CN110342702A - The method that photodissociation cooperates with electrical reactions processing waste water - Google Patents
The method that photodissociation cooperates with electrical reactions processing waste water Download PDFInfo
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- CN110342702A CN110342702A CN201910566228.XA CN201910566228A CN110342702A CN 110342702 A CN110342702 A CN 110342702A CN 201910566228 A CN201910566228 A CN 201910566228A CN 110342702 A CN110342702 A CN 110342702A
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- photodissociation
- waste water
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- dehydration
- processing waste
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- 239000002994 raw material Substances 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
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- 239000011248 coating agent Substances 0.000 claims description 8
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
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- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
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- 238000004043 dyeing Methods 0.000 abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- 239000010865 sewage Substances 0.000 abstract description 10
- 238000007639 printing Methods 0.000 abstract description 9
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 8
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
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- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
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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
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/465—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electroflotation
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
- C02F2001/46157—Perforated or foraminous electrodes
- C02F2001/46161—Porous electrodes
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
Abstract
The present invention relates to a kind of methods of photodissociation collaboration electrical reactions processing waste water: step S1: Wastewater by Electric flocculation-air floating precipitation process；Step S2: step S1 treated waste water repeats step S2 0-N time through photodissociation collaboration electrochemical reaction processing, step S3, and N is the natural number more than or equal to 1.Materializing strategy+biochemical treatment process+denitrification used at present may replace using the new technology and new process of electrical-optical combined reaction processing dyeing and printing sewage completely, electric flocculation is instead of coagulation, photodissociation cooperates with electrochemistry to replace biochemical treatment, and the effect in terms of drop COD, decoloration, except ammonia nitrogen and total nitrogen of the waste water after the process is obvious.
Description
Technical field
The present invention relates to a kind of sewage water treatment method, in particular to a kind of side of photodissociation collaboration electrical reactions processing waste water
Method.
Background technique
The textile printing and dyeing industry economic industry important as China, in its desizing, kiering, mercerising, dyeing, stamp and washing
A large amount of oil, acid, alkali, fiber impurity, inorganic salts, surfactant, slurry, dyestuff and chemical assistant can be used Deng during
Deng, cause generated waste water not only to be measured greatly, average 1 ton of every dyeing and printing process, 100~200 tons of textile water consumption, wherein 80~
90% becomes waste water, and waste water quality variation greatly, organic concentration is high, coloration height, pH high and biodegradability are poor, belong to difficulty
One of industrial wastewater of degradation.
Since China is one there is a serious shortage of the country of water resource, water scarcity have become restrict China's dyeing into
The limiting factor of one step development, limited water resource also determine that dyeing must walk Practice of Developing Cycle Economic, therefore, greatly
Waste water reuse is the wise selection based on future in power development.Waste water reuse is solved, due to containing centainly in waste water
Organic matter and coloration need to carry out waste water ability reuse after advanced treating.
Major part dye house effluents treatment effect is undesirable at present, and reclamation rate is very low, and reason substantially has following several feelings
Condition:
(1) printing and dyeing mill does not analyze itself waste water speciality (water quality, water), indiscriminately imitates his factory's experience, is as a result often not satisfactory.I.e.
Make waste water similar in production technology, similar treatment process can be used, but also to be joined according to water quality, water appropriate adjustment technology
Number guarantees that processing is horizontal.
(2) by the design specification of municipal sewage treatment, it is used for treatment of dyeing wastewater, only changes some parameters, especially
In early stage, large-scale dye house effluents centralized processing is all responsible for by larger design institute, and due to not deep enough to dyeing waste water property
Understand, causes very big loss.
(3) new technology, new process fail to incorporate the wastewater treatment of dyeing, with the fast development of environmental protection cause, greatly
Measure the new technology of sewage treatment, new process continues to bring out, although dyeing sewage treatment in recent years in process route and
Technically many improvement are made, but can not jump the circle of biochemical treatment always, this is also that dyeing waste water handles row up to standard
Put difficulty, the low major reason of reuse ratio.
Dyeing and printing sewage uses several main problems of biochemical treatment process for a long time:
1, investment is big
2, it takes up a large area
3, control ability is poor, including to activated sludge bacterium culture and survival ability be difficult to control.
4, ambient enviroment is poor, and a large amount of odorous gas of large area cesspool discharge can not be handled, and causes to plant area and surrounding
The pollution of environment
5, solid waste amount is big, and the especially two heavy a large amount of sludge generated are not only a burdens to unit, to fixed-end forces portion
Door is also a very big pressure, such as burns because having chlorine and aromatic hydrocarbon in sludge, carcinogenic substance dioxin will be generated, if buried
It can polluted underground water.The problem of comprehensive biochemical treatment, according to the characteristics of dyeing and printing sewage and wastewater discharge standard and useless
The requirement of water reuse, a kind of method that the application proposes photodissociation collaboration electrical reactions processing waste water.
Summary of the invention
It is an object of the invention to solve the deficiencies in the prior art, a kind of photodissociation collaboration electrical reactions processing waste water is provided
Method.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of method of photodissociation collaboration electrical reactions processing waste water, the technique include the following steps:
Step S1: Wastewater by Electric flocculation-air floating precipitation process；
Step S2: step S1 treated waste water through photodissociation collaboration electrochemical reaction processing,
Step S3 is repeated step S2 0-N times, and N is the natural number more than or equal to 1.
Preferably, step S2, which is based on photodissociation, cooperates with apparatus for electrochemical treatment, described device includes device noumenon, is inside set
There are multiple anodes and multiple cathodes and reference electrode to constitute three electrode multichannel electric fields, anode uses the load of negative photocatalyst-bearing
Body, carrier are titanium net, and cathode is titanium net of the same area, and the area of positive and negative pole plate is depending on the volume of device noumenon, anode
It is electrically connected with cathode with DC power supply, DC power supply uses the pulse power, the current density tune that anode potential is required according to pole plate
Whole, pole plate spacing is adjusted according to conductivity, and surrounding them also installs several ultraviolet lamps, is used for photodissociation.
Preferably, the load process of catalyst and titanium net, steps are as follows:
S1: titanium net or three-dimensional foam nickel plate being well coated with or are soaked in aqueous binder, Yu Wuchen after taking-up
Natural air drying in environment；
S2: step S1 air-dry after titanium net or three-dimensional foam nickel plate coating or impregnate photochemical catalyst；
S3: after the completion of coating or immersion photochemical catalyst process, in 250-600 DEG C of medium temperature baking oven, 1-1.5h is dried；
S4, repeats step S2 and S30-N times, and N is the natural number more than or equal to 1.
Preferably, in step S1 dustfree environment condition are as follows: environment temperature≤22 DEG C, ambient humidity≤RH55%.
Preferably, for step S1 by the way of coating, coated weight is 0.2-0.3g/ square centimeters.
Preferably, step S1 is by the way of impregnating, soaking time 20-30s.
Preferably, aqueous binder is process by the following raw material of mass percent: 28-38% ethyl orthosilicate, 21-
31% dehydrated alcohol, 1-2% hydrochloric acid, surplus are deionized water, and raw material summation is 100%.
Preferably, steps are as follows for the preparation method of aqueous binder:
Step S1 weighs each raw material of formula ratio first, is individually positioned in dustless closed container；
Step S2 takes in the ethyl orthosilicate of formula ratio to the conical flask with electromagnetic agitation, instills a certain amount of anhydrous second
Alcohol, controls rate of addition 0.05-0.1mL/min, mixing speed 100-500rpm, and hydrolysis obtains high-purity silicon dioxide；
Step S3 carries out the dehydrated alcohol of high-purity silicon dioxide, surplus that step S2 hydrolysis obtains and deionized water
Mixing is placed in a dustless container chamber, is mixed by clean 300-400rpm high speed agitator；
Step S4 is low by clean 100-200rpm in the mixed liquor that hydrochloric acid penetration is entered to step S3 using titration
Fast blender is sufficiently mixed, and is promoted dehydration, is obtained adhesive finished product after the completion of dehydration.
Preferably, photochemical catalyst is formed by the Raw material processing of following mass percent: 10-15% butyl titanate, 0.05-
0.1% platinum nitrate or potassium chloroplatinate, 0.05-0.1% ferric nitrate or iron hydroxide, 0.05-0.1% silver nitrate or silver chlorate, it is remaining
Amount is dehydrated alcohol, and the summation of raw material is 100%.
Preferably, steps are as follows for the preparation method of photochemical catalyst:
Step S1 first mixes the butyl titanate of formula ratio with dehydrated alcohol, forms A liquid；
Step S2 configures 0.05M ammonium hydroxide, is heated to 60-70 DEG C, forms B liquid；
The A liquid of step S1 is heated to 60-70 DEG C, is slowly added in B liquid by step S3, and constant temperature maintains 10-20min, then
Centrifuge separation obtains jelly C；
Step S4 purchases platinum nitrate or potassium chloroplatinate, ferric nitrate or iron hydroxide and the silver nitrate or silver chlorate of formula ratio,
It is added in the mucilage binding object C that step S3 is obtained, dehydration；
Step S5, after dehydration, centrifuge separation；
Step S6, in 400-550 DEG C of drying and processing 4-6h；
Step S7, up to manufactured goods after being ground to the block material of step S6 drying.
Preferably, using centrifuge separation, the revolving speed of centrifuge is 1000-5000rpm for separation in step S2, in step S3,
In step S3, the equipment of dehydration is negative pressure kettle, and the pressure of dehydration is -1000 to -2000pa, the temperature of dehydration
It is 80-100 DEG C, grinding is smashed and ground using nano grinder in step S5, and the partial size of the photochemical catalyst 90% of acquisition is
6-10nm。
Its function of electric flocculation air-flotation process is mainly in the present invention: removing particulate matter, suspended matter and organic colloid, removes a huge sum of money
Belong to and reduces part COD, ammonia nitrogen, total nitrogen.Electric flocculation air bearing combines the advantages of electrochemical process and flocculation-air floating method, electric flocculation gas
It is floating to be summarized as four kinds of mechanisms of action: electrolytic flocculation, electrofloatation, electrolytic oxidation, electroreduction.
1), electrolytic flocculation
Anode uses iron or aluminum metal, under the action of an external electric field anode (solubility) generation oxidation, the iron of generation from
Son or aluminium ion generate a series of multinuclear hydroxo complex and hydroxide, as flocculation in water by hydrolysis, polymerization
Agent is condensed processing to suspended matter in water and organic matter.
2), electrofloatation
Anode has oxygen generation when electrolysis, the hydrogen of nascent state is generated on cathode, after playing reduction reaction with Pollutants in Wastewater
Hydrogen is generated, hydrogen and oxygen are that occur in the form of microbubble, have good adhesion property with suspended particulate, and have
The ability of powerful capture, load, so that suspended particulate be made to float to the water surface.
3), electrolytic oxidation
The dissociation of water and the presence of Cl- in water when due to electrolysis, have the activity for generating and having Strong oxdiative ability in electrolysis
Oxygen, hydroxyl radical free radical and some other strong oxidizer or free radical such as Cl2、H2O2, oxygen occurs with the dissolved organic matter in solution
Change reaction to be allowed to degrade.
4), electroreduction
The hydrogen that nascent state is generated on cathode, has very strong restoring function, can rise also with the organic matter of oxidisability in waste water
Original reaction makes organic matter degradation.And it can be removed hexavalent chrome reduction at trivalent chromium in flocculation with chromium hydroxide precipitation.
Electric flocculation air bearing feature in the present invention:
1), since the complex compound of generation has chain structure, the unformed net of the high surface area of formation is caught floccule body, is played
Net catches, bridging action.The complex ion and hydroxide of generation have very high adsorption activity, and adsorption capacity is higher than general medicament
The hydroxide adsorption capacity that Hydrolyze method (PAC+PAM) obtains, so as to quickly and effectively adsorb the suspended matter in dyeing and printing sewage
(including heavy metal) and dissolved organic matter.
2), by electrolytic oxidation, larger molecular organics (organic colloid) are degraded into small molecule or even oxidable at CO2
And H2O, therefore the sediment that the sediment of electric flocculation generation is generated far fewer than medicament Hydrolyze method, about reduce 1/3.
3) it, is reacted by electrolytic oxidation, electroreduction, part COD, ammonia nitrogen and total nitrogen can be dropped.
4), electric flocculation air bearing module major function is based on flocculation sedimentation, supplemented by oxidation, reduction.
Photodissociation of the invention cooperates with electrochemical reaction processing method, and function is mainly: drop COD, decoloration, except ammonia nitrogen and always
Nitrogen combines electrochemistry and photochemical feature.Can be summarized as four kinds of mechanisms of action: 1), direct oxidation reaction；2), indirectly
Oxidation reaction；3), UV/Fenton oxidation reaction；4), the electrocatalytic reduction of cathode.
1), the direct oxidation reaction of anode: using the high oxidation potential of anode, when organic pollutant and ammonium ion and anode
It is directly oxidized when contact, the organic matter with oxidizing potential is reduced degradation in cathode.
2), indirect oxidation reacts:, can be as ideal electricity due to dyeing and printing sewage ion containing Cl- (salt) the high Cl- of concentration
Xie Zhi, and can be in electrochemical reaction as the medium for generating oxidant.OH-, Cl- in water, generation is oxidized in anode
OH、HClO、Cl2, and the oxygen in cathode water is reduced into [O], H2O2Deng passing through the organic matter in these oxidizing water
And ammonia nitrogen, especially hydroxyl radical free radical OH have extremely strong oxidation potential energy.
3), UV/Fenton oxidation reaction
Under ultraviolet light (254nm) irradiation, oxidant HClO, H of suboxides potential energy2O2High oxidation potential energy can be converted into
Free radical.
HClO+hv→·OH+C1
H2O2+hv→2·OH
4), the electrocatalytic reduction of cathode
Hydrogen in statu nascendi [H] reduction-oxidation organic matter that cathode generates is allowed to degrade, it is often more important that can be reduced directly
Nitroso nitrogen (NO2 -) and nitrato nitrogen (NO3 -), and ammonia nitrogen can be inhibited in the life of oxidation process Central Asia nitrate and nitrato nitrogen
At.
The beneficial effects of the present invention are:
1, object used at present may replace using the new technology and new process of electrical-optical combined reaction processing dyeing and printing sewage completely
Change processing+biochemical treatment process+denitrification, for electric flocculation instead of coagulation, photodissociation cooperates with electrochemistry to replace biochemical treatment, at the technique
Waste water after the reason effect in terms of drop COD, decoloration, removing ammonia nitrogen and total nitrogen is obvious.
2, solid waste amount is few, and other than electric flocculation generates a part precipitating, without secondary precipitation, therefore solid waste amount subtracts significantly
It is few, to greatly alleviate the pressure of fixed-end forces.
3, efficient degradation COD (including BOD) improves electrochemical oxidation efficiency since photodissociation cooperates with electrochemical reaction
50% or more.
4, ammonia nitrogen and total nitrogen are efficiently removed, inorganic nitrogen and organic nitrogen in strong oxidation is lauched are oxidized to nitrogen, really
It is up to standard to protect total nitrogen.
5, invest it is low with operating cost, occupied area is small: new process investment be about biochemical treatment process 1/2, operation at
This is about the 2/3 of biochemical treatment process, and occupied area is about the 1/3 of biochemical treatment process.
Detailed description of the invention
Fig. 1 is the process route chart of step S1 of the present invention；
Fig. 2 is the process route chart of step S2 of the present invention.
Specific embodiment
Below by specific embodiment, and in conjunction with attached drawing, technical scheme of the present invention will be further explained in detail.
Embodiment 1:
A kind of method of photodissociation collaboration electrical reactions processing waste water as shown in Figs. 1-2, the technique include the following steps:
Step S1: dyeing waste water electric flocculation air bearing precipitation process；
Step S2: step S1 treated dyeing waste water is through photodissociation collaboration electrochemical reaction processing；
Step S3 is repeated step S20-N times, and N is the natural number more than or equal to 1.
Specifically, step S2 is based on photodissociation and cooperates with apparatus for electrochemical treatment, and described device includes device noumenon, is inside set
There are multiple anodes and multiple cathodes and reference electrode to constitute three electrode multichannel electric fields, anode uses the load of negative photocatalyst-bearing
Body, carrier are titanium net, and cathode is titanium net of the same area, and the area of positive and negative pole plate is depending on the volume of device noumenon, anode
It is electrically connected with cathode with DC power supply, DC power supply uses the pulse power, the current density tune that anode potential is required according to pole plate
Whole, pole plate spacing is adjusted according to conductivity, and surrounding them also installs several ultraviolet lamps, is used for photodissociation.
The load process of catalyst and titanium net in the present invention, steps are as follows:
S1: fixed bed substrate is well coated in aqueous binder, after taking-up in dustfree environment natural air drying；
S2: step S1 air-dry after fixed bed coated substrate photochemical catalyst；Fixed bed substrate uses three-dimensional structure nickel foam；
S3: after the completion of coating photochemical catalyst process, in 250-300 DEG C of medium temperature baking oven, 1.5h is dried；
S4 repeats step S2 and S31 times.
Specifically, in step S1 dustfree environment condition are as follows: environment temperature≤22 DEG C, ambient humidity≤RH55%, apply
The amount of covering is 0.2g/ square centimeters, and aqueous binder is process by the following raw material of mass percent: 28% ethyl orthosilicate,
21% dehydrated alcohol, 1% hydrochloric acid, surplus are deionized water, and raw material summation is 100%, the preparation method step of aqueous binder
It is as follows:
Step S1 weighs each raw material of formula ratio first, is individually positioned in dustless closed container；
Step S2 takes in the ethyl orthosilicate of formula ratio to the conical flask with electromagnetic agitation, instills a certain amount of anhydrous second
Alcohol, controls rate of addition 0.05mL/min, mixing speed 100rpm, and hydrolysis obtains high-purity silicon dioxide；
Step S3 carries out the dehydrated alcohol of high-purity silicon dioxide, surplus that step S2 hydrolysis obtains and deionized water
Mixing is placed in a dustless container chamber, is mixed by clean 300rpm high speed agitator；
Step S4 in the mixed liquor that hydrochloric acid penetration is entered to step S3 using titration, is stirred by clean 100rpm low speed
It mixes device to be sufficiently mixed, promotes dehydration, obtain adhesive finished product after the completion of dehydration.
In the present embodiment, photochemical catalyst is formed by the Raw material processing of following mass percent: 10% butyl titanate,
0.05% platinum nitrate, 0.05% ferric nitrate, 0.05% silver nitrate, surplus are dehydrated alcohol, and the summation of raw material is 100%, and light is urged
Steps are as follows for the preparation method of agent:
Step S1 first mixes the butyl titanate of formula ratio with dehydrated alcohol, forms A liquid；
Step S2 configures 0.05M ammonium hydroxide, is heated to 65 DEG C, forms B liquid；
The A liquid of step S1 is heated to 65 DEG C, is slowly added in B liquid by step S3, and constant temperature maintains 10min, is then centrifuged for point
From acquisition jelly C；
Step S4 purchases the platinum nitrate, ferric nitrate and silver nitrate of formula ratio, is added in the mucilage binding object C that step S3 is obtained, and takes off
Water process；
Step S5, after dehydration, centrifuge separation；
Step S6, in 400 DEG C of drying and processing 6h；
Step S7, after being ground to the block material of step S6 drying to obtain the final product.
Specifically, using centrifuge separation, the revolving speed of centrifuge is 1000rpm for separation in step S3, in step S4, dehydration
The equipment of processing is negative pressure kettle, and the pressure of dehydration is -1000pa, and the temperature of dehydration is 80 DEG C, is ground in step S7
It is smashed and ground using nano grinder, the partial size of the photochemical catalyst 90% of acquisition is 6-10nm.
Embodiment 2
A kind of method of photodissociation collaboration electrical reactions processing waste water, which is characterized in that the technique includes the following steps:
Step S1: dyeing waste water electric flocculation air bearing precipitation process；
Step S2: step S1 treated dyeing waste water is through photodissociation collaboration electrochemical reaction processing；
Step S3 is repeated step S20-N times, and N is the natural number more than or equal to 1.
Specifically, step S2 is based on photodissociation and cooperates with apparatus for electrochemical treatment, and described device includes device noumenon, is inside set
There are multiple anodes and multiple cathodes and reference electrode to constitute three electrode multichannel electric fields, anode uses the titanium of negative photocatalyst-bearing
Net, cathode are titanium net of the same area, and the area of positive and negative pole plate is depending on the volume of device noumenon, anode and cathode and straight
Power electric connection is flowed, DC power supply uses the pulse power, and anode potential is adjusted according to the current density that pole plate requires, pole plate spacing
It is adjusted according to conductivity, surrounding them also installs several ultraviolet lamps, is used for photodissociation.
Steps are as follows for photochemical catalyst and the bonding coating processes of titanium net in the present invention:
S1: fixed bed substrate is sufficiently soaked in aqueous binder, after taking-up in dustfree environment natural air drying；
S2: step S1 air-dry after fixed bed substrate impregnate photochemical catalyst；Fixed bed substrate uses foamed aluminium；
S3: after the completion of coating or immersion photochemical catalyst process, in 550-600 DEG C of medium temperature baking oven, 1h is dried；
S4 repeats step S2 and S302 times.
Specifically, in step S1 dustfree environment condition are as follows: environment temperature≤22 DEG C, ambient humidity≤RH55%, step
By the way of impregnating, soaking time 20S, aqueous binder is process rapid S1 by the following raw material of mass percent:
38% ethyl orthosilicate, 31% dehydrated alcohol, 2% hydrochloric acid, surplus are deionized water, and raw material summation is 100%, aqueous binder
Preparation method steps are as follows:
Step S1 weighs each raw material of formula ratio first, is individually positioned in dustless closed container；
Step S2 takes in the ethyl orthosilicate of formula ratio to the conical flask with electromagnetic agitation, instills a certain amount of anhydrous second
Alcohol, controls rate of addition 0.1mL/min, mixing speed 500rpm, and hydrolysis obtains high-purity silicon dioxide；
Step S3 carries out the dehydrated alcohol of high-purity silicon dioxide, surplus that step S2 hydrolysis obtains and deionized water
Mixing is placed in a dustless container chamber, is mixed by clean 400rpm high speed agitator；
Step S4 in the mixed liquor that hydrochloric acid penetration is entered to step S3 using titration, is stirred by clean 200rpm low speed
It mixes device to be sufficiently mixed, promotes dehydration, obtain adhesive finished product after the completion of dehydration.
In the present embodiment, photochemical catalyst is formed by the Raw material processing of following mass percent: 15% butyl titanate, ammonium hydroxide
25%, 0.1% potassium chloroplatinate, 0.1% iron hydroxide, 0.1% silver chlorate, surplus is dehydrated alcohol, and the summation of raw material is
100%, steps are as follows for the preparation method of photochemical catalyst:
Step S1 first mixes the tetrabutyl titanate of formula ratio with dehydrated alcohol, forms A liquid；
Step S2 configures 0.05M ammonium hydroxide, is heated to 70 DEG C, forms B liquid；
The A liquid of step S1 is heated to 70 DEG C, is slowly added in B liquid by step S3, and constant temperature maintains 15min, is then centrifuged for point
From acquisition jelly C；
Step S4 purchases the potassium chloroplatinate, iron hydroxide and silver chlorate of formula ratio, and the mucilage binding object C that step S3 is obtained is added
In, dehydration；
Step S5, after dehydration, centrifuge separation；
Step S6, in 450 DEG C of drying and processing 5h；
Step S7, after being ground to the block material of step S6 drying to obtain the final product.
In the present embodiment, using centrifuge separation, the revolving speed of centrifuge is 5000rpm for separation in step S3, in step S4, is taken off
The equipment of water process is negative pressure kettle, and the pressure of dehydration is -1500pa, and the temperature of dehydration is 90 DEG C, is ground in step S7
Mill is smashed and ground using nano grinder, and the partial size of the photochemical catalyst 90% of acquisition is 6-10nm.
Embodiment 3
A kind of method of photodissociation collaboration electrical reactions processing waste water, which is characterized in that the technique includes the following steps:
Step S1: dyeing waste water electric flocculation air bearing precipitation process；
Step S2: step S1 treated dyeing waste water is through photodissociation collaboration electrochemical reaction processing；
Step S3 is repeated step S20-N times, and N is the natural number more than or equal to 1.
Specifically, step S2 is based on photodissociation and cooperates with apparatus for electrochemical treatment, and described device includes device noumenon, is inside set
There are multiple anodes and multiple cathodes and reference electrode to constitute three electrode multichannel electric fields, anode uses the titanium of negative photocatalyst-bearing
Net, cathode are titanium net of the same area, and the area of positive and negative pole plate is depending on the volume of device noumenon, anode and cathode and straight
Power electric connection is flowed, DC power supply uses the pulse power, and anode potential is adjusted according to the current density that pole plate requires, pole plate spacing
It is adjusted according to conductivity, surrounding them also installs several ultraviolet lamps, is used for photodissociation.
The step of bonding coating processes of photochemical catalyst and titanium net in the present invention, bonding coating processes, is as follows:
S1: fixed bed substrate is sufficiently soaked in aqueous binder, after taking-up in dustfree environment natural air drying；
S2: step S1 air-dry after fixed bed substrate impregnate photochemical catalyst；Fixed bed substrate is porous ceramic film material；
S3: after the completion of impregnating photochemical catalyst process, in 400-450 DEG C of medium temperature baking oven, 1.2h is dried；
S4 repeats step S2 and S32 times.
Specifically, in step S1 dustfree environment condition are as follows: environment temperature≤22 DEG C, ambient humidity≤RH55%, step
Rapid S1 is by the way of impregnating, soaking time 30S, the composition of aqueous binder are as follows: 33% ethyl orthosilicate, 26% anhydrous second
Alcohol, 1.5% hydrochloric acid, surplus are deionized water, and raw material summation is 100%, and steps are as follows for the preparation method of aqueous binder:
Step S1 weighs each raw material of formula ratio first, is individually positioned in dustless closed container；
Step S2 takes in the ethyl orthosilicate of formula ratio to the conical flask with electromagnetic agitation, instills a certain amount of anhydrous second
Alcohol, controls rate of addition 0.075mL/min, mixing speed 400rpm, and hydrolysis obtains high-purity silicon dioxide；
Step S3 carries out the dehydrated alcohol of high-purity silicon dioxide, surplus that step S2 hydrolysis obtains and deionized water
Mixing is placed in a dustless container chamber, is mixed by clean 350rpm high speed agitator；
Step S4 in the mixed liquor that hydrochloric acid penetration is entered to step S3 using titration, is stirred by clean 150rpm low speed
It mixes device to be sufficiently mixed, promotes dehydration, obtain adhesive finished product after the completion of dehydration.
In the present embodiment, photochemical catalyst is formed by the Raw material processing of following mass percent: 12% butyl titanate,
0.075% platinum nitrate, 0.075% ferric nitrate, 0.075% silver nitrate, surplus are dehydrated alcohol, and the summation of raw material is 100%, light
Steps are as follows for the preparation method of catalyst:
Step S1 first mixes the tetrabutyl titanate of formula ratio with dehydrated alcohol, forms A liquid；
Step S2 configures 0.05M ammonium hydroxide, is heated to 60 DEG C, forms B liquid；
The A liquid of step S1 is heated to 60 DEG C, is slowly added in B liquid by step S3, and constant temperature maintains 20min, is then centrifuged for point
From acquisition jelly C；
Step S4, platinum nitrate, ferric nitrate and the silver nitrate of formula ratio are added in the mucilage binding object C that step S3 is obtained, at dehydration
Reason；
Step S5, after dehydration, centrifuge separation；
Step S6, in 550 DEG C of drying and processing 4h；
Step S7, after being ground to the block material of step S6 drying to obtain the final product.
In the present embodiment, using centrifuge separation, the revolving speed of centrifuge is 3000rpm for separation in step S3, in step S4, is taken off
The equipment of water process is negative pressure kettle, and the pressure of dehydration is -2000pa, and the temperature of dehydration is 100 DEG C, is ground in step S7
Mill is smashed and ground using nano grinder, and the partial size of the photochemical catalyst 90% of acquisition is 6-10nm.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.
Claims (6)
1. the method that photodissociation cooperates with electrical reactions processing waste water, which is characterized in that the technique includes the following steps:
Step S1: percolate electric flocculation air bearing precipitation process；
Step S2: step S1 treated percolate is through photodissociation collaboration electrochemical reaction processing；
Step S3 is repeated step S20-N times, and N is the natural number more than or equal to 1.
2. the method for photodissociation collaboration electrical reactions processing waste water according to claim 1, which is characterized in that step S2 is based on light
Solution collaboration apparatus for electrochemical treatment, described device includes device noumenon, interior to be equipped with multiple anodes and multiple cathodes and reference electricity
Pole constitutes three electrode multichannel electric fields, and anode uses the carrier of negative photocatalyst-bearing, and carrier is titanium net, and cathode is same area
Titanium net, depending on the volume of device noumenon, anode and cathode is electrically connected the area of positive and negative pole plate with DC power supply, direct current
Power supply uses the pulse power, and anode potential is adjusted according to the current density that pole plate requires, and pole plate spacing is adjusted according to conductivity, electricity
Several ultraviolet lamps are also installed around pole, are used for photodissociation.
3. the method for photodissociation according to claim 1 or claim 2 collaboration electrical reactions processing waste water, which is characterized in that catalyst with
The load process of carrier, steps are as follows:
S1: titanium net or three-dimensional foam nickel plate are well coated with or are soaked in aqueous binder, in dustfree environment after taking-up
Middle natural air drying；The condition of dustfree environment in step S1 are as follows: environment temperature≤22 DEG C, ambient humidity≤RH55%, step S1 are adopted
With the mode of coating, coated weight is 0.2-0.3g/ square centimeters, and step S1 is by the way of impregnating, soaking time 20-30s；
S2: step S1 air-dry after titanium net or three-dimensional foam nickel plate coating or impregnate photochemical catalyst；
S3: after the completion of coating or immersion photochemical catalyst process, in 250-600 DEG C of medium temperature baking oven, 1-1.5h is dried；
S4, repeats step S2 and S30-N times, and N is the natural number more than or equal to 1.
4. according to claim 3 photodissociation collaboration electrical reactions processing waste water method, which is characterized in that aqueous binder by
The following raw material of mass percent is process: 28-38% ethyl orthosilicate, 21-31% dehydrated alcohol, 1-2% hydrochloric acid, surplus
For deionized water, raw material summation is 100%.
5. the method for photodissociation collaboration electrical reactions processing waste water according to claim 4, which is characterized in that aqueous binder
Steps are as follows for preparation method:
Step S1 weighs each raw material of formula ratio first, is individually positioned in dustless closed container；
Step S2 takes in the ethyl orthosilicate of formula ratio to the conical flask with electromagnetic agitation, instills a certain amount of dehydrated alcohol, controls
Rate of addition 0.05-0.1mL/min processed, mixing speed 100-500rpm, hydrolysis obtain high-purity silicon dioxide；
Step S3 mixes the dehydrated alcohol of high-purity silicon dioxide, surplus that step S2 hydrolysis obtains and deionized water
It is placed in a dustless container chamber, is mixed by clean 300-400rpm high speed agitator；
Step S4 in the mixed liquor that hydrochloric acid penetration is entered to step S3 using titration, is stirred by clean 100-200rpm low speed
It mixes device to be sufficiently mixed, promotes dehydration, obtain adhesive finished product after the completion of dehydration.
6. the method for photodissociation collaboration electrical reactions processing waste water according to claim 3, which is characterized in that photochemical catalyst is by such as
The Raw material processing of lower mass percent forms: 10-15% butyl titanate, 0.05-0.1% platinum nitrate or potassium chloroplatinate, 0.05-
0.1% ferric nitrate or iron hydroxide, 0.05-0.1% silver nitrate or silver chlorate, surplus are dehydrated alcohol, and the summation of raw material is
100%, steps are as follows for the preparation method of photochemical catalyst:
Step S1 first mixes the butyl titanate of formula ratio with dehydrated alcohol, forms A liquid；
Step S2 configures 0.05M ammonium hydroxide, is heated to 60-70 DEG C, forms B liquid；
The A liquid of step S1 is heated to 60-70 DEG C, is slowly added in B liquid by step S3, and constant temperature maintains 10-20min, is then centrifuged for
Separation, obtains jelly C, and the revolving speed of centrifuge is 1000-5000rpm；
Step S4 purchases platinum nitrate or potassium chloroplatinate, ferric nitrate or iron hydroxide and the silver nitrate or silver chlorate of formula ratio, is added
In the mucilage binding object C that step S3 is obtained, dehydration, the equipment of dehydration is negative pressure kettle, and the pressure of dehydration is -1000
To -2000pa, the temperature of dehydration is 80-100 DEG C；
Step S5, after dehydration, centrifuge separation, the revolving speed of centrifuge is 1000-5000rpm；
Step S6, in 400-550 DEG C of drying and processing 4-6h；
Step S7, to, up to manufactured goods, grinding is crushed using nano grinder after the block material grinding of step S6 drying
Grinding, the partial size of the photochemical catalyst 90% of acquisition are 6-10nm.
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