WO2015123996A1 - 一种芬顿流化床处理装置及其废水处理方法 - Google Patents

一种芬顿流化床处理装置及其废水处理方法 Download PDF

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Publication number
WO2015123996A1
WO2015123996A1 PCT/CN2014/088710 CN2014088710W WO2015123996A1 WO 2015123996 A1 WO2015123996 A1 WO 2015123996A1 CN 2014088710 W CN2014088710 W CN 2014088710W WO 2015123996 A1 WO2015123996 A1 WO 2015123996A1
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Prior art keywords
water
main reaction
tank
fluidized bed
filler
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PCT/CN2014/088710
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English (en)
French (fr)
Inventor
李爱民
沈科
姜笔存
双陈冬
刘福强
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南京大学
南京大学盐城环保技术与工程研究院
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Priority to AU2014383705A priority Critical patent/AU2014383705B2/en
Priority to JP2016520688A priority patent/JP6340421B2/ja
Priority to US15/118,734 priority patent/US10183878B2/en
Priority to KR1020167024638A priority patent/KR102047772B1/ko
Publication of WO2015123996A1 publication Critical patent/WO2015123996A1/zh

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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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by 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
    • C02F1/72—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
    • C02F1/28—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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • 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
    • C02F2201/002—Construction details of the apparatus
    • 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
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Definitions

  • the invention belongs to the field of wastewater treatment, and more particularly to a Fenton fluidized bed treatment device and a wastewater treatment method thereof.
  • the quality of industrial wastewater in different industries and different plant areas varies greatly, and the content and type of organic matter have great differences.
  • the fluidized bed Fenton can be applied to the treatment of different water quality wastewater by adjusting the dosage and dosage.
  • the dosage is higher than that of general wastewater; for wastewater with higher cellulose or hemicellulose content (such as papermaking wastewater), the amount of ferrous iron is higher.
  • the treatment of wastewater is favorable (the ratio of dosing is different from other wastewater).
  • the fluidized bed Fenton technology uses the filler crystallization technology to make the ferric iron which is easy to form iron mud coating on the surface of the filler particles by forming the crystal of the iron oxide catalyst, which not only effectively solves the problem of catalyst loss with water, but also the crystal. Heterogeneous catalysis and reductive dissolution enhance the catalytic oxidation efficiency. To achieve this technology, the design of the Fenton fluidized bed unit is of paramount importance.
  • the Fenton fluidized bed apparatus disclosed in Chinese Patent Publication No. CN 202898099 U reduces the iron sludge production by the internal fixed catalyst, but the efficiency of heterogeneous catalysis is low, and the water quality of the premixing zone is not uniform due to no special mixing measures.
  • Chinese patent CN 202688073 U discloses a multi-point dosing Fenton fluidized bed device for prolonging the sewage treatment process through a draft tube, which improves the utilization rate of the medicament and the treatment efficiency; however, the device does not consider the separation of the solid filler, and the device Internal loop, even distribution problem, and the operation is cumbersome.
  • the Chinese patent CN 202139138 U discloses a Fenton fluidized bed device connected to the iron bed micro-electrolysis reaction tower without filler separation measures. When the scale is large, it is difficult to achieve uniform water distribution, and the high temperature of the front tower water is not fully utilized. The jet consumes more power.
  • the Fenton fluidized bed device disclosed in the Chinese patents CN 102774953 A and CN 202643404 U is not resistant to the influent impact load, and is prone to splashing water when there is a headroom, and the water quality is uneven after the pump is added without special mixing measures.
  • the cloth water pipe cloth is easily blocked by the packing. When the scale is large, the uneven water distribution is easy to occur, and the slag discharging is difficult to control.
  • the air-lifting Fenton fluidized bed device disclosed in Chinese Patent No. CN 202785780 U also has an inrush load in the inlet tank and is easy to splash due to the headroom.
  • the two reflux waters cannot be mixed thoroughly to affect the reaction effect;
  • the turbulence in the tube is severe, which affects the crystallization effect; in the case of reflux, the stripping forms a fluidized bed, resulting in operating costs and investment costs. l; and the device does not take into account the problem of exclusion of the filler particles after crystal growth.
  • the invention provides a Fenton fluidized bed treatment device and a wastewater treatment method thereof, which can improve the utilization rate of the medicament and maintain an efficient and stable iron removal efficiency.
  • a Fenton fluidized bed processing apparatus comprising a regulating tank, a lifting pump and a main reaction tower, wherein the regulating tank is connected to a water distribution tank at the top of the main reaction tower through a lifting pump, wherein the main reaction tower is filled with a filler, The bottom of the main reaction tower is a reverse cone, the inverted cone is provided with a water inlet, and the bottom of the inverted cone is connected with the slag discharge pipe;
  • a swash plate is disposed above the filler in the main reaction column; a separation groove and a water outlet are disposed at the port of the main reaction column above the swash plate; and the separation groove is divided by a vertical partition Two upper and lower single grooves, the upper ends of the two single grooves are connected with the distribution tank, and the bottom of the separation groove is provided with an opening, and the two single grooves are respectively connected to the reverse cone by the first circulation pump and the second circulation pump Inlet; a sink is located directly opposite the dividing trough.
  • two sets of water inlets are symmetrically arranged at 1/3 and 2/3 of the bottom of the inverted cone, a total of four, so that the mixed liquid flows out from the two single grooves and is evenly distributed after the first circulation pump and the second circulation pump.
  • the split is two.
  • the top of the water distribution tank is provided with a regulating tube to control the water load, and the other end of the regulating tube is connected to the adjusting tank.
  • the cone angle of the inverted cone is 5 to 60°.
  • the filler is: one or more of resin, activated carbon granules, construction sand, quartz sand, zeolite, ceramsite, soapstone, brick scrap, and the average particle diameter of the filler particles is 0.1-3.0 mm. .
  • a plurality of baffles are arranged in the longitudinal direction of the main reaction column in the filler of the main reaction tower, and the baffles divides the main reaction tower into a plurality of ascending spaces, and the bottom edge of the baffles is at a height from the upper end of the inverted cone It is 1 to 4 m.
  • a wastewater treatment method for a Fenton fluidized bed treatment device the steps of which are:
  • a swirling mixed water flow is generated in the inverted cone, reacted with the filler, and then pushed and separated by the deflector, a part of the supernatant enters the single tank of the separation tank from the bottom of the separation tank, and a part enters and exits Sink out;
  • the filler particles are added in two portions, and the total amount of the filler is 75% to 85%, and after the operation for 50 to 500 hours, the remaining 15% to 25% is added.
  • the top of the main reaction tower of the present invention is equipped with a water distribution tank, and the problem of splashing water in the separation tank and the water entering the water from the bottom opening of the separation tank is eliminated by buffering the head balance of the lifting pump; The excess water produced is returned to the conditioning tank.
  • the top of the main reaction tower is provided with a partitioning groove which is open at the bottom of the bottom.
  • the partitioning tank is composed of two single tanks. After adding ferrous sulfate and hydrogen peroxide respectively in the two single tanks, the medicament is refluxed with the water flow; the water load is diluted by the effluent water. Prevent the reaction of ferrous sulfate and hydrogen peroxide in advance, and improve the utilization rate of the agent;
  • the taper angle of the inverted cone is set to 5 to 60°, the angle is too small and there is not enough inclination, and it is difficult to collect large particle packing; the angle is too large to waste the height of the reaction tower, and the swirl is too strong for the deflector The load is large, and the required tower height is also large;
  • the particle size of the filler is selected from 0.1 to 3.0 mm, the particle size is too large and the specific surface area is small, which is not conducive to rapid crystallization; the particle size is too small to be taken away by the water stream, and the fluidized state is unstable;
  • the baffles and the sloping plates are respectively disposed from the bottom to the top in the main reaction tower.
  • the baffle divides the reaction tower into a plurality of ascending spaces to prevent turbulence due to excessive inner diameter and fluctuation of influent water, and at the same time transform the severe swirl at the bottom into a stable push-up Flow, improve the fluidization height and quality of the packing layer; control the distance of the bottom of the baffle, promote the crushing of the thicker packing particles by the action of the swirling flow and the deflector to form a new seed crystal.
  • the sloping plate is used to trap small particle size and friction-crushed packing, prevent particles from entering the reflux pump (without using sufficient height separation), increase the density of the seed crystals in the tower, and maintain the efficiency of crystallization and iron removal.
  • a part of the effluent water is discharged through the sloping plate and the trough which is opposite to the dividing trough, and a part of the effluent is recirculated from the dividing trough, and the outlet trough and the separating trough are arranged oppositely to maintain the appearance and stabilize the water discharge load;
  • the filler dosage is moderate, ensuring the crystallization effect while saving cost, reducing the fluidization load; controlling the pH to 3.0 to 4.0, The best crystallization effect is beneficial to the reduction of iron mud; the control of the rising flow rate is 30-150 m/h, so that the top of the baffle is lower than the top of the suspension layer, and the single zones are balanced with each other; and hydrogen peroxide and sulfuric acid are respectively added in the separation tank.
  • ferrous iron prevents the two from reacting in advance, and at the same time acts as a dilution to increase the utilization rate of the medicament; after one week of operation, the dosage of ferrous sulfate is halved, and ⁇ -FeOOH ( ⁇ -type iron oxyhydroxide) is fully utilized.
  • ⁇ -FeOOH ⁇ -type iron oxyhydroxide
  • the filler is divided into two injections, first adding 75% to 85% of the filler particles, and taking advantage of the higher activity of the fresh filler to achieve better iron removal effect; after one week of operation, with the generation of crystallization With the accumulation, the suspension state of the filler particles is affected, and the surface ⁇ -FeOOH ( ⁇ -type iron oxyhydroxide) will inhibit the further crystallization of Fe 3+ to some extent; at this time, the remaining 15% to 25% is added.
  • ⁇ -FeOOH ⁇ -type iron oxyhydroxide
  • the filler particles can maintain the surface activity of the filler particles; at the same time, since the particle size of the new filler is smaller than that of the particles which have been crystallized, granules of large and small particles may occur in the reaction tower, and the suspension height of the filler layer is increased, and the removal is enhanced. Iron effect.
  • Figure 1 is a front elevational view of a sewage treatment plant of a Fenton fluidized bed
  • Figure 2 is a plan view of the deflector
  • Figure 3 is a plan view of the main reaction tower of Figure 1;
  • Figure 4 is a left side elevational view of the main reaction column of Figure 1.
  • Adjustment tank 1. Adjustment tank; 2. Lifting pump; 3. Water distribution tank; 4. Separation tank; 5. First circulation pump; 6. Second circulation pump; 7. Reverse cone; 8. Main reaction tower; Board; 10, sloping plate; 11, water outlet; 12, regulating tube.
  • the Fenton fluidized bed sewage treatment apparatus of the present embodiment includes: an adjustment tank 1, a lift pump 2, and a main reaction tower 8, and the adjustment tank 1 passes through the lift pump 2 and the water distribution tank 3 at the top of the main reaction tower 8. Connection; the top of the water distribution tank 3 is provided with an adjustment pipe 12 to control the water load, and the other end of the adjustment pipe 12 is connected to the adjustment tank 1.
  • the water distribution tank 3 and the two dividing tanks 4 are respectively connected, and the water discharged from the dividing tank 4 is divided into two by the first circulating pump 5 and the second circulating pump 6, respectively, from the bottom 1/3 and 2/3 of the bottom of the inverted cone 7
  • Two water inlets tangentially entering the bottom of the main reaction tower 8 are formed into a swirling flow by a reverse cone 7 to form a swirling flow.
  • the inclined angle of the tapered cone 7 is 60°; the main reaction tower 8 is filled with a 0.1 mm diameter.
  • the resin is used as a filler; a baffle 9 is provided at a position of 1 m above the inverted cone 7 in the main reaction column 8 for generating a push flow and crushing the crystal particles to generate a new seed crystal; and a swash plate 10 is disposed above the deflector 9 The solid particles and the effluent; finally, a portion of the supernatant passing through the swash plate 10 is returned from the bottom into the separation tank 4, and the other portion is discharged from the outlet 11 opposite to the separation tank 4.
  • the COD of the wastewater after biotechnology treatment in a chemical park is 114mg/L with color.
  • the Fenton fluidized bed sewage treatment device and its wastewater treatment method are used to treat the wastewater.
  • the dosage of hydrogen peroxide is 0.1%.
  • the dosage is 200 mg/L.
  • the Fenton fluidized bed sewage treatment device of the present embodiment is described with reference to Figs. 1 to 4, which comprises: an adjustment tank 1, a lift pump 2 and a main reaction column 8, which is passed through a lifting tank 2 and a distribution tank at the top of the main reaction tower 8. 3 connections; water tank 3 and two compartments
  • the separation tank is divided into four, and the outlet water of the separation tank 4 is divided into two by the first circulation pump 5 and the second circulation pump 6, respectively, and the water inlet device that enters the bottom of the main reaction tower 8 from two heights is inverted.
  • the cone 7 forms a swirling flow, and the inclined angle of the tapered cone 7 is 50°;
  • the main reaction tower 8 is filled with quartz sand having a particle diameter of 0.3 mm as a filler; and the main reaction tower 8 is provided with a reverse cone 7 or more 2 m.
  • the baffle 9 is used to generate the push flow and crush the crystal particles to produce a new seed crystal;
  • the deflector 10 is provided with a swash plate 10 to separate the solid particles and the effluent; finally, a portion of the supernatant passing through the swash plate 10 enters the separation groove from the bottom. 4 is recirculated, and the other portion is discharged from the water outlet 11 opposite to the partitioning groove 4.
  • the wastewater treatment method based on the Fenton fluidized bed sewage treatment device of the present embodiment the steps of which are:
  • the COD of the wastewater after biotechnology treatment in a chemical park is 114mg/L with color.
  • the Fenton fluidized bed sewage treatment device and its wastewater treatment method are used to treat the wastewater.
  • the dosage of hydrogen peroxide is 0.1%.
  • the dosage is 200 mg/L.
  • the results show that the complete decolorization, COD removal rate is as high as 81.25%, the iron removal efficiency is 87.10%, and the COD removal efficiency is still 80.21% after the ferrous reduction.
  • the Fenton fluidized bed sewage treatment device of the present embodiment has basically the same structure, and the difference is that the inclined angle of the taper cone is 40°, and the main reaction tower is filled with the diameter of 0.5 mm.
  • the construction sand is used as a filler; the main reaction tower is provided with a baffle plate 3m above the inverted cone for generating the push flow and crushing the crystal particles to produce a new seed crystal.
  • the wastewater treatment method based on the above device has the following steps:
  • the COD of the wastewater after biotechnology treatment in a chemical park is 114mg/L with color.
  • the Fenton fluidized bed sewage treatment device and its wastewater treatment method are used to treat the wastewater.
  • the dosage of hydrogen peroxide is 0.1%.
  • the dosage is 200 mg/L.
  • the results show that the complete decolorization, COD removal rate is as high as 88.02%, the iron removal efficiency is as high as 93.04%, and the COD removal efficiency is still 85.94% after halving.
  • the Fenton fluidized bed sewage treatment device of the present embodiment has basically the same structure, and the difference is that the inclination angle of the taper cone is 30°, and the main reaction tower is provided with a particle diameter of 0.8 mm.
  • the zeolite is used as a filler; 4 m above the inverted cone in the main reaction tower is provided with a baffle for generating a push flow and crushing the crystal particles to produce a new seed crystal.
  • the COD of the wastewater after biotechnology treatment in a chemical park is 114mg/L with color.
  • the Fenton fluidized bed sewage treatment device and its wastewater treatment method are used to treat the wastewater.
  • the dosage of hydrogen peroxide is 0.1%.
  • the dosage is 200 mg/L.
  • the Fenton fluidized bed sewage treatment device of the present embodiment has basically the same structure, and the difference is that the inclined angle of the tapered surface of the inverted cone 7 is 20°, and the main reaction tower 8 is filled with 1 mm.
  • the diameter of the ceramsite is used as a filler; in the main reaction tower 8, the inverted cone 7 and above 2 m are provided with a baffle 9 for generating a push flow and crushing the crystal particles to produce a new seed crystal.
  • the steps of the wastewater treatment method are as follows:
  • the wastewater COD of a chemical plant treated with nitrification wastewater is 167 mg/L, with chromaticity.
  • the wastewater is treated by the Fenton fluidized bed sewage treatment device and the wastewater treatment method of the present embodiment, and the hydrogen peroxide dosage is 0.15%, ferrous iron.
  • the dosage is 300 mg/L.
  • the Fenton fluidized bed sewage treatment device of the present embodiment has basically the same structure, and the difference is that the inclination angle of the taper cone is 10°; the main reaction tower is filled with 2 mm particle diameter. Saponite as a filler; main reaction tower 2m above the inner cone cone is provided with a baffle for generating the push flow and crushing the crystal particles to produce a new seed crystal.
  • the wastewater COD of the chemical treatment of nitrification wastewater in a chemical plant is 167 mg/L with color.
  • the Fenton fluidized bed sewage treatment device and its wastewater treatment method are used to treat the wastewater.
  • the dosage of hydrogen peroxide is 0.15%.
  • the iron dosage is 300 mg/L. The results showed that the COD removal rate was 72.22%, the iron removal efficiency was 78.41%, and the COD removal efficiency was 72.00% after halving.
  • the Fenton fluidized bed sewage treatment device of the present embodiment has basically the same structure, and the difference is that the inclination angle of the tapered cone is 5°; the main reaction tower is filled with the diameter of 0.5 mm.
  • the brick particles are used as the filler; the baffle is provided 2m above the inverted cone in the main reaction tower for generating the push flow and crushing the crystal particles to produce a new seed crystal.
  • the steps of the wastewater treatment method are as follows:
  • the wastewater COD of the chemical treatment of nitrification wastewater in a chemical plant is 167 mg/L with color.
  • the Fenton fluidized bed sewage treatment device and its wastewater treatment method are used to treat the wastewater.
  • the dosage of hydrogen peroxide is 0.1%.
  • the iron dosage is 200 mg/L. The results showed that the complete decolorization, COD removal rate was 72.28%, iron removal efficiency was 88.71%, and COD removal efficiency was 72.22% after ferrous reduction.
  • the Fenton fluidized bed sewage treatment device of the present embodiment has basically the same structure, and the difference is that the inclination angle of the cone of the reverse cone is 20°; the main reaction tower is filled with the particle size of 3 mm. Activated carbon as a filler; 2m above the inverted cone in the main reaction tower is provided with a baffle for generating the push flow and crushing the crystal particles to produce a new seed crystal.
  • the wastewater treatment method is:
  • the wastewater COD of the chemical treatment of nitrification wastewater in a chemical plant is 167 mg/L.
  • the wastewater is treated by the Fenton fluidized bed sewage treatment device and the wastewater treatment method of the present embodiment.
  • the dosage of hydrogen peroxide is 0.1%, and the amount of ferrous iron is added. It is 200 mg/L.
  • the results show that the COD removal rate is 74.20%, the iron removal efficiency is 85.07%, and the COD removal efficiency after halving of ferrous iron is 72.86%.
  • the Fenton fluidized bed sewage treatment device of the present embodiment has basically the same structure, and the difference is that the inclined angle of the tapered surface of the inverted cone 7 is 10°; the main reaction tower 8 is filled with 0.5 mm.
  • the quartz sand and the building sand of the particle size are used as the filler; and the baffle 7 is provided in the main reaction tower 8 above 3 m, and the baffle 9 is provided for generating the push flow and crushing the crystal particles to produce a new seed crystal.
  • the wastewater treatment method is:
  • the wastewater COD of the chemical treatment of nitrification wastewater in a chemical plant is 167 mg/L with color.
  • the Fenton fluidized bed sewage treatment device and its wastewater treatment method are used to treat the wastewater.
  • the dosage of hydrogen peroxide is 0.15%.
  • the iron dosage is 300 mg/L. The results show that the complete decolorization, COD removal rate is 73.41%, the iron removal efficiency is 89.67%, and the COD removal efficiency after halving of ferrous iron is 72.66%.

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Abstract

本发明公开了一种芬顿流化床处理装置及其废水处理方法，属于废水处理领域。该装置包括调节池、提升泵和主体反应塔，调节池通过提升泵与主体反应塔顶部的配水槽连接，主体反应塔内填充有填料，主体反应塔内填料底部为倒锥斗，倒锥斗上设置有进水口，倒锥斗的底部连接排渣管；主体反应塔内填料上方设置有斜板；在斜板上方且位于主体反应塔端口处设置有分隔槽和出水槽；分隔槽由竖直的隔板均分为左右两单槽，两单槽的上端均与所述的配水槽连通，分隔槽的底部设有开口，该两单槽分别通过第一循环泵和第二循环泵接入所述倒锥斗的进水口；分隔槽的正对面设有出水槽。采用本发明的装置可以提高药剂利用率，维持高效稳定的除铁效率。

Description

一种芬顿流化床处理装置及其废水处理方法 技术领域
本发明属于废水处理领域，更具体地说，涉及一种芬顿流化床处理装置及其废水处理方法。
背景技术
在生物技术处理后的废水中，通常仍存在着许多难降解有机物，造成出水水质不达标，尤其是印染、造纸、硝化等化工废水。而国家对水处理的要求越来越严格，再生水的使用越来越受到重视，因此，针对生物技术处理后废水的深度处理十分必要。芬顿试剂由于产生的羟基自由基具有强氧化能力，针对这些难降解污染物具有良好的处理效果；同时由于芬顿技术操作简单、投资成本较低、处理效果良好而得到了广泛的应用。然而，传统芬顿氧化废水处理工艺存在药剂利用率偏低，含铁污泥产量较大的缺陷。
不同行业、不同厂区内工业废水水质变化较大，有机物含量、种类均具有较大的差异；流化床芬顿通过调整加药量和加药比例，可适用于不同水质废水的处理。例如，针对含难降解有机物或有机物含量高的废水，加药量高于一般废水；针对纤维素或半纤维素含量较高的废水(如造纸废水)，亚铁投加量偏高对该类废水的处理有利(加药比例区别于其他废水)。
流化床芬顿技术通过填料结晶技术，使容易形成铁泥的三价铁通过形成铁氧化物催化剂晶体的形式披覆在填料颗粒表面，不仅有效解决了催化剂随水流失的问题，同时因晶体异相催化和还原溶解作用强化了催化氧化效率。要实现这一技术，芬顿流化床装置的设计至关重用。中国专利公开号CN 202898099 U公开的芬顿流化床装置虽然通过内部固定催化剂降低了铁泥产量，但异相催化的效率低下，且无特殊混合措施容易造成预混合区的水质不均匀。中国专利CN 202688073 U公开了一种通过导流筒延长污水处理历程的多点加药芬顿流化床装置，提高了药剂利用率和处理效率；但是该装置未考虑固体填料的分离、在装置内循环、均匀分布的问题，且操作繁琐。中国专利CN 202139138 U公开的接在铁床微电解反应塔后面的芬顿流化床装置无填料分离措施，当规模较大时难以实现均匀布水，且未充分利用前塔出水的高位而采用射流器，消耗更多动力。中国专利CN 102774953 A和CN 202643404 U公开的芬顿流化床装置进水池不耐进水冲击负荷，有扬程余量时易发生溅水现象，泵后加药无特殊混匀措施造成水质不均匀，布水管布水易被填料堵塞，规模大时易发生布水不均现象，且排渣不易控制。中国专利CN 202785780 U公开的气提式的芬顿流化床装置同样存在进水槽不耐冲击负荷且易因扬程余量而溅水，两支回流水无法进行充分混合而影响反应效果；气提管内湍流剧烈，影响结晶效果；在有回流的情况下气提形成流化床，造成运行成本和投资成本上 升；且该装置未考虑填料颗粒结晶长大后排除的问题。
已公开的专利表明，关于流化床芬顿氧化装置的进水回流、布水、分离、排渣和流化等关键设计有多种表述和方式，然而各装置工程化应用存在或多或少问题。针对传统流化床芬顿氧化装置普遍存在的停留时间较长，布水不均而易产生沟流，药剂利用率低，除铁效果尚有待优化(出水的铁高于混凝沉淀所需量)等缺陷，结合多年流化床芬顿氧化工程设计和运行经验，本发明提出一种改进的流化床芬顿氧化床处理装置。
发明内容
1.要解决的技术问题
针对现有技术中存在的流化床芬顿氧化装置废水的停留时间长，布水不均而易产生沟流，药剂利用率低，除铁效果不佳(出水的铁高于混凝沉淀所需量)等问题，本发明提供了一种芬顿流化床处理装置及其废水处理方法，它可以提高药剂利用率，维持高效稳定的除铁效率。
2.技术方案
本发明的目的通过以下技术方案实现。
一种芬顿流化床处理装置，它包括调节池、提升泵和主体反应塔，调节池通过提升泵与主体反应塔顶部的配水槽连接，所述的主体反应塔内填充有填料，所述的主体反应塔内填料底部为倒锥斗，倒锥斗上设置有进水口，倒锥斗的底部连接排渣管；
所述的主体反应塔内填料上方设置有斜板；在斜板上方且位于所述的主体反应塔端口处设置有分隔槽和出水槽；所述的分隔槽由竖直的隔板均分为左右两单槽，两单槽的上端均与所述的配水槽连通，分隔槽的底部设有开口，该两单槽分别通过第一循环泵和第二循环泵接入所述倒锥斗的进水口；分隔槽的正对面设有出水槽。
优选地，在距离倒锥斗底部1/3和2/3处对称设置有两组进水口，共4个，使得混合液从两个单槽流出经第一循环泵和第二循环泵后均匀分流为两支。
优选地，所述的配水槽顶部设有调节管控制来水负荷，调节管的另一端与所述的调节池相连。
优选地，所述的倒锥斗的锥角角度为5～60°。
优选地，所述的填料为：树脂、活性炭颗粒、建筑砂、石英砂、沸石、陶粒、皂石、砖块碎屑中的一种或一种以上，填料颗粒平均粒径0.1～3.0mm。
优选地，在主体反应塔的填料内沿主体反应塔纵向设置有若干个导流板，导流板将主体反应塔分为若干个上升空间，导流板的底边距离倒锥斗上端的高度为1～4m。
一种所述的芬顿流化床处理装置的废水处理方法，其步骤为：
(a)在主体反应塔内加入主体反应塔体积10％～40％的填料颗粒；
(b)在调节池内调节进水pH，控制主体反应塔内的pH为3.0～4.0；控制水量，保持主体反应塔内的水流停留时间为10～30min；
(c)调节池的水经过提升泵进入配水槽，配水槽出水进入分隔槽，分别由第一循环泵和第二循环泵回流至倒锥斗，再通过倒锥斗上的进水口均匀进入主体反应塔内；调节回流比，控制主体反应塔内的上升流速为30～150m/h，保证导流板顶部低于填料悬浮层顶部；
(d)在分隔槽的两单槽内分别加双氧水和硫酸亚铁溶液(加药量视水质而定)，两种药剂分别随水流经过第一循环泵和第二循环泵进入倒锥斗；
(e)倒锥斗内产生旋流混匀水流，与填料进行反应，再经过导流板推流和分离后，上清液一部分从分隔槽的底部进入分隔槽的单槽内，一部分进入出水槽排出；
(f)运行一周以后，将硫酸亚铁减量50％继续运行；运行6～12个月后排渣。
优选地，所述的步骤(a)中，填料颗粒分两次投加，初次投加填料总量的75％～85％，运行50～500h后，补加剩余的15％～25％。
3.有益效果
相比于现有技术，本发明的优点在于：
(1)本发明主体反应塔顶部装有配水槽，通过缓冲提升泵的扬程余量消除分隔槽溅水以及进水从分隔槽底部开口冲入出水的问题；配水槽顶部设调节管将负荷过大产生的多余水量回流至调节池。主体反应塔顶部设有底部内侧开口的分隔槽，该分隔槽由两个单槽组成，两个单槽内分别加入硫酸亚铁和双氧水后药剂随水流一起回流；利用出水稀释进水负荷的同时防止硫酸亚铁和双氧水提前反应，提高药剂利用率；
(2)在距离倒锥斗底部1/3和2/3处沿锥面同一切线方向的对称设计有进水口，共4个，分隔槽的两个单槽通过第一循环泵和第二循环泵接入倒锥斗上的进水口，四支进水管从两个高度切向进入倒锥斗内形成旋流，充分混匀药剂、水流和填料；旋流布水不仅可消除布水不均而产生短流现象；对反应塔底部结晶的填料也有筛分作用，过大的颗粒会沉入倒锥斗内被排走；同时，高速旋流使得大颗粒填料相互摩擦破碎，产生新的晶种，维持反应塔内的填料活性和流化状态；
(3)倒锥斗的锥角角度设置为5～60°，角度太小没有足够的倾斜度，不易收集大颗粒填料；角度太大浪费反应塔的高度，同时旋流太强对导流板的负荷大，要求的塔高也大；
(4)填料粒径选择0.1～3.0mm，粒径太大比表面积小，不利于快速结晶；粒径太小容易被水流带走而流失，流化状态不稳定；
(5)主体反应塔内从下到上分别设置了导流板和斜板。导流板将反应塔分为多个上升空间，防止因内径过大和进水波动而出现紊流现象，同时将底部剧烈的旋流转变为稳定的上推 流，提高填料层的流化高度与质量；控制导流板底部距离，通过旋流和导流板的撞击作用促进结晶包裹较厚的填料颗粒破碎，形成新的晶种。斜板用于截留小粒径和摩擦破碎的填料，防止颗粒进入回流泵(无需利用足够的高度分离)的同时提高塔内晶种的密集度，维持结晶除铁效率。最后，一部分出水通过斜板上方、分隔槽正对的出水槽排出，一部分从分隔槽回流，出水槽与分隔槽正对设置既保持美观也稳定了出水负荷；
(6)保持导流板和倒锥斗的距离为1～4m，具体距离视反应塔的高度而定；距离太近会影响旋流甚至消除旋流，无法通过旋流使得混合体系充分反应；距离太远撞击力度不够起不到破碎颗粒的作用，同时上端超过填料悬浮层顶部，分隔的区域之间缺少均衡空间，容易造成区域之间推流不均匀；
(7)本发明的方法步骤中，加入反应塔体积10％～40％的填料颗粒，填料投加量适中，保证结晶效果的同时节约成本，降低流化负荷；控制pH至3.0～4.0，为最佳的结晶效果，有利于铁泥的削减；控制上升流速30～150m/h，使得导流板顶部低于悬浮层顶部，实现各单区的相互均衡；在分隔槽内分别加双氧水和硫酸亚铁，一方面防止二者提前反应，同时也起到稀释作用，提高药剂的利用率；运行一周后将硫酸亚铁的投加量减半，充分利用γ-FeOOH(γ型羟基氧化铁)结晶的异相催化效果，降低成本的同时进一步削减铁泥的产量；
(8)填料分为两次投加，先加入总量的75％～85％填料颗粒，充分利用新鲜填料活性较高的优势达到较好的除铁效果；运行一周以后，随着结晶的产生与累积，填料颗粒的悬浮状态受到影响，同时表面的γ-FeOOH(γ型羟基氧化铁)会在一定程度上抑制Fe3+的进一步结晶；此时，再补加剩余的15％～25％的填料颗粒，可以保持填料颗粒的表面活度；同时，由于新填料的粒径小于已经结晶成长的颗粒，在反应塔内会发生大小颗粒分层的现象，提高填料层的悬浮高度，强化除铁效果。
附图说明
图1为芬顿流化床的污水处理装置的主视图；
图2为导流板的俯视图；
图3为图1中的主体反应塔的俯视图；
图4为图1中的主体反应塔的左视图。
图中标号说明：
1、调节池；2、提升泵；3、配水槽；4、分隔槽；5、第一循环泵；6、第二循环泵；7、倒锥斗；8、主体反应塔；9、导流板；10、斜板；11、出水槽；12、调节管。
具体实施方式
下面结合说明书附图和具体的实施例，对本发明作详细描述。
实施例1
结合图1～4，本实施例的芬顿流化床污水处理装置包括：调节池1、提升泵2和主体反应塔8，调节池1通过提升泵2与主体反应塔8顶部的配水槽3连接；配水槽3顶部设有调节管12控制来水负荷，调节管12的另一端与所述的调节池1相连。配水槽3和两格分隔槽4分别连接，分隔槽4的出水经过第一循环泵5和第二循环泵6后分别一分为二，从距离倒锥斗7底部1/3和2/3两个高度切向进入主体反应塔8底部的进水装置一一倒锥斗7而形成旋流，倒锥斗7锥面的倾斜角度为60°；主体反应塔8内装有0.1mm粒径的树脂作为填料；主体反应塔8内倒锥斗7以上1m的位置处设有导流板9用于产生推流并破碎结晶颗粒产生新的晶种；导流板9上方设有斜板10分离固体颗粒和出水；最后经过斜板10的上清液一部分从底部进入分隔槽4回流，另一部分从与分隔槽4相对的出水槽11出水。
结合本实施例芬顿流化床污水处理装置的废水处理方法，其步骤为：
(a)初次在主体反应塔8内加入粒径为0.1mm树脂总量的75％(总量为主体反应塔8体积的10％)；
(b)在调节池1内调节进水pH，控制主体反应塔8内的pH为3.0；控制水量，保持主体反应塔8内的停留时间为10min；
(c)调节池1的水经过提升泵2进入配水槽3，配水槽3出水与部分出水在分隔槽4内混合，分别由第一循环泵5和第二循环泵6回流至倒锥斗7进水；调节回流比，控制主体反应塔8内的上升流速为30m/h，保证导流板9顶部低于填料悬浮层的顶部；
(d)在分隔槽4的两格槽内分别加双氧水和硫酸亚铁溶液，两种药剂分别随水流经过第一循环泵5和第二循环泵6进入倒锥斗7；
(e)倒锥斗7内产生旋流混匀水流与填料，进行反应；流化床经过导流板9推流和分离装置分离后的上清液一部分从分隔槽4的底部进入槽内，一部分进入出水槽11；
(f)运行50h后补加剩余的25％的平均粒径0.1mm树脂；
(g)运行一周以后，将硫酸亚铁减量50％继续运行；运行12个月后排渣。
某化工园区生物技术处理后的废水COD为114mg/L，带有色度，采用本实施例芬顿流化床污水处理装置及其废水处理方法处理该废水，双氧水投加量0.1％，亚铁投加量为200mg/L。结果表明，完全脱色，COD去除率达76.56％，除铁效率达74.34％，亚铁减半后COD去除效率达73.96％。
实施例2
结合图1～4说明本实施例芬顿流化床污水处理装置，它包括：调节池1、提升泵2和主体反应塔8，调节池1通过提升泵2与主体反应塔8顶部的配水槽3连接；配水槽3和两格 分隔槽分4别连接，分隔槽4的出水经过第一循环泵5和第二循环泵6后分别一分为二，从两个高度切向进入主体反应塔8底部的进水装置——倒锥斗7而形成旋流，倒锥斗7锥面的倾斜角度为50°；主体反应塔8内装有0.3mm粒径的石英砂作为填料；主体反应塔8内倒锥斗7以上2m设有导流板9用于产生推流并破碎结晶颗粒产生新的晶种；导流板9上方设有斜板10分离固体颗粒和出水；最后经过斜板10的上清液一部分从底部进入分隔槽4回流，另一部分从与分隔槽4相对的出水槽11出水。
基于本实施例芬顿流化床污水处理装置的废水处理方法，其步骤为：
(a)初次在主体反应塔8内加入粒径为0.3mm石英砂总量的80％(总量为主体反应塔8体积的20％)；
(b)在调节池1内调节进水pH，控制主体反应塔8内的pH为3.5；控制水量，保持主体反应塔8内的停留时间为20min；
(c)调节池1的水经过提升泵2进入配水槽3，配水槽3出水与部分出水在分隔槽4内混合，分别由第一循环泵5和第二循环泵6回流至倒锥斗7进水；调节回流比，控制主体反应塔8内的上升流速为40m/h，保证导流板9顶部低于填料悬浮层的顶部；
(d)在分隔槽4的两格槽内分别加双氧水和硫酸亚铁溶液，两种药剂分别随水流经过第一循环泵5和第二循环泵6进入倒锥斗7；
(e)倒锥斗7内产生旋流混匀水流与填料，进行反应；流化床经过导流板9推流和分离装置分离后的上清液一部分从分隔槽4的底部进入槽内，一部分进入出水槽11；
(f)运行100h后补加剩余的20％的0.3mm石英砂；
(g)运行一周以后，将硫酸亚铁减量50％继续运行；运行11个月后排渣。
某化工园区生物技术处理后的废水COD为114mg/L，带有色度，采用本实施例芬顿流化床污水处理装置及其废水处理方法处理该废水，双氧水投加量0.1％，亚铁投加量为200mg/L。结果表明，完全脱色，COD去除率高达81.25％，除铁效率达87.10％，亚铁减半后COD去除效率仍达80.21％。
实施例3
相比于实施例1，本实施例的芬顿流化床污水处理装置结构基本相同，其不同之处在于，倒锥斗锥面的倾斜角度为40°，主体反应塔内装有0.5mm粒径的建筑砂作为填料；主体反应塔内倒锥斗以上3m设有导流板用于产生推流并破碎结晶颗粒产生新的晶种。
基于上述装置的废水处理方法，其步骤为：
(a)初次在主体反应塔8内加入粒径为0.5mm石英砂总量的85％(总量为主体反应塔8体积的30％)；
(b)在调节池1内调节进水pH，控制主体反应塔8内的pH为4.0；控制水量，保持主体反应塔8内的停留时间为30min；
(c)调节池1的水经过提升泵2进入配水槽3，配水槽3出水与部分出水在分隔槽4内混合，分别由第一循环泵5和第二循环泵6回流至倒锥斗7进水；调节回流比，控制主体反应塔8内的上升流速为50m/h，保证导流板9顶部低于填料悬浮层的顶部；
(d)在分隔槽4的两格槽内分别加双氧水和硫酸亚铁溶液，两种药剂分别随水流经过第一循环泵5和第二循环泵6进入倒锥斗7；
(e)倒锥斗7内产生旋流混匀水流与填料，进行反应；流化床经过导流板9推流和分离装置分离后的上清液一部分从分隔槽4的底部进入槽内，一部分进入出水槽11；
(f)运行200h后补加剩余的15％的0.5mm建筑砂；
(g)运行一周以后，将硫酸亚铁减量50％继续运行；运行10个月后排渣。
某化工园区生物技术处理后的废水COD为114mg/L，带有色度，采用本实施例芬顿流化床污水处理装置及其废水处理方法处理该废水，双氧水投加量0.1％，亚铁投加量为200mg/L。结果表明，完全脱色，COD去除率高达88.02％，除铁效率高达93.04％，亚铁减半后COD去除效率仍达85.94％。
实施例4
相比于实施例1，本实施例的芬顿流化床污水处理装置结构基本相同，其不同之处在于，倒锥斗锥面的倾斜角度为30°，主体反应塔内装有0.8mm粒径的沸石作为填料；主体反应塔内倒锥斗以上4m设有导流板用于产生推流并破碎结晶颗粒产生新的晶种。
结合本实施例芬顿流化床污水处理装置的废水处理方法，其步骤为：
(a)初次在主体反应塔8内加入粒径为0.8mm沸石总量的80％(总量为主体反应塔8体积的40％)；
(b)在调节池1内调节进水pH，控制主体反应塔8内的pH为3.5；控制水量，保持主体反应塔8内的停留时间为30min；
(c)调节池1的水经过提升泵2进入配水槽3，配水槽3出水与部分出水在分隔槽4内混合，分别由第一循环泵5和第二循环泵6回流至倒锥斗7进水；调节回流比，控制主体反应塔8内的上升流速为80m/h，保证导流板9顶部低于填料悬浮层的顶部；
(d)在分隔槽4的两格槽内分别加双氧水和硫酸亚铁溶液，两种药剂分别随水流经过第一循环泵5和第二循环泵6进入倒锥斗7；
(e)倒锥斗7内产生旋流混匀水流与填料，进行反应；流化床经过导流板9推流和分离装置分离后的上清液一部分从分隔槽4的底部进入槽内，一部分进入出水槽11；
(f)运行300h后补加剩余的20％的0.8mm沸石；
(g)运行一周以后，将硫酸亚铁减量50％继续运行；运行9个月后排渣。
某化工园区生物技术处理后的废水COD为114mg/L，带有色度，采用本实施例芬顿流化床污水处理装置及其废水处理方法处理该废水，双氧水投加量0.1％，亚铁投加量为200mg/L。结果表明，完全脱色COD去除率高达87.53％，除铁效率高达92.15％，亚铁减半后COD去除效率仍有87.48％。
实施例5
相比于实施例1，本实施例的芬顿流化床污水处理装置结构基本相同，其不同之处在于，倒锥斗7锥面的倾斜角度为20°，主体反应塔8内装有1mm粒径的陶粒作为填料；主体反应塔8内倒锥斗7以上2m设有导流板9用于产生推流并破碎结晶颗粒产生新的晶种。
结合本实施例芬顿流化床污水处理装置，其废水处理方法步骤为：
(a)初次在主体反应塔8内加入粒径为1mm陶粒总量的80％(总量为主体反应塔8体积的30％)；
(b)在调节池1内调节进水pH，控制主体反应塔内的pH为3.5；控制水量，保持主体反应塔8内的停留时间为30min；
(c)调节池1的水经过提升泵2进入配水槽3，配水槽3出水与部分出水在分隔槽4内混合，分别由第一循环泵5和第二循环泵6回流至倒锥斗7进水；调节回流比，控制主体反应塔8内的上升流速为100m/h，保证导流板9顶部低于填料悬浮层的顶部；
(d)在分隔槽4的两格槽内分别加双氧水和硫酸亚铁溶液，两种药剂分别随水流经过第一循环泵5和第二循环泵6进入倒锥斗7；
(e)倒锥斗7内产生旋流混匀水流与填料，进行反应；流化床经过导流板9推流和分离装置分离后的上清液一部分从分隔槽4的底部进入槽内，一部分进入出水槽11；
(f)运行400h后补加剩余的20％的1mm陶粒；
(g)运行一周以后，将硫酸亚铁减量50％继续运行；运行8个月后排渣。
某化工厂硝化废水生物技术处理后的废水COD为167mg/L，带有色度采用本实施例芬顿流化床污水处理装置及其废水处理方法处理该废水，双氧水投加量0.15％，亚铁投加量为300mg/L。结果表明，完全脱色，COD去除率为71.67％，除铁效率为78.39％，亚铁减半后COD去除效率为70.11％。
实施例6
相比于实施例1，本实施例的芬顿流化床污水处理装置结构基本相同，其不同之处在于，倒锥斗锥面的倾斜角度为10°；主体反应塔内装有2mm粒径的皂石作为填料；主体反应塔 内倒锥斗以上2m设有导流板用于产生推流并破碎结晶颗粒产生新的晶种。
结合本实施例芬顿流化床污水处理装置的废水处理方法，其步骤为：
(a)初次在主体反应塔8内加入粒径为2mm皂石总量的80％(总量为主体反应塔8体积的40％)；
(b)在调节池1内调节进水pH，控制主体反应塔8内的pH为3.5；控制水量，保持主体反应塔8内的停留时间为30min；
(c)调节池1的水经过提升泵2进入配水槽3，配水槽3出水与部分出水在分隔槽4内混合，分别由第一循环泵5和第二循环泵6回流至倒锥斗7进水；调节回流比，控制主体反应塔内的上升流速为150m/h，保证导流板9顶部低于填料悬浮层的顶部；
(d)在分隔槽4的两格槽内分别加双氧水和硫酸亚铁溶液，两种药剂分别随水流经过第一循环泵5和第二循环泵6进入倒锥斗7；
(e)倒锥斗7内产生旋流混匀水流与填料，进行反应；流化床经过导流板9推流和分离装置分离后的上清液一部分从分隔槽4的底部进入槽内，一部分进入出水槽11；
(f)运行500h后补加剩余的20％的2mm皂石；
(g)运行一周以后，将硫酸亚铁减量50％继续运行；运行7个月后排渣。
某化工厂硝化废水生物技术处理后的废水COD为167mg/L，带有色度，采用本实施例芬顿流化床污水处理装置及其废水处理方法处理该废水，双氧水投加量0.15％，亚铁投加量为300mg/L。结果表明，完全脱色，COD去除率为72.22％，除铁效率为78.41％，亚铁减半后COD去除效率为72.00％。
实施例7
相比于实施例1，本实施例的芬顿流化床污水处理装置结构基本相同，其不同之处在于，倒锥斗锥面的倾斜角度为5°；主体反应塔内装有0.5mm粒径的砖块颗粒作为填料；主体反应塔内倒锥斗以上2m设有导流板用于产生推流并破碎结晶颗粒产生新的晶种。
结合本实施例芬顿流化床污水处理装置，其废水处理方法的步骤为：
(a)初次在主体反应塔8内加入粒径为0.5mm砖块颗粒总量的80％(总量为主体反应塔8体积的20％)；
(b)在调节池1内调节进水pH，控制主体反应塔8内的pH为3.5；控制水量，保持主体反应塔8内的停留时间为30min；
(c)调节池1的水经过提升泵2进入配水槽3，配水槽3出水与部分出水在分隔槽4内混合，分别由第一循环泵5和第二循环泵6回流至倒锥斗7进水；调节回流比，控制主体反应塔8内的上升流速为50m/h，保证导流板9顶部低于填料悬浮层的顶部；
(d)在分隔槽4的两格槽内分别加双氧水和硫酸亚铁溶液，两种药剂分别随水流经过第一循环泵5和第二循环泵6进入倒锥斗7；
(e)倒锥斗7内产生旋流混匀水流与填料，进行反应；流化床经过导流板9推流和分离装置分离后的上清液一部分从分隔槽4的底部进入槽内，一部分进入出水槽11；
(f)运行200h后补加剩余的20％的0.5mm砖块颗粒；
(g)运行一周以后，将硫酸亚铁减量50％继续运行；运行6个月后排渣。
某化工厂硝化废水生物技术处理后的废水COD为167mg/L，带有色度，采用本实施例芬顿流化床污水处理装置及其废水处理方法处理该废水，双氧水投加量0.1％，亚铁投加量为200mg/L。结果表明，完全脱色，COD去除率为72.28％，除铁效率为88.71％，亚铁减半后COD去除效率72.22％。
实施例8
相比于实施例1，本实施例的芬顿流化床污水处理装置结构基本相同，其不同之处在于，倒锥斗锥面的倾斜角度为20°；主体反应塔内装有3mm粒径的活性炭作为填料；主体反应塔内倒锥斗以上2m设有导流板用于产生推流并破碎结晶颗粒产生新的晶种。
结合本实施例芬顿流化床污水处理装置，其废水处理方法为：
(a)初次在主体反应塔8内加入粒径为3mm活性炭总量的80％(总量为主体反应塔8体积的20％)；
(b)在调节池1内调节进水pH，控制主体反应塔8内的pH为3.5；控制水量，保持主体反应塔8内的停留时间为30min；
(c)调节池1的水经过提升泵2进入配水槽3，配水槽3出水与部分出水在分隔槽4内混合，分别由第一循环泵5和第二循环泵6回流至倒锥斗7进水；调节回流比，控制主体反应塔8内的上升流速为80m/h，保证导流板9顶部低于填料悬浮层的顶部；
(d)在分隔槽4的两格槽内分别加双氧水和硫酸亚铁溶液，两种药剂分别随水流经过第一循环泵5和第二循环泵6进入倒锥斗；
(e)倒锥斗7内产生旋流混匀水流与填料，进行反应；流化床经过导流板9推流和分离装置分离后的上清液一部分从分隔槽4的底部进入槽内，一部分进入出水槽11；
(f)运行200h后补加剩余的20％的3mm活性炭；
(g)运行一周以后，将硫酸亚铁减量50％继续运行；运行6个月后排渣。
某化工厂硝化废水生物技术处理后的废水COD为167mg/L，采用本实施例芬顿流化床污水处理装置及其废水处理方法处理该废水，双氧水投加量0.1％，亚铁投加量为200mg/L。结果表明，COD去除率为74.20％，除铁效率达85.07％，亚铁减半后COD去除效率为72.86％。
实施例9
相比于实施例1，本实施例的芬顿流化床污水处理装置结构基本相同，其不同之处在于，倒锥斗7锥面的倾斜角度为10°；主体反应塔8内装有0.5mm粒径的石英砂和建筑砂作为填料；主体反应塔8内倒锥斗7以上3m设有导流板9用于产生推流并破碎结晶颗粒产生新的晶种。
基于本实施例芬顿流化床污水处理装置，其废水处理方法为：
(a)初次在主体反应塔8内加入粒径为0.5mm石英砂和建筑砂总量的80％(总量为主体反应塔8体积的20％，石英砂和建筑砂各占50％)；
(b)在调节池内调节进水pH，控制主体反应塔8内的pH为3.5；控制水量，保持主体反应塔8内的停留时间为30min；
(c)调节池1的水经过提升泵2进入配水槽3，配水槽3出水与部分出水在分隔槽4内混合，分别由第一循环泵5和第二循环泵6回流至倒锥斗7进水；调节回流比，控制主体反应塔8内的上升流速为50m/h，保证导流板9顶部低于填料悬浮层的顶部；
(d)在分隔槽4的两格槽内分别加双氧水和硫酸亚铁溶液，两种药剂分别随水流经过第一循环泵5和第二循环泵6进入倒锥斗7；
(e)倒锥斗7内产生旋流混匀水流与填料，进行反应；流化床经过导流板9推流和分离装置分离后的上清液一部分从分隔槽4的底部进入槽内，一部分进入出水槽11；
(f)运行200h后补加剩余的20％的0.5mm石英砂和建筑砂；
(g)运行一周以后，将硫酸亚铁减量50％继续运行；运行9个月后排渣。
某化工厂硝化废水生物技术处理后的废水COD为167mg/L，带有色度，采用本实施例芬顿流化床污水处理装置及其废水处理方法处理该废水，双氧水投加量0.15％，亚铁投加量为300mg/L。结果表明，完全脱色，COD去除率为73.41％，除铁效率达89.67％，亚铁减半后COD去除效率为72.66％。

Claims (8)

  1. 一种芬顿流化床处理装置，它包括调节池(1)、提升泵(2)和主体反应塔(8)，调节池(1)通过提升泵(2)与主体反应塔(8)顶部的配水槽(3)连接，所述的主体反应塔(8)内填充有填料，其特征在于，所述的主体反应塔(8)内填料底部为倒锥斗(7)，倒锥斗(7)上设置有进水口，倒锥斗(7)的底部连接排渣管；
    所述的主体反应塔(8)内填料上方设置有斜板(10)；在斜板(10)上方且位于所述的主体反应塔(8)端口处设置有分隔槽(4)和出水槽(11)；所述的分隔槽(4)由竖直的隔板均分为左右两单槽，两单槽的上端均与所述的配水槽(3)连通，分隔槽(4)的底部设有开口，该两单槽分别通过第一循环泵(5)和第二循环泵(6)接入所述倒锥斗(7)的进水口；分隔槽(4)的正对面设有出水槽(11)。
  2. 根据权利要求1所述的芬顿流化床处理装置，其特征在于，在距离倒锥斗(7)底部1/3和2/3处对称设置有两组进水口，共4个，使得混合液从两个单槽流出经第一循环泵(5)和第二循环泵(6)后均匀分流为两支。
  3. 根据权利要求1所述的芬顿流化床处理装置，其特征在于，所述的配水槽(3)顶部设有调节管(12)控制来水负荷，调节管(12)的另一端与所述的调节池(1)相连。
  4. 根据权利要求1所述的芬顿流化床处理装置，其特征在于，所述的倒锥斗(7)的锥角角度为5～60°。
  5. 根据权利要求1所述的芬顿流化床处理装置，其特征在于，所述的填料为：树脂、活性炭颗粒、建筑砂、石英砂、沸石、陶粒、皂石、砖块碎屑中的一种或一种以上，填料颗粒平均粒径0.1～3.0mm。
  6. 根据权利要求1～5任意一项所述的芬顿流化床处理装置，其特征在于，在主体反应塔(8)的填料内沿主体反应塔(8)纵向设置有若干个导流板(9)，导流板(9)将主体反应塔(8)分为若干个上升空间，导流板(9)的底边距离倒锥斗(7)上端的高度为1～4m。
  7. 一种权利要求1所述的芬顿流化床处理装置的废水处理方法，其步骤为：
    (a)在主体反应塔(8)内加入主体反应塔(8)体积10％～40％的填料颗粒；
    (b)在调节池(1)内调节进水pH，控制主体反应塔(8)内的pH为3.0～4.0；控制水量，保持主体反应塔(8)内的水流停留时间为10～30min；
    (c)调节池(1)的水经过提升泵(2)进入配水槽(3)，配水槽(3)出水进入分隔槽(4)，分别由第一循环泵(5)和第二循环泵(6)回流至倒锥斗(7)，再通过倒锥斗(7)上的进水口均匀进入主体反应塔(8)内；调节回流比，控制主体反应塔(8)内的上升流速为30～150m/h，保证导流板(9)顶部低于填料悬浮层顶部；
    (d)在分隔槽(4)的两单槽内分别加双氧水和硫酸亚铁溶液，两种药剂分别随水流经 过第一循环泵(5)和第二循环泵(6)进入倒锥斗(7)；
    (e)倒锥斗(7)内产生旋流混匀水流，与填料进行反应，再经过导流板(9)推流和分离后，上清液一部分从分隔槽(4)的底部进入分隔槽(4)的单槽内，一部分进入出水槽(11)排出；
    (f)运行一周以后，将硫酸亚铁减量50％继续运行；运行6～12个月后排渣。
  8. 根据权利要求7所述的一种芬顿流化床处理装置的废水处理方法，其特征在于，所述的步骤(a)中，填料颗粒分两次投加，初次投加填料总量的75％～85％，运行50～500h后，补加剩余的15％～25％。
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