WO2019181619A1 - フライアッシュの改質方法 - Google Patents
フライアッシュの改質方法 Download PDFInfo
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- WO2019181619A1 WO2019181619A1 PCT/JP2019/009767 JP2019009767W WO2019181619A1 WO 2019181619 A1 WO2019181619 A1 WO 2019181619A1 JP 2019009767 W JP2019009767 W JP 2019009767W WO 2019181619 A1 WO2019181619 A1 WO 2019181619A1
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- Prior art keywords
- fly ash
- cooling
- classification
- fine powder
- unburned carbon
- Prior art date
Links
- 239000010881 fly ash Substances 0.000 title claims abstract description 111
- 238000002715 modification method Methods 0.000 title abstract 2
- 238000001816 cooling Methods 0.000 claims abstract description 96
- 239000000843 powder Substances 0.000 claims abstract description 69
- 238000010438 heat treatment Methods 0.000 claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000000428 dust Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims description 29
- 239000011362 coarse particle Substances 0.000 claims description 28
- 238000002407 reforming Methods 0.000 claims description 13
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 10
- 239000004568 cement Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 230000001174 ascending effect Effects 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 239000010849 combustible waste Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
- B07B4/00—Separating solids from solids by subjecting their mixture to gas currents
- B07B4/08—Separating solids from solids by subjecting their mixture to gas currents while the mixtures are supported by sieves, screens, or like mechanical elements
-
- 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
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C18/00—Disintegrating by knives or other cutting or tearing members which chop material into fragments
- B02C18/0084—Disintegrating by knives or other cutting or tearing members which chop material into fragments specially adapted for disintegrating garbage, waste or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
- B03B9/04—General arrangement of separating plant, e.g. flow sheets specially adapted for furnace residues, smeltings, or foundry slags
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
- B07B11/00—Arrangement of accessories in apparatus for separating solids from solids using gas currents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
- B07B11/00—Arrangement of accessories in apparatus for separating solids from solids using gas currents
- B07B11/02—Arrangement of air or material conditioning accessories
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
- B07B11/00—Arrangement of accessories in apparatus for separating solids from solids using gas currents
- B07B11/06—Feeding or discharging arrangements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
- B07B4/00—Separating solids from solids by subjecting their mixture to gas currents
- B07B4/02—Separating solids from solids by subjecting their mixture to gas currents while the mixtures fall
- B07B4/025—Separating solids from solids by subjecting their mixture to gas currents while the mixtures fall the material being slingered or fled out horizontally before falling, e.g. by dispersing elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
- B07B9/00—Combinations of apparatus for screening or sifting or for separating solids from solids using gas currents; General arrangement of plant, e.g. flow sheets
- B07B9/02—Combinations of similar or different apparatus for separating solids from solids using gas currents
-
- 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
- C04B18/08—Flue dust, i.e. fly ash
-
- 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
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
-
- 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
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/40—Dehydrating; Forming, e.g. granulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C2201/00—Codes relating to disintegrating devices adapted for specific materials
- B02C2201/06—Codes relating to disintegrating devices adapted for specific materials for garbage, waste or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
- B07B2230/00—Specific aspects relating to the whole B07B subclass
- B07B2230/01—Wet separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/30—Incineration ashes
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
- C04B2111/1087—Carbon free or very low carbon content fly ashes; Fly ashes treated to reduce their carbon content or the effect thereof
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/20—Waste processing or separation
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the present invention relates to a method for modifying fly ash.
- fly ash When fly ash is used as a cement or concrete mixed material, it is generally preferred that the fly ash contains less unburned carbon.
- the heating temperature is preferably set to 780 ° C. or lower. Therefore, the heating temperature for removing unburned carbon is optimally in the range of 700 to 780 ° C. It is very difficult to heat to such a limited temperature.
- JP 2008-126117 A Japanese Patent Laid-Open No. 11-060299
- an object of the present invention is to modify fly ash having various unburned carbon amounts by reducing the unburned carbon amount in a short time with certainty, and the total amount of fly ash after reforming is relatively simple.
- An object of the present invention is to provide a method for modifying fly ash that can be used as a mixed material.
- the present inventors have intensively studied in view of the above problems. And even if it is a modified fly ash containing a lump, it can be efficiently cooled by performing air classification while also serving as a cooling, and it is possible to obtain a modified fly ash having suitable properties as a mixed material As a result, the present invention has been completed.
- the cooling classification apparatus used in the cooling classification step has a basic structure for introducing a classification airflow from below and discharging the cooling classification airflow introduced into the apparatus from above, The heat treatment fly ash charged into the cooling classifier is brought into contact with the air flow for cooling classification, the fine powder contained in the heat treatment fly ash is raised and discharged out of the apparatus, and is included in the heat treatment fly ash.
- the fine powder and coarse particles are separated and cooled,
- a fly ash reforming method wherein the fine powder discharged from the cooling classifier is collected using a dust collector, and the coarse particles are collected from the cooling classifier.
- the following embodiments can be suitably employed.
- Classification in the cooling classifier is performed under watering.
- the amount of unburned carbon is reduced to less than 3% by mass by the heating step.
- Heating in the heating step is performed so that the content of massive particles having a maximum diameter of 150 ⁇ m or more contained in the heat-treated fly ash in which the amount of unburned carbon is reduced does not exceed 50 mass%.
- the classification point is set so that the 45 ⁇ m sieve residue of the fine powder obtained by classification is 34% by mass or less.
- the coarse particles obtained by classification are pulverized until the 45 ⁇ m sieve residue is 34 mass% or less.
- the heating temperature is set to a high temperature of 780 to 1000 ° C. and in a wide range. Therefore, fly ash raw powders having different unburned carbon amounts can be continuously used in a relatively short time. And the modified fly ash suitable as a cement and concrete mixed material can be obtained stably.
- fly ash (heat treated fly ash) heated by a heating device to reduce the amount of unburned carbon is a lump containing lump particles having a large particle size.
- this heat treated fly ash is kept at a high temperature, it is introduced into a cooling classifier, and air classification is performed at the same time as cooling using an air flow for cooling classification, and coarse particles containing large massive particles And separated into fine powder. That is, this cooling classifier supplies an airflow for cooling classification (for example, air) from below, contacts the heat treatment fly ash with such an airflow, lifts the fine powder that is easily cooled, and discharges it from the apparatus. Coarse particles that are difficult to cool are retained in the apparatus.
- airflow for cooling classification for example, air
- the fine powder that is easily cooled is quickly discharged from the apparatus while being in contact with the cooling classification airflow, and the coarse particles that are difficult to be cooled are retained in the apparatus and are always kept in contact with the cooling classification airflow. . For this reason, cooling can be performed efficiently and in a short time. That is, when cooling with a large lump without classifying, the cooling efficiency is poor, and a long time is required for cooling.
- the heat-treated fly ash with a reduced amount of unburned carbon is collected separately for each fine powder obtained by classification and coarsely pulverized product obtained by classification, but both are mixed.
- the entire amount of fly ash in which the amount of unburned carbon is reduced by heat treatment can be efficiently used as a mixture of cement and concrete.
- fly ash raw powder containing unburned carbon is heated by heating device 1 to reduce the amount of unburned carbon (heating process), and the amount of unburned carbon is reduced.
- the heat-treated fly ash is introduced into the cooling classifier 3 while being maintained at a high temperature, and cooling and classification are performed (cooling classification process).
- the fine powder obtained by this cooling classification is collected by the dust collector 5 (fine powder collection process), and the coarse particles obtained by the cooling classification are introduced into the grinding apparatus 7 (pulverization process) and pulverized to a predetermined particle size. Then recovered.
- the fine powder and the pulverized product collected in this way can be used as they are, but usually they are mixed by the mixing device 7 and shipped as a cement or concrete mixed product.
- fly ash raw powder The fly ash raw powder to be subjected to the above-described reforming treatment is a general fly ash generated in a facility for burning coal such as a coal-fired power plant.
- Such fly ash raw powder may be fly ash generated by co-firing coal, fuel other than coal, or other combustible waste.
- the maximum diameter of the particles contained in the fly ash raw powder is usually smaller than 150 ⁇ m and 100 ⁇ m or more.
- Such fly ash raw powder generally contains unburned carbon in an amount of about 1 to 15% by mass.
- a problem arises when fly ash is used as a cement or concrete mixed material (hereinafter sometimes simply referred to as a mixed material).
- unburned carbon may float on the surface of mortar or concrete, and there exists a possibility that a black part may generate
- chemicals such as chemical admixtures mixed with fly ash may be adsorbed on unburned carbon, and the function of the chemicals may be impaired.
- the present invention is particularly applicable to the modification of fly ash with an unburned carbon content exceeding 3% by mass, particularly fly ash exceeding 5% by mass.
- Heating step Said fly ash raw powder is introduce
- heating is performed so that the amount of unburned carbon after heating is usually less than 3% by mass, preferably 1% by mass or less, and particularly preferably 0.1% by mass or less.
- the measuring method of the amount of unburned carbon which fly ash contains is well-known, for example, the following method is known.
- A a method of detecting infrared rays of CO 2 ⁇ CO gas generated by combustion
- B a method of measuring the loss on ignition and estimating the amount of unburned carbon from the ignition raw material
- C a method of calculation based on the methylene blue adsorption amount
- D Method by density specific gravity test
- E A method of estimating the amount of unburned carbon by irradiating microwaves; Therefore, the amount of unburned carbon in the fly ash raw powder introduced into the heating device 1 and the fly ash (modified fly ash) heated at the outlet portion of the heating device 1 is measured by sampling appropriately as described above. Based on these measured values, the heating temperature and the heating time are set.
- the heating temperature by the heating device 1 is set in the range of 780 to 1000 ° C., preferably 800 to 950 ° C.
- the heating temperature is lower than the above range, it takes a long time to reduce the amount of unburned carbon to a predetermined range, and the efficiency is lowered.
- the fusion of fly ash particles becomes an extremely large lump, resulting in inconvenience such as clogging in piping or the like, and fusion to the wall surface of the heating device 1. End up.
- chemical modification of fly ash progresses, making it difficult to use as a mixed material.
- melting of the particles of fly ash arises, and it is inevitably large lump particles simultaneously with fine powder, for example, the largest diameter is 150 micrometers or more Large particles are produced. Since the maximum diameter of the particles contained in the fly ash subjected to heating is smaller than 150 ⁇ m, it can be confirmed that such massive particles are generated by this heating. That is, the higher the heating temperature and the longer the heating time, the more the agglomeration progresses, and more large agglomerated particles are generated. For this reason, in the present invention, cooling classification to be described later is required.
- the amount of unburned carbon is reduced within the above-mentioned range, the amount of large massive particles having a maximum diameter of 150 ⁇ m or more does not exceed 50% by mass, particularly 30% by mass. It is preferable to set the heating temperature and time so as not to exceed.
- a general heating furnace can be used as the heating apparatus 1 used for the heating as described above.
- a swirling airflow type firing furnace or the like is preferably used.
- an external heating type rotary kiln is most preferable because it can easily control the temperature in the range of 780 ° C. to 1000 ° C. and can be continuously processed in a large amount.
- a rotary kiln is used, agglomeration is likely to occur compared to other heating methods, but the effectiveness of applying the method of the present invention is high.
- Cooling classification step the heat treated fly ash in which the amount of unburned carbon is reduced by the heating as described above is introduced into the cooling classifier 3 at a high temperature. That is, the reformed fly ash lump from the heating device 1 is naturally cooled in the pipe or the like while containing fine powder, but is introduced into the cooling and classifying device 3 in a high temperature state. Classified into powder and coarse particles. That is, since the heat-treated fly ash is not heated and held, a temperature drop of about several tens of degrees Celsius to 300 degrees Celsius occurs in the pipe to the cooling classifier 3, but is kept at a high temperature of at least 300 degrees Celsius or higher.
- the fine powder and coarse particles are separated in the cooling classifier 3 in such a high temperature state. Cooling is performed.
- the heat-treated fly ash contains coarse particles that are difficult to cool as described later, it takes a very long time to reach a temperature lower than 300 ° C. by natural cooling, and in the present invention, such a low temperature is obtained. Without waiting for this, it cools intensively while separating coarse particles that are difficult to cool. If the transport efficiency from the heating device 1 to the cooling classifying device 3 is increased, the temperature drop is less likely to occur.
- the heat treatment fly ash at the time when it is introduced into the cooling classifier 3 is transported at such an efficiency that it is preferably 400 ° C. or higher, more preferably 500 ° C. or higher, particularly preferably 550 ° C. or higher.
- the heat-treated fly ash discharged from the heating device 1 coexists with fine powder having a large specific surface area and massive particles having a small specific surface area. Then, it is necessary to continue to cool the whole until some of the hard-to-cool massive particles are completely cooled, the cooling efficiency is poor, and cooling takes a very long time. That is, in the present invention, by separating coarse particles containing a lot of massive particles having poor cooling efficiency and fine powders having a large specific surface area and good cooling efficiency, the coarse particles are intensively cooled, thereby efficiently. Cooling can be performed.
- the cooling classification device 3 performs classification by wind classification, but has a structure in which cooling is performed by an airflow used for classification.
- this apparatus 3 is a hollow cylindrical body, and the bottom wall portion is an inclined wall whose diameter is increased from below to above.
- the inclined wall is connected to a straight straight body portion, and the straight body portion is connected to an upper top wall.
- the top wall portion has a shape of an inclined wall whose diameter is reduced upward.
- an airflow inlet 11 for introducing a cooling airflow is formed in the bottom wall portion, and a raw material inlet 13 is provided in the upper portion of the straight body portion.
- a fine powder outlet 15 that also functions as an air flow outlet is formed on the top wall.
- a coarse grain outlet 17 is provided in the straight body portion, and the inner space of the hollow cylindrical body is partitioned by a dispersion plate 19 in the vicinity of the boundary portion between the straight body portion and the bottom wall portion. It has been.
- a watering nozzle 21 is provided on the upper wall.
- a gas for cooling classification (usually air) is introduced from the air flow inlet 11, and ascending air flow Z of the cooling gas is formed in the apparatus 3 as shown in FIG.
- the dispersion plate 19 has a large number of small holes uniformly distributed, and the upward airflow Z is introduced through the dispersion plate 19 without being drifted.
- the above-described heat-treated fly ash is maintained at a high temperature of, for example, 480 ° C. or higher, and such a high-temperature heat-treated fly ash is introduced from the raw material inlet 13 and the ascending airflow Z passing through the dispersion plate 19. In this way, cooling and classification are performed. That is, of the heat-treated fly ash charged from the raw material charging port 13, the lighter fine powder rides on the ascending current Z and is discharged from the discharge port 15 while being cooled. On the other hand, the heavy coarse particles accumulate on the dispersion plate 19 and stay in the apparatus 3. When the amount exceeds a certain amount, the coarse particles overflow and are discharged from the coarse powder outlet 17.
- the fine powder that is easy to cool is discharged by the ascending air flow Z while being cooled by the ascending air flow Z, but the coarse particles that are difficult to cool are: It separates from the fine powder, stays in the apparatus 3, and is continuously exposed to the rising airflow Z and cooled. Therefore, cooling can be performed efficiently and in a short time.
- a machine-conveying cooling device if cooling is performed in a state where fine grains and coarse grains are mixed, conditions suitable for coarse grains that are difficult to be cooled must be used.
- the fine powder having a small diameter moves to the upper layer portion in the apparatus 3 and is discharged to the outside of the apparatus 3 in a relatively short time.
- the cooling classification device 3 used in the present invention is direct cooling with high cooling efficiency, and by introducing the air flow Z uniformly into the device and fluidizing the particles, the contact area between the particles and the gas is increased. Therefore, the size of the apparatus can be reduced. Furthermore, in said apparatus 3, a reforming process of fly ash can be simplified by performing classification simultaneously with cooling.
- fine powder and coarse particles as described above are cooled to 200 ° C. or less, particularly 100 ° C. or less, respectively. This is advantageous.
- the amount of water spray can be about 1 to 100 L per ton of fly ash.
- the temperature of the recovered fly ash is set to 200 ° C. or lower, preferably 150 ° C. or lower, particularly preferably 100 ° C. or lower.
- the classification point depends on the gas flow rate and the flow velocity, and the flow rate increases, and the faster the flow velocity, the larger the classification point. Large particles can be discharged. Therefore, a classification point is set using this.
- the classification point by the classification device 3 is not particularly limited, but for example, the fly ash JIS standard defines a 45 ⁇ m sieve residue, so it is preferable to set the 45 ⁇ m sieve residue as a target. Specifically, it is preferable to set the classification point so that the 45 ⁇ m sieve residue in the fine particles is 34% by mass or less and 20% by mass or less.
- the fly ash specified by the JIS standard the most general JIS type II standard has a 45 ⁇ m sieve residue of 40% by mass or less, but in the present invention, 34% by mass or less is not limited to JIS.
- the purpose is to conform to foreign fly ash standards at the same time. (For example, in the United States, Taiwan, and India, the 45 ⁇ m sieve residue is 34 mass% or less.)
- the fly ash used in the mixed material has a cumulative volume 50% diameter D 50 (median diameter) of 10 to 40 ⁇ m, and can have a median diameter equivalent to this.
- the recovery rate of the fine powder and coarse particles varies depending on the degree of sintering of the particles of the heat-treated fly ash to be charged, but generally the coarse particles are 50 mass% or less.
- the median diameter D 50 of the above example are measured by a laser diffraction particle size distribution meter.
- the fine fly ash powder separated and cooled by classification in the cooling classifier 3 is a modified fly ash in which the amount of unburned carbon is reduced by heat treatment, and is collected by the dust collector 5.
- the dust collector 5 used for collecting such fine powder there is no particular problem as long as it is industrially used such as an electric dust collector, a bag filter, a cyclone or the like.
- the fine powder collected by the dust collector 5 can be used as a mixed material as it is.
- Coarse grain crushing step The coarse particles taken out from the apparatus 3 due to overflow in the cooling classifier 3 can be used as it is for a cement clinker production raw material or the like, but are used as a cement or concrete mixture. Needs to be crushed. This is because the particle size is remarkably coarse, and there are many cases including huge massive particles exceeding several centimeters to several tens of centimeters. For this reason, it grind
- the pulverizer is not particularly limited, and industrially used tube mills, vibration mills, roller mills, roll crushers, hammer crushers, and the like can be used.
- the fine powder recovered from the dust collector 5 and the coarsely pulverized product recovered from the pulverizer can all be used as modified fly ash as a mixed material of cement or concrete, but unburned. From the viewpoint of the uniformity of the quality of the modified fly ash in which the amount of carbon is greatly reduced, it is preferable to introduce both into the mixing device 9 and mix them into a product.
- Such a mixing device 9 is not particularly limited, and a mixing device used for general powder mixing can be used.
- a stirring mixer or a jet mixer using compressed air is used. It can also be mixed in blending silos, continuous powder transporters, and pneumatic feeders.
- the modified fly ash thus obtained has a reduced amount of unburned carbon and is adjusted to an appropriate fineness, and is used as a cement mixed material or a concrete mixed material by a known method.
- Heating device 3 Cooling and classifying device 5: Dust collector 7: Crushing device 9: Mixing device 11: Gas inlet 13: Raw material inlet 15: Fine powder outlet 17: Coarse grain outlet 19: Dispersion plate 21: Watering nozzle
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Abstract
Description
未燃カーボンを含むフライアッシュ原粉を780~1000℃の温度に加熱して該フライアッシュ原粉に含まれる未燃カーボン量を低減させる加熱工程;
前記加熱工程で得られた未燃カーボン量が低減された熱処理フライアッシュを冷却分級装置に導入して細粉と粗粉とに分離する冷却分級工程;
を含み、
前記冷却分級工程において使用される冷却分級装置は、下方から分級用気流を導入し、該装置内に導入された冷却分級用気流を上方から排出する基本構造を有しており、
前記冷却分級装置内に投入された前記熱処理フライアッシュを、前記冷却分級用気流と接触させ、該熱処理フライアッシュに含まれる細粉を上昇させて装置外に排出させ且つ該熱処理フライアッシュに含まれる粗粒を装置内に滞留させることにより、細粉と粗粒との分離及び冷却とを行い、
前記冷却分級装置から排出された前記細粉は、集塵装置を用いて回収し、前記粗粒は、該冷却分級装置から回収することを特徴とするフライアッシュの改質方法が提供される。
(1)前記冷却分級装置内での分級を、散水下で行うこと。
(2)前記加熱工程により、未燃カーボン量を3質量%未満に低減させること。
(3)前記加熱工程での加熱を、未燃カーボン量が低減された熱処理フライアッシュ中に含まれる最大直径が150μm以上の塊状粒子の含有量が50質量%を超えないように行うこと。
(4)前記冷却分級工程において、分級により得られる前記細粉の45μmふるい残分が34質量%以下となるように分級点を設定すること。
(5)前記冷却分級工程において、分級により得られる粗粒は、45μmふるい残分が34質量%以下となるまで粉砕すること。
(6)前記集塵装置から回収された細粉と、前記粗粒を粉砕して得られた粉砕粉末とを混合すること。
上述した改質処理に供するフライアッシュ原粉は、石炭火力発電所などの石炭を燃焼する設備において発生する一般的なフライアッシュである。かかるフライアッシュ原粉は、石炭や、石炭以外の燃料、その他可燃系廃棄物が混焼されて発生したフライアッシュであってもよい。
また、このフライアッシュ原粉に含まれる粒子の最大直径は、通常、150μmよりも小さく、100μm以上である。
本発明は、特に、未燃カーボン量が3質量%を超えるフライアッシュ、特に5質量%を超えるフライアッシュの改質に適用される。
上記のフライアッシュ原粉は、加熱装置1に導入され、加熱によって、未燃カーボンを燃焼させて、その量を低減させる。例えば、加熱後の未燃カーボン量が通常3質量%未満、好ましくは1質量%以下、特に好ましくは0.1質量%以下となるように加熱が行われる。
(a)燃焼させて発生したCO2・COガスを赤外線検出する方法;
(b)強熱減量を測定し、該強熱原料から未燃カーボン量を推定する方法;
(c)メチレンブルー吸着量に基づいて算出する方法;
(d)密かさ比重試験による方法;
(e)マイクロ波を照射して未燃カーボン量を推定する方法;
従って、適宜サンプリングして、上記の方法により、加熱装置1に導入されるフライアッシュ原粉及び加熱装置1の出口部分で加熱されたフライアッシュ(改質フライアッシュ)の未燃カーボン量を測定し、これらの測定値に基づいて、加熱温度や加熱時間が設定される。
尚、加熱温度が上記範囲よりも低温である場合には、未燃カーボン量が所定の範囲まで低減するのに長時間要し、効率が低下する。また、上記温度よりも高温に加熱すると、フライアッシュの粒子同士の融着が極端に大きな塊状物となり、配管等での詰まりが生じたり、加熱装置1の壁面に融着するなどの不都合を生じてしまう。また、フライアッシュの化学的変質が進み、混合材として使用しがたくなることもある。
本発明では、上記のような加熱によって未燃カーボン量が低減された熱処理フライアッシュを、高温の状態で冷却分級装置3に導入する。即ち、加熱装置1から出た改質フライアッシュの塊状物は、細粉を含んだまま、配管内等での自然冷却はされるものの、高温状態のまま、冷却分級装置3に導入され、細粉と粗粒とに分級される。即ち、熱処理フライアッシュは加熱保持されているわけではないので、冷却分級装置3までの配管内で数十℃~300℃程度の温度降下を生じるが、少なくとも300℃以上の高温に保持されており、このような高温状態のまま、この冷却分級装置3で、塊状物に含まれる細粉と粗粒(粒径の大きき塊状粒子を含む)とに分離し、同時に、細粉及び粗粒の冷却を行うわけである。換言すれば、熱処理フライアッシュは後述するような冷却されにくい粗粒を含むため、自然冷却で300℃を下回る温度となるには極めて長い時間が必要であり、本発明においては、このような低温になるのを待たずに、冷えにくい粗粒を分離しながら重点的に冷却するものである。加熱装置1から冷却分級装置3への輸送効率を高くすると、上記温度低下は起きにくくなる。その観点から、冷却分級装置3に導入される時点での熱処理フライアッシュの温度が、好ましくは400℃以上、より好ましくは500℃以上、特に好ましくは550℃以上であるような効率で輸送する。
分級せずに冷却を先に行うと、加熱装置1から排出された熱処理フライアッシュは、比表面積の大きい細粉と比表面積の小さい塊状粒子が共存しているため、全体を所定温度まで冷却しようとすると、一部の冷えにくい塊状粒子が冷め切るまで全体を冷却しつづける必要があり、冷却効率が悪く、冷却に著しく長時間かかってしまう。即ち、本発明では、冷却効率の悪い塊状粒子を多く含む粗粒と、比表面積が大きくて冷却効率の良好な細粉とを分離しながら、粗粒を重点的に冷却することにより、効率よく、冷却を行うことができる。
ところで、上記の分散板19は、多数の小さな孔が多数均一に分布しているものであり、この分散板19を通って、偏流せずに上昇気流Zが導入されることとなる。
例えば、機械搬送式の冷却装置では、細粒と粗粒とが入り混じった状態で冷却しようとすると、冷却されにくい粗粒に合わせた条件を用いなければならない。しかしながら、上記のような冷却分級装置3では、径の小さい細粉は装置3内の上層部に移動して比較的短時間で装置3外に排出され、径が大きい粗粒は、粒子は装置3内の下層部へ移動して比較的長時間装置内に滞在した後に排出されるため、細粉の冷却と粗粒の冷却とに必要なだけの冷却時間を容易に確保することができ、効率よく冷却を行うことができる。
また、機械搬送式の冷却装置の多くは間接冷却であるため、冷却効率が悪く、伝熱面積を多くするために、装置が大型化してしまう。しかるに、本発明で使用する冷却分級装置3は、冷却効率の高い直接冷却であり、しかも装置内に一様に気流Zを導入して粒子を流動化することにより、粒子と気体との接触面積が大きくなるため、装置の小型化を図ることができる。
さらに、上記の装置3では、冷却と同時に分級を行うことで、フライアッシュの改質工程を簡素化することができる。
上記冷却により、回収されるフライアッシュの温度を200℃以下、好ましくは150℃以下、特に好ましくは100℃以下にする。
尚、上記のメディアン径D50は、例えばレーザー回折式粒度分布計よって測定される。
冷却分級装置3での分級により分離され且つ冷却されているフライアッシュの細粉は、熱処理によって未燃カーボン量が低減された改質フライアッシュであり、集塵装置5により回収される。
このような細粉の回収に用いる集塵装置5としては、電気集塵機、バグフィルター、サイクロン等の工業的に使用されるものであれば特に問題ない。集塵装置5で回収された細粉は、そのまま混合材として使用することが可能である。
上記の冷却分級装置3内でのオーバーフローによって該装置3から取り出された粗粒は、そのままセメントクリンカー製造原料等の用途に使用することも可能であるが、セメントやコンクリートの混合材として使用するためには、粉砕する必要がある。粒径が著しく粗大であり、しかも数cm~十数cmを超えるような巨大な塊状粒子を含んでいる場合が多いからである。このため、前述した細粉と同様、45μmふるい残分が34質量%以下、特に20質量%以下となるまで粉砕する。このとき、粉砕後のメディアン径D50は30μm以下、特に20μm以下となっていることが好ましい。
集塵装置5から回収された細粉や、粉砕装置から回収された粗粒の粉砕物は、何れも改質フライアッシュとして、そのままセメントやコンクリートの混合材として使用することもできるが、未燃カーボン量が大幅に減じられている改質フライアッシュの品質の均一性という点で、両者を混合装置9に導入して混合して製品とすることが好ましい。
3:冷却分級装置
5:集塵装置
7:粉砕装置
9:混合装置
11:気体導入口
13:原料投入口
15:細粉取出口
17:粗粒取出口
19:分散板
21:散水ノズル
Claims (7)
- 未燃カーボンを含むフライアッシュ原粉を780~1000℃の温度に加熱して該フライアッシュ原粉に含まれる未燃カーボン量を低減させる加熱工程;
前記加熱工程で得られた未燃カーボン量が低減された熱処理フライアッシュを冷却分級装置に導入して細粉と粗粉とに分離する冷却分級工程;
を含み、
前記冷却分級工程において使用される冷却分級装置は、下方から分級用気流を導入し、該装置内に導入された冷却分級用気流を上方から排出する基本構造を有しており、
前記冷却分級装置内に投入された前記熱処理フライアッシュを、前記冷却分級用気流と接触させ、該熱処理フライアッシュに含まれる細粉を上昇させて装置外に排出させ且つ該熱処理フライアッシュに含まれる粗粒を装置内に滞留させることにより、細粉と粗粒との分離及び冷却とを行い、
前記冷却分級装置から排出された前記細粉は、集塵装置を用いて回収し、前記粗粒は、該冷却分級装置から回収することを特徴とするフライアッシュの改質方法。 - 前記冷却分級装置内での分級を、散水下で行う請求項1に記載のフライアッシュの改質方法。
- 前記加熱工程により、未燃カーボン量を3質量%未満に低減させる、請求項1に記載のフライアッシュの改質方法。
- 前記加熱工程での加熱を、未燃カーボン量が低減された熱処理フライアッシュ中に含まれる最大直径が150μm以上の塊状粒子の含有量が50質量%を超えないように行う、請求項3に記載のフライアッシュの改質方法。
- 前記冷却分級工程において、分級により得られる前記細粉の45μmふるい残分が34質量%以下となるように分級点を設定する請求項1に記載のフライアッシュの改質方法。
- 前記冷却分級工程において、分級により得られる粗粒は、45μmふるい残分が34質量%以下となるまで粉砕する請求項5に記載のフライアッシュの改質方法。
- 前記集塵装置から回収された細粉と、前記粗粒を粉砕して得られた粉砕粉末とを混合する、請求項6に記載のフライアッシュの改質方法。
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JP2020508234A JP7183251B2 (ja) | 2018-03-19 | 2019-03-11 | フライアッシュの改質方法 |
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US16/978,623 US20210032163A1 (en) | 2018-03-19 | 2019-03-11 | Process for reforming the fly ash |
EP19771265.6A EP3770133A1 (en) | 2018-03-19 | 2019-03-11 | Fly ash modification method |
CN201980019488.3A CN111971259A (zh) | 2018-03-19 | 2019-03-11 | 飞灰的改性方法 |
CA3093644A CA3093644A1 (en) | 2018-03-19 | 2019-03-11 | Process for reforming the fly ash |
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2019
- 2019-03-11 US US16/978,623 patent/US20210032163A1/en not_active Abandoned
- 2019-03-11 CN CN201980019488.3A patent/CN111971259A/zh not_active Withdrawn
- 2019-03-11 EP EP19771265.6A patent/EP3770133A1/en not_active Withdrawn
- 2019-03-11 KR KR1020207026694A patent/KR20200130313A/ko unknown
- 2019-03-11 CA CA3093644A patent/CA3093644A1/en not_active Abandoned
- 2019-03-11 JP JP2020508234A patent/JP7183251B2/ja active Active
- 2019-03-11 WO PCT/JP2019/009767 patent/WO2019181619A1/ja unknown
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Also Published As
Publication number | Publication date |
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CA3093644A1 (en) | 2019-09-26 |
JPWO2019181619A1 (ja) | 2021-04-08 |
EP3770133A1 (en) | 2021-01-27 |
US20210032163A1 (en) | 2021-02-04 |
CN111971259A (zh) | 2020-11-20 |
JP7183251B2 (ja) | 2022-12-05 |
KR20200130313A (ko) | 2020-11-18 |
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