JP2015009999A - Cement composition and method for producing cement composition - Google Patents
Cement composition and method for producing cement composition Download PDFInfo
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- JP2015009999A JP2015009999A JP2013134562A JP2013134562A JP2015009999A JP 2015009999 A JP2015009999 A JP 2015009999A JP 2013134562 A JP2013134562 A JP 2013134562A JP 2013134562 A JP2013134562 A JP 2013134562A JP 2015009999 A JP2015009999 A JP 2015009999A
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- 239000004568 cement Substances 0.000 title claims abstract description 86
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000000428 dust Substances 0.000 claims abstract description 66
- 238000005406 washing Methods 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000460 chlorine Substances 0.000 claims abstract description 29
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010440 gypsum Substances 0.000 claims abstract description 18
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 3
- 238000009614 chemical analysis method Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- -1 KCl Chemical class 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 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
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 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
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011044 quartzite Substances 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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Abstract
Description
本発明は、塩素バイパスダスト装置を備えたセメント製造プラントで回収される塩素バイパスダストを水洗することで得られた水洗ダストをクリンカー粉砕工程で添加しても、セメントの凝結時間に影響を及ぼさないセメント組成物及びセメント組成物の製造方法に関するものである。 The present invention does not affect the setting time of cement even if water washing dust obtained by washing water with chlorine bypass dust recovered in a cement manufacturing plant equipped with a chlorine bypass dust device is added in the clinker grinding process. The present invention relates to a cement composition and a method for producing the cement composition.
セメント業界はセメントの原燃料として、塩素分の多い廃棄物（都市ゴミ焼却灰、廃プラスチックなど）を使用している。しかし、クリンカーの製造において、塩素は、セメント原料焼成系内におけるコーチングトラブルを誘発したり、セメントクリンカー中の塩素分を高めたりする。このため、セメント原料焼成系内における塩化アルカリ等の含有量を低減させることを目的に、例えば、特許文献１に示されるような、塩素バイパス装置がセメントキルンに付加的に設置されている。塩素バイパスダスト中には、ＫＣｌなどの塩化物やセメント原料の仮焼物とそれらの硫酸塩が含まれている。 The cement industry uses chlorine-rich waste (such as municipal waste incineration ash and waste plastics) as a raw material for cement. However, in the production of clinker, chlorine induces a coating trouble in the cement raw material firing system and increases the chlorine content in the cement clinker. For this reason, for the purpose of reducing the content of alkali chloride and the like in the cement raw material firing system, for example, a chlorine bypass device as shown in Patent Document 1 is additionally installed in the cement kiln. Chlorine bypass dust contains chlorides such as KCl, calcined cement raw materials, and sulfates thereof.
一方で、従来より、塩素バイパスダストの有効利用を図るため、種々の方法が提案されている。例えば、特許文献２では、塩素バイパスダストをセメントに添加し、セメントの強度改善を図る方法が提案されている。また、特許文献３では塩素バイパスダストを水洗処理し、塩素を除去したスラッジをセメント原料として添加する方法が提案されている。しかし、塩素バイパスダストは塩素含有量が高いため、セメントへの添加量は制限せざるを得ない。また、水洗ダストをクリンカー原料に添加した場合、その他の廃棄物原単位の低下や変更が必要となる。 On the other hand, various methods have heretofore been proposed for effective use of chlorine bypass dust. For example, Patent Document 2 proposes a method for improving the strength of cement by adding chlorine bypass dust to cement. Patent Document 3 proposes a method in which chlorine bypass dust is washed with water and sludge from which chlorine has been removed is added as a cement raw material. However, since chlorine bypass dust has a high chlorine content, the amount added to cement must be limited. In addition, when washing dust is added to the clinker raw material, it is necessary to reduce or change other waste unit values.
このようなことから、セメントの粉砕工程において、塩素含有量が少ない水洗ダストを添加することは、有効な手段であると考えられる。特許文献４には、水洗ダストをセメントに添加することによって、セメントからのＳｅの溶出を低減できることが開示されている。 For this reason, it is considered that adding washing dust having a low chlorine content in the cement grinding process is an effective means. Patent Document 4 discloses that the elution of Se from cement can be reduced by adding washing dust to cement.
しかしながら、特許文献４では水洗ダストを添加した場合のセメントの凝結時間の変動についての検討は行われていない。
そこで、本発明は、クリンカー粉砕時に、水洗ダストを添加しても、凝結時間に影響を及ぼさないセメント組成物及びセメント組成物の製造方法を提供することを目的とする。
However, Patent Document 4 does not discuss the variation in the setting time of cement when washing dust is added.
Therefore, an object of the present invention is to provide a cement composition that does not affect the setting time even when washing dust is added during clinker grinding, and a method for producing the cement composition.
本発明者らは上記目的を達成すべく鋭意検討した結果、水洗処理した塩素バイパスダスト中の水分含有量を調製した後に、クリンカーに添加することで凝結時間に影響しないセメント組成物が得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have obtained a cement composition that does not affect the setting time by adding to the clinker after preparing the water content in the chlorine bypass dust that has been washed with water. As a result, the present invention has been completed.
すなわち、本発明は、セメントクリンカーと石膏と塩素バイパスダストを水洗処理した水洗ダストを含むセメント組成物であって、前記セメントクリンカーのＣ3Ｓ含有量が４５〜６５質量％、Ｃ２Ｓ含有量が１４〜２４質量％、Ｃ3Ａ含有量が８〜１３質量％及びＣ4ＡＦ含有量が８〜１３質量％、前記水洗ダスト中の水分含有量が５〜２０質量％であり、前記セメント組成物中に水洗ダストを０．０１〜２．０質量％及び石膏をＳＯ３基準で０．５〜３．０質量％含み、前記セメント組成物のブレーン比表面積が３０００〜３５００ｃｍ２/ｇであるセメント組成物に関する。
また、本発明は、前記水洗ダストを乾燥し水分含有量を５〜２０質量％に調整した後、セメントクリンカー及び石膏と、混合及び粉砕し、前記セメント組成物を調製する、セメント組成物の製造方法に関する。
That is, the present invention is a cement composition containing water washing dust obtained by washing with cement clinker, gypsum, and chlorine bypass dust, wherein the C 3 S content of the cement clinker is 45 to 65% by mass, and the C 2 S content. 14-24% by mass, C 3 A content is 8-13% by mass, C 4 AF content is 8-13% by mass, water content in the washing dust is 5-20% by mass, The composition contains 0.01 to 2.0% by weight of washing dust and 0.5 to 3.0% by weight of gypsum based on SO 3 , and the cement composition has a Blaine specific surface area of 3000 to 3500 cm 2 / g. It relates to a certain cement composition.
Further, the present invention provides the cement composition, wherein the washing dust is dried to adjust the water content to 5 to 20% by mass, and then mixed and pulverized with cement clinker and gypsum to prepare the cement composition. Regarding the method.
本発明によれば、塩素バイパスダストならびに水洗ダストを有効利用できるとともに、クリンカー粉砕時に、水洗ダストを添加しても、水洗ダスト中の水分含有量を調整しておくことで、凝結時間に影響を及ぼさないセメント組成物及びセメント組成物の製造方法を提供することができる。 According to the present invention, chlorine bypass dust and water washing dust can be used effectively, and even if water washing dust is added during clinker grinding, the water content in water washing dust is adjusted, thereby affecting the setting time. It is possible to provide a cement composition that does not exert any effect and a method for producing the cement composition.
以下に本発明を詳しく説明する。 The present invention is described in detail below.
＜セメント組成物＞
本発明のセメント組成物は、セメントクリンカーと石膏と塩素バイパスダストを水洗処理した水洗ダストを含む。
セメントクリンカーのＣ3Ｓ含有量は４５〜６５質量％、好ましくは４７〜６３質量％、より好ましくは４９〜６１質量％、更に好ましくは５０〜６０質量％であり、Ｃ２Ｓ含有量は１０〜３０質量％、好ましくは１２〜２８質量％、より好ましくは１４〜２６質量％、更に好ましくは１５〜２５質量％であり、Ｃ3Ａ含有量は８〜１３質量％、
好ましくは８．５〜１２．５質量％、より好ましくは９．０〜１２．０質量％である。Ｃ4ＡＦ含有量は８〜１３質量％、好ましくは８．５〜１２．５質量％、より好ましくは９．０〜１２．０質量％である。このような組成範囲であれば、水洗ダストの水分含有量を調整することで、セメントの凝結時間への影響を小さくすることができる。
<Cement composition>
The cement composition of the present invention includes a washing dust obtained by washing a cement clinker, gypsum, and chlorine bypass dust.
The C 3 S content of the cement clinker is 45 to 65% by mass, preferably 47 to 63% by mass, more preferably 49 to 61% by mass, still more preferably 50 to 60% by mass, and the C 2 S content is 10%. 30 wt%, preferably from 12 to 28 wt%, more preferably 14 to 26 wt%, more preferably from 15 to 25 wt%, C 3 a content of 8-13% by weight,
Preferably it is 8.5-12.5 mass%, More preferably, it is 9.0-12.0 mass%. C 4 AF content is 8-13 wt%, preferably from 8.5 to 12.5 wt%, more preferably 9.0 to 12.0 wt%. If it is such a composition range, the influence on the setting time of cement can be made small by adjusting the water content of washing dust.
セメントクリンカーは、ＳＰ方式（多段サイクロン予熱方式）又はＮＳＰ方式（仮焼炉を併設した多段サイクロン予熱方式）等の既存のセメント製造設備を用いて、石灰石、珪石、石炭灰、粘土、高炉スラグ、建設発生土、下水汚泥、高炉ダスト、銅からみ、脱鉄スラグ及び焼却灰からなる群より選ばれる原料を混合し、焼成して製造することができる。石炭灰や高炉スラグのような産業廃棄物・副産物を比較的多く使用することにより、天然資源である石灰石や珪石の使用量を低減しかつ、エネルギー消費量等を低減することができるため、石灰石の熱分解や燃料の燃焼に起因するＣＯ２排出量を低減することができる。 Cement clinker uses limestone, quartzite, coal ash, clay, blast furnace slag, using existing cement manufacturing facilities such as SP method (multistage cyclone preheating method) or NSP method (multistage cyclone preheating method with calcining furnace). It can be manufactured by mixing and firing raw materials selected from the group consisting of construction generated soil, sewage sludge, blast furnace dust, copper, deiron slag and incinerated ash. By using relatively large amounts of industrial waste and by-products such as coal ash and blast furnace slag, it is possible to reduce the consumption of natural resources, such as limestone and silica, and reduce energy consumption. CO 2 emissions resulting from thermal decomposition of the fuel and combustion of the fuel can be reduced.
塩素バイパスダストは、塩素バイパス装置によって抽気された排ガスから集塵されたダストである。この塩素バイパスダストの固形物は、ＫＣｌ、ＮａＣｌ、ＣａＣｌ２等の塩化物やセメント原料の仮焼物、それらの硫酸塩等から成る。また、その塩素バイパスダストを水洗処理することによって塩素濃度が低い水洗ダストを得ることができる。
水洗ダスト中の水分含有量は、５〜２０質量％、好ましくは５．５〜１８質量％、より好ましくは６〜１７質量％、更に好ましくは６．５〜１６質量％である。この範囲であれば、凝結時間に影響を及ぼさないセメント組成物を得ることが可能である。
水洗ダスト中の水分含有量の調整は、キルンからの排ガスの利用や乾燥機を用いて行うことができる。本発明の水分含有量とは、１０５℃で乾燥して恒量になったときの重量減少量（％）である。
Chlorine bypass dust is dust collected from the exhaust gas extracted by the chlorine bypass device. The solid substance of this chlorine bypass dust consists of chlorides such as KCl, NaCl, CaCl 2 , calcined cement raw materials, sulfates thereof, and the like. Moreover, washing dust with a low chlorine concentration can be obtained by washing the chlorine bypass dust with water.
The water content in the washing dust is 5 to 20% by mass, preferably 5.5 to 18% by mass, more preferably 6 to 17% by mass, and still more preferably 6.5 to 16% by mass. Within this range, a cement composition that does not affect the setting time can be obtained.
The water content in the washing dust can be adjusted by using exhaust gas from the kiln or using a dryer. The water content of the present invention is the weight loss (%) when dried at 105 ° C. to become a constant weight.
水和停止を行った（結晶水以外の付着水を除去）後の水洗ダストのＳｉＯ２含有量は５〜２５質量％、好ましくは７〜２３質量％、より好ましくは９〜２３質量％、更に好ましくは１０〜２０質量％であり、Ａｌ２Ｏ３含有量は１．０〜１５．０質量％、好ましくは２〜１４質量％、より好ましくは２．５〜１３質量％、更に好ましくは３〜１２質量％であり、Ｆｅ２Ｏ３含有量は０．１〜３．０質量％、好ましくは０．５〜２．６質量％、より好ましくは０．７〜２．４質量％、更に好ましくは０．９〜２．２質量％であり、ＣａＯ含有量は３０〜６０質量％、好ましくは３３〜５７質量％、より好ましくは３５〜５５質量％、更に好ましくは３７〜５３質量％である。 The SiO 2 content of the washing dust after hydration stop (removal of adhering water other than crystal water) is 5 to 25% by mass, preferably 7 to 23% by mass, more preferably 9 to 23% by mass, preferably 10 to 20 wt%, Al 2 O 3 content of 1.0 to 15.0% by weight, preferably from 2 to 14 wt%, more preferably from 2.5 to 13 wt%, more preferably 3 a 12 wt%, Fe 2 O 3 content of 0.1 to 3.0 wt%, preferably from 0.5 to 2.6 wt%, more preferably 0.7 to 2.4 mass%, further Preferably it is 0.9-2.2 mass%, CaO content is 30-60 mass%, Preferably it is 33-57 mass%, More preferably, it is 35-55 mass%, More preferably, it is 37-53 mass%. is there.
また、Ｎａ２Ｏ含有量は０．１〜２．０質量％、好ましくは０．１５〜１．８質量％、より好ましくは０．２〜１．７質量％、更に好ましくは０．２５〜１．６質量％であり、Ｋ２Ｏ含有量は０．１〜３．０質量％、好ましくは０．４〜２．７質量％、より好ましくは０．６〜２．５質量％、更に好ましくは０．７〜２．４質量％であり、Ｃｌ含有量は０．１〜２．０質量％、好ましくは０．３〜１．８質量％、より好ましくは０．４〜１．７質量％、更に好ましくは０．５〜１．６質量％であり、ｆ．ＣａＯ含有量は５〜４０質量％、好ましくは７〜３８質量％、より好ましくは９〜３６質量％、更に好ましくは１０〜３５質量％である。
これらの範囲であれば、凝結時間に影響を及ぼさないセメント組成物を得ることが可能である。
Further, Na 2 O content of 0.1 to 2.0 wt%, preferably from 0.15 to 1.8 wt%, more preferably 0.2 to 1.7 wt%, more preferably 0.25 to 1.6 wt%, K 2 O content is 0.1 to 3.0% by weight, preferably from 0.4 to 2.7 wt%, more preferably 0.6 to 2.5 mass%, further Preferably it is 0.7-2.4 mass%, Cl content is 0.1-2.0 mass%, Preferably it is 0.3-1.8 mass%, More preferably, it is 0.4-1.7. % By mass, more preferably 0.5 to 1.6% by mass, f. The CaO content is 5 to 40% by mass, preferably 7 to 38% by mass, more preferably 9 to 36% by mass, and still more preferably 10 to 35% by mass.
Within these ranges, it is possible to obtain a cement composition that does not affect the setting time.
本発明のセメント組成物中に水洗ダストを０．０１〜２.０質量％、好ましくは０．１〜１．７質量％、より好ましくは０．２〜１．５質量％含む。含有量が０．０１質量％よりも少なければ、塩素バイパスダストならびに水洗ダストの有効利用に寄与できなくなる。一方、２質量％よりも多くなれば、強度発現性の低下を引き起こす。
本発明のセメント組成物中に石膏をＳＯ３基準で０．５〜３．５質量％、好ましくは１．０〜３．０質量％、より好ましくは１．５〜２．７質量％、更に好ましくは１．７〜２．５質量％含む。これらの範囲であれば、凝結時間に影響を及ぼさないセメント組成物を得ることが可能である。
The cement composition of the present invention contains water-washed dust in an amount of 0.01 to 2.0% by mass, preferably 0.1 to 1.7% by mass, and more preferably 0.2 to 1.5% by mass. If the content is less than 0.01% by mass, it cannot contribute to the effective use of chlorine bypass dust and washing dust. On the other hand, if it exceeds 2 mass%, strength development will be reduced.
The gypsum in the cement composition of the present invention is 0.5 to 3.5% by mass, preferably 1.0 to 3.0% by mass, more preferably 1.5 to 2.7% by mass, based on SO 3. Preferably it contains 1.7-2.5 mass%. Within these ranges, it is possible to obtain a cement composition that does not affect the setting time.
本発明に用いる石膏は、ＪＩＳ Ｒ ９１５１「セメント用天然石膏」に規定される品質を満足することが望ましい。具体的に二水石膏、半水石膏、不溶性無水石膏が好適に用いられる。
セメント組成物のブレーン比表面積は３０００〜３５００ｃｍ２/ｇ、好ましくは３０５０〜３４００ｃｍ２/ｇ、より好ましくは３１００〜３３００ｃｍ２/ｇ、更に好ましくは３１５０〜３２５０ｃｍ２/ｇである。これらの範囲であれば、凝結時間に影響を及ぼさないセメント組成物を得ることが可能である。
本発明では、必要に応じて、混合材を添加してもよい。混合材は、ＪＩＳ Ｒ ５２１１「高炉セメント」に規定される高炉スラグ、ＪＩＳ Ｒ ５２１２「シリカセメント」に規定されるシリカ質混合材、ＪＩＳ Ａ ６２０１「コンクリート用フライアッシュ」に規定されるフライアッシュ、石灰石微粉末を利用することができる。
また、本発明では、塩素バイパスダストをさらに添加することができる。
It is desirable that the gypsum used in the present invention satisfies the quality defined in JIS R 9151 “Natural gypsum for cement”. Specifically, dihydrate gypsum, hemihydrate gypsum, and insoluble anhydrous gypsum are preferably used.
3000~3500cm 2 / g, the Blaine specific surface area of the cement composition is preferably from 3050~3400cm 2 / g, more preferably 3100~3300cm 2 / g, more preferably 3150~3250cm 2 / g. Within these ranges, it is possible to obtain a cement composition that does not affect the setting time.
In this invention, you may add a mixing material as needed. The mixed material is a blast furnace slag defined in JIS R 5211 “Blast Furnace Cement”, a siliceous mixed material defined in JIS R 5212 “Silica Cement”, fly ash defined in JIS A 6201 “Fly Ash for Concrete”, Limestone fine powder can be used.
In the present invention, chlorine bypass dust can be further added.
＜セメント組成物の製造方法＞
本発明のセメント組成物の製造方法は、上述した水洗ダストを乾燥し水分含有量を５〜２０質量％、５．５〜１８質量％、より好ましくは６〜１７質量％、更に好ましくは６．５〜１６質量％に調整する。この範囲であれば、凝結時間に影響を及ぼさないセメント組成物を製造することが可能である。
<Method for producing cement composition>
In the method for producing the cement composition of the present invention, the above-mentioned washing dust is dried and the water content is 5 to 20% by mass, 5.5 to 18% by mass, more preferably 6 to 17% by mass, and still more preferably 6. Adjust to 5-16 mass%. Within this range, it is possible to produce a cement composition that does not affect the setting time.
次に、乾燥した水洗ダストと、セメントクリンカー及び石膏とを混合及び粉砕し、上述したセメント組成物を調製する。混合及び粉砕する方法としては、水洗ダストとセメントクリンカーを同時に粉砕した後に、石膏を混合する方法や全てを同時に粉砕する方法が挙げられる。
水洗ダストを乾燥する温度は２０〜４０℃、好ましくは２２〜３８℃、より好ましくは２４〜３６℃、更に好ましくは２５〜３５℃である。この範囲であれば、凝結時間に影響を及ぼさないセメント組成物を製造することが可能である。
Next, the dried water washing dust, cement clinker and gypsum are mixed and pulverized to prepare the above-described cement composition. Examples of the mixing and pulverizing method include a method in which the washing dust and the cement clinker are simultaneously pulverized, and then a method of mixing gypsum and a method in which all are simultaneously pulverized.
The temperature for drying the washing dust is 20 to 40 ° C., preferably 22 to 38 ° C., more preferably 24 to 36 ° C., and further preferably 25 to 35 ° C. Within this range, it is possible to produce a cement composition that does not affect the setting time.
以下に、実施例及び比較例を挙げて本発明の内容を詳細に説明する。なお、本発明はこれらの例によって限定されるものではない。 The contents of the present invention will be described in detail below with reference to examples and comparative examples. Note that the present invention is not limited to these examples.
[セメントの調製]
セメントの調製には、試験ボールミルを使用し、クリンカー、石膏および乾燥後の水洗ダストを同時に粉砕した。また、石膏の添加量はセメントＳＯ３含有量が１．９質量％となる量とし、水洗ダストの添加量は、全粉砕物に対して内割で１．２質量％とした。セメントのブレーン比表面積は３２００±１００cm2/gとした。また、参考として、水洗ダスト無添加のセメントも作製した。
[Preparation of cement]
For the preparation of the cement, a test ball mill was used, and the clinker, gypsum and water-washed dust after drying were ground at the same time. The amount of gypsum added was such that the cement SO 3 content was 1.9% by mass, and the amount of water-washed dust added was 1.2% by mass relative to the total pulverized product. The cement specific surface area of cement was 3200 ± 100 cm 2 / g. Also, as a reference, a cement without water washing dust was also prepared.
ここで、各種材料のキャラクターを示す。クリンカーの鉱物組成を表１に示す。なお、ポルトランドセメントクリンカーの鉱物組成は、ＪＩＳ Ｒ ５２０２：２０１０「セメントの化学分析方法」に準じて化学成分を定量し、Ｃ3Ｓ含有量、Ｃ２Ｓ含有量、Ｃ3Ａ含有量、Ｃ4ＡＦ含有量は式（１）〜（４）により求めた。 Here, characters of various materials are shown. Table 1 shows the mineral composition of the clinker. The mineral composition of the Portland cement clinker is determined by quantifying chemical components according to JIS R 5202: 2010 “Chemical chemical analysis method”, C 3 S content, C 2 S content, C 3 A content, C 4 AF content was calculated | required by Formula (1)-(4).
Ｃ３Ｓ＝４．０７×（ＣａＯ−ｆ.ＣａＯ）−７．６０×ＳｉＯ２−６．７２×Ａｌ２Ｏ３−１．４３×Ｆｅ２Ｏ３・・・式（１）
Ｃ２Ｓ＝２．８７×ＳｉＯ２−０．７５×Ｃ３Ｓ・・・式（２）
Ｃ３Ａ＝２．６５×Ａｌ２Ｏ３−１．６９×Ｆｅ２Ｏ３・・・式（３）
Ｃ４ＡＦ＝３．０４×Ｆｅ２Ｏ３・・・式（４）
C 3 S = 4.07 × (CaO -f.CaO) -7.60 × SiO 2 -6.72 × Al 2 O 3 -1.43 × Fe 2 O 3 ··· Equation (1)
C 2 S = 2.87 × SiO 2 -0.75 × C 3 S ··· Equation (2)
C 3 A = 2.65 × Al 2 O 3 −1.69 × Fe 2 O 3 Formula (3)
C 4 AF = 3.04 × Fe 2 O 3 Formula (4)
水洗ダストの化学組成を表２及び表３に示す。化学成分は、ＪＩＳ Ｒ ５２０２：２０１０「セメントの化学分析方法」に準じて求めた。ｆ.ＣａＯ含有量はセメント協会標準試験法のＪＣＡＳ Ｉ−０１：１９９７「遊離酸化カルシウムの定量方法」に準じて測定した。なお、水洗ダストの化学組成は、アセトンによる洗浄を行って水和停止した後、２０℃で６時間真空乾燥したものの値（結晶水以外の付着水を除去した値）である。 Tables 2 and 3 show the chemical composition of the washing dust. The chemical component was determined according to JIS R 5202: 2010 “Chemical analysis method of cement”. f. The CaO content was measured according to JCAS I-01: 1997 “Quantitative determination method of free calcium oxide” of the Cement Association standard test method. The chemical composition of the water washing dust is a value obtained by washing with acetone to stop hydration and then vacuum drying at 20 ° C. for 6 hours (a value obtained by removing adhering water other than crystal water).
水洗ダストは、３０℃、６０℃、１０５℃で加熱乾燥して水分含有量を調整した。得られた水洗ダストの水分含有量を表４に示す。なお、ここに示す水分含有量は水和停止を行っていない状態の水洗ダストを対象とした。 Washing dust was heated and dried at 30 ° C., 60 ° C., and 105 ° C. to adjust the water content. Table 4 shows the water content of the obtained washing dust. The water content shown here was for washing dust in a state where hydration was not stopped.
石膏の化学成分は表５に示すとおりである。これらの化学成分はＪＩＳ Ｒ ５２０２：２０１０「セメントの化学分析方法」に準じて求めた。 The chemical composition of gypsum is as shown in Table 5. These chemical components were determined according to JIS R 5202: 2010 “Chemical chemical analysis method”.
次に、JIS R５２０１：１９９７に規定された「セメントの物理試験方法」に従って、凝結試験を行った。 Next, a setting test was performed according to “Physical Test Method for Cement” defined in JIS R5201: 1997.
表６に結果を示す。水洗ダスト中の水分含有量が９．７％の実施例１が、水洗ダスト無添加（参考値１）のセメントに近い凝結時間となることがわかる。 Table 6 shows the results. It can be seen that Example 1 having a water content of 9.7% in the washing dust has a setting time close to that of the cement with no washing dust added (reference value 1).
水洗ダスト中の水分含有量によってセメントの凝結時間が異なる理由についてはよくわからないが、水洗ダスト中の水分が、水酸化カルシウムの被粉砕性に影響しているためと考えられる。 The reason why the setting time of the cement varies depending on the water content in the washing dust is not well understood, but it is considered that the moisture in the washing dust affects the grindability of calcium hydroxide.
Claims (4)
前記セメントクリンカーのＣ3Ｓ含有量が４５〜６５質量％、Ｃ２Ｓ含有量が１４〜２４質量％、Ｃ3Ａ含有量が８〜１３質量％及びＣ4ＡＦ含有量が８〜１３質量％、前記水洗ダスト中の水分含有量が５〜２０質量％であり、
前記セメント組成物中に水洗ダストを０．０１〜２．０質量％及び石膏をＳＯ３基準で０．５〜３．０質量％含み、
前記セメント組成物のブレーン比表面積が３０００〜３５００ｃｍ２/ｇであることを特徴とするセメント組成物。 A cement composition comprising water-washed dust obtained by washing a cement clinker, gypsum and chlorine bypass dust,
The cement clinker has a C 3 S content of 45 to 65 mass%, a C 2 S content of 14 to 24 mass%, a C 3 A content of 8 to 13 mass%, and a C 4 AF content of 8 to 13 mass%. %, The water content in the washing dust is 5 to 20% by mass,
The 0.01 to 2.0% by weight and gypsum washing dust in the cement composition comprises 0.5 to 3.0% by weight SO 3 basis,
A cement composition, wherein the cement composition has a Blaine specific surface area of 3000 to 3500 cm 2 / g.
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| JP2018162200A (en) * | 2017-03-27 | 2018-10-18 | 宇部興産株式会社 | Cement composition and method for producing the same |
| JP2018162199A (en) * | 2017-03-27 | 2018-10-18 | 宇部興産株式会社 | Cement composition and method for producing the same |
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