CN108993514A - A kind of black TiO2Foamed nickel catalyst agent and its preparation method and application - Google Patents
A kind of black TiO2Foamed nickel catalyst agent and its preparation method and application Download PDFInfo
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- CN108993514A CN108993514A CN201810826471.6A CN201810826471A CN108993514A CN 108993514 A CN108993514 A CN 108993514A CN 201810826471 A CN201810826471 A CN 201810826471A CN 108993514 A CN108993514 A CN 108993514A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 130
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000006260 foam Substances 0.000 claims abstract description 55
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 51
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 35
- 239000004411 aluminium Substances 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000015556 catabolic process Effects 0.000 claims abstract description 24
- 238000006731 degradation reaction Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- 235000019441 ethanol Nutrition 0.000 claims description 24
- 238000006722 reduction reaction Methods 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000003708 ampul Substances 0.000 description 13
- 239000010453 quartz Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229930040373 Paraformaldehyde Natural products 0.000 description 7
- 229920002866 paraformaldehyde Polymers 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007868 Raney catalyst Substances 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- -1 hard board Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 208000030961 allergic reaction Diseases 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000005303 weighing 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of black TiO2The preparation method of foamed nickel catalyst agent is related to photochemical catalyst preparation technical field.The present invention is using aluminium powder to TiO2It is restored, aluminium powder can capture the oxygen atom in TiO2, so that black TiO be prepared2；By controlling reduction temperature, black TiO can be made2The light absorption of visible region is greatly increased, and corresponding forbidden bandwidth narrows, thus more light induced electrons and hole can be generated, visible light photocatalysis active is improved, to achieve the purpose that degradation of formaldehyde；The nickel foam, which has, contains a large amount of holes inside excellent mechanical performance, uniform open-celled structure and open-celled structure, have good hydrodynamic characteristic and biggish specific surface area, as black TiO2Carrier, can be improved the black TiO2The catalysis reaction efficiency of foamed nickel catalyst agent, while the black TiO can be prevented2The loss of foamed nickel catalyst agent powder.
Description
Technical field
The present invention relates to photochemical catalyst preparation technical fields, and in particular to a kind of black TiO2Foamed nickel catalyst agent and its
Preparation method and application.
Background technique
Indoor air quality problems (IAQ) are since nineteen fifty-three always by domestic and international extensive concern.It is big because using
Finishing material is measured, interior can accumulate the volatile organic matters such as a large amount of formaldehyde, benzene, toluene (VOC (s)), aggravate room air pollution.
The one kind of formaldehyde as VOC (s), is present in the finishing materials such as hard board, paint, coating, wallpaper.It is exposed to for a long time low dense
It spends in formaldehyde (≤0.1ppm) environment, will lead to nauseous, uncomfortable in chest, fash and allergic reaction occur, furthermore formaldehyde is also recognized
To be mankind's potential carcinogen matter.Therefore, studying efficient, stable purifying formaldehyde technology becomes current urgent problem to be solved.
Photocatalytic oxidation utilizes photocatalyst (TiO2) under ultraviolet light, generate electronics, the direct or indirect oxygen in hole
Change formaldehyde pollutants, has the characteristics that low energy consumption, easy to operate, avirulent, and can be at normal temperatures and pressures effectively by organic dirt
Dye object is converted into CO2And H2The small molecules such as O, avoid secondary pollution.However TiO2Powder forbidden bandwidth is big (3.2eV), only absorbs
Wavelength is lower than the ultraviolet light of 387nm, and atmosphere middle-ultraviolet lamp only accounts for 4% or so of sunlight, and account for sunlight 50% or so can
It is light-exposed but to utilize.In recent years, people use the methods of noble metal loading, dye sensitization, doped transition metal ions pair
TiO2Be modified, though however the element of doping can extend visible light-responded range, while also as electronics, in hole-recombination
The heart, to reduce its visible light activity.
Summary of the invention
The purpose of the present invention is to provide a kind of black TiO2Foamed nickel catalyst agent and its preparation method and application uses
The black TiO that method provided by the invention is prepared2The visible light photocatalysis active of foamed nickel catalyst agent is good, PARA FORMALDEHYDE PRILLS(91,95)
Degradation rate is high.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of black TiO2The preparation method of foamed nickel catalyst agent, comprising the following steps:
By TiO2Raw material and aluminium powder carry out reduction reaction under the conditions of 350~420 DEG C, obtain black TiO2；
By the black TiO2It is mixed with ethyl alcohol, obtains black TiO2Alcohol dispersion liquid；
By the black TiO2Alcohol dispersion liquid is coated in the surface of nickel foam, dry, obtains black TiO2Nickel foam is urged
Agent.
Preferably, the reduction reaction the following steps are included:
By TiO2Raw material and aluminium powder are respectively placed in the both ends of reaction vessel, control pressure in the reaction vessel be 8~
Aluminium powder is heated to 750~850 DEG C, by TiO by 12pa2Raw material is heated to 350~420 DEG C, carries out 4~6h of reduction reaction, obtains
Black TiO2。
Preferably, the black TiO2Quality and ethyl alcohol volume ratio be 2g:(95~105) mL.
Preferably, the black TiO2It being carried out with being blended under ultrasound condition for ethyl alcohol, time of the ultrasound is 15~
25min。
Preferably, the size of the nickel foam is 2mm × 20cm × 20cm, the foam nickel surface coated in the size
Black TiO2Black TiO in alcohol dispersion liquid2Quality be 1.8~2.2g.
Preferably, described applied to spraying.
Preferably, the nickel foam is pre-processed before use, it is described pretreatment the following steps are included:
It is washed after nickel foam is impregnated 4~6min in the hydrochloric acid that concentration is 0.04~0.06mol/L, after the washing
Nickel foam impregnate 8~12min in ethanol.
Preferably, the temperature of the drying is 75~85 DEG C, and the time is 22~26h.
The present invention provides the black TiO that preparation method described in above-mentioned technical proposal is prepared2Foamed nickel catalyst agent,
Including nickel foam and the black TiO being supported in the nickel foam2。
The present invention provides black TiO described in above-mentioned technical proposal2Foamed nickel catalyst agent is in formaldehyde degradation by photocatalytic oxidation process
Using.
The present invention provides a kind of black TiO2The preparation method of foamed nickel catalyst agent, by TiO2Raw material and aluminium powder are 350
Reduction reaction is carried out under the conditions of~420 DEG C, obtains black TiO2；By the black TiO2It is mixed with ethyl alcohol, obtains black TiO2-
Alcohol dispersion liquid；By the black TiO2Alcohol dispersion liquid is coated in the surface of nickel foam, dry, obtains black TiO2Foam
Raney nickel.The present invention is using aluminium powder to TiO2It is restored, aluminium powder can capture TiO2In oxygen atom, to be prepared
Black TiO2；By controlling reduction temperature, the black TiO enabled to2All Anatases, to make black TiO2It is right
The light absorption of visible region greatly increases, and corresponding forbidden bandwidth narrows, thus can generate more light induced electrons and hole,
With back cavitation and it is adsorbed on black TiO2The H on surface2O and OH-Reaction generates the hydroxyl radical free radical with Strong oxdiative ability, by first
Aldehyde complete oxidation generates CO2And H2O, to achieve the purpose that degradation of formaldehyde；The nickel foam has excellent mechanicalness
It can, contain a large amount of holes inside uniform open-celled structure and open-celled structure, have good hydrodynamic characteristic and biggish
Specific surface area, as black TiO2Carrier, can be improved the black TiO2The catalysis reaction efficiency of foamed nickel catalyst agent, together
When can prevent the black TiO2The loss of foamed nickel catalyst agent powder.The experimental results showed that black TiO provided by the invention2-
Foamed nickel catalyst agent visible light photocatalysis active is good, and the degradation rate of PARA FORMALDEHYDE PRILLS(91,95) is high, and after light reaction 240min, the degradation rate of formaldehyde reaches
To 78.3%.
In addition, preparation method provided by the invention is highly-safe, easy to operate, it is easy to accomplish large-scale production.
Detailed description of the invention
Fig. 1 is black TiO prepared by embodiment 12The formaldehyde of catalyst prepared by foamed nickel catalyst agent and comparative example 1~2
Degradation efficiency with light application time change curve；
Fig. 2 is black TiO prepared by embodiment 12Black TiO prepared by foamed nickel catalyst agent and comparative example 3~42Foam
The Degradation Formaldehyde efficiency of Raney nickel with light application time change curve.
Specific embodiment
The present invention provides a kind of black TiO2The preparation method of foamed nickel catalyst agent, comprising the following steps:
By TiO2Raw material and aluminium powder carry out reduction reaction under the conditions of 350~420 DEG C, obtain black TiO2；
By the black TiO2It is mixed with ethyl alcohol, obtains black TiO2Alcohol dispersion liquid；
By the black TiO2Alcohol dispersion liquid is coated in the surface of nickel foam, dry, obtains black TiO2Nickel foam is urged
Agent.
The present invention is by TiO2Raw material and aluminium powder carry out reduction reaction, obtain black TiO2.The present invention is for the TiO2Raw material
Source there is no special restriction, using TiO well known to those skilled in the art2Commercial goods or those skilled in the art are known
The TiO that is prepared of method2Product.In the present invention, the TiO2Raw material is preferably P25 type TiO2Commercial goods or
Person is prepared using method comprising the following steps:
Under 40~45 DEG C and stirring condition, 20mL butyl titanate is added dropwise in 45~55mL water, keep the temperature into
1~1.5h of row hydrolysis；Gained hydrolysate is placed in 80~85 DEG C of thermostat water baths and is dried, is put into horse later
280~320 DEG C not are warming up to the rate of 5 DEG C/min in furnace, heat preservation carries out 1.5~2.5h of calcining, certainly by resulting material finally
It is so cooled to room temperature, grinds, obtain the TiO2Raw material.
The present invention does not have the aluminium powder special restriction, is using commercial goods well known to those skilled in the art
It can.In the present invention, the aluminium powder first can oxygen atom in consumption of reactor, when in reactor oxygen atom consumption completely after,
Aluminium powder can further capture TiO2In oxygen atom.The present invention does not have the usage amount of the aluminium powder special restriction, according to
Practical reduction reaction situation can guarantee the aluminium powder excess, specifically, such as weighing 2g P25 type TiO2With 2g aluminium powder point
It is not placed in the both ends of quartz ampoule, the quartz ampoule for being contained with raw material is placed in pipe reaction furnace；Control the pressure in the quartz ampoule
Power is 10pa, aluminium powder is heated to 800 DEG C, by TiO2400 DEG C are heated to, reduction reaction 5h is carried out.
In the present invention, the reduction reaction preferably includes following steps:
By TiO2Raw material and aluminium powder are respectively placed in the both ends of reaction vessel, control pressure in the reaction vessel be 8~
Aluminium powder is heated to 750~850 DEG C, by TiO by 12pa2Raw material is heated to 350~420 DEG C, carries out 4~6h of reduction reaction, obtains
Black TiO2。
The present invention does not have the reaction vessel special restriction, can go on smoothly the reduction reaction.This
Invention preferably uses quartz ampoule as reaction vessel；In an embodiment of the present invention, specifically by the TiO2Raw material and aluminium powder
The both ends of quartz ampoule are respectively placed in, then the quartz ampoule for being contained with raw material is placed in pipe reaction furnace and carries out reduction reaction.
In the present invention, when carrying out the reduction reaction, the temperature of aluminium powder is preferably 800 DEG C；TiO2The temperature of raw material is excellent
It is selected as 400 DEG C.In the present invention, the time of the reduction reaction is preferably 5h.
Obtain black TiO2Afterwards, the present invention is by the black TiO2It is mixed with ethyl alcohol, obtains black TiO2Alcohol dispersion liquid.
In the present invention, the black TiO2Quality and the volume ratio of ethyl alcohol be preferably 2g:(95~105) mL, more preferably 2g:
100mL.In the present invention, the black TiO2Mixing with ethyl alcohol preferably carries out under ultrasound condition, the time of the ultrasound
Preferably 15~25min；The present invention does not have special restriction for the power of the ultrasound, using known to those skilled in the art
Ultrasonic power.
The present invention is using ethyl alcohol as black TiO2Dispersing agent, in subsequent drying process temperature increase it is readily volatilized,
It may advantageously facilitate black TiO2The formation of foamed nickel catalyst agent.
Obtain black TiO2After dispersion liquid, the present invention is by the black TiO2Alcohol dispersion liquid is coated in the table of nickel foam
Face, it is dry, obtain black TiO2Foamed nickel catalyst agent.In the present invention, the nickel foam preferred is located in advance using preceding
Reason, the pretreatment preferably include following steps:
It is washed after nickel foam is impregnated 4~6min in the hydrochloric acid that concentration is 0.04~0.06mol/L, after the washing
Nickel foam impregnate 8~12min in ethanol.
In the present invention, the nickel foam is preferably dimensioned to be 2mm × 20cm × 20cm, the foam coated in the size
The black TiO of nickel surface2Black TiO in alcohol dispersion liquid2Quality be preferably 1.8~2.2g, more preferably 2g.
In the present invention, the coating preferably sprays；Present invention spy no for the concrete operation method of the spraying
Different restriction, using the technical solution of spraying well known to those skilled in the art.
In the present invention, the temperature of the drying is preferably 75~85 DEG C, and more preferably 80 DEG C；Time is preferably 22~
26h, more preferably for 24 hours.
The present invention provides the black TiO that preparation method described in above-mentioned technical proposal is prepared2Foamed nickel catalyst agent,
Including nickel foam and the black TiO being supported in the nickel foam2.In the present invention, the black TiO2All anatases
Phase, to make black TiO2The light absorption of visible region is greatly increased, and corresponding forbidden bandwidth narrows, thus can generated more
More light induced electrons and hole with back cavitation and is adsorbed on black TiO2The H on surface2O and OH-Reaction, generating has Strong oxdiative energy
Formaldehyde complete oxidation is generated CO by the hydroxyl radical free radical of power2And H2O, to achieve the purpose that degradation of formaldehyde；Meanwhile it is described
Nickel foam, which has, contains a large amount of holes inside excellent mechanical performance, uniform open-celled structure and open-celled structure, have good
Hydrodynamic characteristic and biggish specific surface area, as black TiO2Carrier, can be improved the black TiO2Nickel foam
The catalysis reaction efficiency of catalyst, and the black TiO can be prevented2The loss of foamed nickel catalyst agent powder.
The present invention provides black TiO described in above-mentioned technical proposal2Foamed nickel catalyst agent is in formaldehyde degradation by photocatalytic oxidation process
Using.The present invention does not have the application special restriction, using the technical solution of application well known to those skilled in the art
?.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
Weigh 2g P25 type TiO2It is respectively placed in the both ends of quartz ampoule with 2g aluminium powder, the quartz ampoule for being contained with raw material is placed in
In pipe reaction furnace；The pressure controlled in the quartz ampoule is 10pa, aluminium powder is heated to 800 DEG C, by TiO2It is heated to 400
DEG C, reduction reaction 5h is carried out, black TiO is obtained2；
Weigh 2g black TiO2It is mixed with 100mL ethyl alcohol, ultrasonic disperse 20min obtains black TiO2Alcohol dispersion liquid；It will
Nickel foam (2mm × 20cm × 20cm) impregnates 5min in the hydrochloric acid that concentration is 0.05mol/L, and the nickel foam after immersion is steamed
Distilled water washing, impregnates 10min for the nickel foam after washing, by the black TiO in ethanol2Alcohol dispersion liquid is sprayed on pre-
The surface for nickel foam that treated, drying for 24 hours, obtains black TiO under the conditions of 80 DEG C later2Foamed nickel catalyst agent.
Comparative example 1
Nickel foam (2mm × 20cm × 20cm) is impregnated into 5min in the hydrochloric acid that concentration is 0.05mol/L, after immersion
Nickel foam is washed with distilled water, and the nickel foam after washing is impregnated 10min in ethanol, obtains pretreated nickel foam conduct
Blank control catalyst.
Comparative example 2
Weigh 2g P25 type TiO2It is mixed with 100mL ethyl alcohol, ultrasonic disperse 20min obtains TiO2Alcohol dispersion liquid；It will bubble
Foam nickel (2mm × 20cm × 20cm) impregnates 5min in the hydrochloric acid that concentration is 0.05mol/L, and the nickel foam after immersion is distilled
Nickel foam after washing is impregnated 10min by water washing in ethanol, by the TiO2Alcohol dispersion liquid sprays after the pre-treatment
Nickel foam surface, later under the conditions of 80 DEG C it is dry for 24 hours, obtain TiO2Foamed nickel catalyst agent.
Comparative example 3
Black TiO is prepared according to the method for embodiment 12Foamed nickel catalyst agent, the difference is that, it is anti-restore
At once, by TiO2It is heated to 300 DEG C.
Comparative example 4
Black TiO is prepared according to the method for embodiment 12Foamed nickel catalyst agent, the difference is that, it is anti-restore
At once, by TiO2It is heated to 500 DEG C.
Embodiment 2
Quartz ampoule (internal diameter 6mm) fixed-bed flow reactor (under condition of normal pressure) is used, prepared by embodiment 1 black
Color TiO2Foamed nickel catalyst agent is tested for the property (including formaldehyde absorbing process and formaldehyde degradation by photocatalytic oxidation process process), and with it is right
Catalyst prepared by ratio 1~2 is compared, and actual conditions are as follows:
Simulation indoor gas is N2、O2With the mixed gas of formaldehyde, N2And O2Volume ratio be 4:1, total flow 160mL/
Min, mass space velocity (GHSV) are 3.4 × 105m3/(m3·h)；Concentration of formaldehyde is 3.5 × 10-6(volume fraction), passes through thermostatted water
Bath controls the temperature of paraformaldehyde solid to control the concentration of formaldehyde；
After simulation indoor gas is stablized, 2g catalyst is added in the reactor, filling length is 100mm；When absorption is full
With rear, opening 60w fluorescent lamp, wherein fluorescent lamp is located at reactor two sides at a distance of 10cm, exports concentration of formaldehyde every 10min by beauty
The measurement of state interscan4160 type Formaldehyde analyzer.
Fig. 1 is black TiO prepared by embodiment 12The formaldehyde of catalyst prepared by foamed nickel catalyst agent and comparative example 1~2
Degradation efficiency with light application time change curve.As shown in Figure 1, with the increase of light application time, nickel foam pair in comparative example 1
The removal efficiency increase of formaldehyde is unobvious, this illustrates that simple nickel foam PARA FORMALDEHYDE PRILLS(91,95) gas does not have degradation；In comparative example 2
TiO2The degradation rate of foamed nickel catalyst agent PARA FORMALDEHYDE PRILLS(91,95) is gradually increased with the increase of light application time, after light reaction 240min,
The degradation rate of formaldehyde is 48.9%；Black TiO in embodiment 22The degradation rate of foamed nickel catalyst agent PARA FORMALDEHYDE PRILLS(91,95) is with light application time
Increase and dramatically increase, after light reaction 240min, the degradation rate of formaldehyde reaches 78.3%.Illustrate black provided by the invention
TiO2The degradation effect of foamed nickel catalyst agent PARA FORMALDEHYDE PRILLS(91,95) is substantially better than TiO2Foamed nickel catalyst agent.
Embodiment 3
The black TiO according to the method for embodiment 2 prepared by embodiment 12It is prepared by foamed nickel catalyst agent and comparative example 3~4
Black TiO2Foamed nickel catalyst agent is tested for the property, and as a result sees Fig. 2.Fig. 2 is black TiO prepared by embodiment 12Foam
Black TiO prepared by Raney nickel and comparative example 3~42The Degradation Formaldehyde efficiency of foamed nickel catalyst agent with light application time variation
Curve graph.As shown in Figure 2, in the same time degradation efficiency of formaldehyde with TiO when reduction reaction2The raising of heating temperature occurs
The phenomenon that first increases and then decreases: work as TiO2When heating temperature is 300 DEG C, after reacting 240min, Degradation Formaldehyde efficiency is 65.1%；
But work as TiO2When heating temperature increases to 400 DEG C and 500 DEG C, after reacting the same time, Degradation Formaldehyde efficiency is respectively 78.3%
With 52.6%.This is because when heating temperature is lower than 400 DEG C, resulting black TiO2Crystal form crystallinity is smaller, is unfavorable for light
The progress of catalytic reaction process.And when heating temperature is higher than 400 DEG C, more Anatases are converted to Rutile Type, black
TiO2Middle rutile content increases, and photocatalytic activity is caused to decrease；In addition, the excessively high of heating temperature can also make black TiO2
There is sintering phenomenon, catalyst granules is caused to increase, reduces photocatalytic.
Embodiment 4
Under 40 DEG C and stirring condition, 20mL butyl titanate is added dropwise in 50mL water, heat preservation is hydrolyzed anti-
Answer 1h；Gained hydrolysate is placed in 80 DEG C of thermostat water baths and is dried, is put into Muffle furnace later with 5 DEG C/min's
Rate is warming up to 300 DEG C, and heat preservation carries out calcining 2h, and finally by resulting material cooled to room temperature, grinding obtains TiO2；
Weigh 2g TiO2It is respectively placed in the both ends of quartz ampoule with 2g aluminium powder, the quartz ampoule for being contained with raw material is placed in tubular type
In reacting furnace；The pressure for controlling the quartz ampoule is 10pa, aluminium powder is heated to 800 DEG C, by TiO2400 DEG C are heated to, is carried out
Reduction reaction 5h obtains black TiO2；
Weigh 2g black TiO2It is mixed with 100mL ethyl alcohol, ultrasonic disperse 20min obtains black TiO2Alcohol dispersion liquid；It will
Nickel foam (2mm × 20cm × 20cm) impregnates 5min in the hydrochloric acid that concentration is 0.05mol/L, and the nickel foam after immersion is steamed
Distilled water washing, impregnates 10min for the nickel foam after washing, by the black TiO in ethanol2Alcohol dispersion liquid is sprayed on pre-
The surface for nickel foam that treated, drying for 24 hours, obtains black TiO under the conditions of 80 DEG C later2Foamed nickel catalyst agent.
According to the method for embodiment 2 to the black TiO2The performance of foamed nickel catalyst agent is tested, as a result with implementation
Black TiO prepared by example 12The performance of foamed nickel catalyst agent is almost the same.
As seen from the above embodiment, the present invention is using aluminium powder to TiO2It is restored, aluminium powder can capture TiO2In oxygen it is former
Son, so that black TiO be prepared2；By controlling reduction temperature, black TiO can be made2Significantly to the light absorption of visible region
Increase, and corresponding forbidden bandwidth narrows, thus more light induced electrons and hole can be generated, it is living to improve visible light photocatalysis
Property, to achieve the purpose that degradation of formaldehyde；The nickel foam has excellent mechanical performance, uniform open-celled structure and aperture
Inside configuration contains a large amount of holes, has good hydrodynamic characteristic and biggish specific surface area, as black TiO2Load
Body can be improved the black TiO2The catalysis reaction efficiency of foamed nickel catalyst agent, while the black TiO can be prevented2Foam
The loss of Raney nickel powder.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of black TiO2The preparation method of foamed nickel catalyst agent, comprising the following steps:
By TiO2Raw material and aluminium powder carry out reduction reaction under the conditions of 350~420 DEG C, obtain black TiO2；
By the black TiO2It is mixed with ethyl alcohol, obtains black TiO2Alcohol dispersion liquid；
By the black TiO2Alcohol dispersion liquid is coated in the surface of nickel foam, dry, obtains black TiO2Foamed nickel catalyst
Agent.
2. preparation method according to claim 1, which is characterized in that the reduction reaction the following steps are included:
By TiO2Raw material and aluminium powder are respectively placed in the both ends of reaction vessel, and controlling the pressure in the reaction vessel is 8~12pa,
Aluminium powder is heated to 750~850 DEG C, by TiO2Raw material is heated to 350~420 DEG C, carries out 4~6h of reduction reaction, obtains black
TiO2。
3. preparation method according to claim 1 or 2, which is characterized in that the black TiO2Quality and ethyl alcohol volume
Than for 2g:(95~105) mL.
4. preparation method according to claim 3, which is characterized in that the black TiO2Ultrasonic item is blended in ethyl alcohol
It is carried out under part, the time of the ultrasound is 15~25min.
5. preparation method according to claim 1, which is characterized in that the size of the nickel foam be 2mm × 20cm ×
20cm, the black TiO of the foam nickel surface coated in the size2Black TiO in alcohol dispersion liquid2Quality be 1.8~
2.2g。
6. preparation method according to claim 1 or 5, which is characterized in that described applied to spraying.
7. preparation method according to claim 1 or 5, which is characterized in that the nickel foam is pre-processed before use,
It is described pretreatment the following steps are included:
It is washed after nickel foam is impregnated 4~6min in the hydrochloric acid that concentration is 0.04~0.06mol/L, by the bubble after the washing
Foam nickel impregnates 8~12min in ethanol.
8. preparation method according to claim 1, which is characterized in that the temperature of the drying is 75~85 DEG C, and the time is
22~26h.
9. the black TiO that any one of claim 1~8 preparation method is prepared2Foamed nickel catalyst agent, including nickel foam
With the black TiO being supported in the nickel foam2。
10. black TiO described in claim 92Application of the foamed nickel catalyst agent in formaldehyde degradation by photocatalytic oxidation process.
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