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DESALINATION

ELSEVIER Desalination 153 (2002) 155-160


www.elsevier.comhcate/desal

Investigation of membrane fouling

T. Mohammadi”, S.S. Madaeni, M.K. Moghadam


Research Laboratory for Separation Processes, Faculty of Chemical Engineering, Iran University of Science and
Technology, Iust Narmak, Tehran, Iran
Tel. + 98 (21) 7896621; Fax +98 (21) 7896620; emailr torajmohammadi@yahoo.com

Received 30 March 2002; accepted 15 April 2002

Abstract

Fouling of ultrafiltration membranes in milk industries is mostly due to precipitation of microorganisms, proteins,
fats and minerals on the membrane surfaces. Thus, chemical cleaning of the membranes is essential. In this paper,
results obtained from investigations on a polysulfon ultrafiltration membrane fouled by precipitation of milk
components have been presented. In this research the effect of different cleaning agents on the recovery of the
fouled membrane has been studied. Results show that a combination of sodium dodecyl sulfate and sodium hydroxide
can be used as a cleaning material to reach the optimum recovery of the polysulfon membranes used in milk
concentration industries. Also a mixture of sodium hypocholorite and sodium hydroxide shows acceptable results,
where washing with acidic material has no considerable performance.

Keywords: Membrane; Ultrafiltration; Milk; Fouling; Chemical cleaning

1. Introduction decline. To overcome this problem, a cleaning process


must be used. Cleaning usually performs in three
Membrane foulingphenomenapresent important
forms: physical, chemical and biological [l].
limitations on the technology applied. Fouling is
Chemical methods are used more often. The first
defined as existence and growth of micro-
step of chemical washing is finding appropriate
organisms and irreversible collection of materials
materials as cleaning agents. The choice of the
on the membrane surface which results in a flux
best materials depends on feed composition and
precipitated layers on the membrane surface and
*Corresponding author.

Presented at the EuroMed 2002 conference on Desalination Strategies in South Mediterranean Countries:
Cooperation between Mediterranean Countries of Europe and the Southern Rim of the Mediterranean.
Sponsored by the European Desalination Society and Alexandria University Desalination Studies and Technology
Center, Sharm El Sheikh, Egypt, May 4-6, 2002.

001 I -9164/02/$- See front matter 0 2002 Elsevier Science B.V. All rights reserved
PII:SOOll-9164(02)01118-9
196 7:Mohammadi et al. / Desalination 153 (2002) 155-160

in most cases is performed by trial and error [2]. 3. Fouling and cleaning processes
The selected materials should be chemically stable,
All of the ultrafiltration experiments have been
safe, cheap and washable with water [3]. These
performed in a cell in the form of crossflow on the
materials must also be able to dissolve most of the
membranes having a surface of 29.24 cm2. Mem-
precipitated materials on the surface and remove
brane is put in its special location and the permeation
them from the surface while not damaging the
flux of distilled water, <,#,at a temperature of 3ti 1“C
membrane surface [4].
and a pressure of 3 bar is measured in 10 min.
Some of these cleaning agents are acids, bases,
In the second step - fouling, feed at a temp-
enzymes, surfactants, disinfectants and combined erature of 5O*l”C and pressure of 3 bar enters the
cleaning materials [l ,Sj. While using these materials
system. The fouling operation has been performed
as cleaner, effect of some parameters like pH, con- for all samples in 30 min to make similar fouling
centration and washing time 143 and operating
conditions and particle precipitation on membranes
conditions like crossflow velocity, pressure and
in all samples. Feed is passed through the membrane
temperature [6,7] must be considered . In order surface continuously with a linear crossflow velocity
to clean the membranes fouled with milk and
of 1 m/s. The flux of this step is introduced as Jl,?
whey, one base washing step followed by an acid
In the next step, the fouled membrane is washed
washing step was advised [6] and to get better with distilled water and then the permeation flux
results one enzyme washing step could be used of distilled water, J,,,,,is measured.
before chemical washing [2]. Thus to reach the
Then, chemical washing at a temperature of
optimum conditions for cleaning processes, having 30&l OCand with no pressure is performed within
enough information about operating conditions 30 min and then the final flux of distilled water,
and effects of cleaning materials is necessary [3,8]. J,, is measured. Thus, in all experiments distilled
In this paper, results of investigations on the
water flux is measured three times: (&, J, ,,,“,JJ.
polysulfone membrane used in milk concentration
Formation of cake or gel on the membrane surface
are presented. In these studies, effects of different or into its network increases fouling due to the
washing materials on the performance of the
fact that present pores are blocked or become narrow
membrane recovery have also been investigated.
and this finally decreases the permeation flux.
Fouling was evaluated using resistance removal
2. Experiments and flux recovery [9].
Therefore using these two parameters (RR and
In all experiments a polysulfone membrane
FR), effectiveness of different chemicals with
with a molecular weight cutoff (MWCO) of 30
different concentrations and operating conditions
KD produced by Dow Company in Denmark has
can be compared.
been used.
In all experiments, feed was supplied from
Tehran pasteurized milk factory. The following 3. Results and discussion
chemicals have been used as cleaning agents:
After feed filtration, some materials which are
Material Company
not adsorbed on the membrane surface can be
Sodium hydroxide Panreac
Fluka
washed with distilled water. This requires less
Sodium hypocholorite
Hydrochloric acid Merck chemicals for cleaning [9]. As shown in Fig. 1,
Sulfuric acid Merck flux recovery increases within 20 min and then it
Nitric acid Merck remains almost constant. So, it seems that 20 min
Ethylene diamine Tetra acetic acid (EDTA) Merck washing with water before chemical cleaning
Sodium dodecyl sulfate Merck must be enough and is quite effective. During the
T. Mohammadi et al. / Desalination 153 (2002) 155-160 157

WRR IJFR 100

5 15 30 60 1 10 20 30 40
Time (min) Time (min)
Fig. 1. Effect of washing time on resistance removal and Fig. 2. Effect of cleaning time on flux recovery and
flux recovery. resistance removal.

washing step, crossflow velocity ofwater is adjusted


IOOfj
to a value of 1 m/s to take the materials away from P

the membrane surface.


Using an optimum time for cleaning of
membranes can reduce the operational cost. In
chemical cleaning, chemicals need enough time
to react with the precipitated materials. Therefore,
it is predicted that increasing cleaning time increases
flux recovery at the beginning of cleaning step.
As shown in Fig. 2, flux recovery increases within
30 min using sodium hydroxide solution (0.5 M),
but more cleaning time has no effect on the flux
0. 01 0. 05 0. 2 0. 35
recovery.
Concentration, ww %
Fig. 3 shows the effect of sodium hydroxide
concentration on cleaning efficiency. Increasing Fig. 3. Effect of sodium hydroxide concentrations on
the concentration up to 0.8, increases the flux cleaning efficiency.
recovery considerably. There is no considerable
effect when concentration is between 0.8 and 1.1 hypochlorite concentration on cleaning efficiency
and at concentrations more than 1 .l the flux is shown in Fig. 4. This figure shows that with a
recovery decreases. Also in the range of 0.6-l .2, change in concentration from 0.01 to 0.02 a rapid
there is no sensible difference in resistance removal. improvement occurs in efliciency and flux recovery
Therefore sodium hydroxide can well dissolve increases from 32 to 87 and resistance removal
molecules of proteins, fats and other precipitated increases from 6 1 to 97. Efficiency more than 100%
materials at a concentration of 0.6-0.8 and make at a concentration of more than 0.4 is an unexpected
them far from the membrane surface. result. Here, two general reasons can explain the
Sodium hypochlorite with its oxidizing charac- matter. First, the structure of the membrane is
teristic can remove particles from the membrane damaged as a result of contact with sodium hypo-
surface. It sometimes enters the pores and increases chlorite with concentration more than 0.4 and it
their effective diameter as a result of absorbed is partially destroyed. Therefore pores’ shape is
material removal. Therefore it can increase the changed and they may be larger and an efficiency
amount ofthe permeation flux. The effect of sodium more than 100% is observed.
158 T Mohammadi et al. /Desalination 153 (2002) 155-160

on the membrane surface than fats and proteins


' n FR
I- which form external layers of precipitation and
acids cannot dissolve upper layers of the cake but
bases can. On the other hand, acids can dissolve
minerals. Therefore, in cleaning processes of
membranes fouled with milk, base washing
followed by acid washing has been advised. It
should also be mentioned that acids can sometimes
cause cake layer to be compressed, and this con-
sequently increases the resistance.
In the previous section, it was mentioned that
acids cannot dissolve upper layers of cake and
Concentration, ww % remove them. This is also correct for nitric acid.
Fig. 4. Effect of sodium hypochlorite concentrations on As Fig. 6 shows, the lowest nitric acid concen-
cleaning efficiency. tration has a relatively better performance, but
generally none of the concentrations shows
Second, sodium hypochlorite causes the mem- acceptable results.
brane to be more hydrophilic and in addition to Ethylene diamine tetra acetic acid (EDTA) has
membrane cleaning, it makes the permeation flux six positions to form bonds. Thus it is expected to
to increase. form complexes with some particles and separate
According to Fig. 5, at a hydrochloric acid con- them from the membrane surface. Experimental
centration of 0.01, the flux recovery is maximum. results show that although increasing the concen-
Increasing the concentration, decreases the flux tration increases the. flux recovery, it is not con-
recovery. To explain this phenomenon it can be siderable as shown in Fig. 7.
said that materials precipitated on the membrane Sodium dodecyl sulfate (SDS) is a surfactant
surface are mainly proteins, fats and minerals and it decreases the surface tension of molecules
which exist in milk. Minerals are adsorbed faster which are in contact with it. This material can
also improve hydrophilic&y of polysulfone mem-
branes. Therefore, it is expected to have acceptable
results as a cleaning material. Fig. 8 shows that
this material has no considerable effect on the flux
recovery. Following the results, it is observed that
with increasing the concentration up to 0.5%, the
efficiency increases and then decreases.
Regarding the previous section and the fact
that sodium hydroxide has an ability to dissolve
proteins and fats, it can be expected that the
combination of these two materials is effective
for membrane recovery. Fig. 9 shows that the
expectation is right. In chart 1, the membrane has
0. 01 0. 05 0. 1 been submerged in a solution of 0.5% SDS and
Concentretign, ww % 0.5% NaOH for 2 h. In chart 2, the concentration
Fig. 5. Effect of hydrochloric acid concentrations on of NaOH has been changed to its optimum value
cleaning efficiency. (%0.8). After submerging in the solution for 2 h,
I: Mohammadi et al. / Desalination 153 (2002) 155-160 159

0. 5 0. 7 1
0. 01 0. 05 0. 1 1
Concentration, ww %
Concentration, ww %
Fig. 6. Effect of nitric acid concentrations on cleaning Fig. 7. Effect of EDTA concentrations on cleaning
efficiency. efficiency.

RR n FR
60
100

50

s* 40

p 3o
0.5/0.5 OS/O.8 0.710. 8 O.!
20
Concentration, ww %

IO Fig. 9. Membrane recovery for different concentrations of


NaOH and SDS at different time.
0
0. 1 0. 5 0. 7

Concentration, ww % was considered (i.e. 0.5% NaOH and 0.3% SDS).


The result was not in the expectes range (chart 6).
Fig. 8. Effect of SDS concentrations on cleaning effkiency.
Finally, concentration of SDS has been changed
to 0.5% and this caused the membrane recovery
an acceptable result has been observed. In chart 3, efficiency to reach the maximum limit (chart 7).
the membrane has been submerged for 3 h in the Thus for a continuous system, the use of the con-
same solution and no important changes in effl- centration described in the last experiment was
ciency have been observed compared to chart 2. recommended.
In charts 4 and 5, the SDS concentration has been
changed to 0.7% and the membrane has been
5. Conclusions
submerged for 1 and 2 h subsequently. The flux
recovery results were not acceptable. From the It can be concluded that for all parameters and
results, it was expected that washing with these factors which affect cleaning and ultrafiltration
mixtures should cause more acceptable results. processes, there is an optimum value which can
Thus a lower concentration for this combination be determined depending on the type of solution
160 7: Mohatnmadi et al. i Desalination 1.53 (2002) 155-160

to be processed. Experimental results show the J 11’1,’- Fouled membrane permeation flux, I/m’.h
optimum operating values as follows: 4,‘ - Cleaned membrane permeation flux, l/m2.h
Sodium’hydro~ide in the concentration range R,,, - New membrane resistance, m-’
of 0.6-0.8 causes the best result. Higher con- - Fouled membrane resistance, In-’
R,
centrations cause the efficiency of the flux R‘ - Cleaned membrane resistance, m-’
recovery to decrease, thus for chemical washing AP - Pressure difference, Pa
of polysulfone membranes, this concentration RR - Resistance removal indicator
range is optimum . FR - Flux recovery indicator
Sodium hypochlorite with the concentration
of 0.2 shows a good result, but using the chemical
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