Documente Academic
Documente Profesional
Documente Cultură
Lectures at Fritz-Haber-Institut
28.11.2008
Cornelia Breitkopf
TU Bergakademie Freiberg
Outline
Introduction
Porosity (definition, IUPAC)
Diffusion (laws, effective quantities, Knudsen diffusion, examples)
General transport equations for gases
Influence of transport on
Activation energy, Reaction order, Selectivity
Recommended Literature
Pore types
Pressing of support material leads to a network of micro/meso-porous and macroporous areas: powder particles
are micro-/mesoporous, pores between particles build up
a macroporous network
Types of pores
open pores: surface ~, column ~, hollow ~
isolated pores: inclusion ~
see IUPAC
IUPAC - Definitions
Porous solid: a solid with pores, i.e. cavities, channels or
interstices, which are deeper than they are wide
Pore size: (generally pore width): the distance between
two opposite walls of the pore
Micropores (< 2 nm),
Mesopores (2-50 nm)
Macropores (> 50 nm)
Types of porosity
Difference between bed porosity and particle porosity
Bed porosity (or void fraction) B is defined as the
volume of voids per volume of reactor
The pellet void fraction or porosity is denoted by and
= P * Vg (P effective particle density, Vg pore volume)
Jakubith
Diffusion Background
Diffusion In general
is the transport of mass in gases, liquids and solids
under the influence of a concentration gradient
proceeds spontaneously due to microscopic
movement of mass
is an irreversible process which leads to an increase
in entropy and is only reversible by supply of work
Diffusion In special
mechanisms differ for gases/liquids and solids
for gases/liquids: statistical movement according to T
for solids: different mechanisms possible:
i) direct exchange of lattice places
ii) movement via interstitial lattice sites
iii) movement via lattice vacancies
iv) movement via lattice defects or on the grain surface
v) exchange of sites on the crystal surface
TC Anorg. Chemie
Diffusion - quantitatively
generally increases with temperature and decreases
with increasing density
the equilibration takes
minutes for gases
days/weeks for liquids
with measurable rate only close to the melting point
H2 in O2
N2 in O2
H2O vapour in air
CH3OH in water
Sugar in water
Au in Cu
Fe in Al
36Cl- in AgCl
D [cm2/s]
0.78
0.19
0.23
1.2*10-5
0.5*10-5
2.1*10-11
6.2*10-14
3.2*10-16
T [K]
298
298
298
298
298
1023
623
623
Lexikon Chemie
Transport by Diffusion
Transport
Mass
Heat
Energy
dc
jn = D i
dz
dT
jQ =
dz
du z
j P =
dy
Ficks Law
Fouriers Law
Newtons Law
= Di
t z z z
Configurational diffusion
pore diameter within molecular dimensions (0.3-1 nm) as for
zeolites
diffusion coefficients are smaller by some orders of magnitude
2 kT kT
DM =
3 m d 2 p
3
2
1 1
1
DM ~ T , ~ , ~ , ~ 2
p m d
gs
DAB
= 0.001834
, m 2 s 1
2
p AB
D
T
p
Temperature [K]
Pressure [bar]
M r,A , M r,B
2
AB
1
v d p ; v... average velocity; d p ...pore diameter
3
1
8RT
D Kn = d p
3
M
Depends not on pressure !
1
2
1
D Kn ~ T , ~ , ~ d p
M
1
1
1
=
+
*
D D M D Kn
Catalysts: irregular network of pores effective D
For very heterogeneous pore size distributions the term
effective D is not valid complex models necessary
Effective diffusivities
Use of porosity and tortuosity factor
D eff
= D
Fixed-bed Catal.
International Conferences:
5th International Conference on
Diffusion in Solids and Liquids
Literature examples
continued
Transport regimes
Transport
External
Diffusion to exterior
surface of particle
Internal
Diffusion in pores
Catalytic circle
Physical
processes
(see Baerns)
k g transfer coefficient
a specific surface area
reff = k c m1,s
k = ks a
Case studies:
reff = k c m1,s =
k
kg a
k
c1, g
k
1+ a
kg
reff = k c1,g
<< 1
k c m1,g
DaII =
k g a c1,g
for any m
reff
r
depending on m
dp v
dpparticle diameter
v velocity of gas
viscosity of gas
dR
> 30
dp
dR reactor diameter
dp particle diameter
kg p
vM
Sc
2/3
Sc =
DM
Experimental check
Fixed bed reactor:
for the condition of a constant residence time increase of
linear velocity of the fluid around the particles until the
resulting rate keeps constant
no influence of external transfer
! residence time decreases with increasing velocity of
fluid, increase the bed height to compensate this
see Jakubith
D gs
eff
1 gs
D
10
D eff
d 2c
kc = 0
2
dz
c
c0
z
l
c0
l
D eff
c
c0
c0
c
c
k
=0
0
2
2
c0
l z
d
l
d 2 l2 k
=0
2
D eff
d
2
l
k
2
=
Quotient
is a dimensionless term
D eff
Thiele modulus
k
=l
D eff
Thiele Modulus
The single dimensionless group appearing in the model
is referred to as the Thiele number or Thiele modulus in
recognition of Thieles pioneering contribution to this
area:
E.W. Thiele. Relation between catalytic activity and size of particle.
Ind. Eng. Chem. 31(7) (1939) 916-920.
k
reaction rate
=
D eff diffusion rate
d 2
2
=
2
d
Solve with appropriate initial and boundary conditions
free
gas space
1. for z = 0 , c = c0
2. for z = l , dc/dz = 0
decrease of c
due to reaction
or for = 0 , = 1
or for = 1 , d/d = 0
or
z
cosh (1 )
c
l
=
c0
cosh
RT
or
z
cosh (1 )
c
l
=
c0
cosh
k
=l
D eff
Criteria:
<< 1
chemical reaction is rate-limiting
diffusion is fast, reactand can enter the pores of
the catalyst and the concentration of the reactand
is constant for the whole catalyst volume
>> 1
limitation of overall rate by diffusion of reactand in
the pores
inside the pores the reactand converts fast
concentration of reactand decreases already close
to the boundary layer
rs = l * rv
rs
rs , max
k c (z) dz
0
k l c0
rs
rs , max
reaction rate
max . reaction rate
tanh
=
Fixed-bed catal. r.
ln [k] = ln k 0
E A ,s
RT
1.
pore diffusion
regime
kinetic regime
E A ,s E A
ln [k * ] = ln k ln l k
D eff
k
ln [k * ] = ln k ln l
D eff
ln [k * ] =
1
ln k
2
ln l +
1
ln D eff
2
E A ,s
1
1
ln [k * ] = ln k 0
ln l + ln D eff
2
2RT
2
E A ,s =
EA
2
E A ,s 0
k eff =
1
1
1
+
k kga
keff = kga
kg is determined by D; D ~ T3/2 thus kg ~ T3/2; formal
E eff
k g exp
2RT
Eeff = EDiff
EDiff~ 5 kJ/mol
E A ,s 0
0
0.5
1
1
2
1.5
k g rp
D
k g rp
D
Fixed-bed catal. r.
1
1 2
+
k 3 Bi
Experimental check
For a porous catalyst the limiting effect of pore diffusion
would be decreasing if it is possible to reduce the length
of the pores
Practically: crush catalyst, grade into sizes;
measurement of apparent rate depending on size
fractions; with decreasing size the apparent rate
increases until a constant value is reached
Check the external transport; both limitations may occur
simultaneously
Elegant way of separation of pore diffusion and
microkinetics: use of single pellet diffusion reactor
Summary
9 Definition of porous systems
9 Definition of diffusion and diffusion coefficients
9 External transfer processes
9 Production rate via effectiveness factor
9 Case studies with use of Re, DaII
Summary
9 Influence of transport on
9 Apparent activation energy
9 Reaction order
9 Selectivity
III
II
rpore
I Knudsen diffusion
II potentials of opposite pore walls overlap thus the resulting
interaction of substrates and walls is effectively decreased
and the diffusion coefficient increases
III pore diameter is in the range of the substrate diameter; strong
dependence of D from the effective substrate diameter