CN112047558A - Fluorine-containing wastewater treatment device and treatment method - Google Patents
Fluorine-containing wastewater treatment device and treatment method Download PDFInfo
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- CN112047558A CN112047558A CN202010690536.6A CN202010690536A CN112047558A CN 112047558 A CN112047558 A CN 112047558A CN 202010690536 A CN202010690536 A CN 202010690536A CN 112047558 A CN112047558 A CN 112047558A
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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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/24—Treatment of water, waste water, or sewage by flotation
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- 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
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Abstract
The invention relates to a method and a device for treating fluorine-containing wastewater, wherein the method comprises the following steps: the method comprises the following steps: the method comprises the following steps of (1) enriching fluorine ions in wastewater to a certain area by using an external electrostatic field; step two: separating the wastewater in the fluorine ion-enriched area and the wastewater in the less fluorine ion area; step three: removing most of fluoride ions from the wastewater enriched with fluoride ions by using a chemical precipitation method; step four: the wastewater after the third step is processed is subjected to external electrostatic field again to enrich fluorine ions in the wastewater to a certain area; step five: separating the wastewater in the fluorine ion-enriched area and the wastewater in the less fluorine ion area again; step six: removing most of the residual fluorine ions from the wastewater enriched with fluorine ions and separated again by using a flocculation precipitation method; step seven: forcibly separating sediments, flocculates, floaters and clear liquid in the wastewater by centrifugation; the method can obviously improve the defluorination efficiency of the fluorine-containing wastewater, reduce the defluorination cost, has small occupation range and can realize the wastewater defluorination with continuous and high efficiency.
Description
Technical Field
The invention relates to the field of environmental protection and emission reduction, in particular to a fluorine-containing wastewater treatment device and a treatment method.
Background
Fluorine is one of trace elements necessary for human bodies, and the suitable fluorine mass concentration of the drinking water is 0.5-1 mg/L. When the fluorine content in the drinking water is insufficient, the drinking water is easy to suffer from dental caries; however, if drinking water with fluorine mass concentration higher than 1 mg/L for a long time, dental fluorosis will be caused; long-term drinking of water with fluorine mass concentration of 3-6 mg/L can cause fluorosis. Fluorine-containing underground water in China is widely distributed, and about 7000 thousands of people drink water with excessive fluorine content particularly in northwest arid areas, so that fluorine poisoning of different degrees is caused. In industry, wastewater discharged from industries such as fluorine-containing ore mining, metal smelting, aluminum processing, coke, glass, electronics, electroplating, chemical fertilizers, pesticides and the like often contains high-concentration fluoride, so that environmental pollution is caused.
For the fluorine-containing wastewater, most domestic production plants have no perfect treatment at present, the index of the fluorine content in the discharged wastewater does not reach the national discharge standard, and the environment on which human beings rely for survival is seriously polluted. According to the national industrial wastewater discharge standard, the concentration of fluorine ions is less than 10 mg/L; for drinking water, the fluorine ion concentration is required to be 1 mg/L or less. There are many methods for treating fluorine-containing wastewater, and methods commonly used at home and abroad are roughly classified into two types, namely a precipitation method and an adsorption method.
For high-concentration fluorine-containing industrial wastewater, a calcium salt precipitation method is generally adopted, namely lime is added into the wastewater to enable fluorine ions and calcium ions to generate CaF2 precipitate for removal. The process has the advantages of simple method, convenient treatment, low cost and the like, but has the defects of difficult standard reaching of treated effluent, slow sedimentation of sludge, difficult dehydration and the like, particularly, the produced CaF2 sediment is coated on the surface of Ca (OH)2 particles, so that the Ca (OH)2 can not be fully utilized due to low solubility of lime which is cheap.
The flocculating agent commonly used in the flocculation precipitation method of fluoride ion wastewater is aluminum salt. After the aluminum salt is added into water, the fluorine ions in the water are removed by utilizing the complexation of Al3+ and F-, the ligand exchange, physical adsorption and rolling sweeping action of the aluminum salt hydrolysis intermediate product and the finally generated Al (OH)3(am) alumen ustum on the fluorine ions. Compared with the calcium salt precipitation method, the aluminum salt flocculation precipitation method has the advantages of small dosage of medicament, large treatment capacity and capability of reaching the national discharge standard after one-time treatment; the aluminum salt flocculation precipitation method also has obvious defects, namely, the use range is small, and if the fluorine content is large, the coagulant is used in a large amount, the treatment cost is large, and the sludge amount is large.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a fluorine-containing wastewater treatment device and a treatment method, the fluorine-containing wastewater treatment device can obviously improve the fluorine removal efficiency of fluorine-containing wastewater and reduce the fluorine removal cost, and compared with the traditional large pool, the device has a small floor area and can continuously and efficiently realize the fluorine removal of wastewater.
The technical scheme of the invention is as follows:
a fluorine-containing wastewater treatment method comprises the following steps of sequentially carrying out:
the method comprises the following steps: the method comprises the following steps of (1) enriching fluorine ions in wastewater to a certain area by using an external electrostatic field;
step two: separating the wastewater in the fluorine ion-enriched area and the wastewater in the less fluorine ion area;
step three: removing most of fluoride ions from the wastewater enriched with fluoride ions by using a chemical precipitation method;
step four: the wastewater after the third step is processed is subjected to external electrostatic field again to enrich fluorine ions in the wastewater to a certain area;
step five: separating the wastewater in the fluorine ion-enriched area and the wastewater in the less fluorine ion area again;
step six: removing most of the residual fluorine ions from the wastewater enriched with fluorine ions and separated again by using a flocculation precipitation method;
step seven: the precipitate, floc, float and clear liquid in the wastewater are forcibly separated by centrifugation.
A processing device for realizing the fluorine-containing wastewater processing method comprises an anion displacement section for realizing the first step and the second step; the negative ion displacement section comprises a first cylinder made of a non-conductor; a water inlet pipe is connected above the first cylinder; the diameter of the water inlet pipe is slightly larger than that of the first cylinder; a first anode electric field is sleeved outside the first cylinder; a horn-shaped first flaring part is connected below the first cylinder; the first flaring part is a first cambered surface which is slightly inwards convex, and the joint part of the first cambered surface and the lower end of the first barrel body is in smooth transition; a first liquid receiving cylinder is arranged below the first cylinder body, the first liquid receiving cylinder is positioned in the first flared part, the diameter of the first liquid receiving cylinder is slightly smaller than that of the first cylinder body, a gap is formed between the first liquid receiving cylinder and the first cylinder body to form a first outflow opening, and a first outer flow passage is defined between the first outflow opening and the first flared part; the first cylinder is of a structure that the upper and lower diameters are larger than the diameter of the middle part and the diameter changes into continuous change, the lower end of the first cylinder is in smooth transition with the first flared part, and the upper end of the first cylinder is in smooth transition with the water inlet pipe.
A treatment device for realizing the fluorine-containing wastewater treatment method, which comprises a calcium ion precipitation section for realizing the third step to the fifth step; the calcium ion precipitation section comprises a second cylinder; the second cylinder is made of a non-conductor; the upper end of the second cylinder is connected with the first flared part; the upper part of the second cylinder and a first liquid receiving cylinder sleeved in the second cylinder form an annular first defluorination cavity in an enclosing manner; an annular defluorination cylinder is sleeved in the first defluorination cavity; the middle part of the second cylinder is recessed inwards to form a reducing part; the reducing part is a second cambered surface and is in smooth transition with the inner wall of the second cylinder body above and below the reducing part; a second liquid receiving cylinder is arranged below the reducing part; the second liquid receiving cylinder is positioned in the second cylinder body; the diameter of the second liquid receiving cylinder is slightly larger than the minimum inner diameter of the diameter-reduced part and is smaller than the diameter of the non-diameter-reduced part of the second cylinder body; a second anode electric field is sleeved outside the second cylinder below the defluorination cylinder and above the second liquid receiving cylinder; and a gap is arranged between the second liquid receiving cylinder and the diameter reducing part to form a second external flow port, and a second external flow channel is enclosed between the second liquid receiving cylinder and the non-diameter reducing part of the second cylinder body.
The fluorine removal cylinder comprises a plurality of layers of water filtering clapboards, and each water filtering clapboard comprises an outer ring, an inner ring and a fixing ring from outside to inside; a plurality of ribs are connected between the outer ring and the inner ring, and metal separation nets are fixed in other spaces between the outer ring and the inner ring; a plurality of electrostrictive sheets which deform and swing horizontally left and right under the action of voltage are uniformly arranged between the fixed ring and the inner ring; the electrostriction sheets are distributed between the fixing ring and the inner ring in a scattered manner and are connected with the fixing ring and the inner ring, and the water filtering partition plate is detachably and fixedly sleeved on the outer circumference of the first liquid receiving cylinder through the fixing ring; all electrostrictive sheets of the same water filtering clapboard synchronously swing; the corresponding outer rings of the two water filtering clapboards which are adjacent up and down are mutually abutted, and the corresponding inner rings of the two water filtering clapboards are also mutually abutted; a lime layer is filled between the metal separation screens of the upper and lower water filtering separation plates; the lime filled in the lime layer is small blocky calcium oxide, and steel grit is uniformly mixed in the lime layer; the electrostrictive sheets of the two water filtering clapboards which are adjacent up and down swing in opposite directions at the same moment, so that the two water filtering clapboards which are adjacent up and down rotate in a relative friction way.
Wherein, the device also comprises a flocculation precipitation section for realizing the sixth step; the flocculation precipitation section comprises a third cylinder; the upper end of the third cylinder is connected with the lower end of the second cylinder, and the third cylinder and the second liquid receiving cylinder enclose an annular second defluorination cavity; an annular liquid spraying pipe is arranged in the second defluorination cavity; the aluminum salt solution is conveyed by external pressurization and sprayed through a spray pipe.
A treatment device for realizing the fluorine-containing wastewater treatment method comprises a horizontal centrifugal device for realizing the seventh step; the horizontal centrifugal device comprises a centrifugal disc with a circumferential baffle and a centrifugal impeller arranged in the center of the centrifugal disc; the centrifugal disc rotates at a high speed; the rotating direction of the centrifugal impeller is opposite to that of the centrifugal disc, the rotating speed of the centrifugal impeller is lower than that of the centrifugal disc, and a plurality of gaps are uniformly and vertically formed in the circumferential baffle; each gap corresponds to a drainage plate; the drainage plate is an arc-shaped plate, one end of the drainage plate is smoothly connected with one side of the gap, the other end of the drainage plate extends out of the circumferential baffle, the convex part of the arc-shaped plate faces one side of the gap, and the flow direction of the wastewater along the circumferential baffle is from one side of the gap where the drainage plate is located to the other side of the gap relative to the movement direction of the centrifugal disc; sharpening the other side of the gap, and polishing the inner wall of the gap to a certain depth to enable the thickness of the other side of the gap to be slightly smaller than that of the side where the drainage plate is located; an annular liquid receiving groove is arranged outside the circumferential baffle; and wastewater led out by the drainage plate flows into the annular liquid receiving groove.
Wherein the centrifugal disc is a slightly concave butterfly shape as a whole; an openable slag discharge port is arranged in an annular area of the centrifugal disc close to the center; a plurality of tiny air outlets are uniformly formed in the centrifugal disc outside the slag discharge port, and pressurized air is discharged upwards through the air outlets and is mixed with the wastewater on the centrifugal disc to promote suspended matters or flocculates in the wastewater to float.
The invention has the following beneficial effects:
1. the fluorine-containing wastewater treatment device can obviously improve the fluorine removal efficiency of the fluorine-containing wastewater, has a small occupied area compared with the traditional large pool, and can continuously and efficiently realize the fluorine removal of the wastewater.
2. The invention utilizes the action of an external electric field to enrich the fluoride ions to the inner circumferential surfaces of the first cylinder and the second cylinder, and then utilizes the coanda effect to separate the fluoride ion-enriched wastewater from the other part of wastewater with greatly reduced fluoride ions for respective treatment, thereby having the most remarkable advantage of greatly reducing the amount of wastewater to be treated, and realizing equal or even better fluoride removal effect by only a small amount of additives compared with the prior art; the method for enriching the fluorine ions and separating the fluorine ion-containing wastewater is simple, utilizes the structural characteristics, and has simple and convenient operation and low cost.
3. The defluorination cylinder adopts a multi-layer water filtering partition plate structure, is matched with the deformation function of the electrostriction sheet under the inverse piezoelectric effect, can simply and controllably realize the rapid and repeated relative rotation of each layer of water filtering partition plate of the defluorination cylinder, and is matched with the steel grit mixed in the lime, so that the repeated grinding of the lime can be realized, the lime can be continuously granulated in a small way, the reaction area of the lime and fluorine ions is increased, the lime consumption time is prolonged, and the utilization rate of the lime is improved; moreover, due to the grinding effect in the process, even if the produced CaF2 precipitate is coated on the surface of the Ca (OH)2 particles, the Ca (OH)2 particles can be quickly ground and fall off, so that the problem that the generated CaF2 precipitate is coated on the surface of the Ca (OH)2 particles and cannot be fully utilized can be solved; but also can increase waste water and pass the required time and the route of a fluorine removal section of thick bamboo, improve the reaction rate, simultaneously because the inside is dynamic of a fluorine removal section of thick bamboo, the difficult condition that takes place to block up consequently can ensure the stable permanent operation of device to the convenience is dismantled to a fluorine removal section of thick bamboo, only needs the inside lime of periodic replacement can use repeatedly, kills a lot of.
4. The diameter-reducing structure and the second anode electric field are arranged at the position, below the fluorine removal cylinder, of the second cylinder, the wastewater enriched with fluorine ions and the part removed with the fluorine ions after the reaction of the fluorine removal cylinder are separated again by utilizing the coanda effect and the solid inertia, and the structure is designed skillfully, so that stable, efficient and energy-saving separation is realized.
5. The invention leads the waste water which is separated again and is rich in fluorinion to pass through a third cylinder body, fully reacts and utilizes the waste water which is rich in fluorinion in a way of spraying aluminum salt under pressure, and flocculate is formed by the complexation of Al3+ and F-, intermediate products of aluminum salt hydrolysis and Al (OH)3(am) which is finally generated; the defluorination method can make full use of the high efficiency, can quickly reach the national discharge standard, and can improve the reaction efficiency and meet the requirement of full reaction in the falling process of the fluoride ion-enriched wastewater because the aluminum salt is sprayed under pressure.
6. The horizontal centrifugal device provided by the invention utilizes the characteristics of different specific gravities of different substances in the centrifugal process, meanwhile, the structure of the centrifugal device is designed in a targeted manner, and the separation of sediments, flocculates, floaters and water is simply and conveniently realized automatically by utilizing the Keynda effect to be matched with the characteristics in the centrifugal process, so that the traditional natural sedimentation method is replaced, and the time consumed by the method is more.
Drawings
FIG. 1 is a schematic diagram of the apparatus of the present invention;
FIG. 2 is a schematic cross-sectional view of a defluorination cartridge;
FIG. 3 is a schematic view of a water filtration partition;
fig. 4 is a schematic top view of a horizontal centrifuge.
The reference numbers in the figures denote:
1-negative ion displacement section, 11-first cylinder, 12-water inlet pipe, 13-first anode electric field, 14-first flared section, 15-first liquid receiving cylinder, 16-first outflow port, 17-first outer flow channel, 2-calcium ion precipitation section, 21-second cylinder, 211-reduced diameter section, 22-first defluorination cavity, 23-defluorination cylinder, 230-water filtration clapboard, 231-outer ring, 232-inner ring, 233-fixing ring, 234-rib, 235-metal separation net, 236-electrostriction sheet, 24-second liquid receiving cylinder, 25-second anode electric field, 26-second outflow port, 27-second outer flow channel, 3-flocculation precipitation section, 31-third cylinder, 32-second defluorination cavity, 33-liquid spraying pipe, 34-a drainage switch, a 4-horizontal centrifugal device, 41-a centrifugal disc, 411-a circumferential baffle, 412-a gap, 413-a flow guide plate, 42-a centrifugal impeller, 43-a slag discharge port, 44-an air outlet hole and 45-an annular liquid receiving groove.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments.
Referring to fig. 1, a fluorine-containing wastewater treatment device comprises an anion displacement section 1, a calcium ion precipitation section 2, a flocculation precipitation section 3 and a horizontal centrifugal device 4 which are sequentially arranged from top to bottom; the negative ion displacement section 1 comprises a first cylinder 11 made of a non-conductor such as PVC and other plastics; a water inlet pipe 12 is connected above the first cylinder 11; the diameter of the water inlet pipe 12 is slightly larger than that of the first cylinder 11 so as to ensure that the inlet water completely covers the transverse section of the first cylinder 11; a first anode electric field 13, preferably an electrostatic field, is sleeved outside the first cylinder 11; the first anode electric field 13 attracts negative ions, particularly fluorine ions, in the wastewater flowing through the first cylinder 11 to move towards the inner circumferential surface of the first cylinder 11; a horn-shaped first flaring part 14 is connected to the lower part of the first cylinder 11; the first flared part 14 is a first cambered surface which is slightly inward convex, and the joint part of the first cambered surface and the lower end of the first cylinder 11 is in smooth transition; a first liquid receiving cylinder 15 is further arranged below the first cylinder 11, the first liquid receiving cylinder 15 is located in the first flared part 14, the diameter of the first liquid receiving cylinder 15 is slightly smaller than that of the first cylinder 11, a gap is formed between the first liquid receiving cylinder 15 and the first cylinder 11 to form a first outer flow port 16, and a first outer flow channel 17 is defined between the first outer flow port and the first flared part 14; in the downward flowing process of the wastewater, the water flow close to the inner circumferential surface of the first cylinder 11 is rich in fluorine ions, and the water flow is tightly attached to the first cambered surface under the action of the coanda effect, passes through the first outflow port 16, enters the first outflow channel 17 and continues to flow downward; the rest water flow contains less fluorine ions after the action of the electric field, the water flow directly falls into the first liquid receiving cylinder 15 downwards and continues to flow downwards, the first cylinder 11 can be a structure with the upper and lower diameters larger than the diameter of the middle part and the diameter change into continuous change, the lower end of the first cylinder has smooth transition with the first flared part 14, and the upper end of the first cylinder has smooth transition with the water inlet pipe 12.
The calcium ion precipitation section 2 comprises a second cylinder 21; the second cylinder 21 is made of a non-conductor such as PVC or other plastics; the upper end of the second cylinder 21 is connected with the first flared part 14; the upper part of the second cylinder 21 and the first liquid receiving cylinder 15 enclose to form an annular first defluorination cavity 22; an annular fluorine removal cylinder 23 is sleeved in the first fluorine removal cavity 22;
referring to fig. 2 and 3, the fluorine removing cartridge 23 comprises a multi-layer water filtering baffle 230, wherein the water filtering baffle 230 comprises an outer ring 231, an inner ring 232 and a fixing ring 233 from outside to inside; a plurality of ribs 234 are connected between the outer ring 231 and the inner ring 232, and metal separation nets 235 are fixed in other spaces between the outer ring 231 and the inner ring 232; a plurality of electrostrictive sheets 236 which deform and swing horizontally left and right under the action of voltage are uniformly arranged between the fixed ring 233 and the inner ring 232; the electrostrictive sheets 236 are distributed between the fixing ring 233 and the inner ring 232 in a scattered manner and are connected with the fixing ring 233 and the inner ring 232, and the water filtering baffle plate 230 is detachably fixed and fixedly arranged on the outer circumference of the first liquid receiving cylinder 15 through the fixing ring 233; the electrostrictive sheets 236 of the same water filtering partition 230 synchronously swing; the corresponding outer rings 231 of the two water filtering clapboards 230 which are adjacent up and down are mutually abutted, and the corresponding inner rings 232 are also mutually abutted; the upper and lower water filtering clapboards 230 are filled with a lime layer between the metal separating nets 235; the lime filled in the lime layer is small blocky calcium oxide, and steel grit is uniformly mixed in the lime layer; the electrostrictive sheets 236 of the two vertically adjacent water filtering separators 230 swing in opposite directions at the same time, so that the two vertically adjacent water filtering separators 230 rotate in a relative friction manner.
The middle part of the second cylinder 21 is concave inwards to form a reducing part 211; the reducing part 211 is a second cambered surface and is in smooth transition with the inner wall of the second cylinder 21 above and below the reducing part;
a second liquid receiving cylinder 24 is arranged below the diameter reducing part 211; the second liquid receiving cylinder 24 is positioned in the second cylinder body 21; the diameter of the second liquid receiving cylinder 24 is slightly larger than the minimum inner diameter of the diameter reducing part 211 and is smaller than the diameter of the part of the second cylinder 21 which is not diameter reduced;
a second anode electric field 25, preferably an electrostatic field, is sleeved outside the second cylinder body 21 below the fluorine removing cylinder 23 and above the second liquid receiving cylinder 24.
A gap is arranged between the second liquid receiving cylinder 24 and the diameter reducing part 211 to form a second external flow port 26, and a second external flow channel 27 is enclosed between the second liquid receiving cylinder 24 and the non-diameter reducing part of the second cylinder body 21; the water flow passing through the first outer flow channel 17 continues to flow downwards after being defluorinated by the defluorination cylinder 23, the water flow close to the inner circumferential surface of the second cylinder 21 is rich in fluoride ions under the action of the second anode electric field 25, and the water flow closely adheres to the second cambered surface under the action of the coanda effect, passes through the second outer flow port 26, enters the second outer flow channel 27 and continues to flow downwards; the rest water flow contains less fluorine ions after the action of the electric field, the water flow directly falls into the second liquid receiving cylinder 24 downwards and continues to flow downwards, and the water flow left by the first liquid receiving cylinder 15 also falls into the second liquid receiving cylinder 24; in addition, fluoride ions in the water flow react with lime powder in the fluoride removal cylinder 23 to generate calcium fluoride to precipitate or float, most of the calcium fluoride directly falls into the second liquid receiving cylinder 24, and a small part of the calcium fluoride slides down along or close to the reducing part 211, and the middle part of the reducing part 211 protrudes inwards, so that the calcium fluoride in a solid state is not influenced by the coanda effect, and is easily separated from the water flow tightly attached to the second cambered surface under the action of self inertia and falls into the second liquid receiving cylinder 24; therefore, the reduced diameter portion 211 and the second liquid receiving cylinder 24 function to allow most of the residual fluorine ions to flow down along the first outer flow channel 17 and most of the calcium fluoride generated by the reaction to flow down along the second liquid receiving cylinder 24.
The flocculation precipitation section 3 comprises a third cylinder 31; the upper end of the third cylinder 31 is connected with the lower end of the second cylinder 21, and the third cylinder 31 and the second liquid receiving cylinder 24 enclose an annular second defluorination cavity 32; an annular liquid spraying pipe 33 is arranged in the second defluorination cavity 32; the aluminum salt solution is conveyed by external pressurization and sprayed through a spray pipe 33, the spraying direction can be upward or downward, but the spraying range is large, and at least the second defluorination cavity 32 is covered; after the aluminum salt is added into water, the fluorine ions in the water are removed by utilizing the complexation of Al3+ and F-and the ligand exchange, physical adsorption and rolling sweeping effects of aluminum salt hydrolysis intermediate products and finally generated Al (OH)3(am) alumen blossoms on the fluorine ions.
Through the first waste water that connects a liquid section of thick bamboo 15, a second and connect a liquid section of thick bamboo 24 and a third barrel 31 and leave to assemble in third barrel 31 below, the department of assembling is provided with an open closed drainage switch 34, drainage switch 34 is an solenoid valve, can regularly open and close or according to the weight switching of the waste water of assembling, when the weight of the waste water of assembling surpassed predetermined threshold, and the solenoid valve is automatic to be opened and is discharged waste water downwards, and waste water discharges when being less than predetermined threshold, and the solenoid valve is automatic closed again.
Referring to fig. 1 and 4, the horizontal centrifugal device 4 includes a centrifugal disk 41 having a circumferential baffle 411 and a centrifugal impeller 42 disposed centrally on the centrifugal disk 41; the centrifugal disc 41 rotates at a high speed; the rotation direction of the centrifugal impeller 42 is opposite to that of the centrifugal disc 41, and the rotation speed is lower than that of the centrifugal disc 41, and the main function of the centrifugal impeller is to push the wastewater outwards so as to ensure that the wastewater can be attached to the circumferential baffle 411; the centrifugal disc 41 is a slightly concave butterfly shape as a whole; an openable slag discharge port 43 is arranged in an annular area of the centrifugal disc 41 close to the center; a plurality of tiny air outlet holes 44 are uniformly arranged outside the slag outlet 43 on the centrifugal disc 41, and slightly pressurized gas is discharged upwards through the air outlet holes 44 and is mixed with the wastewater on the centrifugal disc 41, so that suspended matters or flocculates in the wastewater are promoted to float on the water surface; a plurality of gaps 412 are uniformly and vertically formed in the circumferential baffle 411; each slit 412 corresponds to a drainage plate 413; the flow guide plate 413 is an arc-shaped plate, one end of the flow guide plate 413 is smoothly connected with one side of the gap 412, the other end of the flow guide plate extends out of the circumferential baffle 411, the arc-shaped convex part of the flow guide plate faces one side of the gap 412, and the flowing direction of the waste water along the circumferential baffle 411 is from one side of the gap 412 where the flow guide plate 413 is located to the other side of the gap 412 relative to the moving direction of the centrifugal disc 41; meanwhile, the other side of the gap 412 is sharpened, and the inner wall of the position is ground to a certain depth, so that the thickness 411 of the other side of the gap 412 is slightly smaller than that of the side of the drainage plate 413. The bottom of the gap 412 is slightly higher than the bottom of the circumferential baffle 411, so that the settling of suspended particles is promoted during the centrifugal process, and the settled suspended particles are located below the gap 412 and are prevented from being extruded by the centrifugal force. An annular liquid receiving groove 45 is arranged outside the circumferential baffle 411; the wastewater led out by the drainage plate 413 flows into the annular liquid receiving groove 45, the fluorine content in the annular liquid receiving groove 45 is detected at regular time, and if the wastewater meets the discharge or utilization requirement, the wastewater can enter the next procedure for discharge or further treatment; if the fluorine content does not meet the requirement, the wastewater in the annular liquid receiving tank 45 can be pumped into the second cylinder 21 or the third cylinder 31 again by using a water pump, if the wastewater is pumped into the second cylinder 21, the wastewater is pumped into the fluorine removing cylinder 23, and if the wastewater is pumped into the third cylinder 31, the wastewater is pumped into the fluorine removing cylinder 33.
The working principle of the invention is as follows:
fluorine-containing wastewater flows downwards into the first cylinder 11 through the water inlet pipe 12, under the action of the first anode electric field 13, fluorine ions in the wastewater are gathered towards the inner circumferential surface of the first cylinder 11, the wastewater gathered with the fluorine ions flows downwards along the inner wall of the first cylinder 11 under the action of the coanda effect, enters the first fluorine removing cavity 22 through the first outflow port 16 and the first outer flow channel 17, and the rest wastewater falls downwards into the first liquid receiving cylinder 15 to continue to fall;
wastewater entering the first defluorination cavity 22 passes through the defluorination cylinder 23 and is precipitated with calcium ions to generate CaF2 for removal, and in the process, the electrostrictive sheet 236 on each layer of water filtering partition plate 230 synchronously swings left and right, so that the water filtering partition plate 230 rotates left and right in a reciprocating manner at a certain angle; the rotation directions of the adjacent water filtering clapboards 230 at the same time are opposite, so that mutual friction is realized between the water filtering clapboards 230, and the limestone and the steel grit are mutually rubbed due to the fact that the limestone and the steel grit are filled in the water filtering clapboards, so that the lime can be repeatedly ground, the lime can be continuously granulated in a small mode, the reaction area of the lime and fluorine ions is increased, the lime consumption time is prolonged, and the lime utilization rate is improved; moreover, due to the grinding effect in the process, even if the produced CaF2 precipitate is coated on the surface of the Ca (OH)2 particles, the Ca (OH)2 particles can be quickly ground and fall off, so that the problem that the generated CaF2 precipitate is coated on the surface of the Ca (OH)2 particles and cannot be fully utilized can be solved; but also can increase waste water and pass the required time and the route of a fluorine removal section of thick bamboo, improve the reaction rate, simultaneously because the inside is dynamic of a fluorine removal section of thick bamboo, the difficult condition that takes place to block up consequently can ensure the stable permanent operation of device to the convenience is dismantled to a fluorine removal section of thick bamboo, only needs the inside lime of periodic replacement can use repeatedly, kills a lot of.
Most of fluoride ions in the wastewater passing through the fluorine removal cylinder 23 are removed, the fallen wastewater passes through the second anode electric field 25 again, so that the fluoride ions participating in the wastewater are collected on the inner wall of the second cylinder 21 again, the wastewater close to the inner wall of the second cylinder 21 flows downwards along the reduced diameter part 211 under the action of the coanda effect, CaF2 precipitate generated in the wastewater does not or less flow along the reduced diameter part 211 under the action of inertia, but jumps into the second liquid receiving cylinder 24 under the action of inertia, and the wastewater falling into the first liquid receiving cylinder 15 also falls into the second liquid receiving cylinder 24 to continue downwards.
The wastewater flowing downwards along the diameter-reduced part 211 enters the second defluorination cavity 32 through the second external flow port 26 and the second external flow channel 27, and the wastewater reacts with aluminum salt sprayed out by the liquid spraying pipe 33 under pressure in the second defluorination cavity 32 to remove the fluorine ions in the water by utilizing the complexation of Al3+ and F-, the aluminum salt hydrolysis intermediate product and the ligand exchange, physical adsorption and rolling sweeping effects of Al (OH)3(am) alum flowers on the fluorine ions finally generated; if the reaction is not complete, the wastewater continues to react while continuing to flow downwards.
In the process that all the wastewater is mixed and falls into the middle of the centrifugal disc 41 below the second defluorination cavity 32 and is dispersed and thrown out outwards under the action of the centrifugal impeller 42, because the centrifugal disc 41 is arc-shaped, heavier sediments are mainly accumulated at the bottom of the arc, and the slag discharge port 43 is opened at regular time or quantitatively for discharging; lighter liquid flows against the circumferential baffle 411 under the action of centrifugal force, and due to the high-speed rotation of the centrifugal disc 41, the relative speed linear velocity of the circumferential baffle 411 and the wastewater is higher, and because the relative speed is realized by the rotation of the circumferential baffle 411, the radial extrusion force of the wastewater is not higher, and the wastewater is not easily extruded from the gap 412; before the wastewater flows to the circumferential baffle 411, the air overflowed from the air outlet holes 44 combines with the wastewater, in particular with flocs in the wastewater, causing the flocs to float upwards;
the wastewater flows along the circumference of the circumferential baffle 411, and according to the coanda effect, the liquid directly contacted with the inner wall of the circumferential baffle 411 is guided by the drainage plate 413 to flow out of the gap 412; the solid precipitate will directly cross the gap 412 under the inertia and self-size constraint; suspended matter or floes, primarily floes, due to not directly contacting the inner wall of the circumferential baffle 411, will also pass over the gap 412 under the influence of inertia, and under the partial entrainment of liquid not directly contacting the inner wall; the end part of the inner wall at the other side of the gap 412 is cut outwards and polished to a certain depth, and the depth counteracts the outward displacement of the solid sediment or flocculate within the width range of the gap 412 under the action of centrifugal force, so that the solid sediment, the flocculate and the floating object can not or mostly can not pass through the gap 412, and the fine separation of the wastewater is realized; furthermore, the bottom of the gap 412 is slightly higher than the bottom of the circumferential baffle 411, so that the settling of suspended particles is promoted during the centrifugation, and the settled suspended particles are located below the gap 412 and are prevented from being squeezed out by the centrifugal force.
The wastewater led out by the drainage plate 413 flows into the annular liquid receiving groove 45, the fluorine content in the annular liquid receiving groove 45 is detected at regular time, and if the wastewater meets the discharge or utilization requirement, the wastewater can enter the next procedure for discharge or further treatment; if the fluorine content does not meet the requirement, the wastewater in the annular liquid receiving tank 45 can be pumped into the second cylinder 21 or the third cylinder 31 again by using a water pump, if the wastewater is pumped into the second cylinder 21, the wastewater is pumped into the fluorine removing cylinder 23, and if the wastewater is pumped into the third cylinder 31, the wastewater is pumped into the fluorine removing cylinder 33.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (7)
1. A method for treating fluorine-containing wastewater is characterized by comprising the following steps: comprises the following steps which are carried out in sequence:
the method comprises the following steps: the method comprises the following steps of (1) enriching fluorine ions in wastewater to a certain area by using an external electrostatic field;
step two: separating the wastewater in the fluorine ion-enriched area and the wastewater in the less fluorine ion area;
step three: removing most of fluoride ions from the wastewater enriched with fluoride ions by using a chemical precipitation method;
step four: the wastewater after the third step is processed is subjected to external electrostatic field again to enrich fluorine ions in the wastewater to a certain area;
step five: separating the wastewater in the fluorine ion-enriched area and the wastewater in the less fluorine ion area again;
step six: removing most of the residual fluorine ions from the wastewater enriched with fluorine ions and separated again by using a flocculation precipitation method;
step seven: the precipitate, floc, float and clear liquid in the wastewater are forcibly separated by centrifugation.
2. A treatment apparatus for carrying out the method of treating fluorine-containing wastewater according to claim 1, characterized in that: comprises a negative ion displacement section (1) for realizing the first step and the second step; the negative ion displacement section (1) comprises a first cylinder (11) made of a non-conductor; a water inlet pipe (12) is connected above the first cylinder (11); the diameter of the water inlet pipe (12) is slightly larger than that of the first cylinder (11); a first anode electric field (13) is sleeved outside the first cylinder (11); a trumpet-shaped first flaring part (14) is connected below the first cylinder (11); the first flaring part (14) is a first cambered surface which is slightly inwards convex, and the joint part of the first cambered surface and the lower end of the first barrel (11) is in smooth transition; a first liquid receiving cylinder (15) is further arranged below the first cylinder body (11), the first liquid receiving cylinder (15) is located in the first flared part (14), the diameter of the first liquid receiving cylinder (15) is slightly smaller than that of the first cylinder body (11), a gap is formed between the first liquid receiving cylinder (15) and the first cylinder body (11) to form a first outflow opening (16), and a first outer flow passage (17) is defined between the first outflow opening and the first flared part (14); the upper and lower diameters of the first cylinder (11) are larger than the diameter of the middle part, the diameter changes into a continuous change structure, the lower end of the first cylinder is in smooth transition with the first flared part (14), and the upper end of the first cylinder is in smooth transition with the water inlet pipe (12).
3. A treatment apparatus for carrying out the method of treating fluorine-containing wastewater according to claim 1, characterized in that: comprises a calcium ion precipitation section (2) for realizing the steps three to five; the calcium ion precipitation section (2) comprises a second cylinder body (21); the second cylinder (21) is made of a non-conductor; the upper end of the second cylinder (21) is connected with the first flared part (14); the upper part of the second cylinder body (21) and a first liquid receiving cylinder (15) sleeved in the second cylinder body (21) form an annular first defluorination cavity (22) in a surrounding manner; an annular fluorine removal cylinder (23) is sleeved in the first fluorine removal cavity (22); the middle part of the second cylinder (21) is recessed inwards to form a reducing part (211); the reducing part (211) is a second cambered surface and is in smooth transition with the inner wall of the second cylinder (21) above and below the reducing part; a second liquid receiving cylinder (24) is arranged below the reducing part (211); the second liquid receiving cylinder (24) is positioned in the second cylinder body (21); the diameter of the second liquid receiving cylinder (24) is slightly larger than the minimum inner diameter of the diameter reducing part (211) and is smaller than the diameter of the non-diameter reducing part of the second cylinder body (21); a second anode electric field (25) is sleeved outside the second cylinder body (21) below the fluorine removal cylinder (23) and above the second liquid receiving cylinder (24); a gap is arranged between the second liquid receiving cylinder (24) and the diameter reducing part (211) to form a second external flow port (26), and a second external flow channel (27) is enclosed between the second liquid receiving cylinder (24) and the non-diameter reducing part of the second cylinder body (21).
4. The fluorine-containing wastewater treatment apparatus according to claim 3, wherein: the fluorine removal cylinder (23) comprises a multi-layer water filtering partition plate (230), and the water filtering partition plate (230) comprises an outer ring (231), an inner ring (232) and a fixing ring (233) from outside to inside; a plurality of ribs (234) are connected between the outer ring (231) and the inner ring (232), and metal separation nets (235) are fixed in other spaces between the outer ring (231) and the inner ring (232); a plurality of electrostrictive sheets (236) which deform horizontally and swing left and right under the action of voltage are uniformly arranged between the fixed ring (233) and the inner ring (232); the electrostrictive sheets (236) are distributed between the fixing ring (233) and the inner ring (232) in a scattered manner and are connected with the fixing ring (233) and the inner ring (232), and the water filtering partition plate (230) is detachably and fixedly sleeved on the outer circumference of the first liquid receiving cylinder (15) through the fixing ring (233); all electrostrictive sheets (236) of the same water filtering clapboard (230) synchronously swing; the corresponding outer rings (231) of the two water filtering clapboards (230) which are adjacent up and down are mutually abutted, and the corresponding inner rings (232) are also mutually abutted; a lime layer is filled between the metal separation screens (235) of the upper and lower water filtering partition plates (230); the lime filled in the lime layer is small blocky calcium oxide, and steel grit is uniformly mixed in the lime layer; the electrostrictive sheets (236) of the two water filtering clapboards (230) which are adjacent up and down swing in opposite directions at the same moment, so that the two water filtering clapboards (230) which are adjacent up and down rotate in a relative friction way.
5. The fluorine-containing wastewater treatment apparatus according to claim 4, wherein: also comprises a flocculation precipitation section (3); the flocculation precipitation section (3) comprises a third cylinder (31); the upper end of the third cylinder (31) is connected with the lower end of the second cylinder (21), and the third cylinder (31) and the second liquid receiving cylinder (24) enclose to form an annular second defluorination cavity (32); an annular liquid spraying pipe (33) is arranged in the second defluorination cavity (32); the aluminum salt solution is delivered by external pressurization and sprayed through a spray pipe (33).
6. A treatment apparatus for carrying out the method of treating fluorine-containing wastewater according to claim 1, characterized in that: comprises a horizontal centrifugal device (4) for realizing the step seven; the horizontal centrifugal device (4) comprises a centrifugal disc (41) with a circumferential baffle (411) and a centrifugal impeller (42) arranged in the center of the centrifugal disc (41); the centrifugal disc (41) rotates at a high speed; the rotating direction of the centrifugal impeller (42) is opposite to that of the centrifugal disc (41), the rotating speed of the centrifugal impeller is lower than that of the centrifugal disc (41), and a plurality of gaps (412) are uniformly and vertically formed in the circumferential baffle (411); each slit (412) corresponds to a drainage plate (413); the flow guide plate (413) is an arc-shaped plate, one end of the flow guide plate is smoothly connected with one side of the gap (412), the other end of the flow guide plate extends out of the circumferential baffle (411), the arc-shaped convex part of the flow guide plate faces one side of the gap (412), and the flow direction of the wastewater along the circumferential baffle (411) is the other side of the gap (412) from one side of the gap (412) where the flow guide plate (413) is located relative to the movement direction of the centrifugal disc (41); the other side of the gap (412) is sharpened, and the inner wall of the gap is ground to a certain depth, so that the thickness (411) of the other side of the gap (412) is slightly smaller than that of one side of the drainage plate (413); an annular liquid receiving groove (45) is arranged outside the circumferential baffle (411); the wastewater led out by the drainage plate (413) flows into the annular liquid receiving groove (45).
7. The fluorine-containing wastewater treatment apparatus according to claim 6, wherein: the centrifugal disc (41) is a slightly concave butterfly shape as a whole; an openable slag discharge port (43) is arranged in an annular area of the centrifugal disc (41) close to the center; a plurality of tiny air outlet holes (44) are uniformly formed in the centrifugal disc (41) outside the slag outlet (43), and pressurized gas is discharged upwards through the air outlet holes (44) and is mixed with the wastewater on the centrifugal disc (41) to promote suspended matters or flocculates in the wastewater to float.
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