WO2014207837A1 - Réacteur de cristallisation - Google Patents

Réacteur de cristallisation Download PDF

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Publication number
WO2014207837A1
WO2014207837A1 PCT/JP2013/067526 JP2013067526W WO2014207837A1 WO 2014207837 A1 WO2014207837 A1 WO 2014207837A1 JP 2013067526 W JP2013067526 W JP 2013067526W WO 2014207837 A1 WO2014207837 A1 WO 2014207837A1
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Prior art keywords
crystallization reaction
solid
water
raw water
liquid separation
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PCT/JP2013/067526
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English (en)
Japanese (ja)
Inventor
徹 中野
Original Assignee
オルガノ株式会社
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Filing date
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Application filed by オルガノ株式会社 filed Critical オルガノ株式会社
Priority to CN201380077825.7A priority Critical patent/CN105339063B/zh
Priority to SG11201509658PA priority patent/SG11201509658PA/en
Priority to PCT/JP2013/067526 priority patent/WO2014207837A1/fr
Priority to KR1020157033811A priority patent/KR101793809B1/ko
Publication of WO2014207837A1 publication Critical patent/WO2014207837A1/fr

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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
    • 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
    • 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

Definitions

  • the present invention relates to a technology of a crystallization reaction apparatus for treating a crystallization target substance such as fluorine or phosphorus as a hardly soluble salt.
  • a crystallization method or the like is used as a method for recovering and reusing hardly soluble salts such as calcium fluoride and calcium phosphate.
  • the crystallization method for example, when fluorine in the fluorine-containing raw water is recovered as calcium fluoride, the fluorine-containing raw water is allowed to flow into the reaction tank, and the calcium agent is injected to react them, and in the reaction tank For example, calcium fluoride is precipitated on the seed crystal surface.
  • the raw water containing the crystallization target material such as fluorine-containing raw water is supplied to the reaction tank in an upward flow, and the fluidized bed type crystal is processed while flowing the hardly-soluble salt crystals in the reaction tank.
  • An agitation reaction apparatus for example, Patent Document 1
  • a stirrer type crystallization reaction apparatus for example, Patent Document 2
  • Etc. Etc.
  • the drawing step of drawing a part of the hardly soluble salt crystals from the reaction vessel and the replenishment step of newly replenishing seed crystals are repeated.
  • a method of continuously obtaining crystals of poorly soluble salts is employed.
  • JP 2003-225680 A JP 2008-73589 A JP 2002-292202 A JP 2009-226232 A JP 2010-207755 A
  • the surface area of the hardly soluble salt crystal or the like in the reaction tank is kept high, that is, the particles of the hardly soluble salt crystal in the reaction tank. It is important to keep the particle size fine.
  • As a method of keeping the particles (particle size distribution) of the sparingly soluble salt crystals in the reaction tank fine it is conceivable to supply a large amount of seed crystals having a fine particle size distribution in the tank, but the amount of seed crystals supplied increases. As a result, the processing cost increases.
  • an object of the present invention is to provide a crystallization reaction apparatus that can recover a hardly soluble salt at a high recovery rate without increasing the replenishment amount of seed crystals.
  • a crystallization reaction apparatus includes a crystallization reaction unit that includes a stirring unit having a stirring blade and generates a hardly soluble salt crystal by adding a calcium agent to raw water containing a crystallization target substance.
  • An crystallization reaction tank, and a water passage means for passing the raw water to the crystallization reaction part, and an inner peripheral wall facing the outer peripheral wall of the crystallization reaction tank is disposed in the crystallization reaction tank.
  • a solid-liquid separation unit that forms an upward flow between the inner and outer peripheral walls and performs solid-liquid separation between the crystal and the treated water, and the water flow means passes the raw water to the crystallization reaction unit. It is characterized by performing water intermittently.
  • the flow time of the raw water during intermittent water flow by the water flow means is 1 ⁇ 2 times to 5 times the residence time in the solid-liquid separation unit.
  • the flow stop time of the raw water during intermittent water flow by the water flow means is 1/5 times or more and 1 time or less of the residence time in the solid-liquid separation unit.
  • the flow time of the raw water during intermittent water flow by the water flow means is 1 to 24 times the residence time in the solid-liquid separation unit. More preferably, the flow stoppage time of the raw water during intermittent water flow by the water flow means is not less than 1/4 times and not more than 1/2 times the residence time in the solid-liquid separation unit.
  • the treated water is discharged to an outer peripheral wall of the crystallization reaction tank provided with the solid-liquid separation unit.
  • the upper end of the inner peripheral wall is at the same height as the discharge port or at a position lower than the discharge port within a range in which a part of the treated water can be discharged from the discharge port. It is preferable that a part of the treated water in the liquid separation part is returned to the crystallization reaction part across the inner peripheral wall.
  • the hardly soluble salt can be recovered at a high recovery rate without increasing the replenishment amount of the seed crystals.
  • FIG. 2 is a graph showing the particle size distribution of crystals in the crystallization reaction part of Example 1.
  • FIG. 4 is a graph showing a particle size distribution of crystals in a crystallization reaction part of Example 2.
  • FIG. 6 is a graph showing the particle size distribution of crystals in the crystallization reaction part of Example 3.
  • FIG. 6 is a graph showing a particle size distribution of crystals in a crystallization reaction part of Example 4.
  • FIG. 2 is a graph showing a particle size distribution of crystals in a crystallization reaction part of Comparative Example 1.
  • FIG. 6 is a graph showing a particle size distribution of crystals in a crystallization reaction part of Comparative Example 2.
  • FIG. 6 is a graph showing a particle size distribution of crystals in a crystallization reaction part of Comparative Example 3.
  • FIG. 1 is a schematic diagram showing an example of a crystallization reaction apparatus according to an embodiment of the present invention.
  • the crystallization reaction apparatus 1 includes a crystallization reaction tank 10, a seed crystal silo 12, a calcium agent addition line 14 as an example of addition means for adding a calcium agent to the crystallization reaction tank 10, and raw water.
  • a raw water passage line 16 and a valve 18 As an example of inflow means for flowing into the crystallization reaction tank 10, a raw water passage line 16 and a valve 18, a seed crystal addition line 20, a treated water discharge line 22, and a hardly soluble salt discharge line 24 are provided.
  • the crystallization reaction tank 10 is connected with a raw water passage line 16 from a raw water storage tank (not shown) and a calcium agent addition line 14 from a calcium agent storage tank (not shown).
  • a seed crystal addition line 20 is connected between the seed crystal silo 12 and the crystallization reaction tank 10.
  • a treated water discharge line 22 is connected to the treated water discharge port 21 of the crystallization reaction tank 10, and a hardly soluble salt discharge line 24 is connected to the hardly soluble salt discharge port of the crystallization reaction tank 10. .
  • a crystallization reaction section 28 for generating a hardly soluble salt crystal and a solid-liquid separation section 30 for performing a solid-liquid separation between the hardly soluble salt crystal and the treated water there are provided a crystallization reaction section 28 for generating a hardly soluble salt crystal and a solid-liquid separation section 30 for performing a solid-liquid separation between the hardly soluble salt crystal and the treated water.
  • an inner peripheral wall 26 facing the outer peripheral wall of the crystallization reaction tank 10 is provided, and a solid-liquid separation unit 30 is formed between the outer peripheral wall and the inner peripheral wall 26.
  • the inner peripheral wall 26 of this embodiment is provided in the predetermined area of the outer peripheral wall of the crystallization reaction tank 10, the inner peripheral wall 26 may be provided over the perimeter of the outer peripheral wall.
  • the crystallization reaction part 28 and the solid-liquid separation part 30 are partitioned by an inner peripheral wall 26, and a communication port 32 is formed in the lower part of the inner peripheral wall 26 for communication between the crystallization reaction part 28 and the solid-liquid separation.
  • the treated water discharge port 21 described above is provided on the outer peripheral wall of the crystallization reaction tank 10 where the solid-liquid separation unit 30 is formed, and the treated water discharge line 22 is connected to the treated water discharge port 21. ing.
  • the crystallization reaction section 28 of the crystallization reaction tank 10 includes a draft tube 36 and a stirring device 34 as an example of a stirring means for stirring the fluid in the crystallization reaction section 28.
  • the stirring device 34 includes a stirring blade 38, and the stirring blade 38 is disposed in the draft tube 36 and is rotated by a rotational force generated by a motor that is transmitted through the stirring shaft.
  • the valve 18 of the raw water passage line 16 is opened, and the raw water containing the substance to be crystallized such as fluorine and phosphorus (hereinafter sometimes simply referred to as “raw water”) is crystallized through the raw water passage line 16.
  • Water is passed through the crystallization reaction section 28 of the crystallization reaction tank 10.
  • the calcium agent is added to the crystallization reaction part 28 through the calcium agent addition line 14.
  • the seed crystal in the seed crystal silo 12 is preferably added to the crystallization reaction unit 28 through the seed crystal addition line 20 by a motor.
  • the crystallization target substances such as fluorine and phosphorus contained in the raw water react with the calcium agent to produce calcium fluoride and calcium phosphate (slightly soluble calcium salt). As a result, it precipitates on the surface of the seed crystal and forms a hardly soluble salt (slightly soluble calcium salt) crystal.
  • Crystals of sparingly soluble calcium salts such as calcium fluoride and calcium phosphate generated in the crystallization reaction unit 28 are periodically pulled out of the sparingly soluble salt discharge line 24 and discharged out of the system, for example.
  • the method of extracting the hardly soluble calcium salt crystal is not particularly limited, but may be a method of drawing the hardly soluble calcium salt crystal from the crystallization reaction tank 10 using a slurry pump such as a tube pump, As shown in FIG. 1, a method may be used in which a valve 24a is attached to the hardly soluble salt discharge line 24 and the crystal of the hardly soluble calcium salt is simply pulled out from the crystallization reaction tank 10 by gravity.
  • the treated water after the crystallization reaction in the crystallization reaction unit 28 flows into the solid-liquid separation unit 30 from the communication port 32. At this time, some of the crystals of the hardly soluble salt flow into the solid-liquid separation unit 30 together with the treated water.
  • the treated water after the crystallization reaction forms an upward flow to form a solid-liquid solution.
  • the hardly soluble salt crystal and the treated water contained in the treated water are solid-liquid separated after passing through the separation unit 30.
  • the treated water subjected to the solid-liquid separation is discharged out of the system through the treated water discharge line 22 as the final treated water of the present embodiment.
  • crystals of the hardly soluble calcium salt in the crystallization reaction part 28 (including the hardly soluble calcium salt crystals that could not be precipitated on the seed crystal surface), Part of seed crystals and the like replenished from the seed crystal silo 12 is stored in the solid-liquid separation unit 30 while flowing into the solid-liquid separation unit 30 together with the treated water after the crystallization reaction.
  • crystals and seed crystals crystals and seed crystals having a particularly small particle diameter are likely to flow to the solid-liquid separation unit 30.
  • the crystallization reaction unit 28 exists in the crystallization reaction unit 28.
  • the surface area per unit weight of the crystal or seed crystal to be kept cannot be kept large, and the recovery rate of the hardly soluble calcium salt crystal is lowered.
  • the raw water is intermittently passed through the crystallization reaction unit 28, that is, the water recovery and the water supply stop are repeated, thereby improving the recovery rate of the hardly soluble calcium salt crystals.
  • raw water is passed through the crystallization reaction unit 28 to obtain a hardly soluble calcium salt crystal.
  • a part of the crystals (including seed crystals) of the poorly soluble calcium salt obtained, particularly the crystals of the poorly soluble calcium salt having a fine particle diameter flow into the solid-liquid separation part 30 as described above, and are separated into solid and liquid. It is stored in the part 30.
  • the flow of the raw water to the crystallization reaction tank 10 is stopped, and crystals of a slightly soluble salt having a fine particle size staying in the solid-liquid separation unit 30 are naturally precipitated, and at least the crystals etc.
  • An operation is performed to return a part of this to the crystallization reaction unit 28. It is preferable to incline the bottom of the individual liquid separating unit 30 downward toward the crystallization reaction unit 28 so that the crystals or the like deposited on the individual liquid separating unit 30 can easily return to the crystallization reaction unit 28.
  • the operation of intermittently passing water was thought to be difficult to operate the apparatus stably while ensuring the recovery rate of hardly soluble salt crystals, but the apparatus configuration of this embodiment
  • the crystal of the slightly soluble calcium salt with a fine particle size is crystallized at the start of the next raw water flow. Since it is held in the part 28, the surface area per unit weight of the hardly soluble calcium salt crystals in the crystallization reaction part 28 is increased without increasing the replenishment amount of the seed crystal from the seed crystal silo 12, resulting in difficulty.
  • the recovery rate of soluble salt crystals can be improved.
  • the flow time and flow stop time of the raw water in the present embodiment are, for example, to ensure the time for generating crystals of sparingly soluble calcium salt and the time for naturally sedimenting the crystals etc. staying in the solid-liquid separation unit 30.
  • the valve 18 of the raw water flow line 16 is opened, and the raw water flow time to the crystallization reaction unit 28 is within a range of 1 ⁇ 2 times to 5 times the residence time in the solid-liquid separation unit 30. Water is passed to the crystallization reaction unit 28. Thereafter, the valve 18 of the raw water flow line 16 is closed, and the water supply stoppage time of the raw water to the crystallization reaction unit 28 is within the range of 1/5 to 1 time of the residence time in the solid-liquid separation unit 30. The flow of raw water to the reaction unit 28 is stopped. As a result, a sufficient time for the crystals of the slightly soluble calcium salt having a small particle size to settle in the crystallization reaction part 28 is secured and retained in the crystallization reaction part 28.
  • the recovery rate can be further improved. Since a larger number of crystals having a fine particle size of 50 ⁇ m or less are mainly retained in the crystallization reaction part 28, the recovery rate of the hardly soluble calcium salt crystals can be further improved. If all the particles in the device are the same size, the surface area per particle increases in proportion to the square of the particle diameter, but the number of particles per unit weight is inversely proportional to the cube of the particle diameter. Become bigger.
  • the residence time in the solid-liquid separation unit 30 is the residence time of the raw water flowing into the crystallization reaction tank 10, and the inflow amount of the raw water flowing into the crystallization reaction tank 10 by the volume of the solid-liquid separation unit 30. It is expressed as a divided value.
  • the valve 18 of the present embodiment may be opened or closed manually or automatically.
  • the flow time of the raw water to the crystallization reaction unit 28 is less than 1 ⁇ 2 times the residence time in the solid-liquid separation unit 30, the water flow time is short, the amount of water that can be treated by the apparatus is reduced, and the hardly soluble calcium salt The efficiency of recovering the crystals may deteriorate. Further, if the flow time of the raw water to the crystallization reaction unit 28 is more than 5 times the residence time in the solid-liquid separation unit 30, a large amount of finely soluble hardly soluble calcium salt crystals and the like are discharged out of the system, Crystals with a fine particle size may not be sufficiently retained in the crystallization reaction unit 28, and it becomes difficult to improve the recovery rate of the hardly soluble calcium salt crystals.
  • fine particles such as those of a replenished seed crystal having a too small particle diameter or crystals of a hardly soluble calcium salt that could not be precipitated on the surface of the seed crystal cannot be separated by the solid-liquid separation unit 30, and are caused by upward flow. It flows out with treated water and is discharged out of the system.
  • the discharged fine particles are disposed of as sludge without being recovered, but if the fine particles can be grown to a particle size capable of solid-liquid separation, the amount of generated sludge can be reduced. It is possible to reduce the replenishment amount of seed crystals.
  • the upper end of the inner peripheral wall 26 that separates the solid-liquid separation unit 30 and the crystallization reaction unit 28 is the same height as the treated water discharge port 21 or A part of the treated water is set at a position lower than the treated water discharge port 21 within a range where the treated water can be discharged from the treated water discharge port 21.
  • the water level of the crystallization reaction unit 28 is the same height as the treated water discharge port 21, if the upper end of the inner peripheral wall 26 is made the same height as the treated water discharge port 21 or lower than that height, Crystals or the like of the hardly soluble calcium salt in the precipitation reaction part 28 will flow over the inner peripheral wall 26 and to the solid-liquid separation part 30 side.
  • the crystallization reaction unit 1 in order to keep the surface area of the crystals in the crystallization reaction unit 28 high, the crystallization reaction unit 1 is operated in a state where the crystal concentration is high. The specific gravity per unit volume tends to be higher than the specific gravity of the fluid in the solid-liquid separation unit 30.
  • a water level difference occurs between the crystallization reaction unit 28 and the solid-liquid separation unit 30.
  • This water level difference may be a water level difference of several meters depending on the size of the apparatus. Therefore, as in this embodiment, even if the position of the upper end of the inner peripheral wall 26 is lowered as described above, the raw water in the crystallization reaction unit 28 does not flow over to the solid-liquid separation unit 30, and the solid-liquid separation is performed. A part of the treated water in the part 30 can be returned to the crystallization reaction part 28.
  • the addition (injection point) of the calcium agent and raw water to the crystallization reaction unit 28 is preferably performed in the vicinity of the stirring blade 38.
  • the calcium agent and the raw water are immediately diffused when injected into the crystallization reaction unit 28, and the crystallization target substances such as the calcium agent concentration, fluorine, phosphorus, etc. Concentration drops quickly.
  • the formed hardly soluble salt is less likely to be directly deposited in the liquid, and the crystallization target substance (fluorine, phosphorus, etc.) in the liquid as the hardly soluble salt crystal on the seed crystal in the crystallization reaction unit 28. Can be captured carefully.
  • the draft tube 36 it is preferable to install the draft tube 36 so that the stirring blade 38 of the stirring device 34 is located in the cylinder. At this time, the stirring blade 38 preferably forms a downward flow.
  • the draft tube 36 is thus installed, a downward flow is generated toward the lower portion of the tube, and a zone having a relatively large diffusion flow rate is formed. For this reason, raw
  • an upward flow zone with a gentle flow is formed on the outer periphery of the tube.
  • the particles are classified and small particles rise along the outer surface of the tube, and re-enter from the upper end of the tube to the inside of the tube. Recirculate to the stirring zone. Since these small-sized crystals serve as nuclei to promote the crystallization reaction, the recovery rate of the hardly soluble salt crystals can be improved.
  • the crystal having a larger particle size due to the progress of the crystallization reaction does not rise due to the upward flow at the outer periphery of the tube, sinks down and does not enter the draft tube 36 again. Since it can prevent being destroyed by the collision with the blade 38, it can contribute to the improvement of the recovery rate of the hardly soluble salt crystal.
  • acid or alkali is added to the crystallization reaction unit 28 so that the pH of the crystallization reaction solution in the crystallization reaction unit 28 is in the range of 0.8 to 3. It is more preferable to set the range.
  • the raw water containing crystallization target substances such as fluorine and phosphorus in the present embodiment may be raw water of any origin as long as it contains fluorine, phosphorus and the like removed by crystallization treatment, for example, semiconductor related industries.
  • Fluorine, phosphorus, etc. which are crystallization target substances, can be present in the raw water in any state as long as they are crystallized by a crystallization reaction. From the viewpoint that it is dissolved in the raw water, the crystallization target substance is preferably in an ionized state.
  • the calcium agent used in the present embodiment for example, calcium chloride, calcium hydroxide and the like are used.
  • a powder state may be sufficient and a slurry state may be sufficient.
  • the injection amount of the calcium agent is preferably 0.8 to 2 times and 1 to 2 times that of fluorine and phosphorus as the chemical equivalent of calcium, but more preferably 1 to 1.2 times.
  • the chemical equivalent of calcium is more than twice the chemical equivalent of fluorine and phosphorus in the raw water, calcium fluoride and calcium phosphate are not easily deposited on the seed crystal and are easily formed as fine particles, and calcium fluoride and calcium phosphate are mixed into the treated water. If the ratio is less than 0.8 times, the proportion of fluorine and phosphorus in raw water that does not become calcium fluoride and calcium phosphate increases, and fluorine and phosphorus may be mixed into the treated water.
  • seed crystals may exist in advance in the crystallization reaction unit 28, or in the crystallization reaction unit 28 in advance. There may be no seed crystals. In order to perform a stable treatment, it is preferable that a seed crystal is present in the crystallization reaction unit 28 in advance.
  • the seed crystal may be any material as long as it can precipitate a hardly soluble calcium salt crystal formed on the surface thereof, and any material can be selected, for example, filtered sand, activated carbon, zircon sand, garnet sand, It is composed of particles containing oxides of metal elements such as Sac Random (trade name, manufactured by Nihon Cartrit Co., Ltd.) and hardly soluble calcium salts that are precipitates by crystallization reaction.
  • Sac Random trade name, manufactured by Nihon Cartrit Co., Ltd.
  • particles composed of the hardly soluble salt which is a precipitate by a crystallization reaction are preferable.
  • the particles comprising a hardly soluble calcium salt that is a precipitate by crystallization reaction include fluorite when depositing calcium fluoride, and phosphate ore when depositing calcium phosphate. Is mentioned.
  • the flow rate of the raw water flowing to the crystallization reaction unit 28 is preferably in the range of residence time 1 to 4 hours, and more preferably 2 to 4 hours.
  • the flow rate (LV) of the treated water flowing through the solid-liquid separation unit 30 is preferably in the range of 0.1 to 2.0 m / h, preferably 0.2 to 1.0 m / h, from the viewpoint of satisfactory solid-liquid separation. A range is more preferred.
  • FIG. 2 is a schematic diagram showing an example of the configuration of a crystallization reaction apparatus of a reference example.
  • a crystallization reaction apparatus 100 shown in FIG. 2 includes a crystallization reaction tank 110, a seed crystal silo 112, a calcium agent addition line 114 as an example of addition means for adding a calcium agent to the crystallization reaction tank 110, and a crystallization reaction of raw water.
  • a raw water flow line 116, a seed crystal addition line 118, a treated water discharge line 120, and a hardly soluble salt discharge line 122 are provided as an example of an inflow means for flowing into the tank 110.
  • the crystallization reaction tank 110 is connected to a raw water passage line 116 from a raw water storage tank (not shown) and a calcium agent addition line 114 from a calcium agent storage tank (not shown).
  • a seed crystal addition line 118 is connected between the seed crystal silo 112 and the crystallization reaction tank 110.
  • a treated water discharge line 120 is connected to the treated water discharge port 111 of the crystallization reaction tank 110, and a hardly soluble salt discharge line 122 is connected to the hardly soluble salt discharge port of the crystallization reaction tank 110. .
  • a crystallization reaction part 126 for generating a hardly soluble salt crystal and a solid / liquid separation part 128 for performing a solid / liquid separation between the hardly soluble salt crystal and the treated water.
  • an inner peripheral wall 124 facing the outer peripheral wall of the crystallization reaction tank 110 is provided, and a space between the outer peripheral wall and the inner peripheral wall 124 serves as a solid-liquid separation unit 128.
  • the inner peripheral wall 124 of this embodiment is provided in a predetermined section of the outer peripheral wall of the crystallization reaction tank 110, the inner peripheral wall 124 may be provided over the entire periphery of the outer peripheral wall.
  • the crystallization reaction unit 126 and the solid-liquid separation unit 128 are partitioned by an inner peripheral wall 124, and a communication port 130 through which the crystallization reaction unit 126 and the solid-liquid separation unit 128 communicate with each other is formed below the inner peripheral wall 124.
  • a communication port 130 through which the crystallization reaction unit 126 and the solid-liquid separation unit 128 communicate with each other is formed below the inner peripheral wall 124.
  • the treated water discharge port 111 described above is provided on the outer peripheral wall of the crystallization reaction tank 110 where the solid-liquid separation unit 128 is formed, and the treated water discharge line 120 is connected to the treated water discharge port 111. ing.
  • the upper end of the inner peripheral wall 124 that separates the solid-liquid separation unit 128 and the crystallization reaction unit 126 is the same height as the treated water discharge port 111 or a range in which a part of the treated water can be discharged from the treated water discharge port 111. Is set to a position lower than the treated water discharge port 111.
  • the crystallization reaction section 126 of the crystallization reaction tank 110 includes a draft tube 134 and a stirring device 132 as an example of a stirring means for stirring the fluid in the crystallization reaction section 126.
  • the stirring device 132 includes a stirring blade 136.
  • the stirring blade 136 is disposed in the draft tube 134 and is rotated by a rotational force generated by a motor transmitted through the stirring shaft.
  • raw water containing a target substance for crystallization of fluorine and phosphorus (hereinafter sometimes simply referred to as “raw water”) is passed through the raw water flow line 116 to the crystallization reaction unit 126.
  • the calcium agent is added to the crystallization reaction part 126 through the calcium agent addition line 114.
  • the seed crystal in the seed crystal silo 112 is added to the crystallization reaction unit 126 through the seed crystal addition line 118 by the motor.
  • the fluorine and phosphorus crystallization target substances contained in the raw water react with the calcium agent to produce calcium fluoride and calcium phosphate (slightly soluble calcium salt).
  • the calcium agent to produce calcium fluoride and calcium phosphate (slightly soluble calcium salt).
  • the crystals of the poorly soluble calcium salt of calcium fluoride and calcium phosphate generated in the crystallization reaction unit 126 are, for example, periodically pulled out from the hardly soluble salt discharge line 122 and discharged out of the system.
  • the method of extracting the hardly soluble calcium salt crystal is not particularly limited, but may be a method of extracting the hardly soluble calcium salt crystal from the crystallization reaction tank 110 using a slurry pump such as a tube pump, As shown in FIG. 1, a method may be used in which a valve 122a is attached to the hardly soluble salt discharge line 122 and the crystal of the hardly soluble calcium salt is simply extracted from the crystallization reaction tank 110 by gravity.
  • the treated water after the crystallization reaction in the crystallization reaction unit 126 flows into the solid-liquid separation unit 128 from the communication port 130. At this time, a part of the crystals of the hardly soluble salt flows into the solid-liquid separation unit 128 together with the treated water.
  • the treated water after the crystallization reaction forms an upward flow to form a solid-liquid liquid.
  • the hardly soluble salt crystal and the treated water contained in the treated water are separated into solid and liquid.
  • the treated water subjected to the solid-liquid separation is discharged out of the system through the treated water discharge line 120 as the final treated water of the present embodiment.
  • fine particles such as those of a replenished seed crystal having a too small particle diameter or crystals of a hardly soluble calcium salt that could not be precipitated on the seed crystal surface could not be separated by the solid-liquid separation unit 128, It flows out with treated water and is discharged out of the system.
  • the discharged fine particles are disposed of as sludge without being recovered, but if the fine particles can be grown to a particle size capable of solid-liquid separation, the amount of generated sludge can be reduced. It is possible to reduce the replenishment amount of seed crystals.
  • the upper end of the inner peripheral wall 124 that separates the solid-liquid separation unit 128 and the crystallization reaction unit 126 is the same height as the treated water discharge port 111, or A part of the treated water is set at a position lower than the treated water discharge port 111 within a range where the treated water can be discharged from the treated water discharge port 111.
  • the water level of the crystallization reaction part 126 is the same height as the treated water discharge port 111, if the upper end of the inner peripheral wall 124 is made the same height as the treated water discharge port 111 or lower than that height, Crystals or the like of the hardly soluble calcium salt in the precipitation reaction portion 126 will flow over the inner peripheral wall 124 to the solid-liquid separation portion 128 side.
  • the specific gravity per unit volume of the fluid in the crystallization reaction unit 126 tends to be higher than the specific gravity of the fluid in the solid-liquid separation unit 128.
  • the weight per liter of raw water containing the crystals in the crystallization reaction part 126 can be 2.0 kg / L.
  • the specific gravity in the solid-liquid separator 128 is at most about 1.0 kg / L to 1.2 kg / L.
  • the raw material water containing the crystallization target substance in the present embodiment contains fluorine and phosphorus that are removed by the crystallization treatment.
  • raw water of any origin may be used as long as it contains fluorine and phosphorus, for example, raw water discharged from the electronics industry including the semiconductor-related industry, the power plant, the aluminum industry, It is not limited to these.
  • Fluorine and phosphorus as crystallization target substances can be present in the raw water in any state as long as they are crystallized by a crystallization reaction. From the viewpoint of dissolving in raw water, fluorine and phosphorus are preferably in an ionized state.
  • the addition (injection point) of the calcium agent and raw water to the crystallization reaction unit 126 is preferably performed in the vicinity of the stirring blade 136.
  • the calcium agent and the raw water are immediately diffused when injected into the crystallization reaction unit 126, and the calcium agent concentration, the fluorine concentration, and the phosphorus concentration are quickly lowered.
  • the formed hardly soluble salt is less likely to be directly deposited in the liquid, and fluorine and phosphorus in the liquid can be taken in well as the hardly soluble salt crystal on the seed crystal in the crystallization reaction unit 126.
  • the draft tube 134 it is preferable to install the draft tube 134 so that the stirring blade 136 of the stirring device 132 is positioned in the cylinder. At this time, the stirring blade 136 preferably forms a downward flow.
  • the draft tube 134 is thus installed, a downward flow is generated toward the lower portion of the tube, and a zone having a relatively large diffusion flow rate is formed. For this reason, raw
  • an upward flow zone with a gentle flow is formed on the outer periphery of the tube.
  • the particles are classified and small particles rise along the outer surface of the tube, and re-enter from the upper end of the tube to the inside of the tube. Recirculate to the stirring zone. Since these small-sized crystals serve as nuclei to promote the crystallization reaction, the recovery rate of the hardly soluble salt crystals can be improved.
  • the crystals whose particle size has increased due to the progress of the crystallization reaction does not rise due to the upward flow at the outer periphery of the tube, sinks down and does not enter the draft tube 134 again. Since it can be prevented from being destroyed by the collision with the blade 136, it can contribute to the improvement of the recovery rate of the hardly soluble salt crystal.
  • acid or alkali is added to the crystallization reaction tank 110, and the pH of the crystallization reaction solution in the crystallization reaction unit 126 is preferably in the range of 0.8 to 3, preferably 1 to 1.5. It is more preferable to set the range.
  • the concentration of the crystallization target substance of fluorine and phosphorus in the treated water can be reduced.
  • the calcium agent used in the present embodiment for example, calcium chloride, calcium hydroxide and the like are used.
  • a powder state may be sufficient and a slurry state may be sufficient.
  • the injection amount of the calcium agent is preferably 0.8 to 2 times and 1 to 2 times that of fluorine and phosphorus as the chemical equivalent of calcium, but more preferably 1 to 1.2 times.
  • the chemical equivalent of calcium is more than twice the chemical equivalent of fluorine and phosphorus in the raw water, calcium fluoride and calcium phosphate are not easily deposited on the seed crystal and are easily formed as fine particles, and calcium fluoride and calcium phosphate are mixed into the treated water. If the ratio is less than 0.8 times, the proportion of fluorine and phosphorus in raw water that does not become calcium fluoride and calcium phosphate increases, and fluorine and phosphorus may be mixed into the treated water.
  • seed crystals may exist in advance in the crystallization reaction unit 126, or in the crystallization reaction unit 126 in advance. There may be no seed crystals. In order to perform a stable process, it is preferable that a seed crystal is present in the crystallization reaction unit 126 in advance.
  • the seed crystal may be any material as long as it can precipitate a hardly soluble calcium salt crystal formed on the surface thereof, and any material can be selected, for example, filtered sand, activated carbon, zircon sand, garnet sand, It is composed of particles composed of oxides of metal elements such as sacrandom (trade name, manufactured by Nihon Cartrit Co., Ltd.) and the like, and hardly soluble salts that are precipitates by crystallization reaction. Examples thereof include, but are not limited to, particles. From the viewpoint that a purer hardly soluble salt can be obtained as a pellet or the like, particles composed of the hardly soluble salt which is a precipitate by a crystallization reaction are preferable. Examples of the particles composed of a hardly soluble salt that is a precipitate by a crystallization reaction include fluorite when depositing calcium fluoride, and when depositing calcium phosphate, for example, phosphate ore. Etc.
  • Example 1 In Example 1, the crystallization reaction apparatus shown in FIG. 1 was used, and calcium fluoride was recovered from the fluorine-containing raw water under the following conditions.
  • Crystallization reaction part size 130 L (440 mm ⁇ ⁇ 880 mmH)
  • Solid-liquid separation part size 230L (440 ⁇ 590 ⁇ 880mmH)
  • Fluorine-containing raw water flow rate 50 L / h
  • Fluorine concentration of raw water containing fluorine 10000 mg / L
  • Calcium agent A solution in which 10% slurry of slaked lime is dissolved in hydrochloric acid.
  • PH in the crystallization reaction part pH 2 (adjusted by adding NaOH)
  • Initially filled seed crystals in the crystallization reaction section 20 kg (without replenishment of seed crystals thereafter)
  • Slurry concentration in the crystallization reaction section 30 to 35 v / v% (appropriately withdrawn from the hardly soluble salt discharge pipe)
  • the residence time of the solid-liquid separation part of Example 1 was 4.6 h (230 (L) / 50 (L / h)), and the residence time of the crystallization reaction part was 2.6 h.
  • Example 1 the raw water was passed through the crystallization reaction section for 9.2 hours, and then the water flow was stopped for 2.3 hours. This water flow and water flow stop were repeated until the water flow time reached 400 hours.
  • the flow rate (LV) of the treated water in the solid-liquid separation part during water flow was 0.2 m / h. The test was conducted in such a manner that a part of the treated water in the solid-liquid separation part was not returned to the crystallization reaction part.
  • Example 2 In Example 2, the test was performed under the same conditions as in Example 1 except that the raw water was passed through the crystallization reaction section for 4.6 hours and then stopped for 1.15 hours.
  • Example 3 In Example 3, the test was performed under the same conditions as in Example 1 except that the raw water was passed through the crystallization reaction section for 4.6 hours and then the water supply was stopped for 2.3 hours.
  • Example 4 In Example 4, a crystallization reaction apparatus in which the solid-liquid separation part size was changed to 23 L (440 ⁇ 60 ⁇ 880 mmH) was used. In Example 4, the raw water was passed through the crystallization reaction section for 0.46 hours and then stopped for 0.23 hours. This water flow and water flow stop were repeated until the water flow time reached 400 hours. In addition, the flow rate (LV) of the treated water of the solid-liquid separation part at the time of water flow was 2.0 m / h.
  • Example 5 In Example 5, the test was performed under the same conditions as in Example 1 except that the raw water was passed through the crystallization reaction part for 18.4 hours and then stopped for 2.3 hours.
  • Comparative Example 1 In Comparative Example 1, the test was performed under the same conditions as in Example 1 except that the raw water was not stopped and the raw water was passed through the crystallization reaction part for 400 hours.
  • the flow rate (LV) of the treated water in the solid-liquid separation part during water flow was 0.2 m / h.
  • Comparative Example 2 In Comparative Example 2, using the crystallization reaction apparatus whose solid-liquid separation part size was changed to 23 L (440 ⁇ 60 ⁇ 880 mmH), the raw water was passed through the crystallization reaction part for 400 hours without stopping the flow of the raw water. The test was performed under the same conditions as in Example 1 except that. The flow rate (LV) of the treated water in the solid-liquid separation part during water flow was 2.0 m / h.
  • Table 1 shows the flow rate of treated water in the solid-liquid separation parts of Examples 1 to 5 and Comparative Examples 1 and 2, the time for passing raw water to the crystallization reaction part, the time for stopping water flow, and after 400 hours for water flow.
  • the recovery rates of calcium fluoride were summarized.
  • Example 6 In Example 6, in the crystallization reaction apparatus shown in FIG. 1, a part of the treated water in the solid-liquid separation unit was obtained using a crystallization reaction apparatus in which the upper end of the inner peripheral wall was set to the same height as the treated water discharge port. The test was performed under the same conditions as in Example 1 except that the sample was returned to the crystallization reaction part.
  • Example 7 In Example 7, the test was performed under the same conditions as in Example 6 except that the raw water was passed through the crystallization reaction section for 4.6 hours and then stopped for 2.3 hours.
  • Comparative Example 3 In Comparative Example 3, in the crystallization reaction apparatus shown in FIG. 2, using the crystallization reaction apparatus in which the upper end of the inner peripheral wall is set to the same height as the treated water discharge port, the raw water is not stopped without passing the raw water. The test was performed under the same conditions as in Example 5 except that water was passed through the crystallization reaction section for 400 hours.
  • Table 2 shows the flow rate of treated water in the solid-liquid separation sections of Examples 6 to 7 and Comparative Example 3, the flow time of raw water to the crystallization reaction section, the stop time of water flow, and the flow after 400 hours of water flow.
  • the recovery rate of calcium fluoride was summarized.
  • FIG. 3 is a diagram showing the particle size distribution of crystals in the crystallization reaction part of Example 1
  • FIG. 4 is a diagram showing the particle size distribution of crystals in the crystallization reaction part of Example 2
  • FIG. These are diagrams showing the particle size distribution of crystals in the crystallization reaction part of Example 3
  • FIG. 6 is a diagram showing the particle size distribution of crystals in the crystallization reaction part of Example 4
  • FIG. 8 is a diagram showing the particle size distribution of crystals in the crystallization reaction part of Comparative Example 1
  • FIG. 8 is a diagram showing the particle size distribution of crystals in the crystallization reaction part of Comparative Example 2
  • FIG. 9 is a comparative example.
  • FIG. 3 is a diagram showing a particle size distribution of crystals in a crystallization reaction part of 3.
  • the particle size distribution of the crystals in the crystallization reaction part was measured using a particle size distribution meter (LS230 manufactured by Beckman Coulter, Inc.) after 400 hours of water flow.
  • Comparative Example 1 in which calcium fluoride was recovered by continuous flow of raw water without replenishing seed crystals, as can be seen from the results of FIG. 7 and Table 1, crystals having a particle size of 100 ⁇ m or more were formed in the crystallization reaction part. Many were present and the recovery rate was as low as 65%. Furthermore, in Comparative Example 2 in which the flow rate of the treated water in the solid-liquid separation part was increased to 2.0 m / h, as can be seen from the results of FIG. 8 and Table 1, crystals having a particle size of 125 ⁇ m or more were formed in the crystallization reaction part. There were many, and the recovery rate was further reduced to 50%.
  • Example 3 in which the raw water was passed for one time the residence time of the solid-liquid separation unit, and the water passage was stopped for half the residence time of the solid-liquid separation unit.
  • Example 4 where the residence time of the solid-liquid separation unit was 1 time, and the water flow was stopped for 1/2 time of the residence time of the solid-liquid separation unit, the results shown in FIGS.
  • crystals having a particle size of 50 ⁇ m or less are present in the crystallization reaction part, and the recovery rate is 90% or higher, which is higher than in Examples 1 and 2. That is, the raw water is passed through for a time that is one time the residence time of the solid-liquid separation part, and the water passage is stopped for a time that is one-half the residence time of the solid-liquid separation part. It was found that it could be retained in the crystallization reaction part, and the recovery rate of calcium fluoride crystals was further improved.
  • 1,100 crystallization reaction apparatus 10,110 crystallization reaction tank, 12,112 seed silo, 14,114 calcium agent addition line, 16,116 raw water passage line, 18, 24a, 122a valve, 20,118 seeds Crystal addition line, 21,111 treated water discharge port, 22,120 treated water discharge line, 24,122 sparingly soluble salt discharge line, 26,124 inner wall, 28,126 crystallization reaction section, 30,128 solid-liquid separation section 32, 130 communication port, 34, 132 stirring device, 36, 134 draft tube, 38, 136 stirring blade.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

　L'invention concerne l'utilisation d'un réacteur de cristallisation équipé d'une cuve (10) réactionnelle de cristallisation qui possède une unité (28) réactionnelle de cristallisation permettant d'ajouter une préparation de calcium à de l'eau brute contenant une substance à cristalliser et de générer des cristaux d'un sel faiblement soluble. Une paroi périphérique interne (26) faisant face à une paroi périphérique externe de la cuve (10) réactionnelle de cristallisation est disposée dans la cuve (10) réactionnelle de cristallisation. Un séparateur (30) solide-liquide, qui forme un écoulement ascendant entre les parois périphériques interne et externe et qui effectue la séparation solide-liquide sur les cristaux et l'eau traitée, est fourni dans la cuve (10) réactionnelle de cristallisation. Une valve (18) fournie au niveau d'une conduite (16) de passage d'eau brute est ouverte afin que la durée de passage de l'eau brute dans la cuve (10) réactionnelle de cristallisation soit égale à la moitié et jusqu'à cinq fois la durée de rétention dans le séparateur (30) solide-liquide. Après le passage de l'eau brute, la valve (18) fournie au niveau de la conduite (16) de passage d'eau brute est fermée de sorte que la durée pendant laquelle est arrêté le passage de l'eau brute dans la cuve (10) réactionnelle de cristallisation soit égale à un cinquième et jusqu'à une fois la durée de rétention dans le séparateur (30) solide-liquide.
PCT/JP2013/067526 2013-06-26 2013-06-26 Réacteur de cristallisation WO2014207837A1 (fr)

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CN201380077825.7A CN105339063B (zh) 2013-06-26 2013-06-26 析晶反应装置
SG11201509658PA SG11201509658PA (en) 2013-06-26 2013-06-26 Crystallization reactor
PCT/JP2013/067526 WO2014207837A1 (fr) 2013-06-26 2013-06-26 Réacteur de cristallisation
KR1020157033811A KR101793809B1 (ko) 2013-06-26 2013-06-26 정석 반응장치

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61141996A (ja) * 1984-12-17 1986-06-28 Ataka Kogyo Kk 排水の処理方法
JP2001038370A (ja) * 1999-08-03 2001-02-13 Maezawa Ind Inc 排水処理装置
JP2002292204A (ja) * 2001-03-30 2002-10-08 Japan Organo Co Ltd 原水供給制御手段を備えた晶析反応装置および該装置を用いた晶析処理方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4842450B2 (ja) * 2001-03-30 2011-12-21 オルガノ株式会社 濁度測定手段を備えた晶析反応装置および該装置を用いた晶析処理方法
JP4072091B2 (ja) * 2003-04-25 2008-04-02 アタカ大機株式会社 リン資源回収方法
JP4316393B2 (ja) * 2004-01-21 2009-08-19 森田化学工業株式会社 フッ化カルシウムの製造方法と再利用法ならびにそのリサイクル方法
JP5414169B2 (ja) * 2007-11-15 2014-02-12 オルガノ株式会社 晶析反応装置及び晶析反応方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61141996A (ja) * 1984-12-17 1986-06-28 Ataka Kogyo Kk 排水の処理方法
JP2001038370A (ja) * 1999-08-03 2001-02-13 Maezawa Ind Inc 排水処理装置
JP2002292204A (ja) * 2001-03-30 2002-10-08 Japan Organo Co Ltd 原水供給制御手段を備えた晶析反応装置および該装置を用いた晶析処理方法

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CN105339063A (zh) 2016-02-17
KR101793809B1 (ko) 2017-11-03
KR20160004361A (ko) 2016-01-12
CN105339063B (zh) 2017-03-08

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