CN105339063B - Crystallization reaction unit - Google Patents
Crystallization reaction unit Download PDFInfo
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- CN105339063B CN105339063B CN201380077825.7A CN201380077825A CN105339063B CN 105339063 B CN105339063 B CN 105339063B CN 201380077825 A CN201380077825 A CN 201380077825A CN 105339063 B CN105339063 B CN 105339063B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0036—Crystallisation on to a bed of product crystals; Seeding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/005—Selection of auxiliary, e.g. for control of crystallisation nuclei, of crystal growth, of adherence to walls; Arrangements for introduction thereof
- B01D9/0054—Use of anti-solvent
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- 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
- C02F2209/44—Time
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- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
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Abstract
Using crystallization reaction unit，The crystallization reaction unit includes crystallization reactive tank (10)，The crystallization reactive tank (10) has by adding calcium agent in the raw water containing crystallization object material so as to generate the crystallization reacting part (28) of the crystallization of indissoluble salt，In crystallization reactive tank (10)，Being configured with the internal perisporium (26) relative with the periphery wall of crystallization reactive tank (10) and being provided with upper up-flow is formed between internal and external peripheral wall and carry out the separation of solid and liquid portion (30) of the separation of solid and liquid between above-mentioned crystallization and process water，So that the water flowing time for being passed through above-mentioned raw water into crystallization reactive tank (10) becomes more than 1/2 times of holdup time of separation of solid and liquid portion (30) and less than 5 times of mode opens the valve (18) located at raw water water flowing line (16)，After above-mentioned raw water is passed through，So as to stop becoming more than 1/5 times of holdup time of separation of solid and liquid portion (30) to the water flowing dwell time for being passed through above-mentioned raw water in crystallization reactive tank (10) and less than 1 times of mode closes the valve (18) located at raw water water flowing line (16).
Description
Technical field
The present invention relates to a kind of skill of the crystallization reaction unit for processing the crystallization object such as fluorine, phosphorus material as indissoluble salt
Art.
Background technology
Since in the past, as by the method for the indissoluble salt recycling such as calcirm-fluoride, calcium phosphate, using crystallization method.Make
For crystallization method, such as, in the case of reclaiming the fluorine in fluorine-containing raw water as calcirm-fluoride, there is following method etc.：By making to contain
Fluorine raw water flows into reactive tank, and injects calcium agent, so that they react and make to analyse on seed surface of the calcirm-fluoride in reactive tank
Go out.
Since in the past, in crystallization method, using such as understirring type crystallization reaction unit (such as patent document 2) etc.：Utilize
Rise and the raw water containing crystallization object material such as fluorine-containing raw water of supply in reactive tank is flowed to, the slightly solubility in reactive tank is made on one side
The crystallization flowing of salt is while the fluidized bed-type crystallization reaction unit (such as patent document 1) for being processed, the interior setting of reactive tank are stirred
Machine being mixed, so that the crystallization of the indissoluble salt in reactive tank is flowed while being processed.In addition, general
Adopt with the following method：The indissoluble salt in reactive tank crystalline growth to a certain extent when, being repeated in autoreaction groove will
Extraction operation and supplement the additional process of crystal seed again and continuously obtain slightly solubility that a part for the crystallization of indissoluble salt is extracted out
The crystallization of salt.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2003-225680 publication
Patent document 2：Japanese Unexamined Patent Publication 2008-73589 publication
Patent document 3：Japanese Unexamined Patent Publication 2002-292202 publication
Patent document 4：Japanese Unexamined Patent Publication 2009-226232 publication
Patent document 5：Japanese Unexamined Patent Publication 2010-207755 publication
Content of the invention
Problems to be solved by the invention
However, in crystallization reaction unit, in order to reclaim indissoluble salt with the higher rate of recovery, keeping the difficulty in reactive tank
Soluble crystallization etc. surface area higher, i.e. keep reactive tank in indissoluble salt crystallization particle particle diameter tiny be critically important
's.As the tiny method of the particle (particle diameter distribution) of the indissoluble salt crystallization kept in reactive tank, it is considered to a large amount of in oriented groove
The method that supply has the crystal seed of tiny particle diameter distribution, but cause processing cost relative with the amount increased by the magnitude of recruitment of crystal seed
Should ground rising.
Then, it is an object of the invention to provide a kind of magnitude of recruitment that can not increase crystal seed returned with the higher rate of recovery
Receive the crystallization reaction unit of indissoluble salt.
For solution to problem
(1) present invention is a kind of crystallization reaction unit, it is characterised in that the crystallization reaction unit includes：Crystallization reactive tank,
Which includes crystallization reacting part, and the crystallization reacting part includes the mixing component with agitator, and the crystallization reacting part is to containing crystallization
The raw water of object material is added calcium agent and generates the crystallization of indissoluble salt；And water flowing part, which is used for reacting to above-mentioned crystallization
Above-mentioned raw water is passed through in portion, in above-mentioned crystallization reactive tank, is configured with the inner circumferential relative with the periphery wall of above-mentioned crystallization reactive tank
Wall is simultaneously provided with formation upper up-flow between internal and external peripheral wall and carries out the separation of solid and liquid of the separation of solid and liquid between above-mentioned crystallization and process water
Portion, above-mentioned water flowing part are passed through above-mentioned raw water to above-mentioned crystallization reacting part off and on.
(2) the crystallization reaction unit according to above-mentioned (1), it is preferred that when above-mentioned water flowing part carries out interval water flowing
Water flowing time of above-mentioned raw water be more than 1/2 times and less than 5 times of holdup time of above-mentioned separation of solid and liquid portion, above-mentioned water flowing portion
The water flowing dwell time of above-mentioned raw water when part carries out interval water flowing is more than 1/5 times of the holdup time in above-mentioned separation of solid and liquid portion
And less than 1 times.
(3) the crystallization reaction unit according to above-mentioned (1), it is preferred that when above-mentioned water flowing part carries out interval water flowing
Water flowing time of above-mentioned raw water be more than 1 times and less than 4 times of holdup time of above-mentioned separation of solid and liquid portion, above-mentioned water flowing part
The water flowing dwell time of above-mentioned raw water when carrying out interval water flowing be more than 1/4 times of the holdup time in above-mentioned separation of solid and liquid portion and
Less than 1/2 times.
(4) the crystallization reaction unit according to any one of above-mentioned (1)～(3), it is preferred that be provided with above-mentioned solid-liquid
The periphery wall of the above-mentioned crystallization reactive tank of separation unit is formed with the outlet for discharging above-mentioned process water, above-mentioned internal perisporium upper
End be located at and the mutually level position of above-mentioned outlet, or above-mentioned process water a part can from above-mentioned outlet discharge
In the range of positioned at less than above-mentioned outlet position, in above-mentioned separation of solid and liquid portion process water a part cross above-mentioned internal perisporium
Sent back to above-mentioned crystallization reacting part.
The effect of invention
Using the present invention, the magnitude of recruitment of crystal seed can not be increased indissoluble salt is reclaimed with the higher rate of recovery.
Description of the drawings
Fig. 1 is the schematic diagram of of the crystallization reaction unit for representing embodiments of the present invention.
Fig. 2 is the schematic diagram of of the structure of the crystallization reaction unit for representing reference example.
Fig. 3 is the figure of the particle diameter distribution of the crystallization in the crystallization reacting part for represent embodiment 1.
Fig. 4 is the figure of the particle diameter distribution of the crystallization in the crystallization reacting part for represent embodiment 2.
Fig. 5 is the figure of the particle diameter distribution of the crystallization in the crystallization reacting part for represent embodiment 3.
Fig. 6 is the figure of the particle diameter distribution of the crystallization in the crystallization reacting part for represent embodiment 4.
Fig. 7 is the figure of the particle diameter distribution of the crystallization in the crystallization reacting part for represent comparative example 1.
Fig. 8 is the figure of the particle diameter distribution of the crystallization in the crystallization reacting part for represent comparative example 2.
Fig. 9 is the figure of the particle diameter distribution of the crystallization in the crystallization reacting part for represent comparative example 3.
Specific embodiment
Embodiments of the present invention are below described.Present embodiment is that the present invention is not for implementing the one of the present invention
It is defined in present embodiment.
Fig. 1 is the schematic diagram of of the crystallization reaction unit for representing embodiments of the present invention.As shown in figure 1, crystallization
Reaction unit 1 include crystallization reactive tank 10, crystal seed warehouse 12, as crystallization reactive tank 10 add calcium agent interpolation part
The calcium agent of add line 14, as making the raw water for flowing into of part that raw water is flowed into crystallization reactive tank 10 logical
Waterline 16 and valve 18, crystal seed add line 20, process water discharge line 22 and indissoluble salt discharge line 24.
Crystallization reactive tank 10 be connected with the raw water water flowing line 16 from raw water storage tank (not shown), from calcium agent storage tank (not
Diagram) calcium agent add line 14.In addition, being connected with crystal seed between crystal seed warehouse 12 and crystallization reactive tank 10 to add line 20.In addition,
The process water outlet 21 of crystallization reactive tank 10 is connected with process water and discharges line 22, the indissoluble salt outlet of crystallization reactive tank 10
It is connected with indissoluble salt and discharges line 24.
It is provided with crystallization reactive tank 10 for the crystallization reacting part 28 of the crystallization that generates indissoluble salt and for carrying out difficulty
The separation of solid and liquid portion 30 of the separation of solid and liquid between soluble crystallization and process water.It is provided with crystallization reactive tank 10 and reacts with crystallization
The relative internal perisporium 26 of the periphery wall of groove 10, will be set to separation of solid and liquid portion 30 between the periphery wall and internal perisporium 26.This embodiment party
The internal perisporium 26 of formula is in the specified interval of the periphery wall of crystallization reactive tank 10, but internal perisporium 26 can also be whole located at periphery wall
Week.
Crystallization reacting part 28 is divided by internal perisporium 26 with separation of solid and liquid portion 30, is formed with connection analysis in the bottom of internal perisporium 26
Brilliant reacting part 28 and the connected entrance 32 in separation of solid and liquid portion 30.In addition, above-mentioned process water outlet 21 is located at crystallization reactive tank 10
Formation have the periphery wall in separation of solid and liquid portion 30, the process water outlet 21 is connected with process water and discharges line 22.
The crystallization reacting part 28 of crystallization reactive tank 10 includes mozzle 36, as the stream in stirring and crystallizing reacting part 28
The agitating device 34 of of the mixing component of body.Agitating device 34 includes agitator 38, and agitator 38 is configured in mozzle 36
Interior, and using the revolving force rotation produced by transmit via shaft, motor.
The action of the crystallization reaction unit 1 of present embodiment is described.
First, the valve 18 of open raw water water flowing line 16, reacts to the crystallization of crystallization reactive tank 10 via raw water water flowing line 16
The raw water containing the crystallization object material such as fluorine, phosphorus is passed through in portion 28 and (exists below the situation of referred to as " raw water ".).In addition, warp
Line 14 is added by calcium agent, adds calcium agent to crystallization reacting part 28.It is further preferred, that using motor by crystal seed warehouse 12
Crystal seed adds line 20 via crystal seed and adds into crystallization reacting part 28.
Then, in the crystallization reacting part 28 of crystallization reactive tank 10, the crystallization object material such as fluorine contained by raw water, phosphorus with
Calcium agent is reacted and generates calcirm-fluoride, calcium phosphate (slightly solubility calcium salt), and separates out in seed surface, (difficult so as to generate indissoluble salt
Dissolubility calcium salt) crystallization.
By the crystallization of the slightly solubility calcium salts such as the calcirm-fluoride generated in crystallization reacting part 28, calcium phosphate for example termly from hardly possible
Soluble is discharged line 24 and is extracted out, and discharges to its exterior.The extraction method of the crystallization of slightly solubility calcium salt is not particularly limited, can
To be the method extracted the crystallization of slightly solubility calcium salt from crystallization reactive tank 10 out using the slurry such as tube pump pump, or as schemed
Shown in 1, line 24 is discharged in indissoluble salt and valve 24a is installed, merely with gravity by the crystallization of slightly solubility calcium salt from crystallization reactive tank 10
The method of extraction.
On the other hand, the reacted water that processes of crystallization in crystallization reacting part 28 is flowed from connected entrance 32 to separation of solid and liquid portion 30
Enter.Now, a part for the crystallization of indissoluble salt is flowed in separation of solid and liquid portion 30 together with water is processed, but in separation of solid and liquid portion
30, the reacted water that processes of crystallization forms upper up-flow and passes through separation of solid and liquid portion 30, and makes contained slightly solubility in process water
Salt crystallization and process water separation of solid and liquid.Process water after separation of solid and liquid is via process water discharge line 22 as present embodiment
Final process water is discharged to its exterior.
If here, continuing to be passed through raw water to crystallization reacting part 28, the crystallization of the slightly solubility calcium salt in crystallization reacting part 28
A part for (also including cannot be in slightly solubility calcium salt crystallization that seed surface is separated out etc.), the crystal seed supplemented from crystal seed warehouse 12 etc.
Separation of solid and liquid portion 30 is flowed into together with the reacted process water of crystallization, and is retained in separation of solid and liquid portion 30 in this condition.
In these crystallizations, crystal seed, particularly the tiny crystallization of particle diameter, crystal seed are easily flowed into separation of solid and liquid portion 30.Thus, if continue to
Crystallization reactive tank 10 is passed through raw water, then be difficult to crystallization, the crystal seed for keeping particle diameter tiny in crystallization reacting part 28, therefore, it is impossible to
The surface area that will be present in the per unit weight of the crystallization in crystallization reacting part 28, crystal seed remains larger, and causes slightly solubility
The rate of recovery of the crystallization of calcium salt declines.
Then, in the present embodiment, by be intermittently passed through into crystallization reacting part 28 raw water, be repeated logical
Water and water flowing stop, so as to improve the rate of recovery of the crystallization of slightly solubility calcium salt.First, in the present embodiment, react to crystallization
Portion 28 is passed through raw water, obtains the crystallization of slightly solubility calcium salt.Now, the crystallization (also including crystal seed) of the slightly solubility calcium salt for being obtained
A part, the crystallization of the particularly tiny slightly solubility calcium salt of particle diameter are flowed in separation of solid and liquid portion 30 as described above, and indwelling
In separation of solid and liquid portion 30.But, in the present embodiment, stopped raw water being passed through to crystallization reactive tank 10, make to be trapped in
The natural subsidence such as the tiny crystallization of indissoluble salt of particle diameter in separation of solid and liquid portion 30 and make the part of at least crystallization etc. to
The operation that crystallization reacting part 28 is returned.In order that being deposited in the crystallization in separation of solid and liquid portion 30 etc. to easily return to crystallization reacting part 28
Interior, preferably make the bottom in separation of solid and liquid portion 30 downward-sloping towards crystallization reacting part 28.
Generally, carrying out the such operation of water flowing off and on is considered as being difficult in the same of the rate of recovery for guaranteeing indissoluble salt crystallization
When so that device is stably operated, but the apparatus structure using present embodiment, and make the plant running off and on
Raw water is passed through, then when next starting to be passed through raw water, as tiny crystallization of slightly solubility calcium salt of particle diameter etc. is maintained at crystallization
In reacting part 28, therefore, the magnitude of recruitment for not increasing the crystal seed supplemented from crystal seed warehouse 12 can be just made in crystallization reacting part 28
The surface area of the per unit weight of the crystallization of slightly solubility calcium salt etc. becomes big, it is possible to increase the rate of recovery of indissoluble salt crystallization.For example
In order to ensure generating the time of the crystallization of slightly solubility calcium salt and making the natural subsidence such as the crystallization being trapped in separation of solid and liquid portion 30
Time, the appropriate water flowing time for setting the raw water in present embodiment and water flowing dwell time, but it is preferred that raw water
Water flowing time and water flowing dwell time are set according to following condition.
First, the valve 18 of raw water water flowing line 16 is opened, so that the water flowing time for being passed through raw water into crystallization reacting part 28 is
Mode in more than 1/2 times of the holdup time in separation of solid and liquid portion 30 and less than 5 times of scope, is passed through into crystallization reacting part 28
Raw water.Then, the valve 18 of raw water water flowing line 16 is closed, during so as to stop the water flowing stopping for being passed through raw water into crystallization reacting part 28
Between for the mode in more than 1/5 times of holdup time of separation of solid and liquid portion 30 and less than 1 times of scope, stop to crystallization reacting part
28 are passed through raw water.Heavy in crystallization reacting part 28 thereby, it is possible to fully guarantee tiny crystallization of slightly solubility calcium salt of particle diameter etc.
The time of drop, as tiny crystallization of slightly solubility calcium salt of particle diameter etc. is maintained in crystallization reacting part 28, therefore, it is possible to enter one
Step improves the rate of recovery of the crystallization of slightly solubility calcium salt.Due to more keep in crystallization reacting part 28 particle diameter mainly 50 μm with
Under tiny crystallization, therefore, it is possible to improve the rate of recovery of the crystallization of slightly solubility calcium salt further.Assume that the particle in device is complete
Portion is identical size, then the increase that square is directly proportional of the surface area of each particle and particle diameter, but the particle of per unit weight
The increase that cube is inversely proportional to of number and particle diameter.Therefore, the surface area of per unit weight and (particle diameter)3/ (particle diameter)2=particle diameter becomes anti-
Increase than ground, therefore, by carrying out the water flowing of raw water and stopping under conditions of present embodiment, making the less indissoluble of particle diameter
Property calcium salt crystallization etc. be more present in crystallization reacting part 28 such that it is able to make crystallization in crystallization reacting part 28 per single
The surface area of position weight rises tremendously, and the rate of recovery of indissoluble salt crystallization can be greatly improved.Here, separation of solid and liquid portion 30
Holdup time refer to holdup time of the raw water being flowed in crystallization reactive tank 10, by by the volume in separation of solid and liquid portion 30 divided by
Value obtained from the influx of the raw water being flowed in crystallization reactive tank 10 represents.In addition, the opening and closing of the valve 18 of present embodiment
It can also be automatic manually that can both be.
If the water flowing for being passed through raw water into crystallization reacting part 28 has not timed out the 1/2 of the holdup time in separation of solid and liquid portion 30
Times, then the water flowing time is shorter, and the water yield that can be processed by device tails off, and the efficiency that there is the crystallization for reclaiming slightly solubility calcium salt is disliked
The situation of change.If in addition, the water flowing time that raw water is passed through into crystallization reacting part 28 exceedes the holdup time in separation of solid and liquid portion 30
5 times, then tiny crystallization of slightly solubility calcium salt of particle diameter etc. is discharged to its exterior in large quantities, and exist cannot be anti-in crystallization
Answer the situation of the crystallization for fully keeping particle diameter tiny in portion 28, it is difficult to improve the rate of recovery of the crystallization of slightly solubility calcium salt.If to
The water flowing dwell time of raw water is passed through in crystallization reacting part 28 less than 1/5 times of the holdup time in separation of solid and liquid portion 30, then be detained
Cannot completely return in crystallization reacting part 28 in the tiny crystallization of the particle diameter in separation of solid and liquid portion 30, and presence cannot be in crystallization
The situation of the crystallization for fully keeping particle diameter tiny in reacting part 28, it is difficult to improve the rate of recovery of the crystallization of slightly solubility calcium salt.Separately
Outward, if the water flowing dwell time for being passed through raw water into crystallization reacting part 28 exceedes 1 times of the holdup time in separation of solid and liquid portion 30,
Dwell time is longer, and the water yield that can be processed by device tails off, and there is the degradation in efficiency of the crystallization for reclaiming slightly solubility calcium salt
Situation.
Then, it is considered to the fine slightly solubility for not separating with facture in separation of solid and liquid portion 30 and passing through together with water is processed
Crystallization of calcium salt etc..
For example, the excessively fine crystal seed of particle diameter, the slightly solubility calcium salt that cannot be separated out in seed surface in the crystal seed for being supplemented
The minuteness particle such as crystallization will not be kept completely separate in separation of solid and liquid portion 30, and because upper up-flow is flowed out together with water is processed, and arranged
Go out to its exterior.In general, the minuteness particle being discharged is not reclaimed and as Treatment of Sludge, if but this can be made
Minuteness particle grows to the particle diameter for being capable of separation of solid and liquid, then can cut down sludge creation amount, and can also cut down the supplement of crystal seed
Amount.Since in the past, in order that the minuteness particle flowed out together with water is processed grows to the particle diameter for being capable of separation of solid and liquid, motion has one
Plant method (for example, Japanese Unexamined Patent Publication 2002-292202, the Japan spy for making the minuteness particle in process water return to crystallization reacting part
Open 2009-226232, Japanese Unexamined Patent Publication 2010-207755).
In the present embodiment, crystallization reaction unit 1 as shown in Figure 1, by separation of solid and liquid portion 30 and crystallization reacting part 28
The upper end of the internal perisporium 26 of separation is set in and processes 21 mutually level position of water outlet, or is processing the part energy of water
Enough positions less than process water outlet 21 from the range of 21 discharge of process water outlet.
Generally, due to the water level of crystallization reacting part 28 is highly identical with process water outlet 21, therefore, if inner circumferential
The upper end of wall 26 then causes crystallization reacting part with 21 height of process water outlet same or below the height for processing water outlet 21
Crystallization of slightly solubility calcium salt in 28 etc. is crossed internal perisporium 26 and overflows to 30 side of separation of solid and liquid portion.But, in present embodiment
Crystallization reaction unit 1 in, due in order to maintain the surface area of the crystallization in crystallization reacting part 28 higher, and with crystallisation concentration relatively
High state is operated, and therefore, the proportion of the per unit volume of the fluid in crystallization reacting part 28 easily becomes to be above solid-liquid
The proportion of the fluid in separation unit 30.Like this, if producing difference in specific gravity between crystallization reacting part 28 and separation of solid and liquid portion 30,
Water-head is produced between crystallization reacting part 28 and separation of solid and liquid portion 30.The water-head is present becomes several m because of size of device etc.
Water-head situation.Thus, as shown in the embodiment, reduce the position of the upper end of internal perisporium 26 even if described above,
Raw water in crystallization reacting part 28 also to 30 overflow of separation of solid and liquid portion, but will not make one of the process water in separation of solid and liquid portion 30
Part is returned to crystallization reacting part 28.Thus, any power-equipment is not used just can will to process contained microfine in water
Sub (crystallization of slightly solubility calcium salt, crystal seed etc.) is sent back to crystallization reacting part 28, therefore, it is possible to maintain crystallization reacting part 28 further
The crystallization of interior slightly solubility calcium salt, crystal seed particle diameter distribution tiny.As a result, the crystallization of slightly solubility calcium salt can be improved further
The rate of recovery.
Then, other conditions of crystallization reaction unit 1 of present embodiment etc. are described.
In the present embodiment, it is preferred that calcium agent and the interpolation (decanting point) to crystallization reacting part 28 of raw water exist
The vicinity of agitator 38 is carried out.By the agent of interpolation calcium and raw water near agitator 38, so that calcium agent and raw water exist
Spread after being passed into crystallization reacting part 28 at once, and reduce rapidly the crystallization object material concentration such as calcium agent concentration, fluorine, phosphorus.Therefore,
The situation that the indissoluble salt for being formed directly is separated out in a liquid is less, used as the difficulty soluble salt on the crystal seed in crystallization reacting part 28
Crystallization can reliably absorb the crystallization object material (fluorine, phosphorus etc.) in liquid.
In the present embodiment, it is preferred that in the way of the agitator 38 of agitating device 34 is located in cylinder, water conservancy diversion is set
Pipe 36.Now, it is preferred that agitator 38 forms sinking.If arranging mozzle 36 in this wise, under producing towards pipe bottom
Drop stream, forms the comparatively faster region of diffusion flow velocity.Therefore, it is possible to more quickly spread raw water, calcium agent etc., raw water, calcium is made
The region that the concentration local of agent is denseer does not contact each other, and suppresses to directly generate slightly solubility calcium salt particle.
If in addition, mozzle arranged as described above 36 and agitator 38, form flowing in pipe peripheral part more slow
Upwelling regions.In the region, particle is graded, and the particle of small particle rises along pipe lateral surface, also, from pipe upper end again
Invade pipe internal and decline inside pipe, the particle of the small particle to raw water, calcium agent etc. decanting point nearby, the stirring of its underpart
Mix region recycling.Crystallization is promoted to react due to the crystallization nucleation of these small particles, therefore, it is possible to improve indissoluble salt crystallization
The rate of recovery.
And, as crystallization reaction is carried out and particle diameter becomes big crystallization not because the upper up-flow of pipe peripheral part rises, and downward
Sink, and be not again introduced in mozzle 36, therefore, it is possible to prevent the crystallization after growing up from being broken because colliding with agitator 38
Bad, therefore, it is possible to be favorably improved the rate of recovery of indissoluble salt crystallization.
In the present embodiment, it is preferred that add acid or alkali to crystallization reacting part 28 and make the analysis of crystallization reacting part 28
The pH of brilliant reactant liquor in the range of 0.8～3, more preferably in the range of 1～1.5.Reacted with crystallization by adding acid or alkali
The pH in portion 28 is operated in the range of 0.8～3, thus, for example, can be reduced and be processed the crystallization object materials such as fluorine, the phosphorus of water
Concentration.
The raw water of the crystallization object material such as fluorine-containing, phosphorus in present embodiment, as long as remove containing being processed by crystallization
Fluorine, phosphorus etc., it is possible to be the raw water of any origin, for example, there are from the electronic industry headed by semiconductor related industry,
The raw water of the discharges such as power plant, aluminum i ndustry, but it is not limited to this.
As long as become the fluorine of crystallization object material, phosphorus etc. because crystallization react and crystallization, it becomes possible to arbitrary state exist
In raw water.From from the viewpoint of be dissolved in raw water, it is preferred that state of the crystallization object material in ionization.
As the calcium agent used in present embodiment, for example, can use calcium chloride, calcium hydroxide etc..As interpolation calcium agent
Form, can both be pulverulence, or slurry form.
As the injection rate of calcium agent, the chemical equivalent of calcium can both be fluorine, 0.8 times～2 times, or 1 times～2 of phosphorus
Times, but more preferably 1 times～1.2 times.If the chemical equivalent of calcium more than raw water fluorine, stoichiometric 2 times of phosphorus, be fluorinated
Calcium, calcium phosphate will not be separated out on crystal seed and easily be generated as particulate, and exist to process and be mixed into calcirm-fluoride, calcium phosphate in water
Situation, if being less than 0.8 times, cannot become calcirm-fluoride, the fluorine of calcium phosphate, the ratio of phosphorus in fluorine in raw water, phosphorus increases, and deposits
The situation of fluorine, phosphorus is mixed in water is processed.
In the present embodiment, before raw water and calcium agent is added to crystallization reacting part 28, can be in crystallization reacting part
Pre-existing crystal seed, or there is no crystal seed in advance in crystallization reacting part 28 in 28.In order to carry out stable process, excellent
Choosing, pre-existing crystal seed in the crystallization reacting part 28.
As long as crystal seed separates out can the crystallization of the slightly solubility calcium salt in its Surface Creation, arbitrary material can be selected
Matter, for example, can enumerate containing filtration sand, activated carbon and with zircon sand, pomegranate stone sand, Sakurandam (trade name, Japan
Carlit Co. Ltd. system) etc. headed by metallic element oxide particle and containing crystallization reaction precipitate
That is particle of slightly solubility calcium salt etc., but it is not limited to this.From purer indissoluble salt can be obtained as particle etc.
From the viewpoint of obtaining, the precipitate i.e. particle of indissoluble salt of crystallization reaction is preferably comprised.As reacted containing crystallization
Precipitate is the particle of slightly solubility calcium salt, for example, in the case of calcirm-fluoride is separated out, can enumerate fluorite etc., in precipitation of phosphorus
In the case of sour calcium, rock phosphate in powder etc. can be enumerated.
From from the viewpoint of carry out crystallization reaction well, during the delay of the flow of the raw water being passed through to crystallization reacting part 28
Between preferably in the range of 1 hour～4 hours, more preferably at 2 hours～4 hours.
From from the viewpoint of carry out crystallization reaction well, the flow velocity (LV) of the process water of flowing in separation of solid and liquid portion 30
It is preferred that in the range of 0.1m/h～2.0m/h, more preferably in the range of 0.2m/h～1.0m/h.
Fig. 2 is the schematic diagram of of the structure of the crystallization reaction unit for representing reference example.Crystallization reaction dress shown in Fig. 2
Put 100 include crystallization reactive tank 110, crystal seed warehouse 112, as crystallization reactive tank 110 add calcium agent interpolation part
The calcium agent of add line 114, as the raw water for flowing into of part for making raw water flow into crystallization reactive tank 110
Water flowing line 116, crystal seed adds line 118, processes water discharge line 120 and indissoluble salt discharge line 122.
Crystallization reactive tank 110 is connected with from the raw water water flowing line 116 of raw water storage tank (not shown) and from calcium agent storage tank
Line 114 is added in the calcium agent of (not shown).In addition, being connected with crystal seed between crystal seed warehouse 112 and crystallization reactive tank 110 to add line
118.In addition, the process water outlet 111 of crystallization reactive tank 110 is connected with process water discharges line 120, crystallization reactive tank 110
Indissoluble salt outlet is connected with indissoluble salt and discharges line 122.
It is provided with crystallization reactive tank 110 for the crystallization reacting part 126 of the crystallization that generates indissoluble salt and for carrying out
The separation of solid and liquid portion 128 of the separation of solid and liquid between indissoluble salt crystallization and process water.It is provided with and crystallization in crystallization reactive tank 110
The relative internal perisporium 124 of the periphery wall of reactive tank 110, will be set to separation of solid and liquid portion 128 between the periphery wall and internal perisporium 124.
The internal perisporium 124 of present embodiment is in the specified interval of the periphery wall of crystallization reactive tank 110, but internal perisporium 124 can also
Complete cycle located at periphery wall.
Crystallization reacting part 126 is divided by internal perisporium 124 with separation of solid and liquid portion 128, is formed with company in the bottom of internal perisporium 124
Logical crystallization reacting part 126 and the connected entrance 130 in separation of solid and liquid portion 128.In addition, above-mentioned process water outlet 111 is located at crystallization
The formation of reactive tank 110 has the periphery wall in separation of solid and liquid portion 128, and the process water outlet 111 is connected with process water and discharges line
120.
In addition, the upper end of the internal perisporium 124 for being separated separation of solid and liquid portion 128 with crystallization reacting part 126 is set in and process
The mutually level position of water outlet 111, or can be from the range of 111 discharge of process water outlet in the part for processing water
It is set below processing the position of water outlet 111.
The crystallization reacting part 126 of crystallization reactive tank 110 is included as stirring in mozzle 134, crystallization reacting part 126
The agitating device 132 of of mixing component of fluid.Agitating device 132 includes agitator 138, and agitator 138 is configured
In mozzle 134, and using the revolving force rotation produced by the motor transmitted via shaft.
The action of the crystallization reaction unit 100 of present embodiment is described.
First, it is passed through into crystallization reacting part 126 containing fluorine, the crystallization object material of phosphorus via raw water water flowing line 116
Raw water (exists below the situation of referred to as " raw water ".).In addition, adding line 114 via calcium agent, add into crystallization reacting part 126
Plus calcium agent.It is further preferred, that the crystal seed in crystal seed warehouse 112 is added line 118 via crystal seed using motor reacting to crystallization
Portion 126 adds.
Then, in the crystallization reacting part 126 of crystallization reactive tank 110, the fluorine contained by raw water, the crystallization object material of phosphorus
React with calcium agent and calcirm-fluoride, calcium phosphate (slightly solubility calcium salt) is generated, and separate out in seed surface, become indissoluble salt (indissoluble
Property calcium salt) crystallization.
By the calcirm-fluoride generated in crystallization reacting part 126, the slightly solubility calcium salt of calcium phosphate crystallization for example termly from
Indissoluble salt is discharged line 122 and is extracted out, and discharges to its exterior.The extraction method of the crystallization of slightly solubility calcium salt does not have special limit
Fixed, but can both be the method that the crystallization of slightly solubility calcium salt is extracted out from crystallization reactive tank 110 using the slurry such as tube pump pump,
Can be as shown in figure 1, indissoluble salt discharge line 122 install valve 122a, merely with gravity by the crystallization of slightly solubility calcium salt from
The method that crystallization reactive tank 110 is extracted out.
On the other hand, the reacted water that processes of crystallization in crystallization reacting part 126 is from connected entrance 130 to separation of solid and liquid portion
128 flow into.Now, a part for the crystallization of indissoluble salt is flowed into separation of solid and liquid portion 128 together with water is processed, but is divided in solid-liquid
From portion 128, the reacted water that processes of crystallization forms upper up-flow and passes through separation of solid and liquid portion 128, and contained by making in process water
Indissoluble salt crystallization and process water separation of solid and liquid.Process water after separation of solid and liquid is via process water discharge line 120 as this reality
The final process water for applying mode is discharged to its exterior.
However, the excessively fine crystal seed of particle diameter in the crystal seed for being supplemented, the slightly solubility calcium salt that cannot be separated out in seed surface
The minuteness particle such as crystallization will not be kept completely separate in separation of solid and liquid portion 128, and because upper up-flow is flowed out together with water is processed, and arranged
Go out to its exterior.In general, the minuteness particle being discharged is not reclaimed and as Treatment of Sludge, if but can make micro-
Fine particle grows to the particle diameter for being capable of separation of solid and liquid, then can cut down sludge creation amount, and can also cut down the magnitude of recruitment of crystal seed.
Since in the past, in order that the minuteness particle flowed out together with water is processed grows to the particle diameter for being capable of separation of solid and liquid, motion has one kind
The minuteness particle in process water is made to return to method (for example, Japanese Unexamined Patent Publication 2002-292202, the Japanese Unexamined Patent Publication of reactive moieties
2009-226232, Japanese Unexamined Patent Publication 2010-207755).
In the present embodiment, crystallization reaction unit 100 as shown in Figure 2, by separation of solid and liquid portion 128 and crystallization reacting part
The upper end of 126 internal perisporiums 124 for separating is set in and processes 111 mutually level position of water outlet, or is processing the one of water
Part can be set below processing the position of water outlet 111 from the range of 111 discharge of process water outlet.
Generally, due to the water level of crystallization reacting part 126 is highly identical with process water outlet 111, therefore, if interior
The upper end of perisporium 124 then causes crystallization with 111 height of process water outlet same or below the height for processing water outlet 111
Crystallization of slightly solubility calcium salt in reacting part 126 etc. is crossed internal perisporium 124 and overflows to 128 side of separation of solid and liquid portion.But, obtaining
In the case of obtaining calcirm-fluoride, the crystallization of calcium phosphate, the proportion of the per unit volume of the fluid in crystallization reacting part 126 easily becomes
Proportion higher than the fluid in separation of solid and liquid portion 128.For example in the case of obtaining the crystallization of calcirm-fluoride, in crystallization reacting part 126
The weight of every 1L raw water for containing crystallization can become 2.0kg/L.In contrast, the proportion in separation of solid and liquid portion 128 is at most
For 1.0kg/L～1.2kg/L or so.
Like this, if producing difference in specific gravity between crystallization reacting part 126 and separation of solid and liquid portion 128, in crystallization reacting part 126
Water-head is produced between separation of solid and liquid portion 128.Thus, as shown in the embodiment, reduce internal perisporium even if described above
The position of 124 upper end, the raw water in crystallization reacting part 126 also to 128 overflow of separation of solid and liquid portion, but will not make separation of solid and liquid
A part for process water in portion 128 is returned to crystallization reacting part 126.Thus, any power-equipment is not used just will can to locate
In reason water, contained minuteness particle (crystallization of slightly solubility calcium salt, crystal seed etc.) is sent back to crystallization reacting part 126, therefore, it is possible to
Maintain the particle diameter distribution of the crystallization of slightly solubility calcium salt in crystallization reacting part 126, crystal seed tiny further.As a result, can enter
One step improves the rate of recovery of the crystallization of slightly solubility calcium salt.
Then, other conditions of the crystallization reaction unit 100 of present embodiment are described.
The material raw water of object containing crystallization in present embodiment contains fluorine, the phosphorus that can be processed removal by crystallization.But, as long as
Containing fluorine, phosphorus, it is possible to be the raw water of any origin, for example, there are from headed by semiconductor related industry electronic industry,
The raw water of the discharges such as power plant, aluminum i ndustry, but it is not limited to this.
As long as becoming the fluorine of crystallization object material, phosphorus to crystallize because crystallization reacts, it becomes possible to be present in arbitrary state
In raw water.From from the viewpoint of be dissolved in raw water, it is preferred that the state of fluorine, phosphorus in ionization.
In the present embodiment, it is preferred that calcium agent and the interpolation (decanting point) to crystallization reacting part 126 of raw water exist
The vicinity of agitator 138 is carried out.By the agent of interpolation calcium and raw water near agitator 138, so that calcium agent and raw water
Spread after crystallization reacting part 126 is injected at once, and reduce rapidly calcium agent concentration, fluorine, phosphorus concentration.Therefore, the difficulty for being formed
The situation that soluble is directly separated out in a liquid is less, and as the difficulty soluble salt crystal energy on the crystal seed in crystallization reacting part 126
Enough fluorine reliably absorbed in liquid, phosphorus.
In the present embodiment, it is preferred that arrange in the way of the agitator 138 of agitating device 132 is located in cylinder and lead
Flow tube 134.Now, it is preferred that agitator 138 forms sinking.If arranging mozzle 134 in this wise, towards pipe bottom
Sinking is produced, forms the comparatively faster region of diffusion flow velocity.Therefore, it is possible to more quickly spread raw water, calcium agent etc., original is made
Water, the region that the concentration local of calcium agent is denseer do not contact each other, and suppress to directly generate slightly solubility calcium salt particle.
If in addition, mozzle arranged as described above 134 and agitator 138, form flowing in pipe peripheral part slower
Upwelling regions.In the region, particle is graded, and the particle of small particle rises along pipe lateral surface, also, from pipe upper end again
Subintrusion is internal to pipe and declines inside pipe, the particle of small particle to raw water, calcium agent etc. decanting point nearby or its underpart
Stirring region is recycled.Crystallization is promoted to react due to the crystallization nucleation of these small particles, therefore, it is possible to improve indissoluble salt knot
The brilliant rate of recovery.
And, as crystallization reaction is carried out and particle diameter becomes big crystallization not because the upper up-flow of pipe peripheral part rises, and downward
Sink and be not again introduced in mozzle 134, therefore, it is possible to prevent the crystallization that grows up to be destroyed because colliding with agitator 138,
Therefore, it is possible to be favorably improved the rate of recovery of soluble crystallization.
In the present embodiment, it is preferred that add acid or alkali to crystallization reactive tank 110 and make crystallization reacting part 126
The pH of crystallization reactant liquor in the range of 0.8～3, more preferably in the range of 1～1.5.Anti- with crystallization by adding acid or alkali
Answer the pH in portion 126 to be operated in the range of 0.8～3, thus, for example, can reduce fluorine, the phosphorus i.e. crystallization object for processing water
Material concentration.
Calcium agent used in present embodiment can for example use calcium chloride, calcium hydroxide etc..As interpolation calcium agent
Form, can both be pulverulence, or slurry form.
As the injection rate of calcium agent, the chemical equivalent of calcium can both be fluorine, 0.8 times～2 times, or 1 times～2 of phosphorus
Times, but more preferably 1 times～1.2 times.If the chemical equivalent of calcium more than raw water fluorine, stoichiometric 2 times of phosphorus, be fluorinated
Calcium, calcium phosphate will not be separated out on crystal seed and easily be generated as particulate, and exist to process and be mixed into calcirm-fluoride, calcium phosphate in water
Situation, if being less than 0.8 times, cannot become calcirm-fluoride, the fluorine of calcium phosphate, the ratio of phosphorus in fluorine in raw water, phosphorus increases, and deposits
The situation of fluorine, phosphorus is mixed in water is processed.
In the present embodiment, before raw water and calcium agent is added to crystallization reacting part 126, can be in crystallization reacting part
Pre-existing crystal seed, or there is no crystal seed in advance in crystallization reacting part 126 in 126.In order to carry out stable process,
Preferably, pre-existing crystal seed in the crystallization reacting part 126.
As long as crystal seed separates out can the crystallization of the slightly solubility calcium salt in its Surface Creation, arbitrary material can be selected
Matter, for example, can there are containing filtration sand, activated carbon and with zircon sand, pomegranate stone sand, Sakurandam (trade name, Japan
Carlit Co. Ltd. system) etc. headed by metallic element oxide particle and containing crystallization reaction precipitate
That is particle of indissoluble salt etc., but it is not limited to this.From purer indissoluble salt can be obtained as particle etc.
From the viewpoint of, preferably comprise the precipitate i.e. particle of indissoluble salt of crystallization reaction.As the analysis that reacts containing crystallization
Go out the thing i.e. particle of indissoluble salt, in the case of calcirm-fluoride is separated out, for example, fluorite etc. can be enumerated, separate out calcium phosphate
In the case of, can for example enumerate rock phosphate in powder etc..
Embodiment
Hereinafter, embodiment and comparative example are enumerated more specific and explain the present invention, but the present invention be not limited to
Under embodiment.
Embodiment 1
In embodiment 1, using the crystallization reaction unit shown in Fig. 1, according to following condition, carried out from fluorine-containing raw water
Middle recovery calcirm-fluoride.
Crystallization reaction unit
Crystallization reacting part size：130L
Separation of solid and liquid portion size：230L(440×590×880mmH)
Experimental condition
Fluorine-containing raw water flow：50L/h
The Funing tablet of fluorine-containing raw water：10000mg/L
Calcium agent：Solution with the slurry of 10% calcium hydroxide of dissolving with hydrochloric acid
PH in crystallization reacting part：PH2 (by adding NaOH adjustment)
Initial filling crystal seed in crystallization reacting part：20kg (supplement of the crystal seed after no)
Slurry concentration in crystallization reacting part：30～35v/v% (is suitably extracted out from indissoluble salt discharge pipe)
The holdup time in the separation of solid and liquid portion of embodiment 1 is 4.6h (230 (L)/50 (L/h)), the delay of crystallization reacting part
Time is 2.6h.
In embodiment 1, after raw water being passed through 9.2 hours into crystallization reacting part, stop water flowing 2.3 hours.Enter repeatedly
The row water flowing and stopping water flowing, till the water flowing time reaches 400 hours.The process water in separation of solid and liquid portion during water flowing
Flow velocity (LV) is 0.2m/h.In addition, the part for processing water in separation of solid and liquid portion is not sent back to the state of crystallization reacting part
Under tested.
Embodiment 2
In example 2, raw water is being passed through into crystallization reacting part 4.6 hours afterwards, stopping water flowing 1.15 hours, except this
In addition, tested with condition same as Example 1.
Embodiment 3
In embodiment 3, raw water is being passed through into crystallization reacting part 4.6 hours afterwards, stopping water flowing 2.3 hours, except this
In addition, tested with condition same as Example 1.
Embodiment 4
In example 4, reacted using the crystallization by separation of solid and liquid portion dimension modifying for 23L (440 × 60 × 880mmH)
Device.In addition, in example 4, it is being passed through raw water into crystallization reacting part 0.46 hour afterwards, is stopping water flowing 0.23 hour.
The water flowing is repeated and stops water flowing, till the water flowing time reaches 400 hours.In addition, separation of solid and liquid during water flowing
The flow velocity (LV) of the process water in portion is 2.0m/h.
Embodiment 5
In embodiment 5, raw water is being passed through into crystallization reacting part 18.4 hours afterwards, is stopping water flowing 2.3 hours, except this
In addition, tested with condition same as Example 1.
Comparative example 1
In comparative example 1, do not carry out the stopping water flowing of raw water, into crystallization reacting part, be passed through raw water 400 hours, except this with
Outward, tested with condition same as Example 1.The flow velocity (LV) of the process water in separation of solid and liquid portion during water flowing is 0.2m/
h.
Comparative example 2
In comparative example 2, reacted using the crystallization by separation of solid and liquid portion dimension modifying for 23L (440 × 60 × 880mmH)
Device, and do not carry out the stopping water flowing of raw water, is passed through raw water 400 hours into crystallization reacting part, in addition, with embodiment
1 identical condition is tested.The flow velocity (LV) of the process water in separation of solid and liquid portion during water flowing is 2.0m/h.
Summarize in table 1 embodiment 1～5 and comparative example 1～2 separation of solid and liquid portion process water flow velocity, to crystallization
The rate of recovery of water flowing time of raw water, water flowing dwell time and the calcirm-fluoride after water flowing 400 hours is passed through in reacting part.
Table 1
Embodiment 6
In embodiment 6, using in the crystallization reaction unit shown in Fig. 1 by the upper end of internal perisporium be set in and process water
The crystallization reaction unit of the mutually level position of outlet, and it is anti-that a part for the process water in separation of solid and liquid portion is sent back to crystallization
Portion is answered, in addition, is tested with condition same as Example 1.
Embodiment 7
In embodiment 7, being passed through raw water 4.6 hours afterwards to crystallization reacting part, stop water flowing 2.3 hours, except this with
Outward, tested with condition same as Example 6.
Comparative example 3
In comparative example 3, using in the crystallization reaction unit shown in Fig. 2 by the upper end of internal perisporium be set in and process water
The crystallization reaction unit of the mutually level position of outlet, does not carry out the stopping water flowing of raw water, is passed through original into crystallization reacting part
Water 400 hours, in addition, is tested with condition same as Example 5.
The flow velocity of the process water in the separation of solid and liquid portion of embodiment 6～7 and comparative example 3 is summarized in table 2, reacted to crystallization
The rate of recovery of water flowing time of raw water, water flowing dwell time and the calcirm-fluoride after water flowing 400 hours is passed through in portion.
Table 2
Fig. 3 is the figure of the particle diameter distribution of the crystallization in the crystallization reacting part for represent embodiment 1, and Fig. 4 represents embodiment 2
The figure of the particle diameter distribution of the crystallization in crystallization reacting part, Fig. 5 are that the particle diameter of the crystallization in the crystallization reacting part for represent embodiment 3 divides
The figure of cloth, Fig. 6 are the figures of the particle diameter distribution of the crystallization in the crystallization reacting part for represent embodiment 4, and Fig. 7 represents comparative example 1
The figure of the particle diameter distribution of the crystallization in crystallization reacting part, Fig. 8 are that the particle diameter of the crystallization in the crystallization reacting part for represent comparative example 2 divides
The figure of cloth, Fig. 9 are the figures of the particle diameter distribution of the crystallization in the crystallization reacting part for represent comparative example 3.Crystallization in crystallization reacting part
Particle diameter distribution be using particle diameter distribution meter (Beckman coulter society LS230) measurement water flowing 400 hours after crystallization anti-
Answer obtained from the particle diameter distribution in portion.
In the comparative example 1 for not supplementing crystal seed and reclaiming calcirm-fluoride by being continuously passed through raw water, such as according to Fig. 7 and Biao 1
Result clear and definite as, there is crystallization of the particle diameter more than 100 μm in crystallization reacting part in a large number, and the rate of recovery be relatively low,
For 65%.And, bring up in the comparative example 2 of 2.0m/h in the flow velocity of the process water by separation of solid and liquid portion, such as according to Fig. 8 and Biao
As 1 result is clear and definite, there is crystallization of the particle diameter more than 125 μm in crystallization reacting part in a large number, the rate of recovery is also lower, is
50%.On the other hand, it is being passed through the embodiment, specifically of raw water off and on, is being separation of solid and liquid in the water flowing time for making raw water
More than 1/2 times of the holdup time in portion and less than 5 times and make the stopping water flowing time for separation of solid and liquid portion holdup time 1/5
Times above and less than 1 times and in the embodiment 1～5 that carries out, as the result according to Fig. 3～6 and table 1 is clear and definite, in crystallization
There is crystallization of the particle diameter below 100 μm in reacting part in a large number, the rate of recovery also becomes more than 75%, and it is higher than to compare to be obtained in that
The rate of recovery of example 1,2.Particularly, is made for 1 times and the stopping water flowing of the holdup time in separation of solid and liquid portion the water flowing time of raw water
The embodiment 3 for carrying out, the water flowing time for making raw water are separation of solid and liquid for 1/2 times of the holdup time in separation of solid and liquid portion time
1 times of the holdup time in portion and stop the embodiment 4 that the water flowing time carries out for 1/2 times of the holdup time in separation of solid and liquid portion
In, as the result according to Fig. 5, Fig. 6 and table 1 is clear and definite, there is knot of the particle diameter below 50 μm in crystallization reacting part
Crystalline substance, the rate of recovery also become more than 90%, and the rate of recovery being obtained in that higher than embodiment 1,2.That is, by during the water flowing that makes raw water
Between for 1 times of holdup time of separation of solid and liquid portion and make the stopping water flowing time for 1/2 times of the holdup time in separation of solid and liquid portion, energy
Enough crystallizations for keeping particle diameter more tiny in crystallization reacting part, it is also possible to improve the rate of recovery of calcirm-fluoride crystallization further.
As the result of table 2 is clear and definite, in embodiment 6,7, it is passed through raw water off and on, also, makes separation of solid and liquid portion
A part for interior process water is crossed internal perisporium and backs into crystallization reacting part, so as to bring up to the rate of recovery further
More than 95%.
Description of reference numerals
1st, 100, crystallization reaction unit；10th, 110, crystallization reactive tank；12nd, 112, crystal seed warehouse；14th, 114, calcium agent is added
Line；16th, 116, raw water water flowing line；18th, 24a, 122a, valve；20th, 118, crystal seed adds line；21st, 111, process water outlet；22、
120th, process water and discharge line；24th, 122, indissoluble salt discharges line；26th, 124, internal perisporium；28th, 126, crystallization reacting part；30、
128th, separation of solid and liquid portion；32nd, 130, connected entrance；34th, 132, agitating device；36th, 134, mozzle；38th, 138, agitator.
Claims (3)
1. a kind of crystallization reaction unit, it is characterised in that
The crystallization reaction unit includes：Crystallization reactive tank, it include crystallization reacting part, and the crystallization reacting part is included with agitator
Mixing component, the crystallization reacting part to containing crystallization object material raw water add calcium agent and generate the crystallization of indissoluble salt；
And water flowing part, which is used for being passed through above-mentioned raw water into above-mentioned crystallization reacting part,
In above-mentioned crystallization reactive tank, it is configured with the internal perisporium relative with the periphery wall of above-mentioned crystallization reactive tank and is provided with inside and outside
Upper up-flow is formed between perisporium and the separation of solid and liquid portion of the separation of solid and liquid between above-mentioned crystallization and process water is carried out,
Above-mentioned water flowing part is passed through above-mentioned raw water to above-mentioned crystallization reacting part off and on,
The water flowing time of above-mentioned raw water when above-mentioned water flowing part carries out interval water flowing is the holdup time in above-mentioned separation of solid and liquid portion
More than 1/2 times and less than 5 times, the water flowing dwell time of above-mentioned raw water when above-mentioned water flowing part carries out interval water flowing is above-mentioned
More than 1/5 times of the holdup time in separation of solid and liquid portion and less than 1 times.
2. a kind of crystallization reaction unit, it is characterised in that
The crystallization reaction unit includes：Crystallization reactive tank, it include crystallization reacting part, and the crystallization reacting part is included with agitator
Mixing component, the crystallization reacting part to containing crystallization object material raw water add calcium agent and generate the crystallization of indissoluble salt；
And water flowing part, which is used for being passed through above-mentioned raw water into above-mentioned crystallization reacting part,
In above-mentioned crystallization reactive tank, it is configured with the internal perisporium relative with the periphery wall of above-mentioned crystallization reactive tank and is provided with inside and outside
Upper up-flow is formed between perisporium and the separation of solid and liquid portion of the separation of solid and liquid between above-mentioned crystallization and process water is carried out,
Above-mentioned water flowing part is passed through above-mentioned raw water to above-mentioned crystallization reacting part off and on,
The water flowing time of above-mentioned raw water when above-mentioned water flowing part carries out interval water flowing is the holdup time in above-mentioned separation of solid and liquid portion
More than 1 times and less than 4 times, the water flowing dwell time of above-mentioned raw water when above-mentioned water flowing part carries out interval water flowing is above-mentioned solid
More than 1/4 times of the holdup time of liquid separation unit and less than 1/2 times.
3. crystallization reaction unit according to claim 1 and 2, it is characterised in that
The row for discharging above-mentioned process water is formed with the periphery wall of the above-mentioned crystallization reactive tank for being provided with above-mentioned separation of solid and liquid portion
Outlet,
The upper end of above-mentioned internal perisporium is located at and the mutually level position of above-mentioned outlet, or can in the part of above-mentioned process water
From above-mentioned outlet discharge in the range of positioned at less than above-mentioned outlet position, in above-mentioned separation of solid and liquid portion process water one
Part is crossed above-mentioned internal perisporium and is sent back to above-mentioned crystallization reacting part.
Applications Claiming Priority (1)
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|---|---|---|---|
| PCT/JP2013/067526 WO2014207837A1 (en) | 2013-06-26 | 2013-06-26 | Crystallization reactor |
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| CN105339063B true CN105339063B (en) | 2017-03-08 |
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| KR (1) | KR101793809B1 (en) |
| CN (1) | CN105339063B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1906129A (en) * | 2004-01-21 | 2007-01-31 | 森田化学工业株式会社 | Method for producing calcium fluoride, reusing method and recycling method thereof |
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| JPS61141996A (en) * | 1984-12-17 | 1986-06-28 | Ataka Kogyo Kk | Treatment of waste water |
| JP4439040B2 (en) * | 1999-08-03 | 2010-03-24 | 前澤工業株式会社 | Wastewater treatment equipment |
| JP4842450B2 (en) * | 2001-03-30 | 2011-12-21 | オルガノ株式会社 | Crystallization reactor equipped with turbidity measuring means and crystallization treatment method using the same |
| JP2002292204A (en) * | 2001-03-30 | 2002-10-08 | Japan Organo Co Ltd | Crystallization reaction apparatus provided with means for controlling amount of raw water to be supplied and crystallization method to use the same |
| JP4072091B2 (en) * | 2003-04-25 | 2008-04-02 | アタカ大機株式会社 | Phosphorus resource recovery method |
| JP5414169B2 (en) * | 2007-11-15 | 2014-02-12 | オルガノ株式会社 | Crystallization reactor and crystallization reaction method |
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2013
- 2013-06-26 WO PCT/JP2013/067526 patent/WO2014207837A1/en active Application Filing
- 2013-06-26 SG SG11201509658PA patent/SG11201509658PA/en unknown
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|---|---|---|---|---|
| CN1906129A (en) * | 2004-01-21 | 2007-01-31 | 森田化学工业株式会社 | Method for producing calcium fluoride, reusing method and recycling method thereof |
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| SG11201509658PA (en) | 2015-12-30 |
| WO2014207837A1 (en) | 2014-12-31 |
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| KR20160004361A (en) | 2016-01-12 |
| KR101793809B1 (en) | 2017-11-03 |
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