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SMMRE

Academic Session 2012/13

SCHOOL OF MATERIALS & MINERAL RESOURCES ENGINEERING


EBS 315/3: HYDROMETALLURGY

Lecturer: Dr. Norlia Baharun

1.0
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

Ore minerals Gangue Minerals

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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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1.1 Mineral Reserves and Resources

1.1.1 Natural Occurrence of Metals


Naturally occurring Minerals oxides, sulphides and halides in simple chemical composition [eg: hematite: Fe2O3 , chalcopyrite: CuFeS2, dolomite: CaMg(CO3)2 ] Most abundant minerals: silicates The exact nature of association of a metallic element with other elements depends on the reactivity of the metal, distribution of other elements in the neighbourhood as well as the geological conditions to which the mineral deposites are subjected through the ages
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1.1.2 Sources of Metals


Metals and their compounds are available from three sources: (i) Ore deposits in the Earths crust (ii) Ocean waters (iii) Scrap metals A man-made source which is getting more important and freely available with the industrial growth of societies

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1.1.1 Sources of Metals


Increasing amounts of scrap are being recycled in technologically developed countries. Reclaimed and recycled lead and Aluminum constitute about 50% of feedstock for production of respective metals in UK and USA. Table 1.1 and 1.2: show the average chemical analysis of the Earths crust and the sea water respectively. There are several hundred billion tons of nodules in the ocean floor and they continue to form at the rate of about 10m tons/yr Table 1.3 gives some figures to indicate the reseves, the composition and the relative abundance of nodules as compared to deposits in land
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Table 1.1: Average analysis of the Earths Crust


Element O Si Al Fe Ca Na Percent 46.7 27.7 8.1 5.0 3.6 2.8 Element Cr Cu Ni Zn Pb Co Percent 0.01 0.01 0.008 0.004 0.002 0.001

K
Mg Ti Mn Zr V

2.6
2.1 0.44 0.10 0.017 0.014
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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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Table1.2: Average concentration of some elements present in solution in sea water


Element Na Mg Ca K Concentration (g/tonne) 10,500 1,270 400 380 Element Zn Cu Mn Pb Concentration (g/tonne) 0.005-0.014 0.001-0.09 0.001-0.01 0.004-0.005

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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Table 1.3: Reserves of Metals in Pacific ocean nodules


Element Wt % in nodule Estimated reserve (109 tonnes)
25 43

Ratio of Nodule reserve Land reserve


200

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
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1500
150 10 1000 60 1 50
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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

1.1.2 Commercial Production of Metals

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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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Table 1.4: World Production of some metals (1985)

Metal/Alloy Raw steel Pig iron Al Cu (blister) Cu (electrolytic) Zn

Production (Thousands metric tonnes /year) 12,230 11,590 240 39 22 61

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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1.2 EXTRACTIVE METALLURGY A process of separation


Any extraction and refining process consists of some individual sequential steps: unit steps. Each unit steps can be found in more than one process

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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1.2.1 Unit Operations & Unit Process


It refers to physical operations such as comminution, filtration, casting, distillation etc. In all subsequent discussions, the term process will be used to mean both unit operation and unit process

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1.2.2 Separation process


Production of metals of desired purity from natural ores is principally a separation process The separation process may be classified into two stages: (1) Separation of the compound containing the desired metals from other constituents. It is the separation of ore mineral from other gangue minerals. This is known as Concentration and it comes under the discipline of Minerals Engineering
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1.2.2 Separation process


(2) Separation of the desired metal from other constituents of the metallic compound and further purification of the metal. This is known as Extraction and Refining and constitutes the subject matter of
Extractive Metallurgy
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1.2.2 Separation process


For some metals such as Al, the two stages are distinct Pure alumina (Al2O3) is produced by the Bayers process from the ore. The Al metal is extracted by electrolysis. However, for Fe, there is no separate concentration step for the production of iron from high grade ores. The gangue materials are by and large separated during extraction in the blast furnace. Lean ores may, however, require beneficiation
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1.2.3 Classification of Processes


Processes can be classified in various ways depending on the aim Traditionally, methods of extraction and refining have been classified into the following categories: Pyrometallurgy Hydrometallurgy Electrometallurgy
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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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Another way of classification:


In terms of unit operations or unit processes, pyrometallurgy can be classified as follows: 1. Solid-state processing : This does not involve any melting. It is typically carried out in the temperature range of 500-1200 C, as exemplified by roasting of sulphides, calcination, solid state reduction of metal oxides by H2 and CO. Solids are mostly immiscible and hence the product of solid state processing is either pure or is a mechanical mixture. In the later case, it requires further separation.
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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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Table 1.5: Characteristics of some unit processes and unit operations


Name of Process Broad Classification
2 Pyromet, unit process, solid-state processing -doPyromet, unit process, liquidstate processing -do-

~ Temp Range (C)


3 500-1200

Type of Chemical Rxn


4 Oxidation

Purpose

Mode of Energy Input


6 Fuel, exothermic heat of rxn

Contacting Phases
7 Solid, gas

Typical Reactors employed


8 Shaft furnace, fluidized bed reactor, flash roaster, rotary kiln -doBlast furnace, retort, electric arc furnace

1 Roasting of sulphide

5 Pretreatment

Calcining Carbothermic smelting

-do1200-1600

Decomposition Reduction

-doExtraction

Fuel Fuel, electrical energy

-doSolid, liquid, gas

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

Room temp. -200 1000-2000

Dissolution -do-

Pretreatment Refining

Fuel, electrical energy Fuel, sensible heat of input materials Nil

Solid, liquid Liquid, gas

Vats, autoclaves Retort

Room temp.

Exchange

Pretreatment

Liquid

Packed bed, plate column Electrolysis tank

Room temp. -900

Electrochemical

Extraction. Refining

Electrical

Solid, liquid

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1.2

Principles & Uses of Hydrometallurgy & Electrometallurgy

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
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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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1.3 Hydrometallurgy Vs Pyrometallurgy

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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Advantages of Hydrometallurgical Approach


Hydrometallurgical processing is characterized by several distinct advantages: 1. Hydrometallurgical methods are suitable for lean and complex ores. With gradual depletion of rich ore deposits, it is becoming increasingly difficult in many situation to apply conventional pyrometallurgical methods for metal extraction

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Advantages of Hydrometallurgical Approach


If there are too much gangue, then processing of ores at high temperatures causes wastage of energy as well as problems of slag disposal. The siliceous gangue in ore is unaffected by most leaching reagents; whereas in pyrometallurgical smelting processes, the gangue must be slagged.

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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.
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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
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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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From the energy point of view:


Many have the misconception that since pyrometallurgy involves high temperatures, it requires much more energy per metric tonne of metal as compared to hydrometallurgy It is true that, since most hydrometallurgical processes are carried out at room temperatures, there is no direct consumption of large amounts of fuel.

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From the energy point of view:


However, correct comparison may be state as follows: 1. For direct treatment of low-grade ores, pyrometallurgy is inapplicable and therefore, there can be no comparison. On the other hand, for recovery of metals from high-grade ores and concentrates, both methods are feasible.

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From the energy point of view:


But, with one or two possible exceptions, pyrometallurgy requires less energy than hydrometallurgy to produce one metric tonne of metal. The lower energy requirements of many pyrometallurgical processes as compared to hydrometallurgy are ascribed to the following beneficial factors in the former: 1. concentrated process streams 2. accelerated reaction rates and reduced residence times which increase throughput and 3. exothermic nature of many reactions
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From the energy point of view:


Also, heating, evaporation and steam stripping of aqueous solutions in hydrometallurgy are energyintensive despite the low temperature involved. Finally, electrowinning, the most used means of metal recovery, is also energy-intensive. Table 1.5 and Table 1.6, present some data on comparative intensity and energy requirements of the two routes, respectively.

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Process

Table 1.5: Intensity of Pyrometallurgical and Hydrometallurgical Processes


Concentration g.mole/m3 X 10-3 1500 1.6 0.4

Productivity, metric tonne/day/m3

(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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Table 1.5: Intensity of Pyrometallurgical and Hydrometallurgical Processes


Process (a) Hydrometallurgy: Leaching zinc calcine, purifying solution. Electrowinning of zinc Electrowinning of Copper 150 0.10 Concentration g.mole/m3 X 10-3 Productivity, metric tonne/day/m3

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

Steel Ingot Cathode Cu

Refined Pb Special high grade Zn

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

Special high grade Zn

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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