CN105254091A - Method for treating organic wastewater difficult to biochemically degrade - Google Patents

Method for treating organic wastewater difficult to biochemically degrade Download PDF

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CN105254091A
CN105254091A CN201510726959.8A CN201510726959A CN105254091A CN 105254091 A CN105254091 A CN 105254091A CN 201510726959 A CN201510726959 A CN 201510726959A CN 105254091 A CN105254091 A CN 105254091A
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waste water
treatment
organic waste
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concentration
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徐德生
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WUXI JIABANG ELECTRIC POWER PIPELINE FACTORY
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WUXI JIABANG ELECTRIC POWER PIPELINE FACTORY
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Abstract

The invention provides a method for treating organic wastewater difficult to biochemically degrade. The method comprises the following steps: (1) performing photocatalysis treatment on the organic wastewater difficult to biochemically degrade under the action of a SnO2/BiOCl heterojunction photocatalyst; (2) treating the organic wastewater subjected to photocatalysis treatment by hydrogen peroxide and persulfate. According to the method, organic pollutants are degraded by a photocatalysis technology and an advanced oxidization technology; the photocatalysis technology and the advanced oxidization technology can achieve a synergistic effect, thus further improving the efficiency of treating the organic wastewater difficult to biochemically degrade and greatly reducing the cost of treating the organic wastewater difficult to degrade; the method is suitable for large-scale application; meanwhile, side reaction between excessive molysite and SO4<->in a treatment process is reduced, and invalid consumption of SO4<->is avoided; moreover, generation of ferric sludge is alleviated, the treatment time is short, and the pH application range of the wastewater is wide.

Description

A kind for the treatment of process of bio-refractory organic waste water
Technical field
The invention belongs to technical field for the treatment of of organic waste, be specifically related to a kind for the treatment of process of bio-refractory organic waste water.
Background technology
Biochemical oxygen demand (BOD) (BOD 5) and chemical oxygen demand (COD) (COD) the talkative open fire of ratio in organic pollutant have that to be how much microorganism be difficult to decompose.BOD 5/ COD value is less, and the part that biochemistry is difficult to degrade is more.In general BOD 5/ COD is greater than 1/3 and just thinks to have good biodegradability, and bio-refractory organic waste water refers to by the more difficult waste water of common biodegradable, its biodegradability index BOD 5/ COD is less than 0.3.
At present Physical, chemical method and biological process are comprised to the treatment process of bio-refractory organic waste water.Bioremediation occupation area of equipment is large, long processing period, to hardly degraded organic substance poor processing effect.Traditional physico-chemical process such as flocculates and vaporizing extract process etc. just transfers to solid phase or gas phase pollutent from liquid phase, does not eliminate organic pollutant completely, causes secondary pollution.
High-level oxidation technology (AOTs) utilizes the strong oxidizing property free radical generated in reaction, organic pollutant degradation become small-molecule substance, is even mineralized into CO 2, H 2o and corresponding mineral ion.Traditional high-level oxidation technology is for chief active species carry out degradation of contaminant with hydrogen peroxide generation OH.Its shortcoming is that (1) pH value must be adjusted to less than 3, and (2) easily produce iron sludge-polluted thing, and under (3) neutral and alkaline condition, OH activity is not strong.
CN102531144A discloses a kind of method that persulphate process bio-refractory organic waste water worked in coordination with by hydrogen peroxide, the method comprises the steps: (1) measures the CODcr value of bio-refractory organic waste water, to make the ratio of the concentration of dual oxidants in organic waste water and CODcr value be (0.8 ~ 1.2): the 1 overall add-on determining dual oxidants; (2) in waste water, add ferrous salt solution, the mol ratio of dual oxidants and ferrous ion is (1 ~ 2): 1; (3) in waste water, add hydrogen peroxide and persulphate, both mol ratios are (2-4): (8-6).But the method processing costs is higher, also there is certain difficulty in the whole process process being applied to waste water, and the efficiency of the method degraded organic wastewater with difficult degradation thereby needs to improve further.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, the object of the present invention is to provide a kind for the treatment of process of bio-refractory organic waste water.The method can improve the processing efficiency of organic wastewater with difficult degradation thereby further, and greatly reduces the cost of process organic wastewater with difficult degradation thereby, is suitable for large-scale application.
Object of the present invention is achieved through the following technical solutions:
A treatment process for bio-refractory organic waste water, comprises the steps:
(1) by bio-refractory organic waste water at SnO 2photocatalysis treatment is carried out under the effect of/BiOCl heterojunction photocatalyst;
(2) organic waste water after persulphate process photocatalysis treatment worked in coordination with by hydrogen peroxide.
Step (1) described SnO 2the concentration of/BiOCl heterojunction photocatalyst in organic wastewater with difficult degradation thereby is 0.2-5.0g/L, as 0.5g/L, 1.0g/L, 1.5g/L, 2.0g/L, 2.5g/L, 3.0g/L, 3.5g/L, 4.0g/L or 4.5g/L, the time of described catalyzed degradation is 1-5h, as 1.5h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0h or 4.5h, described photocatalysis treatment is carried out under UV-irradiation.
SnO 2energy gap is 3.5-3.6eV, with matching of BiOCl (3.4-3.5eV), and SnO 2/ BiOCl heterojunction photocatalyst, under UV-irradiation, has good photocatalytic activity, is much higher than single semiconductor light-catalyst.Further, described photocatalyst, in photocatalytic degradation organic waste water process, can produce some active groups, as OH and O 2deng, these active groups can act synergistically with advanced oxidation agent in next step advanced oxidation processes, further effective degradable organic pollutant.
Step (2) is specially:
A measures the CODcr value of bio-refractory organic waste water, to make the ratio of the concentration of dual oxidants in organic waste water and CODcr value for (0.8 ~ 1.2): 1;
B adds ferrous salt solution in waste water, and the mol ratio of dual oxidants and ferrous ion is (1 ~ 2): 1; The effect of ferrous salt causes to produce free radical, is equivalent to catalyzer;
C adds hydrogen peroxide and persulphate in waste water, both mol ratios are (2 ~ 4): (8 ~ 6), as 2:8,2:7,2:6,3:8,3:7,3:6,4:8,4:7 or 4:6, fully after reaction, namely bio-refractory organic waste water be purified;
Described persulphate is the mixture of a kind of in Sodium Persulfate, Potassium Persulphate or ammonium persulphate or at least two kinds;
Described bio-refractory organic waste water is azo dye wastewater, organic pollutant major part in waste water from dyestuff is containing one or more-N=N-(azo), its chemical property is more stable, and waste component is complicated, is generally acknowledged high density bio-refractory organic waste water;
The ratio of the concentration of dual oxidants described in step a in organic waste water and CODcr value preferably 1: 1;
Ferrous salt described in step b is more than one in ferrous sulfate, ferrous ammonium sulphate, iron protochloride or Iron nitrate;
The mol ratio of dual oxidants described in step b and ferrous ion preferably 2: 1;
The mol ratio of hydrogen peroxide described in step c and persulphate preferably 3: 7.
Based on SO 4-high-level oxidation technology be the novel Persistent organic pollutants oxidation removal new technology that developed recently gets up, its advantage is SO 4 -not only can produce in wider pH scope, and at neutral and alkaline range, its oxidisability is better than OH, even if at acidic conditions, both also have close oxidation capacity.But shortcoming is OH compares SO 4 -have and stronger take hydrogen and addition ability by force, take hydrogen by force and addition ability is very crucial for degradable pollutent.So by SO 4 -best selection with OH degradation of contaminant of joining together.
The present invention has following advantage and effect relative to prior art:
(1) method associating photocatalysis technology of the present invention and high-level oxidation technology, improve the processing efficiency of organic wastewater with difficult degradation thereby, and greatly reduce the cost of process organic wastewater with difficult degradation thereby, be suitable for large-scale application.
(2) procedure of the present invention is simple, adequate operation, and photocatalyst can be recycled.
(3) the present invention utilizes hydrogen peroxide and the synergy of Sodium Persulfate in the process of degradable organic pollutant, OH and SO 4 -mutually excite, define the system that oxidisability is stronger, reduce the dosage of molysite, cost-saving, reduce excessive molysite and SO 4 -between side reaction, avoid SO 4 -effective consumption, reduce the generation of iron mud, the treatment time is short, and wastewater pH is applied widely, can reach good effect to the biochemical organic waste water of difficulty simultaneously.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
The embodiment of the present invention selects azoic dyestuff orange G as the representative of pollutent, and the degraded of research orange G solution can represent the degraded of difficult biochemical organic waste water to a certain extent.
The treatment process of the embodiment of the present invention first orange G solution is carried out photocatalytic degradation under UV-irradiation, by the photocatalyst separation in the solution after degraded out, in solution after afterwards ferrous salt solution being rendered to degraded, then drop into reactor after dual oxidants is mixed in proportion dissolving.The mol ratio of the overall dosage of dual oxidants and orange G is 20: 1 (it is 1: 1 that this ratio is equivalent to the concentration of dual oxidants in orange G solution with the ratio of the CODcr value of orange G solution).
The concentration of orange G can adopt UV-vis spectrophotometric determination in the absorbancy at 476nm place, obtains corresponding concentration according to absorbancy-concentration standard curve, calculates the percent of decolourization of dyestuff.
R=(C 0-C t)/C 0×100%
C t---the mass concentration (mg/L) of t orange G
C 0---the mass concentration (mg/L) of initial time orange G
Embodiment 1
The method of process azoic dyestuff (orange G) waste water, respectively shown in following A, B, C:
Method A, ferrous ion catalyzed oxidation hydrogen peroxide system
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Waste water from dyestuff volume: 250mL
Waste water ph: 3
Concentration of hydrogen peroxide in waste water: 68mg/L (2mmol/L)
Ferrous ion dosage: 278mg/L (1mmol/L) (adding ferrous sulfate: 69.5mg)
Hydrogen peroxide and ferrous ion mol ratio: 2: 1.
Method B, ferrous ion activation Sodium Persulfate system
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Waste water from dyestuff volume: 250mL
Waste water ph: 3
Sodium Persulfate concentration: 476mg/L (2mmol/L) (adding Sodium Persulfate: 119mg) in waste water
Ferrous ion dosage: 278mg/L (1mmol/L) (adding ferrous sulfate: 69.5mg)
Sodium Persulfate and ferrous ion mol ratio: 2: 1.
Method C, ferrous ion catalyzed oxidation hydrogen peroxide and Sodium Persulfate dual oxidizer system
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Waste water from dyestuff volume: 250mL
Waste water ph: 3
Sodium Persulfate concentration: 238mg/L (1mmol/L) (adding Sodium Persulfate: 59.5mg) in waste water
Concentration of hydrogen peroxide in waste water: 34mg/L (1mmol/L)
The concentration of ferrous ion in waste water: 278mg/L (1mmol/L), adds ferrous sulfate 69.5mg;
Hydrogen peroxide and Sodium Persulfate mol ratio: 1: 1
Dual oxidants and ferrous ion mol ratio: 2: 1.
Method D photochemical catalysis associating high-level oxidation technology
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Waste water from dyestuff volume: 250mL
Waste water ph: 3
Photocatalyst dosage is:
Sodium Persulfate concentration: 119mg/L (1mmol/L) (adding Sodium Persulfate: 30mg) in waste water
Concentration of hydrogen peroxide in waste water: 17mg/L (1mmol/L)
The concentration of ferrous ion in waste water: 139mg/L (1mmol/L), adds ferrous sulfate 35mg;
Hydrogen peroxide and Sodium Persulfate mol ratio: 1: 1
Dual oxidants and ferrous ion mol ratio: 2: 1.
Experimental result is as shown in table 1:
Table 1
The present embodiment compared for ferrous ion catalyzed oxidation hydrogen peroxide (method A), ferrous ion activation Sodium Persulfate (method B), ferrous ion catalyzed oxidation hydrogen peroxide and Sodium Persulfate dual oxidants (method C) and photochemical catalysis associating high-level oxidation technology (method D) four systems are on the impact of orange G decolorizing efficiency, in first three methods, under identical environment, the amount adding ferrous salt is identical, add the oxygenant of 2mmol/L, its orange G decolorizing efficiency is as shown in table 1, in ferrous ion catalyzed oxidation hydrogen peroxide system, after reaction, 60min rear decoloring rate remains unchanged substantially.In ferrous ion activation Sodium Persulfate system, the percent of decolourization of orange G reaction in time and improving.In ferrous ion catalyzed oxidation hydrogen peroxide and Sodium Persulfate dual oxidizer system, the percent of decolourization of orange G is much larger than the first two system.4th kind of method, although the dosage of advanced oxidation agent reduces by half, its percent of decolourization is the highest, illustrates that photocatalysis technology and high-level oxidation technology combined utilization exist synergistic effect, effectively can improve the percent of decolourization of azoic dyestuff orange G.
Embodiment 2
The method of process azoic dyestuff (orange G) waste water, respectively shown in following A, B, C:
The mol ratio of method A, hydrogen peroxide and Sodium Persulfate is 3: 7
The dosage of photocatalyst is: 0.5g/L
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Waste water from dyestuff volume: 250mL
Waste water ph: 3
The dosage of photocatalyst is: 0.5g/L
Dual oxidants overall density: 2mmol/L (353.6mg/L)
The concentration of ferrous ion in waste water: 278mg/L; Add ferrous sulfate: 69.5mg
The mol ratio of hydrogen peroxide and Sodium Persulfate: 3: 7
Dual oxidants and ferrous ion mol ratio: 2: 1.
The mol ratio of method B, hydrogen peroxide and Sodium Persulfate is 5: 5
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Waste water from dyestuff volume: 250mL
Waste water ph: 3
The mol ratio of hydrogen peroxide and Sodium Persulfate: 5: 5
Dual oxidants overall density: 2mmol/L (272mg/L)
The concentration of ferrous ion in waste water: 278mg/L; Add ferrous sulfate: 69.5mg
Dual oxidants and ferrous ion mol ratio: 2: 1.
The mol ratio of method C, hydrogen peroxide and Sodium Persulfate is 7: 3
The dosage of photocatalyst is: 0.5g/L
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Waste water from dyestuff volume: 250mL
Waste water ph: 3
The mol ratio of hydrogen peroxide and Sodium Persulfate: 7: 3
Dual oxidants overall density: 2mmol/L (190.4mg/L)
The concentration of ferrous ion in waste water: 278mg/L; Add ferrous sulfate: 69.5mg
Dual oxidants and ferrous ion mol ratio: 2: 1.
Method D,
The dosage of photocatalyst is: 0.5g/L
The mol ratio of hydrogen peroxide and Sodium Persulfate is 7: 3
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Waste water from dyestuff volume: 250mL
Waste water ph: 3
The mol ratio of hydrogen peroxide and Sodium Persulfate: 7: 3
Dual oxidants overall density: 1mmol/L (96mg/L)
The concentration of ferrous ion in waste water: 139mg/L; Add ferrous sulfate: 35mg
Dual oxidants and ferrous ion mol ratio: 2: 1.Experimental result is as shown in table 2:
Table 2
The present embodiment compared for the dual oxidants of different ratios, when be the mol ratio of hydrogen peroxide and Sodium Persulfate being respectively 3: 7,5: 5,7: 3, orange G percent of decolourization result is as shown in table 2, the dual oxidants degradation effect of different blended composition and division in a proportion has difference, best to orange G decolorizing effect when wherein the mol ratio of hydrogen peroxide and Sodium Persulfate is 3: 7.
Embodiment 3
The method of process azoic dyestuff (orange G) waste water, respectively shown in following A, B, C, D:
Method A, strongly-acid (pH value is 3) waste water
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Photocatalyst dosage is: 1.0g/L
Add ferrous sulfate: 69.5mg
Dual oxidants overall density: 2mmol/L (353.6mg/L)
Hydrogen peroxide and Sodium Persulfate mol ratio: 3: 7
The concentration of dual oxidants in waste water and the ratio of waste water COD cr: 1: 1
Dual oxidants and ferrous ion mol ratio: 2: 1.
Method B, slightly acidic (pH value is 5) waste water
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Waste water from dyestuff volume: 250mL
Photocatalyst dosage is: 1.0g/L
Add ferrous sulfate: 69.5mg
Dual oxidants overall density: 2mmol/L (353.6mg/L)
The concentration of dual oxidants in waste water and the ratio of waste water COD cr: 1: 1
Hydrogen peroxide and Sodium Persulfate mol ratio: 3: 7
Dual oxidants and ferrous ion mol ratio: 2: 1.
Method C, neutrality (pH value is 7) waste water
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Waste water from dyestuff volume: 250mL
Photocatalyst dosage is: 1.0g/L
Add ferrous sulfate: 69.5mg
Dual oxidants overall density: 2mmol/L (353.6mg/L)
The concentration of dual oxidants in waste water and the ratio of waste water COD cr: 1: 1
Hydrogen peroxide and Sodium Persulfate mol ratio: 3: 7
Dual oxidants and ferrous ion mol ratio: 2: 1.
Method D, alkalescence (pH is 9) waste water
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Waste water from dyestuff volume: 250mL
Photocatalyst dosage is: 1.0g/L
Hydrogen peroxide and Sodium Persulfate mol ratio: 3: 7
The concentration of dual oxidants in waste water and the ratio of waste water COD cr: 1: 1
Dual oxidants overall density: 2mmol/L (353.6mg/L)
Add ferrous sulfate: 69.5mg
Dual oxidants and ferrous ion mol ratio: 2: 1.
Experimental result is as shown in table 3:
Table 3
Under compared for identical wastewater environment in the present embodiment, waste water is adjusted to different pH value (pH=3,5,7,9) before adding oxygenant, orange G percent of decolourization is as shown in table 3, although the decolorizing effect of orange G is a little less than the decolorizing effect of orange G under acidic conditions in the basic conditions, equally also good effect can be reached.Describe dual oxide system applied widely to initial pH on wastewater value, generally do not need additional adjustment pH value.
Embodiment 4
The method of process azoic dyestuff (orange G) waste water, respectively shown in following A, B, C, D:
Method A, photocatalyst dosage are: 1.0g/L
In waste water, ferrous iron concentration is 0.15mmol/L
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Waste water from dyestuff volume: 250mL
Add ferrous sulfate: 10.425mg
Hydrogen peroxide and Sodium Persulfate mol ratio: 3: 7
The concentration of dual oxidants in waste water and the ratio of waste water COD cr: 1: 1
Dual oxidants and ferrous ion mol ratio: 40: 3.
Method B, photocatalyst dosage are: 2.0g/L
In waste water, ferrous iron concentration is 0.5mmol/L
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Waste water from dyestuff volume: 250mL
Add ferrous sulfate: 34.75mg
Hydrogen peroxide and Sodium Persulfate mol ratio: 3: 7
The concentration of dual oxidants in waste water and the ratio of waste water COD cr: 1: 1
Dual oxidants and ferrous ion mol ratio: 4: 1.
Method C, photocatalyst dosage are: 3.0g/L
In waste water, ferrous iron concentration is 1mmol/L
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Waste water from dyestuff volume: 250mL
Hydrogen peroxide and Sodium Persulfate mol ratio: 3: 7
The concentration of dual oxidants in waste water and the ratio of waste water COD cr: 1: 1
Add ferrous sulfate: 69.5mg
Dual oxidants and ferrous ion mol ratio: 2: 1.
Method D, photocatalyst dosage are: 4.5g/L
In waste water, ferrous iron concentration is 2mmol/L
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Waste water from dyestuff volume: 250mL
Add ferrous sulfate: 139mg
Hydrogen peroxide and Sodium Persulfate mol ratio: 3: 7
The concentration of dual oxidants in waste water and the ratio of waste water COD cr: 1: 1
Dual oxidants and ferrous ion mol ratio: 1: 1.
Experimental result is as shown in table 4:
Table 4
The present embodiment compared in identical waste water, adds the photocatalyst of different concns before adding oxygenant, and orange G percent of decolourization is as shown in table 4, illustrates that the optimum dosage of method photocatalyst of the present invention is 3.0g/L.
Embodiment 5
The method of process azoic dyestuff (orange G) waste water, respectively shown in following A, B, C, D::
In method A, waste water, the concentration of orange G is 22.6mg/L
The concentration of orange G: 22.6mg/L in waste water
Waste water from dyestuff CODcr:173mg/L
Waste water from dyestuff volume: 250mL
The dosage of photocatalyst is: 5g/L
Hydrogen peroxide and Sodium Persulfate mol ratio: 3: 7
Dual oxidants overall density: 1mmol/L (176.8mg/L)
Orange G and the overall mol ratio of dual oxidants: 1: 20
The concentration of dual oxidants in waste water and the ratio of waste water COD cr: 1: 1
Dual oxidants and ferrous ion mol ratio: 2: 1.
In method B, waste water, the concentration of orange G is 45.2mg/L
The concentration of orange G: 45.2mg/L in waste water
Waste water from dyestuff CODcr:338mg/L
Waste water from dyestuff volume: 250mL
The dosage of photocatalyst is: 5g/L
Dual oxidants overall density: 2mmol/L (353.6mg/L)
Hydrogen peroxide and Sodium Persulfate mol ratio: 3: 7
The concentration of dual oxidants in waste water and the ratio of waste water COD cr: 1: 1
Orange G and the overall mol ratio of dual oxidants: 1: 20
Dual oxidants and ferrous ion mol ratio: 2: 1.
In method C, waste water, the concentration of orange G is 100mg/L
The concentration of orange G: 100mg/L in waste water
Waste water from dyestuff CODcr:852mg/L
Waste water from dyestuff volume: 250mL
The dosage of photocatalyst is: 5g/L
Dual oxidants overall density: 5mmol/L (884mg/L)
The concentration of dual oxidants in waste water and the ratio of waste water COD cr: 1: 1
Hydrogen peroxide and Sodium Persulfate mol ratio: 3: 7
Orange G and the overall mol ratio of dual oxidants: 1: 20
Dual oxidants and ferrous ion mol ratio: 2: 1.
Experimental result is as shown in table 5:
Table 5
The present embodiment contrast orange G waste strength is within the scope of 22.6mg/L-100mg/L, keep orange G and dual oxidants entirety mol ratio 1: 20 constant, keep dual oxidants and ferrous ion mol ratio 2: 1 constant, keep hydrogen peroxide and Sodium Persulfate mol ratio 3: 7 constant, orange G decolorizing efficiency to affect result as shown in table 5, after 120min, orange G can decolour substantially, but along with the increase of orange G concentration, percent of decolourization can diminish a little.Illustrate that the inventive method is not only applicable to low-concentration organic waste water, be also applicable to high concentrated organic wastewater.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (10)

1. a treatment process for bio-refractory organic waste water, is characterized in that comprising the steps:
(1) by bio-refractory organic waste water at SnO 2photocatalysis treatment is carried out under the effect of/BiOCl heterojunction photocatalyst;
(2) organic waste water after persulphate process photocatalysis treatment worked in coordination with by hydrogen peroxide.
2. the treatment process of bio-refractory organic waste water according to claim 1, is characterized in that: step (1) described SnO 2the concentration of/BiOCl heterojunction photocatalyst in organic wastewater with difficult degradation thereby is 0.2-5.0g/L, and the time of described catalyzed degradation is 1-5h.
3. the treatment process of bio-refractory organic waste water according to claim 1 and 2, is characterized in that: step (1) described photocatalysis treatment is carried out under UV-irradiation.
4. according to the treatment process of the bio-refractory organic waste water one of claim 1-3 Suo Shu, it is characterized in that: step (2) is specially:
A measures the CODcr value after photocatalysis treatment in waste water, to make the ratio of the concentration of dual oxidants in organic waste water and CODcr value for (0.8 ~ 1.2): 1;
B adds ferrous salt solution in waste water, and the mol ratio of dual oxidants and ferrous ion is (1-2): 1;
C adds hydrogen peroxide and persulphate in waste water, and both mol ratios are (2-4): (8-6), and fully after reaction, bio-refractory organic waste water is purified;
Described dual oxidants is hydrogen peroxide and persulphate.
5. according to the treatment process of the bio-refractory organic waste water one of claim 1-4 Suo Shu, it is characterized in that: described bio-refractory organic waste water is azo dye wastewater.
6. the treatment process of bio-refractory organic waste water according to claim 5, is characterized in that: described azoic dyestuff is orange G.
7. according to the treatment process of the bio-refractory organic waste water one of claim 1-6 Suo Shu, it is characterized in that: described persulphate is the mixture of a kind of in Sodium Persulfate, Potassium Persulphate or ammonium persulphate or at least two kinds.
8. according to the treatment process of the bio-refractory organic waste water one of claim 4-7 Suo Shu, it is characterized in that: the ratio of the concentration of dual oxidants described in step a in organic waste water and CODcr value is 1: 1.
Preferably, the ferrous salt described in step b is more than one in ferrous sulfate, ferrous ammonium sulphate, iron protochloride or Iron nitrate.
9. according to the treatment process of the bio-refractory organic waste water one of claim 4-8 Suo Shu, it is characterized in that: the mol ratio of dual oxidants described in step b and ferrous ion is 2: 1.
10. according to the treatment process of the bio-refractory organic waste water one of claim 4-9 Suo Shu, it is characterized in that: the mol ratio of hydrogen peroxide described in step c and persulphate is 3: 7.
CN201510726959.8A 2015-10-30 2015-10-30 Method for treating organic wastewater difficult to biochemically degrade Pending CN105254091A (en)

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