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Treatment and Management of Wastewater from an Acrylic Fiber Industry

Conference Paper · December 2006

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GMSARN International Conference on Sustainable Development: Issues and Prospects for GMS 6-7 December 2006

Treatment and Management of Wastewater from an Acrylic Fiber

Industry

Ray B., Lamsam A., and Annachhatre A. P

Abstract— This research focused on developing treatment and management options for the effluent from an acrylic fiber
industry. The study procedure comprised a series of steps, viz., characterization of wastewater outputs from the process,
segregation of wastewater streams and treatability study using biological and physical methods. The study identified and
proposed segregation options for high and low pollution load streams. Treatability studies were conducted for both streams.
The results indicated that the ultrafiltration membrane process could be used effectively in combination with the activated
sludge process to achieve reasonably high COD and TKN removal. Furthermore, after treatment with membrane filtration
process, the low pollution load stream could be reused as make up water in cooling towers.

Keywords— Acrylic Fiber, Industrial Wastewater, Activated Sludge, Membrane Filtration, Reuse and Recycling.

sludge process [6], the current focus is on the

1. INTRODUCTION
Acrylic fiber manufacturing industry occupies a
prominent position in Asia as well as in the global man-
made fiber market. This is due to its superior
characteristics over natural fibers in terms of its
durability, resistance to chemicals and cotton-like texture.
Also, acrylic fiber can be utilized as a raw material for
knitwear including fleece, blankets, soft toys, etc. The
treatment and management of wastewater from the
acrylic fiber manufacturing process, however, poses a big
challenge; mainly because of the recalcitrant nature of the
effluent resisting degradation by conventional biological
treatment methods [1], [2]. This could be attributed to the
fact that the wastewater may contain some amounts of
acrylonitrile, which is used as one of the raw materials in
the production process. Acrylonitrile is not easily
decomposed by microorganisms and can cause severe
environmental pollution due to its high toxicity,
persistence and mutagenicity [3]-[5]. Furthermore,
increasingly stringent standards and commitments
towards total quality management are pressurizing the
acrylic fiber industry, to search for more viable treatment
and management schemes.
Though the conventional approach to treatment of
wastewater from the acrylic fiber industry has been to
utilize the biological treatment methods like the activated
The authors gratefully acknowledge financial support from the
Swedish International Development Corporation Agency (SIDA)
through the Asian Regional Programme on Environmental Technology
Phase II (ARRPET Phase II) project. Sincere appreciation is also
conveyed to acrylic fiber industry for their support and partial funding.
Ray B. is with Environmental Technology Program, Sirindhorn
International Institute of Technology (SIIT), Pathumthani 12121,
Thailand.
Lamsam A and Annachhatre A. P (corresponding author) are with
Environmental Engineering and Management Program, School of
Environment, Resources and Development, Asian Institute of
Technology (AIT), Pathumthani 12120, Thailand. Tel: 66-1-524-5644;
Fax: 66-2-524-5644; E-Mail: ajit@ait.ac.th
development of methods to enhance the biodegradability
of the acrylic substrate, like pretreatment technologies
[7], [8], physico-chemical treatment methods [9] and
microbiological innovations [2].
This research aims to investigate suitable biological and
physical treatment options as well as wastewater
management strategies at a selected acrylic fiber industry
in Thailand. Key issues confronting this industry are the
variable efficiencies for COD removal and high volumes
of discharged effluent.
Background Information of the Research Site
The research site was a medium sized factory which
produces acrylic fiber in Thailand. The current production
capacity of this industry was approximately 77,000 metric
tons per annum. Almost 60% of the factory produce was
exported to countries world-wide, while the remaining
was used domestically. The end products were
extensively used in textile, knitwear, carpet, toys, blanket
and apparel manufacturing industries.
Production Process
Principally, the production process of acrylic fiber can be
divided into two areas including the chemical and textile
area. Each area can be divided further into sections. The
chemical area consists of three sections which are C1, C2
and C3. The textile area includes T1 and T2 sections.
Each section comprises of several unit processes. Flow
chart of production sections is shown in Figure 1. Brief
description of each unit process in each section is as
follows:
C-1 Section: This section consists of chemical mixing and
polymerization processes. Firstly, chemical mixing of the
monomer raw materials such as acrylonitrile and other
catalyst chemicals is performed in aqueous phase. The
monomers solution is then conveyed to the batch
polymerization reactor unit. A large amount of water is
consumed in this section for washing of the resulted
polymer. Thus, high volume of wastewater is generated.
Waste stream A is discharged at this section.

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GMSARN International Conference on Sustainable Development: Issues and Prospects for GMS
Raw materials C-1 C-2
Chemical C-3
area
Waste stream B
Waste stream A
Figure 1: Production Sections of the Selected Acrylic Fiber Industry
C-2 Section: The conditioned polymer from the first
section is transmitted to this section for DOPE making.
The purpose or operating principle of this process is to
obtain a very uniform or homogenized polymer solution
called DOPE suitable for spinning. There is negligible
water demand for this section, and hence, no wastewater
discharges.
C-3 Section: This stage is characterized by two processes:
solvent recovery and purification. Recovery of the solvent
occurs in a wet solvent extraction process where some
water is consumed and wastewater generated. The
extracted solvent is purified by addition of activated
carbon. The activated carbon process generates some
wastewater during bed-backwashing operation. Waste
stream B is generated at this section.
T-1 Section: Wet spinning is performed for the refined
dope solution by extruding the dissolved polymer through
stainless steel spinnerets immersed in a large spinning
baths. As the polymer emerges from the spinnerets, it
coagulates to form fiber bundles. The excess solvent is
recycled to the Section C-3 for recovery and reuse in C-2
section. Negligible amount of water is consumed in this
stage and so there is little wastewater generation.
T-2 Section: Various mechanical operations like washing
for solvent extraction, stretching, drying and heating are
performed in this section to give strength and stability to
the fiber bundles, before product is sent for packaging.
Several waste streams (C, D, E and F) are generated at
this section.
Existing Wastewater Management within the Factory
The waste streams (A to F) are first conveyed separately
via transmission pipelines to the treatment plant site. The
other part of the wastewater coming from the utilities
section like the boilers, cooling towers, toilets, canteens
(via septic tank) and water treatment plant is pumped
directly to polishing pond and later discharged.
In the wastewater treatment plant, the combined stream is
first well-mixed in the equalization tank followed by
extended aeration activated sludge process and secondary
clarifiers. The clarified effluent is then sent to the
polishing pond, and discharged to the natural water body.
2. MATERIALS AND METHODS
Preliminary data about the effluent treatment plant was
collected from the industry personnel before designing
6-7 December 2006
T-1 T-2 Final product
Textile
area
Waste streams
C, D, E, and F
Combined
wastewater
treatment plant
the research layout scheme. Data for production process,
water treatment and wastewater treatment was gathered
later through in-plant monitoring records and further
interviews with the personnel at the site. The combined
and individual wastewater stream characteristics were
subsequently characterized in the Environmental
Engineering Laboratory at AIT. The segregated streams
were then separately into high pollution (Phase I) and low
pollution (Phase II) streams which subjected to
treatability study using activated sludge and membrane
filtration processes. Recycle, reuse and wastewater
minimization strategies were evaluated.
Sampling Methods
Grab sampling method was applied throughout the study
of waste stream characteristics. This was based on the
assumption that each waste stream characteristic did not
fluctuate significantly. Wastewater characterization
covered six waste streams from the production processes
(Figure 1) and one combined effluent stream from the
outlet of the equalization tank.
Chemical Analysis
Characteristics of each waste stream were analyzed for
three data sets and the average, minimum and maximum
values were calculated for representative data. Analysis
included pH, conductivity, temperature, BOD, COD, SS,
TKN, NH3-N and TDS [10]. For flow measurement, the
amount of wastewater from each wet process was
measured by either the bucket and stop watch method or
weir flow estimation method.
Stream Segregation
The stream segregation was based on the relative strength
of the wastewater streams from the production process in
the factory according to the organic load. Mass balance
was used to calculate combined stream organic loads.
Segregated streams were subjected to treatability using
activated sludge and ultrafiltration membrane process.
Treatability Study
Two phases of treatability studies were performed
including Phase I for high pollution load stream A and
Phase II for low pollution load streams C+D+E+F.
Activated Sludge (AS) Process
Seed sludge: Seed sludge from aeration process at the
industrial research site was used as the biomass source.
The biomass was acclimatized separately to the high-
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GMSARN International Conference on Sustainable Development: Issues and Prospects for GMS 6-7 December 2006

COD load and low-COD streams using appropriate
dilutions where required.
Experimental setup: A laboratory scale Completely
Stirred Tank Reactor (CSTR) AS process followed by a
settling tank was operated for the high load COD stream
and the low COD load stream in the continuous mode
(Figure 2a).
Operating procedure: The entire operation was carried out
in the three stages, viz., Stage 1 for process startup at
constant organic load; Stage 2 for step-wise increase in
the organic load; and stage 3 for operation at undiluted
feed conditions. The operation conditions for the process
are summarized in Table 1.
provided with an in-built bioreactor tank, for the current
research; only the physical separation process was used.
Driving force was provided through a circulation pump
working at an operating pressure of 0.28 M Pa
Operating procedure: Each batch was started by filling
the bioreactor tank with the wastewater. Permeate flow
(approximately 2L min-1) and liquid levels in the
bioreactor tank were continually monitored to assess the
progress of the batch. The batch was run until a particular
permeate volume was collected in the tank. The influent,
effluent and retentate samples were analyzed. The
temperature was always maintained below 40oC using an
internal cooling coil inside the bioreactor.

Supplemental nutrients: Additional of micro-nutrients 3. RESULTS AND DISCUSSION

was supplied (CaCl2.2H2O = 0.004 g l-1, MgCl2. 6H2O =
0.005 g l-1, FeSO4 = 0.003 g l-1, CuSO4 = 0.001 mg l-1,
CoCl2 = 0.0003 mg l-1, Na2MoO4 = 0.0007 mg l-1, ZnSO4
= 0.0008 mg l-1) to facilitate the growth of biomass.
Membrane Filtration (MF) Process
Experimental setup: The process was operated in the
batch mode using a pilot plant unit from Triqua (module
type BTU-P4C/02AE with a membrane type 33100). The
membrane unit has Molecular Weight Cut-Off (MWCO)
size of 100, 000 Daltons. The membrane used in this
package plant is a polysulphon crossflow ultrafiltration
(Figure 2b). It is a solid separator type with the
membrane located side stream. Even though the unit was
Characterization of Waste Streams
The total wastewater generated was around 4,460 cubic
meters per day. The characteristics of all the six streams
from the production process and the combined effluent
stream are summarized in Table 2. The combined effluent
from the spinning processes (stream C+D+E+F from T-1
and T-2) constituted around 50 % of the total wastewater
flow rate. The polymer wash wastewater (stream A
generated from C-1) alone constituted around 40 % of the
total wastewater flow.

Aeration Tank (5 L)

Sedimentation
Tank(3.75 L)

Influent
tank Effluent
tank
Return Sludge

a b

Figure 2: Experimental Setup; a: Activated Sludge Process; b: Membrane Filtration Process.

Table 1: Operating Parameters for Activated Sludge Process.

Operating Parameter Unit Value
-1
Flow Rate ld 20
HRT h 6
Recirculation Ratio 1-1.25
Solid Retention Time d 5
-1
F/M g COD (g MLSS.d) 0.33-0.66
o
Temperature C Ambient (27 ± 3)
pH 8 ± 0.5
DO mg l-1 3 ± 1.2

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GMSARN International Conference on Sustainable Development: Issues and Prospects for GMS 6-7 December 2006

of the chemically toxic nature the combined discharge

The combined wastewater had a unique composition of
high COD with relatively low BOD, and very low
suspended solid content. COD was the highest for the
stream A and lowest for the stream D. BOD of waste
streams varied as well as TDS value according to the
chemicals used and process employed. Conductivity and
TDS values were the highest for the backwash
wastewater stream B while the lowest for the spinning
wastewater streams (C, D, E and F). The analysis of
wastewater characteristics was done to see suitability of
waste streams for subsequent biological treatment.
The ratio between BOD and COD for the various streams
in Table 2 indicates several waste streams may not get
easily biodegraded. Stream A had the highest ratio of
0.49 which showed positive sign toward biological
treatment. However, the ratios for the remaining streams
ranged from 0.38 to 0.03, which showed low
biodegradability. Stream B and E had the lowest ratio.
For stream B, this may due to very high pH. On the other
hand, stream E had very low BOD value compared to its
COD.
The least polluted waste stream was considered to be
stream D from the spinning process. This waste stream
characteristic met the standard of discharge for almost
every parameter, apart from pH which was slightly too
acidic. Therefore, this stream could be directly
discharged after only neutralization process, or reused
after simple treatment process.
Wastewater Stream Segregation
There was no wastewater segregation practice at the
factory site. All the wastewater streams were individually
discharged through pipes in to the equalization tank.
Consequently, the treatment plant had to deal with a large
volume of wastewater with high pollution load. In
addition, biological treatment efficiency reduced because
coupled with relatively low BOD.
Based on the individual COD concentrations (loads),
practical feasibility and ease of implementation, a
segregation scheme was developed. The high pollution
load streams A and B should be segregated from low
pollution load streams C, D, E and F. Treatment of these
segregated streams should be carried out separately.
Characteristics of the segregated streams are shown in
Table 3.
Treatability Study for Stream A (Phase I)
Activated Sludge
The investigations were carried out for 147 days. The
entire period comprised various stages: (1) the initial
startup in a batch to find out the optimal HRT, (2)
operation at a constant COD loading rate for sludge
acclimatization, (3) Maturation stage till the steady-state
achievement for removal efficiency, (4) stepwise increase
of COD loading rate and (5) operation at undiluted feed
conditions (Figure 3).
COD removal: There was a random variation of COD
removal rate in all the stages (Figure 4). For the steady
state-operation period ranging from day 79-105, the
average removal efficiency was only around 45%.
However, maximum removal efficiencies around 80-85
% were achieved on the days 9, 50, 59, 116 and day 139.
The efficiency was the minimum at 23% in the
maturation on the 62nd day. The average removal
efficiency for the overall operation period was just about
52% while the efficiencies varied in the range between
40-60%. The reason for this high variation seems to be
the non-biodegradable or partially degradable nature of
the acrylic fiber wastewater also concomitant with the
findings of [11], [12].

Table 2: Summary of Wastewater Characteristics.

Stream Flow pH Temp Cond. BOD COD SS TKN TDS BOD:COD

m3 d-1 ºC µS cm-1 mg l-1 mg l-1 mg l-1 mg l-1 mg l-1
A 1,800 4.1 44.6 2,957 593 1,002 48 125 2,437 0.49
B 457 12.0 48.3 19,300 16 574 13 69 7,697 0.03
C 211 3.3 46.3 1,119 82 213 17 33 941 0.38
D 1,450 3.3 51.7 461 18 91 2 28 253 0.21
E 289 6.6 39.7 109 17 309 7 33 189 0.03
F 253 6.8 42.2 181 142 805 27 133 395 0.24
Combin 4,460 9.3 43.1 1,607 157 669 17 85 1,394 0.29
ed

Table 3: Characteristics of Segregated Wastewater Streams.

Sources pH Cond. COD COD load SS TKN

µS cm-1 mg l-1 kg d-1 mg l-1 mg l-1
High Pollution Load (A)* 4-6.8 1,100-2,957 663-1002 1,193-1,803 27-75 64-85
Low Pollution Load (C + D + E + F) 4.01 298 284 625 16 28

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GMSARN International Conference on Sustainable Development: Issues and Prospects for GMS 6-7 December 2006

Note: * Range of values based on analysis of three sets of samples taken at different times.
TKN Removal: As parts of acrylonitrite polymer
contribute to the TKN [13], [14], concentration of TKN
was found to be significantly high around 100 mg l-1
(Table 2).However, the TKN removal remains low for all
of the different stages of operation. The maximum TKN
removal was found to be around 32% for days 26 and 34
in the startup phase while the average TKN removal was
only around 12% for the entire period which was also
concordant with the steady state average removal value of
11 % (Figure 5). These results are justified, since the
activated sludge process did not incorporate nitrification
process through control of solid retention time. Therefore,
TKN assimilation in the bacterial cells was the only TKN
removal mechanism. Furthermore, break down of
organic-N fraction of the polymer structure was also
possible, as ammonia-N in the effluent was sometimes
found to be higher than in the influent with almost
constant TKN. The overall summary of the steady-state
AS operation is presented in Table 4.

COD Loading and Consumption Rates for the A/S Process

3.5

2.5
COD Influent and Removed

2
(kg COD/ cu.m.d)

1.5

0.5

0
0 50 100
Time (Days) Inf COD Load
COD Load Removal

Figure 3: COD Influent Loading and Removal Rates for Activated Sludge Process (Phase I)

100
90
80
70
CODRemoval

60
50
40
30
20
10
0
0 20 40 60 80 100 120 140 160
Time (Days)

Figure 4: COD Removal Efficiencies for Activated Sludge Process (Phase I)

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GMSARN International Conference on Sustainable Development: Issues and Prospects for GMS 6-7 December 2006
35

30

TKNRemoval %
25

20

15

10

0
0 20 40 60 80 100 120 140

Time (Days)

Figure 5: TKN Removal Efficiencies for Activated Sludge Process (Phase I)

Membrane Filtration Treatability Study for Stream C+D+E+F (Phase II)

Activated sludge
Since the polymer part of the influent wastewater has a
wide range of molecular weight fractions in the range of The low pollution load stream C+D+E+F was fed into the
100,000 to 170,000 Daltons, it was deduced that different AS process and the effluent was filtered through the
amounts of polymer would strain through the pores of the ultrafiltration membrane. The entire process was run for
membrane for different batches. The results from 8 32 days with short period for sludge acclimatization. The
batches in terms of the average and maximum removal overall results are summarized in Table 5. The average
efficiencies are presented in the Figure 6 along with AS COD and TKN removal efficiency were particularly low
summary of removal efficiency results. Although the of around 25 % and 33% respectively. This could be due
activated sludge process can remove the COD more to the low BOD: COD ratios for the spinning section
efficiently than the MF process, the TKN removal wastewater and the inherent refractory nature of the
efficiency is much higher for the MF process. This polymer substrate.
implies that the membrane was successfully able to retain
Table 5: Summary of Results at Steady State for
parts of the bio-refractory polymer part which contributes
Activated Sludge Process (Phase II).
to the TKN.
Table 4: Summary of Results at Steady State for Parameter Unit Avg. Min. Max.
Activated Sludge Process (Phase I).
COD inf mg l-1 441 284 723
Parameter Unit Avg. Min. Max.
COD eff. mg l-1 316 225 457
-1
COD inf mg l 402 349 487
TKN inf. mg l-1 70 28 112
-1
COD eff. mg l 216 163 258
TKN eff. mg l-1 47 14 70
-1
TKN inf. mg l 41 32 49

TKN eff. mg l-1 37 31 42 Membrane Filtration

The overall results for 3 batch experiments in terms of
average removal efficiency and relative comparison with
Removal the AS process for Phase 2 are summarized and presented
Efficiency Activated Sludge Membrane Filtration
(%) in Figure 7. For MF process, the maximum COD and
100 TKN removal achievable were found to be 87 and 81%
90 respectively. For the low pollution load stream, it was
80
70
found that the average removal efficiencies for both COD
60 and TKN are much higher for the MF process than in the
50 AS process. High removal efficiency clearly
40
30 demonstrated ability of the membrane to retain high
20 molecular weight polymer. Since, the process was
10 operated for a short period of time, membrane fouling
0
COD TKN
was not observed. However, for full scale application
membrane fouling plays an important role in selecting the
Figure 6: Removal Efficiency of Activated Sludge and membrane type as well as operating procedure and
Membrane Filtration Process (Phase I). filtration mode.

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GMSARN International Conference on Sustainable Development: Issues and Prospects for GMS 6-7 December 2006

Removal Reuse and Recycle

Efficiency Activated Sludge Membrane Filtration
(%)
The factory has an internal quality standard for use of
different type of water. By comparing the final effluent
100
90 characteristics with criteria in Table 6, it is possible to see
80 the reuse and recycle potential of treated wastewater. The
70 low conductivity and TDS value of the membrane
60
50
permeate using the spinning wastewater makes it an
40 attractive option to reuse the treated effluent as make up
30 water in cooling towers.
20
10
0
COD TKN

Figure 7: Removal Efficiency of Activated Sludge and

Membrane Filtration Process (Phase II).

Table 6: Comparison between Effluent Characteristics and Water Quality Criteria

Source pH Conductivity COD TKN Nitrate Total Alkalinity TDS

-1 -1 -1 -1 -1
µS cm mg l mg l mg l mg l mg l-1

Treated raw water 7-10.5 ≤ 750 n/a n/a n/a ≤ 70 ≤ 400

Membrane permeate (Phase II) 6.0 302 67 12.9 - 6.7 283

industrial wastewaters-the state of the art. Water

4. CONCLUSION
The entire study was divided into several steps. After the
waste stream characterization and review of existing
wastewater management, a segregation scheme was
developed to treat the high pollution load and low
pollution load streams separately. Through the treatability
study, it was concluded that the membrane processes can
be applied effectively in combination with the biological
processes for higher consistency in COD removal from
the acrylic fiber wastewater. It was also deduced that the
membrane process would serve better as a pretreatment
unit for both the high pollution load and low pollution
load streams rather than as a post-treatment step. The
study also established that permeate from membrane
filtration of the low pollution load stream can be reused
as a make up water stream in the turbine generator
cooling towers. Finally, it can be inferred that similar
research methods and techniques can be applied for other
synthetic fiber industries.
5. NOMENCLATURE
AS Activated Sludge
Avg. Average
Eff. Effluent
Inf. Influent
Max. Maximum
MF Membrane Filtration
Min. Minimum
6. REFERENCES
[1] Orhon, D., Tasli, R., and Sozen, S. 1999.
Experimental basis of activated sludge treatment of
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[2] Zhang, Y. L., Zhao, J. F. and Gu, G. W. 2003.
Pretreatment of acrylic fiber wastewater and
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the IWA Specialist Group Conference, Beijing,
China.
[3] WHO, 1983. Environmental Health Criteria for
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[4] USEPA, 1985. Health and Environmental Effects
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Assessment Office, U.S, EPA, Cincinnati, OH.
[5] IARC. 1982. Chemicals, Industrial Processes and
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[6] Wyatt, J. M. and Knowles, C. J. 1995. Microbial
degradation of acrylonitrile waste effluents: the
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manufacture of acrylonitrile. International
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[7] Chang, C. N.; Lin, J. G., Chao, A. C., Cho, B. C., and
Yu, R.F. 1997. Pretreatment of acrylonitrile and
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[8] Morper, M. R. 1999. Combination therapy tackles
wastewater toxins. Canadian Journal of Chemical
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[10] APHA, AWWA and WEF.1998. Standard Method
for the Examination of Water and Wastewater. 20th
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 [11] Orhon, D., Ates, E., Sozen, S. and Cokgor, E. U.
1997. Characterization and cod fractionation of
domestic wastewaters. Environmental Pollution, 2:
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[12] Babuna, G. F., Soyhan, B., Eremektar, G. and Ohron,
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[13] Lamsam, A. 2004. Cleaner Production in Acrylic
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