Lecture Notes on Applied Thermal Engineering 2011

A li d Th
Applied Thermall EEngineering
i i

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Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
 Part 1 Combustion Engineering
Chapter1 Combustion Fundamentals
Ch
Chapter 2 Combustion
C b i and d Thermochemistry
Th h i
Chapter 3 Introduction to Engine Combustion
Ch
Chapter 4M
Mass T
Transfer
f
Chapter5 Chemical Kinetics
Ch
Chapter 6 Some
S IImportant Ch
Chemical
i l Ki
Kinetics
i
Chapter 7 Governing Equations for Reacting Flows
Ch
Chapter 8 Ignition
I i i anddE
Extinction
i i

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 Lecture Notes on Applied Thermal Engineering 2011

Ch t 1
Chapter
Combustion Fundamentals
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Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
 Motivation to Study Combustion Ref : An Introduction to Combustion, by S.
R. Turns, Chapter 1

■ Combustion
C b i and d iits controll are essential
i l to our existence
i
- Energy source :
About 85% of energy came from combustion source
- Use of combustion :
Electricity generation
Transportation system
Industrial process : metals refining, glass melters, dryer, cement manufacturing
Incineration
- Environmental pollution
Partially burned hydrocarbons (UHC)
Nitrogen oxides (NOx)
Carbon monoxide (CO)
Sulfur Oxides (SOx)
Particulate matter (PM)
- Energy Conversion
Combustion Chamber, Boiler, Furnace Engine, Gas Turbine

Chemical Energy Thermal Energy Mechanical Energy

Power Utilization Machine

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 Combustion Ref : An Introduction to Combustion, by S.
R. Turns, Chapter 1

• 불의 발견
• 청동기/철기 시대 : 무기, 농기구 (요로)
• 산업혁명 : 동력발생
• 우주시대 : 로켓 등 추진기관
• 정보혁명 : 광섬유 등의 제조
• 신물질 : 다이아몬드 등
화학반응을 수반하는 유동, 열 및
물질전달 현상

에너지 에너지
(화학적) 연소공학 (열적, 기계적)
환경, 공해 (산성비, 스모그, 오존 등), 지구온난화

연소효율 청정연소

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 Definition of Combustion Ref : An Introduction to Combustion, by S.
R. Turns, Chapter 1

(1) Definition
D fi i i (f
(from Webster's
W b ' di dictionary)
i )
- " Rapid oxidation generating heat, or both light and heat; also, slow oxidation accompanied by little heat
and no light"

(2) Main objective

- Combustion transforms energy stored in chemical bond to heat that can be utilized in variety of ways

(3) Background required

- Thermodynamics, Chemical kinetics, Fluid mechanics, Heat and mass transfer, Turbulence

(4) Governing equations for combustion problems

- Conservation of mass (Continuity equation)
- Conservation
C ti off momentumt
- Conservation of energy (with Radiative heat loss)
- Conservation of molecular species

(5) Theoretical formulation and solution technique requires

- Mathematics
- Numerical methods
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 Combustion Mode and Flame Types Ref : An Introduction to Combustion, by S.
R. Turns, Chapter 1

(1) Flame mode

- A thin zone of intense chemical reaction propagates
through the unburned fuel-air mixture.
- This thin reaction zone is what we commonly refer to as a
flame.
- A combustion wave that travels subsonically is called a
deflagration.
g
- Example of flame mode : a normal spark-ignition engine

((2)) Non-flame
o a e mode ode
- Rapid oxidation reactions occur at many locations within
the unburned gas, leading to very rapid combustion
throughout the volume
- This volumetric heat release in an engine is called
autoignition.
- A combustion wave that travels supersonically is termed a
d
detonation.
i
- Examples of non-flame mode: a knocking in spark-ignition
engine, a compression-ignition engine

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 Classification of Flames (1/2) Ref : 연소공학, 정석호, NGV 연소공학 교
육과정 교재

- Mixing of fuel and oxidizer : Diffusion(Nonpremixed) and Premixed combustion

★
예혼합화염 확산화염
연료/산화제 초기에 분자적으로 초기에 분리, 대류/확
공급 혼합 산 혼합
제어 메커니 화학반응율/확산 열확산/물질확산
즘
화염 위치 특 전파되는 파동특성 화염강도 최대지점에
성 스스로 조절
희박화학종 완전
완전소 연 산화제 완전 소
연료/산화제
연료/산화제
모, 과농화학종 누 모
소모특성
출
유한반응율 무한반응율 (화염면
해석
극한)
Detonation Candle flame, Gas
Gasoline burner, Droplet
Combustion combustion, Jet
예
flame, Boundary layer
burning, Diesel
Combustion

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 Classification of Flames (2/2) Ref : 연소공학, 정석호, NGV 연소공학 교
육과정 교재

- Structures of combustion wave : Deflagration and Detonation

- Phase conditions : Homogeneous and Heterogeneous combustion
- Stream conditions : Laminar and Turbulent flame
- Temporal variation : Steady and Non-steady
Non steady flame
- Spatial variation : Stationary and Traveling flame

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 Chemical Reactions Ref : 공업열역학, by 최병륜, 장영준, 오상
헌, 김덕줄, Chapter 12

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 Applications – Combustion

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 Lecture Notes on Applied Thermal Engineering 2011

Ch t 2
Chapter
Combustion and Thermochemistry
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Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
 Mole Ref : 일반화학, 부산대학교 출판부

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 Equation of State Ref : Introduction to Engineering Thermodynamics, by R.
Sonntag, Chapter 3

¾ Ideal Gas

Pv = nRT , Pv = RT
Where,
n : number of moles , [ kmol ]
= m MW
R : Universal
U i l Gas
G C Constant
t t
= 8.314 kJ kmol ⋅ K
= 8.314 kPa ⋅ m 3 kmol ⋅ K
= 0.08314
0 08314 bar ⋅ m 3 kmol ⋅ K
= 1.986 Btu lbmol ⋅ R
= 10.73 psia ⋅ ft 3 lbmol ⋅ R
= 1545 ft ⋅ lbf lbmol ⋅ R
R : Specific Gas Constant
= R MW
PV = mRT (Q nR = n ⋅ MW ⋅ R = mR )
Pv = RT (Q V m = v )
P = ρ RT (Q 1 v = ρ )

• The
Th id
ideall gas equation
ti off state
t t iis a good
d approximation
i ti att llow d
density
it
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Specific Heat (C) Ref : Thermodynamics – An Engineering Approach, by
Cengel and Boles, Chapter 4

• Specific Heat (比熱) : The amount

amo nt of heat required
req ired per unit
nit mass to raise the temperat
temperature
re
by one degree, [J/kgK]

Q δ Q = dU + δ W
= dU + PdV
{
=0

Q δ Q = dU + δ W
= dU + PdV
= d (U + PV )
= dH
Constant-volume and constant-pressure specific heats are thermodynamic properties
→ Values are tabulated in Appendix A

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Enthalpy (H) Ref : Thermodynamics – An Engineering Approach, by
Cengel and Boles, Chapter 4

Assume (1) quasi-equilibrium

quasi equilibrium constant-pressure
constant pressure process
(2) no changes in KE and PE
(3) taking the gas as control volume
2 2
From the 1st law, , and
1 Q 2 = U 2 − U 1 + 1W 2 1W 2 = ∫ PdV = P ∫ dV = P (V2 − V1 )
1 1

∴ 1 Q 2 = U 2 − U 1 + P2V2 − P1V1 = (U 2 + P2V2 ) − (U 1 + P1V1 )

Heat transfer is obtained from the change in the quantity between
the initial (1) and final (2) states → ∴ point function
U + PV

H ≡ U + PV and
d h ≡u+P
Pv
Enthalpy is one of the independent thermodynamic properties of a pure
substance → Values are tabulated in Appendix in your Thermodynamics
Textbooks

¾ Internal energy (U) : inter-molecular translational, rotational, and

vibrational energy

• sensible energy : kinetic energy of molecules, heat

• latent energy : phase change (bond energy)

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Mass Fraction and Mole Fraction Ref : Thermodynamics – An Engineering Approach, by
Cengel and Boles, Chapter 13

• Mixture Mass and Mole

k k

mm = ∑m
i=1
i
and Nm = ∑N
i=1
i

• Mass Fraction and Mole Fraction

k k

Yi = m i m m and X i = N i N m → ∑ Y = 1 and ∑ X
i=1
i
i=1
i =1

• Apparent
A Molar
M Mass
M and Gas
G C Constant

m
Mm = m =
∑m = ∑N M =∑ N
i i i
i
Mi = ∑X M i i
Nm N mN N m m
Ru
Rm =
Mm
mm mm mm 1 1
Mm = = = = =
Nm
∑N ∑ i
mi
Mi ∑
mi 1
mm M i ∑
Yi
Mi
mi NiMi N Mi Mi
∴ Yi = = = i = Xi
mm N m M m N m M m Mm

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Properties of the Gas Mixture Ref : Thermodynamics – An Engineering Approach, by
Cengel and Boles, Chapter 13

• Extensive Property
k k k

Um = ∑U = ∑ m u = ∑ N u
i=1
i
i=1
i i
i=1
i i

k k k

Hm = ∑H =∑m h =∑N h
i=1
i
i=1
i i
i=1
i i

k k k

Sm = ∑S = ∑m s = ∑N s
i=1
i
i=1
i i
i=1
i i

• Intensive Property
k k

um = ∑ Y u [kJ kg ] and
i=1
i i um = ∑ X u [kJ kmol ]
i=1
i i

k k

hm = ∑ Y h [ kJ kg ] and
i i hm = ∑ X h [ kJ kmol ]
i i
i =11 i =11
k k

sm = ∑ Y h [kJ kgK ] and

i=1
i i sm = ∑ X s [kJ kmolK ]
i=1
i i

• Specific Heat
k k k k
C v ,m = ∑YC
i=1
i v ,i
and C v ,m = ∑XC
i=1
i v ,i C p ,m = ∑YC
i=1
i p ,i
and C p ,m = ∑XC
i=1
i p ,i

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 Hydrocarbon Fuel Ref : Thermodynamics – An Engineering Approach, by
Cengel and Boles, Chapter 14
• Basic Hydrocarbon Families

• Nomenclature
N l t • Molecular
M l l St Structure
t

• 휘발유 : 옥탄(C8H18)
• 디젤유 : 도데칸(C12H26)
• 천연가스 : 메탄(CH4) – CNG, LNG
• 액화석유가스(LPG) : 프로판(C3H8) 90% 이상

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 Combustion and AF Ratio • Air-fuel ratio (AF, A/F) AF =
m air
m fuel
• Methane Combustion
Reactants Products
64748 644744 8
CH 4 + 2O 2 → CO 2 + 2H 2 O

• Mass Conservation

• 1 kmol O2+3.76 kmol N2=4.76 kmol air

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 The Combustion Process Ref : Thermodynamics – An Engineering Approach, by
Cengel and Boles, Chapter 14

• Complete Combustion

★
• Theoretical Air : 연료를 완전연소시키기 위한 최소 공기량
• Theoretical Combustion

• Excess Air

• Deficiency Air
★
• Equivalence Ratio
( A F )stoichiometric (F A )real
Φ= =
( A F )real (F A )stoichiometric
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 Enthalpy of Formation
Ref : Thermodynamics – An Engineering Approach, by
Cengel and Boles, Chapter 14

• Standard Reference State

• Enthalpy of Combustion, hC
25 °C , 1 atm → h ° , u °
주어진 온도와 압력에서 정상유동 연
소과정 동안 1 kmol (1 kg)의 연료가 • Heating Value, LHV and HHV
완전연소하였을 때 방출되는 열량

Q = H prod − H react = −393, 520 kJ kmol

• Enthalpy of Formation, h f° HHV = LHV + mh fg ( ) H2O

• Enthalpy at any T and P

( )
hT , P = h f°
14 298 K ,0.1MPa
4244
+ Δh
3 144
( )
298 K ,0.1M Pa → T , P
42444 3
enthalpy at 25 캜 ,1 atm sensible enthalpy relative
to 25 캜 ,1 atm
=h −h °
h f° = −393, 520 kJ kmol

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 Enthalpy of Formation – Example Ref : Thermodynamics – An Engineering Approach, by
Cengel and Boles, Chapter 14

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1st Law Analysis of Reacting Systems
Ref : Thermodynamics – An Engineering Approach, by
Cengel and Boles, Chapter 14
Q − W = H prod − H react
H prod = ∑ N (h + h − h )
P
°
f
°
p

H react = ∑ N (h + h − h )
r
°
f
°
r

h : 형성엔탈피
°
f
h : 주어진 상태에서의 현열엔탈피
h o : STP 상태에서의 현열엔탈피

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 Adiabatic Flame Temperature Ref : Thermodynamics – An Engineering Approach, by
Cengel and Boles, Chapter 14

★단열화염연도 : 주위로의 열손실 없이 완전연소

를 통하여 얻을 수 있는 최대 온도

∴ H prod = H react
∴ ∑ ( N P h f° + h − h ° ) p

= ∑ N (h r
°
f + h − h° )
r

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Activation Energy, E A Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 4

Activation energy is the energy required for the reaction to occur; that is,
it is the energy required to move the reactants over the energy barrier in
order for reaction to begin.

For exothermic reaction

For catalytic reaction

For endothermic reaction

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Arrhenius Plot Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 4

Chemical reaction rate : Arrhenius Law

k (T ) = A exp ( − E A R uT )
taking natural logarithm on both sides
EA
ln k = ln A −
R uT
Experimentally, E A is found by plotting measured values of
against ln k and computing the slope of the best–fit straight
line through the data points (slope 1 T = − E A R u).
After E A is obtained, the factor A in the Arrhenius
equation may be calculated, using this equation and the
measured values of k .

The Arrhenius equation generally cannot describe the

combustion process over a wide temperature range. For
example, a set of reactions which matches with test data at
l
low temperatures
t t may provide
id erroneous results
lt att hi
high
h
temperature, and vise versa.

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 Appendix
Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 6

Some Useful Relationships among

Mass Fractions
Mole Fractions
Molar Concentrations
and
Mixture Molecular Weights

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 Lecture Notes on Applied Thermal Engineering 2011

Ch t 3
Chapter
Introduction to Engine Combustion
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Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
 Engine Combustion
가솔린 엔진 디젤 엔진
혼합기 예혼합기 비 예혼합기
주요
난류 예혼합화염 난류 확산화염
메카니즘
기본
층류 예혼합화염 액적/분무 연
연소
연소현상
점화 스파크 자발화
이상 자발화, 노킹, 실화,
노킹
연소현상 폭발, 초음속연소파

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 Combustion and Knock in SI Engine (1/2) Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 6

¾ End gas spontaneously ignites, because it has been compressed to high temperature.
¾ Knock depends on engine variables, fuel variables, and ambient conditions.
¾ Knock occurs primarily at WOT – highest pressure and temperature inside the engine.
¾ To avoid knock with gasoline,
gasoline the engine compression ratio is limited to between 9 and 10
10.5.
5 Significant efficiency
gains are possible if the compression ratio could be raised.
¾ Knock sensors and a feedback control are increasingly used to adjust the spark timing so that the engine can operate
close to its knock limit.

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 Combustion and Knock in SI Engine (2/2) Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 4

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 Diesel Combustion – Example Ref : 이기형, 현대자동차 위탁연구결과
보고서, 한양대학교, 2003. 12.

Flame Visualization in DI Diesel Engine

분사압: 50MPa

Cavity

6.13 6.88 9.99 15.17 19.68

Bore 분사압: 100MPa

4.40 5.90 6.65 7.41 9.67

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 Diesel Combustion Characteristics (1/3) Ref : DieselNet, 2002, Technical Notes,
“Combustion in Diesel Engines,”

■ Fuel/Air Distribution in the Fuel Spray of a DI Diesel

¾ Local air-fuel ratio
¾ Near the downstream edge of the spray, most of the droplets will be
completely evaporated before ignition → premixed fuel vapor and air

■ Lean
L Flame
Fl R
Region
i (LFR)
¾ between the core and downstream edge of the spray, where AF may
vary 0~∞
¾ Ignition nuclei → independent nonluminous flame front propagation
¾ NO is formed at high local concentrations as combustion proceeds to its
completion
■ Lean Flame-Out Region (LFOR)
¾ Near the outer edge of the spray, where the mixture is too lean to
ignite or to support stable combustion
¾ Fuel decomposition → lighter HC molecules, Partial oxidation →
aldehydes, oxygenates
¾ In the zone where LFOR and LFR meet
meet, primary combustion takes
place → CO, H2, H2O, CO2, HC, radicals (H, O, OH)
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 Diesel Combustion Characteristics (2/3) Ref : DieselNet, 2002, Technical Notes,
“Combustion in Diesel Engines,”

■ Spray
S C
Core
¾ Larger droplets gain heat by radiation and diffusion from LFR
¾ Completely evaporated → the flame will burn all the mixture
within
ithin the rich ignition limit.
limit
¾ Partially evaporated → individual droplet combustion
¾ P/L : adequate O2 → complete combustion → High NOx
¾ F/L : Fuel
ue rich
c → incomplete
co p ete combustion
co ust o → HC, C, CO, C

■ Spray Tail
¾ △P(Injection-Cylinder P) low → Large droplet → Penetration poor
¾ Cyl.T High → Evaporation High, but, Inadequate O2 → HC,C,CO

■ Fuel Deposited on the Walls

¾ HC, C

■ Progression of Combustion, Cyl. P. and T.

¾①→②→③→④→⑤→⑥

■ Heat Release Rates in DI Engines

¾ Premixed combustion : Initial sharp rise in HRR,
HRR 5%
¾ Diffusion combustion
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 Diesel Combustion Characteristics (3/3) Ref : DieselNet, 2002, Technical Notes,
“Combustion in Diesel Engines,”

■ Typical
T i l DI E
Engine
i H Heatt R
Release
l R
Rate
t Di
Diagram and
d Di
Diesell C
Combustion
b ti P Process
(1) Ignition Delay Period (a-b)
• Between the start of injection (SOI) and the
start of combustion (SOC)
( )
• Fuel vaporized, start to mix
• Pre-ignition chemistry get started
• Negative heat release rate
((2)) Premixed or Rapid
p Burningg Phase ((b-c))
• Fuel+air mixture that has mixed to within
combustible limits burns rapidly
• High heat release
(3) Mixing Controlled Phase – Dominant Phase (c-
d)
• After the “premixed” fuel and air mixture
has burned
• Then, burning rate depends on the rate of
mixing
(4) Late Combustion Phase (d-e)
• Remaining fuel and CO, soot from rich
regions get consumed
• Chemistryy and mixingg control the rate

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 Lecture Notes on Applied Thermal Engineering 2011

Ch t 4
Chapter
Mass Transfer
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Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
Mass Transfer Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 3

¾ 전달현상
• 평형으로 접근하려는 추세
• 분자충돌에 기인
• Rate Process
¾ 확산율 : 단위시간당 면적 퍼짐율, ⎡⎣ L2 T ⎤⎦
과정 작용력 전달계수 확산율
운동량 속도구배 viscosity, μ kinematic viscosity, ν =μ ρ
에너지 온도구배 thermal conductivity, k thermal diffusivity, α = k ρ C p
물질 농도구배 binary diffusion coefficient,
coefficient Dij Dij

¾ 무차원수
• Prandtl Number,
Number
Rate off Momentum Diffusion
ff ν
Pr = =
Rate of Heat Diffusion α
Rate of Momentum Diffusion ν
• Scmidt Number,, Sc = =
Rate of Mass Diffusion D
Rate of Heat Diffusion α
Le = =
• Lewis Number, Rate of Mass Diffusion D

http://procom.chonbuk.ac.kr 38
Fick’s Law of Diffusion (1/2) Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 3

• Mass Flux

& ′′A = m
m &A A, [ kg/s ⋅ m ] 2 : Mass flux of species A, Eq.(3.2)

: Mixture mass flux, Eq.(3.7)

m & ′′A + m
& ′′ = m & ′′B
& ′′ = YA ( m
& ′′A = YA m
m & ′′B )
& ′′A + m : Bulk flux of species A, Eq.(3.3a)

dYA : Diffusional flux of species A, Eq.(3.3b)

& ′′A , diff ≡ − ρD AB
m
dx
where, D AB: Binary diffusivity
• Fick’s Law of Diffusion

dYA
& ′′A =
m YA ( m& ′′A + m& ′′B ) − ρD AB (3.1)
14 4244
2 3 1424 dx
3
mass flow of species A associated with
the bulk flow per unit area mass flow of species A associated with
the molecular diffusion per unit area

http://procom.chonbuk.ac.kr 39
Fick’s Law of Diffusion (2/2) Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 3

For a binary mixture

dYA dYB
& ′′ = YA m
m & ′′ − ρD AB
+ YB m − ρD BA
& ′′ (3.8a)

144 d3 1442443
dx
42444 ddx
& ′′A
m & ′′B
m

d A
dY dY
d B
= (YA + YB ) m& ′′ − ρD AB − ρD BA (3 8b)
(3.8b)
1424
3 dx dx
=1

dYA dYB
∴ − ρD AB − ρD BA =0 (3.9)

14243 dx 14243 dx
diffusional flux of species A diffusional flux of species B

∴∑m
& ′′i , diff = 0 : Sum of the diffusional fluxes of the species is zero.

http://procom.chonbuk.ac.kr 40
 Lecture Notes on Applied Thermal Engineering 2011

Ch t 5
Chapter
Chemical Kinetics
http://procom.chonbuk.ac.kr 41
Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
Global Reaction Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 4

• Chemical Kinetics
The study of the elementary chemical reactions and their rates

• Global Reaction Mechanism

F + aO → bP (4.1)
F
From experimental
i t l study,
t d ththe rate
t att which
hi h th
the ffuell iis consumed
d can b
be expressed
d as

d [X F ]
= − k G (T ) [ X F ] [ X O ] (4.2)
n m

dt
where, [ X i ] : molar concentration, ⎡⎣ kmol m 3 ⎤⎦
k G : global reaction rate coefficient, = f (T )
n , m : reaction
i order,
d nth h wrt ffuel,
l mthh wrt oxidizer,
idi ((n+m)th
) h overallll
(number of molecules participating reaction)
(-) sign : decrease of fuel concentration with time

http://procom.chonbuk.ac.kr 42
Elementary Reaction Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 4

• Global Reaction

2H 2 + O 2 → 2H 2 O (4.3)
• Elementary
El t R
Reaction
ti

H 2 + O 2 → HO 2 + H (4.4)

H + O 2 → OH + O (4.5)
(4 5)

OH + H 2 → H 2 O + H (4.6)

H + O 2 + M → HO 2 + M (4.7)

• Radical : reactive molecules, or atoms, that have unpaired electrons

HO2 : hydroperoxy radical, OH : hydroxyl radical

The collection of elementary reactions necessary to describe an overall reaction is called a

reaction mechanism, which may involve only a few steps (i.e., elementary reactions) or as
many as several hundred.

http://procom.chonbuk.ac.kr 43
Bimolecular Reactions and Collision Theory Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 4

Two molecules collide and react to form two different molecules,

molecules ii.e.,
e A+B→C+D
The rate at which the reaction proceeds is directly proportional to the concentrations of the 2
reactant species, i.e.,
d [A ]
= − k bimolec [A ][ B ] (4 9)
(4.9)
dt
From molecular collision theory, bimolecular rate coefficient becomes
1 2
⎛ 8π k BT ⎞ ⎛ EA ⎞
k (T ) = pN AV σ 2
AB ⎜ μ ⎟ exp ⎜ − ⎟
(4.17)
⎝ ⎠ ⎝ R u T ⎠
where,, p : ggeometrical ((or steric)) factor
N AV : Avogadro number, = 6.022 × 10 26 molecules/kmol
E A : Activation energy

Bimolecular rate coefficient byy empirical

p Arrhenius form,,

k (T ) = A exp ( − E A R uT ) (4.18)

or k (T ) = AT b exp (
p − E A R uT ) (4.19)
where, A : pre-exponential factor (or frequency factor)
A , b , E : three empirical parameters, for example, see Table 4.1
A

http://procom.chonbuk.ac.kr 44
Other Elementary Reactions Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 4

• Uni–molecular
Uni molecular Reaction : A → B or A → B + C
For example, ,
O2 → O + O H2 → H + H
Reactions at (1) high pressure : d [A ] (4 22)
(4.22)
= − k uni [,A ]
dt
(2) at low pressure : d [A ] (4.23)
= − k uni [A ][ M ]
dt

• Ter–molecular Reaction : (4.24)

A+B+M →C+M
For example, H + H + M → H2 + M
, H + OH + M → H 2 O + M
Reactions : d [A ] (4.25)
= − kter [A ][ B ][ M ]
dt
• Third Body : M

http://procom.chonbuk.ac.kr 45
Multistep Reaction Mechanism Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 4

H 2 − O 2 reaction mechanism
kf 1
H2 + O2 HO 2 + H (R.1)
kr 1
kf 2
H + O2 OH + O ((R.2))
kr 2

OH + H 2
kf 3
H 2O + H (R.3)
kr 3

H + O2 + M
kf 4
HO 2 + M ((R.4))
kr 4

The net rate of production of O 2 is the sum of all of the individual elementary rates producing
minus the sum of all of the rates destroying O 2 ; i.e., O 2
d [O 2 ] (4.26)
= k r 1 [ HO 2 ][ H ] + k r 2 [ OH ][ O ] + k r 4 [ HO 2 ][ M ]
dt
− k f 1 [ H 2 ][ O 2 ] − k f 2 [ H ][ O 2 ] − k f 4 [ H ][ O 2 ][ M ]
and for H atoms
d [H ]
= k f 1 [ H 2 ][ O 2 ] + k r 2 [ O OH ][ H 2 ] + k r 4 [ HO
OH ][ O ] + k f 3 [ O O 2 ][ M ] (4.27)
dt
− k r 1 [ HO 2 ][ H ] − k f 2 [ H ][ O 2 ] − k r 3 [ H 2 O ][ H ] − k f 4 [ H ][ O 2 ][ M ]

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Compact Notation and Production Rate Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 4

Compact Notation
N N

∑ν ′ X
j=1
ji j ↔ ∑ ν ′′ X
j=1
ji j for i = 1, 2 ,L , L (4.29)

where, ν ′ji and ν ′′ji are the stoichiometric coefficients on the reactants and products
side of the equation, respectively, for the jth species in the ith reaction.

Production Rate
d ⎡⎣ X j ⎤⎦ L
ω& j ≡ = ∑ ν jji q i for j = 1, 2 ,L , N (4.31)
dt i=1
N N
where, ν ji = (ν ′′ji − ν ′ji ) , and q i = k fi ∏ ⎡⎣ X j ⎤⎦
ν ′ji ν ′′ji
− k ri ∏ ⎡⎣ X j ⎤⎦ (rate-of-progress variable)
j =1 j=1

((4.32 and 33))

http://procom.chonbuk.ac.kr 47
Example 4.2 (pp.135~136) Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 4

Calculate ω& O in H 2 − O 2 reaction mechanism, (R1)

2
(R1)–1(R4).
1(R4).

L
ω& j = ∑ ν ji q i for j = 1, 2 ,L , N
i=1

q 1 = k f 1 [ O 2 ] [ H 2 ] [ H 2 O ] [ HO 2 ] [ O ] [ H ] [ OH ] [ M ] − k r 1 [ O 2 ] [ H 2 ] [ H 2 O ] [ HO 2 ] [ O ] [ H ] [ OH ] [ M ]
1 1 0 0 0 0 0 0 0 0 0 1 0 1 0 0

q 2 = k f 2 [ O 2 ] [ H 2 ] [ H 2 O ] [ HO 2 ] [ O ] [ H ] [ OH ] [ M ] − k r 2 [ O 2 ] [ H 2 ] [ H 2 O ] [ HO 2 ] [ O ] [ H ] [ OH ] [ M ]
1 0 0 0 0 1 0 0 0 0 0 0 1 0 1 0

q 3 = k f 3 [ O 2 ] [ H 2 ] [ H 2 O ] [ HO 2 ] [ O ] [ H ] [ OH ] [ M ] − k r 3 [ O 2 ] [ H 2 ] [ H 2 O ] [ HO 2 ] [ O ] [ H ] [ OH ] [ M ]
0 1 0 0 0 0 1 0 0 0 1 0 0 1 0 0

q 4 = k f 4 [ O 2 ] [ H 2 ] [ H 2 O ] [ HO 2 ] [ O ] [ H ] [ OH ] [ M ] − k r 4 [ O 2 ] [ H 2 ] [ H 2 O ] [ HO 2 ] [ O ] [ H ] [ OH ] [ M ]
1 0 0 0 0 1 0 1 0 0 0 1 0 0 0 1

ν 11 ′′ − ν 11
= ν 11 ′ = 0 − 1 = −1
ν 12 ′′ − ν 12
= ν 12 ′ = 0 − 1 = −1
ν 13 ′′ − ν 13
= ν 13 ′ =0−0 =0
ν 14 ′′ − ν 14
= ν 14 ′ = 0 − 1 = −1

4
∴ ω& O 2 = ω& 1 = ∑ ν 1 i q i = ν 11 q 1 + ν 12 q 2 + ν 13 q 3 + ν 14 q 4
i=1

http://procom.chonbuk.ac.kr 48
Relation between k and K Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 4

For the arbitrary bimolecular reaction,

⎯⎯
k
→C + D d [A ] (4.35 and 36)
A + B ←⎯ → = ω& A = − k f [A ][ B ] + k r [ C ][ D ]
f
⎯ kr dt
for equilibrium,
equilibrium d [A ] dt
d = ω& A = 0

0 = − k f [A ][ B ] + k r [ C ][ D ] → ∴
[ C ][ D ] = kf (4.37 and 38)
[A ][ B ] kr
In Chapter 2,
2 for an arbitrary reaction
reaction, A + B +L → C + D +L

( PC P 0 ) ( PD P 0 ) L
c d
1 P (4.39 and 40)
Kp = and [X i ] = = i → Pi = [ X i ] R uT
(P ) (P
0 c
)
d
A P B P 0
L v i R uT

[ C ] [ D ] L ⎛ R uT ⎞
c d c + d +L − a − b −L
∑ν ′′− ∑ ν ′ k f (T )
∴Kp = ⎜ 0 ⎟ = K C ( R uT P 0 ) → K C (T ) = (4.43)
[14243
A ] [B ] L ⎝ P ⎠
c d
kr (T )
1 3
≡ KC

For a bimolecular reaction, KC = K p

http://procom.chonbuk.ac.kr 49
Steady State Approximation Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 4

In many combustion systems, highly reactive intermediate species, e.g., radicals, are formed. Analyses
of such systems can sometimes be simplified by applying the steady-state approximation.
Physically, what occurs is that, after a rapid initial buildup in concentration, the radical is destroyed as
rapidly as it is formed, so that its rate of formation and its rate of destruction are equal.

Example : Zeldovich mechanism for the formation of NO

O + N 2 ⎯ k⎯
1
→ NO + N
N + O 2 ⎯ k⎯
2
→ NO + O

net production rate of N atoms is

d [N ] (4.44)
= k 1 [ O ] [ N 2 ] − k 2 [ N ][ O 2 ]
dt
Steady-state approximation : d [ N ] dt → 0

k 1 [ O ][ N 2 ]
0 = k 1 [ O ][ N 2 ] − k 2 [ N ]SS [ O 2 ] → ∴ [ N ]SS = (4 47)
(4.47)
k 2 [O 2 ]

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Chain Reaction Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 4

Chain reactions involve the production of a radical species that subsequently reacts to produce
another radical.
(C.1)
Global reaction : A 2 + B 2 → 2AB
Ch i reaction
Chain ti : (1) chain-initiation
h i i iti ti reaction
ti : A 2 + M ⎯ k⎯
1
→A +A +M (C 2)
(C.2)
(2) chain-propagation reaction : (C.3)
A + B 2 ⎯ k⎯
2
→ AB + B
B + A 2 ⎯ k⎯
3
→ AB + A (C.4)
(3) chain
chain-terminating
terminating reaction :
A + B + M ⎯ k⎯
4
→ AB + M (C.5)

reaction rate : d [A 2 ] = − k 1 [A 2 ][ M ] − k 3 [A 2 ][ B ] (4.58)

dt
d [B 2 ] (4.59)
= − k 2 [ B 2 ][ A ]
dt
d [AB ] (4 608)
(4.608)
= k 2 [A ][ B 2 ] + k 3 [ B ][A 2 ] + k 4 [A ][ B ][ M ]
dt
Chain-branching reactions involve the formation of two radical species from a reaction that consumes
only one radical.
radical
O + H2O ⎯ ⎯
→ OH + OH

★연쇄반응
반응
: 반응
반응으로 활성기 화학종이 생성되
생성되고 여기에서 또 다른 활성기가 계속 생성되어 연
연소가
가 진행되는

http://procom.chonbuk.ac.kr 51
 Lecture Notes on Applied Thermal Engineering 2011

Ch t 6
Chapter
Some Important Chemical Mechanisms
http://procom.chonbuk.ac.kr 52
Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
 H2–O2 System : Chain Reaction Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 5

• 1–step global reaction Initiation

reaction

2H 2 + O 2 → 2H 2 O
Chain
reaction
• 4–multistep Reaction

kf 1 Chain-
H2 + O2 kr 1
HO 2 + H terminating
reaction
kf 2
H + O2 kr 2
OH + O 20 step
20-step
kf 3 Chain
OH + H 2 kr 3
H2O + H Reaction
kf 4
H + O2 + M kr 4
HO 2 + M

HO2 reaction
• Chain Reaction

http://procom.chonbuk.ac.kr 53
 H2–O2 System : Explosion Limit
• Region ① (1.0~1.5mmHg)
no explosion ← free radicals from (H.2) and (H.3~6) being
destroyed by reactions on the wall via ④
Radicals ⎯ k⎯⎯
wall
→ absorbed products
1st limit
Region ② (1.5~50mmHg)
explosion ← gas phase chain reaction (H.3~6)
(H.3 6) prevailing
over the radical destruction at the wall
2nd limit ③
Region ③ (50~3,000mmHg)
no explosion ← competition for H between chain-branching
(H.3) and chain-terminating (H.11)
(HO2 is stable at this condition → it can diffuse to the wall
where it is destroyed → (H.11) is chain-terminating)

3rd limit
Region ④ (above 3,000mmHg)
②
explosion ← chain-branching (H.16) opening the H2O2
chain sequence

①
http://procom.chonbuk.ac.kr 54
 Carbon Monoxide (CO) Oxidation
(1) breakdown of the fuel to carbon monoxide (CO)
• Hydrocarbon Combustion
(2) oxidation of carbon monoxide to carbon dioxide (CO2)
¾ CO is slow to oxidize unless there are some hydrogen-containing species present.
¾ Small quantities of H2O or H2 can have a tremendous effect on the oxidation rate.

• CO combustion with H2O

( CO.1 ) CO + O 2 → CO 2 + O slow reaction, initiator of the chain sequence (∵O)

( CO.2 ) O + H 2 O → OH + OH
( CO.3 ) CO + OH → CO 2 + H CO oxidation (chain-propagating) step, key reaction

( CO.4 ) H + O 2 → OH + O
• CO combustion with H2 instead of H2O

( CO.5 ) O + H 2 → OH + H
( CO.6 ) OH + H 2 → H 2 O + H

http://procom.chonbuk.ac.kr 55
 Appendix : Hydrocarbon Fuel (1/2)
A.1 Basic Hydrocarbon Families

A.2 Nomenclature A.3 Molecular structure

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 Appendix : Hydrocarbon Fuel (2/2)
A.4 Saturated/Unsaturated Compound
¾ saturated : alkane
¾ unsaturated : alkene, alkyne

A.5 Normal/Isomer
¾ normal : straight chains of C
¾ isomer : branched chains of C
A.6 Isooctane

A 7 Cyclane
A.7 C l A 8 Aromatic
A.8 A (B
(Benzene d
derivative))

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 Oxidation of Higher Paraffins
The oxidation of paraffins can be characterized by three sequential processes :

I. Decomposition of fuel
Alkane → Olefin + Hydrogen
H d
Hydrogen+Oxygen
O → Water
W
II. Oxidation of Olefin
Olefin+Oxygen → CO+H2
Hydrogen+Oxygen → Water
III. Oxidation of CO
CO+OH → CO2+H
Heat Release

http://procom.chonbuk.ac.kr 58
 Oxidation of Higher Paraffins
Example of C3H8 Oxidation

http://procom.chonbuk.ac.kr 59
 Methane (CH4) Combustion
CH4 Combustion
High ignition temperature, low flame speed, unreactive in photochemical smog chemistry due to stable tetrahedral
molecular structure

Complex Mechanism
277 elementary reactions with 49 species
Low Temperature Reaction

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 Methane (CH4) Combustion
High Temperature Reaction

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 Oxides of Nitrogen (NOx) Formation
Thermal (Zeldovich) NO Mechanism
: dominant mechanism in high temperature combustion over a fairly wide range of equivalence ratios
¾ Zeldovich mechanism

¾ Extended Zeldovich mechanism

Prompt (Fenimore) NO Mechanism

: particularly important mechanism in rich combustion

Fuel NO Mechanism : due to fuel-borne nitrogen

N2O-Intermediate Mechanism : is important in fuel-lean, low-temperature conditions

http://procom.chonbuk.ac.kr 62
 Ref : Barry A. A. L. van Setten, “Development of a

What is PM : Soot Particle Formation Liquid Catalyst for Diesel Soot Oxidation – from
Power to Prototype,” Ph.D. Thesis, de Technische
Universiteit Delft, 2001.02

• Fuel Pyrolsis
CA 1° @2,000rpm - C2Hx→C4Hx
- C3Hx+C3Hx
• Ring(Benzene,C6H6)
Ring(Benzene C6H6)
Formation
- HACA : H-
Abstraction-C2H2-Addition
- Aromatic combination
• Platelet (PAH) : Graphite like
sheets that could be seen as
primary building blocks of soot
particle (Polycyclic Aromatic HC)
- HACA (High T)
- crystallization, PAH
agglomeration (Low T)
• Turbostratic Particle : Particle
that the building blocks (i.e.
platelets) are concentrated
around in a random orientation
around the center of the particle
- coagulation
- surface growth
• Soot Particle
- aggregation
Schematic mechanism of the formation of soot particles
• Larger Soot Particles
http://procom.chonbuk.ac.kr 63
 Ref : Barry A. A. L. van Setten,

What is PM : Condensation Mechanisms “Development of a Liquid Catalyst for

Diesel Soot Oxidation – from Power to
Prototype,” Ph.D. Thesis, de Technische
Universiteit Delft, 2001.02

As the exhaust gas coos down hydrocarbons condenses

along two pathways :

(1) nucleation (2) adsorption

combustion +H2O
S in Fuel → SO2 → SO3 → H2SO4
98% 2%

Illustration of the condensation mechanisms that can operate in diesel exhaust gas Schematic structure of a chain-like aggregate of
primary soot particles and associated compounds

http://procom.chonbuk.ac.kr 64
 Lecture Notes on Applied Thermal Engineering 2011

Ch t 7
Chapter
Governing Equations for Reacting Flows
http://procom.chonbuk.ac.kr 65
Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
 Governing Equations
• Conservation Equations
• Mass Conservation : Continuity Equation
• Momentum Conservation : Navier-Stokes Equation
• Energy
gy Conservation : Energy
gy Equation
q
• Species Conservation : Species Conservation Equation

• Supplementary Equations
• Turbulent Kinetic Energy (TKE) and Dissipation Rate of TKE Equations
• Combustion Chemistry

CH 4 + ν O 2 (O 2 + n N 2 ) → ν CO2 CO 2 + ν H2O H 2 O + ν N2 n N 2 + H v

H v = 5 .03357 × 10 7 J kg
• Reaction Rate Ypr ⎤
ε ⎡ YO2
ω& fu = − ρ A EBU min ⎢Y fu , , B EBU ⎥
k ⎣ s 1 + s ⎦
• Equation of State P
ρ=
Yj
RT ∑
j Wj
• Specific Heat of Mixtures
C p , mix = ∑ Y jC pj
j
http://procom.chonbuk.ac.kr 66
 Analysis of 3D Turbulent Combustion (1/3)

Combustion with Radiation – Formulations

∂ ∂ ⎛ ∂φ ⎞ ¾ Supplementary Equations
¾ Governing
G i EEquations
ti
∂x j
(ρ u jφ = ) ⎜⎜ Γφ
∂ x j ⎝ ∂x j
⎟⎟ + Sφ
h= ∑Y h = ∑ Yk ∫ C p ,k dT
T

⎠ k
k k
k
Tref

⎛ ∂ u ∂ u j ⎞ ∂ui k2
φ Γφ Sφ G k = μT ⎜ i + μT = C μ ρ
⎜ ∂x j ∂ xi ⎟⎟ ∂x j ε
∂p ∂ ⎛ ∂u ⎞ ∂ ⎛ ∂v ⎞ ∂ ⎛ ∂w ⎞ ⎝ ⎠
u μ eff − + ⎜ μ effff ⎟+ ⎜ μ effff ⎟+ ⎜ μ effff ⎟ ¾ Combustion
Comb stion Chemistr
Chemistry
∂x ∂ x ⎝ ∂x ⎠ ∂y ⎝ ∂x ⎠ ∂z ⎝ ∂x ⎠
∂p ∂ ⎛ ∂u ⎞ ∂ ⎛ ∂v ⎞ ∂ ⎛ ∂w ⎞ CH 4 + ν O 2 ( O 2 + n N 2 )
v μ eff − + ⎜ μ eff ⎟+ ⎜ μ eff ⎟+ ⎜ μ eff ⎟
∂y ∂ x ⎝ ∂y ⎠ ∂y ⎝ ∂y ⎠ ∂z ⎝ ∂y ⎠ → ν CO 2 CO 2 + ν H 2 O H 2 O +ν N 2 n N 2 + H v

w μ eff
∂p ∂ ⎛ ∂u ⎞ ∂ ⎛ ∂v ⎞ ∂ ⎛ ∂w ⎞ YCO 2 = γ CO 2 Ypr , YH 2 O = 1 − γ CO 2 Ypr( )
− + ⎜ μ eff ⎟+ ⎜ μ eff ⎟+ ⎜ μ eff ⎟ ν CO WCO
∂z ∂ x ⎝ ∂z ⎠ ∂y ⎝ ∂z ⎠ ∂z ⎝ ∂z ⎠
μ eff γ CO = 2 2

k G − ρε
2
ν CO 2
W CO + ν H O W H
2 2 2O
σk
ε
μ eff ε (
YN 2 = 1 − Y f + YO 2 + YCO 2 + YH 2O )
σε
( C ε 1G − Cε 2 ρε )
k ε ⎡ YO Ypr ⎤
μ eff ω& f = − ρ AEBU min ⎢Y f , 2 , BEBU
h H vω& fuel − ∇ ⋅ q R
k ⎣ s 1 + s ⎥⎦
PrT p
μ eff ρ=
Yf −ω& fuel Yj
Sc T RT ∑
μ eff 2 WO 2 j Wj
YO 2 − ω& fuel C p ,mix = ∑ Y jC pj , C pj = aoj + b0 jT
ScT Wf
Ypr
μ eff (W CO 2 + 2 WH2 O )
ω& fuel ¾ Radiative Heat Transfer
j

ScT Wf
C 1 = 1.44, C 2 = 1.92 , C μ = 0.09, σ k = 1.3, σ ε = 1.0
(
∇ ⋅ q R = κ a 4π I b − ∫ IdΩ
4π
)

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 Analysis of 3D Turbulent Combustion (2/3)

Combustion with Radiation – Results

r
v
1 L eve l k 1 L ev el ε
ε
Le ve l 1 2 3 4 5 6 7 3 3
k 1 3 5 7 9 11 1 3 k 7
5
8
7
8
7
5
7
8
7
240
210
8 6 6 8 6 180
7 4 2 1
k 7
6
5
3
2
8
7
5
4
5
4
8 5
4
150
120
3 3 7 3 90
2 2 2 60
Le ve l 1 2 3 4 1 1 1 30
ω& fu 0. 1 0. 2 0. 3 0. 4

ω& f 4 2
1

L ev el ω& f u L ev el T
Le vel
T
1 2 3 4 5 6 7 8 9 10
1 0 00 1 2 00 1 40 0 16 0 0 18 0 0 200 0 210 0 21 50 2 2 00 2 250
ω& f 7 0 .21
0 .18
18
T 2 6 2 100
2 000
6 3 5
6 2 1
2 2 3 5 7 5 0 .15 4 1 900
4 5
T 1 10 9 8
7
4
3
0 .12
0 .09
6
6
3
2
1 800
1 700
5 5
2 0 .06 1 1 600
7 4
1 0 .03
L ev el 1 2 3
Yf u 1. e-4 1 . e-3 8. e-3

Yf 3 2 1

L ev el 1 2 3 4 5 6
Yf
Le ve?l
8
? Y?fu
0 . 16
YCO 2 2
L e vel Y C O2
6 0 .12
YO2 0 .0 4 0 .0 6 0. 08 0. 1 0. 12 0. 14 5 0 .11
7 0 . 14
5 3 6 0 . 12 3 4 0 .10
YO 2 6 4
1
2
5 0 . 10 4
3 0 .09
1 4 0 . 08 6 2 0 .08
6 0 .07
8 3 0 . 06 5 1
L ev el 1 2 3 4 5 6 7 8 9 2 0 . 04
YC O2 0 .0 4 0 .0 5 0. 06 0. 07 0. 08 0. 09 0 .10 0 .1 1 0 .1 2 1 0 . 02

1 1 2 3 4 5 6 7 8
YCO2 9

http://procom.chonbuk.ac.kr 68
 Analysis of 3D Turbulent Combustion (3/3)
Combustion with Radiation – Results (Continued.)
0.6 0.8
i l
equivalence ratio
ti = 00.6
6 no swirl
i l
0.7 0.6 swirl a ngle = 1 5 degree
0.4 0.8 30 degree
0.9 45 degree
ω& fu
ω& f u 0.4
0.2
0.2

0.0 0.0
250 0 0.5 1.0 2500 0 0.5 1.0 1.5
x (m) x (m)

200 0 2000

T 150 0 T 1500 no swirl

i l
equivalence ratio = 0.6 swirl angle = 15 degree
30 degree
100 0 0.7 1000
0.8 45 degree
0.9
50 0 500
0 .3 0.5 1.0 0.3 0 0.5 1.0 1.5
xequivalence
(m) ratio = 0.6 x (m)
no swirl
0.7 swirl angle = 15 degree
0.8 30 degree
0 .2 0.9
0.2
45 degree
YC O2 YCO2
0 .1 0.1

0 .0 0.0
0 .5 1.0 0 0.5 1.0 1.5
x (m ) x (m)

http://procom.chonbuk.ac.kr 69
 Continuity Equation (1/2) Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 7
1D case
dm cv
= [ m& ]3
x
− [ m& ]x + Δ3x
dx 3
1424 1
424 1424
Mass flow into the Mass flow out of the
Rate of increase of mass control volume control volume
within control volume

Since V = A Δ x, m = ρVcv, and & = ρ vx A

m
cv cv

d ( ρ AΔx )
∴ = [ ρ v x A ]x − [ ρ v x A ]x + Δx
dt
If steady, ∂ ∂t = 0
d ( ρ vx )
∴ =0 → ρ v x = constant
dx

http://procom.chonbuk.ac.kr 70
 Continuity Equation (2/2) Ref : Principles of Combustion, by
K. K. Kuo, Chapter 3

∂ρ r
∂t
( )
+ ∇ ⋅ ρV = 0

http://procom.chonbuk.ac.kr 71
 Species Conservation Equation (1/3) Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 7

1D case

d ⎡ dYA ⎤
& ′′YA
m − ρD AB = & ′′′A
m
dx ⎢⎣ dx ⎥⎦

d (m
& ′′YA ) d ⎛ dYA ⎞
− ⎜ ρD AB ⎟ = & ′′′A
m
dx dx ⎝ 424444 dx ⎠ 3 1
424 3
144244 3 1444 Net ma ss pproduction rate off species
p A
Mass flow
M fl off species
i A due
d tot convection
ti Mass flow of species A due to molecular diffusion (
by chemical reaction per unit volume kg m 3 s )
(
per unit volume kg m 3 s ) (
per unit volume kg m 3 s )

General 1D form of species continuity,

dm& ′′i
∴ & i′′′
=m where, i=1,2,…, N
dx
General vector form for mass conservation of the ith species,
species

∂ ( ρ Yi )
+ & ′′i
∇⋅m = & ′′′
m i
14243∂t 14
4244 3 14
4244 3
Net rate of mass flow of species i out by Net rate of mass production of species i
Rate of gain of mass of species i diffusion and bulk flow per unit volume per unit volume
per unit volume

http://procom.chonbuk.ac.kr 72
 Species Conservation Equation (2/3) Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 7

Definition of various velocities

; mass average velocity of species i : m& ′′i & ′′
m
vi ≡ = i
ρ Yi ρi
vi v i ,diff
; mass average bulk velocity : V = ∑ Yi v i =
∑ρ v i i

; diffusional velocity : v i,diff ≡ v i − V

∑ρ i

Definition of various mass fluxes V

; mass flux of species i : & ′′i ≡ ρ Yi v i
m
; mixture mass flux (=sum of all of the individual species mass fluxes) :
∑ m& ′′ = ∑ ρ Y v
i i i
& ′′ = ρ V
=m
; diffusional mass flux of species i : & ′′i,diff ≡ ρ Yi ( v i − V ) = ρ Yi v i,diff
m
; total species mass flux is the sum of the bulk flow and diffusion contributions :

& ′′i = m
m & ′′Yi + m
& ′′i,di
d ff → ρ Yi v i = ρ Yi V + ρ Yi v i,dd iffff = ρ Yi ( V + v i,diff
d ff )

General species conservation equation

∂ ( ρ Yi )
∂t ⎣ (
+ ∇ ⋅ ⎡ ρ Yi V + v i,diff ⎤ = m
⎦ )
& ′′′i for i=1,2,…,N
i=1 2 N

http://procom.chonbuk.ac.kr 73
 Species Conservation Equation (3/3) Ref : Principles of Combustion, by
K. K. Kuo, Chapter 3

http://procom.chonbuk.ac.kr 74
 Momentum Equation (1/2) Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 7

1D Case

∑ F = m& v out −m
& v in
For 1D case,
[ PA ]x − [ PA ]x + Δx & ([ v x ]x + Δx − [ v x ]x )
=m

dividing by Δ xand taking Δ x → (note

0 that A and are
& constant)
m
dP d
dv dP d
dv
∴− & ′′ x
=m → − = ρ vx x
dx dx dx dx

http://procom.chonbuk.ac.kr 75
 Momentum Equation (2/2) Ref : Principles of Combustion, by
K. K. Kuo, Chapter 3

http://procom.chonbuk.ac.kr 76
 Energy Equation (1/2) Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 7

1st law of thermodynamics in 1D case

⎡⎛ v2 ⎞ ⎛ v2 ⎞ ⎤
( )
Q& x′′ − Q& x′′+ Δx A − W& cv = m
& ′′A ⎢ ⎜ h + x + gz ⎟
2
− ⎜ h + x + gz ⎟ ⎥
2
⎣⎝ ⎠ x + Δx ⎝ ⎠x ⎦
Assumption : steady state, no work, and no change in P.E.

⎡⎛ v x2 ⎞ ⎛ v x2 ⎞ ⎤ dQ& ′′ ⎛ dh dv x ⎞
(
& ′′ & ′′ )
& ′′
− Q x + Δx − Q x = m ⎢ ⎜ h +
2 ⎟ − ⎜ h +
2 ⎟ ⎥ → −
dx
= m
& ′′ ⎜
⎝ dx
+ v x
dx
⎟
⎠
⎣ ⎝ ⎠ x + Δx ⎝ ⎠ x⎦

Heat flux vector

& ′′
Q
{ = −
{ k∇ T + ∑ m
& ′′ h
Heat flux vector C d ti
Conduction1 i ,diff3i
1424
Species diffusion
since & ′′i = ρ v ixYi,
m & ′′ = ρ v x, and
m ∑ Yi hi = h
dT dT dT
Q& x′′ = − k + ∑ ρ Yi ( v ix − v x ) h i = − k + ∑ ρ Yi v ix h i − ρ v x ∑ Yi h i = − k +∑m
& ′′i h i − m
& ′′h
dx dx dx
Energy conservation equation

d d ⎛ dT ⎞ dv d dh dm& ′′i dm& ′′i

dx
( ∑ & ′′i ) +
hi m ⎜ −k
dx ⎝
⎟+m
dx ⎠
& ′′v x x = 0
dx
where,
dx
( ∑ hi m& ′′i ) = ∑ m
& i′′ i + ∑ h i and
dx dx dx
& i′′′
=m

dh d ⎛ dT ⎞ dv
∴∑m & i′′ i + ⎜ −k ⎟+m & ′′v x x = − ∑ hi m& ′′
i
′
dx dx ⎝ dx ⎠ dx

http://procom.chonbuk.ac.kr 77
 Energy Equation (2/2) Ref : Principles of Combustion, by
K. K. Kuo, Chapter 3

http://procom.chonbuk.ac.kr 78
 Lecture Notes on Applied Thermal Engineering 2011

Ch t 8
Chapter
Ignition and Extinction
http://procom.chonbuk.ac.kr 79
Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
Overview Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 8

¾ Flame
• Laminar flame • Premixed flame
• Turbulent flame • Diffusion flame
¾ Laminar Premixed Flame
• gas range, oven, heating appliance, Bunsen burner
a e (propagation)
• flame (p opagat o ) speed
• flame thickness
• quenching, flammability (limit), ignition
• flame stabilization : flashback
flashback, liftoff
¾ Definition

• flame : self-sustaining propagation of a localized combustion zone at subsonic velocity

9 local – the flame occupies only a small portion of the combustible mixture at any one time
9 subsonic – deflagration (↔ detonation)

http://procom.chonbuk.ac.kr 80
Structure of the Laminar Premixed Flame Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 8

Combustion zone ¾ Flame Structure

• preheat zone : little heat is released
• reaction zone : the bulk of chemical
energy is released. (0.1~1mm)
Products • Continuity
ρ u SL A ≡ ρ u vu A = ρ b vb A
Intermediate where, S L : flame propagation speed
species
u : unburned gas
b : burned gas
For the typical hydrocarbon-air flame (1 atm)
ρu ρb 7
∴ There is considerable acceleration of the
gas flow across the flame

¾ Flame Radiation
• blue flame : excess of air,, due to excited CH,, OH radicals in the high-temperature
g p zone
• blue-green flame : Φ<1, due to excited C2, OH radicals
• bright yellow (nearly white) to dull orange flame : due to Φ>1, soot radiation

http://procom.chonbuk.ac.kr 81
Bunsen Burner Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 8

v b,n
vb
v b,t
⎧ v b ,n > v u ,n
⎨
v u,n ⎩ v b ,t = v u ,t
α

v u,t vu
ut

S L = v u ,n = v u sin α
: Laminar burning velocity

¾ The typical Bunsen-burner flame is a dual flame

• inner flame 9 blue-green fuel rich premixed flame
9 preheat / reaction zone, fast combustion
9 yellow diffusion flame of pyrolysed hydrocarbon with ambient air
• outer flame
9 slow combustion

http://procom.chonbuk.ac.kr 82
Laminar Burning Velocity Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 8

v b,n
vb
v b,t
⎧ v b ,n > v u ,n
⎨
v u,n
un
⎩ v b ,t = v u ,t
α

v u,t vu

S L = v u ,n = v u sin α
: Laminar burning velocity

http://procom.chonbuk.ac.kr 83
Quenching, Flammability, and Ignition Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 8

• 천이(임계) 현상 : 동결상태와 연소상태의 천이, 점화, 소염

• 점화/소염 방법 : 열공급/열손실 (온도, 압력, 등), Chain Branching

¾ Flame quenching, ignition : transient process → Here, we will confine our attention to
examining limit behavior
¾ Flame quenching
9 passing through narrow passageway
9 addition of diluents
• water – thermal effect
• halogen
a oge – cchemical
e ca suppressant
supp essa t
9 blowing
9 explosive charge : blowout of a oil-well fire
¾ Quenching distance,
distance flammability limit,
limit and minimum ignition energy → Heat losses are
assumed to control the phenomena

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Ignition Ref : 연소공학, by 송규근, 최병철, Chapter 3

¾ 점화, 착화, 발화 (Ignition) : 연소반응을 개시하고 지속하는 과정

¾ 강제점화, 자연발화
¾ 착화과정

http://procom.chonbuk.ac.kr 85
 Forced Ignition – Minimum Ignition Energy Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 8

¾ Spark ignition : SI engine

engine, gas turbine engine
engine, burner
¾ Simplified Ignition Analysis : Critical Radius
9 R crit ≡ A flame will not propagate if the actual radius is T ( R crit ) = Tb
smaller
ll than
h theh critical
i i l value
l T ( ∞ ) = Tu
4π Rcrit
3
dT
Energy balance : Q ′′′V = Q cond → ( − m
& &
F Δ hc )
& ′′′ = − k ( 4π Rcrit
2
)
3 dr Rcrit
Temperature gradient in the cold gas at the sphere boundary
dT Tu − Tb T − Tu 3 k (Tb − Tu ) α
dr
=
Rcrit
=− b
Rcrit
∴ Rcrit
2
=
−m & ′′′
∴ Rcrit = 6 or Rcrit = ( )
6 2 δ = 1.2247 δ
Rcrit F Δ hc SL
• Critical radius is roughly
g y equal
q to the laminar flame thickness
• In contrast, the quenching distance can be many times larger than the flame thickness

http://procom.chonbuk.ac.kr 86
Flammability Limit Ref : 연소공학, by 송규근, 최병철, Chapter 3

★
¾ 可燃限界 : 물질이 연소할 수 있는 압력, 온도, 농도 등의 범위

p
¾ Experiments show that a flame will p
propagate
p g onlyy within a range
g of mixture strengths
g
between lower and upper limit of flammability
• lower limit : the leanest mixture ( Φ <)1that will allow steady flame propagation
Φ>1
• upper limit : the richest mixture ( )

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Quenching by a Cold Wall Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 8

★
¾ Quenching distance, 소염(消炎)거리

9 화염이 어떤 통로(튜브 또는 관)를 지날 때, 통로가 너무 작으면 화학반응에 의한 열발생률보다 전

도에 의한 열손실이 커서 화염이 전파되지 못하고 꺼짐.
꺼짐 이때의 직경 또는 거리를 소염거리라 한다.
한다
9 Experimentally, quenching distance is determined by observing whether a flame stabilized above a tube
does or does not flashback(逆火) for a particular tube diameter when the reactant flow is rapidly shut off
9 Tube-based quenching distances are somewhat larger (~20-50%) than slit-based ones

¾ Ignition
I iti anddQ
Quenching
hi C Criterion,
it i Willi
Williams (1985)

9 Ignition will only occur if enough energy is added

to the gas to heat a slab about as thick as steadily
propagating laminar flame to the adiabatic flame
temperature.
9 The rate of liberation of heat by chemical
reactions inside the slab must approximately balance
the rate of heat loss from the slab by thermal
conduction

http://procom.chonbuk.ac.kr 88
Flame Stabilization Ref : An Introduction to Combustion, by
S. R. Turns, Chapter 8

¾ Important design criteria for gas burners to

avoid the flashback and liftoff
¾ Flashback (逆火)
9 flame enters and propagates through the
burner tube or port without quenching
9 safety
f h
hazard
d → explosion
l i
¾ Liftoff (火炎浮上)
9 flame is not attached to the burner tube or
port but,
b rather,
h iis stabilized
bili d at some di
distance
from the port
9 undesirable phenomena because
• some escape off unburned
b d gas
• incomplete combustion
• ignition is difficult to achieve above the
lifting limit
• poor heat transfer because accurate control
of the position of a lifted flame is hard to
achieve
• noisyi

http://procom.chonbuk.ac.kr 89
 Part 2 Diesel Engine and Aftertreatments
Chapter 9 Introduction
Chapter 10 What is Catalyst
Chapter 11 The Preparation of Catalytic Materials
Chapter 12 Monolithic Reactors for Environmental Catalysis
Chapter 13 Automotive Substrates
Chapter
p 14 Diesel Catalysts
y
Chapter 15 Diesel Particulate Filter
Chapter 16 Some Numerical Examples
Chapter 17 References

http://procom.chonbuk.ac.kr 90
 Lecture Notes on Applied Thermal Engineering 2011

Ch t 9
Chapter
Introduction – Diesel Aftertreatments
http://procom.chonbuk.ac.kr 91
Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
 대륙별 자동차 생산/판매 통계 (‘2002)
(백만대) 25
생산
19.9 20.0 판매
20
17.3
16.6
14.9
15 14.2

10

5 3.8
2.6 2.4 2.0 1.5
0.3 0.7 -
0
동유럽 서유럽 북미 중남미 아시아 아프리카
아 리카 중동

¾ 전세계 자동차 생산 합계 : 58,954,220대

¾ 전세계 자동차 판매 (신차등록) 합계 : 57,232,774 대

http://procom.chonbuk.ac.kr 92
 Emission Regulations
0.06

Euro 3
0.05
FIE with ks-nozzle, 1600 bar
Particculate [gg/km]

cooled EGR
0.04
FIE 4th
4 h generation
i combustion
b ti systemt
combustion-optimization Euro4 application
0.03
Euro 4

0.02

0.01 Tier2Bin5 Diesel Particulate Filter

0.005 Euro5(Proposal)
Japan2009
0 00
0.00
0.0 0.1 0.2 0.3 0.4 0.5 0.6
NOx + HC [g/km] Euro3 application
ese Particulate
Diesel a t cu ate Filter
te

http://procom.chonbuk.ac.kr 93
 Ref : 김기영, “자동차 배기규제 ”, 대리진급자과정 강의노트, 2002.10.

공해를 유발시키는 인자들

정적 요인 동적 요인
- 화석연료를 사용하는 - 모든 자동차
모든 기계 - 비행기, 동력선, 기차등
- 자연 재해 ; 산불등 동력을 이용하는 열기관
- 화학공장에서 발생하 이 있는 움직이는 모든
는 반응물질 등 것

http://procom.chonbuk.ac.kr 94
 Ref : 김기영, “자동차 배기규제 ”, 대리진급자과정 강의노트, 2002.10.

자동차에서 배출되는 유해가스

- 주,정차중 증발가스
-주유중 증발가스

- 크랭크케이스
-배기연소 가스 블로바이

http://procom.chonbuk.ac.kr 95
 What are Diesel Emissions (1/2) Ref : 길정기, “자동차 촉매에 대하여”, 금속재료연
구팀, 2001.9.

■ Di
Diesell C
Combustion
b ti Products
P d t
¾ CO2 : 2~12%
¾ H2O : 2~12%
¾ O2 : 3
3~17%
17%
¾ N2 : 100-(CO2+H2O+O2)
■ Regulated Diesel Emssions
¾ DPM (Diesel Particulate Matter),
Matter) PM (Particulate Matter),
Matter)
TPM (Total Particulate Matter)
¾ SOF (Soluble Organic Fraction) : consisting part of DPM Comparison of regulated emissions – Spark Ignited
and Diesel Engines (MY 1992, 1.7 Liter)
¾ NOx (Nitrogen Oxides) : NO + NO2
¾ HC (Hydrocarbons) : THC (Total Hydrocarbons), NMHC (Non-Methane Hydrocarbons)
¾ CO (Carbon Monoxide)
■ Unregulated Diesel Emssions
¾ PAH (Polynuclear Aromatic Hydrocarbons) : Heavy organic compounds found mostly in the DPM or in the gas phase
¾ Aldehydes, R-CHO : derived from HCs (Formaldehyde, HCHO, is regulated in some applications)
¾ Sulfur Dioxide, SO2 : from sulfur present in the fuel
¾ Nitrous Oxide, N2O (is not included in NOx)
¾ Dioxins : diesel emissions are suspected to be a potential source of dioxin emissions
¾ Metal Oxides : from engine lubricating oil or fuel additives

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 What are Diesel Emissions (2/2) Ref : 길정기, “자동차 촉매에 대하여”, 금속재료연
구팀, 2001.9.

z 탄화수소 (Hydrocarbons, HC)

¾ 석유의 주축을 이루는 성분
¾ 상온에서 가스(ex : 프로판(C3H8)가스), 또는 액체(휘발유, 경유)로 존재하기도 함.
¾ 엔진내에서 연료가 미처 연소되지 못하여 발생
¾ 가솔린 자동차의 경우 3,000ppm , 디젤 자동차의 경우 300ppm

z 일산화탄소 (Carbon Monoxide

Monoxide, CO) PM
¾ 무색 무취의 기체로 일명 연탄가스로 잘 알려짐.
¾ 연료가 엔진 연소실내에서 불완전 연소되는 것이 발생 원인 SOF,PAH

z 질소산화물 (Nitric Oxides, NOx) Soot Sulfate

¾ 여름철 오존발생을 일으킴.
¾ 1700℃이상의 엔진 연소실 조건에서 대기의 80%인 질소가
산소와 결합하여 발생

z 입자상물질 (Particulate Matter, PM)

매연(검댕 soot)으로
¾ 경유 자동차에서 주로 발생하는 물질로 연료가 미처 타지 못하고 발생한 매연(검댕,
주 성분은 탄소임.
¾ 경유는 휘발점이 높음으로 연소실 내에서도 미처 기화되지 못하는 경우가 있어 매연으로 배출됨.

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 Ref : 이기형, 현대자동차 위탁 연구결과 보고서, 한양대학교, 2003. 12.

Diesel Combustion – Example

Flame Visualization in DI Diesel Engine

분사압: 50MPa

Cavity

6.13 6.88 9.99 15.17 19.68

Bore 분사압: 100MPa

4.40 5.90 6.65 7.41 9.67

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 Diesel Combustion Characteristics (1/3) Ref : DieselNet, 2002, Technical Notes,
“Combustion in Diesel Engines,”

■ Fuel/Air Distribution in the Fuel Spray of a DI Diesel

¾ Local air-fuel ratio
¾ Near
N the
th downstream
d t edge
d off the
th spray, mostt off the
th ddroplets
l t will
ill b
be
completely evaporated before ignition → premixed fuel vapor and air
■ Lean Flame Region (LFR)
¾ between the core and downstream edge of the spray, where AF may
vary 0~∞
¾ Ignition nuclei → independent nonluminous flame front propagation
¾ NO is formed at high local concentrations as combustion proceeds to its
completion

■ Lean Flame-Out Region (LFOR)

¾ Near the outer edge of the spray, where the mixture is too lean to
ignite or to support stable combustion
¾ Fuel decomposition → lighter HC molecules, Partial oxidation →
aldehydes, oxygenates
¾ In the zone where LFOR and LFR meet, primary combustion takes
place → CO, H2, H2O, CO2, HC, radicals (H, O, OH)

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 Diesel Combustion Characteristics (2/3) Ref : DieselNet, 2002, Technical Notes,
“Combustion in Diesel Engines,”

■ Spray
S C
Core
¾ Larger droplets gain heat by radiation and diffusion from LFR
¾ Completely evaporated → the flame will burn all the mixture
within
ithin the rich ignition limit.
limit
¾ Partially evaporated → individual droplet combustion
¾ P/L : adequate O2 → complete combustion → High NOx
¾ F/L : Fuel
ue rich
c → incomplete
co p ete combustion
co ust o → HC, C, CO, C

■ Spray Tail
¾ △P(Injection-Cylinder P) low → Spray atomization poor →
Large droplet → Penetration poor
¾ Cyl.T High → Evaporation High, but, Inadequate O2 →
HC,C,CO
■ Fuel Deposited on the Walls
¾ HC, C
■ Progression of Combustion, Cyl. P. and T.
¾①→②→③→④→⑤→⑥
■ Heat Release Rates in DI Engines
p rise in HRR,, 5%
¾ Premixed combustion : Initial sharp
¾ Diffusion combustion
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 Diesel Combustion Characteristics (3/3) Ref : DieselNet, 2002, Technical Notes,
“Combustion in Diesel Engines,”

■ Typical
T i l DI E
Engine
i H Heatt R
Release
l R
Rate
t Di
Diagram and
d Di
Diesell C
Combustion
b ti P Process
(1) Ignition Delay Period (a-b)
• Between the start of injection (SOI)
andd the
h start off combustion
b i (SOC)
(mainly, LFR) • Fuel vaporized, start to mix
• Pre-ignition chemistry get started
( i l S
(mainly, Spray Core)
C ) • Negative heat release rate
(2) Premixed or Rapid Burning Phase (b-c)
• Fuel+air mixture that has mixed to
within combustible limits burns
rapidly
idl
• High heat release
(3) Mixing Controlled Phase – Dominant
Phase (c-d)
( )
• After the “premixed” fuel and air
mixture has burned
• Then, burning rate depends on the
rate of mixing
(4) Late Combustion Phase (d-e)
• Remaining fuel and CO, soot from
rich regions get consumed
• Chemistry and mixing control the rate

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 NOx Emissions Ref : DieselNet, 2002, Technical Notes,
“Emission Formation in Diesel Engines,”

■ Thermal NOx
¾ Extended Zel’dovich Mechanism
ƒ O+N2=NO+N
NO+N (1), N+O2=NO+O
NO+O (2), N+OH=NO+H
N+OH NO+H (3)
kf =1.8×1011exp[-38,370/T(K)], 일반적인 탄화수소 화학반응의 Ta∼20,000K. ∴ 매우 높은 온도 필요
반응(1)은 느린반응으로서 반응조절단계이며 1,800K 이상에서 활성화됨. 활성화에너지 ∼76 kcal/mol
∴ Thermal NOx 생성되려면 고온지역內 충분한 잔류시간 ((약,10ms)
, ) 필요함.
■ Prompt NOx
¾ Fenimore Mechanism
ƒ CH+N2=HCN+N (1), HCN→NCO→NH→N→NO (2)
ƒ반응(1)의 활성화에너지 ∼14~22 kcal/mol, 상대적으로 작음. ∴ 저온반응
∴ Prompt NOx는 저온, 잔류시간이 짧은 작동영역에서 중요. 매우 빠른 반응이므로 제어 안됨.
■ Fuel NOx
ƒ 연료중 함유된 N 성분에 의하여 생성. 석탄의 Fuel-Borne Nitrogen ∼1%. 화력발전소에서 중요

■ At typical flame temperature NO2/NO ratio is negligibly small in spark engine.

¾ Spark Ignition engine : ∼ max.
max 2%
¾ Diesel engine : 10~30%
■ NOx control
ƒ 연소온도 제어 EGR byy ((1)) Dilution of the intake air with inert gases
g and ((2)) Heat absorption
p byy CO2

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 NOx Control by EGR Ref : DieselNet, 2002, Technical Notes,
“Exhaust Gas Recirculation,” 2000.07

¾ EGR configuration ¾ NOx reduction mechanism with EGR

• HPL (High Pressure Loop) • Dilution of the intake air with inert gases
d ( NO )
= k1 ( N 2 , O 2 ) − k2 ( NO, NO 2 )
dt
k1 , k2 = f (Tcomb ) , [ NO x ] = f (τ res )
O 2 , Tcomb , τ res ↓ NO x ↓
• Heat absorption of EGR stream

• LPL (Low Pressure Loop)

c p of CO2 , H 2O , N 2 = 36.0, 33.5, 29.2 kJ kmolK

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 What is PM – Soot Particle Formation
Ref : Barry A. A. L. van Setten, “Development of a
Liquid Catalyst for Diesel Soot Oxidation – from
Power to Prototype,” Ph.D. Thesis, de Technische
Universiteit Delft, 2001.02

• Fuel Pyrolsis
CA 1° @2,000rpm - C2Hx→C4Hx
- C3Hx+C3Hx
• Ring(Benzene,C6H6)
Ring(Benzene C6H6)
Formation
- HACA : H-Abstraction-
C2H2-Addition
- Aromatic combination
• Platelet (PAH) : Graphite like
sheets that could be seen as
primary building blocks of soot
particle (Polycyclic Aromatic
HC)
- HACA (High T)
- crystallization, PAH
agglomeration (Low T)
• Turbostratic Particle : Particle
that the building blocks (i.e.
platelets) are concentrated
around in a random
orientation around the center
of the particle
- coagulation
- surface growth
Schematic mechanism of the formation of soot particles • Soot Particle
104 - aggregation
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• Larger Soot Particles
 What is PM – Condensation Mechanisms
Ref : Barry A. A. L. van Setten,
“Development of a Liquid Catalyst for
Diesel Soot Oxidation – from Power to
Prototype,” Ph.D. Thesis, de Technische
U i
Universiteit
it it D
Delft,
lft 2001
2001.02
02

As the exhaust gas coos down hydrocarbons condenses

alongg two p
pathways
y :

(1) nucleation (2) adsorption

combustion +H2O
Sulfur in Fuel → SO2 → SO3 → H2SO4
98% 2%

Illustration of the condensation mechanisms that can operate in diesel exhaust gas Schematic structure of a chain-like aggregate of
primary soot particles and associated compounds

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 Soot Particle Formation Ref : DieselNet, 2002, Technical Notes,
“Emission Formation in Diesel Engines,”

■ Soot particles ■ Diesel engine variables affecting soot particle formation

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 Soot Particle Oxidation Ref : DieselNet, 2002, Technical Notes,
“Emission Formation in Diesel Engines,”

■ Diesel engine variables affecting soot particle oxidation

■ Other sources of particulate matter

¾ Loss of oil control
¾ Black smoke from excessive richness (over fueling
fueling, poor combustion
combustion, transients)
¾ White smoke (cold start, misfire)
¾ Other HC origins (nozzle dibble, secondary injections, after injections)
¾ Fuel q
qualityy (sulfur
( content,, aromatic content,, cetane number))

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 What is PM – Particle Size Distribution
Ref : Barry A. A. L. van Setten, “Development
of a Liquid Catalyst for Diesel Soot Oxidation –
from Power to Prototype,” Ph.D. Thesis, de
Technische Universiteit Delft, 2001.02

0.25
Nuclei Mode- Usually consists of Mass Weighting Number Weighting Surface Weighting
particles formed from volatile
precursors as exhaust
h t mixesi
Fine Particles
otal/dlogDp

with air during dilution

0.2 Dp < 2.5 μ m
Nanoparticles PM10
to

Dp < 50 nm
Normalizeed Concenttration,dC/C

Dp < 10 μ m
0.15

Accumulation Mode- Usually consists

In some cases this Ultrafine Particles mainly of carbonaceous agglomerates

0.1 mode may D < 100 nm that have survived the combustion process
p
consist of very
small p
particles
below the rang of
conventional
Coarse Mode- Usually
0.05 instruments, Dp consists of re-entrained
< 10 nm particles, crankcase fumes

0
0.001 0.010 0.100 1.000 10.000
Diameter (μm)
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 EM Comparison between Gasoline and Diesel
Ref : 인치범, “촉매와 자동차 공해제어기술 : 디젤배기가스 후처리”, 2000 전문능력향상교육과정, 금속재료연구팀, 2000.8

* PM : Particulate Matter (입자상물질)

10
가솔린(삼원촉매)
10
( )
디젤(촉매無)
디젤(산화촉매)
7
6 5.7

1.41.0 1 0.7
07
0
HC CO NOx PM

• NOx 및 PM 저감이 디젤엔진 후처리기술의 KEY POINT

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 Summary – Emission Control Technology Ref : “Diesel Emission Control,” DieselNet Technology Guide, www.dieselnet.com, 2003.8

T h l
Technology E i i Impact
Emission I t Si ifi
Significance
(1) Engine Design Technologies
Fuel Injection System
~90% PM reduction, ~75% NOx reduction, Combination of these engine design techniques was the major source of
Charge Air System
large reductions in HC/CO emissions achieved diesel emission reduction through the end of 1990’s; Potential for further
Combustion Chamber
i the
in h 1980-1990
1980 1990 timeframe
i f emission
i i reductions
d i in
i the
h ffuture
Electronic Control
Exhaust Gas Recirculation 30 ~ 50%+ NOx reduction Light-duty; Major heavy-duty engine applications from 2002 (USA)
(2) Fuel, Oil & Additive Technologies
Only limited direct emission impact in modern Sulfur content remains the critical property due to its effect on catalytic
Fuel & Lube Oil
engines aftertreatment technologies
Short term: emission-driven niche markets; Long term: critical importance
Alternative Diesel Fuels Variable, depending on fuel and emission
due to depletion of petroleum reserves
Small emission effect with modern engines and
Fuel Additives Possible use to assist particulate filter regeneration
quality diesel fuels
Niche markets: marine and stationary engines; centrally fueled fleets
Water Addition 1% NOx reduction for every 1% added water
(emulsions)
(3) Exhaust Gas Aftertreatment
High reduction of HC/CO emissions; PM Widely used on Euro 2/3 cars and on 1994 and later heavy
heavy-duty
duty urban
Diesel Oxidation Catalyst conversion depends on fuel sulfur, usually bus engines in the U.S.; Will remain a component of future emission
limited to maximum 20-30% (DOC) control Systems
Expected widespread use for (heavier) Euro 4 cars and heavy-duty
Diesel Particulate Filters 70-90%+ PM emission reduction (DPF)
US2007 engines; Currently used in retrofit programs
NOx reduction
d i potential i l off ~10-20%
10 20% in
i
Uncertain; NOx reduction potential insufficient for long-term regulatory
Lean NOx Catalysts passive systems, up to 50% in active systems
Objectives
(HC-SCR .or. LNC)
Future technology for Euro 5 heavy-duty diesel engines; Currently used in
Urea-SCR Catalysts ~90% NOx reduction (Urea-SCR)
stationaryy engines
g and other niche markets
Potential future technology for light duty engines worldwide and for
NOx Adsorber Catalysts ~90% NOx reduction potential (LNT)
heavy-duty engines in the U.S. (2007/2010)
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110
 Gasoline 3-Way Catalyst

• 3원촉매 (3-Way Catalyst)

¾ 1980년대 도입
¾ CO, HC, NOx 정화
¾ 이론공연비에서 작동
¾ 엔진의 한 부속품 개념
• 반응식
¾ HC + O2 = CO2 + H2O
¾ CO + O2 = CO2 + H2O
¾ NOx + HC/CO = N2 + CO2 + H2O

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 Lecture Notes on Applied Thermal Engineering 2011

Ch t 10
Chapter
What is Catalyst
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Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
 w/o catalyst with Pt or Pd

What is Catalyst Temperature ~ 700 ℃ ~ 100 ℃

Ea ~ 40 kcal/mol ~ 20 cal / mol

Reaction of adsorbed
Rate-limiting Dissociation of O2
CO with adsorbed O
step into O atoms
Without Catalyst atoms

CO + ½ O2
(Gas Phase)

With Catalyst

O O O CO2
(Gas Phase)
C O C
Adsorption Desorption
Pd Pd
Adsorbed CO and
Absorption Adsorbed O
Adsorbed CO2

¾ 촉매 : 자신은 변하지 않고 반응 대상 물질의 반응을 쉽게 일어나도록 도와주는 것

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 Closed-Coupled Catalytic Converter (CCC) and
U d fl
Underfloor C l i C
Catalytic Converter (UCC)

CCC

CCC
UCC
엔진

UCC
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 Catalytic Converter
¾ Structure

¾ Operating Conditions of Catalytic Converters

Gasoline Diesel
Temperature Range, °C 300~1,100 100~650
Temperature Gradient, °C 100~300 100~200
Space Velocity, 1/hr 30,000~100,000* 60,000~150,000*
* - higher S.V. may be used in aftermarket applications

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 Components and Precious Metals
¾ Components of the Catalytic Converter
• 담층 (Washcoat) : 촉매물질을 포함하고 있는 코팅물질. 주로 알루 Pore
미나(Al2O3) 분말로
미나( 말 구성되어 있 있으며 며어
어느 배기가
배기가스를 정화할 것인
가에 따라 첨가되는 조촉매가 달라짐.
• 담체 (Substrate) : 담층이 코팅되는 벌집모양의 형태로서, 배기가스
가 지나가는 통로가 되며, 담체의 형상 및 담체의 벽 두께에 따라서
배기가스 저감효과가 달라진다.
• 지지체 (Support) : 담체가 고정되어 파손되지 않도록 지지하는 역할
을 함. 스테인레스 와이어나 매트를 사용하여 담체를 지지함. 최근
매트 가 주로 사용됨. 팽창/비팽창 매트가 있으며 주로 팽창매트를
사용.
¾ Components of the Precious Metals
• Pd : 주로 HC를 정화하는데 이용되며 내열성이 우수하여 CCC 용으로 사용됨. CCC 위치에서 주로 Pd 단
독으로 사용되며 Pd-Rh의 형태로도 사용됨.
• Pt : 주로 CO와 NOx의 정화에 사용되며 Pd에 비하여 내열성이 떨어지므로 UCC에 사용됨. Pt-Rh의 형태로
사용되나 Pd-Pt-Rh의 형태로도 사용.
• Rh : HC, CO, NOx 정화성능이 Pd과 Pt 보다 우수하나, 주로 NOx 정화를 위하여 사용함. Pd이나 Pt에 비하
여 3~4 배 정도의 고가이므로 사용량의 제한을 받음.

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 Cellular Properties of Monoliths (1/2) Ref : “Cellular Monolith Substrates,” DieselNet Technology Guide, www.dieselnet.com, 1998.8

¾ Cell density, N
• The number of channels per unit cross-sectional area
N = 1 s2
• unit : cells per square inches (cpsi) or cells per square
centimeters (1/cm2)
• Usually, 200~300 cpsi cells are used in diesel catalysts

¾ Specific geometric surface area, GSA, ag

• Total channel surface area per unit of substrate volume, for
square cells :
ag = 4 ( s − w ) s 2 = 4 ( 1 − w s ) N 0.5
¾ Open Frontal Area., OFA, AF, (or substrate void fraction)

• Part of the total substrate cross-sectional area which is available

for the gas flow, for square cells, the ratio of the open area to
the total cross
cross-sectional
sectional channel area :
AF A = ( s − w ) s 2 = ( 1 − w s )
2 2

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 Cellular Properties of Monoliths (2/2) Ref : “Cellular Monolith Substrates,” DieselNet Technology Guide, www.dieselnet.com, 1998.8

¾ Hydraulic diameter, dh
• A measure of size for non circular channels in all hydraulics
dh = 4 Ach Och
Ach : channel open area
Och : channel wetted perimeter
• For cellular catalyst substrates,
dh = 4 ( AF A ) ag
y, ρb
¾ Bulk density,
ρb = ρm ( 1 − P ) ( 1 − AF A )
ρm : material density, kg m 3
P : material porosity,
porosity dimensionless
¾ Total surface area, AT
AT = Vag
¾ Heat
H capacity,
i C
C = c p ρbV
c p : specific heat capacity of the substrate material

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 Canning Methods Ref. : “Catalytic Converters,” DieselNet
Technology Guide, www.dieselnet.com, 2004.03

■ Overview ■ Stuffing

■ Tourniquet

■ Clamshell
■ Swaging

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 Basic Terms on Conversion of Pollutants Ref : “Emission Control Catalysts,” DieselNet Technology Guide, www.dieselnet.com, 1998.8

¾ Conversion Efficiency
• If an exhaust gas component (A) reacts over a
catalyst with another component (B) :
A + B → Products
• Conversion efficiency of A
Ci − Co
Conversion Efficiency
ff = × 100%
%
Ci
Ci : concentration of A at the catalyst inlet
C o : concentration of A at the catalyst outlet
¾ Space Velocity
¾ Light-Off Temperature, LOT
V
• Minimum temperature necessary to initiate the SV = [1 hr]
Vr
catalytic behavior,
behavior T50 V : volumetric gas flow rate at STP, ⎡⎣m 3 hr ⎤⎦

¾ Catalyst (Temperature) Window Vr : reactor volume, ⎡⎣m 3 ⎤⎦

• curve B ¾ Noble Metal Loading
• Typical for SCR by hydrocarbon or ammonia • Pt : Pd : Rh
• 50g, 4:0:1 means Pt=40g/ft3 and
Rh=10g/ft3
• 1 g/ft
/ft3 = 0.03531
0 03531 g/liter
/lit

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 Catalyst Fundamentals Ref : “Catalyst Fundamentals,” DieselNet
Technology Guide, www.dieselnet.com,
2000.11

¾ Chemical Reaction Kinetics and Equilibrium ¾ Activity

aA + bB + cC + ⋅⋅⋅ ↔ rR + sS + ⋅⋅⋅ • Catalyst’s ability to enhance reaction rates
Forward reaction rate : r = kC Aa C BbCCc ⋅⋅⋅ ¾ Selectivity
Backward reaction rate : r ′ = k′C Rr CSs ⋅⋅⋅ • Catalyst’s ability to accelerate certain reaction
Net rate of reaction : in preference to others
r0 = r − r ′ = kC Aa C BbCCc ⋅⋅ − k′C Rr CSs ⋅⋅⋅ C 2 H5 OH = C 2 H4 + H2 O ( Al 2 O3 , 354°C )
At equilibrium, equilibrium constant, K :
C 2 H5 OH = CH3CHO + H2 ( Cu )
• often depends on temperature
r0 = 0 → C Rr CSs ⋅⋅⋅ C Aa C BbCCc ⋅⋅⋅ = k k′ = K
2C 2 H5OH = ( C 2 H5 )2 + H2 O ( Al 2 O3 , 269°C )
Reaction rate constant, k :
k = k0 exp ( Ea RT ) • Empirical Sabatier Rule : Catalyst selectivity
¾ Catalyst Definition improvement is always accompanied by a
deterioration in its activityy
¾ Classification of Catalyst System
• Homogeneous catalyst
• Heterogeneous
g catalyst
y
• Supported catalyst
• Unsupported catalyst

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 Reaction Steps in Heterogeneous Catalyst
Ref : “Catalyst
Catalyst Fundamentals,”
Fundamentals, DieselNet Technology Guide, www.dieselnet.com, 2000.11

① Bulk Diffusion of Reactants

② Pore Diffusion of Reactants
③ Adsorption of Reactants
④ Catalytic Reaction
⑤ D
Desorption
i off Products
P d
⑥ Pore Diffusion of Products
⑦ Bulk Diffusion of Products

①②③ ④ ⑤⑥⑦

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 Reaction Mechanism and Reaction Rates
Ref1 : “Catalyst
Catalyst Fundamentals,
Fundamentals,” DieselNet Technology Guide, www.dieselnet.com, 2000.11
¾ Bulk
B lk mass transfer
f Ref2 : R. M. Heck and R. J. Farrauto, 2002, Catalytic Air Pollution Control, 2nd Ed., Wiley Inter-Science, p.7

① Bulk Diffusion of Reactants 30 kcal/mol ~

⑦ Bulk Diffusion of Products
Chemical
¾ Pore
P diff
diffusion
i
② Pore Diffusion of Reactants reaction
⑥ Pore Diffusion of Products
¾ Chemical reaction 6 ~ 10kcal/mol
③ Adsorption of Reactants Pore
④ Catalytic Reaction
⑤ Desorption of Products
diffusion
¾ Rate limiting steps 2 ~ 4kcal/mol
Bulk mass exp(−Ea /RT )
transfer
k
3
T 2
rateof
condition porediffusion chemisorption

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 Significance of the Rate Limiting Step
Ref : R. M. Heck and R. J. Farrauto, 2002, Catalytic Air Pollution Control, 2nd Ed., Wiley Inter
Inter-Science,
Science, p.10
¾ If chemical kinetics are rate-limiting
• High catalyst surface area
• increase catalyst component loading & uniform dispersion

¾ If pore diffusion limitations

• Larger pores and catalyst component located as
close
l to
t th
the surface
f
• Decrease the thickness of the carrier or washcoat
¾ If bulk mass transfer is rate-limiting
• Increase turbulence in the bulk gas
• Increase geometry surface area (i.e. external area)

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 Catalyst Deactivation Mechanism
Ref : “Catalyst
Catalyst Fundamentals,”
Fundamentals, DieselNet Technology Guide, www.dieselnet.com, 2000.11

(1) Poisoning
¾ Selective Catalyst Poisoning
• Pb,
Pb Hg,
Hg Cd 등에 의한 피독
• SO2 등에 의한 활성점 차단
• 열처리, 세척 등을 통한 회복 가능

¾ Catalyst Fouling (Masking)

• nonselective poisoning, masking
• 윤활유의 P 등에 의한 침전현상 Selective Catalyst Poisoning Catalyst Fouling

(2) Thermal Deactivation

¾ Catalyst Sintering
• 귀금속의 소결/응집
• 촉매소결 감소를 위하여 CeO2,
La2O3 등의 Stabilizer 사용

¾W
Washcoat
h t SiSintering
t i
• 담층의 소결, 세공막힘 현상 발생
Catalyst Sintering Washcoat Sintering • 담층소결 감소를 위하여 BaO,
La2O3, SiO2, ZrO2 등의 Stabilizer 사
용
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 Lecture Notes on Applied Thermal Engineering 2011

Ch t 11
Chapter
The Preparation of Catalytic Materials
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Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
 Carriers Ref : R. M. Heck and R. J. Farrauto, 2002, Catalytic
Air Pollution Control, 2nd Ed., Wiley Inter-Science,
p.11

¾ Catalyst
▶ Novel metal, Novel metal oxide : Pt, Pd, Rh, V2O5
▶ Dispersed on a high-surface-area carrier such as Al2O3, SiO2, TiO2, or crystalline alumina
silicates
ili t or zeolite
lit
¾ Carrier (or Washcoat)
▶ A high-surface-area inorganic material containing a complex pore structure through which
catalytic
l i materials
i l suchh as P
Pt, Pd
Pd, Rh
Rh, andd V2O5 are deposited.
d i d
▶ Al2O3, SiO2, TiO2, Zeolites
▶ It does play a critical role : Activity, Selectivity, Durability
¾ Critical
C i i l details
d il off the
h preparation
i are maintained
i i d as trade
d secrets
▶ To maintain an advantage over the competitor

¾ BET (Brunauer
(Brunauer-Emmett-Teller)
Emmett Teller) Surface Area, [m2/g]
vm
S= NAm
V
V : 표준온도와 압력에서 흡착하는 기체의 몰부티
N : 아보가드로 수
Am : 한 분자가 차지하는 면적 (질소분자의 경우 0.162 mm2)
vm : 단분자층 흡착량

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 Carriers – Al2O3 Ref : R. M. Heck and R. J. Farrauto, 2002, Catalytic
Air Pollution Control, 2nd Ed., Wiley Inter-Science

¾ The most common carrier

z Its properties depend on its preparation, purity, and thermal history
¾ The high surface area is created by heat-treating
heat treating or calcining in air
z At about 500 oC : 20 – 50 Å diameter, polymer-type chains
¾ Calcination at different temperature
p
Name Aluminum Oxide
z Physical surface area change
Formula Al2O3
z Boehmite (monohydrate, Al2O3H2O)
Formula Weight 101.94
h γ -monohydrate ( 500 ~ 850 C), 100-200
2
o 100 200 m /g
Appearance White powder
h δ -monohydrate ( 850 ~ 1050 o C)
Density 4 g/cc
h θ -monohydrate
y ( 1050 ~ 1150 C) o
M lti Point
Melting P i t 1999 to
t 2032 ℃
h α -monohydrate ( > 1150 oC), 1-5 m /g, ~1000 Å
2
LaRoche, Condea-Vista, Alcoa,
Suppliers
z Bayerite (trihydrate, Al2O33H2O) W.R. Grace

h η -monohydrate
h d ( 300 ~ 500 oC )
h θ -monohydrate ( 850 ~ 1150 oC ) Al2O3 is highly
h α -monohydrate
y ( > 1150 oC)
reactive with SO3
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 Carriers – Al2O3 Ref : R. M. Heck and R. J. Farrauto, 2002, Catalytic
Air Pollution Control, 2nd Ed., Wiley Inter-Science

Surface area of ~150 m2/g Surface area of 1~5 m2/g

Scanning electronmicrograph (SEM) of (a) gamma-Al2O3 (80,000 magnification) and (b)

alpha-Al
p 2O3 (
(80,000
, magnification).
g )

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 Carriers – SiO2 and TiO2 Ref : R. M. Heck and R. J. Farrauto, 2002, Catalytic
Air Pollution Control, 2nd Ed., Wiley Inter-Science

SiO2 ¾ Silicon Dioxide

¾ The inertness towards reacting with sulfur-bearing compounds
z In contrast, alumina is highly reactive with SO3
¾ Low thermal stability Name Silicon dioxide

¾ Surface area : 300 ~ 400 m2/g

Surface-area Formula SiO2

Formula Weight 60.06

Appearance White powder

TiO2 ¾ Titanium dioxide

Titanium
¾ The inertness to sulfate formation Name
dioxide
z Carrier for vanadia in selective catalytic reduction of NOx Formula TiO2
¾ Two crystal structure Formula Weight 79.9
z Anatase
3.84 g/cc
h Precipitation from titanate solution, decomposition of organo-
Density (anatase), 4.26
titanates g/cc (rutile)
2
h Surface area : 50 ~ 80 (or 120) m /g
h Thermal stability up to 500 oC
z Rutile : Surface area : < 10 m2/g
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 Carriers – Zeolite Ref : R. M. Heck and R. J. Farrauto, 2002, Catalytic
Air Pollution Control, 2nd Ed., Wiley Inter-Science

¾ High specific surface area ~ 400 m2/g

¾ Pore structure dimensions : 3~8 Å
¾ Molecular sieves
¾ Its properties depend on Si/Al
z ZSM-12 (large pore zeolite),
z ZSM-5 (medium pore zeolite),
z ZSM-8 (small pore zeolite)
¾ Application
z Mordenite : Na8(Al2O3)8(SiO2)404H2O,The
O The high-temperature
high temperature selective
reduction of NOx
Name Zeolites, molecular sieves
z Others : Hydrocarbon trapping components
Formula x SiO2 y Al2O3
¾ Thermal stability : up to 500 oC GSA, UOP, Degussa, Zeolyst,
Suppliers
Zeochem

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 Monolithic Materials Ref : R. M. Heck and R. J. Farrauto, 2002, Catalytic
Air Pollution Control, 2nd Ed., Wiley Inter-Science

¾ Monolithic or Honeycomb Materials : A unitary structure composed of inorganic oxides

or metals in the structure of a honeycomb with uniform-sized and parallel channels that may
be square,
square sinusoidal,
sinusoidal triangular,
triangular hexagonal,
hexagonal round,
round and so on.
¾ Commercial ceramic monoliths
• They have large pores and low surface areas (e.g., 0.3 m2/g)
• It
I is
i necessary to d
deposit
i a hi
high-surface-area
h f carrier,
i which
hi h iis subsequently
b l catalyzed,
l d
onto the channel walls.
• The catalyzed coating is composed of a high-surface-carrier such as Al2O3
impregnated with a catalytic component → Catalyzed Washcoat

double washcoat

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 Ceramic Monoliths Ref : R. M. Heck and R. J. Farrauto, 2002, Catalytic
Air Pollution Control, 2nd Ed., Wiley Inter-Science,
p.20

¾ Synthetic cordierite ( 2MgO ⋅ 2Al 2 O 3 ⋅ 5SiO 2) is by far the most commonly used ceramic
for monolithic catalyst support applications
¾ Sizes up to about 11 in.(27.94
in (27 94 cm) in diameter and 7 in.(17.78
in (17 78 cm) long,
long with
9~1,200 cpsi can be made
¾ Characteristics :
• low
l pressure ddrop
• thermal shock resistance : low
thermal expansion coefficient
−7 o
about 10 × 10 C
• mechanical strength : axial
strength
g over 3,, 000 lb in 2
• melting point : over 1, 300 oC
• catalyst compatibility : automotive ceramic monoliths have
well designed pore structures (of ~ 3 − 4 μ m ) that allow good
channel and mechanical bonding to the washcoat

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 Metal Monoliths Ref : R. M. Heck and R. J. Farrauto, 2002, Catalytic
Air Pollution Control, 2nd Ed., Wiley Inter-Science,
p.21
¾ Monoliths made of high-temperature-resistant aluminum-containing steels are becoming
increasingly popular as catalyst supports, mainly because of they can be prepared with
thinner walls than a ceramic This offers the potential for higher cell densities (lower
wallll thickness)
hi k ) with
i h lower
l pressure d
drop
¾ Thermal conductivity is considerably higher (~15-20 times) than the ceramic, resulting
in faster heatup good for oxidizing HC and CO when a vehicle is cold
¾ Problem :
• adhesion of the oxide-based washcoat to the metallic
surface and
• corrosion of the steel in high-temperature steam
environments, and
• more expensive
p than their ceramic counterpart
p
¾ Applications :
• low-temperature applications such as NOx in power plants,
O3 abatement in airplanes, CO and VOC abatement, and
abatement of oil based emissions from restaurants
• as they are electrically conductive, they have found limited
use in electrically heated catalytic converters for rapid
conversions of emissions during startup
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 Lecture Notes on Applied Thermal Engineering 2011

Ch t 12
Chapter
Monolithic Reactor for Environmental Catalysis
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Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
 Chemical Kinetic Control Ref : R. M. Heck and R. J. Farrauto, 2002, Catalytic Air
Pollution Control, 2nd Ed., Wiley Inter-Science, pp.45-55

¾ For pollution abatement application it is common to utilize a monolith or honeycomb-

supported catalyst to minimize the pressure drop associated with high flowrates
¾ Th
The incoming
i i pollutant
ll laden
l d stream is i often
f h
hot, iit can b
be preheated
h d to a sufficient
ffi i
temperature to initiate the catalytic reactions.
¾ A material balance across anyy reactor ggives the followingg equation
q assumingg one-
dimensional, plug flow, and steady-state operation :
v = velocity, [ cm s ]
d( vC ) C = molar
l concentration,i ⎡⎣gmoll cm 3 ⎤⎦
= −r
dz z = length, [ cm ]
r = rate of reaction, ⎡⎣ggmol cm 3 ⋅ s ⎤⎦

¾ When conversion or the reactant concentration is low, the reactor is considered

isothermal; hence
dC
v = −r
dz

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 Chemical Kinetic Control - VHSV
¾ Assuming the oxidation of C2H6 to CO2 and H2O in a large excess of O2 in a fixed bed
of catalyst
7 dC(C2 H6 )
C 2 H 6 + O 2 → 2CO 2 + 3H 2 O v = − k′C(C2 H6 )
2 dz
Integrating this equation between the inlet (i) and outlet (o) gives
Co k′z
ln =− = − k′t
Ci v
where t is actual residence time (seconds) that the C2H6 spends in the catalyst bed.

¾ Space Velocity, SV=volume flowrate of feed /

physical volume of catalyst
1
SV =
( residence ) time
Co k′′
ln =−
Ci SV

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 Bulk Mass Transfer
¾ When the reaction rate is controlled by bulk phase mass transfer

⎛ N Sh ( a /ε )L ⎞
Fractional conversion= 1 − exp ⎜ − ⎟
⎝ N Sc N Re ⎠
geometric surface area per unit volume, ⎡⎣ cm cm ⎤⎦
2 3
• Sherwood number a=
K g dch D= diffusivity of pollutant in air, ⎡⎣ cm 2 s ⎤⎦
N Sh =
D L= h
honeycomb
b length,
l h [ cm ]
• Schmidt number W = total mass flowrate to honeycomb catalyst, [g s ]
μ A= frontal area of honeycomb, ⎡⎣ cm 2 ⎦⎤
N Sc =
ρD dch = hydraulic diameter of homeycomb channel, ⎡⎣ cm 2 ⎤⎦

• channel Reynolds number ρ= gas density at operating conditions, ⎡⎣g cm 3 ⎤⎦

μ= conditions, [g s ⋅ cm ]
gas viscosity at operating conditions
⎛ W ⎞ dch
N Re = ⎜ ⎟ ε= void fraction of honeycomb, dimensionless
⎝ Aε ⎠ μ

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 Example

http://procom.chonbuk.ac.kr
http://www.ngvtek.com 139 http://procom.chonbuk.ac.kr
 Example

http://procom.chonbuk.ac.kr
http://www.ngvtek.com 140 http://procom.chonbuk.ac.kr
 Reactor Bed Pressure Drop
¾ The velocity in the channel

W flowrate, [g s ]
W = mass fl
v= ρ = density, ⎡⎣g cm 3 ⎤⎦
ρ Aε ε = void friction, dimensionless
A = cross-sectional area, ⎡⎣ cm ⎤⎦
2

¾ Reactor bed pressure drop

2 ffL ρ vch2 f = friction factor, dimensionless

P= ρ = gas density, ⎡⎣g cm 3 ⎤⎦
gc dch dch = channel diameter, [ cm ]
gc = gravitational constant,
constant
= 980.665 ⎡⎣ cm s 2 ⎤⎦
g , [ ccm ]
L = channel length,

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 Lecture Notes on Applied Thermal Engineering 2011

Ch t 13
Chapter
Automotive Substrates
http://procom.chonbuk.ac.kr 142
Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
 Requirements for Substrates Ref : R. M. Heck and R. J. Farrauto, 2002, Catalytic
Air Pollution Control, 2nd Ed., Wiley Inter-Science

¾ Requirements that an ideal substrate must meet :

• It must be coatable with high BET area washcoat.
• It must have low thermal mass, low heat capacity,
and efficient heat transfer to permit gaseous heat
to heat up the catalyst carrying washcoat quickly,
notably during lightoff.
lightoff
• It must provide high surface area per unit volume
to occupy minimum space while meeting emission
requirements
requirements.
• It must withstand high-use temperature.
• It must have good thermal shock resistance due to
Parameters affecting performance of catalytic
severe temperature
t t gradients
di t arising
i i ffrom ffuell converter
management and/or engine malfunction.

• It must minimize backpressure to conserve engine power for rapid response to transient loads.
loads
• It must have high strength over the operating temperature range to withstand vibrational loads
and road shocks.

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 Design and Sizing of Substrates Ref : R. M. Heck and R. J. Farrauto, 2002, Catalytic
Air Pollution Control, 2nd Ed., Wiley Inter-Science

¾ Nomenclature
• n : cell density
• GSA : geometric surface area
• OFA : open frontal area
measure of temperature gradient the
• Dh : hydraulic diameter substrate can withstand prior to crush
• ρ : bulk densityy
• TIF : thermal integrity factor measure of crush strength of substrate
in the diagonal direction
• MIF : mechanical integrity factor
• Rf : resistance to flow measure of backpressure
• Hs : heat transfer measure of steady-state heat transfer
• LOF : lightoff measure of lightoff performance
These parameters affect both performance and durability of the catalytic converter
¾ An ideal substrate must offer high Dh, GSA, OFA, TIF, MIF, Hs, and LOF values and low
ρ and Rf values
• For good lightoff performance → High LOF value
• For high conversion efficiency → High n, high GSA, high Hs Values
• For low backpressure → High OFA, large Dh, low Rf values
• For high mechanical and thermal durability → High MIF and TIF
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 Geometric Properties of Various Substrates
Ref : R. M. Heck and R. J. Farrauto, 2002, Catalytic Air Pollution Control, 2nd Ed., Wiley Inter-Science

¾ Square Cell Substrates ¾ Triangular Cell Substrates ¾ Hex Cell Substrates

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 Example Geometric Properties of Honeycomb Substrates
Ref : R. M. Heck and R. J. Farrauto, 2002, Catalytic Air Pollution Control, 2nd Ed., Wiley Inter-Science

¾ 200/12□ substrate – The initial substrate (‘1975)

• Low n, GSA, and LOF → meet less stringent
emission requirement
• Large Dh, low Rf, modest OFA → minimize the
backpressure and conserve engine power
• High MIF and modest TIF → meet durability
requirement
¾ 300/12□, 236/11.5 △ substrate – The 2nd substrate
• Higher LOF, GSA, Hs, and MIF → to meet more
stringent emission and durability requirements
• lower Dh, and higher Rf → adverse effect on
backpressure
¾ 400/6.5□ substrate – The standard substrate (early
‘1980s)
• Highest LOF, GSA, Hs, OFA, and TIF → to meet
more stringent emission regulations
• No compromise in Dh and Rf
• Adequate MIF
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 Physical Property – Mechanical Durability
Ref : R. M. Heck and R. J. Farrauto, 2002, Catalytic Air Pollution Control, 2nd Ed., Wiley Inter-Science

¾ Holding pressure ¾ Ranking of contours of substrate for optimum durability

¾ Shear cracking during clamshell canning of misaligned substrate

Ff ≥ Fv + Fb
⎛ d ⎞ ⎛ d ⎞
pm ≥ ⎜ ⎟ ρc a + ⎜ ⎟ pb
⎝ 4μ ⎠
http://procom.chonbuk.ac.kr ⎝ 4μl ⎠ 147
 Advances in Substrate Development Ref : R. M. Heck and R. J. Farrauto, 2002, Catalytic Air Pollution Control, 2nd Ed., Wiley Inter-Science

¾ Ceramic – Thin wall cordierite ¾ Metallic

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 Lecture Notes on Applied Thermal Engineering 2011

Ch t 14
Chapter
Diesel Catalysts
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Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
 EURO-5 ?

HDDE DePM System DeNOx System

DOC DPF SCR

Urea Injection
CO(NH
( 2)2 → 2NH2+CO
4HC 5O2 → 4CO2+2H
4HC+5O 2H2O
CO(NH2)2+H2O → 2NH3+CO2
2CO + O2 → 2CO2
C (Soot) + O2 → CO/CO2 NH2+NO → N2+H2O
SOF + O2 → CO2+2H2O
C (Soot)
(S t) + NO2 → CO/CO2 + NO 6NO+4NH3 → 5N2+6H2O
NO + O2 → NO2 4NO+4NH3+O2 → 4N2+6H2O
CO + O2 → CO2 ((CO from 6NO2+8NH3 → 7N2+12H2O
Soot)
HC,CO + O2 → CO2+ 2NO2+4NH3+O2 → 3N2+6H2O
H2 O
((residual gaseous
g HC,, CO)) NO2+NO2+2NH3 → 2N2+3H2O

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 System Layout for Aftretreatments Development
ECU CAN DATA Additional Logging
Data
• TPS or Fuel flow DATA Logger
• RPM
• Temp. (Total ~20 ch)
• Water Temp.
• 가속도 센서 (2 ch)
• Oil Temp.
• Speed ECU CAN DATA
• Intake P & T 재생제어유닛 Urea제어유닛

Fuel Returrn
Fuel
Tank CRDi Post Urea Urea
HC 분사
injection을 Pump Filter
분사 조절기 Urea
Intake 펌프 구현하기 Tank
CRl Pump 위한 경유
Euro-4, HMC ★ engine 분사장치 Urea Feed Line

Urea Urea Return Line

Injector
HC노즐
Exhaust
DOC DPF SCR
AOC

T_exh B.P NOx-1 T1 T2 Del.P T3 NOx- T4 NOx-

2 3

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 Overview Ref : SwRI, “Post-Combustion Emission Control
Devices for Diesel Applications”, 2000.5

NOx / PM Control

NOx PM

SOFs Solids

DeNOx LNT SCR DOC DPF

¾ LNT (Lean NOx Trap, 흡장형촉매) Active Passive

¾ SCR (Selective Catalytic Reduction,
Reduction 선택적촉매환원)
¾ DOC (Diesel Oxidation Ctalytst, 디젤산화촉매)
¾ DPF (Diesel Particulate Filter, 매연여과장치) Combination

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 Diesel Catalysts - Overview Ref : “Diesel Catalysts,” DieselNet Technology Guide,
www.dieselnet.com, 2004.05

■ Diesel Catalyst Technologies

Catalyst Technology Reaction Type Reduced Emissions Commercial Status
Diesel Oxidation CO, HC (incl. PAH),
Oxidation Established commercial technology
Catalyst PM (SOF), odor
Commercial technology for stationary and
SCR (or Urea/NH3- Selective catalytic reduction by
NOx marine engines, under development for truck
SCR) ammonia/urea
and car engines
Some commercial oxidation catalysts
DeNOx (Lean NOx) Selective catalytic reduction by NOx, CO, HC, PM
incorporate small NOx reduction activity
Catalyst (or HC-SCR) Hydrocarbons (SOF)
(passive DeNOx)
Adsorption (trapping) of NOx from lean
NOx Adsorbers (or Technology under development,
exhaust,
h t followed
f ll db by release
l and
d catalytic
t l ti NOx, CO
CO, HC
LNT) commercialized on lean burn gasoline engines
reduction under rich conditions

■ DOC ■ Urea-SCR ■ LNT (NOx Adsorber)

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 DOC – Diesel Oxidation Catalyst (1/3)
¾ Reducing Emissions :
• Gas phase hydrocarbons (HC)
g
• The organic fraction of diesel
particulates (SOF)
• Carbon monoxide (CO) Washcoat Monolith
• Aldehyde, PAHs, diesel odor
Soot Soot
S
¾ Reaction (Oxidation) SOF H2O+CO2
PM
[Hydrocarbons]+O2=CO2+H2O Sulfate Sulfate
CO+1/2O2=CO2
¾ Undesirable Reaction Gaseous Sulfate
SO2
2SO2+O2=2SO3
SO3+H2O=H2SO4 C
Conversion
i off CO and
d HC iin Di
Diesell O
Oxidation
id ti C Catalyst
t l t
When temperature decreases, gaseous sulfuric
acid (SO3) combines water molecules to form
hydrated sulfuric acid particles (H2SO4) called
s lfate particulates,
sulfate partic lates which
hich can significantl
significantly
increase the total PM emissions
¾ Other Reaction
NO+1/2O2=NO2

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 DOC – Diesel Oxidation Catalyst (2/3)
¾ Platinum and Palladium DOC ¾ Nitrogen Oxides
• Total NOx emissions are in most cases not
changed by the DOC
• Some DOCs claim small Nox reductions,
usually 10~20%, due to
(1) lean Nox performance by selective
reactions of HC
(2) storage of nitrates in the washcoat by Ba
6.925 liter DI turbocharged aftercooled diesel engine,
(stabilizer)
HD FTP Transient test (400 cpsi substrates of 5.07 liter volume )
• Catalytic generation of NO2
• Pt > Pd, opposite to gasoline emission
• Gasoline HCs : short carbon chain, NO+1/2O2=NO2
unsaturated
• Diesel
Di l HCs
HC : llong carbon
b chain,
h i saturated
t t d

¾ Heat Effects
• Gasoline > Diesel
• Concentrations of CO and HC
: Gasoline > Diesel

Concentration of NO2 with Diesel Oxidation Catalyst

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DOC – Diesel Oxidation Catalyst (3/3)
¾ Sulfate Formation
¾ Particulate Matter (PM)
• Catalyst selectivity became the focus in the
■ Impact of Diesel Oxidation Catalyst on PM Emission development of DOC, i.e. high activity for
HCs and low activity for SO2 and sulfate
particulate
• The generation of sulfates in the DOC
depends on :
(1) Sulfur content in the fuel
(2) Catalyst temperature
(3) Catalyst formulation

• The net effect of the DOC on PM is a simple

combination of the SOF and SO4
• The desired SOF effect prevails at low
temperature
• If S is present in the fuel
fuel, there is always a
temperature above which an increase of PM ¾ Storage and release of sulfates from the
• Wet particulates with high SOF contents can washcoat
be effectively controlled by a DOC
(1) Al2(SO4)3=Al
Al2O3+3SO
3SO3
(2) Al2O3SO2=Al2O3+SO2
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 Diesel De-NOx Catalysts Ref : 인치범, “촉매와 자동차 공해제어기술 : 디젤배기가스 후
처리”, 2000 전문능력향상교육과정, 금속재료연구팀,
2000.8

Potential for Lean

Control Strategies Issues
NOx Conversion
Passive HC-SCR
HC SCR 0 15%
0~15% ♣ Limited to Engine-out
Engine out Chemistry
♣ Fuel Penalty and HC-slip
DeNOx Active HC-SCR ♣ Durable High Temperature Catalyst
15~35%
((HC Injection)
j ) ♣ Transient Control
♣ N2O Formation
♣ Requirement for Rich Regeneration
♣ Sulfate Poisoning of Trap Sites
Lean NOx Trap (LNT) 40~70% ♣ Durability of Pt at High Temperature
♣ SV and Temp. Limits on Trapping Efficiency
♣ Low Temp. Kinetics of NO2 Formation
♣ Infrastructure
I f t t for
f U Urea D
Delivery
li
Urea-SCR System 60~90% ♣ Transient Reductant Injection
♣ Ammonia Slip Minimization
♣ Plasma Reactor + Urea SCR
Plasma Enhanced ♣ Enhanced Low Temperature Conversion
70~90%
SCR System ♣ Electric Power Limitation
♣ High Cost

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 Lean NOx Catalyst (LNC or HC-SCR) Ref : “Lean NOx Catalyst,” DieselNet Technology Guide, www.dieselnet.com, 2001.4

¾ Terminology ¾ Passive and Active DeNOx systems

Catalysts selectively promoting the reduction of
Nox byy HCs have been termed “Lean NOx
Catalysts (LNC) or “DeNOx Catalysts”

¾ Chemical Reactions
In the selective catalytic reduction, HCs react
with NOx, rather than O2, to form nitrogen,
CO2, and water :
(1) {HC}+NOx=N
{HC}+NO N2+CO2+H2O
(2) CmHn+(2m+1/2n)NO
=(m+1/4n)N2+mCO2+1/2nH2O - Exhaust injection : accurate, but complex and costly
- Post injection : wall wetting (oil, wear)
The competitive,
p , non-selective reaction with - Late injection : partial combustion / cracking before reaching
oxygen : catalyst
(3) {HC}+O2=CO2+H2O
(4) CmHn+(2m+1/4n)NO
=mCO
mCO2+1/2nH2O
DeNOx catalysts have to be optimized to
selectively promote the desired reaction (1-2)
with HCs over the undesired reaction with O2
(3-4)
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 LNT (1/2) Ref : “NOx Adsorbers,” DieselNet Technology
Guide, www.dieselnet.com, 2001.4

¾ Concept ¾ NOx trapping/reduction mechanism

• Adsorption and storage of NOx in the
y duringg lean drivingg conditions
catalyst
• Releasing and regeneration it under rich
operation

NOx absorption and reduction mechanism

• Adsorption
NO + 1 2 O 2 = NO 2
BaO + 2NO 2 + 1 2 O 2 = Ba ( NO 3 )2
• Reduction
• The catalyst washcoat combines three Ba ( NO 3 )2 = BaO + 2NO + 3 2 O 2
active components : Ba ( NO 3 )2 = BaO + 2NO 2 + 1 2 O 2
(1) an oxdiation catalyst (for example, Pt)
(2) an adsorbant (for example, barium NO + CO = 1 2 N 2 + CO 2
oxide BaO)
oxide, BaO), and • Undesirable reaction : Barium Sulfate,
Sulfate BaSO4
(3) a reductant catalyst (for example, Rh) SO 2 + 1 2 O 2 = SO 3
BaO + SO 3 = BaSO 4

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 LNT (2/2) Ref : “NOx Adsorbers,” DieselNet Technology
Guide, www.dieselnet.com, 2001.4
• Regeneration
¾ Catalyst System
• NOx adsorber = TWC + NOx storage component
• NOx storageg component
p
- Alkaline earths : Ba, Ca, Sr, Mg
- Alkali metals : K, Na, Li, Cs
- Rare earth metals : La, Y
¾ Performance
• Conversion efficiency (Temperature Window)

NOx adsorber regeneration (1.7 liter adsorber on a 1.9 liter DI

diesel engine, 1,200 rpm / 15~50 Nm, SV=20,000~60,000 1/hr,
fuel sulfur 2 ppm, cycled 58 s lean and 2 s rich)

• Inhibition by Sulfur

NOx adsorber
efficiency at
different fuel sulfur
levels
NOx adsorber temperature window (2.47
(2 47 liter adsorber on 1
1.8
8 liter
SI engine cycled 59 s lean and 1 s rich

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 Selective Catalytic Reduction (1/3) Ref : “Selective Catalytic Reduction,” DieselNet
Technology Guide, www.dieselnet.com, 2000.8

¾ Introduction : SCR has been • Ammonium nitrate (100~200degreeC)

(9) 2NH3+2NO2+H2O=NH4NO3+NH4NO2
• Well proven in a number of industrial stationary
• Ammonium sulfate (below 250 degreeC)
pp
applications
(10) NH3+SO3+H2O=NHO NH4HSO3
• Used since 1970s in such applications as (1)
(11) 2NH3+SO3+H2O=(NH4)2SO4
plant, (2) refinery heater and boilers in
• Ammonium slip
chemical processing industry, (3) gas turbines,
and (4) coal-fired
coal fired cogeneration plants
• The application of SCR for mobile diesel engines
requires overcoming several problems
¾ Reductant : Ammonia
• Nox reduction reactions
(1) 6NO+4NH3=5N2+6H2O
(2) 4NO+4NH3+O2=4N 4N2+6H2O
(3) 6NO2+8NH3=7N2+12H2O
(4) 2NO2+4NH3+O2=3N2+6H2O
(5) NO+NO2+2NH3=2N2+3H2O - It increases with increasing NH3/NOx ratio
• Competitive,
C ii nonselective
l i reactions
i and d temperature
(6) 2NH3+2O2=N2O+3H2O - In practice, ratios 0.9~1.0 are used, which
(7) 4NH3+3O2=2N2+6H2O minimize the ammonia slip while still providing
(8) 4NH3+5O2=4NO+6H2O satisfactory NOx conversions

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 Selective Catalytic Reduction (2/3) Ref : “Selective Catalytic Reduction,” DieselNet
Technology Guide, www.dieselnet.com, 2000.8

¾ Reductant : Urea
Catalyst Temperature (degreeC)
• From the commercial perspective, the perfect
reductant would be non-toxic,, easyy to transport
p Pt 175 ~ 250
and handle, inexpensive and commonly available V2O5 300 ~ 450
• The most widely accepted and already Zeolite 350 ~ 600
commercialized reductant is urea, CO(NH2)2
• At 1,600
1 600 decreeC urea starts to decompose • Pt catalyst loses activity above 250 degreeC
and hydrolyze : (1) Low T : (1)~(5) dominate over Pt
CO(NH2)2=2NH2+CO catalyst
CO(NH2)2+H2O=2NH3+CO2 (2) High T : (8) becomes dominate
• V2O5/Al2O3 is to form Al2(SO4)3 resulting
¾ Catalysts in catalyst deactivation
• V2O5/TiO2 + WO, MoO3 as promotor
- High T (500~550)
00 0 : anatase phase of
TiO2 irreversibly converts to rutile with a
surface area of less than 10 m2/g
• Zeolite for higher temperature

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 Selective Catalytic Reduction (3/3) Ref : “Selective Catalytic Reduction,” DieselNet
Technology Guide, www.dieselnet.com, 2000.8

■ Class 8 Truck Prototype with Urea-SCR System ■ NOx Emissions Over US FTP Transient Test

■ Emission Performance with SCR Catalyst (US FTP)

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 Comparison of NOx Conversion Ref : “Selective Catalytic Reduction,” DieselNet
Technology Guide, www.dieselnet.com, 2000.8

■ NOx Conversion Using Different Catalyst Technologies

Slightly aged catalysts. Shaded areas indicate typical temperature ranges for underfloor converters over LD test cycles.
SV = 30,000 1/h (catalyst volume about equal to the engine displacement).

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 4-Way Catalyst (DOC+Passive DeNOx)
Ref : 인치범, “촉매와 자동차 공해제어기술 : 디젤배기가스 후처리”, 2000 전문능력향상교육과정, 금속재료연구팀, 2000.8

산화촉매 De-NOx 촉매

4HC + 5O2 6NO + 4HC

+
4CO2 + 2H2O 5N2 +4CO2 + 2H2O
2CO + O2 CO2
2NO + 2H2
SOF + O2
N2 + 2H2O
CO2 + H2O
산화촉매로 대응 가능 De-NOx 촉매 개발 필요

¾ 산소과잉 분위기에서 산화/환원 반응이 동시에 진행,, HC + CO + NOx + PM 저감

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 Lecture Notes on Applied Thermal Engineering 2011

Ch t 15
Chapter
Diesel Particulate Filter
http://procom.chonbuk.ac.kr 166
Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
 What is PM – Summary Ref : “Diesel Particulate Matters,” DieselNet Technology
Guide, www.dieselnet.com, 2002.11

■ Particulate Matter (PM)의 구성

• Solid fraction (SOL)

- elemental carbon
- ash
• Soluble organic fraction (SOF)
- organic material from engine oil
- organic material from fuel

• Sulfate p
particulates ((SO4)
- sulfuric acid
- water

PM 성분 SOL SOF SO4

저감기술 DPF DOC 저유황유 Composition of Diesel Particulate Matter (HD Diesel Engine,
US FTP Transient Cycle)

http://procom.chonbuk.ac.kr 167
 What is DPF
¾ 원리 : 디젤엔진의 배기가스 중 입자상물질(SOOT)을
TRAP을 이용하여 물리적으로 포집한 후 입자상물질의 발화온
도 이상으로 승온시켜 입자상물질을 제거
¾ PM 포집 효율 : 90 % 이상

디젤엔진
포집된 SOOT
SOOT 연소반응
세라믹필터
C + O2 = CO2

통상적으로 550℃
이상에서 연소시작
배기가스 흐름

배압증가 (압력손실)

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 Wall-Flow Type Ref : “Diesel Particulate Filters,” DieselNet Technology
Guide, www.dieselnet.com, 2001.07

■ Types of Filter

• 기존의 Flow-through 형태의 촉매에서는 soot의 산화 율이 매우 낮아 배기 가스로 분출됨

• 물리적으로 Residence time을 증대하여 soot를 산화하고자 함 (Soot 산화온도: 550~600)

■ DPF : Wall-Flow Type

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 Current Types of DPF Ref : DieselNet Technology Guide, www.dieselnet.com

• Cordierite
C di i DPF • (Si)SiC Diesel
Di l DPF • Metal
M l DPF

• Thermal properties of SiC filter versus Cordierite filter:

Thermal Properties Dimension SiC Cordierite
Thermal Conductivity cal/cm℃ 0.076 0.0025
Thermal Expansion Coefficient 10-6 /℃ 4 1
Thermal Resistance ℃ 2,220 1,430
+ High thermal conductivity avoids temperature peaks in SiC-filter during regeneration
+ High expansion coefficient reduces increase of gap during driving cycle.
+ High thermal resistance allows high soot loading rate for a given size of filter

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 Ref : DieselNet Technology Guide, www.dieselnet.com

Soot Filtration
■ Types of Filtration

■ Types of Depth Filtration : main Mechanism in DPF

Diffusional deposition Inertial deposition Flow-line interception

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 Soot Oxidation by O2 Ref : DieselNet Technology Guide, www.dieselnet.com

■ Diesel Soot Oxidation by Oygen in Air

■ Exhaust
E ha st Gas Temperature
Temperat re Map (HSDI Diesel Engine)

• C + O2 → CO2
• Soot 산화온도: 550~600 ℃

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 Soot Oxidation by NO2 Ref : DieselNet Technology Guide, www.dieselnet.com

■ Oxidation of PM by Oxygen and Nitrogen Dioxide ■ NO / NO2 Shift in Diesel Oxdiation Catalyst

• Exothermic Reaction → Catalytic Burner

4HC+5O2 → 4CO2+2H2O
• Soot Oxidation by O2
C + O2 → ½ CO2 2CO + O2 → 2CO2
• Soot Oxidation by NO2 SOF + O2 → CO2+2H2O
NO2 + C → NO + CO
• Formation of NO2 → Continuous Regeneration
NO2 + C → ½ N2 + CO2
NO + ½ O2 → NO2

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 Regeneration Methods for DPF Ref : DieselNet Technology Guide, www.dieselnet.com

■ Currently Used Regeneration Methods

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 Active Regeneration Ref : DieselNet Technology Guide, www.dieselnet.com

■ Electrically Regenerated Traps ■ Engine Management

• EGR
• Post Injection
• Increase of Exhaust Gas Pressure
• Retarded Injection Timing
• Intake Air Temperature Increase

■ Traps with Fuel Burner

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 DPF Regeneration – Temperature Management
No additional measures
required

bmeep
+ post injection

+ boost pressure reduction

+ advanced pilot injection,
increased pilot quantity + EGR shut off
+ CAC-Bypass,
Intake air heating
+ retarded main injection
high idle
auxiliaries
(windshield,rear window, + throttling
mirror heating, air
conditioning + reduced injection
fan, etc pressure

critical area for

temp. management
rpm

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 DPF Regeneration – Multiple Injection
¾ DPF Regeneration Strategy in Passenger Car

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 Regeneration – Example (HMC D2.0-VGT, 4bar@1,750rpm)
Ref : 강중훈, “DPF 재생조건 달성을 위한 커먼레일 분사계 파라미터 최적화에 관한 연구,” 2003 사내연구논문발표회, 승용디젤엔진시험팀

1200 DOC 입구온도

온도 [deg.]

1000 DPF 입구온도

DPF 내부온도
800
600
초기 400
재생온도 200 시간 [s ec ]
((550 도)) 0 60 120 180 240 300 360 420 480 540 600 660 720

40 11
DOC + DPF 차압

산소농도[%]
DPF 출구 산소농도
30 9
[kPa]
차압[

20 7

10 5
시간 [s e c ]
0 3
0 60 120 180 240 300 360 420 480 540 600 660 720
①
② ④ 재생종료 비재생모드로 전환
③
(산소농도 평형점 기준)

① Transition 구간 : 주행모드에서 재생모드로의 전환시,, 재생조건 도달 시간

② 초기재생구간 : 재생시작되어 차압이 줄어드나, 산소소모량이 급격하지 않음
③ 급격재생구간 : 산소소모량이 급격히 많아지며, DPF 담체 내부의 급격한 연소(내구성 우려)
④ 후기재생구간 : 차압의 감소폭이 줄어들며,
줄어들며 연소요구 산소량 줄어드는 말기 재생

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 Passive Regeneration Ref : DieselNet Technology Guide, www.dieselnet.com

■ CRT (Continuously Regenerating Trap) Types

■ Oxidation Temperature

C fi
Configuration
ti B l
Balance Temperature
T t
DPF with Passive Regeneration 550 ~ 650 °C
CDPF 325 ~ 420 °C
Fuel Additive 300 ~ 400 °C
CRT (oxicat + uncatalyzed DPF) 280 °C
Oxicat + CDPF 250 °C

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 DPF Regeneration Strategies

■ Thermal Engine Management (not possible without Diesel Oxidation

Catalyst (DOC) as “Catalytic Burner”)

■ Continuously Regenerating DOC +DPF (CR-DPF)

■ DOC + DPF + Fuel Additive

■ Catalysed Soot Filter (CSF)

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 CRT Type of Filter (1) CRTTM Ref : DieselNet Technology Guide, www.dieselnet.com

■ Cutaway View of CRTTM (Johnson Matthey) ■ Effect of Fuel Sulfur Content

PM Reduction
Red ction Efficienc
Efficiency in CRT Filter (CAT 3126 engine)

PM Reduction, %
Fuel Sulfur Level, ppm
• 필터 전단에 고농도의 Pt 촉매를 적용하여 SOOT의 연소온도를 낮춤 ESC Test Peak Torque
(약 230℃) 3 95 91
• 반응식 @ Pt Catalyst : 2NO + O2 = 6NO2 30 72 73
@ Soot Filter : C + 2NO2 = CO2 + 2NO, C + O2 = CO2 150 -3 19
• 저유황연료 필요 (50 ppm S 이하)
350 -155 -139
• 단점 : 고농도의 Pt 촉매로 인한 황산염 생성, 생성 입자상물질 증가

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 CRT Types of Filter (2) DOC + (Uncoated) DPF

C (Soot) + O2 CO/CO2
C ((Soot)) + NO2 CO/CO2 + NO

DOC CS F
DOC DPF

HC (SOF) + O2 CO2 + H2O

HC,CO + O2 CO2 + H2O (CO from Engine)
NO + O2 NO2

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 Rating for a DOC+DPF System

+ Simple System Configuration

+ Used in for Retrofit Systems (Trucks and Busses)

NO2 Effect is a function of the DOC and Engine Out NOx

- Gap Between the NO2 Regeneration and the Area of Active Regeneration
- Quite Frequent Active Regeneration Required for Car Applications
(penalty in CO2 Emissions)
- Engine Out NOx probably not sufficient for most EURO 5 Engines

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 Chemical Reactions : DOC+DPF+Additive (MOx)

C (Soot) + MOx CO/CO2 + MOx-1

Fuel Additive added
C (Soot) + O2 CO/CO2

C (Soot) + NO2 CO/CO2 + NO

DOC CS F
DOC DPF

HC (SOF) + O2 CO2 +
H2O
HC,CO + O2 CO2 + H2O (CO from Engine)
NO + O2 NO2

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 양산적용차 : Peugeot 607 2.2HDi (1/2) Ref : http://www.psa.fr

• 특징
- 승용차중 DPF 재생시스템 최초 양산
- EURO-III 대응 (PM : EURO-IV 대응)
• DPF 재생 시스템
- Post-Injection에 의한 200~250℃ 상승
- 산화촉매에 의한 100℃ 이상 상승
- 연료첨가제(CeO2, Rhodia社의 “Eloys”)
에 의한 SOOT 연소온도 저하
(550℃→450℃)
- SiC 필터 (IBIDEN 社)
- 400~500 km 마다 재생
• DPF 도입결과
- 주행 안정성 획득
- Nearly Zero PM (0.004 g/km, GDI 수준)

Ref
e : 김석재, “디젤디젤 입자상물질 필터 ((DPF)) 시
시스템
템
개발 - Peugeot 607 모니터링”, DAS-TFT 발표자
료, 금속재료연구팀, 2002.03
http://procom.chonbuk.ac.kr 185 http://procom.chonbuk.ac.kr
 양산적용차 : Peugeot 607 2.2HDi (2/2)

Ref
e : 김석재, “디젤디젤 입자상물질 필터 ((DPF)) 시
시스템
템
개발 - Peugeot 607 모니터링”, DAS-TFT 발표자
료, 금속재료연구팀, 2002.03
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 Rating of DOC+DPF+Fuel Additive

+ Proven technology
+ Potential to meet Euro 4

- Additive forms ashes, leads to cleaning requirement during live of vehicle

- Steep temperature increase during active regeneration
- Fuel Additives are only allowed in closed systems, OBD has to check for leaks
and shut off additive system if crack of DPF is observed (health concerns)

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 Catalyzed Soot Filter (CSF) Ref : “입자상물질 저감장치(DPF System) 개발 세
부계획서”, 금속재료연구팀, 2000.12

■ 엥겔하드社(미국) CSF (Catalyzed Soot Filter)

• 담체에 촉매물질을 직접 코팅 (조촉매 + 저농도Pt촉매)
• 연료중 S 함유량의 영향이 적음 (조촉매 사용으로 황산염 생성효과 미약)

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 Catalyzed Soot Filters (CSF) – Configuration

1st Generation Soot

DOC CC + CSF-UF
DOC-CC CSF UF Burning

+
2nd Generation
HC/CO
CSF-CC
CSF CC Integrated DOC
Conversion

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 Chemical Reactions 1st Generation – DOC+CSF
¾ Main Function is Soot Burning, however, Chemical Reactions are Multi-Functional

C (Soot) + O2 CO/CO2

C (Soot) + NO2 CO/CO2 + NO

NO + O2 NO2

CO + O2 CO2 (CO from Soot)

HC,CO + O2 CO2+ H2O

(residual gaseous HC,CO)

DOC CS F
DOC CSF

HC (SOF) + O2 CO2 + H2O

HC,CO + O2 CO2 + H2O (CO from Engine)

NO + O2 NO2

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 Outlook : 3rd Generation
¾ Future System Combines DOC and CSF Functions NOx Reduction also under Investigation

Catalyzed
y Soot Filter with
Integrated NOx Trap

CSF

DOC Functions CSF Functions for Soot Burningg

ƒ SOF (Soluble Organic Fraction) to CO2 and H2O ƒ Oxidation of Soot via O2 and NO2
ƒ CO to CO2 ƒ NO and CO is formed
ƒ NO to NO2 ƒ CO from soot burn to CO2
ƒ NO to NO2 (Recycle)

NOx Reduction Functions

ƒ NO to NO2
ƒ NOx storage under lean conditions
ƒ NOx reduction under rich conditions

DOC
191
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 Low Emission PC Diesel Engines with Aftertreatments
■ Supercharging (single stage: VNT or 2 stages), intercooler
■ 4 Valves/cyl., controlled intake swirl
■ Closed-loop controlled and high efficient cooled EGR
■ Closed-loop controlled air/fuel management (e.g. control of A/F ratio)
■ High pressure Injection (>1600 bar) for high power output
■ Sophisticated system control strategies
■ Pilot injection (< 1,2 mg/str), multiple injection
Intake Throttle
■ Oxidation catalyst High Pressure Pump

■ Particulate Trap Common Rail

■ DeNox catalyst EGR Valve

VGT

■ “Sulfur-free” diesel fuel (< 10 ppm S) DPF DOC

P
Pressure T
Temperature S
Sensor
Difference

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 Lecture Notes on Applied Thermal Engineering 2011

Ch t 16
Chapter
Some Numerical Examples
http://procom.chonbuk.ac.kr 193
Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea
 3D and/or 1D Modelling
HDDE DePM System DeNOx System

DOC DPF SCR

3D Modeling
¾ Subrenat, A., Bellettre, J., and Cloirec, P. Le., 2003, “3-D Numerical Simulations of Flows in a Cylindrical Pleated Filter Packed with
Activated Carbon Cloth,” Chemical Engineering Science, vol. 58, pp. 4965-4973
¾ Braun, J., Hauber, T., Tobben, H., Zacke, P., Chatterjee, D., Deutschmann, O., and Warnatz, J., 2000, “Influence of Physical and
Chemical Parameters on the Conversion Rate of a Catalytic Converter : A Numerical Simulation Study,” SAE 2000-01-0211

1D Modeling
¾ Konstandopoulos, A. G., Kostog;ou, M., Skaperdas, E., Papaioannou, E., Zarvalis, D., and Kladopoulou, E., 2000, “Fundamental
Studies of DPF : Transient Loading, Regeneration and Aging,” SAE 2000-01-1016
¾ Kim, M. Y., 2003, Performance Prediction of SCR-DeNOx System for Reduction of Diesel Engine NOx Emission,” Trans. KSAE, vol.
11, no. 3, pp. 71-76
¾ Ciardelli, C., Nova, I., Tronconi, E., Konrad, B., Chatterjee, D., Ecke, K., and Weibel, M., 2004, “SCR-DeNOx for Diesel Exhaust
Aftertreatment : Unsteady-State Kinetic Study and Monolith Reactor Modelling,” Chemical Engineering Science, vol. 59, pp. 5301-
5309
¾ Watanabe, Y., Asano, A., Banno, K., Yokota, K., and Sugiura, 2001, “Application of Numerical Modeling of Selective NOx
Reduction by HC under Diesel Transient Conditions in Consideration of HC Adsorption and Desorption Processes,” Catalysis Today, vol.
69,pp. 209-216

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 Urea-SCR Modelling
¾ Kim, M. Y., 2003, Performance Prediction of SCR-DeNOx System for Reduction of Diesel Engine NOx Emission,” Trans.
KSAE, vol. 11, no. 3, pp. 71-76 (HMC)

NO Reaction where
(
−Ed0 1 − αθNH3 )θ
4NO + 4NH3 + O 2 → 4N 2 + 6H2 O ra = k CNH3 1 − θNH3 0
a ( ) rd = k 0
d
RT
NH3
Concentration of NH3 and NO
∂CNH3 ∂CNH3 ∂CNO ∂C
rNO = kNOCNOθ NH
*
⎡1 − exp −θNH θ NH
3 ⎣ 3
*
⎤
3 ⎦
( )
= −v − Ω ( rd − ra ) = − v NO − ΩrNO
∂t ∂z ∂t ∂z
100
800 WO3-V2O5/TiO2
T=493K NH3/NO=1.0
700
90
600

Conversion (%)
entration (ppm)

NO
500 80

400 NH3/NO=0.9
70

NO C
Conce

300

◆● Lietti et al. (1997) V2O5/TiO2

200
Present 60
NH3
100

0 50
0 500 1000 1500 2000 2500 3000 600 650 700 750 800 850 900
Time (s) Temperature (K)

Comparison of NH3 and NO concentration with

Effect of temperature on NO conversion for
experiment of NH3 step-feed (t=0s) and shutoff
NH3/NO=1.0 and 0.9 over the WO3-V2O5/TiO2
(t=1,250s)
(t 1,250s) over the WO3-V
V2O5/TiO2 catalyst at T
T=493
493
and
d V2O5/TiO2 catalysts
t l t
K
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 촉매 삽입형 머플러 (Catalytic Muffler)
역할

• 소음기 (고압의 배기가스를 저압으

로 변환시켜 배기가스 소음 감소)
• 촉매변환기 (배출가스 저감)

Baffle
구조

Gool Wool
orated Bafffle

B
• Tube, Baffle, Plate, Catalytic
Catalytic Muffler Converter, Gool Wool

특징
Perfo

• 적은공간에 설치 가능
• 소음기로 촉매 보호, 내구성 향상
Tube • 활성화온도 저하
Flow In 양산

• S社 설계
Flow
Fl • D社 제작
• H社 차량 장착
Out

Case

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 촉매 삽입형 머플러 (Catalytic Muffler)

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 Variation – 2 Module (Metal Filter)
ƒ Catalytic Muffler Variations #1
z Metal Filter Type (2-Module) z Cell Number : 864,090

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 Case 1 – 2 Module Catalytic Muffler (Metal Filter)
구분 유량
z Velocity Distributions
촉매 1 0.0853kg/s 48.7%
Velocity(m/s)
y( ) 촉매 2 0.0897kg/s 51.3%

CAT.1

CAT. 2

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 Case 1 – 2 Module Catalytic Muffler (Metal Filter)
Velocity(m/s)

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 Case 1 – 2 Module Catalytic Muffler (Metal Filter )
z Pressure Distributions
Pressure Drop
Total Pressure (Pa)
5 kPa

100.5 kPa
103 kPa
101 kPa
103.4 kPa

105 kPa 100 kpa

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 Chapter 17 References
¾ R. M. Heck and R. J. Farrauto, 2002, Catalytic Air Pollution Control – Commercial Technology,
Wiley Inter-Science
¾ R. E. Hayes and S. T. Kolaczkowski, 1997, Introduction to Catalytic Combustion, Gordon and
Breach Science Publishers
¾ http://www.dieselnet.com
¾ http://procom.chonbuk.ac.kr/dieselnet.htm

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http://procom.chonbuk.ac.kr
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http://procom.chonbuk.ac.kr
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http://procom.chonbuk.ac.kr
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http://procom.chonbuk.ac.kr
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 Th k You
Thank Y …

Lecture Notes on Applied Thermal Engineering 2011

Applied
pp Thermal Engineering
g g
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Prof. Man Young Kim, Spring 2011, ⓒ[email protected], Aerospace Engineering, Chonbuk National University, Korea