AU2014258396B2 - Fluidity improvement type cement clinker - Google Patents
Fluidity improvement type cement clinker Download PDFInfo
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- AU2014258396B2 AU2014258396B2 AU2014258396A AU2014258396A AU2014258396B2 AU 2014258396 B2 AU2014258396 B2 AU 2014258396B2 AU 2014258396 A AU2014258396 A AU 2014258396A AU 2014258396 A AU2014258396 A AU 2014258396A AU 2014258396 B2 AU2014258396 B2 AU 2014258396B2
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- cement clinker
- cement
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- 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
- C04B7/02—Portland cement
-
- 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
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00215—Mortar or concrete mixtures defined by their oxide composition
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
This Portland cement clinker, which has a hydraulic modulus of 1.8-2.2, a silica modulus of 2.0-2.8, an iron modulus of 1.7-2.0, and a TiO
Description
DESCRIPTION
FLUIDITY IMPROVEMENT TYPE CEMENT CLINKER TECHNICAL FIELD
The present invention relates to Portland cement clinker. More specifically, it relates to cement clinker which provides a cement composition having excellent fluidity even when it contains ТЮ2 derived from a raw material.
BACKGROUND ART
Portland cement clinker is essentially composed of Si02, А120з, CaO and ЕегОз. These components are contained in the clinker as minerals. More specifically, the minerals contained in the clinker are C3S (3Ca0-Si02), C3A (3CaO • A1203) , C2S (2Ca0-Si02) and C4AF (4CaO • A1203 • Fe203) , and it is disclosed that the existence ratio of these components has a great influence upon the physical properties of cement.
Various studies are being made on the influences of minor components contained in cement. For example, the content of magnesium oxide, the total content of alkalis and the content of a chloride ion in cement are specified by JIS standards (JIS R 5210).
The disposal of wastes and by-products is becoming a social problem. Examples of these include water sludge, incinerated ash of sewage sludge, incinerated ash of city garbage, blast furnace water granulated slag, blast furnace air-cooled slag and iron and steel slag. It is expected that the number of types and the amounts of wastes and by-products which are difficult to be disposed of will increase in the future, and further studies on the establishment of effective methods for disposing of these and reusing and recycling methods are required.
For the manufacturing of cement, the above wastes and byproducts have been recycled as raw materials and heat energy sources. However, there are many cases in which various components except for main components constituting cement and minor components specified by JIS standards are contained in the above wastes and by-products in relatively large quantities.
One of the components is a Ti component (chemical species containing a titanium atom). Especially when neutralized slag (titanium slag) produced in the purification step of titanium is used as a cement raw material, the content of ТЮ2 in the manufactured cement clinker often becomes about 1 mass%. Coal ash which is generally used as a cement raw material may contain a relatively large amount of a Ti component (refer, for example, to JP-A 2010-120832).
In this respect, JP-A 2012-224503 reports that although the fluidity of cement degrades when it contains ТЮ2, the cement exhibits excellent fluidity by setting a specific iron modulus and a specific silica modulus even when the content of Ti02 becomes about 1 mass%.
The discussion of documents, acts, materials, devices, articles and the like is included in this specification solely for the purpose of providing a context for the present invention. It is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application.
Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification (including the claims) they are to be interpreted as specifying the presence of the stated features, integers, steps or components, but not precluding the presence of one or more other features, integers, steps or components, or group thereof.
DISCLOSURE OF THE INVENTION
However, since the presence ratio of clinker minerals has a great influence upon physical properties, when the iron modulus and the silica modulus change, the physical properties of the obtained cement deviate from those of normal Portland cement. When a large amount of waste having a high content of a Ti component is used as a raw material, a cement composition having the same iron modulus and the same silica modulus as those of normal Portland cement becomes unsatisfactory in terms of fluidity.
The present invention was made to break through this situation.
It is therefore an aspect of the present invention to provide cement clinker which provides a cement composition having excellent fluidity even when the content of TiCk becomes high in the same mineral composition as that of normal Portland cement clinker.
The inventors of the present invention conducted intensive studies in view of the above problem. As a result, they found that excellent fluidity is ensured by adjusting the content of MnO in cement clinker when the content of TiCk is high in the same mineral composition as that of normal Portland cement clinker. The present invention was accomplished based on this finding.
That is, the present invention provides Portland cement clinker which has a hydraulic modulus of 1.8 to 2.2, a silica modulus of 2.0 to 2.8 and an iron modulus of 1.7 to 2.0 and contains 0.3 to 1.0 mass% of TiCk and MnO in an amount which is 1.5 times or more the mass of ТЮ2.
In another aspect, the present invention provides a Portland cement clinker having a hydraulic modulus of 1.8 to 2.2, a silica modulus of 2.0 to 2.8 and an iron modulus of 1.7 to 2.0 and а Ti02 content of 0.5 to 1.0 mass% and containing MnO in an amount which is 1.5 times or more the mass of Ti02.
BEST MODE FOR CARRYING OUT THE INVENTION
The Portland cement clinker of the present invention (may also be simply referred to as "cement clinker" hereinafter) has a hydraulic modulus of 1.8 to 2.2, a silica modulus of 2.0 to 2.8 and an iron modulus of 1.7 to 2.0. Preferably, it has a hydraulic modulus of 1.9 to 2.1, a silica modulus of 2.3 to 2.6 and an iron modulus of 1.8 to 2.0.
The above hydraulic modulus, silica modulus and iron modulus (three modulus) are calculated by inserting the results of chemical composition analysis obtained for cement clinker into the following equations, respectively, as is well known. Hydraulic modulus = CaO/ (Si02+Al203+Fe203)
Silica modulus = Si02/ (Al203+Fe203)
Iron modulus = Al203/Fe203
In the above equations, the terms represented by the chemical formulas mean the contents of the species obtained by the chemical composition analysis of the cement clinker (based on mass).
The values of the above three modulus of the cement clinker of the present invention fall within the same ranges as those of Portland cement clinker which exhibit normal properties.
However, the cement clinker of the present invention contains 0.3 to 1.0 mass% of Ti02. It is disclosed that when the cement clinker contains Ti02, the fluidity of the obtained cement composition degrades. The present invention relates to a technology for restoring fluidity impaired by containing Ti02 by further containing MnO in cement clinker containing Ti02. When the content of Ti02 is lower than 0.3 mass%, the reduction of fluidity by Ti02 can be substantially ignored and accordingly, it is meaningless to apply the present invention.
When the content of TiCh is higher than 1.0 mass%, even if other requirements for the cement clinker of the present invention are satisfied, the restoration of fluidity in the obtained cement composition may become unsatisfactory, thereby causing a big practical problem. The content of TiCk in the cement clinker of the present invention is preferably 0.5 to 1.0 mass%.
The cement clinker of the present invention contains MnO in an amount which is 1.5 times or more the mass of TiC>2. In this text, when the content of MnO satisfies the above requirement, fluidity which is degraded by the Ti component can be restored to such an extent that the cement clinker becomes industrially useful. Meanwhile, as the content of MnO becomes higher, the compressive strength of a hardened body becomes lower. Therefore, the content of MnO is preferably not more than 2.5 mass%, more preferably not more than 2.0 mass%.
The content of ТЮ2 and the content of MnO in this text are not limited to the contents of chemical species existent in the form of Ti02 and MnO, respectively. These values are calculated from the amounts of a titanium atom and a manganese atom determined by the chemical composition analysis of the cement clinker in terms of the masses of Ti02 and Mno, r e s p e c t i v e 1 у.
The chemical composition analysis (quantitative analysis) of components contained in the cement clinker may be carried out in accordance with, for example, the chemical analysis method specified in JIS R 5202 or the fluorescent X--ray analysis method specified in JIS R 52 04.
The process for manufacturing the cement clinker of the present invention is not particularly limited.
Since the three modulus of the cement clinker of the present invention fall within the same ranges as those of conventionally known cement clinker having normal properties, as for the selection and preparation technology of main raw materials such as limestone and silica, conventionally known methods may be used as they are.
Since the cement clinker of the present invention may have a high content of Ti02( it has an advantage that a large amount of waste containing a Ti component can be used as a raw material. A conventionally known process for producing cement clinker may be suitably selected and employed except that the blending ratio of the raw materials is adjusted by further adding a suitable Mn source to the raw materials so as to ensure that cement clinker after burning has the above three modulus and the above content of Ti02 and the above content of MnO.
As the raw materials which can be used, not only natural raw materials such as limestone, clay, silica stone and iron ore but also wastes and by-products may be used. Specific examples of the wastes and the by-products include blast furnace slag, steel slag, nonferrous slag, coal ash, sewage sludge, water purification sludge, paper making sludge, с о nst г исt i оn generated s о i 1, no1di ng s a nd, d u s t, incineration fly ash, molten fly ash, wood, waste white clay, coal refuse, waste tires, shells, city garbage and incineration ash of city garbage (some of these become the raw materials of the; cement clinker and heat energy sources) .
Raw1 materials having a nigh consent of a T'r component include titanium slag, coal ash and blast furnace slag; and raw materials having a high content of a Mn component (chemical species containing a manganese: atom} used to set the content of MnO to the above range include manganese minerals and waste batteries. ' The Ti component anci the Mn component contained in the raw materials are often contained: in a form (for example, oxide, composite oxide or alloy) having almost no volatility at a clinker burning temperature. Therefore, calculation may be carried out to determine the blending ratio based on the condition that all of titanium atoms and manganese atoms contained in the Ti component and the Mn component contained in the raw materials move into cement clinker. When it is known in advance that there are/is a Ti component and/or a Mn component which volatilize in the raw material grinding step or burning step and are not introduced into the cement clinker, calculation must be carried out by taking this into consideration as a matter of course. When calculation is carried out in accordance with a determined method for the control of composition at the time of manufacturing cement clinker, the composition of components of the cement clinker after burning can be generally controlled to a range of с a 1 c u 1 a t e d v a 1 u e 10.0 5 raa s s % .
Cement clinker can be obtained by burning the raw materials whose blending ratio has been adjusted as described above in accordance with a determined method in the industry. The burning method is not particularly limited, and a conventionally known method is suitably selected to burn the raw materials. For example, a cement kiln such as NSP kiln or SP kiln which is capable of high-temperature heating is used to burn the raw materials at a temperature of 1,450°C or higher for preferably 20 to 120 miniates.
The cement clinker manufactured as described above may be used as a JlS-standard cement composition, a cement composition based on standards other than JIS standards or the raw material of a cement-based solidifying agent in accordance with a known method.
The JlS-standard cement composition or the cement composition based on standards other than JIS standards preferably contains at least a ground product of the cement clinker manufactured as described above and a ground product of gypsum. In addition to these, the composition may contain a ground product of at least one selected from blast furnace slag, limestone (calcium carbonate) , fly ash and silica fume.
The content of a ground product of gypsum in the above cement composition is preferably 0.5 to 5 parts by mass, more preferably 1.5 to 3 parts by mass in terms of S03 based on 100 parts by mass of a ground product of the cement clinker. The preferred contents of other components based on 100 parts by mass of a ground product of the cement clinker are given below.
Blast furnace slag: preferably not more than 7 0 parts by mass, more preferably 0.5 to 60 parts by mass, much more preferably 0.5 to 30 parts by mass
Limestone (calcium carbonate): preferably not more than 30 parts by mass, more preferably 0.5 to 10 parts by mass Fly ash: preferably not more than 50 parts by mass, more preferably 0.5 to 30 parts by mass
Silica fume: preferably not more than 2 0 parts by mass, more preferably 0.5 to 10 parts by mass
The above cement composition may be produced by grinding the above components after they are mixed together, mixing the components after they are each ground, or a combination of these methods. A suitable grinding aid may be added at the time of grinding.
The above cement composition has a Blaine specific surface area of preferably not less than a value determined by JIS standards, more preferably 2,800 to 5, 000 cm2/g. This specific surface area can be achieved by suitably adjusting the degree of the above grinding.
The cement composition obtained as described above may be used to produce a hardened body by adding water directly or after it is mixed with a suitable material such as an aggregate or water reducing agent and may also be used as blast furnace slag cement or fly ash cement by mixing blast furnace slag or fly ash.
EXAMPLES
Although the constitution and effect of the present invention will be explained with reference to the following examples, it is to be understood that the present invention is not limited to these examples.
The following reagents were used as the raw materials of the cement clinker in the following examples and comparative examples.
Ti02 source: titanium dioxide (special grade) of Wako Pure Chemical Industries, Ltd.
CaO source: calcium carbonate (special grade) of Wako Pure Chemical Industries, Ltd. ,
Si02 source: silicon dioxide (special grade) of Wako Pure Chemical Industries, Ltd. A1203 source: aluminum oxide (special grade) of Wako Pure Chemical Industries, Ltd.
Fe2Ch source: iron oxide (first grade) of Wako Pure Chemical Industries, Ltd.
MnO source: manganese oxide (first grade) of Wako Pure Chemical Industries, Ltd.
The gypsum used to prepare the cement composition was byproduct gypsum generated from a thermal power plant.
Reference Example, Examples 1 to 5 and Comparative Examples 1 t о 5 (1) Preparation of cement clinker and analysis of c ompо s i t i оn
The above cement composition raw materials were fed to an electric furnace and fully mixed together to ensure that the contents of C3S, C2S, C3A and C4AF calculated by Bogue' s equations and also the contents of Ti02 and MnO became values shown in Table 1 below and burned in the atmosphere at 1,450°C for 1.5 hours to obtain cement clinker.
The chemical composition obtained by fluorescent X-ray analysis based on JIS R 5204 of the cement clinker obtained above, the three modulus calculated from the composition and the composition of clinker minerals obtained by inserting the composition into the Bogue's equations are shown in Table are shown in Table 1.
Table 1: Composition of cement clinker and cement paste flow
Ex.; Example, C.Ex.: Comparative Example
Reference Example is an example of normal Portland cement having no Ti02. In Comparative Examples 1 to 5, the ' content of Ti02 is 0.5 mass% and i.Q massl, respectively. The cement paste flow values of these comparative examples are smaller than that of the reference example.
In contrast to this, in Examples 1 to 5 in which MnO is contained in an amount which is 1.5 times or more the mass of Ti02, it is understood that a large i low value is obtained even when TiCg is contained.
Effect of the Invention
According to the present invention, even when Ti02 is contained in cement clinker by using a recycled raw material, a cement composition having excellent fluidity can be obtained by increasing the content of MnO m the clinker.
Therefore, it is possible to use a raw material having a high content, of a Ti component in a larger amount than before, thereby promoting the effective use of waste.
Claims (4)
- THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:1. Portland cement clinker having a hydraulic modulus of 1.8 to 2.2, a silica modulus of 2.0 to 2.8 and an iron modulus of 1.7 to 2.0 and a Ti02 content of 0.5 to 1.0 mass% and containing MnO in an amount which is 1.5 times or more the mass of Ti02.
- 2. The Portland cement clinker according to claim 1, wherein the content of MnO is 1.5 to 2.5 times the mass of Ti02.
- 3. A cement composition comprising a ground product of the Portland cement clinker of claim 1 or 2 and a ground product of gypsum.
- 4. The cement composition according to claim 3 which further comprises a ground product of at least one selected from blast furnace slag, limestone, fly ash and silica fume.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013091284 | 2013-04-24 | ||
| JP2013-091284 | 2013-04-24 | ||
| PCT/JP2014/061344 WO2014175294A1 (en) | 2013-04-24 | 2014-04-16 | Improved-fluidity cement clinker |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2014258396A1 AU2014258396A1 (en) | 2015-11-05 |
| AU2014258396B2 true AU2014258396B2 (en) | 2017-07-27 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2014258396A Active AU2014258396B2 (en) | 2013-04-24 | 2014-04-16 | Fluidity improvement type cement clinker |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6353264B2 (en) |
| AU (1) | AU2014258396B2 (en) |
| WO (1) | WO2014175294A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109608075B (en) * | 2018-12-24 | 2021-10-29 | 攀枝花环业冶金渣开发有限责任公司 | High-titanium blast furnace slag composite admixture micro powder and preparation method thereof |
| JP7436249B2 (en) * | 2020-03-13 | 2024-02-21 | 株式会社トクヤマ | cement clinker |
| CN112661489A (en) * | 2020-12-31 | 2021-04-16 | 山西富森能源科技有限公司 | Method for preparing ceramsite proppant by using self-ignition low-aluminum coal gangue and composite mineralizer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012224503A (en) * | 2011-04-19 | 2012-11-15 | Tokuyama Corp | Fluidity improvement type cement clinker |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52155623A (en) * | 1976-06-22 | 1977-12-24 | Kobe Steel Ltd | Method of manufacturing portland cement |
| JPS5846461B2 (en) * | 1977-10-15 | 1983-10-17 | 株式会社神戸製鋼所 | Manufacturing method of cement clinker using converter slag as raw material |
| JPH10152354A (en) * | 1996-11-22 | 1998-06-09 | Tosoh Corp | Manganese slag treatment method |
| KR100415659B1 (en) * | 1998-11-25 | 2004-03-19 | 주식회사 포스코 | A cement composition and a method thereof using ladle slag |
| FR2864074B1 (en) * | 2003-12-18 | 2006-05-19 | Lafarge Sa | HYDRAULIC MINERAL COMPOSITION AND PROCESS FOR THE PRODUCTION THEREOF, CEMENTITIOUS PRODUCTS AND HYDRAULIC BINDERS CONTAINING SUCH A COMPOSITION |
| JP5006088B2 (en) * | 2007-03-30 | 2012-08-22 | Ｊｆｅスチール株式会社 | Method for selecting granulated blast furnace slag for cement and method for producing cement composition |
| JP5398236B2 (en) * | 2008-11-21 | 2014-01-29 | 株式会社トクヤマ | Cement clinker manufacturing method |
| CN101544485B (en) * | 2009-04-20 | 2011-07-27 | 西安建筑科技大学 | Method for preparing geopolymer and organic macromolecule composite gelled material |
-
2014
- 2014-04-16 WO PCT/JP2014/061344 patent/WO2014175294A1/en not_active Ceased
- 2014-04-16 JP JP2014084146A patent/JP6353264B2/en active Active
- 2014-04-16 AU AU2014258396A patent/AU2014258396B2/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012224503A (en) * | 2011-04-19 | 2012-11-15 | Tokuyama Corp | Fluidity improvement type cement clinker |
Non-Patent Citations (1)
| Title |
|---|
| TOMIKAZU KOYAMA, "Tenrosai o Cement Tetsu Genryo to shite Shiyo shita Baai no Manganese no Eikyo", PROCEEDINGS OF JAPAN CEMENT ENGINEERING ASSOCIATION, (19811210), vol. 35, pages 65 - 68 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014224033A (en) | 2014-12-04 |
| JP6353264B2 (en) | 2018-07-04 |
| AU2014258396A1 (en) | 2015-11-05 |
| WO2014175294A1 (en) | 2014-10-30 |
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Free format text: THE NATURE OF THE AMENDMENT IS: AMEND THE INVENTION TITLE TO READ FLUIDITY IMPROVEMENT TYPE CEMENT CLINKER |
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