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Preparation and Properties Of Microcrystalline Cellulose From Local Raw Materials

Thesis Submitted By

Mona Tawfik Kamar Alshemy

Supervisors
Prof. Dr. Zienab Helmy AbdProf. Dr.

Elwahab
Professor of inorganic Chemistry Alazher University (Girls Branch)

Atef AbdAlaziz Ibrahim

Professor of Cellulose and Paper National Research Center

Assist. Prof.

Abeer Mohamed Adel

Assistant professor of Cellulose and Paper National Research Center

Aim of the work

Aim of the work

The main objective of this work is :

An attempt to overcome some environmental pollutions

resulted from the industrial treatment of waste materials.

Preparation of microcrystalline cellulose from

agricultural residues as rice and bean hulls.

Understanding the mode of complexation of cellulosic

materials to study the effect on metal ion via the interaction with different metal ion to prepare binary complexes.
Modification of cellulosic materials via the complexation

process with another ligand to increase the functional group coordinated to the metal and formation of ternary complexes.
Using the different cellulosic materials and metal

complexes in different application as the tablet preparation as well as their antimicrobial activity.

Experimental

Characterizationof RH & BH

(Lignocellulosic materials)

Identification of raw materials under study

Prehydrolysis treatment

Pentosan extraction

Pulping & bleaching process

get rid off lignin

Agriculture residues (Rice & Bean hulls)

Acid hydrolysis process (MCC preparation)

Hydrolysis of cellulose amorphous regions

Organosolve etherification (carboxymethylation) method

Preparation of soluble cellulose derivative (P-NaCMC)

Complex formation

Study the properties of metal complex

Antimicrobial assessments

Evaluation of antimicrobial activity of synthesized compounds

Results and Discussion

Chapter I Acid catalyzed hydrolysis of lignocellulosic materials

Determination of the optimum condition for pentosane extraction

Compositional analysis of lignocellulosic materials

Effect of acid

Effect of temperature

Effect of contact time

I- Compositional analysis of lignocellulosic materials (rice and bean hulls).

Lignocellulosic materials Rice hulls (RH) Bean hulls (BH)

Lignocellulosic materials composition

Hollocellulose % 63.66 78.37 -Cellulose % 30.98 51.87 Pentosane % 32.67 26.49 Lignin % 16.21 10.42 Extractives % 2.12 0.29 Ash % 16.52 3.36 Silica in ash % 13.40 -

II-Prehydrolysis of rice hulls by water and mineral acids (HCl, H2SO4) at different concentrations
Lignocellulosic materials Acid prehydrolysis concentration % w/w 0 0.5 1 2 4 5 RH** 0.5 1 2 4 5

Lignocellulosic materials composition

Yield %

Hollocellulose %
60.13 62.09 61.70 56.97 53.38 50.66 61.35 57.99 55.47 52.97 49.97

-Cellulose %
30.43 32.93 33.25 33.25 37.54 39.02 31.11 32.68 32.97 37.85 37.51

Pentosane %
29.70 29.16 28.45 23.72 15.84 11.64 30.23 25.31 22.50 15.13 12.46

Lignin %
22.52 17.07 20.65 23.18 26.20 28.62 20.38 23.21 26.31 27.68 29.21

Ash %
20.44 18.02 18.58 21.58 22.20 23.26 20.01 21.86 22.21 22.83 23.83

RH RH*

59.44 59.94 57.16 55.59 46.55 45.59 60.28 57.49 52.06 46.91 45.66

III- Effect of temperature at constant concentration and time

Lignocellulosic materials composition Lignocellulosic materials RH* Temp. C Yield % Hollocellulose % 53.47 54.36 56.97 54.04 55.12 55.47 -Cellulose % 27.65 30.19 33.25 31.69 32.36 32.97 Pentosane % 25.81 24.16 23.72 22.34 22.76 22.50 Lignin % 31.17 25.29 23.18 31.08 29.62 26.31 Ash % 17.71 19.40 21.58 18.78 20.48 22.21

80 100 120

61.73 59.08 55.59 63.93 60.76 52.06

RH**

80 100 120

IV- Effect of time at constant concentration and temperature

Lignocellulosic materials RH*

Time min.

Yield %

Lignocellulosic materials composition Hollocellulose % -Cellulose % Pentosane % Lignin % Ash %

30 60 90
120 30 60 90 120

62.07 60.18 55.59

49.08 60.69 60.19 52.06 49.97

54.47 54.78 56.97

57.92 52.42 53.88 55.47 57.31

30.07 30.55 33.25

39.07 30.01 31.83 32.97 40.19

24.39 24.24 23.72

18.85 22.41 22.05 22.50 17.12

28.55 28.16 23.18

25.33 28.71 28.73 26.31 26.32

20.79 20.78 21.58

21.95 21.53 21.02 22.21 23.02

RH **

Characterization of samples at optimum conditions

FTIR spectroscopy X-ray diffraction

TGA analysis

Characterization of prepared compound at optimum conditions: 1- FTIR spectroscopy

RH*** BH***

RH**

BH**

RH*

BH*

RH

BH

2- X-ray diffraction patterns

RH***

BH***

RH**

BH**

RH*

BH*

RH

BH

3- TG analysis
RH*** BH***

RH**

BH**

RH*

BH*

RH

BH

Chapter II Characterization of microcrystalline cellulose prepared from lignocellulosic materials

Characterization of samples under study

Identification of raw materials chemical composition
FTIR spectroscopy X-ray diffraction TGA analysis SEM Tablets mechanical properties

I- Chemical composition of raw, pulped and bleached rice and bean hulls.

Rice hulls RH Yield % Hollocellulose % -Cellulose % Pentosane % Lignin % Ash % Silica in ash % Extracted % 63.66 30.98 32.67 16.21 16.52 13.40 2.12 P RHI 31.29 84.72 68.24 16.70 12.00 4.04 B RHI 77.58 91.67 76.64 15.02 2.39 2.98 P RHII 26.55 82.51 67.00 15.51 10.91 5.01 B RHII 75.72 87.25 72.32 14.93 3.81 4.48 Yield % Hollocellulose % -Cellulose % Pentosane % Lignin % Ash % Silica in ash % Extracted % BH 78.37 51.87 26.49 10.42 3.36 0.29 P BHI 56.95 93.18 84.48 8.71 6.03 2.63 -

Bean hulls B BHI 73.84 94.16 86.16 8 1.29 0.74 P BHII 50.38 94.00 86.56 8.00 4.03 1.87 B BHII 89.01 95 87.13 7.87 1.01 0.12 -

II- FTIR spectroscopy

Commercial MCC MCC BHII B BHII MCC BHI B BHI MCC RHII B RHII MCC RHI B RHI

III- X-ray diffraction patterns

IV- TG analysis

V- SEM graphs
Commercial MCC

(X500)

MCC rice hulls (HCl)

(X1000)

(X500) MCC rice hulls (H2SO4)

(X1000)

(X500)

(X1000)

Chapter III Binary and ternary complexes of prepared sodium carboxymethylcellulos (Extracted from bean hulls)

Degree of substitution

DS value of P-NaCMC was found to be 0.70 indicating that the presence of one carboxymethyl group for each unhydroglucose unit

Moisture content

P-NaCMC still contained amounts of water molecules=1

C%=37.11found
Elemental data for P-NaCMC

(36.93calc.)
H%= 5.01found (5.05calc.)

Mass spectrum of P-NaCMC

Mwt.= found257.00 (260.20calc.)

TGA

FTIR spectroscopy

Suggested fragmentation pathway of P-NaCMC

FTIR spectroscopy

TGA

120

100

P-NaCMC C-NaCMC

Weight %

80

60

40

20 0 100 200 300 400 500 600 700

Temperature oC

P-NaCMC water content found 7.70% (calculated 6.93%) C-NaCMC water content found 8.47%

Characterization of binary and ternary polymeric metal complexes

Elemental analysis FTIR spectroscopy Mass spectrum UV spectroscopy X-ray diffraction TGA analysis

2- IR spectra of binary and ternary metal complexes

Binary metal complexes Ternary metal complexes

3- Mass spectrum of Binary metal complexes

Ni+2 Cu+2

Ag+1

UO2+2

5- X-ray diffraction patterns of Binary and Ternary metal complexes

Binary metal complexes Ternary metal complexes

6- TG profile of Binary and Ternary metal complexes

Binary metal complexes

Ternary metal complexes

9- The tentative structures of the metal complexes

(1) [Ni(CMC)Cl(H2O)2].1H2O

(2) [Cu(CMC)Cl(H2O)2].2H2O

Binary complexes

(3) [Ag2(CMCd)(H2O)4].4H2O

(4) [UO2(CMCd)(H2O)3].1H2O

7- Antibacterial activity of all compounds under study

S. Aureus S. Pyogenes P. Phaseolicola P. fluorescens

at high con. 2mg/ml

S. Aureus S. Pyogenes P. Phaseolicola

at low con. 1mg/ml

P. fluorescens

8- Antifungi activity of all compounds under study

F. Oxysporum A. fumigatus

at high conc. 2mg/ml

F. Oxysporum

at low conc. 1mg/ml

A. fumigatus

Conclusion

Conclusion
Residues from annual plants such as rice and bean hulls are interesting alternatives as cellulose source for several applications. Such materials are renewable and vastly available in many regions of the world, and are generally burned or disposed for ambient degradation. Rice and bean hulls could be used for the preparation of MCC using either HCl or H2SO4 hydrolysis. BH is more convenient for preparation of microcrystalline cellulose than RH. MCC prepared in this work similar to that of commercial MCC.

MCC prepared in this work can be used for different applications specially to prepare the pharmatheutical tablets.
The design and synthesis of binary and ternary complexes of Ni2+, Cu2+, Ag+ and UO22+ with carboxymethyl cellulose in its sodium salt (P-NaCMC) and pyridine (py) in aqueous media have been successfully demonstrated. Generally, ternary complexes are more stable than the binary complexes and this trend may be related to presence of pyridine moiety. The presence of pyridine moiety has an effect on the crystalline nature of P-NaCMC. Incorporating of metal ions enhances the antimicrobial properties of P-NaCMC against all the test organisms under identical experimental conditions .