CN106040232B - For wastewater treatment catalyst, prepare the method for catalyst and including the sewage treatment equipment of catalyst - Google Patents
For wastewater treatment catalyst, prepare the method for catalyst and including the sewage treatment equipment of catalyst Download PDFInfo
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- CN106040232B CN106040232B CN201610124275.5A CN201610124275A CN106040232B CN 106040232 B CN106040232 B CN 106040232B CN 201610124275 A CN201610124275 A CN 201610124275A CN 106040232 B CN106040232 B CN 106040232B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 29
- 239000010865 sewage Substances 0.000 title claims abstract description 15
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 64
- 239000010935 stainless steel Substances 0.000 claims abstract description 64
- 239000000758 substrate Substances 0.000 claims abstract description 62
- 239000011148 porous material Substances 0.000 claims abstract description 51
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 27
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002105 nanoparticle Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 238000007540 photo-reduction reaction Methods 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910010062 TiCl3 Inorganic materials 0.000 claims description 7
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229940074391 gallic acid Drugs 0.000 claims description 3
- 235000004515 gallic acid Nutrition 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 235000005979 Citrus limon Nutrition 0.000 claims 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 244000131522 Citrus pyriformis Species 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 11
- 230000006641 stabilisation Effects 0.000 abstract description 5
- 239000013049 sediment Substances 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000002085 persistent effect Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000001973 Ficus microcarpa Species 0.000 description 1
- 241001593750 Turcica Species 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229910000960 colored gold Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/40—
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
Disclose the catalyst for wastewater treatment.Catalyst includes the stainless steel nanometer substrate that nano-pore is formed on its surface and the metal nanoparticle being loaded into nano-pore.The catalyst has excellent corrosion resistance and wearability and very stable to pH and temperature change.Particularly, when being applied to the wastewater treatment based on advanced oxidation method, which increase to wastewater treatment rate twice or more.Therefore, significantly reduce cost for wastewater treatment using the catalyst.The catalyst can be reused repeatedly without carrying out special stabilisation after being used in use.Different from other existing catalyst, which does not leave sediment, eliminates the demand to subsequent processing.The catalyst is easy to prepare.In addition, the catalyst can simple application in existing equipment.Therefore, the catalyst can be directly used in the case where needing to handle waste water.Also disclose the method for preparing catalyst and the sewage treatment equipment including catalyst.
Description
Technical field
The present invention relates to for wastewater treatment catalyst, be used to prepare the method for the catalyst and including the catalyst
Sewage treatment equipment.
Background technique
In recent years, the environment regulations for increased wastewater effluent have become more stringent.Therefore, occur to
In the demand of the technology economically and efficiently of wastewater treatment.Existing biological effluent treatment technology is in terms of meeting stringent regulation
Deficiency, and it is in terms of the waste water for handling ever-increasing amount and unsatisfactory.It is difficult to go completely by biologic treating technique
Except persistent organism and micropollutants.Such persistent organism and micropollutants flow into water system and are considered as waters
The main reason for ecosystem is unbalance.In this case, exist and meet to compared with the prior art based on biological treatment
For the strict regulations of effluent, in terms of the waste water for handling ever-increasing amount effectively and can be used to completely remove it is lasting
The demand of the advanced technology of property organic matter and micropollutants.
At this point, Korean government is planned to be studied to propose about total organic carbon in effluent (TOC)
Standard, and expected proposition effluent quality standard quickly.Therefore, more concerns have been concentrated on from effluent removal persistence and have
Machine object and micropollutants.However, this polluter completely removes so that needing to introduce modern advanced oxidation equipment.Some Korea Spro
Mechanism, state and company are managing the waste water treatment plant based on advanced oxidation method, but because of the intrinsic problem of method, they
Difficulty with operation waste water treatment plant.
Many advanced oxidation methods are applied to wastewater treatment at present.For example, Fenton method is in the acid range of pH 3 to 5
The aspect of oxidized waste water is most effective.However, the disadvantages of this method is, the pH of waste water should be adjusted to the acidity for reaction
Range, and the pH of processed water should be increased after the completion of oxidation to discharge.Fenton method also needs subsequent processing step
To remove a large amount of sediments generated during reaction.As another example, it is known that be based on ultraviolet light/hydrogen peroxide (UV/
H2O2) advanced oxidation method.According to this method, the decomposition of ultraviolet acceleration by light hydrogen peroxide is to improve the OH of oxidation stain object certainly
By the synthesis speed of base.Based on UV/H2O2Method be effective in terms of removing pollutant, but have a problem in that for
Realization high efficiency, needs a large amount of hydrogen peroxide.Another problem is: the use of a large amount of hydrogen peroxide causes economical negative
Load, and lead to the increase of the COD (COD) of final effluent, make it difficult to meet effluent quality standard.
On the contrary, being based on ozone (O3) method to have the advantage that as long as electric power is available as needed
Ozone is prepared, and by directly reacting with ozone in the short time and can pollutant effectively be sterilized and be aoxidized.Due to
These advantages, the method based on ozone have attracted many concerns.Another advantage of method based on ozone is can to make
Lyophobic dust such as persistent organism hydrophiling, and can be by easily biodegradable.Therefore, based on the method for ozone
It is environmental-friendly, therefore is suitble in the processed and applied for requiring high water quality as the technology for being used for Wastewater Pretreatment.However, because
It is the method based on ozone dependent on being contacted with pollutant, so they are only effective in terms of removing specific target substance.This
Lead to the selectivity of difference, and limiting can be by directly reacting the amount of the organic substance of removal.Method based on ozone its
He the disadvantage is that: the presence of bromine may cause the generation of carcinogen, and need to promote using other energy sources for subtracting
The indirect reaction of few organic substance.
Stainless steel has excellent corrosion resistance and wearability, and is not susceptible to pH and temperature change with other metal phase ratios
The influence of change.That is, stainless steel has extraordinary physical and chemical stability.It is different from other materials based on iron, stainless steel
Environmental-friendly catalysis material, this is because it be it is rustless, do not leave sediment.Because of this advantage, stainless steel energy
It is enough directly to be applied in various water treatment fields.In this regard, Korean Patent No. 0403275 discloses one kind and is administered to stainless steel
The photocatalytic coating composition of substrate, it includes organosilan, metal oxide, storage stabilizing agents etc..In addition, Korean Patent
It discloses No. 2007-0113551 and discloses a kind of equipment complex for by advanced oxidation method processing persistence waste liquid.It should
Equipment complex is based on ozone electrolysis and semiconductor catalysis, and the stainless steel anode of titanium and iridium is coated with including surface.
However, the prior art only disclose to the relevant technology of the part coating of metallic particles on stainless steel material, and
And do not disclose for by effectively constructing stainless steel carrier structure and the metallic particles that is loaded on carrier make to pollute
The maximized technology of the degradation of object.
Summary of the invention
The present invention is completed to solve the problems, such as Conventional waste water processing technique, and the present invention is intended to provide one kind is used for
The catalyst of wastewater treatment, the durability having had promote wastewater treatment, can repeatedly reuse without with after use
Special stabilisation or subsequent processing, easily prepared and can simply directly be applied to existing equipment are carried out, the present invention is also
The method for being used to prepare the catalyst and the sewage treatment equipment including the catalyst are provided.
One aspect of the present invention provides a kind of catalyst for wastewater treatment, and the catalyst includes being formed on surface
There are the stainless steel nanometer substrate of nano-pore and the metal nanoparticle being loaded into nano-pore.
An embodiment according to the present invention, metal nanoparticle, which can be at least one selected from silver and titanium, coloured gold
The nano particle of category.
Another embodiment according to the present invention, the average diameter and 20nm that nano-pore can have 70nm to 90nm are extremely
The mean depth of 100nm.
Another embodiment according to the present invention, (1 μm of the per unit surface area of stainless steel substrate2) nanometer hole number can
To be 160 to 200.
Another embodiment according to the present invention, metal nanoparticle can be the ball that average diameter is 15nm to 50nm
Body.
Another embodiment according to the present invention, the ratio of the average diameter of the average diameter and nano particle of nano-pore can be with
It is 2:1 to 5:1.
Another embodiment according to the present invention, the average diameter of nano-pore and the ratio of depth can be 3:1 to 1:1.
Another aspect of the present invention provides a kind of method for preparing the catalyst for wastewater treatment comprising passes through anode
Oxidation forms nano-pore on the surface of stainless steel substrate and is filled metal nanoparticle by electronation or photoreduction
It is downloaded in nano-pore.
An embodiment according to the present invention, can be in 5 DEG C to 9 DEG C of temperature under stiring with the voltage of 20V to 60V
Anodic oxidation is carried out with the electric current of 0.1A to 6A.
Another embodiment according to the present invention can carry out electronation by following steps: stainless steel substrate is soaked
Reducing agent is added in the aqueous solution containing metal salt and acid, and to aqueous solution.
Another embodiment according to the present invention, metal salt can be selected from AgNO3、TiCl3And TiCl4Water solubility have
Non-ferrous metal salt, acid can be the acid at least one hydroxyl group or carboxylic group and can be selected from sodium citrate, galla turcica
Acid and its mixture, reducing agent can be the highly basic selected from sodium hydroxide, sodium borohydride and its mixture.
Another embodiment according to the present invention can add metal salt with the concentration of 0.001M to 0.05M.
Stainless steel substrate can be immersed 1 hour or shorter time by another embodiment according to the present invention.
Another embodiment according to the present invention can carry out photoreduction by following steps: in the dark, true
Stainless steel substrate is immersed in the aqueous solution containing metal salt and acid in the air, cleans stainless steel substrate with distilled water and nitrogen, and
The stainless steel substrate cleaned is irradiated with UV-C light.
Another embodiment according to the present invention, metal salt can be selected from AgNO3、TiCl3And TiCl4Water solubility have
Non-ferrous metal salt.
Another embodiment according to the present invention can add metal salt with the concentration of 0.001M to 0.05M.
Another embodiment according to the present invention can immerse stainless steel substrate 6 hours to 12 hours, and UV-C light
It can irradiate 0.5 hour to 2 hours.
Another aspect of the present invention provides a kind of sewage treatment equipment based on advanced oxidation method comprising ozone reaction
Device and UV generator, wherein ozone reactor includes the catalyst for wastewater treatment.
Catalyst of the invention has excellent corrosion resistance and wearability, and very stable to pH and temperature change.It is special
Not, when being applied to the wastewater treatment based on advanced oxidation method, catalyst of the invention makes to give up compared with existing catalyst
Rates of water treatment increases to twice or more.Therefore, the use of catalyst according to the invention drops cost for wastewater treatment significantly
It is low.Catalyst of the invention can be reused repeatedly without carrying out special stabilisation after being used in use.It existing is urged with other
Agent is different, and catalyst of the invention does not leave sediment, eliminates the demand to subsequent processing.Catalyst of the invention is easy to
Preparation.In addition, catalyst of the invention can be simply applied to existing equipment.Therefore, in the case where needing to handle waste water
Catalyst of the invention can directly be used.
Detailed description of the invention
In conjunction with attached drawing, according to the description of following embodiments, these and or other aspects of the invention and advantage can become
It is obvious and easier to understand, in the attached drawing:
Fig. 1 is to show catalyst of the invention to be applied to advanced oxidation method (AOP) Shi Fasheng based on UV/ozone
Photochemically reactive mechanism schematic diagram；
Fig. 2 a to 2d is shown respectively the nano-pore stainless steel substrate prepared in embodiment 1, uses hydroboration in embodiment 2.1
Sodium by the catalyst of chemical reaction preparation, in embodiment 2.1 by using the catalyst of the chemical reaction preparation of sodium hydroxide,
With the field emission scanning electron microscope (FE- of the surface topography of the catalyst prepared in embodiment 2.2 by photochemical reaction
SEM) figure；
Fig. 3 a and 3b are the energy for showing the catalyst of catalyst and supported titanium of the load silver prepared in embodiment 2 respectively
The figure of the result of Dispersible X-Ray spectrum；
Fig. 4 schematically shows the sewage treatment equipment of the invention based on AOP；
Fig. 5 is to show the stainless steel substrate prepared in embodiment 1 and the catalyst for preparing in embodiment 2 is applied to and is based on
UV/O3AOP when COD removal efficiency variation figure；
Fig. 6 is to show the stainless steel substrate prepared in embodiment 1 and the catalyst for preparing in embodiment 2 is applied to and is based on
UV/O3AOP when TOC removal efficiency variation figure；With
Fig. 7 is shown based on UV/O3AOP in reuse during catalyst of the invention performance change figure.
Specific embodiment
It should be understood that term and word used in description and claims should not be construed as with common meaning and dictionary
Meaning, but people can suitably define the concept of term and word to describe his/her with the best way according to the present invention
The principle of invention is understood as having concept corresponding with technical spirit of the invention.Therefore, real described in specification
It applies scheme and structure shown in the accompanying drawings is only provided with illustrative purpose, be not intended to represent all technical spirits of the invention.
It will be understood, therefore, that when submitting the application various equivalent replacements and adjustment can be carried out to these embodiments and structure.
Now with reference to attached drawing and following embodiment part, the present invention will be described in more detail.
The catalyst that the present invention relates to a kind of for wastewater treatment is used to prepare the method for the catalyst and including the catalysis
The sewage treatment equipment of agent.Specifically, it sets when being applied to the wastewater treatment based on AOP including ozone reactor and UV generator
When standby, make to catalyst stabilization of the invention the maximization of reacting with UV, and the formation of hydroxyl radical free radical can be promoted, this is advantageous
In significantly improving for contaminant removal efficiency.
Particularly, catalyst of the invention includes being formed with the stainless steel substrate of nano-pore on surface and being loaded into nano-pore
In metal nanoparticle.
Fig. 1 is to show catalyst of the invention to be applied to advanced oxidation method (AOP) Shi Fasheng based on UV/ozone
Photochemically reactive mechanism schematic diagram.Referring to Fig.1, it is based on UV/O3AOP usually carry out in the following manner: will be by ultraviolet
Lamp 120 generate ultraviolet light 121 be irradiated on catalyst 110, conduction band is excited electronic to by luminous energy, the electronics excited with
Oxygen present in water is reacted to form the superoxide radical for degradation of contaminant.When electronics is excited to conduction band, they
Hole is left in valence band.Hole and water molecule reaction formed also with the OH free radical of pollutant reaction.
The conduction band of the electronics for the energy excitation that metal nanoparticle 130 generates after being used to make to be mapped to by illumination on catalyst
(being represented by dotted lines in figure) reduces.According to the mechanism, i.e., electronics can be also excited using the energy of relatively small amount, use equal amount
Energy can excite further amounts of electronics, this leads to increased superoxide radical and OH free radical synthesis speed.Therefore, according to
The use of catalyst of the invention is effective in terms of promoting contaminant degradation.
It is those of common that metal nanoparticle can be in this field catalyst of the preparation for wastewater treatment.For example, golden
Metal nano-particle can be the nano particle of at least one non-ferrous metal selected from silver and titanium.
In the present invention, the spatial form and arrangement and metal nanoparticle of the nano-pore formed on stainless steel substrate
Shapes and sizes on the degradation property of catalyst have significantly affect.Nano-pore can have the average diameter of 70nm to 90nm
With the mean depth of 20nm to 100nm.(1 μm of the per unit surface area of stainless steel substrate2) nanometer hole number can be 160 to
200 holes.Metal nanoparticle can be the sphere that average diameter is 15nm to 50nm.
If the average diameter of nano-pore is less than above-mentioned lower limit, metal nanoparticle can not be received by being effectively loaded into
In metre hole.Meanwhile if the average diameter of nano-pore is greater than the above-mentioned upper limit, stainless steel substrate may have asking for durability
Topic.If the depth of nano-pore is less than above-mentioned lower limit, metal nanoparticle can not be effectively loaded into nano-pore.Together
When, if the problem of depth of nano-pore is greater than the above-mentioned upper limit, and stainless steel substrate may have durability.
Nano-pore can with 160 to 200 holes of stainless steel substrate/μm2Density formed.The density of nano-pore too it is low then
The reaction efficiency (i.e. contaminant degradation performance) of catalyst is undesirably set to be deteriorated.Meanwhile the density of nano-pore too high then not phase
Ground is hoped to lead to the reduction of average diameter of nano-pore.
The nano particle being loaded into nano-pore can be the sphere that average diameter is 15nm to 50nm.If nano particle
Diameter be less than 15nm, then they may be insufficient to the cohesive force of stainless steel substrate.Meanwhile if nano particle diameter
More than 50nm, then their loadings into nano-pore may be inefficient.
Preferably, the average diameter and depth of nano-pore and the average diameter of nano particle meet scheduled relationship.When
The ratio of the average diameter of the average diameter and nano particle of nano-pore is the average diameter and depth of 2:1 to 5:1 and nano-pore
When than for 3:1 to 1:1, suitable durability and adhesion can be effectively realized.
Catalyst of the invention can be prepared by the following method.
Specifically, method includes nano-pore being formed on the surface of stainless steel substrate by anodic oxidation, and pass through chemistry
Metal nanoparticle is loaded into nano-pore by reduction or photoreduction.
Term " anodic oxidation " generally refers to following reaction: wherein substrate such as metal base immersed in electrolyte solution,
Anode is connected to substrate, electric current is made to flow into substrate, generates oxygen in anode as a result, to form porous coating in substrate surface.?
In method of the invention, firstly, forming nano-pore on stainless steel substrate by anodic oxidation.The nanometer formed on substrate surface
The 3 dimension structures in hole can change according to specific anodic oxidation condition.In order to realize the detailed construction size of above-mentioned nano-pore,
Anodic oxidation can be carried out with the electric current of the voltage of 20V to 60V and 0.1A to 6A under stiring in 5 DEG C to 9 DEG C of temperature.
Later, metal nanoparticle is loaded into the nano-pore formed on stainless steel substrate by anodic oxidation, it is complete
At the preparation of catalyst.
In the method for the invention, the method for loading metal nanoparticle is segmented into two kinds of approach in a broad sense.
A kind of approach is based on electronation.Electronation can be by immersing stainless steel substrate in the aqueous solution containing metal salt and acid
It is carried out with reducing agent is added to aqueous solution.
Metal salt is the salt compound of the metal wait be supported on stainless steel substrate.Metal salt is water-soluble non-ferrous metal
Salt.The example of suitable metal salt includes but is not limited to AgNO3、TiCl3And TiCl4.Acid can be at least one hydroxyl base
The acid of group or carboxylic group simultaneously can be selected from sodium citrate, gallic acid and its mixture.Reducing agent can be selected from hydroxide
The highly basic of sodium, sodium borohydride and its mixture.
Metal salt can be added with the concentration of 0.001M to 0.05M.If the concentration of metal salt is lower than 0.001M, cannot
Ensure the uniformity of desired metal nanoparticle.Meanwhile if the concentration of metal salt is more than 0.05M, nano-pore structure can
It can be blocked.
Another way is based on photoreduction.Photoreduction can be carried out by following steps: in the dark, true
Stainless steel substrate is immersed in the aqueous solution containing metal salt and acid in the air, cleans stainless steel substrate with distilled water and nitrogen, and
The stainless steel substrate cleaned is irradiated with UV-C light.
The concentration of the type and metal salt of metal salt and acid is identical as those of restriction in electronation.It can will be stainless
Steel substrate immerses in metal salt solution 6 hours to 12 hours.It, cannot be by the gold of sufficient amount if immersing the time to be shorter than 6 hours
Metal nano-particle is loaded into the nano-pore formed on substrate surface.Meanwhile if immersing the time is more than 12 hours, spend very
The long time carrys out Method Of Accomplishment, this is economically undesirable.Adjustable UV-C light irradiation time is 0.05 hour to 2 small
When.Shorter than 0.5 hour irradiation time leads to the low rate of reduction of metal ion.Meanwhile the irradiation time for being longer than 2 hours is passing through
It is undesirable in Ji.
When being applied to various sewage treatment equipments, catalyst of the invention can show improved wastewater treatment
Energy.Specifically, such as visible from the experimental result in following embodiment part, occur when applied to including ozone reactor and UV
Catalyst shows high COD removal efficiency and TOC removal efficiency when the sewage treatment equipment based on AOP of device, and can be with
It repeatedly reuses even without carrying out special stabilisation after use.
Therefore, the present invention also provides the sewage treatment equipments for being based on advanced oxidation method (AOP) comprising ozone reactor
With UV generator, wherein ozone reactor includes the catalyst for wastewater treatment.
Fig. 4 schematically shows the sewage treatment equipment of the invention based on AOP.Referring to Fig. 4, equipment packet of the invention
Include: ozone generator 420 is suitable for generating ozone by the air supplied from air tank 410；Ozone reactor 430, ozone into
Enter wherein and with waste water reaction to be processed；With UV generator 440 comprising the ultraviolet lamp 441 around ozone reactor.Such as
Shown in the figure, catalyst 450 is arranged in ozone reactor 430 and reacts with ozone 431 etc. to realize that wastewater treatment is set
The standby waste water treatment efficiency significantly improved.
The present invention can be described in more detail referring to following embodiment.However, these embodiments are to help and understand this hair
It is bright and offer, it is not intended to limit the scope of the present invention.
Embodiment
Embodiment 1: the preparation of nano-pore stainless steel substrate
Stainless steel (304L) film is set to carry out anodic oxidation to prepare the stainless steel substrate for being formed with nano-pore on surface.It is logical
Cross be scaling up the size (10mm × 10mm) of existing stainless steel substrate porous stainless steel substrate is designed to 50mm ×
The size of 60mm.Anodic oxidation is carried out under following treatment conditions.
Recycle collet of the water in the thermostat of 5 DEG C of temperature across double jacket reactor continuously.Made using blender
The temperature of electrolyte is kept constant.The constant voltage of 40V is kept during entire reaction.Divide stainless steel substrate anodic oxidation 10
Clock.
Fig. 2 a shows the Flied emission scanning electron microscopy of the surface topography of the nano-pore stainless steel substrate prepared in embodiment 1
Mirror (FE-SEM) figure.Observe the mean depth of average diameter and 55nm of the nano-pore with 80nm.The image of Fig. 2 a is further
Nano-pore is disclosed with (1 μm of per unit surface area of nano-pore stainless steel substrate2) density in 160 to 200 holes formed.
Embodiment 2: metal-doped on the surface of stainless steel substrate
The stainless steel substrate prepared in embodiment 1 is doped to prepare the catalyst for being used for wastewater treatment with metal.
Silver or titanium is used to be doped as doping metals and by electronation or photoreduction.
Embodiment 2.1: electronation
The stainless steel substrate prepared in embodiment 1 is immersed into 0.001M to 0.05M AgNO3、TiCl3Or TiCl4And 20mL
10 minutes in the aqueous solution of sodium citrate or gallic acid, and it is added to it the 10mM sodium hydroxide or sodium borohydride of 0.5mL.
Embodiment 2.2: photoreduction
The stainless steel substrate prepared in embodiment 1 is immersed into 0.001M to 0.05M AgNO under vacuum in the dark3、
TiCl3Or TiCl4Aqueous solution in 12 hours, cleaned 5 to 10 minutes with distilled water and nitrogen, and with UV-C irradiate 1 to 2 hour.
Fig. 2 b to 2d is shown respectively the catalyst prepared using sodium borohydride by chemical reaction in embodiment 2.1, implemented
It is prepared in the catalyst and embodiment 2.2 for passing through chemical reaction preparation using sodium hydroxide in example 2.1 by photochemical reaction
Field emission scanning electron microscope (FE-SEM) figure of the surface topography of catalyst.Fig. 3 a and 3b are shown in embodiment 2 respectively
The figure of the result of the energy dispersive X-ray spectrum (EDX) of the catalyst of the catalyst and supported titanium of the load silver of preparation.Fig. 2 b is extremely
2d and Fig. 3 a to 3b demonstrates silver and successful doping of the titanium in nano-pore stainless steel substrate surface.
Embodiment 3: application catalyst being applied in the sewage treatment equipment based on advanced oxidation method
In this embodiment, the performance characteristic of the catalyst prepared in embodiment 2 is had rated.Specifically, using from China
The effluents of production of butanol plant emissions evaluate the COD removal efficiency and TOC removal efficiency of catalyst.Repetition is also evaluated
Use the performance characteristic of rear catalyst.
It is tested in neutral range and is adjusted without individual pH.With the fixed rate of 5 ml/mins to waste water
The ozone generated in ozone supply generator.UV light is generated using UV lamp with the wavelength of the power of 5W and 254nm.
Embodiment 3.1:COD removal efficiency
Initial COD concentration is set as 500mg/L.Target COD value is set as to be less than 100mg/L, this is the effluent of China
COD standard.Fig. 5 is to show the stainless steel substrate prepared in embodiment 1 and the catalyst for preparing in embodiment 2 is applied to and is based on
UV/O3AOP when COD removal efficiency variation figure.Referring to Fig. 5, when there is no applications catalyst (A), obtain within 60 minutes
62.35% COD removal efficiency.In contrast, the nano-pore stainless steel substrate (B) for preparing in using embodiment 1, embodiment
When catalyst (D) for being mounted with titanium prepared in the catalyst (C) for being mounted with silver nano-grain and embodiment 2 prepared in 2,
64.44%, 70.42% and 77.35% COD removal efficiency is obtained respectively.According to these results, it can be seen that doped with silver
The catalyst of nano particle and the removal significantly improved is shown compared with other situations doped with the catalyst of titanium nano particle
Efficiency.Under four kinds of different conditions, i.e., in the absence of a catalyst and there are nanometer stainless steel substrate (embodiment 1),
Catalyst (embodiment 2) doped with silver nano-grain and doped with titanium nano particle catalyst (embodiment 2) in the case where,
Final COD concentration is respectively 148mg/L, 128mg/L, 99mg/L and 70mg/L.These results prove the catalysis of only embodiment 2
Agent meets the effluent COD standard (100mg/L) of China.
Embodiment 3.2:TOC removal efficiency
Initial TOC concentration is set as 500mg/L.Fig. 6 is to show the stainless steel substrate prepared in embodiment 1 and embodiment 2
The catalyst of middle preparation is applied to based on UV/O3AOP when TOC removal efficiency variation figure.Referring to Fig. 6, when not applying
When catalyst (A), 58.06% TOC removal efficiency is obtained within 60 minutes.In contrast, the nanometer prepared in using embodiment 1
It is prepared in the catalyst (C) for being mounted with silver nano-grain and embodiment 2 prepared in hole stainless steel substrate (B), embodiment 2
When being mounted with catalyst (D) of titanium nano particle, 65.32%, 73.79% and 82.06% TOC removal efficiency is obtained respectively.
According to these results, it can be seen that catalyst doped with silver nano-grain and doped with the catalyst of titanium nano particle and other
Situation compares the removal efficiency for showing to significantly improve.The use of catalyst causes the TOC bigger than the difference of COD removal efficiency to go
Except the difference of efficiency.
Embodiment 3.3: the performance of rear catalyst is reused
Every kind of catalyst, which is reused, to be amounted to 100 times.In order to consistent, experiment carries out at identical conditions.Fig. 7 is to show
It is being based on UV/O3AOP in reuse during catalyst performance change figure.Referring to Fig. 7, with the number of reuse without
It closes, catalyst all shows almost the same removal efficiency.Before and after use, the feature of material is all without obvious poor
Not.It is therefore contemplated that catalyst can be used semi-permanently.
Claims (12)
1. a kind of catalyst for wastewater treatment, the catalyst include be formed on surface nano-pore stainless steel substrate and
The metal nanoparticle being loaded into the nano-pore, wherein the metal nanoparticle is at least one selected from silver and titanium
The nano particle of non-ferrous metal；The mean depth of average diameter and 20nm to 100nm of the nano-pore with 70nm to 90nm；
Every 1 μm of the stainless steel substrate2The quantity of the nano-pore of surface area is 160 to 200.
2. catalyst according to claim 1, wherein the metal nanoparticle is that average diameter is 15nm to 50nm
Sphere.
3. catalyst according to claim 1, wherein the average diameter of the nano-pore is averaged with the nano particle
The ratio of diameter is 2:1 to 5:1.
4. catalyst according to claim 1, wherein the average diameter of the nano-pore and the ratio of depth are 3:1 to 1:
1。
5. a kind of method for preparing the catalyst for wastewater treatment, the method includes passing through anodic oxidation in stainless steel substrate
Surface on formed and nano-pore and metal nanoparticle be loaded into nano-pore by electronation or photoreduction,
Wherein, the temperature at 5 DEG C to 9 DEG C carries out the anode under stiring with the electric current of the voltage of 20V to 60V and 0.1A to 6A
Oxidation,
Wherein, the electronation is carried out by following steps: the stainless steel substrate is immersed to the water containing metal salt and acid
In solution, and to the aqueous solution add reducing agent,
Wherein, the photoreduction is carried out by following steps: in the dark, in a vacuum immersing the stainless steel substrate
In aqueous solution containing metal salt and acid, the stainless steel substrate is cleaned with distilled water and nitrogen, and irradiated and cleaned with UV-C light
The stainless steel substrate crossed.
6. according to the method described in claim 5, wherein, the metal salt in the electronation is selected from AgNO3、TiCl3
And TiCl4Water-soluble non-ferrous metal salt, the acid is the acid at least one hydroxyl group or carboxylic group and selected from lemon
Lemon acid sodium, gallic acid and its mixture, the reducing agent are the highly basic selected from sodium hydroxide, sodium borohydride and its mixture.
7. according to the method described in claim 5, wherein, being added in the electronation with the concentration of 0.001M to 0.05M
The metal salt.
8. according to the method described in claim 5, wherein, the stainless steel substrate in the electronation is immersed 1 hour
Or the shorter time.
9. according to the method described in claim 5, wherein, the metal salt in the photoreduction is selected from AgNO3、
TiCl3And TiCl4Water-soluble non-ferrous metal salt.
10. according to the method described in claim 5, wherein, being added in the photoreduction with the concentration of 0.001M to 0.05M
The metal salt.
11. according to the method described in claim 5, wherein, it is small that the stainless steel substrate in the photoreduction is immersed 6
Up to 12 hours, and UV-C light irradiated 0.5 hour to 2 hours.
12. a kind of sewage treatment equipment based on advanced oxidation method, the sewage treatment equipment include ozone reactor and UV
Generator, wherein the ozone reactor includes the catalysis according to any one of claim 1 to 4 for wastewater treatment
Agent.
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