CN117244384A - Antioxidant less aqueous amine liquid for capturing carbon dioxide in flue gas and application thereof - Google Patents
Antioxidant less aqueous amine liquid for capturing carbon dioxide in flue gas and application thereof Download PDFInfo
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- CN117244384A CN117244384A CN202311425327.9A CN202311425327A CN117244384A CN 117244384 A CN117244384 A CN 117244384A CN 202311425327 A CN202311425327 A CN 202311425327A CN 117244384 A CN117244384 A CN 117244384A
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- amine
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 236
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 118
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 118
- 150000001412 amines Chemical class 0.000 title claims abstract description 104
- 239000007788 liquid Substances 0.000 title claims abstract description 55
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 24
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 24
- 239000003546 flue gas Substances 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
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000006731 degradation reaction Methods 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000010525 oxidative degradation reaction Methods 0.000 claims abstract description 51
- 230000015556 catabolic process Effects 0.000 claims abstract description 47
- 239000007789 gas Substances 0.000 claims abstract description 40
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002738 chelating agent Substances 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 11
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 4
- 239000003345 natural gas Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 106
- 239000007864 aqueous solution Substances 0.000 claims description 42
- 239000003112 inhibitor Substances 0.000 claims description 33
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 23
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 23
- 229960003330 pentetic acid Drugs 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 claims description 7
- VSZSIEBALNXIFG-UHFFFAOYSA-N 2-hydroxyethyl 2,2-bis(sulfanyl)acetate Chemical compound OCCOC(=O)C(S)S VSZSIEBALNXIFG-UHFFFAOYSA-N 0.000 claims description 7
- -1 biogas Substances 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000004568 cement Substances 0.000 claims description 2
- 239000002440 industrial waste Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 83
- 238000003795 desorption Methods 0.000 abstract description 79
- 208000022120 Jeavons syndrome Diseases 0.000 abstract description 71
- 238000006243 chemical reaction Methods 0.000 abstract description 42
- 238000002485 combustion reaction Methods 0.000 abstract description 10
- 239000006096 absorbing agent Substances 0.000 abstract description 4
- 230000003064 anti-oxidating effect Effects 0.000 abstract description 2
- 239000003034 coal gas Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 description 23
- 239000002250 absorbent Substances 0.000 description 20
- 230000002745 absorbent Effects 0.000 description 20
- 230000008929 regeneration Effects 0.000 description 15
- 238000011069 regeneration method Methods 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- 238000005265 energy consumption Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000011835 investigation Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 5
- 150000002923 oximes Chemical class 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 150000003335 secondary amines Chemical class 0.000 description 5
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 4
- 238000005262 decarbonization Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 4
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000001177 diphosphate Substances 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 3
- 229940074439 potassium sodium tartrate Drugs 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- YOINMAMSTLSLOX-UHFFFAOYSA-N 2-(2,3-diaminobut-1-enyl)phenol Chemical compound CC(N)C(N)=CC1=CC=CC=C1O YOINMAMSTLSLOX-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- HXMVNCMPQGPRLN-UHFFFAOYSA-N 2-hydroxyputrescine Chemical compound NCCC(O)CN HXMVNCMPQGPRLN-UHFFFAOYSA-N 0.000 description 1
- PYSGFFTXMUWEOT-UHFFFAOYSA-N 3-(dimethylamino)propan-1-ol Chemical compound CN(C)CCCO PYSGFFTXMUWEOT-UHFFFAOYSA-N 0.000 description 1
- 241000948268 Meda Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003275 alpha amino acid group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001926 trapping method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/80—Organic bases or salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/05—Biogas
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention provides an antioxidation less aqueous amine liquid for capturing carbon dioxide in flue gas and application thereof, wherein the less aqueous amine liquid comprises the following components in percentage by mass of 10-30wt% of N-ethylethanolamine; 50-80wt% of N, N-diethyl ethanolamine; piperazine water solution with the mass percentage of 5-20wt%; the sulfur-containing antioxidant and/or chelating agent accounts for 0.1-5.0wt%. After the sulfur-containing antioxidant and/or chelating agent are added into the amine liquid with little water, the reaction is not affected, the absorption and desorption performance of the regenerated solution after thermal degradation or oxidative degradation can be improved, the content of main absorber EMEA of the amine liquid with little water is greatly reserved, and the degradation degree is reduced. The antioxidant amine liquid with little water has excellent degradation resistance and good stability, and is suitable for recycling carbon dioxide in various chemical reaction tail gases, combustion flue gases, ore decomposition gases, natural gas, coal gas and biogas.
Description
Technical Field
The invention belongs to the field of chemical gas separation, and particularly relates to an antioxidant amine liquid with little water for capturing carbon dioxide in flue gas and application thereof.
Background
In the current background of rapid industrial development, environmental protection, deterioration and other problems become the focus of general attention in the world, and gradually become the core problem of each country. The greenhouse effect has great influence, and the severe problems brought by the greenhouse effect, especially serious climate disasters, become global environmental problems. Gases that cause global warming mainly include: carbon dioxide (CO) 2 ) Methane (CH) 4 ) Nitrous oxide (N) 2 O), and the like. CO 2 The content in the atmosphere is far greater than that of other greenhouse gases, and the greenhouse effect is mainly caused. CO from fossil fuels 2 The emission amount reaches 200 hundred million tons each year, and the flue gas generated by fossil fuel plants is used as a main source of greenhouse gases and has large gas amount and CO 2 Low partial pressure. Thus, CO in flue gas is developed 2 Is not suitable for the recovery method.
The existing carbon dioxide trapping technology mainly comprises pre-combustion trapping, oxygen-enriched trapping and post-combustion trapping. The pre-combustion trapping is mainly used for medium-high concentration CO 2 The trapping energy consumption is low, but the investment cost is higher; oxygen-enriched capture of CO in combustion products 2 The concentration is high, and the oxygen can be directly recovered by a physical method, but the demand for high-concentration oxygen is large, and the investment cost is too high; the post-combustion trapping is arranged behind the combustion system, the process configuration is not required to be changed, the effect of treating low-concentration and low-pressure gas is good, the application range is wide, the potential is huge, and the cost is lower than that of the former two trapping methods, so that most trapping modes adopt post-combustion trapping. Post combustion CO capture 2 The method of (2) includes chemical absorption method, physical absorption method, membrane separation method, pressure swing adsorption method, temperature swing adsorption method, low temperature separation method, etc. Wherein the chemical absorption process is carried out by and CO 2 The chemical reaction takes place to absorb the gas and separate out the CO in the flue gas 2 And can be heated to produce the reaction productThe method of decomposing the substance reaches CO 2 The regeneration purpose has the advantages that: the separation degree is high, and the CO with low concentration can be separated out by higher absorption efficiency 2 Flue gas. The existing chemical absorption methods include a hot potassium alkaline method, a benzene Phil method, an organic amine method, an ionic liquid method and the like, and the former two methods are widely applied to industrial production as well as research mature methods; organic alcohol amine compounds are used as common absorbents for the organic amine process proposed in the 30 s, at least one of which reduces the vapor pressure of the compound and provides hydroxyl groups of basicity in the organic molecular structure, while containing an amino group that facilitates the absorption of acid gases. To further enhance the capture of CO by organic amine solvents 2 The development of more efficient and stable adsorbents is important, as well as the ability to enhance their stability, reduce corrosiveness and reduce energy consumption. The research has been carried out for many years, and the aqueous solution of MEA with single components is gradually developed into a composite low-energy-consumption absorbent, and the composition and stability of the absorbent are still the key contents of the research in the related fields.
Chinese patent document CN100418610C discloses a composite decarbonization solution for recovering carbon dioxide in exhaust gas: the absorbent is 20-60% of composite amine water solution, which contains one or more quick reaction rate amine (MEA, DEA, PZ) with lower concentration and one or more slow reaction rate amine (AMP, MEDA, TEA) with higher concentration; 5-10% of polyol ether, 1-5% of antioxidant, 1-5% of corrosion inhibitor and the balance of water, wherein the treatment capacity of flue gas per hour is 30000Nm 3 Recovering 3 ten thousand tons of CO with 99% purity 2 。
Chinese patent document CN101804286B discloses a mixed absorbent for capturing or separating carbon dioxide: the components mainly comprise 3-dimethylamino-1-propanol: 10-50wt%; primary and/or secondary amine: 5-10wt%; the rest is water. For capturing CO in flue gas 2 CO at 40 DEG C 2 Absorbing CO at 120deg.C at 15kPa 2 Desorption is carried out at a partial pressure of 50kPa, and 1 liter of absorbent aqueous solution can collect and separate CO 2 The amount of (2) was 70 g.
Chinese patent document CN106039936a discloses a two-phase amine absorbent for capturing carbon dioxide and its application, characterized in that: the water-based paint is a ternary component system composed of diethylenetriamine, pentamethyldiethylenetriamine and water, wherein the total concentration of the diethylenetriamine and the pentamethyldiethylenetriamine in the water is 4-5mol/L, and the mol ratio of the diethylenetriamine to the pentamethyldiethylenetriamine is 1:4-4:1; the two-phase amine absorbent is a homogeneous ternary mixed aqueous solution system before absorbing carbon dioxide, is separated into two phases after absorbing carbon dioxide and is enriched in the aqueous phase after being saturated.
Chinese patent (CN 102527192 a) discloses a carbon dioxide absorbent containing ionic liquid, wherein the content of ionic liquid in the absorbent is 5-50wt%, the content of alcohol amine is 5-50wt% and the content of water is 0-90wt%; the anion is an anion with an amino acid structure; the cation is organic amine salt cation and organic alcohol amine cation; the alcohol amine is monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, 2-amino-2-methyl-1-propanol; corrosion inhibitors and antioxidants may also be added.
In summary, the currently mainly applied amine liquid formula mainly uses MEA, DEA, AEEA as a main absorbent and PZ, MDEA, primary amine and secondary amine as auxiliary absorbents, and forms a carbon trapping solution by matching with various corrosion inhibitors and inhibitors for improving stability, so that the carbon trapping capability is low, the industrial energy consumption is high due to the existence of a large amount of aqueous solution, and the equipment corrosion can be increased during cyclic trapping. The mass fraction of the active components of the main absorption amine liquid is generally between 30% and 40%, the rest components are water, and under the conditions that the rich liquid circulates and the temperature is higher than 100 ℃, not only can the solution components be decomposed into unstable intermediates in a large amount, but also a large amount of water vapor is evaporated to bring about more energy consumption; oxygen existing in the flue gas can cause a great deal of degradation of main absorption quality, and the loss of solvent can reduce carbon capturing capacity and reduce economic benefit; the condensing system at the top of the regeneration tower also needs a large amount of circulating water to keep the components of the carbon capture solution balanced, thus bringing about more economic burden. Thus, there is still a great space for optimizing the carbon capture solution.
For this reason, the present subject group has developed a nonaqueous solution system against the problem of excessively high water content in the solution. Chinese patent CN104492226B discloses a nonaqueous decarbonizing solution for capturing carbon dioxide in a mixed gas: main suctionThe collecting component is N-ethylethanolamine, and the solvent is N, N-diethylethanolamine. Because the nonaqueous decarbonization liquid has high boiling point and low viscosity, and simultaneously, secondary amine which has high absorption rate, large absorption capacity and easy regeneration is used as a main absorption solvent, the absorption capacity, the purification degree and the desorption rate of carbon dioxide are improved, the reaction temperature range is enlarged, the volume of a regeneration tower is reduced, the regeneration energy consumption is greatly reduced, and the equipment investment and the operation cost are reduced. But the non-aqueous solution is used for capturing CO 2 When the catalyst is used, the catalyst is easy to react with oxygen in mixed flue gas, so that part of main absorbent of the solution is oxidized to lose absorption activity, the stability of the solution system is poor, and the energy consumption loss caused by overhigh water content in the solution is reduced, but the degradation of main active components causes unavoidable cost problems.
The subject group in 2018 chinese patent CN109012090B discloses an antioxidative nonaqueous decarbonization solution for capturing carbon dioxide in a mixed gas: the non-aqueous decarbonization solution consists of N-ethylethanolamine as main absorption component and N, N-diethylethanolamine as solvent, and has high boiling point, low viscosity, fast carbon dioxide absorption rate, great absorption capacity and easy regeneration. The antioxidant 2-butanone oxime, pyrogallol, carbohydrazide and N, N-bis (salicylidene) -1, 2-propanediamine are added, so that the main absorption component and the solvent can be effectively prevented from being oxidized by oxygen, and the good performance and the service life of the nonaqueous decarburization solution are ensured. However, there is still a great room for improvement, and the energy consumption is reduced, and the energy consumption still needs to be reduced; in industrial environment (in high temperature condition), a small amount of water vapor is inevitably generated, and the problem of serious moisture absorption exists in a non-aqueous solution system, so the problem of the non-aqueous solution still needs to be improved, and the improvement space of the non-aqueous solution is still huge.
Disclosure of Invention
The invention aims to develop the oxidation-degradation-resistant low-water amine liquid for capturing carbon dioxide in mixed flue gas, so as to solve the problems of low capturing capacity of decarbonized aqueous solution and non-aqueous solution, high regeneration energy consumption, unstable solution system, high degradation rate of main absorbent after being easily oxidized and degraded, poor capturing capacity and the like, and to maintain the high-efficiency capturing capacity of the low-water amine liquid in the flue gas with low carbon dioxide concentration and low pressure and improve the solution stability.
The technical scheme of the invention is as follows:
an oxidation resistant amine-lean liquid for capturing carbon dioxide in flue gas, the amine-lean liquid comprising:
solute: n-ethylethanolamine (EMEA) accounting for 10-30wt% of the water-less amine solution;
solvent one: n, N-diethyl ethanolamine (DEEA) accounts for 50-80wt% of the water-less amine solution;
solvent II: the Piperazine (PZ) aqueous solution accounts for 5-20wt% of the small aqueous amine solution.
Oxidation inhibitor: the sulfur-containing antioxidant and/or chelating agent accounts for 0.1-5.0wt% of the water-less amine liquid.
The concentration of the Piperazine (PZ) aqueous solution is 0.5-3.0mol/L.
The sulfur-containing antioxidant comprises one or more of 1,3, 4-thiadiazole-2, 5-dithiol (DMcT) and ethylene glycol dimercaptoacetate (EGBTG); the chelating agent comprises one or more of ethylenediamine tetraacetic acid (EDTA), diethylenetriamine pentaacetic acid (DTPA) and ethane-1-hydroxy-1, 1-diphosphonic acid (HEDP).
The invention also provides an application of the amine liquid with little water in capturing carbon dioxide in mixed gas, which is applied to the carbon dioxide-containing industrial waste gas of power plant flue gas, oil refinery, steel mill, cement plant, chemical plant tail gas, water gas, biogas, natural gas or carbonate ore decomposition gas, and captures carbon dioxide gas generated in the production process, thus having wide application prospect. In addition, the low-water amine liquid can still have better solution stability after thermal degradation caused by high temperature of industrial devices and oxidative degradation caused by oxygen.
The use conditions are as follows: the pressure is 0-1.2MPa, and the temperature is 110-140 ℃.
The invention takes N-ethylethanolamine (EMEA) as solute, and has the advantages that:
1) EMEA is secondary amine, has an atmospheric boiling point of 170.0 ℃, is not easy to volatilize, and has a certain space positionResistance effect on CO 2 Is loaded with 30-40wt% of EMEA low-water amine solution to CO under the condition of 313K and normal pressure 2 Is loaded in an amount of 0.80-1.20mol CO 2 /molamine。
2) Absorption of CO by EMEA with less aqueous amine solutions 2 Is faster, 40wt% of EMEA less aqueous amine liquid absorbs CO 2 Average reaction rate 96Nm 3 CO 2 /m 3 amine/h, which has a higher reaction rate than the conventional secondary amine Diethanolamine (DEA), diisopropanolamine (DIPA).
3) The corrosion resistance of the high concentration EMEA solution is higher than that of the traditional MEA solution.
4) EMEA is not volatile, and its volatility is significantly lower than MEA.
5) The regeneration energy consumption of EMEA is low.
6) EMEA can be prepared from renewable resources, and really realizes green production and use.
N, N diethyl ethanolamine DEEA is used as a solvent, and has the advantages that:
1) DEEA has a boiling point of 163 ℃ under normal pressure and is not easy to volatilize; the viscosity is 4.05mPas at 25 ℃ and 1.50mPas at 60 ℃, the viscosity is small, so that the mass transfer in the absorption process is fast, and the absorption rate is accelerated.
2) DEEA is a tertiary amine, capturing CO in EMEA 2 DEEA can be used as absorbent to participate in the reaction to improve CO 2 Loading and absorption rate of CO 2 The reaction rate with DEEA is higher than that of the traditional tertiary amine N-Methyldiethanolamine (MDEA).
3) DEEA has high physical and chemical stability.
4) DEEA can be prepared from renewable resources, and really realizes green production and use.
The Piperazine (PZ) water solution is used as a solvent, and has the advantages that:
1) The boiling point of PZ under normal pressure is 146 ℃, and the PZ is not easy to volatilize; the viscosity of the PZ aqueous solution is 3.15mPas at 25 ℃, and the viscosity is 1.40mPas at 60 ℃, so that the mass transfer in the absorption process is fast, and the absorption rate is accelerated.
2) PZ can enhance amine liquid stability and reduce degradation of less aqueous amine liquid.
3) The PZ has better antioxidation inhibition effect and stable performance.
4) PZ can be prepared from renewable resources, and really realizes green production and use.
The invention has the following effects and benefits: firstly, the antioxidant amine liquid with little water can capture 2 to 95 percent of carbon dioxide in mixed gas and has 0.934mol of CO 2 High solution uptake of/molamine, 0.878molCO 2 High solution desorption amount of molamine, complete desorption in 60min, and desorption rate over 94%. The traditional multi-aqueous solution has low desorption rate and desorption amount, the desorption can be completed within 90 minutes, and the desorption rate is between 50 and 70 percent. Because the traditional solution absorbs carbon dioxide before, the desorption temperature is generally higher than 100 ℃, and the water used as a solvent is evaporated after the desorption temperature is higher than the normal boiling point of water, so that a large amount of heat energy is lost, and a small amount of steam cannot be generated in industrial capturing, the invention uses DEEA with high boiling point and PZ aqueous solution, and has the advantages of low viscosity, fast mass transfer, low regeneration temperature, almost no volatilization during regeneration and greatly reduced regeneration energy consumption. Meanwhile, the defects of high solution viscosity and slow mass transfer caused by the influence of water vapor in the trapping process of most nonaqueous solvents are overcome.
After the sulfur-containing antioxidant and/or chelating agent are added into the amine liquid with little water, the reaction is not affected, the absorption and desorption performance of the regenerated solution after thermal degradation or oxidative degradation can be improved, the content of main absorber EMEA of the amine liquid with little water is greatly reserved, and the degradation degree is reduced. Especially chelating agents EDTA and DTPA can greatly improve the degradation resistance of the solution and the CO of the regenerated solution 2 Absorbing and desorbing capacity. In addition, even in the presence of both thermal and oxidative degradation, the chelant-added low-water amine solution still exhibits good stability, with the main absorber EMEA degrading to a lesser extent than the non-inhibitor-added low-water amine solution. In a word, the antioxidant amine liquid with little water has excellent degradation resistance and good stability, and is suitable for recycling carbon dioxide in various chemical reaction tail gases, combustion flue gases, ore decomposition gases, natural gas, coal gas and biogas.
Drawings
FIG. 1 is a diagram of a device for absorbing and desorbing carbon dioxide from a small aqueous amine solution.
FIG. 2 is a first degradation apparatus.
FIG. 3 is a second degradation device.
Fig. 4 is the EMEA mass concentration after oxidative degradation of the reduced aqueous amine solution with the addition of a sulfur-containing antioxidant.
Fig. 5 is the EMEA mass concentration after oxidative degradation of the amine-lean liquid with the addition of a chelating agent.
Figure 6 is the capture capacity after oxidative degradation of a reduced aqueous amine liquid with the addition of a sulfur-containing antioxidant.
FIG. 7 is the capture capacity after oxidative degradation of a less aqueous amine liquid with the addition of a chelating agent.
Fig. 8 is a graph showing the change of EMEA mass concentration after oxidative degradation of a small aqueous amine solution with EDTA and DTPA added to a No. two degradation apparatus, respectively.
FIG. 9 is a graph of the change in EMEA mass concentration of EMEA less aqueous amine solution under thermal degradation conditions; EMEA mass concentration change pattern of EMEA low-water amine liquid and low-water amine liquid added with EDTA and DTPA respectively under the condition of simultaneous thermal degradation and oxidative degradation.
FIG. 10 is EMEA reduced water amine solution CO 2 Absorption desorption performance characterization graph.
Fig. 11 is a graph of EMEA mass concentration change after oxidative degradation of EMEA low water amine liquid.
Fig. 12 is the trapping capacity after EMEA low water amine hydrothermal degradation and oxidative degradation.
FIG. 13 is the capture capacity after oxidative degradation of a less aqueous amine solution with an oxime inhibitor added.
FIG. 14 is the capture capacity after oxidative degradation of amine-lean liquid with the addition of an oxide film inhibitor. Wherein 1 is mass flowmeter, 2 is the drying bottle, 3 is the condenser, 4 is the three-necked flask, 5 is the thermometer, 6 is the rotor, 7 is the oil bath, 8 is the buffer bottle, 9 is the wet gas flowmeter, 10 is the oven, 11 is the admission valve, 12 is the air outlet valve, 13 is the manometer, 14 is the autoclave, 15 is the gas phase valve, 16 is the hasp, 17 is the handle, 18 is the snap ring, 19 is the heat exchanger, 20 is operating panel, 21 is the liquid valve.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings and technical schemes.
Example 1 investigation of the Property of oxidative degradation of amine liquid containing a Sulfur-containing antioxidant
Two sets of a small water EMEA amine solution of 200g25wt% EMEA+70wt% DEEA+5% PZ aqueous solution (the concentration of the PZ aqueous solution is 1 mol/L) were prepared, and a sulfur-containing antioxidant 1,3, 4-thiadiazole-2, 5-dithiol (DMcT) aqueous solution and an ethylene glycol dimercaptoacetate (EGBTG) aqueous solution, each having a mass of 3.0g and a concentration of 0.01mol/L, were added to each of them, to obtain a small water amine solution containing a sulfur-containing antioxidant, and the small water amine solution was added to a degradation apparatus I (the apparatus was composed of four 300mL high-pressure reaction kettles, see FIG. 2), and two sets of oxidative degradation experiments were performed. In the first set of experiments, 1,3, 4-thiadiazole-2, 5-dithiol (DMcT) was added and labeled as pot number 1. In a second set of experiments, ethylene glycol dimercaptoacetate (EGBTG), labeled as kettle number 2, was added. In order to ensure the accuracy of the reaction result, the reaction period is not sampled, and the concentration of the solution is respectively tested after the reaction is finished. Because the experiment needs to control variables, the two groups of experiments are ensured to be different in inhibitor removal and the rest conditions are the same. In order to simulate the oxidative degradation in industry, the solutions in the two groups of reaction kettles respectively absorb 2L of carbon dioxide in an absorption and desorption device shown in figure 1 (the absorption temperature is 40 ℃ and the flow rate is 250ml/min, and CO with the concentration of 99.995% is introduced in 8 minutes before the oxidative degradation is carried out) 2 ) Other variables such as temperature of 70℃and 13% O were introduced into the two kettles 2 +87％N 2 The pressure of the mixed gas is 0.4MPa. Finally, the reaction was continued under the above conditions for 15 days, and regeneration was performed, and the mass fractions of EMEA after the addition of 1,3, 4-thiadiazole-2, 5-dithiol (DMcT), ethylene glycol dimercaptoacetate (EGBTG) were examined to be 19.9wt% and 18.5wt%, respectively (see fig. 4).
Example 2 Property investigation of oxidative degradation of amine liquid with less aqueous chelating agent
Three sets of EMEA (25 g, 25 wt.%) EMEA (70 wt.%) DEEA (5 wt.%) PZ aqueous solution (PZ aqueous solution with a concentration of 1 mol/L) EMEA water-less amine solution were prepared, and 3.0g of chelating agent ethylenediamine tetraacetic acid (EDTA), diethylene Triamine Pentaacetic Acid (DTPA) aqueous solution and ethane-1-hydroxy-1, 1-diphosphate (HEDP) aqueous solution with a concentration of 0.01mol/L were added to obtain a chelating agent water-less amine solutionAmine liquid was added to the degradation apparatus one (see fig. 2) and three oxidative degradation experiments were performed. In the first set of experiments, ethylenediamine tetraacetic acid (EDTA) was added and labeled as kettle No. 1. In a second set of experiments, diethylenetriamine pentaacetic acid (DTPA) was added, labeled as kettle No. 2. In a third set of experiments, ethane-1-hydroxy-1, 1-diphosphate (HEDP) was added and labeled as kettle number 3. In order to ensure the accuracy of the reaction result, the reaction period is not sampled, and the concentration of the solution is respectively tested after the reaction is finished. Because the experiment needs to control variables, the three groups of experiments are ensured to be different in inhibitor removal and the rest conditions are the same. In order to simulate industrial oxidative degradation, the solutions in the three groups of reaction kettles respectively absorb 2L of carbon dioxide in an absorption and desorption device shown in figure 1 (the absorption temperature is 40 ℃ and the flow rate is 250ml/min, and CO with the concentration of 99.995% is introduced in 8 minutes before the solution is subjected to oxidative degradation 2 ) Other variables such as temperature of 70 ℃ and three kettles are introduced with 13% O 2 +87％N 2 The pressure of the mixed gas is 0.4MPa. Finally, the reaction was continued under the above conditions for 15 days, and regeneration was performed, and mass fractions of EMEA after addition of ethylenediamine tetraacetic acid (EDTA), diethylenetriamine pentaacetic acid (DTPA) and ethane-1-hydroxy-1, 1-diphosphate (HEDP) were examined, respectively, to be 23wt%, 22.7wt% and 20wt% (see fig. 5).
Example 3 absorption Desorption Performance test of amine liquid containing less water after oxidative degradation with Sulfur inhibitor
The aqueous amine solutions of 1,3, 4-thiadiazole-2, 5-dithiol (DMcT) and ethylene glycol dimercaptoacetate (EGBTG) added as described in example 1 were subjected to oxidative degradation and then charged into 500ml of a reactor equipped with a constant temperature oil bath stirrer, respectively (experimental apparatus see FIG. 1). Introducing CO with the pressure of 0.2MPa and the concentration of 99.995% at the temperature of 40 ℃ and the flow rate of 250ml/min 2 The absorption rate and the absorption amount of carbon dioxide were calculated by continuously measuring the carbon dioxide with a wet type corrosion-resistant flowmeter. After the solution reached saturation, desorption was performed by setting the temperature of the oil bath to 120℃and measuring the desorption amount and desorption rate at 60 minutes. Absorption of 0.822molCO after addition of 1,3, 4-thiadiazole-2, 5-dithiol (DMcT) 2 Molamine, desorption 0.755mol CO 2 Molamine, desorption efficiency 91.8%; the absorption amount after adding ethylene glycol dimercaptoacetate (EGBTG) is 0.774molCO 2 Molamine, desorption amount 0.713molCO 2 Molamine, desorption efficiency 92.1% (see FIG. 6).
Example 4 absorption Desorption Performance test of amine liquid containing less Water after oxidative degradation with chelating agent inhibitor
The aqueous amine solutions of ethylenediamine tetraacetic acid (EDTA), diethylenetriamine pentaacetic acid (DTPA) and ethane-1-hydroxy-1, 1-diphosphonic acid (HEDP) described in example 2 were subjected to oxidative degradation and then charged into 500ml of a reactor equipped with a constant temperature oil bath stirrer, respectively (experimental apparatus see FIG. 1). Introducing CO with the pressure of 0.2MPa and the concentration of 99.995% at the temperature of 40 ℃ and the flow rate of 250ml/min 2 The absorption rate and the absorption amount of carbon dioxide were calculated by continuously measuring the carbon dioxide with a wet type corrosion-resistant flowmeter. After the solution reached saturation, desorption was performed by setting the temperature of the oil bath to 120℃and measuring the desorption amount and desorption rate at 60 minutes. Absorption of 0.924molCO after EDTA addition 2 Molamine, desorption amount 0.855mol CO 2 Molamine, desorption efficiency 92.5%; absorption of 0.925mol CO after addition of DTPA 2 Molamine, desorption 0.862molCO 2 Molamine, desorption efficiency 93.1%; absorption of 0.804mol CO after addition of HEDP 2 Molamine, desorption 0.742mol CO 2 Molamine, desorption efficiency 92.2% (see FIG. 7).
Example 5 investigation of Performance of oxidative degradation of amine Dihydroamide with added inhibitor EDTA, DTPA
Two sets of 200g of 25wt% EMEA+70wt% DEEA+5% PZ aqueous solution (PZ aqueous solution having a concentration of 1 mol/L) were prepared, and 3.0g of 0.01mol/L EDTA aqueous solution and DTPA aqueous solution were added, respectively, to carry out an oxidative degradation experiment. The apparatus was a Micro-Reactor manufactured by the petrographic instruments company, and the Reactor body was made of 250mL stainless steel 316L. On the one hand, the highest temperature allowed to be used by the equipment is 573.15K, the temperature can be accurately controlled to +/-1 ℃, the temperature range of oxidative degradation and thermal degradation of EMEA solution can be met, and meanwhile, the equipment is provided with a safety interlock: the over-temperature and over-pressure alarm is given, the work is stopped, the heating is cut off, and the upper limit temperature can be customized. On the other hand, the stirring speed of the equipment can reach 1500r/min at the highest, the + -2 r/min can be accurately controlled, the amine liquid and the gas can be fully reacted, and the product is producedThe raw vortex increases the reaction area, and the stirring speed is set to be 350r/min in the experiment. Meanwhile, the liquid sample to be detected is taken out every 72 hours, and the normal reaction is not affected by the property of the analysis solution. Finally, the device can bear the highest pressure of 25Mpa, and the two solutions absorb 2LCO 2 And introducing 0.4Mpa mixed gas (13% O) 2 And 87% N 2 ) The pressure is usually less than 1Mpa later, and a temperature control monitoring and pressure detecting system can be preset to ensure that the degradation reaction is more accurately carried out. The two groups of solutions were each subjected to 2L of carbon dioxide absorption in an absorption/desorption apparatus shown in FIG. 1 (absorption temperature: 40 ℃ C., flow rate: 250ml/min, and CO having a concentration of 99.995% was introduced for 8 minutes) 2 ) Then the mixture is added into a second degradation device (see figure 3), the temperature of the reaction kettle is kept at 70 ℃, and 13 percent of O is introduced into the kettle 2 +87％N 2 The pressure of the mixed gas is 0.4MPa. The final degradation reaction time was 15 days, and samples were taken every 3 days for analysis, and the mass fraction of EMEA was examined separately (see fig. 8). It can be found that under oxidative degradation conditions, the inhibitors EDTA and DTPA show good stability, the mass concentration of the main absorber EMEA can reach more than 22wt%, the degradation rate is lower than that of the less aqueous amine solution without the inhibitor by 18% and the decrease trend is slow.
Example 6 investigation of the Performance of the inhibitors EDTA, DTPA in the Presence of thermal and oxidative degradation
Two groups of aqueous amine solutions of 200g25wt% EMEA+70wt% DEEA+5% PZ (PZ aqueous solution concentration of 1 mol/L) were prepared, and 3.0g EDTA and DTPA were added to the one group and the other group, respectively, at a concentration of 0.01mol/L, and oxidative degradation and thermal degradation were performed simultaneously. The two groups of solutions were each subjected to 2L of carbon dioxide absorption in an absorption/desorption apparatus shown in FIG. 1 (absorption temperature: 40 ℃ C., flow rate: 250ml/min, and CO having a concentration of 99.995% was introduced for 8 minutes) 2 ) Then the mixture is added into a second degradation device (see figure 3), the temperature of the reaction kettle is kept at 140 ℃, and 13 percent of O is introduced into the kettle 2 +87％N 2 The pressure of the mixed gas is 0.4MPa. The final degradation reaction time was 15 days, and samples were taken every 3 days for analysis, and the mass fraction of EMEA was examined separately (see fig. 9). It was found that the inhibitors EDTA and DTPA still exhibited both oxidative and thermal degradationThe stability is good, and the degradation rate of the main absorbent is lower than that of the less aqueous amine liquid without the inhibitor.
Comparative example 1 absorption and desorption Performance test of EMEA less aqueous amine solution
200g of an EMEA-reduced aqueous amine solution of 25wt% EMEA+70wt% DEEA+5% PZ in water (PZ in water at a concentration of 1 mol/L) were charged into a 500ml reactor equipped with a constant temperature oil bath stirrer (experimental apparatus see FIG. 1). Introducing CO with the pressure of 0.2MPa and the concentration of 99.995% at the temperature of 40 ℃ and the flow rate of 250ml/min 2 The absorption rate and the absorption amount of carbon dioxide were calculated by continuously measuring the carbon dioxide with a wet type corrosion-resistant flowmeter. After the solution reached saturation, desorption was performed by setting the temperature of the oil bath to 120℃and measuring the desorption amount and desorption rate at 60 minutes (see FIG. 10). EMEA aqueous-amine-reduced solution absorption of 0.934mol CO 2 Molamine, desorption 0.878molCO 2 Molamine, desorption efficiency 94.1%.
Comparative example 2 investigation of the Property of oxidative degradation of EMEA less aqueous amine liquid
200g of an EMEA-reduced aqueous amine solution of 25wt% EMEA+70wt% DEEA+5% PZ aqueous solution (the concentration of the PZ aqueous solution is 1 mol/L) was prepared, an antioxidant was not added, and the mixture was added to a second degradation apparatus (see FIG. 3), the EMEA-reduced aqueous amine solution was labeled as a No. 1 kettle, and samples were taken every 3 days during the reaction. In order to simulate the oxidative degradation in industry, the solution in the No. 1 kettle absorbs 2L of carbon dioxide in an absorption and desorption device shown in FIG. 1 (the absorption temperature is 40 ℃, and CO with the concentration of 99.995% is introduced for 8 minutes at the flow rate of 250 ml/min) 2 ) Maintaining the temperature of the reaction kettle at 70 ℃, and introducing 13% O by volume into the kettle 2 +87％N 2 The pressure of the mixed gas is 0.4MPa. Finally, the mass fraction of EMEA was examined after 15 days of degradation (see FIG. 11), and after oxidative degradation, the mass fraction of EMEA in the amine-lean solution was 17wt%.
Comparative example 3 investigation of the Property of thermal degradation of EMEA less aqueous amine solutions
200g of an EMEA-reduced aqueous amine solution of 25wt% EMEA+70wt% DEEA+5% PZ aqueous solution (PZ aqueous solution concentration of 1 mol/L) was prepared, and added to a second degradation apparatus (see FIG. 3), the EMEA-reduced aqueous amine solution was labeled as a No. 1 pot, and samples were taken every 3 days during the reaction. In order to simulate industrial thermal degradation, the No. 1 kettle is internally dissolvedThe liquid was subjected to absorption of 2L of carbon dioxide in an absorption/desorption apparatus shown in FIG. 1 (absorption temperature: 40 ℃ C., flow rate: 250ml/min, and CO having a concentration of 99.995% was introduced for 8 minutes) 2 ) Maintaining the temperature of the reaction kettle at 140 ℃, and introducing protective gas N into the kettle 2 The pressure was 0.4MPa. Finally, the degradation reaction is carried out for 15 days, and the mass fraction of EMEA (see figure 9) is examined, wherein after thermal degradation, the mass fraction of EMEA in the low-water amine solution is 17.8wt%.
Comparative example 4 investigation of Performance in the Presence of both thermal and oxidative degradation of an EMEA-reduced aqueous amine solution
200g of an EMEA-reduced aqueous amine solution of 25wt% EMEA+70wt% DEEA+5% PZ aqueous solution (PZ aqueous solution concentration of 1 mol/L) was prepared, and added to a second degradation apparatus (see FIG. 3), the EMEA-reduced aqueous amine solution was labeled as a No. 1 pot, and samples were taken every 3 days during the reaction. In order to simulate industrial thermal degradation and oxidative degradation, the solution in the No. 1 kettle was subjected to 2L of carbon dioxide absorption in an absorption and desorption apparatus shown in FIG. 1 (absorption temperature was 40 ℃ C., and CO with a concentration of 99.995% was introduced at a flow rate of 250ml/min for 8 minutes) 2 ) Maintaining the temperature of the reaction kettle at 140 ℃, and introducing 13% O by volume into the kettle 2 +87％N 2 The pressure of the mixed gas is 0.4MPa. Finally, the mass fraction of EMEA was examined 15 days after the degradation reaction (see FIG. 9), and the mass fraction of EMEA in the amine-lean solution was 16wt% after thermal degradation and oxidative degradation.
Comparative example 5 examination of absorption and desorption capacities after degradation of EMEA minor aqueous amine solution
The EMEA little aqueous amine solution after oxidative degradation of comparative example 2 or thermal degradation of comparative example 3 was charged into a 500ml reactor equipped with a constant temperature oil bath stirrer (experimental apparatus see fig. 1). Introducing CO with the pressure of 0.2MPa and the concentration of 99.995% at the temperature of 40 ℃ and the flow rate of 250ml/min 2 The absorption rate and the absorption amount of carbon dioxide were calculated by continuously measuring the carbon dioxide with a wet type corrosion-resistant flowmeter. After the solution reached saturation, desorption was performed by setting the temperature of the oil bath to 120℃and measuring the desorption amount and desorption rate at 60 minutes (see FIG. 12). After the EMEA less aqueous amine solution is oxidized and degraded, the absorption capacity of the EMEA less aqueous amine solution is 0.757mol CO 2 Molamine, desorption amount 0.701molCO 2 Molamine, desorption efficiency 92.6%. After EMEA little water amine solution is thermally degraded, the absorption amount of CO is 0.765mol 2 Molamine, desorption amount 0.711molCO 2 The desorption efficiency of the amine/mol is 92.9 percent.
Comparative example 7 absorption and desorption Performance test after oxidative degradation of less aqueous amine solution after addition of oxime inhibitors
Two sets of oxidative degradation experiments were performed by preparing two sets of 200g of an EMEA-less aqueous amine solution of 25wt% emea+70wt% deea+5% PZ aqueous solution (the concentration of the PZ aqueous solution is 1 mol/L), adding 3.0g of oxime inhibitors butanone oxime and acetoxime, respectively, and adding them to the degradation apparatus one (see fig. 2). In the first set of experiments, butanone oxime labeled as kettle number 1 was added. In the second set of experiments, acetone oxime, labeled kettle number 2, was added. In order to ensure the accuracy of the reaction result, the reaction period is not sampled, and the concentration of the solution is respectively tested after the reaction is finished. Because the experiment needs to control variables, the two groups of experiments are ensured to be different in inhibitor removal and the rest conditions are the same. In order to simulate the oxidative degradation in industry, the solutions in the two groups of reaction kettles respectively absorb 2L of carbon dioxide in an absorption and desorption device (see figure 1) (the absorption temperature is 40 ℃, the flow rate is 250ml/min, and CO with the concentration of 99.995% is introduced for 8 minutes) 2 ) Other variables such as temperature of 70℃and 13% O were introduced into the two kettles 2 +87％N 2 The mixture gas, the pressure of which is 0.4MPa, is continuously reacted for 15 days under the above conditions, and regeneration is carried out. The small aqueous amine solutions added with butanone oxime and acetoxime are respectively filled into 500ml reactors equipped with constant temperature oil bath agitators after oxidative degradation (experimental apparatus see figure 1). Introducing CO with the pressure of 0.2MPa and the concentration of 99.995% at the temperature of 40 ℃ and the flow rate of 250ml/min 2 The absorption rate and the absorption amount of carbon dioxide were calculated by continuously measuring the carbon dioxide with a wet type corrosion-resistant flowmeter. After the solution reached saturation, desorption was performed by setting the temperature of the oil bath to 120℃and measuring the desorption amount and desorption rate at 60 minutes (see FIG. 13). Absorption of 0.630mol CO after addition of acetoxime 2 Molamine, desorption 0.586mol CO 2 Molamine, desorption efficiency 93.1%; absorption of 0.536mol CO after butanone oxime addition 2 Molamine, desorption 0.486molCO 2 Molamine, desorption efficiency 90.2%.
Comparative example 8 absorption and desorption Performance test after oxidative degradation of less aqueous amine solution after addition of Oxidation film inhibitor
Two sets of EMEA small aqueous amine solutions of 200g25wt% emea+70wt% deea+5% PZ aqueous solution (the concentration of the PZ aqueous solution is 1 mol/L) were prepared, 3.0g of an aqueous potassium sodium tartrate solution and an aqueous sodium metavanadate solution, which are oxide film inhibitors, were added to a degradation apparatus one (see fig. 2), respectively, and two sets of oxidative degradation experiments were performed. In the first set of experiments, sodium potassium tartrate was added and labeled as kettle number 1. In the second set of experiments, sodium metavanadate, labeled as kettle number 2, was added. In order to ensure the accuracy of the reaction result, the reaction period is not sampled, and the concentration of the solution is respectively tested after the reaction is finished. Because the experiment needs to control variables, two groups of experiments are ensured to be different in inhibitor removal, and other conditions are the same. In order to simulate the oxidative degradation in industry, the solutions in the two groups of reaction kettles respectively absorb 2L of carbon dioxide in an absorption and desorption device (see figure 1) (the absorption temperature is 40 ℃, the flow rate is 250ml/min, and CO with the concentration of 99.995% is introduced for 8 minutes) 2 ) Other variables such as temperature of 70℃and 13% O were introduced into the two kettles 2 +87％N 2 The mixture gas, the pressure of which is 0.4MPa, is continuously reacted for 15 days under the above conditions, and regeneration is carried out. The aqueous amine solutions containing potassium sodium tartrate and sodium metavanadate were subjected to oxidative degradation, and then were respectively charged into 500ml reactors equipped with constant-temperature oil bath agitators (experimental apparatus see fig. 1). Introducing CO with the pressure of 0.2MPa and the concentration of 99.995% at the temperature of 40 ℃ and the flow rate of 250ml/min 2 The absorption rate and the absorption amount of carbon dioxide were calculated by continuously measuring the carbon dioxide with a wet type corrosion-resistant flowmeter. After the solution reached saturation, desorption was performed by setting the temperature of the oil bath to 120℃and measuring the desorption amount and desorption rate at 60 minutes (see FIG. 14). Adding sodium metavanadate to absorb 0.628mol CO 2 Molamine, desorption 0.578mol CO 2 Molamine, desorption efficiency 92.1%; absorption of 0.667mol CO after addition of Potassium sodium tartrate 2 Molamine, desorption 0.617molCO 2 Molamine, desorption efficiency 92.4%.
The EMEA water-free amine solution has high absorption and desorption rate and high desorption efficiency. After thermal degradation and oxidative degradation, the stability is obviously improved greatly compared with other solutions (such as an MEA aqueous solution system and the like), the regenerated solution not only well maintains the mass concentration of the main absorbent, but also has higher absorption performance and good degradation resistance.
After the sulfur-containing antioxidant, the chelating agent, the oxime antioxidant and the oxide film corrosion inhibitor are respectively added into the EMEA water-free amine liquid in different proportions, the mass concentration of the main absorbent is maintained to a certain extent by all the inhibitors, and the degradation rate is reduced. However, after oxidative degradation, oxime inhibitors and oxide film inhibitors are poor in performance, and the trapping capacity of the amine liquid with little water is not improved; after different sulfur-containing inhibitors are added, the carbon dioxide capturing capacity is improved; chelating agent inhibitor greatly improves CO capture 2 Wherein: absorption of 0.924molCO after EDTA addition 2 Per mole of amine, desorption amount of 0.855 mole of CO 2 Molamine, desorption efficiency 92.5%; absorption of 0.925molCO after addition of DTPA 2 Molamine, desorption 0.862molCO 2 The desorption efficiency of molamine is 93.1%, which is different from EMEA water-reduced amine solution in the aspect of absorption and desorption capacity by less than 5%, and the desorption efficiency is almost the same. The degradation rate of the main absorbent is only 15-20%, and the degradation rate of the EMEA aqueous solution without the inhibitor is as high as more than 35%, so that the stability of the amine liquid with little water is obviously improved. And under the condition that oxidative degradation and thermal degradation exist simultaneously, the inhibitor EDTA and DTPA still show good stability, and the degradation rate of the main absorbent is lower than that of the less aqueous amine liquid without the inhibitor. However, as the reaction time increases, the oxidation resistance gradually decreases until it is completely consumed and becomes ineffective, so that the solution needs to be periodically replenished according to the actual content.
Claims (6)
1. An oxidation resistant, low water amine liquid for capturing carbon dioxide in flue gas, characterized by: the components comprise:
solute: n-ethylethanolamine accounts for 10-30wt% of the water-less amine solution;
solvent one: n, N-diethyl ethanolamine accounts for 50-80wt% of the water-less amine solution;
solvent II: the mass fraction of the piperazine aqueous solution and the small aqueous amine solution is 5-20wt%.
Oxidation inhibitor: the sulfur-containing antioxidant and/or chelating agent accounts for 0.1-5.0wt% of the water-less amine liquid.
2. An oxidation resistant amine lean liquid for capturing carbon dioxide in flue gas according to claim 1, wherein: the concentration of the piperazine aqueous solution is 0.5-3mol/L.
3. An oxidation resistant amine lean liquid for capturing carbon dioxide in flue gas according to claim 1, wherein: the sulfur-containing antioxidant comprises one or more of 1,3, 4-thiadiazole-2, 5-dithiol and ethylene glycol dimercaptoacetate; the chelating agent comprises one or more of ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid and ethane-1-hydroxy-1, 1-diphosphonic acid.
4. Use of the oxidation resistant amine-lean liquid of claim 1 for capturing carbon dioxide in a mixed gas, characterized in that: the method is applied to the carbon dioxide-containing industrial waste gas of power plant flue gas, oil refinery, steel mill, cement plant, chemical plant tail gas, water gas, biogas, natural gas or carbonate ore decomposition gas.
5. The use of the oxidation resistant amine-lean liquid of claim 4 for capturing carbon dioxide in a gas mixture, wherein: the method is applied to the environments of thermal degradation caused by high temperature and oxidative degradation caused by oxygen in industrial devices.
6. The use of the oxidation resistant amine-lean liquid of claim 4 for capturing carbon dioxide in a gas mixture, wherein: the use conditions are as follows: the pressure is 0-1.2MPa, and the temperature is 110-140 ℃.
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