CN110156074B - Preparation method of titanium dioxide microspheres - Google Patents
Preparation method of titanium dioxide microspheres Download PDFInfo
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- CN110156074B CN110156074B CN201910502057.4A CN201910502057A CN110156074B CN 110156074 B CN110156074 B CN 110156074B CN 201910502057 A CN201910502057 A CN 201910502057A CN 110156074 B CN110156074 B CN 110156074B
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- titanium
- titanium dioxide
- sulfate
- dioxide microspheres
- foam
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 30
- 239000004005 microsphere Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- 239000010936 titanium Substances 0.000 claims abstract description 24
- 239000006260 foam Substances 0.000 claims abstract description 17
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000008259 solid foam Substances 0.000 claims abstract description 10
- 238000004729 solvothermal method Methods 0.000 claims abstract description 10
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 10
- 230000008014 freezing Effects 0.000 claims abstract description 8
- 238000007710 freezing Methods 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- -1 disodium fatty alcohol Chemical class 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 claims description 8
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 5
- UUWJHAWPCRFDHZ-UHFFFAOYSA-N 1-dodecoxydodecane;phosphoric acid Chemical compound OP(O)(O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC UUWJHAWPCRFDHZ-UHFFFAOYSA-N 0.000 claims description 4
- QZXSMBBFBXPQHI-UHFFFAOYSA-N N-(dodecanoyl)ethanolamine Chemical compound CCCCCCCCCCCC(=O)NCCO QZXSMBBFBXPQHI-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000271 synthetic detergent Substances 0.000 claims description 4
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 4
- IXOCGRPBILEGOX-UHFFFAOYSA-N 3-[3-(dodecanoylamino)propyl-dimethylazaniumyl]-2-hydroxypropane-1-sulfonate Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC(O)CS([O-])(=O)=O IXOCGRPBILEGOX-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- JNGWKQJZIUZUPR-UHFFFAOYSA-N [3-(dodecanoylamino)propyl](hydroxy)dimethylammonium Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)[O-] JNGWKQJZIUZUPR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 claims description 3
- 229940063953 ammonium lauryl sulfate Drugs 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- GWTCIAGIKURVBJ-UHFFFAOYSA-L dipotassium;dodecyl phosphate Chemical compound [K+].[K+].CCCCCCCCCCCCOP([O-])([O-])=O GWTCIAGIKURVBJ-UHFFFAOYSA-L 0.000 claims description 3
- 229940079886 disodium lauryl sulfosuccinate Drugs 0.000 claims description 3
- GLSRFBDXBWZNLH-UHFFFAOYSA-L disodium;2-chloroacetate;2-(4,5-dihydroimidazol-1-yl)ethanol;hydroxide Chemical compound [OH-].[Na+].[Na+].[O-]C(=O)CCl.OCCN1CCN=C1 GLSRFBDXBWZNLH-UHFFFAOYSA-L 0.000 claims description 3
- KHIQYZGEUSTKSB-UHFFFAOYSA-L disodium;4-dodecoxy-4-oxo-3-sulfobutanoate Chemical compound [Na+].[Na+].CCCCCCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O.CCCCCCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O KHIQYZGEUSTKSB-UHFFFAOYSA-L 0.000 claims description 3
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229940026210 lauramidopropylamine oxide Drugs 0.000 claims description 3
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000000344 soap Substances 0.000 claims description 3
- 229940096501 sodium cocoamphoacetate Drugs 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 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 3
- QJRVOJKLQNSNDB-UHFFFAOYSA-N 4-dodecan-3-ylbenzenesulfonic acid Chemical compound CCCCCCCCCC(CC)C1=CC=C(S(O)(=O)=O)C=C1 QJRVOJKLQNSNDB-UHFFFAOYSA-N 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229940098691 coco monoethanolamide Drugs 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000013742 energy transducer activity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- TWMFGCHRALXDAR-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]dodecanamide Chemical compound CCCCCCCCCCCC(=O)NCCCN(C)C TWMFGCHRALXDAR-UHFFFAOYSA-N 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 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 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a rapid preparation scheme of titanium dioxide microspheres, wherein the method comprises the steps of adding a surfactant into water, and preparing foam by stirring; taking out the foam, and quickly freezing to obtain a solid foam template; adding the titanium source solution into the solid foam template to enable the titanium source and water in the foam template to react to generate titanium hydroxide; the titanium hydroxide is converted into titanium dioxide microspheres by high-temperature calcination or solvothermal method. The preparation method is simple, the reaction time is short, the synthesis process is green and pollution-free, and the synthesized titanium dioxide microsphere is hundreds to thousands of nanometers in size and is a novel photosensitive material.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of titanium dioxide microspheres.
Background
Environmental pollution control and new energy development are always important issues which must be faced in the human development process. The semiconductor photocatalysis technology provides a way for effectively treating environmental pollution and carrying out solar energy conversion, and is a green technology with wide application prospect. Among them, titanium dioxide is a photocatalytic material which is the most widely studied and applied because of its non-toxic, non-corrosive and high chemical stability. However, in the practical application of the titanium dioxide photocatalyst, the widely used suspension system is easy to inactivate, easy to agglomerate, difficult to recover and not beneficial to reuse, so that the key problem that the practical application of the titanium dioxide photocatalyst technology is restricted by the condition that the powder catalyst is easy to agglomerate and difficult to recover in the practical application is solved.
At present, two main approaches are used for improving the material recycling performance, the first approach is to design and optimize the shape and prepare micron-sized hollow spheres so as to improve the specific surface area and the photon capture efficiency of the material; the second type is to load high-activity powdery titanium dioxide on other porous materials, so as to avoid performance reduction caused by powder agglomeration and solve the problem of difficult catalyst recovery. The first kind of thought can improve the performance of the material, but because of the inherent poor mechanical strength of the hollow structure, the material gradually disintegrates into a powder system in the use process, and the requirement for recycling in practical application cannot be met. The second category of thinking is helpful for material recycling, but the volume ratio of the carrier is large, and the actual catalytic efficiency of the material per unit volume is low. And the two ideas have the problems of expensive equipment, complex preparation process, long period and the like, and the actual operability is not strong. Therefore, a brand-new titanium dioxide preparation process is developed, the cost is reduced, the period is shortened, the performance is improved, the material can be recycled, and the method has important theoretical and practical values.
Disclosure of Invention
The invention aims to solve the problems of poor adsorption and photocatalytic performances and difficult separation after reaction in the conventional preparation of titanium dioxide microspheres in the prior art, and provides a preparation method of a novel titanium dioxide microsphere.
The preparation method of the titanium dioxide microspheres comprises the following steps: firstly, adding a surfactant into water, and preparing foam by stirring, wherein the stirring speed is 300-10000r/min, and the stirring time is 5-120 min; secondly, taking out the foam and quickly freezing to obtain a solid foam template; adding a titanium source solution into a solid foam template, and enabling the titanium source and water in the foam template to react to generate titanium hydroxide, wherein the content of the titanium source is 5-100 vol%; fourthly, converting the titanium hydroxide into titanium dioxide microspheres by using a high-temperature calcination or solvothermal method.
The surfactant in the first step is disodium lauryl sulfosuccinate, disodium fatty alcohol polyoxyethylene ether (3) sulfosuccinate, disodium coconut monoethanolamide sulfosuccinate, monolauryl phosphate, potassium monolauryl phosphate, lauryl alcohol ether phosphate, potassium lauryl alcohol ether phosphate, fatty alcohol polyoxyethylene ether (EO = 3) ammonium sulfate, coconut monoethanolamide, coconut diethanolamide, cocamidopropyl dimethylamine caprolactone, lauramidopropyl dimethylamine ethylene lactone, cocamidopropyl hydroxysultaine, lauramidopropyl amine oxide, disodium laurylimino secondary acid, fatty acid potassium soap, fatty alcohol benzene sulfonic acid, sodium linear alkyl polyoxyethylene ether sulfate, sodium lauryl sulfate, alpha-alkenyl sulfonate, lauryl dimethyl betaine, sodium lauryl sulfate, sodium lauryl dimethyl betaine, sodium lauryl sulfate, sodium lauryl ether phosphate, sodium lauryl ether phosphate, fatty alcohol polyoxyethylene ether (EO = 3) ammonium sulfate, coco, Dodecyl betaine, cocamidopropyl ammonium oxide, sodium cocoamphoacetate, ammonium lauryl sulfate or synthetic detergents.
And step two, the medium adopted for rapidly freezing the template is liquid carbon dioxide, liquid ammonia, liquid nitrogen, liquid oxygen, liquid argon or liquid helium.
And step three, the titanium source used in the titanium source solution is titanium tetrachloride, butyl titanate, isopropyl titanate, titanium sulfate or titanyl sulfate.
And step three, the dispersing agent used in the titanium source solution is methanol, ethanol, isopropanol or n-butanol.
The high-temperature calcination temperature in the fourth step is 400-1200 ℃, the high-temperature calcination time is 1-12h, the high-temperature calcination atmosphere is air or oxygen, the solvothermal reaction temperature is 120-240 ℃, the solvothermal reaction time is 6-48h, and the solvothermal reaction solvent is water, methanol, ethanol, isopropanol or n-butanol.
The prepared titanium dioxide microspheres are subjected to degradation research, and have excellent degradation performance on toxic and harmful substances such as formaldehyde and benzene and simulated pollutants such as methyl orange and rhodamine B through ultraviolet irradiation test for 1-10 h. The titanium dioxide microspheres can be recycled by sedimentation after the reaction.
Detailed Description
The technical solution of the present invention will be described in detail by the following specific examples. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The first embodiment is as follows: the preparation method of the titanium dioxide microspheres of the embodiment is carried out according to the following steps: firstly, adding a surfactant into water, and preparing foam by stirring, wherein the stirring speed is 300-10000r/min, and the stirring time is 5-120 min; secondly, taking out the foam and quickly freezing to obtain a solid foam template; adding a titanium source solution into a solid foam template, and enabling the titanium source and water in the foam template to react to generate titanium hydroxide, wherein the content of the titanium source is 5-100 vol%; fourthly, converting the titanium hydroxide into titanium dioxide microspheres by using a high-temperature calcination or solvothermal method.
The method of the embodiment adopts the direct hydrolysis method to prepare the titanium dioxide microspheres, the raw materials are simple, only water, a titanium source, a dispersing agent and a detergent are used, and the investment is low; a disperse system is not needed in the preparation process, and the emission is low; the preparation and hydrolysis reaction period of the foam template is only a few minutes, and the preparation period is short; the product titanium dioxide microspheres have excellent mechanical properties, can be recycled by sedimentation, and have practical application significance.
The second embodiment is as follows: the difference between this embodiment and the specific embodiment is that the surfactant in the step one is disodium lauryl sulfosuccinate, disodium fatty alcohol polyoxyethylene ether (3) sulfosuccinate, disodium cocomonoethanolamide sulfosuccinate, monolauryl phosphate, potassium monolauryl phosphate, lauryl alcohol ether phosphate, potassium lauryl alcohol ether phosphate, ammonium fatty alcohol polyoxyethylene ether (EO = 3) sulfate, cocomonoethanolamide, cocodiethanolamide, cocoamidopropyl dimethylamine caprolactone, lauramidopropyl dimethylamine caprolactone, cocamidopropyl hydroxysultaine, lauramidopropyl amine oxide, disodium lauriminosecondary acid, fatty acid potassium soap, linear alkylbenzene sulfonic acid, sodium fatty alcohol polyoxyethylene ether sulfate, sodium lauryl sulfate, Alpha-olefin sulfonate, dodecyl dimethyl betaine, dodecyl betaine, cocamidopropyl ammonium oxide, sodium cocoamphoacetate, ammonium lauryl sulfate or synthetic detergents. Other steps and parameters are the same as in the first embodiment.
The third concrete implementation mode: the difference between this embodiment and the first or second embodiment is that the medium used for rapidly freezing the template in the second step is liquid carbon dioxide, liquid ammonia, liquid nitrogen, liquid oxygen, liquid argon or liquid helium. Other steps and parameters are the same as in one or both of the embodiments.
The fourth concrete implementation mode: the present embodiment is different from the third embodiment in that the titanium source used in the titanium source solution described in the third step is titanium tetrachloride, butyl titanate, isopropyl titanate, titanium sulfate, or titanyl sulfate. Other steps and parameters are the same as those of the third embodiment.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is that the dispersant used in the titanium source solution in the third step is methanol, ethanol, isopropanol or n-butanol. Other steps and parameters are the same as in one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between the present embodiment and one of the first to fifth embodiments is that the high-temperature calcination temperature in the fourth step is 400-. Other steps and parameters are the same as in one of the first to fifth embodiments.
The seventh embodiment: the preparation method of the titanium dioxide microspheres comprises the following steps of firstly, adding a synthetic detergent into water, and preparing foam by stirring, wherein the stirring speed is 600r/min, and the stirring time is 5 min; secondly, taking out the foam, and quickly freezing the foam by using liquid nitrogen to obtain a solid foam template; adding a titanium source solution into a solid foam template, and enabling the titanium source and water in the foam template to react to generate titanium hydroxide, wherein the content of the titanium source is 35 vol%; and fourthly, converting the titanium hydroxide into titanium dioxide microspheres by using a high-temperature calcination method, wherein the high-temperature calcination temperature is 600 ℃, the high-temperature calcination time is 2 hours, and the high-temperature calcination atmosphere is air.
The titanium dioxide microspheres obtained by the embodiment are characterized, the diameter of the microspheres is 200-500nm, the microspheres are anatase titanium dioxide, the obtained titanium dioxide microspheres are used for degrading 5mg/L methyl orange under a 100W ultraviolet lamp, and the product has high photocatalytic degradation performance.
Claims (5)
1. A preparation method of titanium dioxide microspheres is characterized by comprising the following steps: firstly, adding a surfactant into water, and preparing foam by stirring, wherein the stirring speed is 300-10000r/min, and the stirring time is 5-120 min; secondly, taking out the foam and quickly freezing to obtain a solid foam template; adding a titanium source solution into a solid foam template, and enabling the titanium source and water in the foam template to react to generate titanium hydroxide, wherein the content of the titanium source is 5-100 vol%; fourthly, converting the titanium hydroxide into titanium dioxide microspheres by using a high-temperature calcination or solvothermal method;
the surfactant in the first step is disodium lauryl sulfosuccinate, disodium fatty alcohol polyoxyethylene ether (3) sulfosuccinate, disodium coconut monoethanolamide sulfosuccinate, monolauryl phosphate, potassium monolauryl phosphate, lauryl alcohol ether phosphate, potassium lauryl alcohol ether phosphate, fatty alcohol polyoxyethylene ether (EO 3) ammonium sulfate, coconut monoethanolamide, coconut diethanolamide, cocamidopropyl dimethylamine caprolactone, lauramidopropyl dimethylamine ethylene lactone, cocamidopropyl hydroxysultaine, lauramidopropyl amine oxide, disodium laurimido secondary acid, fatty acid potassium soap, linear alkylbenzene sulfonic acid, sodium fatty alcohol polyoxyethylene ether sulfate, sodium lauryl sulfate, alpha-olefin sulfonate, dodecyl dimethyl betaine, sodium lauryl sulfate, sodium lauryl dimethyl betaine, sodium lauryl sulfate, sodium lauryl ether phosphate, or sodium lauryl ether phosphate, Dodecyl betaine, cocamidopropyl ammonium oxide, sodium cocoamphoacetate, ammonium lauryl sulfate or synthetic detergents.
2. The method for preparing titania microspheres according to claim 1, wherein the medium for rapid freezing of the template in step two is liquid carbon dioxide, liquid ammonia, liquid nitrogen, liquid oxygen, liquid argon or liquid helium.
3. The method for preparing titanium dioxide microspheres according to claim 2, wherein the titanium source used in the titanium source solution of step three is titanium tetrachloride, butyl titanate, isopropyl titanate, titanium sulfate, or titanyl sulfate.
4. The method for preparing titanium dioxide microspheres according to claim 1 or 3, wherein the titanium source solution in step three uses a dispersant which is methanol, ethanol, isopropanol or n-butanol.
5. The method for preparing titanium dioxide microspheres as claimed in claim 4, wherein the high temperature calcination temperature in step four is 400-1200 ℃, the high temperature calcination time is 1-12h, the high temperature calcination atmosphere is air or oxygen, the solvothermal reaction temperature is 120-240 ℃, the solvothermal reaction time is 6-48h, and the solvothermal reaction solvent is water, methanol, ethanol, isopropanol or n-butanol.
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| CN105593312A (en) * | 2013-09-27 | 2016-05-18 | 惠普发展公司，有限责任合伙企业 | White pigment dispersions |
| CN108855017A (en) * | 2017-05-09 | 2018-11-23 | 中国科学院上海硅酸盐研究所 | A kind of three-dimensional porous titanium dioxide foam block and preparation method thereof |
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| CN105593312A (en) * | 2013-09-27 | 2016-05-18 | 惠普发展公司，有限责任合伙企业 | White pigment dispersions |
| CN108855017A (en) * | 2017-05-09 | 2018-11-23 | 中国科学院上海硅酸盐研究所 | A kind of three-dimensional porous titanium dioxide foam block and preparation method thereof |
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