Supplementary Material

Sustainable Wastewater Purification with Crab Shell-Derived Biochar:

Advanced Machine Learning Modeling & Experimental Analysis

Amina Bibi,a, Hammad Khana*, Sajjad Hussaina, Muhammad Arshadb, Fazal Wahaba, Muhammad

Usamaa, Khurram Khanc, Feryal Akbald

a
Faculty of Materials and Chemical Engineering, GIK Institute of Engineering Sciences and
Technology, Topi, Pakistan
b
Department of Chemical Engineering, College of Engineering, King Khalid University, Abha, Saudi
Arabia
c
Faculty of Computer science and Engineering, GIK Institute of Engineering Sciences and Technology,
Topi, Pakistan
d
Department of Environmental Engineering, Ondokuz Mayıs Üniversitesi, Samsun, Turkey

*
Corresponding Author e-mail Addresses:

hammad@giki.edu.pk

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Table S1a: Description and formulation of statistical function for ML evaluation, Kinetics,
Isotherms and Thermodynamics.
Formula Equ. Description
qe (mg g–1): amounts of CR
S1
adsorbed at equilibrium,
S2 qt : amounts of CR adsorbed at a
given time t,
Kinetics

k1 (min-1)/ k2 (g mg-1 min-1): P1O

and P2O constants.
kid (mg g. min-0.5): intra-particle
S3 diffusion rate constant,
Ci: constant reflecting the extent of
the boundary layer effect,
Ci: boundary layer's thickness
S4 Ce, (mg L-1): equilibrium
concentration
S5 qm (mg g-1): maximum adsorption
capacity
Isotherms

kL (L mg-1), kF , kT, : Langmuir,

Freundlich and Temkin constants.
n= heterogeneity parameter,
S6 respectively.
R: universal gas constant (8.314 J
K−1 mol−1), and
T:temperature (K).
ΔGo (kJ mol-1): Gibbs free energy
Thermo S7 change
dynamics ΔSo (kJ mol-1K-1): entropy change,
S8 ΔHo (kJ.mol-1): enthalpy change

S9
Evaluation of ML frameworks

S10
n: total number of data points,
k: number of variables examined.
S11 yi,cal: predicted value,
yi,exp: experimental value, and
ӯexp: average experimental values
of the response parameter.
S12

S13

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Table S1b: Kinetic parameter for CR adsorption onto CB900.
Model/
50 (mg L-1) 150 (mg L-1) 300 (mg L-1) 600 (mg L-1) averag
Parameters
e
Temp 15 oC 25 oC 35 oC 45 oC 15 oC 25 oC 35 oC 45 oC 15 oC 25 oC 35 oC 45 oC 15 oC 25 oC 35 oC 45 oC

qe (mg g-1) 40.56 46.75 47.52 50.69 92.35 102.51 152.43 150.12 205.44 196.53 267.04 392.09 327.26 278.31 446.94 859.15 228.5
qe,exp (mg
40.02 45.73 47.83 50.61 87.02 103.92 141.87 146.87 149.11 170.84 207.87 291.85 224.89 241.82 277.23 588.56 173.8
g-1)
PFO

k1 (L mg-1) 0.08 0.07 0.11 0.26 0.04 0.05 0.04 0.10 0.02 0.03 0.02 0.03 0.02 0.03 0.02 0.02 0.0577

R2 0.992 0.995 0.995 0.999 0.963 0.972 0.973 0.992 0.976 0.952 0.956 0.935 0.982 0.992 0.991 0.928 0.974

χ2 0.71 0.41 0.34 0.04 8.19 5.91 8.92 1.90 10.21 20.66 21.72 49.74 9.35 3.76 8.38 174.58 20.30

qe (mg g-1) 49.20 58.03 55.08 53.41 122.57 132.37 210.49 177.78 313.19 272.16 396.92 611.26 531.01 398.30 731.54 1489.8 348.6
1.83E- 1.33E- 2.54E- 1.02E- 3.23E- 3.81E- 1.41E- 6.37E- 4.24E- 8.29E- 3.86E- 3.07E- 2.17E- 5.15E- 1.43E- 7.42E-
k2 (L mg-1) 0.0011
PSO

03 03 03 02 04 04 04 04 05 05 05 05 05 05 05 06
R2 0.986 0.984 0.979 0.989 0.972 0.985 0.981 0.975 0.978 0.960 0.961 0.930 0.982 0.989 0.991 0.924 0.973

χ2 0.91 1.41 1.64 0.62 6.02 3.19 5.86 5.70 8.60 16.32 18.52 51.54 9.62 5.21 7.93 161.82 19.85

kid 5.22 6.16 5.82 4.95 11.38 13.11 17.67 18.89 16.98 20.02 23.29 40.27 25.89 27.60 33.39 71.54 21.4

C 4.99 4.17 9.59 20.40 1.66 3.98 0.01 24.61 0.00 0.01 0.16 0.02 0.01 0.01 0.16 0.00 4.4
ID

R2 0.915 0.916 0.834 0.619 0.990 0.994 0.994 0.858 0.958 0.982 0.959 0.885 0.927 0.962 0.939 0.846 0.911

χ2 3.55 5.76 7.80 10.34 1.68 0.72 1.11 22.39 15.14 4.28 11.30 119.36 85.54 42.45 62.98 635.86 64.39

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4
Table S2: Installation, Equipment, and Total production cost of CB900 production on pilot
scale

Equipment Name Area (sq. ft) Equipment cost ($) Installation cost ($)
Storage Tank-1 400 27000 29700
Screens-1 80 32940 45900
Storage Tank-2 180 27000 29700
Rotary Kiln 405 108756 216000
Hammer Mill 170 23400 30600
Washing Tank 180 179280 296640
Rotary Dryer 70 32760 54360
Belt Conveyors 995 23400 14400
Air Cooler 45 36900 58500
Screens-2 80 32940 45900
Total 2605 $524,376 $821,700
Total Production
1042
Area (+40%)
Transport Area
1042
(+40%)
Miscellaneous
521
(+20%)
Total Area 5210

Total Capital Cost [USD] $1,450,429

Total Operating Cost [USD/Year] $2,597,940
Total Utilities Cost [USD/Year] $80,290
Crab shells Cost $3/kg
Raw Material Cost [USD/Year]
Total Direct Cost [USD/Year] $11,291,563
Indirect Cost [USD/Year] $2,822,890
Total Production Cost [USD/Year] $14,114,454

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Fig. S1. Effect of a)- pH, b)- CR con, c)- Adsorbent dose, and d)- contact time, on CR-RR (%)
and qCR (mg g-1). Standard conditions include pH: 05.0±0.2, time: 120 min, CR dye conc: 300±3
mg L-1, adsorbent dose: 0.2±0.02 g, temperature, 24±2 oC, and solution volume: 200 ml.

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Fig. S2. Effect of adsorption capacity with time for varying concentrations of CR dye onto CB900 at a)- 15 oC, b)- 25 oC, c)- 35 oC and d)- 45 oC

7
Fig. S3 Langmuir, Freundlich, Langmuir-Freundlich isotherms for the adsorption of of CR dye onto biochar CB900 at various temperatures