CN107151039A - Use the method for treating water of stainless steel nano-tube array - Google Patents
Use the method for treating water of stainless steel nano-tube array Download PDFInfo
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- CN107151039A CN107151039A CN201610120527.7A CN201610120527A CN107151039A CN 107151039 A CN107151039 A CN 107151039A CN 201610120527 A CN201610120527 A CN 201610120527A CN 107151039 A CN107151039 A CN 107151039A
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- stainless steel
- tube array
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- water
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 102
- 239000010935 stainless steel Substances 0.000 title claims abstract description 101
- 239000002071 nanotube Substances 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 65
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 83
- 230000003647 oxidation Effects 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 238000012545 processing Methods 0.000 claims description 19
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 10
- 238000005286 illumination Methods 0.000 claims description 7
- 239000011800 void material Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 16
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 14
- 239000002957 persistent organic pollutant Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- -1 hydroxyl radical free radical Chemical class 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 5
- 229940012189 methyl orange Drugs 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 231100001239 persistent pollutant Toxicity 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical class ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 208000028804 PERCHING syndrome Diseases 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 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
- 238000003486 chemical etching Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Abstract
Disclose the water treatment facilities and method using stainless steel nano-tube array.According to the water treatment facilities and method, the stainless steel nano-tube array with the specific surface area improved using pH and temperature stabilization is used as photochemical catalyst.It is different from using existing photochemical catalyst, the demand for limiting external environmental factor is eliminated using stainless steel nano-tube array.Stainless steel nano-tube array is applied in combination with UV light and hydrogen peroxide.The combination is highly effective in terms of efficiently degradation of contaminant.The water treatment facilities and method do not need other equipment, help to reduce initial equipment cost.Stainless steel nano-tube array substantially can be from losing and damaging during aoxidizing.Therefore, continuous water purifying is cost that is feasible and can substantially reducing production, management and water process.In addition, stainless steel nano-tube array corrosivity and toxicity compared with conventional photochemical catalyst is much lower, and prevent the possibility of secondary pollution.Therefore, the apparatus and method realize environment-friendly water process.
Description
Technical field
The present invention relates to the efficient water treatment process using stainless steel nano-tube array.More specifically, this
Invention is related to for being prepared not using by the way that stainless steel surfaces are carried out with anodic oxidation formation nanotube
Rust steel nano-tube array effectively removes the method for treating water of pollutant from water system.
Background technology
With recent quickly industrial development, the problem of environmental pollution has changed into one seriously.
Various schemes have been formulated to provide the solution of problem of environmental pollution.Specifically, increased life rubbish
Rubbish and industrial wastewater are the reason for a large amount of persistent pollutants are discharged into water system.This persistence
Pollutant causes the severe contamination of water resource, making it difficult to provide clean water.In these cases, it is right
In can effectively prevent the water treatment facilities of water resource pollution from there is the demand of growth.
Some in the method for treating water developed so far are related to the use of microorganism.This quasi-biology
Method for treating water is because their environment friendly is without causing secondary pollution and not destroying ecosystem
System.In spite of these advantages, biology method for treating water pollutes object space present in degraded water system
Face has limited effect, and needs substantial amounts of processing, maintenance and management to meet more and more tighter into original
The effluent quality requirement of lattice.
The purpose of bleaching and sterilization can be realized using the method for treating water of chlorine chemistry product.However, chlorination
Product easily produce carcinogenic substance with the organic compound reaction in water, such as chloramines, and this may cause two
Secondary pollution.In the case where chlorinated water is released in river, the chlorine remained in the water through processing into
Many problems may be caused by dividing.For example, remaining chlorine component is for perching in the various types of of river region
Microorganism is fatal, so as to destroy the ecosystem.
In order to overcome the limitation of above-mentioned method for treating water, it has been already proposed to use strong oxidizing property is ultraviolet (UV)
Light, hydrogen peroxide, ozone and photochemical catalyst and the various advanced oxidation methods for not causing secondary pollution.
Advanced oxidation method refers to more advanced water technology, wherein using ozone/hydrogen peroxide, mistake
Hydrogen oxide/UV light etc. is used as oxidation and pollution degradation water to produce strong oxidizing property hydroxyl radical free radical (OH)
In organic pollution medium.Develop advanced oxidation method come persistent pollutant of degrading (for example,
Synthetic detergent and agricultural chemicals) or the pollutant of high concentration is disposed in a short time, it is described
Persistent pollutant is not easy to be degraded by general processing method.
Be used alone ozone come carry out water process suppress THM produce, improve mouthfeel, prevent aggregation or
It is effective in terms of precipitation and raising bioactivity.In addition, it can be anticipated that the Strong oxdiative ability of ozone.
However, the slow reaction of ozone and most of organic compounds causes the ozone supply means of processing equipment
Capacity increase.Ozone not with some organic compounds react, these organic compounds therefore still
It is not removed.That is, ozone very optionally with organic compound reaction.The selectivity makes
The exclusive use for obtaining ozone is not suitable for water process.
Ozone is there may be carcinogenic substance in the presence of bromine in raw water, and with high corrosiveness and poison
Property.In addition, ozone gas has limited solubility in water.For these reasons, ozone is utilized
Water process it is limited and cause many problems.
In the method for treating water using ozone and hydrogen peroxide, oxygen is used as by the way that UV illumination is mapped to
Strong oxidizing property hydroxyl radical free radical is produced with simple and effective manner on the hydrogen peroxide of agent.However,
The hydroxyl for the amount for needing excessive hydrogen peroxide to obtain the organic pollution present in raw water that is enough to degrade
Free radical, which results in financial burden.
Fenton methods are based on using iron (II) ion (Fe2+) it is used as catalyst combination hydrogen peroxide (H2O2)。
Catalyst increases the oxidability of hydrogen peroxide.Fenton methods be in 3 to 5 pH scopes it is effective,
Therefore other equipment or step is needed to be adjusted for pH, for example, what the pH for raw water was adjusted
Equipment or step, for pH to be readjusted to higher level to go iron ions after the completion of oxidation
Equipment or step and the step of for removing the sediment produced by iron ion.This other equipment
Or step makes complex disposal process, this is in processing cost and huge financial burden is caused in terms of the time.
[prior art document]
[patent document]
(patent document 1) Korean patent publication the 10-2012-0048420th
(patent document 2) Korean patent publication the 1997-0065435th
The content of the invention
The present invention is completed in view of problem of the prior art, and it is an object of the present invention to provide
A kind of water treatment facilities, it is stable for external environmental factor, and using with the increased ratio of index
The stainless steel nano-tube array of surface area is effectively to handle various types of pollutions present in water system
Thing.
It is a further object of the present invention to provide a kind of method for treating water, it need not control raw water and anti-
Accessory substance, such as sediment are not produced in the case of the condition (for example, pH and temperature conditionss) for answering device,
Realize high degradation efficiency simultaneously.
One aspect of the present invention provides a kind of water treatment facilities, and it includes hollow with predetermined volumes
Reactor, for raw water is fed into reactor feed pump, for by the water through processing from reaction
Device is transferred to the shifting pump of outside, install in the reactor at least partly to contact with raw water at least one
Individual stainless steel nano-tube array, for ultraviolet (UV) illumination to be mapped on stainless steel nano-tube array
UV irradiation units and the hydrogen peroxide delivery device for hydrogen peroxide to be supplied to reactor.
Stainless steel nano-tube array is attached to the inner side of reactor, or pre- with being separated on the inside of reactor
Fixed distance.
UV irradiation units are the circles in the centre for being rotatably mounted and being axially arranged at reactor
Cylindrical form.
UV irradiation units include be disposed axially in cylinder at least one UV lamp, be attached at cylinder
The blade of the top and bottom of body and hollow rotating shaft is connected to provide the variable-speed motor of revolving force,
The hollow rotating shaft is integratedly attached to the upper end of cylinder.
Stainless steel nano-tube array is prepared by carrying out anodic oxidation to stainless steel film.
Stainless steel nanotube has 10nm to 500nm external diameter and 1nm to 100nm average length.
Another aspect of the present invention provides a kind of method for treating water, and it includes I) by feed pump by raw water
It is fed into reactor, II) in the reactor with UV light, hydrogen peroxide and stainless steel nano-tube array
Handle raw water, and III) water through processing is turned into pressure moved on to outside reactor.
In step II) in, with 200nm to 400nm wavelength UV light irradiation stainless steels nanotube battle array
Row.
Stainless steel nanotube has 10nm to 500nm external diameter and 1nm to 100nm average length.
According to the water treatment facilities and method of the present invention, pH and the ratio with raising of temperature stabilization are used
The stainless steel nano-tube array of surface area is used as photochemical catalyst.It is different from using existing photochemical catalyst, make
The demand of limitation external environmental factor is eliminated with stainless steel nano-tube array.Stainless steel nano-tube array with
UV light and hydrogen peroxide are applied in combination.The combination is highly effective in terms of efficiently degradation of contaminant.
In addition, the water treatment facilities and method of the present invention do not need other equipment, such as precipitating
The equipment of thing separation, the equipment supplied for photochemical catalyst and the equipment reclaimed for photochemical catalyst,
This helps to reduce initial equipment cost.Stainless steel nano-tube array can substantially exempt from during aoxidizing
Suffer a loss and damage.Therefore, continuous water purifying is feasible and can substantially reduce production, manage
The cost of reason and water process.
In addition, stainless steel nano-tube array corrosivity and toxicity compared with conventional photochemical catalyst is much lower,
And prevent the possibility of secondary pollution.Therefore, apparatus and method of the invention are realized environmentally friendly
Carry out water process.
Brief description of the drawings
With reference to accompanying drawing, according to the description of embodiments below, these and/or other aspect of the invention and
Advantage can become obvious and easier to understand, in the accompanying drawing：
Fig. 1 is the horizontal stroke for the structure for illustrating water treatment facilities according to the first embodiment of the invention
Sectional view；
Fig. 2 is to illustrate the UV installed in water treatment facilities according to the second embodiment of the invention
The cross-sectional view of the structure of irradiation unit；
Fig. 3 is the FE-SEM of the surface topography of stainless steel nano-tube array for showing to prepare in preparation example 1
Figure；
Fig. 4 be show when by using the stainless steel nano-tube array prepared in preparation example 1, hydrogen peroxide,
UV light or its combination are handled the figure of the experimental result obtained when carrying out degradable organic pollutant；
Fig. 5 is will to be used as photochemical catalyst and UV light and peroxidating by using unprocessed stainless steel film
Hydrogen combination is handled the experimental result that is obtained when carrying out degradable organic pollutant, and by using stainless steel
Nano-tube array combines with UV light and hydrogen peroxide as photochemical catalyst and is handled mutually similar to degrade
The figure that the experimental result obtained during the organic pollution of type is compared；With
Fig. 6 is to show to be combined with UV light and hydrogen peroxide according to the present invention when repeatedly using preparing
The figure of the life characteristics of the stainless steel nano-tube array prepared in example 1.
Embodiment
It is the purpose of the present invention, specific excellent according to described in detail below and preferred embodiment combination accompanying drawing
Point and novel feature can become readily apparent from.It should be noted that in the case of any possible, identical member
Element is indicated with identical reference, even if they are depicted in various figures.It will be appreciated that at this
Although term first, second etc. can be used to describe different elements in text, these elements are not
These terms should be limited to.These terms are only used for distinguishing an element and another element.
In description of the invention, when think correlation technique explain in detail may unnecessarily make the present invention reality
When matter is not known, omitted.
The preferred embodiments of the invention are described in detail now with reference to accompanying drawing.
Fig. 1 is the horizontal stroke for the structure for illustrating water treatment facilities according to the first embodiment of the invention
Sectional view.On Fig. 1, water treatment facilities include the void reactor 100 with predetermined volumes, are used for
Raw water is fed into feed pump 200 in reactor 100, for by the water through processing from reactor 100
Be transferred to outside shifting pump 300, in reactor 100 with raw water at least partly contact to
Lack a stainless steel nano-tube array 400, for UV illumination to be mapped into stainless steel nano-tube array 400
On UV irradiation units 500 and for hydrogen peroxide is supplied to reactor 100 hydrogen peroxide supply
To device 600.
Feed pump 200 is arranged in pipeline outside raw water being fed into reactor 100.
UV irradiation units 500 be arranged on reactor 100 in, and can with illumination shot-light, particularly
High-pressure sodium lamp is as an example.
Reactor 100 is may be mounted at as at least one illumination shot-light of UV irradiation units 500
Top, side or bottom.The size of illumination shot-light can be adjusted suitably.
Hydrogen peroxide delivery device 600 is connected with hydrogen peroxide holding vessel, and is connected to instead with one end
Answer top, the pipeline of side or bottom of device 100.By hydrogen peroxide delivery device 600 by peroxide
Change hydrogen to be fed into reactor 100.
Preferably, the inner side of stainless steel nano-tube array 400 and reactor 100 is in close contact, or
Inner side with reactor 100 is spaced apart.Desirably 0.1cm to 30cm distance is kept.
Preferably, stainless steel nanotube has 10nm to 500nm external diameter and 1nm to 100nm's
Average length.Stainless steel nanotube with the size smaller than size defined above prepare it is complicated,
The complicated preparation condition being difficult to is needed, and may be unsatisfactory in intensity.Meanwhile, than
The stainless steel nanotube of the big size of size defined above can not be provided enough to be had for degraded
The surface area of organic pollutants, causes organic pollutant degradation efficiency than method of the routine based on titanium dioxide
Or Fenton methods are low.Most preferably in the case where considering raw water state etc. by stainless steel nanotube
Size is properly selected in scope defined above.
The shape of stainless steel nano-tube array 400 is not particularly limited, can be according to nano-tube array 400
Determine location-appropriate in the reactor.Stainless steel nano-tube array 400 is preferably rectangular shape,
Except when when it is attached to the inner side of reactor.Rectangular shape make stainless steel nano-tube array 400 with
It is favourable in terms of the contact area maximization of raw water and hydrogen peroxide.
The stainless steel nano-tube array 400 of rectangle can have 1 to 3 length-width ratio.In view of getting dirty
The amount of water or the size of reactor are contaminated, most preferably by the length and width of stainless steel nano-tube array 400
Properly select in scope defined above.
Exist in two forms as the titanium dioxide of representational photochemical catalyst：Powder and immobilization phase.
Verified titania powder due to its big specific surface area be efficient in terms of water process.However,
Titania powder is difficult to be separated from the water and reclaimed.In order to reuse photochemical catalyst and be cleaned
Water, titanium dioxide needs to be essentially completely recovered.Therefore, additionally needing the technology of costliness.Titanium dioxide
Fine powder granules are easily gathered into bigger particle during water process.With the progress of aggregation, dioxy
The separative efficiency for changing titanium is gradually reduced.As fine powder gradually increases from a distance from light source, close rate is fast
Prompt drop is low.For these reasons, titania powder is dfficult to apply to high power capacity water treatment facilities.
Developed the skill for photochemical catalyst such as titanium dioxide being immobilized in substrate or carrier
Art.However, be attached to the stability of the immobilization photochemical catalyst of substrate or carrier with increased water at
Manage frequency and decline, cause the loss of photochemical catalyst.The loss causes degradation efficiency poor.
Stainless steel nano-tube array 400 is by carrying out anodic oxidation to stainless steel film with stainless at this
Nanotube is formed on the surface of steel film to prepare.It is different from conventional photochemical catalyst, stainless steel nanometer
Pipe array 400 does not exist in the form of a powder, but provides in the form of a film.Therefore, stainless steel
Nano-tube array 400 undergoes less reduction in terms of stability is adhered to during processing.As a result, to the greatest extent
Pipe is used for a long time, and stainless steel nano-tube array is from losing or damaging, so that can prevent it from floating
Float in water system.Even if when stainless steel nano-tube array 400 is attached to the inner side of reactor 100,
It can be replaced during processing with new stainless steel nano-tube array without stopping reactor
100 operation.Therefore, to the form of the stainless steel nano-tube array 400 in reactor 100
Without concrete restriction.
Stainless steel nano-tube array 400 for external environmental factor as pH, temperature and heat be it is stable,
This realizes high degradation efficiency without the condition for the raw water for controlling to be fed into reactor 100.
It is different from using ozone or the water treatment facilities of oxychloride agent, use non-toxic stainless steel nanotube
The water treatment facilities of array 400 do not cause secondary pollution, therefore are environment-friendly.
The water treatment facilities of the present invention can also include rotary shaft 110 to provide rotation in reactor 100
Turn power.Rotary shaft 110 can be arranged in the centre of reactor 100.Preferably rotary shaft 110
It is spaced apart with stainless steel nano-tube array 400 in reactor 100.Distance is preferably
For 1cm to 20cm.The motion of rotary shaft 110 make it that the raw water for entering reactor 100 is flowable, leads
Cause raw water and the contact area increase of hydrogen peroxide, UV light and stainless steel nano-tube array.This is increased
The time that contact area spends processing raw water shortens.
Compared with the use of hydrogen peroxide and UV light in conventional water treatment method, according to the present invention's
Stainless steel nano-tube array 400, UV irradiation units 500 and mistake in the water treatment facilities of the embodiment
The combination of oxidation hydrogen supplier 600, which is added, can produce the possibility of substantial amounts of hydroxyl radical free radical,
This helps to handle substantially reducing for the time that raw water is spent.
The present invention method for treating water be that cost benefit is good compared with conventional water treatment method, this be because
It is substantial amounts of can also to be produced when a small amount of hydrogen peroxide is supplied by stainless steel nano-tube array
Free radical.
Hereinafter, understand reference picture 2 to illustrate water treatment facilities according to the second embodiment of the invention.
Fig. 2 is the cross-sectional view of water treatment facilities.
According to the first embodiment of the invention it is as overall with the water treatment facilities of the second embodiment
It is similar, but difference is to be configured such that to reaction according to the water treatment facilities of the second embodiment
Device 100 ' more efficiently provides UV light and revolving force, as shown in Figure 2.Specifically, no
The steel nano-tube array 400 ' that becomes rusty is the centre for being rotatably mounted and being disposed axially in reactor 100 '
The form of cylinder 401 ', blade 402 ' is attached at the top and bottom of cylinder 401 ', variable speed power
Machine 404 ' is connected with rotary shaft 403 ' to provide revolving force, and rotary shaft 403 ' is integratedly attached to cylinder
401 ' upper end.
Same parts in the water treatment facilities of the first embodiment and the second embodiment are eliminated herein
Repeat specification.
Another aspect of the present invention is related to a kind of method for treating water, and it includes I) by feed pump by raw water
It is fed into reactor, II) in the reactor with UV light, hydrogen peroxide and stainless steel nano-tube array
Handle raw water, and III) by outside the water forced branch through processing to reactor.
Stainless steel nano-tube array is prepared by forming nanotube on the surface of stainless steel film
's.Nanotube will not be stripped from stainless steel film during water process.
Stainless steel nano-tube array is prepared by anodic oxidation.Specifically, by by Thin Stainless Steel
Film and another conductive material such as platinum or copper are immersed in electrolyte solution and film and conductive material are applied
Voltage carries out anodic oxidation.As the result of anodic oxidation, in the whole surface of stainless steel film
Form the nanotube with uniform-dimension.
In method for treating water, light is used as using the stainless steel nano-tube array prepared by anodic oxidation
Catalyst.
According to method for treating water, first, raw water is fed into reactor by feed pump.
Afterwards, stainless steel nano-tube array is installed in the reactor and supplies hydrogen peroxide and UV light
It is given to reactor.In the reactor, organic pollution present in raw water is fallen by oxidation processes.
After the completion of reaction, the water through processing is transferred to outside reactor.
Preferably, stainless steel nanotube has 10nm to 500nm external diameter and 1nm to 100nm's
Average length.Stainless steel nanotube with the size smaller than size defined above prepare it is complicated,
The complicated preparation condition being difficult to is needed, and may be unsatisfactory in intensity.Meanwhile, than
The stainless steel nanotube of the big size of size defined above can not be provided enough to be had for degraded
The surface area of organic pollutants, causes organic pollutant degradation efficiency than method of the routine based on titanium dioxide
Or Fenton methods are low.Most preferably in the case where considering raw water state by the chi of stainless steel nanotube
It is very little to properly select in scope defined above.
In step II) in, preferably with 200nm to 400nm wavelength UV light irradiations stainless steel nanometer
Pipe array.It is poorly efficient that UV irradiations are carried out using all band UV lamp, because the hydroxyl produced
The amount of free radical is not significantly correlated with energy expenditure.
The raw water that method for treating water can also be included from reactor is fed into, which is removed, has big particle chi
Very little suspended material.The pretreatment ensures and by the existing water process based on UV light/hydrogen peroxide
Method compares the faster water process of the method for treating water by the present invention with Fenton methods, and allows to connect
Continuous water process is without because external environmental factor such as pH and temperature loss degradation efficiency.
Stainless steel nano-tube array can be used semi-permanently, it is to avoid stopped processing and exchanged photocatalysis
Agent or the demand using the other device for continuous feed photochemical catalyst.That is, this hair
Not the problem of bright method for treating water does not have to run into existing method for treating water.Therefore, from business efficiency
From the point of view of angle, method for treating water of the invention is very favorable.
The present invention can be described in more detail with reference to following examples.However, these embodiments should not be managed
Solve to define or limit the scope of the present invention and disclosure.It should be understood that being based on including following examples
The teachings of the present invention, those skilled in the art can easily implement what experimental result was not expressly provided
Other embodiments of the present invention.It will also be understood that, it is intended to this modifications and variations scheme is included in institute
In the range of attached claim.
<Preparation example 1>
Stainless steel (304L) film is cut into 10mm × 10mm size, this is conducive to anodic oxygen
Change and electroreduction.Etched by physical/chemical from the surface of stainless steel film and remove possible impurity, such as
Organic substance.Etched stainless steel film is cleaned with distilled water and ethanol.Thing is carried out using sand paper
Reason etching, uses hydrofluoric acid, nitric acid and distilled water (1:4:5, v/v/v) solution carries out chemical quarter
Erosion.Chemical etching was carried out in 30 seconds to prevent being formed and toxicity for the metal defect caused by hydrogen brittleness
The generation of gas.Nanotube is formed on using the pretreated stainless steel surfaces of anodic oxidation system.
Using the 5 volume % of perchloric acid (70%) in ethanol solution as anodic oxidation electrolyte.
Under the conditions of constant voltage anodic oxidation is carried out using electric power system (EP1605, PNCYS).Thin Stainless Steel
Film is arranged as anode, and the film of 95% platinum or copper or the wire rod wound with 5cm uniform intervals are arranged as the moon
Pole.Use 5 DEG C of constant temperature of cooler holding.Anodizing time is 10 minutes to 20 minutes.Afterwards,
Stainless steel through anodic oxidation is cleaned with distilled water and ethanol, and is stored before for next experiment
In drier.
Fig. 3 is the FE-SEM figures for the surface topography for showing stainless steel nano-tube array.The figure is shown in
Nanotube is formed uniformly in the whole surface of stainless steel film.It was observed that nanotube has about 100nm
External diameter.
Following experiment is carried out to evaluate the method for treating water of the present invention for work in artificial contamination's solution of degrading
For the efficiency of the methyl orange of organic pollution.The pH of artificial contamination's solution is about 6 to 8.
It is used as the hydrogen peroxide (30%) that the stainless steel nano-tube array of catalyst, fixed concentration are 1%
With power artificial contamination's solution is handled for 5W UV lamp.
Fig. 4 be show when by using stainless steel nano-tube array, hydrogen peroxide, UV light or its combine into
Row processing carrys out the figure of the experimental result obtained during degradable organic pollutant.In the figure, SSNT, H2O2
Refer to the processing using stainless steel nano-tube array, hydrogen peroxide and UV light respectively with UV.
Only with after hydrogen peroxide treatment, measuring the organic pollution methyl remained in artificial contamination's solution
The concentration of orange.As a result, methyl orange is not still removed.Only handled or received with stainless steel with UV light
After the combined treatment of mitron array and hydrogen peroxide, about 5% to 7% methyl orange is eliminated.With UV
After the combined treatment of light and stainless steel nano-tube array, it was observed that only about the 1% to 4% of methyl orange removal
Increase.
By contrast, with UV light/hydrogen peroxide in the case of without stainless steel nano-tube array
10 minutes and 20 minutes after reason, about 80% and 99% removal efficiency is realized respectively.
Especially, when being handled simultaneously with stainless steel nano-tube array/UV light/hydrogen peroxide, preceding 10
Minute eliminates 99% methyl orange, and this proves the method for treating water of the present invention in degradation efficiency and with making
The time that being compared with the conventional advanced oxidation method of UV light/hydrogen peroxide is spent processing reduces half
Or more aspect be excellent.
Fig. 5 is will to be used as photochemical catalyst and UV light and peroxidating by using unprocessed stainless steel film
Hydrogen combination is handled the experimental result that is obtained when carrying out degradable organic pollutant, and by using stainless steel
Nano-tube array combines with UV light and hydrogen peroxide as photochemical catalyst and is handled mutually similar to degrade
The figure that the experimental result obtained during the organic pollution of type is compared.As control, do not add
Photochemical catalyst.
As shown in Figure 5, caused using stainless steel nano-tube array as photochemical catalyst advanced with routine
In method for oxidation UV light compared with the use of hydrogen peroxide processing time reduce it is half or more.
Fig. 6 is to show to be combined repeatedly with UV light and hydrogen peroxide according to the method for treating water of the present invention
The figure of the life characteristics of stainless steel nano-tube array when using.
As shown in Figure 6, it is stainless even if stainless steel nano-tube array is reused 1 to 100 time
The degradation property of steel nano-tube array also keeps constant, and stainless steel nano-tube array is not observed
Weight loss.Based on these discoveries, conclusion is the water of the invention using stainless steel nano-tube array
Processing method continuously and can be used consistently.
Claims (8)
1. a kind of water treatment facilities, it includes the void reactor with predetermined volumes, for by raw water
It is the feed pump that is fed into the reactor, outer for the water through processing to be transferred to from the reactor
The shifting pump in portion, in the reactor with raw water at least partly contact at least one is stainless
Steel nano-tube array, for ultraviolet (UV) illumination to be mapped on the stainless steel nano-tube array
UV irradiation units and the hydrogen peroxide delivery device for hydrogen peroxide to be supplied to the reactor.
2. water treatment facilities according to claim 1, wherein, the stainless steel nano-tube array
The inner side of the reactor is attached to, or with separating predetermined distance on the inside of the reactor.
3. water treatment facilities according to claim 1, wherein, the UV irradiation units are can
Rotatably install and be disposed axially in the cylinder form in the centre of the reactor, and including
At least one UV lamp for being disposed axially in the cylinder, the upper end for being attached at the cylinder and
The blade of lower end and hollow rotating shaft is connected to provide the variable-speed motor of revolving force, it is described hollow
Rotary shaft is integratedly attached to the upper end of the cylinder.
4. water treatment facilities according to claim 1, wherein, the stainless steel nano-tube array
Prepared by making stainless steel film carry out anodic oxidation.
5. water treatment facilities according to claim 1, wherein, the stainless steel nanotube has
10nm to 500nm external diameter and 1nm to 100nm average length.
6. a kind of method for treating water, it includes：I) raw water is fed into reactor by feed pump,
II the raw water) is handled with UV light, hydrogen peroxide and stainless steel nano-tube array in the reactor,
And III) by outside the water forced branch through processing to the reactor.
7. method according to claim 6, wherein, in step II) in, with 200nm to 400nm
Stainless steel nano-tube array described in the UV light irradiations of wavelength.
8. method according to claim 6, wherein, the stainless steel nanotube has 10nm
To 500nm external diameter and 1nm to 100nm average length.
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| US20060076299A1 (en) * | 2004-10-08 | 2006-04-13 | The Hong Kong University Of Science And Technology | Synthesis of bentonite clay-based iron nanocomposite and its use as a heterogeneous photo fenton catalyst |
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