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chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504

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Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Design journal homepage: www.elsevier.com/locate/cherd A review of the kinetics adsorption models and their
Design journal homepage: www.elsevier.com/locate/cherd A review of the kinetics adsorption models and their

A review of the kinetics adsorption models and their application to the adsorption of lead by an activated carbon

application to the adsorption of lead by an activated carbon L. Largitte a , ∗ ,

L. Largitte a, , R. Pasquier b

a COVACHIM M2E, Université des Antilles de la Guyane, Campus de Fouillole, BP 250, 97157 Pointe-à-Pitre Cedex, France

b C3I, Université des Antilles de la Guyane, Campus de Fouillole, BP 250, 97157 Pointe-à-Pitre Cedex, France

a r t

i c

l e

i n f o

a b s t r a c t

Article history:

 

10 kinetic models are studied in detail and used after to model the adsorption kinetics of

Received 20 July 2015

lead on an activated carbon. All the kinetics parameters are determined: coefficients of

Received in revised form 28 January

diffusion, rate constants and maximum lead adsorption, then, compared to the literature

2016

data. The data are better simulated by the nonlinear models in the order: simpli-

Accepted 5 February 2016

Available online 11 February 2016

Keywords:

Adsorption

Kinetics

Modelling

Heavy metal removal

Crank long times > pseudo order

2 > Crank > Weber and Morris > Langmuir, pseudo order 1 > pore volume and surface diffu-

sion model by Leyva Ramos > simplified Crank short times. It is one of the first times that the

kinetics of adsorption are fitted by the entire true Crank model. The kinetics of lead adsorp-

tion by the activated carbon are best described by the Elovich equation: Q = (1/ˇ) Ln (˛ˇt)

with ˛ equal to 0.035 mg g 1 s 1 and ˇ to 0.134 g mg 1 .

© 2016 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

fied Elovich > Elovich > Bangham > pseudo order

n > Boyd,

1.

Introduction

An adsorption process includes one or more than one adsor- bate which is fixed though physical or chemical bonds onto an adsorbent. Adsorption is widely used in wastewater treat- ment process (Foo and Hameed, 2009) to remove the pollutants from water because this technique is simple, efficient, eco- nomically viable and socially acceptable (Sreejalekshmi et al.,

2009).

The adsorbents generally used are the activated carbons because they possess large porous surface area, controllable pore structure, thermo-stability, interesting acid/base proper- ties and low cost if the preparation comes from byproducts. The activated carbons are very efficient for the removal of a broad type of organic and inorganic pollutants dissolved in aqueous or in gaseous media (Li and Wang, 2009).

In this study, the adsorbent used is an activated carbon from Coconut shells, the adsorbate is lead and one of the objective of this work is to study the kinetics of lead removal in aqueous environment by this activated carbon. It is essential to describe precisely the kinetics of adsorp- tion (Gerc¸el and Gerc¸el, 2007), to compare the predicted adsorption parameters calculated by models to the experi- mental adsorbent behavior, in different adsorbent adsorbate systems and in varied experimental conditions (Mishra and Patel, 2009; Shekinah et al., 2002). The determination of the models adsorption parameters permits to optimize the adsorption mechanism pathways, to express the dependence of the surface properties of the adsorbent to the sorption results, to determine the adsorbent capacities and design effectively the adsorption systems (Ho et al., 1996; Thompson et al., 2001).

Corresponding author. Tel.: +33 590 590483403; fax: +33 590 590483403. E-mail address: lucie.largitte@univ-ag.fr (L. Largitte).

http://dx.doi.org/10.1016/j.cherd.2016.02.006

0263-8762/© 2016 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

496

chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504

Nomenclature

t

time (s)

Q

amount of adsorbate sorbed at instant t

Q max

(mg g 1 )

maximum amount of adsorbate sorbed

(mg g 1 )

Q r amount of adsorbate sorbed at t in the particle

of adsorbent at a distance r (mg g 1 ) Q exp experimental amount of adsorbate sorbed at instant t (mg g 1 )

Q mean mean of experimental amount of adsorbate sorbed at instant t (mg g 1 ) Q calc amount of adsorbate sorbed at instant t pre- dicted by the model (mg g 1 ) C 0 initial concentration of adsorbate in solution

(mg L 1 )

C concentration of adsorbate in solution at the

moment t (mg L 1 )

C r concentration of adsorbate in the particle of adsorbent at a distance r (mg cm 3 )

k constant (Fick constant, simplification Crank short times constant, Weber and Morris con- stant, Bangham constant)

D

D ep diffusion coefficient in the pore volume

diffusion coefficient at the surface (cm 2 s 1 )

s

(cm 2 s 1 )

external mass transfer coefficient (cm s 1 )

k

k

k ad pseudo adsorption rate constant (unit for

order 1: s 1 , order 2: g mg 1 s 1 , order n:

mg 1n g n1 s 1 , unit for Langmuir: s 1 ) desorption rate constant (s 1 )

L

ad

adsorption rate constant (L mg 1 s 1 )

k d

˛ initial sorption rate in the Elovich model

(mg g 1 s 1 )

constant related to the extent of surface cover- age and activation energy for chemisorption in the Elovich model (g mg 1 ) order of reaction to the adsorbate

ˇ

n order of reaction to the adsorbent in the pseudo order n model or parameter in the Crank model

ϑ parameter in the Bangham model

S surface of adsorbate (cm 2 g 1 )

V volume of adsorbate (mL)

r distance in radial direction of adsorbent; 0 < r < R (cm)

D adsorbent dose (g L 1 )

void fraction in the adsorbent particle density of adsorbent (g cm 3 )

weight of adsorbent (g) activation energy (J mol 1 )

R gas constant (8.314 J mol 1 K 1 ) or Radius of the particle of adsorbent in the Crank model (cm)

T temperature (K)

Ea

m

P

ε

N number of experimental data

Over the years, a wide variety of kinetics models (Langmuir, Pseudo order 1, Pseudo order 2, Pseudo order n, Elovich, Crank, Boyd, Bangham, Weber and Morris, pore volume and surface diffusion) have been formulated. This paper presents an explained and detailed state of the art review of adsorption kinetics modelling by linear

and nonlinear analysis, their application on the study of lead adsorption by an activated carbon derived from Coconut shells, the determination of the kinetics parameters and their comparison with the literature data and finally the selection of the best model to fit the kinetics experimental data.

2. Materials and methods

2.1. Reagents

The 69.4% HNO 3 solution and the NaOH used to fix the pH, the Pb(NO 3 ) 2 which is the lead ions source and the NaNO 3 used to fix the ionic strength of the solution are AR grade and all obtained from Prolabo. All the solutions are prepared with deionized water.

2.2. The activated carbon

The activated Coconut shell carbon is a commercial carbon, NC60, from the PICA Company. It is prepared by physical acti- vation with carbon dioxide and water vapor. The activated carbon sample, as received, is dried at 105 C for 2 days prior to the sorption experiments.

2.2.1.

Characterization

2.2.1.1.

Texture. The texture of the activated carbon is charac-

terized via adsorption of nitrogen at 77 K using a Micromeritics ASAP 2010 apparatus. About 0.30 g of sample is outgassed at 250 C for 48 h, prior to the adsorption measurements. The BET surface area (S BET ) (Brunauer et al., 1938), the DR- micropore volume (V mi ) (Dubinin, 1960), the mesopore volume (V me ) and the DFT pore size distribution of the activated car- bon are determined from the N 2 adsorption isotherm. The mesopore volume is calculated as the volume of N 2 adsorbed at P/P = 0.99 minus the micropore volume and the density functional theory (DFT) pore size distribution is calculated by assuming a slit like geometry for the micropores (Olivier, 1995).

2.2.1.2. Surface properties. The surface properties of the acti-

vated carbon are characterized via the well-known Boehm method (Boehm, 1994). The pH PZC of the activated carbon is determined using the potentiometric titration method as described by (Noh and Schwarz, 1990). All the titrations for Boehm and pH PZC are performed on a 809 SM Titrino auto- matic titrator (Metrohm) and the maximum titrant dosing rate selected is 0.25 mL min 1 . Duplicates are performed for each sample and the relative standard error is equal or less than

3%.

2.3. Kinetic sorption studies

All glassware is presoaked in a 5% HNO 3 solution, rinsed with deionized water and oven dried. All the batch sorption tests and the absorption measurements are duplicated. In the operating mode, 1 g of activated carbon is put in contact with 1 L of lead ion solution, at pH 5 (the adsorbent dose D is equal to 1 g L 1 ). The flask is put in a stirred water bath maintained at a constant temperature of 30 C. The initial concentration of lead is 150 mg L 1 . At regular intervals, 5 mL of solution is removed from the flask, filtered through a Whatmann 32 filter paper and the con- centration of the remaining lead in solution (C) is measured. Note that the stirring is stopped before each removal and that

chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504

497

the total volume removed does not exceed 10% of the initial volume of lead ion solution. The concentrations of lead are measured with an atomic absorption spectrometer AA240FS from Varian. The amount of lead adsorbed at a time t, Q is calculated by the difference between the initial (C 0 ) and the instantaneous lead concentra- tion (C):

Q

mg g 1 = C 0 C

D

(1)

Q max (mg g 1 ) is the maximum amount of lead adsorbed by the activated carbon.

3. Adsorption kinetics models

3.1. Kinetics models

There are three steps in an adsorption process. First, the exter- nal mass transfer of the adsorbate from the bulk solution to the external surface of the adsorbent, followed by the inter- nal diffusion of the adsorbate to the sorption sites and finally the sorption itself. Some models are based on the fact that the sorption is the rate limiting step in the adsorption process, others suppose that the diffusion is the rate limiting step. So, the fitting to the models permits elucidation of the adsorption mechanism.

3.1.1. Diffusional models

The diffusional models assume that the diffusion is the rate limiting step. They are divided in two parts, the external mass transfer model and the internal diffusional models.

3.1.1.1. External mass transfer model. Mass transfer from the

bulk liquid to the solid surface is assumed to be the slowest step. It is characterized by a mass transfer coefficient. How- ever, it seems implausible to the authors that for an adsorption process the approach of the adsorbate to the surface of the adsorbent is the slowest step. Moreover, the effect of trans- port is eliminated by mechanical mixing with the rapid and constant stirring of the solution.

3.1.1.2. Internal diffusional models. The mass transfer into the

interior of the particle, characterized by an intraparticle diffu- sion coefficient, can be the slowest step.

The equation

describing homogeneous diffusion of an adsorbate in an adsorbent modelled as a sphere and assuming a constant sur- face diffusivity D s at all points in the particle is

3.1.1.2.1. Crank

model

(Crank,

1956).

∂Q

∂t

= D S

r

2

∂r r 2 ∂Q

∂r

,

(2)

r being the distance in the radial direction. Crank gives an exact solution to this equation for the aver- age concentration in the solid at any given time for the case where the sphere is initially free of solute and the concentra- tion of the solute at the surface remains constant (that is to say in the absence of external mass transfer). For short times, or more precisely for Q/Q max < 0.3, this equation may be simplified, idem for long duration (more precisely for Q/Q max > 0.85). The simplified Crank long times equation is also known as the Boyd equation (Boyd et al., 1947). The different Crank equations are given in Table 1.

3.1.1.2.2. Weber and Morris model (Weber and Morris,

1963). Weber and Morris have studied the batch adsorption of alkyl benzene sulfonates by activated carbon. They have shown that the plot of Q/Q max versus t 1/2 could be decomposed in two linear plots, the first one corresponding to the equation

Q

Q max =

Cte × t 1/2

(3)

and the second one to the equation

Q

max = Cte × t 1/2 + Cte .

Q

(4)

Some authors suggest for the Weber and Morris model that the first part of the plot also must be modelled by Eq. (4). They explain the presence of the term Cte by the external mass transfer which is not negligible. The authors are not convinced this is true as there is no apparent reason for the amount of lead adsorbed at t = 0 to be different from zero.

The Bangham model can be

understood as the generalization of the Weber and Morris model or the application of the Freundlich and Helle (1939) model to kinetics. The equation is given in Table 1.

3.1.1.2.3. Bangham model.

3.1.1.3. Complex diffusional model. More realistic models for

the solid phase can be used to describe the diffusion pro- cess. However, their greater complexity makes their use mathematically more difficult. An example of a complex dif- fusional model is the pore volume and surface diffusion model (PVSDM) suggested by Geankoplis and Leyva-Ramos (1985). It is a complex diffusional model which takes into account adsorption, external mass transfer and intraparticle diffusion. It is assumed that the intraparticle diffusion is due both to pore volume diffusion and surface diffusion. All the equations needed to solve the model are given in Table 1.

3.1.1.4. Adsorption models. In the adsorption models, the

adsorption is considered to be the slowest process. This is usu- ally the case when the adsorbate uptake on the adsorbent is of chemical nature (i.e., chemisorption). In the following equations S is the adsorption sites, M is the adsorbate, C is the concentration of the adsorbate in solution,

, the order of reaction to the adsorbate, SM is the concentra- tion of adsorbate bound to the sorbent, k ad is the adsorption rate constant and k d the desorption rate constant. The sorp- tion rate is equal to dQ/dt.

3.1.1.4.1. Pseudo first order model (Lagergren, 1898).

The pseudo first order model is described by the non-reversible equation:

S + M MS

(5)

The kinetic equation rests on five assumptions:

1. Sorption only occurs on localized sites and involves no interaction between the sorbed ions.

2. The energy of adsorption is not dependent on surface cov- erage.

3. Maximum adsorption corresponds to a saturated mono- layer of adsorbates on the adsorbent surface.

4. The concentration of M is considered to be constant.

5. The metal ion uptake on the activated carbons is governed by a first-order rate equation.

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chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504

Table 1 – Kinetic models of adsorption.

 

Process control

Kinetic law

Nonlinear form

 

Linear form

 

Linear plot

External mass transfer

Fick equation

 

(Q/Q max ) = 1 6/ 2 n=1 1/n 2 exp D S n 2 2 t/R 2

 

Internal diffusion

Crank

Ln (Q/Q max )

 

 

(Q/Q max ) = 6 D s t/R 2 1/2 1/2 (1/2) D s t/R 2 1/2

=

(1/2) Ln t + Ln 1/2 (1/2) D s t/R 2 1/2

 

Crank (short times) Q/Q max < 0.3

+ (1/2) Ln D s /R 2 + Ln 6

Simplification Crank short times Weber and Morris Bangham

Q

= kt 1/2

with

k = 6 D s / R 2 1/2

 

Ln Q = (1/2) Ln (t) + Ln (k)

 

Ln Q = f(Ln t)

Q = kt 1/2 + Cte Q = kt ϑ

 

– Ln Q = ϑLn (t) + Ln (k)

 

– Ln Q = f(Ln t)

Boyd, Crank long times:

Q/Q max = 1 6/ 2 exp D s 2 t/R 2

 

Ln (1 (Q/Q max )) = Ln 6/ 2 D S 2 t/R 2

Ln (1 cteQ) = f(t)

Q/Q max > 0.85

Complex diffusional

Geankoplis and

V (dC/dt) = −mSk L (C C r | r=R )

 

model

Leyva-Ramos

ε (∂C r /∂t) + P (∂Q/∂t)

 
 

= 1/r 2 (∂/∂r) r 2 (D ep (∂C r /∂r) + D S P (∂Q/∂r))

 
 

(C r /∂t)

r=0 = 0

 

D

ep (∂C r /∂r) + D S P (∂Q/∂r) = k L (C C r | r=R )

 

t =0; C=C 0

 

t=0; C r =0; 0 r R

Adsorption

Langmuir (1 site)

Q(r) = f(C r )

ad +k d t ad / k ad + k d 1 e k

Q = Q max k

Ln 1 Q/Q max k

=

k ad + k d t

ad / k

ad + k d

Ln (1 cteQ) = f(t)

Pseudo order 1

Pseudo order 2

Q = Q max 1 e k ad

t

Q = k

ad Q

2

max t/ 1 + k ad Q max t

 

Ln (1 (Q/Q max )) = −k

ad t

t/Q = (t/Q max ) + 1/k

2

ad Q max

t/Q t =f(t)

Pseudo order n for n =/ 0

Q = Q max 1 1/ 1 + k ad (n 1)Q

max n1 t 1/(n1)

Elovich

Q = (1/ˇ) Ln (1 + ˛ˇt)

 

Ln Q = Ln (1/ˇ) + Ln 2 (1 + ˛ˇt)

Simplification of Elovich: 1 ˛ˇt

Q

= (1) Ln (˛ˇt)

Q = (1) Ln (˛ˇ) + (1) Ln t

 

Q = f(Ln t)

chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504

499

Then, the sorption rate can be written as

k ad C Q max Q

Q

max

2

= k ad (Q max Q)

(6)

and the resulting equation after integration is given in Table 1.

3.1.1.4.2. Pseudo second order model (Ho et al., 1996; Ho

and McKay, 1999). The kinetics of metal ion removal are described by the pseudo second order model as follows:

2S + M M(S) 2

(7)

The assumptions are almost the same as for the pseudo first order model except the metal ion uptake on the activated carbons is governed by a second-order rate equation. Then, the sorption rate can be written as

k ad C Q max Q

Q

max

2

=

k ad (Q max Q) 2

(8)

The resulting equation by integration is given in Table 1.

3.1.1.4.3. Pseudo n order model for n different from zero

(Ritchie, 1977). The kinetics of metal ion removal can be described by the pseudo n order model. The equation is

nS + M M(S) n

(9)

The assumptions are the same as for the pseudo first order model except the last one as the metal ion uptake on the activated carbons is governed by a rate equation of order n. Then, the sorption rate can be written as

k ad C Q max Q

Q

max

n

=

k ad (Q max Q) n

(10)

The result of the integration is given in Table 1.

The kinet-

ics of metal ion removal are described by the Langmuir model using this reversible equation:

3.1.1.4.4. Langmuir model (Langmuir, 1918).

S + M MS

(11)

The four assumptions are the same as for the pseudo first- order model but now the rate of desorption is not negligible compared to the rate of adsorption. Then, the sorption rate can be written as

k ad C Q max Q

Q

max

k d

Q max = k

Q

ad (Q max Q) k d Q

(12)

and the integrated equation is given in Table 1.

The

kinetics of metal ion removal is described by the Elovich model as follows:

3.1.1.4.5. Elovich model (Elovich and Larinov, 1962).

S + M MS

(5)

1. Sorption only occurs on localized sites and there is inter- action between the sorbed ions.

2. The energy of adsorption increases linearly with the sur- face coverage according to the law:

Ea = Ea 0 + RTˇQ

(13)

Then, the adsorption rate constant k ad can be written, using the Arrhenius equation, as:

Ea k ad = Cte × exp RT =

with

˛ = Cte × exp Ea 0 RT

˛ × exp (ˇQ)

(14)

(15)

3. The concentration of M is considered to be constant.

4. The metal ion uptake on the activated carbons is negligible before the exponential (equivalent to a metal ion uptake governed by a zero order rate equation).

Then, the sorption rate can be written as:

˛ × exp (ˇQ)

(16)

 

with

˛

= C ˛

(17)

and the resulting integration is given in Table 1.

3.2.

Fitting the kinetics models to the experimental

data

All these models are tested to describe the sorption of lead on the activated carbon from Coconut shells using a home- made program. The experimental sorption data are fitted to the linear and the nonlinear form of the models. So, linear and nonlinear least squares analysis is applied to each set of adsorption data using the Ceres solver library [ht*tp://co*de.go*ogle.co*m/p/ceres-solver/]. The root mean square error (E) is calculated by the expres- sion:

E =

1

N

N

i=1

(Q exp Q calc ) 2

(18)

N being the number of experimental points. The best model

describing the experimental data is the one with the lowest E. The correlation coefficient of determination R 2 is also cal- culated as

R 2 = 1 SS res

SS tot

(19)

With the residual sum of squares,

SS res =

N

i=1

(Q exp Q calc ) 2 ;

(20)

With the total sum of squares,

SS tot =

N

i=1

(Q exp Q mean ) 2

(21)

The Fisher test (FR 2 ) of two models seem close to each other in order to discriminate without any doubt the best model.

F is determined through the ratio of the residual sum of

squares (SS res ) of the two models.

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chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504

The P value (P value) is then calculated via the F cumulative distribution function (cdf):

P

value = 1 cdf(F, df 1 , df 2 )

(22)

df 1 , df 2 is respectively the degree of freedom for each of the two models. It is calculated as the number of experimental data less the number of parameters to estimate in the model. Other error functions like E or R 2 to compute the difference between the experimental data and the predicted values are given in Foo and Hameed (2009). Note that the modelling for the Crank model and the pore volume and surface diffusion model suggested by Geankoplis and Leyva Ramos are explained with precision in other papers (Largitte and Laminie, 2015; Largitte and Pasquier, 2016a). Note that also the linear and nonlinear Boyd, Crank (long times) modelling and linear pseudo order 1 modelling need to fix a Q max to begin the computation. Q max is fixed at 52 mg g 1 , the next higher entire value than the experimental one.

4. Results and discussion

4.1. Characterization of the activated carbon

The textural properties of the activated carbon have been studied. The nitrogen adsorption/desorption isotherm for

the activated Coconut shells carbon is shown in Fig. 1. The isotherm is of type I according to the BDDT classification, characteristic for microporous materials (Gregg and Sing,

1982).

The values of S BET , V mi , V me obtained from the isotherm are listed in Table 2. The mesopore volume is negligible; the micro- pore volume is in high agreement with such a high surface area. The micropore size distribution of the activated carbon is studied according to the DFT model. The DFT plot shows

that there are many micropores of size 6 A, close to the size of

the hydrated lead cation (Nightingale, 1959). The chemical surface properties of the activated carbon are also listed in Table 2. The total number of acid groups on the surface of the activated carbon is low (0.3 mmol g 1 ) compared to the total number of basic groups (0.9 mmol g 1 ). The distribution of the acidity is narrow because only alcohol groups are present. The activated coconut shells carbon is a basic activated carbon with a pH PZC equal to 9.2.

´

˚

activated carbon with a pH P Z C equal to 9.2. ´ ˚ Fig. 1 –

Fig. 1 – Adsorption/desorption isotherm of N 2 at 77 K on the activated Coconut shells carbon. Pore size distribution of the activated carbon from Coconut shells by applying the DFT method to the nitrogen adsorption isotherm at 77 K.

Table 2 – Characterization of the activated carbon.

Activated carbon from coconut shells

S BET (m 2 g 1 )

1058

V mi (cm 3 g 1 ) V me (cm 3 g 1 )

0.49

0

Total of acid oxygenated surface groups (mmol g 1 ) Carboxyl groups Hydroxyl groups Lactone groups Total of basic oxygenated surface groups (mmol g 1 )

0.3

0

0.3

0

0.9

pH PZC

9.2

50 40 short mes 30 long mes Weber and Morris 20 Data 10 0 0
50
40
short mes
30
long mes
Weber and Morris
20
Data
10
0
0 1000
2000
3000
4000
Amount of lead adssorbed (mg.g -1 )

Time (min)

50 40 short 30 mes long mes 20 Bangham 10 0 0 1000 2000 3000
50
40
short
30
mes
long mes
20
Bangham
10
0
0 1000
2000
3000
4000
Amount of lead adssorbed (mg.g -1 )

Time (min)

50 40 30 short mes long mes, Boyd 20 Crank Data 10 0 0 1000
50
40
30
short mes
long mes, Boyd
20
Crank
Data
10
0
0 1000
2000
3000
4000
Amount of lead adssorbed (mg.g -1 )

Time (min)

Fig. 2 – Experimental kinetics adsorption (the points) and (a) modelled kinetics adsorption by Weber, Morris equations; (b) by Bangham equations and (c) by Crank equations using all the data and only the data at short times or long times.

chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504

501

50 40 Data 30 Crank Bangham 20 Weber and Morris 10 Geankoplis 0 0 1000
50
40
Data
30
Crank
Bangham
20
Weber and Morris
10
Geankoplis
0
0 1000
2000
3000
4000
Amount of lead adsorbed (mg.g -1 )

Time (min)

50 40 30 Data 20 Order 2 Elovich Order 1, Langmuir Order n = 2.8
50
40
30
Data
20
Order 2
Elovich
Order 1, Langmuir
Order n = 2.8
Simplified Elovich
10
0
0
1000
2000
3000
4000
Amount of lead adsorbed (mg.g -1 )

Time (min)

Fig. 3 – Experimental kinetics adsorption (the points) and modelled kinetics adsorption (the lines); (a) by the diffusional equations (b) by the adsorption equations.

4.2. Application of the kinetics models

The experimental uptake rate of lead by the activated carbon from Coconut shell is studied at pH 5 for an initial lead concen- tration of 150 mg L 1 and an adsorbent dose of 1 g L 1 at 30 C. The sorption is quite rapid as can be seen in Figs. 2–4: 16% of the lead is removed within the first two hours followed by a slow approach to equilibrium. Equilibrium is reached after 50 h and the value of the experimental maximum amount of lead adsorbed is 50.2 mg g 1 .

50 40 Data 30 n = 2.8 n = 6 20 n = 40 10
50
40
Data
30
n
= 2.8
n
= 6
20
n
= 40
10
0
0 1000
2000
3000
4000
Amount of lead adsorbed (mg.g-1)

Time (min)

Fig. 4 – Experimental kinetics adsorption (the points) and modelled kinetics adsorption by Pseudo order n equation (the lines).

The kinetic results are fitted according to the linear and nonlinear form of the kinetics models. The results of the fitting are given in Table 3.

4.2.1.

Comparison between the linear and the nonlinear

models

Globally, the order of magnitude of the root mean square error E follows the same trend for the linear and the nonlinear mod- els except for the Boyd, Crank long duration model which has the lowest E in the linear modelling and one of the worst in the nonlinear modelling. However, as the linearization is not possible for all the mod- els, the comparison between the linear and nonlinear models is truncated. Moreover, other authors have pointed that the linearization bias the estimate of model’s parameter set (Ho, 2006). This means that the use of nonlinear expressions must be favored. Then, only the results obtained from nonlinear modelling will be further discussed.

4.2.2. Comparison between the time range for the kinetic

modelling

As it can be seen from Figs. 2–4, the whole models are com- pared in the entire time range available except for the Crank short duration and long duration models which are, by default, limited to a short duration range. However, restricting the study to the beginning or the latest stage of the process, as it can be seen in Fig. 2, is not representative for the whole pro- cess and can lead to an under or overestimation of the kinetics parameters. Then, the best way to obtain an average is to take the data for the entire uptake process. Consequently, it is better to use the Crank model in the entire duration range instead of the Crank short times or long times models in short duration ranges as can be seen in Fig. 2. This result can be generalized and the models describing the entire time range of the process must be favored. This is the case for the Crank, Bangham, Leyva Ramos, Langmuir, Elovich and Pseudo order 1, 2 and n models.

4.2.3. Comparison between the kinetics parameters

Fig. 3 presents the kinetics data and the fitting plots for all the diffusional and all the adsorption models and Table 3, the kinetics parameters obtained from the modelling. According to the diffusional models, that is to say, the Crank, Bangham, Leyva Ramos, Weber and Morris and Geankoplis models, the diffusion coefficient (D s , D ep ) or the rate constant k can be calculated. The maximum amount of lead adsorbed Q max predicted by the model can also be calcu- lated and compared to the experimental maximum amount which is 50.2 mg g 1 . As it has been previously assumed, the diffusion coeffi-

cient at the surface D s is different in the Crank long times

model (here, underestimated) compared to the entire Crank

model. However, the maximum amount of lead predicted by

the Crank long times model (52 mg g 1 ) is closer to the exper- imental result. On the contrary, the pore volume and surface diffusion model suggested by Leyva Ramos shows that when one assumes only diffusion inside the pore volume, D s is equal to zero and D ep /R 2 is 7.5E 03 s 1 , a value four times higher than the one obtained for D s /R 2 in the simplified Crank short duration model (1.71E 03 s 1 ). The simplified Crank model and the Weber and Morris model can be compared to each other because they both use

502

chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504

Table 3 – Kinetics modelling results.

 

Kinetics laws

Nonlinear form

 

Results for the nonlinear form

E in the linear form

Results for the linear form

 
 

E

R 2

Crank

2.600

0.923

Q max = 46.8 mg g 1 ; D s /R 2 = 4.74E 06 s 1 na

 

Crank short times Q/Q max < 0.3 (not enough points) Simplification Crank short times

na

na

na

na

10.469

na

k = 0.140 mg g 1 s 1/2 =

15.674

Ln k = 1.708, then

 

6 D s / R 2 1/2 ;

D s /R 2 = 1.71E 03 mg 2 g 2 s 1 k = 0.07 mg g 1 s 1/2 ; Cte = 22.350 mg g 1 k = 4.639 mg g 1 s ; ϑ = 0.198

k

D

= 0.181 mg g 1 s 1/2 ;

s /R 2 = 2.86E 03 mg 2 g 2 s 1

Weber and Morris:

2.694

0.917

kt 1/2 + Cte Bangham: kt

1.175

0.984

1.288

Ln k = 1.398, then

 

= 4.047 mg g 1 s ; ϑ = 0.210

k

Boyd, Crank long times Q/Q max > 0.85 (only 4 points) Geankopolis and Leyva-Ramos

1.802

na

Q max = 52.05 mg g 1 ; D s /R 2 = 1.90E 06 s 1

 

0.360

D

s /R 2 = 1.61E 06 s 1

6.774

0.479

D ep /R 2 = 7.50E 03 s 1 ; D s = 0 cm 2 s 1 ; k L = 4.60E 02 cm s 1

Langmuir (1 site)

3.785

0.837

Q max k ad / k

ad + k d = 45.76

Pseudo order 1

k ad + k d = 1.03E 04 Then, k ad Q max = 45.13E 04 Q max = 45.76 mg g 1 ; k ad = 1.03E 04 s 1

10.795

k

ad = 1.94E 05 s 1

Pseudo order 2

2.323

0.939

k

ad Q

max = 0.0072;

2

k

ad Q max =

1.46E 04 Then, k ad = 2.96E 06 g mg 1 s 1 ; Q max = 49.33 mg g 1

3.917

ad Q max 2 = 0.0041;

k

Q

max = 53.75 mg g 1 Then

 

k

ad = 1.44E 06 g mg 1 s 1

Pseudo order n

1.686

0.968

k ad = 1.27E 07 mg 1n g n1 s 1 ; Q max = 54.18 mg g 1

for n = 2.8

0.839

0.992

k ad = 7.16E 14 mg 1n g n1 s 1 ; Q max = 76.83 mg g 1

 

for n = 6

0.462

0.99758

k ad = 4.14E 103 mg 1n g n1 s 1 ; Q max = 331.76 mg g 1

 

for n = 40

Elovich

0.468

0.99751

(1/ˇ) = 7.524;

˛ˇ = 0.004

 

Then ˇ = 0.133 g mg 1 ;

 

˛ = 0.033 mg g 1 s 1

 

Simplification of Elovich: 1 ˛ˇt

0.461

0.99758

1= −39.77;

˛ˇ = 7.44

0.461

1= −39.77;

˛ˇ = 7.44

 

Then, = 0.134 g mg 1 ; = 0.035 mg g 1 s 1 ;

ˇ = 0.134 g mg 1 ; ˛ = 0.035 mg g 1 s 1

the parameters k and t 0.5 , however this is not the case for the Bangham model which uses a dependence of k and t 0.2 . The parameter k is the double for the simplified Crank model than for the Weber and Morris one (0.14 mg g 1 s 1/2 against 0.07 mg g 1 s 1/2 ). The results obtained from the Weber and Morris modelling, from the Crank long duration modelling and the Bangham modelling are in agreement with the literature data found for the sorption of lead by activated carbons (Sreejalekshmi et al., 2009; Li and Wang, 2009; Gerc¸el and Gerc¸el, 2007; Mishra and Patel, 2009; Shekinah et al., 2002; Ho et al., 1996; Nadeem et al., 2006; Wang et al., 2010; Ayyappan et al., 2005). Concerning the adsorption models, Langmuir, Elovich, Pseudo order 1, 2 and n models, the pseudo adsorption rate constant or the sorption rate and sometimes the maximum amount of lead adsorbed Q max can be calculated. Note that the pseudo adsorption rate constant in the Lang- muir model (k ad ) and the desorption rate constant k d cannot be calculated solely with the results of the Langmuir kinetics

modelling because there are two unknown parameters and only one equation. A method to determine the constants k ad and k d is to use Q max exp = 50.2 mg g 1 or Q max predicted by the Lang- muir equilibrium model equal to 47.7 mg g 1 (Largitte and Pasquier, 2016b). Knowing the sum of the constants k ad and k d equal to 1.03E 04 and k ad Q max equal to 45.13E 04, k ad can be deduced. It is equal to 8.99E-05 (9.5E 05) s 1 and k d to 1.31E 05 (8.4E 06) s 1 . Considering that the value of k ad is higher than k d , one can consider the adsorption to be easier than the desorption on the surface of this activated carbon. These results are near those of Machida et al. (2005) and Sekar et al. (2004). Note that he knowledge of the ratio k ad /k d obtained though the fitting of the isotherm data by the Langmuir equilibrium model can also permit to determine k ad . According to Largitte and Pasquier (2016b), the ratio k ad /k d is equal to 0.749. Solving the equation yields k ad equal to 9.8E 06 (6.3E 06) L mg 1 s 1 .

chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504

503

The kinetics are better described by the pseudo order n model and the pseudo order 2 model than by the pseudo 1 model.

For the pseudo second order model, the pseudo rate con- stant k ad is equal to 2.96E 06 g mg 1 s 1 and the maximum amount predicted by the model is 49.33 mg g 1 . In the case of the pseudo order n model, a higher value of

n gives a better fitting (see Fig. 4 and Table 3), but produces

predicted maximum amounts that are very different from the experimental one. The most coherent result is obtained for

n equal to 2.8, which gives a predicted maximum amount of

54.2 mg g 1 . Many data are available on the pseudo rate constant for the pseudo first order model (Sreejalekshmi et al., 2009; Li and Wang, 2009; Gerc¸el and Gerc¸el, 2007; Mishra and Patel, 2009; Shekinah et al., 2002; Nadeem et al., 2006; Wang et al., 2010; Ayyappan et al., 2005; Ibrahim et al., 2012; Inyang et al., 2012; Largitte et al., 2012, 2014; Ricordel et al., 2001), pseudo second order model (Sreejalekshmi et al., 2009; Li and Wang, 2009; Gerc¸el and Gerc¸el, 2007; Mishra and Patel, 2009; Nadeem et al., 2006; Wang et al., 2010; Ibrahim et al., 2012; Inyang et al., 2012;

Largitte et al., 2012, 2014] and pseudo nth order model (Ricordel et al., 2001) which can be compared to our results. Concerning the Elovich model, there is only a minor dif- ference between the results of the Elovich model and the simplified Elovich model. The initial sorption rate ˛ changes from 3.3E 02 to 3.5E 02 mg g 1 s 1 and the constant related to the extent of surface coverage and activation energy for chemisorption, ˇ, from 0.133 to 0.134 g mg 1 . These results are concordant with previous results from other authors (Li and Wang, 2009; Wang et al., 2010; Ibrahim et al., 2012; Inyang et al.,

2012).

The initial sorption rate can also be calculated from the pseudo second order model using the expression k ad Q max 2 and can be compared to the value ˛ obtained by the Elovich model. The result gives 7.2E 03 mg g 1 s 1 and is five times smaller than the value obtained from Elovich (3.5E 02 mg g 1 s 1 ). To conclude, the value of the maximum amount of lead adsorbed obtained for this activated carbon, from the experi- ment or from the fitting, is really well compared to literature data. This result is in agreement with the high surface area of the activated carbon, the high micropore volume and the presence of alcohol groups on its surface which can promote the complexation of lead to the carbon surface.

4.2.4. Comparison between the error values

The values of the error E and R 2 are presented in Table 3 and Fig. 3 presents the fitting of the different diffusional and sorp- tion models to the experimental data. The lowest value of E and the best coherent fitting of the models is for the simplified Elovich model and the error increases in the order: sim- plified Elovich < Elovich < Bangham < pseudo order n < pseudo order 2 < Crank < Weber and Morris < Langmuir, pseudo order 1 < pore volume and surface diffusion model by Leyva Ramos. According to these error results, Elovich is the best model which describes the experimental data. However, the

E value for Bangham and Elovich are very proximate. So

a F test is made to choose undoubtedly the best model.

F = SS(Bangham)/SS(Elovich) = 6.30517; then, the calculated

value is equal to 0.0087. The P value, inferior to 0.01, shows that the Elovich model is statistically better than the Bangham model with a false-rejection probability inferior to 0.01.

P

55 y = 7.5474x - 10.173 50 R² = 0.98 45 40 35 y =
55
y = 7.5474x - 10.173
50
R² = 0.98
45
40
35
y = 7.9469x - 12.069
R² = 0.992
30
25
20
4
5
6
7
8
9
Ln(t+t 0 )
With t 0 = 1/(αβ)
Amount of lead adsorbed (mg.g -1 )

Fig. 5 – The two types of sorption sites implied in the sorption process according to Elovich model.

From these results, a simplified Elovich model can be put forward for the sorption of lead by the activated Coconut shells carbon. This means the rate limiting step in the process is the chemical sorption between the lead and the active sites of the carbon and that the activation sorption energy increases with the process. So, the experimentally demonstrated observation of the sorption rate slowing down with time is explained by the Elovich model that explains, at first, the lower energy surface sites of the carbon saturate, and then, the adsorption shifts to the higher energy surface sites, resulting in a decrease of the sorption rate. According to the Elovich model assumptions and to the break of slope in the derivative Elovich plot (Fig. 5), there are two types of sorption sites implying in this sorption process. Two sorption sites, probably relative to the both ways of sorp- tion of lead cations on the adsorbent surface, one with the oxygen of the alcohol surface groups by complexation and the other one with the electrons of the graphene layers of the activated carbon by electrostatic interaction. Consequently, the kinetics of the adsorption of lead by the activated carbon from Coconut shell can be described though the equation:

Q =

1 ˇ Ln (˛ˇt)

(23)

with ˛ equal to 0.035 mg g 1 s 1 and to 0.134 g mg 1 .

5.

Conclusion

This paper aims to study in detail the different existing models of kinetics adsorption and to apply them to the sorption of lead onto an activated carbon. The kinetics is studied at 30 C, ini- tial pH 5, initial lead concentration 150 mg L 1 and adsorbent dose 1 g L 1 for an activated carbon from Coconut shells. The objectives are to explain, with precision, all the kinetics mod- els, to determine all the kinetics parameters, to compare them to the literature data and finally to find the model that can bet- ter describe the experimental results of adsorption kinetics of the activated carbon. The screening is made via the root mean square error and the correlation coefficient of determination. So, 10 mathematical models of adsorption are studied and several kinetic parameters (coefficient of diffusion, rate constant, sorption rate and maximum of lead adsorbed) are calculated. The results show that the Crank, the Bangham, the pore volume and surface diffusion by Geankoplis and Leyva Ramos,

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chemical engineering research and design 1 0 9 ( 2 0 1 6 ) 495–504

the Langmuir, the Elovich, the pseudo order 1, 2 and n models fit the experimental data quite well over a wide time range. This is in contrast to the Crank short or long times (simplified or not). So the first group of models cited must be preferred to describe the kinetics of adsorption. It can also be noted that it is one of the first times, to our knowledge, that the Crank model is used to model all the kinetic data. In the case of this activated coconut shell carbon, the sorp- tion data are better simulated by the nonlinear models in the order: simplified Elovich > Elovich > Bangham > pseudo order n > pseudo order 2 > Crank > Weber and Morris > Langmuir, pseudo order 1 > pore volume and surface diffusion model by Geankoplis and Leyva Ramos. Based on the lowest value of the root mean square error, it can be said that the adsorption of lead on this activated carbon is best described by the simplified Elovich model. The kinetics correspond to the equation: Q = (1/ˇ) Ln (˛ˇt) with ˛ equal to 0.035 mg g 1 s 1 and ˇ to 0.134 g mg 1 .

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