JP2007169141A - Method for producing burnt products - Google Patents
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- JP2007169141A JP2007169141A JP2006035052A JP2006035052A JP2007169141A JP 2007169141 A JP2007169141 A JP 2007169141A JP 2006035052 A JP2006035052 A JP 2006035052A JP 2006035052 A JP2006035052 A JP 2006035052A JP 2007169141 A JP2007169141 A JP 2007169141A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 63
- 239000000047 product Substances 0.000 claims abstract description 223
- 239000002994 raw material Substances 0.000 claims abstract description 106
- 239000002699 waste material Substances 0.000 claims abstract description 48
- 239000006227 byproduct Substances 0.000 claims abstract description 44
- 239000002440 industrial waste Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000428 dust Substances 0.000 claims description 59
- 239000002689 soil Substances 0.000 claims description 22
- 239000011398 Portland cement Substances 0.000 claims description 21
- 238000010276 construction Methods 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 19
- 239000004568 cement Substances 0.000 claims description 16
- 238000000746 purification Methods 0.000 claims description 6
- 239000002918 waste heat Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 235000015173 baked goods and baking mixes Nutrition 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 42
- 239000000463 material Substances 0.000 description 36
- 238000010521 absorption reaction Methods 0.000 description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 229910052785 arsenic Inorganic materials 0.000 description 18
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 18
- 238000010304 firing Methods 0.000 description 17
- 238000002156 mixing Methods 0.000 description 17
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 238000005245 sintering Methods 0.000 description 14
- 239000011651 chromium Substances 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000004927 clay Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 235000019738 Limestone Nutrition 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 8
- 235000012255 calcium oxide Nutrition 0.000 description 8
- 239000010883 coal ash Substances 0.000 description 8
- 239000004567 concrete Substances 0.000 description 8
- 239000006028 limestone Substances 0.000 description 8
- 239000010881 fly ash Substances 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 238000005273 aeration Methods 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- -1 etc.) Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000010440 gypsum Substances 0.000 description 4
- 229910052602 gypsum Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002956 ash Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 239000011396 hydraulic cement Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000010801 sewage sludge Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003141 anti-fusion Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 239000010920 waste tyre Substances 0.000 description 1
- 239000002023 wood 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Landscapes
- Treatment Of Sludge (AREA)
Abstract
Description
本発明は、産業廃棄物や建設発生土等の廃棄物を主原料として使用することができ、特に、副産物の発生をなくすか又は極端に少なくすることができる焼成物の製造方法に関する。 The present invention relates to a method for producing a calcined product that can use industrial waste or waste such as construction generated soil as a main raw material, and in particular, can eliminate or extremely reduce the generation of by-products.
建設現場や工事現場等から発生する土壌や残土、あるいは産業廃棄物や一般廃棄物の発生量は、年間数百万トンにも達し、その大部分は有効利用されることなく、埋立て処分されているのが現状である。近年、その受け入れ側である埋立て処分場については、その枯渇化が深刻化しており、発生する廃棄物を全て受け入れられない状況である。
また、これらを廃棄するために必要な費用についても、年々高騰の一途を辿っており、このような状況から、廃棄物を不法投棄するなどの社会的問題も発生している。
The amount of soil and residual soil generated from construction sites and construction sites, industrial waste and general waste reaches millions of tons per year, most of which is landfilled without being effectively used. This is the current situation. In recent years, the landfill disposal site on the receiving side has become increasingly depleted, and all the generated waste cannot be received.
In addition, the costs necessary for disposing of these materials are also increasing year by year, and from such a situation, social problems such as illegal dumping of waste have also occurred.
このような処分場の枯渇化の背景や、さらには、産業廃棄物は無機質な鉱物が主成分であることから、産業廃棄物にセメントと水を添加し、養生固化したものを裏打材、埋め戻し材等として再利用する方法が提案されている（特許文献１）。
しかしながら、特許文献１に記載されている再利用の方法は、処理費用が高い割には、利用価値が低く、その実用化が進んでいないのが現状である。
The background of the depletion of such a disposal site, and furthermore, industrial waste is mainly composed of inorganic minerals, so cement and water are added to the industrial waste and cured and solidified as a backing material and buried. A method of reusing as a return material has been proposed (Patent Document 1).
However, the reuse method described in Patent Document 1 has a low utility value for a high processing cost, and its practical use is not progressing.
また、セメント産業においても、産業廃棄物等をセメントの原料代替として利用しつつあるが、所定品質のセメントクリンカーを得るためには、使用し得る産業廃棄物等の種類及び使用量にも限界があり、また、近年のセメント需要の低迷に伴う減産の影響を受け、産業廃棄物等の発生量に対し、その処理量が追いついていない。 Also, in the cement industry, industrial waste is being used as a raw material substitute for cement, but in order to obtain cement clinker of a predetermined quality, there is a limit to the type and amount of industrial waste that can be used. In addition, due to the impact of reduced production due to the recent decline in cement demand, the amount of industrial waste, etc., has not caught up.
一方、廃棄物の大量有効利用方法として、石炭灰を種類や性状に応じて、焼成温度１１００〜１４００℃、滞留時間２０〜１２０分、キルンフルネス２〜１０％の運転条件に制御されたロータリーキルンに投入し、転動造粒させながら焼成する人工骨材の製造方法が提案されている（特許文献２）。
しかしながら、特許文献２に記載の方法においては、人工骨材の製造時に、砒素等の重金属や、硫黄分が含まれるキルン排ガスダスト等の副産物、すなわち新たな廃棄物が発生するという問題がある。
However, the method described in Patent Document 2 has a problem in that by-products such as heavy metal such as arsenic and kiln exhaust gas dust containing sulfur content, that is, new waste, are generated during the production of the artificial aggregate.
従って、本発明の目的は、産業廃棄物等の大量使用を可能にするとともに、新たな廃棄物を発生させることがないか、極端に少なくすることができる焼成物の製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a method for producing a baked product that enables large-scale use of industrial waste and the like, and does not generate new waste or extremely reduces it. is there.
本発明者らは、斯かる実情に鑑み、鋭意検討した結果、水硬率（H.M.）が０．４以上１．８未満である焼成物Ｂでは、砒素や硫黄を固定する能力に優れること、水硬率（H.M.）が０．４未満である焼成物Ｃでは、鉛及びCr6+を固定する能力に優れること、さらには、焼成物Ｂを製造する際に発生する副産物には鉛及びCr6+が多く含まれ、焼成物Ｃを製造する際に発生する副産物には砒素や硫黄が多く含まれることを見出し、本発明を完成した。 As a result of intensive studies in view of such circumstances, the inventors have excellent ability to fix arsenic and sulfur in the fired product B having a hydraulic modulus (HM) of 0.4 or more and less than 1.8. In the calcined product C having a hydraulic modulus (HM) of less than 0.4, the ability to fix lead and Cr 6+ is excellent. Furthermore, by-products generated when the calcined product B is manufactured include lead and Cr. It has been found that a large amount of 6+ is contained and by-products generated when the calcined product C is produced contain a large amount of arsenic and sulfur, and the present invention has been completed.
すなわち、本発明は、水硬率（H.M.）が１．８〜２．５である焼成物Ａ、水硬率（H.M.）が０．４以上１．８未満である焼成物Ｂ及び水硬率（H.M.）が０．４未満である焼成物Ｃの製造において、焼成物Ａ〜Ｃのいずれかを製造する際に発生する副産物を、他の焼成物の原料として使用することを特徴とする焼成物の製造方法を提供するものである。 That is, the present invention includes a fired product A having a hydraulic modulus (HM) of 1.8 to 2.5, a fired product B having a hydraulic modulus (HM) of 0.4 or more and less than 1.8, and a hydraulic modulus. In the production of a calcined product C having an (HM) of less than 0.4, a by-product generated when the calcined product A to C is produced is used as a raw material for another calcined product. The manufacturing method of a thing is provided.
本発明によれば、水硬率（H.M.）が１．８〜２．５である焼成物Ａ、水硬率（H.M.）が０．４以上１．８未満である焼成物Ｂ及び水硬率（H.M.）が０．４未満である焼成物Ｃを、新たな廃棄物（副産物）を発生させることがないか又は極端に少なくして、製造することができる。
また、産業廃棄物等を原料として大量に使用することができるので、廃棄物の有効利用の促進にも貢献することができる。
According to the present invention, a fired product A having a hydraulic modulus (HM) of 1.8 to 2.5, a fired product B having a hydraulic modulus (HM) of 0.4 or more and less than 1.8, and a hydraulic modulus. The fired product C having (HM) of less than 0.4 can be produced without generating or extremely reducing new waste (by-product).
Moreover, since industrial waste etc. can be used in large quantities as a raw material, it can also contribute to promotion of effective utilization of waste.
本発明で製造する焼成物Ａは、水硬率（H.M.）が１．８〜２．５、好ましくは１．８〜２．４、特に好ましくは１．８〜２．３のものである。このような水硬率の焼成物は、石膏等と粉砕・混合することにより、水硬性セメントとして使用することができる。このような焼成物としては、各種（低熱、中庸熱、普通、早強等）ポルトランドセメントクリンカーや、エコセメントクリンカーなどが挙げられる。 The fired product A produced in the present invention has a hydraulic modulus (H.M.) of 1.8 to 2.5, preferably 1.8 to 2.4, particularly preferably 1.8 to 2.3. Such a fired product having a hydraulic modulus can be used as a hydraulic cement by pulverizing and mixing with gypsum and the like. Examples of such fired products include various (low heat, moderate heat, normal, early strength, etc.) Portland cement clinker, eco cement clinker and the like.
焼成物Ａの原料としては、後記焼成物Ｂ及び／又は焼成物Ｃを製造する際に発生する副産物のほか、通常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。 As a raw material of the calcined product A, in addition to the by-product generated when the calcined product B and / or the calcined product C described later, a normal Portland cement clinker raw material, that is, a CaO raw material such as limestone, quicklime, slaked lime; SiO 2 raw material such as clay; Al 2 O 3 raw material such as clay; Fe 2 O 3 raw material such as iron cake and iron cake can be used.
また、本発明においては、焼成物Ａの原料として、更に、産業廃棄物、一般廃棄物及び建設発生土から選ばれる１種以上を用いることができる。これらを用いれば、廃棄物の有効利用を促進することができ、好ましい。ここで、産業廃棄物としては、例えば、生コンスラッジ、各種汚泥（例えば、下水汚泥、浄水汚泥、建設汚泥、製鉄汚泥等）、建設廃材、コンクリート廃材、ボーリング廃土、各種焼却灰（例えば、石炭灰、焼却飛灰、溶融飛灰等）、鋳物砂、ロックウール、廃ガラス、高炉２次灰等が挙げられる。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。建設発生土としては、例えば、建設現場や工事現場等から発生する土壌や残土、更に廃土壌などが挙げられる。
なお、本発明においては、廃棄物の有効利用促進の観点から、焼成物Ａの原料として、産業廃棄物、一般廃棄物及び建設発生土から選ばれる１種以上を、６０質量％以下用いるのが好ましい。
Moreover, in this invention, 1 or more types chosen from an industrial waste, a general waste, and construction generation | occurence | production soil can be used as a raw material of the baked product A further. If these are used, effective use of waste can be promoted, which is preferable. Here, as industrial waste, for example, raw consludge, various sludges (for example, sewage sludge, purified water sludge, construction sludge, iron sludge, etc.), construction wastes, concrete wastes, boring wastes, various incineration ash (for example, coal Ash, incinerated fly ash, molten fly ash, etc.), foundry sand, rock wool, waste glass, blast furnace secondary ash, and the like. Examples of the general waste include sewage sludge dry powder, municipal waste incineration ash, and shells. Examples of construction generated soil include soil and residual soil generated from construction sites and construction sites, and waste soil.
In the present invention, from the viewpoint of promoting effective utilization of waste, 60% by mass or less of at least one selected from industrial waste, general waste, and construction generated soil is used as the raw material of the fired product A. preferable.
焼成物Ａは、通常のポルトランドセメントクリンカーや、エコセメントクリンカーの製造設備等を使用して、これらに用いられる通常の方法により製造することができる。
本発明で製造される焼成物Ａは、砒素や硫黄を固定する能力に優れるので、砒素や硫黄を含む廃棄物等や、後記焼成物Ｃを製造する際に発生する副産物を原料として有効に活用することができる。
The fired product A can be manufactured by a normal method used for these by using a normal Portland cement clinker, an eco-cement clinker manufacturing facility, or the like.
Since the fired product A produced in the present invention is excellent in the ability to fix arsenic and sulfur, wastes containing arsenic and sulfur and by-products generated when the fired product C described later is produced are effectively used as raw materials. can do.
なお、焼成物Ａの製造においては、排ガスダストや微粉（ロータリーキルンから排出されるもので粒径が１mm以下のもの）等の副産物、より具体的には、キルン排ガスダスト、集塵装置で回収されたダスト（ＥＰダスト等）、廃熱ボイラダスト、スタビライザダスト、ドライヤダスト、クーラー排気ダスト、クーラーダスト、塩素バイパスダスト、排ガス浄化処理で発生するダスト、製品篩下等が発生する。これら副産物は、後記焼成物Ｂ、Ｃの原料として使用することができるので、新たな廃棄物が発生することはないか、又は極端に少なくすることができる。 In the production of the fired product A, it is collected by by-products such as exhaust gas dust and fine powder (which is discharged from a rotary kiln and having a particle size of 1 mm or less), more specifically, by kiln exhaust gas dust and a dust collector. Dust (EP dust, etc.), waste heat boiler dust, stabilizer dust, dryer dust, cooler exhaust dust, cooler dust, chlorine bypass dust, dust generated in exhaust gas purification treatment, product sieving, etc. are generated. Since these by-products can be used as raw materials for the calcined products B and C described later, new waste is not generated or can be extremely reduced.
焼成物Ａは、石膏やその他混和材（高炉スラグ粉末、フライアッシュ等）と粉砕・混合し、水硬セメント（ポルトランドセメント、混合セメント、エコセメント等）として使用することができる。 The fired product A can be used as hydraulic cement (Portland cement, mixed cement, eco cement, etc.) after being pulverized and mixed with gypsum and other admixtures (blast furnace slag powder, fly ash, etc.).
本発明で製造する焼成物Ｂは、水硬率（H.M.）が０．４以上１．８未満、好ましくは０．６５〜１．５、特に好ましくは０．７〜１．１のものである。水硬率が０．４未満では、砒素や硫黄を固定する能力が低下し、後記焼成物Ｃを製造する際に発生する副産物を原料として使用することが困難になる。また、前記範囲外では、原料として使用できる廃棄物等の量が少なくなり、廃棄物等の有効利用の観点からも好ましくない。 The fired product B produced in the present invention has a hydraulic modulus (HM) of 0.4 or more and less than 1.8, preferably 0.65 to 1.5, particularly preferably 0.7 to 1.1. . When the hydraulic modulus is less than 0.4, the ability to fix arsenic and sulfur is lowered, and it is difficult to use as a raw material a by-product generated when the calcined product C described later is manufactured. Further, outside the above range, the amount of waste etc. that can be used as a raw material decreases, which is not preferable from the viewpoint of effective use of waste etc.
焼成物Ｂの化学組成としては、ＣａＯが２８〜６５質量％、特に３８〜６０質量％、更に４０〜５４質量％であるのが好ましく；ＳｉＯ2が１８〜５０質量％、特に２２〜４７質量％、更に２８〜４４質量％であるのが好ましく；Ａｌ2Ｏ3が５〜３０質量％、特に７〜２５質量％、更に１０〜２０質量％であるのが好ましく；Ｆｅ2Ｏ3が１〜１０質量％、特に１〜８質量％、更に１〜７質量％であるのが好ましい。これらの範囲内であれば、水硬率（H.M.）が０．４以上１．８未満の焼成物Ｂを得るのに好適である。 As a chemical composition of the baked product B, it is preferable that CaO is 28 to 65% by mass, particularly 38 to 60% by mass, and further 40 to 54% by mass; SiO 2 is 18 to 50% by mass, particularly 22 to 47% by mass. %, More preferably 28-44% by mass; Al 2 O 3 is preferably 5-30% by mass, in particular 7-25% by mass, more preferably 10-20% by mass; Fe 2 O 3 is 1%. It is preferably 10 to 10% by mass, particularly 1 to 8% by mass, and more preferably 1 to 7% by mass. Within these ranges, it is suitable for obtaining a fired product B having a hydraulic modulus (HM) of 0.4 or more and less than 1.8.
焼成物Ｂの原料としては、前記焼成物Ａ及び／又は後記焼成物Ｃを製造する際に発生する副産物のほか、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原料などを使用することができる。 As a raw material of the calcined product B, in addition to by-products generated when the calcined product A and / or the calcined product C described later are manufactured, a general Portland cement clinker raw material, that is, a CaO raw material such as limestone, quicklime, slaked lime; SiO 2 raw material such as clay; Al 2 O 3 raw material such as clay; Fe 2 O 3 raw material such as iron cake and iron cake can be used.
また、本発明においては、焼成物Ｂの原料として、更に、産業廃棄物、一般廃棄物及び建設発生土から選ばれる１種以上を用いることができる。これらを用いれば、廃棄物の有効利用を促進することができるので好ましい。ここで、産業廃棄物、一般廃棄物、建設発生土としては、前記と同様のものを用いることができる。
なお、本発明においては、廃棄物の有効利用促進の観点から、焼成物Ｂの原料として、産業廃棄物、一般廃棄物及び建設発生土から選ばれる１種以上を、４０質量％以上用いるのが好ましい。
Moreover, in this invention, 1 or more types chosen from an industrial waste, a general waste, and construction generation | occurence | production soil can further be used as a raw material of the baked product B. Use of these is preferable because effective use of waste can be promoted. Here, as industrial waste, general waste, and construction generated soil, the same materials as described above can be used.
In the present invention, from the viewpoint of promoting the effective use of waste, 40% by mass or more of one or more selected from industrial waste, general waste, and construction generated soil is used as a raw material for the fired product B. preferable.
焼成物Ｂの製造においては、まず、前記原料を、水硬率（H.M.）が０．４以上１．８未満となるように混合する。原料の混合は、ナウターミキサー、エアーブレンデングサイロ等の公知の混合機を用いて行うことができ、連続式、バッチ式のいずれでも良い。
なお、粒度の粗い原料を用いる場合や、混合度を高めたい場合は、チューブミル等の粉砕を伴うものを使用することもでき、公知の粉砕機であれば、連続式、バッチ式のいずれを用いることもできる。粉砕混合時間は、経済性や混合性から、概ね３０分〜１時間程度が好ましく、使用する設備に応じて、適宜設定すれば良い。
In the production of the fired product B, first, the raw materials are mixed so that the hydraulic modulus (HM) is 0.4 or more and less than 1.8. The mixing of the raw materials can be performed using a known mixer such as a Nauter mixer or an air blending silo, and may be either a continuous type or a batch type.
In addition, when using raw materials with coarse particles, or when it is desired to increase the degree of mixing, it is possible to use a tube mill or other pulverizer, and any known pulverizer can be either a continuous type or a batch type. It can also be used. The pulverization and mixing time is preferably about 30 minutes to 1 hour from the viewpoint of economy and mixing properties, and may be appropriately set according to the equipment used.
混合された原料は、２０mm以下、好ましくは１０mm以下の粉状及び／又は粒状の状態で、好ましくはロータリーキルンに投入し、造粒しながら焼成することにより、焼成物Ｂを得ることができる。 The mixed raw material can be obtained in a powdery and / or granular state of 20 mm or less, preferably 10 mm or less, preferably in a rotary kiln and baked while granulating to obtain a fired product B.
原料は、粉状のままロータリーキルンに投入することができるが、野外ホッパーからベルトフィーダーを介してキルンに送入する場合など、発塵や周辺環境に配慮が必要な場合、あるいはハンドリング面において問題を生じさせる可能性がある場合は、原料粉末を２０mm以下の粒状に整粒して、ロータリーキルンに投入しても良い。 The raw material can be put into the rotary kiln as it is in powder form, but it may cause problems in terms of handling such as dust generation and the surrounding environment, such as when sending it to the kiln via a belt feeder from an outdoor hopper. If there is a possibility of generating the raw material powder, the raw material powder may be sized to a particle size of 20 mm or less and charged into a rotary kiln.
この際、整粒にパンペレタイザーや押し出し成形機を用いることもできるが、これらは習熟された技能を必要とすることや、設備コストの観点から好ましくなく、例えば、パグミルやスクリューフィーダーを使用し、原料輸送経路、あるいは整粒中の原料に直接散水するのが、設備を簡素にでき、特別な技能も必要としないことから好ましい。また、整粒物の粒子径のコントロールは、散水量で調整することができ、最適な散水量は、原料粉末の粉末度や含水量によって異なるため、整粒物の状態を見ながら、適宜調節するのが好ましい。 At this time, a pan pelletizer or an extrusion molding machine can be used for sizing, but these require skilled skills and are not preferable from the viewpoint of equipment costs, for example, using a pug mill or a screw feeder, It is preferable to spray water directly on the raw material transport route or the raw material being sized because the equipment can be simplified and no special skills are required. In addition, the control of the particle size of the sized product can be adjusted by the amount of water spray, and the optimal water spray amount varies depending on the fineness and water content of the raw material powder. It is preferable to do this.
原料粉末の整粒物は、粒径が２０mm以下であれば、どのような形状でも良く、整粒ののち、解砕や分級にて２０mm以下に調整したものを用いても良い。整粒物の粒径が２０mm以下であれば、内部まで均質に焼成することができるので好ましい。 The raw powder sized product may have any shape as long as the particle size is 20 mm or less, and may be adjusted to 20 mm or less by pulverization or classification after sizing. If the particle size of the sized product is 20 mm or less, it is preferable because the inside can be uniformly fired.
このように混合された粉状又は２０mm以下に整粒された粒状の原料は、好ましくはロータリーキルンで焼成される。
ロータリーキルンを使用すると、安定した品質の焼成物が連続して得られ易く、工業生産に向いていることに加え、前記の原料の配合調整による相乗効果も合わさって、極めて安定的に焼成物を製造することが可能となる。また、セメント産業における、遊休設備の有効活用の観点からも好ましい。
The mixed powdery or granular raw material adjusted to 20 mm or less is preferably fired in a rotary kiln.
When a rotary kiln is used, it is easy to obtain a fired product of stable quality continuously, and it is suitable for industrial production. In addition, a synergistic effect by adjusting the blending of the above raw materials is combined to produce a fired product extremely stably. It becomes possible to do. It is also preferable from the viewpoint of effective utilization of idle facilities in the cement industry.
ロータリーキルンを用いた焼成物Ｂの焼成は、８００〜１５００℃、特に１１５０〜１３５０℃で行うのが好ましく、所望の焼成物の品質（絶乾密度、吸水率等）を勘案して、適宜調整すれば良い。
なお、焼成温度が８００℃未満では、十分な焼成が行われず、原料が造粒されないまま排出される憂いがあり好ましくなく、１５００℃を超えると、原料が溶融してしまい、運転に支障をきたすため好ましくない。
Firing of the fired product B using a rotary kiln is preferably performed at 800 to 1500 ° C., particularly 1150 to 1350 ° C., and may be adjusted as appropriate in consideration of the desired fired product quality (absolute density, water absorption, etc.). It ’s fine.
If the firing temperature is less than 800 ° C., there is a concern that sufficient firing is not performed and the raw material is discharged without being granulated, and if the temperature exceeds 1500 ° C., the raw material melts, which hinders operation. Therefore, it is not preferable.
ロータリーキルンは、排気系にサイクロン等の原料循環予熱設備、プレヒーター、廃熱ボイラー、粉砕設備、乾燥設備、排ガス浄化処理設備、集塵設備等を付設していても良い。また、窯尻にリフターを備えているものや、ロータリーキルンの内径を途中で窄めたり、広げるなどの加工を加えたものであっても良い。
なお、ロータリーキルンに原料循環予熱設備、プレヒーターが付いているものは、それらのどこからでも、及びキルンに直接原料を投入しても良い。
The rotary kiln may be provided with a material circulation preheating facility such as a cyclone, a preheater, a waste heat boiler, a pulverization facility, a drying facility, an exhaust gas purification treatment facility, a dust collection facility and the like in an exhaust system. Moreover, what provided the lifter in the kiln bottom, and what added processing, such as narrowing or expanding the internal diameter of a rotary kiln on the way, may be used.
If the rotary kiln is equipped with a raw material circulation preheating facility and a pre-heater, the raw material may be fed directly from anywhere in the kiln.
燃料としては、重油、微粉炭、再生油、ＬＰＧ、ＮＰＧ等の一般に用いられているものであれば、単独又は混合して使用することができ、所定の焼成温度になるよう、焚き込み量を調整する。近年、セメントキルンにおいては、廃プラスチック、廃タイヤ、廃木材や肉骨粉などが、燃料代替として用いられているが、これらを燃料の一部に用いても良い。 As fuel, if it is generally used, such as heavy oil, pulverized coal, reclaimed oil, LPG, NPG, etc., it can be used individually or in mixture, and the amount of penetration is set so that it may become a predetermined calcination temperature. adjust. In recent years, waste plastics, waste tires, waste wood, meat and bone powder and the like have been used as a fuel substitute in cement kilns, but these may be used as part of the fuel.
ロータリーキルンでの焼成時間は、経済性の観点から概ね１５〜１２０分とするのが好ましく、所定品質の焼成物が得られるよう、適宜調整すれば良い。また、焼成時のロータリーキルン内のＯ2分圧は、特に制限されず、一般的な焼成範囲である１〜１２％に調整すれば良い。また、サイクロン等の原料循環系を備えていないロータリーキルンにて焼成を行う場合は、原料が系外に飛散するのを防ぐため、ロータリーキルン窯尻の風速が概ね５m/s以下となるよう、ドラフトを調整するのが好ましい。 The firing time in the rotary kiln is preferably approximately 15 to 120 minutes from the viewpoint of economy, and may be appropriately adjusted so that a fired product of a predetermined quality is obtained. Further, the O 2 partial pressure in the rotary kiln at the time of firing is not particularly limited, and may be adjusted to 1 to 12% which is a general firing range. Also, when firing in a rotary kiln that does not have a material circulation system such as a cyclone, in order to prevent the material from scattering outside the system, the draft should be set so that the wind speed at the bottom of the rotary kiln kiln is approximately 5 m / s or less. It is preferable to adjust.
焼成中は、焼成物Ｂの品質をより高める目的、またより安定した運転を目的として、融着防止材をロータリーキルンの窯前から吹き込むこともできる。
融着防止材としては、珪石、アルサイト、アルミナ、セメントの粉末や、セメントの主要鉱物であるエーライト、ビーライト粉末などを用いることができる。
During firing, an anti-fusing material can be blown from the front of the kiln of the rotary kiln for the purpose of further improving the quality of the fired product B and for more stable operation.
As the anti-fusing material, silica powder, alusite, alumina, cement powder, alite, belite powder and the like, which are the main minerals of cement, can be used.
融着防止材は、平均粒子径が１０〜１０００μmのものを用いるのが、融着防止効果が得られ易いので好ましく、その純度は高いものほど好ましい。融着防止材の平均粒子径が１０μm未満では、焼成中に原料化して焼成物中に取り込まれる可能性が高く、融着防止材としての効果が減少してしまい、焼成物の品質低下を生じるために好ましくない。また、融着防止材の平均粒子径が１０００μmを超えると、送入部位等の磨耗が著しく、これら消耗部位や部品の交換が頻繁になるために好ましくない。さらに融着防止材の平均粒子径が数ミリを超えると、融着防止材としての効果が減少し、また焼成物に融着したものとの分離が困難になるために好ましくない。 It is preferable to use an anti-fusing material having an average particle diameter of 10 to 1000 μm because an anti-fusing effect is easily obtained, and the higher the purity, the better. If the average particle size of the anti-fusing material is less than 10 μm, it is highly likely that the material will be used as a raw material during firing and taken into the fired product, resulting in a decrease in the effect as the anti-fusion material, resulting in a reduction in the quality of the fired product. Therefore, it is not preferable. In addition, if the average particle diameter of the anti-fusing material exceeds 1000 μm, wear of the feeding site and the like is remarkable, and replacement of these consumable sites and parts is not preferable. Further, if the average particle diameter of the anti-fusing material exceeds several millimeters, the effect as the anti-fusing material is reduced, and separation from the one fused to the fired product becomes difficult, which is not preferable.
融着防止材の吹き込み方法としては、焼点に融着防止材が所定量吹き付けられるものであれば、特に限定されないが、例えば、水冷管、空冷管などの送入管をロータリーキルンの窯前に挿入し、エジェクタ等の空気圧送や、モノーポンプ等の輸送ポンプによって、融着防止材を吹き付けるのが、装置を簡便にできるので好ましい。
また、融着防止材の吹き込み量は、ロータリーキルンに送入する混合原料に対し、３〜１０質量％であるのが、融着防止材としての効果が十分に得られるので好ましい。
The method of blowing the anti-fusing material is not particularly limited as long as a predetermined amount of the anti-fusing material can be sprayed on the burning point. For example, a water-cooled tube, an air-cooled tube, or the like is provided before the rotary kiln kiln. It is preferable to insert and blow the anti-fusing material with a pneumatic pump such as an ejector or a transport pump such as a mono pump because the apparatus can be simplified.
Moreover, it is preferable that the blowing amount of the anti-fusing material is 3 to 10% by mass with respect to the mixed raw material fed into the rotary kiln because the effect as the anti-fusing material can be sufficiently obtained.
上記のように、ロータリーキルンで原料を焼成することにより、絶乾密度が１．５〜３．０ｇ／cm3、２４時間吸水率、減圧吸水率が０．１〜１５％、直径５〜１０mmの焼成物の圧壊荷重が０．２kN以上、又は直径１０〜１５mmの焼成物の圧壊荷重が０．５kN以上の焼成物Ｂを得ることができる。 As described above, by firing the raw material in a rotary kiln, the absolute dry density is 1.5 to 3.0 g / cm 3 , the 24-hour water absorption rate, the reduced pressure water absorption rate is 0.1 to 15%, and the diameter is 5 to 10 mm. A fired product B can be obtained in which the crushing load of the fired product is 0.2 kN or more, or the crushing load of the fired product having a diameter of 10 to 15 mm is 0.5 kN or more.
本発明で製造される焼成物Ｂは、砒素や硫黄を固定する能力に優れ、かつ、排ガスとして砒素や硫黄を排出することもないので、砒素や硫黄を含む廃棄物等や、後記焼成物Ｃを製造する際に発生する副産物を原料として有効に活用することができる。
なお、焼成物Ｂの製造においては、排ガスダストや微粉（ロータリーキルンから排出されるもので粒径が１mm以下のもの）等の副産物、より具体的には、キルン排ガスダスト、集塵装置で回収されたダスト（ＥＰダスト等）、廃熱ボイラダスト、スタビライザダスト、ドライヤダスト、クーラー排気ダスト、クーラーダスト、塩素バイパスダスト、排ガス浄化処理で発生するダスト、製品篩下等が発生する。これら副産物には鉛やCr6+が含まれているが、該副産物は、前記焼成物Ａや、後記焼成物Ｃの原料として使用することができるので、新たな廃棄物が発生することはないか、又は極端に少なくすることができる。なお、本発明においては、該副産物を、焼成物Ｃの原料として使用するのが好ましい。
The fired product B produced in the present invention has an excellent ability to fix arsenic and sulfur and does not discharge arsenic and sulfur as exhaust gas. By-products generated when producing can be effectively used as raw materials.
In the production of the calcined product B, it is recovered by by-products such as exhaust gas dust and fine powder (discharged from the rotary kiln and having a particle size of 1 mm or less), more specifically, by the kiln exhaust gas dust and the dust collector. Dust (EP dust, etc.), waste heat boiler dust, stabilizer dust, dryer dust, cooler exhaust dust, cooler dust, chlorine bypass dust, dust generated in exhaust gas purification treatment, product sieving, etc. are generated. These by-products contain lead and Cr 6+, but since the by-products can be used as raw materials for the calcined product A and the calcined product C described later, no new waste is generated. Or extremely low. In addition, in this invention, it is preferable to use this by-product as a raw material of the baked product C.
本発明で製造する焼成物Ｃは、水硬率(H.M.)が０．４未満、好ましくは０．２５以下、特に好ましくは０．２以下のものである。水硬率が０．４を超えると、鉛やCr6+を固定する能力が低下し、前記焼成物Ｂを製造する際に発生する副生物を原料として使用することが困難となる。 The calcined product C produced in the present invention has a hydraulic modulus (HM) of less than 0.4, preferably 0.25 or less, particularly preferably 0.2 or less. When the hydraulic modulus exceeds 0.4, the ability to fix lead and Cr 6+ decreases, and it becomes difficult to use by-products generated when the fired product B is produced as a raw material.
焼成物Ｃの化学組成は、ＣａＯが１〜３０質量％、特に１〜２２質量％、更に１〜１７質量％であるのが好ましく；Ｓｉ０2が３０〜８０質量％、特に３５〜７５質量％、更に４０〜７０質量％であるのが好ましく；Ａ１2０3が５〜４０質量％、特に１０〜３５質量％、更に１５〜３０質量％であるのが好ましく；Ｆｅ2０3が１〜１２質量％、特に１〜８質量％、更に１〜５質量％であるのが好ましい。これらの範囲内であれば、水硬率０．４未満の焼成物Ｃを得るのに好適である。 The chemical composition of the fired product C is preferably 1 to 30% by mass of CaO, particularly 1 to 22% by mass, more preferably 1 to 17% by mass; 30 to 80% by mass of SiO 2 , particularly 35 to 75% by mass. , more preferably in the range of 40 to 70 wt%; A1 2 0 3 5 to 40% by weight, in particular 10 to 35 wt%, more of preferably 15 to 30 wt%; Fe 2 0 3 is 1 It is preferably 12% by mass, particularly 1 to 8% by mass, and more preferably 1 to 5% by mass. Within these ranges, it is suitable for obtaining a fired product C having a hydraulic modulus of less than 0.4.
焼成物Ｃの原料としては、前記焼成物Ａ及び／又は焼成物Ｂを製造する際に発生する副産物のほか、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Ａ１2Ｏ3原料、鉄滓、鉄ケーキ等のＦｅ2Ｏ3原料を使用することができる。 As a raw material of the calcined product C, in addition to by-products generated when the calcined product A and / or the calcined product B are produced, a general Portland cement clinker raw material, that is, a CaO raw material such as limestone, quicklime, slaked lime, silica stone, clay An SiO 2 raw material such as clay, an A1 2 O 3 raw material such as clay, and an Fe 2 O 3 raw material such as iron cake and iron cake can be used.
また、本発明においては、焼成物Ｃの原料として、更に、産業廃棄物、一般廃棄物及び建設発生土から選ばれる１種以上を用いることができる。これらを焼成物の原料として、使用することは、廃棄物の有効利用を促進させることができるので好ましい。ここで、産業廃棄物、一般廃棄物、建設発生土としては、前記と同様のものを用いることができる。
なお、本発明においては、廃棄物の有効利用促進の観点から、焼成物Ｃの原料として、産業廃棄物、一般廃棄物及び建設発生土から選ばれる１種以上を、７０質量％以上使用するのが好ましい。
Moreover, in this invention, 1 or more types chosen from an industrial waste, a general waste, and construction generation | occurence | production soil can be further used as a raw material of the baked product C. It is preferable to use these as raw materials for the baked product because the effective use of waste can be promoted. Here, as industrial waste, general waste, and construction generated soil, the same materials as described above can be used.
In the present invention, from the viewpoint of promoting the effective use of waste, 70% by mass or more of at least one selected from industrial waste, general waste, and construction generated soil is used as a raw material for the fired product C. Is preferred.
焼成物Ｃの製造においては、まず、前記原料を、水硬率（H.M.）が０．４未満となるように混合する。原料の混合は、前記焼成物Ｂの製造の際に使用する装置と同様のものを用いて行うことができる。 In the production of the fired product C, first, the raw materials are mixed so that the hydraulic modulus (H.M.) is less than 0.4. The mixing of the raw materials can be performed using the same apparatus as that used for manufacturing the fired product B.
混合された原料は、２０mm以下、好ましくは１０mm以下の粉状及び／又は粒状の状態で、好ましくはロータリーキルンに投入し、造粒しながら焼成することにより、焼成物Ｃを得ることができる。
ロータリーキルンでの焼成条件等は、前記焼成物Ｂの焼成と同様の条件で行うことができる。
なお、焼成物Ｃの焼成においては、酸性ガスが発生するおそれがあるので、排ガス浄化処理設備を付設することが望ましい。
The mixed raw material is in a powdery and / or granular state of 20 mm or less, preferably 10 mm or less, and is preferably charged into a rotary kiln and fired while granulating to obtain a fired product C.
The firing conditions in the rotary kiln can be performed under the same conditions as the firing of the fired product B.
In the firing of the fired product C, an acid gas may be generated. Therefore, it is desirable to provide an exhaust gas purification treatment facility.
また、焼成物Ｃの焼成においては、焼結助剤を使用することができる。焼結助剤とは、焼結反応を促すために添加するものであり、主原料である廃棄物等にすでに焼結性が備わっていれば、特に添加する必要はないが、原料成分では十分な焼結性が確保できない場合には、焼結助剤を添加するのが好ましい。 In firing the fired product C, a sintering aid can be used. Sintering aid is added to promote the sintering reaction. If the waste, which is the main raw material, already has sinterability, it is not necessary to add it. When it is not possible to ensure sufficient sinterability, it is preferable to add a sintering aid.
焼結助剤としては、例えば、粘土やカオリン、ベントナイト、各種のＡｌ2Ｏ3源、セメント等が挙げられる。また、ＭｇＯも焼結を促す効果を有しており、ＭｇＯは勿論のこと、この成分を含有するＭｇ（ＯＨ）2やＭｇＣＯ3、或いはＣａＣＯ3・ＭｇＣＯ3（ドロマイト）、ＭｇＯ・Ａｌ2Ｏ3（スピネル）、２ＭｇＯ・Ｓｉ０2（フオルステライト）なども好適である。また、鉄鋼副産物であるフェロニッケルスラグなども、ＭｇＯの含有量が高いばかりでなく、その有効利用といった観点からもより好適な材料である。 Examples of the sintering aid include clay, kaolin, bentonite, various Al 2 O 3 sources, cement, and the like. MgO also has an effect of promoting sintering. Mg (OH) 2 , MgCO 3 , CaCO 3 .MgCO 3 (dolomite), MgO.Al 2 O containing MgO as well as MgO are of course included. 3 (spinel), 2MgO · Si0 2 (Fuorusu Te write) is also preferred, such as. Further, ferronickel slag, which is a by-product of steel, is a more suitable material from the viewpoint of not only the high content of MgO but also its effective use.
Ｋ、Ｎａ等のアルカリ金属の酸化物や複合酸化物、例えば炭酸ナトリウム、炭酸カリウム等も焼結反応を促進する効果を示すことが知られており、その複合酸化物である正長石、曹長石等の長石族、硝石、雲母族、霞石も好適である。また、廃ガラスや赤泥なども、その有効利用の観点から好適な材料である。 Alkali metal oxides and composite oxides such as K and Na, such as sodium carbonate and potassium carbonate, are also known to show the effect of promoting the sintering reaction. Also suitable are feldspars such as feldspar, glass, mica and meteorite. Waste glass and red mud are also suitable materials from the viewpoint of their effective use.
焼結助剤の粒度は、廃棄物等との反応性から、平均粒子径１〜３００μmであるのが好ましく、特に平均粒子径１〜５０μmが好ましい。３００μmを超える場合は、粉砕等によって粒度を調整したものを用いることができる。
焼結助剤の粒度が１μm未満では、粉砕等の費用が高騰するため好ましくなく、３００μmを超えると、廃棄物等との反応性が悪くなり、焼結肋剤としての効果が得られないために好ましくない。
The particle size of the sintering aid is preferably an average particle size of 1 to 300 μm, particularly preferably an average particle size of 1 to 50 μm, in view of reactivity with wastes and the like. When exceeding 300 micrometers, what adjusted the particle size by grinding | pulverization etc. can be used.
If the particle size of the sintering aid is less than 1 μm, the cost of pulverization and the like will increase, and if it exceeds 300 μm, the reactivity with the waste will deteriorate, and the effect as a sintering glaze will not be obtained. It is not preferable.
また、焼結助剤の添加量は、焼成物中の焼結助剤成分元素の酸化物換算値として、ＭｇＯが０．１〜１０質量％、Ｒ2Ｏが０．１〜１０質量％とするのが好ましい。なお、Ｒ2Ｏは、アルカリ金属酸化物の総称で、Ｒ2Ｏ（質量％）＝Ｎａ2Ｏ（質量％）＋０．６８５Ｋ2Ｏ（質量％）で表すことができる。 The amount of sintering aid, the oxide equivalent value of the sintering auxiliary component elements in the sintered product, MgO 0.1 to 10 wt%, and R 2 O is 0.1 to 10 mass% It is preferable to do this. R 2 O is a generic name for alkali metal oxides and can be represented by R 2 O (mass%) = Na 2 O (mass%) + 0.685 K 2 O (mass%).
ＭｇＯが０．１〜１０質量％であれば、焼結助剤としての効果が十分に得られるので好ましい。Ｒ2Ｏが０．１〜１０質量％であれば、焼結助剤としての効果が十分得られるとともに、焼成時の液相の発生が急激にならず、安定した運転が行えるので好ましい。 If MgO is 0.1-10 mass%, since the effect as a sintering aid is fully acquired, it is preferable. When R 2 O is 0.1 to 10% by mass, the effect as a sintering aid is sufficiently obtained, and generation of a liquid phase during firing is not abrupt, and stable operation can be performed.
上記のように、ロータリーキルンで原料を焼成することにより、絶乾密度が１．０〜２．５ｇ／cm3、２４時間吸水率、減圧吸水率が０．１〜１５％、直径５〜１０mmの焼成物の圧壊荷重が０．２kN以上、又は直径１０〜１５mmの焼成物の圧壊荷重が０．５kN以上の焼成物Ｃを得ることができる。 As described above, by firing the raw material in a rotary kiln, the absolute dry density is 1.0 to 2.5 g / cm 3 , the 24-hour water absorption rate, the reduced pressure water absorption rate is 0.1 to 15%, and the diameter is 5 to 10 mm. A fired product C can be obtained in which the crushing load of the fired product is 0.2 kN or more, or the crushing load of the fired product having a diameter of 10 to 15 mm is 0.5 kN or more.
本発明で製造される焼成物Ｃは、鉛やCr6+を固定する能力に優れ、かつ、排ガスとして、鉛やクロムを排出することもないので、鉛やCr6+を含む廃棄物等や、前記焼成物Ｂを製造する際に発生する副産物を原料として有効に活用することができる。
なお、焼成物Ｃの製造においては、排ガスダストや微粉（ロータリーキルンから排出されるもので粒径が１mm以下のもの）等の副産物、より具体的には、キルン排ガスダスト、集塵装置で回収されたダスト（ＥＰダスト等）、廃熱ボイラダスト、スタビライザダスト、ドライヤダスト、クーラー排気ダスト、クーラーダスト、塩素バイパスダスト、排ガス浄化処理で発生するダスト、製品篩下等が発生する。これら副産物には砒素や硫黄が含まれるが、該副産物は、前記焼成物Ａ、Ｂの原料として使用することができるので、新たな廃棄物が発生することはないか、又は極端に少なくすることができる。
Calcined product C produced in the present invention is excellent in ability to fix lead and Cr 6+, and as an exhaust gas, since nor discharging lead and chromium, Ya waste containing lead and Cr 6+ By-products generated when the fired product B is produced can be effectively used as a raw material.
In the production of the fired product C, it is recovered by by-products such as exhaust gas dust and fine powder (which is discharged from a rotary kiln and having a particle size of 1 mm or less), more specifically, by kiln exhaust gas dust and a dust collector. Dust (EP dust, etc.), waste heat boiler dust, stabilizer dust, dryer dust, cooler exhaust dust, cooler dust, chlorine bypass dust, dust generated in exhaust gas purification treatment, product sieving, etc. are generated. These by-products contain arsenic and sulfur, but since the by-products can be used as raw materials for the fired products A and B, no new waste is generated or extremely reduced. Can do.
なお、本発明の焼成物の製造方法においては、（１）２本以上のロータリーキルンを使用して、焼成物Ａ〜Ｃを並行して製造しても良いし（この場合、ロータリーキルンは同一工場内のものでも良いし、別の工場のものでも良い）、（２）１本のロータリーキルンを使用して、焼成物Ａ〜Ｃを交互に製造しても良い。 In addition, in the manufacturing method of the baked product of this invention, (1) You may manufacture baked products AC in parallel using two or more rotary kilns (in this case, rotary kilns are in the same factory. (2) The baked products A to C may be produced alternately by using one rotary kiln.
本発明で製造される焼成物Ｂ及び焼成物Ｃは、２４時間吸水率が低いばかりでなく、減圧吸水率も低いのが特徴であり、前記のように２４時間吸水率、減圧吸水率が０．１〜１５％である焼成物が得られるのはもちろん、２４時間吸水率、減圧吸水率が共に０．１〜６％で、直径５〜１０mmの焼成物の圧壊荷重が０．５kN以上、又は直径１０〜１５mmの焼成物の圧壊荷重が１．０kN以上の焼成物も容易に得ることができる。 The calcined product B and the calcined product C produced by the present invention are not only low in water absorption for 24 hours, but also characterized by low water absorption at reduced pressure. As described above, the water absorption rate at 24 hours and the water absorption under reduced pressure are 0. Of course, a fired product of 1 to 15% is obtained, and both the 24-hour water absorption and the reduced-pressure water absorption are 0.1 to 6%, and the crushing load of the fired product having a diameter of 5 to 10 mm is 0.5 kN or more. Alternatively, a fired product having a crushing load of 1.0 kN or more can be easily obtained.
ここで、減圧吸水率とは、一定の減圧下にて強制的に吸水を行う方法であり、具体的には、密閉容器中に焼成物を水没させ、真空ポンプで−４００mmHgまで容器内を減圧し、１５分間静置した後に徐々に大気に開放し、焼成物に含水した水量から減圧時の吸水率を測定した値である。
この減圧吸水率は、コンクリートのポンプ圧送時の配管内における骨材の吸水性を推察する指標となるものであり、焼成物をコンクリート用の骨材として使用する場合には、コンクリートとした際の良好なワーカビリティーを確保するために、焼成物は、２４時間吸水率のみならず、減圧吸水率を低くすることが重要になる。
Here, the reduced-pressure water absorption is a method of forcibly absorbing water under a certain reduced pressure. Specifically, the fired product is submerged in a sealed container and the inside of the container is decompressed to −400 mmHg with a vacuum pump. Then, after standing for 15 minutes, it was gradually opened to the atmosphere, and the water absorption at the time of depressurization was measured from the amount of water contained in the fired product.
This reduced water absorption is an index for inferring the water absorption of the aggregate in the pipe when pumping concrete, and when using the fired product as an aggregate for concrete, In order to ensure good workability, it is important for the fired product to have a reduced water absorption rate as well as a 24-hour water absorption rate.
本発明で製造する焼成物Ｂ及び焼成物Ｃは、高強度で且つ低吸水率の焼成物であるため、コンクリート用の骨材、路盤材、埋め戻し材、アスファルト用の骨材、盛土材、充填材、セメント原料の粘土の代替等として好適に使用することができる。 Since the fired product B and the fired product C produced by the present invention are fired products having high strength and low water absorption, aggregates for concrete, roadbed materials, backfill materials, aggregates for asphalt, embankment materials, It can be suitably used as an alternative to fillers, clay as a raw material for cement, and the like.
本発明においては、焼成物Ａ〜Ｃのいずれかを製造する際に発生する副産物を、他の焼成物の原料として使用することができるが、特に、(1)焼成物Ｂを製造する際に発生する副産物を焼成物Ｃの原料として使用し、かつ、焼成物Ｃを製造する際に発生する副産物を焼成物Ｂの原料として使用すること；(2)焼成物Ａを製造する際に発生する副産物を焼成物Ｃの原料として使用し、かつ、焼成物Ｃを製造する際に発生する副産物を焼成物Ａの原料として使用することが好ましい。 In the present invention, the by-product generated when producing any one of the fired products A to C can be used as a raw material for other fired products, and in particular, (1) when producing the fired product B. Use the generated by-product as a raw material for the calcined product C, and use the by-product generated when the calcined product C is produced as the raw material for the calcined product B; (2) Generated when producing the calcined product A It is preferable to use the by-product as a raw material of the baked product C and to use a by-product generated when the baked product C is manufactured as the raw material of the baked product A.
次に、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらに何ら制限されるものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not restrict | limited to these at all.
実施例１
（１−１）焼成物Ａ１の製造：
普通ポルトランドセメントクリンカーの製造において、実施例２の焼成物Ｂ２の製造の際に発生したＥＰダスト（以下、副産物Ａと称す）を原料として使用し、焼成物Ａ１（普通ポルトランドセメントクリンカー）を製造した。焼成物Ａ１の水硬率は２．１０である。
なお、焼成物Ａ１の製造は、通常のポルトランドセメントクリンカーの製造と同様に行った。
Example 1
(1-1) Production of fired product A1:
In the production of ordinary Portland cement clinker, EP dust (hereinafter referred to as byproduct A) generated during the production of the fired product B2 of Example 2 was used as a raw material to produce a fired product A1 (ordinary Portland cement clinker). . The hydraulic modulus of the fired product A1 is 2.10.
In addition, manufacture of the baked product A1 was performed similarly to manufacture of a normal Portland cement clinker.
得られたポルトランドセメントクリンカーに、二水石膏をＳＯ3換算で２．０質量％添加し、ブレーン比表面積３２００cm2／ｇに粉砕して、普通ポルトランドセメントを調製した。
この普通ポルトランドセメントを使用し、「ＪＩＳ Ｒ ５２０１」に準じて圧縮強度試験を行った。その結果、材齢７日の圧縮強度は４５Ｎ／mm2、材齢２８日の圧縮強度は６３Ｎ／mm2であった。
この結果より、焼成物Ａの製造において、焼成物Ｂの製造の際に発生したＥＰダストを原料として使用できることが確認された。
To the obtained Portland cement clinker, 2.0% by mass of dihydrate gypsum was added in terms of SO 3 and pulverized to a Blaine specific surface area of 3200 cm 2 / g to prepare ordinary Portland cement.
Using this ordinary Portland cement, a compressive strength test was conducted according to "JIS R 5201". As a result, the compressive strength at age 7 was 45 N / mm 2 and the compressive strength at age 28 was 63 N / mm 2 .
From this result, it was confirmed that in the production of the fired product A, EP dust generated during the production of the fired product B can be used as a raw material.
（１−２）焼成物Ａ２の製造：
普通ポルトランドセメントクリンカーの製造において、実施例３の焼成物Ｃ２の製造の際に発生したＥＰダスト（以下、副産物Ｂと称す）を原料として使用し、焼成物Ａ２（普通ポルトランドセメントクリンカー）を製造した。焼成物Ａ２の水硬率は２．１５である。また、焼成物Ａ２の砒素含有量は１１mg／kg、ＳＯ3含有量は０．８５質量％であった。
なお、焼成物Ａ２の製造は、通常のポルトランドセメントクリンカーの製造と同様に行った。
(1-2) Production of fired product A2:
In the production of ordinary Portland cement clinker, the EP dust (hereinafter referred to as byproduct B) generated during the production of the calcined product C2 of Example 3 was used as a raw material to produce a calcined product A2 (ordinary Portland cement clinker). . The hydraulic modulus of the fired product A2 is 2.15. Further, the baked product A2 had an arsenic content of 11 mg / kg and an SO 3 content of 0.85% by mass.
In addition, manufacture of baked product A2 was performed similarly to manufacture of a normal Portland cement clinker.
得られたポルトランドセメントクリンカーに、二水石膏をＳＯ3換算で２．０質量％添加し、ブレーン比表面積３２００cm2／ｇに粉砕して、普通ポルトランドセメントを調製した。
この普通ポルトランドセメントを使用し、「ＪＩＳ Ｒ ５２０１」に準じて圧縮強度試験を行った。その結果、材齢７日の圧縮強度は４３Ｎ／mm2、材齢２８日の圧縮強度は６２Ｎ／mm2であった。また、材齢２８日の試験体からの砒素の溶出量を、環境省告示４６号法に準じて測定した。その結果、砒素の溶出量は、０．００１mg／Ｌ未満であった。
以上の結果より、焼成物Ａの製造において、焼成物Ｃの製造の際に発生したＥＰダストを原料として使用できることが確認された。
To the obtained Portland cement clinker, 2.0% by mass of dihydrate gypsum was added in terms of SO 3 and pulverized to a Blaine specific surface area of 3200 cm 2 / g to prepare ordinary Portland cement.
Using this ordinary Portland cement, a compressive strength test was conducted according to "JIS R 5201". As a result, the compressive strength at the age of 7 days 43N / mm 2, compression strength at the age of 28 days was 62N / mm 2. In addition, the amount of arsenic eluted from a specimen with a material age of 28 was measured according to the Ministry of the Environment Notification No. 46 method. As a result, the elution amount of arsenic was less than 0.001 mg / L.
From the above results, it was confirmed that in the production of the fired product A, EP dust generated during the production of the fired product C can be used as a raw material.
実施例２
（２−１）焼成物Ｂ１の製造：
原料として、建設発生土、石炭灰、石灰石及び普通ポルトランドセメント製造の際に発生したＥＰダスト（以下、副産物Ｃと称す）を使用し、水硬率が０．８５の焼成物Ｂ１を製造した。焼成物Ｂ１の製造は、各原料を、水硬率が０．８５になるよう配合し、該原料を、１３０m3のエアーブレンディングサイロに投入し、エアーによる曝流混合を６時間行った。
Example 2
(2-1) Production of fired product B1:
As the raw material, construction-generated soil, coal ash, limestone and EP dust (hereinafter referred to as by-product C) generated during the production of ordinary Portland cement were used to produce a fired product B1 having a hydraulic modulus of 0.85. In the production of the fired product B1, the raw materials were blended so that the hydraulic modulus was 0.85, the raw materials were put into a 130 m 3 air blending silo, and aeration mixing with air was performed for 6 hours.
続いて、得られた原料を、内径１．５ｍ、長さ２０ｍのロータリーキルンに、１ton／hで投入し、滞留時間が６０分となる条件で、緻密質な焼成物が得られるよう、燃料であるＡ重油の焚き量を調整しながら、約１３００℃で焼成した。
なお、本実施例において、焼成物Ｂ１の原料中の廃棄物等（石灰石以外の原料）の割合は、５６質量％である。
Subsequently, the obtained raw material is introduced into a rotary kiln having an inner diameter of 1.5 m and a length of 20 m at 1 ton / h, and fuel is used so that a dense fired product is obtained under the condition that the residence time is 60 minutes. It baked at about 1300 degreeC, adjusting the amount of burning of a certain A heavy oil.
In addition, in a present Example, the ratio of the waste etc. (raw materials other than limestone) in the raw material of baked product B1 is 56 mass%.
（２−２）焼成物Ｂ１の評価：
５〜１５mmの焼成物Ｂ１について、絶乾密度、吸水率を、ＪＩＳ Ａ １１１０に準拠して測定した。これに併せて、−４００mmHgの減圧下で、１５分間吸水させた減圧吸水率を測定した。また、土木学会基準の高強度フライアッシュ人工骨材の圧壊荷重試験方法に準拠して、５〜１０mmの焼成物Ｂ１、１０〜１５mmの焼成物Ｂ１の圧壊荷重を測定した。結果を表１に示す。
(2-2) Evaluation of fired product B1:
About 5-15mm baked product B1, the absolute dry density and the water absorption were measured based on JISA1110. In conjunction with this, the reduced-pressure water absorption after 15 minutes of water absorption was measured under a reduced pressure of -400 mmHg. Further, the crushing load of the fired product B1 of 5 to 10 mm and the fired product B1 of 10 to 15 mm was measured in accordance with the crushing load test method of the high strength fly ash artificial aggregate of the Japan Society of Civil Engineers. The results are shown in Table 1.
表１の結果より、焼成物Ｂ１は、高強度で且つ低吸水率の焼成物であることが分かる。従って、焼成物Ｂ１は、コンクリート用の骨材、路盤材、埋め戻し材等として好適に使用することができる。
以上の結果より、焼成物Ｂの製造において、焼成物Ａの製造の際に発生したＥＰダストを原料として使用できることが確認された。
From the results in Table 1, it can be seen that the fired product B1 is a fired product having high strength and low water absorption. Therefore, the fired product B1 can be suitably used as an aggregate for concrete, a roadbed material, a backfill material, and the like.
From the above results, it was confirmed that in the production of the fired product B, EP dust generated during the production of the fired product A can be used as a raw material.
（２−３）焼成物Ｂ２、Ｂ３の製造：
原料として、建設発生土、石炭灰、石灰石及び実施例３の焼成物Ｃ２の製造の際に発生したＥＰダスト（以下、副産物Ｄと称す）を使用し、表２に示す焼成物Ｂ２、Ｂ３を製造した。焼成物Ｂ２、Ｂ３の製造は、表３に示した原料を、表２示す水硬率になるよう配合し、該原料を、１３０m3のエアーブレンディングサイロに投入し、エアーによる曝流混合を各々６時間行った。
(2-3) Production of fired products B2 and B3:
As the raw material, construction generated soil, coal ash, limestone and EP dust (hereinafter referred to as by-product D) generated during the production of the calcined product C2 of Example 3 were used, and calcined products B2 and B3 shown in Table 2 were used. Manufactured. The baked products B2 and B3 are produced by blending the raw materials shown in Table 3 so as to have the hydraulic modulus shown in Table 2, and putting the raw materials into a 130 m 3 air blending silo, and mixing by aeration with air. It went for 6 hours.
続いて、得られた原料を、内径１．５ｍ、長さ２０ｍのロータリーキルンに、１ton／hで投入し、滞留時間が６０分となる条件で、緻密質な焼成物が得られるよう、燃料であるＡ重油の焚き量を調整しながら、約１３００℃で焼成した。
使用した建設発生土、石炭灰、石灰石及び副産物Ｄの化学組成（質量％）は、表３に示すとおりである。
なお、本実施例において、焼成物Ｂ２、Ｂ３の原料中の廃棄物等（石灰石以外の原料）の割合は、４０〜５５質量％である。また、排ガス中のＳＯx（ＪＩＳ Ｋ ０１０３）と砒素（ＪＩＳ Ｋ ００８３）の濃度を測定したところ、ＳＯx濃度は１ppm以下であり、砒素は検出されなかった。
Subsequently, the obtained raw material is introduced into a rotary kiln having an inner diameter of 1.5 m and a length of 20 m at 1 ton / h, and fuel is used so that a dense fired product is obtained under the condition that the residence time is 60 minutes. It baked at about 1300 degreeC, adjusting the amount of burning of a certain A heavy oil.
Table 3 shows the chemical composition (mass%) of the construction-generated soil, coal ash, limestone, and byproduct D used.
In addition, in a present Example, the ratio of the waste etc. (raw materials other than limestone) in the raw material of baked products B2 and B3 is 40-55 mass%. Further, when the concentrations of SO x (JIS K 0103) and arsenic (JIS K 0083) in the exhaust gas were measured, the SO x concentration was 1 ppm or less, and no arsenic was detected.
（２−４）焼成物Ｂ２、Ｂ３の評価：
得られた焼成物Ｂ２、Ｂ３を、目開き５、１０、１５mmで篩い分けし、５〜１５mmの焼成物について、砒素及びSO3含有量を測定し、表２に併記した。
なお、砒素含有量は、ＪＣＡＳ Ｉ−５１により前処理後、水素化物発生原子吸光法により測定し、SO3含有量は、蛍光Ｘ線分析により測定した。
また、５〜１５mmの焼成物について、絶乾密度、吸水率を、ＪＩＳ Ａ １１１０に準拠して測定した。これに併せて、−４００mmHgの減圧下で、１５分間吸水させた減圧吸水率を測定した。また、土木学会基準の高強度フライアッシュ人工骨材の圧壊荷重試験方法に準拠して、５〜１０mmの焼成物、１０〜１５mmの焼成物の圧壊荷重を測定した。さらに、環境省告示４６号法に準拠した焼成物からの砒素の溶出量を測定した。その結果を表４に示す。
(2-4) Evaluation of fired products B2 and B3:
The obtained baked products B2 and B3 were sieved with an opening of 5, 10 and 15 mm, and the arsenic and SO 3 contents of the baked product having a size of 5 to 15 mm were measured.
The arsenic content was measured by hydride generation atomic absorption after pretreatment with JCAS I-51, and the SO 3 content was measured by fluorescent X-ray analysis.
Moreover, the absolute dry density and the water absorption rate were measured based on JIS A1110 about the 5-15 mm baked product. In conjunction with this, the reduced-pressure water absorption after 15 minutes of water absorption was measured under a reduced pressure of -400 mmHg. Further, the crushing load of the fired product of 5 to 10 mm and the fired product of 10 to 15 mm was measured in accordance with the crushing load test method of the high strength fly ash artificial aggregate according to the Japan Society of Civil Engineers. Furthermore, the amount of arsenic eluted from the fired product according to the Ministry of the Environment Notification No. 46 was measured. The results are shown in Table 4.
表４の結果より、焼成物Ｂ２、Ｂ３は、高強度で且つ低吸水率の焼成物であることが分かる。従って、焼成物Ｂ２、Ｂ３は、コンクリート用の骨材、路盤材、埋め戻し材等として好適に使用することができる。
また、焼成物Ｂは、砒素及び硫黄の固定能力に優れており、実施例３の焼成物Ｃ２の製造の際に発生したＥＰダストを原料として使用できることが確認された。
From the results of Table 4, it can be seen that the fired products B2 and B3 are fired products having high strength and low water absorption. Accordingly, the fired products B2 and B3 can be suitably used as aggregates for concrete, roadbed materials, backfill materials, and the like.
In addition, it was confirmed that the fired product B was excellent in the ability to fix arsenic and sulfur, and EP dust generated during the production of the fired product C2 of Example 3 could be used as a raw material.
実施例３
（３−１）焼成物Ｃ１の製造：
原料として、建設発生土、石炭灰及び普通ポルトランドセメント製造の際に発生したＥＰダスト（以下、副産物Ｅと称す）を使用し、水硬率が０．２の焼成物Ｃ１を製造した。焼成物Ｃ１の製造は、各原料を、水硬率が０．２になるよう配合し、該原料を、１３０m3のエアーブレンディングサイロに投入し、エアーによる曝流混合を６時間行った。
Example 3
(3-1) Production of fired product C1:
As the raw material, construction generated soil, coal ash, and EP dust generated during the production of ordinary Portland cement (hereinafter referred to as by-product E) were used to produce a fired product C1 having a hydraulic modulus of 0.2. In the production of the fired product C1, the respective raw materials were blended so that the hydraulic modulus was 0.2, the raw materials were put into a 130 m 3 air blending silo, and aeration mixing with air was performed for 6 hours.
続いて、得られた原料を、内径１．５ｍ、長さ２０ｍのロータリーキルンに、１ton／hで投入し、滞留時間が６０分となる条件で、緻密質な焼成物が得られるよう、燃料であるＡ重油の焚き量を調整しながら、約１２５０℃で焼成した。
なお、本実施例において、焼成物Ｃ１の原料中の廃棄物等の割合は、１００質量％である。
Subsequently, the obtained raw material is introduced into a rotary kiln having an inner diameter of 1.5 m and a length of 20 m at 1 ton / h, and fuel is used so that a dense fired product is obtained under the condition that the residence time is 60 minutes. It baked at about 1250 degreeC, adjusting the amount of burning of a certain A heavy oil.
In the present example, the ratio of wastes and the like in the raw material of the fired product C1 is 100% by mass.
（３−２）焼成物Ｃ１の評価：
５〜１５mmの焼成物Ｃ１について、絶乾密度、吸水率を、ＪＩＳ Ａ １１１０に準拠して測定した。これに併せて、−４００mmHgの減圧下で、１５分間吸水させた減圧吸水率を測定した。また、土木学会基準の高強度フライアッシュ人工骨材の圧壊荷重試験方法に準拠して、５〜１０mmの焼成物Ｃ１、１０〜１５mmの焼成物Ｃ１の圧壊荷重を測定した。結果を表５に示す。
(3-2) Evaluation of fired product C1:
With respect to the fired product C1 having a thickness of 5 to 15 mm, the absolute dry density and water absorption were measured in accordance with JIS A 1110. In conjunction with this, the reduced-pressure water absorption after 15 minutes of water absorption was measured under a reduced pressure of -400 mmHg. Further, the crushing load of the fired product C1 of 5 to 10 mm and the fired product C1 of 10 to 15 mm was measured in accordance with the method for testing the crushing load of the high strength fly ash artificial aggregate according to the Japan Society of Civil Engineers. The results are shown in Table 5.
表５の結果より、焼成物Ｃ１は、高強度で且つ低吸水率の焼成物であることが分かる。従って、焼成物Ｃ１は、コンクリート用の骨材、路盤材、埋め戻し材等として好適に使用することができる。
以上の結果より、焼成物Ｃの製造において、焼成物Ａの製造の際に発生したＥＰダストを原料として使用できることが確認された。
From the results of Table 5, it can be seen that the fired product C1 is a fired product with high strength and low water absorption. Therefore, the fired product C1 can be suitably used as an aggregate for concrete, a roadbed material, a backfill material, and the like.
From the above results, it was confirmed that in the production of the fired product C, EP dust generated during the production of the fired product A can be used as a raw material.
（３−３）焼成物Ｃ２、Ｃ３の製造：
原料として、建設発生土、石炭灰及び実施例２の焼成物Ｂ２の製造の際に発生した微粉（以下、副産物Ｆと称す）を使用し、表６に示す焼成物Ｃ２、Ｃ３を製造した。焼成物Ｃ２、Ｃ３の製造は、表７に示した原料を、表６に示す水硬率になるよう配合し、該原料を、１３０m3のエアーブレンディングサイロに投入し、エアーによる曝流混合を各々６時間行った。
(3-3) Production of fired products C2 and C3:
As the raw material, construction generated soil, coal ash and fine powder (hereinafter referred to as by-product F) generated during the production of the fired product B2 of Example 2 were used to produce the fired products C2 and C3 shown in Table 6. For the production of the fired products C2 and C3, the raw materials shown in Table 7 were blended so as to have the hydraulic modulus shown in Table 6, and the raw materials were put into a 130 m 3 air blending silo and subjected to aeration mixing with air. Each was performed for 6 hours.
続いて、得られた原料を、内径１．５ｍ、長さ２０ｍのロータリーキルンに、１ton／hで投入し、滞留時間が６０分となる条件で、緻密質な焼成物が得られるよう、燃料であるＡ重油の焚き量を調整しながら、約１２２０℃で焼成した。
使用した建設発生土、石炭灰及び副産物Ｆの化学組成（質量％）は、表７に示すとおりである。
なお、本実施例において、焼成物Ｃ２，Ｃ３の原料中の廃棄物等の割合は１００質量％である。また、排ガス中の鉛と全クロム（ＪＩＳ Ｋ ００８３）の濃度を測定したところ、いずれも検出されなかった。
Subsequently, the obtained raw material is introduced into a rotary kiln having an inner diameter of 1.5 m and a length of 20 m at 1 ton / h, and fuel is used so that a dense fired product is obtained under the condition that the residence time is 60 minutes. It baked at about 1220 degreeC, adjusting the amount of burning of a certain A heavy oil.
Table 7 shows the chemical composition (mass%) of the construction generated soil, coal ash, and by-product F used.
In the present embodiment, the ratio of wastes and the like in the raw materials of the fired products C2 and C3 is 100% by mass. Further, when the concentrations of lead and total chromium (JIS K 0083) in the exhaust gas were measured, none were detected.
（３-４）焼成物Ｃ２、Ｃ３の評価：
得られた焼成物を、目開き５、１０、１５mmの篩い分けし、５〜１５mmの焼成物について鉛およびクロム含有量を測定し、表６に併記した。
なお、鉛およびクロム含有量は、ＪＣＡＳ Ｉ−５１により前処理後、ＩＣＰ発光分析法により測定した。
また、５〜１５mmの焼成物について、絶乾密度、吸水率を、ＪＩＳ Ａ １１１０に準拠して測定した。これに併せて、−４００mmHgの減圧下で、１５分間吸水させた減圧吸水率を測定した。また、土木学会基準の高強度フライアッシュ人工骨材の圧壊荷重試験方法に準拠して、５〜１０mmの焼成物、１０〜１５mmの焼成物の圧壊荷重を測定した。さらに、環境省告示１９号に準拠した焼成物中の鉛とCr6+の含有量、および環境省告示４６号法に準拠した焼成物からのそれらの溶出量をそれぞれ測定した。
その結果を表８に示す。
(3-4) Evaluation of fired products C2 and C3:
The obtained fired product was sieved with openings of 5, 10, and 15 mm, and the lead and chromium contents of the fired product of 5 to 15 mm were measured.
The lead and chromium contents were measured by ICP emission analysis after pretreatment with JCAS I-51.
Moreover, the absolute dry density and the water absorption rate were measured based on JIS A1110 about the 5-15 mm baked product. In conjunction with this, the reduced-pressure water absorption after 15 minutes of water absorption was measured under a reduced pressure of -400 mmHg. Further, the crushing load of the fired product of 5 to 10 mm and the fired product of 10 to 15 mm was measured in accordance with the crushing load test method of the high strength fly ash artificial aggregate according to the Japan Society of Civil Engineers. Furthermore, the content of lead and Cr 6+ in the fired product according to Ministry of the Environment Notification No. 19 and the amount of elution from the fired product according to the Ministry of the Environment Notification No. 46 method were measured.
The results are shown in Table 8.
表８の結果より、焼成物Ｃは、高強度で且つ低吸水率の焼成物であることが分かる。従って、焼成物Ｃは、コンクリート用の骨材、路盤材、埋め戻し材等として好適に使用することができる。
また、焼成物Ｃは、鉛及びCr6+の固定能力に優れており、実施例２の焼成物Ｂ２の製造の際に発生した微粉を原料として使用できることが確認された。
From the results in Table 8, it can be seen that the fired product C is a fired product having high strength and low water absorption. Therefore, the fired product C can be suitably used as an aggregate for concrete, a roadbed material, a backfill material, and the like.
In addition, it was confirmed that the fired product C was excellent in the ability to fix lead and Cr 6+ , and fine powder generated during the production of the fired product B2 of Example 2 could be used as a raw material.
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| JP7437210B2 (en) | 2020-03-26 | 2024-02-22 | Ｕｂｅ三菱セメント株式会社 | Cement-based solidifying material and method for producing cement-based solidifying material |
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| KR20140004152A (en) * | 2010-12-28 | 2014-01-10 | 다이헤이요 세멘토 가부시키가이샤 | Cement admixture, cement additive and method for producing mixed cement |
| KR101950525B1 (en) * | 2010-12-28 | 2019-02-20 | 다이헤이요 세멘토 가부시키가이샤 | Cement admixture, cement additive and method for producing mixed cement |
| JP7437210B2 (en) | 2020-03-26 | 2024-02-22 | Ｕｂｅ三菱セメント株式会社 | Cement-based solidifying material and method for producing cement-based solidifying material |
| JP7128557B1 (en) * | 2021-07-30 | 2022-08-31 | ▲寧▼波工程学院 | Controlled low-strength material using steelmaking slag desulfurization by-product and construction surplus soil and its manufacturing method |
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