New Catalyst Exhibits Deactivation

during a Di-Olefins Hydrogenation in a

Non-Isothermal CSTR
PREPARED FOR
DR. JAMES SPIVEY OF BLACK DIAMOND CHEMICALS

Presented by
Kinetic Investigations and Special Services (KISS)
Representative: Breanna Lee, Researcher
 Di-olefins hydrogenation requires a catalyst
to promote the formation of product

https://en.wikipedia.org/wiki/Hydrogenation
http://philschatz.com/chemistry-book/contents/m51104.html
Intrinsic rate of reaction is evaluated in a
non-isothermal CSTR
Power Law Rate Equation

=
First Order, =1

Design Equation
, ,
=

= .

Linearization of the rate law determines
reaction order and intrinsic rate constant
= + ( ) 0.25 0.45 0.65 0.85 1.05 1.25

-0.9
= . .
-1.1 y = 1.09x - 2.55
= . R = 0.995
-1.3

, 95 = 0.0817
ln(r)
-1.5

, 95 = 0.0747 -1.7

-1.9
Feed Flow Rate Range :
3 -2.1
1.0 6.0

-2.3 ln(C)
 Arrhenius equation produces intrinsic
activation energy and pre-exponential factor
0.0027 0.0029 0.0031 0.0033 0.0035
= 0

-2

= . .
-4

= .
ln(k)
-6

, 95 = .
-8
y = -9892.4x + 25.504
, 95 = . R = 0.9998
-10

-12 1/T [K ]
Temperature Range: 280 K - 360 K
 Diffusion factors limit rate at high T,
while the intrinsic rate limits rate at lower T
Temperature Dependence

Peak moves
More
to molecules
higher
exceed
energyactivation
energy

Fogler. "Diffusion and Reaction." (2008): 813-66. University of Michigan. Web.

 Diffusion factors limit rate at high T,
while the intrinsic rate limits rate at lower T

Fogler. "Diffusion and Reaction." (2008): 813-66. University of Michigan. Web.

 Diffusion factors neglibly affect activation
energy at high temperatures from first run
4

2
= 1 , Ea = 82.3 KJ/mol
0 At low
0.0023 0.0028 0.0033 = 0.892 , Ea = 77.9 KJ/mol
temperatures,
-2 =1
ln(k)

Intrinsic Rate Limiting

-4
At high Projected Trend
-6 temperatures,
expect < 1 Diffusion Limiting
-8

-10
1/T K-1
 Additional runs indicate neglible mass
transfer limitations beyond 400 K
5
3
440 K
425 K 3
2
1
1
-10.0021 0.0025 0.0029 0.0033

ln (k)
0
ln (k)

0.0021 0.0023 0.0025 0.0027 0.0029 -3

-1
-5
420 K
-2 < 1 at T > 400K -7 Overall Ea = 91.1 8.4
Intrinsic Ea = 83.0 0.2
-3 = 1 Ea= 82.4 0.1 kJ -9

-4 1/T [K] -11 1/T [K]

Catalyst deactivation must be accounted
for in evaluation of reaction rate
()
=
(0 )

First Order Deactivation Model

Second Order Deactivation Model

1
=
1 +
Intrinsic Rate Constant and Deactivation Rate Constant Relationship
() ln 0 ln ln()
= = =
(0 )
At T= 350K, the 1st order deactivation
model indicates catalyst deactivation
1.2 =
= .
1 Error = 0.0435
Activity

0.8

0.6

0.4

0.2

0
0 50 100 150 200 250 300 350
Hours on Oil (t)
At T= 350K, the 1st order deactivation
model indicates catalyst deactivation
Experimental Data Trend
0.2
=
0.1 No Deactivation

0
0 50 100 150 200 250 300 350 400 450
-0.1
ln (a(t))

-0.2

-0.3

-0.4

-0.5

-0.6 = 0.000615 0.0004 1

-0.7 Hours on Oil (t)
At T= 350K, the 2nd order deactivation
also indicates catalyst deactivation

= = .
+
1.2 Error = 0.0395

0.8
Activity

0.6

0.4

0.2

0
0 50 100 150 200 250 300

Hours on Oil (t)

 Catalyst deactivation is detected, however
effectiveness factor remains consistent
Best Fit : 2nd Order Decay Model Parameter Experimental Value

1.2

Intrinsic Rate, r .

1
Intrinsic Rate Constant, .
0.8 Reaction Order, . .
Activity

0.6 Intrinsic Activation Energy,

. .

0.4
Intrinsic Pre-Exponential
.
Factor, A
0.2

Effectiveness Factor, Remains statistically 1

0
0 100 200 300
Deactivation Rate
.
Hours on Oil (t) Constant,
1st Order Linearized Decay Model With
Adjusted Y-Intercept
0.2

0.1

0
0 50 100 150 200 250 300 350 400 450
-0.1
ln (a(t))

-0.2

-0.3

-0.4

-0.5
Experimental Data Trend
-0.6
Linear (No Deactivation) y = -0.0011x
-0.7 R = 0.1892
Hours on Oil (t)