CN105728052B - A kind of method that highlight catalytic active nano titanium dioxide is prepared using waste and old wool - Google Patents
A kind of method that highlight catalytic active nano titanium dioxide is prepared using waste and old wool Download PDFInfo
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- CN105728052B CN105728052B CN201610055563.XA CN201610055563A CN105728052B CN 105728052 B CN105728052 B CN 105728052B CN 201610055563 A CN201610055563 A CN 201610055563A CN 105728052 B CN105728052 B CN 105728052B
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- 210000002268 wool Anatomy 0.000 title claims abstract description 97
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000002699 waste material Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 16
- 239000000835 fiber Substances 0.000 claims abstract description 46
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 98
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 91
- 238000006243 chemical reaction Methods 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000008367 deionised water Substances 0.000 claims description 39
- 229910021641 deionized water Inorganic materials 0.000 claims description 39
- 235000019441 ethanol Nutrition 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 26
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 16
- 239000004408 titanium dioxide Substances 0.000 claims description 16
- 239000004115 Sodium Silicate Substances 0.000 claims description 13
- 238000005119 centrifugation Methods 0.000 claims description 13
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 13
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 13
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 13
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 150000003608 titanium Chemical class 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 239000013078 crystal Substances 0.000 abstract description 8
- 230000007062 hydrolysis Effects 0.000 abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 150000003384 small molecules Chemical class 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- -1 amino acids small-molecule Chemical class 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 230000001360 synchronised effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 26
- 239000010936 titanium Substances 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 11
- 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 11
- 229910052719 titanium Inorganic materials 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 10
- 230000003750 conditioning effect Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 229940043267 rhodamine b Drugs 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000010129 solution processing Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 210000004209 hair Anatomy 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 241001494479 Pecora Species 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229960003067 cystine Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 241000345998 Calamus manan Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000372132 Hydrometridae Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 125000002228 disulfide group Chemical group 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of methods that highlight catalytic active nano titanium dioxide is prepared using waste and old wool, in acid condition so that hydrolysis generation amino acids small-molecule substance occurs for wool, the nano-titanium dioxide crystal grain finally generated in hydrothermal reaction process is doped modification, one layer of organic substance film is wrapped up in grain surface, the nano-titanium dioxide of high photocatalysis performance is made.The present invention uses hydro-thermal method, wool staple fiber is added in low-temperature hydrothermal, strong acidic environment, nano titanium dioxide crystal is during generating, growing up, wool fiber synchronous hydrolysis generates the organic matter of small molecule, so as to carry out hydridization and surface graft modification to titania, without adding other chemical reagent and surfactant, preparation process is simple, solution is finally in neutrality, and emission will not cause secondary pollution to environment.
Description
Technical field
The invention belongs to textile engineering technical fields, and in particular to a kind of waste and old wool of utilization prepares highlight catalytic active and receives
The method of rice titanium dioxide.
Background technology
The photocatalysis characteristic of titanium dioxide since the Tokyo Univ Japan rattan the 1970s clear professor in island has found for the first time,
Since it is with good double compatibilities and sterilising, it is widely used to anti-ultraviolet material at present, weaving, photocatalysis are touched
In the industries such as matchmaker, glass with clean, suncream, coating, ink, packaging material for food, paper industry, aerospace industry, lithium battery.Water
Thermal synthesis technology is a kind of important method for preparing nano-oxide, and hydro-thermal method can not only prepare some one pack systems
Tiny crystals, and bi-component or multi-component material can be prepared, overcome the unavoidable hard aggregation of certain hot conditions
Etc. unfavorable factors, research shows that, the position of energy band of titanium dioxide and the reduction potential of adsorbed material determine that its photocatalysis is lived
The ability of property.
At present, people are based on hydro-thermal method, before being with butyl titanate, isopropyl titanate, titanium sulfate, titanium tetrachloride etc. respectively
Body is driven, has successfully prepared the nano-titanium dioxide of anatase or rutile-type；Or addition metallic element (such as silver, iron, copper),
Nonmetalloid (such as carbon, nitrogen, sulphur), rare earth element (such as europium, neodymium, lanthanum) are lived with enhancing the photocatalysis of nano-titanium dioxide
Property, improve the absorbability to visible ray.Wool is mainly by keratin texture into wherein protein content in angle accounts for 97%, inorganic matter
Account for 1~3%.The essential element for forming angle protein includes carbon, oxygen, nitrogen, sulphur and hydrogen etc..Angle protein is by a variety of a-amino acid residue structures
Into, it is intermolecular to form salt type bond and hydrogen bond etc. containing the groups such as carboxyl, amido and hydroxyl on macromolecular chain, between long-chain by
The disulfide bond of cystine is coupled.Wool is more acidproof but not alkaline-resisting, this is because alkali easily decomposes the disulfide group of cystine in wool.
Until today, the recycling of waste and old wool well solve not yet.It is hydrolyzed in an acidic solution using wool, generation is rich
Small-molecule substance containing organic principle is prepared in butyl titanate (or isopropyl titanate, titanium sulfate, titanium tetrachloride) hydro-thermal reaction
During nano-titanium dioxide, the organic elements such as carbon, nitrogen, the sulphur of wool hydrolysis generation are entrained in titanium dioxide granule surface shape
Into a thin clad layer, photocatalytic activity of the nano-titanium dioxide to ultraviolet light and visible ray is improved.It is related at present to use waste and old sheep
Hair has not been reported to prepare the relevant technologies of highlight catalytic active nano titanium dioxide.
Invention content
The object of the present invention is to provide a kind of method that highlight catalytic active nano titanium dioxide is prepared using waste and old wool,
Waste and old wool is hydrolyzed, the organic elements such as carbon therein, nitrogen, sulphur is made to be entrained in titanium dioxide granule surface and form a thin cladding
Layer improves photocatalytic activity of the nano-titanium dioxide to ultraviolet light and visible ray.
The technical solution adopted in the present invention is, a kind of to prepare highlight catalytic active nano titanium dioxide using waste and old wool
Method, specific preparation process is：
Step 1, precursor solution is prepared using titanium salt；
Step 2, waste and old wool pretreatment, obtains wool staple fiber；
Step 3, nano-titanium dioxide is carried out using the precursor solution obtained by step 1 and step 2 gained wool staple fiber
The preparation of powder.
It is of the invention to be further characterized in that,
In step 1, the process for preparation of precursor solution is：
Titanium salt is weighed, is dissolved into absolute ethyl alcohol, after stirring evenly, deionized water is slowly added to, obtains white " milky "
Clear solution recycles hydrochloric acid or sulfuric acid to adjust its pH to 1~2, obtains precursor solution, spare.
Titanium salt is one kind in butyl titanate, isopropyl titanate, titanium tetrachloride or titanium sulfate.
The amount ratio of titanium salt and absolute ethyl alcohol is 1 in gained precursor solution:1；The dosage of deionized water is titanium salt and nothing
7 times of water-ethanol total amount.
In step 2, the detailed process of wool pretreatment is：
Step 2.1：Waste and old wool is weighed, places it in 30~50min of immersion treatment in alkaline mixed solution, then with 30 DEG C
~50 DEG C of ethanol solutions impregnate 10~20min, then are rinsed 1~3 time with deionized water, finally by clean wool at 80 DEG C
It is dried under the conditions of~110 DEG C；
Step 2.2：Step 1.1 gained wool is cut into length with rotation torsion blade fibre cutting machine and is less than the short of 5mm
Fiber.
In step 2.1, the pH of alkaline mixed solution is 8.5~9.5, and alkaline mixed solution is by hydrogen peroxide, sodium carbonate and sodium metasilicate
It mixes, wherein, 10~20ml/L of hydrogen peroxide, sodium carbonate 0.5g/L~2g/L, the sodium metasilicate 0.5g/L of mass concentration 30%
~2g/L.
In step 2.1, the bath raio of waste and old wool and alkaline mixed solution is 1：30~50.
In step 3, the specific preparation process of nano-titanium dioxide powder is：
Step 3.1：Step 2 gained wool staple fiber is immersed in step 1 gained precursor solution after 5~10min, is turned
Move in high-temperature high-pressure reaction kettle, high-temperature high-pressure reaction kettle be placed in homogeneous reactor after sealing, with 1 DEG C/min~3 DEG C/
Min rates are warming up to 110 DEG C~130 DEG C, after 100~200 turns/min rate isothermal reactions 2h~5h, are cooled to room temperature, into
Row centrifugal treating；
Step 3.2：Supernatant liquor after centrifugation is outwelled, raffinate is immersed in acetone soln, in frequency 40kHz, power
It is cleaned by ultrasonic 10~20min under the conditions of 100W, is then immersed in 10~20min of ultrasonic cleaning in ethanol solution, then uses
Deionized water is cleaned by ultrasonic 3 times, every time 5~10min, finally the vacuum drying under the conditions of 100 DEG C~120 DEG C, after grinding to get
Nano-titanium dioxide powder.
In step 3.1, the dosage of wool staple fiber is 1~10% of titanium salt dosage in precursor solution.
The invention has the advantages that
(1) present invention is using hydro-thermal method, with butyl titanate (or isopropyl titanate, titanium sulfate, titanium tetrachloride) for forerunner
Body, in low-temperature hydrothermal, strong acidic environment add wool staple fiber, nano titanium dioxide crystal during generating, growing up,
Wool fiber synchronous hydrolysis generates the organic matter of small molecule, so as to carry out hydridization and surface graft modification to titania,
Other chemical reagent and surfactant need not be added, preparation process is simple, and solution is finally in neutrality, and emission will not be to environment
Cause secondary pollution.
(2) when the present invention uses butyl titanate, isopropyl titanate and titanium sulfate as presoma, anatase can be prepared
Type titanium dioxide nanoparticle, and use titanium tetrachloride be presoma when, rutile type nano titanic oxide can be prepared.Instead
The nano-titanium dioxide of both crystal forms can be doped for the small organic molecule that wool hydrolysis generates during answering and table
Face graft modification, but not destroy the crystal structure of titanium dioxide.A small molecule ball of string for the generation of wool fiber hydrolysis simultaneously can
Titania size is controlled, nano-titanium dioxide can be effectively prevent to generate reunion.
(3) not only photocatalytic activity is strong for the nano-titanium dioxide of doping organic element that the present invention prepares, but also uses
Long lifespan repeated multiple times can use, even if the organic principle for being coated on titanium dioxide granule surface is immersed in acetone, anhydrous second
It will not be dissolved in the organic solvents such as alcohol.
Description of the drawings
Fig. 1 is the stereoscan photograph of 3 gained nano-titanium dioxide of the embodiment of the present invention；
Fig. 2 is the stereoscan photograph of 6 gained nano-titanium dioxide of the embodiment of the present invention；
Fig. 3 is the energy spectrum diagram of 3 gained nano-titanium dioxide of the embodiment of the present invention；
Fig. 4 is the energy spectrum diagram of 6 gained nano-titanium dioxide of the embodiment of the present invention；
Fig. 5 is the embodiment of the present invention 3, the X ray of 2 gained nano-titanium dioxide of embodiment 6, comparative example 1 and comparative example spreads out
Penetrate spectrogram；
Fig. 6 is the embodiment of the present invention 3, the UV, visible light of 2 gained nano-titanium dioxide of embodiment 6, comparative example 1 and comparative example
The light diffusing reflection curve of spectrum；
Fig. 7 is the embodiment of the present invention 3, the ultraviolet light spoke of 2 gained nano-titanium dioxide of embodiment 6, comparative example 1 and comparative example
Irradiation catalytic degradation rhodamine B curve；
Fig. 8 is the embodiment of the present invention 3, the visible ray spoke of 2 gained nano-titanium dioxide of embodiment 6, comparative example 1 and comparative example
Irradiation catalytic degradation rhodamine B curve.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
The present invention is used before butyl titanate (or isopropyl titanate, titanium sulfate, titanium tetrachloride) preparation of nano titanium dioxide
Liquid solution is driven, then in acid condition so that wool generation hydrolysis generation amino acids small-molecule substance, finally anti-in hydro-thermal
The nano-titanium dioxide crystal grain that should be generated in the process is doped modification, and one layer of organic substance film is wrapped up in grain surface, with
Improve the photocatalysis performance of nano-titanium dioxide.
A kind of method that highlight catalytic active nano titanium dioxide is prepared using waste and old wool of the present invention, waste and old wool is existed
Acidic solution hydrolysis is doped package into small-molecule substance and to nano-titanium dioxide crystal grain, and specific preparation process is：
Step 1 prepares butyl titanate (or isopropyl titanate, titanium sulfate, titanium tetrachloride) precursor solution；
Butyl titanate (or isopropyl titanate, titanium sulfate and urea liquid, titanium tetrachloride) solution is measured, it is then that its is molten
It in solution to ethanol solution, and constantly stirs, is subsequently added into deionized water, rapidly while being slowly added into and stir
It mixes, forms white " milky " clear solution, it is 1~2 finally to adjust mixed solution pH value using hydrochloric acid (or sulfuric acid)；Wherein, metatitanic acid
The amount ratio of four butyl esters (or isopropyl titanate, titanium sulfate, titanium tetrachloride) solution and absolute ethyl alcohol is 1:1, the use of deionized water
Measure 7 times for titanium salt and absolute ethyl alcohol total amount.
The cleaning and crushing of step 2, waste and old wool；
Step 2.1, according to bath raio 1：30~50, weigh a certain amount of waste and old wool, 50~60 DEG C, pH value for 8.5~
Under the conditions of 9.5, with the 10~20ml/L of hydrogen peroxide, sodium carbonate 0.5g/L~2g/L, sodium metasilicate 0.5g/L of mass concentration 30%~
The mixed solution that 2g/L is configured to handles 30~50min, then impregnates 10~20min with 30 DEG C~50 DEG C ethanol solutions,
It is rinsed 1~3 time with deionized water, finally dries clean wool under the conditions of 80 DEG C~110 DEG C again.
Step 2.2 turns round blade fibre cutting machine with rotation and the scoured wool that step 2.1 obtains is cut into length is less than
The staple fiber of 5mm.
The preparation of nano-titanium dioxide powder in step 3, thermal and hydric environment；
1~10% according to butyl titanate (or isopropyl titanate, titanium sulfate, titanium tetrachloride) dosage weighs the short fibre of wool
Dimension, and add it in the prepared precursor solution of step 1, transfer them to high-temperature high-voltage reaction after impregnating 5~10min
In kettle, mixed solution accounts for the 70%~90% of reaction kettle volume, and high-temperature high-pressure reaction kettle is placed in homogeneous reactor after sealing,
110 DEG C~130 DEG C are warming up to 1 DEG C/min~3 DEG C/min rates, with 100~200 turns/min rate isothermal reactions 2h~5h.
After reaction kettle is cooled to room temperature, the supernatant liquor after centrifugation is outwelled, residual night is immersed in acetone soln, in frequency
Under the conditions of rate 40kHz, power 100W be cleaned by ultrasonic 10~20min, be then immersed in ethanol solution be cleaned by ultrasonic 10~
20min is then cleaned by ultrasonic 3 times, every time 5~10min with deionized water, and finally vacuum is dried under the conditions of 100 DEG C~120 DEG C
Dry, grinding is spare.
Embodiment 1
The butyl titanate for measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stir, Ran Houhuan
The deionized water of slow addition 70mL simultaneously rapidly stirs, and it is 1 to form white " milky " clear solution hydrochloric acid conditioning solution pH value.It presses
According to bath raio 1：30, weigh waste and old wool, in 50 DEG C, pH value under the conditions of 8.5, with the hydrogen peroxide 10ml/L of mass concentration 30%,
The mixed solution processing 30min that sodium carbonate 0.5g/L, sodium metasilicate 0.5g/L are configured to, is then impregnated with 30 DEG C of ethanol solutions
10min, then rinsed 1 time with deionized water, finally clean wool is dried under the conditions of 80 DEG C.Blade fiber is turned round with rotation to cut
Clean wool is cut into staple fiber of the length less than 5mm by off line.1% according to butyl titanate dosage weighs the short fibre of wool
Dimension, adds it in precursor solution, is transferred them in high-temperature high-pressure reaction kettle after impregnating 5min, liquor capacity accounts for reaction
Reaction kettle, after sealing is placed in homogeneous reactor and is warming up to 110 DEG C with 1 DEG C/min rates, with 100 by the 70% of autoclave body product
Turn/min rate isothermal reactions 2h.After reaction kettle is cooled to room temperature, the supernatant liquor after centrifugation is outwelled, residual night is immersed in third
In ketone solution, it is cleaned by ultrasonic 10min under the conditions of frequency 40kHz, power 100W, is then immersed in ethanol solution ultrasonic
10min is cleaned, is then cleaned by ultrasonic 3 times, each 5min with deionized water, finally the vacuum drying under the conditions of 100 DEG C, grinds
Afterwards to get nano-titanium dioxide powder.
Embodiment 2
The butyl titanate for measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stir, Ran Houhuan
The deionized water of slow addition 70mL simultaneously rapidly stirs, and it is 2 to form white " milky " clear solution hydrochloric acid conditioning solution pH value.It presses
According to bath raio 1：50, a certain amount of waste and old wool is weighed, under the conditions of 60 DEG C, pH value are 9.5, with the hydrogen peroxide of mass concentration 30%
The mixed solution processing 50min that 20ml/L, sodium carbonate 2g/L, sodium metasilicate 2g/L are configured to, then with 50 DEG C of ethanol solutions
20min is impregnated, then is rinsed 3 times with deionized water, finally dries clean wool under the conditions of 110 DEG C.Blade is turned round with rotation
Clean wool is cut into staple fiber of the length less than 5mm by fibre cutting machine.10% according to butyl titanate dosage weighs
Wool staple fiber, adds it in precursor solution, is transferred them in high-temperature high-pressure reaction kettle after impregnating 10min, solution
Volume accounts for the 90% of reaction kettle volume, and reaction kettle is placed in homogeneous reactor after sealing and is warming up to 130 with 3 DEG C/min rates
DEG C, with 200 turns/min rate isothermal reactions 5h.After reaction kettle is cooled to room temperature, the supernatant liquor after centrifugation is outwelled, residual night
It is immersed in acetone soln, is cleaned by ultrasonic 20min under the conditions of frequency 40kHz, power 100W, it is molten to be then immersed in absolute ethyl alcohol
It is cleaned by ultrasonic 20min in liquid, is then cleaned by ultrasonic 3 times, each 10min with deionized water, finally vacuum is dried under the conditions of 120 DEG C
It is dry, to get nano-titanium dioxide powder after grinding.
Embodiment 3
The butyl titanate for measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stir, Ran Houhuan
The deionized water of slow addition 70mL simultaneously rapidly stirs, and it is 1.5 to form white " milky " clear solution hydrochloric acid conditioning solution pH value.
According to bath raio 1：40, a certain amount of waste and old wool is weighed, under the conditions of 55 DEG C, pH value are 9, with the hydrogen peroxide of mass concentration 30%
The mixed solution that 15ml/L, sodium carbonate 1.5g/L, sodium metasilicate 1g/L are configured to handles 40min, then molten with 40 DEG C of absolute ethyl alcohols
Liquid impregnates 15min, then is rinsed 2 times with deionized water, finally dries clean wool under the conditions of 100 DEG C.Knife is turned round with rotation
Clean wool is cut into staple fiber of the length less than 5mm by formula fibre cutting machine.6% according to butyl titanate dosage weighs
Wool staple fiber, adds it in precursor solution, is transferred them in high-temperature high-pressure reaction kettle after impregnating 8min, solution body
Product accounts for the 80% of reaction kettle volume, and reaction kettle is placed in homogeneous reactor after sealing and is warming up to 120 with 2 DEG C/min rates
DEG C, with 150 turns/min rate isothermal reactions 3h.After reaction kettle is cooled to room temperature, the supernatant liquor after centrifugation is outwelled, residual night
It is immersed in acetone soln, is cleaned by ultrasonic 15min under the conditions of frequency 40kHz, power 100W, it is molten to be then immersed in absolute ethyl alcohol
It is cleaned by ultrasonic 15min in liquid, is then cleaned by ultrasonic 2 times, each 7min with deionized water, finally vacuum is dried under the conditions of 110 DEG C
It is dry, to get nano-titanium dioxide powder after grinding.
Embodiment 4
The titanium tetrachloride for measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stir, then slowly
It adds the deionized water of 70mL and rapidly stirs, it is 1 to form white " milky " clear solution hydrochloric acid conditioning solution pH value.According to
Bath raio 1：35, waste and old wool is weighed, under the conditions of 50 DEG C, pH value are 8.5, with hydrogen peroxide 10ml/L, the carbon of mass concentration 30%
The mixed solution processing 35min that sour sodium 0.8g/L, sodium metasilicate 0.8g/L are configured to, is then impregnated with 30 DEG C of ethanol solutions
10min, then rinsed 1 time with deionized water, finally clean wool is dried under the conditions of 90 DEG C.Blade fiber is turned round with rotation to cut
Clean wool is cut into staple fiber of the length less than 5mm by off line.1% according to titanium tetrachloride dosage weighs the short fibre of wool
Dimension, adds it in precursor solution, is transferred them in high-temperature high-pressure reaction kettle after impregnating 6min, liquor capacity accounts for reaction
Reaction kettle, after sealing is placed in homogeneous reactor and is warming up to 115 DEG C with 1 DEG C/min rates, with 130 by the 70% of autoclave body product
Turn/min rate isothermal reactions 3h.After reaction kettle is cooled to room temperature, the supernatant liquor after centrifugation is outwelled, residual night is immersed in third
In ketone solution, it is cleaned by ultrasonic 12min under the conditions of frequency 40kHz, power 100W, is then immersed in ethanol solution ultrasonic
12min is cleaned, is then cleaned by ultrasonic 3 times, each 8min with deionized water, finally the vacuum drying under the conditions of 100 DEG C, grinds
Afterwards to get nano-titanium dioxide powder.
Embodiment 5
The titanium tetrachloride for measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stir, then slowly
It adds the deionized water of 70mL and rapidly stirs, it is 2 to form white " milky " clear solution hydrochloric acid conditioning solution pH value.According to
Bath raio 1：48, a certain amount of waste and old wool is weighed, under the conditions of 60 DEG C, pH value are 9.5, with the hydrogen peroxide of mass concentration 30%
The mixed solution processing 50min that 20ml/L, sodium carbonate 2g/L, sodium metasilicate 2g/L are configured to, then with 50 DEG C of ethanol solutions
20min is impregnated, then is rinsed 3 times with deionized water, finally dries clean wool under the conditions of 105 DEG C.Blade is turned round with rotation
Clean wool is cut into staple fiber of the length less than 5mm by fibre cutting machine.10% according to titanium tetrachloride dosage weighs sheep
Hair staple fiber, adds it in precursor solution, is transferred them in high-temperature high-pressure reaction kettle after impregnating 10min, solution body
Product accounts for the 90% of reaction kettle volume, and reaction kettle is placed in homogeneous reactor after sealing and is warming up to 125 with 3 DEG C/min rates
DEG C, with 190 turns/min rate isothermal reactions 5h.After reaction kettle is cooled to room temperature, the supernatant liquor after centrifugation is outwelled, residual night
It is immersed in acetone soln, is cleaned by ultrasonic 20min under the conditions of frequency 40kHz, power 100W, it is molten to be then immersed in absolute ethyl alcohol
It is cleaned by ultrasonic 20min in liquid, is then cleaned by ultrasonic 3 times, each 10min with deionized water, finally vacuum is dried under the conditions of 120 DEG C
Dry, grinding is spare.
Embodiment 6
The titanium tetrachloride for measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stir, then slowly
It adds the deionized water of 70mL and rapidly stirs, it is 1.5 to form white " milky " clear solution hydrochloric acid conditioning solution pH value.It presses
According to bath raio 1：38, a certain amount of waste and old wool is weighed, under the conditions of 56 DEG C, pH value are 9, with the hydrogen peroxide of mass concentration 30%
The mixed solution that 16ml/L, sodium carbonate 1.5g/L, sodium metasilicate 1g/L are configured to handles 40min, then molten with 40 DEG C of absolute ethyl alcohols
Liquid impregnates 15min, then is rinsed 2 times with deionized water, finally dries clean wool under the conditions of 100 DEG C.Knife is turned round with rotation
Clean wool is cut into staple fiber of the length less than 5mm by formula fibre cutting machine.5% according to titanium tetrachloride dosage weighs sheep
Hair staple fiber, adds it in precursor solution, is transferred them in high-temperature high-pressure reaction kettle after impregnating 7min, liquor capacity
The 80% of reaction kettle volume is accounted for, reaction kettle is placed in homogeneous reactor after sealing and is warming up to 120 DEG C with 2 DEG C/min rates,
With 150 turns/min rate isothermal reactions 3h.After reaction kettle is cooled to room temperature, the supernatant liquor after centrifugation is outwelled, residual night leaching
Bubble is cleaned by ultrasonic 15min under the conditions of frequency 40kHz, power 100W, is then immersed in ethanol solution in acetone soln
Middle ultrasonic cleaning 15min is then cleaned by ultrasonic 2 times, each 7min, the last vacuum drying under the conditions of 110 DEG C with deionized water,
To get nano-titanium dioxide powder after grinding.
Embodiment 7
The isopropyl titanate for measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stir, Ran Houhuan
The deionized water of slow addition 70mL simultaneously rapidly stirs, and it is 1.5 to form white " milky " clear solution hydrochloric acid conditioning solution pH value.
According to bath raio 1：45, a certain amount of waste and old wool is weighed, under the conditions of 53 DEG C, pH value are 9, with the hydrogen peroxide of mass concentration 30%
The mixed solution processing 40min that 16ml/L, sodium carbonate 1.5g/L, sodium metasilicate 1.3g/L are configured to, then with 40 DEG C of absolute ethyl alcohols
Solution impregnates 15min, then is rinsed 2 times with deionized water, finally dries clean wool under the conditions of 90 DEG C.Knife is turned round with rotation
Clean wool is cut into staple fiber of the length less than 5mm by formula fibre cutting machine.7% according to isopropyl titanate dosage weighs
Wool staple fiber, adds it in precursor solution, is transferred them in high-temperature high-pressure reaction kettle after impregnating 8min, solution body
Product accounts for the 80% of reaction kettle volume, and reaction kettle is placed in homogeneous reactor after sealing and is warming up to 120 with 2 DEG C/min rates
DEG C, with 150 turns/min rate isothermal reactions 3.5h.After reaction kettle is cooled to room temperature, the supernatant liquor after centrifugation is outwelled, it is residual
Night is immersed in acetone soln, is cleaned by ultrasonic 15min under the conditions of frequency 40kHz, power 100W, is then immersed in absolute ethyl alcohol
It is cleaned by ultrasonic 15min in solution, is then cleaned by ultrasonic 2 times, each 7min with deionized water, the last vacuum under the conditions of 110 DEG C
Drying, to get nano-titanium dioxide powder after grinding.
Embodiment 8
The urea of titanium sulfate and 10g for measuring 4g is dissolved in the ethanol solution of 5mL, and constantly stir,
Then it is slowly added the deionized water of 70mL and rapidly stirs, form white " milky " clear solution hydrochloric acid conditioning solution pH value
It is 1.5.According to bath raio 1：38, a certain amount of waste and old wool is weighed, under the conditions of 57 DEG C, pH value are 9, with mass concentration 30%
The mixed solution that hydrogen peroxide 15ml/L, sodium carbonate 1.5g/L, sodium metasilicate 1g/L are configured to handles 40min, then anhydrous with 40 DEG C
Alcohol solution dipping 15min, then rinsed 3 times with deionized water, finally clean wool is dried under the conditions of 95 DEG C.With rotation
It turns round blade fibre cutting machine and clean wool is cut into staple fiber of the length less than 5mm.8% according to titanium sulfate dosage weighs
Wool staple fiber, adds it in precursor solution, is transferred them in high-temperature high-pressure reaction kettle after impregnating 9min, solution body
Product accounts for the 80% of reaction kettle volume, and reaction kettle is placed in homogeneous reactor after sealing and is warming up to 130 with 2 DEG C/min rates
DEG C, with 180 turns/min rate isothermal reactions 2.5h.After reaction kettle is cooled to room temperature, the supernatant liquor after centrifugation is outwelled, it is residual
Night is immersed in acetone soln, is cleaned by ultrasonic 15min under the conditions of frequency 40kHz, power 100W, is then immersed in absolute ethyl alcohol
It is cleaned by ultrasonic 15min in solution, is then cleaned by ultrasonic 2 times, each 8min with deionized water, the last vacuum under the conditions of 110 DEG C
Drying, to get nano-titanium dioxide powder after grinding.
Comparative example 1
The butyl titanate for measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stir, Ran Houhuan
The deionized water of slow addition 70mL simultaneously rapidly stirs, and it is 1.5 to form white " milky " clear solution hydrochloric acid conditioning solution pH value
Precursor solution.Precursor solution is transferred in high-temperature high-pressure reaction kettle, liquor capacity accounts for the 80% of reaction kettle volume, close
It is honored as a queen and reaction kettle is placed in homogeneous reactor and is warming up to 120 DEG C with 2 DEG C/min rates, it is anti-with 150 turns/min rate constant temperature
Answer 3h.After reaction kettle is cooled to room temperature, the supernatant liquor after centrifugation is outwelled, residual night is immersed in acetone soln, in frequency
It is cleaned by ultrasonic 15min under the conditions of 40kHz, power 100W, is then immersed in ethanol solution and is cleaned by ultrasonic 15min, then
It is cleaned by ultrasonic 2 times, each 7min with deionized water, the last vacuum drying under the conditions of 110 DEG C, to get nano-silica after grinding
Change titanium valve body.
Comparative example 2
The titanium tetrachloride for measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stir, then slowly
It adds the deionized water of 70mL and rapidly stirs, it is 1.5 to form white " milky " clear solution hydrochloric acid conditioning solution pH value
Precursor solution.Precursor solution is transferred in high-temperature high-pressure reaction kettle, liquor capacity accounts for the 80% of reaction kettle volume, sealing
Reaction kettle is placed in homogeneous reactor afterwards and is warming up to 120 DEG C with 2 DEG C/min rates, with 150 turns/min rate isothermal reactions
3h.After reaction kettle is cooled to room temperature, the supernatant liquor after centrifugation is outwelled, residual night is immersed in acetone soln, in frequency
It is cleaned by ultrasonic 15min under the conditions of 40kHz, power 100W, is then immersed in ethanol solution and is cleaned by ultrasonic 15min, then
It is cleaned by ultrasonic 2 times, each 7min with deionized water, the last vacuum drying under the conditions of 110 DEG C, to get nano-silica after grinding
Change titanium valve body.
Nano titanium dioxide photocatalysis rhodamine B degradation dyestuff performance test of the present invention uses photochemical reaction instrument, specifically
Process is：It is molten that volume 50mL, the rhodamine B of mass percent concentration 5mg/L are added in the quartz glass test tube of diameter about 2cm
Liquid, then add the nano-titanium dioxide powder of 0.01g and be put into magnetic rotor, magnetic agitation 60min in darkroom is placed in, reaches suction
The test tube equipped with rhodamine B solution is positioned in photochemical reaction instrument after attached balance and is irradiated with the mercury lamp of 1000W, is tried
Pipe is away from light source 15cm.Photocatalytic activity during ultraviolet irradiation is measured with below 400nm optical filters, one is taken out every 10min
The solution spectrophotometer for determining volume measures absorbance at 554nm.Visible light exposure is measured with upper filter with 400nm
When photocatalytic activity, every 15min take out certain volume solution spectrophotometer absorbance is measured at 554nm.And
The degradation rate D of rhdamine B is calculated according to formula (1).
In formula：C0It is the initial concentration of rhodamine B solution after adsorption saturation, CtIt is to irradiate rhodamine B solution after a certain period of time
Concentration, t is exposure time.
Test result is：1 gained nano-titanium dioxide of embodiment of the present invention degradation rate after ultraviolet irradiation 60min is
94%, it is seen that degradation rate is 92% after light irradiation 90min.2 gained nano-titanium dioxide of the embodiment of the present invention is in ultraviolet irradiation
Degradation rate is 95% after 60min, it is seen that degradation rate is 94% after light irradiation 90min.3 gained nanometer titanium dioxide of the embodiment of the present invention
Titanium degradation rate after ultraviolet irradiation 60min is 99%, it is seen that degradation rate is 98% after light irradiation 90min.
Fig. 1 is the stereoscan photograph of 3 gained nano-titanium dioxide of the embodiment of the present invention.As can be seen that addition crushes
Wool fiber with the titanium dioxide that butyl titanate is prepared be nanoscale, particle size is than more uniform.Fig. 2 is this hair
The stereoscan photograph of bright 6 gained nano-titanium dioxide of embodiment.As can be seen that addition four chlorinations of chippy wool fiber
The titanium dioxide that titanium is prepared is nanoscale, and particle size is relatively.Fig. 3 is 3 gained nanometer titanium dioxide of the embodiment of the present invention
The energy spectrum diagram of titanium.As can be seen that butyl titanate add in the nano-titanium dioxide that wool is prepared containing it is a certain amount of it is organic into
Point, other than O, Ti element, also containing C, N, S and Cl element.Fig. 4 is the energy of 6 gained nano-titanium dioxide of the embodiment of the present invention
Spectrogram.As can be seen that titanium tetrachloride adds in the nano-titanium dioxide that wool is prepared containing a certain amount of organic principle, in addition to O,
Outside Ti elements, also containing C, S and Cl element.Fig. 5 is embodiment 3,2 gained nano-silica of embodiment 6, comparative example 1 and comparative example
Change the X-ray diffraction spectrogram of titanium.As can be seen that spread out using the nano-titanium dioxide that butyl titanate (comparative example 1) is prepared
Firing angle is anatase to there is apparent diffraction maximum at 25.3 °, 37.8 °, 48.0 °, 55.1 °, 62.7 °, 68.8 ° and 75.0 °
Type, and butyl titanate adds the nano-titanium dioxide that wool (embodiment 3) is prepared diffraction maximum also occur in same position, but
Intensity is reduced, and shows particle size smaller.The nano-titanium dioxide powder prepared using titanium tetrachloride (comparative example 2) is existed
The angle of diffraction is rutile-type to there is stronger diffraction maximum at 27.5 °, 36.1 °, 41.3 °, 54.4 °, 62.8 °, 69.1 °, and
Titanium tetrachloride adds the nano-titanium dioxide that wool (embodiment 6) is prepared diffraction maximum also occur in same position, and intensity is
Reduction shows that particle size is reduced.Fig. 6 is embodiment 3,2 gained nanometer titanium dioxide of embodiment 6, comparative example 1 and comparative example
The UV-Vis reflective spectrum curve of titanium.Compared with the nano-titanium dioxide that titanium tetrachloride (comparative example 2) is prepared, tetrachloro
Change the nano-titanium dioxide that titanium adds wool (embodiment 6) to prepare to significantly increase the absorption of ultraviolet light and visible ray.Compared with metatitanic acid
The nano-titanium dioxide that four butyl esters (comparative example 1) are prepared, butyl titanate add the nano-silica that wool (embodiment 3) is prepared
Change titanium the absorbability of ultraviolet light and visible ray is also remarkably reinforced, it is meant that the nano-titanium dioxide light that wool is prepared is added to urge
Change active higher.Fig. 7 is the ultraviolet irradiation of embodiment 3,2 gained nano-titanium dioxide of embodiment 6, comparative example 1 and comparative example
Photocatalytic degradation rhodamine B curve.As can be seen that during ultraviolet irradiation photocatalytic degradation rhodamine B, butyl titanate adds wool
The photo-catalytic activity of nano titanium dioxide that (embodiment 3) is prepared is better than the nanometer that butyl titanate (comparative example 1) is prepared
Titanium dioxide；The photo-catalytic activity of nano titanium dioxide that titanium tetrachloride adds wool (embodiment 6) to prepare also is better than four chlorinations
The nano-titanium dioxide that titanium (comparative example 2) is prepared.Fig. 8 is embodiment 3,2 gained nanometer of embodiment 6, comparative example 1 and comparative example
The visible light exposure photocatalytic degradation rhodamine B curve of titanium dioxide.It can be seen that visible light exposure photocatalytic degradation rhodamine
During B, the photo-catalytic activity of nano titanium dioxide that butyl titanate adds wool (embodiment 3) to prepare is better than butyl titanate
The nano-titanium dioxide that (comparative example 1) is prepared；The nano-titanium dioxide light that titanium tetrachloride adds wool (embodiment 6) to prepare is urged
Change activity and be equally also better than the nano-titanium dioxide that titanium tetrachloride (comparative example 2) is prepared.
Claims (6)
- A kind of 1. method that highlight catalytic active nano titanium dioxide is prepared using waste and old wool, which is characterized in that specific to prepare Process is：Step 1, precursor solution is prepared using titanium salt, the process for preparation of precursor solution is：Titanium salt is weighed, is dissolved into nothing In water-ethanol, after stirring evenly, deionized water is slowly added to, obtains white " milky " clear solution, hydrochloric acid or sulfuric acid is recycled to adjust Its pH to 1~2 obtains precursor solution, spare；Step 2, waste and old wool pretreatment, obtains wool staple fiber, and the detailed process of wool pretreatment is：Step 2.1：Waste and old wool is weighed, places it in 30~50min of immersion treatment in alkaline mixed solution, then with 30 DEG C~50 DEG C ethanol solution impregnates 10~20min, then rinses 1~3 time with deionized water, finally by clean wool 80 DEG C~ It is dried under the conditions of 110 DEG C；Step 2.2：Blade fibre cutting machine is turned round with rotation, and step 1.1 gained wool is cut into staple fiber of the length less than 5mm；Step 3, nano-titanium dioxide powder is carried out using the precursor solution obtained by step 1 and step 2 gained wool staple fiber Preparation, the specific preparation process of nano-titanium dioxide powder is：Step 3.1：Step 1 gained wool staple fiber is immersed in step 2 gained precursor solution after 5~10min, is transferred to In high-temperature high-pressure reaction kettle, high-temperature high-pressure reaction kettle is placed in homogeneous reactor after sealing, with 1 DEG C/min~3 DEG C/min speed Rate is warming up to 110 DEG C~130 DEG C, after 100~200 turns/min rate isothermal reactions 2h~5h, is cooled to room temperature, is centrifuged Processing；Step 3.2：Supernatant liquor after centrifugation is outwelled, raffinate is immersed in acetone soln, in frequency 40kHz, power 100W Under the conditions of be cleaned by ultrasonic 10~20min, be then immersed in ethanol solution 10~20min of ultrasonic cleaning, then spend from Sub- water is cleaned by ultrasonic 3 times, every time 5~10min, finally the vacuum drying under the conditions of 100 DEG C~120 DEG C, to get nanometer after grinding Titanium dioxide powder.
- 2. a kind of method that highlight catalytic active nano titanium dioxide is prepared using waste and old wool according to claim 1, It is characterized in that, the titanium salt is one kind in butyl titanate, isopropyl titanate, titanium sulfate or titanium tetrachloride.
- 3. a kind of method that highlight catalytic active nano titanium dioxide is prepared using waste and old wool according to claim 2, It is characterized in that, the amount ratio of titanium salt and absolute ethyl alcohol is 1 in gained precursor solution:1；The dosage of deionized water for titanium salt with 7 times of absolute ethyl alcohol total amount.
- 4. a kind of method that highlight catalytic active nano titanium dioxide is prepared using waste and old wool according to claim 1, It is characterized in that, in the step 2.1, the pH of alkaline mixed solution is 8.5~9.5, alkaline mixed solution by hydrogen peroxide, sodium carbonate and Sodium metasilicate mixes, wherein, 10~20ml/L of hydrogen peroxide, sodium carbonate 0.5g/L~2g/L, the sodium metasilicate of mass concentration 30% 0.5g/L~2g/L.
- 5. a kind of method that highlight catalytic active nano titanium dioxide is prepared using waste and old wool according to claim 4, It is characterized in that, in the step 2.1, the bath raio of waste and old wool and alkaline mixed solution is 1：30~50.
- 6. a kind of method that highlight catalytic active nano titanium dioxide is prepared using waste and old wool according to claim 1, It is characterized in that, in the step 3.1, the dosage of wool staple fiber is 1~10% of titanium salt dosage in precursor solution.
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| CN106984353A (en) * | 2017-03-22 | 2017-07-28 | 浙江理工大学 | A kind of method of doped semiconductor photochemical catalyst |
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