0deec51ec02c556e15000000

7/23/2019 0deec51ec02c556e15000000

1/6

See discussions, stats, and author profiles for this publication at: http://www.researchgate.net/publication/228616243

Capacity loss in an organically fouled anionexchanger

ARTICLE in DESALINATION MARCH 2006

Impact Factor: 3.76 DOI: 10.1016/j.desal.2005.07.012

CITATIONS

10

4 AUTHORS:

Zeren Beril Gnder

Istanbul University

12PUBLICATIONS 115CITATIONS

SEE PROFILE

Yasemin Kaya

Istanbul University


SEE PROFILE

Ilda Vergili

Istanbul University


SEE PROFILE

Hulusi Barlas

Istanbul University


SEE PROFILE

Available from: Ilda Vergili

Retrieved on: 12 October 2015
http://www.researchgate.net/profile/Ilda_Vergili?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_4http://www.researchgate.net/profile/Ilda_Vergili?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_4http://www.researchgate.net/institution/Istanbul_University?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_6http://www.researchgate.net/profile/Zeren_Goender?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_5http://www.researchgate.net/institution/Istanbul_University?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_6http://www.researchgate.net/profile/Yasemin_Kaya2?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_5http://www.researchgate.net/?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_1http://www.researchgate.net/profile/Hulusi_Barlas?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_7http://www.researchgate.net/institution/Istanbul_University?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_6http://www.researchgate.net/profile/Hulusi_Barlas?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_5http://www.researchgate.net/profile/Hulusi_Barlas?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_4http://www.researchgate.net/profile/Ilda_Vergili?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_7http://www.researchgate.net/institution/Istanbul_University?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_6http://www.researchgate.net/profile/Ilda_Vergili?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_5http://www.researchgate.net/profile/Ilda_Vergili?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_4http://www.researchgate.net/profile/Yasemin_Kaya2?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_7http://www.researchgate.net/institution/Istanbul_University?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_6http://www.researchgate.net/profile/Yasemin_Kaya2?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_5http://www.researchgate.net/profile/Yasemin_Kaya2?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_4http://www.researchgate.net/profile/Zeren_Goender?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_7http://www.researchgate.net/institution/Istanbul_University?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_6http://www.researchgate.net/profile/Zeren_Goender?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_5http://www.researchgate.net/profile/Zeren_Goender?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_4http://www.researchgate.net/?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_1http://www.researchgate.net/publication/228616243_Capacity_loss_in_an_organically_fouled_anion_exchanger?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_3http://www.researchgate.net/publication/228616243_Capacity_loss_in_an_organically_fouled_anion_exchanger?enrichId=rgreq-9ea90db5-8970-4231-a9b1-5cc0238847b6&enrichSource=Y292ZXJQYWdlOzIyODYxNjI0MztBUzoxMDQzMzQ5MjI2MTY4MzdAMTQwMTg4Njc5MzE4Mg%3D%3D&el=1_x_2

7/23/2019 0deec51ec02c556e15000000

2/6

0011-9164/06/$ See front matter 2006 Elsevier B.V. All rights reserved

Desalination 189 (2006) 303307

Capacity loss in an organically fouled anion exchanger

Z. Beril Gnder*, Yasemin Kaya, Ilda Vergili, Hulusi BarlasEnvironmental Engineering Department, Faculty of Engineering, Istanbul University, 34320 Avcilar-Istanbul, Turkey

email: [email protected]

Received 27 April 2005; accepted 29 July 2005

Abstract

One of the most important contaminants that ion-exchange resins are exposed to is fouling by organic materials.Especially, anion-exchange resins are more sensitive to fouling by organic materials. The fouling of anion-exchangeresins by organic materials is primarily caused by the degradation of products of cation ion exchangers and humic andfulvic acids. Organic fouling causes product water with low quality and few anion exchangers and shortens the servicetime. Also the need for rinsing water and the use of regeneration chemicals increase. Operating capacity lossesoccurring due to the fouling of anion-exchange resin by humic acid were quantitatively determined. SAK254(SpektralerAbsorptions Koeffizient = spectral absorption coefficient), DFZ436(DurchsichtsFarbZahl = indexes of transparency),conductivity and sulfate measurements were made to determine capacity losses, which were obtained as 21%, 23%,25% and 30% after the fouling studies of anion-exchange resin by the amounts of 0.13, 0.25, 0.5 and 1.0 mg/L humicacid, respectively. It was found that even small concentrations of humic acid resulted in a considerable amount ofcapacity losses in anion-exchange resin.

Keywords: Organic fouling; Humic acid; DFZ436; SAK254; Operating capacity

1. Introduction

Very high quality water is needed through

various stages of processing in many industries

(e.g., semiconductor, pharmaceutical, chemical,etc.). Ion-exchanger systems currently have wide-

spread use for this purpose. Some problems are

encountered during their use (loading, back-

washing and regeneration), which affect the

*Corresponding author.

performance of ion-exchange resins. The most

important one amongst these problems is the

fouling of ion-exchange resins [1,2].

Fouling with organic materials is the mostimportant one that ion-exchange resins encounter.

Organic fouling is an irreversible fixation of or-

ganic materials to the ion-exchange resin. Especi-

ally, anion exchange resins are more sensitive to

fouling with organic materials [3].

7/23/2019 0deec51ec02c556e15000000

3/6

Z. Beril Gnder et al. / Desalination 189 (2006) 303307304

The fouling of anion-exchange resins byorganic materials is primarily caused by thedegradation products of cation exchangers and

humic and fulvic acids. Organic fouling results inproduction of low-quality (high conductivity, lowpH), low amounts of water and some great prob-

lems such as early breakthrough and long wash-ing periods after regeneration. The capacity of theion-exchanger bed decreases and water with

desired quality is not produced due to the foulingthat was not removed fully by means of regene-

ration and backwashing [3,4].Natural waters contain organic, inorganic andbiological compounds in various ratios. Organicmaterials have a high share amongst these com-

pounds. Sources of organic materials in thesewaters are decomposition products of wood andleaves or industrial and domestic wastes [5].

Organic materials are largely composed of humicmaterials. Humic materials are classified intothree groups according to their solubilities in

water [6]: (1) humin, that is the part which is notsoluble at any pH value; (2) humic acid, that is

the part which is not soluble in (pH

7/23/2019 0deec51ec02c556e15000000

4/6

Z. Beril Gnder et al. / Desalination 189 (2006) 303307 305

quantitatively by searching fouling of resin withhumic acid which is a fraction of humic material.

Lewatit M 500, frequently used in deminerali-

sation applications, was chosen as the strongly

basic anion exchanger. Technical specifications

of the resin (Lewatit M 500), provided from

Bayer Leverkusen, are given in Table 1.

A laboratory-scale glass column with a 2 cm

diameter and 45 cm height was used throughout

the experiments. The column was filled with a

strong anion-exchange resin of 50 mL in volume.

Synthetic water, prepared by dissolving Na2SO4in distilled water with appropriate amounts resul-

ting 150 mg/L SO42!content, was used. The syn-

thetic water was supplied to the system by using

a peristaltic pump (Prominent) and the feed rate

was adjusted to V= 5.0 m/h (specific flow rate =

31 bed volume/h). A humic acid solution was

used in the fouling studies. This solution was

prepared according to the Urano method: 1 g

humic acid was dissolved in 100 mL 0.1 N NaOH

solution and then distilled water was added up to

1 L after waiting for 1 day [14].

The following method was used for the deter-

mination of changes occuring in ion-exchange

capacity in the studies performed for the fouling

Table 1

Technical specifications of the strongly basic anion

exchanger (Lewatit M 500)

Properties Strongly basic

anion exchanger

Ionic form Cl!

Functional group Quarternary amine,

Type 1

Structure Gel

Total capacity, min. eq /L 1.4

Bead size, mm 0.47

Flow rate, max. m/h 40

Regenerant NaOH

Regenerant level, g/L 100

Regenerant con., % 24

of ion-exchange resins. The method is based uponthe comparison of resin after being regenerated

with a new resin sample [15,16]. In this study this

method is taken as a reference.

Changes in resin capacity during the fouling

of the anion-exchange resin were determined by

using humic acid in the amounts of 0.13, 0.25, 0.5

and 1.0 mg/L. The amount of 15 mg/L SO42!value

was taken as the breakthrough point and column

loading was continued until this value was

reached at the outlet. SAK254(Spektraler Absorp-

tionsKoeffizient = spectral absorption coefficient)[17], DFZ (Durchsichts Farbzahl = indexes of

transparency) [18] and conductivity measure-

ments were performed for the samples taken from

the column outlet during fouling.

SAK254and DFZ436measurements were made

by using Jenway UV-Vis (model 6105) and

Pharmacia LKB-Novaspec II spectrophotometers,

respectively. Conductivity measurements were

carried out by a WPA CM35 conductivity device.

Sulphate measurements were implemented

according to the turbidimetric method as defined

in Standard Methods [19].

A 4% NaOH (12 bed volume/h) solution of

300 mL (6 bed volume) in volume was used for

the strong anion-exchange resin regeneration.

Cocurrent regeneration was carried out in the

study. The regenerated resin was backwashed

with distilled water until the conductivity of the

effluent was less than 1 S/cm.

3. Results and discussion

A strong basic anion-exchanger was fouled

with 0.13, 0.25, 0.5 and 1.0 mg/L humic acid and

raw water was passed through after regeneration.

The capacity of the ion exchanger was calculated

by obtaining breakthrough curves belonging to

the cycles of raw water passed through fresh ion-

exchanger resin and through ion-exchanger resin

fouled with humic acid and subsequently regene-

rated (see Figs. 14).

7/23/2019 0deec51ec02c556e15000000

5/6

Z. Beril Gnder et al. / Desalination 189 (2006) 303307306

Fig. 1. Breakthrough curves obtained from the fouling ofstrong anion exchanger with 0.13 mg/L humic acid.(a) raw water, (b) raw water containing 0.13 mg/L humic

acid, (c) raw water after regeneration.



The capacity loss was found to be 21% for the

fouling of anion-exchange resin with 0.13 mg/L

humic acid. In this case, organic material causes

high capacity losses even in small amounts. The

capacity losses were found to be 23% and 25%for the humic acid amounts of 0.25 and 0.5 mg/L,

respectively. A 30% capacity loss was observed

as the humic acid amount reached 1.0 mg/L

value. The capacity losses are shown in Fig. 5.

Capacity losses increased as the humic acid

amounts increased. The reason for this is that

humic acid which is a high molecular organic

material blocks the pores of anion exchange resin

which in turn prevents ions moving into the resin.





This situation could not to be ceased even by the

regeneration process [4].

DFZ436and SAK254parameters measured for

the samples taken from the outlet of the ion-

exchange column were evaluated during foulingstudies. DFZ was measured as zero for the

samples taken up to 15 mg/L SO4=value which

was chosen as the breakthrough point during the

fouling studies made with 0.13, 0.25, 0.5 and

1.0 mg/L humic acid values. In other words, no

colour was observed in the samples taken from

the column outlet. SAK254 values were deter-

mined to be zero for samples taken up to the

breakthrough point during the fouling of anion-

7/23/2019 0deec51ec02c556e15000000

6/6

Z. Beril Gnder et al. / Desalination 189 (2006) 303307 307

Fig. 5. Capacity losses occurring in strong anionexchange.

exchange resin with 0.13 and 0.25 mg/L humic

acid. When the humic acid amount was 0.5 mg/L,

SAK254 values were observed for the samples

taken from column outlet after the passage of

15.3 L water fouled by humic acid (bed volume

= 306). SAK254value was measured as 0.9 m!1at

the breakthrough point. When the humic acid

amount was 1.0 mg/L, SAK254 values were

observed for the samples from the column outlet

after the passage of 14.5 L water fouled by humic

acid (bed volume = 290), and this value became

2.6 m!1at the breakthrough point. The reason for

this is the blockage of ion-exchange points

existing in ion-exchangers structure by a large

amount of humic acid. As a result, the capacity of

resin decreases.

References

[1] F.N. Kemmer, Ion Exchange, Nalco Water Hand-

book, 2nd ed., Mc Graw-Hill, New York, 1988,

pp. 12.112.45.

[2] P.N. Cheremisinoff and N.P. Cheremisinoff, Water

Treatment and Waste Recovery: Advanced Tech-

nology and Applications, Prentice Hall, Englewood,

NJ, 1993, pp. 288289.

[3] K. Dorfner, Ion Exchange Types, Ion Exchangers

Properties and Applications, 2nd ed., Ann Arbor

Science, Michigan, 1972, pp. 168170.

[4] G.C. Lee, G.L. Foutch and A. Aranuchalam, Reac-

tive Func. Polym., 35(10) (1997) 5573.

[5] H. Yldrm, Contribution of ionic strength to the

interaction of natural organic matter and metal oxide

surface, Masters Thesis, Bogazici University, Istan-

bul, Turkey, 2000.

[6] APHA-AWWA-WEF, Standard Methods for the

Examination of Water and Wastewater, 19th ed.,

Washington, 1995, pp. 5.275.28.

[7] S.A. Suphandag, Adsorption capacity of natural

organic matter on semi-conductor powders, Master

Thesis, Bogazici University, Istanbul, Turkey, 1998.

[8] M. McCoy, Ion Exchange, Ultrapure Water, TallOaks, Littleton, CO, 1996, pp. 2031.

[9] R.G. Alther, Preventing Resin and Membrane

Fouling with Clay Prepolish, Biomin, MI, 2000.

[10] W. Bornak, Resin Analysis and Chemical Cleaning,

39th Liberty Bell Water Treatment Course, Atlantic

City, New Jersey, 2001.

[11] Purolite Company, The fouling of ion exchange

resins and methods of cleaning, Purolite Technical

Bulletin, 1998.

[12] H. degard, B. Eikbrokk and R. Storhaug, Water

Sci. Technol., 40 (1999) 3746.

[13] J.F. Desilva, Removing organics with ion exchange

resin, Water Conditioning Purification, (1997) 13.[14] S.C. Uyguner, Trace-level metals and natural organic

matter interactions: Oxidative/adsorptive removal

pathways, Master Thesis, Bogazici University,

Istanbul, Turkey, 1999.

[15] Deutsche norm, DIN 54 402: Bestimmung der

Totalen Kapazitt von Anionenaustauschern, Beuth,

Berlin, 1982.

[16] Deutsche norm, DIN 54 403: Bestimmung der

Totalen Kapazitt von Kationenaustauschern, Beuth,

Berlin, 1982.

[17] DIN 38404, Deutsche einheitsverfahren zur wasser-,

abwasser-und schlammuntersuchung- physikalisch-chemische kenngren (gruppe C), Teil 3: Bestim-

mung der absorption im bereich der UV-strahlung;

spektraler absorptionskoeffizient (C3), Beuth, Berlin,

2003.

[18] H. Barlas and T. Akgun, Fresenius Environ. Bull., 9

(2000) 597602.

[19] APHA-AWWA-WEF, Standard Methods for the

Examination of Water and Wastewater, 19th ed.,

Washington, 1995, pp. 4.1364.137.

0deec51ec02c556e15000000

Documents