CN101693574A - Method for treating waste water with high pH value, high sulfide content, high ammonia nitrogen content and high COD content - Google Patents
Method for treating waste water with high pH value, high sulfide content, high ammonia nitrogen content and high COD content Download PDFInfo
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- CN101693574A CN101693574A CN200910044304A CN200910044304A CN101693574A CN 101693574 A CN101693574 A CN 101693574A CN 200910044304 A CN200910044304 A CN 200910044304A CN 200910044304 A CN200910044304 A CN 200910044304A CN 101693574 A CN101693574 A CN 101693574A
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Abstract
The invention provides a method for treating waste water with high pH value, high sulfide content, high ammonia and nitrogen content and high COD content. The method comprises the following steps: firstly, pretreating the waste water by adopting acidification-malysite flocculation sedimentation to reduce the concentration of S2- in the waste water, eliminate the restraining function of the S2- to biological treatment, remove COD caused by the S2- and decompose substances which are easily acidized and decomposed in the waste water; secondly, carrying out biological treatment, wherein the biological treatment consists of processes of hydrolytic acidification and autotrophy SBR, organisms which are difficultly decomposed are decomposed in the hydrolytic acidification process to provide a carbon source for denitrification, oxygen is provided by aeration for the autotrophy SBR, the COD in the waste water is removed by using aerobic microorganisms, NaHCO3 is additionally added to adjust the pH value to ensure an optimal growth environment for autotrophy nitrobacteria, and ammonia and nitrogen are oxidized and removed by using oxygen and HCO32-; and finally, carrying out deep treatment by adopting flocculation sedimentation and -ClO2 oxidation to remove the color of the waste water and ensure that all indexes achieve the discharge standard.
Description
Technical field
The present invention relates to the wastewater treatment field of environment protection, be specifically related to a kind of " high pH, high sulfide, high ammonia nitrogen, high COD " wastewater treatment method.
Technical background
China is one of more rich country of Mineral resources in the world, and identified Mineral resources total amount accounted for 12% of the world by 2003, and its potential is worth and occupies the third place in the world.Wherein, 6,708 ten thousand tons of copper, its reserves occupy the tenth in the world; 25.5 hundred million tons in bauxite, its reserves occupy the 9th in the world; Plumbous 3,757 ten thousand tons, its reserves occupy the third place in the world; 9,267 ten thousand tons on zinc, its reserves occupy the third place in the world; 8,130,000 tons in nickel, its reserves occupy the 9th in the world; 5,690,000 tons in tungsten, 2,070,000 tons in antimony, 8,909 ten thousand tons of rare earths, its reserves all occupy first place in the world; 9,990,000 tons of molybdenums, 810,000 tons in tin, its reserves Jun Ju second place of the world.But China's nonferrous metal resource also has the characteristics of self: 1), " little metal " Mineral resources are abundanter, and large Mineral resources reserves relative deficiency; 2), lean ore is more, the rich ore rareness, the development and use difficulty is big; 3), symbiosis, association mineral deposit be many, single mineral deposit is few; 4), have a very wide distribution.
Hunan Province's element is celebrated with " township of non-ferrous metal ", Mineral resources are very abundant, the proven reserve rank whole nation first of tungsten, antimony, bismuth mineral wherein, the reserves of tin, lead, mercury ore occupy the first five position, the whole nation, and exploitation of mineral resources and the ore dressing production history in more than 100 year arranged, most of non-ferrous metal ore productions all depend on beneficiation reagent floatation recovery valuable mineral, so beneficiation reagent production becomes one of requisite industry of our province.In recent years, develop rapidly along with global economic integration, national economy grows with each passing day to the demand of non-ferrous metal, drives the unprecedented soaring of upstream nonferrous metals ore digging, sorting, smelting output thereupon, and beneficiation reagent production is as the also corresponding increase of related industries output.
The principle that beneficiation reagent carries out ore-dressing practice is to utilize the surperficial hydrophilic and hydrophobic of mineral that different minerals is separated, and adds an amount of medicament in ore pulp, and medicament and the absorption of purpose mineral also form hydrophobic group, and emerging reaches the isolating purpose of mineral.Main beneficiation reagent product has: receive and catch agent class, pore forming material class, to adjust agent class three major types other, wherein receive and catch the agent class xanthate series, black powder series, thiocarbamate, amine four big series product kind more than 20 are arranged; Pore forming material has 5 kinds of products; Adjust agent product kind more than 10 is arranged.The beneficiation reagent production process is the chemosynthesis process, owing to contain sulfide, ammonia and organic substance in products material, production intermediate product and the product, cause that " four height " arranged in the beneficiation reagent factory effluent: high pH (pH=11.0), high sulfide (300mg/L), high ammonia nitrogen (600mg/L), high COD (4000mg/L), and the relatively poor B/C=0.3 of wastewater biodegradability～0.5 belongs to one of unmanageable industrial production waste water.
Processing to high ammonia-nitrogen wastewater, high waste water sulfide at present has one or more treatment processs commonly used:
High ammonia-nitrogen wastewater is one of more difficult waste water, and on the engineering there be technology commonly used at present: stripping, break point chlorination, the MAP precipitator method and biological denitrificaion.Stripping, break point chlorination, the MAP precipitator method are physics, method of chemical treatment, and cost for wastewater treatment is higher, and just ammonia nitrogen does not change the valence state and the character of nitrogen from the transfer process of waste water to atmosphere and bed mud.The biological denitrificaion treating processes need be passed through two phase process of nitrification and denitrification.Nitrifying process is an aerobic processes, and ammonia-state nitrogen is converted into nitrate and nitroso-group nitrogen under the effect of nitrifier; Denitrification process is anaerobic process, and nitrate and nitroso-group nitrogen are converted into nitrogen under the effect of denitrifying bacteria.Biological denitrification process commonly used at present has A/O, A
2Technologies such as/O, but the concentration of working as biological denitrificaion is generally below 400mg/L, biological denitrificaion is handled high-concentration ammonia nitrogenous wastewater just need carry out big multiple dilution, and need add COD defect of insufficient in the additional waste water of organic carbon source, this not only feasible the bulky of facility of carrying out a biological disposal upon, and the also corresponding raising of energy consumption.High ammonia-nitrogen wastewater is directly carried out a biological disposal upon not have temporarily and is used in the present engineering, all will carry out physico-chemical pretreatment as the high ammonia-nitrogen wastewater biological treatment is last, and processing technological flow is longer, and working cost is higher.The expert has also proposed many ammonia nitrogen waste waters and has handled new technology both at home and abroad in recent years, as: technology such as short-cut nitrification and denitrification treatment technology, synchronous nitration and denitrification, whole process autotrophic denitrification, but substantially still be in laboratory stage at present.The progress of high ammonia-nitrogen wastewater treatment technology is still based on traditional treatment process.
Hydrogen sulfide toxicity is bigger, and hydrobiont is had the stronger ability of killing livestock, so can produce toxic action to biochemical system during the sulfides from wastewater too high levels, must carry out pre-treatment, its content is lower than suppresses bioactive threshold concentration.The pretreatment process of hydrogen sulfide has at present: oxidation style, gas are carried recovery, flocculation sediment etc.Because sulfide has reductibility, therefore easily and the oxygenant effect, be oxidized to sulphur or vitriol and from waste water, remove.It is to utilize water vapour in stripping tower the hydrogen sulfide in the waste water to be separated that gas is put forward absorption method, and absorb system sodium sulphite with sodium hydroxide and recycle and reuse, this method clearance is higher, the treatment process maturation, but energy consumption and facility investment are all bigger, be applicable to the processing of the sulfur-containing waste water that the water yield is big, concentration is high, the waste water little to the water yield is not suitable for.Flocculent precipitation is to utilize some metals and sulfide effect to generate insoluble precipitation and removed.The most frequently used precipitation agent is a molysite, comprises ferrous salt and ferric salt.The coagulant sedimentation investment is little, simple to operate, also be a kind of duration of service of method early, but the tiny precipitate that this method generates is relatively poor, the mud-water separation difficulty.Sulphide-containing waste water is generally chemical industry, petrochemical industry waste water, and the waste water situation is different, and the treatment process that is suitable for is also different, therefore must carry out analysis of experiments, can select best treatment process than choosing the removal method of sulfide.
At present, similar beneficiation reagent " four height " production wastewater treatment is domestic does not still have ripe a, treatment process efficiently.Treatment process is handled the processing target that can't reach expection routinely, so waste water disposal facility, and often because of flocculation sediment weak effect, biochemical system can't normally start, effluent quality exceeds standard and be in paralyzed state.
Summary of the invention
For overcoming the various defectives in above-mentioned high pH, high sulfide, high ammonia nitrogen, the high-COD waste water treatment technology, fill up the blank of handling " four height " waste water technology simultaneously, the technology that a kind of technology is simple, treatment effect is excellent is provided, and technical scheme provided by the invention is the treatment process of a kind of high pH, high sulfide, high ammonia nitrogen, high-COD waste water.
Above-mentioned method of wastewater treatment may further comprise the steps:
(1) in waste water, adds 600mg/L-800mg/L FeSO
47H
2O, adding diluted acid adjustment wastewater pH simultaneously is 6.0-7.5, adds flocculation agent then and makes it form precipitation, separates and removes precipitation;
(2) mix through step (1) waste water of handling and the recirculation water of handling through aerobe, and carry out acidication, reflux ratio is 150%-200%, and hydraulic detention time is 5h-8h, adds potassium primary phosphate 30mg/L-50mg/L, and the pH value is controlled at 6.5～7.0;
(3) water outlet enters the sbr reactor pond after step (2) is handled, the aeration oxygen supply, and the reaction tank dissolved oxygen is controlled at more than the 2mg/L, adds NaHCO simultaneously
3Control pH is 7.2-7.8, and hydraulic detention time is 2-4 days;
(4) after water outlet adds 50mg/L-200mg/L Tai-Ace S 150 flocculation sediment after step (3) is handled, add 10mg/L-50mg/L ClO again
2Oxidation;
Wherein, the recirculation water of the described aerobe processing of step (2) is that the back water outlet is handled in step (3) sbr reactor pond.
The described flocculation agent of step (1) is an alum, and add-on is 200-400mg/L; The recirculation water that described technology aerobe of step (2) handled is the water outlet after handle in step (3) sbr reactor pond, and the water quality situation is: the about 150mg/L of COD, S
2-＜0.1mg/L, NH
3-N＜10mg/L; The described SBR of step (3) is operating as aerobic 3-5h, precipitation 0.5-1.0h, and draining 0.5-1.0h, water inlet 2-4h begins aeration behind the water inlet 0.5-1.0h.
Above-mentioned high pH, high sulfide, high ammonia nitrogen, the preferred beneficiation reagent factory effluent of high-COD waste water are the comprehensive incomes that common beneficiation reagent is produced each workshop gained waste water.The beneficiation reagent product category is many, and raw material, the production technique of each product have nothing in common with each other, and cause wastewater source many, and instantaneous waste water quality, the water yield change greatly, waste water composition complexity.
Know-why of the present invention comprises:
1) in waste water, adds FeSO
47H
2O, Fe
2+With make S in the waste water
2-React generation FeS precipitation, add diluted acid simultaneously and adjust the wastewater pH environment, change the electrical of FeS particle surface.Flocculation agent selects for use alum flocculation sediment effect better, and supernatant liquor water white transparency, flocculation agent make FeS assemble form volume, particle that density is bigger, and are deposited to the bottom, realize mud-water separation, finish the desulfurization pre-treatment to waste water.
The molysite flocculent precipitation is removed the treatment process of sulfides from wastewater, because the FeS fine particle settleability of producing is poor, the mud-water separation difficulty is so this method application is not extensive.The present invention adds acidization on the basis of molysite flocculent precipitation, by adjusting the pH environment, zeta-potential between the FeS colloidal solid of stable suspersion in the water is reduced or disappear, the further loss of stability of particulate under the effect of flocculation agent, collision coalescence formation volume, the flco that proportion is bigger, precipitation rapidly.Acidification has overcome the shortcoming of molysite deposition method settling property difference, and the precipitation beginning muddy water layering just occurred in 1 minute in the beaker test, leaves standstill that all FeS flcos all are sunken to the bottom after 30 minutes, and supernatant liquor is as clear as crystal.Therefore, the acidification in the flocculation sediment process has shortened sedimentation time greatly, has dwindled the settling tank volume, has improved the settling property of FeS, and the tiny precipitate that has thoroughly solved this method generation is relatively poor, the mud-water separation problem of difficult.
2) recirculation water of handling through the pretreated waste water of step 1) and aerobe is mixed into the hydrolysis acidification pool of biological treatment system.Anaerobion and amphimicrobe are decomposed into the larger molecular organics in the waste water small organic molecule of readily biodegradable in anaerobic environment; The COD that nitrate in the aerobic backwater, nitrite then utilize the waste water of step 1) to be rich in is reduced into nitrogen and removes from water under the effect of denitrifying bacteria, remove a part of COD simultaneously.
3) step 2) water outlet enters the sbr reactor pond, provides aerobic microbiological required oxygen by the gas blower aeration, makes good use of the COD in the oxygen animalcule effect degrading waste water, simultaneously by adding NaHCO
3Control pH makes it utilize oxygen and CO at the optimum growh environment of autotrophy nitrobacteria
3 2-For inorganic carbon source is converted into nitrate, nitrite with ammonia nitrogen.Handle through SBR, the ammonia nitrogen in the waste water, sulfide is far below emission standard, and COD is near emission standard, but effluent color dilution exceeds standard and need carry out advanced treatment.
The waste water aerobic biological treatment requires waste water C: N: P=100: 5: 1, C: N: the inharmonic waste water of P ratio is generally adjusted C by adding organic carbon source, nitrogenous source or phosphorus source: the ratio of N: P guaranteed the normal operation of biological treatment of waste water system.Beneficiation reagent waste water belongs to C: N: the P ratio is waste water on the low side obviously, if replenish the load that organic carbon source must increase system in proportion, increases cost of investment and working cost.The present invention is at waste water C: under the situation that the N ratio is on the low side, it is not to guarantee C: the N ratio by replenishing organic carbon source, but control the pH value environment of aerobic biosystem, for the ammoxidation in growth, breeding and the vital movement thereof of autotrophy nitrifier provides enough basicity and inorganic carbon sources, under the best pH of vital movement, the autotrophy nitrifier utilizes inorganic carbon source CO
3 2-In aerobic environment, ammonia nitrogen is converted into nitrate, nitrite and with ammonia nitrogen removal.
4) the step 3) water outlet adds ClO again behind the Tai-Ace S 150 flocculation sediment
2Oxidation, water outlet COD, colourity are all up to standard, satisfy the requirement of discharging and production reuse.
Method of the present invention is at the waste water of high pH, high sulfide, high ammonia nitrogen, high COD, especially the comprehensive factory effluent of beneficiation reagent is handled, operational path is simple, has saved working cost and energy consumption effectively, and is applicable to the processing of various beneficiation reagent factory effluents.Water after handling by this method, objectionable impurities clearance height, every index is good, can cyclically utilizing, reduced the waste of water resources and the pollution of environment.It is the waste water treatment process of a suitability for mass industrialized application.
Description of drawings
Fig. 1 is the technology course diagram of method of wastewater treatment of the present invention.
Embodiment
Embodiment
Each beneficiation reagent workshop waste water has formed beneficiation reagent factory comprehensive wastewater after collecting the adjusting homogeneous.Waste water at first carries out pre-treatment, and acidifying-ferrous salt precipitator method are adopted in pre-treatment, and the ferrous salt consumption is 0.7kg/m
3, sulfuric acid 2.21kg/m
3, alum 0.3kg/m
3The ferrous salt precipitating phase can be removed in the waste water because of S
2-The COD that causes, acidization also makes in the waste water organic substance with acidification hydrolization decompose and removes portion C OD, and pre-treatment COD clearance is about 61.05%, sulfide clearance 52.85%, ammonia nitrogen go to handle 27.31%.
Pretreated waste water is carried out biological treatment through post precipitation, and biological treatment adopts acidication-autotrophy SBR technology, and acidication section hydraulic detention time 6h, effluent recycling be than 100%, biphosphate potassium application rate 40mg/L.The acidication section is utilized the effect of anaerobion to fall larger molecular organics and is decomposed into small organic molecule, and utilizing partial organic substances in the waste water to be used for self growth and breeding, the anaerobic denitrifying bacterium also utilizes organism that pretreated waste water provides with nitrate in the recirculation water nitrate reduction to be become nitrogen and removes ammonia nitrogen in anaerobic environment.Acidication section COD clearance is 44.05%, ammonia nitrogen removal frank is 48.32%, the sulfide clearance is 48.60%.
Autotrophy SBR section hydraulic detention time 3d, NaHCO
3Consumption 0.8kg/m
3, dissolved oxygen is more than 2mg/L.Autotrophy SBR section is made good use of organism, oxidation S in the oxygen animalcule degrading waste water in aerobic environment
2-The autotrophy nitrifier is at NaHCO
3Oxidation ammonia nitrogen in the basicity environment that provides; Autotrophy SBR section is the main processing unit of denitrogenation, the main contamination index of the water outlet after this section processing ammonia nitrogen, S
2-All reached emission standard, COD is near emission standard, and the COD clearance is 62.80%, ammonia nitrogen removal frank is 92.86%, the sulfide clearance is 98.36%.
Autotrophy SBR water outlet enters advanced treatment, colourity and further the remove COD of main purpose for removing waste water.Advanced treatment adopts coagulating sedimentation-ClO
2Oxidation.The consumption of coagulating sedimentation Tai-Ace S 150 is 0.1kg/m
3, ClO
2Oxidation ClO
2Consumption is 0.03kg/m
3Through coagulating sedimentation-ClO
2Water outlet COD68mg/L after the oxidation, ammonia nitrogen 7.5mg/L, S
2-0.22mg/L.
This sewage treatment technology process figure as shown in Figure 1, wastewater treatment result and each section efficient see Table 1.The total clearance 96.42% of COD, the total clearance 98.17% of ammonia nitrogen, the total clearance 99.85% of sulfide.The every index of water outlet all reaches " integrated wastewater discharge standard " (GB8978-1996) primary standard, and satisfies the requirement of production technique quality of reused water.
Each section of table 1 waste water treatment process treatment effect
Claims (4)
1. the treatment process of a high pH, high sulfide, high ammonia nitrogen, high-COD waste water is characterized in that, may further comprise the steps:
(1) in waste water, adds 600mg/L-800mg/L FeSO
47H
2O, adding diluted acid adjustment wastewater pH simultaneously is 6.0-7.5, adds flocculation agent then and makes it form precipitation, separates and removes precipitation;
(2) mix through step (1) waste water of handling and the recirculation water of handling through aerobe, and carry out acidication, reflux ratio is 150%-200%, and hydraulic detention time is 5h-8h, adds potassium primary phosphate 30
Mg/L-50mg/L, the pH value is controlled at 6.5～7.0;
(3) water outlet enters the sbr reactor pond after step (2) is handled, the aeration oxygen supply, and the reaction tank dissolved oxygen is controlled at more than the 2mg/L, adds NaHCO simultaneously
3Control pH is 7.2-7.8, and hydraulic detention time is 2-4 days;
(4) after water outlet adds 50mg/L-200mg/L Tai-Ace S 150 flocculation sediment after step (3) is handled, add 10mg/L-50mg/L ClO again
2Oxidation;
Wherein, the recirculation water of the described aerobe processing of step (2) is that the back water outlet is handled in step (3) sbr reactor pond.
2. method according to claim 1 is characterized in that, the described flocculation agent of step (1) is an alum, and add-on is 200-400mg/L.
3. method according to claim 1 is characterized in that, the described SBR of step (3) is operating as aerobic time 3-5h, precipitation 0.5-1.0h, and draining 0.5-1.0h, water inlet 2-4h begins aeration behind the water inlet 0.5-1.0h.
4. method according to claim 1 is characterized in that, described high pH, high sulfide, high ammonia nitrogen, high-COD waste water are the comprehensive factory effluent of beneficiation reagent.
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| CN103524003A (en) * | 2013-10-30 | 2014-01-22 | 铁岭选矿药剂有限公司 | Treating apparatus and method for wastewater of beneficiation reagent production |
| CN103693785A (en) * | 2014-01-10 | 2014-04-02 | 韶关学院 | Method for removing exceeding sulfides from lead-zinc beneficiation wastewater |
| CN105776659A (en) * | 2016-03-30 | 2016-07-20 | 安徽兴安电气设备股份有限公司 | Method for treating sewage |
| CN105836946A (en) * | 2016-06-02 | 2016-08-10 | 陈昌 | Method for treating high-sulfur sewage |
| CN106007057A (en) * | 2016-06-13 | 2016-10-12 | 深圳市绿恩环保技术有限公司 | Treatment method for COD and ammonia nitrogen mixed waste liquor |
| CN106698632A (en) * | 2016-12-30 | 2017-05-24 | 四川师范大学 | Treatment method of mercury-containing wastewater |
| CN107487952A (en) * | 2017-09-22 | 2017-12-19 | 中南大学 | A kind of combination treatment method of the residual beneficiation wastewater containing xanthate |
| US9884779B2 (en) | 2010-12-02 | 2018-02-06 | The Hong Kong University Of Science And Technology | Biological wastewater treatment and reuse utilizing sulfur compounds as electron carrier to minimize sludge production |
| CN108191161A (en) * | 2018-01-25 | 2018-06-22 | 轻工业环境保护研究所 | It is a kind of to handle biogas slurry technique using sulfate reducing bacteria |
| US10301204B2 (en) | 2015-01-14 | 2019-05-28 | The Hong Kong University Of Science And Technology | Internal sulfur cycling SANI (ISC-SANI) process for biological wastewater treatment |
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| US9884779B2 (en) | 2010-12-02 | 2018-02-06 | The Hong Kong University Of Science And Technology | Biological wastewater treatment and reuse utilizing sulfur compounds as electron carrier to minimize sludge production |
| CN103524003A (en) * | 2013-10-30 | 2014-01-22 | 铁岭选矿药剂有限公司 | Treating apparatus and method for wastewater of beneficiation reagent production |
| CN103693785A (en) * | 2014-01-10 | 2014-04-02 | 韶关学院 | Method for removing exceeding sulfides from lead-zinc beneficiation wastewater |
| US10301204B2 (en) | 2015-01-14 | 2019-05-28 | The Hong Kong University Of Science And Technology | Internal sulfur cycling SANI (ISC-SANI) process for biological wastewater treatment |
| CN105776659A (en) * | 2016-03-30 | 2016-07-20 | 安徽兴安电气设备股份有限公司 | Method for treating sewage |
| CN105836946A (en) * | 2016-06-02 | 2016-08-10 | 陈昌 | Method for treating high-sulfur sewage |
| CN106007057A (en) * | 2016-06-13 | 2016-10-12 | 深圳市绿恩环保技术有限公司 | Treatment method for COD and ammonia nitrogen mixed waste liquor |
| CN106007057B (en) * | 2016-06-13 | 2020-01-21 | 深圳市绿恩环保技术有限公司 | Treatment method of COD (chemical oxygen demand) and ammonia nitrogen mixed waste liquid |
| CN106698632A (en) * | 2016-12-30 | 2017-05-24 | 四川师范大学 | Treatment method of mercury-containing wastewater |
| CN107487952B (en) * | 2017-09-22 | 2020-09-29 | 长沙华时捷环保科技发展股份有限公司 | Combined treatment method for beneficiation wastewater containing xanthate residues |
| CN107487952A (en) * | 2017-09-22 | 2017-12-19 | 中南大学 | A kind of combination treatment method of the residual beneficiation wastewater containing xanthate |
| CN108191161A (en) * | 2018-01-25 | 2018-06-22 | 轻工业环境保护研究所 | It is a kind of to handle biogas slurry technique using sulfate reducing bacteria |
| CN108191161B (en) * | 2018-01-25 | 2020-12-29 | 轻工业环境保护研究所 | Process for treating biogas slurry by using sulfate reducing bacteria |
| CN110772876A (en) * | 2019-10-31 | 2020-02-11 | 深圳市深投环保科技有限公司 | Treatment method of RGB waste liquid |
| CN111960527A (en) * | 2020-07-14 | 2020-11-20 | 中原环保知和(郑州)水环境科技有限公司 | ClO (ClO)2Method for deeply treating biochemical tail water of sewage by effervescent tablets |
| CN112479369A (en) * | 2020-11-10 | 2021-03-12 | 大连民族大学 | Toilet sewage treatment device and method |
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