Chemical Project Economics Assignment

DESIGN A PLANT FOR TREATMENT OF 10000 LITHIUM ION BATTERIES

NAME: ABHIJEET SUBUDHI
ROLL NO. 14CHE1032
GUIDE: - PROF. Ashwin W. Patwardhan

INTRODUCTION
A lithium-ion battery or Li-ion battery (abbreviated as LIB) is a type of rechargeable
battery in which lithium ions move from the negative electrode to the positive electrode during
discharge and back when charging. Li-ion batteries use an intercalated lithium compound as
one electrode material, compared to the metallic lithium used in a non-rechargeable lithium
battery. The electrolyte, which allows for ionic movement, and the two electrodes are the
constituent components of a lithium-ion battery cell. The use of lithium-ion batteries (LIBs) is
expected to increase in the near future. The main reason for this will be the use of electric cars,
which use LIBs as the power source. LIBs are also widely used in portable electronic devices
(e.g. cellular phones and laptops). The popularity of LIBs is due to their high energy density,
high voltages and low weight to volume ratio (Xu et al., 2008). LIBs have an expected lifespan
of 3-5 years. Over the next few years, an increasingly large waste stream of LIBs is expected.
LIBs contain toxic and flammable components, as well as valuable metals such as Li, Ni, Cu
and Co. For these reasons, there are benefits to recycling used LIBs, instead of disposal in
landfills.
According to the directives published in many countries, the adequate destination of spent
batteries may involve methods such as landfill disposition, stabilization, incineration and/or
recycling processes. Safe disposal in landfills or stabilization of battery residues becomes more
and more expensive due to the increasing amount of waste produced, and also due to the limited
storage capacity of sanitary landfills and/or special waste dumpsites. Incineration of batteries
is an expensive method as well and it can even cause mercury, cadmium and dioxin emissions
into the environment.

Fig 1. Waste management hierarchy is one presentation and recommendation of waste treatment options

In a closer examination, the level of recycling can be specified. When the recycled material can
substitute a large share of virgin material in a new product and has properties close to the
original quality, the level of recycling is considered high. Using the material in a commodity
that has clearly lower quality or functionality than the original one is in turn referred to as
“downcycling”. (Worrell 2014a, p. 499). It is hence thought that more of the original material
value and the energy investments made for it are restored by higher level of recycling.

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LITHIUM-ION BATTERIES
In an LIB, the cathode is an aluminium plate coated with the cathode material, which is a
lithium metal oxide. The typical composition of LIBs is provided in Xu et al (2008).
Polyvinylidene fluoride (PVDF) is used to bind the electrode coating to the plate.

Fig 2: Typical composition of an LIB

BATTERY RECYCLING
The recycling of LIBs has an enormous potential for economically strategic industrial metals.
However, there is a growing amount of diverse lithium-ion subsystems, operating with
different metals and lithium compounds in the cathode material. The Li-ion battery is named
after the used cathode material such as LCO (lithium cobalt oxide), NCM (lithium nickel
manganese cobalt oxide), NCA (lithium nickel cobalt aluminum oxide) and LFP (lithium iron
phosphate). As a result of missing industrial agreement on standards it is not possible to distinct
these systems visually. This severely complicates the efficient recycling processes. Recycling
processes for LIBs are combinations of different unit operations. Fig 3 summarizes possible
process options for the involved unit operations such as deactivation, mechanical treatment, as
well as the subsequent pyro- and hydrometallurgical treatments. The scheme displayed in Fig3
depicts the advantage of combining different unit operations in order to fulfill the goal of high
recovery rates. Thus, the casing, copper and aluminum foil, and the most valuable components
such as nickel, cobalt, and manganese can be recovered using a combination of mechanical and
hydrometallurgical treatments.

Fig 3. Unit operations in battery recycling and their possible combinations to establish efficient recycling
process routes.

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INDUSTRIAL PROCESS CHAINS

In the following section, some processes that aim to recycle LIBs are introduced. Both existing
industrial scale processes and emerging processes in pilot plant phase or under
commercialization are discussed. The often-used classification to hydrometallurgical and
pyrometallurgical processes (Bernardes et al. 2004) or additionally to physical/mechanical
processes.
1. Retriev Technologies Inc. (former Toxco Inc.)

Fig 4. Flowchart of Toxco’s (Retriev Technologies Inc.) hydrometallurgical recycling process for LIBs.

2. Umicore (Val’Eas Process)

Fig 5. Flowchart of Umicore’s pyrometallurgical recycling process for LIBs.

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3. Recupyl

Fig 6. Flowchart of Recupyl’s hydrometallurgical recycling process for LIBs.

4. Accurec

Fig 7. Flowchart of Accurec’s recycling process for LIBs.

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COMPARISON OF THE PROCESS

RETRIEV
PROCESS/TREATMENT UMICORE RECUPYL ACCUREC
TECHNOLOGIES

Overview to the recycling processes

FEED LiB LiB LiB LiB
DISCHARGE In furnace In crushing In crushing In furnace
MECHANICAL - Brine / N2 Ar / CO2 Ambient
H20, LiOH, H2SO4,
HYDRO HCl Na2CO3 / CO2 Steel, NaClO, H2SO4
Li3PO4
Coke, Slag
PYRO - - 2 slag binders
Formers, Air
LCO/CO(OH)2/Co, Co-alloy,
MAIN END PRODUCTS CoCl2 MeO-C-cake, Li2CO3
Other cell materials Li2CO3
Recycling processes in relation to cathode material recovery
FOCUS Co Co Co Co

CATHODE RECYCLING
CoCl2 MeO + C cake LCO/CO(OH)2/Co Co-alloy
PRODUCT

Cathode
END USE Metal manufacturing unknown As such
material
Ready for
LEVEL VS CATHOD hydrothermal
- - -
PRECURSOR synthesis of
LCO
In furnace,
BINDER but not Not discussed Not discussed In furnace
discussed

The status and the methods of Li recovery in different recycling technologies

LI RECOVERED No Yes Yes Yes

PRODUCT - Li2CO3 Li2CO3 / Li3PO4 Li2CO3
Precipitation with Precipitation with
METHOD - Precipitation
Na2CO3 / CO2 CO2
90% probably in the
RECYCLING EFFICIENCY - presence of primary - 76 - 90%
Li batteries
GRADE - Technical - > 99%
Glass
production /
TARGETED USE OF active
- Metals manufacturing -
PRODUCT cathode
powder
synthesis
Recycling of foil and casing materials

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Polymer
Fe partly Steel recovered evaporated,
recovered in with magnetic Fe recovered
Steel, Al and plastics
alloy, separator; Al, Cu with
CASINGS recovered with shaker
Al slagged, and plastics with magnetic
table
Polymer used densimetric separator, Al
as energy separator with air
separator
Recovered with
Al slagged, Recovered
Recovered with densimetric table
AL AND CU FOILS Cu recovered with air
shaker table Impurity Cu also
in alloy separator
precipitated
From
CATHODE MATERIAL cathode to From cathode to raw From cathode
-
LOOP cathode material to alloy
precursor
Processes using mechanical separation methods and the methods used
Shredder and/or Rotary shear,
COMMINUTION - Mill
hammer mill Impact mill

MAGNETIC SEPERATOR - - High intensity X

Vibrating
SIZE SEPERATION - Not mentioned Vibrating screen
screen
Zig zag air
GRAVITY SEPERATOR - Densimetric table Densimetric table
separator
Treating of graphite in different technologies
Partly burnt;
partly used in
Used as
carbo-
reducing Recovered in MeO + Filtered off in
GRAPHITE reductive
agent in C filter cake leaching step
melting;
furnace
finally,
slagged

SELECTION OF ROUTE
1. In the case of the Recupyl process, complete dissolution of the metals was very difficult to
achieve. Since recovering the lithium on its own did not satisfy the aim of recovering all the
valuable components (e.g. copper, aluminium) partial dissolution was not acceptable.
2. Lab-scales tests at the high temperatures required for the Umicore process were also
difficult to achieve. Smelting at the lower ranges quoted for the Umicore process did not
produce a clean separation of metal and slag. It does not aim at the recovery of lithium which
is the main disadvantage. Furthermore, ignoble metals are slagged and organic materials as
well as carbon are lost. Ultimately the failure of these tests led to a re-evaluation of other
approach.
3. Therefore, an alternative competing recycling process based on pyro- and
hydrometallurgical process steps should also consider an appropriate pre-treatment to recover
as many battery components as possible.
4. In the case of the Toxco’s process recycle efficiency was better for primary lithium
batteries and not for LiB.
5. In Accurec process high recovery rate of Co alloy and Li2CO3 is pursued by a combination
of physical separation, hydrometallurgical and pyrometallurgical methods (Vezzini 2014, p.
542), although it is also mentioned that the target is to recover as many battery components as
possible (Georgi-Maschler et al. 2012).
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6. Combination of mineral processing, hydro-and pyrometallurgy is beneficiation to enriched

material streams where raw material streams to existing processes-flexibility. Also, Accurec
process is new process under commercialization.

The criteria used to select a process for the recycling of LIBs are listed below:
➢ The process must recover lithium and cobalt from the batteries treated.
➢ It must be possible to test the process steps at a lab scale within the budget of this
project.
➢ The process should be made up of steps which have been demonstrated at a
commercial scale.
➢ The product should be of a battery grade, so that it can be used in production of new
batteries.
➢ The process should be simple to design and operate.
➢ The process should be scalable.
➢ All products can be fed into another industry (zero waste).

So, I select Accurec process for recycling of LIBs.

PROCESS DESCRIPTION
(recently modified in south Africa)

Step 1: Battery Dismantling

It is assumed that batteries can be safely dismantled, and the main components separated. The
steel casings can be sent to scrap metal consumers (e.g. iron smelters), and the plastic to suitable
recyclers.
Step 2: Roasting
Each sample was roasted under a nitrogen blanket at 600°C for an hour. The purpose of the
nitrogen blanket was to minimize oxidation of the copper electrode, which improved selectivity
in the first stage leach. An average of 16.6% mass loss was experienced.

Element Al electrode Cu electrode Combined

Al 11.0% 0.0% 6.93%
Ca 0.0% 0.0% 0.04%
Co 0.0% 0.0% 0.00%
Cu 0.0% 34.9% 12.89%
Fe 26.7% 0.1% 16.85%
Li 3.0% 0.5% 2.09%
Mg 0.3% 0.5% 2.09%
Mn 0.1% 0.0% 0.05%
Na 0.0% 0.0% 0.02%
Ni 0.0% 0.0% 0.00%
Zn 0.0% 0.0% 0.01%

Table 1: Roasted battery (Al and Cu electrodes) composition

Step 3: Leaching
The first stage of leaching was done on the roasted product. The purpose of this leach was to
selectively dissolve lithium, with minimal dissolution of other metals. Leaching was done at
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60°C in 1 M hydrochloric acid (HCl). The solid to liquid ratio was 1:10. Agitation was achieved
by swirling every 10 minutes. Leaching was done for varying lengths of time. It was found that
40 mins of leaching resulted in the highest lithium extraction, with the lowest copper
dissolution.
Element Leach Extent
Al 85.8%
Ca 27.7%
Co 17.0%
Cu 4.2%
Fe 40.2%
Li 76.0%
Mg 71.0%
Mn 83.2%
Na 42.5%
Ni 6.4%
Zn 90.0%

Table 2: Leaching extents in the low acid concentration leach (1 M HCl, 60°C, 40 mins)

After filtration, the residue from the low concentration leach was then re-leached in 2M HCl,
with hydrogen peroxide (50%) added to oxidise the copper.

Element Leach Extent

Al 96.7%
Ca 63.3%
Co 29.5%
Cu 99.2%
Fe 39.4%
Li 82.5%
Mg 76.4%
Mn 93.5%
Na 93.1%
Ni 8.5%
Zn 100%

Table 3: Leaching extents in the high concentration leach (2 M HCl, 60°C, 60 mins with H 2O2)

The scoping tests indicated the technical viability of the two-stage leach process.

Step 4: PH Adjustment
Solution from the first leaching stage is fed to the pH adjustment step. The pH of the leach
solution is increased prior to the lithium precipitation step. This is achieved by adding lithium
hydroxide. The target pH is 9. As a result of the increase in pH, copper, aluminum, iron,
magnesium and manganese precipitate from solution. These precipitates are removed by
filtration. The filtrate solution is fed to lithium precipitation.

Step 5: Lithium Precipitation

In this step, CO2 gas is bubbled through the lithium-containing solution. Lithium precipitates
as lithium carbonate. The precipitation reaction produces HCl. The product is filtered and the
solution is recycled to the first leach stage as a source of HCl. The cake is dried to form the
lithium carbonate product. Part of this product can be treated to produce LiOH needed in the
pH adjustment step. The remaining product can be used to regenerate cathode material.

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Step 6: Metal Precipitation

Solution from the second leach stage is treated in the metal precipitation step, in order to
recover dissolved copper. The pH of the leach solution pH is adjusted to 9 by the addition of
hydrated lime. This results in precipitation of copper, aluminium, iron, manganese and
magnesium as hydroxides. The product is filtered and can be sold to copper smelters. The
solution is then passed on to acid regeneration.

Step 7: Acid Regeneration

Calcium remains in solution after metal precipitation, along with chloride ions. To remove
calcium, it is precipitated as insoluble gypsum (calcium sulfate). The gypsum is formed by
adding sulfuric acid, and hydrochloric acid is generated as a by-product (Al-Othman, A. &
Demopoulos, G.P., 2009). The gypsum is filtered, and may be a valuable product stream if the
purity is sufficiently high. The solution, which is free of metals and high in hydrochloric acid
(approximately 56 g/L), can be recycled to the plant feed as acid make-up.

Step 8: Final Leach Residue Disposal

The final leach residue will consist mainly of inert carbon. The solid-liquid separation stage
includes washing to remove any residual leach liquor (which will contain dissolved metals).
The final filter cake should be an inert material consisting primarily of carbon. This should be
easy to dispose of, or possibly form a feed stream for other industries such as tyre manufacture.

Mass Balance Results

Parameter Units Value

Nominal feed rate t/a 10000
Mass ratio of aluminum to copper 1.6
electrodes
Plant availability and utilization % 90
Design flowrate of aluminum electrodes t/h 0.78
Lithium composition in aluminum % 2.51
electrodes
Design flowrate of copper electrodes t/h 0.49
Lithium composition in copper electrodes % 0.37
Table 4: Feed rate for mass balance

Parameter Units Value

Feed rate of solids to process Dry t/h 1.268
Lithium carbonate product flowrate Dry t/h 0.0857
Lithium composition in product % 18.78
Net lithium production t/h 0.0161
Lithium recovery % 74.9
Metal precipitate flowrate Dry t/h 0.712
Gypsum production rate Dry t/h 0.777
Residue flowrate Dry t/h 0.679
Table 5: Summary of mass balance results

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Chemical Project Economics Assignment

Basis: - 1 year

1) Lithium ion battery = 10000 tonnes

1 LIB = Rs 600/unit (110g)
= Rs 4.948*106 / tonne

So, Total cost = Rs 4.948 * 1010

2) Lithium carbonate = 0.0857 *365*24 tonnes = 750.732 tonnes

1 Lithium carbonate = $0.33/unit (150mg)
= 129.89 * 106 / tonne

So, Total cost = Rs 9.75 * 1010

3) Gypsum = 0.777*365*24 = 6806.52 tonnes

1 Gypsum (powder) = $ 2.5/kg
= Rs 147.6 * 103 / tonne
= Rs 1.005 * 109
Vent
Al
Electrodes
Feed
Roasting
Preparation
Cu
Electrodes

H20 Low
concentration L pH L
HCl Leaching S adjustment S

LiOH Li Lithium
precipitation product
CO2

L
S

Vent

H202 High
L Mixed
concentration
L
precipitation Hydroxide
Leaching
S S
H20 Product

Leach
HCl
Residue

Lime
Gypsum L Gypsum
Removal S Precipitate
H2SO4

Recycling

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Net cost considering above three = Rs 4.9025 * 1010

Here there is no consideration of other elements which are recovered in other streams which
can be send to other industries and also there is 80% electrolyte recovery which can be used
also again.

If we compare other process/treatment there the recycling efficiency was less compare to this
selected route and plus they not focus on recovery of each and every element. So, we can say
that this selected route is economically feasible.

References: -
1. Shin, S.M., Kim, N.H., Sohn, J.S., Yang, D.H. & Kim, Y.H., 2005. Development of a metal
recovery process form Li-ion battery wastes, Hydrometallurgy, 79, p. 172 – 181.
2. Zhang, P. Yokoyama, T., Itabashi, O. Suzuki, T.M. & Inoue, K., 1998. Hydrometallurgical
process for recovery of metal values from spent lithium-ion secondary batteries,
Hydrometallurgy, 47, p. 259 – 271.
3. Xu, J., Thomas, H.R., Francis, R.W., Lum, K.R., Wang, J. & Liang, B. (2008) A review of
processes and technologies for the recycling of lithium-ion secondary batteries, Journal of
Power Sources, 177, p. 512 – 527.
4. Kondas, J., Jandova, J. & Nemeckova, M., 2006. Technical note: Processing of spent
Li/MnO2 batteries to obtain Li2CO3, Hydrometallurgy, 84, p. 247 – 249.
5. Contestabile, M., Panero, S. & Scrosati, B., 1999. A laboratory-scale lithium battery
recycling process, Journal of Power Sources, 83, p. 75 – 78.
6. Castillo, S., Ansart, F., Laberty-Robert, C. & Portal, J., 2002. Advances in the recovering of
spent lithium battery compounds, Journal of Power Sources, 112, p. 247 – 254.

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