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Marek Lebiedowski Biological Removal of Impurities

Technical University of Łódź from Textile Industry Wastewaters:


An Assessment
Faculty of Civil Engineering,
Architecture and Environmental Engineering
Department of Water Management
Al. Politechniki 6, 90-924 Łódź, Poland

Abstract
Textile wastewaters (WW) contain specific impurities that impede their biological treatment.
Thus, to be treated biologically, they require technological pre-treatment, mostly composition
equalisation and neutralisation. If biological oxygen demand (BOD) is determined in WW,
a biodegradation test may be used to determine whether biological treatment is possible.
The phenomenon may be described mathematically, provided that the removal of impurities
occurs in a homogenous velocity field. The functional relationships of the biodegradation
process and continuous pollution removal in overflow tanks are described, and changes in
chemical oxygen demand (COD) concentration and permanganate value (PV) occurring in
cotton industry WW treatment are discussed.

Key words: textile industry water wastes, biodegradation, activated sludge.

that, apart from some wool industry WW place. The importance of the velocity
and WW from preliminary treatment of field generated by micro-organisms dur-
natural silk, these wastes are considered to ing the transport of the adapted substrate
be poor in organic, biogenic compounds. structures to biochemical reaction centres
However, if BOD5 is used as an indicator is also emphasised.
of the WW biogenic impurity concentra-
tion, then the mean concentration of this
type of WW is mostly comparable with
Pollution Degree of Textile
that of municipal sewage. The ratio be- Wastewater
tween BOD5 and the total concentration Textile plants continue to be a source of
of organic pollution is a different criterion, specific environmental pollution because
and rather unfavourable. Volatile sub- of considerable amounts of mineral
stance content may be a general indicator substances (mostly simple salts but also
of organic substance concentration, easy to complex organic compounds) that are
determine analytically in this WW type. It used to process textile raw materials and
may range between 30 and 40% of the dry semi-finished products. Wet treatment
residue indicator in textile WW, and even processes influence WW salinity and or-
up to 70% of the indicator in WW from ganic pollution indicators, such as COD
n Introduction wool laundries. The volatile substance (chemical oxygen demand), TOC (total
Biological treatment of textile industry content in total solids in typical municipal organic carbon), detergents or colour.
wastewaters (WW) is used only excep- sewage equals about 47%.
tionally, mostly when biological oxygen Industrial WW from extensive production
demand for five days (BOD5) must be WW composition in cotton plants, as
cycles is characterised by a more balanced
decreased and the reduction level ex- well as in the production and finishing
composition than those from small plants.
ceeds 60%. It is also advisable to add at of fabrics made from synthetic fibres, is
Individual technological procedures, es-
least 50% of municipal sewage to textile least favourable for biological treatment.
pecially dyeing, washing, bleaching and
Unfortunately, at the beginning of the 21st
industry WW. However, it should be notid finishing, have a particular impact on the
century these plants are particularly im-
that despite such precautions, operational WW composition in small plants.
portant because of the production size and
difficulties caused by the uneven flow of
the volume of water used. Other branches,
loads of specific impurities (including In keeping with the traditional division of
including the wool industry, also process
toxic pollutants) which are not normally textile branches used in Poland, qualita-
considerable amounts of synthetic raw
encountered in municipal sewage treat- materials. As a result, the qualitative tive WW composition may range widely.
ment must be overcome. Additionally, composition of textile WW has become WW quality parameters are given in
textile industry WW are characterised by considerably homogenised. Table 1 [1].
a great variability of composition, which
results not only from the multiphase The aim of this paper is to examine the For the purposes of biological treatment
nature of most technological processes biological treatment of textile WW on the of textile WW, biodegradable properties
but also from the chemicals used and the basis of a biodegradation test and its math- of organic pollution in treated wastes
composition of the processed textile raw ematical interpretation. The mathematical should be determined. The ratio between
materials. description of the process offered by the BOD5, or possibly COD or permanganate
author includes the participation of the value (PV) and the values of the volatile
Reluctance to use biological textile WW water environment in which biochemi- substances mentioned above, may be used
treatment is also brought about by the fact cal changes to the organic substrate take as a preliminary criterion.

FIBRES & TEXTILES in Eastern Europe January / March 2005, Vol. 13, No. 1 (49) 75
Table 1. Textile industry quality determinants - ranges [1]. WW qualitative composition equalisation
is another prerequisite for the biological
WW composition in the following industries treatment of textile WW [3]. As pollution
Parameter Unit
cotton wool silk knitting flax combed yarn
concentrations vary greatly, the application
of efficient and suitable tanks to equalise
pH - 5-140 4.0-9.5 3.7-9.5 4.0-11.0 3.0-11.2 6.0-8.8
WW qualitative composition ensures a
Alkalinity mval/dm3 5-140 0-40 0-40 0-120 0-120 0-40 steady operation of the biological equip-
CODMn mg O2/dm3 80-900 70-650 40-550 30-700 60-3900 100-2800 ment. Additionally, it is also necessary to
BOD5 mg O2/dm3 50-700 30-450 30-700 30-650 30-1800 60-4000 separate WW into concentrated WW and
CODCr mg O2/dm3 100-1100 50-850 60-2800 60-1000 50-3600 50-2900 so-called washery effluent.
Chlorides mg Cl/dm3 60-650 50-600 40-1200 30-1800 30-300 100-300
Sulphates mg SO4/dm3 50-750 50-450 50-540 30-450 35-180 100-1000 An excessive reaction connected with
Detergents mg/dm3 1-70 5-100 4-35 0-120 - 5-120 the presence of alkalis (mostly sodium
Total dissolved solids mg/dm3 80-3600 50-2700 40-2900 40-2900 200-1900 400-1200
hydroxide and sodium sulphide, as well
as reactive dyes and detergents) impedes
Total suspended solids mg/dm3 50-500 60-400 40-400 50-600 50-800 50-2400
direct biological treatment of concentrated
Temperature °C 30-60 25-50 35-700 35-60 25-65 20-50
WW. Attempts to treat concentrated WW
Colour test solution degree 1:10-1:700 1:10-1:550 1:8-1:400 3:5-1:400 1:2-1:200 1:10-1:300
biologically, even after its equalisation,
usually fail because of the factors given
above. Excessive alkalinity hinders the
The main load of organic impurities in Prerequisites for Textile WW respiratory processes. This is also true to
textile WW, almost equivalent to the
Biological Treatment a smaller degree of dyes and surfactants
volatile substance mass, comes from the
dyes used, as well as (sometimes) from The biological treatment of textile WW (detergents). In the case of cotton industry
finishing agents. They are products of depends on the preliminary technological WW, the adaptation of activated sludge
processing of WW, which in turn facili- micro-organisms to their environment is
chemical synthesis whose composition
tates the most important procedure, i.e. the possible as long as pH does not exceed
is often unidentified and even protected
biochemical adaptation of pollution in the 9. Surfactant concentration below 50 mg/
by the manufacturer. Their removal and
final stage. dm3 does not disturb the operation of the
decomposition in chemical and biological
adapted sludge either; it only impedes the
treatment processes are particularly dif- operation of aeration tanks. The biologi-
ficult and pose the greatest problem. As studies on textile WW treatment con-
ducted under the supervision of the present cal treatment of textile WW pre-treated
author at the Technical University of Łódź using the chemical precipitation method
Only some products of hydrolysis of fibre-
demonstrate, similarly to municipal and does not pose any difficulties.
forming substance from natural raw ma-
terials are biologically degradable. As the domestic sewage treatment, floating mat-
Coagulation eliminates the basic load of
present author’s analysis shows, the loss ter, including specific fibrous impurities,
dyes and dissolved substances from WW.
of the mass of fibre-forming raw material must first be removed. This is particularly
Activated sludge easily adapts to the en-
that undergoes hydrolysis in finishing necessary before the neutralisation proc-
vironment of these WW; however, the
processes is as follows: ess is conducted, if saturation with stack
operation of a two-phase treatment plant
§ animal fibres (wool) 2-3 %; approximate gases is used. Precipitates which form as
is complex. The same final reduction rate
statistical formula: C21H3O15N6S a result of saturation (mostly carbonates
of the pollution load and concentration is
§ natural silk 36-42 %; approximate and bicarbonates, together with fibres)
achieved for concentrated WW, or pos-
produce felt-like crystallising settlings
statistical formula: C3H7O3N sibly total sewage, when preliminary fer-
that impede the appropriate operation of mentation is used. A technological system
§ cotton fibres 1-3.3 %; approximate
the neutralisation equipment. that uses anaerobic processes can also be
statistical formula: C6H7O2(OH)3
§ flax fibres 17-20 %; approximate sta- recommended for many textile factories
Neutralisation is required in cotton indus- that deliver WW to the municipal sewage
tistical formula: C10H12O2
try plants with the full production cycle, system, especially when local authorities
where bleachers are used, as well as in object to the adverse influence of textile
The loss of the mass of synthetic fibre bleacheries of artificial fibres. WW from
raw material usually does not exceed WW on the operation of the municipal
dyeing shops in which sulphur dyes are sewage biological treatment plant.
1%. However, these products are spar- used may be alkaline; however, when
ingly soluble in water, but solve well in mixed with other technological baths, It should be noted that textile WW (apart
concentrated alkalis. As the comparative this WW type does not require separate from flax industry WW) do not require any
analysis of WW qualitative composition neutralisation. preliminary sedimentation. The amount of
demonstrates, textile WW parameters are suspended solids after preliminary quali-
fairly suitable for biological treatment, Fine fibres are inevitably present in WW, tative composition equalisation is always
approaching those of municipal sewage. even if filtration membranes are used. Fi- lower than 150 mg/dm3. After two hours of
In the case of municipal wastewaters, brous impurities do not obstruct biological sedimentation, sludge volume does not ex-
it is generally accepted that the ratio treatment, and are sometimes even helpful, ceed 1 cm3/dm3, and the SS concentration
BOD5/organic substance of total solids provided that their amount and form are reduction usually does not exceed 40%.
equals 1:1.5 (300:450 - for sewage with not indicative of wasteful usage of raw Preliminary removal of SS from textile
average concentration) [2]. materials. WW is thus not technologically justified.

76 FIBRES & TEXTILES in Eastern Europe January / March 2005, Vol. 13, No. 1 (49)
Mechanism of Biological the stream of water particles alone, as the pollution concentrations is observed over
smallest structures taking part in metabo- defined time periods under the condition
Removal of Impurities
lism of living organisms, guarantees a zero of lacking inflow of impurities from ex-
WW may be treated biologically provided water balance, i.e. the difference between ternal sources. The periodic dynamics of
that polluting substances can be used as the amount of the inflow, and the effluent the test may be presented in the following
the nutritive substrate for micro-organ- in an area with the volume of the system differential equation:
isms. The adapted substrate is removed examined (V) containing micro-organism (3)
from the WW solution as a result of its structures with a mean concentration of X,
where (besides the determinations used in
transport in a water stream into cellular is close to zero. The velocity field – i..e
equations 1 and 2):
structures of micro-organisms through the vector field, regardless of the nature
S - the substrate concentration (of remov-
their surface. The micro-organisms’ of determining factors (electric, magnetic, able impurities), kg/m3
contact surface with the surrounding hydraulic) – characterises, in keeping with S’ - the substrate concentration in the
environment of WW treated is large. The the general definition of the velocity field, stream leaving micro-organism
unfolded surface of one gram of unicel- the stream q induced by the velocity vector structures participating in the proc-
lular organisms and algae equals 1.1×1012 of particles that are in this field, . The
µm2. For WW treatment with, for instance, ess, kg/m3.
characteristic stream of this field may be
activated sludge, the micro-organism mass presented mathematically in the general
concentration is about 3-6 kg/m3, which Using equation (2) and organising it with
formula equation (3), the following relation is
corresponds to an unfolded contact surface
of between 3300 and 6600 m2/m3. obtained:
(1)
(4)
It is the hydrolysis of polluting substances For a defined mass of micro-organisms X
and the formation of enzyme-substrate that are in WW volume V, the velocity field In equation (4), it may be accepted that
structures, as well as the absence of toxic may be considered to be homogenous, and the product KXS’ is proportional to the
and inhibiting substances in the removed the field stream may be expressed with the substrate concentration So at the begin-
load of impurities, that allows the transport following formula: ning of the process:
of polluting substances. The removal of , (5)
(2)
impurities is a series process whose result-
where: then equation (4) is as follows:
ant velocity is determined by its slowest
stage. The present author believes that q - the field stream, m3/h
(6)
the flow of the water stream containing X - the micro-organism concentration in
adapted substrate structures is the slowest the system, kg/m3 possibly having determined:
stage of this process. Actual biochemical V - the volume of the system examined,
reactions, so often emphasised in the m3
literature on the subject, only take place K - the kinetic constant of the process,
in intracellular structures, and are the last m3/kgh.
(7)
stage of the process. The efficiency of
biochemical reactions is then controlled The constant K is defined by the prod- If the contact mass concentration X is
by the velocity of the substrate transport to uct: constant in a given period, then after
micro-organism cells in the water stream. integrating equation (7), the following
A simple proof of this is the fact that a equation is obtained:
drop of water content in the environment where:
surrounding micro-organisms below 40% vn - the module of the projection of the (8)
causes a slowing-down and inhibition of vector of the velocity field stream
the process [4]. on the direction of the normal to the Determining in the formula above:
field surface, m/h
According to biochemical criteria, the - the coefficient characterising the
driving force of the process is the so- relationship between the total mi-
called homocellular system, which ensures cro-organism contact surface and
the transport of nutrients to living cells the active (exchange) surface
(micro-reactors) even when the substrate Aw - the mean specific surface of the mi-
concentration in the external environment cro-organisms, m2/kg.
is very low. It is believed then that the The total velocity field stream of a defined
volume of treated WW, V, always fulfils then the shortened notation of equation
substrate flow occurs against the concen-
the condition of zero water balance. (8), describing the progress of the bio-
tration gradient [5].
degradation process, is as follows:
As a result of the occurrence of the phe- Tests for Biological Removal (9)
nomenon of the ‘flow’, the system ‘sew- of Impurities
age environment - micro-organism struc- The nature of the substrate concentration
tures’ should be treated as a defined vector Biodegradation test changes described in the above equation is
velocity field that organises the travel of To examine the process of the loss of im- shown in Figure 1. The presented decrease
substrate-enzyme structures together purities, WW are usually tested using a in pollution concentration expressed by
with water particles. At the same time, preliminary biodegradation test. A drop in COD was determined to examine the

FIBRES & TEXTILES in Eastern Europe January / March 2005, Vol. 13, No. 1 (49) 77
900 3
800
2.5
700
COD, S, mgO2 /dm 3

600 0.73 g/dm3 2 0.73 g/dm3

log(S-S')
500 1.45 g/dm3 1.45 g/dm3
1.5
400 2.90 g/dm3 2.90 g/dm3
300 4.10 g/dm3 1 4.10 g/dm3
200
0.5
100
0 0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 0 1 2 3 4 5 6 7 8 9 10 11 12 13
time, h time, h

Figure 1. Decrease in pollution concentration (COD) in non-flow tanks for different micro-organism concentrations.

process of biodegradation using activated As on the basis of (2) q=KXV, then from given in Figure 2. Two laboratory aeration
sludge from a cotton industry plant [6]. equation (10) tanks were used in the studies conducted in
As the analysis shows, pollution con- the Department of Water Management at
centration in the recirculated stream (10a) the Technical University of Łódź in 1999.
(S’) was numerically close to the con- WW retention times for each tank were
centration of the unremovable substrate 4 and 6 hours, and their active volume was
(S’=228 mg O2/dm3). Determining above: 12 dm3. Each tank was connected with
- removed pollution concen- a secondary settling tank whose volume
Thus, equation (9) may be rearranged into tration was 3 dm3. The pollution concentration in
a linear form by finding its logarithm: and the inflow (So), determined as PV, ranged
between 152 and 228 mg O2/dm3, while
- WW retention (aeration) time in
that of treated sewage (S) was between
the reactor,
and then values Ko and K for different 64 and 88 mg O2/dm3.
then the following statement is obtained
contact mass concentrations of activated
from (10a):
sludge may be determined. The values of Inflow concentration (expressed as COD)
constant Ko were 0.1077; 0.2154; 0.4308; (11) changed from So=480-888 mg O2/dm3,
0.6462 respectively; and of constant K, and was S=152-360 mg O 2/dm 3 after
0.1473; 0.1476; 0.1486; 0.1576 dm3/gh. and substituting: S’=K’So, and rearrang- treatment. A distinct linear relationship
ing, the following equation is obtained: consistent with equation (12) was ob-
Tests of continuous removal of impuri- tained for the treatment results described
ties (12) by COD. The mean value of constant K
When the substrate is continuously de- for this indicator was 0.0465 dm3/gh, and
livered to the contact chamber, which where: 0.298 dm3/gh for oxygen demand. The
usually takes place in biological WW - treatment efficiency: values of constant K’ also varied greatly
treatment, the fundamental mechanisms for both indicators, and were 0.033 for
of the process, defined in statements COD and 0.285 for PV. A greater range
(1-2), are retained. The interpretation of continuous treat- of results was obtained for the retention
ment in activated sludge reactors using time of 6 h, which may be explained by
The balance of the process which mostly the above equation makes it possible to the fact that the mean sludge content in this
occurs in complete mixing reactors is ex- achieve a very high degree of consistency tank ranged between 2.7 and 6.17 g/dm3.
pressed by the following equation: In the tank with the retention time of 4 h,
in the results of experimental studies with
(10) the accepted model. the amount of sludge was greater and at the
same time steadier, ranging only between
where:
5.58 and 6.74 g/dm3. This influenced the
Q - the rate of sewage flowing to the reac- The findings for the cotton industry WW
indicator of sludge contact with WW for a
tor, m3/h. treatment in complete mixing chambers are
defined aeration time (product ), and
thus the treatment outcome which was
1 mostly influenced by the substrate (WW)
quality change.
0.8
S/So=0,033+21,5n/Xt

0.6
S/So

0.4
Summary
S/So=0,285+3,35n/Xt
Figure 2. Textile
0.2
WW treatment in Textile WW, having been technologically
complete mixing pre-processed in qualitative composition
0
chambers with acti- equalisation and neutralisation, may be
0 0.01 0.02 0.03 0.04 0.05
vated sludge (decre-
ase in PV and COD); treated biologically. In biological treat-
n/Xt
o - COD + PV. ment, a load of impurities adapted by mi-

78 FIBRES & TEXTILES in Eastern Europe January / March 2005, Vol. 13, No. 1 (49)
cro-organisms as a substrate is removed The constant K is a measure for the trans-
from WW. The substrate is used by micro- port of the adapted substrate to the cells of
organisms for synthesis, regeneration and micro-organisms, and may not be treated
maintenance of living activity as a source as a constant characteristic parameter,
of energy. The adapted impurities are part in the sense of the kinetics of chemical
of the volatile substance load. Biological reactions. The constant K is exclusively a
oxygen demand (BOD) is a measure for parameter of the kinetics of the process.
the adaptability of this pollution load by
micro-organisms. Alternatively, other It should be noticed that in equation (9),
indicators characterising the presence of which describes the change in the pollution
substances that oxidise easily, principally concentration in non-flow tanks, the value
PV and COD, may be used, provided that R2 may be determined approximately not
BOD is also determined in the WW exam- only on the basis of the examinations but
ined. If BOD is not detected in WW, then also analytically. The characteristic curve
such WW are toxic. described by the equation shows that value
R2 may be determined from the relation:
Micro-organisms adapted to a specific
nutritive substrate must be used in the (13)
biological treatment of textile WW, as
only such groups tolerate toxic and in- where:
hibiting substances. S1, S2 - any two extreme S values, read
from the diagram of the treatment
The loss of impurities from treated WW progress for any time t1 and t2,
and
occurs as a result of the flow of available
S3 - corresponds to the value S read
substrate structures into micro-organ-
from the diagram for
isms through the cell membrane in the
water stream. Appropriate reactions and
metabolic processes take place within
micro-organisms that are miniature bio-
This condition is fulfilled by all the
reactors.
biodegradation curves obtained in the
examinations in which the adapted mass
The values of standard pollution indicators of micro-organisms was used.
of textile sewage, such as COD, BOD5
and PV, fully confirm the consistence of
the experiment results with the accepted
interpretative model. At the same time, References
the parameters characteristic of the treat- 1. Bartkiewicz B, Królikowski A., Lebiedowski
ment processes in the non-flow system M.: Waste water treatment, Monograph,
and the complete mixing system are also Komitet Inżynierii Środowiska Polskiej
confirmed. Indicator equation (3) and bal- Akademii Nauk, Vol. 9, Lublin, 2002.
ance equation (10) summarily present all 2. Imhoff K., Imhoff K.R.: Taschenbach
der Stadtentwässerung, R. Oldenbourg
the basic parameters necessary to describe
Verlag München Wien, 1993.
biological treatment in conditions of the 3. Lebiedowski M.: Dimensioning of Surge
full adaptation of micro-organisms to the Tanks in Treatment Plants in Textile
substrate. Factories, Fibres & Textiles in Eastern
Europe, July/September, 2001.
For treatment of textile WW in which 4. Lebiedowski M.: Selected unit proc-
BOD is determined, the process of sub- esses in water and sewage treatment
- a mathematical approach. Monograph.
strate removal in a biodegradation test is
Wydawnictwo Politechniki Łódzkiej, 2004
a continuous function over time. (in Polish).
5. Lehninger A.L.: Bioenergetics, The
Biological treatment is characterised Molecular Basis of Biological Energy
by two parameters: concentration of Transformations, (Polish translation)
unremovable substances S’ and kinetic PWN, Warszawa, 1978.
constant Ko proportional to the concen- 6. Avoidance of environmental pollutions
tration of the micro-organism mass. The by decoloration of textile waste waters
and their partial re-use. Final Report
qualitative composition of micro-organ-
EGProject CIPA-CT 92-3004, Working
isms determines the value of the constant Period: 01.07.93-30.06.95, ITV Institut für
Ko, which is the product of the constant K Textil- und Verfahrenstechnik, Denkend-
and the concentration of micro-organisms orf, Department of Water Management.
X, and which is influenced by the specific
qualitative composition of the substrate. Received 23.06.2004 Reviewed 10.01.2005

FIBRES & TEXTILES in Eastern Europe January / March 2005, Vol. 13, No. 1 (49) 79