CHEN 3010 Reaction Engineering

Lab-1 Report
Experiment 6 Armfields catalytic reactor (Exercise A)

Date of Experiment: Friday 31st March 2017

Time: 8:00 11:00

Date Due: Friday 28th April 2017

Lab Demonstrator: Dr. Anteneh Yeneneh

Group Number: G8-2

Group members:

Name ID % contribution Signature

Chunguang Su 16348149 100
Jessica Tedja 17240592 100
Lawrence Alago 17761161 100
Table of Contents
Introduction ............................................................................................................................................ 1
Objectives ............................................................................................................................................... 1
Experimental setup ................................................................................................................................. 1
Experimental Procedure ......................................................................................................................... 2
Results ..................................................................................................................................................... 3
Data analysis Calculations .................................................................................................................... 5
Steady-state conversions .................................................................................................................... 6
Thieles modulus and Efficiency .......................................................................................................... 6
Sensitivity analysis .............................................................................................................................. 7
Temperature sensitivity .................................................................................................................. 7
Feed volumetric flow rate sensitivity .............................................................................................. 8
Discussion................................................................................................................................................ 8
Interpretation of results...................................................................................................................... 9
Comment on FIA (Fluid Injection Analysis) ..................................................................................... 9
Determination of k .......................................................................................................................... 9
Sensitivity Analysis Comments...................................................................................................... 10
Comment on Thieles Modulus and efficiency factor ................................................................... 10
Unexpected events during the experiment ...................................................................................... 10
Initial disturbance during the experiment .................................................................................... 11
Broken tube................................................................................................................................... 11
Wrong concentration addition ..................................................................................................... 11
Contributing error factors ................................................................................................................. 11
Accuracy of Absorption values...................................................................................................... 11
Effect of de-gassed feed solution.................................................................................................. 12
Reliability and precision of the data ................................................................................................. 12
Possible improvements to increase reactor performance ............................................................... 12
Conclusion ............................................................................................................................................. 13
References ............................................................................................................................................ 14
List of Figures
Figure 1: Simplified process of the CEU for Experiment 6 ...................................................................... 1
Figure 2 - Glucose standard curve .......................................................................................................... 3
Figure 3 - Absorbance for the two chemical reactors............................................................................. 3
Figure 4 - Glucose standard concentrations vs. Peak Optical absorbance ............................................. 4
Figure 5 Graph to determine rate constant (Reed and Dranoff 1974) ................................................ 5
Figure 6: Graphical representation of the efficiency factor vs Thiele's modulus for a spherical catalyst
................................................................................................................................................................ 8
Figure 7: Reactions involved with dye formation as mentioned from the lab manual .......................... 9
Figure 8: Uncropped absorption recorded values throughout the experiment ................................... 11
Figure 9: Comparison of the kinetic constants for the SSS/HEMA-T fiber and Amberlite IR-120B on
sucrose inversion (Mizota, et al. 1994, 2218) ....................................................................................... 13

List of Tables
Table 1 - Corresponding concentrations from peak optical absorbance................................................ 4
Table 2 Plotted and obtained data through Figure 5 ........................................................................... 6
Table 3: Sensitivity analysis on Temperature and its effects on the kinetic constant ............................ 7
Table 4: Sensitivity analysis on feed volumetric flow rate and its effects on the space time value....... 8
Lab 1: Armfields Exercise A Group 8-6

Introduction
There are many types of reactor in chemical processes. Such as continuous stirred reactors (CSTR),
batch reactors (BR) and packed bed reactors (PBR). Each of type of reactor has different interaction
amount reactants and result in different products. The catalytic reactor consisting of three packed bed
reactors (two chemical reactors and one biological reactor) was used in this experiment. Two catalysts
were considered. Strong cationic exchange resin and immobilized enzyme invertase. It would be
worked out by automated analytics technique FIA. Also, this method can be used widely in chemical
and industry area.

Objectives
The purpose of this experiment is to study the sucrose inversion using a catalytic reactor. Data was
logged using the CEU software Corresponding kinetic constants, efficiency factors and Thieles
modulus can be calculated.

Experimental setup
The experiment consists of control console, three packed bed reactor columns (two chemical packed
bed reactor columns and one biological reactor), feed pump, hot water circulation system, optical
sensor, and FIA.

Figure 1: Simplified process of the CEU for Experiment 6

1
Lab 1: Armfields Exercise A Group 8-6

Experimental Procedure
1. Ensure that all the valve position is correct for the reactor to be used. Ensure enough volume
of solution and that they are made to the appropriate concentrations.
2. Turn the power on.
3. Set the feed pump to give a flow rate of 10 ml min-1.
4. Set the FIA valve to the load position and turn the pump on, adjust the absorbance to 0 prior
to pumping.
5. Direct the 3-way valve so that each of the glucose standards optical absorbance is measured.
Ensure that between standards, it is loaded for a sufficient time to avoid contamination.
6. Turn on HWC system and allow temperature to rise to 70oC then turn on the feed pump.
7. Wait 15 minutes for it to reach steady state and then take a measurement of the reactor
product stream.
8. Stop the feed pump and change the set-up for the next reactor, then after 15 minutes when
it reaches steady state, collect the measurement of the reactor product stream.
9. Flush the reactors.

2
Lab 1: Armfields Exercise A Group 8-6

Results
Absorbance vs Time
1.400

1.200

1.000
Absorbance

0.800

0.600

0.400

0.200

0.000
00:00 07:12 14:24 21:36 28:48 36:00 43:12 50:24
Time (minutes)

Figure 2 - Glucose standard curve

Absorbance vs Time
0.900

0.800

0.700

0.600
Absorbance

0.500

0.400

0.300

0.200

0.100

0.000
57:36 04:48 12:00 19:12 26:24 33:36 40:48
Time

Figure 3 - Absorbance for the two chemical reactors

3
Lab 1: Armfields Exercise A Group 8-6

Concentration vs Absorbance
4.5
4
3.5
3
Concentration (g/L)

2.5
2
1.5 y = 4.186x - 1.1021
1 R = 0.9703
0.5
0
0.45 0.55 0.65 0.75 0.85 0.95 1.05 1.15 1.25
Absorbance

Figure 4 - Glucose standard concentrations vs. Peak Optical absorbance

By plotting the concentration standards against the peak absorbance in Figure 4, an almost linear
trend line was observed. By inputting the absorbance peak values in the trend line equation, the
concentration for reactor 1 and reactor 2 is found and is tabulated in table 1.

Table 1 - Corresponding concentrations from peak optical absorbance

Absorbance Concentration (g/L)

Standard 1 0.475 1
Standard 2 0.771 2
Standard 3 1.037 3
Standard 4 1.159 4
Reactor 1 0.82 2.33
Reactor 2 0.823 2.34

4
Lab 1: Armfields Exercise A Group 8-6

Data analysis Calculations

Vreactor = 100 ml Reactor 2 (0.71 0.35) mm

Q = 10 cm3/min-1 Ea=66.67 KJ/mol

Reagent loop = 52 cm L = 19 cm

Product loop = 30 cm t = 15 mins (1.5 x space time as per Manual)

Reactor 1 (1-0.71) mm

100
= = =
3
10

1 + 0.71
, 1 = = .
2

1 0.855
, = = = .
2 2

0.71 + 0.355
= = .
2

2 0.533
, = = = .
2 2

Effect of particle size on rate

8.00

7.00
y = 5.9575x + 1.5182
6.00 R = 0.99
1/k (min-1)

5.00

4.00

3.00

2.00
0.45 0.55 0.65 0.75 0.85 0.95 1.05
Dr (mm)

Figure 5 Graph to determine rate constant (Reed and Dranoff 1974)

From Figure 5, the trend line equation is obtained through points in table 2 from Reed and Dranoff
(1964). Using the equation, 1/k is calculated and inverted to find our corresponding kinetic constants
k1 = 0.151 min and k2 = 0.214 min

5
Lab 1: Armfields Exercise A Group 8-6

Table 2 Plotted and obtained data through Figure 5

dr (mm) k (min) 1/k (min-1)

1.010 0.134 7.463
0.715 0.168 5.952
0.505 0.226 4.425
0.855 0.151 6.612
0.530 0.214 4.676

Steady-state conversions
0.1 3
1 (1000 3 ) ( 0.19 ) (0.000855)
1 = = = 450
1 103 /2

0.1 3
2 (1000 3 ) ( 0.19 ) (0.000533)
2 = = = 280.53
1 103 /2

Since Re<1000,

190
1 = 0.6 = 0.6 ( ) = 133.33
1 0.855

190
2 = 0.6 = 0.6 ( ) = 213.88
2 0.533

1 1 ()2
( )
= (1 1 ) 4 = 0.7754 = . %
2 3
0

2 2 ()2
2 ( )
= (1 ) 4 = 0.8799 = . %
2 3
0

Thieles modulus and Efficiency

1

2
, = 0 ( )

Where,

r0 radius of catalyst particle

k Kinetic constant

De Effective diffusivity

1 0 ,1 0.4275
= = = 1.604
2 0,2 0.2665

1
2 =
1.604

6
Lab 1: Armfields Exercise A Group 8-6

3 1 1
, 1 = [ ]
1 1 1

3 1 1 1 1
1 1 1 [1 1 ] 0,2 1 1

= = =
2 2 3 1 1 1 1
[ ] 01 0,2
2 2 2 (1 ) 1 0,2
0,1 0,1

1 1
1 0.151 0.2665
1 1
= =
2 0.214 0.4275 1 1

0.2665 0.2665
(1 ) 1
0.4275 0.4275

Solving the above equations, we obtain = . (using excel solver)

6.135
= = .
1.604

3 1 1
= [ ] = 0.409 = . %
1 1 1

2 0.214
= 1 = (40.9) ( ) = . %
1 0.151

Sensitivity analysis
Temperature sensitivity
With the reaction temperature being 70C (343 K), k1 and k2 are 0.151 and 0.214 min-1 respectively.
Using the Arrhenius equation to do sensitivity analysis:
1 1
( )
2 = 1 1 2

2 is the kinetic constant at temperature 2

1 is the known kinetic constant at temperature 1 = 373 K for the specific reactor

E is the activation energy of sucrose inversion with the use of Amberlite IR 120 catalyst = 66 670

R is the gas constant 8.314

Table 3: Sensitivity analysis on Temperature and its effects on the kinetic constant

T k1 k2
(degrees) T(K) (min) k1 error % (min) k2 error %
69 342 0.141 6.61 0.200 6.61
70 343 0.151 0 0.214 0
71 344 0.162 7.03 0.229 7.03

From Table 3, a temperature change of 1C can result in an average of 6.8% on the kinetic constant
as a percentage error.

7
Lab 1: Armfields Exercise A Group 8-6

Feed volumetric flow rate sensitivity

Table 4: Sensitivity analysis on feed volumetric flow rate and its effects on the space time value

Q
(cm3/min) (min) error (%)
9 11.1 11.1
10 10 0
11 9.09 9.09

From Table 4, a volumetric flow rate change of 1 cm3/min can result in an average of 10.1% on the
space time as a percentage error.

Discussion
The experiment was designed to investigate the effects of catalyst particle size in a Packed Bed Reactor
for the inversion of sucrose to glucose and fructose.

Results show that the efficiency factor for the catalytic reaction is larger when a smaller particle size
was used for the catalyst. Efficiency factor for the first reactor, 1 (with the larger particle diameter
for the catalyst Thieles modulus of 6.135) yielded 40.9% whereas for the second reactor with a
smaller diameter with a Thieles modulus of 3.825, 2 was 57.96%. These values are concordant to
Figure 6 below which is from the laboratory manual.

2 1

Figure 6: Graphical representation of the efficiency factor vs Thiele's modulus for a spherical catalyst

It was found that the Reynolds number on the fluid flow across the catalyst particles were below
1000, so the simplified version of the Peckel equation (for Re<1000) was used. Simultaneously, the
conversion of reactor 1 with the larger diameter catalyst was 77.53% compared to reactor 2 with a
smaller diameter catalyst with 87.98% conversion.

8
Lab 1: Armfields Exercise A Group 8-6

Interpretation of results
Comment on FIA (Fluid Injection Analysis)
When the glucose standards and feed were loaded, 60% on the knob was used during loading. Whilst
during injection stage, 30% on the knob was used.

In the manual, 5 second intervals for recording the absorption values were specified. However, during
the experiment this interval was lowered down to 2 seconds.

FIA allows sample from the product stream (which contains glucose, fructose and unreacted sucrose)
to be mixed with the assay reagent in a specific ratio mixture. This mixture is then pumped through a
holding tube giving it enough residence time for the dye formation to occur before passing the mixture
through an optical flow cell where its absorbance value is measured. The reagent and product loop
were 52 and 30 cm respectively.

To increase the sensitivity of the analysis, the assay reagent and the product would need to be mixed
evenly for reaction to be homogenous to analyse all the formation of glucose as it is completely
reacted for dye formation. Dispersion of the reagent-product mixture is enhanced by looping the
tubes. Increasing the loop lengths also yields a larger volume to reduce error however, with larger
volume problems such as higher pressure drop due to longer length and reading time lag will occur.

Figure 7: Reactions involved with dye formation as mentioned from the lab manual

The manual also mentions that the reaction rate of the dye formation is temperature sensitive. This
means that if the loops are not long enough (indicating a smaller residence time), complete conversion
to the dye will not undergo 100% causing the absorption values to be imprecise and not completely
match the conversion of sucrose to glucose and fructose.

Determination of k
The kinetic constants (k) for both reactors were found by interpolating the results correlating 1/k and
diameter of Amberlite IR 120 catalyst from Reed and Dranoff (1964) which can be seen in Figure 5. It
is valid to assume this values as the reaction occurring and the temperature conditions match with
this experiment.

An improvement would be measuring the kinetic constant from the experiment by plotting the
corresponding differential method approach curve given that the inversion of sucrose through its
hydrolysis is first order (from the lab manual):

, = =

ln( ) = ln() + ln( )

9
Lab 1: Armfields Exercise A Group 8-6

Plotting this correlation would yield a y-intercept of ln(k). This could be done for both reactors to find
their k values correspondingly. The value of CA can be determined through its conversion to glucose
which is known from the absorption value of the reactor at specific intervals of time.

Sensitivity Analysis Comments

The only major variables that could be subjected to sensitivity errors were the temperature and feed
volumetric flow rate values (as other variables such as the volume of the reactor and catalyst particle
size were fixed).

As determining the Thieles modulus, required the use of both the kinetic constants for reactor 1 and
2, the calculated 1 and 2 and consequently the calculated efficiency values 1 and 2 will have an
average percentage error of 13.6% if the temperature was 1C off.

Moreover, determining the conversion in each reactor requires the use of the k value once and the
space time value 4 times, this means that if the feed volumetric flow rate was to be 1 cm3/min off, a
percentage error of 40.4% will be associated with the calculated conversion value, whilst 6.8%
percentage error will be associated with the calculated conversion values if the temperature was 1C
off.

Comment on Thieles Modulus and efficiency factor

The lab manual states that the efficiency factor determines if the reaction is chemical or diffusion
controlled. It states that diffusional control occurs at high values of the Thieles modulus, , resulting
in to be approximately 3/. Using results from reactor 1 which has a larger catalyst diameter:
3 3
= = 0.489 1 ( 0.409)
1 6.135

Thus, indicating that at the particle size diameter of the catalyst for reactor 1, the reaction rate is
governed by diffusion. The lab manual states that sucrose inversion is controlled by diffusion.

However, for the reactor 2 with a smaller catalyst diameter:

3 3
= = 0.784 2 ( 0.5796)
2 3.825

For a reaction to be chemically controlled, it must have a low Thieles modulus and that the efficiency,
approximates to 1. From reactor 2s condition, it does not align to be chemically controlled. This
indicates that at the specific diameter of the catalyst in reactor 2 results in the reaction being either
governed by both kinetics and chemically or neither.

Unexpected events during the experiment

All the absorption readings for the glucose standards as well as the products from the 2 reactors were
analysed within one time frame/in one sitting. Figure 8 below shows the true absorbance recording
times. Figure 8 is the sum consecutive recordings as seen in Figures 1 and 2.

10
Lab 1: Armfields Exercise A Group 8-6

Absorbance readings throughtout the experiment

1.6
Calibration curve Reactor 1 and 2
1.4 determination reactions
1.2

1
A
Absorbance

0.8

0.6
B
0.4
C
0.2

0
Time (min)

Figure 8: Uncropped absorption recorded values throughout the experiment

Initial disturbance during the experiment

From Figure 8, the sectioned area A shows that initially in the experiment, absorbance readings were
anomalous (due to the experiment just being started up) until the problem was rectified. This section
was removed to produce the calibration absorbance readings as shown in Figure 2.

Broken tube
After the first absorbance curve was attained from the first glucose standard solution (as shown in
sectioned area B in Figure 8), it was observed that the recorded absorption value would not
decrease. Upon further inspection, this erroneous result was caused by a broken tube situated behind
the absorbance reading display. Once this broken tube was fixed, the absorption values were once
correct again through fixing the disruption in the loop to measure the absorbance.

Wrong concentration addition

After the second absorbance curve was achieved, sectioned area C from Figure 8 was due to the fact
that glucose standard 2 was not changed to 3 prior the reading, so it was ceased and sufficient time
was allowed for the curve to drop back to 0 before moveing on to reading the absorbance values for
the real third glucose standard solution.

Contributing error factors

Accuracy of Absorption values
By inspecting Figures 1 and 2, the absorbance values for when the glucose standards are completed
as well as for the reactor product assays, the absorbance values do not return to 0. This means that
all the recorded values have systematic error associated with them. However, this error is not
significant so it was ignored and not corrected.

11
Lab 1: Armfields Exercise A Group 8-6

Effect of de-gassed feed solution

De-gassing the feed is an important pre-experiment condition because it affects the performance of
the reactor as well as the optical batch cell module.

For the reactor, bubble production results to no contact between the liquid feed solution and the solid
catalyst. This affects the results obtained from the model as the models assume that the reactant
solution is purely liquid.

When air bubbles are present in the FIA, this causes a large increase in the optical absorbance due to
the high absorption value of a gas bubble compared to the dye that was formed to measure the
amount of glucose present.

If the feed solution was not properly de-gassed, not only will it cause error in the efficiency of the
catalyst of specific particle size, it will also indicate a larger conversion value due to the higher
absorbance reading produced indicating a larger amount of glucose produce than what it did.

Reliability and precision of the data

To allow the data to be reliable, the experiment would need to be replicated multiple times with the
same experimental conditions.

Precision of the data would require better measurements of the experimental variables such as
volumetric feed flow rate, temperature, diameter size of the catalyst for each reactor to eliminate any
sensitivity errors involved.

Possible improvements to increase reactor performance

To increase efficiency factor of the catalysed reaction, this can be achieved with decreasing the
catalyst particle size as seen with the experimental trend. Doing this will shift the reaction rate
dependence from diffusional to chemical control which will be determined more with the chemical
nature of the reaction (i.e. temperature dependence being significant). However, decreasing the
particle size of the catalyst will lead to an increase in pressure drop in the column according to the lab
manual. A solution to this would be increasing the use of wider pores in the packed bed reactor to
achieve higher catalytic efficiency without significant pressure losses but the downside to this is the
reduction in the concentration of active centres for that specific reactor. Hence the catalyst size and
its pore size distribution need to be optimised to achieve the optimal catalytic reactor performance
without affecting the reactor conditions to an extent.

Another way to improve the catalytic inversion of sucrose would be to change the catalyst used.
Mizota et al. (1994) studied the kinetics of using a SO3H group containing grafter polymer as a catalyst
for sucrose inversion called SSS/HEMA-T fiber. Figure 9 below shows that this catalyst has a better
kinetic constant value than Amberlite IR 120 when temperature is 70C = 343K.

12
Lab 1: Armfields Exercise A Group 8-6

Figure 9: Comparison of the kinetic constants for the SSS/HEMA-T fiber and Amberlite IR-120B on sucrose inversion (Mizota,
et al. 1994, 2218)

As residence time is linked to conversion, to increase the conversion of the reactor, the residence time
could be increased by slowing down the volumetric feed flow rate (flowrate of sucrose feed).
Alternatively, the reacting system could be changed so that it goes through the reactor more than 1.5
times the space time (this was the experimental condition).

Conclusion
In conclusion, the experimental results show that the use of a smaller catalyst particle size not only
improves the efficiency factor of that reaction, it also improves the conversion percentage for sucrose
inversion compared to the use of a larger catalyst particle size. It was found that at large particle size
diameter (found in reactor 1), it follows the principle of sucrose inversion being diffusional controlled
but for reactor 2 with a smaller catalytic particle size diameter, it does not agree with this statement.

Furthermore, sensitivity analysis shows that if the temperature reading were to be 1C off, it would
have an effect of 6.8% and 13.6% percentage errors on both the conversion and efficiency values
respectively.

The inversion of sucrose can be improved through optimisation of the catalytic particle size diameter
vs its pore size, changing the catalyst to one with a larger resulting kinetic constant compared to
Amberlite IR 120 at the same experimental conditions and through increasing space time/ recycle time
for each reaction trial.

13
Lab 1: Armfields Exercise A Group 8-6

References
Mizota, Tomotoshi, Satoshi Tsuneda, Kyoichi Saito, and Takanobu Sugo. 1994. Hydrolysis of Methyl
Acetate and Sucrose in SO3H-Group-Containing Grafter Polymer Chains Prepared by
Radiation-Induced Graft Polymerization. Ind. Eng. Chem. Res. 33 (9): 2215-2219. doi:0888-
5885/94/2633-2215$04.50/0.

Reed, Eldon W., and Joshua S. Dranoff. 1964. Ion Exchange Resin Catalysis of Sucrose Inversion in
Fixed Beds. I&EC Fundamentals 304-307.