KR20240097421A - Method of production of ferrous sulfate - Google Patents
Method of production of ferrous sulfate Download PDFInfo
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- KR20240097421A KR20240097421A KR1020220179452A KR20220179452A KR20240097421A KR 20240097421 A KR20240097421 A KR 20240097421A KR 1020220179452 A KR1020220179452 A KR 1020220179452A KR 20220179452 A KR20220179452 A KR 20220179452A KR 20240097421 A KR20240097421 A KR 20240097421A
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- iron
- sulfuric acid
- ferrous sulfate
- containing material
- acid solution
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 title claims abstract description 51
- 239000011790 ferrous sulphate Substances 0.000 title claims abstract description 43
- 235000003891 ferrous sulphate Nutrition 0.000 title claims abstract description 43
- 229910000359 iron(II) sulfate Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 137
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 132
- 229910052742 iron Inorganic materials 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000010802 sludge Substances 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 12
- 238000009628 steelmaking Methods 0.000 claims description 7
- 239000000428 dust Substances 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000004568 cement Substances 0.000 description 9
- 229910000358 iron sulfate Inorganic materials 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- -1 mill scale Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
-
- 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
- Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
황산제일철 제조방법이 제공된다.
본 발명은, 철 함유 물질에 황산 수용액을 혼합하여 황산제일철을 제조하는 방법으로서, 상기 황산 수용액의 농도는 20 내지 90%이고, 상기 철 함유 물질에 대한 황산 수용액의 혼합비는 중량비로 0.2 내지 0.5를 만족한다. A method for producing ferrous sulfate is provided.
The present invention is a method of producing ferrous sulfate by mixing an aqueous sulfuric acid solution with an iron-containing material, wherein the concentration of the aqueous sulfuric acid solution is 20 to 90%, and the mixing ratio of the aqueous sulfuric acid solution to the iron-containing material is 0.2 to 0.5 by weight. Satisfies.
Description
본 발명은 황산제일철 제조방법에 관한 것으로, 보다 상세하게는, 철 함유 물질 및 황산수용액을 사용하여 황산철 수용액 제조 단계를 생략하고 곧바로 황산제일철을 얻을 수 있는 황산제일철 제조방법에 관한 것이다. The present invention relates to a method for producing ferrous sulfate, and more specifically, to a method for producing ferrous sulfate that uses an iron-containing material and an aqueous sulfuric acid solution to obtain ferrous sulfate directly, omitting the step of preparing an aqueous iron sulfate solution.
수처리 응집제로 널리 쓰이는 황산제일철은 시멘트 중 6가크롬을 3가크롬으로 환원시킴으로써 각종 암과 질병 문제가 개선된 안전한 시멘트 제조를 위해 사용되고 있다. 통상 황산제일철은 철강재 산세, 이산화티타늄 제조 등 주로 타제품 제조공정에서 발생하는 황산철 용액으로부터 제조되고 있다.Ferrous sulfate, widely used as a water treatment coagulant, is used to manufacture safe cement that improves various cancer and disease problems by reducing hexavalent chromium in cement to trivalent chromium. Typically, ferrous sulfate is manufactured from iron sulfate solutions generated in other product manufacturing processes, such as steel pickling and titanium dioxide manufacturing.
한편 황산제일철은 철과 황산의 반응을 통해 제조될 수 있는데, 최근에는 자원 재활용 및 제조비용 저감 측면에서 철과 황산을 함유한 각종 부산물, 폐기물 등을 활용하는 기술에 많은 관심이 집중되고 있다. 철강산업에서는 Mill scale 뿐만 아니라 제선, 제강 공정 등의 공정에서 철 함량이 높은 더스트, 슬러지 등 철 성분을 다량 함유한 부산물이 발생된다. 또한 반도체산업에서는 높은 농도의 폐황산이 다량 발생되므로, 이러한 부산물들을 활용하여 황산제일철을 제조함으로써 폐기물 처리비용 저감, 자원의 효율적 활용 등의 효과를 구현할 수 있다.Meanwhile, ferrous sulfate can be manufactured through the reaction of iron and sulfuric acid. Recently, much attention has been focused on technologies that utilize various by-products and wastes containing iron and sulfuric acid in terms of resource recycling and reduction of manufacturing costs. In the steel industry, by-products containing large amounts of iron, such as dust and sludge with high iron content, are generated in processes such as iron making and steelmaking processes as well as mill scale. Additionally, since a large amount of high-concentration waste sulfuric acid is generated in the semiconductor industry, effects such as reducing waste disposal costs and efficient use of resources can be realized by using these by-products to manufacture ferrous sulfate.
상기 언급한 철강재 산세, 이산화티타늄 제조 공정에서 발생하는 황산철 용액으로부터 황산제일철을 제조하기 위해서는 증발 또는 냉각을 통한 결정화 과정이 필요하며, 이를 위해 다량의 에너지 및 복잡한 설비가 필요한 단점이 있다. 또한 철과 황산을 함유한 부산물, 폐기물 등을 활용하는 경우에도, 일반적인 습식공정을 사용하게 되면 황산철 용액이 발생하고 에너지 및 설비 측면에서 불리한 결정화 과정을 거쳐야만 하는 단점이 있다. 더불어 결정화 과정 후 황산제일철을 여액으로부터 분리하기 위해 여과 과정을 거쳐야만 한다.In order to produce ferrous sulfate from the iron sulfate solution generated in the above-mentioned steel pickling and titanium dioxide manufacturing processes, a crystallization process through evaporation or cooling is required, which has the disadvantage of requiring a large amount of energy and complex equipment. In addition, even when using by-products and wastes containing iron and sulfuric acid, using a general wet process has the disadvantage of generating an iron sulfate solution and having to go through a crystallization process that is disadvantageous in terms of energy and equipment. In addition, after the crystallization process, a filtration process must be performed to separate the ferrous sulfate from the filtrate.
특허문헌 1에에서는 철 함유 부산물로서 제철소 탈황더스트를 사용하여 황산용액과의 반응을 통해 황산철 수용액을 제조하는 방법을 제시하고 있으며, 이와 같은 습식공정은 상기 언급한 바와 같이 결정화 및 여과 과정을 거쳐야만 한다. Patent Document 1 proposes a method of producing an aqueous iron sulfate solution through reaction with a sulfuric acid solution using steel mill desulfurization dust as an iron-containing by-product, and this wet process requires crystallization and filtration as mentioned above. do.
이러한 단점을 극복하기 위해, 특허문헌 2에서는 철원과 황산용액을 반응시켜 황산철 수용액을 제조한 후 농황산을 추가하여 황산제일철을 제조하는 방법을 제시하고 있다. 그러나 이를 통해 결정화 공정은 생략 가능하나 황산제일철이 용액과 혼합되어 있는 슬러리 형태로 제조되므로 여전히 여과 과정을 거쳐야 하는 단점이 있다. 또한 90wt% 이상의 농황산이 필요하므로 주로 90wt% 이하의 농도로 발생되는 폐황산만으로 황산제일철을 제조하는 것이 어려운 단점이 있다.To overcome these shortcomings, Patent Document 2 proposes a method of producing ferrous sulfate by reacting an iron source with a sulfuric acid solution to prepare an aqueous iron sulfate solution and then adding concentrated sulfuric acid. However, although this allows the crystallization process to be omitted, it has the disadvantage of still having to go through a filtration process because it is manufactured in the form of a slurry in which ferrous sulfate is mixed with the solution. In addition, since concentrated sulfuric acid of 90 wt% or more is required, there is a disadvantage in that it is difficult to produce ferrous sulfate only with waste sulfuric acid, which is mainly generated at a concentration of 90 wt% or less.
본 발명은 철 함유 물질 및 황산수용액을 사용하여 황산철 수용액 제조 단계를 생략하고 황산제일철을 제조하는 방법을 제공함을 목적으로 하며, 구체적으로, 철 함유 물질 및 황산수용액을 사용하여 결정화 및 여과 과정을 거치지 않고 철원과 황산을 반응시켜 곧바로 황산제일철을 제조하는 방법을 제공함을 목적으로 한다. The purpose of the present invention is to provide a method for producing ferrous sulfate using an iron-containing material and an aqueous sulfuric acid solution, omitting the step of preparing an aqueous iron sulfate solution. Specifically, the crystallization and filtration processes are performed using an iron-containing material and an aqueous sulfuric acid solution. The purpose is to provide a method for producing ferrous sulfate directly by reacting an iron source with sulfuric acid without going through the process.
본 발명의 과제는 상술한 내용에 한정되지 아니한다. 본 발명이 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명 명세서의 전반적인 사항으로부터 본 발명의 추가적인 과제를 이해하는데 아무런 어려움이 없을 것이다.The object of the present invention is not limited to the above-described content. Anyone skilled in the art to which the present invention pertains will have no difficulty in understanding the additional problems of the present invention from the overall details of the present invention specification.
본 발명의 일 측면은,One aspect of the present invention is,
철 함유 물질에 황산 수용액을 혼합하여 황산제일철을 제조하는 방법으로서,A method of producing ferrous sulfate by mixing an aqueous sulfuric acid solution with an iron-containing material,
상기 황산 수용액의 농도는 20 내지 90%이고, 상기 철 함유 물질에 대한 황산 수용액의 혼합비는 중량비로 0.2 내지 0.5인, 황산제일철 제조방법에 관한 것이다. The concentration of the aqueous sulfuric acid solution is 20 to 90%, and the mixing ratio of the aqueous sulfuric acid solution to the iron-containing material is 0.2 to 0.5 by weight.
상기 철 함유 물질은 자체 중량%로 철 성분이 50중량% 이상일 수 있다. The iron-containing material may have an iron content of 50% by weight or more.
상기 철 함유 물질은 철 스크랩, 철광석, 밀스케일(Mill scale), 철 함유 더스트, 철 함유 슬러지를 포함하는 군으로부터 선택된 1 종 이상일 수 있다. The iron-containing material may be one or more selected from the group including iron scrap, iron ore, mill scale, iron-containing dust, and iron-containing sludge.
상기 철 함유 슬러지는 제강 OG 슬러지일 수가 있다.The iron-containing sludge may be steelmaking OG sludge.
상기 황산 수용액은 반도체 폐황산일 수 있다.The sulfuric acid aqueous solution may be semiconductor waste sulfuric acid.
상술한 구성의 본 발명에 의하면 철 함유 물질과 황산수용액을 혼합하는 간단한 공정으로 황산제일철을 곧바로 제조함으로써 결정화 및 여과 과정을 거쳐야 하는 종래 기술 대비 에너지 비용이 감소되고 제조설비도 단순화할 수 있는 장점이 있다. According to the present invention of the above-described configuration, ferrous sulfate is directly produced through a simple process of mixing iron-containing materials and an aqueous sulfuric acid solution, which has the advantage of reducing energy costs and simplifying manufacturing facilities compared to the conventional technology that requires crystallization and filtration processes. there is.
또한 철 함유 물질과 황산을 함유한 각종 부산물, 폐기물 등을 활용함으로써 폐기물 처리비용 저감 및 자원의 효율적 활용이 가능하다는 잇점이 있다.In addition, there is the advantage of reducing waste disposal costs and efficient use of resources by utilizing various by-products and wastes containing iron-containing materials and sulfuric acid.
이하, 본 발명을 설명한다. Hereinafter, the present invention will be described.
철 함유 물질과 황산의 반응은 발열반응으로서 두 물질을 혼합하면 다량의 열이 발생하여 반응에 참여하지 않은 잉여의 물을 증발시키게 된다. 그런데 혼합 및 증발 후, 잔여 물의 양이 황산철 용액이 생성되지 않을 정도로 적게 되면 황산제일철은 고체 형태로 곧바로 생성된다. 즉, 본 발명자는 철 함유 물질과 황산의 반응에 의한 생성열과 초기 물의 양, 즉 황산의 농도를 적절히 조절하면 고체 형태의 황산제일철을 곧바로 얻을 수 있음을 확인하고, 본 발명을 제시하는 것이다. The reaction between iron-containing substances and sulfuric acid is an exothermic reaction, and when the two substances are mixed, a large amount of heat is generated, causing excess water that did not participate in the reaction to evaporate. However, after mixing and evaporation, when the amount of remaining water is small enough to prevent the formation of an iron sulfate solution, ferrous sulfate is immediately generated in solid form. That is, the present inventor has confirmed that ferrous sulfate in solid form can be obtained immediately by appropriately controlling the heat of formation from the reaction between iron-containing materials and sulfuric acid and the initial amount of water, that is, the concentration of sulfuric acid, and proposes the present invention.
이러한 본 발명은, 철 함유 물질에 황산 수용액을 혼합하여 황산제일철을 제조하는 방법으로서, 상기 황산 수용액의 농도는 20 내지 90%이고, 상기 철 함유 물질에 대한 황산 수용액의 혼합비는 중량비로 0.2 내지 0.5를 만족한다. This invention is a method of producing ferrous sulfate by mixing an aqueous sulfuric acid solution with an iron-containing material, wherein the concentration of the aqueous sulfuric acid solution is 20 to 90%, and the mixing ratio of the aqueous sulfuric acid solution to the iron-containing material is 0.2 to 0.5 by weight. satisfies.
먼저, 본 발명에서 상기 철 함유 물질(철원)이란 철 성분을 함유한 물질을 의미하며, 철 스크랩, 철광석 등 철 함유 원료뿐만 아니라 Mill scale, 철 함유 더스트, 철 함유 슬러지 등 각종 철 함유 부산물도 포함된다. First, in the present invention, the iron-containing material (iron source) refers to a material containing iron components, and includes not only iron-containing raw materials such as iron scrap and iron ore, but also various iron-containing by-products such as mill scale, iron-containing dust, and iron-containing sludge. do.
상기 철 함유 물질은 자체 중량%로 철 성분을 50% 이상 함유되는 것이 바람직한데, 이는 다른 성분이 황산과 반응하는 것을 최소화하여 황산제일철을 용이하기 제조하기 위해서이다. The iron-containing material preferably contains more than 50% iron by weight, in order to easily produce ferrous sulfate by minimizing the reaction of other components with sulfuric acid.
본 발명에서 상기 황산은 신산, 폐황산을 포함한 어떤 형태의 황산이라도 무방하나 고체 형태의 황산제일철을 곧바로 제조하기 위해서는 적절한 농도의 황산을 사용해야 한다. 황산의 농도가 너무 낮으면 철과 황산의 반응에 의해 생성되는 열에 비해 물의 양이 상대적으로 많아 황산제일철이 용액 형태로 제조된다. 이에 반하여, 황산 농도가 너무 높으면 황산의 점도가 높아 철원과의 반응 및 황산제일철 생성이 효과적으로 이루어지지 못한다. In the present invention, the sulfuric acid may be any type of sulfuric acid, including acidic acid and spent sulfuric acid, but in order to directly produce ferrous sulfate in solid form, sulfuric acid of an appropriate concentration must be used. If the concentration of sulfuric acid is too low, the amount of water is relatively large compared to the heat generated by the reaction between iron and sulfuric acid, so ferrous sulfate is produced in solution form. On the other hand, if the sulfuric acid concentration is too high, the viscosity of the sulfuric acid is high and the reaction with the iron source and the production of ferrous sulfate cannot be effectively performed.
본 발명에서 상기 황산의 농도 범위는 20 ~ 90% 범위가 바람직하다.In the present invention, the concentration of sulfuric acid is preferably in the range of 20 to 90%.
한편, 상기 철 함유 물질과 황산수용액은 적절한 비율로 혼합이 되어야 한다. 철 함유 물질이 상대적으로 많으면 황산이 부족하여 황산제일철의 생성량이 적게 되며, 황산수용액이 상대적으로 많으면 잉여 황산이 잔류하게 되므로 제조된 황산제일철이 폐수처리, 시멘트 등에 사용될 때 나쁜 영향을 줄 수 있다. 철 함류 물질 대비 황산수용액의 혼합비는 0.2~0.5가 바람직하다. Meanwhile, the iron-containing material and the sulfuric acid aqueous solution must be mixed in an appropriate ratio. If the iron-containing material is relatively high, sulfuric acid is insufficient and the amount of ferrous sulfate produced is small. If the sulfuric acid aqueous solution is relatively high, excess sulfuric acid remains, so the produced ferrous sulfate may have a negative effect when used in wastewater treatment, cement, etc. The mixing ratio of the sulfuric acid aqueous solution to the iron-containing material is preferably 0.2 to 0.5.
상기 철 함유 물질과 황산수용액의 혼합은 통상의 교반이 가능한 반응기를 사용할 수 있다.For mixing the iron-containing material and the aqueous sulfuric acid solution, a reactor capable of ordinary stirring can be used.
본 발명은 철 함유 불질에서 Fe 함량이 상대적으로 낮은 제강 OG슬러지(Fe 57.5%)를 사용하므로 상대적으로 황산 사용량이 줄일 수가 있다. 만일 종래기술과 같이, 철 함유 물질로서 Fe, FeO 분말을 이용할 경우, 이들의 Fe 함량은 각각 98%, 76%로서 상대적으로 높기 때문에 소용되는 황산량도 더 필요하게 되는 것이다. 따라서 본 발명은 제강 OG 슬러지를 철 함유 물질로 선택함으로서 황산제일철을 제조함에 소요되는 황산량을 줄일 수 있다. Since the present invention uses steelmaking OG sludge (Fe 57.5%), which has a relatively low Fe content among iron-containing materials, the amount of sulfuric acid used can be relatively reduced. If, as in the prior art, Fe and FeO powders are used as iron-containing materials, their Fe content is relatively high at 98% and 76%, respectively, so more sulfuric acid is needed. Therefore, the present invention can reduce the amount of sulfuric acid required to produce ferrous sulfate by selecting steelmaking OG sludge as the iron-containing material.
이하 본 발명의 바람직한 실시예를 통하여 본 발명을 상세히 설명한다. 그러나 하기 실시예는 본 발명의 바람직한 일 실시예일뿐 본 발명이 하기 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail through preferred embodiments of the present invention. However, the following example is only a preferred example of the present invention and the present invention is not limited to the following example.
(실시예 1)(Example 1)
철 함유 물질로서 제강공정에서 발생하는 OG슬러지를 사용하였으며, 하기 표 1에 그 성분을 나타내었으며 그 단위는 중량%이다. 그리고 황산으로는 반도체산업에서 발생하는 폐황산을 사용하였으며, 황산의 농도는 50중량%인 것을 사용하였다.OG sludge generated in the steelmaking process was used as an iron-containing material, and its components are shown in Table 1 below, and the unit is weight%. And as sulfuric acid, waste sulfuric acid generated in the semiconductor industry was used, and the concentration of sulfuric acid was 50% by weight.
한편 상기 철 함유 물질과 황산수용액의 혼합 조건과, 반응으로 생성된 물질의 황산제일철 함유량을 하기 표 2에 각각 나타내었다. 황산제일철 함량의 측정은 하기 표 2에 나타난 바와 같은 혼합비로 철 함유 물질과 황산수용액을 5분간 혼합한 후, 그 생성물을 건조 및 분쇄하여 얻어진 분쇄물 중 황산제일철 함량을 측정하여 나타낸 것이다. Meanwhile, the mixing conditions of the iron-containing material and the aqueous sulfuric acid solution and the ferrous sulfate content of the material produced through the reaction are shown in Table 2 below. The ferrous sulfate content was measured by mixing iron-containing materials and an aqueous sulfuric acid solution for 5 minutes at the mixing ratio shown in Table 2 below, drying and pulverizing the product, and measuring the ferrous sulfate content in the pulverized product.
상기 표 1-2로부터 알 수 있는 바와 같이, 철 함유 물질과 황산수용액과의 혼합을 통해 황산제일철 함량이 20% 이상인 물질의 제조가 가능함을 확인할 수 있다. 다만 황산수용액의 혼합량이 적은 비교예 1은 황산제일철 함량이 20% 미만이었으나, 황산수용액의 혼합량이 과도한 비교예 2는 황산제일철 함량은 75%로 높게 나타났다. 그러나 폐황산 혼합비율이 50%를 초과하면 잉여 황산이 잔류하게 되어 황산제일철의 pH가 낮아지고, pH가 낮은 황산제일철을 시멘트에 혼합하면 시멘트의 강도가 낮아질 수 있는 문제가 있다. 또한 폐수처리 약품으로 사용하는 경우에도 pH가 낮은 물질을 사용하게 되면 폐수의 pH가 낮아지게 되므로 추가적인 중화제를 사용해야 하는 단점도 있다. As can be seen from Table 1-2, it can be confirmed that it is possible to produce a material with a ferrous sulfate content of 20% or more by mixing an iron-containing material with an aqueous sulfuric acid solution. However, in Comparative Example 1, where the mixing amount of the aqueous sulfuric acid solution was small, the ferrous sulfate content was less than 20%, but in Comparative Example 2, where the mixing amount of the aqueous sulfuric acid solution was excessive, the ferrous sulfate content was as high as 75%. However, if the mixing ratio of waste sulfuric acid exceeds 50%, excess sulfuric acid remains, lowering the pH of ferrous sulfate, and mixing ferrous sulfate with a low pH into cement may lower the strength of cement. In addition, when used as a wastewater treatment chemical, there is a disadvantage that an additional neutralizing agent must be used because the use of a low pH substance lowers the pH of the wastewater.
한편 상기 표 2에서 제조된 물질 중 철원과 황산의 혼합비가 100:30인 발명예 2의 물질을 사용하여, 그 첨가량을 달리하면서 시멘트의 6가 크롬 저감 성능을 평가하여 그 결과를 하기 표 3에 나타내었다.Meanwhile, among the materials prepared in Table 2, the material of Inventive Example 2, in which the mixing ratio of iron source and sulfuric acid was 100:30, was used to evaluate the hexavalent chromium reduction performance of cement while varying the amount added, and the results are shown in Table 3 below. indicated.
또한 비교를 위하여, 황산제일철을 사용하지 않은 종래예와, 일반 시중에서 시판되는 황산제일철을 그 첨가량을 달리하는 비교예에 대한 시멘트의 6가 크롬 저감 성능을 각각 평가하여 그 결과를 하기 표 3에 또한 나타내었다. In addition, for comparison, the hexavalent chromium reduction performance of cement was evaluated for the conventional example without using ferrous sulfate and the comparative example in which commercially available ferrous sulfate was added in different amounts, and the results are shown in Table 3 below. Also shown.
사용량(g)Commercially available ferrous sulfate
Usage (g)
혼합 생성물 사용량(g)Cheorwon/sulfuric acid of the present invention
Mixed product usage (g)
상기 표 3에 나타난 바와 같이, 본 발명의 철 함유 물질과 황산수용액의 혼합을 통해 제조된 물질의 시멘트 6가크롬 저감 성능은 시판되는 황산제일철에 육박하는 것을 알 수 있다As shown in Table 3 above, it can be seen that the cement hexavalent chromium reduction performance of the material prepared by mixing the iron-containing material of the present invention and an aqueous sulfuric acid solution is close to that of commercially available ferrous sulfate.
본 발명은 상기 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 제조될 수 있으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다.The present invention is not limited to the above-mentioned embodiments, but can be manufactured in various different forms, and those skilled in the art will be able to form other specific forms without changing the technical idea or essential features of the present invention. You will be able to understand that this can be implemented. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive.
Claims (5)
상기 황산 수용액의 농도는 20 내지 90%이고, 상기 철 함유 물질에 대한 황산 수용액의 혼합비는 중량비로 0.2 내지 0.5인, 황산제일철 제조방법.
A method of producing ferrous sulfate by mixing an aqueous sulfuric acid solution with an iron-containing material,
The concentration of the aqueous sulfuric acid solution is 20 to 90%, and the mixing ratio of the aqueous sulfuric acid solution to the iron-containing material is 0.2 to 0.5 by weight.
The method of claim 1, wherein the iron-containing material contains 50% by weight or more of iron by weight.
The method of claim 1, wherein the iron-containing material is one or more selected from the group including iron scrap, iron ore, mill scale, iron-containing dust, and iron-containing sludge.
The method of claim 3, wherein the iron-containing sludge is steelmaking OG sludge.
The method of claim 1, wherein the aqueous sulfuric acid solution is waste semiconductor sulfuric acid.
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| KR100874739B1 (en) | 2002-09-24 | 2008-12-19 | 재단법인 포항산업과학연구원 | Method for manufacturing iron sulfate and gypsum using deoiled dust |
| WO2011144927A1 (en) | 2010-05-17 | 2011-11-24 | Tioxide Europe Limited | Process for the production of ferrous sulphate monohydrate |
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| KR100874739B1 (en) | 2002-09-24 | 2008-12-19 | 재단법인 포항산업과학연구원 | Method for manufacturing iron sulfate and gypsum using deoiled dust |
| WO2011144927A1 (en) | 2010-05-17 | 2011-11-24 | Tioxide Europe Limited | Process for the production of ferrous sulphate monohydrate |
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