Journal of Membrane Science 456 (2014) 167174

Contents lists available at ScienceDirect

Journal of Membrane Science

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

Treating laundry waste water: Cationic polymers for removal

of contaminants and decreased fouling in microltration
Hyun-Chul Kim a, Xia Shang a, Jin-Hui Huang b, Brian A. Dempsey a,n
a
b

Department of Civil and Environmental Engineering, Pennsylvania State University, University Park, PA 16802, USA
College of Environmental Science and Engineering, Hunan University, China Changsha 410082, PR China

art ic l e i nf o

a b s t r a c t

Article history:
Received 25 November 2013
Received in revised form
10 January 2014
Accepted 11 January 2014
Available online 21 January 2014

The goal was to select coagulants and a coagulation process for treating laundry wastewater. The longterm goal is for application in Army mobile treatment units with solids removal using microltration
(MF) and for which a robust operation with small coagulant volumes are desirable. Laundry wastewater
usually has very high pH thus strong base cationic polymers are good coagulant candidates. Seven
quaternary amine polymers were examined to determine effects of coagulant dose on zeta potential (ZP).
Four of the polymers were further evaluated for sedimentation of contaminants, specic resistance to
ltration, and cake compressibility during ltration. A low molecular-weight epichlorohydrin/dimethylamine (epi/DMA) polymer was tested further because of greatest increase in ZP with low polymer dose,
lowest specic resistance to ltration, and good removal of contaminants. Flocculation for 10 min
resulted in greatly improved removal of cake by hydraulic washing compared to 2 and 5 min occulation.
Fouling during multi-cycle membrane operation was greatly reduced with coagulant additions less than
half the charge-neutralization (CN) dose. Low polymer dose results in decreased chemical demand and
reduced sludge production. Successful treatment using from 50% to 100% of the CN dose provides more
robust operation under eld conditions.
& 2014 Elsevier B.V. All rights reserved.

Keywords:
Laundry lint
Wastewater reuse
Cationic polymer
Coagulation
Microltration
Fouling

1. Introduction
This paper deals with coagulation of laundry wastewater with
quaternary amine polymers and solids removal by sedimentation
or low-pressure membrane ltration. The research is motivated by
the need to recycle laundry wastewater at Army forward operating
bases using the Tricon Shower Water Reuse System (SWRS) in
which microltration (MF) of laundry wastewater without prior
coagulation can result rapid membrane fouling. The results will be
useful for treatment of laundry wastewater in any venue.
The most widely employed strategies for treatment of laundry
wastewater are coagulation, adsorption, otation, adsorption,
ltration with media, and membrane ltration [18]. Coagulation
can be effective for removal of chemical oxygen demand (COD),
phosphates, and anionic surfactants. Coagulation produces oc that
must be removed by a solid separation process. MF or ultraltration
(UF) membranes are increasingly used for solid separation and

n
Correspondence to: Department of Civil & Environmental Engineering,
Pennsylvania State University, 212 Sackett Building, University Park, PA
16802-1408, USA. Tel.: 1 8148651226; fax: 1 8148637304.
E-mail addresses: animaplus@hanmail.net (H.-C. Kim),
xqs5036@psu.edu (X. Shang), huangjinhui_59@163.com (J.-H. Huang),
bad5@psu.edu (B.A. Dempsey).

0376-7388/$ - see front matter & 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.memsci.2014.01.028

these processes are compatible with in-line application of coagulants [9].

Inorganic coagulants are typically effective only when a precipitate forms, usually with a net charge opposite to the charge on
the contaminants. For example, alum or ferric chloride work best
when the nal pH results in precipitation of the metal oxides and
when the initially formed precipitates have sufcient positive
charge to neutralize negative charge on humic materials, clays,
and other common constituents in water. Laundry wastewater,
however, typically has very high pH and is well-buffered with
respect to pH. Ge and coworkers [7] reported that contaminant
removals from laundry wastewater were poor when using inorganic coagulants for pH o 4 or 49. Similarly, electrocoagulation
did not improve ux compared with raw water in polyvinylidine
uoride (PVDF) MF [10]. Strong base cationic polymers retain a
high positive charge at high pH values are consequently are good
candidates for coagulation of laundry wastewater.
The goal was to identify coagulants and coagulation processes
to achieve the following objectives during treatment of laundry
wastewater at high pH: (1) remove contaminants especially total
suspended solids (TSS), total chemical oxygen demand (TCOD),
and total phosphorus (TP); (2) effective removal of coagulated
solids by sedimentation or MF; (3) substantial decrease in MF
fouling compared to raw laundry wastewater; and (4) effective
operation over a wide range of coagulant doses to achieve simple

168

H.-C. Kim et al. / Journal of Membrane Science 456 (2014) 167174

and robust operation. Experiments were conducted in three

phases: (1) seven strong-base cationic polymers were screened
to determine charge-neutralization (CN) effectiveness at pH 11;
(2) four cationic polymers were selected for evaluation of contaminant removal by sedimentation, specic resistance to ltration, and cake compressibility; (3) one cationic polymer was
selected for additional tests including effect of occulation time
and chemical dose on MF performance during multi-cycle tests
meant to simulate continuous operation of the SWRS.

2. Materials and methods

2.1. Laundry wastewater
Wastewater was collected from an industrial laundry in Centre
County PA during hours when only commercial uniforms were
washed. Temperature and pH were measured onsite. The sample
was immediately transported to the laboratory, ltered with
10 m polypropylene mesh lters, pH adjusted to 11, and stored
in a walk-in-refrigerator for further experiments. Table 1 shows
the wastewater characteristics.
2.2. Coagulant titrations and jar tests
Seven quaternary amine (strong base) cationic polymers were
initially selected to provide a range of apparent molecular weight,
composition, and form (water solution, emulsion, and dispersion).
Table 1
The characteristics of laundry wastewater samples
collected on six different dates from a local industrial laundry.
Parameter

Value

pH
Temperature (1C)
Zeta potential (mV)
Conductivity (S cm  1)
Total dissolved solids (mg L  1)
Turbidity (NTU)
TSS (mg L  1)
TCOD (mg L  1)
TP (mg P L  1)

12.5 7 0.5
407 1.0
 57.4 7 8.5
7247 123
3577 52
858 7 111
3597 82
11387 58
227 4

All polymers were diluted according to manufacturer's specications with deionized water to 1% (v/v) just before use. The 1%
solutions were typically stored at room temperature. Prior to some
experiments the 1% solutions were stored at 4 1C or 40 1C. All
polymer doses are expressed in ppm (v/v). Characteristics of the
polymers are shown in Table 2.
Coagulant titration tests were conducted by adding increasing
volume of polymer beneath the water surface in the vortex of a
rapidly stirred wastewater sample and measuring pH and zeta
potential (ZP). Polymer doses were increased until several positive
ZP readings had been recorded. Zero ZP is an indicator for the CN
condition, i.e., the negative charge on contaminants has been
exactly titrated by positive charge from the coagulant. Underdosing (UD) refers to coagulant additions less than the CN dose
resulting in residual negative charge on the coagulated ocs, while
over-dosing (OD) means coagulant addition greater than the CN
condition resulting in net positive charge on the ocs. Four
signicantly different polymers were selected based on the titration tests for jar tests and specic resistance to ltration tests.
Jar tests were performed using the four selected polymers to
measure removals of turbidity, TSS, TCOD, and TP after sedimentation. Total means dissolved plus suspended contaminants after
1 hr sedimentation. Tests were conducted with a Phipps & Bird
stirrer with conventional blades (Model 7790-400) by adding
selected volumes of 1% solutions of polymer into wastewater with
1 min high speed mixing and then 30 min mixing at a velocity
gradient of 200 s  1. Samples were collected at the end of the
mixing for ZP measurement. Supernatant was collected for the
other analyses from just below the water surface after 1 h
quiescent settling. Most jar tests were conducted at room temperature (E22 1C) but some tests were conducted in water baths
at 40 1C.

2.3. Effects of coagulants on specic resistance to ltration

and compressibility
Flat-sheet hydrophobic 0.22 m PVDF MF membranes
(GVHP04700, Millipore) were used. Membranes were wetted in
methanol and then soaked in deionized water overnight. A deadend ltration system was used to estimate cake characteristics
(Fig. 1a). Head loss from velocity head (v2/2g) and elevation (h)
were negligible, where v is the uid velocity (m s  1) and g is
gravitational acceleration (9.8 m s  2).
The pre-wetted membrane was placed in a commercial ltration cell (polycarbonate lter holder, Pall Sciences) with 9.6 cm2

Removals of turbidity, TSS, TCOD, and TP by preltration with 10 m polypropylene mesh lters
were 177 6, 347 3, 147 6, and 2 71%, respectively.

Table 2
The characteristics of polymers (in alphabetic order) provided by manufacturer.
Polymer brand

Cat-oc 8102 plus

Cat-oc 8108 plus
Core shell 71301
Core shell 71303
Core shell 71305
Nalcolyte 8105
Ultimer 1460

Ionicity

Cationic
Cationic
Cationic
Cationic
Cationic
Cationic
Cationic

Charge density
(%)a

(meq g  1)b

100
100
5080
2050
130
100
5080

6.2
6.2
3.84.7
2.13.8
0.12.8
7.3
4.35.6

Molecular weight

Composition

Form

Medium
High
High
Very high
Very high
Low ( o50 K)
High

PolyDADMAC
PolyDADMAC
AcAm/DMAEA.MCQ
AcAm/DMAEA.MCQ
AcAm/DMAEA.MCQ
Epi/DMA
AcAm/DADMAC

Water solution
Water solution
Emulsion
Emulsion
Emulsion
Water solution
Dispersion

(Poly)DADMAC (poly)diallyldimethyl-ammonium chloride (C8H16NCl).

AcAm acrylamide (C3H5ON).
DMAEA.MCQ dimethylaminoethylacrylate methyl chloride salt (C8H16O2NCl).
Epi/DMA epichlorohydrin and dimethylamine (C5H12ONCl).
a
b

Mole percent of charged groups (e.g., the mole% of DMAEA.MCQ in AcAm/DMAEA.MCQ).

The amount of cationic charge per gram of polymer was calculated with the mole percent of charged groups.

H.-C. Kim et al. / Journal of Membrane Science 456 (2014) 167174

Pressure
regulator

The coefcient of compressibility (n) varies from zero for an

incompressible layer to greater than 1 for a highly compressible
cake and was calculated by regression analysis using the following
equation:

Pressure
gauges

c o P nc
h

Nitrogen
gas

Pressure
vessel

Membrane
module

Nalcolyte 8105 was selected for further membrane ltration

experiments based on best values of c and n. The desired polymer
dose was added to 2 L wastewater while agitating at a velocity
gradient of 425 s  1 for 10 min.
Dead-end constant pressure experiments were performed
using only CN coagulation conditions. The wastewater was ltered
through 0.22 m PVDF MF membranes under N2 at constant feed
pressure of 10 psi for 1 h. Permeate ux and trans-membrane
pressure (TMP) values were continuously recorded.
Recirculated-ow constant ux experiments were performed
using UD, CN, and OD coagulation conditions. The coagulated
wastewater was pumped to the membrane ltration module
through a feed-side peristaltic pump. Multi-cycle ltration runs
were conducted using eight sequential cycles of ltration (15 min),
backwash (1 min at 10 psi N2), and surface ush (0.5 min). Retentate was recirculated to the supply vessel. Less than 40% of initial
sample volume was ltered in any experiment. Permeate ux (by
permeate mass) and TMP were continuously recorded.
The MF membrane was removed at the end of each membrane
ltration test, rinsed with deionized water to remove the cake
layer, and replaced in the lter assembly for measurement of pure
water ux. Subsequent chemical cleanings were performed by
soaking the membrane sheets in 0.1 M NaOH and then 0.1 M citric
acid for 12 h per each. A pure water ux test was conducted to
determine hydraulic resistance and ux recovery of the membrane
sheets after each cleaning step.

Digital
balance

1
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.

Feed tank
Feed pump
Dampener
Membrane module
Pressure control valve
Digital pressure gauge
Permeate pump
Digital balance
Pressure vessel for backwash
Nitrogen gas cylinder
Precision pressure regulator

8
11

DI water

10

2.5. Analytical methods

Fig. 1. (a) Schematic for dead-end ltration to determine specic resistance to

ltration, coefcient of compressibility, and effect of occulation time. (b) Schematic
for a multi-cycle recirculating-ow microltration tests.

effective ltration area. Raw or coagulated wastewater from a

pressure vessel (Model 720340, Advantec MFS Inc., CA) was passed
through the membrane under constant pressure (2 psi) for 25 min
while recording the ltered mass. After 25 min the feed pressure
was step-wise increased every 10 min while feed and permeate
pressures were continuously recorded. The cake mass was based
on the wastewater TSS and the permeate volume. Specic resistance to ltration was calculated using data from the separate
step-pressure experiments using the following equation [1113]:

c A=CVP=J  Rm 

2.4. Dead-end and recirculated-ow membrane ltration tests

Discharge

Cationic polymer
(1% Nalcolyte 8105)

169

where c is specic cake resistance (m kg  1), A is the effective

membrane area (m2), C is the TSS in the wastewater feed (kg m  3),
V is cumulative permeate volume (m3), P is total pressure drop
(Pa), is uid viscosity calibrated by temperature (kg m  1 s  1), J
is the permeate ux (m s  1), and Rm is the intrinsic membrane
resistance (m  1) measured using particle-free electrolyte solution.
Rm is usually obtained by determining the total pressure drop (P)
at the initial water ux (Jo) on the assumption that cake resistance
(Rc) is zero when no cake has deposited on the lter surface
[13,14]. In this study hydraulic resistance from cake itself as a
function of trans-cake pressure was determined using the continuous ltration method.

Particle size distributions (4 1 mm) were measured using

micro-ow imaging (DPA 4200 ow microscope, Brightwell Technologies Inc., Canada) on samples taken after rapid mixing at
425 s  1 for 10 min. An aliquot was diluted up to 100 times with
pre-ltered (0.2 mm) laundry wastewater, 1 mL of the diluted
suspension was introduced to the ow microscope, and the images
were analyzed by MFI View Analysis Suite (MVAS) software to
compile a database containing count, size, and shape parameters.
ZP was measured using a Zen 3600 Zetasizer (Malvern Instruments Ltd., Malvern, UK). A coagulant charge analyzer, CCA3100
(Chemtrac Systems Inc., Georgia), was used to measure streaming
current. Turbidity (Hach 2100P), conductivity (Orion, 115A ), and
pH (Orion, 290A) were measured. TSS was determined according
to the Standard Methods for the Examination of Water and
Wastewaters [15]. TCOD and TP were measured using Hach 2010
spectrophotometer. The Reactor Digestion Method was used for
TCOD. The acid persulfate method was used to digest samples for
TP (USEPA Method 365.2).

3. Results and discussion

3.1. Titration of negative charge by cationic polymers
Coagulation can occur by means of double layer compression,
adsorption of oppositely-charged species resulting in reduced
surface potential, or polymer bridging. Adsorption of oppositelycharge species results in a reduction of charge on the particle

H.-C. Kim et al. / Journal of Membrane Science 456 (2014) 167174

neat product is shipped in water solution. Both polyDADMAC

polymers performed well in neutralizing charge and one was

100

Residual turbidity (%)

surfaces so that approaching particles will collide (and hopefully

stick) rather than repel one another. ZP is considered the most
accurate way to determine when the charge on the particles has
been reduced. CN occurs when the ZP is zero. ZP is difcult to
apply on-line in real-time situations. Streaming current (SC) is an
alternative electro-kinetic measurement that is easily adapted for
real-time application and is discussed in a later section of
this paper.
ZP values for raw and coagulated laundry wastewater were
measured as a function of coagulant dose for the seven coagulants.
Results are shown in Fig. 2a with coagulant dose expressed in
ppm (v/v) and in Fig. 2b with coagulant dose in meq of added
cationic charge per liter. Nalcolyte 8105 (epi/DMA) was the most
effective coagulant based on volumetric additions while the
polyDADMAC coagulants and one coreshell polymer provided
the steepest rise in ZP as a function of added cationic charge.
Nalcolyte 8105 has the highest cationic charge per liquid volume
due to higher charge density (see Table 2) and higher liquid
density compared to the other polymers. These factors explain
the change in relative position of 8105 in Fig. 2b compared to 2a.
Two of the coreshell polymers displayed signicantly poorer
performance than the other polymers in Fig. 2b. Ester linkages in
the coreshell polymers are susceptible to base catalyzed hydrolysis resulting in decreased cationic charge [16]. Laundry wastewater pH of 11 could have partially hydrolyzed some of the ester
linkages in the coreshell polymers, resulting in apparently higher
cationic demand for CN.
Four of the seven polymers were selected for further testing.
The selection was based on several criteria including performance
in neutralizing negative charge and the desire to retain a diversity
in polymeric composition and form. Epi/DMA Nalcolyte 8105
partially neutralized negative charge at the lowest dose and the

40

20

100

200

300

400

500

100

200

300

400

500

100

200

300

400

500

80
60
40

20
0

100

0
-20

Residual TCOD (%)

Zeta potential (mV)

60

100

20

Cat-floc 8102 plus

Cat-floc 8108 plus

-40

Core shell 71301

Core shell 71303
Core shell 71305

-60

Nalcolyte 8105
Ultimer 1460

-80

100

200

300

400

500

80
60
40

20

600

Polymer dose (ppm)

20

100

0
-20

Residual TP (%)

Zeta potential (mV)

80

Residual TSS (%)

170

Cat-floc 8102 plus

Cat-floc 8108 plus

-40

Core shell 71301

Core shell 71303
Core shell 71305

-60

Nalcolyte 8105

80
60
Cat-floc 8108 plus

40

Core shell 71301

Nalcolyte 8105

20

Ultimer 1460

Ultimer 1460

-80

0.2

0.4

0.6

0.8

1.2

Polymer dose (meq-cationic charge L -1)

Fig. 2. Zeta potential versus polymer addition for the coagulation of laundry
wastewater at pH 11 and room temperature: (a) polymer dose expressed in partpermillion (v/v); (b) polymer dose expressed as meq L  1 of cationic charge added.

100

200

300

400

500

Polymer dose (ppm)

Fig. 3. Removals of turbidity, TSS, TCOD, and TP after sedimentation. Polymer dose
in ppm (v/v). Flocculation was 30 min at a velocity gradient of 200 s  1 and
sedimentation for 1 h.

H.-C. Kim et al. / Journal of Membrane Science 456 (2014) 167174

1.E+06

80

Particle concentration
(number 102 mL-1)

Residual turbidity (%)

100

Raw wastewater
Cat-floc 8108 plus (148 ppm)

60

Core shell 71301 (118 ppm)

Nalcolyte 8105 (99 ppm)

40
20
0

10

20

30

40

50

60

70

1.E+05

1.E+04
Raw wastewater

1.E+02

16

y = 0.8x + 11.1
y = 0.7x + 11.2

15

y = 0.5x + 12.9

y = 0.9x + 8.7

y = 0.5x + 11.3

4.3

4.8

5.3

5.8

log (specific resistance, c) [m kg-1]

log (Pc) [Pa, N m-2]

17

y = 0.8x + 11.7

15
y = 0.7x + 11.7

y = 0.8x + 10.5
y = 0.7x + 9.6

13
12

3.8

4.3

4.8

15

20

25

50
Raw wastewater
40% of the dose for CN
50% of the dose for CN
100% of the dose for CN
250% of the dose for CN

10

100

Fig. 6. Flocculated particle sizes as a function of mixing time and Nalcolyte 8105
coagulant dose: (a) total particle concentrations as a function of dose and mixing
time; (b) cumulative particle counts (50th percentile crossover is the median
diameter for each dose. Velocity gradient was 425 s  1 for 10 min. Polymer doses
80, 100, 200 (charge neutralization), or 500 ppm(v/v).

3.2. Coagulation and sedimentation of laundry wastewater

y = 0.7x + 11.2

14

10

difculties in preparing a 1% solution in the eld. Ultimer 1460

was the only polymer in the AcAm/DADMAC category and was
retained as the fourth polymer.

Raw wastewater
Cat-floc 8108 plus (100 ppm)
Core shell 71301 (60 ppm)
Nalcolyte 8105 (80 ppm)
Ultimer 1460 (80 ppm)

16

Particle diameter (m)

13

3.8

100

14

250% of the dose for CN

Elapsed mixing time (min)

Cumulative %
less than indicated size

log (specific resistance, c) [m kg-1]

Raw wastewater
Cat-floc 8108 plus (290 ppm)
Core shell 71301 (120 ppm)
Nalcolyte 8105 (158 ppm)
Ultimer 1460 (235 ppm)

50% of the dose for CN

100% of the dose for CN

Fig. 4. Residual turbidity of raw and coagulated laundry wastewater as a function

of settling time. Flocculation mixing was 10 min at velocity gradient of 425 s  1.
Samples collected from an outlet port 5 cm above the bottom of a 2.4 L-volume
rectangular beaker.

17

40% of the dose for CN

1.E+03

Settling time (min)

12

171

5.3

5.8

log (Pc) [Pa, N m-2]

Fig. 5. Specic resistance to ltration and coefcient of compressibility (slope of
lines) during dead-end constant pressure ltration of raw and coagulated laundry
wastewater through 0.22 m PVDF membranes. Two coagulation regimes for each
polymer were employed: (a) polymer dose that achieved maximum contaminant
removals after sedimentation and (b) lower polymer doses that achieved signicant
contaminant removal by sedimentation (see Fig. 3).

retained. Among the coreshell polymers, 71301 had the highest

charge density and neutralized negative charge in laundry wastewater most effectively. It was retained despite difculties presented by the very high MW and emulsion form which can present

Sedimentation is often used in wastewater treatment applications where space and equipment mobility are not limiting factors.
Fig. 3 shows removals of turbidity, TSS, TCOD, and TP after
application of variable doses of the four selected polymers,
30 min occulation, and quiescent settling for 1 h. Good removals
of turbidity and TSS indicate good removal of occulated particles
by sedimentation. The coreshell polymer was the most effective
of the four remaining polymers for sedimentation and a 118 ppm
(v/v) dose achieved 93% removal of TSS, 74% removal of TCOD, and
22% removal of TP. The highest coreshell polymer dose
( 300 ppm) did not result in signicantly decreased removals of
contaminants. High doses of the other three polymers resulted
poor settled removals due to charge reversal, as happened with
the other three polymers.
The Core shell 71301 polymer also produced the fastest settling
ocs as shown in Fig. 4. In these experiments sufcient polymer
was added to a new sample of laundry wastewater to achieve ZP
between 8 and  10 mV, a ZP range that typically results in rapid
coagulation. Addition of 118 ppm of the coreshell polymer produced very large ocs resulting in 490% removal of turbidity
within 1 min. Coagulation with Nalcolyte 8105 (epi/DMA) achieved
91% removal of turbidity within 60 min of settling. Cat-oc 8108

172

H.-C. Kim et al. / Journal of Membrane Science 456 (2014) 167174

(polyDADMAC) was less effective for sedimentation removal. The

results shown in Figs. 3 and 4 indicate that the coreshell polymers
should be considered for coagulation of laundry wastewater when
solids are removed by sedimentation.
The evidence points to polymer bridging as the dominant
mechanism for core shell polymer 71301 based on the following
observations: (1) the coreshell polymers are higher MW than
other polymers; (2) the coreshell polymers were less effective at
neutralizing charge as shown in Fig. 2; (3) high doses of the core
shell polymers did not result in charge re-stabilization; and
(4) very low doses of Core shell 71301 were effective in removing
contaminants after sedimentation as shown in Fig. 3. However, the
coreshell polymers are delivered as emulsions, which are more
difcult to use in remote eld locations and it will be shown below
that coreshell polymers resulted in increased resistance to
ltration.
3.3. Specic resistance to ltration after coagulation
of laundry wastewater

sedimentation. The specic resistance results are shown in Fig. 5a

for higher coagulant doses and in Fig. 5b for the lower coagulant
doses. Nalcolyte 8105 decreased the specic resistance to ltration
to less than 2% of the specic resistance for raw wastewater for both
polymer doses. The Core shell 71301 (AcAm/DMAEA.MCQ) and
Ultimer 1460 (AcAm/DADMAC) polymers increased specic resistance to ltration in comparison with raw wastewater. Coefcients
of compressibility of the cakes (n) are indicated by the regression
line slopes and ranged from 0.5 to 0.9.
The results indicated that epi/DMA Nalcolyte 8105 was the
most promising of the seven polymers for the MF experiments
based on the following evidence: (1) lowest coagulant dose for
neutralization of the negative charge on laundry waste contaminants shown in Fig. 2; (2) good removal of contaminants during
sedimentation as shown in Fig. 3; (4) lowest specic resistance to
ltration in dead-end ltration as shown in Fig. 5; and (5) easiest
preparation of diluted feed solution due to low MW and delivery
of the neat product in water solution.
3.4. Effects of mixing time and coagulant dose on occulation

The SWRS uses dead-end ltration and solids accumulate on

the membrane during the ltration cycle. The accumulated solids
are usually the dominant contributor to total resistance to ltration. The solids cake that has accumulated on the membrane
surface will compress with increasing TMP. This can result in
exponentially increasing resistance to ltration during MF operation since solids accumulation means that greater TMP is required
to maintain constant ux, resulting in further compression and
additional increase in resistance to ltration.
The specic resistance to ltration of laundry wastewater was
evaluated for raw wastewater and for wastewater treated with two
coagulant doses of each of the four polymers. The coagulant doses
were selected to achieve similar accumulation of cake solids on the
membrane. Higher coagulant doses were based on best removals of
TSS during sedimentation in Fig. 3b. Lower doses were selected to
achieve approximately 60% removal of TSS during sedimentation
except for Core shell 71301 for which even UD resulted in good

Mixing time after addition of Nalcolyte 8150 had a signicant

effect on particle size distribution. Coagulation with polymer doses
ranging from 40% to 100% of CN and 10 min slow mixing resulted
in 495% decrease in total number of particles (Fig. 6a) and a large
increase in median particle size (Fig. 6b). Coagulation with 250% of
CN, a strong OD condition, also resulted in a large decrease in
particle numbers and increased particle size.
The mixing time after coagulant addition had substantial effects
on membrane fouling and recovery of membrane permeability by
hydraulic rinsing. Table 3 shows that the resistance to ltration (Rf)
after 1 h of MF ltration of laundry wastewater (case #1 with total
permeate ow of 46 L m  2) rose to 172  1011 m  1. The Rf after
addition of 60 ppm of Nalcolyte 8105, 10 min of slow mixing, and 1 h
ltration (case #4) was only 5.6  1011 m  1 and there was almost
complete removal of the incremental resistance with a hydraulic
wash, resulting in 98% of the pure water ux of a fresh membrane.

Table 3
Effect of mixing time on membrane fouling. The pH was 11 before coagulation, coagulant was Nalcolyte 8105, and the coagulated wastewater was dead-end ltered through
0.22 m PVDF membranes at constant feed pressure of 10 psi prior to cleaning operations.
Case

#
#
#
#
#

1
2
3
4
5

Descriptiona

Raw wastewater
Coagulated
Coagulated
Coagulated
Coagulated

Mixing intensity,
G (s  1)  t (min)

N/A
425  2
425  5
425  10
425  20

Total permeate
volume (L m  2)

46
628
707
770
716

Rf (1011 m  1)b

172
7.1
6.2
5.6
6.5

Rf (1011 m  1) [percent permeability recovery]c

Cumulative COD
removal (%)

After hydraulic wash

After 0.1 M NaOH

After 0.1 M citric acid

0.58 70.01
2.00 70.02
0.55 70.01
0.48 70.01
0.49 70.01

0.517 0.01
0.707 0.02
0.52 7 0.02
0.45 7 0.01
0.46 7 0.01

0.517 0.01
0.59 7 0.01
0.497 0.01
0.45 7 0.01
0.46 7 0.01

[82]
[24]
[85]
[98]
[96]

[88]
[64]
[86]
[99]
[98]

[88]
[77]
[92]
[99]
[98]

74
81
82
81
82

a
All coagulation pretreatments of laundry wastewater were conducted using a Nalcolyte 8105 dose of 60 ppm, which resulted in ZP between 5.8 70.6 mV corresponding
to typical charge-neutralization.
b
Hydraulic resistance to ltration at the end of ltration test.
c
Percent permeability recovery of fouled membranes after sequential cleanings was determined based on the pure water permeability measured for each fresh
membrane before the ltration tests.

H.-C. Kim et al. / Journal of Membrane Science 456 (2014) 167174

Backwash

0.1M NaOH

0.1M citric acid

100

Flux recovery (%)

Hydraulic resistance (1011 m-1)

50
40
30
A:
B:
C:
D:
E:

20
10
0

80
60
40
20

0
Raw wastewater
40% of the dose for CN
50% of the dose for CN
100% of the dose for CN
250% of the dose for CN

50

100

150

200

250

300

350

Specific permeate volume (L m-2)

Fig. 7. Effects of Nalcolyte 8105 polymer doses on hydraulic resistance of 0.22 m
PVDF membranes during cyclic ltration of laundry wastewater. Eight MF ltration
cycles of 15 minutes at constant ux of 150 L m  2 h  1 were each followed by
backwash (1 min) and surface ush (0.5 min). The inset shows percent recovery of
the initial pure water ux after sequential cleanings following the eight cycles of
operation. The occulation velocity gradient was 425 s-1 for 10 min.

Streaming current (mV)

1.0
y = 0.0216x - 0.0821
R2 = 0.9525

0.5
0.0

pH 7

-0.5

173

CN dose. Samples were mixed at 425 s  1 for 10 min, previously

identied as optimal mixing. Results are shown in Fig. 7.
MF operation with the raw wastewater was terminated during
the rst 15 min cycle due to excessive TMP. Coagulation to zero ZP
(CN) eliminated almost all fouling. The two UD conditions resulted
in very small increases in resistance during the 15 min runs and
most fouling was removed by the hydraulic wash. OD coagulation
using 250% of the CN dose resulted in steadily increasing fouling
that was incompletely removed by the hydraulic wash between
cycles. The inset in Fig. 7 shows recoveries of permeate ux after
chemical cleaning and indicates poor recoveries by chemical cleaning for the raw wastewater and the OD coagulation conditions.
3.6. Operational issues temperature, aging, coagulant control
ZP titrations and 0.22 m PVDF MF tests on laundry wastewater using fresh and aged Nalcolyte 8105 showed no change in
the effectiveness of the polymer after aging 1% solutions for up to
8 days. Aging was conducted over a range of temperatures from
4 to 45 1C.
ZP and SC measurements were simultaneously performed on
samples that were coagulated with 20520 ppm of Nalcolyte
8105, over a pH range from 7 to 11. Results are shown in Fig. 8.
The linear relation and the simultaneous indications of CN (zero ZP)
demonstrate that SC can be used to control coagulant dosing in
laundry wastewaters. SC monitors are widely used and provide
simple and robust operation [17,18]. SC readings were stable as a
function of time from addition of coagulant.

pH 8
-1.0

pH 9

-2.0

4. Summary and conclusions

pH 10

-1.5

pH 11
-80

-60

-40

-20

20

40

Zeta potential (mV)

Fig. 8. Correlation between streaming current (SC) and zeta potential (ZP). SC is a
robust analytical method that is used to achieve real-time coagulant dosing. The
good correlation over a wide range of coagulant doses and pH values shows that SC
can be used to control coagulant dosing of laundry wastewater. The laundry
wastewater pH was adjusted between 7 and 11 before coagulation with Nalcolyte
8105 using polymer doses from 20 to 520 ppm (v/v). All SC and ZP measurements
were conducted immediately after occulation with a velocity gradient of 425 s  1
for 10 min.

The photographs at the bottom of Table 3 show the MF

membranes after 1 hr ltration plus hydraulic wash and sequential
NaOH and citric acid cleanings. Photograph #1 (no coagulant)
shows that particles remained small and attached particles were
poorly removed. Photograph #4 (coagulant and 10 min mixing)
shows a clean membrane, consistent with almost complete recovery of initial permeability. Coagulation followed by 2 or 5 min
occulation (photographs #2 and #3) resulted in dramatically
improved permeability after 1 h of ltration compared to raw
wastewater, but the occulated particles were incompletely
removed by the cleaning processes. Coagulation also increased
removal of TCOD from 74% with raw wastewater to 81% with any
of the coagulation doses.

The feasibility of using coagulation as a pre-treatment prior to

MF of laundry wastewater was evaluated with emphasis on using
quaternary amine coagulants that retain a high cationic charge
even at high pH values. Seven coagulants were tested. The following
conclusions were drawn from this study.

 A high MW coreshell polymer was optimal for sedimentation

3.5. Multi-cycle MF runs

Multi-cycle ltration runs were used to evaluate the effect of
coagulation by Nalcolyte 8105. A fresh sample of laundry wastewater was used. Eight cycles of MF operation included 15 min of
ltration at 150 L m  2 h  1, 1 min of backwash, and 0.5 min of
surface ush for each coagulant dose. A ZP titration was performed
and coagulant dosing was set at 40%, 50%, 100%, and 250% of the

processes for removal of contaminants. Cationic polyacrylamide polymer (Core shell 71301) achieved 490% removal of
turbid materials in laundry wastewater at pH 11 within 1 min
of settling time after coagulation.
A low MW epi/DMA polymer was the best for decreasing specic
resistance to ltration in MF operations. Epi/DMA (Nalcolyte
8105) and polyDADMAC (Cat-oc 8108 plus) decreased clogging
of PVDF MF membranes by a factor of 10 at pH 11, but other
acrylamide copolymers rather increased specic resistance to
ltration in comparison with raw lint wastewater.
Multi-cycle MF tests showed that coagulant additions from 40%
to 100% of the CN dose were effective at reducing fouling. These
doses also produced a cake that was easily removed by
hydraulic cleaning between the ltration cycles. A large overdose of the cationic polymer (250% of CN) substantially reduced
fouling compared to raw laundry wastewater, but resulted in
increasing baseline fouling that was not removed by chemical
cleaning.
Mixing time was important. Initial fouling was reduced with
2 min mixing at 425 s  1 and recovery after hydraulic washing
was greatly improved when 10 min mixing was provided.
The epi/DMA polymer was very effective over a wide range of
doses, from 40% to 100% of the CN condition. The 1% polymer
solution was stable with aging at 4451C. In addition there was
excellent correlation between ZP and SC readings over a wide
range of pH and coagulant dosing. The wide range of coagulant
dosing, temperature stability, and ability to use SC make the

174

H.-C. Kim et al. / Journal of Membrane Science 456 (2014) 167174

epi/DMA polymer a good candidate for use in remote locations

where accurate control of dosing is difcult and storage conditions can be harsh.

Acknowledgment
This material is based upon work supported by the U.S. Army
Research Laboratory and the U.S. Army Research Ofce under
Contract/Grant no. W911NF1010224. The mention or use of any
commercial products does not imply ofcial U.S. Army endorsement.
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