CN105084589B - The processing method and system of wet-type magnesium method desulfurization waste water - Google Patents
The processing method and system of wet-type magnesium method desulfurization waste water Download PDFInfo
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- CN105084589B CN105084589B CN201510483875.6A CN201510483875A CN105084589B CN 105084589 B CN105084589 B CN 105084589B CN 201510483875 A CN201510483875 A CN 201510483875A CN 105084589 B CN105084589 B CN 105084589B
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Abstract
The present invention discloses a kind of processing method and system of wet-type magnesium method desulfurization waste water, is designed mainly for improving desulfurization wastewater treatment effect.The processing method of wet-type magnesium method desulfurization waste water of the present invention, the pH value at least including carrying out the desulfurization wastewater Air Exposure regulation desulfurization wastewater is 10, ammonia nitrogen is removed to adding phosphate, zeolite powder in the desulfurization wastewater, organic matter, colourity, phosphate, fluoride, heavy metal that coal combustion is produced are removed to feeding lime, molysite in the desulfurization wastewater, desulfurization wastewater PH to 7 is adjusted.The present invention makes the clearance of the COD in desulfurization wastewater bring up to more than 95%, ammonia nitrogen removal frank to more than 90.
Description
Technical field
The present invention relates to a kind of processing method and system of wet-type magnesium method desulfurization waste water.
Background technology
Magnesium oxide method is the another main desulfurization technology for being only second to calcium method in Wet Flue Gas Desulfurization Technology.
Wet-type magnesium method desulfurization technique can be divided into again magnesia/magnefite process, magnesia/magnesium sulfate abandon method, magnesia/
Magnesium sulfate absorption method etc..
Herein at the main desulfurization wastewater introduced in magnesia/magnesium sulfite technique that application is larger, have a extensive future
Science and engineering skill.There is desulfurization wastewater process problem in wet fuel gas desulfurizing technology, although the desulphurization system for there are many power plant is equipped with
Desulfurization wastewater treatment system, but the domestic handling process research at present to desulfurization wastewater is less, wherein it is at most lime to pay close attention to
The desulfurization wastewater that stone/gypsum is produced, the research of the desulfurization wastewater produced for magnesium processes desulfurization is just less.Magnesium processes desulfurization wastewater
Processing is now mostly to be reference and uses for reference limestone/gypsum method desulfurization wastewater process experience.In order to maintain desulfurizer serum recycle
The balance of system material, prevents that soluble substance exceedes setting and ensures accessory substance quality in flue gas, it is necessary to from the circulatory system
Discharge a certain amount of desulfurization wastewater.
The characteristics of magnesium processes desulfurization wastewater, is as follows:
(1) magnesium processes desulphurization system desulfurization wastewater pH value is high compared with calcium method (calcium method is generally 4~6), typically 7~8；
(2) suspension (magnesium sulfite particle, SiO2) content is very high, and concentration is up to tens of thousands of mg/L；
(3) fluoride, COD and heavy metals exceeding standard, COD are up to tens of thousands of mg/L, and ammonia nitrogen is up to more than 500mg/L
(4) salinity is high, and containing substantial amounts of SO42-, Cl- and SO32- plasma, wherein SO42- mass fractions are reachable
12%, Cl- mass fraction are 1%~2%.
(5) water that wet-type magnesium method desulfurization is produced is more much larger than the water of calcium method.
Traditional desulfurization wastewater treatment system includes：Neutralize, react, flocculate, clarify.
But these traditional processing methods can only remove oil removal and part heavy metal, there was only 30% to COD clearance,
Ammonia nitrogen removal frank is almost nil.
It is very big that this desulfurization wastewater is discharged into water body environmental pollution.Can only be outer with other desulfurization wastewater integrated treatments dilution
Row.As country is more and more stricter to discharge into water standard, desulfurization wastewater has to carry out processing COD and ammonia nitrogen, outer could arrange.
Because CL ion concentrations are high, it is impossible that bioanalysis, which removes ammonia nitrogen and COD, can only be removed using other methods, external at present
Useful ultrafiltration and nanofiltration remove the ammonia nitrogen and COD of desulfurization wastewater, but its processing cost is too high, one ton of about 30 yuan of water, but also
The strong brine for having 50% needs after-treatment.
The content of the invention
In view of the above-mentioned problems, the present invention, which provides a kind of clearance that can make COD, brings up to more than 95%, ammonia nitrogen removal frank
To the processing method and system of more than 90 wet-type magnesium method desulfurization waste water.
To reach above-mentioned purpose, the processing method of wet-type magnesium method desulfurization waste water of the present invention, methods described at least includes to institute
It is 10 to state desulfurization wastewater to carry out Air Exposure to adjust the pH value of desulfurization wastewater, to adding phosphate, zeolite in the desulfurization wastewater
Powder removes ammonia nitrogen, and organic matter, colourity, phosphate, fluorine that coal combustion is produced are removed to feeding lime, molysite in the desulfurization wastewater
Compound, heavy metal, adjust desulfurization wastewater PH to 7.
Specifically, methods described specifically includes following steps：
S1 desulfurization wastewaters carry out primary sedimentation concentration, carry out mud-water separation, discharge sludge；
Sodium hydroxide is added in S2 desulfurization wastewaters, the pH value of regulation desulfurization wastewater is 10, and oxygenation carries out Air Exposure, stops
5 to 6 hours, wherein air water ratio 40:1；
Phosphate is added in S3 desulfurization wastewaters and zeolite powder is stirred 20 minutes, is precipitated 3 hours；
Feeding lime and molysite coagulating sedimentation in S4 desulfurization wastewaters, are stirred 20 minutes, are precipitated 3 hours；
Sodium hypochlorite stirring and HCL regulation PH to 7,30 minutes residence times are added in S5 desulfurization wastewaters.
Further, also wrap and precipitation concentration is carried out to the sludge being settled out in S2, mud-water separation is carried out, wherein taking supernatant
Repeat step S1 takes to S5 and carries out centrifugal dehydration treatment with sludge.
To reach above-mentioned purpose, the processing system of wet-type magnesium method desulfurization waste water of the present invention, including the first sludge concentration tank, exposure
Between gas pond, the first mixed precipitation pond, the second mixed precipitation pond, oxidation pond and charging, wherein,
Desulfurization wastewater carries out mud-water separation by the progress primary sedimentation concentration of the first sludge concentration tank, discharges sludge, takes off
Sulphur waste water is exported to aeration tank；
To adding sodium hydroxide in the desulfurization wastewater in aeration tank, the pH value of regulation desulfurization wastewater is 10, be oxygenated into
Row Air Exposure, stops 5 to 6 hours, wherein air water ratio 40:1, output desulfurization wastewater to the first mixed precipitation pond；
To adding sodium hydroxide phosphate and zeolite powder stirring in the desulfurization wastewater in the first mixed precipitation pond
20 minutes, precipitate 3 hours, output desulfurization wastewater to the second mixed precipitation pond；
To feeding lime and molysite coagulating sedimentation in the desulfurization wastewater in the second mixed precipitation pond, stir 20 minutes,
Precipitation 3 hours, output desulfurization wastewater to oxidation pond；
To adding sodium hypochlorite stirring and HCL regulation PH to 7, residence time in the desulfurization wastewater in the oxidation pond
30 minutes；
Described sodium hydroxide, sodium hydroxide phosphate, zeolite powder, lime and molysite is stored in charging.
Further, in addition to the second sludge concentration tank and centrifugal dehydrator, wherein the dirt in the first mixed precipitation pond
Mud is exported to the second sludge concentration tank, is carried out mud-water separation, is taken supernatant to the first mud thickener, remove sludge to centrifugal dehydration
Machine.
The present invention increases aerating system, second coagulation settling system and oxidation pond than traditional technique, makes COD clearance
Bring up to more than 95%, ammonia nitrogen removal frank to more than 90.
It is relative low by more than 70% with external embrane method removal COD and ammonia nitrogen ton water cost.
Brief description of the drawings
Fig. 1 is FGD Wastewater Treatment Process figure described in the embodiment of the present invention.
Embodiment
The present invention will be further described below in conjunction with the accompanying drawings.
Embodiment 1
As shown in figure 1, the processing method of the present embodiment wet-type magnesium method desulfurization waste water, specifically includes following steps：
1) desulfurization wastewater will carry out primary sedimentation concentration, carry out mud-water separation, discharge sludge；
2) increase aeration tank, adjust PH to 10, about 5 hours residence times, gas-water ratio 40:1, remove ammonia nitrogen and COD；
3) secondary flocculation sediment, phosphorate hydrochlorate and zeolite powder are stirred 20 minutes, are precipitated 3 hours, form water insoluble phosphorus
Sour ammonium magnesium precipitate, removes ammonia nitrogen；
4) three flocculation sediments, feeding lime and molysite coagulating sedimentation, are stirred 20 minutes, are precipitated 3 hours, remove part
Other noxious materials such as COD (organic matter that coal combustion is produced), colourity, phosphate, fluoride, heavy metal；
5) last oxidation pond, is mainly carried out to total water outlet plus sodium hypochlorite stirs and adds HCL regulation PH to 7, residence time
30 minutes, to COD (coal combustion produce organic matter) and colourity progress advanced oxidation, the ammonium oxidation in water into nitrogen.
By taking certain city steel works sintering wet-type magnesium method desulfurization wastewater treatment as an example, day discharge capacity water be about 850m3/d, table
It is the actual Inlet and outlet water water quality table of the factory in 1, after the handling process, it is similar wet that COD compares other with the clearance of ammonia nitrogen
The processing of formula magnesium processes desulfurization wastewater is respectively increased to more than 90% and more than 95%, water outlet is stably reached COD<300mg/L, ammonia nitrogen
<35mg/L。
The monthly water-in and water-out water quality average value running situation table of table 1
Unit mg/L
In the present embodiment, mainly by the first concentrating and precipitating of desulfurization wastewater after, water outlet adjusts PH being aerated, oxidation removal
COD, stripping part ammonia nitrogen；Again by Zeolite Addition powder and phosphate, physical chemistry precipitation is carried out, part ammonia nitrogen, zeolite is removed
Absorbed portion ammonia nitrogen again；Water outlet is adding other materials such as lime and molysite removal part COD, colourity, phosphate, heavy metal；
Finally by sodium hypochlorite is added, partial organic substances, colourity and ammonia nitrogen are removed, water outlet is reached COD<300mg/L, ammonia nitrogen<
35mg/L, then arranged with outside other waste water integrated treatments.
Desulfurization wastewater will carry out primary sedimentation concentration first, and mainly suspension is too high in waste water, removes oil removal.
Secondly increase aerating system, carries out hydrogenation sodium oxide molybdena, regulation is arrived pH value 10, filled to desulfurization wastewater precipitation water outlet
Oxygen is aerated, and gas-water ratio is according to 40:1, stripping part ammonia nitrogen is carrying out absorbing the ammonia of stripping, ammonia nitrogen has 30% with dilute sulfuric acid water
Clearance；Overwhelming majority COD is caused by magnesium sulfite, by increasing oxygenic aeration formation magnesium sulfate, drop in desulfurization wastewater
Low COD, COD clearance are up to more than 95%.
Pass through second coagulation settling system again, be mainly sufficiently stirred for, made in water by Zeolite Addition powder and phosphate
Magnesium salts, ammonia and phosphate form water insoluble magnesium ammonium phosphate sediment, remove part ammonia nitrogen, and zeolite can absorbed portion ammonia again
Nitrogen, makes the clearance more than 80% of ammonia nitrogen.
Again by three coagulating sedimentation systems, main adds sodium hypochlorite, lime and molysite coagulating sedimentation, removal portion again
Divide other noxious materials such as COD (organic matter that coal combustion is produced), colourity, phosphate, fluoride, heavy metal, oxidation changes weight
The valence state of metal, becomes easy deposit, and such as thallium is oxidized to trivalent from monovalence, obtains and is removed by coagulating sedimentation.
Last oxidation pond, is mainly carried out to total water outlet plus sodium hypochlorite stirs and adds HCL regulation PH to 7, and to COD, (coal fires
Burn the organic matter produced) and colourity progress advanced oxidation, the ammonium oxidation in water into nitrogen.
Embodiment 2
The processing method of the present embodiment wet-type magnesium method desulfurization waste water, on the basis of above-described embodiment 1, is also wrapped to being settled out
Sludge carry out precipitation concentration, carry out mud-water separation, wherein taking the step of supernatant repeats above-described embodiment 1, take and enter with sludge
Row centrifugal dehydration treatment.
Embodiment 3
The processing system of the present embodiment wet-type magnesium method desulfurization waste water, including the first sludge concentration tank, aeration tank, the first mixing
Between sedimentation basin, the second mixed precipitation pond, oxidation pond and charging, wherein,
Desulfurization wastewater carries out mud-water separation by the progress primary sedimentation concentration of the first sludge concentration tank, discharges sludge, takes off
Sulphur waste water is exported to aeration tank；
To adding sodium hydroxide in the desulfurization wastewater in aeration tank, the pH value of regulation desulfurization wastewater is 10, be oxygenated into
Row Air Exposure, stops 5 to 6 hours, wherein air water ratio 40:1, output desulfurization wastewater to the first mixed precipitation pond；
To adding sodium hydroxide, phosphate and zeolite powder stirring in the desulfurization wastewater in the first mixed precipitation pond
20 minutes, precipitate 3 hours, output desulfurization wastewater to the second mixed precipitation pond；
To adding sodium hypochlorite, lime and molysite coagulating sedimentation in the desulfurization wastewater in the second mixed precipitation pond, stir
Mix 20 minutes, precipitate 3 hours, output desulfurization wastewater to oxidation pond；
To adding sodium hypochlorite stirring and HCL regulation PH to 7, residence time in the desulfurization wastewater in the oxidation pond
30 minutes；
Described sodium hydroxide, sodium hydroxide phosphate, zeolite powder, lime and molysite is stored in charging.
The present embodiment, in addition to the second sludge concentration tank and centrifugal dehydrator, wherein the dirt in the first mixed precipitation pond
Mud is exported to the second sludge concentration tank, is carried out mud-water separation, is taken supernatant to the first mud thickener, remove sludge to centrifugal dehydration
Machine.
The processing method of wet-type magnesium method desulfurization waste water described in above-described embodiment can be using described in the present embodiment
System is handled, but is not limited to the system described in the present embodiment.
More than, only presently preferred embodiments of the present invention, but protection scope of the present invention is not limited thereto, and it is any to be familiar with sheet
Those skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in should all be covered
Within protection scope of the present invention.Therefore, the protection domain that protection scope of the present invention should be defined by claim is defined.
Claims (4)
1. a kind of processing method of wet-type magnesium method desulfurization waste water, it is characterised in that：Methods described at least includes useless to the desulfurization
The pH value that water carries out Air Exposure regulation desulfurization wastewater is 10, and ammonia is removed to adding phosphate, zeolite powder in the desulfurization wastewater
Nitrogen, organic matter, colourity, phosphate, fluoride that coal combustion produces, again are removed to feeding lime in the desulfurization wastewater, molysite
Metal, adjusts desulfurization wastewater pH to 7；
Specifically include following steps：
S1 desulfurization wastewaters carry out primary sedimentation concentration, carry out mud-water separation, discharge sludge；
Sodium hydroxide is added in S2 desulfurization wastewaters, the pH value of regulation desulfurization wastewater is 10, and oxygenation carries out Air Exposure, stops 5 to 6
Hour, wherein air water ratio 40:1；
Phosphate is added in S3 desulfurization wastewaters and zeolite powder is stirred 20 minutes, is precipitated 3 hours；
Feeding lime and molysite coagulating sedimentation in S4 desulfurization wastewaters, are stirred 20 minutes, are precipitated 3 hours；
Sodium hypochlorite stirring and HCl regulation pH to 7,30 minutes residence times are added in S5 desulfurization wastewaters.
2. the processing method of wet-type magnesium method desulfurization waste water according to claim 1, it is characterised in that：Also include to being sunk in S1
The sludge that forms sediment carries out precipitation concentration, carries out mud-water separation, wherein taking supernatant repeat step S1 to S5, takes sludge to be centrifuged
Dewater treatment.
3. a kind of processing system of wet-type magnesium method desulfurization waste water, it is characterised in that：Including the first sludge concentration tank, aeration tank,
Between one mixed precipitation pond, the second mixed precipitation pond, oxidation pond and charging, wherein,
Desulfurization wastewater carries out primary sedimentation concentration by the first sludge concentration tank, carries out mud-water separation, discharges sludge, desulfurization wastewater
Export to aeration tank；
To adding sodium hydroxide in the desulfurization wastewater in aeration tank, the pH value of regulation desulfurization wastewater is 10, and oxygenation is carried out at aeration
Reason, stops 5 to 6 hours, wherein air water ratio 40:1, output desulfurization wastewater to the first mixed precipitation pond；
Stirred 20 minutes to adding sodium hydroxide, phosphate and zeolite powder in the desulfurization wastewater in the first mixed precipitation pond,
Precipitation 3 hours, output desulfurization wastewater to the second mixed precipitation pond；
To feeding lime and molysite coagulating sedimentation in the desulfurization wastewater in the second mixed precipitation pond, stir 20 minutes, precipitation 3
Hour, output desulfurization wastewater to oxidation pond；
To adding sodium hypochlorite stirring and HCl regulation pH to 7,30 minutes residence times in the desulfurization wastewater in the oxidation pond；
Described sodium hydroxide, phosphate, zeolite powder, lime and molysite is stored in charging.
4. the processing system of wet-type magnesium method desulfurization waste water according to claim 3, it is characterised in that：Also include the second sludge
Concentration basin and centrifugal dehydrator, wherein the sludge in the first mixed precipitation pond is exported to the second sludge concentration tank, carry out muddy water
Separation, takes supernatant to the first mud thickener, takes sludge to centrifugal dehydrator.
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| CN106145445A (en) * | 2016-08-08 | 2016-11-23 | 田静 | A kind of method of wastewater treatment |
| CN106430794A (en) * | 2016-12-20 | 2017-02-22 | 大唐国际化工技术研究院有限公司 | Resourceful treatment method and treatment system for desulfuration wastewater |
| CN109092043A (en) * | 2018-09-07 | 2018-12-28 | 丽水市杭丽热电有限公司 | boiler flue gas desulfurization device |
| CN109320015A (en) * | 2018-10-31 | 2019-02-12 | 中冶华天工程技术有限公司 | The processing method and system of emulsified waste liquid denitrogenation dephosphorizing |
| CN109574315A (en) * | 2018-12-28 | 2019-04-05 | 东莞市三人行环境科技有限公司 | A kind of PID waste water treatment system |
| CN110436671B (en) * | 2019-08-30 | 2024-05-14 | 中冶赛迪工程技术股份有限公司 | Zero discharge treatment method and system for sintering wet desulfurization wastewater |
| CN110655228A (en) * | 2019-08-31 | 2020-01-07 | 广东韶钢松山股份有限公司 | Wastewater treatment process and system |
| CN115385501A (en) * | 2021-05-25 | 2022-11-25 | 中国石油天然气股份有限公司 | System for handle and retrieval and utilization high COD gas field waste water that contains sulphur |
| CN113402055A (en) * | 2021-06-09 | 2021-09-17 | 金隆铜业有限公司 | Flue gas desulfurization wastewater treatment method and treatment system |
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| JP2003136092A (en) * | 2001-11-02 | 2003-05-13 | Mitsubishi Heavy Ind Ltd | Method and apparatus for treating exhaust gas desulfurization wastewater |
| JP2007175673A (en) * | 2005-12-28 | 2007-07-12 | Idemitsu Kosan Co Ltd | Treatment method of ammonia-containing drain |
| CN101555077B (en) * | 2008-04-11 | 2011-02-09 | 中国科学院广州地球化学研究所 | Method for treating highly concentrated ammonian wastewater with poor biodegradability by using a multiple-technique combination |
| CN102153228B (en) * | 2011-01-26 | 2013-04-24 | 中节能六合天融环保科技有限公司 | Method for treating wet magnesium desulfuration wastewater |
| CN103318867A (en) * | 2013-06-13 | 2013-09-25 | 江苏远东环保工程有限公司 | Method for recovering magnesium ammonium phosphate from magnesia process desulfurization waste liquid and equipment system of method |
| CN204111467U (en) * | 2014-09-03 | 2015-01-21 | 重庆远达水务有限公司 | A kind of Novel desulphurization Waste Water Treatment |
| CN104803504B (en) * | 2015-02-09 | 2017-05-03 | 江苏源能环境工程有限公司 | Novel desulfurization waste water treatment method |
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