A study of lead removal using sargassum tenerrimum (brown algae): Biosorption in column study

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A study of lead removal using sargassum tenerrimum (brown algae): Biosorption in column study M. Tukarambai ⇑, P. Venakateswarlu Andhra University, Visakhapatnam 530003, India

a r t i c l e

i n f o

Article history: Received 7 September 2019 Accepted 22 November 2019 Available online xxxx Keywords: Biosorption Column study Lead Sargassum tenerrimum powder Bohart-Adams Bed Depth Service Time (BDST) Thomas and Yoon Nelson

a b s t r a c t The sorption capacity of sargassum tenerrimum powder is studied for various flow rates i.e., 10, 20 and 30 mL/min. The initial pH of aqueous solution is maintained at 5. For the flow rates of 10, 20 and 30 mL/min, the breakthrough times are 32, 26 and 18 min respectively while the exhaust times are 90, 85 and 75 min respectively. The time taken to achieve breakthrough has decreased with increase of flow rate. A glass column having 2.54 cm internal diameter (ID) and length of 40 cm were used. The experiments are conducted for two different bed heights (5 and 10 cm) using 2 and 4 g of biosorbent. A flow rate of 30 mL/min of aqueous solution (Co = 20 mg/L) is maintained. With an increase in bed height, the throughput volume is increased to achieve the saturation and this increase in input volume, would result in higher contact time, thereby increasing the uptake capacity. Lead biosorption uptakes are increased from 13.852 to 20.839 mg/g as the bed height is increased from 5 to 10 cm. the breakthrough curve models BDST, Thomas and Yoon-Nelson models were studied for discussing the fixed bed column onto biosprion of lead. Ó 2019 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of the scientific committee of the First International Conference on Recent Advances in Materials and Manufacturing 2019.

1. Introduction Rapid industrialization and urbanization are the two prominent reasons for the pollution of our environment [1]. Heavy metals from the anthropogenic activities are the one of the important root cause for the aquatic pollution [2]. They are released directly or indirectly to the environment from the industrial waste water. Lead is one of the harmful pollutant which is very complicated for the treatment. The US Environment protection Agency listed lead as the 129 priority pollutant. Even the presence of low concentrations in the drinking water it causes anemia, encephalopathy with permanent damage, hepatitis and nephritic syndrome [3]. In humans lead poisoning results in damage to kidney and also to various organs of the humanbeing. Hence the treatment of the industrial effluents are very essential. Various conventional technologies have been developed for the treatment methods like chemical precipitation, Ion exchange, Electro-chemical deposition, Biosorption, Liquid Liquid Exchange, membrane separation, Reverse osmosis etc. [4]. ⇑ Corresponding author. E-mail address: [email protected] (M. Tukarambai).

Biosorption has been selected for the present investigation due to its economic feasibility, ease of operation and high efficiency. The objective of the present work is to study the potential of biosorption technique for the removal of lead from aqueous solutions using low cost, non-conventional, easily and abundantly available the sargassum tenerrimum biomass powder (a brown algae) powder in a fixed bed column. Sargassum is commonly found in the beach drift. There are floating populations of Sargassum in few cases. The study evaluates the performance of the biosorption for varying process design parameters like bed height and flow rates using a fixed bed column. The author of the present paper conducted batch studies and fixed bed parameter studies on the biosorption of lead using sargassum tennerimum powder and published earlier in reference, tukarambai et al. [5]. The present research work is the continuation of that work [5]. In the present investigation, the resulted experimental data from fixed bed parameters like: flow rate and biosorbent bed height are used to explain the breakthrough curves were analyzed by the BDST model, Thomas and Yoon-Nelson models are applied to predict breakthrough curves and to determine the characteristic parameters of the column. The presence of functional groups like hydroxyl, carboxylic, amines etc., of the sargassum tennerimum (a brown

https://doi.org/10.1016/j.matpr.2019.11.254 2214-7853/Ó 2019 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of the scientific committee of the First International Conference on Recent Advances in Materials and Manufacturing 2019.

Please cite this article as: M. Tukarambai and P. Venakateswarlu, A study of lead removal using sargassum tenerrimum (brown algae): Biosorption in column study, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.11.254

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Biosorbent : sargassum tenerrimum powder

algae) indicates that biosorption capacity of the saragassum tenerrimum powder for the removal of lead is possible.

3. Results and discussions In the present experimentation 32, 26 and 18 min of respective breakthrough times and 90, 85 and 75 min are the respective exhaust times at various flow rates 10, 20 and 30 mL/min. 3.1. Breakthrough curve models In the present study, the lead sorption in a fixed bed onto the sargasum tenerrimum powder is explained with four mathematical models: Bohart-Adams, Bed Depth Service Time (BDST), Thomas and Yoon-Nelson. Many investigations have been reported using Bohart-Adams model for testing of biosorption kinetics in fixed beds [6,7,8–13]. The other models tested for fixed bed biosorption data include BDST [6,14–17], Thomas and Yoon-Nelson models [11,17]. In this research work it is aimed to find out the better model to describe biosorption kinetic breakthrough curves. 3.1.1. Bohart-Adams model This model describes the preliminary part of the breakthrough curve. The Bohart-Adams model, based on surface reaction rate theory [16], is given as Eq. (1)

ð1Þ

The characteristic parameters like N0, mg/L (saturation concentration), kAB (kinetic constant) are estimated by plotting a graph between ln (C2/C1) and ‘t’ for flow rates of Q = 10, 20 and 30 mL/ min for bed height of 5 cm is shown in Fig. 1 and it also includes the plot for 30 mL/min at the bed height of 10 cm. From the graph, slope is kAB C1 and intercept is kAB N0 z/U0. It is found that kAB is increased with an increase in flow rate and decrease in bed height. In the initial part of biosorption, the whole system kinetics is overcome by external mass transfer [12]. 3.1.2. Bed Depth Service Time (BDST) model The column data are modelled by establishing a term named service time that is defined as the time required for lead concentration in the aqueous solution to reach 1 mg/L. The bed height (z) and service time (t) holds a linear relationship as given by BDST (Bed Depth Service Time) model [17], and expressed in Eq. (2)

t ¼ CN10uz  kC11 ln



C1 C2

1



ð2Þ

Fig. 2 indicates the BDST curve plotted between ln(C1/C2  1) and time. From the plot the resulted slope gives the value of k and from intercept N0 can be calculated.

ln (C2/ C1)

-1 Q, mL / min 10 at L= 5 cm 20 at L= 5 cm 30 at L= 5 cm 30 at L = 10 cm

-2 -3 -4 -5 0

20

40

60 80 Time, t, min

100

120

140

Fig. 1. Bohart – Adams plot.

3.1.3. Thomas model The important feature in the design of fixed bed adsorption column is the prediction of concentration time profile or the breakthrough curve for the aqueous solution and a mathematical model to fit them. One of the simple and generally used models [8,12] reported by many researchers is Thomas model, expressed in linear form as in Eq. (3),

  k C V ln CC 12  1 ¼ kTh qF0 ms  Th F1 eff

ð3Þ

The graph is drawn between ln (C2/C1  1) against effluent volume (Veff) as shown in Fig. 3. From the plot correlation coefficient resulted greater than 0.96. With this value of correlation coefficient it is evident that the Thomas model is better fitted to experimental data. It is also observed that with raise in flow rate Thomas rate constant (kTh) and maximum solid phase concentration (qo) are increased. Thomas model has indicated that the external and internal diffusions are not the rate limiting steps [12]. 3.1.4. Yoon Nelson model Yoon-Nelson’s model is envisaged to study the breakthrough behavior of lead biosorption on sargassum tenerrimum powder and is given as Eq. (4)

Biosorbent : sargassum tenerrimum powder

160 140

Q, mL / min 10 at L = 5cm 20 at L = 5cm 30 at L = 5cm 30 at L = 10 cm

120 Time, t, min

The sargassum tenerrimum (species of brown algae), are collected from Rushikonda beach in Visakhapatnam, Andhra Pradesh, India. 20 mg/L lead stock solution was prepared. 0.1 N HNO3 or 0.1 N NaOH solution were used for pH adjustment. Atomic absorption spectrophotometer: (Perkin Elmer A Analyst 200 model) (AAS) was used to analyze the initial and final concentrations of the samples. The design of present column study with 2.54 cm internal diameter (ID) of 40 cm length. To control any loss of biosorbent material, Glass wool/sponge was arranged at inlet and outlet of the column. From the bottom of the column lead solution was sent by using a peristaltic pump and samples were collected from the top of the column at regular intervals. Until inlet and outlet lead concentrations are equal, the pumping was continued and flow rate is constantly monitored.

lnCC 21 ¼ kAB C 1 t  kAB N0 Uz0

pH = 5 Co = 20 mg/L

0

2. Materials and methods

100 80 60 pH = 5 Co= 20 mg/L

40 20 0 -6

-4

-2

0 ln [(C1 / C2)-1]

2

4

6

Fig. 2. Bed Depth Service Time (BDST) plot.

Please cite this article as: M. Tukarambai and P. Venakateswarlu, A study of lead removal using sargassum tenerrimum (brown algae): Biosorption in column study, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.11.254

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Biosorbent : sargassum tenerrimum powder

6

pH = 5 Co= 20 mg/L

Q, mL / min 10 at L = 5 cm 20 at L = 5 cm 30 at L = 5 cm 30 at L = 10 cm

2

1.0

L = 5 cm pH = 5 Co= 20 mg/L

0.8 C2 / C1

ln [(C1 / C2)-1]

4

Biosorbent : sargassum tenerrimum powder

1.2

0

-2

Q, mL / min

0.6

10 exp 20 exp 30 exp 10 cal 20 cal 30 cal

0.4

-4

0.2

-6 0

1000

2000

3000

4000

5000

0.0

6000

0

Veff, mL Fig. 3. Thomas plot.

20

40

60 80 Time, t, min

100

120

140

Fig. 5. Experimental and theoretical breakthrough curves at different flow rates based on Bohart – Adams model.

  2 ln C 1CC ¼ kYN t  skYN 2

ð4Þ

ð5Þ

Q = 30 mL / min pH = 5 Co= 20 mg/L

1.0 0.8 0.6

L, cm 5 exp 10 exp 5 cal 10 cal

0.4 0.2

3.1.5. Comparison between two models To study the initial part experimentation (10 to 50% initial biosorbate concentration) of the breakthrough curve BohartAdams model is applicable. The linearity of the three models namely BDST, Thomas and Yoon-Nelson are represented by Eq. (5).

lnðC 2 =C 1  1Þ ¼ k1c  k2c t

Biosorbent : sargassum tenerrimum powder

1.2

C 2 / C1

To study the Yoon nelson model the graph is drawn between ln (C2/C1  C2) and time ‘t’ as shown in Fig. 4. kYN (Yoon Nelson rate constant) L/min. is decreased with increase in bed height and flow rate. The value of s (time required for 50% adsorbate breakthrough) increased with increase in bed height and decrease in flow rate. The uptake capacity is very close to that predicted by Yoon-Nelson model. The experimental and theoretical breakthrough curves for various flow rates and bed heights for Bohart Adams, BDST, Thomas and Yoon-Nelson models are shown in Figs. 5–12 respectively. BDST, Thomas and Yoon-Nelson models are fitted for the overall experimental data but Bohart Adam model is explaining the initial part of the breakthrough curve.

0.0 0

20

40

60

80

100

120

140

160

Time, t, min Fig. 6. Experimental and theoretical breakthrough curves for two bed heights based on Bohart – Adams model.

where k1c = N0kL/u = kThq0m/F = skYN and k2c = kC1 = kThC1 = kYN. Biosorbent : sargassum tenerrimum powder

6

Biosorbent : sargassum tenerrimum powder

1.1 1.0

pH = 5 Co = 20 mg/L

L = 5 cm pH = 5 Co= 20 mg/L

0.9 0.8

2

0.7 C2 / C1

ln [C2/(C1- C2)]

4

0

Q, mL / min 10 at L = 5 cm 20 at L = 5 cm 30 at L = 5 cm 30 at L = 10 cm

-2

-4

0.6 Q, mL / min 10 exp 20 exp 30 exp 10 cal 20 cal 30 cal

0.5 0.4 0.3 0.2 0.1 0.0 0

-6 0

20

40

60

80

100

120

140

160

20

40

60

80

100

120

140

Time, t, min

Time, t, min Fig. 4. Yoon Nelson plot.

Fig. 7. Experimental and theoretical breakthrough curves at different flow rates based on BDST model.

Please cite this article as: M. Tukarambai and P. Venakateswarlu, A study of lead removal using sargassum tenerrimum (brown algae): Biosorption in column study, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.11.254

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Biosorbent : sargassum tenerrimum powder

1.2 Q = 30 mL / min pH = 5 Co= 20 mg/L

1.0

0.8

C2 / C 1

C2 / C1

L = 5 cm pH = 5 Co= 20 mg/L

1.0

0.8 0.6 L, cm 5 exp 10 exp 5 cal 10 cal

0.4 0.2

0.6 Q, mL / min 10 exp 20 exp 30 exp 10 cal 20 cal 30 cal

0.4 0.2 0.0

0.0 0

20

40

60

80 100 Time, t, min

120

140

0

160

60

100

120

140

Q = 30 mL / min pH = 5 Co= 20 mg/L

1.0

0.8 0.6

C2 / C1

0.8

Q, mL / min 10 exp 20 exp 30 exp 10 cal 20 cal 30 cal

0.4 0.2

0

20

40

60

80

100

120

0.6 L, cm 5 exp 10 exp 5 cal 10 cal

0.4 0.2

0.0

0.0

140

0

20

40

60

Time, t, min Fig. 9. Experimental and theoretical breakthrough curves at different flow rates based on Thomas model.

Biosorbent : sargassum tenerrimum powder

1.2

80 100 Time, t, min

120

140

160

Fig. 12. Experimental and theoretical breakthrough curves at different flow rates based on Yoon – Nelson model.

Table 1 Comparison of characteristic features of various models at C0 = 20 mg/L. BDST model parameters, z = 5 cm

Q = 30 mL / min pH = 5 Co= 20 mg/L

1.0 0.8 C2 / C 1

80

Biosorbent : sargassum tenerrimum powder

1.2

L = 5 cm pH = 5 Co= 20 mg/L

1.0

40

Fig. 11. Experimental and theoretical breakthrough curves for two bed heights based on Yoon – Nelson model.

Biosorbent : sargassum tenerrimum powder

1.2

20

Time, t, min

Fig. 8. Experimental and theoretical breakthrough curves for two bed heights based on BDST model.

C2 / C1

Biosorbent : sargassum tenerrimum powder

1.2

Flow rate, mL/min

texp

tcal

10 20 30

64.31 61.93 52.11

66.00 58.23 47.4

Bed height, cm

texp

tcal

5 10

52.11 66.00

47.4 66.60

Q = 30 mL/min

0.6 L, cm 5 exp 10 exp 5 cal 10 cal

0.4 0.2

Yoon-Nelson model parameters, L = 5 cm

0.0 0

20

40

60

80

100

120

140

160

Time, t, min Fig. 10. Experimental and theoretical breakthrough curves for two bed heights based on Thomas model.

Flow rate, mL/min

texp

tcal

10 20 30

64.5 62.5 52.14

61.9 58.66 47.68

Q = 30 mL/min Bed height, cm

texp

tcal

5 10

52.14 65.6

47.6 66.00

Please cite this article as: M. Tukarambai and P. Venakateswarlu, A study of lead removal using sargassum tenerrimum (brown algae): Biosorption in column study, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.11.254

M. Tukarambai, P. Venakateswarlu / Materials Today: Proceedings xxx (xxxx) xxx Table 2 Comparison of R2 Values for various models at C0 = 20 mg/L.

5

References

Flow rate, mL/min

Bed height, cm

R2 Bohart Adam’s

BDST Model

Thomas Model

Yoon – Nelson model

10 20 30 30

5 5 5 10

0.85 0.90 0.87 0.81

0.98 0.97 0.95 0.98

0.99 0.98 0.96 0.97

0.98 0.97 0.95 0.98

The characteristic parameters associated with these models vary but all the three models predict essentially similar uptake capacity for a particular data. Hence R2 values and other statistical parameters are similar and shown in Table 2. Further comparison is carried out based on prominent and unique characteristic features of the respective models like service time (BDST model), biosorption capacity (Thomas model) and time for 50% breakthrough (Yoon-Nelson model). Table 1 presents comparison of characteristic features of various models. Among all the models, Thomas and Yoon Nelson models are observed as best fitted for the biosorption of lead by sargassum tenerrimum powder. 4. Conclusions The characteristic parameters of the column were determined by the BDST model, Thomas and Yoon-Nelson models and they are also applied to predict breakthrough curves. The BDST, Thomas and Yoon-Nelson models are found to be suitable for explaining lead biosorption. Acknowledgement We acknowledge Andhra University College of Engineering for providing all the laboratory and analysis facilities for our completion of work.

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Please cite this article as: M. Tukarambai and P. Venakateswarlu, A study of lead removal using sargassum tenerrimum (brown algae): Biosorption in column study, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.11.254