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Removal of Methylene Blue and Orange-G from Waste Water Using Magnetic Biochar

Article  in  International Journal of Nanoscience · January 2015

DOI: 10.1142/S0219581X1550009X

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International Journal of Nanoscience

Vol. 14, Nos. 1 & 2 (2015) 1550009 (13 pages)
1 #.c World Scienti¯c Publishing Company 53
2 DOI: 10.1142/S0219581X1550009X 54
3 55
4 56
5 57
6 58
7 59
8 Removal of Methylene Blue and Orange-G from Waste 60
9 Water Using Magnetic Biochar 61
10 62
11 63
12 N. M. Mubarak*,†,||,††, Y. T. Fo*,**,††, Hikmat Said Al-Salim*, 64
13 J. N. Sahu‡, E. C. Abdullah§, S. Nizamuddin†, N. S. Jayakumar† and P. Ganesan¶ 65
*Department of Chemical and Petroleum Engineering
14 66
15 Faculty of Engineering, UCSI University, Kuala Lumpur-56000, Malaysia 67
16 †Department of Chemical Engineering, Faculty of Engineering 68
17 University of Malaya, 50603 Kuala Lumpur, Malaysia 69
18 ‡Petroleum and Chemical Engineering Programme Area 70
19 Faculty of Engineering, Institut Teknologi Brunei (A Technology University) 71
20 Tungku Gadong, P. O. Box 2909, Brunei Darussalam 72
21 § 73
Malaysia – Japan International Institute of Technology (MJIIT)
22 74
Universiti Teknologi Malaysia, Jalan Semarak, 54100 Kuala Lumpur, Malaysia
23 75
¶Department of Mechanical Engineering, Faculty of Engineering
24 76
25 University of Malaya, 50603 Kuala Lumpur, Malaysia 77
||mubarak.yaseen@gmail.com
26 78
**foothailim@gmail.com
27 79
28 80
29 Received 11 September 2014 81
30 Accepted 15 January 2015 82
31 Published 83
32 84
33 85
The study on the removal of methylene blue (MB) and orange-G dyes using magnetic biochar
34 derived from the empty fruit bunch (EFB) was carried out. Process parameters such as pH, 86
35 adsorbent dosage, agitation speed and contact time were optimized using Design-Expert Soft- 87
36 ware v.6.0.8. The statistical analysis reveals that the optimum conditions for the maximum 88
37 adsorption of MB are at pH 2 and pH 10, dosage 1.0 g, and agitation speed and contact time of 89
38 125 rpm and 120 min respectively. While for orange-G, at pH 2, dosage 1.0 g, and agitation 90
39 speed and contact time of 125 rpm and 120 min respectively. The maximum adsorption capacity 91
40 of 31.25 mg/g and 32.36 mg/g for MB and orange-G respectively. The adsorption kinetic for 92
41 both dyes obeyed pseudo-second order. 93
42 94
Keywords: Magnetic biochar; methylene blue; orange-G; adsorption; separation.
43 95
44 96
45 97
46 1. Introduction of life, but with the growing industrialization 98
47 all over us, it creates a deep impact on human 99
48 De¯ciency of clean water is a global concern where 100
its primary cause is very much due to water pollu- health as well as to the environment by producing
49 101
50 tion. Water is the most basic necessity requirement large quantities of untreated wastewater into the 102
51 †† Corresponding authors.
103
52 104
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N. M. Mubarak et al.

1 surrounding environment. One of the industries obtained from industry as well as agriculture, re- 53
2 which consume the most water is the textile in- quiring lower cost yielding higher e±ciency.7 For a 54
3 dustry and is listed as the main contributor of water very long time, carbon substances which are highly 55
4 pollution due to the tremendous amount of waste- mesoporous have been used for several applications 56
5 water containing dyes released to the environment. such as catalyst support, separation, drug delivery,8 57
6 As recorded, more than 7
10 5 tonnes of dyes are adsorbents,9 batteries running on lithium ion,10 and 58
7 produced annually by this particular industry1 and supercapacitors.11 Nevertheless, the separation of 59
8 it was estimated by the World Bank that approxi- carbon from the products obtained at the ¯nal stage 60
9 mately 17% to 20% of the world industrial water is a di±cult process and usually involves intricate 61
10 pollution emanates from both treatment and dyeing steps. The choices of raw materials to choose from 62
11 of textiles. In addition, 72 toxic chemicals were for the production of activated carbon are so wide 63
12 identi¯ed to be present in our water wholly from the and they can be easily obtained from the agriculture 64
13 textile dyeing in which 30 of these chemicals are or any plant-based sectors. These materials are 65
14 unable to be removed. One of the chemicals iden- such as the coconut tree sawdust, silk cotton 66
15 ti¯ed, tributyl phosphate is a hazardous chemical hull, palm kernel shell, pea shells,12 peel of cucumis 67
16 used by this industry as a plasticizer and to act as sativa fruit,13 rice husk,14 perlite,15 bagasse °y ash,3 68
17 an antifoaming agent and is capable to cause irri- casuarinas charcoal16 and teak sawdust.17 However, 69
18 tation to the nose, throat, and lungs and even coma. di®erent types of adsorbents have di®erent physical 70
19 Hence, discharged wastewater containing dyes even properties, although they have similar working 71
20 in the smallest amount can form harmful by-pro- principles as well as di®erent selectivity towards 72
21 ducts from hydrolysis, oxidation, or other danger- di®erent dyes. Due to their nature of selectivity, ac- 73
22 ous chemical reactions it the wastewater phase.2 tivated carbons can e±ciently remove water-soluble 74
23 Dyes can be categorized as cationic which are the dyes which are present in the wastewater. However, it 75
24 basic dyes, anionic which are the acid, direct, and is not capable of adsorbing suspended solids and in- 76
25 reactive dyes, and nonionic which are the disperse soluble dyes. Another downside of activated carbon is 77
26 dyes.3 Due to the stability of dye to light and re- that it is not recommended to be used directly in the 78
27 sistant to biodegradation, as well as the oxidizing most fundamental textile wastewater treatment and 79
28 agents, the application of some traditional methods it is commonly used at a lower concentration value for 80
29 for the treatment of dye-containing wastewater dye wastewater treatment due to its high cost for the 81
30 is limited. In recent years, a number of di®erent regeneration process.18 Recently magnetic biochar is 82
31 techniques have been developed in the research for used to remove various pollutants, including phos- 83
32 removal of dye from wastewater. Plenty of methods phate, heavy metals, and organic compounds, from 84
33 have been implemented for the treatment of aqueous solutions.19,20 Introducing magnetic biochar, 85
34 wastewater. However, due to the high stability of to the commercial sorbent (e.g., active carbon and 86
35 modern dyes, both the conventional biological and carbon nano tubes) by chemical co-precipitation is an 87
36 physicochemical water puri¯cation methods are e±cient method, to enable the sorbent to be e®ectively 88
37 found to be ine±cient to remove dyes.4 Other con- separated by magnetic separating technique.21 89
38 ventional methods used for dye removal are the In this research, statistical optimization and the 90
39 coagulation and °occulation,4 ozonation or oxida- comparative study on the removal of methylene 91
40 tion,5 liquid-liquid extraction, and membrane sep- blue (MB) and orange-G from aqueous solution by 92
41 aration.6 These methods are not favored as they using magnetic biochar derived from the empty 93
42 require high cost and possess economic dis- fruit bunch (EFB) were carried out. The kinetic and 94
43 advantages. The °occulation and coagulation using isotherm studies for the removal of dyes were also 95
44 metallic compounds techniques, form and discharge investigated. 96
45 sludge and this causes the concentration of metallic 97
46 contaminants to increase.2 Hence, to solve this 98
47 problem, the liquid phase adsorption process was 2. Materials and Methods 99
48 developed as an alternative technique to treat waste 100
49 e®luents containing dye. In this adsorption process 2.1. Raw materials 101
50 for the discoloration of wastewater discharged from Magnetic biochar involved in this project is synthe- 102
51 the textile industry, nonconventional adsorbents sized via a method similar to that reported by 103
52 derived from natural materials and waste materials Mubarak et al.22 Analytical grade MB (C16 H18 N3SCI) 104
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Removal of Methylene Blue and Orange-G from Waste Water Using Magnetic Biochar

1 and orange-G (C16 H10 N2Na2O7S2) and molecular Table 1. Experimental design for the batch adsorption study. 53
2 weight of 319.85 g/mol and 452.38 g/mol of MB and 54
No. Variable Range
3 orange-G respectively was purchased from Merck 55
4 and used as received. 1 Dosage of magnetic 0.25 g, 0.63 g, 1.00 g 56
5 biochar 57
6 2 pH of dye solution pH 2, pH 6, pH 10 58
7 2.2. Preparation of magnetic biochar 3 Contact time 30 min, 75 min,
59
120 min
8 The schematic of microwave reactor for production 60
9 of magnetic biochar as describe in my previous work.22 61
10 EFB was grinded to approximately the 120
m par- solution was agitated with varying dosage of mag- 62
11 ticle size and was treated chemically by using the ferric netic biochars, di®erent pH values with di®erent 63
12 chloride (FeCl3). After the chemical treatment, it was contact time based on the design obtained from the 64
13 agitated for 4 h, followed by drying at 100  C for 24 h. version 6.0.8 of Design Expert. All experiments in 65
14 The pyrolysis of biomass was carried out in the this research were carried out at a constant room 66
15 HAMiab-C1500 microwave mu®le system oven where temperature by using a water bath. The pH values 67
16 a sample of biomass was prepared and placed inside a of the dye stock solutions were altered by using ei- 68
17 quartz tube. The conditions of process during this ther 1.0 M of hydrochloric acid or 1.0 M sodium 69
18 reaction are such as the power of microwave to be hydroxide, depending on the value of desired pH. 70
19 800 W, reaction time of 30 min and a ratio of im- Table 1 shows the variables used for this research. 71
20 pregnation of 0.5. The ratio of impregnation is the For the magnetic biochar used in this research, its 72
21 weight of the activating agent/weight of the biomass. adsorption capacity at time t was determined by 73
22 The carrier gas used in this chemical activation pro- using Eq. (1). As for the adsorption equilibrium of 74
23 cess was the nitrogen gas, which provides iron oxide the dye, it was determined based on Eq. (2). 75
24 magnetite formation. It is this formation which pro- 76
ðCo  Ct ÞV
25 vides the magnetic characteristics to the biochar. At qt ¼ ð1Þ 77
26 the completion of the activation process, the sample m 78
27 was allowed to cool at room temperature. Next, the ðC  Ce ÞV 79
qe ¼ o ð2Þ
28 sample was removed from the quartz tube and the m 80
29 weight in order to ¯nd out the yield of the product. where Co represents the initial concentration of the 81
30 The obtained biochar sample was placed and stored in dye solution (mg/L), Ct is the concentration of dye 82
31 closed bottles, which were closed tightly. The ¯nal solutions at time t (mg/L) and Ce is the equilibrium 83
32 step was to wash this magnetic biochar by using dis- concentration of dye soltion (mg/L). V is the vol- 84
33 tilled water in order to achieve a neutral pH. ume of dye solution (L) and m is the weight of 85
34 magnetic biochar adsorbent used (g). 86
35 87
36 2.3. Preparation of stock solutions 88
37 Stock solutions of MB and orange-G which were 3. Results and Discussion 89
38 obtained from Merck were prepared for this research. 90
39 The initial concentrations of the stock solutions were 3.1. The e®ect of process parameters 91
40 set at 30 mg/L. First of all, 30 mg of the dye powder, on the removal of colors 92
41 for instance, MB powder, was weighed by using the E®ect of process parameters on the removal of MB 93
42 weighing machine. Then, 1 L of distilled water was and orange-G were carried out by conducting an 94
43 prepared. Next, both the prepared dye powder and experiment using three parameters; the pH of the 95
44 distilled water were mixed and stirred to ensure a dye stock solution, the dosage of the magnetic bio- 96
45 homogeneous solution was obtained. A similar pro- char adsorbent and the contact time. The e®ects of 97
46 cedure was repeated for the next dye stock solution; each process parameter were further discussed in 98
47 orange-G. the following section. 99
48 100
49 101
2.4. Batch adsorption experiment 3.1.1. The e®ect of pH of dye stock solutions
50 102
51 The batch adsorption experiment was carried out The pH of the stock solution was altered by adding 103
52 using 200 mL of 30 mg/L MB dye solution. The dye hydrochloric acid or sodium hydroxide, depending 104
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N. M. Mubarak et al.

1 53
2 54
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6 58
7 59
8 60
9 61
10 62
11 63
12 64
13 65
14 66
15 67
16 68
17 69
18 70
(a) (b)
19 71
20 Fig. 1. 3-D interaction plots for the removal of methylene blue by using empty fruitbunch derived magnetic biochar, (a) rela- 72
21 tionship between pH of stock solution and its contact time, (b) relationship between pH of stock solution and the dosage of 73
adsorbent.
22 74
23 75
24 on which desired pH was required. The adjustment occurred at a lower pH due to the protonation 76
25 of the pH values was carried out by using the pH property of the adsorbent. The lower the pH value, 77
26 meter model Eutech Instruments. There are three the higher is the concentration of hydrogen 78
27 desired pH values being studied which are pH 2, pH ions.25–28 Hence, the negative charges on the surface 79
28 6, and pH 10. Figure 1(a) shows the 3-dimensional of internal pores will be neutralized and new sites 80
29 interaction plot relating the pH with a percentage of for adsorption will be formed. Hence, the surface of 81
30 dye removal. On average, pH 10 has the highest the adsorbent will supply the positive charges for 82
31 removal percentage. This is because with an in- the anionic orange-G dyes to be adsorbed. Figure 3 83
32 crease in pH value, the density of the surface charge shows the relationship between pH of stock solution 84
33 decreases and this causes a lowering in the electro- with the percentage removal of dyes. Hence, it can 85
34 static repulsion between the surface of the magnetic be observed from Fig. 3 that pH 2 and pH 10 are the 86
35 biochar and the positively charged MB and thus, optimum pH for the removal of MB and pH 2 is the 87
36 elevating the rate of dye adsorption. On another optimum pH for the removal of the orange-G. 88
37 note, the highest dye removal recorded belongs to 89
38 the run with pH 2 with a removal percentage of 90
96.68%. The reason behind this excellent adsorption 3.1.2. The e®ect of contact time
39 91
40 characteristic even at such low pH is due to the The e®ect of contact time of removal of MB and 92
41 replacement of the hydrogen ions on the surface of orange-G is illustrated in Fig. 1(a). The contact 93
42 the adsorbent with the cationic dye molecules in the time values were set at 30 min, 75 min and 120 min. 94
43 solution.23,24 Figure 1(a), it is observed that as the contact time 95
44 Hence, it can be concluded that the removal of increases, the removal percentage of MB decreases. 96
45 MB can be achieved by using stock solutions of ei- Thus, it can be said that why the three-dimensional 97
46 ther low or high pH values by using EFB derived plot showed such result was due to the combination 98
47 magnetic biochar. According to Fig. 2(a) for the of these variables. So, regardless of how long of the 99
48 removal of orange-G, it is shown that removal per- agitation time was given to the interaction between 100
49 centage increases as pH value decreases. Highest the adsorbent and adsorbate, if the quantity of 101
50 dye removal was achieved at pH 2 with 90.76% adsorbent used is insu±cient, the removal percent- 102
51 and the lowest adsorption process belongs to run age of dye will still be low. As for Fig. 2(a), it is 103
52 with pH 10 with just 78.78%. High removal of dye shown that as contact time increases, the removal 104
1550009-4
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Removal of Methylene Blue and Orange-G from Waste Water Using Magnetic Biochar

1 53
2 54
3 55
4 56
5 57
6 58
7 59
8 60
9 61
10 62
11 63
12 64
13 65
14 66
15 67
16 68
17 69
18 70
19 (a) (b) 71
20 Fig. 2. 3-D interaction plots for the removal of orange gelb by using empty fruit bunch derived magnetic biochar, (a) relationship
72
21 between pH of stock solution and its contact time, (b) relationship between pH of stock solution and the dosage of adsorbent. 73
22 74
23 percentage of orange-G dye increases as well. This removal percentage of the two dyes. These graphs 75
24 dye removal pattern was observed because as the were plotted by using a constant dosage of adsor- 76
25 interaction time increases, the adsorbent and ad- bent of 1.00 gram and pH value of 10 at room 77
26 sorbate were allowed to interact with one another. temperature. Hence, it is proven that as contact 78
27 Also, during the initial stage of the removal process, time increase, the removal percentage of the two 79
28 plenty of unoccupied surface sites are available and dyes increases as well. 80
29 made accessible for the orange-G dyes to be adsor- 81
30 bed onto. However, after a period of time, the 82
31 remaining unoccupied sites are di±cult to be occu- 3.1.3. The e®ect of dosage of adsorbent 83
32 pied due to the repulsive forces between the solute The dosage values of magnetic biochar used in this 84
33 molecules of the solid and bulk phases. Figure 4 study are 0.25 g, 0.63 g and 1.00 g. The e®ect of this 85
34 show the relationship of contact time with the variable was studied by carrying out analysis on the 86
35 87
36 88
37 89
38 90
39 91
40 92
41 93
42 94
43 95
44 96
45 97
46 98
47 99
48 100
49 101
50 102
51 103
52 Fig. 3. E®ect of pH on removal of MB and orange-G. Fig. 4. E®ect of contact on removal of MB and orange-G. 104
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N. M. Mubarak et al.

1 time of 120 min at room temperature. It is observed 53

2 that from these two ¯gures, the removal percentage 54
3 increases with an increase in dosage. 55
4 56
5 57
6 3.2. Statistical analysis for the removal 58
7 of MB and orange-G 59
8 Statistical analysis of the percentage removal of the 60
9 color of MB and orange-G from the prepared stock 61
10 solutions were studied where the Design Expert 62
11 software was fully utilized. In order to carry out the 63
12 experiments, the \design of experiment" (DOE) was 64
13 ¯rst obtained from Design Expert. Table 1 shows 65
14 the design of experiment for the removal of MB and 66
15 orange-G dyes by using the magnetic biochar as well 67
16 Fig. 5. E®ect of dosage on removal of MB and orange-G. as the removal percentage. The research was con- 68
17 tinued by carrying out an analysis using the 69
18 percentage of dye removal at the end of each run. \analysis of variance" (ANOVA) from the Design 70
19 According to the 3-dimensional plots from Figs. 1 Expert. Tables 2 and 3 tabulate the analysis 71
20 (b) and 2(b), as the amount of adsorbents used in- obtained from this ANOVA application for the re- 72
21 crease, the percentage removal of both dyes in- moval of MB and orange-G from the stock solutions 73
22 creased as well. For methylene blue, the highest respectively. 74
23 removal of dye took place when 1.00 g of adsorbent The ¯sher-F test value was used to prove the 75
24 were used with a percentage removal of 96.68%, e±ciency of a particular model, whereas the F test 76
25 whereas, the lowest removal percentage which is at value increases, the e±ciency of the model increases 77
26 just 48.62% occurred when only 0.25 g of adsorbent as well. This F value can be correlated with the 78
27 was used. As for orange-G, the highest removal was mean square of the regressed model where this 79
28 achieved when 1.00 g adsorbent was used by 90.76% allows the comparison of the mean square of the 80
29 and low at 0.25 g with just 78.78% removal. This is residuals which is the error to be carried out. A high 81
30 because when more adsorbents are used, the avail- value of probability, P implies lower signi¯cance of 82
31 ability of vacant adsorption sites is higher. This the regression model. The ¯sher-F test value was 83
32 pattern occurs due to the reason that as more ad- used to prove the e±ciency of a particular model, 84
33 sorbent is used, the higher is the access for adsor- whereas the F test value increases, the e±ciency of 85
34 bate to the surface of adsorbent. This increases the the model increases as well. This F value can be 86
35 chance for the adsorption process to take place and correlated with the mean square of the regressed 87
36 thus, more MB can be removed from the stock so- model where this allows the comparison of the mean 88
37 lution prepared. Figure 5 are plots of graphs show- square of the residuals which is the error to be 89
38 ing the relationship between the percentage removal carried out. A high value of probability, P implies 90
39 of dye solution with the quantity of adsorbent. lower signi¯cance of the regression model. Thus, 91
40 Additional run was carried out to prove the earlier from Table 2, the F-test value for the removal of 92
41 explanation by using a pH value of 10 and contact MB is 2377466.21 where this value simply implies 93
42 94
43 Table 2. The analysis of variance (ANOVA) for the removal of MB. 95
44 96
45 Source Sum of squares DF Mean square F value Prob > F Status 97
46 Model 3138.26 3 1046.09 2.377Eþ006 < 0.0001 Signi¯cant 98
47 A 825.8 1 825.8 1.877Eþ006 < 0.0001 — 99
48 B 1248 1 1248 2.836Eþ006 < 0.0001 — 100
49 C 1064.45 1 1064.45 2.419Eþ006 < 0.0001 — 101
50 Curvature 67.91 1 67.91 1.543Eþ005 < 0.0001 Signi¯cant 102
Pure Error 2.20E03 5 4.40E04
51 Cor Total 3206.17 9
103
52 104
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Removal of Methylene Blue and Orange-G from Waste Water Using Magnetic Biochar

1 Table 3. The analysis of variance (ANOVA) for the removal of orange-G. 53

2 54
Source Sum of squares DF Mean square F value Prob > F Status
3 55
4 Model 6184.92 3 2061.64 92325.99 < 0.0001 Signi¯cant 56
5 A 2020.89 1 2020.89 90501.13 < 0.0001 57
6 B 1967.84 1 1967.84 88125.4 < 0.0001 58
C 2196.19 1 2196.19 98351.45 < 0.0001
7 59
Curvature 433.95 1 433.95 19433.57 < 0.0001 Signi¯cant
8 Pure Error 0.11 5 0.022 60
9 Cor Total 6618.98 9 61
10 62
11 63
12 64
13 that the model is signi¯cant. Besides the F value, Figs. 6(a) and 6(b), there was very little pores 65
14 R-Squared as well as the Adj R-squared values both available on the surface of the precursor. However, 66
15 play important roles in order to determine the sig- after the activation process under the optimum 67
16 ni¯cance of a model. Based on Table 2, both the R- condition pores of di®erent size and di®erent shape 68
17 Squared value and Adj R-Squared value are 0.9982 were developed as shown in Figs. 6(c) and 6(d). 69
18 and 0.9967. As for the removal of the orange-G, During chemical activation by N2 gas, the di®usion 70
19 according to Table 3, the F-test value was found to of the oxidizing agent through the carbonaceous 71
20 be 2549.68 and again, this value implies that the matrix involves the removal of impurities and the 72
21 model is signi¯cant and the R-Squared value is consumption of carbon to create porosity. The 73
22 0.9993 and Adj R-Squared is 0.9990. Equations (3) microspores are opened and widened with even a 74
23 and (4) shown are the evolved model equation for shift to meso- and macrospores the removal of the 75
24 the color removal of MB and orange-G from the exterior of the particle is signi¯cant at high burn- 76
25 prepared stock solution using magnetic biochar de- o®s.29 This shows that N2 were e®ective in creating 77
26 rived from empty fruit bunch respectively. well developed pores on the surfaces of the precur- 78
27 sor, hence leading to novel MB with large surface 79
Removal of MB ¼ 82:82 þ 10:16A  12:49B þ 11:54C area and porous structure, which had a high ad-
28 80
29 ð3Þ sorption capacity on removal of arsenic from aque- 81
30 ous solution. 82
31 Removal of orange-G ¼ 85:71  4:14A 83
32 þ 0:93B þ 1:82C ð4Þ 84
33 3.4. FTIR analysis of magnetic biochar 85
34 where A represents the coded value of the pH of the The magnetic biochars were examined using the 86
35 stock solution, B represents the contact time be- Fourier Transform Infrared Spectrometer (FTIR) in 87
36 tween the adsorbent and adsorbate, and C repre- order to carry out analysis on these adsorbents for 88
37 sents the dosage of adsorbent used. Positive sign in the determination of the surface functional groups. 89
38 these two equations simply imply the synergistic Besides the porosity of the adsorbent, the chemical 90
39 e®ect meanwhile negative sign implies the antago- reactivity of the surface, especially in the form of 91
40 nistic e®ect. chemisorbed oxygen in various forms of functional 92
41 groups is another factor which in°uences the be- 93
42 havior of the novel magnetic biochar. Figure 7 94
3.3. Characterization of magnetic
43 shows the FTIR image of the surface functional 95
biochar derived from the empty
44 group of the raw empty fruit bunch and magnetic 96
45 fruit bunch biochar. The results indicate that the functional 97
46 Field Emission Scanning Electron Microscopy groups have been successfully impregnated on the 98
47 (FESEM) (Brand: Zeiss Model: Auriga) technique surface of the adsorbent. The band located at 3714- 99
48 was employed to observe the surface physical mor- 341 cm 1 is related to the N–H groups, while the 100
49 phology of the raw material and produced novel MB band 2361 is grouped as CC stretch of alkynes 101
50 samples. Figure 6 shows the images of raw EFB and Vibration of CN is ascribed at intensity 102
51 the prepared novel MB with di®erent magni¯cation 1995 cm 1 . The transmittance at 1652–1498 cm 1 is 103
52 scale (1
m and 100
m). As can be seen from similar to the O–H (hydroxyl) group, and CH2 and 104
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N. M. Mubarak et al.

1 53
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12 64
13 65
14 (a) (b) 66
15 67
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17 69
18 70
19 71
20 72
21 73
22 74
23 75
24 76
25 77
26 78
27 79
28 80
29 (c) (d) 81
30 82
Fig. 6. FESEM images of magnetic biochars (a,b) before, (c,d) after adsorption.
31 83
32 84
C–O–C (ether, ester and phenol) functionalities absorption peak of 1557 cm 1 recommends the oc-
33 are shown with intensive peaks at 1425 cm 1 and currence of aromatic with C–C stretch (ester and 85
34 86
1276 cm 1 . The transmittance at 1652–1497 cm 1 phenol) whereas the peak observed at 1071 cm 1
35 is similar to the O–H (hydroxyl) group, and represents the presence of either group. On the 87
36 88
other hand, the peak observed at 668 cm 1 reveals
37 alkynes with C–H blends is present. These result 89
38 90
good agreement with previous researchers.30–33
39 91
40 92
41 93
3.5. Adsorption kinetic studies
42 94
43 of MB and orange-G 95
44 The experiments for kinetic study were carried out 96
45 for ¯ve hours where three di®erent pH values of 97
46 the MB stock solution were used for the runs. For 98
47 these three di®erent beakers with di®erent pH 99
48 values of pH 2, pH 6 and pH 10, the volumes of 100
49 solutions were maintained constant at 200 mL and 101
50 the agitation speed maintained at 125 rpm. The 102
51 dye solution was ¯ltered every 20 min where later 103
52 Fig. 7. FTIR image of (a) before, (b) after adsorption. on the concentration at that speci¯c time was 104
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Removal of Methylene Blue and Orange-G from Waste Water Using Magnetic Biochar

1 concentration after 24 h. At this time, the concen- 53

2 tration of the stock solutions was found to be similar 54
3 to the ¯nal value of the concentration measured at 55
4 time 300 min. As for Fig. 8(b), equilibrium was 56
5 quickly achieved at a time 50 min for all three stock 57
6 solutions. As the ¯ve hours of agitation period sei- 58
7 zes, a perfect equilibrium for all pH values using 59
8 both types of magnetic biochar were obtained. All 60
9 six beakers of stock solutions were allowed to be 61
10 stirred for a continuous for 24 h in order to deter- 62
11 mine the ¯nal concentration after 24 h. At this time, 63
12 the concentrations of the stock solutions were found 64
13 to have the same concentration value with the 65
14 ¯nal value of the concentration measured at time 66
15 300 min. 67
16 (a) 68
17 69
18
3.6. Adsorption isotherm studies of MB 70
19 and orange-G 71
20 The adsorption isotherm studies for the removal of 72
21 MB and orange-G dyes were carried out by using 73
22 three di®erent stock solutions of dyes of varying 74
23 initial concentration values. Three beakers of 75
24 200 mL of MB solution with three di®erent con- 76
25 centrations of 50 mg/L, 80 mg/L and 100 mg/L 77
26 were used for this isotherm study where a constant 78
27 dosage of adsorbent of 1.00 g, stirring time of three 79
28 hours, stock solutions of pH 10, and an agitation 80
29 speed of 125 rpm which were maintained constant 81
30 for the entire isotherm runs. The optimization of the 82
31 design for the adsorption of methylene blue, it is 83
32 crucial to set up the most appropriate correlation 84
33 (b) for the equilibrium curves.4 In this research, the 85
34 Fig. 8. E®ect of contact time on adsorption capacity (a) MB, equilibrium data for the adsorption of the two dyes 86
35 (b) orange-G. with varying concentrations of were ¯tted to two 87
36 important equations; Langmuir equation and the 88
37 Freundlich equation. The Langmuir isotherm could 89
38 checked by using the UV-Vis Spectrophotometer. give a good relation between the solid phase con- 90
39 The optimized variable which is the quantity of centration at equilibrium, qe and the equilibrium 91
40 adsorbent of 1.00 g was obtained from Design concentration of the dye solution, Ce , as shown in 92
41 Expert. Figures 8(a) and 8(b) are graphs of amount Eq. (5). 93
42 of dye adsorbed at time t, qt against the contact Ce 1 C 94
43 time for MB and orange-G respectively. According ¼ þ e ð5Þ 95
qe KL qm qm
44 to Fig. 8(a), equilibrium was immediately attained 96
45 at a time 60 min for the stock solution with pH 10. where Ce (mg/L) is the equilibrium concentration of 97
46 As for the other two pH values, equilibrium was dye solution, qe is the amount of dye adsorbed at 98
47 achieved at approximately time 160 min. As the ¯ve equilibrium (mg/g), KL is the adsorption equilibri- 99
48 hours of agitation period seizes, a perfect equilibri- um constant (L/mg) and qm is a constant and it 100
49 um for all pH values using both types of magnetic re°ects a complete monolayer (mg/g). KL is a 101
50 biochar were obtained. All six beakers of stock constant which links the a±nity of the binding sites 102
51 solutions were allowed to be stirred for a continu- and qm represents the maximum adsorption capac- 103
52 ous for 24 h in order to determine the ¯nal ity of the magnetic biochar as an adsorbent. 104
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N. M. Mubarak et al.

1 53
2 54
3 55
4 56
5 57
6 58
7 59
8 60
9 61
10 62
11 63
12 64
13 65
14 66
15 (a) 67
(a)
16 68
17 69
18 70
19 71
20 72
21 73
22 74
23 75
24 76
25 77
26 78
27 79
28 80
29 81
30 82
31 (b) 83
32 (b) 84
Fig. 9. Langmuir adsorption isotherm for removal of (a) MB,
33 Fig. 10. Freundlich adsorption isotherm for removal of (a) 85
(b) orange-G.
34 MB, (b) orange-G. 86
35 87
36 According to Eq. (5), this equation can be broken 88
37 down into the form of y ¼ mx þ c where Ce =qe is KL and qm can be obtained. According to Fig. 9(a), 89
38 the y-axis, Ce is the x-axis, 1=qm is the gradient of the calculated value of qm was found to be 90
39 the graph and 1=KL qm is the y-intercept of the 31.25 mg/g and KL to have a value of 0.4150 L/mg 91
40 graph. Figures 9(a) and 9(b) are the linearized and for Fig. 9(b), the qm value was calculated to be 92
41 Langmuir models of Ce =qe against Ce for isotherm 32.36 mg/g and KL is 0.4221 L/mg. The Langmuir 93
42 studies for the removal of MB and orange-G dyes isotherm produces good ¯ts over the range of 94
43 respectively. From these two ¯gures, the values of concentration for the removal of these two dye 95
44 96
45 97
46 Table 4. Langmuir and Freundlich isotherm parameters for adsorption of MB and orange-G. 98
47 Langmuir isotherm Freundlich isotherm
99
48 100
49 Dye qm (mg/g) KL (L/mg) R2 n KF (L/mg) R2 101
50 102
Methylene blue 31.25 0.415 0.9584 1.8639 9.5506 0.931
51 Orange-G 32.36 0.4221 0.982 1.767 9.713 0.9644
103
52 104
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AQ: Please check position of

Figure ok as set?

Removal of Methylene Blue and Orange-G from Waste Water Using Magnetic Biochar

1 53
2 54
3 55
4 56
5 57
6 58
7 59
8 60
9 61
10 62
11 63
12 64
13 65
14 66
15 (a) 67
(a)
16 68
17 69
18 70
19 71
20 72
21 73
22 74
23 75
24 76
25 77
26 78
27 79
28 80
29 81
30 82
31 (b) 83
32 (b) 84
Fig. 11. Pseudo-¯rst order plot for the removal of (a) MB,
33 (b) orange-G.
85
Fig. 12. Pseudo-second order plot for the removal of (a) MB,
34 (b) orange-G. 86
35 87
36 solutions with R 2 values of 0.9584 for MB and 88
37 0.9820 for orange-G. removal of MB and orange-G dyes by using magnetic 89
38 Another model of the equation to be studied is biochar derived from the empty fruit bunch. In these 90
39 the Freundlich model. Equation (6) shows the two ¯gures, the relationship between the uptake of 91
40 Freundlich equation for heterogeneous surface dyes, qe (mg/g) and the residual dye equilibrium 92
41 energy systems. concentration, Ce (mg/L) based on Eq. (6) is shown. 93
42 From this equation, KF value is can be determined 94
1
43 ln qe ¼ ln KF þ ln Ce ð6Þ from the y-intercept of the graphs in Figs. 10(a) 95
44 n and 10(b). The value n can also be determined from 96
45 where KF and n are both the Freundlich constants the gradient of these two graphs. For Fig. 10(a), the 97
46 that will be determined from the plot of ln qe against value of n is 1.8639 and KF to have a value of 98
47 ln Ce . KF and 1=n are interrelated to both the sorp- 9.5506 L/mg and the R 2 value is 0.9310. As for the 99
48 tion capacity as well as the intensity of the sorption of removal of the orange-G based on Fig. 10(b), the KF 100
49 the system. Besides, from the magnitude of the 1=n value is 9.713 L/mg and n is 1.767. The R 2 value for 101
50 term, one can determine the favorability of the sor- the removal of this dye was found to be 0.9644. Based 102
51 bent/adsorbate systems.6 Figures 9(a) and 9(b) are on Table 4, the R 2 values obtained prove that these 103
52 plots of the Freundlich adsorption isotherm for the two Langmuir and Freundlich isotherm models can 104
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N. M. Mubarak et al.

1 Table 5. Kinetic parameters for pseudo-¯rst order and pseudo-second order. 53

2 54
Pseudo-¯rst order Pseudo-second order
3 55
4 Methylene blue Orange-G Methylene blue Orange-G 56
5 57
6 pH qe K1 R2 qe K1 R2 qe K2 R2 qe K2 R2 58
7 2 26.62 0.0002 0.6295 12.67 0.004 0.1737 5.78 0.0227 0.9993 5.82 0.0764 0.9998 59
8 6 26.49 0.0002 0.692 26.88 0.027 0.8705 6.00 0.0199 0.9989 5.79 0.082 0.9999 60
9 10 25.97 0.0606 0.3825 27.00 0.0337 0.8724 5.86 0.0642 0.9998 5.73 0.0638 0.9998 61
10 62
11 63
be used to determine the adsorption of MB and or- they increase as the pH decreases from pH 10 to pH 2.
12 64
ange gelb dyes from aqueous solutions. Based on the These obtained results prove that the adsorption of
13 65
qm values obtained, it can be said that by using an MB and orange-G from the aqueous solutions obey
14 66
empty fruit bunch derived magnetic biochar as the the pseudo-second order kinetic model.
15 67
adsorbent, the removal of the orange-G dye is higher
16 68
than that of methylene blue.
17 69
The kinetic studies for the pseudo-¯rst order and 4. Conclusions
18 70
pseudo-second order was also carried out in this
19 Magnetic biochar is proven to possess excellent 71
research. The purpose of carrying out this study is
20 adsorption capacity for the removal of MB and 72
to develop a better understanding of the dynamics
21 orange-G dyes. The process parameters for the 73
of adsorption process. The linearized Eqs. (7)
22 maximum adsorption of MB were pH values of 2 74
and (8) both are used to study the pseudo-¯rst order
23 and 10, adsorbent dosage of 1.00 g, and contact time 75
and second order models respectively.
24 of 120 min. As for orange-G, the optimized process 76
25 lnðqe  qt Þ ¼ ln qe  K1 t ð7Þ parameters are pH 2, an adsorbent dosage of 1.00 g, 77
26 t 1 1 and contact time of 120 min. The equilibrium data 78
27 ¼ þ t ð8Þ for this research ¯tted very well in both Langmuir 79
qt k2 q e qe
2
28 and Freundlich isotherms and were best described 80
29 where qe represents the amount of dye being by the Langmuir model with a maximum adsorp- 81
30 adsorbed onto the adsorbent at equilibrium (mg/g), tion capacity of 31.25 mg/g for MB and 32.36 mg/g 82
31 qt represents the amount of dye being adsorbed onto for orange-G at room temperature. As for the order 83
32 the adsorbent at time t (mg/g), K1 (min 1 ) is the of the reaction, the rates of adsorption for both dyes 84
33 rate constant for pseudo-¯rst order adsorption and were found to comply with the pseudo-second order 85
34 K2 (g mg 1 min 1 ) represents the rate constant for kinetic model. 86
35 the pseudo-second order adsorption. Based on 87
36 Fig. 11 which are the plots for pseudo ¯rst order, it 88
37 can be seen that the graphs failed to produce the Acknowledgments 89
38 linear graphs for the three pH values. However, 90
39 according to Fig. 12 which are the plots for pseudo- The authors are grateful to UCSI University for 91
40 second order, the graphs converged well and funding environmental & sustainable engineering 92
41 straight lines were obtained. Besides, based on cluster project code Proj-In-FETBE-015. The 93
42 Table 5, the obtained R 2 values for pseudo-second authors are thankful to the authorities of University 94
43 order that is approaching unity are way higher than of Malaya for FESEM & FTIR analysis under 95
44 that of the pseudo-¯rst order. Besides, the values of Ministry of Higher Education High Impact Re- 96
45 qe and K2 for pseudo-second order for the removal search (UM.C/HIR/MOHE/ENG/20). 97
46 of MB are proven to be consistent with the pH 98
47 values. As discussed earlier, as the pH increases, the 99
48 removal of MB increases as well, which is proven by References 100
49 the increment of qe values. Also, as discussed pre- 1. E. Forgacs, T. Cserhati and G. Oros, Environment. 101
50 viously, the removal of the orange-G dye increases International 30, 953 (2004). 102
51 with a decrease in pH value. This statement is also 2. K. Arzani, B. G. Ashtiani and A. H. A. Kashi, J. 103
52 proven by the qe values obtained from Table 5 where Inorg. Mater. 27, 660 (2012). 104
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Removal of Methylene Blue and Orange-G from Waste Water Using Magnetic Biochar

1 3. I. D. Mall, V. C. Srivastava and N. K. Agarwal, Dye. 19. N. M. Mubarak, M. Ruthiraan, J. N. Sahu, E. C. 53

2 Pigment. 69, 210 (2006). Abdullah, N. S. Jayakumar, N. R. Sajuni and 54
3 4. Y. Zhu, D. Wang, X. Zhangand and H. Qin, Fresen. J. Tan, Int. J. Nanosci. 12, 1350044 (2013). 55
4 Environment. Bullet. 18, 369 (2009). 20. N. M. Mubarak, R. F. Alicia, J. Tan. E. C. Abdul- 56
5 5. Y. Yasin, M. Z. Hussein and F. H. Ahmad, Malays lah, J. N. Sahu, N. S. Jayakumar and A. B. Ayu, 57
J. Analyt. Sci. 11, 400 (2007). Adv. Environmen. Bio. 8, 686 (2014).
6 58
6. D. Pathania, S. Sharma and P. Singh, Arab. J. Chem. 21. G. Zhang, J. Qu, H. Liu, A. T. Cooper and R. Wu,
7 (2013), doi.org/10.1016/j.arabjc.2013.04.021. Chemosphere 68, 1058 (2007).
59
8 7. A. Geethakarthi and B. R. Phanikumar, Inter. J. 22. N. M. Mubarak, A. Kundu, J. N. Sahu, E. C. 60
9 Env. Sci. Tech. 8, 561 (2011). Abdullah and N. S. Jayakumar, Biomass Bioenergy 61
10 8. Y. Fang, D. Gu, Y. Zou, Z. Wu, F. Li, R. Che, 61, 265 (2014). 62
11 Y. Deng, B. Tu and D. Zhao, Angew. Chem., Int. 23. S. Wang, Y. Boyjoo, A. Choueib and Z. H. Zhu, 63
12 Edit. 49, 7987 (2010). WaterRes. 39, 129 (2005). 64
13 9. D. Saha and S. Deng, Langmuir. 25, 12550 (2009). 24. M. A. Rahman, S. M. R. Amin and A. M. S. Alam, 65
14 10. R. B. Zheng, X. W. Meng, F. Q. Tang, L. Zhang and Dhaka Univ. J. Sci. 60, 185 (2012). 66
15 J. Ren, J. Phys. Chem. C. 113, 13065 (2009). 25. I. D. Mall, V. C. Srivastava and N. K. Agarwal, Dye 67
16 11. H. J. Liu, W. J. Cui, L. H. Jin, C. X. Wang and Y. Pigment. 69, 210 (2006). 68
17 Y. Xia, J. Mater. Chem. 19, 3661 (2009). 26. G. Crini, Dyes Pigment. 77, 415 (2008). 69
12. U. Gecgel, G. Ozcan and G. C. Gurpinar, J. Chem. 27. D. Kavitha and C. Namasivayam, Bioresource.
18 70
167, 1 (2013). Technol. 98, 14 (2007).
19 13. S. Thirumalisamy and M. Subbian, Bio. Resourc. 5, 28. M. Dogan, Y. Ozdemir and M. Alkan, Dyes Pig-
71
20 419 (2010). ment. 75, 701 (2007). 72
21 14. M. A. Rahman, S. M. R. Amin and A. M. S. Alam, 29. M. S. Amran, K. M. Dalia, A. Norzeti, W. Azlina 73
22 Dhaka Univ. J. Sci. 60, 185 (2012). and I. Azni, J. Purity. Utility. React. Environ. 1, 74
23 15. G. Vijayakumar, R. Tamilarasan and M. Dharmen- 472 (2012). 75
24 dirakumar, J. Mater. Environ. Sci. 3, 157 (2011). 30. R. F. Rodriquez-Reinoso and M. Molina-Sabio, 76
25 16. V. M. Kanimozhi and S. Sridhar, Advanced Biotech Carbon. 30, 1111 (1992). 77
26 12, 5 (2013). 31. R. Pietrzak, K. Jurewicz, P. Nowicki, K. Babel and 78
27 17. S. B. Hartono, S. Ismadji, Y. Sudaryanto and W. H. Wachowska, Fuel. 86, 1086 (2007). 79
28 Irawaty, J. Ind. Eng. Chem. 11, 864 (2005). 32. C. Bouchelta, M. S. Medjram and O. J. P. Bertrand, 80
29 18. Z. Wang, M. Xue, K. Huang and Z. Liu, Textile J. Anal. Appl. Pyrol. 82, 70 (2008). 81
dyeing wastewater treatment, Advances in Treating 33. R. C. Sun and J. Tomkinson, Sep. Purif. Technol.
30 82
Textile E®luent, ed. Peter Hauser (InTech, Croatia, 24, 529 (2001).
31 2011).
83
32 84
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37 89
38 90
39 91
40 92
41 93
42 94
43 95
44 96
45 97
46 98
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