JP2002265242A - Cement clinker and cement composition - Google Patents
Cement clinker and cement compositionInfo
- Publication number
- JP2002265242A JP2002265242A JP2001064517A JP2001064517A JP2002265242A JP 2002265242 A JP2002265242 A JP 2002265242A JP 2001064517 A JP2001064517 A JP 2001064517A JP 2001064517 A JP2001064517 A JP 2001064517A JP 2002265242 A JP2002265242 A JP 2002265242A
- Authority
- JP
- Japan
- Prior art keywords
- content
- cement
- cement clinker
- mass
- clinker
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 239000004568 cement Substances 0.000 title claims abstract description 74
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 36
- 239000002699 waste material Substances 0.000 claims abstract description 24
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010801 sewage sludge Substances 0.000 claims abstract description 10
- 239000010440 gypsum Substances 0.000 claims abstract description 8
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- 239000002893 slag Substances 0.000 claims abstract description 7
- 238000009628 steelmaking Methods 0.000 claims abstract description 5
- 238000004056 waste incineration Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 239000002956 ash Substances 0.000 claims description 10
- 239000010883 coal ash Substances 0.000 claims description 5
- 230000006835 compression Effects 0.000 abstract 1
- 238000007906 compression Methods 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 39
- 239000000395 magnesium oxide Substances 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- -1 phosphorus compound Chemical class 0.000 description 7
- 239000011398 Portland cement Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- 235000012255 calcium oxide Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 210000004556 brain Anatomy 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 239000010882 bottom ash Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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
- C04B7/24—Cements from oil shales, residues or waste other than 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
- 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
- C04B2111/00198—Characterisation or quantities of the compositions or their ingredients expressed as mathematical formulae or equations
-
- 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
Landscapes
- 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)
- Processing Of Solid Wastes (AREA)
Abstract
(57)【要約】
【課題】 高リン含有量であっても圧縮強度の低下割合
が改良されたセメントクリンカおよび該クリンカから製
造されるセメント組成物を提供すること。
【解決手段】 リン含有量の高い廃棄物（下水汚泥焼却
物、都市ゴミ焼却灰、製鋼スラグなど）を含むセメント
クリンカ用原料を焼成して得られるＰ2Ｏ5含有量が０．
３〜２．５質量％のセメントクリンカにおいて、水硬率
（ＨＭ）；１．８〜２．１５、ケイ酸率（ＳＭ）；１．
３〜２．４、かつ、ＭｇＯ含有量；１．０〜５．０質量
％であるセメントクリンカ、および該セメントクリンカ
に、総ＳＯ3量が１．５〜４．０質量％となるように石
膏を混合して粉砕したもの／または互いに個別に粉砕し
たのち混合したセメント組成物。PROBLEM TO BE SOLVED: To provide a cement clinker having an improved compression strength reduction ratio even with a high phosphorus content and a cement composition produced from the clinker. SOLUTION: The P 2 O 5 content obtained by calcining a raw material for cement clinker containing waste having a high phosphorus content (sewage sludge incineration, municipal waste incineration ash, steelmaking slag, etc.) is reduced to 0.
In a cement clinker of 3 to 2.5 mass%, hydraulic set rate (HM): 1.8 to 2.15, silicic acid rate (SM);
3 to 2.4, and, MgO content: 1.0-5.0 cement clinker by mass%, and the cement clinker, as total SO 3 content is 1.5 to 4.0 mass% A cement composition in which gypsum is mixed and pulverized or / and separately pulverized and then mixed.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、セメントクリンカ
およびセメント組成物に関し、特に、リン含有量の高い
廃棄物を含む原料を焼成して得られるセメントクリン
カ、および該クリンカから製造されるセメント組成物に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cement clinker and a cement composition, and more particularly to a cement clinker obtained by firing a raw material containing waste having a high phosphorus content, and a cement composition produced from the clinker. About.
【０００２】[0002]
【従来の技術】近年、都市ゴミの焼却灰、下水汚泥及び
該汚泥の焼却灰、並びに製鋼過程で生ずるスラグなどの
産業副産物（以下、これらを総称して“廃棄物”とい
う）は、増加の一途であり、その有効利用および再資源
化が社会的に注目されている。その再資源化の具体策と
して、廃棄物をポルトランドセメントの製造用原料に利
用することが研究されている。2. Description of the Related Art In recent years, incineration ash of municipal waste, sewage sludge and incineration ash of the sludge, and industrial by-products such as slag generated in a steelmaking process (hereinafter, collectively referred to as "waste") have been increasing. It is indispensable, and its effective use and recycling are attracting social attention. As a specific measure of recycling, utilization of waste as a raw material for manufacturing Portland cement has been studied.
【０００３】セメント工業において、上記廃棄物を原料
として用いた場合、焼成過程において、廃棄物に多量に
含まれているリン化合物（一般的に、Ｐ2Ｏ5換算で０．
３〜３０質量％含まれている）の大半は、セメントクリ
ンカ中に残存する。そして、該クリンカ中のリン含有量
が多いほど、セメントの圧縮強度に著しく悪い影響を与
えることが知られている。In the cement industry, when the above-mentioned waste is used as a raw material, a phosphorus compound contained in a large amount in the waste (generally 0.1 ppm in terms of P 2 O 5) in the firing step.
Most of the cement clinker remains in the cement clinker. It is known that the greater the phosphorus content in the clinker, the more significantly the compressive strength of the cement is adversely affected.
【０００４】[0004]
【発明が解決しようとする課題】一般に、普通ポルトラ
ンドセメントクリンカのＰ2Ｏ5含有量は、多くても０．
３質量％程度、大部分のポルトランドセメントクリンカ
は０．１〜０．２質量％である。その程度の含有量で
は、セメントの特性、特に圧縮強度への影響は殆ど無視
できるものであった。Generally, the portland cement clinker generally has a P 2 O 5 content of at most 0.1.
About 3% by weight, most Portland cement clinkers are 0.1-0.2% by weight. At such a content, the effect on the properties of the cement, especially on the compressive strength, was almost negligible.
【０００５】しかし、前記廃棄物を原料に使用した場
合、上記クリンカ中のＰ2Ｏ5含有量が１．０質量％に達
することも稀ではない。そのために、圧縮強度が著しく
低下する。例えば、上記のような高Ｐ2Ｏ5含有量のクリ
ンカから製造されたセメントは、廃棄物を使用しない場
合の圧縮強度（材齢７日）に比べ、Ｐ2Ｏ5含有量が０．
５質量％のときの該強度は８９％、０．８質量％のとき
７９％、１．０質量％のとき７４％、１．３質量％のと
き５９％というように、圧縮強度が急激に低下する（表
２、比較例参照）、という問題点があった。[0005] However, when the waste is used as a raw material, it is not rare that the P 2 O 5 content in the clinker reaches 1.0% by mass. Therefore, the compressive strength is significantly reduced. For example, cements prepared from clinker high content of P 2 O 5 as described above, compared to the compressive strength in the case of not using the waste (age of 7 days), P 2 O 5 content is 0.
The compressive strength sharply increases, such as 89% at 5% by mass, 79% at 0.8% by mass, 74% at 1.0% by mass, and 59% at 1.3% by mass. (See Table 2, Comparative Example).
【０００６】本発明は、上記問題点に鑑みなされたもの
であって、その目的は、高リン含有量であっても ・圧縮強度の低下割合が改良されたセメントクリンカお
よび該クリンカから製造されるセメント組成物を提供す
ることにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has an object to provide a cement clinker having an improved compressive strength reduction ratio even if it has a high phosphorus content, and to be manufactured from the clinker. It is to provide a cement composition.
【０００７】[0007]
【課題を解決するための手段】本発明は、Ｐ2Ｏ5含有量
が特定の範囲にあるセメントクリンカは、水硬率（Ｈ
Ｍ）、ケイ酸率（ＳＭ）およびＭｇＯ含有量の３特性の
組合せによって強度低下の割合が小さくなることを見出
だし、それら特性の範囲を特定し、これにより、上記の
目的を達成することができるものである。According to the present invention, a cement clinker having a P 2 O 5 content in a specific range has a hydraulic set (H).
It has been found that the combination of the three properties of M), silicic acid ratio (SM) and MgO content reduces the rate of strength reduction and specifies the range of these properties, thereby achieving the above object. You can do it.
【０００８】すなわち、本発明の第一（セメントクリン
カ）は、「リン含有量の高い廃棄物を含むセメントクリ
ンカ用原料を焼成して得られるＰ2Ｏ5含有量が０．３〜
２．５質量％のセメントクリンカにおいて、 ・水硬率（ＨＭ）が１．８〜２．１５、 ・ケイ酸率（ＳＭ）が１．３〜２．４であり、かつ、 ・ＭｇＯ含有量が１．０〜５．０質量％である」（請求
項１） ことを要旨とする。Namely, the first invention (cement clinker) is, P 2 O 5 content obtained by firing cement clinker raw material comprising a high waste of "phosphorus content 0.3
In a cement clinker of 2.5% by mass, the hydraulic hardness (HM) is 1.8 to 2.15, the silicate ratio (SM) is 1.3 to 2.4, and MgO content Is 1.0 to 5.0% by mass "(claim 1).
【０００９】また、本発明の第一（セメントクリンカ）
は、 ・廃棄物が下水汚泥、下水汚泥焼却物、都市ゴミ焼却灰
および製鋼スラグから選ばれる１種以上であること（請
求項２）、および ・セメントクリンカ用原料として、石炭灰を使用するこ
と（請求項３）、を特徴とする。The first (cement clinker) of the present invention
The waste must be at least one selected from sewage sludge, sewage sludge incineration, municipal waste incineration ash, and steelmaking slag (Claim 2); and • Use of coal ash as a raw material for cement clinker (Claim 3).
【００１０】さらに、本発明の第二（セメント組成物）
は、「請求項１〜３のいずれかに記載のセメントクリン
カに、総ＳＯ3量が１．５〜４．０質量％となるように
石膏を混合して粉砕したもの／または互いに個別に粉砕
したのち混合したものである」（請求項４）、ことを要
旨とする。Furthermore, the second (cement composition) of the present invention
Is "according to the cement clinker according to any one of claim 1 to 3, total SO 3 content is 1.5 to 4.0% by mass so as to, ground by mixing gypsum / or to each other individually pulverized After that, they are mixed "(claim 4).
【００１１】[0011]
【発明の実施の形態】以下、本発明について詳細に説明
する。まず、本発明の第一（セメントクリンカ）につい
て説明する。通常、廃棄物には、種々のリン化合物が含
有されており、廃棄物の履歴によって含まれるリン化合
物も、また、含有量も異なる。例えば、下水汚泥に含ま
れるリン化合物と、熱処理後の下水汚泥焼却灰に含まれ
るリン化合物とは同一ではないし、また、それらのＰ2
Ｏ5換算値も必ずしも一致しない。さらに、同種の廃棄
物であっても、リン化合物の含有量が一定しないことの
方が多い。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the first (cement clinker) of the present invention will be described. Normally, waste contains various phosphorus compounds, and the content of the phosphorus compounds contained in the waste varies depending on the history of the waste. For example, the phosphorus compound contained in sewage sludge and the phosphorus compound contained in sewage sludge incineration ash after heat treatment are not the same, and their P 2
O 5 converted values do not always match. Furthermore, even in the case of the same kind of waste, the content of the phosphorus compound is often not constant.
【００１２】本発明の第一は、従来使用されている原料
のほかに、上記のようなリン化合物を含む廃棄物を添加
した調合原料を焼成して製造されたＰ2Ｏ5（換算）を
０．３〜２．５質量％含有するセメントクリンカに適用
するものである。A first aspect of the present invention is to convert P 2 O 5 (converted) produced by calcining a blended raw material to which the above-mentioned waste containing a phosphorus compound is added in addition to the conventionally used raw material. It is applied to a cement clinker containing 0.3 to 2.5% by mass.
【００１３】セメントクリンカ中のＰ2Ｏ5含有量の範囲
を限定した理由は、 ・０．３質量％未満の場合、従来のセメントクリンカと
変りないので、圧縮強度に対する影響がない。したがっ
て、本発明の第一は、０．３質量％以上の場合について
適用するものである。 ・２．５質量％を超える場合、水硬率（ＨＭ）、ケイ酸
率（ＳＭ）およびＭｇＯ含有量が前述した範囲内に該当
していても、特に、短期材齢での強度発現の低下が著し
いので好ましくない。The reason for limiting the range of the P 2 O 5 content in the cement clinker is as follows: When the content is less than 0.3% by mass, there is no difference from the conventional cement clinker, and there is no influence on the compressive strength. Therefore, the first aspect of the present invention is applied to the case where the content is 0.3% by mass or more. -If it exceeds 2.5% by mass, even if the hydraulic modulus (HM), the silicic acid ratio (SM) and the MgO content fall within the above-mentioned ranges, the decrease in strength development particularly at short-term aging is achieved. Is not preferable because it is significant.
【００１４】そして、上記セメントクリンカは、 ・水硬率（ＨＭ） ；１．８〜２．１５、好ましくは
２．０〜２．１５、 ・ケイ酸率（ＳＭ）；１．３〜２．４、かつ、 ・ＭｇＯ ；１．０〜５．０質量％ の範囲に調整されていることが重要である。[0014] The cement clinker includes:-Hydraulic modulus (HM): 1.8 to 2.15, preferably 2.0 to 2.15;-Silicic acid rate (SM): 1.3 to 2. It is important that the content of MgO is adjusted to the range of 1.0 to 5.0% by mass.
【００１５】水硬率（ＨＭ）は、セメントクリンカの最
も重要な化学的係数である。その水硬率（ＨＭ）が ・２．１５を超える場合、ＭｇＯ含有量の多少に拘ら
ず、強度低下の割合の改良が低くなるので、また、 ・１．８未満の場合、Ｐ2Ｏ5含有量が多くなるにつれ
て、その低下割合の改良が小さくなるので、いずれの場
合も好ましくない。[0015] Hydraulic modulus (HM) is the most important chemical coefficient of cement clinker. When the hydraulic modulus (HM) is more than 2.15, the improvement in the rate of strength reduction is low irrespective of the MgO content, and when it is less than 1.8, P 2 O 5 As the content increases, the improvement in the reduction ratio decreases, and either case is not preferable.
【００１６】次に、ケイ酸率（ＳＭ）について説明す
る。ケイ酸率（ＳＭ）が ・２．４を超える場合、Ｐ2Ｏ5含有量が多いと、強度発
現が低下するうえ、凝結遅延が生じる、 ・１．３未満の場合、混練物の流動性が低下する上、水
和発熱量が大きくなる、ことなど強度以外の各種特性に
も悪影響が生じるので好ましくない。Next, the silicate ratio (SM) will be described. When the silicic acid ratio (SM) exceeds 2.4, if the content of P 2 O 5 is large, the strength development is reduced and the setting delay is caused. If it is less than 1.3, the fluidity of the kneaded material In addition, various properties other than strength, such as a decrease in heat generation and an increase in the calorific value of hydration, are not preferred.
【００１７】ＭｇＯは、Ｐ2Ｏ5含有量が多い程、多量に
含まれている方が強度低下を抑制する傾向にあり好まし
い。例えば、下記のように含まれているのが好適であ
る。 ・Ｐ2Ｏ5含有量＜１．０質量％ ：ＭｇＯ＝１．
０〜５．０質量％ ・Ｐ2Ｏ5含有量＝１．０〜２．５質量％：ＭｇＯ＝２．
０〜５．０質量％The greater the content of MgO, the more the content of P 2 O 5, the more the content of MgO tends to suppress the decrease in strength. For example, it is preferable to include the following.・ P 2 O 5 content <1.0% by mass: MgO = 1.
0 to 5.0 wt% · P 2 O 5 content = 1.0 to 2.5 mass%: MgO = 2.
0 to 5.0% by mass
【００１８】ＭｇＯ含有量の限界点について説明する。
その含有量が５．０質量％を超えた場合（注）、 ・セメント硬化体が膨張しやすく長期安定性を阻害する
原因となる、ことから好ましくない。 （注）一般のセメントについて、ＪＩＳ Ｒ ５２１０
「ポルトランドセメント」には、セメント硬化体の膨張
と長期安定性を主な理由として「ＭｇＯ含有量の上限；
５．０質量％」と規定する。The limit of the MgO content will be described.
If the content exceeds 5.0% by mass (note), it is not preferable because the hardened cement body is likely to expand and cause long-term stability to be impaired. (Note) For general cement, JIS R 5210
"Portland cement" has an "upper limit of MgO content" mainly because of the expansion and long-term stability of the hardened cement.
5.0% by mass ".
【００１９】・１．０質量％未満の場合、強度の低下割
合の改良効果が小さく好ましくない。この場合、前述し
たように、水硬率（ＨＭ）を高くしても殆ど効果が見ら
れない。If the amount is less than 1.0% by mass, the effect of improving the rate of decrease in strength is undesirably small. In this case, as described above, even if the hydraulic hardness (HM) is increased, almost no effect is seen.
【００２０】セメントクリンカの化学成分を特定する係
数として上記のほかに、鉄率（ＩＭ）が知られている。
この鉄率（ＩＭ）について、本発明では、特に、限定し
ないが好ましい範囲は１．５〜１．８である。[0020] In addition to the above, iron factor (IM) is known as a coefficient for specifying a chemical component of cement clinker.
In the present invention, the iron ratio (IM) is not particularly limited, but a preferable range is 1.5 to 1.8.
【００２１】本発明の第一において、リン含有量の高い
廃棄物には、 ・下水汚泥、およびその焼却灰、 ・都市ゴミ焼却灰、 ・製鋼過程で生じるスラグ（工業副産物） などが挙げられる。In the first aspect of the present invention, wastes having a high phosphorus content include: • sewage sludge and its incineration ash; • municipal waste incineration ash; • slag (industrial by-product) generated in the steelmaking process.
【００２２】セメントクリンカは、次のようにして製造
する。使用する廃棄物は、そのリン化合物の含有量を考
慮して、セメントクリンカ中のＰ2Ｏ5含有量が０．３〜
２．５質量％になるように配合する。水硬率（ＨＭ）お
よびケイ酸率（ＳＭ）の調整は、使用される廃棄物の成
分も含め、従来から使用されているＣａＯ原料、ＳｉＯ
2原料、Ｆｅ2Ｏ3原料および必要に応じてＡｌ2Ｏ3原料
を用いて行なう。The cement clinker is manufactured as follows. The waste used has a P 2 O 5 content in the cement clinker of from 0.3 to 0.3 in consideration of the content of the phosphorus compound.
It mix | blends so that it may become 2.5 mass%. Hydraulic modulus (HM) and silicic acid rate (SM) are adjusted by using the conventionally used CaO raw material, SiO 2
This is performed using two raw materials, a Fe 2 O 3 raw material and, if necessary, an Al 2 O 3 raw material.
【００２３】上記３原料は、具体的に、 ・ＣａＯ原料 ；石灰石、生石灰、消石灰など、 ・ＳｉＯ2原料 ；珪石、粘土など、 ・Ｆｅ2Ｏ3原料；鉄滓、鉄ケ−キなど、 ・Ａｌ2Ｏ3原料；粘土など、 が使用できる。[0023] The 3 raw material, specifically, - CaO raw material; limestone, quick lime, etc. slaked lime, - SiO 2 raw material; silica, such as clays, & Fe 2 O 3 raw material; Tetsukasu, Tetsuke - key etc., - al 2 O 3 raw material; and clays, can be used.
【００２４】なお、ＳｉＯ2原料として、石炭灰（注）
を使用することができる。石炭灰は、火力発電所、各種
工場などで石炭を燃焼したさい大量に発生するので、そ
の有効活用という観点から好ましい。 （注）例えば、フライアッシュ、シンダ−アッシュ、ボ
トムアッシュ、クリンカアッシュなどである。As a raw material for SiO 2 , coal ash (note)
Can be used. Coal ash is generated in large quantities when burning coal in thermal power plants and various factories, and is therefore preferable from the viewpoint of effective utilization. (Note) For example, fly ash, cinder ash, bottom ash, clinker ash and the like.
【００２５】上記原料のほかにセメントクリンカ中のＭ
ｇＯ含有量を１．０〜５．０質量％の範囲に調整するた
め、ＭｇＯ用原料を使用することができる。ＭｇＯ用原
料は、前記ＣａＯ原料、ＳｉＯ2原料、Ｆｅ2Ｏ3原料、
Ａｌ2Ｏ3原料および廃棄物を配合したさい、ＭｇＯ含有
量が上記の範囲内にあれば、必ずしも使用しなくて良
い。ＭｇＯ用原料は、具体的に、酸化マグネシウム、炭
酸マグネシウム、水酸化マグネシウム、ドロマイト、蛇
紋岩、スピネル、高炉スラグなどが挙げられる。In addition to the above raw materials, M in cement clinker
In order to adjust the gO content to a range of 1.0 to 5.0% by mass, a raw material for MgO can be used. The raw material for MgO is the above-mentioned CaO raw material, SiO 2 raw material, Fe 2 O 3 raw material,
When mixing the Al 2 O 3 raw material and the waste, if the MgO content is within the above range, it is not always necessary to use the MgO content. Raw materials for MgO include, specifically, magnesium oxide, magnesium carbonate, magnesium hydroxide, dolomite, serpentine, spinel, blast furnace slag, and the like.
【００２６】本発明の第一のセメントクリンカは、前記
Ｐ2Ｏ5含有量、水硬率（ＨＭ）、ケイ酸率（ＳＭ）およ
びＭｇＯ含有量が所定範囲内に入るように、各原料を配
合・混合・粉砕し、焼成することによって製造される。
上記混合方法は、慣用の装置で行なえばよい。焼成方法
も、慣用の装置（ポルトランドセメントクリンカの焼成
に用いられるＮＳＰキルン、ＳＰキルンなど）で行なえ
ばよい。これらについて、本発明は、特に限定するもの
ではない。The first cement clinker of the present invention uses each raw material so that the P 2 O 5 content, hydraulic modulus (HM), silicate content (SM) and MgO content fall within predetermined ranges. It is manufactured by blending, mixing, crushing, and firing.
The mixing method described above may be performed using a conventional apparatus. The firing method may also be performed using a conventional apparatus (such as an NSP kiln or an SP kiln used for firing Portland cement clinker). With respect to these, the present invention is not particularly limited.
【００２７】次に、本発明の第二（セメント組成物）に
ついて説明する。セメント組成物は、本発明の第一に示
したセメントクリンカに総ＳＯ3量が１．５〜４．０質
量％の範囲内に納まるように石こうを配合し、粉砕して
製造されるものである。Next, the second (cement composition) of the present invention will be described. Cement composition, in which the total SO 3 content in the first place shows the cement clinker of the present invention is blended with gypsum as fall within the scope of 1.5 to 4.0 wt%, is prepared by grinding is there.
【００２８】総ＳＯ3量が ・１．５質量％未満の場合 ；瞬結や流動性の低下が生
じる ・４．０質量％を超える場合；強度低下の割合の改良効
果が小さく、かつ、凝結遅延が生じる、など、いずれの
場合も好ましくない。When the total SO 3 amount is less than 1.5% by mass; instantaneous setting or a decrease in fluidity is caused. When the amount exceeds 4.0% by mass; the effect of improving the rate of strength reduction is small and coagulation occurs. Either case, such as a delay, is not preferred.
【００２９】セメント組成物のブレ−ン比表面積は、３
０００〜４５００ｃｍ2／ｇが好ましい。The cement composition has a Brain specific surface area of 3
000~4500cm 2 / g is preferable.
【００３０】使用される石こうは、２水・半水・無水石
こうの１種またはそれらの混合物である。The gypsum used is one of dihydrate / hemihydrate / anhydrite or a mixture thereof.
【００３１】セメント組成物の製造方法は、前記セメン
トクリンカおよび石こうを ・混合粉砕する方法、 ・個別に粉砕し混合する方法 のいずれかの方法で慣用の設備を利用して行なう。The cement composition is produced using any of the following methods: a method of mixing and grinding the cement clinker and gypsum; and a method of individually grinding and mixing.
【００３２】[0032]
【実施例】以下、本発明を実施例により説明する。 １．使用原料 使用した原料（石灰石、粘土、珪石、鉄滓、下水汚泥焼
却灰、ドロマイトおよび石炭灰）、および、それらの成
分を表１に記載した。なお、石こうの成分も同表に併記
した。The present invention will be described below with reference to examples. 1. Raw Materials Used The raw materials used (limestone, clay, silica, iron slag, sewage sludge incineration ash, dolomite and coal ash) and their components are shown in Table 1. The components of gypsum are also shown in the table.
【００３３】[0033]
【表１】 [Table 1]
【００３４】（実施例１〜７、比較例１〜５） ２．セメントクリンカの製造 前記原料を用いて、表２に示すＰ2Ｏ5含有量、水硬率
（ＨＭ）、ケイ酸率（ＳＭ）およびＭｇＯ含有量となる
ように、慣用の方法で配合・混合して調合原料を造っ
た。各調合原料をＳＰロ−タリ−キルンを用い１４５０
℃で焼成して、セメントクリンカを製造した。該クリン
カの成分を同表に示した。(Examples 1 to 7, Comparative Examples 1 to 5) Manufacture of cement clinker Using the above raw materials, compounding and mixing by a conventional method so that the P 2 O 5 content, hydraulic modulus (HM), silicate ratio (SM) and MgO content shown in Table 2 are obtained. To make the ingredients. Each compounded raw material is 1450 using SP rotary kiln
The mixture was fired at ℃ to produce a cement clinker. The components of the clinker are shown in the same table.
【００３５】３．セメント組成物の製造と強度測定 各セメントクリンカに、表１に示す副産２水石こうを添
加し混合粉砕して、表２に示す総ＳＯ3量を有する試製
セメント組成物（ブレ−ン比表面積；３２００±５０ｃ
ｍ2／ｇ）を製造した。3. Production of Cement Composition and Strength Measurement To each cement clinker, by-product dihydrate gypsum shown in Table 1 was added, mixed and pulverized, and a trial cement composition having a total SO 3 amount shown in Table 2 (Brain specific surface area) 3200 ± 50c
m 2 / g).
【００３６】各セメント組成物について、ＪＩＳ Ｒ
５２０１「セメントの物理試験方法」の『１０．強さ試
験』」に準じて、材齢７日の圧縮強度を測定し、その結
果を表２に示した。なお、比較例１のセメント組成物
は、普通ポルトランドセメントに相当し、その圧縮強度
を基準値（１００）として試製セメント組成物の圧縮強
度の割合（強度比）を同表に併記した。For each cement composition, JIS R
510 “Physical test method of cement”, “10. Strength test ", the compressive strength was measured at 7 days of age, and the results are shown in Table 2. Note that the cement composition of Comparative Example 1 corresponds to ordinary Portland cement, and the compressive strength ratio (strength ratio) of the trial cement composition is also shown in the same table, with the compressive strength as a reference value (100).
【００３７】[0037]
【表２】 [Table 2]
【００３８】上記表２から、実施例１〜７の強度比は、
比較例のそれらに比して高く、圧縮強度が改良されるこ
とが判明した。From the above Table 2, the intensity ratios of Examples 1 to 7 are as follows:
It was found that the compressive strength was improved, which was higher than those of the comparative examples.
【００３９】また、セメントクリンカ中のＰ2Ｏ5含有量
が過多の場合、強度比が著しく低下する点からその含有
量に上限が存在すること（比較例５）、および、ＭｇＯ
の含有量が本発明で規定する規定の範囲外の場合、例え
Ｐ2Ｏ5含有量、ＨＭ、ＳＭなどが規定内にあっても強度
比が改良されないこと（実施例４と比較例４）が明らか
になった。When the content of P 2 O 5 in the cement clinker is excessive, there is an upper limit in the content because the strength ratio is remarkably reduced (Comparative Example 5).
In the case where the content of is out of the range specified in the present invention, the strength ratio is not improved even if the P 2 O 5 content, HM, SM, etc. are within the specified range (Example 4 and Comparative Example 4). Was revealed.
【００４０】さらに、比較例２、３から、セメント組成
物の総ＳＯ3含有量が特定の範囲内であれば、目的を達
成できることも明らかになった。。Further, from Comparative Examples 2 and 3, it was clarified that the object could be achieved if the total SO 3 content of the cement composition was within a specific range. .
【００４１】[0041]
【発明の効果】本発明は、リン含有量の高い廃棄物を含
むセメントクリンカ用原料から製造され、Ｐ2Ｏ5含有量
が０．３〜２．５質量％のセメントクリンカにおいて、
特定の化学的比率［水硬率（ＨＭ）およびケイ酸率（Ｓ
Ｍ）］およびＭｇＯ含有量を特定の範囲に限定した、高
リン含有量のセメントクリンカであること、および、該
セメントクリンカを用いて特定量の総ＳＯ3量に調製さ
れたセメント組成物であることを特徴とし、これによ
り、圧縮強度の低下割合を改良できる、という効果を奏
する。According to the present invention, there is provided a cement clinker manufactured from a raw material for cement clinker containing waste having a high phosphorus content and having a P 2 O 5 content of 0.3 to 2.5% by mass.
Specific chemical ratios [Hydraulic modulus (HM) and silicic acid rate (S
M)] and a cement phosphorus clinker having a high phosphorus content in which the content of MgO is limited to a specific range, and a cement composition prepared to a specific amount of total SO 3 using the cement clinker. This has the effect that the reduction rate of the compressive strength can be improved.
【００４２】本発明は、リンによる弊害（強度低下）を
軽減する手段が化学成分を調整による方法であるから、
その実施が容易であり、かつ、廃棄物処理の促進ができ
る、という効果をも有している。In the present invention, the means for reducing the adverse effects (strength reduction) due to phosphorus is a method by adjusting the chemical components.
There is also an effect that the implementation is easy and the waste disposal can be promoted.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 本間 健一 千葉県佐倉市大作２−４−２ 太平洋セメ ント株式会社中央研究所内 (72)発明者 市川 牧彦 千葉県佐倉市大作２−４−２ 太平洋セメ ント株式会社中央研究所内 (72)発明者 鯉淵 清 神奈川県川崎市川崎区浅野町１−１ 第一 セメント株式会社内 (72)発明者 山口 博之 神奈川県川崎市川崎区浅野町１−１ 第一 セメント株式会社内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kenichi Honma 2-4-2 Daisaku, Sakura City, Chiba Pref. Central Research Institute, Pacific Cement Co., Ltd. (72) Makihiko Ichikawa 2-4-2 Daisaku, Sakura City, Chiba Pref. Central Research Institute of Pacific Cement Co., Ltd. (72) Kiyoshi Koibuchi 1-1, Asano-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Daiichi Cement Co., Ltd. (72) Hiroyuki Yamaguchi 1-1, Asano-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Daiichi Cement Co., Ltd.
Claims (4)
クリンカ用原料を焼成して得られるＰ2Ｏ5含有量が０．
３〜２．５質量％のセメントクリンカにおいて、水硬率
（ＨＭ）が１．８〜２．１５、ケイ酸率（ＳＭ）が１．
３〜２．４であり、かつ、ＭｇＯ含有量が１．０〜５．
０質量％であることを特徴とするセメントクリンカ。1. The P 2 O 5 content obtained by calcining a raw material for cement clinker containing waste having a high phosphorus content is reduced to 0.
In the cement clinker of 3 to 2.5% by mass, the hydraulic modulus (HM) is 1.8 to 2.15 and the silicic acid ratio (SM) is 1.
3 to 2.4, and the MgO content is 1.0 to 5.
A cement clinker, which is 0% by mass.
廃棄物が下水汚泥、下水汚泥焼却物、都市ゴミ焼却灰お
よび製鋼スラグから選ばれる１種以上であることを特徴
とする請求項１に記載のセメントクリンカ。2. The waste according to claim 1, wherein the waste contained in the raw material for cement clinker is at least one selected from sewage sludge, sewage sludge incineration, municipal waste incineration ash, and steelmaking slag. Cement clinker.
炭灰を使用することを特徴とする請求項１または請求項
２に記載のセメントクリンカ。3. The cement clinker according to claim 1, wherein coal ash is used as the raw material for the cement clinker.
トクリンカに、総ＳＯ3量が１．５〜４．０質量％とな
るように石膏を混合して粉砕したもの／または互いに個
別に粉砕したのち混合したものであることを特徴とする
セメント組成物。4. A cement clinker according to any one of claims 1 to 3, which is ground and mixed with gypsum so that the total SO 3 content is 1.5 to 4.0% by mass. A cement composition characterized by being ground and mixed.
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|---|---|---|---|
| JP2001064517A JP4164242B2 (en) | 2001-03-08 | 2001-03-08 | Cement composition |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005087681A1 (en) * | 2004-03-11 | 2005-09-22 | Taiheiyo Cement Corporation | Hydraulic composition |
| WO2010020079A1 (en) * | 2008-08-22 | 2010-02-25 | Tan Jilin | Sewage sludge cement and preparation thereof |
| CN103466970A (en) * | 2013-08-28 | 2013-12-25 | 句容联众科技开发有限公司 | Preparation method of sulfate corrosion resistance cement |
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| JPN3013000422; 横山滋 他: '都市ゴミ焼却灰を主原料としたセメントクリンカーに及ぼす塩素並びにリンの影響とセメント物性の研究' セメント・コンクリート Ｎｏ． ６４６, 20001210, ＰＡＧＥＳ ４４-５０, （社）セメント協会 |
| JPN3013000423; 近藤連一: 'ネオ鉄セメントの研究開発' 日本建築学会大会学術講演梗概集 , 197610, ＰＡＧＥＳ １-２ |
| JPN3013000424; 廣田洋二 他: 'セメント製造と下水汚泥：セメント工場での安定処理・有効利用技術' セメント・コンクリート Ｎｏ． ６２１, 199811, ＰＡＧＥＳ ２４-２９, （社）セメント協会 |
| JPN3013000425; 下田孝: '２１世紀のセメント・コンクリート研究開発とセメント産業の役割' セメント・コンクリート Ｎｏ． ６３５, 20000110, ＰＡＧＥＳ ２-９, （社）セメント協会 |
| JPN3013000426; 田村浩章: 'セメント工場の未来像 循環型社会への貢献の可能性' セメント・コンクリート Ｎｏ． ６２３, 19990110, ＰＡＧＥＳ ４-８, （社）セメント協会 |
| JPN3013000427; 後英太郎: 新しいセメントとセメント技術 第１版, 19710125, ＰＡＧＥＳ ２２-２３， ４６-４７, （株）誠文堂新光社 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005087681A1 (en) * | 2004-03-11 | 2005-09-22 | Taiheiyo Cement Corporation | Hydraulic composition |
| US7722717B2 (en) | 2004-03-11 | 2010-05-25 | Taiheiyo Cement Corporation | Hydraulic composition |
| WO2010020079A1 (en) * | 2008-08-22 | 2010-02-25 | Tan Jilin | Sewage sludge cement and preparation thereof |
| CN103466970A (en) * | 2013-08-28 | 2013-12-25 | 句容联众科技开发有限公司 | Preparation method of sulfate corrosion resistance cement |
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| JP4164242B2 (en) | 2008-10-15 |
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