CN108101209A - It is a kind of using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation - Google Patents
It is a kind of using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2846—Anaerobic digestion processes using upflow anaerobic sludge blanket [UASB] reactors
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/16—Nitrogen compounds, e.g. ammonia
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Abstract
The invention discloses it is a kind of using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation, belong to advanced treatment of wastewater technical field.The present invention will contain S2‑The sulfur-bearing iron chemical sludge that Wastewater Pretreatment generates carries out denitrogenation using thiobacillus denitrificans and nitrate sections oxidation bacteria as electron donor to containing nitrate wastewater.Compared with the prior art, the present invention has the following advantages：(1) the startup time is short, easy to operate without biofilm, non-secondary pollution；(2) sulfur-bearing iron chemical sludge can come into operation by simple process, make the engineering application at low cost, efficient, easy of entire processing procedure, while also carried out effective resource reclaim to the sulfur-rich iron chemical sludge of high pollution；(3) reactor stirring system of the invention is different from traditional UASB reactors, is stirred using jet-flow aeration, generates nitrogen as the source gas body of aeration agitation by the use of reactor itself, operation is convenient, saves the energy.
Description
Technical field
The invention belongs to Water Pollution Control Engineerings and solid waste technical field of comprehensive utilization, and in particular to a kind of to utilize sulfur-bearing iron
Chemical sludge is to the method for waste water advanced denitrogenation.
Background technology
Developing industry be unable to do without rational development of water resources and the scientific and technological progress of water environment protection, according to State Statistics Bureau
Statistics in 2016, about 20,000,000,000 tons of discharged volume of industrial waste water, NH4 +About 250,000 tons of-N discharge capacitys.Industrial circle generally existing work
Skill long flow path, raw materials species are more, the process of multimedium conversion/exchange, and the waste water given off generally contains high concentration
The characteristics of ammonia nitrogen and sulfide, such as the NH of coking wastewater4 +- N 200~500mg/L of concentration, 200~800mg/L of sulfide concentration.
The S of its high concentration2-Stronger biological inhibition toxicity is shown, generally adding molysite in wastewater treatment process makes toxicant sub-prime
Separation, forms the sulfur-bearing iron chemical sludge precipitation of black, and main component is Fe-S compounds.Although the use of divalent iron salt can be with
Efficiently realize the control of sulfide, but the sulfur-bearing iron chemical sludge subsequently generated is difficult to handle, at present general and biological sludge with
And materialized mud mixed processing, it fills or cures as dangerous waste, not only cause final sludge quantity increase, operating cost increase,
The burden of enterprise is improved, while wherein harmful components such as heavy metal, toxicant and foul smell are formed to the potential of environmental sanitation
Harm.For such sulfur-bearing iron chemical sludge, there is presently no the treatment technologies of comparative maturity.
The denitrogenation technology of sewage treatment plant is limited by denitrogenation processing skill generally using traditional nitration denitrification technique at present
The constraint of art, water quality stability, processing energy consumption etc., realizes that the liquid zero-emission of nitrogen in waste water is very difficult.China's municipal sewage
Handle plant effluent NH4 +- N can realize the level-one emission standard A limit value requirement less than 5.0mg/L substantially, and TN (total nitrogen) is universal
More than 20.0mg/L, the Main Morphology of nitrogen is NO3 -- N, concentration is substantially in 50~100mg/L.Some typical Industry Wastes of China
Water can realize NH by denitrification process4 +The effective conversion or removal of-N, as coking wastewater, coal chemical industrial waste water, petrochemical industry are given up
The processing of water, water outlet NH4 +- N is less than 10.0mg/L, but TN concentration is difficult to the limit value requirement for reaching below 20.0mg/L.Largely contain
Accumulation of the nitrogen compound in natural environment, not only breaks up the ecological balance, causes body eutrophication, and with carcinogenic, cause
Abnormal, mutagenic " three cause " effect.If carbon source is added on the basis of water process main process, raising reflux ratio can cause material consumption
And the increase of energy consumption, destroy the stability of existing process；Therefore conventional denitrogenation technology faces the challenge, and need to add advanced treating list
Member.For the two stage biological water outlet of low c/n value, if completing heterotrophism by additional carbon (such as methanol, acetic acid, glucose)
Denitrification, operation difficulty is big, adds operation cost, also has COD spillings or the risk of Nitrite accumulation.Autotrophy
Denitrification, because it utilizes inorganic compound (such as S, S2-、Fe、Fe2+、H2Deng) as denitrification electron donor, there is sludge yield
It the advantages that low, secondary pollution is lacked, gets growing concern at present.
Thiobacillus (Thiobacillus) and nitric acid salt form anaerobic ferrite oxidization bacterium (Nitrate-dependent
Anaerobic ferrous/iron oxidation microorganism, NAFOM) in the anaerobism ring such as underground water and deposit
Generally existing in border, this two classes bacterium can be under anaerobic respectively with reduced sulfur (S2-、S0、S2O3 2-Deng) and iron (Fe0、Fe2 +Deng) it is electron donor, autotrophic denitrification is carried out using nitrate as electron acceptor, the nitrate nitrogen in water is reduced to nitrogen.It is de-
Nitrogen Thiobacillus (Thiobacillus denitrificans) and nitric acid salt form anaerobic ferrite oxidization bacterium can be with natural magnetic Huang iron
Ore deposit (Fe(1-x)S, X are between 0-0.1) autotrophic denitrification reduction nitrate in groundwater is carried out as electron donor, still, at present
By recycling sulfur-bearing iron chemical sludge realize city have stable political situation industrial wastewater secondary effluent advanced nitrogen research yet there are no report
Road.
Entitled " a kind of synchronously to remove nitrate in groundwater and the method for arsenic using natural magnetic iron ore ", Application No.
201611012006.6 Chinese patent application is disclosed synchronously removes nitre in water removal using anaerobism sulphur, iron oxidation, thiobacillus denitrificans
The method of hydrochlorate and arsenic.This method is using thiobacillus denitrificans and nitric acid salt form anaerobic ferrite oxidization bacterium respectively with the sulphur and iron of reduction-state
The nitrate in denitrification removal underground water, while the Fe generated are carried out for electron donor3+The adsorbable arsenic of oxide.But this method
For the removal of low concentration nitrate in underground water, under the conditions of magnetic iron ore adds sufficiently, the startup time of the reaction needs
Want 10d；Intake nitrate nitrogen concentration 34.9mg/L, reach more than 95% removal rate, it is necessary to hydraulic detention time be about 5
~15d；In addition, Surface of Pyrrhotite is easily passivated after reaction a period of time, the further generation of reaction is hindered.Due to the use of side
Method is indirect batch experiment, and natural magnetic iron ore needs purchase, attrition grinding, surface preparation, and dosage is big, and reaction starts
The shortcomings such as the time is long, and processing nitric acid salt load is low, cause to be restricted in terms of the nitrate wastewater processing of high load capacity.Therefore need
Find a kind of low cost, the startup time is short, bears the high autotrophic denitrification denitrogenation electron donor of nitric acid salt load.
The content of the invention
For the high industrial wastewater of sulfide and total nitrogen concentration, at present generally using ferrous sulfate sulphur removal pretreatment and biology
The technique that denitrogenation technology is combined, ferrous ion and sulphion combine the FeS sludge for generating corresponding chemical metering ratio, are with nitrification
End process total nitrogen concentration is easily exceeded, and the sludge of discharge and the equal composing environment of total nitrogen entered in water environment pollute.For upper
Problem is stated, the present invention provides a kind of method of sulfur-bearing iron chemical sludge advanced nitrogen, has grain size spy to add ferrous salt and obtain
The high sulfur-bearing iron chemical sludge of chemism of seeking peace (abbreviation sulphur iron cement), it is real by an anaerobism up flow type sludge suspension reactor
Now efficient, the quick removal of TN containing nitrate wastewater (total nitrogen).
To solve the above-mentioned problems, the technical solution used in the present invention is as follows：
It is a kind of using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation, comprise the following steps：
(1) preparation of sulfur-bearing iron chemical sludge：Industrial wastewater ferrous salt containing ammonia nitrogen in high density and sulfide is pre-
Processing, the isolated sulfur-bearing iron chemical sludge of sludge phase discarded object solid-liquid that ferrous salt pretreatment is generated；It is described containing highly concentrated
Spend NH in the industrial wastewater of ammonia nitrogen and sulfide4 +- N content is 200~500mg/L, S2-Content is 200~800mg/L；
(2) vaccination target strain is to reactor：It will be equivalent to the denitrogenation sulphur of reactor working volume 30%~50% (v/v)
Bacillus (Thiobacillus denitrificans) is seeded in reactor, then by every liter of reactor working volume 15~
The dosage of 20g adds in step (1) described sulfur-bearing iron chemical sludge；
(3) sewage disposal：Pending waste water continuum micromeehanics are vaccinated with target strain to step (2) and have added sulfur-bearing iron
The reactor advanced nitrogen of chemical sludge.
Preferably, the industrial wastewater containing ammonia nitrogen in high density and sulfide described in step (1) is coking wastewater.
Preferably, the specific preparation process of sulfur-bearing iron chemical sludge is in step (1)：To containing ammonia nitrogen in high density and sulfide
Industrial wastewater in continuously add ferrous sulfate solution, obtaining sludge under the conditions of mechanical agitation collaboration microbubble nitrogen gas stirring mutually gives up
Gurry, gravity concentration, it is the sulfur-bearing iron chemical sludge to be then centrifuged for wet mud of the isolated moisture content less than 70%,
In washed with water in centrifugal separation processes removal absorption the surface of solids organic matter.
The sulfur-bearing iron chemical sludge is the Fe-S compounds of about 25 μm~75 μm of grain size, may have reunion between particle, member
The gross mass accounting of Fe and S is more than 70% in plain ingredient, remaining impurity component is on testing without influence.Microbubble nitrogen gas stirring exists
Perforated pipe in reactor/structures is installed or nanopore device exposes nitrogen, realizes the purpose being stirred.
The addition of ferrous sulfate solution can be adjusted according to the sulfur content in actual waste water, according to formula below：
Fe2++S2-——→FeS↓
So what is generated is measurable chemical sludge.
It is furthermore preferred that the concentration of the ferrous sulfate solution is 20% (w/w).
Preferably, reactor described in step (2) is an anaerobism up flow type sludge suspension reactor, including reactor sheet
Body (i.e. the workspace of reactor), temperature control system, water inlet system, jet-flow aeration stirring system and outlet system, water intake mode are
Reactor bottom is intake, and water-out manners are upper end overflow water outlet, and exhaust outlet is arranged on reactor top, by the way of water seal.
The anaerobism up flow type sludge suspension reactor is in addition to jet-flow aeration stirring system, other structures and tradition UASB reactor phases
Together, entire reactor assembly control is in anaerobic condition.The jet-flow aeration stirring system generates nitrogen using reactor itself
As source gas body, aeration agitation is carried out to the substance in reactor body.
Thiobacillus denitrificans (Thiobacillus denitrificans) described in step (2) are commercially available,
It can also be screened from sludge, the main component and concentration of screening and culturing medium are respectively NaS2O3·5H2O 5g/L、KNO3 2g/
L、KH2PO4 2g/L、NaHCO3 1g/L、MgCl2·6H2O 0.5g/L、NH4Cl 0.5g/L、FeSO4·7H2O 0.01g/L。
Preferably, the startup time of reactor is 2d in step (2), and the HRT (hydraulic detention time) of startup stage is
48h。
It will be equivalent to the thiobacillus denitrificans of reactor working volume 30%~50% (v/v) in above-mentioned steps (2)
(Thiobacillus denitrificans) is seeded in reactor, then by every liter of 15~20g's of reactor working volume
Dosage adds in step (1) described sulfur-bearing iron chemical sludge.The inoculum concentration of the target strain is according to universally recognized at present
Aerobic or anaerobic unit sludge concentration determines in water treatment technology, thiobacillus denitrificans (Thiobacillus
Denitrificans it is) autotrophic bacterium, increasess slowly, during reactor stable operation, sludge concentration is basically unchanged, and strain is not
It requires supplementation with.Likewise, the dosage of sulfur-bearing iron chemical sludge is also without being supplemented.
Thiobacillus, Thaobacaldar, Gram-negative, the one of non-photosynthetic effect belongs to bacterium, including sulfur oxide sulphur bar
Bacterium (Thiobacillus Thiooxidans), grate sulfur thiobacillus (Thiobacillus thioparus), ferrous oxide sulphur bar
Bacterium (Thiobacillus ferrooxidans), thiobacillus denitrificans (Thiobacillus denitrificans) etc..Denitrogenation sulphur
Bacillus (Thiobacillus denitrificans) is obligate inorganization energy autotroph, is obtained in the process of sulfur oxide compound
Energy is obtained, and nitrogen is generated by electron acceptor of nitrate, so, this is one kind in waste water simultaneous desulfurization and denitrification treatment process
In major function microorganism.Thiobacillus denitrificans distribution is very wide, can be at 10~37 DEG C, and pH is grown under conditions of being 4.0~9.5,
Optimum growth temperature is 28~30 DEG C, optimal pH 6.5~7.0.
Thiobacillus denitrificans (Thiobacillus denitrificans) are only vaccinated in step (2), but are transported for a long time
New biological community structure can be formed during row in reactor, after running 90d, detects nitric acid salt form anaerobic ferrite oxidization bacterium
(Nitrate-dependent anaerobic ferrous/iron oxidation microorganism, NAFOM) has one
Determine abundance, high-flux sequence analyzes thiobacillus denitrificans and the ratio of nitric acid salt form anaerobic ferrite oxidization bacterium is about 7:1.
The inoculum concentration of target strain, the dosage of sulfur-bearing iron chemical sludge have material impact to technique effect.Object bacteria
The very few sludge concentration (MLSS) that can reduce of the inoculum concentration of kind influences contaminant removal efficiency, and sludge concentration is excessively high, can cause to react
Heterotrophic denitrification reaction or heterotrophism anaerobic reaction occur in device.The dosage of sulfur-bearing iron chemical sludge is according to pollutant concentration and instead
The device cycle of operation is answered to determine, dosage deficiency can influence the removal effect of pollutant, excessively cause that the cycle of operation is long, resource is unrestrained
Expense, sulfur-bearing iron chemical sludge is hardened, can reduce the reaction efficiency in operation later stage.
Preferably, the temperature of step (3) sewage disposal is 15~35 DEG C, and pH is 7.0~8.5.
Preferably, step (3) TN load ranges are the TN loads=TN concentration/HRT within 4.16mg/ (Lh).
Preferably, step (3) the pending waste water can be the work containing ammonia nitrogen in high density and sulfide of step (1)
The waste water or other industrial wastewaters for needing to remove nitrate reduction total nitrogen that industry waste water generates after ferrous salt pre-processes
With other waste water.Therefore method of the present invention can be realized in water treatment process in situ using waste, reduce energy
The purpose that waste water TN depth efficiently removes is realized in consumption, material consumption.
Preferably, the TN of step (3) the pending waste water：70~80mg/L, COD：150~200mg/L.
The principle of the present invention is：For the high industrial wastewater of sulfide and TN concentration, generally removed at present using ferrous sulfate
The technique that sulphur pre-processes and bio-denitrification technology combines, ferrous ion and sulphion combine the FeS for generating corresponding chemical metering ratio
Sludge, it is easily exceeded for end process total nitrogen concentration with nitrification, lack carbon source, TN mainly exists in the form of nitrate nitrogen, discharge
Sludge and the equal composing environments of TN entered in water environment pollute.In the present invention, by the use of sulfur-bearing iron chemical sludge as denitrogenation sulphur bar
The inorganic electron donors of bacterium and nitric acid salt form anaerobic ferrite oxidization bacterium carry out the nitrate anion in the biological water outlet of denitrification removal；Realization contains
The recycling and depth of sulphur iron chemical sludge (dangerous waste) remove the TN in two stage biological water outlet, wherein key reaction metering side
Formula is as follows：
Fe2++S2-——→FeS↓
Fe2++OH-=Fe (OH)2↓
Compared with the prior art, beneficial effects of the present invention are：
(1) the present invention provides it is a kind of using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation, thiobacillus denitrificans
With nitric acid salt form anaerobic ferrite oxidization bacterium using this discarded sulfur-bearing iron chemical sludge as electron donor, depth removal two stage biological
The advantages that TN in water outlet, the time is short with starting, easy to operate, at low cost, non-secondary pollution.
(2) the sulfur-bearing iron chemical sludge that the present invention is utilized carrys out self-contained ammonia nitrogen in high density and the industrial wastewater of sulfide is located in advance
Black precipitate, that is, Fe-S compound sulfur-bearing iron the chemical sludges generated are managed, and the present invention provides discarded sulfur-bearing iron chemical sludge
Sourceization using in water process advanced nitrogen technical aspect, ask by the disposal for playing resource reclaim and the sulfur-rich iron chemical sludge of mitigation
Topic.
(3) reactor of the invention is anaerobism up flow type sludge suspension reactor, in addition to jet-flow aeration stirring system,
Other structures are identical with tradition UASB reactors, and the jet-flow aeration stirring system generates nitrogen as exposure by the use of reactor itself
The source gas body of gas agitating, operation is convenient, saves the energy.
(4) present invention realizes the treatment of wastes with processes of wastes against one another, improves effluent quality, is a kind of water resource purification skill for reducing environmental risk
Art.Sulfur-bearing iron chemical sludge only need to simply clean the organic matter of removal sulfur-bearing iron chemical sludge adsorption with tap water, without
The special operationals such as grinding, calcining can be used to the further removal of TN in waste water, and the chemistry for embodying sulfur-bearing iron chemical sludge is living
Property it is high, denitrogenation speed is fast, the technical characteristic being combined in situ using waste, green with clean manufacturing in water treatment process,
With potential engineering application value.
Description of the drawings
Fig. 1 is the structure of reactor figure used in various embodiments of the present invention, wherein：1- is intake, and 2- temperature control system water, 3- is penetrated
Aerator is flowed, 4- constent temperature heaters, 5- sample taps, 6- exhaust outlets, 7- water outlets, 8-10 is logistics number：8- is intake, 9- air inlets,
10- Warm water circulations.
Fig. 2 is the EDS phenograms of sulfur-bearing iron chemical sludge used in various embodiments of the present invention.
Fig. 3 is the effect for the treatment of of laboratory simulated wastewater advanced nitrogen in the embodiment of the present invention 1.
Fig. 4 is that the second stage of the project A/O/H/O process stabilizings operation of Shaoguan Treatment of Coking Effluent factory is handled in the embodiment of the present invention 2
Two stage biological water outlet advanced nitrogen effect.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
The reactor that the embodiment of the present invention uses is anaerobism up flow type sludge suspension reactor, and structure is as shown in Figure 1, structure
It is similar with traditional UASB reactors, including reactor body, temperature control system, water inlet system, jet-flow aeration stirring system and water outlet
System, water inlet system include water inlet, intake pump and water inlet pipe, and outlet system includes water outlet and outlet pipe；Temperature control system bag
Include constent temperature heater and water circulating pump, recirculated water；Jet-flow aeration stirring system includes jet aerator, and jet aerator is using anti-
Device itself is answered to generate nitrogen as source gas body, gas enters from reactor body bottom (water inlet), in reactor body
Substance carries out aeration agitation；Reactor body is the column type reactor of an organic glass material, internal diameter 5cm, high 50cm, work
Make volume 1000mL, sample tap is provided at reactor body 10cm and 45cm height；Water inlet is located at reactor body bottom
Portion one side；Water intake mode is intake for reactor bottom, and water outlet is located at reactor body top side；Water-out manners overflow for upper end
Outflow water, exhaust outlet is arranged on reactor body top, by the way of water seal.Entire reactor assembly control is in anoxic shape
State.
Fig. 2 be embodiment in sulfur-bearing iron chemical sludge used EDS spectrograms, generally about 50 μm, but particle of basic grain size
Between may have reunion, elemental composition is：Fe 51.55%；S 18.93%；C 15.40%；O11.77%；Na 1.67%；Ca
0.56%；The total content accounting of Al 0.13%, wherein Fe and S are 74.48%.
The target strain thiobacillus denitrificans (Thiobacillus denitrificans) of inoculation of the embodiment of the present invention, use
Document (Baalsrud K, Baalsrud K S.Studies on thiobacillus denitrificans [J] .Archiv
Für Mikrobiologie,1954,20(1):The method openly delivered in 34-62.) is dripped using screening and culturing medium domestication Guangzhou
The municipal sludge of Kau sewage treatment plant AAO technique secondary settling tanks obtains enrichment bacterium solution；Then the bacterium being enriched in bacterium solution is divided
It is obtained from purifying.Thiobacillus denitrificans (Thiobacillus denitrificans) and document identified, obtained
(Baalsrud K,Baalsrud K S.Studies on thiobacillus denitrificans[J].Archiv Für
Mikrobiologie,1954,20(1):34-62；Simultaneous removal of nitrogen and
phosphorus from wastewater by means of FeS-based autotrophic denitrification
[J].Water Science&Technology A Journal of the International Association on
Water Pollution Research,2013,67(12):2761.) thiobacillus denitrificans (Thiobacillus disclosed in
Denitrificans it is) consistent.
The main component and concentration of screening and culturing medium are respectively NaS2O3·5H2O 5g/L、KNO3 2g/L、KH2PO4 2g/
L、NaHCO3 1g/L、MgCl2·6H2O 0.5g/L、NH4Cl 0.5g/L、FeSO4·7H2O 0.01g/L。
Embodiment 1
It is a kind of using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation, process object is given up for laboratory simulation
Water, main component and concentration are respectively sodium nitrate 0.45g/L, sodium acid carbonate 0.5g/L, and its step are as follows：
(1) using coking wastewater raw water as object, it is micro- in mechanical agitation collaboration continuously to add ferrous sulfate solution 20% (w/w)
It is obtained under the conditions of bubble nitrogen gas stirring, gravity concentration needs simply to be cleaned removal absorption with tap water on surface after centrifuging
Organic matter, about 50 μm of the basic grain size of sulphur iron cement may have a reunion between particle, the total content accounting of wherein Fe and S are 74.48%,
And the content concn of the sulphur iron cement after quantitative analysis cleaning.
(3) reactor design is anaerobism up flow type sludge suspension reactor, and structure is as shown in Figure 1；Inoculation is equivalent to reaction
Body accumulates the thiobacillus denitrificans (Thiobacillus denitrificans) of 40% (v/v) in reactor, then anti-by every liter
The dosage of device working volume 15g is answered to add in the sulfur-bearing iron chemical sludge that step (1) obtains；Reactor operation the startup time be
2 days, the HRT of startup stage was 48h.
(4) the continuous water distribution laboratory simulation waste water in bottom is to being vaccinated with target strain and added sulfur-bearing iron chemical sludge
Anaerobism up flow type sludge suspension reactor, reaction temperature are 25 DEG C of room temperature, and inlet flow-patterm is 7.53 ± 0.06.The outer row's supernatant of detection
Liquid, the removal effect of nitrate nitrogen is as shown in figure 3, water outlet TON (NO3 --N+NO2 -- N) concentration is less than 5mg/L, and removal efficiency is big
In 95%, stable operation 90d.
The relation of water inlet TN loads, water outlet TN loads and removal rate is：Removal rate=(water inlet TN loads-water outlet TN is born
Lotus)/water inlet TN loads.
Embodiment 2
It is a kind of using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation, process object is at the coking wastewater of Shaoguan
Manage the two stage biological water outlet of factory's the second stage of the project A/O/H/O process stabilizings operation, water quality index COD150-200mg/L, TN 70-
80mg/L, the Main Morphology of nitrogen is nitrate nitrogen.Processing step is with reference to embodiment 1, by the laboratory simulation waste water in embodiment 1
The two stage biological water outlet of Shaoguan Treatment of Coking Effluent factory the second stage of the project A/O/H/O process stabilizings operation is substituted for, remaining step is not
Become.
System stable operation 90d takes outer row's supernatant detection index of correlation every 2d, and the removal effect of nitrate nitrogen is as schemed
Shown in 4, when HRT is 18h, water outlet TON concentration is less than 5mg/L, and removal efficiency reaches more than 95%.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. it is a kind of using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation, which is characterized in that comprise the following steps：
(1) preparation of sulfur-bearing iron chemical sludge：Industrial wastewater containing ammonia nitrogen in high density and sulfide is pre-processed with ferrous salt,
The isolated sulfur-bearing iron chemical sludge of sludge phase discarded object solid-liquid that ferrous salt pretreatment is generated；It is described to contain ammonia nitrogen in high density
With NH in the industrial wastewater of sulfide4 +- N content is 200~500mg/L, S2-Content is 200~800mg/L；
(2) vaccination target strain is to reactor：It will be equivalent to the thiobacillus denitrificans of reactor working volume 30%~50% (v/v)
It is seeded in reactor, then adds in step (1) described sulfur-bearing iron by the dosage of every liter of 15~20g of reactor working volume
Learn sludge；
(3) sewage disposal：Pending waste water continuum micromeehanics are vaccinated with target strain to step (2) and have added sulfur-bearing iron chemistry
The reactor advanced nitrogen of sludge.
2. it is according to claim 1 using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation, which is characterized in that step
Suddenly the industrial wastewater containing ammonia nitrogen in high density and sulfide described in (1) is coking wastewater.
3. it is according to claim 1 using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation, which is characterized in that step
Suddenly the specific preparation process of sulfur-bearing iron chemical sludge is in (1)：It is continuous into the industrial wastewater containing ammonia nitrogen in high density and sulfide
It adds ferrous sulfate solution, obtains sludge phase discarded object under the conditions of mechanical agitation collaboration microbubble nitrogen gas stirring, gravity concentration, so
It is the sulfur-bearing iron chemical sludge to be centrifugally separating to obtain wet mud of the moisture content less than 70% afterwards, wherein in centrifugal separation processes
In wash with water removal absorption the surface of solids organic matter.
4. it is according to claim 3 using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation, which is characterized in that institute
The Fe-S compounds that sulfur-bearing iron chemical sludge is about 25 μm~75 μm of grain size are stated, the gross mass accounting of Fe and S is big in elemental composition
In 70%.
5. it is according to claim 1 using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation, which is characterized in that step
Suddenly reactor described in (2) is an anaerobism up flow type sludge suspension reactor, including reactor body, temperature control system, water inlet
System, jet-flow aeration stirring system and outlet system, water intake mode are intake for reactor bottom, and water-out manners go out for upper end overflow
Water, exhaust outlet are arranged on reactor top, by the way of water seal.
6. it is according to claim 1 using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation, which is characterized in that step
Suddenly the startup time of reactor is 2d in (2), and the HRT of startup stage is 48h.
7. it is according to claim 1 using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation, which is characterized in that step
Suddenly the temperature of (3) sewage disposal is 15~35 DEG C, and pH is 7~8.5.
8. it is according to claim 1 using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation, which is characterized in that step
Suddenly TN load ranges are the TN loads=TN concentration/HRT within 4.16mg/ (Lh) in (3).
9. it is according to claim 1 using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation, which is characterized in that step
Suddenly (3) described pending waste water is that the industrial wastewater containing ammonia nitrogen in high density and sulfide of step (1) is pre-processed through ferrous salt
The waste water generated afterwards or other waste water for needing to remove nitrate reduction total nitrogen.
10. it is according to claim 1 using sulfur-bearing iron chemical sludge to the method for waste water advanced denitrogenation, which is characterized in that
The TN of step (3) the pending waste water：70~80mg/L, COD：150~200mg/L.
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