Cite this article Research Article

Mostafa NA, Farouk SM, Abdelhamid SMS and Monazie AM (2021) Paper 2100026
Optimisation and characterisation of bio-adsorbent based on barley straw and coconut shell. Received 08/06/2021; Accepted 14/09/2021
Journal of Environmental Engineering and Science XXXX(XXXX): 1–XX,
https://doi.org/10.1680/jenes.21.00026 ICE Publishing: All rights reserved

Journal of Environmental Engineering and Science

1 1
2 Optimisation and characterisation of bio- 2
3 3
4
5
adsorbent based on barley straw and coconut 4
5
6
7
shell 6
7
8 Q1 Q2 N.A. Mostafa SMS Abdelhamid 8
Professor, Department of Chemical Engineering, Minia University, El Minya, Professor, Department of Chemical Engineering, Egyptian Academy for
9 Egypt Engineering and Advanced Technology, Cairo, Egypt 9
10 Sabah Mohamed Farouk Aliaa M. Monazie 10
11 MSc student, Department of Chemical Engineering, Egyptian Academy for Assistant Professor, Department of Engineering Mathematics and Physics, 11
12 Engineering and Advanced Technology, Cairo, Egypt Fayoum University, Fayoum, Egypt (Orcid:0000-0003-0403-8025) 12
(corresponding author: amm17@fayoum.edu.eg)
13 13
14 14
15 Cost efficiency and environmental friendliness biomass-derived adsorbents for wastewater treatment are explored. 15
16 Preparation of bio-adsorbents which are economically and environmentally sustainable has achieved an enormous 16
17 interest in water treatment. A single-step method for preparing a high-capacity adsorbent is shown in this study by 17
18 refluxing barley straw (BS) and coconut shell (CS) in concentrated sulfuric acid. Using response surface methodology 18
19 predicts the optimum parameters for production of the bio-adsorbent based on the yield and the adsorption 19
20 capacity for methylene blue dye. Optimal conditions for the sulfuric acid refluxing stage were obtained at 94% 20
21 sulfuric acid, 10 liquid/solid (L/S) ratio for 2 h and 98% sulfuric acid, 4 L/S ratio for 2.5 h for BS and CS, respectively. 21
22 The produced bio-adsorbent was characterised by scanning electron microscopy coupled with energy dispersive 22
23 X-ray scattering, X-ray diffraction, Fourier transform infrared spectroscopy, thermo gravimetric analysis, Raman 23
24 spectroscopy, and Brunauer–Emmett–Teller specific surface area analysis. The detailed analysis showed that the bio- 24
25 adsorbent produced from BS and CS has good adsorptive properties – thermal stability and high specific surface area 25
26 which are 11.759 and 1.165 m2/g, respectively. The results indicated that BS and CS are critical and potential low-cost 26
27 raw materials for the production of bio-adsorbents. 27
28 Keywords: bio-adsorbent/characterisation & modelling 28
29 29
30 30
Introduction to adsorb big molecules (McKay et al., 1998). Physical and
31 31
Environmental sustainability has received considerable attention chemical treatment methods are used for production of activated
32 32
due to the benefits of biomass conversion into fuel and carbon. Physical treatment requires raw material carbonisation
33 33
commodity products. Although the conversion of biomass into without oxygen and inert gasses then oxidisation by air, steam
34 34
biofuels is being emphasised, the development of new methods and carbon dioxide, while chemical treatment includes
35 35
for the generation of bio-derived products such as bio-plastics, carbonisation with strong dehydrating and oxidising agents such
36 36
bio-oils, biogas, bio-molecules, bio-char and bio-carbon products H3PO4, ZnCl2, KOH and NaOH (Yahya et al., 2018).
37 37
have increased. Bio-adsorbents are also highly significant, as they
38 38
can provide an environmentally friendly and sustainable way to There are several methods used to produce activated carbon from
39 39
remove pollutants from wastewater (Islam et al., 2018). different agriculture wastes. Activated carbon can be synthesised
40 40
from rice husk by washing, filtration of rice husk and heating
41 41
Activated carbon is mainly atomic carbon; it has a high porosity gradually up to 500°C then the temperature increased to 900°C
42 42
and complexity structure. Its pores form an unorganised channels for the activation step (Masoud et al., 2016). Kadirvelu et al.
43 43
network connecting to a rigid skeleton (Setoyama et al., 1998). (2000) have produced activated carbon from coconut tree sawdust
44 44
after drying and carbonating in a furnace at 700°C. It is found that
45 45
Activated carbon can be produced from coconut shells, peat, soft toxic heavy metals and organics are adsorbed remarkably using
46 46
wood, hard wood and pits of olive (Fiuza Jr et al., 2015; carbonised sawdust (Kadirvelu et al., 2000). Bagasse, coconut
47 47
Gundogdu et al., 2013). shells and husks were treated by using nitrogen in a fixed bed
48 48
reactor. After carbonisation, the product was dried, ground and
49 49
The adsorption process is efficiently depending on the unique screened. It was found that microcrystallinity of activated carbon
50 50
properties of activated carbon, which include large surfaces and depends on the high content of cellulose, oxygen, hydrogen and
51 51
favourable pores (Shahrokhi-Shahraki et al., 2021). These volatile matters in the raw material (Mortley et al., 1988). The
52 52
properties vary depending on the source material and activation peanut shells based activated carbon were washed, dried, crushed
53 53
conditions (Wang et al., 2021). The liquid adsorption process and sieved. Chemical activation of precursor was conducted using
54 54
requires deep pores of activated carbon. The pores are fairly large microwave. Maximum adsorption capacity is 284.5 mg/g in
55 55

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 Journal of Environmental Engineering Optimisation and characterisation of
and Science bio-adsorbent based on barley straw
Volume XXXX Issue XXXX and coconut shell
Mostafa, Farouk, Abdelhamid and Monazie

1 removing Reactive Red 141 dye (Georgin et al., 2016). Banana Batch adsorption experiments 1
2 peel was dehydrated in an oven until it was fully dried, then Twenty milligrams of sulfonated barley straw (BS-SO3H) or 2
3 crushed. The samples were subjected to the carbonisation and sulfonated coconut shell (CS-SO3H) was mixed with 20 ml of 3
4 chemical activation in a muffle furnace (Budiyanto et al., 2017). 1000 ppm MB at neutral pH. The mixture was moved to a 4
5 Bagasse fly ash was treated with hydrogen peroxide at 60°C for reciprocal shaker at 100 rpm for 6 h. The blend was filtered 5
6 24 h, and then it was cleaned with water, and dried at 100°C. The through a Gooch funnel (G4), then adsorption capacity was 6
7 adsorbent exhibits good adsorption capacity (Gupta et al., 2003). calculated. The optical density of MB dye was measured at 7
8 Watermelon rinds were washed, dried, ground and sieved before 630 nm to calculate the MB dye concentration then calculate the 8
9 impregnation with concentrated sulfuric acid (Jawad et al., 2019). adsorption capacity of both BS-SO3H and CS-SO3H using 9
10 Pine cone and peanut shell were used for production of bio- ultraviolet visible spectrophotometer (model SPECTRO DR 2800) 10
11 adsorbent. Samples were mixed in the presence of sulfuric acid at the National Research Centre (NRC). 11
12 placed in bottomed flask, which was connected with a reflux 12
13 condenser (Islam et al., 2018, 2019). Experimental design and data analysis 13
14 In the current study, RSM based on Box–Behnken experimental 14
15 In this work a high-capacity adsorbent is prepared by following a design, with five runs at the centre point, giving a total of 17 15
16 one-step method, where carbonisation and sulfonation of barley experimental runs, was applied for optimising responses (yield 16
17 straw (BS) and coconut shell (CS) have proceeded. We selected and adsorption capacity) and to evaluate the effect of the 17
18 the two biomasses as they are abundant waste in Egypt. BS independent process variables (time, 1–3 h; H2SO4 concentration, 18
19 represents straw waste while CS represents woody cellulose 82–98%; liquid/solid (L/S) ratio, 4–12 ml/g). Experimental 19
20 waste. This method is performed by refluxing barley straw and process variables and levels for Box-Behnken design are given in 20
21 coconut shell in concentrated sulfuric acid. The yield and Table 1. Design-Expert 10.0.1 software was used for the statistical 21
22 adsorption capacity of bio-adsorbent is affected by the sulfuric analysis, modelling and optimisation. 22
23 acid concentration, the contact time and the ratio between solid 23
24 (raw material) and liquid (sulfuric acid). Consequently, the Characterisation of produced bio-based adsorbent 24
25 response surface methodology (RSM) model is applied to predict The Brunauer–Emmett–Teller surface area 25
26 the optimum parameters that affect the bio-adsorbent production. The Brunauer–Emmett–Teller (BET) model was used to calculate the 26
27 total surface area of the prepared materials. The BET surface area 27
28 was estimated from nitrogen adsorption isotherm data obtained at 28
29 Experimental part 77 K. QuantachromeNovaWin 3200, USA, was used at the Egyptian 29
30 Materials Petroleum Research Institute EPRI. Before the measurements, the 30
31 Barley straw from a field in Minia, Egypt, was collected, washed samples were degassed at 120°C overnight. 31
32 with water to remove dust, sun dried and then ground using 32
33 kitchen's grinder. The coconut shell was supplied by Frucherer, Thermo gravimetric analysis 33
34 Minia, Egypt, washed with water to remove dust, sun dried and Thermo gravimetric analysis (TGA) was used to study the 34
35 then crushed to small pieces by mortar and pestle. Chemicals physico-chemical changes (decomposition or oxidation) that took 35
36 were used with no further treatment. Sulfuric acid 98% and place during heating the material (Olphen and Fripiat, 1979). 36
37 methylene blue (MB) dye were purchased from Alpha Chemika TGA Q500 V20.10 with nitrogen as an inert atmosphere installed 37
38 Pharmaceuticals and Chemicals Company. at the Science and Technology Center of Excellence (STCE) with 38
39 a flow rate of 50 ml/min, a heating rate of 10°C /min and a 39
40 temperature range of 25–900°C/min. 40
41 41
42 Procedures Fourier transform infrared (FTIR) 42
43 Preparation of the bio-based adsorbent by sulfuric acid Infrared spectroscopy is a characterisation technique according to 43
44 reflux the vibration modes at various infrared wave numbers; function 44
45 Ten grams of sample was mixed with different quantities of groups in molecules are identified, and it is used for observation 45
46 H2SO4 (40, 80, and 120 ml) at different concentrations (82, 90, 46
47 and 98%). The reactants were refluxed in boiling H2SO4 for 47
48 various duration times (1, 2 and 3 h). Once reflux was finished, Table 1. Experimental variables and levels for Box–Behnken 48
49 the reaction mixture was cooled down to room temperature and design 49
50 250 ml of ice-cold water was gradually poured to the mixture with Level 50
51 care to prevent overheating. After the mixture was diluted, the Variables Symbols 51
–1 0 +1
52 excess H2SO4 was filtered and washed with de-ionised water. 52
53 Then the sulfonated sample was dried by placing it in a drying Time: h A 1 2 3 53
54 oven at 110°C for 12 h. Samples were dried and ground into fine H2SO4 concentration: % B 82 90 98 54
Liquid/solid (L/S) ratio C 4 8 12
55 powder using mortar and pestle. 55

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 Journal of Environmental Engineering Optimisation and characterisation of
and Science bio-adsorbent based on barley straw
Volume XXXX Issue XXXX and coconut shell
Mostafa, Farouk, Abdelhamid and Monazie

1 of any changes resulting from interactions. The samples are Results and discussion 1
2 measured at Egyptian academy and advanced technology labs The response surface models of the bio-adsorbent production 2
3 using Class1 Laser Product IEC/EN 60825-1/A2:2001 Avatar outcomes (yield and adsorption capacity) 3
4 Series (USA). 4
5 The experimental and predicted values for the bio-adsorbent 5
6 production outcomes (yield and adsorption capacity) responses at 6
Raman spectroscopy
7 the design points and all the three uncoded independent process 7
Raman spectroscopy is a molecular spectroscopic method used in
8 variables are set in Table 2. 8
the interaction of light with matter to gain insight into a material's
9 9
Q3 make up or characteristics (Mettler, 2020). Raman analysis was
10 The experimental data was analysed and the following regression 10
performed using a dispersive Raman microscope Sentera Bruker
11 equations in terms of coded factors were obtained for the 11
instrument at the Egyptian Petroleum Research Institute (EPRI).
12 predicted values of output responses (yield and adsorption 12
A laser source of 532 nm and maximum power of 20 mW was
13 capacity) for both barley straw and coconut shell: 13
used to excite the samples.
14 14
15 For barley straw: 15
16 X-ray powder diffraction analysis Yield = 0.54 − 0.049A − 0.06B − 0.071C + 0.015AB + 16
17 XRD analysis is used to identify the crystalline phases present in 0.033AC + 0.015BC − 0.031A2 − 0.089B2 − 0.11C2 17
18 Q4 a material to detect its chemical composition (Element, 2020). 18
19 Crystal-phase structure was investigated by Powder X-ray Adsorption capacity = 265.02 − 1.89A + 9.08B + 19
20 diffraction (XRD) analysis; it was carried out with a PAN 6.89C + 2.82AB − 3.45AC + 14.08BC − 33.04A2 − 18.61B2 − 20
21 analytical x, PERT PRO, using CuKa X-ray radiation (l = 18.63C2 21
22 1.540 Å) at the Egyptian Petroleum Research Institute (EPRI). 22
23 For coconut shell: 23
24 24
25 Scanning electron microscope coupled with energy Yield = 0.57 − 0.051A − 0.15B − 0.064C − 0.028AB + 25
26 dispersive X-ray scattering 0.04AC − 0.068BC − 0.03A2 − 0.077B2 + 0.051C2 26
27 Scanning electron microscopy (SEM) is a technique that provides 27
28 high-resolution electronic images by scanning with an electron Adsorption capacity = 208.94 + 0.46A + 7.68B + 28
29 beam. The analytical technique of energy-dispersive X-ray 0.31C + 13.45AB − 0.63AC − 6.9BC + 4.12A2 + 6.59B2 + 29
30 spectroscopy (EDX) was used for obtaining information about the 10.02C2 30
31 elemental composition (Arenas-Lago et al., 2017). SEM was 31
32 recorded on equipment QUANTA FEG250, installed at the NRC, Figure 1 shows that the predicted values for the bio-adsorbent 32
33 and SEM–EDX using Sigma300 VP (Zeiss, Germany) at the production responses (yield and adsorption capacity) are 33
34 Egyptian Petroleum Research Institute (EPRI). reasonably close to the actual values for both BS-SO3H and 34
35 35
36 Table 2. Experimental and predicted responses for the bio-adsorbent production using barley straw and coconut shell 36
37 37
B: Yield: g/g Adsorption capacity: mg/g
38 A:
H2SO4
C: L/S 38
39 Run Time: ratio: Barley straw Coconut shell Barley straw Coconut shell 39
conc.:
h ml/g
40 % Experimental Predicted Experimental Predicted Experimental Predicted Experimental Predicted 40
41 1 3 98 8 0.27 0.39 0.21 0.29 208.7 213.37 247.5 230.1 41
42 2 2 98 4 0.4 0.45 0.52 0.53 221.2 227.78 242.5 226.6 42
43 3 1 90 12 0.35 0.46 0.51 0.61 216.2 213.35 232.5 219.0 43
44 4 3 82 8 0.44 0.51 0.57 0.60 207.4 213.37 201.2 187.8 44
5 2 90 8 0.53 0.54 0.6 0.57 266.3 265.02 208.7 208.9
45 45
6 3 90 12 0.35 0.46 0.54 0.51 212.4 213.35 223.7 219.0
46 7 2 90 8 0.6 0.54 0.58 0.57 262.5 265.02 211.2 208.9 46
47 8 2 82 12 0.26 0.43 0.71 0.70 206.2 227.78 222.4 211.3 47
48 9 3 90 4 0.39 0.60 0.6 0.64 217.4 213.35 214.9 219.0 48
49 10 2 90 8 0.54 0.54 0.54 0.57 266.3 265.02 211.2 208.9 49
11 2 90 8 0.55 0.54 0.6 0.57 265 265.02 207.4 208.9
50 50
12 1 82 8 0.6 0.51 0.67 0.70 223.7 213.37 218.7 214.7
51 13 1 98 8 0.37 0.39 0.42 0.40 213.7 213.37 211.2 203.2 51
52 14 1 90 4 0.52 0.60 0.73 0.74 207.4 213.35 221.2 219.0 52
53 15 2 82 4 0.47 0.57 0.69 0.70 208.7 227.78 217.4 211.3 53
54 16 2 90 8 0.48 0.54 0.55 0.57 265 265.02 206.2 208.9 54
17 2 98 12 0.25 0.31 0.27 0.26 275 227.78 219.9 226.6
55 55

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 Journal of Environmental Engineering Optimisation and characterisation of
and Science bio-adsorbent based on barley straw
Volume XXXX Issue XXXX and coconut shell
Mostafa, Farouk, Abdelhamid and Monazie

1 BS BS 1
2 2
0.6 280
3 3
4 4
5 5

Predicted adsorption capacity: mg/g

260
6 0.5 6
7 7
Predicted yield: g/g

8 8
240
9 9
10 0.4 10
11 220
11
12 12
13 13
0.3
14 200 14
15 15
16 16
17 0.2 180 17
18 18
19 0.2 0.3 0.4 0.5 0.6 180 200 220 240 260 280 19
20 Actual adsorption capacity: mg/g 20
Actual yield: g/g
21 (a) (b) 21
22 CS
22
CS
23 23
24 0.8 250 24
25 25
26 0.7 240 26
Predicted adsorption capacity: mg/g

27 27
28 28
0.6
Predicted yield: g/g

29 230 29
30 30
31 0.5 220 31
32 32
33 33
0.4 210
34 34
35 35
36 0.3 200 36
37 37
38 38
0.2 190
39 39
40 40
0.2 0.3 0.4 0.5 0.6 0.7 0.8 190 200 210 220 230 240 250
41 Actual yield: g/g 41
Actual adsorption capacity: mg/g
42 (c) 42
(d)
43 43
44 Figure 1. Predicted and actual values for BS-SO3H yield (a), adsorption capacity (b) and CS-SO3H yield (c), adsorption capacity (d) 44
45 45
46 46
47 47
48 48
49 49
Table 3. ANOVA for the predicted quadratic models of the bio-adsorbent production responses
50 50
51 Source Sum of squares Mean square F value P value prob >F Lack of fit F-value Std. dev. Squared-R 51
52 BS-SO3H Yield 0.19 0.021 5.79 0.0152 3.19 0.06 0.8816 52
53 Adsorption capacity 10240.61 1137.85 5.69 0.0159 192.36 14.14 0.8798 53
54 CS-SO3H Yield 0.31 0.034 26.55 0.0001 2.49 0.036 0.9715 54
Adsorption capacity 2133.5 237.06 4.43 0.0312 23.43 7.31 0.8508
55 55

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 Journal of Environmental Engineering Optimisation and characterisation of
and Science bio-adsorbent based on barley straw
Volume XXXX Issue XXXX and coconut shell
Mostafa, Farouk, Abdelhamid and Monazie

1 1
2 2
0.6 280
3 3
4 4

Adsorption capacity: mg/g

0.5 260
5 5
6 240 6
0.4
7 7
Yield: g/g

220
8 8
0.3
9 200 9
10 10
0.2
11 180 11
12 12
13 98 3.0 98 3.0 13
14 B:
Ac
94 2.5
B: 94 2.5 14
id 90 Ac
15 co
nc
2.0
e:
h id
co 90 2.0 15
en 86 1.5 Tim nc e :h
16 tra
tio A:
en
tra 86 1.5 T im 16
n: 82 1.0 tio A:
17 % n:
%
82 1.0 17
(a)
18 (b) 18
19 19
0.6
20 280 20
21 21
0.5 260
22 22
Adsorption capacity: mg/g

23 240 23
0.4
24 24
Yield: g/g

25 220 25
0.3
26 26
200
27 27
0.2
28 180 28
29 29
12
30 3.0
12 30
3.0
31 10 2.5
10 2.5 31
8 2.0 h
32 C: im
e: 8 2.0 32
L/S 6 1.5 T h
A: C: e:
33 4 1.0 L/S 6 1.5 T im 33
A:
34 4 1. 34
(c) (d)
35 35
36 36
0.6
37 280 37
38 38
0.5 260
39 39
Adsorption capacity: mg/g

40 240 40
0.4
Yield: g/g

41 41
220
42 42
0.3
43 200 43
44 44
0.2 180
45 45
46 46
12 98 12
47 94
98 47
10 %
48 o n: 10 94 :% 48
8 90 ati on
C: ntr 8 90 r ati
49 L/S 6 86
con
ce C:
L/S 6 86 cen
t 49
cid con
50 4 82
B:
A 4 82 Ac
id 50
(e) B:
51 (f) 51
52 52
Figure 2. The 3D plot for the effect of time and acid concentration (a, b), time and L/S ratio (c, d) acid concentration and L/S ratio (e, f) on
53 BS-SO3H yield and adsorption capacity
53
54 54
55 55

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 Journal of Environmental Engineering Optimisation and characterisation of
and Science bio-adsorbent based on barley straw
Volume XXXX Issue XXXX and coconut shell
Mostafa, Farouk, Abdelhamid and Monazie

1 CS-SO3H, thus confirming the consistency of the models adsorption capacity based on the relevant developed mathematical 1
2 established for creating a relationship concerning the independent models (Gratuito et al., 2008). 2
3 process variables and the responses. 3
4 The optimal parameters for BS-SO3H and CS-SO3H were as follows: 4
5 The statistical significance of yield and adsorption capacity time, 1.976 and 2.428 h; H2SO4 concentration, 94.249 and 98%; 5
6 models was assessed by ANOVA (Table 3). Table 3 indicates that liquid/solid ratio, 10.01 and 4 ml/g, respectively. The target yields 6
7 the F-values of the predicted models for barley straw bio- achieved at this condition were 0.425 and 0.47 g/g with maximum 7
8 adsorbent were 5.79 and 5.69 for yield and adsorption capacity, adsorption capacities of 267.133 and 246.791 mg/g, respectively. The 8
9 respectively, implying that the two models are significant. The practical confirmatory experiment results (Table 4) were found to be 9
10 ‘lack of fit F-values’ of 3.19 and 192.36 indicates that there was a very close and in good agreement with the predicted results. The 10
11 bad correlation with the pure error for the model representing ultimate errors were very low (less than 1.5%) for the predicted 11
12 adsorption capacity. responses (yield and adsorption capacity) obtained using the 12
13 developed models for both BS-SO3H and CS-SO3H. This shows that 13
14 Also, the model F-values for coconut shell bio-adsorbent response surface methodology was able to forecast the experimental 14
15 responses were 26.55 and 4.43 for yield and adsorption capacity, results very well. As a result, the models developed were considered 15
16 respectively, implying that the two models are significant. The to be accurate and reliable (Government et al., 2019). 16
17 ‘lack of fit F-values’ of 2.49 and 23.43 indicating that there was a 17
18 bad correlation with the pure error for the model representing Characterisation of bio-adsorbents 18
19 adsorption capacity. The Brunauer–Emmett–Teller surface area 19
20 To estimate the specific surface area of the bio-adsorbents material, 20
21 The R-squared values for the four models equations (0.8816, 0.8798, N2 gas adsorption analysis Brunauer–Emmett–Teller (BET) was 21
22 0.9715 and 0.8508) were larger than 0.75, which displayed the fitting carried out. It was found that the BS-SO3H and CS-SO3H had a 22
23 degree of the quadratic models were good (Zhang et al., 2020). specific surface area of about 11.759 and 1.165 about m2/g, 23
24 respectively; when compared with the surface area of the untreated 24
25 Effect of process parameters barley straw and coconut shell, it was found to be 0.06 m2/g (Jazini 25
26 The 3D curves for both types of bio-adsorbents (BS-SO3H and et al., 2018) and 0.84 m2/g (Lee et al., 2017), respectively. The 26
27 CS-SO3H) were drawn to show the effects of the independent higher surface area of the BS-SO3H is confirmed by its high 27
28 variables (time, acid concentration and L/S ratio) on the dependent adsorption capacity for MB compared with CS- SO3H. Also, the BS- 28
29 variables (yield and absorption capacity) for the four developed SO3H surface area is higher than that of other sulfonated material in 29
30 models. These 3D surface graphs and their consistent contour plots the literature as shown in Table 5. 30
31 (Figures 2 and 3) show the influence of two variables within their 31
32 studied ranges, with the other variable fixed to the zero level. The Thermo gravimetric analysis 32
33 nature and extents of interactions between two independent variables The thermo gravimetric analysis (TGA) is utilised to limit the 33
34 are predicted from the shape of contour plots. An elliptical contour thermal stability and the decomposition profile of the BS-SO3H and 34
35 plot indicates a prominent interaction, whereas a negligible effect CS-SO3H as revealed in Figure 4. The absorbed water was 35
36 appears as a circular contour plot (Das and Mishra, 2017; Dwivedi evaporated at a temperature range from 50–150°C. The bio-adsorbent 36
37 and Sharma, 2015). major decomposition started from about 200°C and a complete 37
38 decomposition was observed at a temperature of about 600°C and 38
39 Figures 2 and 3 indicate that there was a relative significant above. Thus, the TGA curve indicated that the BS-SO3H and CS- 39
40 interaction between every two variables (time and acid concentration, SO3H have good thermal stability, but CS-SO3H is more stable than 40
41 time and L/S ratio, acid concentration and L/S ratio). The bio- BS-SO3H; therefore, they could be utilised for the adsorption of 41
42 adsorbent yield generally decreased as the time increased. This pollutants at high temperature (Islam et al., 2019). 42
43 behaviour can be explained by the fact that the destructive effect on 43
44 raw material fibre increased by time, while the BS-SO3H yield and X-ray powder diffraction analysis 44
45 adsorption capacity increased with the increasing acid concentration, As shown in Figure 5, the XRD patterns of BS-SO3H (A) and of 45
46 but the trend was reversed when the acid concentration reached a CS-SO3H (B) have a major diffraction peak at 25. The peak at 25 46
47 certain value (Figure 2(a) and (b)). The same result was observed for could be indexed to the (002) planes of hexagonal graphite 47
48 L/S ratio (Figure 2(c) and (d)). Therefore, the increase of either acid (JCPDS no. 41-1487) (Qie et al., 2012), indicating that all 48
49 concentration or L/S ratio encourages the sulfonation of raw fibre to samples of bio-adsorbents exhibit the diffuse characteristics 49
50 a certain limit, then the destructive effect became prevalent. pattern of an amorphous phase. 50
51 51
52 Optimisation of the operating parameters to enhance Fourier transform infrared 52
53 bio-adsorbent production Fourier transform infrared (FTIR) spectroscopy was applied on 53
54 The optimum values for the bio-adsorbent production were identified the barley straw and coconut shell before and after the sulfonation 54
55 by the midpoints of the yield to achieve the maximisation of the to distinguish the differences in the functional groups and 55

jees2100026.pdf 6 Manila Typesetting Company 10/02/2021 1:01pm

 Journal of Environmental Engineering Optimisation and characterisation of
and Science bio-adsorbent based on barley straw
Volume XXXX Issue XXXX and coconut shell
Mostafa, Farouk, Abdelhamid and Monazie

1 1
2 250
2
0.8
3 3
4 0.7 240 4

Adsorption capacity: mg/g

5 0.6 230 5
6 6
0.5 220
7 7
Yield: g/g

8 0.4 210 8
9 0.3 200 9
10 10
0.2 190
11 11
12 12
13 98 3.0 98 3.0 13
14 B: A 94 2.5
B: A 94 2.5 14
cid
15 con 90 2.0 cid 15
cen e: h con 90 2.0
e: h
tra 86 1.5 Tim cen Tim
16 tion A: tra 86 1.5
A: 16
:% 82 1.0 tion 82 1.0
17 (a) :% 17
(b)
18 18
19 0.8 19
250
20 20
0.7
21 240 21
22 22
Adsorption capacity: mg/g

0.6 230
23 0.5 23
Yield: g/g

220
24 24
0.4
25 210 25
26 0.3 200 26
27 0.2 27
190
28 28
29 12
29
3.0
30 10 2.5
12 3.0 30
31 8 2.0 10 2.5 31
C: e: h
32 L/S 6 1.5 A:
Tim C: 8 2.0
e: h
32
L/S
33
6 1.5 Tim 33
4 1.0 A:
(c) 4 1.0
34 (d) 34
35 35
0.8
36 250 36
37 0.7
240
37
38 0.6 38
Adsorption capacity: mg/g

230
39 39
0.5
40 40
Yield: g/g

220

41 0.4
210 41
42 0.3 200 42
43 0.2
43
190
44 44
45 45
12 98 12
46 98 46
10 94 :% 10 94
47 ion ion
:% 47
8 90 t rat 8 90 rat
48 C: ce n C: cent 48
L/S 6 86 con L/S 6 86 on
49 4 82 A cid 4 82 cid c 49
B: B:A
50 (e) (f) 50
51 51
Figure 3. The 3D plot for the effect of time and acid concentration (a, b), time and L/S ratio (c, d), acid concentration and L/S ratio
52 (e, f) on CS-SO3H yield and adsorption capacity
52
53 53
54 54
55 55

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 Journal of Environmental Engineering Optimisation and characterisation of
and Science bio-adsorbent based on barley straw
Volume XXXX Issue XXXX and coconut shell
Mostafa, Farouk, Abdelhamid and Monazie

1 Table 4. Model validation at optimum conditions for bio-adsorbent produced from barely straw and coconut shell 1
2 Yield: g/g Adsorption capacity: mg/g
2
3 Model Time: h Acid conc.: % L/S ratio 3
Predicted Experimental % Error Predicted Experimental % Error
4 4
5 BS-SO3H 1.976 94.249 10.01 0.425 0.430 1.18 267.133 265.9 0.46 5
6 CS-SO3H 2.428 98 4 0.470 0.474 0.85 246.791 245.4 0.56 6
7 7
8 Table 5. Different surface area of sulfonated adsorbents depicted in Figure 6. As revealed in Figure 6(a), the FTIR spectra 8
9 Surface area: of the barley straw showed the being of OH, aliphatic CH, 9
Adsorbents
10 m2/g carbonyl (C=O), and aromatic ring C=C functional groups at 10
11 Sulfonated pine cone (Islam et al., 2018) 4.55 3435.62, 2924.42, 1642.87, and 1380.79 cm−1, respectively. Also, 11
12 Sulfonated peanut shell (Islam et al., 2019) 3.7 as given in Figure 6(c), the FTIR spectra of the coconut shell 12
13 Sulfonated cotton linter (Dong et al., 2013) 1.58 showed the same function groups. After the sulfuric acid reflux 13
14 Sulfonated poly (arylene ether nitrite) (Zhou 4.18 (Figure 6(b) and (d)), new peak originated at 1101.51 and 14
et al., 2019)
15 1175.41 cm−1, which could be accredited to the S=O stretching 15
16 sulfonic acid hydrate in the BS-SO3H and CS-SO3H, respectively 16
17 100 (Donald et al., 2014). Also, some characteristic peaks disappeared 17
18 indicating the change in functional groups after the sulfuric acid 18
19 Barely straw reflux. 19
Coconut shell
20 80 20
21 Raman spectroscopy 21
22 Raman spectroscopy was used to examine the carbonaceous 22
23 60 23
Weight: %

nature of the material. Crystalline graphite only displays one peak

24 24
25 25
26 40 26
27 A 27
28 28

466.31
29 20 29

605.13
1380.79

30 30
31 31
2924.42

1642.87

32 0 32
1098.45

0 200 400 600 800 1000 B

33 33
%Transmittance: arbitrary units

799.62

Temperature: ºC
34 34
3435.62

35 Figure 4. Thermal gravimetric curve of BS-SO3H and CS-SO3H

35
1716.13

36 36
1612.95
3408.53

464.32

37 37
38 38
C
39 39
40 40
1101.51

(a)
41 80 41
2356.98

42 42
2855.82

548.43
1458.80
1738.99

1035.56

43 43
Intensity: arbitrary units

(b)
1631.45

60
2923.59

44 44
45 45
46 40 D 46
3420.68 3433.32

47 47
1706.76

400.00

48 48
2922.63

1597.71

20
49 49
175.41

50 50
51 0 4000 3500 3000 2500 2000 1500 1000 500 51
10 20 30 40 50 60 70 Wave number: cm−1
52 52
2θ: º
53 53
Figure 6. FTIR spectrum of barley straw (a) before and (b) after
54 Figure 5. XRPD pattern (a) of BS-SO3H and (b) of the CS-SO3H and coconut shell (c) before and (d) after sulfuric acid reflux 54
55 55

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 Journal of Environmental Engineering Optimisation and characterisation of
and Science bio-adsorbent based on barley straw
Volume XXXX Issue XXXX and coconut shell
Mostafa, Farouk, Abdelhamid and Monazie

1 at around 1582 cm−1 which is characterised as graphite peak or G 1

2 peak while amorphous carbon or disordered carbon shows a 2
3 peak called D peak at around 1350 cm−1 (Jänes et al., 2007). In 3
4 µm 4
Figure 7, BS-SO3H and CS-SO3H have two bands located at .45
18
5 1579.76, 1329.26 cm−1 and 1558.1, 1315.1 cm−1, respectively. 5
m
6 The ratio (ID/IG) which utilised to assess the structural disorder for 6µ 6
9
7 BS-SO3H and CS-SO3H, were found to be 0.841 and 0.844, 1 8. m 7
µ
8 .78 8
respectively, which displayed that the BS-SO3H and CS-SO3H 14
9 had high degree of defects and disorder and were more µm 9
.67
26
10 amorphous. The amorphous shape of the prepared bio-adsorbent µm 10
01
24.

m
11 was confirmed by XRD analysis, as given in Figure 5. 11

0µ
.6
12 12

32
Spot 9/14/2020 100 µm
13 13
HV Mag. WD Det. HFW
Scanning electron microscopy coupled with energy 20.00 kV ×800 5.0 9.3 mm BSED 518 µm 12:09:05 PM QUANTA FEG250 (NRC)

14 dispersive X-ray scattering (a) 14

15 The apparent morphology of the BS-SO3H and CS-SO3H were 12 12.59 µm 15
6. 9 .53
16 studied using scanning electron microscope (SEM) and represented 98 µm 13. 27 µm 16
µm
17 in Figure 8(a) and (b). The SEM images revealed that the BS-SO3H 17
20.50 µm
18 18

8.3
and CS-SO3H consist of particles with random size and shape. The

84
19 particles were found mostly in the micrometer size range with a large 19

9.878
25.17 µm

µm
20 degree of aggregation. The surface of the BS-SO3H and CS-SO3H 16. 20
41

µm
21 µm 14 21
24

are heterogeneous and highly porous. The pore size ranges from 14 10 .75
.73
.86

22 to 28 µm and from 9 to 24 µm for BS-SO3H and CS-SO3H, µm 12. µm 22

55
µm

23 respectively. µm 23
24 10.35 µm 24
25 25
The qualitative and quantitative composition of the BS-SO3H and
µm

26 26
.28

CS-SO3H were obtained from the EDX spectrum analysis; it was 16.01 µm
27 27
13

observed that the BS-SO3H and CS-SO3H were elementally

28 HV Mag. Spot WD Det. HFW 10/6/2020
11:22:35 AM
50 µm
28
composed of approximately (41.69%C; 49.68%O; 8.62%S) and 20.00 kV ×1500 5.0 10.4 mm BSED 276 µm QUANTA FEG250 (NRC)

29 (b) 29
30 30
31 Figure 8. SEM images (a) of BS-SO3H and (b) of S-SO3H 31
1558.10

32 32
33 33
1315.10

34 (63.93%C; 35.8%O; 0.27%S) by weight, respectively. The higher 34

35 carbon content in the coconut shell compared with barley straw may 35
36 be due to the more efficient carbonisation of coconut shell. On the 36
Raman intensity: arbitrary units

37 other hand, the sulfonation of barley straw is more efficient than that 37
38 of coconut shell and this is because of the hard structure fibre in 38
39 coconut shell. 39
40 40
41 Conclusion 41
42 Response surface methodology model is able to forecast the 42
43 experimental results very well. The target yields achieved at 43
44 optimum condition were 0.425 and 0.47 g/g, with maximum 44
BS-SO3H
45 adsorption capacities of 267.133 and 246.791 mg/g, respectively. 45
46 46
47 The BS-SO3H surface area is higher than that of CS-SO3H and other 47
1329.26
1579.76

48 sulfonated material in the literature. TGA curve indicated that the 48

49 BS-SO3H and CS-SO3H have good thermal stability; therefore, they 49
CS-SO3H
50 could be used for the adsorption of pollutants at high temperature. 50
51 The surface of the BS-SO3H and CS-SO3H are heterogeneous and 51
4000 3500 3000 2500 2000 1500 1000 500
52 highly porous with high carbon, oxygen and sulfur content; therefore, 52
Wave number: cm–1
53 the produced bio-adsorbent from both barley straw and coconut shell 53
54 Figure 7. Raman spectra for BS-SO3H and CS-SO3H is an environmentally friendly, low-cost and sustainable material to 54
55 be used in wastewater treatment. 55

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 Journal of Environmental Engineering Optimisation and characterisation of
and Science bio-adsorbent based on barley straw
Volume XXXX Issue XXXX and coconut shell
Mostafa, Farouk, Abdelhamid and Monazie

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the editor at journals@ice.org.uk. Your contribution will be
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 Author Queries

Q1: Please provide forename for authors NA Mostafa and SMS Abdelhamid. Please note that name should be presented in first name
last name order.
Q2: Please provide post-nominal qualification for all authors.
Q3: The citation https://www.mt.com has been changed to Mettler, 2020 with respect to the reference list provided; please check and
confirm the change.
Q4: The citation https://www.element.com has been changed to Element, 2020 with respect to the reference list provided; please
check and confirm the change.
Q5: Please provide the editors and publisher location for reference Budiyanto et al. (2017).
Q6: Please provide the publisher name and location for reference Donald et al. (2014).
Q7: Please provide the issue number for references Dong et al.(2013), Fiuza et al. (2015), Gundogdu et al. (2013), Jawad et al.
(2019), Lee et al. (2017), Qie et al. (2012), Shahrokhi-Shahraki et al. (2021), Wang et al. (2021) and et al. (2020).
Q8: If the proceedings of the conference in reference Yahya et al. (2018) have been published, please provide the title of the
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location details – town/city, state (if USA) and country – of where the conference took place.