CHG 8191 C:

Wastewater Treatment
Topic: Bioreactor Fundamentals

Fall 2019 CHG 8191 C - Wastewater Treatment 1 / 26

 Quick Refresher – Reaction Kinetics

Sample Stoichiometry Single Reagent Reactions

0thth Order
 𝑣 𝑎 𝐴+ 𝑣 𝑏 𝐵 → 𝑣 𝑐 𝐶 0 Order
1st Order
2stndOrder
1 Order
Empirical Rate of Reaction
𝛼 𝛽 𝛾 2nd Order
 𝑟 =− 𝑘 [ 𝐴 ] [ 𝐵 ] → 𝑘 [ 𝐶 ]
𝐴

Fundamental Rate of Reaction

𝑣𝑎 𝑣𝑏 𝑣𝑐
 𝑟 =− 𝑘 [ 𝐴 ] [ 𝐵 ] → 𝑘 [ 𝐶 ]
𝐴

Reaction Order
 𝑂𝑟𝑑𝑒𝑟= ( 𝛼 + 𝛽 ) ∨γ

Fall 2019 CHG 8191 C - Wastewater Treatment 2 / 26

 Quick Refresher – Reactor Design
Batch Reactor
 
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛=𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 −𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛
Single Reagent Second Order
Sample Calculation

dሺ𝑉ሾ𝐴ሿሻ
= −𝑘ሾ𝐴ሿ2 𝑉
dt
dሺሾ𝐴ሿሻ
𝑉 = −𝑘ሾ𝐴ሿ2 𝑉
dt
dሺሾ𝐴ሿሻ
= −𝑘ሾ𝐴ሿ2
dt
ሾ𝐴ሿ0
ሾ𝐴ሿ=
𝑘𝑡ሾ𝐴ሿ0 + 1

Fall 2019 CHG 8191 C - Wastewater Treatment 3 / 26

 Quick Refresher – Reactor Design
Plug Flow Reactor (PFR)
 
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛=𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 −𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛
Single Reagent Second Order
Sample Calculation

dሺ𝑉ሾ𝐴ሿሻ
= −𝑘ሾ𝐴ሿ2 𝑉
dx
dሺሾ𝐴ሿሻ
𝑉 = −𝑘ሾ𝐴ሿ2 𝑉
dx
dሺሾ𝐴ሿሻ
= −𝑘ሾ𝐴ሿ2
dx
ሾ𝐴ሿ0
ሾ𝐴ሿ=
𝑘𝑥ሾ𝐴ሿ0 + 1

Fall 2019 CHG 8191 C - Wastewater Treatment 4 / 26

 Quick Refresher – Reactor Design
Continuous Stirred Tank Reactor (CSTR)
 
𝐼𝑛 −𝑂𝑢𝑡 =𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 −𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛
Single Reagent Second Order
Sample Calculation

𝑄ሾ𝐴ሿ𝑖𝑛 − 𝑄 ሾ𝐴ሿ= 𝑘ሾ𝐴ሿ2 𝑉

0 = 𝑘𝜏ሾ𝐴ሿ2 + ሾ𝐴ሿ− ሾ𝐴ሿ𝑖𝑛
−1 + ඥ1 + 4𝑘𝜏ሾ𝐴ሿ𝑖𝑛
ሾ𝐴ሿ=
2𝑘𝜏

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 Quick Refresher – Reactor Design
Continuous Stirred Tank Reactor in Series (CSTR)
 
𝐼𝑛 −𝑂𝑢𝑡 =𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 −𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛

Single Reagent Second Order

Sample Calculation

𝑄 ሾ𝐴ሿ𝑖−1 − 𝑄 ሾ𝐴ሿ𝑖 = 𝑘ሾ𝐴ሿ2𝑖 𝑉𝑖

0 = 𝑘𝜏𝑖 ሾ𝐴ሿ2𝑖 + ሾ𝐴ሿ𝑖 − ሾ𝐴ሿ𝑖−1
−1 + ඥ1 + 4𝑘𝜏𝑖 ሾ𝐴ሿ𝑖−1
ሾ𝐴ሿ𝑖 =
2𝑘𝜏𝑖

Fall 2019 CHG 8191 C - Wastewater Treatment 6 / 26

 Quick Refresher – Reactor Design
Semibatch
 
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛=𝐼𝑛+𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 −𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛
OR
 
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛=−𝑂𝑢𝑡 +𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 −𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛
Single Reagent Second Order dሺ𝑉ሾ𝐴ሿሻ
Sample Calculation = 𝑄ሾ𝐴ሿ𝑖𝑛 − 𝑘 ሾ𝐴ሿ2 𝑉
dt
dሺሾ𝐴ሿሻ dሺ𝑉 ሻ
𝑉 + ሾ𝐴ሿ = 𝑄ሾ𝐴ሿ𝑖𝑛 − 𝑘 ሾ𝐴ሿ2 𝑉
dሺ𝑉 ሻ dt dt
=𝑄 dሺሾ𝐴ሿሻ
dt 𝑉 + ሾ𝐴ሿሺ𝑄ሻ = 𝑄ሾ𝐴ሿ𝑖𝑛 − 𝑘 ሾ𝐴ሿ2 𝑉
dt
𝑉 = 𝑉0 + 𝑄𝑡 dሺሾ𝐴ሿሻ 𝑄
=൬ ൰ሺሾ𝐴ሿ𝑖𝑛 − ሾ𝐴ሿሻ− 𝑘ሾ𝐴ሿ2
dt 𝑉0 + 𝑄𝑡

Fall 2019 CHG 8191 C - Wastewater Treatment 7 / 26

 Terminology
Oxidative Environment
Aerobic Organism An organism that either requires or can grow in the presence of free oxygen (O 2)
• Obligate aerobes: require the presence of free oxygen
Facultative Organism An organism that can either use or can grow in both the presence and absence of free oxygen (O 2)

Anaerobic Organism An organism that does not require or cannot grow in the presence of dissolved oxygen (O 2)
• Obligate anaerobes: require the absence of free oxygen
• Facultative anaerobes: can function both anaerobically and aerobically
• Aerotolerant anaerobes: only function anaerobically but can tolerate the presence of free oxygen
Oxic Environment An environment containing free oxygen (O2)

Anoxic Environment An environment absent of free oxygen (O2)

Anaerobic Environment An environment absent of all common electron acceptors (O2, NOx, SOx, etc.)

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 Terminology
Growth Environment
Cryophilic/Psychrophilic Organisms that grow optimally at temperatures below 20 oC, usually between 12oC and 18oC
Mesophilic Organisms that grow optimally at temperatures between 25oC and 40oC, typically at 35oC
Thermophilic Organisms that grow optimally at temperatures between 50oC and 75oC, typically at 55oC
Extremophilic Organisms that grow optimally in or tolerate an environment that is atypical for most life (ex. pH
< 2.0, near deep sea hydrothermal vents, extreme salinity)

Carbon and Energy Source

Heterotrophic Organisms that use organic compounds for both their carbon and energy source
Mixotrophic Organisms that can switch between inorganic and organic compounds as their carbon source
and/or can switch between sunlight, organic or inorganic compounds as their energy source
Autotrophic Organisms that use inorganic compounds for their carbon source and sunlight or inorganic
compounds as their energy source
• Photoautotrophs: Use sunlight as an energy source and CO2 as a carbon source
• Chemoautotrophs: Use inorganic compounds as an energy source and CO 2 as a carbon source

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 Terminology
Cellular Structure
Prokaryotic Nuclear material is undivided (i.e. one DNA molecule) and distributed freely within the
cytoplasm. The only known prokaryotes are bacteria and archaebacteria
Eukaryotic Nuclear material is divided into chromosomes and contained within a nuclear membrane within
the cytoplasm (the nucleus)

Fall 2019 CHG 8191 C - Wastewater Treatment 10 / 26

 Terminology Comparison
Table 7-5 Classification of microorganisms by electron donor, electron acceptor, sources of cell carbon, and end products
Type of Organism Common Reaction Carbon Source Electron Donor Electron Acceptor Products
Name
Aerobic Aerobic Oxidation Organic Compound Organic Compounds O2 CO2, H2O
Heterotrophic
Aerobic Autotrophic Nitrification CO2 NH4+ O2 NO2-, NO3-
Iron Oxidation CO2 Fe (II) O2 Fe (III)
Sulfur Oxidation CO2 H2S, So, S2O32- O2 SO42-
Facultative Dentrification Organic Compounds Organic Compounds NO2-, NO3- N2, CO2, H2O
Heterotrophic
Anaerobic Acid Fermentation Organic Compounds Organic Compounds Organic Compounds VFAs
Heterotrophic
Iron Reduction Organic Compounds Organic Compounds Fe (III) Fe(II), CO2, H2O
Sulfate Reduction Organic Compounds Organic Compounds SO4 H2S, CO2, H2O
Methanogenesis Organic Compounds VFAs CO2 CH4
Anaerobic Anammox CO2 NH4+ NO2- N2, NO3-
Autotrophic

Fall 2019 CHG 8191 C - Wastewater Treatment 11 / 26

 Biological Wastewater Treatment
Objectives:
1. Transform dissolved and particulate biodegradable constituents into desired end products
(i.e. chemically inert of easily separable compounds)
2. Capture and incorporate suspended and colloidal solids into biological flocs and/or
biofilms
3. Transform or remove nutrients of concern, such as nitrogen and phosphorus
4. Remove or reduce amount of trace compounds of note

𝑣  1 ( 𝑂𝑟𝑔𝑎𝑛𝑖𝑐𝑠 ) +𝑣 2 O 2+ 𝑣 3 N H 3+ 𝑣 4 P O 34 − + 𝑣5 ( 𝑇𝑟𝑎𝑐𝑒 ) 𝑚 𝑖𝑐𝑟𝑜𝑜𝑟𝑔𝑎𝑛𝑖𝑠𝑚𝑠 𝑣 6 ( 𝑁𝑒𝑤 𝐶𝑒𝑙𝑙𝑠 )+ 𝑣 7 C O 2+ 𝑣 8 H 2 O + 𝑣 9 N 2

→

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 What’s in the Soup? Bacteria
• Unicellular prokaryotic organisms
• Generally fall into the size range of 0.5 – 5.0 μm
• Bacillus = rod shape
• Cocci = sphere shape
• Vibrio = curved rod shape
• Gram-negative = Thin peptidoglycan cell wall sandwiched
between an outer membrane and an inner cytoplasmic
membrane
• Biomass is approximately 80% water/20% solids
• Solid mass is approximately 90% organic/10% inorganic
• Rough chemical formula of C60H87O23N12P
Fall 2019 CHG 8191 C - Wastewater Treatment
• Only metabolize soluble compounds (may need to release
enzymes to break down solid compounds)
• Spirochaetes = spiral shape
• Strepto = chain forming
• Staphylo = bunch forming
• Gram-negative = Thick peptidoglycan cell wall wrapped around
an inner cytoplasmic membrane
• Contain a cell wall for structure and osmotic stability
• Contain a cytoplasmic membrane for metabolic regulation and
protection from the environment
13 / 26
 What’s in the Soup? Bacteria

From Riffat, R. (2012). Fundamentals of Wastewater Treatment and Engineering (1st edition). CRC Press. pg.42. Print;

Fall 2019 CHG 8191 C - Wastewater Treatment 14 / 26

 What’s in the Soup? Archaea/Protozoa
Archaea
• Unicellular, prokaryotic microorganisms • The methanogens (methanobacterium,
• Structurally and genetically distinct from bacteria methanosarcina, methanothrix, etc.) belong to this
• Many extremophiles belong to the archaea domain

Protozoa
• Mostly unicellular eukaryotes that lack cell walls
• Mostly aerobic heterotrophs
• Range in size from 1 – 800 µm (for wastewater
components)
• Consume bacteria, algae, and particulate matter
• Amoeba: Can cause amoebic dysentery
• Giardia lamblia: Parasite that causes giardiasis.
Coagulation-flocculation followed by filtration and
disinfection is required to kill them
• Cryptosporidium: causes cryptosporidiosis. Chlorination
does not work! Must be removed by coagulation-
flocculation and ozone disinfection

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 What’s in the Soup? Algae/Fungi/Viruses
Algae
• Single and multicellular photosynthetic organisms • Excessive algae cause taste and odour problems
• Size range from 5 – 100 μm • Note of huge concern for traditional wastewater
• Can be used in aerobic oxidation ponds to replenish O2 treatment but can be a cause of concern for the
receiving environment due to algal blooms

3−
CO
  2 + PO 4 + NH 3 + H 2 O 𝑠 𝑢𝑛𝑙𝑖𝑔h𝑡 𝐶𝑒𝑙𝑙𝑠 +O 2 + H 2 O
→

Fungi
• Multicellular, heterotrophic eukaryotes • Some fungi can be used to degrade solid wastes (like
• Most are obligate or facultative aerobes breaking down cellulose)
• Not a huge component of wastewater treatment

Virus
• Noncellular genetic element that requires a host cell • Viruses of concern in wastewater include polio, hepatitis
• Obligate intracellular parasites A, and enteroviruses
Fall 2019 CHG 8191 C - Wastewater Treatment
• Drinking water must remove > 99.99% of viruses

16 / 26
 Normal Phases of Growth
Lag Phase Period during which the microorganisms acclimate to
their environment. This involves activating cellular
processes and producing enzymes necessary to
metabolize and reproduce using nutrients from the
surrounding environment
Exponential Also known as saturated growth. Substrate is in such
abundance that growth rate is largely independent of
Phase substrate concentration and follows an exponential
curve
Transition Growth slows as substrate reaches levels low enough
that concentration now plays a role in growth kinetics
Phase
Stationary Substrate concentration is now low enough that growth
slows to the point that it equals the death plus
Phase endogenous respiration rate
Death Phase Substrate is now completely exhausted and the
microorganisms slowly eat themselves (endogenous
decay) and start to die

Most biological wastewater treatment processes operate

in the stationary to death phase region. Remember that
we are trying to bring substrate values down to 0!!!

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 Abnormal Phases of Growth
Extended Acclimation Toxic Environment

• Presence of inhibitory compounds • Presence of toxic compounds

• Key nutrients only available in small quantities
• Substrate is insoluble

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 The Major Kinetics
Monod Kinetics Haldane Kinetics Specific growth rate
(Substrate Inhibition) Maximum
Maximum specific
specific growth
growth rate
rate
Endogenous decay constant
Droop Kinetics Death/Endogenous Endogenous decay constant
Half saturation constant
(Luxury Uptake) Decay Kinetics Half saturation constant
Substrate inhibition constant

Droop Kinetics Death/Endogenous Substrate

Minimum inhibition
cell quotaconstant
Hydrolysis Reaction Rate
(Luxury Uptake) Decay Kinetics Bulk substrate concentration
Minimum cell quota
Biomass concentration
Bulk substrate
Particulate concentration
substrate
concentration
Biomass concentration
Hydrolysis Reaction Rate Cell quota →
Particulate substrate
Yield coefficient
concentration

Yield coefficient

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 Sample Kinetic Plots - Monod

Representative Monod Plot

1

0.9

0.8

0.7

  𝑆𝐶
Specific Growth Rate, µ

0.6

0.5

0.4
𝜇= 𝜇
´
(𝑆𝐶 + 𝐾 𝐶 )
0.3

0.2

0.1

0
0 2 4 6 8 10 12 14 16 18 20

Substrate Concentration, Sc

Fall 2019 CHG 8191 C - Wastewater Treatment 20 / 26

 Sample Kinetic Plots - Haldane

Representative Haldane Plot

0.7

0.6

0.5
Specific Growth Rate, µ

 𝜇= 𝜇 𝑆𝐶

( )
0.4
´ 2
𝑆𝐶
0.3
𝑆𝐶 + 𝐾 𝐶 +
( )
𝐾𝐼

0.2

0.1

0
0 2 4 6 8 10 12 14 16 18 20

Substrate Concentration, Sc

Fall 2019 CHG 8191 C - Wastewater Treatment 21 / 26

 Sample Kinetic Plots - Droop

Representative Droop Plots

1.2

0.8
Specific Growth Rate, µ

  𝐾𝑄
0.6
X = 0.1 X = 0.5 (
𝜇= 𝜇´ 1−
𝑄 )
0.4
X = 2.0 X = 10.0

0.2

0
0 2 4 6 8 10 12 14 16 18 20

Substrate Concentration, Sc,internal

Fall 2019 CHG 8191 C - Wastewater Treatment 22 / 26

 Sample Kinetic Plots - Hydrolysis

Representative Hydrolysis Plot

1.2

0.8
Specific Growth Rate, µ

  ( 𝑋𝐶 / 𝑋 )
0.6
𝜇= 𝜇
´
( ( 𝑋𝐶 / 𝑋 )+ 𝐾 𝐶 )
0.4
X = 0.1 X = 0.5

0.2 X = 2.0 X = 10.0

0
0 2 4 6 8 10 12 14 16 18 20

Substrate Concentration, Xc

Fall 2019 CHG 8191 C - Wastewater Treatment 23 / 26

 Sample Model Derivation
• Hydrolysis
  ( 𝑋𝐶 / 𝑋 )
 𝑋 𝐶 𝑋 𝑆𝐶
→
𝑟 𝑋 =𝜇
´𝑋 𝐶 𝐶
( ( 𝑋 𝐶 / 𝑋 )+ 𝐾 𝑋 𝐶
) 𝑋

• Luxury Nitrogen Uptake

 𝑆 𝑁 𝑋 𝑆 𝑁 ,𝑖𝑛𝑡
  𝑆𝑁
→
𝑟 𝑆 = ´𝜇𝑆𝑁 𝑁
( 𝑆𝑁 + 𝐾 𝑆 𝑁
) 𝑋

• Biomass Growth
  𝑆𝐶 𝐾𝑄
 𝑆 𝐶 +𝑄 𝑋𝑋
→
𝑟 𝑋 = ´𝜇 𝑋
( 𝑆𝐶 + 𝐾 𝑆 𝐶
)( 1−
𝑄
𝑋 )
• Death/Endogenous Decay
 𝑋 𝑋 𝑋𝐶  𝑟
→ 𝐷 =𝑘 𝑑 , 𝑋 𝑋

Fall 2019 CHG 8191 C - Wastewater Treatment 24 / 26

 Sample Model Derivation
 
𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛=𝐼𝑛−𝑂𝑢𝑡 +𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 −𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛
• Assume perfect mixing
• Assume constant density system
• Assume physical and chemical properties are constant

dሺ𝑉𝑋𝐶 ሻ d𝑉
= 𝑄𝑖𝑛 𝑋𝐶,𝑖𝑛 − 𝑄𝑜𝑢𝑡 𝑋𝐶 − 𝑟𝑋𝐶 𝑉 + 𝑌𝑋𝐶 Τ𝑋 𝑟𝐷 𝑉 = 𝑄𝑖𝑛 − 𝑄𝑜𝑢𝑡
dt dt
d𝑋𝐶 d𝑉
𝑉 + 𝑋𝐶 = 𝑄𝑖𝑛 𝑋𝐶,𝑖𝑛 − 𝑄𝑜𝑢𝑡 𝑋𝐶 − 𝑟𝑋𝐶 𝑉 + 𝑌𝑋𝐶 Τ𝑋 𝑟𝐷 𝑉 d𝑋𝐶 𝑄𝑖𝑛 ൫𝑋𝐶,𝑖𝑛 − 𝑋𝐶 ൯
dt dt = − 𝑟𝑋𝐶 + 𝑌𝑋𝐶 Τ𝑋 𝑟𝐷
d𝑋𝐶 dt 𝑉
𝑉 + 𝑋𝐶 ሺ𝑄𝑖𝑛 − 𝑄𝑜𝑢𝑡 ሻ= 𝑄𝑖𝑛 𝑋𝐶,𝑖𝑛 − 𝑄𝑜𝑢𝑡 𝑋𝐶 − 𝑟𝑋𝐶 𝑉 + 𝑌𝑋𝐶 Τ𝑋 𝑟𝐷 𝑉 d𝑆𝐶 𝑄𝑖𝑛 ൫𝑆𝐶,𝑖𝑛 − 𝑆𝐶 ൯
dt = + 𝑌𝑆𝐶 Τ𝑋𝐶 𝑟𝑋𝐶 − 𝑌𝑆𝐶 Τ𝑋 𝑟𝑋
d𝑋𝐶 𝑄𝑖𝑛 ൫𝑋𝐶,𝑖𝑛 − 𝑋𝐶 ൯ dt 𝑉
= − 𝑟𝑋𝐶 + 𝑌𝑋𝐶 Τ𝑋 𝑟𝐷
dt 𝑉 d𝑆𝑁 𝑄𝑖𝑛 ൫𝑆𝑁,𝑖𝑛 − 𝑆𝑁 ൯
= − 𝑟𝑆𝑁
dt 𝑉
d𝑆𝑁,𝑖𝑛𝑡 𝑄𝑖𝑛 𝑆𝑁,𝑖𝑛 𝑡
=− + 𝑟𝑆𝑁 − 𝑌𝑆𝑁 Τ𝑋 𝑟𝑋
dt 𝑉
d𝑋 𝑄𝑖𝑛 𝑋
=− + 𝑟𝑋 − 𝑟𝐷
dt 𝑉

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 Dissolved Oxygen Sag Curve
A river or pond is nature’s bioreactor!!!  • Dissolved Oxygen Deficit

• Reaeration Rate

• Oxygen Consumption

• Dissolved Oxygen Deficit Balance

• Assuming first order reactions

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