AU2020104367A4 - Cement Filling Material for Co-solidifying Arsenic and Preparation Method Thereof - Google Patents
Cement Filling Material for Co-solidifying Arsenic and Preparation Method Thereof Download PDFInfo
- Publication number
- AU2020104367A4 AU2020104367A4 AU2020104367A AU2020104367A AU2020104367A4 AU 2020104367 A4 AU2020104367 A4 AU 2020104367A4 AU 2020104367 A AU2020104367 A AU 2020104367A AU 2020104367 A AU2020104367 A AU 2020104367A AU 2020104367 A4 AU2020104367 A4 AU 2020104367A4
- Authority
- AU
- Australia
- Prior art keywords
- arsenious
- blast furnace
- filling material
- furnace slag
- reducing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000011049 filling Methods 0.000 title claims abstract description 57
- 239000004568 cement Substances 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052785 arsenic Inorganic materials 0.000 title claims description 26
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims description 26
- 239000002893 slag Substances 0.000 claims abstract description 82
- 239000002920 hazardous waste Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 239000010959 steel Substances 0.000 claims abstract description 39
- 239000010440 gypsum Substances 0.000 claims abstract description 35
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 35
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 30
- 230000023556 desulfurization Effects 0.000 claims abstract description 30
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 26
- 230000002195 synergetic effect Effects 0.000 claims abstract description 20
- 239000002910 solid waste Substances 0.000 claims abstract description 17
- 238000003801 milling Methods 0.000 claims abstract description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000011812 mixed powder Substances 0.000 claims abstract description 3
- 238000002386 leaching Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002699 waste material Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000002474 experimental method Methods 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 231100001261 hazardous Toxicity 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 239000010878 waste rock Substances 0.000 claims description 4
- 239000003651 drinking water Substances 0.000 claims description 3
- 235000020188 drinking water Nutrition 0.000 claims description 3
- 235000005979 Citrus limon Nutrition 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims description 2
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 229960004887 ferric hydroxide Drugs 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 2
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 150000002790 naphthalenes Chemical class 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229920005646 polycarboxylate Polymers 0.000 claims description 2
- 238000009628 steelmaking Methods 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019976 tricalcium silicate Nutrition 0.000 claims description 2
- 229910021534 tricalcium silicate Inorganic materials 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 1
- 235000012241 calcium silicate Nutrition 0.000 claims 1
- 229910052918 calcium silicate Inorganic materials 0.000 claims 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims 1
- 150000007974 melamines Chemical class 0.000 claims 1
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 26
- 238000001723 curing Methods 0.000 description 15
- 238000005065 mining Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 231100000419 toxicity Toxicity 0.000 description 7
- 230000001988 toxicity Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000035622 drinking Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229910001653 ettringite Inorganic materials 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- -1 i.e. Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000805 Pig iron Inorganic materials 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000002384 drinking water standard Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 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
- 229940000489 arsenate Drugs 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229940095672 calcium sulfate Drugs 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940057307 dihydrate calcium sulfate Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000003895 groundwater pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
-
- 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
- C04B18/0463—Hazardous waste
- C04B18/0472—Waste material contaminated by heavy metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B1/00—Dumping solid waste
- B09B1/008—Subterranean disposal, e.g. in boreholes or subsurface fractures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
- B09B3/25—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/144—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being a flue gas desulfurization product
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/21—Mixtures thereof with other inorganic cementitious materials or other activators with calcium sulfate containing activators
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0051—Water-absorbing polymers, hydrophilic polymers
-
- 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
- C04B2111/00017—Aspects relating to the protection of the environment
-
- 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
- C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Civil Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a mine cement filling material for co-solidifying arsenious
hazardous wastes and a preparation method thereof, and belongs to environment
protection fields, such as mine cement filling, solid waste resource utilization and
synergetic disposal of the arsenious hazardous wastes. The preparation method
comprises the following steps: milling the required raw materials, i.e., blast furnace
slag, steel slag and desulfurization gypsum, with 0.01%-1% of moisture content
according to the dry basis weight percentage of 45%-50% of the blast furnace slag,
10%-30% of the steel slag and 10%-15% of the desulfurization gypsum, milling
independently or milling by mixed powder until the specific surface area is 200-600
m<2>/Kg, adding 10%-35% of calcium hydroxide, uniformly mixing to obtain a
cementing agent, and drying the arsenious hazardous wastes until the moisture
content is 0.01%-1%, according to the weight ratio of the cementing agent/aggregate
of 1/4-1/8, the weight ratio of the arsenious hazardous wastes/(cementing agent +
aggregate) of 1/1000-1/100, adding 0%-1% of water reducing agent, until the mass
fraction of slurry is 65%-86%, and uniformly stirring to obtain the qualified mine
cement filling material. The preparation method provided by the invention has the
characteristics of simple and easy operation, low energy consumption, low cost, no
new solid waste generation, less environmental pollution, and environmental
protection.
Description
Cement Filling Material for Co-solidifying Arsenic and Preparation
Method Thereof
The invention relates to the technical field of mine cement filling, solid
waste resource utilization and synergetic disposal of arsenious hazardous
waste, in particular to a mine cement filling material for co-solidifying
arsenious hazardous wastes and a preparation method thereof.
The current industrial system is actually a process of extracting resources
and discharging waste. Tailings, waste rock, coal gangue, fly ash and
smelting slag produced in the process of the development and utilization of
domestic mineral resources have become the largest industrial solid waste
emissions, accounting for 85% of the total solid waste emissions in the
country.
Steel slag is a solid slag body composed of slag-making materials,
smelting reactants, eroded furnace body and fettling materials, impurities
brought in by metal burden and slag-making materials specially added to
adjust the properties of steel slag in the process of steel production. In our
country, the total amount of steel slag accumulated in steel mills nationwide
exceeds 200 million tons, covering an area of more than 6,666,667 square
meters, and still increases by more than 30 million tons per year.
Blast furnace slag is composed of gangue, ash, flux and other impurities
that cannot enter pig iron. It is a fusible mixture. Judging from its chemical composition, blast furnace slag belongs to silicate material. It has potential hydraulicity and potential activity, and its output is generally about 25% of pig iron output.
Desulfurization gypsum is a by-product of wet flue gas desulfurization
technology adopted in thermal power plants. In recent years, with the vigorous
implementation and promotion of wet flue gas desulfurization as the
mainstream technology in our country, the emission of flue gas desulfurization
gypsum, a by-product, is increasing day by day. Long-term stacking has
resulted in rising stacking costs and environmental pollution.
Mine mining leaves a large area of goaf, and the piled-up waste rock,
waste residue yard and the constructed tailings dam bring serious hidden
dangers in the safety area and environmental load. Tailings dam break and
heavy metal pollution incidents emerge one after another, such as Liuyang
cadmium pollution incident, Jiyuan lead pollution incident, Fengxiang blood
lead incident and Zijin mining leakage incident. The storage of these
hazardous wastes seriously threatens human health and social harmony and
stability.
Effective joint and synergetic disposal of all kinds of industrial wastes is
an effective measure and general trend to realize environmental treatment
and resource utilization.
At present, the commonly used methods for treating arsenious waste
residue at home and abroad include stabilization/solidification treatment
technology and resource utilization technology. Stabilization technology is to
convert it into insoluble and relatively stable metal arsenate and arsenite under natural conditions by adding different chemical additives and using chemical reactions, and then stabilize the leaching solution. Curing is to use cured materials to fix arsenic and reduce its migration and leakage. Common curing methods of arsenic include cement curing, lime/fly ash curing, organic polymer curing, plastic curing and melt curing. The resource utilization technology of arsenious waste residue is to extract arsenious products from arsenious waste residue as secondary resources. Common methods include pyrolysis and wet leaching.
After cement solidifies heavy metals, landfill is usually carried out, which
is similar to underground cemented filling mining technology. Cemented filling
method generally adopts gravel, river sand or tailings or gobi aggregate as
aggregate (sometimes mixed with block stone), which is mixed with cement or
lime cementing materials to form slurry or paste, which is transported to the
filling area by pipeline pumping or gravity flow. Mine filling mining method has
the advantages of high recovery rate, low ore dilution rate, effective control of
ground pressure, prevention of ground subsidence, protection of mine
environment, etc. However, the mining technology and filling technology are
relatively complex, and mining and filling affect each other. If the problem of
mechanization of mining operation cannot be properly solved, the production
efficiency and capacity are relatively low. In addition to the mining, processing,
transportation and other series of expenses of filling materials, the raw ore
cost is relatively high.
Ordinary Portland cement is the most commonly used cementing agent,
but its production process itself has the characteristics of high energy
consumption and serious pollution. In recent years, a large number of new cementing materials have appeared, which are basically improved on the basis of ordinary Portland cement or blast furnace slag cement, i.e., slag, fly ash, red mud and the like with a history of high heat are used to replace some cement clinker. However, raw materials are limited, the amount of replaced clinker is low, and the cementing result is not ideal, etc., thus their popularization and application are restricted. Cement filling material contains a certain proportion of cementing agent, which has higher strength and integrity and higher operation safety. It can meet various underground support requirements and improve ore recovery rate and stope operation efficiency.
With the popularization and application of mine filling mining technology, filling
cementing agents are also continuously updated, providing an effective way
for the resource utilization of bulk industrial solid wastes.
The invention relates to a mine cement filling material for synergetic
disposal of arsenious hazardous waste and a preparation method thereof,
which aims at solving the following problems in the prior art:
1. Cement filling mining has high cost, large cement consumption and low
early strength;
2. The massive storage of bulk industrial solid wastes such as tailings,
blast furnace slag, steel slag and desulfurization gypsum causes waste of
resources and environmental pollution;
3. In the process of safe disposal of arsenious solid waste, the cost is
high, the capacity-increasing ratio is large, and the safe landfill site occupies a
large area.
The invention realizes the preparation of mine cement filling material with
which cement is replaced and synergetic disposal of arsenious solid waste;
The synergetic and safe disposal of arsenious hazardous waste is realized,
and the toxicity of the leaching solution obtained by the toxic leaching method
reaches the drinking water standard; the industrial solid waste after
"harmless" solidification treatment is filled into the underground mining empty
area, thus saving a large area of land required for a safe landfill site.
The technical solution adopted to realize the above-mentioned object of
the invention is as follows:
A mine cement filling material for synergetic disposal of arsenious
hazardous wastes, comprising a cementing agent, an aggregate, a water
reducing agent and arsenious hazardous waste, characterized in that: the
cementing agent comprises 45%-60% of blast furnace slag, 20%-35% of steel
slag and 10%-20% of desulfurization gypsum in weight percentage.
Calcium hydroxide can also be added into the cementing agent to replace
part of blast furnace slag, steel slag and desulfurization gypsum, and the
content range of the cementing agent is as follows: 45-50% of blast furnace
slag, 10-30% of steel slag, 10-15% of desulfurization gypsum and 10-35% of
calcium hydroxide.
the aggregate comprises one or more of mountain sand, river sand,
tailings or waste rock.
the water reducing agent is one or more of lignosulfonate water reducing
agent, naphthalene series high-efficiency water reducing agent, melamine
series high-efficiency water reducing agent, sulfamate series high-efficiency water reducing agent, fatty acid series high-efficiency water reducing agent and polycarboxylate series high-efficiency water reducing agent.
the arsenious hazardous waste is a hazardous solid waste whose
leaching experiment is carried out according to the leaching method specified
in Solid Waste-Extraction Procedure for Leaching Toxicity-Horizontal Vibration
Method (HJ557-2009), and the concentration of arsenic in the leaching
solution exceeds 10pg/L specified in Standards for Drinking Water Quality
(GB5749-2006).
The blast furnace slag is granular blast furnace slag formed after the slag
generated in the ironmaking process of the metallurgical blast furnace is
rapidly cooled with water, also known as water slag or water-quenched slag,
and the main chemical composition ranges from: 38%-49% of CaO, 26%-42%
of SiO 2 , 6%-17% of A1203, 1%-13% of MgO, 0.1%-2% of MnO, 0.07%-2.5%
of FeO, and 0.2%-1.5% of S. Other indexes meet the requirements of Ground
Granulated Blast Furnace Slag Used for Cement and Concrete (GB/T18046
2008).
The steel slag is furnace slag produced in the process of steelmaking
process, containing 5%-30% of tricalcium silicate, 5%-30% of dicalcium
silicate (C2S), 10%-38% of RO phase, 2%-8% of ferric oxide, 0.5%-5% of
calcium hydroxide, 0.5%-5% of ferric hydroxide, 0.01%-3% of free calcium
oxide, 0.01%-10% of calcium carbonate, 0.01%-8% of magnesium carbonate,
0.01%-3% of ferric carbonate and 0.01%-3% of other impurities. Other
indexes meet the requirements of Steel Slag Powder used for Cement and
Concrete (GB/T20491-2006).
The desulfurization gypsum can be replaced with industrial by-product
gypsum, which refers to an industrial by-product generated by chemical
reaction in industrial production with calcium sulfate (mainly anhydrous and
dihydrate calcium sulfate) as the main component, and comprises one or
more of phosphogypsum, fluorogypsum, lemon gypsum and waste pottery
mold gypsum.
The action mechanism of the cementing agent is as follows:
The core problem is that the filling material can obtain good strength so
that the cementing agent in the filling material can be hydrated to produce
sufficient C-S-H gel. However, the molar ratio of (SiO2+Al203)/(CaO+MgO) in
C-S-H gel, which contributes the most to the strength of the filling material, is
within the range of 0.6-0.8. Sufficient research results show that the higher the
ratio in C-S-H gel within this range, the greater its contribution to the strength
of the filling material. C-S-H gel is a chain-like silicate formed by silicon
oxygen tetrahedron, and the molar ratio of (SiO2+Al203)/(CaO+MgO) in
water quenched granulated blast furnace slag is above 0.9.
The ratio of (SiO2+Al203)/(CaO+MgO+FeO) in steel slag is very low,
generally lower than 0.15. Therefore, if the steel slag is ground into fine
powder, the ability of the steel slag fine powder to provide silicon (aluminum)
oxygen tetrahedron for cementation hardening and strength growth of the
filling material is extremely weak. In C-S-H gel, not only a large number of
silicon-oxygen tetrahedrons can be replaced by aluminum-oxygen
tetrahedrons and a certain amount of iron-oxygen tetrahedrons, but also
calcium ions can be replaced by a large number of divalent ions such as magnesium ions and ferrous ions. Therefore, if the steel slag powder can be ground into micron-sized fine powder so that the hydration reaction can occur quickly, a large amount of divalent metal cations can be provided for the cementing system.
The content of alumina in granulated blast furnace slag is generally high
and is linked with silicon oxide tetrahedron in the form of aluminum oxide
tetrahedron in the glass body of blast furnace slag. When the blast furnace
slag comes into contact with the higher pH solution formed by the steel slag,
the aluminum oxide tetrahedron tends to depolymerize from the link of the
silicon oxide tetrahedron into the solution. When there is more gypsum in the
system, ettringite crystallization reaction can occur rapidly.
4H3AI042-+6Ca2++6CaSO4-2H20+40H
+44H20--*2(3CaO-Al203-3CaSO4-32H20)
Ettringite is a double salt with very low solubility. The solubility product
constants of ettringite reported by C. B. Satish et al. in Pages 1-19, Chemical
Geology, (148) 1998 are 10-111.6. Its continuous crystallization leads to the
decrease of A13+ ion concentration in the solution, which moves the balance
of the above reaction formula to the right and makes reaction continue. The
dissolution of a large amount of A13+ ions breaks the link between the
aluminum-oxygen tetrahedron and the silicon-oxygen tetrahedron in the
granulated blast furnace slag micropowder, and greatly improves the activity
of the remaining silicon-oxygen tetrahedron, thus continuously producing the
depolymerization of the silicon (aluminum)-oxygen tetrahedron, creating
conditions for the formation of a large amount of C-S-H gel.
The formation of a large amount of C-S-H gel requires not only a large
amount of active silicon (aluminum) oxygen tetrahedrons, but also a large
number of divalent cations such as calcium, magnesium and iron. The
hydration of steel slag can effectively provide these divalent metal cations.
Therefore, ultra-fine steel slag powder ground into micron scale, blast furnace
water quenched slag powder and desulfurization gypsum powder can be
combined to make mine filling cementing agent instead of cement.
The invention relates to a preparation method of mine cement filling
material used for synergetic disposal of arsenious hazardous waste, which is
characterized in that: The milled cementing agent is uniformly mixed with
aggregate, arsenious hazardous waste, water reducing agent and water, and
the specific steps are as follows:
(1) milling the required raw materials, i.e., blast furnace slag, steel
slag and desulfurization gypsum, with 0.01%-1% of moisture content
according to the dry basis weight percentage of 45%-50% of the blast furnace
slag, 10%-30% of the steel slag and 10%-15% of the desulfurization gypsum,
milling independently or milling by mixed powder until the specific surface
area is 200-600 m<2>/Kg, adding 10%-35% of calcium hydroxide, and
uniformly mixing to obtain a cementing agent;
(2) drying the arsenious hazardous wastes until the moisture
content is 0.01%-1%, according to the weight ratio of the cementing
agent/aggregate of 1/4-1/8, the weight ratio of the arsenious hazardous
wastes/(cementing agent + aggregate) of 1/1000-1/100, adding 0%-1% of water reducing agent, until the mass fraction of slurry is 65%-86%, and uniformly stirring to obtain the qualified mine cement filling material.
After the filling material is solidified, the leaching concentration of arsenic
is lower than the drinking water standard, i.e., lOpg/L.
Compared with the prior art, the invention has the advantages of:
1. More than 90% of the raw materials of mine cement filling material are
from industrial solid wastes.
2. The mine cement filling material not only treats steel slag and
desulfurization gypsum, but also synergistically disposes of arsenious
hazardous waste to realize waste treatment.
3. The strength of mine cement filling material for synergetic disposal of
arsenious hazardous wastes meets the requirements of filling mining method.
At the same time, the leaching concentration of arsenic is lower than the living
standard of drinking water, thus avoiding groundwater pollution, realizing
"harmlessness" and saving a large area of land required for safe landfill.
4. The preparation method of mine cement filling material for synergetic
disposal of arsenious hazardous waste is simple to operate, low in energy
consumption and conventional in equipment, so that the cost is low, no new
solid waste is generated, environmental pollution is small, and it is cleaning
and environmental-friendly.
The invention will be described in detail with reference to embodiments.
Embodiment 1
A mine cementing material, which is prepared from the following raw
materials by weight percentage:
60% of blast furnace slag
30% of steel slag
10% of desulfurization gypsum
The invention relates to a preparation method of mine cement filling
material used for synergetic disposal of arsenious hazardous waste, which is
characterized in that: The milled cementing agent is uniformly mixed with
aggregate, arsenious hazardous waste, water reducing agent and water, and
the specific steps are as follows:
(1) drying the required raw materials, i.e., blast furnace slag, steel
slag and desulfurization gypsum respectively until the moisture content is
0.01%-1%, then milling the blast furnace slag, steel slag and desulfurization
gypsum according to the dry basis weight percentage of 60%, 30% and 10%
separately to the specific surface area of 400m<2>/Kg, 400m<2>/Kg and
360m<2>/Kg, and uniformly mixing to obtain a cementing agent;
(2) The arsenious hazardous waste disposed of is lead-zinc mine
tailings, which are also used as aggregates. According to the weight ratio of
cementing agent/aggregate of 1/4, add 1% of polycarboxylic acid water
reducing agent, with slurry mass fraction of 86%, and mix evenly to obtain
qualified mine cement filling material.
The toxic leaching result of arsenic in lead-zinc mine tailings is 62pg/L.
Experiment I. The cement filling material prepared in Embodiment 1 for
co-solidifying of arsenious hazardous waste is subjected to uniaxial infinite
compressive strength test and arsenic toxicity leaching test.
1. Experimental method
1)Experimental group: The filling material described in Embodiment 1 is
injected into a 70.7x70.7x7.7mm standard test mold and shaken with a
shaking table for 30s;
2)Control group: Grade 42.5 cement is used as cementing agent, and
other steps are exactly the same as those of the test group;
3)The films of experimental group and the control group are removed
after static maintenance for 24h, and put into 40°C steam curing box for
maintenance respectively. Uniaxial unconfined compressive strength test and
arsenic toxicity leaching test are respectively carried out at the nodes of age.
2. Experimental results
1)The test results of uniaxial unconfined compressive strength are shown
in the following table:
Uniaxial unconfined compressive
Age strength/MPa
Experimental group Control group
3d 10.09 6.68
7d 16.67 9.56
28d 23.29 16.75
2) The concentration results of arsenic leaching solution of all solid waste
cements in the test group are as follows:
Arsenic leaching concentration/pg/L
Drinking Age Experim Control Detectio water ental group group n limit standard
3d 25 ND
7d 6 4 10 4
28d 9 ND
Embodiment 2
The invention relates to a mine gelling agent, which is prepared from the
following raw materials by weight percentage:
Blast furnace slag 50%
Steel slag 30%
Desulfurization gypsum 10%
Sodium hydroxide 10%
The invention relates to a preparation method of mine cement filling
material used for synergetic disposal of arsenious hazardous waste, which is
characterized in that: The milled cementing agent is uniformly mixed with
aggregate, arsenious hazardous waste, water reducing agent and water, and
the specific steps are as follows:
(1) drying the required raw materials, i.e., blast furnace slag, steel slag
and desulfurization gypsum respectively until the moisture content is 0.01-1%,
then milling the blast furnace slag, steel slag and desulfurization gypsum to
the specific surface area of 400m<2>/Kg, 400m<2>/Kg and 360m<2>/Kg
respectively, and uniformly mixing 50%, 30%, 10% and 10% of analytically
pure calcium hydroxide according to the dry basis weight percentage to obtain
a cementing agent;
(2) Arsenious hazardous waste is lead-zinc mine tailings, which are also
used as aggregates. Dry until the moisture content is 0.01%-1%. According to
the weight ratio of cementing agent/aggregate of 1/4, add 1% of
polycarboxylic acid water reducing agent, with slurry mass fraction of 86%,
and mix evenly to obtain qualified mine cement filling material.
The toxic leaching result of arsenic in lead-zinc mine tailings is 62pg/L.
Experiment II. The cement filling material prepared in Embodiment 2 for
co-solidifying arsenious hazardous waste is subjected to uniaxial infinite
compressive strength test and arsenic toxicity leaching test.
1. Experimental method
1) Experimental group: The filling material described in Embodiment 2 is
injected into a 70.7x70.7x70.7mm standard test mold and shaken with a
shaking table for 30s;
2) Control group: Grade 42.5 cement is used as cementing agent, and
other steps are exactly the same as those of the test group;
3) The experimental group and the control group are subjected to static
curing 24h, then the film is removed and put into a 40°C steam curing box for
curing, and the uniaxial unconfined compressive strength test and arsenic
toxicity leaching test are carried out at the age node
. 2. Experimental results
1) The test results of uniaxial unconfined compressive strength are
shown in the following table:
Uniaxial unconfined compressive
Age strength/MPa
Experimental group Control group
3d 0 13.18
7d 12.67 18.83
28d 17.83 24.70
2) The concentration results of arsenic leaching solution of all solid waste
cements in the test group are as follows:
Arsenic leaching concentration/pg/L
Drinking Age Experim Control Detectio water ental group group n limit standard
3d ND 7
7d 12 7 10 4
28d 7 ND
Embodiment 3
The invention relates to a mine gelling agent, which is prepared from the
following raw materials by weight percentage:
Blast furnace slag 45%
Steel slag 10%
Desulfurization gypsum 10%
Sodium hydroxide 35%
The invention relates to a preparation method of mine cement filling
material used for synergetic disposal of arsenious hazardous waste, which is
characterized in that: The milled cementing agent is uniformly mixed with
aggregate, arsenious hazardous waste, water reducing agent and water, and
the specific steps are as follows:
(1) drying the required raw materials, i.e., blast furnace slag, steel slag
and desulfurization gypsum respectively until the moisture content is 0.01-1%,
then milling the blast furnace slag, steel slag and desulfurization gypsum to
the specific surface area of 435m<2>/Kg, 444m<2>/Kg and 360m<2>/Kg
respectively according to the dry basis weight percentage of 45%, 10% and
%, and uniformly mixing 35% of calcium hydroxide according to the dry
basis weight percentage to obtain a cementing agent;
(2) drying the arsenious hazardous wastes until the moisture content is
0.01%-1%, according to the weight ratio of the cementing agent/aggregate of
1/4, adding 1% of polycarboxylic acid water reducing agent, until the mass
fraction of slurry is 84%, and uniformly stirring to obtain the qualified mine
cement filling material.
The toxic leaching result of arsenic in lead-zinc mine tailings is 62pg/L.
Experiment III. The cement filling material prepared in Embodiment 3 for
co-solidifying of arsenious hazardous wastes is subjected to uniaxial infinite
compressive strength test and arsenic toxicity leaching test.
1. Experimental method
1) Experimental group: The filling material described in Embodiment 3 is
injected into a 70.7x70.7x70.7mm standard test mold and shaken with a
shaking table for 30s;
2) Control group: Grade 42.5 cement is used as cementing agent, and
other steps are exactly the same as those of the test group;
3) The experimental group and the control group are subjected to static
curing 24h, then the film is removed and put into a 40°C steam curing box for
curing respectively, and the uniaxial unconfined compressive strength test
and arsenic toxicity leaching test are carried out at the age node
2. Experimental results
1) The test results of uniaxial unconfined compressive strength are
shown in the following table:
Uniaxial unconfined compressive
Age strength/MPa
Experimental group Control group
3d 10.8 6.68
7d 9.56 9.56
28d 12.84 16.75
2) The concentration results of arsenic leaching solution of all solid waste
cements in the test group are as follows:
Arsenic leaching concentration/pg/L
Drinking Age Experim Control Detectio water ental group group n limit standard
3d ND ND 10 4
7d ND 4
28d ND ND
From the compressive strength test results and arsenic leaching
concentration results of tests 1 to 3, it can be seen that the 28-day strength of
the cementing agent solidified body for mine filling provided by the invention
far exceeds the requirement of general mines for filling body strength 3MPa;
The arsenic leaching concentration of solidified body at 28-day age is less
than lOpg/L, which is lower than the limit stipulated by the national drinking
water hygiene standard. The raw materials of the cement filling material used
for synergetic disposal of arsenious hazardous wastes are all solid wastes,
the preparation process is simple, the strength meets the requirements, and
the curing effect of arsenic is excellent, thus it is worthy of popularization and
application.
Lastly, the above preferred embodiments are intended to be illustrative
only and not limiting of the technical solutions of the invention. Although the
invention has been described in detail by way of the above preferred
embodiments, it will be understood by those skilled in the art that various
changes may be made in form and detail without departing from the scope
defined in the claims of the invention.
Claims (6)
1.A mine cement filling material for synergetic disposal of arsenious
hazardous wastes, comprising a cementing agent, an aggregate, a water
reducing agent and arsenious hazardous waste, characterized in that: the
cementing agent comprises 45%-60% of blast furnace slag, 20%-35% of steel
slag and 10%-20% of desulfurization gypsum in weight percentage;
the aggregate comprises one or more of mountain sand, river sand,
tailings or waste rock;
the water reducing agent is one or more of lignosulfonate water reducing
agent, naphthalene series high-efficiency water reducing agent, melamine
series high-efficiency water reducing agent, sulfamate series high-efficiency
water reducing agent, fatty acid series high-efficiency water reducing agent
and polycarboxylate series high-efficiency water reducing agent;
the arsenious hazardous waste is a hazardous solid waste whose
leaching experiment is carried out according to the leaching method specified
in Solid Waste-Extraction Procedure for Leaching Toxicity-Horizontal Vibration
Method (HJ557-2009), and the concentration of arsenic in the leaching
solution exceeds 1Opg/L specified in Standards for Drinking Water Quality
(GB5749-2006).
2. The mine cement filling material for synergetic disposal of arsenious
hazardous wastes according to claim 1, characterized in that calcium
hydroxide is added into the cementing agent to replace part of blast furnace
slag, steel slag and desulfurization gypsum, and the content range of the cementing agent is: 45-50% of blast furnace slag, 10-30% of steel slag, 10-15% of desulfurization gypsum and 10-35% of calcium hydroxide.
3. The mine cement filling material for synergetic disposal of arsenious
hazardous wastes according to claim 1, characterized in that the blast furnace
slag is granular blast furnace slag formed after furnace slag generated in the
ironmaking process of a metallurgical blast furnace is rapidly cooled with
water, and the main chemical composition ranges from: 38%-49% of CaO,
26%-42% of SiO2, 6%-17% of A1203, 1%-13% of MgO, 0.1%-2% of MnO,
0.07%-2.5% of FeO and 0.2%-1.5% of S; other indexes meet the
requirements of Ground Granulated Blast Furnace Slag Used for Cement and
Concrete (GB/T18046-2008).
4. The mine cement filling material for synergetic disposal of arsenious
hazardous wastes according to claim 1, characterized in that the steel slag is
furnace slag produced in the process of steelmaking process, containing 5%
% of tricalcium silicate, 5%-30% of dicalcium silicate (C2S), 10%-38% of
RO phase, 2%-8% of ferric oxide, 0.5%-5% of calcium hydroxide, 0.5%-5% of
ferric hydroxide, 0.01%-3% of free calcium oxide, 0.01%-10% of calcium
carbonate, 0.01%-8% of magnesium carbonate, 0.01%-3% of ferric carbonate
and 0.01%-3% of other impurities; other indexes meet the requirements of
Steel Slag Powder Used for Cement and Concrete (GB/T20491-2006).
5. The mine cement filling material for synergetic disposal of arsenious
hazardous wastes according to claim 1, characterized in that the
desulfurization gypsum can be replaced with industrial by-product gypsum, including one or more of phosphogypsum, fluorogypsum, lemon gypsum and waste pottery mold gypsum.
6. A preparation method for the mine cement filling material for synergetic
disposal of arsenious hazardous wastes according to claim 2, characterized in
that the cementing agent is uniformly mixed with aggregate, arsenious
hazardous wastes, water reducing agent and water, and the specific steps are
as follows:
(1) milling the required raw materials, i.e., blast furnace slag, steel
slag and desulfurization gypsum, with 0.01%-1% of moisture content
according to the dry basis weight percentage of 45%-50% of the blast furnace
slag, 10%-30% of the steel slag and 10%-15% of the desulfurization gypsum,
milling independently or milling by mixed powder until the specific surface
area is 200-600 m<2>/Kg, adding 10%-35% of calcium hydroxide, and
uniformly mixing to obtain a cementing agent;
(2) drying the arsenious hazardous wastes until the moisture
content is 0.01%-1%, according to the weight ratio of the cementing
agent/aggregate of 1/4-1/8, the weight ratio of the arsenious hazardous
wastes/(cementing agent + aggregate) of 1/1000-1/100, adding 0%-1% of
water reducing agent, until the mass fraction of slurry is 65%-86%, and
uniformly stirring to obtain the qualified mine cement filling material.
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| CN114180862A (en) * | 2022-02-16 | 2022-03-15 | 涉县清漳水泥制造有限公司 | Method for preparing solid waste base cementing material through ultra-low carbon and ultra-low emission step grinding |
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