WO2012105102A1 - PROCÉDÉ POUR PRODUIRE β-2CAO·SIO2 - Google Patents

PROCÉDÉ POUR PRODUIRE β-2CAO·SIO2 Download PDF

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Publication number
WO2012105102A1
WO2012105102A1 PCT/JP2011/076113 JP2011076113W WO2012105102A1 WO 2012105102 A1 WO2012105102 A1 WO 2012105102A1 JP 2011076113 W JP2011076113 W JP 2011076113W WO 2012105102 A1 WO2012105102 A1 WO 2012105102A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
sio
brick
raw material
mortar
Prior art date
Application number
PCT/JP2011/076113
Other languages
English (en)
Japanese (ja)
Inventor
樋口　隆行
茂 富岡
渡辺　晃
山本　賢司
盛岡　実
慎 庄司
Original Assignee
電気化学工業株式会社
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
Application filed by 電気化学工業株式会社 filed Critical 電気化学工業株式会社
Priority to JP2012555690A priority Critical patent/JP5867734B2/ja
Priority to CN201180065734.2A priority patent/CN103328383B/zh
Publication of WO2012105102A1 publication Critical patent/WO2012105102A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/24—Alkaline-earth metal silicates
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/043—Alkaline-earth metal silicates, e.g. wollastonite
    • 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
    • C04B18/02—Agglomerated materials, e.g. artificial aggregates
    • C04B18/023—Fired or melted materials

Definitions

  • the present invention mainly relates to a method for producing ⁇ -2CaO ⁇ SiO 2 that can be appropriately used as a cement admixture.
  • Non-patent Document 1 Non-Patent Document 2 and Non-Patent Document 3).
  • An object of the present invention is to provide a process for producing ⁇ -2CaO ⁇ SiO 2 which has high whiteness, does not contain harmful substances, and does not inhibit the setting and hardening of cement.
  • the present inventors have selected a specific raw material, granulated one having a specific particle size, and fired with a rotary kiln using a specific brick or specific mortar as a firing zone, It was found that ⁇ -2CaO.SiO 2 was easily formed. That is, the present invention is mainly composed of CaO and SiO 2 , the CaO / SiO 2 molar ratio is 1.8 to 2.2, and after heating at 1000 ° C., the total of Al 2 O 3 and Fe 2 O 3 A raw material having a content of less than 5% by mass and a total content of boron, phosphorus, barium, strontium, and molybdenum of less than 0.5% by mass in terms of oxide is selected.
  • a granulated raw material having a 150 ⁇ m sieve under 90% by mass that is, a granulated raw material having a 150 ⁇ m sieve under 90% by mass, and the granulated raw material is 45 to 80% by mass of Al 2 O 3 and 20 to 55% of SiO 2 in the firing zone.
  • ⁇ -2CaO ⁇ SiO 2 of the manufacturing method of the present invention high whiteness, toxic substances not contain, continuously manufactured easily ⁇ -2CaO ⁇ SiO 2 nor inhibit also condensation curing of the cement It becomes possible to do.
  • ⁇ -2CaO ⁇ SiO 2 referred to in the present invention is a kind of so-called dicalcium silicate (2CaO ⁇ SiO 2 ) among compounds mainly composed of CaO and SiO 2 .
  • dicalcium silicate 2CaO ⁇ SiO 2
  • a CaO raw material and a SiO 2 raw material are used as main components.
  • the main component preferably means that the total content of CaO and SiO 2 in the raw material is preferably 80% or more, more preferably 90% or more, and the content of other components is as low as possible.
  • the CaO raw material calcium carbonate, calcium hydroxide, calcium oxide, or the like can be used.
  • the SiO 2 raw material can be selected quartzite powder, clay, silica fume, fly ash, amorphous silica, etc., and materials of siliceous by-produced from each industry. However, in the present invention, it is necessary to limit the presence of impurities.
  • the total of Al 2 O 3 and Fe 2 O 3 mixed from the CaO raw material and the SiO 2 raw material needs to be less than 5% in the raw material after heating at 1000 ° C.
  • the total of Al 2 O 3 and Fe 2 O 3 is more preferably less than 4%, and most preferably less than 3%.
  • the content of Fe 2 O 3 is preferably less than 2%, more preferably less than 1.5%, and most preferably less than 1% in the raw material after heating at 1000 ° C. .
  • the total content of boron, phosphorus, barium, strontium, and molybdenum is preferably less than 0.5% in terms of oxide, and more preferably 0.3% or less. If it is not within the above range, it may be undesirable from the viewpoint of whiteness, inclusion of harmful substances, and inhibition of cement hardening.
  • the blending ratio of the CaO raw material and the SiO 2 raw material must be adjusted so that the CaO / SiO 2 molar ratio in the raw material is 1.8 to 2.2.
  • the CaO / SiO 2 molar ratio of the raw material is less than 1.8, ⁇ -type wollastonite is produced as a by-product, and the content of ⁇ -2CaO ⁇ SiO 2 in the product becomes low.
  • the CaO / SiO 2 molar ratio of the raw material exceeds 2.2, 3CaO ⁇ SiO 2 and free lime are by-produced, and the content of ⁇ -2CaO ⁇ SiO 2 in the product is also lowered.
  • the raw material CaO / SiO 2 molar ratio is preferably 1.8 to 2.2, more preferably 1.9 to 2.1.
  • the particle size of the CaO raw material and the SiO 2 raw material needs to be adjusted so that the 150 ⁇ m passage rate is 90% or more, that is, the 150 ⁇ m sieve is 90% or more, and the 100 ⁇ m passage rate is 90% or more, that is, 100 ⁇ m. It is more preferable to prepare so that the sieve bottom is 90% or more. If the particle size of the raw material is not fine within the above range, the purity of ⁇ -2CaO ⁇ SiO 2 will be deteriorated. Specifically, free lime and insoluble residue tend to increase.
  • the amount of water used is less than 10%, the granulated raw material tends to collapse, and the firing reaction may not sufficiently proceed during firing in the rotary kiln. Moreover, when the usage-amount of water exceeds 30%, the granulated raw material will become watery, and after all, it will become easy to collapse
  • the granulated raw material is fired in a rotary kiln.
  • the temperature needs to be fired at a baking point temperature of 1350 to 1600 ° C., preferably 1375 to 1550 ° C., more preferably 1400 to 1500 ° C.
  • the burning point temperature is less than 1350 ° C.
  • the purity of ⁇ -2CaO ⁇ SiO 2 is deteriorated. Specifically, free lime and insoluble residue tend to increase.
  • the baking point temperature exceeds 1600 ° C., it may melt and the coating will adhere to the kiln, making it difficult to operate, or mixing of ⁇ -2CaO ⁇ SiO 2 may become significant.
  • the firing energy is large and it is uneconomical.
  • the burning point temperature said by this invention means the highest temperature in a kiln. Usually, the highest temperature in the kiln is near the front of the flame (flame shape) extending from the burner.
  • the material of bricks and mortar used for the rotary kiln firing zone is important.
  • at least one brick or mortar selected from the group consisting of the following (1) to (4) is used.
  • the content of Al 2 O 3 is 45 to 80%, preferably 55 to 70%
  • the content of SiO 2 is 20 to 55%, Preferably 30-45% silica-alumina brick.
  • magnesia bricks defined in JIS R 2302 magnesia bricks having a MgO content of 85% or more, preferably 90% or more.
  • the production rate of ⁇ -2CaO ⁇ SiO 2 may be lowered, or the brick may melt and react with the raw material to produce a coating.
  • the shape and thickness of the brick are not particularly limited, and it is desirable to select an appropriate size according to the rotary kiln diameter.
  • the Al 2 O 3 content is 25 to 80%, preferably 35 to 70%
  • the SiO 2 content is 20-75%, preferably 30-65% silica-alumina mortar.
  • the mortar when used for the firing zone, it is preferable that these mortars are applied to the surface of the brick of the firing zone of the rotary kiln.
  • the use conditions of the mortar to be applied are not particularly limited, but the thickness of the mortar is usually 5 to 10 mm, preferably 6 to 9 mm.
  • the amount of water used for coating varies depending on the type of mortar, but is preferably 15 to 35% with respect to the mortar component. In particular, the amount of water used for coating is preferably 30 to 35% for silica-alumina mortar and 15 to 20% for magnesia mortar. Outside the above range, the content of ⁇ -2CaO.SiO 2 may be low, or the brick may melt and react with the raw material to generate a coating.
  • both bricks and mortar are for a cement rotary kiln and are chromium-free.
  • a cooling operation is performed after firing, but the cooling conditions are not particularly limited, and a special rapid cooling operation may be omitted. Specifically, it may be a method according to the general cooling conditions of Portland cement clinker, and after firing with a rotary kiln, it may be cooled through a cooler or the like in an atmospheric environment.
  • the heat treatment method is not particularly limited, and a rotary kiln, electric furnace, tunnel furnace, shaft kiln, fluidized bed incinerator or the like can be used.
  • Example 1 The following CaO raw material, SiO 2 raw material, Al 2 O 3 component, and Fe 2 O 3 component are blended using a vibration pot mill (manufactured by Chuo Kako Co., Ltd.), and the CaO / SiO 2 molar ratio as shown in Table 1 Of 2.0, and various raw materials having different Al 2 O 3 content after heating at 1000 ° C. and Fe 2 O 3 content were prepared.
  • the rotary kiln used in the experimental example of the present invention has a cylindrical shape with an inner diameter of 1 m and a length of 20 m, and the refractory on the inner surface of the rotary kiln firing zone is brick (thickness 120 mm) or mortar (thickness) on the brick surface. 7 mm).
  • ⁇ Material of firing zone material of refractory on the inner surface of firing zone>
  • Firing zone material (3) Magnesia refractory mortar (manufactured by Yotai Co., trade name Yotai Heatset M, maximum particle size 0.6 mm) on the inner surface of the brick of (1) above, with a water / mortar mass ratio of 0 .17, applied with a thickness of 7 mm.
  • CaO raw material Limestone fine powder. CaO is 55.4%, MgO is 0.37%, Al 2 O 3 is 0.05%, Fe 2 O 3 is 0.02%, and SiO 2 is 0.10%. C) was 43.57%, and no carbon content was detected. 150 ⁇ m passage rate; 97.0%, 100 ⁇ m passage rate; 91.9%. SiO 2 raw material: silica fine powder. CaO 0.02%, MgO 0.04%, Al 2 O 3 2.71%, Fe 2 O 3 0.27%, SiO 2 95.83%, and TiO 2 0.23% No carbon content is detected.
  • Example 2 The raw material CaO / SiO 2 molar ratio is fixed at 2.0, the Fe 2 O 3 content is fixed at 0.3%, and the Al 2 O 3 content is fixed at 1.4%. The procedure was the same as in Experimental Example 1 except that the above was changed. The results are shown in Table 2.
  • Firing zone material (5) Silica-alumina brick (commercially available) having an Al 2 O 3 content of 45% and an SiO 2 content of 55%.
  • Firing zone material (6) Silica-alumina brick (commercially available) having an Al 2 O 3 content of 80% and an SiO 2 content of 20%.
  • Firing zone material (7) Magnesia brick with 85% MgO content (commercially available).
  • Firing zone material (8) Magnesia brick with 95% MgO content (commercially available).
  • Firing zone material (11) Magnesia-spinel refractory mortar (trade name: Yawtai Heatset M, maximum particle size: 0.6 mm) manufactured on the inner surface of the brick of (1) above, with water / mortar mass ratio Is 0.17 and applied with a thickness of 7 mm.
  • Al45 means the material of the fired zone with an Al 2 O 3 content of 45%
  • Mg85 means the fired zone with an MgO content of 85%. Means the material.
  • the other examples are similar examples.
  • Example 6 The experiment was performed in the same manner as in Experimental Example 1 except that the water ratio during granulation was changed as shown in Table 6. The results are shown in Table 6.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

La présente invention concerne un procédé pour produire β-2CaO·SiO2, comprenant : le choix d'une matière première qui comprend CaO et SiO2 en tant que composants principaux et a un rapport molaire CaO/SiO2 de 1,8 à 2,2 et qui, après avoir été chauffée à 1000 °C, présente une teneur totale de Al2O3 et Fe2O3 inférieure à 5 % en masse, et une teneur totale en bore, phosphore, baryum, strontium et molybdène inférieure à 0,5 % en masse en termes d'oxydes; la préparation, à partir de la matière première, d'un mélange dans lequel le rapport de particules traversant un tamis ayant des ouvertures de 150 μm est de 90 % en masse ou plus; la granulation du mélange; et la cuisson du mélange granulé à une température de cuisson de 1350 à 1600 °C dans un four rotatif dans lequel de la brique ou du mortier est utilisé sur la surface intérieure de la zone de cuisson. La brique ou le mortier est au moins l'un choisi dans le groupe constitué de briques de silice-alumine comprenant de 45 à 80 % en masse de Al2O3 et de 20 à 55 % en masse de SiO2, mortiers de silice-alumine comprenant de 25 à 80 % en masse de Al2O3 et de 20 à 75 % en masse de SiO2, briques de magnésie comprenant au moins 85 % en masse de MgO, et mortiers de magnésie comprenant au moins 85 % en masse de MgO.
PCT/JP2011/076113 2011-02-03 2011-11-11 PROCÉDÉ POUR PRODUIRE β-2CAO·SIO2 WO2012105102A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2012555690A JP5867734B2 (ja) 2011-02-03 2011-11-11 β−２ＣａＯ・ＳｉＯ２の製造方法
CN201180065734.2A CN103328383B (zh) 2011-02-03 2011-11-11 β-2CaO·SiO2的制造方法

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2011-021614 2011-02-03
JP2011021614 2011-02-03
JP2011-021658 2011-02-03
JP2011021658 2011-02-03
JP2011-128708 2011-06-08
JP2011128708 2011-06-08
JP2011172188 2011-08-05
JP2011-172188 2011-08-05

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WO2012105102A1 true WO2012105102A1 (fr) 2012-08-09

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CN (1) CN103328383B (fr)
WO (1) WO2012105102A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021017379A (ja) * 2019-07-18 2021-02-15 デンカ株式会社 セメント混和材、膨張材、及びセメント組成物
CN113155072A (zh) * 2021-02-09 2021-07-23 鞍钢股份有限公司 一种球团回转窑结圈料厚度的在线检测方法
JP2021147248A (ja) * 2020-03-16 2021-09-27 太平洋セメント株式会社 ビーライトクリンカ、およびその製造方法
WO2023022173A1 (fr) * 2021-08-19 2023-02-23 デンカ株式会社 Adjuvant de ciment, procédé de production d'un adjuvant de ciment et composition de ciment
WO2023063236A1 (fr) * 2021-10-13 2023-04-20 株式会社トクヤマ PROCÉDÉ DE FABRICATION D'OBJET CUIT COMPRENANT UN γ－２ＣＡＯ・ＳＩＯ２

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105712362A (zh) * 2016-04-25 2016-06-29 武汉科技大学 一种β-硅酸二钙及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4314980A (en) * 1980-02-28 1982-02-09 The United States Of America As Represented By The United States Department Of Energy Preparation of reactive beta-dicalcium silicate
JPS6217013A (ja) * 1985-07-11 1987-01-26 Onoda Cement Co Ltd γ型珪酸二石灰粉末の製造方法
JPH07291618A (ja) * 1994-04-26 1995-11-07 Sumitomo Metal Mining Co Ltd 珪酸二石灰微粉末の製造方法
JPH1036110A (ja) * 1996-07-26 1998-02-10 Inax Corp 珪酸二カルシウムの製造方法
WO2003016234A1 (fr) * 2001-08-21 2003-02-27 Denki Kagaku Kogyo Kabushiki Kaisha Adjuvant de ciment, composition de ciment, et procede destine a eliminer la carbonation au moyen de ceux-ci

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1039582C (zh) * 1994-11-30 1998-08-26 桦甸市松源水泥有限公司 早强膨胀水泥的生产方法
JPH1034110A (ja) * 1996-07-25 1998-02-10 Okawara Mfg Co Ltd ゴミの低温乾燥方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4314980A (en) * 1980-02-28 1982-02-09 The United States Of America As Represented By The United States Department Of Energy Preparation of reactive beta-dicalcium silicate
JPS6217013A (ja) * 1985-07-11 1987-01-26 Onoda Cement Co Ltd γ型珪酸二石灰粉末の製造方法
JPH07291618A (ja) * 1994-04-26 1995-11-07 Sumitomo Metal Mining Co Ltd 珪酸二石灰微粉末の製造方法
JPH1036110A (ja) * 1996-07-26 1998-02-10 Inax Corp 珪酸二カルシウムの製造方法
WO2003016234A1 (fr) * 2001-08-21 2003-02-27 Denki Kagaku Kogyo Kabushiki Kaisha Adjuvant de ciment, composition de ciment, et procede destine a eliminer la carbonation au moyen de ceux-ci

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021017379A (ja) * 2019-07-18 2021-02-15 デンカ株式会社 セメント混和材、膨張材、及びセメント組成物
JP2021147248A (ja) * 2020-03-16 2021-09-27 太平洋セメント株式会社 ビーライトクリンカ、およびその製造方法
JP7341089B2 (ja) 2020-03-16 2023-09-08 太平洋セメント株式会社 ビーライトクリンカ、およびその製造方法
CN113155072A (zh) * 2021-02-09 2021-07-23 鞍钢股份有限公司 一种球团回转窑结圈料厚度的在线检测方法
WO2023022173A1 (fr) * 2021-08-19 2023-02-23 デンカ株式会社 Adjuvant de ciment, procédé de production d'un adjuvant de ciment et composition de ciment
WO2023063236A1 (fr) * 2021-10-13 2023-04-20 株式会社トクヤマ PROCÉDÉ DE FABRICATION D'OBJET CUIT COMPRENANT UN γ－２ＣＡＯ・ＳＩＯ２

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CN103328383B (zh) 2015-05-27
JP5867734B2 (ja) 2016-02-24
CN103328383A (zh) 2013-09-25
JPWO2012105102A1 (ja) 2014-07-03

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