표제지
초록
목차
제1장 서론 9
제1절 연구개발의 현황과 목적 9
제2절 연구개발의 범위 및 내용 12
제3절 탄탈륨 니오븀 자원 14
제2장 기술개발 내용 및 방법 17
제1절 염화반응 기초 실험 17
1. CCl₄에 의한 Ta₂O5의 염화반응(이미지참조) 18
2. 탄탈륨 광석의 염화반응 23
제2절 폐탄탈륨콘덴서로부터 Ta 회수 및 염화반응 실험 29
1. 페탄탈륨으로부터 Ta 음극의 물리적 선별 32
2. Ta 음극의 염화반응 32
제3절 염화반응 Scale-up 실험 37
1. Attrition mill type 반응기에 의한 염화반응 38
2. 고정 층 반응기를 이용한 염화반응 41
제4절 희유금속 염화물의 분리정제를 위한 공정설계 자료 연구 46
1. 기술개발 내용 48
2. 기술개발 방법 51
3. 열역학적 고찰 52
4. 분리공정 모사 61
5. 실험 62
제5절 분리 정제 실험 67
1. 분별증류에 의한 염화물의 분리정제 67
2. 용매추출에 의한 분리정제 71
제3장 결과 및 고찰 83
제1절 염화반응 기초 실험 83
1. CCl₄에 의한 Ta₂O5의 염화반응(이미지참조) 83
2. 탄탈륨 광석의 염화반응 101
제2절 폐탄탈륨콘덴서로부터 Ta 회수 및 염화반응 실험 109
제3절 염화반응 Scale-up 실험 117
1. Attrition mill type 반응기를 이용한 염화반응 117
2. 고정층 반응기를 이용한 염화반응 117
제4절 희유금속 염화물의 분리정제를 위한 공정설계 자료 연구 130
1. SiCl₄ 혼합계의 등온 기-액 평형 130
2. SiCl₄ 혼합계의 광잉몰부피와 점도편차 131
3. 탄탈륨 염화물(TaCl5)의 용해도 측정 142
4. Ti-butoxide 혼합계의 이성분 및 삼성분계 과잉물부피 144
5. SiCl₄ 혼합계 분리공정모사 155
6. TaCl5 혼합계 분리공정모사(이미지참조) 158
제5절 분리 정제 실험 170
1. 분별증류에 의한 염화물의 분리정제 170
2. 용매추출에 의한 분리정제 172
제4장 결론 177
참고문헌 185
부록 I. PLC Ladder program for distillation and chlorination 189
Table 1-1-1. Composition of tantalum - niobium containing minerals 15
Table 1-1-2. Niobium-tantalum minerals resources 16
Table 2-2-1. Chemical analysis of Ta anode 33
Table 2-3-1. Chemical composition of 2nd tantalum ore 38
Table 2-3-2. Particle size of the tantalum ore with milling time. 42
Table 2-4-1. The basic properties of TiCl₄, FeCl₂, TaCl5 and NbCl5(이미지참조) 62
Table 2-5-1. Physical properties of metal chlorides 67
Table 2-5-2. Spec. of the distillation columns 68
Table 2-5-3. Chemical composition of hydroxide 72
Table 2-5-4. Some properties of MIBK, TBP and 2-octanol. 75
Table 3-1-1. Initial reaction rate constants at various partial pressure of CCl₄ 102
Table 3-1-2. Initial reaction rate constants at various reaction temperature 102
Table 3-3-1. Chemical composition of the residue after chlorination with attrition mill type reactor 117
Table 3-3-2. Chemical compositions of initial product gas from fixed bed 119
Table 3-3-3. Chemical compositions of partially chlorinated ore at the variable position in the reactor 119
Table 3-3-4. Gibbs free energy change and equilibrium constant of chlorination 120
Table 3-3-5. Chemical composition of the residue after chlorination 127
Table 3-4-1. Experimental VLE data and gE model parameters of the SiCl₄(1)+benzene(2) system at 323.15K(이미지참조) 132
Table 3-4-2. Experimental VLE data and gE model parameters of the SiCl₄(1)+toluene(2) system at 323.15K(이미지참조) 133
Table 3-4-3. Experimental densities, excess molar volumes, viscosities and viscosity deviations of the SiCl₄(1)+benzene(2), SiCl₄(1)+toluene(2), SiCl₄(1)+ o-xylene(2) and SiCl₄(1)+SiCH₃Cl₃(2) at 298.15K 136
Table 3-4-4. Fitted Redlich-Kister parameters with standard deviations for VE and Δη of binary systems of SiCl₄(1)+benzene(2) and SiCl₄(1)+toluene(2), SiCl₄(1)+ o-xylene(2) and SiCl4(1)+SiCH₃Cl₃(2) at 298.15K 141
Table 3-4-5. Partial excess molar volumes at infinite dilution for the systems of SiCl₄(1)+benzene(2), SiCl₄(1)+toluene(2), SiCl4(1)+ o-xylene(2) and SiCl₄(1)+ SiCH₃Cl₃(2) at 298.15K 141
Table 3-4-6. The result of TaCl5 solubility according to different solvents 143
Table 3-4-7. Experimental densities and excess molar volumes for the Ti-butoxide(1)+ethanol(2), Ti-butoxide(1) +1-propanol(2), Ti-butoxide(1) +1-butanol(2), ethanol(1)+1-propanol(2), 1-propanol+1-butanol(2) and ethanol(1)+ 1-propanol(2) at 298.15K 146
Table 3-4-8. Fitted Redlich-Kister parameters with standard deviations for VE of binary systems of Ti-butoxide(1)+ethanol(2), Ti-butoxide(1)+1-propanol(2)Ti-butoxide(1)+1-butanol(2),ethanol(1)+1-propanol(2),1-propanol(1) + 1-butanol(2) and ethanol(1)+1-butanol(2) at 298.15 K 152
Table 3-4-9. Summary for the simulation results of the separation process for the SiCl₄+Benzene, SiCl₄+Toluene mixture 157
Table 3-4-10. The basic properties of TiCl₄, FeCl₂, TaCl5 and NbCl5(이미지참조) 159
Table 3-4-11. Feedstock information 161
Table 3-4-12. Input conditions for simulation 162
Table 3-4-13. Heat and material balance for direct sequence 166
Table 3-4-14. Heat and material balance for indirect sequence 167
Table 3-4-15. Process simulation results summary for direct sequence and indirect sequence 168
Table 3-5-1. Feed stock compositions are as 170
Table 3-5-2. Calculation of numbers. of stage using methanol/water binary system 170
Table 3-5-3. Yields of solvent extraction process 176
Table 3-5-4. Chemical analysis of final product 176
Fig. 1-1-1. Processing of niobium and tantalum resources 11
Fig. 2-1-1. Flow sheet of the total process. 19
Fig. 2-1-2. Flow sheet of process suggested. 20
Fig. 2-1-3. Schematic diagram of the experimental apparatus. 22
Fig. 2-1-4. XRD peaks of raw ore 25
Fig. 2-1-5. Schematic diagram of experimental apparatus for chlorination kinetics 29
Fig. 2-2-1 Photograph and Schematic Diagram of chip type tantalum condenser 31
Fig. 2-2-2. Schematic diagram of the process for separation of Ta anode from obsolete condenser 35
Fig. 2-3-1. Schematic diagram of attrition mill type reactor 40
Fig. 2-3-2. Schematic diagram of fixed bed reactor 45
Fig. 2-4-1. Schematic diagram of the HSGC system. 64
Fig. 2-4-2. Schematic diagram of the digital vibrating tube densimeter. ① computer ② printer cable ③ compatible printer ④ cable for PC ⑤ control unit 65
Fig. 2-4-3. Schematic connection diagram of viscometer. 65
Fig. 2-4-4. Ebulliometer and pressure cell for the determination of solubility. 66
Fig. 2-4-5. Glass triple jacket for the determination of solubility. 66
Fig. 2-5-1. The picture of control system of the distillation column and the chlorinator 69
Fig. 2-5-2. Behavior of tantalum and niobium fluoride in aqueous solution 73
Fig. 2-5-3. Collective extraction 76
Fig. 2-5-4. Selective extraction 76
Fig. 2-5-5. Schematic diagram of solvent extraction apparatus. 77
Fig. 2-5-6. Predominant presence fields of NbOF5 -² and NbF6 complexes in a Nb₂O5-HF-H₂O system(이미지참조) 81
Fig. 2-5-7. Flow sheet of solvent extraction 82
Fig. 3-1-1. Mass of sample-time curves measured from TGA experiments under the partial pressure of carbon tetrachloride gas of 36.5 kPa and the reaction temperature of 773 °K. 85
Fig. 3-1-2. Conversion-time curves of tantalum pentoxide calculated from the results in Fig. 3-1-1. 86
Fig. 3-1-3. Mass of sample-time curves measured from TGA experiments at the reaction temperature of 773 °K 88
Fig. 3-1-4 Conversion-time curves of tantalum pentoxide calculated from the results in Fig. 3-1-3 89
Fig. 3-1-5. Mass of sample-time curves measured from TGA experiments at the partial pressure of carbon tetrachloride gas of 49.6 kPa. 90
Fig. 3-1-6. Conversion-time curves of tantalum pentoxide calculated from the results in Fig. 3-1-5. 91
Fig. 3-1-7. Schematic representation of a Ta₂O5 particle.(이미지참조) 92
Fig. 3-1-8. Plot of the results in Fig. 3-1-4 according to Eqn. (3-1-3) 97
Fig. 3-1-9. Plot of the results in Fig. 3-1-6 according to Eqn. (3-1-3). 98
Fig. 3-1-10. Dependence of the reaction rate on carbon tetrachloride partial pressure from the results of Fig. 3-1-4. 99
Fig. 3-1-11. Arrhenius plot of the rate constants. 100
Fig. 3-1-1. XRD Peaks of Chlorinated Samples(PCCl4=0.5, Temp.=550℃, Reaction time:100min.) (a)-20 +25#, (b)-25 +35#, (c)-35 +50#, (d)-50 +70#, (e)-70#, C : Manganese chloride hydrate(MnCl₂ 2H₂O), N : Manganocolumbite (MnNb2O6), T : Tantalum Oxide(TaO₂)(이미지참조) 104
Fig. 3-1-2. Particle size effect on chlorination with CCl₄ at reaction temp.=550℃, CCl₄ partial pressure=0.5atm. 105
Fig. 3-1-3. CCl4 partial pressure effect on chlorination with CCl₄ at reaction temp.=550℃, particle size=-70#. 106
Fig. 3-1-4. Reaction temp. effect on chlorination with CCl₄ at CCl₄ partial pressure=0.5atm., particle size=-70#. 107
Fig. 3-1-5. Arrhenius plot of the rate constants for chlorination of tantalite ore with CCl₄, ( E = 10.527 Kcal/mole ) 108
Fig. 3-2-1. TGA curves of chlorination between non-oxidized Ta anode and Cl₂(Pcl2=0.5) at various temperature(이미지참조) 111
Fig. 3-2-2. TGA curves of chlorination between CCl₄ and oxidized and non-oxidized Ta anode at Temp.=500℃ and PCCl4=0.5(이미지참조) 112
Fig. 3-2-3. XRD peaks of Ta anode with time of oxidation at 850 ℃ under atmosphere. A : metallic Ta, M : manganese tantalate, O : tantalum pentoxide, T : manganese tapiolite 113
Fig. 3-2-4. TGA curves for the effect of reaction temperature on chlorination of oxidized Ta anode with CCl₄ at Pccl4=0.5.(이미지참조) 114
Fig. 3-2-5. 1-(1-X)1/3 vs. Time curves for chlorination of oxidized Ta anode with CCl₄ at Pccl4=0.5.(이미지참조) 115
Fig. 3-2-6. Arrhenius plot of the reaction rate constants for the oxidized Ta anode 116
Fig. 3-3-1. CCl4 flow rate : 1.8g/min. Reaction temp.:500℃, Particle size : -14# ~ +20# 118
Fig. 3-3-2. The effect of particle size on the Ta concentration in the product gas, reaction condition = CCl₄ flow rate : 1.8g/min. Reaction temp.:500℃ 123
Fig. 3-3-3. The effect of particle size on the Ta/Nb ratio in the product gas, reaction condition = CCl₄ flow rate : 1.8g/min. Reaction temp.:500℃ 124
Fig. 3-3-4. The effect of particle size on CCl₄ consumption, reaction condition = CCl₄ flow rate : 1.8g/min. Reaction temp.:500℃ 125
Fig. 3-3-5. The effect of CCl₄ flow rate on the Ta/Nb ratio in the product gas, particle size : 0.2㎛, reaction temp. : 500℃ 126
Fig. 3-4-1. Isothermal VLE for the binary system of SiCl₄(1)+benzene(2) at 323.15K. 134
Fig. 3-4-2. Isothermal VLE for the binary system of SiCl₄(1)+toluene(2) at 323.15K. 134
Fig. 3-4-3. Excess molar volumes for the binary systems of SiCl₄(1)+benzene(2) and SiCl₄(1)+toluene(2) at 298.15K. 138
Fig. 3-4-4. Excess molar volumes for the binary systems of SiCl₄(1)+ o-xylene(2) and SiCl₄(1)+SiCH₃Cl₃(2) at 298.15K. 139
Fig. 3-4-5. Viscosity deviations for the binary systems of SiCl₄(1)+benzene(2), SiCl₄(1)+toluene(2), SiCl₄(1)+ o-xylene(2) and SiCl₄(1)+SiCH₃Cl₃(2) system at 298.15K. 140
Fig. 3-4-6. Excess molar volumes for the binary systems of Ti-butoxide(1)+ethanol(2) at 298.15K. 148
Fig. 3-4-7. Excess molar volumes for the binary systems of Ti-butoxide(1)+1-propanol(2) at 298.15K. 149
Fig. 3-4-8. Excess molar volumes for the binary systems of Ti-butoxide(1)+1-butanol(2) at 298.15K. 149
Fig. 3-4-9. Excess molar volumes for the binary systems of ethanol(1)+1-propanol(2) at 298.15K. 150
Fig. 3-4-10. Excess molar volumes for the binary systems of 1-propanol+1-butanol(2) at 298.15K. 150
Fig. 3-4-11. Excess molar volumes for the binary systems of ethanol(1)+ 1-butanol(2) at 298.15K. 151
Fig. 3-4-12. Calculated VE for the ternary system of Ti-butoxide+ethanol+1-propanol at 298.15 K. 153
Fig. 3-4-13. Calculated VE for the ternary system of Ti-butoxide+ethanol+1-butanol at 298.15 K. 153
Fig. 3-4-14. Calculated VE for the ternary system of Ti-butoxide+1-propanol+1-butanol at 298.15 K. 154
Fig. 3-4-15. Schematic diagram of separation process for SiCl₄ + benzene system with n-heptane as a solvent 155
Fig. 3-4-16. Schematic diagram of separation process for SiCl₄ + benzene system with n-hexadecane as a solvent 156
Fig. 3-4-17. Schematic diagram of separation process for SiCl₄ + toluene system 157
Fig. 3-4-18. A Schematic Diagram for a Direct Sequence(a) and for a indirect Sequence (b) 160
Fig. 3-4-19(a) Flow sheet for direct sequence using Aspen Plus13.1 163
Fig. 3-4-19(b) Flow sheet for indirect sequence using Aspen Plus13.1 163
Fig. 3-4-20. Plot of liquid mole fraction of each component vs. stage nNumber for direct sequence. 169
Fig. 3-4-21. Plot of liquid mole fraction of each component vs. stage number for indirect sequence. 169
Fig. 3-5-1. The effect of time on extraction yield of MIBK 173
Fig. 3-5-2. The effect of acid amount on Nb distribution coefficient 175
Fig. 4-1-1. Proposed flow sheet of production of tantalum and niobium 184
Photo. 2-1-1. Microphotograph of hornblende in the raw ore 24
Photo. 2-1-2. SEM Image and EDX Analysis 26
Photo. 2-1-3. Experimental apparatus for chlorination kinetics with CCl₄ 28
Photo. 2-2-1. Photograph of stamp mill 34
Photo. 2-2-2. Photograph of air classifier 34
Photo. 2-2-3. Phograph of the products produced by the step of Fig.2-2-2 36
Photo. 2-3-1. Phograph of attrition mill type reactor 40
Photo. 2-3-2. Photograph of continuous milling system 43
Photo. 2-3-3. Pellet of the tantalum ore 43
Photo. 2-3-3. Photograph of fixed bed reactor system 44
Photo. 2-5-1. Photograph of distillation system 70
Photo. 2-5-2. Chloride prepared from fixed bed chlorination 71
Photo. 2-5-3. Photograph of hydroxide 72
Photo. 2-5-2. Photograph of extraction column 78
Photo. 3-1-1. SEM Images of the Residue after Chlorination 103
Photo. 3-3-1. Photograph of chlorination reactor and residue after chlorination 129
Photo. 3-5-1. Picture of solid state chlorides at 250℃ 171
Photo. 3-5-1. Photograph of final product (Ta₂O5)(이미지참조) 174