CN105060457A - Method for treating printing and dyeing wastewater by utilizing gas-phase free mixed radicals - Google Patents
Method for treating printing and dyeing wastewater by utilizing gas-phase free mixed radicals Download PDFInfo
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- CN105060457A CN105060457A CN201510554341.8A CN201510554341A CN105060457A CN 105060457 A CN105060457 A CN 105060457A CN 201510554341 A CN201510554341 A CN 201510554341A CN 105060457 A CN105060457 A CN 105060457A
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Abstract
The invention relates to a method for treating wastewater by means of electrocatalysis aeration and belongs to the field of wastewater treatment. Against the shortcoming that at present, during wastewater treatment by utilizing a Fenton reagent method, free radicals need to be generated in acid solution with the pH of 3-4, plenty of acid solution needs to be consumed, so that the acid solution is wasted and the treatment cost is too high, the method for treating printing and dyeing wastewater by utilizing gas-phase free mixed radicals is provided. According to the method, mixed gas of hydrogen chloride gas, hydrogen peroxide gas, steam and oxygen undergoes corona discharge and then generates plenty of gas-phase free mixed radicals mainly dominated by hydroxyl radicals, and then the gas-phase free mixed radicals are mixed with oxygen and then led into the wastewater to perform aeration, and the wastewater is treated. According to the method, plenty of hydroxyl radicals can be generated without high acid solution so as to treat the wastewater, plenty of acid solution can be saved, and the wastewater treatment effect is remarkable.
Description
Technical field
The present invention relates to a kind of method utilizing the free mixed base treatment of dyeing and printing of gas phase, belong to field of waste water treatment.
Background technology
In municipal sewage treatment, lower to organic clearance to be precipitated as main coagulation, suspended solids clearance is generally 40% ~ 60%, BOD
5it is about 50% that clearance is only 20% ~ 30%, COD clearance.Only adopt coagulation, be difficult to effectively control water pollutions.Enhabced primary treatment improves the clearance of organism and other pollutent significantly by less input, and therefore, enhabced primary treatment technology causes the attention of domestic and international engineering of water treatment circle gradually, becomes new study hotspot.The usable condition of sewage in urban area coagulation mainly contains: (1) for the municipal effluent of lower concentration through the direct qualified discharge of enhabced primary treatment.The sewage disposal of the many Small Urbans of China adopts this kind of mode, less investment can cut down relatively large pollution load.(2) first build one-level half treatment plant at no distant date, obtain good investment environment benefit through enhabced primary treatment, in time having ready conditions, build complete second-stage treatment technique again.(3) be treated to main municipal sewage plant for two stage biological, by enhabced primary treatment, remove the organism, heavy metal and the inorganic salt that are difficult to remove with biochemical treatment, alleviate the load of second-stage treatment simultaneously, reduce energy consumption.
In recent years, the high and constitutionally stable organic waste water of concentration constantly occurs, the organic waste water how effectively removing these difficult degradations has become the hot issue of water treatment.Hydroxyl radical free radical (OH) has high oxidizing potential (2.80EV) because of it, and its oxidation capacity is extremely strong, with most organic pollutants, chain reaction fast can occur, and non-selectivity objectionable impurities is oxidized to CO
2, H
2o or mineral salt, non-secondary pollution.Many investigators are had to carry out utilizing the research of OH process organic waste water both at home and abroad at present.
Aeration allows water and air fully contact the water treatment method exchanging gaseous substance and remove volatile matter in water, or gas is overflowed from water, as removed stink or the obnoxious flavour such as carbonic acid gas and hydrogen sulfide of water, or make oxygen dissolve in water, to improve dissolved oxygen concentration, reach deironing, demanganization or promote the object of aerobic microorganism degradation of organic substances.
Summary of the invention
The technical problem that the present invention mainly solves: need in pH value to be carry out in 3 ~ 4 acidic solutions for producing free radical when utilizing Fenton reagent method process waste water at present, need to consume a large amount of acid solutions, acid solution is caused to be wasted, the drawback that processing costs is too high, provide a kind of method utilizing the free mixed base treatment of dyeing and printing of gas phase, the method is by hydrogen chloride gas, hydrogen peroxide gas, water vapour, the mixed gas of oxygen produces a large amount of free mixed base of gas phase based on hydroxyl radical free radical after corona discharge, pass in waste water and carry out aeration afterwards with after oxygen mix, waste water is processed, the method does not need under strongly acidic solution, can produce great amount of hydroxy group free radical process waste water yet, a large amount of acid solutions can be saved, and process waste water Be very effective.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:
Utilize a method for the free mixed base treatment of dyeing and printing of gas phase, its concrete steps are:
(1) first use the technical hydrochloric acid of 120 ~ 140g/L to carry out surface cleaning on the wire netting of two block length 3m, wide 3m, scavenging period is 5 ~ 10min, immediately with water, wire netting surface washing is clean after cleaning, cleans its natural air drying of relief;
(2) on the above-mentioned wire netting surface cleaned, evenly last layer ZrO is coated with
2/ Ni
2o
3metal catalyst, thickness is 1 ~ 3cm;
(3) by the mode that the electric wire that 3 ~ 4m is long draws with string, two pieces of wire nettings are fixed into the state be parallel to each other, then electric wire is started energising, arranging voltage is 2 ~ 3kV, make one piece of wire netting with negative pole, another block is with positive pole, to between the wire netting with positive and negative electrode, hydrogen chloride gas is passed into while energising, hydrogen peroxide gas, water vapour, oxygen take volume ratio as the mixed gas of 2:2:3:3 composition, carry out under making the High Pressure of mixed gas between positive and negative electrode discharging and generate a large amount of free mixed bases of gas phase, wherein based on hydroxyl radical free radical, conduction time is 100 ~ 120min,
(4) be that 1:1 mixes by free for above-mentioned gas phase mixed base and oxygen with volume ratio, mixed gas aeration blower passed into waste water, carries out aeration, aeration time 2 ~ 4h.
Metal catalyst preparation method is:
(1) nickelous nitrate of 40 ~ 60g massfraction 25% is put into the beaker of 500mL, in cup, add 200 ~ 300mL distilled water stir, in solution, the zirconium nitrate of people 20 ~ 22g is added after stirring and dissolving, add 10 ~ 20g SODIUMNITRATE precipitation agent after being dissolved and stir, after stirring, regulator solution pH value is 5 ~ 6, and the NaCIO then adding 3 ~ 4g is oxidized, and carries out violent stirring 12h, by mixing solutions thermal treatment 20 ~ 24h at 60 ~ 70 DEG C of temperature, carry out filtration afterwards and obtain mixed sediment;
(2) above-mentioned throw out is added with deionized water wash repeatedly, until there is no nitrate ion and hydroxyl, carry out centrifugation afterwards, taking precipitate;
(3) baking oven above-mentioned throw out being put into 90 ~ 100 DEG C is dried, and be put in after oven dry in the retort furnace of 500 DEG C again and carry out roasting 2 ~ 3h, roasting is complete obtains ZrO
2/ Ni
2o
3catalyzer.
Application method of the present invention: in the dyeing waste water pond of 10m × 10m, Organic pollutants parameter (COD) in first wastewater measurement is 88%, after utilizing method of the present invention to process, then the mensuration Organic pollutants parameter (COD) processed in waste water is 8%, and removal rate arrives 90%.
The invention has the beneficial effects as follows:
(1) the method does not need strongly acidic solution can produce great amount of hydroxy group free radical to carry out wastewater treatment yet, saves a large amount of acid solutions;
(2) low, the Be very effective of this method of wastewater treatment cost, the COD clearance in waste water reaches 90%.
Embodiment
First use the technical hydrochloric acid of 120 ~ 140g/L to carry out surface cleaning on the wire netting of two block length 3m, wide 3m, scavenging period is 5 ~ 10min, immediately with water, wire netting surface washing is clean after cleaning, cleans its natural air drying of relief, the wire netting surface cleaned, is evenly coated with last layer ZrO
2/ Ni
2o
3metal catalyst, thickness is 1 ~ 3cm, by the mode that the electric wire that 3 ~ 4m is long draws with string, two pieces of wire nettings are fixed into the state be parallel to each other, then electric wire is started energising, arranging voltage is 2 ~ 3kV, make one piece of wire netting with negative pole, another block is with positive pole, to between the wire netting with positive and negative electrode, hydrogen chloride gas is passed into while energising, hydrogen peroxide gas, water vapour, oxygen take volume ratio as the mixed gas of 2:2:3:3 composition, carry out under making the High Pressure of mixed gas between positive and negative electrode discharging and generate a large amount of free mixed bases of gas phase, wherein based on hydroxyl radical free radical, conduction time is 100 ~ 120min, be that 1:1 mixes by free for gas phase mixed base and oxygen with volume ratio, mixed gas aeration blower passed into waste water, carries out aeration, aeration time 2 ~ 4h.
Metal catalyst preparation method is:
(1) nickelous nitrate of 40 ~ 60g massfraction 25% is put into the beaker of 500mL, in cup, add 200 ~ 300mL distilled water stir, in solution, the zirconium nitrate of people 20 ~ 22g is added after stirring and dissolving, add 10 ~ 20g SODIUMNITRATE precipitation agent after being dissolved and stir, after stirring, regulator solution pH value is 5 ~ 6, and the NaCIO then adding 3 ~ 4g is oxidized, and carries out violent stirring 12h, by mixing solutions thermal treatment 20 ~ 24h at 60 ~ 70 DEG C of temperature, carry out filtration afterwards and obtain mixed sediment;
(2) above-mentioned throw out is added with deionized water wash repeatedly, until there is no nitrate ion and hydroxyl, carry out centrifugation afterwards, taking precipitate;
(4) baking oven above-mentioned throw out being put into 90 ~ 100 DEG C is dried, and be put in after oven dry in the retort furnace of 500 DEG C again and carry out roasting 2 ~ 3h, roasting is complete obtains ZrO
2/ Ni
2o
3catalyzer.
Application method of the present invention: in the dyeing waste water pond of 10m × 10m, Organic pollutants parameter (COD) in first wastewater measurement is 88%, after utilizing method of the present invention to process, then the mensuration Organic pollutants parameter (COD) processed in waste water is 8%, and removal rate arrives 90%.
Example 1
The wire netting of two block length 3m, wide 3m is first carried out surface cleaning with the technical hydrochloric acid of 120g/L, and scavenging period is 5min, immediately with water, wire netting surface washing is clean after cleaning, cleans its natural air drying of relief, the wire netting surface cleaned, is evenly coated with last layer ZrO
2/ Ni
2o
3metal catalyst, thickness is 1cm, by the mode that the electric wire that 3m is long draws with string, two pieces of wire nettings are fixed into the state be parallel to each other, then electric wire is started energising, arranging voltage is 2kV, make one piece of wire netting with negative pole, another block is with positive pole, to between the wire netting with positive and negative electrode, hydrogen chloride gas is passed into while energising, hydrogen peroxide gas, water vapour, oxygen take volume ratio as the mixed gas of 2:2:3:3 composition, carry out under making the High Pressure of mixed gas between positive and negative electrode discharging and generate a large amount of free mixed bases of gas phase, wherein based on hydroxyl radical free radical, conduction time is 100 ~ 120min, be that 1:1 mixes by free for gas phase mixed base and oxygen with volume ratio, mixed gas aeration blower passed into waste water, carries out aeration, aeration time 2h.
Metal catalyst preparation method is:
The nickelous nitrate of 40g massfraction 25% is put into the beaker of 500mL, in cup, add 200mL distilled water stir, in solution, the zirconium nitrate of people 20g is added after stirring and dissolving, add 10g SODIUMNITRATE precipitation agent after being dissolved and stir, after stirring, regulator solution pH value is 5, and the NaCIO then adding 3g is oxidized, and carries out violent stirring 12h, by mixing solutions thermal treatment 20h at 60 DEG C of temperature, carry out filtration afterwards and obtain mixed sediment; Throw out is added with deionized water wash repeatedly, until there is no nitrate ion and hydroxyl, carry out centrifugation afterwards, taking precipitate; Baking oven throw out being put into 90 DEG C is dried, and is put in the retort furnace of 500 DEG C again and carries out roasting 2h after oven dry, and roasting is complete obtains ZrO
2/ Ni
2o
3catalyzer.
The method is disposed of sewage, and cost is low, manipulation is simple, and before process, in waste water, COD is 88%, and the COD processed in waste water is that the COD clearance in the waste water of 7% process reaches 92%.
Example 2
In the wastewater disposal basin of 6m × 6m, the wire netting of 6 long 3m, wide 2m is allowed in pond, at a distance of 1m between each wire netting, and make it exceed water surface 0.5m, draw with electric wire string between wire netting between two and be fixed; The ZrO2/Ni that uniform application one deck is thick on securing wire netting
2o
3/ TiO
2metal catalyst; Electric wire starts energising, and arranging voltage is 2.5kV, and energising is simultaneously to the mixed gas passing into hydrochloric acid, water vapour, hydrogen peroxide, oxygen between wire netting in water, and volume percent is 2:2:3:3, is energized to carrying out catalytic ionization to gas, and conduction time is 110min; In the middle of every two wire nettings, 9 aeration heads are installed under water, in its water, fill air with aeration blower, carry out aeration, aeration time 3h.
Described metal catalyst preparation method is:
The nickelous nitrate of 50g massfraction 25% is put into the beaker of 500mL, in cup, add 250mL distilled water stir, in solution, the zirconium nitrate of people 21g is added after stirring and dissolving, add 15g SODIUMNITRATE precipitation agent after being dissolved and stir, after stirring, regulator solution pH value is 5, and the NaCIO then adding 3.5g is oxidized, and carries out violent stirring 12h, by mixing solutions thermal treatment 22h at 65 DEG C of temperature, carry out filtration afterwards and obtain mixed sediment; Throw out is added with deionized water wash repeatedly, until there is no nitrate ion and hydroxyl, carry out centrifugation afterwards, taking precipitate; Baking oven throw out being put into 95 DEG C is dried, and is put in the retort furnace of 500 DEG C again and carries out roasting 2.5h after oven dry, and roasting is complete obtains ZrO
2/ Ni
2o
3catalyzer.
The method is disposed of sewage, and cost is low, manipulation is simple, and before process, in waste water, COD is 90%, and the COD processed in waste water is that the COD clearance in the waste water of 7% process reaches 92%.
Example 3
The wire netting of two block length 3m, wide 3m is first carried out surface cleaning with the technical hydrochloric acid of 140g/L, and scavenging period is 10min, immediately with water, wire netting surface washing is clean after cleaning, cleans its natural air drying of relief; The wire netting surface cleaned, is evenly coated with last layer ZrO
2/ Ni
2o
3metal catalyst, thickness is 3cm; By the mode that the electric wire that 4m is long draws with string, two pieces of wire nettings are fixed into the state be parallel to each other, then electric wire is started energising, arranging voltage is 3kV, make one piece of wire netting with negative pole, another block is with positive pole, to passing into the mixed gas that hydrogen chloride gas, hydrogen peroxide gas, water vapour, oxygen take volume ratio as 2:2:3:3 composition between the wire netting with positive and negative electrode while energising, carry out under making the High Pressure of mixed gas between positive and negative electrode discharging and generate a large amount of free mixed bases of gas phase, wherein based on hydroxyl radical free radical, conduction time is 120min; Be that 1:1 mixes by free for gas phase mixed base and oxygen with volume ratio, mixed gas aeration blower passed into waste water, carries out aeration, aeration time 4h.
Metal catalyst preparation method is:
The nickelous nitrate of 60g massfraction 25% is put into the beaker of 500mL, in cup, add 300mL distilled water stir, in solution, the zirconium nitrate of people 22g is added after stirring and dissolving, add 20g SODIUMNITRATE precipitation agent after being dissolved and stir, after stirring, regulator solution pH value is 6, and the NaCIO then adding 4g is oxidized, and carries out violent stirring 12h, by mixing solutions thermal treatment 24h at 70 DEG C of temperature, carry out filtration afterwards and obtain mixed sediment; Throw out is added with deionized water wash repeatedly, until there is no nitrate ion and hydroxyl, carry out centrifugation afterwards, taking precipitate; Baking oven throw out being put into 90 ~ 100 DEG C is dried, and is put in the retort furnace of 500 DEG C again and carries out roasting 2 ~ 3h after oven dry, and roasting is complete obtains ZrO
2/ Ni
2o
3catalyzer.
The method is disposed of sewage, and cost is low, manipulation is simple, and before process, in waste water, COD is 90%, and the COD processed in waste water is that the COD clearance in the waste water of 6% process reaches 93%.
Claims (2)
1. utilize a method for the free mixed base treatment of dyeing and printing of gas phase, its concrete steps are:
(1) first use the technical hydrochloric acid of 120 ~ 140g/L to carry out surface cleaning on the wire netting of two block length 3m, wide 3m, scavenging period is 5 ~ 10min, immediately with water, wire netting surface washing is clean after cleaning, cleans its natural air drying of relief;
(2) on the above-mentioned wire netting surface cleaned, evenly last layer ZrO is coated with
2/ Ni
2o
3metal catalyst, thickness is 1 ~ 3cm;
By the mode that the electric wire that 3 ~ 4m is long draws with string, two pieces of wire nettings are fixed into the state be parallel to each other, then electric wire is started energising, arranging voltage is 2 ~ 3kV, make one piece of wire netting with negative pole, another block is with positive pole, to between the wire netting with positive and negative electrode, hydrogen chloride gas is passed into while energising, hydrogen peroxide gas, water vapour, oxygen take volume ratio as the mixed gas of 2:2:3:3 composition, carry out under making the High Pressure of mixed gas between positive and negative electrode discharging and generate a large amount of free mixed bases of gas phase, wherein based on hydroxyl radical free radical, conduction time is 100 ~ 120min,
(3) be that 1:1 mixes by free for above-mentioned gas phase mixed base and oxygen with volume ratio, mixed gas aeration blower passed into waste water, carries out aeration, aeration time 2 ~ 4h.
2., according to a kind of method utilizing the free mixed base treatment of dyeing and printing of gas phase according to claim 1, it is characterized in that described metal catalyst preparation method is:
(1) nickelous nitrate of 40 ~ 60g massfraction 25% is put into the beaker of 500mL, in cup, add 200 ~ 300mL distilled water stir, in solution, the zirconium nitrate of people 20 ~ 22g is added after stirring and dissolving, add 10 ~ 20g SODIUMNITRATE precipitation agent after being dissolved and stir, after stirring, regulator solution pH value is 5 ~ 6, and the NaClO then adding 3 ~ 4g is oxidized, and carries out violent stirring 12h, by mixing solutions thermal treatment 20 ~ 24h at 60 ~ 70 DEG C of temperature, carry out filtration afterwards and obtain mixed sediment;
(2) above-mentioned throw out is added with deionized water wash repeatedly, until there is no nitrate ion and hydroxyl, carry out centrifugation afterwards, taking precipitate;
(3) baking oven above-mentioned throw out being put into 90 ~ 100 DEG C is dried, and be put in after oven dry in the retort furnace of 500 DEG C again and carry out roasting 2 ~ 3h, roasting is complete obtains ZrO
2/ Ni
2o
3catalyzer.
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| CN201510554341.8A CN105060457A (en) | 2015-09-02 | 2015-09-02 | Method for treating printing and dyeing wastewater by utilizing gas-phase free mixed radicals |
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| CN102897869A (en) * | 2012-10-30 | 2013-01-30 | 哈尔滨工程大学 | Turntable type ultraviolet and ozone catalytic oxidation organic sewage treatment device |
| CN103318990A (en) * | 2013-07-04 | 2013-09-25 | 哈尔滨工业大学 | Method for removing organic pollutants in water through electrochemical cathode catalytic ozonation |
| CN103877978A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | Preparation and application of catalyst for advanced treatment of printing and dyeing waste water by Fenton-like process |
-
2015
- 2015-09-02 CN CN201510554341.8A patent/CN105060457A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513753A (en) * | 2003-06-13 | 2004-07-21 | 大连海事大学 | Method of producing sulfuric acid using hydroxg oxidation of sulfur dioxide |
| CN1569679A (en) * | 2003-07-18 | 2005-01-26 | 中国科学院大连化学物理研究所 | Method for catalytic oxidation treatment of anisole waste water |
| CN101939450A (en) * | 2009-02-09 | 2011-01-05 | 北京有色金属研究总院 | The intermediate processing of one metal ion species |
| CN102897869A (en) * | 2012-10-30 | 2013-01-30 | 哈尔滨工程大学 | Turntable type ultraviolet and ozone catalytic oxidation organic sewage treatment device |
| CN103877978A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | Preparation and application of catalyst for advanced treatment of printing and dyeing waste water by Fenton-like process |
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Application publication date: 20151118 |