WO2017163595A1 - 製鋼スラグからカルシウムを溶出させる方法、および製鋼スラグからカルシウムを回収する方法 - Google Patents
製鋼スラグからカルシウムを溶出させる方法、および製鋼スラグからカルシウムを回収する方法 Download PDFInfo
- Publication number
- WO2017163595A1 WO2017163595A1 PCT/JP2017/002651 JP2017002651W WO2017163595A1 WO 2017163595 A1 WO2017163595 A1 WO 2017163595A1 JP 2017002651 W JP2017002651 W JP 2017002651W WO 2017163595 A1 WO2017163595 A1 WO 2017163595A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- calcium
- steelmaking slag
- aqueous solution
- slag
- water
- Prior art date
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- 239000002893 slag Substances 0.000 title claims abstract description 316
- 239000011575 calcium Substances 0.000 title claims abstract description 184
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 161
- 238000000034 method Methods 0.000 title claims abstract description 131
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 28
- 239000010959 steel Substances 0.000 title claims abstract description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 186
- 239000007864 aqueous solution Substances 0.000 claims abstract description 128
- 238000006703 hydration reaction Methods 0.000 claims abstract description 98
- 230000036571 hydration Effects 0.000 claims abstract description 97
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 93
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 93
- 238000009628 steelmaking Methods 0.000 claims description 244
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 128
- 238000011282 treatment Methods 0.000 claims description 77
- 238000000227 grinding Methods 0.000 claims description 11
- 230000000887 hydrating effect Effects 0.000 claims description 9
- 229940043430 calcium compound Drugs 0.000 abstract description 27
- 150000001674 calcium compounds Chemical class 0.000 abstract description 27
- 239000002245 particle Substances 0.000 description 51
- 230000008569 process Effects 0.000 description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 38
- 239000007789 gas Substances 0.000 description 37
- 238000010828 elution Methods 0.000 description 31
- 239000000243 solution Substances 0.000 description 29
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 28
- 230000001965 increasing effect Effects 0.000 description 28
- 239000007787 solid Substances 0.000 description 23
- 238000011084 recovery Methods 0.000 description 21
- 229910052698 phosphorus Inorganic materials 0.000 description 20
- 239000011574 phosphorus Substances 0.000 description 20
- 229910052742 iron Inorganic materials 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 16
- 238000007654 immersion Methods 0.000 description 16
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 15
- 235000010216 calcium carbonate Nutrition 0.000 description 14
- 239000000920 calcium hydroxide Substances 0.000 description 14
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 14
- -1 calcium iron aluminum Chemical compound 0.000 description 14
- 235000012241 calcium silicate Nutrition 0.000 description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 description 13
- 239000000378 calcium silicate Substances 0.000 description 13
- 229910052918 calcium silicate Inorganic materials 0.000 description 13
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 11
- 235000011941 Tilia x europaea Nutrition 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- 239000004571 lime Substances 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 230000004048 modification Effects 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- HDYBUJBCJPAOLV-UHFFFAOYSA-N [O-2].[Fe+2].[Ca+2].[Al+3] Chemical compound [O-2].[Fe+2].[Ca+2].[Al+3] HDYBUJBCJPAOLV-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- 239000003570 air Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000000292 calcium oxide Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- 229940087373 calcium oxide Drugs 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 5
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 5
- 235000012255 calcium oxide Nutrition 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000009751 slip forming Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000004611 spectroscopical analysis Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910001872 inorganic gas Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BVJRIMBTLVPCFB-UHFFFAOYSA-N [Fe+2].[O-2].[Ca+2].[O-2] Chemical compound [Fe+2].[O-2].[Ca+2].[O-2] BVJRIMBTLVPCFB-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- VMLAJPONBZSGBD-UHFFFAOYSA-L calcium;hydrogen carbonate;hydroxide Chemical compound [OH-].[Ca+2].OC([O-])=O VMLAJPONBZSGBD-UHFFFAOYSA-L 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- LRKMVRPMFJFKIN-UHFFFAOYSA-N oxocalcium hydrate Chemical compound [O].O.[Ca] LRKMVRPMFJFKIN-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0087—Treatment of slags covering the steel bath, e.g. for separating slag from the molten metal
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/26—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
- C04B18/142—Steelmaking slags, converter slags
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B3/00—General features in the manufacture of pig-iron
- C21B3/04—Recovery of by-products, e.g. slag
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/36—Processes yielding slags of special composition
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to a method of eluting calcium from steelmaking slag and a method of recovering calcium from steelmaking slag.
- Steelmaking slag (converter slag, pretreatment slag, secondary refining slag, electric furnace slag, etc.) generated in the steelmaking process is used for a wide range of applications including cement materials, roadbed materials, civil engineering materials, and fertilizers (non-patented) Reference 1 to 3). Moreover, some steelmaking slag which is not used for the said use is disposed by landfill.
- Steelmaking slag is known to contain elements such as phosphorus (P), calcium (Ca), iron (Fe), silicon (Si), manganese (Mn), magnesium (Mg), and aluminum (Al). It has been.
- the element contained most in steelmaking slag is calcium used in large quantities in the steelmaking process. Usually, about 20% by mass to 50% by mass of the total mass of the steelmaking slag is calcium.
- calcium is calcium hydroxide (CaO) which is produced by reacting quick lime (CaO) input in the steelmaking process as it is or free lime deposited during solidification, free lime reacts with water vapor or carbon dioxide in the air ( Ca (OH) 2 ) or calcium carbonate (CaCO 3 ), or calcium silicate (such as Ca 2 SiO 4 or Ca 3 SiO 5 ) or calcium iron oxide produced by free lime reacting with silicon or aluminum during solidification It exists in the form of aluminum (Ca 2 (Al 1-X Fe X ) 2 O 5 ) or the like (hereinafter, the compounds containing calcium present in the steelmaking slag are collectively referred to as “calcium compound”). ).
- Calcium carbonate and calcium oxide are the main slag forming materials in the steelmaking process and steelmaking process in the steelmaking process, and are used as regulators of the basicity and viscosity of the slag, and as a dephosphorizing agent from molten steel. Yes.
- calcium hydroxide obtained by adding water to calcium oxide is used as a neutralizing agent such as acid in the drainage process. Therefore, if the calcium compound contained in the steelmaking slag is recovered and reused in the ironmaking process, it is expected that the cost of ironmaking can be reduced.
- Calcium in steelmaking slag can be recovered by eluting it into an acidic aqueous solution such as hydrochloric acid, nitric acid or sulfuric acid.
- an acidic aqueous solution such as hydrochloric acid, nitric acid or sulfuric acid.
- the salt of calcium and the acid produced in this method is difficult to reuse.
- calcium chloride produced by eluting calcium in steelmaking slag into hydrochloric acid can be reused if heated to oxides, but there is a problem that the cost of processing harmful chlorine gas generated during the heating is high.
- calcium in steelmaking slag is eluted and collected in an acidic aqueous solution, there is a problem that the cost of purchasing the acid and discarding the acid after the elution treatment is high.
- Patent Document 1 describes a method of recovering precipitated calcium carbonate by blowing carbon dioxide into an aqueous solution from which calcium in converter slag has been eluted. At this time, in order to suppress the production of calcium bicarbonate having high solubility in water, the lower limit of pH is maintained at about 10. Although Patent Document 1 does not describe a specific method for maintaining the pH at 10 or higher, it is considered that the pH is maintained at 10 or higher by adjusting the amount of carbon dioxide blown.
- Patent Document 2 the crushed steelmaking slag is separated into an iron-concentrated phase and a phosphorus-concentrated phase, and a calcium compound in the phosphorus-concentrated phase is dissolved in washing water in which carbon dioxide is dissolved.
- a method is described in which it is heated to about 0 ° C. to precipitate and recover calcium bicarbonate in the wash water as calcium carbonate.
- Patent Document 3 describes a method in which a calcium compound is eluted from steelmaking slag by being eluted multiple times and recovered.
- steelmaking slag pretreatment slag
- steelmaking slag is immersed in water into which carbon dioxide has been blown multiple times, so that 2CaO ⁇ SiO 2 phase and phosphorus dissolved in this phase are preferentially eluted. Yes.
- the recovery rate of calcium is increased, the recovery process becomes complicated, so that the recovery takes time and the recovery cost is increased.
- the elution amount of the calcium compound in the CO 2 aqueous solution can be increased, the calcium recovery rate can be easily increased.
- Patent Documents 1 and 2 do not suggest any device for increasing the elution amount of the calcium compound in the CO 2 aqueous solution.
- Patent Document 3 it is considered that the total amount of calcium elution increases when the number of steps of dissolving the calcium compound is increased.
- this method makes the process complicated and is recovered. There is a problem that the cost becomes high.
- the present invention provides a method for eluting calcium from steelmaking slag, which can elute a larger amount of calcium from steelmaking slag into a CO 2 aqueous solution, and a method for recovering calcium eluted by this method.
- the purpose is to do.
- the present invention includes a steelmaking slag including a step of hydrating a steelmaking slag and a step of bringing the hydrated steelmaking slag into contact with an aqueous solution containing carbon dioxide in this order.
- the present invention relates to a method for eluting calcium from slag.
- the present invention also relates to a method for eluting calcium from a steelmaking slag, comprising a step of bringing an aqueous solution containing carbon dioxide into contact with the steelmaking slag while grinding the steelmaking slag or grinding the surface of the steelmaking slag. .
- the present invention also relates to a method for recovering calcium from steelmaking slag, including a step of eluting calcium from steelmaking slag by any one of the methods described above and a step of recovering the eluted calcium.
- FIG. 1 is a flowchart of a method for eluting calcium according to an embodiment of the present invention.
- FIG. 2 is a flowchart of the hydration process in the above embodiment.
- FIG. 3 is a flowchart of the hydration process in the first modification of the above embodiment.
- FIG. 4 is a flowchart of a second modification of the above embodiment.
- FIG. 5 is a flowchart of a method for recovering calcium according to another embodiment of the present invention.
- FIG. 6 is a flowchart of a process of bringing the CO 2 aqueous solution and steelmaking slag into contact with each other according to another embodiment of the present invention.
- FIG. 7 is a flowchart of the process of recovering calcium in another embodiment of the present invention.
- calcium in steelmaking slag is free lime, calcium hydroxide (Ca (OH) 2 ), calcium carbonate (CaCO 3 ), calcium silicate (Ca 2 SiO 4 , Ca 3 SiO 5 ), and calcium oxide. It exists in the form of iron aluminum (Ca 2 (Al 1-X Fe X ) 2 O 5 ).
- free lime although easily soluble in CO 2 aqueous solution, usually, only contains less than about 10% by weight in the steelmaking slag.
- calcium silicate is usually contained in the steelmaking slag by about 25% by mass to 70% by mass
- calcium iron oxide is usually contained by about 2% by mass to 30% by mass in the steelmaking slag. Therefore, if the calcium contained in the calcium compound other than free lime (such as calcium silicates and calcium oxide iron aluminum) easily eluted with CO 2 aqueous solution, to increase the dissolution of calcium into CO 2 solution from steelmaking slag It is possible to recover calcium from steelmaking slag in a shorter time.
- calcium silicate, calcium iron aluminum oxide, and the like usually have a low dissolution rate in an aqueous CO 2 solution.
- Calcium has a high solubility in a CO 2 aqueous solution, but silicon, aluminum, iron, and the like have a low solubility in a CO 2 aqueous solution. Therefore, when calcium silicate and calcium iron oxide aluminum dissolve in the CO 2 aqueous solution, calcium is eluted, but silicon, aluminum and iron become hydroxide, carbonate or hydrate and become the surface of steelmaking slag. May remain. In addition, silicon, aluminum, iron, and the like having low solubility in the CO 2 aqueous solution may be eluted on the surface of the steelmaking slag after being once eluted. Note that iron and manganese contained in iron oxide, calcium iron aluminum and the like in the steelmaking slag also have low solubility.
- the present inventors have either subjected to pre-hydration processing steelmaking slag, or while milling grinding or the surface of steel slag of steelmaking slag by contacting the CO 2 aqueous solution and the steel slag, The inventors have conceived that the calcium compound is easily dissolved by the CO 2 aqueous solution, thereby completing the present invention.
- FIG. 1 is a flowchart of a method for eluting calcium from steelmaking slag according to one embodiment of the present invention.
- the method of eluting calcium from steelmaking slag according to the present embodiment includes a step of hydrating steelmaking slag (step S110: hereinafter also referred to as “first step”), and A step of bringing the steelmaking slag subjected to the hydration treatment into contact with the CO 2 aqueous solution (step S120-1: hereinafter also referred to as “second step”).
- the type of steelmaking slag is not particularly limited as long as it is slag discharged in the steelmaking process.
- steelmaking slag include converter slag, pretreatment slag, secondary refining slag and electric furnace slag.
- crushed slag particles (hereinafter also referred to simply as “slag particles”. Note that when simply referred to as “steel slag”, both crushed slag particles and non-crushed slag particles are used.
- the maximum particle size is preferably 1000 ⁇ m or less. When the maximum particle size is 1000 ⁇ m or less, the surface area per volume becomes large, and water or CO 2 aqueous solution can sufficiently penetrate into the steelmaking slag, so that many calcium compounds are hydrated in this step. In the second step described later, a larger amount of calcium can be eluted.
- Steelmaking slag can be crushed to the said range with a well-known crusher.
- the maximum particle size of the slag particles is preferably 500 ⁇ m or less, more preferably 250 ⁇ m or less, and even more preferably 100 ⁇ m or less.
- the maximum particle size of the slag particles can be reduced to the above range by, for example, further crushing the crushed slag particles with a pulverizer including a hammer mill, a roller mill, a ball mill, and the like.
- metallic iron may be removed from the steelmaking slag before the hydration treatment.
- Metallic iron can be removed from the steelmaking slag by a known magnetic separator. From the viewpoint of increasing the removal efficiency of metallic iron, it is preferable to remove metallic iron after crushing steelmaking slag, and it is more preferable to remove metallic iron after crushing steelmaking slag.
- the steelmaking slag is obtained by filtering after putting steelmaking slag into a container containing water, leaching free lime and calcium hydroxide, and leaching calcium on the surface of the calcium compound. Slag may be used. Since the slag from which calcium is eluted to some extent can be used by using the filtration residual slag, the load of the second step described later can be reduced.
- the filtered water leached with calcium simultaneously obtained at this time is a highly alkaline aqueous solution having a pH of 11 or more (hereinafter also simply referred to as “high alkaline leached water”). As will be described later, the highly alkaline leachate can be used for precipitation of solid components containing calcium (fourth step) when calcium is recovered.
- the highly alkaline leachate can be used for applications requiring an alkaline aqueous solution such as a neutralizing agent for acid waste water.
- an alkaline aqueous solution such as a neutralizing agent for acid waste water.
- the hydration treatment may be performed by a method and conditions capable of hydrating a calcium compound contained in steelmaking slag, preferably any calcium compound other than free lime, more preferably calcium silicate or calcium iron oxide aluminum.
- the specific example of the hydration process includes a process of immersing steelmaking slag in water (step S112: , Simply referred to as “immersion in water”), a process of adding water to the slag particles, kneading into a paste, and then allowing to stand (step S113: hereinafter, also simply referred to as “water-containing standing”), and A process of allowing steelmaking slag to stand still in a container having a water vapor amount with a relative humidity of 70% or more (step S114: hereinafter, also simply referred to as “wet standing”) is included.
- the relative humidity is 70% or more from the viewpoint of sufficiently aggregating water vapor between the slag particles by the capillary agglomeration phenomenon and reliably attaching the water to the slag particles. It is preferable that
- a hydration process may give only one type, such as immersion in the said water (process S112), water-containing stationary (process S113), and wet stationary (process S114). Two or more types may be performed in any order.
- the hydration treatment includes a step (step S111) for selecting which treatment method to perform the hydration treatment, as well as immersion in the water (step S112).
- a modified first step (step S112-1) to be described later may be selected.
- Ca hydrate When these hydration treatments are performed on steelmaking slag, for example, calcium silicate hydrate and calcium hydroxide (Ca (OH) 2 ) are produced from calcium silicate by the reaction shown in the following (formula 1), A calcium oxide-based hydrate is formed from calcium iron oxide aluminum by the reaction shown in the following (formula 2) (hereinafter, compounds containing calcium that can be generated by hydration treatment are collectively referred to as “Ca hydrate”. Also called.).
- Ca hydrate produced by the above reaction or the like is easily dissolved in an aqueous CO 2 solution. Therefore, by performing the hydration treatment, calcium derived from calcium silicate and calcium iron oxide aluminum contained in the steelmaking slag can be more easily eluted.
- generated by a hydration process becomes larger than the sum total of the volume of the compound before reaction normally.
- a part of the free lime in the steelmaking slag is eluted in the water for treatment. Therefore, when hydration is performed, cracks are generated in the slag particles, and the slag particles are likely to collapse starting from the cracks. When the slag particles collapse in this way, the particle size of the slag particles decreases, the surface area per volume increases, and water or CO 2 aqueous solution can sufficiently penetrate into the steelmaking slag. Many calcium compounds can be hydrated, and more calcium can be eluted in the second step described below. Therefore, it is possible to sufficiently increase the calcium elution amount only by the exemplified hydration treatment.
- the water used for the hydration treatment is free carbonic acid that has not been ionized and ionized bicarbonate ions (HCO 3 ⁇ ). It is preferable that the content of carbon dioxide including the above is less than 300 mg / l. If the content of carbon dioxide is less than 300 mg / l, free lime and calcium compounds other than calcium hydroxide are difficult to elute into the water used for the hydration treatment. Therefore, most of the calcium contained in the steelmaking slag is second. It can be eluted in a CO 2 aqueous solution in the process, and the calcium recovery process is less likely to be complicated.
- the carbon dioxide content of water is large, calcium carbonate produced by the reaction of calcium and carbon dioxide eluted from free lime, calcium hydroxide, etc., precipitates and covers the surface of the slag particles.
- the carbon dioxide content is less than 300 mg / l, inhibition of the hydration reaction due to the precipitation of calcium carbonate hardly occurs.
- content of the said carbon dioxide in industrial water is usually less than 300 mg / l. Therefore, it is preferable that the water used for the hydration process by immersion in the water (step S112) or standing with water (step S113) is industrial water to which carbon dioxide is not intentionally added or contained.
- the temperature of water used for the hydration treatment may be a temperature at which water does not evaporate vigorously.
- the temperature of water is preferably 100 ° C. or lower.
- the temperature of the water may be 100 ° C. or more as long as it is not higher than the boiling point of water at the pressure during the hydration treatment.
- the temperature of water when the hydration treatment is performed by immersion in water (step S112) is preferably 0 ° C.
- the temperature of the water at the time of performing a hydration process by water-containing stationary is 0 degreeC or more and 70 degrees C or less.
- step S114 water vapor is introduced into gas such as air, nitrogen (N 2 ), oxygen (O 2 ), argon (Ar), helium (He), etc.
- gas such as air, nitrogen (N 2 ), oxygen (O 2 ), argon (Ar), helium (He), etc.
- the relative humidity may be increased, or a gas consisting only of water vapor may be used.
- the relative humidity and temperature in the container can be arbitrarily set.
- the temperature of the gas is preferably 0 ° C. or higher and 100 ° C. or lower, preferably May be 10 ° C. or more and 100 ° C. or less and a relative humidity 70% or more.
- the gas may be stirred so that the calcium compound can be more uniformly hydrated.
- step S114 when a hydration process is performed on the steelmaking slag by wet standing using a gas consisting only of water vapor (step S114), it is preferable to heat the water vapor so that the water vapor pressure is equal to or higher than atmospheric pressure.
- the temperature of water vapor with the water vapor pressure set to atmospheric pressure or higher can be, for example, 100 ° C. or higher.
- the upper limit of the temperature is not particularly limited, but is preferably 300 ° C. or less from the standpoint of pressure resistance of the apparatus and economical aspect.
- the duration of performing the hydration treatment can be arbitrarily set according to the average particle diameter of the slag and the temperature at which the hydration treatment is performed (temperature of air containing water or water vapor).
- the duration of the hydration treatment may be shorter as the average particle size of the slag is smaller, and may be shorter as the temperature at which the hydration treatment is performed is higher.
- the duration of the hydration treatment is continuously about 8 hours. It can be 3 hours or more and 30 hours or less.
- the duration time of the hydration treatment is continuously 0.6 hours or more and 8 hours or less.
- the duration of the hydration process should be continuously about 7 hours It is preferable that the time be 3 hours or longer and 30 hours or shorter.
- the duration of the hydration treatment is preferably continuously 0.5 hours or more and 8 hours or less.
- the duration of the hydration process is It can be continuously about 10 hours, and is preferably 1 hour or more and 40 hours or less.
- the duration time of the hydration treatment is continuously 0.2 hours or more and 5 hours or less.
- the average particle diameter of steelmaking slag and the conditions for hydration treatment are determined in advance. You may refer to an average particle diameter and the conditions of a hydration process.
- the hydration treatment is preferably performed to such an extent that calcium silicate sufficiently becomes a hydrate and calcium hydroxide, and calcium iron aluminum oxide sufficiently becomes a calcium oxide hydrate.
- the hydration treatment is preferably performed until the amount of calcium silicate contained in the steelmaking slag is 50% by mass or less, or until the amount of calcium iron oxide aluminum is 20% by mass or less.
- the steelmaking slag may be immersed in water in which carbon dioxide has been previously dissolved, or carbon dioxide may be dissolved in water after the steelmaking slag is immersed in water.
- carbon dioxide may be dissolved in water after the steelmaking slag is immersed in water.
- Carbon dioxide can be dissolved in water, for example, by bubbling a gas containing carbon dioxide. From the viewpoint of enhancing the elution of calcium from steelmaking slag, it is preferable that 30 mg / l or more of non-ionized carbon dioxide (free carbonic acid) is dissolved in the CO 2 aqueous solution.
- the amount of free carbonic acid that can be contained in general tap water is 3 mg / l or more and 20 mg / l or less.
- the gas containing carbon dioxide may be pure carbon dioxide gas or a gas containing components other than carbon dioxide (for example, oxygen or nitrogen).
- the gas containing carbon dioxide include exhaust gas after combustion, and a mixed gas of carbon dioxide, air and water vapor. From the viewpoint of increasing the concentration of carbon dioxide in the CO 2 aqueous solution and improving the elution of calcium compounds (such as calcium silicate) from the steelmaking slag into the CO 2 aqueous solution, the gas containing carbon dioxide increases the carbon dioxide content. It is preferable to contain by density
- the amount of slag in the CO 2 aqueous solution is preferably 1 g / l or more and 100 g / l or less, and more preferably 2 g / l or more and 40 g / l or less. preferable.
- the immersion is preferably performed for 3 minutes or more, and more preferably for 5 minutes or more.
- a calcium compound contained in steelmaking slag preferably calcium silicate and calcium iron aluminum oxide
- a calcium compound contained in steelmaking slag can be hydrated to form a Ca hydrate that is more easily eluted into a CO 2 aqueous solution. Therefore, a larger amount of calcium can be eluted in the CO 2 aqueous solution in a shorter time.
- this embodiment can be easily performed, the burden of cost for implementation is small.
- FIG. 3 is a flowchart of the hydration process (step S110) in the first modification of the above embodiment.
- the hydration treatment step S110
- the immersed steelmaking slag is added.
- Crushing or crushing, or grinding the surface of the steelmaking slag (hereinafter also simply referred to as “crushing etc.”) (step S112-1: hereinafter also referred to as “deformation first step”).
- the second step can be performed in the same manner as in the above-described embodiment, and thus description thereof is omitted.
- the steelmaking slag immersed in water can be crushed by using a known crusher that can be used wet. Further, the slag particles can be pulverized in water by rotating a ball mill charged with slag particles, water and pulverized balls, and simultaneously hydrated.
- the duration of this step is preferably 0.1 hours to 5 hours continuously, and preferably 0.2 hours to 3 hours. More preferred.
- this step is preferably performed until the maximum particle size of the slag particles is 1000 ⁇ m or less, preferably 500 ⁇ m or less, more preferably 250 ⁇ m, and even more preferably 100 ⁇ m or less.
- FIG. 4 is a flowchart of a method of eluting calcium from steelmaking slag according to another embodiment of the present invention (hereinafter also referred to as “second modified example”).
- the method for eluting calcium from the steelmaking slag according to the present modification includes a step of selecting whether or not to hydrate the steelmaking slag (step S100), optionally hydrating the steelmaking slag.
- a step of performing the treatment step S110
- a step of bringing the CO 2 aqueous solution into contact with the steelmaking slag while crushing the steelmaking slag step S120-2: hereinafter also referred to as “deformation second step”).
- a modified second step is performed after the step of hydrating the steelmaking slag (step 110).
- step S110 the step of performing the hydration treatment
- the step S110 may be either the first step or the modified first step. Since the first step and the modified first step can be performed in the same manner as the above-described embodiment, the description thereof is omitted.
- the method of crushing steelmaking slag in this step can be the same method as the method of crushing steelmaking slag in the first deformation step.
- the steelmaking slag immersed can be crushed by dipping the steelmaking slag in a CO 2 aqueous solution and simultaneously using a known crusher that can be used in a wet state.
- slag particles by rotating the ball mill was charged CO 2 solution and grinding balls, the slag particles were ground in a CO 2 aqueous solution, it is possible to crush such slag particles simultaneously.
- this step is performed until the maximum particle size of the slag particles is 1000 ⁇ m or less, preferably 500 ⁇ m or less, more preferably 250 ⁇ m, and even more preferably 100 ⁇ m or less. preferable.
- FIG. 5 is a flowchart of a method for recovering calcium from steelmaking slag according to another embodiment of the present invention.
- the method for recovering calcium from the steelmaking slag according to the present embodiment includes a step of eluting calcium from the steelmaking slag by any of the methods described above and a step of recovering the eluted calcium. Including. Specifically, in the method for recovering calcium from the steelmaking slag according to the present embodiment, a step of selecting whether or not to hydrate the steelmaking slag (step S100), optionally hydrating the steelmaking slag.
- step S110 A step of applying (step S110), a step of bringing the CO 2 aqueous solution into contact with the steelmaking slag (step S120), and a step of recovering calcium eluted in the CO 2 aqueous solution (step S130).
- step S100 and step S110 can be performed by any of the methods described above, and thus description thereof is omitted.
- FIG. 6 is a flowchart of a step (step S120) of bringing the aqueous CO 2 solution and steelmaking slag into contact with each other in the present embodiment.
- step S120 the contact of the CO 2 aqueous solution and steelmaking slag (step S120), the step of selecting whether crushing etc. steelmaking slag in contact with CO 2 aqueous solution (step S121), and The aqueous CO 2 solution and the steelmaking slag are selected by a method selected from the second step (step S120-1) for contacting without crushing or the second modified step (step S120-2) for contacting while crushing. Contacting.
- step S120-1 and step S120-2 can be performed by the above-described method, and thus description thereof is omitted.
- FIG. 7 is an exemplary flowchart of a step (step S130) of collecting calcium eluted in the CO 2 aqueous solution in the present embodiment.
- the step of recovering calcium includes, for example, a step of separating steelmaking slag and a CO 2 aqueous solution (step S131: hereinafter also referred to as “third step”), calcium.
- Steps for precipitation step S132: hereinafter also referred to as “fourth step”
- steps for recovering the precipitated solid component step S133: hereinafter also referred to as “fifth step”
- step S131 separation of steelmaking slag and CO 2 aqueous solution
- the CO 2 aqueous solution (supernatant solution) in which calcium is dissolved is separated from the steelmaking slag (step S131).
- Separation can be performed by a known method. Examples of the separation method include filtration and a method in which a steelmaking slag is precipitated by allowing a CO 2 aqueous solution to stand.
- the separation method include filtration and a method in which a steelmaking slag is precipitated by allowing a CO 2 aqueous solution to stand.
- the supernatant liquid may be collected, or in the two-component system including the supernatant liquid and the precipitated steelmaking slag as long as the solid component precipitated in the subsequent step is not mixed with the steelmaking slag.
- the subsequent steps may be performed only on the supernatant.
- Calcium eluted in the CO 2 aqueous solution can be precipitated by a known method as a solid component containing calcium (step S132).
- a method for precipitating calcium eluted into CO 2 aqueous solution as a solid component includes a method of increasing the pH of the methods and CO 2 aqueous solution to remove carbon dioxide from the CO 2 solution.
- step S131 Carbon dioxide is removed from the CO 2 aqueous solution separated from the steelmaking slag in the third step (step S131), and calcium eluted in the CO 2 aqueous solution in the second step (step S120) can be precipitated.
- the calcium compound precipitated at this time include calcium carbonate, calcium carbonate hydrate, and calcium hydroxide.
- a method for removing carbon dioxide from the CO 2 aqueous solution is not particularly limited. Examples of methods for removing carbon dioxide include (1) introduction of gas, (2) decompression and (3) heating.
- the carbon dioxide can be removed from the CO 2 aqueous solution by diffusing (transferring) the carbon dioxide into the gas bubble substituted or introduced with the gas.
- the gas to be introduced may be a gas that reacts with water (chlorine gas, sulfurous acid gas, etc.), but the calcium produced by the formation of a salt between the ions generated by introduction into the CO 2 aqueous solution and the calcium eluted in the water. From the viewpoint of suppressing the decrease in the amount of precipitation, a gas having low reactivity with water is preferable.
- the gas introduced into the CO 2 aqueous solution may be an inorganic gas or an organic gas.
- inorganic gas is more preferable because there is little possibility of combustion or explosion even if it leaks to the outside.
- the inorganic gas having low reactivity with water include air, nitrogen, oxygen, hydrogen, argon and helium, and a mixed gas thereof.
- the mixed gas includes air in an environment in which this step is performed, which includes nitrogen and oxygen in a ratio of approximately 4: 1.
- organic gases that are less reactive with water include methane, ethane, ethylene, acetylene, propane, and fluorocarbons.
- carbon dioxide can be removed from the CO 2 aqueous solution by placing the CO 2 aqueous solution in a reduced pressure environment.
- carbon dioxide can be removed by putting a CO 2 aqueous solution into a sealed container, exhausting (degassing) the air in the container with a pump or the like, and making the inside of the container a reduced pressure atmosphere.
- the application of ultrasound to the CO 2 solution or the stirring of the CO 2 aqueous solution may be performed simultaneously.
- the above (1) to (3) may be combined. Note that these combinations may be selected in consideration of the supply system of gas and heat, the location, the use of by-product gas in the factory, and the like.
- the effect of removing carbon dioxide by introducing the gas into the CO 2 aqueous solution, exhausting the gas more than the amount of gas introduced, and reducing the atmosphere, the effect of removing carbon dioxide by introducing the gas and the stirring effect, and the reduced pressure of the CO 2 aqueous solution
- the effect of removing carbon dioxide is obtained, and carbon dioxide can be efficiently removed.
- the effect of removing carbon dioxide is further promoted by further heating.
- carbon dioxide can be easily removed by the effect of introducing the gas into the CO 2 aqueous solution and the reduced pressure of the CO 2 aqueous solution, so there is no need to increase the heating temperature. Heating cost can be reduced.
- the solid component containing calcium can be deposited in the CO 2 aqueous solution by raising the pH of the CO 2 aqueous solution separated from the steelmaking slag.
- the pH is increased, the amount of hydrogen ions (H + ) in the CO 2 aqueous solution decreases. Therefore, in the following equilibrium equation (Formula 3), hydrogen carbonate ions (HCO 3 ⁇ ) are replaced with hydrogen ions (H + ) and carbonate ions.
- the equilibrium moves in the direction of separation into (CO 3 2 ⁇ ).
- the increased carbonate ions are considered to be precipitated by combining with calcium ions to form poorly soluble calcium carbonate (CaCO 3 ).
- HCO 3 ⁇ ⁇ H + + CO 3 2 ⁇ (Formula 3)
- step S131 When calcium begins to precipitate, white turbidity due to calcium carbonate occurs in the CO 2 aqueous solution. It is sufficient to raise the pH of the CO 2 aqueous solution to such an extent that this cloudiness can be confirmed visually. From the viewpoint of further precipitating calcium and increasing the recovery rate of calcium, the pH is raised by 0.2 or more with respect to the pH of the CO 2 aqueous solution separated from the steelmaking slag in the third step (step S131). Is preferable, more preferably 0.3 or more, further preferably 1.0 or more, further preferably 1.5 or more, and further preferably 2.0 or more.
- the measurement is preferably performed while measuring the pH of the aqueous CO 2 solution.
- the pH of the aqueous CO 2 solution can be measured by a known glass electrode method.
- a solid component containing not only calcium but also other elements such as phosphorus is precipitated.
- a solid component that precipitates immediately after starting to raise the pH (hereinafter, referred to as “initial precipitate”). ) Is a compound containing phosphorus (hereinafter, also simply referred to as “phosphorus compound”), and the solid component (hereinafter also referred to as “late precipitate”) that precipitates later is phosphorus.
- the content ratio is lower.
- a step of recovering (step S133), which will be described later, is performed while raising the pH, and the initial precipitate is recovered to separate a solid component having a higher phosphorus ratio and a solid component having a lower phosphorus ratio. Can be recovered.
- the phosphorus compound recovered from steelmaking slag can be reused as phosphorus resources. Therefore, when a solid component having a high phosphorus compound content is recovered, the reuse of phosphorus becomes easy.
- recovered from steelmaking slag can be reused as an iron-making raw material, when this iron-making raw material contains the phosphorus compound, iron will become weak. Therefore, it is better for the solid component reused as the iron-making raw material to have a lower content of the phosphorus compound. Therefore, if a solid component having a high phosphorus compound content and a solid component having a low phosphorus compound content are separately obtained from a CO 2 aqueous solution containing phosphorus and calcium, purification of the recovered solid component becomes easy or unnecessary. And the quality of the product using the recovered solid component can be further improved.
- the initial precipitate may be recovered before the pH increases by 1.0.
- the waste liquid generated when calcium carbide (calcium carbide) and water are reacted to produce acetylene can be added to the CO 2 aqueous solution.
- slag leaching water prepared by immersing steelmaking slag in water or water used for hydration in the first step or modified first step may be added to the CO 2 aqueous solution.
- Slag leaching water may be obtained by immersing steelmaking slag from which calcium is to be recovered in water before hydration (step S110), or by immersing another steelmaking slag in water. .
- the CO 2 aqueous solution after recovering calcium by the method according to the present embodiment can simplify or eliminate the wastewater treatment, and can reduce the cost of the wastewater treatment.
- step S133 the solid component precipitated in the fourth step is collected (step S133).
- the precipitated solid component can be recovered by a known method including vacuum filtration and pressure filtration.
- This solid component includes calcium derived from steelmaking slag.
- Experiment 1 shows an example in which the steelmaking slag is hydrated and then brought into contact with an aqueous solution containing carbon dioxide to elute calcium from the steelmaking slag.
- Steelmaking slag having the component ratios shown in Table 1 was prepared.
- the component of steelmaking slag was measured by the ICP emission spectroscopic analysis method and the chemical analysis method.
- the slag was pulverized using a hammer mill so that the maximum particle size was 200 ⁇ m.
- the maximum particle size of the pulverized slag was confirmed using a laser diffraction / scattering particle size distribution measuring device and a sieve having an opening of 200 ⁇ m.
- the aqueous solution was separated, and the amount of calcium eluted into the aqueous solution (kg / 50 l) was measured by ICP spectroscopy and chemical analysis.
- the amount of calcium measured is divided by the value obtained by multiplying the mass of the immersed steelmaking slag by the component ratio of Ca in the steelmaking slag, and the elution rate (%) of calcium by the above treatment is measured. (Examples 1 to 15).
- the type, temperature and time of hydration treatment applied to the immersed steelmaking slag, the amount of immersed steelmaking slag, the method of contacting with an aqueous solution containing carbon dioxide (Ca elution method), and the amount of calcium elution (kg / kg) 50 l) and calcium elution rate (%) are shown in Table 2.
- Experiment 2 shows an example in which the steelmaking slag is brought into contact with an aqueous solution containing carbon dioxide while being pulverized, and calcium is eluted from the steelmaking slag.
- the aqueous solution was separated, and the amount of calcium eluted into the aqueous solution (kg / 100 l) was measured by ICP spectroscopy.
- the amount of calcium measured is divided by the value obtained by multiplying the mass of the immersed steelmaking slag by the component ratio of Ca in the steelmaking slag, and the elution rate (%) of calcium by the above treatment is measured. (Examples 21 to 27).
- a steelmaking slag not subjected to the above hydration treatment was immersed in 100 l of water in a container, and an impeller was used while blowing carbon dioxide having a flow rate of 15 l / min at room temperature (20 to 30 ° C.).
- the steelmaking slag suspension was stirred for 30 minutes without being crushed (Comparative Example 21). Thereafter, the amount of calcium eluted and the dissolution rate of calcium were measured by the same method.
- the type, temperature and time of hydration treatment performed on the immersed steelmaking slag, the amount of immersed steelmaking slag, the method of contacting with an aqueous solution containing carbon dioxide (Ca elution method), and the calcium elution amount (kg / kg) 100 l) and calcium elution rate (%) are shown in Table 3.
- Experiment 3 shows an example in which calcium is eluted from the steelmaking slag by hydrating the steelmaking slag while contacting it with an aqueous solution containing carbon dioxide.
- Hydration treatment Steel slag prepared in Experiment 1 and pulverized to a maximum particle size of 200 ⁇ m, 2.5 liters of water, and pulverized balls having an apparent volume of 1.0 liter are placed in a ball mill container.
- the hydration treatment was performed by rotating the container at a normal speed (20 to 30 ° C.) and a peripheral speed of 180 m / min.
- the ball diameter of the pulverized ball was 10 mm.
- the steelmaking slag after the above hydration treatment from which the contact pulverized balls were removed while being pulverized was transferred to another ball mill, and water was added so that the amount of water became 50 l.
- a ground ball having an apparent volume of 10 l is put into a container of a ball mill, and carbon dioxide with a flow rate of 7 l / min is blown into the container at a normal temperature (20 to 30 ° C.) while the peripheral speed is 100 m / min.
- the container was rotated in min.
- the ball diameter of the pulverized ball was 10 mm.
- the aqueous solution was separated, and the amount of calcium eluted into the aqueous solution (kg / 50 l) was measured by ICP spectroscopy and chemical analysis.
- the amount of calcium measured is divided by the value obtained by multiplying the mass of the immersed steelmaking slag by the component ratio of Ca in the steelmaking slag, and the elution rate (%) of calcium by the above treatment is measured. (Examples 31 to 33).
- a steelmaking slag not subjected to the above hydration treatment is immersed in 50 l of water in a container and an impeller is used while blowing carbon dioxide having a flow rate of 7 l / min at room temperature (20 to 30 ° C.).
- the steelmaking slag suspension was stirred for 30 minutes. Thereafter, the amount of calcium eluted and the dissolution rate of calcium were measured by the same method (Comparative Example 31).
- the type, temperature and time of hydration treatment performed on the immersed steelmaking slag, the amount of immersed steelmaking slag, the method of contacting with an aqueous solution containing carbon dioxide (Ca elution method), and the calcium elution amount (kg / kg) 50 l) and calcium elution rate (%) are shown in Table 4.
- the method for eluting calcium according to the present invention can easily increase the elution amount of calcium in steelmaking slag into an aqueous solution containing carbon dioxide, and can easily increase the recovery rate of calcium from steelmaking slag. Therefore, it is useful as a method for recovering calcium resources in iron making.
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Abstract
Description
図1は、本発明の一実施の形態に係る製鋼スラグからカルシウムを溶出させる方法のフローチャートである。図1に示されるように、本実施の形態に係る製鋼スラグからカルシウムを溶出させる方法は、製鋼スラグに水和処理を施す工程(工程S110:以下、「第1工程」ともいう。)、および前記水和処理を施した製鋼スラグとCO2水溶液とを接触させる工程(工程S120-1:以下、「第2工程」ともいう。)を含む。
本工程では、製鋼スラグに水和処理を施す(工程S110)。
2(2CaO・SiO2) + 4H2O → 3CaO・2SiO2・3H2O + Ca(OH)2 (式1)
2CaO・1/2(Al2O3・Fe2O3) +10H2O → 1/2(4CaO・Al2O3・19H2O) + HFeO2 (式2)
(式(2)は、酸化カルシウム鉄アルミニウム(Ca2(Al1-XFeX)2O5)においてX=1/2の場合の例を示す。)
本工程では、CO2水溶液に製鋼スラグを浸漬して、製鋼スラグ中のカルシウムを水溶液中に溶出させる(工程S120-1)。
本実施の形態によれば、製鋼スラグに含まれるカルシウム化合物、好ましくはケイ酸カルシウムおよび酸化カルシウム鉄アルミニウム、を水和させて、よりCO2水溶液に溶出しやすいCa水和物にすることができるため、より短時間でより多量のカルシウムをCO2水溶液に溶出させることができる。また、本実施の形態は、容易に行うことができるため、実施する際のコストの負担が少ない。
図3は、上記実施の形態の第1の変形例における水和処理(工程S110)のフローチャートである。図3に示されるように、本変形例に係る製鋼スラグからカルシウムを溶出させる方法では、水和処理(工程S110)を水への浸漬によって施し、このとき、同時に、浸漬している製鋼スラグを破砕もしくは粉砕するか、または製鋼スラグの表面を摩砕(以下、単に「破砕等」ともいう。)する(工程S112-1:以下、「変形第1工程」ともいう。)。なお、本変形例において、第2工程は上述した実施の形態と同様に行い得るので、説明を省略する。
上述した水和処理による反応は、製鋼スラグの表面近傍または内部でカルシウム化合物と水とが接触することで生じる。ここで、製鋼スラグの内部へもある程度の水は浸透するものの、表面近傍のほうが水との接触量は多い。そのため、Ca水和物は、製鋼スラグの表面近傍でより生成しやすい。また、製鋼スラグに含まれる成分が水和処理に使用する水に溶解すると、上述したCO2水溶液へ溶解するときと同様に、シリコン、アルミニウム、鉄およびマンガンまたはこれらの水酸化物、炭酸化物および水和物などが製鋼スラグの表面に残存または析出することがある。これらの残存または析出した物質が製鋼スラグの内部への水の浸透を阻害すると、製鋼スラグの内部ではCa水和物が生成しにくくなる。
第1の変形例によれば、さらに短時間でより多量のカルシウムをCO2水溶液に溶出させることができる。また、本実施の形態は、たとえば製鋼スラグの破砕またはスラグ粒子の粉砕と同時に行うことができるなど、工程を煩雑にせずに行うことができるため、実施する際のコストの負担が少ない。
図4は、本発明の別の実施の形態に係る製鋼スラグからカルシウムを溶出させる方法(以下、「第2の変形例」ともいう。)のフローチャートである。図4に示されるように、本変形例に係る製鋼スラグからカルシウムを溶出させる方法は、製鋼スラグに水和処理を施すか否かを選択する工程(工程S100)、任意に製鋼スラグに水和処理を施す工程(工程S110)、および、製鋼スラグを破砕等しながら、CO2水溶液と製鋼スラグとを接触させる工程(工程S120-2:以下、「変形第2工程」ともいう。)を含む。工程S100で水和処理を施すことを選択したときは、前記製鋼スラグに水和処理を施す工程(工程110)の後に変形第2工程(工程S120-2)行う。工程S100で水和処理を施さないことを選択したときは、前記第1工程または前記変形第1工程を行わずに、変形第2工程(工程S120-2)のみを行う。なお、本変形例において、水和処理を施す工程(工程S110)は、前記第1工程および前記変形第1工程のいずれでもよい。第1工程および変形第1工程は上述した実施の形態と同様に行い得るので、説明を省略する。
製鋼スラグからのカルシウムの溶出は、製鋼スラグの表面近傍または内部でカルシウム化合物またはCa水和物とCO2水溶液とが接触することで生じる。ここで、上述した製鋼スラグと水との接触と同様に、製鋼スラグの内部へもある程度のCO2水溶液は浸透するものの、表面近傍のほうがCO2水溶液との接触量は多い。そのため、カルシウムは、製鋼スラグの表面近傍からより溶出しやすい。また、製鋼スラグに含まれる成分がCO2水溶液に溶解すると、上述したように、シリコン、アルミニウム、鉄およびマンガンまたはこれらの水酸化物、炭酸化物および水和物などが製鋼スラグの表面に残存または析出することがある。これらの残存または析出した物質が製鋼スラグの内部へのCO2水溶液の浸透を阻害すると、製鋼スラグの内部からはカルシウムが溶出しにくくなる。
第2の変形例によれば、さらに短時間でより多量のカルシウムをCO2水溶液に溶出させることができる。また、本変形例は、容易に行うことができるため、実施する際のコストの負担が少ない。
図5は、本発明の別の実施の形態に係る製鋼スラグからカルシウムを回収する方法のフローチャートである。図5に示されるように、本実施の形態に係る製鋼スラグからカルシウムを回収する方法は、前記したいずれかの方法で製鋼スラグからカルシウムを溶出させる工程と、溶出したカルシウムを回収する工程とを含む。具体的には、本実施の形態に係る製鋼スラグからカルシウムを回収する方法は、製鋼スラグに水和処理を施すか否かを選択する工程(工程S100)、任意に製鋼スラグに水和処理を施す工程(工程S110)、CO2水溶液と製鋼スラグとを接触させる工程(工程S120)、およびCO2水溶液に溶出したカルシウムを回収する工程(工程S130)を含む。なお、本実施の形態において、工程S100および工程S110は、前述したいずれかの方法で行い得るので、説明を省略する。
本工程では、カルシウムが溶解したCO2水溶液(上澄み液)と、製鋼スラグとを分離する(工程S131)。分離は、公知の方法で行うことができる。分離方法の例には、濾過、およびCO2水溶液を静置して製鋼スラグを沈殿させる方法が含まれる。スラグを沈殿させたときは、さらに上澄み液のみを回収してもよいし、後の工程で析出する固体成分が製鋼スラグと混じらない限りにおいて、上澄み液および沈殿した製鋼スラグを含む2成分系において、上澄み液に対してのみこれ以降の工程を行ってもよい。
CO2水溶液に溶出したカルシウムは、カルシウムを含む固体成分として、公知の方法で析出させることができる(工程S132)。CO2水溶液に溶出したカルシウムを固体成分として析出させる方法の例には、CO2水溶液から二酸化炭素を除去する方法およびCO2水溶液のpHを高くする方法が含まれる。
たとえば、第3工程(工程S131)で製鋼スラグと分離したCO2水溶液から二酸化炭素を除去して、第2の工程(工程S120)でCO2水溶液中に溶出したカルシウムを析出させることができる。このとき析出されるカルシウム化合物の例には、炭酸カルシウム、炭酸カルシウム水和物、および水酸化カルシウムが含まれる。
CO2水溶液中の二酸化炭素の平衡圧力よりも低い二酸化炭素分圧を有するガスをカルシウムが溶解したCO2水溶液中に導入することで、溶解している二酸化炭素と導入したガスとを置換または導入したガスのバブル中に二酸化炭素を拡散(移行)させて、二酸化炭素をCO2水溶液から除去することができる。導入するガスは、水と反応するガス(塩素ガス、亜硫酸ガスなど)でもよいが、CO2水溶液中に導入することによって生成するイオンと水中に溶出したカルシウムとが塩を形成することによる、カルシウムの析出量の減少を抑制する観点からは、水との反応性が低いガスであることが好ましい。CO2水溶液中に導入するガスは、無機系ガスでもよく、有機系ガスでもよい。これらのうち、外部に漏れても燃焼や爆発の可能性が少ないことから、無機系ガスがより好ましい。水との反応性が低い無機系ガスの例には、空気、窒素、酸素、水素、アルゴンおよびヘリウムならびにこれらの混合ガスが含まれる。混合ガスには、窒素と酸素とをおおよそ4:1の割合で含む、本工程を実施する環境の空気が含まれる。水との反応性が低い有機系ガスの例には、メタン、エタン、エチレン、アセチレン、プロパンおよびフルオロカーボンが含まれる。
1気圧(約100kPa)付近およびそれ以下の圧力環境下では、CO2水溶液にかかる圧力が低くなると、二酸化炭素の溶解度が減少する。そのため、CO2水溶液を減圧環境下に置くことで、二酸化炭素をCO2水溶液から除去することができる。たとえば、CO2水溶液を密閉容器に入れて、ポンプなどによって容器内の空気を排出(脱気)して、容器内を減圧雰囲気にすることによって、二酸化炭素を除去することができる。二酸化炭素の除去量をより多くする観点からは、減圧に加えて、CO2水溶液への超音波の印加、またはCO2水溶液の攪拌を同時に行ってもよい。
1気圧(約100kPa)付近およびそれ以下の圧力環境下では、CO2水溶液の温度が高くなると、二酸化炭素の溶解度が減少する。そのため、CO2水溶液を加熱することによって、二酸化炭素をCO2水溶液から除去することができる。このとき、加熱コストを低くする観点から、水の蒸気圧が雰囲気圧力を超えない範囲内の温度に加熱することが好ましい。たとえば、雰囲気圧力が1気圧であるときは、加熱温度は、100℃未満であることが好ましい。CO2水溶液を加熱すると、二酸化炭素が除去されるだけでなく、カルシウム化合物(炭酸カルシウム)の溶解度が低下するため、カルシウムがより析出しやすくなる。
また、製鋼スラグと分離したCO2水溶液のpHを上げることで、カルシウムを含む固体成分をCO2水溶液中に析出させることができる。pHを上げると、CO2水溶液中の水素イオン(H+)量が減少するため、下記の平衡式(式3)において、炭酸水素イオン(HCO3 -)が水素イオン(H+)と炭酸イオン(CO3 2-)とに分離する方向に平衡が移動する。本工程では、こうして増加した炭酸イオンが、カルシウムイオンと結合して難溶性の炭酸カルシウム(CaCO3)となることによって、カルシウムが析出すると考えられる。
HCO3 - ⇔ H+ + CO3 2- (式3)
本工程では、第4工程で析出した固体成分を回収する(工程S133)。析出した固体成分は、減圧濾過および加圧濾過を含む公知の方法によって回収することができる。この固体成分には、製鋼スラグ由来のカルシウムが含まれる。
実験1では、製鋼スラグに水和処理を施し、その後、二酸化炭素を含有する水溶液と接触させて、製鋼スラグからカルシウムを溶出させた例を示す。
上記粉砕した製鋼スラグに、以下のいずれかの方法で水和処理を施した。
製鋼スラグの質量に対して50質量%の量の水の中に上記製鋼スラグを入れ、撹拌した後、表2に示す時間、静置した。静置中は、製鋼スラグは水の中に沈んだ状態にした。静置中の水温は25℃または50℃に調整した。
製鋼スラグの質量に対して27%の水を上記製鋼スラグに添加して、ペースト状になるように混練して、製鋼スラグ全体を含水させた。上記ペースト状の含水製造スラグを容器に入れ、乾燥しないように蓋をして、表2に示す時間、静置した。静置中のペーストの温度は25℃に調整した。
温度25℃、相対湿度95%の大気が充填されており、横型の攪拌機で内部の気体成分が撹拌されているチャンバー内に、製鋼スラグを、表2に示す時間、静置した。静置中のチャンバー内の圧力は大気圧(約1気圧(約0.1MPa))とした。
上記水和処理後の製鋼スラグを、容器内で50lの水に懸濁させた。なお、製鋼スラグの粒子同士が低い強度で結合した粒径の大きい塊ができていたときは、ローラで上記塊がなくなるまで潰した後に、上記水に浸漬させた。この製鋼スラグが懸濁した水に、常温(20~30℃)で、流量を8l/minとした二酸化炭素を吹き込みながら、インペラを用いて撹拌した。
実験2では、製鋼スラグを、粉砕しながら、二酸化炭素を含有する水溶液と接触させて、製鋼スラグからカルシウムを溶出させた例を示す。
実験1で準備した、最大粒径が200μmとなるように粉砕した製鋼スラグに、実験1と同様の手順によって、水への浸漬、含水静置または湿潤静置のいずれかによって水和処理を施した。なお、水和処理は、表3に示す時間、行った。なお、上記準備した製鋼スラグの一部には、上記水和処理を施さなかった。
上記水和処理後の製鋼スラグおよび上記水和処理を施していない製鋼スラグのいずれかと、100lの水と、見かけ体積が20lとなる量の粉砕ボールとを、ボールミルの容器内に投入し、常温(20~30℃)で、流量を15l/minとした二酸化炭素を容器内に吹き込みながら、周速100m/minで容器を回転させた。粉砕ボールのボール径は10mmだった。
実験3では、製鋼スラグを粉砕しながら水和処理を施した後、二酸化炭素を含有する水溶液と接触させて、製鋼スラグからカルシウムを溶出させた例を示す。
実験1で準備した、最大粒径が200μmとなるように粉砕した製鋼スラグと、2.5lの水と、見かけ体積が1.0lとなる量の粉砕ボールを、ボールミルの容器内に投入し、常温(20~30℃)で、周速180m/minで容器を回転させて水和処理を施した。粉砕ボールのボール径は10mmだった。
上記水和処理を施した製鋼スラグを、以下のいずれかの方法で二酸化炭素を含有する水溶液に接触させた。
粉砕ボールを取り除いた上記水和処理後の製鋼スラグを別の容器に移し、水量が50lとなるように水を投入した。その後、常温(20~30℃)で、流量を7l/minとした二酸化炭素を吹き込みながら、インペラを用いて製鋼スラグ懸濁液を撹拌した。
粉砕ボールを取り除いた上記水和処理後の製鋼スラグを別のボールミルに移し、水量が50lとなるように水を投入した。さらに、見かけ体積が10lとなる量の粉砕ボールをボールミルの容器内に投入し、常温(20~30℃)で、流量を7l/minとした二酸化炭素を容器内に吹き込みながら、周速100m/minで容器を回転させた。粉砕ボールのボール径は10mmだった。
Claims (10)
- 製鋼スラグに水和処理を施す工程と、
前記水和処理を施した製鋼スラグと二酸化炭素を含有する水溶液とを接触させる工程と、をこの順で含む、
製鋼スラグからカルシウムを溶出させる方法。 - 前記水和処理は、前記製鋼スラグを水に浸漬する処理である、請求項1に記載の方法。
- 前記水和処理を施す工程において、水に浸漬した前記製鋼スラグを破砕もしくは粉砕するか、または水に浸漬した前記製鋼スラグの表面を摩砕する、請求項2に記載の方法。
- 前記水和処理に使用する前記水の二酸化炭素の含有量は、300mg/l未満である、請求項2または3に記載の方法。
- 前記水和処理は、破砕または粉砕した前記製鋼スラグに水を添加してペースト状に混練し、その後静置する処理である、請求項1に記載の方法。
- 前記水和処理は、相対湿度が70%以上の水蒸気が存在する容器の中に製鋼スラグを静置する処理である、請求項1に記載の方法。
- 前記接触させる工程において、前記二酸化炭素を含有する水溶液に接触させている前記製鋼スラグを破砕もしくは粉砕するか、または前記二酸化炭素を含有する水溶液に接触させている前記製鋼スラグの表面を摩砕する、請求項1~6のいずれか1項に記載の方法。
- 製鋼スラグを粉砕しながら、または製鋼スラグの表面を摩砕しながら、二酸化炭素を含有する水溶液と製鋼スラグとを接触させる工程を含む、製鋼スラグからカルシウムを溶出させる方法。
- 前記製鋼スラグは、水和処理を施した製鋼スラグである、請求項8に記載の方法。
- 請求項1~9のいずれか1項に記載の方法により製鋼スラグからカルシウムを溶出させる工程と、
前記溶出したカルシウムを回収する工程とを含む、
製鋼スラグからカルシウムを回収する方法。
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RU2018130504A RU2718879C1 (ru) | 2016-03-24 | 2017-01-26 | Способ элюирования кальция из сталеплавильного шлака и способ извлечения кальция из сталеплавильного шлака |
EP17769642.4A EP3434655A4 (en) | 2016-03-24 | 2017-01-26 | METHOD FOR ELIMINATING CALCIUM FROM STEEL SLAG AND METHOD FOR RECOVERING CALCIUM FROM STEEL SLAG |
CA3016281A CA3016281A1 (en) | 2016-03-24 | 2017-01-26 | Method for eluting calcium from steel slag and method for recovering calcium from steel slag |
KR1020187025670A KR20180112808A (ko) | 2016-03-24 | 2017-01-26 | 제강 슬래그로부터 칼슘을 용출시키는 방법, 및 제강 슬래그로부터 칼슘을 회수하는 방법 |
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MX2018010941A MX2018010941A (es) | 2016-03-24 | 2017-01-26 | Metodo para eluir calcio a partir de escoria de acero y metodo para recuperar calcio a partir de escoria de acero. |
BR112018069422A BR112018069422A2 (pt) | 2016-03-24 | 2017-01-26 | método para eluição de cálcio de escória de aço e método para recuperação de cálcio de escória de aço |
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WO2019107116A1 (ja) * | 2017-11-30 | 2019-06-06 | 日新製鋼株式会社 | 製鋼スラグからカルシウムを溶出させる方法、製鋼スラグからカルシウムを回収する方法、および製鋼スラグからカルシウムを溶出させる装置 |
WO2019107115A1 (ja) * | 2017-11-30 | 2019-06-06 | 日新製鋼株式会社 | 製鋼スラグからカルシウムを溶出させる方法、製鋼スラグからカルシウムを回収する方法、および製鋼スラグからカルシウムを溶出させる装置 |
JP2019162610A (ja) * | 2018-03-19 | 2019-09-26 | Jfeスチール株式会社 | スラグからセレンを除去する方法および装置並びにスラグの再利用方法および再生スラグの製造方法 |
JP2020132456A (ja) * | 2019-02-15 | 2020-08-31 | Jfeミネラル株式会社 | スラグのエージング方法、土木材料の製造方法、およびスラグのエージング処理用水和促進剤 |
JP2020132457A (ja) * | 2019-02-15 | 2020-08-31 | Jfeミネラル株式会社 | スラグのエージング方法、土木材料の製造方法、およびスラグのエージング処理用炭酸化促進剤 |
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TW201802253A (zh) | 2018-01-16 |
US20190078170A1 (en) | 2019-03-14 |
BR112018069422A2 (pt) | 2019-01-22 |
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