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Analysis of SCG Olefin Metathesis Process Issues

Jonathan H. Worstell
25 October 2015
Abstract
This report contains an analysis of trickle-bed olefin metathesis with regard to the
process operated by SCG. It concludes with a list of recommended actions to prove or
disprove various possibilities.
Introduction
SCG currently metathesize 2-butene with ethylene to produce propylene. The feed to
their reactor is a mixture of ethylene and 1-butene; however, the 1-butene stream
contains various C4 components. This feed mixture enters an MgO catalyst bed that
isomerizes 1-butene to 2-butene; at full isomerization, the mole ratio is 25:75,
respectively.
This isomerized feed then enters an MgO/WO3 mixed catalyst bed that
metathesizes 2-butene and ethylene to produce propylene. The WO3 catalyzes the
metathesis reaction while the MgO isomerizes 1-butene to 2-butene. This latter reaction
is necessary because, as metathesis occurs, the concentration of 2-butene declines;
thus, propylene formation declines. However, the MgO catalyst maintains 2-butene
concentration at full isomerization; i.e., at 75 mole percent, by isomerizing 1-butene.
Note that the 2-butene can also metathesize with 1-butene and 2-butene. The former
reaction produces a propylene molecule and 2-pentene while the latter reaction simply
occupies catalytic sites.
SCG have developed catalysts to replace one or both of the above catalysts.
SCG are now preparing to test their new catalysts in their laboratory and pilot plant
facilities. Unfortunately, testing the current catalysts in their laboratory facility has
identified a problem. The problem is: at equivalent weight hourly space velocities
(WHSV in per hours), their laboratory process demonstrates lower conversion than
either their pilot plant or plant processes; and, their laboratory process demonstrates
poorer catalyst stability; i.e., shorter catalyst life, than either their pilot plant or plant
processes. The following illustrative information encapsulates their problem.1

WHSV = 10 hr-1 (commercial scale WHSV which is used to test lab & pilot
scale too)
Conversion
- Lab (3 g MgO, 9 g WO3 catalyst): conversion = < 10%
- Pilot (35 g MgO, 105 g WO3 catalyst): conversion = 40%
- Commercial (4.7 ton MgO, 14.2 ton WO3 catalyst): conversion =
60%
Catalyst stability days
- Lab (3 g MgO, 9 g WO3 catalyst): stability = 1 day (TGA weight loss
did not imply more cokes formed)

Wiroon Tanthapanichakoon, e-mail communication, 5 October 2015.

Pilot (35 g MgO, 105 g WO3 catalyst): stability = 3 days


Commercial (4.7 ton MgO, 14.2 ton WO3 catalyst): stability = 30
days

The question is: what is causing this disconnect between the laboratory process
and the pilot plant and plant processes?

1.
2.
3.
4.
5.
6.
7.

Assumptions for Process Analysis


The catalyzed process comprises one reactor containing two catalyst beds in series.
The first bed encountered by the olefin feed comprises MgO pellets.
The second bed comprises a mixture of MgO pellets and granulated WO3.
The MgO catalyst isomerizes the butenes present in the olefin feed.
The WO3 catalyst metathesizes the ethylene and butenes in the olefin feed.
The butene feed is a mixture and enters the reactor as a liquid.
The ethylene is gaseous (critical temperature is 49.1 oF or 9.5 0C and critical
pressure is 742.7 barg, which is 49.5 atmospheres or 50.2 barg; operating
conditions are 350 oC and 20 barg).
Derivation of Pertinent Equations

1-butene Isomerization
SCG first isomerize their 1-butene to 2-butene through a reactor containing MgO
pellets.2 MgO is a solid base, which, if properly activated, isomerizes carbon-carbon
double bonds. For this analysis, we assume the SCG MgO catalyst to be porous.
The butene mass balance, in circular cylindrical coordinates, is

1 B 1 2B 2B
B
B v B
B
vr

vz
DB
2 RB
r
2
2
t
r
r
z
z
r r r r
where B represents butene molar concentration (mols/m3); t is time is seconds (s); r is
the radial distance from the container centerline to the inner wall of the container; i.e.,
reactor; is the azimuthal angle about the container centerline (dimensionless); z is the
physical height of the catalyst bed in the container (m); vr; v, and vz are the linear fluid
velocities in the radial, azimuthal, and axial directions, respectively (m/s); D B is the
1 B 1 2B 2B

diffusivity constant for butene in a butene mixture (m 2/s);


r

r r r r 2 2 z 2
represents the diffusion of butene in each direction; and, R B is the rate of butene
isomerization.
The information provided for this analysis appears to be for the mixed MgO/WO3
catalyst bed and not for the separate MgO catalyst bed. Therefore, nothing can be said
about dispersion effects in the MgO catalyst bed. Thus, we make these assumptions
with regard to the MgO catalyst bed.
2

We define a reactor as a discrete, distinct bed or charge of catalyst. Such a reactor can be in a
container with a separate, distinct charge of a second catalyst, which comprises a second reactor in the
same container.

0 ; the process is at steady state;


t
vr = v = 0; axial flow only;
1 B 1 2B 2B

0 ; no dispersion of any kind.


r

r r r r 2 2 z 2

We make these assumptions to arrive at a simple model. If we need a more complex


model, we can relax one of our assumptions to discuss a particular issue at that time.
Implementing these assumptions, we can reduce the above mass balance to

vz

d BBF
RB
dz

Multiplying this equation by the ratio ACS/ ACS, where ACS is the cross sectional area of
the empty container or reactor, we obtain

vz

A CS d B BF
RB
A CS d z

which reduces to

Q d B BF
RB
A CS d z
where Q is ACSvz. Rearranging and integrating the left side of the above equation gives

d B BF
V

Q
RB
V/Q is space time; its inverse, Q/V is space velocity.
Since the publication of Hougen and Watsons classic volume Chemical Process
Principles: Kinetics and Catalysis in 1947, the parameter used for scaling fixed-bed
processes, catalytic and non-catalytic, has been space velocity. 3 Space velocity is
defined as process volumetric flow rate divided by the volume of solid material through
which the process fluid flows. Thus, its units are

m3

s 1
s
m
3

O. Hougen and K. Watson, Chemical Process Principles: Kinetics and Catalysis, John Wiley and Sons,
Inc, New York, NY, 1947.

Space velocity has the same dimensionality as a first-order reaction rate constant. This
equivalence between a physical inverse time and a chemical inverse time is generally
made when scaling a fixed-bed process. However, these two inverse times are only
equivalent when the process is reaction rate limited and the reaction mechanism is firstorder. These two inverse times are not equivalent if the process is diffusion rate limited.
To evaluate R B , we must develop a simplified mechanism for butene
isomerization. Figure 1 presents such a mechanism. It shows a schematic of olefin
isomerization by a porous solid catalyst. When a fluid flows over a solid surface, a
boundary layer forms along that surface. This boundary layer forms a stagnant film.
Little or no convective mass transport occurs in this stagnant film. Thus, mass transport
from the bulk fluid to the solid surface occurs via molecular diffusion.
The reactant concentration at the bulk fluid/stagnant film boundary is the
concentration of reactant in the feed. Movement of reactant from the bulk fluid/stagnant
film boundary to the catalyst surface occurs by molecular diffusion, which is generally
modeled as a linear concentration difference. That difference is BBF BSF, where BSF is
the concentration of reactant at the surface of the catalyst and CBF is the concentration
of reactant in the bulk fluid, both in mol/m3. Reactant must then diffuse from the surface
of the catalyst along pores to the catalytic sites inside the porous solid. Movement of
reactant in the pore is also by molecular diffusion, which is modeled as a linear
concentration difference. Catalytic sites occur along the length of the pore, thus
reactant concentration in a pore is a function of pore length. In other words, reactant
concentration decreases along the length of the pore.
Reactant concentration at a given catalyst site is BAS (mol/m3). Thus, the
concentration difference to that point in the pore is BSF BAS. Equilibrium may be
established at the catalytic site; reactant concentration at equilibrium is BEQ (mol/m3).
For 1-butene isomerization, the mole ratio of 2-butene to 1-butene is 75:25,
respectively.
Olefin isomerization follows a first-order reaction mechanism with respect to
olefin. Thus, for our case, reactant conversion rate is given as

rRxn k Rxn B AS BEQ


Equation 1
where rRxn is the reaction rate for olefin isomerization at the catalytic site (mol/m3*s); kRxn
is the reaction rate constant (1/s).
The rate of reactant movement along the pore is
rPD k PD aP B SF B AS
vP
Equation 2

where rPD is the molar rate at which olefin moves along the pores (mol/m 3*s); kPD is the
velocity at which olefin moves along the pores (m/s); aP is the cross sectional area of

the pore (m2); and, vP is the average catalyst pore volume (m3). The units of k PD a P
vP
3
3
are m /m *s.
The rate of reactant movement through the stagnant film surrounding the catalyst
pellet is

V B

rSF k SF S

BF

B SF

Equation 3
where rSF is the molar rate at which olefin moves along the pores (mol/m 3*s); kSF is the
velocity at which olefin moves through the stagnant film (m/s); S is the exterior surface
area of the catalyst pellet (m2), and V is the volume of the catalyst pellet (m3). The units
of k SF S
are m3/m3*s.
V
The only reactant concentrations known with any accuracy are BBF and BEQ.
Thus, the mathematical expression for the rate of reactant conversion must be in terms
of BBF and BEQ. Solving Equation 1 for BAS yields

rRxn
BEQ B AS
k Rxn
Solving Equation 2 for BSF gives

rPD
B AS B SF
aP

k PD

vP
Substituting for BAS gives

rPD
r
Rxn CEQ C SF
a
k PD P k Rxn
vP
Solving Equation 3 for BBF yields

rSF
k SF S

V B

SF

BBF

then substituting for BSF provides us with

rPDs
rSF
rRxn

BEQ BBF
k Rxn k aP k SF S

V
PD
vP

Rearranging the above equation gives reactant conversion rate in terms of BBF and BEQ.
Thus

rPDs
rSF
rRxn

BBF BEQ
k Rxn k aP k SF S

V
PD
vP

Assuming rRxn = rPD = rSF = r, then rearranging the above equation, yields conversion in
terms of BBF and BEQ

1
1
1

k Rxn k PD a P k SF S V

vP

B BF B EQ

or

r
1
1
1

k Rxn k a P k SF S

V
PD

vP

B BF B EQ

The overall process rate constant kOverall (1/s) is, by definition

k overalll
1
1
1

k Rxn k a P k SF S

V
PD

vP
Inverting kOverall yields

1
k Overall

1
k Rxn

1
1

S
a
k PD P k SF V
vP

Equation 4
Equation 4 has the same mathematical form as a series of resistors in an
electrical circuit. Thus, the overall resistance to olefin isomerization; i.e., 1-butene to 2butene formation, is represented by 1/kOverall. The portion of the overall resistance
6

attributed to the chemical reaction rate is 1/kRxn. Pore diffusion resistance and film
1
diffusion resistance are represented by
and 1
, respectively.
aP

k SF S
k PD

V
vP
Equation 4 can be simplified to yield

1
k Overall

k PD

aP

k
v P Rxn

k PD a P k Rxn
vP

1
k SF S

which reduces to

1
k Overall

1
1

k Rxn k SF S

Equation 5
where is defined as

k PD a P
vP

k PD a P k Rxn
vP
Thus, the overall resistance to 1-butene isomerization is the sum of two resistances:
one related to film diffusion, the other to pore diffusion and reaction rate combined. If
k PD aP k Rxn , then = 1, which describes a reaction rate limited chemical
vP
process. If k PD aP k Rxn , then < 1, which describes a pore diffusion rate limited
vP
chemical process.
Olefin isomerization also depends upon the number of catalyst sites on the
porous solid. Let NIsom
represent the number of isomerization catalyst sites functioning at
t
time t. Note that NIsom
is on a solids basis. However, r is on a fluid basis. Multiplying
t
by
NIsom
t
1

where is the void fraction for the catalyst bed, converts NIsom
from a solids basis to a
t
fluid basis. Therefore, R for olefin isomerization is
7

1 Isom
1 Isom
R
Nt r
Nt k Overall BBF BEQ

Substituting this equation into the integral equation above yields


B

BF
Exit
d BBF
V
1

Q BBF BFeed 1 Isom


1 Isom

Nt k Overall BBF BEQ


Nt k Overall

BBF BExit

BBF BFeed

d BBF
BF BEQ

where BFeed is the concentration of 2-butene entering and BExit is the 2-butene
concentration exiting the MgO catalyst bed. Integrating gives

1 Isom
k Overall
Nt V
B BEQ

ln Exit

Q
BFeed BEQ
Note that N(t) changes with time as active catalyst sites deactivate or become
poisoned. Levenspiel has proposed a method for evaluating the change in N(t) as a
function of time.4
Assume the rate at which the number of active catalyst sites disappears with
respect to time is a power law equation; namely

dNIsom
t
k DecayNIsom
t
dt
where kDecay is the catalyst decay rate constant. Integrating the above equation yields

NIsom
NIsom
e
t
0

kDecayt

where NIsom
is the number of active catalyst sites at any time greater than t = 0 and is
t
defined as

NIsom

Isomerization Rate at time t


Isomerization Rate at t 0

is the number of active catalyst sites at t = 0. NIsom


and NIsom
are indications of
NIsom
0
t
0
catalyst efficiency. NIsom
is assumed to be unity.
0
Substituting NIsom
into the isomerization equation above yields
t

O. Levenspiel, Journal of Catalysis, 25, 265 (1972).


k Overall

V
B BEQ
k
t

NIsom
e Decay ln Exit

0
Q

BFeed BEQ

Taking the logarithm again gives us

1 Isom
k Overall N0 V

B BEQ
- k Decay t lnln Exit

BFeed BEQ

B BEQ
Therefore, plotting lnln Exit
as a function of time produces a straight line with a
BFeed BEQ
declining slope of kDecay. This analysis allows us to quantify kDecay.
Butene isomerization in the MgO/WO3 catalyst bed can be evaluated using the
above equations.
Ethylene Diffusion
The liquid phase ethylene mass balance, in circular cylindrical coordinates, is

1 EL 1 2EL 2EL
EL
EL v EL
EL
vr

vz
DEB

r
2
2
t
r
r
z
z 2
r r r r

REL

where EL represents ethylene molar concentration of ethylene in the butene mixture


(mols/m3); t is time is seconds (s); r is the radial distance from the container centerline
to the inner wall of the container; i.e., reactor; is the azimuthal angle about the
container centerline (dimensionless); z is the physical height of the catalyst bed in the
container (m); vr; v, and vz are the linear fluid velocities in the radial, azimuthal, and
axial directions, respectively (m/s); DEB is the diffusivity constant for ethylene in the
1 EL 1 2EL 2EL
butene mixture (m2/s);
represents the diffusion of ethylene

r r r r 2 2
z 2
in each direction; and, REL is the rate of ethylene appearance or disappearance as the
case may be.
To simplify the above mass balance, we make these assumptions

EL

0 ; the process is at steady state;


t
vr = v = 0; axial flow only;
1 EL 1 2EL 2EL

0 ; no dispersion of any kind.


r

r r r r 2 2
z 2
9

We make these assumptions to arrive at a simple model. If we need a more complex


model, we can relax one of our assumptions to discuss a particular issue at that time.
Implementing these assumptions, we can reduce the above mass balance to
vz

d EL
R EL
dz

To evaluate REL , we must develop a simplified mechanism for the consumption


of ethylene. Figure 2 presents such a mechanism. Gaseous ethylene moves from the
left of Figure 2 to a gas-liquid interface where it is absorbed into the liquid butene
mixture. Henrys Law controls the amount of ethylene absorbed by the butene mixture.
Absorbed ethylene attains some concentration in the butene mixture. That ethylene
concentration remains constant. Dissolved ethylene then diffuses across the stagnant
liquid film surrounding each porous, solid catalyst pellet. Ethylene eventually enters one
of the pores of the catalyst, diffuses along the length of the pore, and finally encounters
a catalyst site where metathesis occurs. Each of these steps has a rate.
The rate at which the mixed butene liquid absorbs ethylene is
rAbs k Abs PE PI

where rAbs is the molar absorption rate of ethylene (atm/s); kAbs is the absorption mass
transfer coefficient (1/s); PE is ethylene pressure (atm); and, PI is ethylene pressure at
the gas-liquid interface (atm). We discount the presence of a stagnant gas film on the
gas side of this physical interface because

the ethylene is essentially pure;


the process operating pressure is high enough to preclude
significant butene vaporization.

Henrys Law controls the dissolved ethylene concentration at the gas-liquid


interface. That ethylene interface concentration is
PI = (He) EI
where He is Henrys Law constant (atm*m3/mol) and EI is ethylene concentration at the
gas liquid interface (mol/m3). Substituting for PI in rAbs gives
rAbs k Abs PE He EI

Rearranging this last equation yields

rAbs
P
E EI
He k Abs He
10

There is a stagnant liquid film on the liquid side of the gas-liquid interface. This
stagnant film develops due to the mixing of ethylene and butene molecules near the
physical interface. The rate of ethylene movement through this liquid stagnant film is
rGLSF k L aL EI EB
vL

where rGLSF is the molar rate of ethylene movement through the gas-liquid stagnant film
(mol/m3*s); kL is the velocity at which ethylene moves through the gas-liquid stagnant
film (m/s); aL
is the ratio of the cross sectional area through which ethylene diffuses
vL
to the volume of that stagnant film (m2/m3); and, EB is the ethylene concentration in the
bulk mixed butene liquid (mol/m3). Rearranging rGLSF gives
rGLSF
E B EI
aL

kL

vL

There is a liquid-solid stagnant film surrounding each catalyst pellet in the


container. The rate of ethylene movement through this liquid-solid stagnant film is

VE

rLSF k LSF S

EPS

where rLSF is the molar rate of ethylene movement through the liquid-solid stagnant film
(mol/m3*s); kLSF is the velocity at which ethylene moves through the liquid-solid stagnant
film (m/s); S is the ratio of the surface area of the catalyst pellet to the volume of the
V
catalyst pellet (m2/m3); and, EPS is the ethylene concentration at the surface of the
catalyst pellet (mol/m3). Rearranging rLSF gives

rLSF
k LSF S

V E

PS

EB

At the catalyst pellet surface, ethylene molecules enter pores leading to the
interior of each catalyst pellet. The rate at which ethylene diffuses along these catalyst
pores is
rPD k PD aP EPS E AS
vP

where rPD is the molar rate of ethylene movement along the catalyst pores (mol/m3*s);
a
kPD is the velocity at which ethylene moves along the catalyst pores (m/s); P
is the
vP
ratio of the cross sectional area of the catalyst pores to the volume of catalyst pores
11

(m2/m3); and, EEQ is the equilibrium ethylene concentration of ethylene at an active


catalytic site (mol/m3). There will be an equilibrium ethylene concentration, E EQ, for this
reaction due to the various metathesis reactions occurring at each catalytic site, such as
C1=C2 + C3=C4 C1=C3 + C2=C4
C1=C2 + C3=C4-C5-C6 C1=C3 + C2=C4-C5-C6
C1=C2-C3-C4 + C5=C6-C7-C8 C1=C5 + C4-C3-C2=C6- C7-C8
Rearranging rPD gives

rPD
EEQ EPS
k PD aP
vP
Back substituting each of the concentrations yields
rAbs
rGLSF
rLSF
rPD
P

E EEQ
He k Abs k a L k LSF S
a
He

V k PD P v
L
v
L
P

But, ethylene cannot diffuse through the process faster than the slowest molar rate;
therefore
r = rAbs = rGLSF = rLSF = rPD
Making the appropriate substitution gives

P
1
1
1
1
E EEQ
r

S
He k Abs k a L k LSF
a
He

V k PD P v

L
v
L
P

koverall for ethylene diffusion, in resistance notation, is


1
k Overall

1
1
1
1

He k Abs k aL k LSF S
a

V k PD P v
L
v
L
P

The form of kOveral for ethylene diffusion is thus similar to that found for 1-butene
isomerization.
Ethylene/2-butene Metathesis
The desired metathesis reaction is
12

C=C + C-C=C-C 2 C=C-C


However, other metathesis reactions can occur at an active catalyst site. Those
reactions are
C=C-C + C=C-C-C C=C + C-C=C-C-C
C1=C2-C3 + C4-C5=C6-C7 C1=C5-C6 + C3-C2=C6-C7
C1=C2 + C3=C4-C5-C6 C1=C3 + C2=C4-C5-C6
C1=C2-C3 + C4=C5 C2=C3-C4 + C1=C4
The above are the main metathesis reactions that we will consider in this
analysis. The first metathesis reaction above produces the product, propylene. The
second metathesis reaction above consumes propylene and produces an unwanted byproduct, which can enter into various metathesis reactions as well; however, we will not
consider those reactions in this analysis. The last three metathesis reactions above
produce no change in the overall product distribution exiting the reactor. They do,
however, occupy the active catalytic site. Therefore, they act as a diluent in the process.
From the above two sections, using the same assumptions, the mass balance for
propylene formation is

V
dP

Q
RP
where P is propylene molar concentration (mol/m 3) and RP is the molar rate of
propylene formation (mol/m3*s). RP is
1 Meta
1 Meta
EEQ 2 B k Meta
k Meta
Nt
Nt 1- BP
Overall
Overall

where k Meta
Overall is the overall metathesis rate constant, which we assume to be the same
for the metathesis reaction forming propylene and for the metathesis reaction
consuming propylene; NMeta
represents the number of active metathesis catalytic sites
t
at time t of the catalyst bed life; and (EEQ), (2-B), (P), and (1-B) are the molar
concentrations of ethylene, 2-butene, propylene, and 1-butene (mol/m3). The above
mass balance then becomes

dP
1 Meta
1 Meta
EEQ 2 B k Meta
k Meta
Nt
Nt 1- BP
Overall
Overall

13

If we let
1 Meta
EEQ 2 B
a k Meta
Nt
Overall

and
1 Meta
b k Meta
Nt 1- B
Overall

we can then write the above integral equation as

V
d P

Q
a bP
The boundary conditions are: at z = 0, P = PFeed; at z = L, P = PProduct. L is the length of
the catalyst bed in the reactor. Integrating the above equation gives

V
1 a bPProduct 1 a bPFeed
ln
ln

Q
b a bPFeed b a bPProduct
If PFeed = 0, the above becomes

V
1 a bPProduct 1
a
ln
ln

Q
b
a
b a bPProduct
Substituting for a and b gives us
Meta 1 Meta

1 Meta
EEQ 2 B k Meta
k Overall
Nt
Nt 1 - BPProduct
Overall

V
1

ln
Q

Meta 1
Meta
Meta 1
Meta
EEQ 2 B
k Overall
k Overall
Nt 1 - B
Nt

Note that k Meta


Overall is

1
k

Meta
Overall

1
k Rxn

1
1

S
a
k PD P k SF V
vP

Flow Patterns through Trickle-bed Reactors


Inlet distributors and local catalyst packing characteristics have an inordinate impact on
the process performance of trickle-bed reactors. This situation arises because the liquid
flow through such reactors is generally slow. If liquid flow is gravity-driven, then there
14

are few degrees of freedom with which to adjust the liquid distribution through the
catalyst mass. Depending upon catalyst pellet properties and liquid flow rate, void-filling
liquid flow may be as films, rivulets, pendular structures, or filaments. Stagnant fluid
pockets may also exist in trickle-bed catalyst masses.5 Figure 3 illustrates these flow
patterns.
The flow patterns in Figure 3 control the residence time distribution of the
process. In other words, it is the wetted area of the catalyst mass that defines residence
time for a catalyst mass. Normalizing conversion with catalyst wetted area can lead to
correlations between process units, but the issue is: how to determine catalyst wetted
area?
Since so many flow types may occur in a trickle-bed catalyst mass and since
there are so few variables for controlling flow type, it is not surprising that these
processes are so difficult to upscale and downscale. We should not necessarily expect
a laboratory tickle-bed reactor to correlate well with a pilot plant trickle-bed reactor,
which, in turn, may not correlate well with a plant trickle-bed reactor.6
Analysis of SCG Olefin Metathesis Processes
Mass Transport
Each reaction, 1-butene isomerization and 2-butene metathesis, have a variety of
resistances. While butene isomerization and metathesis occur in the liquid phase, it is
doubtful that metathesis is pore diffusion rate limited. Porous, solid catalyzed olefin
metathesis is generally not pore diffusion rate limited at molecular weights less than
octene or decene. It is unlikely that the current SCG olefin metathesis process is pore
diffusion rate limited.
The same cannot be said for the 1-butene isomerization process. The number of
catalytically active isomerization sites depends upon the MgO activation procedure. If
few sites are activated during a particular activation procedure, then the SCG
isomerization process could become pore diffusion rate limited. If fewer catalytically
active isomerization sites are generated in the SCG laboratory process than in the SCG
plant process, then the laboratory process will demonstrate lower conversion and
shorter catalyst life. Of course, the same is true for the SCG pilot plant.
It is doubtful that either the SCG isomerization process or the metathesis process
are liquid-solid stagnant film diffusion rate limited.7
Most likely, the SCG olefin metathesis process is reaction rate limited, which
means it becomes highly dependent upon the number of active sites generated during
each activation procedure. It also becomes highly dependent upon the pattern of liquid
flow through the catalyst mass.
Process Poisons
All the above process rate equations contain the term NIsom
or NMeta
, which measure in
t
t
some fashion the number of catalytically active sites for each process. If the catalyst

V. Ranade, R. Chaudhari, and P. Gunjal, Trickle-bed Reactors: Reactor Engineering and Applications,
Elsevier, Amsterdam, The Neatherlands, 2011.
6
L. Ross, Chemical Engineering Progress, 61(10), 77 (1965).
7
D. Mears, Chemical Engineering Science, 26, 1361 (1971).

15

activation procedure varies, then NIsom


and NMeta
will vary. For low NIsom
and NMeta
,
t
t
t
t
process conversion will be low and catalyst life will be short compared to a catalyst
activation procedure that produces larger NIsom
and NMeta
numbers.
t
t
Also, if the olefin metathesis process contains a poison, then NIsom
and NMeta
will
t
t
decline faster than normal; thus, the olefin metathesis process will demonstrate lower
process conversion and shorter catalyst life.
The MgO solid base catalyst is poisoned by Lewis acids; it is particularly
sensitive to water. The WO3 metathesis catalyst is most likely susceptible to water
poisoning. If isomerization catalyst sites are decaying preferentially to metathesis
catalyst sites, then 3-hexene will accrue in the process. If metathesis catalyst sites are
decaying preferentially to isomerization catalyst sites, then 2-pentene will accrue in the
process.
Axial Aspect Ratio --- Axial Dispersion

2E L
, can be neglected if the axial
Carberry suggests that axial dispersion, DEB
2
z
aspect ratio, Z , where Z is the physical height of the catalyst mass or bed and d P is
dP
the diameter of the catalyst pellet, is greater than 150.8 Carberrys criterion is
considerably more conservative than the common rule of thumb for axial dispersion;
namely, Z 30 to ensure against axial dispersion.9 Mears has published a more
dP
general rule for deciding whether a concurrent, gas-liquid, trickle-bed reactor suffers
axial dispersion. His general rule is
CIn
Z
20n

ln
dP dP v z
COut

D
a

where n is reaction order; vz is superficial liquid velocity; Da is the axial diffusivity


coefficient; [C]In is the concentration of reactant entering the trickle-bed reactor, and
[C]Out is the concentration of reactant exiting the trickle-bed reactor. If axial dispersion
occurs in a process, then its conversion will be less than expected.
Radial Aspect Ratio --- Radial Dispersion

1 EL
The opposite is true for radial dispersion, DEB
r
. If the radial aspect ratio
r r r
R where R is the radius of the container and dP is the diameter of the catalyst pellet,
dP
is less than 3 or 4, then we can neglect radial dispersion.10 However, radial dispersion
8

J. J. Carberry, Canadian Journal of Chemical Engineering, 36, 207 (1958).


D. Mears, Chemical Engineering Science, 26, 1361 (1971).
10
H. Lee, Heterogeneous Reactor Design, Butterworth Publishers, Boston, MA, 1985, page 291.
9

16

arises only when a fixed-bed reactor is externally cooled. In other words, the reaction
has to be exothermic, thereby requiring external cooling. It is the temperature difference
between the centerline portion of the catalyst mass and the container wall that induces
radial flow; i.e., radial dispersion. Since olefin isomerization is nearly thermally neutral
and olefin metathesis is thermally neutral, it is doubtful that radial dispersion occurs in
the SCG olefin metathesis processes.
Pellet Aspect Ratio
There is also a pellet aspect ratio. It is D

dP

, where D is the diameter of the container

10 , then we generally assume


dP
process fluid is channeling along the container wall.11 If wall channeling occurs, then
process conversion will be lower than expected. Mears writes that at ninety-two percent
conversion, a wall flow of 1.1 percent is sufficient to increase the required reactor length
by five percent.12
and dP is the diameter of the catalyst pellet. If D

Summary of Aspect Ratios


The below table gives the aspect ratios for the various SCG olefin metathesis
processes.13
Process Scale
Laboratory
Pilot Plant
Plant

Axial Aspect Ratio


3.5
13
758

Radial Aspect Ratio


1.6
3.8
300

Pellet Aspect Ratio


3
8
600

The above table indicates that the SCG laboratory and pilot plant olefin metathesis
process conversions might be lower than expected due to axial dispersion. Conversion
at the plant does not suffer from axial dispersion. On the other hand, the plant may
experience radial dispersion, but it is doubtful that such dispersion adversely impacts
process conversion. The laboratory process does not experience radial dispersion. The
pilot plant may or may not experience radial dispersion. The above table does indicate
that conversion in the laboratory process is probably adversely impacted by wall
channeling. Conversion in the pilot plant process probably suffers from some wall
channeling. Conversion at the plant is not impacted by wall channeling.
Recommendations
1. Determine koverall for isomerization as a function of MgO activation temperature
and activation procedure.
2. Monitor the process for 2-pentene and 3-hexene and determine whether they can
be correlated to specific catalyst poisoning.

11

H. Rase, Chemical Reactor Design for Process Plants, Volume One, Principles and Techniques, John
Wiley and Sons, Inc, New York, NY, 1977, page 537.
12
D. Mears, Chemical Engineering Science, 26, 1361 (1971).
13
Wiroon Tanthapanichakoon, e-mail communication, 5 October 2015.

17

3. Determine whether pre-wetting the catalyst bed improves process performance.


If pre-wetting improves process performance, then channeling through the
catalyst bed is most likely happening.14
4. Determine whether increasing ethylene velocity through the catalyst bed
improves process performance. Increasing gas velocity increases the local liquid
flow through the central portion of the catalyst bed, which will improve process
conversion.15
5. Determine whether spherical catalyst pellets improve process performance.
Cylindrical catalyst pellets are more likely to create wall channeling than are
spherical pellets.16
6. Determine the impact of catalyst bed length on process performance. If wall
channeling is occurring, then process performance will improve as a function of
catalyst bed length. Process performance will increase as catalyst bed length
increases and eventually it will plateau.17
7. Confirm the presence of wall channeling by building and operating a laboratory
reactor with a minimum diameter of 50 mm. Such a reactor will give D 10 .
dP
Or, reduce the catalyst pellet diameter so that the present process meets
D 10 .
dP
8. Start measuring kDecay for all process catalysts. Use these kDecay to compare
catalyst stability.
9. Start developing process performance correlations between each SCG tricklebed process. Because of the various liquid flow patterns through a trickle-bed
catalyst mass, it is unlikely that a fundamental scaling rule will work. SCG will
have to develop empirical correlations between their various sized trickle-bed
processes.

14

A. Sederman and L. Gladden, Chemical Engineering Science,56, 2615 (2001).


N. Sylvester and P. Pitayagulsarn, Canadian Journal of Chemical Engineering, 53, 599 (1975).
16
M. Borda et al, American Institute of Chemical Engineering Journal, 24, 439 (1978).
17
D. Mears, Chemical Engineering Science, 26, 1361 (1971).
15

18

Figure 1.
Schematic of Butene Isomerization

Bulk Fluid
BBF

Pore
BAS

Catalytic Site
BEQ

(BSF BAS)
(BAS BEQ)
(BBF BSF)
Stagnant Film
BSF

19

Figure 2.
Schematic of Ethylene Absorption into Mixed Butenes with Reaction.

Gaseous
Ethylene
PE
PE = HeEPI
Bulk Fluid
EB

Pore
EPD

Catalytic Site
ERxn

(ESF EPD)

Stagnant
Film
(EI EB)

Stagnant
Film
ESF
(EB ESF)

20

(EPD ERxn)

Figure 3.
Liquid Flow Patterns through a Trickle-bed Catalyst Mass
(From: V. Ranade, R. Chaudhari, and P. Gunjal, Trickle-bed Reactors: Reactor
Engineering and Applications, Elsevier, Amsterdam, The Neatherlands, 2011,
page186.)

21