초록 ▼

최종목표
▪ 저품위 황동광 고효율 침출 기술 개발 (침출률 > 85 %)
▪ 저품위 복합동광(산화광/Cu₂S)으로부터 산/환원 침출 및동/유가금속 회수 조건 확립
(침출률 > 80%, 동/유가금속 회수율 ≥ 97/80 %)
▪ 건식염화법을 이용한 저품위 동광의 고품위화 공정기술 개발
(황동광 내 철 제거율 ≥ 79 %)

개발내용 및 결과
▪ 제이염화철-염산 및 과산화수소-황산 시스템에서 황동광침출 특성 평가 및 우수 침출률 확보
: 침출률 ≥ 87%(염산+Fe

최종목표
▪ 저품위 황동광 고효율 침출 기술 개발 (침출률 > 85 %)
▪ 저품위 복합동광(산화광/Cu₂S)으로부터 산/환원 침출 및동/유가금속 회수 조건 확립
(침출률 > 80%, 동/유가금속 회수율 ≥ 97/80 %)
▪ 건식염화법을 이용한 저품위 동광의 고품위화 공정기술 개발
(황동광 내 철 제거율 ≥ 79 %)

개발내용 및 결과
▪ 제이염화철-염산 및 과산화수소-황산 시스템에서 황동광침출 특성 평가 및 우수 침출률 확보
: 침출률 ≥ 87%(염산+FeCl₃)/침출률 ≥ 91%(황산+H₂O₂)
▪ 황동광 가압 침출 조건 확립
: 침출률 92% 이상 (220℃)
▪ 전해생성 과황산 및 염소 활용 황동광 침출 특성 평가 및 최적 조건 확립
: 침출률 ≥ 85%(과황산)/침출률 ≥ 98%(염소)
▪ 저품위 동광 침출 거동 평가 및 최적 조건 확립
: 침출률 97% 이상 (3M H₂SO₄, 80℃)
▪ LIX984N을 이용하여 Cu 추출율 99% 이상 달성(15v/v%,향류 3단:모의침출용액, 30v/v%, 향류 3단:고온가압침출용액, 5v/v% 저품위 동광(1.5% Cu)침출용액)
▪ 황화동광의 선택염화반응 메커니즘 규명 및 고품위 chalcocite 제조 : 황화동광의 탈철률 98.0 – 99.8 %
▪ 염화철과 산화동광의 염화반응에 의한 염화구리 및 산화철생성 메커니즘 규명 : 산화동광의 염화율: 92.0 – 99.0 %

기대효과
▪ 저품위 황동광의 습식 제련 기술 확립은 고품위 광석의 고갈에 따른 구리 함유 광석의 저품위화 가속화에 현상에 대한 선제적 대응할 수 방안 확립 및 국내 구리 제련산업의 지속 가능 성장 기반을 마련하는데 기여할 수 있을 것으로 판단됨

적용분야
▪ 저품위 복합광 개발시 기반기술 적용 가능
▪ 황동광의 습식공정 기반기술 확보 및 습득된 단위 기술을 활용한 전략금속 제련기술 개발에 활용 가능

Abstract ▼

Ⅳ. Results
1. Leaching of copper ore at ambient pressure

◦ Hydrochloric acid leaching
- Hydrochloric acid leaching of chalcopyrite using FeCl₃ showed 83% of leaching efficiency of copper at the condition of 0.1M hydrochloric acid, 0.25M FeCl₃, leachng temperature o

Ⅳ. Results
1. Leaching of copper ore at ambient pressure

◦ Hydrochloric acid leaching
- Hydrochloric acid leaching of chalcopyrite using FeCl₃ showed 83% of leaching efficiency of copper at the condition of 0.1M hydrochloric acid, 0.25M FeCl₃, leachng temperature of 90℃, pulp density of 1%(w/v) and leaching time of 6hrs, where leaching reaction is controlled by ash layer diffusion.
- Upon the ultrasonic irradiation, increased leaching efficiency of 87% was obtained, where leaching reaction is controlled by chemical reaction.

◦ Sulfuric acid leaching
- Sulfuric acid leaching of chalcopyrite using H₂O₂ is much dependent on the stability of H₂O₂.
- Decomposition of H₂O₂ in sulfuric acid is markedly suppressed by the addition of ethylene glycol.
- At the condition of 1M H₂O₂, 2M sulfuric acid, 10mL/L ethylene glycol, leaching temperature of 60℃and leaching time of 240min, 95% of leaching efficiency of copper was obtained.

◦ Pressure leaching of copper ore
- Leaching condition : H₂SO₄ conc. 5 g/L, oxygen pressure 7 bar, solution 1 liter, pulp density 10%, temperature 230℃, time 1 hour, agitation speed 500rpm
- Cu leaching efficiency 100%, iron conc. in leaching solution 0.18g/L, pH of leaching solution 0.70
- Behaviour of residue
· main minerals : hematite와 SiO₂ / particle size : - 30㎛ hematite, + 30㎛ SiO₂
· filtration of residue : very good

◦ Leaching of copper ore by use of electrogenerated Cl₂
- Upon leaching of chalcopyrite in NaCl(0.5 ~ 2M) and Sulfuric acid(0.5 ~ 6M) solutions at pulp density of 15(w/v) and temperature of 25℃ by use of electrogenerated Cl₂ as an oxidant, very high leaching efficiency of 98% for copper is obtained
- Leaching yield of copper is much affected by the supply rate of Cl₂, however, is not dependent on the concentration of sodium chloride or sulfuric acid and the temperate of leaching solution.

◦ Leaching of copper ore by use of electrogenerated S₂O₈^2-
- Upon leaching of chalcopyrite in sulfuric acid solution by use of S₂O₈^2- as an oxidant, leaching yield of shows the value of more than 50%. The addition of Clions in to leaching solution increases the leaching efficiency, which is due to the suppression in passivation by sulfur of by-product and higher leaching efficiency than 90% for copper is obtained upon leaching of chalcopyrite in hydrochloric acid solution by use of S₂O₈^2-
- S₂O₈^2- is effectively generated in the solution of 0.3M Na₂SO₄ and 2.7M (NH₄)₂SO₄ by the apply of current(500mA/cm²) and leaching efficiencies of 70% and 85% for copper are observed in the absence and presence of Cl- ions, respectively upon leaching of chalcopyrite in sulfuric acid solution by use of electrogenerated S₂O₈^2-

2. Separation and extraction of copper from chalcopyrite leachant

◦ Cu, Fe Separately cementation from copper ore simulated leachant
- Fe²⁺and Cu²⁺ are co-precipitated in pH 2.5∼4.0 and Fe³⁺ is previously precipitated in pH 2.0∼2.5
- When C₂H₂O₄ is put into the leachant, Cu is precipitated as CuC₂O₄ (Efficiency of precipitation: Cu 99%, Fe 5%)
- When NaBH₄ is put into the leachant, Cu is precipitated as Cu and Cu₂O.

◦ Solvent Extraction of Cu from copper ore simulated leachant
- By using 20v/v% LIX 984N as extractant, initial feed pH 1.5, O/A ratio 2, 2 stage counter current extraction: Cu 99.8%, Fe 0.6% as extraction efficiency 3 stage counter current extraction: Cu 99.3%, Fe 0.6% as extraction efficiency

◦ Separation of Cu, Fe from high temperature – pressure chalcopyrite ore leachant
- When NaBH₄ and C₂H₂O₄ are put into the leachant, Cu is precipitated above 99%.
- By using 30v/v% LIX 984N as extractant, Cu is extracted above 99.3% and other metals are extracted below 0.2%.

3. Leaching and separation/extraction of copper from complex copper ore

◦ Leaching of complex copper ore
- Preparation of 1.5% Cu sample for leaching test by liberation.
- Leaching tests with H₂SO₄ concentration and temperature(optimum condition: 3M H₂SO₄, 80℃, Leaching efficiency of Cu: 97%)

◦ Separation and extraction of Cu from complex copper ore
- Solvent extraction test with LIX 984N concentration (Initial feed pH 1.5, O/A ratio
1): Extraction efficiency of Cu 98%
- Above 20 v/v% LIX 984N, Fe is co-extracted about 2∼3%. Therefore multi stage count-current solvent extraction is carried out below 15 v/v% LIX 984N.
- 2 stage count-current solvent extraction by 10, 15 v/v% LIX 984N has problem(emulsion occurrence)
- 2 stage count-current solvent extraction by 5 v/v% LIX 984N: Extraction efficiency of Cu 98%, Fe 1.7ppm

4. Production of high-grade chalcocite from low-grade Cu-sulfide ore

◦ Thermodynamic analysis using chemical potential diagrams of Cu-S-Cl and Fe-S-Cl systems at 1100 K was conducted. The results showed that high-grade chalcocite can be obtained through the selective removal of iron from low-grade Cu-sulfide ore when cuprous chloride is used as a chlorinating agent. In addition, the feasibility of the selective chlorination process was demonstrated by the experiments.

◦ When Cu-sulfide ore was reacted with cuprous chloride at 800 – 1100 K for 5 h in the presence or absence of sulfur under an Ar gas atmosphere, the concentration of iron in Cu-sulfide ore was decreased from 23.6 – 31.5 % to below 0.37 % and the concentration of copper was increased from 34.6 – 39.8 % to 58.7 – 78.3 %, and high-grade chalcocite was produced.

◦ Iron removal ratio by the selective chlorination process using CuCl for Cu-sulfide ore was 98.0 – 99.8 %

◦ Thermodynamic analysis using chemical potential diagrams of Cu-O-Cl and Fe-O-Cl systems at 1100 K and vapor pressure diagram of some selected chlorides and oxides at the elevated temperatures was conducted. The results showed that iron oxide and cuprous chloride can be obtained through the chlorine recovery process by reacting ferrous chloride and Cu-oxide ore. In addition, the feasibility of the chlorine recovery process was demonstrated by the experiments.

◦ When Cu-oxide ore was reacted with ferrous chloride at 1000 – 1100 K for 1 – 9 h under an Ar gas atmosphere, the concentration of copper in Cu-oxide ore was decreased from 6.03 – 7.70 % to 0.06 – 0.53 % and the concentration of iron was increased from 1.55 – 2.20 % to 5.10 – 35.9 %, and cuprous chloride and iron oxide were obtained after the chlorine recovery process

◦ Chlorination ratio of the Cu-oxide ore by the chlorine recovery process using ferrous chloride was 92.0 – 99.0 %

목차 Contents

• 표지 ... 1제 출 문 ... 2최종보고서 요약서 ... 4요 약 문 ... 6SUMMARY ... 11목차 ... 18제 1 장 연구개발 과제의 개요 ... 20 제 1 절 연구개발의 목적 및 필요성 ... 20 1. 연구개발의 필요성 ... 20 2. 연구개발의 목적 ... 21 제 2 절 연구개발 범위 ... 23제 2 장 국내외 기술개발 현황 ... 24 제 1 절 황동광의 습식침출 ... 24 1. 상압침출 ... 24 2. 가압침출 ... 29 제 2 절 황동광 침출액의 분리정제 ... 33 1. 황동광 분리정제 ... 33 제 3 절 염화법에 의한 저품위 동광의 고품위화 공정개발 ... 38 1. 건식 동제련법의 개요 및 현황 ... 38 2. 건식 동제련법의 연구개발 현황 ... 40제 3 장 연구개발 수행내용 및 결과 ... 43 제 1 절 황동광의 습식침출 ... 43 1. 상압침출 ... 43 2. 가압침출 ... 58 3. 전해침출 ... 64 제 2 절 황동광 침출액의 분리정제 ... 73 1. 동광 모의 침출용액으로부터 동 및 유가금속 회수 ... 73 2. 황동광 고온가압 침출용액으로부터 동 및 유가금속 회수 ... 100 제 3 절 복합동광 습식 침출 및 분리정제 ... 116 1. 복합 동광 습식 침출 ... 116 2. 복합 동광 분리 정제 ... 121 3. 결론 ... 125 제 4 절 저품위 동광의 고품위화 공정개발 ... 125 1. 선택염화법과 염소회수법을 이용한 동광의 고품위화 공정 개요 ... 125 2. 황화동광의 선택염화법을 위한 열역학적 분석 ... 126 3. 황화동광의 선택염화법 실험 방법 ... 128 4. 황화동광의 선택염화법 실험결과 및 고찰 ... 130 5. 염화철로부터 염소회수를 위한 염소회수법의 열역학적 분석 ... 142 6. 염화철로부터 염소회수를 위한 염소회수법의 실험 방법 ... 144 7. 염화철로부터 염소회수를 위한 실험결과 및 고찰 ... 148 8. 결론 ... 153제 4 장 목표달성도 및 관련분야에의 기여도 ... 155 제 1 절 연구개발 목표 달성도 ... 155 제 2 절 대외(기술발전) 기여도 ... 156제 5 장 연구개발 결과의 활용계획 ... 158제 6 장 참고문헌 ... 160끝페이지 ... 165