qwertyuiopasdfghjklzxcvbnmqw

ertyuiopasdfghjklzxcvbnmqwert
yuiopasdfghjklzxcvbnmqwertyui
CHNG3807 Project 2 Large
Scale Carbon Nanotube
opasdfghjklzxcvbnmqwertyuiop
Synthesis
Plant design
asdfghjklzxcvbnmqwertyuiopas
dfghjklzxcvbnmqwertyuiopasdf
ghjklzxcvbnmqwertyuiopasdfgh
jklzxcvbnmqwertyuiopasdfghjkl
zxcvbnmqwertyuiopasdfghjklzx
cvbnmqwertyuiopasdfghjklzxcv
bnmqwertyuiopasdfghjklzxcvbn
mqwertyuiopasdfghjklzxcvbnm
qwertyuiopasdfghjklzxcvbnmqw
ertyuiopasdfghjklzxcvbnmqwert
yuiopasdfghjklzxcvbnmqwertyui
opasdfghjklzxcvbnmqwertyuiop
asdfghjklzxcvbnmrtyuiopasdfgh
Hasara Fernando (306142988), Erin McMullen
(306191504), Thomas McCrossin (305167103), Sally
Rewell (306156865), Adam Jeffrey (306128152)

Contents
Executive Summary............................................................................................... 6
Overall Mass Balance............................................................................................. 7
Overall Process flow Diagram................................................................................8
Overall Cost Estimate............................................................................................ 9
1.

Storage Hopper Design................................................................................. 10

1.1

Description:................................................................................................ 10

1.1.1

Hopper................................................................................................. 10

1.1.2

Pneumatic conveying...........................................................................10

1.1.3

Rotary Valve......................................................................................... 10

1.2

Alternatives for design:..............................................................................10

1.3

Mass and Energy Balances:........................................................................11

1.4

Process Flow Diagram:............................................................................... 13

1.5

Design Calculations:................................................................................... 14

1.5.1

Hopper Design:.................................................................................... 14

1.5.2

Pneumatic Conveying Design:.............................................................17

1.5.3

Ethanol Tank:....................................................................................... 18

1.6

Cost Estimate:............................................................................................ 19

1.6.1

Hoppers:.............................................................................................. 19

1.6.2

Ethanol Tank:....................................................................................... 19

1.6.3

Rotary Valve:........................................................................................ 20

1.6.4

Pneumatic Conveying Lines:................................................................20

1.7
2.

Conclusion:................................................................................................. 20
Catalyst Preparation..................................................................................... 21

2.1

Alternatives for Design............................................................................... 21

2.2

Assumptions............................................................................................... 22
2.2.1

Mass Balance.................................................................................... 22

2.2.2

Terminal Velocity...............................................................................22

2.2.3

Fluidisation....................................................................................... 22

2.2.4

Slurry................................................................................................ 22

2.2.5

Hydrocyclone.................................................................................... 22

2.2.6

Drying............................................................................................... 22

2.2.7

Pumping............................................................................................ 22

2.2.8

Filter.................................................................................................. 23
2

2.3

Preliminary Mass Balance...........................................................................23

2.4

Preliminary Energy Balance........................................................................23

2.5

Preliminary Process Flow Diagram..............................................................24

2.6

Design Calculations................................................................................. 26

2.6.1

Fluidisation and Terminal Velocity.....................................................26

2.6.2

Slurry................................................................................................ 28

2.6.3

Hydrocyclone...................................................................................28

2.6.4

Drying............................................................................................... 29

2.7

Preliminary Cost estimate..........................................................................30

2.8

Conclusion.................................................................................................. 30

3.

Fluidised Bed Reactor.................................................................................... 31

3.1

Description of the basic technology and its purpose..................................31

3.2

Alternatives to design................................................................................32

3.3

General Assumptions used in the design...................................................32

3.4

Mass Balances............................................................................................ 33

3.4.1

Laboratory scale FBR...........................................................................33

3.4.2

Commercial Scale FBR........................................................................33

3.4.2.1 Gas entering the FBR........................................................................33

3.4.2.2 Catalyst particles entering the FBR..................................................33
3.4.2.3

Particles leaving the FBR through the solid discharge...................34

3.4.2.4 Gas leaving the FBR.........................................................................34

3.5

Energy Balance:...................................................................................... 35

3.5.1

4.

Energy from Gas streams:...............................................................35

3.6

Preliminary PFD....................................................................................... 38

3.7

Design Calculations................................................................................. 39

3.8

Preliminary costs estimates....................................................................41

3.9

Conclusions............................................................................................. 42

Gas Cleaning System..................................................................................... 42

4.1

Description of Basic Technology and its Purpose.....................................42

4.2 Alternative for design................................................................................. 43

Separating Larger Particles...........................................................................43
Separating Smaller Particles..........................................................................43
4.3 Assumptions............................................................................................... 44
Reasonable Cyclone Diameter.......................................................................44
Particle Diameters......................................................................................... 44
3

4.4 Mass Balance.............................................................................................. 44

4.5 Process Flow Diagram................................................................................. 47
4.6 Design Calculations.................................................................................... 48
4.6.` Calculation Method...............................................................................48
4.6.2 Cyclone Diameter and Dimensions.......................................................49
4.6.3 Cyclone Velocity................................................................................... 51
4.6.4 Pressure Drop....................................................................................... 51
4.6.5 Summary of Results............................................................................. 52
4.6.6 Design Choice....................................................................................... 52
4.6.7 Cyclone Efficiency................................................................................ 53
4.7 Cost Estimate............................................................................................. 53
4.7.1 Cyclone Cost......................................................................................... 53
4.7.2 Furnace Cost......................................................................................... 54
Conclusion........................................................................................................ 54
5.

Purification.................................................................................................... 56
5.1

Description of Process and Technology...................................................56

5.1.1

Acid Purification................................................................................ 56

5.1.2

Filtration............................................................................................ 57

5.1.3

Drying............................................................................................... 57

5.2

Mass/Energy Balance.............................................................................. 57

5.3

Process Flow Digram...............................................................................58

5.4

Design Calculations................................................................................. 59

5.6

Alternative Designs................................................................................. 63

5.7

Cost Estimation....................................................................................... 63

5.8

Assumptions............................................................................................ 66

5.9 Conclusion.................................................................................................. 67
Bibliography......................................................................................................... 68
Appendix B: Calculations..................................................................................70
Nomenclature................................................................................................... 70
Mass Balance.................................................................................................... 70
Mass Balance Matrix......................................................................................... 72
Terminal Velocity............................................................................................... 73
Terminal Velocity Matrix.................................................................................... 73
Fluidisation....................................................................................................... 74
Slurry................................................................................................................ 77
4

Slurry Matrix..................................................................................................... 78
Hydrocyclones.................................................................................................. 78
Hydrocyclone Matrix......................................................................................... 80
Drying............................................................................................................... 81
Drying Matrix.................................................................................................... 82

Executive Summary
Ultra Nano is a company that produces Multi-wall Carbon Nanotubes (MWCNTs)
using Fe2O3/MgO. These MWCNTs are used in the production of electrochemical
double layer capacitors and flat panel displays. Ultra Nano plans to use the
manufacturers of these products as its target market. This report explores the
design to produce these MWCNTs using a system composed of a storage system
for the catalysts, a catalyst preparation system, a fluidised bed. The waste and
products out of the fluidised bed is cleaned using gas cleaning and purification.
The hoppers used to store the raw materials, use mass flow and stainless steel to
help avoid erosion. Three hoppers were designed, with rotary valves, that are
connected to a pneumatic conveying system to transport the raw materials to
the catalyst preparation stage.
The catalyst preparation system focuses on the use of a scaled up fluidised bed
reactor. It combines MgO, Fe(NO3)3.9H2O, and ethanol to form 12092kg per day of
a supported metal oxide catalyst in the form of Fe 2O3/MgO. The waste products
over the system are NO2 and water, while the ethanol is recycled. The entire
process uses 131.8kW, while the system costs approximately $606,690 to
construct.
The Fluidised Bed Reactor uses Ar gas and C 2H2 has to produce carbon
nanotubes using MgO /Fe 2O3 catalysts. The reactor works in 30min batches
producing a total of 4750kg of CNT per day. Reactor has a diameter of 1.5m and
a height of 6.187 m.
The fluidised bed produces a un-purified product at 16964 kg/day. This product is
mixed with 57154L of 40 wt% HCl and processed in a microwave assisted
digester to remove the catalyst and substrate. The liquid and dissolved ions are
removed via a decanting centrifuge and the resulting cake dried to produce 5000
kg of product per day at 95% purity.
For the gas cleaning system, two Stairmand High Flow Rate Cyclones in parallel
were designed, with a flow rate of 4.57m3/s each and a cut diameter of 10m.
The diameter of these cyclones was 0.75m, velocity of 10.20m/s and a pressure
drop of 1049.14Pa. These dimensions all lie within the typical values for a well
designed cyclone. It is recommended that the solids discharge from the cyclone
be fed back into the stream from the FBR heading to the Purification stage.
The overall cost of equipment for the entire plant come to $8,279,274

Overall Mass Balance

mass of MgO
Mass of iron nitrate
mass of Ar
mass of C2H2
mass of air going in
mass of water going
in

0.13
0.024
3.9701
23
0.5540
44
13337
00
5.11E+
09

kg/s
kg/s
kg/s
kg/s
kg/s
kg/s

CNT production system

mass of NO2
mass of Water
mass of HCL
mass of MgCl2
mass of FeCl3
mass of
amorphous carbon

12910320
0
19841064
884
20443872
8.3
22789886
81
94168318
.26

kg/s
kg/s
kg/s
kg/s
kg/s

1468494 kg/s

Overall Process flow Diagram

System

Total Fixed
Capital ($)
871,460

Overall
Estimate

Catalyst raw materials

storage

The table
the total fixed
for the various
plant.

Catalyst preparation

606,690

Fluidised bed reactor

4,945,010

Gas cleaning system

156,114

CNT purification
Total cost

Cost
below gives
capital costs
systems in the

1,700,000
$8,279,274

The total cost is $8,279,274 which when looking at a plant producing 5000kg per
day of a high value product, seems like a small investment. Granted that this
report does not include a running costs, it the value appears rather small.
The deviations in the cost for the various systems within the plant require further
attention. Whilst varying values are to be expected, the differing order of
magnitude between the largest value of $4,945,010 and the smallest of
$156,114 could be attributed to several reasons. The most probable reason
would be due to the amount of detail that each individual went to on their
respective system. Those who focused not only on the core equipment and
processes present, but went further and added additional extras such as
conveyor beds and valves etc., would obviously have a greater total fixed capital
cost.
The alternative reasoning behind the large value deviation would be sources to
the use of PTW. Whilst the book provides excellent detail on more common
process instruments, those that are less common and more difficult to establish
size to cost relationships are void from the book.
Unfortunately this cost estimate is rather dry. Various improvements could be
made in the form of a running cost estimate and the expected product values.
However a report such as this focuses on good design and scale up
primarily, and economic feasibility secondly.

1.

Storage Hopper Design

1.1 Description:
1.1.1 Hopper
The short-term storage of particulate solids in process plants can present
problems which are often underestimated and can frequently cause flow
stoppages.
1.1.2 Pneumatic conveying
Pneumatic conveying is the transportation of particulate solids using pressurised
gases most commonly air. Until quite recently most pneumatic transportation
systems were done in dilute suspension, using large volumes of air at high
velocity (Rhodes M. , 2008). Today there is an increased interest in dense phase
(where particles are not fully suspended) transportation. Dense phase results in
low air requirements, thus reducing energy costs, and also lower pipeline erosion
rates.
1.1.3 Rotary Valve
A rotary valve is often used to enter or extract material from two chambers with
different pressures. This is extremely useful in pneumatic conveying as solids can
be fed into the air stream at a controlled rate against air pressure.

1.2 Alternatives for design:

There are two main flow designs for hopper storage devices; Mass Flow and
Funnel/Core Flow. Mass flow has many advantages over funnel flow. In mass flow,
the motion of the powder is uniform, in funnel flow the powder can remain in
dead zones and rat holes can form. While mass flow is ideal, it is not always
possible due to the possible erosion of the hopper wall. In these cases, funnel
flow must be used.

10

Figure 1: Mass Flow and Funnel Flow in Hoppers: (a) Funnel Flow; (b) Mass
Flow (Rhodes M. , 2008)

Apart from the different flows, there are many different shapes of hoppers
available. Figure 2 shows a few of the different mass flow bins available. The
conical hopper (a) is the simplest design.

Figure 2: Different Mass Flow Bins (Perry R. , 1997)

While there are many alternatives for hopper design, the simplest and most ideal
cases were selected for this project; Mass flow and a conical hopper.
Alternatives to pneumatic conveying and the rotary valve are less likely.
Pneumatic conveying is a highly successful technique used to transport
particulate solids, thus it is the most appropriate technique to use. The same
applies for rotary valves.

1.3 Mass and Energy Balances:

A mass balance over the catalyst raw materials storage and delivery system (=
is displayed below. As it is the beginning of the system, there is no feed into it. It
is assumed that the storage vessels are resupplied on a regular basis, however
this is not displayed. The values presented below are specified for a production
capacity of 5000kg per day.
MgO = 11227.72kg
Catalyst raw materials storage and delivery system
Fe(NO3)3.9H2O = 4374.17kg
Ethanol = 72008.75kg
Whilst not displayed here, pneumatic conveying is used to deliver the 12092kg of
Fe2O3/MgO supported metal oxide catalyst from the catalyst preparation system
11

to the fluidised bed reactor. MgO and Fe(NO 3)3.9H2O flows are also transported
via pneumatic conveying.
An important part of this system that is not accounted for within the mass
balance is that of the air that is used in the pneumatic conveyors. From the
calculations in the following sections, the volume of air was approximated to be
0.11m3s-1 for the MgO, 0.42m3s-1 for the Fe(NO3)3.9H2O, and 0.12m3s-1 for the
Fe2O3/MgO conveyors.
An energy balance was not needed over this system due its nature and the way
it as designed. By using gravity to feed the ethanol, any power requirements
associated with the ethanol in this stream are negated. Whilst the pneumatic
conveying does require some power to reach the superficial gas velocity, under
these circumstances the power requirement was determined to be negligible.
Hence the power requirement over the catalyst raw materials storage and
delivery system is assumed to be 0.

12

1.4 Process Flow Diagram:

13

1.5 Design Calculations:

1.5.1 Hopper Design:
No sheer cell test data could be found for Magnesium Oxide (MgO) or Iron
Nitrate, thus another particle that was similar in properties was used to calculate
the hopper. JSC-1 (McKay, 1994) was used in place of MgO. MgO is found in the
composition of JSC-1, and therefore they both have similar properties.
Figure 3: Sheer Cell Test Data

y
c

14

Figure 3 is the sheer cell test used to calculate (angle of internal friction), c
(compacting stress) and y (unconfined yield stress).
The angle of internal friction was already calculated to be = 45. c and y were
determined from the ends of the semi-circle as shown in Figure 3
Table 1: Compacting and Unconfined Yield Stresses

237.705 kPa

482.3 kPa

654.55 kPa

34.45 kPa

68.9 kPa

96.46 kPa

Kinematic angle of wall friction W=24.2

Using Figure 4 (Rhodes M. , 2008)and a safety margin of 10, the hopper flow
factor was found to be = 1.4, and the semi-included angle of conical hopper
wall slope, = 14.
While a safety margin of 3 is usually used, 10 was used in this case. As no Flow
Factor Charts could be found for =45, the flow factor chart for =40 was used
instead. For this reason it was decided to increase the safety margin.
Graphing the results from Table 1 produced the powder flow function. On the
same plot the equation (

C
= y Error: Reference source not found) for the
ff

limiting condition for flow was also graphed, revealing the conditions under
which flow will occur for the powder in the hopper.

C
= y
ff

Equation 1

15

Figure 4: Hopper Flow Factor Value for Conical Channels, =40

P
oy
lw
yd
ne
or
F
m
il
ao
lw
(
PF
ou
n
w
dc
et
ri
Fo
ln
o
w
F
u
n
c
t
i
o
n
)

Figure 5: Determination of critical conditions for flow

Figure 5 clearly shows the critical value for flow is crit=7.5 kPa. All stresses above
this value will cause flow in the hopper.
The minimum hopper outlet diameter is determined by the equation:

B=

H () crit
B g

Equation 2

crit
Where H() is a factor determined by the slope of the hopper wall.

H ( )=2.0+

60

Equation 3

From Error: Reference source not found andError: Reference source not found; B=
42.4 cm for the MgO hopper.
Summarizing, to achieve mass flow without risk of blockage, we require a
stainless steel conical hopper with maximum semi-included angle of cone, 14
and a circular outlet with a diameter of at least 42.4 cm.
The same procedure was followed for the other two hoppers containing iron
nitrate and the other containing magnesium oxide impregnated with iron oxide.
Table 2: Summary of Hopper Design Parameters

Maximum

14

Minimum
B
42.4 cm

Volum
e
8.40
m3

Heig
ht
4.75
m

Diamet
er
1.5 m

Iron Nitrate Hopper

14

101.4 cm

3.64
m3

1.16
m

2.0 m

MgO/Fe2O3 Hopper

14

43.6 cm

3.09
m3

1.75
m

1.5 m

Magnesium Oxide
Hopper

Each hopper is made from stainless steel and has the capacity to store 3 days
worth of raw materials.

1.5 m

2.0 m

1.5 m

16

42.4

43.6

101.4

MgO

MgO/Fe2O3

Iron Nitrate
Figure 6: Dimensions of each hopper

1.5.2 Pneumatic Conveying Design:

Pneumatic conveying requires trial and error in selecting the correct pipe
diameter. Firstly an initial pipe diameter of 51mm is selected. From here the gas
velocity if found using the saltation velocity. (Note that air is used in this system
as the conveying gas as it is cheap and readily assessable.)

U salt =

/2

4 M P 10 g D
f

( 2 )2

1/( +1 )

Equation 4

Where = 1440x + 1.96 and = 1100x + 2.5

Therefore superficial gas velocity,

U = 1.5Usalt

U = 1.5 x 8.962
U = 13.44 m/s
The next step is to calculate the pressure losses through the horizontal and
vertical sections and the bends.
Horizontal Sections:
The pressure loss in the horizontal sections of the transport line is given by:
2

U 2 p ( 1 H ) U pH 2 f g f U 2 L H 2 f p p ( 1 H ) U pH L H
p H = f H fH +
+
+
2
2
D
D

Equation

Hinkles correlation gives UpH:

U pH =U ( 10.0638 x 0.3 0.5

p )

Equation 6

Therefore UpH=10.00 m/s

From continuity,

G= p (1 H ) U pH

Equation

Thus,

H =1

G
=0.998 , and,
p U pH

U fH =

U
=13.46
H

m/s

Rep was calculated using the transitional equation and therefore C D = 2.853
17

U U p
3 f D
f p=
CD f
=0.019
8 p x
Up

Therefore using Error: Reference source not found, pH = 16297.24 Pa, taking fg
= 0.005
Vertical Sections:
The pressure loss in the vertical sections of the transport line is given by:

2 f g f U 2 LV
g
pv =
+0.057 GL v
+ ( 1 v ) g Lv + f v g Lv
D
D p

U pv =

U
U T
v

Equation 8

Equation 9

Combining Error: Reference source not foundError: Reference source not

foundand From continuity,
Equation 7, creates a quadratic in v which only
has one possible root.

2v U T U T +U +

G
+ U=0
p v

Equation 10

Solving the quadratic equation, v = 0.999, and thus pv = 1561.545 Pa

Bends:
The pressure loss across each 90 bend is taken to be equivalent to that across
7.5m of vertical pipe. (Rhodes M. , 2008)
Pressure loss per metre of vertical pipe = 156.154 Pa

Therefore, loss across two 90 bends = 2 x 7.5 x 156.154 = 2342.3 Pa.

And so,

Total pressure loss = loss across vertical sections + loss across horizontal
sections + loss across bends

18

= 1561.545 + 16297.24 + 2342.3

= 20201 Pa
= 0.2 bar
The allowable system pressure loss is 0.2 bar; therefore the size selected for the
pipe diameter is within the range.

These calculations were repeated for the other conveying lines. Table 3:
Summary of Pneumatic Conveying Lines shows the summary of results for all the
pneumatic conveying lines.

Table 3: Summary of Pneumatic Conveying Lines

Pipe
Diameter
(mm)

PH
(Pa)

Pv
(Pa)

Ben
ds

Allowable
Pressure
loss (bar)

Total
Pressure
loss (bar)

MgO

51

16297.
24

1561.5
45

0.2

0.2

Iron
Nitrate

27

7443.8
7

710.36

0.1

0.1

MgO/Fe2
O3

55

5310.3
5

1443.6
46

0.1

0.99

1.5.3 Ethanol Tank:

The ethanol tank has the capacity to hold 3 days worth of the raw material.
There is the option of recycling ethanol back through the system, which will
reduce the frequency of renewing the raw material.

The best way to feed ethanol into the Catalyst Preparation is through a gravity
fed tank, eliminating the need for a pump. The tank is again to be made from
19

stainless steel, with a volume of 0.75 m 3. The diameter is 1 m giving a height of

96 cm.

96 cm

V = 0.75 m3

1m

Figure 7: Dimensions of the Ethanol Storage Tank

1.6 Cost Estimate:

1.6.1 Hoppers:
Table 4: Cost estimate of hoppers

Purchased
Cost CITATION Pet03 \l 3081
Total Physical Plant
Cost CITATION Pet03 \l 3081

MgO
$30,000

Iron Nitrate
$20,000

MgO/Fe2O3
$15,000

$84,000

$56,000

$42,000

CITATION Pet03 \l 3081 Purchased cost calculated from (Peters, Timmerhaus, &
West, 2003) fig12-52, pg557 for stainless steel
20

Total Fixed
Capital CITATION Pet03 \l 3081

$113,400

$75,600

$56,700

1.6.2Ethanol Tank:
Table 5: Cost estimate of ethanol tank

Purchased Cost1

Ethanol Tank
$50,000

Total Physical Plant Cost2

$170,000

Total Fixed Capital3

$246,500

1.6.3 Rotary Valve:

Table 6: Cost estimate of rotary valves

Purchased Cost CITATION Pet03 \l 3081

Rotary Valve (3 valves in total)

$10,000 per valve

Total Physical Plant Cost2

$94,500

Total Fixed Capital3

$132,300

1.6.4Pneumatic Conveying Lines:

Table 7: Cost estimate of pneumatic conveying lines

Purchased
Cost CITATION Pet03 \l 3081
Total Physical Plant Cost2

Pneumatic Conveying Lines (4 lines in

total)
$14,000 per line
$176,400

CITATION Pet03 \l 3081 Total physical plant cost calculated from (Sinnott,
2006)table 6.1, pg 252. Includes installation, piping, instrumentation, electrical,
buildings, utilities, storages, site development and ancillary buildings
CITATION Pet03 \l 3081 Total fixed capital calculated from (Sinnott, 2006) table
6.1, pg 252. Includes design and engineering, contractors fee and contingency.
CITATION Pet03 \l 3081 Purchased cost calculated from (Peters, Timmerhaus, &
West, 2003) fig 12-64, pg 575
CITATION Pet03 \l 3081 Purchased cost calculated from (Peters, Timmerhaus, &
West, 2003) fig 12-63, pg 575
21

Total Fixed Capital3

$246,960

Total Cost of storage of raw materials = $871,460 (US Dollars)

1.7Conclusion:
Overall, 3 hopper storage devices (with rotary valves) will be used to store the
raw materials. These are connected to a pneumatic conveying system that will
transport the particulates to the catalyst preparation. These hoppers use mass
flow and are made from stainless steel to help avoid corrosion.
The final fixed capital investment for the storage of raw materials = $871,460
(US dollars). Depending on the current exchange rate this value will
increase/decrease.

22

2.

Catalyst Preparation

The term catalyst preparation defines itself. It is the preparation of a catalyst that
will be used further on in another reaction. A catalyst increases the rate of a
chemical reaction without be consumed in the reaction itself. Preparing one can
be as simple as adding two chemicals together, or more complex such as the one
that this chapter outlines
The catalyst preparation method used with the report Mauron et al. utilises a
supported metal oxide as a catalyst to the reaction. The conventional
approaches to preparing this material include equilibrium adsorption, grafting,
co-precipitation and impregnation. The key function in characterising supported
metal oxides is the amount of the supported metal oxide relative to the
underlying support surface area. Thus it is important to use an underlying
support substance with a high surface area as the catalytic activity correlates to
the surface density-dependant structure of the supported species (Regalbuto,
2006).
The method utilised by Mauron et al. involves a magnesium oxide (100 m 2 g-1)
supported iron oxide powder, produced by impregnation in an iron nitrate
ethanol solution. Its purpose is to aid in the deposition of carbon nanotubes from
acetylene by chemical vapour deposition

2.1 Alternatives for Design

Within the design of the system there are virtually a limitless number of methods
to prepare the supported metal oxide (SMO). A variety of equipment can be used
to varying efficiencies. Does one use a cyclone or a filter? One large pump or
several smaller pumps? Essentially the final design only ends when the process
engineers are satisfied that the product, energy, and cost balances are
sufficiently viable. Within this catalyst preparation section, the differing methods
fall into one of four categories:
Impregnation: This chapter is an example of impregnation, where a porous
support substance (MgO) is immersed in a solution (ethanol) where a reaction
occurs and the desired catalytic agent (Fe 2O3) impregnates/adsorbs to the
support substance.
Equilibrium adsorption: Similar to the impregnation method, the solid support is
immersed in an excess solution of dissolved surface oxide precursor for long
periods of time. The dominant driving forces within this reaction are the
concentration gradient and electrostatic interactions. It is generally thought to
yield better dispersion of surface metal oxide overlayers than impregnation
(Regalbuto, 2006).
Grafting: Deposition involving the formation of a strong bond, usually covalent,
between the support substance and the active element. It is achieved through a
chemical reaction between a functional group (e.g. hydroxal groups) on the
23

surface of the support and an appropriately selected inorganic, or organometallic

compound of the active element (Louis & Che, 1995).
Co-precipitation: Involves precipitating the solid from a solution containing
soluble precursors of both the support and surface oxides. It is primarily focused
around the precursor condensation that forms oxides or hydroxides when the pH
of the solution changes (Regalbuto, 2006).

24

2.2 Assumptions
Due to the nature of the problem and various undefined elements within the
recipe, several assumptions have been made throughout the calculations so as
to give the best model of data.
2.2.1 Mass Balance
The major impurities within the final product consist of Fe 2O3, MgO, and
amorphous carbon.
Amorphous carbon accounts for 1% of the final impurities.
All carbon in the product are CNTs.
CNT yield is 28% of unpurified mass (Mauron et al., 2003).
2.2.2

Terminal Velocity
The Fe2O3/MgO density is a combination of 95wt% MgO, and 5wt% Fe 2O3.
The particle diameter is 100m.
Particle diameters are of homogenous size when entering the fluidised
bed.

2.2.3 Fluidisation
The recipe states it takes 20 minutes to produce the mixture, thus it is
assumed that at any point in time, there is 20 minutes worth of catalyst
reactants present.
The particles are all spherical and pack tightly together.
An approximate ratio of 1:3 for radius to height for the column.
The NO2 released in the fluidised bed reactor (FBR) will evaporate from the
reactor solution as its boiling point is 21.1C.
The Fe2O3/MgO will settle to the bottom of the FBR provided the ethanol
flowrate is kept below its terminal settling velocity, and above the MgO
terminal settling velocity.
The minor dilution of the ethanol with water has a negligible effect on the
solution density, and therefore any results using this value.
2.2.4 Slurry
The dilution of the ethanol with a minor amount of water has negligible
effects on the viscosity, density, and therefore any results using this value.
2.2.5 Hydrocyclone
A low flow, high efficiency Stairmand hydrocyclone is used.
The hydrocyclone operates at 90% efficiency.
2.2.6 Drying
Initial temperature is 21.1C.
The heat capacity of the Fe2O3/MgO is the equivalent to the heat capacity
of MgO.
Only Fe2O3/MgO is left after the drying process.
The heat exchangers are only 95% efficient.
25

2.2.7 Pumping
The only drops in pressure in the system are attributed to the various
pieces of equipment.
The centrifugal pumps used are only 60% efficient.
2.2.8 Filter
Due to a lack of supporting calculations, the filter was not included in the
mass, energy, and cost balances. Whilst it would be valuable to have this
data, the filter was included to show how almost all of the SMO could be
retrieved for later use.

2.3 Preliminary Mass Balance

A simplified mass balance over the catalyst preparation system is displayed
Figure 1, while a more detailed balance over the system can be found in
Appendix B. It is designed to cater to a production rate of 5000kg of product per
day and thus all the corresponding values in the mass balance are over a period
of one day.
NO2 = 1494.25kg

MgO = 11227.72kg
Fe(NO3)3.9H2O = 4374.17kg
Ethanol = 72008.75kg

Catalyst Preparation

Fe2O3/MgO = 12092.14kg

Ethanol = 72008.75kg
Water = 1755.69kg
Figure 8: Catalyst preparation mass balance
Due to the undefined nature of the recipe in terms of the products final
composition and quality, it is assumed the three major impurities accounting for
5% of the final product are amorphous carbon (assumed to be 1% of the total
waste), Fe2O3, and MgO. The yield was determined to be 28% (Mauron et al.,
2003) at the system specifications, thus denoting that the amount of Fe 2O3/MgO,
the supported metal oxide (SMO), required was approximately 12092kg per day.
With an iron to magnesium oxide ratio of 5% this corresponded to 4374kg of
Fe(NO3)3.9H2O, and 11228kg of MgO.
A substantial amount of NO2, 1494kgper day, is formed from the degradation of
Fe(NO3)3.9H2O to Fe2O3. This product is not required on site and could potentially
be sold externally. Potential uses for NO 2 include use as an anesthetic and use
within the automotive industry to provided extra power to engines. Water is also
produced from of Fe(NO3)3.9H2O and as can be seen in the PID, will be used
within the heat exchanger CP-HX01 as an extra source of energy, thus saving
money.

26

While a large amount of ethanol, 72009kg per day, flows through the system on
a daily basis, it will be recycled hence saving money and reducing the storage
requirement to approximately 1 to 2 days.

2.4
Name
Power
CP-D01
Balance343.16k
W
There
are
preparation
CP595.35k
to dry the
DC01
W
the pumps.
CPfor
the
-45.83kW
HX01
calculated
heat
the
CPthe
latent
HX02
781.87k
energy
W
heat
for
the
Total
110.81k
power
to
W
plus
the
Name
pressure
Q (L s-1)
of
following
P CP-

CPCP01

CPCP02

1.181

0.506

300000

Preliminary Energy
two sections to the catalyst
energy balance; the power used
SMO, and the power required for
The amount of power required
drying section of the system is
by finding the energy required to
fluids to their boiling points plus
heat of vapourisation, minus the
conserved through the use of
exchangers. The power required
centrifugal pumps includes the
pump to the desired flow rate
power required to overcome the
drops across the various pieces
equipment, as shown in the
equation:

HX02

Table
8
power
Table
9
power
(heat
been
energy
Appendix B.

P CPHX02

300000

P CPC01

1405.7
7

Total

2.767k
W

18.2kW

Table 8: Power requirements for drying

for pumping

Power=

Q Pumping
pump efficiency

gives an estimation of the total

required by drying system while
gives an estimation of the total
required by the pumping system
exchanger pressure drops have
estimated (Che Plus)). Further
calculations can be found in
Table 9:Power requirements

27

The total energy use is 131.8kW. This is a realistic amount of energy for a
process of this scale and whilst further energy savings can be made by
increasing the efficiency of the components, a large savings in energy could only
come from the alteration of the design.

2.5 Preliminary Process Flow Diagram

The preliminary process flow diagram (PPFD) below gives a detailed breakdown
of the components and the material flowrates. The four primary components
within the system are the fluidised bed reactor (CP-FBR01), the hydrocyclone
(CP-C01), the dryer (CP-D01) and the distillation column (CP-DC01). The
secondary components include two heat exchangers (CP-HX01 and CP-HX02) and
the two centrifugal pumps (CP-CP01 and CP-CP02).
The PPFD is designed to give an understanding of the composition of the catalyst
preparation stage in terms of equipment and flowrates. It is not designed to
function as a two dimensional structural placement guide and hence one cannot
assume that this will resemble the final scaled up plant in any form. This also
indicates that various structural necessities such as piping cannot be estimated
until all the total system balance PPFD is compiled and rough site placement is
established. This is outside the scope of this report.
The PPFD does not provide any insight into why it was designed that way;
justifications and reasoning will be explained in further detail in the design
calculations section.

28

Figure 9 - Catallyst preparation PPFD

29

2.6 Design Calculations

2.6.1 Fluidisation and Terminal Velocity
The batch defined by Mauron et al., 2003, involves dissolving MgO and
Fe(NO3)3.9H2O in ethanol before mixing together and sonicating to produce a
homogenous product. This process takes approximately 20 minutes. Following
this the SMO product is dried, and then grinded into a fine powder. For a scaled
up process of 500okg per day this is not feasible and thus alternative methods
must be employed.
Combing single particle physics with FBR technology, this problem can be
overcome and provide continuous production of the SMO catalyst.
Before designing the FBR, the terminal velocities of the SMO and MgO were
determined. These two values are important within the FBR as a different
terminal settling velocity would allow the faster one to sink while the other to
stay suspended in the solution.
Table 10:Key factors for designing a FBR

Shape

Fe2O3

Density (kg m3
)
5240

MgO

3580

cubic

Fe(NO3)3.9H2O

1680

monoclinic

Ethanol

789

Fe2O3/MgO

3663

trigonal

trigonal

Whilst there is no specific density of the SMO catalyst, it suggested that there is
1-6 wt.% uptake rate (Stobbe et al., 1991) of the Fe in the Fe 2O3/MgO
combination, which corresponds to the 5% ratio used within the recipe. Assuming
the Fe2O3 is deposited on the inside of the MgO, a density can be estimated using
the values in Table 10by:
3

Catalyst density=0.05 5240+0.95 3580=3663 kg m

Determining the drag coefficient using equation 1.1 for both the MgO and the
SMO and then substituting them into equation 1.2 gives terminal velocities of
0.0532ms-1 and 0.0517ms-1 for the SMO and MgO respectively. The terminal
velocity of the Fe(NO 3)3.9H2O is not required because it is less dense than the
MgO and is assumed to have a much lower terminal velocity and hence will not
be a problem.

CD=

4 g d 3p ( p )
3 2

1.1
30

V t=

p
1.2
d p

The significance of these values cannot be stressed enough. They imply that
provided the flowrate of the ethanol in the FBR is above 0.0517ms -1 and below
0.0532ms-1 the desired product, the SMO, will settle out of the solution using
gravity settling. Provided these flowrates are above the minimum fluidisation
velocities for the FBR, any need for costly apparatus or energy requirements are
prevented.
However this theory relies on the assumption that all particle sizes are
homogenous on entering the FBR and do not clump together. Provided this
assumption holds, it is feasible that the terminal velocity of the SMO will actually
increase as the MgO attracts the Fe 2O3. While the changing density has already
been accounted for, the increase in size has not. Thus as the SMO develops, it
the Fe2O3 would not only develop on the inside of the MgO, but also the surface
resulting in a larger size and therefore a faster settling velocity.
Due to the nature of the gravity settling method (the SMO will deposit when it is
ready) there is no real need to specify how long the particles should remain in
the FBR thus it is up to the designers discretion to determine the size of the
reactor. To keep consistent with the recipe, it was assumed that the reactor can
hold 20 minutes worth of reactants.
Before determine the FBR dimensions, and despite knowing the shapes of
particles (as shown in Table 8), it was assumed that all the particles were
spherical and the bed packed tightly. This was to simplify things greatly and
allowed the voidage to be determined easily by equation 1.3.

( 3 2 ) 1.3
=

The first step in designing a FBR is determining the pressure drop. Through the
use of equation 1.4 this was determined to be 13250Pa.

P=

weight of particlesupthrust on particle M B gM B (f / p) g

=
1.4
crosssectiononal area
A

Following this calculation the bed height and was calculated to be 0.64m using
equation 1.5. The bed height and the cross-sectional area of the bed are
functions of each other thus to give the reactor a realistic shape a ratio of 1:3 for
the radius to height was aimed for.

H=

P
1.5
( 1 ) ( p f ) g

The final and most important calculation was the determination of the minimum
fluidisation velocity using equation 1.6. It is important that this value is below the
31

terminal velocity of the MgO because if it is not then the gravity settling is no
longer be a viable option as the MgO particles would also settle out and further
processing would be required.

U mf =

( p ) g d 2p
1650

1.6

The minimum reactor volume of 79.94L was simply determined from the crosssectional area multiplied by the height of the reactor. However if one was to
assume that the reaction requires fresh ethanol then the volume would be closer
to 1371L, in which case the dimensions would be different to those currently
stated. In this case the volume of 79.94L will be used so as to reduce the cost of
the plant.
Provided the FBR is operated at approximately 21.1C or above (easy as this is
almost room temperature), the NO2 in the solution will boil and can be collected
for sale.
2.6.2 Slurry
After the FBR the SMO will come out as a slurry in a water/ethanol solution with a
ratio of 1.89% to 98.11% respectively. The viscosity of a slurry can be measured
if the particles settle slowly. For dilute suspensions of fine particles, slurries may
exhibit Newtonian behaviour. In this case, the viscosity of a very dilute
suspension (solids volume fraction less than 2%) of uniform, spherical particles
can be described by the theoretical equation derived by Einstein (Einstein,
1906).

s = f ( 1+2.5 C v ) 1.7
Solving this equation gives a resulting solution viscosity of 0.0013Pa.s, a minor
change from the previous viscosity of 0.0012Pa.s. This increase, though minor,
will increase the amount of friction in the pipe and hence the amount of power
required to pump the fluid. The required pressure per unit length of pipe is solved
using equation 1.8 and determined to be 0.156Pam -1.

P 32 U
=
1.8
2
L
dp
An important factor to keep in mind is the critical deposition velocity. If the flow
of the slurry is to reach this value then the SMO will deposit on the bottom of the
pipe, resulting blockage problems at bends and pump problems. Using equation
1.9 a critical deposition value of 0.037ms -1 was determined. This will not be a
problem unless the pipe has an unnecessarily large cross-sectional area.

Vc=F gD

p
1 1.9
f

A centrifugal pump will be used as it offers an economic advantage. The lower

pressures required generally restricts the pump to a shorter distance which in
32

this case will result in lower power requirement and hence cost less to run
(Rhodes M. , 1998).
2.6.3 Hydrocyclone
A hydrocyclone operates very similarly to a cyclone, with the only difference
being that instead of a gas as the fluid medium, a liquid is used. The purpose of
this cyclone is to reduce the amount of SMO that needs to filtered prior to being
sent to the next stage in the system. Using the excel function Goalseek and
setting the collection efficiency to 90%, the equiprobable cut diameter was found
to be 33m using equation 1.10. Using this value the cyclone body diameter was
determined to be 0.12m and the characteristic velocity is 0.099ms -1.

(d p)=

1
1.10
d 50 2
1+
dp

( )

Using equation 1.11 a pressure drop of 1405Pa was calculated. This is a low
value and in the long run will savings made due to decrease filtration costs will
repay the initial investment.

f U2
P=Eu
1.11
2

( )

Combing Table 4 with Figure 4, a rough estimation of the dimensions of the

cyclone can be given.

Figure 10: Stairmand high effeciency cyclone (Rhodes M. , 1998)

Table 11:Dimensions relative to diameter (D =0.12) in m

33

Cyclone
type
Stairmand
, H.E.
Final

2.5

0.5

0.40
2

0.25
1

0.05
0

0.37
5
0.03
8

0.5

0.2

0.5

0.5

0.05
0

0.02
0

0.05
0

0.05
0

2.6.4 Drying
The drying stage is the most energy intensive stage with the catalyst preparation
system. It is here that the majority of the running costs will be incurred. It
consists of two different drying apparatuses, a traditional dryer and a distillation
column. The dimensions of these two systems have not been presented, however
the most important aspect of energy consumption has.
The method of drying involves the 90% SMO stream and its respective
water/ethanol solution being dried in a traditional drier. The SMO is then carried
on towards the next system, while the water/ethanol gas flows to the distillation
column. From here it is met with the fine flow from the cyclone. The SMO from
the fine flow deposits at the bottom of the distillation column before being
collected and joined the SMO from the coarse flow. The ethanol and water then
separate at their respective boiling points of 100C and 78.4C. From here the
water enters the heat exchanger stream after CP-HX02 while the ethanol is
condensed in CP-HX02 to be recycled.
Using equation 1.12, a total power requirement of 938.52kW was determined.

Q=m C p T + H vap 1.12

2.7 Preliminary Cost estimate

Before construction on any plant can begin, it needs to be determined whether it
is a financially feasible option. This includes initial costs such as equipment and
construction, as well as ongoing costs such as labour, utilities, and maintenance.
The equipment costs shown in Table 5 are derived from PTW and adjusted to
current day value by assuming 3% annual inflation.
Table 12: Preliminary Cost Estimate

FBR

Cyclone

Dryer

2 Pumps

20,000

Distillati
on
Column
30,000

27,000

8,500

2 Heat
exchange
rs
30,000

Purchased
Cost ($)

25,000

Total
physical
plant cost
($)

70,000

56,000

84,000

76,500

23,800

84,000

Total Fixed

94,500

75,600

113,400

102,060

32,130

113,400
34

capital ($)
Several assumptions were made when calculating the costs for the equipment.
Stainless steel was selected as the material of choice due to is properties. It is
secure choice as it has high corrosive resistance, tension strengths, and
longevity, despite its slightly higher price. The total physical plant cost is
calculated from (Sinnott, 2006) table 6.1, pg 252. It includes the installation,
piping, instrumentation, electrical, buildings, utilities, storages, site development
and ancillary buildings. The total fixed capital is calculated from (Sinnott, 2006)
table 6.1, pg 252. This also includes design and engineering, contractors fee and
contingency.
When combining the costs of the individual components, a total value $606,690
reached. For a plant of this scale the total cost appears somewhat low, however
the simple explanation exists that this is a preliminary report and various
components were left out so as to provide greater detail on the major equipment
pieces within the plant.

2.8 Conclusion
The scaling up of a literature recipe to a 5000kg per day plant is difficult. Major
challenges included selecting the correct equipment so as to minimise initial
costs and running costs. The equipment chose within this report costs a total of
$606,690 to purchase and install while the power required for the plant is
131.8kW. A more detailed cost analysis is required so as to determine the costs
of materials as well as the selling prices of the potential product. Labour,
maintenance, and other utilities also need to be calculated to get close to a
realistic estimate of economic feasibility. This chapter focused on the design and
calculations process over the economic feasibility of the plant, thus if a more
detailed analysis of the financial situation of the plant is desired, then further
investigation is required.

3.

Fluidised Bed Reactor

3.1 Description of the basic technology and its purpose

In this design Multiwall Carbon Nanotubes (MWCNT) are produced using
Chemical Vapour Deposition (CVD). CVD is a method in which a gaseous
hydrocarbon is cracked into carbon and hydrogen by thermal degradation using
a transitional metal catalyst. When using a fluidised bed reactor (FBR) to
undertake a CVD process the bed is made up of catalyst particles. The gaseous
hydrocarbon is sent through the FBR at a velocity higher than the minimum
fluidisation velocity to ensure that the catalysts have maximum contact with the
hydrocarbon so that it will break into the carbon and hydrogen. The carbon uses
the catalysts as a template to grow on in order to produce chains of Carbon
Nanotubes (CNT).

35

Figure 11: diagram of the FBR

The figure above is a basic image of the FBR being used. (Refer to section 3.6 for
PFD) The FBR runs in 30min batches ensuring that those reactants are in contact
with each other for the 20 min residual time. The gas ( argon and acetylene)
enter the FBR through the streams called argon in and acetylene in. Before
entering the FBR the gases are stored in tanks at double the atmospheric
pressure. The catalyst (Fe 2O3 and MgO) enters the FBR from a bucket conveyer
belt from the solid feed stream above. There is an automatic valve at the
entrance of the solid feed stream to the FBR which is only opened for the first 30
sec of each batch to ensure that all the catalyst required reacts and contacts the
gas for the required amount of time. There is another valve at the exit of the FBR
into the solid discharge stream (through which the CNT and catalysts and
amorphous carbon are released). The valve is only opened for the last 10mins of
each batch and the solid discharge falls directly to a tank where the smaller
amorphous carbon (Fujita, Ishida, Ichihashi, Ochiai, Kaito, & Matsui, 2003) is
filtered out and is collected into a tank for disposal. There is a valve in the
filtering tank which is opened after 10 mins to allow the CNTs + catalyst to fall
into another tank to be purified (see section 5). The gas out stream contains
hydrogen gas, argon, and a minute amount of CNT and catalysts. This stream is
connected to the cyclone (see section 4).

3.2 Alternatives to design

Methods to produce CNTs beside CVD include plastic pyrolysis, flame synthesis,
liquid hydrocarbon synthesis, arc discharge, and laser ablation. From these five
methods for large scale production only arc discharge and laser ablation can be
used. In arc discharge, two graphite rods are placed less than 1mm apart in a
container containing inert gas at low pressures. A driving force of a potential
difference of 20V results in a current between 50 to 100A to cause a high
temperature discharge between the two graphite rods. This results in one of the
surfaces of the electrodes to vaporise resulting in the production of CNTs on the
36

other electrode. (Cheap Tubes Inc, 2008). Arc Discharge and laser ablation are
similar in that they both use thermal energy to produce CNTs. Laser ablation uses
a laser source to cause high temperatures on a carbon electrode so that carbon
is vaporised. This carbon is then cooled using a carrier gas stream. This results in
the formation of CNTs and other carbon by-products.

3.3 General Assumptions used in the design

In the laboratory design (Mauron, Emmenegger, Sudan, Wenger, Rentsch,

& Zuttel, Fluidised-bed CVD synthesis of carbon nanotubes on Fe2O3/MgO,
2003), 0.001g of CNTs were produced per batch.
The 5000kg/day product being produced is 95% pure. (Mauron,
Emmenegger, Sudan, Wenger, Rentsch, & Zuttel, Fluidised-bed CVD
synthesis of carbon nanotubes on Fe2O3/MgO, 2003)
The density of the catalysts and the CNT are all the same in the FBR.
The diameter of the catalysts and the CNT are all 100m.
All the particles in the FBR are sphere shaped.
Diameter of the FBR is 1.5 m
All the argon that enters the FBR leaves the FBR through the gas outlet.
All the carbon that enters the FBR in the acetylene is in the CNTs
produced.
All the remaining hydrogen from the acetylene forms hydrogen gas.
The FBR is performing at 650OC and no heat is being lost.
1% of the CNTs and catalyst particles are lost from the FBR through the
gas stream.
The FBR has a ceramic lining with a mild-steel vessel.
The FBR is being run in 30 min batched for 24 hrs a day, 365 days an year.

3.4 Mass Balances

3.4.1

Laboratory scale FBR

For the laboratory scale assume:

the gases are entering the FBR at atmospheric temperature and pressure
0.001g of CNT is being produced
Each batch is 30 min

The volume of argon (Ar) going into the FBR is 42cm 3 per batch. (Mauron,
Emmenegger, Sudan, Wenger, Rentsch, & Zuttel, Fluidised-bed CVD synthesis of
carbon nanotubes on Fe2O3/MgO, 2003) Using PV=nRT (assuming an ideal gas),
there is 0.00172 moles of Ar going into the FBR per batch. (as P = 101325 Pa, R
= 8.314 m3Pa/(molK), T = 298 K)
The volume of Acetylene (C2H2) going into the FBR is 368 cm 3 per batch.
(Mauron, Emmenegger, Sudan, Wenger, Rentsch, & Zuttel, Fluidised-bed CVD
37

synthesis of carbon nanotubes on Fe2O3/MgO, 2003) Using PV=nRT (assuming

an ideal gas, there is 0.0151 moles if C2H2 going into the FBR per batch. (as P =
101325 Pa, R = 8.314 m3Pa/(molK), T = 298 K)

3.4.2

Commercial Scale FBR

Total production of product per day = 5000 kg/day

Assuming the purity of the product is 95%, amount of CNT produced = 4750
kg/day = 104.17 kg/30min (assuming one batch is 30 min and that the process is
being run for 24 hrs, 365 days a year)
3.4.2.1
Gas entering the FBR
Assume that the gas is stored in tanks at double the atmospheric pressure and at
room temperature.

mole of Ar coming
moles of Ar beingused thelabarotary amount of product

be p roduced per batchby Ultra Nano

amount produced per batchthe labarotary
Thus, mole of Ar required per batch = 178923.9 moles
Using PV=nRT volume of Ar going into the FBR was found to be 2187.6 m 3/30
min (using P = 202640 Pa, T = 298 K, R = 8.314 m 3Pa/(molK))
Similarly the moles of C2H2 were determined to be 38333.3 mole/batch and the
volume per batch was found to be 468.68 m 3.
3.4.2.2
Catalyst particles entering the FBR
From Section 4 it can be seen that 864.4 kg/day of Fe 2O3 and 11227.72 kg/day of
MgO will be required. This indicates that there is 112.77 mole/30min batch of
Fe2O3 and 6251.11 mole/30min batch of MgO entering the FBR (as the molar
mass of Fe2O3 = 159.7 g/mole and the molar mass of MgO = 40.3 g/mole). Thus
per batch there is 18.01 kg of Fe 2O3 entering the FBR and 233.92 kg of MgO
entering the FBR.
3.4.2.3
Particles leaving the FBR through the solid discharge
From the beginning of Section 3.42 it can be seen that the amount of CNT being
produced per batch is 104.17 kg. It can be assumed that the catalysts (251.92kg
per batch) are attached to the CNT particles. Thus the mass of the solids in the
FBR = 356.09 kg per batch. It is assumed that 99% of these solids exit the FBR
through the solids discharge stream. Therefore the mass of the CNT + catalyst in
the solid discharge stream = 352.53 kg/30min batch. The total mass of the
carbon entering the FBR was found to be 920 kg per batch. The carbon that is
not converted to CNT (that is 815.83 kg per batch) can be assumed to be
amorphous carbon. This carbon is smaller than the CNT + catalyst particles
(Fujita, Ishida, Ichihashi, Ochiai, Kaito, & Matsui, 2003) so it can be filtered out
before sending the CNT + catalyst particles to the purification process.
38

3.4.2.4
Gas leaving the FBR
Assuming that all the Ar entering the FBR leaves the FBR at the gas outlet, moles
of Ar leaving the FBR per batch = 178923.9 moles. The FBR is operating at 650 OC
(Mauron, Emmenegger, Sudan, Wenger, Rentsch, & Zuttel, Fluidised-bed CVD
synthesis of carbon nanotubes on Fe2O3/MgO, 2003). Assuming the Ar is an ideal
gas and is leaving the FBR at atmospheric pressure, using PV=nRT the volume of
Ar leaving the FBR is 13551.42 per batch.
Assuming that all the hydrogen in the C 2H2 that enters the FBR becomes
hydrogen gas that leaves the FBR through the gas outlet, moles of H 2 leaving the
FBR per batch = 38333.33 moles. Assuming that the H 2 is leaving the FBR at the
same conditions as the Ar, volume of H2 leaving the FBR per batch = 2903.31 m3.
It can also be assumed that 1% of the CNT + catalysts are lost through the gas
outlet in the FBR. Thus the amount of CNT + catalyst in the gas outlet of the FBR
per 30 min batch = 3.56 kg (1% of 356.09kg see section 3.423).

Solid feed
MgO = 6251.11 mole
Fe2O3=112.77 mole

Gas discharge
MgO = 62.51 mole
Fe2O3=1.13 mole
C (in CNT) =
104.17*0.01*103/12mole=86.80mole
Ar=178923.9 moles
H2 = 38333.3 mole (that is moles of H
=76666.6 mole)
Solid discharge
MgO = 6188.60 mole
Fe2O3=111.64 mole
C (in amorphous Carbon) =
815.83*103/12mole = 67985.8 mole
C (in CNT) =
104.17*0.99*103/12mole=8594.0mole

Ar gas
178923.9 moles

3.5 Energy

C2H2 gas =38333.3 mole

C = 76666.6 mole
H = 76666.6 mole
Figure 12: mole balance over
the FBR over a 30 min batch
Balance:

3.5.1 Energy from Gas streams:

Solid feed
2141.45 KW

Ar gas
0 KW

Gas discharge
512.84KW
Heating required by the FBR =
energy in energy out (assuming no
heat loss)
= (512.84+92236186.1)(2141.45+0+4828.94)KW
=92229728.55
Solid discharge
92236186.1 KW
39
C2H
Figure 13: energy balance
over
FBR refer to
2 gas
Table 13 for calculations4828.94KW

Table 13: calculation of energy per stream

Stream

Hf^

Cp

C P dT

^
H

Total
energy
from
stream

C2H2 stream going in

226.75
KJ/mole#

NA

NA

NA

NA

NA

25OC

226.75
KJ/mole

4828.94KW

Ar stream going in

0
KJ/mole##

NA

NA

NA

NA

NA

25OC

0 KJ/mole

0 KW

Catalysts
going in

MgO

601.8
KJ/mole#

NA

NA

NA

NA

NA

25OC

601.8
KJ/mole

2089.95KW

Fe2O3

822.2
KJ/Mole#

NA

NA

NA

NA

NA

25OC

822.2
KJ/Mole

51.50 KW

Total
Gas
discharge
stream

2141.45
KW

Ar

0 KJ/mole
#

1.3439*1
0-5##

1.9894*1
0-3

11.043

2.8*109

650OC

2797069.2
1 KJ/mol

278034758
.5 KW

MgO

601.8
KJ/mol#

10.86##

0.001197

208700

7718.45

650OC

8320.26
KJ/mol

288.95 KW

Fe2O3

822.2
KJ/mol#

24.72##

0.01604

423400

22532.35

650OC

23354.55
KJ/mol

14.63KW

H2

0 KJ/mol#

3.249##
#

0.000422

8300

2210.504

650OC

2210.50
KJ/mol

47075.55
KW

CNT(i.e. C)

0 KJ/mol#

1.771##

0.000771

-86700

1204.05

650OC

1204.05

512.84KW

40

KJ/mol

Total
Solid
discharge

278082650
.5

MgO

601.8
KJ/mol#

10.86##

0.001197

208700

7718.45

650OC

8320.26
KJ/mol

28605.95
KW

Fe2O3

822.2
KJ/mol#

24.72##

0.01604

423400

22532.35

650OC

23354.55
KJ/mol

1448.49
KW

C
(including
CNT and
amorphou
s)

0 KJ/mol#

1.771##
#

0.000771

-86700

1204.05

650OC

1204.05
KJ/mol

92206131.
64 KW

Total

92236186.
1

# (Coulson, Richardson, Backhurst, & Harker, 1954)

## (Perry & Green)
### (Winnik, 1997)
^reference temperature=25OC

41

3.6 Preliminary PFD

Figure 14: PFD of the FBR design (refer to section 3.1 for description)

42

3.7 Design Calculations

Using the conditions determined in section 3.42 the density (0.4382 kg/m3) and
viscosity (0.0000503 Pa) of the gas in the FBR was determined using Hysys.
From section 3.422 the calculated masses of Fe 2O3 and MgO entering the FBR
can be observed. The density of Fe 2O3 (5240 kg/m3 (Environment, Health &
Safety - US, 2007)) and MgO (3700 kg/m 3 (Science STuff inc) enables the
estimation of the volumes of the catalysts entering the FBR. (0.004867232 m3 of
Fe2O3 and 0.044639482 m3 of MgO per each 30 min batch). The density of CNT is
1300 kg/m3 (Physical properties of carbon nanotubes). Using this the volume of
the CNT was found to be 0.078321m 3 per batch. Using the total volume and
total mass of the CNT and the catalysts the average density of particles in the
FBR was determined to be 2785.68kg/m 3.
Umf (0.003290 m/s) was calculated using these densities and viscosities. Since
the flow rate of the gases is known an assumption is made that the gas is always
travelling at minimum fluidisation velocity allowing for the calculation of the
cross-sectional area of the FBR which results in 321.81m 2. This number is too
high and indicates that the gas is not flowing at minimum fluidisation velocity.
Thus, the diameter of the FBR is assumed to be 1.5 m (resulting in a crosssectional area of 1.767 m2 and a velocity of 0.835m/s).
As the particle size was assumed to be 100m the Baeyens and Geldart
correlation was used (Rhodes M. , 2008)

p f

0.934 0.934 1.8

g
xp

U mf =
This gave a minimum fluidisation velocity of 0.00459m/s. From this Re mf was
calculated to be 0.003992.
U*

and

d =d p

d*

( p ) g
2

were

calculated

by

2
U =U
( p ) g

1
3

and

from

1
3

The graph in (Harris, 2008) was used to determine that the particles in the FBR
are class A particles which are suitable for conventional fluidised beds. The
terminal velocity (UT) was then calculated (assuming that the particles are all
spheres). Using this, the bubble size and the bubble velocity was determined
through
43

UT
( 2)
2
g
d BV =
Using

B=

0.5

U B = A ( g d BV ) where A =2.5 as D>1 m

UU mf
UB

B was found to be 0.4328. The mf was assumed to be 0.4

(Rhodes M. , 2008). Thus using (1-)=(1- B)(1-mf) the voidage in the FBR can be
determined. This allows for the determination of the bed density 948.09kg/m 3 (as
bed density = (1-)*particle density). As the mass of the particles in the bed is
known (356.09kg/30 min) the volume of the bed can be determined (0.3756 m 3).
Using this and the cross-sectional area of the bed the height of the bed can be
determined as 0.213m.
Assuming Umf=Umb (Rhodes M. , 2008) U-U mb = 0.830. Using this and the 1.5m
FBR diameter the Transport disengagement height (TDH) is determined to be 3.5
m (figure 17-8 (Perry & Green)). Assuming the splash zone is 10% of the TDH,
and the dilute transport height is 50% of the TDH, the splash zone height =
0.021m and the dilute transport height = 1.75m. This results in a total freeboard
height of 5.271m. The height of the plenum chamber is assumed to be 0.7 m to
allow room for maintenance when required. The quartz layer place in between
the sieve and the bed can be assumed to be 0.003m (Mauron, Emmenegger,
Sudan, Wenger, Rentsch, & Zuttel, Fluidised-bed CVD synthesis of carbon
nanotubes on Fe2O3/MgO, 2003). This results in a total height of 6.187m.

44

1.75m

Total height
of FBR =
6.187m

5.271
m

3.5m

0.021
m
0.213
m
0.7
m
Figure 15: Heights of the FBR (Rhodes M. , 2008)

The pressure drop over the FBR is then calculated to be 1976.44 Pa using

P=H ( 1 ) ( p f ) g

. Given the pressure drop over the cyclone is 1049.141

Pa (see section 4) and that that gas leaves the FBR at the top at atmospheric
pressure, the assumption that the inlet gas is pressurised to 2 atm is a sufficient
assumption. This is because the addition of the pressure drop over both the FBR
and cyclone to the atmospheric pressure (104345.58 Pa) is less than 2 atm
(202640 Pa). This confirms the view that this pressure will be enough to cause a
driving force that forces the gas to move into the FBR when the valve at the gas
inlet to the FBR is opened.
The solid feed stream is a bucket conveyer that must carry 251.92kg to the valve
at the FBR by the time each new batch begins. This it can be assumed that the
conveyer takes 20 mins to carry all the mass to the valve. There will be 10 mins
in between each batch for the conveyer. Thus the conveyer belt needs to be
able to carry 0.21 kg/min of the catalyst to the valve at the FBR. This valve will
open for 30 secs ensuring that all the catalyst falls into the FBR.
The pressurised tanks from which the Ar and the C 2H2 enters the FBR must be
large enough to have enough gas to last a week. Thus the Ar tank must be large
enough to have 735036.3m3 (2187.60795*2*24*7) while the C2H2 tank must be
large enough to carry 157476.9 m3 (468.681*2*24*7).
45

The solid discharge from the FBR drops by gravity to a tank which contains a
filter that has sieves with a diameter of 8nm. This is so the amorphous carbon
(with a diameter of 5nm (Fujita, Ishida, Ichihashi, Ochiai, Kaito, & Matsui, 2003))
formed in the FBR can be separated from the CNT and catalyst particles. The
discharge straight from the FBR will stay in the 2 m3 filter tank for 5 mins. The
amorphous carbon will be collected and disposed of After the 5mins a valve will
open which will allow the CNT + catalyst particles (352.5254kg/30 min batch) to
move into another 2 m3 tank, from where they will be purified (see section 5).
In designing the furnace used for this heat exchanger, it can be assumed that
coal will be used as the fuel. Thus the specific heat capacity of carbon can be
used. An assumption can be made that the coal will be heated from 25 OC to
650OC.
The
mass
of
carbon
required
will
be
919.2
kg/s
(92229728.55*12/1204.0*1000kg/s).

3.8 Preliminary costs estimates

Table 14: Purchsed costs, Total physical costs and total fixed costs of the
equipment

Ar Feed
tan
k
CITATION Pe
t03 \l 3081

C2H2
feed
tan
k

FBR

Bucket
convey
e
r

CITATION Pet03 \l 3
081

CITATION

CITATION

Pet03 \l 3081

Filter
tan
k
CITATION Pet
03 \l 3081

Pet03 \l

Storag
e
tan
k
CITATION Pe
t03 \l 3081

3081

Purcha
sed
cost

$300000

$300000

$20000
0

$7000

$28000

$28000

Total
Physica

$1020
000

$1020
000

$63000
0

$19600

$78400

$78400

CITATION Pet03 \l 3081 Purchased cost calculated from (Peters, Timmerhaus, & West, 2003)
Figure12-52 pg 557
CITATION Pet03 \l 3081 Purchased cost calculated from (Peters, Timmerhaus, & West, 2003)
Figure12-52 pg 557
CITATION Pet03 \l 3081 Purchased cost calculated from (Peters, Timmerhaus, & West, 2003)
figure 15-34 pg 848

CITATION Pet03 \l 3081 Purchased cost calculated from (Peters, Timmerhaus, & West, 2003)
Figure 12-61 pg 574
CITATION Pet03 \l 3081 Purchased cost calculated from (Peters, Timmerhaus, & West, 2003)
Figure12-52 pg 557
CITATION Pet03 \l 3081 Purchased cost calculated from (Peters, Timmerhaus, & West, 2003)
Figure12-52 pg 557
46

l
cost
s
CIT
ATION
Pet03 \l
3081

Total
Fixed
cost
s

$435000

$435000

$28000
0

$9450

$38080

$38080

CITATI
ON Pet03 \l
3081

3.9 Conclusions
This design of a FBR allows for the production of 5000kg of 95 % pure CNTs per
day. The FBR itself has a diameter of 1.5m and a height of6.187m. The system
requires a large amount of heating by the furnace to keep the FBR at the
required temperature. In fact the required amount of heating is unreasonable. A
method to reduce this required amount of heating is to heat the products coming
in (that is the gases and the catalysts). While this requires more heat exchangers
throughout the system, the overall energy required to heat the system will
reduce as the products in the FBR will not have to be increased to such a great
temperature in a short period of time. In addition, the gas products can be stored
at lower pressures. In order to ensure that that the gas enters the FBR a blower
can be used. The total cost of the FBR section of the system is $4 945 010.

4.

Gas Cleaning System

4.1 Description of Basic Technology and its Purpose

Gas emissions from the Fluidised Bed Reactor contain very fine particles which
are in suspension, and thus easily captured in the gas emissions stream. The
particles in the gas are made up of catalyst particles, 100m in diameter,
catalyst particles with CNTs still attached with diameter greater than 100m,
and CNT particles which has broken off from the catalyst, ranging from 0.4500nm (Langrish, 2008) in diameter. The technology used to separate the
particles from the gas is determined by the particle size. Table 15 below shows a
range of particle sizes and the technology commonly used for separation.
CITATION Pet03 \l 3081 Total physical plant cost calculated from (Sinnott,
2006)table 6.1, pg 252. Includes installation, piping, instrumentation, electrical,
buildings, utilities, storages, site development and ancillary buildings
CITATION Pet03 \l 3081 Total fixed capital calculated from (Sinnott, 2006) table 6.1, pg
252. Includes design and engineering, contractors fee and contingency.

47

Table 15- Particle Size and Separation Technique (Rhodes, 2008)

Particle Size
>100m

Separation Technique
Gravity settling techniques

<10m

Filtration, Wet Scrubbing or

Electrostatic Precipitation

>10m and as large as 1mm

Gas cyclones

It can be seen from Table 15 above, a gas cyclone would be the most suitable
technology to use, as it can easily remove the catalyst particles and the catalyst
particles with the CNTs still attached, and this solids stream can then be taken to
the next stage for purification. The cleaned gas, contained carbon nanotubes can
be disposed of, by burning them in a furnace.
The reverse flow gas cyclone is the gas cyclone most commonly used in industry
and is shown in Figure 16 below.

Figure 16- Reverse Flow Cyclone (Rhodes, 2008)

It works by creating a vortex within the body of the cyclone, when the inlet gas
into the cylindrical section is introduced tangentially. Centrifugal forces act on
the particles in the gas, which cause the particles to move rapidly outwards
towards the inside surface of the cyclone, while the gas flows inwards, causing
the particles to separate from the gas. Solids are pushed down through the
bottom outlet (which is sealed to gas) by the outer vortex and out via the solids
exit. The cleaner gas containing fine nanotubes particles leaves the cyclone via
the outlet at the top.

48

4.2 Alternative for design

Separating Larger Particles
Separation techniques, such as Gravity Settling or Filters can be used before the
unclean gas enters the cyclone, to remove the larger particles, such catalyst
particles and catalyst with CNT particles attached, which potentially have
diameters greater than 100m.
Separating Smaller Particles
Additional separation devices, such as electrostatic precipitators, wet scrubbers
or fabric filters could also be employed downstream to help remove more of the
finer CNT particles still left in suspension. This use of this alternative device
should be considered, as gas cyclones are not always suitable for separation with
a large quantity of particles less than 10m. Since CNT particles are very fine,
they can easily break away from the catalyst, and therefore, on occasions, the
gas flow could have a large proportion of CNT particle.
An electrostatic precipitator is a highly effective filtration device, as shown by the
efficiency graph in Appendix A.2. An induced electrostatic charge forces the
particles to be removed from the gas. However, this is a more energy intensive
technology and is more expensive to purchase than gas cyclones.
Electrostatic precipitators are currently used in industries such as cement, pulp
and paper, petrochemical and steel to clean gas emissions so they are suitable
to be released to the environment. (Dayley & Holbert, 2003)

4.3 Assumptions
Reasonable Cyclone Diameter
After reading a variety of literature about designing cyclones, typical
diameters in these papers were around 0.3-1.3m. Therefore, it is assume that
the average diameter for a typical well designed cyclone is around 0.8m
Particle Diameters
From the FBR section, it is assumed that the catalyst particles have a
diameter of 100m.

Particle Cut Diameter was assumed to be 10m. This is because cyclones are
not very good at removing particles sizes less than 10m. Setting the particle
cut diameter at this value means that the cyclone will definitely remove the
catalyst particles and the catalyst particles that have CNT attached to them,
thus getting full recovery of the catalyst particles. Not all nanotubes
particulates of diameter 0.4-500nm will be lost via the gas outlet.

49

4.4 Mass Balance

Figure 17 Standard Performance Curve for Stairmand High Flow Rate Cyclone
at a given particle diameter (Sinnott, 2005) (pg 451)

From Figure 17, it can be determined that the efficiency of Stairmand H.R cyclone
is around 70%. This means that 70% of the mass of particles in will be captured
and will exit the cyclones via the solids outlet, and the remaining 30% of the
particles stay suspended in the gas.
Mass (particles in) = 1.878g/s
Mass (particles out via solids) = 70% x 1.878g/s
=1.385g/s
Mass (particles out with gas) = 30% x 1.878g/s
=0.59g/s
From this, it can be recommended that 0.59g/s of clean gas can be added to the
flow taken to the CNT Purification stage. It is also recommended that the
particles out of the top of the cyclone be collected in a furnace for burning. The
carbon burnt, with oxygen is released as CO 2 into the atmosphere.

50

Figure 18 Mass Balance over the two cyclones

Mass of particles accumulated over the reaction time of 30 minutes:

Total Mass of solids in = 3.561kg/30mins

Solids (to furnace) = 1.062kg/30mins

Particulates (in clean gas) =2.493kg/30mins

51

4.5 Process Flow Diagram

Figure 19- Gas Cleaning Process Flow Diagram

52

Unclean gas emissions from the FBR enter two cyclones in parallel so that the
gas can be cleaned by removing the particles in suspension (Cyclone 1 and
Cyclone 2). The solid particles collected at the bottom of the cyclone contain
catalysts and catalyst with CNT particles still attached. These solid particles are
taken to the purification section, so that CNTs collected from the cyclones can be
washed and cleaned. This stream minimises catalyst and CNT loss through the
gas stream, and also increases the overall product of CNTs.
It is recommended that the clean gases from the top of the cyclones are sent to
a furnace for burning. Burning the CNTs particles allows CO 2 to be released into
the atmosphere, with little environmental effects. CNTs are thought to be
carcinogenic, and have the same effects are that of Asbestosis. It is therefore
important that the particles are burnt before they are released to the
atmosphere.
Valves, are placed at the gas entrance (Valve 1 and Valve 2) and gas exit (Valve
3 and Valve 5) of both cyclones, as well as the solids exit of the cyclones (Valve 4
and Valve 6), to allow one cyclone to keep running if the other is having
mechanical problems, and also, allow one or both cyclones to shut for cleaning,
or scheduled plant shutdown periods. Check Valves (Check Valve 1 and Check
Valve 2) are placed in the gas exit stream to prevent backflow of the gas.

4.6 Design Calculations

4.6.` Calculation Method
The total unclean gas flow, Q, coming out of the Fluidised Bed Reactor was equal
to 9.14m3/s, at a temperature of 650oC and 1atm. Of this, there was 7.529m3/s
Argon and 1.613m3/s Hydrogen. Values for the density and viscosity of the
unclean gas stream were obtained from Hysys (using the Peng-Robinson Fluid
Package) and were found to be =0.4382kg/m 3 and =5.03 x 10-5Pa.s. Particles
coming from the Fluidised Bed reactor are equal to p=4023.357kg/m3.
Design calculations were performed, based on the Stairmand High Efficiency
(Stairmand H.E.) and Stairmand High Flow (Stairmand H.R) cyclones. Stokes
Number (St) and Eulers Number (Eu) for each cyclone are given below.
Stairmand, H.E: St = 1.4 x 10-4 and Eu = 320
Stairmand, H.R: St = 6 x 10-3 and Eu = 46
In order to size gas cyclones, a particle cut diameter must first be assumed. From
this assumption, cyclone diameter and relative dimensions, velocity, and
pressure drop can then be calculated. With the flow rate of 9.14m 3/s, calculations
over both the Stairmand H.E and Stairmand H.R cyclones were performed. The
particle cut diameter, dc was assumed to be 10m. It was also found that having
two cyclones in parallel, each with a flow rate of 4.57m 3/s, instead of just 1
cyclone, allowed the characteristic velocity and the pressure drop to lie within a
suitable range.
53

A full worked method, for two cyclones in parallel with cut diameter of 10m over
both the Stairmand H.E and Stairmand H.R are shown below.
4.6.2 Cyclone Diameter and Dimensions
From this assumption of the particle cut diameter, Cyclone Diameter, D, can be
calculated, using the equation below, by manipulation of both the cut diameter
equation and the characteristic velocity equation and solving simultaneously.

4Q
D2

d2c
and

18D I
St
pU

18D I
St
pd2c

4Q 18D I

St
D2 pd2c

D 3

4Q pdc2
18StI

A well designed cyclone is assumed to have a diameter of around 0.3m-1.3m.

(Rhodes, 2008)
Table 16- Diameter Calculation over Stairmand H.E and Stairmand H.R Cyclones

Stairmand H.E Cyclone Diameter

4Q d

18St

9.14
4023
.357 0.000001
2
D
18 1.4 104 5.033 102
3

Stairmand H.R Cyclone Diameter

2
p c
I

D = 2.10m

4Q pdc2
18StI

9.14
4023
.357 0.000001
2
18 6 103 5.033 102

D = 0.75m

Once, the cyclone diameter is determined, the dimensions listed below can be
determined relative to the diameter length.
Dimension
Diameter of
Cyclone

Letter Reference
(in Figure 20 below)
D

Inlet height

Inlet width

L
54

Outlet length

Outlet diameter

Cylinder height

Overall height

Dust outlet
diameter

Conical Height

Figure 20- Cyclone Dimensions

Table 17 below shows the dimensions for both Stairmand H.E and Stairmand H.R
cyclones for the calculated cyclone diameters of 2.10m and 0.75m respectively.
Table 17- Dimensions of Stairmand H.E and Stairmand H.R Cyclones

Dimensio
ns
A
B
C
E
J
L
K
N

Dimensions
Relative to
Diameter (H.E
Cyclone)
4.0 x D
2.5 x D
1.5 x D
0.375 x D
0.5 x D
0.2 x D
0.5 x D
0.5 x D

Stairmand
H.E
Cyclone
(m)
8.390332
5.243957
3.146374
0.786594
1.048791
0.419517
1.048791
1.048791

Dimensions
Relative to
Diameter (H.R
Cyclone)
4.0 x D
2.5 x D
1.5 x D
0.575 x D
0.875 x D
0.375 x D
0.75 x D
0.75 x D

Stairmand
H.R
Cyclone
(m)
3.02075
1.887968
1.132781
0.434233
0.660789
0.283195
0.566391
0.566391
55

4.6.3 Cyclone Velocity

Once the diameter of the cyclone is found, the characteristic velocity is then
calculated using either the characteristic velocity equation shown below.

4Q
D2

Typical velocity for well designed cyclones is around 10-20m/s (Sinnott, 2005)
Table 18- Velocity Calculation over Stairmand H.E and Stairmand H.R Cyclones

Stairmand H.E Cyclone Velocity

Stairmand H.R Cyclone Velocity

4Q
D2

4Q
D2

9.14
2
U
2.102

9.14
2
U
0.752

U = 0.66m/s

U = 10.20m/s

4.6.4 Pressure Drop

A pressure drop is then calculated by the manipulation of the Eulers number
equation, shown below.

Eu

P
U2
g
2

EuU2
2

For correctly designed cyclones at ambient conditions, the recommended

pressure drop range for cyclones to operate is around 500-1500Pa. (Rhodes,
2008)
Table 19- Pressure Drop Calculation over Stairmand H.E and Stairmand H.R
Cyclones

Stairmand H.E Cyclone Pressure

Drop

Stairmand H.R Cyclone Pressure

Drop

EuU2
P
2

EuU2
P
2

320 0.4382 0.662

2

P = 30.66 Pa

46 0.4382 10.202
2

P = 1049.14 Pa
56

4.6.5 Summary of Results

Table 20 below shows a comparison of the calculated results for both Stairmand
H.E and Stairmand H.R cyclones with a total flow of 9.14m 3/s from the FBR.
Table 20- Summarised calculation values over both Stairmand H.E and
Stairmand H.R Cyclones

Stairmand H.E

Stairmand H.R

Typical Values
(Rhodes,
2008)
(maximum flow
25m3/s)

Stokes Number
Eulers Number
Total Flow
(m3/s)

1.4 x 10-4
320
9.14

6 x 10-3
46
9.14

Number of
Cyclones
(in parallel)
Flow into each
Cyclone (m3/s)
Particle Cut
Diameter
Dc (m) (assumed)
Diameter of
Cyclone
D (m)
Velocity
U(m/s)
Pressure Drop
P (Pa)

4.57

4.57

10m

10m

2.10

0.75

0.3 - 1.3

0.66

10.20

10 - 20

30.66

1049.14

500 - 1500

Detailed Calculations, over a range of both cut diameter and number of cyclones
can be found in Appendix A1.
By comparing the calculated values for Stairmand H.E and Stairmand H.R
cyclones in Table 20 above, it can be seen that the diameter, velocity and
pressure drop over the Stairmand H.R lie closer to the typical values, and thus
the design is best suited to our needs.
4.6.6 Design Choice
From the design calculations, 2 Stairmand High Flow Rate cyclones in parallel
where chosen as the gas cleaning system, the dimensions of which are shown in
Figure 21 below.

57

Figure 21- Dimensions of Designed Cyclone

Cyclone Diameter = 0.75m

Inlet = 0.57m x 0.28m
Outlet = 0.57m
Cylindrical Height = 1.13m
Conical Height = 1.89m
4.6.7 Cyclone Efficiency
Cyclone Efficiency was determined using the curve shown in Figure 17 in the
mass balance section. The curve shows that at a particle size cut diameter, the
efficiency of the cyclone is around 70%.

4.7 Cost Estimate

4.7.1 Cyclone Cost
Table 21 below shows the costs for 2 Carbon Steel Cyclones, each with
volumetric gas rate of 4.57m3/s was determined using Figure 15-48 (Peters,
Timmerhaus, & West, 2003) pg 868. It includes the pruchase cost, Total Physical
Plant Cost and Total Fixed Captial Cost.
Table 21- Costing Cyclones

Cost
Purchased Cost

For Two Cyclones

$11,800
58

($5,900 each)
Total Physical Plant Cost

$111,510 CITATION Pet03 \l 3081

Total Fixed Capital Cost

$156,114 CITATION Pet03 \l 3081

Full worked values can be found in Appendix A3.

Total Cost of Gas Cleaning System = $156,114 (US$)
4.7.2 Furnace Cost
Purchase Costs of Furnaces range between $540 to $560. (Sinnott R. , 2006)
Conversion of this value into Australia dollars with vary each day, depending on
exchange rates.

Conclusion
It can be seen from the design calculations that having two Stairmand H.R
cyclones in parallel with a cut diameter of 10m is a well suited design to the
needs of our process. This is due to the fact that the diameter and dimensions of
the cyclones, the velocity and the pressure all lie within the typical values range.
The cyclone also operates with a high efficiency of 70%. Electrostatic
precipitators are not necessary in this process, as they are very energy intensive
and expensive, just the equipment costing $100.700(US) (for carbon steel) from
Figure15-48 pg 868 (Peters, Timmerhaus, & West, 2003). The two cyclones are a
much cheaper option costing only $5,900 and a total fixed capital cost of
$156,114. By mass balance calculations, it can be seen that if the efficiency of
the electrostatic precipitator was operating at its maximum, it would only recover
1.062kg per 30 minutes (reaction time), and is therefore not worth the cost.
It is recommended that the particles that are not captured by the cyclones are
sent to a furnace and burnt. Burning carbon with oxygen forms CO 2 and can be
released to the atmosphere in small amounts.
Safety is also an important factor when using cyclones to clean carbon
nanotubes particulates from Argon and Hydrogen gas. The fine CNT particles are
thought to be carcinogenic, and are thought to have the same affects as
asbestosis. It is therefore important that great care is taken when burning these
particles, and that they are not released into the atmosphere. The gas cyclone
system must be checked regularly for leaks. This is because hydrogen gas is a
stable, but very flammable gas, igniting spontaneously at 560 oC (Oxford, 2008).
Leaking of hydrogen gas may spontaneously combust, the fire being extremely
hot and invisible. Argon gas must also be monitored, as it is a simple asphyxiant,
CITATION Pet03 \l 3081 Total physical plant cost calculated from (Sinnott, 2006) Table
6.1, pg 252. Includes installation, piping, instrumentation, electrical, buildings, utilities,
storages, site development and ancillary buildings.

CITATION Pet03 \l 3081 Total fixed capital calculated from (Sinnott, 2006) table
6.1, pg 252. Includes design and engineering, contractors fee and contingency.
59

that causes rapid breathing, fatigue, impaired muscular coordination and

sometimes death if it is released in a confined space (BOC Gases, 1996). The
effects of these gases leaking is extremely harmful to all employees.

60

5.Purification
The purification process is one of the most important parts of the CNT
manufacturing process, transforming the impure raw CNTs into the
product to be sold to the consumer. A purity of 95% is required for the
application of the CNTs in consumer electronics, and so a robust
purification process is essential. The purification process is inherently
simple due to the solubility of the magnesium oxide substrate used. The
purification process will focus solely on the removal of the catalyst and its
substrate, assuming that amorphous carbon is present in such small
amounts as to be negligible. The process is run as a continuous process
as this is a more commercial viable mode of operation, reducing both the
capital expenditure compared to a batch process, and also providing the
possibility of scale up.

5.1 Description of Process and Technology

The process can be broken down into 3 main steps, each with several unit
operations;

Acid Purification This stage involves mixing the un-purified CNT

product with concentrated HCl to dissolve the catalyst and its
substrate, under microwave assisted digestion.
Filtration The next step removes the CNT particles from the slurry by
physical separation. During this separation most of the water present
and all of the acid and dissolved substrate are removed.
Drying The last stage dries product through thermal evaporation to
produce the ready to ship product.

5.1.1 Acid Purification

Since the CNT synthesis process is a batch operation, The first step in designing
the continuous process is to insert a raw CNT holding tank holding, so the raw
CNTs can be delivered to the purification process in a continuous stream. The
CNTs are fed by gravity into a stirred tank where they are mixed with the
concentrated HCl (40 wt %) and pumped into a Plug Flow Reactor where they are
processed for 30 minutes. The PFR is fitted with microwave emitters to provide
the energy to maintain the reaction temperature at 160C. This increases the
reaction kinetics and allows such a short residence time within the digester. The
resulting slurry is then washed with distilled water over a cellulose nitrate filter
beds to remove the remaining HCl and the dissolved catalyst and its substrate.
While the pores in a cellulose nitrate membrane filter are larger than the 1
61

micron size of the nanotube agglomerations, an initial layer of nanotube particles

will fill the pores not allowing any of the particles to escape

5.1.2 Filtration
The filtration process uses a screen bowl decanter centrifuge to force the
nanotubes to sediment out of solution. A decanter centrifuge, will operate by
feeding the slurry into the centre of the horizontal centrifuge, where the solids
settle at the edges and are removed by a helical screw, rotating a different speed
from the centrifuge. The type of decanter centrifuge used is a specialised type of
centrifuge called a screen bowl centrifuge. In this type of centrifuge an extra
screen is added at teh solids collection outlet allowing extra washing of the solid
with pure water. It is in this step that the majority of the water, the remaining HCl
and the dissolved ions are removed. CITATION Pet03 \l 3081 The liquid is discharged to
waste water treatment and recycling while the sediment moves on to the final
drying process.

5.1.3Drying
The cake from the centrifuge is then fed into the rotary dryer, where any
remaining moisture is removed by the passage of dried air. The final granular
product is the moved by conveyor belt to product storage from where it can be
shipped.

5.2 Mass/Energy Balance

The mass balance was calculated based on a producing 5000 kg/day of 95% pure
carbon nanotube product. The mass balance was conducted using the simplifying
assumptions 1-7, from section 5.8. The summary of the mass balance is listed in
section 5.2 while calculations and excel spreadsheets are detailed in appendix I.
A simple energy balance was calculated to determine the temperature of each
stream. Assumptions 11-12 from section 5.8 were used to calculate the energy
flows.

CITATION Pet03 \l 3081 Assumption 2

62

5.3 Process Flow Digram

63

5.4 Design Calculations

5.4.1 Storage Tanks
As the synthesis of CNTs is a batch process, a reservoir of the un-purified CNT
product must be stored to provide a continuous feed to the purification process.
Four batches or two hours of product are to be stored, i.e.:

kg
hr
V
=0.51m3. Using a safety factor of 25% to account for any
kg
2785.68 3
m
2 hr 7.06

process disruptions V=0.68m3. For a 1.5 m high tank this corresponds to a

diameter of 0.76m
The HCl storage tank is constructed of Fibreglass Reinforced Plastic (FRP) in order
to withstand the corrosive effects of concentrated acid. The HCl tank will hold 2
days storage plus the safety margin.

64

2 day 58550.8
V

kg
1035 3
m

kg
day

=113m3 = 150.8m3 with safety factor. For a tank of this

size 12 m high the diameter must be 4m to give the required volume.

Un-Purified Product Tank
Material of
Carbon
Construction
Steel
Height

1.5m

Diameter

0.76m

HCl Storage Tank

Material of
FRP
Construction
Height

12m

Diameter

4m

5.4.2 Mixer
Using assumption 16, with a residence time of 0.25 hour and flow rate of
7515.1kg/m3 the volume of the tank must be 0.55 m 3. Under assumption 15, the
dimensions of a stirred tank of 0.55 m3, to mix the fluid would be D=0.80, H=1.10
Using the guidelines set out in (Perry R. , 1997) and assumption 17, an off centre
fluid foil impellor should be used. The H/D ratio of 1.375 falls within the
acceptable range of 0.75-1.75. The rest of the specifications were assumed from
the ranges outlined in (Perry R. , 1997). The mixer was lined with FRP to protect it
from corrosion.

Material of
Construction

Mixer
FRP lined carbon
steel

Height

1.10m

Diameter

0.8m
65

Impellor Type

Off Centre fluidfoil

RPM

400

Residence time

0.25 h

5.4.3 Plug flow Reactor

The plug flow reactor was chosen as this made it easier to expose the fluid to the
microwaves necessary to heat it to drive the reaction. The PFR was designed
assuming a residence time of 0.5 hours CITATION Mau03 \l 3081 . This gave a required
volume of 1.10m3 which led to dimensions of D=0.6 m, L=3.90 m.
The energy requirements of the PFR were calculated as the energy required to
heat the feed stream to 180C, as it was at this point that the reaction kinetics
were optimised without thermally degrading the CNTs.
PFR
Material of
Construction

FRP lined steel

Length

3.90 m

Diameter

0.6 m

Residence time

0.25 h

Velocity (u)

7.79m/hour

95 kW

5.4.4Screen Bowl Decanter (Centrifuge)

When designing the centrifuge the first step was to calculate the amount of
throughput required. This was calculated from the mass balance to be 75515.1
kg of slurry per day. In order to handle this volume a continuous screen bowl
decanting centrifuge was used. While the calculations for designing a decanting
centrifuge go beyond the scope of this report, a commercially available
centrifuge was examined and assumed appropriate for application. A Brandt
1850 decanting centrifuge CITATION Mau03 \l 3081 can handle up to 100kg/min and so is
more than capable of processing the process stream of roughly 90kg/min
Table 22: A Brandt 1850 decanting centrifuge

Screen Bowl Decanting

Centrifuge
length
1.12 m
Width

0.32 m
66

bowl length

0.34 m

bowl diameter

0.11 m

bowl speeds

900-2000rpm

Flow rate

92 kg/min

In order to characterise the performance of the centrifuge, the capacity value

was calculated from equation 9.19 (C&R v2) CITATION Mau03 \l 3081 .
(3)
The terminal sedimentation velocity u0 was calculated from equation 4

(4)
Once u0 was found equation 3 could be re-arranged to find the sigma value of
8.52
5.4.5 Rotary Dryer
In order to calculate the dimensions of the rotary drier the following data was
used:
Inlet air temperature (assumed)

650 K

Inlet product
mass balance)

286.9 K

temperature (from

Solid temperature rise (assumed)

163 K

The energy required evaporate the moisture in the filter cake was calculated to
be

product
T dew pt T

Qwater =mliq C p liquid

While the energy required to heat up the solid granules was calculated as:

product
T product out T
Q solid =mC p solid
67

This led to the overall heat duty of the dryer

Qtot al =Qwater +Q solid

Qtotal=2931.1 kW
From here a specific gas flow rate of 5 kg/m 2s was chosen as this lies in the usual
range for a rotary dryer CITATION Mau03 \l 3081 . Then using the method outlined in C&R
v.6 the diameter necessary to permit the volume of gas needed to transfer

1931.1 kW was calculated, with a temperature drop of

airT airout .

The results of the design calculations can be seen in Table 23 below. The final
diameter to length ration was 1:6, similar to that of a typical rotary dryer. For full
calculations see appendix C.
Table 23- Results for Rotary Dryer

Rotary Dryer
Material of
Carbon
construction
Steel
Diameter

2.06m

Length

12.76m

Number of flights

18

RPM

12

2931.1kW

T air in

650 K

T air out

473 K

T product in

286.9 K

T product out

450 K

68

5.4.6 Pumps
P101
Material of
Construction

FRP lined steel

Flow rate

0.04 m3/min

Pressure drop
Efficiency
Power`
P102
Material of
Construction

Carbon steel

Flow rate

0.001m3/min

Pressure drop
Efficiency
Power`

5.6 Alternative Designs

There are many different design alternatives for the purification process. Starting
with the acid digestion, it has been shown that the type of acid used has little
effect on the rate and extent of purification CITATION Mau03 \l 3081 , and so a variety of
different mineral acids (H2SO4, HCl, HNO3) can be used in the digestion process.
HCl was used as it widely available with well documented properties. It is also a
very strong acid, fully de-protonating in water.
Once the type of acid was chosen the method of acid digestion also has to be
determined. There are many options for the acid digestion, including large
CSTRs and acid reflux. The common factor between the other methods however
is a long processing time, with residence times between 12 and 24 hours. It was
for this reason that microwave assisted digestion was used as the energy
provided by the microwave emitters improve the reaction kinetics, decreasing
the reaction time. This allows a smaller digester to be used and so reduces cost.
Fibreglass Reinforced Plastic was used as construction material for unit
operations dealing with concentrated HCl. However other choices exist, such as
steel tanks lined with glass, plastic or glass fibre. FRP was chosen due to its low
cost and also corrosion resistance.

5.7Cost Estimation
The costs need to be estimated for the following pieces of plant:
69

5.7.1 Tanks and Mixers

Table 24- Summary of Costs for tanks and mixers

Raw Product
Storage

HCl
Storag

Mixer (with
agitator

Purchased
Cost CITATION Pet03 \l 3081

$5000

e CITATION Pet03 \l 3081

$75 000

) CITATION Pet03 \l 3081

$7000

Total Physical
Plant
Cost CITATION Pet03 \l 3081

$15 750

$236 250

$22 050

Total Fixed
Capita
l CITATION Pet03 \l 3081

$22 050

$330 750

$30 870

5.7.2Plug Flow Reactor

Table 25- Cost of Plug Flow Reactor

PFR
Purchased Cost

$25000

Total Physical Plant

$78 750
d
CITATION Pet03 \l 3081 Using assumption 21, section 5.8
Cost
e
Total
FixedPet03
Capital
$110
025
CITATION
\l 3081
Using
assumption 21, section 5.8

CITATION Pet03 \l 3081 Purchased cost calculated from (Peters, Timmerhaus, &
West, 2003) fig12-52, pg557
CITATION Pet03 \l 3081 Total physical plant cost calculated from (Sinnott,
2006)table 6.1, pg 252. Includes installation, piping, instrumentation, electrical,
buildings, utilities, storages, site development and ancillary buildings
CITATION Pet03 \l 3081 Total fixed capital calculated from (Sinnott, 2006) table
6.1, pg 252. Includes design and engineering, contractors fee and contingency.
70

5.7.3Screen Bowl Decanting Centrifuge

Table 26- Costs of Sceen Bowl Decanting Centrifuge

Screen Bowl Decanting

Centrifuge
$190 000

Purchased Cost
Total Physical Plant
Costd

$598 500

Total Fixed Capitale

$837 900

5.7.4Rotary Dryer
Table 27- Cost of Rotary Dryer

Installed Cost

Rotary Dryer
$120 000

Total Fixed Capitale

$294 000

5.7.5Pumps
Table 28- Costs for P101 and P102

P101

P102

Purchased
Cost CITATION Pet03 \l 3081

$15 000

$3 000

Total Physical Plant

Costd

$47 250

$7 875

Total Fixed Capitale

$66 150

$11 025

5.7.6Total Capital Cost

Therefore the total capital cost of the plant equipment can be calculated as the
sum of the total fixed capital costs of the respective parts and is equal to $1 702
770 US.

5.8 Assumptions
1. Negligible amounts of CNTs are lost through the process. That is the
centrifuge and rotary drier all have 100% capture of the CNTs.
2. That all the dissolved ions and all the remaining HCl are removed in
the centrifuge
3. That while HCl isnt very effective at removing amorphous carbon,
when the amorphous carbon is present in such small amounts, HCl
digestion is capable of removing all the amorphous carbon.
CITATION Pet03 \l 3081 Purchased cost calculated from (Peters, Timmerhaus, &
West, 2003) fig12-21, pg518 for stainless steel
71

4. From Mauron et al CITATION Jun08 \l 3081 the yield of CNT to impurities is

28%.
5. Amorphous
carbon
makes
up
1%
of
the
un-purified
CITATION Mau03 \l 3081
mass.
6. The impurities in the CNTs consist solely of amorphous carbon and
catalyst + substrate.
7. HCl is used at 1.11 stochiometry as a safety factor to ensure
complete consumption of substrate.
8. The amount of water needed to completely remove all HCl and
dissolved catalyst + substrate is equal the amount of HCl used.
9. All residual HCl and ions in solution are removed during washing
process.
10.
Assume Centrifuge removes 90% by weight of water from
solution.
11.
Assume centrifuge cake contains 15% water by weight of
cake.
12.
Kinetic and potential energy changes of the streams are
negligible.
13.
There are no heat losses over any of the equipment.
14.
The density of slurries can be approximated by combining the
densities of the constituent solids and liquids, taking into account
their percentage contribution by mass.
15.
A stirred tank will approximate a mixer.
16.
Fifteen minutes residence time in the mixer will homogenously
mix the slurry.
17.
The specifications for a mixer in a small diameter tank taken
from Perrys CITATION Mau03 \l 3081 will provide homogenous mixing of the
slurry.
18.
The designed centrifuge will capture all particles of 100
micron size at the volumetric throughput.
19.
By the time the slurry passes to the centrifuge, the majority of
the acid has reacted, relieving the need for FRP corrosion protection.
20.
There are no heat losses from the dryer
21.
The cost relative to carbon steel for FRP is 0.75 for pure FRP
and 1.25 for FRP lined carbon steel tank. Calculated from (Peters,
Timmerhaus, & West, 2003) fig12-53, pg558 for
Material adjustments based on carbon steel
22.That the cost of the screen bowl centrifuge from (Peters, Timmerhaus, &
West, 2003) fig15-47, pg868, with a solid product capacity of 1kg/s will
approximate the cost of the designed centrifuge.
23.That the cost of a Stirred reactor from (Peters, Timmerhaus, & West,
2003) will approximate the cost of the designed PFR

5.9 Conclusion
A purification process for producing 5000 kg/ day, of 95% purity CNTs has been
developed. The process consists of storage tanks feeding into a mixer and a
microwave assisted acid digester to remove all the catalyst and substrate. The
72

water and dissolved solids are then removed in a screen bowl decanting
centrifuge. The resulting cake is dried in a rotary dryer to produce the granular
final product. The design specifications for these unit operations have been
listed. The purification section of the plant is expected to cost US$1.7 million.

73

Bibliography
Brandt. A Varco Corperation. (2004). 1850 Decanting Centrifuge. Retrieved 10
20, 2008, from Product specifications.
Che Plus. (n.d.). Design considerations for shell and tube heat exchangers.
Retrieved 10 23, 2008, from Che Plus:
http://www.cheresources.com/designexzz.shtml
Cheap Tubes Inc. (2008). Carbon Nanotubes, Production Methods for Carbon
Nanotubes Including Arc Discharge, Laser, Chemical Vapor Depsition and Ball
Milling by Cheap Tubes Inc. Retrieved October 20, 2008, from
http://www.azonano.com/Details.asp?ArticleID=1561
Coulson, J., Richardson, J., Backhurst, J., & Harker, J. (1954). Coulson and
Richardson's Chemical Engineering: Fluid Flow, Heat Transfer and Mass Transfer
(Volume 1). Oxford: Pergamon Press.
Einstein, A. (1906). Eine neue Bestimmung der Molekuldimension. Ann. Physik.
Environment, Health & Safety - US. (2007). Ferric Oxide. Retrieved October 20,
2008, from http://www.jtbaker.com/msds/englishhtml/f1306.htm
Fujita, J., Ishida, M., Ichihashi, T., Ochiai, Y., Kaito, T., & Matsui, S. (2003).
Graphitized wavy traces of iron particles observed in amorphous carbon nanopillars.
Gillies, R. G., Schaan, J., Summer, R. J., McKibben, M. J., & Shook, C. A. (2000).
Deposition velocities for Newtonian slurries in turbulent flow. Can. J. Chem. Eng.
Harris, A. (n.d.). 3805-Product Formulation and design. Lecture KL10FLuidisation . Univeristy of Sydney.
Jun, L., & Harris, A. T. (2008). Microwave assisted acid digestion of alumina
supported carbon nanotubes. Seperation and Purification Technology , 602-608.
Louis, C., & Che, M. (1995). Preparation of solid catalysts. Wiley-VCH.
Mauron, P., Emmenegger, C., Sudan, P., Wegner, P., Rentsch, S., & Zuttel, A.
(2003). Fluidised Bed CVD synthesis of carbon nanotubes on Fe2O3/MgO.
Dianmond and Related Materials , 780-785.
Mauron, P., Emmenegger, C., Sudan, P., Wenger, P., Rentsch, S., & Zttel, A.
(2003). Fluidised-bed CVD synthese of carbon canotubes on Fe2O3/MgO.
Fribourg: Diamond and Related Materials.
Mauron, P., Emmenegger, C., Sudan, P., Wenger, P., Rentsch, S., & Zuttel, A.
(2003). Fluidised-bed CVD synthesis of carbon nanotubes on Fe2O3/MgO.
Diamond and Related Materials , 780-785.
74

McKay, D. (1994). JSC-1: A NEW LUNAR SOIL SIMULANT. Retrieved October 20,
2008, from http://www.lpi.usra.edu/lunar/strategies/jsc_lunar_simulant.pdf
Overcamp, T. J., & Manth, S. V. (1998). A simple method for estimating cyclone
efficiency. Anderson: Environmental Progress.
Perry, R. H., & Green, D. W. (Eds.). Perrys chemical engineers handbook (7 ed.).
Perry, R. (1997). Perry's Chemical Engineers' Handbook. United States: McGraw
Hill.
Peters, M., Timmerhaus, K., & West, R. (2003). Plant Design and Economics for
Chemical Engineers. New York: McGraw Hill.
Physical properties of carbon nanotubes. (n.d.). Retrieved October 22, 2008, from
http://www.pa.msu.edu/cmp/csc/ntproperties/equilibriumstructure.html
Regalbuto, J. (2006). Catalyst Preparation: Science and Engineering. CRC.
Rhodes, M. (1998). Introduction to Particle Technology. Sussex: John Wiley & Sons
Ltd.
Rhodes, M. (2008). Introduction to Particle Technology. West Sussex: John Wiley.
Science STuff inc. (n.d.). MSDS:: Magnesium Oxide. Retrieved October 20, 2008,
from http://www.sciencestuff.com/msds/C2026.html
See, H. (2008). CHNG3805: Product formulation and design. Sydney: The
University of Sydney.
Sinnott, R. (2006). Chemical Engineering Design. Oxford: Elsevier.
Stobbe, D. E., van Buren, F. R., Stobbe-Kreemers, A. W., van Dillen, A. J., & Geus,
J. W. (1991). Iron oxide dehydrogenation catalysts supported on magnesium
oxide. J. Chem. Soc.
Winnik, J. (1997). Chemical Engineering Thermodynamics. John Wiley and Sons
Inc.

75

Appendix B: Calculations
Nomenclature
Nomenclat
ure
Fe2O3/MgO

Definition

Nomenclat
ure
Cp

Definition

MgO

Magnesium oxide

Particle density

Fe2O3

Iron oxide

Fluid density

Fe(NO3)3.9
H2O

Iron nitrate

Viscosity

C2H5OH

Ethanol

Re

Reynolds Number

(s)

Solid

Vt

Terminal velocity

(l)

Liquid

CD

Drag coefficient

(g)

Gas

Voidage

Gravity

Pi

dp

Particle diameter

Change in pressure

Umf

Minimum fluidization
velocity

Mixture density

Ar

Archimedes number

Vc

Critical deposition

(dp)

Collection efficiency

Velocity

Eu

Eulers number

St

Stokes number

Hvap

Latent heat of
vapourisation

Supported metal oxide

catalyst

Heat capacity

Mass Balance
Several production variables are defined in the project briefing:

Mass Product: 5000kg

Mass CNT: 95% of product i.e. 4750kg
Yield: Fig.6 (Mauron et al., 2003) gives a yield of 28%. Therefore the total
unpurified mass is 16964kg.

Amount amorphous carbon:

amorphous carbon ( s )=0.01 ( 169644750 )=122 kg

76

The ratio of the MgO to Fe in the precursor is given as 5wt% (Mauron et al.,
2003)
Amount of total catalyst:

catalyst ( s )=169644740122=12092.14 kg
Composition:

5 Fe=12092.14 0.005=604.61kg

Fe2 O3 (s)= ( 604.61/55.85 ) 0.5 ( 3 16+2 55.85 )=864.42kg

MgO (s)=12092.14864.42=11227.72 kg

Number of moles:

255.85
(+3 16)=5.41 kgmol
Fe2 O3 (s)=864.42/
N O 3 3 .9 H 2 O( s)=2 5.41=10.83 kgmol
Fe
Amount of iron nitrate:

N O3 3 .9 H 2 O(s)=10.83 M .W .=10.83 404.06=4374.17 kg

Fe
Total Feed:

11227.72+4374.17=15601.89 kg
Amount of ethanol:
The recipe used by Mauron et al., 2003, specifies an amount of 200ml of ethanol
per batch.

25+9.19
() 15601.89=91265.84 L=72008.75 kg
200/
ethanol (l , g)=
Amount of by-products:

water ( g)=( 9 10.83 ) ( 2 1.01+16.00 )=1755.69 kg

NO2 (g)=( 3 10.83 ) (14.01+2 16.01 ) =1494.25 kg
77

Mass Balance Matrix

Catalyst Prep
Balance

Known Values

Impurities consist of amorphous carbon,

Fe2O3, and MgO

Mass product

5000 kg

Amorphous Carbon

1%

Mass CNT

4750 kg

Amorphous Carbon

122.14 Kg

Assume all carbon

is CNT:

Fe(5%) or
MgO(95%)

Yield

28%

Catalyst

12092.
14 kg

Unpurified Mass

Fe2O3

864.42 kg

M.W.

MgO

11227.
72 kg

Fe

55.85

12.01

16.00

Mg

24.31

Iron Oxide
Iron Nitrate

5.41 kg mol
10.83 kg mol

16964.
29 kg

Mol Wt Iron Nitrate

404.06 g mol-1

14.01

Mass Iron Nitrate

4374.1
7 kg

1.01

Ethanol

46.07

Feed to Cat. Prep

15601.
9 kg

ethanol

91265.
84 L

Catalyst Prep
Balance

ethanol

72008.
75 kg

Fe

604.61

Fe2O3

864.42

Density of ethanol

0.789 kg L-1

5%

Mass Balance
IN

kgmol
e

mass(k
g)

MgO

278.53

11227.

kgmol
e

OUT
water

97.43

mass(k
g)
1755.6
78

72
Fe(NO3)3.9H2O
ethanol

10.83

4374.1
7

NO2

1563.1
3

72008.
75

ethanol
Catalyst:

Total (exclude
ethanol)

15601
.90

32.48

1494.2
5

1563.1
3

72008.
75
12092.
14
15601
.90

79

Terminal Velocity
Assumptions:

The Fe2O3/MgO density is a combination of 95wt% MgO, and 5wt% Fe 2O3.

The particle diameter is 100m.
Assume particle is spherical.
Particle diameters are of homogenous size when entering the fluidised
bed.

Fe2O3/MgO density:

Catalyst density=0.05 5240+0.95 3580=3663 kg m3

Fe2O3/MgO drag coefficient:
3

CD=

4 g d p ( p )
3 2

4 9.81 0.00013 789 ( 3663789 )

=20.59 at =1
3 0.00122

Using figure 2.3 on page 34 of Rhodes 1998, the Re p is determined to be 3.5.

Fe2O3/MgO terminal velocity:

V t=

p
d p

3.5 0.0012
=0.0532m s1
789 0.0001

MgO drag coefficient:

CD=

4 9.81 0.00013 789 ( 3580789 )

=20.00 at =1
3 0.00122

Using figure 2.3 on page 34 of Rhodes 1998, the Re p is determined to be 3.4.

MgO terminal velocity:

V t=

3.4 0.0012
=0.0517 ms1
789 0.0001

80

Terminal Velocity Matrix

Fe2O3/MgO Terminal
Velocity
at Re =
20.59 1

CD
Rep

3.5
0.0532 ms-1

Vt

MgO Terminal
Velocity

Rep

Fe2O3/MgO
Density

3663 kg m-3

MgO Density

3580 kg m-3

Dimension

0.0001 m

Ethanol Viscosity

0.0012 Pa.s

Ethanol Density
at Re =
20.00 1

CD

Constants

Gravity

789 kg m-3
9.81 m s-2

3.4
0.0517 ms-1

Vt

Fluidisation
Assumptions:

The recipe states it takes 20 minutes to produce the mixture, thus it is

assumed that at any point in time, there is 20 minutes worth of catalyst
reactants present.
The particles are all spherical and pack tightly together.
An approximate ratio of 1:3 for radius to height for the column.
The NO2 released in the fluidised bed reactor (FBR) will evaporate from the
reactor solution as its boiling point is 21.1C.
The Fe2O3/MgO will settle to the bottom of the FBR provided the ethanol
flowrate is kept below its terminal settling velocity, and above the MgO
terminal settling velocity.
The minor dilution of the ethanol with water has a negligible effect on the
solution density, and therefore any results using this value. Cross-sectional

Voidage:

( 3 2 )=0.26
=

Pressure drop:

P=

weight of particlesupthrust on particle M B gM B (f / p) g

=
crosssectiononal area
A
81

 P=

( ( 155.94+60.75 ) 9.81 )( 155.94+60.75 ) (792.98 /3663 ) 9.81

0.13

P=13250.48 Pa

Bed height:

H=

P
( 1 ) ( p f ) g

13250.48
=0.64 m
( 10.26 ) ( 3663789 ) 9.81

Minimum fluidisation velocity:

U mf =

( p ) g d 2p
1650

( 3663789 ) 9.81 0.000 12

1

=0.00014 m s
1650 0.0012
Minimum reaction volume:

Volume=bed height area 1000

0.64 0.13 1000=79.94 L

82

Fluidisation Matrix
Fluidisation
Total Mass MgO
Total Volume MgO
Total Mass Fe(NO3)3.9H2O
Total Volume
Fe(NO3)3.9H2O

Total Mass Ethanol

Total Volume Ethanol
Total Mass Water
Total Volume Water
Total Volume

Constants
11227.72 kg day-1

Cross-sectional
Area

3.14 m3 day-1

Radius

4374.17 kg day-1

Gravity

2.60 m day

-1

Density of Water

0.13 m2
0.2 m
9.81 m s-2
kg
1000 m-3

72008.75 kg day-1

Density of Ethanol

kg
789 m-3

91.27 m3 day-1

Fe2O3/MgO Density

kg
3663 m-3

1755.69 kg day-1
3

1.76 m day

-1

98.76 m3 day-1

Dimension

0.0001 m

Ethanol Viscosity

1.20E03 Pa.s

Voidage

0.26

Temperature

21.1 C

20 minute Fluidisation
Total Mass MgO

155.9405 kg
56 20mins-1

Water-Ethanol
Mixture

Total Volume MgO

m3
0.043559 20mins-1

Water

Total Mass Fe(NO3)3.9H2O

60.75236 kg
1 20mins-1

Ethanol

Total Volume
Fe(NO3)3.9H2O

m3
0.036162 20mins-1

Density

Total Mass Ethanol

1000.121 kg
528 20mins-1

Total Volume Ethanol

m3
1.267581 20mins-1

Total Mass Water

24.38455 kg
8 20mins-1

Total Volume Water

m3
0.024385 20mins-1

1.89%
98.11%

kg
792.98 m-3

83

Total Volume

m3
1.37169 20mins-1

Total Reactant Volume

1371.69 L 20mins-1

Pressure Drop

Bed Height

Min Fluidisation
Velocity
Minimum Reaction
Volume

13250.48 Pa

0.64 M

0.00014 m s-1
79.94 L

84

Slurry
Assumptions:

The dilution of the ethanol with a minor amount of water has negligible
effects on the viscosity, density, and therefore any results using this value.

Volume fraction:

C v=

( volume particles )
volume particles+ volume liquid

0.000038
=0.0323
000038+001143

Mixture density:

m=Cv p +(1C v ) f
3
0.0323 3663+ ( 10.0323 ) 789=881.96 kg m

Slurry viscosity:

s = f ( 1+2.5 C v )=0.0012 (1+2.5 0.0323 )=0.0013 Pa s

Reynolds number:

UD 881.96 0.001181 0.1

=
=80.3

0.0013

Archimedes number:

4
d
(
3)
Ar =

3
p

f ( p f ) g
s

( 43 ) 0.000 1 789 ( 3663789) 9.81 =17.63

3

0.0013 2

F value:
0.4

0.4

F=0.197 A r =0.197 17.6 3 =0.621

Critical Deposition:

Vc=F gD

p
1
f

)
85

0.621 9.81 0.001

1 )=0.037 ms
( 3663
789

Change in pressure velocity relationship:

P 32 U
=
L
d p2

32 0.0013 0.0376
=0.156 Pam1
2
0.1

Slurry Matrix

Slurry

Constants

Volume Ethanol/water

0.0011 m3 s43 1

Fe2O3/MgO
Density

Volume Particles

0.0000 m3 s38 1

Ethanol
Density

Volume Fraction

0.0323

Ethanol
Viscosity

Mixture Density

kg
881.96 m-3

Slurry Viscosity
Reynolds numer

kg
789 m-3
0.0012 Pa s
m s-

Fe2O3/MgO Vt

0.0013 Pa s
80.3

Flowrate
Pipe Diameter
Cross-sectional
Area

Archimedes Number

kg
3663 m-3

17.63

Velocity

0.053

0.00118 m3
1 s-1
0.1 m
0.0314 m2
0.03760 m s3 1
m s-

F
Critical Deposition
Velocity

P Velocity
relationship

0.621
0.037 m s

Gravity
-1

Particle
Diamter

9.81

0.0001 m

0.1560 Pa
69 m-1

86

Hydrocyclones
Assumptions:

A low flow, high efficiency Stairmand hydrocyclone is used.

The hydrocyclone operates at 90% efficiency.

Equiprobable cut diameter and collection efficiency:

Using goalseek, the collection efficiency was set to 90% and the resulting
equiprobable cut diameter was found using this equation:

(d p)=

1
d
1 + 50
dp

( )

A d p of 0.0001m witha 90 cut efficiency requires d 50=0.000033m

Hydrocyclone body diameter (both U and D are unknown):

d 50
( 2 p 4 Q )/(18 St )
D=3
18 0.0013 0.00014
(0.000033 3663 4 0.001181)/( )=0.12 m
D= 3
2

Characteristic velocity:

U=

4Q
D

4 0.001181
1
=0.099 m s
0.12

Pressure drop:

P=Eu(( f U 2)/2)
320((889.326 0.0992 )/2)=1405 Pa
Exit areas and volumes calculated by applying the ratios of the dimensions
relative to the diameter to the coarse and fine exit of the hydrocyclone, E and N
respectively.

87

Hydrocyclone Matrix

Hydrocyclone

Constants

Hydrocyclone
Body Diameter

Flowrate

0.00118 m3 s1 1

Mixture Density

kg
889.326 m-3

Characteristic
Velocity
Pressure Drop
d50
- collection
efficiency

0.12 m
0.099 m s-1
1405.77 Pa
0.000033 m

90.00%

Slurry Viscosity

0.0013 Pa s

dp

0.0001 m

Eu

320

St50

0.00014

Exit Areas

Volume
Ethanol/water

0.00107 m3 s7 1

0.0119 m2

Volume
Particles

0.00003 m3 s8 1

0.0067 m

N percentage area

64%

E percentage area

36%

Ethanol Density
Fe2O3/MgO
Density

kg
789 m-3
kg
3663 m-3

Exit Volumes
N Exit Fe2O3/MgO

0.000003
8 m3 s-1

N Exit
Ethanol/water

0.000689
216 m3 s-1

N Total

0.000693
0 m3 s-1

E Exit Fe2O3/MgO

0.000034
4 m3 s-1

E Exit
Ethanol/water

0.000387
684 m3 s-1

E Total

0.000422
1 m3 s-1
88

Dimensions relative to diameter (D) in

metres
Hydrocycl
one type
Stairmand
, H.E.
Final

2.5

0.5

0.3
75

0.5

0.2

0.5

0.5

0.4
02

0.2
51

0.0
50

0.0
38

0.0
50

0.0
20

0.0
50

0.0
50

89

Drying
Assumptions:

Initial temperature is 21.1C.

The heat capacity of the Fe2O3/MgO is the equivalent to the heat capacity
of MgO.
Only Fe2O3/MgO is left after the drying process.

Energy equation:

Q=m C p T + H vap
Dryer
Water:

Q=0.00779 4.187 78.9+0.00779 2257=20.15 kj s1

Ethanol:
1

Q=0.31892 2.440 57.3+ 0.31892 846=314.40 kj s

Fe2O3/MgO:

Q=0.12454 0.877 78.9=8.62 kj s1

Total:

Total dryer power requirement=343.16 kW

Distillation
Water:

Q=0.01383 4.187 78.9+0.01383 2257=35.80 kj s1

Ethanol:
1

Q=0.56663 2.440 78.9+ 0.56663 846=558.89 kj s

Fe2O3/MgO:

Q=0.01392 0.877 78.9=0.96 kj s1

Total:

Total distillation power requirement =595.35 kW

Total drying power requirement=343.16+ 595.35=938.52 kW

90

Drying Matrix

Consta
nts

Drying
Q = mCpT +
Hvap
Dryer
(E)

Distillatio
n(N)

Water
mCpT
Hvap
Q

2.57
17.57
20.15

-1

4.57 kj s

-1

31.23 kj s

-1

35.80 kj s

Density of
Water

1000 kg m-3

Density of
Ethanol

789 kg m-3

Density
Fe2O3/MgO

3663 kg m-3
kj kg-1 K-

Cp Ethanol

kj kg-1 KCp Water

4.187

kj kg-1 KCp Fe2O3/MgO

B.P.
Water@1bar
B.P.
Ethanol@1bar

Ethanol

2.440

79.22 kj s-1 Hvap Ethanol

mCpT

44.59

Hvap

269.8
1

479.37 kj s-1 Hvap Water

314.4
0

558.59 kj s-1

mCpT

8.62

0.96 kj s-1

8.62

0.96 kj s-1

0.877

373 K
351.4 K
846 kj kg-1
2257 kj kg-1

Fe2O3/MgO

Q Total

343.1
6

System Total

938.5
2 kW

595.35 kW

91

Dryer(E
)

Distillatio
n(N)

Fe2O3/MgO

0.00003
40

0.0000038 m3 s-1

Ethanol/water

0.00041
20

0.0007320 m3 s-1

Ethanol

0.00040
42

0.0007182 m3 s-1

Water

0.00000
78

0.0000138 m3 s-1

Mass Ethanol

0.31892

0.56663 kg s-1

Mass Water

0.00779

0.01383 kg s-1

Mass Fe2O3/MgO

0.12454

0.01392 kg s-1

92

CITATION Mau03 \l 3081 (Jun & Harris, 2008)

CITATION Mau03 \l 3081 (Brandt. A Varco Corperation, 2004)
CITATION Mau03 \l 3081
CITATION Mau03 \l 3081 C&R v2
CITATION Mau03 \l 3081 (Jun & Harris, 2008)
CITATION Jun08 \l 3081 (Mauron, Emmenegger, Sudan, Wenger, Rentsch, & Zuttel,
Fluidised-bed CVD synthesis of carbon nanotubes on Fe2O3/MgO, 2003)
CITATION Mau03 \l 3081 FIND SOURCE
CITATION Mau03 \l 3081