CN105712468B - A method of processing waste water difficult for biological degradation - Google Patents
A method of processing waste water difficult for biological degradation Download PDFInfo
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- CN105712468B CN105712468B CN201410724006.3A CN201410724006A CN105712468B CN 105712468 B CN105712468 B CN 105712468B CN 201410724006 A CN201410724006 A CN 201410724006A CN 105712468 B CN105712468 B CN 105712468B
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Abstract
The present invention discloses a kind of method for handling waste water difficult for biological degradation, the following steps are included: (1) adds active carbon into biochemistry pool, form active carbon-microbial bacteria micelle biochemical system, activated carbon addition is 0.5 ~ 50 g active carbon/g COD, and active carbon content meter by weight contains 0.05 ~ 10% transition metal oxide；(2) sludge containing active carbon formed in step (1) enters ozone reactor progress ozonation treatment in secondary settling tank after precipitation and separation；(3) by step (3), treated that sludge reflux containing active carbon is recycled into biochemistry pool.This method has not only recycled Powdered Activated Carbon, but also reduces the yield of sludge, improves waste water difficult for biological degradation treatment effect, greatly reduces the operating cost of PACT technique.
Description
Technical field
The invention belongs to field of waste water treatment, are related to a kind of group technology for handling waste water difficult for biological degradation, specifically
It is related to a kind of method using PACT process waste water difficult for biological degradation.It is useless that this method can be widely applied to difficult for biological degradation
The processing of water.
Background technique
With the worsening shortages of domestic crude resources, oil property it is increasingly severe, more and more Petrochemical Enterprises start
Process high-sulfur, high-acid crude oil.Since significant change has occurred in oil property, the master in the discharge amount and sewage of Shi Quan factory sewage
Pollutant concentration is wanted to obtain the increase of certain amplitude.Oil refining sewerage is after traditional oil removal, flotation processing, still containing big in water
Polycyclic, heterocycle and phenol compound are measured, these organic matters are difficult to biodegrade, and therefore, conventional Biochemical Treatment is universal
It is poor.
Adding Powdered Activated Carbon to traditional activated Sludge System is the PACT technology that DuPont Corporation develops, PACT skill
Art is to combine activated sludge and Powdered Activated Carbon, and the two collective effect increases the removal to pollutant.Since powder is living
The large specific surface area of property charcoal, refractory organic in adsorbable water, hard-degraded substance in such macro environment and toxic
The concentration of substance is reduced, also opposite to the inhibiting effect of microorganism to weaken.On the other hand, microorganism can adhere to Powdered Activated Carbon
Upper growth, while the degradable organic pollutant being adsorbed on Powdered Activated Carbon.This synergistic effect is the growth generation of microorganism
Good environment has been built in the activity of thanking, and enhances the processing to waste water difficult for biological degradation.
In the process of running, the biological activated sludge containing Powdered Activated Carbon enters secondary settling tank to PACT technique, can generate big
The sludge containing active carbon of amount, causes secondary pollution, and Powdered Activated Carbon is not recycled, operating cost is higher.
CN102616922A proposes a kind of renewable PACT new process for recycling Powdered Activated Carbon processing waste water difficult for biological degradation.Two
Through drying, destructive distillation and activation processing after the sludge dewatering with active carbon generated in heavy pond, make powder electroless plating has
Machine object decomposes volatilization, while activated sludge pyrolysis is that active carbon carries out reuse.Although Powdered Activated Carbon can be recycled in this method,
Pyrolysis temperature is at 500 ~ 600 DEG C, and for activation temperature at 800 ~ 950 DEG C, application process energy consumption is huge, and high temperature regeneration active carbon is to it
Structure also has destruction, causes active carbon intensity and reduced performance, and long-term circulation will cause water treatment effect decline.
Summary of the invention
To solve the deficiencies in the prior art, the present invention proposes a kind of PACT method for handling waste water difficult for biological degradation.The party
Method has not only recycled Powdered Activated Carbon, but also reduces the yield of sludge, improves waste water difficult for biological degradation treatment effect, significantly
Reduce the operating cost of PACT technique.
A method of processing waste water difficult for biological degradation, comprising the following steps:
(1) active carbon is added into biochemistry pool, forms active carbon-microbial bacteria micelle biochemical system, activated carbon addition
For 0.5 ~ 50 g active carbon/g COD, preferably 1.5 ~ 10 g active carbons/g COD, further preferred 3.5 ~ 6 g active carbon/g
COD, active carbon content meter by weight contain 0.05 ~ 10% transition metal oxide, and preferably 0.1 ~ 1.5%, it is further excellent
Select 0.4 ~ 0.8%；
(2) sludge containing active carbon formed in step (1) enters ozone reactor in secondary settling tank and carries out after precipitation and separation
Ozonation treatment；
(3) by step (3), treated that sludge reflux containing active carbon is recycled into biochemistry pool.
In the method for the present invention step (1), the operating condition of biochemistry pool are as follows: 0.1 ~ 3.0 kgCOD/ (m of volumetric loading3D),
4 ~ 12 h of hydraulic detention time, 1.0 ~ 1.2 kgCOD/ (m of preferable volume load3D), 6 ~ 8 h of hydraulic detention time.
In the method for the present invention step (1), the transition metal oxide includes in Fe, Mn, Co, Ni, Cu, La, Ce
One or more, preferably Ni or Cu.
In the method for the present invention step (1), the active carbon containing transition metal oxide can use commercial goods,
It is prepared such as the activated-carbon catalyst that Beijing Bishuiyuan Science and Technology Co., Ltd produces, or using the prior art, such as
Transition metal oxide is loaded on active carbon using conventional infusion process, crosses volume impregnation or incipient impregnation.
In the method for the present invention step (1), the active carbon containing transition metal oxide is prepared with the following method:
A) soluble transition metal salt is added into deionized water, then forms it into colloidal solution with lye conciliation；
B) active carbon is added in the colloidal solution of step a) and is beaten into active carbon slurries, stirred 1 ~ 6 hour；
C) then continue stirring 0.5 ~ 3 hour with lye adjusting active carbon slurry pH value to 11 ~ 12, be filtered, washed,
The active carbon of carrying transition metal oxide is made after roasting under inert atmosphere protection.
In the above method, the soluble transition metal salt includes transition metal nitrate, carbonate, sulfate or chlorine
The mixing of one or more of salt dissolving.
In the above method, the mass ratio of active carbon and water is 1:5 ~ 20, preferably 1:5 ~ 15 in the active carbon slurries.
In the above method, the lye is NaOH, NaCO3、NaHCO3、KOH、KCO3、KHCO3、(NH2)2One kind of CO
Or any several mixing, the mass percent concentration of lye are 0.1 ~ 30 %.
In the method for the present invention step (2), ozonation treatment condition is 2 ~ 20 mg/gSS, preferably 5 ~ 10 mg/gSS, is stopped
10 ~ 30 min of time.
In the method for the present invention step (3), the active carbon containing transition metal oxide of 10 ~ 20wt% can be supplemented.
Beneficial effects of the present invention are as follows: by adding to the biochemical system of processing waste water difficult for biological degradation containing transition gold
The active carbon of category, the especially homemade active carbon containing transition metal oxide can hardly possible biology drop in quick adsorption sewage
Organic matter is solved, to reduce this type organic to the inhibiting effect of microorganism.Microorganism in activated sludge is to contain transition gold
Centered on the active carbon for belonging to oxide, wraps up the active carbon containing transition metal oxide and form zoogloea wadding body, enhance micro-
Biological metabolism ability, the active carbon sludge containing transition metal oxide of formation are back to primary after ozonizing regeneration treatment
Change system has reached the dual of active carbon sludge regeneration that low-temperature atmosphere-pressure contains transition metal oxide and sludge Sources decreasing
Purpose greatly reduces the operating cost of PACT technique, with good economic efficiency.
Specific embodiment
By the following examples and comparative example further illustrates the process and effect of the method for the present invention, embodiment and compares
Example in unless otherwise specified wt% be mass fraction, the active carbon of homemade carrying transition metal oxide, active carbon buying in
Shanghai Ji Bao active carbon Co., Ltd, the property of active carbon is following: greater than 90% activated carbon particle size range in 0.63 ~ 2.0 mm,
450 ~ 550 g/L of loading density, intensity 94.
Embodiment 1
The air bearing for handling certain domestic oil plant is discharged (i.e. total water inlet of biochemistry pool), main water quality indicator are as follows: COD 275
Mg/L, BOD5For 58.3 mg/L, pH value 6.79,19.1 mg/L of volatile phenol, the active carbon buying for loading nickel oxide is green in Beijing
The activated-carbon catalyst of water source Science and Technology Co., Ltd. production, the weight content of nickel oxide are 0.1%.Air bearing is discharged through PACT
Biochemical treatment, returned sludge are handled through catalytic ozonation, and concrete operations condition and treatment effect are shown in Table 1.
Table 1
Embodiment 2
Handle the anaerobic effluent of certain alcohol waste water, main water quality indicator are as follows: COD is 2460 mg/L, BOD5For 320 mg/
L, pH value 7.56, ammonia nitrogen 56 mg/L, COD are 2460 mg/L, BOD5For 320 mg/L, pH value 7.56,56 mg/L of ammonia nitrogen is born
The active carbon of carried copper oxide is 1.5% using conventional equi-volume impregnating preparation, the weight content of copper oxide.Anaerobic effluent warp
PACT biochemical treatment, returned sludge are handled through catalytic ozonation, and concrete operations condition and treatment effect are shown in Table 2.
Table 2
| Processing unit Title | Processing unit scale And main composition | Main service condition and control parameter | Treatment effect |
| Biochemical system | PACT reactor, Organic glass material Matter, reactor hold 20 L of product | 1.2 kg COD/ (m of volumetric loading3•d)；Hydraulic retention 16 h of time；Copper oxide active Pd/carbon catalyst dosage 5 g/g COD；8000 mg/L of sludge concentration | It is discharged 280 mg/ of COD L；BOD516 mg/L； 3.1 mg/L of ammonia nitrogen； |
| Sludge ozone Catalysis oxidation System | Stainless steel material, Treating capacity 2L | 20 mg/g SS of ozone dosage；30 min of reaction time | Mud decrement 42% |
Embodiment 3
With embodiment 1, the active carbon (load capacity is with embodiment 1) for only loading nickel oxide is prepared with the following method: to
Nickel nitrate is added in deionized water, the sodium hydroxide conciliation that then mass concentration is 5% makes its 8.5 formation colloidal solution of pH value；
Active carbon is added in colloidal solution and is beaten into active carbon slurries, the mass ratio of active carbon and water is 1:5, is stirred 2 hours；Then
Continue to adjust active carbon slurry pH value to 12 with sodium hydroxide solution, continues stirring 1 hour, be filtered, washed, nitrogen atmosphere is protected
It is made after the lower roasting of shield.
Air bearing water outlet COD 50 mg/L, BOD after the processing of PACT biochemical system54.1 mg/L, 0.2 mg/ of volatile phenol
L；Returnedactivatedsludge is reduced 62% after catalytic ozonation is handled.
Embodiment 4
With embodiment 2, only the active carbon (load capacity is with embodiment 2) of loaded copper oxide is prepared with the following method: to
Copper nitrate is added in deionized water, the sodium hydroxide conciliation that then mass concentration is 25% makes its 9 formation colloidal solution of pH value；
Active carbon is added in colloidal solution and is beaten into active carbon slurries, the mass ratio of active carbon and water is 1:15, is stirred 5 hours；So
Continue to adjust active carbon slurry pH value to 11 with sodium hydroxide solution afterwards, continues stirring 2 hours, be filtered, washed, nitrogen atmosphere
It is made after the lower roasting of protection.
Anaerobic effluent COD160 mg/L, BOD after the processing of PACT biochemical system512 mg/L, 2.7 mg/L of ammonia nitrogen；It returns
Stream activated sludge is reduced 70% after catalytic ozonation is handled.
Comparative example 1
With embodiment 1, the active carbon for not loading nickel oxide is only added.Air bearing water outlet is after the processing of PACT biochemical system
COD 86 mg/L, BOD512 mg/L, 2.1 mg/L of volatile phenol；Returnedactivatedsludge is reduced after catalytic ozonation is handled
26%。
Claims (13)
1. a kind of method for handling waste water difficult for biological degradation, it is characterised in that: the following steps are included:
(1) active carbon is added into biochemistry pool, forms active carbon-microbial bacteria micelle biochemical system, activated carbon addition 0.5
~ 50 g active carbons/g COD, active carbon content meter by weight contain 0.05 ~ 10% transition metal oxide；
(2) sludge containing active carbon formed in step (1) enters ozone reactor progress ozone in secondary settling tank after precipitation and separation
Change processing；
(3) by step (3), treated that sludge reflux containing active carbon is recycled into biochemistry pool；
Wherein, the active carbon of step (1) containing transition metal oxide is prepared with the following method:
A) soluble transition metal salt is added into deionized water, then forms it into colloidal solution with lye conciliation；
B) active carbon is added in the colloidal solution of step a) and is beaten into active carbon slurries, stirred 1 ~ 6 hour；
C) active carbon slurry pH value then is adjusted to 11 ~ 12 with lye, continue stirring 0.5 ~ 3 hour, be filtered, washed, inertia
The active carbon of carrying transition metal oxide is made after roasting under atmosphere protection.
2. according to the method described in claim 1, it is characterized by: step (1) activated carbon addition be 1.5 ~ 10 g active carbons/
G COD, active carbon content meter by weight contain 0.1 ~ 1.5% transition metal oxide.
3. according to the method described in claim 1, it is characterized by: step (1) activated carbon addition is 3.5 ~ 6 g active carbons/g
COD, active carbon content meter by weight contain 0.4 ~ 0.8% transition metal oxide.
4. according to the method described in claim 1, it is characterized by: the operating condition of step (1) biochemistry pool are as follows: volumetric loading
0.1~3.0 kgCOD/(m3D), 4 ~ 12 h of hydraulic detention time.
5. according to the method described in claim 4, it is characterized by: the operating condition of biochemistry pool are as follows: volumetric loading 1.0 ~ 1.2
kgCOD/(m3D), 6 ~ 8 h of hydraulic detention time.
6. according to the method described in claim 1, it is characterized by: transition metal oxide as described in step (1) include Fe,
One or more of Mn, Co, Ni, Cu, La, Ce.
7. according to the method described in claim 6, it is characterized by: the transition metal oxide is Ni or Cu.
8. according to the method described in claim 1, it is characterized by: the soluble transition metal salt includes transition metal nitre
The mixing of one or more of hydrochlorate, carbonate, sulfate or chlorate.
9. according to the method described in claim 1, it is characterized by: in the active carbon slurries active carbon and water mass ratio
For 1:5 ~ 20.
10. according to the method described in claim 1, it is characterized by: the lye is NaOH, NaCO3、NaHCO3、KOH、
KCO3、KHCO3、(NH2)2The mixing of the one or any of several of CO, the mass percent concentration of lye are 0.1 ~ 30 %.
11. according to the method described in claim 1, it is characterized by: ozonation treatment condition is 2 ~ 20 mg/ in step (2)
GSS, 10 ~ 30 min of residence time.
12. according to the method for claim 11, it is characterised in that: ozonation treatment condition is 5 ~ 10 mg/gSS.
13. according to the method described in claim 1, it is characterized by: 10 ~ 20wt%'s of the middle supplement of step (3) contains transition metal
The active carbon of oxide.
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| CN109626795A (en) * | 2019-01-18 | 2019-04-16 | 宝钢湛江钢铁有限公司 | A kind of mud dewatering method containing powdered carbon of sintering device flue gas purification Wastewater from Acid Preparation |
| CN110127855A (en) * | 2019-05-10 | 2019-08-16 | 河南省图天新能源科技有限公司 | A kind of enhanced biological deamination technique of novel biogas slurry advanced treating |
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| CN102616922A (en) * | 2012-04-23 | 2012-08-01 | 重庆康达环保产业（集团）有限公司 | PACT (Production Analysis Control Technique) novel process for treating non-biodegradable waste water by using circularly-reproducible powdered activated carbon |
| CN103086503A (en) * | 2013-02-26 | 2013-05-08 | 广东新大禹环境工程有限公司 | PACT (powdered activated carbon treatment) process and device, and activated carbon-microbial zoogloea culture method using same |
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2014
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5341049A (en) * | 1976-09-27 | 1978-04-14 | Toyobo Co Ltd | Process for treating dirty water |
| JPH0999293A (en) * | 1995-10-06 | 1997-04-15 | Ebara Corp | Treatment of organic sewage |
| JPH09122679A (en) * | 1995-11-01 | 1997-05-13 | Ebara Corp | Method for processing organic waste water and its apparatus |
| JPH09206781A (en) * | 1996-01-31 | 1997-08-12 | Ebara Corp | Treatment of organic sewage and treating device |
| CN102616922A (en) * | 2012-04-23 | 2012-08-01 | 重庆康达环保产业（集团）有限公司 | PACT (Production Analysis Control Technique) novel process for treating non-biodegradable waste water by using circularly-reproducible powdered activated carbon |
| CN103086503A (en) * | 2013-02-26 | 2013-05-08 | 广东新大禹环境工程有限公司 | PACT (powdered activated carbon treatment) process and device, and activated carbon-microbial zoogloea culture method using same |
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