CN103394277B - A kind of organic amine composite absorber removing carbon dioxide in coal-fired flue-gas - Google Patents
A kind of organic amine composite absorber removing carbon dioxide in coal-fired flue-gas Download PDFInfo
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- 239000006096 absorbing agent Substances 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 150000001412 amines Chemical class 0.000 title claims abstract description 37
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000003546 flue gas Substances 0.000 title claims abstract description 20
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 58
- 230000007797 corrosion Effects 0.000 claims abstract description 29
- 238000005260 corrosion Methods 0.000 claims abstract description 29
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 13
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims abstract description 11
- HXMVNCMPQGPRLN-UHFFFAOYSA-N 2-hydroxyputrescine Chemical compound NCCC(O)CN HXMVNCMPQGPRLN-UHFFFAOYSA-N 0.000 claims abstract description 10
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 8
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 claims abstract description 6
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000013530 defoamer Substances 0.000 claims abstract description 5
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims abstract description 4
- JPIGSMKDJQPHJC-UHFFFAOYSA-N 1-(2-aminoethoxy)ethanol Chemical compound CC(O)OCCN JPIGSMKDJQPHJC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims abstract description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims abstract description 3
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229940043237 diethanolamine Drugs 0.000 claims abstract description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229960001124 trientine Drugs 0.000 claims abstract description 3
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical group O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 11
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 11
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical group [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229940008099 dimethicone Drugs 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 abstract description 27
- 230000008929 regeneration Effects 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000003795 desorption Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 32
- 239000007789 gas Substances 0.000 description 19
- 230000002745 absorbent Effects 0.000 description 16
- 239000002250 absorbent Substances 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 15
- 229920006395 saturated elastomer Polymers 0.000 description 11
- 239000003595 mist Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910000975 Carbon steel Inorganic materials 0.000 description 7
- 239000010962 carbon steel Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 5
- 238000005261 decarburization Methods 0.000 description 5
- 150000003335 secondary amines Chemical class 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 150000003141 primary amines Chemical group 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- -1 tertiary alcohol amine Chemical class 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004164 analytical calibration Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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 a kind of organic amine composite absorber removing carbon dioxide in coal-fired flue-gas, it is made up of the component of following mass fraction: main absorber component 10% ~ 45%, absorbefacient component 0 ~ 10%, corrosion inhibiter 0.01% ~ 6%, antioxidant 0.01 ~ 3%, defoamer 0 ~ 5%, surplus is water; Wherein, main absorber component is made up of the following component accounting for organic amine composite absorber total amount mass percent: monoethanolamine MEA3% ~ 20%, 2-amino-2-methyl-1-propanol AMP0 ~ 12%, the summation 1% ~ 15% of piperazine PZ and N-aminoethylpiperazine AEP, the summation 1% ~ 12% of amino ethyl ethanolamine AEEA and 2-Methylaminoethanol MMEA; Absorbefacient component is one or more in diethanol amine DEA, diethylenetriamine DETA, triethylene tetramine TETA, N methyldiethanol amine MDEA, sulfolane, tertiary fourth aminoethoxyethanol TBEE.The present invention has good stability, absorptive capacity is large, degree of purification is high, regeneration energy consumption is low, desorption effect is good, significantly can reduce the advantages such as in use composite absorber degraded loss.
Description
Technical field
The present invention relates to a kind of organic amine composite absorber, be specifically related to a kind of organic amine composite absorber removing carbon dioxide in coal-fired flue-gas.Belong to gas pollution control technical field.
Background technology
As everyone knows, carbon dioxide causes " greenhouse effects ", causes the main greenhouse gas that terrestrial climate warms.In recent years, along with countries in the world are to the concern of global greenhouse effect, the emission problem of carbon dioxide causes global attention.
Flue gas discharged from coal-fired boiler is one of primary discharge source of carbon dioxide, has flue gas flow large, divides and forces down, containing a large amount of inert gas N
2, containing O
2and H
2o, containing pollutant SO
2, the feature such as NOx and flue dust.That commonly uses at present traps CO from mixed flue gas
2method have the methods such as chemical absorbing, physical absorption, membrane separation process and cryogenic condensation.Wherein Physical Absorption method needs under high pressure to carry out, and is mainly applicable to the source of the gas that carbon dioxide content is higher; And chemical absorption method can carry out under normal pressure or lower pressure, therefore this method is more suitable for processing the lower source of the gas of carbon dioxide content.
Existing decarburization composite absorber major part is with K
2cO
3or MDEA or MEA is main body, though there is its respective advantage, its comprehensive decarburization capacity is general lower, and corrosivity is strong, easy to foaming, and energy consumption is higher, and operating pressure is slightly high, therefore all leaves some room for improvement in a lot.Also there are some follow-on technology in addition, but often can only be used for the mist reclaiming carbon dioxide at low pressures.
Although separating carbon dioxide technology is ripe from flue gas (mist), for large discharge, low CO that coal fired boiler of power plant flue gas is such
2content flue gas, it is not high enough to there is absorption rate in carbon dioxide removal, and equipment investment is excessive, and absorbent degraded is rotten, and regeneration hear rate is higher, and burn into such as easily to foam at the problem, decarburization high cost.For 600MW supercritical generating sets, generation CO per hour
2about 500 tons, CO per ton
2remove the minimum in the public data of expense 217.7 yuan/t(data) calculate, decarburization expense per hour is up to 10.9 ten thousand yuan, and 600MW unit 1 hour generating price only about 210,000 yuan.High cost makes enterprise and society be difficult to bear.
Summary of the invention
The object of the invention is for overcoming above-mentioned the deficiencies in the prior art, a kind of organic amine composite absorber removing carbon dioxide in coal-fired flue-gas is provided.
For achieving the above object, the present invention adopts following technical proposals:
Remove an organic amine composite absorber for carbon dioxide in coal-fired flue-gas, it is made up of the component of following mass fraction: main absorber component 10% ~ 45%, absorbefacient component 0 ~ 10%, corrosion inhibiter 0.01% ~ 6%, antioxidant 0.01% ~ 3%, defoamer 0 ~ 5%, surplus is water; Wherein, described main absorber component is made up of the following component accounting for organic amine composite absorber total amount mass percent: monoethanolamine MEA3% ~ 20%, 2-amino-2-methyl-1-propanol AMP0 ~ 12%, the summation 1% ~ 15% of piperazine PZ and N-aminoethylpiperazine AEP, the summation 1% ~ 12% of amino ethyl ethanolamine AEEA and 2-Methylaminoethanol MMEA; Described absorbefacient component is one or more in diethanol amine DEA, diethylenetriamine DETA, triethylene tetramine TETA, N methyldiethanol amine MDEA, sulfolane, tertiary fourth aminoethoxyethanol TBEE.
Described corrosion inhibiter is V
2o
5, potassium chromate, sodium metavanadate, natrium nitrosum, one or more in sodium nitrate or sodium phosphate.
Described antioxidant is one or more in sodium potassium tartrate tetrahydrate, sodium thiosulfate, sodium pyrosulfite or sodium hydrogensulfite.
Described defoamer is any one in dimethicone, enanthol, octanol, nonyl alcohol, polyethers or polyether modified silicon oil.
Described a kind of preparation method removing the organic amine composite absorber of carbon dioxide in coal-fired flue-gas is mixed to get each component of recipe ratio.
Beneficial effect of the present invention is, improves absorbent to CO
2absorption rate and absorptive capacity, reduce regeneration energy consumption, thus make to remove CO
2equipment size diminishes, and reduces investment, reduces energy consumption, reduces decarburization cost.MEA is to CO
2absorption rate is fast, is applicable to low dividing potential drop CO
2trapping, but the continuous action time is short, and regeneration energy consumption is high, easily degrades, and corrosivity is strong.PZ in main absorbent components belongs to cyclammonium, and be easy to hydrolysis, its molecule contains 2 secondary amine.Another main absorbent components AEP (N-aminoethylpiperazine) belongs to the derivative of piperazine.Because also belong to cyclammonium, therefore character and piperazine have close place, have 1 primary amine groups and 1 secondary amine in AEP molecule, and MEA and PZ and AEP reciprocation can improve absorption CO
2reaction rate and absorptive capacity, the constant absorption time is elongated, absorptive capacity increase.The absorption CO of 0.7mol/LMEA+0.3mol/LPZ combination
2experiment effect curve as in Figure 1 and Figure 2 shown in, as seen from the figure, absorbability significantly improves.The absorption test step that the present invention relates to is as follows:
Absorption test device comprises the raw material gas tank and reactor that connect successively, and raw material gas tank is connected to the entrance point of reactor successively through preheater, soap film flowmeter I, the port of export of reactor is provided with soap film flowmeter II and pH analyzer.After all electronic instrument calibrations, the air-tightness of inspection package unit, configuration organic amine composite absorber also adds in reactor, and reactor adopts the thermostatic container of belt stirrer, and the measuring probe of pH analyzer gos deep into reactor bottom as far as possible; By N
2+ CO
2mist fully mixes in raw material gas tank, and utilizes preheater to preheat it, to reach preset temperature; Start timing while mist in raw material gas tank enters reactor, keep in reactor stirring, once import and export flow and pH value every 5 minutes records; When reaction reaches saturated, stop test.Absorption rate utilizes formula p Δ V=nRT to carry out calculating, and (p is CO
2dividing potential drop, Δ V for absorb CO
2volume, n is CO
2amount of substance, T is temperature), be solution absorption per second CO
2amount of substance; The absorption rate calculating mensuration, to the integration of time, is CO
2molar absorbance amount.
Main absorbent components AMP is a kind of typical sterically hindered amines.Owing to its atom N being connected to a huge functional group, hydramine and CO can be hindered
2key link, thus the stability of carbamic acid root is reduced, and make carbamic acid root very easily reductive hydrolysis become hydramine and bicarbonate ion, therefore, its absorption rate is suitable with I and II hydramine, maximum absorbance capacity is identical with tertiary alcohol amine, therefore MEA and AMP reciprocation makes absorbability strengthen.Absorption rate and the absorptive capacity of 0.7mol/LMEA+0.3mol/LAMP combination are shown in Fig. 1 and Fig. 2, and visible high-efficiency continuous soak time increases, and absorptive capacity increases, and absorbability is improved significantly.In addition, due to the space steric effect of AMP, the amino-acid salt that it is formed is very unstable, and the energy required for regeneration is less, and reproduction ratio is easier to.The regeneration temperature of 0.7mol/LMEA+0.3mol/LAMP combination is 102 DEG C, lower than 103 DEG C of 1mol/LMEA.Regeneration rate is 97.28%, apparently higher than 93.68% of 1mol/LMEA.The regeneration test step that the present invention relates to is as follows:
Organic amine composite absorber of the present invention absorbs CO
2after saturated, put into isothermal reactor, design temperature by filling the absorption bottle absorbing rear solution, isothermal reactor is connected with condenser, and condenser is connected to saturated calcium hydroxide absorption bottle through concentrated sulfuric acid Drexel bottle, soap film flowmeter successively.Soap film flowmeter III is utilized to measure regeneration gas speed, with saturated aqua calcis absorption and regeneration gas.When soap film flowmeter III gas flow is less than 5mL/min, regeneration test terminates.Absorb saturated By Amine Solutions and be called rich solution, the absorbing liquid again obtained after regeneration is lean solution.In regeneration test, absorb saturated rich solution by thermal regeneration solution sucking-off CO
2, again become lean solution.Thermal regeneration obtains the saturated absorption amount of lean solution and the ratio of organic amine composite absorber saturated absorption amount is regeneration rate.
Concrete expression formula is as follows:
In formula: η-regeneration rate, %;
L '-regeneration lean solution saturated absorption amount, mol;
L-organic amine composite absorber uptake, mol.
AEEA in main absorbent components, its molecule contains 1 primary amine groups and 1 secondary amine, absorbs CO
2reaction rate is fast, and absorptive capacity is large, and boiling temperature is high, and evaporation loss is few, not easily degrades, itself and MEA compound, can improve absorbability, reduce degraded loss.
MMEA in main absorbent components, its absorption rate and MEA close, containing a methyl in its molecular structure, have the effect of some steric hindrances, be suitable for regeneration, the regenerability of absorbent can be improved.
Help the DETA in absorbent components, containing 2 primary amine groups and 1 secondary amine, TETA contains 2 primary amine groups and 2 secondary amine, and they absorb CO
2reaction rate is far above MEA, and absorptive capacity is 3 times and 4 times of MEA respectively, these two kinds of compositions add the absorption rate and absorptive capacity that improve composite absorber.
Although help the DEA absorption rate in absorbent components low, boiling point comparatively MEA is high, and evaporation loss is few, not easily degrades, and can reduce the loss of absorbent in running.
Help the MDEA in absorbent components, although reaction rate is low, itself and MEA reciprocation, can improve reaction rate, and the constant absorption time increases.Be combined in the constant absorption later stage from Fig. 1 and Fig. 2,0.50mol/LMEA+0.50mol/LMDEA, absorption rate is higher than 1mol/LMEA, and absorptive capacity also increases to some extent.What is more important, MDEA absorbs CO
2generate metastable bicarbonate, easily regenerate, the regeneration energy consumption of composite absorber is reduced.The regeneration temperature of 0.50mol/LMEA+0.50mol/LMDEA combination is 102 DEG C, and regeneration rate is 96.33%.The regeneration temperature of 1mol/LMEA is 103 DEG C, and regeneration rate is 93.68%.Visible, regenerability is improved obviously than MEA.
Beneficial effect of the present invention is also, the degraded loss of absorbent reduces, and by the interpolation of antioxidant, makes the degradation rate of MEA decrease 40.2% ~ 49.6%.Antioxidant destroys the degradation reaction chain of MEA and oxygen, interrupts the linksystem of reaction, to reach the degradation suppressing MEA.In 12%MEA+8%AMP composite solution, add sodium potassium tartrate tetrahydrate, suppress MEA degraded situation as shown in table 1.
Table 1, antioxidant suppress MEA degradation effect
As can be seen from Table 1, the gross mass mark of organic amine be 20% MEA solution degrade in the presence of oxygen, degradation amount about 15%, the sodium potassium tartrate tetrahydrate antidegradant that experiment is investigated is when adding minute quantity (mass fraction is 0.5% and 1%), good anti-degradation can be played to MEA solution, under the condition of sodium potassium tartrate tetrahydrate of adding mass fraction 1%, the loss of solution nearly 50% can be reduced.
Beneficial effect of the present invention is also, by the compound of organic amine and adding of corrosion inhibiter, solves the etching problem of absorbent to equipment.Experimental result shows, and organic amine composite absorber is lower than MEA by 30.1% ~ 37.2% to the rate of corrosion of carbon steel, lower than MEA by 30.8% ~ 38.4% to stainless rate of corrosion.After adding corrosion inhibiter, for Q235-A carbon steel, corrosion inhibition rate reaches 90% ~ 97%, and corrosion rate can be down to 0.05gm
-2h
-1, carbon steel material can be protected preferably.Be 90% ~ 98% to 304 type stainless steels (0Cr18Ni9 stainless steel) corrosion inhibition rate.The present invention carries out corrosion test in conjunction with the method for dynamic weight loss and static steel, in 12%MEA+8%AMP composite solution, add corrosion inhibiter, adopts Q235-A carbon steel lacing film and 0Cr19Ni9 lacing film to carry out corrosion experiment, measures different corrosion inhibiter corrosion mitigating effect.Under the condition of not adding corrosion inhibiter, investigated respectively total amine concentration be MEA, MEA+PZ and MEA+AMP(of 20wt% wherein, the mass concentration ratio of MEA and PZ or MEA and AMP is 1.5: 1) solution is to Q235-A carbon steel and the stainless corrosion condition of 304 types, and result is as shown in table 2.
Table 2, solution are to carbon steel and stainless corrosion condition
As can be seen from Table 2, the MEA solution of 20wt% to carbon steel and stainless corrosion condition still more serious, reach 1.96gm respectively
-2h
-1and 1.33gm
-2h
-1.The corrosivity of simple MEA solution is not high, but itself and CO
2after reaction, owing to generating a series of compound as carbaminate, bicarbonate etc., its corrosivity is caused significantly to increase.And PZ and AMP and CO
2the product that reaction generates does not have obvious corrosivity, so after adding both, the corrosion rate of absorbent solution to material declines to some extent.PZ and AMP in a sense, is also equivalent to a kind of corrosion inhibiter, and from the effect of inhibition, PZ outline is better than AMP, so choose the composite absorbent combination of MEA+PZ.
Accompanying drawing explanation
Fig. 1 is absorption rate and time curve;
Fig. 2 is uptake and time curve.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further elaborated, should be noted that following explanation is only to explain the present invention, not limiting its content.
Embodiment 1
Get two parts based on the 15wt% organic amine composite absorber of monoethanolamine MEA, wherein, the content of monoethanolamine MEA is 8%, AEEA is 1%, PZ is 1%, DETA is 1.5%, AMP is 1.5%, and sulfolane is 1%, DEA is 1%, corrosion inhibiter potassium chromate 0.1%, antioxidant sodium potassium tartrate tetrahydrate 0.5%, surplus is water.Described a kind of preparation method removing the organic amine composite absorber of carbon dioxide in coal-fired flue-gas is mixed to get each component of recipe ratio.Composite absorber temperature is 40 DEG C, gas phase CO
2partial pressure is respectively the experiment 1 in 15kPa(table 3), experiment 2 in 45kPa(table 3), will containing CO
2and N
2mist pass into two parts of above-mentioned composite absorbers respectively, after gas-liquid two-phase reaches balance, CO in composite absorber
2molal quantity and composite absorber in CO in the ratio of molal quantity sum of each organic amine and composite absorber
2solubility see table 3.
Table 3,40 DEG C, the composite absorber experimental result of 15wt%
Embodiment 2
Get two parts based on the 15wt% organic amine composite absorber of monoethanolamine MEA, wherein, the content of monoethanolamine MEA is 8%, AEEA is 1%, PZ is 1%, DETA is 1.5%, AMP is 1.5%, and sulfolane is 1%, DEA is 1%, corrosion inhibiter potassium chromate 0.1%, antioxidant sodium potassium tartrate tetrahydrate 0.5%, surplus is water.Described a kind of preparation method removing the organic amine composite absorber of carbon dioxide in coal-fired flue-gas is mixed to get each component of recipe ratio.Under condition of normal pressure, gas phase CO
2experiment 1 in dividing potential drop 15kPa(table 4), experiment 2 in 45kPa(table 4), containing CO
2and N
2mist input two parts of described composite absorbers respectively, be issued to saturated in temperature 40 DEG C of situations, absorb and saturatedly rear composite absorber is warmed to 112 DEG C, control CO in regeneration gas
2dividing potential drop is respectively 15kPa, 45kPa, after gas-liquid two-phase reaches balance, and CO in lyosoption
2with CO in the mol ratio of composite absorber and composite absorber
2solubility see table 4.
Table 4,112 DEG C, the composite absorber experimental result of 15wt%
Embodiment 3
Get two parts based on the 20wt% organic amine composite absorber of monoethanolamine (MEA), wherein, the content of monoethanolamine (MEA) is 8%, AEEA is 1%, MMEA be 1%, AMP is 1%, PZ is 1%, DETA is 1%, and sulfolane is 2%, DEA is 2%, DETA be 1%, TETA is 1%, TBEE is 1%, corrosion inhibiter potassium chromate 0.1%, antioxidant sodium potassium tartrate tetrahydrate 0.5%, surplus is water.Described a kind of preparation method removing the organic amine composite absorber of carbon dioxide in coal-fired flue-gas is mixed to get each component of recipe ratio.Composite absorber temperature is 45 DEG C, under condition of normal pressure, gas phase CO
2partial pressure is the experiment 1 in 60kPa(table 5), experiment 2 in 85kPa(table 5), will containing CO
2and N
2mist pass into two parts of above-mentioned composite absorbers respectively, after gas-liquid two-phase reaches balance, CO in lyosoption
2with CO in the mol ratio of composite absorber and composite absorber
2solubility see table 5.
Table 5,45 DEG C, the composite absorber experimental result of 20wt%
Embodiment 4
Get two parts based on the 20wt% organic amine composite absorber of monoethanolamine (MEA), wherein, the content of monoethanolamine (MEA) is 8%, AEEA be 1%, MMEA is 1%, AMP is 1%, PZ be 1%, DETA is 1%, and sulfolane is 2%, DEA is 2%, DETA be 1%, TETA be 1%, TBEE is 1%.Corrosion inhibiter potassium chromate 0.1%, antioxidant sodium potassium tartrate tetrahydrate 0.5%, surplus is water.Described a kind of preparation method removing the organic amine composite absorber of carbon dioxide in coal-fired flue-gas is mixed to get each component of recipe ratio.Under condition of normal pressure, gas phase CO
2experiment 1 in dividing potential drop 60kPa(table 6), experiment 2 in 85kPa(table 6), containing CO
2and N
2mist input two parts of described composite absorbers respectively, be issued to saturated in temperature 45 C situation, absorb and saturatedly rear composite absorber is warmed to 115 DEG C, control CO in regeneration gas
2dividing potential drop is respectively 60kPa, 85kPa, after gas-liquid two-phase reaches balance, and CO in composite absorber
2with CO in the mol ratio of composite absorber and composite absorber
2solubility see table 6.
Table 6,115 DEG C, the composite absorber experimental result of 20wt%
Embodiment 5
Get two parts based on the 20wt% organic amine composite absorber of monoethanolamine (MEA), wherein, the content of monoethanolamine (MEA) is 8%, AEEA is 1.5%, AMP is 2%, PZ be 2%, TETA is 2%, sulfolane is 1.5%, DEA is 2%, TBEE is 1%, corrosion inhibiter sodium metavanadate 0.3%, antioxidant sodium potassium tartrate tetrahydrate 0.5%, surplus is water.Described a kind of preparation method removing the organic amine composite absorber of carbon dioxide in coal-fired flue-gas is mixed to get each component of recipe ratio.Getting composite absorber temperature is 40 DEG C, under condition of normal pressure, gas phase CO
2partial pressure is the experiment 1 in 40kPa(table 7), experiment 2 in 70kPa(table 7), will containing CO
2and N
2mist pass into two parts of above-mentioned composite absorbers respectively, after gas-liquid two-phase reaches balance, CO in composite absorber
2with CO in the mol ratio of monoethanolamine (MEA) composite absorber and composite absorber
2solubility see table 7.
Table 7,40 DEG C, the composite absorber experimental result of 20wt%
Embodiment 6
Get two parts based on the 20wt% organic amine composite absorber of monoethanolamine (MEA), wherein, the content of monoethanolamine (MEA) is 8%, AEEA is 1.5%, AMP is 2%, PZ be 2%, TETA is 2%, sulfolane is 1.5%, DEA is 2%, TBEE is 1%, corrosion inhibiter sodium metavanadate 0.3%, antioxidant sodium potassium tartrate tetrahydrate 0.5%, surplus is water.Described a kind of preparation method removing the organic amine composite absorber of carbon dioxide in coal-fired flue-gas is mixed to get each component of recipe ratio.Under condition of normal pressure, gas phase CO
2experiment 1 in dividing potential drop 40kPa(table 8), experiment 2 in 70kPa(table 8), containing CO
2and N
2mist input two parts of described composite absorbers respectively, be issued to saturated in temperature 40 DEG C of situations, absorb and saturatedly rear composite absorber is warmed to 113 DEG C, control CO in regeneration gas
2dividing potential drop is respectively 40kPa, 70kPa, after gas-liquid two-phase reaches balance, and CO in composite absorber
2with CO in the mol ratio of composite absorber and composite absorber
2solubility see table 8.
Table 8,113 DEG C, the composite absorber experimental result of 20wt%
As can be seen from embodiment 1 and embodiment 2, CO at 40 DEG C
2divide when being pressed in 45kPa and absorb, CO at 112 DEG C
2carry out desorb when dividing potential drop is 45kPa, 1 liter of 15% composite absorber can absorption and separation CO
2amount be 157-64=93 gram.
As can be seen from embodiment 3 and embodiment 4, CO at 45 DEG C
2dividing potential drop absorbs when being 85kPa, CO at 115 DEG C
2carry out desorb when dividing potential drop is 85kPa, 1 liter of 20% composite absorber can absorption and separation CO
2amount be 177-46=131 gram.
As can be seen from embodiment 5 and embodiment 6, CO at 40 DEG C
2dividing potential drop absorbs when being 70kPa, CO at 113 DEG C
2carry out desorb when dividing potential drop is 70kPa, 1 liter of 20% composite absorber can absorption and separation CO
2amount be 174-58=116 gram.
Although above-mentioned, the specific embodiment of the present invention is described; but not limiting the scope of the invention; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (3)
1. one kind removes the organic amine composite absorber of carbon dioxide in coal-fired flue-gas, it is characterized in that, it is made up of the component of following mass fraction: main absorber component 10% ~ 45%, absorbefacient component 0 ~ 10%, corrosion inhibiter 0.01% ~ 6%, antioxidant 0.01% ~ 3%, defoamer 0 ~ 5%, surplus is water; Wherein, described main absorber component is made up of the following component accounting for organic amine composite absorber total amount mass percent: monoethanolamine MEA3% ~ 20%, 2-amino-2-methyl-1-propanol AMP is 0 ~ 12%, the summation 1% ~ 15% of piperazine PZ and N-aminoethylpiperazine AEP, the summation 1% ~ 12% of amino ethyl ethanolamine AEEA and 2-Methylaminoethanol MMEA; Described absorbefacient component is one or more in diethanol amine DEA, diethylenetriamine DETA, triethylene tetramine TETA, N methyldiethanol amine MDEA, sulfolane, tertiary fourth aminoethoxyethanol TBEE;
Described defoamer is any one in dimethicone, enanthol, octanol, nonyl alcohol, polyethers or polyether modified silicon oil.
2. organic amine composite absorber according to claim 1, is characterized in that, described corrosion inhibiter is sodium metavanadate.
3. organic amine composite absorber according to claim 1, is characterized in that, described antioxidant is sodium potassium tartrate tetrahydrate.
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