JP6002495B2 - Earthwork materials - Google Patents
Earthwork materials Download PDFInfo
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- JP6002495B2 JP6002495B2 JP2012169050A JP2012169050A JP6002495B2 JP 6002495 B2 JP6002495 B2 JP 6002495B2 JP 2012169050 A JP2012169050 A JP 2012169050A JP 2012169050 A JP2012169050 A JP 2012169050A JP 6002495 B2 JP6002495 B2 JP 6002495B2
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- calcium aluminate
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- 239000000463 material Substances 0.000 title claims description 47
- 238000010828 elution Methods 0.000 claims description 54
- 239000002956 ash Substances 0.000 claims description 53
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 52
- 239000010802 sludge Substances 0.000 claims description 40
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 38
- 239000002689 soil Substances 0.000 claims description 33
- 239000010881 fly ash Substances 0.000 claims description 31
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 27
- 229910052785 arsenic Inorganic materials 0.000 claims description 27
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 27
- 229910052796 boron Inorganic materials 0.000 claims description 27
- 229910052731 fluorine Inorganic materials 0.000 claims description 27
- 239000011737 fluorine Substances 0.000 claims description 27
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 25
- 229910052711 selenium Inorganic materials 0.000 claims description 25
- 239000011669 selenium Substances 0.000 claims description 25
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 24
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 21
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 21
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 21
- 239000004571 lime Substances 0.000 claims description 21
- 230000002378 acidificating effect Effects 0.000 claims description 15
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical group [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 8
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 4
- 235000011009 potassium phosphates Nutrition 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 86
- 235000012255 calcium oxide Nutrition 0.000 description 46
- 239000000292 calcium oxide Substances 0.000 description 45
- 238000000034 method Methods 0.000 description 28
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 24
- 239000000126 substance Substances 0.000 description 19
- 229910001385 heavy metal Inorganic materials 0.000 description 17
- 230000007613 environmental effect Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000002265 prevention Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 230000003405 preventing effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 5
- 235000011116 calcium hydroxide Nutrition 0.000 description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical class [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000003916 acid precipitation Methods 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000003440 toxic substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- 238000004056 waste incineration Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- -1 aluminum sulfate Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
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- 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)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Description
本発明は、フライアッシュおよび／またはペーパースラッジ灰を使用し、埋め戻し材などに利用される土工材料に関し、フライアッシュあるいはペーパースラッジ灰に含まれる有害物質（ふっ素、ほう素および重金属類（砒素、セレン））の酸性環境下における溶出量を土壌環境基準以下に抑制した土工材料に関する。 The present invention relates to an earthwork material that uses fly ash and / or paper sludge ash and is used as a backfill material, etc., and relates to harmful substances (fluorine, boron, and heavy metals (arsenic, arsenic) contained in fly ash or paper sludge ash. The present invention relates to an earthwork material in which the amount of selenium)) dissolved in an acidic environment is suppressed to the soil environment standard or less.
フライアッシュは石炭火力発電所または石炭ボイラーなどで石炭の燃焼にともない発生する焼却灰で年間約１千万ｔ発生しており、一部はセメント原料あるいは土工材料として埋め戻し土、路盤材、コンクリ−ト製品用混和材などに利用されているものの、その多くは産業廃棄物として地中又は海面に埋立処分されている。同様に、ペーパースラッジ灰は製紙工場から排出されるペーパースラッジを焼却・減容化することで発生する焼却灰で年間数百万ｔ発生しているが、有効利用されている量はごく僅かであり、大半は廃棄物として処分されている。今後、廃棄物処分場の逼迫や環境負荷低減という社会情勢に対応するためには、フライアッシュやペーパースラッジ灰の有効利用を最大限進めていく必要がある。しかし、フライアッシュやペーパースラッジ灰には重金属類や有害物質の溶出という環境安全面の課題があり、具体的には、主にふっ素、ほう素、砒素、セレンの溶出量が土壌環境基準（環境庁告示第４６号）を超える恐れがあることが有効利用の妨げとなっている。表１に土壌環境基準（環境庁告示第４６号）に規定されているふっ素、ほう素、砒素、セレンの溶出量を示す。 Fly ash is about 10 million tons of incinerated ash generated during the combustion of coal at coal-fired power plants or coal boilers, and some of it is backfilled as cement raw materials or earthwork materials, roadbed materials, concrete -Although it is used for admixtures and other products, most of it is disposed of in the ground or on the sea as industrial waste. Similarly, paper sludge ash is incinerated ash generated by incineration and volume reduction of paper sludge discharged from paper mills, and it is generated in millions of tons per year. Yes, most are disposed of as waste. In the future, it will be necessary to maximize the effective use of fly ash and paper sludge ash in order to respond to the social situation of tighter waste disposal sites and reduced environmental impact. However, fly ash and paper sludge ash have environmental safety issues such as the elution of heavy metals and harmful substances. Specifically, the amount of elution of fluorine, boron, arsenic, and selenium is mainly based on soil environmental standards (environmental The possibility of exceeding the Office Notification No. 46) hinders effective use. Table 1 shows the elution amounts of fluorine, boron, arsenic, and selenium specified in the soil environmental standards (Environment Agency Notification No. 46).
従来、ふっ素の不溶化技術としては、消石灰などのカルシウム塩を使用して難溶性のふっ化カルシウムを生成させる方法、硫酸アルミニウムなどのアルミニウム塩を使用して水酸化アルミニウムが生成される過程でふっ素を吸着・不溶化する方法、硫酸マグネシウムなどのマグネシウム塩を使用して水酸化マグネシウムが生成される過程でふっ素を吸着・不溶化する方法などが知られている。ほう素の不溶化技術としては、硫酸アルミニウムなどのアルミニウム塩の使用、あるいは、硫酸アルミニウムと消石灰を併用することで、ほう素を吸着・不溶化する方法が知られている。砒素の不溶化技術としては、硫酸アルミニウムなどのアルミニウム塩を使用して水酸化アルミニウムが生成される過程で砒素を吸着・不溶化する方法、塩化第二鉄などの鉄塩を使用して水酸化鉄が生成される過程で砒素を吸着・不溶化する方法などが知られている。セレンの不溶化技術としては、鉄塩などを使用した吸着・不溶化方法が知られている。
しかし、これらの方法では、不溶化の効果が低く、フライアッシュやペーパースラッジ灰からのふっ素、ほう素、砒素及びセレンの溶出量を前記土壌環境基準以下に抑制することは困難であった。
Conventionally, fluorine insolubilization techniques include the use of calcium salts such as slaked lime to produce sparingly soluble calcium fluoride, and the process in which aluminum hydroxide is produced using aluminum salts such as aluminum sulfate. There are known methods for adsorption and insolubilization, methods for adsorption and insolubilization of fluorine in the process of producing magnesium hydroxide using a magnesium salt such as magnesium sulfate. As a boron insolubilization technique, a method of adsorbing and insolubilizing boron by using an aluminum salt such as aluminum sulfate or using aluminum sulfate and slaked lime together is known. Arsenic insolubilization technologies include a method of adsorbing and insolubilizing arsenic in the process of producing aluminum hydroxide using aluminum salts such as aluminum sulfate, and iron hydroxide using ferric chloride and other iron salts. A method of adsorbing and insolubilizing arsenic in the process of generation is known. As an insolubilization technique of selenium, an adsorption / insolubilization method using an iron salt or the like is known.
However, in these methods, the effect of insolubilization is low, and it has been difficult to suppress the elution amounts of fluorine, boron, arsenic and selenium from fly ash and paper sludge ash below the soil environmental standard.
このような観点から、フライアッシュやペーパースラッジ灰などの廃棄物における有害物質の溶出抑制方法がいくつか提案されている。例えば、砒素や６価クロムをキレート剤であるジチオカルバミン酸塩あるいはジチオカルバミン酸誘導体で捕捉・不溶化する技術（特許文献１、２）、汚染土壌や焼却灰にチオ硫酸化合物を添加するとともに焼却灰を加熱することで、焼却灰などに含まれる砒素やセレンなどの重金属類を不溶化する装置に関する技術（特許文献３）、焼却灰に水硬性結合材であるセメントまたは石灰を添加することで、焼却灰に含まれるふっ素やほう素の溶出を抑制する技術（特許文献４）、製鋼スラグなどの産業廃棄物にカルシウムアルミネートなどの粉末を添加することで、産業廃棄物からのふっ素の溶出を抑制する技術（特許文献５）、石炭や製紙スラッジなどを燃焼して発生するほう素含有燃焼灰に酸化カルシウム類及び/または水酸化カルシウム類、硫酸カルシウム類、アルミナセメント、水を加えて混合処理することにより、その燃焼灰からのほう素の溶出を抑制する技術（特許文献６）、カルシウムアルミネートとケイ酸カルシウムとを含有する不溶化剤を用いたフッ素及び／又はホウ素の不溶化方法であり、フッ素及び／又はホウ素を含む固形物と該不溶化剤と水を混合してから所要期間養生することでフッ素及び／又はホウ素を不溶化する技術（特許文献７）、汚染土壌や焼却灰に対し、硫酸アルミニウムとチオ硫酸ナトリウムおよび鉄粉を必須成分として含む汚染物質の溶出防止剤を添加・混合することで、砒素やセレンなどの重金属類およびほう素やふっ素の溶出を抑制する技術（特許文献８）、鉄粉、酸化カルシウム、酸化アルミニウムを必須成分として含む有害元素の溶出抑制剤を用いることで、フライアッシュからのふっ素、ほう素および砒素やセレンなどの重金属類の溶出を抑制する技術（特許文献９）が報告されている。 From this point of view, several methods for suppressing the elution of harmful substances in waste such as fly ash and paper sludge ash have been proposed. For example, technologies for capturing and insolubilizing arsenic and hexavalent chromium with chelating agents such as dithiocarbamate or dithiocarbamate derivatives (Patent Documents 1 and 2), adding thiosulfate compounds to contaminated soil and incineration ash, and heating incineration ash By adding a cement or lime, which is a hydraulic binder, to the incineration ash, a technology related to a device that insolubilizes heavy metals such as arsenic and selenium contained in the incineration ash, etc. (Patent Document 3) Technology that suppresses the elution of fluorine and boron contained (Patent Document 4), Technology that suppresses elution of fluorine from industrial waste by adding powder such as calcium aluminate to industrial waste such as steelmaking slag (Patent Document 5), calcium oxides and / or calcium hydroxides in boron-containing combustion ash generated by burning coal, paper sludge, etc. , Calcium sulfate, alumina cement, a technique for suppressing elution of boron from combustion ash by adding water (Patent Document 6), an insolubilizer containing calcium aluminate and calcium silicate Is a method for insolubilizing fluorine and / or boron by mixing the solid material containing fluorine and / or boron, the insolubilizing agent and water, and then curing for a required period of time. Patent Document 7) Adds and mixes anti-elution agents containing pollutants containing aluminum sulfate, sodium thiosulfate and iron powder as essential components to contaminated soil and incinerated ash so that heavy metals such as arsenic and selenium and boron Technology for suppressing elution of elemental and fluorine (Patent Document 8), dissolution of harmful elements including iron powder, calcium oxide, and aluminum oxide as essential components By using the inhibitor, fluorine from fly ash, boron and arsenic and heavy metals eluted suppressing technology, such as selenium (Patent Document 9) have been reported.
また、有害物質を含むフライアッシュやペーパースラッジ灰を土工材料として有効利用するためには、不溶化処理したフライアッシュやペーパースラッジ灰における重金属等の溶出防止効果が、環境条件によらず安定的に保たれる必要がある。
フライアッシュやペーパースラッジ灰とは異なるが、不溶化処理した汚染土壌において重金属等の有害物質が溶出する環境条件としては、ｐＨが最も重要な要因であることが既往の調査結果から明らかになっている。ｐＨ変化に対する重金属等の溶出挙動については、重金属等で汚染した土壌を不溶化処理したものについて、pH4.0 の酸性雨に年間降雨量2,000mm で100 年間曝された場合を考慮した評価試験方法が社団法人土壌環境センターより提案されており（GEPC技術標準TS-02-S1 重金属等不溶化処理土壌のｐＨ変化に対する安定性の相対的評価方法）、不溶化処理したフライアッシュやペーパースラッジ灰についても、このような酸性環境下での重金属等の溶出を防止する必要がある。
Also, in order to effectively use fly ash and paper sludge ash containing hazardous substances as earthwork materials, the elution prevention effect of heavy metals, etc. in insolubilized fly ash and paper sludge ash is stably maintained regardless of environmental conditions. Need to be drunk.
Although it is different from fly ash and paper sludge ash, it is clear from past survey results that pH is the most important factor for environmental conditions in which toxic substances such as heavy metals are eluted in insolubilized contaminated soil. . Regarding the dissolution behavior of heavy metals, etc. in response to changes in pH, there is an evaluation test method that considers the case where soil contaminated with heavy metals, etc. is insolubilized and exposed to acid rain at pH 4.0 at an annual rainfall of 2,000 mm for 100 years. It has been proposed by the Soil Environment Center (GEPC Technical Standard TS-02-S1 Relative evaluation method for the stability of insolubilized soils such as heavy metals), and insolubilized fly ash and paper sludge ash are also It is necessary to prevent elution of heavy metals in such an acidic environment.
このような観点から、酸性雨に曝された状況において焼却灰などの廃棄物からの有害物質の溶出を抑制する方法が提案されている。すなわち、ゴミ焼却灰を廃白土と固化材で固化して鉛やカドミウムの溶出を防ぐ技術（特許文献１０）、ゴミ焼却灰等の廃棄物に鉄塩または鉄塩と鉱酸を添加混合して鉛等の重金属の溶出を防止する技術（特許文献１１、１２）、焼却炉で発生するアルカリ飛灰からの鉛やカドミウムの溶出を炭酸ガスとリン酸塩を用いて防止する方法（特許文献１３）が報告されている。 From such a viewpoint, a method for suppressing the elution of harmful substances from waste such as incineration ash in a situation exposed to acid rain has been proposed. In other words, waste incineration ash is solidified with waste white clay and solidification material to prevent elution of lead and cadmium (Patent Document 10), iron salt or iron salt and mineral acid are added and mixed with waste incineration ash and other waste Technologies for preventing elution of heavy metals such as lead (Patent Documents 11 and 12), and methods for preventing elution of lead and cadmium from alkaline fly ash generated in an incinerator using carbon dioxide and phosphate (Patent Document 13) ) Has been reported.
しかしながら、これら従来の有害物質の溶出防止技術は、高価な成分を使用する、大がかりな装置を使用する、さらに一部の有害物質だけの溶出抑制ができる手段にすぎず前記４種の有害物質の溶出を抑制できるものではない等の問題があり、特に酸性環境下で溶出防止を図る技術については、不溶化に必要な薬剤量が多い、特別な処理設備が必要になるなどの課題があった。そのため、これらの技術では、有害物質を含むフライアッシュやペーパースラッジ灰を経済的かつ効率的に不溶化処理し、酸性環境下において溶出防止効果を保つことが困難であった。
従って、本発明の課題は、フライアッシュやペーパースラッジ灰を使用した土工材料において、下水汚泥焼却灰に含まれる有害物質であるふっ素、ほう素および重金属類（ひ素、セレン）の酸性環境下における溶出量を土壌環境基準以下に抑制できる経済的かつ効率的な土工材料の処方を提供することにある。
However, these conventional toxic substance elution prevention techniques are merely means that use expensive components, use large-scale devices, and can suppress elution of only some toxic substances. There is a problem that elution cannot be suppressed, and the technique for preventing elution particularly in an acidic environment has problems such as a large amount of chemicals required for insolubilization and the need for special treatment equipment. Therefore, with these techniques, it has been difficult to economically and efficiently insolubilize fly ash and paper sludge ash containing harmful substances and maintain the elution prevention effect in an acidic environment.
Therefore, the object of the present invention is to elute fluorine, boron and heavy metals (arsenic, selenium), which are harmful substances contained in sewage sludge incineration ash, in an earth environment using fly ash and paper sludge ash in an acidic environment. An object of the present invention is to provide an economical and efficient prescription for earthwork materials that can control the amount below the soil environmental standard.
そこで本発明者は、検討を重ねた結果、ふっ素、ほう素および重金属類（砒素、セレン）を含むペーパースラッジ灰を土工材料として使用するに際し、該ペーパースラッジ灰に溶出防止成分としてカルシウムアルミネート、硫酸アルミニウム、石灰及びアルカリ金属リン酸塩を組み合わせた配合とすることで、該土工材料を水と混合して得られる混合物からの有害物質の溶出量を酸性雨に長期間曝される条件を想定した酸性環境下でも土壌環境基準以下に低減できることを見出し、本発明を完成させるに至った。 Therefore, as a result of repeated studies, the present inventor, when using paper sludge ash containing fluorine, boron and heavy metals (arsenic, selenium) as an earthwork material, calcium aluminate as an elution preventing component in the paper sludge ash, By combining aluminum sulfate, lime and alkali metal phosphate, the amount of elution of harmful substances from the mixture obtained by mixing the earthwork material with water is assumed to be exposed to acid rain for a long time. The present inventors have found that it can be reduced below the soil environmental standard even under an acidic environment.
すなわち、本発明は、次の［１］〜［４］に係るものである。
[１]（Ａ）ふっ素、ほう素、砒素及びセレンから選ばれる１種以上の酸性環境下における溶出量（社団法人土壌環境センターの技術標準：ＧＥＰＣ ＴＳ−０２−Ｓ１で測定）が、土壌環境基準を超えるペーパースラッジ灰、（Ｂ）ＣａＯとＡｌ2Ｏ3が等モル比の結晶質カルシウムアルミネートと、ＣａＯとＡｌ2Ｏ3の含有モル比がＣａＯ／Ａｌ2Ｏ3＝１．６〜２．６の非晶質カルシウムアルミネートとを１００：１０〜１００：２００の質量比で含むカルシウムアルミネート、（Ｃ）硫酸アルミニウム、（Ｄ）石灰及び（Ｅ）アルカリ金属リン酸塩を含有し、
（Ｂ）カルシウムアルミネート１００質量部に対して、（Ｃ）硫酸アルミニウム３〜４０質量部、（Ｄ）石灰２〜２０質量部及び（Ｅ）アルカリ金属リン酸塩０．５〜４質量部であり、
（Ａ）ペーパースラッジ灰１００質量部に対し、（Ｂ）カルシウムアルミネート、（Ｃ）硫酸アルミニウム、（Ｄ）石灰、（Ｅ）アルカリ金属リン酸塩の合計が０．５〜１０質量部である土工材料。
[２]（Ａ）ふっ素、ほう素、砒素及びセレンから選ばれる１種以上の酸性環境下における溶出量（社団法人土壌環境センターの技術標準：ＧＥＰＣ ＴＳ−０２−Ｓ１で測定）が、土壌環境基準を超えるペーパースラッジ灰およびフライアッシュ、（Ｂ）ＣａＯとＡｌ 2 Ｏ 3 が等モル比の結晶質カルシウムアルミネートと、ＣａＯとＡｌ 2 Ｏ 3 の含有モル比がＣａＯ／Ａｌ 2 Ｏ 3 ＝１．６〜２．６の非晶質カルシウムアルミネートとを１００：１０〜１００：２００の質量比で含むカルシウムアルミネート、（Ｃ）硫酸アルミニウム、（Ｄ）石灰及び（Ｅ）アルカリ金属リン酸塩を含有し、
（Ｂ）カルシウムアルミネート１００質量部に対して、（Ｃ）硫酸アルミニウム３〜４０質量部、（Ｄ）石灰２〜２０質量部及び（Ｅ）アルカリ金属リン酸塩０．５〜４質量部であり、
（Ａ）ペーパースラッジ灰およびフライアッシュ１００質量部に対し、（Ｂ）カルシウムアルミネート、（Ｃ）硫酸アルミニウム、（Ｄ）石灰、（Ｅ）アルカリ金属リン酸塩の合計が０．５〜１０質量部である土工材料。
[３]（Ｅ）アルカリ金属リン酸塩が、リン酸カリウムである[１]又は[２]に記載の土工材料。
[４]ふっ素、ほう素、砒素及びセレンの酸性環境下における溶出量（社団法人土壌環境センターの技術標準：ＧＥＰＣ ＴＳ−０２−Ｓ１で測定）が、土壌環境基準以下に抑制されたものである[１]〜[３]のいずれかに記載の土工材料。
That is, the present invention relates to the following [1] to [ 4 ].
[1] (A) The amount of elution in one or more acidic environments selected from fluorine, boron, arsenic and selenium (technical standard of soil environment center: measured by GEPC TS-02-S1) is the soil environment Paper sludge ash exceeding the standard, (B) crystalline calcium aluminate in which CaO and Al 2 O 3 are equimolar ratio, and the molar ratio of CaO and Al 2 O 3 is CaO / Al 2 O 3 = 1.6 to and amorphous calcium aluminate 2.6 100: 10 to 100: calcium aluminate containing 200 weight ratio, (C) aluminum sulfate, containing (D) lime and (E) an alkali metal phosphate ,
(B) With respect to 100 parts by mass of calcium aluminate, (C) 3 to 40 parts by mass of aluminum sulfate, (D) 2 to 20 parts by mass of lime, and (E) 0.5 to 4 parts by mass of alkali metal phosphate Yes,
(A) The total of (B) calcium aluminate, (C) aluminum sulfate, (D) lime, and (E) alkali metal phosphate is 0.5 to 10 parts by mass with respect to 100 parts by mass of paper sludge ash. Earthwork material.
[2] (A) The amount of elution in one or more acidic environments selected from fluorine, boron, arsenic and selenium (technical standard of soil environment center: measured by GEPC TS-02-S1) is the soil environment. Paper sludge ash and fly ash exceeding the standard, (B) crystalline calcium aluminate in which CaO and Al 2 O 3 are equimolar ratio, and the molar ratio of CaO and Al 2 O 3 is CaO / Al 2 O 3 = 1 Calcium aluminate comprising amorphous calcium aluminate of .6 to 2.6 in a mass ratio of 100: 10 to 100: 200, (C) aluminum sulfate, (D) lime and (E) alkali metal phosphate Containing
(B) With respect to 100 parts by mass of calcium aluminate, (C) 3 to 40 parts by mass of aluminum sulfate, (D) 2 to 20 parts by mass of lime, and (E) 0.5 to 4 parts by mass of alkali metal phosphate Yes,
(A) The total amount of (B) calcium aluminate, (C) aluminum sulfate, (D) lime, and (E) alkali metal phosphate is 0.5 to 10 mass based on 100 parts by mass of paper sludge ash and fly ash. Earthwork material that is part.
[3] The earthwork material according to [1] or [2], wherein the (E) alkali metal phosphate is potassium phosphate.
[4] The amount of elution of fluorine, boron, arsenic and selenium in an acidic environment (technical standard of Soil Environment Center: measured by GEPC TS-02-S1) is suppressed below the soil environment standard. The earthwork material according to any one of [1] to [3].
本発明のペーパースラッジ灰を使用した土工材料は、経済的な処方でペーパースラッジ灰に含まれる有害物質であるふっ素、ほう素および重金属類（ひ素、セレン）の酸性環境下での溶出量を土壌環境基準以下に抑制できるため、該土工材料が酸性雨に長期間曝されても環境安全性を保つことができる。よって、本発明はフライアッシュやペーパースラッジ灰の有効利用の促進に極めて有用な技術である。 The earthwork material using the paper sludge ash of the present invention is an economical prescription for the amount of elution in the acidic environment of fluorine, boron and heavy metals (arsenic, selenium), which are harmful substances contained in the paper sludge ash. Since the earthwork material can be suppressed below the environmental standard, the environmental safety can be maintained even if the earthwork material is exposed to acid rain for a long time. Therefore, the present invention is a very useful technique for promoting effective utilization of fly ash and paper sludge ash.
フライアッシュは、石炭火力発電所または石炭ボイラーなどで石炭の燃焼にともない発生する焼却灰である。また、ペーパースラッジ灰は、製紙工場から排出されるペーパースラッジを焼却・減容化する際に発生する焼却灰である。本発明の土工材料に用いる（Ａ）フライアッシュまたはペーパースラッジ灰は、有害成分としてふっ素、ほう素、砒素及びセレンから選ばれる１種以上の溶出量が土壌環境基準を超えるものである。フライアッシュまたはペーパースラッジ灰は、最大粒径が１．２ｍｍ以下のものが好ましい。 Fly ash is incinerated ash generated by the combustion of coal in a coal-fired power plant or a coal boiler. Paper sludge ash is incinerated ash generated when paper sludge discharged from a paper mill is incinerated and volume-reduced. (A) Fly ash or paper sludge ash used in the earthwork material of the present invention has one or more elution amounts selected from fluorine, boron, arsenic and selenium as harmful components exceeding the soil environment standard. The fly ash or paper sludge ash preferably has a maximum particle size of 1.2 mm or less.
本発明の土工材料に用いる（Ｂ）カルシウムアルミネートは、基本的にはＣａＯ原料とＡｌ2Ｏ3原料を熱処理することにより得られる物質である。カルシウムアルミネートは化学成分としてＣａＯとＡｌ2Ｏ3からなる結晶質やガラス化が進んだ構造の水和活性物質であれば良く、ＣａＯとＡｌ2Ｏ3に加えて他の化学成分が加わった化合物、固溶体、ガラス質物質又はこれらの混合物等でもよい。前者（結晶質）としては例えば１２ＣａＯ・７Ａｌ2Ｏ3、ＣａＯ・Ａｌ2Ｏ3、３ＣａＯ・Ａｌ2Ｏ3、ＣａＯ・２Ａｌ2Ｏ3、ＣａＯ・６Ａｌ2Ｏ3等が挙げられ、後者（ガラス質）としては例えば、４ＣａＯ・３Ａｌ2Ｏ3・ＳＯ3、１１ＣａＯ・７Ａｌ2Ｏ3・ＣａＦ2、Ｎａ2Ｏ・８ＣａＯ・３Ａｌ2Ｏ3等が挙げられる。 The (B) calcium aluminate used in the earthwork material of the present invention is basically a substance obtained by heat-treating a CaO raw material and an Al 2 O 3 raw material. Calcium aluminate may be a hydrated active substance with a crystallized structure composed of CaO and Al 2 O 3 and a vitrified structure as a chemical component, and other chemical components are added in addition to CaO and Al 2 O 3 . It may be a compound, a solid solution, a glassy substance, or a mixture thereof. The former (crystalline) The example 12CaO · 7Al 2 O 3, CaO · Al 2 O 3, 3CaO · Al 2 O 3, CaO · 2Al 2 O 3, CaO · 6Al 2 O 3 and the like, the latter (Glass the quality) for example, 4CaO · 3Al 2 O 3 · SO 3, 11CaO · 7Al 2 O 3 · CaF 2, Na 2 O · 8CaO · 3Al 2 O 3 and the like.
本発明で用いる（Ｂ）カルシウムアルミネートとしては、結晶質カルシウムアルミネートと非晶質カルシウムアルミネートとを含むものが好ましく、ＣａＯとＡｌ2Ｏ3が等モル比の結晶質カルシウムアルミネートと、ＣａＯとＡｌ2Ｏ3の含有モル比がＣａＯ／Ａｌ2Ｏ3＝１．６〜２．６の非晶質カルシウムアルミネートとを含むものがより好ましい。 As the calcium aluminate (B) used in the present invention, those containing crystalline calcium aluminate and amorphous calcium aluminate are preferable, and crystalline calcium aluminate with an equimolar ratio of CaO and Al 2 O 3 ; those containing a molar ratio of CaO and Al 2 O 3 comprises an amorphous calcium aluminate CaO / Al 2 O 3 = 1.6~2.6 is more preferable.
ＣａＯとＡｌ2Ｏ3が等モル比の結晶質カルシウムアルミネートは、前記のようなＣａＯ源とＡｌ2Ｏ3源をそれぞれＣａＯ換算及びＡｌ2Ｏ3換算して等モル比となるよう混合したものを、例えば１６００℃で加熱し、これを徐冷すれば得られる。また、徐冷は加熱装置内での自然放冷が一般的に採用できるが、加熱装置の構造上急激な温度低下が起こる場合は、概ね１０℃／分以下の降温速度になるよう加熱調整するのが好ましい。ＣａＯ源は特に限定されないが、例えば石灰石粉、消石灰や生石灰粉を好適に挙げることができ、Ａｌ2Ｏ3源は例えばボーキサイト粉、水酸化アルミニウム、炭酸アルミニウム、アルミ残灰、アルミナ粉末等を好適に挙げることができる。該結晶質カルシウムアルミネートのブレーン比表面積は、３０００〜１００００ｃｍ2／ｇが好ましく、これと共に使用する非結晶質カルシウムアルミネートのブレーン比表面積と概ね同じものとするのが好ましい。 The crystalline calcium aluminate having an equimolar ratio of CaO and Al 2 O 3 was mixed so that the CaO source and the Al 2 O 3 source were equimolar ratios in terms of CaO and Al 2 O 3 , respectively. A thing is obtained by heating at 1600 degreeC, for example, and cooling this slowly. In addition, natural cooling in the heating device can be generally used for the slow cooling, but if a sudden temperature drop occurs due to the structure of the heating device, the heating is adjusted so that the temperature lowering rate is approximately 10 ° C./min or less. Is preferred. Although the CaO source is not particularly limited, for example, limestone powder, slaked lime and quick lime powder can be preferably mentioned, and as the Al 2 O 3 source, bauxite powder, aluminum hydroxide, aluminum carbonate, aluminum residual ash, alumina powder, etc. are suitable, for example. Can be listed. The crystalline calcium aluminate preferably has a Blaine specific surface area of 3000 to 10000 cm 2 / g, and is preferably substantially the same as the Blaine specific surface area of the amorphous calcium aluminate used therewith.
ＣａＯとＡｌ2Ｏ3の含有モル比がＣａＯ／Ａｌ2Ｏ3＝１．６〜２．６の非晶質カルシウムアルミネートは、ＣａＯ源とＡｌ2Ｏ3源をそれぞれＣａＯ換算及びＡｌ2Ｏ3換算して当該モル比の範囲に混合したものを、例えば１４００〜１９００℃で加熱溶融し、これを急冷することによって得られる。急冷は、例えば溶融物の該加熱温度からの炉外取り出し、水中急冷、冷却ガスの吹き付け等の公知の急冷手法で行うことができる。ＣａＯとＡｌ2Ｏ3の含有モル比（ＣａＯ／Ａｌ2Ｏ3）が１．６未満では反応性が低下し、溶出防止効果が十分得られない場合がある。またモル比（ＣａＯ／Ａｌ2Ｏ3）が２．６を超えると、ガラス化には極めて高い融点と当該温度からの急冷操作が必要になり、製造が困難となるため実用的でない。また前記非晶質カルシウムアルミネートは、粉砕・分級・篩い分け等を適宜行うことによって粒度を調整し、ブレーン比表面積で３０００〜１００００ｃｍ2／ｇにしたものを用いるのが好ましい。なお、ＣａＯ源及びＡｌ2Ｏ3源は、前記結晶質カルシウムアルミネートの場合と同じものが使用できる。 Amorphous calcium aluminate molar ratio CaO / Al 2 O 3 = from 1.6 to 2.6 of CaO and Al 2 O 3 is, CaO source and Al 2 O 3 source, respectively as CaO and Al 2 O What is converted into 3 and mixed in the range of the molar ratio is obtained by, for example, heating and melting at 1400 to 1900 ° C. and rapidly cooling it. The rapid cooling can be performed by a known rapid cooling method such as taking out the melt from the heating temperature from the furnace, quenching in water, or blowing a cooling gas. When the molar ratio of CaO to Al 2 O 3 (CaO / Al 2 O 3 ) is less than 1.6, the reactivity is lowered and the elution preventing effect may not be sufficiently obtained. On the other hand, if the molar ratio (CaO / Al 2 O 3 ) exceeds 2.6, vitrification requires an extremely high melting point and a rapid cooling operation from the temperature, which makes the production difficult, which is not practical. The amorphous calcium aluminate is preferably adjusted to a particle size by appropriately performing pulverization, classification, sieving, etc., and a Blaine specific surface area of 3000 to 10000 cm 2 / g. In addition, the same thing as the case of the crystalline calcium aluminate can be used for the CaO source and the Al 2 O 3 source.
本発明で用いる（Ｂ）カルシウムアルミネートは、前記のＣａＯとＡｌ2Ｏ3が等モル比の結晶質カルシウムアルミネートと、前記のＣａＯとＡｌ2Ｏ3の含有モル比がＣａＯ／Ａｌ2Ｏ3＝１．６〜２．６の非晶質カルシウムアルミネートを、１００：１０〜１００：２００の質量比で含むものが好ましく、１００：１５〜１００：１２０の質量比で含むものがより好ましい。この質量比のカルシウムアルミネート混合物を用いることで、有害物質を含むフライアッシュやペーパースラッジ灰と組み合せた土工材料とした場合に溶出防止効果を特に良好に発揮することができる。 (B) used in the present invention the calcium aluminate has a crystalline calcium aluminate of the of CaO and Al 2 O 3 equal molar ratio, the molar ratio of said CaO and Al 2 O 3 is CaO / Al 2 O It is preferable that the amorphous calcium aluminate of 3 = 1.6 to 2.6 is included at a mass ratio of 100: 10 to 100: 200, and more preferable that the amorphous calcium aluminate is included at a mass ratio of 100: 15 to 100: 120. . By using the calcium aluminate mixture having this mass ratio, the elution prevention effect can be exhibited particularly well when the earthwork material is combined with fly ash or paper sludge ash containing harmful substances.
本発明に用いる（Ｃ）硫酸アルミニウムは、化学成分としてＡｌ2（ＳＯ4）3・ｎＨ2Ｏで表される水和物、あるいはＡｌ2（ＳＯ4）3で表される無水塩の何れでも良い。好ましくは、有害物質の溶出抑制効果に優れていることからｎが１４〜１８の水和物が良い。 The aluminum sulfate (C) used in the present invention is either a hydrate represented by Al 2 (SO 4 ) 3 .nH 2 O as a chemical component or an anhydrous salt represented by Al 2 (SO 4 ) 3. good. Preferably, a hydrate having n of 14 to 18 is preferable because it is excellent in the elution suppression effect of harmful substances.
本発明に用いる（Ｄ）石灰は、化学成分としてＣａＯで表される酸化カルシウムを主成分とするもの、あるいは化学成分としてＣａ（ＯＨ）2で表される水酸化カルシウムを主成分とするものが使用でき、これら両方を含むものであっても良い。好ましくは、有害物質の溶出抑制効果に優れていることから酸化カルシウムの含有量が多い石灰が好ましい。石灰の粉末度はブレーン比表面積として２０００ｃｍ2／ｇ以上のものが好ましい。 The (D) lime used in the present invention is mainly composed of calcium oxide represented by CaO as a chemical component, or composed mainly of calcium hydroxide represented by Ca (OH) 2 as a chemical component. It can be used and may include both. Preferably, lime having a high calcium oxide content is preferable because it is excellent in the elution suppressing effect of harmful substances. The fineness of lime is preferably 2000 cm 2 / g or more as the Blaine specific surface area.
本発明に用いる（Ｅ）アルカリ金属リン酸塩としては、リン酸ナトリウムやリン酸カリウムなどの易溶性の塩が挙げられる。本発明では、アルカリ金属リン酸塩を配合することにより、良好な溶出抑制効果が得られる。アルカリ金属リン酸塩としては下記式（１）〜（３）で表されるリン酸カリウムが好ましく、溶出抑制効果に優れていることから下記式（２）で表されるリン酸二水素カリウムがより好ましい。 Examples of the (E) alkali metal phosphate used in the present invention include readily soluble salts such as sodium phosphate and potassium phosphate. In this invention, a favorable elution inhibitory effect is acquired by mix | blending an alkali metal phosphate. As the alkali metal phosphate, potassium phosphate represented by the following formulas (1) to (3) is preferable, and potassium dihydrogen phosphate represented by the following formula (2) is preferable because of its excellent elution suppression effect. More preferred.
Ｋ2ＨＰＯ4 （１）
ＫＨ2ＰＯ4 （２）
Ｋ3ＰＯ4 （３）
K 2 HPO 4 (1)
KH 2 PO 4 (2)
K 3 PO 4 (3)
本発明において、溶出防止成分である（Ｂ）カルシウムアルミネート（Ｃ）硫酸アルミニウム、（Ｄ）石灰および（Ｅ）アルカリ金属リン酸塩の配合割合は、（Ｂ）カルシウムアルミネート１００質量部に対して（Ｃ）硫酸アルミニウム３〜４０質量部、（Ｄ）石灰２〜２０質量部及び（Ｅ）アルカリ金属リン酸塩０．５〜４質量部となるように配合すると、良好な溶出防止効果が得られるため好ましい。 In the present invention, the blending ratio of (B) calcium aluminate (C) aluminum sulfate, (D) lime and (E) alkali metal phosphate which is an elution preventing component is based on 100 parts by mass of (B) calcium aluminate. (C) 3 to 40 parts by weight of aluminum sulfate, (D) 2 to 20 parts by weight of lime and (E) 0.5 to 4 parts by weight of alkali metal phosphate, Since it is obtained, it is preferable.
本発明の土工材料において、（Ａ）フライアッシュおよび／またはペーパースラッジ灰と溶出防止成分である（Ｂ）カルシウムアルミネート、（Ｃ）硫酸アルミニウム、（Ｄ）石灰、（Ｅ）アルカリ金属リン酸塩の配合割合は、（Ａ）フライアッシュおよび／またはペーパースラッジ灰１００質量部に対し、（Ｂ）カルシウムアルミネート、（Ｃ）硫酸アルミニウム、（Ｄ）石灰、（Ｅ）アルカリ金属リン酸塩の合計が０.５〜１０質量部となるように配合するのが好ましく、経済性の面から０.５〜５質量部とするのがより好ましい。 In the earthwork material of the present invention, (A) fly ash and / or paper sludge ash and elution preventing component (B) calcium aluminate, (C) aluminum sulfate, (D) lime, (E) alkali metal phosphate The blending ratio of (A) fly ash and / or paper sludge ash is 100 parts by mass of (B) calcium aluminate, (C) aluminum sulfate, (D) lime, and (E) alkali metal phosphate. It is preferable to mix | blend so that it may become 0.5-10 mass parts, and it is more preferable to set it as 0.5-5 mass parts from the surface of economical efficiency.
本発明の土工材料の用途は特に限定されず、盛土材、埋め戻し材、裏込材、土壌改良材、道路資材、コンクリートなどのセメント製品用混和材などに有効活用できる。また、本発明の土工材料の製造方法についても特に限定はされず、一般的な製造方法を用いることができる。例えば、本発明の土工材料を埋め戻し材として使用する場合は、現場でパン型ミキサーや強制二軸ミキサーなどの一般的なミキサーを用いて本発明の土工材料をスラリー状または塊状の混合物に加工して埋め戻し作業を行うことができる。 The use of the earthwork material of the present invention is not particularly limited, and can be effectively used as an embedding material for cement products such as embankment material, backfill material, backing material, soil improvement material, road material, and concrete. Moreover, it does not specifically limit about the manufacturing method of the earthwork material of this invention, A general manufacturing method can be used. For example, when the earthwork material of the present invention is used as a backfill material, the earthwork material of the present invention is processed into a slurry or block mixture using a general mixer such as a bread mixer or a forced biaxial mixer on site. Can be backfilled.
次に実施例を挙げて本発明をさらに詳細に説明する。 EXAMPLES Next, an Example is given and this invention is demonstrated still in detail.
（Ａ）フライアッシュ、ペーパースラッジ灰
最大粒径が１．２ｍｍ以下のフライアッシュとペーパースラッジ灰を使用した。このフライアッシュとペーパースラッジ灰について、社団法人土壌環境センターの技術標準（ＧＥＰＣ ＴＳ−０２−Ｓ１：重金属等不溶化処理土壌のｐＨ変化に対する安定性の相対的評価方法）に準じた方法で測定した酸性環境下でのふっ素、ほう素、砒素及びセレンの溶出量を表２に示す。
(A) Fly ash and paper sludge ash Fly ash and paper sludge ash having a maximum particle size of 1.2 mm or less were used. About this fly ash and paper sludge ash, the acidity measured by a method according to the technical standard of the Japan Soil Environment Center (GEPC TS-02-S1: Relative evaluation method for the stability of insolubilized soil such as heavy metals against pH change) Table 2 shows the elution amounts of fluorine, boron, arsenic and selenium in the environment.
（Ｂ）カルシウムアルミネート
ＣａＯ源に石灰石（ＣａＯ含有量；５６質量％）、Ａｌ2Ｏ3源にバン土頁岩（Ａｌ2Ｏ3含有量；８８質量％）のそれぞれ粗砕粒（粒径約１ｍｍ以下）を用い、以下のＡ１〜Ａ６で表すカルシウムアルミネートの粉末を作製した。その作製方法は、ＣａＯ源とＡｌ2Ｏ3源を所定のモル比に配合したものを、電気炉で１８００℃（±５０℃）に加熱し、６０分間保持した後、加熱を停止して炉内で自然放冷して得た（Ｂ１〜Ｂ３）。同様に１８００℃（±５０℃）に加熱し、６０分間保持した後、温度１８００℃の電気炉から加熱物を常温下に取り出し、取り出し後は直ちに加熱物表面に流量約１００ｃｃ／秒で窒素ガスを吹き付けて急冷して得た（Ｂ４〜Ｂ６）。得られた冷却物はボールミルで粉砕し、ブレーン比表面積が５０００±５００ｃｍ2／ｇとなるよう粉砕時間を変えて粉末度を調整した。
Ｂ１；ＣａＯ／Ａｌ2Ｏ3＝モル比１．０の結晶質カルシウムアルミネート
Ｂ２；ＣａＯ／Ａｌ2Ｏ3＝モル比１．７の結晶質カルシウムアルミネート
Ｂ３；ＣａＯ／Ａｌ2Ｏ3＝モル比０．５の結晶質カルシウムアルミネート
Ｂ４；ＣａＯ／Ａｌ2Ｏ3＝モル比１．７の非晶質カルシウムアルミネート
Ｂ５；ＣａＯ／Ａｌ2Ｏ3＝モル比２．３の非晶質カルシウムアルミネート
Ｂ６；ＣａＯ／Ａｌ2Ｏ3＝モル比２．９のガラス化率１０％のカルシウムアルミネート
(B) Calcium Aluminate Coarse crushed grains (particle size: about 1 mm) of limestone (CaO content: 56 mass%) as the CaO source and van earth shale (Al 2 O 3 content: 88 mass%) as the Al 2 O 3 source The following were used to prepare calcium aluminate powders represented by the following A1 to A6. The production method is as follows: a mixture of a CaO source and an Al 2 O 3 source in a predetermined molar ratio is heated to 1800 ° C. (± 50 ° C.) in an electric furnace, held for 60 minutes, and then the heating is stopped and the furnace It was obtained by natural cooling in the inside (B1 to B3). Similarly, after heating to 1800 ° C. (± 50 ° C.) and holding for 60 minutes, the heated product is taken out from the electric furnace at a temperature of 1800 ° C. at room temperature, and immediately after removal, nitrogen gas is applied to the surface of the heated product at a flow rate of about 100 cc / sec. Were obtained by spraying and quenching (B4 to B6). The obtained cooled product was pulverized by a ball mill, and the fineness was adjusted by changing the pulverization time so that the specific surface area of the brane was 5000 ± 500 cm 2 / g.
B1; CaO / Al 2 O 3 = crystalline calcium aluminate B2 in molar ratio B2; CaO / Al 2 O 3 = crystalline calcium aluminate B3 in molar ratio 1.7; CaO / Al 2 O 3 = mol A crystalline calcium aluminate B4 with a ratio of 0.5; CaO / Al 2 O 3 = amorphous calcium aluminate B5 with a molar ratio of 1.7; CaO / Al 2 O 3 = amorphous calcium with a molar ratio of 2.3 Aluminate B6; CaO / Al 2 O 3 = calcium aluminate with a molar ratio of 2.9 and a vitrification rate of 10%
（Ｃ）硫酸アルミニウム１４−１８水和物：関東化学社製 粉末試薬
（Ｄ）酸化カルシウム：関東化学社製 粉末試薬
（Ｅ）リン酸二水素カリウム：関東化学社製 粉末試薬
(C) Aluminum sulfate 14-18 hydrate: powder reagent manufactured by Kanto Chemical Co., Ltd. (D) Calcium oxide: powder reagent manufactured by Kanto Chemical Co., Ltd. (E) Potassium dihydrogen phosphate: powder reagent manufactured by Kanto Chemical Co., Ltd.
Ｂ１〜Ｂ６のカルシウムアルミネートと上記（Ｃ）（Ｄ）（Ｅ）から選定される材料を用い、表３に示す配合割合でヘンシェル型ミキサーを用いて３分間乾式混合し、本発明の土工材料および比較品の土工材料に使用する溶出防止成分を調合した。 Using the materials selected from B1 to B6 calcium aluminate and the above (C), (D), and (E), dry mixing for 3 minutes using a Henschel mixer at the blending ratio shown in Table 3, and the earthwork material of the present invention And the elution prevention component used for the earthwork material of a comparative product was prepared.
（土工材料の作成、溶出量の測定）
（Ａ）フライアッシュまたはペーパースラッジ灰に表３の溶出防止成分を表５に示す配合割合で配合し、本発明の土工材料および比較品の土工材料を作成した。次に、該土工材料１００質量部に対して水を６０質量部加え、モルタルミキサーで３分間混合して混合物を調整した。該混合物をビニール袋内に封入して２０℃の温度で養生し、養生期間１、７日経過後に、社団法人土壌環境センターの技術標準（ＧＥＰＣ ＴＳ−０２−Ｓ１：重金属等不溶化処理土壌のｐＨ変化に対する安定性の相対的評価方法）に準じた方法で、酸性環境下でのふっ素、ほう素、砒素及びセレンの溶出量を測定した。溶出量の測定結果を表５に示す。
(Creation of earthwork materials, measurement of elution amount)
(A) The elution prevention component of Table 3 was mix | blended with fly ash or paper sludge ash by the mixing | blending ratio shown in Table 5, and the earthwork material of this invention and the earthwork material of a comparative product were created. Next, 60 parts by mass of water was added to 100 parts by mass of the earthwork material, and mixed for 3 minutes with a mortar mixer to prepare a mixture. The mixture is enclosed in a plastic bag and cured at a temperature of 20 ° C. After a curing period of 1 or 7 days, the technical standard of the soil environment center (GEPC TS-02-S1: pH of insolubilized soil such as heavy metals) The amount of elution of fluorine, boron, arsenic and selenium in an acidic environment was measured by a method according to the method of relative evaluation of stability against change. Table 5 shows the measurement results of the elution amount.
〔ＧＥＰＣ ＴＳ−０２−Ｓ１に準じた溶出量測定方法〕
（１）所定期間養生後の試料を粗砕し、ふるい２ｍｍ通過分を採取混合する。
（２）容積１０００ｍＬのポリ容器に試料５０ｇを計りとり、溶媒として硫酸水溶液(０．７６９ｍｍｏｌ／Ｌ)５００ｇを加え、振とう機（振とう回数２００回／分）で６時間振とうする。
（３）ポリ容器を３０分静置した後、試料液の上澄みを孔径０．４５μｍのメンブレンフィルターでろ過して検液とする。
（４）採取した検液の成分を表４に示す方法で測定する。
[Method for measuring elution amount according to GEPC TS-02-S1]
(1) Roughly crush the sample after curing for a predetermined period, collect and mix the sieve 2 mm passage.
(2) Weigh 50 g of sample into a 1000 mL capacity plastic container, add 500 g of sulfuric acid aqueous solution (0.769 mmol / L) as a solvent, and shake for 6 hours with a shaker (number of shakes: 200 times / min).
(3) After allowing the polycontainer to stand for 30 minutes, the supernatant of the sample solution is filtered through a membrane filter having a pore diameter of 0.45 μm to obtain a test solution.
(4) The components of the collected test solution are measured by the method shown in Table 4.
表５の結果より、本発明の土工材料は、養生期間が７日の場合はいずれもふっ素、ほう素、砒素及びセレンの溶出量が土壌環境基準（環境庁告示第４６号）の規定値以下に抑制されており、酸性環境下での溶出防止効果が良好に発揮されていることが分かる。また、Ｎｏ．１〜４の溶出防止成分を使用した本発明１〜７、１３および１４では、養生期間が１日の場合でもふっ素、ほう素、砒素及びセレンの溶出量が土壌環境基準の規定値以下に抑制されており、特に溶出防止効果が良好であることが分かる。これに対し、比較品の土工材料では、Ｎｏ．１１の溶出防止剤を使用した比較品２とＮｏ．１２の溶出防止剤を使用した比較品３における養生期間が７日のときのふっ素とセレンの溶出量、およびＮｏ．１２の溶出防止剤を使用した比較品８と９の養生期間１日のセレンの溶出量と養生期間７日の砒素とセレンの溶出量を除いてはいずれも土壌環境基準を超過しており、有害物質を含むフライアッシュやペーパースラッジ灰を土工材料として使用するには溶出防止効果が不十分であった。 From the results in Table 5, the earthwork material of the present invention has an elution amount of fluorine, boron, arsenic and selenium below the specified value of the soil environment standard (Environment Agency Notification No. 46) when the curing period is 7 days. It can be seen that the elution prevention effect in an acidic environment is well exhibited. No. In the present invention 1 to 7, 13 and 14 using 1 to 4 elution prevention components, even when the curing period is 1 day, the elution amount of fluorine, boron, arsenic and selenium is suppressed below the specified value of the soil environment standard. It can be seen that the effect of preventing elution is particularly good. On the other hand, in comparative earthwork materials, No. Comparative product 2 using No. 11 dissolution inhibitor and No. 11 No. 12 elution amount of fluorine and selenium in the comparative product 3 using the elution inhibitor when the curing period is 7 days, Except for the leaching amount of selenium for the curing period 1 day and the leaching amount of arsenic and selenium for the curing period 7 days for the comparative products 8 and 9 using 12 dissolution inhibitors, both exceeded the soil environmental standards. In order to use fly ash and paper sludge ash containing hazardous substances as earthwork materials, the elution prevention effect was insufficient.
Claims (4)
（Ｂ）カルシウムアルミネート１００質量部に対して、（Ｃ）硫酸アルミニウム３〜４０質量部、（Ｄ）石灰２〜２０質量部及び（Ｅ）アルカリ金属リン酸塩０．５〜４質量部であり、
（Ａ）ペーパースラッジ灰１００質量部に対し、（Ｂ）カルシウムアルミネート、（Ｃ）硫酸アルミニウム、（Ｄ）石灰、（Ｅ）アルカリ金属リン酸塩の合計が０．５〜１０質量部である土工材料。 (A) The amount of elution in one or more acidic environments selected from fluorine, boron, arsenic and selenium (technical standard of the soil environment center: measured by GEPC TS-02-S1) exceeds the soil environment standard paper sludge ash, (B) CaO and Al 2 O 3 and the crystalline calcium aluminate equimolar ratio, CaO and Al 2 molar ratio of O 3 is CaO / Al 2 O 3 = from 1.6 to 2.6 A calcium aluminate containing a mass ratio of 100: 10 to 100: 200, (C) aluminum sulfate, (D) lime, and (E) an alkali metal phosphate ,
(B) With respect to 100 parts by mass of calcium aluminate, (C) 3 to 40 parts by mass of aluminum sulfate, (D) 2 to 20 parts by mass of lime, and (E) 0.5 to 4 parts by mass of alkali metal phosphate Yes,
(A) The total of (B) calcium aluminate, (C) aluminum sulfate, (D) lime, and (E) alkali metal phosphate is 0.5 to 10 parts by mass with respect to 100 parts by mass of paper sludge ash. Earthwork material.
（Ｂ）カルシウムアルミネート１００質量部に対して、（Ｃ）硫酸アルミニウム３〜４０質量部、（Ｄ）石灰２〜２０質量部及び（Ｅ）アルカリ金属リン酸塩０．５〜４質量部であり、(B) With respect to 100 parts by mass of calcium aluminate, (C) 3 to 40 parts by mass of aluminum sulfate, (D) 2 to 20 parts by mass of lime, and (E) 0.5 to 4 parts by mass of alkali metal phosphate Yes,
（Ａ）ペーパースラッジ灰およびフライアッシュ１００質量部に対し、（Ｂ）カルシウムアルミネート、（Ｃ）硫酸アルミニウム、（Ｄ）石灰、（Ｅ）アルカリ金属リン酸塩の合計が０．５〜１０質量部である土工材料。(A) The total amount of (B) calcium aluminate, (C) aluminum sulfate, (D) lime, and (E) alkali metal phosphate is 0.5 to 10 mass based on 100 parts by mass of paper sludge ash and fly ash. Earthwork material that is part.
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