CN110142038A - The method for preparing the nano amorphous titanium dioxide of tin dope using chloridising intermediate - Google Patents
The method for preparing the nano amorphous titanium dioxide of tin dope using chloridising intermediate Download PDFInfo
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- CN110142038A CN110142038A CN201910440556.5A CN201910440556A CN110142038A CN 110142038 A CN110142038 A CN 110142038A CN 201910440556 A CN201910440556 A CN 201910440556A CN 110142038 A CN110142038 A CN 110142038A
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- titanium dioxide
- tin
- tin dope
- tetrachloride
- chloridising
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 222
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 120
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 78
- 239000013078 crystal Substances 0.000 claims abstract description 37
- 239000012065 filter cake Substances 0.000 claims abstract description 28
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 27
- 238000003825 pressing Methods 0.000 claims abstract description 27
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 27
- 230000002572 peristaltic effect Effects 0.000 claims abstract description 26
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 25
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 238000010792 warming Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 18
- 238000000746 purification Methods 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 18
- 239000013067 intermediate product Substances 0.000 abstract description 15
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 19
- 239000010936 titanium Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 13
- 241000790917 Dioxys <bee> Species 0.000 description 12
- 230000008859 change Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000007146 photocatalysis Methods 0.000 description 11
- 239000000975 dye Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000009775 high-speed stirring Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910003910 SiCl4 Inorganic materials 0.000 description 2
- 229910010270 TiOCl2 Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000001934 delay Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000009283 thermal hydrolysis Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000007144 microwave assisted synthesis reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/24—Chlorinating
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The method for preparing the nano amorphous titanium dioxide of tin dope using chloridising intermediate, belong to the preparation technical field of photocatalytic nanometer new material, the following steps are included: A, at room temperature, with peristaltic pump by by the intermediate product titanium tetrachloride of the Preparation of Cajuelite Titania Powders by Chlorination Process refined and tin tetrachloride, cocurrent is added in the NaOH mixed aqueous solution containing surfactant simultaneously, add ammonium carbonate solution, it is warming up to 70~80 DEG C, continue to stir, after curing, it is cooled to room temperature, tin dope TiO is made2Hydrate；B, by tin dope TiO2Hydrate carries out filters pressing, and filter cake is made less than 10 μ s/cm in washing to filtrate conductivity；C, filter cake is dried in microwave dryer, the non-crystal titanium dioxide of tin dope is made；D, by the non-crystal titanium dioxide of tin dope, air-flow crushing is carried out, the nano amorphous titanium dioxide of tin dope is made.The nanometer amorphous titanium dioxide of tin dope prepared by the present invention has the function of efficient degradation organic pollutant under visible light.
Description
Technical field
The invention belongs to the preparation technical fields of photocatalytic nanometer new material, and in particular to be prepared using chloridising intermediate
The method of the nano amorphous titanium dioxide of tin dope.The present invention uses the intermediate product four of Preparation of Cajuelite Titania Powders by Chlorination Process
Titanium chloride is basic raw material, prepares the nanometer amorphous titanium dioxide visible light catalyzer of tin dope, under visible light, is had efficient
The effect of degradable organic pollutant.
Background technique
Titanium dioxide has many advantages, such as that chemical property is stable, nontoxic, UV absorbance is strong as photochemical catalyst, in light
Many fields such as catalysis, photoelectric conversion and self-cleaning material have a wide range of applications.Due to crystalline state TiO2With biggish band
Gap energy (3.2eV) cannot utilize visible absorption, carry out light-catalyzed reaction, therefore, it is seen that light-catalysed defect is puzzlement TiO2
The one of the major reasons of photocatalysis technology development.
Due to amorphous state TiO2Frame mode with " shortrange order " and " longrange disorder ", so in amorphous state TiO2Knot
Both exist and crystalline state TiO in structure2The basic band structure of similar valence band and conduction band, and exist and the different valence band of crystalline state
With the localized state magnetic tape trailer on conduction band, and due to amorphous state TiO2With the presence of a large amount of dangling bonds in semiconductor, in band structure
Again there are gap band between valence band and conduction band, the difference of the two band structure is the presence of localized state magnetic tape trailer and gap band；In addition, non-
Crystalline state TiO2In electron transition can occur between the electronic state between valence band and conduction band and valence band and conduction band, electronics jump
A possibility that moving increases considerably.Therefore, amorphous state TiO2With some and crystalline state TiO2Different optical properties, can be effective
Using visible light, light-catalyzed reaction is carried out.
Although SnO2It is wide bandgap semiconductor, direct band gap 3.189eV, but since there are several intrinsic defects for it:
Lacking oxygen, tin vacancy, oxygen calking and tin calking etc., cause its indirect band gap between 2.162~2.190eV, and making it, there are non-
The structure of stoichiometric ratio, calculation shows that oxygen defect and tin calking have especially low combination energy in various defects.Due to it
There are a large amount of dangling bonds and unsaturated bond in surface, and dangling bond band or impurity band, property and amorphous state titanium dioxide are formed in forbidden band
Titanium has similarity, while quantum size effect leads to SnO2The increase of indirect band gap transition probability, thus, SnO2Doping
Among amorphous titanium dioxide, the electron transfer rate in amorphous titanium dioxide can be effectively improved, delays its electron-hole
Pair it is compound, to further improve the photocatalysis performance of its visible light.
Adan Luna-Flores etc. reports the amorphous state TiO to about 300nm2Carbon doping is carried out, in radiation of visible light
Under, it degrades to rhodamine B solution, 100min degradation rate about 90% has embodied photocatalytic activity under preferable visible light
(Economical and Efficient Carbon-Doped Amorphous TiO2Photocatalyst Obtained
by Microwave Assisted Synthesis for the Degradation of Rhodamine B[J].Mater.,
2017,10(12):1447).It can be seen that doping has the function of very big the activity of raising photochemical catalyst.But about utilization
Chloridising intermediate prepares the nano amorphous TiO of tin dope of the low forbidden bandwidth with large specific surface area2, instead of crystalline state
TiO2To improve the research of its visible light photocatalysis performance, then there is not been reported at present.
The prior art is by dichloride in anatase type TiO2Be doped modification, noble metal loading, semiconductors coupling etc. compared with
It is active to improve its ultraviolet light photocatalysis for complicated preparation method.For titanium dioxide amorphous nano particle, researcher also tastes
A variety of methods are tried, for example, sol-gel method, direct precipitation method, microemulsion method etc., finally require the temperature at 300 DEG C or so
Under degree, amorphous nano-titanium dioxide is made after carrying out calcination processing, in the prevalence of the production of preparation in existing preparation method
Product particle size calcines environmental pollution problem with the problem for reuniting more serious and to product greatly.
Summary of the invention
The purpose of the present invention is in Preparation of Cajuelite Titania Powders by Chlorination Process technical process, refining titanic chloride it
Afterwards, it by technical process such as control alkaline thermal hydrolysis, filters pressing, microwave drying and air-flow crushings, provides a kind of using among chloridising
The method that body prepares the nano amorphous titanium dioxide of tin dope when reducing chloridising and preparing crystalline titania photochemical catalyst, needs
The technical process that high-temperature oxydation and post-processing etc. are complicated, dangerous is carried out, the microcosmic knot of titanium dioxide optical catalyst is optimized
Structure makes it have large specific surface area and lower forbidden bandwidth, compensates for crystalline titania photocatalytic under visible light
The poor defect of energy.
The present invention be realize its purpose the technical solution adopted is that:
The method that the present invention prepares the nano amorphous titanium dioxide of tin dope using chloridising intermediate, the technical solution of use
Are as follows:
Including following step of preparation process:
The method for preparing the nano amorphous titanium dioxide of tin dope using chloridising intermediate, which is characterized in that including following
Step:
A, at room temperature, titanium tetrachloride and tin tetrachloride while cocurrent are added to containing surfactant with peristaltic pump
NaOH mixed aqueous solution in, while be added while high-speed stirred, revolving speed be 3000~3500r/min, after addition, add carbon
Sour aqueous ammonium is warming up to 70~80 DEG C, continues to stir, and revolving speed is 500~600r/min, cures 3~4h, is cooled to room temperature,
Tin dope TiO is made2Hydrate；
B, the tin dope TiO for preparing step A2Hydrate carries out filters pressing with filter press, then is washed with deionized to filter
Filter cake is made less than 10 μ s/cm in liquid conductivity；
C, it by the filter cake after step B filters pressing, is dried in microwave dryer with 180~200 DEG C of temperature, when dry
Between be 3~4h, be made the non-crystal titanium dioxide of tin dope；
D, by the non-crystal titanium dioxide of tin dope prepared by step C, air-flow crushing is carried out in airslide disintegrating mill, and tin is made
The non-crystal titanium dioxide of dopen Nano.
Titanium tetrachloride described in step A is that the intermediate of the Preparation of Cajuelite Titania Powders by Chlorination Process by purification produces
Object, TiCl4The molar ratio of mass percentage >=98%, titanium tetrachloride additional amount and NaOH are 1:5~6.
Tin tetrachloride additional amount described in step A is the 2~5% of titanium tetrachloride quality.
Described in step A plus the flow velocity of titanium tetrachloride peristaltic pump is 5mL/min, adds the flow velocity of tin tetrachloride peristaltic pump to be
0.25mL/min。
In NaOH mixed aqueous solution described in step A containing surfactant, the mass concentration of NaOH is 10~
15%, the mass concentration of surfactant is 0.1~0.3%, and the surfactant is neopelex.
The mass concentration of ammonium carbonate solution described in step A is 10~20%, and ammonium carbonate additional amount is titanium tetrachloride matter
The 0.3~0.5% of amount.
Titanium tetrachloride of the present invention is the intermediate product of the Preparation of Cajuelite Titania Powders by Chlorination Process by purification,
Specific refining titanic chloride technical matters are as follows:
It is former that Preparation of Cajuelite Titania Powders by Chlorination Process technical process of the present invention, which is with ilmenite or high titanium slag,
Material, by techniques such as ingredient, chlorination, purification, oxidation and post-processings.The crude titanic chloride wherein generated after chlorination is impure
More, major impurity has SiO2、TiO2、SiCl4、FeCl3、VOCl3、TiOCl2、Cl2, HCl etc..Wherein subtractive process technique are as follows:
Crude titanic chloride after chlorination is carried out the insoluble solid suspension of sedimentation separation (such as SiO first by the first step2、TiO2Deng)；
Second step makes titanium tetrachloride clear liquid gasify, and controlled at 140~145 DEG C, pressure is 0.4~0.6MPa；Third step,
SiCl is removed by rectificating method4Equal low boiling impurities, control tower top temperature are 57~60 DEG C, and column bottom temperature is 139~141
DEG C, pressure is 15~20kPa；4th step, then FeCl is removed with distillating method3Equal high-boiling-point impurities, control tower top temperature are 136
~137 DEG C；5th step, then VOCl similar in boiling point and titanium tetrachloride is removed with aluminium displacement chemical method3Equal impurity, controlled at
137~139 DEG C, the average grain diameter of aluminium powder is≤50 μm, and content >=98wt%, additional amount is 60~70g/L, finally collects temperature
For the refining titanic chloride liquid that 135~137 DEG C of gaseous titanium tetrachlorides are condensed by the condenser, essence used in the present invention is obtained
Titanium tetrachloride raw material (TiCl processed4Mass percentage >=98%).
The beneficial effects of the present invention are:
It (1) is original with the intermediate product titanium tetrachloride of the Preparation of Cajuelite Titania Powders by Chlorination Process Jing Guo refinement treatment
Material, while tin tetrachloride is added in cocurrent, using technical process such as alkaline thermal hydrolysis, filters pressing, microwave drying and air-flow crushings, carries out tin
The preparation of dopen Nano amorphous titanium dioxide, instead of in Preparation of Cajuelite Titania Powders by Chlorination Process to the height of titanium tetrachloride
The complexity such as temperature oxidation, post-processing, dangerous operating procedure；The nano amorphous titanium dioxide of tin dope prepared by the present invention, have compared with
Good visible absorption effect, compensates for the crystalline titania defect weak to visible absorption performance, can under visible light,
The effect of efficient degradation dirt organic pollutants.In addition, the titanium tetrachloride by purification, purity is higher, thus prepared
Amorphous nano titanium dioxide purity is also high, improves the performance of photocatalysis electronics transfer, has effectively delayed its light induced electron-sky
The recombination time in cave has improvement result to its photocatalytic degradation efficiency.
(2) during the preparation process, titanium tetrachloride and tin tetrachloride are added dropwise to containing surface simultaneously using peristaltic pump
In the NaOH aqueous solution of activating agent, it can effectively delay the hydrolysis rate for controlling titanium tetrachloride and tin tetrachloride, make TiCl4And SnCl4
It is hydrolyzed more completely, while high-speed stirred, makes to be formed by Ti (OH)4With Sn (OH)4Precipitated particle size is fine and uniform,
Simultaneously because the effect of surfactant, greatly reduces the reunion situation of precipitating particle；The Ti (OH) of formation4With Sn (OH)4?
Grain passes through further slaking reaction in 70~80 DEG C of hot water, forms tin dope TiO2Hydrate, simultaneously because carbonic acid
The decomposition of ammonium generates a large amount of ammonia and carbon dioxide gas, can not only preferably control tin dope TiO2The nanometer of hydrate
Partial size also to prepare there is the tin dope amorphous titanium dioxide of large specific surface area to provide the foundation condition.
(3) filter cake is sufficiently washed with deionized water after filters pressing, washes off tin dope TiO2The inorganic salts contained in hydrate, one
Aspect greatly reduces the reunion between particle, improves its water dispersion, on the other hand improve due to reducing inorganic salts
The purity of prepared tin dope amorphous titanium dioxide has preferable improve to its photocatalytic activity.
(4) filter cake after washing, carries out microwave drying at a temperature of 180~200 DEG C, in the drying process, utilizes microwave
Tin dope TiO can on the one hand be eliminated2On the other hand the moisture of hydrate adsorption loses its constitution water to form tin and mix
Miscellaneous amorphous titanium dioxide.Then using air-flow crushing, the nanometer amorphous titanium dioxide of tin dope is formed.The present invention adopts
It with microwave drying is interacted using microwave and water, by material molecules such as dry materials, generates molecular polarization, orientation, mill
Wipe, absorb etc., microwave energy makes material self-heating, and entire material is heated simultaneously, i.e., so-called " volume heating " process.Due to
Microwave energy penetrates into heating object in moment, is not necessarily to heat transfer process, microwave can be converted to the heat of substance for several minutes
Can, TiO2Combination water rapidly remove, heating speed is fast, and drying efficiency is high, and reduces particle growth and reunite
Possibility, to be easier to obtain evengranular tin dope Amorphous nano-powder.
(5) present invention is in nano amorphous titanium dioxide preparation process, while carrying out the non-crystal titanium dioxide of tin dope, due to
SnO2Surface has a large amount of dangling bonds and unsaturated bond, dangling bond band or impurity band is formed in forbidden band, also due to its quantum ruler
Very little effect leads to SnO2The increase of indirect band gap transition probability can effectively improve the electronics transfer speed in amorphous titanium dioxide
Rate delays the compound of its electron-hole pair, to further improve the photocatalysis performance of its visible light.
(6) equipment used in this preparation process is simple, easy to operate, energy-saving and environment friendly, and prepared tin dope is received
The non-crystal titanium dioxide of rice, has biggish specific surface area, preferable water dispersible, lesser band-gap energy and efficient visible light light
Catalytic performance.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.
One, specific embodiment
Raw material titanium tetrachloride used in the embodiment of the present invention 1~8 and comparative example 1~2 is the chloridising preparation by purification
The intermediate product of rutile titanium dioxide, specific refining titanic chloride technical matters are as follows:
It is former that Preparation of Cajuelite Titania Powders by Chlorination Process technical process of the present invention, which is with ilmenite or high titanium slag,
Material, by techniques such as ingredient, chlorination, purification, oxidation and post-processings.The crude titanic chloride wherein generated after chlorination is impure
More, major impurity has SiO2、TiO2、SiCl4、FeCl3、VOCl3、TiOCl2、Cl2, HCl etc..Wherein subtractive process technique are as follows:
Crude titanic chloride after chlorination is carried out the insoluble solid suspension of sedimentation separation (such as SiO first by the first step2、TiO2Deng)；
Second step makes titanium tetrachloride clear liquid gasify, and controlled at 140~145 DEG C, pressure is 0.4~0.6MPa；Third step,
SiCl is removed by rectificating method4Equal low boiling impurities, control tower top temperature are 57~60 DEG C, and column bottom temperature is 139~141
DEG C, pressure is 15~20kPa；4th step, then FeCl is removed with distillating method3Equal high-boiling-point impurities, control tower top temperature are 136
~137 DEG C；5th step, then VOCl similar in boiling point and titanium tetrachloride is removed with aluminium displacement chemical method3Equal impurity, controlled at
137~139 DEG C, the average grain diameter of aluminium powder is≤50 μm, and content >=98wt%, additional amount is 60~70g/L, finally collects temperature
For the refining titanic chloride liquid that 135~137 DEG C of gaseous titanium tetrachlorides are condensed by the condenser, essence used in the present invention is obtained
Titanium tetrachloride raw material (TiCl processed4Mass percentage >=98%).
Embodiment 1
A, the peristaltic pump for being at room temperature, 5mL/min with flow velocity will prepare rutile-type dioxy by the chloridising of purification
Change the intermediate product titanium tetrachloride (TiCl of titanium4Mass percentage is the 98.0%) peristaltic pump for being 0.25mL/min with flow velocity
By tin tetrachloride, while cocurrent is added to the (quality of NaOH in the NaOH mixed aqueous solution that 10L contains neopelex
Concentration is 10% and the mass concentration of neopelex is that 0.1%), the molar ratio of titanium tetrachloride additional amount and NaOH are
1:5, tin tetrachloride additional amount are the 2.0% of titanium tetrachloride quality, carry out high-speed stirring when being added with the revolving speed of 3000r/min
It mixes, after addition, adds the ammonium carbonate solution that mass concentration is 10%, ammonium carbonate additional amount is titanium tetrachloride quality
0.3%, 71 DEG C are then heated to, continues to stir with the revolving speed of 520r/min, 3.0h is cured, is cooled to room temperature, tin dope is made
TiO2Hydrate；
B, the tin dope TiO for preparing step A2Hydrate carries out filters pressing with filter press, then is washed with deionized to filter
Filter cake is made less than 10 μ s/cm in liquid conductivity；
C, it by the filter cake after step B filters pressing, is dried in microwave dryer with 180 DEG C of temperature, drying time is
The non-crystal titanium dioxide of tin dope is made in 3.0h；
D, by the non-crystal titanium dioxide of tin dope prepared by step C, air-flow crushing is carried out in airslide disintegrating mill, and tin is made
The non-crystal titanium dioxide of dopen Nano.
Embodiment 2
A, the peristaltic pump for being at room temperature, 5mL/min with flow velocity will prepare rutile-type dioxy by the chloridising of purification
Change the intermediate product titanium tetrachloride (TiCl of titanium4Mass percentage is the 98.2%) peristaltic pump for being 0.25mL/min with flow velocity
By tin tetrachloride, while cocurrent is added to the (quality of NaOH in the NaOH mixed aqueous solution that 10L contains neopelex
Concentration is 11% and the mass concentration of neopelex is the 0.12%) molar ratio of titanium tetrachloride additional amount and NaOH
For 1:5.2, tin tetrachloride additional amount is the 2.5% of titanium tetrachloride quality, carries out high speed when being added with the revolving speed of 3100r/min
Stirring after addition, adds the ammonium carbonate solution that mass concentration is 12%, and ammonium carbonate additional amount is titanium tetrachloride quality
0.32%, then heat to 70 DEG C, continue to stir with the revolving speed of 600r/min, cure 3.3h, be cooled to room temperature, obtained tin is mixed
Miscellaneous TiO2Hydrate；
B, the tin dope TiO for preparing step A2Hydrate carries out filters pressing with filter press, then is washed with deionized to filter
Filter cake is made less than 10 μ s/cm in liquid conductivity；
C, it by the filter cake after step B filters pressing, is dried in microwave dryer with 185 DEG C of temperature, drying time is
The non-crystal titanium dioxide of tin dope is made in 3.2h；
D, by the non-crystal titanium dioxide of tin dope prepared by step C, air-flow crushing is carried out in airslide disintegrating mill, and tin is made
The non-crystal titanium dioxide of dopen Nano.
Embodiment 3
A, the peristaltic pump for being at room temperature, 5mL/min with flow velocity will prepare rutile-type dioxy by the chloridising of purification
Change the intermediate product titanium tetrachloride (TiCl of titanium4Mass percentage is the 98.3%) peristaltic pump for being 0.25mL/min with flow velocity
By tin tetrachloride, while cocurrent is added to the (quality of NaOH in the NaOH mixed aqueous solution that 10L contains neopelex
Concentration is 12% and the mass concentration of neopelex is the 0.15%) molar ratio of titanium tetrachloride additional amount and NaOH
For 1:5.5, tin tetrachloride additional amount is the 3.0% of titanium tetrachloride quality, carries out high speed when being added with the revolving speed of 3200r/min
Stirring after addition, adds the ammonium carbonate solution that mass concentration is 14%, and ammonium carbonate additional amount is titanium tetrachloride quality
0.35%, then heat to 72 DEG C, continue to stir with the revolving speed of 510r/min, cure 3.5h, be cooled to room temperature, obtained tin is mixed
Miscellaneous TiO2Hydrate；
B, the tin dope TiO for preparing step A2Hydrate carries out filters pressing with filter press, then is washed with deionized to filter
Filter cake is made less than 10 μ s/cm in liquid conductivity；
C, it by the filter cake after step B filters pressing, is dried in microwave dryer with 190 DEG C of temperature, drying time is
The non-crystal titanium dioxide of tin dope is made in 3.5h；
D, by the non-crystal titanium dioxide of tin dope prepared by step C, air-flow crushing is carried out in airslide disintegrating mill, and tin is made
The non-crystal titanium dioxide of dopen Nano.
Embodiment 4
A, the peristaltic pump for being at room temperature, 5mL/min with flow velocity will prepare rutile-type dioxy by the chloridising of purification
Change the intermediate product titanium tetrachloride (TiCl of titanium4Mass percentage is the 98.5%) peristaltic pump for being 0.25mL/min with flow velocity
By tin tetrachloride, while cocurrent is added to the (quality of NaOH in the NaOH mixed aqueous solution that 10L contains neopelex
Concentration is 12.5% and the mass concentration of neopelex is the 0.2%) molar ratio of titanium tetrachloride additional amount and NaOH
For 1:5.7, tin tetrachloride additional amount is the 3.5% of titanium tetrachloride quality, carries out high speed when being added with the revolving speed of 3300r/min
Stirring after addition, adds the ammonium carbonate solution that mass concentration is 16%, and ammonium carbonate additional amount is titanium tetrachloride quality
0.4%, then heat to 73 DEG C, continue to stir with the revolving speed of 530r/min, cure 3.8h, be cooled to room temperature, obtained tin is mixed
Miscellaneous TiO2Hydrate；
B, the tin dope TiO for preparing step A2Hydrate carries out filters pressing with filter press, then is washed with deionized to filter
Filter cake is made less than 10 μ s/cm in liquid conductivity；
C, it by the filter cake after step B filters pressing, is dried in microwave dryer with 195 DEG C of temperature, drying time is
The non-crystal titanium dioxide of tin dope is made in 3.7h；
D, by the non-crystal titanium dioxide of tin dope prepared by step C, air-flow crushing is carried out in airslide disintegrating mill, and tin is made
The non-crystal titanium dioxide of dopen Nano.
Embodiment 5
A, the peristaltic pump for being at room temperature, 5mL/min with flow velocity will prepare rutile-type dioxy by the chloridising of purification
Change the intermediate product titanium tetrachloride (TiCl of titanium4Mass percentage is the 99.0%) peristaltic pump for being 0.25mL/min with flow velocity
By tin tetrachloride, while cocurrent is added to the (quality of NaOH in the NaOH mixed aqueous solution that 10L contains neopelex
Concentration is 13% and the mass concentration of neopelex is the 0.25%) molar ratio of titanium tetrachloride additional amount and NaOH
For 1:5.9, tin tetrachloride additional amount is the 4.0% of titanium tetrachloride quality, carries out high speed when being added with the revolving speed of 3400r/min
Stirring after addition, adds the ammonium carbonate solution that mass concentration is 17%, and ammonium carbonate additional amount is titanium tetrachloride quality
0.45%, then heat to 75 DEG C, continue to stir with the revolving speed of 540r/min, cure 3.6h, be cooled to room temperature, obtained tin is mixed
Miscellaneous TiO2Hydrate；
B, the tin dope TiO for preparing step A2Hydrate carries out filters pressing with filter press, then is washed with deionized to filter
Filter cake is made less than 10 μ s/cm in liquid conductivity；
C, it by the filter cake after step B filters pressing, is dried in microwave dryer with 200 DEG C of temperature, drying time is
The non-crystal titanium dioxide of tin dope is made in 3.8h；
D, by the non-crystal titanium dioxide of tin dope prepared by step C, air-flow crushing is carried out in airslide disintegrating mill, and tin is made
The non-crystal titanium dioxide of dopen Nano.
Embodiment 6
A, the peristaltic pump for being at room temperature, 5mL/min with flow velocity will prepare rutile-type dioxy by the chloridising of purification
Change the intermediate product titanium tetrachloride (TiCl of titanium4Mass percentage is the 98.7%) peristaltic pump for being 0.25mL/min with flow velocity
By tin tetrachloride, while cocurrent is added to the (quality of NaOH in the NaOH mixed aqueous solution that 10L contains neopelex
Concentration is 14% and the mass concentration of neopelex is the 0.27%) molar ratio of titanium tetrachloride additional amount and NaOH
For 1:6, tin tetrachloride additional amount is the 4.5% of titanium tetrachloride quality, carries out high-speed stirring when being added with the revolving speed of 3500r/min
It mixes, after addition, adds the ammonium carbonate solution that mass concentration is 19%, ammonium carbonate additional amount is titanium tetrachloride quality
0.5%, 78 DEG C are then heated to, continues to stir with the revolving speed of 550r/min, 3.2h is cured, is cooled to room temperature, tin dope is made
TiO2Hydrate；
B, the tin dope TiO for preparing step A2Hydrate carries out filters pressing with filter press, then is washed with deionized to filter
Filter cake is made less than 10 μ s/cm in liquid conductivity；
C, it by the filter cake after step B filters pressing, is dried in microwave dryer with 193 DEG C of temperature, drying time is
The non-crystal titanium dioxide of tin dope is made in 3.9h；
D, by the non-crystal titanium dioxide of tin dope prepared by step C, air-flow crushing is carried out in airslide disintegrating mill, and tin is made
The non-crystal titanium dioxide of dopen Nano.
Embodiment 7
A, the peristaltic pump for being at room temperature, 5mL/min with flow velocity will prepare rutile-type dioxy by the chloridising of purification
Change the intermediate product titanium tetrachloride (TiCl of titanium4Mass percentage is the 98.8%) peristaltic pump for being 0.25mL/min with flow velocity
By tin tetrachloride, while cocurrent is added to the (quality of NaOH in the NaOH mixed aqueous solution that 10L contains neopelex
Concentration is 15% and the mass concentration of neopelex is that 0.3%), the molar ratio of titanium tetrachloride additional amount and NaOH are
1:5.3, tin tetrachloride additional amount are the 5.0% of titanium tetrachloride quality, carry out high-speed stirring when being added with the revolving speed of 3450r/min
It mixes, after addition, adds the ammonium carbonate solution that mass concentration is 20%, ammonium carbonate additional amount is titanium tetrachloride quality
0.48%, 80 DEG C are then heated to, continues to stir with the revolving speed of 580r/min, 4.0h is cured, is cooled to room temperature, tin dope is made
TiO2Hydrate；
B, the tin dope TiO for preparing step A2Hydrate carries out filters pressing with filter press, then is washed with deionized to filter
Filter cake is made less than 10 μ s/cm in liquid conductivity；
C, it by the filter cake after step B filters pressing, is dried in microwave dryer with 197 DEG C of temperature, drying time is
The non-crystal titanium dioxide of tin dope is made in 4.0h；
D, by the non-crystal titanium dioxide of tin dope prepared by step C, air-flow crushing is carried out in airslide disintegrating mill, and tin is made
The non-crystal titanium dioxide of dopen Nano.
Embodiment 8
A, the peristaltic pump for being at room temperature, 5mL/min with flow velocity will prepare rutile-type dioxy by the chloridising of purification
Change the intermediate product titanium tetrachloride (TiCl of titanium4Mass percentage is the 98.0%) peristaltic pump for being 0.25mL/min with flow velocity
By tin tetrachloride, while cocurrent is added to the (quality of NaOH in the NaOH mixed aqueous solution that 10L contains neopelex
Concentration is 10% and the mass concentration of neopelex is that 0.1%), the molar ratio of titanium tetrachloride additional amount and NaOH are
1:5, tin tetrachloride additional amount are the 5.0% of titanium tetrachloride quality, carry out high-speed stirring when being added with the revolving speed of 3000r/min
It mixes, after addition, adds the ammonium carbonate solution that mass concentration is 10%, ammonium carbonate additional amount is titanium tetrachloride quality
0.3%, 71 DEG C are then heated to, continues to stir with the revolving speed of 520r/min, 3.0h is cured, is cooled to room temperature, tin dope is made
TiO2Hydrate；
B, the tin dope TiO for preparing step A2Hydrate carries out filters pressing with filter press, then is washed with deionized to filter
Filter cake is made less than 10 μ s/cm in liquid conductivity；
C, it by the filter cake after step B filters pressing, is dried in microwave dryer with 180 DEG C of temperature, drying time is
The non-crystal titanium dioxide of tin dope is made in 3.0h；
D, by the non-crystal titanium dioxide of tin dope prepared by step C, air-flow crushing is carried out in airslide disintegrating mill, and tin is made
The non-crystal titanium dioxide of dopen Nano.
Comparative example 1
A, the peristaltic pump for being at room temperature, 5mL/min with flow velocity will prepare rutile-type dioxy by the chloridising of purification
Change the intermediate product titanium tetrachloride (TiCl of titanium4Mass percentage is 98.0%), to be added to 10L and contain dodecyl benzene sulfonic acid
(mass concentration of NaOH is 10% and the mass concentration of neopelex is in the NaOH mixed aqueous solution of sodium
0.1%), titanium tetrachloride additional amount and the molar ratio of NaOH are 1:5, carry out high-speed stirring when being added with the revolving speed of 3000r/min
It mixes, after addition, adds the ammonium carbonate solution that mass concentration is 10%, ammonium carbonate additional amount is titanium tetrachloride quality
0.3%, 71 DEG C are then heated to, continues to stir with the revolving speed of 520r/min, 3.0h is cured, is cooled to room temperature, TiO is made2Water
Close object；
B, the TiO for preparing step A2Hydrate carries out filters pressing with filter press, then is washed with deionized to filtrate conductance
Filter cake is made less than 10 μ s/cm in rate；
C, it by the filter cake after step B filters pressing, is dried in microwave dryer with 180 DEG C of temperature, drying time is
Non- crystal titanium dioxide is made in 3.0h；
D, by non-crystal titanium dioxide prepared by step C, air-flow crushing is carried out in airslide disintegrating mill, is made nano amorphous
Titanium dioxide.
Comparative example 2
A, the peristaltic pump for being at room temperature, 5mL/min with flow velocity will prepare rutile-type dioxy by the chloridising of purification
Change the intermediate product titanium tetrachloride (TiCl of titanium4Mass percentage is 98.0%), to be added to 10L and contain dodecyl benzene sulfonic acid
(mass concentration of NaOH is 10% and the mass concentration of neopelex is in the NaOH mixed aqueous solution of sodium
0.1%), titanium tetrachloride additional amount and the molar ratio of NaOH are 1:5, carry out high-speed stirring when being added with the revolving speed of 3000r/min
It mixes, after addition, adds the ammonium carbonate solution that mass concentration is 10%, ammonium carbonate additional amount is titanium tetrachloride quality
0.3%, 71 DEG C are then heated to, continues to stir with the revolving speed of 520r/min, 3.0h is cured, is cooled to room temperature, TiO is made2Water
Close object；
B, the TiO for preparing step A2Hydrate carries out filters pressing with filter press, then is washed with deionized to filtrate conductance
Filter cake is made less than 10 μ s/cm in rate；
C, the filter cake for preparing step B carries out calcining 3.5h in Muffle furnace at a temperature of 500 DEG C, anatase titanium dioxide dioxy is made
Change titanium；
D, by anatase titanium dioxide prepared by step C in airslide disintegrating mill, air-flow crushing is carried out, anatase titanium dioxide is made
Nano-titanium dioxide.
Comparative example 3
This comparative example utilizes the universal anatase titanium dioxide dioxy of prior art production using Hebei Mai Sen titanium dioxide Co., Ltd
Change titanium (NA-100), through ultra-fine grinding, particle size range is 0.2~0.4 μm.NA-100 size distribution is relatively uniform, it is with high purity,
Whiteness is good, good luster, the excellent performance with stronger reducing power, covering power and water dispersible.Its performance indicator is shown in Table 1 institute
Show.
1 anatase titanium dioxide of table (NA-100) performance indicator
Two, effect test
1, performance test
Tin dope amorphous nano titanium dioxide prepared by Examples 1 to 8 is tested for the property, wherein band-gap energy is adopted
It is tested with uv-visible absorption spectra (UV-vis) method, the band-gap energy of sample is then calculated using the method for tangent line,
Other testing performance indexes are carried out referring to relevant national standard, and test result is shown in Table 2, as a comparison, by comparative example 1
Titanium dioxide testing performance index result prepared by~3 is also included in table 2.
2 titanium dioxide testing performance index result of table
Tin dope amorphous nano titanium dioxide prepared by the embodiment of the present invention 1~8 is shown by the test result of table 2
There is biggish specific surface area, preferable water dispersible and lesser with amorphous nano titanium dioxide prepared by comparative example 1
Band-gap energy, specific surface area, average grain diameter, water dispersible and band-gap energy are substantially better than dichloride in anatase type described in comparative example 2~3
TiO2Performance.Preparation method of the invention, it is found that in drying stage, is existed compared with 2 preparation process of comparative example using Muffle furnace
500 DEG C of high temperature calcinings, can be converted into anatase titanium dioxide, due to forming anatase crystal structure, it be made to compare table
Area reduces and band gap can increase.Present invention process creatively uses 180~200 DEG C of microwave dryings of low temperature, instead of Muffle furnace
Amorphous titanium dioxide has been made in high-temperature calcination.
2, visible light catalytic is tested
For tin dope amorphous nano titanium dioxide prepared by the verifying present invention, photocatalysis effect under visible light,
The sample prepared by Examples 1 to 8 carries out visible light catalytic test, and test selects common methylene blue, rhodamine B, first
Four kinds of dye wastewaters of base orange and crystal violet are used as the target contaminant of light-catalyzed reaction, made for characterizing Examples 1 to 8
The photocatalysis performance of standby sample under visible light illumination.Dye solution initial concentration used is 10mg/L, test specimen
Additive amount is 0.4g/L, using the xenon lamp of 300W, irradiation condition of the filter plate of additional 400nm as visible light.It is urged in light
Before changing degradation, the dye solution of 100mL is taken, the test specimen of phase homogenous quantities is added in four kinds of dye solutions respectively, in dark-state
Lower stirring 30min makes test specimen reach absorption-desorption balance, then carries out photocatalytic degradation test, light-catalyzed reaction again
After 4.0h, dye solution is centrifuged, isolates remaining sample in solution.Then UV-vis spectroscopy light is used
The absorbance of degree meter measurement supernatant.By measuring concentration variation of the variation of solution absorbance for dyestuff in analytical solution,
And then test specimen is characterized under visible light to the photocatalytic activity of dyestuff, test result is shown in Table 3.As a comparison, with
Same test conditions have also carried out photocatalysis test to comparative example 1~3, and test result is included in together in table 3.
The test result of 3 four kinds of dyestuffs of photocatalytic degradation of table
By 3 test result of table it is found that by 4h four kinds of dye solutions of visible light photocatalytic degradation, the embodiment of the present invention 1~8
Amorphous nano titanium dioxide prepared by prepared tin dope amorphous nano titanium dioxide and comparative example 1 compares comparative example
Anatase titanium dioxide described in 2~3 is obviously improved to the degradation rate of four kinds of dyestuffs；And tin dope amorphous nano
Titanium dioxide is also improved than degradation rate of the amorphous nano titanium dioxide to four kinds of dyestuffs, it is seen that since the doping of tin is further
The visible light catalysis activity of amorphous nano titanium dioxide is improved, and with SnO2The increase of doping, amorphous nano
Four kinds of dyestuff degradation rates are also respectively increased in titanium dioxide.Same tin dope amount is compared by embodiment 7 and 8, due to implementing
Example 8 is reduced than titanium tetrachloride purity used in embodiment 7, tin dope amorphous nano titanium dioxide pair prepared by embodiment 8
The photocatalytic activity of four kinds of dyestuffs also reduces, it is seen that the purity of titanium tetrachloride is higher to raising tin dope amorphous nano two
Titanium oxide photochemical catalyst active function is bigger.And two kinds of anatase titanium dioxide samples described in comparative example 2~3 are under visible light, photocatalysis drop
The effect of Xie Si kind dyestuff is obviously poor.
Solves the crystalline state TiO of existing chloridising preparation according to the technical solution of the present invention2Photochemical catalyst can to sunlight
Light-exposed non-absorbent defect.The nano amorphous titanium dioxide of tin dope prepared by the present invention is used for degradation of contaminant, shines in visible light
There is efficient photocatalysis performance under the conditions of penetrating, optimize the microstructure of titanium dioxide optical catalyst, solve nano-TiO2
To the responsiveness of visible light, the visible light catalytic performance of nano amorphous titanium dioxide is further improved.
Claims (6)
1. the method for preparing the nano amorphous titanium dioxide of tin dope using chloridising intermediate, which is characterized in that including following step
It is rapid:
A, at room temperature, titanium tetrachloride and tin tetrachloride while cocurrent are added to containing surfactant with peristaltic pump
In NaOH mixed aqueous solution, the high-speed stirred when being added, revolving speed is 3000~3500r/min, after addition, adds carbonic acid
Aqueous ammonium is warming up to 70~80 DEG C, continues to stir, and revolving speed is 500~600r/min, cures 3~4h, is cooled to room temperature, and makes
Obtain tin dope TiO2Hydrate；
B, the tin dope TiO for preparing step A2Hydrate carries out filters pressing with filter press, then is washed with deionized to filtrate electricity
Filter cake is made less than 10 μ s/cm in conductance；
C, it by the filter cake after step B filters pressing, is dried in microwave dryer with 180~200 DEG C of temperature, drying time is
The non-crystal titanium dioxide of tin dope is made in 3~4h；
D, by the non-crystal titanium dioxide of tin dope prepared by step C, air-flow crushing is carried out in airslide disintegrating mill, and tin dope is made
Nano amorphous titanium dioxide.
2. the method according to claim 1 for preparing the nano amorphous titanium dioxide of tin dope using chloridising intermediate,
It is characterized in that, titanium tetrachloride described in step A is that the intermediate of the Preparation of Cajuelite Titania Powders by Chlorination Process by purification produces
Object, TiCl4The molar ratio of mass percentage >=98%, titanium tetrachloride additional amount and NaOH are 1:5~6.
3. the method according to claim 1 for preparing the nano amorphous titanium dioxide of tin dope using chloridising intermediate,
It is characterized in that, tin tetrachloride additional amount described in step A is the 2~5% of titanium tetrachloride quality.
4. the method according to claim 1 for preparing the nano amorphous titanium dioxide of tin dope using chloridising intermediate,
It is characterized in that, described in step A plus the flow velocity of titanium tetrachloride peristaltic pump is 5mL/min, adds the flow velocity of tin tetrachloride peristaltic pump to be
0.25mL/min。
5. the method according to claim 1 for preparing the nano amorphous titanium dioxide of tin dope using chloridising intermediate,
It being characterized in that, in the NaOH mixed aqueous solution described in step A containing surfactant, the mass concentration of NaOH is 10~
15%, the mass concentration of surfactant is 0.1~0.3%, and the surfactant is neopelex.
6. the method according to claim 1 for preparing the nano amorphous titanium dioxide of tin dope using chloridising intermediate,
It is characterized in that, the mass concentration of ammonium carbonate solution described in step A is 10~20%, and ammonium carbonate additional amount is titanium tetrachloride matter
The 0.3~0.5% of amount.
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