CN109305735A - Defluorination method and defluorination system for flue gas desulfurization wastewater - Google Patents
Defluorination method and defluorination system for flue gas desulfurization wastewater Download PDFInfo
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- CN109305735A CN109305735A CN201710639212.8A CN201710639212A CN109305735A CN 109305735 A CN109305735 A CN 109305735A CN 201710639212 A CN201710639212 A CN 201710639212A CN 109305735 A CN109305735 A CN 109305735A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 64
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 13
- 230000023556 desulfurization Effects 0.000 title claims abstract description 13
- 239000003546 flue gas Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 33
- 238000006115 defluorination reaction Methods 0.000 title claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 30
- 239000011737 fluorine Substances 0.000 claims abstract description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000001112 coagulating effect Effects 0.000 claims abstract description 8
- 238000005345 coagulation Methods 0.000 claims description 38
- 230000015271 coagulation Effects 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000007667 floating Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims 1
- -1 fluorine ions Chemical class 0.000 abstract description 6
- 238000004062 sedimentation Methods 0.000 abstract description 4
- 238000009297 electrocoagulation Methods 0.000 abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 17
- 230000005611 electricity Effects 0.000 description 16
- 238000005868 electrolysis reaction Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000012545 processing Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 239000010802 sludge Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000005189 flocculation Methods 0.000 description 5
- 230000016615 flocculation Effects 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 238000005354 coacervation Methods 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 210000001367 artery Anatomy 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 210000003462 vein Anatomy 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical group 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
-
- 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
- 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4616—Power supply
- C02F2201/46175—Electrical pulses
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a fluorine removal system for treating Flue Gas Desulfurization (FGD) wastewater of a coal-fired power plant and application of the fluorine removal system, wherein fluorine ions in the FGD wastewater of the coal-fired power plant are removed through operations of high-frequency pulse electrocoagulation, alkali-added coagulating sedimentation and the like.
Description
Technical field
Defluorination method and fluorine removal system of the present invention about waste water, especially with respect to the flue gas desulfurization from coal-fired power plant
The defluorination method and fluorine removal system of waste water.
Background technique
Known power plant or steam power plant are all by fire coal to generate electricity, wherein in coal-fired process, sulphur contained by coal
Part can release, and be present in flue gas in the form of oxysulfide.Therefore, it in order to lower air pollutant emission, discharges fume
Desulfurization (flue gas desulfurization, FGD) becomes as the important process program for gas produced by fire coal, herein
Manage and then generate a large amount of FGD waste water.However, the complicated component of this kind of waste water, electrical conductivity are high, or even have fluorine superorder target and ask
Topic.
For waste water caused by FGD, generally corresponding processing method can be selected according to each factory FGD wastewater characteristics.Mesh
It is preceding to have for the usually used processing method of fluoride waste: chemical coagulation-sedimentation method, absorption method, electrolytic coagulation etc..
Chemical coagulation is common wastewater treatment method, and the principle for being used for fluorine removal is led under pH value condition appropriate
The addition of chemical agent is crossed, generates glue pterophorid matter directly or indirectly to react in conjunction with pollutant and then by heavy
It forms sediment and removes.However, according to coagulant sedimentation, adding new coagulant will lead to for the FGD waste water of ion component complexity
Water intermediate ion ingredient is more complicated and generates competitive relation, to influence defluorination effect；Therefore, or even multiple dosing is needed
Preferable effect is had, but therefore can also generate a large amount of sludge, increases processing cost.Such as Chinese patent CN
In 102276034A, to add calcium chloride as first of fluorine removal process, then adding coagulant, (ingredient is aluminium chloride, phosphoric acid
Aluminium, aluminum sulfate or kaolin) second fluorine removal is carried out, add flocculant (ferric trichloride or polyacrylamide) finally to handle electricity
The high-concentration fluorine-containing waste water of factory.Chinese patent CN 103693770A then uses the Cr VI in multi-part approach processing FGD waste water
Ion, fluorine ion and COD；By addition calcium hydroxide solution, calcium aluminate powder and liquor ferri trichloridi to reach place
Manage purpose.
Absorption method is to use adsorbent (such as: the materials such as activated aluminum, activated carbon, resin) to carry out absorption or ion exchange
To handle the fluorine in industrial wastewater.In general, different adsorbents has the pH value of waste water different requirements.In addition, mistake
After the fluoride waste of high concentration is directly entered adsorption system, then it will lead to adsorbent and easily reach saturation, and then lead to pollutant
Removal effect reduces.Therefore, waste water is directly handled according to absorption method, expense is usually very high.Disclosed in patent document with
The example of absorption method processing fluoride waste includes, such as 104843818 A of Chinese patent CN, uses and is coated with surface
Chelating resin containing chloro- aluminum ions aminophosphonic acid compound carries out absorption to the fluorine in fluoride waste and by the fluorine of fluoride waste
Ion concentration is down to 10ppm or less.
Electric coagulation (electrocoagulation, EC) rule is a kind of emerging drinking water and industrial wastewater defluorinate skill
Art, it is many studies have shown that use aluminium (Al) or iron (Fe) as sacrificial electrode be effective defluorination method；In addition, being led for height
The waste water of electric degree, then the aluminium or iron ion that can be released by increasing anodic oxidation reactions, and then increase current efficiency, at raising
Manage effect.However, the disadvantages of existing electrolytic coagulation has electrolysis time, and sludge yield is big.Such as Chinese patent CN
103086550 B use direct current electrolysis method, and using ti-based coating as anode, stainless steel plate carries out FGD waste water as cathode
Electrolysis processing 60~80 minutes, and the FGD waste water is stirred while electrolysis, because containing a large amount of chloride ions in waste water, through electricity
The oxygen and chlorine with Strong oxdiative ability, and then oxygenolysis Organic substance in water are generated after solution.Chinese patent CN
101817575 B are using heavy metal, the chlorine, COD, ammonia nitrogen in electric flocculation method processing FGD waste water；Its used reactor is pipe
The acyclic type variable-frequency pulse electric flocculation reactor of formula structure, 0.15~0.2kHz of pulse frequency, electrolysis time 30~60 minutes,
Anode material is aluminium or iron.
In view of technology today, for the processing method of FGD waste water, there are still aforesaid drawbacks, and various countries are for sewage discharge
Standard is increasingly stringent, therefore, need a kind of method that can meet economic benefit and can effectively remove the FGD wastewater treatment of fluorine with
System, the present invention thus provide the defluorination method and fluorine removal system of a kind of novel FGD waste water.
Summary of the invention
It is an object of the present invention to provide a kind of defluorination methods of flue gas desulfurization waste-water, including the following steps:
(a) electric coagulating, and
(b) it is stirred.
Wherein, the electric coagulating of step (a) carries out in electric coagulation device, and electricity coagulation device outfit is provided with high frequency arteries and veins
Rush the power supply unit of electric current.Step (b) adds alkali while being stirred mixing then to adjust the pH value of the waste water to pH
5~8.
Optionally, the high-frequency pulse current pulses range be 0.5~60kHz.
Optionally, step (b), which is stirred, can be divided into two stages progress, and the first stage is to mix fastly, and second stage is
It is slow mixed.
Optionally, it is precipitated or is floated after step (b) is stirred.
It is another object of the present invention to provide a kind of fluorine removal systems of flue gas desulfurization waste-water, including following devices:
(a) electric coagulation device, and
(b) it is stirred slot.
The electricity coagulation device includes: anode and cathode, the reactive tank and offer high-frequency electrical pulses of one or more groups of pairings
The power supply unit of stream, wherein the material of the anode and cathode is aluminium or iron and this is stirred slot and adds structure equipped with alkali
Part.
Optionally, for fluorine removal system of the present invention other than including electric coagulation device and being stirred slot, it is heavy to also comprise
Shallow lake slot or floating upward groove.
Optionally, slot is stirred equipped with mixing speed controller to control mixing speed.
Optionally, two groove bodies that slot can be tandem are stirred, wherein first groove body is to mix slot fastly, second
Groove body is to mix slot slowly.
For above-mentioned purpose of the invention, technical characteristic and advantage can be clearer and more comprehensible, hereafter with a variety of specific embodiment parties
Case is described in detail.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the flow chart of an embodiment of the defluorination method of flue gas desulfurization waste-water according to the present invention；
Fig. 2 is the flow chart of the another embodiment of the defluorination method of flue gas desulfurization waste-water according to the present invention.Appended drawing reference
Explanation
A step
B, b1, b2 step
C step.
Specific embodiment
Definition
As above and used in full text of the present invention, unless otherwise noted, otherwise following term is interpreted as having following meanings.
The meaning of coagulation (coagulation) is to destroy the stable state of colloidal particle, to reduce between particle and particle
Mutual exclusion current potential, so that particle is contacted with each other and is agglomerated, form biggish glue plumage after particle coacervation, then by precipitating or float
It removes.
Flocculation, also referred to as gelling (flocculation), expression form larger glue in coagulation process, after particle coacervation
The stage of plumage.
Electric coagulation (electrocoagulation, EC) indicates: including equipped with yin-yang by aqueous solution feeding to be processed
The reactive tank of electrode, and apply voltage and form field effect, cause water body fine with cation that sacrificial electrode releases is closed
The effect that particle is separated with water body is reached in the generation of particle coacervation phenomenon.
Multiple specific embodiments according to the present invention explained below；But without departing from the spirit of the present invention, originally
Scheme still in many different forms is invented to practice, the scope of the present invention specification should not be interpreted as being limited to and be stated
Content.In addition, unless in addition Wen Zhongyou illustrates, in this manual (especially in detail in the claims) used in
" one ", "the" and similar term are interpreted as comprising odd number and plural form.
FLUORIDE REMOVAL IN WASTEWATER method provided by the present invention is a kind of electric coagulation method of improvement, is particularly suitable for processing electricity
Factory's FGD waste water.In specific words, FLUORIDE REMOVAL IN WASTEWATER method of the invention is a kind of high-frequency electrical pulses coagulation and closes plus the fluorine removal side of alkali
Method.
In FLUORIDE REMOVAL IN WASTEWATER method according to the present invention, involved high-frequency electrical pulses coagulation is using high-frequency (preferable model
Enclose: 0.5~60kHz, optimum range: 3~10kHz) power supply unit of pulse, generated electric current belongs to the one of direct current
Kind, which is high-frequency repetition pulse process, i.e. the high-frequency arteries and veins that repeats " power supply-power-off-power supply "
Rush electrolytic process.During pulse power supply, higher current density can be generated.In pulse electrolysis, since conduction time is small
Total reaction time is handled in electrolysis, so the meltage when meltage of metallics is by less than DC electrolysis.Therefore, pulse electricity
For solution compared with DC electrolysis, pole plate consumption is also greatly lowered in the former while economize on electricity.In addition, being grasped in high-frequency electrical pulses coagulation
In work, pulse signal has the characteristics that periodic reverse, i.e., closely follows a reverse impulse (anode afterwards in direct impulse (cathode pulse)
Pulse) so that electrode plate not only has pulse electrolysis, but also has the characteristics that the two poles of the earth are solvable, it is more advantageous to released metal
Flocculation between ion and colloid, and the polar frequent variation in the two poles of the earth, to preventing electrode passivation from also functioning to positive effect.Cause
This this method not only has the advantages that the reaction speed of traditional electrolytic coagulation is fast, stable water outlet, and has that electrolysis time is short, saves energy
Consumption, the characteristics of pole plate consumption is reduced, sludge yield is low etc..
Embodiment shown in referring to Fig.1, FGD waste water carry out following steps sequentially to remove the fluorine in water: electric coagulation stirs
Mixing and precipitating are mixed, wherein each processing step is described in more detail in down.
As shown in Figure 1, fluoride waste is first sent into the reactive tank of electric coagulation device with carry out electric coagulating (step a),
Wherein, cathode and anode are equipped in electric coagulation device, aluminium or iron can be used in cathode and an anode material.During electric coagulating
Generated size of current determines according to waste water electrical conductivity, FGD waste water electrical conductivity range be generally 18~21 milli Siemens/li
Rice (mS/cm), therefore cause generate current range be 5~10A, corresponding to current density are as follows: 8A/dm2~15A/dm2；Electricity
Solving the time is 1~15 minute.If cathode and anode are all made of aluminium sheet and carry out fluorine removal, under energization action, electricity can occur for anode
Aluminum ions reaction is solved, the reaction of electrolysis water can then occur for cathode.It is different according to the pH value of handled waste water, will lead to aluminium from
Son has different existence forms in water.Such as when pH value is 1~3, mainly Al in water3+；When item of the pH value 4~5.5
Under part, aluminium starts to hydrolyze, under this condition predominantly metal complex (predominantly Al (OH)n·(H2O)n n+), and in high ph-values
It is metal hydroxides (predominantly Al (OH) under conditions of (5.5~10)3).Therefore, at different conditions caused by aluminium object
Different reactions can occur from fluorine ion for matter, mainly include the following three types reaction: network occurs for aluminium ion and fluorine ion in the first
Reaction is closed, generating complex compound mainly has AlF2+、AlF2 +、AlF3；Second is coprecipitation reaction, i.e. nAl3++(3n-m)OHˉ+mFˉ
→AlnFm(OH)(3n-m)；The third is the adsorption reaction of aluminium hydroxide, i.e. Aln(OH)3n+mFˉ→AlnFm(OH)(3n-m)+mOHˉ。
Aforementioned three kinds are reacted the effect for having Natural zeolite.If cathode and anode are all made of iron plate and carry out fluorine removal, mechanism is logical
Under electro ultrafiltration, the Fe of anode generation2+It is reacted with water and oxygen and generates Fe (OH)3Sediment, the substance can adsorb fluorine ion, anti-
Answer formula are as follows: Fe (OH)3(s)+3Fˉ→FeF3+3OHˉTo achieve the purpose that Natural zeolite.
Referring again to FIGS. 1, waste water (is walked after electric coagulation, being then admitted to be stirred slot and be stirred mixing
Rapid b) mixing speed is 20~500rpm, and the time is 2~30 minutes, while adding alkali and the pH value of waste water being turned up to pH 5~8,
Pass through OH caused by addition alkaliˉIt can be with Al free in water3+And the reaction of aluminum-based metal complex compound, it further generates effective
Except fluorine material；And contain a large amount of magnesium ion in waste water, it is anti-co-precipitation to occur with aluminium ion, hydroxide ion and fluorine ion
It should further generate effectively except fluorine material, improve defluorination effect.This is stirred the type of alkali added by the stage not
Any special limitation, and added alkali is preferably the hydroxide of alkali metal group, for example, sodium hydroxide or potassium hydroxide.
Waste water is finally subjected to precipitating operation (step c), to reach the purpose being separated by solid-liquid separation.The residence time of the precipitating is 15
To between 60 minutes, in addition, can be optionally with stirring during precipitating, wherein the speed of the stirring is 5 between 20rpm.
Preferably, its pH-value can first be adjusted before waste water is precipitated to pH 5~7.
Referring to Fig. 2, another embodiment according to the present invention is shown, FGD waste water carries out following steps sequentially to remove water
In fluorine: electric coagulation, fast mixed, slow mixed and precipitating, wherein each processing step is described in more detail in down.
As shown in Fig. 2, first by the reactive tank that fluoride waste is sent into electric coagulation device carry out electric coagulating (step a),
Anode involved in middle electricity coagulating and cathode reaction refer to explanation above.
Mixing then is stirred to the waste water after electric coagulation.As shown in Fig. 2, in this embodiment, stirring is mixed
Conjunction carries out in two stages, that is, the waste water after electric coagulation is first sent into mixed slot fastly and carries out mixing (step b1) fastly 2~5 minutes, stirs
Mixing speed is 100~500rpm.Alkali, such as sodium hydroxide are added simultaneously in the fast mixed stage.It then will be after too fast mixed slot processing
Waste water be sent into mixed slot slowly and carry out mixing (step b2) slowly 10~30 minutes, mixing speed is 20~100rpm；The purpose is to slow
Under the action of mixed, assemble small glue plumage, to form bigger glue plumage, is conducive to the sedimentation of suspended material.
Finally carrying out precipitating operation to waste water, (step c) makes its separation of solid and liquid.The residence time of precipitating was at 15 to 60 minutes
Between, in addition, can be optionally with stirring during precipitating, wherein the speed of the stirring is 5 between 20rpm.Preferably, useless
Water first adjusts its pH-value to pH 5~7 before being precipitated.
Hereinafter, preferred embodiment is proposed, more specifically to illustrate the present invention.However, providing following embodiment and being only
The present invention being illustrated, and those skilled in the art obviously will be understood that, these embodiments are not intended to limit the range of claims, and
It is that can make various changes and retouching within the scope and spirit of this invention.These changes and retouching are contained in accompanying power certainly
In sharp claim range.
Embodiment
Raw wastewater to be processed used in embodiment herein is that flue gas desulfurization (FGD) waste water is gone by pre-treatment in factory
Except the waste water after partial suspended solid (SS).
Embodiment 1
Waste water quality parameter is measured first, measurement item includes pH value, electrical conductivity, SS, fluorinion concentration, knot
Fruit is as shown in table 1.1.Then, using two panels aluminium sheet as cathode and anode, with high-frequency impulse electrolytic coagulation of the present invention not
It handles FGD waste water under the conditions of same electrolysis time (5 minutes, 10 minutes, 15 minutes) to be tested, experiment uses FGD waste water water about
500ml then and by the pH value of treated FGD waste water is adjusted to neutrality, and result is as shown in table 1.2.It is high in experimentation
The pulse frequency of frequency pulse power power supply unit is about 7kHz.
Table 1.1
Table 1.2
By table 1.2 as can be seen that the cell reaction of long period can further decrease fluorinion concentration, but can also lead
Cause the generation of a large amount of sludge.
Embodiment 2
FGD waste water, experiment FGD waste water water about 500ml are handled with high-frequency electrical pulses coagulation system, electrolysis time is
5 minutes, it is stirred mixing later while adding the alkali of different volumes amount, used alkali are as follows: 5% sodium hydroxide adds alkali body
Accumulated amount is respectively as follows: 0mL, 2mL, 4mL, 8mL, 12mL, 24mL；Experimental result is as shown in table 2.
Table 2
According to table 2 it can be found that after high-frequency electrical pulses Coagulation with Treatment, then a small amount of alkali is added, had preferably
Defluorination effect.
Embodiment 3
It is tested with high-frequency impulse electrolytic coagulation combination alkali adding method processing FGD waste water.Experiment uses FGD waste water water about
500ml carries out repeating ten experiments with identical two panels aluminum electrode plate, and the cell reaction time is 5 minutes；Then it is mixed fastly,
Revolving speed is 120rpm, and adds the sodium hydroxide 3mL that concentration is 5%, and doing time fastly is 2 minutes；It is mixed slowly again, revolving speed is
30rpm, doing time slowly is 10 minutes.Every time after experiment, electrode plate surface attachment is scraped off and carries out next experiment again.
Experimental result is as shown in table 3.
Table 3
It can be seen that the variation tendency of fluorinion concentration in repeated experimentation according to table 3, population mean fluoride removing rate is
70.4%, population mean fluorine residual concentration is 35.5mg/L.
Embodiment 4
Compare the effect of high-frequency electrical pulses coagulation system and the electric coagulation system processing FGD waste water of Traditional DC electricity.Comparative run
Mesh includes electrolysis time, sludge yield, fluorinion concentration.Experiment FGD waste water water about 500ml, through the different electricity of two kinds of systems
The FGD waste water that solves that treated the reaction time；It is all mixed fastly, while pH value of waste water being adjusted to neutrality, revolving speed 120rpm,
Do time fastly is 2 minutes；It is mixed slowly again, revolving speed 30rpm is done time slowly as after ten minutes, the results are shown in Table 4.From
Table 4 is it can be seen that when raw wastewater is through high-frequency electrical pulses coagulation system phase approximate with tradition electricity mixing system treated fluorinion concentration
In the case where (one kind is 47.19mg/L, and one kind is 51.25mg/L), high-frequency electrical pulses coagulation system is mixed compared to traditional electricity
System has the advantage that shorter reaction time and sludge yield are low.
Table 4
| High-frequency electrical pulses coagulation | Traditional electricity coagulation | |
| Electrolysis time (minute) | 5 | 30 |
| Sludge yield (mg/L) | 2620 | 3920 |
| Fluorine ion (mg/L) | 47.19 | 51.25 |
Claims (8)
1. a kind of defluorination method of flue gas desulfurization waste-water, characterized in that it comprises the following steps:
(a) electric coagulating, and
(b) it is stirred,
Wherein, step (a) carries out in electric coagulation device, which is equipped with the power supply confession for being provided with high-frequency pulse current
Alkali is added while answering device and step (b) to be stirred mixing adjusts the pH value of the waste water to pH 5~8.
2. defluorination method as described in claim 1, which is characterized in that the pulses range of the high-frequency pulse current is 0.5
~60kHz.
3. defluorination method as described in claim 1, which is characterized in that be additionally carried out precipitating or floating step after step (b).
4. defluorination method as described in claim 1, which is characterized in that be divided into two stages progress, first stage in step (b)
To mix fastly, second stage is slow mixed.
5. a kind of fluorine removal system of flue gas desulfurization waste-water, which is characterized in that including following devices:
(a) electric coagulation device, and
(b) it is stirred slot,
Wherein, which includes: anode and cathode, the reactive tank and offer high-frequency impulse of one or more groups of pairings
The power supply unit of electric current, wherein the material of the anode and cathode is aluminium or iron and this is stirred slot and adds equipped with alkali
Component.
6. fluorine removal system as claimed in claim 5, which is characterized in that also comprise precipitation tank or floating upward groove.
7. fluorine removal system as claimed in claim 5, which is characterized in that this be stirred slot equipped with mixing speed controller with
Control mixing speed.
8. fluorine removal system as claimed in claim 5, which is characterized in that it is two that the mode that is concatenated connects that this, which is stirred slot,
Groove body, first groove body are that mixed slot, second groove body are slow mixed slot fastly.
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| TW106125552A TWI637917B (en) | 2017-07-28 | 2017-07-28 | Fluoride removal method of flue-gas desulfurization wastewater and fluoride removal system thereof |
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| TWI742986B (en) * | 2021-01-13 | 2021-10-11 | 國立成功大學 | Method for removing fluorine and boron from a solution |
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| CN1986435A (en) * | 2006-12-22 | 2007-06-27 | 清华大学 | Process of treating fluoride and organic matter in drinking water and its electrical flocculator |
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| CN103819036B (en) * | 2014-02-27 | 2015-03-04 | 盛发环保科技（厦门）有限公司 | Treating method for desulfurization waste water of power plant |
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| CN1986435A (en) * | 2006-12-22 | 2007-06-27 | 清华大学 | Process of treating fluoride and organic matter in drinking water and its electrical flocculator |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110498490A (en) * | 2019-08-30 | 2019-11-26 | 南京友智科技有限公司 | A kind of electric flocculation reactor and its application |
| CN110498490B (en) * | 2019-08-30 | 2023-08-18 | 南京友智科技有限公司 | Electric flocculation reactor and application thereof |
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| TWI637917B (en) | 2018-10-11 |
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