THE ELECTROCHEMICAL

EXTRACTION OF LITHIUM
FROM BRINE FOR LITHIUM
CARBONATE PRODUCTION
 ⒼⓇⓄⓊⓅ
Hello! 𝕋𝕂 𝟙𝟚
FARADILLA ANDIANI P. (1606886173)
JESSICA ADELINE S. (1606879943)
M. AZKIA RIFQI A. (1606891223)
SULTAN SHIDDIQI S. (1606905374)
TITA TRI YOLANDINI (1506673403)
2
1.
Introduction
Background
▫ Technology development to mobile devices

4
Background
▫ Lithium is sourced from ores and salt lake brine

5
Lithium for Battery Application
Advantages Disadvantages
▫ Highest cell potential ▫ Need protection circuit
and energy density and experience aging
▫ Development to safer ▫ Higher production cost
battery lithium-ion than other batteries
▫ Minimal maintenance
and less limitation
6
Lithium Carbonate
▫ Used as cathode in lithium ion batteries
▫ Suitable for cathode’s protective layer construction
▫ For battery industry minimum 99.5% purity in
powder crystal form

7
Lithium Extraction Method
▫ Conventional Precipitation Process
▫ Solvent Extraction
▫ Ion-sieve Adsorption
▫ Electrochemical Process
▫ Membrane Technology

8
Lithium Electrochemical Extraction
▫ Salt Capturing Battery System
 Uses Li+ cathode to extract Li+ and Ag anode to extract Cl-
 Uses recovery solution
 High selectivity, low energy consumption

9
Lithium Electrochemical Extraction (cont’d)
▫ Salt Capturing Battery System

10
Lithium Electrochemical Extraction
▫ Selective Exchange Battery System
 Extract lithium by cation exchange, avoiding the use of Ag
 Uses recovery solution
 Fast, efficient, has low environmental impact and low energy
consumption

11
Lithium Electrochemical Extraction
▫ Selective Exchange Battery System

12
Lithium Electrochemical Extraction
▫ Rocking Chair Battery System
 Good chemical stability, economical friendliness, and excellent
reversibility
 LiFePO4/FePO4 electrode pair has been used to selectively extract
lithium from brines
 By adjusting the potential, Li+ in brines will intercalate into the
negative electrode (FePO4) to form LiFePO4.
 At the same time, lithium in the positive electrode (LiFePO 4) would
be released into an appropriate electrolyte.
13
Lithium Electrochemical Extraction
▫ Rocking Chair Battery System

14
Raw Material Analysis

Spodumene Seawater Brine

15
Raw Material Analysis
▫  
Pertamina Cooling Water Return
▫ (+) Have more Li content than sea water (130 ppm)
▫ (+) Enough Supply for the lithium plant ()
▫ (+) Minimalize the purification process
▫ (-) Have Capital Cost on the Brine Water transfer (pipeline)

16
Market and Production Capacity

Lithium Fastest gains in

consumption lithium demand
CHINA
increasing each through 2019
year Asia Pacific

Electronic devices, electric

vehicles, electric tools, etc. 57% GLOBAL DEMAND
178,000 METRIC TONS OF LITHIUM CARBONATE 17
Market and Production Capacity
China's low lithium reserve
Supply and demand gap Market share
grade

50,000 metric tons of 178,000 – 50,000 0.2% of the total estimated metric
lithium carbonate tons oof lithium carbonate
production per year ecported to China.
128,000 metric tons gap
178,000 metric tons of
lithium carbonate demand Production Capacity
(2019) Exported to China
= 0.2% x 128,000 metric tons
= 267.696 metric tons

18
Plant Location
▫ Kariangau, West Balikpapan

▫ Close to raw material

▫ Proximity to market
▫ Land development
availability

19
2.
Process Synthesis
Process Route

Extraction Carbonation Purification

2𝐿𝑖𝐶𝑙(𝑎𝑞)+𝑁 𝑎2 𝐶𝑂3(𝑎𝑞)→𝐿𝑖2 𝐶𝑂3(𝑠)+2𝑁𝑎𝐶𝑙(𝑎𝑞)

▫  

21
 Process Selection
Electrochemical Extraction Method Selection Criteria
Scoring Criteria
Weight
Parameter
(%) 1 2 3 4

Has not proven to be Proven to be able to Proven to be able to Proven to be able to

Maturity 30 able to extract Li ions extract Li ions, but hardly extract Li ions, relatively extract Li ions, deep and
researched new research comprehensive research
Could not extract Li Extract mostly Li ions Extract mostly Li ions, Extract only Li ions and
Selectivity 30 ion separately from but still has noticeable with minor content of very small amounts of
another similar ion amount of similar ion similar ion similar ion
Very expensive Expensive electrode Cheap Electrode Very Cheap Electrode
Capital Cost 20
electrode
Energy More than 10 W 5-10 W h/mole Li+ 3-5 W h/mole Li+ Less than 3 W h/mole
20
Consumption h/mole Li+ recovered recovered recovered Li+ recovered 22
Process Selection
Electrochemical Extraction Method Selection
Salt Capturing Selective Exchange Rocking Chair
Parameter Weight (%)
Rating Score Rating Score Rating Score

Maturity 30 3 0.9 4 1.2 2 0.6

Selectivity 30 4 1.2 4 1.2 1 0.3

Capital Cost 20 2 0.4 4 0.8 2 0.4

Energy
20 4 0.8 2 0.4 1 0.2
Consumption
Total 3.3 3.6 1.8

Rank 2 1 3 23
Process Selection
Electrochemical Pair Selection

Parameter Simplicity Availability Recovery Lifetime

LiFePO4/NiHCF 0 0 0 0

LiMn2O4/PPy 0 + + +

LiMn2O4/Zn - 0 0 +

LiMn2O4/PPy. : the method is fast, efficient, has low energy consumption and has low environmental
impact since no water is lost and no chemicals are added.
24
Reactor Selection
▫ Electrochemical Extraction Reactor
 Electrochemical rectangular channel filter-press reactor
 Consists of two porous packed bed electrodes separated by a porous
insulating membrane filled with electrolyte.
 Both porous electrodes have current collectors and the electrolyte is fed from
the base of the reactor at a constant flow rate with outflow on the top.
 The positive electrode is LMO, as lithium insertion electrode.
 The negative electrode is chloride selective PPy electrode.

25
Reactor Selection
▫ Electrochemical Extraction Reactor
 Current collectors are made with
304 stainless steel and separated by
thick porous polyethylene battery
separator.
 The electrolytes employed is the
brine, and the recovery electrolyte
is 0.05 M LiCl solution (Romero et
al, 2018).

26
Reactor Selection
▫ Precipitation Reactor
 The reactor chosen for the precipitation process in
carbonation process is Batch Stirring Reactor
 The cost is cheaper
 The wanted product’s requirement is already
 Since the reactor is endothermic, it is necessary to
add heating element by using steam jacket

27
Process Description
▫ Evaporation
 Use multistage evaporator (3 - stages)
 In the first stage low pressure steam of 50 psig is used to evaporate brine.
 The vapor from the first stage becomes the heating source for the second stage, and so
on.
 First stage = 117.15°C (at 1.53 bar)
 Second stage = 114.88°C (at 1.34 bar)
 Third stage = 112.41°C (at 1.05 bar)
 The evaporated water from the third stage is condensed in the steam condenser using
cooling water on other side.
28
Process Description
▫ Electrochemical Extraction
▫ Using LiMn2O4 as cathode and Polypyrrole as anode
▫ Operating condition at 25oC and 1 bar
Discharge Charge
▫ Extracting LiCl from brine ▫ Release of LiCl to recovery solution
▫ 17.5 hours process ▫ 210 minutes process
▫ Producing 1.76 Wh/gram ▫ Consuming 4.24 Wh/gram lithium
lithium
29
Process Description
▫ Electrochemical Extraction Reaction
Cathode
▫  

Anode

Overall

30
Process Description
▫ Lithium Carbonate Synthesis
▫ T: 90°C
▫ P: 1 atm
▫ Endothermic ∆H363=54.77 kJ/mol
▫ Constant Heating with Steam Jacket

31
Lithium Carbonate Synthesis (cont’d)

▫  

Kinetic Parameters Value Unit

Reaction order with respect to LiCl, m 0.59 -

Reaction order with respect to Na2CO3, n 0.89 -

Overall order (m+n) 1.48 -
Activation Energy, 56.8 Kj/mol
Frequency factor, 1.35 x 108 32
Process Description
▫ Purification

Filtration Drying Crushing

33
Process Description
▫  Filtration
The goal is to separate the solution to be dissoluted
from the compound.
▫ P = 1 atm
▫ T=
▫ 90% filter efficiency
34
 Process Description
▫  Drying
The goal is to separate the solution and water to be in a perfect
solid condition.
▫ P = 1 atm
▫ T=
▫ Product Moisture <0.01%
▫ Using Disk Plate Dryer
▫ Plus additional cooling time without cooler 35
 Process Description
▫  Crushing
The goal is to decrease the size solid into smaller particles of
<7 microns (preferably 2-5 microns)
▫ P = 1 atm
▫ T=
▫ The crushing unit is called the micronizer

36
Block Flow Diagram

37
Process Flow Diagram

38
 Stream No 101 102 103 104 105 106 107 108
Component (kg/hr)
H2O 193,414.00 193,414.00 193,414.00 193,414.00 156,287.00 37,127.04 156,287.00 112,072.00
Li+ 31.89 31.89 31.89 31.89 31.89 0.00 31.89 31.89
Process Flow Diagram

Ca 2+

3,899.80 3,899.80 3,899.80 3,899.80 3,899.80 0.00 3,899.80 3,899.80

Mg 2+

492.99 492.99 492.99 492.99 492.99 0.00 492.99 492.99

N+ 13,244.60 13,244.60 13,244.60 13,244.60 13,244.60 0.00 13,244.60 13,244.60
K+ 1,250.88 1,250.88 1,250.88 1,250.88 1,250.88 0.00 1,250.88 1,250.88
SO ­ 2-
4

37.30 37.30 37.30 37.30 37.30 0.00 37.30 37.30

HCO3-
55.83 55.83 55.83 55.83 55.83 0.00 55.83 55.83
Cl -
30,080.23 30,080.23 30,080.23 30,080.23 30,080.23 0.00 30,080.23 30,080.23
Sr 2+

154.52 154.52 154.52 154.52 154.52 0.00 154.52 154.52

B3+
63.16 63.16 63.16 63.16 63.16 0.00 63.16 63.16
Br - 102.51 102.51 102.51 102.51 102.51 0.00 102.51 102.51
39
Total 242,827.71 242,827.71 242,827.71 242,827.71 205,700.71 37,127.04 205,700.71 161,485.71
Properties
Temperature (oC) 28 28.042 90 117.147 117.147 117.147 114.884 114.884
 Stream No 109 110 111 112 113 114 115 116
Component (kg/hr)
H2O 44,214.86 112,072.00 60,029.97 52,041.82 37,127.04 44,214.86 60,029.97 52,041.82
Li+ 0.00 31.89 31.89 0.00 0.00 0.00 31.89 0.00
Process Flow Diagram

Ca 2+

0.00 3,899.80 3,899.80 0.00 0.00 0.00 3,899.80 0.00

Mg 2+

0.00 492.99 492.99 0.00 0.00 0.00 492.99 0.00

N+ 0.00 13,244.60 13,244.60 0.00 0.00 0.00 13,244.60 0.00
K+
0.00 1,250.88 1,250.88 0.00 0.00 0.00 1,250.88 0.00
SO ­ 2-
4

0.00 37.30 37.30 0.00 0.00 0.00 37.30 0.00

HCO3-
0.00 55.83 55.83 0.00 0.00 0.00 55.83 0.00
Cl -
0.00 30,080.23 30,080.23 0.00 0.00 0.00 30,080.23 0.00
Sr 2+

0.00 154.52 154.52 0.00 0.00 0.00 154.52 0.00

B3+
0.00 63.16 63.16 0.00 0.00 0.00 63.16 0.00
Br - 0.00 102.51 102.51 0.00 0.00 0.00 102.51 0.00
40
Total 44,214.86 161,485.71 109,443.68 52,041.82 37,127.04 44,214.86 109,443.68 52,041.82
Properties
Temperature (oC) 114.884 112.405 112.405 112.405 29.147 29.884 25 101.02
Process Flow Diagram (cont’d)

41
 Stream No 201 202 203 204 205 206 207 208
Component (kg/hr)
H2O 60,029.97 20,893.29 13,965.56 13,965.56 15,220.40 1,522.04 0.00 0.00
Li +
31.89 33.70 23.12 23.12 16.07 1.60712 0.00 0.00
Ca2+ 3,899.80 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Process Flow Diagram

Mg2+ 492.99 0.00 0.00 0.00 0.00 0.00 0.00 0.00

Na +
13,244.60 0.00 0.00 0.00 231.79 23.18532 0.00 0.00
K+ 1,250.88 0.00 0.00 0.00 0.00 0.00 0.00 0.00
SO­42- 37.30 0.00 0.00 0.00 0.00 0.00 0.00 0.00
HCO3- 55.83 0.00 0.00 0.00 18.20 1.819928 0.00 0.00
Cl- 30,080.23 172.16 118.11 118.11 118.11 11.80823 0.00 0.00
Sr2+ 154.52 0.00 0.00 0.00 0.00 0.00 0.00 0.00
B3+ 63.16 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Br­­ -
102.51 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Na­­2CO3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Li2CO3 (s) 0.00 0.00 0.00 0.00 37.56 33.80 33.80 33.80
CO32- 0.00 0.00 0.00 0.00 254.13 25.40611 0.00 0.00
OH -
0.00 0.00 0.00 0.00 5.18 0.518266 0.00 0.00
O2+N2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Total 109,443.68 21,099.15 14,106.80 14,106.80 15,901.44 1,620.19 33.80 33.80
Properties
Temperature (oC) 25 25 25 25 90 90 115 25
Pressure (bar) 1 1 1 1.1 1 1 1 1 42
 Stream No 209 210 211 212 213 214 215 216
Component (kg/hr)
H2O 0.00 20,893.29 60,029.97 0.00 0.00 1,522.04 1,260.11 13,965.56
Li +
0.00 10.58 8.77 0.00 0.00 1.61 0.00 0.00
Ca2+ 0.00 0.00 3,899.80 0.00 0.00 0.00 0.00 0.00
Process Flow Diagram

Mg2+ 0.00 0.00 492.99 0.00 0.00 0.00 0.00 0.00

Na +
0.00 0.00 13,244.60 0.00 0.00 23.19 231.79 0.00
K+ 0.00 0.00 1,250.88 0.00 0.00 0.00 0.00 0.00
SO­42- 0.00 0.00 37.30 0.00 0.00 0.00 0.00 0.00
HCO3- 0.00 0.00 55.83 0.00 0.00 1.82 0.72 0.00
Cl- 0.00 54.05 29,962.12 0.00 0.00 11.81 0.00 0.00
Sr2+ 0.00 0.00 154.52 0.00 0.00 0.00 0.00 0.00
B3+ 0.00 0.00 63.16 0.00 0.00 0.00 0.00 0.00
Br­­ -
0.00 0.00 102.51 0.00 0.00 0.00 0.00 0.00
Na­­2CO3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Li2CO3 (s) 33.80 0.00 0.00 0.00 0.00 0.00 0.00 0.00
CO3 2-
0.00 0.00 0.00 0.00 0.00 25.41 301.82 0.00
OH -
0.00 0.00 0.00 0.00 0.00 0.52 0.20 0.00
O2+N2 0.00 0.00 0.00 100.00 100.00 100.00 0.00 0.00
Total 33.80 20,957.92 109,302.45 100.00 100.00 1,686.38 1,794.65 13,965.56
Properties
Temperature (oC) 25 25 25 25 119 118.779 115 25
Pressure (bar) 1 1 1 1 2 2 1 1 43
 Stream No 217 218 219 220
Component (kg/hr)
H2 O 6,927.73 6,927.73 20,893.29 13698.36
Li+ 10.58 10.58 10.58 14.46
Process Flow Diagram
Ca 2+
0.00 0.00 0.00 0.00
Mg2+ 0.00 0.00 0.00 0.00
Na+ 0.00 0.00 0.00 208.67
K+ 0.00 0.00 0.00 0.00
SO­42- 0.00 0.00 0.00 0.00
HCO3- 0.00 0.00 0.00 16.38
Cl- 54.05 54.05 54.05 106.27
Sr2+ 0.00 0.00 0.00 0.00
B 3+
0.00 0.00 0.00 0.00
Br­-­ 0.00 0.00 0.00 0.00
Na­­2CO3 0.00 0.00 0.00 0.00
Li2CO3 (s) 0.00 0.00 0.00 3.76
CO32- 0.00 0.00 0.00 228.65
OH- 0.00 0.00 0.00 4.66
O2+N2 0.00 0.00 0.00 0.00
Total 6,992.36 6,992.36 20,957.92 14281.22
Properties
Temperature (oC) 25 25 25 90
44
Pressure (bar) 1 1.1 1 1
3.
Mass and Energy Balance
Mass Balance for Seawater Evaporation
V-101
Mass Flow In (kg/hr) Mass Flow Out (kg/hr)
Component
104 105 106
H2O 193414 156287 37127.04
Li+ 31.89 31.89 0
Ca2+ 3899.80 3899.80 0
Mg 2+
492.99 492.99 0
N +
13244.60 13244.60 0
K +
1250.88 1250.88 0
SO­42- 37.30 37.30 0
HCO3- 55.83 55.83 0
Cl- 30080.23 30080.23 0
Sr 2+
154.52 154.52 0
B3+
63.16 63.16 1.23E-78
Br -
102.51 102.51 0
46
Total 242827.71 205700.71 37127.04
Mass Balance for Seawater Evaporation
V-102
Mass Flow In (kg/hr) Mass Flow Out (kg/hr)
Component
107 108 109
H2O 156287 112072 44214.86
Li+ 31.89 31.89 0
Ca2+ 3899.80 3899.80 0
Mg 2+
492.99 492.99 0
N +
13244.60 13244.60 0
K +
1250.88 1250.88 0
SO­42- 37.30 37.30 0
HCO 3
-
55.83 55.83 0
Cl -
30080.23 30080.23 0
Sr 2+
154.52 154.52 0
B3+
63.16 63.16 2.19E-78
Br -
102.51 102.51 0
47
Total 205700.71 161485.71 44214.86
Mass Balance for Seawater Evaporation
V-103
Mass Flow In (kg/hr) Mass Flow Out (kg/hr)
Component
110 111 112
H2O 112072 60029.97 52041.82
Li+ 31.89 31.89 0
Ca2+ 3899.80 3899.80 0
Mg 2+
492.99 492.99 0
N +
13244.60 13244.60 0
K +
1250.88 1250.88 0
SO­42- 37.30 37.30 0
HCO 3
-
55.83 55.83 0
Cl -
30080.23 30080.23 0
Sr 2+
154.52 154.52 0
B3+
63.16 63.16 5.22E-78
Br -
102.51 102.51 0
48
Total 161485.71 109443.68 52041.82
Mass Balance for Electrochemical Extraction
R-201
Mass Flow In (kg/hr) Mass Flow Out (kg/hr)
Component
201 219 202 211
H2O 60029.97 20893.29 20893.29 60029.97
Li+ 31.89 10.5765 33.6985 8.768
Ca 2+ 3899.8 0 0 3899.8
Mg2+ 492.99 0 0 492.99
Na+ 13244.6 0 0 13244.6
K+ 1250.88 0 0 1250.88
SO­42- 37.3 0 0 37.3

HCO3- 55.83 0 0 55.83

Cl- 30080.23 54.0493 172.1623 29962.117
Sr2+ 154.52 0 0 154.52
B3+ 63.16 0 0 63.16
Br­-­ 102.51 0 0 102.51
Na­­2CO3 0 0 0 0

Li2CO3 (s) 0 0 0 0

CO32- 0 0 0 0
OH - 0 0 0 0
49
O2+N2 0 0 0 0
Total 109443.68 20957.9158 21099.1508 109302.445
Mass Balance for Electrochemical Extraction
M-201
Mass Flow In (kg/hr) Mass Flow Out (kg/hr)
Component
216 218 219

H2O
13965.56 6927.73 20893.29
Li+ 0 10.5765 10.5765
Ca2+
0 0 0
Mg2+
0 0 0
Na +

0 0 0
K+
0 0 0

SO­42-
0 0 0

HCO3-
0 0 0
Cl -

0 54.0493 54.0493
50
Sr 2+

0 0 0
B3+
Mass Balance for Carbonation
R-202
Mass Flow In (kg/hr) Mass Flow Out (kg/hr)
Component
204 215 205

H2O
13,965.56 1,260.11 15,220.40
Li+ 23.12 231.79 16.07
Ca 2+

0.00 0.00 0.00

Mg2+
0.00 0.00 0.00
Na+
0.00 0.00 231.79
K+

0.00 0.00 0.00

SO ­ 2-
4

0.00 0.00 0.00

HCO3 -

0.00 0.72 18.20

Cl-
118.11 0.00 118.11 51
Sr 2+

0.00 0.00 0.00

B3+
Mass Balance for Purification
F-201
Mass Flow In (kg/hr) Mass Flow Out (kg/hr)
Component
205 206 220
Li+ 16.07117 1.607117 14.4641
Na+ 231.79 23.18532 208.60468
K+ 0 0 0
Cl- 118.11 11.80823 106.30177
LiCl 0 0 0
MgCl 0 0 0
H2O 15220.4 1522.04 13698.4
HCO3- 18.19928 1.819928 16.3794
Li2CO3 (s) 37.557 33.8013 3.7557
CO32- 254.13 25.40611 228.72389
OH -
5.182655 0.5182655 4.6643895
Total 15901.44011 1620.18627 14281.2538
52
Mass Balance for Purification
V-201
Mass Flow In (kg/hr) Mass Flow Out (kg/hr)
Component
206 213 207 214
Li+ 1.607117 0 0 1.607117
Na +
23.18532 0 0 23.18532
K+
0 0 0 0
Cl -
11.80823 0 0 11.8082
LiCl 0 0 0 0
MgCl 0 0 0 0
H2O 1522.04 0 0 1522.04
HCO3- 1.819928 0 0 1.819928
Li2CO3 (s) 33.8013 0 33.8013 0
CO3 2-
25.40611 0 0 25.40611
OH- 0.5182655 0 0 0.5182655
O2 + N2 0 100 0 100
53
Total 1620.18627 100 33.8013 1686.38497
Energy Balance for Evaporation Process
Enthalpy Flow Out
Equipment Enthalpy Flow In (MJ/h) Heat Duty (MJ/h)
(MJ/h)
P-101 -2,655,100.00 -2,655,066.39 33.61
E-101 -2,655,100.00 -2,604,182.60 50,917.00
E-102 -527,678.00 -633,760.00 -106,082.00
V-101 -2,604,200.00 -2,498,118.00 106,082.00
E-103 -491,928.00 -588,360.10 -96,432.00
V-102 -2,006,190.00 -1,909,757.90 96,432.00
E-104 -586,033.00 -700,550.00 -114,517.00
V-103 -1,323,724.90 -1,209,208.00 114,517.00
E-105 -519,205.00 -541,436.50 -22,232.00
E-106 -690,003.00 -808,536.00 -118,533.00
54
Total -89,814.39
Energy Balance for Extraction Process
Enthalpy Flow Out
Equipment Enthalpy Flow In (MJ/h) Heat Duty (MJ/h)
(MJ/h)
R-201 -1,638,970.00 -1,638,970.00 0.00
R-202 -245,243.00 -244,901.00 342.00
Total 342.00

55
Energy Balance for Drying Process
Enthalpy Flow Out
Equipment Enthalpy Flow In (MJ/h) Heat Duty (MJ/h)
(MJ/h)
V-201 -23,575.80 -23,400.80 175.00
E-201 -552.13 -556.21 -4.08
Total 170.92

56
Total Energy Balance
Enthalpy Flow Out
Equipment Enthalpy Flow In (MJ/h) Heat Duty (MJ/h)
(MJ/h)
P-101 -2,655,100.00 -2,655,066.39 33.61
E-101 -2,655,100.00 -2,604,182.60 50,917.00
E-102 -527,678.00 -633,760.00 -106,082.00
V-101 -2,604,200.00 -2,498,118.00 106,082.00
E-103 -491,928.00 -588,360.10 -96,432.00
V-102 -2,006,190.00 -1,909,757.90 96,432.00
E-104 -586,033.00 -700,550.00 -114,517.00
V-103 -1,323,724.90 -1,209,208.00 114,517.00
E-105 -519,205.00 -541,436.50 -22,232.00
E-106 -690,003.00 -808,536.00 -118,533.00
R-201 -1,638,970.00 -1,638,970.00 0.00
R-202 -245,243.00 -244,901.00 -342.00
V-201 -23,575.80 -23,400.80 -175.00
E-201 -552.13 -556.21 4.08
Total -15,967,502.83 -16,056,803.50 -90,327.31 57
Overall Mass Balance for Brine Evaporation
Mass Flow In (kg/hr) Mass Flow Out (kg/hr)
Component
101 113 114 115 116
H2O 193414 37127.04 44214.86 60029.97 52041.82
Li+ 31.88516 0 0 31.88516 0
Ca2+ 3899.8 0 0 3899.8 0
Mg2+ 492.9936 0 0 492.9936 0
N +
13244.6 0 0 13244.6 0
K +
1250.879 0 0 1250.879 0
SO­42- 37.29948 0 0 37.29948 0
HCO3 -
55.82891 0 0 55.82891 0
Cl- 30080.23 0 0 30080.23 0
Sr 2+
154.5204 0 0 154.5204 0
B3+
63.16287 1.23E-78 2.191E-78 63.16287 5.22E-78
Br -
102.5134 0 0 102.5134 0
Total 242827.7128 37127.04 44214.86 109443.7 52041.82
58
Overall Mass Balance for Lithium Carbonate Synthesis
Mass Flow In (kg/hr) Mass Flow Out (kg/hr)
Component
201 212 215 218 209 211 214 220
H2O 60,029.97 0.00 1,260.11 13965.56 0.00 60029.97 1,522.04 13698.36
Li+ 31.89 0.00 0.00 0 0.00 8.768 1.61 14.46
Ca2+
3,899.80 0.00 0.00 0 0.00 3899.8 0.00 0.00
Mg 2+

492.99 0.00 0.00 0 0.00 492.99 0.00 0.00

Na+
13,244.60 0.00 231.79 0 0.00 13244.6 23.19 208.67
K+
1,250.88 0.00 0.00 0 0.00 1250.88 0.00 0.00
SO ­ 2-
4

37.30 0.00 0.00 0 0.00 37.3 0.00 0.00

HCO3 -

55.83 0.00 0.72 0 0.00 55.83 1.82 16.38

Cl- 30,080.23 0.00 0.00 0 0.00 29962.12 11.81 106.27
Sr2+
154.52 0.00 0.00 0 0.00 154.52 0.00 0.00 59
B3+
63.16 0.00 0.00 0 0.00 63.16 0.00 0.00
Br­­ -
102.51 0.00 0.00 0 0.00 102.51 0.00 0.00
Overall Energy Balance
 

60
Product Conversion Efficiency
▫  

61
Yield
▫  

 
Energy Efficiency 𝑀𝐽
90,327.31
𝐷𝑢𝑡𝑦 h 𝑀𝐽
𝐸𝑛𝑒𝑟𝑔𝑦 𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛=𝑇𝑜𝑡𝑎𝑙 𝐻𝑒𝑎𝑡 =− =2,672.39
𝑚
˙ 𝑘𝑔 𝑘𝑔 Li 2 C O 3
33.8
h
62
4.
Heat Exchanger
Networking
 Network Design
▫ ∆T: 5°C
Streams Involved

Equipment T supply (°C) T supply (°C) Heat Duty (kW) Type Equipment

E-101 28.04 90 50,900 COLD E-101

E-102 90 117.15 -106,080 COLD E-102

E-105 112.41 25 -22,230 HOT E-105

E-106 112.41 101.02 -118,540 HOT E-106

64
Composite
Curve

Minimum Utility Requirement Value (kW), estimated

65
Hot (Qhmin) 40,000
Cold (Qcmin) 20,000
Problem Table
Shifted Temperature Data
Shift
Deficit/
Temperature Interval T(i+1)-Ti (°C) CPnet (kW/°C) ∆H (kW)
Surplus
(°C)
119.647
1 9.737 -3907.6878 -38049.1559 deficit
109.91
2 11.39 6752.4142 76921.3872 surplus
98.52
3 6.02 -3653.3316 -21993.1439 deficit
92.5
4 61.958 -567.4425 -35158.5026 deficit
30.542
5 8.042 254.3562 2045.4152 surplus
22.5
66
Cascade
Table

PINCH

67
HEN Design

68
HEN Design (cont’d)

69
PFD After HEN

70
71
72
5.
Utility
WATER
 Source : Ocean, 300 m away from the plant (seaside of West Balikpapan)
 To remove the impurities in seawater, water treatment needs to be done by desalination
unit with some membrane filter units.
 Cooling water is assumed that Tin of cooling water is 28oC and Tout 50oC (Walles, 2002)
 The calculation of water loss from evaporation, drift loss, and blowdown to calculate the
number of makeup water that is needed by this plant.
  1
𝐸𝑣𝑎𝑝𝑜𝑟𝑎𝑡𝑖𝑜𝑛 𝐿𝑜𝑠𝑠=
( 0.85 ×
100
×∆𝑇)
× 𝐶𝑖𝑟𝑐𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝐹𝑙𝑜𝑤
10

𝐷𝑟𝑖𝑓𝑡
  𝐿𝑜𝑠𝑠=%  𝐷𝑟𝑖𝑓𝑡 𝐿𝑜𝑠𝑠 ×𝐶𝑖𝑟𝑐𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝐹𝑙𝑜𝑤
  𝐸𝑣𝑎𝑝𝑜𝑟𝑎𝑡𝑖𝑜𝑛 𝐿𝑜𝑠𝑠
𝐵𝑙𝑜𝑤𝑑𝑜𝑤𝑛 𝐿𝑜𝑠𝑠=
𝐶𝑦𝑐𝑙𝑒𝑠 𝑜𝑓 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 −1 74
WATER
Cooling Water Requirement Before HEN
Cp
Equipme T in T out Q Q Mass Flow
Water
nt (oC) (oC) (MW) (kJ/h) (kg/h)
(kJ/kg.K)
E-105 28 50 6.18 22,231,500 4.18 241,751.85
130,168,00
E-106 28 50 32.93 4.18 1,415,484.99
0
Total Cooling Water Needed (kg/h) 1,657,236.84

Calculation of Makeup Cooling Water Before HEN

Losses Number Amount (kg/h)
Evaporation Loss 22oC 30,990.33
Drift Loss 0.20% 3,314.47
Blowdown Loss 4 cycles 10,330.11
Total Makeup Cooling Water (kg/h) 44,634.91 75
WATER
Cooling Water Requirement After HEN
T in T out Q Cp water Mass flow
Equipment Q (MW)
(oC) (oC) (kJ/h) (kJ/kg.K) (kg/h)
E-106 28 50 9,411 33,879,600 4.18 368,416.7
E-107 28 50 12.8 46,080,000 4.18 501,087.43
Total Cooling Water Needed (kg/h) 869,504.13

Calculation of Makeup Cooling Water After HEN

Losses Number Amount (kg/h)
Evaporation Loss 22oC 16,259.73
Drift Loss 0.20% 1,739.01
Blowdown Loss 4 cycles 5,419.91
Total Makeup Cooling Water (kg/h) 23,418.64
76
WATER

77
 PFD of Cooling Water

78
STEAM
▫ P = 50 psig, T = 148oC

Steam Requirement in Plant Before HEN

Specific
Stream Stream T In T Out Latent Mass Flow
Equipment Q (MJ/h) Heat
In Out (oC) (oC) (kg/h)
(MJ/kg)
E-101 102 103 28.042 90 50,917.4 2.126 23,949.86
E-102 103 104 90 117.15 106,082 2.126 49,897.46
R-202 204 205 25 90 4,130.5 2.126 1,942.85
Total Steam Needed (kg/hr) 75,790.17

 
assumed that 90% of steam condensate is reusable, the total addition of water per hour:

79
STEAM
Steam Requirement in Plant After
HEN
Specific
Mass
Stream Stream Latent
Equipment T In T Out Q (MJ/h) Flow
In Out heat
(kg/h)
(MJ/kg)
E-102 103 104 43.64 90 38,099 2.126 17,920.51
R-202 204 205 25 90 4,130.5 3.126 1,942.85
Total Steam Needed (kg/hr) 19,863.36

 
The total addition of water per hour :

80
 PFD of Steam Generation

81
ELECTRICITY
▫ Plant operating time
      24 hours with 330 days per year
▫ Not all of the plant equipment needs electricity
▫ The electricity will be supplied by PLN.
▫ Electricity cost per kWh by PLN = IDR1300

82
 ELECTRICITY
Equipment  Code  Usage Time (hr)  Energy Duty (MJ/H)  Power (Kw)  Power (Kwh/Day) 

P-101  24  33.61  11.67  280.06 

P-201  24  0.3  0.1  2.49 

Pump P-202  24  0.15  0.05  1.24 

P-Steam  24  0.35  10.86  260.64 

P-Cool  24  673.2  187  4476.07 

Electricity
Compressor  C-201  24  9  3  62.78 
requirement R-201 (Discharge)  17.5  51.14  14.2  248.57 
Reactor 
before HEN R-201 (Charge)  0.58  3695.67  1026.58  598.84 

Agitator  R-202  24  4  1.06  25.44 

Conveyor  E-201  24  27  7.5  180 

Total  1261.14  6136.12 

Total Electricity Needed Per Year  2,441,097.48  kWh 

Total Electricity Cost Per Year  3,173,426,729  Idr 

83
 ELECTRICITY
Equipment  Code  Usage Time (h)  Energy Duty (MJ/H)  Power (kW)  Power (kWh/Day) 

P-101  24  33.6  11,67  280,06 

P-201  24  0.3  0.1  2.49 

Pump P-202  24  0.15  0.05  1.23 

P-Steam  24  13.36  3.71  89.09 

P-Cool  24  45.21  12.56  301.43 

Electricity
Compressor C-201  24  9  3  62.78 
requirement R-201
17.5  51.14  14.2  248.57 
(Discharge) 
after HEN Reactor 
R-201 (Charge)  0.58  3695.68  1026.57  598.84 

Agitator  R-202  24  4  1.06  25.44 

Conveyor  E-201  24  27  7.5  180 

Total  1080.05  1789.92 

Total Electricity Needed Per Year  947,093.43  kWh 

Total Electricity Cost Per Year  1,231,221,463  IDR 

84
FUEL
▫ Steam generation process (boiler) needs fuel
▫ Fuel type used             diesel
▫ Mass flowrate of steam needed = 19,863.36 kg/hr
▫ Diesel heating value = 45,600 kJ/kg
▫ Specific latent heat of steam = 2.126 kJ/kg
▫ Assumed burning efficiency = 0.85

85
WASTEWATER
TREATMENT
In this plant, the by-product
produced will be treated by
external parties.

86
Comparison of Utility
Requirement Before and After HEN

Energy (MJ/hr)  Mass (kg/hr) 
HOT 
Before  After  % Saving  Before  After  %Saving 
161,129.90  42,229.50  73.79  75,790.17  19,863.36  73.79 
COLD 
Before  After  % Saving  Before  After  %Saving 
152,399,500.00  79,959,600.00  47.53  1,657,236.84  869,504.13  47.53 

87
Conclusion
▫ In order to substitute the current use of spodumene and mineral ore as the main
source of Li2CO3, this plant utilize the brine from the waste of petroleum industry
utility water with a high concentration of lithium.
▫ The plant will operate in Balikpapan, East Kalimantan with the main consideration
of proximity to raw materials.
▫ Li2CO3 as the main product will be supplied throughout China to meet their lithium
carbonate demand, with the production capacity of 267,696 kg of lithium carbonate
per year.
▫ LiCl that has been electrochemically extracted from brine is reacted with Na 2CO3,
resulting in Li2CO3 and NaCl solution. The operating condition is 90 °C and 1 bar.
88
Conclusion (cont’d)
▫ A product of 33.8013 kg/hr Li2CO3(s) is extracted from the purification process with
a total feed of 15,901.44 kg/hr and going through the filter at 90 oC and 1 bar, a dryer
at 119oC and 1 bar, conveyor at 115oC and 1 bar, and the crusher at 25oC and 1 bar.
▫ The conversion efficiency raw materials into useful product is 0.01388%. The yield
of product of Li2CO3 is 0.063342 kg Li2CO3/Na2CO3 and 0.000139 kg Li2CO3/kg
brine. The energy consumption per unit product is 2,672.39 MJ/ kg Li 2CO3.
▫ To optimize utilities usage, heat exchanger network design is made. It is a single
pinch problem. The result is the utility energy requirement can be reduced to 22,211
kW (cold) and 38,099 kW (hot).

89
Conclusion (cont’d)
▫ The utilities required for running the plant is water, steam, electricity, fuel, and
wastewater treatment. The water requirement is classified to cooling water
requirement that is a combination of 846,085.49 kg/hr and by make-up water is
23,418.64 kg/hr. The steam needed is about 75,790.17 kg/hr before HEN and
19,863.36 kg/hr after HEN. The total electricity needed per year before HEN is
2,441,097.48 kWh and 947,093.43 kWh after HEN. The fuel needed is 1.09 kg/hr.
The wastewater treatment that is going to be treated by external parties.

90
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Thank
You
93
CP of Each Streams

94
95
96
97
98
99