CN109133419A - A kind of efficient coagulation method of the pre-oxidation-for the desized wastewater containing polyvinyl alcohol - Google Patents
A kind of efficient coagulation method of the pre-oxidation-for the desized wastewater containing polyvinyl alcohol Download PDFInfo
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- 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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02F1/722—Oxidation by peroxides
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/38—Polymers
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- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses one kind to be directed to (the Polyvinyl alcohol containing polyvinyl alcohol, PVA) the efficient coagulation method of the pre-oxidation-of desized wastewater, it include: to adjust wastewater pH using hydrochloric acid or sulfuric acid, green vitriol solution and hydrogenperoxide steam generator are sequentially added in PVA waste water, it is stirred at room temperature, it is accurate to control degree of oxidation, the solid of venting preliminary sedimentation after standing.Wastewater pH is adjusted again using sodium hydroxide or potassium hydroxide, the inorganic flocculating agents such as calcium chloride or zinc chloride are added in supernatant, is first quickly gradually slowed down after stirring, so that the high molecular contaminants Quick Coagulation such as PVA.The present invention is by accurately controlling the degree of oxidation of PVA pollutant, so that great amount of hydroxy group radical oxidation is carboxyl or aldehyde, ketone structure, it is a kind of processing method of desized wastewater containing PVA easy to operate and economical and practical to be easy and fast to coagulation.
Description
Technical field
The present invention relates to a kind of efficient coagulation technologies of the pre-oxidation-for the processing of desized wastewater containing polyvinyl alcohol, belong to water
Process field has good development prospect in terms of the processing of dyeing waste water or other industrial wastewaters containing PVA.
Background technique
Polyvinyl alcohol (Polyvinyl alcohol, hereinafter referred to as PVA) has good film forming and adhesiveness, as
The primary raw material of textile sizing is applied to existing more than 70 years history of warp yarn sizing, still rarely has substitute so far.In dyeing and printing process
Before, for the part natural impurity on the slurry and cotton fiber on removal cotton, it is necessary to carry out desizing.According to statistics, China is spun every year
The PVA amount of slurry consumption is knitted up to 250,000 t or more, the desized wastewater generated every year is more up to ten thousand t more than 2500, causes to environment
Huge pressure.
Desized wastewater biodegradability containing PVA is poor, BOD5/CODCrValue usually less than 0.1, traditional biochemical method handles difficult
It is imitated with gathering.Since PVA is in electroneutral, gel method treatment effect of only saltouing in conventional physico-chemical process is relatively preferable, mainly utilizes
Borax is crosslinked with PVA molecule to react, and forms the gel of the double diol type structures of PVA- borax.Although the method is to PVA desizing
The COD removal efficiency of waste water is ideal, but the gel water content generated is larger, and subsequent processing is difficult.In addition, PVA is typical case
High molecular polymer, it is also difficult to it is separated using traditional membrane separation technique, under the film permeation flux as caused by fouling membrane
Drop and reduced service life are major technology bottleneck.High-level oxidation technology (Advanced Oxidation Processes, referred to as
AOPs), the addition between the extremely strong free radical (such as OH) of activity and organic pollutant can be utilized, substitution, electronics transfer, broken
The effects of key, makes the hardly degraded organic substance in water body be degraded to CO2And H2O, organic wastewater with difficult degradation thereby is effectively reduced
COD value.However, textile sizing is higher (usually 1700 or so) with the degree of polymerization of PVA, and in desized wastewater also containing starch with
Other slurries such as sodium alginate and surfactant, fiber hair etc., the processing effect of the tradition high-level oxidation technology such as Fenton method
Rate is unsatisfactory.It improves oxidant concentration simply for qualified discharge, can not only be obviously improved treatment effeciency, will also generate
A large amount of iron cements or excessive oxidant bring secondary pollution.
To sum up, the reluctant main cause of waste water containing PVA is in addition to the high polymeric of PVA molecule, also because of in its structure
The great amount of hydroxy group group contained, so that PVA macromolecular is in electroneutral in aqueous solution, and hydrophily is stronger, it is difficult to using conventional
It is difficult to be dehydrated after the sedimentation of coagulating sedimentation technology and gel.Although the high-level oxidation technologies such as Fenton are difficult to the such high score of permineralization
Sub- polymer, but may make that a large amount of hydroxyl group is oxidized to carboxyl or aldehyde, ketone structure in PVA strand, thus be easy to often
Rule coagulant occurs electrostatic interaction or complexing and is able to rapid subsidence.
Summary of the invention
The object of the present invention is to provide a kind of methods of economy and facility to pre-oxidize to promote the desized wastewater containing PVA
Into the efficient coagulation of pollutant, so that the PVA concentration and COD value of desized wastewater are effectively reduced, slurry pollutant Quick Coagulation is simultaneously
Convenient for separation, to improve the low bottleneck of the treatment effeciency of desized wastewater containing PVA.
In order to achieve the above object, the technical solution of the present invention is to provide a kind of for the desized wastewater containing polyvinyl alcohol
The efficient coagulation method of pre-oxidation-, which comprises the following steps:
Desized wastewater pH value is adjusted using hydrochloric acid or sulfuric acid, successively by green vitriol solution and hydrogenperoxide steam generator
It is added in desized wastewater and is pre-oxidized, be stirred at room temperature, accurately control degree of oxidation, pass through primary sedimentation tank or pneumatically supported side
Formula removes solid precipitate；Desized wastewater pH value is then adjusted again using sodium hydroxide or potassium hydroxide, is added in supernatant
Enter inorganic flocculating agent, first quickly gradually slows down after stirring, so that macromolecule pollutant Quick Coagulation.
Preferably, the temperature of the desized wastewater is 30~50 DEG C, fabric slurry concentration range contained therein: polyethylene
Alcohol content is 5~10g/L, and the concentration of sodium alginate is 0~5g/L, and the concentration of starch is 0~5g/L.
Preferably, the adjustable range that the pH value of the desized wastewater is adjusted using the hydrochloric acid or sulfuric acid is 2~4.
Preferably, in the pre-oxidation, the mass concentration of the hydrogenperoxide steam generator is 30%, dosage 0.25wt%
~1.5wt%；The dosage of the green vitriol is 4g/L~10g/L.
Preferably, 30~60min of reaction time of the pre-oxidation.
Preferably, the dosage of the inorganic flocculating agent solution is 4~20g/L.
Preferably, mixing time when being stirred at room temperature is 5~15min；In first quickly gradually slowing down after stirring,
Quick mixing speed is 120rpm, is subsequently agitated for speed and gradually slows down to 30rpm.
Preferably, when adjusting the pH value of the desized wastewater again, the adjustable range of pH value is 8~12.
Preferably, when adjusting the pH value of the desized wastewater again, the sodium hydroxide or potassium hydroxide solution that use
Concentration be 0.1~4mol/L.
Preferably, the coagulation sedimentation time of macromolecule pollutant Quick Coagulation is 5~20min.
Compared with prior art, the beneficial effects of the present invention are: the present invention carries out at normal temperatures and pressures, utilizes advanced oxygen
Hydroxyl group a large amount of in PVA strand is oxidized to carboxyl or aldehyde, ketone structure by change technology, to be easy to send out with conventional coagulant
It gives birth to electrostatic interaction or complexing and is able to rapid subsidence.The method is simple, easy to operate, environmental-friendly, can significantly improve
The COD removal efficiency of the desized wastewater containing PVA, there is very big application potential in textile-dyeing wastewater process field.
Detailed description of the invention
Fig. 1 is to carry out pre-oxidizing-coagulation the phenomenon that handling figure, moving back before processing using practical desized wastewater containing polyvinyl alcohol
Pulp waste water as shown in the first from left in figure, solution be creamy white it is thick, it is molten by pre-oxidation containing a large amount of white flock bodies
Liquid layering, upper layer are PVA and Fe3+, liquid color is in yellowish-brown color, and the wadding body that lower layer is part PVA precipitates；Add flocculant into
After row coagulation, wastewater supernatant fluid clarification divides the macromoleculars such as PVA, sodium alginate, the starch in water, is added in preoxidation process
Iron ion is most of by polymeric precipitation, and the COD in desized wastewater is substantially reduced, and lower sediment is in dark brown.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
The desized wastewater 100mL that concentration containing PVA is 10g/L, sodium alginate concentration 2g/L, starch concentration are 2g/L is taken,
The pH for adjusting PVA solution is 3, and 1.08g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into,
It is stirred 30min at 30 DEG C, is staticly settled after stirring, lower sediment thing is removed, again adjusting pH value of solution to alkalinity,
Flocculant calcium chloride 2.0g is added, is stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Embodiment 2
The desized wastewater 100mL that concentration containing PVA is 10g/L, sodium alginate concentration 2g/L, starch concentration are 2g/L is taken,
The pH for adjusting PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into,
It is stirred 30min at 30 DEG C, is staticly settled after stirring, lower sediment thing is removed, again adjusting pH value of solution to alkalinity,
Flocculant calcium chloride 2.0g is added, is stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Embodiment 3
The desized wastewater 100mL that concentration containing PVA is 10g/L, sodium alginate concentration 2g/L, starch concentration are 2g/L is taken,
The pH for adjusting PVA solution is 3, and 0.6g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into,
It is stirred 30min at 30 DEG C, is staticly settled after stirring, lower sediment thing is removed, again adjusting pH value of solution to alkalinity,
Flocculant calcium chloride 2.0g is added, is stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Comparative example 1
The desized wastewater 100mL that concentration containing PVA is 10g/L, sodium alginate concentration 2g/L, starch concentration are 2g/L is taken,
The pH for adjusting PVA solution is 3, and 2.0g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into,
It is stirred 30min at 30 DEG C, is staticly settled after stirring, lower sediment thing is removed, again adjusting pH value of solution to alkalinity,
Flocculant calcium chloride 2.0g is added, is stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Comparative example 2
The desized wastewater 100mL that concentration containing PVA is 10g/L, sodium alginate concentration 2g/L, starch concentration are 2g/L is taken,
The pH for adjusting PVA solution is 3, and 0.2g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into,
It is stirred 30min at 30 DEG C, is staticly settled after stirring, lower sediment thing is removed, again adjusting pH value of solution to alkalinity,
Flocculant calcium chloride 2.0g is added, is stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Comparative example 3
The desized wastewater 100mL that concentration containing PVA is 10g/L, sodium alginate concentration 2g/L, starch concentration are 2g/L is taken,
The pH for adjusting PVA solution is 3, and 30min is stirred at 30 DEG C, staticly settles after stirring, lower sediment thing is removed,
PH value of solution is adjusted again to alkalinity, is added flocculant calcium chloride 2.0g, is stirred evenly at 30 DEG C, to stand after reaction,
Measure the removal rate of PVA in supernatant, sodium alginate, starch and COD.
It takes respectively and PVA, sodium alginate, shallow lake is carried out by the supernatant of embodiment 1,2,3 and comparative example 1,2,3 after the reaction
The measurement of the removal rate of COD in powder and desized wastewater solution, the results are shown in Table 1 for removal.
Influence of the 1 green vitriol dosage of table to the treatment effeciency of desized wastewater containing PVA
As shown in Table 1, when the quality of the green vitriol added is between 0.6g~1.08g, the removal rate of PVA
It is all relatively good with the removal rate of COD.When green vitriol dosage is very few, it is catalyzed H2O2Decompose the energy for generating OH
Power is insufficient；When its dosage is excessive, Fenton reacts remaining Fe2+Competitive OH can be consumed, oxidation efficiency can also reduce；
The reaction speed that will lead to oxidation PVA slows down, and oxidation efficiency reduces, and is not enough to for the great amount of hydroxy group in PVA structure being oxidized to
The structures such as carboxylic, aldehyde, ketone, so that the coagulation efficiency of second stage is decreased obviously.As shown in comparative example 3, do not pre-oxidized
It is directly flocculated using conventional method, except part sodium alginate and a small amount of starch can be moved back with calcium ion complexing and in addition to precipitating
The removal of PVA and COD in pulp waste water are all very low.It can be seen that controlling the pre-oxidation of PVA in effective range, PVA is tied
- OH in structure is oxidized to the structures such as carboxylic, aldehyde, ketone, so that it easily interacts with flocculant, thus effectively enhancing coagulation effect
Fruit.
Embodiment 4
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 30min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 2.0g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Embodiment 5
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 45min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 2.0g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Embodiment 6
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 60min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 2.0g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Comparative example 4
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, is slow added into2ML hydrogenperoxide steam generator, 30
It is stirred 15min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 2.0g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Comparative example 5
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 120min at DEG C, is staticly settled after stirring, lower sediment thing is removed, again adjusting pH value of solution to alkalinity,
Flocculant calcium chloride 2.0g is added, is stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
It takes respectively and PVA, sodium alginate, starch is carried out by the supernatant of embodiment 4,5,6 and comparative example 4,5 after the reaction
And in desized wastewater solution the removal rate of COD measurement, removal the results are shown in Table 2.
Influence of the 2 pre-oxidation time of table to the treatment effeciency of desized wastewater containing PVA
As shown in Table 2, when Fenton preoxidation time is between 30min~60min, the removal rate of PVA and its COD
All very high, effect is preferable.When there was only 15min between when reacted, preoxidation degree is inadequate, and being not enough to will be a large amount of in PVA structure
Hydroxyl is oxidized to the structures such as carboxylic, aldehyde, ketone, so that the coagulation efficiency of second stage is decreased obviously；It crosses and is up between when reacted
When to 120min, PVA is excessively oxidated, and except hydroxyl-removal group is oxidized, strand is oxidized degradation, forms molecular weight phase
To lesser intermediate product, it is unfavorable for the coagulation of second stage, causes COD removal rate not high.
Embodiment 7
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 30min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 2.0g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Embodiment 8
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 4mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 30min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 2.0g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Comparative example 6
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 1mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 30min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 2.0g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Comparative example 7
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 10mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 30min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 2.0g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
By changing Fe2+/H2O2Ratio, study H2O2Dosage to pre-oxidation effect influence.Change Fe respectively2+/
H2O2Molar ratio be respectively 1.36,2.72,5.44,13.6, take the supernatant after the reaction by embodiment 7,8 and comparative example 6,7
The measurement of the removal rate of COD in progress PVA, sodium alginate, starch and desized wastewater solution, the results are shown in Table 3 for removal.
3 H of table2O2Influence of the dosage to the treatment effeciency of desized wastewater containing PVA
As shown in Table 3, work as Fe2+/H2O2Molar ratio between 2.72~5.44 when, for desized wastewater pre-oxidation imitate
Fruit is good.Work as H2O2When dosage is too low, preoxidation degree is lower, be not enough to for the great amount of hydroxy group in PVA structure being oxidized to carboxylic,
The structures such as aldehyde, ketone, so as to be decreased obviously PVA degradation rate lower for the coagulation efficiency of second stage；Work as H2O2Dosage is excessively high
When, PVA is oxidized excessively, and except hydroxyl-removal group is oxidized, strand is oxidized degradation, and it is relatively small to form molecular weight
Intermediate product interrupts to form small molecule, and the coagulation flocculating effect for being unfavorable for second stage is deteriorated, and causes COD removal rate not high.
Embodiment 9
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 2, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 30min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 2.0g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Embodiment 10
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 30min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 2.0g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Embodiment 11
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 4, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 30min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 2.0g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Comparative example 8
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 5, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 30min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 2.0g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Taken in embodiment 9,10,11 and comparative example 8 supernatant after the reaction carry out PVA, sodium alginate, starch with
And in desized wastewater solution the removal rate of COD measurement, removal the results are shown in Table 4.
Table 4 pre-oxidizes influence of the pH to the treatment effeciency of desized wastewater containing PVA
As shown in Table 4, when pH is 2~4, PVA, COD removal rate highest in desized wastewater.When pH value is excessively high, H2O2Point
It solves and too fast causes decomposition, and Fe in solution2+It is precipitated in the form of hydroxide and loses catalytic capability, lead to desized wastewater
Middle PVA degradation rate is low.
Embodiment 12
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 30min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 1.0g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Embodiment 13
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 30min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 1.5g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Embodiment 14
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 30min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 2.0g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Comparative example 9
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 30min at DEG C, is staticly settled after stirring, lower sediment thing is removed, again adjusting pH value of solution to alkalinity,
It is stirred evenly at 30 DEG C, to stand after reaction, measures the removal rate of PVA in supernatant, sodium alginate, starch and COD.
Comparative example 10
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 30min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 0.2g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
Comparative example 11
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 30min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusts pH value of solution again to alkalinity, throws
Add flocculant calcium chloride 4.0g, stirred evenly at 30 DEG C, to stand after reaction, measures PVA, alginic acid in supernatant
The removal rate of sodium, starch and COD.
The input amount for changing flocculant calcium chloride in embodiment 12,13,14 and comparative example 9,10,11 is flocculated.
Take supernatant carry out PVA, sodium alginate, in starch and desized wastewater solution the removal rate of COD measurement, remove division result such as table
Shown in 5.
Influence of 5 flocculant dosage of table to the treatment effeciency of desized wastewater containing PVA
As shown in Table 5, from the point of view of comparative example 9, inorganic flocculating agent is not added after pre-oxidation, the removal rate of the PVA in waste water
It is very high, but the removal rate of COD is lower, and this illustrates that the PVA molecule in solution has become fundamental property (great amount of hydroxy group after pre-oxidizing
Being oxidized can not be in conjunction with color developing agent), but its carbochain keeps stabilization that mineralising does not occur.In conjunction with comparative example 3, it can be deduced that,
Pre-oxidation and the removal of flocculant added to the desized wastewater containing PVA appropriate all have a major impact.When flocculant dosage exists
When 0.5~2.0g, flocculating effect is all good, but flocculant dosage, since flocculation dosage is very little, causes in solution in 0.2g
PVA molecule is not flocculated completely, and COD value is higher；But when flocculant concentration excess, flocculant can become stable colloid again,
Reaction efficiency is caused to reduce.
Comparative example 12
The desized wastewater 100mL that concentration containing PVA is 5g/L, sodium alginate concentration 1g/L, starch concentration are 2g/L is taken, is adjusted
The pH for saving PVA solution is 3, and 0.8g green vitriol is dissolved in wherein, 2mL hydrogenperoxide steam generator is slow added into, 30
It is stirred 30min at DEG C, is staticly settled after stirring, lower sediment thing is removed, adjusting pH value of solution again is 5, is added
Flocculant calcium chloride 2.0g, stirs evenly at 30 DEG C, to stand after reaction, measure supernatant in PVA, sodium alginate,
The removal rate of starch and COD.
PH when changing flocculating setting in embodiment 14 is 8,9,10, and pH is 5 when flocculating setting in comparative example 12, respectively
Take supernatant carry out PVA, sodium alginate, in starch and desized wastewater solution the removal rate of COD measurement, remove division result such as table
Shown in 6.
Influence of the pH to the treatment effeciency of desized wastewater containing PVA when 6 flocculating setting of table
As shown in Table 6, when flocculation precipitation reaction adjusts pH 8~10, in desized wastewater PVA, sodium alginate, starch with
And the removal rate of COD is relatively high.Since solubility is lower under alkaline condition for calcium ion and zinc ion, after they and pre-oxidation
PVA, after sodium alginate and starch combines, be easier to be precipitated and Quick Coagulation from waste water.
Claims (10)
1. a kind of efficient coagulation method of pre-oxidation-for the desized wastewater containing polyvinyl alcohol, which is characterized in that including following step
It is rapid:
Desized wastewater pH value is adjusted using hydrochloric acid or sulfuric acid, green vitriol solution and hydrogenperoxide steam generator are sequentially added
It is pre-oxidized in desized wastewater, is stirred at room temperature, accurately control degree of oxidation, gone by primary sedimentation tank or pneumatically supported mode
Except solid precipitate；Desized wastewater pH value is then adjusted again using sodium hydroxide or potassium hydroxide, and nothing is added in supernatant
Machine flocculant first quickly gradually slows down after stirring, so that macromolecule pollutant Quick Coagulation.
2. a kind of efficient coagulation method of pre-oxidation-for the desized wastewater containing polyvinyl alcohol as described in claim 1, feature
It is, the temperature of the desized wastewater is 30~50 DEG C, fabric slurry concentration range contained therein: polyvinyl alcohol content 5
~10g/L, the concentration of sodium alginate are 0~5g/L, and the concentration of starch is 0~5g/L.
3. a kind of efficient coagulation method of pre-oxidation-for the desized wastewater containing polyvinyl alcohol as described in claim 1, feature
It is, the use of the adjustable range that the hydrochloric acid or sulfuric acid adjust the pH value of the desized wastewater is 2~4.
4. a kind of efficient coagulation method of pre-oxidation-for the desized wastewater containing polyvinyl alcohol as described in claim 1, feature
It is, in the pre-oxidation, the mass concentration of the hydrogenperoxide steam generator is 30%, and dosage is 0.25wt%~1.5wt%；
The dosage of the green vitriol is 4g/L~10g/L.
5. a kind of efficient coagulation method of pre-oxidation-for the desized wastewater containing polyvinyl alcohol as described in claim 1, feature
It is, 30~60min of reaction time of the pre-oxidation.
6. a kind of efficient coagulation method of pre-oxidation-for the desized wastewater containing polyvinyl alcohol as described in claim 1, feature
It is, the dosage of the inorganic flocculating agent solution is 4~20g/L.
7. a kind of efficient coagulation method of pre-oxidation-for the desized wastewater containing polyvinyl alcohol as described in claim 1, feature
It is, mixing time when being stirred at room temperature is 5~15min；In first quickly gradually slowing down after stirring, speed is quickly stirred
Degree is 120rpm, is subsequently agitated for speed and gradually slows down to 30rpm.
8. a kind of efficient coagulation method of pre-oxidation-for the desized wastewater containing polyvinyl alcohol as described in claim 1, feature
It is, when adjusting the pH value of the desized wastewater again, the adjustable range of pH value is 8~12.
9. a kind of efficient coagulation method of pre-oxidation-for the desized wastewater containing polyvinyl alcohol as described in claim 1, feature
It is, when adjusting the pH value of the desized wastewater again, the concentration of the sodium hydroxide or potassium hydroxide solution that use is 0.1
~4mol/L.
10. a kind of efficient coagulation method of pre-oxidation-for the desized wastewater containing polyvinyl alcohol as described in claim 1, special
Sign is that the coagulation sedimentation time of macromolecule pollutant Quick Coagulation is 5~20min.
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