CN102284227A - Method for capturing carbon dioxide in mixed gas by using composite decarbonizing solution - Google Patents
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- CN102284227A CN102284227A CN2011102305706A CN201110230570A CN102284227A CN 102284227 A CN102284227 A CN 102284227A CN 2011102305706 A CN2011102305706 A CN 2011102305706A CN 201110230570 A CN201110230570 A CN 201110230570A CN 102284227 A CN102284227 A CN 102284227A
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Abstract
The invention relates to composite decarbonizing solution for capturing carbon dioxide in mixed gas, and belongs to the technical field of the capturing of carbon dioxide gas. The composite decarbonizing solution consists of benzyl alcohol, phenethyl alcohol, N-methyl pyrrolidone or a mixture thereof which serve as solvents, mono etobaccool amine (MEA) serving as a main absorption ingredient, ethidene diamine (EDA), diethylenetriamine (DETA) and triethylenetetramine (TETA) which serve as assistant absorption ingredients, piperazidine (PZ) and 2,3-butanedione which serve as active ingredients, sodium chromate serving as a corrosion inhibitor and sodium metavanadate and copper carbonate which serve as antioxidants. In the composite decarbonizing solution, due to the adoption of the mixed solvents, the absorption capacity, purification degree and deabsorption rate on carbon dioxide are improved, the range of reaction temperature is enlarged, the volume of a deabsorption tower is reduced, the regenerated energy consumption is reduced greatly, and the investment of equipment and operating cost are reduced. The composite decarbonizing solution is used for capturing various chemical reaction tail gases, ore decomposition gases, combustion flue gases, natural gases, city gases and the carbon dioxide in methane, and has a bright application prospect.
Description
Technical field
The invention belongs to gas separation technique field, relate to a kind of method that captures carbon dioxide in the mist with composite decarbonizing solution.
Background technology
The greenhouse effects that CO2 emission causes have made our earth be subjected to serious climatic effect.The world's majority state that comprises China has at present all been signed Kyoto Protocol, and the control emission amount of carbon dioxide is described, has become the problem that countries in the world are extremely paid close attention to.Carbon dioxide can be widely used in multiple fields such as machinery, chemical industry, food, medicine as a kind of carbon resource of preciousness simultaneously, if can just can reduce atmosphere pollution effectively with its recycling, provides carbon resource for us continuously.The source of China's carbon dioxide is very abundant, but because to reclaim the measure of carbon dioxide unfavorable, the amount of carbon dioxide of annual recycling also not enough total release 1%, therefore, the recycling problem that effectively solves carbon dioxide is extremely urgent.And the solvent absorption trapping and recovering carbon dioxide is present industrial topmost method.
The method of collecting carbonic anhydride mainly contains: solvent absorption, physisorphtion, membrane separation process, O
2Production by Catalytic Combustion Process etc.Wherein chemical solvent method absorbing carbon dioxide technology is widely used in discharging sources of the gas such as natural gas, refinery gas, synthesis gas and flue gas.For the absorbability that further improves absorbent, reduce corrosivity, the energy consumption when reducing the loss that causes because of volatilization and regeneration, people are devoted to develop chemical solution absorbent efficiently always, through years of researches, developed into the absorbent of present compounding ingredients low energy consumption, and the composition component of absorbent and content problem still are the emphasis of scholar's research from the absorbent of one pack system high energy consumption of beginning.
1985 Chinese patent (CN 103855A) a kind of method of removing carbon dioxide from admixture of gas is disclosed, its absorbent is K
2CO
315-30%, diethanol amine 10-30 grams per liter, amion acetic acid 10-20 grams per liter, boric acid 15-30 grams per liter, total vanadium is (with KVO
3Meter) 5-10 grams per liter.Its solution absorbs CO
2Ability be 21-26NM
3CO
2/ M
3Solution.
1999, United States Patent (USP) (US09,329,259) disclose a kind of from unstripped gas the method for absorbing carbon dioxide, will be in composite solution from the carbon dioxide absorption in the unstripped gas, preferred double solvents contains one or more fast response rate amines (MEA or DEA mass fraction are 5%～35%) than small concentration and one or more long response time rate amines (the MDEA mass fraction is 5%～50%) of higher concentration.
Calendar year 2001, United States Patent (USP) (US 6,290,754 B1) discloses a kind of method that removes carbon dioxide from mist, and its absorbent is for to add active component in the MDEA amine aqueous solution.Wherein MDEA concentration is 1-6mol/L.Active component is H
2N-C
nH
2n-NH-CH
2-CH
2OH, (1≤n≤4), its concentration be total amine molar concentration 0.01 to 0.5 between.
2002, Chinese patent (CN 1340374A) discloses a kind of composite decarbonizing solution that removes carbon dioxide in the gas, gas amine percentage by weight is made up of following raw material: MDEA A.30～50%, B.0.1～1.5% dimethylethanolamine, C.0.5～1.5% methylethanolamine, D.1～2% two piperazines, all the other are water for E..Its solution absorbs CO
2Ability be 22-26NM
3CO
2/ M
3Solution.
2007, Chinese patent (CN 101053751A) discloses a kind of composite decarbonizing solution that reclaims carbon dioxide in the waste gas, the composition and the mass percent of this kind composite solution are as follows: compound ammonia spirit 20～60%, wherein contain the fast response rate amines of lower one or more of concentration and one or more long response time rate amines of higher concentration; Polyalcohol ether 5～10%; Antioxidant 1～5%; Corrosion inhibiter 1～5%; All the other are water.
2007, (KR 10 for Korean Patent, 2007,0097560) composite absorber that is used for separating carbon dioxide is disclosed, absorbent comprises formula 2 heterocyclic compounds of at least 1 amino on ring of formula 1 compound of 100 weight portions and 1～60 mass parts, wherein contain a hydroxyl and primary amine groups on the described compound molecule of 1 formula, closing on unsubstituted on the described amino α carbon potential, and alkyl substituent and alcoholic extract hydroxyl group substituting group are positioned on the β carbon.
In sum, main at present application MEA, DEA etc. are main absorbent, for helping absorption, the decarburization aqueous solution that cooperates strong active component of multiple absorbability and anticorrisive agent, corrosion inhibiter or the like to form is though there is its advantage separately with MDEA etc., but its comprehensive decarburization capacity is generally lower, regeneration energy consumption height, the solvent internal circulating load is big, and equipment corrosion is strong, can not make economic benefit reach optimization, therefore also have perfect leeway.
Summary of the invention
The invention provides a kind of method, solved problems such as the decarbonizing solution decarburization capacity is low, regeneration energy consumption height, CO is preferably arranged under lower pressure condition with carbon dioxide in the composite decarbonizing solution capture mist
2Organic efficiency.
The technical solution adopted for the present invention to solve the technical problems is:
The said composite decarbonizing solution of the present invention mainly by solvent, main absorbent components, help absorbent components, active component, corrosion inhibiter and antioxidant to form.Solvent adopts phenmethylol, benzyl carbinol, N-methyl pyrrolidone and composition thereof.Main absorbent components is monoethanolamine (MEA), and as main absorbent components, absorption rate is fast with MEA, and uptake is big, and desorption temperature is low, but corrosivity is slightly high; Help absorbent components to comprise ethylenediamine (EDA), diethylenetriamine (DETA) and triethylene tetramine (TETA), these three kinds of materials can use separately, also can mix use, that adds helps absorbent components, the main absorption load that improves solvent that rises reduces its desorption temperature, owing to help absorbent uptake temperature influence bigger, reduce along with the rising of temperature, thereby along with its uptake of absorption reaction variation of temperature also changes thereupon; Active component is mainly by piperazine (PZ) and 2 in addition, and the 3-diacetyl constitutes, and two kinds of materials can be used alone, but also also mix together, and mainly plays the main absorbent of activation and helps the absorbent effect, improves reaction rate and uptake, makes it to reach capacity fast; In order to reduce absorption liquid to the corrosion of equipment and the degraded of self, in this composite decarbonizing liquid, added corrosion inhibiter simultaneously, corrosion inhibiter adopts sodium chromate; Antioxidant adopts inferior sodium metavanadate and copper carbonate.
It is 0～80% that the composite decarbonizing solution of carbon dioxide in the above-mentioned capture mist, solvent summation can adopt the mass percent that accounts for composite decarbonizing solution.The mass percent that main absorbent components (MEA) can adopt is 10～40%.The mass percent that helps the summation of absorbent components to adopt is 5%～30%.The mass percent that the summation of active component can adopt is 1%～10%.The mass percent that corrosion inhibiter can adopt is 0.05%～1.0%.It is 0.05%～1.0% that antioxidant is adopted to adopt distant mass percent.
Effect of the present invention and benefit are: the said NEW TYPE OF COMPOSITE decarbonizing solution of the present invention, the volume fraction that can capture carbon dioxide in the mist is 2%～90%, has per hour 50～70Nm
3CO
2/ m
3The big uptake of solution has 35～50Nm
3CO
2/ m
3The higher desorption quantity of solution, and in the time of 70～90 ℃, begin desorb, complete desorb during 60min.And that traditional Dan Yishui is the solution uptake and the desorption quantity of solvent is all very low, needs desorb fully about 90min.Therefore the present invention be suitable for reclaiming that multiple chemical reaction tail gas, combustion flue gas, ore branch are vented one's spleen, the carbon dioxide in the natural gas, coal gas, biogas.Maximum feature of the present invention, water that need not be traditional is solvent exactly, and uses phenmethylol, benzyl carbinol, N-methyl pyrrolidone or its mixture instead.Because behind former traditional solution absorbing carbon dioxide, desorption temperature generally all is higher than 100 ℃, and after being higher than the normal boiling point of water, will evaporate as the water of solvent and cause a large amount of heat-energy losses, so the present invention uses high boiling phenmethylol, benzyl carbinol, N-methyl pyrrolidone or its mixture, be difficult for not even volatilization during regeneration, greatly reduce the consumption of regenerated heat energy.
Description of drawings
Fig. 1 is that the 200g mass fraction is that 40%MEA and benzyl carbinol mixed liquor absorb desorb figure.
Among the figure:
The specific embodiment
Come detailed description preferred embodiment below with reference to instantiation, for its industrial applications provides basic data.
Embodiment
With the wherein total amine mass content of 200g is 40% MEA, the benzyl carbinol mass content be 60% mixed liquor as absorbent solution, in the reactor of being furnished with the constant temperature oil bath agitator of the 500ml that packs into, be under 40 ℃ of conditions, with 0.012M in temperature
3/ h flow velocity, feeding pressure are that 0.2MPa, concentration are 99% CO
2, carry out METHOD FOR CONTINUOUS DETERMINATION with the anticorrosion flowmeter of wet type, calculate the absorption rate of carbon dioxide thus, uptake and absorption load.After solution reached capacity, oil bath temperature was set to 120 ℃ and carries out desorb, and measured its complete desorption quantity and desorption rate, through three absorption desorption experiment, saw its stability (seeing Figure of description).
In example, under anhydrous situation, the solution uptake slightly descends, but desorption efficiency is fast, and saturated carbon dioxide absorption liquid is when carrying out desorb for 120 ℃, along with the increase desorption rate reduction in reaction time.And each example absorbs desorb through three times, and its uptake desorption quantity is close, reaches stable, can carry out industrial applications.
In sum, carbon dioxide absorption solution of the present invention has good absorption and desorption effect.Especially in desorption process, owing to used novel mixed solvent phenmethylol, benzyl carbinol, N-methyl pyrrolidone or its mixture, under the prerequisite that total desorption quantity does not have to reduce, the volatile quantity of solvent when having reduced desorb, improved desorption rate, vast scale has reduced the desorption and regeneration energy consumption, has also reduced the employed cooling water inflow of cooling solvent flashing simultaneously, can increase economic efficiency.And through three absorption desorbs, absorbent still has good effect, so the present invention has good industrialized application prospect.
Claims (7)
1. one kind captures the method for carbon dioxide in the mist with composite decarbonizing solution, this decarbonizing solution by solvent, main absorbent components, help absorbent components, activating component, corrosion inhibiter and antioxidant to form; It is characterized in that: solvent adopts one or more in phenmethylol, benzyl carbinol, the N-methyl pyrrolidone, main absorbent components adopts monoethanolamine (MEA), help absorbent components to adopt in ethylenediamine (EDA), diethylenetriamine (DETA), the triethylene tetramine (TETA) one or more, active component adopts piperazine (PZ), 2, in the 3-diacetyl one or more, corrosion inhibiter is a sodium chromate, and antioxidant adopts sodium metavanadate and copper carbonate.
2. method according to claim 1 is characterized in that: the mass percent that solvent accounts for composite decarbonizing solution is 0～80%.
3. method according to claim 1 is characterized in that: the mass percent of main absorbent components (MEA) is 10～40%.
4. method according to claim 1 is characterized in that: the mass percent that helps absorbent components is 5%～30%.
5. method according to claim 1 is characterized in that: the mass percent of active component is 1%～10%.
6. method according to claim 1 is characterized in that: the mass percent of corrosion inhibiter is 0.05%～1.0%.
7. method according to claim 1 is characterized in that: the mass percent of antioxidant is 0.05%～1.0%.
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Cited By (9)
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|---|---|---|---|---|
| CN104117265A (en) * | 2014-08-13 | 2014-10-29 | 中电投远达环保工程有限公司 | Composite absorber suitable for absorbing CO2 gas in flue gas of IGCC power plant |
| CN104190210A (en) * | 2014-08-26 | 2014-12-10 | 中国船舶重工集团公司第七一八研究所 | Composite organic alcohol amine absorbing agent for carbon dioxide |
| CN104548903A (en) * | 2013-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | Organic amine solvent for capturing carbon dioxide |
| CN105854529A (en) * | 2016-06-08 | 2016-08-17 | 中石化炼化工程（集团）股份有限公司 | Non-aqueous solvent carbon dioxide capture liquid, method and system |
| TWI619540B (en) * | 2017-02-18 | 2018-04-01 | 國立清華大學 | Carbon dioxide absorber composition and method for capturing carbon dioxide |
| CN109012090A (en) * | 2018-07-30 | 2018-12-18 | 大连理工大学 | It is a kind of can oxidation resistant non-aqueous decarbonizing solution for trap carbon dioxide in gas mixture |
| JP2019055371A (en) * | 2017-09-21 | 2019-04-11 | 株式会社東芝 | Carbon dioxide absorbent and carbon dioxide removal device |
| CN110479044A (en) * | 2019-03-13 | 2019-11-22 | 中国石油大学(北京) | A kind of gas trapping agent and its preparation method and application |
| CN112138511A (en) * | 2019-06-27 | 2020-12-29 | 中石化南京化工研究院有限公司 | Non-water-based amine solution for capturing carbon dioxide in mixed gas |
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Cited By (11)
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| CN104548903A (en) * | 2013-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | Organic amine solvent for capturing carbon dioxide |
| CN104117265A (en) * | 2014-08-13 | 2014-10-29 | 中电投远达环保工程有限公司 | Composite absorber suitable for absorbing CO2 gas in flue gas of IGCC power plant |
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| CN105854529A (en) * | 2016-06-08 | 2016-08-17 | 中石化炼化工程（集团）股份有限公司 | Non-aqueous solvent carbon dioxide capture liquid, method and system |
| 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 |
| JP2019055371A (en) * | 2017-09-21 | 2019-04-11 | 株式会社東芝 | Carbon dioxide absorbent and carbon dioxide removal device |
| US11123683B2 (en) | 2017-09-21 | 2021-09-21 | Kabushiki Kaisha Toshiba | Carbon dioxide absorbent and apparatus of separating and recovering carbon dioxide |
| CN109012090A (en) * | 2018-07-30 | 2018-12-18 | 大连理工大学 | It is a kind of can oxidation resistant non-aqueous decarbonizing solution for trap carbon dioxide in gas mixture |
| CN110479044A (en) * | 2019-03-13 | 2019-11-22 | 中国石油大学(北京) | A kind of gas trapping agent and its preparation method and application |
| CN112138511A (en) * | 2019-06-27 | 2020-12-29 | 中石化南京化工研究院有限公司 | Non-water-based amine solution for capturing carbon dioxide in mixed gas |
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