CN107694554A - A kind of preparation method of nano-zinc oxide composite photocatalyst - Google Patents
A kind of preparation method of nano-zinc oxide composite photocatalyst Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 36
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229960000892 attapulgite Drugs 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 30
- 239000000725 suspension Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 21
- 238000009835 boiling Methods 0.000 claims abstract description 20
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004246 zinc acetate Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000002270 dispersing agent Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 239000002114 nanocomposite Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 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 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000009715 pressure infiltration Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/345—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of ultraviolet wave energy
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- 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
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- 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
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Abstract
The invention discloses a kind of preparation method of nano-zinc oxide composite photocatalyst, its preparation method is to add zinc acetate in the aqueous dispersion with nano-attapulgite, pressurized expansion reacts to obtain mixing suspension, oxalic acid is then slowly added into, thick half solid-liquid is formed in micro-boiling back flow reaction and vacuum distillation reaction；Finally half solid-liquid is sintered to obtain nano-zinc oxide composite photocatalyst.The present invention has the characteristic of Large ratio surface using the attapulgite after expansion, is compounded to form Large ratio surface photochemical catalyst with nano zine oxide, substantially increases the photocatalysis performance of zinc oxide.
Description
Technical field
The invention belongs to photocatalysis technology field, and in particular to a kind of preparation side of nano-zinc oxide composite photocatalyst
Method.
Background technology
With increasing rapidly for industry, environmental pollution getting worse, especially organic matter in paper-making industry, textile printing and dyeing industry,
Widely using for the industries such as leather manufacture industry generates substantial amounts of industrial wastewater, if not dealing carefully with, can give human health
And ecological environment causes high risks.Thus, seek a kind of processing method of efficient, economic organic pollution and seem abnormal heavy
Will, this also promotes catalysis material to get more and more people's extensive concerning, and turns into study hotspot.Photocatalysis is semi-conducting material in illumination
Under, the Electron absorption energy in valence band is excited to conduction band, while hole is left in valence band, and these light induced electrons and hole participate in
Carry out the process that organic matter is decomposed into carbon dioxide and water by redox reaction.The energy gap of zinc oxide (ZnO) is
3.3eV, it is wide bandgap semiconductor, it is non-toxic because it has better photosensitivity, the features such as broad-band gap and by wide as photochemical catalyst
General research is applied to light degradation organic pollution.But there is following defect in ZnO in light-catalyzed reaction：First, light induced electron
High with the recombination rate in hole, efficient carrier concentration is low, reduces photocatalysis efficiency, limits its practical application；On the other hand, in light
Under the irradiation of source, photoetch phenomenon easily occurs for ZnO surfaces, and the stability and catalytic activity for causing catalyst reduce, it is difficult to reach
Expected catalytic efficiency.
The content of the invention
The purpose of the present invention is in view of the deficiencies of the prior art, there is provided a kind of nano-zinc oxide composite photocatalyst
Preparation method, has the characteristic of Large ratio surface using the attapulgite after expansion, and Large ratio surface is compounded to form with nano zine oxide
Photochemical catalyst, substantially increase the photocatalysis performance of zinc oxide.
In order to solve the above-mentioned technical problem, technical scheme is as follows：
A kind of preparation method of nano-zinc oxide composite photocatalyst, its preparation process are as follows：
Step 1, nano-attapulgite is added into reactor, adds dispersant and distilled water, formed after being dispersed with stirring suspended
Liquid；
Step 2, zinc acetate is added into suspension, carries out Pressurized-heated stirring reaction 2-4h, constant pressure constant temperature stands 3-5h, so
Natural cooling obtains suspended precursor liquid after quick pressure releasing afterwards；
Step 3, oxalic acid is slowly added into suspended precursor liquid, thermostatic ultrasonic reaction 2-5h, then micro-boiling back flow reaction 1-3h,
Obtain expanding suspension；
Step 4, expansion suspension is put into distillation reaction in vacuum distillation apparatus until being formed thick；
Step 5, the thick reactant in step 4 is put into Muffle furnace, sintering reaction 2-4h, it is compound obtains nano zine oxide
Photochemical catalyst.
The proportioning of the preparation process is：
Nano-attapulgite 10-25 parts, dispersant 3-7 parts, distilled water 20-25 parts, zinc acetate 4-8 parts, oxalic acid 10-14 parts.
The dispersant uses any one in polyvinylpyrrolidone, polyacrylic acid or Tissuemat E.
Being dispersed with stirring using mechanical mixing method in the step 1, the mixing speed are 1500-3000r/min, the step
Suddenly nano-attapulgite will be subjected to decentralized processing, it is dispersed into distilled water in attapulgite.
The pressure of Pressurized-heated stirring reaction in the step 2 is 10-15MPa, and temperature is 120-150 DEG C, stirring speed
Spend for 1000-1500r/min, the pressure that the constant pressure constant temperature is stood is 8-10MPa, and temperature is 120 DEG C；The step passes through pressurization
The mode of stirring reaction is heated, water vapor will be distilled, so as to add pressure, while pressure is also formed inside attapulgite；
It is uneven to prevent internal pressure from disperseing, particle agglomeration problem is caused, ensures its internal pressure by the way of constant temperature and pressure
Infiltration, prevents from forming pressure extrusion；The mode of quick pressure releasing discharges pressure, can quickly be arranged in the pressure inside attapulgite
Go out, so as to reach the purpose of expansionization, while can also prevent the flocculation of nano-attapulgite；And as the zinc acetate of dissolved matter,
It is dissolved in water, with the increase of temperature and pressure, continues to dissolve, and be directly dispersed in nano-attapulgite after pressure release
Portion, reach equally distributed purpose.
Preferably, the mode of the quick pressure releasing is that pressure is down into atmospheric pressure in 10-20s.
The temperature of thermostatic ultrasonic reaction in the step 3 is 40-70 DEG C, and ultrasonic frequency is 1.5-3.5kHz, described
The reaction temperature of micro-boiling backflow is 110-120 DEG C, and backflow uses water cooled reflux method；The low frequency ultrasound side that the step passes through room temperature
Formula, ensure that oxalic acid is dispersed into solution, form oxalic acid liquid, and clutch caused by low frequency ultrasound can not possess degraded solutions
Middle organic matter can, while the purpose of ultrasonic disperse can be reached；The mode of micro-boiling back flow reaction can act in hot kinetic energy
Under, promote the conversion between oxalic acid and acetic acid, at a temperature of micro-boiling, acetic acid ion forms volatilization, quickly spills into air, ensures
The formation of zinc oxalate precipitation, and be dispersed on the body of nano-attapulgite.
The pressure of distillation in the step 4 is the 70-80% of atmospheric pressure, and temperature is 110-140 DEG C, passes through vacuum distillation
Mode deionized water is removed, formed it is thick, the stability of zinc oxalate structure can be protected by the way of vacuum distillation.
Sintering temperature in the step 5 is 200-250 DEG C, by the temperature can by the dispersant on surface and oxalic acid and
Oxalate conversion is gaseous state, and stable zinc oxide structures are formed in attapulgite's surface.
The preparation method also includes step 6, and nano-zinc oxide composite photocatalyst is put into UV reactive device, leads to
Enter ozone gas and illumination reaction 10-30min, you can obtain the nano composite photo-catalyst of high activity.
The ozone gas is ozone-nitrogen mixture of the ozone concentration between 50%-80%, the ultraviolet lighting intensity
For 1.5mW/cm2-5.5mW/cm2。
The present invention to add zinc acetate in the aqueous dispersion of nano-attapulgite, pressurized expansion react to obtain mix it is suspended
Liquid, oxalic acid is then slowly added into, thick half solid-liquid is formed in micro-boiling back flow reaction and vacuum distillation reaction；Finally by half solid-liquid
Sintering obtains nano-zinc oxide composite photocatalyst.
Compared with prior art, the invention has the advantages that：
（1）The present invention has the characteristic of Large ratio surface using the attapulgite after expansion, and big ratio is compounded to form with nano zine oxide
Surface photocatalyst, substantially increase the photocatalysis performance of zinc oxide.
（2）The present invention solves the problems, such as that the photocatalysis performance of nano zine oxide is unstable and attapulgite photocatalysis performance
Inapparent problem, it is compound after photocatalysis performance stablize, good weatherability.
（3）Three wastes problem is not present in preparation method provided by the invention, meets environmental requirement, and preparation method is simple and quick,
It is adapted to big industrialized production.
Embodiment
The present invention is described further with reference to embodiment：
Embodiment 1
A kind of preparation method of nano-zinc oxide composite photocatalyst, its preparation process are as follows：
Step 1, nano-attapulgite is added into reactor, adds dispersant and distilled water, formed after being dispersed with stirring suspended
Liquid；
Step 2, zinc acetate is added into suspension, carries out Pressurized-heated stirring reaction 2h, constant pressure constant temperature stands 3h, then soon
Natural cooling obtains suspended precursor liquid after fast pressure release；
Step 3, oxalic acid is slowly added into suspended precursor liquid, thermostatic ultrasonic reaction 2h, then micro-boiling back flow reaction 1h, is obtained
Expand suspension；
Step 4, expansion suspension is put into distillation reaction in vacuum distillation apparatus until being formed thick；
Step 5, the thick reactant in step 4 is put into Muffle furnace, sintering reaction 2h, obtains nano zine oxide complex light
Catalyst.
The proportioning of the preparation process is：
10 parts of nano-attapulgite, 3 parts of dispersant, 20 parts of distilled water, 4 parts of zinc acetate, 10 parts of oxalic acid.
The dispersant uses polyvinylpyrrolidone.
Being dispersed with stirring using mechanical mixing method in the step 1, the mixing speed are 1500r/min.
The pressure of Pressurized-heated stirring reaction in the step 2 is 10MPa, and temperature is 120 DEG C, and mixing speed is
1000r/min, the pressure that the constant pressure constant temperature is stood are 8MPa, and temperature is 120 DEG C, and the mode of the quick pressure releasing is in 10s
It is interior that pressure is down to atmospheric pressure.
The temperature of thermostatic ultrasonic reaction in the step 3 is 40 DEG C, and ultrasonic frequency is 1.5kHz, the micro-boiling backflow
Reaction temperature be 110 DEG C, backflow use water cooled reflux method.
The pressure of distillation in the step 4 is the 70% of atmospheric pressure, and temperature is 110 DEG C.
Sintering temperature in the step 5 is 200 DEG C.
Embodiment 2
A kind of preparation method of nano-zinc oxide composite photocatalyst, its preparation process are as follows：
Step 1, nano-attapulgite is added into reactor, adds dispersant and distilled water, formed after being dispersed with stirring suspended
Liquid；
Step 2, zinc acetate is added into suspension, carries out Pressurized-heated stirring reaction 4h, constant pressure constant temperature stands 5h, then soon
Natural cooling obtains suspended precursor liquid after fast pressure release；
Step 3, oxalic acid is slowly added into suspended precursor liquid, thermostatic ultrasonic reaction 5h, then micro-boiling back flow reaction 3h, is obtained
Expand suspension；
Step 4, expansion suspension is put into distillation reaction in vacuum distillation apparatus until being formed thick；
Step 5, the thick reactant in step 4 is put into Muffle furnace, sintering reaction 4h, obtains nano zine oxide complex light
Catalyst.
The proportioning of the preparation process is：
25 parts of nano-attapulgite, 7 parts of dispersant, 25 parts of distilled water, 8 parts of zinc acetate, 14 parts of oxalic acid.
The dispersant uses any one in polyvinylpyrrolidone, polyacrylic acid or Tissuemat E.
Being dispersed with stirring using mechanical mixing method in the step 1, the mixing speed are 3000r/min.
The pressure of Pressurized-heated stirring reaction in the step 2 is 15MPa, and temperature is 150 DEG C, and mixing speed is
1500r/min, the pressure that the constant pressure constant temperature is stood are 10MPa, and temperature is 120 DEG C, and the mode of the quick pressure releasing is in 20s
It is interior that pressure is down to atmospheric pressure.
The temperature of thermostatic ultrasonic reaction in the step 3 is 70 DEG C, and ultrasonic frequency is 3.5kHz, the micro-boiling backflow
Reaction temperature be 120 DEG C, backflow use water cooled reflux method.
The pressure of distillation in the step 4 is the 80% of atmospheric pressure, and temperature is 140 DEG C.
Sintering temperature in the step 5 is 250 DEG C.
Embodiment 3
A kind of preparation method of nano-zinc oxide composite photocatalyst, its preparation process are as follows：
Step 1, nano-attapulgite is added into reactor, adds dispersant and distilled water, formed after being dispersed with stirring suspended
Liquid；
Step 2, zinc acetate is added into suspension, carries out Pressurized-heated stirring reaction 3h, constant pressure constant temperature stands 4h, then soon
Natural cooling obtains suspended precursor liquid after fast pressure release；
Step 3, oxalic acid is slowly added into suspended precursor liquid, thermostatic ultrasonic reaction 4h, then micro-boiling back flow reaction 2h, is obtained
Expand suspension；
Step 4, expansion suspension is put into distillation reaction in vacuum distillation apparatus until being formed thick；
Step 5, the thick reactant in step 4 is put into Muffle furnace, sintering reaction 3h, obtains nano zine oxide complex light
Catalyst.
The proportioning of the preparation process is：
20 parts of nano-attapulgite, 5 parts of dispersant, 22 parts of distilled water, 6 parts of zinc acetate, 12 parts of oxalic acid.
The dispersant uses Tissuemat E.
Being dispersed with stirring using mechanical mixing method in the step 1, the mixing speed are 2500r/min.
The pressure of Pressurized-heated stirring reaction in the step 2 is 12MPa, and temperature is 130 DEG C, and mixing speed is
1300r/min, the pressure that the constant pressure constant temperature is stood are 9MPa, and temperature is 120 DEG C.
Preferably, the mode of the quick pressure releasing is that pressure is down into atmospheric pressure in 15s.
The temperature of thermostatic ultrasonic reaction in the step 3 is 60 DEG C, and ultrasonic frequency is 2.5kHz, the micro-boiling backflow
Reaction temperature be 120 DEG C, backflow use water cooled reflux method.
The pressure of distillation in the step 4 is the 70% of atmospheric pressure, and temperature is 130 DEG C.
Sintering temperature in the step 5 is 230 DEG C.
Embodiment 4
A kind of preparation method of nano-zinc oxide composite photocatalyst, its preparation process are as follows：
Step 1, nano-attapulgite is added into reactor, adds dispersant and distilled water, formed after being dispersed with stirring suspended
Liquid；
Step 2, zinc acetate is added into suspension, carries out Pressurized-heated stirring reaction 2h, constant pressure constant temperature stands 3h, then soon
Natural cooling obtains suspended precursor liquid after fast pressure release；
Step 3, oxalic acid is slowly added into suspended precursor liquid, thermostatic ultrasonic reaction 2h, then micro-boiling back flow reaction 1h, is obtained
Expand suspension；
Step 4, expansion suspension is put into distillation reaction in vacuum distillation apparatus until being formed thick；
Step 5, the thick reactant in step 4 is put into Muffle furnace, sintering reaction 2h, obtains nano zine oxide complex light
Catalyst,
Step 6, nano-zinc oxide composite photocatalyst is put into UV reactive device, is passed through ozone gas and illumination reaction
10min, you can obtain the nano composite photo-catalyst of high activity.
The proportioning of the preparation process is：
10 parts of nano-attapulgite, 3 parts of dispersant, 20 parts of distilled water, 4 parts of zinc acetate, 10 parts of oxalic acid.
The dispersant uses polyvinylpyrrolidone.
Being dispersed with stirring using mechanical mixing method in the step 1, the mixing speed are 1500r/min.
The pressure of Pressurized-heated stirring reaction in the step 2 is 10MPa, and temperature is 120 DEG C, and mixing speed is
1000r/min, the pressure that the constant pressure constant temperature is stood are 8MPa, and temperature is 120 DEG C, and the mode of the quick pressure releasing is in 10s
It is interior that pressure is down to atmospheric pressure.
The temperature of thermostatic ultrasonic reaction in the step 3 is 40 DEG C, and ultrasonic frequency is 1.5kHz, the micro-boiling backflow
Reaction temperature be 110 DEG C, backflow use water cooled reflux method.
The pressure of distillation in the step 4 is the 70% of atmospheric pressure, and temperature is 110 DEG C.
Sintering temperature in the step 5 is 200 DEG C.
The ozone gas is ozone-nitrogen mixture of the ozone concentration between 50%, and the ultraviolet lighting intensity is
1.5mW/cm2。
Embodiment 5
A kind of preparation method of nano-zinc oxide composite photocatalyst, its preparation process are as follows：
Step 1, nano-attapulgite is added into reactor, adds dispersant and distilled water, formed after being dispersed with stirring suspended
Liquid；
Step 2, zinc acetate is added into suspension, carries out Pressurized-heated stirring reaction 4h, constant pressure constant temperature stands 5h, then soon
Natural cooling obtains suspended precursor liquid after fast pressure release；
Step 3, oxalic acid is slowly added into suspended precursor liquid, thermostatic ultrasonic reaction 5h, then micro-boiling back flow reaction 3h, is obtained
Expand suspension；
Step 4, expansion suspension is put into distillation reaction in vacuum distillation apparatus until being formed thick；
Step 5, the thick reactant in step 4 is put into Muffle furnace, sintering reaction 4h, obtains nano zine oxide complex light
Catalyst,
Step 6, nano-zinc oxide composite photocatalyst is put into UV reactive device, is passed through ozone gas and illumination reaction
30min, you can obtain the nano composite photo-catalyst of high activity.
The proportioning of the preparation process is：
25 parts of nano-attapulgite, 7 parts of dispersant, 25 parts of distilled water, 8 parts of zinc acetate, 14 parts of oxalic acid.
The dispersant uses polyacrylic acid.
Being dispersed with stirring using mechanical mixing method in the step 1, the mixing speed are 3000r/min.
The pressure of Pressurized-heated stirring reaction in the step 2 is 15MPa, and temperature is 150 DEG C, and mixing speed is
1500r/min, the pressure that the constant pressure constant temperature is stood are 10MPa, and temperature is 120 DEG C, and the mode of the quick pressure releasing is in 20s
It is interior that pressure is down to atmospheric pressure.
The temperature of thermostatic ultrasonic reaction in the step 3 is 70 DEG C, and ultrasonic frequency is 3.5kHz, the micro-boiling backflow
Reaction temperature be 120 DEG C, backflow use water cooled reflux method.
The pressure of distillation in the step 4 is the 80% of atmospheric pressure, and temperature is 140 DEG C.
Sintering temperature in the step 5 is 250 DEG C.
Ozone gas in the step 6 is ozone-nitrogen mixture of the ozone concentration between 80%, the ultraviolet light
It is 5.5mW/cm according to intensity2。
Embodiment 6
A kind of preparation method of nano-zinc oxide composite photocatalyst, its preparation process are as follows：
Step 1, nano-attapulgite is added into reactor, adds dispersant and distilled water, formed after being dispersed with stirring suspended
Liquid；
Step 2, zinc acetate is added into suspension, carries out Pressurized-heated stirring reaction 3h, constant pressure constant temperature stands 4h, then soon
Natural cooling obtains suspended precursor liquid after fast pressure release；
Step 3, oxalic acid is slowly added into suspended precursor liquid, thermostatic ultrasonic reaction 4h, then micro-boiling back flow reaction 2h, is obtained
Expand suspension；
Step 4, expansion suspension is put into distillation reaction in vacuum distillation apparatus until being formed thick；
Step 5, the thick reactant in step 4 is put into Muffle furnace, sintering reaction 3h, obtains nano zine oxide complex light
Catalyst,
Step 6, nano-zinc oxide composite photocatalyst is put into UV reactive device, is passed through ozone gas and illumination reaction
20min, you can obtain the nano composite photo-catalyst of high activity.
The proportioning of the preparation process is：
15 parts of nano-attapulgite, 6 parts of dispersant, 23 parts of distilled water, 6 parts of zinc acetate, 12 parts of oxalic acid.
The dispersant uses Tissuemat E.
Being dispersed with stirring using mechanical mixing method in the step 1, the mixing speed are 2500r/min.
The pressure of Pressurized-heated stirring reaction in the step 2 is 13MPa, and temperature is 130 DEG C, and mixing speed is
1200r/min, the pressure that the constant pressure constant temperature is stood are 9MPa, and temperature is 120 DEG C.
Preferably, the mode of the quick pressure releasing is that pressure is down into atmospheric pressure in 10s.
The temperature of thermostatic ultrasonic reaction in the step 3 is 60 DEG C, and ultrasonic frequency is 2.5kHz, the micro-boiling backflow
Reaction temperature be 120 DEG C, backflow use water cooled reflux method.
The pressure of distillation in the step 4 is the 75% of atmospheric pressure, and temperature is 120 DEG C.
Sintering temperature in the step 5 is 240 DEG C.
Ozone gas in the step 6 is ozone-nitrogen mixture of the ozone concentration between 70%, the ultraviolet light
It is 3.5mW/cm according to intensity2。
Embodiment 7
The composite photo-catalyst prepared using embodiment is as embodiment, using P25 as comparative example, using 365nm uviol lamp as illumination
Lamp source, photocatalytic degradation methylene blue experiment is carried out, methylene blue concentration is 15mg/L, its degradation rate such as table 1；Repeating 50 times
During stability after experiment compares, the stability that the stability of embodiment 6 is 99.3%, P25 is 87.1%.
Table 1
| Time | The degradation rate of embodiment 6 | P25 degradation rates |
| 30min | 51.2% | 38.1% |
| 60min | 87.2% | 62.3% |
| 90min | 93.1% | 78.2% |
| 120min | 98.9% | 83.0% |
Embodiment 8
The composite photo-catalyst prepared using embodiment 6 is as embodiment, using P25 as comparative example, with 12 points of lamp of high noon
For illumination lamp source, photocatalytic degradation rhodamine B experiment is carried out, rhodamine B concentration is 5mg/L, its degradation rate such as table 2.
Table 2
| Time | The degradation rate of embodiment 6 | P25 degradation rates |
| 30min | 37.2% | 17.1% |
| 60min | 75.2% | 28.3% |
| 90min | 90.2% | 32.2% |
| 120min | 96.3% | 35.0% |
Several embodiments of the present invention are the foregoing is only, are not intended to limit the present invention, it is all using equivalent substitution or equivalent transformation
The technical scheme that mode is obtained, all falls within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of nano-zinc oxide composite photocatalyst, its preparation process are as follows：
Step 1, nano-attapulgite is added into reactor, adds dispersant and distilled water, formed after being dispersed with stirring suspended
Liquid；
Step 2, zinc acetate is added into suspension, carries out Pressurized-heated stirring reaction 2-4h, constant pressure constant temperature stands 3-5h, so
Natural cooling obtains suspended precursor liquid after quick pressure releasing afterwards；
Step 3, oxalic acid is slowly added into suspended precursor liquid, thermostatic ultrasonic reaction 2-5h, then micro-boiling back flow reaction 1-3h,
Obtain expanding suspension；
Step 4, expansion suspension is put into distillation reaction in vacuum distillation apparatus until being formed thick；
Step 5, the thick reactant in step 4 is put into Muffle furnace, sintering reaction 2-4h, it is compound obtains nano zine oxide
Photochemical catalyst.
2. the preparation method of a kind of nano-zinc oxide composite photocatalyst according to claim 1, it is characterised in that described
The proportioning of preparation process is：Nano-attapulgite 10-25 parts, dispersant 3-7 parts, distilled water 20-25 parts, zinc acetate 4-8 parts, grass
Sour 10-14 parts, the dispersant use any one in polyvinylpyrrolidone, polyacrylic acid or Tissuemat E.
3. the preparation method of a kind of nano-zinc oxide composite photocatalyst according to claim 1, it is characterised in that described
Being dispersed with stirring using mechanical mixing method in step 1, the mixing speed are 1500-3000r/min.
4. the preparation method of a kind of nano-zinc oxide composite photocatalyst according to claim 1, it is characterised in that described
The pressure of Pressurized-heated stirring reaction in step 2 is 10-15MPa, and temperature is 120-150 DEG C, mixing speed 1000-
1500r/min, the pressure that the constant pressure constant temperature is stood be 8-10MPa, and temperature is 120 DEG C, the mode of the quick pressure releasing for
Pressure is down to atmospheric pressure in 10-20s.
5. the preparation method of a kind of nano-zinc oxide composite photocatalyst according to claim 1, it is characterised in that described
The temperature of thermostatic ultrasonic reaction in step 3 is 40-70 DEG C, and ultrasonic frequency is 1.5-3.5kHz, and the micro-boiling flows back anti-
It is 110-120 DEG C to answer temperature, and backflow uses water cooled reflux method.
6. the preparation method of a kind of nano-zinc oxide composite photocatalyst according to claim 1, it is characterised in that described
The pressure of distillation in step 4 is the 70-80% of atmospheric pressure, and temperature is 110-140 DEG C.
7. the preparation method of a kind of nano-zinc oxide composite photocatalyst according to claim 1, it is characterised in that described
Sintering temperature in step 5 is 200-250 DEG C.
8. the preparation method of a kind of nano-zinc oxide composite photocatalyst according to claim 1, it is characterised in that described
Preparation method also includes step 6, and nano-zinc oxide composite photocatalyst is put into UV reactive device, is passed through ozone gas simultaneously
Illumination reaction 10-30min, you can obtain the nano composite photo-catalyst of high activity.
9. the preparation method of a kind of nano-zinc oxide composite photocatalyst according to claim 9, it is characterised in that described
Ozone gas is ozone-nitrogen mixture of the ozone concentration between 50%-80%, and the ultraviolet lighting intensity is 1.5mW/cm2-
5.5mW/cm2。
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|---|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103191696A (en) * | 2013-04-10 | 2013-07-10 | 合肥工业大学 | Method for improving adsorption property of attapulgite by using hydrothermal process |
| CN106006708A (en) * | 2016-05-23 | 2016-10-12 | 渤海大学 | Preparation method of lengthened octahedral hierarchical structure material of ZnO |
-
2017
- 2017-09-27 CN CN201710886915.0A patent/CN107694554A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103191696A (en) * | 2013-04-10 | 2013-07-10 | 合肥工业大学 | Method for improving adsorption property of attapulgite by using hydrothermal process |
| CN106006708A (en) * | 2016-05-23 | 2016-10-12 | 渤海大学 | Preparation method of lengthened octahedral hierarchical structure material of ZnO |
Non-Patent Citations (3)
| Title |
|---|
| 吕百龄 主编: "《实用工业助剂全书》", 31 August 2001, 化学工业出版社 * |
| 彭勇刚 等: "氧化锌/凹凸棒石复合光催化材料的制备及其光催化性能研究", 《印染助剂》 * |
| 白敏冬 等著: "《海洋外来有害生物和病原体防治新技术》", 31 August 2010, 海洋出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116478488A (en) * | 2023-06-25 | 2023-07-25 | 广州澳通电线电缆有限公司 | Anti-aging photovoltaic cable and preparation method thereof |
| CN116478488B (en) * | 2023-06-25 | 2023-08-25 | 广州澳通电线电缆有限公司 | Anti-aging photovoltaic cable and preparation method thereof |
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