CN116037079A - Adsorbent for purifying formaldehyde and preparation method thereof - Google Patents
Adsorbent for purifying formaldehyde and preparation method thereof Download PDFInfo
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- CN116037079A CN116037079A CN202310026302.5A CN202310026302A CN116037079A CN 116037079 A CN116037079 A CN 116037079A CN 202310026302 A CN202310026302 A CN 202310026302A CN 116037079 A CN116037079 A CN 116037079A
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 234
- 239000003463 adsorbent Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229920001661 Chitosan Polymers 0.000 claims abstract description 51
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical class O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 43
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000010457 zeolite Substances 0.000 claims abstract description 43
- 239000002808 molecular sieve Substances 0.000 claims abstract description 42
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 39
- 150000002696 manganese Chemical class 0.000 claims abstract description 36
- 229910052582 BN Inorganic materials 0.000 claims abstract description 24
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 24
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000005750 Copper hydroxide Substances 0.000 claims abstract description 24
- 229910001956 copper hydroxide Inorganic materials 0.000 claims abstract description 24
- IOAOAKDONABGPZ-UHFFFAOYSA-N 2-amino-2-ethylpropane-1,3-diol Chemical compound CCC(N)(CO)CO IOAOAKDONABGPZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 19
- ZUKSLMGYYPZZJD-UHFFFAOYSA-N ethenimine Chemical compound C=C=N ZUKSLMGYYPZZJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 35
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000440 bentonite Substances 0.000 claims description 19
- 229910000278 bentonite Inorganic materials 0.000 claims description 19
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 10
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 10
- 239000001095 magnesium carbonate Substances 0.000 claims description 10
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 10
- 229940099596 manganese sulfate Drugs 0.000 claims description 10
- 239000011702 manganese sulphate Substances 0.000 claims description 10
- 235000007079 manganese sulphate Nutrition 0.000 claims description 10
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 10
- 229920000609 methyl cellulose Polymers 0.000 claims description 10
- 239000001923 methylcellulose Substances 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 8
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000011085 pressure filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 17
- 238000002144 chemical decomposition reaction Methods 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000006378 damage Effects 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- -1 silicon-aluminum-oxygen Chemical compound 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 208000024891 symptom Diseases 0.000 description 2
- 208000004998 Abdominal Pain Diseases 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 210000000349 chromosome Anatomy 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000003907 kidney function Effects 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000003908 liver function Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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
- B01J20/22—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
-
- 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
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0222—Compounds of Mn, Re
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- 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
-
- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention belongs to the technical field of adsorbent preparation, and particularly relates to an adsorbent for purifying formaldehyde and a preparation method thereof. The adsorbent for purifying formaldehyde consists of the following raw materials in parts by weight: 21-24 parts of chitosan modified bentonite, 13-15 parts of modified manganese-based particles, 6-8 parts of activated 10X-type zeolite molecular sieve, 2.0-2.5 parts of 2-amino-2-ethyl-1, 3-propanediol, 3.1-4.2 parts of vinyl imine, 1.5-1.7 parts of boron nitride and 0.8-1.2 parts of nano copper hydroxide. The raw materials of the adsorbent for purifying formaldehyde are matched with each other, and the adsorbent for purifying formaldehyde has synergistic effect, physical adsorption and chemical degradation simultaneously exist, so that formaldehyde in the air can be removed in a short time.
Description
Technical Field
The invention belongs to the technical field of adsorbent preparation, and particularly relates to an adsorbent for purifying formaldehyde and a preparation method thereof.
Background
Formaldehyde, a common indoor pollutant, is a carcinogen identified by world health organization, is listed as the second place in a priority control list of toxic chemicals in China, can greatly harm human health, and can cause symptoms such as dizziness, abdominal pain and respiratory tract injury, serious symptoms such as liver and kidney function injury and even cause chromosome lesions according to the difference of formaldehyde concentration, exposure time and individual physique in an exposure environment.
The traditional purification method of indoor formaldehyde mainly comprises an adsorption method, a catalytic oxidation method, a plasma technology, an ozone oxidation method, a biological purification method and the like. The purification principle of adsorption technology consists in exploiting the imbalance of the stress of contaminants on the surface of porous adsorbents. Activated carbon is generally considered to be the most reliable physical adsorptionThe material, however, has the problems of black carbon powder decomposition, easy saturation, serious desorption, secondary pollution and the like in the adsorption of the activated carbon. The photocatalytic oxidation method is carried out by using air or O 2 As an oxidant for oxidation reaction, compared with activated carbon adsorption, the photocatalysis technology has slower purification speed of pollutants, high requirements on light quality and low catalyst efficiency. Ozone oxidation technology is to remove pollutants by utilizing the strong oxidizing property of ozone, and although various pollutants can be removed, the adopted ozone has an influence on health. The plasma technology mainly uses inelastic collision of particles, under the action of an external electric field, high-energy electrons generated by discharge impact pollutant molecules to dissociate the pollutant molecules into atoms with higher activity, and the method has wider application range but O 3 Intermediate products such as CO and the like are produced. Biological purification techniques refer to formaldehyde degradation using the metabolic system of plants, but the effectiveness of this method needs to be further verified.
In summary, the adsorption method is more feasible than other purification methods, but the existing adsorption method has the problems of short acting time, low formaldehyde removal efficiency, incomplete degradation and the like, so that a novel adsorbent for purifying formaldehyde needs to be explored.
Disclosure of Invention
The purpose of the invention is that: an adsorbent for purifying formaldehyde is provided. The adsorbent for purifying formaldehyde realizes the removal of formaldehyde through the cooperation of physical adsorption and chemical degradation; the invention also provides a preparation method of the composite.
The adsorbent for purifying formaldehyde disclosed by the invention comprises the following raw materials in parts by weight: 21-24 parts of chitosan modified bentonite, 13-15 parts of modified manganese-based particles, 6-8 parts of activated 10X-type zeolite molecular sieve, 2.0-2.5 parts of 2-amino-2-ethyl-1, 3-propanediol, 3.1-4.2 parts of vinyl imine, 1.5-1.7 parts of boron nitride and 0.8-1.2 parts of nano copper hydroxide.
Preferably, the adsorbent for purifying formaldehyde provided by the invention comprises the following raw materials in parts by weight: 23 parts of chitosan modified bentonite, 14 parts of modified manganese-based particles, 8 parts of activated 10X-type zeolite molecular sieve, 2.0 parts of 2-amino-2-ethyl-1, 3-propanediol, 4.2 parts of ethylenimine, 1.6 parts of boron nitride and 1.0 part of nano copper hydroxide.
Wherein:
the preparation method of the chitosan modified bentonite comprises the steps of dissolving chitosan in acetic acid solution, adding bentonite, stirring for reacting for a period of time, centrifuging, drying at 85-90 ℃, grinding and sieving with a 150-mesh sieve for standby.
Wherein:
the mass volume ratio of chitosan to acetic acid solution is 1:45, the unit is g/mL, and the mass concentration of acetic acid solution is 5%.
The mass ratio of the chitosan to the bentonite is 1:20.
Stirring and reacting at 50-55deg.C for 4.5-5 hr; the centrifugal speed is 3500r/min, and the centrifugal time is 6-8min.
The main component of bentonite in the chitosan modified bentonite is montmorillonite, and montmorillonite minerals contain more unsaturated charges and have larger specific surface area, so that the bentonite has good adsorptivity and cohesiveness. The bentonite is modified by chitosan, the chitosan enters between layers of the bentonite, so that the specific surface area of the prepared chitosan-bentonite composite material is increased, the outer montmorillonite has good adsorption effect on bacteria, and the formaldehyde is removed by chemical adsorption of the interlayer chitosan, which is mainly due to-NH existing in chitosan molecules 2 Can generate nucleophilic addition reaction with formaldehyde to finally form imine compounds containing C=N double bond.
The preparation method of the modified manganese-based particles comprises the following steps:
(1) Uniformly mixing a potassium permanganate solution and a manganese sulfate solution in a reaction container, stirring for reaction, then carrying out reduced pressure filtration, washing with distilled water to obtain a filter cake, drying the filter cake to constant weight to obtain manganese oxide, and grinding for later use;
(2) And (3) uniformly mixing the manganese oxide, basic magnesium carbonate, silica sol, methylcellulose and water which are prepared in the step (1), extruding and granulating, and finally performing heat treatment to prepare the modified manganese-based particles.
Wherein:
the ratio of the amount of the substances of the potassium permanganate solution to the manganese sulfate solution in the step (1) is 1:0.85.
In the step (1), the stirring reaction temperature is 25-30 ℃, and the stirring reaction time is 6.5-7h; the drying temperature of the filter cake is 55-58 ℃.
In the step (2), the mass ratio of the manganese oxide, the methylcellulose, the silica sol and the basic magnesium carbonate in the aqueous solution is 0.4:0.4:1.3:1.5.
The heat treatment temperature in the step (2) is 415-420 ℃, and the heat treatment time is 3-3.5h.
The modified manganese-based particles play a role of pore-forming agent in the preparation process, and the number of pores and the pore size of the modified manganese-based particles are increased through roasting heat treatment, so that the modified manganese-based particles have a mesoporous structure with larger pore diameter, and further have better adsorption capacity on formaldehyde.
The preparation method of the activated 10X zeolite molecular sieve comprises the following steps: the 10X zeolite molecular sieve is activated for 4.5 hours at the temperature of 410-415 ℃.
The 10X zeolite molecular sieve is zeolite formed by cations and a silicon-aluminum-oxygen framework with negative charges, is a polar substance and can polarize molecules through electrostatic induction; aldehyde substances such as formaldehyde contain carbonyl polar groups, are polar adsorbents, and are easily adsorbed by zeolite. After activation treatment, the 10X-type molecular sieve has a silicon-aluminum-oxygen framework structure of faujasite, and adsorbed formaldehyde molecules are easy to move into a super cage, so that more formaldehyde molecules can enter holes of the zeolite, and the 10X-type molecular sieve can keep a higher removal rate for a long time.
The adsorbent for purifying formaldehyde provided by the invention has a synergistic effect relationship among chitosan modified bentonite, modified manganese-based particles and activated 10X zeolite molecular sieve. The bentonite is modified by chitosan, so that the specific surface area of the bentonite is increased, and the adsorptivity of the bentonite is enhanced; and secondly, chitosan is filled between the layers of bentonite, and formaldehyde is degraded through chemical reaction of the chitosan and the formaldehyde, so that the formaldehyde is decomposed. In order to realize rapid adsorption of formaldehyde in air, the activated 10X-type zeolite molecular sieve and modified manganese-based particles are creatively selected for compound use, and the polarity of the activated 10X-type zeolite molecular sieve is enhanced, so that the adsorption effect of formaldehyde is enhanced, and the manganese-based particles have a mesoporous structure after modification treatment, so that formaldehyde can be adsorbed, and other volatile organic matters in the air can be well adsorbed due to the increase of the pore diameter of the manganese-based particles. The compound of 2-amino-2-ethyl-1, 3-propanediol and ethylenimine is additionally added, and the formaldehyde is chemically degraded by chemical reaction with formaldehyde. The addition of boron nitride and nano copper hydroxide can enable the prepared adsorbent to have an additional sterilization function, and in addition, the chemical stability of the adsorbent can be enhanced.
The preparation method of the adsorbent for purifying formaldehyde provided by the invention comprises the following steps:
(1) Crushing chitosan modified bentonite and modified manganese-based particles, sieving with a 200-mesh sieve, and then adding 2-amino-2-ethyl-1, 3-propanediol to mix uniformly at 40-42 ℃;
(2) Adding activated 10X zeolite molecular sieve, vinyl imine, boron nitride, nano copper hydroxide and water into the mixture prepared in the step (1) for granulating, and drying at room temperature after granulating to obtain the adsorbent for purifying formaldehyde.
Wherein:
the mass of the added water accounts for 23-25% of the mass sum of the activated 10X zeolite molecular sieve, the ethylenimine, the boron nitride, the nano copper hydroxide and the mixture prepared in the step (1).
Compared with the prior art, the invention has the following beneficial effects:
(1) The adsorbent for purifying formaldehyde disclosed by the invention is compounded by chitosan modified bentonite, modified manganese-based particles and activated 10X zeolite molecular sieve, formaldehyde is adsorbed and degraded through physical adsorption and chemical degradation of chitosan, and in order to ensure the removal rate and efficiency of formaldehyde, a compound of 2-amino-2-ethyl-1, 3-propanediol and ethylimine is additionally added to eliminate formaldehyde through chemical action, but if the physical adsorption provided by the chitosan modified bentonite, modified manganese-based particles and activated 10X zeolite molecular sieve is not provided, the chemical degradation of the compound of 2-amino-2-ethyl-1, 3-propanediol and ethylimine is greatly reduced. In addition, in order to make the prepared adsorbent for purifying formaldehyde have a sterilizing effect, boron nitride and nano copper hydroxide are additionally added.
(2) The raw materials of the adsorbent for purifying formaldehyde are matched with each other, and the raw materials are synergistic, so that physical adsorption and chemical degradation exist simultaneously, formaldehyde in the air can be removed in a short time, and a high removal rate is maintained.
(3) The preparation method of the adsorbent for purifying formaldehyde has the advantages of simple process and easy preparation, and the prepared adsorbent can remove formaldehyde with a small amount of adsorbent.
Detailed Description
The invention is further described below with reference to examples.
Example 1
The adsorbent for purifying formaldehyde described in the embodiment 1 comprises the following raw materials in parts by weight: 23 parts of chitosan modified bentonite, 14 parts of modified manganese-based particles, 8 parts of activated 10X-type zeolite molecular sieve, 2.0 parts of 2-amino-2-ethyl-1, 3-propanediol, 4.2 parts of ethylenimine, 1.6 parts of boron nitride and 1.0 part of nano copper hydroxide.
Wherein:
the preparation method of the chitosan modified bentonite comprises the steps of dissolving chitosan in acetic acid solution, adding bentonite, stirring for reacting for a period of time, centrifuging, drying at 87 ℃, grinding and sieving with a 150-mesh sieve for later use.
Wherein:
the mass volume ratio of chitosan to acetic acid solution is 1:45, the unit is g/mL, and the mass concentration of acetic acid solution is 5%.
The mass ratio of the chitosan to the bentonite is 1:20.
Stirring reaction temperature is 53 ℃, and stirring reaction time is 4.7h; the centrifugal speed is 3500r/min, and the centrifugal time is 7min.
The preparation method of the modified manganese-based particles comprises the following steps:
(1) Uniformly mixing a potassium permanganate solution and a manganese sulfate solution in a reaction container, stirring for reaction, then carrying out reduced pressure filtration, washing with distilled water to obtain a filter cake, drying the filter cake to constant weight to obtain manganese oxide, and grinding for later use;
(2) And (3) uniformly mixing the manganese oxide, basic magnesium carbonate, silica sol, methylcellulose and water which are prepared in the step (1), extruding and granulating, and finally performing heat treatment to prepare the modified manganese-based particles.
Wherein:
the ratio of the amount of the substances of the potassium permanganate solution to the manganese sulfate solution in the step (1) is 1:0.85.
In the step (1), the stirring reaction temperature is 27 ℃, and the stirring reaction time is 6.8h; the cake drying temperature was 57 ℃.
In the step (2), the mass ratio of the manganese oxide, the methylcellulose, the silica sol and the basic magnesium carbonate in the aqueous solution is 0.4:0.4:1.3:1.5.
The heat treatment temperature in the step (2) is 417 ℃, and the heat treatment time is 3.3 hours.
The preparation method of the activated 10X zeolite molecular sieve comprises the following steps: the 10X zeolite molecular sieve was activated at 410 ℃ for 4.5 hours.
The preparation method of the adsorbent for purifying formaldehyde described in the present example 1 comprises the following steps:
(1) Crushing chitosan modified bentonite and modified manganese-based particles, sieving with a 200-mesh sieve, and then adding 2-amino-2-ethyl-1, 3-propanediol and uniformly mixing at 40 ℃;
(2) Adding activated 10X zeolite molecular sieve, vinyl imine, boron nitride, nano copper hydroxide and water into the mixture prepared in the step (1) for granulating, and drying at room temperature after granulating to obtain the adsorbent for purifying formaldehyde.
Wherein:
the mass of the added water accounts for 24% of the mass sum of the activated 10X zeolite molecular sieve, the ethylenimine, the boron nitride, the nano copper hydroxide and the mixture prepared in the step (1).
Example 2
The adsorbent for purifying formaldehyde described in the embodiment 2 comprises the following raw materials in parts by weight: 21 parts of chitosan modified bentonite, 15 parts of modified manganese-based particles, 6 parts of activated 10X-type zeolite molecular sieve, 2.5 parts of 2-amino-2-ethyl-1, 3-propanediol, 3.7 parts of ethylenimine, 1.7 parts of boron nitride and 0.8 part of nano copper hydroxide.
Wherein:
the preparation method of the chitosan modified bentonite comprises the steps of dissolving chitosan in acetic acid solution, adding bentonite, stirring for reacting for a period of time, centrifuging, drying at 85 ℃, grinding and sieving with a 150-mesh sieve for standby.
Wherein:
the mass volume ratio of chitosan to acetic acid solution is 1:45, the unit is g/mL, and the mass concentration of acetic acid solution is 5%.
The mass ratio of the chitosan to the bentonite is 1:20.
Stirring reaction temperature is 50 ℃, and stirring reaction time is 4.5h; the centrifugal speed is 3500r/min, and the centrifugal time is 6min.
The preparation method of the modified manganese-based particles comprises the following steps:
(1) Uniformly mixing a potassium permanganate solution and a manganese sulfate solution in a reaction container, stirring for reaction, then carrying out reduced pressure filtration, washing with distilled water to obtain a filter cake, drying the filter cake to constant weight to obtain manganese oxide, and grinding for later use;
(2) And (3) uniformly mixing the manganese oxide, basic magnesium carbonate, silica sol, methylcellulose and water which are prepared in the step (1), extruding and granulating, and finally performing heat treatment to prepare the modified manganese-based particles.
Wherein:
the ratio of the amount of the substances of the potassium permanganate solution to the manganese sulfate solution in the step (1) is 1:0.85.
In the step (1), the stirring reaction temperature is 30 ℃, and the stirring reaction time is 7 hours; the cake drying temperature was 58 ℃.
In the step (2), the mass ratio of the manganese oxide, the methylcellulose, the silica sol and the basic magnesium carbonate in the aqueous solution is 0.4:0.4:1.3:1.5.
The heat treatment temperature in the step (2) is 420 ℃, and the heat treatment time is 3.5h.
The preparation method of the activated 10X zeolite molecular sieve comprises the following steps: the 10X zeolite molecular sieve was activated for 4.5h at 415 ℃.
The preparation method of the adsorbent for purifying formaldehyde described in the present example 2 comprises the following steps:
(1) Crushing chitosan modified bentonite and modified manganese-based particles, sieving with a 200-mesh sieve, and then adding 2-amino-2-ethyl-1, 3-propanediol and uniformly mixing at 42 ℃;
(2) Adding activated 10X zeolite molecular sieve, vinyl imine, boron nitride, nano copper hydroxide and water into the mixture prepared in the step (1) for granulating, and drying at room temperature after granulating to obtain the adsorbent for purifying formaldehyde.
Wherein:
the mass of the added water accounts for 23% of the mass sum of the mixture prepared in the step (1) and the activated 10X zeolite molecular sieve, the ethylenimine, the boron nitride and the nano copper hydroxide.
Example 3
The adsorbent for purifying formaldehyde described in the embodiment 3 comprises the following raw materials in parts by weight: 24 parts of chitosan modified bentonite, 13 parts of modified manganese-based particles, 7 parts of activated 10X-type zeolite molecular sieve, 2.2 parts of 2-amino-2-ethyl-1, 3-propanediol, 3.1 parts of ethylenimine, 1.5 parts of boron nitride and 1.2 parts of nano copper hydroxide.
Wherein:
the preparation method of the chitosan modified bentonite comprises the steps of dissolving chitosan in acetic acid solution, adding bentonite, stirring for reacting for a period of time, centrifuging, drying at 90 ℃, grinding and sieving with a 150-mesh sieve for later use.
Wherein:
the mass volume ratio of chitosan to acetic acid solution is 1:45, the unit is g/mL, and the mass concentration of acetic acid solution is 5%.
The mass ratio of the chitosan to the bentonite is 1:20.
Stirring reaction temperature is 55 ℃, and stirring reaction time is 5h; the centrifugal speed is 3500r/min, and the centrifugal time is 8min.
The preparation method of the modified manganese-based particles comprises the following steps:
(1) Uniformly mixing a potassium permanganate solution and a manganese sulfate solution in a reaction container, stirring for reaction, then carrying out reduced pressure filtration, washing with distilled water to obtain a filter cake, drying the filter cake to constant weight to obtain manganese oxide, and grinding for later use;
(2) And (3) uniformly mixing the manganese oxide, basic magnesium carbonate, silica sol, methylcellulose and water which are prepared in the step (1), extruding and granulating, and finally performing heat treatment to prepare the modified manganese-based particles.
Wherein:
the ratio of the amount of the substances of the potassium permanganate solution to the manganese sulfate solution in the step (1) is 1:0.85.
In the step (1), the stirring reaction temperature is 25 ℃, and the stirring reaction time is 6.5h; the cake drying temperature was 55 ℃.
In the step (2), the mass ratio of the manganese oxide, the methylcellulose, the silica sol and the basic magnesium carbonate in the aqueous solution is 0.4:0.4:1.3:1.5.
The heat treatment temperature in the step (2) is 415 ℃, and the heat treatment time is 3 hours.
The preparation method of the activated 10X zeolite molecular sieve comprises the following steps: the 10X zeolite molecular sieve was activated at 413℃for 4.5h.
The preparation method of the adsorbent for purifying formaldehyde described in the present example 3 comprises the following steps:
(1) Crushing chitosan modified bentonite and modified manganese-based particles, sieving with a 200-mesh sieve, and then adding 2-amino-2-ethyl-1, 3-propanediol to mix uniformly at 41 ℃;
(2) Adding activated 10X zeolite molecular sieve, vinyl imine, boron nitride, nano copper hydroxide and water into the mixture prepared in the step (1) for granulating, and drying at room temperature after granulating to obtain the adsorbent for purifying formaldehyde.
Wherein:
the mass of the added water accounts for 25% of the mass sum of the activated 10X zeolite molecular sieve, the ethylenimine, the boron nitride, the nano copper hydroxide and the mixture prepared in the step (1).
Comparative example 1
The method for producing the adsorbent for purifying formaldehyde described in this comparative example 1 is the same as in example 1, except that the raw material composition of the adsorbent for purifying formaldehyde is different from that of example 1. The adsorbent for purifying formaldehyde described in the comparative example 1 comprises the following raw materials in parts by weight: 14 parts of modified manganese-based particles, 8 parts of activated 10X-type zeolite molecular sieve, 2.0 parts of 2-amino-2-ethyl-1, 3-propanediol, 4.2 parts of ethylenimine, 1.6 parts of boron nitride and 1.0 part of nano copper hydroxide; wherein: the modified manganese-based particles and the activated 10X zeolite molecular sieve were prepared in the same manner as in example 1.
Comparative example 2
The method for producing the adsorbent for purifying formaldehyde described in this comparative example 2 is the same as in example 1, except that the raw material composition of the adsorbent for purifying formaldehyde is different from that of example 1. The adsorbent for purifying formaldehyde described in the comparative example 2 comprises the following raw materials in parts by weight: 23 parts of chitosan modified bentonite, 8 parts of activated 10X-type zeolite molecular sieve, 2.0 parts of 2-amino-2-ethyl-1, 3-propanediol, 4.2 parts of ethylenimine, 1.6 parts of boron nitride and 1.0 part of nano copper hydroxide; wherein: the preparation method of the chitosan modified bentonite and the activated 10X zeolite molecular sieve is the same as that of the example 1.
Comparative example 3
The preparation method of the adsorbent for purifying formaldehyde described in this comparative example 3 is the same as in example 1, except that the raw material composition of the adsorbent for purifying formaldehyde is different from that of example 1. The adsorbent for purifying formaldehyde described in the comparative example 3 comprises the following raw materials in parts by weight: 23 parts of chitosan modified bentonite, 14 parts of modified manganese-based particles, 2.0 parts of 2-amino-2-ethyl-1, 3-propanediol, 4.2 parts of ethylenimine, 1.6 parts of boron nitride and 1.0 part of nano copper hydroxide; wherein: the preparation method of the chitosan modified bentonite and the modified manganese-based particles is the same as that of the example 1.
Comparative example 4
The method for producing the adsorbent for purifying formaldehyde described in this comparative example 4 is the same as in example 1, except that the raw material composition of the adsorbent for purifying formaldehyde is different from that of example 1. The adsorbent for purifying formaldehyde described in the comparative example 4 comprises the following raw materials in parts by weight: 23 parts of chitosan modified bentonite, 14 parts of modified manganese-based particles, 8 parts of activated 10X-type zeolite molecular sieve, 2.0 parts of 2-amino-2-ethyl-1, 3-propanediol, 1.6 parts of boron nitride and 1.0 part of nano copper hydroxide; wherein: the preparation methods of the chitosan modified bentonite, the modified manganese-based particles and the activated 10X zeolite molecular sieve are the same as in example 1.
To further illustrate the adsorption effect of the adsorbents for purifying formaldehyde prepared in examples 1 to 3 and comparative examples 1 to 4 of the present invention, the removal rate of formaldehyde in air was examined under the following conditions: the test is carried out in a test chamber with a volume of 2.0m 3 The temperature is 25+/-3 ℃, and the relative humidity is 45+/-10% RH; the amount of the adsorbent for purifying formaldehyde was 25g. The detection steps are as follows: the adsorbent for purifying formaldehyde was uniformly placed in the test chamber, and the removal rate of formaldehyde was measured after 24 hours, and the results are shown in table 1 below:
TABLE 1 detection results of adsorbents for purifying formaldehyde
Claims (9)
1. An adsorbent for purifying formaldehyde, characterized in that: the composite material consists of the following raw materials in parts by weight: 21-24 parts of chitosan modified bentonite, 13-15 parts of modified manganese-based particles, 6-8 parts of activated 10X-type zeolite molecular sieve, 2.0-2.5 parts of 2-amino-2-ethyl-1, 3-propanediol, 3.1-4.2 parts of vinyl imine, 1.5-1.7 parts of boron nitride and 0.8-1.2 parts of nano copper hydroxide.
2. The adsorbent for purifying formaldehyde according to claim 1, characterized in that: the composite material consists of the following raw materials in parts by weight: 23 parts of chitosan modified bentonite, 14 parts of modified manganese-based particles, 8 parts of activated 10X-type zeolite molecular sieve, 2.0 parts of 2-amino-2-ethyl-1, 3-propanediol, 4.2 parts of ethylenimine, 1.6 parts of boron nitride and 1.0 part of nano copper hydroxide.
3. The adsorbent for purifying formaldehyde according to claim 1, characterized in that: the preparation method of the chitosan modified bentonite comprises the steps of dissolving chitosan in acetic acid solution, adding bentonite, stirring for reacting for a period of time, centrifuging, drying at 85-90 ℃, grinding and sieving with a 150-mesh sieve for standby.
4. The adsorbent for purifying formaldehyde according to claim 3, characterized in that: the mass-volume ratio of chitosan to acetic acid solution is 1:45, the unit is g/mL, and the mass concentration of the acetic acid solution is 5%;
the mass ratio of the chitosan to the bentonite is 1:20;
stirring and reacting at 50-55deg.C for 4.5-5 hr; the centrifugal speed is 3500r/min, and the centrifugal time is 6-8min.
5. The adsorbent for purifying formaldehyde according to claim 1, characterized in that: the preparation method of the modified manganese-based particles comprises the following steps:
(1) Uniformly mixing a potassium permanganate solution and a manganese sulfate solution in a reaction container, stirring for reaction, then carrying out reduced pressure filtration, washing with distilled water to obtain a filter cake, drying the filter cake to constant weight to obtain manganese oxide, and grinding for later use;
(2) And (3) uniformly mixing the manganese oxide, basic magnesium carbonate, silica sol, methylcellulose and water which are prepared in the step (1), extruding and granulating, and finally performing heat treatment to prepare the modified manganese-based particles.
6. The adsorbent for purifying formaldehyde according to claim 5, characterized in that: the ratio of the amount of the substances of the potassium permanganate solution to the manganese sulfate solution in the step (1) is 1:0.85;
in the step (1), the stirring reaction temperature is 25-30 ℃, and the stirring reaction time is 6.5-7h; the drying temperature of the filter cake is 55-58 ℃;
in the step (2), the mass ratio of the manganese oxide, the methylcellulose, the silica sol and the basic magnesium carbonate in the aqueous solution is 0.4:0.4:1.3:1.5;
the heat treatment temperature in the step (2) is 415-420 ℃, and the heat treatment time is 3-3.5h.
7. The adsorbent for purifying formaldehyde according to claim 1, characterized in that: the preparation method of the activated 10X zeolite molecular sieve comprises the following steps: the 10X zeolite molecular sieve is activated for 4.5 hours at the temperature of 410-415 ℃.
8. A method for preparing the adsorbent for purifying formaldehyde according to claim 1, characterized in that: the method comprises the following steps:
(1) Crushing chitosan modified bentonite and modified manganese-based particles, sieving with a 200-mesh sieve, and then adding 2-amino-2-ethyl-1, 3-propanediol to mix uniformly at 40-42 ℃;
(2) Adding activated 10X zeolite molecular sieve, vinyl imine, boron nitride, nano copper hydroxide and water into the mixture prepared in the step (1) for granulating, and drying at room temperature after granulating to obtain the adsorbent for purifying formaldehyde.
9. The method for producing an adsorbent for purifying formaldehyde according to claim 8, characterized in that: the mass of the added water accounts for 23-25% of the mass sum of the activated 10X zeolite molecular sieve, the ethylenimine, the boron nitride, the nano copper hydroxide and the mixture prepared in the step (1).
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| CN104437422A (en) * | 2014-10-21 | 2015-03-25 | 繁昌县倍思生产力促进中心有限公司 | Adsorbent for formaldehyde-scavenging haze-preventing gauze mask and preparation method thereof |
| CN105665000A (en) * | 2016-01-11 | 2016-06-15 | 盘锦盛世康环保科技有限公司 | Room temperature formaldehyde catalytic material and preparation method thereof |
| CN107261813A (en) * | 2017-08-11 | 2017-10-20 | 广州康滤净化科技有限公司 | Air purifying preparation and its preparation method and application |
| CN110776797A (en) * | 2019-11-14 | 2020-02-11 | 立邦涂料（中国）有限公司 | Two-dimensional boron nitride modified emulsion paint and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104437422A (en) * | 2014-10-21 | 2015-03-25 | 繁昌县倍思生产力促进中心有限公司 | Adsorbent for formaldehyde-scavenging haze-preventing gauze mask and preparation method thereof |
| CN105665000A (en) * | 2016-01-11 | 2016-06-15 | 盘锦盛世康环保科技有限公司 | Room temperature formaldehyde catalytic material and preparation method thereof |
| CN107261813A (en) * | 2017-08-11 | 2017-10-20 | 广州康滤净化科技有限公司 | Air purifying preparation and its preparation method and application |
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