CN107311340A - A kind of processing method of boracic, fluorine containing organic waste water - Google Patents
A kind of processing method of boracic, fluorine containing organic waste water Download PDFInfo
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- CN107311340A CN107311340A CN201710495899.2A CN201710495899A CN107311340A CN 107311340 A CN107311340 A CN 107311340A CN 201710495899 A CN201710495899 A CN 201710495899A CN 107311340 A CN107311340 A CN 107311340A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- 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
- C02F2101/108—Boron compounds
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- 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
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Abstract
The invention discloses the processing method of a kind of boracic, fluorine organic wastewater, it the described method comprises the following steps：(1) oxidant sylvite and molysite are added into pending waste water, is carried out after oxidation reaction and precipitation reaction, standing separation precipitation；(2) after precipitation separation, hydrolytic reagent aluminium salt, calcium salt, sylvite, water-soluble biological flocculant is added in supernatant, is carried out after precipitation reaction and flocculation reaction, separation of solid and liquid, the waste water after being handled.The method of the present invention can simply, effective, the processing BF of non-secondary pollution4 ‑1, F‑1, COD contents high waste water reaches discharge standard after wastewater treatment.
Description
Technical field
The invention belongs to field of industrial waste water treatment, a kind of boracic, the processing method of fluorine organic wastewater are related generally to.
Background technology
Resin is produced using cationic polymerization, often with boron trifluoride complex as catalyst, by neutralizing, washing
After Removal of catalyst, boracic, fluorine organic wastewater can be produced, the pH value of waste water is about 10, the concentration of boron is 1500-2000mg/L models
In enclosing, main with the presence of fluoro boron acid ion form in Boron in Wastewater, the concentration of fluorine is in the range of 4000-6000mg/L, useless
It is main in water to exist with fluorine ion form, also containing many unreacted unsaturated olefin such as styrene, Alpha-Methyl in waste water
The C5 such as styrene, dicyclopentadiene, pentadiene, cyclopentene, C9 alkene and oligomer, these unsaturated olefins and oligomer are led
The COD contents of waste water are caused to be up between 4000mg/L-6000mg/L.
With the increasingly raising to environmental consciousness, boracic, fluorine organic wastewater pollution on the environment cause everybody strong
Concern, fluorine-containing, boron organic wastewater is discharged into after environment, can cause the pollution of water body, soil, underground water, and can be in soil, terrestrial
It is enriched with plant, aquatile, the long-term hazards to environment are very big.If to boracic, fluorine treatment of Organic Wastewater is improper can be to people
Body health, Environmental security cause to seriously endanger, according to《Integrated wastewater discharge standard》(GB8978-1996) requirement, one-level row
Put the content of F in standard<10mg/L, B content<10mg/L.
BF4 -Treatment technology mainly includes chemical hydrolysis, and (rain pool, Li Yahong, Shao Huai opens《BF4 -Waste water Hydrolyze method is real
Test》), (Guo Ruiguang passes peaceful to the sylvite precipitation method slowly《The processing of fluoroborate plating waste water》), absorption method (Dong Lijun, Wang Yuze,
The glad of Sun Li《Natural limestone activation Fluoride-Absorption Capacity research》), F-Treatment technology have the precipitation method (emerging rainbow《At calcium salt precipitation method
Manage the research of fluoride waste》), (Jiang Shuanying, shine absorption method for the high court of a feudal ruler《Clay is ground to fluorine ion Adsorption mechanism in water
Study carefully》), (Wu Huaxiong, Meng Linzhen tie up ancestor to hyperfiltration perhaps《Hyperfiltration handles the experimental study of fluoride waste》) etc..
There is some following deficiency in current boracic, the processing method of fluorine organic wastewater：
1st, current all kinds of processing methods all do not account for COD influence；
2nd, the time that chemical hydrolysis processing procedure needs is long, even up to 2 hours；
3rd, the precipitation method generally require to adjust waste water pH value, and relatively difficult boron and Oil repellent by waste water is reduced to acceptable mark
It is accurate；
4th, chemical flocculation often causes secondary pollution；
5th, absorption method and hyperfiltration are adapted to the low waste water of processing boron, Oil repellent, and processing cost is higher.
The content of the invention
It is an object of the invention to overcome the defect of prior art, it is proposed that the low processing boracic of a kind of efficiency high, cost,
The method of fluorine organic wastewater, using oxidation/hydrolysis/precipitation/flocculation technique, the content of Boron in Wastewater and fluorine after processing is reduced
To below 10mg/L, national grade one discharge standard is reached.
Specifically, the step of methods described includes following be carried out continuously：
(1) oxidant sylvite and water-soluble molysite are added into pending waste water, oxidation reaction and precipitation reaction is carried out
Afterwards, standing separation is precipitated；
(2) after precipitation separation, hydrolytic reagent aluminium salt, precipitating reagent calcium salt and sylvite, water-soluble biological wadding are added in supernatant
Solidifying agent, is carried out after precipitation reaction and flocculation reaction, separation of solid and liquid, the waste water after being handled.
In step (1), the pH value of the waste water is between 9-11, and the concentration of boron is between 1500-2000mg/L, in waste water
Middle boron is main to be existed with fluoro boron acid ion form, and the concentration of fluorine is in the range of 4000-6000mg/L, mainly with fluorine in waste water
Ionic formses are present, also containing unsaturated olefin such as styrene, α-methylstyrene, dicyclopentadiene, penta 2 in waste water
The C5 such as alkene, cyclopentene, C9 alkene and its oligomer, these unsaturated olefins cause the COD contents up to 4000mg/L- of waste water
Between 6000mg/L.
In step (1), one or more complex salts of the sylvite in potassium hydrogen persulfate, potassium permanganate etc.；It is excellent
Elect potassium hydrogen persulfate as.
In step (1), the quality of the sylvite is 0.5-3 times of COD gross masses in waste water；Preferably 1 times.
In step (1), the molysite can provide ferric ion, it is to avoid cause the water-soluble molysite of secondary pollution；
One or more of the molysite in ferric nitrate, ferric sulfate, ferric trichloride etc.；Preferably ferric nitrate and/or ferric sulfate.
In step (1), the Fe in the molysite3+Molal quantity is F in waste water-0.4-2 times of ion molar equivalent；Preferably
1 times.
In step (1), Fe3+Synergy can be played by being added together with sylvite (such as potassium hydrogen persulfate), can be by waste water
COD reduce half, never before processing 4000-6000mg/L, 2000-3000mg/L is reduced to, while K+With BF4 -Reaction life
Into KBF4Precipitation, Fe3+With F-The borontrifluoride iron precipitation of reaction production, can be by BF in waste water by the step4 -Concentration be reduced to
100mg/L is between 300mg/L, F-Concentration be reduced to 100mg/L between 300mg/L.
In step (1), the temperature of precipitation reaction is 10 DEG C -50 DEG C；Preferably 20 DEG C -30 DEG C.
In step (1), precipitation reaction is being sufficiently stirred for lower progress, and the reaction time is no less than 10min；Preferably 10-45min
Or 15-45min, such as 10min, 20min, 30min.
In step (1), the time of the standing is defined by precipitating to separate, such as can be, but not limited to be 10min,
20min, 30min etc..
In step (2), one or more of the aluminium salt in alum, aluminum sulfate, aluminum nitrate etc. or its hydrate；Preferably
Alum, aluminum sulfate.
In step (2), aluminium salt and fluoboric acid root BF in supernatant4 -Mol ratio be (1~3)：1；Preferably (0.6~
1.5)：1.
In step (2), the calcium salt is water-soluble Ca salt, one kind or many in calcium chloride, calcium oxide, calcium nitrate etc.
Kind；Preferably calcium chloride.
In step (2), the molal quantity of the calcium salt is F in supernatant-1-3 times of molar equivalent；Preferably 1.5 times.
In step (2), the sylvite is water-soluble sylvite, one kind or many in potassium chloride, potassium nitrate, potassium phosphate etc.
Kind；Preferably potassium chloride.
In step (2), the molal quantity of the sylvite is BF in supernatant4 -0.5-2 times of molar equivalent；Preferably 1 times.
In step (2), water-soluble biological flocculant is the water-soluble protein-based biological flocculant containing hydrophobic amino acid, is put down
Equal weight average molecular weight is 50-200 ten thousand, preferably 100-150 ten thousand.The water-soluble biological flocculant is selected from water solubility r- polyglutamics
One or more in acid, polyglycine, poly-aspartate, polylalanine etc.；Preferably water solubility r- polyglutamic acids, it is put down
Equal weight average molecular weight is 100-150 ten thousand.
In step (2), the quality of the water-soluble biological flocculant is the 0.001%-0.01% of wastewater quality；Preferably
0.005%.
In step (2), the precipitation reaction and flocculation reaction are being sufficiently stirred for lower progress, the temperature of the precipitation reaction
10℃-50℃；Preferably 20 DEG C -30 DEG C.
In step (2), the time of the precipitation reaction and flocculation reaction is no less than 10min；Preferably 10-45min or 15-
45min, such as 10min, 20min, 30min.
In step (2), the time of the standing is defined by precipitating to separate, preferably 10-30min, such as can with but not
It is limited to 10min, 20min, 30min etc..
In step (2), hydrolytic reagent aluminium salt is added, is contributed to remaining BF4 -Hydrolysis generation F-Ion, and Al3+With F-Reaction
Generation fluorination aluminum precipitation, the Ca of water-soluble Ca salt2+With F-, B2O3 2-, B4O7 2-, the K of sylvite+With unhydrolysed BF4 -Generate KBF4It is heavy
Form sediment, water-soluble biological flocculant can catch boron salt and other positive and negative ions, form solid suspended particle, substitute what is commonly used at present
Chemical floc polyacrylamide, the catabolite of polyacrylamide is neurotoxin, harmful to human nerve, can be produced secondary
Pollution.Aluminium salt, calcium salt, sylvite, water-soluble biological flocculant are added together, cooperative effect can be produced, than being individually added into effect
It is good.Step (2) precipitation, flocculation reaction are being sufficiently stirred for lower progress, and the reaction time is no less than 10min, preferably 15-
45min.By step (2) processing after, Boron in Wastewater, Oil repellent all in the range of 5-10mg/L,<10mg/L, reaches country one
Level discharge standard.
In the present invention, the oxidation that is related to, hydrolysis, precipitation chemical equation it is as follows：
CnHmOk→CO2+H2O
CnHmOkThe mixture of each type organic, oligomer, wherein n scopes between 5-40, m scopes between 5-60,
K scope is between 1-10.
K++BF4 -→KBF4
BF4 -+H2O→H3BO3+F-
Fe3++F-→FeF3
Ca2++F-→CaF2
Al3++F-→AlF3
Ca2++B2O3 2-+B4O7 2-→CaB2O3+CaB4O7
Compared with prior art, the beneficial effects of the present invention are：
(1) oxidant sylvite (such as potassium hydrogen persulfate) and trivalent iron salt is used to compound as oxidant and precipitating reagent, at place
Manage BF in waste water4 -, F-While, COD contents are reduced, handling process is simplified, improves treatment effeciency；
(2) by compounding hydrolytic reagent, precipitating reagent, water-soluble biological flocculant, hydrolysis, precipitation, the efficiency of flocculation, contracting are improved
The time of short wastewater treatment；
(3) PH conditioning agents need not be added, pH value is adjusted；
(4) biological flocculant is used, it is to avoid cause secondary pollution；
(5) method of the invention is simple, effective, can handle BF4 -1, F-1, COD contents high waste water reached after wastewater treatment
Discharge standard.
Embodiment
With reference to specific examples below, the present invention is described in further detail.Implement the present invention process, condition,
Experimental method etc., is the universal knowledege and common knowledge of this area in addition to the following content specially referred to, the present invention does not have
Especially limit content.
First, the method for testing of waste water
BF4 -The measure of concentration uses ion selective electrode method, with BF4 -Select electrode as indicator electrode, calomel electrode is made
For reference electrode, 0.1mol/LNa2SO4Solution is used as ionic strength buffer.
F-The measure of concentration uses ion selective electrode method, with F-Select electrode as indicator electrode, calomel electrode is used as ginseng
Than electrode, 0.5mol/L sodium citrate -0.4mol/L sulfosalicylic acid -0.1mol/L disodium ethylene diamine tetraacetates are strong as ion
Degree regulation cushioning liquid.
Embodiment 1
Cationic polymerization is taken to produce in resin process, the boracic, fluorine-containing organic produced after neutralized, washing Removal of catalyst
Waste water (waste water containing boron trifluoride complex) 100ml, wherein, BF4 -Concentration is about 1610mg/L, F-Concentration is about 4956mg/
L, COD are about 4768mg/L, and PH is about 10 or so.
At room temperature (20 DEG C -25 DEG C) first into waste water add 1.43g potassium hydrogen persulfates, 8.8g ferric nitrates (molecular weight=
241.86) it is, stirring while adding, 10min is sufficiently stirred for, 20min is stood, after layering to be precipitated, supernatant is separated, detects supernatant
Liquid：BF4 -Concentration is about 182mg/L, F-Concentration is about 165mg/L, and COD is about 2061mg/L.
At room temperature (20 DEG C -25 DEG C), then into supernatant alum (molecular weight=474.4) 0.184g is added, is added
0.056g potassium chloride (molecular weight=74.5), adds 0.102g calcium chloride (molecular weight=111), adds the life of 0.2g microbial fermentations
Into the water-soluble biological flocculant of mixing (water-soluble r- polyglutamic acids mass percent is 5%), stir while adding, fully stir
10min is mixed, 20min is stood, after layering to be precipitated, supernatant is separated, detects supernatant：BF4 -Concentration is about 6mg/L, F-Concentration
About 8mg/L, COD are 2043mg/L.
Embodiment 2
Cationic polymerization is taken to produce in resin process, the boracic, fluorine-containing organic produced after neutralized, elution Removal of catalyst
Waste water (waste water containing boron trifluoride complex) 100ml, wherein, BF4 -Concentration is about 1610mg/L, F-Concentration is about 4956mg/
L, COD are about 4768mg/L, and PH is about 10 or so.
In the range of 10 DEG C -20 DEG C of temperature, 0.238g potassium hydrogen persulfates, 2.9g ferric sulfate (molecules are first added into waste water
Amount=399.86), it is stirring while adding, 20min is sufficiently stirred for, 30min is stood, after layering to be precipitated, separated in supernatant, detection
Clear liquid：BF4 -Concentration is about 324mg/L, F-Concentration is about 275mg/L, and COD is about 2832mg/L.
Alum (molecular weight=474.4) 0.109g is added in the range of 10 DEG C -20 DEG C of temperature, then into supernatant, is added
0.026g potassium chloride (molecular weight=74.5), adds 0.17g calcium chloride (molecular weight=111), adds the life of 0.02g microbial fermentations
Into the water-soluble biological flocculant of mixing (water-soluble r- polyglutamic acids mass percent is 5%), stir while adding, fully stir
20min is mixed, 30min is stood, after layering to be precipitated, supernatant is separated, detects supernatant：BF4 -Concentration is about 8mg/L, F-Concentration
About 7mg/L, COD are 2815mg/L.
Embodiment 3
Cationic polymerization is taken to produce in resin process, the boracic, fluorine-containing organic produced after neutralized, elution Removal of catalyst
Waste water (waste water containing boron trifluoride complex) 100ml, wherein, BF4 -Concentration is about 1610mg/L, F-Concentration is about 4956mg/
L, COD are about 4768mg/L, and PH is about 10 or so.
In the range of 40 DEG C -50 DEG C of temperature, 0.715g potassium hydrogen persulfates, 2.35g iron chloride (molecules are first added into waste water
Amount=162.2), it is stirring while adding, 30min is sufficiently stirred for, 20min is stood, after layering to be precipitated, separated in supernatant, detection
Clear liquid：BF4 -Concentration is about 187mg/L, F-Concentration is about 179mg/L, and COD is about 2832mg/L.
Aluminum sulfate (molecular weight=342.15) 0.068g is added in the range of 40 DEG C -50 DEG C of temperature, then into supernatant, plus
Enter 0.03g potassium chloride (molecular weight=74.5), add 0.165g calcium chloride (molecular weight=111), add 0.05g microbial fermentations
The water-soluble biological flocculant of the mixing of generation (polylalanine mass percent is 5%), stirs while adding, is sufficiently stirred for
30min, stands 20min, after layering to be precipitated, separates supernatant, detects supernatant：BF4 -Concentration is about 8mg/L, F-Concentration is about
For 5mg/L, COD is 2815mg/L.
Embodiment 4
Cationic polymerization is taken to produce in resin process, the boracic, fluorine-containing organic produced after neutralized, elution Removal of catalyst
Waste water (waste water containing boron trifluoride complex) 100ml, wherein, BF4 -Concentration is about 1610mg/L, F-Concentration is about 4956mg/
L, COD are about 4768mg/L, and PH is about 10 or so.
At room temperature (20 DEG C -25 DEG C), the first addition 0.96g potassium permanganate into waste water, 4.4g ferric nitrates (molecular weight=
241.85) it is, stirring while adding, 45min is sufficiently stirred for, 20min is stood, after layering to be precipitated, supernatant is separated, detects supernatant
Liquid：BF4 -Concentration is about 145mg/L, F-Concentration is about 91mg/L, and COD is about 2756mg/L.
At room temperature (20 DEG C -25 DEG C), then into supernatant aluminum nitrate (molecular weight=375.13) 0.08g is added, is added
0.04g potassium chloride (molecular weight=74.5), adds 0.12g calcium chloride (molecular weight=111), adds the life of 0.04g microbial fermentations
Into the water-soluble biological flocculant of mixing (poly-aspartate mass percent is 5%), stir while adding, be sufficiently stirred for
45min, stands 20min, after layering to be precipitated, separates supernatant, detects supernatant：BF4 -Concentration is about 8mg/L, F-Concentration is about
For 5mg/L, COD is 2714mg/L.
Comparative example 1
Cationic polymerization is taken to produce in resin process, the boracic, fluorine-containing organic produced after neutralized, elution Removal of catalyst
Waste water (waste water containing boron trifluoride complex) 100ml, wherein, BF4 -Concentration is about 1610mg/L, F-Concentration is about 4956mg/
L, COD are about 4768mg/L, and PH is about 10 or so.
At room temperature (20 DEG C -25 DEG C), first into waste water, addition 0.5g hydrogen peroxide is stirring while adding, is sufficiently stirred for 30min,
20min is stood, after layering to be precipitated, supernatant is separated, detects supernatant：BF4 -Concentration is about 1532mg/L, F-Concentration is about
4942mg/L, COD are about 2432mg/L.Addition hydrogen peroxide, which makees oxidant, can only reduce COD, it is virtually impossible to reduce boron, fluorine ion
Concentration.
At room temperature (20 DEG C -25 DEG C), then into supernatant aluminum sulfate (molecular weight=342.15) 0.7g is added, is added
1.5g potassium chloride (molecular weight=74.5), adds 4.5g calcium chloride (molecular weight=111), adds 0.2g polyacrylamides, Bian Jia
Enter side stirring, be sufficiently stirred for 30min, stand 20min, after layering to be precipitated, separate supernatant, detect supernatant：BF4 -Concentration is about
For 76mg/L, F-Concentration is about 94mg/L, and COD is 2413mg/L.
Comparative example 2
Cationic polymerization is taken to produce in resin process, the boracic, fluorine-containing organic produced after neutralized, elution Removal of catalyst
Waste water (waste water containing boron trifluoride complex) 100ml, wherein, BF4 -Concentration is about 1610mg/L, F-Concentration is about 4956mg/
L, COD are about 4768mg/L, and PH is about 10 or so.
Temperature first adds 0.715g potassium hydrogen persulfates, 2.35g iron chloride (molecules in the range of 30 DEG C -40 DEG C into waste water
Amount=162.2), it is stirring while adding, 30min is sufficiently stirred for, 20min is stood, after layering to be precipitated, separated in supernatant, detection
Clear liquid：BF4 -Concentration is about 127mg/L, F-Concentration is about 119mg/L, and COD is about 2832mg/L.
Temperature adds 0.03g potassium chloride (molecular weight=74.5) in the range of 30 DEG C -40 DEG C, then into supernatant, adds
0.1g calcium chloride (molecular weight=111), adds water-soluble biological flocculant (the poly L- third of mixing of 0.2g microbial fermentations generation
Propylhomoserin mass percent is sufficiently stirred for 30min 5%), to stir while adding, and 20min is stood, after layering to be precipitated, in separation
Clear liquid, detects supernatant：BF4 -Concentration is about 23mg/L, F-Concentration is about 35mg/L.Experimental result illustrates, is added without hydrolytic reagent
(such as aluminum sulfate), can influence boracic, the treatment effect of fluorine waste water, and COD is 2809mg/L.
Comparative example 3
Cationic polymerization is taken to produce in resin process, the boracic, fluorine-containing organic produced after neutralized, elution Removal of catalyst
Waste water (waste water containing boron trifluoride complex) 100ml, wherein, BF4 -Concentration is about 1610mg/L, F-Concentration is about 4956mg/
L, COD are about 4768mg/L, and PH is about 10 or so.
In the range of 10 DEG C -20 DEG C of temperature, 2.9g ferric sulfate (molecular weight=399.86), side edged are first added into waste water
Stirring, is sufficiently stirred for 20min, stands 30min, after layering to be precipitated, separates supernatant, detects supernatant：BF4 -Concentration is about
911mg/L, F-Concentration is about 398mg/L, and COD is about 4739mg/L.
Alum (molecular weight=474.4) 0.34g is added in the range of 10 DEG C -20 DEG C of temperature, then into supernatant, is added
0.09g potassium chloride (molecular weight=74.5), adds 0.27g calcium chloride (molecular weight=111), adds the life of 0.02g microbial fermentations
Into the water-soluble biological flocculant of mixing (water-soluble r- polyglutamic acids mass percent is 5%), stir while adding, fully stir
20min is mixed, 30min is stood, after layering to be precipitated, supernatant is separated, detects supernatant：BF4 -Concentration is about 38mg/L, F-Concentration
About 7mg/L, COD are 4733mg/L.Experimental result illustrates, is added without oxidant, can influence waste water COD and BF4 -The place of ion
Effect is managed, COD does not almost decline, BF4 -Ion concentration is also not reaching to discharge standard.
In summary, the present invention use oxidant sylvite (such as potassium hydrogen persulfate) and trivalent iron salt compounding as oxidant with
Precipitating reagent, the BF in processing waste water4 -, F-While, COD contents are reduced, handling process is simplified, improves treatment effeciency；It is logical
Compounding hydrolytic reagent, precipitating reagent, water-soluble biological flocculant are crossed, hydrolysis, precipitation, the efficiency of flocculation is improved, shortens wastewater treatment
Time；The inventive method need not add PH conditioning agents, adjust pH value；Using biological flocculant, it can avoid causing secondary pollution.
The protection content of the present invention is not limited to above example.Under the spirit and scope without departing substantially from inventive concept, this
Art personnel it is conceivable that change and advantage be all included in the present invention, and using appended claims as protect
Protect scope.
Claims (10)
1. the processing method of a kind of boracic, fluorine containing organic waste water, it is characterised in that the described method comprises the following steps：
(1) oxidant sylvite and water-soluble molysite are added into pending waste water, is carried out after oxidation reaction and precipitation reaction, it is quiet
Put precipitation and separation；
(2) after precipitation separation, hydrolytic reagent aluminium salt, precipitating reagent calcium salt and sylvite, water-soluble biological flocculant are added in supernatant,
Carry out after precipitation reaction and flocculation reaction, separation of solid and liquid, the waste water after being handled.
2. according to the method described in claim 1, it is characterised in that in step (1), the pH value of the waste water is between 9-11.
3. according to the method described in claim 1, it is characterised in that in step (1), the sylvite is selected from potassium hydrogen persulfate, height
One or both of potassium manganate；The quality of the sylvite is 0.5-3 times of COD gross masses in waste water.
4. according to the method described in claim 1, it is characterised in that in step (1), the molysite be selected from ferric nitrate, ferric sulfate,
One or more in ferric trichloride；Fe in the molysite3+Molal quantity is 0.4-2 times of fluorinion in waste water molar equivalent.
5. according to the method described in claim 1, it is characterised in that in step (1), the precipitation reaction is carried out under agitation；
The temperature of the precipitation reaction is 10 DEG C -50 DEG C, and the reaction time is no less than 10min；In step (2), the precipitation reaction and wadding
Solidifying reaction is carried out under agitation, and the temperature of the precipitation reaction and flocculation reaction is 10 DEG C -50 DEG C, and the reaction time is no less than
10min。
6. according to the method described in claim 1, it is characterised in that in step (2), the hydrolytic reagent aluminium salt is selected from alum, sulphur
One or more in sour aluminium, aluminum nitrate or its hydrate；In the aluminium salt and supernatant the mol ratio of fluoboric acid root for (1~
3)：1.
7. according to the method described in claim 1, it is characterised in that in step (2), the calcium salt is water-soluble Ca salt, it is selected from
One or more in calcium chloride, calcium oxide, calcium nitrate；The molal quantity of the calcium salt is fluorine ion molar equivalent in supernatant
1-3 times.
8. according to the method described in claim 1, it is characterised in that in step (2), the sylvite is water-soluble sylvite, it is selected from
For the one or more in potassium chloride, potassium nitrate, potassium phosphate；The molal quantity of the sylvite is fluoboric acid ion mole in supernatant
0.5-2 times of equivalent.
9. according to the method described in claim 1, it is characterised in that in step (2), the water-soluble biological flocculant is water-soluble
Property the protein-based biological flocculant containing hydrophobic amino acid, average weight-average molecular weight be 50-200 ten thousand；The water-soluble biological wadding
The quality of solidifying agent is the 0.001%-0.01% of wastewater quality.
10. according to the method described in claim 1, it is characterised in that in step (2), the water-soluble biological flocculant is selected from
One or more in water-soluble r- polyglutamic acids, polyglycine, poly-aspartate, polylalanine.
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| CN110453097B (en) * | 2019-09-17 | 2021-12-17 | 广东先导稀材股份有限公司 | Method for distilling and extracting germanium from fluorine-containing germanium concentrate |
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