CN108117224A - A kind of preprocess method of desulfurization wastewater - Google Patents

A kind of preprocess method of desulfurization wastewater Download PDF

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CN108117224A
CN108117224A CN201611073715.5A CN201611073715A CN108117224A CN 108117224 A CN108117224 A CN 108117224A CN 201611073715 A CN201611073715 A CN 201611073715A CN 108117224 A CN108117224 A CN 108117224A
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fstb
waste water
unit
cgmcc
denitrogenation
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CN108117224B (en
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高会杰
孙丹凤
郭志华
赵胜楠
陈明翔
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • 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
    • 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
    • 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

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)

Abstract

The present invention relates to a kind of preprocess methods of desulfurization wastewater, mainly include（1）Neutralisation unit：Mainly remove the Mg in waste water2+、Zn2+、Cu2+、Ni2+、Cr3+Deng most of heavy metal ion；（2）Sulfate reduction unit：Remaining metal ion in waste water mainly after removal neutralisation treatment；（3）Denitrogenation unit：The removal of nitrogen-containing pollutant and organic pollution is realized mainly under hypersaline environment, water part is back to step（2）In；（4）Sedimentation unit：Supernatant enters subsequent cell and is handled after mud-water separation.The present invention is combined heavy metal ion, organic pollution and nitrogen-containing pollutant in removal waste water by chemical precipitation method and bioanalysis, total nitrogen concentration is less than 15mg/L in processed waste water, COD concentration is less than 60mg/L, guarantee is provided for the follow-up zero-emission of desulfurization wastewater and recycling, has the characteristics that simple possible, small investment, reagent cost are low, effect is good.

Description

A kind of preprocess method of desulfurization wastewater
Technical field
The invention belongs to environment-protection wastewater processing technology fields, and in particular to a kind of preprocess method of desulfurization wastewater.
Background technology
During flue gas desulfurization process, in order to maintain the balance of desulfurizer serum recycle system, it is necessary to periodically from suction Receive tower waste discharge, i.e. desulfurization wastewater.Containing substantial amounts of impurity in the waste water, such as suspended matter, inorganic ion, heavy metal ion Deng, it is necessary to which water body could be discharged by carrying out purified treatment.Domestic most common method for treating desulfurized wastewater is chemical precipitation method at present, This method be using physics, chemical method by neutralize, settle, flocculate clarification etc. means removal desulfurization wastewater in major part hang Float, heavy metal ion etc. make desulfurization wastewater reach national existing discharge standard.
Many desulfuration waste water treatment process newly developed in recent years, such as evaporation, reuse, clarification technique.Room moral is liked by Denmark Power plant's trial replaces chemical precipitation method to handle desulfurization wastewater, it is necessary to add in a certain amount of Gao Meng into fluidized system with fluid bed Sour potassium by a large amount of bivalent manganeses contained in desulfurization wastewater with ferrous ions into manganese dioxide and iron hydroxide, in heavy metal table Face forms coating, removes the heavy metal in waste water.The countries in Europe such as Holland are de- using chemical precipitation-micro-filtration embrane method processing Sulphur waste water is, it is necessary to add in NaOH or Ca (OH) into sedimentation basin2And Na2The substances such as S make most of metal and heavy metal in waste water Ion formation is insoluble in the substance of water and precipitates removal.The integrated application of these above-mentioned technologies is although all achieve good processing Effect, treated, and waste water can meet stringent pollutant emission standard, the zero-emission that can realize desulfurization wastewater having and Recycling, but additional chemical agent ability heavy-metal ion removal is required for, the salinity in sewage is added additional, Increase the intractability of subsequent cell；Also exist simultaneously because sulfide improper use generates the risk of more serious contaminated wastewater； And existing method is without reference to the removal of Organic Pollutants in Wastewater and nitrogen-containing pollutant.
Some flue gas desulfurization techniques are in application process using oxygen deprivation regeneration, due to the missing of oxygen, nitrogen quilt Ammonia is reduced to, and then substantial amounts of ammonia nitrogen is had in waste liquid.Particularly some oxidizing and denitrating ozones+sodium method desulfurization technology, Also substantial amounts of nitrate can be generated in waste liquid.The presence of these nitrogen-containing pollutants brings difficulty to the processing of desulfurization wastewater, more Limit zero-emission and the recycling of the waste water.
Chinese patent CN201510878477.4 discloses the pretreatment side before a kind of heat-engine plant desulfurized waste water evaporative crystallization Method, by carrying out coagulating successively to heat-engine plant desulfurized waste water, more medium filter filters, strong male form Na-ion exchanger is soft Change, adjust four steps of pH value, complete the pretreatment before crystallization is evaporated to desulfurization wastewater.CN201510625606.9 is public A kind of desulfurization wastewater processing equipment for recycling and its method have been opened, efficient group is carried out using film process and evaporative crystallization treatment technology Design is closed, including pretreatment system, film concentrating and treating system, evaporative crystallization processing system.Above method does not all account for desulfurization The processing of Organic Pollutants in Wastewater and nitrogen-containing pollutant has larger impact to membranous system.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preprocess methods of desulfurization wastewater.Passing through of the present invention It learns the precipitation method and bioanalysis is combined heavy metal ion, organic pollution and the nitrogen-containing pollutant removed in waste water, give up after processing Total nitrogen concentration is less than 15mg/L in water, and COD concentration is less than 60mg/L, is carried for the follow-up zero-emission and recycling of desulfurization wastewater It has supplied to ensure, has had the characteristics that simple possible, small investment, reagent cost are low, effect is good.
The preprocess method of desulfurization wastewater of the present invention, it is main to include with lower unit：
（1）Neutralisation unit：It is 8-10 that alkali is added, which to adjust pH, mainly removes the Mg in waste water2+、Zn2+、Cu2+、Ni2+、Cr3+Deng big Part heavy metal ion；
（2）Sulfate reduction unit：It is residual in waste water mainly after removal neutralisation treatment using anaerobism sulfate reduction processing system The Hg stayed2+、Pb2+、Cr3+Wait metal ions；
（3）Denitrogenation unit：Using denitrogenation biochemical treatment system, nitrogen-containing pollutant and organic dirt are realized mainly under hypersaline environment The removal of object is contaminated, water part is back to step（2）In；
（4）Sedimentation unit：Settlement treatment is carried out, supernatant enters subsequent cell and handled after mud-water separation.
Step of the present invention（1）It adjusts pH and mainly adds in NaOH, Ca (OH)2Alkaline matters are waited, it is excellent by pH controls in 8-10 Select 8.5-9.5, the Mg in waste water2+、Zn2+、Cu2+、Ni2+、Cr3+Etc. heavy metal ion generation hydroxide precipitation removed.
Step of the present invention（2）Sulfate reduction unit for conventional anaerobic sulfate reduction system for handling, mainly reduce Part of sulfuric acid salt generates the Hg in hydrogen sulfide, with waste water2+、Pb2+、Cr3+Reactions generation sulfide precipitation is waited, and then removes a huge sum of money Belong to ion.
Step of the present invention（3）The denitrogenation unit realizes nitrogen-containing pollutant and organic dirt mainly under hypersaline environment Contaminate the removal of object.Existing denitrogenation biochemical treatment system may be employed, such as A/O, SBR may be employed.
In the present invention, step（3）According to specific effluent quality, rate-determining steps（3）To step（2）Reflux ratio be 50%- 200%.Work as step（2）, it is necessary to gradually increase reflux ratio when removal of heavy metal ions rate is less than 90% in water outlet, amplitude of accommodation 5- 15 percentage points, make oxidation-reduction potential（ORP）In -300~-200mV, until heavy metal removing rate is up to 95%.Work as step（2） , it is necessary to continuously decrease reflux ratio when sulphion concentration is more than 2.0mg/L in water outlet, the amplitude of accommodation is 5-15 percentage points, makes oxygen Change reduction potential（ORP）In -200~-50mV, part inhibits the activity of sulfate reducing bacteria, generates a small amount of H2S, until sulphur from Sub- concentration is less than 0.2mg/L.Pass through above-mentioned regulation and control, it is ensured that heavy metal ion effectively removes, while will not generate excess Sulphion.
It is possible to further be inoculated with denitrifying activated sludge or denitrogenation microbial inoculum in denitrogenation unit, it is preferable to use denitrogenation microbial inoculum, Such as can be presently disclosed various denitrogenation microbial inoculums, more preferably using following salt tolerant microbial inoculum, in microbial inoculum containing secondary coccus FSTB-2, At least one of microbacterium FSTB-4, Pseudomonas stutzeri FSTB-5 are seen in north, simultaneously containing marsh cock Salmonella（Kocuria palustris）FSDN-A and Staphylococcus cohnis (Staphylococcus cohnii）FSDN-C contains arthrobacterium simultaneously （Arthrobacter creatinolyticus）FDN-1 and Shui Shi Flavobacteriums（Flavobacterium mizutaii）FDN-2 At least one of, simultaneously containing Paracoccus denitrificans (Paracoccus denitrificans) DN-3 and Methylobacterium (Methylobacterium phyllosphaeraeAt least one of) SDN-3.
In salt tolerant microbial inoculum of the present invention, secondary coccus FSTB-2, north have been shown in microbacterium FSTB-4, Pseudomonas stutzeri FSTB-5 " China Committee for Culture Collection of Microorganisms's common micro-organisms center " is preserved on June 1st, 2015, deposit number is CGMCC No.10938, CGMCC No.10939, CGMCC No.10940, preservation address：BeiChen West Road, Chaoyang District, BeiJing City 1 No. 3 Institute of Microorganism, Academia Sinica of institute.Wherein pair coccus FSTB-2 has applied for disclosure in CN201510737219.4, and Having submitted preservation and survival proves；North sees that microbacterium FSTB-4 has applied for disclosure in CN201510737150.5, and has submitted Preservation and survival prove；Pseudomonas stutzeri FSTB-5 has applied for disclosure in CN201510737176.X, and has submitted preservation And survival proves.Marsh cock Salmonella FSDN-A, Staphylococcus cohnis FSDN-C, arthrobacterium FDN-1, Shui Shi Flavobacterium FDN-2, Paracoccus denitrificans DN-3, the deposit number of Methylobacterium SDN-3 are respectively CGMCC NO.5061, CGMCC NO.5062, CGMCC No.3657, CGMCC No.3659, CGMCC No.3658 and CGMCC No.3660, in CN103103141A, Disclosed in CN103014128A, CN102465106A, CN102465105A, CN102465104A, CN102465103.
In salt tolerant microbial inoculum of the present invention, " secondary coccus FSTB-2, north are shown in microbacterium FSTB-4, Pseudomonas stutzeri FSTB-5 At least one ", " marsh cock Salmonella FSDN-A ", " Staphylococcus cohnis FSDN-C ", " arthrobacterium FDN-1 and Shui Shi Huang bars At least one of bacterium FDN-2 ", " at least one of Paracoccus denitrificans DN-3 and Methylobacterium SDN-3 ", the body of five bacteroids Product is than being 1-5:1:1:0.1-10:0.1-10.（By thalline stereometer, thalline volume for culture after under the conditions of 10,000 turns per minute Obtained thalline volume after five minutes is centrifuged, similarly hereinafter）.It is preferred that simultaneously containing secondary coccus FSTB-2, Pseudomonas stutzeri FSTB-5, marsh cock Salmonella FSDN-A and Staphylococcus cohnis FSDN-C.With specific reference to influent quality, effluent index requirement, The requirements such as the stability of whole set process device select the formula of salt tolerant microbial inoculum.
In salt tolerant microbial inoculum of the present invention, microbacterium FSTB-4 and Pseudomonas stutzeri FSTB- are seen in the pair coccus FSTB-2, north 5 can be applied individually to any the efficient removal of COD in the brine waste of salt content 10000-50000mg/L.Secondary coccus FSTB-2, North sees that the seed liquor of tri- kinds of bacterium of microbacterium FSTB-4 and Pseudomonas stutzeri FSTB-5 can individually amplify culture or three Culture is amplified after the seed liquor mixing of kind bacterium.The seed liquor of marsh cock Salmonella FSDN-A and Staphylococcus cohnis FSDN-C Need individually amplification culture；The seed liquor of arthrobacterium FDN-1 and Shui Shi Flavobacterium FDN-2 can individually amplify culture, can also It is the common amplification culture of seed liquor mixing of two kinds of bacterium；The seed liquor of Paracoccus denitrificans DN-3 and Methylobacterium SDN-3 can be single Solely amplification culture or the common amplification culture of the seed liquor mixing of two kinds of bacterium.
In the present invention, step（3）Salt tolerant microbial inoculum dosage according to handled wastewater volume per hour 0.001%- 0.1%, preferably 0.005%-0.05% is added.It can be specifically adjusted according to the index request of water quality and processing water outlet.
Step of the present invention（4）The subsidence styles such as sloping plate deposition, gravitational method precipitation may be employed in the settlement treatment, realize Mud-water separation.Work as step（4）Supernatant be unsatisfactory for subsequent processing requirement when, be back to step（2）, after entering after meeting the requirements Continuous unit is handled or reuse, and evaporative crystallization is carried out after such as can carrying out concentration.
The specific water quality of desulfurization wastewater of the present invention is：PH is 4-6, SS（Suspended matter）For 5000-15000mg/L, Ca2+ For 1000-2000mg/L, Mg2+For 3000-7000mg/L, Cl-For 7000-17000mg/L, SO4 2-For 4000-8000mg/L, SiO2It is 16000-36000mg/L for 5-50mg/L, TDS (total dissolved solid), COD concentration is 400-1000mg/L, total Nitrogen concentration is 100-300mg/L, simultaneously containing heavy metal ion such as mercury, chromium, cadmium, nickel, lead, zinc, copper.
The present invention be combined using chemical precipitation method and bioanalysis heavy metal ion in removal waste water, organic pollution and Nitrogen-containing pollutant, and the control for passing through reflux ratio and oxidation-reduction potential realizes the mesh for efficiently removing removing heavy metals, total nitrogen and COD , total nitrogen concentration is less than 15mg/L in processed waste water, and COD concentration is less than 60mg/L, and concentration of heavy metal ion is below sewage The limit value of comprehensive discharge standard defined provides guarantee for the follow-up zero-emission of desulfurization wastewater and recycling, has letter Single feasible, small investment, the features such as reagent cost is low, effect is good.The present invention is by adding the synergistic effect of denitrogenation microbial inoculum, further Realize the purpose for efficiently removing removing heavy metals, total nitrogen and COD.
Through the pretreated waste water of the present invention into subsequent concentration and evaporation crystalline element, the operation that can reduce film is born Lotus extends the service life of film.The present invention solves existing process by using Chemical treatment heavy metal so as to bring into This increase and secondary pollution problem, organic pollution and nitrogen-containing pollutant in desulfurization wastewater can not be handled by solving existing process The problems such as.
Description of the drawings
Fig. 1 is a kind of flow diagram of inventive desulfurization Wastewater Pretreatment；
Wherein, 1- neutralisation units, 2- sulfate reduction units, 3- denitrogenation units, 4- sedimentation units.
Specific embodiment
Below in conjunction with the accompanying drawings 1 and embodiment to the present invention specific embodiment and effect be described in detail, but not because This is limited the scope of the invention.
Using attached process flow shown in FIG. 1, desulfurization wastewater is initially entered in neutralisation unit 1, by adding in NaOH or Ca (OH)2Alkaline matters are waited, by pH controls between 8-10, the Mg in desulfurization wastewater2+、Zn2+、Cu2+、Ni2+、Cr3+Deng most of weight Metal ion generation hydroxide precipitation is removed.In treated by adding alkali neutralization waste water still containing it is most of with from Hg existing for sub- form2+、Pb2+、Cr3+Deng, into sulfate reduction unit 2, the S of sulfate reduction generation2-With Hg2+、Pb2+ Wait heavy metals reaction generation sulfide precipitation.Processed waste water enters denitrogenation unit 3 and carries out the further of nitrogen-containing pollutant and COD Removing, denitrogenation unit water part are back in sulfate reduction unit, and it is 50%-200% to control reflux ratio.Work as sulfate reduction , it is necessary to gradually increase reflux ratio when removal of heavy metal ions rate is less than 90% in unit water outlet, the amplitude of accommodation is 5-15 percentage Point, makes oxidation-reduction potential（ORP）In -300~-200mV, until heavy metal removing rate is up to 95%.Work as step（2）Sulphur in water outlet , it is necessary to continuously decrease reflux ratio when ion concentration is more than 2.0mg/L, the amplitude of accommodation is 5-15 percentage points, makes redox electric Position（ORP）In -200~-50mV, part inhibits the activity of sulfate reducing bacteria, generates a small amount of H2S, until sulphion concentration is low In 0.2mg/L.Pass through above-mentioned regulation and control, it is ensured that heavy metal ion effectively removes.It is useless after three cell processings Water enters in sedimentation unit 4, is arranged after indices qualification outside supernatant, sulfate reduction unit 2 is back to if unqualified In continue with, the final efficient removal for realizing heavy metal, organic pollution and nitrogen-containing pollutant in desulfurization wastewater.
The salt tolerant microbial inoculum that the present invention uses is prepared using CN201510737425.5 the methods, secondary coccus FSTB-2, north See that the FSTB Liquid Culture based formulas used in microbacterium FSTB-4 and Pseudomonas stutzeri FSTB-5 is：FeSO4•7H2O:25mg/ L, NH4NO3:286mg/L, KCl:929mg/L, CaCl2:2769mg/L, NaCl:21008mg/L, beef extract:5g/L, albumen Peptone:10g/L, pH value 6.0-8.0；Solid medium is the agar of addition 2% in liquid medium.Marsh cock Salmonella The thalline of FSDN-A is activated is with the culture medium prescription used in seed liquor culture：Beef extract:10g/L, peptone:15g/L, NaNO2:1.0g/L, KNO3:0.8g/L.Culture medium used in the thalline activation and seed liquor culture of Staphylococcus cohnis FSDN-C It is formulated and is：Beef extract:10g/L, peptone:15g/L, NaNO2:1.0g/L, methanol:1.0mL/L.Arthrobacterium FDN-1 and Shui Shi The thalline of Flavobacterium FDN-2 is activated is with the culture medium prescription used in seed liquor culture：Beef extract:5g/L, peptone:10g/L, NaNO2:1g/L, solid medium add in the agar of 1.5-2.5%.The Liquid Culture based formulas of Paracoccus denitrificans DN-3 is：KNO3: 1g/L, sodium succinate:8g/L, KH2PO4:1g/L, FeCL2:0.5g/L；Solid medium adds in the agar of 20g/L.Methylobacterium The Liquid Culture based formulas of SDN-3 is：Ammonium sulfate:0.5g/L, methanol:0.75mL/L, KH2PO4:1g/L, FeCL2:0.5g/L； Solid medium adds in 2% agar.Specifically follow the steps below：
（1）Secondary coccus FSTB-2, north are seen that microbacterium FSTB-4 and Pseudomonas stutzeri FSTB-5 are inoculated in FSTB solids respectively It is activated on culture medium；By marsh cock Salmonella FSDN-A, Staphylococcus cohnis FSDN-C, arthrobacterium FDN-1, Shui Shi Huang bar Bacterium FDN-2, Paracoccus denitrificans DN-3 and Methylobacterium SDN-3 are inoculated on corresponding solid medium and are activated respectively；Coating Temperature is placed on after uniformly to be activated in 35 DEG C of constant incubators.
（2）See microbacterium FSTB-4 and Pseudomonas stutzeri FSTB- with make even secondary coccus FSTB-2 on plate, north of collarium is connect 5 bacterium colonies are inoculated in respectively in corresponding FSTB fluid nutrient mediums, are made even marsh cock Salmonella FSDN-A on plate, section with collarium is connect Family name staphylococcus FSDN-C, arthrobacterium FDN-1, Shui Shi Flavobacterium FDN-2, Paracoccus denitrificans DN-3 and Methylobacterium SDN-3 bacterium Fall and be inoculated in respectively in corresponding fluid nutrient medium, shake culture 48 hours to logarithm is given birth under the conditions of 30 DEG C of temperature, 150rpm For a long time, liquid bacterial agent seed liquor is obtained.
（3）Microbacterium is shown in secondary coccus FSTB-2, north respectively in the reactor with good aeration and stirring condition FSTB-4, Pseudomonas stutzeri FSTB-5, marsh cock Salmonella FSDN-A, Staphylococcus cohnis FSDN-C, arthrobacterium FDN-1, Shui Shi Flavobacteriums FDN-2, Paracoccus denitrificans DN-3 and Methylobacterium SDN-3 seed liquors are amplified culture, and COD is dense in culture solution It spends for 2000mg/L, total nitrogen concentration 100mg/L, salt content 2.5wt%, pH value 8.0.Condition of culture is：Temperature is 30 DEG C, dissolved oxygen 2.0-3.0mg/L when incubation time 72 is small, is derived from the dense bacterium solution of nine plants of bacterium.
Above-mentioned dense bacterium solution is collected, is prepared according to ratio described in table 1, concrete composition and proportioning are as shown in table 1.
The composition and ratio of 1 salt tolerant microbial inoculum of table
Embodiment 1
Certain power plant generate the specific water quality of desulfurization wastewater be：PH is 4-6, SS 5000-8000mg/L, Ca2+For 1000- 1200mg/L, Mg2+For 3000-3500mg/L, Cl-For 7000-8000mg/L, SO4 2-For 4000-5000mg/L, SiO2For 15- 20mg/L, TDS 16000-18000mg/L, COD 400-500mg/L, total nitrogen 100-150mg/L.Also contain simultaneously Metal ion, wherein total mercury are 0.3-0.4mg/L, total chromium is 2-3mg/L, total cadmium is 0.5-0.6mg/L, nickel 2-3mg/L, lead For 3-4mg/L, zinc 5-6mg/L.
Using the flow of the method for the present invention, desulfurization wastewater initially enters neutralisation unit, adds in NaOH and controls pH in 8.5- Between 9.0, the Mg in waste water is removed2+、Zn2+、Cu2+、Ni2+、Cr3+Etc. heavy metal ion.After alkali neutralization is added to handle Waste water enters in anaerobism sulfate reduction unit, the S that sulfate reduction generates2-With Hg2+、Pb2+、Cr3+Wait heavy metals reaction generation Sulfide precipitation.The waste water of heavy-metal ion removal enters denitrogenation unit, and the water outlet of denitrogenation unit flows back according to 50% reflux ratio To sulfate reduction unit.When removal of heavy metal ions rate is less than 90% in sulfate reduction unit water outlet, reflux is continuously decreased Than reducing by 10 percentage points every time, making ORP in -300~-250mV, until removal rate is up to 95%；When sulphion concentration in water outlet During more than 2.0mg/L, reflux ratio is gradually increased, increases by 10 percentage points every time, makes ORP in -100~-50mV, until sulphion Concentration is less than 0.2mg/L.Waste water after three cell processings carries out settlement treatment, and COD concentration is less than in supernatant 60mg/L, total nitrogen concentration can't detect heavy metal ion less than 15mg/L.
Embodiment 2
Waste water, technique and operating condition are handled with embodiment 1.Difference is：In denitrogenation unit according to handled waste water per hour The 0.05% of volume adds salt tolerant microbial inoculum 1#.Waste water after three cell processings carries out settlement treatment, COD in supernatant Concentration, less than 10mg/L, can't detect heavy metal ion less than 50mg/L, total nitrogen concentration.
Embodiment 3
Waste water, technique and operating condition are handled with embodiment 1.Difference is：In denitrogenation unit according to handled waste water per hour The 0.005% of volume adds salt tolerant microbial inoculum 2#.Waste water after three cell processings carries out settlement treatment, COD in supernatant Concentration, less than 10mg/L, can't detect heavy metal ion less than 50mg/L, total nitrogen concentration.
Embodiment 4
Certain power plant generate the specific water quality of desulfurization wastewater be：pH：4-6、SS：8000-10000mg/L、Ca2+：1500-2000mg/ L、Mg2+：3500-4500mg/L、Cl-：8000-9000mg/L、SO4 2-：5000-6000mg/L、SiO2：15-20mg/L、TDS： 18000-20000mg/L、COD：500-600mg/L, total nitrogen：150-200mg/L.Also contain heavy metal, wherein total mercury simultaneously： 0.4-0.5mg/L, total chromium：3-4mg/L, total cadmium：0.6-0.7mg/L, nickel：2-3mg/L, lead：4-5mg/L, zinc：6-8mg/L.
Using the flow of the method for the present invention, desulfurization wastewater initially enters neutralisation unit, adds in NaOH and controls pH in 9.0- Between 9.5, the Mg in waste water is removed2+、Zn2+、Cu2+、Ni2+、Cr3+Etc. heavy metal ion.After alkali neutralization is added to handle Waste water enters in anaerobism sulfate reduction unit, the S that sulfate reduction generates2-With Hg2+、Pb2+、Cr3+Wait heavy metals reaction generation Sulfide precipitation.The waste water of heavy-metal ion removal enters denitrogenation unit, and the water outlet of denitrogenation unit is returned according to 100% reflux ratio It flow to sulfate reduction unit.Still the heavy metal ion not removed is contained after operation a period of time in sulfate reduction unit, Removal rate is 88%, continuously decreases reflux ratio, reduces by 10 percentage points every time, makes ORP in -250~-200mV, until removal rate Up to more than 95%；When sulphion concentration is more than 2.0mg/L in water outlet, reflux ratio is gradually increased, increases by 10 percentage points every time, Make ORP in -200~-100mV, until sulphion concentration is less than 0.2mg/L.Waste water after three cell processings carries out Settlement treatment, COD concentration can't detect heavy metal ion less than 60mg/L, total nitrogen concentration less than 15mg/L in supernatant.
Comparative example 1
Waste water, technique and operating condition are handled with embodiment 1.Difference is：The effluent recycling of denitrogenation unit is controlled than always 50%.After running a period of time, waste water after three cell processings carries out settlement treatment, in supernatant COD at concentrations up to 80mg/L, total nitrogen concentration reach 40mg/L, moreover it is possible to detect the metal ions such as the mercury of 0.1-0.2mg/L and the lead of 1mg/L or so.
Comparative example 2
Waste water, technique and operating condition are handled with embodiment 1.Difference is：The ORP of sulfate reduction unit control always- 300~-200mV.After running a period of time, waste water after three cell processings carries out settlement treatment, COD in supernatant For concentration less than 50mg/L, total nitrogen concentration less than 10mg/L, sulphion concentration reaches 5.0mg/L.

Claims (12)

1. a kind of preprocess method of desulfurization wastewater, it is characterised in that including with lower unit：
（1）Neutralisation unit：It is 8-10 that alkali is added, which to adjust pH, removes the Mg in waste water2+、Zn2+、Cu2+、Ni2+、Cr3+Heavy metal ion；
（2）Sulfate reduction unit：Using anaerobism sulfate reduction processing system, remaining Hg in waste water is removed after neutralisation treatment2 +、Pb2+、Cr3+Metal ion；
（3）Denitrogenation unit：Using denitrogenation biochemical treatment system, nitrogen-containing pollutant and organic pollution are realized under hypersaline environment Removal, water part is back to step（2）In；
（4）Sedimentation unit：Settlement treatment is carried out, supernatant enters subsequent cell and handled after mud-water separation.
2. according to the method described in claim 1, it is characterized in that：Step（1）It adjusts pH and adds in NaOH or Ca (OH)2。
3. according to the method described in claim 1, it is characterized in that：Step（2）Sulfate reduction unit be anaerobism sulfate Reduction treatment system, reduction part of sulfuric acid salt generate the Hg in hydrogen sulfide, with waste water2+、Pb2+、Cr3+Reaction generation sulfide sinks It forms sediment.
4. according to the method described in claim 1, it is characterized in that：Rate-determining steps（3）To step（2）Reflux ratio be 50%- 200%。
5. method according to claim 1 or 5, it is characterised in that：Work as step（2）Removal of heavy metal ions rate is low in water outlet When 90%, reflux ratio is continuously decreased, makes oxidation-reduction potential in -300~-200mV, until removal rate is up to more than 95%；Work as step Suddenly（2）When sulphion concentration is more than 2.0mg/L in water outlet, gradually increase reflux ratio, make oxidation-reduction potential -200~- 50mV, until sulphion concentration is less than 0.2mg/L.
6. according to the method described in claim 1, it is characterized in that：Step（3）The denitrogenation unit using existing A/O or SBR denitrification systems are inoculated with denitrifying activated sludge or denitrogenation microbial inoculum in denitrogenation unit.
7. according to the method described in claim 6, it is characterized in that：Following denitrogenation microbial inoculum is inoculated in denitrogenation unit, is contained in microbial inoculum There are secondary coccus FSTB-2, north to see at least one of microbacterium FSTB-4, Pseudomonas stutzeri FSTB-5, examined simultaneously containing marsh Kirschner bacterium FSDN-A and Staphylococcus cohnis FSDN-C, simultaneously containing in arthrobacterium FDN-1 and Shui Shi Flavobacterium FDN-2 at least one Kind, simultaneously containing at least one of Paracoccus denitrificans DN-3 and Methylobacterium SDN-3；Wherein secondary coccus FSTB-2, north are shown in micro- Bacillus FSTB-4, the deposit number of Pseudomonas stutzeri FSTB-5 are CGMCC No.10938, CGMCC No.10939, CGMCC No.10940；It is marsh cock Salmonella FSDN-A, Staphylococcus cohnis FSDN-C, arthrobacterium FDN-1, Shui Shi Flavobacterium FDN-2, de- Nitrogen pair coccus DN-3, the deposit number of Methylobacterium SDN-3 are respectively CGMCC NO.5061, CGMCC NO.5062, CGMCC No.3657, CGMCC No.3659, CGMCC No.3658 and CGMCC No.3660.
8. according to the method described in claim 7, it is characterized in that：" microbacterium FSTB- is seen in secondary coccus FSTB-2, north in microbial inoculum 4th, at least one of Pseudomonas stutzeri FSTB-5 ", " marsh cock Salmonella FSDN-A ", " Staphylococcus cohnis FSDN-C ", " at least one of arthrobacterium FDN-1 and Shui Shi Flavobacteriums FDN-2 ", " in Paracoccus denitrificans DN-3 and Methylobacterium SDN-3 It is at least one ", the volume ratio of five bacteroids is 1-5:1:1:0.1-10:0.1-10.
9. the method according to claim 7 or 8, it is characterised in that：Microbacterium is seen in secondary coccus FSTB-2, north in microbial inoculum The seed liquor of tri- kinds of bacterium of FSTB-4 and Pseudomonas stutzeri FSTB-5 individually amplifies culture or the seed liquor mixing of three kinds of bacterium After be amplified culture；The seed liquor of marsh cock Salmonella FSDN-A and Staphylococcus cohnis FSDN-C need individually amplification training It supports；The seed liquor of arthrobacterium FDN-1 and Shui Shi Flavobacterium FDN-2 individually amplifies culture or the seed liquor mixing of two kinds of bacterium Common amplification culture；The seed liquor of Paracoccus denitrificans DN-3 and Methylobacterium SDN-3 individually amplify culture or two kinds of bacterium The common amplification culture of seed liquor mixing.
10. the method according to claim 7 or 8, it is characterised in that：Microbial inoculum dosage is according to handled waste water body per hour Long-pending 0.001%-0.1% is added.
11. according to the method described in claim 1, it is characterized in that：Step（4）Settlement treatment use sloping plate deposition or gravity Method precipitates, and works as step（4）Supernatant be unsatisfactory for subsequent processing requirement when, be back to step（2）.
12. according to the method described in claim 1, it is characterized in that：The specific water quality of the desulfurization wastewater is：PH is 4-6, SS For 5000-15000mg/L, Ca2+For 1000-2000mg/L, Mg2+For 3000-7000mg/L, Cl-For 7000-17000mg/L, SO4 2-For 4000-8000mg/L, SiO2It is 400-1000mg/ for 5-50mg/L, TDS 16000-36000mg/L, COD concentration L, total nitrogen concentration is 100-300mg/L, simultaneously containing mercury, chromium, cadmium, nickel, lead, zinc, copper ion.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110078209A (en) * 2019-05-16 2019-08-02 桂林电子科技大学 A kind of method of micro-reduction sulfate formation cadmium sulphur mine
CN111099784A (en) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 Treatment method of desulfurization wastewater
CN112875984A (en) * 2021-01-12 2021-06-01 衡阳师范学院 Treatment method of uranium ore wastewater

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4705638A (en) * 1984-05-03 1987-11-10 The University Of Toronto Innovations Foundation Waste water treatment
CN101244859A (en) * 2007-02-13 2008-08-20 中国科学院成都生物研究所 Method for processing heavy metal wastewater
CN102153228A (en) * 2011-01-26 2011-08-17 中节能六合天融环保科技有限公司 Method for treating wet magnesium desulfuration wastewater
US20120305479A1 (en) * 2011-06-01 2012-12-06 David Falatko Mixed substrates for anaerobic bioremediation in aquifers
CN103819061A (en) * 2014-03-12 2014-05-28 武汉凯迪电力环保有限公司 Physicochemical and biochemical combined treatment technology for flue gas desulfurization sewage and device thereof
CN104773925A (en) * 2015-04-23 2015-07-15 合肥工业大学 Method for simultaneously treating refuse leachate and acidy mine drainage
CN104801166A (en) * 2015-04-22 2015-07-29 华南师范大学 Method and device for cooperative flue gas desulfurization and sewage organic matter degradation and denitrification
CN105600991A (en) * 2016-02-03 2016-05-25 大唐环境产业集团股份有限公司 Pretreatment device and method for softening desulphurization waste water
CN105712487A (en) * 2014-12-05 2016-06-29 中国石油化工股份有限公司 Biological processing method of ammonia-containing wastewater
CN105765091A (en) * 2013-11-22 2016-07-13 芬兰国家技术研究中心股份公司 Method for recovering rare earth metals from waste sulphates

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4705638A (en) * 1984-05-03 1987-11-10 The University Of Toronto Innovations Foundation Waste water treatment
CN101244859A (en) * 2007-02-13 2008-08-20 中国科学院成都生物研究所 Method for processing heavy metal wastewater
CN102153228A (en) * 2011-01-26 2011-08-17 中节能六合天融环保科技有限公司 Method for treating wet magnesium desulfuration wastewater
US20120305479A1 (en) * 2011-06-01 2012-12-06 David Falatko Mixed substrates for anaerobic bioremediation in aquifers
CN105765091A (en) * 2013-11-22 2016-07-13 芬兰国家技术研究中心股份公司 Method for recovering rare earth metals from waste sulphates
CN103819061A (en) * 2014-03-12 2014-05-28 武汉凯迪电力环保有限公司 Physicochemical and biochemical combined treatment technology for flue gas desulfurization sewage and device thereof
CN105712487A (en) * 2014-12-05 2016-06-29 中国石油化工股份有限公司 Biological processing method of ammonia-containing wastewater
CN104801166A (en) * 2015-04-22 2015-07-29 华南师范大学 Method and device for cooperative flue gas desulfurization and sewage organic matter degradation and denitrification
CN104773925A (en) * 2015-04-23 2015-07-15 合肥工业大学 Method for simultaneously treating refuse leachate and acidy mine drainage
CN105600991A (en) * 2016-02-03 2016-05-25 大唐环境产业集团股份有限公司 Pretreatment device and method for softening desulphurization waste water

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111099784A (en) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 Treatment method of desulfurization wastewater
CN110078209A (en) * 2019-05-16 2019-08-02 桂林电子科技大学 A kind of method of micro-reduction sulfate formation cadmium sulphur mine
CN112875984A (en) * 2021-01-12 2021-06-01 衡阳师范学院 Treatment method of uranium ore wastewater

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