CN106673295A - Method for treating high-concentration formaldehyde wastewater - Google Patents
Method for treating high-concentration formaldehyde wastewater Download PDFInfo
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- CN106673295A CN106673295A CN201610965882.4A CN201610965882A CN106673295A CN 106673295 A CN106673295 A CN 106673295A CN 201610965882 A CN201610965882 A CN 201610965882A CN 106673295 A CN106673295 A CN 106673295A
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
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Abstract
The invention relates to the field of wastewater treatment, relates to a method for treating high-concentration formaldehyde wastewater, particularly to a catalytic oxidation method for treating high-concentration formaldehyde wastewater generated in a glyoxal gas phase oxidation synthesis process. The method comprises the following steps: (1) performing pre-adjustment, namely, adding Cu(II) into raw formaldehyde wastewater, and adjusting the pH value to be within 8-12; (2) performing reaction-deposition, namely, performing heating oxidation inside a reaction-deposition tank, after the reaction is completed, leaving to stand so as to obtain sludge and supernate, feeding the supernate into an ion exchange column, and flowing into a biochemical system; (3) recycling the sludge, namely, performing concentration and filter pressing on the sludge obtained in the step (2) so as to obtain dehydrated sludge; (4) regenerating a catalyst, namely, mixing the dehydrated sludge with raw water phase, performing catalytic oxidation, feeding into the reaction-deposition tank, and repeating steps (2) to (4). The method is simple and convenient to operate, high in efficiency, low in consumption, low in investment and low in operation cost, and compared with a conventional ash method for treating the high-concentration formaldehyde wastewater, the method is free of solid waste treatment cost, and relatively high in COD (Chemical Oxygen Demand) removal rate.
Description
Technical field
The present invention relates to field of waste water treatment, in particular to a kind of method of process high-concentration formaldehyde wastewater, more particularly to
A kind of catalysed oxidation processes of the high-concentration formaldehyde wastewater produced in glyoxal vapour phase oxidation process synthesis technique.
Background technology
At present, the method that high-concentration formaldehyde wastewater is processed both at home and abroad can be divided mainly into：Physical, chemical method and bioanalysis etc.
Three major types.
（1）Physical mainly has absorption method and blow-off method.The general principle of absorption method is exactly ought to contain the waste water of formaldehyde and consolidate
Body particle, when particularly for example activated carbon, bentonite are contacted with some porous particles, some of fluid component is just enriched in solid
In body particle, adsorb.Therefore adsorbent not only needs larger specific surface area and suitable pore-size distribution, surface sense
The species of group is also particularly significant.The defect of absorption method is difficult desorption；
Blow-off method be using formaldehyde low boiling point, volatile feature, stripping pretreatment is carried out with steam to the formaldehyde in waste water with
Reach a kind of method of removal formaldehyde purpose, it is adaptable to the formaldehyde of high concentration（General concentration of formaldehyde is more than 10,000 milligrams per liter）,
Have the disadvantage high energy consumption.
（2）Chemical method mainly has combustion method, advanced oxidation processes and Coagulation Method etc..
Combustion method is a kind of method for thoroughly removing formaldehyde in waste water, is adapted to more than 30000 milligrams per liter of concentration of formaldehyde.Will
Waste water jet pipe sprays into burner hearth atomization, and by flame combustion, clearance can reach more than 99%, but energy consumption and equipment investment
It is larger.
Authorization Notice No. discloses one kind for the Chinese invention patent of CN 1168667C《Formaldehyde waste water processing method》, will
Formaldehyde waste water is sprayed on high temperature furnace slag after atomization, realization react and be cracked into water and carbon dioxide, its shortcoming also show and
It is clear to, i.e. equipment investment is larger.
Advanced oxidation processes common are Fenton oxidation method, wet oxidation process, photocatalytic oxidation etc..Fenton oxidation method advantage
It is that clearance is high, has the disadvantage that oxidizer is high, the formaldehyde waste water that about 10000 milligrams per liter of general concentration for the treatment of, oxidating chemicals
Cost is more than 100 yuan of waste water per ton；In addition the first investment of wet oxidation process and photocatalytic method is big.
Coagulation Method using natural sedimentation method remove waste water in fine suspension and colloidal particles, reduce waste water turbidity and
Colourity, can also remove formaldehyde etc., be a kind of method conventional when processing industry high-concentration formaldehyde waste water, have the disadvantage treatment effect not
Good, solid waste amount is big, and filtration difficulty, dehydration difficulty often occurs in Jing in engineering.
（3）It is using the metabolism of microorganism, to the formaldehyde in waste water that biochemical process processes high-concentration formaldehyde wastewater
Converted, be allowed to innoxious processing method.The clearance of formaldehyde can reach more than 90%, and operating cost is low.But formaldehyde
To the active inhibited of microorganism, the maximum concentration of conventional microbiological tolerance methanal is about 200 milligrams per liter.
As Chinese invention patent of the application publication number for the A of CN 105399279 is disclosed at a kind of chemical-biological combination method
The method of reason high-concentration formaldehyde wastewater, before biochemical treatment is carried out, its PARA FORMALDEHYDE PRILLS(91,95) waste water has carried out Membrane Materials pretreatment so that
Waste water meets the condition for carrying out biochemical treatment, it may have equipment investment is big, the shortcoming of high energy consumption.
The content of the invention
The formalin of the main technical finesse high concentration by copper ion catalytic air oxidation formaldehyde of the invention, it is proposed that
A kind for the treatment of by catalytic oxidation of new high-concentration formaldehyde wastewater, cleverly switched by reaction-sedimentation basin, sludge it is dense
Contracting, the regeneration of catalyst, the clearance of formaldehyde and COD in waste water can reach respectively 85%, more than 90%.
For achieving the above object, a kind of method of process high-concentration formaldehyde wastewater of present invention design, comprises the steps：
1. precondition：Add Cu (II) in pending formaldehyde waste water raw water, and with alkali lye by its pH value adjust to 8 ~ 12 it
Between；
2.-precipitation is reacted：Formaldehyde waste water after preconditioning is aoxidized in reaction-precipitation pool heating process, in oxidizing process constantly
Ground addition alkali lye is undergone mutation up to the color in the reaction-sedimentation basin, and stewing process after the completion of reaction obtains red or brown
The sludge and supernatant of color, the supernatant is reclaimed into ion exchange column to bivalent cupric ion, then flows into department of biochemistry
System；
The biochemical system can be preposition or comprising the first regulating reservoir, for adjusting the solution parameter into before biochemical system；
3. sludge is reclaimed：The separated entrance sludge concentration tank of sludge that step is obtained after 2. standing, in the sludge concentration tank
Concentrated and obtained dewatered sludge Jing after plate and frame filter press process；
The sludge is segregated into sludge concentration tank by the mud scraper of bottom, and the moisture content of the dewatered sludge is 60% or so；
4. catalyst regeneration：The dewatered sludge is mixed with the raw water of formaldehyde waste water, in catalyst regenerated reactor air is used
Aeration carries out aoxidizing the solution for obtaining blueness, and this blue solution alkali lye is adjusted pH value between 8 ~ 10, enters back into described
In reaction-sedimentation basin；
Dewatered sludge is set to mix and dissolve here with the acidity of formaldehyde waste water raw water, then the subsequent treatment such as row aeration；
Aeration rate is raised with concentration of formaldehyde and raised.Whole process, oxidant is oxygen, need to only add liquid caustic soda to maintain oxidation-precipitation
Pond pH is 8 ~ 10.
5. circular treatment：Repeat step 2. ~ 4..
The present invention principle be：
Formaldehyde Jing Cu in formaldehyde waste water（II）Oxidation in the basic conditions generates formic acid, and part formic acid is in Cu（II）Enter under catalysis
The oxidation of one step generates carbon dioxide and water, therefore puts into practice the discovery technique PARA FORMALDEHYDE PRILLS(91,95) and COD with the effect for removing simultaneously.
The water intake mode of reaction-sedimentation basin can be with intermittent water inflow or continuum micromeehanics, when pond volume is big, water inlet formaldehyde is dense
When spending high, its water inlet can take multipoint water feeding mode；High-concentration formaldehyde wastewater can be delayed into water speed, for low concentration first
Aldehyde waste water, water inlet speed can suitably be accelerated.
As the preferred of above-mentioned technical proposal, step 1. with step 4. in alkali lye used be mass concentration be 28%-32%
Sodium hydroxide solution.
As the preferred of above-mentioned technical proposal, step 1. middle alkali lye addition quality for formaldehyde waste water quality 1.5% ~
20%。
As the preferred of above-mentioned technical proposal, step 1. middle addition Cu (II) add quality be wastewater quality 1% ~
10%。。
Used as the preferred of above-mentioned technical proposal, the temperature of step 2. middle heated oxide is maintained between 60 ~ 85 DEG C, during reaction
Between be 30 ~ 60 minutes, wherein constantly add in oxidizing process alkali lye until the reaction-sedimentation basin in color undergo mutation
React again afterwards 15 ~ 30 minutes.
As the preferred of above-mentioned technical proposal, step 4. in the raw water of the dewatered sludge and formaldehyde waste water is mixed after
The pH value of mixed liquor is adjusted between 3 ~ 5 with concentrated hydrochloric acid, then carries out air aeration.
As the preferred of above-mentioned technical proposal, step 2. described in reaction-sedimentation basin be two, one of them reaction
When, another is automatically controlled by valve and is carried out into water and water outlet carrying out stratification, two reaction-sedimentation basins.
Used as the preferred of above-mentioned technical proposal, the reaction-sedimentation basin is using the sbr reactor for including mixing-aeration-precipitation
The AAO structure of reactor of device structure or anaerobic reaction-hypoxia response-aerobic reaction-precipitation.
SBR is the abbreviation of sequencing batch active sludge, is a kind of activated sludge sewage run by intermittent aerating mode
Treatment technology.Its orderly and intermittently operated being mainly characterized by operationally, the core of SBR technologies is sbr reactor pond, the pond
Collect homogenizing, it is just heavy, biodegradable, two the function such as sink in a pond, without sludge recirculation system.It is particularly suited for intermittent discharge and flow
The occasion for changing greatly.It is widely used at home at present.
AAO is also known as A2O, is the abbreviation of English Anaerobic-Anoxic-Oxic first letters（Anaerobic- anoxic- oxic
Method）, it is a kind of conventional sewage treatment process, can be used for B-grade sewage and process or three-level sewage disposal, and Treated sewage reusing.
As the preferred of above-mentioned technical proposal, the reaction-sedimentation basin adopt sbr reactor device structure, the now reaction-
The pond depth of sedimentation basin is 4 ~ 6 meters, and the wide ratio with pond length in pond is 1:1~1:2.
Used as the preferred of above-mentioned technical proposal, it is molten that the catalyst regenerated reactor is divided into sludge mixing according to fluid flow direction
Xie Qu and air aeration oxidation regeneration area.
The present invention compared with prior art, with advantages below and beneficial effect：
（1）Described technique water inlet operation is easy, efficient, low consumption, more flexibility simple to operate, reduced investment, running cost
With low；
（2）Described method compared with traditional lime method processes high-concentration formaldehyde wastewater, without solidification disposal of waste cost, and to COD
Clearance is higher；
（3）Described formaldehyde waste water catalyst copper ion is cheap and easy to get, the water outlet not copper ions Jing after Copper Ion Exchange post, copper from
The bio-toxicity that son causes is extremely low, can be directly entered biochemical system.
Description of the drawings
Fig. 1 is the method flow block diagram of Cu (II) catalytic oxidation treatment of high concentration formaldehyde waste water, and wherein dotted line is sludge biography
Defeated route, solid line is feed liquid transmission route.
In figure：Reaction-sedimentation basin 1, ion exchange column 2, biochemical system 3, sludge concentration tank 4, plate and frame filter press 5, catalysis
Agent regenerated reactor 6.
Specific embodiment
Below in conjunction with the accompanying drawings the present invention is described in further detail with specific embodiment：
Embodiment 1：Certain medicine company Science and Technology Co., Ltd. produces glyoxal intermediate using vapour phase oxidation process, and workshop produces
The high-concentration formaldehyde wastewater of 1000t/d, water quality is as follows：, in 6000 ~ 11000mg/L, COD is in 8500 ~ 15000mg/ for concentration of formaldehyde
L, raw water clear, pH=3.5, in addition containing a small amount of methyl alcohol（Within concentration 100mg/L）.Process through this technological process, ginseng
Fig. 1 is examined, i.e.,：
1. precondition：Add Cu (II) in pending formaldehyde waste water raw water, and with the sodium hydroxide solution of 28%-32% by its
PH value is adjusted between 8 ~ 12；
2.-precipitation is reacted：The heating in reaction-sedimentation basin 1 of formaldehyde waste water after preconditioning is aoxidized, in oxidizing process constantly
Ground addition alkali lye until the reaction-sedimentation basin 1 in color undergo mutation, stewing process after the completion of reaction, obtain redness or
The sludge and supernatant of brown, the supernatant is reclaimed into ion exchange column 2 to bivalent cupric ion, is then flowed into biochemical
System 3；
3. sludge is reclaimed：The separated entrance sludge concentration tank 4 of sludge that step is obtained after 2. standing, in the sludge concentration tank 4
Inside concentrated and obtained dewatered sludge Jing after the process of plate and frame filter press 5；
4. catalyst regeneration：The dewatered sludge is mixed with the raw water of formaldehyde waste water, in the interior air of catalyst regenerated reactor 6
Aeration carries out aoxidizing the solution for obtaining blueness, this blue solution is adjusted pH value to 8 with the sodium hydroxide solution of 28%-32% ~
Between 10, enter back into the reaction-sedimentation basin 1；
5. circular treatment：Repeat step 2. ~ 4..
The temperature of heated oxide is maintained between 60 ~ 70 DEG C, and the reaction time is 30 ~ 35 minutes, wherein in oxidizing process not
Add alkali lye disconnectedly until the color in the reaction-sedimentation basin 1 reacts again 15 ~ 20 minutes after undergoing mutation；Whole process liquid
Alkali dosage is 10 ~ 20%, it is not necessary to add concentrated hydrochloric acid, adopts cupric Cu (II) catalyst amountses for 5% ~ 10%（According to water
Matter fluctuation is adjusted）；
Whole technique cupric catalysis oxidation water outlet concentration of formaldehyde is 156 ~ 188mg/L, bio-chemical effluent concentration of formaldehyde 0.5 ~
0.7mg/L, meets《GB8978-2002 national sewage comprehensive emission standards》In one-level A standard.
Embodiment 2：Certain medicine company Science and Technology Co., Ltd. produces glyoxal intermediate using vapour phase oxidation process, and workshop produces
The high-concentration formaldehyde wastewater of 600t/d, water quality is as follows：, in 9500 ~ 17000mg/L, COD is in 13000 ~ 21000mg/ for concentration of formaldehyde
L, raw water clear, pH=2.9, in addition containing a small amount of methyl alcohol（Within concentration 100mg/L）.Process through this technological process, ginseng
Fig. 1 is examined, i.e.,：
1. precondition：Add Cu (II) in pending formaldehyde waste water raw water, and with the sodium hydroxide solution of 28%-32% by its
PH value is adjusted between 8 ~ 12；
2.-precipitation is reacted：The heating in reaction-sedimentation basin 1 of formaldehyde waste water after preconditioning is aoxidized, in oxidizing process constantly
Ground addition alkali lye until the reaction-sedimentation basin 1 in color undergo mutation, stewing process after the completion of reaction, obtain redness or
The sludge and supernatant of brown, the supernatant is reclaimed into ion exchange column 2 to bivalent cupric ion, is then flowed into biochemical
System 3；Reaction-the sedimentation basin adopts the sbr reactor device structure for including mixing-aeration-precipitation, the reaction-sedimentation basin 1
Chi Shen is 4 meters, and the wide ratio with pond length in pond is 1:2；
3. sludge is reclaimed：The separated entrance sludge concentration tank 4 of sludge that step is obtained after 2. standing, in the sludge concentration tank 4
Inside concentrated and obtained dewatered sludge Jing after the process of plate and frame filter press 5；
4. catalyst regeneration：The dewatered sludge is mixed with the raw water of formaldehyde waste water, in the interior air of catalyst regenerated reactor 6
Aeration carries out aoxidizing the solution for obtaining blueness, this blue solution is adjusted pH value to 8 with the sodium hydroxide solution of 28%-32% ~
Between 10, enter back into the reaction-sedimentation basin 1；
5. circular treatment：Repeat step 2. ~ 4..
That is the temperature of heated oxide is maintained between 80 ~ 85 DEG C, and the reaction time is 50 ~ 60 minutes, wherein in oxidizing process
Constantly add alkali lye until the color in the reaction-sedimentation basin 1 reacts again 25 ~ 30 minutes after undergoing mutation；Whole process
Liquid caustic soda dosage, without concentrated hydrochloric acid, adopts cupric Cu (II) catalyst amountses for 8% ~ 10% 16 ~ 20%（According to water quality
Fluctuation is adjusted）；
Whole technique cupric catalysis oxidation water outlet concentration of formaldehyde is 198 ~ 256mg/L, bio-chemical effluent concentration of formaldehyde 0.5 ~
0.8mg/L, meets《GB8978-2002 national sewage comprehensive emission standards》In one-level A standard.
Embodiment 3：Certain pharmacy corporation high-concentration formaldehyde wastewater, containing a small amount of phenol, water quality is as follows：Concentration of formaldehyde 4000 ~
6500mg/L, COD are in 8600 ~ 14700mg/L, raw water clear, pH=5, within 700 ~ 860mg/L of phenol concentration.Through this
Technological process is processed, with reference to Fig. 1, i.e.,：
1. precondition：Add Cu (II) in pending formaldehyde waste water raw water, and with the sodium hydroxide solution of 28%-32% by its
PH value is adjusted between 8 ~ 12；
2.-precipitation is reacted：The heating in reaction-sedimentation basin 1 of formaldehyde waste water after preconditioning is aoxidized, in oxidizing process constantly
Ground addition alkali lye until the reaction-sedimentation basin 1 in color undergo mutation, stewing process after the completion of reaction, obtain redness or
The sludge and supernatant of brown, the supernatant is reclaimed into ion exchange column 2 to bivalent cupric ion, is then flowed into biochemical
System 3, the reaction-sedimentation basin 1 is using the sbr reactor device structure for including mixing-aeration-precipitation, the reaction-sedimentation basin 1
Pond depth be 6 meters, the wide ratio with pond length in pond is 1:1；
3. sludge is reclaimed：The separated entrance sludge concentration tank 4 of sludge that step is obtained after 2. standing, in the sludge concentration tank 4
Inside concentrated and obtained dewatered sludge Jing after the process of plate and frame filter press 5；
4. catalyst regeneration：The dewatered sludge is mixed with the raw water of formaldehyde waste water, in the interior air of catalyst regenerated reactor 6
Aeration carries out aoxidizing the solution for obtaining blueness, this blue solution is adjusted pH value to 8 with the sodium hydroxide solution of 28%-32% ~
Between 10, enter back into the reaction-sedimentation basin 1；
5. circular treatment：Repeat step 2. ~ 4..
The temperature of heated oxide is maintained between 70 ~ 80 DEG C, and the reaction time is 35 ~ 45 minutes, wherein in oxidizing process not
Add alkali lye disconnectedly until the color in the reaction-sedimentation basin 1 reacts again 20 ~ 25 minutes after undergoing mutation；Whole process liquid
6 ~ 14%, concentrated hydrochloric acid dosage 1 ~ 3% adjusts the material liquid PH value before aeration between 3 ~ 5 to alkali dosage；Using cupric
Cu (II) catalyst amountses are 5% ~ 8%（Adjusted according to variation water quality）；
Whole technique cupric catalysis oxidation water outlet concentration of formaldehyde is less than 200mg/L, bio-chemical effluent 0.3 ~ 0.5mg/ of concentration of formaldehyde
L, meets《GB8978-2002 national sewage comprehensive emission standards》In one-level A standard.
Embodiment 4：Certain pharmacy corporation high-concentration formaldehyde wastewater, containing a small amount of phenol, water quality is as follows：Concentration of formaldehyde 6000 ~
8500mg/L, COD are in 12500 ~ 16600mg/L, raw water clear, pH=5.2）.Process through this technological process, with reference to figure
1, i.e.,：
1. precondition：Add Cu (II) in pending formaldehyde waste water raw water, and with the sodium hydroxide solution of 28%-32% by its
PH value is adjusted between 8 ~ 12；
2.-precipitation is reacted：The heating in reaction-sedimentation basin 1 of formaldehyde waste water after preconditioning is aoxidized, in oxidizing process constantly
Ground addition alkali lye until the reaction-sedimentation basin 1 in color undergo mutation, stewing process after the completion of reaction, obtain redness or
The sludge and supernatant of brown, the supernatant is reclaimed into ion exchange column 2 to bivalent cupric ion, is then flowed into biochemical
System 3, the reaction-sedimentation basin 1 adopts the AAO structure of reactor of anaerobic reaction-hypoxia response-aerobic reaction-precipitation, quantity
For two,, in reaction, another is carrying out stratification, and two reaction-sedimentation basins 1 are automatic by valve for one of them
Control is carried out into water and water outlet；
3. sludge is reclaimed：The separated entrance sludge concentration tank 4 of sludge that step is obtained after 2. standing, in the sludge concentration tank 4
Inside concentrated and obtained dewatered sludge Jing after the process of plate and frame filter press 5；
4. catalyst regeneration：The dewatered sludge is mixed with the raw water of formaldehyde waste water, in the interior air of catalyst regenerated reactor 6
Aeration carries out aoxidizing the solution for obtaining blueness, this blue solution is adjusted pH value to 8 with the sodium hydroxide solution of 28%-32% ~
Between 10, the reaction-sedimentation basin is entered back into（1）Interior, the catalyst regenerated reactor 6 is divided into sludge according to fluid flow direction to be mixed
Close dissolving area and air aeration oxidation regeneration area；
5. circular treatment：Repeat step 2. ~ 4..
The temperature of heated oxide is maintained between 75 ~ 85 DEG C, and the reaction time is 45 ~ 55 minutes, wherein in oxidizing process not
Add disconnectedly after alkali lye is undergone mutation up to the color in the reaction-sedimentation basin 1 and react again 20 ~ 30 minutes, wherein；Whole mistake
1.5 ~ 10%, concentrated hydrochloric acid dosage 1 ~ 3% adjusts the material liquid PH value before aeration between 3 ~ 5 to journey liquid caustic soda dosage；Using
Cupric Cu (II) catalyst amountses are 1% ~ 7%（Adjusted according to variation water quality）；
Whole technique cupric catalysis oxidation water outlet concentration of formaldehyde is less than 200mg/L, bio-chemical effluent 0.3 ~ 0.6mg/ of concentration of formaldehyde
L, meets《GB8978-2002 national sewage comprehensive emission standards》In one-level A standard.
Claims (10)
1. it is a kind of process high-concentration formaldehyde wastewater method, it is characterised in that comprise the steps：
1. precondition：Add Cu (II) in pending formaldehyde waste water raw water, and with alkali lye by its pH value adjust to 8 ~ 12 it
Between；
2.-precipitation is reacted：Formaldehyde waste water after preconditioning is in reaction-sedimentation basin（1）Interior heating is aoxidized, in oxidizing process not
Add alkali lye disconnectedly until reaction-the sedimentation basin（1）Interior color is undergone mutation, stewing process after the completion of reaction, obtains red
The sludge and supernatant of color or brown, the supernatant enters ion exchange column（2）Bivalent cupric ion is reclaimed, is then flowed
Enter biochemical system（3）；
3. sludge is reclaimed：The separated entrance sludge concentration tank of sludge that step is obtained after 2. standing（4）, in the sludge concentration tank
（4）Inside carry out concentrating and Jing plate and frame filter press（5）Dewatered sludge is obtained after process；
4. catalyst regeneration：The dewatered sludge is mixed with the raw water of formaldehyde waste water, in catalyst regenerated reactor（6）It is interior to use empty
Gas aeration carries out aoxidizing the solution for obtaining blueness, and this blue solution alkali lye is adjusted pH value between 8 ~ 10, enters back into institute
State reaction-sedimentation basin（1）It is interior；
5. circular treatment：Repeat step 2. ~ 4..
2. according to claim 1 it is a kind of process high-concentration formaldehyde wastewater method, it is characterised in that：Step is 1. with step 4.
In alkali lye used be mass concentration be 28%-32% sodium hydroxide solution.
3. according to claim 2 it is a kind of process high-concentration formaldehyde wastewater method, it is characterised in that：Step 1. middle alkali lye
Addition quality is the 1.5% ~ 20% of formaldehyde waste water quality.
4. according to claim 1 it is a kind of process high-concentration formaldehyde wastewater method, it is characterised in that：Step 1. middle addition Cu
(II) add quality be wastewater quality 1% ~ 10%.
5. according to claim 1 it is a kind of process high-concentration formaldehyde wastewater method, it is characterised in that：Step 2. middle heating oxygen
The temperature of change is maintained between 60 ~ 85 DEG C, and the reaction time is 30 ~ 60 minutes, alkali lye is wherein constantly added in oxidizing process straight
To the reaction-sedimentation basin（1）Interior color reacts again 15 ~ 30 minutes after undergoing mutation.
6. according to claim 1 it is a kind of process high-concentration formaldehyde wastewater method, it is characterised in that：Step 4. in will be described
The raw water of dewatered sludge and formaldehyde waste water is adjusted the pH value of mixed liquor between 3 ~ 5 with concentrated hydrochloric acid after mixing, then carries out sky
Gas aeration.
7. according to claim 1 it is a kind of process high-concentration formaldehyde wastewater method, it is characterised in that：Step 2. described in it is anti-
Should-sedimentation basin（1）For two,, in reaction, another is carrying out stratification, two reaction-sedimentation basins for one of them
（1）Being automatically controlled by valve is carried out into water and water outlet.
8. according to claim 1 it is a kind of process high-concentration formaldehyde wastewater method, it is characterised in that：Reaction-the precipitation
Pond（1）Using the sbr reactor device structure or anaerobic reaction-hypoxia response-aerobic reaction-precipitation for including mixing-aeration-precipitation
AAO structure of reactor.
9. according to claim 8 it is a kind of process high-concentration formaldehyde wastewater method, it is characterised in that：Reaction-the precipitation
Pond（1）Using sbr reactor device structure, the now reaction-sedimentation basin（1）Pond depth be 4 ~ 6 meters, the ratio of pond width and pond length is
1:1~1:2。
10. according to claim 1 or 6 it is a kind of process high-concentration formaldehyde wastewater method, it is characterised in that：The catalyst
Regenerated reactor（6）It is divided into sludge mixed dissolution area and air aeration oxidation regeneration area according to fluid flow direction.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107473481A (en) * | 2017-08-31 | 2017-12-15 | 河海大学 | The garbage percolation liquid treating system and method for ultrasonic stripping film distillation technology combination |
| CN110327579A (en) * | 2019-07-26 | 2019-10-15 | 广州超威生物科技有限公司 | It is a kind of efficiently to remove formaldehyde composition |
| CN113698022A (en) * | 2021-09-15 | 2021-11-26 | 武汉森泰环保股份有限公司 | High-concentration formaldehyde wastewater treatment device and method |
| CN114804422A (en) * | 2022-04-28 | 2022-07-29 | 山东诺尔生物科技有限公司 | Pretreatment method and pretreatment system for acrylic acid wastewater |
| CN115231778A (en) * | 2022-07-29 | 2022-10-25 | 杭州胜澜科技有限公司 | Method for treating wastewater by polymethoxy dimethyl ether |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4980857A (en) * | 1972-11-18 | 1974-08-05 | ||
| CN101844827A (en) * | 2010-05-21 | 2010-09-29 | 华东理工大学 | Method for degrading formaldehyde pollutant with catalyzing wet oxidation process |
| CN104628184A (en) * | 2015-01-22 | 2015-05-20 | 博天环境集团股份有限公司 | Method for treating formaldehyde wastewater by use of calcined hydrotalcite |
-
2016
- 2016-10-28 CN CN201610965882.4A patent/CN106673295A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4980857A (en) * | 1972-11-18 | 1974-08-05 | ||
| CN101844827A (en) * | 2010-05-21 | 2010-09-29 | 华东理工大学 | Method for degrading formaldehyde pollutant with catalyzing wet oxidation process |
| CN104628184A (en) * | 2015-01-22 | 2015-05-20 | 博天环境集团股份有限公司 | Method for treating formaldehyde wastewater by use of calcined hydrotalcite |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107473481A (en) * | 2017-08-31 | 2017-12-15 | 河海大学 | The garbage percolation liquid treating system and method for ultrasonic stripping film distillation technology combination |
| CN110327579A (en) * | 2019-07-26 | 2019-10-15 | 广州超威生物科技有限公司 | It is a kind of efficiently to remove formaldehyde composition |
| CN113698022A (en) * | 2021-09-15 | 2021-11-26 | 武汉森泰环保股份有限公司 | High-concentration formaldehyde wastewater treatment device and method |
| CN114804422A (en) * | 2022-04-28 | 2022-07-29 | 山东诺尔生物科技有限公司 | Pretreatment method and pretreatment system for acrylic acid wastewater |
| CN115231778A (en) * | 2022-07-29 | 2022-10-25 | 杭州胜澜科技有限公司 | Method for treating wastewater by polymethoxy dimethyl ether |
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