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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


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]

Paragraph 2

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 chlorines observed
high reactivity & strong oxidizing capacity.
1860s discovery of elements chemistrys frontier.
Mendeleevs 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
1858
Fownes

Cu

31.71

31.7

63

63.4

1876
Hunt &
Douglas
31.75

Fe

27.18

28

----

56

28

55.85

Cl

35.47

35.5

35.5

35.5

35.5

35.45

8.01

16

16

16

Element

1840
Graham

1858
1869
Cannizzaro Medeleev

Modern
63.55

Table 2: Formula and Terminology


Comparison Chart
Modern
Molecula
r/Ionic
Formulas
Cu2O/
Cu2+O2
CuO/
Cu2+O2CuCl/
Cu+ClCuCl2/
Cu2+Cl2FeCl2/
Fe2+Cl2FeO/
Fe2+O2Fe2O3/
Fe22+O32FeOCl/
Fe3+O2-ClNaCl/
Na+Cl-

Hunt &
Douglas
(1876)
Formula
Cu2O
Cu2O2

Hunt &
Douglas
(1869) Patent
oxides of
copper/red
oxides of
copper/black

Cu2Cl

FeO

dichloride of
copper
protochloride
of iron
ferrous oxyd

F2O3

ferric oxyd

FeCl

iron
oxychloride
chlorid of
sodium

Hunt (1869)
Scientific
Copper
Article
cuprous oxyd

Other Hunt
& Douglas
(1869)
Terminology
suboxide

oxidum
cuprosum
cuprous
chlorid
cupric chlorid

protoxide

ferrous
chlorid
ferrous oxyd

iron
dichloride

Hunt & Douglas


(1876)
Promotional
Booklet
dinoxyd of
copper
protoxyd of
copper
protochlorid of
copper
dichloride of
copper
protochloride of
iron
hydrated ferrous
oxide

ferric oxyd

chlorid of
sodium

oxychloride
of iron
common salt

chlorid of
sodium

Modern
Latin
System
Names
cuprous
oxide
cupric oxide
cuprous
chloride

ferrous
chloride
ferrous
oxide
ferric oxide

sodium
chloride

Modern
Stock System
Names
copper (I)
oxide
copper (II)
oxide
copper (I)
chloride

iron (II)
chloride
iron (II) oxide
iron (III)
oxide
iron (III)
oxychloride
sodium
chloride

Who Were the Patent Holders?


James Douglas

T. Sterry Hunt

Their Careers

Douglas CV

Born 1837 Quebec City, Canada


Education: University of Edinburgh &
Queens College, Kingston, Canada
Degree in theology, with some studies of
medicine (chemistry) at Laval University
1864 took charge of family investment at
Harvey Hill Copper Mine as high-grade
ore exhausted (bornite)
1867 tested Whelpley & Storer Process
1869 patented copper process with Hunt
1871 consulting in Chile nine months
1875 Chemical Copper Corporation
1880 Phelps Dodge & Arizona
Published some 300 articles, 5 books
Died 1918 New York City

Hunt CV

Born 1826 Norwich, Connecticut


Education: Yale University with B. Silliman
Geological Survey of Canada 1846-72
Laval University, Prof. Chemistry 1856-62
McGill University, Prof. Chemistry
MIT, Prof. geology 1872-78
Patents with Douglas 1869-1892
Published 6 scientific books
Published 346 scientific articles
Member & officer of most USA, Canadian
& European scientific societies
Questioned atom theory in favor of
continuous matter
Died: 1892 New York City

Hunt & Douglas Process Plants


Harvey Hill Mine, St-Jacques de Leeds, Quebec
1869-75.
Compaia 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

Compaia de Minas de la Invernada


Chile had venture capital.
Investors with a correct
diagnosis of the looming
crisis in Chile.
Copper investors
assuming great risk to
move the industry and
the country ahead.
Chile lagged in science &
engineering to keep at it.

Para que V.E. pueda juzgar mejor


del valor del procedimiento y los
grandes ventajas que va a reportar al
pas dice, que existen grandes
cantidades del desmontes de cobre
de 4 a 5% en Chile que hasta ahora
se han considerado de ningn valor,
tambin hay cerros inmensos de
minerales de baja ley que
actualmente nadie esplota por no
conocer un mtodo barato de
beneficiar."
-Juan Stewart Jackson, President,
Compaia de Minas de la Invernada, to
Pres. Jos Joaqun Prez, 1871

Ore Knob, North Carolina, USA


water, ore, solution

Roasting
furnace

Leaching tanks
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
Patentee

Title of Patent
(solvent/product)

Extraction
Method

1869 86.754

H&D

Improvement in Processes of Extracting Copper from Its Ores


(protochloride of iron & common salt /cuprous chloride)

iron precipitate

1874 151,763

D, H, S

iron precipitate

1880 227,902

H&D

Improvement in Extracting Silver, Gold, and Other Metals from


Their Ores
(protochloride of iron & common salt/chloride of copper )
Extracting Copper from Ores
(chloride & sulphurous acid/dichloride of copper)

1887 364,174

H&D

Process of Extracting Copper from Its Ores


(ferrous chloride & common salt/cuprous & cupric chloride)

iron precipitation
or filter

1893 506,985

Methods of Separating and Recovering Copper


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

iron precipitation
or filter

1896 563,144

Process of Extracting Copper from Ores


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

Electrolysis

1900 664,537

Process of Extracting Copper


(chlorid/cuprous chloride)

Electrolysis

iron precipitation
or filter

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 humanitys 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.