CN107398143A - Non- water absorbent for carbon dioxide removal in admixture of gas - Google Patents
Non- water absorbent for carbon dioxide removal in admixture of gas Download PDFInfo
- Publication number
- CN107398143A CN107398143A CN201610329274.4A CN201610329274A CN107398143A CN 107398143 A CN107398143 A CN 107398143A CN 201610329274 A CN201610329274 A CN 201610329274A CN 107398143 A CN107398143 A CN 107398143A
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- carbon dioxide
- gas
- absorbent
- admixture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1475—Removing carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/202—Alcohols or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/202—Alcohols or their derivatives
- B01D2252/2021—Methanol
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/202—Alcohols or their derivatives
- B01D2252/2023—Glycols, diols or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
- B01D2252/20494—Amino acids, their salts or derivatives
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention provides the non-water absorbent for carbon dioxide removal in admixture of gas, described absorbent is made up of amino-acid salt and alcohol organic solvent.Amino-acid salt weight percent is 10%~45% in the absorbent.Absorbent can produce precipitation after being characterised by its absorbing carbon dioxide in the present invention, the characteristics of system is undergone phase transition, with the advantage such as absorption rate is fast, absorptive capacity is big, regeneration energy consumption is low, the trapping and purification of carbon dioxide in the admixture of gas such as power plant flue gas, natural gas, synthesis gas can be applied to.
Description
Technical field
The invention belongs to gas separation technique field, is related to a kind of non-aqueous suction for being used for carbon dioxide removal in admixture of gas
Receive agent.
Background technology
Greenhouse effects have had a strong impact on climate change and atmospheric environment caused by CO2 emission.Global burningization in 2013
CO2 emissions caused by stone fuel reach 36,000,000,000 tons, wherein Chinese total carbon emission is 10,400,000,000 tons, more than America and Europe's
With.Wherein the industrial gasses such as coal-fired plant flue gas are as main emission source.Solves dioxy using energy-efficient technology and method
The emission problem for changing carbon is extremely urgent.
Treatment method of carbon dioxide mainly has absorption method, absorption process, membrane separation process etc..Utilize chemical absorbent such as Organic Alcohol
The aqueous solution of amine absorbs CO2It is current the most frequently used more ripe separation and concentration CO2One of method, mainly using absorbent water
Solution and CO2Reaction is absorbed, and CO is desorbed by thermal regeneration2The regeneration cycle of solvent is realized, vaporizes moisture and CO2
Together CO is purified in regeneration overhead condensation separation2, condensed water returns in tower or technique, consumes substantial amounts of cold or heat, about
The regeneration that 60-80% energy expenditure is used for lyosoption in regenerator causes processing cost higher.Recent study personnel endeavour
In the nonaqueous solvents processing CO using absorbent2It is expected to obtain more more preferable than water solution system absorption and reproducing characteristic, and absorbent
Component and content also turn into research emphasis.Publication No. CN104096453 A patent document discloses a kind of high selection
Property Physical decarburization absorption agent, use ionic liquid and NHD class complex solvent as absorbent, only have it is higher
Carbon dioxide absorption amount and the selectivity that can significantly improve separation of methane and carbon dioxide, wherein ionic liquid concentration are by weight
Percentage is calculated as 10%~90%.Publication No. CN104492226 A patent document discloses that to provide a kind of trapping mixed
The non-aqueous decarbonizing solution of carbon dioxide in gas is closed, its main absorbent components is N- ehtylethanolamines, solvent N, N- diethyl second
Hydramine.The compound decarburization that Publication No. CN104492226 A patent document discloses trapping carbon dioxide in gas mixture is molten
Liquid, by solvent phenmethylol, benzyl carbinol, 1-METHYLPYRROLIDONE or its mixture, main absorbent components MEA, help absorbent components
EDA, DETA and TETA, active component PZ and diacetyl, corrosion inhibiter are sodium chromate, antioxidant be sodium metavanadate and
Copper carbonate.
In summary, its main absorption composition of the non-water absorbent being related in disclosed patent and document is mainly organic amine,
Although improving absorption rate or selectivity to a certain extent, regeneration energy consumption is reduced, it is molten can not fundamentally to solve organic amine
Agent volatilization loss in regeneration is big, degraded, toxicity are big etc. is unfavorable for the puzzlements of the factors such as the person and environment.The present invention is waved using low
Hair property, chemically and thermally stability are preferable, environment-friendly nontoxic amino-acid salt and CO2The larger alcohol organic solvent shape of solubility
Into new non-aqueous absorption system, precipitation can be produced after its absorbing carbon dioxide and improves absorption driving force, there is phase transformation solid-liquid point
From the characteristics of, while have that absorptive capacity is big, separate after solid phase that individually the regeneration energy consumption of absorbent can be also greatly reduced in regeneration.
The content of the invention
It is an object of the invention to overcome the weak point of the non-water absorbent such as organic amine, it is used for gas so as to provide one kind
The non-aqueous phase transformation absorbent of carbon dioxide removal in mixture, absorption rate is improved, while reduce energy consumption.
Technical scheme provided by the invention is a kind of non-water absorbent for being used for carbon dioxide removal in admixture of gas, its
It is characterised by that the absorbent is made up of amino-acid salt and alcohols solvent, precipitation can be produced after its absorbing carbon dioxide, system occurs
The characteristics of phase transformation；The percetage by weight composition of composition is wherein in absorbent：
Amino-acid salt：10%~45%；
Alcohols solvent：Surplus；
Described amino-acid salt is the sylvite or sodium salt of lysine or proline；Described alcohols solvent be methanol, ethanol and
One or more in ethylene glycol.
Described a kind of non-water absorbent for being used for carbon dioxide removal in admixture of gas, it is characterised in that the absorbent should
Trapping and purification for carbon dioxide in the admixture of gas such as power plant flue gas, natural gas, synthesis gas.
The present invention has following beneficial effect compared with conventional absorbents：
1) present absorbent is alcohols non-aqueous system, and absorption mechanism is different from conventionally employed water solution system, part
Absorption product has such as 50-70 DEG C of relatively low decomposition temperature；
2) the amino-acid salt nonaqueous solvents that the present invention uses low volatility, stability is preferable, nontoxic is as absorbent, tool
There are high absorptive capacity and absorption rate, better than traditional organic amine absorbent；
3) precipitation can be produced after absorbent absorbing carbon dioxide in the present invention, there is the characteristics of phase transformation separation, with reference to two
The reaction product of carbonoxide is mainly enriched with precipitation, is easy to absorbent regeneration to handle；
4) absorbent solution is without significant change when lyosoption recycles in the present invention, and regeneration temperature is low, and energy consumption is small.
Embodiment
Embodiment 1
The methanol solution that mass fraction is 10% proline potassium is added in high 20cm, external diameter 3cm split type cold hydrazine
80ml, device are placed in 25 DEG C of waters bath with thermostatic control；The gaseous mixture (nitrogen is indifferent gas) of the carbon dioxide of content 15% is passed through,
Flow is about 0.2 liter/min, gas bubble absorption in cold hydrazine, after tail gas is by form snake type condenser, is dried by gas
Enter the content of capnograph METHOD FOR CONTINUOUS DETERMINATION outlet after device, stop experiment when carbon dioxide content is more than 13%；Will
Absorbing liquid takes sample 2.0ml after shaking up, be transferred in conical flask, adds the dilute sulfuric acid for instilling that concentration is 0.3M, and measurement is released
Gas volume, calculate in the absorbing load amount ie in solution of carbon dioxide amino-acid salt in the molal quantity of carbon dioxide and absorbing liquid
The ratio between molal quantity, mol CO2/mol AAS；Then by the static placement of absorbent solution, the changing features of absorbing liquid are observed.
The carbon dioxide loaded amount for measuring absorbing liquid sample is 0.69mol CO2/mol AAS。CO2Solution is outstanding after absorption
Turbid, room temperature is after static 12 hours, it is seen that the separation of obvious supernatant and precipitated phase, wherein supernatant is about 20ml.
Embodiment 2
The ethanol solution 80 that mass fraction is 45% proline potassium is added in high 20cm, external diameter 3cm split type cold hydrazine
Ml, device are placed in 25 DEG C of waters bath with thermostatic control；The gaseous mixture of the carbon dioxide of content 35% is passed through, flow is about 0.2 liter/min
Clock, gas bubble absorption in cold hydrazine, after tail gas is by form snake type condenser, by entering carbon dioxide after gas-drying apparatus
The content of analyzer METHOD FOR CONTINUOUS DETERMINATION outlet, stop experiment when carbon dioxide content is more than 30%；Sampled after absorbing liquid is shaken up
Product 2.0ml, measures the carbon dioxide loaded amount of solution, and observes the split-phase situation of absorbing liquid.
The be absorbed carbon dioxide loaded amount of liquid sample of survey calculation is 0.82mol CO2/mol AAS。CO2After absorption
After solution stand 12 hours, supernatant and precipitation are separated substantially, and wherein supernatant is about 45ml.
Embodiment 3
The ethanol solution that mass fraction is 20% proline potassium is added in high 20cm, external diameter 3cm split type cold hydrazine
80ml, device are placed in 25 DEG C of waters bath with thermostatic control；It it is about 0.2 liter/min by flow, the carbon dioxide of content 100% is passed through suction
Receive, stop experiment when carbon dioxide content is more than 90%；The body of static split-phase after the completion of absorption, measure supernatant and precipitation
Product；Separately sampled 1.5 grams of two-phase is transferred in conical flask, adds the dilute sulfuric acid for instilling that concentration is 0.3M, measures the gas of releasing
Body volume, solid phase and the molal quantity and absorbing liquid of carbon dioxide in the uptake ie in solution of carbon dioxide in upper phase are calculated respectively
Mass ratio, mol CO2/Kg。
The volume for measuring supernatant and precipitated phase respectively may be about 56ml and 22ml；The carbon dioxide loaded amount of phase solution up and down
Respectively 0.35 and 1.68mol CO2/ Kg, about 70% CO2It is enriched in the solid phase of precipitation.
Embodiment 4
The ethylene glycol solution 80ml that mass fraction is 20% lysine potassium is added in above-mentioned cold hydrazine, device is placed in 25 DEG C of constant temperature
In water-bath；It it is about 0.2 liter/min by flow, the carbon dioxide of content 100% is passed through absorption, when carbon dioxide content exceedes
Stop experiment when 90%；Absorb the split-phase situation for completing observation absorbing liquid, the absorbing load amount of sampling and measuring carbon dioxide.
CO2Solution is single liquid phase after absorption, has no obvious solid generation, the carbon dioxide loaded amount of solution is 1.61
mol CO2/mol AAS；The static split-phase of room temperature is after 24 hours, it is seen that obvious supernatant and flocculent deposit phase.
Embodiment 5
The alcoholic solution 200ml of various concentrations proline salt or lysine salt is added in stainless steel stirred tank, in identical magnetic
Under power stir speed (S.S.), device is placed in 26 DEG C of waters bath with thermostatic control；The gaseous mixture of the carbon dioxide of content 14.5% is passed through the full of solvent
And solution, flow are about 0.6 liter/min, gas is by disperser bubble absorption, after tail gas is by condenser, gas-drying apparatus
Into the change of the content of capnograph METHOD FOR CONTINUOUS DETERMINATION outlet；Different solutions take after absorbing liquid is shaken up after the completion of absorbing
Sample measures the absorbing load amount of carbon dioxide.The 1.0M aqueous solution under the same terms is contrast test.As a result such as the institute of table 1
Show.
The different non-water absorbents of table 1 absorb CO2Feature and effect compare
Embodiment 6
Obtained solidliquid mixture is added in embodiment 3 in 250ml four-hole boiling flask after absorbing, and device is placed in thermostatical oil
Normal pressure static regeneration experiment is carried out in bath, is discharged after gas is condensed；It is 65 DEG C -85 DEG C to adjust oil bath temperature section, each
Thermostatic takes the sample of mixed liquor to determine load capacity after 2 hours.As a result it is as shown in table 2.
The load capacity of the carbon dioxide of regenerated liquid under the different temperatures of table 2
Embodiment 7
The ethanol solution 500ml that mass fraction is 20% proline potassium is added in 1000ml four-hole boiling flask, device is placed in
In 30 DEG C of constant temperature oil baths；It it is 0.2 liter/min by flow, the gaseous mixture of the carbon dioxide of content 10% is passed through bubble absorption, tail gas
After form snake type condenser, by entering the content of capnograph METHOD FOR CONTINUOUS DETERMINATION outlet after gas-drying apparatus, inhale
3 hours between time receiving, the molal quantity and absorbing liquid quality of carbon dioxide in the absorbing load amount ie in solution of sample measurement carbon dioxide are taken
The ratio between, mol CO2/Kg；The mixture that will be obtained after absorption, it is placed in constant temperature oil bath in 75 DEG C of constant temperature, is passed through flow as 0.2
Liter/min nitrogen, discharge after gas is condensed, stop after 3 hours, the load capacity of sample measurement carbon dioxide is taken, by four times
Absorption and desorption is tested, and understands the steadiness of absorbent.It the results are shown in Table shown in 3.
The absorbing liquid absorption of table 3-regenerating stability effect
Claims (2)
- A kind of 1. non-water absorbent for being used for carbon dioxide removal in admixture of gas, it is characterised in that the absorbent by amino-acid salt and The characteristics of alcohols solvent is formed, and precipitation can be produced after its absorbing carbon dioxide, and system is undergone phase transition；Wherein component in absorbent Percetage by weight composition be：Amino-acid salt：10%~45%；Alcohols solvent：Surplus；Described amino-acid salt is the sylvite or sodium salt of lysine or proline；Described alcohols solvent is methanol, ethanol and second two One or more in alcohol.
- 2. a kind of non-water absorbent for being used for carbon dioxide removal in admixture of gas as claimed in claim 1, it is characterised in that should Absorbent is applied to the trapping and purification of carbon dioxide in the admixture of gas such as power plant flue gas, natural gas, synthesis gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610329274.4A CN107398143A (en) | 2016-05-18 | 2016-05-18 | Non- water absorbent for carbon dioxide removal in admixture of gas |
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| CN201610329274.4A CN107398143A (en) | 2016-05-18 | 2016-05-18 | Non- water absorbent for carbon dioxide removal in admixture of gas |
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| CN107398143A true CN107398143A (en) | 2017-11-28 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087003A (en) * | 2020-01-09 | 2021-07-09 | 国家能源投资集团有限责任公司 | Carbon dioxide absorption and utilization method and application thereof |
| CN113731155A (en) * | 2021-09-29 | 2021-12-03 | 大连海事大学 | Carbon dioxide emission reduction and utilization device and method for dredging ship |
| FR3136683A1 (en) * | 2022-06-20 | 2023-12-22 | Vicat | METHOD FOR CAPTURING AND STORING CO 2 |
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| JP2012143760A (en) * | 2006-05-18 | 2012-08-02 | Basf Se | Carbon dioxide absorbent whose energy requirement for regeneration is reduced and method for removing carbon dioxide from gaseous flow |
| WO2014012808A1 (en) * | 2012-07-17 | 2014-01-23 | Siemens Aktiengesellschaft | Scrubbing solution for absorption of carbon dioxide and method for accelerating the absorption by germanium dioxide |
| CN103657382A (en) * | 2013-11-29 | 2014-03-26 | 浙江大学 | Method for removing carbon dioxide from gas mixture through biphasic absorption |
| CN104492226A (en) * | 2014-12-12 | 2015-04-08 | 大连理工大学 | Non-aqueous decarburization solution for capturing carbon dioxide in mixed gas and application thereof |
| CN104548874A (en) * | 2013-10-17 | 2015-04-29 | 胡亮 | Deacidification process and system for gas mixtures containing acid gases |
| CN105080326A (en) * | 2015-09-16 | 2015-11-25 | 广东电网有限责任公司电力科学研究院 | Mixed absorption liquid for capturing carbon dioxide |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20090263302A1 (en) * | 2006-04-07 | 2009-10-22 | Liang Hu | Self-Concentrating Absorbent for Acid Gas Separation |
| JP2012143760A (en) * | 2006-05-18 | 2012-08-02 | Basf Se | Carbon dioxide absorbent whose energy requirement for regeneration is reduced and method for removing carbon dioxide from gaseous flow |
| WO2014012808A1 (en) * | 2012-07-17 | 2014-01-23 | Siemens Aktiengesellschaft | Scrubbing solution for absorption of carbon dioxide and method for accelerating the absorption by germanium dioxide |
| CN104548874A (en) * | 2013-10-17 | 2015-04-29 | 胡亮 | Deacidification process and system for gas mixtures containing acid gases |
| CN103657382A (en) * | 2013-11-29 | 2014-03-26 | 浙江大学 | Method for removing carbon dioxide from gas mixture through biphasic absorption |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087003A (en) * | 2020-01-09 | 2021-07-09 | 国家能源投资集团有限责任公司 | Carbon dioxide absorption and utilization method and application thereof |
| CN113087003B (en) * | 2020-01-09 | 2022-12-09 | 国家能源投资集团有限责任公司 | Carbon dioxide absorption and utilization method and application thereof |
| CN113731155A (en) * | 2021-09-29 | 2021-12-03 | 大连海事大学 | Carbon dioxide emission reduction and utilization device and method for dredging ship |
| FR3136683A1 (en) * | 2022-06-20 | 2023-12-22 | Vicat | METHOD FOR CAPTURING AND STORING CO 2 |
| WO2023247872A1 (en) * | 2022-06-20 | 2023-12-28 | Vicat | Method for trapping and storing co2 |
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Application publication date: 20171128 |