CN109748454A - A kind of novel process technique of organic pigment production waste water with high salt - Google Patents
A kind of novel process technique of organic pigment production waste water with high salt Download PDFInfo
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- CN109748454A CN109748454A CN201711090935.3A CN201711090935A CN109748454A CN 109748454 A CN109748454 A CN 109748454A CN 201711090935 A CN201711090935 A CN 201711090935A CN 109748454 A CN109748454 A CN 109748454A
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Abstract
The invention discloses a kind of processing methods of organic pigment production waste water with high salt to carry out sufficient homogeneous mixing to waste water by organic pigment waste water with high salt through pipeline to conditioning tank；Effect of the conditioning tank water outlet through pumping enters electrocatalytic oxidation system, the water outlet of electrocatalytic oxidation system enters hydrolysis acidification system, bio-film colonization and base sludge through culture domestication adsorb the organic matter in water body, are agglomerated, are degraded, insoluble matter in water sinks to bottom, supernatant flows out after the collection of top catch basin, effect of the hydrolysis acidification system water outlet through pumping enters CMBR system, waste water after hydrolysis acidification is reacted by bioreactor, wherein organic matter obtains oxygenolysis under the action of the mixed active sludge of high concentration, completes the processing of waste water.Compared with prior art, electrocatalytic oxidation system of the invention has higher efficiency, most harmful substances in most waste water can be carried out a degree of removal, so that the toxicity of waste water be made to substantially reduce.
Description
Technical field
The present invention relates to water-treatment technology field more particularly to a kind of novel process works of organic pigment production waste water with high salt
Skill.
Background technique
Pigment production waste water is primarily generated at the filters pressing after diazo-reaction and coupling reaction, in rinsing two procedures.Pressure
The waste water that filter generates is commonly referred to as waste liquor, its main component is in the azo pigments being lost, raw materials for production and production process
By-product；What rinsing process generated crosses 3~4 times or so that the low concentration wastewaters waters such as drainage, flushing water are waste liquor water.
Therefore azo pigments waste water has following characteristics:
(1) CODCrHeight, some are up to hundreds of thousands mg/L, and property is stablized, or even cannot degrade completely.
(2) coloration is high, and from 500 ~ 500000 times, bright color and opaque is presented in some waste water.
(3) compound in waste water containing a large amount of not degradable inorganic salts, heavy metal and non-metal Ns, P, S, also contains
There are nitro, alkyl, amino, halogen, alkyl, sulfonic group, aromatic hydrocarbon, the polycyclic aromatic for completing acidic group and the mixing substitution of above-mentioned group
Hydrocarbon, heteroaromatic hydrocarbon, aliphatic hydrocarbon, unsaturated fat hydrocarbon compound, and due to containing by-product, impurity, unreacted in waste water
Raw material and leakage filter product (it is reported that during DYE PRODUCTION, 1 ton of dyestuff of every production will lose 2% product with waste water), therefore
The B/C of waste water is lower, difficult for biological degradation；
(4) the process multi items of the production of pigment are more, yield is small, thus drain water quality and quantity with pigment production variation influence compared with
Greatly.
Based on the production technology to pigment, performance, structure, the research in feature, pigment wastewater has very strong toxicity.Have
Malicious ingredient can be divided into inorganic and organic two major classes.Main inorganic toxic component has heavy metal classes, such as copper, chromium, mercury；Salt,
Such as nitrite, sylvite；There is also iron, selenium, halide etc..Toxic organic principle mainly has: benzene, naphthalene, anthracene, quinones have
Machine object, aromatic amine compounds, aromatic nitro compound etc., wherein more phenyl ring substituted compounds such as biphenyl, are more toxic.Face
If material waste water, which is discharged into public water system toxic component therein, will seriously pollute environment.
Domestic and foreign scholars' azo dyes wastewater treatment has done a large amount of research work at present, due in pigment wastewater
Content of organics is very high, and wastewater flow rate is larger, simply uses the processing methods such as physics, chemistry from considerations such as processing costs and carries out
Toeatment period processing cost is very high, exceeds enterprise's tolerance range, and simple physico-chemical process is also difficult to ensure the treatment effect of waste water,
Therefore currently used method is mainly physical method, chemical method, bioanalysis and combinations thereof method.Common processing method such as table
Shown in 1.
1 common dyes wastewater treatment method of table and its advantage and disadvantage
Each method has its specific advantage and disadvantage as seen from the above table, and any method exclusive use is all difficult to give up pigment
Water process is to perfect condition.
Summary of the invention
The present invention provides a kind of novel process techniques of organic pigment production waste water with high salt, to solve organic pigment with high salt
The processing problem of waste water.
A kind of processing method of organic pigment production waste water with high salt, comprising the following steps:
(1) by organic pigment waste water with high salt through pipeline to conditioning tank, residence time 12h.Bottom of pond is equipped with aerating system pair
Waste water carries out sufficient homogeneous mixing, makes waste water homogeneous average, provides stable water inlet for follow-up system.
(2) effect of the conditioning tank water outlet through pumping enters electrocatalytic oxidation system, and the main purpose of the system is to degrade useless
Larger molecular organics to small organic molecule in water is even directly mineralized into CO2+H2O, to reduce the COD in waste waterCr。
Using graphite as cathode in this electrocatalytic oxidation system, Ti-Ru electrode is anode, with the filling of multiphase composite catalyst
Directly or indirectly reaction occurs in catalyst column, on anode:
The service condition of electrocatalytic oxidation system is as shown in the table:
Anode 2Cl--2e-→Cl2
Cl2+H2O→HClO+HCl
OH-Ion is diffused into the liquid layer around anode and hypochlorous acid reaction generates ClO-:
HClO+OH-→H2O+ClO-
In ClO-Next step process when building up can be regarded as and obtain chloric acid and O2Electrochemical process:
12ClO-+6H2O-12e-→4HClO3+8HCl+3O2
OH-Ion directly loses electronics in anode, while releasing oxygen:
4OH--4e-→2H2O+O2
Cathode 2H++2e-→H2
Na++OH-→NaOH
The indirect degradation of organic substances of hydrogen peroxide generated is restored, the total carbon degradation in fracturing outlet liquid is cooperateed with, to reduce CODCr
O2+2H++2e-→H2O2 。
Since electrocatalytic oxidation system is applied in CODCrIn the higher organic wastewater of concentration, it is immersed in for a long time this useless
Pollutant, which can be formed, in electrode surface in water influences treatment effeciency, therefore in the electrocatalytic oxidation to reduce electrode life
Regularly cleaning and activation are carried out to electrode by the way of pole in change system, are detached from the pollutant for being attached to electrode in time
Electrode surface.The COD of the time of pole and the frequency and waste water processedCrProportional, as the COD of waste waterCrIt is fallen when higher
The frequency of pole is higher, and the time is longer.Conditioning tank water outlet enters this electrocatalytic oxidation system by water inlet pipe.When long for anti-locking system
Between when running caused by pole plate corrosion or waste water the sticking substances of some tools stick on pole plate to reduce pole plate operation effect
Rate.Timing pole is provided in the system, when (time is with influent COD after a certain period of time for the system continuous operationCrDifference can
Modify) pole can be automatically switched to down, so that original anode be made to become cathode, original cathode becomes anode, in electric current
Under the action of, pollutant on pole plate etc. then can Automatic-falling into the waste water of the system, by electrocatalytic oxidation chemical conversion small molecule have
Machine object is directly mineralized into CO2+H2O, to achieve the purpose that clean pole plate.The gas generated in operational process is via gas-liquid point
Enter in absorption tower from device and absorbed, absorption tower is built-in to be filled with lye, is regularly replaced after adsorption saturation.
Due in pigment wastewater in addition to containing the hardly degraded organic substances such as a large amount of inorganic salts, condensed-nuclei aromatics, heterocyclic hydrocarbon, these
Under the action of electrocatalytic oxidation system, azo group (- N=N-) is destroyed organic matter, and cyclic structure is opened, thus CODCr?
To reduction, toxicity is weakened, some to be originally characterized into CODCrSubstance after this electrocatalytic oxidation system its structure
In rock-steady structure be broken, also can be by CODCrIt characterizes, the waste water COD after electrocatalytic oxidationCrIt is reduced to 6000 ~
7000mg/L。
(3) electrocatalytic oxidation water outlet enters subsequent hydrolysis acidification system, the waste water after obtaining hydrolysis acidification.
Hydrolysis acidification uses bottom in and top out structure, is internally provided with for wastewater of chemical industry with high concentration anaerobic organism filler, should
Biologic packing material has the features such as large specific surface area, porosity is high, long service life, compares other common fillers, which can mention
High about 10% ~ 20% removal rate to ammonia nitrogen, COD.Hydrolysis acidification system bottom is equipped with interval mud discharging device, through culture domestication
Bio-film colonization and base sludge adsorb the organic matter in water body, are agglomerated, are degraded, and the insoluble matter in water sinks to bottom, on
Clear liquid flows out after the collection of top catch basin.
Water outlet after electrocatalytic oxidation is entered the reaction zone of hydrolysis acidification system by the effect pumped, is made by water distribution coil pipe
The water flow of water inlet can be full and uniform enter reaction zone, realize mixing well and combining for sludge and waste water, muddy water mixing is without dead
Agitating device is not added at angle additionally, the dissolved oxygen brought into due to agitating device is reduced, to accelerate the starting of hydrolysis acidification system
Rate.Reaction zone water outlet is from settling zone is flow to, and since sludge has very strong biological flocculation and precipitation effect, most sludge can be with bacterium
The form automatic sedimentation of micelle, and supernatant then passes through outlet conduit into subsequent CMBR system.
The service condition of hydrolysis acidification system is as shown in the table:
Hydrolysis acidification system is to be readily biodegradable by larger molecular organics in sewage and not with biodegradable organic matter degradation
Small organic molecule (such as acetic acid, propionic acid, butyric acid), these small organic molecules to get off that are degraded easily pass through cell membrane into
Enter and carry out biochemical metabolism in thallus, subsequent aerobic unit is made to continue to drop with less energy consumption and in the shorter residence time
Solution.Compared to the methane phase process that whole anaerobism is subjected to, the hydraulic detention time of hydrolysis acidification is short, easily operated, starting
Fastly, forming small molecule acid can be continued with by the bioprocess including aerobic.
Electrocatalytic oxidation water outlet after the effect pumped reach hydrolysis acidification system, hydrolysis acidification system be collection precipitating, absorption,
In the efficient process unit of one, which is for biological flocculation and precipitation, biodegrade
Continue to improve biodegradability, still there are some organic matters that can not be degraded into small point by the system in previous step electrocatalytic oxidation system
The biochemical type organic matter of son, these organic matters can not more be degraded under complete aerobic condition, therefore add hydrolysis acidification system
System, in such a system these can not be by role transformations of acid-producing bacteria by biochemical substance can be by methanogen or aerobic bacteria
The small molecule volatile acid utilized is so as to improve wastewater biodegradability.In this Hydrolysis Acidification, CODCrThere is a degree of drop
Low, removal rate is 40% or so, is discharged CODCrIt is reduced to 4000mg/L or so, is largely reduced to subsequent CMBR
The load impact of system.
(4) effect of the hydrolysis acidification system water outlet through pumping enters CMBR system, a kind of contact film biology of CMBR system
Reactor is made of flat plate ultrafiltration film separation unit and biological processing unit two parts.Flat plate ultrafiltration film separation unit includes flat
Plate membrane module and aerator, wherein plate film assembly is by rectangle diaphragm, sealing ring, spacer bar, central collecting pipe, two side bumpers
The compositions such as plate, wherein diaphragm, sealing ring etc. are successively through in central collecting pipe, then by two side guards compress seal, waste water by
Grid after membrane filtration among inlet membrane, then it is pooled to negative pressure extraction of the central collecting pipe through suction pump, pass through point of film
From effect, purified water then becomes processing water outlet by film, and activated sludge is blocked in except diaphragm.
Flat membrane ultrafiltration separative unit is placed in inside bioreactor, and the underface of membrane module is arranged in aerator.
After hydrolysis acidification waste water enters bioreactor, organic matter obtains oxidation point under the action of the mixed active sludge of high concentration
Solution.The aerator being arranged below membrane module, which not only has, to be provided enough dissolved oxygens for the microorganism in biological processing unit and promotees
Into the function being thoroughly mixed, simultaneously because bubble stirring and its playing in the recycle stream that film surface is formed to film surface
Wash away and shear action, can effectively prevent pollutant film surface adhere to and deposit.
The activated sludge used in the biological processing unit is the model of Suzhou Environmental Protection Technology Co., Ltd, Ju Zhi Tontru
For JZ-halophile-001, be carried out for organic pigment with high salt production waste water professional separation, domestication, reinforcing and come it is efficient
Activated sludge has very strong adaptability.
The service condition of CMBR system is as shown in the table, and wherein dissolved oxygen is adjusted by adjusting aeration quantity, wherein film
Flux specifically regards influent COD Cr and the variation of water is adjustable.
| Unit | Operating parameter | |
| Hydraulic detention time | h | 12 |
| Water inlet pH value | 6~9 | |
| Inflow temperature | °C | < 40 |
| Influent COD Cr | mg/L | < 4000 |
| Dissolved oxygen | mg/L | 2~5 |
| Membrane flux | LMH | 15~20 |
| MLSS | mg/L | 8000 |
CMBR technique has the characteristics that load height, impact resistance, effluent quality is limpid, suspended matter is practically negligible, processing effect
Fruit is much higher than traditional activated sludge process.Plate membrane is used in flat plate ultrafiltration film unit, compared to traditional hollow-fibre membrane
Speech, plate membrane have more obvious advantage --- high-throughput stable operation can be kept under higher activated sludge concentration, no
Will appear hair, fracture of wire or fiber winding etc. hollow-fibre membranes FAQs, simultaneously because the aerator of the bottom CMBR
Diaphragm can be carried out effective sluicing, to make the pollution feelings for the control film surface that it in the process of running can be effectively stable
Condition increases its service life to extend the cleaning frequency of film, reduces operating cost.CMBR system is discharged limpid, CODCrGood
It is reduced under the action of oxygen bacterium lower than 500 mg/L, meets industrial park sewage disposal system and receive pipe standards.
The present invention has CODCrThe feature that removal rate is high, treatment effect is stable, it is ensured that water outlet that treated can enter subsequent
Urban sewage treatment system reduces pigment wastewater to the load impact of follow-up system.
Compared with prior art, electrocatalytic oxidation system of the invention has higher efficiency, can will be in most waste water
Azo group, condensed-nuclei aromatics, benzene, naphthalene, anthracene, quinones organic matter, aromatic amine compounds, aromatic nitro compound etc. all obtain
A degree of removal, so that the toxicity of waste water be made to substantially reduce.Addition hydrolysis acidification step makes to be dropped by electrocatalytic oxidation system
The organic matter of solution continues to be degraded to small molecule volatile acid, so that the biodegradability of waste water is largely improved, after being
Continuous CMBR system, which provides, stablizes water inlet water source.Halophiles is used in CMBR system, which still maintains very under high salt conditions
Strong bioactivity, the stable small molecule volatile acid by waste water of energy continue degradation and are even mineralized into CO2+H2O, to guarantee
It is discharged CODCr< 500mg/L, satisfaction receive Guan Yaoqiu.
Detailed description of the invention
Fig. 1 is the novel process process flow chart that organic pigment with high salt produces waste water.
Specific embodiment
The 100m of certain company workshop discharge3/ day organic pigment production waste water with high salt uses treatment process of the present invention, passes through
Following steps handle waste water:
Organic pigment with high salt production waste water is discharged into conditioning tank 1, homogeneous average is carried out to waste water by bottom of pond aerating system, is adjusted
It is 12000mg/L that CODCr average value is discharged in pond, subsequently into electrocatalytic oxidation system；
Operating parameter in electrocatalytic oxidation system is respectively as follows: 7 cms-1 of compartment flow velocity, pH value 6 ~ 9 of intaking, running current 3
A, working voltage 28 ~ 30 V, 40 ~ 60min of residence time, the electrode in system use graphite electrode for cathode, Ti-Ru electrode
For anode, it is catalyzed in column and loads IR series of high efficiency catalyst.Be discharged in electrocatalytic oxidation system CODCr be degraded to 6000 ~
7000mg/L, subsequently into hydrolysis acidification system；
Operating parameter difference in hydrolysis acidification system is as shown in the table, and the hydrolysis acidification system is in the process of running due to will be even
Nitrogen groups (- N=N-) are destroyed to keep the ammonia-nitrogen content in system higher, form ammonia system buffer solution to make in system
Alkalinity is presented in pH value, therefore real-time pH value detection is arranged in system at runtime, once the pH value in system is more than systemic presupposition value,
Acid is added from trend system by medicine machine then to keep pH value.Water outlet CODCr in hydrolysis acidification system is reduced to
3000 ~ 4000mg/L, subsequently into the CMBR system of next step；
| Unit | Operating parameter | |
| Hydraulic detention time | h | 24 |
| Run pH value | 6~9 | |
| Inflow temperature | °C | < 50 |
| Influent COD Cr | mg/L | < 8000 |
| MLSS | mg/L | 4500~5500 |
Operating parameter in CMBR system is as shown in the table, and the strain used in system is Halophiles, and the bacterial strain is in salt content height
Certain activity is still kept in the environment of to extreme 15%, organic pigment production waste water with high salt by electrocatalytic oxidation early period with
Its biodegradability is greatly improved after hydrolysis acidification, guarantees water outlet CODCr < 500mg/L after the operation of CMBR system,
Guan Yaoqiu is received to meet.
| Unit | Operating parameter | |
| Hydraulic detention time | h | 8 |
| Water inlet pH value | 6~9 | |
| Inflow temperature | °C | < 50 |
| Influent COD Cr | mg/L | < 5000 |
| Dissolved oxygen | mg/L | 2~5 |
| Membrane flux | L/(m2·H) | 15 |
| MLSS | mg/L | 8000。 |
System Inlet and outlet water water quality difference is as shown in the table:
| Index item | Water inlet | Water outlet |
| pH | 6-9 | |
| CODCr | 14000 | 450 |
| Ammonia nitrogen | 450 | 2.1 |
Foregoing description has illustrated illustrating and describing for invention.It is not configured to limit the invention to disclosed shape
Formula and mode.According to above mode, it can be modified or be changed accordingly.Discuss that example is in order to which this hair is better described
Bright principle and the practicality, to be carry out various modifications using the present invention and meet other specific demands.It is all these to repair
Change and change and interpreted when according to fair and legal right, and according to accessory claim, these modifications and variations are belonged to
In the scope of the present invention.
Claims (6)
1. a kind of processing method of organic pigment production waste water with high salt, which is characterized in that at least include the following steps:
1) by organic pigment waste water with high salt through pipeline to conditioning tank, bottom of pond is equipped with aerating system and carries out adequately to waste water
Homogeneous mixes, and makes waste water homogeneous average；
2) effect of the conditioning tank water outlet through pumping enters electrocatalytic oxidation system, using graphite as cathode in the electrocatalytic oxidation system,
Ti-Ru electrode is anode, is filled in catalyst column with multiphase composite catalyst, and directly or indirectly reaction occurs on anode, will
Larger molecular organics, small organic molecule in degrading waste water are converted to CO2+H2O；
3) water outlet of electrocatalytic oxidation system enters hydrolysis acidification system, which uses bottom in and top out structure, internal
It is provided with the anaerobic organism filler for wastewater of chemical industry with high concentration, ammonia nitrogen, the COD in waste water are removed；Hydrolysis acidification system
Bottom unite equipped with interval mud discharging device, bio-film colonization and base sludge through culture domestication inhale the organic matter in water body
Attached, cohesion is degraded, and the insoluble matter in water sinks to bottom, and supernatant flows out after the collection of top catch basin, after obtaining hydrolysis acidification
Waste water；
4) effect of the hydrolysis acidification system water outlet through pumping enters CMBR system, wherein mixed active of the organic matter in high concentration
Obtain oxygenolysis under the action of sludge, water outlet, which meets, receives Guan Yaoqiu.
2. a kind of processing method of organic pigment production waste water with high salt as described in claim 1, it is characterised in that: the CMBR
A kind of membrane bioreactor of system, is made of, flat plate ultrafiltration membrane flat plate ultrafiltration film separation unit and biological processing unit two parts
Separative unit includes plate film assembly and aerator, wherein plate film assembly be by rectangle diaphragm, sealing ring, spacer bar, in
The compositions such as heart collector pipe, two side guards, wherein diaphragm, sealing ring etc. are successively through in central collecting pipe, then by two side guards
Sealing is compressed, waste water is by the grid among inlet membrane after membrane filtration, then is pooled to negative pressure of the central collecting pipe through suction pump
Extracting, by the centrifugation of film, purified water then becomes processing water outlet by film, and activated sludge is blocked in except diaphragm；It exposes
The underface of membrane module is arranged in device of air；It is raw to organic pigment with high salt using high-efficiency activated sludge in the biological processing unit
It produces waste water and carries out biological respinse.
3. a kind of processing method of organic pigment production waste water with high salt as described in claim 1, it is characterised in that: waste water is in institute
Stating the residence time in conditioning tank is 12h.
4. a kind of processing method of organic pigment production waste water with high salt as described in claim 1, it is characterised in that: the electricity is urged
Change the service condition of oxidative system are as follows: 5 ~ 10cms-1 of compartment flow velocity；Water inlet pH value 6 ~ 9；1.5 ~ 3 A of running current；Operation electricity
Press 28 ~ 30V；20 ~ 60 min of residence time；Influent COD Cr < 15000mg/L；40 DEG C of inlet water temperature <.
5. a kind of processing method of organic pigment production waste water with high salt as described in claim 1, it is characterised in that: the hydrolysis
The service condition of acidification system are as follows: hydraulic detention time is for 24 hours；Run pH value 6.5 ~ 7.5；40 °C of inflow temperature <；Influent COD Cr
< 8000mg/L；MLSS 5500~7500mg/L.
6. a kind of processing method of organic pigment production waste water with high salt as claimed in claim 2, it is characterised in that: the CMBR
The service condition of system is 12 h of hydraulic detention time, pH value 6 ~ 9 of intaking；40 °C of inflow temperature <；Influent COD Cr <
4000mg/L, 2 ~ 5mg/L of dissolved oxygen, membrane flux 15 ~ 20LMH, MLSS 8000mg/L；Wherein dissolved oxygen is by adjusting aeration dress
The aeration quantity set is adjusted, and wherein membrane flux specifically regards influent COD Cr and the variation of water is adjustable.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111687206A (en) * | 2019-03-15 | 2020-09-22 | 中国石油化工股份有限公司 | In-situ enhanced biological ventilation restoration method for petroleum hydrocarbon polluted site |
| CN112551818A (en) * | 2020-12-17 | 2021-03-26 | 广州中国科学院先进技术研究所 | High-salinity organic wastewater treatment system and treatment method |
| CN114132898A (en) * | 2021-12-02 | 2022-03-04 | 海南昂扬科技有限公司 | Method for recovering hydrobromic acid |
| CN115072926A (en) * | 2022-07-22 | 2022-09-20 | 沈阳工大蓝金环保产业技术研究院有限公司 | Full-quantitative treatment method for pigment and dye intermediate wastewater |
-
2017
- 2017-11-08 CN CN201711090935.3A patent/CN109748454A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111687206A (en) * | 2019-03-15 | 2020-09-22 | 中国石油化工股份有限公司 | In-situ enhanced biological ventilation restoration method for petroleum hydrocarbon polluted site |
| CN112551818A (en) * | 2020-12-17 | 2021-03-26 | 广州中国科学院先进技术研究所 | High-salinity organic wastewater treatment system and treatment method |
| CN114132898A (en) * | 2021-12-02 | 2022-03-04 | 海南昂扬科技有限公司 | Method for recovering hydrobromic acid |
| CN114132898B (en) * | 2021-12-02 | 2023-01-17 | 海南昂扬科技有限公司 | Method for recovering hydrobromic acid |
| CN115072926A (en) * | 2022-07-22 | 2022-09-20 | 沈阳工大蓝金环保产业技术研究院有限公司 | Full-quantitative treatment method for pigment and dye intermediate wastewater |
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