WO2010055703A1 - 工業塩、工業塩の製造装置及び製造方法 - Google Patents
工業塩、工業塩の製造装置及び製造方法 Download PDFInfo
- Publication number
- WO2010055703A1 WO2010055703A1 PCT/JP2009/057562 JP2009057562W WO2010055703A1 WO 2010055703 A1 WO2010055703 A1 WO 2010055703A1 JP 2009057562 W JP2009057562 W JP 2009057562W WO 2010055703 A1 WO2010055703 A1 WO 2010055703A1
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- WO
- WIPO (PCT)
- Prior art keywords
- filtrate
- industrial salt
- drying
- dust
- washing
- Prior art date
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- 150000003839 salts Chemical class 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 83
- 239000000428 dust Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000001035 drying Methods 0.000 claims abstract description 44
- 239000007789 gas Substances 0.000 claims abstract description 41
- 239000004568 cement Substances 0.000 claims abstract description 35
- 238000005406 washing Methods 0.000 claims abstract description 35
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011575 calcium Substances 0.000 claims abstract description 27
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 27
- 239000007921 spray Substances 0.000 claims abstract description 21
- 239000000567 combustion gas Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000000460 chlorine Substances 0.000 claims description 61
- 229910052801 chlorine Inorganic materials 0.000 claims description 61
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 60
- 238000004519 manufacturing process Methods 0.000 claims description 40
- 229910001385 heavy metal Inorganic materials 0.000 claims description 18
- 238000000605 extraction Methods 0.000 claims description 7
- 238000005259 measurement Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 13
- 238000002425 crystallisation Methods 0.000 abstract description 10
- 230000008025 crystallization Effects 0.000 abstract description 10
- 230000001603 reducing effect Effects 0.000 abstract description 7
- 239000004615 ingredient Substances 0.000 abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 2
- 230000000740 bleeding effect Effects 0.000 abstract 1
- 238000000502 dialysis Methods 0.000 abstract 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 239000001103 potassium chloride Substances 0.000 description 9
- 235000011164 potassium chloride Nutrition 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000011669 selenium Substances 0.000 description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 7
- 229910052711 selenium Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 229960002089 ferrous chloride Drugs 0.000 description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000909 electrodialysis Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052981 lead sulfide Inorganic materials 0.000 description 4
- 229940056932 lead sulfide Drugs 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- BXJGLLKRUQQYTC-UHFFFAOYSA-N thallium(1+);sulfide Chemical compound [S-2].[Tl+].[Tl+] BXJGLLKRUQQYTC-UHFFFAOYSA-N 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000008267 milk Substances 0.000 description 3
- 210000004080 milk Anatomy 0.000 description 3
- 235000013336 milk Nutrition 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- -1 alkali metal salt Chemical class 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/60—Methods for eliminating alkali metals or compounds thereof, e.g. from the raw materials or during the burning process; methods for eliminating other harmful components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/08—Preparation by working up natural or industrial salt mixtures or siliceous minerals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to an industrial salt obtained from the combustion exhaust gas of a cement kiln constituting a cement firing facility, and an industrial salt manufacturing apparatus and manufacturing method.
- An object of the present invention is to provide an industrial salt that can be reduced and manufactured at low cost, and can stabilize the quality by suppressing component fluctuations, and an industrial salt manufacturing apparatus and manufacturing method.
- the present invention is an industrial salt, and a part of combustion gas is extracted from a kiln exhaust gas passage from a kiln bottom of a cement kiln to a lowermost cyclone, and dust in the extracted gas is extracted. It is characterized by being obtained by recovering and washing with water, and drying the filtrate after washing in an air stream.
- the equipment for electrodeposition and crystallization equipment is not required, and further, the power cost for electrodeposition and the heavy oil used for crystallization are no longer required. The operating cost can be greatly reduced, and inexpensive industrial salt can be provided.
- the industrial salt can be obtained by removing calcium content from the filtrate and drying the filtrate from which the calcium content has been removed in an air stream, and removing the sulfate radical from the filtrate to obtain the sulfate radical.
- the filtrate from which the water has been removed can be obtained by drying in an air stream.
- the industrial salt can be obtained by removing heavy metals from the filtrate after washing with water and then drying the filtrate from which the heavy metals have been removed in an air stream. According to this, a higher quality industrial salt is provided. be able to.
- Exhaust gas discharged from the clinker cooler can be used for drying the industrial salt, and the operation cost for drying the filtrate from which heavy metals have been removed can be suppressed, and an inexpensive industrial salt can be provided.
- a spray dryer for the above drying, a spray dryer, a spray fluidized granulator or a gate dryer can be used, and an industrial salt having a desired particle diameter can be easily obtained without performing wastewater treatment or the like.
- the particle size after drying in the air flow of the industrial salt can be 20 ⁇ m or more and 500 ⁇ m or less, and it is possible to provide an industrial salt suitable for the application.
- the present invention also relates to an industrial salt production apparatus, which extracts a part of combustion gas from a kiln exhaust gas flow path from the bottom of the kiln of a cement kiln to the lowermost cyclone, and performs extraction with the extraction apparatus.
- a device According to the present invention, as in the case of the above-described invention, it is possible to produce industrial salt at a low cost by reducing equipment costs and operating costs, and it is possible to obtain an industrial salt with stable quality by suppressing component fluctuations. Become.
- the present invention is a method for producing industrial salt, in which a part of combustion gas is extracted from a kiln exhaust gas passage from a kiln bottom of a cement kiln to a lowermost cyclone, and dust in the extracted gas is removed.
- the industrial salt is obtained by recovering and washing with water, and drying the filtrate after washing with water in an air stream.
- the amount of washing water of the dust or / and the amount of dust supplied to the washing device can be adjusted, and the chlorine concentration of the filtrate can be adjusted to a target value or more.
- the chlorine concentration of the liquid can be measured, and the amount of dust washing water and / or the amount of dust supplied to the washing device can be adjusted according to the measurement result. According to this, the chlorine concentration of a filtrate can be adjusted suitably and it becomes possible to obtain the industrial salt which has desired potassium chloride purity suitably.
- Using the manufacturing apparatus of a conventional industrial salt is a graph showing a change in the K 2 O concentration in the case of manufacturing industrial salt for several days. It is a graph showing the relationship between the chlorine concentration of the total amount filtrate of calcium components and SO 4 dissolving in the washing filtrate of chlorine bypass dust. It is a graph showing the relationship between the solubility of the solubility and SO 4 calcium content.
- FIG. 1 shows an embodiment of an industrial salt production apparatus according to the present invention.
- the industrial salt production apparatus 1 is roughly divided into a cement production apparatus 11, a water washing apparatus 21, a heavy metal removal apparatus 31, and a drying apparatus.
- the apparatus 41 is comprised.
- the cement manufacturing apparatus 11 includes a cement kiln 12 provided with a clinker cooler 12a, an extraction device (hereinafter referred to as “probe”) 14 for extracting a part of combustion gas from the kiln bottom 12b of the cement kiln 12, and an extraction gas.
- a classifier 15 for separating the coarse powder C contained in G1 a cooler 16 for cooling the exhaust gas G2 of the classifier 15, a bag filter 17 for collecting the exhaust gas G3 cooled by the cooler 16, and a cooler 16
- the tank 18 stores the chlorine bypass dust D collected by the bag filter 17 and the tank 20 stores the chlorine bypass dust D transported by the vehicle 19. All of these devices and the like constituting the cement manufacturing apparatus 11 are usually used.
- the water washing device 21 is a dissolution tank 22 for dissolving chlorine in the chlorine bypass dust D stored in the tank 20, and a filter 23 for solid-liquid separation of the slurry S discharged from the dissolution tank 22 into cake CA and filtrate L1. And a hot water tank 24 for supplying hot water H to the dissolution tank 22 and the filter 23, and an electric conductivity meter 25 for measuring the chlorine concentration of the filtrate L1.
- the hot water tank 24 is provided to store the industrial water I used for industrial use, which is heated by the exhaust gas G6 used for drying the industrial salt described later.
- the hot water H stored in the hot water tank 24 is circulated and used in the water washing device 21, the heavy metal removing device 31 and the drying device 41.
- the heavy metal removing device 31 solidifies the chemical solution reaction tank 32 (32A, 32B) for removing heavy metals in the filtrate L1 discharged from the filter 23, and the slurry R discharged from the chemical solution reaction tank 32 into the residue R and the filtrate L2.
- the filter press 33 is configured to separate the liquid, and the filtrate tank 34 stores the filtrate L2 discharged from the filter press 33.
- the chemical reaction tank 32A is prepared to add sodium hydrosulfate to the filtrate L1 to produce lead sulfide and thallium sulfide, adjust the pH with hydrochloric acid, and then add ferrous chloride to reduce selenium. .
- the reason for adding hydrochloric acid is to enhance the reduction effect of ferrous chloride.
- the chemical liquid reaction tank 32B is provided for adjusting pH by adding slaked lime to the filtrate L1 supplied from the chemical liquid reaction tank 32A. The reason for adjusting the pH is to condense and precipitate the ferrous hydroxide produced by the addition of ferrous chloride.
- the filter press 33 is provided for solid-liquid separation of the filtrate L1 discharged from the chemical reaction tank 32B and separating it into a residue R and a filtrate L2 such as thallium sulfide, lead sulfide and selenium.
- the drying device 41 includes a bag filter 42 that collects dust DA in the exhaust gas G4 discharged from the clinker cooler 12a, and a spray dryer 43 that dries the filtrate L2 stored in the filtrate tank 34 to obtain industrial salt S.
- the bag filter 44 collects the industrial salt S in the exhaust gas G5 discharged from the spray dryer 43, and the heating device 45 for warming the working water I and the like.
- the spray dryer 43 includes an atomization device, a hot air introduction device, a drying chamber, a dry powder separation / collection device, an exhaust treatment device, and a product cooling device, although not shown below.
- the atomization device sprays the filtrate L2 with a nozzle
- the hot air introduction device is a device that introduces the exhaust gas G4 discharged from the clinker cooler 12a into the drying chamber.
- the supply liquid amount, supply liquid concentration, hot air temperature of hot air (exhaust gas G4), hot air amount, chamber temperature, exhaust air temperature, nozzle pressure, and droplets are controlled in the spray dryer 43.
- the average particle size and the like are adjusted as appropriate.
- the heating device 45 is provided to heat the industrial water I and the like with the exhaust gas G6 discharged from the bag filter 44 and supply the hot water H to the hot water tank 24.
- the coarse powder C is separated from the extracted gas G1 by the classifier 15, and returned to the kiln system.
- the exhaust gas G2 discharged from the classifier 15 is cooled by the cooler 16, and the dust in the exhaust gas G3 is collected by the bag filter 17. Then, the chlorine bypass dust D collected from the cooler 16 and the bag filter 17 is stored in the tank 18 and returned to the kiln system by the vehicle 19 or conveyed to the tank 20.
- the chlorine bypass dust D stored in the tank 20 is supplied to the dissolution tank 22 and the water-soluble chlorine content contained in the chlorine bypass dust D is dissolved in the warm water H.
- the hot water H is passed through the cake obtained by dehydrating the slurry S discharged from the dissolution tank 22, and the slurry S is washed with water. To do.
- the cake CA from which the chlorine content has been removed is used as a cement raw material.
- the filtrate L1 containing chlorine is supplied to the chemical reaction tank 32A, and the chlorine concentration is measured by the electric conductivity meter 25 in the process. Then, referring to the measured chlorine concentration, the supply amount of chlorine bypass dust D to the dissolution tank 22 and the washing water amount in the filter 23 are increased and decreased, and the chlorine concentration of the filtrate L1 is the target value (about 1.7%) ) Adjust so that it becomes the above.
- the supply amount of the chlorine bypass dust D is increased, and the amount of washing water in the filter 23 is decreased to be discharged from the dissolution tank 22.
- Increase the chlorine concentration of the slurry S It is not always necessary to increase or decrease both the supply amount of chlorine bypass dust D to the dissolution tank 22 and the amount of washing water in the filter 23.
- the chlorine concentration of the filtrate L1 can be increased. You may make it adjust.
- sodium hydrosulfide is added as a sulfiding agent to the filtrate L1 in the chemical reaction tank 32A, and lead and thallium in the filtrate L1 are sulfided to produce lead sulfide and thallium sulfide.
- ferrous chloride is added and selenium is reduced.
- the filtrate L1 is supplied from the chemical reaction tank 32A to the chemical reaction tank 32B, lime milk is added to the filtrate L1 to adjust the pH to 7.0 to 10.0, and then ferrous chloride is added. The ferrous hydroxide produced by is precipitated.
- the filtrate L1 discharged from the chemical solution reaction tank 32B is solid-liquid separated by the filter press 33 into the residue R and the filtrate L2.
- the residue R containing heavy metals such as lead sulfide, thallium sulfide and selenium is reused as a cement raw material.
- the filtrate L2 discharged from the filter press 33 is stored in the filtrate tank 34.
- the industrial salt After drying, the industrial salt is separated and collected by a dry powder separation and collection device, cooled by a product cooling device, and then industrial salt S having a particle size of 20 ⁇ m or more and 500 ⁇ m or less is obtained.
- the industrial salt S thus obtained is shipped after packing and used as a chemical fertilizer.
- the exhaust gas G4 used for drying the industrial salt S is introduced into the bag filter 44 through an exhaust treatment device, and after the solid-gas separation, the heating water 45 is heated by the heating device 45, and the obtained hot water H is heated. It is stored in the water tank 24.
- the industrial salt S collected by the bag filter 44 is packaged and shipped together with the industrial salt S dried in an air stream by the spray dryer 43.
- the conventional electrodeposition apparatus and crystallization apparatus are unnecessary, so that the electric power used for electrodeposition and the heavy oil used for crystallization are not required. Moreover, since the chemical
- the filtrate L2 is dried by airflow drying using the spray dryer 43, sodium chloride is not concentrated in the drying process of the filtrate L2, and the concentration of potassium chloride in the industrial salt S varies. Can be suppressed.
- the spray dryer 43 since water is evaporated in the form of droplets, all the ions contained in the sprayed filtrate L2 are crystallized, and the sprayed components can be used as industrial salt components as they are. . By these, the component fluctuation
- the heavy metal is removed from the filtrate L2 and then immediately dried in an air stream.
- potassium carbonate is added to the filtrate L2 after the heavy metal is removed.
- the precipitate may be precipitated, and the filtrate may be solid-liquid separated to remove calcium from the filtrate.
- the purity of potassium chloride can be increased, and it is inexpensive and has the same purity as conventional industrial salts obtained by electrodeposition and crystallization. A salt can be obtained.
- a pH adjuster alkaline agent containing calcium
- lime milk is added to adjust the pH of the filtrate L2 to 8.5 to 10.0.
- the purity of the recovered salt can be increased by increasing the amount of calcium eluted into the liquid L2 and suppressing the elution of sulfate radicals (sulfate ions (SO 4 2 ⁇ )).
- the sulfate radical may be removed by an electrodialysis apparatus.
- a pH adjusting agent such as lime milk is added to adjust the pH of the filtrate L2 to 7.0 to 8.5, and the elution of calcium content is suppressed to increase the concentration of sulfate radicals.
- the purity of the recovered salt can be increased.
- heavy metals are removed from the filtrate L1 before airflow drying.
- the heavy metal removal treatment can be omitted depending on the heavy metal content and the state of use of industrial salts.
- the lowermost cyclone 13 is supplied from the kiln bottom 12b.
- a part of the combustion gas can be extracted from the kiln exhaust gas flow path up to.
- the classifier 15 is disposed between the probe 14 and the cooler 16, but the extraction gas may be directly introduced into the cooler 16 from the probe 14 without providing the classifier 15. Good.
- the exhaust gas G4 from the clinker cooler 12a is used when drying with the spray dryer 43.
- the exhaust gas from the uppermost cyclone of the preheater attached to the cement kiln 12 is cooled. It may be used after adjusting the temperature.
- the nozzle type spray dryer 43 is used as the drying device.
- a spray fluidized granulation drying device that granulates while drying may be used to produce industrial salts having different particle sizes. It is also possible to deal with various uses. Further, in a general spray dryer, it takes about 5 seconds from spraying to drying, but an industrial salt having a smaller particle diameter can be obtained by using a gate dryer in which droplets are dried within a few microseconds after spraying.
- FIG. 4 shows the relationship between the chlorine concentration of the filtrate L1 of the filter 23 (see FIG. 1) and the concentration of K 2 O in the industrial salt
- FIG. 5 shows the chlorine concentration of the chlorine bypass dust D. It shows the relationship between the K 2 O concentration in the industrial salt. 3 to 6, the concentration of K 2 O is an average value of industrial salt produced in one day.
- the calcium content and SO 4 dissolution amount in the filtrate L1 of the filter 23 were measured while increasing the chlorine concentration by increasing the supply amount of chlorine bypass dust.
- the measurement results are shown in FIG. In FIG. 7, the vertical axis represents the total amount of calcium and SO 4 dissolved in the filtrate L1.
- the solubility of calcium and SO 4 has an inversely proportional relationship. For example, when calcium is dissolved at a high concentration, SO 4 is dissolved only at a low concentration. It was. Therefore, if calcium content is removed from the filtrate L1 in a state where a high concentration calcium content is dissolved in the filtrate L1, only low concentration SO 4 remains in the filtrate L1, and the industrial salt K 2 O The concentration can be increased effectively.
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- Ceramic Engineering (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
Description
11 セメント製造装置
12 セメントキルン
12a クリンカクーラー
12b 窯尻
13 最下段サイクロン
14 プローブ
15 分級機
16 冷却器
17 バグフィルタ
18 タンク
19 車両
20 タンク
21 水洗装置
22 溶解槽
23 ろ過機
24 温水槽
25 電気伝導度計
31 重金属除去装置
32(32A、32B) 薬液反応槽
33 フィルタープレス
34 ろ液槽
41 乾燥装置
42 バグフィルタ
43 スプレードライヤー
44 バグフィルタ
45 加熱装置
Claims (11)
- セメントキルンの窯尻から最下段サイクロンに至るまでのキルン排ガス流路より燃焼ガスの一部を抽気し、抽気したガス中のダストを回収して水洗し、水洗後のろ液を気流中で乾燥させて得られることを特徴とする工業塩。
- 前記ろ液からカルシウム分を除去し、該カルシウム分を除去したろ液を気流中で乾燥させて得られることを特徴とする請求項1に記載の工業塩。
- 前記ろ液から硫酸根を除去し、該硫酸根を除去したろ液を気流中で乾燥させて得られることを特徴とする請求項1に記載の工業塩。
- 水洗後のろ液から重金属を除去し、該重金属を除去したろ液を気流中で乾燥させることを特徴とする請求項1、2又は3に記載の工業塩。
- 前記気流に、前記セメント製造設備のクリンカクーラーから排出される排気を用いることを特徴とする請求項1乃至4のいずれかに記載の工業塩。
- 前記乾燥に、スプレードライヤー、スプレー流動造粒乾燥装置又はゲートドライヤーを用いることを特徴とする請求項1乃至5のいずれかに記載の工業塩。
- 前記気流中で乾燥した後の粒径が20μm以上500μm以下であることを特徴とする請求項1乃至6のいずれかに記載の工業塩。
- セメントキルンの窯尻から最下段サイクロンに至るまでのキルン排ガス流路より燃焼ガスの一部を抽気する抽気装置と、
該抽気装置で抽気したガス中のダストを回収する集塵装置と、
該集塵装置で回収したダストを水洗する水洗装置と、
該水洗装置における水洗により発生したろ液を気流中で乾燥させて工業塩を得る乾燥装置とを備えることを特徴とする工業塩の製造装置。 - セメントキルンの窯尻から最下段サイクロンに至るまでのキルン排ガス流路より燃焼ガスの一部を抽気し、
該抽気したガス中のダストを回収して水洗し、
該水洗後のろ液を気流中で乾燥させて工業塩を得ることを特徴とする工業塩の製造方法。 - 前記ダストの水洗水量又は/及び水洗装置への該ダストの供給量を調整し、前記ろ液の塩素濃度を目標値以上に調整することを特徴とする請求項9に記載の工業塩の製造方法。
- 前記ろ液の塩素濃度を測定し、測定結果に応じて前記ダストの水洗水量又は/及び前記水洗装置へのダストの供給量を調整することを特徴とする請求項10に記載の工業塩の製造方法。
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CN2009801449903A CN102216218A (zh) | 2008-11-12 | 2009-04-15 | 工业盐、工业盐的制造装置及制造方法 |
US13/128,183 US8808651B2 (en) | 2008-11-12 | 2009-04-15 | Industrial salt and apparatus and process for producing industrial salt |
EP09825956.7A EP2347998B1 (en) | 2008-11-12 | 2009-04-15 | Apparatus and process for producing industrial salt |
JP2010537718A JP5566904B2 (ja) | 2008-11-12 | 2009-04-15 | 工業塩、工業塩の製造装置及び製造方法 |
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US (1) | US8808651B2 (ja) |
EP (1) | EP2347998B1 (ja) |
JP (1) | JP5566904B2 (ja) |
KR (1) | KR101552650B1 (ja) |
CN (2) | CN102216218A (ja) |
HK (1) | HK1205732A1 (ja) |
TW (1) | TWI486308B (ja) |
WO (1) | WO2010055703A1 (ja) |
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JP2011042510A (ja) * | 2009-08-19 | 2011-03-03 | Taiheiyo Cement Corp | 肥料並びにその製造方法及び製造装置 |
AT511410A1 (de) * | 2011-04-21 | 2012-11-15 | Holcim Technology Ltd | Verfahren zur behandlung und verwertung von bypass-stäuben aus dem zementherstellungsprozess |
WO2019181385A1 (ja) * | 2018-03-23 | 2019-09-26 | 太平洋セメント株式会社 | 塩素含有粉体の脱塩処理方法及び塩素含有粉体の脱塩処理装置 |
JP2020006365A (ja) * | 2018-06-28 | 2020-01-16 | 三菱マテリアル株式会社 | 重金属含有ダストの処理方法 |
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JPWO2010055703A1 (ja) | 2012-04-12 |
EP2347998A4 (en) | 2012-04-04 |
TWI486308B (zh) | 2015-06-01 |
CN102216218A (zh) | 2011-10-12 |
US20110305905A1 (en) | 2011-12-15 |
US8808651B2 (en) | 2014-08-19 |
TW201018646A (en) | 2010-05-16 |
EP2347998B1 (en) | 2019-10-16 |
EP2347998A1 (en) | 2011-07-27 |
JP5566904B2 (ja) | 2014-08-06 |
HK1205732A1 (en) | 2015-12-24 |
CN104671259A (zh) | 2015-06-03 |
KR20110095861A (ko) | 2011-08-25 |
KR101552650B1 (ko) | 2015-09-11 |
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