100 Years of Blowing Bubbles for Profit (With an Emphasis on the Bubbles)

Jan E. Nesset CIM Distinguished Lecturer 2008-9 Original presentation

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Outline...
What is flotation and why this talk now? Lets step back 100 years The Inventors The Implementers Lawsuits (always a good sign) The Chilean and Canadian perspectives

...Outline
The next 70 years people forgot
about the bubbles in the process

Renewed interest 1990s Last word to the historians

What is froth flotation?

Consider 2 different types of mineral particles in water

IN WATER
UNDESIRED MINERALS

DESIRED MINERAL

The desired mineral particles are selectively coated with a hydrocarbon chemical collector making them hydrophobic (water-hating)

Consider 2 different types of mineral particles in water

Approaching gas bubble

Consider 2 different types of mineral particles in water

rising gas bubble collects hydrophobic particles only

Role of Frother controls bubble size created and prevents coalescence of bubbles

Courtesy of McGill University, Materials Engineering

Modern plants use large capacity equipment

38 ft diameter SAG mill

160 m3 flotation cells

Flotation is widely used (examples)

Base metals: Cu, Pb, Zn, Ni, Mo, Fe, Sn, Ti Precious metals: Au, Ag, Pt, Pd Industrial minerals: graphite, potash,
phosphate, even diamonds

Environmental: Waste water treatment,

contaminated soil remediation

Recycling: ink from paper, plastics from scrap Energy: coal, bitumen from oil sands, uranium

Lets step back about 100 years... Comminution and Mineral Separation Circuits at the end of the 19th Century.. ...not much change over the previous 300 years

Stamp Mills

Deadwood, South Dakota gold mill, 1888 mid-1500s

Hand Sorting of Ore

Sullivan Mine, BC, circa 1910 mid-1500s

Gravity jigs, sluices and tables

mid-1500s

Sullivan Mine, BC, circa 1940 Jig, early 1900s

Mineral Processing was at an impasse....

Gravity methods and hand

sorting prevailed

Metal recoveries were

typically 50-70% at best

Recovery of smaller particles

(slimes) and concentration of lower density materials was not possible

The example of Broken Hill, Australia, at the turn of the 19th Century
new BHP ore dressing plant, 1899 An enormous Pb-Zn-Ag deposit in New South Wales (20%Pb, 18%Zn 300 gpt Ag)

+6 million tonnes of zinc rich tailings in huge piles

At the BHP mine the mineral processing methods could not treat the sulphides efficiently
800 Annual Ore Production Bonuses & Dividends 1200

Production, kTonnes

600 800 400 600 400 200 200 0 1886 1888 1890 1892 1894 1896 1898 1900 1902 0

Year of Production

Profits plummeted as the mining moved from the upper oxides to the lower sulphide ore

Dividends, A$ x 1000

1000

Other mines were running into similar problems

1. Britannia Beach copper

mine in British Columbia.

2. Sullivan lead, zinc, silver

mine in south-eastern B.C.

3. Porphyry copper mines in

the U.S. mid and south-west and in Chile (Braden)

Other mines were running into similar problems

Britannia Beach
copper mine on British Columbia coast Discovered in 1888 Relatively fine-grained Cu finally began production in 1904. Used hand-sorting Gravity circuit was a disaster

Other Mines were running into similar problems

Sullivan lead,
zinc, silver mine in British Columbia Discovered in 1892 direct smelting of ore 1898-1907 grades decreased from Hand-sorting kept 43%Pb, 600 gpt Ag to the mine operating 16.5%Pb, 230 gpt Ag from 1910-1914 High zinc contamination

Other Mines were running into similar problems

Concentrate Grade, % Cu

The U.S. Copper

porphyry mines

40 30 20 10 0 50 60 70 80
Early 1900's

Modern porphyry plants

Utah Chino Ray Nevada

90

100

Cu Recovery, %

Feed grades 1-2% Cu Cu recoveries only 60-70% with gravity methods Unable to treat slimes

Other Mines were running into similar problems

Braden Copper Co. El Teniente mine (1906)

Feed grades 3.4%Cu, 250 tpd Cu recoveries 45-55% with gravity methods High costs, barely economic, tried Elmore cells

The Industry Faced Immediate Challenges

1. The sulphide problem as

oxide deposits depleted

2.The porphyry problem of

low Cu recoveries

3.The zinc problem of no/low

recovery and contamination (poor differential separation of lead from zinc)

What else was happening in the World?

1891 1st 60-cycle AC power distribution system
1892-3 GE and Westinghouse formed 1900 Max Plancks Quantum Theory

1900 - U.S Gold Standard Act

1901 1st Nobel prizes 1903 - Ford motor company founded

1903 Wright brothers 1st powered flight

1903 electric washing machine and vacuum cleaner 1905 Einsteins Theory of Relativity 1909 Plastic is invented 1913 electric refrigerator

The Result
DEMAND

SUPPLY

Demand for metals (Cu, Pb, Zn, Au) was increasing rapidly while the supply was becoming scarcer Technology was at the forefront. People expected engineers/scientists to find the solution

The Inventors

The Europeans

In 1860 William Haynes (Britain) patented a process for separating sulphides from ground ore by mixing with oil (1-10%) and separated in water. He called it bulk-oil flotation. There was no commercial application. The agglomeration of oil/sulphides likely had a density less than water so floated to the top. In 1877 the Bessel brothers, Georg and Adolph (Germany), owners of a graphite business making crucibles, patented a process for mixing oil and graphite and then boiling the mixture in water to produce high grade graphite (90%) in the froth. The process was a commercial success.A modified patent in 1886 substituted lime and acid to produce the bubbles. The first true commercial application of froth flotation

An American Woman

In 1885, Rebecca (Carrie) Everson (U.S.), wife of a physician who had invested in a failed mining enterprise that she wanted to help, patented a process for separating sulphides by mixing with small quantities of oil and adding water and sulphuric acid. Entrained gas in the agglomerated mixture likely resulted in flotation. Attempts to commercialize on several ore types failed. She was unable to raise further funding.

More Europeans...

In 1898 Francis and Alexander Elmore (Britain) patented a bulk oil flotation process involving intimate mixing of oil and lead sulphide ore in mixing drums before adding to a water-filled separation vessel. Entrained air resulted in flotation of the agglomorated mixture. The process was successfully applied at the Glasnir lead mine in Wales. This bulk oil flotation process was widely applied. A second successful patent (1904) involved applying vacuum to generate small bubbles.

1898 Patent

Vacuum process

...Still More Europeans

In 1902 Alcide Froment (Italy) patented (UK) a process for the use of any kind of gas bubbles to float sulphide particles treated with a minute quantity of oil/fatty substance. His was the first link between oil flotation and gas flotation but he failed to specify that the bubbles be generated by air. The British engineering firm Minerals Separation bought Froments patent in 1903 and it became the basis for their string of patents covering froth flotation

In Summary

It took over 40 years to make the link that both minute quantities of oil and small gas bubbles were needed for successful froth flotation of sulphides It would take only another 10 years for the implementers to make an effective flotation machine and sort out most of the key operational issues

The Implementers

Back to Broken Hill, NSW, Australia, where zinc tailings were piling up and profits had disappeared

There were several competing companies: Zinc Corporation, Broken Hill Proprietary (BHP), De Bavay Company, British Total estimated value of tailings, Broken Hill (Ag, Zn, Pb) over 33 million

BHP was first out (1903) with the Delprat process (later Potter-Delprat)
They added acid or sodium sulphate (salt cake) to hot tailings pulp to generate CO2 bubbles, no oil added directly (residual ?) Used until 1923 1st 50 tons of zinc concentrate produced from tailings (1903)

Each Plant used different patented device to avoid licence fees

PotterDelprat Used at BHP until 1923

Elmore vacuum Used at Zinc Corp. until 1917

De Bavay Used at his plant until 1913

The Mineral Separation Co. The true developers of froth flotation

A British company formed in 1905 to exploit flotation for separation of sulphide ores
They bought up patents and charged royalties

Alcide Froment (1903) gas bubbles and oil together Sulman, Picard, Ballot (1905 U.S.) - pneumatic cell

Constructed a new cell design for use Sulman, Picard, Ballot on zinc tailings at Broken Hill patent

The Mineral Separation Co. The true developers of froth flotation

The key was to add a very small quantity of oil (<<1%) and subject the pulp to violent agitation before feeding to a froth separation chamber

Stll did not have the notion of blowing in air

Design circa 1910

The Hoover Brothers... ...Key Connection to Flotation

Herbert Hoover, mining engineer (1895,Stanford) Managed mines in Australia and China made a fortune Founder of Zinc Corporation (Broken Hill) 1906 Brought MS to Australia to solve zinc flotation problem

Theodore Hoover, mining engineer (1901,Stanford) Managing Director of Mineral Separation, 1906-1910 Wrote one of first texts on flotation, 1916 Prof of Mining/Met - Stanford

At last...Pneumatic Flotation Machines Circa 1915

Mineral Separation subaeration machines Air introduced with stirred mechanical agitator

Callow machines Air blown in through a permeable cloth on bottom

Leslie Bradford Developer of Activators and Depressants for Differential Flotation for Lead and Zinc at Broken Hill Use of CuSO4 as activator for zinc
flotation (1912)

Use of SO2 and sulphite as depressants for zinc mineral (1913)

Implemented close air control, alkaline flotation circuits Mineral Separation introduced a sub-aeration flotation cell by 1916 True differential flotation fully implemented by 1916 at the Broken Hill mines

Froth Flotation moves to North America.

The Basin Reduction Co. Plant, Basin Montana (Butte and Superior Copper Company), 1911

Retreatment of zinc tailings in a lead-zinc operation Ultimate objective was to apply to porphyry copper recovery James Hyde was a Mineral Separation employee until 1910 when he left at the urging of Herbert Hoover to implement flotation at the Basin plant

Hyde was a classmate of Theodore James Hyde running Hoover, who also left MS in 1910 a flotation test

The Basin Reduction Co. Plant, Basin Montana (Butte and Superior Cooper Company), 1911

Start-up in Aug, 1911 on zinc recovery from lead tailings

Used a modified cell adapted from Mineral Separation 1st application of a rougher-cleaner circuit
A lawauit with MS shut the mill down after 6 months The Basin Plant Rougher cells above, cleaner cells below

The Lawsuit (Hyde vs Mineral Separation)

Mineral Separation Patent June 28, 1910

T. Hoover Patent

April 5, 1910

Hyde countered with a 2nd patent Applied Nov 10, 1911

The Judgement (U.S. and Britain) (Dec 11, 1916)

The evidence of infringement is clear
the patent must be confined to the results obtained by the use of oil within the proportions often described in the testimony and in the claims of the patent as 'critical proportions,' 'amounting to a fraction of 1 per cent on the ore,'

This was the final litigation battle Mineral Separation claimed royalties from many operations for the use of a froth flotation licence provided the oil use was below 1% of the ore

The Canadian and Chilean Connections

Braden Copper Mine (El Teniente) Britannia Beach Copper Mine

The Sullivan Lead-Zinc-Silver Mine

The Application of Froth Flotation at Bradens El Teniente mine -1912

Cu Concentrate Grade (%)

The first Chilean application of froth flotation (on gravity tailings) 30% increase in Cu Recovery Revolutionized Chilean copper industry

25 20

Pre-1911 1911 1912 1913 1914

15 10 5
30 50 70 90 Cu Recovery (%)
Pre-flotation gravity only Flotation started Nov 16, 1912

1915 1916 1917 1918 1919

Mill Feed, MillionTPY

First production of copper by froth flotation?

Mineral Separation cells at Sewell concentrator

2.0

1.5
1.0

Flotation started Nov 16, 1912

0.5
0.0

The Britannia Beach Copper Mine West Coast of B.C., 1912

The first North American application of froth flotation to copper (gravity tailings feed) Used Mineral Separation cell technology
Cu recovery improved dramatically to 94% and the mine became profitable for the first time First Canadian froth flotation mill

The original Britannia flotation mill with gravity mill behind, 1912.

The Porphyry Problem Solved

..At the Britannia Mine in British Columbia where the plant has been in operation for many months, recoveries of over 94 per cent are being regularly obtained, .

Times of London June 18, 1913

The Brittania Beach float plant was operating before any of the U.S. Copper plants

Solving the metallurgy of the highly complex Sullivan Pb-Zn-Ag deposit

Differential Pb-Zn flotation used in Australia did not work: high pyrrhotite, very fine grained Mineral Separation offered little help. Other ores were far easier and more plentiful
The Sullivan mill started operation in 1923

The impact on Cominco (Consolidated Mining & Smelting Co.) All elements of complex sulphide differential flotation
were developed: 3-stage grinding, regrinding middlings, stage/starvation reagents, multi-stage cleaning, heated pulp

The successful flotation plant at Sullivan changed the fortunes of the Trail Smelter and Cominco

Flotation Began

Production by year from the Sullivan Mine

Smelting Practices had to change to accomodate more fine concentrates instead of lump ore
Multi-hearth roaster

Victoria Roast Yard, Sudbury, 1890s

Reverberatory furnaces, Anaconda 1915

Open roasting of lump ore gave way to multihearth roasters and large reverberatory furnaces

The Impact on World Pb, Zn, Cu Production It is clear that Pb, Zn and Cu production increased
rapidly following the introduction of flotation
Trends in World Lead, Zinc and Copper Output 1800 to 1920 2

Output, million tonnes

1.5 1

Advent of Flotation 1905 - Australia

Lead

0.5 0
1800 1820 1840 1860

Zinc Copper

1880

1900

1920

Year

The Insight of Thomas. A. Rickard

Mining engineer (RSM, 1885)

Friend of the Hoovers

Historian, writer and publisher of Mining & Engineering Press

we know that the key to the flotation process is to be found, not in the oil, not in the acid, or in the apparatus, but in the bubbles. The man who understands the mystery of a soap bubble has mastered the chief mystery of flotation The Flotation Process (1916)

Key Role in Technology Transfer

In 1910, the true role of bubbles in flotation was misunderstood

By 1920, the significance of the bubbles and how to make them was understood

Mechanical, sub-aeration flotation machines Need for frothers separate from collectors: Pine oil, pine-tar oil, cresylic acid, eucalyptus oil were still in use 60 years later

For the next 70 years people forgot about the bubbles in the process

1990s: The Study of Gas Dispersion and Cell Hydrodynamics

Barun Gorain (JKMRC) validated the key k-BSAF relationship Gorain

Finch and Gomez (McGill) developed industrial sensors now used in plants all over the world

Gas Hold-up (Conductivity) Bubble Size (Imaging)

Jim Finch and Cesar Gomez Gas Velocity (Pressure)

What do the Technology Historians Have to Say ?

The development of flotation was the greatest single metallurgical improvement of the modern era.....it is not overstating the case to claim that flotation was of central importance to the smooth functioning of the global economy Jeremy Mouat (1996) both the internationalism of the mining industry and the nature of its technology transfer blurr the lines between invention, innovation and adaptation. Mining machinery, techniques and people were all highly mobile. Hence attributing national origins to mining technology often seems irrelevant. Diane Menghetti (2005)

Final Thoughts (mine)

The development of flotation took a long time because it involved physical and chemical concepts that were entirely new Flotation was the enabling technology for modern mining business. The economical processing of new ores by flotation created companies that became mining giants, many of which are still here today, and changed global business Rickard was right, understanding the bubbles was, and continues to be, the key to improving the flotation process

Acknowledgements....Many Thanks to

Canadian Mineral Processors

Robertina Pillo and the Canadian Institute of Mining and Metallurgy Bob Hartzell, U.S. National Mining Hall of Fame Prof. Jeremy Mouat, University of Alberta

Frances Noone, Teck Cominco Archives, Trail BC

Jo-Anne Colby, CP Archives, Montreal Dr. Phillip Mackey, Xstrata Process Support Don Wilson, Crowsnest Highway Project, BC Prof. Mike Nelson, University of Utah Dr. Peter Koh, CSIRO, Melbourne, Australia Michael Allan, Teck Cominco Dr. Michael Fairweather, Consultant Prof. Jim Finch, Dr. Cesar Gomez, McGill University, Montreal Dr. Alban Lynch, Rick West, Angie Spry, AusIMM, Australia Dr. Glenn Dobby, SGS-Minnovex

Diane Mitchell, B.C. Mining Museum

Canadian Mining Hall of Fame

Thank you

Acknowledgements....Many Thanks to

Canadian Mineral Processors

Robertina Pillo and the Canadian Institute of Mining and Metallurgy Bob Hartzell, U.S. National Mining Hall of Fame Prof. Jeremy Mouat, University of Alberta

Frances Noone, Teck Cominco Archives, Trail BC

Jo-Anne Colby, CP Archives, Montreal Dr. Phillip Mackey, Xstrata Process Support Don Wilson, Crowsnest Highway Project, BC Prof. Mike Nelson, University of Utah Dr. Peter Koh, CSIRO, Melbourne, Australia Michael Allan, Teck Cominco Dr. Michael Fairweather, Consultant Prof. Jim Finch, Dr. Cesar Gomez, McGill University, Montreal Dr. Alban Lynch, Rick West, Angie Spry, AusIMM, Australia Dr. Glenn Dobby, SGS-Minnovex

Diane Mitchell, B.C. Mining Museum

Canadian Mining Hall of Fame