CN1005381B - Separation co2 from other gas of mixture - Google Patents

Separation co2 from other gas of mixture Download PDF

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CN1005381B
CN1005381B CN85103423.3A CN85103423A CN1005381B CN 1005381 B CN1005381 B CN 1005381B CN 85103423 A CN85103423 A CN 85103423A CN 1005381 B CN1005381 B CN 1005381B
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solution
amine
gas
grams per
per liters
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CN85103423A (en
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施亚钧
涂晋林
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East China University of Science and Technology
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East China University of 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
    • 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

Abstract

The present invention provides an improved solution separating CO2 from gas mixtures. The solution comprises carbonate and borate of alkali metal to be used as main absorbing agents for CO2. The solution also contains various isopolyacid salts and heteropoly acid salts of a proper quantity of amine, vanadate and vanadium boron, and the monomers and the polymers can activate the absorption and the desorption of CO2. The solution of the present invention has the obvious characteristics of high CO2 absorbing capacity, high speed rate on absorption and desorption, low energy consumption for regeneration and wide range of application (can be used for separating CO2 from gas mixtures containing oxygen). Therefore, the present invention can be used for separating CO2 from natural gas, synthetic gas, coal gas, smoke gas, kiln gas, fermentation gas, etc.

Description

Separating carbon dioxide from gaseous mixture
The present invention relates to a kind of from gaseous mixture the improvement solution of separating carbon dioxide.
Separation of C O from gaseous mixture 2Two purposes are arranged, the one, Purge gas to be satisfying processing and the service requirements to them, and the one, recycle CO 2In many industrial sectors.
From gaseous mixture, absorb CO with a kind of solution in the absorption stage 2, absorbed CO 2Solution in the regeneration stage with CO 2Desorb, solution just circulates between two stages absorbing and regenerate, and this is the technological process that generally adopts.
Alkaline carbonate (U.S.Patent No2,886,405) is a kind of solution of knowing that early adopts.In order to accelerate the normally absorption and desorption CO of solution of potassium carbonate of carbonate 2Speed, invented many kinds of methods in succession after some years, certain methods is to add different inorganic activators in solution of potassium carbonate, for example: add white arsenic AS 2O 3(U.S.Patent No.3,037,844); Add tellurous acid or selenous acid (British Patent No.791,150); Add borate and vanadate (British Patent No.819,215 and U.S.Patent3,907,969).Other methods are to add organic class activator in solution of potassium carbonate, for example: add alcamines (Monoethanolamine MEA BASF MEA or diethanolamine DEA or trolamine TEA, Rritish Patent No.1,084,526); Add amino acid (British Patent No.786,669); Add Padil (France Patent2,272,720); Add amine borate (British Patent No.1,063,517 and U.S.Patent No.3,851,041); Also invented the method (British Patent2,037,723) that in solution of potassium carbonate, adds amine and white arsenic dual activator in recent years; The method (U.S.Patent4,112,050) that adds sterically hindered amines.More than the many important activator in the invention is in industrial application.
But the above-mentioned AS that adds 2O 3The potash method tend to superseded because of solution severe toxicity; Add the easy oxidative degradation of potash rule amine of amine, make the scope of application wideless, and CO 2The desorb energy consumption still higher, absorptive capacity is lower.
The objective of the invention is to, adopt a kind of novel solution, it and traditional absorbent solution relatively, CO 2Absorptive capacity bigger, the speed of absorption and desorption is faster, the regeneration energy consumption of solution is lower, activator is difficult for oxidative degradation, can be used for oxygen-containing gas and removes CO 2, thereby method of the present invention is more economical, suitability is wider.
In view of above-mentioned purpose, the novel solutions that the present invention proposes has following characteristics:
1. be CO with alkali-metal carbonate and borate 2Main absorber.
2. the vanadate that contains proper concn in the solution is as solution absorption or desorb CO 2The time, the variation range of its pH value is 8 to 13, in this pH value scope, the existence form of vanadate is that example will be K with sylvite 3VO 4, K 4V 2O 7And K 3V 3O 9Or K 4V 4O 12Deng, and exist multiple polymerization equilibrium between them.This just makes pyrovanadate and vanadate become solution absorption CO 2Or desorb CO 2The time good activator.
3. be another kind of activator with more a spot of amine (as diethanolamine DEA, Padil Glycine, Diethylenetriaminee (DETA) DETA etc.), these amine can absorb CO with very high speed 2, generating carbaminate, the carboxylamine salt hydrolysis generates hydrocarbonate and restores amine, makes amine as CO 2Carrier, between liquid-gas interface and liquid phase main body, shuttle.Particularly as vanadate, when borate exists, the activation of amine has obtained reinforcement, thereby the concentration of amine can reduce exponentially with in the past method comparison.Thereby some shortcomings (, having reduced regeneration impellent etc.) of having avoided the amine activator to bring as easy oxidative degradation.
4. in the solution of the present invention, the amount of borate, vanadate and amine should keep optimum mole ratio, and solution is absorbing CO 2And desorb CO 2In the process, between these monomers such as borate, vanadate and multiple isopoly-acid salt and boron vanadium heteropolyacid salt, exist moving of polymerization equilibrium, so they are to CO 2Absorption and desorption play multiplicity reactivation, this has just improved the performance of solution further.
5. solution of the present invention also has another distinguishing feature, and promptly chemical stability is good, and not oxidated degraded is applicable to separation of C O from the oxygen-containing gas mixture 2, even available heat air gas is carried regeneration soln.
In addition, similar with prior art basically because of the absorption and the regeneration situation of solution, the temperature when promptly absorbing is 70～100 ℃, and the temperature during regeneration is 90～120 ℃, so be convenient to implement.
Solution absorption CO of the present invention 2Principal reaction as follows:
With the carbonate of potassium and borate to CO 2The example that is absorbed as have
CO 2+ OH -/ HCO - 3(soon) (1)
CO 2+ H 2O/HCO - 3(slowly) (2)
Amine in the solution is example with RR ' NH, absorbs CO 2Reaction have again:
CO 2+ RR ' NH/RR ' NCOOH(is very fast) (3)
RR′NCOOH+OH -/HCO - 3+RR′NH
(soon) (4)
HCO - 3/H ++CO - 3（5）
RR′NH+H +/RR′NH + 2（6）
Characteristics of the present invention are to exist the following polymerization equilibrium in the solution:
2V 2O 4- 7+4H +/V 4O 4- 12+2H 2O（7）
2KBO 2+K 3VO 4+2CO 2+3H 2O /
K 3〔B 2O（OH） 4（VO 4）〕+2KHCO 3（8）
Solution mesoboric acid salt also has K 2B 4O 7; Vanadate also has other existence forms, as K 3VO 4, K 3HV 2O 7, K 3V 3O 9, K 4V 4O 12Deng, thereby be similar to formula (7) and (8), also can write out the other polymerization equilibrium, can find out significantly, when solution particularly liquid film absorbed CO 2The time, the pH value descends, and polymerization equilibrium will move right, and make the concentration and the OH of amine in the film -Concentration has obtained shock absorption timely.Thereby strengthened the activation of amine, improved CO 2Absorbed speed.In like manner, desorb CO 2The time, polymerization equilibrium is moved to the left, and makes CO 2Desorption rate improve, this is the distinguishing feature of amine of the present invention, boron, vanadium heteropolyacid and isopoly-acid multiplicity reactivation potash lye.
Solution of the present invention is example with the borate and the vanadate of potassium, can obtain by following reaction easily:
K 2CO 3+2H 3BO 3△/2KBO 2+CO 2+3H 2O （9）
2K 2CO 3+V 2O 3△/K 4V 2O 7+CO 2（10）
Various forms of borates are with KBO 2KBO is write a Chinese character in simplified form in the form metering 2; Various forms of vanadate are with K 4V 2O 7K is write a Chinese character in simplified form in the form metering 4V 2O 7, (down together).
The small amount of amine that solution is contained can be hydramine such as diethanolamine DEA, amino acid such as Padil (GLycine), and alkene is pressed as Diethylenetriaminee (DETA) DETA, and sky is asked bulky amine.
Embodiment 1.Contain K 2CO 3, KBO 2, K 4V 2O 7And the absorbent solution of DEA, experimental result sees Table 1.
Experiment shows, DEA and boron, vanadium heteropolyacid potassium, when isopoly-acid potassium activates solution of potassium carbonate jointly, and solution is to CO 2Absorption and regenerability be better than traditional DEA activation potash lye.The concentration of DEA can be between 5 to 40 grams per liters, but would rather select 5 to 20 grams per liters for use.
Embodiment 2: contain K 2CO 3, KBO 2, K 4V 2O 7And the absorbent solution of Padil (GLYcine), experimental result sees Table 2.
Experiment shows that Padil and boron, vanadium heteropolyacid potassium, the common activatory carbonic acid soln of isopoly-acid potassium are better than traditional Padil activation potash lye, and wherein Padil concentration should be in 10～40 grams per liter scopes.
Embodiment 3: contain K 2CO 3, KBO 2, K 4V 2O 7And the absorbent solution of Diethylenetriaminee (DETA) (DETA), experimental result sees Table 3.
Experiment shows, DETA and boron, vanadium heteropolyacid potassium, and the common activatory solution of potassium carbonate of isopoly-acid potassium 3-4 is better than 3-1 respectively, three kinds of solution of 3-2 and 3-3, wherein the concentration of DETA should be in 2～20 grams per liter scopes.
With the same 1-1 of solution 1-2,3-3 compares with 3-2, it can also be seen that, it is suitable basically that boron, vanadium heteropolyacid potassium, isopoly-acid potassium activatory potash lye and amine activate potash solution.
Embodiment 4: in order to guarantee that vanadate has the polymerization equilibrium existence shown in formula (7) and (8) etc., then pyrovanadic acid potassium K in the solution 4V 2O 7Content should for example select 20 to 50 grams per liters for use greater than 20 grams per liters, suitable 0.05 to 0.13 mol.
The experimental result of table 4 shows, KBO 2: K 4V 2O 7Mol ratio can promptly work as K for 4 to 14 4V 2O 7Content is 0.05 to 0.13 mol, KBO 2Content should be 0.2～1.8 mol and (be equivalent to KBO 2Content be 16 grams per liters～147.4 grams per liters), but must be pointed out: KBO wherein 2The content height is though absorb CO 2Ability still not poor, but CO 2Absorption and desorption speed slack-off, so should decide their concentration to total effect of absorption and desorption two processes according to activator.
Same amine content also should not be too high, between 0.01～0.32 mol.K in the solution 2CO 3Concentration can be between 100～280 grams per liters.
After having taken all factors into consideration the whole process of absorption and desorption, in the solution of the present invention, amine, KBO 2, K 4V 2O 7Optimum mole ratio between the three is between 0.2: 4: 1 to 2.5: 14: 1.Such solution is compared (seeing above-listed embodiment) with existing amine potash solution, has CO 2The absorptive capacity height, absorption and desorption speed is fast, the regeneration low power consumption and other advantages.And the amine consumption in the solution can quite lack, and mainly plays activation, thereby can be used for separation of C O in the oxygen-containing gas by inorganic boron, the isopoly-acid salt and the heteropolyacid salt of vanadium 2, can be widely used in Sweet natural gas, separation of C O in synthetic gas, coal gas, stack gas, kiln gas, the fermentation gas 2
Example 1 to example 4, K 2CO 3, KBO 2, K 4V 2O 7These sylvite replace with sodium salt respectively, and amine asks that with sky bulky amine replaces, and also can obtain similar result.
Solution of the present invention is when being used for oxygen-containing gas mixture separation of C O 2Or when absorbing rich solution and selecting for use warm air gas to propose regeneration, the amine content in the solution should be used lower concentration values, can avoid the oxidative degradation of amine like this.
Solution of the present invention is only used one section flow process (comprise absorb and two processes of regenerating) usually, but as processing requirement when high when very high (to the gas cleaning requirement), can adopt two sections flow processs, promptly adopt two sections absorptions, the flow process of two-stage regeneration is to satisfy the demanding occasion of gas purification degree.
Table 1, (KBO in the table 2By K 2CO 3And H 3BO 3Make)
Table 2, (KBO in the table 2By K 2CO 3And H 3BO 3Make)
Figure 85103423_IMG2
Table 3, (KBO in this table 2By KOH and H 3BO 3Make)
Table 4, (KBO in the table 2By KOH and H 3BO 3Make)
Figure 85103423_IMG4

Claims (12)

1, a kind of from gaseous mixture the improvement solution of separating carbon dioxide, formed by the solution that contains absorption agent and activator, the invention is characterized in:
(1) contains main absorption agent carbonate (K or Na), borate (K or Na) and activator vanadate (K or Na), amine (diethanolamine, Diethylenetriaminee (DETA), Padil) in the said absorbent solution, wherein between amine, borate, the vanadate three suitable mol ratio is arranged, that is:
Amine: KBO 2(or NaBO 2): K 4V 2O 7(or Na 3V 2O 7)=0.2: 4: 1 was to 2.5: 14: the 1(mol ratio)
(2) its suitable concentration range of contained main absorption agent and activator is in the absorbent solution:
K 2CO 3: 100～280 grams per liters,
KBO 2(metering form): 16～150 grams per liters,
K 4V 2O 7(metering form): 20～50 grams per liters,
Amine-diethanolamine: 5～20 grams per liters,
Or Diethylenetriaminee (DETA): 2～20 grams per liters,
Or Padil: 10～40 grams per liters.
2, improvement solution as claimed in claim 1, when it was used to handle the gaseous mixture of oxygen containing carbonic acid gas, wherein amine concentration should be used low limit value.
3, improvement solution as claimed in claim 1, when the absorption rich solution was used regenerated with hot air, wherein amine concentration should be used low limit value.
CN85103423.3A 1985-04-20 1985-04-20 Separation co2 from other gas of mixture Expired CN1005381B (en)

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Application Number Priority Date Filing Date Title
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Application Number Priority Date Filing Date Title
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CN1005381B true CN1005381B (en) 1989-10-11

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Publication number Priority date Publication date Assignee Title
CN1055872C (en) * 1992-03-14 2000-08-30 南京化学工业(集团)公司研究院 Removing carbon dioxide from mixed gas by compound activator
WO2004089512A1 (en) * 2003-04-04 2004-10-21 Board Of Regents, The University Of Texas System Polyamine/alkali salt blends for carbon dioxide removal from gas streams
CN101125651B (en) * 2007-06-05 2010-09-08 浙江大学 Method for reclaiming carbon dioxide from tail gas of calcium formate producing process
CN101066516B (en) * 2007-06-06 2011-04-20 华东理工大学 Decarbonizing solution comprising borate
CN102173416B (en) * 2011-02-15 2012-11-14 中电投远达环保工程有限公司 Ion additive for carbon dioxide absorbent of organic amines
FR2993352B1 (en) * 2012-07-13 2018-07-13 L'air Liquide,Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude METHOD AND APPARATUS FOR SEPARATING CARBON DIOXIDE-RICH GAS
CN103170318A (en) * 2012-12-20 2013-06-26 新疆德蓝股份有限公司 Preparation method of carbon dioxide adsorbent
CN103657382A (en) * 2013-11-29 2014-03-26 浙江大学 Method for removing carbon dioxide from gas mixture through biphasic absorption
CN113491941B (en) * 2020-04-08 2023-08-29 中国石油化工股份有限公司 Aqueous solution for removing carbon dioxide from reaction recycle gas

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