Note: Descriptions are shown in the official language in which they were submitted.
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PYROMETALLURGICAL PROCESS FOR TREATING
METAL6CONTAINING MATERIALS
FIELD OF THE INVENTION
The present invention is directed to the--
pyrometallurgical treatment of inetal-containing materials
and, in a preferred embodiment, the formation of.tungsten
carbide using a two stage pyrometallurgical process.
BACKGROUND OF THE INVENTION
Two stage processes for producing tungsten carbide
(WC) are known. For example, in U.S. Patent No. 3,373,097
entitled "Method For Separation Of A Metal-Containing
Halide Phase From A Gangue-Containing Silicate Phase and
Electrolysis of Halide Phase To Obtain The Metal" by Gomes
et al., issued March 12, 1968, a process for producing
tungsten carbide is disclosed. The process involves a
molten phase separation employing sodium chloride (NaCl) in
which the tungsten reports to a less dense upper halide
phase while impurity elements such as calcium, manganese
and iron are recovered in a denser lower silicate phase.
The separation is effected by heating a mixture of halide
salts, concentrates of either scheelite (CaWO
4) or
wolframite ((Fe,Mn) W04) , and a slag former such as sodium
silicate to 900 C to 1,100 C. After fifteen minutes to an
hour at the elevated temperature, the phase separation is
completed and the halide phase is decanted for processing
by molten salt electrolysis.
U.S. Patent No. 4,489,044 entitled, "Formation Of
Tungsten Monocarbide From A Molten Tungstate-Halide Phase
By Gas Sparging" by Gomes et al., issued December 18, -1984,
reissued as Re 32,612 on February 23, 1988, discloses a
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process for producing tungsten carbide. The process
involves the formation of a sodium chloride/sodium__
tungstate (Na2WO4) phase by molten phase separation, similar
to.the process described above. The tungsten monocarbide
is produced by sparging the melt of sodium chloride and
sodium tungstate with a hydrocarbon gas, particularly
methane (CH4) or natural gas. According to the disclosure,
other alkali halides can be substituted for sodium
chloride.
In May, 1985, Gomes, Raddatz and Caranahan made a
presentation at the Third Tungsten Symposium in Madrid,
Spain (May 13-17, 1985) regarding a two step technique for
producing a granular tungsten carbide powder directly from
scheelite or wolframite concentrates. The concentrates
were first reacted at 1,050 C with a sodium chloride/sodium
metasilicate (NaZSiO3) melt. The reaction produces two
immiscible liquids: a lighter tungstate-halide (NaCl-NaZWOy)
phase containing 99 percent of the input tungsten and a
denser silicate slag phase containing 90 to 96 percent of
the iron, manganese and calcium oxides. After phase
separation, the tungstate-halide phase is sparged with
methane gas in a second step to yield granular tungsten
carbide. The tungsten carbide is recovered from the
reactor by decanting excess salt, cooling, water leaching
'and scraping. See "Preparation of Tungsten Carbide by Gas
Sparging Tungstate Melts", Gomes et al., Journal of Metals,
December 1985, pps. 29-32.
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The processes described above all include an inztial
slagging operation in which a tungsten concentrate is
combined with a siliceous flux and sodium chloride (other
halide sources can be substituted). The tungsten compounds
contained in the concentrate (e.g., calcium, iron, or
manganese tungstates) react with the sodium chloride and
the sodium silicate to produce two immiscible phases: a
molten salt and a molten silicate slag. The tungsten
preferentially reports to the molten salt phase, while the
majority of the impurities are rejected to the slag phase.
The viscous slag is more dense than the salt and settles to
the bottom of the furnace crucible. The salt phase, which
chiefly consists of sodium chloride and sodium tungstate,
is forwarded to a second stage for processing into tungsten
carbide.
A problem with the methods described above is that the
lower density tungsten-containing phase also includes a
halide salt (e.g., sodium chloride). During subsequent
sparging operations, this halide salt volatilizes and
deposits within various components of the gas handling
system. This accretion of salt eventually leads to
downtime in order to clear the obstructions. The sodium
chloride also represents an operating cost. Additionally,
the sodium chloride is extremely corrosive and its presence
increases the cost of the materials due to the need to
employ corrosion resistant materials and results in higher
operating costs due to the corrosion. Furthermore, the
sodium chloride dilutes the sodium tungstate in the
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sparging operation, effectively reducing the chemical
activity of the tungstic oxide (Wo3).
It would be advantageous to provide a method for
forming metal carbide (e.g., tungsten carbide) from a
metal-containing mineral using a pyrometallurgical process.
Additionally, it would be advantageous to form metal (e.g.,
tungsten) carbide without the need for forming a fused
metal-halide salt. It would be advantageous to provide a
process in which a majority of the tungsten input to the
system is converted to tungsten carbide. It would be
advantageous to provide a process in which tungsten carbide
can be formed.efficiently and economically without a large
amount of system downtime.
SUMMARY OF THE INVENTION
In accordance with one embodiment of the invention, a
method is provided for concentrating the metal in a metal-
containing material by employing a pyrometallurgical
operation. The pyrometallurgical operation includes a
heating step in which the metal-containing material is
heated in the presence of at least one sodium or potassium
compound to melt the metal-containing material and form a
high density metal-containing phase and a low density slag
phase. The majority of the metal reports to the high
density metal-containing phase. The two phases are
immiscible and the high density metal-containing phase
separates by gravity from the low density slag phase.
Because of its higher density the high density metal-
containing phase will settle to the bottom of a furnace
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.acjm
crucible. The two phases can then be separated.
Preferably, the high density metal-containing phase is
,
subjected to a second pyrometallurgical operation, i.e.,
sparging with a carbon-containing gas, to form metal
carbide.
Although the methods of the present invention have
been found particularly applicable to tungsten-containing
materials, the methods can be employed to recover other
metals from metal-containing materials. Examples of such
other metals are Group III-B metals (e.g., thorium), Group
IV-B metals (e.g., titanium, zirconium, hafnium), Group V-B
metals (e.g., vanadium, niobium, tantalum), Group VI-B
metals (e.g., tungsten) and Group VII-B metals (e.g.,
manganese and rhenium). More preferred are refractory
metals such as tungsten, titanium and tantalum. Most
preferred are tungsten-containing materials. Examples of
tungsten-containing materials include tungsten ores such as
huebnerite (MnWO4), scheelite (CaWO4), ferberite (FeWO4) and
wolframite ((Fe,Mn)W04). Additionally, the method of the
present invention can be effective with other tungsten-
containing materials such as flue dusts and various
secondary materials (e.g., slag and scrap). While the
methods of the present invention are useful in connection
with a numberof materials, for purposes of clarity, the
following description will be of a preferred embodiment
employing a tungsten-containing material. It is to be
expressly understood that other materials, such as those
listed above, can also be employed.
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In accordance with another embodiment of the present
invention, tungsten carbide is formed from a tungsten _
mineral concentrate. The tungsten mineral concentrate is
heated in the presence of a sodium or potassium compound to
a temperature from about 900 C to about 1,200 C in order to
obtain a first melt. The first melt is maintained at
temperature until it separates into a higher density
tungsten-containing phase and a lower density slag phase.
The higher density tungsten-containing phase is then
separated from the lower density slag phase. The higher
density tungsten-containing phase is heated to a
temperature of about 1,050"C to about 1,200 C to obtain a
second melt. Methane gas is then sparged through the
second melt to form tungsten carbide. The tungsten carbide
enriched portiori of the second melt is removed and purified
in order to obtain purified tungsten carbide. Preferably,
the first melt is formed in the substantial absence of
sodium chloride. In a preferred embodiment, a portion of
a sparged, spent salt-containing mate"rial is recycled from
the second melt to the first melt in order to aid in the
separation of the higher density tungsten-containing phase
from the lower density slag phase and to recycle tungsten
not converted to tungsten carbide in the sparging stage.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a flow diagram of one embodiment of the
process of the present invention.
Figure 2 is a ternary phase diagram of the WO3- NaZ0-
SiOZ system at 1,200 C.
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Figure 3 is an illustration of a pilot scale slagging
system in accordance with an embodiment of the present ~
invention.
Figure 4 is an illustration of a pilot scale sparging
system in accordance with an embodiment of the present
invgntion.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with one embodiment of the present
invention, a pyrometallurgical process is provided for
forming a tungstate salt, for example, sodium tungstate or
potassium tungstate and preferably sodium tungstate, from
a tungsten-containing material. Preferably, the tungsten-
containing material is a tungsten ore such as huebnerite
(MnWO4) , scheelite (CaWO4) , ferberite (FeWO4) and wolframite
((Fe,Mn)WO4) or a tungsten-containing material such as flue
dust and various secondary materials_ (e.g., slag and
scrap). The pyrometallurgical slagging process comprises
heating the tungsten-containing material in the presence of
a slag forming silicate (preferably 'silica and an alkali
metal silicate). The melt separates into two immiscible
phases, a denser tungsten-containing phase, preferably
sodium or potassium tungstate, and a less dense slag phase.
In accordance with another embodiment of the present
invention, a process for forming tungsten carbide from a
tungsten-containing material is provided. Preferably, the
process includes two pyrometallurgical stages, a first
slagging stage and a second sparging stage.
CA 02623200 2008-03-27
Figure 1 illustrates a flow diagram of a preferred
embodiment of the present invention. A tungsten-containing =
concentrate 12 together with silica 14 and sodium silicate
16-are introduced into a slagging furnace 18. The slagging
furnace 18 is heated to a temperature in the range from
about 900 C to about 1,200 C, preferably from about 1,050 C
to about 1,150 C and more preferably to approximately
1,050 C for approximately 0.5 to 2.0 hours. The feed
materials separate into two immiscible phases. A higher
density tungsten-containing phase (tungstate) 20 settles to
the bottom of the furnace crucible due to gravity and a
less dense slag phase (silicate) 22 segregates to the upper
portion of the furnace crucible. The higher density
tungsten-containing phase 20 is introduced into a sparging
furnace 24. The lower density slag phase 22 can be
disposed of, or subjected to further treatment. The higher
density tungsten-containing phase 20 can be separated from
the lower density slag phase 22 by any number of
appropriate processes. For example; the higher density
phase 20 and lower density phase 22 can be poured
sequentially from the mouth of a tilting or rotating
furnace into separate appropriate vessels such as ladles.
Alternatively, an outlet can be provided in the crucible to
draw off the higher density tungsten-containing phase 20.
Gas 26 from the slagging furnace 18 can be subjected to
particulate control 28. The recovered particulate matter
can be recycled to the slagging furnace 18 and the
treated gas 32 can be vented to the atmosphere.
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The higher density tungsten-containing phase 20 is
introduced into a sparging furnace 24. The higher density
tungsten-containing phase 20 is heated to a temperature in
the range of from about 1,050 C to about 1,200 C,
preferably from about 1,050 C to about 1,150'C and more
preferably to a temperature of approximately 1,100 C. A
carbon-containing gas 34, such as methane, is introduced
into the sparging furnace 24. The carbon-containing gas 34
is cracked at the sparging furnace temperatures and the
carbon is available for the formation of tungsten carbide.
Gas 36 from the sparging furnace 24 can be subjected to an
afterburner 38 with the addition of an oxygen-containing
gas such as air 40 and a hydrocarbon, such as methane 42.
The afterburner gas 44 can be subjected to particulate
control 46. Recovered particulate matter 48 can be
recycled to the slagging furnace 18 and treated gas 50 can
be vented to the atmosphere. Sparged, spent salt 51 can be
recycled to the slagging furnace 18.
The sparging step 24 results in a crude tungsten
carbide product 52 which resembles a gray sintered
material. The crude tungsten carbide product 52 is
subjected to a water leaching step 54 after addition of
water 55, followed by solid/liquid separation 56. The
liquid portiori 58 is fed to a crystallizer 60 and the
crystals 62 can be recycled to the sparging furnace 24.
The solid crude tungsten carbide crystals 64 are comminuted
66 in water 68 and subjected to acid leaching 70 with a
suitable acid 72 (e.g., HC1). In a preferred embodiment,
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Z(lm
the comminution 66 and acid leaching 70 take place in a
single operation. The comminution 66 is preferably
conducted in a ball mill using tungsten carbide grinding
media. The crude tungsten carbide crystals 64 are first
slurried in a dilute aqueous 68 solution of hydrochloric
acid 72, and the comminution 66 is continued for a period
of time sufficient to liberate and solubilize impurities.
The comminuted and acid leached suspension 74 is subjected
to solid/liquid separation 76. The solid high purity
tungsten carbide 78 preferably has a purity level of at
least 90 percent tungsten carbide, more preferably at least
95 percent tungsten carbide, and more preferably at least
99 percent tungsten carbide. The liquor 80 is subjected to
neutralization and precipitation 82 of solid materials 84.
The solid precipitate 84, after drying, can be recycled to
the slagging furnace 18.
In the first pyrometallurgical operation, a furnace
charge consisting of a blend of tungsten concentrate and
siliceous flux is treated at approximately 1,050 C. The
tungsten compounds contained in the concentrate (e.g.,
calcium, iron, or manganese tungstates) react with the
siliceous flux (preferably sodium silicate and silica) to
produce two immiscible phases: a molten salt and molten
silicate slag. The tungsten is preferentially segregated
in the molten salt phase, while the majority of the
impurities are rejected in the slag. The salt is more
dense than the slag and settles to the bottom of the
furnace crucible. The salt phase, which chiefly consists
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of sodium tungstate, is then forwarded to the second s-eage
of pyrometallurgical processing, i.e., sparginga
The concentrate used in the examples contained
huebnerite (MnWO4) as the primary tungsten mineral. When a
blended charge is treated as described above, the following
chemical reaction ensues:
MnWO4(c) + NaZSiO3(c) = Mn0=SiOZ(i) + Na2W04M
Segregation of the salt and slag phases is predicated upon
the exploitation of the immiscibility region existing
within the tungstic oxide-sodium oxide-silica system shown
in Figure 2. When the tungsten concentrates enter the
1,050 C melt, they react with the sodium silicate to
produce sodium tungstate and slag. At this temperature,
the slag and tungstate are immiscible, and they separate by
gravity. .
The precise chemistry of the slag will depend upon the
relative amounts of excess silica and sodium oxide in the
system. Sodium oxide is a desirable slag constituent
because its presence reduces the slag melting point
sufficiently to ensure the formation of a completely liquid
phase. In the absence of sodium oxide or another flux
compound which will effectively lower the slag's melting
point, a liquid slag cannot be formed in the manganese
oxide-silica system at temperatures below approximately
1,250 C.
An example of a slagging system is illustrated in Fig.
3. With the exception of a gas injection system, the same
basic furnace configuration useful in the sparging
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m12
operatzon (described below) can be employed for the
slagging operation. Because the slagging operation is
simply a melting and separating exercise, no gas lances or
nitrogen purge lines are required.
The second pyrometallurgical process effects the
crystallization of tungsten carbide within the molten salt
phase. This feat is accomplished by heating the tungsten-
bearing molten salt from the first stage to within the
range of approximately 1,080 to 1,100 C and then sparging
with a large stoichiometric excess of hydrocarbon gas, such
as methane or propane. Under these conditions, the
hydrocarbon gas cracks and provides the reductant and
carbon source necessary for forming the tungsten carbide.
The tungsten carbide phase forms as micron-sized crystals,
which are insoluble in the molten salt phase. The crystals
are also denser than the salt and are segregated near the
bottom of the reactor. At the conclusion of the sparging
operation, the spent salt is decanted from the crystals.
When methane is employed as the hydrocarbon source,
the net chemical reaction leading to the formation of the
tungsten carbide (WC) product is believed to be:
4CH 4(g) + NaZWO4M = WC(s) + 3CO(9) + 8H 2(g) + Na2O(1)
Because a large stoichiometric excess of hydrocarbon
gas is needed, some of the excess gas also cracks to
produce carbon and hydrogen gas, as illustrated by the
following reaction:
CH4(9) C(S) + 2HZ(9)
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The hydrogen gas and much of the elemental carbon are
oxidized in the afterburner. However, some of the carbon
remains as a contaminant within the salt phase. Thus,
minimization of excess carbon formation in the sparging
furnace is desirable.
Other hydrocarbon gases, such as propane or ethylene
(CZH4), can be used in place of methane. For instance, the
use of ethylene might enhance the sparging efficiency
(i.e., increase the yield of tungsten carbide per unit of
carbon added to the melt).
After separation of the free-flowing spent salt phase,
the resultant tungsten carbide crystals are contained in a
separate phase having a gray, sintered appearance. The
gray material retains appreciable quantities of salt. The
salt and other impurities are removed via a process of dry
and/or wet grinding and sequential leaching in hydrochloric
acid, caustic, and water. After this treatment, the
resultant crystals can assay between approximately 99.3 and
99.4% tungsten carbide. However, the tungsten carbide
produced in preliminary tests contains substantially higher
impurity concentrations. The elevated impurity
concentrations, mainly chromium and nickel, are believed to
result from chemical attack of the fused salt on the
reaction crucible.
An example of a suitable system for slagging (Fig. 3)
and sparging (Fig. 4) includes a tilting furnace 110 with
a cover at the top which has room for two sparging lances
112, 114, two thermocouples 116, 118, one dedicated*
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nitrogen line 120, one exhaust line 122, and one pressure
gauge 124. The main component is a 12.9 kW resistance- =
heated furnace 110. The furnace 110 has a hot zone 0.914
meter long by 12.7 cm diameter; it can attain a maximum
operating temperature of about 1,200 C. Within the furnace
shell, the process reaction vessel, or crucible 126, is
constructed of 10.2 cm diameter Inconel 600 pipe; the
maximum bath depth is about 45.7 cm. The crucible 126 may
be removed for cleaning or maintenance by opening the
hinged split shell furnace.
The same furnace can be employed for slagging (Fig. 3)
and sparging (Fig. 4). In either slagging or sparging
operations, the initial charge is typically added to the
cold crucible 126, and then power is applied to the furnace
110 in order to elevate the bath temperature to the desired
target. Subsequent charges can be made to the hot furnace
110. To facilitate removal of molten products, the furnace
110 can be tilted a full 180 degrees from its vertical
= operating position to pour products into ladles.
For operation in the gas sparging mode (Fig. 4), a
facility was designed with the capability to purge the
crucible 126'with nitrogen 127 and sparge the molten bath
with methane, propane, ethylene or any mixture of these
hydrocarbon -source gases 128. Seven access ports are
located in the reactor lid. Two of the ports admit gas
lances 112, 114 during sparging operations. Hydrocarbon
gases 128 are injected into the crucible 126 through one of
the lances 112, with the other lance 114 held in reserve
CA 02623200 2008-03-27
15
in case the first lance 112 becomes obstructed.
Preferably, the lances 112, 114 have a relatively small w.
inner diameter (e.g., 0.14 cm) to provide relatively high
velocity flow, thus minimizing cracking in the lances 112,
114. The inlet hydrocarbon gases 126 are directly injected
intq the melt at a point approximately 5 cm above the
crucible 126 bottom. During each sparging test, nitrogen
120 can also be injected through a third inlet port at a
point approximately 2.5 cm below the reactor lid. The
dedicated nitrogen lance 120 assures positive pressure
inside the freeboard to prevent air from entering the
crucible 126. All of the inlet gas flows are controlled by
flow meters 130, 132, 134. Three other lid ports serve as
thermocouple wells, and the main (central) port 122 serves
as the process gas offtake.
A primary concern in the system design is to ensure
efficient transport of the nascent hydrogen, which is
formed by cracking or as a product of the sparging reaction
to the afterburner 136. Preferably, in one embodiment, the
pressure inside the furnace 110 is first adjusted to 0.25
to 0.50 millimeters (mm) of water by balancing the flow of
reacting gas with the extraction draft. Then the pressure
is increased to 2.5 to 5.0 mm of water by adjusting the
flow of the dedicated nitrogen lance 120. Note that the
tip of this lance 120 is positioned only about 5 cm from
the top of the crucible 126 so that most of the draft is
utilized to extract the reaction product gases and not
nitrogen. In this way, most of the nitrogen flows through
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the top cover, maintaining an inert atmosphere at the top
of the crucible 126 and preventing any air from contacting__
the product gases inside the furnace 110. The reaction
gases are drawn into the afterburner 136 and combusted to
HZ0 and COZ. Carryover salt can be collected at the
baghouse 138 or scrubber 140. The afterburner 136 offgases
can be air cooled 142 to 120 C before reaching the baghouse
138 or scrubber 140. When the baghouse 138 is employed,
the gases go through the scrubbing system; then they can be
discharged into the atmosphere. In the embodiment shown in
Figure 4, the afterburner 136 offgas passes through the
scrubber 140, while the baghouse 138 is used to treat
possible fugitive emissions from the furnace 110.
Process gases exit the crucible 126 through the single
exit port 122 leading to the gas handling system. The
gases are fed directly into a 20.3 cm diameter by 55.9 cm
long natural gas-fired, stainless steel afterburner 136
through a 5 cm diameter pipe. The afterburner 136 is
designed to operate with a pressure pilot burner which
remains ignited throughout the tests. Oxygen 144 is fed
into the afterburner 136 at a controlled rate for
combustion of the nascent hydrogen, residual hydrocarbon
gases, and carbon fines entrained in the offgas stream.
After exiting the afterburner 136, the gases pass through
a ball valve 146 (used to balance the system gas pressure
profile) and then into the scrubber 140.
The scrubber 140 is constructed of a 208-liter polymer
drum and polyvinyl chloride (PVC) piping. The scrubber is
CA 02623200 2008-03-27
17
filled with approximately 114 liters of water; the
afterburner discharge gases are bubbled into the reservoir
to condense and remove any soluble material in the gas
stream. The afterburner exhaust gases are cooled by air
dilution 142 and by an external chiller coil system 148
before entering the scrubber 140. Gases are pulled through
the scrubbing system by a 25 cm diameter blower 150. Exit
gases from the blower 150 can be vented to the atmosphere.
An external baghouse 138 and blower assembly was set
up to collect fugitive emissions from the crucible lid.
The baghouse 138 was fitted with two inlet hoses, each 10.2
cm in diameter, that were placed near the crucible lid.
Fugitive emissions were thus drawn into the baghouse 138,
filtered, and then blown into the atmosphere.
Temperature was monitored at several key points
throughout the system. Readings were measured by two
thermocouples 116, 118 which are placed through two
separate lid ports. One thermocouple 116 measured the melt
temperature near the point of gas injection, while the
other thermocouple 118 was used to monitor the temperature
of the head space, or freeboard, in the crucible 126 above
the melt.
Examples and Comparative Tests
The tungsten concentrate sample used in the following
examples was shipped from a commercial source. The 817 kg
sample was packed in two unlined 30 gallon metal drums.
The contents of both drums were thoroughly blended together
prior to initiating any testing. Approximately half of the
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sample was stored in a plastic-lined 55 gallon drum. The
remaining half of the sample was split into lots of
approximately 45 kg. Subsamples were drawn from three of
the lots for comparative analysis to ascertain the
efficiency of the blending operation. Duplicate samples
were retained on inventory for verification analyses. The
blended master samples were then stored in sealed
containers pending their use in the various tests.
The three subsamples of the tungsten concentrate were
initially screened by semiquantitative analytical methods,
such as x-ray diffraction (XRD), x-ray fluorescence (XRF),
and emission spectrography, to approximate its mineralogy
and chemical composition. Subsequently, all major and
minor components detected by the screening methods were
analyzed by more exacting techniques, including wet
quantitative analytical chemistry, atomic absorption
spectroscopy (AA), and inductively-coupled plasma
spectroscopy (ICP). In some cases, multiple analytical
techniques were employed in order to firmly establish the
chemical composition of the concentrate sample. In
addition to the chemical analysis, the tungsten concentrate
sample characterization also included a limited amount of
physical characterization.
Comparative Tests A, B and C
Three comparative slagging tests, designated as A, B
and C, were completed within a 5 kW induction furnace
system. In view of the huebnerite mineralogy of the
concentrate sample, the tests were performed to obtain a
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preliminary indication of the behavior of the MnO-NazO-Si02
system slag. The charge components included varying
amounts of concentrate, sodium chloride, and slag-formers
s.odlum silicate and silica. These were added according to
the respective charge compositions detailed in Table I.
f During these experiments, excessive salt fumes were
evident at times, and thin layers of salt condensed on the
internal surface of the dome of the bell jar induction
furnace containment.
Table I. Charge Compositions for Comparative Slagging
Tests A, B and C
Charge Component Test A Test B Test C
and Mass
Concentrate, g 10.73 10.68 12.10
NaCl, g 16.36 16.40 18.64
Na Si0=9H 0, g 23.03 28.93 16.89
Si0 , g 3.36 3.37 0
Visual inspection of the slag and salt products
indicated no problems with phase separation. The three
slag samples had a vitreous appearance and were tinted
green, ranging from light green in Test A to emerald green
in Test C. Most of the sodium chloride was volatilized
during the first test, leaving a deposit of dark solids on
the slag surface. In the other two tests, the halide phase
was off-white with a yellow tint on each surface. The slag
and halide phase samples produced in each test were
recovered and submitted for XRF analysis; the amount of
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s20-
halide phase recovered from Test A was insufficient for XRF
analysis.
The XRF data, summarized in Table II, suggest that a
fav-orable partitioning of the tungsten between the slag and
the halide phase occurred in two of the three tests. The
tungstic oxide (WO3) concentrations in the slag samples
generated in Tests A and C were 0.5 and 0.7%, respectively,
while the tungstic oxide concentration in the B slag was
1.8%.
Table II. XRF Analysis of Slag Samples from Comparative
Slagging Tests
Compound A B C
Weight % Weight % Weight %
NaCl 7.1 8.7 3.1
A1 O 3.5 2.6 1.2
FeO 0.7 0.5 0.9
MnO 14.4 10.2 28.7
Na O 22.7 21.2 14.4
Si0 47.7 51.2 42.4
WO 0.5 1.8 0.7
Total 96.6 96.2 91.4
As shown in Table III, the halide phase samples from
Tests B and C consisted primarily of chlorine, sodium, and
tungsten. According to the XRF data, the halide phase
samples from Tests B and C contained 39 and 40% tungstic
oxide, respectively. The iron and manganese concentrations
were each below 0.1 % in both halide samples. Trace levels
of several other elements were also detected.
CA 02623200 2008-03-27
21~
Table III. XRF Analysis of Halide Phase Samples from
Preliminary Slagging Tests
Element B C
Weight ~ Weight %
C1 46.5 44.5
Na 23.0 23.3
W 31.0 32.0
Total 100.5 99.8
Example 1
Sodium Tungstate Production
Example 1 is designed to demonstrate the feasibility
of forming a discrete sodium tungstate phase in the absence
of sodium chloride in the charge. For the test to be
successful, it is necessary that the sodium tungstate and
slag would be present as immiscible liquids at the
temperature of interest. This test was conducted in a 5 kW
induction furnace. This charge composition is presented in
Table IV.
Table IV. Charge Components and Masses for Sodium Tungstate
Production
Charge Component Example 1
and Mass
Concentrate, grams 66.57
NaCl, grams 0
Na Si0 , grams 62.16
S i0 ,' grams 21.27
Total, grams 150.00
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m22
Visual inspection of the test products indicates the
formation of two distinct phases, sodium tungstate and
slag. The slag phase has a dark green appearance and is at
the-top, while the sodium tungstate phase is off-white and
located at the bottom of the crucible. The fact that the
sodj-um tungstate phase is located at the bottom of the
crucible is due to its higher density and its immiscibility
with the lower density slag phase.
Example 1 was conducted without difficulty and phase
separation was excellent. The products of this experiment
were submitted for analysis to determine their respective
tungsten and manganese distribution between the two product
phases. As shown in Table V, the analytical results for
Example 1 confirmed the feasibility of favorable tungsten
and manganese distributions between the slag and salt
phases. Judging from these results, the separation of
tungsten from the concentrate as sodium tungstate, in the
absence of sodium chloride, presents an attractive
alternative.
Table V. Analytical Results from Example I
Charge Composition Chemical Analysis
Species Weight t Element ~ in Salt o in Slag
Na Si0 41.45 Mg 0.06 0.34
Si0 14.17 Na 12.80 16.70
MnWO 44.38 W 59.25 0.10
Mn 2.05 12.40
cl
Si 0.21 19.50
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23-
Comuarative Tests D. E. F and G
Variation of the Manganese-to-Sodium
Silicate Ratio in the Charge
The objective of Comparative Test D is to evaluate the
effect of a high manganese-to-sodium silicate (Mn:Na2Si03)
ratio on the distribution of tungsten and manganese between
the slag and salt phases. While not wishing to be bound by
any theory, it is believed that is important to maintain a
certain level of sodium in the system. In conducting tests
where the slag composition was the independent variable,
the respective distribution of manganese between the salt
and slag phases was adversely affected as the manganese
oxide level of the slag increased. This problem became
apparent when the molar ratio of manganese to sodium
silicate in the charge was raised above 1. It is believed
that this phenomena occurred because an insufficient amount
of sodium was present to complete the following reaction:
MnWO4(s) + NaZSiO3(s) = Mn0= Si02(,) + Na2WO4(0.
If Mn:Na2SiO3 molar ratios of greater than one are
desired to reduce flux consumption, additional sources of
sodium are needed to maximize the formation of sodium
tungstate and minimize the dissolution of unreacted
manganese tungstate into the salt phase. The additional
source of sodium utilized in this experiment was sodium
hydroxide (NaOH) according to the composition presented in
Table VI.
CA 02623200 2008-03-27
24
Table VIo Charge Composition for Test D
Compound Test D
Concentrate, grams 41.23
NaCl, grams 64.33
Na Si0 , grams 12.26
NaOH, grams 3.24
Total, grams 121.06
Although two distinct phases were again formed, the
appearance of the slag was different than that observed in
previous experiments. The slag in this test had a sandy
appearance which, when observed under the microscope (30X
magnification), gave evidence of different phases and
incomplete fusion of the charge. The halide phase had the
same appearance as in the previous tests. As evidenced
from the analytical results given in Table VII, the use of
sodium hydroxide yielded unsatisfactory tungsten and
manganese distributions in both the slag and salt phases.
Three additional induction furnace tests were
conducted to further explore the effect of altering the
Mn:NazSi03 ratio in the furnace charge, and to investigate
the use of alternative sources of sodium and silica. The
specific objective of Test E was to study the effects of a
slag composition with a Mn:Na2SiO3 molar ratio of one on the
distributions of tungsten and manganese between the halide
and slag phases. As indicated in Table VII, the 0.55%
concentration of tungsten in the slag and the 0.14%
concentration of manganese in the halide indicate' that
reduction in flux consumption to realize a slag molar ratio
CA 02623200 2008-03-27
25-
of Mn:NazSiO3 of less than or equal to one is feasible and
worth pursuing.
In Test F, an attempt was made to increase the
manganese:silicon ratio to 1.35, under conditions similar
to those of Test D but using sodium carbonate (Na2CO3)
instead of sodium hydroxide as the additional sodium
source. The objective was to determine whether the choice
of,.additional sodium source had any significant effect on
the tungsten and manganese distributions. As seen in Table
VII, a tungsten -concentration of 1.08% in the slag
suggests, when compared to 3.9% from Test D, that the
source of additional sodium can have an effect on the
distribution of tungsten in the halide phase.
In Test G the objective was to study the feasibility
of using silica and sodium carbonate as the sole sources of
sodium and silica in an attempt to substitute less
expensive raw materials for sodium metasilicate. As shown
in Table VII, the 0.13% tungsten concentration in the slag
and the 0.03% manganese concentration in the halide
suggested that the substitution is feasible.
CA 02623200 2008-03-27
2- 6
Table Vleo AnaWtical Results for Comparative Tests D. E, F.
and G
Charge Composition Chemical Analysis
Test Comments
Species Weight % Element % in % in
Salt Slag
Comparative NaZSiO$ 10.13 Mg 0.01 1.35
Test D NaOH used
Si02 0.00 Na 34.90 5.82 as
MnWO4 34.05 W 17.50 9.44 additional
sodium
NaCI 53.14 Mn 0.22 33.60 source for a
NaOH 2.68 CI 46.00 0.75 basic slag.
Si 0.19 11.90
Comparative Na2SiO3 20.24 Mg 0.01 0.69
Test E Mn:NazSiO3
Si02 0.00 Na 30.70 14.80 molar ratio
MnWO4 31.40 W 25.60 0.55 of one in
the slag.
NaCI 48.36 Mn 0.14 24.50
CI 37.00 0.06
L Si 0.12 12.30
Comparative Na2SiO3 13.89 Mg 0.01 0.39
Test F Na2CO3
0.00 Na 30.30 11.10 used as
MnWO4 32.56 W 23.40 1.08 additional
sodium
NaCi 50.28 Mn 0.10 32.70 source
Na2CO3 3.27 CI 38.00 0.39 (basic slag).
Si 0.31 12.40
Comparative NaZSiO3 0.00 Mg 0.03 0.72
Test G Si0Z and
Si0Z 18.85 Na 30.50 15.60 Na
2CO3 as
MnWO4 24.20 W 23.60 0.13 sole
sources of
NaCI 37.36 Mn 0.03 13.20 silicon and
Na2C03 19.59 CI 40.50 0.10 sodium.
Si 0.17 16.95
Example 2
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27=.
In Example 2, no sodium chloride was included in the
chargeo The slag composition was selected to ensure the.
formation of two immiscible liquids. The formation of the
two immiscible phases, as well as the favorable
distributions of tungsten and manganese in the salt and
slac, was predicted by the results of Example 1.
The mass balance for Example 2 is shown in Table VIII.
The mass closure for this Example was 96.8%. A tungsten
mass balance indicates that 92.9% of the charged tungsten
reported to the halide phase and 3.3% to the slag. Only
3.8% of the tungsten in the charge was unaccounted.
Table VIII. Mass Balance for Slagging Example 2
Material In Kilograms Material Out Kilograms
Concentrate 4.43 Halide Phase 3.94
Silica 1.41 Slag 5.74
Sodium Metasilicate 4.15
Total 10.00 Total 9.68
The tungsten distribution for Example 2, as calculated
from the analytical data, indicates that approximately 97%
of the input tungsten was segregated in the tungstate
phase, with the difference reporting to the slag. While
these results siuggest that an efficient slagging operation
in the absence of sodium chloride is indeed possible, those
skilled in the art can improve the tungsten distribution
without undue experimentation. Entrainment of salt from
the reactor walls during slag pouring may have contributed
CA 02623200 2008-03-27
o28e
to the relatively high tungsten concentration in the slag
from Example 2.
From an operational point of view, although the sodium
tungstate phase was segregated below the slag in the
reactor (due to the higher density of the salt), it poured
first, due to its lower viscosity and the geometry of the
reactor. There were only a few minor traces of slag
entrained in the salt, and these had floated to the surface
before the salt solidified in the ladle.
Example 3
Recycling Sparged, Spent Salt to the Slagging
Operation
This Example is designed to demonstrate the
effectiveness of recycling the spent salt from the sparging
unit operation to the slagging unit operation. This
practice is desirable for two reasons. First, the spent
salt typically contains an appreciable concentration of
tungsten (approximately 15% by weight) which is not
converted to tungsten carbide during the sparging step.
Returning the salt to the slagging operation keeps the
tungsten within the processing circuit and is useful in
achieving economic levels of tungsten recovery in the
overall operation. Second, it is believed that the sodium
oxide in the sparged salt can serve as the sodium source in
the production of sodium tungstate during the slagging
operation. Therefore, recycling the spent salt is expected
to reduce the consumption of raw materials. This Example
CA 02623200 2008-03-27
29
was designed to determine whether recycling the spent salt
would affect the distribution of tungsten between the salt -
and slag phases.
The Example consists of three charging cycles
conducted sequentially. The Cycle 1 charge represents a
typi-cal slagging operation charge without salt recycled
from the sparging operation and consists of a 5 kg blend of
260% huebnerite concentrate, 24.7% sodium metasilicate
(Na2Si03), 8.4% silica (Si0Z) and 40.6% sodium chloride
(NaC1). The Cycle 2 charge consisted of 1 kg of spent salt
(generated during a previous sparging test) plus 4 kg of
the same components used in Cycle 1, mixed in the identical
proportions. The Cycle 3 charge contained 2 kg of spent
salt plus 4 kg of the components used in Cycle 1, again
mixed according to the Cycle 1 proportions.
At the beginning of each test cycle, the charge
materials were blended together, added to the furnace, and
processed at a nominal temperature of 1,O50 C for one hour.
The fused salt was then removed by tilting the furnace and
pouring the melt into a ladle where it was allowed to
solidify. The furnace was restored to its vertical
operating position, and the process was repeated with the
next charge. The slag phase was not removed until all
three cycles had been completed. The slag was then poured
into a ladle and allowed to solidify. Samples of the slag
and of each of the three salt products were prepared and
submitted for chemical analysis.
CA 02623200 2008-03-27
G3Qe
The analyses of the slag and salt products are
summarized in Table IX. As calculated from the measured-_
product weights and associated tungsten analyses,
approximately 99.1% of the tungsten reported to the salt.
Comparison of the salt analyses from Cycles 1, 2 and 3
indicates favorably low concentrations of impurities in all
three cycles.
CA 02623200 2008-03-27
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CA 02623200 2008-03-27
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Examples 4 and 5
Sparging Sodium Tungstate to Produce Tungsten Carbide
It has been demonstrated that tungsten carbide of
reasonably high purity can be obtained by sparging a molten
mixture of sodium tungstate and sodium chloride with
methane. However, elimination of the sodium chloride from
the operation improves the process for several reasons.
Consequently, two additional Examples are presented to
demonstrate whether crystalline tungsten carbide powder can
be produced by sparging molten sodium tungstate with
methane gas.
In each Example, the initial melt consists of sodium
tungstate produced in previous slagging tests. During the
Examples, the sodium tungstate bath is maintained at
approximately 1,100 C, while methane gas is injected below
its surface at a flow rate of approximately 11.4 liters per
minute. Methane sparging is continued for three hours in
Example 4 and for 90 minutes in Example 5. At the
conclusion of each Example, the molten products are poured
into a steel ladle and allowed to solidify.
After the products have solidified and cooled
sufficiently, two separate phases are observed: a white
"spent ash" and a denser, medium gray phase. The two
phases are separated and prepared for x-ray diffraction
(XRD) analysis. The products from Example 4 were selected
for the XRD analysis because they were more easily and
cleanly separated after cooling. XRD analysis of the white
spent salt indicates that it is predominantly composed of
CA 02623200 2008-03-27
-33-
unreacted sodium tungstate (Na2WO4) with trace concentration
of another unidentified crystalline phase. Nore==
significantly, the dense graph phase was found to contain
sodium tungstate, with lesser concentrations of tungsten
carbide (WC) and ditungsten carbide (W2C) and trace
concentrations of metallic tungsten and the same
unidentified crystalline phase that occurred in the white
salt.
Although those skilled in the art will be able to
further optimize the process, the x-ray diffraction results
demonstrate that it is possible to form tungsten carbide
via the methane sparging method.
While various embodiments of the present invention
have been described in detail, it is apparent that
modifications and adaptations of those embodiments will
occur to those skilled in the art. It is to be expressly
understood, however, that such modifications and
adaptations are within the scope of the present invention,
as set forth in the following claims:
CA 02623200 2008-03-27
-34 ,
List of Reference Numerals
Tungsten-Containing Concentrate 12
Silica 14
Silicate 16
Slagging Furnace 18
Tungstate Salt 20
Slag 22
Sparging Furnace 24
Slagging Furnace Gas 26
Particulate Control 28
Part'iculates 30
Treated Gas 32
Carbon-Containing Gas 34
Sparging Furnace Gas 36
Afterburner 38
Oxygen-Containing Gas 40
Methane 42
Afterburner Gas 44
Particulate Control 46
Particulates 48
Treated Gas 50
Sparged, Spent Salt 51
Crude Tungsten Carbide Product 52
Water Leaching Step 54
Water 55
Solid/Liquid Separation 56
Liquid Portion 58
Crystallizer 60
Crystals 62
Solid Crude Tungsten Carbide Crystals 64
Comminution 66
Water 68
Acid Leaching 70
Acid 72
Comminuted and Acid Leached Suspension 74
Solid/Liquid Separation 76
High Purity Tungsten Carbide 78
Liquor 80
Neutralization and Precipitation 82
Solid Precipitate 84
Tilting Furnace 110
Sparge Lances 112, 114
Thermocouples 116, 118
Nitrogen Line 120
Exhaust Line 122
Pressure Gauge 124
Crucible 126"
Nitrogen 127
Hydrocarbon Gas(es) 128
Flow Meters 130, 132, 134
Afterburner 136
Baghouse 138
Scrubber 140
Cooling Air Intake 142
Oxygen 144
CA 02623200 2008-03-27
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ValVe 146
Chiller Coil System 148
Blower 150
