CN101830586B - Treatment method of high-concentration fluorine-contained industrial wastewater - Google Patents
Treatment method of high-concentration fluorine-contained industrial wastewater Download PDFInfo
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- CN101830586B CN101830586B CN201010186936XA CN201010186936A CN101830586B CN 101830586 B CN101830586 B CN 101830586B CN 201010186936X A CN201010186936X A CN 201010186936XA CN 201010186936 A CN201010186936 A CN 201010186936A CN 101830586 B CN101830586 B CN 101830586B
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Abstract
The present invention relates to a treatment method of high-concentration fluorine-contained industrial wastewater, belonging to the fields of environmental protection and petrochemical industry. The treatment method of high-concentration fluorine-contained industrial wastewater comprises the following steps of: washing fluoride salt wastewater in polyether ketone with water at 90 DEG C, wherein the weight is 4.0 ton/kettle and the concentration is 6000-10000 mg/L ; adding 91kg of CaO with mass fraction of 85 percent, 0.21kg of chitosan and 0.29kg of lignin to the water; stirring and reacting for 30 min; adding 40kg of CaCl2, 2kg of FeCl2, 2kg of AlCl3 and 0.4kg of polyacrylamide; then, stirring and reacting for 30 min; and detecting, draining, entering a settlement pond to settle, detecting and draining. Wastewater has high temperature reaching 80-90 DEG C, can reach standard by treatment at room temperature; and the invention also has the advantages of simple process, one time treatment, little use equipment, one time settlement, short time and very stable effluent concentration reaching the international first-level emission standard.
Description
Technical field
The invention belongs to environment protection and petrochemical industry, particularly a kind of disposable processing reaches the method for GB first discharge standard about high-concentration fluorine-contained trade effluent.
Background technology
In the polyetherketone production process, the F in the organic fluorocompound
-Quilt displacement back generates inorganic fluoride salt and is entrained in the product, and villiaumite spins off by washing then, and contains F in a large number
-The problem that has been processed into of waste water.Adopting evaporation mode that villiaumite is reclaimed is a kind of feasibility way.But wastewater flow rate is big, and the villiaumite mass content has only 0.6-0.7%, and the energy consumption height is very uneconomical.Existing fluorine-containing wastewater treatment method adopts electrochemical process, ionic adsorption exchange process, liquid-film method, chemical coagulation-sedimentation method, flocculence usually.But consider from aspects such as treatment process, facility investment, working cost and secondary pollutions, better with chemical coagulation-sedimentation method.Adopt chemical coagulation-sedimentation method, promptly in fluoride waste, add the method for unslaked lime, stirring, flocculating settling.The fluoride waste that mass content is 0.6%～0.7%, concentration is 6000～10000mg/L handled to be needed to handle several times below reaching GB emission standard 10mg/L, and technological process is loaded down with trivial details.Particularly when F-concentration reaches 15～17mg/L, reduce F
-Concentration is more difficult.It mainly is to utilize Ca that employing adds methods such as unslaked lime
2+With F
-Reaction generates the CaF that is insoluble in water
2Precipitation, thus F got rid of
-Pollution to discharge water.But (or other contain Ca to unslaked lime
2+Thing) water-soluble back forms Ca (OH)
2, be a kind of milk (can precipitate after rest time is long), free Ca
2+Ion is less relatively, and is even more important, because product C aF
2Particle is thinner, is coated on Ca (OH)
2Deng Ca is provided
2+The particulate outside in source stops F
-With Ca
2+Reaction.Although in handling stirring is arranged, effect is very not obvious.And, cause containing in this fluoride waste portion C O owing to add the excess carbon hydrochlorate in the reaction at the initial stage of production
3 2-, employing is added Ca
2+Method is handled F
-Very adverse influence is arranged again.Because Ca
2+With CO
3 2-Reaction generates the CaCO that granularity is thinner, the coating effect is stronger
3, further suppressed F
-With Ca
2+Reaction, and sedimentation time is long.Do not reach requirement even add the disposable processing of flocculation agent such as polyacrylamide, PFAS yet.
At above fluoride waste, we study by experiment, and through actual production, obtained high-concentration fluorine-contained trade effluent (general concentration in 6000～10000mg/L) disposable intensive treatment, reach the improvement method of GB emission standard.
Summary of the invention
At the deficiencies in the prior art and defective, the invention provides the disposable processing of a kind of high-concentration fluorine-contained waste water and reach the improvement method of GB emission standard.
The present invention is design like this:
1, a kind of improvement method of high-concentration fluorine-contained waste water, the waste water that villiaumite generates in the washing polyetherketone, temperature is that 90 ℃, heavily about 4.0 tons/still, concentration are 6000～10000mg/L.
Step 1 a. sends into fluoride waste in 4.0 tons of reactors 4, b. be mass percent 85% CaO 91kg, chitosan 0.21kg, xylogen 0.29kg pours in the troughing 1, c. open the still bottom valve and in troughing 1, put into fluoride waste, d. start beating motor 3 and stir three fens kinds, e. startup immediately then send stock pump 2, and slurries in the troughing 1 are all sent in the reactor 4, stop to send stock pump 2, f. starts the reactor agitator motor and stirred 30 minutes;
Step 2 a. continues to stir at the reactor agitator motor, pours 40kg CaCl into to troughing 1 simultaneously
2, 2kgFeCl
2, 2kg AlCl
3And 0.4kg polyacrylamide, b. when stopping to stir, opens by reactor 4 the still bottom valve, put into waste water to troughing again, close the still bottom valve after having put, c. start beating motor 3 and stir three fens kinds, d. start and send stock pump 2 all to squeeze in the reactor 4 again the mixed solution in the troughing 1, stop to send stock pump 2, e. starting for the second time the reactor agitator motor stirred 30 minutes, f. stir and finish back detection fluorinion concentration, fluorinion concentration is lower than 10mg/L and reaches requirement, can be that turbid liquid detects, g. then water mixed liquid in the reactor is put into settling bowl 5 sedimentations 1 hour, can be emitted waste water in the pond by going out water regulating valve 6.Emit F in the waste water this moment
-Concentration all is lower than 10mg/L, reaches the GB first discharge standard.This process is a chemical reaction precipitation-flocculence.
In addition, in the actual treatment, elder generation puts into troughing with the part fluorinated water and pulls an oar, and the partly precipitated thing then, pumps into stirring in the fluorinated water, reaction with lime white as the reaction crystal seed, and the treatment effect ratio is directly with better in the input reactors such as CaO.
Because the water-soluble back of CaO forms Ca (OH)
2, free Ca
2+Ion and F
-Reaction generates the thinner CaF of particle
2Precipitation.Be distributed in the aqueous solution after chitosan, xylogen are water-soluble, form the 3-d tree-like adsorbent, have bridgings, absorption, roll up and sweep, quicken settled effect.Secondary adds CaCl
2For with F
-Reaction generates CaF
2Precipitation provides more competent Ca
2+The source.Simultaneously, the FeCl that together adds
2, AlCl
3The Fe that can inhale mutually with the product microballoon is provided
2+, Al
3+, can further reduce Ca
2+Source absorption, increasing contain F
-The particle diameter of microballoon quickens settlement action.Polyacrylamide is a kind of obvious results flocculation agent, has promoted that effectively suspended substance is assembled and sedimentation in the water.
Experimentation: reactor is glass there-necked flask 500ml; Stirring velocity 60 commentaries on classics/min; 20 ℃, primary treatment adds medium CaO, settling velocity graduated cylinder.Production process: reactor industrial reaction still 4500L; Stirring velocity 60 commentaries on classics/min; 20 ℃, add medium: invention material and ratio.Settling velocity is with the scale settlement barrel with self-control.
The beneficial effect of this high-concentration fluorine-contained wastewater treatment is: (1) wastewater temperature height, 80 ℃～90 ℃ (normal temperature is handled also can be up to standard).(2) technology is simple, primary treatment.(3) use equipment is few, only needs a sedimentation.(4) time is short.Enter into and to discharge from waste water, be no more than 2.5 hours.(5) guarantee out that water concentration is lower than 10mg/L.As long as reinforced and according to the technological process operation according to this patent material, it is bad, very stable can fashion the time to go out water concentration.Rational allocation CaO, chitosan, xylogen, CaCl
2, FeCl
2, AlCl
3And the ratio of polyacrylamide, according to the operation of accompanying drawing technological process, concentration can reach the GB emission standard in the disposable processing of the fluoride waste of 6000～10000mg/L.
Description of drawings
Fig. 1 is sewage treatment technology process figure of the present invention.
1 is troughing among Fig. 1; 2 for sending stock pump; 3 is beating motor; 4 is reactor; 5 settling bowls; 6 go out water regulating valve
Embodiment
In detail a kind of improvement method of high-concentration fluorine-contained trade effluent is described with reference to the accompanying drawings below: the waste water that villiaumite generates in the washing polyetherketone, temperature are that 90 ℃, heavily about 4.0 tons/still, concentration are 6000～10000mg/L.
Step 1 a. at first sends into fluoride waste in 4.0 tons of reactors 4, as shown in Figure 1, b. is mass percent 85% CaO 91kg then, chitosan 0.21kg, xylogen 0.29kg, pour in the troughing 1, c. opens the still bottom valve and put into fluoride waste in troughing 1, and d. starts beating motor 3 and stirs three fens kinds, e. start immediately then and send stock pump 2, slurries in the troughing 1 are all sent in the reactor 4, stopped to send stock pump 2, f. starts the reactor agitator motor and stirred 30 minutes;
Step 2 a. continues to stir at the reactor agitator motor, pours 40kg CaCl into to troughing 1 simultaneously
2, 2kgFeCl
2, 2kg AlCl
3And 0.4kg polyacrylamide, b. when stopping to stir, opens by reactor 4 the still bottom valve, put into waste water to troughing again, close the still bottom valve after having put, c. start beating motor 3 and stir three fens kinds, d. start and send stock pump 2 all to squeeze in the reactor 4 again the mixed solution in the troughing 1, stop to send stock pump 2, e. starting for the second time the reactor agitator motor stirred 30 minutes, f. stir and finish back detection fluorinion concentration, fluorinion concentration is lower than 10mg/L and reaches requirement, can be that turbid liquid detects, g. water mixed liquid in the reactor is put into settling bowl 5 sedimentations 1 hour, can be emitted waste water in the pond by going out water regulating valve 6.Emit F in the waste water this moment
-Concentration all is lower than 10mg/L, reaches the GB first discharge standard.This process is a chemical reaction precipitation-flocculence.
In addition, in the actual treatment, elder generation puts into troughing with the part fluorinated water and pulls an oar, and the partly precipitated thing then, pumps into stirring in the fluorinated water, reaction with lime white as the reaction crystal seed, and the treatment effect ratio is directly with better in the input reactors such as CaO.
Because the water-soluble back of CaO forms Ca (OH)
2, free Ca
2+Ion and F
-Reaction generates the thinner CaF of particle
2Precipitation.Be distributed in the aqueous solution after chitosan, xylogen are water-soluble, form the 3-d tree-like adsorbent, have bridgings, absorption, roll up and sweep, quicken settled effect.Secondary adds CaCl
2For with F
-Reaction generates CaF
2Precipitation provides more competent Ca
2+The source.Simultaneously, the FeCl that together adds
2, AlCl
3The Fe that can inhale mutually with the product microballoon is provided
2+, Al
3+, can further reduce Ca
2+Source absorption, increasing contain F
-The particle diameter of microballoon quickens settlement action.Polyacrylamide is a kind of obvious results flocculation agent, has promoted that effectively suspended substance is assembled and sedimentation in the water.
Experimentation: reactor is glass there-necked flask 500ml; Stirring velocity 60 commentaries on classics/min; 20 ℃, primary treatment adds medium CaO, settling velocity graduated cylinder.Production process: reactor industrial reaction still 4500L; Stirring velocity 60 commentaries on classics/min; 20 ℃, add medium: invention material and ratio.Settling velocity is with the scale settlement barrel with self-control.
Rational allocation CaO, chitosan, xylogen, CaCl
2, FeCl
2, AlCl
3And the ratio of polyacrylamide, according to the operation of accompanying drawing technological process, concentration can reach the GB first discharge standard at the fluoride waste of 6000～10000mg/L through disposable intensive treatment.
The experiment of table 1 fluoride waste, production processing data (F
-Concentration is mg/L)
Claims (1)
1. the improvement method of a high-concentration fluorine-contained trade effluent, it is characterized in that, comprise the steps: that step 1 a. is that the fluoride waste of 6000mg/L～10000mg/L is sent in 4.0 tons of reactors (4) with concentration, b. be mass percent 85% CaO 91kg, chitosan 0.21kg, xylogen 0.29kg, pour in the troughing (1), c. open the still bottom valve and in troughing (1), put into fluoride waste, d. start beating motor (3) and stir three fens kinds, e. startup immediately then send stock pump (2), and the interior slurries of troughing (1) are all sent in the reactor (4), stop to send stock pump (2), f. starts the reactor agitator motor and stirred 30 minutes;
Step 2 a. reactor agitator motor continues to stir, and pours 40kg CaCl into to troughing (1) simultaneously
2, 2kg FeCl
2, 2kg AlCl
3And 0.4kg polyacrylamide, b. open the still bottom valve when stopping to stir when reactor (4), put into waste water to troughing again, close the still bottom valve after having put, c. start beating motor (3) and stir three fens kinds, d. start and send stock pump (2) that the mixed solution in the troughing (1) is all squeezed in the reactor (4) again, stop to send stock pump (2), e. starting for the second time the reactor agitator motor stirred 30 minutes, f. stir and finish back detection fluorinion concentration, fluorinion concentration is lower than 10mg/L and reaches requirement, g. then water mixture in the reactor is put into settling bowl (5) sedimentation after 1 hour, all sedimentation finishes, and improvement finishes, and emits waste water in the pond by going out water regulating valve (6) at last.
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|---|---|---|---|
| CN201010186936XA CN101830586B (en) | 2010-05-31 | 2010-05-31 | Treatment method of high-concentration fluorine-contained industrial wastewater |
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|---|---|---|---|
| CN201010186936XA CN101830586B (en) | 2010-05-31 | 2010-05-31 | Treatment method of high-concentration fluorine-contained industrial wastewater |
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| CN101830586A CN101830586A (en) | 2010-09-15 |
| CN101830586B true CN101830586B (en) | 2011-10-05 |
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| CN105016417A (en) * | 2015-03-05 | 2015-11-04 | 中霖中科环境科技（安徽）股份有限公司 | Water circulation treatment method for removal of fluorine ions in water |
| CN108911091A (en) * | 2018-07-24 | 2018-11-30 | 湖北蓝钴环保科技有限公司 | A kind of compound defluorinating agent and preparation method thereof |
| CN109626628A (en) * | 2018-12-07 | 2019-04-16 | 江西赣锋循环科技有限公司 | A kind of processing method of high fluorine waste water |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1765763A (en) * | 2004-10-28 | 2006-05-03 | 力晶半导体股份有限公司 | Method for treating fluorine-containing waste water |
| CN1962475A (en) * | 2006-12-05 | 2007-05-16 | 谢发达 | Method and device for treating fluorine-containing waste water using limestone |
| CN101402493A (en) * | 2008-10-31 | 2009-04-08 | 浙江汉盛氟化学有限公司 | Method for treating high-fluorine sewage water |
-
2010
- 2010-05-31 CN CN201010186936XA patent/CN101830586B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1765763A (en) * | 2004-10-28 | 2006-05-03 | 力晶半导体股份有限公司 | Method for treating fluorine-containing waste water |
| CN1962475A (en) * | 2006-12-05 | 2007-05-16 | 谢发达 | Method and device for treating fluorine-containing waste water using limestone |
| CN101402493A (en) * | 2008-10-31 | 2009-04-08 | 浙江汉盛氟化学有限公司 | Method for treating high-fluorine sewage water |
Non-Patent Citations (1)
| Title |
|---|
| 韩建勋等.含氟废水处理方法.《有机氟工业》.2004,(第3期),第27-36页. * |
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