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The Water Adsorption Isotherm Models on Activated Alumina SHI Yun Fei, LIU Xiang Juna, NIE Hui Jiao, LIU Yin Shu

School of Mechanical Engineering, University of Science & echnology !ei"ing, !ei"ing, #$$$%&, 'hina

a

liu(")*e+ust,+e-u+cn

Abstract. The adsorption isotherm model of water vapor on activated alumina is an essential equation in designing the performance of adsorption. In this paper, the currently existed 14 isotherm models of water adsorption are summarized. The correlations among these models are analyzed. These isotherm models are evaluated by fitting the water adsorption data on hone!"oulenc activated alumina. The results show that #$!Toth, #$!% &, #$!'(I%#( and $)#" can fit the experimental data well. 1.Introduction *ver the past decades, the removal of water vapor from air is receiving increasing attention because of emerging needs in air reparation, purification, and environmental protection applications+1!,-. #ctivated alumina adsorbents are currently widely used as desiccants in both heated .Temperature /wing #dsorption0 and heatless ."ressure /wing #dsorption0 dryers+1!4-. The adsorption characteristics of water vapor on activated alumina are essential data in determining the energetic performance of adsorption+4-. )any researches have been carried to study the water adsorption isotherms and models on activated alumina. (umerous studies of water vapor adsorption on different activated alumina can be found in the literature, and various adsorption isotherm equations for water vapor adsorption on alumina are also established by researchers. In this article, the currently existed 14 isotherm models on water adsoption isotherm equations are summarized. The correlations among these equations are analysed. These isotherm models are evaluated by fitting the water adsorption data on hone!"oulenc activated alumina. . 2. Summary of Adsorption Isotherm Models 1arious adsorption isotherm equations for water vapor adsorption on different activated alumina are established by researchers. There are totally 14 models which can be divided into four groups according to the correlativity among these models. 2.1 Langmuir, Freundlich, Langmuir-Freundlich Load !atio "orrelation#, $oth models. )odels in this first group can be used to describe adsorption isotherms when the partial pressure of water vapor is low. The %angmuir, 2reundlich, %angmuir!2reundlich .%oad atio &orrelation0, Toth models can be expressed as follows, The %angmuir+3-4 The 2reundlich model+3-+,-4 the %angmuir and 2reundlich .% &0 model+,- 4 The Toth equation+,-4

q 5 qm = bp 5 .1 + bp 0

.10

15 n

q = kf p

q=

.30

15 n

qm bP 1 + bP15 n

.,0 .40

q bP = qm +1 + .bP015 n -n

2.2 %&$, n-layers %&$, Langmuir-%&$, the single-component modified %&$ models. )odels based on 67T theory are classed into the second category. 2or adsorption layers are infinite, the normal 67T model is written as+4-,

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of TTP, www.ttp.net. (ID: 130.88.99.226, The University of Manchester, Manchester, United Kingdom-18/02/14,16:16:36)

101

.80 2or adsorption layers are limited layers, not more than n, the n!layers 67T equation is as follow ,

+8-

.90

The single!component modified 67T equation is written as+9-, CBET . P 5 Ps 0 q = qm .1 kP 5 Ps 0+1 + .CBET k 0 P 5 Ps +4-

.:0

2.' A( Models. #ranovich and $onohue proposed an isotherm model of the following form 4 q 5 qm = f . P 0 5 .1 P 5 PS 0 d .;0 d <here the modification term 1 5 .1 P 5 PS 0 describes the singularity. f . P 0 can be substituted with the %angmuir, Toth, % & and '(I%#( equation. #nd thus the #$!%angmuir, #$!% &, #$!Toth and #$!'(I%#( model can be obtained respectively+4-+8-. 2or example, if f . P 0 = '(I%#( equation, the obtained #$!'(I%#( model is , ( c + Pe+ s ) ( c + Pe s ) q ln = .>0 qm 3 s .1 P 5 Ps 0 d #ccording to the equation proposed by #ranovich and $onohue, q . P 0 = f . P 0 g . P 5 PS 0 , ?hang substituted f . P 0 with %angmuir equation and g . P 5 PS 0 with e nP 5 P , and got the 7xtended %angmuir .7%0 isotherm model. The expression is+:-, q bP nP 5 Ps = e .1@0 qm 1 + bP 2.) (!, (A, (MA* models. There is another series of models based on potential theory+;-. In the earlier literatures, research of adsorption on activated carbon led to the derivation of $! equation. <hen the adsorption potential is squared, $!# model can be obtained+;ln q = ln qs + D ln. P 5 Ps 0-n .110 <here D = Rg T 5 E . $)#" model can be derived from 7q..110 by reserving the first two terms. (ote that the first term is actually a 2reundlich form, which can be replaced by %angmuir form when a linear nature in low pressure range is wanted. The $)#" equation is expressed as+>- 4 A A q = qs1 exp. 0 + . qs 3 qs1 0 exp. 0 .130 E1 E3

s

In this paper, the above 14 isotherm models are used to fit the water adsorption data on activated. <e choose the experimental data of adsorption isotherm for hone!"oulenc activated alumina at 39 from reference+1-. '.1 Lo+ *ressure !ange Fitting )odels in the first group can be used to describe adsorption isotherms when the partial pressure of water vapor is low. 2ig.1a and 1b show the fitting results by %angmuir and 2reundlich models. It can observed that 2reundlich model has a wider applicable range than %angmuir model. 2ig.1c and 1d show the fitting results by % & and Toth models. The fitting results of % & and Toth model are close, and the accuracy will decrease if we fit experimental data at higher pressure. 2ig. 1 shows that, the 2reundlich, %angmuir!2reundlich and Toth models can all be used to describe the water adsorption isotherms in a wider pressure range than %angmuir model. The performances of % & and Toth model are similar, but a main important difference between them is that Toth model can be reduced to the AenryBs form as the pressure is very low, which is a very practical property.

102

2 :7*ol;<g9 E(/eri*ental Lang*uir7 5 /oints9 Lang*uir7 6 /oints9 Lang*uir7## /oints9 Lang*uir7#& /oints9 :7*ol;<g9

&

&

$+1

$+2

$+4 /7<@a9

$+%

#+1

$+1

$+2

$+4 /7<@a9

$+%

#+1

.a0

3 2+3 2 &+3 & :7*ol;<g9 1+3 1 #+3 # $+3 $ E(/eri*ental LB'7 5 /oints9 LB'7 6 /oints9 LB'7## /oints9 :7*ol;<g9 3 2+3 2 &+3 & 1+3 1 #+3 # $+3 $

.b0

$+#

$+1

$+& /7<@a9

$+2

$+3

$+4

$+#

$+1

$+& /7<@a9

$+2

$+3

$+4

.c0 .d0 2ig. 1 %ow pressure range fitting .a, %angmuir. b, 2reundlich. c, % &. d, Toth 0

'.2 -hole *ressure !ange Fitting Isotherm models of the other three groups can be used to fit data in whole pressure range. <e use 67T series , #$ series and $" series models to fit the experimental data of water adsorption isotherm for hone!"oulenc activated alumina respectively. 2ig.9 shows the fitting results of 67T series models. This figure shows that normal 67T model can not fit the data at medium and high pressure well. The main difference between these 67T series models is the predicting for saturation adsorbance. The n!layer 67T and the )!67T are obviously more suitable for the entire pressure range compared to 67T.

1$ #% #4 #2 #1 :7*ol;<g9 #$ % 4 2 1 $ E(/eri*ental !E n=!E M=!E

1$ #% #4 #2 #1 :7*ol;<g9 #$ % 4 2 1

$ #$ 1$ &$ 2$ 3$ 4$ Hu*+789 5$ %$ 6$ #$$

#$

1$

&$

2$

3$ 4$ Hu*+789

5$

%$

6$

#$$

2ig.: shows the fitting results of the $# series models on hone!"oulenc activated alumina. It can be observed that $# equation is only suitable to fit the data at low and medium pressures. $)#" model fit the data well for the entire pressure range.

103

2ig.; shows the fitting results of the #$ series models. #ll the #$ models can fit the data well and their fitting performances are similar. The defect of the #$ series models is that the prediction at high pressure approaching saturation is unreasonable. #$ models will predict an infinite adsorbance at saturated pressure. In 2ig ;b, 7% model can not fit the isotherm data well at medium and high concentration. Aowever, it shows a reasonable fact that activated alumina limites a maximum adsorbance for water vapor.

1$ #% #4 #2 #1 :7*ol;<g9 #$ % 4 2 1 $ :7*ol;<g9 e(/eri*ental ?>=Lang*uir ?>=toth ?>=Si/s7LB'9 ?>=UNIL?N 1$ #% #4 #2 #1 #$ % 4 2 1 $ e(/eri*ental EL

#$

1$

&$

2$

3$ Hu*+8

4$

5$

%$

6$

#$$

#$

1$

&$

2$

3$ Hu*+8

4$

5$

%$

6$

#$$

.b0 .a0 2ig ; The fitting results of #$ models and 7% model on activated alumina # /ummary of fitting standard errors./70 and relativities. 0 are shown in Table 1. Table 1 2itting standard errors and relativities of the above models

)odel /7 ! 67T @.9:: @.>;818 7% @.,8@ @.>>,:: #$! %angmuir @.,@3 @.>>8,8 n!67T @.3;4 @.>>8>, )!67T @.383 @.>>9:: #$ !Toth @.3:1 @.>>9@> $)#" @.18; @.>>;:, #$! /ips.% &0 @.119 @.>>>,1 #$! '(I%#( @.118 @.>>>,,

). "onclusion

The currently existed 14 isotherm models on water adsoption isotherms are summarized. These isotherm models are evaluated by fitting the water adsorption data on hone!"oulenc activated alumina. The fitting results show that, models such as #$!Toth, #$!% &, #$!'(I%#( and $)#" models, taCen as many as four parameters to describe the isotherms, can fit the experimental data well. The 7% model cannBt fit the isotherm data well at medium and high concentration. Aowever, it shows a reasonable fact that activated alumina limites a maximum adsorbance for water vapor.

!eferences

. $esai, ). Aussain, $. ). uthven. #dsorption of water vapour on activated alumina. I D equilibrium behaviour. The &anadian Eournal of &hemical 7ngineering, 1>>3, :@ .40, 9>>!:@9. +3- ?. ?hao. Theory and #pplication on #dsorption. &hemical "ress. 3@@8.@> . in &hinese0 . +,- /. '. ege, . T. Fang, ). #. 6uzanowsCi. /orbents for air prepurification in air separation. &hemical 7ngineering /cience, 3@@@, 88.310, 4;3:!4;,;. +4- $. 2erreira, . )agalhaes, ". Taveira, et al. 7ffective adsorption equilibrium isotherms and breaCthroughs of water vapor and carbon dioxide on different adsorbents. Ind. 7ng. &hem. es., 3@11, 8@ .1:0, 1@3@1D1@31@. +8- E. Gim, &. %ee, <. Gim, E. %ee, et al. #dsorption equilibria of water vapor on alumina, zeolite 1,x, and a zeolite x5activated carbon composite. E. &hem. 7ng. $ata, 3@@,, 4; .10, 1,:D141. +9- H. %i, ". Iiao and ". <ebley. 6inary adsorption equilibrium of carbon dioxide and water vapor on activated alumina. %angmuir, 3@@>, 38 .1;0, 1@999D1@9:8. +1-

104

+:- ". ?hang, %. <ang. 7xtended langmuir equation for correlating multilayer adsorption equilibrium data. /eparation and "urification Technology, 3@@>, ,9:!,:1. +;- #. /erbezov. #dsorption equilibrium of water vapor on f!3@@ activated alumina. E. &hem. 7ng. $ata, 3@@,, 4; .30, 431D438. +>- E. )oore, #. /erbezov. &orrelation of adsorption equilibrium data for water vapor on f!3@@ activated alumina. #dsorption, 3@@8, 11.10, 98!:8.

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