NATURAL GRAPHITE PURIFICATION THROUGH CHLORINATION IN FLUIDIZED BED

REACTOR

*K. Adham
Hatch Ltd. - Mississauga, Ontario, Canada L5K 2R7
(*Corresponding author: kadham@hatch.ca – 905-403-3877)

G. Bowes
Northern Graphite Corporation - Ottawa, Ontario, Canada K1Z 8P8

ABSTRACT

For use in many existing and emerging applications, the purification of natural graphite is required
to achieve +99.9% carbon content with minimum metallic impurities. Currently, the hydrofluoric acid
process is used, which carries certain environmental and workplace health and safety impacts. While thermal
purification of graphite at temperatures over 2500 °C is a known alternative, such high-temperature furnaces
are expensive to build and operate. Using chlorine at lower temperatures to purify graphite is also known
and patented, but is currently limited to treating solid synthetic graphite shapes in small-scale batch furnaces.
Chlorine treatment of natural flake graphite resources can be used commercially, if certain drawbacks are
addressed through process improvements that can be helped with the use of fluidized bed reactor technology.

KEYWORDS

Purification, Natural graphite, Flake graphite, Micronized graphite, Metallic impurities, Hydrofluoric acid,
Environmental impact, Health and safety impact, Thermal purification, High-temperature furnace, Chlorine
treatment, Fluidized bed reactor.
 INTRODUCTION

Increasing popularity of electronic devices and electric vehicles has caused a surge in demand for
rechargeable lithium ion batteries (LiB). Announcements are made of new battery production facilities
around the world, resulting in an increased demand for superior quality natural graphite. For use in many
existing and emerging applications, the purification of natural graphite is required to achieve +99.9% carbon
content with minimum metallic impurities. Mineral processing techniques, including flotation, can typically
upgrade a natural graphite ore to the 85%-96% range. However, removal of the remaining impurities requires
secondary thermal and/or chemical treatments.

HIGH PURITY NATURAL GRAPHITE APPLICATION

Graphite is the anode material in the lithium ion battery (LiB) and currently there is no economically
viable substitute for it. LiB anode material must be purified to 99.95% and some specific impurities, such as
Fe, must be less than 50 ppm. Sulfur and silica are other commonly occurring impurities in the typical natural
graphite deposits.

Graphite can be sourced from two routes, natural and synthetic. Natural graphite is obtained from
mines, whereas synthetic graphite is produced from petroleum coke. Both types of graphite can be utilized
for the LiB anode production, but currently more than half is sourced from the natural graphite. LiB
manufacturers may consider synthetic graphite because of its higher consistency and purity compared with
natural graphite, and it provides a longer battery life. However, with modern chemical and thermal
purification processes, natural graphite can achieve a purity of +99.9%. Moreover, natural flake graphite has
a more crystalline structure and can offer better electrical and thermal conductivity than the synthetic graphite.
Natural graphite can also provide a lower cost profile for many LiB applications.

WET PURIFICATION PROCESS

Graphite ores can be milled to liberate the gangue material, optimally with minimum size reduction
below the most profitable range (100 to 600 micron) for the natural flakes. The liberated graphite particles
are naturally hydrophobic, and therefore, can be subsequently floated with suitable oils at optimized pH
conditions [1]. Figure 1 shows a typical natural graphite ore milling and flotation circuit to physically release
and remove the gangue impurities.

Figure 1: Typical Graphite Ore Milling and Flotation

 Following the mineral processing beneficiation of a natural graphite mined ore to make a graphite
concentrate, further purification can be done by chemical leaching. Hydrofluoric (HF) acid can be used for
its ability to leach both the metallic impurities and the silica (quartz) content of natural graphite. Dissolution
of silica by HF has been widely known, for example as applied to the etching of silicate crystals in the glass
industry, and successfully used for the purification of natural graphite [6]. Typical impurity removal reactions
can be shown as follows:

𝑆𝑖𝑂2 + 4 𝐻𝐹 → 𝑆𝑖𝐹4 + 2 𝐻2 𝑂
𝐹𝑒𝑆 + 2 𝐻𝐹 → 𝐹𝑒𝐹2 + 𝐻2 𝑆
𝐶𝑎𝑂 + 2 𝐻𝐹 → 𝐶𝑎𝐹2 + 𝐻2 𝑂

The key variables to be optimized during the HF leach are acid strength, solid-to-liquid ratio,
leaching temperature, and leaching time. Essentially this type of purification is currently done in China using
the wet chemical approach, which is largely based on the use of hydrofluoric acid. This is difficult and/or
expensive to do in the West due to environmental and workplace health and safety concerns [4]. As the
electric vehicle market expands and the demand for LiB anode material grows exponentially, it is critical
that the West develop an alternative to current graphite purification processes.

THERMAL PURIFICATION PROCESS

The electro-thermal Acheson furnace was first patented in 1896 to produce graphite and silicon-
carbide (Figure 2). Acheson developed an efficient electric furnace based on resistive heating, which is the
basis of most silicon carbide manufacturing today. In the Acheson furnace, the electric current passes through
a graphite core, which is surrounded by sand and carbon.

Figure 2 – Acheson furnace’s typical cross section

More recently [2] thermal purification of natural graphite at temperatures over 2500℃ has been
achieved. The thermal method can use an electrically-heated fluidized bed; however, such high-temperature
furnaces are expensive to build and operate.

When electricity is passed through a bed of particulate graphite, the bed presents an electric
resistance to the current flow. The bed resistance depends on many parameters, including the physical
property of the graphite (particle size and density), the bed height, and the electrode geometry. If the graphite
bed is fluidized by passing a gas to suspend the particles, the resistance of the bed increases with the increased
bed voidage. The current flow though the conducting particles generate ohmic heat (I2R) within the bed,
which can be controlled to maintain the bed temperature within such electrothermal fluidized beds [3].

A typical electrothermal fluidized bed reactor arrangement can consist of a chemically inert
refractory (e.g. graphite) crucible, multiple thermal insulating layers, fluidizing gas inlet and outlet, and at
least two electrodes, as depicted in Figure 3.
 Figure 3: Schematic of a typical electrothermal fluidized bed

The electrothermal fluidized bed can be very energy efficient, because no external heating is
required and energy is released where it is required, right within the bed of graphite. Various configurations
of the electrothermal fluidized bed reactor are possible. The reactor vessel or the fluidizing column itself can
serve as one of the two electrodes, with the other electrode being centrally suspended from the top of the
reactor and submerged inside a fluidized bed of conducting solids.

As the electrothermal fluidized beds used for graphite purification operate at high temperatures (up
to 3000°C), it is essential to have excellent thermal insulation and a proper temperature resistant reactor
vessel design (mechanically stable from the installed room temperature all the way to the operating
temperature). Such a high temperature is required to volatilize most of the silica and other metallic oxides,
as shown in Table 1 [5].

Table 1: Typical oxide impurities’ melting and boiling points

Oxide Melting Boiling
impurity point point
(°C) (°C)
Silica 1,670 2,230
(SiO2)
Iron 1,420 3,400
oxide
(FeO)
Calcium 2,570 2,850
oxide
(CaO)

For most experimental or large-scale reactors, graphite is chosen as the construction material and
the column is generally insulated with suitable refractory bricks or granules. In order to reduce radiation heat
losses, radiation shields in the form of graphite plates above the bed and graphite central electrodes may also
be used.
 CHLORINE PURIFICATION PROCESS IN FLUIDIZED BED

Using chlorine at lower temperatures to purify graphite is also known and patented, but is currently
limited to treating solid synthetic graphite shapes in small-scale batch furnaces. Previous processes have
achieved very limited commercial success because of the costs associated with high reagent consumption,
long furnace retention times, batch processing, and the requirement for catalysts and other chemicals. Also,
high purity levels were often not achieved and the corrosive nature of chlorine at temperature caused
mechanical, structural and safety problems with the furnaces.

Chlorine treatment of natural flake graphite resources can be used commercially, if these drawbacks
are addressed through process improvements that can be helped with the use of fluidized bed reactor
technology.

Although the chlorine purification can be done for graphite pieces in stationary arrangements, the
use of a fluidized (suspended) bed is beneficial for natural graphite particulates. Figure 4 shows the different
fluidizing regimes that can be achieved by suspending a bed of particles in an upward flow of gas. The
bubbling regime is typically considered for particulate graphite treatment.

Figure 4: Suspended particulate solids as fluidized by the upward flow of gas

Chemical reactions that occur between the graphite impurities and the chlorine gas are generally
categorized as carbochlorination and can be simplified as the following general formula, where some of the
carbon value that is present in excess in graphite structure, reduces the oxides (turning into CO) and the
chlorine gas reacts with the metallic values to turn them into volatile chlorides.

𝑆𝑖𝑂2 + 2 𝐶𝑙2 + 2 𝐶 → 𝑆𝑖𝐶𝑙4 + 2 𝐶𝑂

𝐹𝑒𝑂 + 𝐶𝑙2 + 𝐶 → 𝐹𝑒𝐶𝑙2 + 𝐶𝑂
𝐶𝑎𝑂 + 𝐶𝑙2 + 𝐶 → 𝐶𝑎𝐶𝑙2 + 𝐶𝑂

Most of the metallic impurities can be chlorinated and volatilized at lower temperatures than
1000°C, but some (e.g. Si) require higher temperatures (up to 1500°C) as depicted in the following simplified
chemical species stability diagrams, at a low oxygen potential (excess graphite presence).
 Figure 5: Lower chlorination temperature required for iron and higher for silica

Northern Graphite has performed chlorination testing at Hazen Research facilities that has
succeeded in purifying spherical graphite 99.99% graphitic carbon (“Cg”) and large flake graphite to 99.83%
Cg. Requirements of battery manufacturers vary in particle size and purity, with the latter specification
usually in the 99.9% to 99.95% Cg range. Large flake graphite was purified to levels ranging from 99.73%
to 99.83% Cg with further improvements possible. The next steps will be to further scale up the process in a
Pilot Plant test that will enable Northern Graphite and its technology partner (Hatch) to define operating
parameters at a commercial level and to estimate capital and operating costs.

CONCLUSIONS

The ultimate objective is to define a purification process that works not only with spherical graphite
for battery use, but also flake graphite and micronized flake graphite for other applications requiring high
purity. Spherical graphite is used to make the anodes in Li ion batteries and is manufactured from the flake
concentrate produced by graphite mining operations. Almost all natural spherical graphite is currently
produced in China and purified using strong acids, which results in large volumes of acidic and toxic waste.
Thermal purification at temperatures as high as 3000°C can be used, but it is expensive in terms of capital
and operating costs. The proprietary purification technology developed by Northern Graphite and its
technology partner (Hatch) can be much more environmentally friendly than the Chinese approach and
operates at significantly lower temperatures (<1500 °C) than traditional thermal methods.

REFERENCES

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3. Gupta, C. K., Sathiyamoorthy, D. (1998). Fluid Bed Technology in Materials Processing (pp. 310-311).
United States: CRC Press.

4. Kaya, Ö. and Canbazoğlu, M. (2009). Chemical demineralization of three different graphite ores from
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5. Perry, R. H. and Chilton, C. H. (1973). Chemical Engineers’ Handbook (pp. 3-6 to 3-24), McGraw Hill.

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