CN108187651A - A kind of preparation method and application for carrying zinc nano-titanium dioxide - Google Patents
A kind of preparation method and application for carrying zinc nano-titanium dioxide Download PDFInfo
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- CN108187651A CN108187651A CN201711461153.6A CN201711461153A CN108187651A CN 108187651 A CN108187651 A CN 108187651A CN 201711461153 A CN201711461153 A CN 201711461153A CN 108187651 A CN108187651 A CN 108187651A
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- zinc
- titanium dioxide
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 24
- 239000011701 zinc Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 150000003751 zinc Chemical class 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical group [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 238000001514 detection method Methods 0.000 abstract description 3
- 239000004744 fabric Substances 0.000 abstract description 3
- 239000007921 spray Substances 0.000 abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 28
- 239000000463 material Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 238000004887 air purification Methods 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- -1 hydroxyl radical free radical Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 230000000505 pernicious effect Effects 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-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
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
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Abstract
The invention discloses a kind of preparation methods for carrying zinc nano-titanium dioxide, include the following steps：(1) inorganic dispersant and zinc salt dispersion liquid are added in pure water, then under low-temperature heat stirring, adds titanium tetrachloride aqueous solution；(2) heating is hydrolyzed under stiring, and control temperature stirs 2 hours at 80 150 DEG C, stops heating；(3) plus alkali is neutralized, and then precipitation, press filtration, washing, vacuum drying, dispersion grinding, obtain carrying zinc nano-titanium dioxide.The highly stable application liquid that zinc nano-titanium dioxide is configured to 0.1% is carried made of preparation method disclosed in this invention, using high-pressure spray gun, to surfaces such as indoor wall, roof, cloth curtain, furniture, beds, the effect for removing removing and harmful gas formaldehyde clearly, reaches national indoor formaldehyde Permissible limit 0.1mg/M by detection3Below.
Description
Technical field
The present invention relates to a kind of preparation method and application for carrying zinc nano-titanium dioxide.
Background technology
In recent years, people have Health risk caused by interior decoration and house decorative material very deep cognition, for
The harm of indoor harmful gas, which carries out radical cure, very urgent requirement, has more inspired germinating and the hair of indoor air purification industry
Exhibition.
In recent years, application of the nano titanium dioxide photocatalyst indoors in air purification is commonplace.It is domestic
There are many manufacturer, for the quality of this kind of product on standard market, by national environmental protection product quality supervision and inspection center, Foochow
The units such as photocatalysis research institute of university, China Institute of Standardization are drafted《Purify air photoactivation agent GB/T27870-
2011》National standard, and implemented in 2012.
According to the improvement of indoor air purification for many years, surely belong to " photocatalyst material ", still, photocatalyst using commonplace
The very big characteristic of material is to obtain the energy of ultraviolet light, activation light induced electron transition generate the very strong hydroxyl radical free radical of oxidisability and
Peroxylradicals.This material is fine for outdoor purifying harmful gas effect under ultraviolet light, still, applied to room
Interior due to not having the energy of ultraviolet light, effect is not satisfactory, affects the wide spectrum application of this material to a certain extent.
In order to enable it is section always that the photoresponse range of this material, which expands to visible region and improves its over-all quantum efficiency,
The very active research of skill circle.In order to reduce band gap, broadening photoresponse range and increase electronics -- the separative efficiency in hole pair
Etc. can be carried out efficiently light-catalyzed reaction, have many different process methods at present, including doping metals or it is nonmetallic from
Son and narrow gap semiconductor coupling, auto-dope, heat treatment etc..
Also very active for the research and development of the nano photo-catalytic of modified doping at present, this new material is in visible ray or faint light
Persistently progress catalytic degradation can be discharged under line by PARA FORMALDEHYDE PRILLS(91,95), and the term of validity will theoretically reach 15 years as long as.
There are the improvement that indoor harmful gas is carried out using noble metal or rare earth element, still, this noble metal, transition in the country
It is also less universal in metal, rare earth, the application of the improvement of pernicious gas indoors of nonmetallic loading nanometer titanic oxide material.Have
Following reason：
1st, in the preparation method of nano-titanium dioxide area load metal nanoparticle, key technology is effectively to control
The grain size of metallic processed realizes the crystal form of titanium dioxide and the human controllable of pattern, and can be uniform by metal nanoparticle
It is supported on titanium dioxide surface to ground, polymolecularity.
2nd, the metal nanoparticles such as silver, platinum, zinc have been supported on anatase titania nano particle by document report, but
It is that preparation condition is more harsh, step is relatively complicated, and the grain size of metallic particles is larger and uneven, in titanium dioxide surface
Dispersibility it is also poor.
3rd, this material must be anatase, anatase and rutile ore mixed crystal crystal structure, load in process micro
Element, big Alternative can all obtain the nano material of doping by high-temperature calcination.
4th, the material to make the transition by high-temperature calcination obtains high dispersive aqueous solution using grinding, and technological requirement is harsher.
In this way, the processing cost of this material is just very high, the commonly used of downstream product is affected.
Invention content
In order to solve the above technical problems, the present invention provides a kind of preparation method for carrying zinc nano-titanium dioxide, to reach
It can be by the effective progress of dirt of the interior pernicious gases such as formaldehyde and bacterium caused by decoration, finishing material in visible-range
Absorption degradation, and without the purpose of secondary pollution.
In order to achieve the above objectives, technical scheme is as follows：
A kind of preparation method for carrying zinc nano-titanium dioxide, includes the following steps：
(1) inorganic dispersant and zinc salt dispersion liquid are added in pure water, then under low-temperature heat stirring, adds four chlorinations
Titanium aqueous solution；
(2) heating is hydrolyzed under stiring, and control temperature stirs 2 hours at 80-150 DEG C, stops heating；
(3) plus alkali is neutralized, and then precipitation, press filtration, washing, vacuum drying, dispersion grinding, obtain carrying zinc nano-silica
Change titanium.
In said program, the parts by weight of each substance are respectively：80-90 parts of pure water, 0.05-1 parts of inorganic dispersant, zinc salt
8-15 parts of dispersion liquid, 0.2-0.5 parts of titanium tetrachloride aqueous solution.
In said program, the inorganic dispersant is calgon, sodium tripolyphosphate, sodium pyrophosphate or sodium metasilicate.
In said program, the zinc salt dispersion liquid for zinc salt is added in EDTA or ammonium hydroxide, the zinc salt is zinc nitrate,
Zinc chloride, zinc sulfate or zinc acetate.
In said program, a concentration of 0.1-0.5mol/L of titanium tetrachloride aqueous solution.
In said program, the temperature of low-temperature heat is 30-50 DEG C in the step (1).
In said program, a concentration of 1-5% of the zinc salt dispersion liquid.
In said program, a concentration of the 2% of the zinc salt dispersion liquid.
In said program, a concentration of 0.15mol/L of titanium tetrachloride aqueous solution.
It is a kind of to carry zinc nano-titanium dioxide indoors except the application in formaldehyde.
The nano titanic oxide sol powder is as follows except the mechanism of formaldehyde：
TiO2With photocatalysis determined by the structure of itself, due to TiO2It is a kind of semiconductor, its energy
Bands of a spectrum are not continuous, there are a forbidden band between valence band (VB) and conduction band (CB), TiO during stable state2Electronics riddle valence band
Among, conduction band is a series of aggregate of unoccupied level tracks, has forbidden band to separate between valence band and conduction band, and energy gap is about
3.0—3.2eV.When the ultraviolet light that 387nm is approximately less than by wavelength irradiates, the electronics in valence band is the energy for obtaining photon
And conduction band is transitted to, form light induced electron (e-)；And photohole (h+) is then correspondingly formed in valence band, thus in semiconductor
Inside forms electronics -- hole pair.Due to the discontinuity of semiconductor energy gap, electrons and holes last a long time, light induced electron --
Oxidation or reduction reaction occur for substance of the hole respectively with adsorbing on semiconductor catalyst particle surface.
It is reacted by valence band hole induced oxidation, hole energy 7.5eV or so, oxidizing potential about+3.0V, there is extremely strong oxygen
Change ability, can oxidation of organic compounds, reach the degree of permineralization, generation carbon dioxide, water and inorganic matter.Hole and water
Reaction generation hydroxyl radical free radical.Conduction band electron then induces reduction reaction, and electronics has reproducibility, energy and TiO2The O of adsorption2
Reduction reaction generation peroxy radical occurs for molecule.
Its chemical reaction mechanism is as follows：
TiO2+hv→TiO2+e-+h+
H2O+h+→·OH+H+
OH-+h+→·OH
O2+e-→·O2-
H2O+·O2-→·OOH+OH-
2·OOH→H2O2+O2
·OOH+H2O+e-→H2O2+OH-
H2O2+e-→·OH+OH-
Doping is a kind of change TiO2The effective method of light abstraction width, this technique is in titanium dioxide synthesis with mixing
Miscellaneous method changes TiO2Energy gap and reduce electronics -- hole it is compound.Zinc ion is previously added, purpose is exactly so that zinc
Ion enters its intracell in nano-titanium dioxide forming process, so as to improve the responding ability to visible ray.
Hydroxyl radical free radical and peroxy radical are the extremely strong free radicals of oxidisability, can be by various organic matter direct oxidations
The inorganic molecules such as water, carbon dioxide.Free hydroxyl (OH) has extremely strong oxidisability, and reaction can be about 240Kcal/mol,
Its oxidability is only second to periodic acid, and the oxidability than typical oxidizers such as ozone will be strong, can almost have all compositions
The chemical bond cut-out of machine object molecule is decomposed.Therefore, when free hydroxyl (OH) encounters the organic compounds such as formaldehyde or bacterium, disease
When the microorganisms such as poison, it is oxidized decomposition.
By taking formaldehyde as an example, reaction equation is as follows：
HCHO (formaldehyde)+(OH) → H2O+CO2
Through the above technical solutions, the preparation method provided by the invention for carrying zinc nano-titanium dioxide is in nanometer titanium dioxide
A kind of nano material adulterated zinc ion in titanium hydrolytic process and formed, without high-temperature calcination, can form in aqueous solution
Grain size is in 4--35nm hereinafter, specific surface area is in 100--200M2The anatase of/g range and rutile-type crystal sol, visible
Optical range can the dirt of the pernicious gases such as formaldehyde and bacterium effectively carries out absorption drop caused by decoration, finishing material by interior
Solution, and without secondary pollution.
This good Nano sol powder of dispersibility in aqueous solution is configured to 0.1% highly stable application liquid, adopts
With dedicated high-pressure spray gun, to surfaces such as indoor wall, roof, cloth curtain, furniture, beds, removing and harmful gas formaldehyde is removed
Effect clearly, reach national indoor formaldehyde Permissible limit 0.1mg/M by detection3Below.
Specific embodiment
The technical solution in the embodiment of the present invention will be clearly and completely described below.
The present invention provides a kind of preparation method for carrying zinc nano-titanium dioxide, specific embodiment is as follows：
Embodiment one：
In a reaction kettle with agitating and heating, 800 kilograms of pure water is added in, inorganic dispersion is added with stirring at 30 DEG C
1.5 kilograms of agent sodium metasilicate；By 2.0 kilograms of zinc chloride, it is dissolved in 90 kilograms of pure water containing 2.0 kilograms of EDTA, adds as loading
Add material, be then added in the reaction kettle containing pure water and inorganic dispersant.Add four chlorinations of a concentration of 0.15mol/L
Titanium, addition are 2.5 kilograms, and heating under stiring is hydrolyzed, and temperature reaches 120 DEG C, continues stirring 2 hours, stop adding
Heat.According to hydrolysis acid solution molar ratio, equimolar aqueous slkali is configured and is neutralized, precipitated, press filtration, washing, vacuum drying, divided
Grinding is dissipated, obtains a kind of dispersibility in aqueous solution Nano sol powder well.
Embodiment two
In a band agitating and heating reaction kettle, 850 kilograms of pure water is added in, inorganic dispersant three is added with stirring at 40 DEG C
2.5 kilograms of polyphosphate sodium；By 2.0 kilograms of zinc sulfate, it is dissolved in 90 kilograms of pure water containing 2.0 kilograms of ammonium hydroxide, adds as loading
Add material, be then added in the reaction kettle containing pure water and inorganic dispersant.The tetrachloro of a concentration of 0.20mol/L is added successively
Change titanium, addition is 3.5 kilograms, and heating under stiring is hydrolyzed, and temperature reaches 150 DEG C, continues stirring 2 hours, stops
Heating.According to hydrolysis acid solution molar ratio, be configured equimolar aqueous slkali neutralized, precipitated, press filtration, washing, vacuum drying,
Dispersion grinding obtains a kind of dispersibility in aqueous solution Nano sol powder well.
Embodiment three
In a band agitating and heating reaction kettle, 880 kilograms of pure water is added in, inorganic dispersant three is added with stirring at 45 DEG C
3.0 kilograms of polyphosphate sodium；By 3.0 kilograms of zinc acetate, it is dissolved in 90 kilograms of pure water containing 3.0 kilograms of EDTA, adds as loading
Add material, be then added in the reaction kettle containing pure water and inorganic dispersant.The tetrachloro of a concentration of 0.25mol/L is added successively
Change titanium, addition are 4.5 kilograms, and heating under stiring is hydrolyzed, and temperature reaches 80 DEG C, continues stirring 2 hours, stop adding
Heat.According to hydrolysis acid solution molar ratio, equimolar aqueous slkali is configured and is neutralized, precipitated, press filtration, washing, vacuum drying, divided
Grinding is dissipated, obtains a kind of dispersibility in aqueous solution Nano sol powder well.
Example IV
In a band agitating and heating reaction kettle, 900 kilograms of pure water is added in, inorganic dispersant coke is added with stirring at 50 DEG C
4.0 kilograms of sodium phosphate；By 4.0 kilograms of zinc nitrate, it is dissolved in 90 kilograms of pure water containing 4.0 kilograms of ammonium hydroxide, is added as loading
Material is then added in the reaction kettle containing pure water and inorganic dispersant.Four chlorinations of a concentration of 0.30mol/L are added successively
Titanium, addition are 5 kilograms, and heating under stiring is hydrolyzed, and temperature reaches 100 DEG C, continues stirring 2 hours, stops heating.
According to hydrolysis acid solution molar ratio, be configured equimolar aqueous slkali neutralized, precipitated, press filtration, washing, vacuum drying, dispersion
Grinding obtains a kind of dispersibility in aqueous solution Nano sol powder well.
Dispersibility very well, is configured to 0.1% to Nano sol powder made from above-described embodiment one, two, three, four in aqueous solution
It is highly stable apply liquid, using dedicated high-pressure spray gun, to indoor wall, roof, cloth curtain, furniture, bed etc.
Surface, the effect for removing removing and harmful gas formaldehyde clearly, reach national indoor formaldehyde Permissible limit 0.1mg/M by detection3
Below.
The foregoing description of the disclosed embodiments enables professional and technical personnel in the field to realize or use the present invention.
A variety of modifications of these embodiments will be apparent for those skilled in the art, it is as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and the principles and novel features disclosed herein phase one
The most wide range caused.
Claims (10)
1. a kind of preparation method for carrying zinc nano-titanium dioxide, which is characterized in that include the following steps：
(1) inorganic dispersant and zinc salt dispersion liquid are added in pure water, then under low-temperature heat stirring, adds titanium tetrachloride water
Solution；
(2) heating is hydrolyzed under stiring, and control temperature stirs 2 hours at 80-150 DEG C, stops heating；
(3) plus alkali is neutralized, and then precipitation, press filtration, washing, vacuum drying, dispersion grinding, obtain carrying zinc nanometer titanium dioxide
Titanium.
A kind of 2. preparation method for carrying zinc nano-titanium dioxide according to claim 1, which is characterized in that the weight of each substance
Measuring number is respectively：80-90 parts of pure water, 0.05-1 parts of inorganic dispersant, 8-15 parts of zinc salt dispersion liquid, titanium tetrachloride aqueous solution
0.2-0.5 parts.
3. a kind of preparation method for carrying zinc nano-titanium dioxide according to claim 1, which is characterized in that described inorganic point
Powder is calgon, sodium tripolyphosphate, sodium pyrophosphate or sodium metasilicate.
A kind of 4. preparation method for carrying zinc nano-titanium dioxide according to claim 1, which is characterized in that the zinc salt point
For dispersion liquid for zinc salt is added in EDTA aqueous solutions or ammonium hydroxide, the zinc salt is zinc nitrate, zinc chloride, zinc sulfate or zinc acetate.
A kind of 5. preparation method for carrying zinc nano-titanium dioxide according to claim 1, which is characterized in that four chlorination
Titanium concentration of aqueous solution is 0.1-0.5mol/L.
A kind of 6. preparation method for carrying zinc nano-titanium dioxide according to claim 1, which is characterized in that the step
(1) temperature of low-temperature heat is 30-50 DEG C in.
A kind of 7. preparation method for carrying zinc nano-titanium dioxide according to claim 4, which is characterized in that the zinc salt point
A concentration of 1-5% of dispersion liquid.
A kind of 8. preparation method for carrying zinc nano-titanium dioxide according to claim 7, which is characterized in that the zinc salt point
A concentration of the 2% of dispersion liquid.
A kind of 9. preparation method for carrying zinc nano-titanium dioxide according to claim 5, which is characterized in that four chlorination
Titanium concentration of aqueous solution is 0.15mol/L.
10. a kind of load zinc nano-titanium dioxide as described in claim 1 is indoors except the application in formaldehyde.
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Application publication date: 20180622 |