CN104524928A - Absorbent for collecting carbon dioxide - Google Patents
Absorbent for collecting carbon dioxide Download PDFInfo
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- CN104524928A CN104524928A CN201410852922.5A CN201410852922A CN104524928A CN 104524928 A CN104524928 A CN 104524928A CN 201410852922 A CN201410852922 A CN 201410852922A CN 104524928 A CN104524928 A CN 104524928A
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- Prior art keywords
- carbon dioxide
- absorbent
- piperazine
- ethoxy
- amino
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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
Abstract
The invention provides an absorbent for collecting carbon dioxide. The absorbent for collecting carbon dioxide is characterized by comprising a solution containing 1-amidogen-4-(2-ethoxy)-piperazine or a -amidogen-4-(2-ethoxy)-piperazine solution. The absorbent for collecting carbon dioxide has the advantages that the rate of absorption and the absorption capacity are high, and energy consumption for absorption release is low.
Description
Technical field
The invention belongs to gas separation technique field, be specifically related to a kind of from containing the absorbent reclaiming carbon dioxide the admixture of gas of carbon dioxide.
Background technology
Carbon dioxide is a kind of greenhouse gases.Along with countries in the world are to the concern of global greenhouse effect, the discharge of carbon dioxide causes global attention.The known technology removing carbon dioxide from mist has chemical absorbing technology, Physical Absorption technology, membrane separation technique, adsorption separation technology and cold separation technology.
The common method of chemical absorption method removing carbon dioxide.Chemical absorption method in early days for separating of carbon dioxide is hot potash method and hydramine method.But because the hot potassium carbonate absorption rate of one-component is comparatively slow, those skilled in the art have developed the hot potash method of improvement, as patent (CN85103423) adopts the hot potassium carbonate technology of diethanol amine and amion acetic acid activation; The hot potassium carbonate technology that patent (CN90109635.0) adopts vanadate to improve; The hot potassium carbonate technology that patent (CN200480011471.7) adopts piperazine to activate.The absorption rate of hot potassium carbonate technology and the absorptive capacity of activation or improvement are all enhanced, and are widely used in the purification process as synthesis gas and natural gas under condition of high voltage.The amine that hydramine absorbent mainly adopts comprises primary amine, secondary amine, tertiary amine, sterically hindered amines and polyamine.Primary amine has and carbon dioxide reaction speed feature quickly, but absorptive capacity is lower; The reaction rate of secondary amine and carbon dioxide is taken second place, and absorptive capacity is the same with primary amine; The reaction rate of tertiary amine and carbon dioxide is the slowest, but its absorptive capacity is the twice of primary amine; Sterically hindered amines is also a kind of primary amine, but due to the existence of space steric effect, makes the reaction rate of itself and carbon dioxide lower than primary amine; Polyamine then has the character of the amino that it comprises simultaneously according to the amino comprised in its structure.
Hydramine and carbon dioxide reaction have two kinds of reaction mechanisms.During reaction for tertiary amine and carbon dioxide, carbon dioxide hydrolyses forms carbonic acid:
Carbonic acid and then be dissociated into hydrogen ion and bicarbonate radical:
Bicarbonate radical can be dissociated into another hydrogen ion and carbonate further:
Hydrogen ion carries out acid-base reaction with tertiary amine subsequently:
Overall reaction is:
The hydrolysis (formula (1)) of carbon dioxide is long response time, and the acid-base reaction (formula (4)) of remaining reaction, particularly hydrogen ion and tertiary amine molecule is instantaneous.
When carbon dioxide and primary amine or secondary amine react, first carbon dioxide reacts with a primary amine or a secondary amine molecule and forms carbamic acid intermediate:
This carbamic acid intermediate reacts with second amine molecule subsequently and forms amine salt:
Overall reaction is:
Primary amine or secondary amine can generate stable carbaminate with carbon dioxide fast reaction, and the partial hydrolysis of this carbaminate experience forms bicarbonate radical and unhindered amina and hydrogen ion:
MEA is a kind of primary amine, is proved to be the possible technique being separated low fractional pressure carbon dioxide.But the energy that the process need consumption of MEA process absorbing carbon dioxide is a large amount of regenerates rich solution to recycle, and the absorptive capacity of MEA is lower.The reason causing regeneration lot of energy is that MEA and carbon dioxide generate stable carbaminate, and this stable carbaminate needs a large amount of heats to be decomposed.When rich solution being heated to higher temperature, except needing to consume except a large amount of energy, also can causing the decomposition of MEA itself, causing the main component of absorbent to be lost.In order to reduce energy needed for regeneration and improve absorptive capacity, those skilled in the art of the present technique open and have employed following way:
(1) mixed amine of fast response rate amines and long response time rate amines is adopted, the fast response rate amines (MEA) proposed as patent (CN00118089.4) and the mixed amine absorbent of long response time rate amines (DEA/MDEA); The monoethanolamine (MEA) that patent (CN01134103.3) proposes and the mixed amine absorbent of sterically hindered amines (AMP);
(2) sterically hindered amines is adopted, as the mixed amine absorbent being dominant absorption component with sterically hindered amines 2-amino-2-methyl-1-propanol (AMP) that patent (CN94112801.6) proposes, AMP is a kind of sterically hindered amines, is also a kind of primary amine simultaneously;
(3) adopt activation tertiary amine, as patent (CN201010161302.9) propose with tertiary amine (MDEA) for dominant absorption component, the mixed amine absorbent being activator with N-hydroxyethyl morpholine, AMP, PZ;
(4) adopt polyamine, as the mixed amine absorbent being dominant absorption component with AEEA (AEEA) that patent (CN200710011329.8) proposes, AEEA has the character of primary amine and secondary amine simultaneously.
Although above technology reduces desorb energy consumption to a certain extent, but owing to adding the amine slow with carbon dioxide reaction speed in the amine fast with carbon dioxide reaction speed, or to adopt and the slow amine of carbon dioxide reaction is dominant absorption component, reduce the absorption rate of absorbent and carbon dioxide, and sterically hindered amines is easily degraded.
On the other hand, in the composition of gas, O is comprised
2, SO
x, NO
xtime, hydramine absorbent will react with it, causes the consumption of hydramine, and the product of generation has corrosivity, and not by thermal regeneration.Therefore, usually can need to remove in the absorbent of carbon dioxide in hydramine method to add the additives such as antioxidant, anticorrosive and defoamer.
Summary of the invention
The object of this invention is to provide a kind of New Absorbent of capturing carbon dioxide, to solve the not high technical problem of the absorption appearance that is high and absorbent of energy consumption when carbon dioxide removed by existing absorbent from gaseous mixture.
In order to solve the problem, the invention provides a kind of absorbent of capturing carbon dioxide, it is characterized in that, comprise the solution of 1-amino-4-(2-ethoxy)-piperazine or 1-amino-4-(2-ethoxy)-piperazine.
The structure of described 1-amino-4-(2-ethoxy)-piperazine is as follows:
Preferably, the solvent of the solution of described 1-amino-4-(2-ethoxy)-piperazine is any one or a few the mixture in water and organic solvent.
Preferably, in the solution of described 1-amino-4-(2-ethoxy)-piperazine, the mass percent of 1-amino-4-(2-ethoxy)-piperazine is 10% ~ 70%.
Preferably, in the solution of described 1-amino-4-(2-ethoxy)-piperazine, the mass percent of 1-amino-4-(2-ethoxy)-piperazine is 20% ~ 50%.
Preferably, the absorbent of described capturing carbon dioxide also comprises the compound that at least one has the function regulating absorption rate and absorptive capacity.
More preferably, the described compound with the function of adjustment absorption rate and absorptive capacity is any one or a few the mixture in N methyldiethanol amine (MDEA), 2-amino-2-methyl-1-1 propyl alcohol (AMP), AEEA (AEE), N-methyl-N-(-2-ethoxy)-1,3-propane diamine, triethanolamine (TEA), diethanol amine (DEA), monoethanolamine (MEA), piperazine (PZ) and N-hydroxyethyl piperazine.
More preferably, described 1-amino-4-(2-ethoxy)-piperazine is 100: 0 ~ 100 with the weight ratio of the compound with the function regulating absorption rate and absorptive capacity.
Compared with prior art, the invention has the beneficial effects as follows:
The absorbent of capturing carbon dioxide of the present invention has absorption rate quickly and higher absorptive capacity, and separates that to absorb energy consumption lower.
Accompanying drawing explanation
Fig. 1 is boiler flue carbon dioxide recovery pilot-plant flow chart.
In figure, 1 is absorption tower, and 2 is rich solution pump, and 3 is lean/rich liquid heat exchanger, and 4 is desorber, and 5 is lean pump, and 6 is the first cooler, and 7 is reboiler, and 8 is the second cooler, and 9 is gas-liquid separator
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
1-amino-4-(2-ethoxy)-piperazine of the present invention is commercially available prod.
Embodiment 1
Present embodiment discloses the absorbent of seven kinds of capturing carbon dioxides, all be made up of the aqueous solution of 1-amino-4-(2-ethoxy)-piperazine, the mass concentration of described 1-amino-4-(2-ethoxy)-piperazine is respectively 10%, 20%, 25%, 30%, 40%, 50% and 70%.
In the glass reactor being placed in water bath with thermostatic control (40 DEG C), add the absorbent of seven kinds of above-mentioned capturing carbon dioxides respectively, pass into volume at ambient pressure and consist of 14%CO
2, 86%N
2mist, this absorbing liquid stirs under the constant temperature of 40 DEG C simultaneously.Adopt CO in gas phase look instrument (Agilent 7890B) analysis reactor exit gas
2concentration, as the CO of its concentration and import
2when concentration is equal, absorbent just reaches saturated uptake.Then, stop air inlet, simultaneously by the temperature constant of water-bath at 96 DEG C, continuing magnetic force stirs, and adopts chromatographic tail gas CO
2concentration, when its concentration is zero, absorbent just desorb is complete.Absorption and desorption result is as shown in the table:
| Mass concentration | Soak time (min) | Absorptive capacity (mol CO 2/ mol amine) | Desorption time (min) | Desorption efficiency |
| 10％ | 50 | 1.33 | 18 | 75.5 |
| 20％ | 50 | 1.33 | 18 | 75.5 |
| 25％ | 50 | 1.33 | 18 | 75.5 |
| 30％ | 50 | 1.33 | 18 | 75.5 |
| 40％ | 50 | 1.31 | 18 | 71.1 |
| 50％ | 50 | 1.25 | 18 | 67.2 |
| 70％ | 50 | 1.03 | 18 | 65.5 |
Embodiment 2
Present embodiment discloses the absorbent of eight kinds of capturing carbon dioxides, form by 1-amino-4-(2-ethoxy)-piperazine and the compound with the function regulating absorption rate and absorptive capacity.Wherein, what the absorbent of eight kinds of above-mentioned capturing carbon dioxides adopted have regulates compound and 1-amino-4-(2-the ethoxy)-piperazine of absorption rate and the function of absorptive capacity and has and regulate the weight ratio of the compound of the function of absorption rate and absorptive capacity as shown in the table:
Its preparation method is all: 1-amino-4-(2-ethoxy)-piperazine is made with the compound with the function regulating absorption rate and absorptive capacity is water-soluble the aqueous solution that total mass concentration is 30%.
In the glass reactor being placed in water bath with thermostatic control (40 DEG C), add the absorbent of above-mentioned eight kinds of capturing carbon dioxides respectively, pass into volume at ambient pressure and consist of 14%CO
2, 86%N
2mist, this absorbing liquid stirs under the constant temperature of 40 DEG C simultaneously.Adopt CO in gas phase look instrument (Agilent 7890B) analysis reactor exit gas
2concentration, as the CO of its concentration and import
2when concentration is equal, absorbent just reaches saturated uptake.Then, stop air inlet, simultaneously by the temperature constant of water-bath at 96 DEG C, continuing magnetic force stirs, and adopts chromatographic tail gas CO
2concentration, when its concentration is zero, absorbent just desorb is complete.
Embodiment 3
Be applied to by absorbent of the present invention in Shanghai boiler flue carbon dioxide recovery pilot-plant as shown in Figure 1, the flow process of this device is conventional CO
2absorption and desorption flow process, the absorbent of the first capturing carbon dioxide in embodiment 2 is sprayed in absorption tower 1, the flue gas of boiler smoke after absorbent absorbing carbon dioxide after formation processing, the absorbing liquid absorbing carbon dioxide enters desorber 4 successively after rich solution pump 2, lean/rich liquid heat exchanger 3, forms CO through desorb
2product, the absorbing liquid after desorb reenters absorption tower 1 after lean pump 5 and the first cooler 6.Flue gas and CO after boiler smoke, process
2the composition of product sees the following form.Absorption tower mean temperature 50 DEG C, the maximum temperature of desorber is 106 DEG C.CO
2capture rate reach 96%.
| Composition (Vol%) | CO 2 | SO 2 | O 2 | N 2 | H 2O |
| Flue gas | 13.273 | 0.037 | 5.257 | 74.865 | 6.568 |
| Flue gas after process | 0.53 | - | - | 92.09 | 7.38 |
| CO 2Product | 97 | - | - | - | 3 |
Claims (7)
1. an absorbent for capturing carbon dioxide, is characterized in that, comprises the solution of 1-amino-4-(2-ethoxy)-piperazine or 1-amino-4-(2-ethoxy)-piperazine.
2. the absorbent of capturing carbon dioxide as claimed in claim 1, is characterized in that, the solvent of the solution of described 1-amino-4-(2-ethoxy)-piperazine is any one or a few the mixture in water and organic solvent.
3. the absorbent of capturing carbon dioxide as claimed in claim 1, it is characterized in that, in the solution of described 1-amino-4-(2-ethoxy)-piperazine, the mass percent of 1-amino-4-(2-ethoxy)-piperazine is 10% ~ 70%.
4. the absorbent of capturing carbon dioxide as claimed in claim 1, it is characterized in that, in the solution of described 1-amino-4-(2-ethoxy)-piperazine, the mass percent of 1-amino-4-(2-ethoxy)-piperazine is 20% ~ 50%.
5. the absorbent of capturing carbon dioxide as claimed in claim 1, is characterized in that, the absorbent of described capturing carbon dioxide also comprises the compound that at least one has the function regulating absorption rate and absorptive capacity.
6. the absorbent of capturing carbon dioxide as claimed in claim 5, it is characterized in that, the described compound with the function of adjustment absorption rate and absorptive capacity is any one or a few the mixture in N methyldiethanol amine, 2-amino-2-methyl-1-1 propyl alcohol, AEEA, N-methyl-N-(-2-ethoxy)-1,3-propane diamine, triethanolamine, diethanol amine, monoethanolamine, piperazine and N-hydroxyethyl piperazine.
7. the absorbent of capturing carbon dioxide as claimed in claim 5, is characterized in that, described 1-amino-4-(2-ethoxy)-piperazine is 100: 0 ~ 100 with the weight ratio of the compound with the function regulating absorption rate and absorptive capacity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410852922.5A CN104524928A (en) | 2014-12-30 | 2014-12-30 | Absorbent for collecting carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410852922.5A CN104524928A (en) | 2014-12-30 | 2014-12-30 | Absorbent for collecting carbon dioxide |
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| Publication Number | Publication Date |
|---|---|
| CN104524928A true CN104524928A (en) | 2015-04-22 |
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ID=52840661
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|---|---|---|---|
| CN201410852922.5A Pending CN104524928A (en) | 2014-12-30 | 2014-12-30 | Absorbent for collecting carbon dioxide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105435585A (en) * | 2015-10-21 | 2016-03-30 | 中石化节能环保工程科技有限公司 | Composite absorbent for recovering CO2 from exhaust gas |
| CN107158895A (en) * | 2017-07-13 | 2017-09-15 | 斯养武 | A kind of carbon-dioxide absorbent |
| CN114699899A (en) * | 2022-04-07 | 2022-07-05 | 合肥工业大学 | Hydroxyalkyl piperazinyl compound organic amine carbon trapping agent |
| CN114870569A (en) * | 2022-04-11 | 2022-08-09 | 合肥工业大学 | Synthetic method of piperazine-based carbon trapping agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006240966A (en) * | 2005-03-07 | 2006-09-14 | Research Institute Of Innovative Technology For The Earth | Method for recovering carbon dioxide in exhaust gas by absorption and releasing |
| CN101282981A (en) * | 2005-08-11 | 2008-10-08 | 塔甘塔治疗公司 | Phosphonated rifamycins and uses thereof for the prevention and treatment of bone and joint infections |
| CN103221114A (en) * | 2010-09-02 | 2013-07-24 | 加州大学评议会 | Method and system for capturing carbon dioxide and/or sulfur dioxide from gas stream |
-
2014
- 2014-12-30 CN CN201410852922.5A patent/CN104524928A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006240966A (en) * | 2005-03-07 | 2006-09-14 | Research Institute Of Innovative Technology For The Earth | Method for recovering carbon dioxide in exhaust gas by absorption and releasing |
| CN101282981A (en) * | 2005-08-11 | 2008-10-08 | 塔甘塔治疗公司 | Phosphonated rifamycins and uses thereof for the prevention and treatment of bone and joint infections |
| CN103221114A (en) * | 2010-09-02 | 2013-07-24 | 加州大学评议会 | Method and system for capturing carbon dioxide and/or sulfur dioxide from gas stream |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105435585A (en) * | 2015-10-21 | 2016-03-30 | 中石化节能环保工程科技有限公司 | Composite absorbent for recovering CO2 from exhaust gas |
| CN107158895A (en) * | 2017-07-13 | 2017-09-15 | 斯养武 | A kind of carbon-dioxide absorbent |
| CN114699899A (en) * | 2022-04-07 | 2022-07-05 | 合肥工业大学 | Hydroxyalkyl piperazinyl compound organic amine carbon trapping agent |
| CN114870569A (en) * | 2022-04-11 | 2022-08-09 | 合肥工业大学 | Synthetic method of piperazine-based carbon trapping agent |
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Application publication date: 20150422 |