KR0136191B1 - Refining method of iron oxide - Google Patents
Refining method of iron oxideInfo
- Publication number
- KR0136191B1 KR0136191B1 KR1019940035207A KR19940035207A KR0136191B1 KR 0136191 B1 KR0136191 B1 KR 0136191B1 KR 1019940035207 A KR1019940035207 A KR 1019940035207A KR 19940035207 A KR19940035207 A KR 19940035207A KR 0136191 B1 KR0136191 B1 KR 0136191B1
- Authority
- KR
- South Korea
- Prior art keywords
- iron oxide
- aqueous solution
- water
- impurity
- pyrolysis
- Prior art date
Links
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000007670 refining Methods 0.000 title description 2
- 239000007864 aqueous solution Substances 0.000 claims abstract description 39
- 239000012535 impurity Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001450 anions Chemical class 0.000 claims abstract description 19
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002500 ions Chemical class 0.000 claims abstract description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- 238000000197 pyrolysis Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 11
- 150000001768 cations Chemical class 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000908 ammonium hydroxide Substances 0.000 abstract description 4
- 235000013980 iron oxide Nutrition 0.000 description 66
- 230000000694 effects Effects 0.000 description 7
- 229910000859 α-Fe Inorganic materials 0.000 description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 229910000358 iron sulfate Inorganic materials 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- -1 i.e. Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-N iron;hydrochloride Chemical compound Cl.[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000004251 Ammonium lactate Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940059265 ammonium lactate Drugs 0.000 description 1
- 235000019286 ammonium lactate Nutrition 0.000 description 1
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229940001447 lactate Drugs 0.000 description 1
- 150000003893 lactate salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910006540 α-FeOOH Inorganic materials 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
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
본 발명은 열분해법으로 제조된 산화철중의 불순 양이온을 질산 또는 질산염 수용액으로 1차 여과하고, 다시 수산화암모늄 수용액으로 불순음이온을 2차 제거하므로서, 고순도의 산화철을 제조할 수 있는 산화철 정제방법을 제공하고자 하는데, 그 목적이 있다.The present invention provides a method for purifying iron oxide capable of producing high purity iron oxide by first filtering impurity cations in iron oxide prepared by pyrolysis using an aqueous solution of nitric acid or nitrate, and secondly removing impurities with an aqueous ammonium hydroxide solution. I would like to, but its purpose is.
상기 목적 달성을 위한 본 발명은 열분해법으로 제조된 산화철 중의 불순이온을 제거하는 정제방법에 있어서, 질산 또는 질산염 수용액의 pH를 2-4의 범위로 조절한 후 이 수용액에 상기 산화철을 투입하고 완전한 혼합상태에서 수세하여 1차 불순 양이온을 제거하는 단계; 1차 여과된 산화철을 NH4OH 수용액에 투입하여 pH를 8-9의 범위로 유지한 다음 수세하여 2차 불순 음이온을 제거하는 단계; 및 2차 처리된 산화철에 순수를 투입하여 pH를 7-7.5의 범위로 유지되도록 수세하여 여과한 다음 통상의 방법으로 건조하는 단계를 포함하여 구성되는 열분해법으로 제조된 산화철의 정제방법에 관한 것을 그 요지로 한다.The present invention for achieving the above object is a purification method for removing impurity ions in the iron oxide prepared by pyrolysis, the pH of the aqueous solution of nitric acid or nitrate is adjusted to the range of 2-4, the iron oxide is added to the aqueous solution and Washing with water to remove the first impurity cation; Injecting the primary filtered iron oxide in NH 4 OH aqueous solution to maintain the pH in the range of 8-9 and washed with water to remove the secondary impurity anion; And a method of purifying iron oxide prepared by pyrolysis, which comprises the step of adding pure water to the secondary treated iron oxide, washing with water to maintain a pH in the range of 7-7.5, and then drying it in a conventional manner. That's the point.
Description
제 1도는 산화철을 질산 수용액에 투입했을때 수용액의 pH산화철중의 불순 양이온의 제거율과의 관계를 나타내는 그래프1 is a graph showing the relationship between the removal rate of impurity cations in pH iron oxide of aqueous solution when iron oxide is added to aqueous solution of nitric acid
제 2도는 산화철을 질산염 수용액에 투입했을때 수용액의 pH변화와 산화철중의 불순 양이온의 제거율과의 관계를 나타내는 그래프2 is a graph showing the relationship between pH change of aqueous solution and removal rate of impurity cations in iron oxide when iron oxide is added to aqueous solution of nitrate
제 3도는 1차 여과된 산화철을 수산화 암모늄 수용액에 투입했을때 수용액의 pH와 산화철중의 Cl이온의 함량과의 관계를 나타내는 그래프3 is a graph showing the relationship between the pH of the aqueous solution and the content of Cl ions in the iron oxide when the first filtered iron oxide is added to the aqueous ammonium hydroxide solution.
본 발명은 전자부품 소재등에 응용되는 연자성 페라이트 등에 사용되는 산화철의 정제방법에 관한 것으로서, 보다 상세하게는 황산철, 염산철, 질산철 등의 철염을 열분해하여 제조되는 산화철중의 불순물을 제거하는 정제방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying iron oxide used in soft magnetic ferrites and the like applied to electronic component materials, and more particularly, to remove impurities in iron oxide produced by pyrolyzing iron salts such as iron sulfate, iron hydrochloride, and iron nitrate. It relates to a purification method.
통상 철염 등을 열분해하여 산화철을 제조하는 방법에는 철염의 원료에 따라 여려가지 방법이 있다. 18세기 초에는 황산철광에서 황산철을 만들고, 이를 열분해 하여 산화철(α-Fe2O3)를 얻는 방법이 많이 통용되었으나 이러한 황산철을 열분해하여 산화철을 제조하는 방법은 현재 극히 일부에서만 이용되고 있다.Usually, there are various methods for producing iron oxide by pyrolyzing iron salt or the like depending on the raw material of iron salt. In the early 18th century, iron sulfate was made from ferrous sulfate, and pyrolysis of iron oxide (α-Fe 2 O 3 ) was widely used. However, only a few methods of pyrolyzing iron sulfate to produce iron oxide are currently used. .
또한, 이러한 황산철 원료를 이용하는 방법과는 달리, 1930년경에는 산하철 중의 불순물을 피하기 위하여 전기 분해에 의해서 제조된 전해철을 질산으로 용해시켜 질산철(Fe(NO3)3)를 제조하고, 이때 발생하는 반응열을 이용하는 방법이 있었는데, 이 방법은 용액의 온도가 상승되면 일부가 α-FeOOH가 생성되고, 더욱 가열하여 열분해로 NO2를 제거시켜산화철(α-Fe2O3)을 제조하는 방법이었다.In addition, unlike the method of using the iron sulfate raw material, in order to avoid impurities in the iron oxide around 1930, the electrolytic iron produced by electrolysis is dissolved with nitric acid to produce iron nitrate (Fe (NO 3 ) 3 ), wherein There was a method of using the generated heat of reaction, in which part of α-FeOOH is produced when the temperature of the solution increases, and further heating to remove NO 2 by pyrolysis to produce iron oxide (α-Fe 2 O 3 ). It was.
이후, 1969년경 부터 제철소등의 철강공정에서 철강산세용으로 염산이 사용되어 대량의 염산철용액, 즉 폐산이 발생됨에 따라 이 폐산을 처리하여 염산을 회수 공정에서 산화철을 부생시키므로서 부생된 산화철을 정제하여 페라이트용으로 사용되고 있다.Since around 1969, hydrochloric acid has been used for steel pickling in steel processes, such as steel mills, and a large amount of iron hydrochloric acid solution, i.e., waste acid, is treated, thereby treating hydrochloric acid to produce iron oxide in the recovery process. Purified and used for ferrite.
이와같이 산화철을 열분해하여 제조하는 방법에서는 그 철염 원료에 따라 여려가지 방법이 있는데, 통상적으로 열분해법으로 제조되는 산화철 내에는 불순이온, 예를들어 SO4, NO2, Cl등의 성분이 0.2중량%이상 포함되어 있어서 산화철 응용제품제조시에 악영향을 미치므로 가능한한 적게 유지하는 것이 요구되고 있다. 예를들면, 이러한 산화철내의 불순이온에 대하여 JIS K1462 규격에 의하면 1종 산화철의 경우 SO4는 0.2중량%이하, Cl은 0.15중량% 이하가 되도록 정하여 가능한한 불순이온을 규제하고 있다.As described above, there are various methods for the method of pyrolyzing iron oxide, depending on the iron salt raw material. In iron oxide, which is usually produced by pyrolysis, impurities such as SO 4 , NO 2 , and Cl are 0.2% by weight. It is included as described above, and thus adversely affects the manufacture of iron oxide application products, so it is required to keep it as small as possible. For example, according to the JIS K1462 standard, impurities such as SO 4 are 0.2 wt% or less and Cl is 0.15 wt% or less in accordance with the JIS K1462 standard.
특히, 페라이트중에는 산화철이 차지하는 비율은 약 75%정도나 점하고 있기 때문에 산화철은 페라이트의 특성에 가장 큰 영향을 미치므로 산화철내에 포함된 불순물의 정제는 매우 중요한 것이다.In particular, since iron oxide occupies about 75% of the ferrite, the purification of impurities contained in iron oxide is very important because iron oxide has the greatest influence on the properties of ferrite.
한편, 산화철내의 불순물, 특히 불순 음이온을 제거하기 위하여 종래에는 일반적으로 가열에 의해서 음이온이 방출되도록 하는 방법과 수세에 의해서 물속에 음이온을 녹여서 여과를 통하여 제거하는 방법이 사용되고 있다. 이들 방법중 수세에의한 산화철 정제법이 널리 통용되고 있는데, 이 방법은 산화철을 물속에 넣고 암모니아수를 넣어 산화철내에 들어있는 음이온을 중화하고 여과하여 정제하는 방법이다.On the other hand, in order to remove impurities, particularly impurity anions in iron oxide, conventionally, a method of releasing anions by heating and a method of dissolving anions in water by washing with water and removing them through filtration are used. Among these methods, iron oxide refining by water washing is widely used, and this method is a method of neutralizing anion contained in iron oxide by adding iron oxide in water and purifying it by filtration.
이러한 수세에 의한 산화철 정제법에 관한 또 다른 예로서, 일본 특개소 59-50031호에 제시된 바에 의하면, 유산철(II)FeSO4·7H2O·유산철(III) Fe2(SO4)3·9H2O, 유산암모늄(NH4)2SO4등의 유산염의 희석용액을 이용하여 산화철을 세척하여 정제하는 방법이 제안되어 있다.As another example of the method for purifying iron oxide by water washing, as disclosed in Japanese Patent Laid-Open No. 59-50031, iron (II) FeSO 4 · 7H 2 O · iron (III) Fe 2 (SO 4 ) 3 A method of washing and purifying iron oxide using a dilute solution of lactate, such as 9H 2 O and ammonium lactate (NH 4 ) 2 SO 4 , has been proposed.
그러나, 상기의 종래 방법들은 산화철에 암모니아수를 투입하여 세척하므로서 음이온은 어느 정도 제거가 가능하지만, 금속이온의 정제는 불가능하는 문제점이 있으며, 또한 일본특개소 59-50031호에 제시된 바와 같이 유산염류를 사용할때는 유산염류를 제조하여 사용해야 하는 문제점과 SO4음이온을 제거하기 위하여 수차례의 수세가 요구되는 문제점을 지니고 있다.However, in the conventional methods, the anion can be removed to some extent by adding ammonia water to iron oxide, but there is a problem in that the purification of metal ions is impossible, and as shown in Japanese Patent Laid-Open No. 59-50031, When used, it has problems of preparing and using lactates and several times of washing with water to remove SO 4 anions.
이에 본 발명자들은 상기한 종래방법과는 달리, 산화철내의 불순 금속이온과 음이온을 효율적으로 제거하기 위한 연구와 실험을 행하고, 그 결과를 통하여 본 발명을 제안하게 된 것으로서, 본 발명은 열분해법으로 제조된 산화철중의 불순 양이온을 질산 또는 질산염 수용액으로 1차 여과하고, 다시 수산화암모늄 수용액으로 불순 음이온을 2차 제거하므로서, 고순도의 산화철을 제조할수 있는 산화철 정제방법을 제공하고자 하는데, 그 목적이 있다.Accordingly, the present inventors, unlike the above-described conventional method, conducts research and experiments for efficiently removing impurity metal ions and anions in iron oxide, and suggest the present invention through the results, and the present invention is prepared by the pyrolysis method. The primary purpose of the present invention is to provide a method for purifying iron oxide, which can produce high purity iron oxide by first filtering impurity cations in the ferrous oxides with an aqueous solution of nitric acid or nitrate, and secondly removing impurities with an aqueous ammonium hydroxide solution.
이하, 본 발명을 설명한다.Hereinafter, the present invention will be described.
본 발명은 열분해법으로 제조된 산화철 중의 불순이온을 제거하는 정제방법에 있어서, 질산 또는 질산염 수용액의 pH를 2-4의 범위로 조절한 후 이 수용액에 상기 산화철을 투입하고 완전한 혼합상태에서 수세하여 1차 불순 양이온을 제거하는 단계; 1차 처리된 산화철을 NH4OH 수용액에 투입하여 pH를 8-9의 범위로 유지한 다음 수세하여 2차 불순 음이온을 제거하는 단계; 및 2차 처리된 산화철에 순수를 투입하여 pH를 7-7.5의 범위로 유지되도록 수세하여 여과한 다음 통상의 방법으로 건조하는 단계를 포함하여 구성되는 열분해법으로 제조된 산화철의 정제방법에 관한 것이다.The present invention is a purification method for removing impurity ions in iron oxide prepared by pyrolysis method, after adjusting the pH of nitric acid or nitrate aqueous solution to the range of 2-4, the iron oxide is added to the aqueous solution and washed in a complete mixed state Removing the primary impurity cation; Firstly treating the iron oxide in an aqueous NH 4 OH solution to maintain a pH in the range of 8-9, followed by washing with water to remove the secondary impurity anion; And it relates to a method for purifying the iron oxide produced by the pyrolysis method comprising the step of adding pure water to the iron oxide secondary treatment, washing with water to maintain the pH in the range of 7-7.5 and then drying in a conventional manner. .
이하, 본 발명에 대하여 상세히 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
우선, 산화철에 포함된 Ca, Na, K, Mg과 같은 불순양이온을 제거하기 위해서는 알칼리성 수용액에서 보다 산성용액에서 효율적으로 제거가 가능하므로 산화철을 질산또는 질산염수용액에 투입한다. 이 질산 또는 질산염 수용액을 투입하면 산화철중의 불순물은 이온상태에서 산화철에 표면 흡착이 적게되고, 수용액중에 불순이온들이 다량 녹아 있는 상태를 유지하기 때문에 이 수용액을 1차 여과하면 산화철내에 포함된 불순양이온이 감소된다. 이때, 가장 효율적인 산성수용액의 pH는 2에서 4사이가 바람직하다. 만일 수용액의 pH가 2보다 작은 경우는 산화철 그자체를 녹아나게 해서 Fe가 상대적으로 감소하는 현상으로 인하여 불순물의 함량이 오히려 증가되는 현상을 보인다.First, in order to remove impurity ions such as Ca, Na, K, and Mg contained in iron oxide, iron oxide is added to an aqueous solution of nitric acid or nitrate because it can be efficiently removed from an acidic solution in an alkaline aqueous solution. When this nitric acid or nitrate solution is added, impurities in the iron oxide have less surface adsorption on the iron oxide in the ionic state, and a large amount of impurity ions are dissolved in the aqueous solution. Is reduced. At this time, the pH of the most efficient acidic aqueous solution is preferably between 2 and 4. If the pH of the aqueous solution is less than 2, due to the phenomenon that Fe is relatively reduced by melting the iron oxide itself, the content of impurities is rather increased.
또한, pH가 4보다 높은 경우는 불순양 이온인 Ca, Na, K, Mg등을 녹아나게 하는데 비효율성을 지니므로 효과가 저하됨을 나타낸다.In addition, when the pH is higher than 4, the effect is lowered because it has inefficiency in melting the impurity ions Ca, Na, K, Mg and the like.
이와같이 산성 수용액의 pH를 2-4의 범위로 조절하기 위해서 통상 산화철과 질산이온 수용액의 중량비는 1 이상이 되도록 한다.Thus, in order to adjust the pH of the acidic aqueous solution to the range of 2-4, the weight ratio of iron oxide and nitrate aqueous solution is usually 1 or more.
또한, 질산염을 사용하는 경우 Fe(NO)3·9H2O를 사용하면 보다 바람직하다.In the case of using nitrate, Fe (NO) 3 .9H 2 O is more preferable.
상기 질산 또는 질산염 수용액으로 pH 2-4에서 1차 처리한 산화철을 수세 및 여과한 후에 여기서 포함된 음이온을 제거하기 위하여 NH4OH수용액을 투입하여 pH 8-9로 유지하여 완전 혼합한 다음 수세한다. 여기서 산화철내의 음이온은 NH4OH와 반응하여 수용액중에 화학결합을 유지함으로써 쉽게 제거가 가능하다. 이때, NO3 -, Cl-등의 음이온이 수산화암모늄과 반응하는 반응식은 다음과 같다.After washing with water and filtering the iron oxide first treated at pH 2-4 with the nitric acid or nitrate aqueous solution, NH 4 OH aqueous solution was added to keep the pH at 8-9 to remove the negative ions contained therein. . Here, the anion in the iron oxide can be easily removed by reacting with NH 4 OH to maintain a chemical bond in the aqueous solution. At this time, a reaction formula in which anions such as NO 3 − , Cl − and the like react with ammonium hydroxide is as follows.
NH4OH + H++ NO3- ………… NH4(NO)3+ H2ONH 4 OH + H + + NO 3 -... … … … NH 4 (NO) 3 + H 2 O
NH4OH + H++ Cl-………… NH4Cl + H2O NH 4 OH + H + + Cl - ... … … … NH 4 Cl + H 2 O
상기와 같은 반응으로 음이온이 쉽게 제거되며 본 발명에서는 산화철내의 음이온을 500ppm 이하로 유지하기 위해서는 수용액의 pH를 8이상으로 해야하며, 또한 pH가 9보다 클 경우에는 음이온을 제거하는 효과가 그다지 증가하지 않기 때문에 수용액의 pH를 8-9사이가 되도록 함이 바람직하다.The anion is easily removed by the reaction as described above. In the present invention, in order to maintain the anion in the iron oxide at 500 ppm or less, the pH of the aqueous solution must be 8 or more, and when the pH is greater than 9, the effect of removing the anion does not increase much. It is preferable that the pH of the aqueous solution is between 8-9.
한편, 수용액의 온도는 50℃이하에서 실시하는 것이 바람직하며 50℃이상에서는 수증기의 발생양이 많아져서 수증기속의 음이온이 포함되어 방출되므로 인하여 환경공해를 유발문제와 작업성 문제가 야기되기 때문에 50℃ 이하에서 실시하는 것이 바람직하다.On the other hand, the temperature of the aqueous solution is preferably carried out below 50 ℃, 50 ℃ above 50 ℃ because the amount of generation of the water vapor is increased because the anion in the water vapor is released, causing environmental pollution and workability problems cause 50 ℃ It is preferable to carry out below.
그리고 본 발명에서 수용액제조에 사용되는 물은 순수를 사용하며 이러한 순수는 불순이온이 적게 포함된 물일수록 바람직하다.In the present invention, the water used in preparing the aqueous solution uses pure water, and the pure water is more preferable water containing less impurity ions.
이하, 본 발명을 실시예를 통하여 구체적으로 설명한다.Hereinafter, the present invention will be described in detail through examples.
실시예 1Example 1
열분해법으로 제조된 하기표 1과 같은 불순성분을 갖는 산화철을 하기표 2와 같이 pH가 1-6의 범위로 조절된 6종의 질산 수용액에 투입하였다. 이때, 질산 수용액과 산화철의 중량비를 2로 유지하였으며 상기 산화철을 질산 수용액에 완전 혼합시키기 위해 1200rpm으로 약 30분간 교반하였다.Iron oxide having an impurity component as shown in Table 1 prepared by the pyrolysis method was added to six kinds of nitric acid aqueous solutions of which pH was adjusted in the range of 1-6 as shown in Table 2 below. At this time, the weight ratio of the aqueous nitric acid solution and iron oxide was maintained at 2 and stirred for about 30 minutes at 1200rpm to completely mix the iron oxide in the aqueous nitric acid solution.
[표 1]TABLE 1
[표 2]TABLE 2
이후 상기 수용액을 순수로 수세한 후, 여과하여 산화철을 건조하고, 각각의 불순 성분의 농도를 습식 분석과정을 거쳐 최종 ICP(Inductively coupled plasma)기기를 이용하여 분석하고 그 결과를 초기값과 비교하여 제거율을 구한 다음 제 1도에 그 결과를 나타냈다.The aqueous solution was then washed with pure water, filtered to dry iron oxide, and the concentration of each impurity component was analyzed using a final ICP (Inductively coupled plasma) device after a wet analysis process. The removal rate was determined and the result is shown in FIG.
제 1도에 나타난 바와 같이 수용액의 pH가 2-4로 조절된 발명예(1-3)의 경우에는 불순 양이온 제거효율이 50% 이상으로 상당한 효율이 있을수 있으며, 반면에 pH가 2보다 작은 비교예(1)의 경우는 산화철 그자체를 녹아나게 해서 Fe가 상대적으로 감소하는 현상으로 인하여 불순물의 함량이 오히려 증가되는 현상을 보이고, 또한 pH가 4보다 높은 비교예(2-3)의 경우는 불순이온인 Ca, Na, K, Mg이 녹아나게 하는 효과가 저하됨을 알 수 있다.As shown in FIG. 1, in the case of Inventive Example (1-3) in which the pH of the aqueous solution is adjusted to 2-4, the impurity cation removal efficiency may be more than 50%, whereas the pH is less than 2 In the case of Example (1), the content of impurities is rather increased due to the relatively decrease of Fe by melting iron oxide itself, and also in Comparative Example (2-3) having a pH higher than 4 It can be seen that the effect of dissolving the impurities ions Ca, Na, K, Mg is reduced.
실시예 2Example 2
산성수용액으로 질산염(Fe(NO)3·9H2O)을 이용하여 하기표 3과 같이 pH를 2에서 6까지의 5종의 질산이온 수용액을 제조한 다음, 제조된 수용액과 상기표 1과 같은 조성을 갖는 산화철의 중량비를 2로 유지하도록 하여 산화철을 수용액에 완전 혼합 하였다. 이때, 혼합시 1200rpm으로 약 30분간 교반하고 이후, 수세한후 여과하여 산화철을 건조하고 각각의 분순성분의 농도를 습식분석과정을 거쳐 최종 ICP(Inductively couled plasma)기기를 이용하여 분석하여 그 결과를 초기값과 비교하여 제거율을 구하고, 그 결과를 제 2도에 나타냈다.Using nitrate (Fe (NO) 3 · 9H 2 O) as an acidic aqueous solution to prepare five kinds of nitrate aqueous solution of pH 2 to 6 as shown in Table 3, and then the aqueous solution prepared as shown in Table 1 The iron oxide was completely mixed in the aqueous solution so that the weight ratio of the iron oxide having the composition was maintained at 2. At this time, the mixture was stirred at 1200rpm for about 30 minutes, and then washed with water, filtered to dry iron oxide, and the concentration of each minute component was analyzed using a final ICP (Inductively couled plasma) apparatus through a wet analysis process. The removal rate was calculated | required compared with the initial value, and the result was shown in FIG.
[표 3]TABLE 3
제 2도에 나타난 바와같이 질산염을 사용하여 pH를 2-4조절한 발명예(4-6)의 경우 불순이온 제거율이 50% 이상으로 효과가 큼을 알수 있다. 반면에 pH가 2보다 작은 경우는 질산을 사용한 실시예 1의 결과와는 차이가 있는데, 그 이유는 Fe 이온이 다량 녹아있어서 산화철중의 Fe가 상대적으로 녹아나지 않기 때문에 pH가 2이하에서도 효과는 있지만 질산염이 대량 사용되어야하는 문제로 인하여 pH 2이상으로 한정하는 것이 바람직하다.As shown in FIG. 2, in the case of Inventive Example (4-6) in which the pH was adjusted 2-4 using nitrate, the removal rate of impurity ions was greater than 50%. On the other hand, if the pH is less than 2, it is different from the result of Example 1 using nitric acid, because the Fe ions are dissolved in a large amount so that Fe in iron oxide is not relatively dissolved, so the effect is less than 2 However, it is preferable to limit the pH to 2 or more due to the problem that a large amount of nitrate should be used.
또한, pH가 4보다 높은 비교예(4-5)의 경우는 불순이온인 Ca, Na, K, Mg이 녹아나게 하는 효과가 저하됨을 알수 있다.In addition, in the case of Comparative Example (4-5) having a pH higher than 4, it can be seen that the effect of dissolving Ca, Na, K, and Mg as impurity ions is reduced.
실시예 3Example 3
실시예 1과 실시예 2에서 처리하고 난 발명예(2)와 발명예(5)의 산화철 A,B 라고 하고, 이것을 음이온을 제거하기 위한 NH4OH수용액에 투입하고 이 수용액의 pH를 하기표 4와 같이 조절하였다. 이때 각각 pH가 조절된 4종의 수용액과 산화철의 중량비가 2가 되도록 유지하면서 산화철을 수용액에 완전 혼합하기 위해 1200rpm으로 약 30분간 교반하였으며, 제조된 슬러리를 각각 수세한후여과하였다. 그 다음 산화철을 다시 산화철의 중량의 2배의 순수를 혼합교반하고 수세하였다. 수세시에 슬러리의 pH는 7-7.5가 되도록 하였고, 이후 여과 및 건조하여 산화철중의 각각의 불순음이온을 이온 크로마토그래피로 분석하고 그 결과를 제 3도에 나타내었다.The iron oxides A and B of Inventive Example (2) and Inventive Example (5), which were treated in Examples 1 and 2, were referred to as aqueous solution of NH 4 OH for removing anions, and the pH of the aqueous solution was shown in the following table. Adjusted as shown in 4. At this time, while maintaining the weight ratio of the four aqueous solutions and the iron oxide of which pH was adjusted to 2, the mixture was stirred at 1200 rpm for about 30 minutes to completely mix the iron oxide in the aqueous solution, and the prepared slurry was washed with water, respectively. Then, the iron oxide was mixed and stirred and washed with pure water twice the weight of the iron oxide again. The pH of the slurry was adjusted to 7-7.5 at the time of washing, followed by filtration and drying to analyze each impurity ion in iron oxide by ion chromatography, and the results are shown in FIG.
[표 4]TABLE 4
제 3도에 나타난 바와 같이 산화철 중에 포함된 Cl이온의 양은 pH 9이상에서는 거의 효과가 같음을 나타내고 있으며, 또한 pH 7에서는 음이온 Cl이 500ppm이상을 나타내고 있고, pH 8에서 부터 500ppm 이하를 유지함을 알수 있다. 따라서, 산화철내의 음이온 Cl의 양을 500ppm이하로 유지하기 위해서는 발명예(7)(8)의 경우와 같이 산화철이 포함된 슬러리의 pH를 8-9로 조절하는 것이 바람직함을 알수 있다.As shown in FIG. 3, the amount of Cl ions contained in the iron oxide showed almost the same effect at pH 9 or higher, and at pH 7, the anion Cl showed at least 500 ppm and maintained at 500 ppm or lower from pH 8. have. Therefore, in order to maintain the amount of the anion Cl in the iron oxide to 500ppm or less, it can be seen that it is preferable to adjust the pH of the slurry containing iron oxide to 8-9 as in the case of the invention example (7) (8).
상술한 바와 같이, 본 발명에 의하면 열분해로 제조되는 산화철을 정제하여 고순도의 산화철 제조가 가능하므로 이 산화철을 통하여 고품위 전자제품, 특히 고주파수 영역에 사용되는 고급 연자성 페라이트를 제조하는데 사용할수 있으며 현재 국내에서는 고순도 산화철을 전량 수입에 의존하기 때문에 수입대체효과를 동반하는 등의 효과가 있다.As described above, according to the present invention, since it is possible to manufacture iron oxide of high purity by purifying iron oxide produced by pyrolysis, the iron oxide can be used to manufacture high-grade electronic products, especially high-quality soft magnetic ferrites used in high frequency region. In the case of high-purity iron oxide, all depend on imports, so it is accompanied by import substitution effect.
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| KR20020050433A (en) * | 2000-12-21 | 2002-06-27 | 이구택 | A purification method of iron oxide produced by thermal decomposing method and iron oxide having high purity provided by using this method |
| KR100442710B1 (en) * | 2001-11-08 | 2004-08-02 | 오성근 | Synthesis of Iron Oxide Nanoparticles |
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| KR20020050433A (en) * | 2000-12-21 | 2002-06-27 | 이구택 | A purification method of iron oxide produced by thermal decomposing method and iron oxide having high purity provided by using this method |
| KR100442710B1 (en) * | 2001-11-08 | 2004-08-02 | 오성근 | Synthesis of Iron Oxide Nanoparticles |
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