Professional Documents
Culture Documents
______________________________________________________________________
Published By : Dr. B. Sengupta, Member Secretary, Central Pollution Control Board, Delhi 32
Printing Supervision & Layout : P.K. Mahendru and Satish Kumar
Composing, Laser Typesetting & Cover Page Design : Suresh Chander Sharma
Web Version : U.A. Ansari and Shashi Goel
Printed at :
FOREWORD
The release of the Halogenated Organic Compounds in the environment is
increasingly becoming a matter of concern due to their carcinogenic/toxic effects.
Most of these compounds are adsorbable and the level of their presence in
wastewater is assessed in terms of the parameter Adsorbable Organic Halides
(AOX). The formation of these compounds is traceable to the use of Chlorine and
chlorinated compounds in the various industrial processes including the bleaching
process in the pulp and paper industries. The pulp and paper industries also being
one of the major consumers of Chlorine and its compounds, need priority attention
in the context of controlling AOX discharges in their effluents. The Central Pollution
Control board has, therefore undertaken a project for evaluation of the various
bleaching techniques used in the Pulp and Paper industries and their relative
suitability with respect to the minimum discharges of AOX in the effluents.
The present Report covers, a brief description of the pulp bleaching process and
its environmental impact, cleaner technologies for the reduction of AOX
discharges, details and findings of the studies conducted in the nine pulp and
paper units selected for this purpose, and the recommended discharge limits for
AOX.
The able execution of the project by Central Pulp & paper Research Institute,
Saharanpur, is gratefully acknowledged.
We hope that the document would be useful to the pulp and paper industries and
all those concerned directly or indirectly with the management of the Halogenated
Organic Compounds.
(J.M. MAUSKAR)
April, 2007
Development of AOX Standards for Large Scale Pulp and Paper Industries
Project Team
Dr. B. Sengupta,
Member Secretary
Overall guidance
Project execution
Mr. P. M. Ansari,
Additional Director
Project coordination
Dr. R. S. Mahawar,
Additional Director
Mr. H. K. Karforma,
Senior Environmental Engineer
Project coordination
Mr. S. K. Gupta,
Environmental Engineer
PREFACE
Bleach plant effluents from pulp & paper industries are known to exhibit toxicity to
aquatic life. The toxicity is mainly due to discharge of Halogenated Organic Compounds
formed during bleaching of pulp with chlorine based chemicals particularly molecular
chlorine. The increased environmental pressures including the control of the release of
carcinogenic compounds require the paper industries to adopt cleaner technologies
such as the Elemental Chlorine Free bleaching techniques (ECF) and Total Chlorine
Free (TCF) bleaching techniques for reduction of chlorinated organic compounds. Most
of the chlorinated organic compounds that are carcinogenic, are adsorbable and hence
the discharge of AOX needs to be controlled.
Looking into the problems and limitations of the Indian pulp & paper industries in
adoption or up-gradation of their technologies, the Central Pollution Control Board has
undertaken a project on Development of AOX Standards for Large Scale Pulp & Paper
Industries with an objective to assess the status of the technologies and permissible
levels of AOX in effluents in respect of the large scale pulp & paper industries.
The studies were conducted in nine selected pulp & paper industries to collect reliable
information about level of AOX generation. The studies conducted have provided useful
information on the status of the technologies and the levels of AOX discharges in the
large-scale pulp and paper industries.
CONTENTS
1.0
2.0
2.1
2.2
2.3
2.3.1
2.3.2
2.3.3
2.4
3.0
4.0
4.1
4.2
4.3
4.4
4.5
4.6
5.0
6.0
6.1
6.2
6.2.1
6.2.2
6.2.3
6.2.4
6.2.5
6.2.6
7.0
7.1
7.2
7.3
8.0
8.1
8.2
8.3
8.4
9.0
10.0
11.0
INTRODUCTION
PULP BLEACHING AND ITS ENVIRONMENTAL IMPACTS
Bleaching chemicals and Bleaching sequences
Formation of chlorinated compounds
Toxic properties of chloro-compounds
Chlorophenolics
Polychlorinated Dioxins & Furans
Carcinogenic and Mutagenic compounds
Biological effects of Bleach plant effluents
KAPPA NO. AND ITS RELATION TO PULP BLEACHING
CLEANER TECHNOLOGIES FOR AOX REDUCTION
Technologies for Kappa no. reduction
Extended Delignification
Improved Pulp Washing
Oxygen Delignification
Chlorine Dioxide substitution
Oxidative alkali extraction bleaching
NATIONAL/INTERNATIONAL LIMITS FOR AOX DISCHARGES
OBJECTIVE & SCOPE OF THE PROJECT
Criteria for Selection of industries
Methodology
Preliminary Survey of the Selected industries
Identification of Sampling Points
Analysis of samples
Evaluation of Pulp Washing Efficiency
Measurement of AOX
Measurement of Effluent flow rates
INDEPTH STUDIES IN SELECTED INDUSTRIES
Writing & Printing paper manufacturing industries
Newsprint Paper Industries
Rayon Grade Pulp Industries
GENERAL OBSERVATIONS
Writing and Printing Grade Paper Industries
Newsprint Industries
Rayon Grade Pulp Industries
Effluent Treatment Plants
CONCLUSIONS
RECOMMENDATIONS
FINALIZATION AND NOTIFICATION OF AOX STANDARDS
Page No.
1
1
1
3
4
4
4
6
6
6
7
7
7
7
8
8
8
8
9
9
9
9
10
10
10
10
10
11
11
18
23
23
23
28
28
28
31
32
33
1.0
INTRODUCTION
The increasing environmental pressures and changing customer preferences in
all spheres of life has made it essential that the bleaching techniques adopted by
Indian paper industry are also critically evaluated to control and monitor the
discharges of chlorinated organics. It is already known that discharge of
chlorinated organic compounds through effluents and end products from pulp &
paper industries have adverse effect on fauna and flora. The environmental
hazards of bleach plant effluent result from the use of chlorine containing bleach
chemicals especially molecular chlorine. The developed countries specially
Scandinavian countries; Canada and USA have slowly eliminated the use of
molecular chlorine over a period of last two decades and now moving towards
total chlorine free bleaching (TCF) techniques in a phased manner. The Indian
paper industry, which primarily utilises about 20% wood, 60%nonwood and about
20% waste paper, mostly bleach the pulp by chemicals like molecular chlorine,
calcium hypochlorite which are responsible for the formation of chloro
compounds. The quantity of chlorine required for bleaching one tonne of pulp
ranges from 50Kg - 200 Kg. The total available chlorine requirement for different
raw materials is 6-8% in case of Eucalyptus, 8-10% for Bamboo and 8-10% for
Bagasse. It is therefore essential to make an assessment of the existing AOX
levels in the effluents and technologies that are suitable for achieving the AOX
discharge limits that are acceptable in the Indian Pulp and Paper industries. The
present document covers a brief description of the pulp bleaching processes and
its environmental impacts, cleaner technologies for the reduction of AOX
discharges, details of the studies conducted for the characterization of waste
streams in large scale pulp and paper manufacturing industries, and the findings,
and the recommended discharge limits for AOX.
2.0
2.1
Form
Advantages
Disadvantages
Chlorine
Gas
Effective, economical
delignification. Good
practical removal
Hypochlorite
Ca(OCl2), NaOCl
solution 40 gpl
as Cl2
Achieves high
brightness without pulp
degradation. Good
particle removal.
Oxygen
Hydrogen
peroxide
2-5% solution
Expensive, poor
particle bleaching.
Ozone
Gas in low
concentration in
oxygen
Effective, provides
chloride-free effluent
for recovery
Expensive, Degrades
pulp. Poor particle
bleaching
Reductant
Hydrosulfite
(for mechanical
pulps only)
Solution of
Easy to use. Low
Na2S2O4 or
capital cost.
made onsite from
NaBH4 solution
plus SO2)
Decomposes readily.
Limited brightness gain
Alkali Sodium
Hydroxide
5-10% NaOH
solution
Darkens pulp
Effective and
economical
No. of Species
40
40
45
45
20
--
Amounts
upto 500g/t pulp
upto 100g/t pulp
---------------upto 4 kg. Cl/t pulp
2.3.1 Chlorophenolics
The Chlorinated compounds present in the alkali extraction bleach effluent are
found to be more toxic and contribute more than 90% of acute toxicity. The chloro
compounds like trichlorophenol, tri and tetra chloroguaiacols in particular may
accumulate in fish and are responsible for acute toxicity.
2.3.2 Polychlorinated Dioxins & Furans
Among the chlorinated phenolics, the dioxins & dibenzofurans are the groups of
chlorophenoles found to have toxic effects. The prominent among the dioxins
are 2,3,7,8 tetra chloro dibenzo dioxin (TCDD) and 2,3,7,8 tetra chloro dibenzo
furan (TCDF). Dioxins are highly lypophyllic and bioaccumulative compounds.
Such compounds are formed when unchlorinated dibenzo dioxin (DBD) &
dibenzo furan (DBF) present in unbleached pulp are chlorinated in chlorination
stage. The oil based pulp industry additives particularly brown stock defoamers
4
Risk dose*
6.4 x 10-3
1.0
5.7 x 10-2
~20%
Low MW Material
EOX ~ 1%
Relatively Lipophilic
(Fat Soluble).
Potentially Toxic.
Potentially
Bio-accumulable
~ 19%
~80%
High MW Material
Relatively Hydrophilic (Water
Soluble). Mainly Non-aromatic,
Does not Permeate Cell Walls.
1-10% Chlorine By Weight
Relatively Hydorphilic
Includes Compounds
Which can Easily Be
Hydrolysed or Metabolised
(e.g. Tricholoroacetic acid)
1%
Low Pow>3
Highly Lypophyllic
Bio-accumulative.
(e.g. Dioxin 44% Chlorine By weight)
Fig.1. Relative contribution of Chlorophenolic Compounds to AOX
5
3.0
Acute toxicity:
- Egg mortality
- Percentage of fertilized egg.
- Acute toxicity to newly hatched fry.
Late effects: Survival and stress tolerance of fry from exposed parents.
Bioaccumulation:
- Effect on primary production in natural mixed phytoplankton populations.
Genotoxic effects:
- Mutagenic effects
- Carcinogenic effects.
4.0
4.1
4.2
Extended Delignification
The pulp and paper industries normally use kraft process in batch or continuous
digesters to remove the lignin as much as possible during pulping of wood based
fibrous raw material but the process has limitation that the wood based fibrous
raw material can not be delignified to a low kappa number .Since the kappa
number is the main factor which governs the demand of chemicals for bleaching
of the pulp the process was modified to achieve maximum possible delignification
during cooking of raw materials and now most of the industries in developed
countries are employing RDH, modified continuous cooking, super batch
process etc to reduce the kappa number of the unbleached pulp. Modified
pulping processes are energy efficient, require less chemicals for cooking of raw
materials and produce the pulp of low kappa number with better strength
properties as compared to conventional pulping processes. However, the high
capital investment and high level of operation restrict the adoption of these
technologies in Indian pulp & paper industries. Agro based pulp and paper
industries normally use soda pulping process.
4.3
4.4
Oxygen Delignification
Oxygen delignification is a well established technology and most of the pulp mill
abroad are using this process to reduce the kappa number of pulp before
bleaching stage. Single stage oxygen pre bleaching of the pulp reduces the pulp
kappa number by 50-60 % and two stage oxygen pre-bleaching reduces the
pulp kappa number by 80%.
The process is used in large pulp & paper industries in the developed countries.
Indian paper industries have limitations in adopting the process due to high
capital investments involved and low scale of their operation. The process needs
to develop an economically viable oxygen pressure vessel for low scale of
operation as the capacity of small scale pulp mills in the Country varies from 5
100 ton /day or upgrade capacities of their plants for achieving viability in using
these processes.
4.5
4.6
5.0
6.0
MODE
Sweden
<1.0
TOCI
Canada
<1.5
AOX
Germany
<1.0
AOX
India
2.0
TOCl
6.1
6.2
Methodology
10
rectangular notch existing in the drain channels and also by using the float
velocity method.
7.0
7.1
pH
Suspended solids, mg/l
Suspended solids, Kg/ Day
- 84.0
29290
7.2
1080
31633
Contd.
11
9.
e.
Suspended solids, Kg/T Paper
f.
COD, mg/l
g.
COD, Kg/Day
h.
COD , Kg/ T Paper
i.
AOX, mg/l
j.
AOX, Kg/Day
k.
AOX , Kg/ T Paper
Characteristics of treated waste water
a.
Flow , M3 /Day
204
1313
38458
248
18.94
555
3.58
29290
7.4
90
2636
17
269
7879
51
6.48
190
1.22
b.
pH
c.
Suspended solids, mg/l
d.
Suspended solids, Kg/ Day
e.
Suspended solids, Kg/T Paper
f.
COD, mg/l
g.
COD, Kg/Day
h.
COD , Kg/ T Paper
i.
AOX, mg/l
j.
AOX, Kg/Day
k.
AOX , Kg/ T Paper
10.
Efficiency of ETP
a.
Reduction in SS ,%
- 91.67
b.
Reduction in COD,%
- 79.51
c.
Reduction in AOX,%
- 65.78
-------------------------------------------------------------------------------------------------------Unit-2
Details of the industry and findings of the study are given in Table 7.
The industry is manufacturing writing & printing paper, kraft paper & triplex board
from bamboo (50-60%) and mixed hardwoods (40-50%). The unbleached pulp
of Kappa 25 + 2 is used both for writing and printing grade, and also for kraft
packaging & triplex boards. The industry produces 156 t/day writing and printing
paper against a total production of 165 t/day. In case of the production of writing
and printing grade papers, the pulp is bleached by CEHH/CEHHP bleaching
sequence to a brightness level of 78% ISO. The total AOX load generated is
5.03 kg/t of paper (831 kg/day) which is reduced to 2.50 kg/t of paper production
(413 kg/day) after secondary treatment. The overall reduction in AOX in the ETP
is 50.30%.
12
Unit-3
Details of the industry and findings of the study are given in Table 8.
The industry is producing fine variety of paper from bamboo (90%) and
Eucalyptus (10%). The production of paper during sampling period was 252 tpd.
The pulp having kappa no.20-22 is bleached by C/D EoHHD bleaching sequence
to a brightness level of 82-84% ISO. The total AOX load generated is 4.49 kg/t
paper production (1131 kg/day), which is reduced to 2.40 kg/t (603 kg/day) paper
production after secondary treatment. The overall reduction in AOX during in the
ETP is 46.72%.
Unit-4
Details of the industry and findings of the study are given in Table 9.
This industry is mainly based on bagasse, bamboo, and eucalyptus in addition to
little proportion of imported pulp. Presently the industry is producing around
63t/day rayon grade pulp, 110 t/day writing & printing paper from eucalyptus and
bamboo, and about 110t/day writing and printing paper from 90% bagasse
bleached pulp and 10% imported bleached pulp. Rayon grade pulp (kappa
no.16) is bleached by CEHD - SO2 bleaching sequence to a brightness level of
87% ISO, while Eucalyptus & bamboo pulp of kappa no 18-20 is bleached by
CEHHD-SO2 bleaching sequence to a brightness level of 83% ISO and bagasse
pulp of kappa 12-13 by C/DEoD bleaching sequence to brightness level of 85%
ISO. The total AOX load generated is 2.32 kg/t production (662 kg/day) which is
reduced to 1.37 kg/t production (390 kg/day) after secondary treatment and final
discharge. The overall reduction of AOX in the ETP is 41%.
Table - 7 : Details and findings of study in Unit-2
-----------------------------------------------------------------------------------------------------------1.
- 70,000
2.
Raw materials
- Bamboo (50-60%)
Mixed Hardwoods(40-50%)
3.
Total
- 165
b.
Kraft
- 9-10
c.
W & P Grade
- 156
4.
Pulping process
- Sulphate pulping
5.
- 22 - 28
13
Contd.
6.
Bleaching sequence
- CEHHp
7.
- 85.0
8.
9.
10.
a.
Flow , M3 /Day
- 44110
b.
pH
- 8.64
c.
- 3000
d.
- 132330
e.
- 802
f.
COD, mg/l
- 1277
g.
COD, Kg/Day
- 56329
h.
- 341
i.
AOX, mg/l
- 18.83
j.
AOX, g/Day
- 831
k.
- 5.03
Flow , M3 /Day
- 44110
b.
pH
- 7.54
c.
- 260
d.
- 11468
e.
- 70
f.
COD, mg/l
- 272
g.
COD, Kg/Day
- 11998
h.
- 73
i.
AOX, mg/l
- 9.36
j.
AOX, Kg/Day
- 413
k.
- 2.50
Efficiency of ETP
a.
Reduction in SS ,%
- 91.33
b.
Reduction in COD,%
- 78.70
c.
Reduction in AOX,%
- 50.30
-----------------------------------------------------------------------------------------------------------
14
8.
- C/ DEoD ( B)
Bleached pulp brightness,% ISO
- 86 (Eucalyptus, RG)
80 (bagasse, W & P)
83 (Eucalyptus, W & P)
Characteristics of waste water (Influent to ETP)
a.
Flow , M3 /Day
- 61440
b.
c.
d.
e.
f.
g.
h.
i.
j.
k.
pH
Suspended solids, mg/l
Suspended solids, Kg/ Day
Suspended solids,Kg/T paper
COD, mg/l
COD, Kg/Day
COD , Kg/ T Paper
AOX, mg/l
AOX, Kg/Day
AOX , Kg/ T Paper
6.6
370
22733
80
485
29798
105
10.77
662
2.32
Contd.
16
9.
10.
61440
7.3
240
14745
52
390
23962
84
6.35
390
1.37
- 35.14
- 19.59
- 41.00
Unit-5
Details of the industry and findings of the study are given in Table 10
The industry has installed capacity of 300 tonnes/day of manufacturing high
quality bleached paper varieties. The main fibrous raw materials used are bamboo
and wood. The mill has employed cleaner technologies like RDH Pulping, Oxygen
Delignification with chlorine dioxide bleaching. The CDEoPD bleaching sequence
is used for bleaching of the pulp having Kappa No 15-17. The AOX level in effluent
before treatment is 1.92 Kg/tonne of paper while after treatment in ETP its level
comes down to 1.07 Kg/tonne of paper . The over-all reduction in AOX in the ETP
is 44%.
Unit-6
Details of the industry and findings of the study are given in Table 11.
The paper industry has installed capacity of 53868 t/year for manufacturing writing
& printing grade of paper. The main fibrous raw materials used for manufacturing
17
of quality paper are bamboo,wood,bagasse and grasses( Sabai,khar & Kai). The
industry has two pulping street, new pulp mill is used to produce wood pulp having
kappa no.20-21. While the existing old pulp mill with eight nos. of digestors (32 m3
each) is used to produce pulp of kappa no.13-15 from bagasse & grasses. The
industry is practicing both conventional bleaching (CHH) for pulp of low kappa no.
pulp & CDEDD for wood pulp. The AOX level in effluent before treatment is 4.0
Kg/tonne of paper while after treatment in ETP its level comes down to 1.84
Kg/tonne. The over-all reduction in AOX in the ETP is 54%.
7.2
18
Total
- 2,00,000
b.
Newsprint
c.
W & P Grade
2.
Raw materials
3.
Paper production,T/Day:
4.
a.
Total
- 529
b.
Newsprint
- 276
c.
W & P Grade
- 253
Pulping process
5.
- 20 ( Eucalyptus CP)
10 (bagasse CP)
6.
Bleaching sequence
- CEH(bagasse CP)
- CEHH(Euc.CP)
- P(bagasse CMP)
7.
- 85 ( Bagasse, CP)
% ISO
- 65 (Bagasse, CMP)
- 75 (Eucalyptus, CP)
8.
- 69120
b. pH
- 6.3
- 740
- 51149
- 853
g. COD, Kg/Day
- 58959
- 112
i. AOX, mg/l
- 13.69
j. AOX, Kg/Day
- 946
- 1.79
21
9.
- 68160
b. pH
- 6.95
- 90
- 6134
10.
f. COD, mg/l
- 181
g. COD, Kg/Day
- 12337
- 23
i. AOX, mg/l
- 6.22
j. AOX, Kg/Day
- 424
- 0.80
Efficiency of ETP
a. Reduction in SS ,%
- 88.00
b. Reduction in COD,%
- 79.08
c. Reduction in AOX,%
- 55.30
----------------------------------------------------------------------------------------------------------------Unit-8
Details of the industry and findings of the study are given in Table 13.
This newsprint industry is based on hardwoods (Eucalyptus & Casurina) CMP,
CP of hardwoods and bamboo/reed (70:30) and the imported CP of softwood.
The newsprint production was 250t/d during sampling period. The CP produced
from hardwoods & bamboo/reed having Kappa no. around 20 is bleached by
CH/E sequence to a brightness level around 60-65% ISO. While CMP produced
from hardwoods is bleached by Hydrogen peroxide to brightness level around
55% ISO. The newsprint furnish is 70-75% CMP & 25-30% CP including
imported CP. The results indicated that generation of total AOX load is 0.53 kg/t
of newsprint (133 kg/day) which is reduced to 0.14 kg/t newsprint(36kg/d)
production after secondary treatment. The over-all reduction in AOX is about
72.79% during the treatment.
22
7.3
8.0
GENERAL OBSERVATIONS
A summary of the findings of the generation/discharges of AOX, SS and COD in
different pulp and paper industries is given in Table 15.
8.1
9.
7.70
227
4168
38
653
11989
109
4.14
76
0.69
17208
7.30
50
860
7.82
281
4836
44
1.26
22
0.20
b.
pH
c.
Suspended solids, mg/l
d.
Suspended solids, Kg/ Day
e.
Suspended solids,Kg/T paper
f.
COD, mg/l
g.
COD, Kg/Day
h.
COD , Kg/ T paper
i.
AOX, mg/l
j.
AOX, Kg/Day
k.
AOX , Kg/ T paper
10.
Efficiency of ETP
a.
Reduction in SS ,%
- 79.36
b.
Reduction in COD,%
- 59.67
c.
Reduction in AOX,%
- 71.48
-------------------------------------------------------------------------------------------------------------25
1.
Paper production,T/day
2.
Unit-1
Unit-2
Unit-3
Unit-4
Unit-5
Unit-6
Unit-7
Unit-8
Unit-9
a. Total
155
165
252
285
307
198
529
250
110
b. Kraft
45
10
--
--
--
--
--
--
--
c. W & P Grade
110
156
--
222
307
198
253
--
--
d. Rayon pulp
--
--
--
63
--
--
--
--
110
e. Newsprint
--
--
--
--
--
--
276
250
--
26-30
22-28
20
16 (RG)
15-17
2021(W)
10(B)
20
12
13-15(B)
20(E)
CDEDD
(W)
CEH(B)
CHE
CEOHEP
DSO2
CHH(B)
CEHH
(W)
10(B)
20(E)
3.
Bleaching sequence
CEPHH
CEHH
C/DEOH
HD
CEDH
(RG)
CDEOPD
C/DEOD
(B)
CEHHD
(W)
4.
84
85
84
%ISO
86
P(B)
87
82
85
63
84
87
217
129
109
156
80
83
5.
18
267
314
26
216
S.
No
6.
Unit-1
Unit-2
Unit-3
Unit-4
Unit-5
Unit-6
Unit-7
Unit-8
Unit-9
3.58
5.03
4.49
2.32
1.92
4.0
--
--
--
b. Rayon pulp
--
--
--
--
--
--
--
--
0.69
c. Newsprint
--
--
--
--
--
--
1.79
0.53
--
1.22
2.50
2.40
1.37
1.07
1.84
0.80
0.14
0.20
a. W & P grade
7.
8.
8.1
SS in untreated effl.
204
802
320
80
136
118
97
59
38
8.2
SS in treated effl.
17.0
80.0
74.0
52.0
13
12
12.0
15.0
8.0
9.
9.1
248
341
370
105
136
160
112
73
109
9.2
51.0
73.0
91.0
84.0
33
34
23.0
39.0
44.0
10.
Efficiency of ETP
a. Reduction in TSS, %
91.67
91.33
76.89
35.14
89
90
88.0
74.82
79.36
b. Reduction in COD,%
79.51
78.70
75.28
19.59
77
79
79.10
47.16
59.67
c. Reduction in AOX, %
65.78
50.30
46.72
41.00
44
54
55.30
72.78
71.00
Note : Unit-1; Unit-2; Unit-3; Unit -4; Unit -5; Unit -6; Unit -7; Unit -8; Unit -9
CP- Chemical pulp ; CMP :- Chemi-mechanical pulp ;
C - Chlorination; E- Extraction; H- Hypochlorite
P - Hydrogen peroxide D - Chlorine dioxide;O - Oxygen
(RG)- Rayon grade;(W) Wood,(B) Bagasse,(E) Eucalyptus
27
8.2
8.3
8.4
(ii)
(iii)
The generation and discharge of COD measured also vary from industry
to industry depending on end product. The reductions in COD observed
after secondary treatment varied from 47 to 80 % except in Unit-4, where
COD reduction measured was only 20 % which may be because of
unstabilization of new bagasse based pulp industries at the time of sample
collection.
(v)
Table - 16 : AOX generation and discharge in large scale Writing & Printing paper
Industries
S.
No
1.
Parameters
Unit 1
Unit 2
Unit 3
Unit 5
Unit 6
Raw materials
Bamboo,
Pine &
Eucalyptus
Bamboo &
Eucalpytus
Bamboo &
Wood
2.
Pulping process
Sulphate
Bamboo &
wood
(Mixed
hardwood)
Sulphate
Sulphate
3.
4.
5.
26-30
No
CEOHH
22-28
No
CEHHP
20
No
C/DEOHHD
Sulphate
(RDH)
15-17
Yes
C/DEOPD
Bamboo,
wood
grasses &
Bagasse
Sulphate
6.
Total Paper
Production, t/day
Writing & Printing
Others
Total Cl2 Applied %
Total Elemental Cl2,%
Chlorine dioxide,%
AOX content, mg/l
Influent
Effluent (Final)
AOX level, kg/t paper
Generation
Final Discharge
Reduction in AOX, %
Effluent discharge,
m3/t paper
110
45
10.5
6.0
--
156
10
16.2
7.70
--
252
-9.45
5.50
0.25
307
-4.6
3.5
1.10
198
-9.5+14.0
6.0+5.0
3.5
18.94
6.48
18.83
9.36
14.28
7.62
22.01
12.20
18.24
8.32
5.05
1.72
66
189
5.32
2.65
50
267
4.49
2.39
47
314
1.92
1.07
44
88
4.0
1.84
54
220
a.
b.
7.
8.
9.
10.
a.
b.
11.
a.
b.
12.
13.
29
20-21
No
C/DEDDCH
H
20
- Mechanical pulp
--
Bleaching Sequences
Chemial Pulp
CHE
20-Eucalyptus
10-Bagasse
---
P+P
CEH -Bagasse
CEHH-Eucalyptus
P
5.80
9.50
4.00
6.00
Newsprint production,t/d
250
276
Other variety(W&P),t/d
---
253
Total Flow,m3/d
27311
69120#
AOX,Level
-Influent,mg/l
-Effluent " "
4.85
1.32
13.69#
6.22#
AOX,Kg/t product
-Generation
-Final Discharge
0.53
0.14
1.79#
0.80#
Reduction in AOX,%
72.79
55.20
Mechanical Pulp
30
12.8
16.00
Bleaching Sequences
CEoHEPD
CEHD
4.60
5.5
2.50
2.80
110
63
Total Flow,m3/d
18360
61440#
AOX Level,mg/l
Influent
Effluent
4.14
1.26
10.77#
6.25#
AOX,Kg/t pulp
-Generation
-Final Discharge
0.69
0.20
2.32#
1.37#
Reduction in AOX,%
71.48
41.00
-----------------------------------------------------------------------------------------------------------(#)
9.0
Includes writing and printing paper grade streets from Bagasse Eucalyptus
and Bamboo.
CONCLUSIONS
(i)
(ii)
Almost all the paper industries are using diverse raw materials due to non
availability of conventional single raw material and as a consequence, the
performance of existing equipment and technology is usually below the
expected standards.
31
(iii)
(iv)
The generation of AOX measured in effluents from both rayon grade pulp
& newsprint industries was below 1.0 kg AOX/t paper. The degradation of
AOX in biological treatment plant observed is more than 70% and the level
of AOX measured was further reduced below 0.50 kg/t paper in final
discharge. The higher reduction of AOX in these categories of industries
compared to writing & printing paper industries may be because of low
initial concentration of AOX in influents.
(v)
The generation of AOX measured varies from 2.0 to 5.30 kg AOX/t paper.
The lower value i.e 2.0 kg was measured in relatively modern industry (
Unit-5) employing RDH pulping, oxygen delignification with chlorine
dioxide in bleaching processes. In general, the generation of AOX in
writing & printing paper industries varied from 1.92 to 5.32 kg AOX/t
paper. The degradation of AOX in biological treatment plant varies from
44 to 65 % and the level of AOX in final discharge reduced from 2.0-5.3
kg to 1.0 - 2.65 kg of AOX/t paper in these category of industries. The
variation in performance of ETP for removal of AOX may also be due to
initial high concentration of AOX in terms of mg/l due to varying quantity of
water consumed per tone of paper. The main reason of high level of AOX
may be because of use of high dosage of molecular chlorine due to high
carryover of organic matter alongwith pulp to bleaching section & also
requirement of high brightness of end product. The results of AOX
assessed indicate that the generation of AOX at source is lower in the
industries using modified pulping & bleaching processes, where the
generation of AOX is about 2.00 kg which is further reduced to 1.00 kg/t
paper in final discharge. However, some paper industries have already
started the use of chlorine dioxide & oxidative alkali extraction bleaching to
improve the quality of pulp & bleach plant effluent.
(vi)
32
10.0
11.0
RECOMMENDATIONS
(i)
The newsprint grade paper and rayon grade pulp industries may continue
to use the existing pulping & bleaching conditions, since the final
discharge of AOX in these categories of industries is well below 1.0kg
AOX/t of product. However, in rayon grade pulp industries, the generation
& discharge of AOX levels could be further reduced to lower levels by little
substitution of molecular chlorine with chlorine dioxide without any
modification in existing operating conditions. It is observed that the
industries studied are using chlorine dioxide in final stage of bleaching,
where the generation of AOX is negligible.
(ii)
The higher level of AOX appears to be only in writing and printing pulp &
paper industries especially in those which are using molecular chlorine or
very little chlorine dioxide is used to bleach the pulp to high brightness
level where final discharge of AOX varies from 2.40 to 2.70 kg/t of paper
while in industries using modified pulping & bleaching processes, the final
discharge of AOX varies from 1.0 to 2.0 kg/t of paper.
(iii)
Date of implementation
From January 01,2002
From April 01,2002
Ministry of Environment & Forests (GOI) has finalized and notified the following
standards of AOX in case of Large scale pulp & paper industries vide notification
G.S.R.546(E), dated 30.08.2005. The maximum permissible discharge limits for
AOX specified in this notification are:
(A)
1.50 Kg/t of paper produced with effect from the date of notification i.e
30.8.2005, and
(B)
1.00 Kg/t of paper produced with effect from the 1st day of March, 2008.
33