Multiphase Reactor

SLURRY REACTORS
CREATED BY: MA. CHARLENE C. TAPIA
Slurry Reactors
Used for metal-catalyzed hydrogenations of alkenes
and alkynes, hydrogenations of ketones, aldehydes,
nitro compounds.
Three-phase reactor that could cater solid-catalyzed
reaction of a gas with liquid like PBR
Amount of catalyst in the reactor is only 0.01-1% of
the total volume (for PBR: 50-60% of the volume)
Sequence of Steps
Consider the reaction of hydrogen with olefin B (exothermic and irreversible)

Note: if hydrogen is diluted

with solvent vapor, mass
transfer from gas phase to
1. H2 dissolves and diffuses into the bulk liquid gas-liquid interface is an
additional step
2. H2 diffuses to the catalyst particles
3. Reactant B diffuses to the catalyst particles
4. H2 and B diffuses into the catalyst pores, adsorb and react
5. Product C desorbs and diffuses out of the catalyst and into the bulk liquid
Slurry Hydrogenation Model
Simplification:
1. Surface reaction is assumed first order to hydrogen
2. Omit step 3 because CB>>>CH2 in liquid
◦ Low solubility of hydrogen in liquid

3. Exclude step 5 in the model (to be considered in the selectivity with consecutive reactions)
4. Neglect accumulation of hydrogen
5. Assume all the steps in series take place at the same rate
Overall Rate Equation
1. H2 dissolves and diffuses into the bulk liquid

Where,
is volumetric coefficient for gas bubbles
is the concentration of H2 at the gas liquid interface
is the concentration of H2 in the bulk liquid
Overall Rate Equation
2. H2 diffuses to the catalyst particles

Where,
is the external mass transfer coefficient
is the external area per gram
is the catalyst concentration
is the concentration of H2 at the catalyst surface
is the concentration of H2 in the bulk liquid
Overall Rate Equation
3. H2 diffuses into the catalyst pores, adsorb and react

Where,
is the effectiveness factor
is the specific rate constant
is the catalyst concentration
is the concentration of H2 at the catalyst surface
Overall Rate Equation
Assuming steady state, the rates of each steps are equal,

The equations are rearranged as shown below:

Overall Rate Equation
Adding the previous equations since these occur in series gives,
Separating the Resistances

If all the runs are at the same

hydrogen pressure, plot 1/r instead
of Ci/r
Interpreting Reciprocal Plots
• Intercept:

• Gas absorption resistance is large

• CB is lower and is not at saturation value
• Reaction rate is strongly affected by
agitator speed and superficial gas
velocity
Interpreting Reciprocal Plots
• Intercept:

• Gas absorption resistance is close to zero

• Catalyst resistance is controlling
• Reaction rate increases almost in
proportion to the catalyst charge
• Solution is saturated with hydrogen (no
effect if is changed)
Interpreting Reciprocal Plots

• Non linearity in reciprocal plot at high

1/m may be due to catalyst poisoning.
• Impurities can poison a significant
fraction of the catalyst if present in small
amounts.
• Solution: Ignore plots at high 1/m
Interpreting Reciprocal Plots

• Non linearity in reciprocal plot at low

1/m may be due to agglomeration or
incomplete suspension of the catalyst.

• Solution: Ignore plots at low 1/m

Gas-Absorption Coefficient
From separation of resistances, we get:

Estimating :
1. General correlation for gas absorption in stirred reactors
2. Start with published data for a hydrogenation reaction and correct for
differences
Gas-Absorption Coefficient
From the correlation of Van’t Riet (with H2 absorption correction):

Where
is kW/m3
is cm/sec
is 2.4*10^-5 cm2/sec at 25oC
Sample Problem
Soybean oil was hydrogenated at 204oC and 45psig using nickel catalyst in a
stirred reactor. With 0.005% Ni, the iodine value (IV) decreased from 120 to 80
in 26 minutes and with 0.0125% Ni, it took 17 minutes to reach IV=80. Estimate
the gas absorption coefficient and the fraction of the overall resistance due to
gas absorption. (Assume: oil density=0.8 g/cm3)
Sample Problem
Sample Problem
Sample Problem

Fraction of the overall resistance due to gas

absorption:

Run 1:

Run 2:
External Mass Transfer
Recall:

can be predicted from studies of mass transfer to suspended particles,

External Mass Transfer
For spheres in water and viscous
solutions and particle diameter
between 10-100 microns,

For reactors with vigorous agitation,

Note: may be known only to ±50% but even a rough estimate may be useful in
evaluating kinetic data
Sample Problem
The palladium-catalyzed hydrogenation of nitrobenzene in methanol at 1 atm
and 30oC was studied by Acres and Cooper. The rate was proportional to the
amount of catalyst used and independent of the nitrobenzene concentration in
the range 0-20% nitrobenzene. The reaction rate was 2.4 L H2/in g cat and the
average particle size of the Pd/C catalyst was estimated to be 10 microns.
Estimate the effect of external mass transfer for these conditions.

Given:
diffusivity of H2 is 2.04*10^-4 cm2/sec; dry catalyst density = 1.2 g/cm3;
methanol density = 0.79 g/cm3; methanol viscosity=0.52 cp;
Sample Problem
Sample Problem

With vigorous agitation,

Therefore,
 Sample Problem
For a measured rate of 2.4 L H2/min-g cat

Assume ,

External mass transfer resistance is about 8% of the overall resistance, which is

barely significant.
Internal Mass Transfer and
Reaction
Recall:

For very small particles, surface reaction is controlling and

For small to moderate-size particles,

For moderate to large particles,

Limiting Reaction Step:
Resistances vs Diameter

For very small particles (Surface reaction limiting)

For small to moderate-size particles (Internal diffusion limiting)

Limiting Reaction Step:
Resistances vs Diameter
For moderate to large particles (External mass transfer limiting):

Case 1: No shear stress between particles and fluid (Sh=2)

Case 2: Shear between particles and the fluid ()

Limiting Reaction Step:
Resistances vs Diameter
Selectivity
Consider the reaction shown below,

Selectivity is defined as,

Selectivity
• The average L/O ratio in the catalyst is about
half the ratio at the surface which reduces
selectivity by 50%
• With addition of a catalyst, selectivity
increases with increasing catalyst charge.
• Selectivity also increases for decreasing H2
concentration
 End of Chapter Problem
A nickel-catalyzed hydrogenation gives a curved plot
when 1/r is plotted versus 1/m. m,g/L r
a. Ignoring the curvature at high values of 1/m, 0.004 0.025
extrapolate to get the reaction rate when gas 0.005 0.033
absorption is controlling. 0.010 0.055
b. Assume there is a small amount of poison, mp, that 0.015 0.067
0.020 0.077
inactivates the same amount of catalyst for each run.
Find a value for mp, that gives a reasonable straight
line for a plot of 1/r vs 1/(m-mp). What is the
estimated reaction rate for gas aborption control?
 End of Chapter Problem
Plot for given table: Ignoring high 1/m:

R^2= 0.959 R^2= 0.997

Intercept=0.033
Sample Problem
The value of mp was obtained through minimization using MathCAD:
Sample Problem

Reaction rate decreased due to the presence of catalyst poisoning.

Thank you!
References:
Fogler, H.S. (2007). Elements of chemical reaction engineering. Retrieved from
http://www.umich.edu/~elements/fogler&gurmen/html/12chap/html/slurry.pdf
Harriot, P. (2002). Chemical Reactor Design. New York, NY, USA: Marcel Dekker Incorporated.
pp315-357