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Introduction to Hydrometallurgy Material Sources for Hydrometallurgical Processing
INTRODUCTION
Terms
Mineral Ore deposits
Meaning
A naturally occurring compound A naturally occurring aggregate of minerals from which one or more metals or minerals may be extracted economically Useful minerals obtained when the ore deposits are exploited Waste products
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SECTION
TOPIC CONTENTS
Mineral Reserves and Resources Principle and uses of Hydrometallurgy and Electrometallurgy
1.1 1.2
1.3 1.4
1.5
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Hydrometallurgy vs Pyrometallurgy
Reclamation and Recycling, Advantages and Importance of Hydrometallurgical Processing Advancement in Hydrometallurgy / Electrometallurgy
EBS 315 Chapt 1 Slides 1-55
INTRODUCTION
Extractive Metallurgy deals the extraction and refining of metals It is also discipline in Engineering Some of the principles of extractive metallurgy that governs the extraction and refining processes were based on the scientific basis of the subject using principles of physical chemistry The outcome from this is the development of the subject known as Chemical Metallurgy - which deals with the chemical fundamentals of metallurgy
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INTRODUCTION
In Extractive Metallurgy, heat and mass transfer, momentum as well as mathematical techniques constitute the engineering fundamentals & the application of these has led to the development of the subject termed as Process Engineering Metallurgy Physical chemists, chemical and other Engineers have played significant roles besides the Metallurgist Extractive Metallurgy is multi-disciplinary in nature
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K
Mg Ti Mn Zr V
2.6
2.1 0.44 0.10 0.017 0.014
EBS 315 Chapt 1 Slides 1-55
Be
Mo Sn Hg Ag Pt Au
0.001
0.0001 0.0001 0.00001 0.000001 0.0000001 0.0000001
11
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Al
Li Si Fe
0.16-1.9
0.1 0.02-0.04 0.002-0.02
Sn
Ni Au
0.003
0.0001 0.000005
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Mg Al
1.66 2.86
Ti
V Mn Fe Co
0.66
0.05 23.86 13.80 0.35
9.9
0.8 358 207 5.2
4000 4 5000
Ni
Cu Zn Zr Mo Ag
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0.98
0.52 0.46 0.06 0.05 0.0001 0.09
14.7
7.9 0.7 0.93 0.77 0.001
EBS 315 Chapt 1 1.3 Slides 1-55
1500
150 10 1000 60 1 50
13
The availability of metals for use is not only governed by its abundance alone As shown in Table 1.4, although Cu is the third tonnage metal after Fe and Al, its concentration in the Earths crust is quite low (only about 0.01%) Tonnage of metal depends on: - Accessibility of ore deposits - Richness of the Ore deposits - Nature of extraction and refining processes for the metal - physical and chemical properties of the metal and - demand for the metal which is governed by many factors including its physical and chemical properties of the metal
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A fundamental consideration in all the above mentioned factors, is of course, economics. A metal becomes a common one, if it is readily available and easily produced with low processing cost and if it allows development of attractive properties Table 1.4 presents approximate world production figures for some metals It is seen that, iron as steel is by far the most widely produced metal. This is so because, iron ores are available in plenty in easily accessible deposits. Also, the processing of iron ores, is relatively easy and economical. Finally, alloy of iron has a wide range of useful properties
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Pb
Sn
30
0
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Because of the importance of iron and steel, Ferrous Extractive Metallurgy, is a subject on its own right The non-ferrous metals which are produced in large quantities include metals such as, Al, Cu, Pb and Zn The non-ferrous metals strictly means all metals other (common metals) than iron But mMetals such as thorium, Vanadium, which are not commonly used, which are far more expensive, are commonly referred to as rare metals or less common metals
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For eg: (i) electrolysis is practised for Al, Zn, Cu and a variety of other metals (ii) smelting is carried out for the extraction of Fe, Pb, Cu etc. The various extraction and refining routes are formulated essentially by the selective combination of these units The unit steps are classified into: Unit Operations and Unit processes
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Pyrometallurgical processes (in Greek, pyr means more at fire) are carried at high temperatures. Hydrometallurgy (in Greek, hydro means more at water) is carried out in aqueous media at or around room temperature Electrometallurgy employs electrolysis for separation at room temperature as well as at high temperature
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2. Liquid-state processing: This involves melting of at least the metal-containing phase and is carried out at a higher temperature. Examples are blast furnace smelting, steelmaking, distillation refining of zinc from impure lead etc. Liquid state processing separates out the metal either in pure or in impure form. Appreciable compositional changes in the liquid are possible due to miscibility, rapid diffusion and mixing.
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This system of classification can be extended to hydro and electrometallurgy as well. Processes can be also classified according to type of chemical reaction, mode of energy input etc. Based on all the above discussions, an attempt has been made to characterise some important unit processes and unit operations in Extractive Metallurgy as shown in Table 1.5
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Purpose
Contacting Phases
7 Solid, gas
1 Roasting of sulphide
5 Pretreatment
-do1200-1600
Decomposition Reduction
-doExtraction
Metallothermic reduction of metal oxides, chlorides Leaching Distillation, refining Solvent Extraction Electrolysis
900-2400
-do-
-do-
-do-
-do-
Bomb, retort
Hydromet, unit proces, solid-state Pyromet, unit process, liquidstate processing Hydromet, unit proces, liquid-state processing Electromet, unit proces, solid or liquid-state processing
Dissolution -do-
Pretreatment Refining
Room temp.
Exchange
Pretreatment
Liquid
Electrochemical
Extraction. Refining
Electrical
Solid, liquid
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1.2
HYDROMETALLURGY
The development of extractive metallurgical processes for reactive metals and nuclear metals after 1940s gave a great filip to the more sophisticated hydrometallurgical methods The early applications were mainly for oxide ores or native metals
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HYDROMETALLURGY
Later applications: - Leaching of sulphide ores by oxidizing leachants like ferric salts - Ammoniacal pressure leaching (Sherritt Gordon processes) for nickel-cobalt sulphides and arsenides during 1946-55 - Pressure leaching of sulphide ores and concentrates also was actively pursued around 1950 onwards
EBS 315 Chapt 1 Slides 1-55
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HYDROMETALLURGY
The extraction of metals by using aqueous methods, as against pyrometallurgy where reactions at much higher temperatures are involved
In hydrometallurgy, the ore is leached i.e. dissolved slowly using suitable economical leaching agents, which could be acids, alkalis, salts or complex chemicals.
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HYDROMETALLURGY
After leaching, the solutions are purified, concentrated as necessary and may also undergo solid-liquid separation. The metal is recovered from the purified, concentrated solution by precipitation and reduction methods
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Advantages of Hydrometallurgy
Metals can be obtained directly in the pure form from the leach solutions, without any lengthy refining process. The interest in hydrometallurgical approach grew as the pressure of environmental regulations against the SO2 pollution in sulphide ore pyrometallurgy became a major issue. But with developments such as double contact acid plants, modern pyrometallurgical plants are able to meet SO2 requirements.
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2. Hydrometallurgy allows greater control over every step in processing of ores, resulting in recovery of valuable by-products. Metals may be obtained directly in a pure form from the leach liquor using one of several methods. Handling of materials is also easier. 3. Hydrometallurgical operations are often preferable from the point of view of reducing environmental pollution. Thus, while pyrometallurgical processing of sulphide ores eg: copper ores produces SO2 , the leaching of ores keep sulphur in solution.
EBS 315 Chapt 1 Slides 1-55
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SO2, liberated during roasting of sulphides as well as during the other steps in pyrometallurgical processing, is not always suited for use in H2SO4 production. Even if it is used in acid production, there is still also SO2, escaping into the air, unless stringent anti-pollution measures are effected. 4. A hydrometallurgical process may start on a small scale and expand as required. However, a pyrometallurgical process usually must be designed as a large scale operation for reasons of process economy
EBS 315 Chapt 1 Slides 1-55
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There are advantages as well: 5. For example, in some hydrometallurgical recovery, the metal can be produced in a variety of physical forms eg: powder, nodule, coherent surface deposits etc. 6. Again, very reactive metals are difficult to refine by pyrometallurgical methods. Therefore, pure compounds can be first obtained by hydrometallurgy and then reduced to pure metal.
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7. Also, corrosion problems are relatively mild in hydrometallurgy as compared with deterioration of refractory linings which requires periodic shut down in pyrometallurgy.
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Disadvantages of Hydrometallurgy
1. Aqueous solutions employed are generally dilute (1 Molar). Thus, large volumes of solutions are to be handled for relatively, smaller metal outputs. This requires considerable amount of handling as well as space. 2. Some reagents are expensive and must recycled or regenerated for economy. 3. Reactions rates are lower at room temperatures as compared to processing at high temperatures. Hence, tonnage capacity of a plant is lower as compared to that obtainable in pyrometallurgy
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3. Reactions rates are lower at room temperatures as compared to processing at high temperatures. Hence, tonnage capacity of a plant is lower as compared to that obtainable in pyrometallurgy .
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With reference to the environmental aspects, though hydrometallurgical approach avoids sulphur emissions, the effluents carry heavy metals and must be carefully treated or impounded. The gangue rejected by hydrometallurgy in the form of active iron oxides and jarosites can create a considerable cost burden. One may even argue that the slags in pyrometallurgy can be relatively non-reactive and can be easily stored.
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Process
(a) Pyrometallurgy: Iron blast furnace, less auxiliaries. Iron blast furnace, with stoves, dust system. Flash smelting of Cu with O2, less auxiliaries Flash smelting of Cu with O2, including dust collection system
1100
1.0
0.4
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75 35
0.08 0.04
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Table 1.6: Energy requirements for metal production from concentrates per metric tonne of metal
Process (a) Pyrometallurgy: Fe: Blast furnaceoxygen steel making Cu: Flash smelting (O 2) converting electrorefining Pb: Blast fiurnace dross fire refining Zn: ISP blast furnacereflux Product Energy requirements (J) 109 per metric tonne metal 22 23
21 51
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Table 1.6: Energy requirements for metal production from concentrates per metric tonne of metal
Process (a) Hydrometallurgy: Cu: Leaching of sulphide concentrate Zn: Roasting Leaching - Electrowinning Al: Bayer leaching-Hall electrolysis Product Energy requirements (J) 109 per metric tonne metal
Cathode Cu
~ 100
55
Al ingot
280
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On the whole, however, the advantage often outweigh the disadvantages and hydrometallurgy is becoming increasingly important for many non-ferrous metals. The choice therefore is made on the basis of specific details of a particular process and its technical and economic viability for a plant at a given location
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