JP7442971B2 - Slag molded bodies and environmental repair materials - Google Patents
Slag molded bodies and environmental repair materials Download PDFInfo
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- JP7442971B2 JP7442971B2 JP2019022797A JP2019022797A JP7442971B2 JP 7442971 B2 JP7442971 B2 JP 7442971B2 JP 2019022797 A JP2019022797 A JP 2019022797A JP 2019022797 A JP2019022797 A JP 2019022797A JP 7442971 B2 JP7442971 B2 JP 7442971B2
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- iron
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- 239000002893 slag Substances 0.000 title claims description 172
- 239000000463 material Substances 0.000 title claims description 67
- 230000007613 environmental effect Effects 0.000 title claims description 65
- 230000008439 repair process Effects 0.000 title claims description 50
- 238000009628 steelmaking Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000002689 soil Substances 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 22
- 230000002378 acidificating effect Effects 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 94
- 229910052742 iron Inorganic materials 0.000 description 44
- 238000012360 testing method Methods 0.000 description 34
- 238000010828 elution Methods 0.000 description 32
- 239000013049 sediment Substances 0.000 description 32
- 239000013535 sea water Substances 0.000 description 31
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 27
- 230000000694 effects Effects 0.000 description 27
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 26
- 241000195493 Cryptophyta Species 0.000 description 21
- -1 hydrogen sulfide ions Chemical class 0.000 description 19
- 230000009467 reduction Effects 0.000 description 18
- 241001474374 Blennius Species 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 230000007423 decrease Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 239000003864 humus Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229920001732 Lignosulfonate Polymers 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- 230000005791 algae growth Effects 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 230000012010 growth Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000005067 remediation Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- 239000012611 container material Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- GNVXPFBEZCSHQZ-UHFFFAOYSA-N iron(2+);sulfide Chemical compound [S-2].[Fe+2] GNVXPFBEZCSHQZ-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical class COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 235000019733 Fish meal Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 108010082455 Sebelipase alfa Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 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
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000035587 bioadhesion Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004467 fishmeal Substances 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229940041615 kanuma Drugs 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical compound P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002426 superphosphate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Landscapes
- Cultivation Of Seaweed (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Sludge (AREA)
- Artificial Fish Reefs (AREA)
Description
本発明は、水環境で使用されるスラグ成形体、および該スラグ成形体と、該スラグ成形体が装入される容器とを備える環境補修材に関する。 The present invention relates to a slag molded body used in an aqueous environment, and an environmental repair material comprising the slag molded body and a container into which the slag molded body is charged.
近年、沿岸部近傍の海域においては、岩場に海藻が繁殖しなくなり、石灰藻に覆われる磯焼け、水質の悪化、および底質の泥化などに伴う藻場の消失が問題となっており、水産資源の減少が深刻化している。 In recent years, in sea areas near the coast, seaweed has stopped growing on rocky areas, causing rocky shores to become covered in calcareous algae, deteriorating water quality, and disappearing seaweed beds due to muddy bottom sediment. The decline in marine resources is becoming more serious.
水産資源の減少の原因の１つである底質の泥化は、人工的な沿岸地形の変化に伴う海水流動の変化、生活排水からの有機物の流入および海砂の採取などにより、広い範囲に渡って生じている。泥化した底質は貧酸素状態となり易く、嫌気性の硫酸還元菌により毒性の強い硫化水素が生成され、生物生息に多大な支障をきたす。 Mudification of bottom sediment, which is one of the causes of decline in fisheries resources, is occurring over a wide area due to changes in seawater flow due to changes in artificial coastal topography, inflow of organic matter from domestic wastewater, and extraction of sea sand. It is occurring across the country. The muddy sediment tends to become deficient in oxygen, and highly toxic hydrogen sulfide is produced by anaerobic sulfate-reducing bacteria, which greatly impedes the habitat of living things.
このような底質による硫化水素の生成に関わる問題を解決可能な環境補修材の開発は水産資源を確保する上で重要な課題であり、硫化水素を抑制する手段として鉄が有効であることが知られている。 The development of environmental remediation materials that can solve problems related to the generation of hydrogen sulfide from the bottom sediment is an important issue in securing marine resources, and iron is an effective means of suppressing hydrogen sulfide. Are known.
より具体的には、以下の化学反応式に示すように、２価鉄（Ｆｅ２＋）と３価鉄（Ｆｅ３＋）とが、硫化水素イオンまたは硫化水素と反応し、硫化鉄（ＦｅＳ）と単体硫黄（Ｓ０）とを生じる。
ＨＳ－＋Ｆｅ２＋→ＦｅＳ＋Ｈ＋
ＨＳ－＋２Ｆｅ３＋→Ｓ０＋２Ｆｅ２＋＋Ｈ＋
Ｈ２Ｓ＋Ｆｅ２＋→ＦｅＳ＋２Ｈ＋
Ｈ２Ｓ＋２Ｆｅ３＋→Ｓ０＋２Ｆｅ２＋＋２Ｈ＋
水産資源の減少につながる藻場消失の原因として、森林の荒廃やダム建設などによって藻類の生育に必要な鉄分の流入量が減少していることも挙げられる。水産資源の維持、回復のためには、上記硫化水素の生成に関わる問題を解決するだけでなく、鉄分を供給することで、藻場を形成させ、多様な生物が生息可能な場を提供することが重要である。
More specifically, as shown in the chemical reaction formula below, divalent iron (Fe 2+ ) and trivalent iron (Fe 3+ ) react with hydrogen sulfide ions or hydrogen sulfide, and form iron sulfide (FeS). Elemental sulfur (S 0 ) is produced.
HS - +Fe 2+ →FeS+H +
HS - +2Fe 3+ →S 0 +2Fe 2+ +H +
H2S +Fe2 + →FeS+2H +
H 2 S+2Fe 3+ →S 0 +2Fe 2+ +2H +
Another reason for the disappearance of seaweed beds, which leads to a decrease in marine resources, is that the amount of iron necessary for algae growth is decreasing due to deforestation and dam construction. In order to maintain and restore marine resources, it is necessary not only to solve the problems related to the production of hydrogen sulfide mentioned above, but also to supply iron to form seaweed beds and provide a place where a variety of organisms can live. This is very important.
製鋼スラグは製鉄工程で大量に発生する副産物であり、路盤材や造成材など主に陸上での用途でリサイクルされている。製鋼スラグはリサイクル用途の拡大が求められており、海域での利用技術の開発が進められている。 Steelmaking slag is a byproduct generated in large quantities during the steelmaking process, and is recycled primarily for use on land, such as as roadbed material and construction material. There is a need to expand the use of steelmaking slag for recycling, and the development of technology for its use in marine areas is progressing.
製鋼スラグは鉄を含有しているため、上記硫化水素の生成に関わる問題を解決し、藻場形成の助長に資する材料として着目されている。しかし、製鋼スラグは水和固化する性質を持つため、砕石状態でそのまま底質に投入した場合、時間経過とともに環境水と接触した製鋼スラグが水和固化し、底質全体が固化することで生物の生息に適さない状態へ変化する可能性がある。 Since steelmaking slag contains iron, it is attracting attention as a material that solves the above-mentioned problems related to the generation of hydrogen sulfide and contributes to the formation of seaweed beds. However, steelmaking slag has the property of hydrating and solidifying, so if it is put into the bottom sediment in its crushed stone state, the steelmaking slag that comes into contact with environmental water will hydrate and harden over time, solidifying the entire bottom sediment and creating a biological environment. There is a possibility that conditions may change to become unsuitable for habitat.
また、環境水中においては、製鋼スラグ中に含まれる遊離石灰（ｆ－ＣａＯ）や水酸化カルシウムＣａ（ＯＨ）２などがカルシウムイオン（Ｃａ２＋）と共に水酸化物イオン（ＯＨ－）を溶出し、環境水のｐＨを過度に上昇させる可能性がある。特に、海水環境においては、製鋼スラグの施工により、海水のｐＨが上昇して海水が白濁してしまう可能性がある。 In addition, in environmental water, free lime (f-CaO) and calcium hydroxide Ca(OH) 2 contained in steelmaking slag elute hydroxide ions (OH − ) together with calcium ions (Ca 2+ ). There is a possibility of excessively raising the pH of environmental water. In particular, in a seawater environment, the application of steelmaking slag may increase the pH of the seawater and make the seawater cloudy.
製鋼スラグを用いて上記底質悪化の問題を解決する方法として、例えば、自然エージング、蒸気エージング、温水エージングで処理された製鋼スラグを用い、間隙率が１０％以上の改質材を投入する方法が知られている（例えば、特許文献１参照）。上記特許文献１の方法では、改質材に間隙を持たせることで、改質材投入時に巻き上がった泥で製鋼スラグが埋もれないように底質を改善する方法を提供している。 As a method to solve the problem of sediment deterioration using steelmaking slag, for example, a method of using steelmaking slag treated with natural aging, steam aging, or hot water aging and adding a modifying material with a porosity of 10% or more. is known (for example, see Patent Document 1). The method disclosed in Patent Document 1 provides a method of improving the bottom sediment so that the steelmaking slag is not buried in the mud that is stirred up when the reforming material is added by providing a gap in the reforming material.
また、ｐＨを上昇させることなく施工する方法として、炭酸化された製鋼スラグを腐植土と共にココナッツ繊維製の袋につめて海域へ投入する方法が知られている（例えば、特許文献２参照）。上記特許文献２の方法では、腐植土の鉄キレート作用により、生物に有効な鉄分をスラグから供給可能であるという特徴を有する。また、上記特許文献２の方法では、施工前に製鋼スラグを炭酸化するため、製鋼スラグによる海水のｐＨ上昇が抑制される。 Furthermore, as a method for construction without increasing the pH, a method is known in which carbonated steelmaking slag is packed together with humus soil in a coconut fiber bag and thrown into the sea area (see, for example, Patent Document 2). The method of Patent Document 2 is characterized in that iron, which is effective for living things, can be supplied from the slag due to the iron chelating action of humus soil. Moreover, in the method of Patent Document 2, since the steelmaking slag is carbonated before construction, an increase in the pH of seawater due to the steelmaking slag is suppressed.
ｐＨを上昇させることなく、取扱い良好な形状で海底へ施工させる有効な方法として、製鋼スラグを造粒した成形体を用いることが知られている（例えば、特許文献３参照）。上記特許文献３に記載のスラグ成形体は、酸性土壌の被覆部を有しており、この被覆部は、製鋼スラグによる海水のｐＨ上昇を抑制する機能を持つ。また、成形用バインダーとしてリグニンスルホン酸を含有しており、リグニンスルホン酸のキレート効果により水環境において鉄分を多量に供給可能な特徴を有する。 It is known that a molded body made of granulated steelmaking slag is used as an effective method for applying it to the seabed in a shape that is easy to handle without increasing the pH (see, for example, Patent Document 3). The slag molded body described in Patent Document 3 has a covering portion of acidic soil, and this covering portion has a function of suppressing an increase in the pH of seawater caused by steelmaking slag. It also contains ligninsulfonic acid as a molding binder, and has the characteristic of being able to supply a large amount of iron in an aqueous environment due to the chelating effect of ligninsulfonic acid.
しかしながら、上述のような特許文献１の方法では、元来水に溶出しにくい鉄を製鋼スラグから溶出させる工夫がされていないため、底質中で鉄の拡散が少なく、効率良く硫黄と反応しないため、十分な効果を得るために大量の製鋼スラグが必要となる。また、自然エージング処理などにより炭酸化がされているものの、製鋼スラグのアルカリ溶出を完全に抑制できないため、大量に投入すると水環境のｐＨを上昇させる危険性がある。 However, in the method of Patent Document 1 as described above, since iron, which is originally difficult to elute into water, is not eluted from the steelmaking slag, iron diffuses little in the sediment and does not react efficiently with sulfur. Therefore, a large amount of steelmaking slag is required to obtain sufficient effects. Furthermore, although carbonation is carried out through natural aging treatment, etc., alkali elution from steelmaking slag cannot be completely suppressed, so there is a risk of raising the pH of the water environment if a large amount is added.
また、上述の特許文献２の方法では、鉄の溶出促進に必要な腐植土を大量に混合するため、広大な水環境に投入する際、大量の腐食土を調達することが大きな課題となる。 Furthermore, in the method of Patent Document 2 mentioned above, since a large amount of humus soil necessary for promoting iron elution is mixed, procuring a large amount of humus soil becomes a major issue when it is introduced into a vast water environment.
さらに、上述の特許文献３の方法では、鉄を溶出可能な製鋼スラグ成形体およびその製造方法について詳しく記載されているが、底質改善の観点で十分効果を得るための条件が記載されていない。また、被覆部の酸性土壌が剥離するとスラグ成形体への藻類の着生を妨げる可能性がある。 Furthermore, the method of Patent Document 3 mentioned above describes in detail the steelmaking slag molded body that can elute iron and its manufacturing method, but does not describe the conditions for obtaining a sufficient effect from the viewpoint of bottom sediment improvement. . Furthermore, if the acidic soil in the coating section peels off, it may prevent algae from growing on the slag molded body.
本発明の一態様は、取扱性が良好で、水環境の底質を効果的に改善できるスラグ成形体および環境補修材を提供することを目的とする。 One aspect of the present invention is to provide a slag molded body and an environmental repair material that are easy to handle and can effectively improve the bottom sediment of a water environment.
上記の課題を解決するために、本発明の一態様に係るスラグ成形体は、水環境で使用されるスラグ成形体であって、リグニンスルホン酸およびその金属塩の少なくとも一方が製鋼スラグ重量に対して６質量％以上含有される構成である。 In order to solve the above problems, a slag molded body according to one aspect of the present invention is a slag molded body used in an aqueous environment, in which at least one of ligninsulfonic acid and its metal salt is The content is 6% by mass or more.
上記構成によれば、リグニンスルホン酸およびその金属塩は、スラグ成形体における成形性を向上させる。このため、取扱性が良好なスラグ成形体を提供できる。また、リグニンスルホン酸およびその金属塩は、さらに、鉄キレート作用を有し、水環境下においてスラグ成形体の鉄溶出量を増加させる作用を有する。また、上記構成によれば、リグニンスルホン酸およびその金属塩の少なくとも一方が製鋼スラグ重量に対して６質量％以上含有される。このため、水環境の底質を効果的に改善できる。 According to the above configuration, ligninsulfonic acid and its metal salt improve the moldability of the slag molded body. Therefore, it is possible to provide a slag molded body with good handling properties. Furthermore, ligninsulfonic acid and its metal salts have an iron chelating effect, and have the effect of increasing the amount of iron leached from the slag molded body in an aqueous environment. Further, according to the above configuration, at least one of ligninsulfonic acid and its metal salt is contained in an amount of 6% by mass or more based on the weight of the steelmaking slag. Therefore, the bottom sediment in the water environment can be effectively improved.
また、本発明の一態様に係るスラグ成形体は、粒径または全長が１０ｍｍ以上４０ｍｍ以下であることが好ましい。上記構成によれば、スラグ成形体の取扱いがより容易であるとともに水環境での崩壊期間を適宜に調整する観点からより効果的である。 Further, the slag molded body according to one aspect of the present invention preferably has a particle size or a total length of 10 mm or more and 40 mm or less. According to the above configuration, handling of the slag molded body is easier, and it is more effective from the viewpoint of appropriately adjusting the disintegration period in a water environment.
また、本発明の一態様に係るスラグ成形体は、上記スラグ成形体の表面に形成され、酸性土壌を主原料としリグニンスルホン酸およびその金属塩の少なくとも一方を含有する被覆部を備えていても良い。上記構成によれば、水環境における鉄成分の溶出量の増加とｐＨ上昇の抑制との観点からより効果的である。 Further, the slag molded body according to one aspect of the present invention may include a coating portion formed on the surface of the slag molded body and containing acidic soil as a main raw material and at least one of ligninsulfonic acid and a metal salt thereof. good. According to the above configuration, it is more effective from the viewpoint of increasing the elution amount of iron components and suppressing the pH rise in the water environment.
また、本発明の一態様に係る環境補修材は、上記スラグ成形体と、上記スラグ成形体が装入され、上記スラグ成形体と環境水とを接触させるための開口部を有する容器と、を備えていても良い。上記構成によれば、水環境の底質を効果的に改善できる環境補修材を提供することができる。 Furthermore, the environmental repair material according to one aspect of the present invention includes the slag molded body and a container into which the slag molded body is charged and has an opening for bringing the slag molded body into contact with environmental water. It's good to be prepared. According to the above configuration, it is possible to provide an environmental repair material that can effectively improve the sediment in the water environment.
本発明の一態様によれば、取扱性が良好で、水環境の底質を効果的に改善できるスラグ成形体および環境補修材を提供することができる。 According to one aspect of the present invention, it is possible to provide a slag molded body and an environmental repair material that are easy to handle and can effectively improve the bottom sediment of a water environment.
以下、本発明の実施の一形態の構成について詳細に説明する。 Hereinafter, the configuration of one embodiment of the present invention will be described in detail.
〔スラグ成形体〕
本発明の実施の一形態に係るスラグ成形体は、海洋沿岸部のような海水等の水環境において環境補修材等として使用される。そして、水環境へ投入されて、例えば海底に沈設して施工されることで、水環境における鉄溶出により底質改善効果を発揮し、さらに、藻類が定着可能かつ藻類の成長を促進する藻場造成材としての効果も奏する。
[Slag molded body]
The slag molded body according to one embodiment of the present invention is used as an environmental repair material in an aquatic environment such as seawater such as an ocean coastal area. When it is introduced into the aquatic environment, for example, by being deposited on the seabed, it exerts the effect of improving the bottom sediment by leaching iron in the aquatic environment, and it also creates a seaweed bed that allows algae to colonize and promotes algae growth. It is also effective as a construction material.
なお、本明細書において、水環境とは、スラグ成形体を投入することができる環境であり、海、湖沼および河川などが含まれる。図１の（ａ）および（ｂ）に、被覆部の無いスラグ成形体と、被覆部を有するスラグ成形体の一実施形態の構成図を示す。 Note that in this specification, the water environment is an environment into which the slag molded body can be introduced, and includes the sea, lakes, rivers, and the like. FIGS. 1A and 1B show configuration diagrams of an embodiment of a slag molded body without a covering portion and a slag molded body having a covering portion.
図１の（ａ）に示すスラグ成形体には、主原料としての製鋼スラグと、スラグ成形体を製造する際の成形性を向上させる混合物としてリグニンスルホン酸およびその金属塩の少なくとも一方とが混合されている。リグニンスルホン酸およびその金属塩は、分散性および粘結性に優れ、粘結剤として用いられ、スラグ成形体の強度の向上が期待される。 The slag molded body shown in FIG. 1(a) contains a mixture of steelmaking slag as the main raw material and at least one of ligninsulfonic acid and its metal salt as a mixture that improves the formability when manufacturing the slag molded body. has been done. Lignosulfonic acid and its metal salts have excellent dispersibility and caking properties, and are used as caking agents, and are expected to improve the strength of slag molded bodies.
ここで「主原料」とは、製鋼スラグが上記混合物中の成分の最も多い成分であることを意味し、例えば上記混合物における５０質量％以上の量を占める。また、上記主原料としての製鋼スラグは、製造時の成形性やスラグ成形体の強度を考慮すると、平均粒径が０．５ｍｍ以上２５ｍｍ以下であることが好ましい。 Here, the term "main raw material" means that steelmaking slag is the most abundant component in the mixture, for example, accounts for 50% by mass or more in the mixture. Further, the steelmaking slag as the main raw material preferably has an average particle size of 0.5 mm or more and 25 mm or less, considering the formability during production and the strength of the slag molded body.
なお、リグニンスルホン酸は、必要に応じてｐＨ調整可能であるが、スラグ成形体における海水のｐＨ上昇を抑制する観点や、ｐＨ上昇による白濁化を抑制する観点から、非アルカリ性であることが好ましい。特に、リグニンスルホン酸が酸性であると、海水のｐＨ上昇を防止または緩和する効果を奏しやすいためより好ましい。 Although the pH of lignin sulfonic acid can be adjusted as necessary, it is preferably non-alkaline from the viewpoint of suppressing the pH increase of seawater in the slag molded body and from the viewpoint of suppressing clouding caused by the pH increase. . In particular, it is more preferable that the ligninsulfonic acid is acidic because it tends to have the effect of preventing or mitigating an increase in the pH of seawater.
また、リグニンスルホン酸金属塩を用いる場合は、その種類は適宜選択できるが、ナトリウム（Ｎａ）、カリウム（Ｋ）、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、鉄（Ｆｅ）、亜鉛（Ｚｎ）、銅（Ｃｕ）、アルミニウム（Ａｌ）、マンガン（Ｍｎ）およびコバルト（Ｃｏ）などの金属のいずれか１つか、複数を混合して適用可能である。なお、取り扱い性やコストを考慮すると、Ｍｇ、ＣａまたはＮａが好ましい。 In addition, when using ligninsulfonic acid metal salt, the type can be selected as appropriate, but sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), iron (Fe), zinc (Zn), It is possible to apply any one of metals such as copper (Cu), aluminum (Al), manganese (Mn), and cobalt (Co), or a mixture of two or more metals. Note that, considering ease of handling and cost, Mg, Ca, or Na is preferable.
リグニンスルホン酸およびその金属塩の形態は適宜選択でき、粉末の状態や水溶液の状態で添加できる。また、リグニンスルホン酸およびその金属塩は、スルホン基（－ＳＯ３Ｈ）、カルボキシル基（－ＣＯＯＨ）、フェノール性またはアルコール性水酸基（－ＯＨ）を有しており、金属イオンと結合して親水性または疎水性の錯体化合物を形成するキレート性を有している。 The form of ligninsulfonic acid and its metal salt can be selected as appropriate, and it can be added in the form of powder or aqueous solution. In addition, ligninsulfonic acid and its metal salts have a sulfonic group (-SO 3 H), a carboxyl group (-COOH), and a phenolic or alcoholic hydroxyl group (-OH), and bond with metal ions to become hydrophilic. It has chelating properties that form hydrophobic or hydrophobic complex compounds.
そして、リグニンスルホン酸またはその金属塩を添加したスラグ成形体を海水へ投入すると、リグニンスルホン酸のキレート性により、Ｆｅイオンが水酸化物を形成して沈殿することなく、溶存状態で安定的に存在するため、Ｆｅの溶出量が増加する。 When the slag molded body containing ligninsulfonic acid or its metal salt is poured into seawater, Fe ions are stably dissolved in a dissolved state without forming hydroxides and precipitating due to the chelating properties of ligninsulfonic acid. Due to its presence, the elution amount of Fe increases.
製鋼スラグは、鉄鋼製品を製造する過程で副産物として発生し、通常は路盤材や地盤改良材などに有効利用されているものである。このような製鋼スラグとしては、例えば、転炉スラグ、電気炉スラグ、予備処理スラグ、脱炭スラグ、脱硫スラグ、脱リンスラグ、脱珪スラグ、電気炉酸化スラグ、電気炉還元スラグ、二次精錬スラグおよび造塊スラグなどがある。 Steelmaking slag is generated as a byproduct during the process of manufacturing steel products, and is usually effectively used as roadbed material and ground improvement material. Examples of such steelmaking slag include converter slag, electric furnace slag, pretreatment slag, decarburization slag, desulfurization slag, dephosphorization slag, desiliconization slag, electric furnace oxidation slag, electric furnace reduction slag, and secondary smelting slag. and agglomerated slag.
スラグ成型体は必要に応じ、水環境に有用な成分として、窒素（Ｎ）、リン（Ｐ）、カリウム（Ｋ）、マグネシウム（Ｍｇ）、珪素（Ｓｉ）および鉄（Ｆｅ）を含む混合物を加えても良い。混合物の例としては、硫酸アンモニウム、尿素、過リン酸石灰、熔成リン肥、硝酸カリウム、苦土石灰、硝酸マグネシウムおよび珪酸カリウムなどの施肥材料や、植物油かす、家畜の糞尿および魚粉などの農林水産副産物がある。 A mixture containing nitrogen (N), phosphorus (P), potassium (K), magnesium (Mg), silicon (Si) and iron (Fe) is added to the slag molded body as necessary as components useful in the water environment. It's okay. Examples of mixtures include fertilizing materials such as ammonium sulfate, urea, superphosphate, fertilized phosphorus fertilizer, potassium nitrate, magnesia, magnesium nitrate, and potassium silicate, and agricultural, forestry and fishery by-products such as vegetable oil cake, livestock manure, and fishmeal. There is.
（バインダー）
スラグ成形体は、成形用のバインダーであるリグニンスルホン酸およびその金属塩の少なくとも一方を製鋼スラグ重量に対して６質量％以上含有する。リグニンスルホン酸およびその金属塩は、スラグ成型体を製造する際に成形性を向上させ、水環境においては製鋼スラグによる環境水のｐＨ上昇を抑制するとともに製鋼スラグからの鉄溶出量を促進させる効果がある。
(binder)
The slag molded body contains at least one of ligninsulfonic acid and its metal salt, which are binders for molding, in an amount of 6% by mass or more based on the weight of the steelmaking slag. Lininsulfonic acid and its metal salts improve formability when manufacturing slag molded bodies, and in aquatic environments, suppress the increase in pH of environmental water caused by steelmaking slag, and have the effect of promoting the amount of iron leached from steelmaking slag. There is.
スラグ成型体に含有されるリグニンスルホン酸およびその金属塩は、含有量が６質量％未満であると水環境で底質を改善する鉄の溶出量が少なく、製鋼スラグによる環境水のｐＨ上昇を抑制する効果が小さい。水環境のｐＨが高いと、硫化鉄（ＦｅＳ）の生成が進まないため、底質を効果的に改善できない。 If the content of ligninsulfonic acid and its metal salts contained in the slag molded body is less than 6% by mass, the amount of iron elution that improves the sediment in the water environment will be small, and the increase in the pH of environmental water caused by steelmaking slag will be reduced. The suppressing effect is small. If the pH of the water environment is high, the production of iron sulfide (FeS) will not proceed, making it impossible to effectively improve the bottom sediment.
一方、スラグ成形体の成形時にリグニンスルホン酸およびその金属塩を過剰に添加すると、スラグ成形体の強度が低下し、成形性を低下させる場合がある。したがって、上記のリグニンスルホン酸およびその金属塩は６質量％以上が好ましく、より好ましくは、８質量％以上２０質量％以下である。 On the other hand, if ligninsulfonic acid and its metal salt are added excessively during molding of the slag molded body, the strength of the slag molded body may be reduced and the moldability may be reduced. Therefore, the content of the above ligninsulfonic acid and its metal salt is preferably 6% by mass or more, more preferably 8% by mass or more and 20% by mass or less.
スラグ成形体は、本実施の形態の効果が得られる範囲において、製鋼スラグおよび上記のリグニンスルホン酸およびその金属塩以外の他の成分をさらに含有していてもよい。このような他の成分は、一種でもそれ以上でもよく、その例には、底質を改善する金属鉄や鉄化合物に加え、藻類の成長を促進するためのＰまたはＮの化合物も含まれる。 The slag molded body may further contain components other than the steelmaking slag and the above-mentioned ligninsulfonic acid and its metal salt, within a range where the effects of the present embodiment can be obtained. Such other components may be one or more, and examples thereof include metallic iron and iron compounds to improve sediment quality, as well as P or N compounds to promote algae growth.
スラグ成形体が含有するリグニンスルホン酸およびその金属塩は、スラグ成形体の表層や中心部など、スラグ成型体においてどの範囲に含有されても良く、製鋼スラグの特性、スラグ成形体の鉄溶出量や生物着生など諸条件に応じて、スラグ成形体に十分な底質改善性または藻場造成材としての効果を付与することが可能な範囲において適宜に決めることができる。 The ligninsulfonic acid and its metal salts contained in the slag molded body may be contained in any range of the slag molded body, such as the surface layer or the center of the slag molded body, and the characteristics of the steelmaking slag and the iron elution amount of the slag molded body. It can be appropriately determined according to various conditions such as growth and bioadhesion within a range that can provide the slag molded body with sufficient bottom sediment improvement properties or an effect as a seaweed bed creation material.
（スラグ成形体の形状）
スラグ成形体の形状は、使用条件に応じて適宜に決めることが可能である。ただし、運搬や施工等における取扱性の観点や、施工後の水環境における底質の透水性の観点から粒体として成形されることが好ましい。また、スラグ成形体を粒体として成形する場合は、生産性の観点からブリケットマシンを用いることが好ましい。
(Shape of slag molded body)
The shape of the slag molded body can be determined as appropriate depending on the conditions of use. However, from the viewpoint of ease of handling during transportation, construction, etc., and from the viewpoint of water permeability of the bottom sediment in the water environment after construction, it is preferable to form it into granules. Further, when molding the slag molded body into granules, it is preferable to use a briquette machine from the viewpoint of productivity.
スラグ成形体の大きさは使用条件に応じて適宜に決めることが可能である。ただし、スラグ成形体の粒径または全長が４０ｍｍより大きいと、スラグ成型体の比表面積が低下するため、スラグ成形体の重量に対する鉄溶出量が低下する。 The size of the slag molded body can be appropriately determined depending on the conditions of use. However, if the particle size or overall length of the slag molded body is larger than 40 mm, the specific surface area of the slag molded body decreases, and the amount of iron eluted relative to the weight of the slag molded body decreases.
なお、粒径とは、スラグ成形体の形状が粒形状を為す場合の粒の直径のことである。また、全長とは、スラグ成形体の形状が、例えば、矩形形状等を為す場合の最大の径の長さのことである。 Note that the particle size refers to the diameter of particles when the slag molded body has a grain shape. Further, the total length refers to the length of the maximum diameter when the slag molded body has a rectangular shape, for example.
また、スラグ成形体の粒径または全長が１０ｍｍより小さいと発塵しやすくなる可能性が考えられるとともに、生産能率が低下してしまう可能性がある。したがって、スラグ成形体の粒径または全長は、１０ｍｍ以上４０ｍｍ以下が好ましい。これにより、スラグ成形体の取扱いがより容易であるとともに水環境での崩壊期間を適宜に調整する観点からより効果的である。 Furthermore, if the particle size or overall length of the slag molded body is smaller than 10 mm, there is a possibility that dust is likely to be generated, and the production efficiency may be reduced. Therefore, the particle size or overall length of the slag molded body is preferably 10 mm or more and 40 mm or less. This makes handling of the slag molded body easier and is more effective from the viewpoint of appropriately adjusting the disintegration period in a water environment.
（被覆部）
スラグ成形体は水環境下において、製鋼スラグを由来とするアルカリ成分の溶出により環境水のｐＨを上昇させる可能性がある。そこで、図１の（ｂ）に示すように、環境水のｐＨ上昇を抑制するため、スラグ成形体の表面が酸性土壌を含む被覆部で被覆されていてもよい。これにより、水環境における鉄成分の溶出量の増加とｐＨ上昇の抑制との観点からより効果的である。
(covering part)
In a water environment, the slag molded body may increase the pH of the environmental water due to the elution of alkaline components originating from steelmaking slag. Therefore, as shown in FIG. 1(b), the surface of the slag molded body may be covered with a covering portion containing acidic soil in order to suppress the increase in the pH of the environmental water. This is more effective in terms of increasing the amount of iron component eluted and suppressing the pH rise in the aqueous environment.
なお、酸性土壌は、例えば、赤土、鹿沼土、腐植土および泥炭などのように、海水に投入した際にｐＨの低下が生じ、かつ、海水の水質悪化や有害成分の溶出が生じないものであれば良い。なお、赤土とは、関東ローム層などを代表とする酸化鉄を多く含んだ赤褐色または黄褐色で粘土質の土壌である。 Acidic soil is one that causes a decrease in pH when added to seawater, such as red soil, Kanuma soil, humus soil, and peat, and does not cause deterioration of seawater quality or elution of harmful components. It's good to have. Note that red soil is reddish-brown or yellow-brown clay soil containing a lot of iron oxide, such as the Kanto loam layer.
酸性土壌の投入により海水中のｐＨの低下が起こるメカニズムの詳細は不明であるが、次のようなメカニズムが考えられる。酸性土壌中に一般的に含まれている粘度鉱物や腐植物質は、その表面に負電荷を有し、この負電荷を補うように表面には水素イオン（Ｈ＋）、ナトリウムイオン（Ｎａ＋）、マグネシウムイオン（Ｍｇ２＋）およびカルシウムイオン（Ｃａ２＋）などの陽イオンが存在し、電気的に中性を保っている。そして、このような酸性土壌を海水中に投入すると、粒子表面に吸着されている上記陽イオンと海水中のＣａ２＋のイオン交換が起こり、海水中のＨ＋が増加するため、ｐＨが低下する。 Although the details of the mechanism by which the pH of seawater decreases due to the addition of acidic soil are unknown, the following mechanism is considered. Clay minerals and humic substances commonly contained in acidic soil have a negative charge on their surface, and to compensate for this negative charge, hydrogen ions (H + ) and sodium ions (Na + ) are present on the surface. , cations such as magnesium ions (Mg 2+ ) and calcium ions (Ca 2+ ) exist, and maintain electrical neutrality. When such acidic soil is put into seawater, ion exchange occurs between the above cations adsorbed on the particle surface and Ca 2+ in the seawater, and H + in the seawater increases, resulting in a decrease in pH. .
ここで、海水中に酸性土壌を投入すると、ｐＨの低下だけでなく、植物プランクトンや藻類の栄養成分となるアンモニア態窒素、硝酸態窒素およびリン酸態リンなどの溶出が生じる。特に赤土や腐植土は、上述のイオン交換によるｐＨ低下作用も奏しやすいため、被覆部を形成する原料として好ましい。 Here, when acidic soil is introduced into seawater, not only does the pH decrease, but also ammonia nitrogen, nitrate nitrogen, and phosphate phosphorus, which are nutritional components for phytoplankton and algae, are eluted. In particular, red clay and humus soil are preferable as raw materials for forming the coating part because they tend to exhibit the pH lowering effect through ion exchange described above.
また、被覆部は、スラグ成形体の表面の一部を覆う状態でも良く、全部を覆う状態でも良い。スラグ成形体が上記被覆部を有する場合は、造粒性の観点から、スラグ成形体の形状が粒体であることが好ましい。 Further, the covering portion may be in a state of covering a part of the surface of the slag molded body, or may be in a state of covering the entire surface. When the slag molded body has the above-mentioned coating portion, the shape of the slag molded body is preferably granular from the viewpoint of granulation properties.
また、被覆部は、被覆部の強度上昇および鉄溶出量増加の観点から、酸性土壌以外の成分をさらに含有していてよい。例えば、被覆部は、被覆部の形成用バインダーとしてリグニンスルホン酸およびその金属塩の少なくとも一方をさらに含有していることが好ましい。 Further, the covering portion may further contain components other than acidic soil from the viewpoint of increasing the strength of the covering portion and increasing the amount of iron elution. For example, it is preferable that the coating further contains at least one of ligninsulfonic acid and a metal salt thereof as a binder for forming the coating.
リグニンスルホン酸およびその金属塩は、上述したように分散性および粘結性に優れ、粘結剤として用いられ、被覆部の強度の向上や、スラグ成形体と被覆部との密着性の向上が期待される。被覆部は、酸性土壌を主原料として含有していることが、前述のｐＨ上昇抑制効果の観点から好ましい。被覆部における酸性土壌の含有量は、被覆部中の成分で最も多い量であればよく、例えば５０質量％以上である。 As mentioned above, ligninsulfonic acid and its metal salts have excellent dispersibility and caking properties, and are used as binders to improve the strength of the coating and the adhesion between the slag molded body and the coating. Be expected. It is preferable that the covering portion contains acidic soil as a main raw material from the viewpoint of the above-mentioned pH increase suppressing effect. The content of acidic soil in the covering part may be the largest amount among the components in the covering part, and is, for example, 50% by mass or more.
〔容器への装入（環境補修材）〕
本実施形態に係るスラグ成形体は、スラグ成形体と、スラグ成形体が装入され、スラグ成形体と環境水とを接触させるための開口部を有する容器とを備える、環境補修材として使用されても良い。
[Charging into container (environmental repair material)]
The slag molded body according to the present embodiment is used as an environmental repair material, and includes a slag molded body and a container into which the slag molded body is charged and has an opening for bringing the slag molded body into contact with environmental water. It's okay.
スラグ成形体は元来生物が付着する性質を有するが、原料である製鋼スラグから僅かにアルカリ溶出する場合があり、水環境へ設置した初期において藻類など生物の着生を阻害する可能性がある。また、アルカリ溶出を低減した被覆部を有するスラグ成形体においても、設置後の初期において生物が着生した被覆部が剥離して生物着生の妨げとなる可能性がある。 Although slag compacts inherently have the property of attracting living organisms, a slight amount of alkali may be eluted from the steelmaking slag that is the raw material, which may inhibit the attachment of living organisms such as algae during the initial stage of installation in an aquatic environment. . Furthermore, even in the case of a slag molded body having a coating portion that reduces alkali elution, the coating portion on which organisms have adhered may peel off in the early stage after installation, which may hinder the attachment of organisms.
藻場造成効果を向上させるためには、生物を早期に着生させることが重要であり、図１の（ｃ）に示すように、スラグ成形体を、スラグ成形体と環境水とが接触するための開口部を有する容器に装入した環境補修材が藻場造成に好適である。これにより、水環境の底質を効果的に改善できる環境補修材を提供することができる。 In order to improve the effect of creating a seaweed bed, it is important to allow organisms to settle at an early stage. Environmental remediation materials placed in containers with openings for this purpose are suitable for creating seaweed beds. Thereby, it is possible to provide an environmental repair material that can effectively improve the bottom sediment of the water environment.
環境補修材は、スラグ成形体に加え、容器も生物が着生可能な場所となるため、環境補修材を水環境に設置した後、早期に藻類などの生物を安定的に着生させることができる。また、環境補修材は、スラグ成形体が環境水と接触する開口部を有するため、スラグ成形体から溶出した鉄が容器の開口部を介して容器外へ供給され、容器に着生した藻類の成長を促進させる。したがって、環境補修材は、スラグ成形体と容器の相乗効果によって藻類が早期に着生するとともに藻類の成長を促進させる効果を奏し、藻場造成材として優れた効果が得られる。 In addition to the slag molded body, the container of the environmental repair material also provides a place where organisms can settle, so it is possible to stably attach organisms such as algae quickly after installing the environmental repair material in the water environment. can. In addition, since the environmental repair material has an opening where the slag molded body comes into contact with environmental water, the iron eluted from the slag molded body is supplied to the outside of the container through the opening of the container, and the algae that has grown on the container are promote growth. Therefore, the environmental repair material has the effect of allowing algae to settle at an early stage and promoting the growth of algae due to the synergistic effect of the slag molded body and the container, and is excellent as a seaweed bed creation material.
環境補修材に用いる容器は、生物が早期に安定して着生可能な場所を提供することが可能であればどのような素材が使用されても良く、プラスチック、金属、天然石材、セラミックス、ガラス、木材、皮革、ゴムのどれを使用しても良い。また、その素材が繊維状の場合、天然繊維または化学繊維のどちらを使用しても良い。 Containers used for environmental repair materials may be made of any material as long as they can provide a place where organisms can settle in a stable manner at an early stage, including plastic, metal, natural stone, ceramics, and glass. , wood, leather, or rubber may be used. Furthermore, if the material is fibrous, either natural fiber or chemical fiber may be used.
環境補修材に用いる容器の素材は、生物が長期間安定して着生可能であること、および安価であることを考慮すると、天然繊維やプラスチックが好ましいが、容器素材から鉄を溶出させたい場合は鉄または鉄鋼材料を用いることが好ましい。 Natural fibers and plastics are preferable as materials for containers used for environmental repair materials, considering that they allow living things to settle stably over a long period of time and are inexpensive, but if iron is to be leached from the container material, Preferably, iron or steel material is used.
環境補修材に用いる容器の形体は、スラグ成形体の装入重量、容器素材、運搬性、長期保存性、容器としての強度、生物着生など、諸条件を考慮して適宜に決めることができる。容器の形態は、スラグ成形体が環境水と接触し、スラグ成形体から溶出した鉄が効率良く容器外へ供給される必要があるため、元来開口部を多数有する網袋または籠（かご）であることが好ましいが、容器の一部に開口部を有する箱やコンテナを使用しても良い。 The shape of the container used for the environmental repair material can be determined as appropriate by considering various conditions such as the charged weight of the slag molded body, container material, transportability, long-term storage stability, strength as a container, and biological growth. . The form of the container is originally a net bag or basket with many openings because the slag molded body comes into contact with environmental water and the iron eluted from the slag molded body needs to be efficiently supplied to the outside of the container. However, a box or container having an opening in a part of the container may also be used.
生物着生性と開口部からの鉄供給の両方を考慮すると、環境補修材に用いる容器として具体的には、天然繊維製の袋が好ましく、プラスチック製または鉄鋼製の網袋や籠であることが好ましい。図１の（ｃ）に示す環境補修材は、プラスチック製の籠で構成した容器にスラグ成形体を装入したものである。 Considering both biophytic properties and iron supply from the opening, natural fiber bags are preferable as containers for environmental remediation materials, and plastic or steel net bags or baskets are preferable. preferable. The environmental repair material shown in FIG. 1(c) is a container made of a plastic cage in which a slag molded body is charged.
〔実施例〕
以下、スラグ成形体の実施例および比較例について説明する。スラグ成形体の製造に用いる原料として製鋼スラグである転炉スラグを用いた。転炉スラグは製鋼工程で発生した転炉スラグを粉砕した後、篩い分けして５ｍｍ以下に調整したものである。
〔Example〕
Examples and comparative examples of slag molded bodies will be described below. Converter slag, which is steelmaking slag, was used as the raw material for producing the slag compact. Converter slag is obtained by crushing converter slag generated during the steelmaking process and then sieving it to a size of 5 mm or less.
また、スラグ成形体へ混合する物質として、リグニンスルホン酸塩〔日本製紙ケミカル製のサンエキスＭ－１００（サンエキスは登録商標）〕、でんぷん、ベントナイトおよび腐植土を用いた。スラグ成形体を酸性土壌により被覆する場合は、酸性土壌として市販品の赤土を１ｍｍ以下に篩い分けしたものを用いた。製鋼スラグ、でんぷん、ベントナイト、腐植土および赤土の化学成分を下記表１に示す。 In addition, as substances to be mixed into the slag molded body, lignin sulfonate [Sunextract M-100 manufactured by Nippon Paper Chemicals (Sunextract is a registered trademark)], starch, bentonite, and humus were used. When covering the slag molded body with acidic soil, commercially available red soil was sieved to a size of 1 mm or less and used as the acidic soil. The chemical components of steelmaking slag, starch, bentonite, humus, and red clay are shown in Table 1 below.
（実施例１）
転炉スラグおよびリグニンスルホン酸塩に適量の水を添加して混練機にて５分間混合した。リグニンスルホン酸塩の添加量は、転炉スラグの重量に対して６質量％である。混練機での混合後、ブリケットマシンで粒径３０ｍｍの造粒物に成形し、その造粒物を１０５℃で２時間乾燥した。こうして、実施例１のスラグ成形体を製造した。実施例１のスラグ成形体は、酸性土壌の被覆はない。溶出試験では、鉄溶出量が１８μｇ／Ｌとなった。硫化水素低減試験では、硫化物イオンは、未検出であり、ｐＨは、８．６となった。
(Example 1)
An appropriate amount of water was added to the converter slag and lignin sulfonate and mixed for 5 minutes in a kneader. The amount of lignin sulfonate added is 6% by mass based on the weight of converter slag. After mixing in a kneader, the mixture was molded into granules with a particle size of 30 mm using a briquette machine, and the granules were dried at 105° C. for 2 hours. In this way, the slag molded body of Example 1 was manufactured. The slag molded body of Example 1 was not covered with acidic soil. In the elution test, the iron elution amount was 18 μg/L. In the hydrogen sulfide reduction test, sulfide ions were not detected and the pH was 8.6.
（実施例２）
実施例１のスラグ成形体の表面を被覆部で被覆して実施例２のスラグ成形体を製造した。スラグ成形体とリグニンスルホン酸塩と赤土とを回転ドラム式の造粒機を用いて約１０分間混合し、混合の途中で適宜水を添加し、混合造粒することにより、赤土を主原料とする被覆部を作製した。こうして、実施例２のスラグ成形体を製造した。溶出試験では、鉄溶出量が４０μｇ／Ｌとなった。硫化水素低減試験では、硫化物イオンは、未検出であり、ｐＨは、８．１となった。
(Example 2)
The surface of the slag molded body of Example 1 was covered with a coating portion to produce the slag molded body of Example 2. The slag molded body, lignin sulfonate, and red clay are mixed for about 10 minutes using a rotating drum type granulator, water is added as needed during the mixing, and the mixture is granulated, making the red clay the main raw material. A covering part was prepared. In this way, the slag molded body of Example 2 was manufactured. In the elution test, the iron elution amount was 40 μg/L. In the hydrogen sulfide reduction test, sulfide ions were not detected and the pH was 8.1.
（実施例３）
リグニンスルホン酸塩の添加量（１２質量％）が異なること以外は実施例１と同様にして実施例３のスラグ成形体を製造した。溶出試験では、鉄溶出量が２２μｇ／Ｌとなった。硫化水素低減試験では、硫化物イオンは、未検出であり、ｐＨは、８．４となった。
(Example 3)
A slag molded body of Example 3 was produced in the same manner as Example 1 except that the amount of lignin sulfonate added (12% by mass) was different. In the elution test, the iron elution amount was 22 μg/L. In the hydrogen sulfide reduction test, sulfide ions were not detected and the pH was 8.4.
（比較例１）
リグニンスルホン酸塩を加えないこと以外は実施例１と同様にして比較例１のスラグ成形体を製造した。溶出試験では、鉄溶出量が５μｇ／Ｌ未満となった。硫化水素低減試験では、硫化物イオンは、３３ｍｇ／Ｌであり、ｐＨは、１０．５となった。
(Comparative example 1)
A slag molded body of Comparative Example 1 was produced in the same manner as in Example 1 except that lignin sulfonate was not added. In the elution test, the iron elution amount was less than 5 μg/L. In the hydrogen sulfide reduction test, sulfide ions were 33 mg/L and pH was 10.5.
（比較例２）
リグニンスルホン酸塩の添加量（３質量％）が異なること以外は実施例１と同様にして比較例２のスラグ成形体を製造した。溶出試験では、鉄溶出量が１６μｇ／Ｌとなった。硫化水素低減試験では、硫化物イオンは、２０ｍｇ／Ｌであり、ｐＨは、９．４となった。
(Comparative example 2)
A slag molded body of Comparative Example 2 was produced in the same manner as in Example 1 except that the amount of lignin sulfonate added (3% by mass) was different. In the elution test, the iron elution amount was 16 μg/L. In the hydrogen sulfide reduction test, sulfide ions were 20 mg/L and pH was 9.4.
（比較例３、４、５）
混合物の種類をリグニンスルホン酸塩から、でんぷん、ベントナイトまたは腐植土に変更し、混合物の含有量を１０質量％に変更した以外は実施例１と同様にして比較例３、４、５のスラグ成形体を製造した。溶出試験では、鉄溶出量は、それぞれ５μｇ／Ｌ未満、５μｇ／Ｌ未満、２５ｇ／Ｌとなった。硫化水素低減試験では、硫化物イオンは、それぞれ４８ｍｇ／Ｌ、３５ｍｇ／Ｌ、１４ｍｇ／Ｌであり、ｐＨは、それぞれ１０．２、１０．４、９．９となった。
(Comparative Examples 3, 4, 5)
Slag molding of Comparative Examples 3, 4, and 5 in the same manner as Example 1 except that the type of mixture was changed from lignin sulfonate to starch, bentonite, or humus, and the content of the mixture was changed to 10% by mass. manufactured a body. In the elution test, the iron elution amount was less than 5 μg/L, less than 5 μg/L, and 25 g/L, respectively. In the hydrogen sulfide reduction test, the sulfide ions were 48 mg/L, 35 mg/L, and 14 mg/L, respectively, and the pH was 10.2, 10.4, and 9.9, respectively.
（実施例４）
実施例１のスラグ成形体を上部が全面開口した矩形のポリプロピレン製矩形容器に５０ｋｇ装入した。容器の寸法は、幅４５ｃｍ、奥行き７５ｃｍ、高さ４０ｃｍである。こうして、実施例４の環境補修材を製造した。藻類の着生量は比較的多く、藻類の着生位置は、容器およびスラグ成形体となった。
(Example 4)
50 kg of the slag molded body of Example 1 was charged into a rectangular polypropylene container having an open top entirely. The dimensions of the container are 45 cm wide, 75 cm deep, and 40 cm high. In this way, the environmental repair material of Example 4 was manufactured. The amount of algae that settled on the container was relatively large, and the algae settled on the container and the slag molded body.
（実施例５）
実施例１のスラグ成形体を、開口部として１５．１５ｍｍの網目を有するポリエチレン製の網袋に２０ｋｇ装入し、ポリエチレン製のロープで装入口を閉じた。こうして、実施例５の環境補修材を製造した。藻類の着生量は比較的多く、藻類の着生位置は容器となった。
(Example 5)
20 kg of the slag molded product of Example 1 was charged into a polyethylene mesh bag having a 15.15 mm mesh opening, and the charging port was closed with a polyethylene rope. In this way, the environmental repair material of Example 5 was manufactured. The amount of algae growth was relatively large, and the algae growth position was the container.
（比較例６）
比較例２のスラグ成形体を用い、成形体の種類が異なること以外は実施例４と同様にして比較例６の環境補修材を製造した。藻類の着生量は極めて少なく、藻類の着生位置は、容器となった。
(Comparative example 6)
Using the slag molded body of Comparative Example 2, an environmental repair material of Comparative Example 6 was produced in the same manner as in Example 4 except that the type of molded body was different. The amount of algae that settled was extremely small, and the algae settled on the container.
（比較例７）
比較例２のスラグ成形体を用い、成形体の種類が異なること以外は実施例５と同様にして比較例７の環境補修材を製造した。藻類の着生量は極めて少なく、藻類の着生位置は、容器となった。
(Comparative example 7)
Using the slag molded body of Comparative Example 2, an environmental repair material of Comparative Example 7 was produced in the same manner as in Example 5 except that the type of molded body was different. The amount of algae that settled was extremely small, and the algae settled on the container.
〔評価試験〕
（１）溶出試験
実施例１～３および比較例１～５のスラグ成形体の鉄溶量評価のため、溶出試験を実施した。上記溶出試験は、スラグ成形体を海水に浸漬し、浸漬した状態で海水を攪拌させ、スラグ成形体から海水に溶出した鉄の濃度を評価する試験である。溶出試験では、３００ｇのスラグ成形体を２Ｌのガラスビーカー内で１．５Ｌの人工海水に浸し、浸漬直後および１時間経過毎に海水を攪拌棒にて１０回攪拌した。浸漬３時間経過後、海水を吸引ろ過した後、海水中の鉄濃度を酸分解－誘導結合プラズマ質量分析法により測定した。鉄の定量下限は５μｇ／Ｌである。
〔Evaluation test〕
(1) Elution test To evaluate the iron dissolution amount of the slag molded bodies of Examples 1 to 3 and Comparative Examples 1 to 5, an elution test was conducted. The above elution test is a test in which the slag molded body is immersed in seawater, the seawater is stirred in the immersed state, and the concentration of iron eluted from the slag molded body into the seawater is evaluated. In the elution test, a 300 g slag molded body was immersed in 1.5 L of artificial seawater in a 2 L glass beaker, and the seawater was stirred 10 times with a stirring rod immediately after immersion and every hour. After 3 hours of immersion, the seawater was suction filtered, and the iron concentration in the seawater was measured by acid decomposition-inductively coupled plasma mass spectrometry. The lower limit of determination for iron is 5 μg/L.
（２）硫化水素低減試験
実施例１～３および比較例１～５のスラグ成形体の硫化水素低減効果を評価するため、硫化水素低減試験を実施した。硫化水素低減試験は、底質模擬試料とともにスラグ成形体を海水に浸漬し、底質模擬試料表層の海水中硫化水素および硫化水素イオンを硫化物イオンとして測定する試験である。
(2) Hydrogen sulfide reduction test In order to evaluate the hydrogen sulfide reduction effect of the slag molded bodies of Examples 1 to 3 and Comparative Examples 1 to 5, a hydrogen sulfide reduction test was conducted. The hydrogen sulfide reduction test is a test in which a slag molded body is immersed in seawater together with a simulated bottom sediment sample, and hydrogen sulfide and hydrogen sulfide ions in the seawater at the surface layer of the simulated bottom sediment sample are measured as sulfide ions.
瀬戸内沿岸近傍の海底から採取した湿潤状態の砂泥に、砂泥中の硫化物濃度が約１ｍｇ／ｇ（乾燥状態）となるよう硫化ナトリウム試薬を加え、静かに攪拌混合して底質模擬試料とした。 A sodium sulfide reagent was added to wet sand and mud collected from the seabed near the Seto Inland Sea coast so that the sulfide concentration in the sand and mud was approximately 1 mg/g (dry state), and the mixture was gently stirred to create a simulated bottom sediment sample. And so.
攪拌混合時、試薬混合により試料中水分のｐＨが上昇しないよう少量の希塩酸を加えた。試薬を攪拌混合した直後の底質模擬試料６００ｇを湿潤状態のまま２Ｌのガラスビーカーに入れ、３００ｇのスラグ成形体をビーカー内の底質模擬試料の上に設置し、予め脱気したｐＨ８．３の人口海水１．５Ｌを静かにガラスビーカーへ注ぎ、時計皿とテープでビーカー内を密閉し、２１～２４℃の室温下で４８時間静置した。 During stirring and mixing, a small amount of dilute hydrochloric acid was added to prevent the pH of water in the sample from increasing due to reagent mixing. Immediately after stirring and mixing the reagents, 600 g of the sediment simulated sample was placed in a 2 L glass beaker in a wet state, and a 300 g slag molded body was placed on top of the sediment simulated sample in the beaker, and the pH was 8.3, which had been previously degassed. 1.5 L of artificial seawater was gently poured into a glass beaker, the inside of the beaker was sealed with a watch glass and tape, and the beaker was allowed to stand at room temperature of 21 to 24°C for 48 hours.
４８時間後、ガラス電極により海水のｐＨを測定した後、シリンジをビーカー内の海水に挿入し、シリンジ吸入口が底質模擬試料の表層に接触した状態でシリンジ内に海水を採取した。採取した海水を５種Ｃのろ紙でろ過した後、吸光光度法により硫化物イオン濃度を測定した。「５種Ｃ」とは「ろ紙」の目の細かさを示す基準であり、ＪＩＳ規格において、微細沈殿用（７２０秒以下）に分類されている。ここで、括弧内の数字は、水だけを１００ｍｌろ過する際にかかる秒数を示す。 After 48 hours, the pH of the seawater was measured using a glass electrode, and then the syringe was inserted into the seawater in the beaker, and the seawater was collected into the syringe with the syringe inlet in contact with the surface layer of the simulated sediment sample. After filtering the collected seawater through Type 5 C filter paper, the sulfide ion concentration was measured by spectrophotometry. "Type 5 C" is a standard indicating the fineness of "filter paper", and is classified as for fine precipitation (720 seconds or less) in the JIS standard. Here, the number in parentheses indicates the number of seconds it takes to filter 100 ml of water alone.
硫化水素低減試験における硫化物イオン濃度の検出下限は１μｇ／Ｌであり、硫化物イオンが検出されなかった場合に硫化水素低減効果があり、底質改善効果があると判定した。 The lower limit of detection of sulfide ion concentration in the hydrogen sulfide reduction test was 1 μg/L, and if no sulfide ions were detected, it was determined that there was a hydrogen sulfide reduction effect and a bottom sediment improvement effect.
（３）実海域試験
実施例４、５および比較例６、７の環境補修材の藻場造成効果を評価するため、実海域試験を実施した。実海域試験は、環境補修材を海底に設置し、藻場造成効果を評価する試験である。実海域試験を実施した海域は瀬戸内沿岸の湾内であり、通年潮流が無く、海底にシルトが堆積しているため、冬季においても海底に着生した藻類は皆無である。当該海域における底質表層の硫化物濃度（蒸留分離よう素滴定法）は最大で０．５ｍｇ／Ｌであった。
(3) Actual sea area test In order to evaluate the effects of the environmental repair materials of Examples 4 and 5 and Comparative Examples 6 and 7 on creating seaweed beds, an actual sea area test was conducted. The actual sea test is a test in which environmental repair materials are installed on the seabed and their effectiveness in creating seaweed beds is evaluated. The sea area where the actual sea test was conducted is a bay on the Seto Inland Sea coast, where there is no tidal current throughout the year and silt is deposited on the sea bed, so there is no algae that has grown on the sea bed even in winter. The maximum sulfide concentration (distillation separation iodine titration method) in the surface layer of the bottom sediment in the sea area was 0.5 mg/L.
実施例４、５および比較例６、７の環境補修材を２０１８年１２月中旬の同日、瀬戸内の同海域内において沿岸から約５ｍ沖側に離れた海底に設置した。 The environmental repair materials of Examples 4 and 5 and Comparative Examples 6 and 7 were installed on the seabed about 5 m offshore from the coast in the same sea area of the Seto Inland Sea on the same day in mid-December 2018.
実施例４の環境補修材をプラスチックパレットに４つ積載し、海底に設置した。実施例４と同様に、比較例６の環境補修材を実施例４から１０ｍ離れた海底に設置した。 Four pieces of the environmental repair material of Example 4 were loaded onto a plastic pallet and placed on the seabed. Similar to Example 4, the environmental repair material of Comparative Example 6 was installed on the seabed 10 m away from Example 4.
実施例４および比較例６の環境補修材から２０ｍ以上離れた海底に、実施例５の環境補修材を１０個（２００ｋｇ）設置した。実施例５の環境補修材と同様に、比較例７の環境補修材を実施例５の環境補修材から１０ｍ離れた海底に設置した。 Ten pieces (200 kg) of the environmental repair materials of Example 5 were installed on the seabed at least 20 m away from the environmental repair materials of Example 4 and Comparative Example 6. Similar to the environmental repair material of Example 5, the environmental repair material of Comparative Example 7 was installed on the seabed 10 m away from the environmental repair material of Example 5.
実施例４、５および比較例６、７の環境補修材を設置後１年間経過した後、陸上に引揚げて藻類の付着状況を観察した。 One year after the installation of the environmental repair materials of Examples 4 and 5 and Comparative Examples 6 and 7, they were taken to land and observed for algae adhesion.
（スラグ成形体の評価結果）
スラグ成形体の評価結果を下記表２に示す。
(Evaluation results of slag molded body)
The evaluation results of the slag molded body are shown in Table 2 below.
実施例１、２および３のスラグ成形体では、溶出試験において、鉄の溶出が確認された。また、硫化水素低減試験では硫化物イオンが検出されておらず、底質改善効果を有することが分かる。 In the slag molded bodies of Examples 1, 2, and 3, iron elution was confirmed in the elution test. In addition, no sulfide ions were detected in the hydrogen sulfide reduction test, indicating that it has a bottom sediment improvement effect.
比較例１、３、４のスラグ成形体では、溶出試験で鉄が溶出しておらず、硫化水素低減試験において硫化物イオンが検出された。鉄溶出特性に乏しいため底質改善効果が得られなかったと考えられる。 In the slag compacts of Comparative Examples 1, 3, and 4, no iron was eluted in the elution test, and sulfide ions were detected in the hydrogen sulfide reduction test. It is thought that the sediment improvement effect was not obtained due to poor iron elution characteristics.
比較例２、５のスラグ成形体では、溶出試験で鉄の溶出が認められたが、硫化水素低減試験においてｐＨが実施例よりも高く、硫化物イオンが検出された。製鋼スラグによるｐＨ上昇の抑制効果が小さいため、鉄による硫化水素低減効果が低減し、底質改善効果が得られなかったと考えられる。 In the slag molded bodies of Comparative Examples 2 and 5, iron elution was observed in the elution test, but the pH was higher than in the example in the hydrogen sulfide reduction test, and sulfide ions were detected. It is thought that because the effect of suppressing the pH increase by steelmaking slag was small, the hydrogen sulfide reduction effect of iron was reduced, and no bottom sediment improvement effect was obtained.
（環境補修材の評価結果）
次に、環境補修材の評価結果を下記表３に示す。
(Evaluation results of environmental repair materials)
Next, the evaluation results of the environmental repair materials are shown in Table 3 below.
実海域実験で引揚げた環境補修材の写真を図２～５に示す。実施例４および５の環境補修材では、環境補修材の表層に僅かにシルトが堆積していたが、環境補修材に藻類が繁茂しており、藻場改善効果が高いことが分かる。また、使用された容器が藻類の付着場所として機能していることが分かる。 Figures 2 to 5 show photographs of the environmental repair materials salvaged in the actual sea experiment. In the environmental repair materials of Examples 4 and 5, a slight amount of silt was deposited on the surface layer of the environmental repair materials, but algae were thriving on the environmental repair materials, indicating that the effect of improving the seaweed bed was high. It can also be seen that the containers used function as places for algae to attach.
比較例６および７の環境補修材では、藻類の着生量が少なく、環境補修材の表層に僅かにシルトが堆積していた。環境補修材の製造に用いた比較例２のスラグ成形体は鉄による硫化水素低減効果が低いため、シルト中の硫化水素により藻類の成長が阻害され良好な藻場造成効果が得られなかったと考えられる。 In the environmental repair materials of Comparative Examples 6 and 7, the amount of algae adhesion was small, and a slight amount of silt was deposited on the surface layer of the environmental repair materials. Since the slag molded body of Comparative Example 2 used for manufacturing the environmental repair material had a low hydrogen sulfide reduction effect due to iron, it is thought that the growth of algae was inhibited by the hydrogen sulfide in the silt and a good seaweed bed creation effect could not be obtained. It will be done.
〔付記事項〕
本発明は上述した各実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。さらに、各実施形態にそれぞれ開示された技術的手段を組み合わせることにより、新しい技術的特徴を形成することができる。
[Additional notes]
The present invention is not limited to the embodiments described above, and various modifications can be made within the scope of the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. are also included within the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment.
Claims (3)
リグニンスルホン酸およびその金属塩の少なくとも一方が製鋼スラグ重量に対して６質量％以上含有され、
上記スラグ成形体の表面に形成され、酸性土壌を主原料とし、リグニンスルホン酸およびその金属塩の少なくとも一方を含有する被覆部を備えることを特徴とするスラグ成形体。 A slag molded body used in a water environment,
At least one of lignin sulfonic acid and its metal salt is contained in an amount of 6% by mass or more based on the weight of steelmaking slag ,
A slag molded body, characterized in that it is formed on the surface of the slag molded body, and includes a coating portion that is made of acidic soil as a main raw material and contains at least one of ligninsulfonic acid and a metal salt thereof .
粒径または全長が１０ｍｍ以上４０ｍｍ以下であることを特徴とする請求項１に記載のスラグ成形体。 The above slag molded body is
The slag molded body according to claim 1, wherein the particle size or total length is 10 mm or more and 40 mm or less.
上記スラグ成形体が装入され、上記スラグ成形体と環境水とを接触させるための開口部を有する容器と、を備えることを特徴とする環境補修材。 The slag molded body according to claim 1 or 2 ,
An environmental repair material comprising: a container into which the slag molded body is charged and has an opening for bringing the slag molded body into contact with environmental water.
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| JP2014189473A (en) | 2013-03-28 | 2014-10-06 | Nisshin Steel Co Ltd | Slag powder molded body and production method thereof |
| JP2014200195A (en) | 2013-04-04 | 2014-10-27 | 日新製鋼株式会社 | Slug compact and production method thereof |
| JP2017176026A (en) | 2016-03-30 | 2017-10-05 | 日新製鋼株式会社 | Algae growth promoting agents |
| JP2018164430A (en) | 2017-03-28 | 2018-10-25 | 日新製鋼株式会社 | Slag molded body |
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| JP2014189473A (en) | 2013-03-28 | 2014-10-06 | Nisshin Steel Co Ltd | Slag powder molded body and production method thereof |
| JP2014200195A (en) | 2013-04-04 | 2014-10-27 | 日新製鋼株式会社 | Slug compact and production method thereof |
| JP2017176026A (en) | 2016-03-30 | 2017-10-05 | 日新製鋼株式会社 | Algae growth promoting agents |
| JP2018164430A (en) | 2017-03-28 | 2018-10-25 | 日新製鋼株式会社 | Slag molded body |
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