CN117285745A - Nano porous functional spherical resin for removing formaldehyde and preparation method and application thereof - Google Patents
Nano porous functional spherical resin for removing formaldehyde and preparation method and application thereof Download PDFInfo
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- CN117285745A CN117285745A CN202311577699.3A CN202311577699A CN117285745A CN 117285745 A CN117285745 A CN 117285745A CN 202311577699 A CN202311577699 A CN 202311577699A CN 117285745 A CN117285745 A CN 117285745A
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- formaldehyde
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 229920005989 resin Polymers 0.000 title claims abstract description 44
- 239000011347 resin Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 15
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 150000001299 aldehydes Chemical class 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000017 hydrogel Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 abstract description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- 239000007762 w/o emulsion Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 24
- 239000007787 solid Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000499 gel Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000352 supercritical drying Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 244000252337 Epipremnum pinnatum Species 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VFWRNIOSEGGKQE-UHFFFAOYSA-N thiourea;1,3,5-triazine-2,4,6-triamine Chemical compound NC(N)=S.NC1=NC(N)=NC(N)=N1 VFWRNIOSEGGKQE-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08J2361/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08J2361/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The invention relates to a nano porous functional spherical resin for removing formaldehyde, a preparation method and application thereof, in particular to the technical field of nano porous functional resin materials, the preparation method of the nano porous functional spherical resin for removing formaldehyde is characterized in that raw materials are aldehyde and nitrogen-rich compounds, an amino group-containing nano porous functional resin material is synthesized through a sol-gel method by an alkali-acid-alkali method, and a spherical material is polymerized through a water-in-oil emulsion. The sol-gel synthesized nano porous resin material can be used for forming a functional group with high reactivity by physically adsorbing formaldehyde and introducing high proportion of amine groups on the resin, and can react with formaldehyde to form a stable covalent bond compound to play a role in adsorbing formaldehyde.
Description
Technical Field
The invention belongs to the technical field of nano porous functional resin materials, and particularly relates to a nano porous functional spherical resin for removing formaldehyde, and a preparation method and application thereof.
Background
Formaldehyde is a major indoor air pollutant, is a class 1 carcinogen specified by IARC, and in order to solve the problem of volatile pollution of formaldehyde, there are some methods or materials for removing formaldehyde at present:
1. the traditional method comprises the following steps: by utilizing the characteristic that formaldehyde is soluble in water, tea water is put into a living room and is windowed for ventilation, and the pungent smell is basically eliminated; optionally, plants such as scindapsus aureus can be placed indoors: this approach only has a reduced sensory odor, but it is actually just another odor that covers the formaldehyde odor, and harmful gases are still present in the environment.
2. Ventilation method: through the circulation of indoor air, the content of harmful substances in the indoor air can be reduced, so that the harm of the substances to human bodies is reduced.
3. Physical adsorption method: the indoor pollutant purifying method with the most widely used and stable effect is an active carbon physical adsorption method for a long time, and adsorbed substances firstly contact the outer surface of the active carbon and then enter macropores, mesopores and micropores of the active carbon to achieve the purifying effect. However, formaldehyde has low molecular weight and strong polarity, is difficult to thoroughly remove by physical adsorption, and can be reversely released even after adsorption saturation, so that the purification effect is unsatisfactory.
4. Chemical adsorption method: the chemical adsorption method mainly depends on the combination effect generated between the adsorbent and formaldehyde gas, and functional groups such as amino groups, phenolic hydroxyl groups and the like of the adsorbent are subjected to chemical reaction with formaldehyde adsorbate molecules, so that the adsorption is stable and irreversible.
Chinese patent publication No.: CN115304760B discloses a polyamine formaldehyde adsorption material, its preparation and application, the adsorption capacity of the polyamine formaldehyde adsorption material prepared by the patent reaches up to 30.3mg/g, and the adsorption effect is not ideal.
At present, materials which have high specific surface area, developed pore diameter, excellent physical adsorption performance, rich adsorption groups, good chemical adsorption and perfect combination of physical adsorption and chemical adsorption are lacking, and for the reasons, new formaldehyde adsorption technology and adsorption products are necessary to be developed to optimize formaldehyde adsorption effect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the nano porous functional spherical resin for removing formaldehyde, which has excellent physical and chemical properties, simple preparation process and high-efficiency adsorption of formaldehyde, and the preparation method and application thereof.
The invention solves the technical problems by adopting the following technical scheme:
a nano-porous spherical resin for removing formaldehyde is prepared through preparing solution from aldehyde and N-enriched compound in mole ratio of 1-6:1, preparing sol prepolymer solution under catalysis of alkali, emulsion polymerizing with surfactant oil phase, stirring to obtain organic hydrogel, separating, washing, displacing solvent, and drying.
The preparation method of the nano porous functional spherical resin for removing formaldehyde specifically comprises the following steps:
s1, adding aldehyde and strong alkali into deionized water, adjusting the pH to 7.5-10.5, adding into a reactor, stirring and heating to 80-95 ℃ within 15-45min, adding nitrogen-rich compound, and keeping the temperature for 10-60min; then cooling to 50-60 ℃, adding an acidic aqueous solution, regulating the pH to 3.0-5.0, stirring and heating to 80-90 ℃, adding a nitrogen-rich compound, stirring and preserving heat for 10-40min; then adding strong alkali, regulating the pH to 7.5-8.0, and reducing the temperature to 70 ℃ to obtain sol prepolymer solution;
s2, adding the sol prepolymer solution prepared in the step S1 into an oil phase containing a surfactant, wherein the temperature of the oil phase is 80-100 ℃, and stirring to obtain spherical organic hydrogel;
s3, separating, cleaning, replacing a solvent and drying the spherical organic hydrogel prepared in the step S2 to obtain the nano porous spherical resin material.
Preferably, the nitrogen-rich compound may be one or a mixture of at least two of melamine, urea or thiourea.
Preferably, the mass ratio of the aldehyde, the strong base and the deionized water is 1-3:0.1-0.5:7-9.
Preferably, the aldehyde may be one or a mixture of at least two of formaldehyde and thiophenecarboxaldehyde.
Preferably, the molar ratio of aldehyde to nitrogen-rich compound is more preferably 3:1.
preferably, the strong base can be one or a mixture of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Preferably, the acidic aqueous solution can be one or a mixture of at least two of hydrochloric acid, formic acid, phosphoric acid and acetic acid.
Preferably, the surfactant can be one or a mixture of at least two of industrial white oil, span 80, dibutyl phthalate and styrene.
Preferably, the displacement solvent may be one or a mixture of at least two of ethanol and tert-butanol.
Preferably, the drying mode can be normal pressure drying, freeze drying or supercritical drying.
Preferably, the pore diameter of the nano porous functional spherical resin material is between 2 and 100nm, and the specific surface area is between 100 and 600m 2 Between/g.
Preferably, the mass ratio of the aldehyde, the strong base and the deionized water is 1-3: 7 to 9, more preferably 2:8.
preferably, the mass ratio of the sol prepolymer solution to the surfactant is 1:1 to 3, more preferably 1:2.
an application of a nano porous functional spherical resin for removing formaldehyde as an adsorption material for adsorbing formaldehyde in water and air.
The invention has the advantages and positive effects that:
1. the sol-gel synthesized nano porous material can be used for forming a functional group with high reactivity by physically adsorbing formaldehyde and introducing high-proportion amine groups into resin, and can react with formaldehyde to form a stable covalent bond compound to play a role in adsorbing formaldehyde.
2. The raw materials adopted in the invention are conventional chemical raw materials, the equipment used is conventional chemical equipment, and the reaction conditions are mild, so that the input equipment cost is low, and the safety of the process is high; all solvents can be recycled, no pollution is generated to the environment, and the method accords with the principles of environmental protection and economy, so that the method is more suitable for industrialized popularization.
3. The invention adopts a sol-gel reaction mode, takes basic chemical raw materials of aldehyde and nitrogen-rich compound as raw materials, synthesizes spherical organic hydrogel through polymerization of 'water-in-oil' emulsion, and synthesizes the amino group-containing nano porous functional resin material.
4. The invention is synthesized by an alkali-acid-alkali method, and aims to accelerate the further polymerization process between the dimer and the oligomer thereof, thereby improving the crosslinking degree of the prepolymer, reducing the gelation time and enhancing the strength of the material.
Detailed Description
The invention is further illustrated by the following examples, which are intended to be illustrative only and not limiting in any way.
A nano-porous spherical resin for removing formaldehyde is prepared from aldehyde and N-enriched compound (1-6:1) through preparing sol prepolymer solution, polymerizing to obtain spherical organic hydrogel, separating, washing, displacing solvent, drying and drying.
The preparation method of the nano porous functional spherical resin for removing formaldehyde specifically comprises the following steps:
s1, adding aldehyde and strong alkali into deionized water, adjusting the pH to 7.5-10.5, adding into a reactor, stirring and heating to 80-95 ℃ within 15-45min, adding nitrogen-rich compound, and keeping the temperature for 10-60min; then cooling to 50-60 ℃, adding an acidic aqueous solution, regulating the pH to 3.0-5.0, stirring and heating to 80-90 ℃, adding a nitrogen-rich compound, stirring and preserving heat for 10-40min; then adding strong alkali, regulating the pH to 7.5-8.0, and reducing the temperature to 70 ℃ to obtain sol prepolymer solution;
s2, adding the sol prepolymer solution prepared in the step S1 into an oil phase containing a surfactant, wherein the temperature of the oil phase is 80-100 ℃, and stirring to obtain spherical organic hydrogel;
s3, separating, cleaning, replacing a solvent and drying the spherical organic hydrogel prepared in the step S2 to obtain the nano porous spherical resin material.
The particle size of the obtained nano porous functional spherical resin is determined by the type of the surfactant, the mass ratio of the surfactant to the sol prepolymer solution and the stirring rate, and the spherical resin with the size of 0.5-5 microns can be prepared according to the requirement.
Example 1
The preparation method of the nano porous functional spherical resin for removing formaldehyde specifically comprises the following steps:
s1, adding 661.34g of deionized water, 458.63g of 37% formaldehyde and 0.96g of sodium hydroxide solid into a reactor, stirring and heating to 80 ℃, adding 187.57g of melamine, and preserving heat for 30min; cooling to 70deg.C, adding 1.5ml of concentrated hydrochloric acid, regulating pH to about 4.5, stirring for 10min, heating to 80deg.C, adding 50g melamine under the condition, stirring, and maintaining the temperature for 20min; then adding 0.4g of sodium hydroxide solid, and reducing the temperature to 70 ℃ to obtain a sol prepolymer solution;
s2, adding the sol prepolymer solution prepared in the step S1 into a reaction kettle containing 2kg of industrial white oil, stirring for 60min at the oil phase temperature of 90 ℃, and completely changing the sol prepolymer solution into smooth spherical solid;
s3, introducing the mixture of the smooth spherical solid and the industrial white oil prepared in the step S2 into a solid-liquid separator with a 1000-mesh screen, cleaning, replacing the smooth spherical solid with tert-butyl for 3 times, and then freeze-drying to obtain the nano porous functional spherical resin material.
The melamine gel structure is as follows:
example 2
The preparation process of nanometer porous spherical resin for eliminating formaldehyde includes the following steps:
s1, adding 712.26g of deionized water, 536.09g of 37% formaldehyde and 1.00g of sodium hydroxide solid into a reactor, stirring and heating to 85 ℃, adding 171.65g of thiourea, and preserving heat for 30min; cooling to 65deg.C, adding 1.8ml of concentrated hydrochloric acid, regulating pH to about 4.0, stirring for 10min, heating to 80deg.C, adding 80g thiourea under the condition, stirring, and maintaining the temperature for 10min; then adding 0.6g of sodium hydroxide solid, and reducing the temperature to 70 ℃ to obtain a sol prepolymer solution;
s2, adding the sol prepolymer solution prepared in the step S1 into a reaction kettle containing 2kg of industrial white oil, stirring for 60min at the oil phase temperature of 90 ℃, and completely changing the sol prepolymer solution into smooth spherical solid;
s3, introducing the mixture of the smooth spherical solid and the industrial white oil prepared in the step S2 into a solid-liquid separator with a 1000-mesh screen, cleaning, replacing the smooth spherical solid with ethanol for 3 times, and then performing supercritical drying to obtain the nano porous functional spherical resin material.
The thiourea gel structure is as follows:
example 3
The preparation process of nanometer porous spherical resin for eliminating formaldehyde includes the following steps:
s1, adding 727.53g of deionized water, 511.86g of 37% formaldehyde and 0.90g of sodium hydroxide solid into a reactor, stirring and heating to 80 ℃, adding 49.05g of thiourea and 155.68g of melamine, and preserving heat for 20min; cooling to 65deg.C, adding 1.4ml of concentrated hydrochloric acid, regulating pH to about 4.5, stirring for 20min, heating to 80deg.C, adding 10g thiourea and 40g melamine under the conditions, stirring, and maintaining the temperature for 10min; then adding 0.8g of sodium hydroxide solid, and reducing the temperature to 70 ℃ to obtain a sol prepolymer solution;
s2, adding the sol prepolymer solution prepared in the step S1 into a reaction kettle containing 2kg of industrial white oil, stirring for 60min at the oil phase temperature of 90 ℃, and completely changing the sol prepolymer solution into smooth spherical solid;
s3, introducing the mixture of the smooth spherical solid and the industrial white oil prepared in the step S2 into a solid-liquid separator with a 1000-mesh screen, cleaning, replacing the smooth spherical solid with ethanol for 3 times, and then performing supercritical drying to obtain the nano porous functional spherical resin material.
The melamine-thiourea gel structure is as follows:
experimental example 1
10g of the nano porous functional spherical resin materials prepared in examples 1 to 3 were packed in columns, respectively, and formaldehyde concentration was 40mg/m 3 The air of (2) was passed through the resin column at a flow rate of 30 mL/min to trap carbonyl compounds at the outlet, and the concentration of each carbonyl compound was measured with reference to GB/T9733-2008, when the outlet formaldehyde concentration reached 0.5mg/m 3 The air is defined as leakage volume, and the adsorption quantity of each functional resin to formaldehyde is calculated through the leakage volume, wherein the unit is mg/g.
The results are shown in Table 1
Table 1 shows the formaldehyde adsorption results
| Experimental group | Example 1 | Example 2 | Example 3 |
| Formaldehyde adsorption capacity | 50.1 | 46.5 | 55.2 |
The reaction mechanism of removing formaldehyde from amine groups is as follows:
although embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the disclosure of the embodiments.
Claims (10)
1. A nanoporous functional spherical resin for formaldehyde removal, characterized in that: the preparation method comprises the steps of forming a solution by aldehyde and a nitrogen-rich compound in a molar ratio of 1-6:1, preparing a sol prepolymer solution under the catalysis of alkali, performing emulsion polymerization with a surfactant oil phase, stirring and polymerizing to form an organic hydrogel, separating, cleaning, replacing a solvent, and drying to obtain the nano porous functional spherical resin.
2. The nanoporous functional spherical resin for formaldehyde removal according to claim 1, characterized in that: the aldehyde is one or a mixture of at least two of formaldehyde and thiophenecarboxaldehyde.
3. The nanoporous functional spherical resin for formaldehyde removal according to claim 1, characterized in that: the nitrogen-rich compound is one or a mixture of at least two of melamine, urea or thiourea.
4. A process for the preparation of a nanoporous functional spherical resin for formaldehyde removal according to any one of claims 1 to 3, characterized in that: the method specifically comprises the following steps:
s1, adding aldehyde and strong alkali into deionized water, adjusting the pH to 7.5-10.5, adding into a reactor, stirring and heating to 80-95 ℃ within 15-45min, adding nitrogen-rich compound, and keeping the temperature for 10-60min; then cooling to 50-60 ℃, adding an acidic aqueous solution, regulating the pH to 3.0-5.0, stirring and heating to 80-90 ℃, adding a nitrogen-rich compound, stirring and preserving heat for 10-40min; then adding strong alkali, regulating the pH value to 7.5-8.0, and reducing the temperature to 70 ℃ to obtain sol prepolymer solution;
s2, adding the sol prepolymer solution prepared in the step S1 into an oil phase containing a surfactant, wherein the temperature of the oil phase is 80-100 ℃, and stirring to obtain spherical organic hydrogel;
s3, separating, cleaning, replacing a solvent and drying the spherical organic hydrogel prepared in the step S2 to obtain the nano porous spherical resin material.
5. The method for preparing the nano-porous functional spherical resin for removing formaldehyde according to claim 4, wherein the method comprises the following steps: the strong base is one or a mixture of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
6. The method for preparing the nano-porous functional spherical resin for removing formaldehyde according to claim 4, wherein the method comprises the following steps: the acidic aqueous solution is one or a mixture of at least two of hydrochloric acid solution, formic acid solution, phosphoric acid solution and acetic acid solution.
7. The method for preparing the nano-porous functional spherical resin for removing formaldehyde according to claim 4, wherein the method comprises the following steps: the surfactant is one or a mixture of at least two of industrial white oil, span 80, dibutyl phthalate and styrene.
8. The method for preparing the nano-porous functional spherical resin for removing formaldehyde according to claim 4, wherein the method comprises the following steps: the displacement solvent is one or a mixture of at least two of ethanol and tertiary butanol.
9. The method for preparing the nano-porous functional spherical resin for removing formaldehyde according to claim 4, wherein the method comprises the following steps: the mass ratio of the aldehyde, the strong alkali and the deionized water is 1-3:0.1-0.5:7-9.
10. Use of a nanoporous functional spherical resin for formaldehyde removal prepared according to any one of claims 4 to 9 as a formaldehyde adsorbing material.
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| CN102504326A (en) * | 2011-09-28 | 2012-06-20 | 浙江大学 | Method for preparing super thermal isolation polymer materials from polymer nanometer hollow capsules |
| CN108929416A (en) * | 2018-07-03 | 2018-12-04 | 南京林业大学 | A kind of synthetic method and its application of melamine resin nanosphere |
| CN108970556A (en) * | 2018-07-03 | 2018-12-11 | 南京林业大学 | A kind of synthetic method of Lauxite nanosphere |
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| CN102504326A (en) * | 2011-09-28 | 2012-06-20 | 浙江大学 | Method for preparing super thermal isolation polymer materials from polymer nanometer hollow capsules |
| CN108929416A (en) * | 2018-07-03 | 2018-12-04 | 南京林业大学 | A kind of synthetic method and its application of melamine resin nanosphere |
| CN108970556A (en) * | 2018-07-03 | 2018-12-11 | 南京林业大学 | A kind of synthetic method of Lauxite nanosphere |
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