This question paper Data drying sheet on pages 9-11

consists of 11 printed pages,

each of which is identified
by the Code Number
CAPE5340M01

 UNIVERSITY OF LEEDS

School of Chemical and Process Engineering

May/June 2017 Examinations

CAPE5340M01
ADVANCES IN CHEMICAL ENGINEERING

Time allowed: 2 hours

Answer four questions, one question from each Section and one other question

PLEASE SHOW ALL WORKINGS IN ANSWERS TO NUMERICAL QUESTIONS.

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 CAPE5340M01

SECTION A – Colloid Engineering

1 In their 2008 research article in Journal of the American Ceramic Society, Jailani et al.
studied the behaviour of aluminium oxide nanoparticles in suspension. In particular,
one of the commercial samples that they investigated was shown to disperse well in
water with an average particle diameter of 45 nm. The authors measured the particle
zeta potential as a function of pH of the continuous phase as shown in Figure Q1 below.

Figure Q1: Zeta potential of 45 nm aluminium oxide nanoparticles measured as a

function of the pH of the continuous phase. Measurements are made at different
volume fractions of particles – note that in this particular case, changes in the volume
fraction of the particle suspension do not affect the measured values of zeta potential
significantly.

On the basis of the data gathered by these authors, answer the following questions:

(a) Explain the changes observed in zeta potential across the entire pH range
(from pH 4 to pH 12). For this purpose explain what changes occur on the
surface of the particles when the pH is varied. [4 marks]

(b) Explain why measuring zeta potential is a suitable method to estimate the
stability of these particles. Use the equation for the repulsive interactions in the
DLVO theory to demonstrate this. [4 marks]

(c) Draw different plots (one for each pH) representing the net interaction energy
versus inter-particle distance for two approaching aluminium oxide particles in
suspension in water at the following different pH values:

(i) pH 5
(ii) pH 9
(iii) pH 12

and justify the reasons for the differences in the interaction energies that you
have plotted. [9 marks]

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 CAPE5340M01

(d) A similar shaped curve as in 1(a) can be anticipated for the variation of zeta
potential (y axis) as a function of the concentration of a suitable additive (x axis)
mixed in with the particle suspension. Interaction between the additive and the
particle suspension will dictate what this shape will look like. An example of
such a curve is presented in Figure 1(d) below.

Explain what additive can be used to obtain such a graph in the case of the
aluminium oxide nanoparticles described above (the system is kept at pH 5
throughout). In particular describe the critical characteristics of the additive you
have identified and its interaction with the particle surface. [3 marks]

Figure 1(d): Variation of the zeta potential of 45 nm aluminium oxide

nanoparticles at pH 5 anticipated as a function of the concentration of a suitable
additive mixed in the nanoparticle suspension.

2 A 2 wt% aqueous suspension of 500 nm silica particles is obtained at pH 8, where the

surface of the particles is negatively charged.

To the particle suspension a polyelectrolyte (with the chemical structure represented

in Figure Q2 below) is added:

Figure Q2: Chemical structure of poly(diallyldimethylammonium chloride). In this case

the molecular weight of the polyelectrolyte used is 100,000 g.mol-1.

The radius of gyration of the polyelectrolyte (for which water can be considered an
ideal solvent) can be calculated via:

݈ට ‫ ܯ‬ൗ‫ܯ‬
଴
ܴீ =
√6
where l is the segment length, here it can be approximated as 2 nm;
M is the molecular weight of the polyelectrolyte;
M0 is the molecular weight of the monomer, here 161.45 g.mol-1.
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 CAPE5340M01

This polyelectrolyte is added to the particle suspension at two final concentrations, a

low concentration of 0.024 wt% (where the particle surface area is in excess) and a
high concentration of 1 wt% (where the polyelectrolyte is in excess), respectively.

(a) Describe the likely behaviour of the particle suspension upon addition of the
polyelectrolyte in both cases above. Use schematics to represent how the
polyelectrolyte will be interacting with the particles in suspension. [6 marks]

(b) Describe the evolution of the particle diameter as a function of time upon
addition of the polyelectrolyte to the particle suspensions for both cases above.
Estimate the final particle diameter in the case where it is possible and justify
your estimation.
[6 marks]

(c) In their 2004 article in Advances in Colloid and Interface Science, Yan et al.
explored the sedimentation behaviour of such 500 nm silica particles in the
presence of pDADMAC at the concentrations stated above. The data they
gathered for these specific concentrations is extracted in Figure Q2(c) below.

Figure Q2(c): Behaviour of 500 nm silica particles (all samples – 2 wt%

particles) for settling experiments where a pDADMAC polymer is added to the
suspension.
(Left) Particle suspension before the polymer is added.
(Middle) Resulting system after 1 day when the polyelectrolyte is added at a
concentration of 1 wt%.
(Right) Resulting system after 1 day when the polyelectrolyte is added at a
concentration of 0.024 wt%.
The superimposed red lines denote the height of the sedimented bed.

(i) Explain the visualized differences in the suspension behaviour after 1

day for both concentrations of added polyelectrolyte. [3 marks]

(ii) Assuming the particle bed in the case of the 1 wt% added
polyelectrolyte does not significantly change upon complete particle
sedimentation, explain the differences in the particle sedimented beds
for both concentrations of added electrolyte. [5 marks]

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 CAPE5340M01

SECTION B – Particle Engineering

3 A co-current spray dryer is being used to manufacture ceramic particles from an

aqueous slurry of ceramic nano-particles. The dryer air inlet temperature is 230 °C
and the outlet temperature is 80 °C. The slurry moisture content is 40% by mass on a
wet basis and the product moisture content at the outlet is 2% by mass on a wet basis.
The airflow rate of the dryer is 20,000 kg/h and the dryer heat loss is estimated to be
300 kW when the dryer is running at steady state.

(a) Estimate the amount of water evaporated (in kg/h) and the production rate of
the dryer in kg/hr of product. [4 marks]

(b) Considering an ideal drying process, with no heat loss, calculate the theoretical
amount of water that could be evaporated with the airflow and inlet temperature
specified above. Compare with the real evaporation rate calculated in 3(a) and
comment on the dryer efficiency and how it might be improved. [4 marks]

(c) Estimate the maximum, seasonal, relative humidity of the outlet air stream.
[6 marks]

(d) It is proposed that the production rate is increased by increasing the inlet
temperature to 300 °C.

Assuming that the outlet temperature does not change, calculate the new
evaporative capacity of the dryer and comment on the change to the efficiency.
[2 marks]

(e) If the Péclet number, Pe, of the droplet in the initial set-up (based on the radius)
is 1.5, estimate the Pe number with the proposed higher inlet temperature,
assuming the droplet wet-bulb temperature change is relatively small and is in
the range 50 °C to 60 °C in both cases. Comment on possible effects of the
temperature change to the droplet structure. [4 marks]

Data:
Typical ambient conditions in the summer conditions: 30 °C, 80% rH
Typical ambient conditions in the winter conditions: 0 °C, 70% rH
Latent heat of vaporization of water at 80 °C = 2250 kJ/kg
A drying data sheet is also provided on pages 9-11.

4 A vertical axis mixer granulator process is being developed for the manufacture of a
new pharmaceutical formulation. Although lab-scale trials were successful, the first
trials done on a 25 litre scale (mixer diameter 0.4 m) were unsuccessful as the product
had a wide size distribution with large wet granules and lumps along with fine dry
powder. The development team believes that the cause of the problem is poor powder
wetting and nucleation. Two suggestions are made to improve the binder distribution.
The formulation scientist suggests adding some surfactant to improve the wetting,
estimating that the contact angle will move from 80° to 15° and the process engineer
suggests moving from one to four nozzles in order to get a better distribution of the
spray.

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 CAPE5340M01

If for the first trial the values for the dimensionless drop penetration time, τp and the
dimensionless spray flux Ψa were 1.4 and 0.5 respectively.

(a) Locate the current operating conditions on the nucleation regime map and
calculate the expected changes in τp and Ψa with the suggested improvements.
Critically discuss whether either or both changes will achieve better nucleation
and liquid distribution. [9 marks]

Due to time pressures on the development the team is being asked to produce a batch
on the 300 litre scale (mixer diameter 0.914 m), in the very near future.

(b) If the scale-up is done on:

 a geometrically similar unit, with four nozzles;
 the rpm scaled-up on the basis of matched impeller tip speed;
 binder addition time kept constant.

(i) What mixer speed in rpm would be used and what is the mixer Froude
number? (25 litre mixer rpm = 383) [2 marks]
(ii) Would you expect τp, to increase or decrease? [3 marks]
(iii) If the drop size remains constant what is the Ψa at the larger scale?
[2 marks]
(iv) Would you expect the binder distribution and size distribution to be
better or worse than the 25 litre situation? [2 marks]

(c) The lab-scale experiments were done on a non-geometrical granulator, 1 litre,

run at high rpm. Why might this have been successful? [2 marks]

Data:
Spray Set-Up 25 litre trial
Number of nozzles, 1
Spray diameter, m 0.175
Total flowrate, litres/min 0.28
Powder velocity, m/s 0.4
Binder droplet Sauter mean diameter, µm 200
Mixer rpm 383

25 litre mixer diameter = 0.4 m; 300 litre mixer diameter = 0.914 m

Nucleation regime map:

3V
a 
2vLd
tp
P 
tc
R 2
Fr 
g

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 CAPE5340M01

SECTION C - Non-Intrusive Measurement Techniques

5 It was proposed to utilise the ultrasound Doppler effect to measure the volumetric
flowrate of upward slurry flow in a pipe of 50 cm in diameter, according to the setup
given in Figure Q5 below, where the sensor’s incident angle = 50, ultrasound source
frequency fc = 6 MHz, responding frequency fr = 5.99046 MHz, the ultrasound velocity
in the slurry vc = 1550 m/s. The dynamic viscosity of the slurry is 1.125 x 10-3 Pa.s with
5% of fine particles of specific density 2.8. The calibration coefficients in Gesser’s
approximation for the mean velocity over the cross area are assumed as k = 4/3 for
laminar flow and k = 1.07 for turbulent flow ignoring the solids’ slip velocity.

(a) Prove that the mean axial velocity of solids, vm, can be presented as:

( f r  f c ) vc
vm  
2 f c cos  [12 marks]

(b) Calculate the volumetric flowrate of the solids in the pipe. [8 marks]

Figure Q5

6 The measurement principle of multiple energy gamma ray absorption is based on the
fact that the absorption of a narrow beam of gamma rays in a material is a function of
the material and the energy of the gamma rays.

 n 
I m (e)  I v (e)  exp   i  i (e)d 
 i 1  (1)

where Im(e) is the measured count rate, Iv(e) is the count rate when the materials are
evacuated, i denotes the volume fraction of material i, i presents the linear
absorption coefficient per metre for material i, d (in metres) is the distance travelled by
the gamma rays inside the container or pipe and e is the energy level.

(a) Express the linear equations for measuring phase volume fractions of a gas-
oil-water 3 phase flow when a dual-energy gamma ray is used. [10 marks]

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 CAPE5340M01

(b) Calculate the phase fractions for a set-up with two gamma ray sources,
241
Americium (Am) and 137Caesium (Cs), and the internal diameter of the
pipeline is 0.1 m. The measured count rates, oil and water absorption
coefficients are given in Table Q6 below. The attenuation from gas is so small
that it can be neglected. [10 marks]

Table Q6
Im(Am) Im(Cs) Iv(Am) Iv(Cs) wAm oAm wCs oCs
4656 2689 4700 2700 0.17 0.13 0.07 0.06

END