CN107399779A - A kind of processing method of phenol wastewater - Google Patents
A kind of processing method of phenol wastewater Download PDFInfo
- Publication number
- CN107399779A CN107399779A CN201710675963.5A CN201710675963A CN107399779A CN 107399779 A CN107399779 A CN 107399779A CN 201710675963 A CN201710675963 A CN 201710675963A CN 107399779 A CN107399779 A CN 107399779A
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- Prior art keywords
- phenol
- quaternary ammonium
- processing method
- ammonium salt
- remover
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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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Abstract
The invention provides a kind of processing method of phenol wastewater, comprise the following steps：Phenol wastewater and remover are mixed and carry out dephenolize, is separated after stratification, obtains the dephenolize waste water of lower floor and the organic phase containing phenol on upper strata；The remover is organic quaternary ammonium salt compound.The processing method of phenol wastewater provided by the invention only needs by simple mixing and stands the efficient removal that can be achieved to Phenol, and does not have particular/special requirement to treatment temperature and processing pressure, can be achieved at normal temperatures and pressures.
Description
Technical field
The present invention relates to the technical field of wastewater treatment, more particularly to a kind of processing method of phenol wastewater.
Background technology
Phenol wastewater has caused by referring in the industrial productions such as coking, pharmacy, papermaking, pigment and petrochemical industry containing phenols
The waste water of machine thing, it is one of common industrial wastewater.Low concentration phenol wastewater and highly concentrated is divided into according to the concentration of contained pollutant
Phenol wastewater is spent, waste water of the usual phenol content more than 100mg/L is high-concentration phenolic wastewater.
At present, the processing method of phenol wastewater mainly has biological degradation method, solvent treatment method, active carbon adsorption, chemistry
Oxidizing process etc..Wherein biological degradation method is primarily adapted for use in low concentration phenol wastewater, the phenol and its derivatives in high phenol wastewater
There is stronger toxic action to microorganism, the bioactivity of microorganism is impacted very big, causes microorganism to be difficult to degrading phenol
Organic matter.
Extraction and active carbon adsorption are preferable to the treatment effect of high phenol wastewater, but extraction is for extracting environment
There is higher requirement with technique, phenol wastewater is generally alkalescence, and extracts except phenol needs to carry out in acid condition, so extraction
When need larger amount of acid, and extraction needs enough temperature, easily produces secondary pollution, extractant recovery be also required to compared with
High energy consumption；And active carbon adsorption has the shortcomings that easy saturation, parsing is difficult, and regeneration cost is high, also easily causes secondary
Pollution.
Therefore, existing phenolic wastewater treatment method is when handling high phenol wastewater, in the prevalence of intractability is big, place
Manage the problems such as efficiency is low, processing cost is high.
The content of the invention
In view of this, present invention aims at provide at the phenol wastewater that a kind of method is simple, cost is low, treatment effeciency is high
Reason method.Phenolic wastewater treatment method provided by the invention can be with the aldehydes matter in efficient removal waste water, and treatment effect is not
It can be influenceed by Phenol for Waste Water content.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of processing method of phenol wastewater, comprise the following steps：
Phenol wastewater and remover are mixed and carry out dephenolize, is separated after stratification, obtains the dephenolize waste water of lower floor and upper
The organic phase containing phenol of layer；
The remover is organic quaternary ammonium salt compound.
Preferably, the organic quaternary ammonium salt compound is organic quaternary ammonium carbonate, organic quaternary ammonium sulfate and organic season
One or more in ammonium salt hydrochlorate.
Preferably, the organic quaternary ammonium salt is long chain alkyl ammonium salt；
The long chain alkyl ammonium salt class compound is single-long-chain alkyl quaternary ammonium salt, double long-chain alkyl quaternary ammonium salt and three long-chains
One or more in alkyl quaternary ammonium salts；
The C atomicities of the chain alkyl are independently 6~9.
Preferably, the time of the dephenolize is 10~20min.
Preferably, the volume ratio of the remover and phenol wastewater is 1~10:1000.
Preferably, the time of the standing is 10~20min.
Preferably, the organic phase containing phenol is regenerated using regenerative agent；
The regenerative agent is the salting liquid containing carbonate, or the salting liquid containing sulfate radical, or the salt containing chlorion
Solution.
Preferably, the phenolic wastewater treatment is mixer-settler with device.
The invention provides a kind of processing method of phenol wastewater, comprise the following steps：Phenol wastewater and remover are mixed
Close and carry out dephenolize, separated after stratification, obtain the dephenolize waste water of lower floor and the organic phase containing phenol on upper strata；The remover is to have
Machine quaternary ammonium compound.The present invention is removed using organic quaternary ammonium salt compound to Phenol, treated
The anion in phenoxy group substitution organic quaternary ammonium salt in journey in material containing phenol, generation and the immiscible organic phase of water, then pass through
Simple stratification can will contain the organic phase separation of phenol, so as to reach the purpose for removing phenol from waste water, similar to extraction
Principle；The processing method of phenol wastewater provided by the invention is only needed by simple stirring and stood i.e. achievable to phenol wastewater
The efficient removal of middle phenol, and there is no particular/special requirement to treatment temperature processing pressure, it can be achieved at normal temperatures and pressures, and need not
The pH value of phenol wastewater is adjusted.Further, phenol wastewater of the present invention is handled using mixer-settler,
Automation continuous processing is easily realized, operating method is simple, and cost is low, easily carries out industrialized production.Embodiment result shows,
Processing method provided by the invention can be that the high phenol wastewater of 100~10000mg/L is effectively handled to phenol content, handle
Phenol for Waste Water content afterwards can be down to below 15mg/L, and phenol clearance can reach more than 99%, and COD value can drop to
Below 1500mg/L.
Embodiment
The invention provides a kind of processing method of phenol wastewater, comprise the following steps：
Phenol wastewater and remover are mixed and carry out dephenolize, is separated after stratification, obtains the dephenolize waste water of lower floor and upper
The organic phase containing phenol of layer；
The remover is organic quaternary ammonium salt compound.
Phenol wastewater and remover are mixed and carry out dephenolize, is separated after stratification, obtains the dephenolize waste water of lower floor and upper
The organic phase containing phenol of layer.In the present invention, the phenol wastewater is that the industry such as coking, pharmacy, papermaking, pigment and petrochemical industry is raw
Caused phenol wastewater in production, the concentration containing phenol of the phenol wastewater are about 100~10000mg/L, and COD value is 10000~
130000mg/L, phenol wastewater are generally neutral and alkali waste water, and pH value is 7~11.The present invention neutral and alkali condition (pH value be 7~
11) removing to Phenol can be achieved under, without the pH value of phenol wastewater is adjusted.
In the present invention, the remover is organic quaternary ammonium salt compound；The organic quaternary ammonium salt compound is preferred
Including the one or more in organic quaternary ammonium carbonate, organic quaternary ammonium sulfate and organic quaternary ammonium hydrochloride；The organic quaternary ammonium
Salt compounds are preferably long chain alkyl ammonium salt；The long chain alkyl ammonium salt preferably includes single-long-chain alkyl quaternary ammonium salt, double
One or more in long chain alkyl ammonium salt and tri-long-chain alkyl quaternary ammonium salt；The C atomicity independences of the chain alkyl it is excellent
Elect 6~9, more preferably 7~8 as；In an embodiment of the present invention, the organic quaternary ammonium salt compound can be specifically three
Octylmethylammonium chloride, tricaprylmethyl ammonium carbonate, tricaprylmethyl ammonium sulfate, three nonanylmethyl ammonium chlorides or three nonanylmethyls
Ammonium carbonate etc..
In the present invention, the organic quaternary ammonium salt compound is preferably liquid, can be directly added into application
In phenol wastewater.The present invention does not have particular/special requirement to the source of the organic quaternary ammonium salt compound, uses people in the art
The organic quaternary ammonium salt compound in the known source of member, it is specific such as commercial goods.
In the present invention, the addition of the remover is preferably determined according to Phenol content, in this hair
In bright specific embodiment, the volume ratio of the remover and phenol wastewater is preferably 1~10:1000, more preferably 2~8:
1000, most preferably 4~6:1000.
Preferably dephenolize under agitation of the invention, the rotating speed of the stirring is preferably 50~500rpm, and more preferably 100
~400rpm, most preferably 200~300rpm；The time of the stirring is preferably 10~20min, more preferably 13~18min,
Most preferably 15min.
After the dephenolize, the present invention will preferably separate after the material stratification after dephenolize, obtain the dephenolize waste water of lower floor
With the organic phase containing phenol on upper strata.In the present invention, the time of the standing is preferably 10~20min, more preferably 13~
18min, most preferably 15min.The present invention to separation used by specific method there is no particular/special requirement, use people in the art
, can be by dephenolize waste water and the method for organic phase separation containing phenol known to member.
In the present invention, the mixing, stirring, stratification and separation are all carried out under room temperature, normal pressure, without the volume of progress
Outer heating and cooling, without the extra pressure of application.
In the present invention, the aldehydes matter during mixing dephenolize in phenol wastewater can be anti-with organic quaternary ammonium salt compound
Should, the anion in phenoxy group substitution organic quaternary ammonium salt in material containing phenol, generation and the immiscible organic phase of water are (for example, go
When except agent being tricaprylmethyl ammonium carbonate, after phenol ring substitutes carbonate group, tricaprylmethyl ammonium carbonate generation tricaprylmethyl
Phenoxy group ammonium, tricaprylmethyl phenoxy group ammonium are organic phase containing phenol of the present invention), the density of gained organic phase containing phenol is small
Yu Shui, the organic phase separation of phenol can will be contained by simple stratification, so as to reach the purpose for removing phenol from waste water, class
It is similar to extract principle.
Present invention preferably uses the processing that mixer-settler carries out above-mentioned phenol wastewater.Knot of the present invention to mixer-settler
Structure does not have particular/special requirement, and use is well known to those skilled in the art, the conventional mixer-settler of extraction.In the present invention,
The series of the mixer-settler is preferably 2~6 grades, more preferably 4~5 grades, and every grade is a unit, is wrapped in each unit
Include mixed cell and clarification unit；The present invention does not have particular/special requirement to the volume of mixed cell and clarification unit, the present invention's
In specific embodiment, mixed cell can be determined according to the treating capacity of phenol wastewater and clarifies the volume of unit.
In the present invention, carrying out phenolic wastewater treatment using mixer-settler is specially：
Remover is pumped into mixer-settler from the light phase import of mixer-settler, from the heavy phase import of mixer-settler
Phenol wastewater is pumped into mixer-settler；Remover and phenol wastewater are mixed in mixed cell counter current contacting and by mechanical agitation
Close, nature clarification is carried out by gravity in clarification unit, after 2~6 grades of mixing clarifications, pumped out from light phase export organic containing phenol
Phase, dephenolize waste water is pumped out from heavy out.
In the present invention, the speed that is pumped into of the remover is preferably 1~4ml/min, more preferably 2.5ml/min；Institute
The speed that is pumped into for stating phenol wastewater is preferably 20~100ml/min, more preferably 50ml/min；The remover and phenol wastewater
The speed ratio that is pumped into be preferably 1:10~100, more preferably 1:20~40.The present invention is to being pumped into used in phenol wastewater and scavenger
Pump there is no particular/special requirement, it is specific such as peristaltic pump using pump well known to those skilled in the art.
In the present invention, continuous treatment can be realized by carrying out processing using mixer-settler progress phenol wastewater, be operated
It is easy.
In the present invention, the organic phase containing phenol after the dephenolize is preferably regenerated using regenerative agent, and the regenerative agent is excellent
Elect the salting liquid containing carbonate, or the salting liquid containing sulfate radical, or the salting liquid containing chlorion as；It is described to contain carbonic acid
The salting liquid of root is preferably the mixed solution or potassium carbonate and carbon of sodium carbonate liquor, solution of potassium carbonate, sodium carbonate and sodium acid carbonate
The mixed solution of the mixed solution of potassium hydrogen phthalate, more preferably sodium carbonate and sodium acid carbonate；The salting liquid containing sulfate radical is excellent
Elect metabisulfite solution or potassium sulfate solution as；The salting liquid containing chlorion is preferably that sodium chloride solution or potassium chloride are molten
Liquid.
The present invention is regenerated using regenerative agent to organic phase containing phenol, and acid ion substitutes organic phase containing phenol in regenerative process
In phenoxy group, so as to retrieve organic quaternary ammonium salt compound；The present invention does not have special want to the concentration of the regenerative agent
Ask, the phenoxy group in organic phase containing phenol can be substituted completely.
In a particular embodiment of the present invention, the regenerative agent is preferably the mixed solution of sodium carbonate and sodium acid carbonate；Institute
The concentration for stating sodium carbonate in mixed solution is preferably 1~4mol/L, more preferably 2~3mol/L；Carbonic acid in the mixed solution
The concentration of hydrogen sodium is preferably 0.5~2mol/L, more preferably 1~1.5mol/L；Sodium carbonate and bicarbonate in the mixed solution
The mol ratio of sodium is preferably 3~4:2, more preferably 3:2；The volume ratio of the mixed solution and the organic phase containing phenol is preferably 1:5
~10, more preferably 1:6~8.
In the present invention, the regeneration of the organic phase containing phenol preferably includes following steps：
To contain phenol organic phase and regenerative agent mixing after stir, separated after stratification, obtain upper strata regeneration remover and
The regenerative agent containing phenol of lower floor.
In the present invention, the rotating speed of the stirring is preferably 50~500rpm, more preferably 100~400rpm, most preferably
For 200~300rpm；The time of the stirring is preferably 30~60min, more preferably 40~50min, most preferably 45min；
The time of the standing is preferably 30~60min, more preferably 40~50min, most preferably 45min.
The present invention preferably sets regeneration unit in use in waste water treatment mixer-settler, the regeneration for the organic phase containing phenol；
The series of the regeneration unit is preferably 1~2 grade, and each regeneration unit includes mixed cell and clarification unit.In the present invention
Specific embodiment in, the organic phase containing phenol pumped out is pumped into regeneration unit, while regenerative agent is pumped into regeneration unit, contained
After phenol organic phase and regenerative agent carry out mixing clarification, obtain regenerating remover and regenerative agent containing phenol；Regeneration remover can circulate
Use.In the present invention, the speed that is pumped into of the organic phase containing phenol is preferably 5~15ml/min, more preferably 10ml/
min；The speed that is pumped into of the regenerative agent is preferably 0.5~2ml/min, more preferably 1ml/min；The organic phase containing phenol and again
The speed ratio that is pumped into of raw agent is preferably 1:8~12, more preferably 1:10.
In the present invention, the phenoxy group in organic phase containing phenol can be removed by regeneration, obtained regeneration remover can
To reuse；Obtained regenerative agent containing phenol contains phenol solution for high concentration, can pass through acidolysis separation or electrodialytic method
Reclaimed.
The processing method of phenol wastewater provided by the invention is described in detail with reference to embodiment, but can not
They are interpreted as limiting the scope of the present invention.
Embodiment 1
Raw water data：8560mg/L containing phenol, COD：36200mg/L, pH8.5；The mixer-settler used is extraction with often
Mixer-settler is advised, mixer-settler is 6 grades, and every grade is a unit；Unit includes mixed cell and quiet in each unit
Clarification unit is put, unit total measurement (volume) is 5 liters, and mixed cell is 1 liter, and it is 4 liters to stand unit；Remover is tricaprylmethyl carbonic acid
Ammonium；
Remover and phenol wastewater are pumped into simultaneously directly into device using peristaltic pump, it is 2.5mL/min to be pumped into remover,
It is 50mL/min to be pumped into waste water speed；It is to be pumped into phenol wastewater from the heavy liquid inlet of unit 1 to be pumped into direction, by the heavy out of unit 4
Dephenolize waste water is pumped out, remover is pumped into by the light phase inlet of unit 4, organic phase containing phenol is pumped out by the light phase export of unit 1, dephenolize is given up
Water carries out phenol content and COD value detection after collecting；
The organic phase containing phenol pumped out is pumped into buffer pool, then unit 5 is pumped directly into by buffer pool, regeneration is pumped into by unit 6
Agent (mol ratio 1:2 sodium carbonate and sodium acid carbonate mixed solution, concentration of sodium carbonate 1mol/L, sodium acid carbonate concentration are
2mol/L), the speed for being pumped into the organic phase containing phenol is 10mL/min, and the speed for being pumped into regenerative agent is 1mL/min, contains phenol after regeneration
Regenerative agent is discharged by unit 5, and regeneration remover is discharged by unit 6, is recycled.
Waste water after dephenolize：15mg/L containing phenol, COD1500mg/L.
Embodiment 2
Raw water data：2800mg/L containing phenol, COD：26200mg/L, pH8.7；The mixer-settler used is extraction with often
Mixer-settler is advised, mixer-settler is 4 grades, and every grade is a unit；Unit includes mixed cell and quiet in each unit
Clarification unit is put, unit total measurement (volume) is 5 liters, and mixed cell is 1 liter, and it is 4 liters to stand unit；Remover is tricaprylmethyl sulfuric acid
Ammonium；
Remover and phenol wastewater are pumped into simultaneously directly into device using peristaltic pump, it is 2mL/min to be pumped into remover, pump
It is 80mL/min to enter waste water speed；It is to be pumped into phenol wastewater from the heavy liquid inlet of unit 1 to be pumped into direction, by the heavy out pump of unit 2
Go out dephenolize waste water, remover is pumped into by the light phase inlet of unit 2, organic phase containing phenol is pumped out by the light phase export of unit 1, by dephenolize waste water
Phenol content and COD value detection are carried out after collection；
The organic phase containing phenol pumped out is pumped into buffer pool, then unit 3 is pumped directly into by buffer pool, regeneration is pumped into by unit 4
Agent (mol ratio 2:1 ammonium hydrogencarbonate and the mixed solution of ammoniacal liquor, ammonium hydrogencarbonate concentration are 2mol/L, ammonia concn 1mol/
L), the speed for being pumped into the organic phase containing phenol is 10mL/min, and the speed for being pumped into regenerative agent is 1mL/min, being regenerated containing phenol after regeneration
Agent is discharged by unit 3, and regeneration remover is discharged by unit 4, is recycled.
Waste water after dephenolize：13mg/L containing phenol, COD 900mg/L.
Embodiment 3
Raw water data：5000mg/L containing phenol, COD：102000mg/L, pH 10.2；The mixer-settler used is used for extraction
Conventional mixer-settler, mixer-settler are 6 grades, and every grade is a unit；In each unit unit include mixed cell with
Clarification unit is stood, unit total measurement (volume) is 5 liters, and mixed cell is 1 liter, and it is 4 liters to stand unit；Remover is three zinc-base methyl chlorides
Change ammonium；
Remover and phenol wastewater are pumped into simultaneously directly into device using peristaltic pump, it is 2mL/min to be pumped into remover, pump
It is 70mL/min to enter waste water speed；It is to be pumped into phenol wastewater from the heavy liquid inlet of unit 1 to be pumped into direction, by the heavy out pump of unit 4
Go out dephenolize waste water, remover is pumped into by the light phase inlet of unit 4, organic phase containing phenol is pumped out by the light phase export of unit 1, by dephenolize waste water
Phenol content and COD value detection are carried out after collection；
The organic phase containing phenol pumped out is pumped into buffer pool, then unit 5 is pumped directly into by buffer pool, regeneration is pumped into by unit 6
Agent (mol ratio 2:1 ammonium hydrogencarbonate and the mixed solution of ammoniacal liquor, ammonium hydrogencarbonate concentration are 2mol/L, ammonia concn 1mol/
L), the speed for being pumped into the organic phase containing phenol is 8mL/min, and the speed for being pumped into regenerative agent is 1mL/min, the regenerative agent containing phenol after regeneration
Discharged by unit 5, regeneration remover is discharged by unit 6, is recycled.
Waste water after dephenolize：10mg/L containing phenol, COD 850mg/L.
As seen from the above embodiment, it is only the preferred embodiment of the present invention that the present invention is described above, it is noted that for
For those skilled in the art, under the premise without departing from the principles of the invention, can also make it is some improvement and
Retouching, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (8)
1. a kind of processing method of phenol wastewater, comprises the following steps：
Phenol wastewater and remover are mixed and carry out dephenolize, separated after stratification, obtain dephenolize waste water and the upper strata of lower floor
Organic phase containing phenol；
The remover is organic quaternary ammonium salt compound.
2. processing method according to claim 1, it is characterised in that the organic quaternary ammonium salt compound includes organic season
One or more in ammonium carbonate, organic quaternary ammonium sulfate and organic quaternary ammonium hydrochloride.
3. processing method according to claim 2, it is characterised in that the organic quaternary ammonium salt compound is chain alkyl
Quaternary ammonium salt；
The long chain alkyl ammonium salt includes single-long-chain alkyl quaternary ammonium salt, double long-chain alkyl quaternary ammonium salt and tri-long-chain alkyl quaternary ammonium salt
In one or more；
The C atomicities of the chain alkyl are independently 6~9.
4. processing method according to claim 1, it is characterised in that the time of the dephenolize is 10~20min.
5. processing method according to claim 1, it is characterised in that the volume ratio of the remover and phenol wastewater is 1
~10:1000.
6. processing method according to claim 1, it is characterised in that the time of the standing is 10~20min.
7. processing method according to claim 1, it is characterised in that the organic phase containing phenol is carried out again using regenerative agent
It is raw；
The regenerative agent is the salting liquid containing carbonate, or the salting liquid containing sulfate radical, or the salting liquid containing chlorion.
8. processing method according to claim 1, it is characterised in that the phenolic wastewater treatment is mixing clarification with device
Groove.
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| CN201710675963.5A CN107399779A (en) | 2017-08-09 | 2017-08-09 | A kind of processing method of phenol wastewater |
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| CN201710675963.5A CN107399779A (en) | 2017-08-09 | 2017-08-09 | A kind of processing method of phenol wastewater |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1712093A (en) * | 2004-06-22 | 2005-12-28 | 中国科学院过程工程研究所 | Organic substance extraction in water with ionic liquid as extractant |
| CN101092254A (en) * | 2007-07-04 | 2007-12-26 | 中国科学院长春应用化学研究所 | Method for enriching aromatic compounds in wastewater |
| CN102989196A (en) * | 2011-09-16 | 2013-03-27 | 北京化工大学 | Separation method for phenol compounds in oil |
| CN104946303A (en) * | 2015-05-18 | 2015-09-30 | 太原师范学院 | Method for selectively separating phenol mixture from oil |
-
2017
- 2017-08-09 CN CN201710675963.5A patent/CN107399779A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1712093A (en) * | 2004-06-22 | 2005-12-28 | 中国科学院过程工程研究所 | Organic substance extraction in water with ionic liquid as extractant |
| CN101092254A (en) * | 2007-07-04 | 2007-12-26 | 中国科学院长春应用化学研究所 | Method for enriching aromatic compounds in wastewater |
| CN102989196A (en) * | 2011-09-16 | 2013-03-27 | 北京化工大学 | Separation method for phenol compounds in oil |
| CN104946303A (en) * | 2015-05-18 | 2015-09-30 | 太原师范学院 | Method for selectively separating phenol mixture from oil |
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