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GUIDELINES FOR
� � .... PROBES/50/1993-94
ENVIRONMENTAL AUDIT
CENTRAL POLLUTION CONTROL BOARD PARIVESH BHAWAN, EAST ARJUN NAGAR
DELHI - 110032
OCTOBER, 1993
C:ANUL-! PM4
© CPCB. 1993; 500 Copies
t"';,.;!Jlishz.j by Central Pollution Control Board, Delhi - 11 0032 &
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FOREWORD
Environmental Audit is an exercise of self-assessment to minimise the generation of wastes and pollution potential.
A gazette notification on environmental audit has been issued by the Ministry of Environment and Forests o_n March 13, 1992 (amended vide notification GSR 386 (E) dated April 22, 1993). This notification applies to every person carrying on an industry, operation or process requiring consent to operate under Section 25 of the Water (Prevention and Control of Pollution) Act, 1974 (6 of 1974) or under section 21 of the Air (Prevention and Control of Pollution) Act, 1981 (14 of 1981), or both, or authorisation under the Hazardous Waste (Management and Handling) Rules, 1989, issued under the Environment (Protection) Act, 1986 (29 of 1986). The notification requires that an Environmental Statement for the financial year ending the 31st March be submitted to the concerned State Pollution Control Board, on or before the 30th September of the same year.
To assist the industry in carrying out environmental audit, the Central Pollution Control Board has conducted some case studies. This publication deals with the pesticide industry.
I hope, the guidelines and the case studies ""!ill be useful to all concerned with the methodologies for environmental audit.
The cooperation extended by Pesticide Association of India and the pesticide industries is gratefully acknowledged.
October 29, 1993
iii
(DILIP BISWAS) Chairman
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PROJECT TEAM
Audit teamfor case studies
Company 'A' Dr. D.D.Basu Sh. N.Raghu Babu m Dr. AK.Singh z Dr. R.C.Shrivastava < Sh. Subhash Chandra (/) Sh. Mehtab Uikey 0
CD Company 'B' Dr. D.D.Basu ::J ...+
Sh. N.Raghu Babu """"I CD
Dr. AK.Singh 0 Sh. S.S.Pal
Sh. S. Jeypaul "'U 0 Industry's Representatives .OJ -Research Sh. N.Raghu Babu �
Dr. D.D.Basu
� Report preparation Sh. N.Raghu Babu (")
""O (") Technical editing O'" CD & report finalisation Dr. S.P.Chakrabarti ::J <
Typesetting and (/) Computer services Ms. Rajni Arora ::J
Sh. Gopi.P. (") ::J
Drawings Ms. Bonya Basu -
Sh. Ramesh Singh Shahi
Printing Supervision Sh. R.N. Jindal
iv
CONTENTS Page No.
1.0 INTRODUCTION . .. . .. ...... . .. . .. . . .. . ...... . ......... . ... . 1
2.0 PHILOSOPHY OF ENVIRONMENTAL AUDIT 2.1 Definition . . . . . . .. . .. .. . ........... : ................. , 2
2.2 Benefits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.3 Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.0 AUDIT PROCEDURE · . . . . . . . . . . . . . . . . . . . .'' ............. , ....... 5
4.0 CASE STUDIES
5.0
4.1 Organochlorine Pesticides Industry . . . ...... . . . ...... . . .- ...... 21
4.2 Organophosphorus Pesticides Industry 36'
RESOURCE SECTION 5.1
5.2
5.3
5 . 4
5.5
5.6
MINAS for pesticides industry . . ... . .. . .. .. . . .. .. . ... . . . .. 57
Separation technologies for removal of organic and pesticides from wastewater . . . . . . . . . . . . . . . . . . . . . 59
Destruction and detoxification technologies for toxic wastes . . ... .... . ....... . ...... .. .... . . ..... . . , 60
Treatment options for wastewater from pesticides industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
Industry - specific limits for water use and wastewater generation .............. . . ..... . ...... .. 62
.' '
Emission standards for some specific pollutants . . . . . . . . . . . . . . . 64
ANNEXURE I: Gazette notification on environmental statement . ... . ... . . 65
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ANNEXURE U : Questionnaire for environmental audit . . . . . . . . . . . . . . . . 68 ..._...
ANNEXURE Ill : Guidelines to environmental safe layout . . . . . ... . . . .. . 76
ANNEXURE IV :Guidelines to minimise material loses and wastes .. . .... 79
List of Figures :
3.1 Environmental Audit - Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 i)
3.2 Process Flow Diagram of Monocrotophos . . . . . . . . . . . . . . . . . . . . . . . . 1 o
3.3 Typical Components of an Unit Operation . . . . . . . . . . . . . . . . . . . . . . . . 11
v
3.4 Mass Balance of Water Consumption and Effluent Generation in Industries . . . . . . . . . . . . . . .. . .. . . .. .. . . . . . . . . . . . 13
3.5 Wastewater Flow Lines . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . · 14
4 . 1 Sources of Wastewater and Emissions . . . . . . . . . . . . . . . . . . . . . . . . . . 25
4.2 Water Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4.3 Wastewater Discharge Characterisation . . . . . . . . . . . . . . . . . . . . . . . . . 2 8
4.4 Proposed Wastewater Treatment System . . . . . . . . . . . . . . . . . . . . . . . . 35
4.5 Process Flow Diagram of Cypermethrin . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.6 Process Flow Diagram of Dichlorovos ... . . . . . . . . . . . . . . . . . . . . . . . 41
4.7 Process Flow Diagram of Phosphamidon . . . . . . . . . . . . . . . . . . . . . . . . 42
4.8 Raw Water Consumption - Water Balance . . . . . . . . . . . . . . . . . . . . . . 46
List of Tables:
3.1 Data sheet on Inputs and Outputs for the
4.1
4.2
4.3
4.4
4.5
4.6
Manufacture of Monocrotophos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 ;
Raw Material Requirement - Stoichiometric Vs. Actual . . . . . . . . . . . . . . . . 2;4
Process Emissions - Type, Source and Control Equipment . . . . . . . . . . . 29
Ambient Air Quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Ground Water Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Data Sheet on Inputs and Outputs for the Manufacture of Cypermethrin . . . . . . . . . . . . . . . . . .. . .. . . . . . .. . . . . . . . . . . . . . 4 3
Data Sheet on Inputs and Outputs for the Manufacture of Dichlorovos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 4
4.7 Data Sheet on Inputs and Outputs for the Manufacture of Phosphamidon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.8 Details of Emissions . . . . . . . . . . . . . . . . . . . . . . . . . • . . . . . . . . . • . . . 48 '
4.9 Details of Hazardous Waste generated . . . . . . . . . . . . . . . . . . . . . . . . . 49
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1 . 0 INTRODUCTION
Industrial pollution in our country is on increase and is creating a high
risk environment. Various legislations viz. the Water ( Prevention &
Control of Pollution) Act . 1974. the Air ( Prevention & Control of Pollution)
Act. 1 9 81 and the Environment ( Protection) Act. 1 9 86 have come into
force and organisations created to combat pollution. Gone are the days
when industrialisation meant profit-making and environment was
grossly neglected. It is being realised that industry and environment
should go hand-in-han d so as to achieve sustainable development. Also
over the years awareness has brought in realisation to consider
environmental protection a bare necessity. Yet. the investments for such
a protection are still considered a liability by many a i n dustrialists
mainly due to lack of up-to-date scientific practices of environmental
management. Consideration of environmental factors at par with
production helps in minimising material losses and also in reduction of
liabilities in t h e long run.
T h e growing environmental pollution and the complexity o f t h i s problem
with increasing risks from the regulatory controls needs an effective
management tool so as to prevent pollution and to make pollution
control programmes cost- effective and feasible.
'Environmental audit' is a technique being introduced for integrating the
interest of the industry and the environment so that these could be
mutu ally supportive. This technique is basically a part of industry's
internal procedures in meeting their responsibil ities towards better
environment. Also the policy statement for abatement of pollution by the
Government oflndia provides for submission of environmental statement
by all concerned industr ies. which would subsequently evolve into an
environmental audit. A notification under the Environment ( Protection)
Rules. 1 9 86 has been issued on April 22. 1993 . requiring industries to
submit an environmental statement for the financial year ending on
March 31 in Form V to the concerned State Pollution Control Boards on
or before September 30 every year beginning 1993 ( Annexure I). The
Department of Company Affairs also agreed to include this requirement
as a part of the Director's Annual Report. The s u b mission of an
environmental statement is applicable to the following:
i ) Those who require consent under the Water ( Prevention & Control
of Pollution} Act. 197 4:
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ii) Th ose wh o require consent under the Air ( Prevention & Control of
Pollu tion) Act. 198 1: and
iii) Th ose who require authorisat ion u n der Hazardous wastes
( Management & Handling) Rules, 1989.
The present docu ment outlines the guidelines for environmental audit
with particular reference to pesticides indu stry.
2 . 0 PHILOSOPHY O F ENVIRONMENTAL AUDIT
2 . 1 Definition
Environmental auditing is a management tool comprising a systematic,
documented, periodic and objective evalu ation of h ow well t h e
management systems are performing with th e a i m of:
il waste prevention and reduction:
iii assessing compliance with regulatory requirements;
iii) facilitating control of environmental practices by a Company's
management: and
iv) placing environmental information in the pu blic domain .
In the indu stries, especially the chemical indu stries. raw materials are
used in excess of the stoichiometric requirements because of the
limitations on practically achievable operational efflciencies and the raw
materials' purity . These excess usages of raw materials. u nless recovered,
find th eir way to environment causing pollution . Wastes from an
industry include n on-product discharges in gaseou s . liqu id and solid
phases. End-of-the-pipe waste treatment tech n iques , wherein all the
wastes are carried to a common facility for treatment.is proving to b e
in effective and unecon omical du e t o the complexity o f problems
associated with waste gen eration, their quantity and characteristics . Th e
waste gen e ration may vary h ou rly. daily and seasonally. especially in case of the multiplicity of manufacturing produ ct in the same premises .
Th e wastewater characteristics also widely vary from stream to stream
discharged from variou s u n it operations of a particular produ ct . In th is
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growing complexity of problems, the concept of waste prevention and
reduction can workout to be more effective.
It is important to find out whether an industry is complying with
environmental standards and other regulatory requ irements. It is also
very essential to periodically monitor this aspect, determine the gaps and
workou t action plans for implementation with in a reasonable time frame
keeping in view the flnancial and other considerations of a Company. In
cases o f gaps for compliance with the regulatory requ irements . the
regu latory bodies could be apprised of these action plans and time
obtained for implemen tation. Thu s the regu latory risk could be
overcome and effective steps taken for pollu tion control.
Many a times , the top management of a Company or an industry may
not be aware of the factual situation of their indu stry from
environmental angle. Such u nknown facts form hidden liabilities more
often than not expose an industry to regu latory risks . The management
shou ld be able to periodically review the environmental practices of the
Company to formulate/modify the Company's environ mental policy
accordingly.
It is also imperative that the management of a Company shou ld have a
clear picture of 'attitudes' and 'technical capabilities' of their
organisational set-u p for protecting environment . pollu tion control J
status . and their bounden social obligation related to environment so as
to decide on the future mode of actions. Public are to be made aware of
the environmental information o f the Company . especially to those who
are shareholders . so as to bu ild-in among them confidence.
Environmental auditing can be viewed as a 'management tool' internally,
and 'liaison' externally with the public and regulatory bodies.
2.2 Benefi ts of Environmental Audi t
Environmental auditing has far reaching benefits to the industry. to the
society and the nation at large. The benefits of environmental audit are:
ii determines how well the process systems and pollution
control systems are performing, and iclentifles the operations
of poor performance:
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2.3
iii identifies potential cost savings which can be accru ed
through redu ction in raw material consu mption by way of
waste minimisation. and adoption of recycle / recovery I redu ction in pollution load :
iii) increases awareness of environmental requ irements . policies
an d responsibilit ies:
iv) helps in understanding the technical capabilities and attitu de
of the environmental organisation in a Company:
v )
v i )
vil)
viii)
provides u p-to-date environ mental data base fo r use i n plant
modification, emergencies etc.:
unravels su rprises and hidden liabilities du e to which
regu latory risk and exposure to litigation can be redu ced;
ensu res independent verification. identifies matters n eeding
attention . and provides timely warning to management on
potential future problems: and
helps to safegu ard environment. and assists i n complying
with local. regional an d national laws and regulations. with
the Company's policy and with the envir.onmental standards.
Objectives
The environmental audit helps in pollution control. improved production .
safety an d h ealth and conservation of natu ral resou rces and hence its
overall objective can be stated as achieving of sustainable development.
However for condu cting environmental au dit, objectives are t o be denned
clearly. or e lse the au dit procedu re will be subject t o varying
interpretations which may yield and contribute to differences i n
approach thereby infh�encing t h e end resu lts. The objectives o f
environmental au dit in a n indu stry are :
i) to determine the mass balance of various materials used and the
performance of various process equ ipment so as t o identify usage of
materials i n excess than requ ired. t o rev1ew t h e conversion
efficiencies of process equ ipment and accordingly fix up norms for
equ ipment / operation performance an d minimisation of t h e wastes .
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ti ) ( a) to identify the areas of water usage and wastewater
generation and determine the characteristics of wastewater:
(bl to determine tl\e emissions. their sources. quantities and
characteristics; and
( c) to determine the solid wastes and h azardous wastes
generated, their sources. quantities and characteristics.
iii) to identify the possibilities of waste minimisation. and recovery and
recycling of wastes;
iv) to determine the pe rformance of the existing waste treatment/
control systems so as to modify or in stall additional or alternative
control equipment accordingly:
v) to determine the impact on the surrounding environment
(groundwater. stream, residential area, agricultural area, sensitive
zone. etc. ) due to the disposal of wastewater, emissions and solid
wastes from the industry and accordingly identify suitable
preventive measures. if necessa1y:
vi) to verify compliance with the standards and conditions prescribed
by the regulatory bodies under the Water Act, the Air Act and t h e
Environmental ( Protection) Act: and
vii) to check the effectiveness of (a) organisational set-up of t h e indu stry
for decision -making and environmental management with special
reference to their 'technical' view point . 'attitudinal' view point and
training. and (b) environmental policy of the Company.
3.0 AUDIT PROCEDURE
The audit procedure includes broadly the following :
i) Pre- audit activities;
i i ) Activities at t h e site: and
iii) Post-audit activities.
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3 .1
3 .1.1
3 .1.2
The details of th ese activities and the entire au dit procedu re are depicted
in Fig. 3.1. Th is procedt:re is discussed in detail below.
Pre-audit Activities
Preliminary information
Pre - au dit activities include various preparatory works. Having chosen
the industry t o be au dited, preliminary information on the industry are
to be obtained through a qu estionnaire. Th e information include
location of the industry with su rrou nding landuses, climatic conditions,
produ cts manufactu red. raw materials used. details on water utilisation,
wastewater generation and disposal. gaseous emissions, solid
waste / hazardous waste, and organ isational set - u p and policies of the
Company for environmental management. A typical qu es.tionnaire is
given in Annexure I I .
Th e preliminary information received on t h e indu stry shou ld be reviewed
to identify main areas of concern . Thereafter it is requ ired to prepare
and organise audit team and resou rces. and allocate specific tasks to
team members . Resou rces such as the sampling and mon itoring
equ ipment and laboratory facilities for analysis shou ld be checked if
available at site or e lse arrangements shou ld be made for their
availability through external sou rces such as private /government
laboratories. loan from other industries etc. Th e visit programme shou ld
then be intimated to the indu stry mention ing that the environmental
au dit shou ld not be considered as a raid. Th e prior intimation to the
industry helps them convince the sen ior management and staff at
various levels of the pu rpose of au dit and the cooperation they have to
extend to the audit team. Th e staff shou ld not fee l that the au dit wou ld
lead to surfacing problems and hence they would be subject to criticism
by the management. They shou ld be made clear about the pu rpose
and objectives of the audit and how beneficial it wou ld be for the
industry. Th is would also increase employees' awareness towards waste
redu ction and promote input and su pport for the au dit.
Audit team
Audit team shou ld be carefu lly selected to cover variou s as pects of the
au dit. The team shou ld include employees from produ ction. qu ality
control/laboratory. R&D. pollu tion control operations. techn ical staff for
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.---1 PR -AUDI AC IV
OBT Al,N PRELIMINARY INFORMATIONS THROUGH G.UESTIONNAIRE SURVEY
REVIEW AND IDENTIFY HAIN AREAS OF CONSIDERATION
¢.
PREPARE AUDIT TEAH
ORGANISE RESOURCES
DEVELOP VISIT PROGRAH"1£
;\LLOCA TE SPECIFIC TASK TO TEAM MEMBERS
• INTERVIEWS WITH CROSS SECTION OF STAFF
• VERIFICATION OF RECORDS OF THE COMPANY
•FIELD INSPECTION
llA1911AL aal..NC2t. •DETERMINE PROCESS INPUTS,
RECORD WA5n USAGE AND OF RECYCLE/REUSE
•DETERMINE PROCESS OUTPUTS: O.UANTIFY PRODUCTS/8YPRODUCTS, ACCOUNT FOR WA5Tf. WATER, EMISSIONS AND SOUD/HAZ. WASTE
•INCORPORATE DAT A ON PROCESS FLOW SHEETS, DERIVE MATERIAL BALANCE ANO WATER BALANCE
�Pl.OWi .lDENTIFY WASTE FLOW
LINES •OBTAIN OET AILS OF PRE
TREA THENT AND FINAL TREATMENT
•OBTAIN DETAILS OF DISPOSAL
•DESIGN MONITORING NETWORK FOR SAMPLING WASTEWATER. SOLID WASTE, PERFORMANCE STUDY OF TREATHEl''T l=ACILITIES AND THE
RECEVING ENVIRONMENT • IDENTIFY PARAMETERS FOR
ANALYSIS •DETERMINE TYPE AND
FREO.UENCY OF SAMPLING •ANALYSE SAMPLES
CONC1 •l>ltQ IElllON • DRAFT REPORT PREPARATION •PRESENTATION OF DRAFT
REPORT AND DISCUSSION WITH THE MANAGEMENT
� . • EVALUATE PERFORMANCE & ADEQACY
JF THE WASTE TREATMENT FACILITIES • IDENTIFY THE PROBLEMS RELATED TO
WASTE GENERATION. TREATHENT AND DISPOSAL
.SECiREGATE WASTE ANO IDENTIFY WASTE REDUCTION MEASURES
•EVALUATE THE' TECHNICA( AND ATTITUDINA( CAPABILITIES OF STAFF
•FORMULA TE RECOHHENDA TIONS FOR THE BEST PRACTICAeL� \WASTE HANAGEHENT
FINAL REPORT PREPARATION WITH RECOHMENDA TIONI
ACTION PLANS Willi Tlt1E FRAME FOR IHPLEHENT A TION
FOLLOW-UP
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3 .2
3 .2.1
monitoring and analysis of waste samples and environment and an
environment specialist. The number of people may vary from 4 t o 8 depending on the size and complexity of the facility being audited.
The team shou ld be sufficiently detached to provide an independent
view. The members shou ld be so chosen that they would not hesitate
bringing out even criticism. owing to obligations with Supervisor.
Sometimes it is advantageous to include members from the
h eadquarters of the industry.
It is important to have well-defined and systematic procedu res which are
known and understood by all concerned. The audit may take 3 -10 d ays
depending on t h e industry.
Effectiveness of audit is a direct resu lt of the qualification. confidence,
training and proficiency of t h e personnel who conduct au dits. The team
shou ld understand regulatory requirements. relevant waste control
technologies and their operations and process . They should have
capability to examin e , qu estion , sample and analyse waste and interpret
data. The management should be provided with a realistic assessment
of environmental performance.
Acti vi ti es at Site
The activities at site include deriving material balance, identifying waste
flow lines, monitoring of characteristics, evaluating performance of
pollution control equipment/system, assessing environmental quality,
h olding discussions with the management and finally preparing the draft
report. Interviews should be carried out with various cross-sections of
the staff engaged in produ ction. laboratory/ quality control. R&D.
e nvironment management. etc. so as to understand different operational
mechanisms. Having a fair idea on t h e manufactu ring process.
reconnaissance su rveys should be made to be familiar with layout of the
plant and process operations , and to u nderstand possible impact on the
su rrou nding environment. Various activities to be carried out at site are
discussed in detail in t h e following paragraphs.
Materi al balance
The entire manufacturing process of each prod u ct shou ld be drawn into
a process flow sheet representing various u nit operations as blocks. A
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3 .2.2
3.2.3
unit operation is a process where materials are input, a fun ction occurs
and materials are output mostly in a different form, state or composition.
A typical process flow diagram ofmonocrotophos, an organophorphorous
pesticide is given in Fig. 3 .2. This process includes the unit operations
of dehydration, adduct formation, chlorination o f adduct, dissociation,
concentration, toxiflcation. preconcentration and puriflcation. A typical
unit operation with inputs of raw materials, catalyst. water/air, power
and recycled material and outputs of products and by-products,
wastewater, emissions. solid waste· and reusable waste in another
operation is schematically shown in Fig. 3 .3.
T h e quantities o f inputs and outputs at each unit operation s h o u l d b e
worked o u t for the entire process a n d data incorporated i n t h e process
flow sheet . Discussions with the staff, perusal of t h e records of the
Company and the reconnaissance su rvey will help in arriving at these
flow sheets. From these flow sheets, data sheets incorporating the raw
material requirement. water consumption, wastewater and solid waste
generation, and gaseous emissions should be worked out for each
product manufactured. A typical data sheet is shown in Table 3.1.
The water balance sheet which shows areas of water usage and
wastewater generation and their quantities is depicted in Fig. 3.4.
Waste flow
From the material balance, the sources and quantities o f generation of
wastewater. gaseous emissions and solid waste should be identified. The
waste pretreatment. final treatment and disposal path should be
identifled. The production staff should be consulted as these people are
likely to know about waste discharge points and about unplanned waste
generations such as spills. leaks, washings. etc, Also, visits to the
process plants may disclose many other discharge points due to
overflows, spills and other material handling practices which are not
accounted and recorded. The quantities and sources should be
accordingly finalised an� a waste flow sheet prepared. A schematic
wastewater f low sheet is shown in Fig. 3.5.
Monitoring
The characteristics of the wastes as generated from the sources are
important to u n derstand its use for recycle, recovery or treatment, Also,
9
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PR E C O N T F E TECHNICAL 1.0 M ONOCROTOPHOS
Na OH
H AZ. WASTE
IJ
l TO I NCINERAT OR
JET CONDENSATE JET CONDENSATE
, ' D E TO X IFIC AT I O N TAN f<
l NTH
I
AIR STR IPPI NG -TANK
" 12.s TOE
T 0 ET P TP 12.4
i M M A-MONOMETHVL ACtTOACETAM!OE
T M P - TVIMETHVL PH OPHllE
D EC - DICHLOROETHANE
(ALL QUANTITIES ARE IN TONNES)
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0.429 T OLUENE
0.8 0 I T MP. -
0.115 D CE
_. 0
CHLORINE 0.495
l I DE H Y DR ATI O N A D DUC T
ADDUCT C HL O R INATI O N
,....;. I-u ::;, c 0
JET CON JENS TA.TE " (TO ETP) CHLOF.lAL TOLUENE 0.266 0
a: C H3Ci 0 _,
(TO STAC II l 0.227 :t
t u
10XIF !C ATI O N _ CONC
C O NC E NTR ATIO N �DILUTE
D I SS O C IAT 10 N M M ACI MMACI
a. i ! u JET JET.
-
... ... 0 Ill -t "
v :t
__..,.
I
RESIDUE TO INCINERATOR
t S O LVE NT
R E C O V E R Y -
TOLUENE & CHL ORAL
USE
S C R UB B E R
FOR RE
�TO E T P .o 3!
() "U () c:D m z
:L lJJ CONDENSATE CONDE NSATE
CHLOROFORM TO STA 0-SOmg/Nml
CK
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PR E C O N T F E TECHNICAL 1.0 M ONOCROTOPHOS
Na OH
H AZ. WASTE
IJ
1 TO INCINERAT OR
JET CONDENSATE JET CONDENSATE
, II D E TO X IFIC AT I O N TAN f<
l Nl°H '
AIR STR IPPI NG TANK
12.s T 0 ETP
t
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H TOE
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M M A-MONOMETHVL ACt:TOACETAM!OE :::J
T M P - TYIMETHYL PH OPHITE
D EC - DICHLOROETHANE
{ALL QUANTITIES ARE IN TONNES)
RAW MATTERIALS
�ATALYST ' '
r-- -7 GASE OUS EMISSIONS I I I I I I I I
PLANT PRODUCT, PROCESS "
WATER I AIR ' OR BY PRODUCTS, ,I
_POWER ' '
' /
Recycle
UNIT CATALYST, OPERATION /
�1 --�� RECOVERY FROM WASTE I 1-----� WASTEWATER I I LIQUID WASTES FOR �---�STORAGE AND/OR I OFF SITE DISPOSAL I REUSABLE WASTE IN ,,
ANOTHER OPERATION ---..,_ ----' 1- - --�SOLID WASTES FOR
11
� -----
STORAGE AND I OR OFF SITE DISPOSAL
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TABLE 3.1: DATA SHEET ON INPUTS AND OUTPUTS FOR THE MANUFACTURE OF MONOCROTOPHOS
Raw material requirement per tonne of product :
S.No. Raw Material Quantity, klir
Actual Stoichiometric
1. Methyl acetoacetamide 684 516 2. Toluene 429 Not a process
chemical
3. Chloral 266* 661 4. Chlorine 495 319
I 5. I Trimethvl phosphite 801 556
I 6. Dichloroethane 115 Not a process
chemical
* The value indicated is the lose to be made up Chloral i.s recovered by distillation and recycled.
Water requirement per tonne of product :
Process Steam HCl scrubber Cooling (makeup)
Total
w d astewater t?enerate
Nil 25 kl 31 kl 25.4 kl
81.4 kl
oer tonne o
S.No. Source
f nro d uct:
Nature
1. Jet condensate & spills Solvent, traces of toxic material
2. Jet condensate - do -
3. HCI scrubber liquor I ac1 4. Jet condensate & spills Chloroform
E . m1ss11 )nS:
S.No. Source Nature Quantity lill/t
L Chlorination HCI gas 164
2. Toxification CH3Cl 227
3. Air stripping Chloroform 0-50 mg/m3
Solid waste/hazardous waste:
Quan- Pretreatment titv. kl
9.5 Detoxification with NaOH
3.0 - do·
31.0 Nil
12.4 Air stripping at pH 11
Gas flow, Nm3/hr
Control equip.
Chimney ht., m
2200 Water 36 m scrubber
17760 Nil I 441 Ni l
S.No. Source Nature Quantity Pretreat- Method of kJ! disposal ment
1. Residue from chloral Halogenated and toluene recovery hydrocarbon
232 Nil Incineration 2. Product purification Defv:aded
so vents
12
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.OSS WIN
IN EVAPORATION ANO DAGE LOSS
'
C 00 LING TOWER
PROCESS WATER
r-
t
,
D. M. PL ANT
! BOIL ER
I I I I I I I t
-
�
'
INDUSTRIAL USE
'
CONDENSATE
"'" .., I I I I I I I I I I I I *
RAW WATER
l
'
SERVICE WATER
� ir
WASHING FIRE
I I I I I I I
I I L ______ , ________ .:J I I I I I I I I t WAS TE WATER
F!l@a �a4? M!JJ�� BJJlJJ/lr!l©IE ©F WJJ rE!tJ ©©llr!l�{?Jli/fferll@llr!I JJ/lr!llQJ
IEFFll!J!Ellr!lr @!El#JIENJJ r/J@l#J !IN /Jf}!J/g{?J�rnlllff�
POTABLE WATER
I
() "U () OJ m z < (./) () CD :::J r+ ., CD
-:E �
..... �
NoOH
MONOCROTOPHOS
CHLORAL STE AM (PLANT-1)
JET EJECTORCONOEN!>ATE _ ,_11\LO
SPILLS
Na OH JET/EJECTOR CONOEN�TE
HCl SCRUBBER 96KLO
JET/EJECTOR CONDENSATE 6 KLO
n�t:e1u:111e11t C�NOE BE ARIN(, EFFLUENT
P HOSPHAMlOOlf
HCI SCRUBBtR
SP ILLS
.!Ll!.:!..f JET/EJECTOR CO NDENSATE
5PILL5
INCINERATOR 5tRU88ER OISCHARC.E
� BLOW 00 WN
LAUNDRY
TO ILET S
MISCELLANEOUS
H102
Ul\LD
Na OH
50 KLO
H i<LD
175 11 L D
DRI PS DRAINS ORUM WA5HIN(,, L E AK5, Fl�E FIGHTING, ORILLS,YE HICLE WASHING
CHLOROl'OAM
37 II L O
LIME/ACID _....,.r---. EQUALISATION AERATION
e - SAMPLING LOCAHONS
!Jl!L'. - D OYP OR PKOSPHAMIDON ARE IN
P�TION ONLY ONE ATA TIME
CLARIFICATION AERATION CLARIFICATION
I I I I I I I I
�- -���G� __ j L - _5J:LJ,QG!. - j : I I I
� - - �SLUDGE THICKENER�-� I I I
"+--------------! SLUDGE DRYING BEDS
DISPOSAL
0 "U 0 OJ m z < (f) 0 CD ::I ,....... ., CD
I (")
i::::::l (") O'" CD ::I < CJ)
::I
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3.2.4
3 . 2 . 5
t h e performance o f t h e treatment facilities are t o b e monitored so a s t o
check their efficiencies a n d t o modify o r install additional equipment/
facility, if necessary. The surrounding environment - groundwater,
stream, soil. su rrounding land uses - residential, agricultural etc . • and
ambient air qu ality should b e monitored t o determine the impact d u e to
the industry. With the above obj ectives, sampling points should be
identified and monitoring network established. Parameters t o b e
analysed should b e determined from t h e material balances o f t h e wastes
generated.
The frequency of sampling should b e fixed so as t o cover hou rly and
daily variation in characteristics. It should al90 cover atleast one ful l
cycle o f operations. More than o n e such s e t s o f data can result in more
realistic results. Samples collected should b e of 'grab' type where
characteristics do not vary significantly and of 'composite' type where
characteristics fluctuate. 'G rab' sampling means collection o f sample in
one pick while composite sampling requires collection of sample
continuously or at predetermined frequency ( 1 -h r . 2 - h r . etc) and
compositing it in proportion to the flow rate observed at each sampling
time. The method of analysis of samples should be done as per standard
procedure and by trained analysts.
Field observations
The entire plant should be inspected thoroughly. The aspects of site
layou t , material handling and storage. drainage syste m , safety aspects,
lapse s / n egligence in operations and attitude of operators in process and
waste treatment facilities, handling of scrap and wastes. u s age of sign
boards, instruction, colour codes etc. should be observed.
The 'attitude' and 'technical capability' of various staff including senior
management should be observed as is very critical in achieving the goal
of .safer environment. The training requirements can be assessed based
on these observations.
Draft report
After completing the above-mentioned activities including determining
material balance, identifying waste flow, monitoring and analysis of
various samples and field observations, a draft report should be
prepared with findings and possible recommendations.
15
3.3
3.3.1
•
3.3.2
The draft report should b e presented before t h e senior management and
various points should b e thoroughly discussed. The Management should
put forward their views. The participation of the Management an d their
acceptance of various observations and recommendations makes t h e
task o f implementation mean�ngf ul.
Post Audit Activities
Synthesis of data
The requirement of various raw materials according to the mass balance
of chemical equation involved in the manufacture of a product is called
stoichiometric reqt1irement. A comparison of these requirements with
the actually used in the indu stry gives an indication of excess usage of
various raw materials. These excesses may b e presumed to b e finding
their way to air, water and soil thus causing pollution. Hence, i t is
important to reduce these excesses. The unit operation should be
checked up to find out the cause of excess u s age of the materials an d
accordingly modifications made. Norms should t h e n b e fixed for
performance of each of the unit operation s, for wastes generated from
each of these unit operations. The production and environment staff are
simply to adhere to the norms. The Environ ment Manager thus can
have a control over production as well as wastes generation too.
Evaluation of waste treatment facilities
Performance of various pretreatment and final treatment facilities should
b e evaluated based on the analysis reports. I f the treated wastewater,
gaseous emissions and solid waste do not conf arm to the standards
prescribed by the Pollution Control Board. reasons for the same should
b e diagnosed.
From t h e individual streams of wastewater . recyclable and recoverable
materials should be identified and provisions made for the same. All the
'avoidable' wastes should b e complet ely controlled and only the
'unavoidable' allowed for discharge. The wastewater should be
segregated based on the characteristics, such as inorganic, organic,
acidic . alkaline , easily biodegradable, not easily biodegradable and toxic
streams: and pretreatment units viz. oil separator, n eutralisation,
detoxification etc. should be provided, wherever required . at the source
so as t o minimise cost of final treatment.
16
() "U () OJ m z < (J) () CD ::l .......
ro
3.3.2
The wastewater of similar nature should b e combined and common
treatment facilities provided. This would be efflcient and economical.
Many a times, i t is observed that inorganic wastes and
non-biodegradable wastes are treated in biological treatment plants
which on the contrary render biological treatment ineffective. Toxic
wastes should be detoxified before treat ing in biological treatment plant.
Highly toxic wastes may be isolated and incinerated. The rate of
wastewater flow and polluted loads to the effluent treatment plant (ETP)
should be properly regulated to keep off shock loads to micro-organisms.
The designed criteria and the actual operating conditions of various
treatment units should b e compared and norms fixed for the operation
of these units .
Similarly, the problems related to gaseous emission and solid waste
generation may be identified. Recommendations for the best practicable
waste management systems should b e formulated. The guidelines for
environmen tally safe layout are given in Annexure I I I and guidelines for
reduction of raw materials losses, and wastewater and gaseous
emissions are given in Annexure IV.
The Environment Division of the industJy should have an environment
specialist to look into matters related to pollution control and evolve
norms for resource conservat ion/waste minimisation vis- a-vis process
control. Besides, he should also evolve norms for optimal u t ilisation of
resources and performance of various pollution control systems. The
members of this division and the operators of the treatment facilities
should be well-trained.
To oversee the implementation of the measures for pollution control and
the overall management of environment. there should b e a Peer Group
comprising members from production, quality control / laboratory. R&D
and waste treatment divisions. the top management. and an
environment specialist.
Final report
Various aspects discussed above should be compiled and a f inal report
prepared alongwith recommendations. The final report may , i f n ecessary.
be sent to the top management for comments so as to make furth e r
modif ications.
17
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3 . 3 . 3
3. 3. 4
Action plans
The recommendations include measures for best practicable
environmental management . If the annual burden, i.e. the annualised
capital cost of the pollution control measures and their operating cost.
for the implementation of all the recommendations. is h igh and the
investment not feasible for the industry, then these recommendations,
should be implemented in phases. Priorities should be fixed and action
plans with t ime-frame should be formulated.
Follow-up actions
Follow-up actions should be taken to check the progress of
implementation of recommendations. The Environment Division of the
indu stry should meet the other Divisional heads periodically t o review
the progress.
1 8
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4.0 CASE STUDIES
4 . 1 Organo-chlorine Pesticides Industry (Company 'A')
4 . 1 . 1 .
The industry is located in the Northern part of the country. and is
involved in the manufacture of dichloro di phenyl trichloroethane ! DDT).
an organochlorine pesticide. I t is a large scale industry and is in
operation for about 40 years. The indu stry was commenced when there
was not so much consciousness about pollution control . Over t h e
years. residential development blossomed around t h e factory and a situation has arisen wherein t h e i ndustry has to immediately review its
activities thoroughly and effectively manage the wastes generated for its
existence.
Environmental auditing was conducted by a team of scientists /
engineers from the Central Pollution Control Board ( Central Board) ,
Delhi . This was the first pesticides industry to be audited by the team.
The procedure followed and the results obtained are explained below.
Pre-audit activities
4. 1 . 1 . 1 . Preliminary information
A questionnaire was sent to the industry and preliminary information
obtained on products manufactured, raw materials and water used,
wastewater, gaseous emissions, and solid wastes generated, waste
disposal points and details on surrounding land uses . Details in brief
based on the information received are given below.
The industry is involved in the manufacture of technical grade DDT and
its formulations. The raw materials used for technical grade DDT are
benzene . alcohol. chlorine and oleum (20% ), and those u s e d for
formu lations are : technical grade DDT. china clay and soap stone. The
manufacture of DDT involves broadly the following three steps :
Step I
Step I I Step I I I
Manufacture of monochlorobenzene ( MCBJ
Man u facture of chloral
Manufacture of DDT
2 1
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Step I has the u n it operations of dryin g of benzene, chlorination of
benzene . neutralisation and washing of ch lorobenzene , enrichment of
ch lorobenzene and distillation o f monochlorobenzene ( MC B ).
Step I I has the unit operations of chlorination of alcohol, distillation of
ch loral alcoholide in the presence of oleum, and absorption of hydrogen
chloride.
Step I I I inclu des the u n it operations of condensation reactton between
MCB and chloral u sing oleum as a condensing agent , separation of
aqu eous and organic phases, recovery of M C B from organic phase , and
solidification of DDT.
The flow sheet of various operations as provided by the industry is
shown in Fig. 4 . 1 . The total water consumption is 460 kid of which 2 70
kid is for process. 3 0 kid for sanitary. 1 o · kid for services, 1 2 5 kid for
boiler and 25 kid is for cooling water make- u p .
The wastewater generated is 290 kid o f which 2 5 0 k i d i s from process ,
3 0 kid from sanitary and I 0 kid from boiler blow down . Steam is
borrowed from a neighbouring industry a n d hence boilers are not in
regu lar use . The wastewate r is characterised by parameters like , p H , SS,
CO D . BO D , O&G . sulphates, chlorides and DDT. Solid waste generated
is 1 8 t / month ( 70% water) from effluent treatment plant ( ETP) and is
disposed off in to a municipal dumping yard.
Th e gaseous emissions include combustion emissions. from usage of
furnace oil at the boilers whenever required an d process emissions of
benzene . chlorine . HCI and dust of DDT. The industry reported its
problems to bring down CO D within permissible limit of 250 mg/I and
disposal of sludge from ETP .
4 . 1 . 1 . 2 Audit team
An audit team of seven members was constitu ted. Th e team inclu ded a
Senior Environmental Engineer, two specialists on pesticides industry
one scientist and the other an engineer. two members for water
sampling, and two members for emissions sampling. Th e members with
relevant experience were chosen based on the nature of work assessed
from the preliminary information . The members had expertise in their
2 2
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own fields . The two specialists were aware of environmental problems
associated with a pesticides in dustry and various waste management
options. From the factory side, an overall coordinator an d
representatives from production. environment management and
laboratory were identified to assist the au dit team. The members were
allocated with specific tasks.
4 . l . 1 . 3 . Resources
The laboratory of the Central Board at Delhi was chosen for analysis o f
samples . This laboratory has t h e facil ity to analyse various parameters
iden tified, including DDT. The instruments requ ired for sampling were
high volume sampler and han dy sampler for ambient air quality an d
stack mon itoring kit for emissions from stacks. These were made
available by the above laboratory.
4 . 1 . 1 . 4 Visit programme
4. 1 . 2 .
Th e industry being a single product plant having n o complications as
in mu lti-product plants. a visit programme for 3 days was prepared.
The programme was commu n icated to the industry well in advance, and
also informed to confirm back that various operations would be normal
and that there would be no shu t downs or partial operations du ring t h e
auditing period. After receiving confirmation , t h e visit programme was
commun icated to the members and the laboratory.
Activities at the site
On reaching the s ite, a meeting with the management of the industry
was held. The purpose of audit was explained to them. The coordinator
of the industry introduced various representatives who would assist t h e
audit team. The man u facturing processes an d various activities that
take place at the site were explained to the au dit team. The team then
made a reconnaissance su rvey of the in dustry so as to be acquainted
with location of various activities and operations. The team then went
ahead with other activities at the site which are a part of the audit.
23
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4 . 1 .2 . l . Material balance
The chemical reactions involved in the process are given below :
C6H6 ( 78 . 1 )
2 C2 H50H ( 9 2 . 1 )
+
+
Cl2 - - - - - > ( 7 0 . 9 )
C6H 5 Cl ( 1 1 2 . 5 )
+ HCl ( 3 6 . 5 )
4Cl2 - - - - - > CC13 CH(0 Hl OC2H5 ( 283 . 6 ) ( 1 93 .5 )
oleum
+ 5 HCl ( 1 8 2 .2 )
CC1 3CH( O HJO C2H5 ( 1 93 .5 )
- - - - - - - > C Cl3C HO + ( 1 47 . 5 )
C2H50 S03 H ( 1 2 6 )
CC13CHO ( 1 4 7 .5 )
+ H2S04 .S03
2 C6 H5Cl - - - - - - - - - > ( C6 H 5 Cll2 CHCC13 + H20 ( 22 5 ) (3 5 4 .5 ) DDT ( 1 8 )
The process flow chart incorporating various u nit operations alongwith
inpu ts of raw material and water an d outputs of products . by- products,
wastewater, gaseous emission. solid waste and in termediates is shown
in Fig. 4 . 1 . The quantities of inputs and outputs at each u nit operation
could not be worked as the industry had no ready data. As it is a long
procedure an d time consuming, the industry was explained h ow to
carryo�it tl)e work. and was asked to complete the work later. T h e mass
balan ce of ch lorine and oleum derived from the overall usage is given
below.
The requ irements of raw materials per tonne of products are given in
Table 4 . 1 below :
TABLE 4 . 1 : RAW MATERIAL REQUIREMENT- STOICHIOMETRIC VS. ACTUAL
I
Stoichiometric Actual : % Extra '
Raw material requirement ( k g . ) requ irement• (kg. ) : consumption I I I
. - - - - - - - - - - - - - - - - - t--- - - - - - - - - - - - - --- - - - - - -- - - 1- -- - - - - - - - - - - - - � -
- - - - - - 1--- - - - -- - -- - - - --- -B enzene 440 . 7 780 . 7 7 7 . 1 I . I - - - - - - - - - - - - - - - - - - 1 - - - - - - - - - - - - - - - - - - - - - - - - - - - 1- - - - - - - - - - - - - - - - - - - - - - - -r - - - - - - - - - - - - - - - - -
Ch lorine 1 200.2 • 1 7 73 .24 1 4 7. 7 I I - - - - - - - - - - - - - - - - - - 1 - - - - - - - - -
- - - - - - - - -- - - - - - - - - 1- -- - - - - - - - -- - - - - - - - - - - - 1 - - - - - - - - -
- - - - - - - - -
Ethanol 1 2 5 9 . 9 4 0 9 .00 5 7 .4 I . ----- - - --- -- - - --- 1 - - - - ---- - - - - - -- - - - - - - - - - - - - -i - - - - - - - - - - - - - - - - - - - - - - - t--- - - - - - - - - - - - - - - -
Oleum ( 2 0 % ) 1 5 80.58
(•Based on the average of four years)
24
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B E N Z E N E ----�
B E N Z E N E
t-.J (]\
C H L O R I N E
A L C O H O L
B E NZ E NE SC RUBB E R
CHL O R INAT I O N
W A T E R
A B SO R B E R
W A T E R WAi E R
A B SO R B E R AB SO R B E R
2 0 '/, H C I
M C B
D C B ( 8 Y - P R O O V C T )
V E N T A I
_ _j A B SO R B E R T O E T P
V E N T
... I I
_ _ _ _ _ J
T O E T P
3 0 '/, H C I
C O ND E NS E R
C H LO RINAT I O N 1--,---;M
ALC O HOL W A T E R ( H O T )
O L E U M C AU S T I C S O D A
C HL O R AL W A S H A NO C O N D E N SAl I O N l----'�
N EU TR AUSAT I O N
S P E N T A C I D F O R ....----'
R E C O V E R Y --- T O E T P
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M C e V A P O U R S � F O R R E C O V E R Y {-)
D I S TILL AT I O N
"'O (")
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__.
The total water requirement is 460 kid and the wastewater generation
is 290 kid. The water balance sheet is given in Fig. 4 .2 .
4 . 1 . 2 . 2 Waste flow
The wastewater generated from process is 30 kid from H C I scrubber of
MCB plant . 30 kid from HCI scru bber of chloral (CA) plant . 1 40 kid
from washing and neutralisation of DDT condensation, 4 0 kid from
spent sulphuric acid recovery plant and 1 0 kid from floor washing in various plants. Pretreatment u nits include a separator in MCB plant to
remove floating organics. a DDT separator to s ettle down DDT from t h e
wash stream ( 1 40 k id) a n d separate s ettling tanks for wastewater from
CA c:µi d MCB plants and DDT condensation plant. Th e wastewater then
flows through a fina l effluent treatment plant ( ETP) comprising
equalisation tan k. neu tralisation with lime, clarifier and sludge drying
beds. The wastewater is then discharged to a pu blic drain.
The domestic wastewater i s passed through septic tan ks and disposed
into the public drain. The wastewater flow lines are shown in Fig. 4 . 3 .
The gaseous emissions include benzene. chlorine, HCI , alcohol vapou rs.
DDT and fugitive emissions from process. The source of emissions, its
type and details of control equipment provided are given in Table 4 . 2 .
The main source o f solid waste is ETP. The quantity o f waste generated
is 18 t / d on wet basis containing 70% water. I t is dispose d to the
municipal dumping yard. Raw material carrier gu nny bags are burnt
in the factory and drums are sold ou t.
4 . 1 . 2 . 3 . Monitoring & analysis
Sampling points identified for analysing wastewater and performance
of variou s treatment u nits are shown in Fig. 4 . 3 . 4 - h r composite
sampling was made. Parameters analyse d to identify the characteristics
of wastewater and to evaluate performance of various treatment u n its
and the analysis results are incorporated in Fig 4 . 3 .
The stacks could not b e monitored as they were not installed properly
and stack monitoring facilities viz. port hole etc. were not provided.
26
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en
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N .......
+ B O I L E R FEED
1 2 5 K L D I I I I I I I I
� BOILER BLOW DOWN
1 0 � L O
I I I I I I I I I I I I I
<I(; COOLING WAT E R
M A K E U P
2 5 K L D I I 1 I I I
"' BLEED O F F
N I L
L - - - - - - - - - - - - - - -
RAW WAT E R 4 6 0 K L D
I "'17
P R O C ESS USAGE
• A B S O R B E R S AND
. O T H E R S
2 6 0 K L D
• FLOOR WASH 1 0 K L D
I I I
"' PROCESS WAST E WATE R
• M C B SECTION 30 KLD
• CHLORAL SECT/ON . 30 K L D
;;i; S A N I T A R Y
3 0 K L D
I I I I I I I
""' WASTEWAT E R
3 0 K L D r I I I
• NEUTRALISATION AND WASHING OF HzS04 I
I 1 40 K L D • SPENT ACID SECTION
40 K L D • FLOOR WASH
10 K L D
I I
EFFLU E N T TREATMENT PL,\NT
I I I I I I
SE PTI C T A N K
;;i, SERVICES
• F / R E1GARDENING
E TC . 1 0 K L D
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MCB SECllON WASH t-..._---<,.. SEPARATION
HCI SCRUBBER ( C . A . PLANT )
C A PLANT WASH
KLD
1
SETTLING TANK 6 SETTLING TANll
* NO OISCHllRGES Al THE TIME OF SAMPLING Al POINTS 1, 2, 10 * UNITS : OOl tDDE AREIN . ... g / l i t .OTHER PARAMETERS EXCEPT
pH ARE tj mg l i f t
I D D T SECTION ���-'t--------1-1·---oo!EUUALISAllON '----------1�40�11L�D,.... t-...__NBJTRALISATION I-____ CLARIFIER
IO S S AP PLANT
11
OOILER
TOILETS .__--.i SEPTIC TANKS
D D �§l�i 1U �1 �§l ��; 11f:U ���: 345. 5 SAMPLE r : �H�
CHARACTERS Tl P H ; l · b p� : � 4 ��i 31 s g . . s : 5 c o ; 177 C O D: 177 C O O: 420 C l : 91! c i :IOE'inl C I :1 1405 � �504 : 23 5 04 : 33 �504: 3 7
"'
D DT �. 13616
D DOT PP:3158:) DDEPP: 1741'
PH: 2 .e PH; I 0 PH: 1 1 . 6 SS : 52 SS: Tl • SS: 'i3l6 COD: Xl� COD: 3360 COO: 1653 C l : 1825 C l : 8088 C l : �30 s o4: n7 S04: 1 235 S04 77 9 14
��t ��� EPP: � '4 �e p�: 5 : 2� .0 00: 4GO C l : 920&
�504: 50
SLUDGE DRYI NG BEDS
I
t DISPOSAL
BBl��1�� O O E P P: §�r n�111�
��� 26 6 COO: 5199
P�: 1 .7 i5 : 1 7 C 0 : 372S C l : 2336 C I : 1943 5 04 : 495 � 5 04: '535
.,
DOT O P : 0 .43 DOT OP: 1S S� DOT P P: 1 . 77 DDT PP: 57 1 5 DDE P P; 0 .21 ODE PP: 4.26
PH: 7 . 2 PH; 7.0 s S: 83 SS: 75) COO: 1 1 2 COD: 1 1 9 C l : 148 504 : S4 so ' ' � Cl: �� . ,.
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TABLE 4.2: PROCESS EMISSIONS - TYPE, SOURCE AND CONTROL EQUIPMENT
Source of Type of Control Equipment Remarks em1ss10n em1ss10n Provided
MCB Section · Benzene i) Benzene scrubber No provisions in Chlorinator vapours the chimney for ·
monitoring. Emissions to be monitored and suitable chimney height to be provided
• Chlorine i i ) Water absorber to - do -gas scrub HCl & produce
20% acid as by-product
• H C l gas i i i ) Tail gas absorber - do -where H C l gas is further scrubbed with water
CA House ' Alcohol i ) Alcohol vapours removed - do -Chlorinator vapours in a condenser using
cGol ing water and brine
' Chlorine i i ) Water scrubber to absorb - do -gas H C l gas and produce 30-35%
acid as by-product
• H C l gas i i i ) T a i l gas absorber where - do -HCl gas is furthe r scru-bbed with water
Grinding • Dust of Dust extraction system with - do -Section DDT and hoods, ducts, cyclone separ-
inerts a tor and a chimney of 55 m height
29 I
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-
The ambient air quality was monitored at seven locations within t h e
factory premises including the process areas using h igh volume
samplers an d handy samplers. The results are given in Table 4 . 3.
The public drain where the treated wastewater i s discharged was
monitored at upstream an d downstream of the disposal point. Also, t h e
groundwater i n t h e factory premises was monitored . The results are
given in Table 4 . 4 .
The solid waste was analysed for DDT and D D E ( dichloro diphenyl
e thylene) - a breakdown product of DDT. The analysis of this waste
showed DOE ( PP' ) of 1 54 74 !l g / g . but DDT could not be traced .
4 . 1 .2 .4 Field observations
... In the manufacturing process certain side reactions take place .
Durin g the chlorination of benzene. dichlorobenzene ( D C B ) is also
formed alongwith MCB which is recovered and sold as a
by-product to the deodurant products manufacturers. During the
condensation process o f chloral and MCB to form DDT, a small
amount o f chlorobenzene sulphonic acid is also formed. These
side reactions lead to wastage of materials. H2S04 is used as a
catalyst and for absorbing water. It is the major pollutant in the
wastewater as the spent sulphuric acid is not recovered entirely.
Certain process modifications are deemed necessary.
The wastewater collection and drainage system is poor. No
separate storm water drainage system has been provided. The
process wastewater drains are subject t o entry of stormwater due
to which handling of wastewater during rains becomes very
difficult .
The manual dosin g of lime in the neutralisation tan k o f ETP is
inefficient . The operators though are able to test pH. adjusting of
lime dosage is not well known .
The sludge drying beds of ETP are choked. The solid waste is not
properly collected. Scrap was found lying scattered in the plan t .
There i s n o earmarked area for solid waste.
30
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TABLE 4.3 : AMBIENT AIR QUALITY
S.No. Location Sampling Period
Total Sampling
Analysis Results (�cg/m3)
Time ,f---��--�------1 r (minutes)
1 S02 Cl,. I SPM
I 1. Near chloral 1 1 .55 AM · 03.55 PM 240 61 .8 : 8.0 306
lant : I p I I I I I - - - - - - 1 - - - - - - - - - - - - - - - - - - 1 - - - - - - - ----- - - - - - - - - - - - - t- - - - - - - - - - - - - -t-- - - - - 1 - - - - - - 1 - - - - - - - - -
2 . , Near DGM 1 2 . 1 0.PM - 1 4 . 1 0 PM 240 4 3 . 5 2 . 7 276 : building at the I : height of 9 m. : : - - - - - - 1 - - - - - - - - - - - - - - - - - - i--- - - - - - - -- - - - - - - - - - - - - -t - - - - - - - - - - - - -1- - - - - - 1 · - - - - - i· - - - - - - - -
I I & \ 3. Near GM -1 . 1 0.PM - 05. 10 PM 240 46.3 3.6 232
: building at the : height of 4 m. I I I • I � - - - - - - 1--- - - - - - - - - - - - - - - - T-- - - - - - - - - - - - - - - - - - - - - ;- - - - - - - - - - - - - ;-- - - - - - 1 - - - - - - 1 - - - - - - - - -
1 4. , Near Mono- 1 1 .40 AM - 0 1 .40 PM 120 ' 1 2 .5
: chloro benzene : (MCB) unit ' , I I I [ I I - - - - - - 1-- - - - - - - - - - - - - - - - - 1 - - - - - - - - - - - - - - - - - - - - - - - -i-- - - - - - - - - - - - -i--- - - - 1-- - - - - 1- - - - - - - - -I I I I
5. , - do · : 0 1 .45 PM - 03.45 PM : 120 1 ND : - - - - - - -j - - - - - - - - - - - - - - - - - - -j - - - - - - - - - - - - - - - - - - - - - - - -r---- - - - - - - - - - - 1 --- - - - 1-- - - - - -j- - - - - - - - -I I I I � I
6. : Near duct tower : 1 1 .40 AM • 0 1 .40 PM : 120 : : 1 6. 1 : - - - - - - 1 - - - - - - - - - - - - - - - - - - 1--- - - - - - - - - - - - - - - - - - - - - - i- - - - - - - - - - - -- -i-- - - - - 1-- - - - - 1 - - - - - - - - -
I
7. - do - 0 1 .45 PM - 03.45 PM : 120 3.6
(ND - Not detectable)
TABLE 4.4: GROUNDWATER ANALYSIS
i ) ii)
iii) iv) v)
vi) vii)
viii) ix) x)
xi) xii)
pH Chlorides (mgll) Sulphate (mg/l) Total Hardness (mg/I) Conductivity (µ.mhos/cm) Phosphate (P) (mgll) Nitrate(N) (mg/I) Alkalinity (mg/I) DO (mg/I) DDT PP' (µ.gll) DDT OP' (µg/l DDE PP' (µg/l)
6.3
2 1 0 1 573 3480
7380
Not traceable 0.46
463
Not traceable 14569 3627
2829
3 1
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"" Chemical spills . overflows and leaks from pipes in the process
areas were observed almost eve1ywh ere. Final product of DDT.
d u e to a crack in the DDT casting pans, was finding its way to
wastewater drain .
The HCI gases are scrubbed with water and discharged t o ETP.
This wastewater and that from washing in condensation reaction
of DDT is contributing to acidity due to which h uge quantities of
lime has t o be used for treatment. The source of DDT in the
efiluent is from washing in condensation section of DDT ( 1 40 kid ) .
Huge quantities o f HCI fume were observed w h ile loading HCI .
tan ker. Also emissions were observed from t h e HCI storage tan ks.
House-kee ping is poor. Proper colour codes, sign boards and
instructions are not incorporated. The indus.try has n o clearcut
buffer zone or green belt with the surroun dings . Industry is
surrounded by residential areas. Land availability is limit e d at
the site . Site layout is poor.
•
Industry has of late taken steps to improve waste management.
However, the industry's staff are of the opinion that since it is a
very old factory it is very difficult t o make modifications needed
for the best practicable waste management. Industry has a
separate R& D wing t o carry out research for improvement . The
staff are not aware of the latest environmental management
techniques and waste management options.
4 . 1 . 2 . 5 . Draft report
No draft report was prepared at the site as the audit guidelines were yet
to be evolved as this indu stry was the first industry to be audited.
However, detailed discussions were carried out with the management
about the observations and possible recommendations. The
management agreed with the viewpoirits of the audit team and welcomed
a detailed report with recommendations for implementation .
The comparison of the stoichiometric and actual requirements
based on average figures of four consecutive years shows that
there is excess usages of chemicals like benzene - 7 7%, chlorin e
- 48% , a n d ethanol - 5 7%. About 258 k g/ d of HCl ( 1 00% ) and 3 . 7
3 2
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t / d of H2S04 ( 1 0 0 % ) are finding their way to environment. The
excess usage of materials besides con tributing to loss of economy
are causing pollution. The excess usages may be attributed to
inefllcient process techn ology, poor process performance, poor
house-keeping. lack of inplant control measures and poor
material handling.
The wastewater generated is about 40 kld per tonne of product
manufactured . I t con tains sul phuric acid, hydrochloric acid ,
soluble organics in the form of benzene , alcohol . MCB. DCB an d
DDT. The effluent is highly acidic and toxic in natu re . The major
con tributor to water pollution is soda and hot water wash in DDT
condensation section . From DDT cast pans, due to leaks, an
amount of 6 . 6 kg / d of DDT is being contributed to ETP . HCl in
the efflue n t is contributed from HCl scrubbers a n d H2S04 is
contributed from soda and hot water wash a n d H2S04 recovery
plan t.
The solid waste generated is hazardous in nature due to the
presence of DOE and hence cannot be disposed to mun icipal
dumping yard. Also. an authorisation from the pollution control
agency is to be obtained for the disposal of this waste. The open
burning of used raw material bags is not permissible as it causes
air pollution and may generate toxic fu mes .
The scrubbers provided for HCl emissions appear to be
insufficient . Additional caustic soda scrubbers are to be provided .
The fugitive emissions due to material h an dling, from storage
tanl<S and from loading and unloading of tan ks are to be
controlled.
The wastewater treatment system provided is insufllcient . The
D DT separator is not serving any purpose mainly due to
insufllcient detention time provided for DDT to settle down . The
manual dosing of l ime in neutralisation tank of ETP ls ineflkient .
The clarifier is under- designed. The treated wastewater is not
conforming to the prescribed stan dards.
DDT concentration in the wastewater can be reduced by 5 0% by
controlling leak from the DDT cast pans and collecting overflows
or spills occuring while sampling under DDT condensation vessel.
33
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DDT separator is to be modifi.ed to achieve proper detention time
for settling. Alum coagulation aided settling may enhance rate of
DDT.
The groundwater in the factory premises is highly polluted. I t has
a D DT of about 20.000 µg / l and also high concentration of
condu ctivity and chlorides. The process wastewater and leachate
from sludge dumping migh t have caused this pollution of
groundwater.
Industry has air pollution problem due to HCl fumes from
process. HCl storage tanks and loading of HCl road tan kers .
Fugitive emissions were observed at various process sections .
On-l ine gases pose air pollution problem during power failures
since stand-by D . G . set is not available.
.. House-keeping is poor. Spills, leaks an d fumes are generated
from various processes. Drainage system and collection of scrap
and waste are poor.
4 . 1 . 3 . 2 . Final report
A final report incorporating various observations and recommendations
was prepared. The important recommendations include the following:
Review of process technology adopted and performance of process
equipment is deemed necessary to take up modifications
accordingly. Fixing up of norms for performance of process
operation and wastes generated imminent such that the loss of
materials and hence the wastages are minimised. The possibilities
of replacing oleum with a suitable alternative may be explored.
The proposed scheme for waste treatment i s shown in Fig. 4 . 4 .
The top level of process drains are to be kept atleast 1 5 cm above
ground level so that the rain water does not enter these drains.
Storm water drainage is to be kept separate and polluted storm
water carrying spills during the initial hours of rainfall to b e
collected and treated. Flooring in t h e process areas shall b e
3 4
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* M C B PLANT • WAStllNGS ____ .,_ SEFMAlOR
• HO E�� ABSORBER • HCI S lCJRAGE TANK EM�S 8"' • HCI EMSSIONS FIOI 8Q LOADING (ff ROAD :ca
TANK E R S__J °"
* C A PLANT
• HCI EMISSIONS ---ABS(.'q8ER
•WASHINGS * D D T PLANf
N a OH
1----.+-tSCFUBBER
COlLECTION TAH<(Dn HCI ) BY PROOUCT
N a C»I
COLLECTION TANK(OA HCl) BY PRODUCT
SE T TLING TA"l K
•WASHINGS ----- SEPARAlOR UNCREASED 1----------------l O &G SEPARATOR CJIA!ICITY )
SLUDGE DRYING BEDS
*� LME •'N\SHIM:;S ------------------------------' NEUTRALISATION 1!5olSTAGE
• MISCELLANEOUS (FLOOl:i WASHe>,SPR.L.5 E Tt . l ---------------------'
NEUTRALl5.A'OCN 2nd5TAGE
DUAL MEDIA FILTER ( WITH SANO & COAL )
ACTIVATED CAJl!ON BEDS
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..------�-------. - . , i i o - I "'C
- - - -��O� - _ l _ - �.-S-LUDG--E-DR-Y-!N_G_BE_D_S--, g
:::J < Ci)" :::J
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made properly. Treated wastewater to be recycled for floor wash.
making lime solution and for gardening purposes.
Tree plantation in the surrounding sh all be developed t o act as
buff er zone and also to improve the environment.
4.2 Organophosphorous Pesticides Industry (Company 'B' )
4 . 2 .1.
Company 'B' is a large-scale industry involved in t h e m anufacture of
technical grade organophosphorous pesticides and their formulations.
It is relatively a new industry and h ence environmental aspects were
given due consideration at the design stage. Auditing was conducted in
this industry t o probe how best various systems were working and to
look into possibilities for further improvement.
Pre-audit activities
4 . 2.1.1. Preliminary Information
A questionnaire was sent to the industry for collection of preliminary
information. Details based on the information received are given below:
Industry is involved in the manufacture of basic pesticides l ike
monocrotophos, cypermethin, phosphamidon and dichlorouos ( D DVP)
and their formulations. It is located in an industrial area.
involved in the manufacture of above product are as follows:
al Monocrotophos (MCP)
The steps
Step I: Dehydration o f monomethyl acetoacetamide ( M M A ) to obtain
anhydrous MMA.
Step I I : Reaction of M M A w i t h chloral in a toluene m e d i u m t o obtain
MMA adduct.
Step IV: Filtration and dissociation of chloro adduct t o form MMACI.
Step V: MMACl is reacted with trimethyl ph osphite (TMP) in
dichloroethane medium to form monocrotophos. Methyl
chloride gas is evolved.
36
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b l Cypermethrin ( CYPER)
The first step involves condensation of 2 - d imethyl - 3 ( 2 -2 dichlorovinyll
- cyclopropane - 1 . carboxyl chloride ( DVO J . meta phenoxy benzaldehyde
( M PB) and sodium cyanide in xylene media in the presence of a catalyst . The above mixture is washed to remove ionic impurities . The washed
product is dried and purified by distillation . Solvent is recovered and
recycled . The product is cooled and filtered to obtain cyperme.thrin .
c l Dichlorovos ( DDVP)
Chloral and T M P are reacted to produce crude DDVP which is fu rther
distilled to obtain required purity.
d i Phosphamidon (PMNl
Step I : Diethyl acetoacetamide is reacted with chlorine t o produce
diethyl dichloro-acetoacetamide ( DOA) .
Step I I : D O A is reacted with TMP in presence of chlorobenzene t o
crude amide phosphamidon.
Step I l l : Crude phosphamidon is vacuum distilled to preconcentrate
and is fu rther flashed in a thin film evaporator to produce
phosphamidon of required pu rity .
The water requirement is 1 1 60 kid of which 1 4 0 kld is for boiler . 220 kid
for cooling water . 1 60 kid for process (92 kid for monocrotophos . 60 kid
for phosphamidon / DDVP and 8 kid for cypermeth in l . 200 kid for
sanitary and 440 kid for services ( fire . gardening etc ) . The wastewater
generation is 500 kld ofwhich 1 40 kid is from boiler blow down , 200 kld
from sanitary and 1 60 kid from process ( MCP : 92 kid. PMN / DDVP: 60
kld. CYPER : 8 k i d ) . The wastewater characterised by parameters l ike
p H . BO D. CO D , TSS. cyanides . residual chlorin e . pesticides an d toxicity.
The wastewater treatment includes pretreatment of process wastewater for detoxification fol lowed by combined treatment of domestic and
process wastewater in a two-stage biological treatment plant .
The process emissions include . HCI. C H 3 C l . chloroform . H C N . P205 and
SPM . Gaseous emissions also arise from combustion of furnace oil at
boilers.
37
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The solid waste generated is about 5. 0 t /yr. It contains oils , pesticides.
toxic residues, discarded containers etc .
4 . 2 . 1 . 2 . Audit team
The audit team had seven members , same as i n Case S t u dy 4 . 1 .
4 . 2 . 1 . 3 . Resources
The ind u stry has a fu ll- fledged laboratory to analyse various expected
parameters . inclu ding BO D. Pesticides and Toxicity. The laboratory also
has stack monitoring kit and h igh volume samplers. The laboratory of
the Central Pollut ion Control Board at Delhi was chosen as a stand-by.
4 . 2 . 1 . 4. Visit programme
4 . 2 . 2 .
A programme fo r a visit t o t h e industry was prepared fo r s ix days . The
programme was communicated to the ind u stry well in advance and got confirmation of the normal working during those six days.
Activities at the site
A meeting with the Management o f the industry and the representatives
from the indu stry who wou ld assist the team was held and a
reconnaissance survey of the industry, was done. The team then went
ahead with performing various other activities as detailed below.
4 . 2 . 2 . 1 Material balance
i )
The chamical reactions involved i n the manufactu ring process are as
follows:
a) Monocrotophos:
H H toluene I I
C H 3 - CO- C - C O - N H C H 3 + C C 1 3 C H O - - - - - - - - - >C H 3 -CO-C-CO- NHCH3
I H I H O H C C 1 3
( MM A ) ( C h lora l ) ( MMA Adduct )
i i ) MMA Adduct + C l 2 - ------> C H 3 -CO-C -C0-NHCH3 + H C l I
38
H O H C C 1 3 ( C h loro adduct )
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C l
iii ) Chloro adduct I
-- - - ---> C H 3 -CO-C -C O-N H C H 3 + Chloral
OCH3
I H
( MMAC l )
0 H I
iv ) MMA C l + OCH 3 -P - O C H 3 l I
- ---> OCH3 -P-O-C=C -CO -N H C H 3 + C H 3 C l
( TMP )
b ) Cypermethri n :
I I OCH3CH3
( Monocrotopho s )
C a t a l y s t A c i d Chloride + m-Phenoxybenzaldehyde + NaCN - - - - - - - >
N a C l + Cypermet h r i n
C ) DDVP : 0 I
C C 1 3 C H O + ( C H 3 0 ) 3P ---> ( C H 3 0 ) 2 P-O -C H =
( Ch l o ra l ) ( TMP ) ( DDVP ) C C 1 2 + C H 3 C l
d ) Phosphamidon :
0 0 C 2 H5 I
C H 3 -C - C H 2 - C -N + C l 2 I
C 2 H 5
( DE A )
0 0 C l C 2 H 5 I I
- - - - - - - > C H 3 - C - C -C - N + 2 H C 1
I I C l C 2 H 5
( Diethyl Dichloroacetoacetamide )
( DDA)
0 0 C H 3 C 2 H 5
Chlorobenzene I I I - - - - - - - - - - - ---> ( C H 3 0 ) 2-P-O-C= C-C -N + C H 3 C l DDA + ( C H 3 0 ) P
( TMP )
I I C l C 2 H 5
( Phosphamid o n )
The process flow charts for the above produ cts incorporat ing various
unit operations alongwith variou s inputs and outputs of products.
by-products, wastewater, gaseous emissions . and solid waste are given
in Fig. 3 . 2 . 4. 5, 4 . 6 , and 4. 7. The requ irement of raw materials per tonne
of each product and t h e details of wastes generated alongwith
pretreatment details are given in Tables 3 . 1 . 4 . 5 , 4 .6 and 4 . 7 . The total
water requ irement is 1 08 1 kid and 5 70 kid is the wastewater
generation. The water balance is shown in Fig. 4 . 8.
4 . 2 . 2 .2 . Waste flow
The sou rces of the wastewater are identified and their qu antities
determined. The wastewater from monocrotophos i s 1 60 kid, kid from cypermethrin , 60 kid from phosphamidon an d 1 6 k i d from DDVP. The
39
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M P B 0 - 4 9 D V O 0 . 5 8 0
N a C N 0 . 2 0 8 X Y L E N E 0 . 9 6
T O E T P --
----
T O S T A C K N a O H I�
', S C R U B B E R
I
C O N D E N S AT I O N
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C ATA L Y S T
T A N K
I -
-
M P B - tET APHENOXY BENZALDEHYDE D V 0 - ACID CHLORIDE (ALL QUANTITES ARE IN TONNES)
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t-1 1/'l 0 I-
T M P 0 . 5 7 0 I T O X I F I C A T I O N
C R U D E D D V P
C H L O R A L 0.7 7 1 -
w t-<( V'l z UJ Cl z 0 u I-UJ ...,
' - D E T OX I F I C AT I O N
N a O H - T A N K
-
�
C O N C E N T R AT I O N -- T E C H . D D V P 1.0
UJ I-< V1 z UJ 0 z 0 u I-UJ
1( :- T O E T P 4.0
T M P - T R I M E T H Y L P H O S P H I T E
D D V P - D I C H L O R O V O S
( A L L Q U A N T I T I E S A R E I N T O N N E S )
() -u () OJ m z < (/) () CD ::::I -
ro
I ("')
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("')
::::I ...__,
D I E T H Y L A C E T O A C E TA M I O E -----.��
0.5 3'1 . C H L O R I N E --�-.,.
0 - 4 9 0
P H O S P H A M I D O N -ie_'-------1 1.0
H C l GAS 0.244 I
C HLORINA T I O N
WAT E R
'
S C R U B BER t-----� T 0 E T P 2 6.0
D E G A S S I N G D D A DRY I N G
J E T C O N D E N SA T E M E T H V L C H L O RIDE
0 , 1 6 3 T O rA C K
'
t-ie---- T M P Q .649 --------t P R E C O N C E N TRAT ION1"':::'--4,,---i TOX I F ICA T ION P URIF I C A TION -
..,-----SOLV E N T 0 . 1 5
11 H A Z . WAST E TO I NC I N E R A TOR
UJ � I[) z UJ c z 0 u t-w ......
H A Z . W A S T E T O
I N C I N E RA'TOR
JET C O N D E N SAT E _
l D E TOXIF I C A TION ----- T O E T P 9·0
J, J E T C O N D E N S AT E i i .,_______ _____ � N a O H
( A L L Q UA N T I T I E S A R E I N T O N N E S )
0 ""CJ 0 OJ m z < CJ) 0 CD ::::J ........ ., CD
TABLE 4.5: DATA SHEET ON INPUTS AND OUTPUTS FOR THE MANUFACTURE OF CYPERMETlffiIN
Raw material per tonne of product:
Quantity, kg S.No. Raw material
Actual
1 . Acid Chloride (DVO) 580
2 . Metaphenoxy benzaldehide 490
3 . Sod ium cyan ide 208
4. 0-xylene 9 6 0 . 5
5 . Na2C03 1 6 1 . 5
6 . Na C l 280
Water requirement per tonne of product:
Nil (no jet-ejectors) Ni l
Stoichiometric
547
476
1 1 8
Not process chemicals used for
washing
Steam Cool ing Process Washing with Na2C03/NaCl : 675 l
Making solution of NaCN : 250 1
w t t t d as ewa er genera e
S.No. Source
1 . Washing with Na2C03/NaCl
2 . Caustic Scrubber for HCN emission
3 . Drips and drai ns
Emissions:
per t f d t onne o pro UC
Nature
NaCN , Cypermethrin Na2C03, Na C l
Scrubber l iquor
-
Quantity, Pretreatment kg
675 De to xi fication using H 2 0 2 after m a i ntaining pH 9 - 1 0 using aceti c acid
Varyi ng -do-quantity
-do- -do-
S.No. Source Nature Quantity Gas flow Control Chimney Nm3/hr equip. ht •• m.
1 Condensation HCN - 900 Caustic 15 scrubber
Solid waste/hazardous waste: Ni l
43
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TABLE 4.6 : DATA SHEET ON INPUTS AND OUTPUTS FOR THE MANUFACTURE OF DICHLOROVOS
Raw material requirement per tonne of product :
Quantity, kg S.No. Raw Material
Actual
1 . Chloral 7 7 1
2 . Trimethyl phosp hite 570
Water requirement per tonne of product :
Steam Cooling Process
Total
4 . 0
5 . 0
N i l
9 . 0 kl
Wastewater generated per tonne of product:
Quant S.No. Source Nature - i ty,
kl
Solvent traces L Jet condensate & spi l ls o f toxic 4 . 0
material
Emission: r S.No. Source Nature Quantity Gas flow, kg/t Nm3/hr
l. Toxification CH3CI 229 17760
Hazardous waste/Solid waste: Nil
44
I Stoichiometric
668
5 6 1
Pretreatment
Detoxificat ion with NaOH at pH 10-
10.5
Control Chimney equip. ht., m
Nil 39
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TABLE 4.7: DATA SHEET ON INPUTS AND OUTPUTS FOR THE MANUFACTURE OF PIIOSPHAMIDON
Raw material requirement per tonne of product:
Quantity, kg S.No. Raw material
Actual
1 . D iethyl Acetoacetamide 531 2 . Chlorine 490 3. Trimethyl phosphite 649 4 . Solvent 150
Water requirement per tonne of product :
H C I Scrubber Steam Cooling (make up) Process
Total
26 .0 kl 9.0 k l 21 .0 k l N i l
56.0 kl
Wastewater generated per tonne of product:
Stoichiometric
524 474 4 14
Not a process chemical
S.No. Source Nature Quantity, Pretreatment kl
1 . H C l scubber H C I 26 N i l
2 . Jet condensate s p i l l s Solvent traces toxic 9 D etoxification materials
Emission:
S.No. Source Nature Quantity Gas flow Control Chimney kg/t Nm3/hr equi p. ht., m
1. Chlorination H C I 244 3500 Water 39 scrubber
2. Toxification CH3CI 168 17760 N i l -do-
Hazardous waste:
S.No. Nature Nature Quantity, Pretreat Method of
kg -ment disposal
1 . Preconcen tra t i on
2. Product Degraded
HC 216 Nil Inci nera t i o n purificati on
4 5
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C O O L I N G WAT ER
� 1 0 5 M31 DAY
( AL L EVAPORATED )
R A W W A T E R 1 0 81
I I B O I L E R H O U S E
D O M E S T I C WAT ER
I N DUSTRIAL
WATER �
1 4 6 M l/DAY
� 3
-[�����=ate to 1 1 4 M I DAY E T P
2 1 M 3 t DAV
J loss 4 M I DAY
Cypermethrin
3 it M I DAY
Boiler Blow down
.t 5 6 5 M 3/DAY
J90 Mi DAY
Ga rden'tng
3 l 7 5 M / DAY Laundry & Toilets
2 b 5'h/ DAY
7 7 4 M J/ DAY ...._ ______ --flllll EFFLUENT T R E ATMENT 111t-------'
P LAN T
.__ __ -'"_ 5 7 0 M3
1 DAY TO M I D C SEWER
1 4 0 M 3 / 0AY - E T P
H C I Scrubbers
J . 6 J /OAV- E T P Vacuum p u m p ·n Monocrolophos 10 . 4 M1DAY - ET P Caust i c preparation
_ 3 �so Incinerator bleed 1 1 1 M/ DAY
2 4 To air via sla�k
J / DA 37 Or'1ps1 drains, drum washing 4 M Y . leaks, fR: fighting drills ,
Cypermelhll 1n vehicle washing , con!een
29 M3/ DAY
Chloral
loss
( Average for A p r. 9 1 - M::ir. 9 2 )
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other wastewater are 50 kld from incinerator. 28 kid from boiler blow
down. 175 kid from laundry and toilets and 37 kld fr o m drips. drain,
drum washings etc . The toxic streams are detoxified by raising pH to
1 0 - 1 2 using caustic soda, and s u fficiently detaining the wastewater
under agitation. The wastewater from various sources i s t h e n collected
and fu rther treated in eflluent treatment plant ( ET P ) . T h e wastewater
flow lines ar� given in Fig. 3 . 5 .
The process emissions include HCI. CH3Cl . chloroform. C H 3 C l . HCN,
P 2 0 5 , SPM, S02 and NOx. The details of the sources of emissions, gas
flow rate, control equipment provided and height of t h e chimney are
given in Table 4 . 8 . About 5 . 0 t of solid waste is generated per annum.
The details of its typ e , quantity and disposal are given in Table 4 . 9 .
4 . 2 . 2 . 3 . Monitoring and analysis
The sampling points identified to determine the characteristics of
wastewater and performance of wastewater treatment system are shown
i n Fig. 3 . 5 . The stacks could not be monitored d u e to time constraint.
Two ambient air q u ality stations are operated by the i n d u stry at the s i t e .
The available data with the indu stry was collected. The process samples
were analysed for pH. SS, COD. BOD, TDS, chlorides, TOC, sulphates
and COD. The samples from ETP were analysed for p H , COD. TOC,
TSS, pesticides ( M C P . CYPER. DDVP. P M N l and flow rate, and D O .
MLSS. a n d MLVSS i n case of aeration tanks.
Process samples were of grab type but the ETP samples were collected
hou rly for eight hours and composited. The samples were collected on
two consecutive days.
4 . 2 . 2 . 4 . Field observations
Not all the products are manufactured throughout t h e year.
monocrotophos is manufactured throughout the year but
cypermethrin is manufactured for nine months, phosphamidon for
eight months and dichlorovos for two months. M o n o crotophos and
cypermethrin have separate process route but phosphamidon and
D D V P have only one process route due to which only o n e of these
products is manufactured at a t ime. Monocrotophos is
47
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Ci)
TABLE 4.8: DETAILS OF EMISSIONS
S.No. Source I
Nature Quantity of
product kg/t
Gas flow,
Nm9/hr
Control equipment
Chimney ht,m
- - - - - - ... . - - - - - - - - - - - - - - - - ........ - - - - - - - - _....._ - - - - - - - - - - - - - - - - - - -' - - - - - - - - -+- -- - - - - - - -I- - - - - - - - - - - -
A. MONOCROTOPHOS - - - - - - T - - - - - - - - - - - - - - - - T - - - - - - - - T - - - - - - - - - - - - - - - --- 1- -- - - - - T - - - - - - - - T - - - - - - - - - - -
1. : Chlorination HCI 16 4 2, :I> O : Water ' 36 I I I ' 1 scrubber 1 I I I I I I - - - - - - ; - - - - - - - - - - - - - - - - - ; - - - - - - - - - ; · - - - - - - - - - - - - - - - - - - 1-- -- - - - - ;-- - - -- - - - -i- - - - - - - - - - - -
2. : Toxification CH3CI 227 17,760 : Nil 4 1 I I I l I I - - - - - - ; - - - - - - - - - - - - - - -- - i · - - - - - - - - -t - - - - - - � - - - - - - - - - - - -r - - - - - - - ; - - - - -- - - - -i- - - - - - - - - - - -
3. : Air stripping Chloro- : 0-50 mg/Nm3 441 Ni l 20 : chloral effiuent form
' I I I I
-- - - - - _._ _ - - - - - - - - - - - - - - - + - - - - - - - - J � � - - - - - - - - - - - - - - --- ....._ _ -- - - - - _,_ _ - - - - - - - � - - - - - - - - - - -
B. DDVP -- -- - - , - - - - - - - - - - - - - - - - , - - - - -- - - , - - - - - - - - - - - - - - - - - - , - - - - -- - , - -- -- - - - -,- - - - - - - - - - - -
4. : Toxification : CH3CI 229 17,760 : Nil : 39 I t I I ' I
- - - - -- -4- - - - - - - - - - - - - - --- -4- -- - - - - - - ......... - - - - - -- -- - - -- -- - ..... - -I-- - - - - - - - -+- - --- -- - - - --4- - - - - - - - - - - -
C. CYPERMETHRIN -- -- _ _ T _ _ _ - - - - - - - - - - - - - T - - - - - - - - T - - - - - - - - - - - - - - - - - - T - - - - - - - T - -- -- -- - , - - - - - - - - - -
5. : Condensation HCN 1 Traces 900 1 Caustic : 15 , : scrubber : r I I I I I
- - - - - - -'- - - - - - - - - - - - - - - - - � - - - - - - - - -1- - - - - - - - - - - - - - - - - - - + - - - - - - - 4- - - - - - - - - -1- - - - - - - - - - - -
D . PHOSPHAMIDON - - - - - - .- - - - - - - - - - - - - - - - - T - - - - - - --
-. - - - - - - - - - - - - - - - - - - T - - - - -- - T - - - - - - - - T - - - - - - - - - - -
6. : Chlorination HCI I
244 3, 500 j I I
Water : scribber :
I I I 1 I I
39
- - - - - - i- - - - - - - - - - - - - - - - - -i- - - - - - - - - ; - - - - - - - - - - - - - - - - - - - -t- - - - - - - - 1- - - - - - - - - ;- - - - - - - - - - - -7. : Toxification CH3CI 168 17, 760 : Nil 39
I I I I I I - - -- - - ....._ _ _ - - - - - - - - - - - - - - ...,:_ _ _ - - - - - - ..,. _ _ _ - - - - - - - - - - - - - - - � - - - - -- - ....._ _ -- - - - - - -'-. - - - - - - - - - - -
E. INCINERATOR - - - - _ _ T _ _ _ - - - - - - - - - - - - - T - - - - - - - - , - - - - - - - - - - - - - - - - - - T - - - - - - - 1 - - - - - - - - , - - - - - - - - - - -
8. : Liquid waste : incinerator
P205 HCI
0-35 mg1Nm3 695 ' Caustic I • scrubber ' I I 1 i I
30
- - - - - - 1- - - - - - - - - - - - - - - -- i- - - - - - - - - i• - - - - - - - - - - - - -- - - - - 1- - - - - - - - i• - --- - - -
-1 -
- - - --
-- - - - -
9. : Solid waste SPM * ' * Nil ' 30 : inc: - 1erator I I I I
- - - - - - --1- - - - - - - - - - - - - - - - - __,_ - - - - - - - - --1- - - - - - - - - - - - - - - - - - - -4� - - - - - - - -�- -- - - - - - -I- - - - - - - - - - - -
F . BOILER - - - - - - T - - - - - - - - - - - - - - - - T - - - - - - -- T - - - - - - - - - - - - - - - - - - T - - - - - - - I - - - - - - - - T - - - - - - - - - - -
10. Boiler.s 4 nos. Steam gen. capacity 3456
, kg/hr per boilder
SO�,NOx SPM
G. DIESEL GENERATOR
' SPM-85-720 mg.1Nm3 S02- 1 0- 1 4 0-mg1Nm3
N0 .-0.5-2 m�m3
3, 800 Nil 30
- - - - - - - - - - - - - - - - - - - - - - -.- - - -- - - - - ,- - - - - � - - - - - - - - - - - - ,- - - - - - - - , - - - -- - - - -, - - - - - -- - - - -'
• Capacity 365 KV A • * * * * 10 above RL
* iuformatio11 1wt apailable
48
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co
TABLE 4.9 DETAILS OF HAZARDOUS WASTE
S.No. Type o f waste Quantity kg/yr
1. Cyanide waste from 0 . 0 5 - 0 . 1
used cyanide containers
2. Organic residues 165 kl/yr
3 . O i l drips as drains 200-300
4 . Sludge from ETP 3600
5. Waste containing 1 9 5 kl pesticides ( 1 0 .5-3% of
pesticides)
6 . Off-specification and discarded products
7 . Discarded containers 1200
& container l iners of hazardous & toxic waste
4 9
Method o f disposal
Empty container along with plast ic bags is filled with H202, deto-xi fied and the n hurried with alkal i
Incineration
() Collected using saw dust, ""O and incinerated () OJ
m z Land fill ing in factory < premises (j)
() CD :::J
Incineration -' CD
-:;E �
Incineration (") "'O (") O"' CD :::J <
Metalic drums are CJ> detoxified by heating :::J
at h igh temperature and (") then crushed and sent :::J
..._ as scrap
manufactured at 1 . 7 t per batch and batch time is 8. 00 hrs . .
whereas phosphamidon is manufactured at 1 . 95 t per batch and
the batch time is 1 6 hrs. cypermethrin manufactured at is I
t / batch and batch time is 2 days. and DDVP is produced at 3 . 45
t / batch and batch time is 1 6 hrs.
These variations in daily production lead t o variation in characteristics of wastewater received at ETP. Detoxiflcation
systems are provided at the process wastewaters to reduce shock
loads due to toxicity on the ETP.
• The wastewater from various sources is collected through a
well-designed drainage system. Stormwater drains are kept
separate.
..
The treated wastewater is disposed to a pubic sewer which fin ally j oins a river. The river has back waters normally except during
rains.
The location where the industry is existing has not been declared
as air pollution control area under the Air Act. 1 98 1 and hence this
Act i s not applicable. Industry need not obtain consent for
emissions from the State Pollution Control Board.
Industry has good house-keeping practices. Safety and quality
control are give n highest priority. Floor washing is totally avoided.
I n case of spills, saw dust is used t o wipe i t out . Overflows, spills
an d leaks are kept t o the minimum. Manual transfe r of chemicals
is avoide d . Site is well laid out considering compatibility and safety
while locating various activities.
.,. The site is surrounded by hills and valleys.
The staff are qualified, process performance norms are well
understood. However. the operators at the ETP are not fully aware
of 'dont's' .
Land is available in plenty for any addition. if n ecessary.
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4 . 2 . 2 . 5 . Draft report
A draft report was prepared and handed over to the management. The
management was not in favour of recovering a contaminated by-product
and reusing or recycling waste that can contaminate product, b u t
welcomed suggestions for t h e improvement o f environment a n d assured
immediate implementation.
4 . 2 . 3 Post-audit activities
4 . 2 . 3 . 1 Synthetis
i ) A comparison of stoichiometric and actual requirement o f various
chemicals shows that their excess usages are 3 2 - 55% in case of
monocrotophos. Sodium cyan ide use is very high to the order of
76% in excess in case o f cypermethrin , and trimethyl phosphite
used is about 56% excess in case of phosphamidon. The material
usage is not much in excess in case of dichlorovos. These excess
us ages of materials may be presumed to be finding their ways to
environment thereby causing pollution. The cause of these
excesses may be attributed to inefficient process p e rformance and
raw materials impurities.
i i ) The water consumption p e r tonne o f product i s highest with 8 1 .4
kid in case of monocrotophos. 50 kid in case of phosphamidon, 9
kid in case of DDVP and 1 kid in case of cypermethrin. The
wastewater generation from process is 56 kid per tonne of
monocrotophos. about I kid per tonne of cypermethrin, 4 kid per
tonne of DDVP and 35 kid per tonne of phosphamidon. The total
wastewater generation is 540 kid of which 48% is from process.
3 1 % is from laundry & toilets and 2 1 % from boiler blowdown and
steam condensate.
The process wastewater is biodegradable but toxic. The treated
wastewater is conforming to the prescribed standards except for
CO D which is slightly exceeding the limit o f 2 5 0 mg / l . The
wastewater flow rate in the final outlet is seen to be widely varying.
The operators are not aware of how the flow should be regulated i n
the ETP .
5 1
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iii ) The treated effluent is disposed to a public drain which ul timately
joins a river.
iv) About 3 t / d of methyl chloride emission. which is highly toxic is let
into the atmosphere. thereby adding to the risk of environmental
hazard.
v ) The ambient air quality record maintained by the industry does n o t
include all t h e air pollutants emitted.
2 . 3 . 2. Final report
A flnal report incorporating various observations and recommendations
was prepared. The important recommendations included the following:
.. The excess u s age of raw materials especially in case o f
monocrotophos. sodium cyanide in case of cypermethrin a n d
trimethyl phosphite i n case of phosphamidon a r e to be reduced.
Performan ce studies of various process equipment are to be carried
out and norms fixed up for each operation such that maximu m
utilisation of materials takes place and only the u n avoidable wastes
are generated.
..
..
The de-aerator overflow of the steam condensate has been fou n d
t o b e well within limits except for p H . This stream may b e isolated.
neutralised and reused for floor wash or used for gardening or
irrigation purposes in the factory premises at the rate of 3 5
k i d/hectare/ day.
The treated wastewater from ETP should be subjected to tertiary
treatment by activated carbon, ozonation etc. so as t o reduce CO D
and pesticides. and recycled for developing green belt in the factory
premises.
Methyl chloride emission should be recovered as a by-product
through a liqu ifation plant or incinerated.
Rate of flow to aeration tanks in the ETP should be kept constant
t o avoid shock loads.
5 2
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• Ambient air quality monitoring in the factory premises should
include the parameters of HCI. CH3Cl. HCN a n d Cl2 in addition to
SPM. CO, NOx and S02.
A manual for operation of the waste treatment facilities i s to be
prepared for use mainly by the operators.
• An organisational set up for environmental management is to b e
made including people fr o m production, R & D . quality
control / laboratory. management. safety. waste treatment facilities
and an environmental specialist. The operators o f t h e waste
treatment facilities are to be well-trained.
5 3
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REFERENCES
1 . Indu stry and Environment, UNEP. Vol. 1 1 No. 4. O c t / Nov/ Dec, 1 99 1 .
2 . Audit a n d Reduction Manual for Industrial Emissions and Wastes,
UNEP. 1 99 1 .
3 . Bh attacharyya. R . N . . Environmental Audit in Industries : G u idelines,
Ministry of Environment & Forests sponsored course on Environmental
Impact Assessment held in Zoological Su rvey of l ndia, Calcutta. January
18 - Febru ary 1 9 . 1 9 93.
4 .
5 .
6 .
7 .
8 .
Environmental Audit at M I s NOCIL - Agrochemicals Plant. Central
Pollution Control Board. Delhi. 1 993.
Raghu Babu. N . , Basu . D . D . . Chakrabarti. S . P . . Environmental Audit in
Industry. Seminar on 'Environmental Statement (Audit ) ' held on 2 9. 7 . 9 3
at Alwar by Rajasthan Pollution Control Board.
Ragh u Babu. N . . Chakrabarti. S . P . , Environmental Audit - a tool for
Waste Management. Seminar on 'Environmental Triangle - Industry,
Institutions & Regulatory Agencies' held on 7 . 1 0.93 at New Delhi by
Shriram Institute for Industrial Research.
M inimal National Standards - Pesticides Manufacturing and Formulation
Industry, Central Pollution Control Board, Delhi . COINDS/ 1 5 I 1 98 5 - 86 .
Revised Minimal National Standards for Pesticide Manufacturing and
Formulation Industry. Part I. Central Pollution Control Board, Delhi.
COINDS / 3 0 / 19 8 8 - 89 .
5 4
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5. 1 MINAS FOR PESTICIDES INDUSTRY
Compulsory parameters Limiting concentration
Temperature Shall not exceed 5°C above the receiving water
temperature
pH 6 . 5 to 8 . 5
Oils an d grease IO mg/l
Bio-chemical Oxygen Demand 30 mg/I
Total suspended solids I 00 mg/I
Bio-assay test 90% survival after 96 hrs.with fish at I 00% effluent
Optional Parameters
a ) Specific pesticides
Benzene hexachloride
Carbaryl
DDT
Endosulfan
Dimethoate
Fenitrothion
Malathion
Ph orate
Methyl parath ion
Phenthoate
Pyrethrums
Copper oxychloride
Copper sulphate
Ziram
Sulphur
2. 4 D
Limiting concentration
(in µ g / l }
1 0 1 0 1 0 1 0
450
1 0
1 0
1 0 1 0 1 0 1 0 9 , 600 5 0
1 , 000 3 0 300
57
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Paraquat
Propanil
Nitrofen
Phosalone
2 3 ,000
7 . 3 0 0
780
80
b ) Heavy Metals
c l
d )
Notes:
1 .
2 .
3 .
4 .
5 .
Copper
Manganese
Zinc
Nickel
Mercury
Tin
Organics
Phenol and Phenolic
compounds as C6H50H
In organics
Arsenic as As
Cyanide as CN
Nitrate as N03
Phosphate as P
1 . 0
1 . 0
1 . 0
1 . 0
0 . 0 1
0 . 1
1 . 0
0 . 2
0 . 2
50
5
Limits should be complied at the end of the treatment plant before any dilution.
Bio-assay test should be carried out with available species of fish i n receiving water.
State Boards may prescribe total dissolved solids (TDS) . s u lphate and chloride depending
o n the uses o f recipient water body. Industries are advised to analyse pesticides ln wastewate r by advanced analytical method such as GLC.
State Board may prescribe COD limit correlated with B O D limit.
Pesticides are known to ha\•e metabolites and isomers. If they are fou n d i n significant
concentration. standards may be prescribed fo r these i n optional list. by State Board.
58
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5 . 2 SEPARATION TECHNOLOGIES FOR REMOVAL OF ORGANIC AND
PESTICIDAL CHEMICALS FROM WASTEWATER
The following unit operations have been grouped under the Separation
Technology for removal of organic and pesticidal chemicals from waste-
water:
1 . Absorption
2 . Adsorption including bubble adsorption
3 . Centrifugation
4 . Clathration
5. Coagulation
6 . Coalescence
7 . Condensation 8. Cyclonic Action
9. Desorption
1 0 . Dialysis
1 1 . Diffusion Process
1 2 . Electro-phoresis
1 3 . Evaporation . .
1 4 . Extraction
1 5 . Filtration
1 6 . Flash Expansion
1 7. Floatation
1 8 . Foam Fractionation
1 9 . Gravity Settling
20. Impringement
2 1 . Membrane Permeation
22. Precipitation
2 3 . Reverse Osmosis
24. Scrubbing
2 5 . Stripping
26. Ultra- filtration
59
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5 .3 DESTRUCTION & DETOXIFICATION TECHNOLOGIES FOR TOXIC
WASTES
1 . Chlorine dioxide oxidation
2. Dye sensitized photo-oxidation
3 . Electro-chemical oxidation
4. Flameless catalytic oxidation
(Low temperature vapou r oxidation)
5. High energy radiation
6. Hydrogen peroxide oxidation
7. Incineration I c o m b u s ti on process
8. Micro-biological an d other metabolic systems
9. Ozonation and other ultrasonic energy
1 0 . Photo-decomposition - u l traviolet radiation
1 1 . Potassium permanganate oxidation
1 2 . Pyrolysis
1 3 . Reductive dechlorination
1 4. Ultraviolet ray assisted ozonation
1 5 . Wet catalytic oxidation
60
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I< 1 OR 2 0 R 3 C.vl BE OPTED DEPENDING ON WASIEWATER QUALITY
HIQil.Y TOXIC WASTE - I N C I N E RATION
TOXIC WAST E (llOT EASILY DETOXIFICATION BOOEGAAO-
Oil SEPARATOR EQUALISATION
A Bl. E )
SPILLS LEAKS
& �
REACmR
WIPE OUT l51NG COTlON .
SAW DUST E T C . INCINERATION
CSOLVENT VESSEL /j � ��NGS WASH REUSE FOR FORMULATICN
FORMUAT '---�������---' TOILET S. CANTl:EN
CLARIFLOCULATCW'I
AERA'OON STAGE I
. ..
H, 0 2 / N a O C l
OXIDATION
AERATION
STAGE II
INCINERATION
PRE CONCENTRATKJN
NEUTRALISA TIOO
OXIDATION
ACTIVATED CARBON
FILTRATION
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ACTIVATED CARBON Fil TRA TION
FINAL OOLLECTON TANI\
+ DISF'IY.>Al
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5 . 5 WATER USAGE & WASTEWATER GENERATION I N VARIOUS
INDUSTRIES
Name of Industry
Integrated Iron & Steel
Sugar
Fertiliser
Water use
2 0 c u m / t of finishe d steel
2 cum / t of cane crushed
Straight nitrogen- 1 5 cum / t of urea or ous f etiliser equivalent produ
ced
Straight phosphatic 2 cum / t of fertiliser (SSP&TSP) SSP/TSP excluding manufac-ture of any acid
Wastewater generation
1 6 cum i t of f inished steel
0 . 4 c um / t of cane
crushed
5 cu m / t of urea or equivalent produced
0 . 5 cum / t of SSP/TSP
Complex fertiliser Standards of nitrogenous and phosphatic fertiliser applicable depending on primary product
Small Pulp & Paper
Agro-residue based 200 cu m / t of
paper
Waste paper b ased 75 cum / t of paper
Large Pulp & Paper
Pulp & Paper
Rayon grade pulp
250 cum / t of
paper
200 cu m / t of
paper
62
1 5 0 cum / t of
paper
50 cum / t of paper
1 75 c um / t of paper
1 5 0 c u m / t of
paper
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Fermentation
Maltry
Brewery
Distillery
Caustic Soda
Mercury cell process
Membrane cell
process
Textile
Manmade fibre
i ) Nylon & polyester
ii) Viscose rayon
Tanneries
Natural rubber
Starch. glucose
& related products
8 . 5 cum / t of grain processed
1 cum / kl of beer produced 1 5 cum / kl of
alcohol produced
3 . 5 c u m / t of grain processed
0 . 2 5 cu m / kl of beer produced 1 2 c u m / kl o f alcohol
produced
5 cu m / t of caustic 4 c u m / t of caustic
soda produced( excluding soda ( Mercury bear-cooling water) ingl I 0% blow down & 5 c u m / t of caustic permitted for soda produced for cooling water
5 cum / t of caustic
soda in cluding cooling water
1 7 0 cum / t of fi bre produceg��
cooling tower.
1 c u m / t of caustic soda excluding cooling tower blow down
1 2 0 c u m / t of fibre
produced
Limits specified in rayon grade
Pulp & paper applicable
30 cum / t of 28 cu m / t of
raw hide raw hide
6 cum / t of 4 c u m / t of
rubber rubber
1 0 cum / t of 8 cum / t of
maize crushed maize crushed
63
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5 . 6 EMISSION STANDARDS FOR SOME SPECIFIC POLLUTANTS
The emission standards for some of the specific pollutants are yet not laid down by the Central Board. These pollutants generally pertain to chemical process industries and are emitted not through the conventional stacks or chimneys but mostly from the reaction vessels, scrubber outlets and other such equipment. The emission of these pollutants gives rise to environmental pollution and nuisance, especially in t h e vicinity of the industrial plant. It is, t herefore, necessary to determine and lay down the emission limits for these pollutants.
In the absence of adequate literature source which could be helpful in specifying the emission limits for these pollutants. the Threshold Limit Value (TL Vl has been taken as the basis to determine the emission limits. The following formula has been adopted for this purpose :
Emission l imit = TLV
3 x 1 0
X ( 1 00 to 1 5 0 )
= 3 . 3·3 TLV t o 5 . 0 TLV
The constants appearing in the s.bove formula are explained u under :
* The constast 3 is included to reduce the allowab l e concentration to take
care of 24 hours exposure. This is to extrapolate t h e 8-hour span used
in TLV over t h e span o f 24 hours.
The constant 1 0 is included to reduce the concentration in the ambient air to impart additional safety. This is in line with the "application factor" commonly used in fixing water qu ality criteria.
The constant 1 0 0 to 1 50 represent the minimum dilution available i n open atmosphere.
64
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ANNE.KURE I
M I N I STRY OF E N V ! n O N M E N T & FORESTS
NOTIFICATION New Delhi , the 22nd Apri l , 1993
G.S.R. 386(E)-In exercise of the powers conferred by sections 6 and 25 of the Environment (Protection) Act, 1986 (29 of 1986), the Central Government hereby makes the fol lowing ru les further to amend t he Environment (Protection) Rules, 1986, namely -
1 . ( 1 ) These rules may be cal led t he 'Environment (Protection) Amendment Rules, 1993 .
(2) They shal l come into force on the date of their publicat ion in the Offic ia l Gazette.
2. In t he Environment (Protec!ion) Rules, 1986 -
(a) In Rule 14 -(i) for the words ";iudi t report" wherever they occur, the word "statement" shall be substituted :
(ii) for t he figures, letters and word-. " 15 t h d;iy of May" the words " th ir t ie th day of September," sha l l be substituted.
(b) In Appendix 'A " for FORM-V, the following sha l l be substituted, namely : -
" F O R M -V "
(Sec rule 14)
Environmental Statement for the financial year ending the 31st l\farch . . . . . . . . . . . . .
Pt\RT - t\
(i) Name and address of the owner/occupier of the industry operntion or process .
( i i ) Industry category Pr imary - (STC Code) Secondary - (S IC Code)
( i i i ) Production capaci ty - Units -
(iv) Year of establishment
(v) Date of the last environmental st<1tement submitted.
Water and Raw Materi;il Consumption
( 1 ) Water consumption m3AJ Process Cooling Domestic
Pt\Iff - B
Nature of Products Process Water Consumption per uni t of product output
1) 2) 3)
During the previous financial year
6 5
During the current financial year
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{2) Raw material consumption
*Nature of Raw material Process Water Consumption per unit of product output
During the previous financial year
During the current financial year
Industry may use codes if dislosing details of raw material would violate contractu a l obl igations, otherwise all industries have to name the raw materials used.
PART - C
Pollution discharged to environment/u n i t of output
(Parameter as specified in the consent issued)
Pollutants
.
(a) Water
(b) Air '
Quantity of pollutants discharged (mass/day)
' -
-
Concentration of pollutants in discharges
(mass/volume)
. . -
PART - D
HAZARDOUS WASTES
Percentage of variation from prescribed
standards with reasons
'
-
(as specified under Hazardous Wastes/Management and Handling Rules, 1989)
Haza rdous Wastes
(a) From process
(b) From pollution control faci l i t ies
Total Quantity (kg)
During the previous financial year
6 6
During t h e current financial year
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(a) From process
(b) From pollut ion control faci l i ty
( c ) ( 1 ) Quant i ty recycled or reuti l ised w i t h i n t he un i t
(2) Sold
(3) Disposed
PART - E
SOLID WASTE
Total Quanti ty
During the previous financial year
l'ART - F
During the current f inancial year
P lease specify the characterisations ( in terms of compos it ion and quantum) of hazardous as wel l as sol id wastes and indicate disposal practice adopted for both these categories of wastes .
l'ART - G
Impact of the pol lu t ion abatement measures taken on conservation of natural resources and on t he cost o f production.
l'ART - H
Additional measures/investment proposed for environmental protection including abatement of pol lut ion, prevention o f pollu t ion.
PART - I
Any other particulars for improving the qua l i ty of the environment
6 7
(F. No. Q-1501 5/1/90/CPA) Mukul Sanwal, Joint Secretary
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ANNEXURE II
QUESTIONNAIRE FOR ENVIRONMENTAL AUDIT PART I
1 . Name of the industry & location : ( Enclose a map showing surrounding landuses upto 500 m l
2 . Date o f commencement o f production:
3 . Type o f industry:
( i ) LARG E / M E D I U M / SMALL ( based on capital investment) (Small : < Rs 50 lacs: Medium:Rs 50 lacs · Rs 5 crore: Large: > Rs 50 crore)
(ii ) MANUFACTURING I FORM ULA TING I MFG.&FORMULA TING
4. Products manufactured:
Name of the Installed product capacity,
( t / a )
Avg. prod uction ( t / a )
No.of days of prod.per year
Do you have separate process lines for each product ?
Remarks
If n o , state which produts are manufactured in the same process line?
5 . Raw materials used, productwise ( k g / t o f product) :
6 8
Yes / No
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6 ( a ) Details of manufacturing process alongwith process flow ch art sh owing various unit operations and material balances. Indicate point sources o f emission a n d fugitive emission ( Enclose separately)
( b l Give details of the State-of-art technology for the products manufactu red:
c l
( d )
PART II
Do you have plans for expansion?
If yes, give details.
Do you have plans for the modernisation of process technology ? If yes, provide details.
7 . Water requirement:
( a ) Industrial (product wise) :
Process Name of the product operation where
Quantity used, kl
Yes/No
Yes/No
water used Per day Per t of Product
( b l { c l ( d )
Domestic Others Total
kid: kid: kid
(Also incorporate all the above flgures in PROCESS FLOW CHARTS)
8 ) Wastewater generated:
69
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( a ) Industrial :
S . N o . Operation where waste Quantity. k l generated
Per day Per t of Product
( b l Domestic kid
( c l Boiler kid
( d ) Cooling tower kid
( e l Others( specify l k i d
f1 Total kid (Also incorporate the above figu res in process flow chart)
9 (a ) Characteristics of wastewater. stream-wise:
Product Source of wastewater generation
Characteristics
b l Characteristics o f combined wastewater:
Parameter Before treatment After treatment
70
Standards prescribed
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1 0 . Effluent treament system provided:
Describe the treatment system provided to individual streams and combined eff luent . Enclose drawings of the effluent tretment system showing the sizes of the individual units . Also provide analysis reports showing the performance of the individual treatment units . ( Enclose separately).
1 1 . Treated effluent disposal:
( a ) DOMESTIC: ( b l INDUSTRIAL:
(specify t h e place of disposal and mode of discharge using sprinklers.marine outfall. etc . )
1 2 . Storm water drainage system:
* Is it separate from industrial /domestic drainage system ?
Describe the method of storm water collection,tratment and fm al disposal.
1 3 ( a l Solid waste:
Source Composition
( b l Hazardous waste:
Source Composition
Quantity
Quantity
Mode of Mode of Collection Disposal
7 1
Method ojMethod of collection disposal
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PART DI
1 4 . Details o f emission generated
S . N o .
•
( a l Process emission (product wise ) :
Source Type o f Sou rce Std Gas • pollut- Strength pres- flow
a n t (mg/Nm3) cribed Nm3 / h r
Control Cone. i n Stack E q u i p - Stack/ Height
ment Vent (m) above •• {mg/Nm3) GL rool
• • • level
•• Ind icate t h e operation i n the reactor. incinerator. flare . fu rnace.etc Att,!'lcil drawrngs of air pollution control systems alongwith design data Based o n actual monitoring • • •
b l Emissions from combustion o f fuel viz. coal, fire wood, furnace oil , etc.
Cone. of Chimney Fuel u s e d SPM / Height
Type of Gas flow S02 in (m) above
Type Qty. Purpose control in Stack Stack/ G L / Rool equipment m g / N m3 Vent Level ( k g / h r ,
day) provided m g / N m3
cl Information regarding principal air contaminants ( Fugitive emissions ) :
Typical toxic Possible sources of Activity Air contaminant concentration emission
( Rangel
eg. Polyvinyl Vinyl chloride 20 m g / c u m Leaks i n chloride pressurised system
d ) Are emission monitoring provisions made i n t h e stacks/vents ? Yes / No
7 2
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1 0 . Ambient air quality in the factory premises:
Parameter Concerntration (Annual) µ g / m3 ( Based o n actual monitoring)
Minimum Maximum Average
SPM S02 co NOX Acid mist HC voe ( n on-methane) Others. specify
PART IV
1 6 . Details of in plant pollution control measures:
1 7 .
1 8 .
Details o f waste (wastewater, gaseous emissions, solid waste) m i nimisation techniques used and recycling/reuse of waste adopted:
Whether the standards and other conditions laid down by the State Pollution Control Board under the Water Act. Air Act. and Environmental(Protection) Act are complied with ?
The Water Act. 1 9 74
The Air Act. 1 98 1
The E ( P )Act, 1 9 86
If no . specify reasons th ereof.
Has valid consent/ Complying with stds. authorisation and other conditions
Y e s / N o Yes / N o
Y e s / N o Yes / No
Y e s / N o Y e s / N o
(Also enclose copies of consent orders)
7 3
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1 9. Details of monitoring facilities available with the industry for emissions. wastewater.solid waste and the receiving environment:
Parameters Instrument Used Analytical Technique
20. Details of organisational set up for environmental management :
S . No . Name of t h e person Designation Qualification
2 1 . Cost of pollution control :
( a ) Annual sales tu rnover o f t h e industry : R s . . . . . ( b l Fixed cost of pollution control system (PCS) : Rs . . . . .
{ M ention details of components included) ( c ) Operating cost o f PCS : Rs . . . . .
Duties
( d ) Annual burden of PCS (Annualised capital cost of PCS + Operating
2 2 .
cost} : R s . . . . . .
Are there any public complaints against pollution from your industry ?
If yes. give details.
Yes/No
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2 3 . Details o f green belt/plantation:
2 4 . Problems faced by t h e indu stry i n pollution control :
2 5 . Name o f the contact person with designation and telephone N o :
Signature: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Name: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Designation : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Date : Place:
7 5
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ANNEXURE III
ENVIRONMENTALLY SAFE LAYOUT CODE FOR MANUFACTURING UNITS
1 . A n environmentally safe layout plan tal<es care of material loss. cost of collection , disposal. recycle and treatment which are parts of the process itself. and consequently of the layout arrangement.
2 . This layout code postulates that environment protection i s a factor for designing any equipment, reaction vessel. material transfer arrangement. storage tank. and service support to operate the production system.
3 .
4 .
5 .
6.
7.
8.
All places of storage of solid and liquid materials are t o be diked without drains. Any spillage is to b e wiped out and cannot be washed out .
Each vessel should have its own catchpit to collect spills.
Each pump must b e mounted on its own catch pit: a suction line of the pump should be connected t <? empty the pit , periodically or regularly or continuously.
As losses of materials take place during charging of the reaction vessels. discharging of produce and dripping of outlet valve s , and as materials may be either solid or solid slu rry or liql.tid, care needs to be exercised to prevent the losses. if necessary by changing the charging / discharging and transfer devices.
In order t o collect spills from a particular vessel before the spilled materials gf;!t a chance of contamination with spills fro m another nearby vessel. the two vessels must b e installed at su fficient distance so t h at inter- contamination cannot tal<e place. The extra distance. 'noncontaminating distance' is to be provided for recycle o f materials.
Flange joints should be avoided wherever avoidable.
9. Corrosion-prone areas and construction materials liable to atmospheric and process induced corrosion should be given special attention for finding better replacement material and stricter preventive maintenance frequency.
1 0 . Exh aust ducts and fan outlets are sources of pollution. if the thrown out air is contaminated with pollutants. These may b e treated before vented. Any vapour l ine should b e connected with either a recovery system or an absorption s�stem.
76
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1 1 .
( .
The engineering code for the operation of pressurised systems and t h e established practice for preventive maintenance are consistent with t h e protection o f t h e environment. These system are fitted w i t h pressure release valves. and in many cases with rupturable discs. The present practice is t o allow the released materials to the atmosphere. To b e environmentally. safe . these lines ought t o b e connected t o recovery I adsorption I absorption arrangements. The rupturing of safety discs i s accompanied with sudden release o f high pressure; t h e design of t h e recovery arrangement o f t h e released materials should b e befitting t h e sudden emerging conditions o f high temperatur e s / pressu r e / volumes.
1 2 . New u n its will build floors with expanded metals. slotted angles. steel gril ls . steel grates. prefabricated industrial f loor gratings. and the like which will make floor washing redundant.
1 3 .
1 4.
1 5 .
1 6 .
I f t h e plant layout demands that vessels should b e installed in upper floors. arrangements should be simultaneou sly made to spill avoidan ce / collection. Vulnerable points of leakage should b e taken special care of. This is necessary not only for pollution control but also for the safety of plant personnel worl<ing in lower floors.
Storage tanks of raw materials for supply to the production vessels. should b e installed on a separate structure located just outside the main plant b u ilding. with arrangement for holding spills and overflow. Level alarms should b e installed where possible: where the same is not feasible because of the nature of the liquid, two overflow pipes at two different levels of the tank should be fitted.
Plant management should evolve its own code for washing equipment, where a particu lar equipment is used for the m a n u facture of different products. Dry scraping of equipment �u rface followed by moping with wet cloth should be carried out before hosing operation. This will reduce the quantity of contaminauts and wastewater volume.
All channels be fitted with wastewater measuring devices, half barrier for t h e s e p a r a t i o n fl o a t i n g i m m i s c i b l e l i q u i d a n d i n - b u i l t separation I sedimentation basins for withholding settleable particulate matters. This provision may be treated as compulsory for wastewater channels in the immediate vicinity of wastewat e r generating u n its .
1 7 . All water usages that do not come in contact with chemicals. should have no opportun ity to mix with process water. Unconta�inated water should have separate outlets from the plant and i f recycle is not possible . should be drained out through separate channels. without any change of getting contaminated.
77
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1 8 . This proposed layout code recognises the solid waste generated i n the process of manufacture must find a place within the factory premises. It will be stored on land/ lagoon which will be lined with compatible geo-textile materials.
1 9 . The detoxification operation is to be carried out outside t h e main production plant. and provision has to be kept for the same.
2 0 . Storm water drains should b e segregated from process water drains. The former may be used for the removal of cooling water and non- process water.
(Source: 'Minimal National Standards-Pesticides manufacturing and formulation
industry ', COINDS I 1 5 I 1 985-86. Central Pollution Control Board, Delhi)
78
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ANNEXURE IV
GUIDELINES TO MINIMISE MATERIAL LOSSES AND WASTES
A) HOW TO REDUCE RAW MATERIAL LOSSES ?
> Keep only an appropriate inventory of raw materials to ensure minimum
material handling l�sses, evaporat ion losses etc .
Adopt mechanical handling of materials with proper monitoring facilities
so as to dose only the predetermined quantities as per norms prescribed.
> Plant layout should be properly made so as t o minimise transfer distance
of materials between storage and process or between unit operations.
>
>
>
>
There is a risl< of cross-contamination due to u s age o f same storage tanks
for different materials depending on the batch product. Separate storages
are to be provided.
Separate process lines for separate products o r separate equipment for
each unit operation can minimise losses d u e t o residues left out in the
equipment which are u s u ally washed out.
Storage t anks should be provided with proper dip arrangements for
exhausts /vents and insulation provided so as to reduce evaporation
losses.
Enclosed and covered material storage areas keep them s e c u r e d and
reduces losses due to carry over by wind and rain.
Enclosures should be made t o collect spills and overflows o f materials at
the material transfer and sampling points. These, if collected properly,
can be recycled.
Regular maintenance should be taken t o check flange leaks,
breaks / cracks, pump failures etc.
> Raw material purity should be ensured. Viscous raw materials lead to
losses due to residues in drums. Raw materials should b e easy t o handle.
Good h o u s e - k eeping practices should be followed.
> Norms for performance of various process operations fixed s o that t h e
material u s ages are minimised and h e n c e the material losses.
79
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B. HOW TO REDUCE WATER USAGE AND WASTEWATER GENERATION?
> Quantities required for each operation should be determined and water usage regulated strictly. Reduced water u sage reduces wastewa
.ter. Good
house-keeping practices reduces water usage.
> .Spills of materials should be restricted to enclosures constructed for this purpose. The floor washings can then be minimised and at times totally avoided.
> Wastewater may be stored and reused. The storage costs may be lower than waste treatment and disposal costs.
>
>
>
c.
>
Storm water drains should be kept separate and provisions should b e made t o collect only t h e rainfall of first few hours which carries contaminants. This can be subsequ ently treated and disposed.
The scrubbing of gaseous emissions with a suitable chemical can yield a n useful by-product. The discharges thus can b e avoided by recycle or recovery of usefu l by-products.
The wastewater is usually treated upto second ary treatment level to conform t o the required standards. By providing tertiary treatment by dual media filtrat ion. chlorination. activated carbon filtration e t c . wastewater can be reused for floor wash. gardening. toilets etc.
HOW TO REDUCE EMISSIONS ?
The process operations where emissions arise, should be provided with control equipment. Condensers can collect certain emissions which can be entirely reused.
The transfer of materials should be done through closed operations.
The areas where fugitive emissions arise and can be avoided should be enclosed and the air exhausted through induced draft and passed through control equipment before venting off. The enclosed area should be provided with atleast three air replacements per minute.
Evaporation losses from storage tanks should be checked by proper insulation and putting the vents in suitable dip columns.
> Loading and u n loading of materials from tankers leads to h u ge quantities of emissions. The material -transfers should be done through pipes/ holes keeping the outlet of the tanker and the inlet of receiving tank covered. While loading the tanker. if the tanker inlet cannot b e covered. a hood can be provided over the inlet and emissions collected through a ducting system and further controlled.
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