CN201010121980 A CN 201010121980A CN 101766947 B CN101766947 B CN 101766947B
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- Prior art keywords
- composite absorber
- gas
- organic amine
- amino alkane
- membrane contactor
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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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- 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
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- Gas Separation By Absorption (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a composite absorber for catching CO2 gas of a membrane contactor; the composite absorber is composed of amino alkane sulfonate and poliamide organic amine; the total concentration of the amino alkane sulfonate and poliamide organic amine in the composite absorber is 0.1-4.0mol/L, and the mole ratio of the amino alkane sulfonate and the poliamide organic amine is 1:0.5-1.2. Compared with the prior art, the performance of the composite absorber for catching CO2 gas is superior to that of the existing CO2 absorber such as MEA (monoethanolamine) and other components, and is better than that of the single amino alkane sulfonate; the composite absorber has high mass transfer coefficient and can be operated stably in the membrane contactor.
Description
Technical field
The present invention relates to the membrane separation technique field, particularly a kind ofly be used to capture CO
2The composite absorber of gas.
Background technology
Global warming has received showing great attention to of the whole world, and carbon dioxide is generally believed it is one of major reason that causes global warming because of having greenhouse effects.Reducing CO2 emission, realize low-carbon economy, reduce atmospheric carbon dioxide levels, is the common difficulty and the challenge of face of mankind.Separation that various high-efficiency low energy consumptions are feasible and capture CO
2Technology receives the great attention of various countries.Various high-performance capture CO
2The exploitation of absorbent is one of theme of this area research, and in recent years, composite absorber captured CO because its particular performances has become
2The heat subject of the research and development of absorbent.
Composite absorber the is compatible premium properties of single absorbent is capturing CO
2Higher mass transfer force, higher absorptive capacity, higher absorption rate and regeneration rate can be provided in the process.Therefore composite absorber has higher premium properties.Be used to absorb CO at present
2The various absorbents of gas have obtained extensive use in industry.Like US4,892,674 propose in pure amine solvent, to add steric hindrance amine salt or steric hindrance amino acid formation double solvents; US4, the sterically hindered amines and the amino acids formed double solvents of steric hindrance of 895,670 propositions.CN1356157A proposes a kind of mixed solvent and is made up of MDEA (N methyldiethanol amine) and a kind of sterically hindered amines.CN1354036A discloses a kind of compound amine solvent and is made up of MEA (monoethanolamine) and a kind of reactive amines.The double solvents that these patents relate to is mainly used in the sour gas H in the selectively removing gaseous mixture
2S and CO
2
Film gas absorption techniques (being called for short film absorbs) is separated the new gas separation process that combines with solvent absorption gas technology as film; It has stable mass transfer interface, high-specific surface area, high mass transfer efficiency; Advantages such as energy consumption is low, and device volume is little, and stable operation and elasticity are big; Microporous barrier in the membrane contactor only is the barrier between the gas-liquid two-phase, and to the separation non-selectivity of gas, absorbent provides high selectivity and high drive in separation process.Therefore develop the meaning that has particular importance with the compatible mutually high-performance absorbent of membrane material.CN1895738 discloses the composite solution of being made up of amino-acid salt and activating component, has excellent absorption and regenerability, and is superior to one-component.At present, be used for membrane contactor to trap CO
2Composite absorber is less, and absorbent properties are still needed and will further be improved, and exists solvent be difficult for to obtain, and costs an arm and a leg, and regenerated heat is higher, and shortcoming such as nip membrane material.
Three, summary of the invention
The object of the present invention is to provide a kind of can be in membrane contactor stable operation be used for membrane contactor to trap CO
2The efficient composite absorber of gas.
Technical scheme of the present invention is: a kind of membrane contactor to trap CO that is used for
2The composite absorber of gas is made up of amino alkane base sulfonate and polyamino organic amine two components.Amino alkane base sulfonate and the total concentration of polyamino organic amine two components in composite absorber are 0.1～4.0mol/L, and the mol ratio of amino alkane base sulfonate and polyamino organic amine is 1.0: 0.1～1.2.
The preferred value of composite absorber total concentration of amino alkane base sulfonate and polyamino organic amine two components is 0.5～3.0mol/L.It is 1.0: 0.5～1.0 that the mol ratio of amino alkane base sulfonate and polyamino organic amine more preferably is worth.
Wherein, the structural formula of amino alkane base sulfonate is:
H
2N-R-SO
3 -M
+
Wherein R is the alkyl that contains 1～3 carbon atom, M
+=K
+Or Na
+Be preferably NSC 209983 salt, 2-taurate, 1-taurate, 1-aminopropanesulfonic acid salt, 2-aminopropanesulfonic acid salt, 3-aminopropanesulfonic acid salt.
The structural formula of polyamino organic amine compound is:
Wherein the n value is 0-5, is preferably: ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA.
Beneficial effect:
The composite absorber that the present invention proposes captures CO
2Performance is superior to existing C O
2Absorbent such as MEA components such as (monoethanolamines) is superior to single amino alkane base sulfonate simultaneously; Have high mass tranfer coefficient, can stable operation in membrane contactor.
Four, description of drawings
Fig. 1 membrane contactor to trap CO
2The composite absorber absorbent properties evaluating apparatus of gas.1-gaseous mixture steel cylinder, 2-gas flowmeter, 3-membrane contactor, 4-first solution storage trough, the 5-measuring pump of wriggling, 6-second solution storage trough, P-pressure gauge, A-sample point.
Fig. 2 membrane contactor to trap CO
2The composite absorber of gas the absorbent properties evaluation result-the composite absorber ratio of component.
Wherein: ● MEA;
NSC 209983 salt; The ■ taurate; ◆ taurate+TEPA;
taurate+triethylene tetramine;
NSC 209983 salt+diethylenetriamine; ▲ taurate+ethylenediamine; The composite absorber total concentration is 1mol/L, and the mol ratio of amino alkane base sulfonate and polyamino organic amine is 1: 0.6.
Fig. 3 membrane contactor to trap CO
2Absorbent properties evaluation result-the total concentration of solutes of the composite absorber of gas and the influence of solute mol ratio.
When the mol ratio of amino alkane base sulfonate and polyamino organic amine was 1: 0.5, curve was ▲ aminopropanesulfonic acid salt+diethylenetriamine among the figure, ● NSC 209983 salt+triethylene tetramine, ■ taurate+TEPA; When the mol ratio of amino alkane base sulfonate and polyamino organic amine is 1: 1; Curve is
taurate+TEPA;
NSC 209983 salt+triethylene tetramine,
aminopropanesulfonic acid salt+diethylenetriamine.
Five, the specific embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.
As shown in Figure 1, the present invention is used for membrane contactor to trap CO
2The capture performance evaluation flow process of the composite absorber of gas is: under the room temperature, contain the CO of 10% (percentage by volume)
2Gaseous mixture is decompressed to the operating pressure of 0.105～0.11MPa by mixing steel cylinder 1 through pressure-reducing valve, and air-flow gets in the membrane contactors 3 through gas flowmeter 2, CO in the gaseous mixture
2Diffuse to the film opposite side through fenestra, captured by composite absorber, get into liquid phase, the gas phase after the absorption is emitted from membrane contactor 3 other end gas vents.Composite absorber in first solution storage trough 4 is extracted out by wriggling measuring pump 5 and is sent in the membrane contactor 3, captures the CO that diffusion is come
2After leave membrane contactor 3 solution get into second solution storage trough 6.Gas phase is imported and exported to be made up of gas analyzer and is measured, and the solution total alkali is measured by acid base titration, liquid phase CO
2The employing chemical analysis is measured.
Evaluation criterion: cumulative volume mass tranfer coefficient K
GA:
G, A and L are respectively gaseous phase volume flow velocity, membrane module cross-sectional area and membrane module length, C in the formula
G, inAnd C
G, outBe respectively gas phase and import and export CO
2Concentration.
A kind of membrane contactor to trap CO that is used for
2The composite absorber of gas is made up of amino alkane base sulfonate and polyamino organic amine two components.Amino alkane base sulfonate and the total concentration of polyamino organic amine two components in composite absorber are 0.5mol/L, and the mol ratio of amino alkane base sulfonate and polyamino organic amine is 1.0: 0.6.The concrete composition as above shown in the table.
A kind of membrane contactor to trap CO that is used for
2The composite absorber of gas is made up of amino alkane base sulfonate and polyamino organic amine two components.Amino alkane base sulfonate and the total concentration of polyamino organic amine two components in composite absorber are 2mol/L, and the mol ratio of amino alkane base sulfonate and polyamino organic amine is 1.0: 1.2.Concrete composition is as shown in the table:
A kind of membrane contactor to trap CO that is used for
2The composite absorber of gas is made up of amino alkane base sulfonate and polyamino organic amine two components.Amino alkane base sulfonate and the total concentration of polyamino organic amine two components in composite absorber are 4mol/L, and the mol ratio of amino alkane base sulfonate and polyamino organic amine is 1.0: 0.5.Concrete composition is as shown in the table:
Can find out obviously that by embodiment composite solution of the present invention has assimilation effect preferably to carbon dioxide.
Fig. 2 is that the absorbent properties of various composite absorbers compare; The cumulative volume mass tranfer coefficient of various composite absorbers is far above the cumulative volume mass tranfer coefficient of one-component absorbent (like MEA, NSC 209983 salt and taurate); The cumulative volume mass tranfer coefficient of composite absorber is 1.25～2.3 times of one-component absorbent, shows simultaneously, along with the increase of amino group in the polyamino organic amine compound; The cumulative volume mass tranfer coefficient increases, and composite absorber of the present invention is one type of good CO
2Absorbent.Fig. 3 has selected three kinds of representative components: taurate+TEPA, amino first and second sulfonate+triethylene tetramine and aminopropanesulfonic acid salt+diethylenetriamine for composite absorber total concentration and mol ratio concentration influence evaluation result to absorbent properties.When the mol ratio of amino alkane base sulfonate and polyamino organic amine was 1: 0.5, curve was ▲ aminopropanesulfonic acid salt+diethylenetriamine among the figure, ● NSC 209983 salt+triethylene tetramine, ■ taurate+TEPA; When the mol ratio of amino alkane base sulfonate and polyamino organic amine was 1: 1, curve was taurate+TEPA, NSC 209983 salt+triethylene tetramine, aminopropanesulfonic acid salt+diethylenetriamine.The result shows that the cumulative volume mass tranfer coefficient increased when total concentration increased, and the polyamino organic amine is when molar ratio increases in composite absorber, and the cumulative volume mass tranfer coefficient increases, and composite absorber of the present invention has high mass tranfer coefficient.
Claims (4)
1. one kind is used for membrane contactor to trap CO
2The composite absorber of gas is characterized in that, solute is made up of amino alkane base sulfonate and polyamino organic amine;
Described amino alkane base sulfonate is: NSC 209983 salt, 2-taurate, 1-taurate, 1-aminopropanesulfonic acid salt, 2-aminopropanesulfonic acid salt, the sylvite or the sodium salt of any one in the 3-aminopropanesulfonic acid salt;
Described polyamino organic amine compound is: ethylenediamine, diethylenetriamine, triethylene tetramine, any one in the TEPA.
2. the membrane contactor to trap CO that is used for according to claim 1
2The composite absorber of gas; It is characterized in that; Amino alkane base sulfonate and the total concentration of polyamino organic amine two components in composite absorber are 0.1～4.0mol/L, and wherein, the mol ratio of amino alkane base sulfonate and polyamino organic amine is 1: 0.1～1.2.
3. the membrane contactor to trap CO that is used for according to claim 2
2The composite absorber of gas is characterized in that, amino alkane base sulfonate and the total concentration of polyamino organic amine two components in composite absorber are 0.5～3.0mol/L.
4. the membrane contactor to trap CO that is used for according to claim 2
2The composite absorber of gas is characterized in that, the mol ratio of amino alkane base sulfonate and polyamino organic amine is 1: 0.5～1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101219802A CN101766947B (en) | 2010-03-11 | 2010-03-11 | Composite absorber for catching CO2 gas of membrane contactor |
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|---|---|---|---|
| CN2010101219802A CN101766947B (en) | 2010-03-11 | 2010-03-11 | Composite absorber for catching CO2 gas of membrane contactor |
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| CN101766947A CN101766947A (en) | 2010-07-07 |
| CN101766947B true CN101766947B (en) | 2012-09-26 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102284227A (en) * | 2011-08-11 | 2011-12-21 | 大连理工大学 | Method for capturing carbon dioxide in mixed gas by using composite decarbonizing solution |
| CN105510530B (en) * | 2015-12-08 | 2018-05-18 | 湖南大学 | The assay method of the overall mass transfer coefficient of carbon dioxide in a kind of alkanolamine solution |
| JP6460974B2 (en) * | 2015-12-22 | 2019-01-30 | 株式会社神戸製鋼所 | Absorbent, method for producing the same, and method for separating and recovering carbon dioxide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1895738A (en) * | 2005-07-12 | 2007-01-17 | 南京理工大学 | Composite solution for membrane contactor to absorb acid gas |
| CN101263216A (en) * | 2005-08-09 | 2008-09-10 | 埃克森美孚研究工程公司 | Absorbent composition containing molecules with a hindered amine and a metal sulfonate, phosphonate or carboxylate structure for acid gas scrubbing process |
| CN101472663A (en) * | 2006-05-18 | 2009-07-01 | 巴斯夫欧洲公司 | Removal of acid gases from a fluid flow by means of reduced coabsorption of hydrocarbons and oxygen |
| CN101657247A (en) * | 2006-12-28 | 2010-02-24 | 康世富技术公司 | Process for the recovery of carbon dioxide from a gas stream |
-
2010
- 2010-03-11 CN CN2010101219802A patent/CN101766947B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1895738A (en) * | 2005-07-12 | 2007-01-17 | 南京理工大学 | Composite solution for membrane contactor to absorb acid gas |
| CN101263216A (en) * | 2005-08-09 | 2008-09-10 | 埃克森美孚研究工程公司 | Absorbent composition containing molecules with a hindered amine and a metal sulfonate, phosphonate or carboxylate structure for acid gas scrubbing process |
| CN101472663A (en) * | 2006-05-18 | 2009-07-01 | 巴斯夫欧洲公司 | Removal of acid gases from a fluid flow by means of reduced coabsorption of hydrocarbons and oxygen |
| CN101657247A (en) * | 2006-12-28 | 2010-02-24 | 康世富技术公司 | Process for the recovery of carbon dioxide from a gas stream |
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