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Section 16

Molybdenum
J . D. Vincent and J. F. Shirley. Section Editors

CONTENTS
GENERAL REFERENCES . . . . . . . . . . . . . . . . . 16-1 Molybdenite byproduct plant operating costs . . . . . 16-24
Plant descriptions . . . . . . . . . . . . . . . . . . . . . 16-24
Chapter I . INTRODUCTION-I . D . VINCENT . . . . . 16-2
Chapter 4 . CONVERSION OPERATIONS-
Chapter 2. PRIMARY MOLYBDENITE OR& 1. BRIGGSAND M . VERTES . . . . . . . . . . . . . 16-30
R. E. CUTHERBERTSON AND J . D . VINCENT. . . 16-2 Technical grade oxide . . . . . . . . . . . . . . . . . 30
General . . . . . . . . . . . . . . . . . . . . . . . . . 2 Molybdic oxide briquettes . . . . . . . . . . . . . . . 31
Geology . . . . . . . . . . . . . . . . . . . . . . . . . 2 Sublimed molybdic oxide . . . . . . . . . . . . . . . 31
Treatment of primary molybdenum ores . . . . . . . 2 Ammonium molybdate . . . . . . . . . . . . . . . . 31
Plant description and flowsheets . . . . . . . . . . . . . . 3 Ferromolybdenum . . . . . . . . . . . . . . . . . . . 31
Climax Molybdenum Co. . . . . . . . . . . . . . . . .
.
Questa mine Molybdenum Corp. of America . . . . .
Endako Mines. Ltd . . . . . . . . . . . . . . . . . . . .
3
4
4
Chapter 5. MOLYBDENUM PRODUCTS AND USES-
J . BRIGGSAND M . VERTES. . . . . . . . . . . . . 16-31
Urad mine. AMAX Inc . . . . . . . . . . . . . . . . . . 6 General . . . . . . . . . . . . . . . . . . . . . . . . . 31
Henderson mill. AMAX Inc . . . . . . . . . . . . . . . 9 Molybdenum metal . . . . . . . . . . . . . . . . . . 32
British Columbia Molybdenum Ltd . . . . . . . . . . . I2 Abrasion-resistant irons and steels . . . . . . . . . . . 32
Molybdenite Corp. of Canada. Ltd . . . . . . . . . . . . 16 High-chromium white irons . . . . . . . . . . . . . . 32
Climax-Treatment of oxidized molybdenum ore . . . 17 Steels . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Engineering steels . . . . . . . . . . . . . . . . . . . 33
Chapter 3. BYPRODUCT MOLYBDENITE- Stainless steels . . . . . . . . . . . . . . . . . . . . . 34
1. F . SHIRLEYAND A . SUTULOV . . . . . . . . Tool steels . . . . . . . . . . . . . . . . . . . . . . . 35
General . . . . . . . . . . . . . . . . . . . . . . . . Chemicals and lubricants . . . . . . . . . . . . . . . . . 35
Geology . . . . . . . . . . . . . . . . . . . . . . . . Catalysts . . . . . . . . . . . . . . . . . . . . . . . . 35
Recovery of molybdenite from copper porphyry ores . Lubricants . . . . . . . . . . . . . . . . . . . . . . . 35
General . . . . . . . . . . . . . . . . . . . . . . . . Pigments . . . . . . . . . . . . . . . . . . . . . . . . 35
Factors affecting the primary recovery . . . . . . . Corrosion inhibitors . . . . . . . . . . . . . . . . . . 35
The recovery of molybdenite from the molybdenum Plants and soils . . . . . . . . . . . . . . . . . . . . . 36
enriched product . . . . . . . . . . . . . . .
Molybdenite-copper sulfide separation processes . . . LIST OF REFERENCES . . . . . . . . . . . . . . . . . . . 16-36
General . . . . . . . . . . . . . . . . . . . . . . . . Manuscript. July 1978

General References
Grimes. G.R., and Witkamp. G., "Climax Conversion Practice 11." Schneider. V.B., "Molybdenum. Mineral Report 6. " 1963. Mineral
Journal of Metals, Feb . 1971. pp. 17-24 .
. .
Killeffer. D.H., and Linz A .. Molybdenum Compounds Their Chemis-
.
Resources Div.. Dept . of Mines and Technical Surveys Ottawa.
Sutulov. A.. Molybdenum Extractive Metallurgy. M . Pease. trans.,
try and Techno1ogy. Interscience Publishers. New York. 1952.
.
Mclnnis W., "Molybdenum-A Materials Survey," U.S. Bureau of
Mines. 1957.
.
University of Conception. Chile. 1965.
Wheeler E.S., "Climax Conversion Practice." AIME Metals Technol-
ogy 1944.
Mineral Facts and Pmblems. U.S. Bureau of Mines. 1970. p . 61.
MOLYBDENUM

1. INTRODUCTION
J. D. VINCENT
Molybdenum, the 42nd element in the periodic table, is now a (PbMoO,) from Arizona and Nevada, and a small amount of molyb-
very important metal in industry of the United States and the world. denite was produced up to the early 1970s as a coproduct from two
Chemically, it is a very complex element having valences of 0, +2. molybdenum-bismuth mines in Quebec, Canada.
+3, +4, +5, and +6, and can exist as a mixture of these valences The first byproduct production of molybdenite from a copper con-
in many compounds. It was discovered and separated by Scheele in centrating operation was achieved at Cananea. Sonora, Mexico, and
1778. was followed shortly by the Utah division of Kennecott Copper Co.
At the present time, molybdenite is the only important commercial in the mid-1930s.
source of molybdenum. Molybdenum occurs in some 12-14 different This section of the Handbook is divided into four main subdivi-
recognized minerals, but practically all of the production is molybde- sions: Chapter 2, which deals with the concentration and recovery
nite. As late as 1915, it was considered a rare metal. Germany made of molybdenite from primary molybdenum ores; Chapter 3. which
extensive use of it during the first world war, which resulted in'the deals with the recovery and separation of molybdenite as a byproduct
establishment of a molybdenum industry in the United States at Cli- from copper production; Chapter 4, which deals with the conversion
max, Colo., in 1917. It was not until the mid-1920s when its introduc- practices employed for convening molybdenite to the oxide or metal
tion to steelmaking developed for the US automobile industry that form; and Chapter 5, which covers the uses of molybdenum in steel-
the metal gained important acceptance. The first notable example making, chemicals, pigments, lubrication, catalysts, etc.
was the Willis-Saint Claire automobile introduced in 1921 by C. The Free World molybdenum production, for the past eight years
Harold Willis, formerly chief metallurgist for Ford Motor Co. from all sources, is shown in Table 1.
Molybdenum has also been produced in the US from wulfenite

Table 1. Free World Molybdenum Supply


Million Ib of molybdenum in concentrates
1965 1966 1967 1968 1969 1910 1971a 1972
U S mine production 77 91 89 94 101 113 112 118
Free World mine production
outside U S 22 35 37 34 43 55 50 45
Imports from Eastern Bloc 1 2 1 0 0 0 0 0
GSA Sales -
3 -9 -
2 -3 - 4 -5 -0 -0
Total Free World 103 137 129 131 148 173 162 163
' Revised.
b Estimated.

2. PRIMARY MOLYBDENITE ORES


AND J. D. VINCENT
General Treatment of Primary Molybdenum Ores
In 1978 there were four primary molybdenite recovery plants in All primary molybdenum ores are low in molybdenite, the content
operation: Climax, Endako. Questa, and Henderson. For over half ranging from less than 0.20% MoS2 to a high of about 0.40% MoS2.
a century the Climax mine has been by far the largest and most A high resistance to grinding is a common ore characteristic combined
important source of molybdenum in the world. During the early 1970s with a habit of very fine dissemination of molybdenite in the siliceous
a few primary molybdenite mines in British Columbia were shut down portion of the ore. Because of low MoS2 content. high hardness,
due to adverse economical conditions. The largest of these was British and fine dissemination of molybdenite in primary ores, it has been
Columbia Molybdenum, formerly owned by Kennecott Copper Corp. necessary to develop a special mill treatment which yields an accepta-
The Climax plant and operations are described in detail and the opera- ble recovery at a reasonably low milling cost. Essentially, the treatment
tlons of the other plants are summarized following a general discussion consists of intensive rougher Rotation at a relatively coarse grind
of recovering molybdenite from primarily molybdenite ores. Recovery with production of a low grade rougher froth containing a substantial
of molybdenite as a byproduct will be taken up in Chapter 3. percentage of the molybdenite in the form of low grade middling
particles, followed with multistage regrinding to liberate the locked
molybdenite and several stages of flotation cleaning to produce a
finished grade concentrate. Rougher flotation on pulp ground to ap-
Molybdenite production from mlnes in which it is the sole or proximately 35 mesh is common practice, even if complete liberation
preponderantly important mineral is confined to ore bodies in granites of molybdenite from siliceous gangue may require regrinding to 200
or igneous-type rocks or pegmatite dikes. More than one state of mesh.
mineralization is sometimes present as at Climax, York, Hardy, and The Rotation of middling particles with a very low content of
Questa. In the case of Climax, important byproduct recovery of tung- molybdenite in the rougher Rotation step has been made possible
sten, tin, pyrite, and monazite is also attained. The molybdenite is by the application of a combination of reagents first developed at
commonly disseminated very finely in the siliceous granitic gangue the Climax mill and used with some modification in the treatment
but does occur in stringers and blebs in silicified mineral solution of all primary molybdenum ores. The reagents commonly employed
channels. and their functions in Rotation are:
PRIMARY MOL.YBDENITE ORES 16-3

Petroleum Hydroarbon. This is the chief collecting reagent used


in molybdenite flotation. It may either be a kerosene-type oil or a Precambrian schists and granites and Tertiary quartz monzonites
special fraction of somewhat higher viscosity classified as a pale neutral and granites, all of which can be orebearing and containing valuable
oil with low content of paraffin wax and relatively free from unsatu- concentrations of molybdenite, wolframite, cassiterite, and pyrite.
rated compounds. It is added in amounts ranging from 0.1 to 0.8 compose the ore body at this mine.
lb per ton of flotation feed.
Wetting Agent or Detergent. The purpose of this reagent is to Concentration
help to incorporate the hydrocarbon oil in the ore pulp and stabilize
the froth. A reagent of this type is sold under the trade name Artic Ore is delivered from the underground operations by trains consist-
Syntex L and is classified as a sulfated monoglyceride of coconut ing of 25 cars; each train holds approximately 207 tons or 8.3 tons
oil origin. A wide range of wetting agents serves the same purpose. per car.
but not many are as well adapted to molybdmite flotation as Artic Primary and Secondary Crushing. Primary crushing is accom-
Syntax L. This type of reagent is employed in a range of 0.01 to plished on the surface for the newly developed open pit by two 48 x M
0.05 Ib per ton of flotation feed. in. Birdsboro Buchanan jaw crushers which are fed from bins with
Pine Oil or Other Frothing Agent The purpose of a frothing Ross chain feeders. On the Stork, or 300-ft level, a 60-in. Nordberg
agent such as pine oil is to act as a froth modifier and a partial gyratory is installed, and on the 600 level, a 54-in. Traylor gyratory.
collector of molybdenite. Pine oil, or its equivalent, aids in producing Primary jaw crushing is followed by secondary crushing with two
a froth that carries a maximum load of free molybdenite and low Nordberg 7-ft standard cone crushers while the Stork level gyratory
grade middling particles. A usual level of addition is from 0.02-0.08 is followed by secondary crushing with two Nordberg 7-ft standard
Ib per ton of flotation feed. cone crushers. P r ~ e n t l y(1973). there are two 7-ft standard gyratory
Pine oil also serves the function of an auxiliary collecting agent. crushers following the 54-in. Traylor on the 600 level.
Lime or Other pH Modifier. The favorable pH for flotation is Tertiary Crushing. Tertiary crushing for all secondary screened
7.5-8.5. The importance of pH control is to neutralize acid salts in product is consolidated, consisting of ten Nordberg 7-ft shorthead
the ore pulp which cause flocculation of any clay-type slime constitu- cone crushers. The product from the tertiary crushing stage is held
ents. Slimes seriously interfere with optimum utilization of collecting to %72% -3 mesh. Single state ball milling in closed circuit with
agents and thus depress recovery. rake classifiers is used throughout the concentrator except for four
Sodium Silicate. If an ore contains an appreciable amount of sections where cyclones are installed. The ball milling circuit consists
clay slime, sodium silicate or some other dispersing rmgent is required of eight 9 x 8-ft Marcy grate discharge mills, four 9 x 9-ft Marcy grate
for optimum recovery. The amount of dispersant is in the range of discharge mills, and eight I3 x 1 2 4 Marcy and Allis-Chalmers over-
0 . 2 0 . 8 0 Ib per ton of flotation feed. Too much dispersant destroys flow discharge mills. Ore is fed to the ball mills by conveyors, which
froth stability; too little is ineffective in combatting the bad effect are equipped with weightometers, from individual fine ore storage
of flocculated slime. bins. Feed tonnage is adjusted to maintain a 3 2 4 0 % + 100-mesh
Sodium Cyanide. This reagent is employed to depress pyrite and classifier overflow. Circulating loads average 250-300%. Ball mill
chalcopyrite. It is customarily employed in cleaning stages of flotation. discharge solids average 78%. Reagents of vapor oil and Syntex are
In case of a serious problem of pyrite control, a small amount of added to the ball mill feed with some staging to flotation. Daily ball
cyanide may be added to rougher flotation to minimize the amount charges amount to 1.55 "soft" balls per ton of ore which are added
of pyrite which otherwise must be reground and eliminated in the to the individual ball mill units. All ball mill feed samples are gathered
one or more stages of regrinding and cleaning. automatically.
Nokes Reagent. This reagent, a reaction product of caustic soda Grinding control is by Foxboror 2-30 computer with direct digital
and phosphorus pentasulfide, is added to depress gakna. It is usually control based on particle size prediction.
added to cleaning stages of flotation, but in severe cases it also may Each unit classifier overflow is pumped to flotation. Flotat~onis
be used in small amounts of rougher flotation. At the Urad mill of accomplished in 36-cu-ft Weinig flotation machines in series except
AMAX lead depressants in the flotation circuits are not adequate for one unit of Denver 300cu-ft cells and two units of Agitair 300
and a leaching step with ferric chloride is applied to cleaned molybde- cu-ft cells. Average flotation retention time for all units is 12-16
nite concentrate. min. Rougher concentrate averages 5 6 % MOSSwith 89% Most re-
covery. Total rougher flotation tailings reports to the byproduct plant.
All concentrate and tailings samples are sampled automatically.
PLANT DESCRIPTIONS AND FLOWSHEETS Cleaner concentration is accomplished with three stages of regrind-
ing and five stages of reflotation. Final concentrate grade is 90%
As indicated previously, the bulk of this chapter on processing MoS, with cleaner plant recovery of approximately 98.5%.
primary molybdmite ores is devoted to descriptions of the four plants Final concentrate is partially retreated to make a high grade lubri-
in operation in 1973-1978--Climax, Endako, Questa, and Henderson. cation grade Most product which forms pan of the production from
Summary descriptions of two Canadian plants-British Columbia the mill.
Molybdenum and Molybdenite Corp. of Canada-shut down in the
The average daily throughput is approximately 47,000 tons and
early 1970s. are also included. This portion of the chapter concludes the feed averages approximately 0.30% MoS, with the rougher con-
with information on Climax's experimental treatment for recovery centrate averaging 5 4 % MoSl and the final tailing approximately
of molybdenum from an onidized fraction of ore.
0.035% MoSz. The overall MoS2 recovery is approximately 86% and
the ratio of concentration is 350 to 1.
Climax Molybdenum Co. The byproduct plant at Climax treats the rougher tailings to pro-
duce a 68% WOStungsten concentrate, a small amount of tin concen-
General
trate, a pyrite concentrate, and on occasion, a monazite concentrate.
Climax (a division of AMAX Inc.) milling and mining operations The treatment is based on gravity concentration followed by magnetic
are located on the summit of Frecmont Pass in the high Colorado separation and cleaning of the concentrates by removal of pyrite and
Rockies at an elevation of 11,300 ft. The operation had its start in monazite by flotation.
I917 but was shut down after World War I. It was resumed in the Tailings are transported down a tm-mile creek to two primary
earlv 19209 and has continued operating to this date with a production tailings dams, #2 and #5, with two emergency dams. Essentially
of over 400million tons of ore. Climax is the largest primary molybde all of the water is returned to the Climax milling circuit with a con-
num producer in the world. Byproduct production of tungsten, tin, sumption of 600 gal per ton of feed. Tailings are not thickened. Table
and pvrite is also a worthwhile feature of this plant. 2 illustrates the reagent type, consumption, and place of addition.
MOLYBDENUM

Table 2 Roapenh, Climax Mdvbdmum b.


--
Usage.
Reagent Ib per ton Purpoee Addition pohta
Rimary Concentratio-Based on Total Rougher Plant Feed
Pine oil 0.035 RLnary frother Ball mill feed
Vapor oil 0.67 Rimary collector 75% Ball mill feed
25% Flotation
0.034 Surfactant and has
frothing 76% Ball mill feed
characteristics 26% Flotation
Lime 0.30 pH regulation Ball mill feed
Sodium silicate 0.50 Slime dispersant Ball mill feed
Nokes reagent 0.03 Lead deprenaant Ball mill feed
Cleaner Coneentration-Based on Total Cleaner Plant Feed
Vapor oil 0.90 Collector Flotation
Sodium cyanide 0.25 Mte&
chalcopyrite
depression Flotation
Nokes reagent 0.90 Lead depression Pebble mills
Dowfmth 250 0.0s Fmther Flotation
Nalco 1601 0.006 Flocculent Thickener feed

The flowsheets for the molybdenum crushing and concentration tions, that is, earth fill with a gravel drainage core. Tailings are spilled
plant are given in Figs. 1-3. The accompanying text following each at one end through spigots and water is decanted at the o p p i t e
flowsheet g i v s the equipment that cornponds to the numbers shown end over a 2&ft long weir. Decant water is returned to the natural
on the bwsheets. drainage area and is not reused.
Power consumption averages 11.44 kw-hr per ton of ore, and
water is supplied from wells and from the surface; only about 10-
15% of this water is reclaimed. Water consumption is approximately
295 gal per ton of ore.
At the Questa mine of Molybdenum Corp. of America, the concen- The running time for the concentrator is approximately 97%.
trator can treat 15,000 tons of ore with a production of 12-14 million Figs. 4-8 give the flowsheet for the Q u s t a mill.
Ib of molybdenum per year. It is located high in the Sangre De Cristo
mountain range in northern New Mexico. Endako Mines, Ltd.
Geology
The Q u s t a ore body is associated with a biotized rock overlying The Endako concentrator in British Columbia has an average
an aplite intrusive about 4,000 ft wide and 10,000 long. The ore capacity of 27.500 tpd and produces 12-16 million Ib of molybdenum
contains only one valuable mineral, molybdenite, and that occurs per year.
in numerous closely spaced veins varying in thickness from "paint"
to over 3 in. and is found in both biotized breccia (andsite) and
porphyritic aplite. Heavy minerals (+2.9 sp gr) consist of pyrite, m e The ore body occurs in granite with dissemination of the molyb
lybdenite, chalcopyrite, sphalerite, galena. fluorite, magnetite, zircon, denite by quartz veining, and the primary concentration is done at
rutile, and manganosiderite. Light gravity minerals (-2.9 sp gr) in- a very coarse grind, 43% -200 m s h . In order to upgrade the molyb
clude quartz, orthoclase, oligoclase, biotite, calcite, and chlorite. denite content the final concentrate, the final product, is reground
Plant Description to 53% -9 pm.
Concentration
The ore is delivered to the mill site by 85-ton trucks. The capacity
of the plant is approximately 15,000 tpd with a production of 1-14 The ore is delivered to the crushing plant by 85-ton trucks to a
million Ib of molybdenum per year. The crushing is in three s t a g s 42 x65-in. Canadian Allis-Chalmers crusher. The crushed ore is
to 5% +M in., 80% -% in. Upgrading of plant feed is accomplished screened on an 8 x 20-ft primary screen which bypanres the undersize
by rejecting barren coarse material. The primary crusher discharge and finished f i n s at approximately %-I in. directly to the fine ore
is screened at 1.5 in. and the oversize up to 4-5 in. in discarded. bin. The oversize is stockpiled, which is common Canadian practice
The molybdenite concentrates in the finer sizes. The fine crushed in order to prevent freezing of the ore, and then conveyed through
ore is ground to 6% +35 mesh for rougher flotation in a single stage, the fine crushing plant to two 17 x 84-in. Canadii Allis-Chalmers
using cyclons for classification. The rougher flotation concentrate hydrocone crushers, while tertiary crushing is done by two 5 x 84-
is r a i d to marketable grade, using three stages of regrinding, one in. Canadian Allis-Chalmers hydrocone crushers in close circuit with
cleaning stage, followed by seven recleaners. The final concentrate two 8 x 20-R Canadian Allis-Chalmers screens.
is filtered, dried, and packed for shipment in 8000 Ib tote bins or The ore is fed to five 12 x 15-ft diam Canadian Allis-Chalmers
drums. The tote bins or drums are shipped via motor truck 88 m i l s rod mills, 1250 hp each, which deliver after classification the coarse
to the railroad, thence by rail to captive refinery or customer. material to two 5 x 15-tt diam Canadian All's-Chalmers ball mills,
Tailings are pumped to disposal site by two banks of LO x 8411. 1500 hp each. A small split of the cyclone undertlow is sent to a
centrifugal pumps in series, through two 10-in. I D polyurethanelined 9 x 1 3 4 Canadian Allis-Chalmers ball mill, 700 hp. Cyclone overtlow
steel pipelines. Pipelines are 8.5 miles long, leaving the mill at the goes to rougher flotation in 12 banks, 18 cell No. 40 Agitator flotation
8109-tt elevation, dropping the 7388-R elevation at 6.8 m i l s from cells, and four 18 cell banks No. 30 Denver cells. Rougher tailings
the plant, and then rising to 7500 ft at the tailings disposal area. It go directly to the tailing ponds; the rougher concentrate froth is cy-
is necessary to continuously maintain and patrol this line to prevent cloned twice and reground in a 6 x 12-ft daim Dominion ball mill,
possible pollution of a recreational area. The berm around the tailings whereas the overtlow from the cyclons is sent to a primary cleaning
dam has been built to meet state water control reservoir dam specifica- operation with two 18 cell No. 40 agitator flotation banks. From
Mine delivery

Storke level Open pit 6 0 0 f t level


7 7-
5 4 in, gyratory
7
54in. gyratory (16)
(I) 60in. gyratory
7 7
( 2 )Apron 8 belt conveyors Apron 8 belt conveyors (17)
7
(3 Surge bin Surge bin (3
7
( 4 ) Apron 8 belt conveyors
(I0)
Apron 8 belt conveyors Apron 8 belt conveyors (18)
t
Underflow Underflow Underflow

(6 ) Std cone crushers

(19)
7Conveyors
(12)
Std cone crusher
: Conveyors (20)
7 'I
Fine ore bin
P4 Y 7
Fine ore bin
1 w t i
c o n v i y o r s ( 2 1)

7
Flash bins
Weightorneter U ' F
*
T (I3)

7
(I4)
Short head cone crushers

1
(15)
m

Trippers conveyors
Milltbins
See flowsheet No. 2
FIG. I. Cliuux k w s h a t NO.I. Tbc quipmet i h W m in ( ) ia: (I) m 60-in. N o d k # gymtory c&, (2) 60-in. S c c p h e o a - A ~apron feeder, 60-in.

-
impact bclt coavcyor. 60-ia bclt a a v y o r 374 ft 1% (3) 5.000ton m e bin; (4) t m 48-h.StephewAdanuan apron feedas, two 48-in. impact bdt mnveyors.
two 48-ia bdt aaveyon 285 ft loale; ( 5 ) two 5 x 9-ft Ty-rock mtem mth 1%-in opninp, (6) two 7-fI et8ndud Symcna coae d s a ; S i n . gyratny; (10) thme
4.9-h apron feedas, two 4&ia i m p w bclt cmvcyors. m 5 C i bclt convey01208 A long; (I I) thme 5 x M Ty-nxk vrrcns with 1%-in. opening; (12) s u q c bina,
tbcn to thne 7 4 ltlndud S y m a ~aae enubss mtb 1%-in. euthg; (13) 41 S y m a ~& Robbiaa md deck with %-in. opmine (14) nine bclt feeders; (15)
nine rbottbad S y m m aae auahcrs witb %-in. senin& (16) m S i n . Tnylor gymtory d, (17) one Wi.S e M a m m n .pm I&, om 60-in bclt
conWO1435 ft h g , 3X) Ipm. o m 60-in. bdt coavcyor 45 ft long; (18) two UL-io. N i .pm kukm I2 Win. bclt convepn 31 and 404 ft @, (19) two 42411.
bclt coavcyom 1.166 and 1.341 ft 10% o m Win. bclt conveyor 185 ft (20)om 4.9-in. bclt convey01 30 ft lmg, LWIC 42-in. bdt umvcyor 3,043 ft long, one 48-
in bclt umvcyor 65 ft long.
( I ) Fine ore bins ore and producing around 21,000 Ib per day molybdenum. The plant
I was designed after the Climax plant, and the same reagent system
t
Feed belt convevors and weiahtometers
is used.
One unusual feature was the use of complete underground crush-
4
Automatic s o m ~ l e r s
ing. Another unusual feature was the leaching of lead from the final
concentrate. This was the first leach plant to leach lead from molyb
denite concentrate. The leach plant was able to leach lead from a
molybdenite concentrate containing 0.1% Pb and produce a product
containing about 0.025% Pb.

The molybdenite in the Urad ore body occurred either as moly

+
Overflow
Wood chio screens
paint or tightly spaced fractures or in veins with quartz, pyrite, fluorite,
and sericite. Closely spaced veins which vary From hairline coatings
to as much as 5 in. in width intersected to form a typical stockwork.
Silicification was not widespread, K-feldspathization gave the rock
a moderate hardness. Subcconomic qualities of galena and sphalerite

fL ~ o n c
(4)
t .
Flotot~on
1 Tailings
Concentrate were not recovered; rhodochrcsite was common. Host rocks of the
ore body were Precambrian granite and Tertiary quartz feldspar por-
phyry.
Scavenger flotation (5) Concentration

4
I
The ore was crushed in an underground station consisting of a

1
Tailings 48 x 60-in. Birdsbaro Buchanan primary jaw crusher, one 7-ft stan-
Automatic samplers dard Symons cone crusher, and two 7-ft shorthead extra heavy duty
Symons wne crushers. The crushing plant product was substantially
To byprod?cts plant -9% in. in size.
To cleaning plant
The grinding section consisted of two I3 x 1 2 4 ball mills with
See f lowsheet No. 3 1000 hp motors, and classification was accomplished by 78-in. Akens
FIG.2. Climax flowsheet No. 2. The equipment identification in ( ) is: (1) 8 classifiers. The grind was 35% +I00 mesh. The flotation circuit was
ore bins 35 x 35 R. I2 ore bins 401 60 ft; (2) eight 9 x 8-R Marcy grate discharge similar to that of Climax with three regrind and four cleaner reflotation
ball mills 450 hp, double scoop. 17 rpm, SIX 9 x 9-R h c y grate discharge ball stages following rougher concentration.
mills 600 hp, double scoop. 20 rpm, six 13 x 12-R Allis-Chalmcrs and h c y Typical results for 1969 were as follows:
overRow ball mills l,m0 hp. double scoop. 14.5 rpm; (3) I2 66-in. Akinsclassifius,
14 78-in. Akins cbifiers; (4) 312 3bin. Weinig flotation machina 290 rpm, 5 Mill feed 0.357% MoS2
hp per cell, 12 Dem No. 24 sub "A," 10 No. 48 Agitair; (5) 607 36in. Weinig Rougher tailing 0.050% MoS,
flotation machins 290 rpm, 5 hp per cell, 24 Deco No. 24 sub "A," 22 No.
48 Agitair. Rougher concentrate 7.37 % MoSI
Regrind tailing 0.206% MoS,
Final concentrate 93.65 % MoS,
that point on the flowsheet is rather typical of Climax and Endako
practice, and practically the same reagent scheme is used as a Climax. The overall ratio of concentration was 332: 1, and the overall
The reagent consumption and distribution is: recovery was 84.38% of the MoS, and the regrind circuit recovery
was 97.48%.
ColleftorSunray DX vapur oil added to rod and ball mills at 0.3 Tailings disposal was to two ponds, one above the plant site and
Ibper TRMF or 0.07 Ib per Ib MoSI. Added ncat and as 10% emulsion.
Frother-Pine oil added to ball mill discharge launder at 0.03 to 0.035 one below. The upper pond received the tailings by way of two sets
Ib per TRMF. Added neat. of 10 x 8-in. SRL pumps in series by means of two 8-in. rubber-hned
Emulsifier-Froth Stabihzer-Anic Syntex-L added to rod mill at 0.03 pipelines to a box above the dam. An 18 in. I D wood stave line
Ib per TRMF; added to 3.7% solution. delivered the tailings to 4-in. pipe spouts during summer months.
DispemtSodium silicate added to cleaner circutt at 0.180 Ib pcr The lower dam was reached by gravity through an 18-in. ID wood
T W F ; added as 25% solution. stave Line to kin. pipe spouts which were used during summer dam
DcprssantSodium cyanide added to cleaner circuit at 0.025 lb pcr building.
T W F ; added as 10% solution. Deprasant used to depress iron and coppcr
sulfids. (TRMF = tonnage rate metric feed.) In the winter, the 4-in. pipe spouts were replaced with 14-in.
discharge lines to fill behind the dams.
The present ore reserves are about 0.15% MoS2, the final wncen- The reagent consumption for 1969 was:
trate averages 90.6% MoS2, and the final tailings average about
0.028% MoS2. Rougher flotation recovery averages approximately Pine oil-frother, 0.059 Ib pcr ton to rougher ball mills. 0 . W Ib pcr
ton to first stage regrind flotation.
83% and cleaner flotation recovery 98.7%. The overall ratio of con- Syntex-A sulfonaled monoglyceride, an emulsifier for the hydrocarbon
centration approaches 700: 1. Power consumption is approximately collector; 0.021 Ib pcr ton on the rougher ball mills.
14.7 kw per ton including roasting, drying, briqueting. canning, and Hydrocarbon+Uector. A ylturated petroleum hydrocarbon Standard
miscellaneous services. The power is furnished by British Columbia Oil R.M. Industrial Oil #ll-P, 0.645 Ib pcr ton to the rougher ball miMs.
Hydro and Power Authority. QuicWimtpH control to rougher ball mills flccculant to thickener feed;
Tailings disposal is by 22 and 27-in. I D wood stave pipes, using flccculant to tailings; total usage 1.00 Ib pcr ton.
Sodium silicate--slime dispersant, 0.431 Ib per ton to rougher ball mills
gravity flow with closed drop boxes to maintain the gradient. Pond and 0.262 Ib pcr ton total to k t and fourth stage pebble mills.
retainment berms are built both by spigotting and cycloning. Phosprous pcntasulfidtlead dcp-t. 0.012 Ib per ton to rougher
The Endako flowsheets are shown in Figs. 9-1 1. ball mills and 0.027 Ib pcr ton total fed to each pcbble miU.
Sodium cyanidc--ooppcr,iron dep-t, 0.002 Ib per ton to rougher
Urad Mine ball mills and 0.027 Ib pcr ton total to regrind pbble milla.
General Automation
At the Urad mine of AMAX Inc. in Empire, Colo., no longer Crusher. TV cameras were used to monitor critical load points.
in operation, but in 1970 the operation was processing 6000 tpd of Horsepower control was used on the shorthead crusher to provide
PRIMARY MOLYBDENITE ORES

Rougher concentrate
7
Automatic sampler
I

+Fed
0 ' f low .)
cyclones ( I)

0'f low ,Iflow


1 ,'flow
-Thickeners -
*Pumps--4
f -fFrsit
0 ' f low f
stage cyclones ( 3 )
Tailings
I I~

(5)
First stage f l o t a t i o n
Conc
7 I
U-flow
First stage grinding ( 4 )

4-
I I
t
-Scavenger f lotation ( 6 )
7
Tailings
- O'flow
Pumps-

4
cyclones ( 7 )
t
I

Scavenaer flotation (10) &


Second stage grinding

+ Pumps- 4
PIG. 3. CLimu nosrahce No. 3. The
cquipmcnt idcntihtion in ( ) is: (I) --
four 2Cin. cyclones; (2) two 125-fi
thickmeners, o m 175-A thickener, (2)
8-D 15 B Kreha cyclones; (4) t h
6 R 8-in. by 20-A Marey grate din- Third stage flotation (13)
c h u g pbbk mills 22 rpn. Ua hp.
one 8 x 20-A b y grate dimcharge
pebble mill 22 rpm, MO hp; (5) 24
4
36in. Wchig Bot.tion ah with 21- -Tailings Conceit rate
in. impellers. 290 rpm. 5 hp per d l ;
(6) 48 3 6 i . Weinill Bomtion a h with --$-
21-in. impellua, 290 rpn. 5 hp pr Conditioners (14)
all; O D-I0 B Krrba cydonea; (8) I--
twn 8 x 20-A M u c y grate discharge
pbbk mills 22 rpm. 200 bp; (9) nine
36in. W* Boution cdla with 21-
I C
Fourth stage flotation (15)
in. impellers 290 rpm, 5 bp per a l l ;
(10) 44 36in. Wcinig dotation cdla L T a i hnas
4
Concentrate
with 21-in. impellax 290 rpm. 5 hp
p r a U ; ( l l ) 6 D 10BKrcbacyclonee;
(12) two 8x20-R b y grate die- 0 ' f low
c h u p pbbk mib 22 rpm. UX) hp; (16) T hickeners-1
(13) eight 36in. Wcini#Batuion alls
with 21-in. impdlun 290 rpm. 5 bp
per all; (14) two 8 x &A Dcvaaux
caditiamtm 875 rpm. 5 hp per condi- 7 Filtrate
J *Makeup water

ti- (15) w e n 36in. Wcini.gdoc.- t


ti00 & witb 21 in. impdlax 290 (18) Dryer
rpm. 5 bp per a4. (16) two 2Cin. I
thickeners; (17) two &A Agidis ffl- t
las;(18)mc21-in.~PdEcdrys, Packing
Cbarth or or-nmi.
MOLYBDENUM

-Alternate
- - - - - - - - - - - - - - - - - - - - - - - - -- I
I 85 ton ore trucks
I
I
I Oversize Alternate
6in. grizzly -- - - - - -7
1 4 8 i n . x 72in.

Unders~ze .- - - - - - - - - - - - - - - - - -- - - - ---
I: Alternate
L - - - -- - -
F-use

,..-..-..-...7-- ---
Not in use
Coarse ore bins
4
Weightometer
I

r-Undersize I - 6 f t x 1 6 f t double deckt vibrating screen--1Oversize


t
I-7ft standard cone crusher
I
d
.f
2 - 6 f t x l o f t double deck vibrating screens
I
t
2 - 7 f t shorthead cone crushers d
-1
Fine ore bins
t
5 Weiahtometers

1-15ftx19ft 2in. 3-13ft x l 4 f t + 1-11 b f t x14ft


overflow ball mill
v
Underflow Overflow Overflow
grate discharge b a l l mills
I 7
3-26in. cyclones 16-20 in. cyclones
T1
Denver cleaner Fag cleaner I
cell tails cell tails I
t
2 Only distributors
I h e : No. 3 ball mill
+ cyclone overflow can
--------- go directly to NO. 7
To 7 rows of 18-59 CU. f t row of 18-59 CU. f t
Fag. rougher cells Fag rougher cells.
RG.4. Molycorp Qusta mill flowsh& No. I , crushing.
PRIMARY MOLYBDENITE ORES

Fine ore bins


-7--
5 Weightometers
I

I-15ftx i9ft 2in. 3-13ftx 14ft + 1-11 b f t x14ft


overflow ball mill grate discharge ball mills

Underflow Underflow
Overflow Overflow
3-26in. cyclones 16-20 in. cyclones
T I

Denver cleaner Fag. cleaner I


cell tails cell tails 1
e
2 Onlv distributors
I
II Note: No. 3 ball mill
cyclone overflow can
p---------'
To 7 rows of 18-59 cu. f t
go directly to No. 7
row of 18-59 cu. ft
Fag. rougher cells Fag. rougher cells.
FIG. 5. mill flowabat
Molycorp QUCII~ No. 2, grinding.

maximum loading and overload protection. There was a centrally


located control room with trouble-light monitors and stopstart but-
tons. The Henderson molykdenite ore body contains in excess of 300
MUI. There was a centrally located control room with T V moni- million tons averaging 0.49% MOSS.The deposit has the shape of
tors, trouble-light monitors, and stopstart buttons. There was grind an inverted cup, slightly elongated in one direction and is a quartz-
control on the rougher ball mill circuit. Horsepower on classifier molyWenite stockwork that lies within a sequence of rhyolite porphy-
motors controlled water at the mill discharge. Automatic pH control- ries of mid-Tertiary age that have intruded the Prsambria Silver
lers of pH at the flotation cell regulated milk of lime addition to Plume granite. There are minor amounts of galma, chalcopyrite,
maintain a set pH. sphalerite, and about 3% pyrite. The major rock type is potassium
L e d P h t . Pulp density in leach tanks was controlled by read- feldsparquartz with a Bond Work Index of 12.5.
ing the density of Ohmart nuclear gage which then controlled the
valve adding FeCI. to system. AMAX filters were a batch-type air
pressure filter, which operated fill, blow, wash, and dump cycles via The ore is dumped continuously from side-hinged, bottomdump,
a control panel consisting of a series of Eagle timers. 20-ton cars to the crusher, which reduces the rock size to -9 in.
One of the unusual features of the plant was the leaching by See Table 3 for a list of the major equipment in the crusher and
hydrochloric acid and ferric chloride of the molykdenite concentrate the mill. The mill flowsheet is shown in Fig. 12. From the crusher,
to reduce the lead content of the final concentrate. The lead content the ore is conveyed to an open stockpile and in turn to each of the
was reduced to about 0.025% from approximately 0.10%. three primary mills.
Urad operations were discontinued in 1974. In comparing the Henderson plant to other molykdenum mius,
it is unique in that single-stage, semiautogenous grinding is used.
Each grinding line has a 28 x 14-Ft miU with two 3 , m h p motors.
Curmtly the mills are run at 69% critical speed with a 10% ball
charge, and 5-in. makeup balls are added during each shift.
The Henderson mill, owned and operated by AMAX. Inc., is The variables in the grinding circuit, which can be controlled or
located 20 miles southeast of Parshall, Colo., and is accessible from measured from the mill control room, are: feed rate, variable speed
Parshall on Grand Count Road 3 or from State Highway 9 via Ute pan feeders, and conveyor (the pan feeders can be ratiaed to each
Pass. The mine is on the east side of the Continental Divide near other); powm, sound; feed bearing pressure; discharge bearing pres-
Em- Colo.. while the mill is on the west side. To deliver the sure; feed water volume and ratio to feed rate; discharge water volume;
ore to the mill, a 14.2-mile twetrack railroad was built, 9.4 miles cyclone presstue; number of cyclones (the cyclones can be cut in or
of which is through a 14.5 x 16.5-ft tunnel. The loading drifts under- out with pneumatic valves from the control room); cyclone ovedow
ground are at 7,XYXft elevation and the primary crusher is at 9.175 density and particle size; the stockpile level; and the pH of flotation
ft. feed.
MOLYBDENUM

+=
t
I*--------
Ro tailings
7 rows of 18-59 cu. f t
Fag rougher cells
I I I
Conc. cells 5-18
Denver cleaner cel Is
(alt. 9-18)

1st scavenger Tailings


18-59 cu. f t Fag cleaner cells

I I 2nd scbvenger
8-59 cu. f t Fag cleaner cells
Concentrate I Underflow
1-
7 5 f t No. 2 thickener
I I

Overflow

I-8ft x 2 0 f t 'regrind mill

2-loin. cvclones
5 0 f t No. [ thickener-

Reclaim water tank


Tailings
b 3 r d scavenger
8-23 cu. f t Agitair cleaner cells
Concentrate
Tailings i
4
4 t h scavenger
6-23 cu, f t Agitair cleaner cells
Concentrate
Regrind pebble mills
FIG.6. Molycorp Qucsta mill flowsheet No.3, flotation scavenger.

The reagent scheme is similar to Climax, and all the reagents- returned to the head of the bank. This is done to make a certain
vapor oil, syntex, pine oil, sodium cyanide. Nokes, silicate, and lime grade so that the regrind~leanerplant does not have to be excessively
are added to the primary mills. In addition, there are capabilities large. It should be noted here that all the flotation cells, both in
of adding pine oil and syntex at the head of the roughers and stage the rougher and cleaner circuit have double launders, providing the
adding vapor oil and syntex at the two drops in the roughers. option to send the froth either as "concentrate" or "mids."
Esch primary mill has its own rougher flotation section, which The rougher concentrate is fed to 20-111. cyclones with the overflow
consists of two banks of 300-c~-ftcells in a 5-5-5 configuration, a going to the thickener and the undedow to the first-stage regrind
total of 30 cells for a 15-min retention time. The first five cells are mill. The total feed to the first-stage regrind is the rougher cyclone
concentrate and the last ten cells are considered mids, which are underflow and thickener underflow, which consists of first-stage
PRIMARY MOLYBDENITE ORES

t
-- I
---I------
Ro tailings
---- - --- -- ------- -- 14 7 Rows of 1 8 - 5 9 c u f t
Fag, rougher cells
, I Alternate iI
+
I

I
I
I
I
I 50-50split
iI (a l t.1- 8)
feed at cell 7
f
I
I
I------
~lternat:;
II
-'---I u ' f low L-- A l e - 1 0 0 c u f t Denver cleaner cells
I
I
I
Conc Conc
cells 1-6 cells 7-18
I
I < ,-\ Y
I
I
I Water reclaim I
- - -- - - -- -
I
I
C - - - - _- _---- 1

Not in use 2

3 - l o i n , diam 8,5mile
long tailings line 8 - 4 0 c u f t Agitair cells
I-12in. diam loop
3 mi Ies long
7 Tailings dam
7
E f f l u e n t to original
drainage basin 6- 23 c u f t Agitair cells
I

I Conc k p ,
L Tailings 4 t h reeieaners
-
4- 23 cu f t Aaitair c e l l s
Cone
I
Not in use-
r - - --- - -- - -- - - - - --- - - - -. 5 t h recleaners
- -*Iternate
I

-----42 - 2 3 c u f t Agitair c e l l s
Final conc
To 6 f t d i s k f i l t e r
L ---,- J ----------- - ------
FIG. 7. Molywrp Q u e b mill flowshat No. 4, Robtion cleaner, recleaner

cleaner middlings, second-stage cleaner tailings. cleanup from the the feed to No. 1 primary mill. The only reagents added in this
floor sumps, and, as previously mentioned, rougher cyclone ovedow. circuit are the deprasants, sodium cyanide and Nokes reagent, to
To m&e an acceptable ooneentrate grade, three stages of regrind- the regrind mills and a small amount of vapor oil and DF2YJ to
ing and four stages of cleaner flotation are used. Grinding media in the first flotation cells.
the regrind mills is 1% x 3-in. pebbles, which were screened out from As can be noted from the flowsheet, Fig. 12, the final tailings
16-12 MOLYBDENUM

2 - Leaves of 6 f t disk filter and transported by 10 and 25-ton flatdeck trucks 4% miles from
dock to mill site. Concentrate was shipped by 5 W I b cans to Vancouver
by barge.
The concentrator was a 6000 tpd design, but it was found possible
2 - D 1 6 2 0 - 6 t w i n screw at times to put as much as 9-10,000 tpd through the plant.
The ore average to the mill was 0.20 to 0.250% M o b ; the concen-
Holoflite driers trate produced an average 88.0-92.096 Mas, the tailings from the
mill averaged 0.02 to 0.025% MoS,. The ratio of concentration varied
from 400475: 1 with an overall recovery of 88.5-91.596. The plant
is now shut down but is held by AMAX Inc. to which it was sold
some time ago and may be expanded and reactivated in the near
future.
120,000 1b &To bulk t r u c k s
Geology
storage bin I or drums The ore-bearing zone is contained equally in three rock types:
I
I biotite hornfels, quartz monzonite porphyry, and quartz diorite. Mw
lybdenite and its associated minerals occur in a complex stockwork
of fractures and quartz veins. Associated sulfide are pyrite, chalwpy-
To tote bins rite, galena, sphalerite, and tetrhedrite. Molybdenite disseminated
within the rock is of minor importance.
Lamprophyre dikes are common within the ore zone. These post-
rucks to mineralization dikes are wmpoaed of altered olivine and hornblende
and are barren of molybdenite. Both hornfels and dikes are extremely
railhead abrasive, causing considerable attrition of wearing parts. Oxidation
extends about 30 ft below the erosion surface. In this interval some
FIG. 8. Molywrp Questa mill flowsheet No. 5, packing and drying. of the molybdenite is oxidized and much of the pyrite has formed
limonite. The oxidized molybdenite is not recoverable in the prevnt
mill circuit. Although the ore contains silver, gold, tungsten, and
consist of the rougher and first cleaner tailings, while all others are base metals in varying amounts, molybdenite is the only mineral that
recycled back to some other portion of the circuit. can be recovered economically at the present time.
The final product is filtered on disk filters and then dried to about
2-3% moisture in 16-ft long holoflite dryers. The concentrate is loaded Concentration
into tote bins and trucked to Kremmling, Colo., some 34 miles to The ore was delivered to the plant by 654011 trucks to a 42-in.
the north, and transferred to rail cars for shipment to the conversion gyratory crusher followed by one 7-ft standard cone crusher and
plants. one shorthead 7-ft cone crusher. The product of the crushing plant
Tailings are transported to the pond in a 36-in. concrete pipe was all -1 in. and substantially -34 in.
and the water is reclaimed by a decant system and pumped back to The grinding circuit was composed of one circuit of two rod and
the mill. three ball mills and the grind w& approximately 65% -100 mesh.
The reagent consumption was as follows:
Brltlsh Columbla Molybdenum
Kerosene wllcctor at the rate of approximately 0.28 Ib per ton was
General added in the ball mills and the roughing and scavenging stages of flotation.
MlBC frother at the rate of approximately 0.1 Ib per ton was added
At British Columbia Molybdenum Ltd., Alice Arms, BC, Canada. at the ball mills.
ore delivery was by 65-ton Haulpak units on a one-mile haulage route. Anic Syntcx I used at the rate of approximately 0.W3 Ib per ton was
Supplies were barged o r air freighted 600 miles from Vancouver, added at the rod mill.

Table 3. Maior Equipmer~t List, Henderson Mill


No. Manufacturer Size HP
Primary crusher Traylor 54x84 in. 500
Apmn feeder, 4-speed Stephens-Adamson 84 in. 100
No. 1 conveyor 60in. 3 @ 400
Primary grinding lines
each containing:
Apmn feeders, variable speed National Imn Ca. 48 in. 20
Primary mill Allis-Chalmers 28 x 14 f t 7,000
Cyclone feed pumps (one Georgia Imn Works 14x12 in.
standby)
Cyclones Krebs 26 in.
Rougher flotation cells DECO 300 cu f t
Rougher concentrate cyclones 20 in.
Thickener 200 ft diam
F i b a t a g e regrind mills 10 ft 8 in. x 20 in. 500
Firststage flotation cells 100 cu f t
Secondstage regrind mill 10 ft 8 in. x 20 in. 500
Second-stage flotation cells 100 eu f t
Thirdstage regrind mill 10 ft 8 in.x20 in. 500
Thirdstage flotation cells DECO 40 eu f t
Fourth-stage flotation cells DECO 40 cu f t
Vacuum filters, 6 disk DECO 7% ft diam
Dryers, holoflite DECO 24 in. d i m
PRIMARY MOLYBMNITE ORES

Truck haulage-85 ton Electrahaul trucks


f I-42in.x 65in.CAC gyratory crusher
i.
2 - 6 0 i n . x 102 in. Syntron vibrating feeders
a
I-54in. x 2 7 f t B L conveyor - 3 7 5 fprn, 15 hp
t
1-54in. x 3 7 2 f t B L conveyor-500fprn, 2 0 0 hp
Undersize .)
I - 8 f t x 2 0 f t primary screen CAG Model X X H
Oversize

+
I- 4 8 i n . x 64 f t B L conveyor -375fprn, 3 0 hp

t.
I - 4 8 i n . x 2 5 9 f t BLconveyor-400 fprn, 150 hp
I

2-8ft x 20ft
t
C A C Model SH screens
4 Oversize
I

2-36in. x 1 7 f t B L conveyors-30Ofprn, 10 hp
t
2 - 5 i n . x 8 4 i n . GAC Hydrocone crushers

I - 4 8 i n . x 5 0 8 f t B L con'veyor -400 fprn, 150 hp


+
Conveyor scoles transweigh

1-48in. x 35511 B L corfveyor - 410 fprn, 50hp

I-Stephen Adornson
t
tripper- 2 0 fprn , 5 hp

12-Variable speed c o t hering conveyors,


2 under y c h bin

5 - 3 0 in. conveyors-200 fprn, I0 hp


t
5-Conveyor scales tronsweigh
t .
To r o d mills
FIG. 9. Endako Mined B o w No. (see concentrator flowsheet)
1, d u g .
MOLYBDENUM

F r o m f i n e ore bins via 5 feeder convevors

5 - 1 2 f t diam 11511 CACtrod m i l l s - 1250 ho ea


Portion
r-5-12
4
in. x I 0 in. SRL - C pumps with spares
of pulp I

10 - 3 0 i n . Dorr cyclones ( 3 - 3 6 i n . plus4-30in. spares)


Underflow Overflow
5 - 1 2 f t d i a m x 1 5 f t CAC b a l l m i l l s - 1500 hp
I

+
I - 3 0 in. Dorr cyclone Overflow

I-gftdiam x13ft CAC ball mill -700hp

12- 18 c e l l No. 4 0 Agitair and 4 - 1 8 c e l l No. 3 0 Denver cel IS-)+ Tailings


Rougher Middling
froth froth
cyclone L1
- A Underflow

I - 6 f t d i a m x 12ft
1,
Underflow
D o m ~ n ~ obna l l m ~ l l -2 0 0 hp
lt

2 - Tailings ponds
-- ,--.
t overflow ?I - 5 0 f t d i a m T ~ o r thickener
r

Underflow Underflow
I - 6 f t d i a m x 1 2 f t Dominion ball mill

12 -
t
N o . 4 0 Agitair flotation cells
Tailings \ J

2- 14 c e l l No, 15 Denver flototion cells


Final
concentration

I---- Overflow T
I - 2 0 f t diam x l o f t Dorr thickener
1 Underflow
Internal-
reclaim 1
- 1 - 2 0 f t d i a m x 12 f t stock tank w i t h 3 lightning m i x e r s
4
1-10 f t diam x 10 f t stock tank with I l i g h t n i n g m i x e r

To filtration and roasting


4( s e e roaster flowsheet )
FIG. 10. Endako Mina flowsheet No. 2, mncentration.
PRIMARY MOLYBDENITE ORES

From stock tanks


I
$-
I - 6 f t diam, 4 disc Eimco Agidisc filter
Solids
-
To conc
16-15

thickener

I - 16ft diam, 6 hearth Nichols Hereschof f dryer


Discharge Flue dust
Sulfide bin storag<- 90 ton capacity I -Rotoclone,Type N, Size 6
Portion to roasting Solids
I - 5 ton roaster feed bin
To atmosphere
packing 7
A:'
I 18f t diam. I 2 hearth Nichols Hereschoff roaster
-

I - Field Joy electrostatic precipitator

I I - 4 f t 6in. diam x'148ft high stack


t
I I
To atmosphere

i
I -Sulfide storage bin, 90 ton capacity
i
I-Sturtevant No, 00 hammer mill
0

Toledo scale
t
I PA----- lA
-- - L ! - _ i _ - 3-Oxide storaae
" bins-25 t o n capacity
aroruye unu srllpplrlg
-
Pitch bin
I - Blknder
t 7
I - Pa l l e t box packer
I - Feed hopper
I
TOI edo'scale $-
I
+
Storage and shipping
I -Hydraulic briauette Dress
~ o d e CU-1,
l 3 0 0 'ton
1
I - ~ u a d u m tic'packinq
a machine
.)
Storage a n d shipping
FIG. I I . Endako Miner l o w h e t No. 3, roasting packing. and briquetting.
16-16 MOLYBOENUM

-
Henderson Mine ore by railroad t
First cleaner flotation
3 0 , 0 0 0 tpd , 0 . 4 5 % MoS2 34-100 cu.ft. Deco cells
v
4
I 4

1 1 Fixed drizzly
t
Tailing Concentrate
I
WII:;;~ ;,da'm
Tailing
gyratory crusher
-!- kPl
Second stage regrind mill

I
4
8 4 in, apron feeder
4
I i
, Cyclones , I1
58,000 live tons stockpile
I
t
3 - 4 8 i n . apron feeders per mill SecAnd cleaner flotation

4
3 - 2 8 f t x 14ft semioutogenous
20-40cu. ft. Deco cells

Tailings Concentrate
mills 8. 1 - 3 0 f t x I l f t semiautogews
m i l l 7 0 0 0 h.o. each
4
3- screens

f-
71
oversized 1 Cyclones
4 - pump sumps r

t underflow
4-12in. x 14in. pumps
(3-standbys)
Third cleaner flota;ion
10-40cu,ft. Deco cells
I ,
t
Lunde?flow overflow
I- s a m p l e r f r division)
7
Distributor
I
t
Rougher flotation
120-300cu. f t . Deco cells
3 0 per division holding tanks
I I
4 .. 4 t
Rougher taillng Rougher concentra te Disc filters
1 (4divisionsi 2-6 Disc, 7112Deco
t
Sampler Leach c i r c u i t y
7
t
Rougher ckncentrale
Tailing dam c;clones ( 2 0 in.) 4-Holoflite dryers
1 7
t t
underflow overflow
T
I T
Z O Ot i c k e e
I
I

FIG.12. Henderson mill Rowshat

Sodium dithiophosphatedepressant for copper, iron, and l e d was added water from Clary Lake to the plant site, and interlocked conveyor
at the rate of lpproxinutcly 0.5 Ib pcr ton in the cleanm and equipment systems.
Sodium silicate variable was added for insol mnovd at the cleaners. Tailings were disposed of by gravity into the sea.
Lime for conditioning was added at the rate of approximately
0.05 Ib per ton. There was considerable automation and instrumenta- Molybdenlte Corp. of Canada
tion in the mill consisting of gamma level gages on the coarse ore
bins. Ramsey weightometers, secondary crusher and mill feed con-
trols, periodic error integrating controls on secondary crusher and The capacity of the MolyWenite Corp. of Canada Ltd. plant in
mill feed, density control on rod mill feed, remote control of process Quebec was some 1200 tpd and the mill feed 0.206% MoS1. 0.033%
BYPRODUCT MOLYBDENITE

Bi; the final concentrate before leaching assayed 75.8% Ma%, 10% Cllmax Molybdenum
Bi, and the tailings 0.02 1% MoSz, 0.009% Bi. Trentment of Oxidized Molybdenum Ore
The ore was ground to 98% -35 mesh (65% -100 mesh) and
treated to recover M a and bismuth. The concentrate containing A chemical process employed by Climax during the period August
75% MoSz, 10% Bi, 12% Cu was then leached in muriatic and nitric 1966-August 1968 for recovery of molybdenum from an oxidized
acid to recover the bismuth in the liquor. The bismuth was precipitated fraction of ore is briefly described for general information. Such s u p
by adding water, then dried and sent to a bismuth smelter for further plementary treatment of molybdenum may be important in the future
treatment. for treating newly mined ores with a small content of oxidized mineral
After the MoSa was dried, it was shipped to the roaster and became or for retreating enormous tonnages of impounded tailings. The steps
Moo3, the final product. The ratio of concentration was 409 and employed at Climax were as follows:
recovery of MoS2 averaged 89.8%. I) The MoS, content in partially oxidized o n war 6r3t recovered by
flotation in t h usual manner.
2) Tailings from MOSS flotation were upgraded in nonsulMe molybde-
Two sets of vein systems composed the ore body as follows: (I) num content by s e p ~ t i n gthe 6nes from the sands at about 400 mab.
North-south pegmatitic quartz 2, with microdine feldspar, muscovite. NotuulMc molytdcnum war anccntnted in the h e fraction with an u p
grading frtor of about 3: 1. A small .dditiod rccmny of fine nonsul6de
biotite, minor bismuth. fluorite, and molybdenite associated with gran- molybdenum wu achieved by attrition scrubbing of the sand fraction. b
ite. (2) East-west milky quartz, cleavlandite feldspar, minor beryl, nomics of this step were margid.
bismuth and molybdenite, muscovite (sericitic) and biotite, and some 3) The fine fraction war thickened to abwt 60% solids and leached
minor pyrite and chalcopyrite associated with schist. with a combination of sulfuric and sulfurous acids wing activated charcod
to absorb selectively dissolved molybdenum in a char-in-pulp p.- The
Concentration dissolved molybdenum war in the form of a colloidal sol called molybdenum
blue.
Transportation consisted of hoisting the ore to the surface where 4) Losdcd charcoal war separated fmm the pulp by screening and then
it was crushed and thence to the mill bin by conveyor. Tailing dispcsal eluted with ammonia The eluate war air-blown to convert the molvbdmum
was made by using dams of rock waste, gravel, and tailings. The to ammonium molybdate. Thk solution war t m t d with magnesium sulfate.
ore was ground to 98% -35 mesh and treated to recover M a and and a sludge containing magnaium phosphate, iron, and ore slime war
bismuth. The concentrate containing 75% MoS., 10% Bi, and 1.2% moved by filtntion and divrrdcd with plant tailings.
Cu was leached in muriatic and nitric acid to recover the bismuth 5) Ammonium molybdate crystlls were pmduud by mpontion and
in the liquor. The bismuth was precipitated by adding water, then wnvcrted to molybdenum trioxidc by calcining the Rnal product to a purity
of 99.8%.
dried and sent to a bismuth smelter for further treatments. 6) Ammonia war ~kovercdfrom p- gasa in an absorption tower
ARer the MoS. was dried it was shipped to the roaster and became and reused for stripping molybdenum fmm loaded c h d .
MoSJ, the final product. 7) Barren chnrcoal war reactivated by h a t tmtmenl m a cyclic &
The -gent consumption follows in Table 4. ar required, to maintain loading &cicncy.

lablo 4. R q o n b , Molybdonlk Corp. of bnada


Name No. tons Point add Function
Potassium Final middling
Amylxanthate conditioner Collector for M a , Bi
Aem 25 h l middling Collector for Bi
Aem 208 Rod mill Collector for Bi
Kerosene Conditioner Collector for MoS.
Dowfmth Conditioner F'mther
Pine oil Conditioner CoUeetor for M a
Sodium cyanide Conditioner Depression for Cu, FeS.
Sodium sulfite Rod mill Depressioo for Cu, FeS,
Sodium silicate Conditioner Depression for quartz
and silicates

2. BYPRODUCT MOLYBDENITE
JOSPEHSHIRLEY AND

today most plants producing byproduct molybdenite are treating ores


Since 1933, when the first byproduct molybdenite was recovered wntaining0.01-0.03% Mo. Kennecott's Utah Div. was the first opera-
by the G m e Consolidated Copper Co., in Sonora. Mexico, its impor- tion to recover molybdenite from a low grade ore. In 1936 this com-
tance as a source of molybdenum has steadily increased. However, pany produced I million Ib of molybdenum contained in a Ma%
it was not until after World War 11, with the development of the concentrate from ore containing approximately 0.04% Mo (Fig. 14).
huge copper porphyry d-ts in the southwestern United States, Contracts for the sale of byproduct molybdenite vary from p r o p
western South America,and the Soviet Union, that byproduct molyb. erty to property as far as grade of product and price are concerned.
denite began commanding a large pacentage of the total molybdenum The prices to be paid for a specific grade product is usually a percent-
production in the world. By the early 1960s over oncthird of the age of the "Climax Price" which published monthly in Engineering
molybdenite production in the Free World was produced as a bypr* d Mining JourwL Normally the price is based on the molybdmum
duct of the copper industry. content minus penalties for impurities such as copper, lead, iron (as
Although Cananea was the first to produce byproduct molybde- pyrite), phosphorus, and anrcnic. A typical salable grade of concen-
nite, its operation was not typical of the presentday plants due to trate would contain over 90% M a with under 1% Cu. However,
the fact that Cananea ore contained 0 . 2 4 5 % Mo (Fig. 13). while in 1971 molybdenite concentrates containing only 70% MoSa with
MOLYBDENUM

Ground ore Copper Copper scavenger


17%Cu, 0.25% Mo) concentrate concentrate
( 28%Cu, 0.9%Mo) ( 8 % C u , 2 . 4 % Mo)
No contained con tains
fuel oil fuel oil
1
7 5 f t thickener
2 - 7 5 f t thickeners
C o ~ ~ fel or t a t i o n
Moly deprission circuit
t t 1st staae . 7 rows of 5

-
Concentrate Tailinas
5 6 i i ~ a g cells
.
(0.I0/o Mo)

1
.
F
Molybdenite rougher
Kerosene
Pine o i l

Moly depression circuit


2nd stage.7 rows of 4
5 - 1 8 f t x 5 hearth roasters

t
Insoluble f l o a t
Concentrate
Tailings 5 6 i n j Fag. cells 2 rows of 5

7-
(10% Mo)
T n
Froth
I
Tailings m
5 6 in. Fag, cells

Tailings-
2 4 f t Thickener Tailings disposal
I
w-J,
lnsoluble cleaner
Na2s+
Phosphate Kerosene 2-56in. Fog, c e l l s per row
concentrate
r e n v e r ;leaneri
f i l t e r plant
9
C
~ " 1
Tailinas Concentrate
lnsoluble recleaner
1 t t I-56in.Fag. cell per row
Filter
7
t
v
-Tailinas Froth
Cyanide leach
v
&
Filter
t
drver

Final molybdenite concentrate


ft
4 0 f t thickener

(57% Mo, 0.25% Cu) I t


Moly rougher and scavenger I
FIG. 13. Rowsheet for Cananea mill byproduct molybdenite rsovery I 3 rows of 9 - 5 6 in. Fag. ce-11s
I I
under 2.5% Cu were sold on a regular basis from some properties.
I n the Soviet Union a few concentrators produce a low grade molyb-
denite concentrate which later is upgraded using hydrometallurgical
processes.
Table 5 lists the world's byproduct molytdenite plants along with
their reported metallurgical results.
Table 6 summarizes the metallurgical treatment and procedures I C
Concentrate
I
Tailings
I
used at these plants. u t
Two stages of recleaning

I
,
1 - 5 6 in.Fog.cell e a c h
Usually, molytdenite i n a copper porphyry ore body is deposited
at a different geological time than the wpper mineralization. Very
rF - - - 7
Tailings Concentrate 1 Cyanide. l e a c h
often the distribution of molytdenite i n the ore body does not corre-
spond to the pattern o f wpper mineralization. For this reason bypro-
duct molytdenite production at some properties varies greatly from + 2-411 x 4 & z t 411 x 4 f i S c f i l t e r
month to month. I t is not uncommon to have a byproduct plant
down one month due to a lack of molytdenite i n the ore and the
following month have the plant produce over 100,000 I b o f concen-
t
I + l o f t x 3 hearth dryer
I
Repulper
1
trates (at one plant 500,000 Ib is not uncommon). A t most wpper
properties molytdenite is simply considered a byproduct while at
t
M o S 2 concentrate u
others, such as Brenda Mines and Duval Sienita, i t is considered ( 5 4 % M 0 , I%Cu)
to be an important coproduct. Storage bins
Molytdenite can occur i n a given copper porphyry ore body i n FIG. 14. Flowsheet for molybdenitc recovery from low grade ore at Arthur
one or more o f the following ways: (I) i n well crystallized veins, mlll, K m n a t t Coppcr Corp.
(2) dispersed i n quartz veins and veinlets, (3) as a film filling the
cracks and vugr o f the rock.
The type o f molytdenite mineralization can greatly atTect recovery
and grade of product produced i n a molybdenite recovery plant. For
BYPROOUCT MOLYBDENITE 16-19

Table 5. Metalluqlcal Results of Byproduct Molybdenlte Plants


% remvery of molybdenum Yearly
Molybdenite recovery circuit Over- production
Ore Grade Heads Tailings Concentrate Copper Moly all capacity
% Cu % Mo % Mo % Mo % Mo % Cu circuit plant total Ib of Mo
United States
Utah
Chino
Ray
Silver Bell
Mission
Twii Buttes
Bagdad
Pima
Ebperanvl
Mineral Park
Sierrita
Inspiration
San Manuel
Pinto Valley
Canada
Brenda
C=pe
Island Copper
Lornex
Gibralter
Latin America
El Teniente
Chuquicamata
El Salvador
Toquepala
Soviet Union
Almalyk
Agarak
Balkhash
Kadzharan
Sorski
Tuimski
Bulgaria
Medet
Philippines
Sipalay
NA-not available.

example, if the molybdenite is finely dispersed in quartz veins, it I) The molytdenite is floated with the copper sulfide minerals
will be extremely difficult to produce a 90% M o S concentrate. On into the copper concentrate and either concentrated in that product
the other hand, if the molybdenite occurs as a film on the rock, or depressed in the wpper cleaner circuit making the copper cleaner
there should be no problem in producing a 90% MoS, concentrate. tailings the molybdenite-enriched product.
However, in this case it probably will be very difficult to obtain an 2) Float the wpper sulfide minerals from the ore prior to Boating
80% recovery level in the molybdenite plant. Vein molybdenite usually the molybdenite.
does not present any serious problems either in obtaining a satisfactory 3) Float the molybdenite from the ore prior to floating the copper
grade or recovery level. It must be stressed that most wpper porphyry sulfide minerals.
ore bodies contain more than one type of molybdmite. Therefore, a The first approach is used almost universally today because molyb-
given property might have a grade problem one month and a recovery denite normally floats quite readily with the copper sulfide minerals,
problem the next month. and its value is usually small in comparison to the value of the wpper.
The presence of MWfloating minerals in the ore body, such The third approach was used at Cananea; however, it has generally
as graphite, talc, and sulfur, can greatly complicate the design of a been rejected due to the difficulties involved in keeping the molybde-
byproduct molybdenite plant. because they have a tendency to wncen- nite depressed (Fig. 13). I t must be added that Kmnecott at their
trate with the molybdmite. The copper and iron sulfide minerals Utah property (Fig. 14) and ASARCO at their Mission unit (Fig.
will reduce to some extent the number of p r o c a w which can be 15) in addition to their wpper concentrates, also treat wpper rougher
effectivelyused to recover the molybdmite. Some prooessg are much scavenger and cleaner scavenger concentrates for molybdenite recov-
more effective in treating a molybdenitemriched product containing ery.
chiefly chalwcite than in treating a product wntaining chalcopyrite The third approach has been used at a few very small mills where
and vice versa. If the ore body contains carbonate minerals in close the value of the molybdenite far exceeds the value of the wpper
association with either the copper and iron sulflde minerals or the content of the ore.
molybdenite, it is doubtful that acid conditioning would be effective.
-
Factom Afloctins the Ri- Recoven
RECOVERY O F MOLYBOENITE FROM
The cause of molybdenite losses in a wpper concentrator is nor-
COPPER PORPHYRY ORES
mally the fineness of the grind. Usually, the ore is ground to the
General
point where the copper is liberated. This may or may not be the
Listed are the three general approaches for producing a molybde- point where the molybdenite is effectively liberated. Very often it is
nite enriched wpper concentrate from wpper porphyry or molybde- not. Generally, the finer an ore is ground, the higher the molybdenite
num-bearing copper ore: recovery.
l x x x l x x X x x l x ~ I I X * I I I X X I I I I I I I X
X I I I X I X ~ I I I I I 1 1 x 1 I I I I X X X X l X X X X
I I I I I I I X I I I X I 1 1 x 1 I I I X I I I I I I I I I
I I I I X ~ I I I I I I I/ I l l X I I I I I I I I I I I I
* X X X X l X I X X X X I I I I X I I I X I I I I I I I I X
X I I I I I I X I I I I I 1 x 1 1 1 1 1 1 I X l X X X I 1 I
X X X X X X X X X X X X X X X X X x l x x X X X X X X X X X
X I I ~ ~ I I I I I I I I Il l 1 I I I I I I I I I I I I I
I I X I I I I I I I X X I 1 x 1 1 I I I I I I I I I I I I I
X I X I I I I I I I X I X I I I I X X X * I I I I I I I I X
I I I I I I I ~ I I I I XI I I I I I I I I I I I I I I I I
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I I X I I I I I X X I X I I I I I I l l 1 I I I I I I I I X
I I X X X I X X / I I 1 X x x x x I X X X I I I I I I I I x
X I I x I J I I x x x x I X I I / x x x x x x x x l x x x I
w z q m s ~ z m m t - m t - ~l ~ m m4 ~ 2 m m W W ~ W W w t~- I
g a a 8 8 ~ 3 m m o m m o mmmm mmmo ~3mmmo
m-mNm-m8 N N O ~-morn N N - N A ~ 88 2
9 Y 9 9 Y 9 V 9 0 . Y Y 9 9 9999 Y 9 9 9 0.Y9Y99 0.9
-mmt-o+c-t-csmq
A A A A =mq= m=== =s=qm= s m
X X I X X I I I X X I I I 1 1 x 1 1 1 1 1 I I I I I I I I I
I X I I I I X I X X X I I / I l l I I I I X X X X I I X X X
%%%%%Z%%%%X~ l %%%% 1 2 8 % 8 8 2 % I I 8% 3
I I I I I X I X I I I I I 1 x 1 1 X I I I X I X I I X I I I
I X I I I I I X I I X I X I l l 1 1 x 1 1 I * I X X I I I I
X I X X X ~ X X x x x X l X I X I I I I X I I I I I I I I I
I X I I X I X I I I I I X I I I I l X X X I X I I I I X X X
X I I X I I I I I I I I I I l l 1 I I I I I I X I I I I I I
I I I I I I I I I I I I I X I 1 1 I I I X I I I I I I I 1 X
~ x I I I I I x x x I ~ /I I l l I I I I m ~ a I I~ I~ I
I I I I I I I I I I I I I I l l 1 X I X I I I I I I I I I I
I I I I I I I I I I X X I I l l 1 X I I I I I I I I I I 1 I
X I I X I I I I I I I I X 1 1 x 1 X X I I I I I I I I X I X
~ X X X X X X X X X X X X X X X l l x x x X X X X X X X X X
moaomqmmmmmmq
GAAA-AA.4AAm.eA
ooo
6 251 qqyy y
AmqN
qmqm
qmq yq 2
'ns
A A d A A d - A d d A A A I A A
aaa a s a a
8488888888888 8888 BSSU 88488'8 88 B
-
BYPRODUCT MOLYEDENITE 1e21

Copper and copper such as a d i i t h o g c n in the primary grind is uscd to promote the
scavenger concentrates molybdenite. At Sen Manuel it has bmr found neocssary to add fuel
oil both in the primary grind and regrind mills in order to obtain a
F maximum recovery of molybdenite. If the molybdenite is poorly crys-
6 5 f t thickener tallized, the watcr-aoluble wpper collectors such as xanthates and
thiihoaphates will also tend to promote it.'
4 f t x 6 f t conditioner It is believed at mast plants that the use of Lime (CaO) and the
resulting pH range (9.6-1 1.8) in the wpper flotation circuits ha9 little
if any d e c t on the molybdenite recovery. However, a lime or pH

+
10-No.48 Agitair c e l l s sensitivity of the molybdenite at Chuquicamata where a higher recov-
I
Concentrate Tailings
cry of molybdenite can be obtained at 9.6 than at 11.3 is noted. At
Toquepala exactly the opposite effect has been o k e d . It should
be noted that in the fvst case no oily coUector is used and in the
second the oily collector AF-3302 (the ally1 ester of isopropyl xan-
concentrate thate) is added to the primary grind.
filter plont Anotha possible c a w of molybdenite lossa, in the copper con--
trator can be an oxide coating on the molybdenite particle. A layer
4-No. 15 Denver cells of powellite on the surf- of some of the molybdenite particles at
El Teniente ha9 bmr found responsible for some of their prLnary
Concntrate Tailings It should be mentioned that at El Teniente and Chwuicamata
oxide molyWolum m i n d often account for a l u g e portion of the
t molybdenum in the ore treated; mast m i n e periodically assay for
2 0 f t thickener oxide molybdenum. Slime coating of molybdenite can also cause a
7
6 f t x 6 f t drum fllter
primary loss of this mineral. At Pima highly altered e-nd products
of serpentine and minerals having a t a l m nature tend to depress
t the molydenite. This ha9 also been observed at Twin Buttes, Mission,
13,5 f f x 5 hearth roaster and Climax.s
7
Screw conveyor The quantity and character of the froth in the copper rougher
circuit can greatly dect the recovery of molybdenite when the mineral
enters the flotation circuit as relatively large tlnkes. These Aakes tend
7
3 f t x 6 f t regrlnd mill. to drop out of the froth quite easily. If chalcopyrite is the primary
Closed circuit with copper mineral present in the ore, it will tend to crowd out the molyb-
4in. ceramic cyclone denite in the copper cleaner circuit. If middling thickeners are used
7
3 f t x 3 f t conditioner
in the wpper circuit, it is not uncommon to lose fine molybdenite
in the thickener overflows. It should be noted that most of the corn-
v Insoluble float
monly uscd flocculants can have a depressing effect on molybdenite.
An effective depression of the coarse molybdenite in the rougher opera-
6 - N a 2 4 Agitair cells tions of two plants when an excessive amount of flocculant was added
to the molybdenite section feed thickener ha9 been observed.
4
Tailings Conceitrote
I I The Recovery of MdyWenlh from the
4 4
IJ
Mdybdenum-Enriched Product
3 f t x 3 f t conditioner Insoluble cleaner
2-No. 2 4 Aaitoir cells
~ol$float After the molybdenite has been concentrated into the enriched
6-No. 2 4 Agitairs Conc!ntrate &T product, which is normally the copper wncentrate, it must be concen-
trated into a salable product. The main constituents in the feed to

*
l st 8 2 n d cleaners 3-4ft x4ft
a byproduct molybdenite recovery plant are usually the wpper and
iron sulfideminerals. Therefore, the main problem becomes separating
molyWenite from a pulp containing these minerals. Several successful
5-No. 15 Denver holding tanks procedure have been developed for accomplishing this objective, but
m
-Tailings concentrate 3ft x 4 f t
the situation is often complicated by the presence of what are wm-
monly called mhurl 0oa.ters such as talc p p h i t e , and sulfur in
I
the copper-molybdenum wncentrate. The problem of separating the
3rd-8th
t
cleaners molybdenite from a pulp containing these and other strongly hydro-
7-No. 15 Denver phobic minerals can be difficult and can make what would otherwise
f
Toilings
concentrate Screw dryer
be a rather simple flowsheet relatively complicated. Also, it is not
uncommon to find that a large portion of the molybdenite is locked
. P

with gangue miner&, usually quartz.


5 5 goi, drums Quartz-Molybdenite Middling and the Edge Elfeet Probably
the mast common of the problems referred to is a locking problem
FIG. 15. Flowshat for rnolybdenitc raovery at Miasion UN~,
ASARCO. between quartz and molybdenite. The solution is either to regrind
to liberate the molybdenite or produce a low grade final molybdenite
concentrate which can be further refined using a hydrometallurgical
procss. The mines in the Soviet Union appear to favor the latter
The percentage of molybdenite recovered in a copper concentrator procedure, while the mines in the westem hemisphere use the former.
usually can be improved by using an oily type reagent. At a few Two or three companies have recently developed procedures for pr*
plants a fuel oil is added in the principal grinding section to promote cessing low-grade concentrates in the United States, but as yet they
molybdenite. At other plants the use of an oily type copper collector have not gone beyond the pilot plant.
A majority of the US plants contain one stage of regrinding and as naturally occurring sulfur is distilled off from the baking furnace
a few contain two. This situation is complicated by the fact that at 260C.6
molybdenite can be easily overground. This phenomenon is due to Tale and Pyropbyllite. At a few plants it becomes necessary
what is commonly called the edge effect. The surfaces or faces of to separate molybdenite from strongly hydrophobic insoluble minerals
the molybdenite flakes are quite hydrophobic; however, the edges such as talc. Sometimes this problem is confused with the more com-
tend to be hydrophyllic.' As the molybdenite is ground finer, the mon quartz middling problem, because the effect on the molybdenite
edges become a greater proportion of the total surface area and the concentrate grade is the same. It should be mentioned that both prob-
molybdenite becomes more sensitive to the copper depressant used. lems can and do occur at the same time. Normally. the molybdenite
Therefore, it is important that molybdenite middlings be ground no is not closely associated with talc; however, at Pima there are strong
finer than necmary to obtain liberation. indications that some of their molybdenite is very finely locked with
This problem is very serious at Chuquicamata where some of talc.
the quartz from the mine has a purple tint due to finely dispersed The classic solution to this problem is to subject a molybdenite-
molybdenite. At this property it has been observed on occasion that talc enriched product to a skin roast, whereby the surfaces of the
regrinding did not lower the insoluble content in the final molybde- molybdenite particles areoxidized so that they tend to be hydrophyllic
nite concentrate; it only reduced the quantity of final product. In other in nature. On the other hand, the talc is unaffected by the roast
words, the molybdenite was being overground as fast as it was being and floats quite readily. In the dextrine process used at Kennecott's
liberated. Chuquicamata does not use a collector for the molybdenite Utah plants,' in which the molydenite is depressed, the molybdenite-
in either the copper concentrator or molybdenite recovery plant. enriched tailings are subjected to a roast to burn off the dextrine
Another phenomenon that must be mentioned is the fact that (Fig. 14). The roast appears to activate some of the insoluble minerals,
ferric ions tend to depress molybdenite, at least in the presence of a causing them to float along with the talc in the subsequent insoluble
copper depressant. This can often be observed after a regrind stage float stage. It should be noted that the talc is effectively depressed
has been down for a prolonged period of time. Usually for about with dextrine along with the molybdenite.
an hour after start-up the molybdenite does not float readily in the At two mines the standard operating procedure has been to concen-
cleaner stages following the regrind. A few plants are using rubber trate the talc and molybdenite into an intermediate concentrate before
liners in their mills to reduce this effect. Also, porcelain balls or separating them. In the past Pima used a multihearth roaster and
tungsten carbide cylinders can be used in place of steel balls, if it is Twin Buttes (Anamax) used a spray dryer for this purpose. Neither
necessary to eliminate this factor completely. procedures was completely satisfactory. Pima developed a process
Sulfur m d Covemite. At a few properties the presence of sulfur whereby the talc is depressed with zinc or aluminum sulfate and
and/or covellite in the copper-molybdenite concentrate can create sodium silicate at a neutral pH (US Patent No. 3,921,810). Twin
problems in the production of a satisfactory grade of molybdenite Buttes now uses lignin sulfonate and milk of lime to depress the
concentrates. The reaction of certain forms of covellite will be similar molybdenite.
to that of chalcocite in a molybdenite recovery circuit; however, there Kennecott's Research Center has developed an acid-bake process,
are other forms of this mineral which will not depress with any of which effectively depresses the talc and allows the molybenite to be
the commonly used copper and iron sulfide mineral depressants. Nor- enriched in several flotation stages6
mally, the problem of floating covellite into the final molybdenite Graphite and Other Carbonaceous Material. Fortunately, none
concentrate is only minor due to the relatively small proportion of of the existing molybdenite byproduct plants have a problem with
this mineral in most copper porphyry ore bodies. The usual solution graphite. However, two plants. Island Copper and Morenci, had a
to the covellite problem is to dissolve it from the final molybdenite serious problem with coal type substances. At Island Copper coal
concentrate with sodium cyanide. In the early years of the Toquepala and a naturally occurring tar are widely distributed in the ore body.
mine it occasionally would be necessary to shut down the molybdenite The carbonaceous material floats quite readily into the final molybde-
recovery plant due to a preponderance of covellite in the plant feed. nite concentrate. Several approaches were investigated for solving this
This problem has been most serious at Inspiration, due to the problem, including fluid bed roasting, tabling, and cycloning. Banks
fact they produce covellite synthetically from chalcocite in the copper of I-in. cyclones operated at 40 psi appear to have produced the
leaching plant prior to the sulfide concentrator. The staff at Inspiration most satisfactory results. At Morenci coal was inadvertently added
has worked on the theory that the reason the covellite floats in the to the pulp in the copper concentrator as an impurity in the precipitant
presence of copper and iron sulfide mineral depressants is a very used in their LPF circuit. It floated quite readily into the final molyb-
thin layer of sulfur on the surface, which is also produced in the denite concentrate. The most successful approach to its removal was
leaching operation. Therefore, the solutions developed at Inspiration to subject the precipitating reagent to a froth flotation step prior to
for the covellite problem are also possible solutions to the sulfur its use. Morenci has not operated their molybdenite plant for several
problem. Inspiration's first solution to the problem was to submit years.
the molybdenite plant feed to a skin roast in a multihearth roaster. Other Special Problems. Usually. byproduct molybdenite sales
Although the procedure was metallurgically successful, it was difficult contracts call for very low concentrations of lead, arsenic, and phos-
to operate. The second solution was to heat the plant feed with live phorus. Normally, molybdenite concentrates produced from the cop-
steam in autoclaves to the melting point of sulfur. The sulfur would per porphyry ore bodies meet these specifications easily. At this writ-
then react with lime in the pulp. In I973 a cleaner concentrate was ing, no byproduct molybdenite plant is treating molybdenite
treated in a similar manner for sulfur removal and for covellite depres- concentrates specifically for lead removal. However. Brenda Mines
sion (Fig. 16). is subjecting its final molybdenite concentrates to a hot ferric chloride
Laboratory test work conducted at lnspiration indicates that the leach for the primary purpose of dissolving residual ~halcopyrite.~
covellite can be depressed with Nokes reagent following a prolonged At the same time essentiallyall the lead, present as galena, is dissolved.
conditioning period with ammonium sulfide. Ammonium sulfide is Those plants using either the phosphate or arsenic Nokes processes
a good solvent for sulfur. M i m i conditions their thickened molybde- must be careful that these reagents do not carry over into the final
nite rougher concentrate to remove sulfur and to activate the molybde- concentrates. For example. Chuquicamata (arsenic Nokes) filters and
nite so that it floats rapidly in the molybdenite ~ l e a n e r s . ~ repulps its final molybdenite concentrate three times to insure that
At Morenci, the sulfur problem was solved by operating a multi- it meets the arsenic specificationas well as a very low alkali specifica-
hearth roaster under strong reducing conditions. The sulfur was dis- tion.
tilled off. A procedure has becn developed by Kennecott to treat Numerous plants leach their final molybdenite concentrates with
low grade molybdenite concentrates produced at their McGill plant sodium cyanide to remove residual amounts of chalcocite and covel-
using an acid bake prcress. Sulfur produced in the process as well lite. Often it is more economical to produce a lower grade product
BYPRODUCT MOLYBDENITE

Copper concentrate
(28 to 5 4 % CU, 0.40 to 1.50% Mo)
170 to 2 5 0 t p d
I
t Overflow
2-loin. c y c l ~ n e s - ~ ( N H ~ ) ~ S

ODs pump

Nokes reagent
~ o l bdeniie
y rougher

-
6-No. 3 6 Agitairs
1 4

y
-
2-stage scavenger

I
8-No. 3 6 Agitairs each

-
Tailings Concentrate
t
Copper smelter

k ~ o k e reagent
s
t
4 Stages of cleaning
4No. 3 6 Agitairs each

concentrate
I Tailings
t
Thickener
-team
3 - 3 0 cu. f i autoclaves

Coolina sumD
. )
Rearind
t
Holding tank

I- Fuel oil
Nokes reagent
4 Stages of cleaning
10-No. 15 Denver Sub A
m
Concentrate

T
T~CN
3 Cyanide leach tanks Previous cleaner
7 stage

"i""
Screw type dryer
(Electric heated)
7
Final molybdenite concentrate
FIG.16. Rowshe* for molybden- (53% Mo, 0.50% CU)
ite recovery at Inspiration mill.
16-24 MOLYBDENUM

as far as copper content is concerned in the flotation circuit and using a molybdenite depression circuit, an oily type collector cannot
leach with cyanide rather than produce a high grade product origi- be used ahead of it without adversely affecting the depression. In
nally. these circuits molybdenite is reactivated by conditioning with a fuel
oil ahead of the cleaner circuit. Other reagents commonly used in
MolyWenltbCopper Sulfide !Xeparatlon P r o c e s s e s molybdenite byproduct plants are frothers, antifoams, and dispersants.
General Also. very often acid or caustic is added for pH control.
Common to all molybdenite recovery operations is water. The
With two notable exceptions all of the commercially developed quality of the water used in a molybdenite plant is extremely impor-
processes for separating molybdenite from a molybdenitecopper en- tant. Essentially all the companies in the western world use fresh
riched product use the general flotation approach of depressing the water in their molybdenite recovery circuits.
copper and iron sulfide minerals and floating the molybdenite. The
two exceptions depress the molybdenite in the initial flotation step.
Several excellant depressants for copper and iron sulfide minerals MolyWenlte Byproduct Plant Operating C o s b
have been found and are in use today. The most important of these Operating costs are calculated on the basis of a ton of plant feed
are: (1) sodium ferr~cyanide,~ (2) Nokes magent ( P a s diwlved in (copper concentrate) and on a pound of contained molybdenum p r e
NaOH),Io (3) arsenic Nokes (AS.0, dissolved in Na2S)." (4) sodium d u d . The figure for cost per ton of feed is more meaningful to
sulfide, (5) sodium hydrosulfide," (6) sodium cyanide, and (7) thiogly- the plant metallurgist, because most of the operating costs are propor-
colic acid. tional to the tonnage treated. The operating costs of a plant treating
Several plants simply add one or more depressants in several stages 1000 tpd of copper concentrates containing 0.5% Mo are summarized
of flotation in order to produce a satisfactory grade of concentrate. in Table 7 (1972). It should be noted that the cost of reagents was
while other plants include an operation whereby the copper collectors separated from the other costs. This was done because it varies greatly
added in the copper concentrator are either completely removed or from plant to plant, depending on the process used.
altered in some way to destroy their Mectiveness. This is done to Since the dollar is constantly losing purchasing power and at vari-
improve the dficiency of the copper depressants. This operation usu- ous yearly percentage rates, the following ball p r k type operating
ally is performed on the feed to the molybdenite plant; however, cost formula was developed on the basis of the average cost of a
some plants treat an in-circuit product. The ways in which this objec- man per shift:
tive is achieved are: (I) steaming,13.l4 (2) pressure steam,15 (3) skin
2NC
roasting (a light roast),'s (4) cooking (indtrect heating of the pulp)."
(5) conditioning with acid and hydrogen peroxide.le (6) conditioning
Cost per ton of plant feed in $ =-
T
+R
with sodium hyp~chlorite.~'and (7) simply aging the pulp.ls Some
where N is number of men required to operate plant (obtained from
of these procedures not only remove or alter the copper promoters,
Table 8). C is average cost of a man per s h i i in dollars. T is the
but also change the surface of the copper minerals, so that a depressing
daily feed tonnage, and R is the reagent cost per ton of feed in
agent may not be needed.
dollars.
Many substances have been discovered that will very effectively
This formula does not consider capital cost of the plant and general
depress molybdenite. These include starch, dextrine, saporin, various
overhead nor does it cover, in most cases,a prorated cost of mining,
organic dyes, and f o ~ m a l d e h y d e . ~ ~these
- ~ O fsubstances only dextrine
stripping, or concentration prior to the byproduct operation.
is used commercially for this purpose. The main reason for this is
cost and problems associated with the need to reactivate the molybde-
nite for cleaning after the initial separation. As yet, no process has Plant D e s r l p t l o n s
been developed whereby a final grade molybdenite concentrate can
be produced through the use of repeated depression stages. At El
Teniente, in the old copper sand circuit, the molybdenite was effec- The final copper concentrate containing 0.3 to 1.2% MoS. with
tively depressed along with the pyrite with calcium cyanide and lime sodium sulfide, butyl xanthate, and pyridine frother is the feed to
(CaO).? the molybdmite recovery circuit. The feed is thickened to 55 to 60%
In almost all plants. a tight fuel oil is added to promote the molyb solids, heated to 70 to 80C for 40 to 60 min with superheated steam
denite. There is good evidence that light vapor oils containing a large in the presence of a hydrocarbon emulsion and lime (800-1000 g
percentage of aromatics are better promoters for molybdenite than per Cu m), diluted and cooled with water to 2&27% solids, condi-
the more commonly used diesel fuels or stove oils.z1 In thme plants tioned with an emulsion of hydrocarbons and sodium sulfide (10 Ib

Tabla 7. O ~ m t l n ob s t s far 1.000 Tod Plon11 TroaHng Faod b n b l n l n g 0.5% Mo (1978)


$ per Ib of contained
$ per ton molybdenum pmduced
Cost item of feed At 60% r e . At 80% rec.
Supervision
Operating labor
Repair labor
Operating supplies
Repair supplies
Asaaying
Loss of cu
Special handling
Power cost
Total base eost
Reagent mat: Low
High
Total operating
costa
BYPRODUCT MOLYBDENITE

S i of plant, tpd of feed (Cu concentrate)


Type of labor 200to500 500to1500 1500 to 2500
Operators 3
Helpers 19
Maintenance Lh
Asssying Lh
Supervision H-1
Average total daily manpower 6

per ton), and floated in the rougher for I5 min. In the heat treatment phenol frother (from coke distillation) is the feed to the molybdenite
it has been found critical to keep the percent solids below 60 in recovery circuit. The feed is thickened to 45% solids, conditioned
order to prevent the smearing of oxides from the copper sulhde miner- with sodium sulfide (1CL12 Ib per ton), sodium silicate (2 lb per ton)
als on to the pyrite, which apparently causes it to float. The rougher and kerosene (0.6 Ib per ton), and floated in the rougher at about
concentrate is cleaned five times using sodium sulfide and the hydro- 40% solids and 85-90C. Special heating coils are installed in the
carbon emulsion producing a product wntaining about 30% Mo with flotation machines. The rougher wncentrate containing about 0.6%
a 70% average recovery. In the future it is planned to use an oxidizing MOSS is cleaned six times with two in-circuit thickening steps to
steaming treatment for a longer period of time and operate the rougher maintain the desired pulp density in the flotation stages and eliminate
float at 3CL35% solids to lower the sodium sulfide consumption to reagents. Sodium sulfide is added to the cleaning steps to maintain
about 1.0 Ib per ton. Also, it has b a n found that an addition of at least 3 gpl of active sodium sulfide in the pulp. Sodium silicate
about 0.5 Ib of copper sulfate per ton of feed to the steaming circuit is the only other reagent used in the cleaner circuit. The final flotation
tends to activate the molybdenite. They feel that the lime usage is concentrate, which contains about 36% Mo, is roasted to the oxide,
responsible for a Icss of 15-17% of the molybdenite and that an leached, and then converted into technical grade calcium molybdate
addition of more than 6 Ib per ton of sodium sulfide causes some with calcium chloride.
loss of molybdenite in the rougher.
Brenda Mines Ltd., Canada"
The copper concentrate containing approximately 5% MoSz with
There are four plants in Armenia producing byproduct molybde- AF 3302, Z-11, and MIBC is the feed to the molybdenite recovery
nite: Kadzhavan, Dastaket, Alaquez, and Agarak. These plants all circuit. The feed is thickened to 6045%. conditioned with 20 to
use a similar flowsheet for recovering molybdenite. At Kadzharan 25 Ib per ton of sodium hydrosulfide, diluted to about 25% solids
a recleaner wpper wncentrate wntaining about 10% Cu and 1.5- with fresh water and/or the first cleaner tailings and then floated
2.0% MoSl with butyl xanthate, polypropylene-glycol frother (OPSB). in the rougher. The rougher concentrate is cleaned once, reground,
sodium sulfite, and kerosene is the feed to the molybdenite recovery cleaned three times, reground, and recleaned eight more times to
circuit. At Agarak the wpper rougher concentrate containing about produce a wncentrate grade averaging 55% Mo and about 0.3%
17% Cu and 1.5% MoS, with sodium sulfide, butyl xanthate, OPSB. Cu. This concentrate is then leached with fenic chloride to reduce
pine oil, kerosene, and sodium carbonate is the plant feed. At both the copper content below 0. I %. The cleane~tailings are all countercur-
these plants the feed is thickened, conditioned with lime, heat-treated rented with the first cleaner tailing either being returned to the rougher
with steam for 30 to 40 min at SOo-90C. diluted and -led with or being scavenged and combined with the rougher tailing. Sodium
water to about 25% solids, conditioned with kerosene and sodium hydrosulfide is added to the first cleaner and sodium cyanide is added
sulfide, and floated in the rougher. At Agarak pine oil and sodium to the other cleaners. Fuel oil is added to several points in the circuit.
silicate are also used. At Kadzharen the rougher wncentrate is re-
Chino Mines Div., Kennemtt Copper
ground, steam treated again, and refloated five times producing a
product containing 50% Mo with under 1.0% Cu at around 75% The copper concentrate wntaining 0 . 2 4 5 % MoSa with butyl
recovery. At Agarak the rougher concentrate is also reground and xanthate, burner oil, pine oil, Dowfroth 250, and sodium hydrosulfide
cleaned five times using sodium sulfide and a concentrate containing is the feed to the molybdenite recovery circuit. The feed is thickened
about 48% Mo with under 0.5% Cu. is produced at around 85% to 50% solids. then steamed for about an hour at 209"F, diluted
recovery. with fresh water to approximately 15% solids, and then floated in
Cyprus-Bagdad Copper Corp. the rougher with burner oil, MIBC, and soda ash. The rougher concen-
trate is cleaned six to eight times, filtered, roasted in a 12-ftdiam
The copper concentrate containing 1-2.5% MOSZwith 2-4, AF404 four-hearth roaster at 550-6LMF, repulped, and recleaned in four
MIBC, and pine oil is the feed to the molybdenite recovery circuit. to six flotation stages producing a concentrate grade containing 50%
The feed is thickened to 5 5 4 0 % solids, conditioned with sulfuric Mo and under 1.25% Cu. The cleaner tailings are countercurrented
acid at a pH of about 7.0 (automatically controlled), cooked for I with the first cleaner tailing being returned to the plant feed thickener.
hr just below the boiling point in hot oil jacketed vessels, conditioned Cells are available to conduct an insoluble float following the roaster.
with thioglycolic acid reagent at a pH of 8.CL8.5, diluted to approxi- if required. Burner oil, MIBC, soda ash, and Nokes reagent can be
mately 15% solids with the first cleaner tailings and fresh water, added to the recleaner as required. In 1983 a new molybdenite plant
and then floated in the rougher. One heat exchanger is used to preheat using the sodium hydrosulfide process was built.
the cooker feed and cool the cooker discharge. The rougher wncen-
trate is reground in closed circuit with a cyclone and is then cleaned Chuquicamata, Cia. de Cobre, Chile'z. 32

in 13 countercurrent cleaner flotation stages to a concentrate grade The copper concentrate containing 0.8-3.0% MoSz with Z-l I,
of 54% Mo and under 1.0% Cu. MIBC and fuel oil are added to AF238. Dowfroth 250, and pine oil is the feed to the molybdenite
the rougher feed, thioglycolic acid is added to the first cleaner. and recovery circuit. The feed is thickened to approximately 45% solids.
sodium cyanide is used in the other cleaner stages. diluted to 35% solids with fresh water, and then floated in the rougher
with approximately 15-20 Ib per ton of Anamol "D" (Anaconda's
trade mark for an arsenic Nokes reagent containing one part As.0,
The wpper concentrate wntaining 0 . 3 4 4 % MoSz with sodium and four parts NazS). The first cleaner concentrate is thickened, put
sulfide, butyl xanthate, copper sulfate, lime, kerosene, and a pyridine- in large storage tanks used to maintain a constant feed rate to the
16-26 MOLYBDENUM

cleaner circuit, diluted with fresh water, recleaned in four to seven cleaner tailings are countercurrented with the second cleaner tailing
cleaner stages using 6 Ib per ton of Anamol " D to produce a concen- being combined with the rougher tailings. It should be noted that
trate grade containing 55% Mo and 1-2% Cu. This product is then this is theonly plant in the western world usingconcentrator reclaimed
leached with sodium cyanide to reduce the copper content to below water in the molybdenite circuit. Normally, their final flotation con-
0.3%. Sodium cyanide is also added to the last two cleaner stages. centrate contains 57% Mo with under 0.2% Cu. However, steam
There are regrind stages in close circuit with cyclones after storage heated cyanide leach tanks are available to leach excess copper, if
of first cleaner concentrate and the fourth cleaner stage. The cleaner required.
tailings are countercurrent with the first cleaner tailing being combined
with the rougher tailings. Chuquicamata is now using sodium hydro- El Teniente, Cis. de Cobre, Chilez
sulfide in the rougher circuit and the Anamol "0"only in the cleaner At El Teniente about half the ore is treated in an acid circuit
circuit. (pH 4.2) with Minerec "A" and a frother, and half is treated in an
Duval Sierrita Corp alkaline circuit with Z-200 and DF-1012. The copper rougher wncen-
trates from the two circuits are cleaned together to produce a product
There was no description of this plant's operation available. Pre- containing over 30% Cu and about 1.0% MoSz, which is the feed
sumably they are using a procedure similar to that described for to the molybdenite recovery circuit. This material is thickened and
Esperanza. They are one of the larger producers of byproduct molyb- treated with LR-744 and kerosene prior to the rougher flotation.
denite with an annual production close to 18 million Ib of molybde- The rougher concentrate is cleaned four times, thickened, reground,
num. They have the capability of producing technical grade Moo3. cleaned six times, thickened, filtered, reground, recleaned five times,
El Salvador, Cis. de Cobre, Chilez4 thickened, cyanide leached, filtered, and dried. LR-744 is added to
the various cleaner and recleaner stages and NaCN is added to the
The copper concentrate containing 0.7-1 1% MoSz with 2-200, second regrind stage. The cleaner tailings are generally countercur-
Z-l I, and pine oil is the feed to the molybdenite recovery circuit. rented with the first cleaner tailings being returned to the rougher.
The feed is thickened to 5 M % solids, conditioned with fuel oil, A second leaching circuit is available if needed. The final concentrate
and 1 6 1 6 Ib per ton of Anamol "D" (one part ASz03 dissolved in contains about 55% Mo and under 0.5% Cu.
four parts of NazS), diluted with the first cleaner tailings. and floated
in the rougher at 45% solids (Fig. 17). The rougher concentrate is
cleaned seven times with Anamol " D being added to the first four The copper concentrate containing 2.&2.5% MoSz with AF3302,
cleaner stages and sodium cyanide to the fifth and sixth stages. The potassium ethyl xanthate, potassium amyl xanthate. MIBC, and stove
oil is the feed to the molybdenite recovery circuit. The feed is thickened
to 50% solids. steamed under pressure in a continuous now autoclave,
Copper concentrate conditioned with sodium ferrocyanide, and floated in the rougher
147% Cu, 0 80% Mo, 650 tpd) at about 20% solids. Heat exchangers are used for preheating the
P incoming feed and cooling the steamer discharge. The rougher wncen-

-F1
150 ft thickener
trate is thickened, reground, and cleaned eight times to produce a
7
D~aphragm pump concentrate grade of over 50% Mo with about 1.5% Cu.The cleaner
tailings are countercurrented with the first cleaner tailings being re-
k ~ u e oil
l turned to the plant feed thickener. The molybdenite concentrate is
roasted to MOO,; the roasted calcine is leached to remove copper
before being filtered and dried. The final product contains 58% Mo
with under 0.2% Cu. Sulfuric acid is added automatically to the
Molybdenite rougher rougher and cleaner circuits to maintain approximately 7.0 pH. MIBC,
16-No. 4 8 Aa~tairs fuel oil, and ferrocyanide are added to the various flotation stages

Tnamo
F~rst cleaner
.D,.
Tatllngs

Copper smelter
(Fig. 18). The copper-molybdenite concentrates p r o d u d at Esper-
anza are now treated in the Duval Sierrita molybdenite plant using
a similar process.
Gaspi! Copper Mines Ltd., Canndn
4-Na.48 Agito~rs The copper concentrate containing 0.25-0.70% MoS2 with isopre
1 pyl xanthate, and BHB frother is the feed to the molybdenite recovery
circuit (no lime is added in the concentrate). The feed is thickened.
steamed at 2WF, and floated in the rougher at 25% solids. A heat
Sodium cyanide exchanger is used to preheat the incoming feed and cool the steamer
6 Stages of flnal cleanlng discharge. Sodium cyanide (1.35 Ib per ton), fuel oil (0.44 Ib per
18-No 18 Denver Sub A ton), and pine oil are added to the rougher feed. The rougher concen-
trate is cleaned six to scven times, reground, and recleaned 14 times
t
concentrate Ta~llngs to produce a final concentrate containing 51-54% Mo with under
0.5% Cu. Sodium cyanide is used in the cleaner circuit up to the
7 a . N last six stages where sodium dichromate is added. The cleaner tailings
Cyantde leach tanks are countercurrented with the first cleaner tailings being added to
(Steam heated) the rougher feed. In 1976, the plant was changed to a straightforward
t sodium hydrosulfide procss using sodium cyanide in the cleaners.
Two staae f~lter~no In 1977 they switched their circuit to tbe sodium hydrosulfide process,
1
Kiln type dryer
using sodium cyanide only in the cleaners. Two large. 40 ft deep
air cells were incorporated in the cleaner circuit, which greatly reduces
(Steam heated1 the number of cleaner stages.
7
F~nal molybden~teconcentrate Inspiration Comlidated Copper Co.
(55% Mo. 0.3% Cul Prior to 1978, Inspiration's molybdenite recovery circuit had been
FIG.17. flowsheet for molyMcnitc rcmvcry circuit at El Salvador. shut down for several years, due to low molybdenite content in the
BYPRODUCT MOLYBDENITE 16-27

Copper concentrate Island Copper, U h h I n t e m t i o d , t3mda


( 2 5 % CU, 1.3 O/oMo) The copper wncentrate containing 0.5-1.0% MOSSwith AF238,
-I
5 0 f t thickener
2-6, and MIBC is the feed to the molybdenite recovery circuit. The
feed is thickened, pumped to tanks where it is stored 8-12 hr, condi-
tioned with sodium hydrosuffide (12 Ib per ton), and floated in the

r -
7 rougher at 35% solids. The rougher wncentrate is cleaned once with
hydrosulfide, reground, cleaned three times using sodium zinc cyanide,
Heat exchanger
reground, and recleaned with sodium cyanide, sodium silicate, and
Exfoam 636 to produce a final product containing 45% Mo with
Pressure stjaming vessel under 1.0% Cu. The cleaner tailings are countercurrented with the
first cleaner tailings joining the rougher tailings. Carbonamus mate-

+ Rougher f l o t a t i o n
rial is removed from the final molybdenite concentrates by using small
high-pressure cyclones.
Lamex Mining Carp. Ltd.2s
1 2 - N o . 4 8 Galigher cells
m
Tailings Concentrate
The final copper concentrate containing approximately 0.5% MOSS
is the feed to the molybdenite recovery operation. The feed is thick-
ened. conditioned with sodium hydrosulfide and fuel oil, and floated
fCopper
7
4 0 ft th~kener
in the rougher at about 35% solids. The rougher wncentrate is re-
ground, and cleaned seven times to produce a product containing
concentrate over 50% Mo with under I % Cu. The cleaner tailings are countercur-
filtering plant rented with the first cleaner tailings being scavenged; the scavenger
5 f t x 6 f t ball mill concentrate is reground before being returned to the first cleaner.
Closed circuit with Nokes reagent and sodium cyanide are used in the cleaner stages.
6 in. Cyclone In 1983 Lornex started to replace some of their mechanical cleaner
I cells with column cells. Lornex now uses a hot ferric chloride leach
.c
F i r s t cleaner
to improve the quality of the final molybdenite concentrate.
10-No.18 Spec Sub -A Medet P h t Bulgnrin2
Denver cells Published pilot plant data indicate that Medet recovers molybde-
.
) nite from their final copper concentrate wntaining 14% Cu and about
4 Tailings

r
Final cleaners
Concentrate

1 0 - N O . 18 S u b - A
0.8% MoSl by means of a steaming procedure. The pilot plant feed
was thickened to 50% solids, steamed for 40 min at 80C at a pH
less than 9.5. The pulp was cooled and floated with fuel oil at 20%
solids at a pH of 8.0. After six cleaning stages a 36% Mo concentrate
was obtained at around 87% recovery. The only reagent mentioned
was sodium silicate added for gangue depression and slimes dispersion.
Denver c e l l s
m- Tailings
Pinto Valley, Cities Service 24

The copper concentrate containing 0.25460% MoSz with Aero-


float 2-14, and Dowfroth 250 is the feed to the molybdenite recovery
circuit. The feed to the molyMenite plant is thickened, conditioned
with Nokes reagent, fuel oil, and enough lime (CaO) to raise the
pH above I2 before being floated in the rougher at about 25% solids.
The rougher concentrate is cleaned once with more Nokes reagent
3 f t x 2 f t drum filter added and thickened. This rougher-cleaner wncentrate is conditioned
7
8 f t 9 i n x 10 hearth roaster
with ammonium sulfide (about 5 Ib per ton of molybdenite plant
feed), reground, recleaned two times with added Nokes reagent, re-
ground with sodium cyanide, recleaned three more times to produce
7
Copper l e a c h i n g
a concentrate analyzing about 53% Mo and 1.2% Cu. The cleaner
tails are countercurrented with the first recleaner tailings going back
f to rougher flotation. The recleaners are operated only on day shift.

5=
4 f t x 4 hearth dryer
Mineral Park. Duval C ~ r p . ~ '
The copper concentrate containing 2.0-2.5% MOSSwith AF3302,
potassium ethyl xanthate, potassium amyl xanthate, MIBC, and stove
t
F i n a l M o o 3 product
oil is the feed to the molybdenite recovery circuit. The procedure
used to produce a molybdenum product is almost identical to the
(58%Mo,O.25%Cu) Esperanza flowsheet.
FIG. 18. Flowshat for molybdmitc plant at Espcranza, Duval Corp M i i o n Unit, ASARCO1'
The copper concentrate containing 0.4-1.0% MoS2 with 2-6,
AF238, Stepenflot 97A, and pine oil and a copper-molybdenite en-
riched scavenger product produced from the copper rougher and
ore. They plan on starting up the plant in the future. utilizing an cleaner tailings, wntaining 2-6 and fuel oil, are the feed to the molyb
ammonium sulfide conditioning step to dissolve sulfur and depress denite recovery circuit (Fig. IS). The feed is thickened to 60% solids.
covellite, and sodium hydrosulfide or Nokes reagent as the primary conditioned with a mixture of sodium sulfide and sodium hydrosulfide.
depressant. diluted with fresh water, and floated in the rougher at about 35%
16-28 MOLYBDENUM

solids. The rougher wncentrate is thickened, filtered, roasted, re- with sodium zinc cyanide at about 8.0 pH (automatically controlled),
ground, subjected to an insoluble float, conditioned with fuel oil to conditioned for about 40 min with hydrogen peroxide and sulfuric
reactivate the molybdenite, and cleaned eight times to produce a con- acid at a pH of 6.8 to 7.0 (automatically controlled), conditioned
centrate grade of 51% Mo with under 1.0% Cu. Aerofroth 65 and with sodium ferrocyanide, and floated in the rougher at about 30%
dextrine are used in the insoluble float, and sodium cyanide is added solids. The rougher concentrate is cleaned once with sodium ferro-
in the cleaner circuit. The fuel oil is added as an oil-water emulsion. cyanide and then five more times with potassium ferrocyanide. Sodium
Morenci. Phelps Dodge Corp. hypochlorite is added to the second cleaner, Exfoam 636 is added
to the last three cleaner stages, and fuel oil is added to the rougher
Prior to 1978, Morenci's molybdenite recovery circuit had been feed. The cleaner tailings are countercurrented with the first cleaner
shut down for several years, due to low molybdenite content in the tailings being scavenged twice before being wmbined with the rougher
wpper concentrates. Although the situation is continually being re- tailings (Fig. 19). The final concentrate contains 55% Mo and under
viewed, it is doubtful that the plant will be started up in the foreseeable 1.0% Cu. In 1981 they changed to the sodium hydrosulfide process,
future. using sodium zinc cyanide and sodium cyanide in the cleaner circuit.
Nevada Mines Div., Kennecon Copper Corp. A 40-ft deep air cell has been incorporated in the circuit to scavenge
the cleaner tailings.
The Nevada mine concentrator was down in I978 due to the
low price of copper. If and when it is started up, a new process Siberian Plants, USSRZ
will be used in the molybdenite recovery circuit. No information was There are two plants in Siberia producing byproduct molybdenite:
available concerning the proposed process at this writing (1978). Tuimski and Sorski. These plants have similar flowsheets. At Tuimski.
Pima Mining Co. the final copper wncentrate containing 18% Cu and 0.8 MoSz with
sodium sulfide, butyl xanthate, fuel oil, and pyridine frother is the
The copper wncentrate wntaining 0.>1.50% MoSz with amyl feed to the molybdenite recovery plant. At Sorski the final copper
xanthate. Shell frother 10, R-17 fmther, and fuel oil is the feed to wncentrate containing 10% Cu and 3.3% MOSSwith kerosene, xan-
the molybdenite plant. The feed is wnditioned with fuel oil and/or thate, zinc sulfate, cyanide, sodium sulfide, OPSB frother, and lime
pine oil and a sodium tripolyphosphate-zinc sulfate solution, thickened is the plant feed. At both plants the molybdenitecopper rougher
to 50% solids, conditioned with a sodium hydrosulfide-ammonium separation is carried out using sodium sulfide, the consumption of
sulfide mixture, and floated in the rougher at approximately 35% which is about 40 Ib per ton. At Tuimski, the rougher concentrate
solids. The rougher concentrate is cleaned twice with the sulfide mix- is cleaned nine times with sodium sulfide, reground to 90% -400
ture, reground, recleaned three times using sodium cyanide and/or mesh. and recleaned two more times to produce a product containing
sodium zinc cyanide, conditioned with zinc sulfate at a pH of 6.5. 42% Moat around 70% recovery. At Sorski. the rougher concentrate
and recleaned three more times with sodium silicate added. The last is reground to 95% -200 mesh and cleaned five times to produce a
cleaning step is to depress talc. A roaster and insoluble float circuit concentrate containing 50% Mo with under 1.0% Cu at around 87%
is available, if required, to remove talc. Exfoam 636 is also used in recovery.
the cleaner circuit. The cleaner tailings are countercurrented with
Silver Bell Unit, ASARCO'a
the first cleaner being scavenged and then combined with the rougher
tailings. The copper concentrate containing about 0.9% MoSz with hexyl
Ray Mines Div., Kemeeon Copper Corp. xanthate. AF238. DF250,and pine oil is the molybdenite plant feed.
The feed is thickened, conditioned with dextrine (2 Ib per ton) and
The copper wncentrate containing 0.3-1.0% MoSz with butyl lime. diluted to 20% solids, and floated. In this initial separation
xanthate and Shell frother 10 is the feed to the molybdenite recovery the molytdenite is depressed into the tailings, the flotation wncentrate
circuit. The feed is thickened to 60% solids; conditioned with sodium (copper-enriched product) conditioned again with dextrine and re-
zinc cyanide; wnditioned for about 40 min with hydrogen peroxide floated. The tailings from this float are combined with the first tailings,
and sulfuric acid at a pH of 6.5 to 7.0; conditioned with sodium thickened, filtered, roasted, repulped with lime, frother, and fuel oil
ferrocyanide, fuel oil, and MIBC; and floated in the rougher at 15- to promote the molybdenite, and floated. The wncentrate from this
20% solids. The rougher wncentrate is cleaned once with sodium float (molybdenite-enriched product) is cleaned twice, reground, re-
ferrocyanide, cleaned several times with Nokes reagent, recleaned cleaned five times, and then leached with sodium cyanide to produce
several times with cyanide, thickened, reground, and recleaned twice a concentrate wntaining 52% Mo with under 0.5% Cu. Sodium cya-
more to produce a final product containing 51% Mo with under nide and frother are added to the recleanen. The cleaner tailings are
1.0% Cu. The first cleaner tailings, the Nokes circuit tailings, and countercurrented with the recleaner tailings being returned to the
the cyanide circuit tailings are all returned to the plant feed thickener. roaster feed thickener and the primary molytdenite float tailings be-
Another stage of regrind is to be added following the first cleaner. coming part of the final copper concentrate. An insoluble float is
They are now using a standard sodium hydrosulfide circuit for the made after the roaster, with concentrate going to final copper concen-
rougher and some of the cleaners. trate.
Rmen Plant, Bulgarian Sipalay Mining Co., PhUlppine
The final copper concentrate wntaining 0.5% M o b , butyl xan- The final copper concentrate containing 25% Cu and 0.40% M o b ,
thate, aemfloat, pine oil, and lime is the feed to the molybdenite recov- with 2-6.AF242, AF194, pine oil, sodium sulfide, and sodium silicate,
ery circuit. The feed is steamtreated at 85'-WC, conditioned with is the feed to the molybdmite recovery circuit. The feed is thickened
kerosene and sodium sulfide, and floated. The rougher concentrate to 55% solids, heated to 210F and wnditioned with ferrocyanide
is again steamed and d a t e d five times to produce a concentrate at 80F. This is followed by conditioning with kerosene and Nokes
wntaining 31.5% Mo at around 30% recovery. The sodium sulfide reagent prior to rougher flotation. The rougher concentrate is re-
consumption is about 50 Ib per ton. Sodium silicate (3 Ib per ton) ground, cleaned once with Nokes reagent, conditioned with hydrogen
is also used in the circuit. peroxide and sodium silicate, cleaned. and recleaned several times
with sodium cyanide. MIBC is used as a frother where needed. The
San Manuel, Magma Copper Co.I6
final concentrate contains 54% Mo with under 1.0% Cu.
The copper wncentrate containing approximately 1.0% MoSl Toquepala, Southern Peru Coppr Corp., P e n P
with Mincrec SM-8, fuel oil, Shell frother 1639, and Z-l 1 is the feed
to two similar molybdenite recovery circuits (one plant is smaller The final wpper concentrate containing about 28% Cu and 0.4
than the other). The feed is thickened to 55% solids, conditioned to 1.0% MoS, with AF3302. Z-ll, pine oil, and AF73 is the feed
A
Copper concentrate Second cleaner
(27% CU, 0.5% Mo) 6-No. 18 Spec Denver cells
w

- -
7 Tailings Concentrate

I I-T
lOOft thickener

Two
7
conditioners, loft xlOft

I 4 f\

Final cleaners
Rougher flotation 6-No. 18 Spec Denver cells
=-No. 3 6 Galigher cells in a 2-2-1 arrangement

Tailings concentrate Tailings Concentrate


4

IF
Copper concentrate
filtering plant

A
- - 1 f

First :leaner \ Gold


16-No. 3 6 Galigher cells cyanidation
.
) plant
Tailings

4
+ -
Concentrate

A
7
7
Leached residue
(Moly concentrate)
1
First scavenger 4 f t x 2 di+sc filter
18-No. 3 6 Galigher cells
7 4 f t x 4 hearth dryer

4 +
Concentrate Tailings
7-
Second scavenger
20-No. 3 6 Galigher cells
7
Final molybdenite concentrate
(92% MoS2, under I% Cu)

I
Tailings conceit rate
-r RG.19. Florvlheet for molybdenite ramvery at San Manual, Magma Copper Co.

to the molybdenite recovery circuit. The feed is thickened to 60% from this circuit contains 40% Mo or more, it is then thickened,
solids, conditioned with fuel oil, diluted with fresh water, and floated dried in a spray dryer. stored, and packaged. If the molybdenum
with Asmol (a N o k s type reagent) at 35% solids. The rougher concen- content is below 40%. the concentrate is conditioned with lignin
trate is reground, cleaned four times with Asmol and/or sodium cya- sulfonate and milk of lime (pH1 1-9) to depress the molybdenite.
nide, cooked 10 min at 160F. recleaned three times with sodium The flotation tailings are then thickened prior to filtering and drying.
cyanide, reground, and cleaned once again with sodium cyanide. Cya- The final molybdenite concentrate is sold with over 40% Mo content
nide leaching tanks are available, if required. The final concentrate and under 2% Cu. Sulfur dioxide gas is added to lower the pH to
grade varies between SO and 54% Mo, depending on how intimately about 4.5 in the insoluble float and Dowfroth 250 is added to produce
locked the molybdenite is with quartz in the ore, with under 1.0% a satisfactory froth condition. It should be noted that there are two
to 1.5% Cu,depending on the type and quantity of chalcopyrite in regrind mills availabk in the plant, but normally they are not required.
the plant feed. The recovery level is around 65%. In 1981 an additional molybdenite recovery circuit was built to treat
the sand fraction of the copper rougher tailings. In 1982 a bank of
Twin Buttes, AJIMUIXMining Co.91
totally enclosed self-asperating flotation machines were incorporated
The feed to the molybdenite recovery plant is the final copper into the rougher circuit of the byproduct plant. By using the same
concentrate containing 0.&1.0% Mo with amyl xanthate and Union air over and over again the hydrosulfide consumption in the rougher
Carbide frother R-23 added. The plant feed is thickened to 65% was reduced by over 60%.-
solids, stored for 4 to 10 hr, briefly conditioned with sodium hydrosul-
Utah Dlr., Kellweott Copper Corp.'
Me (12 Ib per ton), diluted with hot water, and floated in the rougher
at 25% solids. The rougher concentrate is cleaned in seven stages The Arthur and Magma concentrators have almost identical plants
of flotation with sodium hydrosulfide. If the concentrate produced for the recovery of molybdenite. The copper concentrate containing
16-30 MOLYBDENUM

approximately 1.5% MoS2 with sodium dicresyl dithiophosphate, cre- will be diluted and cleaned twice, reground, and recleaned three more
sylic acid, and an alcohol frother is the primary feed to the molybdenite times. The cleaners are to be operated countercurrently with the first
plants (Fig. 14). In addition, a scavenger product containing about cleaner tailings being returned to the rougher. At the time of this
3.0% MoSZ, 8% Cu, and fuel oil feeds the molybdenite recovery writing (1978) no information was available concerning the reagents
circuits after the initial separation stage. The primary feed is thickened; to be used.
diluted to 21% solids; conditioned with dextrine (0.50 Ib per ton),
sodium ethyl xanthate, and an alcohol frother; and floated. The tailings Cuajone. Southern Peru Copper Corp.
from this float, which is the molybdenite-enriched product, is com-
A byproduct molybdenite plant began operation in 1980 at Cua-
bined with the scavenger feed product, thickened, filtered, roasted,
jone. The flowsheet and reagents to be used are similar to those used
subjected to an insoluble float, conditioned with fuel oil to promote
at Toquepala. Important differences are 24-hr storage of thickened
the molybdenite, and floated three times with Nokes reagent to pro-
plant feed, attrition machines prior to the rougher flotation, and the
duce a final product containing 54% Mo with under 1% Cu. A second
scavenging and discarding of the second cleaner tailings. First cleaner
roasting and insoluble float stage is available, if required. tailings are returned to rougher. Nitrogen gas is used to "aerate"
Cornpanin Minera Andina, CODELCO the rougher and first two stages of cleaning. The use of N2 in place
of air in these cells reduced the Nokes reagent consumption by about
In 1977, a byproduct molybdenite recovery plant was started at
50%.38
Andina. The feed to the plant contains primarily chalcopyrite and
is thickened to about 50% solids. It is conditioned with sodium hydro- Ajo, Phelps Dodge Corp.
sulfide and fuel oil, floated in the rougher at 30% solids, cleaned
twice, reground, recleaned twice, reground, and recleaned an addi- In November 1980 byproduct molybdenum recovery commenced.
tional four times. The cleaner tailings are countercurrented with the A standard sodium hydrosulfide is used with sulfuric acid addition
first cleaner tailings being discarded along with the rougher tailings. to the rougher to maintain the pH between 8.5 and 9.0. Eight stages
The only copper depressant used in the circuit is sodium hydrosulfide. of cleaning are used with sodium cyanide used in the last five. Cleaner
The final flotation concentrate is leached with ferric chloride to lower tailings are countercurrented back to the rougher.
the copper content to below 0.1% copper.
Sar Cheshmeh, National Iranian Copper Industries In 1982 a byproduct molybdenite plant was started at La Caridad.
A byproduct molybdenite plant is scheduled to begin operation The process uses sodium ferrocyanide with pH control in the rougher
in 1979 at Sar Cheshmeh. The thickened plant feed will be conditioned and first two cleaners. Sodium cyanide is used in the final cleaners.
prior to the rougher flotation conducted at 30% solids, cleaned twice, The cyanide cleaner is returned to the plant feed thickener. The first
thickened, reground, and stored at 50% solids. The stored concentrate cleaner tailings are scavenged add discarded.

4. CONVERSION OPERATIONS
JANETBRIGGSAND MICHAEL
VERTFS
Other than a small quantity that is upgraded for use in lubricant burden is gradually moved towards and through the drop holes and
formulations, molybdenite concentrates are convened to technical on to succeeding lower hearth levels.
grade oxide, which is the starting material for a variety of products As the concentrate is fed at the top hearth level, the flotation
for the metallurgical and chemical industries. Typical concentrations oil present burns and the concentrate ignites. The reaction, once
in the analysis range of molybdenite concentrates are: started, is exothermic. Operating temperatures range between 1000"
and 1300F. By regulating the air flow to individual hearths and
Wt % the overall air inlet and gas outlet flows, these temperatures are main-
Total molybdenum 40 -59 tained through the roaster. Fig. 20 depicts a roaster operating tempera-
Sulfur 34.4 -37.6 ture profile. The major portion of the oxidation occurs on the upper
Acid insol. 1.6 -15.0 hearths. Additional heat to complete the reaction is provided by fuel
Lead 0.002- 0.03 burners at the lower hearth levels. The overall chemical reaction is:
Tin
Zinc
Bismuth
0.003- 0.006
0.002- 0.02
0.006- 0.09
+
7
-
MoSl - Oz MOO, 2S0,.
2
+
Phosphorus 0.002- 0.04 Efficient dust collection systems employing electrostatic precipita-
Iron 0.3 - 1.0 ton, cyclone. or multiclones installed in the flue gas handling system
Copper 0.006- 2.0 are utilized for improved product recovery and protection of the envi-
Oil 0.5 - 8.3 ronment.
Water 0.5 - 8.4 Roasting temperatures above l m F lead to serious operating
problems because of partial melting and softening of the charge. The
It be out that marked variations be wible, de- problems manifest themselves as excessive wear and corrosion of rab-
pending on the nature and of the ore and the beneficiation ble teeth and plugging of drop holes. Additional -I due to volatili-
procedure employed. zation result at about 13WF, with some sublimation occumng as
The initial phase of the conversion practice involves the roasting low as lIOOoF.
of the concentrate in a multiple hearth roaster. The concentrate is
moved from storage by a belt conveyor or other means to the roaster Oxide
feeder and from there on to the top hearth level of the roaster. Rabble
arms extending fmm the central rotary shaft provide plowing action. The roasted concentrate is discharged from the furnace and either
Drop hole are located either at the center or periphery so that the marketed as technical grade oxide or subjected to additional conver-
MOLYBDENUM PRODUCTS AND USES

or rotating hearth electric furnace. At 2 0 0 0 - ~ 0 Fall of the subox-


ides are oxidized to Moos, which sublimes. The oxide vapors are
drawn off, cooled, and collected in a bag filter. The h e white powder
is well suited for dissolution and hydrometallurgical treatment for
the removal of additional impurities. Without further treatment, sub-
limed molybdic oxide is used as starting material for the manufacture
ofcolor compounds, catalysts, and c e d n grades of pure molybdenum
metal.
A typical analysis of the sublimed oxide is (courtesy Climax Mo-
lybdenum Co.):

Wt %
Molybdic oxide 99.95
Aluminum 0.0010
Calcium 0.0010
Chromium <0.0005
Copper 0.0010
Iron 0.0010
Lead 0.0010
Magnesium <0.0005
Nickel <0.0005
Silicon 0.0075
Sulfur 0.0150
Tin 0.0040
Titanium <0.0005

Hearth Specialized and often proprietary procedures are used to produce


ammonium molybdate with very low impurity levels. For some appli-
FIG.20. Roster temperature profile depicting maximum. minimum, and ideal.
cations, the existence of certain contaminants must be reduced to
extremely low levels. A general route followed begins with molybdic
sion operations to remove impurities. A typical analysis range ofcom- oxide which is dissolved in ammonium hydroxide. Specific impurities
mercially available t e e b n i d grade molybdic oxide is: are removed by selective precipitation and, after filtration, the molyb-
date is recovered from the filtrate by crystallization. lon exchange
Wt % and solvent extraction processs also are being used to separate and
remove impurities.
Molybdenum 56 4 2 There are many forms of ammonium molytdates available. All
Sulfur 0.02 - 0.25 of the molyWates are compounds of ammonia, molybdic oxide, and
Insolubles 5.00 -11.00 water in varying molecular ratios. Sodium and potassium molytdates
Iron 0.50 - 1.00 can be produced when molybdic oxide is dissolved in the correspond-
Copper 0.015- 1.00 ing alkalies and then crystallized. These compounds find uses primar-
CaO 0.05 - 0.20 ily in coloring preparations, toners, and dyes.
ZnO 0.10 - 0.20
Ferromolybdenum
Technical molybdic oxide is marketed either in bulk or in drums. Ferromolybdenum, a molybdenum-iron alloy of varying composi-
bags, or cans containing a predetermined amount of molybdenum. tion is another form of molybdenum used in iron and steel melts.
This is a convenience to the users in the steel industry. When added It is available in low carbon and high carbon grades. It is produced
to molten steel, molybdenum oxides are reduced to the metallic form in a smelting operation which removes most impurities in the form
and alloyed. The gangue minerals are removed with the slag. of a throwaway slag. The high carbon alloy is made by fusion in
electric furnaces. Technical grade molybdic oxide (Moo3), molybde-
Molybdic Oxide Briquettes
nite (MoSz), calcium molybdate (CaMoO,), or sodium molytdate
The technical grade molybdic oxide can be formed into briquettes (Na~Moo,) can be used as the furnace charge. Carbon is added as
which facilitate additions of molybdenum in electric and foundry the reducing agent along with lime or fluorspar which function as
steelmaking processes. In the briquette form losses experienced in fluxes. The furnace is water-jacketed and has a refractory-lined inte-
blowoff when oxide is added to the furnace charge are minimized. rior. After the alloy is fused, it is cooled and the mass broken into
Storage and handling are also simplified. To prepare the briquettes, pieces and sized according to specific requirements.
technical grade oxide of known composition is mixed with pitch or The thermit reduction procgs producing the low carbon alloy
other binder and formed into briquettes in a hydraulic press. The is more widely practiced in industry. Technical molybdic oxide, alumi-
size of a briquette is adjusted so that each briquette unit corresponds num, ferrosilicon, iron oxide, limestone, burned lime, and fluorspar
to a known quantity of molybdenum. In this way, the addition of a are mixed and discharged into a bottomless carborundum brick-lined
briquette to the steelmaking furnace will add a known amount of steel reaction pot that is set in a shallow sand bed. The sand is graded
molybdenum to the heat. about the pot and the reaction mix fused for ignition. The fumes
Sublimed Molybdic Oxide and dust from the very rapid reaction are drawn away by fans in a
dust hood placed above the reaction vessel. A bag filter is used to
To produce purified molybdic oxide, technical grade oxide is sub- recover the particulate matter from the fumes. The reaction is com-
jected to a sublimation procedure using either a retort-tube furnace pleted in 5 to 7 min, and the pot is lifted. After 8 to 10 hr. the still
16-32 MOLYBDENUM

hot solidified mass is removed from the sand pit and the "button" form in which molybdenum was added to steel but this has largely
quenched with water. The cap of slag is then knocked off the button. been replaced by adding technical grade molybdic oxide directly to
The quenching produces fine fractures and permits the breaking of the melt. In present day (1973) steelmaking ferromolybdenum is usu-
the alloy m a s into pieces. suitable for crushing and sizing. ally added as a final composition adjustment or when there is no
In older steelmaking practice, ferromolybdenum was the favored opportunity to remove slag from the melt.

5. MOLYBDENUM PRODUCTS AND USES


JANETBRIGGSA N D MICHAELVERTES
General Sprayed molybdenum metal is used on automotive piston rings and
- ..
There are four maior aoolications in which molvbdenum is used:
in alloy additions, in the metallic form as pure molybdenum, molybde-
tools as ways resist wear and

num chemicals and catalysts, and as molybdenum disulfide lubricants Abrasion-Redstant Irons and Steels
(see Table 9). In each of these applications, molybdenum has to be
separated from associated gangue minerals at some stage during the
processing. In the case of alloy additions, gangue minerals are removed The mining industry is particularly interested in wearing parts
as molten slag during the preparation of the alloys. Chemicals, cata- having a superior combination of abrasion resistance and toughness.
lysts, and molybdenum metal are produced from molybdic oxide puri- Relatively highly alloyed irons and steels, which might not have been
economically attractive 10 or 15 years ago, are now assuming increas-
fied by sublimation or chemical means. Lubricant grade molybdenum
disulfide is separated from the gangue minerals by beneficiation. ing importance, while certain materials having a lower first coat are
The MoSa concentrate produced by milling and as described in no longer in demand. One major reason for this trend is the growth
the preceding sections can be either purified to a high grade form in large high-powered machinery and equipment, where good reliabil-
+
of the mineral (99 % MoSz), or it can be converted to the technical
ity and high abrasion resistance of wearing parts are essential to reduce
+
grade oxide. The 99 % MoSI concentrate is produced by additional
shutdown time for maintenance or replacement. On many of these
machines, such as those in the new ore crushing and grinding plants,
flotation circuits and acid leaching procedures. This purified concen-
operation is largely by automatic or computer control to minimize
trate is extensively used in the manufacture of lubricants because of
manpower per unit of production. When one of these machines must
the laminar crystal arrangement of the molybdenite structure that
be shut down to replace worn or broken parts, it can be very costly
retains lubricity over a wide temperature range.
in terms of both manpower and lost production.
Molybdenum Metal
High-Chromium White Irons
Molybdenum metal powders are produced by hydrogen reduction
of ammonium molybdate or molybdic oxide. Those powders made The high-alloy chromium-molybdenum white irons shown in Ta-
from the oxide are used in certain catalyst applications or are subse- ble 10 are being adopted in increasing amounts by the mining, cement,
quently formed into pellets or briquettes for alloying in specialty steels and steel industries. These alloys, with the highest abrasion resistance
and high temperature alloys. The somewhat high purity powders made of any of the commonly used alloys in the mining field (except for
from ammonium molybdate are generally used as starting material tungsten carbide), are changing our concepts as to the type of applica-
for sheet. bar, and wire type products. This is accomplished in either tion where white irons can be used. The old- types of white iron
of two ways. The metallic powders may be mechanically or hydrostati- had a good wear resistance but their deficiencies in impact resistance
cally compacted, then sintered to high density, followed by direct and hardenability restricted their use to small parts not subject to
conversion to miU products, or may be formed into electrodes that impact loading. On the other hand, the new chromium-molybdenum
are melted under high vacuum into water-cooled molds forming ingots white irons are being utilizcd for parts such as ball-mill liners, wear
weighing more than a ton. These are subsequently extruded and rolled shoes, grinding balls, and rolling-mill rolls to give longer life and
to mill product shapes. greater economy per unit throughput than other materials.
Molybdenum metal is used extensively in many aerospace, elec- One distinct advantage of the high-chromium irons is their ability
tronic. high tempemture furnace, and die casting and hot work tooling to respond favorably to heat treatment. They can be annealed for
applications in a nonoxididng environment and at extremely high machining, then hardened to a martmsitic structure by reaustenitiz-
temperatures. It also has excellent resistance to many corrosive media ing, followed by a quench in air, oil or molten salt.
such as molten glasses, fused salts, acids, and liquid metals so it The compositions in Table I I are listed in the approximate order
finds applications in the glass, nuclear, and chemical industries. of decreasing abrasion resistance. In making selections for a specific
application, however, it is n-ry to consider both relative cost
and the effect of section size or design.
The ISCr-3Mo alloy, when used in light to moderate sections.
Tablo 9. Estlmatod 1972 UHS of MoI).bdonum has consistently shown the best abrasion resistance of the moderate
in tho F m World cost fmous alloys in both service environments and laboratory tests.
It is now extensively used in abrasion-resistant castings for shot or
Use
grit blasting equipment, impact pulverizers, sand classifiers, sinter
Alloy steel (other than stainless screens, and liners for chutes and ore-grinding mills.
and tool steels) The ISCr-2Mo-ICu and 2OCr-2Mo-ICu mmpositions listed in
Stainless steel Table 10 appear to be better adapted to heavy-section castings than
Tool and high-speed steel the highcarbon grades of 15Cr-3Mo. The 12Cr-5Mo type with its
Chemical and lubricants relatively low alloy coat is well suited to light-section castings such
Cast imn and steel mill mlh
Supenlloya as small grinding balls. The small molybdenum content is very etfective
Moly&num metal in suppresing the formation of undesired pearlite, which can impair
Miscellaneous the wear resistance. Molybdenum is frequently added to the 27Cr
irons for use in the heavy sections such as in dredge pump castings
for the same reason.
MOLYBDENUM PRODUCTS AND USES 1-

Tablo 10. High-Qlrocnlurn Mortonsltlc Whlh Irons


Typical composition, % Heat
Grade C Mn Si Cr Mo Other treatmenta
16Cr-3Mo 2.4-3.6 0.7 0.6 15 3 - AQ & Td
15Cr2M~lCu 3.4 0.7 0.6 15 2 1.0 Cub AQ&T
20Cr2Mo-1Cu 3.0 0.7 0.6 20 1.7 1.0 Cub AQ&T
l2CrMo 3.2 0.7 0.6 12 0.5 - Q&Tc
25-32Cr 2.3-3.0 1.0 1.0 21 0.5 - AQ&T
a The wmpoaitiona can also be used a s a t and atreen-relieved if cooled rapidly enough below about 1650F to supress pearlite formation.
In aome eases 0.5-1.08 Ni in used in place of l.W Cu in these compositions.
'A relatively rapid quench in air, molten salt, or oil in required to suppress pearlite in thii mmpoaition.
d AQ, airquenched, Q, quenched, T. tempered.

A 6Mn-IMo alloy has given good results for parts such as ball mill
steels discharge grates, scoop Lips, and grizzly screens.
Molybdenum is contained in many, if not most, of the steels used
Engineering Steels
by the minerals industry for wear resistance because of its economical
contribution to hardenability. Alloy steels, excluding stainless and tool steels, make up almost
Table I I lists some of the typical high and medium carbon fully half of the molybdenum market. In addition to mining machinery
hardened steels used as abrasion-resistant castings for parts such as these steels are found in automotive, raihad, structural, pipeline.
grinding balls and ball-mill liners. Production of steels of this type aircraft, and many other fields. Alloy steels are finding increasing
has been limited to s p e c i a l ' i applications and to the relatively few use over carbon steels because of their higher strength, which permits
foundries equipped with suitable heat-treating facilities. lighter weight in addition to other advantages. Molybdenum, alone
The steels listed in Table 12 are used to produce castings with a or in combination with other alloying elements such as manganese,
"hard pearlitic" structure having a Brinell hardness between 300 and chromium, and nickel, is widely used because of its economical contri-
440,depending on section size and heat treatment. They are relatively bution to strength. Not only is it more efective but it can be recovered
foolproof and easy to produce. Grades I to 4 are extensively used substantially completely from additions and from scrap.
in many large grinding mill liners where impact conditions are too MediumCubon Steel. Medium-carbon steels are widely used
severe to permit application of white irons. Grades 5 and 6 are de- for parts such as shafts and acoount for an appreciable amount of
signed for grinding balls, 2-5 in. in d a m , for the grinding of high- the molybdenum consumed in alloy steel. One of the major reasons
silica ores, and where impact is too severe to permit the use of martens- why molybdenum is used in this type of steel is its economical contri-
itic steel or iron grinding balls. bution to hardenability so it is possible to obtain a given strength
In addition, quenched and tempered high-strength low-alloy steels in larger sections with a specific heat treatment.
are used in both the wrought and cast form where combinations of Optimum strength and toughness are obtained when the harden-
structural strength, impact toughness, and abrasion resistance are ability is high enough to give a wholly martensitic structure with the
required. Basically these steels contain 0.10-0.40% C with sufficient cooling rate obtained in quenching. The appearance of bainite and.
alloy content so they can be fully hardened by quenching. Molybde- particularly. of ferrite detracts from these properties. In relatively
num, usually from O . Z M . M % , is used in practically all steels of small and medium size parts where the best performance is desired.
this type and frequently is combined with other alloys such as manga- composition and treatment are selected to produce a t e m p e d mar-
nese, silicon, chromium. nickel, vanadium, and boron. Steels of this tensitic structure. In massive forgings, on the other hand, the danger
type are extensively used, for example, in teeth for shovel dippers of quenching cracks makes a compromise of a bainitic structure desira-
and are increasingly diplacing unalloyed steel beeause of the more ble. In both cases molybdenum performs vital and specific functions
favorabk cost figures per unit throughput. in controlling the microstructure obtained by heat treatment.
Molybdenum likewise has proved useful in austenitic manganese Toughness is a factor that cannot be ignored in the selection of
steels of the Hadfield type. Service and laboratory results have shown mediumwbon alloy steels. In part, it can be controlled through
that the abrasion resistance of this 12% Mn steel increases as the hardenability since more complete hardening confers higher tough-
carbon content increases from about 0.7 up to 1.4%. There is, how- ness. There is the additional aspect of temper brittleness, however,
ever, a tendency for the steel to become embrittled by the formation which is the embrittlement m u r r i n g on slow cooling or isothermal
of grain-boundary carbide films as the carbon is increased, especially holding of quenched and tempered steel between about 800" and
in heavy-section castings. The addition of I % Mo is effective in inhibit- 1100'F. A somewhat similar form of embrittlement is observed on
ing or suppressing carbide embrittlement during heat treatment or long-time service in this temperature range.
upon subsequent exposure in service to temperatures above 7WaF. The unique function of molybdenum in minimizing temper brittle-
Decreasing the manganese content of the Hadfield-type steels ness accounted for some of the first commercial applications of molyb-
results in a substantial improvement in resistance to high-stress abra- denum. Practically we know that molyMenum is the only common
sion. It is then essential to add molybdenum to retain sufficient ductil- alloying element that can ameliorate temper brittleness but the mecha-
ity and toughness in applications involving heavy-section castings. nism is not entirely clear.

lablo 11. Martonsltic Hiph and Medium Carbon Cast Stools


Typical composition, % Heat
C Mn Si Cr Mo treatmentm
0.7 0.9 0.1 1.3 0.4 Salt Q & T
1.0 0.7 0.6 6.0 1.0 AQ & T
1.2 0.7 0.6 1.0 0.3 OQ & T
0.5 0.7 0.6 0.9 0.5 OQ&T
a Salt Q, saltquenched, AQ, airquenched, 0 Q oilquenched, T, tempered.
MOLYBDENUM

Table 12. Hard Pearlltic Low-Alloy Shwh


Typical composition, %
Grade C Mn Si Cr Mo Ni Heat treatments

--> - -
5 1.1 0.7 0.6 1.0 0.2 - Ascast, air-cooled
6 0.8 0.7 0.6 1.0 0.2 - Ascast, airsooled
AQ, airquenched; T,tempered

Carburizing Steels. With low-carbon steels intended for carbur- sures where the hydrogen will attack the carbon in unalloyed steel
ized gears and similar parts, hardenability is again the key factor as with resultant cracking and damage. The addition of 0.5% Mo materi-
it is with the medium-carbon steels. It has been proved that molybde- ally increaws the same temperature limit where hydrogen damage
num is the most effective element in conferring hardenability to both will not occur while chromium further enhances resistance at higher
the carburized high-carbon case and the low-carbon core. temperatures.
Molybdenum additions. generally in the range of 0.104.25%, Maraging Steels. A final subject under alloy steels might be
have long been used in carburizing steels to produce the required mention of the effect of molybdenum in maraging steels, which are
hardenability. More recently. a closer understanding of the contribu- gaining increasing stature for aerospace and metalworking applica-
tions of the various alloying elements and changes in the relative tions. These steels are quenched to martensite and then aged to give
cost of these alloys has led to the introduction of higher molybdenum a yield strength of 200 ksi or higher. The most widely used grade
contents, up to 0.60%. in combination with small amounts of chro- contains about 18% Ni, 8% Co, 5% Mo, and 0.5% Ti. Molybdenum
mium or chromium plus nickel. confen both solid-solution and age hardening. While cobalt produces
High-Strength Struchunl Steels. High-strength structural steels no hardening of the iron-nickel binary alloys, the combination of mo-
have low carbon contents for weldability with sufficient alloy to give lybdenum and cobalt as in the commercial alloys has a cumulative
a strength superior to that of unalloyed steels with the same carbon effect. The cobalt is believed to decrease the solubility of the molybde-
content. The required combination of strength, weldability, and tough- num and to produce more precipitate at higher supersaturations. In
ness can be obtained in various ways. contrast to other elements that could be used for age hardening, molyb
Arctic Grade is a high-strength low-alloy steel developed specifi- denum permits retention of high impact toughness to high strength
cally for pipelines although further work is underway on its application levels. The toughening effect, which is attributed to a retardation of
to the transportation industry for automotive bumpen, railroad can, grain-boundary precipitation, appears to be unique to molybdenum.
and heavy mobile equipment. Due to its acicular ferrite structure, Stainless Steels
this grade with a nominal c o m p i t i o n of 0.05% C, 1.6% Mn, 0.25%
Mo, and 0.06% Cb combines high strength and toughness to make As indicated in Table 9, stainless steels represent the sccond largest
it an ideal material for line pipe, especially where good impact strength use of molybdenum. Today it is mainly utilized in the austenitic grades
at subzero temperatures is required. This was the fint steel meeting although this picture may change in the future.
X-70 requirements (with a minimum yield strength of 70 ksi) to go Austeaitlc Steels. Molybdenum additions to austenitic stainless
into service on an operating pipeline anywhere in the world. steels improve corrosion resistance and elevated-temperature strength
Molybdenum also makes a significant strengthening contribution but have no significant effect on room-temperature mechanical proper-
to the quenched and tempered grades. The use of these types for ties. Molybdenum improves general corrosion resistance in many me-
wear resistance in the mining field has already been mentioned. They diums and has a pronounced effect in increasing resistance to pitting
also have proved economical in many other applications. For example, and contact corrosion.
in tanks transporting liquefied gases at room temperature, the use The most universal of the molybdenum-containing austenitic steels
of molybdenum-containing quenched and tempered steels with a yield is AISI Type 316. Typical of its applications would be in scrubber
strength of 100 ksi minimum has permitted a reduction in shell thick- emission-control devices where molybdenum-free grades do not have
ness that directly contributes to the payload operaton can haul. sufficient cormsion resistance in most cases to resist the high-sulfur
Molybdenum lad Cbromlum-Molybdenum Steels for Use Above high-humidity gases.
Room Tempemhue. Two factors-resistance to embrittlement and There is also a move to higher molybdenum contents for service
softening-have led to extensive use of molybdenum in steels for where the conventional AISl Type 316 and 317 (19Cr-13Ni-3.5Mo)
service above room temperature. As a matter of fact, molybdenum do not have sufficientcorrosion resistance and where resort to nickel-
is the most common strengthening element in nonaustenitic steels base alloys would be uneconomic. As an example in point, proprietary
for elevated temperature service. Most of the high-temperature steels grades with about 20% Cr. 25% Ni, and 4.5% Mo are being produced
that have been developed for service in this area are based on molybde- in the US and Europe. They are being used to combat the extreme
num additions to increase hot strength and confer resistance to embrit- corrosion encountered in wet-pr- phosphoric-acid plants and are
tlement and chromium additions for resistance to oxidation and hot coming into consideration for other processes, such as pulp and paper
corrosion. A popular steel for hydrocracking reactors, for instance. bleaching where AlSl T y p e 3 16 and 3 17 are totally inadequate.
contains 2.25Cr- IMo. Mnrtensltic Steels. The second major classification of stainless
In view of demands from the petroleum and chemical industries steels is the martensitic type, which can be hardened by normal
for larger and larger capacity vessels, hardenability becomes a factor quenching and tempering with the attainable hardness a functiotr of
with these steelsas well since accelerated normalizing or dip quenching the carbon and chromium contents. These grades often contain up
is used to obtain the higher strengths needed to keep wall thickness to 1% Mo or even more to improve corrosion resistance, particularly
and weight within the limits of what can be produced and transported. to commercial detergents, and to increase the edge-holding ability.
Hydrogen attack at elevated temperatures is encountered in the F e d t i c Steels. The third major cla.siication of stainless steels
pr-ing of many of the important chemicals in today's industrial is the ferritic type, which in the past has not had the stature of the
economy. In the petroleum-refining field, for instance, the growth austenitic grades because of its lack of corrosion resistance under
of hydrogenation p r o c e s s for treating hydrocarbons has been phe- mcst conditions and its relatively poor formability. Recent work as
nomenal. This and other pmcescs operate at temperatures and pres- well as improved melting facilities have now changed this picture
MOLYBDENUM PRO[ UCTS AND USES 1-5

to the extent that it seems assured that a family of ferritic chmmium- ered as relatively Low-alloy high-speed steels with about 0.4% C,
molybdenum steels will assume a strong position in the stainless-steel one might have expected changes in composition corresponding to
field. t h m that have occurred in the high-speed steels. Instead, industry
The first of what we might consider the modern ferritic chromium- has gone to an entirely different type, a 5% Cr steel with about
molybdenum steels was developed for automotive trim when it was 1.5% Mo and 0.4% C, which was developed originally for aluminum
found that the 17% Cr steel was corroded by salt used for deicing die-casting dies. This grade of steel (and its modifications) has been
streets. The solution proved to be the addition of molybdenum, which found to present so many advantages of the tungsten types that the
has similar dfects in improving the corrosion resistance of the ferritic latter have practically disappeared in the US.
steels as it does in austenitic steels. As a result, 17Cr-IMo steel is One of the outstanding characteristics of the chromium-molybde-
now a standard in various wuntries for automotive trim. It is expected num steels is their much higher toughness, both at room and elevated
that other applications of this grade will be developed. temperatures, as compared with the 9W-3Cr-V steel. The toughness
The next step-up in corrosion resistance is the so-called "444" of the tungsten steel may be further decreased by incomplete harden-
with 18% Cr, 2% Mo, and small amounts of columbium or titanium. ing, such as may occur even in sections of 4 x 4 x 4 in. On the other
It has a general wrrosion resistance equal to or better than that of hand, the chromium-molybdenum steels have superior hardenability
the general purpose 18Cr-9Ni steels but is a lower cost steel. Moreover, so they can be air-hardened to substantially full hardness even in
this grade is not subject to the stresscorrosion cracking that plagues very large sections.
austenitic steels such as the 18Cr-9Ni in a number of media, notably The whole field of hot-work dies is still in the process of change.
seawater and other chloridecontaining solutions. Compared with a While the 5Cr-Mc+V grades have won acceptance as the standard
17% Cr steel (AISI Type 430) and other molybdenum-free ferritic material in most cases, they are facing competition from some of
steels, the "444" has vastly improved corrosion resistance and needs the newer materials that appear to have economic justification for
no postweld heat treatment. long-run and special dies. Among these newer materials are the marag-
A free-machining modification of the 18Cr-2Mo type has machin- ing steels, the superalloys, and molybdenum-base alloys. The molybde-
ability characteristics comparable to t h m of any of the available free- num-base TZM alloy (M04.5Tib.08Zr) is used for a number of hot-
machining stainless grades with equivalent or superior wrrosion resis- working applications because of its high hot hardness and resistance
tance. to heat checking.
A third grade in the series, which is being produced commercially, Cold-Work Steels. Two major points to be noted in recent years
is a high-purity 26Cr-IMo steel with outstanding wrrosion resistance are the increasing emphasis being placed on hardenability and the
at least equal to that of any of the present stainless grades. It requires introduction of a new family of steels intermediate between the old
special melting to reduce the carbon and nitrogen contents. Other 12% Cr grades and the oil-hardening manganese steels.
companies are studying different chromium-molybdenum ratios with Oil hardening offers advantages over water quenching because it
18 to 28% Cr and I to 4% Mo to get different combinations of decreases the chances of cracking during hardening and gives less
mechanical properties and wrrosion resistance. size change and higher toughness. Air hardening gives the same advan-
tages over oil hardening. One clue to the importance of molybdenum
in the cold-work steels is clear when it is realized that the use of
Tool Steels air hardening requires higher hardenability than is needed in oil hard-
Tool steels cover a number of different types ranging from high- ening and molybdenum is the most effective of the common alloying
speed down to unalloyed steels. Molybdenum is widely used in all elements in increasing the hardenability of these high-carbon steels.
the alloyed types to contribute resistance to softening, hot hardness. Following along these lines, an entire family of medium-alloy air-
hardenability, wear resistance, and toughness. hardening steels, all of which contain molybdenum in amounts from
High-Speed Steels. Either tungsten or molybdenum is needed I to 1.5%. has been introduced. The most widely used of these is a
to confer the characteristic red hardness to high-speed steels. The 5Cr-IMo steel with 1% C. It gives a life about twice that of carbon
effectiveness of these two elements is more or less in proportion to tool steel or oil-hardening manganese steel but about half that of
their atomic weights so 1% Mo produces approximately the same the 12% Cr types. Therefore, it is suitable for intermediate-life dies
results as 2% W. and for dies where the amount of finishing and machining makes it
Since the introduction of the first of the modem molybdenum- desirable to use the lower alloy steel with better machinability than
containing grades in 1933, there has been a steady growth in the the 12% Cr types.
percentage of high-speed steels represented by the molybdenum and
molybdenum-tungsten types. The usage of molybdenumcontaining
types now accounts for about 93% of the high-speed production in Chemicals and Lubricants
the US. The growth rate has been slower in other wuntries than in
the US but today, even in Great Britain, one of the last countries The fourth highest category in Table 9 is represented by chemicals
to make the shift, about 70% of the total high-speed production where the principle applications are in the areas of catalysts, lubri-
contains molybdenum. cants, pigments, dyes, coating systems, corrosion inhibitors, and ferti-
Various reasons have lead to the conquest of the high-speed steel lizer supplements.
field by molybdenum. One major factor is the price. While the relative
prices vary from country to country, at present 6W-5Mo-4Cr-2V costs
about 62% as much in the US as 1 8 W X r - I V but gives at least Molybdenum is one of the more widely used catalytic elements.
equivalent cutting performance. A second advantage is the lower den- The very properties that contribute to the complexity of molybdenum
sity of the molybdenum-containing types, which is important since chemistry are responsible for its wide usefulness in catalysis. Ease
large tool producers buy by weight but sell by volume. This weight of transition from one valence state to another allows it to function
saving compared to 1 8 W X r - I V ranges from about 6% for the 5W- readily as an electron acceptor or donor.
5Mo-4Cr-2V type to 9% for the 8Mo-4Cr-2V grade. There are other Molybdenum compounds are used commercially to catalyze many
benefits in addition to these. One is the superior toughness of the types of reactions, such as oxidation and reduction, hydrogenation
molybdenumcontaining grades, which may be utilized either to obtain and desulfurization, isomerization, and many others. They may func-
tougher tools at the same hardness or to increase the hardness and tion as the principal catalysts or as promotors and activators of other
wear resistance for equivalent toughness. catalysts. In reactions involving petroleum and natural gases, the fre-
Hot-Work Steels. Before World War 11, the most popular hot- quent interchangeability of sulfur and oxygen in molybdenum com-
work steels were the tungsten types with around 9-14% W, 3 4 % pounds is a highly useful property since sulfur can poison other cata-
Cr, and small amounts of vanadium. Since t h e e might well be wnsid- lyst systems but not those that rely upon molybdenum.
16-36 MOLYBDENUM

Lubricants Molydbenum oranges have been standard paint pigments for many
Molybdenum disulfide is an important lubricant that is used either years and will probably continue to be so for outside usage. Molybde-
alone as a dry-film coating, mixed with greases or oils, or blended num is also found in various organic dyes and color lakes.
with plastics used to make molded parts. Corrosion Inhibitors
Dry-film coatings find many applications in pa- such as bearings
and gears where, for any of several reasons, conventional lubricants Sodium molydate has long been known as an effectivecorrosion
are not practical, For example, gears working in an area with dust inhibitor in aqueous systems. It did not find wide acceptance in this
or din in the air often cannot on oil or lubricants because application.for
.
many years because of the widespread and long-stand-
of the tendency to pick up the air -wntaminat;s. newide temperature lng usage of chromate. Sodium m o l y U t e is now receiving considera-
range over which disulfide is stable is another ble attention and some application as a corrosion inhibitor h a u s e
for its selection over and disulfide of its much lower level of toxicity as compared with the chromate.
mixed with greases and oils increases the effectiveness of the system
because of its tendency to "plate out" on bearing surfaces and provide P h t s and Soils
lubricity over extended periods of time. Molybdenum is commonly accepted as a trace element essential
Pigments to the normal metabolism of higher plants. The need apparently varies
considerably with different plant t y p . Legumes in particular are
An important new inhibiting-pigment system based on molybdates sensitive to molybdenum levels because the symbiotic bacteria in the
is on the market. This pigment combines nontoxicity, whiteness, and root nodules require molybdenum for the fixation of atmospheric
corrosion inhibition. Furthermore, it is cost competitive with several nitrogen. Where sufficient molybdenum is not available in the soil,
currently used materials regarded as toxic. it can be added in fertilizers, foliar sprays, or seed treatment.

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