JP2014001122A - Fired product - Google Patents
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- JP2014001122A JP2014001122A JP2012205751A JP2012205751A JP2014001122A JP 2014001122 A JP2014001122 A JP 2014001122A JP 2012205751 A JP2012205751 A JP 2012205751A JP 2012205751 A JP2012205751 A JP 2012205751A JP 2014001122 A JP2014001122 A JP 2014001122A
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- 239000002699 waste material Substances 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 239000011737 fluorine Substances 0.000 claims abstract description 19
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 19
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000002689 soil Substances 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010276 construction Methods 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000002440 industrial waste Substances 0.000 claims description 5
- 239000000356 contaminant Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 32
- 239000004567 concrete Substances 0.000 abstract description 19
- 239000004570 mortar (masonry) Substances 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000010304 firing Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000010410 dusting Methods 0.000 description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 5
- 235000012255 calcium oxide Nutrition 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000004568 cement Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000010801 sewage sludge Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000010436 fluorite Substances 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010920 waste tyre Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 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
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-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
- 239000010883 coal ash Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Description
本発明は、モルタルやコンクリート用の骨材、路盤材、盛土材及び埋め戻し材等の土木・港湾材料として好適に用いることができる焼成物に関する。 The present invention relates to a fired product that can be suitably used as civil engineering and port materials such as aggregates for mortar and concrete, roadbed materials, embankment materials, and backfill materials.
近年、経済成長や都市部への人口集中等に伴い、産業廃棄物や一般廃棄物等が急増している。従来より、これら廃棄物の大半は、焼却することによって減容化した後、埋め立て処分されているものの、埋め立て処分場における残余容量が逼迫化しつつある現状下では、新しい廃棄物処理方法の確立が急務である。かかる急務に対応すべく、例えば、特許文献１には、原料として廃棄物等を有効に使用することができる焼成物が提案されている。
In recent years, with the economic growth and population concentration in urban areas, industrial waste, general waste, etc. are rapidly increasing. Conventionally, most of these wastes have been disposed of in landfills after being reduced in volume by incineration. However, under the current situation where the remaining capacity at landfill sites is becoming tight, new waste disposal methods have been established. There is an urgent need. In order to respond to such an urgent need, for example,
かかる焼成物は、粉砕することによりセメント添加材として使用することもでき、また粉砕せずとも、そのままモルタルやコンクリート用の骨材、路盤材、盛土材や埋め戻し材等の材料として使用することもできる。 The fired product can be used as a cement additive by being pulverized, and can be used as a material for mortar, concrete aggregate, roadbed material, embankment material, backfill material, etc. without pulverization. You can also.
しかしながら、近年、我が国におけるセメント生産量は減少傾向にあるため、上記焼成物をセメント添加材として使用するのみでは、急増する廃棄物等を多量に消費するのは困難である。また、かかる焼成物を骨材や路盤材等に用いたとしても、これらに用いるのに好適な高い圧壊強度を実現する上で十分な容重や粉砕耐性を付与するには、依然として改善の余地がある。 However, in recent years, the amount of cement production in Japan has been declining, and it is difficult to consume a large amount of rapidly increasing waste and the like only by using the fired product as a cement additive. Moreover, even if such fired products are used for aggregates, roadbed materials, etc., there is still room for improvement in order to provide sufficient weight and crushing resistance to achieve high crushing strength suitable for use in these. is there.
したがって、本発明の目的は、原料として廃棄物等を有効に使用することができるとともに、モルタルやコンクリート用の骨材、路盤材、盛土材及び埋め戻し材等の好適な材料として使用することができる焼成物を提供することにある。 Therefore, the object of the present invention is to be able to use wastes and the like effectively as raw materials, and to be used as suitable materials such as aggregates, roadbed materials, embankment materials and backfill materials for mortar and concrete. It is in providing the baked product which can be performed.
そこで本発明者は、種々検討したところ、特定の鉱物組成を有するとともに特定量のフッ素を含有することにより、圧壊強度を十分に高め得る容重及び粉砕耐性を兼ね備えた焼成物が得られることを見出し、本発明を完成させるに至った。 Therefore, the present inventor has conducted various studies and found that by containing a specific amount of fluorine while having a specific mineral composition, a fired product having sufficient weight and crushing resistance capable of sufficiently increasing the crushing strength can be obtained. The present invention has been completed.
すなわち、本発明は、２ＣａＯ・ＳｉＯ2（以下、Ｃ2Ｓと称する）１００質量部に対して、２ＣａＯ・Ａｌ2Ｏ3・ＳｉＯ2（以下、Ｃ2ＡＳと称する）を１０〜１００質量部含有し、かつ３ＣａＯ・Ａｌ2Ｏ3（以下、Ｃ3Ａと称する）の含有量が２０質量部以下である焼成物であって、焼成物１００質量％中に、フッ素を０．０３〜０．２質量％含有する焼成物を提供するものである。 That is, according to the present invention, 10 parts by mass of 2CaO.Al 2 O 3 .SiO 2 (hereinafter referred to as C 2 AS) is 10 parts by mass with respect to 100 parts by mass of 2CaO · SiO 2 (hereinafter referred to as C 2 S). A fired product containing 3CaO · Al 2 O 3 (hereinafter referred to as C 3 A) is 20 parts by mass or less, and 0.03 to 0 fluorine in 100% by mass of the fired product. The present invention provides a fired product containing 2% by mass.
本発明の焼成物によれば、原料として廃棄物等を用いても、容重を増大することができるとともに粉砕耐性をも高めることができるため、優れた圧壊強度をもたらし、モルタルやコンクリート用の骨材、路盤材、盛土材及び埋め戻し材等の材料として好適に用いることが可能である。したがって、急増する廃棄物等を多量に消費する上でも、非常に有用な焼成物である。 According to the fired product of the present invention, even if waste or the like is used as a raw material, the weight can be increased and the crushing resistance can be increased. It can be suitably used as materials such as materials, roadbed materials, embankment materials and backfill materials. Therefore, it is a very useful baked product even in the case of consuming a large amount of rapidly increasing waste.
以下、本発明について詳細に説明する。
本発明の焼成物は、Ｃ2Ｓ１００質量部に対して、Ｃ2ＡＳを１０〜１００質量部含有し、かつＣ3Ａの含有量が２０質量部以下である焼成物であって、焼成物１００質量％中に、フッ素を０．０３〜０．２質量％含有する。
Hereinafter, the present invention will be described in detail.
The calcined product of the present invention is a calcined product containing 10 to 100 parts by mass of C 2 AS with respect to 100 parts by mass of C 2 S, and the content of C 3 A is 20 parts by mass or less. In 100% by mass, 0.03 to 0.2% by mass of fluorine is contained.
上記Ｃ2Ｓは、水硬性を有しており、コンクリートや路盤等中で緩和に反応を進行させ、これらコンクリートや路盤等を緻密化して強度を高めることができる。また、上記Ｃ2ＡＳは、水硬性を有しないものの、炭酸化によって緻密化するため、コンクリートの中性化を抑制したり、路盤等の強度を高めたりする効果を発揮することができる。 The C 2 S has hydraulic properties, and can react with relaxation in concrete, roadbed, etc., and can increase the strength by densifying the concrete, roadbed, etc. In addition, although the C 2 AS does not have hydraulic properties, the C 2 AS is densified by carbonation, and thus can exert an effect of suppressing the neutralization of concrete or increasing the strength of a roadbed or the like.
本発明の焼成物中におけるＣ2ＡＳの含有量は、Ｃ2Ｓ１００質量部に対して、１０〜１００質量部であって、好ましくは２０〜９０質量部であり、より好ましくは２５〜８０質量部である。Ｃ2Ｓ１００質量部に対し、Ｃ2ＡＳの含有量が１０質量部未満であると、焼成物の吸水率が増大するおそれがあるとともに、冷却の際に焼成物が粉状化する現象（ダスティング）が生じるおそれがある。また、１００質量部を超えると、高温において融液が増加するおそれがあるので、焼成可能温度の幅が狭まる傾向にある。 The content of C 2 AS in the fired product of the present invention is 10 to 100 parts by weight, preferably 20 to 90 parts by weight, and more preferably 25 to 80 parts by weight with respect to 100 parts by weight of C 2 S. Part. When the content of C 2 AS is less than 10 parts by mass relative to 100 parts by mass of C 2 S, the water absorption rate of the calcined product may increase, and the calcined product becomes powdery during cooling (dummy Sting) may occur. Moreover, since there exists a possibility that a melt may increase at high temperature when it exceeds 100 mass parts, it exists in the tendency for the breadth of the temperature which can be baked to narrow.
上記Ｃ3Ａは、焼成物の吸水率を低下させる観点、及び骨材や路盤材等として用いた際に膨張破壊が発生するのを防止して、コンクリートや路盤等の耐久性が低下するのを抑制する観点から、その含有量を減じるのがよい。具体的には、本発明の焼成物中におけるＣ3Ａの含有量は、Ｃ2Ｓ１００質量部に対して、２０質量部以下であって、好ましくは０〜１０質量部である。 The above C 3 A reduces the water absorption rate of the fired product, and prevents the occurrence of expansion failure when used as an aggregate or roadbed material, thereby reducing the durability of concrete, roadbed, etc. From the viewpoint of suppressing the content, the content should be reduced. Specifically, the content of C 3 A in the fired product of the present invention is 20 parts by mass or less and preferably 0 to 10 parts by mass with respect to 100 parts by mass of C 2 S.
本発明の焼成物は、フッ素を含有する。これにより、十分に容重を増大させながら粉砕耐性を増強させることができ、圧壊強度を十分に高めることが可能となる。本発明の焼成物中におけるフッ素の含有量は、焼成物１００質量％中に、０．０３〜０．２質量％であって、好ましくは０．０３５〜０．１５質量％であり、より好ましくは０．０４〜０．１質量％である。焼成物１００質量％中におけるフッ素の含有量が０．０３質量％未満であると、容重が小さくなるおそれがあるとともに、粉砕耐性が低下するおそれがある。また、焼成物１００質量％中におけるフッ素の含有量が０．２質量％を超えると、水に浸漬した際、環境基準値を超える量のフッ素が焼成物から溶出するおそれがある。 The fired product of the present invention contains fluorine. Thereby, the crushing resistance can be enhanced while sufficiently increasing the weight, and the crushing strength can be sufficiently increased. The fluorine content in the fired product of the present invention is 0.03 to 0.2% by weight, preferably 0.035 to 0.15% by weight, more preferably 100% by weight of the fired product. Is 0.04 to 0.1 mass%. When the fluorine content in 100% by mass of the fired product is less than 0.03% by mass, the weight may be reduced and the crushing resistance may be reduced. Moreover, when the content of fluorine in 100% by mass of the fired product exceeds 0.2% by mass, when immersed in water, an amount of fluorine exceeding the environmental standard value may be eluted from the fired product.
本発明の焼成物における亜鉛の含有量は、優れた粉砕耐性を実現する等の観点から、焼成物１００質量％中に、好ましくは０．０３〜０．５質量％であり、より好ましくは０．０４〜０．４質量％であり、さらに好ましくは０．０５〜０．２質量％である。焼成物１００質量％中における亜鉛の含有量が０．０３質量％未満であると、粉砕耐性が低下するおそれがある。また、焼成物１００質量％中における亜鉛の含有量が０．５質量％を超えると、コンクリートを製造した際、焼成物から水中に亜鉛が溶出して凝結を遅延させる等の要因となるおそれがある。 The content of zinc in the fired product of the present invention is preferably 0.03 to 0.5% by weight, more preferably 0, in 100% by weight of the fired product, from the viewpoint of realizing excellent crush resistance. 0.04 to 0.4 mass%, more preferably 0.05 to 0.2 mass%. If the zinc content in 100% by mass of the fired product is less than 0.03% by mass, the crushing resistance may decrease. Moreover, when the content of zinc in 100% by mass of the fired product exceeds 0.5% by mass, when concrete is produced, zinc may be eluted from the fired product into the water to delay the setting. is there.
本発明の焼成物におけるＳＯ3の含有量は、焼成処理を容易にする観点、焼成物における高い圧壊強度や耐摩耗性を保持する観点、及び吸水率を低減して安定性を高める観点から、焼成物１００質量％中に、好ましくは１．５質量％以下であり、より好ましくは１．０質量％以下である。 The content of SO 3 in the fired product of the present invention is from the viewpoint of facilitating the firing process, from the viewpoint of maintaining high crushing strength and wear resistance in the fired product, and from the viewpoint of increasing the stability by reducing the water absorption rate. It is preferably 1.5% by mass or less, and more preferably 1.0% by mass or less, in 100% by mass of the fired product.
このような組成の焼成物を製造するための原料としては、一般のポルトランドセメントクリンカー原料、すなわち、石灰石、生石灰、消石灰等のＣａＯ原料、珪石、粘土等のＳｉＯ2原料、粘土等のＡｌ2Ｏ3原料、鉄滓、鉄ケーキ等のＦｅ2Ｏ3原料を使用することができる。
フッ素原料としては、蛍石、フッ素汚泥等を使用することができる。
亜鉛原料としては、工業用酸化亜鉛のほか、廃タイヤ、廃油、金属スラグ等を使用することができる。
ＳＯ3原料としては、廃石膏ボード、廃硫酸等の廃棄物原料を使用することができる。また、石膏も使用することができる。さらに、ペトコークス等の高硫黄含有燃料を使用することもできる。
As a raw material for producing a fired product having such a composition, a general Portland cement clinker raw material, that is, a CaO raw material such as limestone, quicklime, and slaked lime, a SiO 2 raw material such as silica and clay, and an Al 2 O such as clay 3 Raw materials, Fe 2 O 3 raw materials such as iron cake and iron cake can be used.
As the fluorine raw material, fluorite, fluorine sludge and the like can be used.
As the zinc raw material, in addition to industrial zinc oxide, waste tires, waste oil, metal slag, and the like can be used.
As the SO 3 raw material, waste raw materials such as waste gypsum board and waste sulfuric acid can be used. Gypsum can also be used. Furthermore, a high sulfur content fuel such as pet coke can also be used.
さらに、本発明の焼成物におけるＰ2Ｏ5の含有量は、ダスティングを防止する観点から、好ましくは０．３質量％以上であり、より好ましくは０．４質量％以上であり、さらに好ましくは０．５質量％以上である。焼成物１００質量％中におけるＰ2Ｏ5含有量が０．３質量％未満であると、ダスティングが発生して粉状物が多くなる場合がある。また、焼成物１００質量％中におけるＰ2Ｏ5の含有量は、焼成物のコスト等の観点から、好ましくは２０質量％以下であり、より好ましくは１５質量％以下であり、さらに好ましくは１０質量％以下である。
なお、焼成物中のＰ2Ｏ5の含有量は、下水汚泥等のリン含有廃棄物を原料として使用したり、リン酸水素カルシウム等の工業材料を使用したりすることによって調整することができる。
Furthermore, the content of P 2 O 5 in the fired product of the present invention is preferably 0.3% by mass or more, more preferably 0.4% by mass or more, and further preferably from the viewpoint of preventing dusting. Is 0.5% by mass or more. If the P 2 O 5 content in 100% by mass of the fired product is less than 0.3% by mass, dusting may occur and the amount of powdery material may increase. Further, the content of P 2 O 5 in 100% by mass of the fired product is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% from the viewpoint of the cost of the calcined product. It is below mass%.
The content of P 2 O 5 in the fired product can be adjusted by using phosphorus-containing waste such as sewage sludge as a raw material or using industrial materials such as calcium hydrogen phosphate. .
上記のように、焼成物１００質量％中におけるＰ2Ｏ5の含有量が０．３質量％未満であると、ダスティングが発生する場合があるが、これを効果的に防止するには、焼成物中のＫ2Ｏ及び／又はＮａ2Ｏの合計含有量を調整するのがよい。すなわち、本発明の焼成物におけるＰ2Ｏ5の含有量が０．３質量％未満であるとき、ダスティング防止や焼成のし易さ向上の観点から、Ｋ2Ｏ及び／又はＮａ2Ｏの合計含有量は、好ましくは１．０〜５．０質量％であり、より好ましくは１．５〜４．５質量％であり、さらに好ましくは２．０〜４．０質量％である。
なお、焼成物中のＫ2Ｏ及び／又はＮａ2Ｏの合計含有量は、廃ガラス等の廃棄物を原料として使用したり、炭酸ナトリウム等の工業材料を使用したりすることによって調整することができる。
As described above, dusting may occur when the content of P 2 O 5 in the fired product is less than 0.3% by mass. To effectively prevent this, It is preferable to adjust the total content of K 2 O and / or Na 2 O in the fired product. That is, when the content of P 2 O 5 in the fired product of the present invention is less than 0.3% by mass, from the viewpoint of preventing dusting and improving the ease of firing, the content of K 2 O and / or Na 2 O Total content becomes like this. Preferably it is 1.0-5.0 mass%, More preferably, it is 1.5-4.5 mass%, More preferably, it is 2.0-4.0 mass%.
The total content of K 2 O and / or Na 2 O in the fired product should be adjusted by using waste materials such as waste glass as raw materials or using industrial materials such as sodium carbonate. Can do.
また、本発明においては、焼成物の原料として、産業廃棄物、一般廃棄物、汚染物及び建設発生土から選ばれる１種以上を用いることもでき、廃棄物の有効利用を促進させることができるので、天然資源や環境保護の面からも好ましい。ここで、産業廃棄物としては、例えば石炭灰；生コンスラッジ；下水汚泥、浄水汚泥、建設汚泥、製鉄汚泥等の各種汚泥；ボーリング廃土、各種焼却灰、鋳物砂、ロックウール、廃ガラス、高炉２次灰、建設廃材、コンクリート廃材などが挙げられる。一般廃棄物としては、例えば下水汚泥乾粉、都市ごみ焼却灰、貝殻等が挙げられる。汚染物としては、重金属汚染土壌、有機物汚染土壌、フッ素汚染土壌等が挙げられる。建設発生土としては、建設現場や工事現場等から発生する土壌や残土、さらには廃土壌等が挙げられる。 Moreover, in this invention, 1 or more types chosen from an industrial waste, a general waste, a pollutant, and construction generation | occurence | production soil can also be used as a raw material of a baked product, and the effective utilization of a waste can be promoted. Therefore, it is preferable from the viewpoint of natural resources and environmental protection. Here, industrial waste includes, for example, coal ash; raw consludge; various sludges such as sewage sludge, purified water sludge, construction sludge, and iron sludge; Secondary ash, construction waste, concrete waste, etc. are listed. Examples of the general waste include sewage sludge dry powder, municipal waste incineration ash, and shells. Examples of contaminants include heavy metal contaminated soil, organic matter contaminated soil, and fluorine contaminated soil. Examples of construction generated soil include soil and residual soil generated from construction sites and construction sites, and waste soil.
なお、焼成物の原料組成によっては、特に、上記産業廃棄物、一般廃棄物、汚染物及び建設発生土から選ばれる１種以上（以下、廃棄物原料と称する）を原料として用いた場合、４ＣａＯ・Ａｌ2Ｏ3・Ｆｅ2Ｏ3（以下、Ｃ4ＡＦと称する）が生成することがあるが、本発明の焼成物においては、好ましくはＣ2ＡＳの一部、より好ましくはＣ2ＡＳ中の７０質量％以下がＣ4ＡＦで置換されてもよい。Ｃ4ＡＦがこの範囲を超えて置換されると、焼成の温度範囲が狭くなって製造の管理が困難となるおそれがある。 Depending on the raw material composition of the fired product, in particular, when one or more selected from the above industrial waste, general waste, pollutant and construction generated soil (hereinafter referred to as waste raw material) is used as the raw material, 4CaO · Al 2 O 3 · Fe 2 O 3 (hereinafter referred to as C 4 AF) may be produced, but in the fired product of the present invention, preferably a part of C 2 AS, more preferably C 2 AS 70 mass% or less of the inside may be substituted with C 4 AF. When C 4 AF is substituted beyond this range, the firing temperature range becomes narrow, and the production control may become difficult.
本発明の焼成物の鉱物組成（Ｃ4ＡＦ、Ｃ3Ａ、Ｃ2ＡＳ、Ｃ2Ｓ）は、使用原料や焼成物中のＣａＯ、ＳｉＯ2、Ａｌ2Ｏ3、Ｆｅ2Ｏ3の各含有量（重量％）から、次式により求めることができる。
Ｃ4ＡＦ＝３．０４×Ｆｅ2Ｏ3
Ｃ3Ａ＝１．６１×ＣａＯ−３．００×ＳｉＯ2−２．２６×Ｆｅ2Ｏ3
Ｃ2ＡＳ＝−１．６３×ＣａＯ＋３．０４×ＳｉＯ2＋２．６９×Ａｌ2Ｏ3＋０．５７×Ｆｅ2Ｏ3
Ｃ2Ｓ＝１．０２×ＣａＯ＋０．９５×ＳｉＯ2−１．６９×Ａｌ2Ｏ3−０．３６×Ｆｅ2Ｏ3
Mineral composition of the burned material of the present invention (C 4 AF, C 3 A , C 2 AS, C 2 S) is, CaO in the raw materials used and the fired product in each of SiO 2, Al 2 O 3, Fe 2 O 3 From the content (% by weight), it can be obtained by the following formula.
C 4 AF = 3.04 × Fe 2 O 3
C 3 A = 1.61 × CaO−3.00 × SiO 2 −2.26 × Fe 2 O 3
C 2 AS = −1.63 × CaO + 3.04 × SiO 2 + 2.69 × Al 2 O 3 + 0.57 × Fe 2 O 3
C 2 S = 1.02 × CaO + 0.95 × SiO 2 -1.69 × Al 2 O 3 −0.36 × Fe 2 O 3
なお、本発明の焼成物におけるフッ素、亜鉛及びＳＯ3の含有量は、得られた焼成物の組成から求められる値である。したがって、例えば、使用原料中にフッ素が不足する場合、その不足分を調整するために、上記フッ素原料を混合して用いればよい。混合割合は、使用原料の組成に応じて、得られる焼成物中の含有量が本発明の範囲内になるよう、適宜決定すればよい。 The contents of fluorine, zinc and SO 3 in the fired product of the present invention are values determined from the composition of the obtained fired product. Therefore, for example, when fluorine is insufficient in the raw material used, in order to adjust the shortage, the fluorine raw material may be mixed and used. What is necessary is just to determine a mixing ratio suitably according to the composition of a raw material to be used so that content in the obtained baked product may become in the range of this invention.
本発明の焼成物は、上記のような原料を適宜混合し、焼成することにより製造することができる。各原料を混合する方法は特に限定されず、慣用の装置等を用いて行えばよい。また、焼成する際の焼成温度は、１０００〜１３５０℃が好ましく、１１５０〜１３５０℃であるのがより好ましい。焼成温度が１０００℃未満であると、フリーライム量を低減させることが困難となるおそれがあり、１３５０℃を超えると、原料混合物が溶融してしまうおそれがある。 The fired product of the present invention can be produced by appropriately mixing and firing the above raw materials. The method for mixing the raw materials is not particularly limited, and may be performed using a conventional apparatus or the like. Moreover, 1000-1350 degreeC is preferable and the firing temperature at the time of baking has more preferable 1150-1350 degreeC. If the firing temperature is less than 1000 ° C, it may be difficult to reduce the amount of free lime, and if it exceeds 1350 ° C, the raw material mixture may be melted.
焼成に用いる装置は特に限定されず、例えばロータリーキルン等を用いることができる。また、ロータリーキルンを用いて焼成する際には、燃料代替廃棄物、例えば廃油、廃タイヤ、廃プラスチック等を使用することもできる。 The apparatus used for baking is not specifically limited, For example, a rotary kiln etc. can be used. Moreover, when baking using a rotary kiln, a fuel alternative waste, for example, waste oil, a waste tire, a waste plastic, etc. can also be used.
なお、焼成物中にフリーライム（遊離石灰）が多く存在すると、コンクリート用骨材として使用した場合に、膨張破壊する可能性がある。したがって、焼成物１００質量％中におけるフリーライム量は、好ましくは０．４質量％以下であり、より好ましくは０．２質量％以下であり、さらに好ましくは０．１質量％以下である。 In addition, if there is a lot of free lime (free lime) in the fired product, there is a possibility of expansion and destruction when used as a concrete aggregate. Therefore, the amount of free lime in 100% by mass of the fired product is preferably 0.4% by mass or less, more preferably 0.2% by mass or less, and further preferably 0.1% by mass or less.
本発明の焼成物の容重は、高い圧壊強度を実現する観点から、好ましくは１２５０〜１４５０ｇ／Ｌであり、より好ましくは１２８０〜１４００ｇ／Ｌである。なお、容重とは、 図１に示す測定容器（内容積２５０ｍＬ）及び漏斗を用い、漏斗を介して焼成物を測定容器に充填したときの質量と測定容器自体の質量とから、次式（Ｘ）により求められる値を意味する。
容重（ｇ／Ｌ）＝（焼成物が充填された測定容器質量（ｇ）−測定容器自体の質量（ｇ））×４．０・・・（Ｘ）
The weight of the fired product of the present invention is preferably 1250 to 1450 g / L, more preferably 1280 to 1400 g / L, from the viewpoint of realizing high crushing strength. In addition, the capacity means the following formula (X) from the mass when the measurement vessel (inner volume 250 mL) and the funnel shown in FIG. ).
Weight (g / L) = (mass of measurement container filled with fired product (g) −mass of measurement container itself (g)) × 4.0 (X)
より具体的には、測定容器及び漏斗は、 図１に示す形状及び寸法で、材質及び厚さは特に制限されない。
ＪＩＳ Ｚ ８８０１に規定された標準網ふるい９．５mm及び４．７５mm、又はこれらに準ずる板ふるいを用い、焼成物２kgをふるい分け、９．５mmふるいを通過し、４．７５mmふるい残分の粒径の焼成物を試料とする。 図２に示すように、測定容器中に挿入された漏斗上に焼成物試料を、すりきりいっぱいまで静かに注ぎ入れる。次に、注意して、静かに漏斗を引き上げる。なお、焼成物が漏斗脚部に詰まり、円滑に流れ落ちない場合は、試料を容器に充填する操作からやり直す。
More specifically, the measurement container and the funnel have the shape and dimensions shown in FIG. 1, and the material and thickness are not particularly limited.
Using standard mesh sieves 9.5 mm and 4.75 mm specified in JIS Z 8801, or plate sieves equivalent to these, screen 2 kg of fired product, pass through 9.5 mm sieve, and particle size of 4.75 mm sieve residue The fired product is used as a sample. As shown in FIG. 2, the fired product sample is gently poured onto the funnel inserted in the measurement container. Then carefully, gently raise the funnel. If the fired product is clogged in the funnel leg and does not flow smoothly, the procedure is repeated from the operation of filling the sample into the container.
漏斗を引き上げた後、容器内の試料の表面は、その突出した部分と窪んだ部分が同じ程度になるよう、指先でならす。試料の充填が終了したら、容器とともにその質量を１ｇ単位まで正確にはかりとり、上記式によって容重の値を算出する。なお、容重の測定は、原則として２回実施し、その平均値を用いるが、２回の測定値の差は２０ｇ／Ｌ以内としなければならない。 After pulling up the funnel, the surface of the sample in the container is leveled with a fingertip so that the protruding portion and the recessed portion are at the same level. When the filling of the sample is completed, the mass of the container is accurately measured to the 1 g unit, and the weight value is calculated by the above formula. In principle, the weight is measured twice, and the average value is used, but the difference between the two measured values must be within 20 g / L.
本発明の焼成物の吸水率は、焼成物における高い圧壊強度や耐摩耗性を保持しつつ安定性を高める観点から、好ましくは５％以下、より好ましくは３．５％以下である。なお、吸水率とは、「ＪＩＳ Ａ １１１０（粗骨材の密度及び吸水率試験方法）」に準じて測定される値を意味する。 The water absorption rate of the fired product of the present invention is preferably 5% or less, more preferably 3.5% or less, from the viewpoint of improving stability while maintaining high crushing strength and wear resistance in the fired product. The water absorption means a value measured according to “JIS A 1110 (Coarse aggregate density and water absorption test method)”.
本発明の焼成物のすりへり減量は、焼成物における高い圧壊強度を保持しつつ良好な耐摩耗性を付与する観点から、好ましくは３０％以下であり、より好ましくは２５％以下であり、さらに好ましくは２０％以下である。 The wear loss of the fired product of the present invention is preferably 30% or less, more preferably 25% or less, and still more preferably from the viewpoint of imparting good wear resistance while maintaining high crushing strength in the fired product. Is 20% or less.
本発明の焼成物は、コンクリート用の骨材、路盤材、埋め戻し材等の土木・港湾材料として用いることができる。コンクリート用の骨材としては、細骨材、粗骨材のいずれにも使用することができる。 The fired product of the present invention can be used as civil engineering and harbor materials such as concrete aggregates, roadbed materials and backfill materials. As an aggregate for concrete, it can be used for both fine aggregate and coarse aggregate.
本発明の焼成物の粒度は、上記土木・港湾材料として好適に用いる観点から、好ましくは０．１〜１００ｍｍであり、特に粗骨材として使用する場合には、ふるい分け等により、例えば粒度を５ｍｍ以上に調整して用いるのがよい。 The particle size of the fired product of the present invention is preferably 0.1 to 100 mm from the viewpoint of being suitably used as the above-mentioned civil engineering / portal material, and particularly when used as a coarse aggregate, the particle size is, for example, 5 mm by sieving. It is good to adjust and use above.
以下、本発明について、実施例に基づき具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
［実施例１］
（１）焼成物の製造
石灰石、粘土、下水汚泥、土及び蛍石の原料を使用して、表１に示す鉱物組成（Ｃ2Ｓ１００質量部に対するＣ2ＡＳ、Ｃ4ＡＦ及びＣ3Ａの質量部）、並びにフッ素、亜鉛、ＳＯ3及びフリーライムの含有量（焼成物１００質量％中における質量％）である焼成物を製造した。焼成は、小型ロータリーキルンを用いて、１３００℃で行った。この際、燃料として、一般的な重油のほか、廃油や廃プラスチックを使用した。
[Example 1]
(1) Manufacture of calcined product Using raw materials of limestone, clay, sewage sludge, soil and fluorite, the mineral composition shown in Table 1 (C 2 AS, C 4 AF and C 3 A of C 2 S 100 parts by mass) Mass part), and a baked product having a content of fluorine, zinc, SO 3 and free lime (mass% in 100% by mass of the baked product). Firing was performed at 1300 ° C. using a small rotary kiln. At this time, in addition to general heavy oil, waste oil and waste plastic were used as fuel.
（２）焼成物の物性評価
得られた焼成物について、容重、吸水率、すりへり減量及び粉砕耐性を評価した。結果を表１に示す。
(2) Physical property evaluation of baked product The obtained baked product was evaluated for weight, water absorption, wear loss and crush resistance. The results are shown in Table 1.
（i）容重（ｇ／Ｌ）
ＪＩＳ Ｚ ８８０１に規定された標準網を用い、上記の測定方法にしたがって、上記式（Ｘ）により求めた。
(I) Weight (g / L)
It calculated | required by said formula (X) according to said measuring method using the standard net | network prescribed | regulated to JISZ8801.
（ii）吸水率（％）
ＪＩＳ Ａ １１１０（粗骨材の密度及び吸水率試験方法）に準じて測定した。
(Ii) Water absorption rate (%)
Measured according to JIS A 1110 (Drug and water absorption test method for coarse aggregate).
（iii）すりへり減量（％）
ＪＩＳ Ａ １１２１（ロサンゼルス試験機による粗骨材のすりへり試験方法）に準じて測定した。
(Iii) Abrasive weight loss (%)
The measurement was performed according to JIS A 1121 (Coarse aggregate test method using a Los Angeles testing machine).
（iv）粉砕耐性（ダスティングの防止）：０．６ｍｍ通過分・１００μｍ通過分（質量％）
得られた焼成物約５ｋｇを、下部間隔約１０ｍｍに調整した大型ジョークラッシャで粉砕した。次いで、粉砕した焼成物を、目開き９．５２ｍｍのふるいにかけ、ふるい上の試料に対し、さらに下部間隔約３ｍｍに調整した小型ジョークラッシャで粉砕した。得られたふるい通過分と小型ジョークラッシャで粉砕した試料を混ぜ合わせ、４．０ｋｇ秤量した。秤量した試料を、粉砕助剤のジエチレングリコール１．８ｍＬとともにボールミルに加え、７０ｒｐｍで５００回転した後、５０回転で払出をした。得られた粉砕物の０．６ｍｍ通過分（質量％）及び１００μｍ通過分（質量％、ただし０．６ｍｍ通過分を１００質量％とする）を測定し、粉砕耐性やダスティングの防止効果を評価する上での指標とした。かかる通過分の値が小さいほど、粉砕耐性が高い焼成物であり、特に１００μｍ通過分の値が小さいほど、ダスティングを有効に防止して良好な焼成物が得られていると判断できる。
結果を表３に示す。
(Iv) Crush resistance (prevention of dusting): 0.6 mm passage / 100 μm passage (mass%)
About 5 kg of the obtained fired product was pulverized with a large jaw crusher adjusted to a lower interval of about 10 mm. Next, the pulverized fired product was passed through a sieve having an opening of 9.52 mm, and the sample on the sieve was further pulverized with a small jaw crusher adjusted to a lower interval of about 3 mm. The obtained sieve passage and the sample crushed with a small jaw crusher were mixed and weighed 4.0 kg. The weighed sample was added to a ball mill together with 1.8 mL of a grinding aid diethylene glycol, and after 500 rotations at 70 rpm, the samples were discharged at 50 rotations. Measure the 0.6 mm passage (mass%) and 100 μm passage (mass%, where 0.6 mm passage is 100 mass%) of the obtained pulverized product, and evaluate the crush resistance and dusting prevention effect. It was used as an index for doing this. It can be judged that the smaller the value of the passing portion is, the higher the pulverization resistance is, and in particular, the smaller the value of 100 μm passing portion is, the more effectively the dusting is prevented and a good fired product is obtained.
The results are shown in Table 3.
表１の結果より、Ｃ2Ｓ１００質量部に対し、１０〜１００質量部のＣ2ＡＳ、２０質量部以下のＣ3Ａを含有し、かつフッ素を０．０３〜０．２質量％含有する焼成物１〜５は、高い容重を有しつつ優れた粉砕耐性を示し、良好な物性を兼ね備えることがわかる。
From the results of Table 1, with respect to C 2 S100 parts by weight containing C 2 AS, 20 parts by weight or less of C 3 A of 10 to 100 parts by weight, and fluorine containing 0.03 to 0.2 wt% It can be seen that the fired
（３）コンクリートの調製
下記材料を用い、表２に示す配合割合で、コンクリートを調製した。
セメント（Ｃ）：普通ポルトランドセメント（太平洋セメント（株）製）
細骨材（Ｓ）：静岡県小笠郡産陸砂
粗骨材（Ｇ）：表１に示す焼成物Ｎｏ.２及び焼成物Ｎｏ.３
普通ポルトランドセメントクリンカー
硬質砂岩砕石
水（Ｗ）：水道水
ＡＥ減水剤（ＷＲＡ）：リグニンスルホン酸系減水剤（ポゾリスNo.70、ＢＡＳＦポゾリス社製）
(3) Preparation of concrete Concrete was prepared using the following materials at the blending ratio shown in Table 2.
Cement (C): Ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd.)
Fine aggregate (S): Land sand from Ogasa-gun, Shizuoka Prefecture Coarse aggregate (G): Firing product No. 2 and calcining product No. 3 shown in Table 1
Ordinary Portland cement clinker Hard sandstone crushed water (W): tap water AE water reducing agent (WRA): lignin sulfonic acid water reducing agent (Pozoris No. 70, manufactured by BASF Pozoris)
（４）コンクリートの物性評価
表２で得られた各コンクリートについて、圧縮強度、中性化及び長さ変化を評価した。結果を表３に示す。
(4) Physical property evaluation of concrete About each concrete obtained in Table 2, compressive strength, neutralization, and length change were evaluated. The results are shown in Table 3.
（ｉ）圧縮強度
ＪＩＳ Ａ １１０８（コンクリートの圧縮強度試験方法）に準じて、材齢２８日、９１日及び１年の圧縮強度を測定した。
(I) Compressive Strength According to JIS A 1108 (Concrete Compressive Strength Test Method), compressive strengths of 28 days, 91 days and 1 year were measured.
（ii）中性化
材齢２８日まで標準養生し、その後、温度２０℃、相対湿度６０％の室内で２８日間乾燥させた供試体について、ＣＯ2濃度５％、温度２０℃、相対湿度６０％の条件下で、促進中性化試験を行なった。フェノールフタレインの１％エタノール溶液を噴霧し、未着色部分の厚さから、中性化深さを求めた。
(Ii) Neutralization Specimens that were standardly cured until the age of 28 days and then dried for 28 days in a room at a temperature of 20 ° C. and a relative humidity of 60% were tested. Under these conditions, an accelerated neutralization test was conducted. A 1% ethanol solution of phenolphthalein was sprayed, and the neutralization depth was determined from the thickness of the uncolored portion.
（iii）長さ変化
水中養生３ヶ月後のコンクリートの長さ変化を、ＪＩＳ Ａ １１２９−３に準じて測定した。
(Iii) Length change The length change of the concrete after 3 months of underwater curing was measured according to JIS A 1129-3.
表１の結果より、Ｃ2Ｓ１００質量部に対し、１０〜１００質量部のＣ2ＡＳ、２０質量部以下のＣ3Ａを含有し、かつフッ素を０．０３〜０．２質量％含有する焼成物１〜５、及び８〜９は、高い容重を有しつつ優れた粉砕耐性を示し、良好な物性を兼ね備えることがわかる。
From the results of Table 1, with respect to C 2 S100 parts by weight containing C 2 AS, 20 parts by weight or less of C 3 A of 10 to 100 parts by weight, and fluorine containing 0.03 to 0.2 wt% It can be seen that the fired
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