Technological, Environmental and Policy Issues

in the Chemical
&
Petrochemical Industry Sector with Particular
Emphasis on SMEs

Dr. D. D. Basu, Senior Scientist

Central Pollution Control Board
 Chemical Industries
Synthetic organic chemical industries
 Petrochemicals (basic & intermediates)
 Basic Organic Chemicals (esters, aldehyde, ketone, nitrates, chloride,
amine substituted organic compounds)
 Dye & dye intermediates
 Pesticides (technical & formulation)
 Bulk-drugs (Technical & formulation)
 Plastic, polymer & resins
 Paints
 Ink & ink printing
 Soap & detergent
Inorganic chemicals Agrochemicals
 Soda ash Fertilizer
 Chlor-alkali
 Inorganic chemicals
 PETROCHEMICAL PRODUCT TREE
 
  Building Block Intermediate Downstream Products
 
EDC PVC
 
  Ethylene Polyethylene
(Ld/Hd) Glycol Ethers
  Enthaloamines
EDC
  - Ethylene dichloride EO/EG
EO - Ethylene oxide
EG
  - Ethylene glycol
Isopropyl Alcohol/ Dye Stuff and
DMT   - Dimethyl terephathalate
Acetone Chemicals
PVC   - Polyvinyl chloride Intermediate
Propylene
PBR   - Polybutadiene rubber Polypropylene
SBR   - Styrene butadiene rubber Acrylonitrile
  Acrylic Fiber
  Plasticisers
  2 Ethyl Hexanol
  A B S Plastics
  Olefins PBR
Butadiene SBR
  Pharmaceuticals
Cumene/Phenol
 
  Thermoset Resins
  Cyclohexane/
  Caprolactum
Naphtha Nylon
  Benzene
  Detergents
  Alkylate Detergent
 
Polyester
  Aromatics Maleic Anhydride
  Alkyd Resins
 
Phthalic
 
Anhydride Plasticisers
 
Xylene Polyester
 
DMT Fibre
 
 
 RISK DEFINITION
 Risk is the chance of encountering the potential adverse effects of human or
ecological exposures to environmental hazards.

 Hazard is a descriptive term that characterizes the intrinsic capability of a

pollutant to cause harm.

 Risk is inherent in all forms of life.

 Risk assessment process of estimating the probability of occurrence of an

event and the probable magnitude of adverse effects.
Accident

Poisoning
Stroke Car Home Fires Lightening

1 chance 1 chance 1 chance 1 chance 1 chance 1 chance

in 10 in 100 in 1,000 in 10,000 in 1,00,000 in 10,00,000
 Risk Assessment /
Risk analysis type

Health Risk Assessment Safety Hazard Analysis

(human health focus) (human safety focus)
High probability, low low probability, high
consequence, ongoing, consequence, accidental,
chronic, delayed effect acute, immediate effect

Ecological Risk Assessment

(habitat/ecosystem focus)
Subtle changes, latency, complex
interaction, macro impacts
 THE 4-STEP RISK ASSESSMENT PROGRAMME

Hazard
Identification
What health problems are
caused by the pollutant?

Exposure Dose-Response
Assessment Assessment
How much of the pollutant What are the health
do people inhale during a problems at different
specific time period? How exposure?
may people are exposed?

Risk Characterization
What is the extra risk of
health problems in the
exposed population?
RISK MINIMISATION PROGRAMME

 Assessment and monitoring

 Leak detection and repair (LDAR)

 Impact assessment
ENVIRONMENTAL MANAGEMENT WHAT IT MEANS?

 Risk reduction due to continuous release of

pollutants to environment and its impact with respect
to health and ecology.

 Risk reduction due to sudden release (accidental

release) and its consequence.

 Resource conservation.
 INDUSTRY AND ENVIRONMENT
Reduction of Effects of
supporting assimilative
capacity capacity

Polluted water
Water resource resources

Waste
Withdrawn of water
raw material
Haz. waste
Industry Land

Effect flora
fauna Emission Health
Economic
value
Air pollution
Effect human
settlement Flora &
fauna
 PICTORIAL REPRESENTATION OF BALANCE
Gaseous Emissions
Raw materials

Catalyst Product
PLANT
Water / Air PROCESS By-product
OR
Power UNIT Catalyst
OPERATION

Recovery from waste

Recycle
Wastewater

Liquid wastes for storage

Reusable waste in and / or
off site disposal
another operation Solid wastes for
storage and / or
off site disposal
PRINCIPALS OF WASTE MINIMISATION

1. Control of raw material losses

2. Recovery and recycle / reuse

3. Recycling and reuse of wastewater

4. In-plant control
CONTROL OF RAW MATERIAL LOSSES

1. Optimisation of reactions and raw material use

2. Elimination of sources of leaks and spills

3. Installation of close system

4. Equipment standardisation

5. Installation of DCS.
 RECOVERY AND RECYCLE / REUSE
 The solvents used in the manufacture of various products can
be recovered and recycled / reused.

 In most of the chemical reactions, there are more products

formed than the required products. These unwanted products
form wastes if left un-recovered. These can be recovered as
valuable by-products by employing a suitable technique such
as condensation, distillation, absorption etc.

 Condensate water can be collected and recycled / reused.

 Floor washing, at times, can be collected, treated if necessary

and recycled / reused.

 Seal pot water, vacuum pump water and cooling water can be
recycled and reused in operations such as neutralisation,
washing etc.
 RECYCLING AND REUSE OF WASTEWATER
 From the investigation of material balance and unit
operations of a particular process, it will be possible to
characterize the waste and identify the possibilities of
recycling or recovery of useful products. The process of
identification of recoverable matter and recycling of
wastewater can be made effective through
‘environmental audit’.

 Treating some or all process wastewater to make it

suitable for plant process, cooling water make-up, floor
wash etc.

 Re-circulating the same water within an unit operation

several times before it becomes unfit.

 Sequential use of effluent from one process with

treatment, if necessary, as input into another.
 4R CONCEPT

 REUSE

 RECYCLING

 RENOVATION

 RECHARGING

4 R Concept and its combination is appropriate technology

for sustainable use.
PRECIPITATION PROCESS FROM NICKEL RECOVERY
WASTE NICKEL SULFATE SOLUTION

Chlorine Oxidation and

Calcium Carbonate pH adjustment

Calcium Sulfate
Filter Press
Impurities

pH adjustment and
precipitation

Zinc and Iron Phosphate

Filter Press
Calcium Sulfate

Phosphoric Acid
Precipitation

Filter Press

Sodium Carbonate pH adjustment and

precipitation

Filter Press Sodium Sulfate Solution

Solid Cake
Dissolution

Electro-winning Evaporation Water

NICKEL
 RECYCLING OF ZINC SULFATE IN RAYON
MANUFACTURING PROCESS
IMPURE ZINC SULFATE WASTE

Mining zinc sulfate

from stored waste

Preheat

Heat treatment to improve

Steam
crystal structure

Filter Press Liquor to waste

Solid impure zinc solution

Hydrogen Peroxide
Acid digestion
Sulfuric acid
Impure zinc sulfate solution
Calcium Sulfate,
Filter Press organic and
other impurities

Hydrogen Peroxide Oxidation of ferrous iron to

ferric pH adjustment to
Caustic Soda precipitate ferric hydroxide

Rotary vacuum filter Iron Hydroxides

Purified zinc sulfate solution to rayon plant

HYDROCHLORIC ACID PICKLE LIQUOR REGENERATION
SPENT PICKLE LIQUOR
(~20% FeCl2, 5% HCl)

Pre-heater

Hot Air Iron Oxide

Hydrolysis Reactor
~ 700°C

Cyclone

Water Hydrogen Chloride Absorber Stack

Regenerated Hydrochloric Acid

(18-20% HCl)
 IN-PLANT CONTROL
 Good house keeping is the least expensive means
to reduce the overall burden on treatment and
disposal.

 Loss of raw material, solvent and product can be

restricted by installing monitoring devices.

 The steam jet ejectors and barometric condensers

can be replaced in some cases by vacuum pumps
and surface condenser systems.

 Waste segregation and treatment also form an

important step in in-plant control of pollution.
RESOURCE
CONSERVATION
 4R CONCEPT

 REUSE

 RECYCLING

 RENOVATION

 RECHARGING

4 R Concept and its combination is appropriate

technology for sustainable use.
 TWO KEY WORDS

REUSE is applied to wastewaters that are discharged and

then withdrawn by a user other than the discharger.
Wastewaters potentially available for reuse include
discharges from municipalities, industries and the
agricultural irrigation.

RECYCLING is frequently defined as the internal use of

wastewater by the original user prior to discharge to a
treatment system of other point of disposal. The wastewater
is recovered, treated or untreated, and then recycled for
repetitive use by the same user.
RENOVATION THE PREREQUISITE
WATER
RECYCLING MATERIALS PROCESS

WASTEWATER

TECHNOLOGY
RENOVATION
RECHARGING THE OTHER ARM

PROCESS

WASTEWATER

TECHNOLOGY
RENOVATION

RECHARGING

REUSE
 IN-PLANT CONTROL
 Good house keeping is the least expensive means
to reduce the overall burden on treatment and
disposal.

 Loss of raw material, solvent and product can be

restricted by installing monitoring devices.

 The steam jet ejectors and barometric condensers

can be replaced in some cases by vacuum pumps
and surface condenser systems.

 Waste segregation and treatment also form an

important step in in-plant control of pollution.
 EQUAL OBJECTIVES

Objective of environment = Objective of production

management

Conservation of Cost effective

Raw materials
Energy
Water

Loss prevention and

control of production Reliability & variance
control
Standardization and
optimization of unit Quality of product
process Loss of man days

SUSTAINABLE DEVELOPMENT
 SUSTAINABLE DEVELOPMENT
PRODUCTIVITY

SUSTAINABLE POLLUTION
SAFETY DEVELOPMENT CONTROL

HEALTH CONSERVATION
 CLASSIFICATION OF PRIORITY
CHEMICALS WITH RESPECT TO
TOXIC AND HAZARD POTENTIAL
 CLASSIFICATION SCHEME

 Classification of chemicals

 Classification of Volatile Organic

Compounds (VOC)

 Classification of Persistent Organic

Pollutant (POP)

DDB SLIDES
PARAMETERS RELEVANT TO EVALUATION OF ECOLOGICAL
AND TOXICOLOGICAL PROFILE OF CHEMICALS

DDB SLIDES
SCHEMATIC OVERVIEW OF THE TRANSPORT AND TRANSFORMATION
PROCESSING IN THE ENVIRONMENT

DDB SLIDES
 FACTORS FOR ASSESSMENT OF CHEMICALS

 Persistency = BOD1/2

 Bioaccumulation = BCF / Log Poct

 Acute toxicity to mammals = LD50 (Oral/dermal

and fish route)

 Long term effects = Carcinogenicity

= Mutagenicity
= Teratogenicity

DDB SLIDES
SCORING CRITERIA BASED ON PERSISTENCE

Score Persistence (based on BOD1/2)

(Days)
10 > 100
7 >50 to < 100
4 > 10 to < 50
0 < 10

DDB SLIDES
SCORING CRITERIA BASED ON ACUTE TOXICITY

Score Oral LD50 Dermal LD50 Acute LD50

(mg/l) (mg/l) (mg/l)
10 <5 <5 <1
7 > 5 to < 50 > 5 to < 50 > 1 to < 10
4 > 50 to < 500 > 5 to < 500 > 10 to < 100
0 > 500 > 500 > 100

DDB SLIDES
 SCORING CRITERIA BASED ON LONG TERM EFFECT
Score Carcinogenicity * Mutagenicity Teratogenicity
10 Group ½ A Confirmed Confirmed
7 Group 2 B -------- --------
4 Group 3 Experimental Experimental
0 Group 4 -------- --------
* Carcinogenic Groups as assigned by IARC / USEPA

Group 1: Confirmed Human Carcinogen

Group 2A: Probable Human Carcinogen
(sufficient animal & limited human evidence)
Group 2B: Possible Human Carcinogen
(limited animal & no human evidence)
Group 3: Not classifiable w.r.t. carcinogenicity to humans
Group 4: Probably not carcinogenic to humans.
DDB SLIDES
 PRIORITY CHEMICALS
Names Usage Sector
Benzidine Dye Intermediate
P-Amino azobenzene Dye Intermediate
P-Chloro-o-Nitro Aniline Dye Intermediate
O-Chloro Phenol Dye / Drug Intermediate
P-Chloro Phenol Dye / Drug Intermediate
3,4- Dichloro aniline Dye / Drug Intermediate
Hydroquinone Dye Intermediate
C.I Basic Violet 1 Dye stuff
C.I Pigment Red 3 Dye Stuff
2,4- Dichloro Phenol Pesticide / Drug Intermediate
Dibutyl Phthalate Drug Intermediate
Hydrazo Benzene Drug Intermediate
DDB SLIDES
CLASSIFICATION OF VOCs

DDB SLIDES
 CRITERIA FOR CLASSIFICATION OF VOCs

• Photochemical Oxidant Creation Potential (POCP)

• Global Warming Potential (GWP)

• Ozone Depleting Potential (ODP)

• Threshold Limit Value (TLV)

• International Agency for Research in Cancer (IARC)

Classification

DDB SLIDES
DECISION TREE FOR CATEGORISATION OF VOCs

DDB SLIDES
SOURCES OF EMISSIONS OF VOC IN PETROCHEMICALS /
POLYMER PROCESSES
S. No. Plant Pollutant Expected
1 Ethylene / Propylene Ethylene / Propylene
2 Butadiene Butylene / Propylene
3 Benzene / Toluene / Benzene / Toluene / o,m,p - Xylene
Xylene
4 Methanol Methanol
5 Ethylene Oxide Ethylene Oxide / Ethylene Glycols
6 Ethylene Glycols Mono, do, tro ethylene glycols
7 EDC / VCM EDC, Ethyl Chloride, Vinyl Chloride, Ethylene,
Hydrogen Chloride, Chlorine
8 Vinyl Acetate Monomer Acetaldehyde, Ethylene, Acetic Acid
9 Propylene Oxides / Propylene oxide, propylene glycol,
Glycols Epichlorohydrin
10 Acrylonitrile Acrylonitrile, Hydrogen cyanide, Acetonitrile,
Nitrogen Oxides
11 Isopropanol Acetaldehyde, Ethyl Benzene, Acetophenone,
Isopropyl Benzene, Methyl Ethyl Ketone,
12 Phenol / Acetone Phenol, Acetone, Cumene

DDB SLIDES
 CATEGORISATION OF VOC’S
 15 are high priority;
 17 are medium priority and balance; and
 20 are low priority.

LIST OF HIGH PRIORITY VOC’s

1. 1,3 Butadiene 2. Benzene

3. Toluene 4. Ethylene oxide
5. Vinyl Chloride 6. Propylene oxide
7. Acrylonitrile 8. Caprolactum
9. Maleic anhydride 10. Phthalic anhydride
11. TDI 12. Carbon tetra chloride
13. Epichloro hydrin 14. Hydrogen cyanide
15. Phosgene

DDB SLIDES
RISK MINIMISATION PROGRAMME

 Assessment and monitoring

 Leak detection and repair (LDAR)

 Impact assessment
LDAR
 AIR EMISSION ASSESSMENT – THE POSSIBLE INVENTORY

• What are the possible point sources (channelised) in the

complex?

• What are the sources of combustion, how much load of

particulate matter, sulfur dioxide, nitrogen oxides and
carbon di-oxides are generated (in terms of tonnes per day?

• What are the sources of conventional parameter from

channelised sources of process?

• Identification of most probable pollutants from vent off and

purge gases.

• Budget of fugitive emission.

 EMISSION PROFILE

Classification of pollutants Sources of air

pollutants
    Cracking units
  Combustion Incineration
  Gen set etc.
Point
Flare
  Sources
Channelised
 
Emissions emissions
Process
Vent off

Purge gases
    Equipment leaks
Fugitive VOCs Loading
Storage tanks
ETP
SOURCES OF EMISSIONS
 TYPICAL RANGE OF AIR EMISSIONS
(All figures are in tonnes / Annum)

S.No Feed Naphtha/ Gas Naphtha

Gas Oil (C2+C3)
1. Type of the Olefin Olefin Aromatics
Complex
2. Capacity (1000 400 –500 400 -500 300
TPA as
Ethylene)
3. Uncontrolled 6000 to 3000 - 2500 -3700
organic release 8000(+) 4000(+)
( C2 -C6 HC) from
complex
4. Sulphur Oxides 25- 40 (+) 18- 20 15- 25 (+)
(SO2) (+)
5. Nitrogen Oxide 80- 450 100- 350 -
(Nox) (+)
6. Carbon 22- 47 (+) 15- 25 12- 18 (+)
Monoxide (CO) (+)
Notes: 1) Excludes balance of Plant Facilities viz. Power etc.
 TYPICAL PERCENT SHARE OF EMISSIONS

S.NO Source % Typical

1 Fugitive emissions from 40-60

equipment

2 Process vents 5-15

3 Storage tanks 5-15

4 Loading /unloading facilities 15-25

5 WWTP 10-20
 PRESENTATION ON LEAK DETECTION AND
REPAIR CONTROL (LDAR) TECHNIQUES
PRESENTATION COVERAGE
• WHY LDAR PROGRAM

• WHAT IS LDAR PROGRAMME

• VOC CLASSIFICATION

• DEVELOPMENT OF LDAR PROGRAM

• PROCEDURES FOR LEAK EMISSION INVENTORY – AN OVERVIEW

• DEVELOPMENT OF LEAK EMISSION ESTIMATES

• LEAK CONTROL TECHNIQUES EFFICIENCIES

• LDAR CONTROL EFFECTIVENESS

• SUGGESTED INDUSTRY RESPONSE

 WHY LDAR PROGRAMME

LET US HAVE AN OVERVIEW OF 300,000 TPA OLEFIN

COMPLEX BASED ON GAS/ NAPTHA AS FEED STOCK
(TYPICAL EMISSION LOAD)

S. NO POLLUTANT POLLUTANT LOAD

(KG/DAY)

1 SULPHUR OXIDES(SO2) 25-90

2 PARTICULATES (SPM) 700-1200
3 CARBON MONOXIDE (CO) 250-900
4 NITROGEN OXIDES (NOX) 1100-2500
5 VOLATILE ORGANIC 2400 - 4000
COMPOUNDS (VOC’S)
 WHY LDAR PROGRAM

ETROCHEMICAL EMISSION OVERVIEW

VIDENT THAT EMISSION FROM PETROCHEMICAL COMPLEX IS UNIQU
• LESS CONVENTIONAL AIR POLLUTANTS (EXCEPT NOX)

• LARGE VOLATILE ORGANIC COMPOUNDS (VOC) EMISSION

• SOME OF THESE VOC’S ARE EXTREMELY HAZARDOUS TO

HEALTH (VOC –HAPS) - LOCAL CRITICAL CRITERIA

• SOME OF THESE VOC’S PARTICIPATES IN COMPLEX REACTION

WITH NOX IN ATMOSPHERE AND RESULTS IN
PHOTOCHEMICAL OZONE CREATION POTENTIAL (POCP) –
LOCAL CRITERIA

• VOC’S (VIZ METHANE, N2O RESULTING IN GLOBAL WARMING

POTENTIAL (GWP) - GLOBAL CRITERIA
 WHY LDAR PROGRAM
DOMINANT VOC EMISSION SOURCES AND ITS TYPICAL DISTRIBUTION FROM A
PETROCHEMICAL COMPLEX
S No Emission Typical Source General Control Techniques
Source Distribution Classification

1 Process Vents 5-20 Point Source Flare, Incinerator, Restrict,

Recycle / Recovery etc
2 Process 40-70 Fugitive LDAR, Modification and / or
Equipment (Non Point High Integrity Equipment
Leaks Source)
3 Storage Tanks 5-15 Point Source Improved Equipment / Seal
Design, Recovery as Fuel gas
etc
4 Loading 15-20 Point Source Vapour Recovery, Modification,
Stations Flare

5 Waste Water 10-15 Fugitive Closed System Design,

Collection and (Non Point Improved System System
Treatment Source) Modifications
 WHAT IS LDAR PROGRAMME

• LEAK DETECTION AND REPAIR (LDARR) IS AN IMPROVED O&M APPROACH

TO RESTRICT/MINIMIZE VOC FUGITIVE EMISSION RESULTING FROM
EQUIPMENT LEAK

• FOLLOWING INTRODUCTION OF STATUTORY REGULATION AND STANDARDS

ADDRESSING VOC EMISSIONS WORLDWIDE DURING EARLY 90’S, LDAR
PROGRAM HAS RECEIVED WIDE ACCEPTANCE IN PETROCHEMICAL
REFINERIES, PETROCHEMICALS, PHARMACEUTICAL AND FINE CHEMICAL
INDUSTRIES

• LDAR PROGRAM ARE BEAST APPLIED TO EQUIPMENT AND/OR PIPING

SYSTEM / ACCESSORIES THAT CAN BE REPAIRED “ON-LINE’ AND THUS
RESULTING IN AN IMMEDIATE EMISSION REDUCTION INVOLVING MINIMUM
COST AND TIME. FURTHER; WHERE EQUIPMENT/SYSTEM MODIFICATIONS
ARE NOT FEASIBLE – THE LDAR PROGRAM IS THE VIABLE SOLUTION

• LDAR PROGRAM IS BEST SUITED FOR THE FOLLOWING EQUIPMENT /

SYSTEM
= PUMPS - VALVES
= PIPING / CONNECTOR SYSTEM
 VOC CLASSIFICATION

• VOC Definition

VOC represents a diverse group of organic compounds

released to the air (atmosphere) in gas phase which
broadly includes hydrocarbons and substituted
hydrocarbons (generally in C2-C8 carbons)

• Methane (C1) is recognized as contributing gas in (6)

Green House gases for Global Warming (GWP)

• Depending on Regulatory “Focus” the VOC is considered

on the following basis i.e including/excluding Methane
(C1)

-------- Non Methane VOC (nm –voc)

-------- Total VOC (Including Methane)
 VOC CLASSIFICATION
VOC HAP’S ARE CLASSIFIED BROADLY IN TWO GROUPS BASED ON IARC WITHIN GROUP
CLASSIFICATION WITHIN GROUP

--- CARCINOGEN WITHOUT THRESHOLD VALUES ( CLASS – A)

--- CARCINOGEN WITH THRESHOLD VALUES ( CLASS –B)

PETROCHEMICAL PRODUCTS/COMPOUNDS CLASSIFIED AS VOC –HAP’S

VOC- SOURCE SOURCE ATM / GLC MAX COMMON PETROCHEM

HAP (MASS FLOW) EMISSION EMISSION CONC PRODUCTS / COMPOUNDS
CLASS IN GM/HR Mg/NM3 NANOGM/m3

A 0.5 TO 25 0.1 TO 0.50 1.0 TO 100 ETHYLENE OXIDE (EO),

ACRYLONITRILE(CAN),
BENZENE, BUTADIENE,
EPICHLOROHYDRIN (ECH),
PROPYLENEOXIDE(PO),
EDC / VCM, EPOXYPROPANE
(EOP)
B 100 20 400 FORMALDEHYDE,
HYDRAZINE,ACRYLIC
ACID,ANILINE,
BISPHENOL –A, PHENOL,
PYRIDINE ETC
OTHER VOC’S ARE CLASSIED AS GENERAL BASED ON THEIR POTENTIAL FOR
POCP AND OTHER GLOBAL EFFECTS VIZ GWP, SODP ETC

VOC – Source, Source Atm. Viz. Example Petrochemical

General Mass Mass con. Emission conc. Compounds
Class Flow in Mg/Nm3 (µg/m3) (GLC-
Gm/Hr MAX)

1.0 2000 100 1.0 Acetic acid, Butanol,

DEA, Cyclohexanol,
Methyl Glycol, Toluene,
Vinyl acetate etc.
2.0 3000 – 150 – 250 1.5 – 3.0 Ethylene, Ethanol, Ether,
5000 Acetone, Iso-butene,
Methanol, Olefinic –
Hydrocarbon, Iso-
propanol etc.
 PROCEDURE FOR LEAK EMISSION INVENTORY

THERE ARE FOUR ESTABLISHED PROCEDURE:

 AVERAGE EMISSSION FACTOR

 SCREENING RANGE APPROACH
 EPA CORRELATION APPROACH
 UNIT SPECIFIC CO-RRELATION APPROACH
TYPICAL APPLICABLE AVERAGE EMISSION FACTOR FOR VARIOUS TYPE
OF EQUIPMENT VIS-À-VIS SCREENING RANGE

S. Equipment type Process Fluid Emission factor in (kg/hr/source)

No. Service Screening valve Screening valve
at 10,000 ppm at 1000 – 10,000
(v) ppm (v)
1 Valves Gas 0.0782 0.000131
2 Valves Light liquid 0.0892 0.00165
3 Valves Heavy liquid 0.00023 0.00023
4 Pump Seal Light liquid 0.243 0.00187
5 Pump Seal Heavy liquid 0.216 0.00210
6 Compressor Seal Gas 1.608 0.0894
7 Relief Valve Gas 1.691 0.0447
8 Piping Gas / Light liquid 0.113 0.000085
Connector,
Flanges
9 Open ended Gas / Light liquid 0.012 0.00150
piping
WATER MANAGEMENT

IN

BULK DRUG INDUSTRY

WATER BALANCE
 WATER BALANCE IN AN INDUSTRY

RAW WATER

LOSS IN
EVAPORATION

PROCESS WATER SERVICE WATER POTABLE WATER

WASH. MISC. FIRE

COOL. TOW. D. M. PLANT IND. USE

BOILER COND.

WASTEWATER
 WATER BALANCE IN PARACETAMOL INDUSTRY
TOTAL WATER
80 m3/day

UTILITIES PROCESS SERVICES SCRUBBER GARDENING

40 m3 40 m3 10 m3 6 m3 3 m3

20 m3

R & D LABS
1 m3

Wastewater 9 m3
Boiler Cooling tower DM
25 m3 20 m3
25 m3 Regeneration
5 m3

Wastewater 6 m3
15 m3

Wastewater 1 m3
EFFLUENT TREATMENT
PLANT 36 m3/day
WATER BALANCE IN RANITIDINE, DICLOFENAC SODIUM
TOTAL WATER
225 m3/day

UTILITIES PROCESS SERVICES SCRUBBER GARDENING

140 m3 13.5 m3 35 m3 32 m3 5 m3

Plant 1 Plant 2
8.5 m3 5.0 m3

Wastewater 5 m3

Wastewater 2 m3
Boiler Cooling tower Chilling Plant
20 m3 110 m3 10 m3
6.5 m3
B/D 2 m3
B/D 0.3 m3

EFFLUENT TREATMENT
PLANT 16 m3/day
 WATER BALANCE IN PESTICIDES INDUSTRY
1081 M3/DAY*

COOLING BOILER DOMESTIC INDUSTRIAL

WATER HOUSE WATER WATER

105 M3/DAY 146 M3/DAY 565 M3/DAY 265 M3/DAY

(ALL EVAPORATED)

140 M3/DAY - ETP

93 M3/DAY HCL SCRUBBER
CONDENSATE 390 M3/DAY
TO ETP GARDENING 3.6 M3/DAY - ETP
114 M /DAY
3 VACUUM PUMP IN
MONOCROTPHOS
21 M3/DAY 175 M3/DAY
LOSS LAUNDRY & 10.4 M3/DAY
4 M /DAY
3
TOILETS CAUSTIC
(CYPERMETHRIN) PREPARATION

28 M3/DAY 111 M3/DAY 50 Incinerator

BOILER BLOW DOWN bleed

24 to air via
175 M3/DAY 4 CYPER stack
37 drips, drains,
29 CHLORAL drum washing,
Leaks, fire fighting
93 + 28 = 121 M3/Day
drills, vehicle
EFFLUENT TREATMENT PLANT washing, canteen
274
loss
To MIDC sewer 570 M3/Day

NOTE: * AVERAGE FOR APR. 91 – MAR. 92)

WASTEWATER CHARACTERIZATION
TDS / BOD / COD RELATIONSHIP
TDS due to
inorganic salts

TDS due to
persistent organic

TDS due to
biodegradable organic
 TDS IN EFFLUENT STREAMS ARISING
FROM
SYNTHETIC ORGANIC PROCESSING
INDUSTRY
Utility process Service Potable water

DM plant
( 5000-10000 mg/l)
TDS (500 mg/l)

Reaction
CT (1000 mg/l))
(50000 mg/l)

Boiler (1000 mg/l) Floor washing

(10000 –50000 mg/l)
WASTEWATER CHARACTERISTICS OF BULK DRUG
(SYNTHETIC ROUTE)

pH COD (mg/l) TDS (mg/l) BOD (mg/l)

5.5 – 8.5 15,000 – 1,15,750 22,000 – 50,000 8,000 – 14,800

 CHARACTERISTICS OF WASTEWATER
Wastewater Generation from a Pharmaceutical (Formulation) unit

S. Source of Average flow of Range of average effluent

No. wastewater wastewater characteristics in mg/l
generation (cum/hr) except pH
1 Sterile products 1.0 to 10 BOD 50 to 100
TSS 20 to 260
2 Syrup preparation 10 to 25 COD 150 to 2500
Cl- 20 to 150
3 Malt preparation 1 to 5 BOD 300 to 2000
SO4-2 20 to 200
4 Pastilles preparation 10 to 25 BOD 2000 to 2500
Heavy metals 1 to 20
TSS 100 to 300
pH 4.0 to 8.0
 CHARACTERISTICS OF WASTEWATER
Wastewater Generation from an Antibiotic Plant

S. Source of Nature of wastewater and Range of average

No. wastewater solid waste characteristics of combined
generation effluent in mg/l except pH
1 Fermentation Floor & equipment washings, pH 4.0 to 8.0
block leakage of values / machines, TSS 100 to 1000
contaminated batches, cooling
waters, laboratory & utility BOD 500 to 6000
wastes
2 Filtration / Mycelium cakes, filter washings, BOD Upto 10,000
Centrifugation floor washings
3 Recovery and Faecal wastes, acid & alkali CN- 0.1 to 1
purification block wastes (from regeneration of Heavy metals 1 to 5
ion-exchangers), floor washings
laboratory wastes Oil & Grease 20 to 50
4 Style and Floor & equipments washings Phenol 1 to 5
finishing block and other utility wastes
(After mycelium cake separation)
EWATER CHARACTERISTICS OF VARIOUS STREAMS OF PAINT INDU

Parameters Caustic Resin house Stiff paints Lab / Liquid

in mg/l cleaning R&D paint*
except pH operations
pH 8.5 – 13.5 3.2 – 6.3 6.5 – 13.5 5.1 – 6.7 13.5

SS 200 – 600 240 – 400 400 – 700 20 – 200 40

COD 1100 - 3800 240 – 78,000 1215 - 6000 150 – 200 560

BOD 475 – 2400 225 – 60,000 380 – 980 18 – 45 60

Oil & Grease 32 – 150 14 – 25 252 --- 6

Phenolic 12.5 6 - 86 6.4 – 100 0.84 – 5.5 5.5

content
* Only one observation
MBINED WASTEWATER CHARACTERISTICS OF PAINT INDUST

Parameters in mg/l Range

except pH
pH 6.5 – 10.5
SS 220 – 1,200
COD 300 – 5,700
BOD 1,700 – 3,100
Oil & Grease 22 – 138
Phenolics 18 - 55
WASTEWATER DISCHARGE AND TREATMENT
EWATER CHARACTERISTICS OF PESTICIDES INDU

pH BOD (mg/l) COD (mg/l)

1.0 – 11.0 400 – 2000 1,000 – 10,000

AN APPROACH TOWARDS TREATMENT
 STREAMWISE BEST PRACTICABLE
TECHNOLOGY
IN CHEMICAL
HIGH
INDUSTRIES
FORCED EVAPORATION FOLLOWED
BY BIOLOGICAL TREATMENT -I

TDS
LOW BIOLOGICAL TREATMENT -II
HIGH
BOD
HIGH INCINERATION - III
LOW
HIGH TDS
LOW SOLVENT / CHEMICAL RECOVERY - IV

COD
FORCED EVAPORATION FOLLOWED
HIGH BY BIOLOGICAL TREATMENT -I
LOW TDS
HIGH LOW BIOLOGICAL TREATMENT -II

BOD
HIGH FORCED EVAPORATION - V
LOW
TDS
LOW SOLVENT / CHEMICAL RECOVERY - IV
 TYPICAL BIOLOGICAL TREATMENT PLANT

Equalization cum Dissolved Air Primary

Neutralization Floatation Clarifier

Sludge
Sludge

Sludge Dryings
Beds

Wastewater
Final disposal Secondary
Clarifier Aeration

Sludge
EGRATED TREATMENT SCHEME THROUGH COMBINED EFF
TREATMENT PLANT IN A CLUSTER OF INDUSTRY

Sewage
Multiple evaporator
Separation: TDS bearing COD
With high TDS Sewer line/marine
water body

Residual COD
CETP
Persistent organic

River/recycling to
agriculture
Bio

Low TDS
d
eg
rad
ab

First step: Residual COD after pH adjustment

le

and solvent extraction by SSI

CO

Solvent extraction
D

followed by
incineration
Second step:
Biological treatment

LARGE INDUSTRY
I have yet to see any problem,
however, complicated, which when
you looked at it in the right way,
did not become still more
complicated

Poul Anderson