KR102654370B1 - Non-cementitious cured composite composition using industrial by-products with high water content - Google Patents
Non-cementitious cured composite composition using industrial by-products with high water content Download PDFInfo
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- KR102654370B1 KR102654370B1 KR1020230112977A KR20230112977A KR102654370B1 KR 102654370 B1 KR102654370 B1 KR 102654370B1 KR 1020230112977 A KR1020230112977 A KR 1020230112977A KR 20230112977 A KR20230112977 A KR 20230112977A KR 102654370 B1 KR102654370 B1 KR 102654370B1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000006227 byproduct Substances 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title description 2
- 239000010802 sludge Substances 0.000 claims abstract description 124
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 64
- 239000010440 gypsum Substances 0.000 claims abstract description 36
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002893 slag Substances 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 23
- 239000000571 coke Substances 0.000 claims abstract description 19
- 239000004568 cement Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 17
- 239000002699 waste material Substances 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 12
- 239000000446 fuel Substances 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 239000004449 solid propellant Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 28
- 238000002156 mixing Methods 0.000 abstract description 16
- 239000000292 calcium oxide Substances 0.000 abstract description 14
- 235000012255 calcium oxide Nutrition 0.000 abstract description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 9
- 239000000920 calcium hydroxide Substances 0.000 abstract description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract description 9
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002075 main ingredient Substances 0.000 abstract description 2
- 239000002689 soil Substances 0.000 description 18
- 239000002006 petroleum coke Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 238000004064 recycling Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 aluminosilicate compound Chemical class 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910017090 AlO 2 Inorganic materials 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 229910010100 LiAlSi Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010805 inorganic waste Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002023 wood 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
- C04B22/062—Oxides, Hydroxides of the alkali or alkaline-earth metals
- C04B22/064—Oxides, Hydroxides of the alkali or alkaline-earth metals of the alkaline-earth metals
-
- 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
- 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
- C04B18/0436—Dredged harbour or river sludge
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/0006—Waste inorganic materials
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
- C04B22/143—Calcium-sulfate
-
- 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
- C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits type
-
- 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
- C04B28/08—Slag cements
-
- 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
- C04B28/24—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 alkyl, ammonium or metal silicates; containing silica sols
-
- 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
- C04B2103/10—Accelerators; 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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/20—Sludge processing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Civil Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Treatment Of Sludge (AREA)
Abstract
본 발명은 함수율이 높은 산업부산물을 이용한 무시멘트계 경화체 조성물에 관한 것이다.
본 발명의 산업부산물을 이용한 무시멘트계 경화체 조성물은 함수율 50∼95% 상태의 오염 준설 슬러지 및 함수율 25∼45%인 리튬 잔사 슬러지를 포함하는 함수율이 높은 산업부산물을 별도의 중화, 건조, 분쇄 및 분급 공정을 거치지 않고 배출 상태 그대로 사용하면서, 주성분이 생석회와 무수석고 성분으로 구성된 페트로 코크스 탈황석고를 혼합하여 함수율을 저감시키고 pH를 9∼12.5로 조절한 혼합슬러지를 수득하고 상기 혼합슬러지를 고로슬래그 미분말의 알칼리 및 황산염 복합 자극제로 활용하여 강도를 발현시킬 수 있으며, 수분과 반응하여 생성된 수산화칼슘과 석고 성분이 고로슬래그 미분말 및 리튬 잔사 슬러지에 함유된 알루미노실리케이트의 잠재수경성을 이끌어내어 경화체를 제공할 수 있다. The present invention relates to a cement-free cured body composition using industrial by-products with high moisture content.
The cement-free cured body composition using industrial by-products of the present invention is used to separately neutralize, dry, grind and classify industrial by-products with high moisture content, including contaminated dredged sludge with a moisture content of 50 to 95% and lithium residual sludge with a moisture content of 25 to 45%. While using the discharged state without going through the process, mixed sludge with the water content reduced and the pH adjusted to 9 to 12.5 was obtained by mixing petrol coke desulfurized gypsum, the main ingredients of which are quicklime and anhydrous gypsum, and mixing the mixed sludge into blast furnace slag fine powder. Strength can be developed by using it as a complex stimulant of alkali and sulfate, and the calcium hydroxide and gypsum components generated by reaction with moisture can provide a hardened body by deriving the potential hydraulic properties of aluminosilicate contained in blast furnace slag fine powder and lithium residual sludge. You can.
Description
본 발명은 함수율이 높은 산업부산물을 이용한 무시멘트계 경화체 조성물에 관한 것으로서, 더욱 상세하게는 함수율 50∼95% 상태의 오염 준설 슬러지 및 함수율 25∼45%인 리튬 잔사 슬러지를 포함하는 함수율이 높은 산업부산물을 별도의 중화, 건조, 분쇄 및 분급 공정을 거치지 않고 배출 상태 그대로 사용하면서, 주성분이 생석회와 무수석고 성분으로 구성된 페트로 코크스 탈황석고를 혼합하여 함수율을 낮춘 혼합슬러지를 수득하고 상기 혼합슬러지를 고로슬래그 미분말의 알칼리 및 황산염 복합 자극제로 활용하여 강도를 발현시킬 수 있는, 함수율이 높은 산업부산물을 이용한 무시멘트계 경화체 조성물에 관한 것이다. The present invention relates to a cement-free cured body composition using industrial by-products with a high moisture content. More specifically, industrial by-products with a high moisture content including contaminated dredging sludge with a moisture content of 50 to 95% and lithium residual sludge with a moisture content of 25 to 45%. While using the product as discharged without going through separate neutralization, drying, grinding and classification processes, mixed sludge with a lowered water content was obtained by mixing petroleum coke desulfurized gypsum, the main components of which are quicklime and anhydrous gypsum, and the mixed sludge was converted into blast furnace slag. The present invention relates to a cement-free cured body composition using an industrial by-product with a high water content that can be used as a fine powder alkali and sulfate complex stimulant to develop strength.
매년 항만 건설 및 유지를 위한 해양 퇴적물의 준설이 활발히 수행되고 있으며, 국내의 준설사업은 골재 채취를 위한 준설과 항로 정비의 목적으로 퇴적토를 준설하거나 유기물, 영양 염류, 중금속 등으로 오염된 퇴적물을 준설하여 수질을 개선하기 위한 목적으로 이루어졌다. Dredging of marine sediments for port construction and maintenance is actively carried out every year. Domestic dredging projects dredge sediments for the purpose of dredging for collecting aggregates and maintaining ports, or dredging sediments contaminated with organic matter, nutrient salts, and heavy metals. This was done with the purpose of improving water quality.
그러나 골재 채취를 위한 준설을 제외하고는 대부분의 준설물질은 응집/침전 후 탈수한 다음 대부분 육상에 단순 매립되고 있으며, 오염된 준설 퇴적물 또한 폐기물 관리법상의 유해물질 함유 기준을 초과하는 폐기물(폐기물 분류번호 51-21-03, 오염하천·오염해양 준설토)로 분류되어 대부분 매립되고 있는 실정이나 오염된 준설 물질을 매립할 수 있는 부지가 부족하다는 문제에 당면해 있다. However, except for dredging for aggregate collection, most dredged materials are dehydrated after coagulation/sedimentation and are then simply buried on land. Contaminated dredged sediments are also wastes that exceed the hazardous substance content standards under the Waste Management Act (waste classification no. 51-21-03, polluted rivers, polluted oceans, and dredged soil) and are mostly being reclaimed, but we are facing the problem of a lack of land where contaminated dredged materials can be buried.
또한, 함수율이 높은 오염 준설물질의 육상 매립과정에서 침출수가 발생하거나 악취와 벌레가 발생하여 주민들의 민원을 야기하는 것도 큰 문제이다.In addition, it is a major problem that leachate is generated during land reclamation of contaminated dredged material with high moisture content, or foul odors and insects are generated, causing complaints from residents.
준설토에 관한 법적인 규제사항을 보면 "폐기물 관리법 시행규칙 별표 1" 및 "토양환경보전법 시행규칙 별표3"의 기준치를 초과하는 경우는 "폐기물 관리법 시행규칙 별표 5에"에 따라 고화재로 고형화 처리하거나 수분함량 85% 이하로 안정화 처리하여 지정폐기물 매립가능한 관리형 매립시설에 매립하여야 한다.According to the legal regulations regarding dredged soil, if it exceeds the standards of "Appendix 1 of the Enforcement Rules of the Waste Management Act" and "Appendix 3 of the Enforcement Rules of the Soil Environment Conservation Act", it must be solidified or treated with solidification material in accordance with "Appendix 5 of the Enforcement Rules of the Waste Management Act". It must be stabilized to a moisture content of 85% or less and buried in a managed landfill facility capable of being buried as designated waste.
이런 실정에서 오염 준설토를 재활용하는 기술이 연구되고 있는데 이들 기술의 대부분은 포틀랜드 시멘트에 기포제나 계면활성제, EPS beads 등을 준설토와 혼합하여 경량화하면서 고형화시키는 방법을 제시하고 있다. In this situation, technologies for recycling contaminated dredged soil are being researched, and most of these technologies suggest a method of mixing Portland cement with foaming agents, surfactants, and EPS beads with dredged soil to lighten the weight and solidify it.
그 일례로 특허문헌 1에는 준설토에 시멘트를 이용하여 기반층을 조성하고 기포 혼합경량토 및 타이어 혼합경량토를 제조하는 준설토를 이용한 경량혼합토를 이용한 연약지반 개량 방법이 개시하고 있다.As an example, Patent Document 1 discloses a method of improving soft ground using lightweight mixed soil using dredged soil, which creates a base layer using cement in dredged soil and produces foam mixed lightweight soil and tire mixed lightweight soil.
또한, 특허문헌 2에는 준설토와 물을 혼합하여 슬러리를 제조한 후 시멘트를 상기 슬러리와 혼합하며, 용해성 실리케이트, 벤토나이트 또는 석회를 상기 슬러리에 첨가하는 단계와 상기 시멘트가 혼합된 슬러리에 기포제를 혼합하는 단계를 가지는 기포혼합처리토 제조방법 및 제조 장치가 개시되고 있다. In addition, Patent Document 2 includes the steps of mixing dredged soil and water to prepare a slurry, mixing cement with the slurry, adding soluble silicate, bentonite, or lime to the slurry, and mixing a foaming agent into the slurry mixed with cement. A method and apparatus for producing mixed foam treated soil having steps are disclosed.
또한, 특허문헌 3에는 시멘트를 주재료로 이용하고 생석회와 석고와 알루미나 분말을 이용한 준설토용 고화제가 개시되어 있다. In addition, Patent Document 3 discloses a solidifying agent for dredged soil using cement as the main material and quicklime, gypsum, and alumina powder.
1종 포틀랜드 시멘트 제조 시 이산화탄소의 배출량은 석회석의 하소 단계에서 약 0.50톤, 화석 연료의 연소를 통한 소성 공정에서 약 0.40톤으로서 결국 1톤의 시멘트를 생산할 때마다 약 0.9톤의 이산화탄소를 배출하게 된다. 따라서 향후 온실가스 감축은 시멘트 업계의 가장 큰 현안으로 등장할 것이다. The amount of carbon dioxide emitted during the production of type 1 Portland cement is approximately 0.50 tons in the limestone calcination stage and approximately 0.40 tons in the calcination process through combustion of fossil fuels, which ultimately results in the emission of approximately 0.9 tons of carbon dioxide for each ton of cement produced. . Therefore, reducing greenhouse gases will emerge as the biggest issue in the cement industry in the future.
따라서, 시멘트의 사용량을 최소화할 수 있는 기술 개발이 시급한 실정이며, 이에 대한 대응방안으로 시멘트의 양을 최소화하고 다양한 산업부산물을 이용하여 시멘트와 동등 수준의 성능 발휘가 가능한 결합재를 제조할 수 있다면 생산원가 절감은 물론 천연자원 및 에너지 고갈 문제와 이산화탄소 배출에 의한 환경오염 문제를 동시에 해결할 수 있을 것으로 예상된다.Therefore, there is an urgent need to develop technology that can minimize the amount of cement used, and as a response to this, it is possible to minimize the amount of cement and manufacture a binder that can perform at the same level as cement by using various industrial by-products. It is expected that it will not only reduce costs, but also solve the problems of natural resource and energy depletion and environmental pollution caused by carbon dioxide emissions.
한편, 리튬은 이차전지용 소재로, 하이브리드 및 전기 자동차의 동력원으로 그 중요성이 최근 대두되고 있으며, 향후 시장 규모는 현재 대비 100배 이상 성장할 것으로 예상되고 있다. 리튬 광석 내 리튬은 약 2∼3% 정도 함유되어 있어, 리튬 추출 후 상당량의 맥석(脈石)이 남게 된다. 예를 들어, 리튬 광석 100만톤을 취급하여 이로부터 2∼3%의 리튬을 추출하고 나면, 잔여 부산물은 97∼98만톤이 남게 된다.Meanwhile, lithium is a material for secondary batteries and its importance as a power source for hybrid and electric vehicles has recently emerged, and the future market size is expected to grow more than 100 times compared to the current size. Lithium ore contains about 2-3% lithium, so a significant amount of gangue remains after lithium extraction. For example, after handling 1 million tons of lithium ore and extracting 2 to 3% of lithium from it, 970,000 to 980,000 tons of residual by-products remain.
그럼에도 불구하고 국내외 기술로 리튬 정광(精鑛)으로부터 리튬을 추출하는 기술 개발은 활발하나, 리튬 추출 후 부산물을 재활용하기 위한 연구 사례는 미흡한 실정이다.Nevertheless, although there is active development of technology to extract lithium from lithium concentrate using domestic and foreign technologies, research cases for recycling by-products after lithium extraction are insufficient.
따라서 리튬 추출 후 부산물을 재활용할 수 있는 효과적인 방법이 제공된다면, 관련 분야에서 경제적 효과를 극대화할 수 있고 더불어 산업부산물을 이용한 순환자원으로의 가치를 높일 수 있다. Therefore, if an effective method to recycle by-products after lithium extraction is provided, economic effects can be maximized in related fields and the value of industrial by-products as circular resources can be increased.
종래의 리튬 추출 후 부산물의 재활용 방안으로서, 특허문헌 4에는 기존 시멘트를 대체하여 리튬 잔사를 사용한 무시멘트계 결합재가 개시되어 있으며, 구체적으로는 pH가 산성인 리튬 잔사를 수세 처리하여 pH를 중성 범위로 조절한 후 이를 건조, 분쇄 및 분급 등의 전처리하고, 상기 리튬 잔사 입도를 0.075㎜ 이하로 조절한 후 수산화나트륨, 수산화칼륨, 수산화칼슘, 수산화마그네슘 등의 알카리 자극제와 혼합하는 공정으로 수행됨으로써, 전처리공정에 따른 비용 증가로 인해 산업부산물의 재활용에 따른 경제적 절감의 효과와는 상충된다. As a method of recycling by-products after conventional lithium extraction, Patent Document 4 discloses a cement-free binder using lithium residue as a replacement for existing cement. Specifically, lithium residue with an acidic pH is washed with water to bring the pH to a neutral range. After adjusting, it is pretreated by drying, grinding, and classifying, and the particle size of the lithium residue is adjusted to 0.075 mm or less, and then mixed with an alkali stimulant such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide. This is a pretreatment process. The resulting cost increase conflicts with the effect of economic savings resulting from recycling of industrial by-products.
특허문헌 5에는 리튬 추출 공정 부산물을 이용한 포졸란 시멘트 조성물에 관한 발명으로서, 리튬 추출 공정에서 발생하는 알루미노실리케이트 화합물(Al-Si-O)을 포함하는 부산물을 건조하는 단계; 상기 건조된 부산물을 분말화하는 단계; 상기 분말화된 부산물을 규사 분말, 실리카퓸 또는 이들의 혼합물과 혼합하여 실리카질 혼합재를 제조하는 단계; 및 상기 실리카질 혼합재를 보통 포틀랜드 시멘트(Ordinary Portland Cement)와 중량비로 3:7 내지 1:9로 혼합하는 단계;를 포함하여 포졸란 시멘트 조성물을 완성한다. Patent Document 5 is an invention regarding a pozzolan cement composition using a by-product of a lithium extraction process, comprising the steps of drying a by-product containing an aluminosilicate compound (Al-Si-O) generated in the lithium extraction process; Powdering the dried by-product; Mixing the powdered by-product with silica sand powder, silica fume, or a mixture thereof to produce a siliceous mixture; And mixing the siliceous mixture with Ordinary Portland Cement in a weight ratio of 3:7 to 1:9 to complete the pozzolan cement composition.
상기 발명 역시 리튬 추출 공정 후 건조, 분말화 공정을 포함하고 있는데, 리튬 추출 후 부산물의 경우, 습식 공정을 거쳐 함수율이 25∼35%일 수 있으므로, 함수율 3% 이하가 되도록 건조하는 단계 수행이 필수적이며, 이후 상기 건조된 부산물을 분말화 단계를 포함하고 있어, 여전히 리튬 추출 공정 후 다단계의 전처리공정이 요구되어, 재활용 비용이 상승되는 문제점이 제기되고 있다.The above invention also includes a drying and powdering process after the lithium extraction process. In the case of by-products after lithium extraction, the moisture content may be 25 to 35% through a wet process, so it is essential to perform a drying step to reduce the moisture content to 3% or less. Since it includes a step of powdering the dried by-product, a multi-step pretreatment process is still required after the lithium extraction process, raising the problem of increased recycling costs.
이에, 본 발명자들은 종래 함수울이 높은 산업부산물의 재활용시 수반되는 문제점을 해소하기 위하여 노력한 결과, 별도의 중화, 건조, 분쇄 및 분급 공정을 거치지 않고 함수율이 높은 함수율 50∼95% 상태의 오염 준설 슬러지와 함수율 25∼45%인 리튬 잔사 슬러지를 배출 상태 그대로 사용하면서 주성분이 생석회와 무수석고 성분으로 구성된 페트로 코크스 탈황석고와 혼합하여 함수율을 낮춘 혼합슬러지를 수득하고 상기 혼합슬러지를 고로슬래그 미분말의 알칼리 및 황산염 복합 자극제로 활용하여 강도 발현을 확인함으로써, 본 발명을 완성하였다. Accordingly, the present inventors have made efforts to solve the problems accompanying the recycling of industrial by-products with high moisture content, and as a result, dredging contamination with a high moisture content of 50 to 95% without going through separate neutralization, drying, grinding, and classification processes. Sludge and lithium residual sludge with a water content of 25 to 45% are used as discharged and mixed with petroleum coke desulfurized gypsum, the main components of which are quicklime and anhydrous gypsum, to obtain mixed sludge with reduced water content, and the mixed sludge is mixed with the alkali of blast furnace slag fine powder. The present invention was completed by confirming the strength development by using a sulfate complex stimulant.
본 발명의 목적은 별도의 중화, 건조, 분쇄 및 분급 공정을 거치지 않고 함수율이 높은 오염 준설 슬러지와 리튬 잔사 슬러지를 배출 상태 그대로 사용하면서 강도를 발현한 무시멘트계 경화체 조성물을 제공하는 것이다. The purpose of the present invention is to provide a cement-free cured body composition that exhibits strength while using contaminated dredged sludge and lithium residual sludge with high moisture content in their discharged state without undergoing separate neutralization, drying, grinding, and classification processes.
상기 목적을 달성하기 위하여, 본 발명은 함수율 50∼95% 상태의 오염 준설 슬러지 및 황산을 이용한 리튬 추출 공정에서 발생하는 함수율 25∼45%인 리튬 잔사 슬러지를 포함하는 함수율이 높은 산업부산물에, 페트로 코크스를 연료로 사용하는 순환 유동층 보일러에서 배출되는 CaO 함량이 40∼70중량%, SO3 함량이 20∼35중량%인 페트로 코크스 탈황석고를 혼합하여 함수율을 낮춘 혼합슬러지 100 중량부에 대하여, 고로슬래그 미분말 10∼300중량부를 포함한 산업부산물을 이용한 무시멘트계 경화체 조성물을 제공한다. In order to achieve the above object, the present invention provides industrial by-products with high moisture content, including contaminated dredged sludge with a moisture content of 50 to 95% and lithium residual sludge with a moisture content of 25 to 45% generated in a lithium extraction process using sulfuric acid, For 100 parts by weight of mixed sludge whose water content was lowered by mixing petrol coke desulfurized gypsum with a CaO content of 40 to 70% by weight and an SO 3 content of 20 to 35% by weight discharged from a circulating fluidized bed boiler using coke as fuel, the blast furnace Provided is a cement-free hardened body composition using industrial by-products containing 10 to 300 parts by weight of slag fine powder.
본 발명에서 사용되는 상기 오염 준설 슬러지와 리튬 잔사 슬러지는 별도의 중화, 건조, 분쇄 및 분급 공정을 거치지 않고 배출 상태 그대로 사용된 것을 특징으로 한다. The contaminated dredging sludge and lithium residual sludge used in the present invention are characterized in that they are used in their discharged state without undergoing separate neutralization, drying, grinding, and classification processes.
이때, 배출 상태 그대로 사용된 리튬 잔사 슬러지는 함수율 25∼45% 및 pH 2∼6이고, 페트로 코크스 탈황석고와의 혼합반응 후 얻어진 혼합슬러지는 함수율 20∼40% 및 pH 9∼12.5로 조절된다. At this time, the lithium residual sludge used as discharged has a water content of 25 to 45% and a pH of 2 to 6, and the mixed sludge obtained after the mixing reaction with petroleum coke desulfurized gypsum is adjusted to a water content of 20 to 40% and pH of 9 to 12.5.
본 발명의 산업부산물을 이용한 무시멘트계 경화체 조성물에 있어서, 혼합슬러지는 상기 오염 준설 슬러지 100중량부에 대하여, 상기 리튬 잔사 슬러지 5∼100중량부 및 상기 페트로 코크스 탈황석고 10∼300중량부가 혼합된 것이다. In the cement-free hardened body composition using industrial by-products of the present invention, the mixed sludge is a mixture of 5 to 100 parts by weight of the lithium residual sludge and 10 to 300 parts by weight of the petrol coke desulfurized gypsum with respect to 100 parts by weight of the contaminated dredged sludge. .
본 발명의 산업부산물을 이용한 무시멘트계 경화체 조성물은 상기 오염 준설 슬러지 100중량부에 대하여, 고형연료를 연료로 사용하는 순환 유동층 보일러 하부에서 배출되는 폐유동사 10∼100중량부를 더 포함할 수 있다. The cement-free cured body composition using industrial by-products of the present invention may further include 10 to 100 parts by weight of waste fluid sand discharged from the lower part of a circulating fluidized bed boiler using solid fuel as fuel, based on 100 parts by weight of the contaminated dredging sludge.
또한, 초기강도를 증진시키기 위하여, 상기 혼합슬러지 100중량부에 대하여, 1종 시멘트를 10∼100중량부 더 포함할 수 있다. Additionally, in order to improve the initial strength, 10 to 100 parts by weight of type 1 cement may be further included based on 100 parts by weight of the mixed sludge.
본 발명은 오염 준설 슬러지와 리튬 잔사 슬러지를 포함하는 함수율이 높은 산업부산물을 사용하되 종래 시멘트를 이용한 준설방안 대신에, 페트로 코크스를 연료로 사용하는 순환 유동층 보일러에서 배출되는 페트로 코크스 탈황석고를 혼합하고, 이를 고로슬래그 미분말의 알칼리 및 황산염 복합 자극제로 활용하여 강도를 발현한 무시멘트계 경화체 조성물을 제공할 수 있다. The present invention uses industrial by-products with a high moisture content, including contaminated dredging sludge and lithium residual sludge, but instead of the conventional dredging method using cement, it mixes petroleum coke desulfurized gypsum discharged from a circulating fluidized bed boiler using petroleum coke as fuel. , it is possible to provide a cement-free hardened body composition that exhibits strength by using this as a combined alkali and sulfate stimulant of blast furnace slag fine powder.
즉, 오염 준설 슬러지를 경화시키기 위해서는 다량의 시멘트가 투입되어야 하나 본 발명에서는 오염 준설 슬러지와 리튬 잔사 슬러지를 포함하는 함수율이 높은 산업부산물에 주성분이 생석회와 무수석고 성분으로 구성된 페트로 코크스 탈황석고의 혼합에 의해, 산성 물질인 리튬 잔사 슬러지의 알칼리화 및 함수율 저감시키고, 수분과 반응하여 생성된 수산화칼슘 성분이 고로슬래그 미분말 및 리튬 잔사 슬러지에 함유된 알루미노실리케이트의 잠재수경성을 이끌어내어 경화체를 형성할 수 있다.In other words, a large amount of cement must be added to harden the contaminated dredged sludge, but in the present invention, industrial by-products with a high water content including contaminated dredged sludge and lithium residual sludge are mixed with petro-coke desulfurized gypsum, which mainly consists of quicklime and anhydrous gypsum. By this, the lithium residue sludge, which is an acidic substance, is alkalized and the moisture content is reduced, and the calcium hydroxide component produced by reacting with moisture induces the potential hydraulic properties of the aluminosilicate contained in the blast furnace slag fine powder and the lithium residue sludge to form a hardened body. .
특히, 본 발명의 함수율이 높은 산업부산물인 오염 준설 슬러지와 리튬 잔사 슬러지는 별도의 중화, 건조, 분쇄 및 분급 공정을 거치지 않고 배출 상태 그대로 사용함으로써, 전처리공정 수행에 따른 비용을 절감하고, 산업부산물을 대량 활용할 수 있다. In particular, the contaminated dredging sludge and lithium residual sludge, which are industrial by-products with high moisture content of the present invention, are used as discharged without going through separate neutralization, drying, grinding, and classification processes, thereby reducing the cost of performing the pretreatment process and reducing industrial by-products. can be utilized in large quantities.
이하, 본 발명을 상세히 설명한다. Hereinafter, the present invention will be described in detail.
본 발명은 함수율 50∼95% 상태의 오염 준설 슬러지 및 The present invention is a contaminated dredged sludge with a moisture content of 50 to 95% and
황산을 이용한 리튬 추출 공정에서 발생하는 함수율 25∼45%인 리튬 잔사 슬러지를 포함하는 함수율이 높은 산업부산물에, Industrial by-products with high moisture content, including lithium residual sludge with a moisture content of 25 to 45% generated in the lithium extraction process using sulfuric acid,
페트로 코크스를 연료로 사용하는 순환 유동층 보일러에서 배출되는 CaO 함량이 40∼70중량%, SO3 함량이 20∼35중량%인 페트로 코크스 탈황석고를 혼합하여 함수율을 낮춘 혼합슬러지 100 중량부에 대하여, Regarding 100 parts by weight of mixed sludge of which the water content was lowered by mixing petrol coke desulfurized gypsum with a CaO content of 40 to 70% by weight and an SO 3 content of 20 to 35% by weight discharged from a circulating fluidized bed boiler using petrol coke as fuel,
고로슬래그 미분말 10∼300중량부를 포함한 산업부산물을 이용한 무시멘트계 경화체 조성물을 제공한다. A cementless hardened body composition using industrial by-products containing 10 to 300 parts by weight of blast furnace slag fine powder is provided.
1) 오염 준설 슬러지1) Contaminated dredging sludge
상기 오염 준설 슬러지는 하천, 하수, 해양 등의 준설 과정 중에 발생되며, 응집 탈수 처리된 경우 함수율이 55∼68%, 응집 탈수 처리가 안된 경우에는 함수율이 87∼95%의 고함수 상태이고, 사업장 일반폐기물(분류번호 51-21-03, 오염하천, 오염해양 준설토)로 배출된다. The contaminated dredging sludge is generated during the dredging process of rivers, sewage, oceans, etc., and has a high moisture content of 55 to 68% when coagulated and dehydrated, and 87 to 95% when not coagulated and dehydrated. It is discharged as general waste (classification number 51-21-03, polluted rivers, polluted oceans and dredged soil).
본 발명은 상기 오염 준설 슬러지를 별도의 중화, 건조, 분쇄 및 분급 공정을 거치지 않고 배출 상태 그대로 사용한다. The present invention uses the contaminated dredged sludge as it is discharged without undergoing separate neutralization, drying, grinding, and classification processes.
폐기물 관리법상 폐기물의 재활용 유형별 세부 분류 상 R-7인 토양이나 공유수면 등에 성토재ㆍ복토재ㆍ도로기층재ㆍ채움재 등으로는 재활용이 불가능하고 R-4-2인 골재, 저강도 콘크리트 등의 경화체 형태로 활용 가능하다. According to the detailed classification of waste by recycling type under the Waste Management Act, recycling is not possible in the form of fill materials, cover materials, road base materials, fill materials, etc. in soil or public waters that are R-7, and in the form of hardened materials such as aggregate and low-strength concrete that are R-4-2. It can be used as
2) 리튬 잔사 슬러지2) Lithium residual sludge
상기 리튬 잔사 슬러지는 일반적으로 주 광물상인 스포듀민(LiAlSi2O6)의 리튬 함유 광석을 900∼1,400℃의 열처리, 미분쇄 및 황산 배소 공정에 의해 광석의 Li+ 이온 자리에 황산으로부터 해리된 H+ 이온으로 이온교환되고, 상기 이온교환된 Li+ 이온이 해리된 SO4 2- 이온과 결합하고, 석출반응이 진행되어 황산리튬(Li2SO4)으로 석출될 수 있다. 석출된 황산리튬(Li2SO4)을 물을 이용하여 침출시킨 다음 고액 분리하면, 황산리튬과 잔여 부산물이 남게 된다. 즉, 황산리튬(Li2SO4)은 물에 용해되어 침출되는 반면, 알루미노실리케이트(Al2O3 4SiO2, AlSi2O6)는 물에 용해되지 않고, 고체 화합물 형태로 잔류하게 되는 것이다. The lithium residual sludge is generally made by heat-treating lithium-containing ore of spodumene (LiAlSi 2 O 6 ), which is the main mineral phase, at 900 to 1,400°C, pulverizing, and sulfuric acid roasting, and H dissociated from sulfuric acid in the Li + ion site of the ore. + ions are exchanged, and the ion-exchanged Li + ions combine with the dissociated SO 4 2- ions, and a precipitation reaction proceeds to precipitate lithium sulfate (Li 2 SO 4 ). When the precipitated lithium sulfate (Li 2 SO 4 ) is leached using water and then separated into solid and liquid, lithium sulfate and remaining by-products remain. In other words, lithium sulfate (Li 2 SO 4 ) dissolves in water and is leached, while aluminosilicate (Al 2 O 3 4SiO 2 , AlSi 2 O 6 ) does not dissolve in water and remains in the form of a solid compound. .
황산을 이용한 리튬 침출 단계를 거쳐 고액 분리에 의해 함수율 약 25∼45%인 리튬 잔사 슬러지가 사업장 일반 폐기물(분류번호 51-02-19, 그 밖의 공정오니 또는 51-02-99, 그 밖의 무기성오니 등)로 배출된다. After a lithium leaching step using sulfuric acid, lithium residual sludge with a water content of about 25-45% is separated into solid-liquid, and is collected as general waste from the workplace (classification number 51-02-19, other process sludge, or 51-02-99, other inorganic waste). sludge, etc.).
황산을 이용한 리튬 침출 단계를 거쳐 고액 분리에 의해 함수율 약 25∼45%인 상태로 배출되고, 상기 리튬 침출 단계에서 황산을 이용하기 때문에 수 침출시에 미반응 상태로 남아 있던 황산이 용해되어 잔류하기 때문에 리튬 잔사 슬러지는 pH 2∼6의 산성을 띈다. After going through the lithium leaching step using sulfuric acid, it is discharged with a moisture content of about 25 to 45% through solid-liquid separation. Since sulfuric acid is used in the lithium leaching step, the sulfuric acid that remained unreacted during water leaching is dissolved and remains. Therefore, lithium residue sludge has an acidic pH of 2 to 6.
본 발명에서 사용되는 산성의 리튬 잔사 슬러지를 별도의 중화, 건조, 분쇄 및 분급 공정을 거치지 않고 배출 상태 그대로 사용된 것을 특징으로 한다. 이때, 본 발명에서 배출 상태 그대로 사용된 리튬 잔사 슬러지는 함수율 25∼45% 및 pH 2∼6인 것이다. The acidic lithium residual sludge used in the present invention is characterized in that it is used in its discharged state without undergoing separate neutralization, drying, grinding, and classification processes. At this time, the lithium residual sludge used in the present invention as discharged has a water content of 25 to 45% and a pH of 2 to 6.
3) 페트로 코크스 탈황석고3) Petrocoke desulfurized gypsum
상기 페트로 코크스 탈황석고는 석유 정제 부산물인 페트로 코크스를 연료로 사용하는 보일러에서 노내 탈황을 위해 석회석을 혼소하는 과정에서 페트로 코크스에 포함되어 있는 황 성분과 석회석이 고온에서 탈탄산된 CaO 성분이 반응하여 CaO 및 CaSO4 형태로 생성된 분진과 같은 입자상 생석회 및 무수석고의 복합물질이다. 최근에는, SOx 대기 규제 강화로 후단 공정에 중탄산나트륨과 추가 반응을 통해 CaO, CaSO4 성분 외에 Na2SO4 성분이 소량 포함되어 배출되기도 한다. 이때, 본 발명에서 사용되는 페트로 코크스 탈황석고는 CaO 함량 40∼70중량% 및 SO3 함량 20∼35중량%를 포함하는 것을 특징으로 한다.The petroleum coke desulfurization gypsum is made by co-firing limestone for in-furnace desulfurization in a boiler using petroleum coke, a by-product of petroleum refining, as fuel. The sulfur component contained in the petroleum coke reacts with the CaO component decarboxylated from the limestone at high temperature. It is a composite material of dust-like granular quicklime and anhydrous gypsum produced in the form of CaO and CaSO 4 . Recently , due to the strengthening of SO At this time, the petroleum coke desulfurized gypsum used in the present invention is characterized by containing a CaO content of 40 to 70% by weight and an SO 3 content of 20 to 35% by weight.
따라서, 함수율이 높은 오염 준설 슬러지와 리튬 잔사 슬러지에 주성분이 생석회와 무수석고 성분을 다량 함유된 페트로 코크스 탈황석고를 혼합하면, 수분과 반응 시 발열 반응과 함께 수산화칼슘이 생성되면서 오염 준설 슬러지와 리튬 잔사 슬러지의 수분이 급격하게 저감하여 함수율 20∼40%가 되고, 리튬 잔사 슬러지에 잔존하는 황산 성분은 수산화칼슘 성분과 반응하여 석고 형태로 전이되게 되며 pH 또한 약 9∼12.5의 알칼리성을 띄게 된다. Therefore, when polluted dredged sludge with high water content and lithium residue sludge are mixed with petroleum coke desulfurized gypsum, which contains a large amount of quicklime and anhydrous gypsum as the main ingredients, calcium hydroxide is generated along with an exothermic reaction when reacting with moisture, which causes the contaminated dredged sludge and lithium residue. The moisture in the sludge decreases rapidly to a water content of 20-40%, and the sulfuric acid component remaining in the lithium residue sludge reacts with the calcium hydroxide component and is converted to gypsum, and the pH also becomes alkaline at about 9-12.5.
또한, 함수율이 높은 오염 준설 슬러지와 리튬 잔사 슬러지를 포함하는 산업부산물에, 상기 페트로 코크스 탈황석고를 혼합한 혼합슬러지의 경우, 준설토 + 알루미노실리케이트 + 수산화칼슘 + 석고 성분이 복합적으로 함유된 물질로 존재하게 된다.In addition, in the case of mixed sludge where the petrol coke desulfurized gypsum is mixed with industrial by-products including contaminated dredged sludge and lithium residual sludge with high moisture content, it exists as a material containing a complex of dredged soil + aluminosilicate + calcium hydroxide + gypsum components. I do it.
상기 수분과 반응하여 생성된 수산화칼슘 성분이 리튬 잔사 슬러지 성분인 알루미노실리케이트 화합물은 잠재수경성 발현을 유도한다. 구체적으로, 상기 알루미노실리케이트 화합물은 수산화칼슘 성분의 OH- 이온이 의해 불투수성 피막이 파괴되면서 불투수성 피막에 의해 용출되지 못하던 SiO4 - 와 AlO2- 이온이 수용액 중으로 용출된다. 수용액 중으로 용출된 SiO4 - 와 AlO2- 이온이 Ca(OH)2와 반응하여, C-S-H gel 또는 C-A-H gel 불용성 염을 형성함으로써 강도가 발현된다. The aluminosilicate compound, in which the calcium hydroxide component produced by reacting with the moisture is a lithium residual sludge component, induces the development of latent hydraulic properties. Specifically, in the aluminosilicate compound, the impermeable film is destroyed by the OH - ions of the calcium hydroxide component, and SiO 4 - and AlO 2 - ions that were not eluted by the impermeable film are eluted into the aqueous solution. Strength is developed when SiO 4 - and AlO 2 - ions eluted into an aqueous solution react with Ca(OH) 2 to form CSH gel or CAH gel insoluble salt.
4) 고로슬래그 미분말4) Blast furnace slag fine powder
본 발명의 경화체 조성물은 상기 함수율이 높은 오염 준설 슬러지+리튬 잔사 슬러지에 페트로 코크스 탈황석고 혼합물을 최소 약 30분 이상 방치시켜 안정적인 화학 반응이 이루어지도록 하여 혼합슬러지를 수득하고, 이후 고로슬래그 미분말을 추가로 투입하여 균질하게 기계적 교반을 실시하는 것이 바람직하다.The hardened body composition of the present invention is obtained by leaving the petrol coke desulfurized gypsum mixture in the contaminated dredged sludge + lithium residual sludge with high moisture content for at least about 30 minutes to achieve a stable chemical reaction to obtain mixed sludge, and then adding blast furnace slag fine powder. It is desirable to mechanically stir the mixture uniformly.
상기 고로슬래그 미분말은 제철 고로 공정에서 부산물로 발생하는 고온 용융상태의 슬래그를 물로 급냉 처리한 부산물을 미분쇄한 물질이다. 고로슬래그 미분말은 물과 접촉하면 비결정질 피막이 형성되어 스스로 수화반응을 하지 않기 때문에 고로슬래그 미분말을 잠재수경성물질이라 한다. The blast furnace slag fine powder is a material obtained by finely pulverizing the by-product of high-temperature molten slag generated as a by-product in the steel blast furnace process and quenched with water. When blast furnace slag fine powder comes in contact with water, an amorphous film is formed and it does not undergo a hydration reaction on its own, so the blast furnace slag fine powder is called a latent hydraulic material.
따라서, 고로슬래그 미분말에 물을 투입하게 되면, 표면에 비결정질 피막이 형성되어, 내부의 Ca2+, Al3+ 등의 이온 용출이 이루어지지 않는다. 그러나 상기 리튬 잔사 슬러지+페트로 코크스 탈황석고 혼합물에 존재하는 Ca(OH)2, CaSO4 및 CaSO4·2H2O 성분이 물과 접촉 후 고로슬래그 미분말의 알칼리 및 황산염 복합 자극 효과에 의해 강도를 발현하게 할 수 있다. 이때, OH-와 SO4 2- 이온이 고로슬래그 미분말의 비결정질 피막을 파괴하여 Ca2+, Al3+ 등의 용출이 용이하게 되고, 용출 이온들이 CaO-SiO2-H2O계 수화물 등을 생성하게 됨으로써 강도를 발현시키고, 잉여 황산화물은 침상형의 구조를 가지는 에트린가이트 수화생성물(3CaO·Al2O3·3CaSO4·32H2O)을 생성시킴으로써 수화체 내부의 조직을 더욱 치밀화하여 경화체의 압축강도를 향상시킬 수 있다. Therefore, when water is added to the blast furnace slag fine powder, an amorphous film is formed on the surface, preventing the elution of internal ions such as Ca 2+ and Al 3+ . However, after the Ca(OH) 2 , CaSO 4 , and CaSO 4· 2H 2 O components present in the lithium residue sludge + petro coke desulfurized gypsum mixture come in contact with water, their strength is developed by the combined stimulation effect of alkali and sulfate of blast furnace slag fine powder. You can do it. At this time, OH - and SO 4 2 - ions destroy the amorphous film of blast furnace slag fine powder, making it easy to elute Ca 2+ , Al 3+ , etc., and the eluted ions form CaO-SiO 2 -H 2 O-based hydrates, etc. By producing this, strength is expressed, and the excess sulfur oxide further densifies the structure inside the hydrated body by generating ettringite hydration product (3CaO·Al 2 O 3 ·3CaSO 4 ·32H 2 O) with a needle-like structure. The compressive strength of the hardened body can be improved.
본 발명에서 사용하는 고로슬래그 미분말은 비표면적 3,000cm2/g 이상의 일반적으로 시중에서 유통되는 제품이면 사용이 가능하다.The blast furnace slag fine powder used in the present invention can be any commercially available product with a specific surface area of 3,000 cm 2 /g or more.
본 발명의 산업부산물을 이용한 무시멘트계 경화체 조성물에 있어서, 상기 혼합슬러지 중량부에 대하여, 고로슬래그 미분말 10∼300중량부를 포함하는 것이 바람직하다. 이때, 상기 고로슬래그 미분말이 10 중량부 미만이면, 강도 발현이 어렵고 300 중량부를 초과하게 되면 상대적으로 알칼리 및 황산염 복합 자극제의 양이 부족하여 오히려 급격히 강도가 저하하게 된다. In the cement-free hardened body composition using the industrial by-product of the present invention, it is preferable to include 10 to 300 parts by weight of blast furnace slag fine powder relative to the mixed sludge. At this time, if the blast furnace slag fine powder is less than 10 parts by weight, it is difficult to develop strength, and if it exceeds 300 parts by weight, the amount of the alkali and sulfate complex stimulant is relatively insufficient, so the strength decreases sharply.
또한, 본 발명의 산업부산물을 이용한 무시멘트계 경화체 조성물에 있어서, 혼합슬러지는 상기 오염 준설 슬러지 100중량부에 대하여, 상기 리튬 잔사 슬러지 5∼100중량부 및 상기 페트로 코크스 탈황석고 10∼300중량부가 혼합된 것이다. In addition, in the cement-free hardened body composition using the industrial by-product of the present invention, the mixed sludge is a mixture of 5 to 100 parts by weight of the lithium residual sludge and 10 to 300 parts by weight of the petrol coke desulfurized gypsum, based on 100 parts by weight of the contaminated dredged sludge. It has been done.
상기 오염 준설 슬러지 100중량부에 대하여, 리튬 잔사 슬러지가 5중량부 미만으로 함유되면, 강도 발현이 어렵고 100중량부 초과일 경우 강도는 증가하나 오염 준설 슬러지의 재활용 의미가 퇴색하게 되는 문제가 있다. If the lithium residual sludge is contained in less than 5 parts by weight relative to 100 parts by weight of the contaminated dredged sludge, it is difficult to develop strength, and if it exceeds 100 parts by weight, the strength increases, but the meaning of recycling the contaminated dredged sludge fades.
또한, 상기 오염 준설 슬러지 100중량부에 대하여, 페트로 코크스 탈황석고 함량이 10중량부 미만이면 함수율을 낮추기가 어렵고 함께 투입되는 산성 물질인 리튬 잔사 슬러지의 pH를 알칼리성으로 전환이 어렵게 되며, 300중량부 초과이면 슬러지 재활용 의미가 퇴색하게 된다.In addition, with respect to 100 parts by weight of the contaminated dredged sludge, if the content of petroleum coke desulfurized gypsum is less than 10 parts by weight, it is difficult to lower the water content and it is difficult to convert the pH of lithium residual sludge, which is an acidic substance, into alkaline. If it is exceeded, the meaning of sludge recycling fades.
나아가, 본 발명의 산업부산물을 이용한 무시멘트계 경화체 조성물은 상기 혼합슬러지에는, 상기 오염 준설 슬러지 100중량부에 대하여, 고형연료를 연료로 사용하는 순환 유동층 보일러 하부에서 배출되는 폐유동사 10∼100중량부를 더 포함하는 바람직하다. Furthermore, the cement-free cured body composition using the industrial by-product of the present invention contains 10 to 100 parts by weight of waste fluid sand discharged from the lower part of a circulating fluidized bed boiler using solid fuel as fuel in the mixed sludge, based on 100 parts by weight of the contaminated dredged sludge. It is desirable to include more.
상기 폐유동사는 보일러 상부에서 배출되는 플라이애시에 비해 0.1∼3mm의 잔모래 크기의 거친 입자로 배출되고 입자 표면에 생석회 성분이 일부 함유되어 있기 때문에 고함수 상태의 슬러지와 페트로 코크스 탈황석고의 혼합 시 수분 저감에 더욱 효과적이며, 페트로 코크스 탈황석고에 비해 거친 입도를 가지고 있어 입자가 필터프레스의 압력 및 수분에 의해 견고하게 뭉쳐있는 슬러지 입자의 단립화에 많은 도움을 준다. Compared to the fly ash discharged from the top of the boiler, the waste flow sand is discharged as coarse particles the size of fine sand of 0.1 to 3 mm, and because it contains some quicklime components on the particle surface, moisture is lost when mixing high-water sludge and petroleum coke desulfurized gypsum. It is more effective in reduction, and has a coarser particle size than petro-coke desulfurized gypsum, so it greatly helps in agglomerating sludge particles that are tightly clumped together by the pressure and moisture of the filter press.
또한, 초기강도를 증진시키기 위하여 상기 혼합슬러지 100중량부에 대하여 1종 시멘트를 10∼100중량부 더 포함하는 것이 바람직하다. 상기 1종 시멘트는 초기 강도를 증진시켜 주는 역할을 수행하며 시중에서 일반적으로 유통되는 제품이면 사용이 가능하다. In addition, in order to improve the initial strength, it is preferable to further include 10 to 100 parts by weight of type 1 cement based on 100 parts by weight of the mixed sludge. The type 1 cement serves to enhance initial strength and can be used as long as it is a product commonly distributed on the market.
이때, 초기강도를 증진시키기 위하여 포함되는 시멘트의 함량이 10중량부 미만이면 초기 강도 증진 효과가 미비하며 반대로 100중량부를 초과하면, 초기강도는 더욱 증진되나 6가 크롬이 용출될 수 있으며 경제성 또한 불리하다. At this time, if the amount of cement included to improve the initial strength is less than 10 parts by weight, the effect of improving the initial strength is minimal. Conversely, if it exceeds 100 parts by weight, the initial strength is further improved, but hexavalent chromium may be eluted and the economic efficiency is also disadvantageous. do.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명하고자 한다. Hereinafter, the present invention will be described in more detail through examples.
본 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것이며, 본 발명의 범위가 이들 실시예에 한정되는 것은 아니다. These examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.
비교예(건조 및 분쇄 공정을 거친 준설토 미분말 + 리튬 잔사 미분말 + 고로슬래그 미분말)Comparative example (fine powder of dredged soil + fine powder of lithium residue + fine powder of blast furnace slag after drying and grinding process)
하천 준설현장에서 발생된 응집/침전 및 탈수 처리가 되지 않은 함수율 88%의 준설 슬러지와 전남 광양 소재 P사에 필터프레스로 탈수 처리되어 함수율 42%, pH가 3.1인 상태로 배출된 리튬 잔사 슬러지를 105℃에서 완전 건조 후 이를 비표면적 2,500cm2/g의 미분말 형태로 분쇄하였다. 상기 준설토 미분말 100중량부에 대하여, 리륨 잔사 미분말 50중량부에 비표면적 4,300cm2/g인 고로슬래그 미분말 150중량부를 혼합한 후 물/고형분비 50%의 페이스트를 제작하여 재령별 일축 압축강도를 측정하였다.Dredged sludge with a water content of 88% that has not been coagulated/settled and dehydrated generated at a river dredging site, and lithium residual sludge that was dehydrated with a filter press and discharged to Company P in Gwangyang, Jeollanam-do with a water content of 42% and a pH of 3.1. After complete drying at 105°C, it was ground into fine powder with a specific surface area of 2,500 cm 2 /g. For 100 parts by weight of the dredged soil fine powder, 50 parts by weight of lyrium residue fine powder were mixed with 150 parts by weight of blast furnace slag fine powder with a specific surface area of 4,300 cm 2 /g, and then a paste with a water/solid ratio of 50% was produced to determine the uniaxial compressive strength by age. Measured.
실시예 1Example 1
하천 준설현장에서 발생된 응집/침전 및 탈수 처리가 되지 않은 함수율 88%의 준설 슬러지와 전남 광양 소재 P사에 필터프레스로 탈수 처리되어 함수율 42%, pH가 3.1인 상태로 배출된 리튬 잔사 슬러지를 건조 및 분쇄 공정 없이 사용되었으며, 상기 오염 준설 슬러지 100중량부에 대하여, 리튬 잔사 슬러지 50중량부 및 페트로 코크스 탈황석고 100중량부를 균질하게 혼합하여 6시간 상온에서 방치하였다. Dredged sludge with a water content of 88% that has not been coagulated/settled and dehydrated generated at a river dredging site, and lithium residual sludge that was dehydrated with a filter press and discharged to Company P in Gwangyang, Jeollanam-do with a water content of 42% and a pH of 3.1. It was used without drying and grinding processes, and with respect to 100 parts by weight of the contaminated dredged sludge, 50 parts by weight of lithium residual sludge and 100 parts by weight of petrol coke desulfurized gypsum were homogeneously mixed and left at room temperature for 6 hours.
상기 6시간 방치한 후 오염 준설 슬러지 + 리튬 잔사 슬러지 + 페트로 코크스 탈황석고가 혼합된 혼합슬러지의 함수율은 36.4%였으며, pH는 11.2로 측정되었다.After being left for 6 hours, the water content of the mixed sludge mixed with contaminated dredged sludge, lithium residual sludge, and petroleum coke desulfurized gypsum was 36.4%, and the pH was measured to be 11.2.
상기 혼합슬러지 100중량부에 대하여, 고로슬래그 미분말 100중량부를 혼합한 후 혼합물의 기존 수분 함유량을 감안하여 물을 추가 투입하여 전체 혼합물의 물/고형분비를 50%로 페이스트를 제작하여 재령별 일축 압축강도를 측정하였다. After mixing 100 parts by weight of blast furnace slag fine powder with 100 parts by weight of the mixed sludge, additional water was added considering the existing moisture content of the mixture to produce a paste with a water/solid ratio of the entire mixture of 50%, and uniaxial compression was performed according to age. The intensity was measured.
실시예 2Example 2
하천 준설현장에서 발생된 응집/침전 및 탈수 처리가 되지 않은 함수율 88%의 준설 슬러지와 전남 광양 소재 P사에 필터프레스로 탈수 처리되어 함수율 42%, pH가 3.1인 상태로 배출된 리튬 잔사 슬러지를 건조 및 분쇄 공정 없이 사용되었으며, 상기 오염 준설 슬러지 100중량부에 대하여, 리튬 잔사 슬러지 50중량부, 페트로 코크스 탈황석고 100중량부 및 우드펠렛을 연료로 사용하는 순환 유동층 보일러 하부에서 배출되는 폐유동사 30중량부를 균질하게 혼합하여 6시간 상온에서 방치하였다. Dredged sludge with a water content of 88% that has not been coagulated/settled and dehydrated generated at a river dredging site, and lithium residual sludge that was dehydrated with a filter press and discharged to Company P in Gwangyang, Jeollanam-do with a water content of 42% and a pH of 3.1. It was used without drying and grinding processes, and for 100 parts by weight of the contaminated dredged sludge, 50 parts by weight of lithium residual sludge, 100 parts by weight of petro-coke desulfurized gypsum, and 30 parts by weight of waste fluid discharged from the bottom of a circulating fluidized bed boiler using wood pellets as fuel. The parts by weight were mixed homogeneously and left at room temperature for 6 hours.
상기 6시간 방치한 후 오염 준설 슬러지 + 리튬 잔사 슬러지 + 페트로 코크스 탈황석고 + 폐유동사가 혼합된 혼합슬러지의 함수율은 30.4%였으며, pH는 11.6으로 측정되었다.After being left for 6 hours, the water content of the mixed sludge, which was a mixture of contaminated dredged sludge + lithium residual sludge + petrol coke desulfurized gypsum + waste fluid sand, was 30.4%, and the pH was measured to be 11.6.
상기 혼합슬러지 100중량부에 대하여, 고로슬래그 미분말 100중량부를 혼합한 후 혼합물의 기존 수분 함유량을 감안하여 물을 추가 투입하여 전체 혼합물의 물/고형분비를 50%로 페이스트를 제작하여 재령별 일축 압축강도를 측정하였다. After mixing 100 parts by weight of blast furnace slag fine powder with 100 parts by weight of the mixed sludge, additional water was added considering the existing moisture content of the mixture to produce a paste with a water/solid ratio of the entire mixture of 50%, and uniaxial compression was performed according to age. The intensity was measured.
실시예 3Example 3
하천 준설현장에서 발생된 응집/침전 및 탈수 처리가 되지 않은 함수율 88%의 준설 슬러지와 전남 광양 소재 P사에 필터프레스로 탈수 처리되어 함수율 42%, pH가 3.1인 상태로 배출된 리튬 잔사 슬러지를 건조 및 분쇄 공정 없이 사용되었으며, 상기 오염 준설 슬러지 100중량부에 대하여 리튬 잔사 슬러지 50중량부 및 페트로 코크스 탈황석고 100중량부를 균질하게 혼합하여 6시간 상온에서 방치하였다. Dredged sludge with a water content of 88% that has not been coagulated/settled and dehydrated generated at a river dredging site, and lithium residual sludge that was dehydrated with a filter press and discharged to Company P in Gwangyang, Jeollanam-do with a water content of 42% and a pH of 3.1. It was used without drying and grinding processes, and 50 parts by weight of lithium residual sludge and 100 parts by weight of petro-coke desulfurized gypsum were homogeneously mixed with 100 parts by weight of the contaminated dredged sludge and left at room temperature for 6 hours.
상기 6시간 방치한 후 오염 준설 슬러지 + 리튬 잔사 슬러지 + 페트로 코크스 탈황석고가 혼합된 혼합슬러지의 함수율은 36.4%였으며, pH는 11.2로 측정되었다.After being left for 6 hours, the water content of the mixed sludge mixed with contaminated dredged sludge, lithium residual sludge, and petroleum coke desulfurized gypsum was 36.4%, and the pH was measured to be 11.2.
상기 혼합슬러지 100중량부에 대하여, 고로슬래그 미분말 100중량부 및 1종 시멘트 50중량부를 혼합한 후 혼합물의 기존 수분 함유량을 감안하여 물을 추가 투입하여 전체 혼합물의 물/고형분비를 50%로 페이스트를 제작하여 재령별 일축 압축강도를 측정하였다.With respect to 100 parts by weight of the mixed sludge, 100 parts by weight of blast furnace slag fine powder and 50 parts by weight of type 1 cement are mixed, and then additional water is added considering the existing moisture content of the mixture to make a paste with a water/solid ratio of the entire mixture of 50%. was manufactured and the uniaxial compressive strength at each age was measured.
실험예 1: 오염 준설 슬러지와 리튬 잔사 부산물을 이용한 경화체 일축 압축강도 시험 결과Experimental Example 1: Uniaxial compressive strength test results of hardened material using contaminated dredged sludge and lithium residual by-products
상기 비교예 및 실시예 1∼3에서 제조된 경화체의 일축 압축강도를 측정하여 하기 표 1에 기재하였다.The uniaxial compressive strengths of the cured bodies prepared in Comparative Examples and Examples 1 to 3 were measured and listed in Table 1 below.
상기 표 1에서 확인되는 바와 같이, 오염 준설 슬러지와 리튬 잔사 슬러지를 건조 및 미분쇄 처리하고, 페트로 코크스 탈황석고와 혼합하지 않은 비교예는 재령 3일까지 미경화 상태로 강도 측정이 불가하였으나, 오염 준설 슬러지와 리튬 잔사 슬러지를 별도의 건조 및 미분쇄 처리없이 페트로 코크스 탈황석고와 혼합 처리한 실시예 1∼3의 경화체에서는 2.32∼4.56MPa의 압축강도를 발현하였으며, 재령 7일 및 28일 재령에서도 비교예에 비하여 약 4∼5배의 일축 압축강도 발현을 확인하였다. As can be seen in Table 1 above, in the comparative example in which contaminated dredged sludge and lithium residual sludge were dried and pulverized and not mixed with petroleum coke desulfurized gypsum, the strength could not be measured in an uncured state until 3 days, but the contamination The hardened bodies of Examples 1 to 3, in which dredged sludge and lithium residual sludge were mixed with petroleum coke desulfurized gypsum without separate drying and pulverizing treatment, developed compressive strengths of 2.32 to 4.56 MPa, even at 7 and 28 days of age. It was confirmed that the uniaxial compressive strength was approximately 4 to 5 times higher than that of the comparative example.
이상으로부터, 본 발명에 의하면 오염 준설 슬러지와 리튬 잔사 슬러지를 별도의 중화, 건조, 분쇄 및 분급 공정을 거치지 않고 배출 상태 그대로 이용이 가능하여 에너지 비용을 크게 저감할 수 있다. From the above, according to the present invention, contaminated dredged sludge and lithium residual sludge can be used in their discharged state without undergoing separate neutralization, drying, grinding, and classification processes, thereby significantly reducing energy costs.
또한, 일반적으로 오염 준설 슬러지를 경화시키기 위해서는 다량의 시멘트가 투입되어야 하나 본 발명에서는 주성분이 생석회와 무수석고 성분으로 구성된 페트로 코크스 탈황석고의 혼합에 의해, 산성 물질인 리튬 잔사 슬러지의 알칼리화 및 함수율 저감이 가능하고, 수분과 반응하여 생성된 수산화칼슘과 석고 성분이 고로슬래그 미분말 및 리튬 잔사 슬러지에 함유된 알루미노실리케이트의 잠재수경성을 이끌어내어 경화체 형성이 가능하였다. In addition, generally, a large amount of cement must be added to harden contaminated dredged sludge, but in the present invention, alkalization and water content reduction of lithium residue sludge, which is an acidic substance, are achieved by mixing petro-coke desulfurized gypsum, which mainly consists of quicklime and anhydrous gypsum. This was possible, and the calcium hydroxide and gypsum components produced by reacting with moisture induced the latent hydraulic properties of the aluminosilicate contained in the blast furnace slag fine powder and lithium residual sludge, making it possible to form a hardened body.
이상에서 본 발명은 기재된 구체예에 대해서만 상세히 설명되었지만 본 발명의 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속함은 당연한 것이다. In the above, the present invention has been described in detail only with respect to the described embodiments, but it is clear to those skilled in the art that various changes and modifications are possible within the technical scope of the present invention, and it is natural that such changes and modifications fall within the scope of the appended patent claims.
Claims (7)
황산을 이용한 리튬 추출 공정에서 발생하는 함수율 25∼45% 및 pH 2∼6인 산성의 리튬 잔사 슬러지를 포함하는 함수율이 높은 산업부산물에,
페트로 코크스를 연료로 사용하는 순환 유동층 보일러에서 배출되는 CaO 함량이 40∼70중량%, SO3 함량이 20∼35중량%인 페트로 코크스 탈황석고를 혼합하여 함수율을 20∼40%로 낮추고 pH 9∼12.5의 알칼리성으로 조절된 혼합슬러지 100 중량부에 대하여,
고로슬래그 미분말 10∼300중량부를 포함하되,
상기 오염 준설 슬러지와 리튬 잔사 슬러지가 별도의 중화, 건조, 분쇄 및 분급 공정을 거치지 않고 배출 상태 그대로 사용된 것을 특징으로 하는 산업부산물을 이용한 무시멘트계 경화체 조성물.Contaminated dredged sludge with a moisture content of 50 to 95% and
Industrial by-products with high moisture content, including acidic lithium residue sludge with a moisture content of 25 to 45% and pH of 2 to 6, generated in the lithium extraction process using sulfuric acid,
Petrocoke desulfurized gypsum with a CaO content of 40 to 70% by weight and an SO 3 content of 20 to 35% by weight, discharged from a circulating fluidized bed boiler using petrol coke as fuel, is mixed to lower the water content to 20 to 40% and pH to 9 to 9. For 100 parts by weight of mixed sludge adjusted to alkalinity of 12.5,
Contains 10 to 300 parts by weight of blast furnace slag fine powder,
A cement-free hardened body composition using industrial by-products, characterized in that the contaminated dredged sludge and lithium residual sludge are used as discharged without undergoing separate neutralization, drying, grinding, and classification processes.
상기 오염 준설 슬러지 100중량부에 대하여,
상기 리튬 잔사 슬러지 5∼100중량부 및
상기 페트로 코크스 탈황석고 10∼300중량부가 혼합된 것을 특징으로 하는 산업부산물을 이용한 무시멘트계 경화체 조성물.The method of claim 1, wherein the mixed sludge
Regarding 100 parts by weight of the contaminated dredging sludge,
5 to 100 parts by weight of the lithium residual sludge and
A cement-free hardened body composition using industrial by-products, characterized in that 10 to 300 parts by weight of the petrol coke desulfurized gypsum is mixed.
초기강도를 증진시키기 위하여 1종 시멘트를 10∼100중량부 더 포함하는 것을 특징으로 하는 산업부산물을 이용한 무시멘트계 경화체 조성물.According to claim 1, with respect to 100 parts by weight of the mixed sludge,
A cementless hardened body composition using industrial by-products, characterized in that it further contains 10 to 100 parts by weight of type 1 cement to improve initial strength.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100901107B1 (en) | 2008-02-05 | 2009-06-08 | 한미기초개발주식회사 | A method and apparatus for manufacturing lightweight foamed soils |
| KR101212196B1 (en) | 2012-08-29 | 2012-12-13 | 우리토양기술 주식회사 | Solidification agent for dredged soils and a soil conditioner using it |
| KR20140092699A (en) * | 2013-01-16 | 2014-07-24 | 주식회사 씨엠디기술단 | Sludge solidified agent and menufacturing method of artificial soil usign the same |
| KR101466563B1 (en) | 2012-11-02 | 2014-11-28 | 한국해양과학기술원 | Method for Soft Ground Improvement using Light-Weighted Foam Soil |
| KR20200066047A (en) | 2018-11-30 | 2020-06-09 | 주식회사 포스코 | Non-cement binder composition and manufacturing method of the same |
| KR20210047480A (en) * | 2019-10-22 | 2021-04-30 | (재)한국건설생활환경시험연구원 | Dredge solidification composition for rapid treatment |
| KR20210155654A (en) * | 2020-06-16 | 2021-12-23 | 주식회사 대웅 | Expandable mortar composition and pile construction method |
| KR20230093138A (en) | 2021-12-17 | 2023-06-27 | 주식회사 포스코 | Pozzolan cement composition and method for preparing the same |
-
2023
- 2023-08-28 KR KR1020230112977A patent/KR102654370B1/en active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100901107B1 (en) | 2008-02-05 | 2009-06-08 | 한미기초개발주식회사 | A method and apparatus for manufacturing lightweight foamed soils |
| KR101212196B1 (en) | 2012-08-29 | 2012-12-13 | 우리토양기술 주식회사 | Solidification agent for dredged soils and a soil conditioner using it |
| KR101466563B1 (en) | 2012-11-02 | 2014-11-28 | 한국해양과학기술원 | Method for Soft Ground Improvement using Light-Weighted Foam Soil |
| KR20140092699A (en) * | 2013-01-16 | 2014-07-24 | 주식회사 씨엠디기술단 | Sludge solidified agent and menufacturing method of artificial soil usign the same |
| KR20200066047A (en) | 2018-11-30 | 2020-06-09 | 주식회사 포스코 | Non-cement binder composition and manufacturing method of the same |
| KR20210047480A (en) * | 2019-10-22 | 2021-04-30 | (재)한국건설생활환경시험연구원 | Dredge solidification composition for rapid treatment |
| KR20210155654A (en) * | 2020-06-16 | 2021-12-23 | 주식회사 대웅 | Expandable mortar composition and pile construction method |
| KR20230093138A (en) | 2021-12-17 | 2023-06-27 | 주식회사 포스코 | Pozzolan cement composition and method for preparing the same |
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