CN108862847A - A kind for the treatment of method and apparatus of industry phenol wastewater - Google Patents
A kind for the treatment of method and apparatus of industry phenol wastewater Download PDFInfo
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- C02F2101/00—Nature of the contaminant
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Abstract
The present invention provides a kind for the treatment of method and apparatus of industrial phenol wastewater, qualified discharge is unable to after solving the problems, such as high-concentration phenolic wastewater biochemical treatment in the prior art, wastewater treatment method of the invention includes buffering, flocculation, physical absorption dephenolize, biochemical-chemical combined dephenolize, the aerobic joint biochemical treatment of anaerobic-aerobic-advanced oxidation-, using flocculation, Phenol for Waste Water content and COD can be greatly lowered in physical absorption dephenolize and biochemical-chemical combined dephenolize, high-concentration phenolic wastewater is able to solve to be directly entered the growth of biochemical treatment inhibition microorganism and cause processing incomplete, the problem of COD removal effect reduces and influences subsequent Aerobic Process for Treatment, advanced treating is carried out by the aerobic joint biochemical treatment of anaerobic-aerobic-advanced oxidation-again, to realize qualified discharge.
Description
Technical field
The invention belongs to field of industrial waste water treatment, and in particular to a kind for the treatment of method and apparatus of industry phenol wastewater.
Background technique
Used water difficult to degradate refers to that difficulty is decomposed by the microorganisms or decomposition rate is slow, decomposes halfway waste water, this kind of waste water
In generally comprise heterocycle compound, organic phenolic compounds, surfactant, halogenated hydrocarbons, polycyclic aromatic hydrocarbon, organic dyestuff or organic
The toxic persistent organic pollutants such as phosphorus pesticide, general microorganism are hardly degraded effect to it, and used water difficult to degradate is given birth to
The property changed is poor, causes single anaerobic ferment process to be difficult to remove the macromolecular organic pollutant in waste water, causes subsequent aerobic
It is excessively high to handle load, qualified discharge is unable to after processing；Furthermore may cause containing to the virose pollutant of microorganism in waste water
Microorganism is dead, more reduces the degradation of subsequent organic matter.
Macromolecular organic pollutant in waste water can be oxidized to small molecule organic pollutant by high-level oxidation technology, but right
The removal ability of small molecule organic pollutant is poor, and it is poor to be used alone to processing refractory wastewater effect.By biochemical technology
Processing used water difficult to degradate is combined with high-level oxidation technology can achieve good treatment effect, but utilize high-level oxidation technology
By the undegradable organic pollutant degradation of biochemical treatment to up to standard, processing cost height.
For example, about to discharge 15 tons of toxic organic chemical industries useless for 1 ton of bigcatkin willow acid product of every production in salicylic acid industrial processes
Water, this kind of waste water is dense (phenol concentration about 1000mg/L) containing phenol, and organic phenol is difficult to degrade as one kind generally acknowledged in the world
Substance has very strong toxic action to organism.Currently, three can be divided mainly into greatly for the processing method of the sewage containing phenols
Class：Physical method, chemical method and biological method.It is industrial at present that the phenolic substances in waste water is carried out using extraction tower mostly
It extracts, the way of distillation is recycled to recycle extractant, the shortcomings that this method is：When carrying out extracting operation using extraction tower, it is easy
Existing serious air-teturning mixed phenomenon, and stage efficiency is not high；And utilizing the energy consumption of way of distillation recycling extractant larger, extractant loss is tight
Weight, higher cost.
Compared to the above, biochemical method is not only more economical, efficient, treating capacity is larger, and more superior is without secondary pollution.
But using in single anaerobic fermentation or anaerobic-aerobic biochemical waste water treatment process, phenol, the heterocycle of Coal Gas Washing Cycling Water
The noxious materials such as compound, the serious growth for inhibiting microorganism even result in microorganism death, and processing is caused not exclusively to cause
COD remove effect reduce, cause subsequent Aerobic Process for Treatment load excessively high, treated water outlet cannot direct qualified discharge, Bu Nengman
The requirement of sufficient discharged wastewater met the national standard.
Summary of the invention
Therefore, single anaerobic fermentation is used in the prior art or is detested the technical problem to be solved in the present invention is that overcoming
The problem of oxygen-aerobic biochemical waste water treatment process is to qualified discharge is unable to after industry high-concentration phenolic wastewater treatment, to propose
A kind for the treatment of method and apparatus of industry phenol wastewater.
For this purpose, the technical solution that the application takes is, a kind of processing method of industry phenol wastewater, successively includes following step
Suddenly：At buffering, flocculation, physical absorption dephenolize, the chemical combined dephenolize of biochemistry-, the aerobic joint of anaerobic-aerobic-advanced oxidation-are biochemical
Reason.
It is further preferred that it is 9.2-10.7 that calcium hydroxide, which is added, and adjusts the pH of waste water, to flocculation basin in flocculation step
Middle investment composite flocculation agent, revolving speed 100-180r/min stir 10-20min, precipitate floccule body after standing 20min, described multiple
Closing flocculant includes organic flocculating polymer body, inorganic polymer floccule body, potassium ferrate and diatomite.
It is further preferred that the organic polymer floccule body is anionic polyacrylamide, the inorganic polymer wadding
Solidifying body is polymeric aluminum sulfate iron.
It is further preferred that in parts by weight, the composite flocculation agent includes that 1-5 parts of anion are poly- in flocculation step
Acrylamide, 20-75 part polymeric aluminum sulfate iron, 10-15 parts of potassium ferrates and 10-15 parts of diatomite.
It is further preferred that in physical absorption dephenolize step, be disposed in phenol adsorption tower active carbon, absorption resin or
Derma has the chitosan magnetic microsphere of ferroso-ferric oxide as adsorbent, and the waste water Jing Guo flocculation step is passed through phenol absorption
Tower, staticaccelerator adsorption reacts 4h under room temperature, and then magnetic liquid separates, obtained low concentration phenol wastewater.
Wherein, the chitosan magnetic microsphere for being coated with ferroso-ferric oxide is by the oxidation of chitosan coated magnetic particle four three
Tie Tong Over emulsfication cross-linking method is prepared, and is the prior art, details are not described herein again, this kind of microballoon not only has the absorption of chitosan
Ability also easily facilitates recycling adsorbent, inhales with the ferromagnetism of ferroso-ferric oxide relative to adsorbents such as active carbon, zeolites
Attached effect enhancing, and by being modified synthesis polyamino chitosan to chitosan, using polyamino chitosan as outer layer
Lapping is conducive to the absorption to phenolic compound or other compounds with anion or negative electron.
It is further preferred that the low concentration that phenol adsorption step obtains is contained in biochemical-chemical combined phenol removal step
Phenol waste water inputs in HCR reactor, and puts into barium chloride as phenol precipitating reagent, every L raw water into the activated sludge of HCR reactor
Middle addition 1-5g barium chloride reacts 5-10h, then passes in precipitation tank and removes phenates and other organic matters precipitating.
It is further preferred that in the aerobic joint biochemical treatment of anaerobic-aerobic-advanced oxidation-, the anaerobic biochemical treatment
Using anaerobism GHBR bioreactor, the aerobic treatment of previous stage uses the aerobic GHBR bioreactor of level-one, described
Be provided in anaerobism GHBR bioreactor and the aerobic GHBR bioreactor of level-one surface through immobilized microorganism it is modified at
The filler of reason is additionally provided with micro-hole aerator and deflector in the aerobic GHBR bioreactor of level-one.
Wherein, GHBR bioreactor is additionally arranged micropore on the basis of existing high-efficiency composite biological reactor (HBR)
Aerator and deflector, wherein deflector is located at GHBR inside bioreactor, while being located at the outside of aerator, deflector
Height lower than the liquid level in GHBR bioreactor, the aeration bubbles diameter of micro-hole aerator is small, gas-oil interfaces are big, bubble
Uniformly, the oxygen-transfer efficiency of bioreactor can be improved in diffusion, enhances oxidation effect.Micro-hole aerator of the present invention uses
The mode of centralized arrangement causes larger so that forming significantly high dissolved oxygen area and low dissolved oxygen area in water body under water jet propulsion
Dissolved oxygen concentration gradient distribution, the transmission speed of oxygen is improved, so that the utilization rate of oxygenation capacity and oxygen is increased.Water conservancy diversion
Plate can make to keep certain horizontal flow velocity in bioreactor, larger to low dissolved oxygen area with the water flow for giving high-solubility oxygen area
Motive force.Deflector of the present invention can make level stream speed reach 0.3m/s or more.The present invention uses micro-hole aerator
With the coefficient oxygen charging method of deflector, oxygenation capacity increases, and the utilization rate of oxygen increases, and improves the effect of bioreactor
Rate.
It is further preferred that dissolved oxygen amount is in anaerobism GHBR bioreactor<0.5mg/l, temperature are 10-40 DEG C of range
Interior, pH 6.8-7.2, the residence time of waste water is 30-100h；The dissolved oxygen amount of the aerobic GHBR bioreactor of level-one is 2-4mg/
L, temperature are pH 6.8-7.5 within the scope of 10-40 DEG C, and the residence time of waste water is 20-40h.
It is a further object of the present invention to provide a kind of device of processing method suitable for the industrial phenol wastewater, packets
It is biochemical to include the aerobic joint of sequentially connected buffer pool, flocculation basin, HCR reactor, phenol adsorption tower, anaerobic-aerobic-advanced oxidation-
Processing unit, the aerobic joint biochemical treatment apparatus of anaerobic-aerobic-advanced oxidation-include the anaerobism GHBR life being serially connected
The aerobic GHBR bioreactor of object reactor, level-one, advanced oxidation pond and the aerobic MBR bioreactor of second level.
It is further preferred that the aerobic MBR bioreactor of second level is provided with the first reflux unit, extremely by return of waste water
The anaerobism GHBR bioreactor, the HCR reactor are provided with the second reflux unit, by return of waste water to the flocculation
Pond.
Technical solution of the present invention has the following advantages that：
1. the present invention provides a kind of processing method of industrial phenol wastewater, by high-concentration phenolic wastewater pass sequentially through flocculation,
Most of phenols in waste water, acids can be effectively removed after physical absorption phenol removal and biochemical-chemical phenol removal and are divided greatly
Sub- organic matter obtains low concentration phenol wastewater (COD<200mg/L, phenol<10mg/L), by passing through low concentration phenol wastewater again
Biochemical treatment is able to solve high-concentration phenolic wastewater and is directly entered the growth of biochemical treatment inhibition microorganism and causes to handle endless
Entirely, COD removes the problem of effect reduces and influences subsequent Aerobic Process for Treatment, to realize qualified discharge.
2. the present invention provides a kind of processing method of industrial phenol wastewater, low concentration phenol wastewater passes through anaerobic-aerobic-height
Qualified discharge is realized in grade oxidation-aerobic joint biochemical treatment, which has efficient in combination with advanced oxidation processing
The advantage for the low cost that rate oxidation and biochemical treatment have, advanced oxidation processing can in potent oxidized waste water larger molecular organics and
Toxic organic compound difficult to degrade can be effectively removed by biochemical-chemical combined dephenolize and anaerobism GHBR bioreactor for treatment
Still remaining phenols, heterocyclic or other toxic organic compounds in waste water afterwards, and then improve these harmful substances to biochemical rank
The influence of section microorganism, enables the microorganism in joint biochemical process preferably to play the effect of degradation of organic substances molecule,
Industrial phenol wastewater after joint is biochemical obtains advanced treating, qualified discharge (COD<20mg/L, phenol<0.1mg/L).
3. the present invention provides a kind of processing method of industrial phenol wastewater, calcium hydroxide and composite flocculation are added in waste water
Agent, composite flocculation agent quickly forms floccule body in waste water can effectively remove the larger molecular organics to suspend in waste water, wherein
Polyacrylamide has good flocculability, can reduce the frictional resistance between liquid, is also used as flocculation aid, promotes poly-
Close the flocculation of aluminium iron sulfate；And the calcium hydroxide in organic acid and water occurs complexation reaction and generates positively charged complex, yin from
Sub- polyacrylamide can form the floccule body of large volume with above-mentioned complex by Electrostatic Absorption, promote the heavy of above-mentioned complex
Drop；Diatomite can adsorb micron-sized macromolecular substances, can also promote acidic group calcium floccule body by the addition of diatomite
Precipitating, therefore, can not only remove larger molecular organics and suspended matter in waste water by composite flocculation agent, and can remove big
Partial acid ion enables flocculation basin to be effectively removed macromolecule organic as level-one depickling carbonization treatment device and have
Machine acid.
4. the present invention provides a kind of processing method of industrial phenol wastewater, waste water inputs HCR (High
Performancecompactreactor biochemical-chemical combined phenol removal) is carried out, wherein HCR reactor is that German industry science is big
It learns object and mutually transmits Research Institute, the water circulating pump of HCR reactor connection generates high pressure water flow and injects in reactor through spray head,
Negative pressure sucking large quantity of air is generated simultaneously, in water flow and under the combined effect of airflow formation High Speed Turbulent shear zone, by sucking
Air is dispersed into tiny bubble, and activated sludge is constantly sheared, and forms fine and closely woven floccule body, compared to traditional active sludge,
The ability of adsorption capacity and decomposing organic matter with enhancing；And under the action of water circulating pump, mixed liquor is in the reactor
Move in circles operation, promotes phenol precipitating reagent barium chloride and phenol organic matter flocculation sedimentation, and in the effect of activated sludge floccule body
Lower enrichment precipitating, effectively reduces the concentration of Phenol for Waste Water substance, it is made to be more easier to remove in subsequent processing.
5. the processing method that the present invention provides a kind of industrial phenol wastewater passes through magnetic microsphere energy in phenol adsorption step
Coloring matter, phenol and the heavy metal ion in waste water are enough adsorbed, and it is additional to utilize magnetization object ferroso-ferric oxide that can utilize
The separation of magnet realization liquid and microballoon.
6. the present invention provides a kind of processing method of industrial phenol wastewater, anaerobism fixed on composite filling in waste water and pond
Bacterium comes into full contact with carry out biochemical reaction, in waste water remaining phenolic compound and and most of quinoline, indoles be containing for representative
Nitrogen heterocyclic is converted and is degraded；And the biological COD that significantly degrades of the biochemical realization of joint, denitrogenation dephosphorizing, relative to
Traditional sludge media, filler in GHBR by bio-immobilized technology by biological fixation on filler, large specific surface area, easily
In biofilm, capacity of resisting impact load is strong, is conducive to the activity for keeping microorganism, and treatment effeciency is high.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the process flow chart of industrial phenolic wastewater treatment method in the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
A kind of processing method of industry phenol wastewater, includes the following steps：
(1) raw water is inputted in conditioning tank and is buffered, COD is 5000mg/L in raw water, and phenol content 1300mg/L, pH are
5.4, coloration was 1200 (again), and raw water enters flocculation basin, and calcium hydroxide is added into flocculation basin, adjusted the pH of raw water in flocculation basin
It is 10.7, composite flocculation agent is put into flocculation basin, dosage is that 30mg composite flocculation agent is added in every L raw water, adjusts flocculation
Pond revolving speed 100r/min stirs 20min, precipitates floccule body after standing 20min, wherein composite flocculation agent is 1 by mass ratio:60:
10:15 anionic polyacrylamide, polymeric aluminum sulfate iron, potassium ferrate and diatomite, which is uniformly mixed, to be made；
(2) by the supernatant input phenol adsorption tower of step (1), derma is disposed in phenol adsorption tower four oxidations three
The chitosan magnetic microsphere of iron is as adsorbent, under room temperature after staticaccelerator adsorption reaction 4h, passes through external magnet auxiliary and realizes magnetic liquid
Separation, obtained low concentration phenol wastewater；
(3) in the low concentration phenol wastewater input HCR reactor obtained step (2), into the active mud of HCR reactor
Put into barium chloride, dosage be every L raw water in be added 2.5g barium chloride, react 10h, then pass in precipitation tank remove it is remaining
Phenates and other organic matters precipitate；
(4) supernatant of step (3) is sequentially input into the aerobic GHBR biological respinse of anaerobism GHBR bioreactor, level-one
Device, advanced oxidation pond and the aerobic MBR bioreactor of second level,
1. dissolved oxygen amount is in anaerobism GHBR bioreactor<0.5mg/l, temperature are pH 7.2 within the scope of 27 DEG C, waste water
Residence time be 75h；
2. the dissolved oxygen amount of the aerobic GHBR bioreactor of level-one is 3mg/L, temperature is pH 6.8 within the scope of 25 DEG C, waste water
Residence time be 40h；
3. waste water enters advanced oxidation device, advanced oxidation device includes being sequentially connected centrifugal pump, venturi ejector, smelly
Oxygen Generator, oxygenerator, air compressor machine, catalytic reactor and heat exchanger, advanced oxidation device are difficult to degrade by remaining phenol, heterocycle etc.
Oxidation operation be small molecule, easily biodegradable organics；
4. waste water enters the aerobic MBR bioreactor of second level, advanced oxidation water outlet is subjected to biochemical reaction and film mistake again
Filter, water outlet reach discharge standard (COD<20mg/L, phenol content<0.1mg/L).
Embodiment 2
A kind of processing method of industry phenol wastewater, includes the following steps：
(1) raw water input conditioning tank is buffered, COD is 4800mg/L in raw water, and phenol content 1210mg/L, pH are
5.4, coloration was 1000 (again), and raw water enters flocculation basin, and calcium hydroxide is added into flocculation basin, adjusted the pH of raw water in flocculation basin
It is 10.0, composite flocculation agent is put into flocculation basin, dosage is that 20mg composite flocculation agent is added in every L raw water, adjusts flocculation
Pond revolving speed 150r/min stirs 20min, precipitates floccule body after standing 20min, wherein composite flocculation agent is 5 by mass ratio:65:
12:13 anionic polyacrylamide, polymeric aluminum sulfate iron, potassium ferrate and diatomite, which is uniformly mixed, to be made；
(2) by the supernatant input phenol adsorption tower of step (1), derma is disposed in phenol adsorption tower four oxidations three
The chitosan magnetic microsphere of iron is as adsorbent, under room temperature after staticaccelerator adsorption reaction 4h, passes through external magnet auxiliary and realizes magnetic liquid
Separation, obtained low concentration phenol wastewater；
(3) in the low concentration phenol wastewater input HCR reactor obtained step (2), into the active mud of HCR reactor
Put into barium chloride, dosage be every L raw water in be added 5g barium chloride, react 7.5h, then pass in precipitation tank remove it is remaining
Phenates and other organic matters precipitate；
(4) supernatant of step (3) is sequentially input into the aerobic GHBR biological respinse of anaerobism GHBR bioreactor, level-one
Device, advanced oxidation pond and the aerobic MBR bioreactor of second level,
1. dissolved oxygen amount is in anaerobism GHBR bioreactor<0.5mg/l, temperature are pH 6.8 within the scope of 25 DEG C, waste water
Residence time be 35h；
2. the dissolved oxygen amount of the aerobic GHBR bioreactor of level-one is 2mg/L, temperature is pH 7.5 within the scope of 22 DEG C, waste water
Residence time be 20h；
3. waste water enters advanced oxidation device, advanced oxidation device includes being sequentially connected centrifugal pump, venturi ejector, smelly
Oxygen Generator, oxygenerator, air compressor machine, catalytic reactor and heat exchanger, advanced oxidation device are difficult to degrade by remaining phenol, heterocycle etc.
Oxidation operation be small molecule, easily biodegradable organics；
4. waste water enters the aerobic MBR bioreactor of second level, advanced oxidation water outlet is subjected to biochemical reaction and film mistake again
Filter, water outlet reach discharge standard (COD<20mg/L, phenol content<0.1mg/L).
Embodiment 3
A kind of processing method of industry phenol wastewater, includes the following steps：
(1) raw water input conditioning tank is buffered, COD is 4000mg/L in raw water, and phenol content 1000mg/L, pH are
5.6, coloration was 800 (again), and raw water enters flocculation basin, and calcium hydroxide is added into flocculation basin, adjusted the pH of raw water in flocculation basin
It is 9.2, composite flocculation agent is put into flocculation basin, dosage is that 20mg composite flocculation agent is added in every L raw water, adjusts flocculation basin
Revolving speed 120r/min stirs 10min, precipitates floccule body after standing 20min, wherein composite flocculation agent is 2 by mass ratio:60:
15:15 anionic polyacrylamide, polymeric aluminum sulfate iron, potassium ferrate and diatomite, which is uniformly mixed, to be made；
(2) by the supernatant input phenol adsorption tower of step (1), derma is disposed in phenol adsorption tower four oxidations three
The chitosan magnetic microsphere of iron is as adsorbent, under room temperature after staticaccelerator adsorption reaction 4h, passes through external magnet auxiliary and realizes magnetic liquid
Separation, obtained low concentration phenol wastewater；
(3) in the low concentration phenol wastewater input HCR reactor obtained step (2), into the active mud of HCR reactor
Barium chloride is put into, dosage is that 1g barium chloride is added in every L raw water, reacts 7h, then passes in precipitation tank and remove remaining phenol
Salt and other organic matters precipitate；
(4) supernatant of step (3) is sequentially input into the aerobic GHBR biological respinse of anaerobism GHBR bioreactor, level-one
Device, advanced oxidation pond and the aerobic MBR bioreactor of second level,
1. dissolved oxygen amount is in anaerobism GHBR bioreactor<0.5mg/l, temperature are pH 7.2 within the scope of 25 DEG C, waste water
Residence time be 55h；
2. the dissolved oxygen amount of the aerobic GHBR bioreactor of level-one is 3mg/L, temperature is pH 6.8 within the scope of 20 DEG C, waste water
Residence time be 40h；
3. waste water enters advanced oxidation device, advanced oxidation device includes being sequentially connected centrifugal pump, venturi ejector, smelly
Oxygen Generator, oxygenerator, air compressor machine, catalytic reactor and heat exchanger, advanced oxidation device are difficult to degrade by remaining phenol, heterocycle etc.
Oxidation operation be small molecule, easily biodegradable organics；
4. waste water enters the aerobic MBR bioreactor of second level, advanced oxidation water outlet is subjected to biochemical reaction and film mistake again
Filter, water outlet reach discharge standard (COD<20mg/L, phenol content<0.1mg/L).
Comparative example 1
The processing method and Chinese patent literature CN102642933A specific embodiment of this comparative example industry phenol wastewater
One is essentially identical, and difference is only in that processing raw water is different, and it is same as Example 1 that this comparative example handles raw water.
Water outlet is not up to discharge standard after handling in this comparative example, and by anaerobic biodegradation process, COD removal rate is
50%, the present invention is 99% or more, in addition, the phenol content of this comparative example processed waste water is 0.1g/L, is discharged below standard.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of processing method of industry phenol wastewater, it is characterised in that：It in turn includes the following steps：Buffering, flocculation, physics are inhaled
Attached dephenolize, the chemical combined dephenolize of biochemistry-, the aerobic joint biochemical treatment of anaerobic-aerobic-advanced oxidation-.
2. the processing method of industry phenol wastewater according to claim 1, it is characterised in that：In flocculation step, it is added
The pH that calcium hydroxide adjusts waste water is 9.2-10.7, composite flocculation agent is put into flocculation basin, revolving speed 100-180r/min is stirred
10-20min is mixed, precipitates floccule body after standing 20min, the composite flocculation agent includes organic polymer coargulator, inorganic high score
Sub- flocculant, potassium ferrate and diatomite.
3. the processing method of industry phenol wastewater according to claim 2, it is characterised in that：The organic polymer flocculation
Body is anion, cation or non-ionic polyacrylamide, and the inorganic polymer floccule body is aluminium polychloride, polyaluminum sulfate
Aluminium or bodied ferric sulfate.
4. the processing method of industry phenol wastewater according to claim 2 or 3, it is characterised in that：In flocculation step, with
Parts by weight meter, the composite flocculation agent includes 1-5 parts of anionic polyacrylamide, 20-75 parts of polyaluminium sulfates, 10-15 parts high
Potassium ferrite and 10-15 parts of diatomite.
5. the processing method of industrial phenol wastewater described in any one of -4 according to claim 1, it is characterised in that：It is inhaled in physics
In attached dephenolize step, the chitosan that active carbon, absorption resin or derma have ferroso-ferric oxide is disposed in phenol adsorption tower
Magnetic microsphere will be passed through phenol adsorption tower by flocculation step, staticaccelerator adsorption reacts 4h under room temperature, then magnetic liquid point as adsorbent
From obtained low concentration phenol wastewater.
6. the processing method of industry phenol wastewater according to any one of claims 1-5, it is characterised in that：In biochemistry-
In chemical combined phenol removal step, the low concentration phenol wastewater that phenol adsorption step is obtained is inputted in HCR reactor, and to
Barium chloride is put into the activated sludge of HCR reactor and is used as phenol precipitating reagent, and 1-5g barium chloride, reaction 5- are added in every L raw water
10h is then passed in precipitation tank and is removed phenates and other organic matters precipitating.
7. the processing method of industry phenol wastewater according to claim 1 to 6, it is characterised in that：In anaerobism-
In the aerobic joint biochemical treatment of aerobic-advanced oxidation-, the anaerobic biochemical treatment uses anaerobism GHBR bioreactor, previous
The aerobic treatment in stage uses the aerobic GHBR bioreactor of level-one, and the anaerobism GHBR bioreactor and level-one are aerobic
Filler of the surface through immobilized microorganism modification, the aerobic GHBR biology of level-one are provided in GHBR bioreactor
Micro-hole aerator and deflector are additionally provided in reactor.
8. the processing method of industry phenol wastewater according to claim 7, it is characterised in that：Anaerobism GHBR bioreactor
Interior dissolved oxygen amount is<0.5mg/l, temperature are pH 6.8-7.2 within the scope of 10-40 DEG C, and the residence time of waste water is 30-100h；One
The dissolved oxygen amount of the aerobic GHBR bioreactor of grade is 2-4mg/L, and temperature is pH 6.8-7.5 within the scope of 10-40 DEG C, waste water
Residence time is 20-40h.
9. a kind of device suitable for industrial phenolic wastewater treatment method of any of claims 1-8, feature exist
In：Including sequentially connected buffer pool, flocculation basin, HCR reactor, phenol adsorption tower, the aerobic joint of anaerobic-aerobic-advanced oxidation-
Biochemical treatment apparatus, the aerobic joint biochemical treatment apparatus of anaerobic-aerobic-advanced oxidation-includes the anaerobism being serially connected
The aerobic GHBR bioreactor of GHBR bioreactor, level-one, advanced oxidation pond and the aerobic MBR bioreactor of second level.
10. device according to claim 9, it is characterised in that：The aerobic MBR bioreactor of second level is provided with first
Reflux unit, by return of waste water to the anaerobism GHBR bioreactor, the HCR reactor is provided with the second reflux unit,
By return of waste water to the flocculation basin.
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