KR20050080681A - Solidifying addition contains calcium sulfo aluminate and manufacturing method thereof - Google Patents
Solidifying addition contains calcium sulfo aluminate and manufacturing method thereof Download PDFInfo
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- KR20050080681A KR20050080681A KR1020040008783A KR20040008783A KR20050080681A KR 20050080681 A KR20050080681 A KR 20050080681A KR 1020040008783 A KR1020040008783 A KR 1020040008783A KR 20040008783 A KR20040008783 A KR 20040008783A KR 20050080681 A KR20050080681 A KR 20050080681A
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- calcium sulfoaluminate
- cement
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- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 53
- 239000011575 calcium Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- -1 calcium sulfo aluminate Chemical class 0.000 title claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000010802 sludge Substances 0.000 claims abstract description 29
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 24
- 239000002440 industrial waste Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000002910 solid waste Substances 0.000 claims abstract 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 40
- 239000011707 mineral Substances 0.000 claims description 40
- 239000004568 cement Substances 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 239000010440 gypsum Substances 0.000 claims description 9
- 229910052602 gypsum Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000010459 dolomite Substances 0.000 claims description 8
- 229910000514 dolomite Inorganic materials 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 231100001261 hazardous Toxicity 0.000 claims description 4
- 210000004556 brain Anatomy 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 1
- 239000011812 mixed powder Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 150000002736 metal compounds Chemical class 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000010842 industrial wastewater Substances 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 235000010755 mineral Nutrition 0.000 description 23
- 238000007711 solidification Methods 0.000 description 13
- 230000008023 solidification Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 238000006703 hydration reaction Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 230000036571 hydration Effects 0.000 description 7
- 239000000654 additive Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229940037003 alum Drugs 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- MYZAXBZLEILEBR-RVFOSREFSA-N (2S)-1-[(2S,3R)-2-[[(2R)-2-[[2-[[(2S)-2-[(2-aminoacetyl)amino]-5-(diaminomethylideneamino)pentanoyl]amino]acetyl]amino]-3-sulfopropanoyl]amino]-3-hydroxybutanoyl]pyrrolidine-2-carboxylic acid Chemical compound C[C@@H](O)[C@H](NC(=O)[C@H](CS(O)(=O)=O)NC(=O)CNC(=O)[C@H](CCCN=C(N)N)NC(=O)CN)C(=O)N1CCC[C@H]1C(O)=O MYZAXBZLEILEBR-RVFOSREFSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108700002400 risuteganib Proteins 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- C04B18/0418—Wet materials, e.g. slurries
-
- 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
- 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
- C04B22/10—Acids or salts thereof containing carbon in the anion
-
- 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
-
- 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
- C04B28/16—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 anhydrite, e.g. Keene's cement
-
- 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
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
-
- 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)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Civil Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Sludge (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
본 발명은 상하수, 하천, 호수, 산업 폐수 등의 수처리에 의해 생긴 슬러지, 산업폐기물 소각재 및 각종 유해 중금속 화합물을 함유하는 산업폐기물 및 슬러지를 고화처리 하는데 있어서 산업부산물을 이용하여 제조된 칼슘설포알루미네이트(CSA)를 주체로 한 광물을 고화재로서 사용한 유해 중금속 함유 산업폐기물 및 슬러지의 고화재 제조방법에 관한 것이다.The present invention is a calcium sulfoaluminate prepared using industrial by-products in solidifying industrial wastes and sludges containing sludge, industrial waste incinerators and various harmful heavy metal compounds produced by water treatment of water, sewage, rivers, lakes, industrial wastewater, and the like. The present invention relates to a method for producing solid wastes containing harmful heavy metal-containing industrial wastes and sludges, using (CSA) as the main solid.
Description
본 발명은 상하수, 하천, 호수, 산업 폐수 등의 수처리에 의해 생긴 슬러지, 산업폐기물 소각재 및 각종 유해 중금속 화합물을 함유하는 산업폐기물 및 슬러지를 고화처리 하는데 있어서 산업부산물을 이용하여 제조된 칼슘설포알루미네이트(Calcium Sulfo Aluminate, CSA, 4CaO,3Al2O3, SO3)를 주체로 한 광물을 고화재로서 사용한 유해 중금속 함유 산업폐기물 및 슬러지의 고화처리에 관한 것이다.The present invention is a calcium sulfoaluminate prepared using industrial by-products in solidifying industrial wastes and sludges containing sludge, industrial waste incinerators and various harmful heavy metal compounds produced by water treatment of water, sewage, rivers, lakes, industrial wastewater, and the like. (C alcium S ulfo a luminate, CSA, 4CaO, 3Al 2 O 3, SO 3) a is a high mineral as the main component solidifies on the treatment of hazardous industrial waste containing heavy metals and the sludge used as a fire.
시멘트는 복잡한 수화과정, 다양한 수화물과 다공성 미세구조에 의해 물리,화학적으로 유해 산업폐기물을 안정화할 수 있는 특징을 가지고 있기 때문에 효과적으로 산업폐기물을 무해화 할 수 있는 재료라 할 수 있다. 그러나, 함수비가 높거나, 유기물 및 중금속 화합물 등이 다량 함유되어 있는 산업폐기물 및 슬러지의 경우에는 시멘트의 수화과정에서 액상 중의 칼슘 2가 이온과 신속하게 결합되어 고화에 기여하지 않는 다른 석회염을 생성하고, 시멘트 입자의 표면을 치밀하게 피복하여 수화반응의 지연 또는 정지시키는 등의 고화 저해가 일어나서 다량의 시멘트를 사용한다 하더라도 목표로 하는 고형화는 곤란하다.Cement is a material that can effectively detoxify industrial wastes because it has the characteristics of stabilizing harmful industrial wastes physically and chemically by complicated hydration process, various hydrates and porous microstructures. However, industrial wastes and sludges with high water content, or large amounts of organic and heavy metal compounds, are rapidly bonded with calcium divalent ions in the liquid phase during the hydration of cement to produce other lime salts that do not contribute to solidification. The target solidification is difficult even if a large amount of cement is used because solidification is inhibited by delaying or stopping the hydration reaction by densely covering the surface of the cement particles.
이 대책으로서 시멘트에 다수의 첨가제를 사용하여 에트린자이트(3CaO,Al2O3,3CaSO4,32H2O) 생성량을 많게 유도하여 초기 수화활성을 도모코자 하고 있으나, 유효하게 고화시키기 어려운 실정이다.As a countermeasure, many additives are used in cement to induce the production of ethrinite (3CaO, Al 2 O 3, 3CaSO 4, 32H 2 O) to increase initial hydration activity, but it is difficult to effectively solidify. to be.
즉, 시멘트계 고화재의 고화 이론은 주로 에트린자이트 생성에 의한 것으로 이에 따라 다량의 수분을 결정수로 고정하고, 팽창에 의한 입밀 효과 및 유해 중금속 이온의 고용 효과를 높이게 한다.That is, the solidification theory of the cement-based solidifying material is mainly due to the formation of ethrinzite, thereby fixing a large amount of water with crystallized water, thereby increasing the effect of granulation due to expansion and the solid-solution effect of harmful heavy metal ions.
이러한 효과를 나타내기 위해 실리카 분말, 염화칼슘, 염화아연 등 첨가제를 혼합한 고화재를 사용할 수도 있으나, 시멘트 자체의 에트린자이트 생성량은 근본적으로 제한을 받기 때문에 유효하게 고화시키기가 어려운 실정이다. 그래서 수화 반응 저해 효과가 큰 슬러지 및 유해 중금속 함유 산업폐기물의 고화에도 화학적 기능을 개선한 고화재가 필연적으로 요구되어 진다.In order to exhibit such an effect, a solidified material mixed with an additive such as silica powder, calcium chloride, and zinc chloride may be used, but since the production amount of ethrinzite of the cement itself is fundamentally limited, it is difficult to effectively solidify. Therefore, solidification materials with improved chemical functions are inevitably required for the solidification of sludge and harmful heavy metal-containing industrial wastes, which have a large hydration inhibitory effect.
그 동안 이와 같은 결점을 보완하기 위해 시멘트계 고화재보다 에트린자이트 생성량이 많고 수화 활성이 높은 칼슘설포알루미네이트 광물을 고화재로 첨가 사용하여 왔다. 그러나 칼슘설포알루미네이트 광물을 제조하는 데는 알루미나 원이 필수적으로 소요되고 추가로 SO3 원의 공급이 필요하기 때문에 보통 보오크사이트, 석회석, 석고를 주로 이용하고 있다.In order to make up for this drawback, calcium sulfoaluminate minerals having a greater amount of ethrinite production and higher hydration activity than cement-based solidified materials have been used as solidified materials. However, bauxite, limestone and gypsum are usually used because the production of calcium sulfoaluminate minerals requires alumina source and additional SO 3 source.
칼슘설포알루미네이트 광물의 경우는 소성온도가 1200∼1300??내외로서 보통 포틀랜드 시멘트(OPC)에 비하여 100∼200?? 낮은 에너지 절약형 시멘트일 뿐만 아니라 속경성, 고강도성, 고유동성 및 팽창성 등의 특성을 나타내 여러 특수시멘트 분야 및 전통적인 시멘트의 결점을 보완할 수 있다.In the case of calcium sulfoaluminate minerals, the firing temperature is around 1200 ~ 1300 ?? and it is usually 100 ~ 200 ?? compared to portland cement (OPC). Not only is it a low-energy-saving cement, it also has properties such as fast stiffness, high strength, high flowability, and expandability to compensate for the shortcomings of many special cement applications and traditional cements.
본 발명에서 사용하고자하는 원료인 철강산업에서 발생되는 부산 슬러지(압연슬러지, 백운석슬러지)와 인산부산석고는 다른 산업에도 사용되고 있으나, 많은 양은 매립 등의 처리방법으로 처리하고 있으며, 환경오염에도 나쁜 영향을 미치고 있는 실정이다.Busan sludge (rolled sludge, dolomite sludge) and phosphate gypsum produced in the steel industry, which are the raw materials to be used in the present invention, are used in other industries, but a large amount is treated by a landfill treatment method, and also has an adverse effect on environmental pollution. The situation is going crazy.
본 발명의 목적은 칼슘설포알루미네이트 광물을 제조함에 있어, 철강산업에서 부산 되어 발생하고 있는 무기성 슬러지인 압연슬러지와 백운석슬러지를 이용하고, 또한 인산부산석고를 사용함으로써, 분말상태로 배출되기 때문에 분쇄가 용이하며, 원료의 단가를 줄일 수 있고 환경저해요인 저감효과와 더불어 폐자원을 실질적으로 실용 있게 활용하는 데에 그 목적이 있다.It is an object of the present invention to produce calcium sulfoaluminate minerals, which are discharged in powder form by using rolled sludge and dolomite sludge, which are inorganic sludges generated by the steel industry, and by using phosphate gypsum. The purpose is to facilitate the pulverization, reduce the unit cost of raw materials, and reduce waste, which is environmentally harmful, and to practically utilize waste resources.
그리고 이와 같이 제조된 칼슘설포알루미네이트 광물을 이용하여 유해 중금속 함유 산업폐기물 및 슬러지를 환경 유해성이 없도록 고화하는데 있어서, 중금속 이온들을 클링커 광물 내에 쉽게 고용 또는 불용화 하여 중금속 이온의 용출이 되지 않도록 첨가제를 사용하여 안정한 화합물 형태로 고화하도록 한 고화재 제조방법인 것이다. In order to solidify the hazardous heavy metal-containing industrial waste and sludge so that there is no environmental hazard by using the calcium sulfoaluminate mineral prepared as described above, the additive is added so that the heavy metal ions are easily dissolved or insolubilized in the clinker mineral so as not to elute the heavy metal ions. It is a method of producing a solid fire to solidify to a stable compound form.
상기한 과제를 해결하기 위한 본 발명에 따른 칼슘설포알루미네이트 광물이 함유된 고화재는 시멘트 100 중량부에 대하여 5 ~ 50의 중량부를 이루는 칼슘설포알루미네이트 분말과, 시멘트 100 중량부에 대하여 1 ~ 5 중량부를 이루는 불용성 무수석고(CaSO4)가 포함된 것을 특징으로 한다.The solidified material containing the calcium sulfoaluminate mineral according to the present invention for solving the above problems is a calcium sulfoaluminate powder forming 5 to 50 parts by weight with respect to 100 parts by weight of cement, and 1 to about 100 parts by weight of cement. 5 parts by weight of insoluble anhydrous gypsum (CaSO 4 ) is characterized in that it is included.
또한, 본 발명에 의한 칼슘설포알루미네이트 광물이 함유된 고화재 제조방법은 칼슘설포알루미네이트 광물을 분쇄하여 분말의 비표면적이 2,000 ∼5,000cm2/g를 이루도록 하는 분쇄단계와, 시멘트 및 상기 시멘트 100 중량부에 대하여 5 ~ 50 중량부를 이루는 칼슘설포알루미네이트 분말, 시멘트 100 중량부에 대하여 1 ~ 5 중량부를 이루는 불용성 무수석고 분말을 섞는 혼합단계가 포함된 것을 특징으로 한다.In addition, the method for producing a solidified material containing a calcium sulfoaluminate mineral according to the present invention is a grinding step of pulverizing the calcium sulfoaluminate mineral to achieve a specific surface area of the powder 2,000 ~ 5,000cm 2 / g, cement and the cement Calcium sulfoaluminate powder forming 5 to 50 parts by weight based on 100 parts by weight, characterized in that the mixing step of mixing insoluble anhydrous gypsum powder consisting of 1 to 5 parts by weight based on 100 parts by weight of cement.
이하 본 발명에 의한 칼슘설포알루미네이트 광물이 함유된 고화재의 일 실시 예를 보다 구체적으로 상술하면 다음과 같다.Hereinafter, an embodiment of the solidifying material containing the calcium sulfoaluminate mineral according to the present invention will be described in more detail.
본 발명은 칼슘설포알루미네이트 광물을 제조하는데 있어서, 표 1과 같이 Al2O3원으로 압연슬러지를, CaO원으로 백운석슬러지를, SO3원으로 인산부산석고를 이용한다. 이와 같은 화학조성을 갖는 산업부산물을 이용하여 칼슘설포알루미네이트 광물이 최대로 되는 배합조건으로 배합한 후 일정 입도로 분쇄한다.In the present invention, in the preparation of calcium sulfoaluminate mineral, as shown in Table 1, a rolled sludge is used as an Al 2 O 3 member, a dolomite sludge is used as a CaO source, and a phosphate gypsum is used as an SO 3 member. Using industrial by-products having such a chemical composition, the calcium sulfoaluminate mineral is blended under the maximum mixing condition and then pulverized to a certain particle size.
여기서, 상기 칼슘설포알루미네이트 광물의 조성은 중량% 30 ~ 70인 백운석슬러지와, 중량% 30 ~ 70인 압연종말슬러지와, 중량% 4 ~ 20인 부산석고가 포함되어 구성되고, 상기 혼합물의 입도가 88㎛, 잔분이 5 ~ 20 중량%로 분쇄되어 이루어진다.Here, the composition of the calcium sulfoaluminate mineral is composed of dolomite sludge of 30% to 70% by weight, rolled terminal sludge of 30% to 70% by weight, and Busan gypsum of 4% to 20% by weight. Is 88 µm, and the residue is pulverized to 5 to 20% by weight.
이후에, 상기 혼합물을 소성로에서 1,000∼1,300??의 소성온도로 1시간 이상 유지한 후 공냉시켜, 칼슘설포알루미네이트 광물을 제조하는 바, 생성된 칼슘설포알루미네이트 광물의 X선회절도는 도 1과 같이 주요 광물상은 칼슘설포알루미네이트 광물이 잘 발달되어 있고, 베라이트(??-C2S) 및 MgO 이다.Subsequently, the mixture was maintained at a firing temperature of 1,000 to 1,300 ° C. for at least 1 hour and then air cooled to prepare calcium sulfoaluminate mineral. The X-ray diffractogram of the calcium sulfoaluminate mineral produced was The main mineral phases are well developed calcium sulfoaluminate minerals, berite (??-C 2 S) and MgO.
[표 1]TABLE 1
이때, 소성온도가 낮거나, 백운석슬러지의 함량이 높은 경우에는 미반응 석회의 량이 많아져 팽창성을 나타내므로 붕괴, 파괴의 염려가 있으며, 소성온도가 높거나 석회석 배합량이 적어도 칼슘설포알루미네이트 광물 생성량이 적어져 소기의 목적을 달성할 수 없다.At this time, when the calcination temperature is low or the content of dolomite sludge is high, the amount of unreacted lime is increased, indicating the expandability, and thus there is a fear of collapse and destruction. It becomes less and cannot achieve the intended purpose.
이와 같이 사용한 원료의 배합비 및 소성온도를 적당히 변화시킴으로써 칼슘설포알루미네이트 분말과 불용성 무수석고의 조성비율을 조절하는 바, 상기 칼슘설포알루미네이트 분말은 시멘트 100 중량부에 대하여 5 ~ 50중량부를 이루도록 하고, 상기 불용성 무수석고 분말은 시멘트 100 중량부에 대하여 1 ~ 5 중량부를 이루도록 조절되어 보통 포틀랜드 시멘트에 혼합되어 고화재를 이룬다.The composition ratio of calcium sulfoaluminate powder and insoluble anhydrous gypsum is controlled by appropriately changing the mixing ratio and firing temperature of the raw materials used. The calcium sulfoaluminate powder is 5 to 50 parts by weight based on 100 parts by weight of cement. , The insoluble anhydrous gypsum powder is adjusted to form 1 to 5 parts by weight based on 100 parts by weight of cement is usually mixed in Portland cement to form a solidified material.
이때, 상기 칼슘설포알루미네이트 분말에는 칼슘실리케이트 및 유리석회 또한 함유되는데 이 조성비율 또한 칼슘설포알루미네이트 제조시에 조절됨으로써, 고화 대상물에 적합하고, 고화 효과가 우수한 고화재를 얻을 수 있다.In this case, the calcium sulfoaluminate powder also contains calcium silicate and free lime, and the composition ratio is also adjusted at the time of preparing calcium sulfoaluminate, thereby obtaining a solidified material that is suitable for a solidification object and has an excellent solidification effect.
특히, 칼슘설포알루미네이트 광물 이외에 부수적으로 생성되는 불용성 무수석고 및 활성 알루미나와 유리석회 성분은 칼슘설포알루미네이트 광물의 에트린자이트 생성을 촉진시키는 작용을 한다.In particular, insoluble anhydrous gypsum and activated alumina and free lime components, which are additionally produced in addition to the calcium sulfoaluminate mineral, serve to promote the formation of ethrinzite of the calcium sulfoaluminate mineral.
한편, 폐기물 중에 유기물 및 유해 중금속이 다량 함유되어 있을 경우, 상기 칼슘설포알루미네이트 광물 이외에 중금속 고정 효과 및 유기물에 의한 시멘트 수화 저해를 방지하기 위한 첨가제로서 알칼리 탄산염, 명반, 염화물 및 황산염 중에서 적어도 1종 이상을 선택하여 0.5∼10중량% 범위 내에서 첨가함으로써 더욱 효과적으로 고화 처리가 가능하다.On the other hand, when the waste contains a large amount of organic matter and harmful heavy metals, at least one of alkali carbonate, alum, chloride and sulfate as an additive for preventing the heavy metal fixation effect and the inhibition of cement hydration by organic matter in addition to the calcium sulfoaluminate mineral. By selecting the above and adding within the range of 0.5 to 10% by weight, the solidification treatment can be performed more effectively.
이하, 실시 예를 들어 보다 상세하게 설명을 한다.Hereinafter, an Example is given and it demonstrates in detail.
[실시예]EXAMPLE
표 2와 같은 유해 중금속을 함유하는 화학공장 폐수처리에서 생성되는 슬러지에 대해 상기와 같이 제조된 칼슘설포알루미네이트(CSA) 광물을 브레인 비표면적 3,000cm2/g으로 분쇄하고, 보통 포틀랜드 시멘트에 5∼50중량% 첨가하여 고화재를 제조하였다. 이 때 고화재 조성물 중에는 알칼리 탄산염 (소다회) 및 황산염(명반) 등을 0.5 ~ 10중량% 첨가하고, 슬러지의 혼합성을 좋게 하기 위해 물을 25중량%를 첨가하여 혼합, 교반하였다. 고화시킨 공시체의 고화강도 측정 결과는 표 3과 같으며, 고화시편의 28일 양생 후 폐기물 공정시험법에 의한 중금속 용출시험 결과는 표 4에 나타난 바와 같이 고화강도가 우수한 특성을 지니며, 또한, 중금속 이온의 포집, 고정 효과도 극히 우수한 특성을 나타내고 있다.Calcium sulfoaluminate (CSA) minerals prepared as described above for the sludge produced in the chemical plant wastewater treatment containing harmful heavy metals as shown in Table 2 were ground to a brain specific surface area of 3,000 cm 2 / g, -50 weight% was added and the solidified material was manufactured. At this time, 0.5-10 weight% of alkali carbonate (soda ash), sulfate (alum), etc. were added to solidified composition, and 25 weight% of water was added, mixed, and stirred in order to improve the mixing property of sludge. The measurement results of solidification strength of the solidified specimens are shown in Table 3, and the heavy metal dissolution test results by the waste process test method after 28 days of curing of the solidified specimens have the characteristics of excellent solidification strength as shown in Table 4, The collection and fixation effect of heavy metal ions is also extremely excellent.
[표 2]TABLE 2
통상 시멘트계 고화재는 석고 및 알루미나 원, 기타 여러 첨가제를 사용하여 에트린자이트 생성량을 많게 유도하고 있으나, 본 발명의 고화재를 이용하면 다음과 같은 반응 특성에 의해 우수한 성능을 발휘하게 된다. 이 칼슘설포알루미네이트 수화물은 침상결정 중의 칼슘 2가 이온의 활성이 커서 유해 중금속 이온 등 시멘트의 수화 및 고화를 저해하는 이온들을 흡착 고용시킨다. 또한, 칼슘설포알루미네이트 수화물 내에 중금속이나 슬러지 등을 안정한 형태로 포집, 고정시킴으로써, 산업폐기물 및 슬러지 등을 안정하고 견고하게 고화시킨다.In general, cement-based solidified materials are used to induce a large amount of ethrinzite using gypsum, alumina source, and various additives. However, when the solidified material of the present invention is used, excellent performance is obtained by the following reaction characteristics. The calcium sulfoaluminate hydrate absorbs and dissolves ions that inhibit the hydration and solidification of cement such as harmful heavy metal ions due to the high activity of calcium divalent ions in the needle crystal. In addition, by collecting and fixing heavy metals and sludges in a stable form in calcium sulfoaluminate hydrate, industrial wastes and sludges are solidified stably and firmly.
[표 3]TABLE 3
[표 4]TABLE 4
본 발명의 고화처리재 반응 특성은 에트린자이트 생성 반응속도가 시멘트계 고화재보다 현저히 빠르고, 생성량도 많아 유기물 및 중금속 화합물 등의 시멘트 경화 저해 물질이 존재하여도 반응이 진행되는 특징을 가지고 있다.The reaction property of the solidified material of the present invention is characterized in that the reaction rate of the ethrinzite formation is significantly faster than that of the cement-based solidified material, and the production amount is large, so that the reaction proceeds even in the presence of cement hardening inhibitors such as organic substances and heavy metal compounds.
이상과 같이 본 발명의 고화재는 상기의 반응 특성에 의해 고함수 슬러지의 고화에 효과적이고, 중금속 고정 능력이 우수하며, 장기적으로 안정한 유해 중금속 함유 산업폐기물 및 슬러지의 고화재를 제공하게 된다.As described above, the solidified material of the present invention provides the solidified material of the industrial heavy waste and sludge containing harmful heavy metals which is effective in solidifying high-functional sludge by the above reaction characteristics, and has excellent heavy metal fixing ability and is stable in the long term.
도1은 본 발명에 따른 칼슘설포알루미네이트 광물의 X선회절도이다.1 is an X-ray diffraction diagram of calcium sulfoaluminate mineral according to the present invention.
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