KR102414870B1 - Method of manufacturing iron powder for treatment of contaminated water and iron powder for treatment of contaminated water - Google Patents
Method of manufacturing iron powder for treatment of contaminated water and iron powder for treatment of contaminated water Download PDFInfo
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- KR102414870B1 KR102414870B1 KR1020217007948A KR20217007948A KR102414870B1 KR 102414870 B1 KR102414870 B1 KR 102414870B1 KR 1020217007948 A KR1020217007948 A KR 1020217007948A KR 20217007948 A KR20217007948 A KR 20217007948A KR 102414870 B1 KR102414870 B1 KR 102414870B1
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- contaminated water
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 329
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 107
- 239000002245 particle Substances 0.000 claims abstract description 60
- 239000002244 precipitate Substances 0.000 claims abstract description 51
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 28
- 239000011651 chromium Substances 0.000 claims abstract description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 22
- 239000012535 impurity Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000002506 iron compounds Chemical class 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 20
- 239000011737 fluorine Substances 0.000 abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 229910000616 Ferromanganese Inorganic materials 0.000 description 6
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 238000009692 water atomization Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000013124 brewing process Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 229940091258 selenium supplement Drugs 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- PMYDPQQPEAYXKD-UHFFFAOYSA-N 3-hydroxy-n-naphthalen-2-ylnaphthalene-2-carboxamide Chemical compound C1=CC=CC2=CC(NC(=O)C3=CC4=CC=CC=C4C=C3O)=CC=C21 PMYDPQQPEAYXKD-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 206010040844 Skin exfoliation Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- KOLXPEJIBITWIQ-UHFFFAOYSA-L disodium hydrogenarsenate heptahydrate Chemical compound O.O.O.O.O.O.O.[Na+].[Na+].O[As]([O-])([O-])=O KOLXPEJIBITWIQ-UHFFFAOYSA-L 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- -1 it cools rapidly Chemical compound 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 229960001881 sodium selenate Drugs 0.000 description 1
- 235000018716 sodium selenate Nutrition 0.000 description 1
- 239000011655 sodium selenate Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Classifications
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- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
본 발명은, 오염수 중의 중금속류 및 불소를 제거할 수 있는 오염수 처리용 철분말을 제공하는 것을 과제로 한다. 본 발명에 따른 오염수 처리용 철분말은, 오염수 중의 중금속류를 제거하는 오염수 처리용 철분말로서, 철을 주성분으로 하고, 실리콘, 망간, 인, 황 및 크로뮴 중 적어도 1종을 포함하는 철계 석출물을 입자 내에 갖는다.An object of the present invention is to provide an iron powder for treatment of contaminated water capable of removing heavy metals and fluorine in contaminated water. The iron powder for treatment of contaminated water according to the present invention is an iron powder for treatment of contaminated water that removes heavy metals in contaminated water. The iron-based precipitate contains iron as a main component and contains at least one of silicon, manganese, phosphorus, sulfur and chromium. has in the particle.
Description
본 발명은 오염수 처리용 철분말 및 오염수 처리용 철분말 제조 방법에 관한 것이다.The present invention relates to iron powder for treatment of contaminated water and a method for manufacturing iron powder for treatment of contaminated water.
중금속 등에 의해 오염된 물을 정화하는 방법으로서는, 응집제를 이용하는 방법 및 다공질 흡착제를 이용하는 방법에 더하여, 예를 들면 일본 특허공개 2009-082818호 공보에 기재된 바와 같이 철분말(처리제)의 표면에 중금속 등을 석출시켜 제거하는 방법이 제안되어 있다. 상기 공보에 기재된 철분말은, 황을 포함하는 것이고, 셀레늄, 납, 카드뮴 및 크로뮴 중 적어도 1종의 중금속류를 철분말 표면에 석출시켜 제거할 수 있다고 되어 있다.As a method for purifying water contaminated with heavy metals, in addition to the method using a coagulant and the method using a porous adsorbent, for example, as described in Japanese Unexamined Patent Publication No. 2009-082818, heavy metals, etc. on the surface of iron powder (treatment agent) A method of removing the precipitates has been proposed. It is said that the iron powder described in the above publication contains sulfur and can be removed by depositing at least one heavy metal among selenium, lead, cadmium and chromium on the surface of the iron powder.
수도법에서는, 상기 공보에 기재된 방법에 의해 제거되는 셀레늄, 납, 카드뮴 및 크로뮴 등의 중금속류 이외에도, 불소에 대해서도 함유량이 기준치 이하가 아니면 안 된다고 되어 있다.In the water supply method, in addition to heavy metals such as selenium, lead, cadmium and chromium, which are removed by the method described in the above publication, the content of fluorine must be below the standard value.
상기 사정에 비추어, 본 발명은, 오염수 중의 중금속류 및 불소를 제거할 수 있는 오염수 처리용 철분말 및 오염수 처리용 철분말 제조 방법을 제공하는 것을 과제로 한다.In view of the above circumstances, an object of the present invention is to provide an iron powder for treatment of contaminated water and a method for manufacturing iron powder for treatment of contaminated water, which can remove heavy metals and fluorine in contaminated water.
상기 과제를 해결하기 위해서 이루어진 본 발명의 일 태양에 따른 오염수 처리용 철분말은, 오염수 중의 중금속류를 제거하는 오염수 처리용 철분말로서, 철을 주성분으로 하고, 실리콘, 망간, 인, 황 및 크로뮴 중 적어도 1종을 포함하는 철계 석출물을 입자 내에 갖는다.Iron powder for treatment of contaminated water according to an aspect of the present invention made to solve the above problems is an iron powder for treatment of contaminated water that removes heavy metals in contaminated water, and contains iron as a main component, silicon, manganese, phosphorus, sulfur and It has iron-type precipitates containing at least 1 sort(s) of chromium in particle|grains.
당해 오염수 처리용 철분말은, 실리콘, 망간, 인, 황 및 크로뮴 중 적어도 1종을 포함하는 철계 석출물을 입자 내에 갖는 것에 의해, 이 철계 석출물과 철 기재 사이에 전위차가 생기는 국부 전지 작용에 의해 철의 애노드 반응이 촉진되고, 오염수 중의 오염 원소의 환원 반응 또는 불용화 반응이 촉진된다. 이 때문에, 당해 오염수 처리용 철분말은, 오염수 중의 중금속류에 더하여 불소를 철분말 입자의 표면에 석출시켜 제거할 수 있다.The iron powder for the treatment of contaminated water contains iron-based precipitates containing at least one of silicon, manganese, phosphorus, sulfur and chromium in the particles, thereby generating a potential difference between the iron-based precipitates and the iron substrate. The anode reaction of iron is accelerated, and the reduction reaction or insolubilization reaction of the polluting element in the polluted water is accelerated. For this reason, the said iron powder for treatment of contaminated water can be removed by depositing fluorine on the surface of iron powder particles in addition to heavy metals in contaminated water.
당해 오염수 처리용 철분말에 있어서, 입자 단면에 있어서의 상기 철계 석출물의 평균 면적률로서는 0.8% 이상 50% 이하가 바람직하다. 이와 같이, 입자 단면에 있어서의 상기 철계 석출물의 평균 면적률이 상기 범위 내인 것에 의해, 당해 오염수 처리용 철분말은, 철 기재의 애노드 반응을 효과적으로 촉진하여, 오염수 중의 중금속류 및 불소를 효율적으로 제거할 수 있다.In the iron powder for treatment of contaminated water, the average area ratio of the iron-based precipitates in the particle cross section is preferably 0.8% or more and 50% or less. As described above, when the average area ratio of the iron-based precipitates in the particle cross section is within the above range, the iron powder for treating contaminated water effectively promotes the anode reaction of the iron substrate, and the heavy metals and fluorine in the contaminated water are efficiently removed. can be removed
당해 오염수 처리용 철분말에 있어서, 입자 내의 평균 공극률로서는 5% 이하가 바람직하다. 이와 같이, 입자 내의 평균 공극률을 상기 상한 이하로 하는 것에 의해, 당해 오염수 처리용 철분말은, 아토마이즈법에 의해 제조할 수 있으므로, 조성의 조정이 용이하고, 또한 상기 철계 석출물을 확실히 형성할 수 있기 때문에, 효율적으로 제조할 수 있다.In the iron powder for treating contaminated water, the average porosity in the particles is preferably 5% or less. In this way, by setting the average porosity in the particles to be below the upper limit, the iron powder for treating contaminated water can be produced by the atomization method, so that the composition can be easily adjusted and the iron-based precipitates can be reliably formed. Therefore, it can be efficiently manufactured.
본 발명의 다른 일 태양에 따른 오염수 처리용 철분말 제조 방법은, 오염수 중의 중금속류를 제거하는 오염수 처리용 철분말의 제조 방법으로서, 노에서 용철을 조제하는 공정과, 취과(取鍋)에서 상기 용철에 실리콘, 망간, 인, 황 및 크로뮴 중 적어도 1종을 포함하는 부원료를 첨가하는 공정과, 상기 부원료 첨가 후의 상기 용철에 물을 분사하여 분말화하는 공정을 구비한다.A method for manufacturing iron powder for treatment of contaminated water according to another aspect of the present invention is a method for manufacturing iron powder for treatment of contaminated water for removing heavy metals in contaminated water, comprising the steps of: preparing molten iron in a furnace; a step of adding an auxiliary material containing at least one of silicon, manganese, phosphorus, sulfur and chromium to the molten iron, and a step of powdering the molten iron by spraying water after the addition of the auxiliary material.
당해 오염수 처리용 철분말 제조 방법은, 상기 조제 공정, 상기 첨가 공정 및 상기 분말화 공정을 구비하고, 상기 첨가 공정에 있어서, 취과 중에서 용철에 실리콘, 망간, 인, 황 및 크로뮴 중 적어도 1종을 포함하는 부원료를 첨가하므로, 상기 부원료가 완전히 용융되어 철과 합금화되기 전에 상기 분말화 공정을 행하여, 철을 주성분으로 하고, 실리콘, 망간, 인, 황 및 크로뮴 중 적어도 1종을 포함하는 철계 석출물을 철분말 입자 내에 균일하게 분산시켜 형성할 수 있다. 이 때문에, 당해 오염수 처리용 철분말 제조 방법에 의해 얻어지는 당해 오염수 처리용 철분말은, 그의 입자 내에 상기 철계 석출물을 갖기 때문에, 이 철계 석출물과 철 기재의 국부 전지 작용에 의해 오염수 중의 중금속류에 더하여 불소를 철분말 입자의 표면에 석출시켜 제거할 수 있다.The method for producing iron powder for treatment of contaminated water includes the preparing step, the adding step, and the powdering step, and in the adding step, at least one of silicon, manganese, phosphorus, sulfur and chromium is added to molten iron during the brewing process. Since the additive containing can be uniformly dispersed in the iron powder particles. For this reason, since the iron powder for contaminated water treatment obtained by the method for producing iron powder for contaminated water treatment has the iron-based precipitates in the particles thereof, heavy metals in the contaminated water due to the local cell action of the iron-based precipitates and the iron substrate In addition, fluorine can be removed by precipitating it on the surface of the iron powder particles.
여기에서, 「주성분」이란, 가장 질량 함유율이 큰 성분을 의미한다. 또한, 「용철」이란, 탄소 함유량을 불문하고, 용융된 철 및 강 전반을 포함하는 개념이다.Here, the "main component" means the component with the largest mass content. In addition, "molten iron" is a concept including molten iron and steel in general regardless of carbon content.
전술한 바와 같이, 본 발명의 오염수 처리용 철분말 및 오염수 처리용 철분말 제조 방법에 의해 제조되는 오염수 처리용 철분말은, 오염수 중의 중금속류 및 불소를 제거할 수 있다.As described above, the iron powder for contaminated water treatment and the iron powder for contaminated water treatment produced by the method of the present invention can remove heavy metals and fluorine in contaminated water.
도 1은, 본 발명의 일 실시형태에 따른 오염수 처리용 철분말의 입자 단면의 전자 현미경 화상이다.
도 2는, 오염수 처리용 철분말의 시작예를 이용한 오염수 처리 시험에 있어서의 오염 원소의 제거율을 나타내는 그래프이다.BRIEF DESCRIPTION OF THE DRAWINGS It is an electron microscope image of the particle|grain cross section of the iron powder for contaminated water treatment which concerns on one Embodiment of this invention.
Fig. 2 is a graph showing the removal rate of contaminants in a contaminated water treatment test using a trial example of iron powder for treatment of contaminated water.
이하, 적절히 도면을 참조하면서, 본 발명의 실시의 형태를 상세히 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail, referring drawings suitably.
[오염수 처리용 철분말][Iron powder for treatment of contaminated water]
본 발명의 일 실시형태에 따른 오염수 처리용 철분말은, 오염수 중의 비소, 셀레늄, 납, 카드뮴 및 크로뮴을 포함하는 중금속류를 제거하기 위해서 이용되는 것이다. 또, 당해 오염수 처리용 철분말은, 중금속류에 더하여 불소를 제거할 수 있다.The iron powder for treatment of contaminated water according to an embodiment of the present invention is used to remove heavy metals including arsenic, selenium, lead, cadmium and chromium in contaminated water. Moreover, the said iron powder for contaminated water treatment can remove fluorine in addition to heavy metals.
당해 오염수 처리용 철분말은, 철을 주성분으로 하고, 실리콘, 망간, 인, 황 및 크로뮴(이하, 포괄해서 특정 원소라고 하는 경우가 있다) 중 적어도 1종을 포함하는 철계 석출물을 입자 내에 갖는다. 즉, 당해 오염수 처리용 철분말은, 철 또는 철 합금으로 이루어지는 철 기재의 입자 내에 상기 철계 석출물을 갖는다.The iron powder for treatment of contaminated water contains iron-based precipitates containing iron as a main component and at least one of silicon, manganese, phosphorus, sulfur, and chromium (hereinafter, collectively referred to as a specific element) in the particles. . That is, the said iron powder for contaminated water treatment has the said iron-type precipitate in the particle|grains of the iron base material which consists of iron or an iron alloy.
당해 오염수 처리용 철분말은, 예를 들면 아토마이즈 철분말, 주철 분말, 환원철 분말 등이어도 되지만, 성분이나 입경을 맞추기 쉽고, 상기 철계 석출물을 효율적으로 형성할 수 있는 점에서, 물 아토마이즈 철분말인 것이 바람직하다.The iron powder for the treatment of contaminated water may be, for example, atomized iron powder, cast iron powder, reduced iron powder, etc., but it is easy to adjust the components and particle size, and the iron-based precipitate can be efficiently formed. It is preferable to be a horse.
당해 오염수 처리용 철분말이 함유하는 철 및 상기 특정 원소 이외의 원소로서는, 예를 들면 탄소, 산소, 구리, 니켈, 몰리브데넘, 아연, 알루미늄, 코발트 등을 들 수 있다. 또한, 당해 오염수 처리용 철분말은, 의도적으로 첨가되는 원소 이외의 불가피적 불순물을 포함할 수 있다. 본 발명에 있어서는, 상기 불가피적 불순물은, 상기 철계 석출물에 포함되는 상기 특정 원소의 대상으로는 하지 않는다. 즉, 불가피적으로 실리콘, 망간, 인, 황 또는 크로뮴이 포함되더라도, 철계 석출물이 「실리콘, 망간, 인, 황 및 크로뮴 중 적어도 1종을 포함한다」고는 간주하지 않는 것으로 한다. 한편, 상기 불가피적 불순물은, 원소 단체(單體)의 함유량으로 통상 1질량% 미만이고, 바람직하게는 0.01질량% 미만이다.Examples of the iron contained in the iron powder for treatment of contaminated water and elements other than the above specific elements include carbon, oxygen, copper, nickel, molybdenum, zinc, aluminum and cobalt. In addition, the iron powder for treating contaminated water may contain unavoidable impurities other than the intentionally added element. In this invention, the said unavoidable impurity is not made into the object of the said specific element contained in the said iron-type precipitate. That is, even if silicon, manganese, phosphorus, sulfur, or chromium is unavoidably contained, it is not considered that the iron-based precipitate "contains at least one of silicon, manganese, phosphorus, sulfur and chromium". On the other hand, the said unavoidable impurity is less than 1 mass % normally in content of a single element, Preferably it is less than 0.01 mass %.
도 1에, 당해 오염수 처리용 철분말의 입자의 단면을 주사형 전자 현미경을 이용하여 촬영한 화상의 일례를 도시한다. 도면에 있어서, 흑점 형상의 부분이 철계 석출물이다. 이와 같이, 당해 오염수 처리용 철분말은, 입자 내에 복수의 철계 석출물을 분산시켜 갖는 것이 바람직하다.An example of the image which image|photographed the cross section of the said particle|grains of the said iron powder for contaminated water treatment in FIG. 1 using a scanning electron microscope is shown. In the figure, the dark spot-shaped portion is an iron-based precipitate. As described above, it is preferable to have a plurality of iron-based precipitates dispersed in the particles of the iron powder for treating contaminated water.
당해 오염수 처리용 철분말의 철계 석출물은, 상기 특정 원소를 핵으로 해서 형성되는 것이며, 철을 주성분으로 하고, 통상은 산소를 포함한다.The iron-based precipitate of the iron powder for treatment of contaminated water is formed by using the specific element as a nucleus, and has iron as a main component, and usually contains oxygen.
당해 오염수 처리용 철분말의 평균 입경의 하한으로서는, 1μm가 바람직하고, 10μm가 보다 바람직하다. 한편, 당해 오염수 처리용 철분말의 평균 입경의 상한으로서는, 1000μm가 바람직하고, 500μm가 보다 바람직하며, 100μm가 더 바람직하다. 당해 오염수 처리용 철분말의 평균 입경이 상기 하한에 미치지 않는 경우, 당해 오염수 처리용 철분말의 생산 효율이나 취급성이 불충분해질 우려가 있다. 반대로, 당해 오염수 처리용 철분말의 평균 입경이 상기 상한을 초과하는 경우, 전체 철분말의 합계 표면적이 작아짐으로써 오염수 중의 중금속류 및 불소를 충분히 제거할 수 없을 우려가 있다. 한편, 「평균 입경」이란, JIS-Z8801(2006)에 규정되는 체를 이용한 건식 체분리 시험에 의해 입자경 분포를 구하여, 이 입자경 분포에 있어서 누적 질량이 50%가 되는 입경을 말한다.As a lower limit of the average particle diameter of the said iron powder for contaminated water treatment, 1 micrometer is preferable and 10 micrometers is more preferable. On the other hand, as an upper limit of the average particle diameter of the said iron powder for contaminated water treatment, 1000 micrometers is preferable, 500 micrometers is more preferable, and 100 micrometers is still more preferable. When the average particle diameter of the iron powder for the treatment of contaminated water does not reach the above lower limit, there is a fear that the production efficiency and handleability of the iron powder for treatment of contaminated water become insufficient. Conversely, when the average particle diameter of the iron powder for treatment of contaminated water exceeds the upper limit, the total surface area of the entire iron powder becomes small, so that there is a fear that heavy metals and fluorine in the contaminated water cannot be sufficiently removed. On the other hand, "average particle size" refers to a particle size at which a particle size distribution is obtained by a dry sieving test using a sieve prescribed in JIS-Z8801 (2006), and the cumulative mass is 50% in this particle size distribution.
당해 오염수 처리용 철분말에 있어서의 상기 특정 원소의 합계 함유량의 하한으로서는, 0.3질량%가 바람직하고, 0.5질량%가 보다 바람직하며, 1질량%가 더 바람직하다. 한편, 당해 오염수 처리용 철분말에 있어서의 상기 특정 원소의 합계 함유량의 상한으로서는, 5질량%가 바람직하고, 3질량%가 보다 바람직하며, 2질량%가 더 바람직하다. 당해 오염수 처리용 철분말에 있어서의 상기 특정 원소의 합계 함유량이 상기 하한에 미치지 않는 경우, 충분한 양의 철계 석출물을 형성하는 것이 곤란해질 우려가 있다. 반대로, 당해 오염수 처리용 철분말에 있어서의 상기 특정 원소의 합계 함유량이 상기 상한을 초과하는 경우, 당해 오염수 처리용 철분말의 제조 비용이 불필요하게 증대될 우려가 있다.As a lower limit of the total content of the said specific element in the said iron powder for contaminated water treatment, 0.3 mass % is preferable, 0.5 mass % is more preferable, 1 mass % is still more preferable. On the other hand, as an upper limit of the total content of the said specific element in the said iron powder for contaminated water treatment, 5 mass % is preferable, 3 mass % is more preferable, and 2 mass % is still more preferable. When the total content of the specific element in the iron powder for the treatment of contaminated water is less than the lower limit, there is a fear that it will be difficult to form a sufficient amount of iron-based precipitates. Conversely, when the total content of the specific element in the iron powder for the treatment of contaminated water exceeds the upper limit, there is a fear that the manufacturing cost of the iron powder for treatment of contaminated water is unnecessarily increased.
당해 오염수 처리용 철분말의 철계 석출물에 있어서의 상기 특정 원소의 합계 함유량의 하한으로서는, 1질량%가 바람직하고, 2질량%가 보다 바람직하다. 상기 특정 원소의 합계 함유량이 상기 하한 미만이면, 오염수 중의 중금속류 및 불소의 제거 효율이 불충분해질 우려가 있다. 한편, 상기 특정 원소의 합계 함유량의 상한은, 특별히 한정되지 않고, 제거 대상이 되는 오염수의 성분 등에 의해 적절히 결정되지만, 예를 들어 50질량%로 할 수 있다.As a minimum of the total content of the said specific element in the iron-type precipitate of the said iron powder for contaminated water treatment, 1 mass % is preferable and 2 mass % is more preferable. There exists a possibility that the removal efficiency of heavy metals and fluorine in contaminated water that the total content of the said specific element is less than the said minimum may become inadequate. In addition, the upper limit of the total content of the said specific element is not specifically limited, Although it determines suitably according to the component etc. of the polluted water used as a removal object, it can be set as 50 mass %, for example.
당해 오염수 처리용 철분말의 입자 내의 평균 공극률의 상한으로서는, 5%가 바람직하고, 3%가 보다 바람직하다. 한편, 당해 오염수 처리용 철분말의 입자 내의 평균 공극률의 하한으로서는 특별히 한정되지 않고, 물리적인 한계치로서 0%이다. 당해 오염수 처리용 철분말의 입자 내의 평균 공극률이 상기 상한을 초과하는 경우, 물 아토마이즈법에 의해 제조하는 것이 어려워지기 때문에, 전체 조성 및 철계 석출물의 함유량을 조절하는 것이 곤란해질 우려가 있다. 즉, 당해 오염수 처리용 철분말은, 평균 공극률을 상기 상한 이하로 하는 것에 의해, 물 아토마이즈법에 의해 비교적 효율적으로 제조할 수 있다. 한편, 공극률은, 입자 단면의 전자 현미경 관찰 화상에 있어서의 공극의 면적률로서 측정된다.As an upper limit of the average porosity in the particle|grains of the said iron powder for contaminated water treatment, 5 % is preferable and 3 % is more preferable. In addition, the lower limit of the average porosity in the particle|grains of the said iron powder for contaminated water treatment is not specifically limited, It is 0 % as a physical limit value. When the average porosity in the particles of the iron powder for treatment of contaminated water exceeds the upper limit, it becomes difficult to produce by the water atomization method, so there is a fear that it may become difficult to control the overall composition and content of iron-based precipitates. That is, the said iron powder for contaminated water treatment can be manufactured comparatively efficiently by the water atomization method by making an average porosity below the said upper limit. In addition, the porosity is measured as the area ratio of the space|gap in the electron microscope observation image of a particle|grain cross section.
당해 오염수 처리용 철분말의 입자 단면에 있어서의 철계 석출물의 평균 면적률의 하한으로서는, 0.8%가 바람직하고, 1.0%가 보다 바람직하다. 한편, 당해 오염수 처리용 철분말의 입자 단면에 있어서의 철계 석출물의 평균 면적률의 상한으로서는, 50%가 바람직하고, 30%가 보다 바람직하다. 당해 오염수 처리용 철분말의 입자 단면에 있어서의 철계 석출물의 평균 면적률이 상기 하한에 미치지 않는 경우, 국부 전지 작용이 불충분해짐으로써 중금속류 및 불소를 효율적으로 석출시킬 수 없어, 오염수 중의 중금속류 및 불소를 충분히 제거할 수 없을 우려가 있다. 반대로, 당해 오염수 처리용 철분말의 입자 단면에 있어서의 철계 석출물의 평균 면적률이 상기 상한을 초과하는 경우, 국부 전지 작용에 있어서 애노드가 되는 철 기재의 면적이 상대적으로 작아짐으로써, 오염수 중의 중금속류 및 불소를 충분히 제거할 수 없을 우려가 있다. 한편, 당해 오염수 처리용 철분말의 입자 단면에 있어서의 철계 석출물의 평균 면적률은, 화상 해석 소프트웨어를 이용하여 입자 단면의 전자 현미경 관찰 화상을 철계 석출물 부분과 철 기재 부분으로 2치화하는 것에 의해 측정할 수 있다. 이 경우, 2치화를 위한 역치가 적절히 설정되지만, 전자 현미경 관찰 화상에 있어서의 철계 석출물과 철 기재의 콘트라스트는 크기 때문에, 역치를 기술 상식에 따라 적절한 범위 내에서 설정하는 한, 2치화에 기인하는 측정 오차는 충분히 작다.As a lower limit of the average area ratio of iron-type precipitates in the particle cross section of the said iron powder for contaminated water treatment, 0.8 % is preferable and 1.0 % is more preferable. On the other hand, as an upper limit of the average area ratio of iron-type precipitates in the particle cross section of the said iron powder for contaminated water treatment, 50 % is preferable and 30 % is more preferable. When the average area ratio of iron-based precipitates in the particle cross section of the iron powder for treatment of contaminated water does not reach the above lower limit, the local battery action becomes insufficient, so that heavy metals and fluorine cannot be efficiently precipitated, and heavy metals and There is a possibility that fluorine cannot be sufficiently removed. Conversely, when the average area ratio of iron-based precipitates in the particle cross section of the iron powder for treatment of contaminated water exceeds the above upper limit, the area of the iron substrate serving as the anode in the local battery action becomes relatively small, so that in the contaminated water There is a possibility that heavy metals and fluorine cannot be sufficiently removed. On the other hand, the average area ratio of iron-based precipitates in the particle cross section of the iron powder for treatment of contaminated water is obtained by binarizing the electron microscope observation image of the particle cross section into an iron-based precipitate portion and an iron base portion using image analysis software. can be measured In this case, the threshold for binarization is appropriately set, but since the contrast between the iron-based precipitate and the iron substrate in the electron microscope observation image is large, as long as the threshold is set within an appropriate range according to common technical knowledge, The measurement error is small enough.
당해 오염수 처리용 철분말의 입자 단면에 있어서의 철계 석출물의 평균 직경(원 상당 직경)의 하한으로서는, 0.1μm가 바람직하고, 0.15μm가 보다 바람직하다. 한편, 당해 오염수 처리용 철분말의 입자 단면에 있어서의 철계 석출물의 평균 직경의 상한으로서는, 10μm가 바람직하고, 1μm가 보다 바람직하다. 당해 오염수 처리용 철분말의 입자 단면에 있어서의 철계 석출물의 평균 직경이 상기 하한에 미치지 않는 경우, 국부 전지 작용이 불충분해질 우려가 있다. 반대로, 당해 오염수 처리용 철분말의 입자 단면에 있어서의 철계 석출물의 평균 직경이 상기 상한을 초과하는 경우, 당해 오염수 처리용 철분말의 입자마다의 중금속류 및 불소를 제거하는 능력에 격차가 생기고, 결과로서 당해 오염수 처리용 철분말 전체로서의 중금속류 및 불소를 제거하는 능력이 불충분해질 우려가 있다.As a lower limit of the average diameter (equivalent circle diameter) of the iron-type precipitate in the particle|grain cross section of the said iron powder for contaminated water treatment, 0.1 micrometer is preferable and 0.15 micrometer is more preferable. On the other hand, as an upper limit of the average diameter of the iron-type precipitate in the particle|grain cross section of the said iron powder for contaminated water treatment, 10 micrometers is preferable and 1 micrometer is more preferable. When the average diameter of the iron-based precipitates in the particle cross section of the iron powder for treatment of contaminated water does not reach the above lower limit, there is a fear that the local battery action may become insufficient. Conversely, when the average diameter of iron-based precipitates in the particle cross section of the iron powder for treatment of contaminated water exceeds the upper limit, there is a difference in the ability to remove heavy metals and fluorine from each particle of the iron powder for treatment of contaminated water. , as a result, there is a fear that the ability to remove heavy metals and fluorine as a whole of the iron powder for treatment of contaminated water may become insufficient.
<이점><Advantage>
당해 오염수 처리용 철분말은, 전술한 철계 석출물을 입자 내에 갖는 것에 의해, 이 철계 석출물과 철 기재 사이에 전위차가 생겨 국부 전지 작용에 의해 철 기재의 애노드 반응이 촉진됨으로써, 중금속류에 더하여 불소도 입자 표면에 석출시켜 비교적 효율적으로 제거할 수 있다.The iron powder for treatment of contaminated water contains the above-mentioned iron-based precipitates in the particles, thereby generating a potential difference between the iron-based precipitates and the iron substrate, and accelerating the anode reaction of the iron substrate by the action of a local battery, thereby fluorine in addition to heavy metals It can be removed relatively efficiently by precipitating it on the particle surface.
[오염수 처리용 철분말 제조 방법][Method for manufacturing iron powder for treatment of contaminated water]
전술한 오염수 처리용 철분말은, 본 발명의 일 실시형태에 따른 오염수 처리용 철분말 제조 방법에 의해 제조할 수 있다.The above-mentioned iron powder for treatment of contaminated water can be manufactured by the method for manufacturing iron powder for treatment of contaminated water according to an embodiment of the present invention.
당해 오염수 처리용 철분말 제조 방법은, 노에서 용철을 조제하는 공정 <조제 공정>과, 취과에서 용철에 실리콘, 망간, 인, 황 및 크로뮴 중 적어도 1종을 포함하는 부원료를 첨가하는 공정 <첨가 공정>과, 부원료를 첨가한 후의 용철에 물을 분사하여 분말화하는 공정 <분말화 공정>을 구비한다.The method for producing iron powder for the treatment of contaminated water includes a step of preparing molten iron in a furnace <preparation step>, and a step of adding an auxiliary material containing at least one of silicon, manganese, phosphorus, sulfur and chromium to the molten iron in the blowing process < Addition process>, and the process <powdering process> of spraying water to the molten iron after adding an auxiliary material to powder it is provided.
<조제 공정><Preparation process>
조제 공정에서는, 예를 들면 전로(轉爐), 전기로 등의 노에 있어서 용철을 조제한다. 이 조제 공정에서는, 예를 들면 탈규, 탈인, 탈탄, 탈산 등의 불순물을 제거하는 공지된 정련 처리를 행해도 되고, 용철의 성분을 조정하기 위해서 철 이외의 원료를 가해도 된다.In a preparation process, molten iron is prepared in furnaces, such as a converter furnace and an electric furnace, for example. In this preparation process, a well-known refining process which removes impurities, such as desiliconization, dephosphorization, decarburization, and deoxidation, for example, may be performed, and in order to adjust the component of molten iron, you may add raw materials other than iron.
<첨가 공정><Addition process>
첨가 공정에서는, 취과에 있어서, 상기 철계 석출물을 형성하는 핵이 되는 특정 원소를 포함하는 부원료를 첨가한다. 이와 같이, 취과에 있어서 부원료를 첨가하는 것에 의해, 부원료의 첨가로부터 다음의 분말화 공정까지의 시간을 짧게 하여, 부원료 중의 특정 원소가 철과 완전히는 합금화되지 않고, 용철 중에 특정 원소의 클러스터가 분산(미시적으로 특정 원소가 편재)되어 있는 상태에서 용철을 분말화할 수 있다고 생각된다. 이에 의해, 용철 중에 분산되어 있는 특정 원소의 클러스터를 핵으로 해서 철계 석출물을 형성할 수 있다.In the addition process, the additive containing the specific element used as the nucleus which forms the said iron-type precipitate is added. In this way, by adding the auxiliary material in the brewing process, the time from the addition of the auxiliary material to the next powdering process is shortened, the specific element in the auxiliary material is not completely alloyed with iron, and the cluster of the specific element is dispersed in the molten iron. It is thought that molten iron can be powdered in a state in which (microscopically, a specific element is ubiquitous). Thereby, an iron-based precipitate can be formed by using clusters of specific elements dispersed in molten iron as the nucleus.
이 첨가 공정에서는, 노로부터 발출한 용철을 저류하고 있는 취과에 나중에 부원료를 투입해도 되지만, 미리 부원료를 투입한 취과에 용철을 부어 넣는 것에 의해, 단시간에 효율적으로 용철에 부원료를 첨가할 수 있다.In this addition step, the auxiliary material may be added later to the culinary bag storing the molten iron extracted from the furnace.
또한, 부원료는, 일부가 합금화되어 얻어지는 오염수 처리용 철분말의 철 기재 중에 혼입된다. 이 때문에, 이 첨가 공정에서 첨가되는 부원료를 고려하여, 앞의 조제 공정에 있어서 조제하는 용철의 조성을 조절하는 것이 바람직하다. 반대로, 부원료의 첨가량이 동일하더라도, 조제 공정에서 조제되는 용철의 조성에 따라, 형성되는 철계 석출물의 양이나 조성이 변화한다. 이 때문에, 첨가 공정에 있어서 용철에 첨가하는 부원료의 종류 및 양은, 조제 공정에서 조제되는 용철의 조성을 고려하여 선택하는 것이 바람직하다.In addition, the auxiliary material is mixed in the iron base material of the iron powder for contaminated water treatment obtained by partially alloying. For this reason, it is preferable to adjust the composition of the molten iron prepared in the previous preparation process in consideration of the auxiliary material added in this addition process. Conversely, even if the additive amount is the same, the amount or composition of the iron-based precipitates to be formed changes depending on the composition of the molten iron prepared in the preparation step. For this reason, it is preferable to select the kind and quantity of the auxiliary material added to molten iron in the addition process in consideration of the composition of the molten iron prepared in the preparation process.
(부원료)(Supplementary Ingredients)
부원료로서는, 예를 들면 페로실리콘, 페로망간, 인 철, 황화 철, 페로크로뮴 등의 특정 원소와 철의 화합물이 적합하게 이용된다. 이들 부원료는, 일부 또는 전부가, 조제 공정에 있어서 정련 처리에 이용되는 처리제 또는 용강의 조성 조정을 위해서 첨가되는 재료와 동일한 것이어도 된다.As the auxiliary material, for example, a compound of iron with a specific element such as ferrosilicon, ferromanganese, iron phosphorus, iron sulfide, or ferrochromium is preferably used. One part or all of these auxiliary materials may be the same as the material added for composition adjustment of the processing agent used for a refining process in a preparation process, or molten steel.
<분말화 공정><Pulverization process>
분말화 공정에서는, 물 아토마이즈법에 의해, 용철을 미세화하면서 급속 냉각하여 분말화한다. 이때, 용철 중에 분산되어 있는 특정 원소의 클러스터가 핵이 되어, 분체 입자 내에 철계 석출물을 형성함으로써, 당해 오염수 처리용 철분말이 얻어진다고 생각된다.In the pulverization step, the molten iron is rapidly cooled and pulverized by the water atomization method while refining the molten iron. At this time, it is thought that the said iron powder for contaminated water treatment can be obtained by the cluster of the specific element disperse|distributed in molten iron becoming a nucleus, and forming an iron-type precipitate in a powder particle.
물 아토마이즈법에서는, 용철을 유하시키고, 유하되고 있는 용철에 물을 분사하는 것에 의해, 용철을 미세화함과 함께 급속 냉각하여 철분말을 얻는다. 용철에 분사하는 물의 양 및 압력을 조절하는 것에 의해, 얻어지는 철분말의 입경을 조절할 수 있다.In the water atomization method, molten iron is made to flow down and water is sprayed to the flowing molten iron, while refining|miniaturizing molten iron, it cools rapidly, and iron powder is obtained. By adjusting the amount and pressure of the water sprayed to the molten iron, the particle size of the obtained iron powder can be adjusted.
<이점><Advantage>
당해 오염수 처리용 철분말 제조 방법은, 상기 조제 공정, 상기 첨가 공정 및 상기 분말화 공정을 구비하고, 첨가 공정에 있어서, 취과 중에서 용철에 특정 원소를 포함하는 부원료를 첨가하므로, 부원료가 완전히 분산되기 전에 분말화 공정을 행하여, 철계 석출물을 철분말 입자 내에 균일하게 분산시켜 형성할 수 있다. 이 때문에, 당해 오염수 처리용 철분말 제조 방법에 의해 얻어지는 오염수 처리용 철분말은, 철계 석출물과 철 기재의 국부 전지 작용에 의해 오염수 중의 중금속류 및 불소를 철분말 표면에 석출시켜 효율적으로 제거할 수 있다.The method for producing iron powder for treatment of contaminated water includes the preparation step, the addition step, and the powdering step, and in the addition step, an auxiliary material containing a specific element is added to molten iron during brewing, so that the auxiliary material is completely dispersed It can be formed by uniformly dispersing the iron-based precipitates in the iron powder particles by performing a pulverization step before forming. For this reason, the iron powder for contaminated water treatment obtained by the method for producing iron powder for contaminated water treatment is efficiently removed by depositing heavy metals and fluorine in the contaminated water on the surface of the iron powder by the local cell action of iron-based precipitates and iron base. can do.
또한, 당해 오염수 처리용 철분말 제조 방법은, 첨가 공정에 있어서, 취과 중에서 용철에 부원료를 첨가하므로, 조제 공정을 행하는 노의 내화물의 융점이 부원료에 의해 저하되는 것을 방지할 수 있다. 이 때문에, 당해 오염수 처리용 철분말 제조 방법은, 제련 공정을 행하는 노의 내화물의 열화가 비교적 작아, 냉각이나 보전을 위한 정지 시간을 억제하여 생산 효율을 향상시킬 수 있다.In addition, in the method for manufacturing iron powder for contaminated water treatment, since an auxiliary material is added to molten iron during the brewing process in the addition step, it is possible to prevent the melting point of the refractory material in the furnace in which the preparation step is performed from being lowered by the auxiliary material. For this reason, in the said iron powder manufacturing method for contaminated water treatment, deterioration of the refractory material of the furnace which performs a smelting process is comparatively small, the downtime for cooling or maintenance can be suppressed, and productive efficiency can be improved.
[그 밖의 실시형태][Other embodiments]
상기 실시형태는, 본 발명의 구성을 한정하는 것은 아니다. 따라서, 상기 실시형태는, 본 명세서의 기재 및 기술 상식에 기초하여 상기 실시형태 각 부의 구성 요소의 생략, 치환 또는 추가가 가능하고, 그들은 모두 본 발명의 범위에 속하는 것으로 해석되어야 한다.The said embodiment does not limit the structure of this invention. Accordingly, in the above embodiment, it is possible to omit, substitute, or add components of each part of the above embodiment based on the description and technical common sense of the present specification, and they should all be construed as belonging to the scope of the present invention.
본 발명에 따른 오염수 처리용 철분말은, 전술한 오염수 처리용 철분말 제조 방법에 의해 제조되는 것으로 한정되지 않는다.The iron powder for treatment of contaminated water according to the present invention is not limited to being manufactured by the above-described method for manufacturing iron powder for treatment of contaminated water.
실시예Example
이하, 실시예에 기초하여 본 발명을 상세히 기술하지만, 이 실시예의 기재에 기초하여 본 발명이 한정적으로 해석되는 것은 아니다.Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not to be construed as being limited based on the description of these Examples.
<시작예 1><Start Example 1>
전기로에서 철 원료를 용해시키고 철 원료비 0.1질량%의 페로망간을 투입하고 불순물을 제거하는 것에 의해 조제된 용철 전량을, 미리 철 원료비 0.1질량%의 페로망간을 투입해 둔 취과에 취출하고 나서, 물 아토마이즈법에 의해 분말화함으로써, 평균 입경 90μm의 오염수 처리용 철분말의 시작예 1을 얻었다. 한편, 「평균 입경」은, JIS-Z8801(2006)에 규정되는 체를 이용한 건식 체분리 시험에 의해 측정한 「입도 분포」로부터 로진 램러 분포로 근사하는 것에 의해 산출했다.The total amount of molten iron prepared by dissolving the iron raw material in an electric furnace, adding ferromanganese having an iron raw material ratio of 0.1 mass % and removing impurities, is taken out into a sieving machine in which ferromanganese having an iron raw material ratio of 0.1 mass % has been added in advance, and then water Prototype example 1 of the iron powder for contaminated water treatment with an average particle diameter of 90 micrometers was obtained by pulverizing by the atomizing method. In addition, the "average particle diameter" was calculated by approximating to the Rosin Lamler distribution from the "particle size distribution" measured by the dry sieving test using a sieve prescribed|regulated to JIS-Z8801 (2006).
<시작예 2><Start Example 2>
전기로에서 철 원료를 용해시키고 철 원료비 0.2질량%의 페로망간을 투입하고 불순물을 제거하는 것에 의해 조제된 용철 전량을, 미리 철 원료비 0.1질량%의 페로망간 및 철 원료비 0.8질량%의 황화 철을 투입해 둔 취과에 취출하고 나서, 물 아토마이즈법에 의해 분말화함으로써, 평균 입경 92μm의 오염수 처리용 철분말의 시작예 2를 얻었다.The total amount of molten iron prepared by dissolving the iron raw material in an electric furnace, adding ferromanganese with an iron raw material ratio of 0.2 mass % and removing impurities, is previously introduced with ferromanganese with an iron raw material ratio of 0.1 mass % and iron sulfide with an iron raw material ratio of 0.8 mass % Prototype example 2 of the iron powder for contaminated water treatment with an average particle diameter of 92 micrometers was obtained by taking out by the preparatory sampling and pulverizing by the water atomization method.
<시작예 3><Start Example 3>
전기로에서 철 원료를 용해시키고 철 원료비 3.5질량%의 황화 철을 투입하고 불순물을 제거하는 것에 의해 조제된 용철 전량을, 미리 철 원료비 0.1질량%의 페로망간 및 철 원료비 0.3질량%의 황화 철을 투입해 둔 취과에 취출하고 나서, 물 아토마이즈법에 의해 분말화함으로써, 평균 입경 88μm의 오염수 처리용 철분말의 시작예 3을 얻었다.The total amount of molten iron prepared by dissolving the iron raw material in an electric furnace, adding iron sulfide of 3.5 mass % of the iron raw material ratio, and removing impurities, ferromanganese of 0.1 mass % of the iron raw material ratio and iron sulfide of 0.3 mass % of the iron raw material ratio are added in advance Prototype example 3 of the iron powder for contaminated water treatment with an average particle diameter of 88 micrometers was obtained by taking out by the preparatory sampling and pulverizing by the water atomization method.
오염수 처리용 철분말의 시작예 1∼3 중의 미량 원소의 함유량을 측정했다. 구체적으로는, C 및 S의 함유량을 적외선 흡수법에 의해 측정하고, Si, Mn 및 P의 함유량을 ICP(유도 결합 플라즈마) 발광 분광 분석법에 의해 측정했다. 이 결과를 다음의 표 1에 나타낸다.Content of the trace element in the trial examples 1-3 of the iron powder for contaminated water treatment was measured. Specifically, the contents of C and S were measured by an infrared absorption method, and the contents of Si, Mn, and P were measured by ICP (inductively coupled plasma) emission spectroscopy. These results are shown in Table 1 below.
또한, 오염수 처리용 철분말의 시작예 1∼3을 수지로 굳힌 시료를 다이아몬드 지립(砥粒)으로 1μm 연마하는 것에 의해, 오염수 처리용 철분말의 입자를 절단했다. 그리고, 이 입자의 단면을 FEI사제의 주사형 전자 현미경 「Quanta200FEG」를 이용하여 촬영했다. 주사형 전자 현미경의 설정은, 전압 15.0kV, 렌즈로부터 물체면까지의 작동 거리 10mm로 해서, BSE(반사 전자상)를 취득했다. 또한, 전자상의 취득에 있어서, 콘트라스트는 90 정도, 휘도는 40 정도의 설정으로 했다. 또, 이 전자 현미경 화상을 미타니 상사사의 화상 해석 소프트웨어 「WIN-ROOF ver5.5.0」을 이용하여, 256계조(0∼255)에서의 휘도 범위 80 이상 175 이하의 화소를 철계 석출물 영역으로서 추출하는 2치화 처리를 행하고, 노이즈 제거(설정치 0.001) 및 필링 처리를 행하여 철계 석출물의 면적률을 산출했다.In addition, the particles of the iron powder for the treatment of contaminated water were cut by grinding the samples obtained by hardening the samples 1 to 3 of the iron powder for the treatment of contaminated water with a resin to 1 μm with a diamond abrasive grain. And the cross section of this particle|grain was image|photographed using the scanning electron microscope "Quanta200FEG" manufactured by FEI. The scanning electron microscope was set to a voltage of 15.0 kV and a working distance from the lens to the object plane of 10 mm, and BSE (reflected electron image) was acquired. In addition, in the acquisition of an electronic image, the contrast was set to about 90, and the luminance was set to about 40. In addition, this electron microscope image is extracted using image analysis software "WIN-ROOF ver5.5.0" by Mitani Corporation, and pixels with a luminance range of 80 or more and 175 or less in 256 gradations (0 to 255) are extracted as iron-based precipitate regions. A value treatment was performed, noise removal (set value of 0.001), and a peeling treatment were performed to calculate the area ratio of iron-based precipitates.
또한, 상기 시료의 단면에 있어서의 철계 석출물의 부분의 조성을 에너지 분산형 X선 분석(EDX)에 의해 분석했다. 구체적으로는, 각 시료 중에서 입자경이 상이한 3개의 입자를 선택하고, 각 입자 내의 3개의 철계 석출물에 대하여 에너지 분산형 X선 분석을 행하고, 각 오염수 처리용 철분말의 시작품의 입도 분포에 기초하여 가중 평균하는 것에 의해, 철계 석출물의 조성을 산출했다.Further, the composition of the iron-based precipitate portion in the cross section of the sample was analyzed by energy dispersive X-ray analysis (EDX). Specifically, three particles having different particle diameters are selected from each sample, and energy dispersive X-ray analysis is performed on three iron-based precipitates in each particle, and based on the particle size distribution of the prototype iron powder for each contaminated water treatment. By weighted averaging, the composition of the iron-based precipitate was calculated.
다음의 표 2에, 오염수 처리용 철분말의 시작예 1∼3의 철계 석출물의 면적률 및 철계 석출물의 조성을 나타낸다. 한편, 표 중의 「-」는, 그 원소가 검출되지 않았던 것을 의미한다.Table 2 below shows the area ratio of iron-based precipitates and the composition of iron-based precipitates in Prototype Examples 1 to 3 of the iron powder for treatment of contaminated water. On the other hand, "-" in the table means that the element was not detected.
시험용 오염수로서, As 농도를 1mg/L로 조정한 비산수소 이나트륨 칠수화물 수용액, Se 농도를 1mg/L로 조정한 셀레늄산 나트륨의 수용액, Cr 농도를 1mg/L로 조정한 이크로뮴산 칼륨의 수용액, Pb 농도를 1mg/L로 조정한 질산 납의 수용액, Cd 농도를 1mg/L로 조정한 질산 카드뮴의 수용액, 및 F 농도를 1mg/L로 조정한 불화 나트륨의 수용액을 준비했다.As the test contaminated water, disodium hydrogen arsenate heptahydrate aqueous solution with As concentration adjusted to 1 mg/L, aqueous sodium selenate solution with Se concentration adjusted to 1 mg/L, potassium dichromate with Cr concentration adjusted to 1 mg/L An aqueous solution, an aqueous solution of lead nitrate with a Pb concentration of 1 mg/L, an aqueous solution of cadmium nitrate with a Cd concentration of 1 mg/L, and an aqueous solution of sodium fluoride with an F concentration of 1 mg/L were prepared.
상기 시험용 오염수에 오염수 처리용 철분말의 시작예 1∼3을 개별적으로 0.1질량% 가하고, 실온에서 24시간 연속 진탕(200rpm, 진탕 폭은 3∼5cm)한 후, 눈크기 0.45μm의 필터로 여과하고 나서, 용액 중의 오염 원소(제거 대상이 되는 중금속 또는 불소)의 농도를 측정하는 오염수 처리 시험을 행했다. 오염 원소의 농도는, JIS-K0102(2016)에 준거하여 측정했다.0.1% by mass of each of Prototype Examples 1 to 3 of iron powder for treatment of contaminated water was individually added to the contaminated water for testing, followed by continuous shaking (200 rpm, shaking width: 3 to 5 cm) at room temperature for 24 hours, followed by a filter with an eye size of 0.45 μm After filtration, a contaminated water treatment test was performed to measure the concentration of a contaminant element (heavy metal or fluorine to be removed) in the solution. The concentration of the contaminant element was measured in accordance with JIS-K0102 (2016).
다음의 표 3에, 오염수 처리용 철분말의 각 시작예 1∼3에 의한 처리 후의 각 시험용 오염수의 잔류 오염 원소의 농도의 측정 결과를 나타낸다.Table 3 below shows the measurement results of the concentrations of the residual pollutants in the contaminated water for testing after the treatment according to each of Prototype Examples 1 to 3 of the iron powder for the treatment of contaminated water.
상기 잔류 오염 원소의 농도의 측정 결과로부터, 오염수 처리용 철분말의 시작예 1∼3에 의한 각 오염 원소의 제거율을 산출하고, 이것을 정리하여 도 2에 나타낸다.From the measurement result of the concentration of the said residual contaminant element, the removal rate of each contaminant element by Trial Examples 1 to 3 of the iron powder for contaminated water treatment is computed, and this is summarized and shown in FIG.
이와 같이, 철계 석출물을 갖는 오염수 처리용 철분말의 시작예 1∼3은, 시험용 오염수 중의 중금속류 및 불소를 제거할 수 있었다. 그 중에서도 입자 단면에 있어서의 철계 석출물의 면적률이 비교적 큰 오염수 처리용 철분말의 시작예 2, 3은, 비교적 제거가 곤란한 크로뮴, 카드뮴 및 불소에 대해서도 충분히 큰 제거율을 얻을 수 있었다.In this way, in Prototype Examples 1 to 3 of the iron powder for treatment of contaminated water having iron-based precipitates, heavy metals and fluorine in the contaminated water for testing were able to be removed. Among them, in Prototype Examples 2 and 3 of the iron powder for contaminated water treatment having a relatively large area ratio of iron-based precipitates in the particle cross section, sufficiently large removal rates were obtained even for chromium, cadmium and fluorine, which are relatively difficult to remove.
본 발명에 따른 오염수 처리용 철분말 및 본 발명에 따른 오염수 처리용 철분말 제조 방법에 의해 얻어지는 오염수 처리용 철분말은, 오염수의 정화에 널리 이용할 수 있다.The iron powder for treatment of contaminated water according to the present invention and the iron powder for treatment of contaminated water obtained by the method for producing iron powder for treatment of contaminated water according to the present invention can be widely used for purification of contaminated water.
Claims (4)
철을 주성분으로 하고, 잔부가 실리콘, 망간, 인, 황 및 크로뮴 중 적어도 1종과 불가피적 불순물로 구성되는 철계 석출물을 입자 내에 갖고,
당해 오염수 처리용 철분말에서 상기 실리콘, 망간, 인, 황 및 크로뮴의 합계 함유량이 0.3질량% 이상 5질량% 이하인 것을 특징으로 하는 오염수 처리용 철분말.As iron powder for treatment of contaminated water that removes heavy metals in contaminated water,
Iron-based precipitates containing iron as a main component and the balance consisting of at least one of silicon, manganese, phosphorus, sulfur and chromium and unavoidable impurities in the particles;
The iron powder for the treatment of contaminated water, wherein the total content of silicon, manganese, phosphorus, sulfur and chromium in the iron powder for treatment of contaminated water is 0.3% by mass or more and 5% by mass or less.
입자 단면에 있어서의 상기 철계 석출물의 평균 면적률이 0.8% 이상 50% 이하인 오염수 처리용 철분말.The method of claim 1,
The iron powder for treatment of contaminated water, wherein the average area ratio of the iron-based precipitates in the particle cross section is 0.8% or more and 50% or less.
입자 내의 평균 공극률이 5% 이하인 오염수 처리용 철분말.3. The method of claim 1 or 2,
Iron powder for treatment of contaminated water with an average porosity of 5% or less in the particles.
노에서 용철을 조제하는 공정과,
취과(取鍋)에서 상기 용철에 실리콘, 망간, 인, 황, 크로뮴 및 이들의 철과의 화합물 중 적어도 1종과 불가피적 불순물로 구성되는 부원료를 첨가하는 공정과,
상기 부원료 첨가 후의 상기 용철에 물을 분사하여 분말화하는 공정
을 구비하고,
오염수 처리용 철분말에서 상기 실리콘, 망간, 인, 황 및 크로뮴의 합계 함유량이 0.3질량% 이상 5질량% 이하인 것을 특징으로 하는 오염수 처리용 철분말 제조 방법.A method for producing iron powder for treatment of contaminated water that removes heavy metals in contaminated water, the method comprising:
A process of preparing molten iron in a furnace;
A step of adding an auxiliary material comprising at least one of silicon, manganese, phosphorus, sulfur, chromium, and a compound of these iron compounds and unavoidable impurities to the molten iron in the process of taking;
A process of powdering by spraying water on the molten iron after the addition of the auxiliary material
to provide
A method for producing iron powder for treatment of contaminated water, characterized in that the total content of the silicon, manganese, phosphorus, sulfur and chromium in the iron powder for treatment of contaminated water is 0.3% by mass or more and 5% by mass or less.
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| PCT/JP2019/037696 WO2020084997A1 (en) | 2018-10-25 | 2019-09-25 | Iron powder for treating contaminated water, and method for manufacturing iron powder for treating contaminated water |
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| CN (1) | CN112469518B (en) |
| WO (1) | WO2020084997A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001073100A (en) | 1999-08-31 | 2001-03-21 | Daido Steel Co Ltd | Ferrous sintered compact, powder for manufacture of ferrous sintered compact, and manufacture of ferrous sintered compact |
| JP2009102708A (en) | 2007-10-24 | 2009-05-14 | Kobe Steel Ltd | Agent and method for treating polluted water containing heavy metals |
| JP2010010673A (en) * | 2008-05-30 | 2010-01-14 | Hitachi Ltd | Soft magnetic powders for magnetic compact, and magnetic compact using the same soft magnetic powders |
| JP2016509126A (en) | 2012-12-14 | 2016-03-24 | ホガナス アクチボラグ （パブル） | New products and their use |
| JP2018161604A (en) * | 2017-03-24 | 2018-10-18 | 株式会社神戸製鋼所 | Purification treatment agent and purification treatment method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4755159B2 (en) | 2007-09-28 | 2011-08-24 | 株式会社神戸製鋼所 | Treatment agent and treatment method for contaminated water containing heavy metals |
| JP5690106B2 (en) * | 2010-09-24 | 2015-03-25 | Ｄｏｗａエコシステム株式会社 | Decomposing agent for organic halogen compounds containing iron particles and method for producing the same |
| CN102248171A (en) * | 2011-07-12 | 2011-11-23 | 中南大学 | Gas atomization method for preparing oxygen supersaturated iron-based alloy powder |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001073100A (en) | 1999-08-31 | 2001-03-21 | Daido Steel Co Ltd | Ferrous sintered compact, powder for manufacture of ferrous sintered compact, and manufacture of ferrous sintered compact |
| JP2009102708A (en) | 2007-10-24 | 2009-05-14 | Kobe Steel Ltd | Agent and method for treating polluted water containing heavy metals |
| JP2010010673A (en) * | 2008-05-30 | 2010-01-14 | Hitachi Ltd | Soft magnetic powders for magnetic compact, and magnetic compact using the same soft magnetic powders |
| JP2016509126A (en) | 2012-12-14 | 2016-03-24 | ホガナス アクチボラグ （パブル） | New products and their use |
| JP2018161604A (en) * | 2017-03-24 | 2018-10-18 | 株式会社神戸製鋼所 | Purification treatment agent and purification treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20210046719A (en) | 2021-04-28 |
| JP6953095B2 (en) | 2021-10-27 |
| JP2020066778A (en) | 2020-04-30 |
| CN112469518A (en) | 2021-03-09 |
| WO2020084997A1 (en) | 2020-04-30 |
| CN112469518B (en) | 2023-02-17 |
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