CN105254115B - A kind of processing method of high salt organic pigment production waste water - Google Patents
A kind of processing method of high salt organic pigment production waste water Download PDFInfo
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- CN105254115B CN105254115B CN201510556978.0A CN201510556978A CN105254115B CN 105254115 B CN105254115 B CN 105254115B CN 201510556978 A CN201510556978 A CN 201510556978A CN 105254115 B CN105254115 B CN 105254115B
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Abstract
The present invention relates to a kind of processing method of high salt organic pigment production waste water, it is concretely comprised the following steps：(1) high salt organic pigment waste water is provided with aerating system and carries out sufficient homogeneous mixing to waste water through pipeline to regulating reservoir, bottom of pond, waste water homogeneous is measured, stable water inlet is provided for follow-up system；(2) effect of the regulating reservoir water outlet through pump enters electrocatalytic oxidation system, obtains the waste water of electrocatalytic oxidation；(3) follow-up hydrolysis acidification pool will be delivered to by delivery pump by the waste water of electrocatalytic oxidation, obtains the waste water after electrocatalytic oxidation processing；(4) effect of the water outlet of hydrolysis acidification system through pump enters MBR system, finally gives the water after processing.The present invention has higher efficiency, azo group in most waste water, condensed-nuclei aromatics, benzene, naphthalene, anthracene, quinones organic matter, aromatic amine compounds, aromatic nitro compound etc. can all be obtained a certain degree of removal, so that the toxicity of waste water substantially reduces.
Description
【Technical field】
The present invention relates to a kind of novel process technique of high salt organic pigment production waste water, and in particular to electrocatalytic oxidation system
System, hydrolysis acidification and MBR system, by the COD in waste waterCrDegraded is to meeting that enterprise's sewage receives pipe standards.
【Background technology】
Pigment production waste water is primarily generated at the press filtration after diazo-reaction and coupling reaction, in rinsing two procedures.Pressure
Waste water is commonly referred to as waste liquor caused by filter, and its main component is in the AZOpigments, raw materials for production and production process of loss
Accessory substance；The low concentration wastewater such as filter water, flushing water water caused by rinsing process is 3~4 times or so of waste liquor water.
Therefore AZOpigments waste water has following characteristics：
(1)CODCrHeight, some are up to hundreds of thousands mg/L, and property is stable, or even can not degrade completely.
(2) colourity is high, has from 500~500000 times, and bright color and light tight is presented in some waste water.
(3) also contain containing a large amount of not degradable inorganic salts, heavy metal and non-metal Ns, P, S compound in waste water
Have nitro, alkyl, amino, halogen, alkyl, sulfonic group, complete acidic group and above-mentioned group mixing substitution aromatic hydrocarbon, polycyclic aromatic
Hydrocarbon, heteroaromatic hydrocarbon, aliphatic hydrocarbon, unsaturated fat hydrocarbon compound, and due to containing accessory substance, impurity, unreacted in waste water
Raw material and leakage filter product (it is reported that during DYE PRODUCTION, often producing 1 ton of dyestuff, 2% product is lost with waste water), therefore
The B/C of waste water is relatively low, difficult for biological degradation；
(4) the process multi items of the production of pigment are more, yield is small, therefore draining water quality and quantity changes influence with pigment production
It is larger.
Based on there is very strong toxicity to the research in the production technology of pigment, performance, structure, feature, pigment wastewater.Have
Malicious composition can be divided into inorganic and organic two major class.Main inorganic toxic component has heavy metal classes, such as copper, chromium, mercury；Salt,
Such as nitrite, sylvite；Other also have iron, selenium, halide etc..Poisonous organic principle mainly has：Benzene, naphthalene, anthracene, quinones have
More phenyl ring substituted compounds such as machine thing, aromatic amine compounds, aromatic nitro compound etc., wherein biphenyl, toxicity are larger.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 substantial amounts of research work at present, due in pigment wastewater
Content of organics is very high, and wastewater flow rate is larger, and simply using the processing methods such as physics, chemistry from considerations such as processing costs is carried out
Toeatment period processing cost is very high, and beyond enterprise's tolerance range, and simple physico-chemical process is also difficult to ensure that the treatment effect of waste water,
Therefore currently used method is mainly Physical, chemical method, bioanalysis and combinations thereof method.Common processing method is as follows
Table 1.
The common dyes method of wastewater treatment of table 1 and its advantage and disadvantage
【The content of the invention】
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of processing of high salt organic pigment production waste water
Method, to solve the processing problem of high salt organic pigment waste water, use COD in the organic pigment waste water after this PROCESS FOR TREATMENTCr≤
500mg/L, satisfaction receive pipe requirement, avoid to the load impact of biochemical system during to follow-up uniformly biochemical treatment, so as to ensure
The stability of final outflow water.
The purpose of the present invention is achieved through the following technical solutions：
A kind of processing method of high salt organic pigment production waste water, it is concretely comprised the following steps：
(1) high salt organic pigment waste water is filled through pipeline to regulating reservoir, bottom of pond provided with aerating system to waste water
The homogeneous divided is mixed, and waste water homogeneous is measured, and stable water inlet is provided for follow-up system；
(2) effect of the regulating reservoir water outlet through pump enters electrocatalytic oxidation system, obtains the waste water of electrocatalytic oxidation；
For electrocatalytic oxidation system using graphite as negative electrode, Ti-Ru electrode is anode, and whole reactor is rectangle, negative electrode and
The pole plate of anode is individually positioned in the both ends of reactor, and plate width is consistent with reactor insied width；Reaction in two-plate
5 reaction zones are divided into, different zones are separated by rubber net panel, and composite catalyzing filler is filled with regional, and its is main
Composition is active powdered carbon and iron, and its mass ratio is 10: 0.1~10: 1, and composite catalyzing filler is pressed into honeycomb oblong-shaped；It is useless
Water enters from one end of reactor, other end outflow；
(3) follow-up hydrolysis acidification pool will be delivered to by delivery pump by the waste water of electrocatalytic oxidation, obtains electro-catalysis
Waste water after oxidation processes；
Hydrolysis acidification technique is to integrate precipitation, absorption, biological flocculation and precipitation, biodegradable efficient process cell process,
Main purpose of the technique in actual motion is to continue with improving biodegradability.Biological rope filler is installed, system is being transported in pond
Biomembrane can be attached with during row on biologic packing material, the material of biological rope filler filler is PP or PF, attached on biological rope filler
A large amount of biomembranes, have had a large amount of and oxygen on≤2mg/L, biomembrane in the Dissolved Oxygen concentration Control of hydrolysis acidification pool inner water
Bacterium, larger molecular organicses can be decomposed into by small organic molecule by the organic matter in biological metabolism Decomposition Wastewater；Hydrolysis acid
Change in pond and be provided with submersible agitator, acted on by hydraulic mixing, to avoid sludge in hydrolysis acidification pool bottom deposit；Hydrolysis acid
It is that one end is water inlet to change pond, and the other end is water outlet, and water inlet pipe is perforated pipe, and water outlet sets effluent trough；Effluent trough open interior leads to
Follow-up MBR ponds.
(4) effect of the water outlet of hydrolysis acidification system through pump enters MBR system, finally gives the water after processing.
Include MBR reaction tanks in MBR system, MBR reaction tanks include collector pipe, membrane module, air blower, aeration tube, sludge
Pump and self priming pump, membrane module include membrane component；Collector pipe is connected by membrane module, and the bottom of membrane module sets aeration tube,
Sludge pump and air blower are set respectively at the bottom both ends of MBR reaction tanks, and sludge pump passes through pipeline and excess sludge floss hole phase
Even, it is connected in the upper end of collector pipe with self priming pump.The bubble of aeration tube bulging can wash away membrane component surface in membrane module, prevent
Pollutant is in film surface attachment.
MBR is the combination of traditional activated sludge process and membrane separation technique, and muddy water is realized by membrane component and membrane module
Separation, instead of the second pond in traditional activated sludge process.Include in MBR system aeration plate, flat plate ultrafiltration membrane component and
Membrane module, sludge pump, aeration tube are used to provide sufficient oxygen to microorganism in pond, it is ensured that dissolved oxygen >=4mg/L in pond, it is necessary to
Given up Organic substance in water by aerobic degradation, organic matter is to be eventually converted into titanium dioxide by microorganism panning as food
Carbon, water and microorganism itself.Flat plate ultrafiltration membrane module is used to realize mud-water separation, and outside has self priming pump and will transmit through film by pond
Water inhale outward, that is to say, that MBR water outlets are exactly the water outlet filtered by membrane component and membrane module, therefore effluent quality is good.It is dirty
Dredge pump is for by the unnecessary sludge discharge pond in MBR ponds, making to keep certain sludge concentration in pond.
A kind of processing method of high salt organic pigment production waste water, comprises the following steps：
(1) high salt organic pigment waste water is filled through pipeline to regulating reservoir, bottom of pond provided with aerating system to waste water
The homogeneous divided is mixed, and waste water homogeneous is measured, and stable water inlet is provided for follow-up system；
(2) effect of the regulating reservoir water outlet through pump enters electrocatalytic oxidation system, and the main purpose of the system, which is to degrade, gives up
Larger molecular organicses in water are even directly mineralized into CO to small organic molecule2+H2O, so as to reduce the COD in waste waterCr.This
The core technology of electrocatalytic oxidation system is electro-catalysis and compounded mix catalytic oxidation technologies, belongs to advanced oxidation one kind, but
It is compared with other general advanced oxidization methods, its operating cost is low, operation is simple to operate, to high salt organic pigment waste water
With very significant treatment effect.Using graphite as negative electrode in this electrocatalytic oxidation system, Ti-Ru electrode is anode, with multiphase
Composite catalyst is filled in catalyst post, and directly or indirectly reaction occurs at different conditions, on anode：
Anode 2Cl-+2e-→Cl2
Cl2+H2O→HClO+HCl
OH-Ion is diffused into the liquid layer around anode and hypochlorous acid reaction generation ClO-：
HClO+OH-→H2O+ClO-
In ClO-Next step process when building up, it can regard as and obtain chloric acid and O2Electrochemical process：
12ClO-+6H2O+12e-→4HClO3+8HCl+3O2
OH-Ion directly loses electronics in anode, while releases oxygen：
4OH-+4e-→2H2O+O2
Negative electrode 2H++2e-→H2
Na++OH-→NaOH
The indirect degradation of organic substances of hydrogen peroxide caused by reduction, the total carbon degraded in fracturing outlet liquid is cooperateed with, so as to reduce
CODCr。
O2+2H++2e-→H2O2
Due in pigment wastewater except containing hardly degraded organic substances such as substantial amounts of inorganic salts, condensed-nuclei aromatics, heterocyclic hydrocarbons, these
Organic matter is in the presence of electrocatalytic oxidation system, and azo group (- N=N-) is destroyed, and cyclic structure is opened, so as to CODCr
To reduction, toxicity is weakened, and some can not originally be characterized into CODCrMaterial after this electrocatalytic oxidation system its structure
In rock-steady structure be broken, also can be by CODCrCharacterize, the waste water COD after electrocatalytic oxidationCrIt is reduced to 6000~
7000mg/L。
(3) hydrolysis acidification：Electrocatalytic oxidation water outlet is delivered to sequential hydrolysis acidification system, hydrolysis acidification technique through delivery pump
It is to integrate precipitation, absorption, biological flocculation and precipitation, biodegradable efficient process cell process, the technique is in actual motion
Main purpose is to continue with improving biodegradability, still has some organic matters can not be by the system in previous step electrocatalytic oxidation system
The biochemical type organic matter of small molecule is degraded into, these organic matters can not more be degraded under complete aerobic condition, therefore add
Hydrolysis acidification system, in such a system these can not by the material of biochemistry by role transformations of acid-producing bacteria for can be by methanogen
Or the small molecule volatile acid that utilizes of aerobic bacteria is so as to improving wastewater biodegradability.In this Hydrolysis Acidification, CODCrHave one
Determine the reduction of degree, its clearance is 40% or so, water outlet CODCr4000mg/L or so is reduced to, is largely reduced
To the load impact of follow-up MBR system.
(4) effect of the hydrolysis acidification system water outlet through pump enters MBR system, and this is a kind of new contact film biology
Reactor, it is made up of flat plate ultrafiltration film separation unit and biological processing unit two parts, in the biological processing unit in the device
Activated sludge be Suzhou Environmental Protection Technology Co., Ltd of Ju Zhi Tontrus (bacterium numbering SGT-GY-1, enterprises numbering) for height
Salt organic pigment production waste water carry out professional separation, domestication, reinforcings and high-efficiency activated sludge, there is very strong adaptability.
MBR techniques have the characteristics that load height, impact resistance, effluent quality is limpid, suspension is practically negligible, and its treatment effect is far above biography
The activated sludge process of system.The Flat Membrane used in flat plate ultrafiltration film unit is my house journal's product, hollow compared to traditional
For tunica fibrosa, the Flat Membrane of my company has more obvious advantage, and flat board MBR can be kept under higher activated sludge concentration
High-throughout stable operation, be not in hair, fracture of wire or fiber winding etc. hollow-fibre membrane FAQs, simultaneously because
The aerating system of MBR bottoms can carry out effective sluicing to diaphragm, so that what it can effectively stablize in the process of running
The pollution condition on film surface is controlled, so as to extend the cleaning frequency of film, increases its service life, reduces operating cost.MBR system
Water outlet is limpid, CODCrIt is reduced to be less than 500mg/L in the presence of aerobic bacteria, meets that industrial park sewage disposal system is received
Pipe standards.
The present invention high salt organic pigment production wastewater treatment technique be further：Waste water residence time in regulating reservoir is
12h；
The present invention high salt organic pigment production wastewater treatment technique be further：The service condition of electrocatalytic oxidation system
It is as shown in the table：
The present invention high salt organic pigment production wastewater treatment technique be further：The service condition of hydrolysis acidification system is such as
Shown in following table：
The present invention high salt organic pigment production wastewater treatment technique be further：The service condition of MBR system such as following table
Shown, wherein dissolved oxygen is adjusted by adjusting aeration quantity, and wherein membrane flux specifically regards influent CODCrChange with water can
Regulation.
The present invention has CODCrThe characteristics of clearance is high, treatment effect is stable, it is ensured that the water outlet after processing can reach enterprise
Pipe requirement is received in place industrial park.
Compared with prior art, technique effect of the invention is：
The electrocatalytic oxidation system of the present invention has higher efficiency, can be by the azo group in most waste water, condensed ring virtue
Hydrocarbon, benzene, naphthalene, anthracene, quinones organic matter, aromatic amine compounds, aromatic nitro compound etc. all obtain a certain degree of removal,
So that the toxicity of waste water substantially reduces.The organic matter that addition hydrolysis acidification step makes to be degraded by electrocatalytic oxidation system continues quilt
Small molecule volatile acid is degraded into, so as to largely improve the biodegradability of waste water, is provided for follow-up MBR system stable
Intake water source.The Halophiles cultivated with great concentration using my company in MBR system, the strain remains in that very strong under high salt conditions
Bioactivity, what can be stablized continues the small molecule volatile acid in waste water degraded even mad chemical conversion CO2+H2O, so as to ensure water outlet
CODCr＜ 500mg/L, satisfaction receive pipe requirement.The activated sludge in biological processing unit in the device is Suzhou Ju Zhi Tontrus ring
Protect Science and Technology Ltd..
【Brief description of the drawings】
The process chart of Fig. 1 present invention.
The structural representation of the MBR system of Fig. 2 present invention；
Mark in annex for：1 collector pipe, 2 membrane components, 3 membrane modules, 4 air blowers, 5 aeration tubes, 6 sludge pumps, 7 is remaining
Mud discharging mouth, 8 self priming pumps.
【Embodiment】
A kind of embodiment of the processing method of high salt organic pigment production waste water of the present invention presented below.
Embodiment 1
The high salt organic pigment production waste water of certain company uses handling process of the present invention, and waste water is carried out as follows
Processing：
1) high salt organic pigment production waste water is discharged into regulating reservoir 1, it is equal to carry out homogeneous to waste water by bottom of pond aerating system
Measure, water outlet COD in regulating reservoirCrAverage value is 12000mg/L, subsequently into electrocatalytic oxidation system；
2) operational factor in electrocatalytic oxidation system is respectively：Water inlet pH value 6~9, running current 3A, working voltage 28
~30V, 30~60min of residence time, the electrode in system uses graphite electrode, and for negative electrode, Ti-Ru electrode is anode, catalysis
The IR series of high efficiency catalyst of my company's research and development is loaded in post.Water outlet COD in electrocatalytic oxidation systemCrBe degraded to 6000~
7000mg/L, subsequently into hydrolysis acidification system；
3) in hydrolysis acidification system operational factor difference it is as shown in the table, the hydrolysis acidification system in the process of running by
In being destroyed azo group (- N=N-) so that the ammonia-nitrogen content in system is higher, formation ammonia system's cushioning liquid is so that be
Alkalescence is presented in pH value in system, therefore system operationally sets real-time pH value to detect, once the pH value in system exceedes system
Preset value, then acid is added from trend system by medicine machine so as to keep pH value.Water outlet COD in hydrolysis acidification systemCrQuilt
3000~4000mg/L is reduced to, subsequently into the MBR system of next step；
4) operational factor in MBR system is as shown in the table, and the strain used in system company is studied with great concentration for many years for me
The Halophiles of domestication, the bacterial strain still keep certain activity, the organic face of the high salt in the environment of salt content up to extreme 15%
Material production waste water by early stage electrocatalytic oxidation be greatly improved with its biodegradability after hydrolysis acidification, through MBR system
Ensure water outlet COD after operationCr＜ 500mg/L, so as to meet to receive pipe requirement.
System Inlet and outlet water water quality difference is as shown in the table：
| Index item | Water inlet | Water outlet |
| pH | 6-9 | 6-9 |
| CODCr | 14000 | 410 |
| Ammonia nitrogen | 45 | 2.1 |
Including MBR reaction tanks in MBR system, MBR reaction tanks include collector pipe 1, membrane module 3, air blower 4, aeration tube 5,
Sludge pump 6 and self priming pump 8, membrane module include membrane component 2；Collector pipe is connected by membrane module, and the bottom of membrane module is set
Aeration tube, sludge pump and air blower are set at the bottom both ends of MBR reaction tanks respectively, and sludge pump is arranged by pipeline and excess sludge
Put mouth to be connected, and be connected in the upper end of collector pipe with self priming pump.The bubble of aeration tube bulging can wash away membrane component table in membrane module
Face, prevent pollutant in film surface attachment.And it is connected in the upper end of collector pipe with self priming pump.The bubble of aeration tube bulging can wash away
Membrane component surface in membrane module, prevent pollutant in film surface attachment.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, without departing from the inventive concept of the premise, can also make some improvements and modifications, these improvements and modifications also should be regarded as
In protection scope of the present invention.
Claims (4)
1. a kind of processing method of high salt organic pigment production waste water, it is characterised in that it is concretely comprised the following steps：
(1) high salt organic pigment waste water is provided with aerating system and waste water is carried out sufficiently through pipeline to regulating reservoir, bottom of pond
Homogeneous is mixed, and waste water homogeneous is measured, and stable water inlet is provided for follow-up system；
(2) effect of the regulating reservoir water outlet through pump enters electrocatalytic oxidation system, obtains the waste water of electrocatalytic oxidation；
(3) follow-up hydrolysis acidification pool will be delivered to by delivery pump by the waste water of electrocatalytic oxidation, obtains electrocatalytic oxidation
Waste water after processing；
(4) effect of the water outlet of hydrolysis acidification system through pump enters MBR system, finally gives the water after processing；
In described step (2), for electrocatalytic oxidation system using graphite as negative electrode, Ti-Ru electrode is anode, whole reactor
For rectangle, the pole plate of negative electrode and anode is individually positioned in the both ends of reactor, and plate width is consistent with reactor insied width；
In described step (2), 5 reaction zones, different zones are divided into the reaction in the two-plate of electrocatalytic oxidation system
Separated by rubber net panel, composite catalyzing filler is filled with regional；
In described step (2), the main component of the composite catalyzing filler of electrocatalytic oxidation system is active powdered carbon and iron, its
Mass ratio is 10:0.1~10:1, composite catalyzing filler is pressed into honeycomb oblong-shaped；Waste water enters from one end of reactor,
The other end flows out；
In described step (3), hydrolysis acidification pool is that one end is water inlet, and the other end is water outlet, and water inlet pipe is perforated pipe, water outlet
Effluent trough is set；Effluent trough open interior leads to follow-up MBR reaction tanks；
In described step (4), MBR system includes MBR reaction tanks, and MBR reaction tanks include collector pipe, membrane module, air blower,
Aeration tube, sludge pump and self priming pump；Collector pipe is connected by membrane module, and the bottom of membrane module sets aeration tube, anti-in MBR
Ying Chi bottom both ends set sludge pump and air blower respectively, and sludge pump is connected by pipeline with excess sludge floss hole, and
The upper end of collector pipe is connected with self priming pump.
2. the processing method of a kind of high salt organic pigment production waste water as claimed in claim 1, it is characterised in that described
In step (3), biological rope filler is installed in the pond in hydrolysis acidification pool.
3. the processing method of a kind of high salt organic pigment production waste water as claimed in claim 1, it is characterised in that described
In step (3), the material of biological rope filler is PP or PE, biomembrane is attached with filler, in the dissolving of hydrolysis acidification pool inner water
Oxygen concentration is controlled in≤2mg/L.
4. the processing method of a kind of high salt organic pigment production waste water as claimed in claim 1, it is characterised in that described
In step (3), solve in acidification pool and be provided with submersible agitator, acted on by hydraulic mixing, to avoid sludge in hydrolysis acidification pool
Bottom deposit.
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| CN111943361B (en) * | 2019-05-17 | 2023-11-10 | 华东理工大学 | Treatment system and method for degrading fracturing flowback fluid organic matters by salt-tolerant bacteria |
| CN112551818B (en) * | 2020-12-17 | 2022-07-19 | 广州中国科学院先进技术研究所 | High-salinity organic wastewater treatment system and treatment method |
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