CN102363549A - Deep treatment system of membraneless industrial organic wastewater - Google Patents
Deep treatment system of membraneless industrial organic wastewater Download PDFInfo
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Abstract
The invention relates to a deep treatment system of membraneless industrial organic wastewater and is suitable for secondary bio-chemical effluent with the water quality COD being less than 300mg/L and the total salt being less than 1%. ''Membraneless'' indicates that physical separation membrane including an MBR system is not necessary in the technology. The invention comprises three treatment units: a wastewater property improvement unit, an ozone catalytic oxidation unit and a biological aerated filter unit. A wastewater modifier is added into the wastewater property improvement pool, so as to reduce the secondary bio-chemical effluent suspension and simultaneously provide a nano-scale catalyst for ozone oxidation. The ozone catalytic oxidation system can be used to reduce COD and chroma, raise the biodegradability of wastewater and decrease the service power of ozone by the utilization of the nano-scale catalyst. Ozone catalytic oxidation effluent enters into the biological aerated filter processing system and pollutants are further reduced by the utilization of the ceramsite surface biomembrane in the biological aerated filter. The treatment technology provided by the invention is efficient, is simple to operate, has strong adaptability and is a potential deep treatment technology of industrial organic wastewater.
Description
Technical field
The invention belongs to field of waste water treatment, relate in particular to a kind of industrial organic waste water advanced treatment system that does not have film.
Background technology
Along with development and national economy; Country's aspect increases the degree of depth and the measure of environmental improvement day by day, effectively controlling under the prerequisite of pollution of area source, strengthens the input and the construction speed of sewage plant; Realize the situation that cities and towns pollution face source control and sewage network spread all over, contained the generation of massive pollution.Simultaneously, occur frequently to the industry emission standard of different industries segmentation, detail specification the emission request of segmentation work post, only pharmaceutical industry just has Chinese medicine class, synthetic type, fermentation type and four kinds of emission standards of biotechnology class.The emission standard of every profession and trade totally presents following four characteristics: (1) discharge index is strict day by day, and average COD concentration is often all below 100mg/L; (2) discharge index of increase characterization factor, the eco-toxicity of controlling features pollutent; (3) advocate the technology of using non-secondary pollution, thorough decomposing pollutant; (4) mostly increased the total nitrogen controlling index.
In view of above-mentioned four characteristics, conventional secondary biochemical technology often is difficult to reach the emission standard of present trade effluent, needs to adopt advanced treatment process could satisfy present emissions requirements.
Technology about advanced treatment of industrial waste water is a lot; Mostly adopt three kinds of schemes at present: (1) is main advanced treatment scheme with the membrane sepn; Adopt ultrafiltration, nf membrane technology; Pollutent is separated concentrate recirculation, (" film " refers to that ultrafiltration, nanofiltration and r-o-are the physical sepn film (comprising the MBR system) of representative); (2) accumulation of various processing schemes adopts ozone, biological filter, coagulating sedimentation, iron-carbon micro-electrolysis unit, aerobic filling system to connect, as yet the importance of the flexibility of taking into account system and processing unit combination not; (3) artificial swamp is the advanced treatment system of representative, adopt undercurrent or surface low artificial wet land system to secondary biochemical water outlet handle;
For first kind of scheme; It only is conventional materialization stripping technique; The film system produces a large amount of dense water will get back to conventional secondary biochemical system; This must cause the problems such as enrichment and long-term disposal decrease in efficiency of hardly degraded organic substance, and the obstruction of film system simultaneously is low with producing water ratio to be the important factor that limits the film system applies always.
For second kind of scheme; Any technology all is to need targetedly; Not existing as yet can be to the treatment and disposal scheme of different properties waste water; Conventional secondary biochemical treatment has often all comprised coagulating sedimentation and biological treatment, and subsequent disposal is eliminated BOD material that front end fully do not remove and residual suspended substance often.Moreover follow-up advanced treatment also relates to comprehensive treating process expense and equipment stable problem.
For the third scheme; Artificial swamp often is fit to the processing of city secondary Sewage Plant treat effluent and is applicable to the area that the place is abundant; Mainly rely on soil is master's filtering system and the root system sorption of plant; Receive the water yield and temperature effect very big, processing efficiency is difficult to surpass 30%, and is slower to microbiological deterioration speed.
Chinese invention patent CN02111402.1 utilizes membrane technique that oil production waste water in oil field is carried out advanced treatment, mainly adopts ultrafiltration, micro-filtration and reverse osmosis membrane processing device, and COD, oil and polymkeric substance are removed, and satisfies the requirement of oil recovery re-injection water.The middle fully membrane separation technique that relies on of system, investment cost is high, the dope difficult treatment.
Chinese invention patent 95112282.7 discloses a kind of deep treatment method of fiber tow production waste water; System synthesis has adopted technology such as " pressurized dissolved air flotation+bio-contact oxidations+mechanical filter+activated carbon adsorption/regeneration+secondary filter "; So tediously long treatment process can satisfy reuse and advanced treatment requirement; But economy and operational suitability a little less than, lack flexibility to water quality.
Chinese invention patent 91107448.1 has attacked a kind of advanced treatment technology of dyeing waste water; Adopt the processing mode of " dissolving gas pressure floatation air+grain active carbon filters "; Terminal COD clearance is reached 60 ~ 70%, and percent of decolourization surpasses 90%, and the initial stage last effect is obvious; Activated carbon penetrates efficiency of post treatment and has decline, and to active and positively charged ion lack of fuel specific aim.
Chinese invention patent 200710130832.5 discloses a kind of advanced treatment scheme of dope dyeing waste water; It is representing the ideological trend of electrochemistry as advanced treatment, and adopting voltage is 30 ~ 80V, and electric current is under 15 ~ 50A condition; COD is 180mg/L in water inlet; When colourity was 100 times, effluent COD concentration was less than 45mg/L, and colourity is less than 20 times.
Chinese invention patent 200710053598.0 discloses a kind of method of yeast wastewater advanced treatment; Add inorganic flocculating agent-bodied ferric sulfate and powder activated carbon in the water outlet of yeast wastewater biochemical treatment system, treat effluent COD concentration is reduced to 40mg/L from 100 ~ 110mg/L.
Chinese invention patent 200910050035.5 discloses a kind of advanced treatment organic wastewater with difficult degradation thereby " ozone+biological filter " treatment system; This also is at present more widely used advanced treatment technology; Can cut down COD to a certain extent to most of secondary biochemical water outlet; But processing cost is higher, is difficult to improve the service efficiency of ozone.Activated carbon adopts amorphous or shell activated carbon.The grain active carbon system applies causes handling load can not amplify, and influent concentration is had certain limitation.
Chinese invention patent CN20101031164.x sky has been opened a kind of advanced treatment technology of refractory organic industrial sewage; Relate to " biological deamination+aerating filter+compound coagulant preparation+BAF is handled " compounding technology, can effectively degrade follow-up suspended substance and biodegradability material.
Always the above is that the advanced treatment technology of representative, suspended substance stripping technique and " ozone+BAF " that coagulating sedimentation is representative are that present advanced treatment develops main direction for the ozonation technology of representative with the membrane sepn.The high investment cost of film system and pollution transportation problem are to influence the widely used principal element of film system.Coagulating agent only can be effective to suspended substance, and is low to the dissolved organic matter processing efficiency, and clearance is often less than 30%.When " ozone+BAF " often can be handled water inlet COD less than 200mg/L, can satisfy the processing horizontal of water outlet COD less than 100mg/L.
For solving present industrial organic waste water after secondary biochemical treatment, problems such as Pollutant levels height, biodegradability difference are badly in need of proposing a kind of economy, feasible, waste water advanced treatment process that processing efficiency is high.
Summary of the invention
For solving the shortage of present industrial organic waste water advanced treatment high efficiency technical; The object of the present invention is to provide a kind of no film industrial organic waste water advanced treatment system; The purpose of entire treatment system is following: chemicals treatment is efficiently selected in (1), the processing mode that adopts reductive agent, oxygenant, coagulating agent, flocculation agent to combine; (2) ozone oxidation adopts the tupe of catalytic ozonation, can reduce the ozone dosage, reduces the power of ozonizer; (3) the aerating filter form of ceramics filling is adopted in the biological filter, and (4) chemicals treatment unit closely links to each other with catalytic ozonation, BAF system, to different condition of water quality flexibility is arranged; (5) whole reason system alternative membrane separation system fully, the emission standard of industry-by-industry is satisfied in the steady running of maintaining system, water outlet.
Goal of the invention of the present invention realizes through following technical scheme.
A kind of advanced treatment system that does not have the film industrial organic waste water; Comprise that wastewater property improves pond, catalytic ozonation tower and BAF, treated organic industrial sewage fully precipitates in second pond, and supernatant gets into wastewater property through gravity flow or pump hoisting way and improves the pond; Add oxygenant or reductive agent, coagulating agent and flocculation agent; Reduce the suspended substance in the waste water to greatest extent on the one hand, reduce the COD total amount of follow-up entering ozone biological filter, prevent the filter tank obstruction; The another one aspect can produce the catalyzer of the inorganic nanoparticles particle diameter of nascent state after reductive agent or oxygenant use, improve the efficient of ozonize.Wastewater property improves the catalytic ozonation tower that the pond water outlet gets into counter current contact; Be provided with water-distributing device and titanium alloy filler in the catalytic ozonation tower, ozone forms the hydroxyl free radical reaction of chain type under the catalytic condition of nano particle in oxidizing tower; Promote the processing efficiency of ozonation system; Water outlet after ozonation system is handled, the general B/C of biodegradability is than surpassing 0.3, and colourity is colourless basically; The water outlet of catalytic ozonation tower gets into BAF; BAF top is provided with water-distributing device, and the middle part is provided with ceramics filling, utilizes the mikrobe of haydite surface enrichment to handle; Further cut down the internal contamination material of waste water; And utilizing haydite and the microbial film that the surface forms to make up filtering system jointly, the BAF water outlet gets into clean water basin, the discharging of sterilization back.
The industrial organic waste water secondary biochemical that is applicable to system of the present invention goes out aqueous nature and is: COD is less than 300mg/L, and the present invention is fit to handle the follow-up organic secondary biochemical water outlet that mainly contains, and general saltiness is no more than 1%.
Improve in the pond at wastewater property; The oxygenant that adds is that concentration is the potassium permanganate of 5 ~ 10mg/L, and reductive agent is iron powder or ferrous hydroxide, and adding concentration is 30 ~ 60mg/L; Coagulating agent is Tai-Ace S 150, bodied ferric sulfate or Poly aluminum Chloride (PAC); Adding concentration is 50 ~ 200mg/L, and flocculation agent is SEPIGEL 305, Dyhard RU 100 yuban or diene methyl dipropyl polymerization ammonium chloride, and adding concentration is 2 ~ 20mg/L.It is 2 ~ 4h that supernatant improves the residence time total in the pond at wastewater property.
Ozone oxidation employing manganese-base oxide or ferrous hydroxide are the counter current contact mode of catalyzer in the catalytic ozonation tower; Hydraulic detention time 0.5 ~ 2h; Ozonizer recommends to use the source of oxygen producer; The O3 contacted oxidation tower adopts the structure of glass reinforced plastic, the inner concentration of using the titanium alloy aerating apparatus to guarantee ozone.The design ratio of ozone and COD is 1:1 ~ 3:1, depends on the characteristics of water quality.
The particle diameter of the haydite ceramics filling at BAF middle part is 1 ~ 3mm, and the load of BAF is designed to 0.8 ~ 1 kg COD/ (m
3D).
The present invention does not have film industrial organic waste water advanced treatment system and does not use any physical sepn film system; Solved salt accumulation and the organic accumulation of non-degradable in the strong brine like this; When water inlet COD concentration during less than 300mg/L, water outlet can be satisfied the emission standard in the industry-by-industry standard.The present invention does not produce secondary pollution, does not let pollutent shift yet, and each section is degradation of organic substances all effectively.Each process section is fully effectively degraded to colourity, COD, total nitrogen and ammonia nitrogen for organically combining.
Description of drawings
Fig. 1 does not have the schema of film industrial organic waste water advanced treatment system for the present invention.
Label declaration among the figure
1-second pond, 2-valve, 3-lift pump, 4-wastewater property improves the pond
5-the first reactive tank, 6-the second reactive tank, 7-the three reactive tank
Water-distributing device 9-ozone release head 10-catalytic ozonation tower 11-pump 12-titanium alloy filler 13-BAF in 8-catalytic ozonation tower
14-ceramics filling, 15-Root's blower, 16-clean water basin, 17-ozonizer
Water-distributing device in 18-BAF
How further specify the present invention below in conjunction with accompanying drawing 1 implements.
Embodiment 1
Industrial organic waste water is through after the secondary biochemical treatment; Often COD concentration is reduced to below the 300mg/L; Second pond 1 supernatant gets into wastewater property through valve 2 with lift pump 3 and improves pond 4; Improve in the pond 4 at wastewater property and to add different water correction medicaments according to water quality characteristics; In waste water, existing with a chain unit is master's organism, and molecular-weight average is higher than at 2,000,000 o'clock, selects to use the improvement prescription (corresponding first reactive tank 5 of difference, second reactive tank 6, the 3rd reactive tank 7) of potassium permanganate, bodied ferric sulfate and SEPIGEL 305; When the organism staple is the benzene series thing in the waste water; Add the improvement prescription (respectively corresponding first reactive tank 5, second reactive tank 6, the 3rd reactive tank 7) of ferrous hydroxide, Tai-Ace S 150 and SEPIGEL 305, when chroma in waste water was higher, the wastewater property activator in the 3rd reactive tank 7 used Dyhard RU 100-yuban instead.The supernatant that wastewater property improves in the pond 4 gets into the catalytic ozonation tower 10 of counter current contact through valve 2 controls; Have water-distributing device 8 and titanium alloy filler 12 in the catalytic ozonation tower 10; Ozonizer 17 carries out ozone output through valve 2; Ozone release head 9 is the titanium alloy aeration head, and 10 water outlets of catalytic ozonation tower get into BAF 13 through valve 2 and pump 11, and water-distributing device 18 is arranged at BAF 13 tops; The middle part is a ceramics filling 14, and aerating system is through Root's blower 15 and valve 2 control aeration intensities.BAF 13 water outlets get into clean water basin 16 through valve 2, the discharging of sterilization back.
Compared with prior art; The present invention does not use any physical sepn film system; Solved salt accumulation and the organic accumulation of non-degradable in the strong brine like this, when water inlet COD concentration during less than 300mg/L, water outlet can be satisfied the emission standard in the industry-by-industry standard.The present invention does not produce secondary pollution, does not let pollutent shift yet, and each section is degradation of organic substances all effectively.Each process section is fully effectively degraded to colourity, COD, total nitrogen and ammonia nitrogen for organically combining.Steady running that conventional membrane treatment process is difficult to realize and high working cost problem are resolved in the present invention.
Embodiment 2
Certain refuse landfill is the maximum refuse landfill in Asia, and percolate COD concentration is up to 30000 ~ 50000mg/L, and the B/C ratio is less than 0.3; Colourity is 2000 times, ammonia nitrogen concentration 1000 ~ 1400mg/L, and COD concentration is 216 ~ 242mg/L; Ammonia nitrogen concentration is 8mg/L, 200 ~ 300 times of colourities.Bio-chemical effluent gets into wastewater property and improves the pond, uses potassium permanganate, bodied ferric sulfate and SEPIGEL 305 to handle, and it is 10mg/L that potassium permanganate adds concentration; It is 80mg/L that bodied ferric sulfate adds concentration, and it is 5mg/L that SEPIGEL 305 adds concentration, wastewater property improve the pond water outlet utilize ozone can with oxidation operation to aldehyde with alcohol form; Substantially improve biodegradability and reduce colourity and COD, at ozone concn: under the COD=1:1 situation, effluent COD concentration is 98 ~ 108mg/L; Ammonia nitrogen and total nitrogen do not change, and colourity is less than 30 times, and BOD/COD increases to 0.31 by 0.05; After the water outlet of catalytic ozonation system got into the BAF system handles, COD concentration was positioned at 50 ~ 60mg/L, and colourity is less than 30 times; BOD is less than 8mg/L, and ammonia nitrogen is less than 5mg/L, and water outlet reaches " household refuse landfill sites pollution control criterion " emission standard in (GB16889-2008); The present invention need not use any film treatment facility, and processing efficiency is stable.
Embodiment 3
Certain pharmaceutical factory's biological fermentation (qingfengmeisu qiong) waste water, secondary biochemical water outlet COD water outlet 160 ~ 200mg/L, 100 ~ 150 times of colourities, BOD/COD is less than 0.1; For satisfying the reuse requirement, effluent COD concentration is less than 50mg/L, and colourity is less than 30 times, and wastewater property improves the pond and adopts ferrous hydroxide (50mg/L), Tai-Ace S 150 (150mg/L), Dyhard RU 100 yuban (50mg/L); The COD clearance is reached 35 ~ 40%, and chroma removal rate is 50%, and water outlet COD is positioned at 80 ~ 100mg/L; When ozone concn and ozone contact tower COD influent concentration were 1:1, effluent COD concentration was less than 70mg/, and colourity is less than 25 times; The B/C ratio reaches 0.3, and after BAF was handled, effluent COD concentration was less than 45mg/L; Colourity satisfies the reuse requirement less than 25 times, also satisfies the emission request of sensitizing range.
Embodiment 4
COD was less than 180mg/L, for realizing that the reuse water-quality COD less than 60mg/L, adopts apparatus of the present invention after Jiangsu recycled writing paper plant adopted secondary biochemical treatment; Waste water improves the pond when adding ferrous hydroxide (50mg/L), Tai-Ace S 150 (50mg/L), SEPIGEL 305 (3mg/L), and up to 40%, effluent COD concentration is less than 110mg/L to the COD clearance; Adopt catalytic ozonation technology; Duration of contact is when being 0.5h, and water outlet COD is less than 80mg/L, after getting into follow-up BAF and handling; Stable water outlet is less than 60mg/L, and this shows that the present invention can realize the switching of technology and the processing of sustainability according to waste water quality.
Embodiment 5
According to the catalytic ozonation system among the embodiment 1, reduction, BOD improvement and molecular weight variation that device for catalyzing and oxidating ozone is handled COD to tail end wastewater are analyzed.
Behind the ozone catalytic ozonation; Biodegradability is promoted between 0.3 ~ 0.4 by B/C=0.1; Ozone and COD concentration ratio are 1:1, and do not exist wastewater property to improve under the prerequisite in pond, and ozone and COD ratio need maintain the level of 2:1 ~ 3:1; Can satisfy similar treatment effect, embodiment effectively reduces the generation power of ozone devices.
Mikrobe toxicity after the table 1 different treatment technology changes
| Handle workshop section | The secondary biochemical water outlet | Wastewater property improves the pond water outlet | Catalytic ozonation |
| The mikrobe inhibiting rate | 60.8% | 28.4% | 14.2% |
Can know by table 1; Improve pond and ozone oxidization combination processing through wastewater property; The mikrobe inhibiting rate of waste water by original 60.8% drop to wastewater property improve the pond water outlet 28.4% with catalytic ozonation after 14.2%; Only a little slightly high than sewage, explain that wastewater biodegradability has reached reasonable level, the catalytic ozonation reaction has certain advantage.
Adopt catalytic ozonation technology and BAF, select the major cause of ozone to comprise: (1) ozone can effectively reduce the COD of waste water; (2) ozone oxidation can be improved wastewater biodegradability; (3) reduced about 80% through the waste water molecular-weight average after the ozonize, and generated material (alcohol, aldehyde, acid) of small molecular weight or the like, clear and definite reason that can biochemical raising.
Claims (9)
1. advanced treatment system that does not have the film industrial organic waste water comprises that wastewater property improves pond, catalytic ozonation tower and BAF, is characterized in that: treated organic industrial sewage abundant deposition in second pond; Supernatant gets into wastewater property and improves the pond; Add oxygenant or reductive agent, coagulating agent and flocculation agent, wastewater property improves the catalytic ozonation tower that the pond water outlet gets into counter current contact, is provided with water-distributing device and titanium alloy filler in the catalytic ozonation tower; The water outlet of catalytic ozonation tower gets into BAF; BAF top is provided with water-distributing device, and the middle part is provided with ceramics filling, and utilizes haydite and the microbial film that the surface forms to make up filtering system jointly; The BAF water outlet gets into clean water basin, the discharging of sterilization back.
2. a kind of advanced treatment system that does not have the film industrial organic waste water according to claim 1 is characterized in that: the water inlet of treatment system requires: COD is less than 300mg/L, and total salinity is no more than 1%.
3. a kind of advanced treatment system that does not have the film industrial organic waste water according to claim 1; It is characterized in that: said wastewater property improves in the pond; The oxygenant that adds is that concentration is the potassium permanganate of 5 ~ 10mg/L, and reductive agent is iron powder or ferrous hydroxide, and adding concentration is 30 ~ 60mg/L; Coagulating agent is Tai-Ace S 150, bodied ferric sulfate or Poly aluminum Chloride (PAC); Adding concentration is 50 ~ 200mg/L, and flocculation agent is SEPIGEL 305, Dyhard RU 100 yuban or diene methyl dipropyl polymerization ammonium chloride, and adding concentration is 2 ~ 20mg/L.
4. according to claim 1 or 3 described a kind of advanced treatment systems that do not have the film industrial organic waste water, it is characterized in that: it is 2 ~ 4h that supernatant improves the residence time total in the pond at wastewater property.
5. a kind of advanced treatment system that does not have the film industrial organic waste water according to claim 1 is characterized in that: it is the counter current contact mode of catalyzer that said catalytic ozonation tower adopts manganese-base oxide or ferrous hydroxide, and hydraulic detention time is 0.5 ~ 2h.
6. according to claim 1 or 5 described a kind of advanced treatment systems that do not have the film industrial organic waste water, it is characterized in that: be provided with ozonizer in the said catalytic ozonation tower, the design ratio of ozone and COD is 1:1 ~ 3:1.
7. a kind of advanced treatment system that does not have the film industrial organic waste water according to claim 6 is characterized in that: said ozonizer is the source of oxygen producer.
8. a kind of advanced treatment system that does not have the film industrial organic waste water according to claim 1 is characterized in that: the particle diameter of the ceramics filling at said BAF middle part is 1 ~ 3mm.
9. according to claim 1 or 8 described a kind of advanced treatment systems that do not have the film industrial organic waste water, it is characterized in that: the load of said BAF is designed to 0.8 ~ 1 kg COD/ (m
3D).
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| CN103214141A (en) * | 2012-12-07 | 2013-07-24 | 北京翰祺环境技术有限公司 | Sewage advanced treatment and recycling method capable of substantially raising economy |
| CN107010782A (en) * | 2017-04-13 | 2017-08-04 | 北京中科康仑环境科技研究院有限公司 | It is a kind of at the same remove industrial park waste water in hardly degraded organic substance, total cyanogen and total nitrogen method |
| CN108409046A (en) * | 2018-04-16 | 2018-08-17 | 中节能工程技术研究院有限公司 | A kind of wastewater treatment equipment and method |
| CN111889507A (en) * | 2020-06-17 | 2020-11-06 | 冯杰英 | Childbirth-simulated biological heavy metal soil remediation ball |
| CN113429082A (en) * | 2021-07-27 | 2021-09-24 | 福建省环境保护设计院有限公司 | Advanced treatment system for non-membrane industrial organic wastewater |
| CN113880297A (en) * | 2021-09-30 | 2022-01-04 | 深水海纳水务集团股份有限公司 | Method for treating chlorinated organic compound sewage |
| CN117069332A (en) * | 2023-09-27 | 2023-11-17 | 中山大学 | Sewage treatment device with low sludge yield and process method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103214141A (en) * | 2012-12-07 | 2013-07-24 | 北京翰祺环境技术有限公司 | Sewage advanced treatment and recycling method capable of substantially raising economy |
| CN107010782A (en) * | 2017-04-13 | 2017-08-04 | 北京中科康仑环境科技研究院有限公司 | It is a kind of at the same remove industrial park waste water in hardly degraded organic substance, total cyanogen and total nitrogen method |
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| CN111889507A (en) * | 2020-06-17 | 2020-11-06 | 冯杰英 | Childbirth-simulated biological heavy metal soil remediation ball |
| CN113429082A (en) * | 2021-07-27 | 2021-09-24 | 福建省环境保护设计院有限公司 | Advanced treatment system for non-membrane industrial organic wastewater |
| CN113880297A (en) * | 2021-09-30 | 2022-01-04 | 深水海纳水务集团股份有限公司 | Method for treating chlorinated organic compound sewage |
| CN117069332A (en) * | 2023-09-27 | 2023-11-17 | 中山大学 | Sewage treatment device with low sludge yield and process method |
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Application publication date: 20120229 |