CN103819061B - A kind of materialization of flue gas desulfurization waste-water and biochemical combined treatment process and device thereof - Google Patents
A kind of materialization of flue gas desulfurization waste-water and biochemical combined treatment process and device thereof Download PDFInfo
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Abstract
The invention belongs to flue gas desulfurization waste-water processing technology field. A kind of materialization of flue gas desulfurization waste-water and biochemical combined treatment process and device thereof, it is characterized in that comprising the following steps: 1), adopt physicochemical method to carry out pretreatment to flue gas desulfurization waste-water at leading portion, comprise: flue gas desulfurization waste-water enters waste water Buffer Pool, then concentrate and clarification through neutralization, sedimentation, cohesion, mud, obtain pretreated flue gas desulfurization waste-water; 2), pretreated flue gas desulfurization waste-water flows automatically in intermediate water tank by overflow mode, in intermediate water tank, inject watery hydrochloric acid and pH value be adjusted to the requirement that meets follow-up biochemical treatment; 3), adopt biochemical method smoke treatment desulfurization wastewater at back segment, comprising: intermediate water tank flue gas desulfurization waste-water after treatment is through Anammox, denitrification, aerobe processing, precipitation, through primary water qualified discharge or the reuse of sedimentation basin processing. This technique and device thereof, the in the situation that of additional carbon not, can efficiently remove the ammonia nitrogen in waste water.
Description
Technical field
The invention belongs to flue gas desulfurization waste-water processing technology field, be specifically related to a kind of physico-chemical process and biochemical process combined treatment cigarette of adoptingThe technique of desulfurization waste water and device thereof. The present invention adopts materialization processing, biochemical treatment two-stage process, step-by-step processing desulfurization wastewater,Especially front end is provided with the wastewater treatment of lime stone-gypsum wet flue gas desulfurizing device of equipment for denitrifying flue gas (this waste water hasThe characteristics such as high ammonia nitrogen, high salinity, high sulfur-bearing, low B/C, are difficult to conventional physical chemistry method or biochemical method processing), the present inventionCan be applicable to electric power, metallurgy, environmental protection and chemical technology field.
Background technology
Along with economic growth and social progress, environmental protection is more and more taken seriously, and China has carried out large-scale SO to coal-burning boiler2Administer engineering, a large amount of desulfurizers builds up and puts into operation, and wherein limestone-gypsum method is current most widely used wet process of FGDTechnology, its technology maturation, absorbent wide material sources, by-produced gypsum can utilize, but limestone-gypsum method flue gas desulfurization is alsoThere is the emission problem of desulfurization wastewater.
Flue gas desulfurization waste-water principal character is to be faintly acid, and pH value is variant with desulfurizer flow process difference, but relatively stable, stateThe pH value of interior power plant effluent is generally 4～6.5; Suspension solid component content is high, and general waste strength is 1%～4%, mainBe lime stone, gypsum particle and other heavy metallic oxides, be easy to bonding, sedimentation function is good; Content of beary metal is high, waste waterIn mainly contain Ca2+，Mg2+，Fe2+，Al3+, other heavy metal ion contents are lower, contain mercury, lead, nickel, zinc simultaneouslyDeng non-metal contaminants such as heavy metal and arsenic, fluorine, because desulfurization wastewater is faintly acid, therefore many heavy metal ion still have wellDissolubility. The method of materialization processing is mainly taked in the processing of flue gas desulfurization waste-water at present, by things such as neutralization, sedimentation, flocculationsChange means are removed suspension and heavy metal ion in waste water, and pH value are transferred to the requirement of discharge standard.
The issuing and implementation of new environmental regulation are to NOXMade more strict regulation, equipment for denitrifying flue gas is extensively implemented, thusCause containing the nitrogen of escaping from equipment for denitrifying flue gas in a large number in flue gas desulfurization waste-water, cause ammonia nitrogen in waste water to exceed standard. And in waste waterAmmonia nitrogen cannot by and the materialization means such as flocculation sediment removed, independent materialization treatment system can not meet, because ofThis need to increase other method and process after materialization is processed.
The method of denitrogenation of waste water is a lot, has Physical, chemical method, bioanalysis etc. For various reasons, Physical, chemical methodApplication be very restricted, the at present both at home and abroad main bio-denitrification technology that adopts. The principle of at present conventional biological denitrificaion isRealize by two separate processes of nitrification and denitrification, wherein nitratedly need to consume a large amount of oxygen, denitrification is wantedUnder anoxia condition, carry out, and need certain carbon source.
But flue gas desulfurization waste-water water quality is very poor, pollution components is a lot, suspension object height, salt content, Cl-、F-Very high concentrations,The B/C(of flue gas desulfurization and denitrification waste water can be biochemical than) be worth low, biodegradability is very poor, adopts common biological treatment to be difficult to openMove and operation, effluent quality after treatment cannot be realized qualified discharge.
Anammox refers to that under anaerobic, anaerobic ammonia oxidizing bacteria is by NH4 +-N is as electron donor, NO2 --N is as electronicsAcceptor, is converted into the nitrogen of these two kinds of forms the bioprocess of nitrogen. Anaerobic ammonia oxidation process one is utilized autotrophic microbe degradedThe treatment process of ammonia nitrogen, does not rely on organic carbon source, and B/C(can biochemically be compared) do not require, be therefore suitable for processing lowThe flue gas desulfurization and denitrification waste water of B/C ratio.
Summary of the invention
The object of this invention is to provide a kind of materialization and biochemical combined treatment process and device thereof of flue gas desulfurization waste-water, not additionalIn the situation of carbon source, can efficiently remove the ammonia nitrogen in waste water.
For achieving the above object, the technical solution used in the present invention is, a kind of materialization of flue gas desulfurization waste-water and biochemical combination placeScience and engineering skill, is characterized in that comprising the following steps:
1). adopt physicochemical method to carry out pretreatment to flue gas desulfurization waste-water at leading portion, comprising: flue gas desulfurization waste-water (cigaretteThe waste water that desulfurization device comes) enter waste water Buffer Pool, then concentrate and clarification through neutralization, sedimentation, cohesion, mud, obtainPretreated flue gas desulfurization waste-water;
2). pretreated flue gas desulfurization waste-water flows automatically in intermediate water tank by overflow mode, injects rare in intermediate water tankHydrochloric acid is adjusted to pH value the requirement that meets follow-up biochemical treatment;
3). adopt biochemical method smoke treatment desulfurization wastewater at back segment, comprising: intermediate water tank flue gas desulfurization after treatmentWaste water, through Anammox, denitrification, aerobe processing, precipitation, passes through the primary water qualified discharge of sedimentation basin processing or returnsWith.
The detailed process of described step 1) is:
(1) during flue gas desulfurization waste-water is introduced into by waste water Buffer Pool and case, in and in case, add milk of lime pH is adjusted to 9～9.5, make the precipitation of hydroxide of most of heavy metal formation indissoluble in flue gas desulfurization waste-water out;
(2) in process, enter in flow tank with the waste water of case processing, in flow tank, add organic sulfur solution, make Pb2+、Hg2＋With the more precipitation of indissoluble of its generation, from waste water, separate;
Described organic sulfur solution (or claiming organic sulfur liquid) is tri-thiol triazine trisodium salt (TMT-15), the joining of organic sulfur solutionConcentration processed is 13wt%～17wt%;
(3) enter flocculation tanks through the waste water of flow tank processing, in flocculation tanks, add Polyferric Sulfate and flocculation aid to make solid suspensionFlocculation, sedimentation rapidly; Described Polyferric Sulfate and the addition of flocculation aid are respectively 65～85ppm and 2.5～3ppm;
Described Polyferric Sulfate is polyaluminum sulfate iron chloride; Described flocculation aid is anion-polyacrylamide solution, 0.1wt% concentration water-solubleLiquid;
(4) enter clarification/inspissator through the waste water of flocculation tanks processing, separated flocculate sedimentation at this flocculate with waterIn bottom, under gravity concentration effect, form concentrated mud; Mud is taken away and is sent into dirt by pump by clarification/inspissator bottom pipeMud treatment system (after sludge dewatering, mud cake outward transport); The supernatant of clarification/inspissator is pretreated flue gas desulfurization waste-water,Pretreated flue gas desulfurization waste-water flows automatically to next stage intermediate water tank (or claiming intermediate pool) by overflow mode.
Step 2) described pH value is 6.5～7.5. Step 2) concentration of described watery hydrochloric acid is 25wt%～35wt%;
The detailed process of step 3) is:
(1) intermediate water tank flue gas desulfurization waste-water after treatment enters anaerobic ammonia oxidation reactor, under anaerobic, and anaerobism ammonia oxygenChange bacterium with NH4 +-N is as electron donor, NO2 --N, as electron acceptor, is converted into nitrogen by the nitrogen of these two kinds of forms;
Anaerobic ammonia oxidation reactor is container or pond airtight, lucifuge; Higher reaction temperature (15-40 DEG C); Higher water inletAmmonia nitrogen concentration (T-N:100～800mg/L); Taking ammonia nitrogen as electron donor, do not need additional organic carbon source; Do not need reactor to enterRow aeration;
(2) enter anoxic reacter through the waste water of Anammox processing, anti-nitration reaction is to complete at anoxic reacter, itBe the biotransformation being completed by denitrifying bacteria,, under anoxia condition, denitrifying bacteria is by the nitrite nitrogen of nitrated generationBe reduced into gaseous nitrogen (N with nitrate nitrogen2)；
Anoxic reacter is airtight container or pond; Under anoxia condition, complete, complete bio-transformation by denitrifying bacteria;
(3) enter aerobic reactor through anoxic reacter waste water after treatment, in aerobic reactor, pass through heterotrophic microorganismBacterium degradation of organic substances, makes COD meet discharge index requirement;
(4) enter sedimentation basin through aerobic reaction waste water after treatment, the Main Function of sedimentation basin is that activated sludge precipitation is refluxedTo aerobic reactor, residual active sludge is outward transport after dehydration, to ensure the amount of aerobe processing section microorganism;
(5) primary water qualified discharge or the reuse of the processing of process sedimentation basin.
This technique is specifically designed to processes desulfurizer waste water, is particularly useful for being provided with equipment for denitrifying flue gas at desulfurizer front endThe desulfurization wastewater that lime stone-gypsum system produces.
In anaerobic ammonia oxidation reactor, adopt anaerobic ammonia oxidizing bacteria, in denitrification reactor, adopt denitrifying bacterium, in aerobic lifeIn thing treatment reactor, adopt heterotrophic microorganism bacterium.
Described biochemical treatment section, the biochemical bacterium adopting (being anaerobic ammonia oxidizing bacteria, denitrifying bacterium, heterotrophic microorganism bacterium),Can bear high salinity, process Cl in water-Concentration be 2000～20000ppm.
Having the Anammox bacterial classification of having a liking for salt characteristic can obtain by following two approach:
1. directly get part ocean bed mud (having a large amount of anaerobic ammonia oxidizing bacterias in seabed);
2. from fresh water environment, get mud, progressively tame anaerobic ammonia oxidizing bacteria by adding salinity, make it have salt tolerance.
We are mainly AnammoxbacteriaumKU2 through qualification by the bacterial classification of inoculation at present, are by selecting in certain sewage treatment plantIn the anaerobically digested sludge of getting, obtain through screening.
Biochemical processing method of the present invention, has following innovation:
1) adopt first Anammox technical finesse desulphurization denitration high ammonia-nitrogen wastewater;
2) adopt first anaerobic ammonia oxidizing bacteria acclimatization technology to process desulphurization denitration high salinity waste water;
3) technique of " Anammox+denitrification coupling technique denitrogenation+aerobe is processed and removed organic matter " is proposed first, canTo reduce ammonia inhibition effect, reduce the consumption of denitrification process carbon source simultaneously.
The present invention not additional carbon and table shown in environmental condition under, can efficiently remove the ammonia nitrogen in waste water, clearance reachesMore than 85%.
Desulfurization wastewater enters water condition
Realize materialization and the biochemical combined treatment device of a kind of flue gas desulfurization waste-water of above-mentioned technique, it is characterized in that it comprises that waste water is slowRush pond, apparatus for physical Chemical treating, intermediate water tank and biochemical treatment apparatus; The waste water delivery outlet of waste water Buffer Pool is by pipeline and materialization placeThe input be connected (described pipeline is provided with valve and pump) of reason device; The output of apparatus for physical Chemical treating and intermediate water tank defeatedEntrance is connected, and the delivery outlet of intermediate water tank is connected with the input of biochemical treatment apparatus by pipeline.
During described apparatus for physical Chemical treating comprises and case, flow tank, flocculation tanks, concentrated/clarifier; In and input port and the waste water of caseThe waste water delivery outlet of Buffer Pool is connected; In be connected with the input port of flow tank by pipeline with the waste water delivery outlet of case, flow tank uselessWater output is connected with the input port of flocculation tanks by pipeline, and the delivery outlet of flocculation tanks is the input port phase with concentrated/clarifier by pipelineConnect, concentrated/clarifier flows automatically to the intermediate water tank of next stage by overflow mode, the mud discharging mouth of concentrated/clarifier by pipeline,Pump is taken away and is sent into sludge treating system.
Described biochemical treatment apparatus comprises anaerobic ammonia oxidation reactor, anoxic reacter, aerobic reactor and sedimentation basin; Anaerobism ammoniaThe input port of oxidation reactor is connected with the delivery outlet of intermediate water tank, and the delivery outlet of anaerobic ammonia oxidation reactor is anti-by pipeline and anoxicAnswer the input port of device to be connected, the delivery outlet of anoxic reacter is connected with the input port of aerobic reactor by pipeline, aerobic reactorDelivery outlet is connected with the input port of sedimentation basin by pipeline, and sedimentation basin is provided with primary water floss hole, activated sludge discharged mouth.
All pipelines are provided with valve, can establish pump.
Device of the present invention can adopt materialization processing, biochemical treatment two-stage process, step-by-step processing desulfurization wastewater, and especially front end is establishedThe wastewater treatment of having put lime stone-gypsum wet flue gas desulfurizing device of equipment for denitrifying flue gas, can be applicable to electric power, metallurgy, ringProtect and chemical technology field.
Compared with traditional wastewater biochemical processing, the invention has the beneficial effects as follows:
1) the present invention is specially adapted to front end and is provided with the waste water of lime stone-gypsum wet flue gas desulfurizing device of equipment for denitrifying flue gasProcess.
2) denitrogenation in the present invention adopts anaerobic ammonia oxidation process, does not need additional organic carbon source, do not need reactor to carry out aeration,Can save energy consumption and expense.
3) the biochemical bacterium (being anaerobic ammonia oxidizing bacteria, denitrifying bacterium, heterotrophic microorganism bacterium) that biochemical process of the present invention adopts,Under high salinity environment, there is equally very high biologically active, still can realize its good denitrification functions, process Cl in water-DenseDu Keda 20000ppm.
4) in the situation that of additional carbon not, can efficiently remove the ammonia nitrogen in waste water, clearance reaches more than 85%, has efficientFeature.
The present invention, for the treatment of desulfurizer waste water, is particularly useful for being provided with at desulfurizer front end the lime of equipment for denitrifying flue gasThe desulfurization wastewater that stone-gypsum system produces.
Brief description of the drawings
Fig. 1 is the process flow diagram of one embodiment of the invention.
Fig. 2 is the structural representation of anaerobic ammonia oxidation reactor.
Fig. 3 is the structural representation of the cover plate of anaerobic ammonia oxidation reactor.
Fig. 4 is the structural representation of the base plate of anaerobic ammonia oxidation reactor.
The structural representation that Fig. 5 is clarification/inspissator.
Fig. 6 is the structured flowchart of apparatus of the present invention.
In Fig. 2-3: 1-exhaust outlet, 2-is incubated water, 3-water intake, 4-insulation water water inlet, 5-mud discharging mouth, 6-support,7-wastewater effluent mouth I, 8-wastewater effluent mouth II, 9-wastewater effluent mouth III, 10-wastewater effluent mouth IV, 11-insulation water delivery port,12-preformed hole I, 13-preformed hole II, 14-preformed hole III, 15-preformed hole IV, 16-screw, 17-preformed hole V.
In Fig. 5: 18-cylindrical shell, 19-central draft tube, 20-mud scraper, 21-railing, 22-inclined tube, 23-supports.
Detailed description of the invention
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not onlyBe confined to the following examples.
The materialization of flue gas desulfurization waste-water and a biochemical combined treatment process, comprise the following steps:
1). adopt physicochemical method to carry out pretreatment to flue gas desulfurization waste-water at leading portion, comprising: flue gas desulfurization waste-water (cigaretteThe waste water that desulfurization device comes) enter waste water Buffer Pool, then and clarification concentrated through neutralization, sedimentation, cohesion, mud (removesThe suspension of flue gas desulfurization waste-water, heavy metal, and regulate its pH value, make water quality after treatment meet follow-up biochemical water inlet and require),Obtain pretreated flue gas desulfurization waste-water; Detailed process is:
1. during flue gas desulfurization waste-water is introduced into by waste water Buffer Pool and case, in and in case, add the milk of lime willpH is adjusted to 9～9.5, make the precipitation of hydroxide of most of heavy metal formation indissoluble in flue gas desulfurization waste-water out;
2. in passing through and the waste water of case processing, most heavy metal ion has generated precipitation of hydroxide, and part Pb at this moment2+、Hg2＋Still exist in waste water with ionic forms; In process, enter in flow tank with the waste water of case processing, in flow tank, add organic sulfur(TMT-15) solution, makes Pb2+、Hg2＋With the more precipitation of indissoluble of its generation, from waste water, separate;
Described organic sulfur solution (or claiming organic sulfur liquid) is tri-thiol triazine trisodium salt (TMT-15), the joining of organic sulfur solutionConcentration processed is 13wt%～17wt%;
3. enter flocculation tanks through the waste water of flow tank processing, in flocculation tanks, add Polyferric Sulfate and flocculation aid to make solid suspension fastSpeed flocculation, sedimentation; Described Polyferric Sulfate (polyaluminum sulfate iron chloride) and flocculation aid (anion-polyacrylamide solution, 0.1wt%The aqueous solution of concentration) addition be respectively 65～85ppm and 2.5～3ppm;
4. enter clarification/inspissator (structure is shown in accompanying drawing 5) through the waste water of flocculation tanks processing, separated with water at this flocculate,Flocculate is deposited in bottom, forms concentrated mud under gravity concentration effect; Mud passes through clarification/inspissator bottom pipe by pumpTake away and send into sludge treating system (after sludge dewatering, mud cake outward transport); The supernatant of clarification/inspissator is pretreated flue gasDesulfurization wastewater, pretreated flue gas desulfurization waste-water flows automatically to next stage intermediate water tank (or claiming intermediate pool) by overflow mode;
Clarification/inspissator (structure is shown in accompanying drawing 5), it comprises cylindrical shell 18, mud scraper 20, central draft tube 19, inclined tube 22, cylinderThe bottom of body is fixed with supports 23, is provided with mud scraper 20, central draft tube 19, inclined tube 22 in cylindrical shell 18, and waste water is from flocculation tanksAfter overflowing, enter into clarification concentrator central tube by Action of Gravity Field. On the inlet channel of clarification concentrator, add and helpSolidifying agent (being generally the anion-polyacrylamide solution of 0.1wt%). Flocculation aid and waste water enter into clear after mixing in pipelineClear inspissator central tube. In flocculation tanks, form the suspension of cotton-shaped particle, by the complexing of flocculation aid, formed thickFloccule body solid greatly, that more easily deposit. By the guide functions of central tube, waste water arrives clarification concentrator middle part, by rearThe promotion of continuous water inlet, waste water starts rising. Due to from central tube out after, waste water rise sectional area suddenly increase,The also rapid drawdown of speed that waste water rises. Go out the waste water of central tube at clarification concentration basin the inside rising, and reacted in waste waterThe bulky grain flock generating relies on Action of Gravity Field to start to fall. Flock in the waste water rising and the flock of whereabouts are intertingIn collision mutually, and become larger flock by the effect of flocculation aid, finally lose activity and deposit to the dirt of clarification concentratorMud storage area. And the upper and lower interior flock due to the flock in the waste water constantly entering and whereabouts of scope of central tube ceaselessly obtainsForm floating zone to supplementing. Waste water upwards flows always, and through inclined tube district, clear water zone, finally covers effluent weir, passes throughOutlet pipe overflows in water tank. Flocculation is carried and is relied on the sewage sludge storage district of gravity sedimentation to clarification concentrator, by mud scraperScraper plate is focused in mud-removing bucket, is regularly expelled to sludge dewatering system dewaters by sludge pump.
2) pretreated flue gas desulfurization waste-water flows automatically in intermediate water tank by overflow mode, injects rare salt in intermediate water tankPH value is adjusted to the requirement that meets follow-up biochemical treatment by acid;
Described pH value is 6.5～7.5, and the concentration of described watery hydrochloric acid is 25wt%～35wt%(mass fraction);
3). adopt biochemical method smoke treatment desulfurization wastewater at back segment, comprising: intermediate water tank flue gas desulfurization after treatmentWaste water (adopts anaerobic ammonia oxidation process to remove total nitrogen, then will detest through Anammox, denitrification, aerobe processing, precipitationThe nitrate nitrogen that anaerobic ammonium oxidation produces carries out denitrification denitrogenation, is finally processed and is removed organic matter by aerobe, makes after treatment uselessWater meets emission request), through primary water qualified discharge or the reuse of sedimentation basin processing; Detailed process is:
1. intermediate water tank flue gas desulfurization waste-water after treatment enters anaerobic ammonia oxidation reactor (its structure is shown in accompanying drawing 2-4), in anaerobismUnder condition, anaerobic ammonia oxidizing bacteria is with NH4 +-N is as electron donor, NO2 --N, as electron acceptor, turns the nitrogen of these two kinds of formsTurn to nitrogen;
Anaerobic ammonia oxidation reactor (its structure is shown in accompanying drawing 2-4), it comprises body, is provided with waste water chamber, water intake in body3, wastewater effluent mouth (7,8,9,10) all communicates with waste water chamber, and the bottom of body is provided with mud discharging mouth (establishing valve control), rowMud mouth communicates with waste water chamber; Outside waste water chamber, be provided with insulation water cavity, insulation water water inlet 4, insulation water delivery port 11 all be incubated waterChamber communicates;
Anaerobic ammonia oxidation reactor is container or pond airtight, lucifuge; Higher reaction temperature (15-40 DEG C); Higher water inletAmmonia nitrogen concentration (T-N:100～800mg/L); Taking ammonia nitrogen as electron donor, do not need additional organic carbon source; Do not need reactor to enterRow aeration;
Anammox reaction condition is as follows:
Temperature: optimum temperature is at 30-35 DEG C;
PH: best pH between 6.8-8.3, water inlet suitable 7.5 left and right that maintain of pH, the highest pH is not suitable for exceeding for a long time8.5 more than;
Hydraulic detention time (HRT): HRT is can be according to the enrichment degree of bacterial classification, and the nitrogen removal performance of reactor is adjusted;HRT can from a couple of days to several h not etc., specifically can simply judge from following two aspects the adjustment of HRT: 1. reactor denitrogenationCan be because of the reducing of HRT, and cause matrix to remain in a large number, cause the accumulation (especially nitrite nitrogen) of matrix; 2. dirtyWhether mud settleability can be because of the reducing of HRT, and causes a large amount of losses of a large amount of activated sludge;
Illumination: need lucifuge operation;
Dissolved oxygen (DO): anaerobic ammonia oxidizing bacteria is more responsive to DO, higher DO can cause reactivity to be suppressed, suitableeerSuitable DO scope is below 0.5mg/L; Higher DO is reversible to the inhibition of reactivity, if waste water does not have deoxidation,Nitrobacteria (aerobic bacteria) in system can part breed, and after consuming the DO in reaction system, anaerobic ammonia oxidizing bacteria againShow reactivity. (postpone the denitrogenation time, cause denitrogenation slow, Simultaneous Nitrification bacterium competes one together with anaerobic ammonia oxidizing bacteriaDivide ammonia nitrogen);
Substrate concentration: the synchronous removal of ammonia nitrogen and nitrite nitrogen is that (Theoretical Mass concentration ratio is the feature that realizes Anammox1:1.32), ammonia nitrogen and nitrite nitrogen are the matrix of carrying out Anammox reaction, but when influent ammonia nitrogen and nitrite nitrogen concentrationWhen too high, can suppress the reaction rate of Anammox; It is generally acknowledged, ammonia nitrogen is less on the impact of reaction system, nitrite nitrogenMore than being not suitable for exceeding 200mg/L, but this inhibition concentration upper limit can increase along with the maturation gradually of the increase of sludge concentration, bacterial classificationAdd;
COD: although anaerobic ammonia oxidizing bacteria is chemoautotrophic bacteria, can better realize the synergy (de-COD) with denitrifying bacterium;It is generally acknowledged that COD is little on its stability of a system impact in 200mg/L left and right;
2. enter anoxic reacter through the waste water of Anammox processing, anti-nitration reaction is to complete at anoxic reacter, and it isThe biotransformation being completed by denitrifying bacteria, under anoxia condition, denitrifying bacteria by the nitrite nitrogen of nitrated generation andNitrate nitrogen is reduced into gaseous nitrogen (N2)；
Anoxic reacter is airtight container or pond; Under anoxia condition, complete, complete bio-transformation by denitrifying bacteria;
Denitrification bacterial strain (being denitrifying bacteria) source: bacterial strain is taken from ASBR anaerobic ammonia oxidation reactor activated sludge, reactorWhen inside there is Anammox effect, NO3--N accumulating value is extremely low, infers in reactor and exists Anammox effect simultaneouslyAlso there is denitrification; Choose a small amount of activated sludge, obtain having the anti-nitre of efficient denitrification carbon elimination ability by separation and purificationChange bacterial strain;
Strain name: bacterial strain order-checking is obtained to the part 16SrDNA sequence that length is 1408bp, by obtained bacterial strain sequenceBe committed in GenBank and retrieve by Blast, application Mega software, grows with Neighbor-Joining method drawing systemTree, determines that bacterial strain thinks that part belongs to pseudomonas (Pseudomonassp.);
Reaction condition: the condition of culture fundamental sum anaerobic ammonia oxidizing bacteria of denitrifying bacterium is similar, this is also that both can realize better working in coordination withReason; Difference shows that denitrifying bacterium has stronger affinity to higher COD, oxygen to its inhibitory action compared with anaerobism ammoniaOxidation bacterium is much weak;
4. enter aerobic reactor through anoxic reacter waste water after treatment, in aerobic reactor, by heterotrophic microorganism bacteriumDegradation of organic substances, makes COD meet discharge index and requires [discharge index is 100mg/L (GB8978-1996)];
Aerobic biodegradation method is to make good use of oxygen animalcule (comprising aerobic-anaerobic microbe) to carry out biology under the condition that has oxygen to existMetabolism, with degradation of organic substances, makes its stable, innoxious processing method; The different oxygen that participates in this process of aerobic degradation organic matter is micro-Biological species various (heterotrophic microorganism bacterium);
Aerobic reactor adopts gallery type plug-flow reactor, and reactor is container or pond, and aeration, oxygen supply are set in reactor,In aerobic reactor, pass through heterotrophic microorganism bacterium degradation of organic substances;
Aerobic reaction condition is as follows:
The nutritive proportion of microorganism: to microorganism, carbon, nitrogen, phosphorus nutrition have certain ratio, are generally BOD5：N：P=100：5:1；
Temperature: the microorganism (be heterotrophic microorganism bacterium) of aerobe in processing belongs to mesophilic micoorganism, its growth and breedingSuitable temperature range is 20-37 DEG C;
PH: the appropriate pH in activated sludge process aeration tank is 6.5-8.5;
Dissolved oxygen (DO): the dissolved oxygen of aerobe processing is generally advisable with 2-3mg/L;
4. enter sedimentation basin through aerobic reaction waste water after treatment, the Main Function of sedimentation basin is that activated sludge precipitation is back toAerobic reactor, residual active sludge is outward transport after dehydration, to ensure the amount of aerobe processing section microorganism;
5. pass through primary water qualified discharge or the reuse of sedimentation basin processing.
In anaerobic ammonia oxidation reactor, adopt anaerobic ammonia oxidizing bacteria, in denitrification reactor, adopt denitrifying bacterium, in aerobic lifeIn thing treatment reactor, adopt heterotrophic microorganism bacterium.
Described biochemical treatment section, the biochemical bacterium adopting (being anaerobic ammonia oxidizing bacteria, denitrifying bacterium, heterotrophic microorganism bacterium),Can bear high salinity, process Cl in water-Concentration be 2000～20000ppm.
Having the Anammox bacterial classification of having a liking for salt characteristic can obtain by following two approach:
1. directly get part ocean bed mud (having a large amount of anaerobic ammonia oxidizing bacterias in seabed);
2. from fresh water environment, get mud, progressively tame anaerobic ammonia oxidizing bacteria by adding salinity, make it have salt tolerance.
We are mainly AnammoxbacteriaumKU2 through qualification by the bacterial classification of inoculation at present, are by selecting in certain sewage treatment plantIn the anaerobically digested sludge of getting, obtain through screening.
This technique is specifically designed to processes desulfurizer waste water, is particularly useful for being provided with equipment for denitrifying flue gas at desulfurizer front endThe desulfurization wastewater that lime stone-gypsum system produces.
The present invention not additional carbon and table shown in environmental condition under, can efficiently remove the ammonia nitrogen in waste water, clearance reachesMore than 85%.
Desulfurization wastewater enters water condition
As shown in Figure 6, realize materialization and the biochemical combined treatment device of a kind of flue gas desulfurization waste-water of above-mentioned technique, it comprises uselessWater Buffer Pool, apparatus for physical Chemical treating, intermediate water tank (or claiming intermediate pool) and biochemical treatment apparatus; Apparatus for physical Chemical treating comprisesIn and case, flow tank, flocculation tanks, concentrated/clarifier (or claiming mud concentrating clarifying device); Biochemical treatment apparatus comprises anaerobism ammoniaOxidation reactor, anoxic reacter (denitrification), aerobic reactor (or claiming aerobic biological processor) and sedimentation basin; Waste water is slowThe waste water delivery outlet that rushes pond (reception flue gas desulfurization waste-water) by pipeline with in be connected with the input port of case, described pipeline is provided with valveDoor and pump, in be connected with the input port of flow tank by pipeline with the waste water delivery outlet of case that (pipeline is provided with valve, on pipeline, can establishPump), the waste water delivery outlet of flow tank is by pipeline be connected with the input port of flocculation tanks (pipeline is provided with valve, can establish pump on pipeline),The delivery outlet of flocculation tanks is connected (pipeline is provided with valve, on pipeline, can establish pump) with the input port of concentrated/clarifier by pipeline, denseContracting/clarifier flows automatically to the intermediate water tank of next stage by overflow mode, the mud discharging mouth of concentrated/clarifier is taken out by pipeline, pumpWalk to send into sludge treating system; The delivery outlet of intermediate water tank is connected (on pipeline with the input port of anaerobic ammonia oxidation reactor by pipelineBe provided with valve, on pipeline, can establish pump), the delivery outlet of anaerobic ammonia oxidation reactor is connected with the input port of anoxic reacter and (is managed by pipelineRoad is provided with valve, on pipeline, can establish pump), the delivery outlet of anoxic reacter is connected with the input port of aerobic reactor and (is managed by pipelineRoad is provided with valve, on pipeline, can establish pump), the delivery outlet of aerobic reactor is connected (on pipeline with the input port of sedimentation basin by pipelineBe provided with valve, on pipeline, can establish pump), sedimentation basin is provided with primary water floss hole, activated sludge discharged mouth.
Claims (8)
1. the materialization of flue gas desulfurization waste-water and a biochemical combined treatment process, is characterized in that comprising the following steps:
1), adopt physicochemical method to carry out pretreatment to flue gas desulfurization waste-water at leading portion, comprising: flue gas desulfurization waste-water enters waste water Buffer Pool, then and clarification concentrated through neutralization, sedimentation, cohesion, mud, obtains pretreated flue gas desulfurization waste-water;
2), pretreated flue gas desulfurization waste-water flows automatically in intermediate water tank by overflow mode, in intermediate water tank, inject watery hydrochloric acid and pH value be adjusted to the requirement that meets follow-up biochemical treatment;
3), adopt biochemical method smoke treatment desulfurization wastewater at back segment, comprising:
(1) intermediate water tank flue gas desulfurization waste-water after treatment enters anaerobic ammonia oxidation reactor, and under anaerobic, anaerobic ammonia oxidizing bacteria is with NH4 +-N is as electron donor, NO2 --N, as electron acceptor, is converted into nitrogen by the nitrogen of these two kinds of forms;
Anaerobic ammonia oxidation reactor is container or pond airtight, lucifuge; The reaction temperature of 15-40 DEG C; The influent ammonium concentration of T-N:100～800mg/L; Taking ammonia nitrogen as electron donor, do not need additional organic carbon source; Do not need reactor to carry out aeration;
(2) enter anoxic reacter through the waste water of Anammox processing, anti-nitration reaction is to complete at anoxic reacter, it is the biotransformation being completed by denitrifying bacteria, and, under anoxia condition, the nitrite nitrogen of nitrated generation and nitrate nitrogen are reduced into gaseous nitrogen by denitrifying bacteria;
Anoxic reacter is airtight container or pond; Under anoxia condition, complete, complete bio-transformation by denitrifying bacteria;
(3) enter aerobic reactor through anoxic reacter waste water after treatment, in aerobic reactor, by heterotrophic microorganism bacterium degradation of organic substances, make COD meet discharge index requirement;
(4) enter sedimentation basin through aerobic reaction waste water after treatment, the Main Function of sedimentation basin is that activated sludge precipitation is back to aerobic reactor, and residual active sludge is outward transport after dehydration, to ensure the amount of aerobe processing section microorganism;
(5) primary water qualified discharge or the reuse of the processing of process sedimentation basin.
2. the materialization of a kind of flue gas desulfurization waste-water according to claim 1 and biochemical combined treatment process, is characterized in that: the detailed process of described step 1) is:
(1) during flue gas desulfurization waste-water is introduced into by waste water Buffer Pool and case, in and in case, add milk of lime that pH is adjusted to 9～9.5, make precipitation of hydroxide that most of heavy metal in flue gas desulfurization waste-water forms indissoluble out;
(2) in process, enter in flow tank with the waste water of case processing, in flow tank, add organic sulfur solution, make Pb2+、Hg2＋With the more precipitation of indissoluble of its generation, from waste water, separate;
Described organic sulfur solution is tri-thiol triazine trisodium salt, and the compound concentration of organic sulfur solution is 13wt%～17wt%;
(3) enter flocculation tanks through the waste water of flow tank processing, in flocculation tanks, add Polyferric Sulfate and flocculation aid to make that solid suspension flocculates rapidly, sedimentation; Described Polyferric Sulfate and the addition of flocculation aid are respectively 65～85ppm and 2.5～3ppm;
Described Polyferric Sulfate is polyaluminum sulfate iron chloride; Described flocculation aid is anion-polyacrylamide solution, the aqueous solution of 0.1wt% concentration;
(4) enter clarification/inspissator through the waste water of flocculation tanks processing, separated with water at this flocculate, flocculate is deposited in bottom, forms concentrated mud under gravity concentration effect; Mud is taken away and is sent into sludge treating system by pump by clarification/inspissator bottom pipe; The supernatant of clarification/inspissator is pretreated flue gas desulfurization waste-water, and pretreated flue gas desulfurization waste-water flows automatically to next stage intermediate water tank by overflow mode.
3. the materialization of a kind of flue gas desulfurization waste-water according to claim 1 and 2 and biochemical combined treatment process, is characterized in that: step 2) described pH value is 6.5～7.5.
4. the materialization of a kind of flue gas desulfurization waste-water according to claim 1 and 2 and biochemical combined treatment process, is characterized in that: step 2) concentration of described watery hydrochloric acid is 25wt%～35wt%.
5. materialization and a biochemical combined treatment device of realizing the flue gas desulfurization waste-water of technique described in claim 1, is characterized in that it comprises waste water Buffer Pool, apparatus for physical Chemical treating, intermediate water tank and biochemical treatment apparatus; The waste water delivery outlet of waste water Buffer Pool is connected with the input of apparatus for physical Chemical treating by pipeline; The output of apparatus for physical Chemical treating is connected with the input port of intermediate water tank, and the delivery outlet of intermediate water tank is connected with the input of biochemical treatment apparatus by pipeline.
6. the materialization of a kind of flue gas desulfurization waste-water according to claim 5 and biochemical combined treatment device, is characterized in that: during apparatus for physical Chemical treating comprises and case, flow tank, flocculation tanks, concentrated/clarifier; In be connected with the input port of case and the waste water delivery outlet of waste water Buffer Pool; In be connected with the input port of flow tank by pipeline with the waste water delivery outlet of case, the waste water delivery outlet of flow tank is connected with the input port of flocculation tanks by pipeline, the delivery outlet of flocculation tanks is connected with the input port of concentrated/clarifier by pipeline, concentrated/clarifier flows automatically to the intermediate water tank of next stage by overflow mode, the mud discharging mouth of concentrated/clarifier is taken away and sent into sludge treating system by pipeline, pump.
7. the materialization of a kind of flue gas desulfurization waste-water according to claim 5 and biochemical combined treatment device, is characterized in that: biochemical treatment apparatus comprises anaerobic ammonia oxidation reactor, anoxic reacter, aerobic reactor and sedimentation basin; The input port of anaerobic ammonia oxidation reactor is connected with the delivery outlet of intermediate water tank, the delivery outlet of anaerobic ammonia oxidation reactor is connected with the input port of anoxic reacter by pipeline, the delivery outlet of anoxic reacter is connected with the input port of aerobic reactor by pipeline, the delivery outlet of aerobic reactor is connected with the input port of sedimentation basin by pipeline, and sedimentation basin is provided with primary water floss hole, activated sludge discharged mouth.
8. the materialization of a kind of flue gas desulfurization waste-water according to claim 5 and biochemical combined treatment device, is characterized in that: the pipeline being connected with the input of apparatus for physical Chemical treating is provided with valve and pump.
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| CN108191050A (en) * | 2018-01-31 | 2018-06-22 | 郑州轻工业学院 | A kind of flue gas desulfurization waste-water and the method for ammonia nitrogen waste water low consumption collaboration processing |
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