CN105833920B - A kind of ultra-dispersed photochemical catalyst and preparation method and application - Google Patents
A kind of ultra-dispersed photochemical catalyst and preparation method and application Download PDFInfo
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- CN105833920B CN105833920B CN201610267420.5A CN201610267420A CN105833920B CN 105833920 B CN105833920 B CN 105833920B CN 201610267420 A CN201610267420 A CN 201610267420A CN 105833920 B CN105833920 B CN 105833920B
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- titanium dioxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000002485 combustion reaction Methods 0.000 claims abstract description 56
- 239000000446 fuel Substances 0.000 claims abstract description 29
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 21
- 150000001298 alcohols Chemical class 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 239000000295 fuel oil Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000011164 primary particle Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- 239000000843 powder Substances 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- 239000002283 diesel fuel Substances 0.000 claims description 7
- PTOQQPHFZLBDFC-UHFFFAOYSA-N SOCCC[Si](C)(C)C Chemical compound SOCCC[Si](C)(C)C PTOQQPHFZLBDFC-UHFFFAOYSA-N 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 6
- 230000003595 spectral effect Effects 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 4
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000004332 deodorization Methods 0.000 abstract 1
- 230000001954 sterilising effect Effects 0.000 abstract 1
- 238000004659 sterilization and disinfection Methods 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 description 19
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- -1 hydroxyl free radical Chemical class 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 229910000048 titanium hydride Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 201000009310 astigmatism Diseases 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
The ultra-dispersed photochemical catalyst of the present invention includes following components：10 ~ 14 parts of 90 ~ 110 parts of alcohols solvent, 2 ~ 6 parts of titanium dioxide and dispersant, the ultra-dispersed photochemical catalyst are translucent solution, and the primary particle size of titanium dioxide is 10 ~ 50nm, and aggregate particle size is less than 100nm, and safe and non-toxic and catalytic effect is notable.Mainly has the following advantages：（1）The photocatalysis response of ultraviolet, visible full spectral region；（2）Suitable for fuel oil combustion catalysis；（3）Notable emission reduction safety and environmental protection.The ultra-dispersed photochemical catalyst preparation method of the present invention（1）Realize nano-titanium dioxide high degree of dispersion in alcohols solvent；（2）Obtaining has part titanium ion auto-dope feature, reduces energy gap, realizes the photocatalysis response of ultraviolet, visible full spectral region；（3）Reduce cost.The application of the ultra-dispersed photochemical catalyst of the present invention is no longer limited to indoor environmental pollution, sterilization, deodorization, may be directly applied to the fuel combustion catalysis of fuel combustion catalysis, particularly car combustion engine.
Description
Technical field
The present invention relates to photocatalyst technology field, more particularly to a kind of ultra-dispersed catalysis of modifying titanium dioxide solution
Agent and preparation method and application.
Background technology
Methanol is substituted into internal combustion engine part fuel oil, becomes the important channel for reducing consumption of petroleum.Diesel oil/methanol binary combustion
Fuel combustion gross efficiency can be improved more than 20% by material system.Methanol becomes most promising by the more energy efficient emission reduction of diesel engine
One of oil replacement fuel.However, during binary fuel combustion oxidation, due to pressure and temp, still there is part
The hydrocarbon that incomplete oxidation is decomposed.How by improving the efficiency of combustion of fuel, promote combustion product oxidation completely into
Emphasis for researcher's concern.
At present, researcher both domestic and external has carried out many research to catalysis burning in gasoline engine and diesel engine.Existing skill
In art, the catalyst type being applied in catalysis burning mainly has noble metal catalyst（Platinum（Pt）, rhodium（Rh）, palladium（Pd）Deng,
It is low to fire temperature, high catalytic efficiency, but poor heat resistance, easy-sintering, and it is expensive, it is mainly used as post-processing.Transiting metal oxidation
Object catalyst： CuO、Al2O3、Cu2O、Fe2O3、Mn3O4, one or more doping derives from a wealth of sources, is cheap, but catalysis work
Property is to be improved, is mainly used for methane catalytic combustion.And photocatalyst catalyst（Based on nano-titanium dioxide, also known as photocatalysis
Agent or photocatalyst）, photocatalyst is catalyst coated in substrate surface, strong catalytic degradation work(is generated under the action of ultraviolet light
Can, catalytic performance is high, but because being affected by temperature and the factor of illumination, is currently used primarily in indoor environmental pollution, sterilizes, remove
It is smelly or by photocatalyst coated in vehicle exhaust of degrading on asphalt road, be hardly directly used in the combustion catalysis of fuel oil.
Chinese invention patent document（103061925 B of publication number CN）Disclosing a kind of utilization, magnetically and optically catalyst and light are made
With the method for improving automotive fuel combustion rate, catalytic oxidation, fuel gas molecule are occurred by the fuel under magnetic environment
Chain fracture releases hydroxyl free radical, and the decomposable asymmetric choice nets such as contained mercaptan, thiophene go out hydrogen, generate a large amount of free radical and hydrogen,
After Raolical polymerizable so that the molecular motion state of free radical polymerization becomes hollow tubulose by past Brownian movement and transports
It is dynamic, burn rate can be improved.The photocatalyst body that the present invention is located in fuel simultaneously is irradiated in the light source that wavelength is 175~400nm
Under, generate electron hole pair due to absorbing luminous energy.These holes pair（Photocarrier）Surface can be rapidly migrated to, and is activated
The H of its surface attachment2O and O2And generate hydroxy（-OH）And active oxygen（-O2-）, to promote to improve the effect of burn rate.The party
By the fuel under magnetic environment catalytic oxidation occurs for method to improve burn rate, and the irradiation photocatalyst of additional light source is needed to urge
Agent competence exertion acts on, it is impossible to photocatalyst catalyst directly be directly applied to automotive fuel combustion catalysis, if according to this
Method implements existing various burners, boiler combustion system and car combustion engine and is required to be transformed, and improvement cost is very
Height, and the structure of burner also becomes more complicated.However, traditional photocatalyst is difficult to alcohols solvent dispersion, in stone
Dispersion in oil, diesel oil and diesel oil/methanol binary system is more difficult to, and catalytic action is difficult to play.
Therefore, for of the prior art there are problem, it is urgent to provide a kind of fuel oil combustion catalysis that may be directly applied to
Photocatalyst catalysis technique is particularly important.
Invention content
A kind of oversubscription for fuel oil burning is provided it is an object of the invention to avoid shortcoming of the prior art
Astigmatism catalyst.
The purpose of the present invention is achieved through the following technical solutions：
A kind of ultra-dispersed photochemical catalyst is provided, includes the component of following parts by weight：
90 ~ 110 parts of alcohols solvent
2 ~ 6 parts of titanium dioxide
10 ~ 14 parts of dispersant
The primary particle size of titanium dioxide is 10 ~ 50nm, and aggregate particle size is less than 100nm.
Wherein, titanium dioxide is auto-dope titanium dioxide.
Preferably, a kind of ultra-dispersed photochemical catalyst includes the component of following parts by weight
100 parts of alcohols solvent
4 parts of titanium dioxide
12 parts of dispersant.
Preferably, dispersant is ethyl orthosilicate, γ-mercapto oxypropyl trimethyl silane, vinyltrimethoxysilane, ethylene
More than one of ethyl triethoxy silicane alkane and propyl trimethoxy silicane.
Preferably, alcohols solvent is methanol.
Preferably, the primary particle size of titanium dioxide is 25 ~ 30nm, and aggregate particle size is less than 100nm.
It is provided a kind of for fuel oil burning another object of the present invention is to avoid shortcoming of the prior art
The preparation method of ultra-dispersed photochemical catalyst.
Another object of the present invention is achieved through the following technical solutions：
A kind of ultra-dispersed photochemical catalyst preparation method, is used to prepare above-mentioned ultra-dispersed photochemical catalyst, includes following
Step,
（1）Take the TiH of 1 parts by weight2Powder is placed in reactor, adds in the water and 15 ~ 20 parts by weight of 50 ~ 100 parts by weight
Hydrogen peroxide, stir 1 ~ 6 hour, obtain yellow-green slurry；
（2）The nano-titanium dioxide powder of 1 ~ 5 parts by weight, after being sufficiently stirred, 45 ~ 60 DEG C of vacuum are added in toward yellow-green slurry
It is 10 ~ 14 hours dry, obtain canescence powder；
（3）By canescence vacuum powder high-temperature calcination, blue and white powder is obtained；
（4）Blue and white powder is added in the mixed liquor of dispersant and alcohols solvent, stirred 1.5 ~ 2.5 hours, ultrasound
Wavelength-division dissipates 10 ~ 20 minutes, obtains translucent titania solution as ultra-dispersed photochemical catalyst.
Preferably, step（3）In, canescence powder is put into the calcining of vacuum drying oven high temperature, calcination temperature is 400 ~ 600
℃。
It is furthermore preferred that a kind of ultra-dispersed photochemical catalyst preparation method includes following steps：
（1）The TiH2 powders of 1 parts by weight are taken, add in the water of 80 parts by weight and the hydrogen peroxide of 17 parts by weight, are stirred 3 hours；
（2）The nano-titanium dioxide powder of 2 parts by weight is added in, after being sufficiently stirred, 50 DEG C are dried in vacuo 12 hours, obtain ash
White powder；
（3）Canescence powder in vacuum high-temperature is calcined, obtains blue and white powder；
（4）Dispersant is ethyl orthosilicate, γ-mercapto oxypropyl trimethyl silane, vinyltrimethoxysilane, vinyl three
More than one of Ethoxysilane and propyl trimethoxy silicane, alcohols solvent are methanol, and blue and white powder is added to dispersion
It in the mixed liquor of agent and methanol, stirs 2 hours, ultrasonic wave disperses 15 minutes, obtains translucent titania solution.
The application that above-mentioned ultra-dispersed photochemical catalyst is also provided of the present invention：Above-mentioned ultra-dispersed photocatalyst applications are in fuel
Combustion catalysis.
Particularly, the fuel oil combustion catalysis applied to internal combustion engine binary fuel system, by ultra-dispersed photochemical catalyst according to need
With the arbitrary multiple of methanol dilution, air intake duct is sprayed by nozzle by internal combustion engine methanol pipeline, enters cylinder catalysis with air
The burning of diesel oil and methanol binary fuel.
Beneficial effects of the present invention：
The ultra-dispersed photochemical catalyst of the present invention includes the component of following parts by weight：90 ~ 110 parts of alcohols solvent, titanium dioxide
10 ~ 14 parts of 2 ~ 6 parts of titanium and dispersant, the ultra-dispersed photochemical catalyst are translucent solution, wherein, in solution, the one of titanium dioxide
Secondary grain size be 10 ~ 50nm, aggregate particle size be less than 100nm, it is not only safe and non-toxic, and applied to fuel combustion contribute to it is energy saving
Emission reduction, clear carbon distribution and raising combustion utilization efficiency, for being applied to automobile engine binary fuel combustion system catalytic combustion-supporting, are imitated
Fruit is notable.Relative to the prior art, mainly have the advantages that：
（1）For the surface area of nano particle/grain size than greatly, easily reuniting, poor compatibility leads to poor dispersion, can be big
The big catalytic performance for reducing photocatalyst catalyst, therefore the dispersibility of nano-titanium dioxide is always to influence the key of its catalytic performance
Sexual factor.In the present invention, the primary particle size of titanium dioxide is 10 ~ 50nm, and aggregate particle size is less than 100nm, dispersability of titanium dioxide
It is good and stable, there is excellent catalytic performance, realize the photocatalysis response of ultraviolet, visible full spectral region.
（2）And the ultra-dispersed photochemical catalyst of the present invention is solution of the alcohols as solvent, suitable for fuel oil combustion catalysis,
Photocatalyst is applied to the new side that internal combustion engine double fuel combustion field is photocatalyst development by special binary fuel oil system catalytic combustion-supporting
To using the spectrum generated in fuel combustion process, gathering materials on the spot, be converted into the power source of catalyst.Meanwhile it is being catalyzed
Under the action of agent, fuel combustion is more complete, and combustion duration increases, and the thermal efficiency of burning significantly improves.
（3）Notable emission reduction safety and environmental protection
Photocatalyst under the action of light, can generate light induced electron as this positive semiconductor（e-）With hole（h+）, and with suction
The dissolved oxygen for being attached to nano grain surface forms superoxide anion, with hydroxide ion and water oxygen chemical conversion hydroxyl free radical.Super oxygen
Anion and hydroxyl free radical have very strong oxidisability, can be by most of oxidation operation to final product CO2And H2O,
Even some inorganic matters also can be decomposed thoroughly.Photocatalyst can promote organic matter in internal combustion engine binary fuel combustion system
Complete oxidation reduces the concentration of carbon monoxide, nitrogen oxides, sulfide.
The main following advantageous effect of ultra-dispersed photochemical catalyst preparation method of the present invention：
（1）High degree of dispersion of the nano-titanium dioxide in alcohols solvent can be achieved, color is semi-transparent clear, and stability is high；
（2）Full spectral response expands spectral absorption threshold value
The quantum yield of nano-titanium dioxide is improved, passes through Low-valent Titanium precursor TiH2（Titanium hydride）Add in water and dioxygen
The previously prepared yellow-green slurry of water, the yellow-green slurry are trivalent titanium and 4 valency titanium mixed gels, then add in times that market is sold
It anticipates a kind of white nano-titanium dioxide powder so that trivalent titanium and 4 valency titanium mixed gels are coated on the surface of nano-titanium dioxide.
Then by means such as high temperature, vacuum calcinings, obtaining has part titanium ion auto-dope feature, real so as to reduce energy gap
The photocatalysis response of existing ultraviolet, visible full spectral region；
（3）Reduce cost
Bright raw material are simple and easy to get, easy to operate, it can be achieved that large-scale production and canned, low production cost.Meanwhile add
Note mode can be operated according to the original methanol feeding mode of internal combustion engine binary fuel combustion system, existing each without changing
The structure of kind burner, boiler combustion system and car combustion engine avoids improvement expenses from lowering and utilizes photochemical catalyst catalysis burning
Use cost.Promote burning adequately at the same time it can also reduce carbon distribution, reduce Motor Maintenance cost.
Specific embodiment
The invention will be further described with the following Examples.
Embodiment 1
The ultra-dispersed photochemical catalyst of the present embodiment includes the component of following parts by weight：
Alcohols solvent 90g
Titanium dioxide 2g
Dispersant 10g
Due to nano-titanium dioxide surface can it is larger it is easy reunite, the grain diameter reunited is different, locate
In in certain range.The primary particle size of particle that the titanium dioxide reunion of the present embodiment forms is 10 ~ 25nm, and aggregate particle size is small
In 100nm.
Embodiment 2
The main technical schemes of the present embodiment are substantially the same manner as Example 1, and the feature not laid down a definition in the present embodiment is adopted
With the explanation in embodiment 1, no longer repeated herein.The ultra-dispersed photochemical catalyst of the present embodiment includes following parts by weight
Component：
Alcohols solvent 110g
Titanium dioxide 6g
Dispersant 14g
The primary particle size of titanium dioxide is 30 ~ 50nm, and aggregate particle size is less than 90nm.
Embodiment 3
The main technical schemes of the present embodiment are substantially the same manner as Example 1, and the feature not laid down a definition in the present embodiment is adopted
With the explanation in embodiment 1, no longer repeated herein.The ultra-dispersed photochemical catalyst of the present embodiment includes following parts by weight
Component：
Alcohols solvent 100g
Titanium dioxide 4g
Dispersant 12g
The primary particle size of titanium dioxide is 25 ~ 30nm, and aggregate particle size is less than 80nm.
When initial temperature is 800k, the catalysis of embodiment 1, implementation 2 and embodiment 3 to diesel oil and methanol binary fuel system
Influence such as table 1：
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Delay period shortens | 0.25ms | 0.20ms | 0.15ms |
| Main combustion period is elongated | 38.6% | 32.8% | 25.2% |
| Heat release starting point shifts to an earlier date | 0.4ms | 0.3ms | 0.2ms |
| Soot production quantity declines | 9.3% | 10.5% | 11.4% |
Embodiment 4
The ultra-dispersed photochemical catalyst preparation method of the present embodiment, is as follows：
（1）Take 1g TiH2 Powder is placed in single-necked flask, then adds in deionized water 50g, hydrogen peroxide 15g, and magnetic force stirs
It mixes 6 hours, forms yellow-green slurry；
（2）Add in 5g Japan stone original st01 nano-titanium dioxide powders.After being sufficiently stirred, it is put into 50 DEG C of temperature of vacuum drying chamber
Degree is lower 14 hours dry, obtains canescence powder；
（3）Powder is put into 400 DEG C of high-temperature calcinations in vacuum drying oven, obtains blue and white powder；
（4）Powder is poured into the methanol solution of γ-mercapto oxypropyl trimethyl silane, stirred 2.5 hours, ultrasonic disperse 20 divides
Clock obtains translucent titania solution as ultra-dispersed photochemical catalyst.
Ultra-dispersed photocatalyst solution obtained is directly applied to the combustion catalysis of car combustion engine, oversubscription astigmatism is urged
1000 times of methanol dilution of agent, then air intake duct is sprayed by nozzle by methanol pipeline, with air enter cylinder catalytic diesel oil and
The burning of methanol fuel.Solution is used.Under different initial temperatures, influence of the observation catalyst to combustion case, obtain with
Lower result：
| Initial temperature | 800k | 850k | 900k |
| Delay period shortens | 0.25ms | 0.15ms | 0.2ms |
| Main combustion period is elongated | 42.9% | 32% | 9.5% |
| Heat release starting point shifts to an earlier date | 0.5ms | 0.4ms | 0.1ms |
| Soot production quantity declines | 8.3% | 24.8% | 10.4% |
Illustrate, the ultra-dispersed photocatalyst solution of the present embodiment is just used applied to the combustion catalysis of car combustion engine
If applying the fuel system in other fuel oils and alcohol, other alcohols solvents can be used as diluent, according to reality in methanol dilution
Need arbitrary times of dilution.
Embodiment 5
The main technical schemes of the present embodiment are substantially the same manner as Example 4, and the feature not laid down a definition in the present embodiment is adopted
With the explanation in embodiment 4, no longer repeated herein.
The ultra-dispersed photochemical catalyst preparation method of the present embodiment, is as follows：
（1）Take 0.1g TiH2 Powder is placed in single-necked flask, then adds in deionized water 10g, hydrogen peroxide 2g, and magnetic force stirs
It mixes 1 hour, forms yellow-green slurry；
（2）Add in 1g Degussa P25 type nano-titanium dioxide powders.After being sufficiently stirred, it is put into 45 DEG C of temperature of vacuum drying chamber
Degree is lower 10 hours dry, obtains canescence powder；
（3）Powder is put into 500 DEG C of high-temperature calcinations in vacuum drying oven, obtains blue and white powder；
（4）Powder is poured into the methanol solution of vinyltriethoxysilane, stirred 1.5 hours, ultrasonic disperse 10 divides
Clock obtains translucent titania solution as ultra-dispersed photochemical catalyst.
Under different initial temperatures, influence of the observation photochemical catalyst to internal combustion engine fuel combustion situation obtains following knot
Fruit：
| Initial temperature | 800k | 850k | 900k |
| Delay period shortens | 0.15ms | 0.05ms | 0.1ms |
| Main combustion period is elongated | 43.8% | 25% | 5.6% |
| Heat release starting point shifts to an earlier date | 0.3ms | 0.2ms | 0.1ms |
| Soot production quantity declines | 6.5% | 22.3% | 7.5% |
Embodiment 6
The main technical schemes of the present embodiment are substantially the same manner as Example 4, and the feature not laid down a definition in the present embodiment is adopted
With the explanation in embodiment 4, no longer repeated herein.
The ultra-dispersed photochemical catalyst preparation method of the present embodiment, is as follows：
（1）Take 0.5g TiH2 Powder is placed in single-necked flask, then adds in deionized water 25g, hydrogen peroxide 10g, magnetic force
Stirring 4 hours forms yellow-green slurry；
（2）Add in the 1g country certain company HLB type nano-titanium dioxide powders.After being sufficiently stirred, it is put into vacuum drying chamber 60
It is 12 hours dry at a temperature of DEG C, obtain canescence powder；
（3）Powder is put into 600 DEG C of high-temperature calcinations in vacuum drying oven, obtains blue and white powder；
（4）Powder is poured into the methanol mixed solution of ethyl orthosilicate, γ-mercapto oxypropyl trimethyl silane, stirring 2 is small
When, ultrasonic disperse 15 minutes obtains translucent titania solution as ultra-dispersed photochemical catalyst.
Under different initial temperatures, influence of the observation photochemical catalyst to internal combustion engine fuel combustion situation obtains following knot
Fruit：
| Initial temperature | 800k | 850k | 900k |
| Delay period shortens | 0.3ms | 0.2ms | 0.1ms |
| Main combustion period is elongated | 27% | 30.5% | 10.5% |
| Heat release starting point shifts to an earlier date | 0.6ms | 0.45ms | 0.25ms |
| Soot production quantity declines | 9.4% | 25% | 15% |
Embodiment 7
In the present embodiment, ultra-dispersed photochemical catalyst of the invention directly applies to the combustion catalysis of boiler combustion system.But
It should be noted that ultra-dispersed photocatalyst applications of the invention are catalyzed in fuel combustion and are not limited to boiler and car combustion engine.
Finally it should be noted that above example is merely to illustrate technical scheme of the present invention explanation rather than will to right
Ask the limitation of protection domain.Those of ordinary skill in the art should be appreciated that with reference to preferred embodiment and can be to the present invention's
Technical solution is modified or replaced equivalently, but belongs to the substantially identical and protection domain of technical solution of the present invention.
Claims (10)
1. a kind of ultra-dispersed photochemical catalyst preparation method, it is characterised in that：Include following steps,
（1）Take the TiH of 1 parts by weight2Powder is placed in reactor, adds in the water of 50 ~ 100 parts by weight and the dioxygen of 15 ~ 20 parts by weight
Water stirs 1 ~ 6 hour, obtains yellow-green slurry；
（2）The nano-titanium dioxide powder of 1 ~ 5 parts by weight is added in toward yellow-green slurry, after being sufficiently stirred, 45 ~ 60 DEG C of vacuum drying
10 ~ 14 hours, obtain canescence powder；
（3）By canescence vacuum powder high-temperature calcination, blue and white powder is obtained；
（4）Blue and white powder is added in the mixed liquor of dispersant and alcohols solvent, stirred 1.5 ~ 2.5 hours, ultrasonic wavelength-division
It dissipates 10 ~ 20 minutes, obtains translucent titania solution as ultra-dispersed photochemical catalyst.
2. a kind of ultra-dispersed photochemical catalyst preparation method according to claim 1, it is characterised in that：Step（3）In, it will be grey
White powder is put into the calcining of vacuum drying oven high temperature, and calcination temperature is 400 ~ 600 DEG C.
3. a kind of ultra-dispersed photochemical catalyst preparation method according to claim 1, it is characterised in that：
（1）Take the TiH of 1 parts by weight2Powder adds in the water of 80 parts by weight and the hydrogen peroxide of 17 parts by weight, stirs 3 hours；
（2）The nano-titanium dioxide powder of 2 parts by weight is added in, after being sufficiently stirred, 50 DEG C are dried in vacuo 12 hours, obtain canescence
Powder；
（3）By canescence vacuum powder high-temperature calcination, blue and white powder is obtained；
（4）Dispersant is ethyl orthosilicate, γ-mercapto oxypropyl trimethyl silane, vinyltrimethoxysilane, three ethoxy of vinyl
More than one of base silane and propyl trimethoxy silicane, alcohols solvent are methanol, by blue and white powder be added to dispersant with
It in the mixed liquor of methanol, stirs 2 hours, ultrasonic wave disperses 15 minutes, obtains translucent titania solution.
4. a kind of ultra-dispersed photochemical catalyst, it is characterised in that：It is made, included by claims 1 to 3 any one preparation method
The component of following parts by weight：
90 ~ 110 parts of alcohols solvent
2 ~ 6 parts of titanium dioxide
10 ~ 14 parts of dispersant,
The primary particle size of titanium dioxide is 10 ~ 50nm, and aggregate particle size is less than 100nm.
5. a kind of ultra-dispersed photochemical catalyst according to claim 4, it is characterised in that：Include the group of following parts by weight
Point：
100 parts of alcohols solvent
4 parts of titanium dioxide
12 parts of dispersant.
6. a kind of ultra-dispersed photochemical catalyst according to claim 4 or 5, it is characterised in that：Dispersant for ethyl orthosilicate,
γ-mercapto oxypropyl trimethyl silane, vinyltrimethoxysilane, vinyltriethoxysilane and propyl trimethoxy silicane
More than one.
7. a kind of ultra-dispersed photochemical catalyst according to claim 4 or 5, it is characterised in that：Alcohols solvent is methanol.
8. a kind of ultra-dispersed photochemical catalyst described in item according to claim 4 or 5, it is characterised in that：The primary grain of titanium dioxide
Diameter is 25 ~ 30nm, and aggregate particle size is less than 100nm.
9. the application of ultra-dispersed photochemical catalyst, it is characterised in that：The ultra-dispersed photochemical catalyst of claim 1 to 8 any one should
It is catalyzed for fuel combustion.
10. the application of ultra-dispersed photochemical catalyst according to claim 9, it is characterised in that：It is fired applied to internal combustion engine binary
The fuel oil combustion catalysis of material system by ultra-dispersed photochemical catalyst as needed with the arbitrary multiple of methanol dilution, passes through internal combustion engine first
Alcohol pipeline sprays into air intake duct by nozzle, and the burning of cylinder catalytic diesel oil and methanol binary fuel is entered with air.
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|---|---|---|---|---|
| CN1199240A (en) * | 1997-05-06 | 1998-11-18 | 三星电管株式会社 | Braun tube having antibacterial coating film and manufacturing method therefor |
| CN1384152A (en) * | 2001-04-28 | 2002-12-11 | 中国科学院化学研究所 | Titania nano-paint for photocatalytic decomposition of organic matter and its prepn |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199240A (en) * | 1997-05-06 | 1998-11-18 | 三星电管株式会社 | Braun tube having antibacterial coating film and manufacturing method therefor |
| CN1384152A (en) * | 2001-04-28 | 2002-12-11 | 中国科学院化学研究所 | Titania nano-paint for photocatalytic decomposition of organic matter and its prepn |
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| Title |
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| "Preparation of Ti3+ self-doped TiO2 nanoparticles and their visible";Xiaotong Wang等;《Chinese Journal of Catalysis》;20150320;第36卷(第3期);第389-399页 * |
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