CN106824293A - A kind of nano titanium dioxide photocatalysis degradation agent and preparation method thereof - Google Patents
A kind of nano titanium dioxide photocatalysis degradation agent and preparation method thereof Download PDFInfo
- Publication number
- CN106824293A CN106824293A CN201710127324.5A CN201710127324A CN106824293A CN 106824293 A CN106824293 A CN 106824293A CN 201710127324 A CN201710127324 A CN 201710127324A CN 106824293 A CN106824293 A CN 106824293A
- Authority
- CN
- China
- Prior art keywords
- nano
- titanium dioxide
- preparation
- silicon
- phenolic resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000015556 catabolic process Effects 0.000 title claims abstract description 27
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 23
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 31
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005011 phenolic resin Substances 0.000 claims abstract description 13
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- 239000004005 microsphere Substances 0.000 claims abstract description 3
- 238000012643 polycondensation polymerization Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 11
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- 229960002380 dibutyl phthalate Drugs 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 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 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 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
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 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
- 238000005406 washing Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000004744 fabric Substances 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 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
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- -1 Phenolic aldehyde Chemical class 0.000 description 2
- 238000002441 X-ray diffraction Methods 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
- 238000005516 engineering process Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YZBOVSFWWNVKRJ-UHFFFAOYSA-N Monobutylphthalate Chemical class CCCCOC(=O)C1=CC=CC=C1C(O)=O YZBOVSFWWNVKRJ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 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
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006378 damage Effects 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
- 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
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical group O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- 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, a kind of nano titanium dioxide photocatalysis degradation agent and preparation method thereof is specifically disclosed.Its structure is：Titanium dioxide nanoparticle is evenly distributed on the surface of phenolic resin hollow microsphere.Preparation method, comprises the following steps：S1, in the basic conditions, nano-silicon dioxide modified phenolic resin is prepared with nano silicon, phenol, formaldehyde by condensation polymerization；S2, nano-silicon dioxide modified phenolic resin and nano titanium oxide prepared by S1 are combined；After compound end, sodium hydroxide solution is added, until being completely dissolved silica, separate, dry, in a nitrogen atmosphere, 450 ~ 550 DEG C of 12 ~ 48h of sintering obtain nano titanium dioxide photocatalysis degradation agent finally.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 technology
Recent years, national wastewater emission amount shows the situation for rising year by year, is caused to ecological environment serious
Destruction, while having threatened the existence water safety of people.COD, BOD and chromatic value of depth optimization reduction waste water, to monolithic
Condition has big change.
The semiconductor titanium dioxide of broad stopband is with performances such as excellent photoelectricity, photochemistry, and simple preparation technology is received
The extensive concern of researchers is arrived.Because its Fermi energy level is higher, absorption oxygen ability and hydroxylation are strong, and change
Learn stable in properties, with photocatalytic oxidation properties, can be excited by sunshine, there is good urging to organic pollutant in water phase
Change degradation so that it has extensive development and applies in terms of decontamination purification waste water.
But existing titanium dioxide is used as photocatalytic degradation agent, its degradation and purified water effect are unsatisfactory.
The content of the invention
To improve existing clean-up effect, it is an object of the invention to provide a kind of nano titanium dioxide photocatalysis degradation agent
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 realize above-mentioned target, the present invention is adopted the following technical scheme that：
A kind of nano titanium dioxide photocatalysis degradation agent, its structure is：Titanium dioxide nanoparticle is evenly distributed on phenolic resin
The surface of hollow microsphere.
Preparation method, comprises the following steps：
The preparation of S1, nano-silicon dioxide modified phenolic resin：
In the basic conditions, nano-silicon dioxide modified phenolic aldehyde is prepared by condensation polymerization with nano silicon, phenol, formaldehyde
Resin；
The preparation of S2, nano titanium dioxide photocatalysis degradation agent：
Nano-silicon dioxide modified phenolic resin prepared by S1 is combined with nano titanium oxide；After compound end, hydrogen-oxygen is added
Change sodium solution, until be completely dissolved silica, separate, dry, in a nitrogen atmosphere finally, 450 ~ 550 DEG C of sintering 12 ~
48h, obtains nano titanium dioxide photocatalysis degradation agent.
Preferably, the step of S1 is：
S1.1, to absolute ethyl alcohol is added in Ludox, then stirring to formed gel, centrifugation, be precipitated, will precipitation drying,
Obtain nano silicon；
S1.2, by NaOH, phenol and water under conditions of 40 ~ 60 DEG C, stir；
S1.3, the formalin for taking mass fraction 35 ~ 40%, nano silicon prepared by S1.1 is put into wherein, and stirring is equal
It is even；
S1.4, S1.2 systems are warming up to 60 ~ 70 DEG C, S1.3 gained formaldehyde mixtures are added 3 ~ 4 times every 10 ~ 15min points；Plus
Enter after formaldehyde mixture finishes, maintain 60 ~ 65 DEG C, react 4 ~ 4.5h；
S1.5, be warming up to 75 ~ 80 DEG C, continue to react 1 ~ 2h, then vacuum distillation to system viscosity it is constant when, naturally cool to 60
Below DEG C, the p-methyl benzenesulfonic acid aqueous solution of mass fraction 60 ~ 70% is added to be solidified, until pH=6-7, obtains nanometer titanium dioxide
Si modification phenolic resin.
Preferably, in S1.1, based on mass volume ratio, Ludox: absolute ethyl 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 silicon=2.8 ~ 5.4g: 188 ~ 276g: 5 ~ 10mL: 290 ~ 300g: 50 ~ 140g.
Preferably, the step of S2 is：
S2.1, Butyl Phthalate and absolute ethyl alcohol are placed in container, sealed, ultrasonic disperse is uniform；
S2.2, well mixed Butyl Phthalate and absolute ethyl alcohol are poured into reaction bulb, add nano-silicon dioxide modified phenol
Urea formaldehyde, 15 ~ 30min of stirring at normal temperature；
S2.3, product is poured into centrifuge tube, be centrifuged, ethanol is outwelled, repeatedly with absolute ethanol washing, until the ethanol on upper strata
Untill water white transparency, the material of centrifuge tube ttom of pipe is collected, the nano-silicon dioxide modified phenolic aldehyde in s2.2 is replaced with the gleanings
Resin, in the same way, repeat step S2.1- S2.3 are for several times；
In S2.4, the centrifuge tube ttom of pipe material to last collection, sodium hydroxide solution is added, until being completely dissolved titanium dioxide
Silicon, separates, dries, and in a nitrogen atmosphere, 450 ~ 550 DEG C of 12 ~ 48h of sintering obtain nano titanium dioxide photocatalysis degraded finally
Agent.
Preferably, in S2.1 and S2.2, according to mass volume ratio, butyl titanate: absolute ethyl alcohol: nano-silicon dioxide modified
Phenolic resin=1 ~ 2mL: 4 ~ 8mL: 10 ~ 15g.
In the present invention, first reacted with phenolic resin with silica, by modified, micro nano structure can be obtained
Phenolic aldehyde microballoon, and then be combined with titanium dioxide, can obtain that specific surface area is big, the nano titanium oxide/phenol more than active site
Urea formaldehyde composite, i.e., nano titanium dioxide photocatalysis degradation agent of the invention.Nano titanium oxide is too big because of its activity, and
Reunion situation is susceptible to, causes specific surface area to reduce, reduce catalytic degradation effect；Silica and phenolic resin are carried out instead
Should, the phenolic aldehyde microballoon of micro-nano structure can be obtained, it is compound with nano titanium oxide afterwards, because silica and titanium dioxide have
Synergy, can make nano titanium oxide dispersed, dissolve internal nano silicon by sodium hydroxide solution afterwards,
Contact area is increased, catalytic degradation ability is improve to a certain extent.Therefore, the introducing of silica is served to titanium dioxide
The growth synergy of titanium and the effect being modified to phenolic resin, nano titanium oxide and phenolic resin realize organic nothing
Machine is combined.
Beneficial effect：
1st, present invention gained nano titanium dioxide photocatalysis degradation agent, compared with current techniques, can not only overcome nano-silica
Change titanium and disperse uneven problem, also effectively increase the contact area of titanium dioxide and harmful substance, improve titanium dioxide
The degradation efficiency of titanium, can effectively lifting waste water treatment efficiency；
2nd, photocatalytic degradation agent of the invention can replace traditional photocatalytic degradation agent for purification of waste water field, solve waste water row
It is rivals in a contest the pollution problem of environment, the characteristics of there is environmental protection while clean-up effect is not influenceed；
3rd, preparation method of the invention, step is simple, and easy to operate, preparation condition is gently easy to control, efficiency high.
Brief description of the drawings
Fig. 1 is the infrared spectrograms of nano-silicon dioxide modified phenolic resin that prepare of step S1 of embodiment 1.
Fig. 2 is the XRDs of nano-silicon dioxide modified phenolic resin that prepare of step S1 of embodiment 1.
Fig. 3 is the TEM figures of the nano-silicon dioxide modified phenolic resin for preparing of step S1 of embodiment 1.
Fig. 4 is the TEM figures of the last centrifuge tube ttom of pipe materials collected of step S2.3 of embodiment 1.
Specific embodiment
The present invention is further introduced below in conjunction with specific embodiment.
Embodiment 1
A kind of preparation method of nano titanium dioxide photocatalysis degradation agent, comprises the following steps：
The preparation of S1, nano-silicon dioxide modified phenolic resin：
S1.1, take 90g Ludox in the beaker of 500ml, add 80mL absolute ethyl alcohols, then stirring is to forming gel, from
The heart, is precipitated, and precipitation is put into baking oven and is dried, and obtains nano silicon；
S1.2, there-necked flask is put into water-bath, 2.8g NaOH, 188g phenol and 10mL water are put into there-necked flask,
Under conditions of 50 DEG C, mechanical agitation 30min；
S1.3, the formalin 292g for taking mass fraction 37%, nano silicon prepared by 90g S1.1 are put into wherein, magnetic
Power stirs；
S1.4, water-bath is warming up to 60 DEG C, S1.3 gained formaldehyde mixtures are added 3 times every 10min points；Add formaldehyde mixing
After thing is finished, 60 DEG C of constant, reaction 4h are maintained；
S1.5, be warming up to 80 DEG C, continue to react 1h, then vacuum distillation to system viscosity it is constant when, naturally cool to 60 DEG C with
Under, the p-methyl benzenesulfonic acid aqueous solution of mass fraction 70% is added, until PH=6-7, obtains nano-silicon dioxide modified phenolic resin.
The preparation of S2, nano titanium dioxide photocatalysis degradation agent：
S2.1, to adding 2mL Butyl Phthalates and 8mL absolute ethyl alcohols to be placed in container in plastic cup, cover preservative film, ultrasound
20min；
S2.2, well mixed Butyl Phthalate and absolute ethyl alcohol are poured into there-necked flask, add 10g nano silicons and change
Property phenolic resin, add magneton, rotated with the speed of 15r/s, stirring at normal temperature 20min；
S2.3, product is poured into centrifuge tube, rotated with 6000r/min with centrifuge, ethanol is outwelled, nothing is repeatedly used repeatedly
Water-ethanol is washed, and untill the ethanol water white transparency on upper strata, collects the material of centrifuge tube ttom of pipe, and s2.2 is replaced with the gleanings
In nano-silicon dioxide modified phenolic resin, in the same way, repeat step S2.1- S2.3 five times；
In S2.4, the centrifuge tube ttom of pipe material to last collection, add sodium hydroxide solution to silica is completely dissolved, divide
From, dry, finally in a nitrogen atmosphere, 500 DEG C sintering 24h, obtain nano titanium dioxide photocatalysis degradation agent.
Fig. 1 is the infrared spectrograms of nano-silicon dioxide modified phenolic resin that prepare of step S1 of embodiment 1（It 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 flexural vibrations characteristic peak of methylol；2900 cm-1And 3050 cm-1The biabsorption peak at place is methylene feature
Peak, represents methylene on phenyl ring（-CH2-）Stretching vibration absworption peak；1250 cm-1The peak at place is hydroxyl carbon-oxygen bond（C-O）It is special
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 that phenyl ring bending is shaken
Dynamic characteristic peak；1050 cm-1The peak at place is the characteristic peak of silicon oxygen bond between nano silicon and phenolic resin.
Fig. 2 is the XRDs of nano-silicon dioxide modified phenolic resin that prepare of step S1 of embodiment 1（Horizontal seat
Mark A represents scanning angle, and ordinate B represents peak strength）, one and only one obviously indefinite form of characteristic peak in figure
SiO2Absworption peak.
Fig. 3 is the TEM figures of the nano-silicon dioxide modified phenolic resin for preparing of step S1 of embodiment 1.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 is the centrifuge tube ttom of pipe material of the step S2.3 finally collections of embodiment 1（I.e. be combined terminate after, hydroxide
Before sodium dissolves and sinters）TEM figure.Can be learnt from Fig. 4：Spherical SiO2Surface has coated three layers well, and innermost layer is
Spherical SiO2, middle one layer is the phenolic resin of cladding, and outermost layer is butyl titanate.The collection of material then passes through hydroxide
Sodium solution dissolves, and the silica of internal layer is to be dissolved, surface area increase so that active site is relatively more；Eventually pass sintering
Afterwards, outermost layer is TiO2, when carrying out photocatalytic degradation to COD, the BOD in the middle of waste water, being uniformly distributed for titanium dioxide is conducive to
The degradation efficiency of degradation agent degraded harmful substance is improved, sufficiently degraded, the effect of lifting sewage treatment is ensured.
Claims (7)
1. a kind of nano titanium dioxide photocatalysis degradation agent, it is characterised in that its structure is：Titanium dioxide nanoparticle uniformly divides
Cloth is on the surface of phenolic resin hollow microsphere.
2. a kind of method for preparing nano titanium dioxide photocatalysis degradation agent as claimed in claim 1, it is characterised in that including with
Lower step：
The preparation of S1, nano-silicon dioxide modified phenolic resin：
In the basic conditions, nano-silicon dioxide modified phenolic aldehyde is prepared by condensation polymerization with nano silicon, phenol, formaldehyde
Resin；
The preparation of S2, nano titanium dioxide photocatalysis degradation agent：
Nano-silicon dioxide modified phenolic resin prepared by S1 is combined with nano titanium oxide；After compound end, hydrogen-oxygen is added
Change sodium solution, until be completely dissolved silica, separate, dry, in a nitrogen atmosphere finally, 450 ~ 550 DEG C of sintering 12 ~
48h, obtains nano titanium dioxide photocatalysis degradation agent.
3. preparation method as claimed in claim 2, it is characterised in that be the step of S1：
S1.1, to absolute ethyl alcohol is added in Ludox, then stirring to formed gel, centrifugation, be precipitated, will precipitation drying,
Obtain nano silicon；
S1.2, by NaOH, phenol and water under conditions of 40 ~ 60 DEG C, stir；
S1.3, the formalin for taking mass fraction 35 ~ 40%, nano silicon prepared by S1.1 is put into wherein, and stirring is equal
It is even；
S1.4, S1.2 systems are warming up to 60 ~ 70 DEG C, S1.3 gained formaldehyde mixtures are added 3 ~ 4 times every 10 ~ 15min points；Plus
Enter after formaldehyde mixture finishes, maintain 60 ~ 65 DEG C, react 4 ~ 4.5h；
S1.5, be warming up to 75 ~ 80 DEG C, continue to react 1 ~ 2h, then vacuum distillation to system viscosity it is constant when, naturally cool to 60
Below DEG C, the p-methyl benzenesulfonic acid aqueous solution of mass fraction 60 ~ 70% is added to be solidified, until pH=6-7, obtains nanometer titanium dioxide
Si modification phenolic resin.
4. preparation method as claimed in claim 3, it is characterised in that：In S1.1, based on mass volume ratio, Ludox: anhydrous
Ethanol=50 ~ 100g: 80 ~ 200mL.
5. preparation method as claimed in claim 3, 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 silicon=2.8 ~ 5.4g: 188 ~ 276g: 5 ~ 10mL: 290 ~
300g∶50~140g。
6. preparation method as claimed in claim 2, it is characterised in that be the step of S2：
S2.1, Butyl Phthalate and absolute ethyl alcohol are placed in container, sealed, ultrasonic disperse is uniform；
S2.2, well mixed Butyl Phthalate and absolute ethyl alcohol are poured into reaction bulb, add nano-silicon dioxide modified phenol
Urea formaldehyde, 15 ~ 30min of stirring at normal temperature；
S2.3, product is poured into centrifuge tube, be centrifuged, ethanol is outwelled, repeatedly with absolute ethanol washing, until the ethanol on upper strata
Untill water white transparency, the material of centrifuge tube ttom of pipe is collected, the nano-silicon dioxide modified phenolic aldehyde in s2.2 is replaced with the gleanings
Resin, in the same way, repeat step S2.1- S2.3 are for several times；
In S2.4, the centrifuge tube ttom of pipe material to last collection, sodium hydroxide solution is added, until being completely dissolved titanium dioxide
Silicon, separates, dries, and in a nitrogen atmosphere, 450 ~ 550 DEG C of 12 ~ 48h of sintering obtain nano titanium dioxide photocatalysis degraded finally
Agent.
7. preparation method as claimed in claim 6, it is characterised in that：In S2.1 and S2.2, according to mass volume ratio, metatitanic acid fourth
Ester: absolute ethyl alcohol: nano-silicon dioxide modified phenolic resin=1 ~ 2mL: 4 ~ 8mL: 10 ~ 15g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710127324.5A CN106824293B (en) | 2017-03-06 | 2017-03-06 | A kind of nano titanium dioxide photocatalysis degradation agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710127324.5A CN106824293B (en) | 2017-03-06 | 2017-03-06 | A kind of nano titanium dioxide photocatalysis degradation agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106824293A true CN106824293A (en) | 2017-06-13 |
| CN106824293B CN106824293B (en) | 2019-05-10 |
Family
ID=59138873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710127324.5A Active CN106824293B (en) | 2017-03-06 | 2017-03-06 | A kind of nano titanium dioxide photocatalysis degradation agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106824293B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108283937A (en) * | 2018-03-12 | 2018-07-17 | 南京科技职业学院 | A kind of laboratory exhaust gas processing method and device |
| US11396920B2 (en) | 2019-06-24 | 2022-07-26 | Shanghai Reinphen New Material Technology Co., Ltd. | Method for improving braking performance of microporous friction materials under wet conditions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996014932A1 (en) * | 1994-11-16 | 1996-05-23 | Toto Ltd. | Photocatalytic functional material and method of production thereof |
| CN102553648A (en) * | 2011-12-21 | 2012-07-11 | 中国科学院青岛生物能源与过程研究所 | Photocatalyst for visible light transformation and preparation method of same |
-
2017
- 2017-03-06 CN CN201710127324.5A patent/CN106824293B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996014932A1 (en) * | 1994-11-16 | 1996-05-23 | Toto Ltd. | Photocatalytic functional material and method of production thereof |
| CN102553648A (en) * | 2011-12-21 | 2012-07-11 | 中国科学院青岛生物能源与过程研究所 | Photocatalyst for visible light transformation and preparation method of same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108283937A (en) * | 2018-03-12 | 2018-07-17 | 南京科技职业学院 | A kind of laboratory exhaust gas processing method and device |
| US11396920B2 (en) | 2019-06-24 | 2022-07-26 | Shanghai Reinphen New Material Technology Co., Ltd. | Method for improving braking performance of microporous friction materials under wet conditions |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106824293B (en) | 2019-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105170097B (en) | A kind of TiO2Nuclear-shell structured nano-composite materials of/ZIF 8 and preparation method thereof | |
| CN101670280B (en) | Titanium dioxide microspheroidal photocatalyst with high active surface and preparation method thereof | |
| CN107658475A (en) | A kind of platinum/black phosphorus@carbon ball methanol fuel cell anode catalyzers and preparation method thereof | |
| CN106268630A (en) | Silicon dioxide-graphene composite material, preparation method thereof and treatment method for removing dye pollutants in water | |
| CN103172897B (en) | Preparation method of nano-fiber supported nano-titania mesoporous material | |
| CN109096504A (en) | A kind of gradient gel, preparation method and application | |
| CN104722281B (en) | A kind of nano titanium oxide/chitosan three-dimensional is composite porous and preparation method thereof | |
| CN107416898A (en) | A kind of titanium dioxide hollow micro-nano ball, its preparation method and application | |
| CN105344334B (en) | A kind of preparation method of polyvinyl alcohol/silicon dioxide complex microsphere | |
| CN101306359A (en) | Composite aerogel photocatalyst for recovering titanium dioxide/silicon dioxide | |
| CN106622128A (en) | Composite nano material for air purification and preparation method of composite nano material | |
| CN110396348A (en) | A kind of road coating and preparation method purifying vehicle exhaust | |
| CN107983415B (en) | Honeycomb TiO using microporous starch as template2Porous microspheres and method for preparing same | |
| CN106824293A (en) | A kind of nano titanium dioxide photocatalysis degradation agent and preparation method thereof | |
| CN107376975A (en) | Visible light catalysis activity N doping nucleocapsid shape titanium dioxide and preparation method thereof | |
| CN105273216B (en) | 3 D stereo surpasses the preparation method of fold polylactic acid microsphere | |
| CN109046450A (en) | A kind of BiOCl/(BiO)2CO3The cellulose acetate of load/fibroin hybridized film preparation method and application | |
| CN103537324B (en) | Porous charcoal based solid acid catalyst and preparation method | |
| CN107459885A (en) | A kind of photo-catalytic coating and preparation method thereof | |
| CN110156038A (en) | A kind of micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve and its preparation method and application | |
| CN101671032B (en) | Calcium silicate multi-level nano-structure mesoporous microsphere and preparation method thereof | |
| CN102389787B (en) | Carbon-doped titanium dioxide hollow spherical photocatalyst and preparation method thereof | |
| CN106957417B (en) | A kind of method that galapectite graphene oxide complex catalysts prepare poly-epsilon-caprolactone | |
| CN106833237A (en) | A kind of photocatalysis dope for inner wall of architecture and preparation method thereof | |
| CN107189692A (en) | A kind of silicon titanium aeroge absorption and photocatalysis interior wall coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |