CN106630084B - Method and system for treating high-fluorine and high-hardness wastewater by two-stage two-phase fluidized bed self-crystallization - Google Patents
Method and system for treating high-fluorine and high-hardness wastewater by two-stage two-phase fluidized bed self-crystallization Download PDFInfo
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a method and a system for treating high-fluorine and high-hardness wastewater by two-stage two-phase fluidized bed self-crystallization, wherein the method comprises the following steps: two self-crystallizing fluidized bed reactors: respectively referred to as a first-stage reactor and a second-stage reactor; the device comprises a reagent A feeding device, a reagent B feeding device, a primary material pool and a secondary material pool; wherein, the raw water pool is connected with the water inlet of the primary reactor through a water inlet pump by a water inlet pipeline; the reagent A feeding device is connected with a feeding port of the primary reactor through a reagent A feeding pipeline; the deslagging port of the primary reactor is connected with the primary material pool through a sludge discharging pipe of the primary reactor; the water outlet of the primary reactor is connected with the water inlet of the secondary reactor through a primary water outlet pipeline; the medicament B feeding device is connected with a medicament feeding port of the secondary reactor through a medicament B feeding pipeline; the deslagging port of the secondary reactor is connected with the secondary material pool through a sludge discharge pipe of the secondary reactor; the water outlet of the secondary reactor is connected with the recovery device through a secondary water outlet pipeline.
Description
Technical Field
The invention relates to a method and a system for treating high-fluorine and high-hardness wastewater by two-stage two-phase fluidized bed self-crystallization, and belongs to the technical field of wastewater treatment.
Background
In the field of wastewater treatment, a method of precipitating a poorly soluble salt by adding a chemical substance to wastewater to react the chemical substance with some of the dissolved substances, is called a chemical precipitation method. The formation of the precipitate goes through a process of occurrence and development from none to none, small to large, which is very complicated.
Briefly, the process of precipitate formation includes both nucleation (nucleation) and growth of precipitate particles.
(1) Nucleation-homogeneous nucleation or heterogeneous nucleation, i.e.: the textured ion is nucleated homogeneously under the action of static electricity to form ion pairs, and the ion pairs form ion aggregates again; or the heterogeneous nucleation of the constitutive crystal ions under the induction effect directly forms ion aggregates, and then the ion aggregates formed by the homogeneous nucleation or heterogeneous nucleation form small grains again;
(2) Growth of precipitated particles (or growth of nuclei) -formation of crystalline or amorphous precipitates, i.e.: the small nuclei form small precipitated particles, which then form crystalline precipitates by directional alignment or amorphous precipitates by agglomeration.
The conventional chemical precipitation method for removing fluorine and hardness is to convert fluorine ions, calcium ions and magnesium ions into calcium fluoride, calcium carbonate and magnesium hydroxide precipitates by using a chemical precipitation principle (solubility product principle), but the process generates precipitates, which are usually amorphous precipitates formed by loosely gathering a plurality of tiny precipitation particles, the arrangement of the precipitation particles is disordered, and the precipitation particles often contain a large amount of moisture and other impurities, so the precipitation particles are loose flocculent precipitates, the whole precipitation volume is large, and the process is often required to be provided with a coagulation, precipitation or clarification process. In the traditional precipitation process, excessive measures such as dosing and coagulant adding are adopted for accelerating precipitation, and impurities of the sludge are increased, so that the precipitated sludge has no recycling value, the difficulty of sludge treatment is increased, the sludge is large in volume and high in water content, and the sludge is difficult to treat separately or even more than water treatment.
Because the internal ions of the crystal form sediment are regularly arranged, the structure is compact, if the sediment result is the crystal form sediment, the sediment efficiency can be greatly improved, and the method has the advantages that: the crystal form sediment is compact and easy to sediment to the bottom of the tank, the coagulation agent is not required to be added, the volume of the sludge is greatly reduced, the water content is low, and the recovery and the final disposal are easy. In recent years, the technology of crystallization-induced precipitation has been developed rapidly, which uses crystallization-induced as a principle and combines a fluidized bed or packed bed reactor form, wherein a carrier or a packing is required to be preset in a crystallization reactor as a seed crystal, so that substances to be removed undergo crystallization-induced reaction on the seed crystal, thereby being deposited on the seed crystal, and then the treatment purpose is achieved through bottom sludge discharge. The core principle of the induced crystallization is: heterogeneous nucleation under induction, directional alignment growth and crystal form precipitation. The seed crystal has the functions of: due to the presence of the seed crystal, the activation energy of the precipitation reaction is reduced, so that the precipitation substance with lower saturation in the solution can be subjected to the precipitation reaction on the surface of the seed crystal to grow in a crystal form. In order to realize induced crystallization, the supersaturation degree of the textured ion of the precipitate is avoided as much as possible so as to avoid spontaneous nucleation of calcium carbonate or calcium fluoride, and the fine crystals cannot adhere to the surface of the seed crystal and can flow out of the reactor along with effluent water, so that the turbidity of the effluent water is increased.
At present, the high-fluorine high-hardness wastewater is treated by an induced crystallization precipitation technology, mainly based on an induced crystallization principle, for example, the following steps:
(1) Test study of high hardness Water with pelletization reactor, gu Yanmei, xu Hang, sun Yuchen, and the like, civil construction and environmental engineering, vol.37, no.3, 2015. The techniques used herein are: the fluidized bed reactor is adopted, fine sand with a certain particle size is used as seed crystals, calcium carbonate formed in the reaction is continuously adsorbed on the surface of the fine sand in the operation process, the weight of the fine sand is gradually increased, the balance of the fluidized bed state is broken, sand and stone filler gradually sinks at the bottom of the reactor, at the moment, the sand and stone filler is invalid, and the invalid filler is required to be taken out and replaced by new filler. The test has good effect under the conditions that the pH value is more than 12, the particle size of the sand and stone filler is 0.2-0.5mm, and the like, the generated calcium carbonate crystal is attached to the surface of the fine sand filler, and the calcium carbonate crystal attached to the surface of the filler reaches saturation after running for about 15 days, so that the sunken filler is required to be taken out and replaced by a new filler.
(2) Fluidized bed crystallization process for treating high concentration fluorine-containing wastewater, li Chengwen, university of south and middle school, environmental engineering treatises, 2011. The method is characterized in that the method adopts the induced crystallization as a principle, adopts a fluidized bed process to treat fluorine-containing wastewater, adds calcium fluoride crystal seeds into the fluidized bed in advance, and then allows the wastewater and calcium liquid to enter the fluidized bed so as to enable the surface heterogeneous nucleation growth of fluorine ions and calcium ion crystal seeds. The PH=6-8 of the effluent, the turbidity of the effluent is controlled below 50NTU, and the fluorine recovery rate is up to 96%. The produced calcium fluoride product has uniform granularity and average grain diameter of 100 microns, and can be used as fluorite grade calcium fluoride product.
(3) Research on softening water and defluorination by a carrier-induced precipitation crystallization method, chen Ping, university of western construction science and technology, environmental engineering doctor paper, 2004. The quartz sand induced CaCO was systematically investigated herein 3 Kinetics, thermodynamics and induction mechanism of precipitation reaction, quartz sand induced precipitation crystallization softening water, and quartz sand induced CaF 2 Crystallization defluorination and its induction mechanism.
(4) The DHV company in the Netherlands successfully realizes the industrialization of the fluidized bed crystallization technology, adopts an induced crystallization method, uses calcium chloride as a defluorination precipitant, and needs to independently add alkali to adjust the pH of wastewater to be neutral before the reaction; the calcium removing precipitant is sodium hydroxide; seed crystals, typically quartz sand, need to be constantly added before and during operation.
Liu Weirui A "self-crystallization softening process for treating concentrated brine" is proposed in "research on high-salt wastewater treatment by high-efficiency crystallization and hardening removal technology" (university of inner Mongolia, environmental engineering thesis, 2014). The process is suitable for removing the hardness of RO concentrated water with higher calcium and magnesium hardness and higher alkalinity, and the typical operation conditions are as follows: the precipitant is NaOH to generate precipitate CaCO 3 、Mg(OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the The crystallization reactor takes stirring as mixed power; taking pH as a main crystallization control parameter, the pH of the decalcification crystallization reactor is=9.5-10.2 (preferably 9.8-10.0), and the pH of the decalcification crystallization reactor is=11-11.5.
The patents related to defluorination and softening of waste water are fewer and are different from or similar to the invention, and the patents are specifically as follows:
(1) Chinese patent CN101941752a discloses a method and apparatus for treating fluorine-containing wastewater. The invention provides a method and a device for treating fluorine-containing wastewater, which take a solid-liquid two-phase fluidized bed as a crystallization reactor, add a certain amount of calcium fluoride crystal seeds into the reactor, send the fluorine-containing wastewater and a calcium-containing precipitant into a solid-liquid fluidized bed treatment device according to the reaction proportion, precipitate fluorine ions on the surface of the calcium fluoride crystal seeds, recover sandy calcium fluoride precipitation sludge obtained after sedimentation, and discharge the primary treatment water reaching the standard after further coagulation sedimentation. The method can precipitate most of fluoride ions in the crystallization and precipitation process of the fluidized bed, and the produced sandy calcium fluoride has low water content and high calcium fluoride content and can be used as fluorine resources for recycling; the flocculant consumption is small in the coagulation sedimentation process of the primary treatment water, and the sludge production amount is small, so that the comprehensive cost of wastewater treatment is low.
(2) Chinese patent CN104860446a discloses a high hardness industrial water softening separation method and system. The invention discloses a high-hardness industrial water softening and separating method, which comprises the following steps: adjusting the pH value of high-hardness industrial water to 8-10 in a sludge pond to enable scale forming ions in the water to form a precipitate; the industrial water which forms sediment in the sludge tank is conveyed to a hollow fiber membrane concentration device, and softened water is obtained through a membrane separation method. The invention adopts a membrane separation method, which is different from the chemical self-crystallization hardening removal method of the invention.
Disclosure of Invention
In order to solve the above-mentioned drawbacks and disadvantages, an object of the present invention is to provide a self-crystallizing fluidized bed reactor.
The invention also aims to provide a system for self-crystallizing high-fluorine and high-hardness wastewater by a two-stage two-phase fluidized bed comprising the self-crystallizing fluidized bed reactor.
The invention also aims to provide a method for treating high-fluorine and high-hardness wastewater by using the two-stage two-phase fluidized bed self-crystallization system.
To achieve the above object, in one aspect, the present invention provides a self-crystallizing fluidized bed reactor comprising:
a reactor cylinder;
the water distributor 22 is arranged at the bottom of the reactor cylinder, when the reactor runs, a water distribution area 23 is arranged below the water distributor 22, and a cavity above the water distributor 22 forms a fluidized bed layer 24;
a water receiving weir 26 is arranged at the periphery of the top of the reactor barrel, a solid-liquid separation area 25 is arranged below the water receiving weir 26, and an annular water receiving pipe 27 is arranged between the solid-liquid separation area 25 and the fluidized bed 24;
the side wall of the reactor cylinder is provided with a water inlet 30, a slag discharging port 31, a medicine adding port 32, a water outlet 33 and a sampling tube 35,
wherein the water inlet 30 and the slag discharging port 31 are respectively positioned below and above the water distributor 22; the dosing port 32 is positioned in the middle of the reactor cylinder; the water outlet 33 is positioned on the side wall of the top of the reactor;
The upper part and the bottom of the side wall of the reactor cylinder are connected with a circulating water system 28, and the circulating water system 28 comprises a circulating pump, a water outlet pipeline and a water return pipeline; wherein, one end of the water outlet pipeline is connected with the annular water collecting pipe 27, and the other end of the water outlet pipeline is connected with the bottom of the reactor cylinder body through a circulating pump and a water return pipeline;
the sampling pipes 35 are uniformly distributed on the side wall of the reactor cylinder between the water outlet pipeline of the circulating water system 28 and the water distributor 22.
According to the self-crystallizing fluidized bed reactor of the present invention, preferably, the number of the sampling tubes 35 is 3 to 4.
According to the self-crystallization fluidized bed reactor of the present invention, preferably, an acid washing medicine inlet 34 for connecting with an acid washing device is arranged above the slag discharging port 31; the side walls of the reactor cylinder above and below the water distributor 22 are connected with an acid washing circulation system 29, the acid washing circulation system 29 comprises an acid washing circulation pump, an acid washing water pipeline and an acid washing water return pipeline, wherein the acid washing water outlet pipeline is arranged above the water distributor 22 and below the acid washing medicine inlet 34; the pickling return line is located below the water distributor 22. In the pickling circulation system 29 of the present invention, the positions of the pickling water pipe and the pickling water return pipe are not necessarily connected to the positions of the water inlet 30 and the slag discharge port 31, and in the embodiment of the present invention, the pickling circulation system 29 is disposed on the opposite side of the water inlet 30 and the slag discharge port 31.
According to the self-crystallization fluidized bed reactor of the present invention, preferably, the solid-liquid separation zone 25 of the reactor vessel is provided with a detachable chute packing or inclined plate packing 36, and the chute packing or inclined plate packing 36 is fixed on the reactor vessel wall below the water receiving weir. When the self-crystallization fluidized bed reactor aims at removing fluorine, the product calcium fluoride particles are small in particle size and difficult to naturally settle by gravity, and in order to strengthen the solid-liquid separation effect, a detachable inclined tube filler or inclined plate filler is arranged in a solid-liquid separation area of the reactor cylinder. The inclined pipe filler or the inclined plate filler is conventional equipment used in the technical field of water treatment.
According to the self-crystallization fluidized bed reactor, a cavity is formed in the reactor cylinder;
the water distributor is used for ensuring uniform water distribution, the annular water receiving pipe is used for ensuring uniform water receiving, the two are important to the necessary hydraulic conditions for forming a crystallization fluidized bed layer, and the two play an important role in stabilizing the flow state required by crystallization;
the medicine inlet is used for adding the medicine A or the medicine B;
the pickling circulation system is used for carrying out pickling cleaning on the water distributor after the reactor stops running;
the circulating water system is used for forming higher ascending flow rate in the reactor and providing a proper flow state for self-crystallization;
The sampling tube is used for sampling and observing the particle content in the water sample so as to determine the height of the fluidized bed layer;
the water outlet is used for discharging the wastewater collected by the water receiving weir from the reactor.
Reactor cavity: and a part between the water distributor and a return water outlet (a water outlet pipeline) of the circulating water system.
On the other hand, the invention also provides a system for treating high-fluorine and high-hardness wastewater by two-stage two-phase fluidized bed self-crystallization, which comprises: two of the above self-crystallizing fluidized bed reactors: respectively marked as a primary reactor 1 and a secondary reactor 2; the device comprises a medicament A feeding device 3, a medicament B feeding device 4, a primary material pool 7 and a secondary material pool 9;
wherein, the raw water pool is connected with the water inlet of the primary reactor 1 through a water inlet pipeline 15 and a water inlet pump 5;
the reagent A feeding device 3 is connected with a reagent feeding port of the primary reactor 1 through a reagent A feeding pipeline 13;
the deslagging port of the primary reactor 1 is connected with the primary material pool 7 through a primary reactor sludge discharge pipe 17;
the water outlet of the primary reactor 1 is connected with the water inlet of the secondary reactor 2 through a primary water outlet pipeline 11;
the drug B adding device 4 is connected with a drug adding port of the secondary reactor 2 through a drug B adding pipeline 14;
the deslagging port of the secondary reactor 2 is connected with the secondary material pool 9 through a secondary reactor sludge discharge pipe 19;
The water outlet 33 of the secondary reactor 2 is connected with the recovery device through a secondary water outlet pipeline 12.
The system according to the invention preferably further comprises a pickling device 10, wherein the pickling device 10 is respectively connected with a pickling medicine inlet of the primary reactor 1 and a pickling medicine inlet of the secondary reactor 2 through a primary pickling pipeline 20 and a secondary pickling pipeline 21.
According to the system of the invention, preferably, the bottoms of the primary material pool 7 and the secondary material pool 9 are respectively provided with a grid. Wherein the interception materials used by the grid mesh comprise calcium carbonate particles or calcium fluoride particles, and when the interception materials are the calcium carbonate particles, the mesh opening of the grid mesh is less than or equal to 16 meshes (1 mm); when the trapped material is calcium fluoride particles, the mesh opening of the grid is less than or equal to 200 meshes (0.075 mm).
In still another aspect, the present invention further provides a method for treating wastewater with high fluorine and high hardness by using the two-stage two-phase fluidized bed self-crystallization of the system, which comprises:
(1) Firstly, injecting raw water into a first-stage reactor according to the flow calculated by the maximum hydraulic retention time, and submerging a water outlet pipeline of a circulating water system by the liquid level in the first-stage reactor; simultaneously adding the reagent A into a cavity of the primary reactor;
then starting a circulating water system, sending the return water to a water distribution area of the primary reactor to be mixed with raw water, and then uniformly rising the mixture into a cavity of the primary reactor through a water distributor, so that the rising flow rate of wastewater in the primary reactor reaches the minimum design rising flow rate to form supersaturated solution; during the circulating flow in the primary reactor, ca 2+ And F is equal to - Or Ca 2+ With CO 3 2- Self-crystallizing the supersaturated solution to form CaF 2 Or CaCO (CaCO) 3 Fine crystal particles, followed by formation of a fluidized bed of particles;
(2) The primary effluent automatically flows into a water distribution area of the secondary reactor, flows to a water outlet pipe of a circulating water system submerged by the liquid level in the secondary reactor, and simultaneously, a reagent B is added into a cavity of the secondary reactor;
then starting a circulating water system of the secondary reactor, and after the return water is sent to a water distribution area of the secondary reactor and mixed with the primary effluent, uniformly rising the mixed wastewater into a cavity of the secondary reactor through a water distributor;
forming a supersaturated solution under such conditions; during the circulating flow in the secondary reactor, ca 2+ With CO 3 2- Self-crystallizing the supersaturated solution to produce CaCO 3 Fine crystal particles, followed by formation of a fluidized bed of particles;
during the start-up phase, the secondary effluent [ Ca ] 2+ ]、[F - ]The concentration is higher, so that the secondary effluent is also required to be returned to the raw water pool for continuous treatment;
and (3) an operation stage:
(1) Raw water and return water of the primary reactor enter a water distribution area from the bottom of the primary reactor to be mixed, uniformly distributed by a water distributor, uniformly lifted into a fluidized particle bed of the primary reactor at a certain air tower lifting flow rate, and simultaneously uniformly lifted into a fluidized particle bed of the primary reactor at a certain [ Ca ] 2+ ]/[F - ]The medicine A is injected into a fluidized particle bed layer of a primary reactor in a molar ratio or a certain total alkalinity mass ratio to form supersaturated solution; under the specific hydraulic conditions of the fluidized bed reactor (including hydraulic retention time and empty tower rising flow rate defined when raw water is high-fluorine high-hardness waste water, high-hardness waste water and high-fluorine waste water respectively), the constitutive crystal ions self-crystallize and grow into crystal particles with a certain particle size, a fluidized crystal particle bed layer is gradually formed in the cavity of the primary reactor, F in the raw water passes through the fluidized bed layer from bottom to top - Or Ca 2+ Can be removed from the water; the raw water further rises to a solid-liquid separation area, crystal particles remain in the primary reactor, supernatant is collected through a water receiving weir at the top, and automatically flows into a water distribution area at the bottom of the secondary reactor;
(2) Mixing the primary effluent with the secondary reactor reflux water in the water distribution area of the secondary reactor, uniformly distributing water by a water distributor, uniformly rising to the inside of the cavity of the secondary reactor at a certain rising flow rate of the empty tower, and simultaneously uniformly mixing with a certain [ Ca ] 2+ ]/[CO 3 2- ]The molar ratio of agent B is injected thereto; in the cavity of the secondary reactor, the primary effluent continuously entering, the secondary reactor reflux water and the medicament B form supersaturated solution, under the specific hydraulic condition of the fluidized bed reactor, the crystal forming ions self-crystallize and grow into crystal particles with certain particle size, a fluidized crystal particle bed layer is gradually formed in the cavity of the reactor, and Ca in the water is in the process of passing through the fluidized bed layer from bottom to top 2+ Is removed; one-stage water outlet into oneAnd (3) rising to a solid-liquid separation area, keeping crystal particles in the secondary reactor under the action of gravity precipitation, collecting supernatant through a top water receiving weir, and finally recycling through a secondary water outlet pipe discharge system.
According to the method of the present invention, preferably, when the removal target is fluoride ion (when the raw water is high-fluorine high-hardness wastewater or high-fluorine wastewater),
parameters of the first stage reactor at start-up stage: the agent A is CaO or Ca (OH) 2 With CaCl 2 Wherein CaCl 2 Accounting for 0 to 25 percent of the total mass of the dry matter mixture; the medicine A is according to [ Ca ] 2+ ]/[F - ]Molar ratio=1.5-2:1;
the maximum hydraulic retention time is 4-5 h, the pH value in the primary reactor is=6-7.5, and the minimum design rising flow rate is 4-10m/h;
parameters of the start-up stage secondary reactor: medicament B is Na 2 CO 3 According to [ Ca ] 2+ ]/[CO 3 2- ]Molar ratio=1:1.5-2;
the maximum hydraulic retention time of the primary effluent is 1 to 1.5 hours; the rising flow rate of the mixed wastewater reaches 10-20 m/h, and the pH value in the secondary reactor is controlled to be 9-10.
According to the method of the present invention, preferably, when the removal target is temporary calcium hardness (when the raw water is high hardness wastewater),
Parameters of the first stage reactor at start-up stage: the agent A is CaO or Ca (OH) 2 The adding amount of the emulsion is 2 to 2.5 times (mass ratio, caCO) of the total alkalinity in water 3 Meter) a meter, a counter controller, a counter,
the maximum hydraulic retention time is 1-1.5 h, the pH value in the primary reactor is 9.5-10, the minimum design rising flow rate is 10-20m/h,
parameters of the start-up stage secondary reactor: medicament B is Na 2 CO 3 According to [ Ca ] 2+ ]/[CO 3 2- ]Molar ratio=1:1.5-2;
the maximum hydraulic retention time of the primary effluent is 1 to 1.5 hours; the rising flow rate of the mixed wastewater reaches 10-20m/h, and the pH value in the secondary reactor is controlled to be 9-10.
According to the method of the invention, the components of the agent A, B are the same in the start-up phase and the run phase, but the dosage (i.e., concentration) is different. The concentration of agent A, B required at start-up is slightly higher than at run-up. In the starting stage, in order to obtain a larger concentration product of the textured crystal ions, the formation of crystal nuclei is ensured; in the operation stage, a certain amount of crystal nuclei are formed in the reactor, and the dosage of the medicament A, B, namely the concentration of the medicament A, B in the reactor, can be properly reduced, so that the dosage is saved.
The method according to the invention, wherein the raw water is injected at a minimum flow rate in the start-up phase while the [ Ca ] is at a maximum 2+ ]/[F - ]Or [ Ca ] 2+ ]/[CO 3 2- ]The reagent A is added in proportion to obtain the maximum ion concentration, so that supersaturated solution is formed, and a large number of fine crystal nuclei are spontaneously generated, which is the nucleation stage of the self-crystallization reaction; after that, the crystal nucleus grows continuously in the process of reflux, namely the growth process of the crystal nucleus.
It should be noted that there are two cases in the primary reactor: when the contaminant is removed as fluoride ions, it is determined according to [ Ca ] 2+ ]/[F - ]Determining the addition amount of the agent A by the molar ratio; when the high-hardness waste water is subjected to hardness removal, temporary hardness is removed according to the alkalinity in the water (mainly bicarbonate alkalinity, caCO 3 Meter) to determine the amount of agent a; the secondary reactor is used for removing calcium ions, i.e. the temporary hardness and the permanent hardness can be removed, and the method only needs to be based on [ Ca ] 2+ ]/[CO 3 2- ]The molar ratio determines the amount of agent a.
According to the method of the present invention, preferably, when the raw water is high-fluorine and high-hardness wastewater,
parameters of the run stage primary reactor: the agent A is CaO or Ca (OH) 2 With CaCl 2 Wherein CaCl 2 Accounting for 0 to 25 percent of the total mass of the dry matter mixture; the medicine A is according to [ Ca ] 2+ ]/[F - ]Molar ratio = 0.7-1.5:1;
the hydraulic retention time HRT is 1-4 h, the surface separation load is 1-4 m/h, the rising flow velocity v of the empty tower is 10-60 m/h, and the pH value in the reactor is less than 7.5, more preferably 4-7; the reflux ratio is 1-20:1, and the temperature range is 10-50 ℃;
The crystal particles discharged from the bottom of the primary reactor are CaF with the particle size of 60-200 mu m 2 Crystal particles;
parameters of the run stage secondary reactor: medicament B is Na 2 CO 3 According to [ Ca ] 2+ ]/[CO 3 2- ]Molar ratio=1:1-2;
the hydraulic retention time HRT is 0.1-1 h, the surface separation load is 4-10 m/h, the empty tower flow rate is 20-100 m/h, the pH value in the reactor is 8-10, the reflux ratio is 1-24:1, and the temperature range is 10-50 ℃;
the crystal particles discharged from the bottom of the secondary reactor are CaCO with the particle size of 1-3 mm 3 And (3) crystal particles.
The method according to the invention, wherein [ F ] in the high-fluorine high-hardness wastewater - ]More than or equal to 300mg/L, and the calcium hardness more than or equal to 500mg/L (CaCO) 3 )。
According to the method of the present invention, preferably, when the raw water is high hardness wastewater,
and (3) an operation stage: the pH value in the primary reactor is 8.5-10, and the medicament A is CaO or Ca (OH) 2 The adding amount of the emulsion is 1.5 to 2 times of the total alkalinity in water (the mass ratio is CaCO) 3 Counting);
in the secondary reactor, the medicament B is Na 2 CO 3 According to [ Ca ] 2+ ]/[CO 3 2- ]The molar ratio=1:1-2 is added, and the pH value in the reactor is controlled to be 8-10;
primary reactor, secondary reactor operating parameters: the hydraulic retention time HRT is 0.1-1 h, the surface separation load is 4-10 m/h, the air tower flow rate is 20-100 m/h, the temperature range is 10-50 ℃, and the reflux ratio is 1-24:1;
The crystal particles discharged from the bottoms of the primary reactor and the secondary reactor are CaCO with the particle size of 1-3 mm 3 And (3) crystal particles.
The method according to the invention, wherein the calcium hardness of the high hardness wastewater is more than or equal to 500mg/L (CaCO) 3 )。
According to the method of the present invention, preferably, when the raw water is high-fluorine wastewater,
parameters of the run stage primary reactor: the agent A is CaO or Ca (OH) 2 With CaCl 2 Wherein CaCl 2 Accounting for 0 to 25 percent of the total mass of the dry matter mixture, and the medicament A is prepared according to [ Ca ] 2+ ]/[F - ]Molar ratio = 0.7-1.5:1;
the hydraulic retention time HRT is 1-4 h, the surface separation load is 1-4 m/h, the rising flow velocity v of the empty tower is 10-60 m/h, the temperature range is 10-50 ℃, the reflux ratio is 1-20:1, and the pH value in the reactor is less than 7.5, more preferably 4-7;
the crystal particles discharged from the bottom of the primary reactor are CaF with the particle size of 60-200 mu m 2 Crystal particles;
parameters of the run stage secondary reactor: medicament B is Na 2 CO 3 According to [ Ca ] 2+ ]/[CO 3 2- ]Molar ratio=1:1-2;
the hydraulic retention time HRT is 0.1-1 h, the surface separation load is 4-10 m/h, the rising flow velocity v of the empty tower is 20-100 m/h, the temperature range is 10-50 ℃, the reflux ratio is 1-24:1, and the pH value in the reactor is 8-10;
The crystal particles in the secondary reactor are CaCO with the particle size of 1-3 mm 3 And (3) crystal particles.
The method according to the invention, wherein [ F ] in the high-fluorine wastewater - ]≥300mg/L。
The method according to the invention, wherein CaCl 2 0 to 25% by weight of the total dry matter mixture means that the dry matter (CaO or Ca (OH) 2 With CaCl 2 ) Percent of total weight, such as: caO powder and CaCl 2 The total weight of the powder was 100g, caCl 2 25g, i.e. CaCl 2 The proportion is 25%.
The method according to the present invention preferably further comprises the step of determining the fluidized bed height and the deslagging frequency of the primary reactor and the secondary reactor:
more preferably, the determination of the fluidized bed height of the primary and secondary reactors comprises the steps of:
taking out a certain amount of mixed liquid in the reactor from the sampling tube, and when the ratio of the settled volume of the settled sinkable solid to the volume of the mixed liquid before standing reaches more than 10-30%, the height of the bed layer is considered to reach the height of the sampling port;
still more preferably, the deslagging frequency of the primary reactor and the secondary reactor is determined according to the height of the corresponding fluidized bed, namely, the height of the fluidized bed is kept to be less than 3/4 of the cavity part (the part between the water distributor and the reflux water outlet) of the reactor, and deslagging is needed when the height of the fluidized bed is more than 3/4 of the cavity part of the reactor;
It is further preferred that the height of the fluidized bed is maintained at 1/2 to 3/4 of the height of the cavity portion of the reactor (the portion above the water distributor and between the return water outlets).
The method according to the invention, wherein the volume of the mixture liquid is usually 1L in the process of determining the heights of the fluidized beds of the primary reactor and the secondary reactor, and the standing is carried out in a measuring cylinder for 5min; and the sinkable solid comprises calcium fluoride particles or calcium carbonate particles; when the sinkable solid is calcium fluoride particles, the ratio of the volume of the sinkable solid to the volume of the mixed solution before standing is a small value, and when the sinkable solid is calcium carbonate particles, the ratio of the volume of the sinkable solid to the volume of the mixed solution before standing is a large value.
According to the method of the invention, the concentration of fluoride ions and calcium ions in raw water are different, and the time difference of fluidized bed formation is large. Therefore, the sampling at the starting stage can be more frequent, and the sampling is carried out once in 1-2 hours; and the operation stage is 2-8 hours for sampling once. In the case of raw water determination, after a certain period of operation, the person skilled in the art can easily find the law of fluidized bed formation, i.e. can easily determine the sampling interval.
The process according to the invention preferably further comprises a post-reactor shutdown treatment operation comprising the steps of:
a. After the reactor is stopped, all the waste water and particles in the reactor are immediately emptied to a primary material pool or a secondary material pool;
b. and (3) starting the acid washing device, injecting acid solution into the first-stage reactor and the second-stage reactor, starting the acid washing circulation system to carry out acid washing on the water distributor after the liquid level of the acid solution is beyond the acid washing water outlet pipeline, and then emptying the acid washing waste liquid, flushing the inside of the reactor by clear water, and stopping the operation for a long time after the reactor is emptied and washed.
The primary material pool and the secondary material pool are not common slag storage pools, the pool capacity of the primary material pool and the secondary material pool used in the invention can accommodate all particles when the reactor reaches the maximum height fluidized bed, grids are arranged at the bottoms of the primary material pool and the secondary material pool, the used trapped materials comprise calcium carbonate particles or calcium fluoride particles, and when the trapped materials are calcium carbonate particles, the grid holes are less than or equal to 16 meshes (1 mm); when the trapped material is calcium fluoride particles, the mesh opening of the grid is less than or equal to 200 meshes (0.075 mm). Large particles are trapped on the grid, and particles with the particle size smaller than that of the sieve holes can leak out and be collected through the grid and periodically returned to the reactor.
According to the method of the invention, in a specific embodiment of the invention, the pickling time in step b is 6-12 hours. The acid and the concentration thereof used for pickling are not particularly required, and a person skilled in the art can select proper acid liquor and prepare reasonable concentration according to the field operation requirement, so long as the purpose of pickling cleaning can be realized.
In addition, the reactor can be stopped for a long time after being emptied and pickled; and because the inside of the reactor is a cavity, no complex components exist, and when necessary, the reactor can be manually entered into the inside of the reactor to carry out more thorough cleaning work.
The method according to the invention, wherein, in the start-up phase, the aim is not to achieve the standard of pollutant removal, but rather to simultaneously form a great deal of crystal form precipitation, crystal growth and formation of a crystal particle fluidized bed by the crystal forming ions in water, because of the fact that [ F - ]、[Ca 2+ ]Possibly still higher, and needs to be refluxed to the originalAnd (5) a pool of water, and re-participating in the reaction.
At this time, the following reaction process occurs in the first stage reactor at the start-up stage: in the circulating flow process in the reactor, the medicament A is fully mixed with raw water, and the crystal substance Ca 2+ And F is equal to - Or CO 3 2- Forming supersaturated solution, in the solid-liquid two-phase fluidized bed reactor, hydraulically stirring to enable water flow to be in a strong turbulence state, continuously updating a solid-liquid two-phase contact interface, and having larger speed difference between the two phases, strengthening mass transfer effect between the two phases, and simultaneously generating a large number of crystal precipitates in the primary reactor; under the action of hydraulic shearing, the formed CaF 2 Or CaCO (CaCO) 3 The fine crystal particles do not aggregate with each other into large particles, but the crystalline substance Ca in the bulk of the aqueous solution 2+ 、F - Or CO 3 2- Stably toward fine CaF 2 Or CaCO (CaCO) 3 The crystal surface diffuses, moves, and then embeds the crystal lattice in some way, thereby increasing the individual crystal particle size and forming uniform and dense crystalline particles; with the time, a fluidized particle bed with a certain height is formed at the bottom of the reactor, and the starting stage is completed.
The process according to the invention, wherein, during the run-up phase, a fluidized bed of crystal particles has been formed, with the aim of defluorination, hardness removal, according to the effluent [ F - ]、[Ca 2+ ]Adjusting the operation parameters of each stage of reactor to make the reactor output water F - ]、[Ca 2+ ]Reaching the processing target.
Raw water and return water of the primary reactor enter a water distribution area from the bottom of the primary reactor to be mixed, uniformly distributed by a water distributor, uniformly lifted into a cavity of the primary reactor at a certain lifting flow rate, and the medicament A also takes a certain [ Ca ] 2+ ]/[F - ]Molar ratio or mass ratio of certain total alkalinity (CaCO) 3 Meter) is injected into the cavity; in the cavity of the first-stage reactor, continuously entering raw water and chemical A form supersaturated solution, under the specific hydraulic condition of the fluidized bed reactor, the crystal forming ions self-crystallize and grow into crystal particles with a certain particle size, and the inside of the reactor cavity gradually forms a fluidized crystal particle bed, and the raw water flows down from bottom to top F in raw water in the process of passing through the fluidized bed - Or Ca 2+ Can be removed from the water; the raw water further rises to a solid-liquid separation area, crystal particles are reserved in the reactor under the separation action of gravity precipitation or inclined tube filler or inclined plate filler, supernatant fluid is collected through a water receiving weir at the top, and the supernatant fluid automatically flows into a water distribution area at the bottom of the secondary reactor.
The primary effluent and the secondary reactor return water are mixed in a water distribution area of the secondary reactor, uniformly distributed by a water distributor, uniformly lifted into a cavity of the secondary reactor at a certain lifting flow rate, and the medicament B also takes a certain [ Ca ] 2+ ]/[CO 3 2- ]The molar ratio is injected thereto; in the cavity of the secondary reactor, the primary effluent continuously entering, the secondary reactor reflux water and the medicament B form supersaturated solution, under the specific hydraulic condition of the fluidized bed reactor, the crystal forming ions self-crystallize and grow into crystal particles with certain particle size, a fluidized crystal particle bed layer is gradually formed in the cavity of the reactor, and Ca in the water is in the process of passing through the fluidized bed layer from bottom to top 2+ Further removed; the primary effluent further rises to a solid-liquid separation zone, crystal particles remain in the reactor under the action of gravity precipitation, supernatant is collected through a top water receiving weir, and finally is discharged out of the system through a secondary water outlet pipe.
Along with the continuous generation and growth of crystals, the height of the fluidized bed layer steadily grows and delaminates, particles with small particle size and light weight are arranged at the upper part of the fluidized bed layer, and particles with large particle size and large weight are arranged at the lower part of the fluidized bed layer, so that the bottom particles need to be discharged periodically at the moment so as to ensure that the reactor always operates under proper hydraulic conditions. Sampling ports are arranged on different heights of the side wall of the reactor, and the height of the fluidized bed layer and the deslagging frequency are determined by observing the content and the size of particles in water samples with different heights; slag discharging pipes are arranged at the lower parts of the primary reactor and the secondary reactor and above the water distributor, slag is discharged periodically through the mud discharging pipes, a fluidized bed layer with a certain height is maintained, and CaF with higher purity is obtained 2 Or CaCO (CaCO) 3 And (3) particles.
In the operation stage, according to different raw water quality (different target pollutants), the medicine A and the medicine B are different in the type of the used medicines, and the operation parameters of the reactor are also different, and are specifically shown in the table 1.
TABLE 1
(1) The method provided by the invention can be used for removing F from high-fluorine high-hardness wastewater - And Ca 2+ (raw water [ F) - ]More than or equal to 300mg/L, and the calcium hardness more than or equal to 500mg/L (CaCO) 3 ))。
Primary reactor operating parameters: the agent A is CaO or Ca (OH) 2 With CaCl 2 (wherein CaCl) 2 0 to 25% by weight of the total dry matter mixture, which acts to adjust the pH in the reactor <7.5 For removing F in waste water - The addition amount is as follows [ Ca ] 2+ ]/([F - ]) Molar ratio= (0.7-1.5): 1. Hydraulic retention time HRT= (1-4) h, surface separation load of 1-4 m/h, empty tower ascending flow velocity v= (10-60) m/h, pH value in the reactor= (4-7.5), reflux ratio (reflux amount/water inflow amount) = (1-20): 1, temperature range (10-50) °c; the primary reactor crystallization product is mainly CaF with the grain diameter of 60-200 mu m 2 And discharging the crystal particles into a primary material pool in the form of precipitated sludge.
Secondary reactor operating parameters: medicament B is Na 2 CO 3 For removing Ca from raw water 2+ First-stage excessive addition of Ca 2+ The addition amount is as follows [ Ca ] 2+ ]/[CO 3 2- ]Molar ratio=1:1-2; hydraulic retention time HRT= (0.1-1) h, surface separation load (4-10) m/h, empty tower flow rate (20-100) m/h, pH value in the reactor= (8-10), reflux ratio (reflux amount/water inflow) = (1-24): 1, temperature range (10-50); the crystallization product of the secondary reactor is mainly CaCO with the grain diameter of 1-3 mm 3 The crystalline particles, in the form of particles, exit the secondary reactor.
(2) The invention can also be used for removing hardness (the hardness of raw water calcium is more than or equal to 500mg/L (CaCO) 3 ) With the main removal target being Ca 2+ 。
In the first-stage reactor, the reaction mixture is mixed with the catalyst, The agent A is CaO or Ca (OH) 2 For removing temporary calcium hardness, the addition amount of the emulsion is 1.5 to 2 times of the total alkalinity in water (the mass ratio is CaCO) 3 Meter), controlling the pH value to be in the range of 8.5-10;
in the secondary reactor, the medicament B is Na 2 CO 3 For removing permanent calcium hardness, in an amount of [ Ca ] 2 + ]/[CO 3 2- ]Molar ratio=1 (1-2), and the pH is controlled to be in the range of 8-10.
Primary reactor, secondary reactor operating parameters: hydraulic retention time hrt=0.1-1 h, surface separation load 4-10 m/h, superficial flow velocity 20-100 m/h, temperature range 10-50 ℃, reflux ratio (reflux/water inflow) = (1-24): 1.
CaCO formed by self-crystallization 3 The grain size of the crystal is 1-3 mm, and the crystal is discharged into a secondary material pool in the form of grains.
(3) The invention can also be used for high-fluorine wastewater ([ F) - ]More than or equal to 300 mg/L) for defluorination. Primary reactor removal target F - The secondary reactor is used for removing Ca which is aimed at excessive addition 2+ 。
Primary reactor operating parameters: the agent A is CaO or Ca (OH) 2 With CaCl 2 Wherein CaCl 2 Accounting for 0 to 25 percent of the total mass of the dry matter mixture, caCl 2 Is used for regulating the pH value in the reactor<7.5, the dosage of the drug A is calculated according to [ Ca ] 2 + ]/[F - ]The mole ratio of = (0.7-1.5): 1, hydraulic retention time HRT = (1-4) h, surface separation load of 1-4 m/h, rising flow velocity v = (10-60) m/h of empty tower, reflux ratio (reflux quantity/water inflow) = (1-20): 1, pH value <7.5, preferably 4 to 7;
secondary reactor operating parameters: medicament B is Na 2 CO 3 The addition amount of the aqueous solution of (C) is as follows [ Ca ] 2+ ]/[CO 3 2- ]The molar ratio=1 (1-2), the hydraulic retention time hrt= (0.1-1) h, the surface separation load is 1-4 m/h, the rising flow velocity v= (20-100) m/h of the empty tower, the reflux ratio (reflux amount/water inflow) = (1-24): 1, and the pH value=8-10.
The precipitated product of the primary reactor is CaF 2 Crystal particles with the particle diameter of 60-200 mu m are discharged in the form of precipitated sludge, and the precipitated product of the secondary reactor is CaCO 3 The grain size of the crystal particles is 1-3 mm.
Full system, in water [ F - ]Removal rate of>97%, in effluent [ Ca ] 2+ ]Removal rate of>99％。
(4) The method does not aim at removing the magnesium hardness, and can not remove the magnesium hardness due to the limitation of reaction conditions.
When the reactor is used for removing fluorine, a detachable inclined tube filler or inclined plate filler can be additionally arranged in a solid-liquid separation area of the reactor in order to strengthen the solid-liquid separation effect.
As the reaction proceeds, the method further comprises the steps of determining the fluidized bed height and the deslagging frequency of the primary reactor and the secondary reactor:
wherein the mud discharging frequency is determined by the height of the bed layer, and the height of the bed layer is kept below 3/4 of the cavity part (the part above the water distributor and between the return water outlets) of the reactor.
Judging the height of the bed: 3-4 sampling ports are uniformly distributed on the side wall of the cavity part of the reactor, sampling is performed regularly, and the content of crystal particles in the water sample is checked, so that the height of the fluidized bed layer surface is determined. The layer surface position of the fluidized bed can also be monitored on line according to a level meter in the automatic control system.
Taking high-fluorine high-hardness raw water as an example, the specific process of the invention comprises the following steps:
(1) Start-up of the reactor:
the raw water is high-fluorine high-hardness wastewater, and the reagent A is CaO or Ca (OH) is determined 2 For removing F - Medicament B is Na 2 CO 3 For removing Ca 2+ 。
Step 1: firstly, raw water is sent into a water distribution area at the bottom of the primary reactor 1 through a water inlet pipeline 15 by a water inlet pump 5 according to the flow calculated by HRT=4-5 h, and the raw water is sent to a water outlet pipe 16 of a liquid level submerged circulation system in the primary reactor 1; simultaneously, the drug A adding device 3 is started according to [ Ca ] 2+ ]/[F - ]The mol ratio=1.5-2:1, and the reagent A is added into the cavity of the primary reactor 1; then start the first stageThe circulating pump 6 of the reactor sends the backwater water to the water distribution area at the bottom, after the backwater water is mixed with the raw water, the backwater water and the raw water are uniformly risen to the cavity of the first-stage reactor 1 through the water distributor, so that the rising flow rate of the wastewater in the reactor reaches 2-10 m/h, and the pH value is controlled<7.5; during the circulating flow in the reactor, ca 2+ And F is equal to - Self-crystallizing the supersaturated solution to form CaF 2 Fine crystal particles. The raw water further rises to a solid-liquid separation area, crystal particles are reserved in the reactor through the separation effect of inclined pipe filler or inclined plate filler, supernatant fluid is collected through a top water receiving weir, and the supernatant fluid automatically flows into a water distribution area at the bottom of the secondary reactor 2 through a primary water outlet pipeline 11.
Step 2: the primary effluent automatically flows into a water distribution area at the bottom of the secondary reactor 2, and flows into a water outlet pipe 18 of a liquid level submerged circulation system in the secondary reactor 2; simultaneously, the drug B adding device 4 is started according to [ Ca ] 2+ ]/[CO 3 2- ]Adding a reagent B into a cavity of the secondary reactor 2 according to the molar ratio of = 1:1.5-2; then a circulating pump 8 of the secondary reactor is started, the backwater water is also sent to a water distribution area at the bottom, after being mixed with the primary effluent, the backwater water and the primary effluent are uniformly risen to a cavity of the secondary reactor 2 through a water distributor, so that the rising flow rate of wastewater in the reactor reaches 10-20 m/h, and the pH=9-10 is controlled; during the circulating flow in the reactor, ca 2+ With CO 3 2- Self-crystallizing the supersaturated solution to produce CaCO 3 Fine crystal particles. The first-stage effluent continuously rises to a solid-liquid separation zone, caCO 3 The crystal particles remain in the reactor under gravity settling, and the supernatant is collected via a top weir and finally discharged from the system through secondary effluent pipe 12. During the start-up phase, water [ Ca ] is discharged 2+ ]、[F - ]The concentration is still higher, and the system effluent returns to the original water pool.
(2) Operation of the reactor:
step 3: in the first-stage reactor 1, with CaF 2 Crystal particles are continuously generated and grown, and CaF is gradually formed in the cavity of the reactor 2 A fluidized bed of crystalline particles; the dosage of the medicament A is reduced to [ Ca ] 2+ ]/[F - ]Molar ratio = (0.7-1.5) 1, according to the thickness and density of fluidized bedIncreasing, and timely adjusting the operation parameters such as the rising flow velocity (10-60 m/h), HRT (1-4 h), reflux ratio (1-20:1) and the like of the empty tower to ensure that water [ F ] is discharged - ]Meeting the processing target; f in raw water in the process of passing through the fluidized bed layer from bottom to top - Is removed.
Wherein, in the implementation process, the bed layer appears through sampling observation, namely the operation stage is considered to be entered, and the dosage of the medicament A is reduced to [ Ca ] 2+ ]/[F - ]The molar ratio is (0.7-1.5): 1; regarding the selection of the specific proportions, regarding the concentration of calcium and fluoride ions in the wastewater, for a particular wastewater, one skilled in the art will be able to know the appropriate operating parameters for that wastewater during the course of the operational tuning process, based on the ranges of operating parameters given.
Step 4: in the secondary reactor 2, with CaCO 3 Crystal particles are continuously generated and grown, and CaCO gradually forms in the cavity of the reactor 3 A fluidized bed of crystalline particles; the dosage of the medicament B is reduced to [ Ca ] 2+ ]/[CO 3 2- ]The molar ratio=1 (1-2), and the operation parameters such as the rising flow rate (20-100 m/h), the HRT (0.1-1 h), the reflux ratio (1-24:1) and the like are timely adjusted along with the increase of the thickness and the density of the fluidized bed layer, so that the water [ Ca ] is discharged 2+ ]Meeting the processing target; in the process that the primary effluent passes through the fluidized bed layer from bottom to top, ca in the primary effluent 2+ Is removed.
Step 5: along with the continuous generation and growth of crystals, the height of the fluidized bed layer steadily increases, and the gaps among particles in the fluidized bed layer are reduced until the reflux water quantity is not matched with the crystal particle quantity, and then the sludge discharge is needed to ensure that the reactor is operated under proper hydraulic conditions all the time. The particle content in the water sample is observed through periodic sampling tube 35 sampling, and the height of the fluidized bed layer is determined; the height of the fluidized bed layer is kept to be 1/2-3/4 of the distance between the circulating water outlet pipe and the water distributor through periodic mud discharge.
The lower part of the primary reactor 1 is provided with a mud pipe 17 for periodically discharging CaF 2 The particles are fed into a first-stage material pool 7, and CaF with higher purity can be obtained 2 And (3) crystal particles. The lower part of the secondary reactor 2 is provided with a mud discharging pipe 19 for periodically discharging CaCO 3 The particles are fed to a secondary material pond 9,can obtain CaCO with higher purity 3 And (3) crystal particles.
(3) The stopping phase of the reactor:
step 6: and stopping each reactor, and immediately emptying all the wastewater and particles in the reactor to a primary material pool or a secondary material pool. The inner bottom of the material pool is provided with a grid, particles are trapped on the grid, and wastewater flows back to the raw water pool.
Step 7: starting a pickling device, injecting an acid solution into the reactor, starting a pickling circulation system after the liquid level of the solution is beyond a pickling water outlet pipeline, specifically performing pickling cleaning on the water distributor, evacuating pickling waste liquid after 6-12 hours, and flushing the interior of the reactor with clear water.
The method according to the present invention, wherein the concentration of the emulsion or aqueous solution of the agent A, B is not particularly limited, provided that the amount of the agent added in the reactor is ensured to be within the scope of the present application. After the quality and the water quantity of raw water are determined, the adding quantity of the medicament A, B is determined, and the concentration of the aqueous solution influences the adding flow and the selecting type of the adding pump. However, a person skilled in the art can determine the appropriate concentration ratio of the emulsion or aqueous solution according to the water pump model selection principle and experience.
The invention provides a wastewater treatment method for organically combining a chemical crystallization process with an upflow two-phase fluidized bed process in the field of sewage treatment, and removing fluorine and hardness by self-crystallization without an inducer for the first time. The invention aims to adopt a self-crystallization technology, i.e. no carrier or filler is needed, and uses specific fluid dynamic conditions and chemical crystallization principles in a two-phase fluidized bed self-crystallization reactor to reasonably regulate and control crystallization process conditions so as to lead a precipitant and F in wastewater - And Ca 2+ Spontaneously crystallizing to obtain CaF with uniform particle size 2 、CaCO 3 And the particles strengthen precipitation separation. The CaF is generated due to no induction crystal nucleus of other components 2 、CaCO 3 The crystal particles have higher purity and certain recovery value.
The invention is different from chemical precipitation method and induced crystallization precipitation technology, and provides a wastewater treatment method for removing fluorine and hardness by self-crystallization without inducer, which has the core principle that: homogeneous nucleation under the action of static electricity, directional growth and crystal form precipitation. The invention relates to a method for organically combining a chemical crystallization process with an upflow two-phase fluidized bed process in the field of sewage treatment, on one hand, crystallization is a most basic chemical process in chemical production, and is used for preparing crystallized substances and purifying other substances (especially organic matters), and is also an indispensible part of a plurality of processes. Because of the need to obtain chemical products, there have been intensive studies and applications on the principles of chemical crystallization processes, process conditions, reactors, etc. On the other hand, in the field of water treatment, although a common knowledge has been made that the crystallization method can be used for purifying water (by precipitating crystals of insoluble compounds, removing impurities in water, thereby purifying water), only obtaining target water quality is of interest, in order to enhance the precipitation separation effect, or in combination with conventional water treatment techniques such as coagulating sedimentation, clarifying, filtering, or the like, or in order to provide inducer enhanced crystallization, a large amount of other impurity components are mixed in the crystals of the insoluble compounds, which can only be regarded as sludge waste, and no or little recycling value is obtained. On the other hand, the crystallizable pollutants in the water treatment process can be in a supersaturated state required by crystallization under normal temperature conditions, a crystallization reactor is not required to be as complex as a chemical process, and a fluidized bed reactor commonly used in the water treatment field can meet the crystallization process requirement, so that the crystallization of the indissolvable compound can be realized by utilizing similar structural forms and operation modes of the reactors, and the indissolvable compound crystallization particles with higher purity and recovery value can be obtained while the water quality is purified.
The invention is based on chemical crystallization principle:
under normal temperature crystallization conditions, supersaturation is the driving force of the crystallization process, i.e. the concentration of the solution exceeds the equilibrium concentration (solubility), the excess being called supersaturation, meaning that the supersaturation can be represented by three values: absolute supersaturation Δc, relative supersaturation δ, and supersaturation coefficient s. They are respectively expressed as:
ΔC＝C-C eq ；
δ＝(C-C eq )/C eq ；
s＝C/C eq ；
wherein C is the concentration, C eq Is the equilibrium concentration.
The method can realize 'bulk crystallization (simultaneous formation and growth of a large number of crystals)' in the chemical process by meeting 3 conditions, namely 'self-crystallization' process in the invention:
a. after the supersaturation coefficient s is larger than a certain value (critical supersaturation degree), the solution spontaneously performs homogeneous nucleation;
b. the relative supersaturation delta is smaller, so that crystal form precipitation is possible to generate;
c. flow state. The crystallization process can be expressed as a function of "concentration-time", a low supersaturation favors the production of larger crystals, but requires a longer time, but stirring (mechanical or hydraulic) can significantly shorten this time. This is because agitation increases the solubility of the precipitate and also increases the rate of ion diffusion in the solution.
The method provided by the invention can be used for removing fluorine from high-fluorine wastewater, such as acidic high-fluorine wastewater in the industries of pesticides, chemical industry, electroplating, rare earth and the like; the method can also be used for removing hardness of high-hardness wastewater, such as RO concentrated water, high-hardness groundwater and the like in steel works; can also be used for removing fluorine and hardness of high-fluorine and high-hardness wastewater, such as stainless steel cold-rolling wastewater after being rinsed by hydrofluoric acid, and the like. The invention is especially suitable for the hardness removal of high-calcium low-magnesium wastewater and the fluorine removal of high-concentration fluorine-containing wastewater, and can obtain calcium carbonate and calcium fluoride crystal products with certain recovery value.
The beneficial effects of the invention are as follows:
(1) The invention organically combines the chemical crystallization process with the upflow two-phase fluidized bed process, and can realize insoluble compound CaF without adding carrier or crystal nucleus 2 And CaCO (CaCO) 3 And under the action of hydraulic shearing, uniform and compact crystal particles are formed.
(2) The invention can obtain CaF with higher purity on the basis of high-efficiency defluorination and hardness removal 2 And CaCO (CaCO) 3 Crystal particles, realizing sludge recycling, are an environmentThe friendly technology has better application prospect.
(3) The medicine agent used in the invention is mainly Na 2 CO 3 、CaO、Ca(OH) 2 These agents are inexpensive; on the premise of not influencing the water quality of produced water, the device can obtain higher water flow rate, has large water yield in unit time, and is suitable for the industrial wastewater treatment scale.
(4) The invention has simple process flow, the structure of the crystallization reactor is simple, the main reaction section structure is a cavity, and not only creates proper fluid dynamic conditions for chemical crystallization, but also has convenient maintenance, thereby being suitable for industrial application.
Drawings
FIG. 1 is a schematic diagram of a system for self-crystallizing high-fluorine and high-hardness wastewater treatment by a two-stage two-phase fluidized bed provided by the invention;
fig. 2-3 are schematic structural diagrams of the self-crystallizing fluidized bed reactor provided by the present invention.
The main reference numerals illustrate:
1. a first stage reactor;
2. a secondary reactor;
3. a medicament A adding device;
4. a medicament B adding device;
5. a water inlet pump;
6. a primary reactor circulation pump;
7. a first-stage material pool;
8. a secondary reactor circulation pump;
9. a secondary material pool;
10. a pickling device;
11. a primary water outlet pipeline;
12. a secondary water outlet pipeline;
13. a medicament A feeding pipeline;
14. a medicine adding pipeline of the medicine B;
15. a water inlet pipeline;
16. a circulating water system return pipeline of the primary reactor;
17. a first-stage reactor sludge discharge pipe;
18. a circulating water system return pipeline of the secondary reactor;
19. a secondary reactor sludge discharge pipe;
20. a primary pickling pipeline;
21. a secondary pickling pipeline;
22. a water distributor;
23. a water distribution area;
24. a fluidized bed layer;
25. a solid-liquid separation zone;
26. a water receiving weir;
27. an annular water collecting pipe;
28. a circulating water system;
29. a pickling circulation system;
30. a water inlet;
31. a slag discharge port;
32. a medicine adding port;
33. a water outlet;
34. acid washing medicine inlet;
35. a sampling tube;
36. inclined tube packing or inclined plate packing.
Detailed Description
In order to make the technical features, objects and advantageous effects of the present invention more clearly understood, the technical solution of the present invention will be described in detail below with reference to the following specific embodiments and the accompanying drawings of the specification, but should not be construed as limiting the scope of the present invention.
Example 1
The present embodiment provides a self-crystallization fluidized-bed reactor, the structural schematic diagram of which is shown in fig. 2, comprising:
a reactor cylinder;
the water distributor 22 is arranged at the bottom of the reactor cylinder, when the reactor runs, a water distribution area 23 is arranged below the water distributor 22, and a cavity above the water distributor 22 forms a fluidized bed layer 24;
a water receiving weir 26 is arranged at the periphery of the top of the reactor barrel, a solid-liquid separation area 25 is arranged below the water receiving weir 26, and an annular water receiving pipe 27 is arranged between the solid-liquid separation area 25 and the fluidized bed 24;
the side wall of the reactor cylinder is provided with a water inlet 30, a slag discharging port 31, a medicine adding port 32, a water outlet 33 and a sampling tube 35,
wherein the water inlet 30 and the slag discharging port 31 are respectively positioned below and above the water distributor 22; the dosing port 32 is positioned in the middle of the reactor cylinder; the water outlet 33 is positioned on the side wall of the top of the reactor;
the upper part and the bottom of the side wall of the reactor cylinder are connected with a circulating water system 28, and the circulating water system 28 comprises a circulating pump, a water outlet pipeline and a water return pipeline; wherein, one end of the water outlet pipeline is connected with the annular water collecting pipe 27, and the other end of the water outlet pipeline is connected with the bottom of the reactor cylinder body through a circulating pump and a water return pipeline;
The 3 sampling pipes 35 are uniformly distributed on the side wall of the reactor cylinder between the water outlet pipeline and the water distributor 22.
A pickling medicine inlet 34 for being connected with a pickling device is arranged above the slag discharging port 31; and the side walls of the reactor cylinder above and below the water distributor 22 are connected with an acid washing circulation system 29, and the acid washing circulation system 29 comprises an acid washing circulation pump, an acid washing water pipeline and an acid washing water return pipeline.
Example 2
The present embodiment provides a self-crystallization fluidized-bed reactor, the structural schematic diagram of which is shown in fig. 3, comprising:
a reactor cylinder;
the water distributor 22 is arranged at the bottom of the reactor cylinder, when the reactor runs, a water distribution area 23 is arranged below the water distributor 22, and a cavity above the water distributor 22 forms a fluidized bed layer 24;
a water receiving weir 26 is arranged at the periphery of the top of the reactor barrel, a solid-liquid separation area 25 is arranged below the water receiving weir 26, and an annular water receiving pipe 27 is arranged between the solid-liquid separation area 25 and the fluidized bed 24;
the side wall of the reactor cylinder is provided with a water inlet 30, a slag discharging port 31, a medicine adding port 32, a water outlet 33 and a sampling tube 35,
wherein the water inlet 30 and the slag discharging port 31 are respectively positioned below and above the water distributor 22; the dosing port 32 is positioned in the middle of the reactor cylinder; the water outlet 33 is positioned on the side wall of the top of the reactor;
The upper part and the bottom of the side wall of the reactor cylinder are connected with a circulating water system 28, and the circulating water system 28 comprises a circulating pump, a water outlet pipeline and a water return pipeline; wherein, one end of the water outlet pipeline is connected with the annular water collecting pipe 27, and the other end of the water outlet pipeline is connected with the bottom of the reactor cylinder body through a circulating pump and a water return pipeline;
the 3 sampling pipes 35 are uniformly distributed on the side wall of the reactor cylinder between the water outlet pipeline and the water distributor 22.
A pickling medicine inlet 34 for being connected with a pickling device is arranged above the slag discharging port 31; and the side walls of the reactor cylinder above and below the water distributor 22 are connected with an acid washing circulation system 29, and the acid washing circulation system 29 comprises an acid washing circulation pump, an acid washing water pipeline and an acid washing water return pipeline.
The solid-liquid separation zone 25 of the reactor bowl is provided with removable diagonal or inclined plate packing 36.
Example 3
The embodiment provides a system for self-crystallizing high-fluorine and high-hardness wastewater by a two-stage two-phase fluidized bed, the structure schematic diagram of the system is shown in fig. 1, and the system comprises: two self-crystallizing fluidized bed reactors as described in example 1 (or example 2): the two-stage reactor is respectively marked as a first-stage reactor 1 (wherein the water circulation system of the first-stage reactor comprises a first-stage reactor circulating pump 6 and a return pipeline 16, the return pipeline 16 comprises a water outlet pipeline and a return pipeline), and a second-stage reactor 2 (wherein the water circulation system of the second-stage reactor comprises a second-stage reactor circulating pump 8 and a return pipeline 18, and the return pipeline 18 comprises a water outlet pipeline and a return pipeline); the device comprises a medicament A feeding device 3, a medicament B feeding device 4, a primary material pool 7 and a secondary material pool 9;
Wherein, the raw water pool is connected with the water inlet of the primary reactor 1 through a water inlet pipeline 15 and a water inlet pump 5;
the reagent A feeding device 3 is connected with a reagent feeding port of the primary reactor 1 through a reagent A feeding pipeline 13;
the deslagging port of the primary reactor 1 is connected with the primary material pool 7 through a primary reactor sludge discharge pipe 17;
the water outlet of the primary reactor 1 is connected with the water inlet of the secondary reactor 2 through a primary water outlet pipeline 11;
the drug B adding device 4 is connected with a drug adding port of the secondary reactor 2 through a drug B adding pipeline 14;
the deslagging port of the secondary reactor 2 is connected with the secondary material pool 9 through a secondary reactor sludge discharge pipe 19;
the water outlet 33 of the secondary reactor 2 is connected with a recovery device through a secondary water outlet pipeline 12;
the system also comprises a pickling device 10, wherein the pickling device 10 is respectively connected with a pickling medicine inlet of the primary reactor 1 and a pickling medicine inlet of the secondary reactor 2 through a primary pickling pipeline 20 and a secondary pickling pipeline 21.
Example 4
The embodiment provides a method for treating high-fluorine and high-hardness wastewater by two-stage two-phase fluidized bed self-crystallization, which is realized by adopting the system for treating high-fluorine and high-hardness wastewater by two-stage two-phase fluidized bed self-crystallization provided by embodiment 3, and specifically comprises the following steps:
The raw water quality is as follows: total hardness = 1462mg/L (CaCO) 3 ) Calcium hardness=1207mg/L (CaCO) 3 ) Alkalinity=283 mg/L (CaCO) 3 )、[Ca 2+ ]＝483mg/L、[F - ]＝7019mg/L，pH＝2.5。
Primary crystallization reactor operating parameters: caO emulsion with agent A of 20% (mass ratio) and adding amount of [ Ca ] 2 + ]/[F - ]The molar ratio=0.7:1, the reflux ratio=10-15:1, the surface separation load is 1.5m/h, the rising flow rate of the empty tower is 30-60 m/h, and the pH value=4.5-6.5;
secondary crystallization reactor operating parameters: medicament B is Na with concentration of 0.5M 2 CO 3 Solution, the addition amount of which is as follows [ Ca ] 2+ ]/[CO 3 2- ]The molar ratio=1:1.1, the reflux ratio (reflux amount/water inflow) =8-13:1, the surface separation load is 4m/h, the rising flow rate of the empty tower is 80-100 m/h, and the pH value=8.0-9.5.
Full system water outlet (secondary water outlet) [ Ca ] 2+ ]＝15mg/L、[F - ]The primary reactor precipitate is mainly CaF with the particle size of 60-200 mu m 2 The particles and the secondary reactor sediment are mainly CaCO with the particle size of 1-3 mm 3 The crystal has good fluidity and no obvious wall hanging phenomenon. The calcium fluoride and calcium carbonate crystal particles have good drying and dehydration properties, the purity of the calcium fluoride is more than 80%, the whiteness value of the calcium carbonate particles is 80, the purity is more than 90%, and the calcium fluoride and the calcium carbonate crystal particles have good recycling value.
Example 5
The embodiment provides a method for treating high-hardness wastewater by two-stage two-phase fluidized bed self-crystallization, which is realized by adopting the system for treating high-fluorine and high-hardness wastewater by two-stage two-phase fluidized bed self-crystallization provided by embodiment 3, and specifically comprises the following steps:
The raw water quality is as follows: total hardness = 3902mg/L (CaCO) 3 ) Calcium hardness=3709 mg/L (CaCO) 3 ) Magnesium hardness=193 mg/L (CaCO) 3 )、[Ca 2+ ]＝1483mg/L、[Mg 2+ ]46mg/L, basicity 850mg/L (CaCO) 3 )，pH＝7。
Primary crystallization reactor operating parameters: agent A was 20% (mass ratio) Ca (OH) 2 According to [ Ca ] 2+ ]Total basicity/[](mass ratio) =2:1, reflux ratio=4-7:1, surface separation load 6m/h, empty tower ascending flow rate 40-80 m/h, pH=9.5-10;
secondary crystallization reactor operating parameters: medicament B is 0.5M Na 2 CO 3 According to [ Ca ] 2+ ]/[CO 3 2- ]The molar ratio=1:1.5 is added, the reflux ratio=4-7:1, the rising flow rate is 40-80 m/h, and the pH value is 8.5-9.8.
Full system water outlet (secondary water outlet) [ Ca ] 2+ ]＝15mg/L，[Ca 2+ ]The removal rate is 99%, the calcium carbonate crystal grows well in the running process of the system, the particle size of the calcium carbonate crystal is 1-3 mm, the fluidity is good, and no obvious wall hanging phenomenon exists. The calcium carbonate crystal particles have good drying and dehydration properties, the whiteness value is 86, and the calcium carbonate crystal particles have good recycling value.
Example 6
The embodiment provides a method for treating high-fluorine wastewater by two-stage two-phase fluidized bed self-crystallization, which is realized by adopting the system for treating high-fluorine and high-hardness wastewater by two-stage two-phase fluidized bed self-crystallization provided by embodiment 3, and specifically comprises the following steps:
The water quality of raw water is F - ]＝2500mg/L，pH＝2.7。
Primary crystallization reactor operating parameters: caO emulsion and CaCl with agent A of 20% (mass ratio) 2 Mixing the solution, wherein CaCl 2 The ratio is 10%. The medicine A is according to [ Ca ] 2+ ]/[F - ]The molar ratio=1.5:1 is added, the reflux ratio=5-10:1, the surface separation load is 1m/h, the rising flow rate of the empty tower is 15-45 m/h, and the pH value is about 5.5;
secondary crystallization reactor operating parameters: medicament B is 0.5M Na 2 CO 3 According to [ Ca ] 2+ ]/[CO 3 2- ]The molar ratio=1:1.5 is added, the reflux ratio=9-14:1, the surface separation load is 4m/h, the rising flow rate of the empty tower is 85-100 m/h, and the pH value is about 9.0.
Full system water outlet (secondary water outlet) [ F ] - ]<15mg/L，[F - ]Removal rate of>99.4 percent, the precipitated product of the primary reactor is calcium fluoride crystal with the particle size of 60 to 100 mu m, the calcium fluoride crystal is discharged out of the reactor in the form of precipitated sludge, and the precipitated product of the secondary reactor is calcium carbonate particles with the particle size of 1 to 3 mm. The sediment has good flow uniformity, no obvious wall hanging phenomenon, good drying and dehydration performance, purity of more than 80 percent and good recycling value.
Claims (17)
1. A method for treating high-fluorine and high-hardness wastewater by two-stage two-phase fluidized bed self-crystallization, which is realized by a system for treating high-fluorine and high-hardness wastewater by two-stage two-phase fluidized bed self-crystallization, wherein the system comprises: two self-crystallizing fluidized bed reactors: the reactor is respectively marked as a primary reactor (1) and a secondary reactor (2); the device comprises a medicament A feeding device (3), a medicament B feeding device (4), a primary material pool (7) and a secondary material pool (9);
Wherein, the raw water pool is connected with the water inlet of the primary reactor (1) through a water inlet pipeline (15) by a water inlet pump (5); the reagent A feeding device (3) is connected with a feeding port of the primary reactor (1) through a reagent A feeding pipeline (13); the deslagging port of the primary reactor (1) is connected with the primary material pool (7) through a primary reactor deslagging pipe (17); the water outlet of the primary reactor (1) is connected with the water inlet of the secondary reactor (2) through a primary water outlet pipeline (11); the medicament B feeding device (4) is connected with a medicament feeding port of the secondary reactor (2) through a medicament B feeding pipeline (14); the deslagging port of the secondary reactor (2) is connected with the secondary material pool (9) through a sludge discharge pipe (19) of the secondary reactor; the water outlet (33) of the secondary reactor (2) is connected with a recovery device through a secondary water outlet pipeline (12), and is characterized in that the method comprises the following steps:
a starting stage:
(1) Firstly, injecting raw water into a first-stage reactor according to the flow calculated by the maximum hydraulic retention time, and submerging a water outlet pipeline of a circulating water system by the liquid level in the first-stage reactor; simultaneously adding the reagent A into a cavity of the primary reactor;
Then starting a circulating water system, sending the return water to a water distribution area of the primary reactor to be mixed with raw water, and then uniformly rising the mixture into a cavity of the primary reactor through a water distributor, so that the rising flow rate of wastewater in the primary reactor reaches the minimum design rising flow rate to form supersaturated solution; during the circulating flow in the primary reactor, ca 2+ And F is equal to - Or Ca 2+ With CO 3 2- Self-crystallizing the supersaturated solution to form CaF 2 Or CaCO (CaCO) 3 Fine crystal particles, followed by formation of a fluidized bed of particles;
(2) The primary effluent automatically flows into a water distribution area of the secondary reactor, flows to a water outlet pipe of a circulating water system submerged by the liquid level in the secondary reactor, and simultaneously, a reagent B is added into a cavity of the secondary reactor;
then starting a circulating water system of the secondary reactor, and after the return water is sent to a water distribution area of the secondary reactor and mixed with the primary effluent, uniformly rising the mixed wastewater into a cavity of the secondary reactor through a water distributor;
under such conditions, supersaturated solution is formedA liquid; during the circulating flow in the secondary reactor, ca 2+ With CO 3 2- Self-crystallizing the supersaturated solution to produce CaCO 3 Fine crystal particles, followed by formation of a fluidized bed of particles;
during the start-up phase, the secondary effluent [ Ca ] 2+ ]、[F - ]The concentration is higher, so that the secondary effluent is also required to be returned to the raw water pool for continuous treatment;
and (3) an operation stage:
(1) Raw water and return water of the primary reactor enter a water distribution area from the bottom of the primary reactor to be mixed, uniformly distributed by a water distributor, uniformly lifted into a fluidized particle bed of the primary reactor at a certain air tower lifting flow rate, and simultaneously uniformly lifted into a fluidized particle bed of the primary reactor at a certain [ Ca ] 2+ ]/[F - ]The medicine A is injected into a fluidized particle bed layer of a primary reactor in a molar ratio or a certain total alkalinity mass ratio to form supersaturated solution; under the specific hydraulic condition of the fluidized bed reactor, the crystal forming ions self-crystallize and grow into crystal particles with certain particle size, a fluidized crystal particle bed layer is gradually formed in the cavity of the primary reactor, and F in raw water passes through the fluidized bed layer from bottom to top - Or Ca 2+ Can be removed from the water; the raw water further rises to a solid-liquid separation area, crystal particles remain in the primary reactor, supernatant is collected through a water receiving weir at the top, and automatically flows into a water distribution area at the bottom of the secondary reactor;
(2) Mixing the primary effluent with the secondary reactor reflux water in the water distribution area of the secondary reactor, uniformly distributing water by a water distributor, uniformly rising to the inside of the cavity of the secondary reactor at a certain rising flow rate of the empty tower, and simultaneously uniformly mixing with a certain [ Ca ] 2+ ]/[CO 3 2- ]The molar ratio of agent B is injected thereto; in the cavity of the secondary reactor, the primary effluent continuously entering, the secondary reactor reflux water and the medicament B form supersaturated solution, under the specific hydraulic condition of the fluidized bed reactor, the crystal forming ions self-crystallize and grow into crystal particles with certain particle size, a fluidized crystal particle bed layer is gradually formed in the cavity of the reactor, and Ca in the water is in the process of passing through the fluidized bed layer from bottom to top 2+ Is removed; the primary effluent further rises to a solid-liquid separation zone, crystal particles are reserved in the secondary reactor under the action of gravity precipitation, supernatant fluid is collected through a top water receiving weir, and finally, the supernatant fluid is recovered through a secondary water outlet pipe discharge system;
in a system for treating high-fluorine and high-hardness wastewater by two-stage two-phase fluidized bed self-crystallization, the self-crystallization fluidized bed reactor comprises:
a reactor cylinder;
the water distributor (22) is arranged at the bottom of the reactor cylinder, when the reactor runs, a water distribution area (23) is arranged below the water distributor (22), and a cavity above the water distributor (22) forms a fluidized bed layer (24);
a water receiving weir (26) is arranged at the periphery of the top of the reactor barrel, a solid-liquid separation area (25) is arranged below the water receiving weir (26), and an annular water receiving pipe (27) is arranged between the solid-liquid separation area (25) and the fluidized bed layer (24);
The side wall of the reactor cylinder is provided with a water inlet (30), a slag discharging port (31), a medicine adding port (32), a water outlet (33) and a sampling tube (35),
wherein the water inlet (30) and the slag discharging port (31) are respectively positioned below and above the water distributor (22); the dosing port (32) is positioned in the middle of the reactor cylinder; the water outlet (33) is positioned on the side wall of the top of the reactor;
a circulating water system (28) is connected above and at the bottom of the side wall of the reactor cylinder, and the circulating water system (28) comprises a circulating pump, a water outlet pipeline and a water return pipeline; one end of the water outlet pipeline is connected with the annular water collecting pipe (27), and the other end of the water outlet pipeline is connected with the bottom of the reactor cylinder body through the circulating pump and the water return pipeline;
the sampling pipes (35) are uniformly distributed on the side wall of the reactor cylinder between the water outlet pipeline of the circulating water system (28) and the water distributor (22).
2. The method according to claim 1, characterized in that the inner bottom of the primary material pool (7) and the inner bottom of the secondary material pool (9) are provided with grid meshes.
3. The method according to claim 1, characterized in that the system further comprises a pickling device (10), wherein the pickling device (10) is respectively connected with a pickling feed port of the primary reactor (1) and a pickling feed port of the secondary reactor (2) through a primary pickling pipeline (20) and a secondary pickling pipeline (21).
4. The method according to claim 1, wherein the number of sampling tubes (35) is 3-4.
5. The method according to claim 1, characterized in that a pickling feed port (34) for connection to a pickling device is arranged above the slag discharge port (31); the side walls of the reactor cylinder above and below the water distributor (22) are connected with an acid washing circulation system (29), the acid washing circulation system (29) comprises an acid washing circulation pump, an acid washing water pipeline and an acid washing return water pipeline, and the acid washing outlet pipeline is arranged above the water distributor (22) and below an acid washing medicine inlet (34); the pickling return pipeline is positioned below the water distributor (22).
6. A method according to claim 1, characterized in that the solid-liquid separation zone (25) of the reactor vessel is provided with a detachable chute packing or inclined plate packing (36), and that the chute packing or inclined plate packing (36) is fixed to the reactor vessel wall below the water receiving weir.
7. The method according to claim 1, wherein when the raw water is high-fluorine high-hardness wastewater,
parameters of the run stage primary reactor: the agent A is CaO or Ca (OH) 2 With CaCl 2 Wherein CaCl 2 0-25% of the total mass of the dry matter mixture; the medicine A is according to [ Ca ] 2+ ]/[F - ]Molar ratio = 0.7-1.5:1;
the hydraulic retention time HRT is 1-4 h, the surface separation load is 1-4 m/h, the rising flow velocity v of the empty tower is 10-60 m/h, and the inside of the reactor is provided with a high-pressure reactorpH value of<7.5; the reflux ratio is 1-20:1, and the temperature range is 10-50 o C；
The crystal particles discharged from the bottom of the primary reactor are CaF with the particle size of 60-200 mu m 2 Crystal particles;
parameters of the run stage secondary reactor: medicament B is Na 2 CO 3 According to [ Ca ] 2+ ]/[CO 3 2- ]The molar ratio=1:1-2;
the hydraulic retention time HRT is 0.1-1 h, the surface separation load is 4-10 m/h, the empty tower flow velocity is 20-100 m/h, the pH value in the reactor is 8-10, the reflux ratio is 1-24:1, and the temperature range is 10-50 o C；
The crystal particles discharged from the bottom of the secondary reactor are CaCO with the particle size of 1-3 mm 3 And (3) crystal particles.
8. The method of claim 7, wherein the pH in the reactor is 4 to 7.
9. The method according to claim 1, wherein when the raw water is high hardness wastewater,
and (3) an operation stage: the agent A is CaO or Ca (OH) 2 The adding amount of the emulsion is 1.5 to 2 times of the total alkalinity in water, and the pH value in the reactor is controlled to be 8.5 to 10;
in the secondary reactor, the medicament B is Na 2 CO 3 According to [ Ca ] 2+ ]/[CO 3 2- ]Adding the catalyst in a molar ratio of 1:1-2, and controlling the pH value in the reactor to be 8-10;
primary reactor, secondary reactor operating parameters: the hydraulic retention time HRT is 0.1-1 h, the surface separation load is 4-10 m/h, the air tower flow velocity is 20-100 m/h, and the temperature range is 10-50 o C, the reflux ratio is 1-24:1;
the crystal particles in the primary reactor and the secondary reactor are CaCO with the particle size of 1-3 mm 3 And (3) crystal particles.
10. The method according to claim 1, wherein when the raw water is high-fluorine wastewater,
parameters of the run stage primary reactor: the agent A is CaO or Ca (OH) 2 With CaCl 2 Wherein CaCl 2 Accounting for 0-25% of the total mass of the dry matter mixture, and the medicament A is prepared by the following formula [ Ca ] 2+ ]/[F - ]Molar ratio = 0.7-1.5:1;
the hydraulic retention time HRT is 1-4 h, the surface separation load is 1-4 m/h, the rising flow velocity v of the empty tower is 10-60 m/h, the reflux ratio is 1-20:1, and the pH value in the reactor is less than 7.5;
the crystal particles discharged from the bottom of the primary reactor are CaF with the particle size of 60-200 mu m 2 Crystal particles;
parameters of the run stage secondary reactor: medicament B is Na 2 CO 3 According to [ Ca ] 2+ ]/[CO 3 2- ]The molar ratio=1:1-2;
the hydraulic retention time HRT is 0.1-1 h, the surface separation load is 4-10 m/h, the rising flow velocity v of the empty tower is 20-100 m/h, and the temperature range is 10-50 o C, the reflux ratio is 1-24:1, and the pH value in the reactor is 8-10;
the crystal particles in the secondary reactor are CaCO with the particle size of 1-3 mm 3 And (3) crystal particles.
11. The method of claim 10, wherein the pH in the reactor is 4 to 7.
12. The method of claim 1, wherein, when the removal target is fluoride ions,
parameters of the first stage reactor at start-up stage: the agent A is CaO or Ca (OH) 2 With CaCl 2 Wherein CaCl 2 0-25% of the total mass of the dry matter mixture; the medicine A is according to [ Ca ] 2+ ]/[F - ]The molar ratio=1.5-2:1;
the maximum hydraulic retention time is 4-5 h, the pH value in the primary reactor is=6-7.5, and the minimum design rising flow rate is 4-10 m/h;
parameters of the start-up stage secondary reactor: medicament B is Na 2 CO 3 According to [ Ca ] 2+ ]/[CO 3 2- ]The molar ratio=1:1.5-2;
the maximum hydraulic retention time of the primary effluent is 1-1.5 h; and the rising flow rate of the mixed wastewater reaches 10-20 m/h, and the pH value in the secondary reactor is controlled to be 9-10.
13. The method of claim 1, wherein, when the removal target is temporary calcium hardness,
parameters of the first stage reactor at start-up stage: the agent A is CaO or Ca (OH) 2 The adding amount of the emulsion is 2 to 2.5 times of the total alkalinity in water,
the maximum hydraulic retention time is 1-1.5 h, the pH value in the primary reactor is 9.5-10, the minimum design rising flow rate is 10-20m/h,
parameters of the start-up stage secondary reactor: medicament B is Na 2 CO 3 According to [ Ca ] 2+ ]/[CO 3 2- ]The molar ratio=1:1.5-2;
the maximum hydraulic retention time of the primary effluent is 1-1.5 h; and the rising flow rate of the mixed wastewater reaches 10-20m/h, and the pH value in the secondary reactor is controlled to be 9-10.
14. The method of claim 5, further comprising a post-reactor shutdown treatment operation comprising the steps of:
a. after the reactor is stopped, all the waste water and particles in the reactor are immediately emptied to a primary material pool or a secondary material pool;
b. and (3) starting the acid washing device, injecting acid solution into the first-stage reactor and the second-stage reactor, starting the acid washing circulation system to carry out acid washing on the water distributor after the liquid level of the acid solution is beyond the acid washing water outlet pipeline, and then emptying the acid washing waste liquid, flushing the inside of the reactor by clear water, and stopping the operation for a long time after the reactor is emptied and washed.
15. The method according to any one of claims 1 to 13, further comprising the step of determining the fluidized bed height and the deslagging frequency of the primary reactor and the secondary reactor.
16. The method according to claim 15, wherein the deslagging frequency of the primary reactor and the secondary reactor is determined according to the corresponding fluidized bed height, namely, the fluidized bed height is kept to be less than 3/4 of the cavity part of the reactor, and deslagging is needed when the fluidized bed height is more than 3/4 of the cavity part of the reactor.
17. The process of claim 16 wherein the fluidized bed is maintained at a height of 1/2 to 3/4 of the reactor cavity portion.
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| CN118529833B (en) * | 2024-07-24 | 2024-09-17 | 东晟环保科技集团(安徽)股份有限公司 | Multistage fluoride ion crystallization and recovery integrated device and treatment method |
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