1. Biological Technology for Resource Recovery from Wastewater and Wasted biosolids (R2W2)
Joonhong Park

3. Chemical Reactions and Energy
Homogenous reactions are governed by relations which require that certain entropy, enthalpy, and energy balances be obeyed among the components or species participating in transformation processes that occur within a single phase.
* Transformation via electron transfer (oxidation-reduction reaction)
- Ionic reaction (give-and-take)
- covalent reaction (sharing)
- coordinate-covalent reaction (forming complexes)
* Transformation via proton (H+) transfer (in water)
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5. Fundamentals of Transformation Processes
3.A Governing concepts
- Stoichiometry: material balance
Chemical equilibrium (thermodynamics): materials and energy distribution between phases and between species
- Kinetics: how fast?
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6. CEE3330 Joonhong Park Copy Right
Stoichiometry
The application of the principle of material balance to a chemical transformation.
bR1 + cR2 => mP1 + nP2
here R1 and R2: reactants
P1 and P2: products
b, c, m, and n: stoichiometric coefficients
Meaning: b molecules of R1 combine with c molecules of R2 to form m molecules of P1 and n molecules of P2
RULE: A chemical reaction must conserve (i) the number of atoms for each element involved in the reaction and (ii) the electrical charge associated with ions.
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7. Thermodynamics/Gibbs Free Energy
of species participating
in a reaction (G)
Free energy
Activation energy (forward rxn)
Reactants ΔG
Change in Gibbs free energy
Products
Progress of reaction
ΔG = Σ Gf,i (products) - Σ Gf,i (reactants)
ΔG < 0: thermodynamically favorable.
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8. Ox-Red Reaction: Oxidation State
Definition: the net electrical charge that it possesses or appears to possess.
An important step in identifying whether a particular transformation process is a redox reaction.
Rules
(1) the oxidation state of an uncharged, uncombined element, whether in atomic or molecular form (as in C, N2 or O2), is zero. The oxidation state of an atomic ion is equal to its charge (ex. Na+, Cl-).
(2) the oxidation state of a compound is equal to the sum of the oxidation states of the respective atoms within the compound.
(3) the oxidation state of a compound is equal to the net electrical charge on the compound. For neutral compounds, the oxidation state is zero. For ions, the oxidation state is equal to the charge of the ion, including the sign.
(4) the oxidation state of oxygen in most compounds is -2
(5) the oxidation state of hydrogen in most compounds is +1.
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9. CEE3330 2008 Joonhong Park Copy Right
Oxidation State
Example) Oxidation states of elements in compounds
Oxidation state of S in sulfuric acid (H2SO4)?
Solution:
Sulfuric acid is a neutral compound. So its oxidation state must be zero (Rule #2 and3). H has oxidation state of +1, and O -2 (Rules $4 and 5). Therefore,
2(+1) + Oxidation state of S + 4(-2) = 0
Oxidation state of S = +6
cf) The oxidation of S in SO42- ?
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10. Oxidation States of Environmentally Important Elements
Species N -3 +2 +3 +4 +5
NH3 N2 NO
NO2-
NO2
NO3- S -2 +6
H2S
SO2
SO42- Cl -1 +1 +7
Cl-
Cl2
HOCl
HClO4
Element
Oxidation state
Species C -4 +2 +4
CH4
C (soot, graphite) CO
CO2 O -2 -1
All compounds
H2O2 O2 H +1 H2 H+
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11. Oxidation-Reduction Reaction
A species is oxidized when its oxidation state increased by losing one or more electrons from its outer shell.
A species is reduced when its oxidation state decreased by gaining one or more electrons.
The oxidation of a species can be accomplished only by a reduction of equal magnitude in another species.
Ex) Overall RXN: CH4 + 2O2 = CO2 + 2H2O (Methane combustion)
Half-RXN for Methane Oxidation: CH4 + 2H2O = CO2 + 8H+ + 8e- (1)
O.S. of C: => +4
Half-RXN for O2 Reduction: 2O H+ + 8e- = 4H2O (2)
O.S. of O: => -2
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12. CEE3330 2008 Joonhong Park Copy Right
Theromdyanmics: Energy scale for various oxidation/reduction couples 60 50 40 30 20 10
-10
-20
-30
-40
-50
-60
-70
-80
∆Go’
(kJ/e- eq)
0.25CO2 + H+ + e- = (1/24)C6H12O H2O (Glucose/CO2)
H+ + e- = 0.5H2 (Hydrogen/H+)
1/6CO2 + H+ + e- = (1/12)CH3CH2OH H2O (Ethanol/CO2)
1/8CO2 + 1/8 HCO3- + H+ + e-
= 1/8 CH3OO- + 3/8H2O (Acetate/CO2)
1/8 CO2 + H+ + e- = 1/8 CH H2O (methane/CO2)
1/8 SO /16H+ + e-
= 1/16 H2S + 1/16 HS H2O (sulfide/sulfate)
1/5 NO3- + 6/5H+ + e- = 1/10 N2 + 3/5H2O (N2/Nitrate)
Fe3+ + e- = Fe2+ (Fe[II]/Fe[III])
1/4O2 + H+ + e- = 0.5H2O (H2O/O2)
½ CCl2CCl2 + ½ H+ + e- = ½ CHClCCl2 + ½ Cl- (PCE)
Electron
Donors
Acceptors
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Kinetics
aA + bB => cC + dD ( at a given temperature, T)
Reaction Rate
Rf = - (1/a) (d[A]/dt) = -(1/b)(d[B]/dt) = (1/c)(d[C]/dt) = (1/d)(d[D]/dt)
In general, Rf = σ (- ΔG)
Rate Laws
Rf = kf [A]α[B]β here kf = rate constant
In elementary rxn, Rf = kf [A]a[B]b
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14. Photosynthesized Biomass & Energy
Photosynthesis (dG > 0; feed stock):
aCO2 + bNO3- + cHPO42- + dH+ + eH2O
=> C106H263O110N16P1 (carbohydrate, lipid, protein) + fO2
Aerobic Oxidation (dG << 0; heat energy):
C106H263O110N16P1+ αO2 => βCO2 + γH2O
Anaerobic Fermentation (dG < 0; heat energy + fuel):
C106H263O110N16P1 => alcohol (CxHy-OH, i.e., ethanol)
alcohol => acid (CxHy-OOH, i.e., acetate)
acid + CO2 => CH4
Methanogenesis (dG <0; heat energy + fuel):
H2 + CO2 => CH4
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15. Biochemical Processes in Anaerobic Digestion
Proteins Carbohydrates Lipids
Amino acids Simple sugars Glycerol
/LCVAs
Methane
Fermentation
Hydrogen/CO Acetate SCVAs
Methane Methane Acetate
CO2
Acid formation
Methanogenesis

16. Photosynthesized Biomass as Feedstock
1세대 유기성자원: 콩, 유채 등 => 바이오디젤
옥수수 등 => 에탄올
2세대 유기성자원: 폐 목재, 짚 등 => 에탄올
3세대 유기성 자원: 미세조류 => 바이오디젤, 수소,
에탄올
식량과 경쟁
Cellulose/Lignin 난분해
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17. Comparison of some sources of biodiesel
Photosynthesizing Microalgae as New Biomass Feedstock
Algae - Sustainable Energy & Material
Comparison of some sources of biodiesel
(Chisti, 2007)
Crop
Oil
yield
(L/ha)
Land area
needed
(M ha)
Corn
172
1540
Soybean
446
594
Canola
1,190
223
Jatropha
1,892
140
Coconut
2,689 99
Oil palm
5,950 45
Microalgaea
136,900 2
Microalgaeb
58,700
4.5

18. 미세조류에서 바이오디젤 생산 전 과정의 개요도
Cultivation
Dehydration
Lipid Extraction
Electricity
Separates algae from water, dewaters, dries
High Speed Centrifugal spray dry algae tower
Physical Pressure
Biodiesel Production
Biodiesel Production by Transesterification

20. Green Chemistry for Algal Biodiesel Production
Dimethyl Carbonate (DMC) is a very promising alternative as a acyl acceptor for biodiesel production from algal lipid because of its eco-friendly properties.
Dimethyl carbonate (DMC) is regarded as eco-friendly chemical in the aspects of chemical reactivity and physical properties. (Fabbri et al., 2007; Su et al., 2007, 2009).
DMC is recently VOC-exempted by Environmental Protection Agency (EPA).
Dimethyl Carbonate
Most important thing is…
No glycerol is produced in the transesterification reaction of algal lipid and DMC in the process of biodiesel production.

21. Environment-friendly solvent choice (Woo, Sung-Geun)
DMC is a not only acyl acceptor but also effective solvent.
DMC is also able to be employed to extract algal lipid instead of other solvent.
Since DMC and lipid are miscible very well, no further co-solvent will be needed and after transesterification reaction, another solvent for dissolving reaction products are not required, because reaction products are easily dissolved in DMC.
Conventional
Algae
Algal
Lipid
FAME
(Bio-diesel)
Extraction
Transesterification
Hexane (or others)
Methanol
Proposed
FAME(Bio-diesel)
Algae
Algal
Lipid
Extraction
Transesterification
DMC

22. Interaction between microalgae and bacteria

23. CEE3330 Joonhong Park Copy Right
유기성 폐자원
가연성 폐기물 (종이, 플라스틱 등)
음식물 폐기물
하수처리장 슬러지
축산분뇨 폐기물
주: 2013년 부터 음식물폐기물, 하수처리장 슬러지, 축산분뇨의 해양투기 금지
기존 위생매립장에는 음식폐기물, 슬러지, 축산분뇨 반입금지
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24. CEE3330 Joonhong Park Copy Right
유기성 폐자원 재활용기술
연소 및 열 회수
가연성 vs. 비가연성 분리 / 유가자원 회수
생물학적 재활용 기술 (혐기성 소화, 퇴비화 및 비료화)
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25. 자원회수시설 폐기물 배출, 운반, 처리공정 배 출 운 반 처 리 생활폐기물 폐기물 폐열 소각재 일반 가정 등 운반업체
적정처리
(감량, 무해, 안정화) 폐열
에너지회수
(냉난방, 전기 생산)
소각재
재활용
(재활용 벽돌 등)
폐기물 배출, 운반, 처리공정
배 출
운 반
처 리
일반 가정 등
운반업체
자원회수시설 반입
투입(소각로) 소각
대기 배출
수거 및 운반
폐기물 배출
(종량제봉투 사용)
유해가스 처리

26. 쓰레기 1톤의 연료대체 효과 원유 1.57배럴 휘발유 292ℓ 17.3일 난방공급 쓰레기 1톤 소각
쓰레기 1톤(발열량 2.7 Gcal) 소각으로
2.27Gcal의 열 생산이 가능하며,
이는 휘발유 292ℓ, 원유 1.57배럴의
연료대체 효과가 있음.
32평 아파트 한가구에 17.3일
난방할 수 있는 열량이다!
원유 1.57배럴
= 원유 250ℓ
휘발유 292ℓ
• 590,000원
• 서울-부산 9회 운행
(32평아파트 기준)
17.3일 난방공급
한가구
2.27Gcal 열량 생산
쓰레기 1톤 소각

27. Composting (Aerobic Process)
Decomposition in tunnels with automatic tunnel discharge equipment

28. Anaerobic Digestion (dry process with solid waste)
Digestion (anaerobic treatment), dry digestion
Dry digestion can be designed as a partial or full stream process with inoculation and turning. Full stream digestion requires a post dewatering. Afterwards the material is treated in post decom-position for the storage or in a landfill. The treatment period in a dry digestion needs three weeks
Gas production rate m3/Mg waste
Use of the fermentation gas

29. Anaerobic Digestion (wet process with high-organic sludge)
Digestion (anaerobic treatment), wet digestion
At first the material is wet-mechanically prepared then transferred in the two-step full-stream digestion which is followed by the wet-aerobic stabilisation through dewatering and thermal drying. The treatment period in the wet digestion needs 3 weeks, the aerobic stabilisation additional 5 days.

30. Top 5 World’s Future Issues
Energy
Water
Food
Health
Environment

31. Resource Recovery from Wastewater
Energy resource chemicals (methane, H2, N2O, electricity)
Nutrient fertilizers (N, P)
Value-added chemicals (medicines, food and/or additives, polymers for industrial purposes)

32. Current wastewater treatment system
Home
-toilet (black water; high BOD)
-bathroom(grey water; low BOD)
-kitchen (food waste + water; low BOD in Korea)
Waste Water
(BOD= 200 mg/l)
Storm water
(우수/오수 합류관거)
Aerobic Activated Sludge Process
in Wastewater Treatment Plant
(aeration cost > 60% of total energy cost)
Effluent
Influent
(BOD < 200 mg/l)
Wasted
Sludge
Problems: energy consuming system without resource recovery

33. Alternative way to RR from WW: Concentration and Anaerobic Digestion
Home (High BOD)
-toilet black-water
-food waste
High-Strength
Waste Water
(BOD > 10,000 mg/l)
Concentration by Membrane or
Reuse by WWT
(중수도)
Home (Low BOD)
-bathroom grey-water
-kitchen grey-water
No storm water
(우수/오수
병류관거)
Post-Treatments
(N, P removal from effluent)
Anaerobic Digestion
(methane production)
Influent
(BOD < 10,000 mg/l)
Disadvantage: Long hydraulic retention time (HRT) and effluent post-treatment required

34. Typical N Removal in Wastewater
Organic N
NH3 / NH4+
NO2-
NO3-
Nitrification (Aerobic Oxidation)
Denitrification (Anaerobic Reduction) N2
N2O NO
NO2-
ATMOSPHERE
ATMOSPHERE
(Green House Gas)

35. New Potential Energy Source, N2O
Exothermic Enthalpy of N2O decomposition(Propellant)
Nitrous oxide Jagur XJS – Top Gear
Powerful oxidant in combustion reactions (Oxidant)
VS.

36. Bioelectrochemical System (BES)
Hamelers et al., 2010, Appl Microbiol Biotechnol.; Pant et al., 2012, RSC Adv

37. CEE3330 2008 Joonhong Park Copy Right
Theromdyanmics: Energy scale for various oxidation/reduction couples 60 50 40 30 20 10
-10
-20
-30
-40
-50
-60
-70
-80
∆Go’
(kJ/e- eq)
0.25CO2 + H+ + e- = (1/24)C6H12O H2O (Glucose/CO2)
H+ + e- = 0.5H2 (Hydrogen/H+)
1/6CO2 + H+ + e- = (1/12)CH3CH2OH H2O (Ethanol/CO2)
1/8CO2 + 1/8 HCO3- + H+ + e-
= 1/8 CH3OO- + 3/8H2O (Acetate/CO2)
1/8 CO2 + H+ + e- = 1/8 CH H2O (methane/CO2)
1/8 SO /16H+ + e-
= 1/16 H2S + 1/16 HS H2O (sulfide/sulfate)
1/5 NO3- + 6/5H+ + e- = 1/10 N2 + 3/5H2O (N2/Nitrate)
Fe3+ + e- = Fe2+ (Fe[II]/Fe[III])
1/4O2 + H+ + e- = 0.5H2O (H2O/O2)
½ CCl2CCl2 + ½ H+ + e- = ½ CHClCCl2 + ½ Cl- (PCE)
Electron
Donors
Acceptors
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38. Nutrient Recovery
Phosphorus (P) mining resource will be completely consumed within 40 years.
Magnesium ammonium phosphate (struvite; MgNH4PO4·6H2O) formation from wastewater has been regarded as nutrient recovery since Booker et al, 1999.
In Swiss, ash from combustion of biomass
is being stored in designated landfills until
P mining resource will be completed.
N/P recovery from no-mix toilet [source-separated urine]: urine contains most of the nutrients in domestic wastewater but makes up less than 1% of total wastewater. In addition, better ways to remove organic micropollutants from human metabolites (see Maurer et al., 2006; Gethke et al., 2007; )
<Crystal structure of struvite>

39. New Toilet - 그 진지함과 진화
Conventional Toilet => No Mix => Vacuum =>
No Mix Vacuum => Future??

40. Importance of microbial ecology in resource recovery
BOD/nutrients in WW and Biosolids
Metabolism by Microbial Communities
Energy Resource Materials
-CH4, H2
-N2O
-Biodiesel
Value-added materials
Succinate/pyruvate/butylate
poly-hydroxylbutylate (PHBs)
Omega-3-FA etc.
VS.
Eco-physiological understanding linkages between the renewable material metabolisms S
LCA based Optimization
(Public health, Environ, Cost, Energy, GHG, Residual Soils, Resource Recovery)

41. E-W-F Nexus: Urban Eco-farming
Vertical Farming
No Soil Farming
Indoor Light
Hydrogel film