CN109317111B - Preparation method of floatable foaming adsorbent loaded with nano photocatalyst - Google Patents
Preparation method of floatable foaming adsorbent loaded with nano photocatalyst Download PDFInfo
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- CN109317111B CN109317111B CN201811308429.1A CN201811308429A CN109317111B CN 109317111 B CN109317111 B CN 109317111B CN 201811308429 A CN201811308429 A CN 201811308429A CN 109317111 B CN109317111 B CN 109317111B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 54
- 239000003463 adsorbent Substances 0.000 title claims abstract description 40
- 238000005187 foaming Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 44
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007822 coupling agent Substances 0.000 claims abstract description 23
- 239000012798 spherical particle Substances 0.000 claims abstract description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 18
- 239000006229 carbon black Substances 0.000 claims abstract description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 17
- 238000007493 shaping process Methods 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 238000007873 sieving Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 238000001723 curing Methods 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 50
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 28
- 239000011787 zinc oxide Substances 0.000 claims description 14
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001940 europium oxide Inorganic materials 0.000 claims description 3
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 3
- KBLRIGLPGMRISA-UHFFFAOYSA-N neodymium(3+) oxygen(2-) praseodymium(3+) Chemical compound [O-2].[Pr+3].[Nd+3].[O-2].[O-2] KBLRIGLPGMRISA-UHFFFAOYSA-N 0.000 claims description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 3
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 claims description 2
- FRWPIQAMIMYSPM-UHFFFAOYSA-N diethoxy-(8-fluorooctyl)-pentadecan-2-yloxysilane Chemical compound C(CCCCCCCCCCCC)C(C)O[Si](OCC)(OCC)CCCCCCCCF FRWPIQAMIMYSPM-UHFFFAOYSA-N 0.000 claims description 2
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 claims description 2
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 239000010865 sewage Substances 0.000 abstract description 20
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 239000011257 shell material Substances 0.000 description 45
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 239000003344 environmental pollutant Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- -1 heptadecafluorodecyltrimethoxysilane ethanol Chemical compound 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000010170 biological method Methods 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 230000035622 drinking Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000034994 death Effects 0.000 description 1
- 231100000517 death Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4881—Residues from shells, e.g. eggshells, mollusk shells
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of environmental protection, in particular to a preparation method of a floatable foaming adsorbent loaded with a nano photocatalyst. The preparation method comprises the following steps: (S.1) pretreatment: cleaning, crushing and sieving shells to obtain shell powder; (S.2) material preparation and shaping: adding a photocatalyst, carbon black, a titanate coupling agent and a polyvinyl alcohol aqueous solution, stirring uniformly, and shaping to obtain spherical particles; (S.3) roasting and grinding: carrying out thermal sintering and then grinding to obtain micro-nano porous shell powder; (S.4) preparing and forming: mixing with a silane coupling agent ethanol solution, pressing for molding, and heating and curing to obtain the floatable type foaming adsorbent carrying the nano photocatalyst. The invention overcomes the problems that the natural shell adsorbent in the prior art can not decompose organic pollutants in the natural shell adsorbent and has limited sewage treatment effect, and has the advantages of (1) effectively treating the organic pollutants in the sewage; (2) the photocatalysis effect is excellent; (3) low cost and simple preparation process.
Description
Technical Field
The invention relates to the field of environmental protection, in particular to a preparation method of a floatable foaming adsorbent loaded with a nano photocatalyst.
Background
A large amount of toxic and harmful substances caused in agricultural production and daily life are released into the environment to cause pollution, thereby forming a great threat to the living safety of human beings and becoming a great obstacle to the sustainable development of human health, economy and society. According to the investigation of world authorities, in developing countries, 80% of all kinds of diseases are spread due to drinking of unsanitary water, causing at least 2000 million deaths worldwide each year due to drinking of unsanitary water, and therefore, water pollution is called world number one killer. Sewage treatment is a big problem of great concern to human society.
The traditional sewage treatment technology mainly comprises a physical method, a chemical method, a biological method and the like. Due to the complex composition of the pollutants in the sewage, the combination of the above methods is often needed to meet the treatment requirements. Most of these conventional sewage treatment technologies have some disadvantages: although the physical method separates the pollutants from the aqueous solution, the pollutants still have larger environmental risks if no subsequent treatment is carried out, and the treatment medium is usually required to be regenerated and recovered in stages; the chemical method can degrade or eliminate pollutants, but chemical agents with higher cost need to be added, and the added chemical agents can bring secondary pollution to the aqueous solution; biological methods utilize biological metabolism to eliminate pollutants, are relatively low in price, but are often limited by the metabolic capacity of microorganisms, and are ineligible for some wastewater restraints with great treatment difficulty.
The defects of the traditional sewage treatment technology can be better solved by utilizing the photocatalysis principle to treat the sewage. The photocatalytic principle is that, in short, under the irradiation of ultraviolet rays, the electrons in the band of some semiconductor materials are excited to the conduction band, so as to generate electron-hole pairs with strong reactivity, and after the electron-hole pairs migrate to the surface of the semiconductor, the electron-hole pairs can participate in redox reaction under the action of an oxidizing agent such as oxygen, water and the like or a reducing agent (such as pollutants or small molecular organic matters), so as to play a role in degrading pollutants. Among the semiconductor catalysts, titanium dioxide is stable in chemical property, insoluble, non-toxic, low in cost, high in catalytic efficiency and very effective for refractory organic matters such as benzene compounds, chlorine organic matters and the like. Therefore, the method is widely used for photocatalytic sewage treatment.
At present, a large amount of shells are piled up as solid waste on the coast, land resources are occupied, and certain pollution is caused to the environment. The shell comprises CaCO as main ingredient3Due to the porous structure of the filter, the filter can effectively intercept oil stains in sewage, thereby reducing organic pollution in the sewageA compound (I) is provided.
For example, the preparation method of natural shell adsorbent disclosed in the Chinese patent literature, whose publication number is CN103585950A, includes the following steps: the method includes the steps of cleaning organic matters and inorganic pollutants on the surfaces of shells with an acid solution, drying and calcining the cleaned shells, primarily crushing the calcined shells, deeply crushing, grinding and sieving the primarily crushed shells to obtain shell powder, pre-burning the shell powder at a low temperature to evaporate water, fully dehydrating, preparing TiO2 sol, loading the dehydrated shell powder on the TiO2 sol, and sequentially performing the steps of drying, washing, drying, burning and the like to obtain the immobilized TiO2 of the shell powder. The invention adopts shells as the raw material of the adsorbent, reasonably uses waste natural resources and realizes the effect of changing waste into valuable. The invention also adopts TiO2 sol for loading, thereby improving the adsorption effect. However, the invention cannot decompose the organic pollutants in the sewage, and after certain oil stains are absorbed, the organic pollutants must be salvaged, and the oil stains in the organic pollutants can be removed for continuous use, so that the sewage treatment effect is limited.
Disclosure of Invention
The invention provides a preparation method of a floatable type foaming adsorbent carrying a nano photocatalyst, which can be used for solving the problems that a natural shell adsorbent in the prior art can not decompose organic pollutants in the natural shell adsorbent and has a limited sewage treatment effect and can be used for photocatalytic degradation of the organic pollutants in sewage and simultaneously can float on the water surface to increase the contact area with the sewage, so that the sewage treatment effect is improved.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a floatable foaming adsorbent carrying a nano photocatalyst comprises the following steps:
(S.1) pretreatment: cleaning the shell, removing silt and oil stain, and then crushing and sieving the shell to obtain shell powder;
(S.2) material preparation and shaping: adding a photocatalyst, carbon black, a titanate coupling agent and a polyvinyl alcohol aqueous solution into the shell powder in the previous step, uniformly stirring, and shaping to obtain spherical particles;
(S.3) roasting and grinding: carrying out thermal sintering on the obtained spherical particles, and then grinding the spherical particles to obtain micro-nano porous shell powder;
(S.4) preparing and forming: and (3) mixing the micro-nano porous shell powder with a silane coupling agent ethanol solution, pressing and molding the mixture, and heating and curing the mixture to obtain the floatable type foaming adsorbent carrying the nano photocatalyst.
The main material of the floatable type foaming adsorbent of the nano photocatalyst is a shell material, the floatable type foaming adsorbent has the characteristics of high yield and reproducibility, the floatable type foaming adsorbent is ground and then is subjected to composite thermal sintering with the photocatalyst, carbon black, a titanate coupling agent, a polyvinyl alcohol aqueous solution and the like to obtain the micro-nano porous shell powder which has a good photocatalytic effect, and after the micro-nano porous shell powder is treated with a silane coupling agent, the micro-nano porous shell powder has a hydrophobic characteristic.
Preferably, the grain diameter of the shell powder obtained by crushing and sieving in the step (s.1) is 40-300 meshes.
Preferably, the photocatalyst in the step (s.2) includes a main catalyst and an auxiliary catalyst, wherein the main catalyst is nano titanium dioxide and nano zinc oxide, and the mass ratio of the main catalyst to the nano zinc oxide is (3-5): 1, the helper catalyst is a rare earth oxide comprising one or more of cerium oxide, lanthanum oxide, yttrium oxide, praseodymium neodymium oxide, or europium oxide.
The photocatalyst comprises a main catalyst and an auxiliary catalyst, wherein the main catalyst is composed of a composition of nano titanium dioxide and nano zinc oxide, and the main catalyst and the auxiliary catalyst have the characteristics of excellent photocatalytic effect and low price, so that the photocatalyst has low price on the premise of excellent photocatalytic effect, and the photocatalytic effect can be obviously improved after the rare earth oxide auxiliary catalyst is added.
Preferably, in the step (s.2), the mass ratio of the main catalyst to the auxiliary catalyst is 100: (0.01-0.1).
Preferably, the titanate coupling agent in step (s.2) is one of isopropoxy tris (dodecylbenzene sulfonyl) titanate, bis (dioctyl pyrophosphato acyloxy) ethylene titanate, neoalkoxy tris (ethylenediamine-based N-ethoxy) titanate, tetrabutyl titanate or bis (acetoacetato ethyl) di-N-butoxy titanate.
Preferably, in the step (s.2), the mass fraction of the polyvinyl alcohol in the polyvinyl alcohol aqueous solution is 60 to 85%.
The polyvinyl alcohol is added in the invention, so that the components can be effectively bonded together.
Preferably, in the step (s.2), the mass ratio of the shell powder, the photocatalyst, the carbon black, the titanate coupling agent and the polyvinyl alcohol aqueous solution is 100: (15-30): (5-10): (3-10): (50-80).
According to the invention, the carbon black and the polyvinyl alcohol can be effectively decomposed to generate bubbles after being baked at high temperature, so that the foaming effect is achieved, the fluffiness is improved, the porosity is greatly improved, and the adsorption of organic pollutants in sewage is more excellent.
Preferably, the heat sintering temperature in the step (S.3) is 600-800 ℃, and the diameter of the ground micro-nano porous shell powder is 100 nm-5 microns.
After sintering, the carbon black and the polyvinyl alcohol in the powder can be effectively decomposed, and holes are left, so that the adsorption effect is greatly improved.
Preferably, the silane coupling agent ethanol solution in the step (s.4) is a fluorine-containing silane coupling agent ethanol solution, and the fluorine-containing silane coupling agent is heptadecafluorodecyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltrimethoxysilane or per (tridecyl) fluorooctyltriethoxysilane, and the mass fraction thereof is 15 to 40%.
The fluorine-containing silane coupling agent has extremely low surface energy, so that the treated adsorbent has good hydrophobic property, can only adsorb organic pollutants in sewage, and increases the pertinence of the adsorbent in treating the organic pollutants.
Preferably, in the step (S.4), the pressing molding pressure is 10-20 Mpa, the curing temperature is 80-150 ℃, and the curing time is 3-4 hours.
Therefore, the invention has the following beneficial effects:
(1) organic pollutants in the sewage are effectively treated;
(2) the photocatalysis effect is excellent;
(3) low cost and simple preparation process.
Detailed Description
The invention is further described below by means of specific examples.
The raw materials and additives of the present invention are commercially available, and the following examples are only for illustrating the technical scheme of the present invention more clearly, and therefore, are only examples, and the scope of the present invention is not limited thereby.
Example 1
A preparation method of a floatable foaming adsorbent carrying a nano photocatalyst comprises the following steps:
(S.1) pretreatment: cleaning shells, removing silt and oil stains, and then crushing and sieving the shells to obtain shell powder with the diameter of 40 meshes;
(S.2) material preparation and shaping: adding a photocatalyst, carbon black, a titanate coupling agent and 60% of polyvinyl alcohol aqueous solution into the shell powder in the previous step, wherein the mass ratio of the photocatalyst to the carbon black to the titanate coupling agent is 100: 15: 5: 3: 50, uniformly stirring and shaping to obtain spherical particles; the photocatalyst comprises a main catalyst and an auxiliary catalyst, wherein the main catalyst is nano titanium dioxide and nano zinc oxide, and the mass ratio of the nano titanium dioxide to the nano zinc oxide is 3: 1, the auxiliary catalyst is cerium oxide, and the mass ratio of the main catalyst to the auxiliary catalyst is 100: 0.01; the titanate coupling agent is isopropoxy tri (dodecyl benzene acyloxy) titanate;
(S.3) roasting and grinding: carrying out thermal sintering on the obtained spherical particles at 600 ℃, and then grinding the spherical particles to obtain micro-nano porous shell powder with the diameter of 100 nm-5 mu m;
(S.4) preparing and forming: mixing the micro-nano porous shell powder with a heptadecafluorodecyltrimethoxysilane ethanol solution with the mass fraction of 15%, pressing and molding the mixture under the pressure of 10Mpa, and heating to 80 ℃ to cure for 3 hours to obtain the floatable type foaming adsorbent carrying the nano photocatalyst.
Example 2
A preparation method of a floatable foaming adsorbent carrying a nano photocatalyst comprises the following steps:
(S.1) pretreatment: cleaning shells, removing silt and oil stains, and then crushing and sieving the shells to obtain shell powder with the diameter of 300 meshes;
(S.2) material preparation and shaping: adding a photocatalyst, carbon black, a titanate coupling agent and 85% polyvinyl alcohol aqueous solution into the shell powder in the previous step, wherein the mass ratio of the photocatalyst to the carbon black to the titanate coupling agent is 100: 30: 10: 10: 80, uniformly stirring and shaping to obtain spherical particles; the photocatalyst comprises a main catalyst and an auxiliary catalyst, wherein the main catalyst is nano titanium dioxide and nano zinc oxide, and the mass ratio of the nano titanium dioxide to the nano zinc oxide is 5: 1, the auxiliary catalyst is lanthanum oxide, and the mass ratio of the main catalyst to the auxiliary catalyst is 100: 0.1; the titanate coupling agent is bis (dioctyl pyrophosphato acyloxy) ethylene titanate;
(S.3) roasting and grinding: carrying out thermal sintering on the obtained spherical particles at 600-800 ℃, and then grinding the spherical particles to obtain micro-nano porous shell powder with the diameter of 100 nm-5 mu m;
(S.4) preparing and forming: mixing the micro-nano porous shell powder with a trifluoropropyltriethoxysilane ethanol solution with the mass fraction of 40%, pressing and molding the mixture under the pressure of 20Mpa, heating to 150 ℃, and curing for 4 hours to obtain the floatable type foaming adsorbent carrying the nano photocatalyst.
Example 3
A preparation method of a floatable foaming adsorbent carrying a nano photocatalyst comprises the following steps:
(S.1) pretreatment: cleaning shells, removing silt and oil stains, and then crushing and sieving the shells to obtain shell powder with the diameter of 200 meshes;
(S.2) material preparation and shaping: adding a photocatalyst, carbon black, a titanate coupling agent and 75% of polyvinyl alcohol aqueous solution into the shell powder in the previous step, wherein the mass ratio of the photocatalyst to the carbon black to the titanate coupling agent is 100: 20: 8: 6: 60, uniformly stirring and shaping to obtain spherical particles; the photocatalyst comprises a main catalyst and an auxiliary catalyst, wherein the main catalyst is nano titanium dioxide and nano zinc oxide, and the mass ratio of the nano titanium dioxide to the nano zinc oxide is 4: 1, the auxiliary catalyst is a yttrium oxide and praseodymium neodymium oxide 1:1 composition, and the mass ratio of the main catalyst to the auxiliary catalyst is 100: 0.05; the titanate coupling agent is neoalkoxy tri (ethylenediamine N-ethoxy) titanate;
(S.3) roasting and grinding: carrying out thermal sintering on the obtained spherical particles at 750 ℃, and then grinding the spherical particles to obtain micro-nano porous shell powder with the diameter of 100 nm-5 mu m;
(S.4) preparing and forming: mixing the micro-nano porous shell powder with 25 mass percent of trifluoropropyltrimethoxysilane ethanol solution, then pressing and molding the mixture under the pressure of 18Mpa, and heating to 120 ℃ to cure for 3.5 hours to obtain the floatable type foaming adsorbent carrying the nano photocatalyst.
Example 4
A preparation method of a floatable foaming adsorbent carrying a nano photocatalyst comprises the following steps:
(S.1) pretreatment: cleaning the shell, removing silt and oil stain, and then crushing and sieving the shell to obtain shell powder with the diameter of 80 meshes;
(S.2) material preparation and shaping: adding a photocatalyst, carbon black, a titanate coupling agent and a polyvinyl alcohol aqueous solution with the mass fraction of 65% into the shell powder in the previous step, wherein the mass ratio of the photocatalyst to the carbon black to the titanate coupling agent is 100: 20: 9: 8: 55, uniformly stirring and shaping to obtain spherical particles; the photocatalyst comprises a main catalyst and an auxiliary catalyst, wherein the main catalyst is nano titanium dioxide and nano zinc oxide, and the mass ratio of the nano titanium dioxide to the nano zinc oxide is 3.5: 1, the auxiliary catalyst is europium oxide, and the mass ratio of the main catalyst to the auxiliary catalyst is 100: 0.095; the titanate coupling agent is bis (ethyl acetoacetate) di-n-butoxy titanate;
(S.3) roasting and grinding: carrying out thermal sintering on the obtained spherical particles at 650 ℃, and then grinding the spherical particles to obtain micro-nano porous shell powder with the diameter of 100 nm-5 mu m;
(S.4) preparing and forming: mixing the micro-nano porous shell powder with 35% of full (tridecyl) fluorooctyl triethoxysilane ethanol solution, pressing and molding the mixture under the pressure of 18Mpa, heating to 135 ℃, and curing for 3 hours to obtain the floatable type foaming adsorbent carrying the nano photocatalyst.
Example 5
A preparation method of a floatable foaming adsorbent carrying a nano photocatalyst comprises the following steps:
(S.1) pretreatment: cleaning the shell, removing silt and oil stain, and then crushing and sieving the shell to obtain shell powder with the diameter of 250 meshes;
(S.2) material preparation and shaping: adding a photocatalyst, carbon black, a titanate coupling agent and a polyvinyl alcohol aqueous solution with the mass fraction of 80% into the shell powder in the previous step, wherein the mass ratio of the photocatalyst to the carbon black to the titanate coupling agent is 100: 28: 6: 6: 70, uniformly stirring and shaping to obtain spherical particles; the photocatalyst comprises a main catalyst and an auxiliary catalyst, wherein the main catalyst is nano titanium dioxide and nano zinc oxide, and the mass ratio of the nano titanium dioxide to the nano zinc oxide is 5: 1, the auxiliary catalyst is cerium oxide, and the mass ratio of the main catalyst to the auxiliary catalyst is 100: 0.1; the titanate coupling agent is tetrabutyl titanate;
(S.3) roasting and grinding: thermally sintering the obtained spherical particles at 800 ℃, and then grinding the spherical particles to obtain micro-nano porous shell powder with the diameter of 100 nm-5 mu m;
(S.4) preparing and forming: mixing the micro-nano porous shell powder with 35% trifluoropropyltrimethoxysilane ethanol solution by mass percent, then pressing and molding the mixture under the pressure of 16Mpa, and heating to 140 ℃ to cure for 3 hours to obtain the floatable type foaming adsorbent carrying the nano photocatalyst.
The nano photocatalyst-loaded floatable type foaming adsorbents prepared in examples 1 to 5 were tested: removing impurities in the sewage, introducing the impurities into a treatment tank, adding a floatable type foaming adsorbent carrying a nano photocatalyst into the tank according to the adding amount of 1.5-2.5 g/L, and testing the content of various treated pollutants, wherein the data is shown in the following table.
TABLE 1 data of the examples
The data in the table show that the floatable type foaming adsorbent loaded with the nano photocatalyst can purify water in a short time, can effectively reduce COD content, and has the advantages of high purification efficiency, low raw material cost and simple preparation method, so that the floatable type foaming adsorbent can be produced and used in a large scale.
The conventional operations in the operation steps are well known to those skilled in the art and will not be described herein.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation method of a floatable foaming adsorbent carrying a nano photocatalyst is characterized by comprising the following steps:
(S.1) pretreatment: cleaning the shell, removing silt and oil stain, and then crushing and sieving the shell to obtain shell powder;
(S.2) material preparation and shaping: adding a photocatalyst, carbon black, a titanate coupling agent and a polyvinyl alcohol aqueous solution into the shell powder in the previous step, uniformly stirring, and shaping to obtain spherical particles; the mass ratio of the shell powder to the photocatalyst to the carbon black to the titanate coupling agent to the polyvinyl alcohol aqueous solution is 100: (15-30): (5-10): (3-10): (50-80); the photocatalyst comprises a main catalyst and an auxiliary catalyst, and the mass ratio of the main catalyst to the auxiliary catalyst is 100: (0.01-0.1), wherein the main catalyst is nano titanium dioxide and nano zinc oxide in a mass ratio of (3-5): 1, the auxiliary catalyst is a rare earth oxide comprising one or more of cerium oxide, lanthanum oxide, yttrium oxide, praseodymium neodymium oxide, or europium oxide;
(S.3) roasting and grinding: carrying out thermal sintering on the obtained spherical particles, and then grinding the spherical particles to obtain micro-nano porous shell powder;
(S.4) preparing and forming: mixing the micro-nano porous shell powder with a silane coupling agent ethanol solution, pressing and molding the mixture, and heating and curing the mixture to obtain the floatable type foaming adsorbent carrying the nano photocatalyst; the silane coupling agent ethanol solution is a fluorine-containing silane coupling agent ethanol solution, the fluorine-containing silane coupling agent is heptadecafluorodecyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltrimethoxysilane or per (tridecyl) fluorooctyltriethoxysilane, and the mass fraction of the fluorine-containing silane coupling agent is 15-40%.
2. The method for preparing the floatable type foaming adsorbent carrying the nano photocatalyst as claimed in claim 1, wherein the particle diameter of the shell powder obtained by crushing and sieving in the step (S.1) is 40-300 meshes.
3. The method for preparing the floatable type foaming adsorbent for carrying the nano photocatalyst according to claim 1, wherein the titanate coupling agent in the step (S.2) is one of isopropoxy tris (dodecylbenzene sulfonyl) titanate, bis (dioctyl pyrophosphato acyloxy) ethylene titanate, neoalkoxy tris (ethylenediamine N-ethoxy) titanate, tetrabutyl titanate or bis (acetoacetato) di-N-butoxy titanate.
4. The method for preparing the floatable type foaming adsorbent carrying the nano photocatalyst as claimed in claim 1, wherein the mass fraction of the polyvinyl alcohol in the polyvinyl alcohol aqueous solution in the step (S.2) is 60-85%.
5. The preparation method of the floatable type foaming adsorbent carrying the nano photocatalyst according to claim 1, wherein the thermal sintering temperature in the step (S.3) is 600-800 ℃, and the diameter of the ground micro-nano porous shell powder is 100 nm-5 μm.
6. The preparation method of the floatable type foaming adsorbent carrying the nano photocatalyst as claimed in claim 1, wherein the compression molding pressure in the step (S.4) is 10-20 Mpa, the curing temperature is 80-150 ℃, and the curing time is 3-4 hours.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005040703A (en) * | 2003-07-22 | 2005-02-17 | Nitto Kagaku Kk | Adsorbent and its production method |
| CN102302922A (en) * | 2011-07-18 | 2012-01-04 | 中国海洋大学 | Formed shellfish-based regular photocatalytic adsorbent and preparation method thereof |
| CN103495272A (en) * | 2013-10-23 | 2014-01-08 | 西安科技大学 | Formaldehyde absorbing material |
| CN103977755A (en) * | 2014-05-07 | 2014-08-13 | 深圳市中纺滤材无纺布有限公司 | Air purifying material with high catalytic oxidation activity |
| CN104841388A (en) * | 2015-04-13 | 2015-08-19 | 浙江海洋学院 | Preparation method for resin adsorbent compounded with mussel shell powder |
| CN106564983A (en) * | 2016-12-22 | 2017-04-19 | 浙江海洋大学 | Method for adsorbing heavy metals by utilizing marine shellfish |
| CN106633158A (en) * | 2016-12-05 | 2017-05-10 | 常州大学 | Preparation method of superhydrophobic coating with favorable binding force with polyolefins |
| CN107715866A (en) * | 2017-11-01 | 2018-02-23 | 浙江海洋大学 | A kind of bismuth tungstate/mussel shell composite photocatalyst material and preparation method thereof |
| CN108587342A (en) * | 2018-05-15 | 2018-09-28 | 张子晗 | A kind of nano titanium oxide photocatalysis disinfectant purification coating |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696209A (en) * | 2005-05-17 | 2005-11-16 | 上海大学 | Method for preparing suspension type filling material of Nano titanium dioxide |
-
2018
- 2018-11-05 CN CN201811308429.1A patent/CN109317111B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005040703A (en) * | 2003-07-22 | 2005-02-17 | Nitto Kagaku Kk | Adsorbent and its production method |
| CN102302922A (en) * | 2011-07-18 | 2012-01-04 | 中国海洋大学 | Formed shellfish-based regular photocatalytic adsorbent and preparation method thereof |
| CN103495272A (en) * | 2013-10-23 | 2014-01-08 | 西安科技大学 | Formaldehyde absorbing material |
| CN103977755A (en) * | 2014-05-07 | 2014-08-13 | 深圳市中纺滤材无纺布有限公司 | Air purifying material with high catalytic oxidation activity |
| CN104841388A (en) * | 2015-04-13 | 2015-08-19 | 浙江海洋学院 | Preparation method for resin adsorbent compounded with mussel shell powder |
| CN106633158A (en) * | 2016-12-05 | 2017-05-10 | 常州大学 | Preparation method of superhydrophobic coating with favorable binding force with polyolefins |
| CN106564983A (en) * | 2016-12-22 | 2017-04-19 | 浙江海洋大学 | Method for adsorbing heavy metals by utilizing marine shellfish |
| CN107715866A (en) * | 2017-11-01 | 2018-02-23 | 浙江海洋大学 | A kind of bismuth tungstate/mussel shell composite photocatalyst material and preparation method thereof |
| CN108587342A (en) * | 2018-05-15 | 2018-09-28 | 张子晗 | A kind of nano titanium oxide photocatalysis disinfectant purification coating |
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