BIOMINING

lecture # 1 Zygmunt SADOWSKI Wroclaw University of Technology Chemical Engineering

Schedule
04.12 Friday 07.12 Monday Lecture #1 Lab. Lecture # 2 Lab.

09. 12 Wednes.
10. 12 Thurday 11. 12 Friday

Lecture # 3
Lecture # 4 Lecture #5

Lab.
Lab. Lab.

14.12 Monday
15. 12 Tuesday 16.12 Wedns.

Lecture #6
Lecture # 8 Lecture #10

Lecture #7
Lecture #9 Exam

Subject of lecture
1. Introduction to biohydrometallurgy 2. Microorganisms involved in bioleaching 3. Physical chemistry of bacterial leaching 4. Mechanism of bacterial oxidation 5. Bioleaching kinetics 6. Copper ores bioleaching 7. BIOXTM process 8. Post mining restoration of environment (Acid mine drainage) 9. Biosorption 10. Desulferization of coal and oil

Books
1. Giovanni Rossi Biohydrometallurgy McGraw-Hill Book Comany GmbH, 1990. 2. D.E.Rawlings (Ed.)Biomining Theory, Microbes and Industrial Processes Springer 1997. 3. D.E.Rawling, B.W.Jonson (Eds.) Biomining Springer 2007. 4. Edgardo R.Donati, Walfgang Sand Microbial Processing of Metal Sulfides, Springer, 2007. 5. Z.Sadowski, Biogeochemia- wybrane zagadnienia, Wydawnictwo P.Wroc. 2006

Definition
Bioleaching is the biological conversion of an insoluble metal compound into a water soluble form. For bioleaching Bacteria and Archaea are used. Bioleaching involves chemical and biological reactions.

Ancient history of hydro- and biohydrometallurgy

Roman writer Glius Plinus Secundus 23-79 A.D. describes haw copper minerals are obtained using a leaching process.

Hydrometallurgical extraction of copper from ore and the precipitation of copper from the solution by treatment with metallic iron is an ancient technology

History of biohydrometallurgy

History of biohydrometallurgy
166A.D. the scientist Galen described in situ leaching in old copper and lead mine at Cyprus. 1494-1555 Georgius Agricola described roasting pyrite (FeS2) to prepare for leaching and produce FeSO4. 1572 Industrial heap leaching of copper sulfides in Rio Tinto (Spain). 1879 Bioleaching of low-grade ore at Rio Tinto. 1947 Thiobacillus ferrooxidns was identified and isolated from acid mine drainage. 1965 Discovery of the first iron and sulfur oxidizing archaea Acidianus Brierlevi from thermal spring in Yellowstone.

What is biohydrometallurgy ?
The various branches of science from which the fundamentals of hydrometallurgy are derived

The recovery of heavy metals from sulfidic ores employing microorganisms

Area of application
Three main areas of application can be identified: Metal extraction from minerals and rocks Environmental protection Pre-treatment of minerals to make them amenable to further processing

Biohydrometallurgy

The main application of biohydrometallurgy is bioleaching

The action of bacteria

1. to convert insoluble metal sulfides ( or oxides in the case of uranium) to water soluble metal sulfates. 2. to open up the structure of the sulfides minerals for other chemical better penetration.

Bioleaching
The mobilization of metal cations from insoluble ores by biological oxidation and complexation process is referred to as bioleaching. Metals for which bioleaching is employed: Copper (Cu) Cobalt (Co) Nickel (Ni) Zinc (Zn) Uranium (U)

Advantages to using bioleaching for the metal extraction

1. The use of naturally occurring components: microorganisms, water, ore, and air. 2. Simple to operate and maintain (stirred tanks, heap leaching). 3. Low pressure (atmospheric) and temperature process. 4. Dust and SO2 free

Advantages of bioleaching
The advantages of bacterial leaching technology are agreeable with these requirements:
Moderate capital investment with low operating costs, Appropriate recovery of metals from lowgrade ores and waste materials, Basic equipment and simple operating procedures.

Advantages
Miroorganisms are responsible for production of ferric iron (Fe3+) and acid. Bioleaching is environmental friendly than many physical metal extraction processes

Disadvantage of biomining
The main disadvantage of bioleaching of sulfides is that the process is perceived to be slow relative to pyrometallurgical processes

Pyro- and hydrometallurgy

Currently 25 % of all copper worldwide, worth more than $ 1 bilion annually, is produced through bioprocessing

Block diagram showing the factors affecting reactor bioleaching profitability

Microorganisms-mineral interaction
Acidolysis formation of organic and inorganic acids (protons).
Sulfuric acid is the main inorganic acid found in bioleaching environments.

Complexolysis the extraction of complexing agents. Redoxolysis oxidation and reduction reactions.

Complexolysis and Acidolysis

Metals in certain non-sulfide minerals may be solubilized by a process of complexation with oxalic, citric or other organic acids.

These organic acid are typically produced by certain type of fungi. Aspergillus niger, Penicillum

Bacteria for biooxidation process

In the processes that operate from ambient temperature to about 40oC, the most important microorganisms are considered to be a consortium of Gram-negative bacteria. These are the iron- and sulfur-oxidizing bacteria (Acidithiobacillus ferrooxidans). the sulfur-oxidizing (Acidithiobacillus thiooxidans and Acidithiobacillus caldus) the iron-oxidizing leptospirilli (Leptospirillum ferrooxidans and Leptospirillum ferriphilum)

Bacteria for biooxidation process

Bacteria Biooxidation reactions

Acidithiobacillus ferrooxidans
Acidithiobacillus thiooxidans Leptospirillum ferroxidans

Fe2+ Fe3+ S2- or S0 SO42S2- or S0 SO42Fe2+Fe3+

Acidophilic metal sulfide oxidizing microorganisms

All acidophilic metal sulfide oxidizing microorganism oxidize Fe2+ and sulfur compound.

Biooxidtion of Fe2+ ions, Redox potential (Eh)

The potential Eh is the ratio of dissolved ferric to ferrous ions.

Fe Eh 771 59 log Fe
3 2

Eh is used as a bioleaching indicator. The best leaching was achieved between 600750 mV

Biooxidation process
The biooxidation conditions typically exhibit a relatively high redox potential around Eh=0.65 0.70 V . One consequence of the high solution potential is that ferric ion readily precipitates as a basic sulphate , like jarosite . 3Fe3+ + 2SO42- +6H2O + Me+MeFe3(SO4)2(OH)6 + 6H+ where Me = K+,Na+, NH4+

Jarosite precipitation

Experimental equipment for biooxidation

Bioleaching
The recovery of heavy metals from sulfidic ores employing microorganisms is now an established branch of biotechnology. Microorganisms are able to regenerate of the oxidizing reagent which chemically reacts with metal sulfides. Bioleaching is currently an economical alternative for treating specific sulfidic ores.

Heap and tank bioleaching

Copper recovery

Gold ores pretreatment

There are two ways of applying bioleaching for metal recovery from sulfide ores, namely heap leaching and tank leaching

Tank bioleaching process

In stirred tank processes highly aerated, continous-flow reactors in series are used to treat the mineral suspension. The stirred tank reactors operate at 400C and 500C. The suspension density is limited to above 20 %, as the pulp density is > 20% the microbial problems occur.

Application of tank bioleaching

Stirred tanks are used as a pretreatment process for gold containing arsenopyrite concentrates. The first bioleaching instalation has been built at Fairview mine, Barberton, South Africa in 1986. The largest is at Sansu in the Ashanti goldfields of Ghana, Wester Africa. Cobalt-containing pyrite is leached at Kasese, Uganda

Stirred tank versus bioheap

The principal disadvantages of aerated, stirred-tank reactors compared to bioheaps are the capital and operating costs. In situ bioleaching In situ bioleaching has been commercially us for extraction uranium and copper from depleted underground mines

Bioheap leaching
The pregnant leach solution containing: 1.5-6 gL-1 soluble copper and up to 20 gL-1 is collected and sent to a recovery plant The common methods for copper recovery: Precipitation with using iron (cementation) Electrowinning Solvent extraction followed by electrowinning

Pirometallurgical methods
The arsenopyrite flotation concentrate contain gold is roasted at 7000C in the presence of oxygen or digested with acid under pressure in oxygen-enriched atmosphere (autoclaved).

Environmental impact of the acid generation

pH = 2.5

1.33 moles of sulfuric acid are produced per mole of pyrite