CN114849653A - Amine modified porous molecular sieve for efficiently trapping carbon dioxide, and preparation method and application thereof - Google Patents
Amine modified porous molecular sieve for efficiently trapping carbon dioxide, and preparation method and application thereof Download PDFInfo
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- CN114849653A CN114849653A CN202210516342.3A CN202210516342A CN114849653A CN 114849653 A CN114849653 A CN 114849653A CN 202210516342 A CN202210516342 A CN 202210516342A CN 114849653 A CN114849653 A CN 114849653A
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- molecular sieve
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 65
- 150000001412 amines Chemical class 0.000 title claims abstract description 51
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 33
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001291 vacuum drying Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000000967 suction filtration Methods 0.000 claims abstract description 8
- 239000012265 solid product Substances 0.000 claims abstract description 6
- -1 amine modified molecular sieve Chemical class 0.000 claims abstract description 4
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 17
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 12
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000003546 flue gas Substances 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000002594 sorbent Substances 0.000 claims 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 7
- 229960001124 trientine Drugs 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- 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
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- 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
- B01D53/81—Solid phase processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/80—Organic bases or salts
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
The invention relates to an amine modified porous molecular sieve for efficiently trapping carbon dioxide, a preparation method and application thereof, wherein the preparation process comprises the following steps: dissolving organic amine in a mixed solution of ethanol and water to obtain a mixed solution A; adding metal salt into the mixed solution A, and stirring at normal temperature to obtain mixed solution B; adding a molecular sieve into the mixed solution B, and oscillating and dipping in a shaking table to obtain a solid-liquid mixture C; and carrying out suction filtration on the solid-liquid mixture C to obtain a solid product D, and carrying out vacuum drying on the solid product D to obtain a modified porous molecular sieve product. Compared with the prior art, the preparation method of the organic amine modified molecular sieve is simple, and the obtained organic amine modified molecular sieve has good carbon dioxide adsorption rate and adsorption capacity, and is a carbon dioxide adsorption material with an industrial application prospect.
Description
Technical Field
The invention relates to the field of carbon dioxide trapping functional materials, in particular to an amine modified porous molecular sieve for efficiently trapping carbon dioxide, a preparation method and application thereof.
Background
The rapid growth of the global population and the dependence of industrial development on the excessive exploitation and use of fossil fuels lead to the continuous rise of carbon dioxide concentration in the atmosphere and the acceleration of climate change, which brings serious threat to human survival. The carbon dioxide capture technology is a technical method for capturing, fixedly storing or converting carbon dioxide in an emission point source or air, is the most economical and feasible carbon emission reduction technology at present, and is an important means for realizing a carbon neutralization target.
In recent years, researchers have developed many advanced carbon dioxide capture methods. Among these methods, the liquid amine absorption method has been industrially applied in carbon dioxide capture. The method has the advantages of high trapping efficiency, large adsorption capacity and the like; but has the defects of poor stability of the absorbent, corrosion on equipment, high regeneration energy consumption and the like, and limits the wide application of the absorbent.
To overcome these disadvantages, researchers have proposed strategies to use porous materials as solid absorbents instead of liquid amines for capturing carbon dioxide, and the development of high adsorption capacity, stable, efficient, and inexpensive porous adsorbents is among them key. The molecular sieve is a porous adsorbent with moderate price, but the unmodified molecular sieve has lower carbon dioxide adsorption capacity, slower adsorption rate and high desorption energy consumption.
Patent CN109046258A discloses a molecular sieve for efficiently adsorbing environmental carbon dioxide, which is modified by organic amine on the inner and outer surfaces of the molecular sieve by a simple impregnation method, wherein the method has high organic amine usage amount and poor organic amine stability. Patent CN107376854A discloses a preparation method of bifunctional KIT-6/ZSM-5 for adsorbing carbon dioxide in flue gas, in the method, organic amine is fixed on a microporous mesoporous composite molecular sieve in a mode of grafting a silane coupling agent, so that the adsorption performance is enhanced, the adsorption stability is improved, and the adsorption capacity of the modified molecular sieve is lower. Patent CN113877539A discloses a CO 2 The patent refers to the field of 'adsorption of volatile compounds in liquids or other substances'. Therefore, research and development of CO with high absorption capacity, high stability and adaptability to different emission sources 2 The trapped adsorbent material is of great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an amine modified porous molecular sieve for efficiently trapping carbon dioxide, a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
the first object of the present invention is to provide a method for preparing an amine modified porous molecular sieve for efficiently capturing carbon dioxide, comprising the steps of:
s1: dissolving organic amine in a mixed solution of ethanol and water to obtain a mixed solution A;
s2: adding metal salt into the mixed solution A, and stirring for 2-4 hours at normal temperature to obtain a mixed solution B;
s3: adding a molecular sieve into the mixed solution B, and oscillating and dipping in a shaking table to obtain a solid-liquid mixture C;
s4: and carrying out suction filtration on the solid-liquid mixture C to obtain a solid product D, and carrying out vacuum drying on the solid product D to obtain a modified porous molecular sieve product.
In S1, the organic amine is a mixture of two or more of ethanolamine, ethylenediamine, diethanolamine, polyvinylamine, imidazole, piperazine, polyethyleneimine, tetraethylenepentamine, triethylenetetramine, and diethylenetriamine. Preferably two or three of triethylene tetramine, diethylene triamine and piperazine. Any mass ratio of the two is 0.01-10: 1, or a combination thereof.
Further, in S1 to S3:
the mass ratio of the organic amine to the ethanol is 1: 1-20, preferably 1: 10-15; the ratio of ethanol to water is 1: 0.1 to 10, preferably 1: 1-2; the mass ratio of the organic amine to the metal salt is 1: 0.01 to 0.2, preferably 1: 0.05 to 0.1; the mass ratio of the molecular sieve to the mixed solution is 1: 1-50, preferably 1: 2 to 10.
Further, in S2, the metal salt is an inorganic salt of one of iron, nickel, manganese, and magnesium. Preferably one or two of ferric nitrate, ferric chloride, nickel nitrate, nickel chloride, manganese nitrate, manganese chloride and magnesium chloride.
Further, in S3, the molecular sieve is A, X, Y or one of ZSM type molecular sieves, mesoporous molecular sieves (SBA-15, MCM-13) and natural zeolites (analcite, chabazite and mordenite), and particularly, the specific surface area of the porous molecular sieve material is 300-1000 m 2 Preferably 3A, 4A, 5A, 13X, Y, spherical or rod shaped molecular sieve particles.
Further, in S3, the temperature of the oscillating shaking table is 20-60 ℃, preferably 35-45 ℃; the oscillation time is 1-24 hours, preferably 4-6 hours.
Further, in S4, the vacuum drying temperature is 80-140 ℃, preferably 120-130 ℃; the drying time is 6-24 hours, preferably 12 hours.
The second object of the present invention is to provide an amine modified porous molecular sieve for efficiently capturing carbon dioxide, which is obtained by the above preparation method.
Further, the components of the amine modified porous molecular sieve comprise a molecular sieve, organic amine and metal salt, wherein the mass ratio of the organic amine is 5-20%, the mass ratio of the metal salt is 0.5-2%, and the balance is the molecular sieve.
The third purpose of the invention is to provide the application of the amine modified porous molecular sieve in the carbon dioxide trapping adsorbent, wherein the service scene of the adsorbent comprises one of air, flue gas, automobile exhaust and industrial exhaust (power plant and cement plant).
Compared with the prior art, the invention has the following technical advantages:
1) the invention is beneficial to improving CO by screening and compounding the organic amine precursor and modifying the molecular sieve by adopting the mixed amine 2 The adsorption rate and the adsorption capacity of the molecular sieve are improved, and the organic amine is dispersed by adopting the alcohol-water mixed solution, so that on one hand, the viscosity of the mixed amine solution is reduced, the organic amine loading capacity on the surface of the molecular sieve is improved, and on the other hand, the hydrolysis of metal salt is facilitated to be converted into an oxide form with a stable structure.
2) The invention adopts the formed molecular sieve as a precursor to be soaked in the mixed solution and is assisted with an oscillation modification mode, thereby accelerating mass transfer and diffusion and improving the loading capacity and the loading rate of amine modification.
3) The molecular sieve adsorbent prepared by the invention has good CO 2 The adsorption rate and the adsorption capacity exist in the form of a formed molecular sieve, and can be directly applied to CO under various environmental conditions 2 And (4) adsorbing.
Drawings
FIG. 1 is a graph showing the adsorption performance of each sample in the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. In the technical scheme, characteristics such as preparation means, materials, structures or composition ratios and the like which are not explicitly described are all regarded as common technical characteristics disclosed in the prior art.
Example 1
The preparation process in this example is as follows, 2 ml of triethylene tetramine, 3 ml of diethylene triamine and 1 g of piperazine are measured and added into a 50 ml conical flask, then 6 ml of ethanol and 6 ml of water are added, the mixture is stirred and fully mixed, 0.464 g of magnesium chloride is added into the mixed solution, and the mixed solution is obtained after 2 hours of stirring. Weighing 5 g of spherical Y-type molecular sieve, adding the spherical Y-type molecular sieve into an organic amine solution, and oscillating the solution in a shaking table for 4 hours (40 ℃, 60 revolutions per minute); and after suction filtration, placing the obtained solid sample in a vacuum drying oven for vacuum drying for 12 hours at 90 ℃ to obtain the amine modified porous molecular sieve for efficiently trapping carbon dioxide, which is marked as A-Y. In the embodiment, the liquid viscosity of the mixed amine can be controlled by adjusting the proportion of the mixed amine and adding proper metal salt, so that the surface and pore channels of the molecular sieve are modified by the amine with higher content, thereby enhancing the adsorption of CO 2 The ability of the cell to perform.
Example 2
The preparation process in this example is as follows, weighing 2 ml of triethylene tetramine and 4 ml of diethylene triamine, adding them into a 50 ml conical flask, then adding 6 ml of ethanol and 6 ml of water, stirring and mixing them thoroughly, adding 0.5 g of manganese chloride into the mixed solution, and stirring for 2 hours to obtain the mixed solution. Weighing 5 g of spherical sodium 4A type molecular sieve particles, adding the particles into an organic amine solution, and oscillating the particles in a shaking table for 24 hours (60 ℃, 60 revolutions per minute); and after suction filtration, placing the obtained solid sample in a vacuum drying oven for vacuum drying for 12 hours at 90 ℃ to obtain the amine modified porous molecular sieve for efficiently trapping carbon dioxide, which is marked as A-Na 4A.
Example 3
The preparation process in this example is as follows, 2 ml of triethylene tetramine and 1 g of piperazine are weighed and added into a 50 ml conical flask, then 6 ml of ethanol and 6 ml of water are added, the mixture is stirred and fully mixed, 0.3 g of ferric nitrate is added into the mixed solution, and the mixed solution is obtained after stirring for 2 hours. Weighing 5 g of rod-shaped ZSM-5 type molecular sieve particles, adding the rod-shaped ZSM-5 type molecular sieve particles into an organic amine solution, and oscillating the mixture in a shaking table for 24 hours (20 ℃, 60 revolutions per minute); and after suction filtration, placing the obtained solid sample in a vacuum drying oven for vacuum drying for 12 hours at the temperature of 140 ℃ to obtain the amine modified porous molecular sieve for efficiently trapping carbon dioxide, which is marked as A-ZSM-5.
Example 4
The preparation process in this example is as follows, measuring 6 ml of diethanolamine and adding into 50 ml of conical flask, then adding 6 ml of ethanol and 6 ml of water, stirring and mixing thoroughly, adding 0.3 g of nickel nitrate into the mixed solution, stirring for 2 hours to obtain the mixed solution. Weighing 5 g of spherical 5A type molecular sieve particles, adding the particles into an organic amine solution, and oscillating the particles in a shaking table for 24 hours (60 ℃, 60 revolutions per minute); and after suction filtration, placing the obtained solid sample in a vacuum drying oven for vacuum drying for 12 hours at the temperature of 80 ℃ to obtain the amine modified porous molecular sieve for efficiently trapping carbon dioxide, which is marked as A-Na 5A.
Example 5
The preparation process in this example is as follows, 1 g of piperazine, 1 ml of triethylene tetramine and 4 ml of diethylenetriamine are weighed and added into a 25 ml conical flask, then 6 ml of ethanol and 6 ml of water are added, the mixture is stirred and fully mixed, 0.5 g of nickel nitrate is added into the mixed solution, and the mixed solution is obtained after stirring for 2 hours. Weighing 5 g of powder MCM-13 molecular sieve, adding the powder into an organic amine solution, and oscillating the solution in a shaking table for 24 hours (60 ℃, 60 revolutions per minute); and after suction filtration, placing the obtained solid sample in a vacuum drying oven for vacuum drying for 12 hours at the temperature of 80 ℃ to obtain the amine modified porous molecular sieve for efficiently trapping carbon dioxide, which is marked as A-MCM-13.
Comparative example 1
The preparation process in this comparative example is as follows, weighing 5 g of spherical Y-type molecular sieve, then adding 6 ml of ethanol and 6 ml of water, shaking for 4 hours (60 ℃, 60 rpm) in a shaker, filtering out the liquid at normal temperature to obtain a solid sample, then placing the solid sample in a vacuum drying oven for vacuum drying for 12 hours at 90 ℃, and cooling to room temperature after the drying is completed to obtain the molecular sieve adsorbent of the comparative example, which is marked as Y. Other molecular sieves Na4A, Na5A, ZSM-5 and MCM-41 were subjected to the same pretreatment procedure to obtain molecular sieve samples.
The adsorbents synthesized in the above examples and comparative examples are used for adsorbing CO in gas 2 The equilibrium adsorption capacity at 60 ℃ for a nitrogen/carbon dioxide gas mixture (15% by volume carbon dioxide) is shown in the following table,the adsorption performance profile of each sample is shown in fig. 1. CO of Y molecular sieve in unmodified molecular sieve 2 The adsorption capacity is the highest, and in the modified molecular sieve, A-Y has the maximum adsorption capacity of 4.5 mmol/g.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of an amine modified porous molecular sieve for efficiently capturing carbon dioxide is characterized by comprising the following steps:
s1: dissolving organic amine in a mixed solution of ethanol and water to obtain a mixed solution A;
s2: adding metal salt into the mixed solution A, and stirring at normal temperature to obtain mixed solution B;
s3: adding a molecular sieve into the mixed solution B, and oscillating and dipping in a shaking table to obtain a solid-liquid mixture C;
s4: and carrying out suction filtration on the solid-liquid mixture C to obtain a solid product D, and carrying out vacuum drying on the solid product D to obtain a modified porous molecular sieve product.
2. The method according to claim 1, wherein in S1, the organic amine is a mixture of two or more selected from ethanolamine, ethylenediamine, diethanolamine, polyvinylamine, imidazole, piperazine, polyethyleneimine, tetraethylenepentamine, triethylenetetramine, and diethylenetriamine.
3. The method for preparing an amine-modified porous molecular sieve for efficiently trapping carbon dioxide as claimed in claim 1, wherein, in S1-S3:
the mass ratio of the organic amine to the ethanol is 1: 1-20;
the mass ratio of the ethanol to the water is 1: 0.1 to 10;
the mass ratio of the organic amine to the metal salt is 1: 0.01 to 0.2;
the mass ratio of the molecular sieve to the mixed solution is 1: 1 to 50.
4. The method of claim 1, wherein in S2, the metal salt is an inorganic salt of one of iron, nickel, manganese and magnesium.
5. The method of claim 1, wherein in S3, the molecular sieve is A, X, Y, ZSM type molecular sieve, mesoporous molecular sieve or natural zeolite;
the specific surface area of the molecular sieve is 300-1000 m 2 /g。
6. The method of claim 1, wherein in S3, the temperature of the shaking table is controlled at 20-60 ℃ during shaking, and the shaking time is 1-24 hours.
7. The method for preparing the amine modified porous molecular sieve for efficiently capturing the carbon dioxide as claimed in claim 1, wherein in S4, the temperature in the vacuum drying process is controlled to be 80-140 ℃, and the drying time is 6-24 hours.
8. An amine-modified porous molecular sieve for efficiently capturing carbon dioxide, which is obtained by the production method according to any one of claims 1 to 7.
9. The amine modified porous molecular sieve for efficiently trapping carbon dioxide as claimed in claim 8, wherein the components of the amine modified porous molecular sieve comprise a molecular sieve, an organic amine and a metal salt, wherein the mass ratio of the organic amine is 5% -20%, the mass ratio of the metal salt is 0.5-2%, and the balance is the molecular sieve.
10. Use of the amine-modified porous molecular sieve of claim 8 in a carbon dioxide capture sorbent, wherein the sorbent has a service scene comprising one of air, flue gas, automobile exhaust, and industrial exhaust.
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