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Session 1 :

Introduction to Anaerobic Digestion


Technology and its Process
fundamentals

by
Prof. P.G. Rathnasiri
Department of Chemical and process engineering
University of Moratuwa
Definition to Bioenergy

Bioenergy is renewable energy made available from


materials derived from biological sources (biomass).

Biomass is any organic material which has stored


sunlight in the form of chemical energy.
Definition to biofuels
When biomass is transformed by using thermochemical
and biochemical processes into intermediate products in gas,liquid
and solid state, they are called BIOFUELS

eg. Biogas, Producer gas Gasious fuel


Charcoal Solid fuel
Ethanol, Biodiesel Liquid fuel

Biofuels are carbon neutral if produced sustainably


What is biomass?
Any plant derived organic matter available on a renewable
basis and animal wastes

 Dedicated energy crops and trees


 Agricultural crop wastes and residues
 Wood wastes and residues
 Municipal wastes
 Industrial wastes
 Animal wastes
 Aquatic plants
 Micro alge
Biomass
Biomass available in Sri
Lanka

Agricultural residues

Fruit and vegetable wastes


Importance of bio waste

Biodegradable organic
materials
CLASSIFICATION OF BIOFUEL PRODUCTION
PROCESSES
• Direct combustion
Thermochemical • Pyrolysis
• Other thermochemical

• Alchohol fermentation
Biochemical • Anaerobic digestion
• Biophotolysis

Agrochemical • Fuel extraction


CLASSIFICATION OF BIOFUEL PRODUCTION
PROCESSES
oxygen

Direct Combustion

Photosynthesis Thermochemical Gases


Pyrolysis & Gasification Liquids
oils
Thermal pretreatment Charcoal
Process heat
Biomass Electricity
Resources Ethanol Mechanical
Alchol fermentation
Power etc

Anaerobic digestion Biogas


Biochemical

Biophotolysis Bio Hydrogen

Agrochemical Liquids
Fuel extraction
oils
Organic humus
And nutrients
recycled
Role of technologist in Bioenergy/
Biofuel discipline
An engineering technologist is a professional trained in certain aspects of
development and implementation of a respective area of technology. Engineering
technology education is even more applied and less theoretical than engineering
education, though in a broad sense both have a focus on practical application

What is Biofuel technology


Biofuels technology can be defined as application of feed stocks in a sequence of
processes leading to the production of different biofuels types. Biofuels processes are
either natural or chemical stages of an industrial or pilot project development leading
to the final production of biofuels.
Large scale AD plant from
Scandinavian country

High rate large scale anaerobic digesters


Job description of large scale
bioenergy plant operator
POSITION TITLE
Reporting to the Operations Supervisor, the Biogas Plant Operator performs skilled work
that is necessary in operating a dairy anaerobic digester, gas conditioning skid,
associated digester and upgrader plant equipment. The facility is composed of a
digester, pumps, gas blowers, compressors, oxygen generators, condensers, chillers and
related auxiliary equipment.

Responsibilities of employment
Monitor gas production of anaerobic digesters with a focus on O2 and H2S concentration.
Complete daily rounds of plant equipment and capture fluid temps, pressures, oil levels,
gas concentrations, process flows. Check equipment for proper operation looking for
excessive vibration, fluid leaks and any conditions needing further attention. Accurately
record all plant operational parameters and respond to unsatisfactory trends.
Operate plant equipment including the pumps, blowers, and other related auxiliary
equipment in accordance with manufacture recommendation and established company
policy. Participate in plant housekeeping programs and material handling safety activities
to ensure safe working conditions.
Let’s See Current state of AD
technology Development In
Europe
How (AD) technology emerged in Europe

John Dalton (1766-1844),


collecting marsh gas with
youngsters nearby Manchester,
England

1800

2020
Integrated solid waste management technology producing
green electricity and fertilizer
The ‘European Biomethane Map 2020’ shows a 51% increase of biomethane
plants in Europe in two years
Major Feed stocks for Biomethane Production
European Biomethane MAP

Source : European Biogas Association (EBA)


Large scale AD plants
For AD process feed stock must be
biodegradable organic wastes
Waste is not waste
•Waste is a misplaced resource

•Waste residues can be converted into reusable/new materials,


energy, and other products with value

•Natural resources are limited and depleting

•Mitigation of waste management problems

Waste to Energy

–Harnessing energy from urban biomass, sewage


sludge, agricultural residues, micro-algae, etc.
Definition to waste according to
SWM policy Sri Lanka 2019
Waste is defined in this policy as any material, substance or by product
eliminated or discarded or as no longer required at a particular time and a

particular place or form and therefore to be used either as a resource or


to be treated and disposed of in an environmentally sound manner if it
does not have a utility value.
Waste management policy statements

• Technology development usage and transfer shall


exclusively focus on holistic integrated waste management systems
considering the inter-linkages with waste forms to prevent transfer of
pollution from one source to the other and maximize resource
utilization.

• Technology development for waste recycling and resource


recovery shall be promoted with appropriate
partnerships covering the entire life cycle.
National waste management policy will change the paradigm from
Linear waste management to circular economy

The Ministry of Environment shall carryout a comprehensive revision of the


relevance, sufficiency, efficiency and effectiveness of the existing laws and
regulations to support implementation of the national policy to achieve
required transformation deviating from ‘linear waste management
approaches’ (means make, use, dispose) and moving forward to ‘circular
systems’ (means keep resources in use for as long as possible, extract the
maximum value from them whilst in use, then recover and regenerate
products and materials at the end of its service life which is refereed as
‘circular economy’).

22
Waste to energy : Different options
Resource management and waste management

PROPERTY OF DEPARTMENT OF CHEMICAL


& PROCESS ENGINEERING (Dr. PG 24
RATNASIRI)
Bio Waste generation

• House hold wastes


• Municipal solid wastes (MSW)
• Waste water and solid wastes from industries
• Market wastes
• Agricultural residues
• Wastes from slaughter
• Manure ( Cow, Pig .etc)
Common waste streams

Municipal Solid Waste (MSW): household waste and waste similar in nature and
composition to household waste.
Market Waste (MW): primarily organic waste, such as leaves, skins, and unsold food, discarded at or near food
markets.
Wastewater (WW): any water that has been used in the home, in a business, or as part of an industrial process.
Fecal Sludge (FS): all liquid and semi-liquid contents of pits and vaults accumulating in on-site sanitations
installations.
Agro-Industrial Waste (AIW): agriculture residues, which are further divided into field residues (present in the field after
the process of crop harvesting, e.g. leaves, stalks, seed pods, and stems) and process residues (present even after the crop
is processed), and industrial residues.

Animal Waste (AW): wastes generated from animal confinement operations


Agro-Industrial Waste (AIW):
agriculture residues, which are further divided into field residues (present in
the field after the process of crop harvesting, e.g. leaves, stalks, seed pods,
and stems) and process residues (present even after the crop is processed),
and industrial residues

Process Residues
Field Residues

Baggase
Field
residues 27
Recovery of Energy from Wastewater
Wastewater is defined as combination of liquid or water carried wastes
removed from residences, institutions and commercials and industrial
establishments together with groundwater, surface water and storm water
as may be present

Discharging wastewater

Industrial wastewater
Sewage wastewater
28
Waste streams and resource recovery

Source: Andersson et al., 2016


Technologies available for solid waste treatment

• Anaerobic Digestion

• Sanitary Land Filling

• Composting

• Incineration
31
CURRENT OPEN DUMPING ISSUES

Still not too late to


take
!!!
32
CURRENT OPERATION
– Odor issues

33
PROPERTY OF DEPARTMENT OF CHEMICAL & PROCESS ENGINEERING (Dr. PG RATNASIRI)

CURRENT OPERATION
– Manual sorting
A

separation of
MSW on-site
34
PROPERTY OF DEPARTMENT OF CHEMICAL & PROCESS ENGINEERING (Dr. PG RATNASIRI)

CURRENT OPERATION
– Manual sorting

Organic fraction of
MSW with

generation
potential

35
Open dumping
– Related issues

collecting naturally

36
Wastewater (Leachate) generation in local open
dumping site
AD technology is a branch of
Environmental Biotechnology
Major Benefits of AD technology
AD functions include:
• Converting biodegradable organic matter into biogas, which can be sold as a
fuel or combusted for on-farm energy use.

• Reducing biochemical oxygen demand (BOD) and chemical oxygen demand


(COD).

• Reducing odors.

• Converting organic nitrogen into more plant-available forms that can be used as
fertilizer.

• Reducing pathogens.

• Capturing CH4 that otherwise would be released and increase GHG emission.
Why anaerobic digestion
WASTE TREATMENT BENEFITS
• Natural waste treatment process
• Requires less land than aerobic composting or landfilling
• Reduces disposed waste volume and weight to be landfilled
ENERGY BENEFITS
• • Net energy producing process
• • Generate high quality renewable fuel
• • Biogas proven in numerous end-use applications

ENVIRONMENTAL BENEFITS
• Significantly reduces carbon dioxide and methane emissions
• Eliminates odours
• Produces a sanitized compost and nutrient-rich liquid fertilizer
• Maximizes recycling benefits

ECONOMIC BENEFITS
• Is more cost-effective than other treatment options from a life-cycle perspective
AD as a sustainable technology
Waste treatment technique

Net energy producing technology

Environmental friendly technology

Socially acceptable technology

PEOPLE – PLANET -PROFIT


Overview of Anaerobic digestion process and benefits as renewable
energy Process heat,space heating,water
Gas burner/boiler heating

Electricity/ Combined heat and power

Gas engine/turbine
Storage Transport

Vehicle

Cleaning
Fibre
composting
Fibre
Digester to Farm
Liquid
Pretreatment
(mixing/screening/choping)
Feedstock
Three stages of AD technology

Discuss why feed stock pre treatment is important


Discuss why post treatment is necessary
Merits and demerits of anaerobic digestion
Merits Demerits
• The production of energy as methane • Slow growth rate of methenogens
( excess of that required for process) • Requires large retention times
• Low production of bilogical sludge • Strict methenogen sensitivity to
• High degree of stabilization process parameters
• Reduction of GHG emission • Auxiliary heating requirements

• Breweries
Energy crops ( eg. Water hysinth) • Distilleries
• Food processing
• Sugar industry
Industrial
FEEDSTOCKS • Slaughterhouse

ORGANIC wastes Agricultural Animal wastes


Residues

Domestic

•Municipal waste water


• MSW
• Sewage sludge
Total solution for solid and liquid waste management using
AD technology
Anaerobic Digestion Process Fundamentals
Definition to Anaerobic Conversion

The use of microbes in the absence of oxygen for


the stabilization of organic material by conversion
to methane, carbon dioxide, new biomass and
inorganic products
John Dalton (1766-1844), collecting marsh gas
with youngsters nearby Manchester, England
Microscopic picture of bacteria from Anaerobic reactor
Anaerobic vs Aerobic
Oxygen
Aerobic treatment CO2

H2O
Influent Organic matter (
C6H12O2N)n
More Sludge
Presence of oxygen

Anerobic treatment
CH4 CO2

Influent
Organic
VFA matter Less Sludge
Acetic
As a
Absence of oxygen fertilizer
Why we call biogas production process as an
anaerobic process ?
PROCESS FUNDAMENTALS of ANAEROBIC CONVERSION

Composite Particulate Material 100COD


Disintegration
Complex organics
Polymeric organic material
Carbohydrates Proteins Lipids 76%
Hyd & fermentation
Hydrolysis
20% Higher organic4%
Sugars Amino acids LC fatty acids acids
Acedogenisis Propionate , Butyrate ,
Valerate
24%
Acetogenisis 52%
Acetogenisis
Acetate Hydrogen Acetic acid Hydrogen

Methenogenisis Methane
72% 28%
Methanogenisis
Methane
Conversion processes in
Anaerobic digestion Substrate flow in COD
Note: 72% of methane is produced
via acetate route !!!!!
Methanogenic bacteria
Microorganisms utilize organic materials and produce methane
General methenogenesis scheme COD flux
Composite Particulate Material
10% inerts
30% Disintegration
30% 30%
Polymeric organic material
Carbohydrates Proteins Lipids

1% 29%
Hydrolysis
Sugars Amino acids LC fatty acids
16%
13% 12% 2%
Acidogenesis
Propionate , Butyrate , 20% 9%
Valer ate
20% 9%
6%

12%
Acetogenesis
Acetate Hydrogen

64% 26% Mehtanogenesis


Methane
The ADM1 superstructure

Complex particulate & Inactive biomass

Inert soluble Carbohydrates Protiens Lipids Inert particulate

MS AA LCFA

Dead/inactive biomass recycling


Hva,Hbu
HPr

HAc H2

Acedogens
CH4,CO2
Acetogens

Methenogens
Conversions based on biochemical and physico chemical reactions
CO2 CH4 H2O H2 H2S Gas phase

Composites
inerts
Gas
Hydrolysis
Liquid phase
Bio chemical reactions

protiens Carbohydrates Lipids

AA
Fermentation
MS
Death/decay

HAc,HPr,Hbu,Hva,CO2,NH3,LCFA Ac-,Pr-,Bu-,Va-,HCO3-,NH4+,LCFA
Acetogenesis
Hac H2 CO2 HCO3-
Growth

Methenogenesis
Biomass CH4

Physico chemical reactions


Definitions to major conversion steps:
• Hydrolysis: Break down of large insoluble polymers into soluble monomers
by extracellular enzymes
• Acedogenisis ( Fermentation) : Soluble organic compounds are converted into
VFA, alchohols, hydrogen, and CO2
• Acetogenisis: Breakdown of volatile fatty acids to acetate and hydrogen

• Methanogenesis : Methane is produced from acetic acid, hydrogen and


carbon dioxide as well as irectly from other substrates such
as methanol and methyl amines.

Major chemical reactions involve in formation of methane from


Different substrates
• From Hydrogen : 4H2 +CO2 CH4 + 2H2O
• From Acetate : CH3COOH CH4 + CO2
• From methanol: 4CH3OH 3CH4 +CO2+ 2H2O

• From methyl amines: 4(CH3)3N + H2O 9CH4 +3CO2 + 6H2O +4NH3


Operating parameters and factors affecting for anaerobic conversion:

The most important operating factors:


• Temperature
• pH
• Alkalinity
• Nutrients and micronutrients
• Toxicity and inhibition

TEMPERATURE
Methanogens growth rate %

100 • Psychrophilic range, from 4 – 150C


Thermophiles
•Mesophilic range, from 20 -400C
80
• Thermophilic range, from 45 – 700C
60
mesophiles

40
Psychrophiles

20
But optimum
0 10 20 30 40 50 60 70 80
• Meshophilic 35C
Temperature 0C • Thermophilic 55 C
pH: Methane formation occurs at pH 6.6 -7.6. A pH below 6.2 inhibits the
methanogenic process. VFA should be less than 250mg/l

Alkalinity or buffer capacity :The buffer capacity is the ability of the reactor
contents to resist a change in pH if acids ( VFA for example) are accumulating
HCO3 alkalinity ranges 1000-5000mg/l.

Nutrients and micronutrients:


C:N ratio range 16 – 19 ( wt basis). N needs for cell growth for all species
Micronutrients are essential for methanogenic bacteria. Eg Na+, Co, Ni, Fe++

Toxicity and inhibition :

These are more common to anaerobic systems and include, volatile fatty
acids (VFA), NH3 , H2S. ( pig manure contains more NH4+ and NH3),
antibiotics, detergents, aldehydes, cyanide, antibiotics
Let’s look at important process parameters:
•Feasibility of waste stream for anaerobic conversion :
COD > 1500mg/l( For waste water)

• COD removal efficiency ( depends on technology used) but around 70-80%

•Volumetric loading rate for reactor = kg COD/ m3.day


( mass of feedstock per unit digester working volume per day)

• Hydrolic retention time (HRT) = V/Q where Q = volumetric flow rate (m3/day)

• Solids retention time (SRT) = HRT for CSTR reactors without recycling solids

• Biogas yield = m3 biogas produced/ kg of COD removed

• Theoritical yield : CH4 + 2O2 CO2 + H2O


64 g COD CH4 = 16 g CH4
1g COD CH4 = 0.25 g CH4
since 1g COD CH4 Eqivalant to 1g COD consumed
1g COD consumed = 0.25 CH4 produced
Classifications of waste treatment
according to Metabolic function
•Aerobic – In the presence of oxygen
•Anaerobic –in the absence of oxygen
•Anoxic – in the absence of oxygen (nitrite or nitrate act as electron
•acceptor)
•Facultative – presence or absence of oxygen
Useful definitions used in waste treatment

Metabolic function Definition

• Aerobic process in the presence of oxygen

• Anaerobic process in the absence of oxygen

• Anoxic process nitrate nitrogen is converted into Nitrogen


gas in the absence of oxygen

• Facultative process in the presence of absence of oxygen

Treatment processes
• Suspended growth maintained in a suspension within a liquid
• Attached growth biofilm process or bacteria attached to inert medium
• Combined process Combination of both

• Carbonaceous COD removal Organic matter into biomass and gaseous products
• Nitrification ammonia is converted into nitrite and nitrate
• Denitrification nitrate is converted into nitrogen gas
Micro organisms are used to oxidize the dissolved and
particulate carbonaceous organic matter into simple end
products and BIOMASS

• Oxidation & Synthesis ( called metabolic reaction)

CHONS + O2 + nutrients bacteria CO2 + NH3 + C5H7NO2 +


other end products

• Endogenous respiration

C5H7NO2 + O2 bacteria CO2 + 2H2O + NH3 + energy


Aerobic respiration
Nutrients New cells

Synthesis
Anaerobic
Organic Bacteria
energy
CO2 and H2O respiration
compounds

Nutrients New cells


O2

Synthesis
Nitrification Organic Bacteria CH4 and H2O
energy
compounds
Nutrients New cells

CO2 Synthesis
Bacteria NO2 and NO3
energy

NH4
O2
Bacteria growth pattern in batch
reactor
Substrate
Stationary
phase death
Lag phase
phase Growth
phase

Biomass

Time
Potential industries for AD technology

Alcohol distillation
Landfill leachate
Breweries
Pharmaceuticals
Chemical manufacturing
Pulp and paper
Dairy and cheese processing
Slaughterhouse and meatpacking
Domestic wastewater
Soft drink beverages
Fish and seafood processing
Sugar processing
Why we treat waste before feeding into
biogas reactor
Pretreatment

Why pre treatment

Anaerobic conversion process is generally limited by the rate of hydrolysis of suspended matter and
organic particulates. This is particularly significant during the anaerobic treatment of solid wastes, slurries and
waste waters with high suspended solids. An alternative means of accelerating the decomposition of these
composite particulate material with lump characteristics are to make them more accessible to enzymatic attack

by means of physical, chemical or biological pre-treatment.


What is hydrolysis

The process of solubilizing complex organic matter

Carried out by extracellular enzymes ie enzyme activity


Outside the cell
Hydrolysis intermediates
hydrolases
Carbohydrates Sugar

proteases,
Protien Amino acids

lipases
Lipids Fatty acids and Glycerols
Hydrolysis

• Since bacteria are unable to take up particulate organic material, first it has to be
broken down into small molecules by the action of extracellular enzymes.

• The molecules or monomers produced are now able to transfer across cell
membranes. This liquefaction or hydrolysis is the first step required for microbial
utilization of complex bio polymers.

• The rate of hydrolysis is determined by both microbial constraints and physical and
chemical characteristics of substrate ( eg. Crystallinity of cellulose, degree of
association with lignin, surface area/ particle size ratio).

Discuss two mechanism of hydrolysis


Acedogenesis

Microbial process of metabolizing hydrolyzed organic materials into organic acids, H2


and CO2

The soluble polymers from hydrolysis are metabolized


intracellularly by acid forming bacteria and produce a range of
organic acids ( propionate, acetate, butyrate), alcohols ( ethanol,
butanol), hydrogen and carbon dioxide. Because these volatile fatty
acids (VFA) are the main products of fermentive organisms, they are
normally called acidifying or acidogenic micro organisms.
Acetogenesis Anaerobic oxidation of
intermediate products
In this stage, hydrogen producing acetogenic
Formation of acetate from bacteria are responsible for the anaerobic
byproducts of acedogenesis. oxidation of the products generated in the
acedogenic phase into substrates suitable for
methanogens. Acetate, H2 and CO2 are the
main products of acetogenic conversion.

Hydrogen producing acetogenic bacteria.


Acetogenesis since acetate is the main carbon product.

The accumulation of hydrogen inhibits the degradation of short chain fatty acid specially
Propionic acid

This step can be rate limiting step of methenogen metabolism


Interspecies hydrogen transfer or Syntropic action between
Acetogens and methenogens
When hydrogen partial pressure is very low, reactor is stable
Equations ”G0,' (kJ/reaction)
1. Proton-reducing (H2-producing) acetogenic bacteria
A. CH3CH2CH2COO- + 2H2O 2 CH3COO- + 2H2 + H+ +48.1

B. CH3CH2COO- + 3H2O CH3COO- + HCO3- + H+ + 3H2 +76.1


2. H2-using methanogens and desulfovibrios
C. 4H2 + HCO3- + H + CH4 + 3 H2O -135.6
Syntrophic
2-
D. 4H2 + S04 + H + -
HS + 4 H2O -151.9
reactions in
3. Co-culture of 1 and 2
-39.4
an anaerobic
A + C 2 CH3CH2CH2COO- + HCO3- + H2O 4 CH3COO- + H+ + CH4
-55.7
reactor
A + D 2 CH3CH2CH2COO- + S042- 4 CH3COO- + H+ + HS-
B + C 4 CH3CH2COO- + 12H2 4 CH3COO- + HCO3- + H+ + 3 CH4 -102.4

B + D 4 CH3CH2COO- + 3 S042" 4 CH3COO- + 4 HCO3- + H+ + 3 HS- -151.3

Explain how co culture works


Methenogenesis
Cleavage of acetic acid into methane done by acetoclastic methenogens

CH3COOH CH4 CO2

Hydrogenotrophic methenogens convert hydrogen and Co2 into methane


CO2 4H2 CH4 H2O

Reaction DG°, (kJ/mol substrate)


1. CO2 + 4 H2 CH4 + 2H2O -130.7
HCO3- + 4 H2 + H+  CH4 + 3 H2O -135.5
2. CH3COO-+ H+  H4 + CO2 -37.0
CH3COO-+ H2O  CH4 + HCO3- -32.3
3. HCOO- + H+  0.25 CH4 + 0.75 CO2 + 0.5 H2O -36.1
4. CO + 0.5 H2O  0.25 CH4 + 0.75 CO2 -52.7
5. CH3OH  0.75 CH4 + 0.25 CO2 + 0.5 H2O -79.9
6. CH3NH3+ + 0.5 H2O  0.75 CH4 + 0.25 CO2 + NH4+ -57.4
7. (CH3)2NH2+ + H2O  1.5 CH4 + 0.5 CO2 + NH4+ -112.2
8. (CH3)2NCH2CH3H+ + H2O  1.5 CH4 + 0.5 CO2 ++H3NCH2CH3 -105.0
9. (CH3)3NH+ 1.5H2O  2.25 CH4 + 0.75 CO2 + NH4+ -170.8
Intermediate products under biogas production process

Delicate balance exists


Among each group
Methenogenesis
• The final step in the overall anaerobic conversion of organic matter into
methane and CO2 is catalyzed by methanogenic bacteria.
• Methanogens utilize only a limited number of substrates, comprising acetate or
the C1 compounds CO2/H2 , formate, methanol, methylamines and CO.. Both
hydrogenotrophic and acetoclastic methanogenesis are crucial in maintaining
the progress of anaerobic digestion.
• Methanogenic bacteria fulfill a crucial role as hydrogen scavengers in overall
anaerobic digestion by keeping the partial pressure of H2 ( 10-4atm) very low,
thereby pulling H2 producing reactions.
• By keeping it very low an accumulation of VFA, which would result in fermenter
performance failure due to acidification, is prevented.
• If soluble organic components are the main substrates for anaerobic digestion,
acetogenesis and methanogenesis have been identified as rate limiting steps
due to the long generation times of these species.

Explain what do you mean by rate limiting steps


of AD process
Factors affecting for anaerobic conversion

Influence of temperature on anaerobic conversion

Three temperature ranges are defined in anaerobic conversion:

Psychrophilic range, from 4 – 150C


Mesophilic range, from 20 -400C
Thermophilic range, from 45 – 700C

Though reactors are effectively operated between these ranges,


optimal temperatures for mesophilic and thermophilic organisms
are 350C and 550C respectively.

Beyond these upper temperature limits the decay rate of the


bacteria starts to exceed the growth rate
Relative growth rate of psychrophilic, mesophilic and
thermophilic methanogens.
Methanogens growth rate %

100
Thermophiles

80

60
mesophiles

40
Psychrophiles

20

0 10 20 30 40 50 60 70 80

Temperature 0C

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