Dr. R.

Nagarajan
Professor
Dept of Chemical Engineering
IIT Madras

Advanced Transport Phenomena
Module 1 Lecture 2
Overview & Hot Corrosion Example
HOT CORROSION
In marine environments, turbines ingest NaCl in
air intake
Fuel contains sulfur as impurity
They react to form molten Na
2
SO
4
The molten salt deposits on turbine blades
(rotors and stator vanes)
and dissolve the protective oxide coating on the
blades, leading to
direct corrosive attack of the exposed nickel-
base super alloy surface, resulting in
catastrophic failure of the blade.
HOT CORROSION
Vapor phase equilibrium (local thermochemical
equilibrium) at the mainstream of gas flow
Vapor/condensate equilibrium at the blade
surface
Chemically-frozen boundary layer in between
THERMODYNAMIC CONSTRAINTS
Flow of combustion product gases past surfaces
of rotor blades and stator vanes
Momentum transfer
Extraction of heat from the combustion gases
Heat transfer
Multi-component Chemical Vapor Deposition of
molten sodium sulphate on blade surfaces
Mass transfer
All occurring in the chemically reactive
environment of a gas turbine combustor.

TRANSPORT PROCESSES INVOLVED
BOUNDARY LAYER CONFIGURATION
DIFFUSION FLUX TO THE BLADE SURFACE



where F
i
(Soret), F(ncp) and F(turb) are, resp.,
augmentation factors to the mass-transfer
Nusselt number, Nu
m,i
due to:

1. thermal diffusion,
2. variable boundary-layer gas properties, and
3. free-stream turbulence



''
, , , , ,
( ) ( )
/ . ( ). ( ). . ( ) . .
( )
i e
i w i m i i e i w i w i
i
D F ncp
j L F Soret F Turb Nu
l F Soret

e e e t
(
= +
(

Chemical element fluxes are related to species
fluxes via:


where

is the mass fraction of the element
in species i.

Total deposition rate is then calculated as:

'' ''
( ), ( ), ,
1
N
k w k i i w
i
j j e
=
=

''
''
( ),
( ),
k w
w
k c
j
m
e
-
=
( ), k l
e
th
k
DIFFUSION FLUX TO THE BLADE SURFACE
CONTD
The elemental molar fluxes must be in the same
ratio as condensate stoichiometry for steady-
state deposition of a non-flowing condensate
i.e., for Na
2
SO
4
(l) to form, must be equal
to two.
For Na
2
CO
3
(s) to form, (when one or
more element is in excess, only the trace
element needs to satisfy non-zero flux
constraint)
( )
( )
Na
S
J
J
( )
0
Na
J >
FLUX RATIO CONSTRAINT
Temperature at which the condensate first forms
as surface is cooled, or
Temperature at which a pre-existing condensate
begins to evaporate as surface is heated
The two may not be the same (hysteresis, or
dew-point shift effect associated with multi-
component diffusion)
Definitions reversed for commercial CVD
application, where higher temperatures favor
film formation
DEW POINT
Operational definition of dew-point:


When T
(surface)
is between T
dp
and T
solidification
, hot
corrosion can occur as salt is molten in nature

''
( ) 0
w
dp
m T
-
=
DEW POINT CONTD
Arrival by vapor diffusion
Film set in motion by aerodynamic and
centrifugal shear
Local thickness, as a function of time, depends
on balance between deposition and flow
phenomena
MOLTEN SALT LAYERS IN FLOW
Local oxide dissolution rate depends on:
local thickness of salt film
its viscosity
oxide diffusivity
oxide solubility
Local hot corrosion rate, hence useful lifetime,
depends on local oxide dissolution rate
MOLTEN SALT LAYERS IN FLOW CONTD
THIN CONDENSATE LAYER DYNAMICS
ON ROTOR BLADES
Objectives:
Primary flow, and its metal oxides
Dissolution Rate Consequences
Relation to observed hot corrosion
patterns?
2
2 3
" "
" "
( ) ''( , , )
.
2 3
l w r
l l
l l l
Arrival fromVapor BL
gas BL shear Centrifugal term
R z m x z t
t x z v
o t
o o

-
( (
c O + c c
+ + =
( (
c c c

OXIDE DISSOLUTION RATE
where k
d
is a rate constant, is liquid layer
density, is local undersaturation of
oxide in liquid, and n
d
the order of the rate
process




( )
''
0 0, , 0,
d
n
d l sat w w
r k e e
-
=
0,sat, w 0,w
-
l

OXIDE DISSOLUTION RATE CONTD

where subscripts w and b represent blade
surface and bulk liquid, resp., and k
m
is a mass-
transfer coefficient.
Under steady-state conditions:
( )
''
0, 0, 0, w m w b
j k e e =
''
''
0,
0,
w
w
r j =
Diffusion in the liquid is calculated via:
HOT CORROSION RATE
Hot corrosion rates will track oxide dissolution
rates
Local oxide thickness, will depend inversely
on local oxide dissolution rate

When falls below a threshold value, ,
catastrophic failure at the local site will occur
Corrosion maps can be generated in this
manner, and compared against field or burner-
rig data
Model can be refined, re-run, results
compared again, etc
Let us now consider another example.
,min l
o
l
o
l
o
In power plants burning fossil fuels, such as coal,
the combustion gases contain unburnt particulate
matter ash
Ash particles deposit on heat exchanger tubes,
and reduce heat transfer efficiency
Ultimately, ash deposits get so thick, they
interfere with the flow of gases
EXAMPLE 3: FOULING OF HEAT
EXCHANGER SURFACES
EXAMPLE 3: FOULING OF HEAT
EXCHANGER SURFACES CONTD
Periodically, plant operation must be stopped
and ash removed or tube replaced
Loss of productivity, cost of replacement
Need to estimate rate of ash deposition so that
proper planning can be done
PC FURNACE + HEAT EXCHANGER
HEAT EXCHANGER TUBE IN CROSS-
FLOW OF COMBUSTION GAS
DESIGN PARAMETERS
Diameter of h.e. tube of circular cross-section = 5
cm
T
e
= 1200 K
p = 1 atm
U
e
= 10 m/s
Ash composition: SiO
2
Size distribution:
d
p
= 0.1 mm at e
p
= 2 X 10
-4
d
p
= 20 mm at e
p
= 1 X 10
-2
DESIGN REQUIREMENTS
Rate of energy gain (kW) per meter of tube
length if outer tube surface temperature is to be
maintained at T
w
= 800K
Rate at which submicron and super-micron ash
will accumulate per unit length of cylinder
ASSUMPTIONS
Gas flow in continuum regime
Forced convection dominates over natural
Negligible viscous dissipation
Mainstream turbulence level not very high
For submicron particle transport, analogy
between mass- and energy-transfer holds

All assumptions must later be validated
ENERGY TRANSFER RATE
Average heat-transfer coefficient for transverse
flow past a circular cylinder is given by:




where Reynolds number

And Prandtl number





( )
( )
( )
Re, Pr
w w
h
w w
q d L
Nu
k T T d
t
-

(

( )
Re
Pr
w
P
U d
v
v
k c

ENERGY TRANSFER RATE CONTD

Approximation:



Rate of energy flow, -q
w
is calculated by:
( ) ( )
.
Pr Pr
comb products air
~
( )
( )
( )
Re, Pr
w
w
h
w w
k T T
q
Nu
d L d t
-

=
ESTIMATED VALUES
For T
w
= 800K and T
e
= 1200K, and P = 1 atm:
Re 4000, 36
and Thermal conductivity
k 1.62 X 10
-4
cal cm
-1
s
-1
K
-1
Heat transfer rate (from combustion gases), -q
w
,
given by:

may be estimated (per meter of heat-exchanger
tube) as 733 cal s
-1
, or 3 kW.
( ) ( )
Re, Pr
w h w
q L k T T Nu t
-

(
=

h
Nu
TUBE-FOULING RATE DUE TO ASH
ACCUMULATION
Mass transfer Nusselt number, , is given by:




where j
p,w
is the rate of ash mass transfer to a
circular cylinder in cross-flow, and
Sc = Schmidt number =

( )
( )
( )
,
, ,
Re,
P W w
m
P P P W W
j d L
Nu Sc
D d
t
e e

m
Nu
/
p
D v

For d
p
= 0.1 mm, Sc 3,000, 1,260,
-j
p,w
0.035 kg/year

For d
p
= 20 mm, Sc 10
8
, 15,600,
-j
p,w
0.011 kg/year


Are these estimates realistic? NO!

TUBE-FOULING RATE DUE TO ASH
ACCUMULATION CONTD
m
Nu
m
Nu
RE-EXAMINING ASSUMPTIONS
A1: Convection & Brownian diffusion are primary
mechanisms of ash particle transport
A2: Particle flow is coupled closely enough to
fluid flow that single-phase flow may be
assumed.
Neither assumption is valid in a high-temperature
flow system involving ash particles of sizes
ranging from sub-micron to mms.
appropriate correction factors must be
developed and applied.
EFFECT OF ANALOGY-BREAKING
PHENOMENA
Thermophoresis:
Particle mass flux induced by a temperature
gradient
Increases ash capture rate to 7.2 kg/year for
0.1 m-sized particles
Inertial Capture:
Significant for Stokes number values near 0.1
and higher
Increases ash capture rate to 9 metric
tonnes/year for 20 m sized particles
SUMMARY SO FAR
Many practical process applications involve
simultaneous transport phenomena, high
temperatures and chemical reactions.
In order to analyze such processes, and develop
control/ optimization strategies, a fundamental
understanding of the interplay between these
phenomena is required.
In the remainder of the course, we will attempt to
develop this understanding.