표제지

목차

세부 1. 화학공정 폐촉매로부터 귀금속 회수 및 촉매용 나노 분말 제조 기술 개발 / 이만승 2

제출문 3

요약서 4

요약문 8

SUMMARY(영문요약문) 11

목차 14

제1장 서론 27

제1절 연구개발과제의 개요 27

1. 연구개발의 목적 및 필요성 27

2. 연구개발대상 기술의 차별성 29

제2절 연구개발의 국내외 현황 31

제3절 연구개발의 내용 및 범위 34

1. 연구개발의 최종목표 34

2. 연도별 연구개발 목표 및 평가방법 35

3. 연도별 추진체계 36

제2장 연구개발 수행내용 및 결과 37

제1절 연구개발 결과 및 토의 37

2.1.1. 섬유화학제조공정에서 발생한 폐촉매에 함유된 귀금속의 침출 37

2.1.2. 백금염 용액에서 백금 나노분말 제조기술 49

2.2.1. 석유화학 정제공정에서 발생한 폐촉매의 염산 침출액으로부터 용매추출과 이온교환에 의한 백금의 분리 76

2.2.2. 팔라듐염용액으로부터 나노 분말제조 99

2.3.1. Bench 규모의 침출장치에서 석유화학 정제공정에서 발생한 폐촉매의 침출 124

2.3.2. Bench 규모의 실험장치에서 나노 백금분말 제조기술 개발 147

2.4.1. 용매추출에 의한 폐촉매 침출액으로부터 백금의 회수 169

2.4.2. Bench 규모의 실험장치에서 나노 팔라듐분말 제조기술 개발 203

2.5.1. 폐촉매의 침출 및 용매추출에 의한 백금의 분리회수 241

2.5.2. 폐촉매 침출액에서 용매추출로 분리한 백금용액으로부터 촉매용 나노 백금 분말 제조 281

제2절 연구개발 결과 요약 290

제3장 목표 달성도 및 관련분야 기여도 291

제1절 연도별 연구개발목표의 달성도 291

제2절 관련분야의 기술발전 기여도(환경적 성과 포함) 292

제4장 연구개발결과의 활용계획 293

제1절 연구개발 결과의 활용계획 293

제2절 연구개발과정에서 수집한 해외 과학기술정보 295

제3절 연구개발결과의 보안등급 299

제4절 NTIS에 등록한 연구시설·장비현황 299

제5장 참고문헌 300

부록(기타 부록, 지침서, 매뉴얼, 안내서, 핸드북 등)[내용없음] 15

세부 2. 재생 귀금속 기반 나노입자 제조를 위한 바이오 융합기술 개발 / 윤영상 302

제출문 303

요약서 304

요약문 307

SUMMARY(영문요약문) 312

목차 316

제1장 서론 326

제1절 연구개발과제의 개요 326

1. 연구개발의 목적 및 필요성 326

2. 연구개발대상 기술의 차별성 333

제2절 연구개발의 국내외 현황 335

1. 해외 기술개발 동향·시장 335

2. 국내 기술개발 동향·시장 340

제3절 연구개발의 내용 및 범위 343

1. 연구개발의 최종목표 343

2. 연도별 연구개발 목표 및 평가방법 344

3. 연도별 추진체계 345

제2장 연구개발 수행내용 및 결과 346

제1절 연구개발 결과 및 토의 346

1. 금속 나노입자 합성을 위한 바이오소재의 선정 346

2. 금속 이온 환원가능 물질의 동정 및 나노입자 분리기술 개발 453

3. 나노입자의 크기/형상 제어 기술 최적화 504

4. 나노촉매, 나노필터 제조 및 성능 평가 550

제2절 연구개발 결과 요약 609

제3장 목표 달성도 및 관련분야 기여도 613

제1절 연도별 연구개발목표의 달성도 613

제2절 관련분야의 기술발전 기여도 614

제4장 연구개발결과의 활용계획 등 616

제1절 연구개발 결과의 활용계획 616

제2절 연구개발과정에서 수집한 해외 과학기술정보 616

제3절 연구개발결과의 보안등급 619

제4절 NTIS에 등록한 연구시설·장비현황 619

제5장 참고문헌 620

세부 3. 폐전지내의 백금족 희유금속 회수 및 활용 기술 개발 / 신장식 624

제출문 625

요약서 626

요약문 630

SUMMARY(영문요약문) 635

목차 638

제1장 서론 647

제1절 연구개발과제의 개요 647

1. 연구개발의 목적 및 필요성 647

2. 연구개발대상 기술의 차별성 650

제2절 연구개발의 국내외 현황 653

1. 해외 기술개발 동향 653

2. 국내 기술개발 동향 654

3. 국내외 관련 분야 기술 분석 655

제3절 연구개발의 내용 및 범위 658

1. 연구개발의 최종목표 658

2. 연도별 연구개발 목표 및 평가방법 658

3. 연도별 추진체계 659

제2장 연구개발 수행내용 및 결과 661

제1절 연구개발 결과 및 토의 661

1. 원료 물질 선정 665

2. 선택된 원료 물질 특성 분석(C사) 669

3. 침출 실험 675

4. 분리 정제 703

5. 백금 나노 분말 제조 759

6. 촉매 적용을 위한 특성 평가 805

7. 시작품 제작 873

제2절 연구개발 결과 요약 884

제3장 목표 달성도 및 관련분야 기여도 889

제1절 연도별 연구개발목표의 달성도 889

제2절 관련분야의 기술발전 기여도(환경적 성과 포함) 894

제4장 연구개발결과의 활용계획 등 895

제1절 연구개발 결과의 활용계획 895

제2절 연구개발과정에서 수집한 해외 과학기술정보 896

제3절 연구개발결과의 보안등급 901

제4절 NTIS에 등록한 연구시설·장비현황 902

제5장 참고문헌 903

부록(기타 부록, 지침서, 매뉴얼, 안내서, 핸드북 등) 905

세부 1. 화학공정 폐촉매로부터 귀금속 회수 및 촉매용 나노 분말 제조 기술 개발 15

2.1.1. 석유화학제조공정에서 발생한 폐촉매에 함유된 귀금속의 침출 15

Table 1. Chemical composition of spent catalyst 37

2.1.2. 백금염 용액에서 백금 나노분말 제조기술 15

Table 1. Materials for synthesis of nano-sized platinum particles. 50

Table 2. 레이저제타전위계 분석 조건 51

Table 3. Effect of PVP molecular weight 54

Table 4. Effect of the PVP(MW 10,000) content. 59

Table 5. Effectof the PVP(MW 40,000) content. 65

Table 6. Effect of H₂PtCl₆ content. 71

2.2.1. 석유화학 정제공정에서 발생한 폐촉매의 염산 침출액으로부터 용매추출과 이온교환에 의한 백금의 분리 15

Table 1. Chemical composition of synthetic chloride solution containing Pt(IV) 76

Table 2. Chemical structure of anion exchane and solvating extractants 76

Table 3. Properties of AG 1-X8 resin 77

Table 4. Stepwise stability constants for the formation of Pt(IV)-chloro complexes at 25℃ 78

Table 5. Equilibrium constants for the formation of ferric complexes with chloride ion at... 79

Table 6. Chemical composition of the elaching solution of spent catalysts containing Pt(IV)... 86

2.2.2. 팔라듐염용액으로부터 나노 분말제조 15

Table 1. Materials for synthesis of nano-sized palladium particles 101

Table 2. 레이저제타전위계 분석 조건 101

Table 3. Effectof PVP molecular weight 105

Table 4. Effectof the PVP(MW 40,000) content 108

Table 5. Effect of PdCl₂ content 112

Table 6. Effectof Reductant content 116

2.3.1. Bench 규모의 침출장치에서 석유화학 정제공정에서 발생한 폐촉매의 침출 16

Table 1. Chemical composition of the spent catalysts used in this study. The concentration... 124

Table 2. Standard leaching conditions employed in this study 125

Table 3. Chemical composition of the spent catalysts used in the first year 127

Table 4. Chemical formula and oxidation state of chloride in the oxidant 129

Table 5. Stoichiometric amount of each oxidant to oxidize Pt contained in the spent... 131

Table 6. Economic evaluation for the various oxidizing agent 141

Table 7. Price of the various oxidizng agent used in this study 142

2.3.2. Bench규모의 실험장치에서 나노 백금분말 제호기술 개발 16

Table 1. Effect of PVP molecular weight. 157

Table 2. Effect of the platinum precursor concentration. 160

Table 3. Effect of the PVP concentration. 162

Table 4. Effect of the platinum precursor concentration. 165

Table 5. Effect of the PVP concentration. 167

2.4.1. 용매추출에 의한 폐촉매 침출액으로부터 백금의 회수 16

Table 1. The geometric characteristics of the RPR(reciprocating plate reactor). 170

Table 2. Chemical composition of synthetic solution. 172

Table 3. Chemical analysis of the roasted and unroasted spent catalysts. 174

Table 4. Standard leaching condition. 174

Table 5. Chemical composition of the leaching solution. 174

Table 6. Mass balance of metals and HCl in the whole processing. 183

Table 7. The composition of the spent catalyst measured by XRF and ICP. 184

Table 8. Standard leaching condition of spent catalysts. 185

Table 9. The composition of the leaching liquor obtained at the optimum leaching... 185

Table 10. Stripping of Fe from the loaded Aliquat 336 by dilute HCl. 186

Table 11. Effect of HClO₄ concentration on the stripping of metals from the loaded... 187

Table 12. Mass balance of metals and HCl in the whole process. 191

Table 13. Summary of the preliminary experiments for the time required for the phase... 192

Table 14. Summary results of Fe extraction process. 193

Table 15. Summary results of Fe stripping process. 193

Table 16. Summary results of Pt extraction process. 195

Table 17. Results of Pt stripping process. 197

Table 18. Results of HCl extraction process. 197

Table 19. Results of HCl stripping process. 199

2.4.2. Bench규모의 실험장치에서 나노 팔라듐분말 제조기술 개발 17

Table 1. Effect of the palladium precursor concentration. 212

Table 2. Effect of the reaction temperature. 217

Table 3. Effect of the Stirring speed. 222

Table 4. Effect of the amount of the solvent. 226

Table 5. Effect of the Reducing agent. 228

Table 6. Effect of the CTAB concentration. 233

Table 7. Effect of the SDS concentration. 238

Table 8. The condition and results of recovery of Pt, Fe and HCl from synthetic solution... 240

2.5.1. 폐촉매의 침출 및 용매추출에 의한 백금의 분리회수 17

Table 1. Standard leaching conditions employed in this work. 243

Table 1-1. Chemical compositions of unroasted/roasted spent catalysts and leaching results. 253

Table 1-2. Chemical composition of real leaching solution obtained from 3L reaction vessel... 258

Table 2-1. Summary of commercial extractors 260

Table 2-2. Comparison of Mxer-Settler, Pulse Column and Centrifugal Contactors 261

Table 2-3. The optimum solvent extraction and stripping conditions for the separation of... 267

Table 2-4. Fe extraction process: 0.3M TBP, O/A＝1, 4 stages, Flow rate＝30ml/min 269

Table 2-5. Fe stripping process: 0.1M HCl, O/A＝1, 3 stages, Flow rate＝30ml/min 270

Table 2-6. Pt extraction process: 0.3 M Aliquat 336, O/A＝1/2, 3 stages, Flow rate＝... 272

Table 2-7. Pt stripping process: 1M HClO₄, O/A＝1, 3 stages, Flowrate＝30ml/min 273

Table 2-8. Results of washing the Pt loaded Aliquat 336 by water 274

Table 2-9. HCl extraction process: 1M TEHA, O/A＝5, 5 stages, Flow rate＝8 ml/min... 276

Table 2-10. HCl stripping process: H20, O/A＝2/5, 5stage, Flow rate＝30ml/min(for... 277

Table 2-11. Summary of the experimental reactions in the whole process 278

Table 2-12. Mass balance of metals and HCl in the whole process 279

세부 2. 재생 귀금속 기반 나노입자 제조를 위한 바이오 융합기술 개발 317

Table 1. 주요 희귀금속의 가격동향 327

Table 2. 선진국과 우리나라의 유가금속 회수 기술 개발 328

Table 3. 촉매의 물질과 기능에 따른 촉매의 분류 330

Table 4. 다양한 나노입자의 합성방법 331

Table 5. 연구실에서 보유하고 있는 바이오소재 관련 특허 기술 334

Table 6. 생물학적 방법을 통한 나노입자생산에 대한 국제특허 337

Table 7. 생물학적 나노입자 생성에 사용되는 바이오 기반 소재 339

Table 8. 금속 나노입자의 제조에 관련된 국내 특허 341

Table 9. 나노메탈시장 가격 동향 342

Table 10. 미생물 기반 원료소재 347

Table 11. Effect of medium and supplement 391

Table 12. Proton-binding model 397

Table 13. 미생물 기반 원료소재 404

Table 14. Result of TOC; HCl 409

Table 15. Result of TOC; Nitric acid 410

Table 16. The main compounds identified in hexane fraction. 467

Table 17. The main compounds identified in HPLC fraction 469

Table 18. Total phenolic content, antioxidant activity, and reducing power of different... 471

Table 19. Ag-CNT 복합체의 항균활성 테스트 결과 598

세부 3. 폐전지내의 백금족 희유금속 회수 및 활용 기술 개발 640

Table 1. The comparison of precious metals recovery technology. 651

Table 2. Waste type patents. 655

Table 3. Comparative patent relates to precious metal recovery. 656

Table 4. Comparison of dry process and wet process. 657

Table 5. Comparison of precious metals treatment. 657

Table 6. Data of EDX of used fuel cell catalyst layer. 672

Table 7. Data of EPMA of used fuel cell catalyst layer. 673

Table 8. ICP-AES Condition. 679

Table 9. The result of ICP(Inducti vely-coupled plasma) analysis after acid... 696

Table 10. The acid leaching efficiency of Cathode layer. 701

Table 11. The acid leaching efficiency of Anode layer. 702

Table 12. Recovery of platinum group metals by ion exchange resin. 720

Table 13. Data of EDX of ion exchange resin. 721

Table 14. Anion exchange resin characteristics. 726

Table 15. Adsorption isotherm parameters for correlation... 727

Table 16. Adsorption isotherm parameters for correlation... 728

Table 17. Adsorption isotherm parameters for correlation... 729

Table 18. Adsorption isotherm parameters for correlation... 730

Table 19. Adsorption isotherm parameters for correlation coefficients... 731

Table 20. Comparison of maximum adsorption capacity of adsorbent for Pt... 733

Table 21. Coefficients of pseudo-first-order, pseudo-second-order kinetic... 739

Table 22. Sorption parameter values for Pt sorption on anion-exchange... 745

Table 23. Calcination conversion of the ashes obtained after calcination at... 747

Table 24. Calcination conversion of the ashes obtained after calcination at... 748

Table 25. The dissolution of calcined adsorption of platinum onto resin in... 752

Table 26. The result of each processes. 758

Table 27. Result of Pt solution effect. 765

Table 28. Effect of Pt concentration. 766

Table 29. Conversion of Pt synthesis at different pH value. 769

Table 30. Result of reductant effect. 773

Table 31. Pt nano particle conversion at different reducing agent. 774

Table 32. Pt size at different reducing agent. 775

Table 33. Result of Surfactant effect. 779

Table 34. Pt size at different dispersing agent. 780

Table 35. ICP-AES analysis of chloroplatinic acid in aqueous solution. 787

Table 36. Properties of A cation exchange resin. 796

Table 37. Properties of B cation exchange resin. 797

Table 38. Removal of a NaCl using A, B cation exchange resin. 798

Table 39. Removal of a NaCl using B cation exchange resin. 799

Table 40. Acid treatment properties of each material. 801

Table 41. ICP results of the solution after acid treatment. 803

Table 42. ICP results of the final recovery solution. 804

Table 43. Amount of alumina coating. 814

Table 44. Component of transition metal and a platinum. 816

Table 45. Amount of transition metal and platinum coating. 817

Table 46. Change in the amount of the catalyst according GHSV(3mm... 825

Table 47. Property of Nation ® PFSA Polyme Dispersion.[이미지참조] 838

Table 48. Catalyst activity area. 862

Table 49. Catalyst activity area of acid and heat treated carbonblack content... 867

Table 50. Catalyst activity area of Pt/C catalyst for addition of 20wt.%... 868

Table 51. The result of CV and ORR test of commercial and recovery... 870

Table 52. The result of processes. 874

Table 53. The purity of platinum in aqua regia. 875

세부 1. 화학공정 폐촉매로부터 귀금속 회수 및 촉매용 나노 분말 제조 기술 개발 18

2.1.1. 석유화학제조공정에서 발생한 폐촉매에 함유된 귀금속의 침출 18

Fig. 1. Effect of HCl concentration on the leaching of metals.(Particle size... 39

Fig. 2. Effect of H₂SO₄ concentration on the leaching of metals.(Particle size... 39

Fig. 3. Effect of HNO₃ concentration on the leaching of metals.(Particle size＝... 40

Fig. 4. Effect of NaOH concentration on the leaching of metals.(Particle size＝... 40

Fig. 5. Effect of adding H₂O₂ to 30% HCl solution on the leaching of metals from... 41

Fig. 6. XRD patterns of spent catalyst after heat treatment at various... 43

Fig. 7. Effect of adding H₂O₂ to 30% HCl solution on the leaching of metals... 44

Fig. 8. Effect of adding H₂O₂ to 30% HCl solution on the leaching of metals from... 45

Fig. 9. Effect of adding H₂O₂ to 30% HCl solution on the leaching of metals from... 45

Fig. 10. Effect of adding H₂O₂ to 30% HCl solution the leaching of metals from... 46

Fig. 11. Effect of adding H₂O₂ to 30% HCl solution on the leaching of metals from... 46

Fig. 12. Variation of the leaching of metals in aqua regia from the spent catalysts... 47

Fig. 13. Effect of temperatureon the leaching percentage of metals from the... 48

2.1.2. 백금염 용액에서 백금 나노분말 제조기술 19

Fig. 1. 백금 나노 입자 합성 실험 기기도 51

Fig. 2. 반응 전·후의 시료색 변화 52

Fig. 3. UV-vis 분석 53

Fig. 4. Particle size histogram 55

Fig. 5. Particle size histogram 56

Fig. 6. Particle size histogram 57

Fig. 7. Particle size histogram 58

Fig. 8. Particle size histogram 60

Fig. 9. Particle size histogram 61

Fig. 10. Particle size histogram 62

Fig. 11. Particle size histogram 63

Fig. 12. Particle size histogram 64

Fig. 13. Particle size histogram 66

Fig. 14. Particle size histogram 67

Fig. 15. Particle size histogram 68

Fig. 16. Particle size histogram 69

Fig. 17. Particle size histogram 70

Fig. 18. Particle size histogram 72

Fig. 19. Particle size histogram 73

Fig. 20. Particle size histogram 74

2.2.1. 석유화학 정제공정에서 발생한 폐촉매의 염산 침출액으로부터 용매추출과 이온교환에 의한 백금의 분리 20

Fig. 1. Distribution of Pt(IV) containing species with HCl... 80

Fig. 2. Distributon of ferric species with HCl concentration.... 81

Fig. 3. Effect of HCl concentration on the extraction of Pt(IV), Fe(III) and Al(III)... 88

Fig. 4. Effect of HCl concentration on the extraction of Pt(IV), Fe(III) and Al(III)... 89

Fig. 5. Effect of HCl concentration on the extraction of Pt(IV), Fe(III) and AI(III)... 90

Fig. 6. Effect of HCl concentration on the extraction of Pt(IV), Fe(III) and Al(III)... 91

Fig. 7. Effect of HCl concentration on the extraction of Pt(IV), Fe(III) and Al(III)... 92

Fig. 8. Effect of HCl concentration on the extraction of Pt(IV), Fe(III) and Al(III)... 93

Fig. 9. Effect of HCl concentration on the extraction of Pt(IV), Fe(III) and AI(III)... 94

Fig. 10. The effect of concentration of AG1-x8 resin on the adsorption of... 95

Fig. 11. Eqilibrium loading of Pt(IV) from 5M HCl solution... 96

Fig. 12. Effect of diphonix concentration on the adsorption of... 97

Fig. 13. Effect of AG1-X8 concentration on the adsorption... 98

2.2.2. 팔라듐염용액으로부터 나노 분말제조 20

Fig. 1. 팔라듐 나노 입자 합성 실험 기기도(H₂ 환원시) 102

Fig. 2. 팔라듐 나노 입자 합성 실험 기기도(NaBH₄ 환원시) 103

Fig. 3. 반응 전·후의 시료색 변화 104

Fig. 4. Particle size histogram 106

Fig. 5. Particle size histogram 107

Fig. 6. Particle size histogram 109

Fig. 7. Particle size histogram 110

Fig. 8. Particle size histogram 111

Fig. 9. Particle size histogram 113

Fig. 10. Particle size histogram 114

Fig. 11. Particle size histogram 115

Fig. 12. Particle size histogram 117

Fig. 13. Particle size histogram 118

Fig. 14. Particle size histogram 119

Fig. 15. Particle size histogram 120

Fig. 16. Particle size histogram 121

Fig. 17. Particle size histogram 122

2.3.1. Bench 규모의 침출장치에서 석유화학 정제공정에서 발생한 폐촉매의 침출 21

Photo 1. Photo of experimental apparatus for 100 mL leaching experiments. 126

Photo 2. Photo of experimental apparatus for 1 and 3L leaching experiments. 127

Fig. 1. Effect of HCl concentration on the leaching of metals from unroasted spent catalyst. 128

Fig. 2. Effect of HCl concentration in the leaching of metals from roasted spent catalyst. 129

Fig. 3. Effect of addition of NaClO in leaching lixivant on the leaching of metals. 132

Fig. 4. Effect of addition of NaClO in leaching lixivant on the leaching of metals. 132

Fig. 5. Effect of addition of NaClO₃ in leaching lixivant on the leaching of metals. 133

Fig. 6. Effect of addition of NaClO₃ in leaching lixivant on the leaching of metals. 134

Fig. 7. Effect of addition of O₃ in HCl lixivant on the leaching of metals.... 135

Fig. 8. Effect of addition of O₃ in HCl lixivant on the leaching of metals.... 135

Fig. 9. Effect of addition of H₂O₂ in the leaching lixivant on the leaching of metals. 136

Fig. 10. Effect of addition of H₂O₂ in the leaching lixivant on the leaching of metals. 137

Fig. 11. Effect of addition of H₂O₂ in the leaching lixivant on the leaching of metals. 137

Fig. 12. Effect of addition of H₂O₂ in the leaching lixivant on the leaching of metals. 138

Fig. 13. Effect of addition of H₂O₂ in the leaching lixivant on the leaching of metals. 139

Fig. 14. Effect of addition of H₂O₂ in the leaching lixivant on the leaching of metals. 139

Fig. 15. Effect of addition of H₂O₂ in the leaching lixivant on the leaching of metals. 140

Fig. 16. Effect of addition of H₂O₂ in the leaching lixivant on the leaching of metals. 140

Fig. 17. Effect of reaction temperture on the leaching percentage of metals... 143

Fig. 18. Effect of pulp density on the leaching of metals by using 20% HCl+3T H₂O₂. 144

Fig. 19. Effect of stirring speed on the leaching of metals by using 20% HCl+3T H₂O₂. 144

Fig. 20. Effect of pulp density on the leaching of metals by using 20% HCl+3T H₂O₂. 145

Fig. 21. Effect of reaction temperture on the leaching percentage of metals... 146

2.3.2. Bench규모의 실험장치 에서 나노 백금분말 제조기술 개발 22

Fig. 1. Bench 규모의 나노 입자 제조 장치 149

Fig. 2. 백금 나노 입자 제조 실험 기기도(환원제 NaBH₄ 이용) 150

Fig. 3. 백금 나노 입자 제조 실험 기기도(환원제 H₂ 이용) 151

Fig. 4. 반응 전·후의 샘플색 변화 153

Fig. 5. UV-vis spectral change. 154

Fig. 6. XRD patterns of platinum nanostructures. 155

Fig. 7. TEM image and metal size distribution diagrams. 156

Fig. 8. TEM image and metal size distribution diagrams. 157

Fig. 9. TEM image and metal size distribution diagrams. 158

Fig. 10. TEM image and metal size distribution diagrams. 159

Fig. 11. TEM image and metal size distribution diagrams. 159

Fig. 12. TEM image and metal size distribution diagrams. 161

Fig. 13. TEM image and metal size distribution diagrams. 161

Fig. 14. TEM image and metal size distribution diagrams. 162

Fig. 15. TEM image and metal size distribution diagrams. 164

Fig. 16. TEM image and metal size distribution diagrams. 164

Fig. 17. TEM image. 165

Fig. 18. TEM image and metal size distribution diagrams. 166

Fig. 19. TEM image and metal size distribution diagrams. 167

2.4.1. 용매추출에 의한 폐촉매 침출액으로부터 백금의 회수 23

Fig. 1. Photo of vibration plate column. 171

Fig. 2. Photo of mixer-settler. 173

Fig. 3. Effect of TBP concentration on the extraction of metals from the real leaching solution. 176

Fig. 4. Effect of HCl concentration on the stripping of metals from 0.3M loaded TBP. 176

Fig. 5. Effect of TBP concentration on the extraction of metals from leaching... 178

Fig. 6. Effect of HCl concentration on the stripping of metals loaded 2.5M TBP. 179

Fig. 7. Effrect of Aliquat336 concentration on the extraction of metals after... 179

Fig. 8. Effect of HCIO₄concentration on the stripping of metals from 0.3M loaded Aliquat336. 180

Fig. 9. McCabe-Thiele plot for HCl extraction. [HCl]Feed solution＝5.9mol/L[이미지참조] 182

Fig. 10. McCabe-Thiele plot for stripping of HCl from loaded TEHA by water. 182

Fig. 11. General scheme for recovery of metals from the spent petroleum leaching... 183

Fig. 12. Effect of Aliquat336 concentration on the extraction of metals after... 186

Fig. 13. McCabe-Thiele plot for extration of HCl with 1.5M TEHA.(The... 188

Fig. 14. Effect of the concentration of HCl on the extraction of HCl with 1.5M TEHA. 189

Fig. 15. McCabe-Thiele plot for stripping of HCl from loaded TEHA by water. 189

Fig. 16. General scheme for recovery of metals from the spent petroleum catalyst by leaching processing followed by solvent extraction and stripping. 190

Fig. 17. McCabe-Thiele plot for Fe extraction with 0.3M TBP. 194

Fig. 18. McCabe-Thiele plot for Fe stripping from loaded 0.3M TBP with 0.1M HCl. 194

Fig. 19. McCabe-Thiele plot for Pt extraction with 0.3M Aliquat336. 196

Fig. 20. McCabe-Thiele plot for Pt stripping from loaded 0.3M Aliquat336 with HClO₄. 196

Fig. 21. McCabe-Thiele plot for HCl extration with 0.75M TEHA 198

Fig. 22. McCabe-Thiele plot for HCl extraction with 1M TEHA 198

Fig. 23. McCabe-Thiele plot for HCl stripping from 1M TEHA with water. 199

Fig. 24. a) Toluene as diluent, obtained raffinate and loaded TBP.... 200

Fig. 25. Effect of vibration frequency on the extraction of Fe from FeCl₃ solution. 201

2.4.2. Bench규모의 실험장치에서 나노 팔라듐분말 제조기술 개발 24

Fig. 1. Bench 규모의 나노 입자 제조 장치 205

Fig. 2. 팔라듐 나노 입자 제조 실험 기기도(환원제 NaBH₄ 이용) 206

Fig. 3. 팔라듐 나노 입자 제조 실험 기기도(환원제 H₂ 이용) 207

Fig. 4. TEM image. 209

Fig. 5. TEM image. 210

Fig. 6. TEM image. 211

Fig. 7. TEM image. 214

Fig. 8. TEM image. 215

Fig. 9. TEM image. 216

Fig. 10. TEM image. 219

Fig. 11. TEM image. 220

Fig. 12. TEM image. 221

Fig. 13. TEM image. 224

Fig. 14. TEM image. 225

Fig. 15. TEM image. 227

Fig. 16. TEM image. 230

Fig. 17. TEM image. 231

Fig. 18. TEM image. 232

Fig. 19. TEM image. 235

Fig. 20. TEM image. 236

Fig. 21. TEM image. 237

2.5.1. 폐촉매의 침출 및 용매추출에 의한 백금의 분리회수 25

Fig. 1. Photo of 3 L water bath leaching reactor equipment. 242

Fig. 2. Photo of the mixer-settler employed in this work. 245

Fig. 1-1. Photo of Disk Mill used in this work. 247

Fig. 1-2. Spent catalysts with 2cm depth were placed in the plate for the heat... 247

Fig. 1-3. Muffle furnace for the treatment of spent catalysts. 248

Fig. 1-4. Metal residue fallen off from the metal plate due to the high temperature. 248

Fig. 1-5. The spent catalysts were mixed evenly in the plastic bag.The catalysts shown... 249

Fig. 1-7. Photo of leaching equipment provided by Sungil HighTech. 251

Fig. 1-8. Photo of filtration equipment. 251

Fig. 1-9. 500 ml scale leaching equipment. 254

Fig. 1-10. Photo of plverizer, supplied by BICO INC. 256

Fig. 1-11. Photo of sieve shaker, Tyler RX-29-16. 256

Fig. 1-12. Muffle furnace used in roasting process, two layers of plate was placed at one... 257

Fig. 1-13. Spent catalysts before(Left picture) and after(Right picture) roasting. 257

Fig. 1-14. Photo of vacuum filter. 259

Fig. 2-1. Schematic of a horizontal mixer-sellers. 262

Fig. 2-2. Side view of one unite if the mixer-settler extractor 263

Fig. 2-3. Diagram of a packed column 264

Fig. 2-4. Pulse Column with perforate plates. 265

Fig. 2-5. Cutaway view of an operating centrifugal contactor. 266

Fig. 2-6. McCabe-Thiele plot for Fe extraction with 0.3 M TBP. 268

Fig. 2-7. Mixer-settler operation on Fe extraction process. 270

Fig. 2-8. McCabe-Thiele plot for Fe stripping from loaded 0.3 M TBP with 0.1 M HCl. 270

Fig. 2-9. McCabe-Thiele plot for Pt extraction with 0.3 M Aliquat 336. 272

Fig. 2-10. McCabe-Thiele plot for Pt stripping from loaded 0.3 M Aliquat 336 with 1 M... 273

Fig. 2-11. McCabe-Thiele plot for HCl extraction with 1 M TEHA 275

Fig. 2-12. HCl loaded THEA and TEHA after stripping. 276

Fig. 2-13. McCabe-Thiele plot for HCl stripping from 1 M TEHA with water. 277

Fig. 4-23. General scheme for recovery ofmetals from the spent petroleum catalysts by leaching processing foilwed by mixer-settler operation. 280

2.5.2. 폐촉매 침출액에서 용매추출로 분리한 백금용액으로부터 촉매용 나노 백금분말 제조 26

Fig. 3-1. Bench 규모의 나노 입자 제조 장치 283

Fig. 3-2. 백금 나노 입자 제조 실험 기기도(환원제 NaBH₄ 이용) 284

Fig. 3-3. XRD patterns of nano platinum particles obtained in this study. 287

Fig. 3-4. TEM image and metal size distribution diagrams. 288

세부 2. 재생 귀금속 기반 나노입자 제조를 위한 바이오 융합기술 개발 318

Figure 1. 금속 나노입자의 생산 위한 기술 전반에 대한 국제 특허출원 현황. 336

Figure 2. 금속 나노입자의 제조관련 SCI급 논문 게재 동향 338

Figure 3. UV-vis spectra of gold nanoparticles using Pseudomonas. 349

Figure 4. UV-vis spectra of silver nanoparticles using Pseudomonas. 350

Figure 5. UV-vis spectra of gold nanoparticles using Bacillus. 352

Figure 6. UV-vis spectra of silver nanoparticles using Bacillus. 353

Figure 7. UV-vis spectra of gold nanoparticles using Staphylococcus. 355

Figure 8. UV-vis spectra of silver nanoparticles using Staphylococcus. 356

Figure 9. TEM images of a) gold and b) silver nanoparticles using Staphylococcus. 357

Figure 10. UV-vis spectra of gold nanoparticles using Lactobacillus. 360

Figure 11. UV-vis spectra of silver nanoparticles using Lactobacillus. 361

Figure 12. TEM images of a) gold, b) silver, c) palladium, and d) platinum... 362

Figure 13. XRD of a) gold, b) palladium, and c) platinum nanoparticles. 363

Figure 14. TEM images of gold nanoparticles using a) Photonacterium sp.,... 365

Figure 15. UV-vis spectra of silver nanoparticles in the absence... 367

Figure 16. TEM images of Ag nanoparticles produced by a) active and b) inactive... 368

Figure 17. X-ray diffraction of Ag nanoparticles produced by (a) active and (b)... 369

Figure 18. Synthesis of AuNPs using 1 mM KI supplemented in marine medium 371

Figure 19. X-ray diffraction patterns of Au nanopartides 372

Figure 20. Synthesis of AuNPs using 1 mM NaBr supplemented in marine medium 374

Figure 21. Synthesis of AuNPs using 1 % Glucose supplemented in marine medium 376

Figure 22. Synthesis of AuNPs using 1 % Starch supplemented in marine medium 378

Figure 23. Synthesis of AuNPs using sulphate medium for cell growth 380

Figure 24. X-ray diffraction patterns of Au nanoparticles 381

Figure 25. Synthesis of Au nanoparticles using cellulose medium for cell growth 383

Figure 26. Synthesis of Au nanoparticles using Phosphate medium for cell growth 385

Figure 27. X-ray diffraction patterns of Au nanoparticles 386

Figure 28. Synthesis of Au nanoparticles using nitrate medium for cell growth 388

Figure 29. TEM images of Au nanoparticles using 390

Figure 30. Enzyme assay for testing synthesis of enzyme broth 393

Figure 31. 2D gel electrophoresis to observe the protein profile of Jeotgalibacillus... 394

Figure 32. Potentiometric titration of the raw biomass(C. glutamicum). 396

Figure 33. FTIR spectrum of the C. glutamicum biomass. 398

Figure 34. Picture of vessel after bioreduction using raw biomass(RB) and... 400

Figure 35. TEM images of Au nanoparticles produced by a) RB and b) PEIB 401

Figure 36. XRD images of Au nanoparticles produced by a) RB and b) PEIB 402

Figure 37. Results of ICP analysis 406

Figure 38. TEM images of platinum nanoparticles 408

Figure 39. Percentage conversion of gold nanoparticles. 412

Figure 40. 여러 가지 식물추출물을 이용하여 제조한 골드 나노입자의 UV-vis spectra 413

Figure 41. TEM images of Au nanoparticles using 동백나무. 416

Figure 42. TEM images of Au nanoparticles using 산유자나무. 417

Figure 43. TEM images of Au nanoparticles using 곰솔(해송). 418

Figure 44. TEM images of Au nanoparticles using 차나무. 419

Figure 45. TEM images of Au nanoparticles using 단풍나무. 420

Figure 46. TEM images of Au nanoparticles using 산뽕나무. 421

Figure 47. TEM images of Au nanoparticles using 쑥. 422

Figure 48. TEM images of Au nanoparticles using 삼나무. 423

Figure 49. TEM images of Au nanoparticles using 소나무. 424

Figure 50. TEM images of Au nanoparticles using 감나무. 425

Figure 51. TEM images of Au nanoparticles using 밤나무. 426

Figure 52. TEM images of Au nanoparticles using 은행나무. 427

Figure 53. TEM images of Au nanoparticles using 분버들. 428

Figure 54. TEM images of Au nanoparticles using 고로쇠나무. 429

Figure 55. TEM images of Au nanoparticles using 고추나무, 머루나무. 430

Figure 56. TEM images of Au nanoparticles using 대추나무. 431

Figure 57. TEM images of Au nanoparticles using 조록나무. 432

Figure 58. TEM images of Au nanoparticles using plant extract; spherical. 434

Figure 59. TEM images of Au nanoparticles by plant extract. 435

Figure 60. Biogenic Au nanoparticles using 산뽕나무. 436

Figure 61. Percentage conversion of a) palladium and b) platinum nanoparticles. 438

Figure 62. Biogenic Au nanoparticles using Piper betle. 440

Figure 63. XRD pattern of Au nanoparticles using Piper betle. 441

Figure 64. UV-vis spectra of Au nanoparticles using Ocimum sanctum. 442

Figure 65. Biogenic Au nanoparticles using Ocimum sanctum. 443

Figure 66. XRD pattern of Au nanoparticles using Ocimum sanctum. 444

Figure 67.(a) UV-vis spectra of gold nanoparticles formation(30 ℃) after biological... 446

Figure 68. TEM images of gold nanoparticles synthesized by the reduction of 1 mM... 447

Figure 69.(a) UV-vis spectra of gold nanoparticles formation(pH 3) after biological... 449

Figure 70. TEM images of gold nanoparticles synthesized by the reduction of 1 mM... 450

Figure 71. Lespedeza cyrtobotrya 추출물을 이용하여 제조된 Ag 나노입자. 452

Figure 72. Scheme used for the preparation of O. sanctum extracts which used... 454

Figure 73. Image of solvent fraction method. 455

Figure 74. UV-vis-NIR adsorption spectra of gold nanoparticles formation after... 457

Figure 75. TEM images of the gold nanoparticles synthesized by (a) O. sanctum... 458

Figure 76. FE-SEM images of the gold nanoparticles synthesized by(a-b) O.... 459

Figure 77. FTIR spectrum of (a) O. sanctum extract(plot a) before reaction with... 461

Figure 78. UV-vis spectra of gold nanoparticles formation after biological reduction... 463

Figure 79. TEM images of gold nanoparticles synthesized by the reduction of 1mM... 464

Figure 80. GC-MS chromatogram of hexane fraction. 466

Figure 81. GC-MS chromatogram of (a) HPLC fraction 1 and... 468

Figure 82. Relationship of antioxidant activity and reducing power... 472

Figure 83. Structure of antioxidants. 474

Figure 84. Antioxidant effect of various antioxidants against electron donating ability 475

Figure 85. FE-TEM image 477

Figure 86. FE-TEM image 478

Figure 87. X-ray diffraction patterns of Pt nanoparticles using antioxidants. 479

Figure 88. TEM image of Pt nanoparticles synthesized by chlorogenic acid. 480

Figure 89. TEM image of Pd nanoparticles synthesized using 0.086 g gallic acid... 481

Figure 90. TEM images of Ag nanowire. 483

Figure 91. TEM image of platinum nanoparticles synthesized using 1 M gallic acid... 484

Figure 92. X-ray diffraction patterns of PtNPs formation using gallic acid... 485

Figure 93. LC-MS chromatogram of(a) bachground; Gold solution,... 487

Figure 94. MS/MS chromatogram of predicted degradation pathway of ferulic acid. 488

Figure 95. Au:FA＝1:5 조건에서 제조된 Au 나노입자의 TEM image. 490

Figure 96. 다양한 Au와 ferulic add의 비율에 따라 제조된 나노입자의 GC-MS. 491

Figure 97. [EMIM]OAc 농도의 영향... 493

Figure 98. (i)(a) 1% [EMIM]OAc와(b) 50% [EMIM]OAc에 의해 정제된 나노입자의 XRD... 494

Figure 99. 다양한 [EMIM]OAc 농도에 따라 제조된 Au 나노입자의 TEM 이미지 495

Figure 100. 제조한 Au 나노입자의 FESEM과 EDAX 496

Figure 101. 다양한 농도의 sodium citrate를 이용하여 정제된 Au 나노입자의... 498

Figure 102. 다양한 농도의 sodium citrate를 아용하여 정제된 Au 나노입지의 TEM 이미지. 499

Figure 103. 다양한 농도의 SDS를 이용하여 정제된 Au 나노입자의... 501

Figure 104. 다양한 농도의 SDS를 이용하여 정제된 Au 나노입자의 TEM 이미지. 502

Figure 105. FESEM과 EDAX 분석 503

Figure 106. 다양한 온도 조건에서 생성된 Au 나노입자 용액의 색깔. 505

Figure 107. 다양한 온도 조건에서 생성된 Au 나노입자 UV-spectrum. 506

Figure 108. 다양한 온도 조건에서 생성된 Au 나노입자의 TEM 이미지. 507

Figure 109. 1 mM ferulic acid를 이용하여 제조된 Au 나노입자의 UV-NIR-vis. 510

Figure 110. 1.5 mM ferulic acid 조건에서 제조된 비등방성 나노입자의 HR-TEM... 511

Figure 111. 1.5 mM ferulic acid 조건에서 제조된 비등방성 나노입자의 AFM image. 512

Figure 112. 다양한 농도의 Au를 이용하여 제조한 나노입자의 UV-NIR-vis spectrum;... 514

Figure 113. 다양한 농도의 Au를 이용하여 제조한 나노입자의 TEM images. 515

Figure 114. 다양한 환원제의 농도에 따라 제조된 Pt 나노입자의 TEM images 517

Figure 115. 다양한 환원제의 농도에 따라 제조된 Pd 나노입자의 TEM images 518

Figure 116. 0.1 M gallic acid를 이용하여 제조된 나노입자의 XRD pattern 520

Figure 117. 0.1 M gallic acid를 이용하여 제조된 나노입자의 HR-TEM과 SAED pattern 521

Figure 118. Pt와 Pd 나노입자의 size distribution. 522

Figure 119. 다른 농도 비율 조건에서 합성된 Pt 나노입자의 TEM images. 524

Figure 120. Pt:CA＝1:1, 1:3 비율 조건에서 합성된 Pt 나노입자의 XRD pattern. 525

Figure 121. 반응 시간에 따른 Pt 나노입자로의 전환율. 527

Figure 122. 다양한 반응 시간에 따라 제조된 Pt 나노입자의 TEM 이미지. 528

Figure 123. 반응 시간에 따른 Pd 나노입자로의 전환율. 529

Figure 124. 다양한 반응시간에 따라 제조된 Pd 나노입자의 TEM 이미지. 530

Figure 125. 반응 시간에따라서 제조된 Au 나노입자의 UV-vis spectra. 532

Figure 126. 반응 시간에따른 Au 나노입자로의 전환율. 533

Figure 127. 다양한 반응시간에 따라 제조된 Au 나노입자의 TEM 이미지. 534

Figure 128. Au 나노입자의 XRD pattern. 535

Figure 129. 다양한 pH 영역에서 제조된 Au 나노입자의 TEM 이미지. 537

Figure 130. 다양한 pH 영역에서 제조된 Au 나노입자의 UV-vis spectra. 538

Figure 131. 다양한 pH 영역에서 제조된 Au 나노입자의 전환율. 539

Figure 132. Au 나노입자의 UV-vis spectra(pre-synthesis). 542

Figure 133. 다양한 counter ion과 할로겐 이온을 이용하여 제조한 Au 나노입자의 TEM... 543

Figure 134. 다양한 counter ion과 할로겐 이온을 이용하여 제조한 Au 나노입자의... 544

Figure 135. Au 나노입자의 XRD pattern. 545

Figure 136. 반응시간에 따른 Au 나노입자로의 전환율. 547

Figure 137. Bromide ions를 이용하여 제조한 Au 나노입자의 TEM 이미지. 548

Figure 138. Iodide ions를 이용하여 제조한 Au 나노입자의 TEM 이미지. 549

Figure 139. 제조한 나노입자의 Cyclic Voltammetry. 551

Figure 140. 상용 Pt 나노입자와 a, b) 합성한 Pt 나노입자의 c, d) TEM image. 552

Figure 141. 상용 Pt 나노입자와 합성한 Pt 나노입자의 CV. 553

Figure 142. UV-vis spectra of Pd NPs recorded as a function of time 555

Figure 143. XRD pattern of PdNPs using EE leaf extract 556

Figure 144. TEM images of monometallic Pd NPs at different magnifications using... 557

Figure 145. Cyclic voltammograms for Pd NPs. 558

Figure 146. UV-vis spectra of 4-nitrophenol reduction with time using Pd NPs. 559

Figure 147. Lespedeza cyrtobotrya 추출물을 이용하여 제조된 Ag 나노입자. 561

Figure 148. Ag 나노입자의 antibacterial activity 평가 562

Figure 149. Ag 나노입자의 antibacterial activity 평가 564

Figure 150. CNT에 담지된 Pt 나노입자의 TEM 이미지. 566

Figure 151. 6시간 동안 제조된 Pt 나노입자(위) CNT 첨가 후의(아래) TEM 이미지. 568

Figure 152. 12시간 동안제조된 Pt 나노입자(위) CNT 첨가 후의(아래) TEM 이미지. 569

Figure 153. 24시간 동안 제조된 Pt 나노입자(위) CNT 첨가 후의(아래) TEM 이미지. 570

Figure 154. 48시간 동안 제조된 Pt 나노입자(위) CNT 첨가 후의(아래) TEM 이미지. 571

Figure 155. 72시간 동안 제조된 Pt 나노입자(위) CNT 첨가 후의(아래) TEM 이미지. 572

Figure 156. 제조된 Pt 나노입자의 TEM images a-b), Pt-CNT TEM images c-d). 573

Figure 157. 제조된 Pt-CNT 복합체 a)와 Pt 나노입자 b)의 XRD pattern. 574

Figure 158. Pt L3 XANES 576

Figure 159. Pt-CNT 복합체 제조 방법에 따른 TEM images. 577

Figure 160. pH에 따라 제조된 Pt-CNT 복합체의 TEM images. 579

Figure 161. pH에 따라 제조된 Pt-CNT 복합체의 XRD pattern. 580

Figure 162. pH에 따라 제조된 Pt-CNT 복합체의 원심분리 후 용액의 사진. 582

Figure 163. pH 12에서 반응 후 pH 2로 낮춘 후의 Pt 나노입자 전환율. 583

Figure 164. pH 12에서 반응 후 pH 2로 낮춘 후의 Pt-CNT 복합체의 TEM images. 584

Figure 165. pH 12에서 반응 후 pH 2로 낮춘 후의 Pt-CNT 복합체의 XRD pattern. 585

Figure 166. Pt-CNT 복합체의 CV. 587

Figure 167. 다양한 pH 조건에서 제조된 Pt-CNT 복합체의 CV. 588

Figure 168. Ag-CNT 제조 방법 모식도 590

Figure 169. CNT, CNT-COOH, CNT-AO, 그리고 Ag-CNT 복합체의 IR spectrum. 592

Figure 170. Ag-CNT 복합체의 XRD pattern. 593

Figure 171. Ag-CNT 복합체의 TEM images. 594

Figure 172. Ag-CNT 복합체의 FE-SEM images 595

Figure 173. Disc method를 이용한 Ag-CNT 복합체의 항균활성 테스트. 596

Figure 174. Hole method를 이용한 Ag-CNT 복합체의 항균활성 테스트. 597

Figure 175. Ag-waste fiber(좌)와 waste fiber(우) 600

Figure 176. 수질정화(a)와 공기정화(b) 실험 모식도. 601

Figure 177. Ag-waste fiber를 이용한 수질정화 결과. 602

Figure 178. Ag-waste fiber를 이용한 공기정화 결과. 603

Figure 179. Ag-waste fiber를 이용한 Cd 흡착 결과. 604

Figure 180. PBBF(위)와 Ag-PBBF(아래) 606

Figure 181. Ag-PBBF를 이용한 수질정화 결과. 607

Figure 182. Ag-PBBF를 이용한 공기정화 결과. 608

Figure 183. 금속 나노입자의 생물합성 모식도. 618

세부 3. 폐전지내의 백금족 희유금속 회수 및 활용 기술 개발 642

Fig. 1. Structure of polymer electrolyte fuel cell stack. 649

Fig. 2. Process of preparing to platinum nano particles. 652

Fig. 3. Raw material - MEA. 662

Fig. 4. Diagram of MEA and Difference between CCM and CCG. 663

Fig. 5. Process of Platinum recovery from used Membrane Electrode... 664

Fig. 6. SEM-EDAX Analysis of MEA(A Company). 666

Fig. 7. SEM-EDAX Analysis of MEA(B Company). 667

Fig. 8. Photo of Used MEA(C Company). 668

Fig. 9. Image of SEM/EDX of used fuel cell catalyst layer(before acid leaching). 670

Fig. 10. Image of SEM/EDX of used f uel cell catalyst layer(after acid leaching). 671

Fig. 11. Image of TGA. 674

Fig. 12. Picture of membrane removing from MEA. 676

Fig. 13. Process of membrane removing from MEA. 677

Fig. 14. Leaching reactor. 678

Fig. 15. Leaching test for the different Oxidizing agent. 680

Fig. 16. Leaching test for different concentration(25%,... 681

Fig. 17. Leaching test for different concentration(0.5M, 1M,... 682

Fig. 18. Leaching test for the different Oxidizing agent... 683

Fig. 19. Leaching test for the different Temperature. 685

Fig. 20. Leaching test for the different Temperature(50-8... 686

Fig. 21. Leaching efficiency for different concentration... 688

Fig. 22. Leaching efficiency for different temperature... 689

Fig. 23. Leaching efficiency for different temperature at... 690

Fig. 24. Leaching efficiency for different stack weight ratio. 692

Fig. 25. Leaching efficiency of repetition of leaching... 693

Fig. 26. Diagram of Acid leaching reactor(3,000ml). 695

Fig. 27. The result of ICP(Inductively-coupled plasma)... 698

Fig. 28. The result of ICP(Inductively-coupled plasma)... 699

Fig. 29. The repeatablillity result of acid leaching... 700

Fig. 30. Speciation of platinum using MEDUSA program. 704

Fig. 31. Chemical precipitation of platinum for the... 707

Fig. 32. Extraction efficiency of simulated Pt solution at... 710

Fig. 33. Repeat extraction experiment. 711

Fig. 34. Extraction efficiency of Pt at different phase... 712

Fig. 35. Stripping efficiency at different HClO₄... 713

Fig. 36. Process of separation, concentration and recovery of... 715

Fig. 37. Sorption isotherm of Pt and Ru onto the ion exchange resins. 716

Fig. 38. Sorption isotherm of Pt and Ru onto the Amberjet-4400. 717

Fig. 39. Desorption of Pt-loaded Amberjet-4400... 718

Fig. 40. Image of SEM/EDX of ion exchange resin. 722

Fig. 41. XPS wide scan, C 1s and Pt 4f core-level spectra. 723

Fig. 42. Equilibrium isotherm of Pt onto simulated Pt... 727

Fig. 43. Freundlich model fitting for adsorption of... 728

Fig. 44. Equilibrium isotherm of Pt onto acid leaching Pt... 729

Fig. 45. Freundlich model fitting for adsorption of acid... 730

Fig. 46. Freundlich model and Langmuir model fitting... 731

Fig. 47. Langmuir model fitting for simulated Pt solution... 732

Fig. 48. Influence of contact time on the adsorption of... 736

Fig. 49. Pseudo-first-order kinetic polts for the... 737

Fig. 50. Pseudo-second-order kinetic polts for the... 738

Fig. 51. The configuration of Continuous adsorption process. 741

Fig. 52. Breakthrough curve of material delivery area of narrow(a) and wide(b). 742

Fig. 53. Continuous adsorption of acid leaching solution using anion-exchange resins. 744

Fig. 54. The breakthrough curve of acid leaching... 745

Fig. 55. X-ray diffraction analysis of the ashes obtained after... 749

Fig. 56. X-ray diffraction analysis of ashes calcining... 751

Fig. 57. Survey of X-ray photoelectron spectra of each... 754

Fig. 58. C 1s X-ray photoelectron spectra of each... 755

Fig. 59. Pt 4f X-ray photoelectron spectra of each... 756

Fig. 60. Final recovery rate. 757

Fig. 61. Process of Pt nano particles. 761

Fig. 62. Diagram of Pt particle synthesis process. 762

Fig. 63. The effect of Platinum... 764

Fig. 64. TEM image of Pt nano particles from different Pt... 767

Fig. 65. Photograph and TEM Image of the platinum nano particles at... 770

Fig. 66. The effect of reductant 3mM, 5mM,... 772

Fig. 67. TEM Image of platinum nano particle at different reducing agent.... 776

Fig. 68. The effect of Surfactant 2mM,... 778

Fig. 69. TEM Image of the platinum nano particle at different dispersing... 781

Fig. 70. Photograph and TEM Image of synthesis of platinum nano... 783

Fig. 71. XPS wide scan(left) and Pt 4f core-level spectra(right) for... 784

Fig. 72. Picture of manufacturing chloroplatinic acid. 786

Fig. 73. XRD analysis of manufacturing chloroplatinic acid. 788

Fig. 74. Schematic representation of the optical changes of a... 789

Fig. 75. Picture of chloroplatinic acid... 791

Fig. 76. TEM image of colloidal platinum nanoparticles. 792

Fig. 77. Picture of chloroplatinic acid... 793

Fig. 78. TEM image of colloidal platinum... 794

Fig. 79. Process for the... 802

Fig. 80. CV result of in the platinum surface at 1M sulfuric acid... 809

Fig. 81. Platinum and platinum alloy catalysts compared to the oxygen... 810

Fig. 82. PrOx reactor system. 812

Fig. 83. Alumina coating before and after(5mm, 3mm alumina ball). 815

Fig. 84. Coating process of recovered the transition metal(Cu, Ce) and... 818

Fig. 85. Power type catalyst for selective oxidation... 819

Fig. 86. Ball type catalyst for selective... 820

Fig. 87. Gas Analyzer(CO measurement... 821

Fig. 88. Gas Chromatography. 822

Fig. 89. According to the amount of GHSV on catalyst... 824

Fig. 90. Catalyst in the selective oxidation reactor. 826

Fig. 91. Evaluation of powder type catalyst. 827

Fig. 92. CO concentration compare of O2/CO ratio. 828

Fig. 93. CO concentration compare of prepared by... 829

Fig. 94. evaluation of ball type catalyst. 830

Fig. 95. Performance evaluation of Ball type(3mm)... 831

Fig. 96. Evaluation of ball type(3mm) catalyst for change... 832

Fig. 97. Recovered using a platinum Pt/C catalyst preparing process. 834

Fig. 98. Preparing of 40wt% Pt/C and ink catalyst. 836

Fig. 99. Amount of Nation by using a commercial platinum for Pt/C... 839

Fig. 100. Pt/C electrocatalyst by Pre-treatment on carbon black(Nafion 10... 840

Fig. 101. Amount of Nation by using a recovered... 841

Fig. 102. XRD result of Pt/C catalyst for using by... 843

Fig. 103. XRD result of Pt/C catalyst for using by... 844

Fig. 104. TGA result of Pt/C catalyst for acid treated... 846

Fig. 105. TGA result of Pt/C catalyst for acid treated... 847

Fig. 106. TGA result of applied to recovered platinum... 848

Fig. 107. TGA result of applied to recovered platinum... 849

Fig. 108. TEM result of catalyst applied to recovered platinum. 851

Fig. 109. TEM result of Pt/C catalyst prepared by recovered platinum(a) and... 852

Fig. 110. Changing the... 853

Fig. 111. Changing the... 854

Fig. 112. Changing the... 855

Fig. 113. Changing the... 856

Fig. 114. The picture of cyclic voltammetry device and experimental. 858

Fig. 115. Cyclic voltammogram of prepared recovered... 859

Fig. 116. Cyclic voltammogram of commercial... 860

Fig. 117. Compare of CV for commercial and recovered... 861

Fig. 118. Effect of Nafion content for a commercial... 863

Fig. 119. Effect of Nafion content for a commercial... 864

Fig. 120. Effect of adding Nafion amount after acid... 865

Fig. 121. Effect of adding Nafion amount after add and... 866

Fig. 122. Cyclic voltammogram result of commercial... 871

Fig. 123. Oxygen reduction reaction result of... 872

Fig. 124. P&ID of leaching and adsorption continuation system. 876

Fig. 125. The arrangement plan of leaching and adsorption continuation system. 877

Fig. 126. The picture of leaching and adsorption continuation system. 878

Fig. 127. The arrangement plan of platinum nano particles synthesis system. 880

Fig. 128. The picture of platinum nano particle production equipment. 881

Fig. 129. Result of TEM image for Pt/C catalyst prepared by platinum... 882

Fig. 130. XRD of compared a trial product with... 883

Fig. 131. Simulation of platinum price response to increased platinum demand... 896

Fig. 132. Forecasted platinum demand for FCVs. 896

Fig. 133. U.S. cost breakdown by fuel cell subsystem. 897

Fig. 134. Platinum supply and demand to 2020. 898

Fig. 135. Platinum demand by application 2010. 898

Fig. 136. World platinum production and annual platinum demand. 899

Fig. 137. The market forecast base on fuel cell vehicle... 900

Fig. 138. Global Fuel Cell Market Forecast. 900