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WO2002004351A1 - Procede de granulation d'hydrate de chlorure de calcium et appareil de granulation - Google Patents

Procede de granulation d'hydrate de chlorure de calcium et appareil de granulation Download PDF

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Publication number
WO2002004351A1
WO2002004351A1 PCT/JP2000/004512 JP0004512W WO0204351A1 WO 2002004351 A1 WO2002004351 A1 WO 2002004351A1 JP 0004512 W JP0004512 W JP 0004512W WO 0204351 A1 WO0204351 A1 WO 0204351A1
Authority
WO
WIPO (PCT)
Prior art keywords
calcium chloride
fluidized bed
particles
aqueous solution
chloride hydrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2000/004512
Other languages
English (en)
Japanese (ja)
Inventor
Mitsuhiro Nishimoto
Kazuhito Nishimoto
Takashi Ichimura
Zenji Kato
Masayasu Ito
Satoshi Suwa
Nobuo Sekido
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AITECH Co Ltd
Tsukishima Kikai Co Ltd
Kaisei Kogyo KK
Original Assignee
AITECH Co Ltd
Tsukishima Kikai Co Ltd
Kaisei Kogyo KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP00701099A priority Critical patent/JP4298032B2/ja
Application filed by AITECH Co Ltd, Tsukishima Kikai Co Ltd, Kaisei Kogyo KK filed Critical AITECH Co Ltd
Priority to CNB008197253A priority patent/CN1297481C/zh
Priority to PCT/JP2000/004512 priority patent/WO2002004351A1/fr
Priority to AU2000258492A priority patent/AU2000258492A1/en
Publication of WO2002004351A1 publication Critical patent/WO2002004351A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/20—Halides
    • C01F11/24—Chlorides
    • C01F11/30—Concentrating; Dehydrating; Preventing the adsorption of moisture or caking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/16—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by suspending the powder material in a gas, e.g. in fluidised beds or as a falling curtain
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/20—Halides
    • C01F11/24—Chlorides

Definitions

  • the present invention relates to a method and an apparatus for granulating calcium chloride hydrate, which form granules of calcium chloride hydrate by a fluidized bed.
  • a calcium chloride aqueous solution is introduced into a flake force to produce a flake-like granulated product, or a rotating disk or the like is used to generate granules in the air.
  • a method of generating granular granules by solidifying by scattering into particles has been used.
  • the shape of the granulated material is limited to a flake shape, whereas when the granulated material is scattered in the air, the granulated material is granulated.
  • the shape of the particles was greatly distorted and the particle size distribution was extremely large, and a large space was required to solidify the scattered calcium chloride aqueous solution.
  • the aqueous calcium chloride solution must be heated to about 180 ° C or higher in advance.
  • the present invention has been made under such a background, and it is not necessary to heat an aqueous solution of calcium chloride to a high concentration by heating it at a high temperature, and it is possible to produce granules having a predetermined number of water molecules. It is an object of the present invention to provide a method and an apparatus for granulating calcium hydrate. Disclosure of the invention
  • the inventors of the present invention indicate that the vapor pressure of these calcium chloride hydrates in the fluidized bed is determined based on a predetermined vapor pressure diagram corresponding to the number of water molecules.
  • the vapor pressure becomes a predetermined value with respect to the temperature.
  • the granulation method of the present invention has been made based on such knowledge, and thus a calcium chloride hydrate that forms granules by spraying an aqueous calcium chloride solution while fluidizing seed particles in a fluidized bed.
  • the sprayed calcium chloride aqueous solution adheres to the seed particles flowing in the fluidized bed and granulates, the dilute aqueous solution is formed. It is possible to produce a granulated product by using this method, and even if the temperature in the fluidized bed is relatively low, by adjusting the partial pressure of steam in the fluidized bed, this temperature can be adjusted to this temperature in the vapor pressure diagram.
  • the vapor pressure of calcium chloride can be set to a corresponding appropriate vapor pressure, and it is possible to granulate calcium chloride hydrate having a predetermined number of water molecules.
  • the above-mentioned seed particles are sprayed, such as particles of hydrated calcium chloride dihydrate, calcium chloride monohydrate, anhydrous calcium chloride, or a mixture thereof, in which the number of water molecules to be hydrated is 2 to 0.
  • Particles such as thorium and magnesium chloride may be used as seed particles.
  • the partial pressure of steam in the fluidized bed it is possible to adjust the moisture content of the fluidizing gas supplied to the fluidized bed.
  • at least the temperature in the fluidized bed and the exhaust humidity from the fluidized bed are measured. It is desirable to control the partial pressure.
  • the granulation method using the above-mentioned flaker and the method of scattering into the air can only produce granules having a specific shape, respectively.
  • calcium chloride is used.
  • the spray height at which the aqueous solution is sprayed it is possible to generate granules having a predetermined shape. That is, according to the results obtained from various experiments, the spray height is set relatively high (for example, 300 mm or more) with respect to the height of the fluidized bed in the stationary bed.
  • the aqueous calcium chloride solution becomes droplets and adheres to the surface of the seed particles, resulting in the formation of granules containing confetti-shaped particles.
  • the spray height is set to a relatively low value (for example, less than 300 MI, preferably less than 280 bandages), the aqueous solution of calcium chloride uniformly adheres to the surface of the seed particles, so that round particles are formed. Can be produced.
  • a granulated product having a predetermined shape can be generated in this manner.
  • the above water vapor partial pressure is made sufficiently lower than the calcium chloride vapor pressure, as in the case where the spray height is increased, the particles in the shape of confetti are increased, and conversely, the water vapor partial pressure is reduced to the calcium chloride vapor pressure. If it approaches, the number of round particles increases.
  • the calcium chloride aqueous solution produced in the fluidized bed is generally used. It is desirable that the granules of the Japanese product be separated into coarse particles having a particle size larger than the above range, medium particles having a particle size within the above range, and fine particles having a small particle size.In this case, the coarse particles crush the particles. And at least with fine particles It is efficient to circulate through the fluidized bed to make new seed particles.
  • the circulation ratio of the generated calcium chloride hydrate is 1.5. It is desirable to set the value in the range of ⁇ 10.If the circulation ratio exceeds the above range, the number of circulating particles increases and the number of medium particles separated as a product decreases, while the circulation ratio falls below the above range. This may lead to a shortage of seed particles supplied to the fluidized bed.
  • the present invention can be applied to shape spines, round particles, or the like without circulating the particles.
  • the granulation apparatus of calcium chloride hydrate of the present invention performs granulation of calcium chloride hydrate by the above granulation method more reliably, that is, while the seed particles are fluidized in the fluidized bed.
  • An apparatus for granulating calcium chloride hydrate for producing granulated material by spraying an aqueous solution of calcium chloride comprising: a temperature sensor for measuring a temperature in the fluidized bed; A humidity sensor for measuring the exhaust humidity of the gas, and by adjusting the partial pressure of water vapor in the fluidized bed by control based on at least the measurement results of the temperature sensor and the humidity sensor, the vapor pressure of calcium chloride in the fluidized bed. Is set to the vapor pressure of calcium chloride hydrate having a predetermined number of water molecules with respect to the temperature in the fluidized bed.
  • the moisture adjusting device when adjusting the partial pressure of water vapor in the fluidized bed in this way, one of the above-mentioned fluidized beds is provided with a moisture adjusting device for adjusting the moisture amount of the fluidizing gas supplied to the fluidized bed.
  • the moisture adjusting device includes a flow rate sensor for measuring the amount of moisture given to the fluidizing gas, a temperature sensor and a humidity sensor for measuring the temperature and humidity of the moisture-regulated flowing gas, It is possible to adjust the water content of the flowing gas by controlling at least based on the measurement results of the flow rate sensor, temperature sensor, and humidity sensor and the measurement results of the temperature sensor and humidity sensor provided in the fluidized bed. It is.
  • the fluidized bed is provided with a concentration adjusting device for adjusting the concentration of the calcium chloride aqueous solution supplied to the fluidized bed in accordance with this or alone, and the concentration adjusting device is provided with a concentration-adjusted device.
  • Calcium chloride aqueous solution A concentration sensor and a flow rate sensor for measuring the concentration and the flow rate of the liquid, and the control is performed based on at least the measurement results of the concentration sensor and the flow rate sensor and the measurement results of the temperature sensor and the humidity sensor provided in the fluidized bed. It is also possible to adjust the concentration of the calcium aqueous solution.
  • the aqueous solution of calcium chloride sprayed on the fluidized bed in this granulator depends on the concentration and temperature, and when the granulation in the fluidized bed is temporarily stopped or the granulation operation is completed, If it stays in the pipes inside it, it tends to be clogged and clogged easily, and when consolidation occurs, the portion clogged by this consolidation must be melted the next time granulation work is resumed. Therefore, it is desirable to provide a caking preventing means so that caking of the calcium chloride aqueous solution does not occur even when such granulation is stopped.
  • consolidation preventing means when the calcium chloride aqueous solution is adjusted to a predetermined concentration in a tank and supplied from the tank to the fluidized bed through a supply pipe and sprayed, consolidation occurs in the supply pipe.
  • a return pipe for returning the aqueous solution of calcium chloride in the supply pipe to the tank can be connected to this supply pipe, and granulation was stopped.
  • the calcium chloride aqueous solution in the supply pipe may be returned to the tank via the return pipe so that the calcium chloride aqueous solution does not remain in the supply pipe.
  • the calcium chloride aqueous solution may solidify in the above-mentioned tank, but after such a granulation operation is completed. It is not economical, for example, to keep the entire amount of the aqueous solution of calcium chloride held in this tank heated until the end of the granulation operation in order to prevent caking of the powder.
  • the granulating apparatus is usually provided with a scrubber for washing the exhaust gas discharged from the fluidized bed with washing water and recovering the calcium chloride component in the exhaust gas.
  • the above-mentioned tank can be connected to this scrubber as the above-mentioned caking prevention means. It is desirable that the aqueous solution of calcium chloride in the tank can be supplied to the scrubber so that it can be held.
  • the aqueous calcium chloride solution may be returned from the scrubber to the tank and sprayed on the fluidized bed.
  • a seed hopper for supplying seed particles to the fluidized bed is connected to the fluidized bed, and the seed particles are supplied from the seed hopper when granulation is performed for the first time such as when the granulation operation is restarted.
  • the seed hopper is selectively used. If it is possible to supply the granulated material to the seed hopper before the end of the granulation work, for example, the granulated material can be supplied and stored in the seed hopper, and then supplied to the fluidized bed as seed particles when the next granulation work is restarted.
  • a granulated product having a large particle size among the granulated calcium chloride hydrates may be required as a product, and thus the chloride formed in the fluidized bed may be added to the fluidized bed.
  • a vibrating sieve device that separates the granulated calcium hydrate into coarse, medium, and fine particles is connected, and at least a portion of the coarse particles can be selectively discharged as product granules. It is desirable to do so.
  • the washing water for cleaning the exhaust gas can be circulated to the scrubber, and at least a part thereof is supplied to the fluidized bed side. It is desirable that the scrubber can concentrate and supply the aqueous solution of calcium chloride to the fluidized bed side and spray it in the scrubber, so that it is easy to adjust the concentration in the above tank during the granulation operation. On the other hand, for example, even when the aqueous solution of calcium chloride is concentrated before resuming the granulation operation, the scrubber, instead of the above-mentioned tank, uses the high-temperature exhaust gas discharged by drying and raising the temperature of the fluidized bed.
  • the aqueous solution can be concentrated in advance, and the concentrated aqueous solution of calcium chloride can be stored in a tank or a moving bed. Since it is possible to directly supply, it is possible to shorten the concentration time.
  • the scrubber is a spray type scrubber in which exhaust gas discharged from the fluidized bed is introduced into a washing tower and washed with washing water sprayed into the washing tower, so that a gas flow rate to be treated is reduced. Exhaust blower with reduced pressure loss Power can be reduced.
  • FIG. 1 is a view showing a first embodiment of a granulator of calcium chloride hydrate of the present invention.
  • FIG. 2 is a vapor pressure diagram of calcium chloride hydrate.
  • FIG. 3 is a view showing a second embodiment of the granulation device for calcium chloride hydrate of the present invention.
  • FIG. 4 is a cross-sectional view of the first and second dampers 24 and 25 of the granulator of the second embodiment shown in FIG.
  • FIG. 5 is a cross-sectional view showing a reservoir 28 of the granulating apparatus according to the second embodiment shown in FIG. BEST MODE FOR CARRYING OUT THE INVENTION
  • FIG. 1 shows a first embodiment of a granulation device for calcium chloride hydrate according to the present invention.
  • reference numeral 1 denotes a fluidized bed, at the bottom of which a pressurizing chamber 3 is formed via a dispersing plate 2, and a pressurizing blower 4 and an incineration
  • a spray nozzle 8 is suspended above the dispersion plate 2 in the fluidized bed 1 so as to be movable up and down.
  • the spray nozzle 8 is provided with a calcium chloride aqueous solution tank 10 having a concentration adjusting device 9. Connected via feed pump 11.
  • a seed hopper 12 is connected to the fluidized bed 1, and seed particles of calcium chloride hydrate can be supplied into the fluidized bed 1 from slightly above the dispersion plate 2.
  • the seed particles include particles of calcium chloride dihydrate, calcium chloride monohydrate, anhydrous calcium chloride, and mixtures thereof, as well as particles of sodium chloride and magnesium chloride. It may be.
  • the moisture adjusting device 7 radiates or sprays steam or water to the heated and dried fluidizing gas supplied from the hot blast stove 6 to the pressurized chamber 3 of the fluidized bed 1.
  • the moisture content of the flowing gas that is, the humidity is determined. It is configured to be adjustable to a fixed value.
  • the (flow rate) is measured by the flow rate sensor F, and the temperature and humidity of the flowing gas whose moisture has been adjusted by the moisture adjusting device 7 are measured by the temperature sensor 1 ⁇ and the humidity sensor H, respectively.
  • the concentration adjusting device 9 is configured such that a steam pipe through which high-temperature steam is supplied is arranged in the above-mentioned tank 10 where the raw material calcium chloride can be supplied.
  • the retained calcium chloride aqueous solution is heated to evaporate water, and the concentration is adjusted to a predetermined value.
  • concentration sensor D concentration sensor
  • concentration sensor Eta 2 concentration sensor in the fluidized layer 1
  • the humidity by the humidity sensor Eta 2 are respectively measured
  • the humidity of the exhaust gas discharged from the fluidized bed 1 is measured further by the humidity sensor Eta 3.
  • a vibrating sieve device 14 is connected to the outlet of the granulated material in the fluidized bed 1 via a packet elevator 13.
  • This vibrating sieve device 14 is provided with a plurality of sieve nets, each having a smaller mesh size from the upper stage to the lower stage, each of which is inclined with respect to a horizontal plane and is provided so as to be vibrated by a vibrating device.
  • the granulated product supplied from 3 can be separated into medium particles within a predetermined range of particle size distribution, which are regarded as products, coarse particles having a larger particle size and fine particles having a smaller particle size.
  • the number of sieves, the size of the mesh, the angle of inclination with respect to the horizontal plane, and the like are appropriately set according to the size and shape of the particles of the granulated material to be separated as a product.
  • a crusher 15 is connected to the upper stage of the vibrating sieve device 14 so that coarse particles larger than a predetermined particle size distribution, which are separated by being sieved through the upper sieving net, can be crushed.
  • the coarse particles pulverized in this manner are partially passed through the lower sieve screen of the vibrating sieve device 14 and separated into a part of the medium particles within a predetermined particle size distribution range, and the predetermined particles having passed through the upper and lower sieve screens.
  • the particles are returned through the supply path from the seed hopper 12 and can be circulated to the fluidized bed 1.
  • the remainder of the above-mentioned medium particles is supplied to the drying cooler 16 to be subjected to an anti-caking treatment, and is discharged as a product.
  • the humidity sensor H 3 is the outlet of the fluidized bed 1, which is provided, in the present embodiment is connected to the scrubber 1 7 Benchiyuri type as shown in FIG. 1, the exhaust gas discharged from the fluidized bed 1, After the scrubber 17 is washed with washing water to remove fine calcium chloride particles contained in the exhaust gas, the exhaust gas can be exhausted by an exhaust blower 18.
  • the scrubber 17, which has taken in the fine chlorinated calcium particles in the exhaust gas, is circulated as scrubber 17 by the scrubber pump 19, and part of the scrubber 17 is added with the raw material calcium chloride.
  • the aqueous solution can be circulated to the tank 10 as an aqueous solution of calcium chloride sprayed on the fluidized bed 1.
  • the air pushed into the hot blast stove 6 from the pushing blower 4 is heated to a predetermined temperature by the heat generated by burning the fuel with the air from the incineration blower 5, and dried in a dry state. It is sent to the adjusting device 7. After the dried air is adjusted to a predetermined moisture content by adding steam or water in a moisture adjusting device 7, the dried air is usually heated at a high temperature of about 120 to 180 ° C.
  • the pressurized chamber 3 of the fluidized bed 1 It is supplied to the pressurized chamber 3 of the fluidized bed 1 as a working gas and is ejected from the dispersion plate 2 to flow the calcium chloride seed particles held in the fluidized bed 1.
  • the seed particles those supplied from the seed hopper 12 are used in the early stage of the operation of the granulator or when there is a shortage of particles in the fluidized bed 1, and the granulator is usually used.
  • fine particles circulated from the vibrating sieve device # 4 some medium particles, and coarse particles crushed by the crusher 15 are used.
  • a spray nozzle 8 is appropriately moved up and down to be arranged at a predetermined spray height, and a calcium chloride aqueous solution whose concentration has been adjusted by the concentration adjusting device 9 is supplied to a tank 10. Is supplied by a supply pump 11 and sprayed from the spray nozzle 8.
  • the concentration of the aqueous solution of calcium chloride adjusted by the concentration adjusting device 9 is lower than that of the conventional molten salt state, and it is as low as about 5 wt% to as high as 60%. And usually about 37-53 wt%.
  • the calcium chloride sprayed in this way The aqueous solution adheres to the surface of the flowing seed particles and dries, and enlarges the seed particles to form granules.
  • the moisture of the fluidizing gas supplied to the fluidized bed 1 is adjusted by the moisture adjusting device 7
  • the moisture of the aqueous solution of calcium chloride sprayed into the fluidized bed 1 is adjusted by the concentration adjustment.
  • the concentration of the aqueous solution is adjusted by the device 9, that is, the amount of water supplied to the fluidized bed 1 is adjusted.
  • the partial pressure of water vapor in the fluidized bed 1 can be adjusted. Therefore, by adjusting the partial pressure of water vapor in the fluidized bed 1, the chloride pressure in the fluidized bed 1 is adjusted based on the vapor pressure diagram according to the number of water molecules of calcium chloride hydrate as shown in FIG.
  • the vapor pressure of calcium is set to the vapor pressure of calcium chloride hydrate having the number of water molecules to be granulated in accordance with the temperature in the fluidized bed 1.
  • the temperature of the fluidized bed 1 is 9 0 ° C
  • calcium chloride vapor pressure when generating the calcium chloride dihydrate (C a CI 2 ⁇ 2 H 2 0) is 5.3
  • the partial pressure of water vapor in the fluidized bed 1 is adjusted by the water adjusting device 7 and the concentration adjusting device 9 so as to be set at about kPa (40 band Hg).
  • the setting of the vapor pressure of calcium chloride in the fluidized bed 1 by adjusting the water vapor partial pressure is performed by the temperature sensor T 2 , the humidity sensor,, the flow rate sensor F, F 2 , and the like.
  • it is automatically controlled based on the measurement results obtained by the concentration sensor D.
  • the spray nozzle 8 for spraying the aqueous solution of calcium chloride on the seed particles flowing in the fluidized bed 1 can be moved up and down.
  • the spray height for spraying the aqueous solution of calcium chloride is adjustable.
  • the spray height is relatively high, the sprayed calcium chloride aqueous solution becomes fine droplets, adheres to the surface of the seed particles and dries, whereby the calcium chloride granulated is formed.
  • the hydrate has a spinous shape in which protrusions are formed on the surface of the round particles in some places.
  • the spray height is relatively low, the sprayed calcium chloride aqueous solution adheres entirely to the surface of the seed particles and dries, producing round particles having a smooth surface.
  • the Rukoto when the spray height is relatively low, the sprayed calcium chloride aqueous solution adheres entirely to the surface of the seed particles and dries, producing round particles having a smooth surface.
  • the granules thus generated in the fluidized bed 1 are transferred to the bucket conveyor 1. 3 into the vibrating sieve device 14 and sieved by a plurality of inclined vibrating sieves, coarse particles having a larger particle size than a predetermined particle size distribution range, and medium particles within a predetermined particle size distribution range. However, it is classified into fine particles having a smaller particle size than this range. Then, as described above, the coarse particles are pulverized by the pulverizer 15 and returned to the fluidized bed 1 together with the fine particles and some of the medium particles, while the remaining medium particles are consolidated by the drying cooler 16. Prevention treatment is applied and discharged as granulated calcium chloride hydrate as a product.
  • the exhaust gas discharged from the fluidized bed 1 is discharged after the fine calcium chloride particles are collected and removed by the scrubber 17, and the washing water of the scrubber 17 in which the fine chloride particles are dissolved. Some of the water is returned to tank 10 and circulated.
  • chlorides 2, 4, and 6 hydrates which are generally used as products, have the following characteristics. If the temperature of the fluidized bed 1 is relatively low, for example, about 60 to 150 ° C., granulation can be performed by appropriately setting the vapor pressure. By heating the flowing gas such as air, the temperature can be raised relatively easily or maintained stably.
  • the number of water molecules of a predetermined calcium chloride hydrate to be granulated is adjusted by adjusting the partial pressure of steam in the fluidized bed 1 according to the temperature in the fluidized bed 1.
  • the vapor pressure of the calcium chloride hydrate in the fluidized bed 1 can be set to the vapor pressure according to the above, whereby calcium chloride hydrate having a desired number of water molecules can be generated. Therefore, according to the method for granulating calcium chloride hydrate having the above structure, the granulated calcium chloride hydrate having an appropriate number of water molecules according to the use as a product is obtained. Can be reliably manufactured, and the subsequent processing can be performed efficiently and simply.
  • the moisture amount of the fluidizing gas supplied to the fluidized bed 1 by the moisture adjusting device 7, that is, The humidity is adjusted, and the concentration of the aqueous calcium chloride solution sprayed and supplied into the fluidized bed 1 is adjusted by the concentration adjusting device 9 described above. It is also possible to configure so that the partial pressure of water vapor is adjusted. However, especially if it is attempted to adjust the water vapor partial pressure only with the concentration adjusting device 9, the responsiveness to fluctuations in the temperature in the fluidized bed 1 may be insufficient, so the temperature in the fluidized bed 1 may be insufficient.
  • the water content of the flowing gas is adjusted by the moisture adjusting device 7 while maintaining the concentration of the aqueous solution of calcium chloride sprayed by the concentration adjusting device 9 at an appropriate concentration in accordance with the time. It is desirable to adjust the water vapor partial pressure in the fluidized bed 1 by using the adjusting device 7 and the concentration adjusting device 9 together.
  • the temperature and humidity (water content) of the flowing gas, the concentration and the flow rate of the calcium chloride aqueous solution, and the flow rate of the calcium chloride aqueous solution are automatically determined using a computer or the like based on the measurement results obtained by other sensors. By controlling the water vapor pressure, it becomes possible to adjust the water vapor partial pressure more accurately.
  • the spray nozzle 8 for spraying the aqueous solution of calcium chloride is capable of moving up and down as described above, and the spray height of this aqueous solution of chlorinated calcium is set to an appropriate height.
  • the predetermined shape according to the spray height Is produced.
  • the spray height is relatively low, the aqueous solution of chlorinated calcium is uniformly and uniformly adhered to the surface of the seed particles in a liquid state, so that the granules are formed into round particles.
  • the spray height is relatively high, the sprayed calcium chloride aqueous solution becomes droplets and adheres to the surface of the seed particles in a dotted manner.
  • the granules are formed into particles in the shape of confetti. Therefore, for example, when the formed granules of calcium chloride hydrate are used as a hygroscopic material, the latter, such as the confetti-shaped granules, secures a sufficient space around the particles and absorbs moisture.
  • the former round granulated material has a higher packing ratio per unit volume than the former, and can exhibit stable moisture absorption over a long period of time. That is, it is possible to obtain a granulated material having a shape suitable for the purpose.
  • the granulated particles have a spinous shape or a round shape depends on the concentration and supply amount of the aqueous solution of calcium chloride, the shape and size of the spray nozzle 8, and the seeds held in the fluidized bed 1. It is expected that it is affected by the amount of particles and the superficial velocity of the fluidizing gas, but as a result of experiments in which the spray height was varied under various conditions, When the spray height was set to 30 Omni or more, it was confirmed that spinous particles were remarkably generated. However, this does not mean that all particles will have a spinous shape when the spray height is set to the above range, and that the particles will have a spinous shape when the spray height falls below the above range by even 1 mm. This does not mean that no particles are produced at all, and that when the spray height is set within the above range, the proportion of particles in the shape of confetti in the produced granules has increased significantly; is there.
  • the partial pressure of steam in the fluidized bed 1 is adjusted by the moisture adjusting device 7 and the concentration adjusting device 9 to change the vapor pressure of chloridizing water. It is also possible to adjust the pressure to a predetermined value.
  • the proportion of confetti-shaped particles will increase as in the case where the spray height is increased.
  • the partial pressure of water vapor in the fluidized bed 1 approaches the vapor pressure of calcium chloride, the ratio of round particles increases.
  • the adjustment of the water vapor partial pressure and the adjustment of the spray height are performed together, the ratio of the particles of each shape becomes higher.
  • the granulated material discharged from the fluidized bed 1 is separated into coarse particles, medium particles, and fine particles by the vibrating sieve device 14, and among these, medium particles within a predetermined particle size distribution range. Only the product is subjected to anti-caking treatment by the drying cooler 16 to produce a product, and the coarse and fine particles and some medium particles pulverized by the pulverizer 15 are circulated to the fluidized bed 1 as seed particles. It has been made like that. Therefore, for example, when the amount of calcium chloride in the calcium chloride hydrate discharged as the above product and the aqueous solution of calcium chloride sprayed into the fluidized bed 1 is balanced, the seed particles from the seed hopper 12 are obtained only during the initial operation. Can be supplied to the fluidized bed 1 and, during normal operation, the seed particles can be covered by the circulating particles, so that efficient operation can be achieved.
  • the ratio of the total weight of the calcium chloride hydrate discharged from the fluidized bed 1 to the weight of the above-mentioned medium particles that are separated and formed into a product that is, the circulation ratio of the calcium chloride hydrate is 1.5 to 1 It is desirable to set in the range of 0.
  • part of the medium particles separated by the vibrating sieve device 14 is also circulated to the fluidized bed 1, but all of the medium particles are sent to the drying cooler 16. It may be sent to the product.
  • the vibrating sieve device 14 is particularly configured to vibrate the multi-stage sieve mesh inclined with respect to the horizontal plane by the vibrator to separate the granulated material.
  • the size of the particles to be separated can be increased with respect to the size of the particles to be separated, and together with vibrating the sieve screen, clogging can be prevented and efficient separation can be achieved. be able to.
  • a part of the washing water obtained by washing the exhaust gas discharged from the fluidized bed 1 with the scrubber 17 is circulated to the tank 10 of the aqueous calcium chloride solution sprayed on the fluidized bed 1.
  • the fine particles of chloride hydrate contained in the exhaust gas are dissolved and the raw material calcium chloride is added to the washing water having a certain concentration and sprayed into the fluidized bed 1, so that the same concentration is obtained.
  • the amount of the raw material calcium chloride to be supplied to the tank 10 can be reduced, and more economical granulation of calcium chloride hydrate can be promoted. .
  • FIG. 3 to FIG. 5 show a second embodiment of the granulating apparatus of the present invention.
  • the basic configuration is the same as that of the first embodiment described above. Since the configuration is the same as that of the granulating apparatus of the embodiment, the same reference numerals are assigned to the same components, and the description is omitted.
  • the second embodiment is characterized in that a means for preventing solidification of an aqueous solution of calcium chloride is provided first. That is, in the present embodiment, first, as a first solidification preventing means, the calcium chloride aqueous solution held in the tank 10 is supplied to the fluidized bed 1 through the supply pump 11 and sprayed from the spray nozzle 8.
  • One end of a return pipe 21 is connected to the supply pipe 11 A near the fluidized bed 1 side, and the other end of the return pipe 21 is connected to the tank 10.
  • a valve 11B is provided between the connection of the supply pipe 11A and the return pipe 21 to the spray nozzle 8 in the fluidized bed 1.
  • one end of the drainage pipe 22 is connected to the supply pump 11 side of the supply pipe 1 ⁇ A via a valve 22 A as a second solidification preventing means.
  • the other end of the drainage pipe 22 is connected to the scrubber 23.
  • a valve 11C is also provided on the fluidized bed 1 side of the supply pipe 11A slightly from the connection with the drainage pipe 22.
  • the scrubber 23 in the present embodiment is not of the bench lily type as in the first embodiment, but is an exhaust from the fluidized bed 1 introduced into the washing tower 23A. It is of a spray type in which air is washed by washing water sprayed from a spray nozzle 23B provided at an upper part in the washing tower 23A, and this exhaust gas is washed and contained in the exhaust gas.
  • the washing liquid having absorbed the calcium chloride component is held in the washing tower 23A bottom P, heated by steam, circulated as washing water by a scrubber pump 19 as in the first embodiment, and Part of the supply is also possible to be circulated to the above-mentioned tank 0.
  • coarse particles separated by the vibrating sieve device 14 are also separated through the first damper 24 in the present embodiment.
  • the supplied medium particles are supplied to a pulverizer 15 together with a part of the medium particles other than discharged as a product, pulverized, and further, together with fine particles, pass through a second damper 25 as seed particles to form a fluidized bed 1. It is possible to circulate.
  • the first and second dampers 24 and 25 supply the separated coarse particles, coarse particles and a part of the medium particles, and fine particles.
  • the feed pipe 26 to be fed is branched into two branches, and a shield plate 27 is swingably attached to a branch portion in the feed pipe 26. By closing one of the feed pipes 26, particles can be selectively fed to the other.
  • the branched feed pipe 26 is connected to the mill 15 and the drying cooler 16 respectively, and is connected to the second damper 25. In other words, the branched feed pipe 26 is connected to the fluidized bed 1 and the seed hopper 12.
  • the medium particles separated by the vibrating sieve device 14 are supplied to a storage device 28 as shown in FIG.
  • the storage device 28 includes a hopper 28A for storing the supplied medium particles, a vibrating conveyor 28B attached to a lower end of the hopper 28A, and a height direction of the hopper 28A. And a supply pipe 28 C connected to the crusher 15 at a middle position in the hopper 28 A, and the medium particles stored in the hopper 28 A are required by the vibrating conveyor 28 B.
  • the medium particles collected in the hopper 28A beyond the position of the supply pipe 28C are discharged from the supply pipe 28C, It is supplied to the crusher 15 and crushed together with the coarse particles as described above. Have been.
  • the same effects as those of the first embodiment can be obtained, as well as the first and second anti-consolidation means. Since the return pipe 21 and the drain pipe 22 are provided, the aqueous solution of calcium chloride stays when the re-granulation work in which the granulation of calcium chloride hydrate is temporarily stopped is completed. This can prevent a situation where re-consolidation occurs and hinders the subsequent restart of granulation. That is, for example, when the spraying of the aqueous solution of calcium chloride from the spray nozzle 8 into the fluidized bed 1 is interrupted and the granulation is stopped, the aqueous solution of calcium chloride is left in the supply pipe 11A and stays there.
  • the calcium chloride solution may not be able to be supplied to the supply pipe 1A even if the calcium chloride solution is sprayed from the spray nozzle 8.
  • the valve 11B by closing the valve 11B, the calcium chloride aqueous solution remaining in the supply pipe 11A is returned to the tank 10 via the return pipe 21.
  • the calcium chloride aqueous solution is circulated through the supply pipe 11A and the return pipe 21 so that the calcium chloride aqueous solution in the supply pipe 11A solidifies due to stagnation. It is possible to prevent.
  • the valve 11 C After returning to the tank 10, the valve 11 C is closed, the valve 22 A of the drain pipe 22 is opened, and the calcium chloride aqueous solution in the tank 10 is drained to the scrubber 23, and this evening.
  • the link 10 can be emptied to prevent consolidation. Therefore, in this case, together with the washing water in which the calcium chloride component, which is the same calcium chloride aqueous solution, is dissolved, Since the aqueous solution of calcium chloride in the tank 10 can be retained in the scrubber 23, it is sufficient to heat only the aqueous solution of calcium chloride in the scrubber 23 so as not to cause caking. However, tank 10 is more economical and efficient than preventing caking.
  • the aqueous solution of calcium chloride may be supplied from the scrubber 23 to the tank 10 by the scrubber pump 19 as described above.
  • the heated fluidizing gas is supplied from the hot blast stove 6 and the inside of the fluidized bed 1 is supplied.
  • the calcium chloride aqueous solution must be concentrated in the tank 10 to adjust the concentration.
  • the washing water can be circulated in the scrubber 23 as described above.
  • the concentration time of the aqueous calcium chloride solution before the restart of the granulation operation can be shortened.
  • an aqueous solution of calcium chloride having a concentration of, for example, about 35 to 37 wt% is supplied and circulated into the scrubber 23, and the fluidized bed 1 is added to the scrubber 23.
  • the chlorination aqueous solution supplied to the scrubber 23 together with the heat of the steam supplied to the scrubber 23 is quickly cooled. For example, it can be concentrated to a concentration of about 501%.
  • the scrubber 23 it is possible to shorten the preparation time required for resuming the granulation work, and, for example, at the beginning of the resumption of the granulation work, the scrubber 23 does not pass through the tank 10. It is also possible to supply and spray the calcium chloride aqueous solution whose concentration has been directly adjusted to the fluidized bed 1 or, in some cases, omit the tank 10 itself. The same applies to the venturi-type scrubber 17 of the first embodiment.
  • the scrubber 23 sprays the exhaust gas introduced into the washing tower 23A from the spray nozzle 23B instead of the venturi scrubber 17 as in the first embodiment. It is a spray type that is washed with washing water. However, such a spray-type scrubber 23 has a lower exhaust gas flow rate than the venturi-type scrubber 17. Since the pressure loss is reduced, the power of the exhaust blower 18 for discharging the exhaust gas washed from the washing tower 23A is also small, and therefore, according to the present embodiment, More economical granulation can be achieved.
  • the seed particles in the fluidized bed ⁇ are discharged in order to prevent solidification.
  • the particles must be supplied into the fluidized bed 1.However, at this time, if the granulated calcium chloride hydrate was supplied from outside the system as seed particles to the seed hopper 12 and charged into the fluidized bed 1, , Inefficient and uneconomical. However, in the present embodiment, on the other hand, during the normal granulation operation, coarse particles of calcium chloride hydrate granules directly supplied to the fluidized bed 1 as seed particles and pulverized particles of medium particles And fine particles can be selectively supplied to the seed hopper 12 by switching the second damper 25.
  • the second damper 25 is switched to supply the coarse and medium particles and the fine particles to the seed hopper 12 as seed particles.
  • the next time the granulation operation is resumed it is possible to supply the fluidized bed 1 without introducing seed particles from outside the system, and it is possible to achieve efficient granulation .
  • the fine particles are stored in the liquid hopper 12 circulated through the fluidized bed 1 and are used as seed particles, so that the particle diameter of the seed particles becomes larger than necessary. In other words, it is possible to prevent the ratio of granulated calcium chloride hydrate separated as coarse particles in the vibrating sieve device ⁇ 4 from increasing, and to promote more efficient granulation.
  • a coarse particle having a larger particle size may be used. Particles may be required as a product.
  • the coarse particles separated in the vibrating sieve device 14 are selectively supplied to the drying cooler 16 by switching the first damper 25 described above. It has the advantage that it can be discharged as a product and can easily respond to the demands described above. are doing.
  • Table 1 shows an example of the present invention, in which the concentration of the aqueous solution of calcium chloride sprayed into the fluidized bed 1 using the granulator of the first embodiment shown in FIG. Salting by changing the spraying rate, the spray gas temperature and the superficial velocity of the fluidizing bed supplied to the fluidized bed 1, the height of the spray nozzle 8 from the height of the fluidized bed 1 at the stationary bed, and the circulation ratio
  • the temperature, water vapor partial pressure, and vapor pressure of calcium chloride dihydrate in the fluidized bed 1 when granulated calcium dihydrate is formed, as well as the shape of the formed particles and salinity as product This study examined how the concentration of calcium dihydrate changed.
  • the average particle size of the produced calcium chloride hydrate particles was 275 m in Example 3, and the particle size distribution was 2 to 4 Ml.
  • the calcium chloride hydrate is comparatively diluted with a dilute calcium chloride aqueous solution.
  • Granules can be produced even at low temperatures, and the partial pressure of water vapor in the fluidized bed is adjusted by adjusting the amount of water in the fluidizing gas or the concentration of the aqueous calcium chloride solution sprayed.
  • the vapor pressure of calcium chloride hydrate in the fluidized bed is set to the vapor pressure of calcium chloride hydrate having a predetermined number of water molecules according to the temperature in the fluidized bed, and the chloride pressure of this number of water molecules is increased.
  • the spray height of the aqueous solution of calcium chloride with respect to the height of the stationary bed of the fluidized bed is set to 30 Oral or more to produce particles in the shape of confetti.
  • the spray height for example, by setting the spray height to less than 300 and generating round particles, a granulated product containing particles of a predetermined shape is generated. It is possible to provide granules having an appropriate shape according to the use of the product calcium chloride hydrate. Also, by adjusting the partial pressure of water vapor in the fluidized bed with respect to the vapor pressure of calcium oxide, a granulated product containing particles of a predetermined shape can be produced.
  • the granulated product of calcium chloride hydrate thus formed in the fluidized bed is separated into coarse particles, medium particles and fine particles, and the coarse particles are pulverized and desirably at least 1.5 to 10 together with the fine particles.
  • the granulation device is provided with a moisture control device by controlling based on the measurement result by a temperature sensor and a humidity sensor provided in the fluidized bed.
  • Measurement results by the flow rate sensor, temperature sensor, and humidity sensor, and by the concentration sensor and flow rate sensor provided in the concentration adjustment device By controlling the partial pressure of water vapor in the fluidized bed by control based on the measurement results, the vapor pressure of calcium chloride in the fluidized bed is more accurately set to a predetermined vapor pressure, and the desired water is surely supplied.
  • Calcium chloride hydrate having the number of molecules can be granulated, and the automation of the operation of the granulator can be promoted.
  • a return pipe returning to the tank can be connected to the supply pipe to the fluidized bed from the tank of the aqueous solution of calcium chloride, or this tank can be connected to a scrubber that processes the exhaust of the fluidized bed.
  • a scrubber that processes the exhaust of the fluidized bed.
  • the washing water obtained by washing the exhaust gas can be circulated to the scrubber, and at least a part thereof can be supplied to the fluidized bed side.
  • the calcium chloride aqueous solution is concentrated in a scrubber instead of such a tank. Then, it can be supplied to the fluidized bed side, that is, the tank or directly to the fluidized bed, and it is possible to shorten the concentration time and promote efficient granulation work. If the scrubber is of a spray type, the power of the exhaust blower of the scrubber can be reduced, which is more efficient and economical.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Glanulating (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention concerne un procédé de granulation d'hydrate de calcium consistant à fluidiser des particules germes dans un lit fluidisé (1) et à pulvériser une solution aqueuse de chlorure de calcium à l'aide d'une buse (8) de pulvérisation sur les particules fluidisées de façon à obtenir des granules d'hydrate de chlorure de calcium, à ajuster la pression partielle de l'eau dans le lit fluidisé (1) par commande d'un dispositif (7) de régulation de la teneur en humidité du gaz de fluidisation et d'un dispositif (9) de régulation de concentration d'une solution aqueuse de chlorure de calcium à partir au moins des valeurs mesurées par un capteur de température T1 servant à mesurer la température du lit fluidisé (1) et un capteur d'humidité H3 servant à mesurer l'humidité du gaz déchargé du lit fluidisé (1), de façon que la pression de vapeur du chlorure de calcium du lit fluidisé (1) possède une valeur égale à celle d'un hydrate de chlorure de calcium contenant un nombre prédéterminé de molécules d'eau à une certaine température dans le lit fluidisé (1).
PCT/JP2000/004512 1999-01-13 2000-07-06 Procede de granulation d'hydrate de chlorure de calcium et appareil de granulation Ceased WO2002004351A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP00701099A JP4298032B2 (ja) 1999-01-13 1999-01-13 塩化カルシウム水和物の造粒方法および造粒装置
CNB008197253A CN1297481C (zh) 2000-07-06 2000-07-06 氯化钙水合物的造粒方法及造粒装置
PCT/JP2000/004512 WO2002004351A1 (fr) 1999-01-13 2000-07-06 Procede de granulation d'hydrate de chlorure de calcium et appareil de granulation
AU2000258492A AU2000258492A1 (en) 2000-07-06 2000-07-06 Method for granulating calcium chloride hydrate and granulation apparatus

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP00701099A JP4298032B2 (ja) 1999-01-13 1999-01-13 塩化カルシウム水和物の造粒方法および造粒装置
PCT/JP2000/004512 WO2002004351A1 (fr) 1999-01-13 2000-07-06 Procede de granulation d'hydrate de chlorure de calcium et appareil de granulation

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Cited By (6)

* Cited by examiner, † Cited by third party
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RU2240976C1 (ru) * 2003-09-22 2004-11-27 Открытое акционерное общество "Научно-исследовательский институт по удобрениям и инсектофунгицидам им. проф. Я.В.Самойлова" Абсорбционная башня
RU2242425C1 (ru) * 2003-07-07 2004-12-20 Открытое акционерное общество "АВИСМА титано-магниевый комбинат" Способ получения гранулированного хлорида кальция
RU2258037C2 (ru) * 2003-10-08 2005-08-10 Открытое акционерное общество "АВИСМА титано-магниевый комбинат" Способ получения гранулированного хлорида кальция и установка для его осуществления
RU2290368C2 (ru) * 2003-11-05 2006-12-27 Общество с ограниченной ответственностью "Зиракс" (ООО "Зиракс") Способ получения гранулированного хлорида кальция
RU2410153C1 (ru) * 2009-06-16 2011-01-27 Открытое акционерное общество "СОДА" (ОАО "СОДА") Аппарат для получения гранулированных продуктов
US11072621B2 (en) * 2017-07-14 2021-07-27 Gj Cheiljedang Corporation Methionine-metal chelate and manufacturing method thereof

Families Citing this family (6)

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JP4298032B2 (ja) * 1999-01-13 2009-07-15 アイテック有限会社 塩化カルシウム水和物の造粒方法および造粒装置
JP3479278B2 (ja) 2000-11-17 2003-12-15 開成工業株式会社 塩化カルシウム造粒物の製造方法および製造装置
WO2003059501A1 (fr) * 2001-12-28 2003-07-24 Kaisei Kogyo Co., Ltd. Appareil et procede de granulation d'hydrates mixtes de chlorure de calcium et de chlorure de sodium et granules de ces hydrates mixtes
RU2243161C1 (ru) * 2003-11-10 2004-12-27 Открытое акционерное общество "АВИСМА титано-магниевый комбинат" Способ получения гранулированного хлорида кальция
CN103028343B (zh) * 2012-12-18 2015-07-29 天津大学 一种球粒状二水氯化钙的生产方法
JP2017088426A (ja) * 2015-11-04 2017-05-25 月島機械株式会社 塩化カルシウム水和物の造粒方法および塩化カルシウム水和物の造粒装置

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DD200423A1 (de) * 1981-09-28 1983-05-04 Heinz Scherzberg Verfahren zur herstellung von calciumchlorid
DD223427A1 (de) * 1984-04-13 1985-06-12 Kali Veb K Verfahren zur herstellung von staubfreiem calciumchlorid
DD223428A1 (de) * 1984-04-13 1985-06-12 Kali Veb K Verfahren zur herstellung von calciumchloridgranulat
DD232905A1 (de) * 1984-12-27 1986-02-12 Kali Veb K Verfahren zur herstellung von hochreinen calciumchlorid-granulaten
JP2000203833A (ja) * 1999-01-13 2000-07-25 Kaisei Kogyo Kk 塩化カルシウム水和物の造粒方法および造粒装置

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DD200423A1 (de) * 1981-09-28 1983-05-04 Heinz Scherzberg Verfahren zur herstellung von calciumchlorid
DD223427A1 (de) * 1984-04-13 1985-06-12 Kali Veb K Verfahren zur herstellung von staubfreiem calciumchlorid
DD223428A1 (de) * 1984-04-13 1985-06-12 Kali Veb K Verfahren zur herstellung von calciumchloridgranulat
DD232905A1 (de) * 1984-12-27 1986-02-12 Kali Veb K Verfahren zur herstellung von hochreinen calciumchlorid-granulaten
JP2000203833A (ja) * 1999-01-13 2000-07-25 Kaisei Kogyo Kk 塩化カルシウム水和物の造粒方法および造粒装置

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2242425C1 (ru) * 2003-07-07 2004-12-20 Открытое акционерное общество "АВИСМА титано-магниевый комбинат" Способ получения гранулированного хлорида кальция
RU2240976C1 (ru) * 2003-09-22 2004-11-27 Открытое акционерное общество "Научно-исследовательский институт по удобрениям и инсектофунгицидам им. проф. Я.В.Самойлова" Абсорбционная башня
RU2258037C2 (ru) * 2003-10-08 2005-08-10 Открытое акционерное общество "АВИСМА титано-магниевый комбинат" Способ получения гранулированного хлорида кальция и установка для его осуществления
RU2290368C2 (ru) * 2003-11-05 2006-12-27 Общество с ограниченной ответственностью "Зиракс" (ООО "Зиракс") Способ получения гранулированного хлорида кальция
RU2410153C1 (ru) * 2009-06-16 2011-01-27 Открытое акционерное общество "СОДА" (ОАО "СОДА") Аппарат для получения гранулированных продуктов
US11072621B2 (en) * 2017-07-14 2021-07-27 Gj Cheiljedang Corporation Methionine-metal chelate and manufacturing method thereof

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