CN101224936A - Process for treating coking wastewater - Google Patents

Process for treating coking wastewater Download PDF

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Publication number
CN101224936A
CN101224936A CNA2008100570387A CN200810057038A CN101224936A CN 101224936 A CN101224936 A CN 101224936A CN A2008100570387 A CNA2008100570387 A CN A2008100570387A CN 200810057038 A CN200810057038 A CN 200810057038A CN 101224936 A CN101224936 A CN 101224936A
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China
Prior art keywords
reactor
coking
anoxic
treatment
electrolysis
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CNA2008100570387A
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曾明
赖鹏
倪晋仁
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BEIJING GAIA ENVIRONMENTAL TECHNOLOGY Co Ltd
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BEIJING GAIA ENVIRONMENTAL TECHNOLOGY Co Ltd
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Priority to CNA2008100570387A priority Critical patent/CN101224936A/en
Publication of CN101224936A publication Critical patent/CN101224936A/en
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/10Biological treatment of water, waste water, or sewage

Abstract

The invention relates to a technique for processing coking waste water, which adopts first grade oxygen deficit plus second grade aerobic biological filter as biological treatment and is coupled with aeration micro-electrolysis materialization processing technology to process the coking waste water. Devices of the technique consists of four reactors; the raw water of the coking waste water after pretreatment enters an oxygen deficit reactor and a second grade aerobic reactor in sequence; effluent after biological treatment enters an aeration micro-electrolysis reactor while effluent after physical treatment returns to the oxygen deficit reactor to form an internal recycle; detailed technique procedure is shown in an instruction book. The invention has the advantages that the reaction system has relatively high volume loading and anti-impact loading capacity, COD, NH3-N and total nitrogen are removed synchronously in the same reactor; the removal rate of COD is more than 93 percent and the removal rate of the NH3-N is more than 96 percent; the invention has relatively high removal capacity of the total nitrogen; the chroma of the effluent is greatly reduced; each effluent index can achieve second grade discharge standard of national waste water comprehensive discharge standards and is close to the requirements of first grade discharge.

Description

The technology of Treatment of Wastewater in Coking
Technical field
The present invention relates to waste water treatment process; belong to environment protection and difficulty and fall the Industrial Wastewater Treatment field, specifically, relate to a kind of technology of Treatment of Wastewater in Coking; adopt anoxic+aerobic biofilter combination process, and the little electrolytic and physical treatment technology of coupling aeration is handled the coking chemical waste water of difficult degradation.
Technical background
Coking chemical waste water is coking charcoal or the high density poisonous organic wastewater of making the difficult for biological degradation that produces in the course of gas, is mainly derived from the coke-oven plant of ferrous metallurgy and coking industry.Mainly contain ammonia nitrogen (NH in the coking chemical waste water 3-N), pollution substances such as the heterogeneous ring compound of prussiate, phenolic compound, polycyclc aromatic compound and nitrogenous, oxygen, sulphur and aliphatic cpd, have " three cause " effect, threaten huge to HUMAN HEALTH and ecotope.Except that forming complexity, coking chemical waste water also has characteristics such as the change of water quality amplitude is big, biodegradability is poor, toxicity is big.
At present, the coking chemical waste water of domestic most of coke-oven plants generally adopts activated sludge process and A still based on biological treatment 2O (anaerobism+anoxic+aerobic) technology.A 2The treatment effect of O technology is better than activated sludge process, still, and through A 2Water outlet after the O art breading is difficult to reach secondary discharge standard, particularly COD and the NH in the discharging standards (GB8978-1996) 3These two indexs of-N are difficult to reach emission request simultaneously, firsts and seconds standard-required water outlet COD and NH among the GB8978-1996 3-N is lower than 100mg/L, 150mg/L and 15mg/L, 25mg/L respectively.It is to contain a certain amount of hardly degraded organic substance in the coking chemical waste water that COD is difficult to major cause up to standard, enters into final outflow water thereby these hardly degraded organic substances are difficult to obtain degraded in bio-reactor; Because COD is higher in the aerobic reactor, all be to be dominant bacteria in traditional reactor with heterotrophic bacterium (mainly being nutrition) with the organic carbon source, suppressed the growth of nitrifier, in addition, hardly degraded organic substance with bio-toxicity also will suppress the growth of nitrifier in higher concentration range, so water outlet NH 3-N also is difficult to up to standard.
Adopt the combination process Treatment of Wastewater in Coking that anoxic+the little electrolytic and physical of two-stage aerobic biological filter reactor coupling aeration is handled, system COD clearance is more than 93%, NH 3-N clearance is more than 96%, and water outlet COD reaches the secondary discharge standard of GB8978-1996 and near the requirement of first discharge standard, NH about 100mg/L 3-N is lower than 10mg/L, reaches the first discharge standard of GB8978-1996.The result shows that this combination process has and well removes COD and NH simultaneously 3-N effect, anoxic biological filter reactor has the effect that good denitrification removes nitre nitrogen, can remove the nitrate in the recirculation water, and can remove partial organic substances, reduces COD; One-level aerobic biofilter reactor has removes COD, NH simultaneously 3The ability of-N and total nitrogen, most COD obtains removing in this reactor, and nitrifier also has higher activity in first step aerobic biofilter reactor, thus degraded part NH 3-N; After the most of removal of COD, the activity of nitrifier is further enhanced in the secondary aerobic biofilter reactor, has removed most of remaining NH 3-N, thus make NH in the bio-chemical effluent 3-N is reduced to only several mg/L.The aeration micro-electrolysis reactor can be removed the part hardly degraded organic substance of bio-chemical effluent, and water outlet COD can reach emission standard, and the NH that can not raise 3-N concentration makes the hardly degraded organic substance concentration that enters in the biochemical reactor reduce behind the effluent recycling, also strengthened biochemical reactor to COD and NH simultaneously 3The ability that-N removes obviously is better than single biochemical treatment system.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, and a kind of technology of effective processing difficult degradation coking chemical waste water is provided, make the COD and the NH of water outlet 3Indexs such as-N can reach national specified discharge standard simultaneously, solve the unmanageable at home present situation of coking chemical waste water.
The present invention seeks to realize: the technical scheme that the invention discloses a kind of anoxic+little electrolysis treatment coking chemical waste water of two-stage aerobic biological filter coupling aeration by following measure.The combination process of Treatment of Wastewater in Coking, be to utilize biomembrance process carry out a biological disposal upon (biological filter anoxic+two-stage aerobic), and utilize little cheaply electrolysis process bio-chemical effluent to be handled and is provided with inner circulating reflux, thus optimize the entire treatment system, its treatment scheme is as follows:
The anoxic of coking chemical waste water+two-stage aerobic biological filter coupling aeration micro-electrolysis combined technology is mainly formed (as shown in Figure 1) by four reactors, enter anoxic reacter A, one-level aerobe reactor B and two aerobe reactor C successively through the coking chemical waste water after the suitable pre-treatment (adjusting, oil removal and air supporting etc.), bio-reactor all adopts the biological filter form, the second aerobe reactor water outlet enters aeration micro-electrolysis reactor D and reacts, and the water outlet of reactor D is back to anoxic reacter A through post precipitation and carries out internal recycle.
Anoxic and aerobic reactor all adopt biomembrance process, bio-reactor is made up of one-level anoxic reacter and two-stage aerobic reactors in series, the concrete placed in-line form in biological filter that adopts, add macropore in the reactor and carry (CN2004100625771), the dried carrier stacking volume that adds accounts for 30~70% of total reactor volume, single carrier bulk is 5-15mm * 5-15mm * 5-15mm, carrier contains hydrophilic active groups such as hydroxyl, epoxy group(ing) and amide group, inside has the macroporous netlike structure, and its wet density is 9.0-1.1g/cm 3, water holding capacity is 2300~2600%, and can be anti-aging and wear-resisting; All inoculate Treatment of Coking Effluent factory or similar chemical plant active sludge in the reactor of biological filter, through intaking continuously after the domestication in 5-7 days, and add engineering bacteria and carry out biological reinforced processing, the original strain B350M of engineering flora is provided by the BIO-SYSTEMS company of the U.S., the following http://www.biobugs.com of its network address.
Adopt the body material of waste and old iron plane flower as reaction in the aeration micro-electrolysis reactor, add a small amount of industrial granulated active carbon or coke and constitute macroscopical electrode, waste and old iron plane flower and industrial activited carbon or coke volume load than being 2: 1.
Because coking chemical waste water has certain water quality difference characteristics, adopt the concrete processing parameter of the biological filter coupling aeration micro-electrolysis combined technology Treatment of Wastewater in Coking of anoxic+two-stage aerobic to determine that by experimental study its reactor basic design parameters is:
Anoxic biological filter hydraulic detention time 15~20h;
Aerobic biofilter hydraulic detention time 15~20h;
The little electrolytic hydraulic detention time of aeration is 2-4 hour, and reactor carried out one time spoil disposal in per 20 days;
Aeration micro-electrolysis reactor effluent recycling is to the anoxic biological filter, and its reflux ratio is 100%~300%.
The advantage and the purposes of the biological filter coupling aeration micro-electrolysis combined technology of anoxic/two-stage aerobic of the present invention:
(1) the coking chemical waste water variation water quality is big, contains the phenolic compound and the NH of high density 3-N, anoxic and aerobic reactor all adopt biofilm reactor, and the carrier of filling makes reactor have higher biomass, makes reactive system have the ability of higher volumetric loading and anti-shock loading.
(2) because the support effect of carrier, heterotrophic bacterium, nitrifier and denitrifying bacteria are able to good syntrophism in the one-level aerobic reactor, though dissolved oxygen concentration is higher in the reactor, but the different zones of carrier can provide the microenvironment of aerobic and double oxygen, nitrifier has suitable activity in the reactor, makes and has realized COD, NH at same reactor 3Remove in the time of-N and total nitrogen; Remove under most of organic condition at the one-level aerobic reactor, the high reactivity of nitrifier makes its most NH of residue that degraded in the secondary aerobic reactor 3-N, the NH of bio-chemical effluent 3-N only instrument is youngster mg/L.
(3) updraft fluidised form design helps the effusion of the nitrogenous gas that denitrification process produces in the anoxic reacter.Simultaneously, filler makes the microenvironment of the capable generation anti-nitration reaction of tool in the anoxic reacter, under the little electrolysis recirculation water of aeration dissolved oxygen concentration condition with higher, the denitrification in the anoxic reacter is not subjected to obvious suppression and interference effect, still has very high total nitrogen and removes ability.
(4) COD has obtained significantly reducing in the two-stage aerobic treating processes, bio-chemical effluent about 200mg/L, utilize the little electrolysis of aeration that bio-chemical effluent is handled after, effluent color dilution descends significantly, simultaneously, water outlet COD drops to about 100mg/L, can reach discharging standards.Simultaneously, little electrolysis is improved the biodegradability of water outlet, has further strengthened COD and NH in the biochemical reactor after little electrolysis water outlet refluxes 3The removal ability of-N.
(5) because little electrolysis process has adopted waste and old iron plane flower as reaction material, greatly reduce its processing costs, and reached the purpose of " treatment of wastes with processes of wastes against one another ".
(6) adopt the new skill (actual process parameter should obtain by test) of biological filter thing anoxic/two-stage aerobic coupling aeration micro electrolysis tech Treatment of Wastewater in Coking to handling through suitable pretreated coking chemical waste water, system's water outlet COD clearance is more than 93%, NH 3-N clearance is more than 96%, can reach the secondary discharge standard of national sewage comprehensive emission standard (GB9878-1996) and near the first discharge standard requirement.
Description of drawings
Fig. 1 is the schema of the technology of Treatment of Wastewater in Coking of the present invention, and label wherein is:
A: biological filter anoxic reacter
B: biological filter one-level aerobe reactor
C: biological filter secondary aerobe reactor
D: aeration micro-electrolysis reactor
1: through suitable pretreated coking chemical waste water
2: the biological treatment system water outlet
3: reflux in the micro-electrolysis reactor water part
4: the micro-electrolysis reactor water outlet
Embodiment
Enumerate 2 embodiment below, in conjunction with the accompanying drawings, the present invention is further specified, but the present invention is not only limited to this 2 embodiment.
Embodiment 1
Utilize aforesaid combination technology to water inlet COD and NH 3The actual coking chemical waste water that-N is respectively about 2000mg/L and 260mg/L carries out lab scale experiment processing, the experiment flooding velocity is 120mL/h, the effective volume of anoxic secondary aerobic biofilter reactor is 5400mL, anoxic biological filter reactor waterpower residence time 15h, single-stage aerobic biological filter tank reactor waterpower residence time 15h, the carrier loadings is 60% in the reactor, and single carrier bulk is 5mm * 5mm * 5mm, and wet density is 0.9g/cm 3Water holding capacity is 2500%, dissolved oxygen concentration is controlled at 4~6mg/L in the aerobic reactor, and replenishes enough basicity, all inoculates Treatment of Coking Effluent factory active sludge in the reactor of biological filter, add engineering bacteria B350M and carry out biological reinforced processing, the hydraulic detention time of aeration micro-electrolysis reactor is 4 hours, carries out spoil disposal one time in per 20 days, and aeration micro-electrolysis reactor effluent recycling is to anoxic biological filter reactor, reflux ratio is 300%, water outlet COD and NH 3-N is respectively about 100mg/L and 5mg/L, and nitrogen removal rate is higher than 85%.
Embodiment 2
Certain coal tar company limited produces comprehensive wastewater 4800m 3/ d adopts above combination process that it is handled.Comprehensive wastewater is promoted to oil removal and air-float technology to remove most of oils and SS in the waste water by pump after equalizing tank is collected, pretreated waste water enters the anoxic pond and the Aerobic Pond of rear end and handles after hydrolysis acidification pool carries out pre-acidification, aerobic most of water outlet direct reuse is made quenching usefulness, and part waste water is directly discharging after advanced treatment is up to standard.
Adopt above combination process to handle coal tar comprehensive discharge waste water, designed water is 4800m 3/ d, the actual treatment water yield is 1200m at present 3/ d, the carrier loadings is 60% in the reaction tank, and single carrier bulk is 15mm * 15mm * 15mm, and wet density is 1.1g/cm 3, water holding capacity is 2500%, all inoculates Treatment of Coking Effluent factory active sludge in the biological reaction tank, adds engineering bacteria B350M and carries out biological reinforced processing.Equalizing tank comes water COD after pre-treatment Cr, BOD 5, ammonia nitrogen, volatile phenol, sulfide and prussiate be respectively 2600-3500mg/L, 1000-1500mg/L, 300-500mg/L, 400-900mg/L, 20-60mg/L and 10-50mg/L, biology aerobic water outlet COD Cr, BOD 5, ammonia nitrogen, volatile phenol, sulfide and prussiate be respectively 180-300mg/L, 14-28mg/L, 3-26mg/L, 0.4-0.9mg/L, 0.6-1.4mg/L and 0.2-0.7mg/L, satisfy the quenching water supply standard fully, the part bio-chemical effluent behind the little electrolysis even depth of aeration treatment process, water outlet COD Cr, BOD 5, ammonia nitrogen, volatile phenol, sulfide and prussiate be respectively 76-123mg/L, 6-16mg/L, 2-14mg/L, 0.2-0.4mg/L, 0.3-0.5mg/L and 0.1-0.3mg/L, can reach the secondary discharge standard in the integrated wastewater discharge standard fully.
Can see by above-mentioned example, no matter be that lab scale experiment or engineering are used, the present invention all has good treatment effect for coking chemical waste water, final outflow water can reach in the integrated wastewater discharge standard secondary discharge standard and near first discharge standard (GB8978-1996).

Claims (4)

1. the technology of Treatment of Wastewater in Coking, it is characterized in that adopting the biological filtering tank process of anoxic+two-stage aerobic, form by four reactors, enter anoxic reacter A, one-level aerobe reactor B and secondary aerobe reactor C successively through suitable pretreated coking chemical waste water, bio-reactor all adopts the biological filter form, second stage aerobe reactor water outlet enters aeration micro-electrolysis reactor D and reacts, and reactor D water outlet is back to anoxic reacter A through post precipitation and carries out internal recycle.
2. the technology of Treatment of Wastewater in Coking according to claim 1, it is characterized in that: anoxic and aerobic reactor all adopt biomembrance process, bio-reactor is made up of one-level anoxic reacter and two-stage aerobic reactors in series, add macropore carrier in the reactor, the dried carrier stacking volume that adds accounts for 30~70% of total reactor volume, single carrier bulk is 5-15mm * 5-15mm * 5-15mm, carrier contains hydroxyl, epoxy group(ing) and amide group hydrophilic active group, inside has the macroporous netlike structure, and its wet density is 9.0-1.1g/cm 3, water holding capacity is 2300~2600%, and can be anti-aging and wear-resisting; All inoculate Treatment of Coking Effluent factory or similar chemical plant active sludge in the reactor of biological filter, through intaking continuously after the domestication in 5-7 days, and add engineering bacteria and carry out biological reinforced processing, the original strain B350M of engineering flora is provided by the BIO--SYSTEMS company of the U.S., the following http://www.biobugs.com of its network address.
3. the technology of Treatment of Wastewater in Coking according to claim 1; it is characterized in that: adopt the body material of waste and old iron plane flower in the aeration micro-electrolysis reactor as reaction; add a small amount of industrial granulated active carbon or coke and constitute macroscopical electrode, waste and old iron plane flower and industrial activited carbon or coke volume load than being 2: 1.
4. the technology of Treatment of Wastewater in Coking according to claim 1 is characterized in that: adopt the reactor basic design parameters of the biological filter coupling aeration micro-electrolysis combined technology Treatment of Wastewater in Coking of anoxic/two-stage aerobic to be:
The anoxic biological filter reactor waterpower residence time 15~20h;
The aerobic biofilter reactor waterpower residence time 15~20h;
The little electrolytic hydraulic detention time of aeration is 2-4 hour, and reactor carried out one time spoil disposal in per 20 days;
Aeration micro-electrolysis reactor effluent recycling is to anoxic biological filter reactor, and reflux ratio is 100%~300%.
CNA2008100570387A 2008-01-29 2008-01-29 Process for treating coking wastewater Pending CN101224936A (en)

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101955285A (en) * 2010-08-27 2011-01-26 武汉科技大学 Pretreatment method before ammonia distillation of coking wastewater
CN101492223B (en) * 2008-12-30 2011-09-28 中钢集团鞍山热能研究院有限公司 Treatment process for sewage water generated from medium-low temperature carbonization of coal
CN102372401A (en) * 2011-09-28 2012-03-14 同济大学 Iron-carbon micro-electrolysis-dynamic membrane wastewater deep treatment process
CN102485667A (en) * 2010-12-02 2012-06-06 中国科学院烟台海岸带研究所 Coking wastewater processing technology
CN102627367A (en) * 2012-04-24 2012-08-08 东北石油大学 Method for advanced treatment of coking wastewater
CN101734826B (en) * 2008-11-18 2013-01-02 南京理工大学 Process method for treating coking wastewater
CN103159369A (en) * 2011-12-08 2013-06-19 新奥科技发展有限公司 Method for denitrification treatment of coking wastewater
CN103553282A (en) * 2013-11-18 2014-02-05 攀枝花钢城集团瑞天安全环保有限公司 Deep treatment process of coking wastewater
CN103553207A (en) * 2013-11-13 2014-02-05 镇江东亚碳素焦化有限公司 Improved two-stage biochemical method for treating coking sewage
CN104445482A (en) * 2014-12-29 2015-03-25 杨子江 Process of treating coking wastewater by utilizing coke quenching heat energy
CN105214625A (en) * 2015-11-02 2016-01-06 山东思源水业工程有限公司 A kind for the treatment of process of coking chemical waste water activating brown coal and apply these activation brown coal
CN106495412A (en) * 2016-12-12 2017-03-15 枣庄学院 A kind of coal chemical industry production sewage processing method and processing device
CN107512831A (en) * 2017-10-09 2017-12-26 常州凯恒纺织品有限公司 A kind of coking waste water treatment method
CN107963719A (en) * 2017-11-28 2018-04-27 贵州锦丰矿业有限公司 A kind of processing unit and method of high concentration rhodanate waste water
CN108394994A (en) * 2017-02-08 2018-08-14 鞍钢股份有限公司 A method of strengthening coking wastewater denitrification denitrogenation
CN111233286A (en) * 2020-03-30 2020-06-05 河南君和环保科技有限公司 Aerobic biochemical treatment tail water retreatment process for APMP pulping wastewater
CN114477457A (en) * 2022-04-18 2022-05-13 北京涞澈科技发展有限公司 Coupling sulfur autotrophic denitrification combined biological filter and sewage treatment method

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101734826B (en) * 2008-11-18 2013-01-02 南京理工大学 Process method for treating coking wastewater
CN101492223B (en) * 2008-12-30 2011-09-28 中钢集团鞍山热能研究院有限公司 Treatment process for sewage water generated from medium-low temperature carbonization of coal
CN101955285A (en) * 2010-08-27 2011-01-26 武汉科技大学 Pretreatment method before ammonia distillation of coking wastewater
CN102485667A (en) * 2010-12-02 2012-06-06 中国科学院烟台海岸带研究所 Coking wastewater processing technology
CN102372401A (en) * 2011-09-28 2012-03-14 同济大学 Iron-carbon micro-electrolysis-dynamic membrane wastewater deep treatment process
CN103159369A (en) * 2011-12-08 2013-06-19 新奥科技发展有限公司 Method for denitrification treatment of coking wastewater
CN102627367A (en) * 2012-04-24 2012-08-08 东北石油大学 Method for advanced treatment of coking wastewater
CN103553207A (en) * 2013-11-13 2014-02-05 镇江东亚碳素焦化有限公司 Improved two-stage biochemical method for treating coking sewage
CN103553282A (en) * 2013-11-18 2014-02-05 攀枝花钢城集团瑞天安全环保有限公司 Deep treatment process of coking wastewater
CN104445482A (en) * 2014-12-29 2015-03-25 杨子江 Process of treating coking wastewater by utilizing coke quenching heat energy
CN105214625A (en) * 2015-11-02 2016-01-06 山东思源水业工程有限公司 A kind for the treatment of process of coking chemical waste water activating brown coal and apply these activation brown coal
CN106495412A (en) * 2016-12-12 2017-03-15 枣庄学院 A kind of coal chemical industry production sewage processing method and processing device
CN108394994A (en) * 2017-02-08 2018-08-14 鞍钢股份有限公司 A method of strengthening coking wastewater denitrification denitrogenation
CN107512831A (en) * 2017-10-09 2017-12-26 常州凯恒纺织品有限公司 A kind of coking waste water treatment method
CN107963719A (en) * 2017-11-28 2018-04-27 贵州锦丰矿业有限公司 A kind of processing unit and method of high concentration rhodanate waste water
CN111233286A (en) * 2020-03-30 2020-06-05 河南君和环保科技有限公司 Aerobic biochemical treatment tail water retreatment process for APMP pulping wastewater
CN114477457A (en) * 2022-04-18 2022-05-13 北京涞澈科技发展有限公司 Coupling sulfur autotrophic denitrification combined biological filter and sewage treatment method

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