CN108404896A - A kind of photochemical catalyst of Liquidity limit dyestuff - Google Patents
A kind of photochemical catalyst of Liquidity limit dyestuff Download PDFInfo
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- CN108404896A CN108404896A CN201810239500.9A CN201810239500A CN108404896A CN 108404896 A CN108404896 A CN 108404896A CN 201810239500 A CN201810239500 A CN 201810239500A CN 108404896 A CN108404896 A CN 108404896A
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- positive ion
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- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 239000000975 dye Substances 0.000 title claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 44
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 44
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 44
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 44
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 44
- 238000010521 absorption reaction Methods 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 19
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 16
- 230000032683 aging Effects 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000002351 wastewater Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000004088 foaming agent Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000004042 decolorization Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- 238000004043 dyeing Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 description 18
- 230000015556 catabolic process Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 10
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241001269238 Data 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
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
Abstract
The invention discloses a kind of photochemical catalysts of Liquidity limit dyestuff, belong to field of material technology.It is pore-foaming agent, absolute ethyl alcohol as solvent that the present invention, which is using polyvinylpyrrolidone (PVP), butyl titanate, tetraethyl orthosilicate, silane coupling agent KH560 are primary raw material, using sol-gal process precursor solution, then will be obtained after aging, drying, calcining can be with the TiO of the efficient absorption dye of positive ion2/SiO2Photochemical catalyst.The dye of positive ion that can effectively in adsorption aqueous solution of the present invention, is provided simultaneously with photocatalytic degradation effect, the catalyst of recycling can recycle after calcining.It can be used for the fields such as the decoloration of discarded dyeing waste water.
Description
Technical field
The present invention relates to a kind of photochemical catalysts of Liquidity limit dyestuff, belong to field of material technology.
Background technology
Textile industry will produce a large amount of dyeing waste waters, the complicated aromatic series of dyestuff in production process and its last handling process
Structure makes them more stablize, it is difficult to be removed from waste water, the discharge of the dyeing waste water of unprocessed mistake can bring serious ring
Border problem.The method of currently processed dyeing waste water has Physical, biodegradation technique and chemical method etc..Wherein, using most
It is chemical method, including Coagulation Method, oxidizing process, electrochemical process and photocatalytic method etc..Photocatalytic degradation is because it is efficient, environmental protection, easily behaviour
The advantages of making and become most promising one of hair method.
Photocatalyst starts from the 1970s, effectively being degraded by luminous energy is transformed into chemical energy organic
Object.Wherein Photocatalytic Oxidation With Semiconductors technology is with efficient, low energy consumption, easy to operate, reaction condition is mild, non-secondary pollution
The advantages that, effectively it can convert organic pollution to inorganic molecules, realization is completely inorganization, and the chloroform that can degrade,
Many conventional methods such as Polychlorinated biphenyls, organic phosphorus compound are difficult to the substance removed.
Methylene blue is a kind of typical dye of positive ion, is normally used in various photocatalysis experiments and adsorption experiment.
Researcher is more by polyurethane foam (PUFs), carbon nanotube (CNTs), the substances such as activated carbon and TiO2Photochemical catalyst
In conjunction with method come improve the absorption property of photochemical catalyst make a return journey water removal in methylene blue to promote dyestuff removal rate.In order to
Adsorption efficiency is improved, achievees the purpose that environmental protection, can be recycled, needs to prepare a kind of new catalyst that absorption property is promoted.
Invention content
The first purpose of the invention is to provide a kind of TiO of the efficient absorption dye of positive ion2/SiO2Photochemical catalyst, be with
Polyvinylpyrrolidone (PVP) is pore-foaming agent, absolute ethyl alcohol is solvent, butyl titanate, tetraethyl orthosilicate, silane coupling agent
KH560 is primary raw material, and precursor solution is prepared using sol-gal process, then will be prepared after its aging, drying, calcining
The TiO of the efficient absorption dye of positive ion2/SiO2Photochemical catalyst.
In one embodiment, the TiO2/SiO2Middle TiO2Mass fraction be 45%-90%, SiO2Quality point
Number is 0%-45%.
In one embodiment, the TiO2/SiO2Middle TiO2Mass fraction be 65%-85%, SiO2Quality point
Number is 15%-35%.
In one embodiment, the TiO2/SiO2Middle TiO2Mass fraction be 65%, SiO2Mass fraction be
35%.
In one embodiment of the invention, Si:Ti:The molar ratio of PVC is 6~15:0~9:1~2.
In one embodiment of the invention, Si:Ti:The molar ratio of PVC is 9:0:1.
In one embodiment of the invention, Si:Ti:The molar ratio of PVC is 15:3:2.
In one embodiment of the invention, Si:Ti:The molar ratio of PVC is 6:3:1.
In one embodiment of the invention, Si:Ti:The molar ratio of PVC is 9:9:2.
In one embodiment, the aging is specifically：Stand 5-8 hours at room temperature.
In one embodiment, described dry is specifically：Gel is in 80 DEG C of baking oven until being completely dried.
In one embodiment, the calcining is to calcine 1-4h at 200-1000 DEG C.
In one embodiment, the calcining is to calcine 2h at 600 DEG C.
Second object of the present invention is to provide a kind of TiO of the efficient absorption dye of positive ion2/SiO2The system of photochemical catalyst
Preparation Method specifically includes：
(1) KH560 is added in salpeter solution；Later, tetraethyl orthosilicate and/or butyl titanate is added, is rubbed
You are than being 6~15:0~9 silicon and the mixed solution of titanium；
(2) using absolute ethyl alcohol as solvent, the PVP/ ethanol solutions of 0.08g/mL are configured, and under magnetic stirring by it
It is added in mixed solution obtained in the previous step；Solution magnetic agitation after a certain period of time, obtains precursor solution；
(3) precursor solution is obtained into colloidal sol in aging 5-8 hours at room temperature, the colloidal sol after aging is placed in 80 DEG C of baking oven
Middle drying obtains xerogel, is then ground to powder；
(4) powdered xerogel is calcined into 1-4h under 200-1000 DEG C of high temperature, to completely remove residual in the solution
PVP, obtained product is by further grinding.
The present invention also provides application of the catalyst in terms of Liquidity limit dyestuff.
In one embodiment of the invention, the application includes carrying out decolorization to waste water.
Advantages of the present invention and effect：
(1) TiO of the invention2/SiO2Photochemical catalyst, it is strong, recyclable sharp simultaneously with adsorption rate height, photo-catalysis capability
With the advantages that, adsorption rate remains at 86% or more after recycling 5 times, and degradation rate approach 100% can be used for dyeing waste water
The fields such as decoloration.
(2) the method for the present invention, by effectively controlling TiO2、SiO2Ratio and calcination temperature etc., have obtained function admirable
TiO2/SiO2。
(3) the method for the present invention it is easy, it is easily-controllable, can flexible operating.
Description of the drawings
Fig. 1 is TiO2/SiO2Photochemical catalyst preparation flow figure；
Fig. 2 a are the TiO that the embodiment of the present invention 2 is prepared2/SiO2Photochemical catalyst electron micrograph；2b is to implement
Absorption degradation curve of the example 2 to the 20mg/L methylene blue solutions of 60ml；
Fig. 3 a are absorption and light degradation reaction unit；3b is embodiment 2 and reference examples to methylene blue solution absorption degradation
Curve.
Specific implementation mode
As shown in Figure 1, for the TiO of the present invention2/SiO2Photochemical catalyst preparation flow figure.Using PVP as pore-foaming agent, absolute ethyl alcohol
For solvent, butyl titanate, tetraethyl orthosilicate etc. are raw material, and precursor sol is prepared using sol-gal process.It is small by 6
When aging obtain gel, in 80 DEG C of baking oven drying obtain xerogel.Then, by the xerogel after grinding through 200-1000
DEG C calcining, obtain TiO2/SiO2Material obtains final photocatalyst powder by further grinding.
To obtained TiO2/SiO2Photochemical catalyst carries out absorption property test, and test method is as follows：
The absorption of sample and light degradation property are tested using the test device in Fig. 3.Sample is placed in reactor
In, certain density aqueous solution of methylene blue is injected in reactor by peristaltic pump, peristaltic pump is opened and is recycled.In dark
It is adsorbed under environment 40 minutes, then opens ultraviolet lamp and carry out light degradation test.The usage amount of sample is 0.1g, methylene in test
Blue aqueous solution usage amount is 60mL, initial concentration 20mg/L.
Test result shows that sample can adsorb 88% methylene blue for 40 minutes.60 minutes or so light degradation stage
Time can be degradable the methylene blue of remainder.
Embodiment 1
TiO is prepared as follows2/SiO2Photochemical catalyst：
(1) solution A is prepared：The KH560 of 1.89g is added in the aqueous solution of nitric acid (pH=2.3) of 0.36ml；Later, above
Tetraethyl orthosilicate, the butyl titanate that 1 stoichiometric ratio of table is sequentially added in solution, obtaining 6mL, to contain silicon, the mixing of titanium molten
Liquid.
(2) 12ml polyvinylpyrrolidones/ethanol solution is prepared, and it is added under magnetic stirring to solution A
In.
(3) precursor solution is stood to aging at room temperature and obtains colloidal sol within 5-8 hours, the colloidal sol after aging is placed in 80 DEG C
Drying obtains xerogel in baking oven, is then ground to powder；
(4) powdered xerogel is calcined into 1-4h under 600 DEG C of high temperature, to remove PVP and other organic matters, obtained
Product finally obtains different TiO by further grinding2、SiO2The TiO of ratio2/SiO2Powder.
Wherein, different TiO2、SiO2, PVP ratios composition of raw materials under (table 1).
1 difference TiO of table2/SiO2Ti, Si, PVP ratio in photochemical catalyst
Embodiment 2
(1) solution A is prepared：The KH560 of 1.89g is added in the aqueous solution of nitric acid (pH=2.3) of 0.36ml；Later, above
Tetraethyl orthosilicate, the butyl titanate that 1 stoichiometric ratio of table is sequentially added in solution, obtaining 6mL, to contain silicon, the mixing of titanium molten
Liquid, wherein Ti:The molar ratio of Si is 2:1.
(2) after, prepare 12ml polyvinylpyrrolidones/ethanol solution, and it is added under magnetic stirring to
In solution A, make Si:The molar ratio of PVP is 3:1.
(3) precursor solution is stood to aging at room temperature and obtains colloidal sol within 5-8 hours, the colloidal sol after aging is placed in 80 DEG C
Drying obtains xerogel in baking oven, is then ground to powder；
(4) 1-4h will be calcined under powdered xerogel at the temperatures shown in table 2 high temperature, had to remove PVP and other
Machine object, obtained product finally obtain different TiO by further grinding2、SiO2The TiO of ratio2/SiO2Powder.
The different calcination temperatures of table 2
Absorption and light degradation experiment carry out in the homemade reactor (such as Fig. 3 a) for having cycle vermiculator.Specific steps
It is as follows：
(1) aqueous solution of methylene blue that 60mL initial concentrations are 20mg/L is placed with 0.1g TiO by peristaltic pump sucking2/
SiO2In the reaction unit of powder；
(2) peristaltic pump is opened, 40min is adsorbed under dark surrounds；
(3) after adsorbing, the high-pressure sodium lamp of 250W is opened as light degradation light source, it is molten that 5mL is extracted in certain intervals
Liquid measures its concentration using UV-1800 ultraviolet-visible light fluophotometers, and the solution after measurement is put back to reaction unit and continued
Light degradation
(4) after measured, the final decoloration performance that the sample obtained under distinct methods obtains is as shown in table 3.
Table 3TiO2/SiO2Photochemical catalyst adsorption capacity and light degradation aptitude tests result
Note：Adsorption rate is that 40 minutes obtained experimental datas are adsorbed under dark surrounds, and degradation rate is 60 minutes gained of light degradation
Experimental data.
Cycle carries out absorption to sample after experiment after centrifugation, filtering, drying, 400 DEG C of calcinings and light degradation is tested, sample
The results are shown in Table 4 for 3 five loop tests of product.
Experimental result is shown, is adsorbed and the TiO after light degradation experiment2/SiO2Powder still has excellent by calcination processing
Absorption and degradation capability.
The TiO of the present invention2/SiO2Photochemical catalyst is high simultaneously with adsorption rate, photo-catalysis capability is strong, can be recycled etc.
Advantage can be used for the fields such as decolorizing printing and dyeing waste water.
Reference examples
In addition, inventor compares the absorption of (table 5) sample and light degradation property under different material formula, as a result such as Fig. 3 b
It is shown.Wherein, specific experiment condition is compared with the parameter of embodiment 2, and only material composition is different.
5 different material ingredient of table
Note：" √ " indicates that addition, "-" expression are not added.
Inventor tests absorption and the light degradation property of embodiment 2 and reference examples using the identical test methods of Fig. 3 a,
Its result is as shown in Figure 3b.PVP is added in material can promote the adsorption capacity of material, in order to illustrate PVP in material preparation
Play the role of pore-foaming agent, the pore structure of material is analyzed, BET specific surface area test result is as shown in table 6.Its result
Pore-foaming agent can be played the role of really by being shown in addition PVP in collosol and gel, and the change of this microstructure improves material
Adsorption capacity.
Table 6BET specific surface area test results
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not limited to the present invention, any to be familiar with this skill
The people of art can do various change and modification, therefore the protection model of the present invention without departing from the spirit and scope of the present invention
Enclosing be subject to what claims were defined.
Claims (10)
1. a kind of TiO of the efficient absorption dye of positive ion2/SiO2Photochemical catalyst, which is characterized in that be with polyvinylpyrrolidone
Pore-foaming agent, absolute ethyl alcohol are solvent, and butyl titanate, tetraethyl orthosilicate, silane coupling agent KH560 are primary raw material, are used
Sol-gal process prepares precursor solution, then will prepare the efficient absorption dye of positive ion after its aging, drying, calcining
TiO2/SiO2Photochemical catalyst.
2. the TiO of the efficient absorption dye of positive ion according to claim 12/SiO2Photochemical catalyst, which is characterized in that described
TiO2/SiO2Middle TiO2Mass fraction be 45%-90%, SiO2Mass fraction be 0%-45%.
3. the TiO of the efficient absorption dye of positive ion according to claim 12/SiO2Photochemical catalyst, which is characterized in that described
TiO2/SiO2Middle TiO2Mass fraction be 65%-85%, SiO2Mass fraction be 15%-35%.
4. according to the TiO of any efficient absorption dye of positive ion of claims 1 to 32/SiO2Photochemical catalyst, feature exist
In Si:Ti:The molar ratio of PVC is 6~15:0~9:1~2.
5. the TiO of the efficient absorption dye of positive ion according to claim 12/SiO2Photochemical catalyst, which is characterized in that described
Aging is to stand 5-8 hours at room temperature.
6. the TiO of the efficient absorption dye of positive ion according to claim 12/SiO2Photochemical catalyst, which is characterized in that described
Drying is completely dried in 60~80 DEG C be dried to.
7. the TiO of the efficient absorption dye of positive ion according to claim 12/SiO2Photochemical catalyst, which is characterized in that described
Calcining is to calcine 1-4h at 200-1000 DEG C.
8. a kind of TiO of the efficient absorption dye of positive ion2/SiO2The preparation method of photochemical catalyst, which is characterized in that specific steps
Including：
(1) KH560 is added in salpeter solution；Later, tetraethyl orthosilicate and/or butyl titanate is added, obtains molar ratio
It is 6~15:0~9 silicon and the mixed solution of titanium；
(2) using absolute ethyl alcohol as solvent, 0PVP/ ethanol solutions are configured, and it is added under magnetic stirring to step (1)
In obtained mixed solution；
(3) mixed solution 5~8h of aging at room temperature that step (2) obtains, is placed in 60~80 DEG C of drying and obtains xerogel, grinding
At powder；
(4) powdered xerogel is calcined to 1~4h under 200-1000 DEG C of high temperature, is remained in the solution with completely removing
PVP, obtained product is by further grinding.
9. the TiO of any efficient absorption dye of positive ion of claim 1~82/SiO2Photochemical catalyst is in Liquidity limit
Application in terms of dyestuff.
10. a kind of method to waste water decoloring processing, which is characterized in that it is any described to add claim 1~8 into waste water
The TiO of the efficient absorption dye of positive ion2/SiO2Photochemical catalyst carries out decolorization.
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