WO2007129752A1 - Procédé de fabrication de ciment alumineux et matériaux réfractaires non façonnés - Google Patents

Procédé de fabrication de ciment alumineux et matériaux réfractaires non façonnés Download PDF

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Publication number
WO2007129752A1
WO2007129752A1 PCT/JP2007/059673 JP2007059673W WO2007129752A1 WO 2007129752 A1 WO2007129752 A1 WO 2007129752A1 JP 2007059673 W JP2007059673 W JP 2007059673W WO 2007129752 A1 WO2007129752 A1 WO 2007129752A1
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WO
WIPO (PCT)
Prior art keywords
alumina cement
cao
slag
twenty
source
Prior art date
Application number
PCT/JP2007/059673
Other languages
English (en)
Japanese (ja)
Inventor
Masateru Umika
Atsunori Koyama
Yuji Koga
Kazuhito Kushihashi
Hirotomo Sakai
Original Assignee
Denki Kagaku Kogyo Kabushiki Kaisha
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 Denki Kagaku Kogyo Kabushiki Kaisha filed Critical Denki Kagaku Kogyo Kabushiki Kaisha
Publication of WO2007129752A1 publication Critical patent/WO2007129752A1/fr

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Classifications

    • 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
    • C04B7/32—Aluminous cements
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Definitions

  • the present invention uses slag, which is industrial waste, and a CaO source and a Z or Al 2 O source as raw materials.
  • the present invention relates to an alumina cement manufacturing method and an amorphous refractory using the same.
  • Alumina cement generally uses limestone or quicklime as a CaO raw material, and Al O raw material.
  • Non-Patent Document 1 Using purified alumina, bauxite, aluminum residual ash, etc., pulverizing clinker (Clinker) produced by firing or melting method alone, or adding alumina and various additives to clinker. And mixed and pulverized.
  • a general method for producing alumina cement and its characteristics are widely known (for example, Non-Patent Document 1).
  • Alumina cement made from this slag is produced by the formation of MgO-AlO.
  • Non-Patent Document 1 Refractory Vol. 29, pp368-374, 1977
  • an object of the present invention is to contain a large amount of industrial waste, CaO and AlO.
  • the purpose is to provide a method for producing alumina cement that effectively uses the slag that it has as a raw material for alumina cement and that exhibits performance equivalent to or better than that of conventional products.
  • Another object of the present invention is to use the obtained alumina cement, which is superior to conventional products.
  • slag containing a specific amount of a specific mineral is used as a raw material, and if necessary, a mixture containing Sarako, CaO source and / or Al O source as a raw material is melted.
  • Alumina cement having the same characteristics is produced.
  • the present invention has the gist characterized by the following.
  • CaO 2 -Al 2 O hereinafter also referred to as CA
  • CaO '2A1 O hereinafter also referred to as CA 2
  • C12A7 C12A1 O
  • one or more ore minerals that are also selected as a group force that also has an amorphous force
  • a method for producing an alumina cement characterized by melting or firing a mixture with 2 3 and crushing.
  • A1 O source power The above (1) or (2) which is refined alumina, bauxite or aluminum residual ash
  • the slag is composed of MgO-Al 2 O (hereinafter also referred to as MA) and
  • the refractory aggregate is magnesia, magnesia spinel, chamotte, alumina, silicon carbide, Group power consisting of ultrafine powder, oil pitch, tar, and scaly graphite power.
  • the amorphous refractory according to (5) which is one or more kinds of refractory aggregates selected.
  • amorphous refractory according to (5) or (6) further comprising a curing retarder, a curing accelerator, or a fluidizing agent.
  • Alumina cement obtained from a raw material has a method for producing an alumina cement having characteristics that are inferior to those of existing ones in terms of various properties such as pot life, fluidity, curing characteristics, and strength development. Provided.
  • the amorphous refractory which has the characteristics which are inferior to the existing thing, such as a fluidity
  • a slurry containing a large amount of CaO and AlO used in the method for producing an alumina cement of the present invention is a slurry containing a large amount of CaO and AlO used in the method for producing an alumina cement of the present invention.
  • CA, CA2, C12A7, and the group power consisting of amorphous are selected, and slag with MA and Z or MgO content of 30% by mass or less, preferably 25% by mass or less is preferred.
  • the present inventor In order to satisfy various properties such as pot life, fluidity, curing characteristics, and strength development, the present inventor also used CA, CA2, C12A7, and amorphous cement as raw materials for alumina cement. It is preferable to use slag containing 60% by mass or more of one or more kinds of minerals, and more preferably by setting the MA and Z or MgO content in the slag to 30% by mass or less. As a result, the present invention was completed upon obtaining the knowledge that the performance was almost the same as that of the existing castable.
  • a slag containing 60% by mass or more of one or more selected minerals and containing MA and / or MgO of 30% by mass or less Used as a raw material and mixed with CaO sources such as limestone and quicklime and Al O sources such as Z or refined alumina, bauxite, and aluminum residual ash as required, at a specified component ratio.
  • the slag containing a large amount of CaO and AlO used in the present invention is not particularly limited.
  • slag generated when melting and purifying petroleum waste catalyst and reducing agent For example, slag generated when melting and purifying petroleum waste catalyst and reducing agent; spent catalytic power containing vanadium; slag generated when recovering useful metals; secondary slag generated in steel processes, etc. Is preferred.
  • transition metal oxides refer to transition metals supported in a catalyst.
  • hydrodesulfurization catalysts include Co, NI, Cu, V, Mo, Pt, and the like.
  • the spent catalyst is first oxidized and roasted, and the C, S, and N components in the waste are decomposed and removed as CO, SOx, and NOx.
  • the transition metal alloy is recovered by mixing with a reducing agent and heating. At this time, CaO— Al O
  • Type 3 slag is by-produced.
  • the used catalyst containing Ni, Mo and Z or Co and V is oxidized and roasted. Lime and Z or iron sources are added and mixed and heated to dissolve, and then a reducing agent is added to produce iron alloy containing crude Ni, Mo and Z or Co, and V-rich CaO-AlO based intermediate slag. So
  • the crude Ni, Mo and / or Co-containing iron alloy is subjected to de-P (phosphorus) and de-S (sulfurized) treatment, and Ni, Mo and / or Co having a P and S content of 0.1% by mass or less. Collect the iron alloy.
  • the V-rich intermediate slag is added with a reducing agent and stirred to reduce the V oxides in the slag. P and S Each produces a FeV alloy and CaO—AlO slag with a content of 0.1% by mass or less.
  • CaO-AlO-based slag can be obtained during fractional collection.
  • the secondary refined slag generated in the steel process is, for example, as follows.
  • the mineral composition is C12A7, C3A (3CaO-Al
  • slag containing at least 60% by mass of CA, CA2, C12A7, and one or more kinds of minerals that are also selected from amorphous moss is more preferable.
  • a melting furnace such as an electric furnace at 1,000 ° C or higher, preferably 1,300 ° C or higher until there is no unreacted raw material.
  • the alumina cement of the present invention is produced by a firing method, it can be obtained by firing the mixed raw materials in the same manner as described above in a rotary kiln. At that time Baking at a high temperature is preferable. Baking at 1,300 ° C or higher is more preferable. In the firing method, the particle size adjustment of the raw material, the firing temperature, and the firing time are important for obtaining the desired mineral composition, and the conditions are appropriately determined according to the raw material used.
  • the pulverization of the alumina cement obtained by the firing or melting is not particularly limited, and a pulverizer usually used for fine pulverization of a powder lump can be used.
  • a roller mill, jet mill, tube mill, ball mill, vibration mill and the like can be used.
  • the cooling conditions for the alumina cement obtained by firing or melting are not particularly limited, and conventional methods can be used.
  • Quantification of CA, CA2, C12A7, MA and MgO in the slag according to the present invention can be determined by Rietveld analysis performed based on a powder X-ray diffraction pattern.
  • the MA content is preferably 20% by mass or less, and more preferably 15% by mass or less from the viewpoint of strength development and fire resistance. If the MA content exceeds 20% by mass, properties such as fluidity, fire resistance, strength development, volume stability of the hardened body under high temperature, and spalling resistance may be adversely affected. .
  • CA, CA2, C12A7, and one or more kinds of minerals that are selected to have a group force of amorphous force are 60% by mass or more, preferably 65% by mass
  • the slag containing above, preferably CA, CA2, C12A7, and one or more kinds of minerals selected from the group consisting of amorphous materials are contained in an amount of 60% by mass or more, preferably 65% by mass or more, and MA and Z or A slag with a MgO content of 30% by mass or less, preferably 25% by mass or less.
  • a CaO source and a Z or Al 2 O source are mixed or mixed at a predetermined ratio.
  • the raw material is pulverized, preferably CaOZAl O molar ratio is 1.5 or more, particularly preferably 1.7
  • the alumina cement of the present invention is used as an impurity in the raw material, for example, SiO, Fe 2 O 3
  • CT has no strength development and hardly affects the hydration reaction of alumina cement.
  • C4AF accelerates the hydration reaction of alumina cement
  • C2AS delays the hydration reaction of cement.
  • additives such as a curing retarder, a curing accelerator, a fluidizing agent, etc., which are usually blended in an amorphous refractory.
  • Examples of the curing accelerator include lithium salts such as Li CO, Ca (OH), NaOH, and KOH.
  • lithium salts are preferred because they have a strong curing promoting effect.
  • the curing retarder include carboxylic acids, alkali metal carbonates, boric acids, polyacrylic acids, polymethacrylic acids, or alkali salts such as hexametaphosphoric acid, tripolyphosphoric acid, and pyrophosphoric acid.
  • the additive blending method is not particularly limited, and each additive is blended in a predetermined ratio and pulverized alumina cement clinker, V-type blender, corn blender, and nauter mixer. Mix evenly using a mixer such as a bread mixer or omni mixer, or after mixing with a clinker at a predetermined ratio, mix and pulverize with a pulverizer such as a vibration mill, tube mill, ball mill, or roller mill. Is possible.
  • the amorphous refractory according to the present invention is magnesia, magnesia spinel, chamotte, alumina, silicon carbide, ultrafine powder, oil pitch, tar, scale-like graphite, etc. in terms of corrosion resistance, durability, and fire resistance.
  • One or two or more types of refractory aggregates selected from the carbonaceous aggregates of the above are blended and used as a low-cement castable of 98-90% by mass of refractory aggregate and 2-10% by mass of alumina cement composition It is preferable.
  • the alumina cement composition means a composition containing alumina, a dispersing agent, a hardening adjusting agent and the like in addition to the alumina cement.
  • the method for producing an amorphous refractory according to the present invention is not particularly limited, and in accordance with an ordinary method for producing an irregular refractory, each constituent raw material is blended in a predetermined ratio, and V It can be mixed uniformly using a blender such as a blender, cone blender, nauter mixer, pan mixer, or omni mixer, or it can be directly weighed into the kneader when it is kneaded at a specified ratio. is there.
  • a blender such as a blender, cone blender, nauter mixer, pan mixer, or omni mixer
  • alumina cement was adjusted to an average particle size of 8 ⁇ 3 ⁇ m with a batch type ball mill, and a mortar test was conducted according to JIS R2521. The results are shown in Table 3.
  • CaO source commercial quicklime (manufactured by Denki Kagaku Kogyo Co., Ltd.).
  • Alumina cement Commercial product (Alumina cement No. 1 manufactured by Denki Kagaku Kogyo Co., Ltd.) (for comparison) ⁇ Evaluation method>
  • Alumina cement was measured by powder X-ray diffraction method (manufactured by Rigaku Corporation, model: mini-fle X), and the diffraction pattern was analyzed and quantified by Rietveld method.
  • the amorphous mineral composition was determined by measuring a mixed powder of ⁇ -Quartz and alumina cement in a known amount by the X-ray diffraction method, and analyzing and quantifying the diffraction pattern by the Rietveld method.
  • Curing strength Put the kneaded material into a 4 x 4 x 16cm mold and cure it in a constant temperature room at 20 ° C for 24 hours. -E).
  • Drying strength Put the kneaded material in a 4 x 4 x 16cm mold and cure in a constant temperature room at 20 ° C for 24 hours. Then, it was further dried for 24 hours at 110 ° C., and the compressive strength was measured.
  • volume stability Place the kneaded material in a 2 x 2 x 8 cm mold, cure in a constant temperature room at 20 ° C for 24 hours, then dry at 110 ° C for 24 hours, and then at 1000 ° C for 3 hours. Baked for hours. Measure the line change rate with calipers. ) As an index of volume stability.
  • slag containing a large amount of CaO and Al 2 O is used as a raw material for alumina cement.
  • the obtained alumina cement can be used as a raw material for an amorphous refractory that exhibits characteristics such as fluidity and volume stability that are comparable to conventional products.
  • amorphous refractory that exhibits characteristics such as fluidity and volume stability that are comparable to conventional products.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Products (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un ciment alumineux présentant des caractéristiques favorables en comparaison des ciments alumineux classiques, ledit procédé utilisant un laitier contenant de grandes quantités de CaO et de Al2O3 en tant que matière première. L'invention concerne également des matériaux réfractaires non façonnés préparés en utilisant le ciment alumineux. Le procédé de fabrication de ciment alumineux est caractérisé en ce qu'il comprend la soumission d'un laitier contenant un ou plusieurs minéraux choisis dans le groupe comprenant CaO•Al2O3, CaO•2Al2O3, 12CaO•7Al2O3 et des minéraux amorphes en une quantité supérieure ou égale à 60 % en masse ou un de leurs mélanges avec une source supplémentaire de CaO et/ou une source supplémentaire d'Al2O3 à une fusion ou une calcination, puis à un broyage. L'invention concerne également des matériaux réfractaires non façonnés préparés en utilisant le ciment alumineux ainsi obtenu.
PCT/JP2007/059673 2006-05-10 2007-05-10 Procédé de fabrication de ciment alumineux et matériaux réfractaires non façonnés WO2007129752A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-130976 2006-05-10
JP2006130976A JP2009173458A (ja) 2006-05-10 2006-05-10 アルミナセメント及び不定形耐火物

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WO2007129752A1 true WO2007129752A1 (fr) 2007-11-15

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015132848A1 (fr) * 2014-03-03 2015-09-11 黒崎播磨株式会社 Béton réfractaire
JP2016003152A (ja) * 2014-06-16 2016-01-12 宇部興産株式会社 セルフレベリング材
JP2016013960A (ja) * 2014-06-11 2016-01-28 宇部興産株式会社 耐酸性水硬性組成物、モルタル組成物及びモルタル硬化体
FR3068965A1 (fr) * 2017-07-11 2019-01-18 Vicat Nouveau materiau de construction prepare a partir d’un nouveau materiau pouzzolanique
CN111960835A (zh) * 2020-08-28 2020-11-20 攀钢集团攀枝花钢铁研究院有限公司 降低电炉镁碳砖氧化的勾缝料及其制备和使用方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0483745A (ja) * 1990-07-25 1992-03-17 Chubu Kohan Kk 電気炉スラグを原料とするアルミナセメントの製造方法
JP2005247618A (ja) * 2004-03-03 2005-09-15 Denki Kagaku Kogyo Kk アルミナセメントセメント及び不定形耐火物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0483745A (ja) * 1990-07-25 1992-03-17 Chubu Kohan Kk 電気炉スラグを原料とするアルミナセメントの製造方法
JP2005247618A (ja) * 2004-03-03 2005-09-15 Denki Kagaku Kogyo Kk アルミナセメントセメント及び不定形耐火物

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015132848A1 (fr) * 2014-03-03 2015-09-11 黒崎播磨株式会社 Béton réfractaire
US10093576B2 (en) 2014-03-03 2018-10-09 Krosakiharima Corporation Unshaped refractory material
JP2016013960A (ja) * 2014-06-11 2016-01-28 宇部興産株式会社 耐酸性水硬性組成物、モルタル組成物及びモルタル硬化体
JP2016003152A (ja) * 2014-06-16 2016-01-12 宇部興産株式会社 セルフレベリング材
FR3068965A1 (fr) * 2017-07-11 2019-01-18 Vicat Nouveau materiau de construction prepare a partir d’un nouveau materiau pouzzolanique
CN111960835A (zh) * 2020-08-28 2020-11-20 攀钢集团攀枝花钢铁研究院有限公司 降低电炉镁碳砖氧化的勾缝料及其制备和使用方法

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