CN206308090U

CN206308090U - Two-stage two-phase fluidization bed is from crystallization treatment fluorine high, the system of high rigidity waste water

Info

Publication number: CN206308090U
Application number: CN201621290681.0U
Authority: CN
Inventors: 梁思懿; 刘寅; 刘全金; 杜兵; 祝群力; 李�杰; 尹航; 曹建平; 何然; 王珊
Original assignee: Zhongye Jingcheng Engineering Technology Co Ltd; Beijing Municipal Research Institute of Environmental Protection
Current assignee: MCC Capital Engineering and Research Incorporation Ltd; Zhongye Jingcheng Engineering Technology Co Ltd; Beijing Municipal Research Institute of Environmental Protection
Priority date: 2016-11-29
Filing date: 2016-11-29
Publication date: 2017-07-07
Anticipated expiration: 2026-11-29

Abstract

The utility model provides a kind of two-stage two-phase fluidization bed from crystallization treatment fluorine high, the system of high rigidity waste water, and it includes：Two crystallize fluidized-bed reactor certainly：First-stage reactor, second reactor are designated as respectively；Medicament A throwing devices, medicament B throwing devices, one-level material pond and two grades of material ponds；Wherein, former pond is connected via intake pump by inlet pipeline with the water inlet of first-stage reactor；Medicament A throwing devices are connected by medicament A dosing pipes with the dosing mouth of first-stage reactor；The slag-drip opening of first-stage reactor is connected by first-stage reactor discharge pipeline with the one-level material pond；The delivery port of first-stage reactor is connected by primary effluent pipeline with the water inlet of the second reactor；Medicament B throwing devices are connected by medicament B dosing pipes with the dosing mouth of second reactor；The slag-drip opening of second reactor is connected by second reactor discharge pipeline with two grades of material ponds；The delivery port of second reactor is connected by secondary effluent pipeline with retracting device.

Description

Two-stage two-phase fluidization bed is from crystallization treatment fluorine high, the system of high rigidity waste water

Technical field

The utility model is related to a kind of two-stage two-phase fluidization bed from crystallization treatment fluorine high, the system of high rigidity waste water, belongs to Technical field of waste water processing.

Background technology

In field of waste water treatment, using to certain chemical substance is added in waste water, make the chemical substance and some of which molten Solution material produces reaction, the method for generating difficulty soluble salt and precipitating, referred to as chemical precipitation method.The formation of precipitation experiencings one From scratch, the process of occurrence and development from small to large, this process is sufficiently complex.

Briefly, the process that precipitation is formed includes two mistakes of growth of the formation (nucleation) of nucleus and precipitation particle Journey.

(1) formation-homogeneous nucleation or heterogeneous nucleation of nucleus, i.e.,：Configurational ion homogeneous nucleation under electrostatic interaction is formed Ion pair, ion pair re-forms ion aggregation；Or configurational ion heterogeneous nucleation under inducing action directly forms ion and gathers Collective, the ion aggregation for then being formed by homogeneous nucleation or heterogeneous nucleation re-forms little crystal grain；

(2) growth (or growth of nucleus) of precipitation particle-generation crystalline precipitate or amorphous sediment, i.e.,：Small crystal nucleus shape Into small depositing particles, then small depositing particles pass through to align to form crystalline precipitate again, or form amorphous heavy by cohesion Form sediment.

Traditional chemical precipitation method fluorine removal, except hard, be with chemical precipitation principle (solubility product principle), by chemical drugs Fluorine ion, calcium ion, magnesium ion are changed into the process of calcirm-fluoride, calcium carbonate and magnesium hydrate precipitate for agent, but this process is produced The often amorphous sediment of precipitation, the amorphous sediment is loosely flocked together and shape by many small precipitation particles Into, the arrangement for precipitating particle is unordered in a jumble, wherein and often include substantial amounts of moisture and other impurities, so being loose cotton-shaped Precipitation, the volume of whole precipitation is larger, therefore its technical process often needs simultaneously to enter equipped with coagulation, precipitation or clarifying process OK.In traditional depositing technology, the measures such as excessive dosing, dosing coagulant are taken to accelerate precipitation, the miscellaneous of sludge is increased again Matter so that precipitating sludge non-recovery value, increased the difficulty of Treatment of Sludge, and sludge volume is big, moisture content is high, sludge Separately disposal even be more difficult to than water process.

Because crystalline precipitate inner ion is regularly arranged, close structure, if precipitation result can be made for crystalline precipitate, can be big Big to improve deposition efficiency, it is advantageous in that：Crystalline precipitate is fine and close, bottom of pond is easily deposited to, without adding coagulated agent, sludge body Product is greatly reduced, and moisture content is low, it is easy to recycled or final disposal.In recent years, " induction crystalline deposit technology " obtains very fast Development, the technology is principle to induce crystallization, and combines fluid bed or packed-bed reactor form, crystallization reactor domestic demand used Preset carrier or filler are wanted as crystal seed, makes the material to be removed occur to induce crystallization reaction on crystal seed, so as to be deposited on crystalline substance In kind, processing intent is then reached by bottom spoil disposal.Inducing the central principle of crystallization is：Heterogeneous nucleation under inducing action → Align growth → generation crystalline precipitate.The effect of crystal seed is：Due to the presence of crystal seed, the activation energy of precipitation reaction drops It is low, so that being able in seed surface precipitation reaction compared with the deposit of low saturation in solution, grown in the form of crystal.For Realize induction crystallization, as far as possible avoid the configurational ion degree of supersaturation of sediment larger, in order to avoid calcium carbonate or calcirm-fluoride it is spontaneous into Core, these fine crystals can not be attached to seed surface, with water outlet outflow reactor delivery turbidity can be caused to increase.

At present to induce crystalline deposit technical finesse fluorine high hard waste water high, induction crystallization principle is based primarily upon, be exemplified below：

(1)《Pellet reactor processes high hardness water experimental study》, Gu Yanmei, Xu Hang, Sun Yuchen etc., civil construction and ring Border engineering, Vol.37, No.3,2015.Technology used herein is：Using fluidized-bed reactor, with the fine sand of certain particle diameter as brilliant Kind, in running, the calcium carbonate formed in the continuous adsorption reaction in fine sand surface, the weight of fine sand gradually increases, fluid bed shape The balance of state is broken, and sandstone filler sinks to reactor bottom gradually, and now the failure of sandstone filler, need to take the filler of failure Go out, be substituted for new filler.Experiment is in pH>12nd, sandstone packing material size is generated to obtain better effects under the conditions of 0.2-0.5mm etc. Calcium carbonate crystal be attached to fine sand filler surface, the calcium carbonate crystal that operation 15d or so filler adhering on surface reaches saturation, The filler for avaling need to be taken out, be replaced with new filler.

(2)《Fluid bed crystallisation processes high-concentration fluorine-containing waste water》, Li Chengwen, Central South University, environmental project Master's thesis, 2011.It is principle to induce crystallization, fluoride waste is processed using fluidized-bed process, it is brilliant to calcirm-fluoride is added in fluid bed in advance Kind, then allow waste water to enter fluidized bed with calcium liquid, fluorine ion is grown up with the surface heterogeneous nucleation of calcium ion crystal seed.Water outlet PH=6- 8, delivery turbidity is controlled in below 50NTU, and the fluorine rate of recovery is up to 96%.The calcirm-fluoride product granularity of generation is uniform, average grain diameter 100 microns, can be used as fluorite level fluorination calcium product.

(3)《Carrier induced precipitation crystallization method softened water and the research of defluorinate》, Chen Ping, Xi'an University of Architecture and Technology, environment Doctor of Engineering's paper, 2004.Quartz sand induction CaCO is systematically have studied in text₃Precipitation reaction dynamics, thermodynamics and its lure Lead mechanism, quartz sand induced precipitation crystallization softened water, quartz sand induction CaF₂Crystallization defluorinate and its induction mechanism.

(4) Dutch DHV companies and Taiwan industrialization research institute, have been successfully realized the industry of fluid bed crystallization technique Change, it uses induction crystallisation, fluorine removal precipitating reagent used is calcium chloride, needed before reaction individually plus alkali adjusts wastewater pH to neutrality； Deliming precipitating reagent used is NaOH；It is required for constantly adding crystal seed before operation and in running, generally quartz Sand.

Liu Weirui exists《Efficient crystallization processes the research of high-salt wastewater except hard technology》(University of the Inner Mongol, environmental project master Paper, 2014) in propose a kind of " treatment strong brine from crystallize softening process ".The technique is higher suitable for calcium and magnesium hardness, And the RO concentrated waters with higher alkalisation are except firmly, its typical service condition is：Precipitating reagent is NaOH, generation precipitate C aCO₃、Mg (OH)₂；Crystallization reactor is hybrid power to stir；It is crystallization main control parameters, deliming crystallization reactor pH=with pH 9.5-10.2 (preferably 9.8-10.0), demagging crystallization reactor pH=11-11.5.

The patent that the relevant FLUORIDE REMOVAL IN WASTEWATER that has authorized, waste water soften is less, and is differed or similar to the utility model, It is specific as follows：

(1) Chinese patent CN101941752A discloses a kind of processing method and processing device of fluoride waste.The invention is provided A kind of processing method and processing device of fluoride waste, is crystallization reactor with solid-liquid two-phase flowization bed, is added in the reactor certain The calcirm-fluoride crystal seed of amount, press fluoride waste and calcic precipitating reagent reaction ratio and sends into liquid-solid fluidized bed processing unit, make fluorine from Son is deposited on calcirm-fluoride seed surface, and the sand shape calcium fluoride precipitate sludge obtained after sedimentation is reclaimed, and coagulation water is through entering one Qualified discharge after step coagulant precipitation.This method can precipitate most of fluorine ion during fluid bed crystalline deposit, produced Sand shape calcirm-fluoride moisture content it is low, Calcium Fluoride Content is high, can be used as fluorine resource recycling；The coagulant precipitation mistake of coagulation water Flocculant usage is few in journey, and sludge yield is few, therefore waste water treatment and integral low cost.

(2) Chinese patent CN104860446A discloses a kind of softening of high rigidity industry water separation method and system.Should A kind of high rigidity industry water of disclosure of the invention softens separation method, including：The pH value of high rigidity industry water is adjusted in sludge-tank To 8-10, incrustation ion forms sediment in making water；The industry water that precipitation is formed in sludge-tank is transported to hollow-fibre membrane dense Compression apparatus, softened water is obtained by membrane separating method.The invention uses membrane separating method, different from chemistry of the present utility model certainly Crystallization removes hard method.

Utility model content

In order to solve above-mentioned shortcoming and defect, the purpose of this utility model is to provide a kind of from crystallization fluidized-bed reaction Device.

The purpose of this utility model is also resided in and provided comprising the above-mentioned two-stage two-phase fluidization bed from crystallization fluidized-bed reactor From crystallization treatment fluorine high, the system of high rigidity waste water.

The purpose of this utility model also reside in provide application said system two-stage two-phase fluidization bed from crystallization treatment fluorine high, The method of high rigidity waste water.

To reach above-mentioned purpose, on the one hand, the utility model provides one kind from crystallization fluidized-bed reactor, should be from crystallization Fluidized-bed reactor includes：

Reactor shell；

The water-locator 22 of reactor shell bottom is arranged at, when reactor runs, the lower section of water-locator 22 is water distributing area 23, cloth The top cavity of hydrophone 22 will form fluidized-bed layer 24；

Reactor shell top perimeter is provided with receipts mill weir 26, and the lower section of receipts mill weir 26 is solid-liquid displacement zone 25, the solid-liquid point Ring-type is provided between area 25 and fluidized-bed layer 24 and receives water pipe 27；

Reactor cylinder side wall is provided with water inlet 30, slag-drip opening 31, dosing mouth 32, delivery port 33 and probe tube 35,

Wherein, the water inlet 30, slag-drip opening 31 are respectively positioned at lower section, the top of water-locator 22；The dosing mouth 32 In reactor shell middle part；The delivery port 33 is located at reactor head side wall；

Reactor cylinder side wall top and bottom are connected with circulation 28, the circulation 28 include circulating pump, Outlet pipeline and water return pipeline；Wherein, one end of outlet pipeline is received water pipe 27 and is connected with the ring-type, the other end of outlet pipeline It is connected with the bottom of reactor shell by water return pipeline again via circulating pump；

The probe tube 35 is uniformly distributed in the reactor shell between the outlet pipeline of circulation 28 and water-locator 22 On the wall of side.

According to described in the utility model from crystallization fluidized-bed reactor, it is preferable that the probe tube 35 is 3-4 roots.

According to described in the utility model from crystallization fluidized-bed reactor, it is preferable that the top of the slag-drip opening 31 is provided with For the pickling feeding opening 34 being connected with acid dip pickle；And be connected with the reactor cylinder side wall over and under of water-locator 22 The pickling circulatory system 29, the pickling circulatory system 29 includes pickling circulating pump and pickling outlet pipeline, pickling water return pipeline, its In, the pickling outlet pipeline is arranged at the top of water-locator 22 and positioned at the lower section of pickling feeding opening 34；The pickling return pipe Road is located at the lower section of water-locator 22.And pickling outlet pipeline, the position of pickling water return pipeline of the utility model pickling circulatory system 29 Put with water inlet 30, slag-drip opening 31 position without positive connection, in the utility model specific embodiment, by pickling cyclic system System 29 is arranged at the relative side of water inlet 30, slag-drip opening 31.

According to described in the utility model from crystallization fluidized-bed reactor, it is preferable that the solid-liquid displacement zone of reactor shell 25 are provided with dismountable inclined tube filler or inclined plate packing 36, and the inclined tube filler or inclined plate packing 36 are fixed on below receipts mill weir On reactor barrel.It is difficult because product calcium fluoride particles particle diameter is small when this is when fluidized-bed reactor is crystallized with fluorine removal as target So that by gravity natural subsidence, in order to strengthen solid-liquid separation effect, the solid-liquid displacement zone of reactor shell is provided with dismountable inclined tube Filler or inclined plate packing.The inclined tube filler or inclined plate packing are the conventional equipment used by water-treatment technology field.

According to described in the utility model from crystallization fluidized-bed reactor, the reactor shell inside is a cavity；

Water-locator is used to ensure that water distribution is uniform that ring-type receives water pipe and is used to ensure to receive water uniformly that the two is to forming crystallization fluidisation The necessary hydraulics of bed are most important, and the stabilization of fluidized needed for crystallization is played an important role；

Feeding opening is used to add medicament A or medicament B；

The pickling circulatory system is used for after reactor is out of service, and pickling is carried out specifically designed for water-locator；

Circulation is used to form upflow velocity higher in reactor, and to provide suitable fluidised form from crystallization；

Probe tube is used to sample the granule content in observation water sample, with the height of this determination fluidized-bed layer；

The waste water that delivery port is used to receive mill weir collection is discharged from reactor.

Reactor cavity：Part between the water-locator and circulation backflow water out (outlet pipeline).

On the other hand, the utility model additionally provides a kind of two-stage two-phase fluidization bed and is given up from crystallization treatment fluorine high, high rigidity The system of water, it includes：Two above-mentioned from crystallization fluidized-bed reactor：First-stage reactor 1, second reactor 2 are designated as respectively；Medicine Agent A throwing devices 3, medicament B throwing devices 4, one-level material pond 7 and two grades of material ponds 9；

Wherein, former pond is connected via intake pump 5 by inlet pipeline 15 with the water inlet of first-stage reactor 1；

Medicament A throwing devices 3 are connected by medicament A dosing pipes 13 with the dosing mouth of first-stage reactor 1；

The slag-drip opening of first-stage reactor 1 is connected by first-stage reactor discharge pipeline 17 with the one-level material pond 7；

The delivery port of first-stage reactor 1 is connected by primary effluent pipeline 11 with the water inlet of the second reactor 2；

Medicament B throwing devices 4 are connected by medicament B dosing pipes 14 with the dosing mouth of second reactor 2；

The slag-drip opening of second reactor 2 is connected by second reactor discharge pipeline 19 with two grades of material ponds 9；

The delivery port 33 of second reactor 2 is connected by secondary effluent pipeline 12 with retracting device.

According to system described in the utility model, it is preferable that the system also includes acid dip pickle 10, the acid dip pickle 10 By 20, two grades of pickling pipelines 21 of one-level pickling pipeline pickling feeding openings respectively with first-stage reactor 1, second reactor 2 Pickling feeding opening is connected.

According to system described in the utility model, it is preferable that the one-level material pond 7 and two grades of inner bottom parts of material pond 9 are equal It is provided with aperture plate.Wherein, aperture plate retention material used includes calcium carbonate granule or calcium fluoride particles, when retention material used is carbonic acid During calcium particle, aperture plate sieve aperture≤16 mesh (1mm)；When it is calcium fluoride particles to retain material, aperture plate sieve aperture≤200 mesh (0.075mm)。

System described in the utility model goes for various different methods and processes fluorine high, high rigidity waste water, in order to Further system of the present utility model is illustrated, the utility model is additionally provided and provides system using the utility model Two-stage two-phase fluidization bed from crystallization treatment fluorine high, the method for high rigidity waste water, it includes：

(1) raw water, is injected into first-stage reactor by the flow that maximum hydraulic detention time is calculated first, to first order reaction Liquid level in device floods the outlet pipeline of circulation；Medicament A is added simultaneously in the cavity of first-stage reactor；

Then circulation is started, recirculation water is delivered to after first-stage reactor water distributing area mixes with raw water, then by water distribution Device is uniformly risen in the cavity of first-stage reactor, waste water upflow velocity in first-stage reactor is reached minimal design upper up-flow Speed, forms supersaturated solution；During circulating in first-stage reactor, Ca²⁺With F^-Or Ca²⁺With CO₃ ^2-It is supersaturated molten Liquid occurs, from crystallization reaction, to generate CaF₂Or CaCO₃Fine crystals particle, subsequently forms fluidized particles bed；

(2), primary effluent gravity flow enters second reactor water distributing area, to second reactor in liquid level flood circulating water The outlet pipe of system, while adding medicament B in second reactor cavity；

Then second reactor circulation is started, recirculation water is delivered to second reactor water distributing area and mixed with primary effluent Afterwards, then by water-locator mixed waste water is made uniformly to rise in the cavity of second reactor；

Supersaturated solution is formed under the conditions of this；During circulating in second reactor, Ca²⁺With CO₃ ^2-Satiety Occur, from crystallization reaction, to generate CaCO with solution₃Fine crystals particle, subsequently forms fluidized particles bed；

Startup stage, [Ca in secondary effluent²⁺]、[F^-] concentration is higher, therefore also need by secondary effluent return former pond after Continuous treatment；

Operation phase：

(1), raw water and first-stage reactor recirculation water mix from first-stage reactor bottom into water distributing area, equal by water-locator After even water distribution, in uniformly rising to first-stage reactor fluidized particles bed with certain void tower upflow velocity, while with certain [Ca²⁺]/[F^-] mol ratio or certain total alkalinity mass ratio inject in first-stage reactor fluidized particles bed medicament A, Form supersaturated solution；In the specific hydraulics of fluidized-bed reactor, (including raw water is respectively fluorine high hard waste water high, high rigidity Hydraulic detention time, the void tower upflow velocity limited when waste water and fluorine waste water high) under, configurational ion grows into from crystallization The crystal grain of certain particle diameter, first-stage reactor cavity inside gradually forms the crystalline particle bed of fluidisation state, and raw water is from lower During above passing through fluidized-bed layer, the F in raw water^-Or Ca²⁺It is able to be removed from water；Raw water is further up to separation of solid and liquid Area, crystal grain is retained in first-stage reactor, and supernatant is received mill weir and collected via top, and gravity flow enters second reactor bottom Water distributing area；

(2), primary effluent mixes with second reactor recirculation water in the water distributing area of second reactor, uniform by water-locator After water distribution, second reactor cavity inside is uniformly risen to certain void tower upflow velocity, while with certain [Ca²⁺]/ [CO₃ ^2-] medicament B flows into this by mol ratio；In second reactor cavity, the primary effluent that continually enters, two grades it is anti- Device recirculation water and medicament B is answered to form supersaturated solution, under the specific hydraulics of fluidized-bed reactor, configurational ion is tied certainly Crystalline substance, and the crystal grain of certain particle diameter is grown into, the crystalline particle bed of fluidisation state, one-level are gradually formed inside reactor cavity During water outlet passes through fluidized-bed layer from bottom to top, the Ca in water²⁺Removed；Primary effluent is further up to solid-liquid point From area, during crystal grain is retained in second reactor under gravitational settling effect, supernatant is received mill weir and is collected via top, finally Reclaimed by secondary effluent pipe discharge system.

According to method described in the utility model, specifically, when removing target and being fluorine ion, (now raw water is that fluorine high is high Hard waste water or fluorine waste water high),

The parameter of startup stage first-stage reactor：Medicament A is CaO or Ca (OH)₂With CaCl₂Mixed liquor, wherein, CaCl₂ Account for the 0~25% of dry mixture gross mass；Medicament A presses [Ca²⁺]/[F^-] mol ratio=1.5~2:1 is added；

The maximum hydraulic detention time is 4~5h, pH value=6~7.5 in the first-stage reactor, the minimal design Upflow velocity is 4-10m/h；

The parameter of startup stage second reactor：Medicament B is Na₂CO₃The aqueous solution, it presses [Ca²⁺]/[CO₃ ^2-] mol ratio =1:1.5~2 are added；

The maximum hydraulic detention time of the primary effluent is 1~1.5h；The mixed waste water upflow velocity reaches 10~20m/h, and control pH value=9~10 in second reactor.

According to method described in the utility model, specifically, when removing target and being temporary transient calcium hardness, (now raw water is height Hardness waste water),

The parameter of startup stage first-stage reactor：Medicament A is CaO or Ca (OH)₂Emulsion, its dosage is pressed total in water 2~2.5 times of (mass ratioes, with CaCO of basicity₃Meter) meter,

The maximum hydraulic detention time is 1~1.5h, and pH value 9.5~10 in the first-stage reactor, the minimum sets Meter upflow velocity is 10-20m/h,

According to method described in the utility model, startup stage and operation phase, medicament A, B composition is identical, but dosage (i.e. concentration) is different.Required medicament A, B concentration during startup, it is slightly higher during than operation.Startup stage, in order to obtain larger structure it is brilliant from Sub- concentration product, to ensure the formation of nucleus；Operation phase, existing a number of nucleus is formed in reactor, can suitably be reduced Medicament A, B dosage, that is, reduce medicament A, B concentration in reactor, to save dosage.

According to method described in the utility model, wherein, startup stage is by minimum discharge injection raw water, while by maximum [Ca²⁺]/[F^-] or [Ca²⁺]/[CO₃ ^2-] ratio adds medicament A, could obtain maximum ion concentration, forms supersaturated solution, and then A large amount of tiny nucleus are spontaneously generated, this is the nucleation stage from crystallization reaction；Hereafter nucleus is constantly grown up in reflux course, just It is " developmental process of nucleus ".

, wherein it is desired to illustrate, first-stage reactor has two kinds of situations：When it is fluorine ion to remove pollutant, according to [Ca²⁺]/[F^-] mol ratio determines the addition of medicament A；When hard wastewater hardness removing high is spent, temporary hardness is removed, according in water Basicity (mainly bicarbonate alkalinity, with CaCO₃Meter) mass ratio determine the consumption of medicament A；Second reactor is used to go Except calcium ion, i.e. temporary hardness, permanent hardness can remove, now only need according to [Ca²⁺]/[CO₃ ^2-] mol ratio determines medicament The consumption of A.

According to method described in the utility model, specifically, when the raw water is fluorine high hard waste water high,

The parameter of operation phase first-stage reactor：Medicament A is CaO or Ca (OH)₂With CaCl₂Mixed liquor, wherein, CaCl₂ Account for the 0~25% of dry mixture gross mass；Medicament A presses [Ca²⁺]/[F^-] mol ratio=0.7~1.5:1 is added；

Hydraulic detention time HRT is 1~4h, and surface segregational load is 1~4m/h, and void tower upflow velocity v is 10~60m/ H, pH value in reactor<7.5, preferably 4~7；Reflux ratio is 1~20:1, temperature range is 10~50 DEG C；

The crystal grain of first-stage reactor bottom discharge is the CaF of 60~200 μm of particle diameter₂Crystal grain；

The parameter of operation phase second reactor：Medicament B is Na₂CO₃The aqueous solution, it presses [Ca²⁺]/[CO₃ ^2-] mol ratio =1:1~2 is added；

Hydraulic detention time HRT is 0.1~1h, and surface segregational load is 4~10m/h, and void tower flow velocity is 20~100m/h, PH value is 8~10 in reactor, and reflux ratio is 1~24:1, temperature range is 10~50 DEG C；

The crystal grain of second reactor bottom discharge is the CaCO of 1~3mm of particle diameter₃Crystal grain.

According to method described in the utility model, wherein, [F in the fluorine hard waste water high high^-] >=300mg/L, calcium hardness ≥500mg/L(CaCO₃)。

According to method described in the utility model, specifically, when the raw water is high rigidity waste water,

Operation phase：PH value is 8.5~10 in first-stage reactor, and medicament A is CaO or Ca (OH)₂Emulsion, it is added Amount (mass ratio, with CaCO based on 1.5~2 times of total alkalinity in water₃Meter)；

In second reactor, medicament B is Na₂CO₃The aqueous solution, it presses [Ca²⁺]/[CO₃ ^2-] mol ratio=1:1~2 enters Row addition, it is 8~10 to control the pH value in reactor；

First-stage reactor, second reactor operational factor：Hydraulic detention time HRT is 0.1~1h, and surface segregational load is 4~10m/h, void tower flow velocity is 20~100m/h, and temperature range is 10~50 DEG C, and reflux ratio is 1~24:1；

First-stage reactor, the crystal grain of second reactor bottom discharge are the CaCO of 1~3mm of particle diameter₃Crystal grain.

According to method described in the utility model, wherein, the calcium hardness >=500mg/L (CaCO of the high rigidity waste water₃)。

According to method described in the utility model, specifically, when the raw water is fluorine waste water high,

The parameter of operation phase first-stage reactor：Medicament A is CaO or Ca (OH)₂With CaCl₂Mixed liquor, wherein, CaCl₂ The 0~25% of dry mixture gross mass is accounted for, medicament A presses [Ca²⁺]/[F^-] mol ratio=0.7~1.5:1 is added；

Hydraulic detention time HRT is 1~4h, and surface segregational load is 1~4m/h, and void tower upflow velocity v is 10~60m/ H, temperature range is 10~50 DEG C, and reflux ratio is 1~20:1, pH value in reactor<7.5, preferably 4~7；

Hydraulic detention time HRT be 0.1~1h, surface segregational load be 4~10m/h, void tower upflow velocity v be 20~ 100m/h, temperature range is 10~50 DEG C, and reflux ratio is 1~24:1, pH value is 8~10 in reactor；

Crystal grain in second reactor is the CaCO of 1~3mm of particle diameter₃Crystal grain.

According to method described in the utility model, wherein, [F in fluorine waste water high^-]≥300mg/L。

According to method described in the utility model, wherein, CaCl₂Account for dry mixture gross mass 0~25% refers to With dry (CaO or Ca (OH)₂With CaCl₂) gross weight percentage calculate, such as：CaO powder and CaCl₂The gross weight of powder is 100g, CaCl₂25g, i.e. CaCl₂Accounting 25%.

According to method described in the utility model, specifically, the method also includes determining first-stage reactor, second reactor Fluidized-bed layer height and the step of the deslagging frequency：

Wherein, first-stage reactor, the determination of second reactor fluidized-bed layer height is comprised the following steps：

Mixed liquor in a certain amount of reactor is taken out from probe tube, after standing, the sunk solid volume and standing for being settled When the ratio between preceding mixeding liquid volume reaches more than 10%~30%, that is, think that bed height has reached the sampling open height；

The first-stage reactor, the fluidized-bed layer of the deslagging frequency according to corresponding to it of second reactor highly determine, i.e., Keep fluidized-bed layer highly to account for less than the 3/4 of reactor cavity part (part more than water-locator, between backflow water out) to be advisable, If fluidized-bed layer highly accounts for reactor cavity part more than 3/4, that is, need deslagging；

Fluidized-bed layer is kept highly to account for the 1/2- of reactor cavity part (part more than water-locator, between backflow water out) 3/4。

According to method described in the utility model, wherein it is determined that first-stage reactor, second reactor fluidized-bed layer is high spends Cheng Zhong, takes mixeding liquid volume usually 1L, and the standing is that 5min is stood in graduated cylinder；And the solid that sinks includes fluorination Calcium particle or calcium carbonate granule；When can sink solid for calcium fluoride particles when, can sink solid volume with stand before mixeding liquid volume it Than taking smaller value, when the solid that can sink is calcium carbonate granule, the solid volume that can sink takes higher value with the ratio between preceding mixeding liquid volume is stood.

According to method described in the utility model, wherein, the concentration difference of fluorine ion, calcium ion, fluidized-bed layer in raw water The time difference of formation can be very big.Therefore, startup stage sampling may relatively frequently, and 1~2h is sampled once；Operation phase 2~ 8h is sampled once.It is determined that in the case of raw water, after operation a period of time, those skilled in the art are easily found fluidized-bed layer The rule of formation, that is, be easily determined sampling interval time.

According to method described in the utility model, specifically, the method also includes the treatment operation after reactor stoppage in transit, its Comprise the following steps：

After a, reactor are stopped transport, the whole waste water and particle in reactor are vented immediately to one-level material pond or two grades of materials Pond；

B, unlatching acid dip pickle, to first-stage reactor, second reactor injection acid solution, when the acid solution liquid level does not have peracid After washing out water lines, open after the pickling circulatory system carries out pickling to the water-locator and empty pickle liquor, then use clear water Inside reactor is rinsed, after reactor emptying, pickling, you can long-term to stop transport.

Wherein, the one-level material pond, two grades of material ponds are not common storage slag bath, the one-level used by the utility model Material pond, the pond in two grades of material ponds hold the whole particles that can be accommodated when reactor reaches maximum height fluidized-bed layer, and one-level Material pond, two grades of material ponds pond inner bottom part are provided with aperture plate, and retention material used includes calcium carbonate granule or calcium fluoride particles, works as institute When stating retention material for calcium carbonate granule, aperture plate sieve aperture≤16 mesh (1mm)；When the retention material is calcium fluoride particles, grid Mesh screen hole≤200 mesh (0.075mm).Bulky grain is trapped to aperture plate, particle diameter less than sieve aperture particle can be spilt by aperture plate, Collect, periodically return in reactor.

According to method described in the utility model, in the utility model specific embodiment, pickling described in step b Time is 6~12h.And the utility model does not make specific requirement, those skilled in the art to the acid used by pickling and its concentration Can need to select suitable acid solution according to field operation and allocate rational concentration, as long as guarantee can realize pickling Purpose.

Additionally, after reactor emptying of the present utility model, pickling, you can long-term to stop transport；And because inside reactor is Cavity, has no complex component, and if necessary, can be manually entered inside reactor carries out more thoroughly cleaning.

According to method described in the utility model, wherein, in startup stage, not by pollutant removal it is up to standard for the purpose of, and It is that configurational ion is simultaneously a large amount of with water form crystalline precipitate, crystal growth, crystal grain fluid bed formed as target, because of water outlet In [F^-]、[Ca²⁺] it is possible to still higher, former pond need to be back to, reaction is participated in again.

Now, there is following course of reaction in startup stage first-stage reactor：During reactor internal circulation flow, medicine Agent A is sufficiently mixed with raw water, crystalline material Ca²⁺With F^-Or CO₃ ^2-Supersaturated solution is formed, in solid-liquid two-phase flow fluidized bed reactor In, hydraulic mixing cause current be in strong turbulence state, solid-liquid two-phase contact interface constantly update, two alternate speed differences compared with Greatly, enhance in two alternate effect of mass transmitting, first-stage reactor and generate a large amount of crystal settlings simultaneously；Under hydraulic shear effect, The CaF for having generated₂Or CaCO₃Fine crystals particle can't each other be gathered into bulky grain, but the crystal in aqueous solution body Matter Ca²⁺、F^-Or CO₃ ^2-Stably to tiny CaF₂Or CaCO₃Plane of crystal diffusion, movement, it is then embedded in some way brilliant Lattice, so that single crystal particle diameter increases, and form uniform and fine and close crystalline particle；Extension over time, reactor bottom Portion is formed the fluidized particles bed of certain altitude, now startup stage completion.

According to method described in the utility model, wherein, in the operation phase, crystal grain fluid bed has been formed, now with Fluorine removal, except firmly be target, according to water outlet [F^-]、[Ca²⁺] each stage reactor of adjustment operational factor, make reactor water outlet [F^-]、 [Ca²⁺] reach treatment target.

Raw water and first-stage reactor recirculation water mix from first-stage reactor bottom into water distributing area, by the uniform cloth of water-locator After water, in uniformly rising to first-stage reactor cavity with certain upflow velocity, medicament A is also with certain [Ca²⁺]/[F^-] mole Than or certain total alkalinity mass ratio (with CaCO₃Meter) flow into this；In first-stage reactor cavity, the original for continually entering Water and medicament A form supersaturated solution, and under the specific hydraulics of fluidized-bed reactor, configurational ion grows from crystallization Into the crystal grain of certain particle diameter, the crystalline particle bed of fluidisation state is gradually formed inside reactor cavity, raw water is from bottom to top During fluidized-bed layer, the F in raw water^-Or Ca²⁺It is able to be removed from water；Raw water is further up to separation of solid and liquid Area, crystal grain retains in the reactor under the centrifugation of gravitational settling or inclined tube filler or inclined plate packing, supernatant warp Mill weir is received by top to collect, gravity flow enters second reactor bottom water distributing area.

Primary effluent mixes with second reactor recirculation water in second reactor water distributing area, by water-locator water distribution uniformity Afterwards, second reactor cavity inside is uniformly risen to certain upflow velocity, medicament B is also with certain [Ca²⁺]/[CO₃ ^2-] rub You flow into this by ratio；In second reactor cavity, primary effluent, second reactor recirculation water and the medicament for continually entering B forms supersaturated solution, and under the specific hydraulics of fluidized-bed reactor, configurational ion grows into certain grain from crystallization The crystal grain in footpath, gradually forms the crystalline particle bed of fluidisation state inside reactor cavity, primary effluent passes through from bottom to top During fluidized-bed layer, the Ca in water²⁺Further removed；Primary effluent is further up to solid-liquid displacement zone, crystal Particle retains in the reactor under gravitational settling effect, and supernatant is received mill weir and collected via top, finally by secondary effluent Pipe discharge system.

Being continuously generated and grow with crystal, the highly stable growth of fluidized-bed layer is simultaneously layered, and particle diameter is small, light weight Particle on bed top, the particle that particle diameter is big, quality is big now needs periodically to discharge bottom particles in bed bottom, with protect Card reactor runs under suitable hydraulics always.Sidewall of reactor different height is provided with sample tap, by observation not With granule content and size in height water sample, fluidized-bed layer height and the deslagging frequency are determined；One-level, second reactor bottom, Water-locator top, is equipped with scum pipe, by the regular deslagging of discharge pipeline, the fluidized-bed layer kept certain height, and obtains higher The CaF of purity₂Or CaCO₃Particle.

It is operation phase, different (target contaminant is different) according to raw water quality, medicament A, medicament B, medicament kind used is not Together, reactor operational factor is also different, specific as shown in table 1.

Table 1

(1) method provided by the utility model can be used for fluorine high hard waste water high except F^-And Ca²⁺(raw water [F^-]≥300mg/ L, calcium hardness >=500mg/L (CaCO₃))。

First-stage reactor operational factor：Medicament A is CaO or Ca (OH)₂With CaCl₂Mixed liquor (wherein CaCl₂Account for dry The 0~25% of matter mixture gross mass, it act as adjusting the pH value in reactor<7.5), it is used to remove the F in waste water^-, its Dosage presses [Ca²⁺]/([F^-]) mol ratio=(0.7~1.5):1 meter.Hydraulic detention time HRT=(1~4) h, surface separates Load is 1~4m/h, void tower upflow velocity v=(10~60) m/h, pH value=(4~7.5) in reactor, reflux ratio (backflow Amount/inflow)=(1~20):1, temperature range (10~50) DEG C；First-stage reactor crystallized product is mainly the μ of particle diameter 60~200 The CaF of m₂Crystal grain, one-level material pond is entered in precipitating sludge form.

Second reactor operational factor：Medicament B is Na₂CO₃The aqueous solution, be used to remove the Ca in raw water²⁺And one-level mistake The Ca that amount is added²⁺, its dosage is by [Ca²⁺]/[CO₃ ^2-] mol ratio=1:1~2 meter；Hydraulic detention time HRT=(0.1~1) H, surface segregational load is (4~10) m/h, void tower flow velocity is (20~100) m/h, pH value=(8~10) in reactor, backflow Than (capacity of returns/inflow)=(1~24):1, temperature range is (10~50) DEG C；Second reactor crystallized product is mainly grain The CaCO of 1~3mm of footpath₃Crystal grain, discharges second reactor in granular form.

(2) the utility model can be additionally used in high rigidity wastewater hardness removing degree (raw water calcium hardness >=500mg/L (CaCO₃)), it is main Target is removed for Ca²⁺。

In first-stage reactor, medicament A is CaO or Ca (OH)₂Emulsion, be used to remove temporary transient calcium hardness, its dosage (the mass ratio, with CaCO based on 1.5~2 times of total alkalinity in water₃Meter), control ph is in the range of 8.5~10；

In second reactor, medicament B is Na₂CO₃The aqueous solution, be used to remove permanent calcium hardness, its dosage press [Ca² ⁺]/[CO₃ ^2-] mol ratio=1:(1~2) count, control ph is in the range of 8~10.

First-stage reactor, second reactor operational factor：Hydraulic detention time HRT=0.1~1h, surface segregational load are 4~10m/h, void tower flow velocity are 20~100m/h, temperature range is 10~50 DEG C, reflux ratio (capacity of returns/inflow)=(1~ 24):1。

From the CaCO of crystallization generation₃Crystal, ripe grain diameter enters two grades of material ponds in granular form in 1~3mm.

(3) the utility model can be additionally used in fluorine waste water ([F high^-] >=300mg/L) fluorine removal.First-stage reactor removes target F^-, second reactor removal target is the excessive Ca for adding²⁺。

First-stage reactor operational factor：Medicament A is CaO or Ca (OH)₂With CaCl₂Mixed liquor, wherein CaCl₂Account for dry 0~25%, CaCl of matter mixture gross mass₂Act as regulation reactor in pH value<The dosage of 7.5, medicament A presses [Ca² ⁺]/[F^-] mol ratio=(0.7~1.5):1 meter, hydraulic detention time HRT=(1~4) h, surface segregational load is 1~4m/h, Void tower upflow velocity v=(10~60) m/h, reflux ratio (capacity of returns/inflow)=(1~20):1, pH value<7.5, preferably 4 ~7；

Second reactor operational factor：Medicament B is Na₂CO₃The aqueous solution, its dosage press [Ca²⁺]/[CO₃ ^2-] mol ratio =1:(1~2) count, hydraulic detention time HRT=(0.1~1) h, surface segregational load is 1~4m/h, void tower upflow velocity v= (20~100) m/h, reflux ratio (capacity of returns/inflow)=(1~24):1, pH value=8~10.

First-stage reactor precipitated product is CaF₂Crystal grain, particle diameter is discharged at 60~200 μm in precipitating sludge form, Second reactor precipitated product is CaCO₃Crystal grain, particle diameter is in 1~3mm.

Total system, [F in water outlet^-] clearance>97%, [Ca in water outlet²⁺] clearance>99%.

(4) the utility model is limited not to remove magnesium hardness as target by reaction condition, it is impossible to remove magnesium hardness.

It is reinforcing solid-liquid separation effect when reactor is used for fluorine removal, can sets up removable in the solid-liquid displacement zone of reactor The inclined tube filler or inclined plate packing for unloading.

With reaction carrying out, the method also include determine first-stage reactor, second reactor fluidized-bed layer height and The step of deslagging frequency：

Wherein, spoil disposal frequency is determined by bed height, keep bed height account for reactor cavity part (it is more than water-locator, Part between backflow water out) less than 3/4 be advisable.

The judgement of bed height：On the side wall of reactor cavity part, uniform 3~4 sample taps, periodically sampling, examines Crystalline particle content in water sample is seen, with the height of this determination fluidized-bed layer aspect.Also can be online according to level meter in robot control system(RCS) Monitoring fluidized-bed layer Plane Location.

Now by taking fluorine high hard raw water high as an example, specific embodiment of the present utility model is as follows：

(1) startup of reactor：

Raw water is fluorine high hard waste water high, determines that medicament A is CaO or Ca (OH)₂, for removing F^-, medicament B is Na₂CO₃, use In removal Ca²⁺。

Step 1：Raw water is calculated by HRT=4~5h flow first, is sent into by intake pump 5 by inlet pipeline 15 The bottom water distributing area of first-stage reactor 1, to first-stage reactor 1 in liquid level flood circulatory system outlet pipe 16；Medicament A is opened simultaneously to throw Feeder apparatus 3, by [Ca²⁺]/[F^-] mol ratio=1.5~2:1 adds medicament A in the cavity of first-stage reactor 1；Then one-level is started Reactor cycles pump 6, recirculation water also delivers to bottom water distributing area, and after mixing with raw water herein, the two is uniformly risen by water-locator Into the cavity of first-stage reactor 1, waste water upflow velocity in reactor is reached 2~10m/h, control pH<7.5；In reactor During circulating, Ca²⁺With F^-Supersaturated solution occur from crystallization reaction, generate CaF₂Fine crystals particle.Raw water is entered One step rises to solid-liquid displacement zone, and crystal grain is retained in the reactor by the centrifugation of inclined tube filler or inclined plate packing, Supernatant is received mill weir and is collected via top, is flow automatically by primary effluent pipeline 11 and enters the water distributing area of the bottom of second reactor 2.

Step 2：Primary effluent gravity flow enters second reactor 2 bottom water distributing area, to second reactor 2 in liquid level flood and follow Loop systems outlet pipe 18；Medicament B throwing devices 4 are opened simultaneously, by [Ca²⁺]/[CO₃ ^2-] mol ratio=1:1.5~2 add medicament B Into the cavity of second reactor 2；Then second reactor circulating pump 8 is started, recirculation water also delivers to bottom water distributing area, herein with one After level water outlet mixing, the two is uniformly risen in the cavity of second reactor 2 by water-locator, makes waste water upflow velocity in reactor 10~20m/h is reached, pH=9~10 are controlled；During reactor internal circulation flow, Ca²⁺With CO₃ ^2-Supersaturated solution hair Crystallization reaction is conigenous, CaCO is generated₃Fine crystals particle.Primary effluent continues to rise to solid-liquid displacement zone, CaCO₃Crystal grain Retain in the reactor under gravitational settling effect, supernatant is received mill weir and collected via top, finally by secondary effluent pipe 12 Discharge system.Startup stage, water outlet [Ca²⁺]、[F^-] concentration is still higher, system water outlet returns to former pond.

(2) operation of reactor：

Step 3：In first-stage reactor 1, with CaF₂Crystal particles are continuously generated and grow, inside reactor cavity by Gradually formed by CaF₂The fluidized-bed layer that crystal grain is constituted；The dosage of medicament A is reduced to [Ca²⁺]/[F^-] mol ratio=(0.7 ~1.5):1, with fluidized-bed layer thickness, the increase of density, in good time adjustment void tower upflow velocity (10~60m/h), HRT (1~ 4h), reflux ratio (1~20:Etc. 1) operational factor, makes water outlet [F^-] meet treatment target；Raw water passes through fluidized-bed layer from bottom to top During, the F in raw water^-Removed.

Wherein, there is bed by sampling observation in implementation process, that is, think to enter into operation phase, medicament A dosages It is reduced to [Ca²⁺]/[F^-] mol ratio be (0.7~1.5):1；As for institute's calcic, fluorine ion in the selection of specific ratio, with waste water Concentration is relevant, and to certain specific waste water, those skilled in the art, can be according to given operational factor in debugging process is run Scope knows appropriate operational factor needed for the waste water.

Step 4：In second reactor 2, with CaCO₃Crystal particles are continuously generated and grow, inside reactor cavity Gradually form by CaCO₃The fluidized-bed layer that crystal grain is constituted；The dosage of medicament B is reduced to [Ca²⁺]/[CO₃ ^2-] mol ratio= 1:(1~2), with fluidized-bed layer thickness, the increase of density, adjust in good time upflow velocity (20~100m/h), HRT (0.1~ 1h), reflux ratio (1~24:Etc. 1) operational factor, makes water outlet [Ca²⁺] meet treatment target；Primary effluent is from bottom to top by stream During changing bed, the Ca in primary effluent²⁺Removed.

Step 5：Being continuously generated and grow, the highly stable growth of fluidized-bed layer, bed endoparticle gap with crystal Reduce, until backflow water yield is mismatched with crystal grain amount, now spoil disposal is needed, to ensure reactor always in suitable water Run under the conditions of power.Granule content in observation water sample is sampled by regular probe tube 35, determines fluidized-bed layer highly；By fixed Phase spoil disposal, keeps the 1/2-3/4 of fluidized-bed layer height distance between circulating water outlet pipe and water-locator.

The bottom of first-stage reactor 1 is provided with discharge pipeline 17, periodically arranges CaF₂Particle can be obtained more high-purity to one-level material pond 7 The CaF of degree₂Crystal grain.The bottom of second reactor 2 is provided with discharge pipeline 19, periodically arranges CaCO₃Particle can be obtained to two grades of material ponds 9 Obtain the CaCO of higher degree₃Crystal grain.

(3) stop phase of reactor：

Step 6：Stop transport each reactor, whole waste water and particle to one-level material pond or two grades of things are vented in reactor immediately Material pond.Material pond inner bottom part is provided with aperture plate, and particle is trapped to aperture plate, return of waste water to former pond.

Step 7：Acid dip pickle is opened, acid solution is injected to reactor, after liquid level of solution does not have overpickling outlet pipeline, opened The pickling circulatory system, pickling is carried out specifically designed for water-locator, and pickle liquor is emptied after 6~12h, and reactor is rinsed with clear water It is internal.

According to method described in the utility model, wherein, the utility model is dense to the emulsion of medicament A, B or the aqueous solution Degree does not make specific requirement, as long as ensureing reactor Chinese medicine addition in the claimed scope of the application.This Utility model is it is determined that after raw water quality, water, medicament A, B dosage determine that now the size of its concentration of aqueous solution, will influence The size of dosing flow, and then influence the selection model of dosing pump.But those skilled in the art can be according to pump selection principle And experience, it is determined that suitable emulsion or concentration of aqueous solution proportioning.

The utility model proposes a kind of up-flow two-phase fluidization by chemical crystallization technique and sewage treatment area first Bed process is organically combined, removes hard method of wastewater treatment without inducer, from crystallization fluorine removal.The purpose of this utility model is to adopt With from crystallization technique, that is, carrier-free or filler are needed, using two-phase fluidization bed specific hydrodynamics bar from crystallization reactor Part and chemical crystallization principle, by the Reasonable Regulation And Control to 4 Crystallization, make the F in precipitating reagent and waste water^-And Ca²⁺Spontaneous knot Crystalline substance, generates the CaF of uniform particle sizes₂、CaCO₃Particle, enhances precipitate and separate.Due to the induced nuclei without other compositions, generation CaF₂、CaCO₃Crystal grain purity is higher, there is certain recovery value.

The utility model is different from chemical precipitation method and induction crystalline deposit technology, the utility model proposes a kind of nothing Need inducer, remove hard method of wastewater treatment from crystallization fluorine removal, its central principle is：Homogeneous nucleation → orientation under electrostatic interaction Aligned growth → generation crystalline precipitate.The utility model is the up-flow two phase flow by chemical crystallization technique and sewage treatment area Change a kind of method that bed process is organically combined, on the one hand, in Chemical Manufacture, crystallization is a most basic chemical technology mistake The purification of journey, the material for producing crystallization, and other materials (especially organic matter), purification, it or many technique mistakes Journey inalienable part.The need for due to obtaining chemical products, people are to the principle of chemicrystallization process, process conditions, anti- Answering device etc. has had in-depth study and application.On the other hand, in water treatment field, although people have built consensus, knot Crystallization can be used for the purification (by insoluble compound crystalline deposit, impurities in water being removed, so that purified water) of water, but because people are closed Note is only to obtain target water quality, is reinforced deposition separating effect, or is coordinated at traditional water such as coagulating sedimentation, clarification, filtering Reason technology, or provide inducer reinforcing crystallization, therefore obtain insoluble compound crystallization in, be mixed with a large amount of other impurities into Point, can only be as body refuse waste, no or rare recycling is worth.Another further aspect, the crystallizable pollution in water treatment procedure Thing generally can be in the hypersaturated state needed for normal temperature condition realizes crystallization, and its crystallization reactor is also without as chemical process Complexity, the conventional fluidized-bed reactor of water treatment field can meet crystallization processes requirement, therefore, it can using these reactors Similar structure type and the method for operation are crystallized realizing insoluble compound, while purifying water, obtained higher degree, are had The insoluble compound crystalline particle of recovery value.

The chemical crystallization principle of the utility model foundation：

Under normal temperature crystallization condition, supersaturation is the motive force of crystallization process, and the concentration of ie in solution is (molten more than equilibrium concentration Xie Du), it is referred to as degree of supersaturation beyond part, represents that degree of supersaturation can use three numerical value：Absolute degree of supersaturation Δ c, relative mistake Saturation degree δ, supersaturation coefficient s.They are expressed as：

Δ C=C-C_eq；

δ=(C-C_eq)/C_eq；

S=C/C_eq；

In formula, C is concentration, C_eqIt is equilibrium concentration.

Meet 3 conditions, you can realize " the large quantities of crystallizations (a large amount of crystal are formed and grown simultaneously) " in chemical process, i.e., " from crystallizing " process in the utility model：

, more than after certain value (Nonlinear effect), solution just can spontaneously occur homogeneous nucleation effect for a, supersaturation coefficient s；

B, relative degree of supersaturation δ are smaller, are possible to generate crystalline precipitate；

C, fluidised form.Crystallization process is represented by the functional relation of " Concentration-time ", and low degree of supersaturation is conducive to larger knot Brilliant production, but the long period is needed, but stirring (mechanical agitation or hydraulic mixing) is to be substantially shorter this time.Because Stirring can increase the solubility of precipitation, also increase the speed of effects of ion diffusion.

The method that the utility model is provided can be used for fluorine FLUORIDE REMOVAL IN WASTEWATER high, such as in agricultural chemicals, chemical industry, plating, rare earth industry Fluorine waste water acid high；Can also be used for hard wastewater hardness removing high, such as steel plant RO concentrated waters, high rigidity underground water；Can be additionally used in height Fluorine, the fluorine removal of hard waste water high such as use the stainless-steel cold-rolling waste water after hydrofluoric acid rinse except hard.The utility model is especially suitable In high-calcium low-magnesium wastewater hardness removing and high-concentration fluorine-containing waste water fluorine removal, while the calcium carbonate of certain recovery value, fluorination can be obtained Calcium crystallized product.

The beneficial effects of the utility model are：

(1) the utility model organically combines chemicrystallization technique and up-flow two-phase fluidization bed process, is carried without addition Body or nucleus, you can realize insoluble compound CaF₂And CaCO₃From crystallizing, and under hydraulic shear effect, formed uniform and caused Close crystalline particle.

(2) the utility model is in high-effective defluorination, except on the basis of hard, can also obtaining the CaF of higher degree₂And CaCO₃Crystal Particle, realizes recycling sludge, is a kind of environmentally friendly technology, with preferable application prospect.

(3) medicament used by the utility model is mainly Na₂CO₃、CaO、Ca(OH)₂, these medicaments are low-cost；In not shadow On the premise of ringing producing water water quality, the flow velocity compared with Gao Shui can be obtained in device, the aquifer yield in the unit interval is big, be suitable to industrialization useless Water process scale.

(4) the utility model technological process is simple, crystallization reactor simple structure used, and its key reaction segment structure is Cavity, it is both for chemicrystallization creates suitable fluid dynamics condition and easy to maintenance, it is adapted to industrial applications.

Brief description of the drawings

Fig. 1 is that two-stage two-phase fluidization provided by the utility model bed shows from crystallization treatment fluorine high, high rigidity waste water system It is intended to；

The structural representation from crystallization fluidized-bed reactor that Fig. 2 is provided by the utility model embodiment 1；

The structural representation from crystallization fluidized-bed reactor that Fig. 3 is provided by the utility model embodiment 2.

Main Reference label declaration：

1st, first-stage reactor；

2nd, second reactor；

3rd, medicament A throwing devices；

4th, medicament B throwing devices；

5th, intake pump；

6th, first-stage reactor circulating pump；

7th, one-level material pond；

8th, second reactor circulating pump；

9th, two grades of material ponds；

10th, acid dip pickle；

11st, primary effluent pipeline；

12nd, secondary effluent pipeline；

13rd, medicament A dosing pipes；

14th, medicament B dosing pipes；

15th, inlet pipeline；

16th, first-stage reactor circulation return line；

17th, first-stage reactor discharge pipeline；

18th, second reactor circulation return line；

19th, second reactor discharge pipeline；

20th, one-level pickling pipeline；

21st, two grades of pickling pipelines；

22nd, water-locator；

23rd, water distributing area；

24th, fluidized-bed layer；

25th, solid-liquid displacement zone；

26th, mill weir is received；

27th, ring-type receives water pipe；

28th, circulation；

29th, the pickling circulatory system；

30th, water inlet；

31st, slag-drip opening；

32nd, dosing mouth；

33rd, delivery port；

34th, pickling feeding opening；

35th, probe tube；

36th, inclined tube filler or inclined plate packing.

Specific embodiment

Implementation process of the present utility model is described in detail with having for producing below by way of specific embodiment and Figure of description Beneficial effect, it is intended to help reader to more fully understand essence of the present utility model and feature, not as can practical range to this case Restriction.

Embodiment 1

A kind of crystallization fluidized-bed reactor certainly is present embodiments provided, should be from the structural representation for crystallizing fluidized-bed reactor As shown in Fig. 2 it includes：

Reactor shell；

3 probe tubes 35 are uniformly distributed on the reactor cylinder side wall between outlet pipeline and water-locator 22.

The top of the slag-drip opening 31 is provided with the pickling feeding opening 34 for being connected with acid dip pickle；And the top of water-locator 22 And be connected with the pickling circulatory system 29 on the reactor cylinder side wall of lower section, the pickling circulatory system 29 include pickling circulating pump and Pickling outlet pipeline, pickling water return pipeline.

Embodiment 2

A kind of crystallization fluidized-bed reactor certainly is present embodiments provided, should be from the structural representation for crystallizing fluidized-bed reactor As shown in figure 3, it includes：

Reactor shell；

The solid-liquid displacement zone 25 of reactor shell is provided with dismountable inclined tube filler or inclined plate packing 36.

Embodiment 3

A kind of two-stage two-phase fluidization bed is present embodiments provided from crystallization treatment fluorine high, the system of high rigidity waste water, this is The structural representation of system is as shown in figure 1, it includes：Crystallization fluidized-bed reaction certainly described in two embodiments 1 (or embodiment 2) Device：(wherein, the water circulation system of first-stage reactor includes first-stage reactor circulating pump 6 and backflow to be designated as first-stage reactor 1 respectively Pipeline 16, return line 16 includes outlet pipeline and water return pipeline), (wherein, the water circulation of second reactor of second reactor 2 System includes second reactor circulating pump 8 and return line 18, and return line 18 includes outlet pipeline and water return pipeline)；Medicament A Throwing device 3, medicament B throwing devices 4, one-level material pond 7 and two grades of material ponds 9；

The delivery port 33 of second reactor 2 is connected by secondary effluent pipeline 12 with retracting device；

The system also includes acid dip pickle 10, and the acid dip pickle 10 passes through 20, two grades of pickling pipelines of one-level pickling pipeline 21 pickling feeding openings respectively with first-stage reactor 1, the pickling feeding opening of second reactor 2 are connected.

Embodiment 4

A kind of two-stage two-phase fluidization bed is present embodiments provided from crystallization treatment fluorine high, the method for high rigidity waste water, it is What the two-stage two-phase fluidization bed provided using embodiment 3 was realized from the system of crystallization treatment fluorine high, high rigidity waste water, the method tool Body is comprised the following steps：

Raw water quality is：Total hardness=1462mg/L (CaCO₃), calcium hardness=1207mg/L (CaCO₃), basicity= 283mg/L(CaCO₃)、[Ca²⁺]=483mg/L, [F^-]=7019mg/L, pH=2.5.

First degree crystalline reactor operational factor：Medicament A is the CaO emulsion of 20% (mass ratio), and its dosage presses [Ca² ⁺]/[F^-] mol ratio=0.7:1, reflux ratio=10~15:1, surface segregational load 1.5m/h, 30~60m/ of void tower upflow velocity H, pH=4.5~6.5；

Secondary crystallization reactor operational factor：Medicament B is the Na of concentration 0.5M₂CO₃Solution, its dosage presses [Ca²⁺]/ [CO₃ ^2-] mol ratio=1:1.1 meters, reflux ratio (capacity of returns/inflow)=8~13:1, surface segregational load 4m/h, on void tower Rise 80~100m/h of flow velocity, pH=8.0~9.5.

Total system water outlet (secondary effluent) [Ca²⁺]=15mg/L, [F^-]=25mg/L, first-stage reactor sediment is main It is 60~200 μm of CaF of particle diameter₂Particle, second reactor sediment is mainly 1~3mm of particle diameter CaCO₃Crystal, crystal grain Mobility is good, without obvious wall built-up phenomenon.Calcirm-fluoride, calcium carbonate crystal particle drying dehydration property are good, calcirm-fluoride purity More than 80%, calcium carbonate granule whiteness value be 80, purity more than 90%, the two is provided with good resource value.

Embodiment 5

A kind of method of two-stage two-phase fluidization bed from crystallization treatment high rigidity waste water is present embodiments provided, it is using real The two-stage two-phase fluidization bed of the offer of example 3 is applied from the system realization of crystallization treatment fluorine high, high rigidity waste water, the method is specifically included Following steps：

Raw water quality is：Total hardness=3902mg/L (CaCO₃), calcium hardness=3709mg/L (CaCO₃), magnesium hardness= 193mg/L(CaCO₃)、[Ca²⁺]=1483mg/L, [Mg²⁺]=46mg/L, basicity=850mg/L (CaCO₃), pH=7.

First degree crystalline reactor operational factor：Medicament A is the Ca (OH) of 20% (mass ratio)₂Solution, by [Ca²⁺]/[total alkali Degree] (mass ratio)=2:1 adds, reflux ratio=4~7:1, surface segregational load 6m/h, void tower upflow velocity 40~80m/h, pH =9.5~10；

Secondary crystallization reactor operational factor：Medicament B is the Na of 0.5M₂CO₃Solution, by [Ca²⁺]/[CO₃ ^2-] mol ratio= 1:1.5 add, reflux ratio=4~7:1,40~80m/h of upflow velocity, pH=8.5~9.8.

Total system water outlet (secondary effluent) [Ca²⁺]=15mg/L, [Ca²⁺] clearance be 99%, in system operation, Calcium carbonate crystal well-grown, calcium carbonate crystal 1~3mm of particle diameter, good fluidity, without obvious wall built-up phenomenon.Calcium carbonate is brilliant Body particle drying dehydration property is good, and whiteness value is 86, possesses good resource value.

Embodiment 6

A kind of method of two-stage two-phase fluidization bed from crystallization treatment fluorine waste water high is present embodiments provided, it is using implementation What the two-stage two-phase fluidization bed that example 3 is provided was realized from the system of crystallization treatment fluorine high, high rigidity waste water, the method specifically include with Lower step：

Raw water quality is [F^-]=2500mg/L, pH=2.7.

First degree crystalline reactor operational factor：Medicament A is the CaO emulsion and CaCl of 20% (mass ratio)₂Mixed solution, Wherein CaCl₂Accounting 10%.Medicament A presses [Ca²⁺]/[F^-] mol ratio=1.5:1 adds, reflux ratio=5~10:1, surface separates Load 1m/h, void tower upflow velocity 15~45m/h, pH=5.5 or so；

Secondary crystallization reactor operational factor：Medicament B is the Na of 0.5M₂CO₃Solution, by [Ca²⁺]/[CO₃ ^2-] mol ratio= 1:1.5 add, reflux ratio=9~14:1, surface segregational load 4m/h, void tower upflow velocity 85~100m/h, pH=9.0 are left It is right.

Total system water outlet (secondary effluent) [F^-]<15mg/L, [F^-] clearance>99.4%, first-stage reactor precipitated product is The calcium fluoride crystal that 60~100 μm of particle diameter, reactor is discharged in precipitating sludge form, and second reactor precipitated product is particle diameter 1 The calcium carbonate granule of~3mm.The equal good fluidity of precipitated product, without obvious wall built-up phenomenon, drying and dehydrating is good, and purity exists More than 80%, possess good resource value.

Claims

1. it is a kind of from crystallization fluidized-bed reactor, it is characterised in that should to include from crystallization fluidized-bed reactor：

Reactor shell；

The water-locator (22) of reactor shell bottom is arranged at, be water distributing area (23) below water-locator (22) when reactor runs, Water-locator (22) top cavity will form fluidized-bed layer (24)；

Reactor shell top perimeter is provided with receipts mill weir (26), and the receipts mill weir (26) lower section is solid-liquid displacement zone (25), the solid-liquid Ring-type is provided between Disengagement zone (25) and fluidized-bed layer (24) and receives water pipe (27)；

Reactor cylinder side wall is provided with water inlet (30), slag-drip opening (31), dosing mouth (32), delivery port (33) and probe tube (35),

Wherein, the water inlet (30), slag-drip opening (31) are respectively positioned at lower section, the top of water-locator (22)；The dosing mouth (32) positioned at reactor shell middle part；The delivery port (33) is positioned at reactor head side wall；

Reactor cylinder side wall top and bottom are connected with circulation (28), the circulation (28) including circulating pump, Outlet pipeline and water return pipeline；Wherein, one end of outlet pipeline and the ring-type are received water pipe (27) and are connected, outlet pipeline it is another End is connected by water return pipeline with the bottom of reactor shell again via circulating pump；

The probe tube (35) is uniformly distributed in the reactor cylinder between circulation (28) outlet pipeline and water-locator (22) On body sidewall.

2. it is according to claim 1 from crystallization fluidized-bed reactor, it is characterised in that the probe tube (35) is 3-4 roots.

3. it is according to claim 1 from crystallization fluidized-bed reactor, it is characterised in that slag-drip opening (31) top is set There is the pickling feeding opening (34) for being connected with acid dip pickle；And on water-locator (22) reactor cylinder side wall over and under The pickling circulatory system (29) is connected with, the pickling circulatory system (29) is returned including pickling circulating pump and pickling outlet pipeline, pickling Water lines, wherein, the pickling outlet pipeline is arranged at water-locator (22) top and positioned at the lower section of pickling feeding opening (34)；Institute Pickling water return pipeline is stated positioned at water-locator (22) lower section.

4. according to the claim any one of 1-3 from crystallization fluidized-bed reactor, it is characterised in that reactor shell is consolidated Liquid Disengagement zone (25) is provided with dismountable inclined tube filler or inclined plate packing (36), and the inclined tube filler or inclined plate packing (36) are fixed On the reactor barrel received below mill weir.

5. from crystallization treatment fluorine high, the system of high rigidity waste water, it includes a kind of two-stage two-phase fluidization bed：Two claim 1- Crystallization fluidized-bed reactor certainly described in 4 any one：First-stage reactor (1), second reactor (2) are designated as respectively；Medicament A is added Device (3), medicament B throwing devices (4), one-level material pond (7) and two grades of material ponds (9)；

Wherein, former pond is connected via intake pump (5) by inlet pipeline (15) with the water inlet of first-stage reactor (1)；

Medicament A throwing devices (3) is connected by medicament A dosing pipes (13) with the dosing mouth of first-stage reactor (1)；

The slag-drip opening of first-stage reactor (1) is connected by first-stage reactor discharge pipeline (17) with the one-level material pond (7)；

The delivery port of first-stage reactor (1) is connected by primary effluent pipeline (11) with the water inlet of the second reactor (2)；

Medicament B throwing devices (4) is connected by medicament B dosing pipes (14) with the dosing mouth of second reactor (2)；

The slag-drip opening of second reactor (2) is connected by second reactor discharge pipeline (19) with two grades of material ponds (9)；

The delivery port (33) of second reactor (2) is connected by secondary effluent pipeline (12) with retracting device.

6. system according to claim 5, it is characterised in that the one-level material pond (7) and two grades of interior bottoms of material pond (9) Portion is equipped with aperture plate.

7. system according to claim 5, it is characterised in that the system also includes acid dip pickle (10), the pickling dress Put (10) by one-level pickling pipeline (20), two grades of pickling pipelines (21) respectively with pickling feeding opening, two of first-stage reactor (1) The pickling feeding opening of stage reactor (2) is connected.