CN114044587A - Manganese-loaded oxide film expanded bed filter and method for removing thallium by adsorption by applying manganese-loaded oxide film expanded bed filter - Google Patents
Manganese-loaded oxide film expanded bed filter and method for removing thallium by adsorption by applying manganese-loaded oxide film expanded bed filter Download PDFInfo
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- 229910052716 thallium Inorganic materials 0.000 title claims abstract description 103
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000011572 manganese Substances 0.000 title claims abstract description 75
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 67
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 234
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 60
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 57
- 230000007704 transition Effects 0.000 claims abstract description 39
- 238000007667 floating Methods 0.000 claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 14
- 238000011010 flushing procedure Methods 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 18
- 239000003651 drinking water Substances 0.000 claims description 16
- 239000002351 wastewater Substances 0.000 claims description 16
- 235000020188 drinking water Nutrition 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 239000008213 purified water Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
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- 239000008187 granular material Substances 0.000 claims description 2
- 239000002384 drinking water standard Substances 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- 239000004576 sand Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
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- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 235000020681 well water Nutrition 0.000 description 4
- 239000002349 well water Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000011001 backwashing Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
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- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052949 galena Inorganic materials 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5281—Installations for water purification using chemical agents
-
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/11—Turbidity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a manganese-loaded oxide film expanded bed filter and a method for removing thallium from water by adsorption by using the same; the manganese-loaded oxide film expanded bed filter comprises a filter tank body, a water collecting tank, an upper transition region, a filter screen plate, a manganese-loaded oxide film expanded filter bed, a lower transition region and a water collecting device, wherein the water collecting tank, the upper transition region, the filter screen plate, the manganese-loaded oxide film expanded filter bed, the lower transition region and the water collecting device are sequentially arranged in the filter tank body from top to bottom, and MnO is loaded on the surface of the manganese-loaded oxide film expanded filter bed2The density of the water-impregnated particles of the oxide film is 0.95 +/-0.5 g/cm3The floating ceramsite is uniformly laid; the KMnO is arranged on the water inlet pipe4A solution feed port. The invention relates to aOver MnO4 ﹣Reduction and Mn2+Oxidation to quickly generate large amount of nascent MnO2The manganese oxide film is slowly thickened along with the continuous addition of potassium permanganate after being adsorbed on the surface of the ceramsite, and the adsorbed thallium can not be saturated and does not need to be regenerated. By applying the method, the thallium concentration of the effluent can be controlled to stably reach the domestic drinking water standard of less than 0.1 mug/L.
Description
Technical Field
The invention relates to the field of water treatment, in particular to a manganese-loaded oxide film expanded bed filter tank and a method for removing thallium by adsorption by applying the manganese-loaded oxide film expanded bed filter tank.
Background
Thallium is a rare and dispersive element and is often associated with mineral reserves such as pyrite and galena. Monovalent thallium has strong migration activity, and trivalent thallium has thousands of times higher toxicity than monovalent thallium. The content of thallium in natural water is generally low, the lake content is 0.001-0.4 mug/L, the river content is 0.01-1.35 mug/L, and the underground water content is 0.001-0.85 mug/L. The thallium-containing ore deposit in China has abundant resources and wide distribution, thallium-polluted water sources also appear along with the thallium-containing ore deposit, and pollution events caused by thallium-containing wastewater in ore fields occur occasionally.
At present, the standard of thallium in domestic drinking water required by China is less than or equal to 0.1 mug/L. In some areas with geological conditions containing thallium, well water or even reservoir water serving as a drinking water source for life may have the problem that the thallium content in raw water exceeds the standard. For monovalent thallium, the existing tap water purification process, including an ultrafiltration membrane process, cannot effectively remove thallium to realize standard water supply. Under the condition that a water source is polluted by thallium, the most effective method is to add potassium permanganate at the water inlet end of a tap water plant with a sand filter and remove part of thallium through the sand filter at present. The thallium removal is actually realized by the sand filter adsorption. The thickness of the filter sand is only about 1m, and the ferro-manganese oxide film attached to the surface is not much, so that the adsorption capacity is limited, the filter sand is easy to penetrate, and the thallium content after the treatment by the technology is difficult to reach the standard aiming at the thallium content of raw water exceeding 0.15 mu g/L. In addition, because the raw water contains more reducing substances, the consumption of potassium permanganate is greatly increased, and in order to avoid red effluent, the addition amount of potassium permanganate is restricted, and the thallium removal effect is also influenced. More risky, most thallium adsorbed by the technology is retained in the sand filter tank, so that the sand filter tank becomes a new thallium pollution source, and once the potassium permanganate adding amount is reduced, thallium adsorbed in the sand filter tank can be adsorbed by Mn in water2+And Fe2+And a large amount of cations which are easily adsorbed by the filter sand are exchanged and separated out into the filtered water, and the standard exceeding times are usually multiple times of that of the thallium-containing raw water. Therefore, the method for removing thallium from tap water by adding potassium permanganate and removing thallium by a sand filter has great disadvantages.
At present, the strictest discharge limit value set by China for thallium-containing industrial wastewater is less than or equal to 2 mug/L, which is 20 times of the standard of domestic drinking water. The limits of industrial wastewater discharge are mainly determined by thallium removal methods and costs. At present, a thallium adsorbing material is adopted to remove thallium for purifying thallium-containing industrial wastewater, and the operation is maintained through regeneration, so that it is difficult if the drainage thallium content can be stably less than or equal to 2 mug/L.
Chinese invention patent 201110231227.3 discloses a method for removing thallium pollution in drinking water source water, which comprises the following steps: a. adjusting the pH value to 9.0-9.5 when the thallium pollution concentration is not higher than 1 mug/L; when the thallium pollution concentration is 1-5 mug/L, adjusting the pH value to 9.5-10.0; b. pre-oxidizing by using potassium permanganate as thallium pre-oxidant+Conversion to Tl3+Adding 1.5-2.5mg/L potassium permanganate, and oxidizing for 20-40 min; c. coagulating, precipitating, adding polyaluminium chloride to make Tl3+Tl (OH)3 precipitate is formed, and thallium in the source water can be removed by filtration. However, the technology needs to adjust the pH value, and the added polyaluminium chloride cannot be reused, so that the water treatment cost is high.
Disclosure of Invention
The invention aims to provide a manganese-loaded oxide film expanded bed filter tank and a method for absorbing and removing thallium by applying the manganese-loaded oxide film expanded bed filter tank, aiming at overcoming the defects of the existing technology for absorbing and removing thallium, being suitable for treating various thallium-containing wastewater, particularly suitable for a thallium-containing water source drinking water supply system, stably reducing the thallium-containing concentration to be less than 0.1 mug/L, and meeting the sanitary standard of drinking water2The oxide film can be reused, only a certain amount of potassium permanganate needs to be properly added, and the treatment cost is low.
The floating haydite is oxidized by potassium permanganate and has one MnO layer supported on its surface2Mainly metal oxide film, then using the loaded manganese oxide film ceramic particles as filter material, and cooperatively adding potassium permanganate after raw water is turbidity removed. The surface oxidation film of the filter material is used for the treatment of Mn in water2+、MnO2、MnO4 ﹣And Fe2+All have strong adsorption effect on MnO4 ﹣Oxidized Mn2+And Fe2+Has strong catalytic action through MnO4 ﹣Reduction and Mn2+The oxidation can rapidly generate a large amount of new ecologyMnO2Adsorbed on the surface of the floating ceramsite. Nascent MnO2The thallium is efficiently adsorbed and removed in a mode of ion exchange between the surface complex hydroxyl and the thallium. New ecological MnO2And the thallium is adsorbed and then continuously attached on the oxide film to form a new manganese film layer. With the continuous addition of potassium permanganate, the manganese oxide film is continuously thickened, thallium is adsorbed and removed without saturation, and regeneration is not needed; the potassium permanganate is added in a quantitative way by MnO4 ﹣Oxidation-promoted nascent MnO of sufficient quantity2Meets the requirements of adsorption and thallium removal, and can sufficiently oxidize and remove Mn in water2+And Fe2+And adsorbed thallium is prevented from being exchanged and separated out, and the thallium removal efficiency is improved. MnO capable of reducing turbidity substance interference on new ecology by raw water turbidity removal pretreatment2And the filter material is prevented from being frequently washed and the stripping is increased to influence the thallium removal efficiency. The floating ceramsite loaded with the manganese oxide film aims to have the advantages of small water loss, low operation energy consumption, simple flushing mode and easy maintenance and management by virtue of the filter of the expanded bed.
The purpose of the invention is realized by the following technical scheme:
the manganese-loaded oxidation film expanded bed filter tank comprises a filter tank body, and a water collecting tank, an upper transition region, a filter screen plate, a manganese-loaded oxidation film expanded filter bed, a lower transition region and a water collecting device which are sequentially arranged in the filter tank body from top to bottom, wherein a water inlet pipe is communicated with a water distribution tank or a bottom water collecting device; the manganese-loaded oxide film expanded filter bed is formed by loading MnO on the surface2The density of the water-impregnated particles of the oxide film is 0.95 +/-0.5 g/cm3The floating ceramsite is uniformly laid; the KMnO is arranged on the water inlet pipe4A solution feed port.
To further achieve the object of the present invention, preferably, the expanded filter bed supported manganese oxide membrane is prepared by the following method: adding Mn2+Adding potassium permanganate into the aqueous solution with the concentration of more than 0.3mg/L, pumping the aqueous solution into a coating tank for placing floating ceramsite, and controlling the concentration of the potassium permanganate in the water to be 0.4-1 mg/L; passing MnO under the catalytic action of the gradually generated manganese oxide film4 ﹣Reduction of (2) and Mn2+Oxidation of (2) rapidly to form a large amount of MnO2Adsorbed on the surface of the floating ceramsite.
Preferably, the floating ceramsite is prepared by the following method: using shale as a raw material, crushing and drying the shale by using a crusher, firing the shale in a rotary kiln for 18-22 min at 1100-1300 ℃, taking the shale out of the kiln, naturally cooling the shale, crushing the shale, and screening ceramsite with the particle size of 5-12 mm to obtain water-impregnated granules with the density of 0.95 +/-0.5 g/cm3The floating ceramsite.
Preferably, an air flushing pipe of the manganese-loaded oxide film expanded bed filter is communicated with a bottom air distribution device; the flushing wastewater drainage pipe is communicated with a water collecting main pipe of the bottom water collecting device; the other end of the air flushing pipe is connected with the blower.
The manganese-loaded oxide film expanded bed filter is a down-flow filter or an up-flow filter; for the down-flow filter, the water inlet pipe is communicated with the water distribution tank, and the water outlet pipe is communicated with the water collecting main pipe of the bottom water collecting device; and the water inlet pipe of the upflow filter is communicated with the water collecting main pipe of the bottom water collecting device, and the water outlet pipe is communicated with the water distribution tank.
Preferably, the horizontal cross section of the filter tank body is rectangular or circular.
Preferably, when the filter tank body is of a reinforced concrete structure, the horizontal section of the filter tank body is rectangular; when the filter tank body is welded by steel plates, the horizontal section of the filter tank body is circular or rectangular.
Preferably, the mesh diameter of the filter screen plate is 3-5 mm; the filter screen plate is made of stainless steel;
the upper transition area is a space between the water distribution tank and the filter screen plate, and the height of the upper transition area is 0.3-1 m;
the lower transition area is a space between the lower part of the manganese-loaded oxide film expansion filter bed and the water collecting device at the bottom, and the height of the lower transition area is 0.3-1 m.
The manganese-loaded oxide film expanded bed filter tank also comprises a bottom gas distribution device, the bottom gas distribution device is positioned in the lower transition zone, and the bottom gas distribution device consists of a gas distribution main pipe and a plurality of perforated gas pipes; the perforated gas pipe is horizontally arranged above the bottom of the tank and is communicated with the gas distribution main pipe;
the water collecting device consists of a water collecting main pipe and a plurality of perforated water pipes; the perforated water pipe is horizontally arranged above the bottom of the pool and is connected with the water collecting main pipe.
Preferably, the water inlet pipe, the water outlet pipe, the air flushing pipe and the flushing wastewater drainage pipe are all provided with valves.
The method for removing thallium by the manganese-loaded oxide film expanded bed filter tank comprises the following steps: if the overflow mode adopts a down-flow mode, raw water added with potassium permanganate enters a water distribution tank from a water inlet pipe, overflows and is distributed in an upper transition region, is gradually and uniformly distributed to the whole filtering surface, flows downwards to pass through a filtering screen plate and enter a floating ceramsite filtering bed, and purified water flows downwards through a lower transition region after adsorption and thallium removal of the floating ceramsite filtering bed, and is collected by a water collecting device to flow out of a water outlet pipe;
if the overflowing mode adopts an upflow mode, raw water added with potassium permanganate enters the water collecting device from the water inlet pipe, is gradually and uniformly distributed to the whole filtering surface after being distributed in the lower transition region, flows upwards to enter the floating ceramsite filtering bed, is adsorbed by the floating ceramsite filtering bed to remove thallium, and then passes through the filtering screen plate upwards to flow through the upper transition region, and is collected by the water distribution tank to flow out of the water outlet pipe.
Preferably, when the raw water is thallium-containing drinking water, the adding amount of potassium permanganate is controlled according to the concentration of potassium permanganate in the water being 0.3-0.5 mg/L; for the water with turbidity of raw water, the raw water is subjected to turbidity removal pretreatment and then potassium permanganate is added, and the adding amount of the potassium permanganate is also controlled according to the concentration of the potassium permanganate in the water being 0.3-0.5 mg/L.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1) the adsorption and thallium removal efficiency of turbid raw water is high by cooperatively adding potassium permanganate in the manganese-loaded oxide film expanded bed filter tank, the method is suitable for treating various thallium-containing wastewater, particularly suitable for adopting a water supply system of a thallium-containing water source, adding potassium permanganate in the raw water, and under the catalytic action of a manganese oxide film, passing through MnO4 ﹣Reduction and Mn2+Oxidation to quickly generate large amount of nascent MnO2New ecological MnO adsorbed on the surface of ceramsite2The thallium is efficiently adsorbed and removed in a mode of ion exchange between the surface complex hydroxyl and the thallium, and the effluent thallium concentration can be stably reduced to the level less than 0.1 mug/L.
2) Different from the existing absorption thallium removal material which adopts a manganese ore raw material, the invention loads a manganese oxidation film on the filter material in a potassium permanganate oxidation treatment mode, so that a proper filter material can be selected according to the water quality condition. Based on the advantages of small filtration water loss, low operation energy consumption, no hardening of the filter bed, simple flushing mode and easy maintenance and management of the filter tank of the floating ceramsite expansion bed, the floating ceramsite is selected to be rich in Mn2+The clear water is oxidized by potassium permanganate, so that a layer of manganese oxide film is loaded on the surface of the floating ceramsite and is tan. The manganese oxide film newly loaded by the filter material only plays a role in adsorbing Mn at the initial running stage2+、Fe2+、MnO2And MnO4 ﹣The manganese oxide film layer is not required to have abrasion resistance and thickness. With the continuous addition of potassium permanganate, the manganese oxide film is thickened and updated continuously and slowly.
3) Different from the principle of thallium removal by oxidation by adding potassium permanganate, the invention has two purposes of cooperatively adding potassium permanganate: one is to use manganese oxide film to MnO4 ﹣Oxidized Mn2+And Fe2+Has strong catalytic action through MnO4 ﹣Reduction of (2) and Mn2+To promote the growth of sufficient amount of nascent MnO2Realizing thallium adsorption and removal; secondly, the Mn is removed by full oxidation2+、Fe2+So as to avoid exchange precipitation of the adsorbed thallium and improve thallium removal efficiency. Nascent MnO continuously generated along with synergistic addition of potassium permanganate2And thallium is adsorbed on the surface and then continuously attached on the oxide film to form a new manganese film. Along with the continuous addition of potassium permanganate, the manganese oxide film is continuously thickened, and thallium is adsorbed and removed without saturation, so that regeneration is not needed.
4) The manganese-loaded oxide membrane expanded bed filter tank only needs to be added with potassium permanganate during operation, has high thallium removal efficiency, does not need regeneration, has small filtration water loss of the membrane expanded bed filter tank, does not harden the filter bed, has simple flushing mode, low operation energy consumption and easy maintenance and management, and has low operation cost.
5) The raw water is preferably subjected to turbidity removal pretreatment by adopting a manganese-loaded oxide film expanded bed filter. Low turbidity of inlet water is favorable forThe quality of the manganese oxide film is maintained, the full contact between water flow and the manganese oxide film is maintained, and MnO caused by frequent washing of filter materials is avoided2Elution is carried out, and the adsorption thallium removal rate is improved.
6) For wastewater treatment, the raw water still contains more organic matters after the turbidity removal pretreatment, and the surface of the filter material is gradually covered with a biological mud membrane, so that the contact between the manganese oxidation membrane and water flow is weakened, and the loss of the filter head of the filter is increased. Therefore, the filter chamber needs to be periodically back flushed, and the intensity and frequency of back flushing are often high, so that the water flow is maintained to be in contact with the manganese oxide film, and the overflowing capacity is recovered. The manganese oxide film-loaded expanded bed filter is suitable for the occasion, and the density of filter material particles is close to that of water, so that the filter has the advantages of small filter water loss, low operation energy consumption, simple washing mode and easy maintenance and management.
7) For water supply treatment, the manganese-loaded oxide film expanded bed filter is suitable for taking water from a clean water tank of a treatment system, the turbidity of raw water after turbidity removal pretreatment can be generally controlled below 3NTU, the filter usually needs to be backwashed once at intervals of weeks due to very low organic matter content in the water, and the configuration of gas and water backwashing facilities is simple. A manganese-loaded oxide film expanded bed filter tank can be adopted, so that the filter water loss is small, the operation energy consumption is low, and the maintenance and the management are easy; and a ceramsite loaded manganese oxide film with the particle density higher than that of water can also be used as a filter material, a filter screen plate is not required to be installed, and the construction cost of the filter tank is reduced.
Drawings
FIG. 1 is a schematic view of a down-flow structure of a manganese-loaded oxide film expanded bed filter tank.
FIG. 2 is a schematic view of an upflow structure of the manganese-loaded oxide film expanded bed filter of the present invention.
FIG. 3 is a flow chart of a method for removing thallium by adsorption of a manganese-loaded oxide film expanded bed filter.
The figures show that: the device comprises an expansion bed filter body 1, a water distribution tank 2, an upper transition region 3, a filter screen plate 4, a manganese oxide film loaded expansion filter bed 5, a lower transition region 6, a bottom gas distribution device 7, a bottom water collecting device 8, a water inlet pipe 9, a water outlet pipe 10, a gas flushing pipe 11 and a flushing wastewater drainage pipe 12.
Detailed Description
For a better understanding of the present invention, the following further description is provided in conjunction with the accompanying drawings, and it should be noted that the detailed description is not intended to limit the scope of the present invention.
As shown in fig. 1 and fig. 2, a manganese-loaded oxide film expanded bed filter comprises a filter tank body 1, and a water distribution tank 2, an upper transition zone 3, a filter screen plate 4, a manganese-loaded oxide film expanded filter bed 5, a lower transition zone 6 and a bottom water collecting device 8 which are sequentially arranged in the filter tank body from top to bottom; in addition, the device also comprises a bottom gas distribution device 7, a water inlet pipe 9, a water outlet pipe 10, a gas flushing pipe 11 and a flushing wastewater drainage pipe 12, wherein valves are arranged on various pipelines to independently control the opening and closing; the air flushing pipe 11 is communicated with the bottom air distribution device 7; the flushing waste water discharge pipe 12 is communicated with a water collecting main pipe of the bottom water collecting device 8; for the downflow filter tank shown in fig. 1, a water inlet pipe 9 is communicated with the water distribution tank 2, and a water outlet pipe 10 is communicated with a water collecting main pipe of a bottom water collecting device 8; for the upflow filter tank shown in fig. 2, the water inlet pipe 9 is communicated with the water collecting main pipe of the bottom water collecting device 8, and the water outlet pipe 10 is communicated with the water distribution tank 2. KMnO is arranged on the water inlet pipe 94A solution feed port for adding KMnO4And (3) solution.
The manganese-loaded oxide film expanded filter bed 5 is formed by loading MnO on the surface2The density of the water-impregnated particles of the oxide film is 0.95 +/-0.5 g/cm3The floating ceramic particles are uniformly paved to form the ceramic particles. The floating ceramsite load manganese oxide film is prepared by the following method: adding Mn2+Adding potassium permanganate into the aqueous solution with the concentration of more than 0.3mg/L, pumping the aqueous solution into a coating tank for placing floating ceramsite, and controlling the concentration of the potassium permanganate to be 0.4-1 mg/L. Passing MnO under the catalytic action of the gradually generated manganese oxide film4 ﹣Reduction of (2) and Mn2+The oxidation can rapidly generate a large amount of nascent MnO2Adsorbed on the surface of the floating ceramsite; the density of the water-impregnated particles is 0.95 +/-0.5 g/cm3The floating ceramsite is prepared by the following method: the method comprises the steps of taking shale as a raw material, crushing and drying the shale by a crusher, firing the shale in a rotary kiln for 18-22 min, controlling the firing temperature to be 1100-1300 ℃, naturally cooling the shale after discharging the shale, crushing the shale by the crusher, screening the shale, and selecting water with the particle size of 5-12 mm to obtain waterThe density of the infiltrated particles is 0.95 +/-0.5 g/cm3The floating ceramsite.
In the invention, MnO is used4 ﹣Reduction and Mn2+Oxidation to quickly generate nascent MnO2Adsorbed on the surface of ceramsite to gradually form brown manganese oxide film which is also opposite to MnO4 ﹣And Mn2+The oxidation reaction of (A) is catalyzed to accelerate the formation of MnO2. The process is suitable for being carried out at the outdoor normal temperature, the time of the floating ceramsite loading manganese oxide film is about 1-2 weeks, and the time is equal to Mn in the aqueous solution2+Concentration and amount of potassium permanganate added are related, Mn2+The concentration and the adding amount of potassium permanganate are large, so that the coating time is shortened.
The expansion bed filter tank can adopt a down-flow type or an up-flow type according to an overflowing mode. The down-flow type is suitable for the occasion that the inlet water contains more suspended matters or easily-wound and blocked pollutants, and the up-flow type is suitable for other situations. The down-flow type is beneficial to the back washing of the filter, but the water level of the filter changes along with the change of the filter head loss; the up-flow type has more strict limitation to impurities in water, and has the advantages of being beneficial to full contact of water flow and filter materials and being beneficial to connection of the water outlet with constant water level with follow-up.
The horizontal section of the filter tank body 1 is rectangular or shaped, and when a reinforced concrete structure is adopted, the filter tank is preferably rectangular; when welded from steel plate, it is preferably round or rectangular.
The upper transition area 3 is a space between the top of the water distribution tank 2 and the filter screen plate 4, preferably has the height of 0.3-1 m, and has the function of forming uniform transition of water flow between the water distribution tank and the whole filter pool surface;
the lower transition zone 6 is a space between the lower part of the manganese oxide film-loaded expanded filter bed 5 and the water collecting device 8, preferably has the height of 0.3-1 m, and has the function of forming uniform transition of water flow between the water collecting device and the whole filter surface. For the heavy ceramsite filter material filter pool, the lower transition zone is a pebble cushion layer;
the filter screen plate 4 is used for limiting the manganese-loaded oxide film expanded filter bed 5 below the filter screen plate 4, so that filter materials cannot run off through meshes of the filter screen plate 4, but no obstruction is generated to overflowing sewage. Preferably, the filter screen plate 4 is made of stainless steel, preferably, the diameter of a mesh is 3-5 mm, and the mesh is smaller than the minimum size of the floating ceramsite by more than 2 mm;
the bottom gas distribution device 7 consists of a gas distribution main pipe and a plurality of perforated gas pipes. The perforated gas pipe is horizontally arranged above the bottom of the tank and is communicated with a gas distribution main pipe, the gas distribution main pipe is communicated with a gas flushing pipe 11, and the other end of the gas flushing pipe 11 is connected with a blower.
The bottom water collecting device 8 consists of a water collecting main pipe and a plurality of perforated water pipes; the perforated water pipe is horizontally arranged above the bottom of the tank and is connected with a water collecting main pipe which is communicated with a flushing waste water drainage pipe 12.
For the down-flow filter, a water inlet pipe 9 is communicated with the water distribution tank 2, and a water outlet pipe 10 is communicated with a water collecting main pipe of a bottom water collecting device 8; the water inlet pipe 9 of the upflow filter is communicated with the water collecting main pipe of the bottom water collecting device 8, and the water outlet pipe 10 is communicated with the water distribution tank 2.
The water inlet pipe 9, the water outlet pipe 10, the air flushing pipe 11 and the flushing wastewater drainage pipe 12 are all provided with valves for independently controlling the opening and the closing.
The method for removing thallium by applying the manganese-loaded oxide film expanded bed filter tank comprises the following steps: the overflow mode adopts a down-flow mode as shown in figure 1, raw water added with potassium permanganate enters a water distribution tank 2 from a water inlet pipe 9, overflows and is distributed into an upper transition zone 3, is gradually and uniformly distributed to the whole filtering surface, and then flows downwards to pass through a filter screen plate 4 to enter a manganese-loaded oxide film expansion filter bed 5. Because the floating ceramsite is slightly lighter than water, the filter bed is in a micro-expansion state by water flow pulsation. After thallium is removed through the manganese oxide film loaded expansion filter bed 5, the purified water flows downwards through the lower transition zone 6 and is collected by the bottom water collecting device 8 to the water outlet pipe 10 to flow out. The overflow mode adopts an up-flow mode as shown in figure 2, raw water added with potassium permanganate enters a bottom water collecting device 8 from a water inlet pipe 9, rises into a lower transition region 6, is gradually and uniformly distributed to the whole filtering surface, flows upwards to enter a loaded manganese oxide film expansion filter bed 5, is adsorbed by the loaded manganese oxide film expansion filter bed 5 to remove thallium, and then purified water upwards passes through a filter screen plate 4 to flow through an upper transition region 3 and is collected by a water distribution tank 2 to flow out of a water outlet pipe 10.
If the expanded bed filter tank needs to be washed after running for a period of time, the water surface can be lowered to the net surface of the filter screen plate 4, the air blower is started, compressed air enters the bottom air distribution device 7 from the air washing pipe 11, is uniformly distributed to the whole tank surface and diffuses upwards, the manganese-loaded oxide film expanded filter bed 5 expands and fluidizes below the filter screen plate 4, the drain valve is started after several minutes, and washing wastewater is discharged out of the tank from the washing wastewater discharge pipe 12.
For thallium removal of domestic drinking water, the filtration speed of the manganese-loaded oxide film expanded bed filter tank can be controlled to be 5-15 m/h, the adding concentration of potassium permanganate is generally not more than 1.0mg/L and is more than 0.5mg/L, pink effluent can be caused, and an active carbon decoloring unit is added if necessary. If the expansion bed filter tank needs to be flushed, the water surface can be lowered to the surface of the filter screen, the air blower is started, compressed air enters the bottom air distribution device from the back flushing air pipe, is uniformly distributed to the whole tank surface and is diffused upwards, the ceramsite filter bed expands and even fluidizes below the filter screen plate, a drain valve is started after a few minutes, and flushing wastewater is discharged out of the tank from a flushing wastewater drain pipe.
As shown in figure 3, thallium-containing raw water is generally subjected to turbidity removal pretreatment, then potassium permanganate is added, and the thallium-containing raw water enters a manganese-loaded oxide film expanded bed filter for adsorption and thallium removal. For raw water with low turbidity, such as underground water and the like, a turbidity removal pretreatment unit can be omitted, and the raw water directly enters the manganese-loaded oxide film expanded bed filter to adsorb and remove thallium. The low turbidity of the inlet water is beneficial to maintaining the quality of the manganese oxide film, keeping the sufficient contact of the water flow and the manganese oxide film and avoiding MnO caused by frequent washing of filter materials2Elution is carried out, the removal rate of adsorption and thallium removal is improved, and the adding amount of potassium permanganate is reduced. The quantitative addition of potassium permanganate before raw water enters the expanded bed filter is the key for thallium removal, and one is to promote the growth of sufficient nascent MnO2Realizing thallium adsorption and removal; secondly, the Mn is removed by full oxidation2+、Fe2+To avoid exchange precipitation of adsorbed thallium by the potassium permanganate, and if the potassium permanganate dosage is insufficient, Mn in water2+、Fe2+And the adsorbed thallium can be exchanged and separated out in a large amount due to insufficient removal, so that the effluent seriously exceeds the standard.
Take the example of removing thallium from well water in a village in Guangdong province. The village adopts deep well water for drinking water, and water is supplied to a stainless steel clear water tank on a hillside by a water pump, and the water pump adopts water tank liquidThe bit control runs automatically. The clear water tank automatically flows into the village tap water pipe and is connected with each user. The water supply amount of the water pump is 5-7 m3The daily water supply amount is 80-150 m3. In recent water quality detection results, the thallium concentration in the water is 0.25-0.45 mug/L, and exceeds the standard of sanitary standard of drinking water by 1.5-3.2 times compared with the standard of sanitary standard of drinking water. The well water has a manganese concentration of 0.014 to 0.049mg/L and an iron concentration of 0.014 to 0.049mg/L<0.0045 mg/L. At present, thallium removal of domestic drinking water adopts a 'coagulation → precipitation → sand filtration' water purification process, and potassium permanganate, sodium hydroxide and a flocculating agent are added in front of a coagulation unit. When the thallium concentration of the raw water exceeds 0.25mg/L, the thallium concentration of the outlet water is difficult to reach the drinking water sanitation standard of less than 0.1 mug/L, the adopted process is complex, at least more than 3 varieties of medicaments, such as potassium permanganate, sodium hydroxide, flocculating agents and the like, need to be added, frequent washing is needed, the management workload is increased, and the operation cost is greatly increased.
The method for removing thallium by adsorption of the manganese-loaded oxide film expanded bed filter is applied, the filling height of a manganese-loaded oxide film expanded filter bed 5 in the manganese-loaded oxide film expanded bed filter is 2.5m, after the manganese-loaded oxide film expanded filter bed filter is put into operation, the empty bed filter speed of the filter is 5-7 m/h, the concentration of raw water after potassium permanganate is added into the raw water is 0.35-0.45 mg/L, and the thallium concentration of the effluent is detected to be 0.01-0.05 mu g/L. For thallium removal of drinking water, the addition concentration of potassium permanganate exceeding 0.5mg/L can cause pink water, and active carbon needs to be added for decolorization when necessary. By adopting the method for removing thallium by adsorption of the manganese-loaded oxide film expanded bed filter, only quantitative addition of potassium permanganate is needed, the expanded bed filter does not need to be washed for a long time, unattended operation is easy to realize, the operation cost is low, and the concentration of thallium in effluent can stably reach the standard of domestic drinking water which is less than 0.1 mug/L.
Claims (10)
1. The manganese-loaded oxidation film expanded bed filter tank comprises a filter tank body, and a water collecting tank, an upper transition region, a filter screen plate, a manganese-loaded oxidation film expanded filter bed, a lower transition region and a water collecting device which are sequentially arranged in the filter tank body from top to bottom, wherein a water inlet pipe is communicated with a water distribution tank or a bottom water collecting device; characterized in that the manganese-loaded oxide film expanded filter bed is formed by loading MnO on the surface2Of oxide filmsThe density of the water-impregnated particles is 0.95 +/-0.5 g/cm3The floating ceramsite is uniformly laid; the KMnO is arranged on the water inlet pipe4A solution feed port.
2. The manganese-loaded oxide film expanded bed filter according to claim 1, wherein the manganese-loaded oxide film of the expanded filter bed is prepared by the following method: adding Mn2+Adding potassium permanganate into the aqueous solution with the concentration of more than 0.3mg/L, pumping the aqueous solution into a coating tank for placing floating ceramsite, and controlling the concentration of the potassium permanganate in the water to be 0.4-1 mg/L; passing MnO under the catalytic action of the gradually generated manganese oxide film4 ﹣Reduction of (2) and Mn2+Oxidation of (2) rapidly to form a large amount of MnO2Adsorbed on the surface of the floating ceramsite.
3. The manganese-loaded oxide film expanded bed filter tank as claimed in claim 2, wherein the floating ceramsite is prepared by the following method: using shale as a raw material, crushing and drying the shale by using a crusher, firing the shale in a rotary kiln for 18-22 min at 1100-1300 ℃, taking the shale out of the kiln, naturally cooling the shale, crushing the shale, and screening ceramsite with the particle size of 5-12 mm to obtain water-impregnated granules with the density of 0.95 +/-0.5 g/cm3The floating ceramsite.
4. The manganese-loaded oxide film expanded bed filter according to claim 1, wherein a gas flushing pipe of the manganese-loaded oxide film expanded bed filter is communicated with a bottom gas distribution device; the flushing wastewater drainage pipe is communicated with a water collecting main pipe of the bottom water collecting device; the other end of the air flushing pipe is connected with the blower.
The manganese-loaded oxide film expanded bed filter is a down-flow filter or an up-flow filter; for the down-flow filter, the water inlet pipe is communicated with the water distribution tank, and the water outlet pipe is communicated with the water collecting main pipe of the bottom water collecting device; and the water inlet pipe of the upflow filter is communicated with the water collecting main pipe of the bottom water collecting device, and the water outlet pipe is communicated with the water distribution tank.
5. The manganese-loaded oxide membrane expanded bed filter according to claim 1, wherein the horizontal cross-sectional shape of said filter body is rectangular or circular.
6. The manganese-loaded oxide film expanded bed filter tank as claimed in claim 5, wherein when the filter tank body is of a reinforced concrete structure, the horizontal cross-sectional shape of the filter tank body is rectangular; when the filter tank body is welded by steel plates, the horizontal section of the filter tank body is circular or rectangular.
7. The manganese-loaded oxide film expanded bed filter according to claim 1, wherein the mesh diameter of the filter screen plate is 3-5 mm; the filter screen plate is made of stainless steel;
the upper transition area is a space between the water distribution tank and the filter screen plate, and the height of the upper transition area is 0.3-1 m;
the lower transition zone is a space between the lower part of the manganese-loaded oxide film expanded filter bed and the bottom water collecting device, and the height of the lower transition zone is 0.3-1 m;
the manganese-loaded oxide film expanded bed filter tank also comprises a bottom gas distribution device, the bottom gas distribution device is positioned in the lower transition zone, and the bottom gas distribution device consists of a gas distribution main pipe and a plurality of perforated gas pipes; the perforated gas pipe is horizontally arranged above the bottom of the tank and is communicated with the gas distribution main pipe;
the water collecting device consists of a water collecting main pipe and a plurality of perforated water pipes; the perforated water pipe is horizontally arranged above the bottom of the pool and is connected with the water collecting main pipe.
8. The manganese-loaded oxide film expanded bed filter according to claim 7, wherein said water inlet pipe, said water outlet pipe, said air flushing pipe and said flushing waste water drain pipe are provided with valves.
9. The method for removing thallium by adsorption in the manganese-loaded oxide film expanded bed filter tank as claimed in any one of claims 1-8, wherein if the overflow mode is downflow, the raw water with potassium permanganate is fed into the water distribution tank from the water inlet pipe, overflows and is distributed into the upper transition zone, and is gradually distributed to the whole filter surface, flows downwards to pass through the filter screen plate and enter the floating ceramsite filter bed, and after thallium is removed by adsorption in the floating ceramsite filter bed, the purified water flows downwards to pass through the lower transition zone, and is collected by the water collecting device and flows out to the water outlet pipe;
if the overflowing mode adopts an upflow mode, raw water added with potassium permanganate enters the water collecting device from the water inlet pipe, is gradually and uniformly distributed to the whole filtering surface after being distributed in the lower transition region, flows upwards to enter the floating ceramsite filtering bed, is adsorbed by the floating ceramsite filtering bed to remove thallium, and then passes through the filtering screen plate upwards to flow through the upper transition region, and is collected by the water distribution tank to flow out of the water outlet pipe.
10. The method for removing thallium through adsorption by the manganese-loaded oxide film expanded bed filter tank as claimed in claim 9, wherein when the raw water is drinking water containing thallium, the potassium permanganate dosage is controlled according to the potassium permanganate concentration in the water being 0.3-0.5 mg/L; for the water with turbidity as raw water, the raw water is pretreated by turbidity removal and then added with potassium permanganate.
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