CN101785954A - Compound solution of membrane absorption CO2 gas - Google Patents

Compound solution of membrane absorption CO2 gas Download PDF

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CN101785954A
CN101785954A CN201010121990A CN201010121990A CN101785954A CN 101785954 A CN101785954 A CN 101785954A CN 201010121990 A CN201010121990 A CN 201010121990A CN 201010121990 A CN201010121990 A CN 201010121990A CN 101785954 A CN101785954 A CN 101785954A
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gas
polyamino
amino alkane
alkane base
ethoxy
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陆建刚
陈敏东
王让会
张慧
方华
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Nanjing University of Information Science and Technology
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Nanjing University of Information Science and Technology
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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
    • 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

Abstract

The invention discloses compound solution of membrane absorption CO2 gas; the compound solution comprises amino alkane sulfonate and polyamino organic alcohol; the total concentration of the two components amino alkane sulfonate and polyamino organic alcohol in aqueous solution is 0.1 to 5.0mol/L, and the molar ratio of amino alkane sulfonate to polyamino organic alcohol is 1:0.5 to 1.5. Compared with the prior art, after the compound solution presented by the invention is used for the membrane absorption CO2, the performance is better than that of the traditional CO2 absorbent, such as MEA (monoethanolamine) and other components, and simultaneously, is better than that of the single amino alkane sulfonate; and the compound solution of membrane absorption CO2 gas has high mass transfer coefficient, and can stably work in a membrane contactor.

Description

A kind of film absorbs CO 2The composite solution of gas
Technical field
The present invention relates to the membrane separation technique field, particularly a kind of film absorbs CO 2The composite solution of gas.
Background technology
Global warming has been subjected to 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 common difficulty and the challenge that the mankind face.Separation that various high-efficiency low energy consumptions are feasible and absorption CO 2Technology is subjected to the great attention of various countries.Various high-performance absorb CO 2The exploitation of solution is one of theme of this area research, and in recent years, composite solution absorbed CO because its particular performances has become film 2The heat subject of the research of solution.
The composite solution compatibility premium properties of single solution, absorb CO at film 2Higher mass transfer force, higher absorptive capacity, higher absorption rate and regeneration rate can be provided in the process.Therefore composite solution has higher premium properties.At present as absorbing CO 2The various composite solutions of gas have obtained extensive use industrial.As US4,892,674 propose to add steric hindrance amine salt or steric hindrance amino acid formation double solvents in pure amine solvent; US4,895,670 disclose sterically hindered amines and the amino acids formed double solvents of steric hindrance.CN1356157A proposes a kind of mixed solvent and is made up of MDEA (N methyldiethanol amine) and a kind of sterically hindered amines.CN1354036A proposes 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 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, solution provides high selectivity and high drive in separation process.Therefore exploitation and membrane material mutually the high-performance solution of compatibility have the meaning of particular importance.CN1895738 discloses the composite solution of being made up of amino-acid salt and activating component, has excellent absorption and regenerability, and is better than one-component.At present, be used for film and absorb CO 2Composite solution 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.
Summary of the invention
The object of the present invention is to provide a kind of film that can stable operation in membrane contactor to absorb CO 2The composite solution of gas.
Technical scheme of the present invention is: a kind of film absorbs CO 2The composite solution of gas is made up of amino alkane base sulfonate and organic pure two components of polyamino.The total concentration of organic pure two components of amino alkane base sulfonate and polyamino in the aqueous solution is 0.1～5.0mol/L, and the mol ratio of amino alkane base sulfonate and the organic alcohol of polyamino is 1.0: 0.5～1.2.
The preferred value of aqueous solution total concentration of organic pure two components of amino alkane base sulfonate and polyamino is 0.5～3.0mol/L.It is 1.0: 0.5～1.0 that the mol ratio of amino alkane base sulfonate and the organic alcohol of polyamino more preferably is worth.
Wherein, the structural formula of amino alkane base sulfonate is:
H 2N-R-SO 3 -M +
R is the alkyl that contains 1～3 carbon atom in the formula, M +=K +Or Na +Be preferably NSC 209983 salt, 2-taurate, 1-taurate, 1-aminopropanesulfonic acid salt, 2-aminopropanesulfonic acid salt, any one in the 3-aminopropanesulfonic acid salt.
The structural formula of polyamino organic alcohol compound is:
Figure GSA00000046480100031
The n value is 0～5 in the formula, is preferably: monoethanolamine, N-(2-ethoxy) ethylenediamine, N-(2-ethoxy) diethylenetriamine, N-(2-ethoxy) triethylene tetramine, N-(2-ethoxy) TEPA.
Beneficial effect:
The composite solution that the present invention proposes absorbs CO 2Performance is better than existing C O 2Absorbent such as MEA components such as (monoethanolamines) is better than single amino alkane base sulfonate simultaneously; Have high mass tranfer coefficient, can stable operation in membrane contactor.
Four, description of drawings
Fig. 1 film absorbs CO 2The composite solution 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 film absorbs CO 2The composite solution of gas the absorbent properties evaluation result-the composite solution ratio of component.
Wherein: zero MEA,
Figure GSA00000046480100032
NSC 209983 salt, the ■ taurate,
Figure GSA00000046480100033
Taurate+N-(2-ethoxy) TEPA, Taurate+N-(2-ethoxy) triethylene tetramine,
● NSC 209983 salt+N-(2-ethoxy) diethylenetriamine, ▲ taurate+N-(2-ethoxy) ethylenediamine, the composite solution total concentration is 1mol/L, the mol ratio of amino alkane base sulfonate and the organic alcohol of polyamino is 1: 0.7.
Fig. 3 film absorbs CO 2Absorbent properties evaluation result-the total concentration of solutes of the composite solution of gas and the influence of solute mol ratio.
Among the figure when the mol ratio of amino alkane base sulfonate and the organic alcohol of polyamino is 1: 0.5, curve is ▲ NSC 209983 salt+N-(2-ethoxy) diethylenetriamine, ● taurate+N-(2-ethoxy) triethylene tetramine, ■ aminopropanesulfonic acid salt+N-(2-ethoxy) TEPA; When the mol ratio of amino alkane base sulfonate and the organic alcohol of polyamino was 1: 1, curve was
Figure GSA00000046480100041
Aminopropanesulfonic acid salt+N-(2-ethoxy) TEPA,
Figure GSA00000046480100042
Taurate+N-(2-ethoxy) triethylene tetramine,
Figure GSA00000046480100043
NSC 209983 salt+N-(2-ethoxy) diethylenetriamine.
The specific embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.
As shown in Figure 1, film of the present invention absorbs CO 2The absorbent properties of the composite solution of gas are estimated flow process: 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 enters in the membrane contactor 3 through gas flowmeter 2, CO in the gaseous mixture 2Diffuse to the film opposite side by fenestra, absorbed by composite solution, enter liquid phase, the gas phase after the absorption is emitted from membrane contactor 3 other end gas vents.Composite solution in first solution storage trough 4 is extracted out by wriggling measuring pump 5 and is sent in the membrane contactor 3, absorbs the CO that diffusion is come 2After leave membrane contactor 3 solution enter 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:
K G a = G ln ( C g , in / C g , out ) AL
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.
Embodiment 1
A kind of film absorbs the composite solution of CO2 gas, is made up of amino alkane base sulfonate and organic pure two components of polyamino.The total concentration of organic pure two components of amino alkane base sulfonate and polyamino in the aqueous solution is 0.5mol/L, and the mol ratio of amino alkane base sulfonate and the organic alcohol of polyamino is 1.0: 0.7.Shown in the concrete table composed as follows:
Figure GSA00000046480100051
Embodiment 2
A kind of film absorbs CO 2The composite solution of gas is made up of amino alkane base sulfonate and organic pure two components of polyamino.The total concentration of organic pure two components of amino alkane base sulfonate and polyamino in the aqueous solution is 3mol/L, and the mol ratio of amino alkane base sulfonate and the organic alcohol of polyamino is 1.0: 1.2.Shown in the concrete table composed as follows:
Figure GSA00000046480100052
Base) ethylenediamine ? ? ? ? ? ?
N-(2-ethoxy) diethylenetriamine ??0.298 ??0.313 ??0.300 ??0.332 ??0.343 ??0.338
N-(2-ethoxy) triethylene tetramine ??0.326 ??0.356 ??0.349 ??0.351 ??0.361 ??0.355
N-(2-ethoxy) TEPA ??0.366 ??0.381 ??0.375 ??0.378 ??0.385 ??0.379
Embodiment 3
A kind of film absorbs CO 2The composite solution of gas is made up of amino alkane base sulfonate and organic pure two components of polyamino.The total concentration of organic pure two components of amino alkane base sulfonate and polyamino in the aqueous solution is 5mol/L, and the mol ratio of amino alkane base sulfonate and the organic alcohol of polyamino is 1.0: 0.5.Shown in the concrete table composed as follows:
Base) TEPA ? ? ? ? ? ?
Composite solution of the present invention as can be seen from the above embodiments has high mass tranfer coefficient.
Absorbent properties by the various composite solutions of Fig. 2 compare, also can find out the cumulative volume mass tranfer coefficient of the cumulative volume mass tranfer coefficient of various composite solutions far above one-component solution (as MEA, NSC 209983 salt and taurate), the cumulative volume mass tranfer coefficient of composite solution is 1.5～2.5 times of one-component solution, show simultaneously, increase along with amino group in the polyamino organic alcohol compound, the cumulative volume mass tranfer coefficient increases, to CO 2Absorb better.Fig. 3 be composite solution total concentration and mol ratio to capturing the performance impact evaluation result, selected three kinds of representative components: aminopropanesulfonic acid salt+N-(2-ethoxy) TEPA, taurate+N-(2-ethoxy) triethylene tetramine and NSC 209983 salt+N-(2-ethoxy) diethylenetriamine.Among the figure when the mol ratio of amino alkane base sulfonate and the organic alcohol of polyamino is 1: 0.5, curve is ▲ NSC 209983 salt+N-(2-ethoxy) diethylenetriamine, ● taurate+N-(2-ethoxy) triethylene tetramine, ■ aminopropanesulfonic acid salt+N-(2-ethoxy) TEPA; When the mol ratio of amino alkane base sulfonate and the organic alcohol of polyamino was 1: 1, curve was
Figure GSA00000046480100071
Aminopropanesulfonic acid salt+N-(2-ethoxy) TEPA,
Figure GSA00000046480100072
Taurate+N-(2-ethoxy) triethylene tetramine,
Figure GSA00000046480100073
NSC 209983 salt+N-(2-ethoxy) diethylenetriamine.The result shows that the cumulative volume mass tranfer coefficient increased when total concentration increased, and the organic alcohol of polyamino is when molar ratio increases in composite solution, and the cumulative volume mass tranfer coefficient increases, and effect is also just better.

Claims (6)

1. a film absorbs CO 2The composite solution of gas is characterized in that, is made up of amino alkane base sulfonate and the organic alcohol of polyamino;
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 +,
The structural formula of polyamino organic alcohol compound is:
Figure FSA00000046470000011
Wherein the n value is 0～5.
2. film according to claim 1 absorbs CO 2The composite solution of gas is characterized in that, the total concentration of organic pure two components of amino alkane base sulfonate and polyamino in the aqueous solution is 0.1～5.0mol/L, and wherein, the mol ratio of amino alkane base sulfonate and the organic alcohol of polyamino is 1: 0.5～1.2.
3. film according to claim 2 absorbs CO 2The composite solution of gas is characterized in that, the total concentration of organic pure two components of amino alkane base sulfonate and polyamino in the aqueous solution is 0.5～3.0mol/L.
4. film according to claim 2 absorbs CO 2The composite solution of gas is characterized in that, the mol ratio of amino alkane base sulfonate and the organic alcohol of polyamino is 1: 0.5～1.
5. absorb CO according to the arbitrary described film of claim 1～4 2The composite solution of gas is characterized in that, described amino alkane base sulfonate is: NSC 209983 salt, 2-taurate, 1-taurate, 1-aminopropanesulfonic acid salt, 2-aminopropanesulfonic acid salt, any one in the 3-aminopropanesulfonic acid salt.
6. film according to claim 5 absorbs CO 2The composite solution of gas is characterized in that, described polyamino organic alcohol compound is: monoethanolamine, N-(2-ethoxy) ethylenediamine, N-(2-ethoxy) diethylenetriamine, N-(2-ethoxy) triethylene tetramine, N-(2-ethoxy) TEPA.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2658645A4 (en) * 2010-12-30 2015-06-24 Chevron Usa Inc Aqueous solutions of amine functionalized ionic compounds for carbon capture processes
EP2658633A4 (en) * 2010-12-30 2015-06-24 Chevron Usa Inc Process for the separation of carbon dioxide from flue gas
TWI619540B (en) * 2017-02-18 2018-04-01 國立清華大學 Carbon dioxide absorber composition and method for capturing carbon dioxide
CN113426249A (en) * 2021-07-19 2021-09-24 重庆大学 Novel mixed organic amine CO2Absorbent agent

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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

Patent Citations (2)

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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

Non-Patent Citations (1)

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Title
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2658645A4 (en) * 2010-12-30 2015-06-24 Chevron Usa Inc Aqueous solutions of amine functionalized ionic compounds for carbon capture processes
EP2658633A4 (en) * 2010-12-30 2015-06-24 Chevron Usa Inc Process for the separation of carbon dioxide from flue gas
US9180403B2 (en) 2010-12-30 2015-11-10 Chevron U.S.A. Inc. Aqueous solutions of amine functionalized ionic compounds for carbon capture processes
US9751044B2 (en) 2010-12-30 2017-09-05 Chevron U.S.A. Inc. Aqueous solutions of amine functionalized ionic compounds for carbon capture processes
US9901863B2 (en) 2010-12-30 2018-02-27 Chevron U.S.A. Inc. Process for the separation of carbon dioxide from flue gas
TWI619540B (en) * 2017-02-18 2018-04-01 國立清華大學 Carbon dioxide absorber composition and method for capturing carbon dioxide
US10549260B2 (en) 2017-02-18 2020-02-04 National Tsing Hua University Carbon dioxide absorbent composition and method for capturing carbon dioxide
CN113426249A (en) * 2021-07-19 2021-09-24 重庆大学 Novel mixed organic amine CO2Absorbent agent

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Application publication date: 20100728