CN106824293B - A kind of nanometer titanium dioxide photocatalytic degradation agent and preparation method thereof - Google Patents
A kind of nanometer titanium dioxide photocatalytic degradation agent and preparation method thereof Download PDFInfo
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- CN106824293B CN106824293B CN201710127324.5A CN201710127324A CN106824293B CN 106824293 B CN106824293 B CN 106824293B CN 201710127324 A CN201710127324 A CN 201710127324A CN 106824293 B CN106824293 B CN 106824293B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 24
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 12
- 238000013033 photocatalytic degradation reaction Methods 0.000 title description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 79
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 34
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 230000015556 catabolic process Effects 0.000 claims abstract description 27
- 238000006731 degradation reaction Methods 0.000 claims abstract description 27
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- 238000007146 photocatalysis Methods 0.000 claims abstract description 19
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005011 phenolic resin Substances 0.000 claims abstract description 12
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000012643 polycondensation polymerization Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 15
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229960004756 ethanol Drugs 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229960002380 dibutyl phthalate Drugs 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 239000004005 microsphere Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 7
- -1 phenolic aldehyde Chemical class 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- FXHVKOJDGLXLAH-UHFFFAOYSA-N C=O.NC(=O)N.[O-2].[O-2].[Ti+4] Chemical compound C=O.NC(=O)N.[O-2].[O-2].[Ti+4] FXHVKOJDGLXLAH-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to technical field of waste water processing, specifically disclose a kind of nano titanium dioxide photocatalysis degradation agent and preparation method thereof.Its structure are as follows: titanium dioxide nanoparticle is evenly distributed on the surface of phenolic resin hollow microsphere.Preparation method, comprising the following steps: S1, under alkaline condition prepares nano-silicon dioxide modified phenolic resin by condensation polymerization with nano silica, phenol, formaldehyde；S2, by S1 preparation nano-silicon dioxide modified phenolic resin and nano-titanium dioxide it is compound；After compound, sodium hydroxide solution is added, until being completely dissolved silica, separation, drying, finally in a nitrogen atmosphere, 450 ~ 550 DEG C of 12 ~ 48h of sintering obtain nano titanium dioxide photocatalysis degradation agent.Gained nano titanium dioxide photocatalysis degradation agent has good the disposal efficiency；Preparation method is easy to operate.
Description
Technical field
The invention belongs to technical field of waste water processing, and in particular to a kind of nano titanium dioxide photocatalysis degradation agent and its system
Preparation Method.
Background technique
Recent years, national wastewater emission amount show the situation risen year by year, cause to ecological environment serious
It destroys, while having threatened the existence water safety of people.Depth optimization reduces COD, BOD and chromatic value of waste water, to monolithic
Condition has big change.
The semiconductor titanium dioxide of broad stopband with performances such as excellent photoelectricity, photochemistry, and simple preparation process by
The extensive concern of researchers is arrived.Since its Fermi energy level is higher, absorption oxygen ability and hydroxylation are strong, and change
It learns property to stablize, there are photocatalytic oxidation properties, can be excited by sunlight, have good urge to organic pollutant in water phase
Change degradation, so that it has extensive development and application in terms of decontamination purifies waste water.
But existing titanium dioxide is as photocatalytic degradation agent, and the effect is unsatisfactory for degradation and purified water.
Summary of the invention
To improve existing clean-up effect, the purpose of the present invention is to provide a kind of nano titanium dioxide photocatalysis degradation agents
And preparation method thereof, gained nano titanium dioxide photocatalysis degradation agent has good the disposal efficiency；Preparation method is easy to operate.
In order to achieve the above objectives, the present invention adopts the following technical scheme that:
A kind of nano titanium dioxide photocatalysis degradation agent, structure are as follows: titanium dioxide nanoparticle is evenly distributed on phenolic aldehyde
The surface of resin hollow microsphere.
Preparation method, comprising the following steps:
The preparation of S1, nano-silicon dioxide modified phenolic resin:
Under alkaline condition, it is prepared with nano silica, phenol, formaldehyde by condensation polymerization nano-silicon dioxide modified
Phenolic resin；
The preparation of S2, nano titanium dioxide photocatalysis degradation agent:
The nano-silicon dioxide modified phenolic resin of S1 preparation and nano-titanium dioxide is compound；After compound, it is added
Sodium hydroxide solution, until it is completely dissolved silica, separation, drying, finally in a nitrogen atmosphere, 450 ~ 550 DEG C of sintering
12 ~ 48h obtains nano titanium dioxide photocatalysis degradation agent.
Preferably, the step of S1 are as follows:
S1.1, dehydrated alcohol is added into silica solution, then stirring is precipitated to gel, centrifugation is formed, and precipitating is dried
It is dry, obtain nano silica；
S1.2, by NaOH, phenol and water under conditions of 40 ~ 60 DEG C, stir evenly；
The S1.1 nano silica prepared is put into wherein, stirring by S1.3, the formalin for taking mass fraction 35 ~ 40%
Uniformly；
S1.4, S1.2 system is warming up to 60 ~ 70 DEG C, every 10 ~ 15min points of 3 ~ 4 addition S1.3 gained formaldehyde mixing
Object；After formaldehyde mixture is added, 60 ~ 65 DEG C are maintained, reacts 4 ~ 4.5h；
S1.5,75 ~ 80 DEG C are warming up to, the reaction was continued 1 ~ 2h, when being then evaporated under reduced pressure constant to system viscosity, natural cooling
To 60 DEG C hereinafter, the p-methyl benzenesulfonic acid aqueous solution that mass fraction 60 ~ 70% is added is solidified, until pH=6-7, obtains nanometer two
Silica modified phenolic resin.
Preferably, in S1.1, based on mass volume ratio, silica solution: dehydrated alcohol=50 ~ 100g: 80 ~ 200mL.
Preferably, in S1.2 and S1.3, based on mass volume ratio, NaOH: phenol: water: the formaldehyde of mass fraction 35 ~ 40%
Solution: nano silica=2.8 ~ 5.4g: 188 ~ 276g: 5 ~ 10mL: 290 ~ 300g: 50 ~ 140g.
Preferably, the step of S2 are as follows:
S2.1, Butyl Phthalate and dehydrated alcohol are placed in container, are sealed, ultrasonic disperse is uniform；
S2.2, uniformly mixed Butyl Phthalate and dehydrated alcohol are poured into reaction flask, adds nano silica and changes
Property phenolic resin, 15 ~ 30min of stirring at normal temperature；
S2.3, product is poured into centrifuge tube, is centrifuged, outwells ethyl alcohol, washed repeatedly with dehydrated alcohol, until upper layer
Until ethyl alcohol is colorless and transparent, the substance of centrifuge tube tube bottom is collected, is replaced with the gleanings nano-silicon dioxide modified in s2.2
Phenolic resin repeats step S2.1- S2.3 for several times in the same way；
S2.4, into the centrifuge tube tube bottom substance finally collected, sodium hydroxide solution is added, until be completely dissolved dioxy
SiClx, separation, drying, finally in a nitrogen atmosphere, 450 ~ 550 DEG C of 12 ~ 48h of sintering obtain nano titanium dioxide photocatalysis drop
Solve agent.
Preferably, in S2.1 and S2.2, according to mass volume ratio, butyl titanate: dehydrated alcohol: nano-silicon dioxide modified
Phenolic resin=1 ~ 2mL: 4 ~ 8mL: 10 ~ 15g.
In the present invention, first reacted with silica with phenolic resin, by modification, available micro nano structure
Phenolic aldehyde microballoon, and then compound nano-titanium dioxide/phenol more than available large specific surface area, active site is carried out with titanium dioxide
Urea formaldehyde composite material, i.e., nano titanium dioxide photocatalysis degradation agent of the invention.Nano-titanium dioxide because its activity it is too big, and
It is easy to happen reunion situation, specific surface area is caused to reduce, reduces catalytic degradation effect；Silica and phenolic resin carry out anti-
It answers, the phenolic aldehyde microballoon of available micro-nano structure is compound with nano-titanium dioxide later, since silica and titanium dioxide have
Synergistic effect, can make nano-titanium dioxide evenly dispersed, dissolve internal nano silica by sodium hydroxide solution later,
Contact area is increased, improves catalytic degradation ability to a certain extent.Therefore, the introducing of silica is played to titanium dioxide
The growth of titanium acts synergistically and realizes organic nothing to the effect that phenolic resin is modified, nano-titanium dioxide and phenolic resin
Machine is compound.
The utility model has the advantages that
1, present invention gained nano titanium dioxide photocatalysis degradation agent can not only overcome nanometer compared with current techniques
Titanium dioxide disperses non-uniform problem, also effectively increases the contact area of titanium dioxide and harmful substance, improves two
The degradation efficiency of titanium oxide is capable of the efficiency of effective lifting waste water processing；
2, photocatalytic degradation agent of the invention can replace traditional photocatalytic degradation agent to be used for purification of waste water field, solve useless
Water discharges the pollution problem to environment, has the characteristics that environmental protection while not influencing clean-up effect；
3, preparation method of the invention, step is simple, easy to operate, and preparation condition is mildly easy to control, high-efficient.
Detailed description of the invention
Fig. 1 is the infrared spectrogram for the nano-silicon dioxide modified phenolic resin that the step S1 of embodiment 1 is prepared.
Fig. 2 is the XRD diagram for the nano-silicon dioxide modified phenolic resin that the step S1 of embodiment 1 is prepared.
Fig. 3 is the TEM figure for the nano-silicon dioxide modified phenolic resin that the step S1 of embodiment 1 is prepared.
Fig. 4 is the TEM figure for the centrifuge tube tube bottom substance that the step S2.3 of embodiment 1 is finally collected.
Specific embodiment
The present invention will be further described below in conjunction with specific embodiments.
Embodiment 1
A kind of preparation method of nano titanium dioxide photocatalysis degradation agent, comprising the following steps:
The preparation of S1, nano-silicon dioxide modified phenolic resin:
S1.1, it takes 90g silica solution in the beaker of 500ml, 80mL dehydrated alcohol is added, then stirring to formation gel,
Centrifugation, is precipitated, and precipitating is put into baking oven to dry, acquisition nano silica；
S1.2, it is put into three-necked flask in water-bath, 2.8g NaOH, 188g phenol and 10mL water is put into three-necked flask
In, under conditions of 50 DEG C, mechanical stirring 30min；
The 90g S1.1 nano silica prepared is put into it by S1.3, the formalin 292g for taking mass fraction 37%
In, magnetic agitation is uniform；
S1.4, water-bath is warming up to 60 DEG C, is added three times formaldehyde mixture obtained by S1.3 every 10min；Formaldehyde is added
After mixture, 60 DEG C of constant, reaction 4h are maintained；
S1.5,80 DEG C are warming up to, the reaction was continued, and 1h naturally cools to 60 when being then evaporated under reduced pressure constant to system viscosity
DEG C hereinafter, the p-methyl benzenesulfonic acid aqueous solution of mass fraction 70% is added, until PH=6-7, nano-silicon dioxide modified phenolic aldehyde is obtained
Resin.
The preparation of S2, nano titanium dioxide photocatalysis degradation agent:
S2.1, into plastic cup, addition 2mL Butyl Phthalate and 8mL dehydrated alcohol are placed in container, cover preservative film, ultrasound
20min；
S2.2, uniformly mixed Butyl Phthalate and dehydrated alcohol are poured into three-necked flask, adds 10g nanometer titanium dioxide
Magneton is added in Si modification phenolic resin, is rotated with the speed of 15r/s, stirring at normal temperature 20min；
S2.3, product is poured into centrifuge tube, is rotated, ethyl alcohol is outwelled, repeatedly repeatedly with 6000r/min with centrifuge
It is washed with dehydrated alcohol, until the ethyl alcohol on upper layer is colorless and transparent, collects the substance of centrifuge tube tube bottom, with gleanings replacement
Nano-silicon dioxide modified phenolic resin in s2.2 repeats step S2.1- S2.3 five times in the same way；
S2.4, into the centrifuge tube tube bottom substance finally collected, sodium hydroxide solution is added to being completely dissolved titanium dioxide
Silicon, separation, drying, finally in a nitrogen atmosphere, 500 DEG C of sintering for 24 hours, obtain nano titanium dioxide photocatalysis degradation agent.
Fig. 1 is that the infrared spectrogram for the nano-silicon dioxide modified phenolic resin that the step S1 of embodiment 1 is prepared is (horizontal
Coordinate unit is cm-1, ordinate B represents peak strength), 3400 cm in figure-1The peak at place is methylol characteristic peak, 1450 cm-1
The peak at place is the bending vibration characteristic peak of methylol；2900 cm-1And 3050 cm-1The biabsorption peak at place is methylene feature
Peak indicates methylene (- CH on phenyl ring2) stretching vibration absworption peak；1250 cm-1The peak at place is hydroxyl carbon-oxygen bond (C-O) spy
Levy peak；1650 cm-1And 1450 cm-1The characteristic peak at place is phenyl ring framework characteristic peak；750 cm-1The peak at place is phenyl ring bending vibration
Dynamic characteristic peak；1050 cm-1The peak at place is the characteristic peak of silicon oxygen bond between nano silica and phenolic resin.
Fig. 2 is XRD diagram (the horizontal seat for the nano-silicon dioxide modified phenolic resin that the step S1 of embodiment 1 is prepared
Mark A represents scanning angle, and ordinate B represents peak strength), one and only one obviously indefinite form of characteristic peak in figure
SiO2Absorption peak.
Fig. 3 is the TEM figure for the nano-silicon dioxide modified phenolic resin that the step S1 of embodiment 1 is prepared.It can from Fig. 3
To learn: in the nano-silicon dioxide modified phenolic resin of synthesis, nano particle is coated by phenolic resin, is formed with nanometer
Resin balls centered on grain.
Fig. 4 be the step S2.3 of embodiment 1 finally collect centrifuge tube tube bottom substance (after i.e. compound end, hydroxide
Sodium dissolution and sintering before) TEM figure.It can be learnt from Fig. 4: spherical SiO2Surface has coated three layers well, and innermost layer is
Spherical SiO2, intermediate one layer is the phenolic resin coated, and outermost layer is butyl titanate.The collection of material then passes through hydroxide
The silica of sodium solution dissolution, internal layer is dissolved, and surface area increases, so that active site is relatively more；Finally through oversintering
Afterwards, outermost layer TiO2, when carrying out photocatalytic degradation to COD, BOD in waste water, being uniformly distributed for titanium dioxide is conducive to
The degradation efficiency for improving degradation agent degradation harmful substance ensures adequately degradation, the effect of lifting sewage processing.
Claims (5)
1. a kind of preparation method of nano titanium dioxide photocatalysis degradation agent, which comprises the following steps:
The preparation of S1, nano-silicon dioxide modified phenolic resin:
Under alkaline condition, nano-silicon dioxide modified phenolic aldehyde is prepared by condensation polymerization with nano silica, phenol, formaldehyde
Resin；
The preparation of S2, nano titanium dioxide photocatalysis degradation agent:
S2.1, Butyl Phthalate and dehydrated alcohol are placed in container, are sealed, ultrasonic disperse is uniform；
S2.2, uniformly mixed Butyl Phthalate and dehydrated alcohol are poured into reaction flask, adds nano-silicon dioxide modified phenol
Urea formaldehyde, 15 ~ 30min of stirring at normal temperature；
S2.3, product is poured into centrifuge tube, is centrifuged, outwells ethyl alcohol, washed repeatedly with dehydrated alcohol, until the ethyl alcohol on upper layer
Until colorless and transparent, the substance of centrifuge tube tube bottom is collected, replaces the nano-silicon dioxide modified phenolic aldehyde in s2.2 with the gleanings
Resin repeats step S2.1- S2.3 for several times in the same way；
S2.4, into the centrifuge tube tube bottom substance finally collected, sodium hydroxide solution is added, until be completely dissolved titanium dioxide
Silicon, separation, drying, finally in a nitrogen atmosphere, 450 ~ 550 DEG C of 12 ~ 48h of sintering obtain nano titanium dioxide photocatalysis degradation
Agent.
2. preparation method as described in claim 1, which is characterized in that the step of S1 are as follows:
S1.1, dehydrated alcohol is added into silica solution, then stirring is precipitated to gel, centrifugation is formed, precipitating is dried,
Obtain nano silica；
S1.2, by NaOH, phenol and water under conditions of 40 ~ 60 DEG C, stir evenly；
The S1.1 nano silica prepared is put into wherein by S1.3, the formalin for taking mass fraction 35 ~ 40%, and stirring is equal
It is even；
S1.4, S1.2 system is warming up to 60 ~ 70 DEG C, every 10 ~ 15min points of 3 ~ 4 addition S1.3 gained formaldehyde mixtures；Add
After entering formaldehyde mixture, 60 ~ 65 DEG C are maintained, reacts 4 ~ 4.5h；
S1.5,75 ~ 80 DEG C are warming up to, the reaction was continued, and 1 ~ 2h naturally cools to 60 when being then evaporated under reduced pressure constant to system viscosity
DEG C hereinafter, the p-methyl benzenesulfonic acid aqueous solution that mass fraction 60 ~ 70% is added is solidified, until pH=6-7, nanometer titanium dioxide is obtained
Si modification phenolic resin.
3. preparation method as claimed in claim 2, it is characterised in that: in S1.1, based on mass volume ratio, silica solution: anhydrous
Ethyl alcohol=50 ~ 100g: 80 ~ 200mL.
4. preparation method as claimed in claim 2, it is characterised in that: in S1.2 and S1.3, based on mass volume ratio, NaOH:
Phenol: water: the formalin of mass fraction 35 ~ 40%: nano silica=2.8 ~ 5.4g: 188 ~ 276g: 5 ~ 10mL: 290 ~
300g∶50~140g。
5. preparation method as described in claim 1, it is characterised in that: in S2.1 and S2.2, according to mass volume ratio, metatitanic acid fourth
Ester: dehydrated alcohol: nano-silicon dioxide modified phenolic resin=1 ~ 2mL: 4 ~ 8mL: 10 ~ 15g.
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