KR100688026B1 - Manufacturing method for activated mineral salt containing ferrous-ferric salts - Google Patents
Manufacturing method for activated mineral salt containing ferrous-ferric salts Download PDFInfo
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- KR100688026B1 KR100688026B1 KR1020060000001A KR20060000001A KR100688026B1 KR 100688026 B1 KR100688026 B1 KR 100688026B1 KR 1020060000001 A KR1020060000001 A KR 1020060000001A KR 20060000001 A KR20060000001 A KR 20060000001A KR 100688026 B1 KR100688026 B1 KR 100688026B1
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- South Korea
- Prior art keywords
- salt
- solution
- mineral
- acid
- trivalent iron
- Prior art date
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- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 61
- 239000011707 mineral Substances 0.000 title claims abstract description 61
- 150000003839 salts Chemical class 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 25
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000011575 calcium Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000013535 sea water Substances 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 241001465754 Metazoa Species 0.000 claims abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000006227 byproduct Substances 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 241001131796 Botaurus stellaris Species 0.000 claims abstract description 4
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 4
- 150000002505 iron Chemical class 0.000 claims description 31
- 239000008188 pellet Substances 0.000 claims description 16
- 150000007524 organic acids Chemical class 0.000 claims description 11
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 claims description 6
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000002509 fulvic acid Substances 0.000 claims description 6
- 229940095100 fulvic acid Drugs 0.000 claims description 6
- 239000003518 caustics Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 229940072056 alginate Drugs 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 235000010443 alginic acid Nutrition 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 19
- 239000003651 drinking water Substances 0.000 abstract description 8
- 235000020188 drinking water Nutrition 0.000 abstract description 8
- 238000004332 deodorization Methods 0.000 abstract description 7
- 238000004065 wastewater treatment Methods 0.000 abstract description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 238000003801 milling Methods 0.000 abstract 1
- 235000010755 mineral Nutrition 0.000 description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003513 alkali Substances 0.000 description 7
- 238000009629 microbiological culture Methods 0.000 description 6
- 159000000014 iron salts Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910001566 austenite Inorganic materials 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052626 biotite Inorganic materials 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 229910052570 clay Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 229910021532 Calcite Inorganic materials 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FRTNIYVUDIHXPG-UHFFFAOYSA-N acetic acid;ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN FRTNIYVUDIHXPG-UHFFFAOYSA-N 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052892 hornblende Inorganic materials 0.000 description 2
- 239000003864 humus Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- -1 microbial culture Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000008262 pumice Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- CMFBGFRHPQTELQ-JQIJEIRASA-N Pulvinic acid Chemical group C=1C=CC=CC=1/C(C(=O)O)=C(C=1O)\OC(=O)C=1C1=CC=CC=C1 CMFBGFRHPQTELQ-JQIJEIRASA-N 0.000 description 1
- 241000282887 Suidae Species 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000490 cosmetic additive Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 235000021107 fermented food Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
- F16B41/00—Measures against loss of bolts, nuts, or pins; Measures against unauthorised operation of bolts, nuts or pins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B25—HAND TOOLS; PORTABLE POWER-DRIVEN TOOLS; MANIPULATORS
- B25B—TOOLS OR BENCH DEVICES NOT OTHERWISE PROVIDED FOR, FOR FASTENING, CONNECTING, DISENGAGING OR HOLDING
- B25B21/00—Portable power-driven screw or nut setting or loosening tools; Attachments for drilling apparatus serving the same purpose
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B25—HAND TOOLS; PORTABLE POWER-DRIVEN TOOLS; MANIPULATORS
- B25B—TOOLS OR BENCH DEVICES NOT OTHERWISE PROVIDED FOR, FOR FASTENING, CONNECTING, DISENGAGING OR HOLDING
- B25B23/00—Details of, or accessories for, spanners, wrenches, screwdrivers
- B25B23/02—Arrangements for handling screws or nuts
- B25B23/08—Arrangements for handling screws or nuts for holding or positioning screw or nut prior to or during its rotation
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Compounds Of Iron (AREA)
Abstract
Description
본 발명은 음용수의 처리공정, 미생물배양공정, 하·폐수처리공정, 탈취처리공정에 사용하는 자화된 2가-3가 철염이 함유된 미네랄 염을 2가 철염과 3가 철염 혼합수용액을 80∼100℃로 가열하면서 알칼리(Alkali)를 주입하여 pH를 12∼14로 조정하여 흑색의 자성 마그네타이트(Magnetite; Fe3O4)를 생성한 다음에 착자(着磁)하여 자화하고, 이를 염산용액에 용해한 다음, 이에 부식토와 해수나 해양 심층수로부터 소금을 생산하면서 부산물로 생산된 간수(苦汁)를 혼합하여 1∼24개월간 숙성한 다음에 펠렛트(Pellet) 형태로 가공한 후에 가열-건조하여 2가-3가 철염이 함유된 활성미네랄 염(Activated mineral salt)과 이의 펠렛트(Pellet)를 제조하는 방법에 관한 것이다.The present invention is a mixed solution of divalent iron salt and trivalent iron salt in the mineral salt containing magnetized divalent trivalent iron salt used in the treatment process of drinking water, microbial culture process, wastewater treatment process, deodorization treatment process Alkali was injected while heating to 100 ° C. to adjust the pH to 12 to 14 to produce black magnetic magnetite (Fe 3 O 4 ), followed by magnetization by magnetization, followed by magnetization in hydrochloric acid solution. After dissolving, the salt is produced from humus and seawater or deep seawater, mixed with by-products produced by by-products, aged for 1 to 24 months, processed into pellets, and heated and dried to form divalent. The present invention relates to a method for preparing activated mineral salts containing -trivalent iron salts and pellets thereof.
일본 특허공보 평(平) 5-6619호의 폐수처리공정에서는 미생물배양공정에 전술한 부식토를 펠렛트(Pellet) 형태로 성형 가공한 것과 유문암(流紋岩) 또는 대사이드(Dacite)질 부석(Pumice)과 함께 생물반응기(Bio-reactor)에 충전(充塡)하여 적용한 결과 일반 생물학적(활성오니) 처리공정에 비해서 처리효율이 월등히 향상되었다.In the wastewater treatment process of Japanese Patent Publication No. Hei 5-6619, the above-mentioned humus soil is formed into pellets in the microbial culture process, and rhyolite or dacite pumice is formed. ) And the bio-reactor was applied to the bio-reactor to improve the treatment efficiency compared to the general biological (active sludge) treatment process.
대한민국 특허 공개번호 2003-0019285호의 경우 전술한 부식토를 펠렛트 형태로 성형 가공한 것과 광물질을 함께 생물반응기에 충전하여 비육돈에 급여하는 음용수를 처리하여 급여한 결과 성장속도의 향상, 육질의 개선, 축사 내의 악취의 저감 ‥·등의 효과가 있었으며, 이를 산란계의 음용수를 처리하여 급여한 결과 산란율의 향상 및 계사 내의 악취발생의 저감 등의 효과가 있었다.In the case of Korean Patent Publication No. 2003-0019285, the above-mentioned humic soil was molded and processed into pellets, and the minerals were filled together with bioreactors and treated with drinking water for feeding pigs. There was an effect of reducing the bad smell of the inside, and the treatment of the drinking water of the laying hens resulted in the improvement of the laying rate and the reduction of the bad smell in the house.
그리고 자화된 2가-3가 철염과 여러 미네랄 염이 함유된 부식토의 경우 전술한 내용 이외에도 공기정화공정, 발효식품제조공정, 탈취처리공정, 토양개량제(土壤改良劑), 사료첨가제, 작물의 생육 및 발아촉진제, 화장품첨가제 등 다방면에 널리 이용되고 있다.And in the case of humic soils containing magnetized divalent trivalent iron salts and various mineral salts, in addition to the above, air purification process, fermented food manufacturing process, deodorization process, soil improving agent, feed additive, and growth of crops And it is widely used in various fields, such as a germination promoter and a cosmetic additive.
일본 나가사키 현(長崎縣)의 가라고(唐比) 함몰습지(陷沒濕地)의 부식토 경우는 습지보존 및 환경보존 측면에서 개발을 억제하고 있는 실정에 있으면서 상당히 고가로 판매되고 있어 구매조달 및 경제적인 문제점이 있으며, 또한 채굴위치 및 지점에 따라서 조성의 차이가 심하며, 2가-3가 철 함량이 낮은 경우에는 효율이 월등히 감소하는 등의 문제점이 있다.The corrosive soils of Kago Recessed Wetlands in Nagasaki Prefecture, Japan, are being sold at a very high price while being under development in terms of wetland conservation and environmental conservation. Phosphorus problem, and also the difference in composition according to the mining location and point, there is a problem such that the efficiency is greatly reduced when the dihydric-3 is low iron content.
그리고 대한민국 특허 출원번호 10-2005-0041392호의 경우 활성미네랄(반응성 미네랄)이 함유된 천매암(千枚岩), 거정석(巨晶石), 유문암(流紋岩) 또는 대사이드(Dacite)질의 부석(浮石), 석영반암(石英斑岩; 麥飯石), 석영섬록영암(石英閃綠玲岩; 醫王石), 태징석(泰澄石), 거정석(巨晶石), 견운모(絹雲母), 감람석(橄欖 石), 각섬석(角閃石), 흑운모(黑雲母), 제올라이트(Zeolite), 패화석(貝化石), 점토(황토), 화산회토(火山灰土)와 같은 광물을 단독 또는 2종류 이상 혼합한 광물을 300∼400메시(Mesh)로 분쇄한 분말을 부식물질(腐植物質)에 유기물/무기물의 무게 비가 0.8∼1.2의 비율이 되게 혼합하여 교반·혼화하고, 여기에 2가-3가 철염용액을 건량기준으로 철의 함량이 3∼15wt% 범위가 되게 혼합하여 1∼24개월간 방치하여 숙성한 다음에 바인더(Binder)로 알긴산소다(Sodium alginate)를 혼합·교반하여 구형이나 펠렛트(Pellet) 형태로 가공한 다음에 2∼3일간 자연건조한 후에 200∼250℃의 열풍공기로 건조하여 미네랄 염이 함유된 2가-3가 철염의 펠렛트(Pellet)를 제조하는 방법이 제시되어 있으나. 천매암, 거정석, 유문암 또는 대사이드질의 부석, 석영반암, 석영섬록영암, 태징석(泰澄石), 거정석, 견운모, 감람석, 각섬석, 흑운모, 제올라이트, 패화석, 점토, 화산회토와 같은 천연의 광물에는 활성미네랄함량이 그리 높지 않으면서 광물의 종류, 채굴장소 등에 따라서 활성미네랄함량의 차이가 심하기 때문에 균일한 제품을 생산할 수 없는 문제점이 있다. In the case of Korean Patent Application No. 10-2005-0041392, pumiceite, macrorite, rhyolite or rhodolite stone containing active minerals (reactive minerals) Quartz, quartz bedrock, quartz diorite yungam, tajing stone, giant stone, mica, Minerals such as olivine, hornblende, biotite, zeolite, zeolite, calcite, clay, clay and volcanic ash A powder obtained by crushing a mineral with 300 to 400 mesh is mixed with a corrosive substance at a weight ratio of organic to inorganic in a ratio of 0.8 to 1.2, followed by stirring and mixing. The solution is mixed so that the iron content is in the range of 3 to 15 wt% on a dry basis and left for 1 to 24 months to mature, followed by sodium alginate as a binder (Sodiu). m-alginate, mixed and stirred, processed into spherical or pellet form, followed by natural drying for 2 to 3 days, followed by drying with hot air air at 200-250 ° C to remove divalent trivalent iron salts containing mineral salts. There is a method of making pellets. Natural minerals such as feldspar, macrorite, rhyolite or large-scale pumice, quartz rock, quartz diorite, talcstone, macrorite, biotite, olivine, hornblende, biotite, zeolite, calcite, clay, and volcanic ash There is a problem in that it is not possible to produce a uniform product because the active mineral content is not so high and the active mineral content is very different depending on the type of mineral and the mining location.
본 발명은 상기와 같은 문제점을 해소하기 위해 2가-3가 철염이 함유된 활성미네랄 염과 이의 펠렛트를 제조하는 방법을 제공하는 데 본 발명의 목적이 있는 것이다.It is an object of the present invention to provide a method for preparing an active mineral salt containing a divalent trivalent iron salt and a pellet thereof in order to solve the above problems.
이와 같은 목적을 달성하기 위한 본 발명은, 제1철염과 제2철염을 혼합한 수용액을 가열하면서 알칼리를 주입하여 pH를 12∼14로 조정하여 고순도의 마그네타 이트(Fe3O4)를 생산되면 탈수건조한 후에 자속밀도가 최대한 높게 착자하여 자화된 마그네타이트를 제조하는 단계, 2가-3가 철염 용액의 제조단계, 2가-3가 철염이 함유된 활성미네랄 염을 제조하는 단계, 2가-3가 철염이 함유된 유기산 미네랄 착염을 제조하는 단계, 펠렛트(Pellet) 형태로 성형가공하는 단계로 이루어진 것에 특징이 있다.In order to achieve the above object, the present invention produces a high purity magnetite (Fe 3 O 4 ) by adjusting the pH to 12-14 by injecting alkali while heating an aqueous solution mixed with ferrous and ferric salts. When dehydrated and dried, the magnetic flux density is magnetized as high as possible to produce magnetized magnetite, the preparation of divalent trivalent iron salt solution, the preparation of active mineral salt containing divalent trivalent iron salt, the divalent- Preparing an organic acid mineral complex salt containing a trivalent iron salt, it is characterized by consisting of the step of molding in the form of pellets (Pellet).
본 발명은 미생물배양공정, 음용수의 처리공정, 정수처리공정, 하 ·폐수처리공정, 탈취처리공정 등에 사용하는 2가-3가 철염의 펠렛트(Pellet) 제조방법은 다음과 같다.The present invention is a method for producing pellets of divalent trivalent iron salt used in microbial culture process, drinking water treatment process, water treatment process, sewage and wastewater treatment process, deodorization treatment process is as follows.
1. 자화된 마그네타이트(Magnetite) 제조단계1. Magnetized Magnetite Manufacturing Step
2가 철염과 3가 철염의 혼합수용액을 80∼100℃로 가열하면서 알칼리(Alkali)를 주입하여 pH를 12∼14로 조정하여 흑색의 마그네타이트(Fe3O4)를 생성한다.Alkali is injected while the mixed aqueous solution of the divalent iron salt and the trivalent iron salt is heated to 80 to 100 ° C. to adjust the pH to 12 to 14 to produce black magnetite (Fe 3 O 4 ).
Fe2 + + 2Fe3 + + 8OH- → Fe3O4 + 4H2O...............................① Fe 2 + + 2Fe 3 + + 8OH - → Fe 3 O 4 + 4H 2 O ...............................
여기서 사용하는 2가 철염은 제1황산철(FeSO4), 제l염화철(FeCl2)을 사용하고, 3가 철염은 제2황산철(Fe2(SO4)3), 제2염화철(FeCl3)을 사용하며, 알칼리는 가성소다(NaOH), 암모니아수(NH4OH), 수산화칼륨(KOH), 탄산소다(Na2CO3)를 사용한다.The divalent iron salt used here is ferrous sulfate (FeSO 4 ), ferric chloride (FeCl 2 ), the trivalent iron salt is ferric sulfate (Fe 2 (SO 4 ) 3 ), ferric chloride (FeCl 3 ) is used, and alkali is used for caustic soda (NaOH), ammonia water (NH 4 OH), potassium hydroxide (KOH), sodium carbonate (Na 2 CO 3 ).
본 발명에서는 반응식①의 반응의 수율을 향상하기 위해서 전자석이 설치된 반응기의 자계(磁界)하에서 교반반응을 한다.In the present invention, in order to improve the yield of the reaction of Scheme ①, the reaction is stirred under the magnetic field of the reactor in which the electromagnet is installed.
반응식①의 반응이 완료되면 반응과정에서 생성된 염을 제거하기 위해서 3∼4회 수세처리를 한 다음에 탈수 후에 건조한다.After the reaction of Scheme ① is completed, to wash the salt generated in the reaction process 3-4 times, and then dried after dehydration.
건조된 마그네타이트의 분발은 플라스틱(Plastic)병과 같은 캡슐(Capsule)에 압축-충전한 것을 착자기의 요크(Yoke)에 주입하고, 자속밀도(磁束密度)가 350∼500G(Gauss) 범위로 착자(着磁)한다.The dried magnetite powder is injected into the yoke of the magnetizer by compressing and filling a capsule such as a plastic bottle into the yoke of the magnetizer, and the magnetic flux density is in the range of 350 to 500 G (Gauss).着 磁).
이때, 보다 자속밀도(磁束密度)가 높은 마그네타이트를 생산하기 위해서는 반응식①에서 생성된 건조된 마그네타이트를 산소분위기 중에서 가열하여 감마산화2철(γ-Fe2O3)을 만들거나, 마그네타이트를 30∼35wt%의 과산화수소(H2O2)와 혼합하여 반응하면 감마 산화2철(γ-Fe2O3)의 생성효율이 향상된다.At this time, in order to produce a magnetite having a higher magnetic flux density, the dried magnetite produced in the reaction formula ① is heated in an oxygen atmosphere to form gamma ferric oxide (γ-Fe 2 O 3 ), or the magnetite is 30 to When the mixture is mixed with 35 wt% hydrogen peroxide (H 2 O 2 ), the production efficiency of gamma ferric oxide (γ-Fe 2 O 3 ) is improved.
다음에 이 감마 산화2철(γ-Fe2O3)을 염산용액에 용해한 다음에 전자석이 설치된 반응기의 자계(磁界) 하에서 80∼100℃로 가열하면서 알칼리(Alkali)를 주입하여 pH를 12∼14로 조정하면 흑색의 마그네타이트를 재생성한다.Next, the gamma ferric oxide (γ-Fe 2 O 3 ) is dissolved in a hydrochloric acid solution, and alkali (Alkali) is injected while heating to 80 to 100 ° C. under a magnetic field of a reactor equipped with an electromagnet, thereby adjusting the pH to 12 to Adjust to 14 to regenerate black magnetite.
4Fe3O4 + O2 → 6γ- Fe2O3 ........................................②4Fe 3 O 4 + O 2 → 6γ- Fe 2 O 3 ....................................... ②
2Fe3O4 + H2O2 → 3γ - Fe2O3 + H2O ...............................③2Fe 3 O 4 + H 2 O 2 → 3γ-Fe 2 O 3 + H 2 O .............................. .③
γ-Fe2O3 + 6HCl → 2FeCl3 + 3H2O .................................④γ-Fe 2 O 3 + 6HCl → 2FeCl 3 + 3H 2 O ................................. ④
FeCl2 + 2FeCl3 + 8NaOH → Fe3O4 + 8NaCl + 4H2O .....................⑤FeCl 2 + 2FeCl 3 + 8NaOH → Fe 3 O 4 + 8NaCl + 4H 2 O .......................... ⑤
FeCl2 + 2FeCl3 + 8NH3 + 4H2O → Fe3O4 + 8NH4Cl .....................⑥FeCl 2 + 2FeCl 3 + 8NH 3 + 4H 2 O → Fe 3 O 4 + 8NH 4 Cl ..................... ⑥
반응식⑤ 또는 ⑥의 반응이 완료되면 반응과정에서 생성된 염을 제거하기 위해서 3∼4회 수세처리를 한 다음에 탈수 후에 건조한다.After completion of the reaction of reaction formula ⑤ or ⑥, to remove the salt generated in the reaction process, it is washed three to four times and then dried after dehydration.
건조된 마그네타이트의 분발은 플라스틱 병과 같은 캡슐에 압축-충전한 것을 착자기의 요크(Yoke)에 주입하고, 자속밀도가 450∼500G 범위로 착자한다.The dried magnetite powder is injected into the yoke of the magnetizer by compression-filling a capsule such as a plastic bottle and magnetized in the magnetic flux density in the range of 450 to 500G.
2. 2가-3가 철염 용액의 제조단계2. Preparation Step of Divalent-Trivalent Iron Salt Solution
착자된 자화 마그네타이트 분말을 5∼10wt%의 염산 수용액에 용해하여 2가-3가 철염용액을 제조한다.The magnetized magnetite magnetite powder is dissolved in 5-10 wt% aqueous hydrochloric acid to prepare a divalent trivalent iron salt solution.
Fe3O4 + 8HCl →FeCl2 + 2FeCl3 + 4H2O ...........................⑦Fe 3 O 4 + 8HCl → FeCl 2 + 2FeCl 3 + 4H 2 O ........................... ⑦
이때 경비절감을 위해서 전술한 반응식⑦의 반응에서 인공제조된 자화 마그네타이트 분말 대신 천연의 자철광(磁鐵鑛)을 300∼400 메시(Mesh)로 분쇄한 분말을 사용할 수도 있다.At this time, instead of the magnetized magnetite powder produced artificially in the reaction of the above reaction formula ⑦ in order to reduce the cost, it is also possible to use a powder pulverized with natural magnetite (300) to 300 to 400 mesh (Mesh).
3. 2가-3가 철염이 함유된 활성미네랄 염을 제조하는 단계3. Preparation of active mineral salt containing divalent trivalent iron salt
활성미네랄(반응성 미네랄)은 해수나 해양 심층수(海洋深層水)로부터 소금을 생산하는 과정에서 부산물로 생산되는 간수(苦汁; Bittern)를 이용하며, 간수는 소금의 제조방법에 따라서 약간의 차이는 있으나, 천일 염전에서 생산되는 간수의 성분은 염화마그네슘(MgSO4)이 15∼19wt%, 황산 마그네슘(MgCl2)이 6∼9wt%, 염화칼륨(KCl)이 2∼4wt%, 염화나트륨(NaCl)이 2∼6wt%, 기타성분이 0.2∼0.4wt% 등으로 되어 있다.Activated minerals (reactive minerals) use bittern, which is produced as a by-product in the process of producing salt from seawater or deep sea water, and there are some differences depending on the salt production method. , the components of the brine produced by the torsion of one thousand and one this is 15~19wt% of magnesium chloride (MgSO 4), magnesium sulfate (MgCl 2) 6~9wt%, potassium chloride (KCl) is 2~4wt%, sodium chloride (NaCl) 2 It is -6 wt%, the other components are 0.2-0.4 wt%, and the like.
해수와 해양 심층수에는 동·식물의 생육에 필요한 다종다양한 광물질 (mineral)이 용해되어 있으면서 대부분의 미네랄성분은 동·식물은 물론이고, 미생물이 용이하게 섭취할 수 있는 수용액상태로 존재하기 때문에 육상의 광물로부터 수용성 미네랄(이를 활성미네랄이라 함)을 용출하는 것보다 용이한 특성이 있다.In seawater and deep sea water, various minerals necessary for the growth of animals and plants are dissolved, and most minerals exist in aqueous solution that can be easily ingested by microorganisms as well as animals and plants. It is easier than eluting water-soluble minerals (which are called active minerals) from minerals.
전술한 간수 중에는 칼슘(Ca)성분이 소금을 생산하는 과정에 염전의 증발지 등에서 칼슘염(CaSO4, CaCO3 등)으로 침전제거되기 때문에 칼슘성분이 거의 존재하지 않은 문제점이 있다.Among the above-described brine, there is a problem in that calcium component is hardly present because calcium (Ca) component is precipitated and removed as calcium salt (CaSO 4 , CaCO 3, etc.) in the evaporation pond of salt during process of producing salt.
그래서 조개 껍질(貝塚)이나 동물뼈를 850∼1,200℃에서 소성(燒成)한 다음, 300∼400메시(Mesh)로 분쇄한 것을 5∼10wt% 염산수용액에 용해한 칼슘용액을 Ca/Mg의 중량비가 2∼6의 비율이 되게 첨가할 필요가 있다.Therefore, the calcined shells or animal bones were calcined at 850-1,200 ° C, and then pulverized with 300-400 mesh and dissolved in a 5-10 wt% aqueous hydrochloric acid solution. It is necessary to add so that it may become a ratio of 2-6.
CaO + 2HCl → CaCl2 + H2O .............................⑧ CaO + 2HCl → CaCl 2 + H 2 O ......................... ⑧
간수에 칼슘용액을 첨가하여 미네랄밸런스를 Ca/Mg의 중량비가 2∼6으로 조정한 용액에 철 함량이 건량기준(乾量基準)으로 3∼15wt% 범위로 2가-3가 철염 용액의 제조단계에서 제조된 2가-3가 철염용액을 첨가하여 2가-3가 철염이 함유된 활성미네랄 염을 제조한다.Preparation of divalent trivalent iron salt solution with iron content in the range of 3-15 wt% in dry weight standard solution by adding calcium solution to the brine and adjusting the mineral balance to 2-6 weight ratio of Ca / Mg The active mineral salt containing the divalent trivalent iron salt is prepared by adding the divalent trivalent iron salt solution prepared in the step.
여기서 제조된 2가-3가 철염이 함유된 활성미네랄 염을 음용수의 처리공정, 미생물배양공정, 하·폐수처리공정, 탈취처리공정에 미네랄공급용으로 사용할 수도 있다.The activated mineral salt containing the divalent trivalent iron salt prepared here may be used for mineral supply in the treatment of drinking water, microbial culture, sewage and wastewater treatment, and deodorization treatment.
4. 2가-3가 철염이 함유된 유기산 미네랄 착염을 제조하는 단계4. Preparing organic acid mineral complex salt containing divalent trivalent iron salt
전술한 2가-3가 철염이 함유된 활성미네랄 염을 제조하는 단계에서 제조된 2 가-3가 철염이 함유된 활성미네랄 염인 무기질 염은 동·식물 및 미생물의 이용효율이 떨어지기 때문에 각종미네랄성분과 착염(錯鹽)을 생성하는 구연산(Citric acid), 주석산(Tartaric acid), 호박산(Succinic acid), 에틸렌디아민테트라아세트산(Ethylendiaminetetraacetic acid, EDTA), 풀브산(Fulvic acid) 중에서 단독 또는 2종류 이상을 혼합한 유기산을 건량기준으로 20∼100wt% 범위로 혼합·교반하여 2가-3가 철염이 함유된 유기산 미네랄 착염을 제조한다.Inorganic salts, which are the active mineral salts containing the divalent trivalent iron salts prepared in the step of preparing the active mineral salts containing the divalent trivalent iron salts, have various minerals since they have low utilization efficiency of animals, plants and microorganisms. Citric acid, tartaric acid, succinic acid, Ethylendiaminetetraacetic acid (EDTA), Fulvic acid, which produce complex salt with components The organic acid mixed with the above is mixed and stirred in the range of 20 to 100 wt% on a dry basis to prepare an organic acid mineral complex salt containing a divalent trivalent iron salt.
유기산 + 미네랄 염 → 유기산 미네랄 착염 .........................⑨ Organic acid + mineral salt → organic acid mineral complex salt ......... ⑨⑨
풀브산(Fulvic acid)은 천연의 부식물질(이탄)을 1차 가성소다(NaOH)와 같은 알칼리를 처리하여 pH를 13∼14로 조정하여 용해된 용액에 염산(HCl)과 같은 강산을 주입하여 pH를 1.0∼2.0으로 조정하였을 때 침전되는 부식산(Humic acid)을 제거하고 난 다음에 용액상태로 추출한다.Fulvic acid is treated with an alkali such as primary caustic soda (NaOH) to adjust the pH to 13-14 by injecting a strong acid such as hydrochloric acid (HCl) into the dissolved solution. When the pH is adjusted to 1.0∼2.0, the precipitated humic acid is removed and then extracted into solution.
여기서 제조된 액상상태의 2가-3가 철염이 함유된 유기산 미네랄 착염을 음용수의 처리공정, 미생물배양공정, 하·폐수처리공정, 탈취처리공정에 미네랄공급용으로 사용한다.The organic acid mineral complex salt containing the divalent trivalent iron salt prepared in the liquid state is used for mineral supply in the treatment of drinking water, microbial culture, sewage and wastewater treatment and deodorization treatment.
4. 펠렛트(Pellet) 형태로 성형가공하는 단계4. Forming process in pellet form
2가-3가 철염이 함유된 유기산 미네랄 착염을 펠렛트(Pellet) 형태로 성형가공하여 미네랄 반응 탑에 충전(充塡)하여 사용하는 경우에는 2가-3가 철염이 함유된 활성미네랄 염을 제조하는 단계에서 제조된 2가-3가 철염이 함유된 활성미네랄 염을 80∼120℃의 건조기에서 수분을 증발한 다음, 850∼1,200℃에서 소성(燒成)한 다음, 300∼400메시(Mesh)로 분쇄한 분말을 부식물질(腐植物質)에 유기물/무기물의 무게 비가 0.8∼1.2의 비율이 되게 혼합하고, 함수율이 50∼60wt% 범위가 되게 물을 가하고. 교반·혼합하면서 5∼10wt%의 염산(HCl)을 pH가 1∼3의 범위로 가한 다음, 1∼24개월간 방치하여 숙성한다.When the organic acid mineral complex salt containing the divalent trivalent iron salt is molded into pellets and filled into the mineral reaction tower, an active mineral salt containing the divalent trivalent iron salt is used. The active mineral salt containing the divalent trivalent iron salt prepared in the manufacturing step was evaporated in a dryer at 80 to 120 ° C., and then calcined at 850 to 1,200 ° C., followed by 300 to 400 mesh ( The powder pulverized into a mesh is mixed with a corrosive substance in a weight ratio of organic matter and inorganic matter in a ratio of 0.8 to 1.2, and water is added so as to have a water content in a range of 50 to 60 wt%. While stirring and mixing, 5-10 wt% hydrochloric acid (HCl) is added in a pH range of 1 to 3, then left to mature for 1 to 24 months.
이때 pH가 1∼3의 산성에서 부식물질은 풀브산(Fulvic acid)은 유리(遊離)의 상태로 유도(誘導)되면서 각종미네랄 산화물과 반응하여 풀브산미네랄착염형태로 된다.At this time, the pH of the acid is 1 to 3, the corrosive substance is pulvic acid (Fulvic acid) is induced in the state of free (誘導) and reacts with various mineral oxides to form the fulbate mineral complex salt.
미네랄산화물 + 풀브산 → 풀브산미네랄착염 .....................⑩Mineral Oxide + Fulvic Acid → Fulvic Mineral Complex Salt .........
1∼24개월간 숙성하여 풀브산미네랄착염형태로 된 것에 바인더(Binder)로 알긴산소다(Sodium alginate)를 6∼10wt %로 가하고, 펠렛트(Pellet)성형이 용이하도록 함수율을 40∼45wt%로 조정하여 반죽한 것을 10∼30㎜φ의 크기로 사출성형가공한 다음에 2∼3일간 자연건조한 후에 200∼250℃의 열풍공기로 건조하여 미네랄착염의 펠렛트(Pellet)를 제조한다.Sodium alginate was added to the form of mineral complex salt in the form of fulbrate mineral complex for 1 to 24 months with 6-10 wt% of binder, and the water content was adjusted to 40 to 45 wt% to facilitate pellet molding. After kneading, the injection molding process was carried out to a size of 10 to 30 mmφ, followed by natural drying for 2 to 3 days, followed by drying with hot air air at 200 to 250 ° C. to prepare pellets of mineral complex salts.
이상에서 상술한 바와 같이 본 발명은, 미생물배양공정, 음용수의 처리공정, 정수처리공정, 하·폐수처리공정, 탈취처리공정 등에 천연산의 2가-3가 철염이 함유된 유기산 미네랄 착염을 사용하는 곳에 대체품으로 널리 보급될 것으로 전망된다.As described above, the present invention uses an organic acid mineral complex salt containing a divalent trivalent iron salt of natural acid in a microbial culture step, drinking water treatment step, water purification step, sewage / wastewater treatment step, deodorization step, and the like. It is expected that it will be widely used as a substitute.
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| KR101037280B1 (en) | 2008-01-31 | 2011-05-31 | 서희동 | Manufacturing method of bed soil using bittern which was produced from deep sea water |
| KR101384992B1 (en) | 2009-01-15 | 2014-04-17 | 서희동 | Method for producing drinking water from deep sea water |
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| KR20050055659A (en) * | 2005-05-18 | 2005-06-13 | 서희동 | Manufacturing method for pellet of ferrous-ferric salts |
| KR100513362B1 (en) * | 2002-12-26 | 2005-09-07 | 서희동 | Manufacturing method of magnetized minerals |
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| KR100513362B1 (en) * | 2002-12-26 | 2005-09-07 | 서희동 | Manufacturing method of magnetized minerals |
| KR20050055659A (en) * | 2005-05-18 | 2005-06-13 | 서희동 | Manufacturing method for pellet of ferrous-ferric salts |
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| KR100945312B1 (en) | 2006-06-30 | 2010-03-10 | 서희동 | Desalination method of deep sea water |
| KR101037280B1 (en) | 2008-01-31 | 2011-05-31 | 서희동 | Manufacturing method of bed soil using bittern which was produced from deep sea water |
| KR101384992B1 (en) | 2009-01-15 | 2014-04-17 | 서희동 | Method for producing drinking water from deep sea water |
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