Waste Management in Molasses

Based Distilleries

Babu Alappat
Professor
Department of Civil Engineering
I.I.T Delhi

alappat@[Link]
Industrial wastewaters Vs Sewage
 Generation of Spent wash
Press mud
~0.05ton/ton
sugarcane crushed
Sugar Cane Sugar Mill Sugar

Bagasse
~0.33ton/ tone of
sugarcane crushed

Distillery
Molasses ~0.43ton/ tone of sugar
Alcohol produced

Spent wash
• Press mud
• Mixed with spent wash for composting

• Bagasse:
• used in pulp and paper industries
• also as fuel in sugar mills / distilleries

• Molasses:
• For manufacture of industrial alcohol
Distillery Industry in India

• Number of sugar mills: 620

• Molasses based distilleries: 300
• Molasses based installed capacity : 4.29 bln
lit.
• Grain based distillery units: 100
• Grain based installed capacity : 1.8 bln lit.
• Molasses based distilleries produce spent wash
having very high pollution load
Spentwash or slop or vinasse or stillage
Yeast propagation: Aerobic. Growth of yeast cells.
Fermentation: Sugar (10-20%) is converted to
alcohol & CO2 anaerobically. Takes bout 15-20
Hours at 30-36 oC (cooling required to maintain this
temp.)

Stripping Column: to separate components from

liquid mixture.
Aldehyde column: to remove aldehydes ( they are
carcinogenic)
Rectification column: to remove fusel oil and lutter
water from alcohol.
 Molasses Distilleries

• Spent wash is the main waste stream

– It has a BOD5 of about 35,000 to 65,000mg/lit
– COD of about 60,000 – 1,20,000 mg/lit
– pH – acidic (4 – 5)
– Colour- dark brown
– Sulfates > 7000 mg/L
– About 12-15% solids content
– Ash contains Potash as K2O
 Target Pollutants
• Organic matter

• pH

• Colour
• Spent wash generation: about 14 to 16 litres
per liter for alcohol produced

• BOD about 50 000 mg/lit

• COD about 95 000 mg/lit

• Pollution load of total spent wash generated

is equivalent to about 6 times the total BOD
generated by the entire population of India
 Attempts with Spent Wash
• For washing sugar cane
• For diluting molasses
• For irrigating sugar cane fields
• For manufacturing cattle feed
• For manufacturing yeast / dry ice / etc

Nothing turned to be sustainable / feasible

 Waste to be managed….
• Reduction at the source – especially by
updating the fermentation unit

• Treatment - Disposal
Hierarchy of waste management options

Source
reduction

On-site/off-site Waste
recycling diversion

Treatment

Final disposal
Source reduction opportunities

Source
reduction

Housekeeping Product Input material Technology

improvement reformulation alteration alteration
 Type of Fermentation units
• Batch and Fed-Batch

• Cascade Continuous

• Biostil Continuous
Cascade Continuous fermentation system
• Not one unit, but many
• Total 05 Fermentation units
• 1st unit – mixing of culture, molasses and air, water
• 2nd unit : aerobic – for yeast growth
• 3rd to 5th units: anaerobic for sugar conversion to
alcohol
Alcohol % increases from 5% to 9%
from fermenter 1 to 5
 Biostil Continuous System
• Single fermenter with a recycle of about 60% of
wash passed through the column for alcohol
recovery for diluting molasses being fed to the
fermenter
• Less water in the fermenter results in concentrated
substrate
• Generates about 6-8 lit of spent wash /lit of
alcohol produced. (15-17 lit /lit for conventional
systems)
• Alcohol yield about 94.68% v/v
 Average fresh water requirement in molasses based distilleries for
different fermentation technologies.
Type of Molass Fresh Non Polluted Unpoll Total Total
Fermen es process Streams for uted Strea fresh
tation Dilutio (RS recycle Strea ms for water
Process n fresh Production) ms for recycle require-
(a) water recycle -ment
(b) (h) (b+c+
(g) d-h)
Cooling Other For For
tower non process non
make process * process
up

(c) (d) (e) (f)

Batch 7.4 – 10.5 1.4 – 4.0 6.0 – 8.8 0.5 – 0.6 0.5 – 0.6 0.5 – 1.0 1.5 – 2.2 13.3–
21.1

Cascade 7.7 – 9.2 3.0 – 4.0 5.5 – 6.5 0.5 – 1.5 0.5 – 0.6 0.5 – 1.0 1.5 – 3.0 14.7–
Continuo 16.7
us
Biostill 4.0 – 5.0 3.0 – 4.0 5.0 – 6.0 2.0 – 4.0 0.5 – 0.6 0.5 – 1.0 3.0 – 5.6 9.0 – 9.4
Continuo
us
* Other than cooling tower
 Average waste water generation in molasses based distilleries for
different fermentation technologies.

Type of Waste water generation

Fermentation
Process
Spent wash Spent lees Other

Batch 11.1- 15.0 0.5 – 1.5 0.2 –0.4

Cascade 8.5 – 11.0 0.5 – 1.5 0.2 –0.4

Continuous

Biostill 6.0 – 8.0 0.5 – 1.5 0.2 –0.4

Continuous
 General characteristics of raw spent wash
[Link]. Parameter Batch process Cascade process Biostil process

1 Volume, L/L Alcohol 14-16 10-12 8-10

2 Colour Dark brown Dark brown Dark brown

3 PH 3.7-4.5 4.0-4.3 4.0-4.2

4 COD 80,000-1,10,000 1,10,000-1,30,000 1,40,000-1,60,000

5 BOD 45,000-50,000 55,000-65,000 60,000-70,000

6 Solid 90,000-1,20,000 1,30,000-1,60,000 1,60,000-2,10,000

Total 60,000-70,000 60,000-75,000 80,000-90,000
Total Volatile 30,000-40,000 35,000-45,000 60,000-90,000
Inorganic dissolved

7 Chlorides 5,000-6,000 6,000-7,500 10,000-12,000

8 Sulphates 4,000-8,000 4,500-8,500 8,000-10,000

9 Total nitrogen 1,000-1,200 1,000-1,400 2,000-2,500

10 Potassium 8,000-12,000 10,000-14,000 20,000-22,000

11 Phosphorus 200-300 300-500 1,600-2,000

12 Sodium 400-600 1,400-1,500 1,200-1,500

13 Calcium 2,000-3,500 4,500-6,000 5,000-6,500

• Spent wash generation: about 8 to 16 litres
per litre for alcohol produced

• 8-9 for new plants (Biostil)

• 15-16 for old plants (batch)
 Fermentation Industry : Effluent Discharge Standards
(Distilleries, Maltries & Breweries)
As notified under the Environment (Protection) Rule, 1986

Sr. Parameter Range

No.
1 pH 5.5- 9.0

2 Colour & Odour Absent

3 BOD3 (at 27oC, 3 days) mgs/L Max.

Disposal into land surface water/ 30

rivers/ streams
Disposal on land or for irrigation. 100

4 Suspended solids, mg/L Max. 100

Industrial Effluent Treatment

Characteristics
Of wastewater

ETP
Treated WW
Effluent Treatment Plant

Disposal standards
Industry
 PARAMETER Surface water Sewer lines irrigation ocean
Suspended solid 100mg/l 600mg/l 200mg/l -

Dissolved solids 2100mg/l - 2100mg/l -

pH 5.5-9 5.5-9 5.5-9 5.5-9

Temperature not>50Cthan the - - Not>5 0C than the

IS – for
receiving water receiving water

Effluent Oil & greese 10mg/l 20mg/l 10mg/l 20mg/l

Discharge Free NH3 5.0 - - 5.0
BOD5d,200C 30 350 100 100
COD 250 - - 250
Arsenic 0.20 0.20 0.20 0.20
Hg 0.01 0.01 - 0.01
Pb 0.01 1.0 - 2.0
Cd 2.0 1.0 - 2.0
Cr+6 0.1 2.0 - 1.0
Total Cr 2.0 2.0 - 2.0
Cu 3.0 3.0 - 3.0
Zn 5.0 15 - 15
Ni 3.0 3.0 - 5.0
Cyanide 0.2 2.0 0.2 0.2
Chlorides 1000 1000 600 -
Fluorides 2.0 15 - 15
Phosphates 5.0 - - -
Sulphates 1000 1000 1000 -
Sulphides 2.0 - - 5.0
Phenolic compounds 1.0 5.0 - 5.0
 Spent wash treatment
BOD/ COD is about 0.50-0.60

Hence biological treatment

It is high strength wastewater – hence

anaerobic treatment
 WASTE TREATMENT ROUTES
• Biological – for sure, THE BEST option
– More eco-friendly
– End products acceptable to the nature
– Low expenditures
– But slow, more uncertainty, affected by weather / temp

• Chemical – for lesser quantities

• Thermal-
usually costlier, probability of pollution, controversial but
very fast, compact reactors, less area required, more fool
proof, not affected by weather / temperature, less
uncertainty
 Biological treatment
• Removal of organic matter using
microorganisms (mostly bacteria, fungi,
actinomycetis, etc)
• Organics used for energy and growth
• Organics get converted to gases (that
escaped the system) and cell mass (has to be
removed)
 Batch reactor – growth of micro-organisams

Live micro- Endogenous decay

organisms
(number or mass)
Log growth phase

compost
acclimatization

Time in days (or hours)

 Biological treatment
• Aerobic: in the presence of Oxygen
Organics + O2 → CO2 + H2O +
Biomass More Biomass

• Anaerobic: in the absence of Oxygen

Biogas (CH4 + CO2+H2S)
No oxygen
Different organisms in action <90 %
Organic carbon
100 % Biomass>10%
 Biological reactors
• Batch or continuous:
• Composting – batch process
• Activated sludge process (ASP) - continuous
• Suspended growth or attached growth
• Suspended growth: microorganisms are suspended
in the waste water: ASP
• Attached growth: microorganisms are attached to
some media like pebbles, plastic balls, etc: Tricking
filters, Rotating Biological Contactor (RBC)
 BIOLOGICAL WASTEWATER
TREATMENT
Aerobic:
• ASP (Activated Sludge Process),
• TF (Trickling Filter),
• RBC (Rotating Biological Contactor)
• SBR (Sequential Batch Reactor)
• MBBR (Moving Bed Bioreactor)
• MBR (Membrane Bioreactor)
Anaerobic:
• Conventional Digester
• Di-phasic digestion
• UASB Reactor (Upflow Anaerobic Sludge Blanket Reactor)
• FB (Fluidized Bed) Anaerobic Reactor
• Hybrid reactor
 Organics + O2 CO2 + H2O +
Biomass More Biomass

Treated effluent
CO2

Organic carbon, N, P

O2 to sludge
treatment
Return Sludge Waste
sludge
ACTIVATED SLUDGE PROCESS (ASP)
 Anaerobic process

Biogas (CH4 + CO2+H2S)

No oxygen
Different organisms in action <90 %
Organic carbon
100 % Biomass>10%
 Comparing aerobic – anaerobic
techniques
• Aerobic
• Faster reaction kinetics
• Hence smaller reactors
• No bad odour
But
• have to provide Oxygen
• No any recovery,
• more sludge to be handled
• Anaerobic

• Fuel Gas recovery

• Less sludge to be handled
• No oxygn to be supplied
But
• Slow reaction kinetics
• Large reactors
• Odour issues are there
 The main treatment strategy
• BOD/COD = 55,000/1,00,000 = > 0.5

Hence biological treatment is effective

Since it is high strength wastewater,

anaerobic treatment technique is better
 Spent wash treatment
• Anaerobic digestion was the mostly tried
option: anaerobic digester, diphasic
anaerobic digester, UASB, Fluidized bed
anaerobic filter, etc.
 pH adjustments Anaerobic reactor
Biogas Gas

Effluent
Raw Spent BOD about 3000 – 4000 mg/L
Wash
BOD =50, 000 mg/L sludge

This effluent cannot be disposed off to a river or sewer line or ocean

Disposal Standard = 30 mg/L for disposal into surface waters

Conventional Anaerobic Digester

Biogas

Effluent Influent

Sludge
UASB (Upflow Anaerobic Sludge
Blanket) Reactor
Anaerobic Fluidized Bed Reactor (AFBR)
Biogas

Treated
water
Recycle line
Biofilm
Carrier

Wastewater
feed
• Anaerobic digestion bring the BOD down to
about 2000 – 4000 mg/lit
• But the discharge standards are normally
much lower (30 or 20 mg/lit)
• Hence normally aerobic systems are used to
bring the BOD down to < 30 or 20 mg/lit

• Hence the process becomes costly

 pH adjustments Anaerobic reactor
Biogas Gas

Effluent
Raw Spent BOD about 3000 – 4000 mg/L
Wash sludge
BOD =50, 000 mg/L

ASP

Effluent
BOD < 30 mg/L Aeration tank
Colour persists sludge
 pH adjustments Anaerobic reactor
Biogas Gas

Raw Spent
Wash sludge
BOD =50, 000 mg/L

Adsorption tower ASP

Effluent Aeration tank

BOD < 30 mg/L sludge
 Sludge Treatment

• Sludge is usually concentrated using a filter press or in

a centrifuge.

• The thickened (concentrated) sludge may be dried in

sludge drying beds (solar energy) and sludge cakes
produced.

• Sludge cake can be used as manure for horticulture, if

it is safe. Or else, to be disposed off in landfills.
 Problems with the Biological
Treatment System
• Requirement of ‘polishing’ after anaerobic
• Uncertainty involved with biological
systems
• Influence of external parameters like
weather, temperature
• Requirement of energy intensive secondary
treatment takes the cost high.
• Colour problem needs to be addressed
• CH4 generated in the first step is used in the
subsequent steps
• Much slower than thermal systems
• More space/volume required
 Thermal Treatment of Spent
wash
• There have been many other attempts to
deal with spent wash
• Burning of concentrated spent wash dates
back to world war 1 period (not in India)
• Production of activated carbon, Solid CO2,
potash, etc was one of them (reported by
Reich in 1945 from US)
Thermal properties of Spent wash
• Specific gravity: 1.04 to 1.05
• Total Solids: 10 to 22 %
• Total VS: 6 to 8 %
• Ash content: 2 to 3 %
• Calorific Value: 3200 to 3800 kCal/kg (for dry
solids)
• Density of concentrated spent wash 1.350 g/cc
 PROCESS OF INCINERATION,

➢ Combustion (controlled burning) of wastes in properly

designed and constructed furnace to sterile ash with
proper care for air pollution and water pollution.

➢ The prime objective of incineration is WASTE

DESTRUCTION, not power generation or ash
recovery. However, power generation makes
incineration economically viable.
Waste
Aux Fuel
FD Fan

Waste Waste
Preparation Feeding FURNACE Flue Gas
and fly ash

Gas out
Bottom Ash Heat
Recovery
S
T
A
Particle
C Acidic Gas
Removal Heat
Removal
K ID Fan
Fly Ash

For treatment & disposal

 Air Pollution Control Equipment

Equipment Pollutant Removed % Removal Pressure Drop

Inches of Water
Column
Settling Chamber Large particles 0 to 30 % 0.5 to 1

Multiple Cyclones Particles 30 to 80 % 3 to 4 (single

cyclone: about 1)
Venturi Scrubber Particles & acidic 80 to 96 % 10 to 50
gases like HCl,
SO2
Packed scrubber Aerosols & acidic 80 to 96 % 6 to 8
gases
ESP Fine particles 90 to 97 % 0.5 to 1

Fabric Filter bag Fine particles 97 to 99.9 % 1 to 8

House

52
Incineration of Distillery Spentwash:
Indian Experience
• First incineration was reported in early
nineteen sixties, but not popular
• Became popular in late nineteen eighties.
Two popular designs were
• Destrotherm from Thermax, Pune
• Sprannihilator from Praj Consultech, Pune
Raw Spent wash
10-15% Solids
content Evaporator

Concentrated
Spentwash of
about 60% Solids
content

Flue Gas
Furnace
Air

Ash (high fertilizer value)

 1st incineration plant for spentwash
• Set up at Dyer Meakin Breweries Ltd.,
Lucknow in 1960
• Capacity: 90 gal spent wash / hour
• Uses forced circulation evaporator for
concentrating spentwash to 60% solids
content
• Ash from spentwash incinerator: contains
high Potash as K2O (37% of the ash)
Raw Spent wash
10-15% Solids
content Quadruple Effect
Evaporator
Concentrated
Spentwash of
About 60% Solids
content

Flue Gas
Furnace
Air

Ash (high fertilizer value)

 Destrotherm from Thermax
• Govt. Distillery at Chitali, Maharshtra in 1984
• Expected performance for a 45KLD distillery
– Spent wash generation: 3000lit/hr
– Ash collection: 700 kg/hr
– Power generation: 700kW (Process electricity
consumption 500 kW)
– Steam generation: 11515 kg/hr (40bars, 400oC) and
steam consumption [Link] (at 5 bars)
Raw Spent wash Steam
10-15% Solids
content Evaporator
Concentrated
Spentwash of
Flue gas for treatment Steam
About 60% Solids
content
Boiler

Flue Gas Water Excess steam

Furnace
Air

Ash (high fertilizer value)

Bag Filter House

60
 Destrotherm
• Spent wash of 60% solids content is sprayed
into the furnace
• Raw spent wash is concentrated to 60% in
external forced draft evaporators using
process steam
• The flue gas generated goes for the
production of steam
• Ash is rich in potash
• Destrotherm did not pick up the expected
popularity may be due to
• The complexity involved in the evaporation system
• Large area / volume occupied by the evaporators
• Clinker formation on the boiler tubes
• High cost involved
 Sprannihilator from Praj
Counseltech
• Aimed at solving some of the problems with
Destrotherm
• Evaporation section made simple and easy
to handle
• Plants becomes more compact
• First plant at Kohlapur (M/S. Gadhinglaj
Taluka Sahakari Sakhar Karkhana Ltd.)
Raw Spent wash Flue gas for treatment
10-15% Solids
content Evaporator
Concentrated
Spentwash of
About 60% Solids
content

Flue Gas

Furnace
Air

Ash (high fertilizer value)

Venturi Scrubber

66
 Sprannihilator
• About 60% solids content spent wash is
sprayed into the furnace

• Raw spent wash is concentrated to 60%

using the flue gas heat in a venturi-
evaporator
• Ash is rich in potash
• More units came up soon at a Cost of about
Rs. 37,000,000 (37 Million)

• One at M/S. Polychem Ltd., Nira

• 45KLD distillery

• Another at Liquors India Pvt. Ltd.,

Hyderabad
• 20 KLD distiller
Problems with Incineration of spent
wash
• Solids content of spent wash is to be
brought to about 60% before firing into the
furnace.
• This brings the economics down as it is
energy intensive. Also, damaging to the
material of construction.
• Spent wash is sticky
• It swells (up to about 5 times the original volume)
while heating
 Protocols/ Guidelines related to Treatment & Disposal
options for distillery effluent

• Existing Molasses based Distilleries:

Zero Effluent Discharge (100% by Dec. 2005) through
– Bio-composting,
– Concentration and Incineration
– Biomethanation followed by two stage secondary treatment
followed by ferti-irrigation
– Biomethanation followed by pre-sown irrigation
– Biomethanation followed by treatment and Discharge into
deep sea.

• New Distilleries & Expansion of Existing Distilleries (Molasses

based)
– Zero Effluent Discharge in surface water/ ground water
Protocols/ Guidelines related to Treatment & Disposal
options for distillery effluent
CPCB Resolution (June 2008)

• New stand alone Distilleries:

➢ Concentration – incineration system

• New attached Distilleries:

➢ Bio-methanation followed by bio-composting
➢ Concentration– incineration system {Reboiler/
Evaporation/ Concentration followed by incineration
of concentrated spent wash in boiler (for power
generation)}

• Existing stand alone Distilleries (expansion):

➢ Concentration – incineration system
 Protocols/ Guidelines related to Treatment &
Disposal options for distillery effluent

CPCB Resolution (June 2008)

• Distilleries (both stand alone and attached)

not complying with the required
environmental standards to switch over to
emerging technologies from existing
technologies of Ferti-irrigation, One time
land application and composting in a time
bound manner.
 Co-Processing of Distillery Spent wash
concentrate in Cement Industry
(CPCB, 2010)

Co-processing of molasses based distillery

spent wash concentrate in Cement Kilns,
furnaces of Thermal Power Plants/ Steel
Plants, Incinerators
Fermentation & Distillation Industries > 400

Molasses based Distilleries ~ 300

Distilleries attached with Sugar Mills ~ 125

Distilleries with RO Concentration 100

system

Distilleries with MEE concentration 100

system
 Concentrating spent wash
• About hundred RO (Reverse Osmosis)
plants working in distilleries

• About hundred MEE (Multiple Effect

Evaporation) system working in distilleries
 Reverse Osmosis
Concentrated
Spentwash of
Raw Spent wash
50-60% Solids
10-15% Solids
Content to
content
Boilers / Incinerators
Cement Kilns / Drying
MEE (Multiple Effect
Evaporator)
Co-Processing
▪ Co-processing in cement industry refers to the substitution
of primary fuel and raw material by waste, recovering
energy and material from waste.

▪ Waste materials used for co-processing are referred to as

alternative fuels and raw materials (AFR).

▪ Raw material for Cement manufacturing: Lime stone & Clay

/ shale: Calcium Carbonate, Alumina, Silica, Oxides of iron)
 Cement Kiln Suitability

❖ High temperatures (1400 O C) and residence time of 4 – 5

seconds in an oxygen–rich atmosphere ensure the
destruction of organic compounds.
❖ Any acid gases formed during combustion are neutralized
by the alkaline raw material and are incorporated into the
cement clinker.
❖ Interaction of the flue gases and the raw material present
in the kiln ensures that the non–combustible part of the
residue is held back in the process and is incorporated
into the clinker in a practically irreversible manner.
❖ No waste is generated that requires subsequent
processing.
 Benefits of Co-processing

➢ Reduction in Green House gases emission

& related benefit of carbon trading

➢ Conversion of waste into energy / as a

raw mix component

➢ Conservation of fossil fuel resource

➢ Reduction in energy / cement production

costs
 Different treatment technology routes for
ZERO LIQUID DISCHARGE (ZLD)

reverse osmosis effluent for use / recharge

Filtrate

Spent wash incineration/co-processing.

multi-effect evaporation

• Concentration through RO/ MEE followed by

incineration/ co-processing.
 Different treatment technology routes for
ZERO LIQUID DISCHARGE (ZLD)

reverse osmosis effluent for use / recharge

Filtrate

Biomethanation incineration/co-processing.

sludge
multi-effect evaporation

• Concentration through RO/ MEE followed by

incineration/ co-processing.