optimization of microcrystalline cellulose production from groundnuts husk

OPTIMIZATION OF PROCESS PARAMETERS
FOR PHARMACEUTICAL GRADE
MICROCRYSTALLINE CELLULOSE (MCC)
PRODUCTION FROM
GROUNDNUT HUSK (GH)
MSc. RESEARCH FINAL DEFENCE
BY
HASSANA GWANDI AUDU
P14EGCE8044
DEPARTMENT OF CHEMICAL ENGINEERING
AHMADU BELLO UNIVERSITY, ZARIA
APRIL, 2020
1

OUTLINE
INTRODUCTION
LITERATURE SURVEY
PROBLEM STATEMENTS
AIM AND OBJECTIVES
JUSTIFICATION
SCOPE
MATERIALS AND METHODOLOGY
DISCUSSION OF RESULTS
REFERENCES
2

INTRODUCTION
Microcrystalline Cellulose is purified, partially depolymerized cellulose
prepared by treating alpha cellulose, obtained as a pulp from fibrous plant
material with mineral acids.
Types of cellulose
There are three types of cellulose:
1. Alpha cellulose
2. Beta cellulose
3. Gamma cellulose
3

4
INTRODUCTION CONT’D
Microcrystalline cellulose obtained from both soft and hard wood differ in
chemical composition:
 Cellulose,
 Hemicellulose
 Lignin
 Structural organization
Table 1: Groundnut husk chemical composition
(Lakshunmu, 2013)
4
CELLULOSE,
wt %
HEMICELLULOSE,
wt %
LIGNIN ,
wt %
ASH,
wt %
37.5-40.5 14.7-18.7 26.4-30.2 0.4-5.9

SOURCES
Sources of cellulose and its derivatives obtained from Agricultural waste are:
 Cotton linters
 Rice husk
 Corn cob
 Groundnut husk
 Sugar cane bagasse
 Calabash
 Bark of palm nut trees and so on (Chukwuemeka, 2012).
5

APPLICATION
Cosmetic, pharmaceutical, food and other industry uses microcrystalline
celluloses as:
 Fat substitute
 Stabilizer
 Thickener
 Filler-binder
 Anticaking agent
 Adsorbent (Matrosovich et al, 2006)
 Plaque tests for counting viruses
 Alternative to carboxymethyl cellulose (Hindi, 2016).
6

7
Process Description
 Alkali Treatment (Sodium hydroxide) : To remove fats and oils, and lignin.
 Acid Hydrolysis (Nitric acid with ethanol) : to remove traces of lignin in the
form of soluble nitrolignins and complete removal of hemicellulose.
 Bleaching with sodium hypochlorite : To obtain white colour.

8
Grades of Microcrystalline Cellulose
MCC are of different particle size, moisture contents, flow, and physical properties
because of the pulp used as raw material and different process conditions.
Different trade names for final product such as: Avicel®: PH 101, PH 102, PH
103, PH 105, PH 113
Vivapur®: 101, 102, 12
Emcocel® 50M, 90M, LP200
Comprecel®: CP- 101, CP 102
Microcel®: MC-102, MC-200,MC- 205 (Glicher, 2005)

9
Percentage Yield of MCC:
Percent yield (%) of MCC=
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑜𝑣𝑒𝑛 𝑑𝑟𝑖𝑒𝑑 𝑓𝑟𝑒𝑒 𝑙𝑖𝑔𝑛𝑖𝑛 (𝑝𝑢𝑟𝑒 𝑐𝑒𝑙𝑙𝑢𝑙𝑜𝑠𝑒)
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑜𝑣𝑒𝑛 𝑑𝑟𝑖𝑒𝑑 𝑟𝑎𝑤 𝑠𝑎𝑚𝑝𝑙𝑒
* 100%
.....(1)
Crystallinity of MCC :
CrI=
𝐼002
−𝐼𝑎𝑚
𝐼002
* 100% .............(2)
Where CrI= crystalline index
I002= maximum intensity of the (002) maximum intensity of the principal peak (at
22.4° of 2θ)
Iam = intensity diffraction attributed to amorphous cellulose (at 15.4° of 2θ)

10
AUTHOR TITLE CONCLUSION REMARKS
Frank et al.
(2009)
Processing
pharmaceutical grade
microcrystalline cellulose
from groundnut husk:
Extraction methods and
characterization
The results showed complete pulping was
achieved by multistage pulping method
given 15% yield. This concludes that
GH-MCC compared favourably with
commercial-grade MCC and conforms to
specifications for MCC in the British
pharmacopoeia.
Effect of process
parameters were not
studied
John et al.
(2011)
Evaluation of several
microcrystalline
celluloses obtained from
agricultural by-products
MCC obtained from rice husk, sugar cane
bagasse, corn cob, and cotton are use as
direct compression agent. The results
offer an inexpensive and a simple method
to produce MCC for use in the
manufacture of solid dosage forms.
Effect of process
parameters were not
studied and groundnut
husk was not
considered.
LITERATURE SURVEY CONT’D
Table 2: Previous Related Research

11
Chukwuemeka
et al.
(2012)
Investigation of physico
technical, spectroscopic and
thermo gravimetric
properties of powdered
cellulose and
microcrystalline cellulose
derived from groundnut
shells
XRD and FTIR spectra analysis showed α-
cellulose had lower crystallinity due to
treatment with 2N hydrochloric acid which
increase the crystallinity index. The physical
properties of microcrystalline celluloses have
better flow properties than the α-cellulose
Effect of
process
parameters
were not
studied
Sirikalaya et al.
(2013)
Optimization of Micro
Crystalline Cellulose
Production
from Corn Cob for
Pharmaceutical Industry
Investment
The degree of crystallinity of alkaline degradation,
bleaching and hydrolysis at 10% of NaOH 95 °C for
2h, NaClO2 1.5 g 10% of C2H4O2 0.5 mL 70 °C for
2h, 2N of HCl, 105 °C for 60 min showed maximum
crystallinity of 77.07%, 75.98% and 86.84%,
respectively. The crystallinity and morphology of
the MCC corresponded to Avicel PH 101. The
investment of the plant will break even over 6 years.
• RSM can be
used for
optimsation
of process
parameters.
• It’s a viable
business.

12
Rani et al.
(2016)
Isolation of
microcrystalline
cellulose and nano
cellulose from peanut
shells
The FTIR spectra indicated extensive removal of
hemicellulose and lignin. XRD pattern showed
that the isolated MCC is crystalline in nature
Effect of process
parameters were
not studied

13
PROBLEM STATEMENT
Optimisation of Microcrystalline Cellulose Production from Corn Cob has been
reported but optimisation MCC from groundnut husk was not reported.

JUSTIFICATION
This research work will establish the following:
1. Production of microcrystalline cellulose with optimum quality for
pharmaceutical applications.
2. Availability of raw material in Northern Nigeria which can substitute wood
pulp and also serve as second income for farmers.
3. Nigeria produce about 3.8 million metric tonnes per annum of Groundnut husk
as an agricultural waste, however, if not used it will becomes abandon
resource.
4. Further production of MCC will reduce dependence on importation.
14

AIM AND OBJECTIVE
Research Aim (s):
This research aims to study the effect of process parameters on
Microcrystalline Cellulose production from Groundnut Husk.
Objective:
The objectives of this research is :
1. To Collect, identify and characterize type of groundnut husk.
2. To select the effect of particle size for the production of
microcrystalline cellulose.
3. To use design expert to study the effect of process parameters: such
as concentration, temperature, time on the production of
microcrystalline cellulose.
4. To characterize the microcrystalline cellulose produced. 15

16
SCOPE OF THE WORK
The scope of this work will cover:
1. To study the effect of particle size of the groundnut husk microcrystalline
cellulose.
2. To study the effects of concentration sodium hydroxide (0.25-0.9 g),
temperature (80-980C) and time (1-2 hr) on the alkali treatment process using
RSM.
3. To study the effect of Nitric acid to ethanol ratio (4-18.7), temperature (81.5-
98.40C) and time (0.5-2.5 hr) on multistage pulping using RSM.
4. To characterize microcrystalline cellulose using pH meter, pycnometer,
scanning electron microscopy (SEM), Fourier-transform infra-red spectra
(FTIR) and X-ray diﬀractometer (XRD)

17
MATERIALS AND METHODOLOGY
List of Material
The material required includes:
 Groundnut Husk- Arachis hypogaea
 Ethanol-70% JHD, China
 Nitric Acid-69% MERCK, Germany
 Sodium Hydroxide- 98% AR, India
 Sodium Hypochloride- 3.5%, Nigeria
 Distilled Water

18
MATERIALAND METHODOLOGY CONT’D
Table 3: List of Equipment
S/NO EQUIPMENT MODEL TYPE LOCATION OF LABORATORY
1. X-ray Diffractometer Rigaku Miniflex, China Beijing Research Institute of Chemical Industry, China
2. Scanning Electron Microscopy S4800 Hitachi, China Beijing Research Institute of Chemical Industry, China
3. Fourier-Transform Infra-red
Radiometer
Shimadzu FTIR-8400S Japan National Research Institute for Chemical Technology, Zaria
4. pH meter Corning, model 10 England A.B.U Chemical Engineering Department, Zaria
6. Pyconometer England A.B.U Chemical Engineering Department, Zaria
7. Dryer DH-9140 Dongguan HongTuo
Instrument
A.B.U Chemical Engineering Department, Zaria
8. Sieves Shaker Endecotts Ltd London
England
A.B.U Civil Engineering Department, Zaria
9. Pulverizer Jas Model TW-MP-4 A.B.U Chemical Engineering Department, Zaria
10. Erlenmeyer flask
Beakers and Cylinders
England A.B.U Chemical Engineering Department, Zaria
11. Thermostatic water Bath HH. S6 USA A.B.U Chemical Engineering Department, Zaria
12. Computer System Predictive Analytical Software
version 22 (PASW, USA)
A.B.U. Department of Mathematics, Zaria

METHODOLOGY
Process Flow Chart: Microcrystalline cellulose process from groundnut husk
Sample collection
and identification (Groundnut Husk)
Figure 1: Process flow chart for Microcrystalline production 19
Washing and filtration
Drying at Room
Temperature Alkali Method
(RSM) Parameters:
1. Time
2. Temperature
3. Concentration
Washing
Characterization using
proximate analysis
Multistage pulping (Hydrolysis)
(RSM) Parameters: conc, time, tempt
Step 1:HNO3 + C2H5OH
Bleaching NaClO (conc, time,tempt)
Characterization of Microcrystalline cellulose : FTIR, XRD,
SEM, physicochemical properties
Washing and Filtration
Washing and Filtration
Selection of
particle sizes
Drying at 60°C for 4hr
Drying at 60°C for 4hr

RESULTS AND DISCUSSION
20
Table 4: Identification of Groundnut Husk
Table 5: Proximate Properties of untreated Groundnut husk
Kingdom: Plantae
Family: Fabaceae
Subfamily: Papilionaceae
Genus: Arachis
Species: Arachis hypogaea
Binomial name Arachis hypogaea
CELLULOSE
wt %
HEMICELLULOSE
wt %
LIGNIN
wt %
ASH
wt %
48.4 17.9 25.7 6.1

21
Sample ID Particle sizes (mm)
F1 3.35
F2 2.80
F3 2.36
F4 2.00
F5 1.70
F6 1.40
F7 1.19
F8 1.18
F9 1.00
F10 0.560
F11 0.500
F12 0.425
F13 0.212
Table 6: Selected Particle sizes of untreated Groundnut
husk

22
Sample
ID
Powder property of Avicel PH101, untreated GH and treated GH
Particle
Size
(µm)
Bulk
density
(g/cm3)
Tap
density
(g/cm3)
True
density
(g/cm3)
Carr’s
Index
Hausne
r ratio
Angle
of
repose
Percentage
yield
microcryst
alline
cellulose
%
Porosity
(%)
pH Crystallinity
index
(%)
F11 500 0.163 0.185 0.811 11.89 1.14 39.11 56 78.97 5.8 91
F9 1000 0.163 0.185 0.877 11.89 1.14 32.72 52 78.90 5.8 89
F12 425 0.163 0.185 0.877 11.89 1.14 33.68 48 78.91 5.8 92
F6 1400 0.163 0.185 0.874 11.89 1.14 32.57 44 78.84 5.8 88
Table 7: The Summary of the favourable results of the GH-MCC

23
Table 8: The Actual Design of the Experiment and Results of Percentage Yield and Percentage Purity of the Alpha
Cellulose
ACTUAL DESIGN
Std Factor 1
A:Time
(hr)
Factor 2
B:Temperature
(0C)
Factor 3
C:
Concentration (g/750ml)
Response 1 Percentage Yield of
Alpha Cellulose (%)
Response 2 Percentage Purity of
Alpha Cellulose (%)
1 1.00 80.00 0.25 78 45.68
2 2.00 80.00 0.25 70 43.57
3 1.00 98.00 0.25 73 47.8
4 2.00 98.00 0.25 74 44.65
5 1.00 80.00 0.90 80 43.3
6 2.00 80.00 0.90 75 44.98
7 1.00 98.00 0.90 70 35.85
8 2.00 98.00 0.90 75 53.2
9 0.66 89.00 0.57 73 45.45
10 2.34 89.00 0.57 68 47.86
11 1.50 73.86 0.57 75 39.3
12 1.50 104.14 0.57 76 38.08
13 1.50 89.00 0.03 74 49.32
14 1.50 89.00 1.12 76 43.35
15 1.50 89.00 0.57 73 43.03
16 1.50 89.00 0.57 70 45.66
17 1.50 89.00 0.57 72 46.6
18 1.50 89.00 0.57 72.19 37.65
19 1.50 89.00 0.57 74 50.93
20 1.50 89.00 0.57 73 41.07

DISCUSSION OF RESULTS CONT’D
Constraints
Lower Upper Lower Upper
Name Goal Limit Limit Weight Weight Importance
A:Time is in range 1 2 1 1 3
B:Tempt is in range 80 98 1 1 3
C:Conc is in range 0.25 0.9 1 1 3
percentage
yield
maximize 68 80 1 1 3
percentage
purity
maximize 35.85 53.2 1 1 3
Table 9: Summary of Factors input and the Responses of Upper and Lower Limits for Alpha Cellulose
24

25
ANOVA for Response Surface Quadratic model
Analysis of variance table [Partial sum of squares - Type III]
Source
Sum of
Squares
df
Mean
Square
F
Value
p-value
Prob > F
Model 133.26 9 14.81 7.01 0.0027 Significant
A-Time 17.39 1 17.39 8.23 0.0167
B-Tempt 6.36 1 6.36 3.01 0.1135
C-Conc 5.12 1 5.12 2.42 0.1506
AB 45.13 1 45.13 21.35 0.0009
AC 6.13 1 6.13 2.90 0.1195
BC 10.12 1 10.12 4.79 0.0535
A2 4.00 1 4.00 1.89 0.1992
B2 22.20 1 22.20 10.50 0.0089
C2 16.33 1 16.33 7.73 0.0195
Residual 21.14 10 2.11
Lack of Fit 11.90 5 2.38 1.29 0.3939not significant
Pure Error 9.24 5 1.85
Cor Total 154.40 19
Table 10: Statistical Analysis (ANOVA) Analysis of Response for the Percentage Yield of Alpha Cellulose

26
Percentage Yield of Alpha Cellulose:
Percent yield (%) of Alpha Cellulose=
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑜𝑣𝑒𝑛 𝑑𝑟𝑖𝑒𝑑 𝑡𝑟𝑒𝑎𝑡𝑒𝑑 𝑠𝑎𝑚𝑝𝑙𝑒
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑜𝑣𝑒𝑛 𝑑𝑟𝑖𝑒𝑑 𝑢𝑛𝑡𝑟𝑒𝑎𝑡𝑒𝑑 𝑠𝑎𝑚𝑝𝑙𝑒
* 100% ........... (1)
Std.Dev--------- 1.45 R-Square ---------------- 0.8631
Mean --------- 73.56 Adj-Square ------------- 0.7399
C.V. % --------- 1.98 Pred R-Square --------- 0.3276
PRESS --------- 103.82 Adeq Precision -------- 10.196
The Model Equation
Percentage Yield = 72.34
-1.13A - 0.68B + 0.61C + 2.38AB + 0.88AC - 1.12BC - 0.53A2 + 1.24B2 + 1.06C2........... (3)

27
Sum of Mean F p-value
Source Squares df Square Value Prob > F
Model 221.81 9 24.65 1.58 0.2433not significant
A-Time 23.26 1 23.26 1.49 0.2503
B-Tempt 0.27 1 0.27 0.017 0.8981
C-Conc 15.21 1 15.21 0.97 0.3470
AB 26.75 1 26.75 1.71 0.2198
AC 73.75 1 73.75 4.72 0.0549
BC 0.74 1 0.74 0.047 0.8323
A2 17.27 1 17.27 1.11 0.3177
B2 42.71 1 42.71 2.74 0.1292
C2 13.88 1 13.88 0.89 0.3679
Residual 156.14 10 15.61
Lack of Fit 48.90 5 9.78 0.46 0.7955not significant
Pure Error 107.24 5 21.45
Cor Total 377.95 19
Table 11: Statistical Analysis (ANOVA) Analysis of Response for the Percentage Purity of Alpha Cellulose

28
Std.Dev--------- 3.95 R-Square ---------------- 0.5869
Mean --------- 44.37 Adj-Square ------------- 0.2151
C.V. % --------- 8.91 Pred R-Square --------- -0.5360
The Model Equation
Percentage Purity = 44.12
1.13A + 0.14B - 1.06C + 1.83AB + 3.04AC - 0.30BC + 1.09A2 - 1.72B2 + 0.98C2........... (4)

29
DISCUSSION OF RESULTS
CONT’D
b
Design-Expert® Software
percentage purity
Color points by value of
percentage purity:
53.2
35.85
Actual
Predicted
Predicted vs. Actual
35
40
45
50
55
35 40 45 50 55
percentage yield
percentage yield:
80
68
Actual
Predicted
68
70
72
74
76
78
80
68 70 72 74 76 78 80
Figure 2: Plot of Predicted verses Actual on the percentage yield (a) and percentage purity of the alpha cellulose (b)
b
a

30
Figure 3: 3D plot of (a) percentage yield and (b) percentage purity of alpha cellulose
Factor Coding: Actual
percentage yield (%)
80
68
X1 = A: Time
X2 = B: Tempt
Actual Factor
C: Conc = 0.58
80.00
83.00
86.00
89.00
92.00
95.00
98.00
1.00
1.20
1.40
1.60
1.80
2.00
68
70
72
74
76
78
80
percentage
yield
(%)
A: Time (hr)
B: Tempt (0C)
percentage purity (%)
Design points above predicted value
Design points below predicted value
53.2
35.85
X1 = A: Time
X2 = B: Tempt
Actual Factor
C: Conc = 0.57
80.00
83.00
86.00
89.00
92.00
95.00
98.00
1.00
1.20
1.40
1.60
1.80
2
35
40
45
50
55
percentage
purity
(%)
A: Time (h
B: Tempt (0C)
a b

Table 12: Solutions of the optimization of the extraction of Alpha Cellulose
OPTIMIZE SOLUTION OF ALPHA CELLULOSE
Number Time (hr) Tempt (0C)
Conc
(g/ml)
Percentage yield
(%)
Percentage purity
(%)
Desirability
1 1.00 80.00 0.90 79.17 41.07 0.93 Selected
2 1.01 80.00 0.90 79.15 41.07 0.92
3 1.00 80.00 0.89 79.13 41.09 0.92
4 1.02 80.00 0.90 79.11 41.08 0.92
5 1.00 80.08 0.90 79.10 41.08 0.92
6 1.00 80.00 0.89 79.10 41.11 0.92
7 1.02 80.00 0.90 79.09 41.09 0.92
8 1.00 80.14 0.90 79.06 41.09 0.92
9 1.04 80.00 0.90 79.04 41.10 0.92
10 1.00 80.00 0.88 79.04 41.15 0.92
11 1.00 80.00 0.88 79.01 41.17 0.91
12 1.05 80.00 0.90 79.01 41.11 0.91
13 1.00 80.24 0.90 78.98 41.11 0.91
14 1.00 80.00 0.87 78.94 41.22 0.91
15 1.08 80.00 0.90 78.90 41.15 0.90
16 1.00 80.44 0.90 78.84 41.14 0.90
17 1.10 80.00 0.90 78.83 41.18 0.90
18 1.10 80.00 0.90 78.81 41.19 0.90
19 1.00 80.00 0.85 78.80 41.32 0.90
20 1.00 80.63 0.90 78.71 41.16 0.89 31

VALIDATED SOLUTION OF ALPHA CELLULOSE
Number
Time
(hr)
Tempt
(0C)
Conc
(g/ml)
Percentage
yield (%)
Percentage
purity (%)
Desirability
1 1.00 80.00 0.90 76.44 40.89 0.93 Selected
2 1.01 80.00 0.90 76.40 39.75 0.92
3 1.00 80.00 0.89 77.16 38.28 0.92
4 1.02 80.00 0.90 78.60 36.56 0.92
5 1.00 80.08 0.90 76.16 39.13 0.92
Table 13: The validated Solutions of the optimized of Alpha Cellulose
32

MULTI STAGE PULPING
The multi stage pulping method was used to obtain the cellulose from groundnut husk. Central Composite
Design was used to design the experiment and presented in Table 12 showing the responses obtained.
33

Table 14: The Actual Design of the Experiment for the multi stage pulping and the results obtained as the Response of
Percentage Yield and Percentage Purity of the Microcrystalline Cellulose
ACTUAL DESIGN
Std Factor 1
A:Temperature
(0C)
Factor 2
B:Time
(hr)
Factor 3
C:
Concentration (g/750ml)
Response 1 Percentage Yield
of Microcrystalline Cellulose
(%)
Response 2 Percentage
Purity of Microcrystalline
Cellulose (%)
1 85 1 4 62.47 75.27
2 95 1 4 43.68 71
3 85 2.5 4 53.73 83.47
4 95 2.5 4 53.79 70.84
5 85 1 15 61 80.94
6 95 1 15 57.95 86.94
7 85 2.5 15 53.58 82.99
8 95 2.5 15 62.89 85.01
9 81.591 1.75 9.5 62.05 72.62
10 98.409 1.75 9.5 57.95 77.84
11 90 0.488655 9.5 51 89.71
12 90 3.01134 9.5 56.37 85.25
13 90 1.75 0.250139 47.05 66.42
14 90 1.75 18.7499 52.95 78.53
15 90 1.75 9.5 51.42 71.99
16 90 1.75 9.5 53.63 72.01
17 90 1.75 9.5 50.26 80.61
18 90 1.75 9.5 55.68 72.07
19 90 1.75 9.5 54.79 70.78
20 90 1.75 9.5 51.16 73.11
34

Constraints
Lower Upper Lower Upper
Name Goal Limit Limit Weight Weight Importance
A:temp is in range 81.5 98.4 1 1 3
B:time is in range 0.5 2.5 1 1 3
C:ethanol:
nitric
is in range 4 18.7 1 1 3
R1 (%) Yield Maximize 43.68 62.89 1 1 3
R2 (%) Purity Maximize 66.42 89.71 1 1 3
Table 15: Summary of Factors input and the Responses of Upper and Lower Limits for the Multi stage pulping
35

Table 16: Statistical Analysis (ANOVA) Analysis of Response for the Percentage Yield of Microcrystalline Cellulose
Source Squares df Square Value Prob > F
Model 440.32 9 48.92 9.87 0.0007 Significant
A-temp 27.46 1 27.46 5.54 0.0404
B-time 4.59 1 4.59 0.93 0.3585
C-ethanol:
nitric
73.45 1 73.45 14.81 0.0032
AB 121.76 1 121.76 24.55 0.0006
AC 78.06 1 78.06 15.74 0.0027
BC 1.85 1 1.85 0.37 0.5547
A2 116.84 1 116.84 23.56 0.0007
B2 5.44 1 5.44 1.10 0.3194
C2 6.82 1 6.82 1.38 0.2679
Residual 49.59 10 4.96
Lack of Fit 25.60 5 5.12 1.07 0.4723 not significant
Pure Error 23.99 5 4.80
Cor Total 489.91 19
36

In this case A, C, AB, AC, A^2 are significant model terms.
Std.Dev--------- 2.23 R-Square ---------------- 0.8988
Mean --------- 54.67 Adj-Square -------------- 0.8077
C.V. % --------- 4.07 Pred R-Square ---------- 0.5163
The Model Equation
Percentage Yield of MCC (R1) = 52.78
-1.42A + 0.58B + 2.32C + 3.90AB + 3.12AC – 0.48BC + 2.85A2 + 0.61B2 – 0.69C2
37

Source Squares Df Square Value Prob > F
Model 722.07 9 80.23 7.08 0.0026 significant
A-temp 7.476E-004 1 7.476E-004 6.599E-005 0.9937
B-time 0.032 1 0.032 2.809E-003 0.9588
C-ethanol:
nitric
226.90 1 226.90 20.03 0.0012
AB 19.03 1 19.03 1.68 0.2240
AC 77.63 1 77.63 6.85 0.0257
BC 7.84 1 7.84 0.69 0.4249
A2 9.66 1 9.66 0.85 0.3775
B2 382.19 1 382.19 33.74 0.0002
C2 0.35 1 0.35 0.031 0.8644
Residual 113.29 10 11.33
Lack of Fit 48.67 5 9.73 0.75 0.6183 not significant
Pure Error 64.62 5 12.92
Cor Total 835.36 19
Table 17: Statistical Analysis (ANOVA) Analysis of Response for the Percentage Purity of Microcrystalline Cellulose
38

In this case C, AC, B^2 are significant model terms.
Std.Dev--------- 3.37 R-Square ---------------- 0.8644
Mean --------- 77.37 Adj-Square -------------- 0.7423
C.V. % --------- 4.35 Pred R-Square ---------- 0.4417
The Model Equation
Percentage Purity of MCC (R2) = 73.40
-7.399E - 003A + 0.048B + 4.08C - 1.54AB + 3.12AC - 0.99BC + 0.82A2 + 5.15B2 - 0.16C2
39

R2
R2:
89.71
66.42
Actual
Predicted
65
70
75
80
85
90
65 70 75 80 85 90
Figure 4: Plot of Predicted verses Actual on the percentage yield (a) and percentage purity (b) of the cellulose
R1
R1:
62.89
43.68
Actual
Predicted
40
45
50
55
60
65
40 45 50 55 60 65
a b
40

R1 (% yield mcc)
62.89
43.68
X1 = A: temp
X2 = B: time
Actual Factor
C: ethanol: nitric = 9.5
1
1.3
1.6
1.9
2.2
2.5
85
87
89
91
93
95
40
45
50
55
60
65
R1
(%
yield
mcc)
A: temp (0C)
B: time (Hr)
R2 (% mcc purity )
89.71
66.42
X1 = A: temp
X2 = B: time
Actual Factor
C: ethanol: nitric = 9.5
1
1.3
1.6
1.9
2.2
2.5
85
87
89
91
93
95
65
70
75
80
85
90
R2
(%
mcc
purity
)
A: temp (0C)
B: time (Hr)
a b
Figure 5: 3D Plot of percentage yield (a) and percentage purity (b) of the cellulose
41

Number Temperature
(0C)
Time
(hr)
Ethanol:
Nitric
Response 1
Cellulose
Yield (%)
Response 2
Cellulose Purity (%)
Desirability
1 98.36 2.45 18.22 75.06 90.67 1 Selected
2 98.39 2.39 18.43 74.72 90.59 1
3 98.38 2.50 17.34 74.81 89.82 1
4 98.19 2.47 17.72 74.24 89.91 1
5 98.15 2.46 17.89 74.15 90.01 1
6 98.03 2.38 18.66 73.64 90.38 1
7 98.28 2.44 17.67 74.18 89.71 1
8 98.03 2.41 18.31 73.63 90.09 1
9 97.74 2.45 18.52 73.23 90.28 1
Sample
ID
Temperatur
e (0C)
Time
(hr)
Ethanol:
Nitric
Response 1
Cellulose Yield (%)
Response 2
Cellulose Purity
(%)
Desirability
V0 98.36 2.45 18.22 73.79 88.08 1 Selected
Table 18: Solutions of the Optimization of the Microcrystalline Cellulose.
Table 19: The validated Solution of the optimized Microcrystalline Cellulose
42

PARAMETERS GROUNDNUT
HUSK CELLULOSE
Percentage Yield (%) 73.79
Percentage Purity (%) 88.08
Bulk density (gcm-3) 0.216
Tapped density (gcm-3) 0.24
True density (gcm-3) 0.84
Carr’s index (%) 10
Hausner ratio 1.11
Powder porosity (%) 71.32
Angle of repose (°) 32
Particle Size (µm) 500
Table 20: Summary of the Optimal
Parameters of the Groundnut husk
Microcrystalline cellulose
Compressibility index
(per cent)
Flow character Angle of Repose Hausner ratio
1-10 Excellent 25-30 1.00-1.11
11-15 Good 31-35 1.12-1.18
16-20 Fair 36-40 1.19-1.25
21-25 Passable 41-45 1.26-1.34
26-31 Poor 46-55 1.35-1.45
32-37 Very poor 56-65 1.46-1.59
> 38 Very, very poor >66 > 1.60
Bulk Density- 0.139- 0.391 g/cm3
Tapped Density- 0.210- 0.481 g/cm3
True Density - 1.56 g/cm3
Carr RL. Evaluating flow properties of solids. Chem Eng 1965; 72:163-168.
Table 21: The Flow Properties of Solid Data Ranges
43

10 20 30 40
-50
0
50
100
150
200
250
300
INTENSITY
ABS
2 THETA (DEGREE)
(15.62)
(34.64)
(23.1)
Figure 6: (a) XRD Pattern of the Optimal Sample V0 of the GH- MCC (b) normal cellulose of Eucalyptus sulphate
b
a
44

45
4000 3500 3000 2500 2000 1500 1000 500
Transmittance
(a.u)
wavelenght (1/cm)
F0
(1257.62976)
(1728.27648)
(3333.10464)
(2924.18208)
Figure 7: FTIR of untreated groundnut husk

4000 3500 3000 2500 2000 1500 1000 500
10
20
30
40
50
60
Transmittance
%
Wavelenght (1/cm)
(3417.97536)
(2908.75104)
(1635.69024)
(1396.50912)
(1064.74176)
(1141.89696)
Figure 8: FTIR spectra of the optimal sample of groundnut husk microcrystalline cellulose produced (V0)
46

47
Peak of
Reference
(Cm¯1)
3600-3200 2970–2850 2349- 2370 1750-1715 1662-1626 1550-1500 1600-1400 1390-1310 1275-1200 1300-1100
Functional
group
O-H
(alcohol)
C-H
(alkanes)
O=C=O
(carbondioxi
de)
C=O
(β-
unsaturated
ester,liginin)
H2O
(water)
N-O (nitro
compound)
C-H2
(alkane)
O-H
(alcohol)
C-O
(alkyl ether)
C-O-C
Type of
Vibration
Stretch,
H-bonded
Stretch Stretch stretch Stretch Stretch Bending Stretch Stretch
Intensity Strong Strong Strong Strong Medium Strong Weak Medium Strong Medium
Sample ID
F0 3333.10 2924.18 2345.52 1728.28 1627.97 1504.53 1419.66 1373.36
1327.07
1257.63
1226.77
-
V0 3402.54 2924.18
2870.17
2345.52 1643.41 - -- 1381.08 - 1141.90
AVICEL PH
101
3275 2887 - - 1638 1425 1363 -- 1154
Table 22: FTIR spectra of untreated Groundnut husk, groundnut husk microcrystalline cellulose andAvicel PH 101

48
Plate 1: Photographs of (a) untreated groundnut husk (b) alkali treated
(c) HNO3/ ethanol refluxed (d) GH-MCC
(a) (b) (c) (d)

Plate 2: Photographs of laboratory work
49

50
The Fourier Transform Infrared Spectroscopy (FTIR) confirmed the removal of hemicellulose
and lignin from the GH- microcrystalline cellulose. The x-ray diffractometer (XRD) shows two
prominent peak of crystallinity.
The scanning electron microscopy (SEM) image of GH-MCC shows that the fibers are uneven,
rod shaped having a rough surface. Also, the physicochemical properties are within the
acceptable range as compared to the Pharmaceutical encyclopedia
The Analysis of variance (ANOVA) showed that temperature is the most influential factor for
alkali treatment and the multi stage pulping of microcrystalline cellulose. Under optimal
conditions, the percentage yield and percentage purity of the cellulose obtained were 73.79 %
and 88.08 % respectively. The theoretical values for the percentage yield of the microcrystalline
cellulose were close to the experimental results having an error difference of 1.27 % percentage
yield and 2.59 % percentage purity respectively. Therefore, RSM technique based on CCD
design is suitable for optimizing the variables influencing the production of microcrystalline
cellulose.
CONCLUSION

51
The Researcher acknowledge
Plateau Tin Mines of Nigeria Ltd and Kaffo Mines Ltd
for
financially supporting
this research
ACKNOWLEDGEMENT

52
H.G Audu, Ameh A.O, and M.T Isa “The effect of particle size of Groundnut Husk for the
Microcrystalline Cellulose Production from Groundnut husk”. ABU NEC2018 170
Hassana A. G, Ameh A.O. and M. T. Isa “Optimization of Process Parameters for the
Alkali Treatment of Alpha Cellulose from Groundnut Husk (Arachis hypogaea)”. Nigeria
Society of Chemical Engineering Annual Conference, P3B‐09:2019
PUBLICATION

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56

58
CHINA SEM IMAGE OF SAMPLE F9
SEM image of sample F9

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