JP6151008B2 - Fired product - Google Patents
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- JP6151008B2 JP6151008B2 JP2012255973A JP2012255973A JP6151008B2 JP 6151008 B2 JP6151008 B2 JP 6151008B2 JP 2012255973 A JP2012255973 A JP 2012255973A JP 2012255973 A JP2012255973 A JP 2012255973A JP 6151008 B2 JP6151008 B2 JP 6151008B2
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- 239000000463 material Substances 0.000 claims description 38
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 26
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 description 30
- 239000002699 waste material Substances 0.000 description 29
- 239000004567 concrete Substances 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 12
- 229910052804 chromium Inorganic materials 0.000 description 12
- 239000011651 chromium Substances 0.000 description 12
- 238000010304 firing Methods 0.000 description 10
- 239000002689 soil Substances 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 9
- 235000012255 calcium oxide Nutrition 0.000 description 9
- 238000010410 dusting Methods 0.000 description 9
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 8
- 235000011941 Tilia x europaea Nutrition 0.000 description 8
- 238000010828 elution Methods 0.000 description 8
- 239000004571 lime Substances 0.000 description 8
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 7
- 238000010276 construction Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000004568 cement Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000010801 sewage sludge Substances 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
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002245 particle 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
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000007787 solid Substances 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
- 238000005299 abrasion Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BCFSVSISUGYRMF-UHFFFAOYSA-N calcium;dioxido(dioxo)chromium;dihydrate Chemical compound O.O.[Ca+2].[O-][Cr]([O-])(=O)=O BCFSVSISUGYRMF-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 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
- 239000004576 sand Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229910052861 titanite Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Processing Of Solid Wastes (AREA)
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, Patent Document 1 proposes a fired product that can effectively use waste as a raw material.
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、これら廃棄物等の原料にはクロムが混入している場合があり、使用する原料中におけるクロムの含有量によっては、これから得られる焼成物を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使用した場合に、６価クロムが溶出するおそれがある。そのため、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使用する焼成物を得るにあたり、廃棄物等におけるクロムの含有量によっては、原料としての使用が制限される可能性がある。 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. In addition, these raw materials such as waste may contain chromium, and depending on the chromium content in the raw materials used, the fired products obtained from this may be used as aggregates for mortar and concrete, roadbed materials, embankments. When used as materials such as materials and backfill materials, hexavalent chromium may be eluted. Therefore, in obtaining a fired product to be used as a material such as aggregate, roadbed material, embankment material and backfill material for mortar and concrete, use as a raw material is limited depending on the chromium content in the waste or the like. there is a possibility.
したがって、本発明の目的は、クロムの含有量に左右されることなく、廃棄物等も原料として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 can be effectively used as a raw material without depending on the chromium content, and can be used effectively as a raw material, as well as aggregates for mortar and concrete, roadbed materials, embankment materials, and backfilling. It is providing the baked material which can be used as suitable materials, such as a material.
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ＴｉＯ2を含有することにより、クロムの含有量に左右されることなく廃棄物等も原料として用い得るとともに、優れた粉砕耐性を備える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 made various studies, and by including a specific amount of TiO 2 with a specific mineral composition, waste and the like can be used as a raw material regardless of the chromium content, and excellent. As a result, it was found that a baked product having crushing resistance was obtained, and the present invention was 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、３ＣａＯ・Ａｌ2Ｏ3（以下、Ｃ3Ａと称する）及び４ＣａＯ・Ａｌ2Ｏ3・Ｆｅ2Ｏ3（以下、Ｃ4ＡＦと称する）の合計量が０質量部超５０質量部以下である焼成物であって、
２ＣａＯ・Ａｌ2Ｏ3・ＳｉＯ2（以下、Ｃ2ＡＳと称する）を０質量部超１０質量部未満含有するとともに３ＣａＯ・ＳｉＯ2（以下、Ｃ3Ｓと称する）を含有せず、又は３ＣａＯ・ＳｉＯ2（Ｃ3Ｓ）を０質量部超５０質量部以下含有するとともに２ＣａＯ・Ａｌ2Ｏ3・ＳｉＯ2（Ｃ2ＡＳ）を含有せず、かつ
焼成物１００質量％中に、ＴｉＯ2を０．２質量％以上含有する焼成物を提供するものである。
That is, in the present invention, 3CaO · Al 2 O 3 (hereinafter referred to as C 3 A) and 4CaO · Al 2 O 3 · Fe are added to 100 parts by mass of 2CaO · SiO 2 (hereinafter referred to as C 2 S). 2 O 3 (hereinafter referred to as C 4 AF) is a calcined product having a total amount of more than 0 parts by mass and 50 parts by mass or less,
2CaO · Al 2 O 3 · SiO 2 ( hereinafter, C 2 AS hereinafter) to 3CaO · SiO 2 with containing less than 0 parts by ultra 10 parts by weight (hereinafter, referred to as C 3 S) does not contain, or 3CaO · SiO 2 (C 3 S) to not contain 2CaO · Al 2 O 3 · SiO 2 (C 2 AS) with containing less 0 parts by ultra 50 parts by weight, and in calcined product 100 wt%, TiO 2 Is to provide a fired product containing 0.2% by mass or more.
本発明の焼成物によれば、仮にクロムを多く含む廃棄物等を原料として用いたとしても、６価クロムの溶出を抑制しつつ、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な優れた粉砕耐性を備える焼成物を得ることができる。したがって、クロムの含有量に左右されることなく、急増する廃棄物、特にクロムを多く含む廃棄物を多量に消費することができ、非常に有用な焼成物である。 According to the fired product of the present invention, even if waste containing a large amount of chromium is used as a raw material, the aggregate, roadbed material, embankment material and embedding material for mortar and concrete are suppressed while suppressing elution of hexavalent chromium. A fired product having excellent crushing resistance that can be suitably used as a material such as a return material can be obtained. Therefore, it is possible to consume a large amount of waste that increases rapidly, particularly waste containing a lot of chromium, regardless of the chromium content, and it is a very useful fired product.
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、Ｃ3Ａ及びＣ4ＡＦの合計量が０質量部超５０質量部以下である焼成物であって、
２ＣａＯ・Ａｌ2Ｏ3・ＳｉＯ2（以下、Ｃ2ＡＳと称する）を０質量部超１０質量部未満含有するとともに３ＣａＯ・ＳｉＯ2（以下、Ｃ3Ｓと称する）を含有せず、又は３ＣａＯ・ＳｉＯ2（Ｃ3Ｓ）を０質量部超５０質量部以下含有するとともに２ＣａＯ・Ａｌ2Ｏ3・ＳｉＯ2（Ｃ2ＡＳ）を含有せず、かつ
焼成物１００質量％中に、ＴｉＯ2を０．２質量％以上含有する。
Hereinafter, the present invention will be described in detail.
The fired product of the present invention is a fired product having a total amount of C 3 A and C 4 AF of more than 0 parts by weight and 50 parts by weight or less with respect to 100 parts by weight of C 2 S,
2CaO · Al 2 O 3 · SiO 2 ( hereinafter, C 2 AS hereinafter) to 3CaO · SiO 2 with containing less than 0 parts by ultra 10 parts by weight (hereinafter, referred to as C 3 S) does not contain, or 3CaO · SiO 2 (C 3 S) and do not contain 2CaO · Al 2 O 3 · SiO 2 (C 2 AS) with containing less 0 parts by ultra 50 parts by weight, and in calcined product 100 wt%, TiO 2 In an amount of 0.2% by mass or more.
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。本発明の焼成物中におけるＣ3Ａ及びＣ4ＡＦの合計量は、Ｃ2Ｓ１００質量部に対して、０質量部超５０質量部以下であって、好ましくは１０〜４８質量部であり、より好ましくは２０〜４５質量部である。Ｃ2Ｓ１００質量部に対し、Ｃ3Ａ及びＣ4ＡＦの合計量が５０質量部を越えると、焼成物の吸水率が大きくなるおそれがあり、Ｃ3Ａ及びＣ4ＡＦの合計量が０質量部であると、焼成物の焼成が困難となるおそれがある。
なお、本発明の焼成物は、Ｃ3Ａ又はＣ4ＡＦの両方を含んでいても良く、どちらか一方を含んでいても良い。
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. The total amount of C 3 A and C 4 AF in the fired product of the present invention is more than 0 parts by mass and 50 parts by mass or less, preferably 10 to 48 parts by mass with respect to 100 parts by mass of C 2 S. More preferably, it is 20-45 mass parts. If the total amount of C 3 A and C 4 AF exceeds 50 parts by mass with respect to 100 parts by mass of C 2 S, the water absorption of the fired product may increase, and the total amount of C 3 A and C 4 AF is 0. If it is part by mass, it may be difficult to fire the fired product.
The firing of the present invention may include both C 3 A or C 4 AF, may include one or the other.
Ｃ3Ａの含有量は、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、Ｃ2Ｓ１００質量部に対して、好ましくは５〜３０質量部であり、より好ましくは５〜２８質量部である。 The content of 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 this, it is preferably 5 to 30 parts by mass, and more preferably 5 to 28 parts by mass with respect to 100 parts by mass of C 2 S.
Ｃ4ＡＦの含有量は、焼成のし易さや焼成物の吸水率を低下させる観点から、Ｃ2Ｓ１００質量部に対して、好ましくは１０〜４０質量部であり、より好ましくは１２〜３５質量部である。 The content of C 4 AF is preferably 10 to 40 parts by weight, more preferably 12 to 35 parts by weight with respect to 100 parts by weight of C 2 S, from the viewpoint of ease of firing and reduction of water absorption of the fired product. Part.
本発明の焼成物は、さらに、Ｃ2ＡＳ又はＣ3Ｓのいずれか一方を含むものである。該鉱物を含むことにより、焼成物の吸水率を低下させることができ、また、原料におけるクロムの含有量が増大しても、得られる焼成物からの６価クロムの溶出を抑制することが可能となる。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。またＣ3Ｓは、水硬性を有し、水和生成物としてＣａ(ＯＨ)2等を生成させるため、コンクリートの中性化を抑制したり、緻密化して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 fired product of the present invention further contains either C 2 AS or C 3 S. By including this mineral, the water absorption of the fired product can be reduced, and even if the chromium content in the raw material is increased, it is possible to suppress elution of hexavalent chromium from the fired product obtained. It becomes. Although C 2 AS does not have hydraulic properties, since it is densified by carbonation, it can exert the effect of suppressing the neutralization of concrete or increasing the strength of the roadbed or the like. C 3 S has hydraulic properties and produces Ca (OH) 2 and the like as hydrated products. Therefore, the effect of suppressing the neutralization of concrete and increasing the strength of the roadbed by densification. Can be demonstrated.
一方、Ｃ2ＡＳ及びＣ3Ｓの合計量が０質量部、すなわちＣ2ＡＳ及びＣ3Ｓの双方とも含まない焼成物を製造するには、原料中におけるＣａＯ、ＳｉＯ2、Ａｌ2Ｏ3、Ｆｅ2Ｏ3の含有量を厳密に管理及び制御する必要があるため、製造に手間がかかる。また、後述するように、例えばＫ2Ｏ及び／又はＮａ2Ｏの合計含有量を調整して、ダスティング防止する場合に、アルカリの溶出量が多くなることがある。 On the other hand, in order to produce a calcined product in which the total amount of C 2 AS and C 3 S is 0 parts by mass, that is, does not contain both C 2 AS and C 3 S, CaO, SiO 2 , Al 2 O 3 in the raw material Since it is necessary to strictly control and control the content of Fe 2 O 3 , production takes time. Further, as will be described later, for example, when the total content of K 2 O and / or Na 2 O is adjusted to prevent dusting, the amount of alkali elution may increase.
本発明の焼成物が、Ｃ2ＡＳを含むとともにＣ3Ｓを含まない場合、かかるＣ2ＡＳの含有量は、Ｃ2Ｓ１００質量部に対して、０質量部超１０質量部未満であって、好ましくは０．５〜９質量部であり、より好ましくは１〜８質量部である。Ｃ2Ｓ１００質量部に対し、Ｃ2ＡＳの含有量が１０質量部以上であると、クロムの含有量が多くなった場合に６価クロムの溶出量が多くなるおそれがある。 When the fired product of the present invention contains C 2 AS and does not contain C 3 S, the content of C 2 AS is more than 0 parts by mass and less than 10 parts by mass with respect to 100 parts by mass of C 2 S. , Preferably it is 0.5-9 mass parts, More preferably, it is 1-8 mass parts. When the content of C 2 AS is 10 parts by mass or more with respect to 100 parts by mass of C 2 S, the elution amount of hexavalent chromium may increase when the chromium content increases.
本発明の焼成物が、Ｃ3Ｓを含むとともにＣ2ＡＳを含まない場合、Ｃ3Ｓの含有量は、Ｃ2Ｓ１００質量部に対して、０質量部超５０質量部以下であって、好ましくは１〜４８質量部であり、より好ましくは２〜４５質量部である。Ｃ2Ｓ１００質量部に対し、Ｃ3Ｓの含有量が５０質量部を越えると、焼成物の吸水率が大きくなるおそれがある。また、焼成物中におけるフリーライム（遊離石灰）量を低減するための温度が高くなり、燃料費が嵩むなど経済的な面でも好ましくない。 When the fired product of the present invention contains C 3 S and does not contain C 2 AS, the content of C 3 S is more than 0 parts by mass and less than 50 parts by mass with respect to 100 parts by mass of C 2 S, Preferably it is 1-48 mass parts, More preferably, it is 2-45 mass parts. If the C 3 S content exceeds 50 parts by mass with respect to 100 parts by mass of C 2 S, the water absorption rate of the fired product may increase. Moreover, the temperature for reducing the amount of free lime (free lime) in the fired product is increased, which is not preferable from an economical viewpoint, such as an increase in fuel cost.
本発明の焼成物は、ＴｉＯ2を０．２質量％以上含有する。これにより、焼成物の吸水率を低下させることができるとともに、焼成物の圧壊強度等を高めることが可能となる。
本発明の焼成物中におけるＴｉＯ2の含有量は、焼成物１００質量％中に、０．２質量％以上であって、好ましくは０．２５質量％以上であり、より好ましくは０．３質量％以上である。焼成物１００質量％中におけるＴｉＯ2の含有量が０．２質量％未満であると、焼成物の吸水率が大きくなるおそれがあり、またフリーライム量が増大するおそれがある。なお、製造コストや焼成のし易さなどの観点から、本発明の焼成物１００質量％中におけるＴｉＯ2の含有量は、好ましくは４．０質量％以下であり、より好ましくは３．０質量％以下である。
The fired product of the present invention contains 0.2% by mass or more of TiO 2 . As a result, the water absorption rate of the fired product can be reduced, and the crushing strength of the fired product can be increased.
The content of TiO 2 in the fired product of the present invention is 0.2% by weight or more, preferably 0.25% by weight or more, and more preferably 0.3% by weight in 100% by weight of the fired product. % Or more. When the content of TiO 2 in 100% by mass of the baked product is less than 0.2% by mass, the water absorption rate of the baked product may be increased, and the amount of free lime may be increased. From the viewpoint of production cost, easiness of firing, etc., the content of TiO 2 in 100% by mass of the fired product of the present invention is preferably 4.0% by mass or less, more preferably 3.0% by mass. % Or less.
本発明の焼成物は、亜鉛を含有することが好ましい。かかる亜鉛を含有することにより、焼成物の圧壊強度等をより高めることができる。本発明の焼成物中における亜鉛の含有量は、圧壊強度等の向上の観点から、焼成物１００質量％中に、０．０３〜０．５質量％であって、好ましくは０．０４〜０．４質量％であり、より好ましくは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、圧壊強度等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 fired product of the present invention preferably contains zinc. By containing such zinc, the crushing strength of the fired product can be further increased. The content of zinc in the fired product of the present invention is 0.03 to 0.5% by weight, preferably 0.04 to 0% in 100% by weight of the fired product, from the viewpoint of improving the crushing strength and the like. .4 mass%, more preferably 0.05-0.2 mass%. If the zinc content in 100% by mass of the fired product is less than 0.03% by mass, the crushing strength and the like may be reduced. 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.
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。
また、ＴｉＯ2原料としては、ルチルやチタン鉄鉱等の天然原料や、顔料、触媒等の廃棄物を使用することができる。
さらに、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。
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 TiO 2 raw material, natural raw materials such as rutile and titanite, and wastes such as pigments and catalysts can be used.
In addition to industrial zinc oxide, waste tires, waste oil, metal slag, etc. can be used as the zinc raw material.
さらに、本発明の焼成物中におけるＰ2Ｏ5の含有量は、ダスティングを防止する観点から、焼成物１００質量％中に、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 weight or more in 100% by weight of the fired product from the viewpoint of preventing dusting, and more preferably 0.8%. It is 4 mass% or more, More preferably, it is 0.5 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、本発明の焼成物中における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、本発明の焼成物１００質量％中に、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、本発明の焼成物中における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, K 2 O and / or Na 2 O is used from the viewpoint of preventing dusting and improving the ease of firing. The total content of is preferably 1.0 to 5.0 mass%, more preferably 1.5 to 4.5 mass%, still more preferably 2 in 100 mass% of the fired product of the present invention. 0.0 to 4.0% by mass.
In addition, the total content of K 2 O and / or Na 2 O in the fired product of the present invention can be obtained by using waste such as waste glass as a raw material or using industrial materials such as sodium carbonate. Can be adjusted.
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、クロム汚染土壌や亜鉛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-contaminated soil, chromium-contaminated soil, and zinc-contaminated soil. Examples of construction generated soil include soil and residual soil generated from construction sites and construction sites, and waste soil.
本発明の焼成物の鉱物組成（Ｃ2Ｓ、Ｃ4ＡＦ、Ｃ3Ａ、Ｃ2ＡＳ、Ｃ3Ｓ）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。
（１）Ｃ2ＡＳを含むとともにＣ3Ｓを含まない場合：
−１．６３×ＣａＯ＋３．０４×ＳｉＯ2＋２．６９×Ａｌ2Ｏ3＋０．５７×Ｆｅ2Ｏ3＞０の場合
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
The mineral composition (C 2 S, C 4 AF, C 3 A, C 2 AS, C 3 S) of the fired product of the present invention is the raw material used and CaO, SiO 2 , Al 2 O 3 , Fe 2 in the fired product. each content of O 3 from (wt%) can be determined by the following equation.
(1) When C 2 AS is included and C 3 S is not included:
−1.63 × CaO + 3.04 × SiO 2 + 2.69 × Al 2 O 3 + 0.57 × Fe 2 O 3 > 0 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
（２）Ｃ3Ｓを含むとともにＣ2ＡＳを含まない場合：
−１．６３×ＣａＯ＋３．０４×ＳｉＯ2＋２．６９×Ａｌ2Ｏ3＋０．５７×Ｆｅ2Ｏ3＜０の場合
Ｃ4ＡＦ＝３．０４×Ｆｅ2Ｏ3
Ｃ3Ａ＝２．６５×Ａｌ2Ｏ3−１．６９×Ｆｅ2Ｏ3
Ｃ3Ｓ＝４．０７×ＣａＯ−７．６×ＳｉＯ2−６．７２×Ａｌ2Ｏ3−１．４３×Ｆｅ2Ｏ3
Ｃ2Ｓ＝１．０２×ＣａＯ＋０．９５×ＳｉＯ2−１．６９×Ａｌ2Ｏ3−０．３６×Ｆｅ2Ｏ3
(2) When C 3 S is included and C 2 AS is not included:
−1.63 × CaO + 3.04 × SiO 2 + 2.69 × Al 2 O 3 + 0.57 × Fe 2 O 3 <0 C 4 AF = 3.04 × Fe 2 O 3
C 3 A = 2.65 × Al 2 O 3 −1.69 × Fe 2 O 3
C 3 S = 4.07 × CaO−7.6 × SiO 2 −6.72 × Al 2 O 3 −1.43 × 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ＴｉＯ2及び亜鉛の含有量は、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ＴｉＯ2又は亜鉛が不足する場合、その不足分を調整するために、上記ＴｉＯ2原料又は亜鉛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 content of TiO 2 and zinc in the fired product of the present invention is a value determined from the composition of the resulting fired product. Therefore, for example, when TiO 2 or zinc is insufficient in the raw material used, the TiO 2 raw material or zinc raw material may be mixed and used in order to adjust the shortage. 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、１１００〜１４５０℃が好ましく、１１５０〜１４５０℃であるのがより好ましい。焼成温度が１１００℃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、１４５０℃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, 1100-1450 degreeC is preferable and the firing temperature at the time of baking has more preferable 1150-1450 degreeC. If the firing temperature is less than 1100 ° C, it may be difficult to reduce the amount of free lime, and if it exceeds 1450 ° 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、本発明の焼成物１００質量％中におけるフリーライム量は、好ましくは２．０質量％以下であり、より好ましくは１．５質量％以下であり、さらに好ましくは１．０質量％以下である。
なお、本発明の焼成物中にフリーライムが２．０質量％以上存在した場合、空気、蒸気または炭酸ガスに一定期間曝して反応させ、水酸化カルシウムや炭酸カルシウムとすることにより、膨張破壊を防止することができる。
If a large amount of free lime is present 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 of the present invention is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and further preferably 1.0% by mass or less. is there.
When 2.0% by mass or more of free lime is present in the fired product of the present invention, it is exposed to air, steam or carbon dioxide gas for a certain period of time to react with calcium hydroxide or calcium carbonate, thereby causing expansion destruction. Can be prevented.
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、廃顔料、リン酸水素カルシウム、クロム酸カルシウム及び廃ガラスを使用して、表１に示す鉱物組成（Ｃ2Ｓ１００質量部に対するＣ4ＡＦ、Ｃ3Ａ、Ｃ2ＡＳ及びＣ3Ｓの質量部）、並びにＴｉＯ2、亜鉛、クロム、Ｐ2Ｏ5、Ｎａ2Ｏ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、１２５０〜１３５０℃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 baked product Using limestone, clay, sewage sludge, soil, waste pigment, calcium hydrogen phosphate, calcium chromate and waste glass, the mineral composition shown in Table 1 (C 4 to 100 parts by mass of C 2 S 100 parts by mass) AF, C 3 A, C 2 AS and C 3 S parts by mass), and TiO 2 , zinc, chromium, P 2 O 5 , Na 2 O and free lime content (mass% in 100% by mass of the fired product) ) Was produced. Firing was performed at 1250 to 1350 ° 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、吸水率、すりへり減量、粉砕耐性（０．６ｍｍ通過分）、及び６価クロム溶出量を評価した。結果を表１に示す。
(2) Physical property evaluation of baked product The obtained baked product was evaluated for water absorption, wear loss, crush resistance (0.6 mm passage), and hexavalent chromium elution amount. The results are shown in Table 1.
（i）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。
(I) Water absorption rate (%)
Measured according to JIS A 1110 (Drug and water absorption test method for coarse aggregate).
（ii）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。
(Ii) Abrasion loss (%)
The measurement was performed according to JIS A 1121 (Coarse aggregate test method using a Los Angeles testing machine).
（iii）粉砕耐性（ダスティングの防止）：０．６ｍｍ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％）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、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。
(Iii) Crush resistance (prevention of dusting): 0.6 mm 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. The obtained pulverized product was measured for 0.6 mm passage (mass%) and used as an index for evaluating the pulverization resistance and dusting prevention effect. It can be determined that the smaller the value of the passing portion, the higher the pulverization resistance, and the better the fired product obtained by effectively preventing dusting.
（iv）６価クロム溶出量
ＪＩＳ Ｋ ００５８−１（スラグ類の化学物質試験方法第1部溶出量試験方法）に準じて（有姿、水固形分比１０）測定した。
結果を表１に示す。
(Iv) Hexavalent chromium elution amount Measured according to JIS K 0058-1 (Slag chemical substance test method part 1 elution amount test method) (solid, water solid content ratio 10).
The results are shown in Table 1.
なお、焼成物１〜９について、さらに１００μｍ篩の通過分を確認したところ、かかる通過分の粉状物は存在しなかった。
焼成物１０〜１２については、ダスティングが発生した。
In addition, about the baked products 1-9, when the passage part of the 100 micrometer sieve was confirmed, the powdery part of this passage part did not exist.
Dusting occurred for the fired products 10-12.
表１の結果より、Ｃ2Ｓ１００質量部に対し、Ｃ3Ａ及びＣ4ＡＦの合計量が０質量部超５０質量部以下で、Ｃ2ＡＳを０質量部超１０質量部未満含有するとともにＣ3Ｓを含有せず、ＴｉＯ2を０．２質量％以上含有する焼成物１〜２及び焼成物７、並びにＣ3Ｓを０質量部超５０質量部以下含有するとともにＣ2ＡＳを含有せず、ＴｉＯ2を０．２質量％以上含有する焼成物３〜６及び焼成物８〜９は、吸水率が低く、またクロムの含有量が多くても６価クロムの溶出を効果的に抑制できることがわかる。 From the results of Table 1, with respect to C 2 S100 parts by, C 3 A and C 4 AF total weight is less 0 parts by ultra 50 parts by weight of, together with the C 2 AS contains less than 0 parts by ultra 10 parts by weight It does not contain C 3 S, containing C 2 AS with containing TiO 2 calcined product 1-2 and calcined product 7 containing more than 0.2 mass%, and C 3 S to the following 0 parts by ultra 50 parts by weight Without firing, the fired products 3 to 6 and the fired products 8 to 9 containing TiO 2 in an amount of 0.2% by mass or more have a low water absorption rate, and the elution of hexavalent chromium is effective even if the chromium content is high. It turns out that it can suppress.
（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) a standard curing until neutralized age of 28 days, then, the temperature 20 ° C., the specimen was dried in a room at 60% relative humidity for 28 days, CO 2 concentration of 5% and a temperature 20 ° C., a relative humidity of 60 The accelerated neutralization test was conducted under the condition of%. 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.
Claims (5)
３ＣａＯ・ＳｉＯ2を１〜１６質量部含有するとともに２ＣａＯ・Ａｌ2Ｏ3・ＳｉＯ2を含有せず、かつ
焼成物１００質量％中に、ＴｉＯ2を０．２質量％以上４．０質量％以下含有する焼成物（ただし、４ＣａＯ・３Ａｌ2Ｏ3・ＳＯ3を含む焼成物を除く）からなる土木・港湾材料。 In the mineral composition of the fired product (2CaO · SiO 2, 4CaO · Al 2 O 3 · Fe 2 O 3, 3CaO · Al 2 O 3, 2CaO · Al 2 O 3 · SiO 2, 3CaO · SiO 2), 2CaO · SiO 2 A fired product having a total amount of 3CaO · Al 2 O 3 and 4CaO · Al 2 O 3 · Fe 2 O 3 of 20 to 50 parts by mass with respect to 100 parts by mass,
It contains 1 to 16 parts by mass of 3CaO.SiO 2 and does not contain 2CaO.Al 2 O 3 .SiO 2, and 0.2% by mass to 4.0% by mass of TiO 2 in 100% by mass of the fired product. calcined product containing less (excluding calcined product containing 4CaO · 3Al 2 O 3 · SO 3) civil engineering and harbor materials consisting of.
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