Você está na página 1de 19

Improved Processes of

Extracting Copper from Its Ores


William W. Culver
State University of New York at Plattsburgh
Hunt & Douglas Copper Process
• What is it?
First commercial “wet” process for low-grade
copper. Patented 1869 in USA, 1870 in Chile.
• Why is it important?
Memory - reminds “us” of the deep roots of
chemical extraction of metals, and pioneering
efforts in Chile to process low-grade copper.
• How did I come to study it?
Good question.
Selection from Patent Paragraph 2 Paragraph 2

“For the extraction of copper ores by this


process it is necessary that it should be in
the state of protoxide [CuO], or suboxide
[Cu2O], or some compound of these oxides…
The pulverized and naturally or artificially
oxidized ore are then digested with a watery
solution of protosalt of iron, with or without
the addition of an earthy or alkaline
chloride. We prefer the neutral
protochloride of iron [FeCl2]… By the action
of a solution of protochloride of iron [FeCl2]
on the oxides of copper [CuO & Cu2O] these
are converted into dichloride of copper
[CuCl2], which is readily soluble in
concentrated solutions of earthy or alkaline
chlorides – such as common salt [NaCl]. At
the same time the iron separates from the
solution as an insoluble oxychloride [FeOCl].”

[bracketed modern formulae are added]


The Chemistry
1869 Hunt in Scientific Paper 1953 Van Arsdale Hydrometallurgy
• First stage reactions: • Molecular Formula
Cu2O + FeCl = CuO + FeCl2 + H2O →
Cu2Cl + FeO CuCl2 + Fe(OH)2
• Second stage reactions:
Cu2Cl + 3FeO = • Balanced Equation
Cu2 + FeCl + Fe2O3 3Cu2+O2-(s) + 2Fe2+Cl2-(aq) + 3H2O →
• Final Result: 2CuCl (aq) + Cu2+Cl2-(aq) +
3Cu2O + 2FeCl = Fe(OH)3(aq)
2Cu2Cl + 2Cu + Fe2O3
(Errors for cuprous chloride & ferrous chloride
traced back to atomic weight errors.)
Context of the Terminology
• Vat leaching method based on chlorine’s observed
high reactivity & strong oxidizing capacity.
• 1860s discovery of elements – chemistry’s frontier.
• Mendeleev’s periodic table published 1869.
• Determination of atomic weights debated.
• Isotopes unknown (atomic weight confusion).
• Ions unknown.
• As issues were clarified, language evolved.
Table 1: Published Atomic Weights
with the Hunt & Douglas Process
1840 1858 1858 1869 1876
Element

Graham Fownes Cannizzaro Medeleev Hunt & Modern


Douglas
Cu 31.71 31.7 63 63.4 31.75 63.55

Fe 27.18 28 ---- 56 28 55.85

Cl 35.47 35.5 35.5 35.5 35.5 35.45

O 8.01 8 16 16 8 16
Table 2: Formula and Terminology
Modern
Comparison Chart
Hunt & Hunt (1869) Other Hunt Hunt & Douglas Modern
Molecula Douglas Hunt & Scientific & Douglas (1876) Latin Modern
r/Ionic (1876) Douglas Copper (1869) Promotional System Stock System
Formulas Formula (1869) Patent Article Terminology Booklet Names Names
Cu2O/ Cu2O oxides of cuprous oxyd suboxide dinoxyd of cuprous copper (I)
Cu2+O2 copper/red copper oxide oxide
CuO/ Cu2O2 oxides of oxidum protoxide protoxyd of cupric oxide copper (II)
Cu2+O2- copper/black cuprosum copper oxide
CuCl/ Cu2Cl cuprous protochlorid of cuprous copper (I)
Cu+Cl- chlorid copper chloride chloride
CuCl2/ dichloride of cupric chlorid dichloride of
Cu2+Cl2- copper copper
FeCl2/ FeCl protochloride ferrous iron protochloride of ferrous iron (II)
Fe2+Cl2- of iron chlorid dichloride iron chloride chloride
FeO/ FeO ferrous oxyd ferrous oxyd hydrated ferrous ferrous iron (II) oxide
Fe2+O2- oxide oxide
Fe2O3/ F2O3 ferric oxyd ferric oxyd ferric oxide iron (III)
Fe22+O32- oxide
FeOCl/ iron oxychloride iron (III)
Fe3+O2-Cl- oxychloride of iron oxychloride
NaCl/ chlorid of chlorid of common salt chlorid of sodium sodium
Na+Cl- sodium sodium sodium chloride chloride
Who Were the Patent Holders?
James Douglas T. Sterry Hunt
Their Careers
Douglas CV Hunt CV
• Born 1837 Quebec City, Canada • Born 1826 Norwich, Connecticut
• Education: University of Edinburgh & • Education: Yale University with B. Silliman
Queen’s College, Kingston, Canada • Geological Survey of Canada 1846-72
• Degree in theology, with some studies of • Laval University, Prof. Chemistry 1856-62
medicine (chemistry) at Laval University • McGill University, Prof. Chemistry
• 1864 took charge of family investment at • MIT, Prof. geology 1872-78
Harvey Hill Copper Mine as high-grade
ore exhausted (bornite) • Patents with Douglas 1869-1892
• 1867 tested Whelpley & Storer Process • Published 6 scientific books
• 1869 patented copper process with Hunt • Published 346 scientific articles
• 1871 consulting in Chile nine months • Member & officer of most USA, Canadian
& European scientific societies
• 1875 Chemical Copper Corporation
• Questioned “atom theory” in favor of
• 1880 Phelps Dodge & Arizona continuous matter
• Published some 300 articles, 5 books • Died: 1892 New York City
• Died 1918 New York City
Hunt & Douglas Process Plants
• Harvey Hill Mine, St-Jacques de Leeds, Quebec
1869-75.
• Compañia de Minas de la Invernada, Tiltil
1870-75.
• Ore Knob Mining Company, 1873-75.
• Sociedad Minera de Andacollo, 1870-?
• Chemical Copper Co., Phoenixville, Penn. 1875-80.
• Stewart Smelter, Georgetown, Colorado, 1874-80.
• Kansas City Smelting & Refining, 1895-97.
Harvey Hill Mine 1860
Compañia de Minas de la Invernada
• “Para que V.E. pueda juzgar mejor
• Chile had venture capital. del valor del procedimiento y los
grandes ventajas que va a reportar al
• Investors with a correct país dice, que existen grandes
cantidades del desmontes de cobre
diagnosis of the looming de 4 a 5% en Chile que hasta ahora
crisis in Chile. se han considerado de ningún valor,
también hay cerros inmensos de
• Copper investors minerales de baja ley que
assuming great risk to actualmente nadie esplota por no
move the industry and conocer un método barato de
beneficiar."
the country ahead. -Juan Stewart Jackson, President,
• Chile lagged in science & Compañia de Minas de la Invernada, to
Pres. José Joaquín Pérez, 1871
engineering to keep at it.
Ore Knob, North Carolina, USA
water, ore, solution

Leaching tanks
Roasting
furnace Precipitation
tanks
Solution
recovery
Chemical Copper Company 1876

Leaching Tank
House
Chemical Copper Company
• Five years custom ore processing allowed for
continual experimentation with varied ores.
• Developed hydrometallurgy as basis for a
custom smelter.
• First copper electrolysis in North America.
• Where Douglas developed his skill as a
metallurgist.
• Bankrupt after a second furnace house fire.
Problems and Subsequent Patents
Year Patent # Name Title of Patent Extraction
Patentee (solvent/product) Method

1869 86.754 H&D Improvement in Processes of Extracting Copper from Its Ores iron precipitate
(protochloride of iron & common salt /cuprous chloride)

1874 151,763 D, H, S Improvement in Extracting Silver, Gold, and Other Metals from iron precipitate
Their Ores
(protochloride of iron & common salt/chloride of copper )
1880 227,902 H&D Extracting Copper from Ores iron precipitation
(chloride & sulphurous acid/dichloride of copper) or filter

1887 364,174 H&D Process of Extracting Copper from Its Ores iron precipitation
(ferrous chloride & common salt/cuprous & cupric chloride) or filter

1893 506,985 D Methods of Separating and Recovering Copper iron precipitation


(chloride of iron & sulphurous acid/sub-chloride of copper) or filter

1896 563,144 D Process of Extracting Copper from Ores Electrolysis


(“chlorid” salt & sulphurous-acid gas/cuprous chloride)

1900 664,537 D Process of Extracting Copper Electrolysis


(chlorid/cuprous chloride)
Hydrotechnology
• Hydrometallurgy vs. Hydrotechnology.
• Shared idea – place ground ore in a solution in
order to manipulate desired metal.
• Leach.
• Precipitate.
• Electrolysis.
• Float off top.
Reflections
• Low-grade metal mining is on defensive today.
• Low-grade metal mining is humanity’s way ahead.
• Considering historical perspectives is one way to
maintain dialogue.
• Hydrometallurgists have a burden to be creative in
solving known problems.
• Investors take a risk, but must balance return with
safety for workers and the environment.
Conclusions
• The Hunt & Douglas Copper Process “worked.”
• It is an early instance of scientific insight leading
to business opportunity.
• Ahead were decades perfecting the necessary
engineering and methods:
-non-selective mining,
-overall mine/plant scale of operation,
-particle sizing and sorting.
• Blind alleys and dead-ends helped find the way
ahead for overcoming the low-grade challenge.

Você também pode gostar