KR20120115921A - Stabilization of Free CaO Components in Steel Slag Using Carbon Dioxide - Google Patents
Stabilization of Free CaO Components in Steel Slag Using Carbon Dioxide Download PDFInfo
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- KR20120115921A KR20120115921A KR20110033984A KR20110033984A KR20120115921A KR 20120115921 A KR20120115921 A KR 20120115921A KR 20110033984 A KR20110033984 A KR 20110033984A KR 20110033984 A KR20110033984 A KR 20110033984A KR 20120115921 A KR20120115921 A KR 20120115921A
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- steel slag
- process water
- sodium hydroxide
- carbon dioxide
- sodium carbonate
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 28
- 230000006641 stabilisation Effects 0.000 title description 3
- 238000011105 stabilization Methods 0.000 title description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 108
- 239000002893 slag Substances 0.000 claims abstract description 98
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 88
- 239000010959 steel Substances 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 84
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 63
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 31
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 24
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 12
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 83
- 239000004571 lime Substances 0.000 claims description 31
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 30
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000011575 calcium Substances 0.000 claims description 16
- 239000002699 waste material Substances 0.000 claims description 13
- 239000004576 sand Substances 0.000 claims description 11
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 239000000292 calcium oxide Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000012530 fluid Substances 0.000 abstract 7
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 11
- 239000000920 calcium hydroxide Substances 0.000 description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000805 Pig iron Inorganic materials 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- POECFFCNUXZPJT-UHFFFAOYSA-M sodium;carbonic acid;hydrogen carbonate Chemical compound [Na+].OC(O)=O.OC([O-])=O POECFFCNUXZPJT-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B3/00—General features in the manufacture of pig-iron
- C21B3/04—Recovery of by-products, e.g. slag
- C21B3/06—Treatment of liquid slag
- C21B3/08—Cooling slag
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
- C04B5/06—Ingredients, other than water, added to the molten slag or to the granulating medium or before remelting; Treatment with gases or gas generating compounds, e.g. to obtain porous slag
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2200/00—Recycling of non-gaseous waste material
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2400/00—Treatment of slags originating from iron or steel processes
- C21B2400/02—Physical or chemical treatment of slags
- C21B2400/022—Methods of cooling or quenching molten slag
- C21B2400/024—Methods of cooling or quenching molten slag with the direct use of steam or liquid coolants, e.g. water
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C2200/00—Recycling of waste material
-
- 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
- Y02W30/20—Waste processing or separation
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Metallurgy (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Processing Of Solid Wastes (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
본 발명은 수산화나트륨, 탄산나트륨이 함유하고 계면활성제가 같이 녹아 있는 공정수에 탄산가스를 공급하여 철강슬래그의 유리석회(Free CaO)성분과 공정수에 있는 탄산 성분과 반응하여 안정화된 철강슬래그를 생산하는 방법으로,The present invention produces stabilized steel slag by supplying carbon dioxide gas to process water containing sodium hydroxide and sodium carbonate and dissolving surfactant together and reacting with free lime component of steel slag and carbonic acid component in process water. In a way,
더욱 상세하게는 철강슬래그의 유리석회(Free CaO)성분을 안정화시키기 위하여 수산화나트륨, 탄산나트륨이 함유하고 계면활성제가 같이 녹아 있는 공정수에 탄산가스를 공급하여 철강슬래그의 유리석회(Free CaO)성분과 공정수의 탄산 성분과 반응하여 철강슬래그의 유리석회(Free CaO)성분을 안정화하도록 한 과정에서, 사용된 공정수를 다시 재활용할 수 있는 공정수로 만들기 위하여 재활용 될 공정수에 탄산가스를 다시 사용된 공정수에 공급하므로서 탄산나트륨이 함유한 공정수로 변환되어, 철강슬래그의 유리석회(Free CaO)성분과 변환된 공정수의 탄산성분이 반응하여 철강슬래그의 유리석회(Free CaO)성분이 탄산석회(CaCO3)로 변환되어 안정화 된 철강슬래그를 생산하면서 공정수를 연속적으로 사용하는 철강슬래그를 안정화 방법이다.More specifically, in order to stabilize the free lime component of the steel slag, carbon dioxide is supplied to the process water containing sodium hydroxide and sodium carbonate and the surfactant is dissolved together with the free lime component of the steel slag. In the process of stabilizing the free lime content of the steel slag by reacting with the carbonic acid component of the process water, carbon dioxide is reused in the process water to be recycled to make the process water used again. It is converted into process water containing sodium carbonate by supplying the processed process water, and the free lime (CaO) component of the steel slag reacts with the carbonate component of the converted process water. It is a method of stabilizing steel slag that uses process water continuously while producing stabilized steel slag converted to (CaCO 3 ).
일반적으로 제철산업은 대량의 원료와 에너지를 소비하며 철강을 생산할 뿐 아니라 다양한 종류의 부산물과 폐기물을 다량 발생시켜 양적으로는 주 제품인 철강의 50％에 이르고 있다. 이러한 부산물과 폐기물은 철, 탄소 및 석회석 등의 재활용이 가능한 유효한 자원을 다량 함유하고 있어 이들을 그대로 매립해 버리는 것은 자원 및 에너지의 낭비이다.In general, the steel industry consumes a large amount of raw materials and energy, not only producing steel, but also generating a large amount of various by-products and wastes, quantitatively reaching 50% of the main product steel. These by-products and waste contain a large amount of effective resources that can be recycled such as iron, carbon and limestone, and it is a waste of resources and energy to bury them as they are.
제철산업의 부산물과 폐기물은 철강슬래그로서, 철강슬래그는 고로슬래그와 제강슬래그(전로슬래그, 전기로슬래그)로 구분된다.By-products and wastes in the steel industry are divided into steel slag, which is divided into blast furnace slag and steel slag (electric furnace slag and electric furnace slag).
고로슬래그는 제철소 고로에서 선철을 제조하는 과정에서 발생하는 생성물을 말하는 것이며, 냉각방식에 따라 급냉슬래그와 서냉슬래그로 구분된다.Blast furnace slag refers to a product generated in the process of manufacturing pig iron in steel mill blast furnace, and is divided into quench slag and slow cooling slag according to the cooling method.
급냉슬래그의 화학성분이 포틀랜드시멘트와 유사하고 수경성이 있어 슬래그시멘트의 원료로 이용된다.The chemical composition of quench slag is similar to Portland cement, and it is used as raw material for slag cement because it is hydraulic.
제강슬래그는 선철을 강을 만들기 위해 쇳물에 녹아 있는 탄소, 규소 성분 등을 제거하는 공정에서 발생하는 생성물을 말하는 것이며, 전로슬래그와 전기로슬래그로 구분되고, 전기로슬래그는 로 내의 분위기를 산화성, 환원성으로 처리하는 방법에 따라 산화슬래그와 환원슬래그로 구분된다.Steelmaking slag refers to a product that is produced in the process of removing carbon and silicon components in molten iron to make pig iron, and is divided into converter slag and electric furnace slag. Depending on the treatment method, it is divided into oxidized slag and reduced slag.
제강슬래그의 화학성분이 포틀랜드시멘트와 유사하지 못하여 시멘트의 원료로 사용하지 못하고 단순 매립용으로 사용되고 있다.The chemical composition of steelmaking slag is not similar to Portland cement, so it is not used as raw material for cement and is used for simple landfill.
철강슬래그의 화학조성은 아래와 같다.The chemical composition of the steel slag is as follows.
철강슬래그는 유리석회(Free CaO)성분이 다량 있어 수분과 반응하여 수산화칼슘(Ca(OH)2)로 되는데, 유리석회(Free CaO)성분보다 수산화칼슘(Ca(OH)2)이 부피가 약 2배 크기로 팽창하기 때문에 슬래그가 팽창되고 붕괴가 되므로 안정화하지 않으면 재활용할 수 없다.Steel slag has a large amount of free lime, which reacts with moisture to form calcium hydroxide (Ca (OH) 2 ), which is about twice the volume of calcium hydroxide (Ca (OH) 2 ) than free lime. As it expands in size, the slag expands and collapses and cannot be recycled unless stabilized.
팽창 붕괴성이 있는 철강슬래그를 도로 및 콘크리트용 골재로 재활용 용도로 활용하기 위해서는 충분히 안정화 시켜야 한다. 철강슬래그를 안정화시키는 방법으로 에이징 처리, 급냉처리, 개질처리 등 다양한 방법들이 있다.The expansion and collapse of steel slag must be sufficiently stabilized to be used for recycling purposes for road and concrete aggregates. As a method of stabilizing steel slag, there are various methods such as aging treatment, quenching treatment, and reforming treatment.
그 중에 일반적인 방법인 에이징 처리방법은, 고온의 철강슬래그를 서냉 시킨 후 적절한 입도로 파쇄한 다음, 사용 전에 대기 중에서 방치하여 인위적으로 유리석회(Free CaO)성분을 수분에 노출시켜 수산화석회(Ca(OH)2)로 변환함으로 재활용 용도로 사용할 시에 팽창 붕괴 현상이 발생하지 않도록 사전에 수화반응을 유도하는 방법이다. 이 방법은 보통 3m정도의 높이로 대기 중에 야적하여 방치하는 것이다. 팽창이 안정하기까지는 유리석회(Free CaO)성분의 함량에 따라 3?12개월 이상의 장기간의 시간을 요구한다. 기간을 단축하기 위하여 여러 가지가 있는데, 그 중 에 온수 에이징 처리방법의 대표적인 기술로는 일본 공개특허공보 평3-13517호가 있는데 유리석회(Free CaO)성분을 수산화석회(Ca(OH)2)로 안정화하는 것이며, 증기 에이징 처리방법의 대표적인 기술로는 일본 공개특허공보 소61-101441호가 있는데 이 역시 유리석회(Free CaO)성분을 수산화석회(Ca(OH)2)로 안정화하는 것이다. 이것들은 처리기간이 48시간 이상 필요하고, 처리비용이 고가이고, 1회 처리량이 적은 점에 문제가 있고, 수산화석회(Ca(OH)2)에 의해 알카리성 침출수가 생성됨에 문제가 있다.Among them, the aging treatment method, which is a general method, is obtained by slowly cooling a high-temperature steel slag, crushing it into an appropriate particle size, and then leaving it in the air before use to artificially expose free lime (Ca) component to moisture to make lime (Ca) OH) 2 ) to induce a hydration reaction in advance so that expansion collapse does not occur when used for recycling. This method is usually about 3m high and left unattended in the air. Until expansion is stable, it requires a long time of 3-12 months or more depending on the content of free lime (Free CaO). In order to shorten the period, there are various methods. Among them, a representative technique of the hot water aging treatment method is Japanese Patent Laid-Open No. 3-13517. The free lime (CaO) component is converted into lime hydroxide (Ca (OH) 2 ). As a representative technique of the steam aging treatment method, there is a Japanese Laid-Open Patent Publication No. 61-101441, which also stabilizes the free lime (Ca) component with lime hydroxide (Ca (OH) 2 ). These require a treatment period of 48 hours or more, have a problem in that the treatment cost is high, the throughput is small, and there is a problem in that alkaline leachate is generated by lime hydroxide (Ca (OH) 2 ).
또한 수분에 탄산가스를 흡수시켜 유리석회(Free CaO)성분을 탄산화를 촉진하는 대표적인 기술로는 한국 등록번호 10-0537345호가 있는데, 유리석회(Free CaO)성분을 탄산화를 촉진하는 효과를 높일 수 있으나, 수분의 탄산가스 흡수량이 상당히 작아 탄산화 시킬 수 있는 량을 많이 할 수 없는 점에 문제가 있다.In addition, as a representative technology for promoting carbonation of free lime (Free CaO) component by absorbing carbon dioxide in water, there is Korea Registration No. 10-0537345, but it is possible to increase the effect of promoting the carbonation of free lime (Ca) However, there is a problem in that the amount of carbonic acid gas absorbed in water is so small that the amount that can be carbonated cannot be large.
본 발명의 목적은 유리석회(Free CaO)성분이 함유한 철강슬래그를 탄산가스와의 반응을 시켜 안정화 된 철강슬래그를 제조하기 위한 것이다.An object of the present invention is to produce a stabilized steel slag by reacting the steel slag containing free lime (Ca) component with carbon dioxide gas.
본 발명에서는 물에 대한 용해도가 높은 탄산나트륨을 이용하여 철강슬래그의 유리석회(Free CaO)성분을 탄산칼슘으로 변환시켜 철강슬래그를 안정화시키고 반응 후의 생성물인 수산화나트륨 수용액에 탄산가스를 투입하므로 재 이용할 수 있는 탄산나트륨 수용액을 형성시키므로 연속적으로 철강슬래그를 안정화 할 수 있다.In the present invention, by converting the free lime (CaO) component of the steel slag into calcium carbonate using sodium carbonate having high solubility in water, the steel slag is stabilized and carbon dioxide gas is added to the aqueous solution of sodium hydroxide, which is a product after the reaction, so that it can be reused. Forming an aqueous sodium carbonate solution can stabilize steel slag continuously.
본 발명에 따르면, 철강슬래그를 안정화하는 과정에서 탄산나트륨, 수산화나트륨의 용해도가 높은 공정수를 공급하여, 철강슬래그에 함유하고 있는 유리석회 성분을 탄산칼슘으로 반응시킬 수 있는 기회를 높임으로 빠른 기간에 안정화 된 철강슬래그를 생산 할 수 있다.According to the present invention, by supplying process water with high solubility of sodium carbonate and sodium hydroxide in the process of stabilizing steel slag, it is possible to increase the chance of reacting the free lime component contained in the steel slag with calcium carbonate in a short period of time. It can produce stabilized steel slag.
또한, 본 발명에서는 반응 후에 형성된 수산화나트륨 공정수에 탄산가스를 투입하므로서 탄산나트륨이 많이 함유한 공정수로 변환되어 연속적으로 공급하여 앙정화 된 철강슬래그를 생산할 수 있다.In addition, in the present invention, by adding carbon dioxide gas to the sodium hydroxide process water formed after the reaction can be converted into process water containing a lot of sodium carbonate and continuously supplied to produce a stabilized steel slag.
규산나트륨을 점결제로 사용된 폐주물사를 철강슬래그를 안정화 하는데 보조제로 활용하여 폐주물사의 재활용 범위를 넓힐 수 있다.The waste foundry sand, which uses sodium silicate as a caking additive, can be used as an aid to stabilize steel slag.
철강슬래그를 안정화시키는데, 철강슬래그의 성분 중의 유리석회(Free CaO)성분이 수분과 반응하여 팽창 붕괴 현상이 일어나기 때문에 안정화 하여야만 재활용할 수 있는 제강슬래그가 될 수 있다.Stabilization of steel slag, because the free lime (CaO) component of the steel slag reacts with moisture to cause expansion and collapse, steel slag can be recycled only when stabilized.
철강슬래그의 성분 중의 유리석회(Free CaO)성분이 물과 반응하여 수산화칼슘으로 변환되면서 약 2배의 부피 팽창을 하고, 물에 약간 용해되어 철강슬래그 용출수의 PH가 12이상이 되므로 수산화칼슘을 물에 녹지 않는 탄산칼슘으로 변환시키 므로 완전한 안정화를 시킬 수 있다. 수산화칼슘(Ca(OH)2)은 물 1리터당 0.82g 밖에 용해되지 않아 철강슬래그의 성분 중의 유리석회(Free CaO)성분이 물과 반응하여 수산화칼슘으로 변환된 것을 탄산칼슘으로 변환하려면 상당히 많은 공정수가 필요하게 되며, 철강슬래그를 안정화시키는데 오래 걸리는 결점이 있었다.Free lime (CaO) component of the steel slag reacts with water and converts to calcium hydroxide, causing about twice the volume expansion, and slightly dissolved in water, so that the pH of the steel slag elution water becomes 12 or more. Conversion to calcium carbonate, which does not dissolve, ensures complete stabilization. Calcium hydroxide (Ca (OH) 2 ) dissolves only 0.82g per liter of water, so a considerable amount of process is required to convert free calcium oxide (Ca) into the calcium hydroxide by reacting with water. In addition, there was a long defect to stabilize the steel slag.
본 발명은 이러한 종래의 결점을 해소하기 위하여 안출된 것으로, 탄산가스를 탄산나트륨, 수산화나트륨이 함유한 공정수에 공급하여 철강슬래그의 성분 중의 유리석회(Free CaO)성분을 안정화할 때에 공정수의 양을 상당히 줄이므로서 안정화 된 철강슬래그를 생산하는 방법을 목적으로 한다.The present invention was devised to solve such a conventional drawback, and the amount of process water when stabilizing the free lime component in the steel slag by supplying carbon dioxide gas to the process water containing sodium carbonate and sodium hydroxide. The aim is to produce a stabilized steel slag with a significant reduction in power consumption.
철강슬래그의 성분 중의 유리석회(Free CaO)성분을 안정화하기 위하여 공정수에 [반응식 1] 에 의해 생성된 탄산가스를 공급하여 철강슬래그의 성분 중의 유리석회(Free CaO)성분과 탄산가스와 화학반응이 일어나므로서 철강슬래그의 성분 중의 유리석회(Free CaO)성분이 탄산칼슘로 변환되어 변환된 탄산칼슘이 물에 불용상태로 되므로 안정화 된 철강슬래그가 생산하게 된다.In order to stabilize the free lime component in the steel slag, the carbon dioxide gas generated by [Scheme 1] is supplied to the process water to chemical reaction with the free lime component and carbon dioxide gas in the steel slag. As a result, the free lime (Ca) component of the steel slag is converted to calcium carbonate, and the converted calcium carbonate becomes insoluble in water, thereby producing a stabilized steel slag.
그렇지만, 철강슬래그의 성분 중의 유리석회(Free CaO)성분은 철강슬래그 총무게에 20?50％ 존재한다.However, the free lime component of the steel slag is present in the steel slag total weight by 20 to 50%.
수산화칼슘은 세척수 1L당 0.82g 밖에 녹지 않고, [반응식 2] 와 같이 탄산가스는 세척수 1L당 20℃에서는 0.88L, 40℃에서는 0.53L 밖에 녹지 않는다.Calcium hydroxide dissolves only 0.82 g per 1 L of washing water, and carbon dioxide gas dissolves only 0.88 L at 20 ° C. and 0.53 L at 40 ° C. per 1 L of washing water, as shown in [Scheme 2].
철강슬래그의 성분 중의 유리석회(Free CaO)성분을 탄산칼슘으로 변환하기 위해서는 [반응식 3] 과 같이 철강슬래그의 성분 중의 유리석회(Free CaO)성분을 수산화칼슘으로 변환하여야 하고, 수산화칼슘이 공정수에 녹아야하고, 탄산가스도 공정수에 녹아야 반응이 일어나 철강슬래그의 성분 중의 유리석회(Free CaO)성분이 안정화 된 철강슬래그를 생산할 수 있다.In order to convert the free lime (CaO) component in the steel slag into calcium carbonate, the free lime (Ca) component in the steel slag must be converted to calcium hydroxide as shown in [Scheme 3], and the calcium hydroxide is dissolved in the process water. In addition, carbon dioxide gas must be dissolved in the process water to react to produce steel slag with stabilized free lime (CaO) component among the steel slag.
철강슬래그의 성분 중의 유리석회(Free CaO)성분은 철강슬래그 총무게에 20?50％ 존재하기 때문에 안정화 된 철강슬래그를 생산하기 위해서는 유리석회(Free CaO)성분이 물과 반응하여 수산화칼슘으로 변환 되고, 변환된 수산화칼슘이 물에 용해된 상태를 유지하여야 탄산가스와 화학반응이 잘 일어날 수가 있다. 또한 탄산가스도 물에 용해된 상태를 유지하여야 수산화칼슘과 화학반응이 일어날 수가 있다.Free CaO in steel slag is present in 20 ~ 50% of total weight of steel slag. To produce stabilized steel slag, free lime is reacted with water and converted to calcium hydroxide. The converted calcium hydroxide must remain dissolved in water so that chemical reactions with carbon dioxide can occur. In addition, carbon dioxide gas must remain dissolved in water to cause chemical reaction with calcium hydroxide.
수산화칼슘과 탄산가스가 물 1L당 용해될 수 양이 너무나 적기 때문에 용해시킬 공정수의 양이 철강슬래그 부피의 200?5000배가 필요하기 때문에 상당히 많은 양이 필요하게 된다.Since calcium hydroxide and carbon dioxide are so small that they can be dissolved per liter of water, the amount of process water to be dissolved is required to be 200 to 5000 times the volume of steel slag, which is quite large.
위와 같은 반응은 아래와 같이 일어나게 된다.The above reaction occurs as follows.
본 발명은 위와 같은 수산화칼슘과 탄산가스의 용해할 수 있는 양이 작기 때문에 공정수의 양이 철강슬래그 부피의 200?5000배가 필요하게 되므로 공정수의 양을 줄일 수 있는 방법을 강구하게 되었다.In the present invention, since the amount of dissolving calcium hydroxide and carbon dioxide gas is small, the amount of process water is required to be 200 to 5000 times the volume of the steel slag, and thus a method for reducing the amount of process water has been devised.
철강슬래그의 성분 중의 유리석회(Free CaO)성분과 화학반응이 일어 날 수 있는 탄산나트륨을 공정수에 용해시키므로써 유리석회(Free CaO)성분과 탄산나트륨의 탄산성분과의 화학반응 속도를 높일 수가 있다.By dissolving the free lime (CaO) component in the steel slag and the sodium carbonate, which can cause a chemical reaction, in the process water, the chemical reaction rate between the free lime (Ca) component and the sodium carbonate carbonate component can be increased.
탄산나트륨은 물 1L당 0℃에는 71g 용해되며, 100℃에서는 455g 용해된다. 따라서, 수산화칼슘이 물에 용해되는 양과 비교하여 보면 거의 100?500배 물에 용해되기 때문에 탄산나트륨을 사용하지 않았을 때의 공정수의 양을 탄산나트륨을 사용하였을 때에는 공정수의 양을 그 비율만큼 줄일 수가 있다.Sodium carbonate dissolves 71 g at 0 ° C. per 1 L of water and 455 g at 100 ° C. Therefore, since calcium hydroxide is nearly 100-500 times dissolved in water compared to the amount dissolved in water, the amount of process water when sodium carbonate is not used can be reduced by that ratio when sodium carbonate is used. .
위와 같은 화학반응은 아래와 같다.The above chemical reaction is as follows.
화학반응이 일어나게 되면 탄산칼슘은 물에 불용하게 되어 침전되고, 공정수 내에는 생성물인 수산화나트륨이 녹아 있게 된다.When a chemical reaction occurs, calcium carbonate becomes insoluble in water and precipitates, and sodium hydroxide as a product is dissolved in process water.
수산화나트륨은 물 1L당 0℃에는 420g 용해되며, 100℃에는 3470g 용해되므로 공정수에 수산화나트륨이 용해된 상태로 유지하게 된다.Sodium hydroxide is dissolved 420g at 0 ℃ per 1L of water, 3470g dissolved at 100 ℃ to maintain the sodium hydroxide dissolved in the process water.
수산화나트륨은 탄산나트륨보다 물에 용해되는 양이 많아 공정수 내에서는 침전이 절대 일어 날 수가 없고, 공정수내에서 용해된 상태로 유지하게 된다.Since sodium hydroxide is more soluble in water than sodium carbonate, precipitation cannot occur in process water, and it is maintained in a dissolved state in process water.
수산화나트륨은 유리석회(Free CaO)성분과는 화학반응이 없으므로, 수산화나트륨이 유리석회(Free CaO)성분과 화학반응이 일어 날 수 있는 탄산나트륨으로 변화시켜야 한다.Sodium hydroxide has no chemical reaction with free lime, so sodium hydroxide should be changed to sodium carbonate, which can react with free lime.
수산화나트륨은 물 1L당 0℃에는 420g 용해되며, 100℃에는 3470g 용해되므로, 탄산가스를 공정수에 투입하였을 때에 탄산가스는 공정수 1L당 20℃에서는 0.88L, 40℃에서는 0.53L 밖에 녹는것 보다는 물 1리터당 0℃에는 420g 용해되며, 100℃에는 3470g 용해될 수 있는 수산화나트륨이 녹아 있는 공정수에서 탄산가스가 화학반응이 500?2000배 일어난다.Sodium hydroxide dissolves 420g at 0 ° C and 3470g at 100 ° C per liter of water, so when carbon dioxide is injected into the process water, carbon dioxide is only dissolved at 0.88L at 20 ° C and 0.53L at 40 ° C. Rather, 420g is dissolved at 0 ° C per liter of water and 500 ~ 2000 times of carbon dioxide chemical reaction occurs in process water in which sodium hydroxide is dissolved, which can be dissolved at 3470g at 100 ° C.
일어나는 [반응식 5] 와 같이 된다.It occurs as in [Scheme 5].
공정수에는 철강슬래그의 성분 중의 유리석회(Free CaO)성분과 탄산나트륨과의 화학반응이 끝나면 탄산칼슘은 물에 불용되어 침전되고 공정수에는 물에 용해된 수산화나트륨이 있게 된다.In the process water, when the chemical reaction between free lime and sodium carbonate in the steel slag is completed, calcium carbonate is insoluble in water and precipitated, and the process water contains sodium hydroxide dissolved in water.
[반응식 5] 과 같이 공정수에 용해된 수산화나트륨에 탄산가스를 공정수에 투입하여 수산화나트륨과 탄산가스와의 화학반응을 시켜 탄산나트륨으로 생성하게 하여, 또 다시 철강슬래그의 성분 중의 유리석회(Free CaO)성분과 탄산나트륨과의 화학반응을 시키게 함으로 공정수를 연속적으로 재 활용, 재 이용할 수가 있다.As shown in [Scheme 5], sodium hydroxide dissolved in the process water was added carbon dioxide gas to the process water, followed by chemical reaction between sodium hydroxide and carbon dioxide gas to produce sodium carbonate, and free lime in the components of the steel slag. By chemical reaction between CaO) and sodium carbonate, process water can be recycled and reused continuously.
규산나트륨을 점결제로 쓰는 주물사에는 규산나트륨에 의해 수산화나트륨, 탄산나트륨으로 변환된 폐주물사로 바뀌게 된다.Foundry sand using sodium silicate as a caking additive is converted to waste foundry sand converted to sodium hydroxide and sodium carbonate by sodium silicate.
이 폐주물사는 다시 주물사로 재활용되는 것이 아니고, 일반 흙이나, 재생골재 등과 50％ 혼합하여 성토재로 활용할 뿐이다.This waste foundry sand is not recycled back to foundry sand, but is mixed with ordinary soil or recycled aggregates by 50% and used as fill material.
폐주물사에 남아 있는 성분이 탄산나트륨, 수산화나트륨이기 때문에 철강슬래그의 성분 중의 유리석회(Free CaO)성분의 무게 대비 1?5％ 혼합하여 분쇄 후 공정수로 처리하는 과정에서 폐주물사에 남아 있는 성분인 탄산나트륨, 수산화나트륨이 물에 용해되어 자연히 공정수 내에는 탄산나트륨, 수산화나트륨이 녹아 있는 공정수로 되기 때문에 위에서 설명한 것과 같이 철강슬래그의 성분 중의 유리석회(Free CaO)성분과 화학반응을 일으켜서 안정화 된 철강슬래그를 생산할 수가 있다.Since the components remaining in the waste foundry sand are sodium carbonate and sodium hydroxide, sodium carbonate, which is a component remaining in the waste foundry sand in the process of pulverizing with 1 ~ 5% of the weight of free lime (CaO) component in the steel slag, is processed after grinding. As sodium hydroxide is dissolved in water and naturally becomes sodium carbonate and sodium hydroxide in the process water, the steel slag stabilized by chemical reaction with free lime (CaO) component of steel slag as described above. I can produce it.
물은 20℃에서 표면장력이 약 72dyne/㎠이지만은, 공정수에 0.0001?0.1％의 계면활성제를 첨가하게 되면, 물의 표면장력이 약 15dyne/㎠까지 낮아질 수 있어 철강슬래그의 표면에 공정수가 더욱 더 흡착할 수 있고, 철강슬래그의 표면에 공정수가 더욱 더 많이 젖게 되고, 철강슬래그 내부에 까지 공정수가 스며들게 할 수 있어 반응을 더 잘 일어나게 도움을 준다.Although water has a surface tension of about 72 dyne / cm2 at 20 ° C, when 0.0001 to 0.1% of surfactant is added to the process water, the surface tension of water can be lowered to about 15 dyne / cm2. More adsorbable, more and more process water is wetted on the surface of the steel slag, and the process water can penetrate the inside of the steel slag to help the reaction occur better.
도면 1 본 발명의 방법으로 탄산나트륨, 수산화나트륨이 함유한 공정수를 이용한 철강슬래그를 안정화하는 공정도.1 is a process chart for stabilizing steel slag using a process water containing sodium carbonate and sodium hydroxide by the method of the present invention.
도면 2 본 발명의 방법으로 폐주물사를 이용한 철강슬래그를 안정화하는 공정도2 is a process chart for stabilizing steel slag using waste casting sand by the method of the present invention
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| CN103992054A (en) * | 2014-02-23 | 2014-08-20 | 济南大学 | Carbonated steel slag aggregate and preparation method thereof |
| CN110128037A (en) * | 2019-05-14 | 2019-08-16 | 中冶节能环保有限责任公司 | A kind of steel slag tailings prepare the processing unit and method of sandstone |
| CN115672950A (en) * | 2022-09-20 | 2023-02-03 | 原初科技（北京）有限公司 | Steel slag carbon fixation device and use method thereof |
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| KR20000041665A (en) * | 1998-12-23 | 2000-07-15 | 이구택 | Seasoning method of electric furnace slag with hot carbonated water |
| JP4434555B2 (en) * | 2002-05-21 | 2010-03-17 | Ｊｆｅミネラル株式会社 | Processing method of granulated blast furnace slag |
| KR100590994B1 (en) * | 2004-09-08 | 2006-06-19 | 재단법인 포항산업과학연구원 | The method for aging a steel making slag |
| KR100807104B1 (en) * | 2007-01-22 | 2008-02-26 | 임정빈 | Removal method of lime component in circulating aggregate using carbon dioxide produced by burning combustible waste |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103992054A (en) * | 2014-02-23 | 2014-08-20 | 济南大学 | Carbonated steel slag aggregate and preparation method thereof |
| CN110128037A (en) * | 2019-05-14 | 2019-08-16 | 中冶节能环保有限责任公司 | A kind of steel slag tailings prepare the processing unit and method of sandstone |
| CN115672950A (en) * | 2022-09-20 | 2023-02-03 | 原初科技（北京）有限公司 | Steel slag carbon fixation device and use method thereof |
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