CN109336172A - The method for preparing photocatalysis nano-titanium dioxide as raw material using metatitanic acid - Google Patents
The method for preparing photocatalysis nano-titanium dioxide as raw material using metatitanic acid Download PDFInfo
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- CN109336172A CN109336172A CN201811280309.5A CN201811280309A CN109336172A CN 109336172 A CN109336172 A CN 109336172A CN 201811280309 A CN201811280309 A CN 201811280309A CN 109336172 A CN109336172 A CN 109336172A
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- metatitanic acid
- titanium dioxide
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- 239000002253 acid Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 52
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 23
- 239000002994 raw material Substances 0.000 title claims abstract description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 48
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000725 suspension Substances 0.000 claims abstract description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 23
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 238000001935 peptisation Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000005360 mashing Methods 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000001816 cooling Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000001376 precipitating effect Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 39
- 229910001868 water Inorganic materials 0.000 description 27
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 26
- 229940012189 methyl orange Drugs 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000005286 illumination Methods 0.000 description 21
- 238000010521 absorption reaction Methods 0.000 description 12
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000004847 absorption spectroscopy Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000012452 mother liquor Substances 0.000 description 8
- 239000013049 sediment Substances 0.000 description 7
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000002479 acid--base titration Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 238000005485 electric heating Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910003890 H2TiO3 Inorganic materials 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910010298 TiOSO4 Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- KADRTWZQWGIUGO-UHFFFAOYSA-L oxotitanium(2+);sulfate Chemical compound [Ti+2]=O.[O-]S([O-])(=O)=O KADRTWZQWGIUGO-UHFFFAOYSA-L 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000009738 saturating 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
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- -1 ultraviolet screener Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- 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
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Abstract
The invention discloses a kind of methods for preparing photocatalysis nano-titanium dioxide as raw material using metatitanic acid, belong to catalytic nanometer field of material technology.The problems such as it is complicated that the invention solves the preparation process flows of prior art nano-titanium dioxide, at high cost.The present invention solves the problems, such as that this technical solution is the method for preparing photocatalysis nano-titanium dioxide as raw material using metatitanic acid.Sulfuric acid solution acidolysis is added in metatitanic acid by this method, obtains titanyl sulfate solution；Titanyl sulfate solution is added inorganic alkali solution and neutralizes to obtain positive metatitanic acid precipitating；Positive metatitanic acid is configured to suspension, hydrogen peroxide is added into suspension and obtains pertitanic acid；Pertitanic acid is carried out hydro-thermal reaction after cooling to carry out being spray-dried to obtain nano-titanium dioxide.The method of the present invention is at low cost, energy conservation and environmental protection, and excellent product performance is extensive using field.
Description
Technical field
The invention belongs to catalytic nanometer Material Fields, and in particular to a kind of to prepare photocatalysis nanometer by raw material of metatitanic acid
The method of titanium dioxide.
Background technique
Nano-titanium dioxide is a kind of nano material being most widely used at present.Nano-titanium dioxide has specific surface area
Greatly, fusing point is low, magnetic strong, characteristics such as absorbing properties are good, resistant to chemical etching, harmless, be widely used in cosmetics,
The fields such as high grade paint, catalyst, fine ceramics, advanced paint, ultraviolet screener, semiconductor material.Nano-titanium dioxide
Photo-generate electron-hole can directly and bacterium cell wall or internal composition occur biochemical reaction, make bacteria inactivation, be one kind very
Good anti-biotic material.The common crystal form of nano-titanium dioxide has anatase, rutile, three kinds of brockite.Anatase and gold at present
Red stone-type nano-titanium dioxide is more widely applied in photocatalysis field.Brockite is former due to its stability and catalytic activity etc.
Cause, application are fewer.The use form of nano-titanium dioxide is mostly powder at present, but powder has easily during direct use
The defects of reunion, difficult low efficiency and recycling, significantly limit the use of nano-titanium dioxide.To improve nano-titanium dioxide
Service efficiency and application range, prepare nano titania slurry and also just necessitate.
CN201410629923.3 discloses the low temperature preparation side of a kind of brockite and rutile titanium dioxide nanometer mixed crystal
Method, key step include: the preparation of (1) presoma: using tetraethyl titanate as titanium source, by ultrapure water, tetraethyl titanate, anhydrous
The volume ratio of ethyl alcohol is that the ratio of 1:3~4:15~20 mixes, and is dried to obtain hydrated titanium dioxide, mass fraction 30% is added
Hydrogen peroxide reacts peroxo titanic acid sol is made completely；(2) pH adjusting agent and template are added in peroxo titanic acid sol；(3)
It is to be stirred under 40~60 DEG C of water bath conditions that colloidal sol, which is placed at temperature, removes excess hydrogen peroxide；(4) colloidal sol is packed into anti-
It answers in kettle, the hydro-thermal reaction time is 24~48h under the conditions of temperature is 160~200 DEG C, and product is washed to neutrality, is dried under reduced pressure
It grinds and multiphase nano-titanium dioxide is made.But the process flow of the technique is complicated, needs that pH adjusting agent and template is added,
During removing excess hydrogen peroxide with the method for water-bath, due to the excessively high complexing that can make between pertitanic acid molecule of temperature, contracting
Poly- reaction carries out thorough, puts up a bridge mutually between condensation polymer, forms three-dimensional net structure, and the hydrone of free state is gradually in colloidal sol
It is wrapping in network structure, the mobility of colloidal sol is made to be deteriorated, viscosity increases；And hydrothermal temperature is higher, hydro-thermal overlong time
It may be such that the TiO 2 particles prepared are thicker.
CN201410274717.5 discloses a kind of preparation method of titania hydrosol, and key step includes: (1)
It provides two and washes qualified metatitanic acid slurry, TiO in the metatitanic acid slurry2Concentration is 260g/L~280g/L；(2) in stirring
It is lower that metatitanic acid slurry is heated to 75 DEG C~85 DEG C and the sodium hydroxide solution that concentration is 48%~50% is added, wherein hydrogen-oxygen
The mass ratio for changing sodium and metatitanic acid is 5:1；(3) slurry obtained by step b is warming up to 116 DEG C~118 DEG C curings, obtained
Positive sodium titanate solution；(4) concentration that deionized water is added in positive sodium titanate solution, and controls positive sodium titanate solution is 90g/L
~110g/L；(5) slurry washing for obtaining step (4), and control Na+Ion concentration is in 500ppm hereinafter, obtaining positive metatitanic acid
Presoma；(6) the control Standard entertion deionized water for being 3g/L~30g/L according to concentration by the titanic acid precursor, and add
Enter acid, adjusts its pH value to 1.2~2.0, and stirring to obtain titania hydrosol.But the technique is at high cost, and technique is cumbersome；
The acid being added is nitric acid, is had a certain impact to environment.
Summary of the invention
It is at high cost the technical problem to be solved by the present invention is to the preparation process flow of existing nano-titanium dioxide complexity.This
Invention solves the problems, such as that this technical solution prepares photocatalysis nano-titanium dioxide by raw material of metatitanic acid there is provided a kind of
Method.Method includes the following steps:
A, metatitanic acid is beaten and is stirred, sulfuric acid solution acidolysis is then added, obtains titanyl sulfate solution；The use of the sulfuric acid
Amount is to make the mass concentration 60% of the sulfuric acid in system.
B, the titanyl sulfate solution after acidolysis is added into deionized water, be then stirred, is added in inorganic alkali solution progress
With when pH value is 7~9, stop stirring, precipitate positive metatitanic acid；
C, positive metatitanic acid being precipitated and is filtered, washing filter cake repeatedly with deionized water until can't detect SO4 2-Until；
D, the positive metatitanic acid after washing is configured to≤the suspension of 0.2mol/L；
E, hydrogen peroxide is added into suspension and carries out peptization, and constantly stir to clarify transparent；
F, the system after clear is continued to stir, is then allowed to stand to obtain pertitanic acid；
G, pertitanic acid is subjected to hydro-thermal reaction, then cooled down, carry out being spray-dried to obtain nano-titanium dioxide.
Wherein, metatitanic acid mashing stirring to concentration is 250g/l~400g/l in step A described in the above method；The acid
Keep system temperature at 120 DEG C~160 DEG C when solution.
Wherein, the concentration of the titanyl sulfate solution in step B described in the above method after acidolysis is 200g/l~250g/l；
The inorganic alkali solution is at least one of sodium hydroxide, potassium hydroxide, ammonium hydroxide or urea.
Wherein, the pH of positive metatitanic acid described in above method step B is 7~9.Preferably, positive metatitanic acid described in step B
PH is 8~9.
Wherein, in above method step E, the hydrogen peroxide is by Ti in suspension4+With H2O2Molar ratio for 1:8~15 plus
Enter；The adding manner is disposably to rapidly join.
Wherein, the pH of pertitanic acid described in above method step E is 7~9.
Wherein, the time for continuing stirring after suspension clear described in above method step F is 30min~90min.
Wherein, the time of standing described in above method step F is 12h~for 24 hours.
Wherein, the temperature of hydro-thermal reaction described in above method step F is 90~150 DEG C；The time of the hydro-thermal reaction
For 8~for 24 hours.
Wherein, described to be cooled to chilling in above method step G, system is cooled to 15~25 DEG C in 20min.It is preferred that
, the mode of the chilling is to be cooled down with water shower reaction vessel.
The beneficial effects of the present invention are；The present invention is from a wealth of sources, be easy to get using metatitanic acid as raw material；The method of the present invention
Easy to operate, required raw and auxiliary material is few, does not need for pH adjusting agent and template to be added in peroxo titanic acid sol, eliminates dioxygen
Cooling down operation when water is reacted with positive metatitanic acid also removes excessive hydrogen peroxide, and the peroxide after standing using the method stood
The pH for changing titanium is neutrality；The temperature of hydro-thermal reaction is lower, and the production cycle is also shorter, and production cost is low.The method of the present invention prepares institute
It obtains nano-titanium dioxide to have excellent performance, 93.07% can reach to the methyl orange degradation rate of 20mg/L in 1h, the solution after degradation is in
It is colourless；Nano-titanium dioxide pH is 7~8, on using medium (such as coating, woodenware) to have a good application prospect without influence.
Detailed description of the invention
Fig. 1 is nano-titanium dioxide preparation technology flow chart of the present invention.
Fig. 2 is the ultraviolet-visible absorption spectroscopy figure of 1 nano titanium dioxide degradable methyl orange of embodiment.
Fig. 3 is the ultraviolet-visible absorption spectroscopy figure of 2 nano titanium dioxide degradable methyl orange of embodiment.
Fig. 4 is the ultraviolet-visible absorption spectroscopy figure of 3 nano titanium dioxide degradable methyl orange of embodiment.
Fig. 5 is the ultraviolet-visible absorption spectroscopy figure of 4 nano titanium dioxide degradable methyl orange of embodiment.
Fig. 6 is the XRD analysis figure of Examples 1 to 4 (1#~4#) nano-titanium dioxide.
Specific embodiment
Specifically, the method for preparing photocatalysis nano-titanium dioxide as raw material using metatitanic acid, comprising the following steps:
A, metatitanic acid is beaten and is stirred, sulfuric acid solution acidolysis is then added, obtains titanyl sulfate solution；The use of the sulfuric acid
Amount is to make the mass concentration 60% of the sulfuric acid in system.
B, the titanyl sulfate solution after acidolysis is added into deionized water, be then stirred, is added in inorganic alkali solution progress
With when pH value is 7~9, stop stirring, precipitate positive metatitanic acid；
C, positive metatitanic acid being precipitated and is filtered, washing filter cake repeatedly with deionized water until can't detect SO4 2-Until；
D, the positive metatitanic acid after washing is configured to≤the suspension of 0.2mol/L；
E, hydrogen peroxide is added into suspension and carries out peptization, and constantly stir to clarify transparent；
F, the system after clear is continued to stir, is then allowed to stand to obtain pertitanic acid；
G, pertitanic acid is subjected to hydro-thermal reaction, then cooled down, carry out being spray-dried to obtain nano-titanium dioxide.
Wherein, metatitanic acid mashing stirring to concentration is 250g/l~400g/l in step A described in the above method；The acid
Keep system temperature at 120 DEG C~160 DEG C when solution.
Wherein, the concentration of the titanyl sulfate solution in step B described in the above method after acidolysis is 200g/l~250g/l；
The inorganic alkali solution is at least one of sodium hydroxide, potassium hydroxide, ammonium hydroxide or urea.
Wherein, the pH of positive metatitanic acid described in above method step B is 7~9.Preferably, positive metatitanic acid described in step B
PH is 8~9.
Wherein, in above method step E, the hydrogen peroxide is by Ti in suspension4+With H2O2Molar ratio for 1:8~15 plus
Enter；The adding manner is disposably to rapidly join.
Wherein, the pH of pertitanic acid described in above method step E is 7~9.
Wherein, the time for continuing stirring after suspension clear described in above method step F is 30min~90min.
Wherein, the time of standing described in above method step F is 12h~for 24 hours.
Wherein, the temperature of hydro-thermal reaction described in above method step F is 90~150 DEG C；The time of the hydro-thermal reaction
For 8~for 24 hours.
Wherein, described to be cooled to chilling in above method step G, system is cooled to 15~25 DEG C in 20min.It is preferred that
, the mode of the chilling is to be cooled down with water shower reaction vessel.
The present invention first obtains positive metatitanic acid with sulfuric acid solution using metatitanic acid as raw material.
Main reaction are as follows:
H2TiO3+H2SO4=TiOSO4+2H2O
TiO2++2OH-+H2O=Ti (OH)4
The dosage of the sulfuric acid is to make the mass concentration 60% of the sulfuric acid in system.The specific dosage of sulfuric acid can refer to down
Formula calculates:
Wherein, the acidolysis of above method step A can be operated specifically according to the following steps takes metatitanic acid concentration mashing as required, adds
Enter into three-neck flask, sulfuric acid solution then is added by reaction ratio requirement, is reacted acutely after sulfuric acid solution is added, temperature is fast
Speed increases, and opens condensed water at this time, keeps the temperature at 120 DEG C~160 DEG C.Complete to sulfuric acid fundamental reaction, temperature can reduce, and be
Make to carry out more abundant, condensed water can be closed, opens electric heating cover, so that temperature is remained at 120 DEG C~160 DEG C, to molten
Liquid becomes clarification, keeps 10min or so, stops heating, is cooled to room temperature.
Then add deionized water to be configured to 200g/l~250g/l the titanyl sulfate solution after acidolysis, be stirred.With
Inorganic alkali solution carries out acid-base titration, when pH value is 7~9, stops stirring, obtains positive metatitanic acid precipitating；Sediment through filtering,
It is washed until can't detect corresponding impurity anions repeatedly with deionized water.Positive metatitanic acid is used further to subsequent step.
The solid content for the positive metatitanic acid being prepared through step A, B, C is generally 10%~30%, pH and must control 7~9,
Otherwise positive metatitanic acid suspension cannot react completely with hydrogen peroxide (when especially positive metatitanic acid pH is less than 7), and obtained solution is muddy,
Unreacted particle is arranged at bottom；In addition, positive metatitanic acid also needs to meet the following conditions: utilizing BaCl2Solution is detected without SO4 2-.Preferably just
Also without other radioactive objectionable impurities of tool in metatitanic acid.
In step E, positive metatitanic acid is mixed with deionized water, positive metatitanic acid suspension can be obtained.Test discovery, positive metatitanic acid are outstanding
The titanium dioxide concentration of supernatant liquid is affected to reaction effect: positive metatitanic acid suspension concentration≤0.2mol/L (based on titanium dioxide)
When, hydrogen peroxide can more rapidly, more completely with reacting for positive metatitanic acid, and the clarity of subsequent gained pertitanic acid solution is also higher；
And with the increase of concentration, the clarity of pertitanic acid solution is declined, until opaque, muddy, bottom occurs insoluble
Particle；Simultaneously as titanic acid concentration improves, the stability decline of the nano-titanium dioxide obtained by subsequent technique hydro-thermal method；
Therefore, the present invention controls positive metatitanic acid suspension concentration≤0.2mol/L.
In step E of the present invention, the adding manner of hydrogen peroxide is to be added at one time rather than be added dropwise.For example it can be used and pour into
Hydrogen peroxide is added in mode in a manner of being added at one time rather than be added dropwise, and not only operation is easy, and equipment is simple, moreover it is possible in short-term
Between (be no more than 15min) just obtain the pertitanic acid of clear；And experimental results demonstrate Ti4+With H2O2Molar ratio extremely
(when molar ratio is lower than 8, react substantially incomplete, solution colour rests on for 1 ︰ 8 pertitanic acid that can just obtain clear less
Buff can not be clarified), and if it exceeds 1 ︰ 15, the additional amount of hydrogen peroxide are too many, it is not only uneconomical, when also consuming a large amount of
Between make excessive hydrogen peroxide fully reacting, also have an impact in hydrothermal reaction process to the preparation of titania slurry, two can be made
The pH value of titania slurry is increased to 9 or more, is easy to be layered titania slurry, particle is thicker.Therefore present invention control is double
The additional amount of oxygen water is with suspension Ti4+With H2O2Molar ratio be that 1 ︰ 8~15 is counted；When molar ratio be 1 ︰ 11, reach best work
Skill condition, the reaction time, which (is no more than 10min) within a very short time, can reach clear state.
Further, since hydrogen peroxide belongs to exothermic reaction with reacting for positive metatitanic acid, therefore generally can all use in the prior art
Cool down (water cooling) measure, guarantees reaction temperature < 50 DEG C, to guarantee that obtained nano-titanium dioxide is not in that layering is existing
As.Although using hydrogen peroxide is added at one time in the present invention, due to controlling the concentration of reaction system, a large number of experiments show that instead
It answers temperature substantially more stable, generally 25 DEG C~40 DEG C of room temperature, eliminates cooling down operation, therefore the method for the present invention reaction is more held
Easy to control, the reaction time is shorter, operates simpler.
After solution becomes clear, there is a large amount of bubble in solution, continue 30~90min of stirring, carries out reaction more
Thoroughly, more completely, the bubble in solution is effectively reduced, avoids bubble from increasing pertitanic acid viscosity, occurs in hydro-thermal reaction
Layering；It is then allowed to stand 12~for 24 hours, the pH value of pertitanic acid can automatically return to 7~9, not need to add any adjusting pH value
Reagent adjust pH；If time of repose is too short, hydrogen peroxide also unreacted is complete, is easy when carrying out hydro-thermal reaction
Existing lamination, and have an impact to the pH value of titanium dioxide.
It was proved that the titanium dioxide that furnace cooling prepares does not have the light of chilling to urge after the completion of hydro-thermal reaction
It is good to change effect, and particle is partially thick, therefore after the completion of hydro-thermal reaction, carries out chilling, not furnace cooling.The chilling is preferably
It is cooled to 15~25 DEG C in 20min.The optional mode of operation of the chilling are as follows: after hydro-thermal reaction, directly carry out shower with water
Reaction vessel is rapidly cooled to room temperature, and is opened counteracting tank and taken out product.
Below by embodiment, invention is further described in detail, but does not therefore limit the scope of the present invention
Among the embodiment described range.
Embodiment 1
A, taking 360.39g solid content is that 45.46% metatitanic acid is beaten by 350g/l, is added in three-neck flask, then
96% sulfuric acid solution of 780.16g is added, opens electric heating cover, setting heating temperature is 140 DEG C, while opening stirring and condensation
Water becomes to solution and clarifies, and keeps 10min or so, stops heating, is cooled to room temperature and closes stirring and condensed water；
B, add deionized water to be configured to the concentration of 200g/l the titanyl sulfate solution after acidolysis, be then stirred.By 2
Ammonia spirit is added in drop/s rate, carries out acid-base titration, when pH value is 7~9, stops that ammonium hydroxide is added, it is heavy to obtain positive metatitanic acid
It forms sediment；
C, sediment is washed repeatedly with deionized water until can't detect SO through filtering4 2-Until；
D, 9.08g solid content is weighed as 16.07% and pH value is in 8 or so positive metatitanic acid, is configured to 0.1mol/L's
White suspension；
E, at room temperature, by Ti4+With H2O2Molar ratio be 1:11 pour into dioxygen into the white suspension of step A
Water carries out peptization, and is stirred continuously；
F, after pouring into hydrogen peroxide 10min, solution gradually becomes clear, continues after stirring 1h, stands 12h, obtain clear
The pertitanic acid that clear bright, pH value is 7；
G, by the pertitanic acid of step C at 120 DEG C of temperature hydro-thermal reaction 14h, it is cold with water shower to after reaction
But to room temperature, solution is taken out, carries out being spray-dried to obtain nano-titanium dioxide in spray drying case；Through XRD analysis, crystal form is sharp
Titanium-type TiO2；Anti-microbial property reaches the I grade of GB/T 21866-2008 standard up to 99.9%, and formaldehyde removal rate reaches 91.0%.
Photocatalysis performance test:
Methyl orange powder 1g is weighed, is dissolved in the deionized water of 1000mL, methyl orange solution mother liquor is obtained；Measure methyl orange
Mother liquor 20mL is added deionized water constant volume, is made into the methyl orange solution of 20mg/L loaded in 1000mL volumetric flask, spare；
It takes the methyl orange solution of the prepared 20mg/L of 650mL to be transferred in glass reactor, is added thereto
0.65gTiO2, it is placed in photo catalysis reactor, sampling 20mL is (i.e. 20mg/L methyl orange in Fig. 2) to be checked；
With magnetic stirrer stirring dark reaction absorption dispersion 30min, take absorption dispersion sample 20mL, centrifuge separation 8 minutes to
Inspection (i.e. no light in Fig. 2 adsorbs 30min)；Cooling water is opened after absorption dispersion and opens Hg lamp irradiation, is sampled every 15min
20mL takes its supernatant to be placed in quartz glass ware and tests its photocatalysis performance (i.e. in Fig. 2 after taking out sample centrifuge separation 8min
Illumination 15min, illumination 30min, illumination 45min and illumination 60min).
The ultraviolet-visible absorption spectroscopy figure of Fig. 2 nano titanium dioxide degradable methyl orange thus, as shown in Figure 2, methyl orange exists
It has been degraded substantially after illumination 60min, by can be calculated, the degradation rate of methyl orange reaches 92.99% after illumination 60min；Drop
Solution after solving 60min is in colourless.
Embodiment 2
A, taking 360.39g solid content is that 45.46% metatitanic acid is beaten by 350g/l, is added in three-neck flask, then
96% sulfuric acid solution of 780.16g is added, opens electric heating cover, setting heating temperature is 140 DEG C, while opening stirring and condensation
Water becomes to solution and clarifies, and keeps 10min or so, stops heating, is cooled to room temperature and closes stirring and condensed water；
B, add deionized water to be configured to the concentration of 200g/l the titanyl sulfate solution after acidolysis, be then stirred.By 2
Ammonia spirit is added in drop/s rate, carries out acid-base titration, when pH value is 7~9, stops that ammonium hydroxide is added, it is heavy to obtain positive metatitanic acid
It forms sediment；
C, sediment is washed repeatedly with deionized water until can't detect SO through filtering4 2-Until；
D, 10.92g solid content is weighed as 16.07% and pH value is in 8 or so positive metatitanic acid, is configured to 0.1mol/L's
White suspension；
E, at room temperature, by Ti4+With H2O2Molar ratio be 1:8 pour into dioxygen into the white suspension of step A
Water carries out peptization, and is stirred continuously；
F, after pouring into hydrogen peroxide 15min, solution gradually becomes clear, continues after stirring 1h, stands for 24 hours, obtain clear
The pertitanic acid that clear bright, pH value is 7；
G, by the pertitanic acid of step C at 120 DEG C of temperature hydro-thermal reaction 14h, it is cold with water shower to after reaction
But to room temperature, solution is taken out, carries out being spray-dried to obtain nano-titanium dioxide in spray drying case, through XRD analysis, crystal form is sharp
Titanium-type TiO2。
Photocatalysis performance test:
Methyl orange powder 1g is weighed, is dissolved in the deionized water of 1000mL, methyl orange solution mother liquor is obtained；Measure methyl orange
Mother liquor 20mL is added deionized water constant volume, is made into the methyl orange solution of 20mg/L loaded in 1000mL volumetric flask, spare；
It takes the methyl orange solution of the prepared 20mg/L of 650mL to be transferred in glass reactor, is added thereto
0.65gTiO2, it is placed in photo catalysis reactor, sampling 20mL is (i.e. 20mg/L methyl orange in Fig. 3) to be checked；
Light source uses 500W mercury lamp, opens instrument master switch, disperses 30min with magnetic stirrer stirring dark reaction absorption,
Absorption dispersion sample 20mL is taken, is centrifugated 8 minutes (i.e. no light in Fig. 3 adsorbs 30min) to be checked；After absorption dispersion, open
Cooling water simultaneously opens 500W Hg lamp irradiation, samples 20mL every 15min, after taking out sample centrifuge separation 8min, its supernatant is taken to be placed in
Its photocatalysis performance (i.e. illumination 15min, illumination 30min, illumination 45min and illumination in Fig. 3 is tested in quartz glass ware
60min)。
The ultraviolet-visible absorption spectroscopy figure of Fig. 3 nano titanium dioxide degradable methyl orange thus, from the figure 3, it may be seen that illumination 60min
The degradation rate of methyl orange is 90.73% afterwards；Solution after degradation 60min is in colourless.
Embodiment 3
A, taking 287.73g solid content is that 45.46% metatitanic acid is beaten by 350g/l, is added in three-neck flask, then
96% sulfuric acid solution of 622.87g is added, opens electric heating cover, setting heating temperature is 140 DEG C, while opening stirring and condensation
Water becomes to solution and clarifies, and keeps 10min or so, stops heating, is cooled to room temperature and closes stirring and condensed water；
B, add deionized water to be configured to the concentration of 200g/l the titanyl sulfate solution after acidolysis, be then stirred.By 2
Sodium hydroxide solution is added in drop/s rate, carries out acid-base titration, when pH value is 7~9, stops that ammonium hydroxide is added, obtains titanic
Acid precipitating；
C, sediment is washed repeatedly with deionized water until can't detect SO through filtering4 2-Until；
D, 12.60g solid content is weighed as 16.98% and pH value is in 8 or so positive metatitanic acid, is configured to 0.2mol/L's
White suspension；
E, at room temperature, by Ti4+With H2O2Molar ratio be 1:11 pour into dioxygen into the white suspension of step A
Water carries out peptization, and is stirred continuously；
F, after pouring into hydrogen peroxide 15min, solution gradually becomes clear, continues after stirring 1h, stands for 24 hours, obtain clear
The pertitanic acid that clear bright, pH value is 7；
G, by the pertitanic acid of step C at 120 DEG C of temperature hydro-thermal reaction 14h, it is cold with water shower to after reaction
But to room temperature, solution is taken out, carries out being spray-dried to obtain nano-titanium dioxide in spray drying case, through XRD analysis, crystal form is sharp
Titanium-type TiO2。
Photocatalysis performance test:
Methyl orange powder 1g is weighed, is dissolved in the deionized water of 1000mL, methyl orange solution mother liquor is obtained；Measure methyl orange
Mother liquor 20mL is added deionized water constant volume, is made into the methyl orange solution of 20mg/L loaded in 1000mL volumetric flask, spare；
It takes the methyl orange solution of the prepared 20mg/L of 650mL to be transferred in glass reactor, is added thereto
0.65gTiO2, it is placed in photo catalysis reactor, sampling 20mL is (i.e. 20mg/L methyl orange in Fig. 4) to be checked；
Light source uses 500W mercury lamp, opens instrument master switch, disperses 30min with magnetic stirrer stirring dark reaction absorption,
Absorption dispersion sample 20mL is taken, is centrifugated 8 minutes (i.e. no light in Fig. 4 adsorbs 30min) to be checked；It is opened after absorption dispersion cold
But water and Hg lamp irradiation is opened, samples 20mL every 15min, after taking out sample centrifuge separation 8min, its supernatant is taken to be placed in quartzy glass
Its photocatalysis performance (i.e. illumination 15min, illumination 30min, illumination 45min and illumination 60min in Fig. 4) is tested in glass ware.
The ultraviolet-visible absorption spectroscopy figure of Fig. 4 nano titanium dioxide degradable methyl orange thus, as shown in Figure 4, illumination 60min
The degradation rate of methyl orange is 89.21% afterwards；Solution after degradation 60min is in colourless.
Embodiment 4
A, taking 360.39g solid content is that 45.46% metatitanic acid is beaten by 350g/l, is added in three-neck flask, then
96% sulfuric acid solution of 780.16g is added, opens electric heating cover, setting heating temperature is 140 DEG C, while opening stirring and condensation
Water becomes to solution and clarifies, and keeps 10min or so, stops heating, is cooled to room temperature and closes stirring and condensed water；
B, add deionized water to be configured to the concentration of 200g/l the titanyl sulfate solution after acidolysis, be then stirred.By 2
Sodium hydroxide solution is added in drop/s rate, carries out acid-base titration, when pH value is 7~9, stops that ammonium hydroxide is added, obtains titanic
Acid precipitating；
C, sediment is washed repeatedly with deionized water until can't detect SO through filtering4 2-Until；
D, 22.60g solid content is weighed as 16.98% and pH value is in 8 or so positive metatitanic acid, is configured to 0.2mol/L's
White suspension；
E, at room temperature, by Ti4+With H2O2Molar ratio be 1:11 pour into dioxygen into the white suspension of step A
Water carries out peptization, and is stirred continuously；
F, after pouring into hydrogen peroxide 10min, solution gradually becomes clear, stands for 24 hours after stirring 1h, and it is saturating to obtain clarification
Pertitanic acid bright, that pH value is 7；
G, by the pertitanic acid of step C at 120 DEG C of temperature hydro-thermal reaction 14h, it is air-cooled to after reaction, in spraying
Drying box carries out being spray-dried to obtain nano-titanium dioxide, and through XRD analysis, crystal form is anatase titanium dioxide TiO2。
Photocatalysis performance test:
Methyl orange powder 1g is weighed, is dissolved in the deionized water of 1000mL, methyl orange solution mother liquor is obtained；Measure methyl orange
Mother liquor 20mL is added deionized water constant volume, is made into the methyl orange solution of 20mg/L loaded in 1000mL volumetric flask, spare；
It takes the methyl orange solution of the prepared 20mg/L of 650mL to be transferred in glass reactor, is added thereto
0.65gTiO2, it is placed in photo catalysis reactor, sampling 20mL is (i.e. 20mg/L methyl orange in Fig. 5) to be checked；
Light source uses 500W mercury lamp, opens instrument master switch, disperses 30min with magnetic stirrer stirring dark reaction absorption,
Absorption dispersion sample 20mL is taken, is centrifugated 8 minutes (i.e. no light in Fig. 5 adsorbs 30min) to be checked；It is opened after absorption dispersion cold
But water and Hg lamp irradiation is opened, samples 20mL every 15min, after taking out sample centrifuge separation 8min, its supernatant is taken to be placed in quartzy glass
Its photocatalysis performance (i.e. illumination 15min, illumination 30min, illumination 45min and illumination 60min in Fig. 5) is tested in glass ware.
The ultraviolet-visible absorption spectroscopy figure of Fig. 5 nano titanium dioxide degradable methyl orange thus, as shown in Figure 5, illumination 60min
The degradation rate of methyl orange is 86.82% afterwards；Solution after degradation 75min is in colourless.
Claims (10)
1. the method for preparing photocatalysis nano-titanium dioxide as raw material using metatitanic acid, it is characterised in that: the following steps are included:
A, metatitanic acid is beaten and is stirred, sulfuric acid solution acidolysis is then added, obtains titanyl sulfate solution；The dosage of the sulfuric acid is
Make the mass concentration 60% of the sulfuric acid in system；
B, the titanyl sulfate solution after acidolysis is added into deionized water, be then stirred, inorganic alkali solution is added and is neutralized, to
When pH value is 7~9, stop stirring, precipitates positive metatitanic acid；
C, positive metatitanic acid being precipitated and is filtered, washing filter cake repeatedly with deionized water until can't detect SO4 2-Until；
D, the positive metatitanic acid after washing is configured to≤the suspension of 0.2mol/L；
E, hydrogen peroxide is added into suspension and carries out peptization, and constantly stir to clarify transparent；
F, the system after clear is continued to stir, is then allowed to stand to obtain pertitanic acid；
G, pertitanic acid is subjected to hydro-thermal reaction, then cooled down, carry out being spray-dried to obtain nano-titanium dioxide.
2. according to the method described in claim 1, it is characterized by: step A metatitanic acid mashing stirring to concentration is 250g/
L~400g/l；Keep system temperature at 120 DEG C~160 DEG C when the acidolysis.
3. method according to claim 1 or 2, it is characterised in that: titanyl sulfate solution after acidolysis described in step B it is dense
Degree is 200g/l~250g/l；The inorganic alkali solution is at least one of sodium hydroxide, potassium hydroxide, ammonium hydroxide or urea.
4. described in any item methods according to claim 1~3, it is characterised in that: the pH value of positive metatitanic acid described in step B be for
8~9.
5. method according to any one of claims 1 to 4, it is characterised in that: in step E, the hydrogen peroxide presses suspension
Middle Ti4+With H2O2Molar ratio be 1:8~15 be added；The adding manner is disposably to rapidly join.
6. described in any item sides for preparing photocatalysis nano-titanium dioxide using metatitanic acid as raw material according to claim 1~5
Method, it is characterised in that: the pH of pertitanic acid described in step E is 7~9.
7. described in any item methods according to claim 1~6, it is characterised in that: in step F, the suspension clear
The time for continuing stirring afterwards is 30min~90min.
8. any one of according to claim 1~7 the method, it is characterised in that: in step F, the time of the standing be 12h~
24h。
9. described in any item methods according to claim 1~8, it is characterised in that: in step F, the temperature of the hydro-thermal reaction
It is 90~150 DEG C；The time of the hydro-thermal reaction be 8~for 24 hours.
10. described in any item sides for preparing photocatalysis nano-titanium dioxide using metatitanic acid as raw material according to claim 1~9
Method, it is characterised in that: it is described to be cooled to chilling in step G, system is cooled to 15~25 DEG C in 20min.
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