Bicol University

College of Engineering
DEPARTMENT OF CHEMICAL
ENGINEERING
Legazpi City

Reactor Design for the Production of Nitrocellulose

from the Nitration of Cellulose
Monforte, Angela Louise D.
BS Chemical Engineering March 2015
ABSTRACT
Nitrocellulose is cotton like polymers derived from cellulose treated with nitric and sulfuric acids
and used in the manufacture of explosives, lacquers , plastics, and solid monopropellants The experiment
f
H 2 SO 4 and HNO3 and to design
aimed to kinetically determine the rate of reaction of the mixture of
a suitable reactor for this type of reaction. At 4 minute interval for 20 minutes a sample 0f 15 mL of
titrated. The rate constant obtained was 0.00004 min

+
H is

. Since the rate order and rate constant were

determined, the rate of reaction was calculated. The designed reactor has conversion of 0.02% after 19
1. Introduction
Nitrocellulose also known as cellulose nitrate,
flash paper, flash cotton, guncotton, flash string
is a highly flammable compound formed by
nitrating cellulose through exposure to nitric
acid or another powerful nitrating agent. When
used as a propellant or low-order explosive, it
was originally known as guncotton. [1]
Cellulose is a naturally occurring polymer
obtained from wood pulp or the short fiber
(linters) that adhere to cotton seeds. It consists
of repeating glucose units that have the chemical
formula

C6 H 7 O2 ( OH )3

molecular structure:

and the following

Highly nitrated cellulosei.e., nitrocellulose

containing more than approximately 12.5
percent nitrogenwill dry to a fluffy white
substance known variously as pyrocellulose and
guncotton. Guncotton is unstable to heat, and
even carefully prepared samples will ignite on a
brief heating to temperatures in excess of 150 C
(300 F). Guncotton is employed in gunpowders,
solid rocket propellants, and explosives.
In the commercial manufacture of nitrocellulose,
wood pulp is the primary of cellulose. Cellulose
sheet and nitrating acids are fed into a reacting
vessel, where nitration proceeds until the acids
have been centrifuged from the nitrated product.
Remaining acid is removed by washing the
nitrocellulose slurry in water and boiling it in a
caustic solution. The product is often treated
with various stabilizers to reduce degradation
under exposure to light and heat. In order to

reduce the likelihood of combustion,

nitrocellulose is usually stored and transported
in water or alcohol. [2]
The purpose of this study is to create an ideal
reactor design for the formation of nitrocellulose
from the nitrating the cellulose. Kinetic data will
be gathered from experimentation and the most
suited reactor design will be considered.

The cotton is then allowed to be left in the

mixture for 20 minutes with occasional stirring.
To stabilize the material after nitration the acid
is to be removed completely. The cotton ball is
washed first with distilled

H 2 O , then with

NaHCO3 solution until

200mL 1 M of

bubbling is no longer observed, then with

H 2 O again.
2. Materials and Methods
2.1 Materials
Mixture of Sulfuric Acid

Nitric Acid

HNO
( 3)

(H 2 SO 4 )

and

is used in the nitration of

cellulose in the form of cotton. The experiment

also used sodium bicarbonate

NaHCO
( 3)

and

distilled water. In the titration process of the

mixture of the two acids, sodium hydroxide

( NaOH )

and

water

was

used.

To determine the reaction rate of the reaction the

optimum time set is 20 minutes. For every 4
minutes a sample of the solution was being
gathered to be titrated. Five samples were
gathered within the optimum time set. Each
sample gathered is to be titrated. The titration
process begins with the preparation of 50mL of
0.1 M

NaOH

by diluting 0.2 g of solid

NaOH with 50 mL of distilled water. 15 mL of

the mixture of acid was placed in a beaker and 3
drops of phenolphthalein were also added. With
the use of the buret,

NaOH

was dropped to

the mixture of acid while it is being stirred. The

end point of the solution was determined when
the color changed into pale pink.

Phenolphthalein was also used as indicator in

the titration.
3. Results and Discussion
2.2 Procedure

3.1 Experimental Data

First 140mL of concentrated

H 2 SO 4

(98% wt volume) was mixed with 60mL of

concentrated

The obtained end points in the titration of the

mixture of acid were as follows:

HNO3 (65% wt volume) in a

250 mL beaker with the use of magnetic stirrer

in an ice bath. Monitoring its temperature should
not increase to more than 18 C. The mixture is
then cooled in room temperature then 0.5 g of
cotton was dropped in the mixture. The cotton
was tamped down with the use of a stirring rod.

Time (min)

mL of

4
8
12
16

7.6
7.5
7.1
6.9

NaOH

20

6.5

Table 1. Time of reaction and mL of

NaOH used

+
HA

From the total number of moles of

which is 3.4 the reacted

+
H

is subtracted

giving the number of unreacted H

7.5

. Data

were as follows:

7
mL of NaOH

6.5

Time (min)

Reacted

6
5.5
0

4
8
12
16
20

5 10 15 20 25

Figure 1. mL of NaOH vs time

Assigning the mixture of

HNO 3 as
titrated vs

H 2 SO 4

and

+
H (mol)

0.00065
0.00069
0.00071
0.00075
0.00076

3.39935
3.39931
3.39929
3.39925
3.39924

Table 3. Reacted and unreacted

+
H

NaOH .

concentration of NaOH

vol NaOH
(mL)
6.5
6.9
7.1
7.5
7.6

Table 2. Volume of

+
H

From the number of unreacted moles of

+
H is computed. Data

Concentration of

vol of NaOH
1000

Unreacted
Time
(min)

mol NaOH
0.00065
0.00069
0.00071
0.00075
0.00076

NaOH used converted into

moles

the concentration of
were as follows:

moles. Data is as follows:

4
8
12
16
20

+
H (mol)

+
HA and considered as one acid

From the given volume of NaOH , convert to

Time (min)

Unreacted

4
8
12
16
20

+
H

unreacted

+
H

(mol)

( molL )

3.39935
3.39931
3.39929
3.39925
3.39924

16.99675
16.99655
16.99645
16.99625
16.9962

Table 4. Unreacted

+
H and its concentration

zero order

3.2 Tests for Order of Reaction

17

In order to know the order of the reaction of

+
HA the data given was plotted against time.

Ca

17
17
17
17
17
zero

f(x) = - 0x + 17
R = 0.97

order

Linear (zero order)

17
17
17
17

3.2.1 Fit test to Zero Order

For a zero order reaction:

10 12 14 16 18 20 22

dCA
=k
dt

Figure 2. Plot of t versus Ca

C A =kt +C AO
k=
Time is plotted against

CA

and the order is

checked if the reaction is valid for zero order.

Time
(s)

concentration
of

+
H

Zero order (

CA )

(C A )
16.99675
16.99655
16.99645
16.99625
16.9962

R =0.9703
3.2.2 Fit size to First Order
For a first order reaction:

d C BA
=k C A
dt

unreacted

4
8
12
16
20

4E-05 L
mol(s)

16.99675
16.99655
16.99645
16.99625
16.9962

dA
=kdt
CA
ln C A =kt+ lnC Ao

Table 5. Kinetic data for a zero order reaction of

+
H

ln C A

is graphed against time to test the

validity of the reaction at first order reaction in

+
H .
Time
(s)

Unreacted

+
H

CA )

First Order
(

ln C A )

4
16.99675
8
16.99655
12
16.99645
16
16.99625
20
16.9962

2.8330221
49
2.8330103
82
2.8330044
99
2.8329927
31
2.8329897
9

Table 6. Kinetic data for a first order reaction of

+
H

C2A

=kdt

1
1
=kdt+
CA
C Ao
Time is plotted against

1/C A

Unreacted

+
H

16.99675
8

2.83

f(x) = - 0x + 2.83
R = 0.97

2.83
2.83

16.99655
first order
Linear (first
order)

2.83
2.83

12
16.99645
16
16.99625
20

2.83
0 5 10152025

Second
Order (

CA )

2.83

and the plot is

checked if the reaction follows a second order

reaction.
Time
(s)

first order

ln Ca

dCA

16.9962

1/C A )
0.0588347
77
0.0588354
7
0.0588358
16
0.0588365
08
0.0588366
81

Table 7. Kinetic data for a second order reaction of

+
H

Figure 3. Plot of t versus ln Ca

k=

2E-06 L
mol( s)

R2= 0.9694

second order
0.06
0.06

f(x) = 0x + 0.06
R = 0.9

0.06

3.2.3 Fit test to Second Order

For a second order reaction:

dCA
=k C 2B
dt

0.06

1/Ca

second order
Linear
(second
order)

0.06
0.06
0.06
0.06
0

10 20 30

Figure 4. Plot of t versus 1/ Ca

k=

8
0.00022352
9

20

1E-07 L
mol(s)

R = 0.9

Table 8. Conversion of

Comparing the

R2 from the three orders, the

of the zero order is nearest to one, this

means that the data obtained for the zero order

reaction are closest to the regression line of the
order compared to the other order therefore the
order of reaction at

+
H

is most possible at

zero order.
3.3 Reactor Sizing
Continuous Stirred Tank Reactor or CSTR is the
reactor to be used in this reaction. CSTR is used
when agitation is required. It runs at steady state
with continuous flow of reactants and products;
the feed assumes a uniform composition
throughout the reactor, exit stream has the same
composition as in the tank. [3]
Given

rA

as a function of conversion, one

can size a reactor. For this reaction the fractional

conversion is acquired using the formula
+original

(1)

moles H
+reacted
H
moles

x A =

Time (mins)

XA

0.00019117
6
0.00020294
1
0.00020882
4
0.00022058

8
12
16

+
H

Obtaining the reactor volume for each

conversion the below formula is to be used.
(2)

V CSTR =

F Ao x A
r A

Assuming that the molar flow rate of the feed is

500 moles per minute, the volume of the reactor
was obtained for each fractional conversion. The
data below were as follows:
Time
(mins)
4
8
12
16
20

XA
0.000191176
0.00020294
1
0.00020882
4
0.00022058
8
0.00022352
9

Reactor Volume
(L)
2389.705882
2536.764706
2610.294118
2757.352941
2794.117647

Table 9. Volume of the reactor for each conversion

Space time was also determined using equation

4. Volumetric flow rate is first determined using
equation 3. Space time is defined as the time
necessary to process one reactor volume, given a
set of particular initial conditions.

(3)

(4)

vo =

F Ao
C Ao
space time ( )=

V
vo

XA

Time
(mins)

Vo

Space
Time

( )
0.000191
176
0.000202
941
0.000208
824
0.000220
588
0.000223
529

4
8
12
16
20

147.058
8
147.058
8
147.058
8
147.058
8
147.058
8

16.25

[4] Geankoplis, C., 1993, Transport processes

and unit operations, 3rd edition, Prentice-Hall
International, Inc., New Jersey.
[5] Levenspiel, O., 1999, Chemical Reaction
Engineering, 3rd edition, Phoenix Color
Corporation, Maryland.

17.25
17.75

Figures

18.75

Figure 1. mL of NaOH vs time

19

Figure 2. Plot of t versus Ca

Table 10. Space time for each conversion

Figure 3. Plot of t versus ln Ca

The data gathered were interpreted as

for the reaction to proceed to a conversion of
0.02%, 2794.12 L rounding up and giving some
allowance to the volume, the CSTR volume
should be 2800 L. It is also stated that for 0.02%
conversion, the space time or the time needed to
process one reactor volume is 19 minutes.

Figure 4. Plot of t versus 1/ Ca

Tables
Table 1. Time of reaction and mL of
Table 2. Volume of

4. Conclusion
The designed Continuous Stirred Tank Reactor
is useful when agitation is required in a
continuous operation. CSTR easily adapts to two
phase runs. CSTR however has the lowest
conversion per unit volume. But overall, the
designed reactor can be considered efficient.
References
[1] WIKIPEDIA, Nitrocellulose, viewed 17
March 2015 from http://en.wikipedia.org/wiki/
[2]
ENCYCLOPEDIA
BRITANNICA,
Nitrocellulose, viewed 16 March 2015 from
http://www.britannica.com/
[3] UMICH, CSTR, viewed 16 March 2015 from
http://www.umich.edu/

NaOH used

NaOH used converted into

moles
Table 3. Reacted and unreacted

Table 4. Unreacted

+
H

+
H and its concentration

Table 5. Kinetic data for a zero order reaction of

+
H

Table 6. Kinetic data for a first order reaction of

+
H
Table 7. Kinetic data for a second order reaction of

+
H

Table 8. Conversion of

+
H

Table 9. Volume of the reactor for each conversion

Table 10. Space time for each conversion