표제지

제출문

보고서 요약서

요약문

SUMMARY

CONTENTS

목차

제1장 연구개발 과제의 개요 23

제1절 기술개발의 개요 23

제2절 기술개발의 내용 24

제2장 국내외 기술개발 현황 27

제1절 해외 금속광물의 일반 현황 27

1. 몰리브덴광 27

2. 니켈광 37

3. 동광 45

4. 코발트광 52

제2절 금속광물의 활용기술 현황 57

1. 국내 기술개발 현황 57

2. 국외 기술개발 현황 58

제3절 금속광물의 품위향상 기술 59

1. 파분쇄 기술 59

2. 부유선별 기술 63

제4절 몰리브덴 정광의 산화배소 기술 68

1. 국내 기술개발 현황 68

2. 국외 기술개발 현황 69

제5절 산업원료화 기술 71

1. 몰리브덴의 초고순도화 기술 71

2. Ni 및 Cu 합금 나노분말 제조 기술 71

3. 슬러리환원법에 의한 미세 니켈 분말 제조 72

제3장 연구개발수행 내용 및 결과 75

제1절 금속광물의 품위향상 기술 개발 75

1. 몰리브덴광의 품위향상 기술 개발 75

2. 산화니켈광의 품위향상 기술 개발 105

3. 동-코발트광의 품위향상 기술 개발 122

제2절 금속광물의 고순도화 및 친환경 제련기술 개발 138

1. 저품위 몰리브덴 정광의 제련 연구 138

2. 납의 휘발 정제 154

3. Co-Cu 광으로부터 유가금속 침출 공정 개발 162

제3절 산업 원료소재화 기술 198

1. 몰리브덴의 플라스마 용해정련 및 극미량 불순물 분석 198

2. 촉매용 금속 분말 제조 기술 206

3. 슬러리환원법에 의한 미세 니켈 분말 제조 217

제4절 콩고민주공화국의 광업 관련법 검토 228

1. 배경 및 정책 방향 228

2. 신광업법 주요 내용 229

3. 광업권 취득 절차 및 소요 비용 240

제4장 목표달성도 및 관련분야에의 기여도 245

제1절 연구개발 목표달성도 245

제2절 대외기여도 248

제5장 연구개발 결과의 활용계획 249

제6장 연구개발과정에서 수집한 해외과학기술정보 250

제7장 참고 문헌 253

컬럼부선을 이용한 미립자 회수 기술 개발 259

제출문 261

요약문 263

SUMMARY 265

Contents 267

목차 268

제1장 서론 269

제1절 연구개발의 목적 및 필요성 269

1. 연구개발의 목적 269

2. 연구개발의 필요성 269

제2장 국내외 기술개발 현황 275

제1절 국내의 경우 275

제2절 국외의 경우 276

제3절 국내외 특허 및 현존 기술과의 관련성 277

1. 국내 특허 277

2. 국외 특허 277

제3장 연구개발수행 내용 및 결과 279

제1절 광물학적 조사 279

1. 기초광물 조사 279

2. 주사전자 현미경(FE-SEM) & 전자현미분석기(EPMA) 조사 281

3. X-ray 광전자분광분석기(ESCA) 286

제2절 입도조절 289

제3절 자력선별 294

제4절 Flotation Test 299

1. AM₂ 적용 실험 301

2. AM28 적용 실험(이미지참조) 302

3. PAX(Potassium Amyl Xanthate) 적용 실험 303

4. Sodium Oleate 적용 실험 304

제5절 Column Flotation 307

1. 포수제 시약량에 따른 컬럼부선 실험 312

2. 기포제 사용량에 따른 컬럼부선 실험 312

3. 급광량에 따른 컬럼부선 실험 313

제4장 결론 314

뉴칼레도니아산 Ni-laterite광의 산침출 연구 315

제출문 317

요약문 319

SUMMARY 323

Contents 325

목차 326

제1장 서론 327

제2장 국내외 기술개발 현황 329

제3장 연구개발 수행 내용 및 결과 333

제1절 실험 방법 및 실험장치 333

제2절 황산용액에서 니켈 라테라이트광의 침출 334

제3절 용매추출에 의한 니켈, 코발트 및 마그네슘의 분리 344

제4절 비누화 D2EHPA에 의한 용매추출과 역추출 350

제5절 농축용액에서 용매추출에 의한 니켈과 코발트의 분리 357

제6절 침전에 의한 니켈과 코발트의 회수 370

제4장 연구개발목표 달성도 및 대외기여도 372

제5장 연구개발결과의 활용계획 373

제6장 참고문헌 375

몰리브덴 배소광 침출액 중의 불순물 정제연구 377

제출문 379

요약문 381

SUMMARY 383

CONTENTS 385

목차 386

제1장 서론 387

제2장 이론적 고찰 389

제1절. 이성분 혼합계의 고-액 상평형 389

제2절. 삼성분 혼합계의 액-액 상평형 391

제3절. gE model 식을 이용한 데이터 상관(이미지참조) 392

제4절. 혼합물의 과잉성질 393

제3장 실험 399

제1절. 시약 399

제2절. 장치 및 실험방법 400

제4장 결과 및 고찰 404

제1절. Solvent 포함 이성분 혼합계의 고-액평형 404

제2절. Solvent 포함 삼성분 혼합계의 액-액 상평형 410

제3절. Solvent 포함 이성분 및 삼성분계 VE 및 △R(이미지참조) 414

제5장 결론 430

제6장 참고문헌 431

Removal of W from Mo by means of anion exchange method 433

Table 1-1. Objective for self-development of strategic mineral resources 23

Table 2-1. Import of molybdenum by nations 28

Table 2-2. Reserve and grade of molybdenum in domestic 29

Table 2-3. Reserve & reserve base of molybdenum in the world 30

Table 2-4. The yield of molybdenum in the world 31

Table 2-5. International price of molybdenum by year 32

Table 2-6. Composition of main molybdenum minerals 35

Table 2-7. Prospect of nickel price 37

Table 2-8. Reserve and grade of nickel in domestic 38

Table 2-9. Import and export of nickel 38

Table 2-10. Reserve & reserve base of nickel in the world 39

Table 2-11. Production of nickel in the world 40

Table 2-12. Minerals containing nickel 43

Table 2-13. Application of nickel alloys. 45

Table 2-14. Reserve of domestic copper ore 46

Table 2-15. World copper price 47

Table 2-16. World copper ore production 48

Table 2-17. World metal copper production 49

Table 2-18. General usage of copper 51

Table 2-19. Domestic cobalt import 52

Table 2-20. International cobalt price 53

Table 2-21. World mining production of cobalt 53

Table 2-22. World refinery production of cobalt 54

Table 2-23. Uses of cobalt 56

Table 2-24. Specifications of crushing and grinding facilities 60

Table 3-1. Chemical analysis of molybdenite minerals used in this study 76

Table 3-2. Chemical analysis of OU concentrate minerals used in this study 77

Table 3-3. Size distribution and chemical analysis of various size fraction 78

Table 3-4. Chemical composition of raw ore 106

Table 3-5. Chemical composition of raw ore for particle size 108

Table 3-6. Chemical composition of copper-cobalt ore 123

Table 3-7. Chemical composition of malachite particle 124

Table 3-8. Chemical composition of fractionated particles of ore 124

Table 3-9. Size distribution by cyclosizer 126

Table 3-10. Chemical composition of flotation products(wt.%) 136

Table 3-11. Recovery and grade of flotation products 137

Table 3-12. Chemical compositions of the molybdenite concentrate 139

Table 3-13. Sulfur contents involved in the samples obtained after the oxidative roasting at 838 K under air atmosphere. 142

Table 3-14. Sulfur contents involved in the samples obtained after the oxidative roasting of 67㎛ for 60 min. 142

Table 3-15. Vapor pressures of PbS, PbO and MoO₃ 156

Table 3-16. The effect of reaction temperature on Pb removals 160

Table 3-17. The effect of reaction time on Pb removals at 850℃ 161

Table 3-18. The effect of reaction time on Pb removals at 850℃ 161

Table 3-19. XRF Analysis of cobalt ore 163

Table 3-20. Weight loss of roasted ore 170

Table 3-21. Chemical analysis of cobalt ore(%) 170

Table 3-22. Chemical composition of the leaching solution of the roasted ore using a sulfuric acid solution(mg/L) 189

Table 3-23. Chemical composition of the leaching solution of the roasted ore using a sulfuric acid solution mixed with H₂O₂(mg/L) 190

Table 3-24. Chemical composition of the leaching solution of the roasted ore using a hydrochloric acid solution(mg/L) 190

Table 3-25. Chemical composition of the leaching solution of the roasted ore using a hydrochloric acid solution mixed with H₂O₂(mg/L) 191

Table 3-26. Chemical composition of the leaching solution of the roasted ore at 300℃ using a nitric acid solution(mg/L) 191

Table 3-27. Chemical composition of the leaching solution of the roasted ore using a nitric acid solution mixed with H₂O₂(mg/L) 191

Table 3-28. Concentration changes of metallic impurities in the Mo samples before and after H-PAM and the average removal degrees of the impurities. 204

Table 3-29. Diameter of Ni-plated Al wire and corresponding alloy composition 211

Table 3-30. Specific surface areas, pore volumes and pore diameters of porous nano particles prepared by leaching for 9 hours 216

Table 3-31. Chemical reagent used for experiments 217

Table 3-32. The Sorts of Mining Right 241

Table 3-33. The Application Procedure of Mining Right 242

Table 3-34. Taxes for area of mining right. 244

Fig. 2-1. Consumption of molybdenum by purpose. 33

Fig. 2-2. Consumption of molybdenum by area. 34

Fig. 2-3. Major molybdenum minerals. 35

Fig. 2-4. Purpose of molybdenum concentrate. 36

Fig. 2-5. Major nickel minerals. 42

Fig. 2-6. Uses of nickel. 43

Fig. 2-7. Major copper minerals. 50

Fig. 2-8. Major cobalt minerals. 54

Fig. 2-9. Jaw crusher. 60

Fig. 2-10. Cone crusher. 61

Fig. 2-11. Roll crusher. 61

Fig. 2-12. Ball mill. 62

Fig. 2-13. Rod mill. 62

Fig. 2-14. Contact angle between bubble and particle. 63

Fig. 2-15. Principle and schematic view of froth flotation. 65

Fig. 2-16. Principle and schematic view of column flotation. 65

Fig. 2-17. Flowsheet of the pyrometallurgical process for producing molybdenum. 69

Fig. 2-18. Schematic cutaway diagram of commercial MLCC. 73

Fig. 2-19. SEM image of inner face of commercial MLCC and human hair. 73

Fig. 3-1. XRD of raw molybdenite sample from Oyuny Undra mine. 75

Fig. 3-2. XRD of concentrate sample from Oyuny Undra mine. 76

Fig. 3-3. Mapping of raw molybdenite sample by SEM-EDAX. 77

Fig. 3-4. Mapping of raw molybdenite sample by SEM-EDAX(×200, ×500). 78

Fig. 3-5. Principle of froth flotation. 79

Fig. 3-6. Flotator used in this test for froth flotation of molybdenite. 80

Fig. 3-7. Flowsheet for froth flotation of molybdenite minerals. 81

Fig. 3-8. Flowsheet of Rougher flotation as particle size. 81

Fig. 3-9. Flowsheet for multistage froth flotation of molybdenite minerals. 82

Fig. 3-10. Flowsheet for froth flotation of Concentrate molybdenite minerals. 83

Fig. 3-11. Flowsheet for multistage froth flotation of molybdenite concentrate. 83

Fig. 3-12. Photo for recovery process of molybdenite in froth flotation. 84

Fig. 3-13. Effect of collector on grade and recovery of molybdenite in froth flotation. 86

Fig. 3-14. Effect of pH on grade and recovery of molybdenite in froth flotation. 86

Fig. 3-15. Effect of frother on grade and recovery of molybdenite in froth flotation. 87

Fig. 3-16. Effect of cleaning time on grade and recovery of molybdenite in froth flotation. 88

Fig. 3-17. Effect of pulp density on grade and recovery of molybdenite in froth flotation. 89

Fig. 3-18. Effect of Pb depressant on grade and recovery of molybdenite in froth flotation. 90

Fig. 3-19. Effect of dosage of depressant on grade and recovery of molybdenite in froth flotation. 91

Fig. 3-20. Separation efficiency of molybdenite as particle size in 1st flotation. 92

Fig. 3-21. Recovery and grade of molybdenite by flotation with a change of pH. 93

Fig. 3-22. Effect of regrinding time on grade and recovery of rougher concentrate(-48mesh, pH 8). 94

Fig. 3-23. Effect of regrinding time on grade and recovery of rougher concentrate.(-48mesh, pH 9). 95

Fig. 3-24. Effect of regrinding time on grade and recovery of rougher concentrate.(-48mesh, pH 10). 96

Fig. 3-25. Effect of dosage of depressant on grade and recovery(48mesh, pH 9). 97

Fig. 3-26. Grade and recovery for molybdenite with a change of collector. 99

Fig. 3-27. Effect of dosage(Na₂SO₃) of Cu depressant on grade and recovery. 99

Fig. 3-28. Effect of dosage (Na₂SO₃) of Cu depressant on grade and recovery. 100

Fig. 3-29. Effect of regrinding time on grade and recovery of molybdenite. 101

Fig. 3-30. Effect of dosage of Cu depressant on grade and recovery(regrinding 3min). 102

Fig. 3-31. SEM/EDAX on concentrate. 103

Fig. 3-32. SEM/EDAX on tailing. 103

Fig. 3-33. SEM/EDAX on raw ore. 104

Fig. 3-34. SEM/EDAX on concentrated ore. 104

Fig. 3-35. Geological map of New caledonia. 105

Fig. 3-36. Profile of laterite ore in New caledonia. 106

Fig. 3-37. XRD pattern of raw ore for color and shape. 107

Fig. 3-38. XRD pattern of raw ore for particle size. 108

Fig. 3-39. The crystal structure of Lizardite. 109

Fig. 3-40. SEM/EDS analysis of Ni ore. 110

Fig. 3-41. EPMA ananlysis of Ni ore. 111

Fig. 3-42. The Schematic of Drum Type Magnetic Separation. 113

Fig. 3-43. High intensity magnetic separator. 114

Fig. 3-44. Cross-belt type magnetic separator. 114

Fig. 3-45. Macro and micro image of grinding. 115

Fig. 3-46. Flowsheet of magnetic separation. 116

Fig. 3-47. XRD pattern of the product by dry magnetic separation. 117

Fig. 3-48. XRD pattern of the products by wet magnetic separation. 117

Fig. 3-49. XRD patterns of Ni ore with various grinding times. 118

Fig. 3-50. FT-IR Spectra of Ni ore with various grinding times. 119

Fig. 3-51. TG-DTA curves Ni ore with various grinding times. 119

Fig. 3-50. Particle size distribution and mean size. 120

Fig. 3-52. SEM of ground Ni ore (a)0min, (b)15min, (c)60min, (d) enlarge of (c). 120

Fig. 3-53. Yield of extraction by (a)0.5N HCl, (b)0.5N H₂SO₄, (c), (d)samples ground 30min. 121

Fig. 3-54. XRD pattern of copper-cobalt ore. 122

Fig. 3-55. XRD pattern of malachite particle. 123

Fig. 3-56. EPMA of malachite particle. 123

Fig. 3-57. XRD patterns of fractionated particles of ore. 125

Fig. 3-58. XRD patterns of fractionated particles by cyclosizer. 126

Fig. 3-59. Wet high intensity magnetic separator. 126

Fig. 3-60. Magnetic products by HIMS at 6,000G. 127

Fig. 3-61. Magnetic products by HIMS at 10,000G. 128

Fig. 3-62. XRD patterns of products by HIMS at 6,000G. 129

Fig. 3-63. Zero point of charge of malachite. 131

Fig. 3-64. Eh-pH of Cu-C-S-O-H system. 132

Fig. 3-65. Recovery of malachite with pH and collectors. 133

Fig. 3-66. Recovery of malachite with different amount of collectors. 134

Fig. 3-67. Recovery of malachite with different types of collectors. 134

Fig. 3-68. Recovery of malachite after sulfurization of ore surface. 135

Fig. 3-69. XRD patterns of flotation products. 136

Fig. 3-70. Schematic diagram of the experimental for TGA thermal analysis. 140

Fig. 3-71. XRD patterns for each particle size of the sample. 141

Fig. 3-72. Standard Gibbs free energy of the sulfide compounds. 143

Fig. 3-73. Effect of oxygen partial pressure on the oxidative roasting 823 K. 143

Fig. 3-74. Effect of reaction temperature on the oxidative roasting of 67 ㎛ in air. 144

Fig. 3-75. TGA of the oxidative roasting of 53, 67 and 103㎛ in air at 838 K. 145

Fig. 3-76. TGA of the oxidative roasting of 53, 67 and 103㎛ in air at 808 K. 145

Fig. 3-77. Effect of reaction temperature on the oxidative roasting of 53 ㎛ in air. 146

Fig. 3-78. Effect of reaction temperature on the oxidative roasting of 103㎛ in air. 146

Fig. 3-79. SEM of particles before and after the oxidative roasting of 67㎛ in air for 60 min at 823 K. 147

Fig. 3-80. Plot of the results in Fig.3-62 according to eq. (3). 148

Fig. 3-81. Plot of the results in Fig.3-63 according to eq. (3). 149

Fig. 3-82. Plot of the results in Fig.3-66. according to eq. (3). 149

Fig. 3-83. Plot of the results in Fig.3-67. according to eq. (3). 150

Fig. 3-84. Dependence on oxygen partial pressure of the oxidative roasting rate constant calculated from the results of Fig. 3-73. 151

Fig. 3-85. Arrhenius plot of the oxidative roasting rate constant obtained from the results of Fig. 3-74. 151

Fig. 3-86. Arrhenius plot of the rate constants obtained from the results of Figs. 75-76.(E₁ is the activation energy of 53 ㎛ molybdenite particle size and E₂is the activation energy of 103 ㎛ molybdenite particle size.) 153

Fig. 3-87. EDS Images of Molybdenite Concentrate 155

Fig. 3-88. Schematic of Pb sublimation refinery. A : Sample Boat, B : Thermocouple, C : Tube Furnace, D: Gas Bomb, E : MFC, F : Temperature Controller, G : Flask, H : Washing Solution 157

Fig. 3-89. Pb content in the residue and the sublimed sample (Holding time : 30 min. air flow rate : 2 ℓ / min.) 158

Fig. 3-90. Sublimation yield of Pb and Mo vs. temperature (Holding time : 30 min. air flow rate : 2 ℓ / min.) 158

Fig. 3-91. Pb content in the residue (Holding time: 10 min. N₂ flow rate : 2 l/min.) 159

Fig. 3-92. Pb content in the residue (Temperature: 850℃ N₂ flow rate : 2 ℓ /min.) 160

Fig. 3-93. Flow chart of Pb removal from molybdenite. 162

Fig. 3-94. Leaching apparatus for cobalt concentrate. 163

Fig. 3-95. XRD pattern of cobalt concentrate. 165

Fig. 3-96. SEM image of cobalt concentrate(×2,000). 165

Fig. 3-97. EDS analysis of cobalt concentrate. 166

Fig. 3-98. EDS image of cobalt concentrate. 167

Fig. 3-99. TG, DT analysis of cobalt concentrate. 168

Fig. 3-100. XRD analysis of roasted cobalt ores. 169

Fig. 3-101. Raw and roasted cobalt ore. (a) Raw Ore, (b) 300℃, (c) 650℃, (d) 800℃ 170

Fig. 3-102. Leaching efficiency of the raw ore according with leaching time.(2M H₂SO₄ 60℃, 200 rpm, 50g/500ml) 171

Fig. 3-103. Leaching efficiency using sulfuric acid solution. (2M H₂SO₄ 60℃, 200 rpm, 50g/500ml, 2hr.) 172

Fig. 3-104. Sulfuric acid leaching efficiency of ore roasted at 300℃ with leaching time. (2M H₂SO₄ 60℃, 200 rpm, 50g/500ml, 2hr) 173

Fig. 3-105. Sulfuric acid leaching efficiency of the ore roasted at 300℃. (2M H₂SO₄ 60℃, 200 rpm, 50g/500ml, 2hr.) 174

Fig. 3-106. Leaching efficiency of the ore roasted at 300℃ with leaching time. (2M H₂SO₄, 5 vol.% H₂O₂, 60℃, 200 rpm, 50g/500ml) 175

Fig. 3-107. Leaching efficiency of the ore roasted at 300℃. (2M H₂SO₄, 5 vol.% H₂O₂, 60℃, 200 rpm, 50g/500ml, 2hr.) 175

Fig. 3-108. Leaching efficiency of the ore roasted at 300℃ with leaching time. (2M HCl, 60℃, 200 rpm, 50g/500ml) 176

Fig. 3-109. Leaching efficiency of the ore roasted at 300℃. (2M HCl, 60℃, 200 rpm, 50g/500ml, 2hr) 177

Fig. 3-110. Leaching efficiency of the ore roasted at 300℃ with leaching time. (2M HCl, 5 vol.% H₂O₂, 60℃, 200 rpm, 50g/500ml) 178

Fig. 3-111. Leaching efficiency of the ore roasted at 300℃. (2M HCl, 5 vol.% H₂O₂, 60℃, 200 rpm, 50g/500ml, 2hr.) 178

Fig. 3-112. Leaching efficiency of the ore roasted at 300℃ with leaching time. (2M HNO₃, 60℃, 200 rpm, 50g/500ml) 179

Fig. 3-113. Leaching efficiency of the ore roasted at 300℃ with leaching time. (2M HNO₃, 60℃, 200 rpm, 50g/500ml, 2hr) 180

Fig. 3-114. Leaching efficiency of the ore roasted at 300℃ with leaching time. (2M HNO₃, 5 vol.% H₂O₂, 60℃, 200 rpm, 50g/500ml) 181

Fig. 3-115. Leaching efficiency of the ore roasted at 300℃. (2M HNO₃, 5 vol.% H₂O₂, 60℃, 200 rpm, 50g/500ml, 2hr.) 181

Fig. 3-116. Sulfuric acid leaching efficiency of ore roasted at 650℃ with leaching time. (2M H₂SO₄, 60℃, 200 rpm, 50g/500ml) 182

Fig. 3-117. Sulfuric acid leaching efficiency of ore roasted at 650℃. (2M H₂SO₄, 60℃, 200 rpm, 0g/500ml, 2hr.) 183

Fig. 3-118. Leaching efficiency of the ore roasted at 650℃with leaching time. (2M H₂SO₄, 5 vol.% H₂O₂, 60℃, 200 rpm, 50g/500ml, 2hr) 184

Fig. 3-119. Leaching efficiency of the ore roasted at 650℃. (2M H₂SO₄, 5 vol.% H₂O₂, 60℃, 200 rpm, 50g/500ml, 2hr.) 184

Fig. 3-120. Leaching efficiency of the ore roasted at 300℃ with leaching time. (2M HCl, 60℃, 200 rpm, 50g/500ml) 185

Fig. 3-121. Leaching efficiency of the ore roasted at 650℃. (2M HCl, 60℃, 200 rpm, 50g/500ml, 2hr.) 186

Fig. 3-122. Leaching efficiency of the ore roasted at 650℃ with leaching time. (2M HCl, 5 vol.% H₂O₂, 60℃, 200 rpm, 50g/500ml) 187

Fig. 3-123. Leaching efficiency of the ore roasted at 650℃. (2M HCl, 5 vol.% H₂O₂, 60℃, 200 rpm, 50g/500ml, 2hr.) 187

Fig. 3-124. Leaching efficiency of the ore roasted at 800℃ with leaching time. (2M H₂SO₄, 60℃, 200 rpm, 50g/500ml) 188

Fig. 3-125. Leaching efficiency of the ore roasted at 800℃. (2M H₂SO₄, 60℃, 200 rpm, 50g/500ml, 2hr.) 189

Fig. 3-126. Leaching efficiency of the ore roasted at 300℃ using various acid solutions. 192

Fig. 3-127. Leaching efficiency of the roasted ore at 300℃ using various acid solutions mixed with H₂O₂. 193

Fig. 3-128. Leaching efficiency of the ore roasted at 650℃ using various acid solutions. 194

Fig. 3-129. Leaching efficiency of the roasted ore at 650℃ using various acid solutions mixed with H₂O₂. 194

Fig. 3-130. Leaching efficiency of the roasted ore at various temperatures using a sulfuric acid solution. 195

Fig. 3-131. Leaching efficiency of the roasted ore at various temperatures using a sulfuric acid solution mixed with H₂O₂. 196

Fig. 3-132. Leaching efficiency of the roasted ore at various temperatures using a hydrochloric acid solution. 196

Fig. 3-133. Leaching efficiency of the roasted ore at various temperatures using a hydrochloric acid solution mixed with H₂O₂. 197

Fig. 3-134. Flow diagram of experimental procedure. 198

Fig. 3-135. (a) Power supply and flow meter for Ar+H₂, (b) main chamber and (c) power controller. 199

Fig. 3-136. Schematic diagram of the plasma arc furnace. 199

Fig. 3-137. Appearance of GDMS VC 9000. 200

Fig. 3-138. Schematic diagram of the sample holder and the cell body. 200

Fig. 3-139. Vapor pressures of Mo and main impurities as a function of temperature. 201

Fig. 3-140. Relation between the temperature of several materials and the output of Ar plasma gas and Ar-10vol%H₂ plasma gas. 202

Fig. 3-141. Photograph of (a)Mo rod, (b)during HPAM and (c)melted Mo ingot. 203

Fig. 3-142. Concentration change of main impurities in the Mo metals refined by Ar+H₂ PAM as a function of added H₂ contents. 205

Fig. 3-143. Schematic of electroplating device. 206

Fig. 3-144. X-ray diffraction patterns of Al-Cu nano powder and leached powders 207

Fig. 3-145. Lattice parameter of pure Cu and Cu crystalline in leached powders 208

Fig. 3-146. Crain sizes of Cu4Al9 phase in raw nano powder, Cu₂O and Cu phases in leached powders.(이미지참조) 208

Fig. 3-147. FE-SEM micrographs of Al-Cu alloy nano powder(a), leached powders for 5 hours, (b) and leached powders for 24 hours(c). 209

Fig. 3-148. Specific surface area with leaching time. 210

Fig. 3-149. X-ray diffraction patterns of Al-Ni alloy nano powders prepared by electrical wire explosion of Ni coated Al wires. 212

Fig. 3-150. X-ray diffraction patterns of porous nano powders leached by alkali aqueous solution. 213

Fig. 3-151. Specific surface areas of porous nano powders with leaching time. 214

Fig. 3-152. The increasing ratios of specific surface areas with leaching time. 214

Fig. 3-153. TEM micrographs of Al-29.3wt%Ni alloy nano powder (a) and leached powders for 9 hours 215

Fig. 3-154. Nitrogen isotherms at 77K for leached nano powders. 215

Fig. 3-155. Pore-size distributions of leached nano powders calculated by the BJH equation in desorption branch. 216

Fig. 3-156. Experiment apparatus for preparation of fine Ni powder. 218

Fig. 3-157. Flow sheet of experiment procedure by slurry reduction methods. 219

Fig. 3-158. Flow sheet of Experiment procedure by polyol process. 219

Fig. 3-159. SEM images of Ni powder from various reaction time. (NiCl₂ ＝ 1.5 M, N₂H₄ ＝ 6 M, NaOH ＝ 4.5 M) 221

Fig. 3-160. XRD patterns of Ni powder on the variation of reaction time. (a) 30min, (b) 60min, (c) 90min 222

Fig. 3-161. XRD patterns and SEM images of Ni powder from initial concentration of precursors in solution. 223

Fig. 3-162. XRD patterns and SEM images of Ni powder from various NaOH concentration. (NiCl₂ ＝ 1.5 M, N₂H₄ ＝ 6 M) (a) NaOH ＝ 4.5 M, (b) NaOH ＝ 6.0 M 224

Fig. 3-163. SEM images and XRD pattern of Ni powder from condition. (NiCl₂ ＝ 0.1M, NH₄OH ＝ 1.2M, PVP ＝ 1.287g, PdCl₂ ＝ 5×10-5M, N₂H₄ ＝ 0.4 M)(이미지참조) 226

Fig. 3-164. PSA data of Ni powder from condition. (Condition NiCl₂ ＝ 0.1M, NH₄OH ＝ 1.2M, PVP ＝ 1.287g, PdCl₂ ＝ 5×10-5M, N₂H₄ ＝ 0.4M)(이미지참조) 226

Fig. 3-165. SEM images and XRD pattern of Ni powder from condition. (Condition NiSO₄ ＝ 0.1M, NH₄OH ＝ 1.2M, PVP ＝ 1.287g, PdCl₂ ＝ 5×10-5M, N₂H₄ ＝ 0.4M)(이미지참조) 227

Fig. 3-166. PSA data of Ni powder from condition. (NiSO₄ ＝ 0.1M, NH₄OH ＝ 1.2M, PVP ＝ 1.287g, PdCl₂ ＝ 5×10-5M, N₂H₄ ＝ 0.4M)(이미지참조) 228

Fig. 3-167. Distribution of Mineral Resources in DRC 229

I. 제목

해외 금속광물 개발을 위한 활용기술 연구

II. 연구개발의 목적 및 필요성

(1) 해외 금속광물의 개발을 위한 조사, 선광, 제련 및 원료소재화 기술개발

(2) 해외 부존 금속 광물로부터 침출, 분리, 정제 등 녹색기술 개발

(3) 5N급 몰리브덴의 초고순도 기술개발 및 순도평가 기반 구축의 필요성 대두

(4) 합금 나노분말 제조 및 입자표면 활성화 공정 개발을 통하여 고효율 촉매개발 향상 및 활용을 위한 물리화학적 처리기술 연구

III. 연구개발의 내용 및 범위

(1) 몰리브덴광, 동-코발트광의 품위향상 기술 연구

(2) 니켈광의 품위 산화배소 속도론적 연구

(4) 몰리브덴광으로부터 Pb 제거기술 개발

(5) 동-코발트광의 유가금속 침출공정 개발

(6) Mo의 플라즈마 용해정련 조건 확립 및 GDMS에 의한 극미량 불순물 분석

(7) Ni, Cu 합금 나노분말제조 및 나노분말의 선택적 침출에 의한 활성표면 극대화

(8) 1-2㎛ 크기의 Ni 분말을 합성하기 위한 최적 조건을 도출하기 위한 기초연구

IV. 연구개발결과

(1) 몰리브덴 및 동-코발트광의 품위향상을 위한 선별기술 개발

○ Mo 품위 54.5%, 회수율 92.3% 정광 회수기술 개발

○ Mo 정광 중 Pb 0.4% 이하 억제기술 개발

○ Malachite 회수를 위한 부유선별 기반기술 확립

○ 동-코발트 원광석의 특성에 따른 Malachite 회수 특성 연구

(2) 산화니켈광의 품위향상 및 활용을 위한 물리화학적 처리기술 개발

○ 건식 및 습식 자력선별을 이용한 품위향상 기술 연구

○ 산화니켈광의 고에너지 분쇄 특성 연구

○ 분쇄 산물의 물리화학적 특성 변화 및 산침출 거동 연구

(3) 몰리브덴광의 산화배소 속도론적 연구 및 품위향상 연구

○ Jander식에 의한 속도론적 데이터 분석 연구

○ Technical grade MoO₃ 제조를 위한 S 함량 5% 미만 제어기술 개발

○ Pb 함량 0.05% 이하, 제거율 99% 제어기술 개발

(4) 동-코발트광의 유가금속 추출기술 개발

○ 동-코발트광의 침출효율 분석

○ 코발트 침출율 96.3%, 동 침출율 87.9% 침출기술 개발

(5) 몰리브덴의 초고순도화 기술

○ 3N급 몰리브덴으로부터 5N급 몰리브덴 제조

○ 몰리브덴 내 대부분의 불순물을 1ppm 이하 제거기술 개발

(6) 전기선 폭발법에 의한 Ni, Cu계 합금 나노분말 제조 및 선택적 침출

○ 전기폭발법에 의해 45.5~127.3nm 크기의 구형 나노 합금분말을 제조

○ 합금 분말의 선택적 Al을 침출로 비표면적 41.3㎡/g분말 제조

○ 분말의 비표면적은 Al-29.3wt%Ni 합금이 21.7㎡/g로 가장 큼

○ 모든 합금조성에서 지름 약 3.0~3.5nm 기공 분포를 보임

(7) 슬러리환원법에 의한 미세 니켈 분말 제조

○ 슬러리 환원법을 이용한 니켈분말 제조

○ 반응시간 90분에서 0.18㎛의 구형 니켈분말을 제조 가능

○ 전구체의 농도 1.5M 이상에서 니켈 분말로 환원

○ NaOH의 농도 4.5M에서 0.18㎛의 구형 니켈분말을 제조 가능

○ NiCl₂을 사용한 polyol 공정으로 약 0.2㎛의 구형 니켈분말 제조 가능

○ NiSO₄를 사용시에는 약 0.1㎛ 이하의 구형 니켈분말 제조 가능

V. 연구개발결과의 활용계획

(1) 개발된 금속광물의 품위향상 및 활용 기술을 해외 자원개발에 적극 활용

(2) 비철금속 제련분야의 친환경 공정 개발에 활용

(3) 고순도 Mo는 Interconnect, barrier metallization 및 gate electrode 제조용 타켓으로 활용

(4) 본 연구로 얻어진 나노분말은 수소개질용, 화학 촉매로 적용 가능

(5) Ni, Co 분말은 초경공구의 점결제, 초합금, 전극재료, 전자파 차폐소재 등에 활용