RESEARCH PROJECT

PREPARATION OF HYDROGEL COMPOSITE FROM RICE HUSK

USING MICROWAVE RADIATION AND ITS POTENTIAL
APPLICATION

Submitted by:

Andre Tjahjono NRP: 5203015013

Ricky Lucano Chandra Prayogo NRP: 5203015019

DEPARTMENT OF CHEMICAL ENGINEERING

FACULTY OF ENGINEERING
WIDYA MANDALA CATHOLIC UNIVERSITY
SURABAYA
2018

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 PREFACE

The authors would like to first thank Jesus Christ for His blessing
grace, and also His inclusion that the Research Project entitled Preparation of
Hydrogel Composite from Rice Husk Using Microwave Radiation and its
Potential Application has been accomplished. This report is a prerequisite in
achieving Bachelor of Engineering degree in Chemical Engineering.
The authors realize that the completion of this report is achieved by
the help of many people. There for, the authors would like to thank the
persons below:
1 Shella P.S, Ph.D as Principal Supervisor and Felycia Edi Soetaredjo,
Ph.D as Co-Supervisor.
2 Wenny Irawati., Ph.D. as Head of the Committees, Ir. Suryadi
Ismadji., Ph.D. and Sandy Budi Hartono, Ph.D as members of
committees
3 Felycia Edi Soetaredjo, Ph.D as the Head of Chemical Engineering
Process laboratory, Dra. Adriana Anteng Anggorowati, M.Si. as the
Head of Chemical Analysis Laboratory and Suryadi Ismadji, Ph.D as
the Head of Instrument Laboratory.
4 Mr. Novi as laborant of Chemical Analysis Laboratory and Mr. Pudjo
as laborant of Chemical Engineering Operation Laboratory and as
laborant of Chemical Engineering Process Laboratory.
5 Sandy Budi Hartono, Ph.D as Head of Chemical Engineering
Department.
6 Suryadi Ismadji, Ph.D as Dean of Engineering Faculty.
7 Our parents and family who have given a lot of help and support, both
materially and morally.
8 Our lecturers, friends and also those who are too many to be listed by
name that had contributed their kind assistance.
The authors realize that this report is far from perfect, therefore any
critics and comments which will better improve the research is gladly
accepted. Lastly the authors hope that the report will be useful to all readers
who need information regarding the research of the report.
Surabaya, June 5th 2018

The authors

viii
 ABSTRACT

Hydrogel composite was successfully prepared and characterized

include condition for synthesis hydrogel-composite ratio cellulose –
NaOH/urea/ECH temperature and reaction time using microwave radiation.
Fourier Transform Infrared Spectra (FTIR), X-Ray Diffraction (XRD),
Scanning Electron Microscopy (SEM), Energy Diffraction-X (EDX)
performed for hydrogel-composite characterization. Rice husk cellulose used
for raw material to synthesis hydrogel. Clay minerals such as zeolites have
been proven to have excellent adsorption capacity for the removal of heavy
metal. The adsorption capacity of hydrogel is further increased by combining
with zeolite. Therefore, In this research cellulose combined with zeolite to
synthesis hydrogel composite and applied to adsorption of Cu in aqueous
solution by using Kinetics and Isotherm Adsorption.
It was found that best ratio cellulose and NaOH/Urea 4 gram with
7:12:81 (NaOH/Urea/Water), has maximum swelling ratio, that is 52.4%
where hydrogel formed. This ratio used to synthesis hydrogel-composite with
cellulose - zeolite ratio of 4:4 (g/g), where it was given the best adsorption
capacity of 1.41029 mg/g. Ratio 4:4 used in kinetic adsorption and found that
adsorption in chemical sorption type. This is proved in Isotherm adsorption
parameter studied at 30, 50, and 70 oC with Langmuir and freundlich model
that Qe has increase along temperature increased. Freundlich model was very
well described adsorption of Cu with Hydrogel Composite. And it was found
that at pH 7 has maximum adsorption capacity Qe = 4.318 mg/g

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 CONTENTS

RESEARCH PROJECT ................................................................................. i

LETTER OF APPROVAL ........................................................................... ii
LETTER OF APPORVAL .......................................................................... iii
COPY RIGHT AGREEMENT .................................................................... iv
COPY RIGHT AGREEMENT ......................................................................v
LETTER OF DECLARATION ................................................................... vi
LETTER OF DECLARATION .................................................................. vii
PREFACE .................................................................................................. viii
ABSTRACT ................................................................................................ ix
CONTENTS ..................................................................................................x
LIST OF FIGURE ..................................................................................... xiii
LIST OF TABLE ....................................................................................... xiv
CHAPTER I ...................................................................................................1
I.1 Background...........................................................................1
I.2 Problem Formulation ............................................................3
I.3 Objective ..............................................................................3
I.4 Problem Limitations .............................................................3
CHAPTER II .................................................................................................4
II.1 Adsorption, Equation of Kinetics Adsorption and Isotherm
Adsorption Equation ............................................................4
II.2 Zeolite ................................................................................13
II.3 Rice Husk ...........................................................................15
II.4 Cellulose .............................................................................15
II.6 Hydrogel and Hydrogel-Composite as Removal Cu in
Aqueous Solution Literatur Review ...................................16

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CHAPTER III ..............................................................................................18
III.1 Experimental Design ..........................................................18
III.1.1 Preparation of hydrogel-composite ...........................18
III.1.2 Adsorption Study Kinetic and Isotherm....................20
III.2 Materials .............................................................................20
III.3 Instruments .........................................................................21
III.4 Variables .............................................................................22
III.4.1 Dependent Variables .................................................22
III.4.2 Independent Variables ..............................................23
III.5 Research Methodology .......................................................23
III.5.1 Delignification of Rice Husk Process .......................21
III.5.2 Chesson Method .......................................................24
III.5.3 Zeolite Activation Process ........................................25
III.5.4 Synthesis of Hydrogel ...............................................25
III.5.5 Synthesis of Hydrogel Composite ............................26
III.5.6 Synthesis of reagent 1,5 diphenylcarbazide and
treatment copper with reagent .................................26
III.5.7 Determine maximum wavelength copper at UV-VIS
Spectrophotometer and make raw curve forcopper .27
III.5.8 Determine High Adsorption Capacity (Qt) of Copper
in Aqueous with Variation of Hydrogel Composite 27
III.5.9 Kinetics Adsorption of Cu Using Hydrogel Composite
................................................................................28
III.5.10 Isotherm Adsorption of Cu Using Hydrogel Composite
................................................................................28
III.5.11 Study the effect of pH in Copper adsorption to adsorption
capacity ...................................................................29

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 III.6 Characteristics ....................................................................29

CHAPTER IV ..............................................................................................30
IV.1 Pretreatment Raw Material and Synthesis Hydrogel and
Hydrogel Composite ...........................................................30
IV.1.1 Pretreatment Rice Husk Before and After
Delignification ....................................................................30
IV.1.2 Synthesis Hydrogel and Hydrogel Composite ........34
IV.1.3 Swelling Ratio Hydrogel Composite .......................36
IV.2 Characterization of Raw Material, Hydrogel and Hydrogel
Composite ...........................................................................37
IV.2.1 Scanning Electron Microscopy (SEM) and Energy
Dispresive X-Ray (EDX) ....................................................38
IV.2.2 Fourier Transform Infrared Attenueated (FTIR) ........42
IV.2.3 Xray Diffraction of Zeolite ........................................48
IV.3 Adsorption ........................................................................50
IV.3.1 Adsorption Kinetic .....................................................50
IV.3.2 Isotherm Adsorption ..................................................54
IV.3.3 pH Effect Adsorption with Adsorption Capacity ......57
CHAPTER V ...............................................................................................59
V.5.1 Conclusion .......................................................................59
V.5.2 Recommendation .............................................................59
REFRENCES...............................................................................................60
APPENDIX A..............................................................................................63
APPENDIX B ..............................................................................................66
APPENDIX C ..............................................................................................72
APPENDIX D..............................................................................................74

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 LIST OF FIGURE

Figure II.1 Structure of Zeolite ................................................................. 13

Figure II.2 Cellulose structure .................................................................. 16
Figure III.1 Stage of cellulose-based hydrogel synthesis process ............. 18
Figure III.2. Zeolite Activated Process ..................................................... 19
Figure III.3. Synthesis of hydrogel composite .......................................... 19
Figure IV.1 Mechanism of Delignification Lignocellulose ...................... 31
Figure IV.2 Rice husk (a) before delignification (b) after delignification
NaOH 11% (c) after bleaching with NaClO 5% (d) after bleaching with H2O2
3% ............................................................................................................. 33
Figure IV.3 Hydrogel Composite 4 :0 – 4 :4 ............................................ 36
Figure IV.4 Morphology Structure of (a) zeolite before activation (5000x) (b)
zeolite after activation (5000x) ................................................................. 38
Figure IV.5 Morphology Structure of (a) rice husk (150x), (b) rice husk
cellulose (5000x), (c) hydrogel (5000x), (d) hydrogel composite (5000x) 39
Figure IV.6 Spectrum of (a) rice husk untreated (b) rice husk cellulose .. 40
Figure IV. 7 Spectrum of (a) hydrogel Composite (b) hydrogel ............... 41
Figure IV.7b Spectrum of (a) zeolite before activation (b) after activation
.................................................................................................................. 42
Figure IV.8 FTIR Zeolite (a) Before Activation (b) After activation ....... 43
Figure IV.9 FTIR (a) Hydrogel, (b) Hydrogel Composite ........................ 45
Figure IV.10 Mechanism Crosslinking between cellulose, zeolite inside and
ECH .......................................................................................................... 46
Figure IV.11 XRD (a) Before Activation (b) After Activation................. 49

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Figure IV.12 t (minutes) vs Qt (mg) pseudo first order (a), pseuod second
order (b) .................................................................................................... 52
Figure IV.13 Isotherm Adsorption Freundlich model Ce (mg/L) vs Qe (mg/g)
.................................................................................................................. 54
Figure IV.14 Isotherm Adsorption Langmuir model Ce (mg/L) vs Qe (mg/g)
.................................................................................................................. 54
Figure IV.15 Effect of PH to adsorbed cu (pH vs Qe) .............................. 56

xiv
 LIST OF TABLE

Table II.1. Recent studied about adsorption Cu ........................................ 7

Table II.2. Natural Zeolite and Synthetic Zeolite ..................................... 14
Table II.3 Rice husk composition in 4 million kilogram sample ............. 15
Table II.4 Literature Review Study Removal Cu in Aqueous Solution .... 17
Table IV.1 Percentage before and after delignification ............................ 30
Table IV. 2 Experiment of synthesis hydrogel based on variation of rice husk
cellulose mass ........................................................................................... 34
Table IV.3 Swelling Ratio of Each Composition ..................................... 36
Table IV.4 Percentage of Element in Before Activation and After Activation
.................................................................................................................. 48
Table IV.5 Ratio Hdrogel Composite and Coper Adsobed in Qt.............. 50
Table IV.6 Pseudo first order and Pseudo Second order ......................... 53
Table IV.7 Freundich Isotherm Adsorption Parameter ............................. 55
Table IV.8 Langmuir Isothem Adsorption Parameter .............................. 55

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 CHAPTER I
INTRODUCTION

I.1. Background
Beside rice stem and its root, rice husk is one type of the largest waste
that generated from agricultural. The processing of rice husk waste into
another product can help to decrease the waste and increase the usability of
the waste (Syahrain, et al., 2016). One type of rice husk waste used as raw
material for synthesis hydrogel (Oliveira, et al., 2016). This hydrogel can be
used for water purification from hazardous heavy metal such as copper (Cu)
(Yang, 2016). Rice husk waste is a potentially raw material because of its
cellulose content for hydrogel based cellulose (Handayani, et al., 2015).
Shukla research in 2013 said that rice husk waste have cellulose content about
35%-42% and hemicellulose 18%-25% (Shukla, 2013).
Research study shown that hydrogel can be applied to biodegradable
materials such as for drug delivery, sensors, contact lenses, and adsorption
(Chang et al, 2010). In this research hydrogel was applied to adsorb Cu in
aqueous solution. Yang research in 2016 states that hydrogel can be used to
adsorb Cu2+ almost 100% from water in 48 hours. The other material proved
to be effective for the adsorption is clay minerals like zeolite. Recent studies
also show that the adsorption capacity of hydrogel can be increased by
combining them with organic materials (Saputro, 2016). Therefore in this
study, the zeolite combined with hydrogel into hydrogel-composite removing
Cu.
Hydrogel composite was studied in preparation and characterization
include the best condition for synthesis hydrogel-composite (such as ratio
between cellulose with urea/sodium hydroxide/ECH, temperature and
reaction time). Fourier Transform Infrared Spectra (FTIR), X-Ray
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Diffraction (XRD), Scanning Electron Microscopy (SEM), Energy

Diffraction-X (EDX), analysed are performed for hydrogel-composite
characterization. Adsorption capacity of the hydrogel-composite against Cu
was studied by using kinetic and isotherm adsorption model. Kinetic
adsorption was performed at intervals of 30 minutes until reach the
equilibrium state. Kinetic adsorption model Pseudo 1st and 2nd order were
used to express the adsorption parameter. Meanwhile, the isotherm
adsorption was studied with Langmuir and Freundlich equation. The effect
of pH on adsorption capacity was studied.

I.2. Problem Formulation

1. How the ratio of cellulose and NaOH/ECH does affected the
properties of hydrogel-composite?
2. What is the effect of hydrogel composite if applied in the adsorption
of Cu ?
3. How much time to reach the equilibrium state in the adsorption of
Cu with hydrogel composite?
4. How does the pH affect the %removal of Cu to hydrogel composite?

I.3. Objective
1. To determine the best ratio between cellulose and urea/sodium
hydroxide/ECH in producing hydrogel with swell-able property.
2. To study effect of hydrogel composite in adsorption of Cu by using
kinetic and isotherm adsorption.
3. To determine time to reach the equilibrium state in copper (Cu)
adsorption by Hydrogel-composite.
4. To study the effect of pH in Copper (Cu) adsorption by Hydrogel-
composite.
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I.4. Problem Limitations

1. Addition of zeolite is limited until certain amount that gives best
appearance of hydrogel.
2. Waste of heavy metal Cu used is synthetic waste from solution of
CuSO4.
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CHAPTER II
LITERATURE REVIEW

Composite materials consisting of two or more mixture can be produced

new materials with better properties. By combining these materials, it can be
used to minimize the deficiencies of the components, respectively. This
composite is generally used for various things in the field of biomaterials.
One of them can be used as adsorbent to increase the removal of Copper metal
(Cu).
Copper is rarely found in its pure form but in the form of compounds
with another molecules, for example in the form CuSO4 and CuCl2, both of
that compounds known for dissolved in water so it can potentially
contaminate the water system. Copper also could not degraded quickly and
included in non-essential trace element in the highest level. If copper enter
the human body in large quantities, it will cause dizziness, nausea, the chronic
effects will damage to the liver, kidney failure, even death (Sekarwati, 2015).
By looking at potential present in hydrogels and zeolites, these two
components can be combined to reduce the pollution of dissolved copper
metal in waste water. Recent studies of hydrogel and zeolite and others shown
in table II.1

II.1. Adsorption, Equation of Kinetics Adsorption and Isotherm

Adsorption Equation
Adsorption is a process that occurs when some fluid (liquid or gas)
(adsorbate) is bonded to surface of solid or liquid (adsorbent), and eventually
forming a thin film or film on its surface. In generally, many factors affect in
 5

the adsorption capacity are the adsorbent used, surface area, the pore size of
the adsorbent. The adsorption of some component can be studied with
kinetics adsorption shown in equation II.1 and equation II.2. Pseudo first
order and the second order equation often used to determine the adsorption
capacity over time or time required to achieve equilibrium state. This
equation also represent adsorption kinetics in many studies, it can represent
the amount of solute adsorbed at any time. Meanwhile, adsorption isotherm
determine information or indicates how the adsorbate molecules distribute
between the liquid phase and the solid phase when the adsorption process
reaches an equilibrium state (Simonin, 2016) & (Kim, et al, 2013).
 Pseudo first order adsorption kinetics
𝑞𝑡 = 𝑞𝑒 (1 − 𝑒𝑥𝑝 −𝑘.𝑡 ) (Equation II.1)
where
1
k is the rate constant of pseudo-first order sorption, ( ),
𝑚𝑖𝑛𝑢𝑡𝑒
𝑚𝑔
qe is the amount of solute sorbed at equilibrium, ( ),
𝑔

qt is amount of solute sorbed on the surface of the fly ash at any time, t,
𝑚𝑔
( )
𝑔

t is the time (minute)

 Pseudo second order adsorption kinetics
𝐾.𝑞𝑒 2 .𝑡
𝑞𝑡 = (Equation. II.2)
(1+(𝑘.𝑞𝑒 2 .𝑡)

Where:
𝑚𝑔
qe is the amount of solute sorbed at equilibrium, ( ),
𝑔
𝑔
k is the rate constant of second order sorption, ( )
𝑚𝑔∙𝑚𝑖𝑛𝑢𝑡𝑒
 6

 Freundlich equation

𝑞𝑒 = 𝐾𝑓 . 𝐶𝑒 1/𝑛 (Equation. II.3)

Where:
𝑚𝑔
qe is the amount of solute sorbed at equilibrium, ( ),
𝑔

𝑚𝑔
Ce is the equilibrium concentration of adsorbate in solution( )
𝐿

𝑚𝑔
Kf and n are the constants for a given adsorbent and adsorbate( 1 )
𝐿 𝑛
𝑔( )
𝑚𝑔

n is heterogenity
 Langmuir equation
𝑞𝑚𝑎𝑥 .𝐾𝐿 .𝐶𝑒
𝑞𝑒 = (Equation. II.4)
1+𝐾𝐿 .𝐶𝑒

Where :
𝑚𝑔
qmax is the maximum amount of adsorbate ( )
𝑔

𝑚𝑔
Ce is the equilibrium adsorption concentration ( )
𝑔

𝐿
KL is the Langmuir equilibrium constant( )
𝑚𝑔

(Kim, et al, 2013)

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Table II.1 Recent studied about adsorption Cu

No. Material
Method of Synthesis Referen
Modification Variables Result
Adsorbent Adsorbate Adsorbent ce
Material Application
1 Hydrogel Copper Cellulose - Removal of Cu  Cellulose dissolving pH At pH ≥ 5.0 the Yang, et
based on N, N′ (II) in aqueous solvent: result was the al, 2016
Cellulose methylene solution APS/MBA/AA (300C gradual increase
bisacrylami for 24 h under (RM almost
de nitrogen) 100%) (copper
 Hydrogel formation: concentration =
frozen for 8 h in an 200 mg.L-1)
ultra-low temperature
freezer at -70 oC.
2 Sodium Copper Hydrogel Removal of Cu  HA was mixed with Contact Hydrogel Barekat,
2 Alginate/hy based on (II) from 50 ml of water and time reached Mirzaei,
droxyapatite Alginate/hy aqueous placed in the equilibrium in 2017
hydrogel droxyapatit solution ultrasonic instrument 120 minutes and
modified by e for 15 minutes for the its maximum
zeolite HA to completely adsorption was
disperse in the water. 60.81 mg/g
 1.5 g of SA were
added to the mixture
and placed on the
mixer until a
homogeneous gel
mixture was formed.
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 Each of the obtained

gels was injected into
0.1M calcium
chloride, and the
granules were placed
in a saline solution
for two hours in order
for them to acquire
their stable form;
then, they were dried.
3 Chitosan – Copper Chitosan Removal of Cu  4 grams chitosan and pH, At pH 3 shown
3 Zeolite and Zeolite (II) from 4 g zeolite (ratio of dosage the maximum of
Composite Activated aqueous 1:1) were mixed in adsorbent adsorption
solution 160 mL (5%, v/v) capacity, and
acetic acid. 0,08 gram of
 A 100 mL of 5% chitosan-zeolite
acetic acid was added composite
to the suspension and almost removed
stirred vigorously. 100% of Cu Ngah
 Finally, the beads Wan, et
were air-dried before al, 2012
grinding to obtain the
desired size ( <200
um). The beads will
be used as an
adsorbent
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4 Cottonsee Copper Protein- Removal of Preparation of pH, At pH 6, has a

4 Protein – poly copper from Cottonseed Protein maximum
PAA (CP- (acrylic aqueous (CP) adsorption fo Zhang,
PAA) acid) or solution  Defatted cottonseed Cu. The et al,
hydrogel cottonseed meal was stirred at Removal of Cu 2012
composite protein and 60oC for 60 min at in aqueous
copolymer pH 10–11 with 0.1 N solution can
(CP-PAA) NaOH solution. maintain over
 The protein content 90% in 200
calculated after minutes
nitrogen analysis was
95,52% (w/w, dry
matter basis), using
the Kjeldahl nitrogen
determination method
with the conversion
factor, 6.25.
Synthesis of CP-PAA
Hydrogel
 NaOH solution was
carefully introduced
into the acrylic acid
to obtain a partial
neutralized AA
solution.
 Cottonseed protein
isolate dissolved
thoroughly in
 10

distilled water at
water bath.
 After stirring MBA
and partly neutralized
AA were added and
the mixture was kept
in water bath for 2
hours.
5 Hydrogel Copper Cellulose Removal of Cu Preparation of GO Equilibiru Equilibrium Chen, et
5 Composite and in aqueous  Graphite, sodium m adsorption at al, 2016
based on Graphene solution nitrate, and adsorption 260 minutes,
cellulose Oxide concentrated sulfuric , pH, and pH
combine acid were dosage of maksimum
with consistently mixed in adsorbent adsorption at
Graphene an ice bath for 1 h. 5,5 where qe 78
Oxide KMnO4 was slowly mg/g. at 0,01 g
added to the of dose of
suspension. adsorbent result
 The resulting solution 75 mg/g of qe
was placed at well adsorption.
below 70 oC – 80 oC
for 30 min.
 After drying under
vacuum for 24 h, the
grey-black powder of
GO was obtained.
 11

Preparation of
GO/Cellulose
Hydrogel
 Cellulose in
NaOH/urea aqueous
solution was prepared
GO was dispersed at -
12.6 oC for further
ultra-sonication for 1
h.
 Cellulose added in
the suspension ECH,
as a crosslinking
agent, was added.
ECH feeding, the
resultant mixtures
were stirred.
6 Chitosan- Copper Chitosan Copper  Chitosan flake was pH (non pH at 5 without Li, and
Cellulose and adsorption added into acetic acid cross- crosslink bead it Bai,
Hydrogel Cellulose in a beaker and the linked has maximum 2004
contents in the beaker beads, and adsorption
were mixed on a hot crosslink capacity (15
plate stirrer at 70 ◦C beads), mg/g), pH at 7
and 200 rpm for 6 h. equilibriu with cross link
 NaOH solution were m state, bead it has
washed with DI water maximum
in a large beaker until adsorption
the solution pH capacity at 14
 12

became the same as mg/g. The

that of the fresh DI adsorption
water. equilibrium was
 DI water in a beaker, reached at about
with the pH being 7 h for the
adjusted to 12 by the cross-linked
addition of 0.1 M chitosan–
NaOH solution. cellulose beads
Cross-linked but took about
chitosan–cellulose 15 h for the
beads were washed in chitosan–
an ultrasonic bath cellulose beads,
with sufficient DI possibly due to
water until the pH of their higher
the solution became adsorption
around 6–6.5 (the capacity
same as the fresh DI
water).
 13

II.2. Zeolite
Zeolite is a mineral crystalline of porous alumina silicate that had
three0dimensional skeletal structures formed from tetrahedral [SiO4]4- and
[AlO4]5-. Both of tetrahedrons above are connected by oxygen atoms,
resulting an open hollow three-dimensional structure and inside this structure
are filled by metal atoms usually alkali or alkaline and freely moving water
molecules (Scot, et al, 2003).
In generally, zeolite structure is a tetrahedral inorganic polymer of TO4
unit, where T is the SiO4+ ion or Al3+ ion with the oxygen atom being between
two T atoms. This tetrahedral inorganic polymer shown in figure 1.1

Figure II.1 Structure of Zeolite

Zeolite structure has the general formula M x/n [AlO2)x(SiO2)y].wH2O where
M is an alkaline or alkaline cation, n is the amount of cation valency, w is the
number of water molecules per unit of cell, x and y are the total number of
tetrahedral per unit of cell unit. y/x ratio is usually 1 to 5, although zeolites
are also found with y/x ratio of 10 to 100 (Bekkum et al., 1991).
There are two type of zeolite were found, i.e. nature zeolite and synthetic
zeolite. Both off them are shown in table below.
 14

Table II.2 Natural Zeolite and Synthetic Zeolite (Georgiev et al., 2009)
Nature Nature Zeolite Synthetic Synthetic Zeolite
Zeolite Composition Zeolite Composition
Analsim Na16(Al16Si32O96). Zeolite A Na2O.Al2O3.2SiO2.4,5
16H2O H2O
Kabasit (Na2,Ca)6(Al12Si24 Zeolite (Na,TMA)2O.Al2O3.4,8
O72).40H2O N-A SiO2.7H2O TMA –
(CH3)4N +
Klinoptilot (Na4K4)(Al8Si40O9 Zeolite H K2O.Al2O3.2SiO2.4H2O
it 6).24H2O
Erionit (Na,Ca5K)(Al9Si27 Zeolite L (K2Na2)O.Al2O3.6SiO2.
O72).27H2O 5H2O
Ferrierit (Na2Mg2)(Al6Si30 Zeolite X Na2O.Al2O3.2,5SiO2.6
O72).18H2O H2O
Synthetic Zeolite are zeolites that combination two or more component that
have a better character than nature zeolites. The basic principle of synthetic
zeolite production is its component consisting of silica and alumina, so it can
be synthesized from various raw materials containing both components
above. Minor components in zeolites can also be added easily with pure
compounds, so synthetic zeolites have a fixed composition with a high degree
of purify. Where as, for nature zeolite are found in the form of minerals with
different compositions, particularly in the Si/Al ratio and the type of metal
being the minor component, as shown in table 1.1 (Mockovciakova et al,
2007).
Zeolite usually used for adsorbent heavy metal such as mercury (Hg),
Copper (Cu) and Cupric (Cu) (Almaraz, 2003; Panic, 2014). The adsorption
ability of zeolite come from ion exchange of solution containing heavy metal
with minerals contained in the zeolite.
 15

II.3. Rice Husk

Rice husk is used as raw material for synthesis hydrogel-composite.
Rice husk is a waste of rice grain milling, this waste is so abundant in agrarian
country such as Indonesia where rice is the main course. Rice husk usually
used for cleaning kitchen utensils (Handayani, 2009). Rice husk is a
lignocellulose biomass that contain lignin, cellulose, and hemicellulose,
shown in table 2.1 (Novia, et al., 2014). Cellulose and hemicellulose is a
polysaccharide that can be utilized for manufacture of hydrogels with
delignification process and cross-linking with ECH (Chang, et al., 2010).
Table II.3 Rice husk composition in 4 million kilogram sample

Composition Content (%) Mass (kg)

Cellulose 42.2 2.017,047.767
Hemicellulose 18.47 882,816.878
Lignin 19.4 927,268.405
Ash 17.33 828,27.91
Water 2.6 124,273.085
Total 100 4,779,734.05
Source: Novia, et al., 2014

II.4. Cellulose
The cellulose chain consists at one end of a D-glucose unit with an
original C4-OH group (the non-reducing end); the other end is terminated
with an original C1-OH group, which is in equilibrium with the aldehyde
structure (the reducing end). Technical cellulose such as bleached wood pulp,
contain additional carbonyl and carboxyl groups as a result of the isolation
 16

and purification processes that play a significant role in the processing of

cellulose (Rohrling, 2002).

Figure II.2 Cellulose structure (Brown, 2012)

II.5. Hydrogel and Hydrogel-Composite as Removal Cu in Aqueous

Solution Literature Review
Hydrogel is polymer that can adsorb water in a high capacity reaching
about 99% (Chang, 2010). In Barekat research at 2017 was performed
hydrogel based sodium alginate/hydroxyl apatite modified by zeolite, can
become a potentially adsorbent for heavy metal. This study presented the
removal of copper ions from aqueous solutions by synthetic hydrogel-
forming adsorbent polymer based on sodium alginate (SA) and hydroxyl
apatite (HA) Nano particles.
In Yang research, at 2016 was performed hydrogel based on cellulose-
graft-poly (acrylic acid) copolymers (C-g-AA) were synthesized by graft
copolymerization in a phosphoric acid solvent. This study presented
adsorption behaviors of the hydrogels adsorbed Cu. The results indicated that
there were very good correlation the adsorption were performed for 48 hours.
In Li research, at 2004 was performed chitosan-cellulose hydrogel beads
as an adsorbent for Cu adsorption from aqueous solutions. Chitosan was
blended with cellulose to make chitosan-cellulose hydrogel beads and the
hydrogel beads were cross linked with ethylene glycol diglycidyl ether
 17

(EGDE). It was found that the addition of cellulose to chitosan made the
hydrogel beads materially denser and the crosslinking reaction improved the
chemical stability of the chitosan-cellulose beads. All study literature were
shown at table II.3 below.
Table II.4 Literature Review Study Removal Cu in Aqueous Solution

Hydrogel Composite Application Result

Hydrogel based sodium Removal of Copper Qe = 75.8 mg/g,
alginate/hydroxyl from Aqueous kinetic indicate at
apatite (Barekat, 2017) Solution pseudo second 120
minutes (Langmuir
matched R2 = 0.99)
Hydrogel based on Removal of Copper Qe = 182 mg/g,
cellulose-graft-poly from Aqueous actual adsorption
(acrylic acid) Solution amount = 181 mg/g
copolymers (C-g-AA) (48 hours).
Performed chitosan- Removal of Copper Qe = 53.2 mg/g
cellulose hydrogel from aqueous Langmuir R2 =
Solution 0.9983. (24 hours)
 CHAPTER III
RESEARCH METODOLOGY

III.1. Experimental Design

III.1.1. Preparation of hydrogel-composite
The research process was performed in 3 stages. The first stage,
begins the pretreatment of rice husk waste to isolate cellulose as a hydrogel
feedstock, as shown in Figure III.1. The method of pre-treatment of rice husk
to obtain cellulose was performed according to the method by Fatmawati
(2012) with slight modification
Delignification stage 1
Washing and drying
Rice husk at 70 - 80 oC NaOH 11%
24 hours
(m/v) (15:200 g/ml);1

Delignification stage 2
Bleaching H2O2 3%
Cellulose NaClO 5% (v/v) (3:50 g/mL)
(v/v);120 ml
at 70 – 80 oC; 90 minutes
Figure
TheIII.1
rice Stage
husk of
thatcellulose-based
obtained was hydrogel synthesis
washed and process
dried for 24 hours.
Subsequently, the raw material was performed with 11% NaOH (15:200
g/mL) at 70 oC – 80 oC (m/v) solution for lignin cleavage (delignification) for
1 hours. After that, the resulting delignification was rinsed 4 times with
aquadest to remove lignin or NaOH that are still attached. Then, NaClO 5%
(v/v) (3:50 g/mL) at 70 oC – 80 oC performed for 90 minutes to remove lignin
and hemicellulose. Finally, bleaching process is required with 120 mL 3%
H2O2 (v/v).
The second stage, zeolite activated was used Saputra method (2016)
with some modification, as shown in Figure 3.2. There are two step to obtain
uniform zeolite size, first step is zeolite sieved with a size of 100 mesh
second, zeolite is stirred in 3 M NaCl (1:10 g/mL), for 24 hours. After that,
18
 19

the bleaching process is also required here to purify zeolite from impurities
with 3% H2O2 (17:30 g/mL) for 2 hours, then the zeolite was washed and
dried with oven at 105 oC for 24 hours. This zeolite activated with 10% H2SO4
(v/v) (17:30 g/mL) for 24 hours. After that, the zeolite was washed until the
pH neutral, and dried with oven at 105 oC for 24 hours.

Size reduction 100 Stirring in 3 M NaCl

Zeolite
mesh (1:10 g/mL) for 24 hours

Activation with
Purification with H2O2
H2SO4 10% (v/v) Washing and
3% (v/v) (17:30 g/mL);
(17:30 g/mL); 24 drying 105 oC; 24
2 hour
hours

Washing and filtering Drying with oven at Activated

o
(neutralization of pH) 105 C; 24 hours Zeolite

Figure III.2 Zeolite Activated Process

This activated zeolite was combined with hydrogels, forming a Hydrogel-
composite that was characterized using FTIR, XRD and SEM.
Third stage is synthesis the hydrogel-composite, as shown in Figure
III.3. The synthesis of hydrogels according to the Chang (2010) method with
slight modification
Microwave at
Dissolving with Crosslinking ECH
Cellulose Medium
(NaOH/urea 7:12) 9% (55oC )
temperature for 6
mintues
Activated
Zeolite
Hydrogel- Washed and
composite dried

Figure III.3 Synthesis of hydrogel composite

 20

The obtained cellulose was reacted with a freeze mixture of NaOH

/ urea with a ratio of 7 : 12. After that, epichlorohydrin (ECH) 9% (v/v) is
added to cellulose solution and stirred until homogeneous. The activated
zeolite added to the cellulose solution and also stirred until homogeneous.
Then, the mixture is heated in microwave at medium temperature for 6
minutes. After that, the mixture was washed and dried to remove NaOH/urea
o
or ECH. Hydrogel composite was stored in water at 30 C (room
temperature).
III.1.2. Adsorption Study Kinetic and Isotherm
Adsorptions were studied in Kinetic and Isotherm, where the
adsorption capacity of hydrogel-composite to adsorp Cu (Copper (II) Sulfate
(CuSO4) in aqueous solution. First step, determined maximum capacity
adsorption (qt (mg/g)) of ratio zeolite and cellulose at 4:0, 4:1, 4:2, 4:3, and
4:4. Ratio zeolite and cellulose that has maximum capacity adsorption used
in kinetic and isotherm.
Second step, the kinetic adsorption parameter is performed at
intervals of 2 hours until reach the equilibrium state and determined by using
Pseudo 1st order and Pseudo 2nd order adsorption model. Meanwhile, the
isotherm adsorption was studied with Langmuir and Freundlich equation. At
adsorption isotherm, equilibrium state from kinetic used at isotherm
adsorption. The effect of pH and %removal on adsorption capacity also
studied.

III.2. Materials
 Rice husk (Surabaya, East Java)
 Zeolite (Bogor, West Java)
 Urea (CH4N2O,
 Aquades
 21

 Benzene (C6H6)
 1,5-Diphenylcarbazide (C13H14N4O)
 Epichlorohydrin (ECH)
 Sodium hydroxide (NaOH 98%) p.a
 Sulfuric acid (H2SO4 98%) p.a
 Filter Paper
 Copper (II) sulfate (CuSO4)
 Hydrogen peroxide (H2O2) (50%)

III.3. Instruments
 Magnetic stirrer (MS–H–Pro GSA)
 Microwave (Nasional NN-S327 WF)
 Hot Plate (Labincotype L-81)
 Oven (Memmert)
 Glasswares
 Analytical balance (Mettler Toledo type AL204)
 Refrigerator (Nasional)
 Centrifuge (Hareus Labofuge 200)
 Heating jacket (Electromantle MA)
 Mixer (Kirin KBB-250P)
 pH Indicator
 Shaking water bath (Memmert type WB-14)
 Fourier Transform Infrared (FTIR) at were performing at National
Taiwan University of Science and Technology (NTUST), No. 43,
Section 4, Keelung Rd, Da’an District, Taipei City, Taiwan.
 Scanning Electron Microscope (SEM) at were performing at
National Taiwan University of Science and Technology
 22

(NTUST), No. 43, Section 4, Keelung Rd, Da’an District, Taipei

City, Taiwan.
 X-ray Diffraction (XRD) at were performing at National Taiwan
University of Science and Technology (NTUST), No. 43, Section
4, Keelung Rd, Da’an District, Taipei City, Taiwan
 UV-VIS Spectrophotometer at Widya Mandala Catholic University,
Surabaya.

III.4. Variables

III.4.1. Dependent Variables

Pre-treatment of raw material :
 Temperature of delignification 70 - 80 oC for 1 hour, mass of rice
husk is 15 gram in 200 mL 11% (m/v) of sodium hydroxide.
 50 mL of sodium hypochlorite 5% (v/v) in every 3 gram rice husk
pretreated in delgnifcation and 3% hydrogen peroxide (v/v) 120 mL.
Zeolite Activation:
 Sodium chloride 3M (1:10 g/mL), hydrogen peroxide 3% (v/v)
(17:30 g/mL), heating temperature at 105 oC for 24 hours, and
concenctration of sulfuric acid is 10% (v/v) (17:30 g/mL)
Hydrogel preparation:
 Heating of hydrogel in medium power (? Watt) of microwave for 6
minutes.
 Volume of Epichlorohydrin 9% (v/v) as cross-linker in 100 mL
NaOH/urea solution
Adsorption study:
 Concentration of CuSO4 is 200 ppm,
 23

III.4.2. Independent Variables

 Cellulose mass 2%, 4%, 6%, and 8% (m/v).
 The ratio of hydrogel and zeolite 4:0, 4:1, 4:2, 4:3, and 4:4.
 The adsorption time is varied with interval by 2 hours until
equilibrium condition is reached.
 pH in the adsorption process was researched at 1, 3 5, and 7.
 Isotherm adsorption was researched dose of adsorbent 0.2 – 1.4
gram with interval 0.2 gram.
 Temperature was researched 30, 50, and 70 oC.

III.5. Research Methodology

III.5.1. Delignification of Rice Husk Process
1. Rice husk was washed with water to remove impurities and dried
with solar heat for 24 hours.
2. 15 grams of rice husk weighed with analytical balance, and put into
200 ml 11% NaOH (m/v) solution and stirred for 1 hour at 70 °C –
80 oC, then washed with aquades to remove the residual NaOH
solution and lignin that are still attached.
3. The resulting rice husk that from delignification with NaOH, then
put into 5% (v/v) NaClO (3:50 g/mL) solution and stirred for 90
minutes at 70 oC – 80 oC to remove hemicellulose and remaining
lignin that still contain inside the rice husk.
4. 120 ml of 3% hydrogen peroxide (v/v) solution is used for bleaching
process to obtain white cellulose.
5. White cellulose then rinsed with aquadest until neutral.
 24

III.5.2. Chesson Method

Rice husk untreated and after treated were performed with chesson
method to determine %cellulose & %lignin with the following method:
1. 1 gram dry sample (a) added 150 mL H2O then refluxed at 100oC in
water bath for 1 hour.
2. The resulting reflux was filtered and the residue washed with hot
water of approximately 300 mL.
3. The obtained residue dried by oven until constant weight reached,
then weighed (b).
4. Added 150 mL H2SO4 1 N in residue, then refluxed in a water bath
for 1 hour at 100oC.
5. The resulting washed until neutral using aquades of approximately
300 mL and dried (c).
6. The dried residue was soaked in 10 mL 72% H 2SO4 at room
temperature for 4 h then 150 mL H2SO4 1 N was added and refluxed
in water bath for 1 h.
7. The obtained residue filtered and washed with H2O until neutral and
then dried in an oven at 105 ° C and the result was weighed (d)
8. The residue placed at furnace at 500 oC and weighed (e).
Calculation of %cellulose and %lignin are shown in equation below:
𝑎−𝑏
%Water = 𝑥100%
𝑎
𝑐−𝑑
%Cellulose = 𝑥100%
𝑎
𝑑−𝑒
%lignin = 𝑥100%
𝑎
𝑒
%ash = 𝑥100%
𝑎

%hemicellulose = 100% - %water - %cellulose - %lignin - %ash

a = sample weight (g), b = dry weight, c = the residue weight (g) at
 25

the third weighing, d = the residue weight (g) at the forth weighing,
e = the weight of ash (g). (Datta, 1981).

III.5.3. Zeolite Activation Process

1. Zeolite sieved with a size of 100 mesh.
2. The resulting zeolite sieved was stirring in 3 M NaCl (1:10 g/mL)
for 24 hours.
3. Zeolite is purified using 3% hydrogen peroxide (v/v) (17:30 g/mL)
for 2 hours, then rinsed with distilled water and heated at 105 ° C for
24 hours.
4. Zeolite is immersed in 10% (v/v) of H2SO4 (17:30 g/mL) solution
for 24 hours.
5. The soaked zeolite is washed and filtered until a neutral pH reached.
Then the zeolite adsorbent heated at 105 oC for 24 hours.

III.5.4. Synthesis of Hydrogel

1. NaOH/urea solution is prepared with a mass ratio of 7 : 12 and
dissolved with 81 mL distilled water.
2. 2%, 4%, 6%, and 8% (m/v) of Cellulose is dissolved in 25 mL
NaOH/urea solution.
3. 9% (v/v) of ECH will be added into the cellulose solution.
4. Cellulose solution is stirred until homogeneous at 20 °C.
5. Cellulose solution was heated in microwave at medium temperature
(around 55 oC) for 6 minutes.
6. Hydrogel obtained washed with aquades to remove urea, NaOH, and
unreacted ECH.
7. Hydrogels are stored in water at 30 °C.
 26

III.5.5. Synthesis of Hydrogel Composite

1. At the same method at III5.4 NaOH/urea solution prepared.
2. Activated zeolite is added to the cellulose solution with a ratio of
hydrogel and zeolite 4:0, 4:1, 4:2, 4:3, and 4:4 (gram).
3. 9% (v/v) of ECH added into the cellulose solution.
4. Cellulose solution stirred until homogeneous at 20 °C.
5. Cellulose solution was heated in microwave at medium temperature
(around 55 oC) for 6 minutes.
8. Hydrogel obtained is washed with aquades to remove urea, NaOH,
and unreacted ECH.
9. Hydrogel Composite with various ratio are stored in water until
equilibrium weight to determine swelling weight.
10. Hydrogel composite dried until equilibrium weight to determine dry
weight and used in adsorption.

III.5.6. Synthesis of reagent 1,5 diphenylcarbazide and treatment

copper with reagent
Synthesis of 1,5 diphenylcarbazide shown in following method :
1. 10 mg were added to 50 mL of benzene and heated to boiling.
2. The resulting solution was cooled and diluted to 100 mL with
benzene.
Trisodium Phosphate method:
1. A saturated solution was prepared by adding 30 grams of trisodium
phosphate to 100 mL aquadest.
2. The mixture of that solution stirred until trisodium phosphate
dissolved in saturated aquadest.
 27

Treatment copper with reagent :

1. To an aliquot of solution containing copper added 2 mL of trisodium
phosphate at the tubes.
2. After the volume had been adjusted to 5 mL, 7 mL of 1,5
Diphenylcarbohydrazide reagent were added.
3. The tubes were stoppered and shaken vigorously for 1 minute.
4. The copper was distribution from aqueous solution to benzene
solution.
5. The benzene layers were transferred to the cuvettes and read at UV-
VIS spectrophotometer at maximum wavelength.

III.5.7. Determine maximum wavelength copper at UV-VIS

Spectrophotometer and make raw curve for copper.
1. 2000 ppm copper in 1 L was prepared in beaker glass.
2. 2000 ppm diluted to 100 ppm in 100 mL, and 100 ppm diluted to 2,
4, 6, 8, and 10 ppm.
3. 6 ppm was used to determine maximum wavelength with spectrum
at UV-VIS Specrophotometer.
4. Maximum wavelength was used to determine absorbance 2, 4, 6, 8
and 10 ppm to made raw curve of copper.

III.5.8. Determine Best Adsorption Capacity (Qt) of Copper in Aqueous

with Variation of Hydrogel Composite
1. 1 gram of each Hydrogel Composite was prepared with ratio 4:0,
4:1, 4:2, 4:3, and 4:4.
2. 25 mL of 100 ppm copper solutions is prepared in 5 Erlenmeyers.
3. The mixture of that solution is placed at shaking water bath in room
temperature with 10x rpm until 2 hours.
 28

4. After 2 hours, 5 samples is measured in UV-VIS Spectrophotometer

to determine best removal of hydrogel composite ratio.
5. Ratio of hydrogel composite that have maximum adsorption
capacity (Qt) was used in kinetic adsorption of Cu

III.5.9. Kinetics Adsorption of Cu Using Hydrogel Composite

1. 25 mL of 200 ppm copper solutions prepared in 9 Erlenmeyers.
2. 1 gram Hydrogel composite that has maximum adsorption capacity
is added to each copper solution.
3. The mixture of that solution is placed at shaking water bath in room
temperature with 10x rpm.
4. Every 30 minutes will be sampled for measured concentration of
copper by using UV-VIS Spectrophotometer until equilibrium state
is reached.

III.5.10. Isotherm Adsorption of Cu Using Hydrogel Composite

1. 25 mL of 200 ppm copper solution is prepared.
2. Ratio of adsorbent between zeolite and hydrogel, and equilibrium
state from adsorption kinetic used in isotherm, with mass of
adsorbent 0.2 – 1.4 interval 0.2 gram.
3. The mixture of that solution placed at shaking water bath at
temperature 30, 50, and 70 oC.
4. Equilibrium time reached at kinetics at 5 hours of each temperature
used for sampled variation of adsorbent mass and measured by using
UV-VIS Spectrophotometer to determine Freundlich and Langmuir
equation.
 29

III.5.11. Study the effect of pH in Copper adsorption to adsorption

capacity
1. 25 mL of 200 ppm copper solution is prepared in 4 erlenmeyer. Each
of solution adjusted by adding a solution of NaOH and H2SO4, until
reach ph at 1, 3, 5, and 7.
2. Ratio of hydrogel composite that has maximum adsorption capacity
(qt) used for determine effect of pH at the equilibrium state with
temperature room.
3. The mixture of that solution is placed at shaking water bath with 10x
rpm.
4. All solution measured by using UV-VIS Spectrophotometer.

III.6. Characteristics
1. X-Ray Diffraction for measured zeolite after and before activation.
2. Fourier Transform Infrared Spectroscopy Attenuated Total
Reflectance for determine chemical character of hydrogel
composite, hydrogel, and zeolite before activation, after activation.
3. Field Emission Scanning Electron Microscope, Energy Dispersive
X-Ray for looking pore structure, morphology, and particle size of
rice husk, rice husk cellulose, hydrogel, hydrogel composite, zeolite
after and before activation.
 30

CHAPTR IV
RESULTS AND DISCUSSION

IV.1. Pretreatment Raw Material and Synthesis Hydrogel and Hydrogel

Composite
In this study, pretreatment raw material, synthesis hydrogel and
hydrogel composite were performed and discussed to obtain properties
of cellulose, swelling ratio in hydrogel and hydrogel composite.
Properties of cellulose was performed by chesson method to
obtain %cellulose, %hemicellulose, %lignin, %ash, and %water in rice
husk and rice husk cellulose. The best ratio between
cellulose/urea/sodium hydroxide/ECH to produced hydrogel discussed
by swelling ratio and qualitative.
IV.1.1. Pretreatment Rice Husk Before and After Delignification
Rice husk is the main raw material for synthesis hydrogel composite.
The aim of this treatment is to obtained white cellulose used to synthesis
hydrogel composite. Cellulose content inside rice husk has a potential
for changing in hydrogel composite by dissolved it in NaOH/urea
solution. Cellulose content before delignification, and after
delignification were tested by chesson method to
Table IV.1 Percentage before and after delignification
Component Before (%) After (%)
Cellulose 49.56±0,1 81.96±0,1
Hemicellulose 12.26±0,1 3.57±0,1
Lignin 8.18±0,1 0.29±0,1
Ash 19.65±0,1 7.27±0,1
Water 10.35±0,1 6.91±0,1
Total 100% 100%
 31

determine %cellulose, %lignin, and %hemicellulose. %cellulose before

delignification and after delignification can be seen in table IV.1.
Before the delignification of rice husk
contains %hemicellulose %cellulose, and %lignin, respectively were
12.26%, 49.56%, and 8.18%. After
delignification, %cellulose, %hemicellulose and %lignin were 81.96%,
3.57%, and 0.29%, respectively. This indicates that the rice husk
delignification method successfully opened the hemicellulose, and
removes lignin, respectively by 8.69%, and 7.89%.
Before delignification, the rice husk is dried using solar thermal for
24 hours. Drying is performed to remove impurities and prevent quickly
damaged by chemical reactions and microbial activity. The color of the
rice husk before delignified has brown color and rice husk surface has a
fairly hard structure. After delignification process with 11% NaOH at
70 ° C - 80 ° C for 1 hour, the resulting solution has brown color due to

Figure IV.1 Mechanism of Delignification Lignocellulose

the reaction mechanism between NaOH with lignocellulose shown in
the figure below:
NaOH acts as a solution which can damage the lignin structure that
are crystalline and amorphous parts and part of hemicellulose.
Hemicellulose has an amorphous structure so that function of NaOH
removed lignin as well as hemicellulose extract. From the above
 32

drawing mechanism, the OH- ion will break the bonding bond from the
lignocellulosic structure of the rice husk, while the Na + ion will bind to
lignin to form sodium phenolate. This phenolate salt is soluble
characterized by a brown color in the solution. After the delignification
process with 11% NaOH (Figure IV.2 (b)), rice husks are rinsed to
remove residual NaOH, and lignin still attached. Then, the resulting rice
husk was soaked with 5% NaClO for 90 minutes. NaClO act as
bleaching solution and remove the remaining lignin and also open the
structure of hemicellulose, so that the cellulose obtained higher content.
The result of cellulose is shown in figure IV.2. To improve cellulose
quality, bleaching process was performed with 3% H2O2 120 mL for 1
hour. The main purpose of bleaching is to remove the remaining ligning
and increase white degree of the cellulose obtained, so that the cellulose
that obtained from NaClO should be bleached with H 2O2. In this case,
HOO- (perhydroxyl anion) has an active role in the bleaching process.
This anion removed the remain lignin in the rice husk and also
impurities from delignification with NaClO and NaOH. NaClO has Na +
ion that also dissolved the lignin, and ClO- opened the surface of lignin
and hemicellulose so that, cellulose inside came out. This is proven
through chesson method that after delignification, %cellulose increased
drastically. The aim of this treatment is obtained white cellulose as a
material for hyrdrogel. The white cellulose obtained indicated that
lignin has been removed, increased %cellulose,
reduced %hemicellulose. In addition, the small fiber cellulose from the
treatment also appeared after treatment, so that this cellulose obtained
can be used as material for synthesis hydrogel. The cellulose fibers
made cellulose swelled and also can be cross-linked with cross-linked
agent. After the treatment cellulose obtained has yellowish white color.
 33

The cellulose produced after the delignification and bleaching H2O2 3%

process is shown in Figure IV.2 (d).
In figure IV.2 were shown about the structure before delignification
and after treatment. Removal of lignin characterized by color changed
from figure IV.2 (a) to (b) to (c) and the final in (d). White cellulose
obtained has a difference results, fiber shown after delignification and
indicated delignification has successful for removing lignin,
hemicellulose and increasing cellulose. This is proven in chesson
method that %cellulose has increased after delignification.

(a) (b)

(c) (d)
Figure IV.2 Rice Husk (a) before delignification (b)
after delignification NaOH 11% (c) after bleaching
with NaClO 5% (d) after bleaching with H 2O2 3%
 34

IV.1.2. Synthesis Hydrogel and Hydrogel Composite

Cellulose obtained from the treatment of NaOH, NaClO, and H 2O2
were using as the main raw material for making hydrogel with activated
zeolite. NaOH/urea is made by dissolving in aquades. The solution
mixture (NaOH/urea) is frozen in the freezer for 24 hours. NaOH /urea
is made with a ratio of 7:12 gram diluted in 81 grams of aquadest.
Cellulose can affect the hydrogel structure. This can be demonstrated
through experiments in table IV.2 below
Table IV.2 Effect of cellulose mass to hydrogel formation
Cellulose Hydrogel Colour Dry Swelling Swelling
Mass Formation weight weight Ratio (%)
(gram) (g) (g)
2 Not Yellow - - -
formed transparent
4 Formed Yellow 32.637 49.751 52.4
transparent
6 Formed Yellow 34.4832 46.8964 35.9
transparent
8 Formed Yellow 36.1294 44.3783 22.8
transparent
From observation and experiment determined the gel used for
composite hydrogel composition is at mass 4 gram in 7:12 NaOH / urea,
due to %SR has high result 52.4% and chewy and smooth rather surface,
where swelling ratio can calculate with equation below :
𝑆𝑤𝑒𝑙𝑙𝑖𝑛𝑔 𝑤𝑒𝑖𝑔ℎ𝑡 − 𝐷𝑟𝑦 𝑤𝑒𝑖𝑔ℎ𝑡
%𝑆𝑅 = 𝑥 100%
𝐷𝑟𝑦 𝑤𝑒𝑖𝑔ℎ𝑡
From the table below shown that increased mass of cellulose could
decrease swelling ratio. The increase of cellulose mass decrease the
ability of hydrogel to hold water. Hydrogels containing higher cellulose
will have a tighter cellulose structure, so that the water loaded in the
hydrogel decreased. %SR from some hydrogel indicate about water
 35

stored inside hydrogel. Therefore, best mass of cellulose that has

high %SR 52.4%, at 4 gram of cellulose, therefore this ratio used to
produced hydrogel composite for adsorption Cu. Cellulose was weighed
4 gram, and frozen NaOH/urea solution was thawed for 5 minutes.
After 5 minutes, the NaOH/urea solution has a temperature of about 12
o
C. At this temperature, the cellulose is soluble therein rather than at
room temperature (30 ° C). This is due to the low temperature of a
compound has a solid phase tendency. The solid phase has a small
entropy, which results in a neat arrangement of particles. Cellulose
dissolved at low temperature will be separated by NaOH/urea ions, the
tendency of particles form again decreased due to of low entropy. At
high temperature or room temperature, after dissolved of cellulose due
to a high entropy give effect at particle to a high movement of particles.
Cellulose particle that dissolved and separated before potency to get
reformed due to high entropy (high movement of particles). Once
dissolved, the cellulose is stirred until a transparent cellulose is
obtained. Then added zeolite and stirred until homogeny. The hydrogel
composite is synthesis according to the ratio of 4:0, 4:1, 4:2, 4:3, 4:4 as
a copper metal adsorber. ECH was added with the ratio of NaOH/urea
to ECH 100:9 (v/v), then stirred until homogeneous. ECH in this case
acts as a crosslink to form a cross-linked between cellulose and zeolite.
Cellulose dissolved in aqueous NaOH/urea solution may be chemically
cross-linked by ECH to form hydrogel, and without addition, due to the
base of the solvent system. On the other hand, physically crossed gels
may be formed in aqueous solutions of NaOH/urea at higher
temperatures (above 30 oC), or lower temperatures (below -3 oC).
Therefore, synthesis hydrogel composite was prepared by heating using
a microwave at medium temperature for 6 minutes. Cross-bonding
 36

processes are considered to be chemically bonded. In the heating

process, the physical crosslinking of the hydrogel is primarily due to
rigid chain shackles for the desolvation of cellulose molecules, forming
amorphous structures. This research has some novelty through
composite have been made. In generally, the hydrogel method by Chang
(2010), is relatively longer which taken 20 hours. Meanwhile, a new
method has found that time needed for synthesis of hydrogel only 6
minutes. Second novelty of this composite, was found in cellulose rice
husk that processing a waste from agriculture into a more use full
material. In generally, the previous hydrogel research only used
cellulose from whatman filter paper (Chang, et al 2010). Hydrogel
composite have been made shown in figure IV.3.

Figure IV.3 Hydrogel Composite 4:0 – 4:4

 37

IV.1.3. Swelling Ratio Hydrogel Composite

Table IV.3 Swelling Ratio of Each Composition
Composition Dry weight (g) Swelling weight (g) Swelling ratio (%)
4:0 32.637 49.751 52.4
4:1 37.6135 40.647 8.065
4:2 29.4888 30.711 4.145
4:3 31.5499 32.2611 2.254
4:4 34.3495 34.5374 0.547
To find the swelling ratio, the hydrogel is immersed in water until it
reaches a constant weight then dried until has reached constant weight
and weighed to determine the dry weight, hydrogels with different
compositions are treated in the same way. Composition of 4 gram
cellulose and 0 gram of zeolite has the largest swelling ratio. In hydrogel
without zeolite, there are small pores. This pores could be kept the water
inside, when the hydrogel swelled (water adsorbed by hydrogel). Then,
the water retained in the hydrogel due to small pore. Where as in the
hydrogel composite, zeolite opened the hydrogel pores so that when the
water absorbed by hydrogel, the waters weren’t retained in the hydrogel
thus swelling ratio hydrogel composite has small percentage. In FTIR
characterization also indicated that pure cellulose hydrogel had a peak
at wavelength of 1630 cm-1 that indicate H-O-H (hydrogel absorbed
water), while the hydrogel composite has a very short peak at
wavelength of 1630 cm-1.

IV.2.Characterization of Raw Material, Hydrogel and Hydrogel

Composite
Scanning electron microscope (SEM) and Energy Dispersive X-Ray
(EDX), Fourier Transform Infrared Attenuated (FTIR), FTIR-
 38

Attenuated Total Reflectance (FTIR-ATR), and X-Ray Diffraction were

performed. Characterization of raw material (rice husk), cellulose,
zeolite before, after activation, hydrogel, and hydrogel composite were
perform in SEM/EDX, FTIR, XRD, FTIR-ATR are discussed in this
section. Rice husks was successfully obtained a cellulose for synthesis
hydrogel. The best ratio between cellulose/urea/sodium
hydroxide/ECH, in producing hydrogel with swell-able property are
also discussed in this chapter. Ratio of hydrogel composite that has
maximum adsorption capacity, kinetic adsorption and isotherm
adsorption also discussed.

IV.2.1. Scanning Electron Microscopy (SEM) and Energy Dispersive X-

Ray (EDX)
Morphology of zeolite before, after activation, rice husk untreated,
rice husk cellulose, hydrogel, and hydrogel composite shown in figure
IV. 4 and IV. 5. Zeolite examined by SEM in Figure IV.4 (a) before
activation and (b) after activation. At figure IV.4 (a) before activation,
the morphology zeolite shown that almost some surfaces has rod-
shaped. At figure IV.4 (b) activation of zeolite was using chemical and

Figure IV.4 Morphology Structure of (a) zeolite before activation (5000x)

(b) zeolite after activation (5000x)
 39

physical methods shown the surface has heterogeneous. After activation

the surface becomes rougher.

Figure IV.5 Morphology Structure of (a) rice husk(150x), (b) rice husk
cellulose (5000x), (c) hydrogel (5000x), (d) hydrogel composite (5000x)
The morphology of rice husk shown in figure IV.5. Images were
obtain in 150x. At 150x, as shown in figure IV.5 (a), the untreated rice
husk before delignification has intact surface, and had a rather smooth
surface. There is a smooth granules in every surface that can be seen at
150x. This indicate, that the surface structure (epidermis) of rice husk
has smooth granules on each surface that is rather smooth surface in
large amounts scattered surface of rice husks. At figure IV.5 (b), is the
structural morphology of cellulose was examined by SEM. This
cellulose resulting from rice husk treated with NaOH, NaClO and H2O2.
Structure cellulose after treatment showed heterogeneous surface and
 40

separate surface. Epidermal layer wasn’t seen at the cellulose surface.

This indicate that delignification of rice husk untreated opens the
epidermal layer and remove epidermal structure of rice husk (Lignin),
and obtain cellulose. Compared to untreated rice husk, the SEM images
indirectly indicate that the surface structure (epidermal) of rice husk
changed significantly after treated with NaOH, NaClO and H 2O2. The
untreated rice husk was intact and had a rather smooth surface (figure
IV.5 (a)), while after treated, the cellulose has a heterogeneous and
separate surface. This proven at spectrum in figure IV.6 spectrum
(EDX), rice husk untreated was found that Si (silica) contained inside
the rice husk. After delignification, silica disappeared at spectrum rice
husk cellulose.

(a)

(b)

Figure IV.6 Spectrum of (a) rice husk untreated (b) rice husk cellulose
 41

Figure IV.5 (c) hydrogel and (d) hydrogel composite shows the SEM
5000x images of cellulose hydrogels prepared by heating in microwave
with 4 grams cellulose dissolved in NaOH/urea 7 : 12, display surface
of hydrogel. At the figure IV. 5 (c) The vast majority of the cross-
sectional images surface of gel has a rather intact surface and also has a
rather smooth surface, indicating that occurs swelling between cellulose
and NaOH/urea. The ra ther smooth surface indicated that cross-linked
with ECH is formed. At figure IV.5 (d) also showed surface of hydrogel
combine with zeolite. The surface of hydrogel composite has rough
surface that indicated particle addition of zeolite in surface. It was found
at spectrum (EDX) between hydrogel and hydrogel composite. At
hydrogel composite, figure IV.7 (a), addition of zeolite Si was found at

(a)

(b)

Figure IV.7 Spectrum of (a) Hydrogel Composite (b) Hydrogel

 42

spectrum. Compared with hydrogel without addition of zeolite, Si

disappeared at figure IV.7, so that indicated that there is addition of
zeolite in the hydrogel composite.
Figure IV.7b also shown EDX zeolite before activation (a), and after
activation (b). Zeolite consists of minerals composed of several layers.
It indicated via EDX graphic before activation. At figure IV.7b it was
found that most of zeolite contains before activation were Ca, O, Na and
Si. After activation, at figure IV.7b (b), acid-activated zeolite and
purified effected in several layers at zeolite, that could opened several
layer at zeolite and remove the impurities. It was proved at figure IV.7b
(b) where Fe and Al were rinsed at some peak. Na and Ca were removed
by using acid-activated zeolite and purified( H2SO4 and H2O2)

(a)

(b)

Figure IV.7b Spectrum of (a) Zeolite Before Activation (b) Afer Activation
 43

IV.2.2. Fourier Transform Infrared Attenuated (FTIR)

FTIR analysis is performed to identification the functional groups
present in the hydrogel, hydrogel composite, zeolite before activation
and after activation. ATR-FITR spectra of hydrogels (hydrogel and
hydrogel composite) compared are shown in figure IV.8 and IV.9.
FTIR performed in zeolite before and after activation to
identification the functional groups present in the zeolite sample. As
shown in figure IV.8, activated zeolite were analysed at wavelength 400
– 4000 cm-1. Zeolites generally have a characteristic infrared absorption

(a)

(b)

Figure IV.8 FTIR Zeolite (a) Before Activation (b) After Activation
region around the wavelength 300 – 1200 cm-1. Based on figure IV.8,
comparison between wave numbers in zeolite before and after
activation, at 783 cm-1 region appeared in after activation that indicated
Al-O bonding. This indirectly indicated that zeolite after activation
gives effect to both of bond between Al and O (Al-Oweini, et al, 2009),
 44

Functional group of Si-O-Si shown at band 1074 cm-1 (1000-1100 cm-

1
), both of zeolite has a same peak, this indicate before and after
activation still has Si-O-Si bonding (Karakassides, et al, 1999). The
band at 1641 cm-1 show O-H bending while, both of zeolite also has
same peak that indicate before and after activation still has same
bonding (Al-Oweini, et al, 2009). The absorption area about 950 - 1000
cm-1 shows an asymmetric stretching vibration of Si-O and Al-O from
the alumina silicate framework. Absorption in this area is indicated by
all synthesized zeolites. Vibration of the Si-O and Al-O symmetry
appear in the absorption area of 600 - 700 cm-1. The bending vibrations
of Si-O and Al-O on the aluminosilicate framework of the zeolite appear
in an absorption area of about 400 cm-1. The existence of vibration and
bending vibration of Si-O and Al-O indicates the formation of
aluminosilicate framework in the zeolite. (Al-Oweini, et al, 2009 &
Elaiopoulos, et al, 2010).
FTIR-ATR at hydrogel and hydrogel composite were shown in
figure IV.9. Both hydrogels are compared in the spectra of the hydrogels
can observe that:
(1) the band at 1030 cm-1 indicate C-O stretching where in this
functional groups indicate cellulose or hemicellulose were found in both
of hydrogel (Chen, et al, 2011) (2) at 1430 cm-1 is indicated band of CH2
symmetric bending, (Ciolacu, et al, 2012 & Carrillo, et al, 2004) indicate
decreased strongly in hydrogel (a), and was found in hydrogel
composite (b), (3) at 1328 cm-1 is indicated band of C-C and C-O
cellulose vibrations, (4) CH deformation for CH3 was occurred at 1455
cm-1, indicated that hydrogel (a) cross-linked with ECH only, at
hydrogel composite (b), 1455 cm-1 was disappeared (Harry, 1973). (5),
in addition, at 1630 cm-1 by comparing both of hydrogel, this band
 45

appeared in hydrogel (a) strongly. This peak indicate that hydrogel

adsorbed water is more intense in hydrogel (a) than in hydrogel
composite (b) (Tsuboi, et al 1957). (6), at 3343 cm-1 (3100-3600) region

(b)

(a)

Figure IV.9 FTIR (a) Hydrogel, (b) Hydrogel Composite

On which is due to the OH-stretching vibration, gives considerable
information concerning the hydrogen bonds. It was found at hydrogel
(a), and disappeared in hydrogel composite became lower intensity, due
to zeolite inside the hydrogel composite.
Both of hydrogels are proven that has cellulose bond at 1030 cm-1
where in this region function group cellulose or hemicellulose were
found in both of hydrogels. At 1328 cm-1 can be related to load of water
inside hydrogel. The band of C-C and C-O cellulose vibrated due to
water stored in hydrogel. at 1430 cm-1 shown in hydrogel composite,
and decreased in hydrogel, this indicate that hydrogel composite has a
low stored water inside the hydrogel so that peak has shifted, and
 46

indicated that zeolite mixed inside hydrogel. This is because of zeolite

inside the hydrogel composite opened the pore of hydrogel, so that when
the water entered the hydrogel, water came out from inside hydrogel
due to open pores of cellulose with zeolite. This is proven at 1630 cm-1
region was appeared in hydrogel, due to hydrogel adsorbed water and
hydrogel composite has a low peak (low of load water). At 1455 cm-1
region that still appear in hydrogel, and disappeared in hydrogel
composite (peak shifted to left) related to CH3 deforming caused by
weak crosslinking bond due to a high load of water inside the hydrogel.
Mechanism crosslinking reaction between cellulose, and zeolite
inside with ECH, in NaOH/urea solution can be assumed and described
in figure IV.10, the hydroxyl groups of the cellulose were cross-linked
with epoxy and form a new epoxide formed by chloride displacement.

Zeolite Cellulose

Hydrogel Composite
Figure IV.10 Mechanism crosslinking between cellulose, zeolite inside
and ECH
 47

From SEM, FTIR, XRD and EDX before and after activation it was
found that the zeolite before activation SEM zeolite shown that most of
surface there are rod shaped and indicated from EDX there are Ca, O,
Na, Al,, and Si containing inside the zeolite before activation. After
activation, SEM zeolite shown that most of surface changed to
heterogenic surface, and rod shaped almost disappear, and indicated
from EDX that some peak was appeared. There are Fe, Mg and Al peak
increased high. This is prove at FTIR before and after activation that at
before activation peak 783 cm-1 (Al-O) still at normal steep, but at after
activation high steep peak shown in after activation FTIR and EDX also
shown high peak of Al after activation was difference with before
activation. This is also proved at XRD zeolite before activation that
explain below at IV.2.3 shown there was a reduction such as quartz in
table IV.4 which effected to addition another component e.g there is no
silicate before activation and increased 9.2% after activation.
From SEM, FTIR and EDX hydrogel, hydrogel composite and rice
husk, it was found that SEM untreated rice husk has intact surface, had
a rather smooth surface, indicated a epidermis surface of rice husk. And
after treated the resulting of cellulose showed heterogeneous surface
with separate surface. Epidermal layer disappear or wasn’t seen at the
cellulose surface, indicated that untreated rice husk open epidermal
layer and removed structure of epidermal. It was proved at EDX that Si
(silica) found at untreated rice husk, and disappeared at rice husk
cellulose (after treated), peak of C atom and O atom were reduced. At
SEM hydrogel has smooth surface indicated that occurs of swelling
between cellulose and NaOH/urea. The rather smooth surface indicated
that cross-linked with ECH is formed. SEM of hydrogel composite
(hydrogel combine with zeolite), has a rough surface that indicated
 48

particle addition of zeolite inside hydrogel mixed well. It was found that
at EDX between hydrogel and hydrogel composite that addition of
zeolite Si was found, and compared with hydrogel without addition of
zeolite, there is no Si peak at hydrogel only. Compare to FTIR Hydrogel
composite and hydrogel only shown about striking differences at peak
1630 cm-1 related to Hydrogel only absorbed a lot water (H-O-H
bending), and 3343 cm-1 (H-O-H bending), as explained above which
gave peak shifts 1328 cm-1 (C-C, C-O vibration after absorbed water),
to 1430 cm-1 (hydrogel composite absorbed less water than hydrogel
only), and deforming CH3 at 1455 cm-1 as explain above.

IV.2.3. X-Ray Diffraction of Zeolite

To analyse the compound of zeolite before activation and zeolite
after activation, X-Ray diffractometry was carried out. Before activation
and activated zeolite XRD patterns were given in figure IV.11, both of
zeolite consists mainly of quarts. In before activation zeolite the
percentage of quartz is 84.6% and reduced to 66.8% while cristoballite
was increased from 10.6% to 13.4%, treatment by heating at temperature
105oC and soaked with H2SO4 degrade the quartz into cristoballite and
another mineral such as almandine and periclase. Fig. IV.11 (a) before
activation and (b) activated zeolite display a similar diffraction peaks at
2θ = 26o.
Table IV.4 Percentage of Element in Before Activation and After
Activation
Element % Weight
Before Activation After Activation
Quartz 84.6 66.8
Cristobalite 10.6 13.4
Silicate - 9.2
Faujasite-Na 3.5 -
 49

Lime Stone 1.3 -

Almandine - 8.6
Periclase - 2.1

(a)

(b)
Figure IV.11 XRD (a) Before Activation (b) After Activation
 50

IV.3.Adsorption
After hydrogel composite was successfully prepared in this research,
this composite used in adsorption application to adsorb Cu in aqueous
solution by using kinetic and isotherm adsorption. UV-VIS
Spectrophotometer was performed to analysed remaining Cu in aqueous
solution by addition of 1.5-diphenylcarbazide to Cu solution.
IV.3.1. Adsorption Kinetic
Kinetics of adsorption hydrogel composite with copper sulfate were
evaluated to understand the mechanism adsorption by using pseudo first
order and pseudo second order. The aim of a kinetic adsorption
experiment is obtain the type adsorption of adsorbent. If the kinetic
model best fits pseudo first order reaction plot by giving R 2 value close
to 1, it indicates that the reaction is more inclined towards physisorption.
Similarly, if the reaction fits well to pseudo second order model, it
indicates an inclination towards chemisorption. Then, this experiment
can be also obtained equilibrium state of adsorbent that can be used in
the isotherm adsorption.
Firstly, there are 5 various of ratio between cellulose and zeolite,
4:0, 4:1, 4:2, 43, and 4:4. Before perform kinetic adsorption, in order to
obtain the maximum adsorption capacity (Qt) from ratio of hydrogel 4:0
– 4:4 were performed. 1 gram of each hydrogel composite from 4:0 until
Tabel IV.5 Ratio Hydrogel Composite and Copper Adsorbed in Qt
Ratio Hydrogel Qt (mg/g) First Qt(mg/g) Second
Composite Experiment Experiment
4:0 0.1395 0.0813
4:1 0.4468 0.3305
4:2 1.2358 1.1611
4:3 1.3023 0.9368
4:4 1.4102 1.368
 51

4:4 ratio were mixture in 100 ppm copper sulfate and placed at shaking
water bath for 2 hours with 10x rpm. After 2 hours, 5 samples is
measured in UV-VIS Spectrophotometer. The resulting of maximum
adsorption capacity (qt), shown in Table IV. 5.
From the table IV. 5 shown, ratio adsorbent that have maximum
adsorption capacity in both of experiment at 4:4, where the has
maximum adsorption capacity is around 1.368 – 1.41 mg/g. This is due
to the amount of zeolite also affects the amount of copper adsorbed.
Mechanism of adsorption in hydrogel composite begins in the hydrogel
adsorbed water containing copper. When the water enters the hydrogel,
the copper is adsorbed by the zeolite and partially retained in the
hydrogel, so that the adsorption proceed faster the adsorption capacity
also increased at the same dose of adsorbent. This ratio was used in
kinetic adsorption to determine equilibrium state, isotherm adsorption
and also pH effect.
Kinetic Adsorption was performing with 25 mL of 200 ppm copper
solutions mixture with 1 gram ratio 4:4 hydrogel composite, and placed
at shaking water bath in room temperature with 10x rpm. Every 2 hours
sampled for measured concentration of copper by using UV-VIS
Spectrophotometer until equilibrium state is reached. The kinetic result
are shown on the figure IV. 12 relationship between t (minutes), and Qt
(mg/g) below.
 52

b
Figure IV.12 t (minutes) vs Qt (mg) pseudo first order (a), pseudo
second order (b)
 53

Tabel IV.6 Pseudo first order and Pseudo Second order

Pseudo first order Pseudo second order
-1) 2
Qe (mg/g) K (minute R Qe (mg/g) K R2
(g/mg.minute)
4.3347 0.0595 0.9853 4.5540 0.0283 0.9961
From equation of pseudo first order, obtain qe 4.3347 mg/g, and k1 value is
0.0595 minute-1 with R2 0.9853. Meanwhile, the equation of pseudo second
order adsorption kinetic obtain qe 4.5540 mg/g, and k2 is 0.0283
g/mg.minute, with R2 = 0.99661. From the R2 value adsorption kinetic model,
hydrogel composite is more suitable with pseudo second order, which means
hydrogel composite was performed chemicalsorption type. Equilibrium is
reached at 300 minutes, where the adsorbent has reach maximum for
adsorbed. This equilibrium state used in isotherm adsorption and pH effect of
adsorption.
Zendelska research at 2015 studied about zeolite kinetic adsorption with
200 ppm of Cu initial concentration for 120 minutes. It was found that Qe =
8.2169 mg/g. Compared with hydrogel composite, zeolite has higher Qe than
Qe from hydrogel composite. It was due to zeolites covered by pores of
cellulose or crosslinking between ECH and cellulose, so that adsorption of
Cu2+ in hydrogel composite more reduced. If compared with zeolite only in
adsorption then zeolite only give better results. However, the advantages of
this composite, hydrogels can be more easily separated when adsorption is
complete, between aqueous solution and adsrobat. It was different with the
zeolite only, it need or required a zeolite separator with a liquid such as a
centrifuge to keep the zeolite settles. But, after zeolite was separated with
centrifuge, zeolite may be suspended back to the solution so that separation
between zeolite and aqueous solution need to be improved. By combinating
zeolite in hydrogel become hydrogel composite really useful for separate the
zeolite well.
 54

IV.3.2. Isotherm Adsorption

Isotherm of adsorption hydrogel composite was performing to study
interaction adsorbate molecule on the adsorbent surface. When the
equilibrium state achieved at kinetic adsorption at 300 minutes, this data is
used in isotherm adsorption. Isotherm adsorption explain the capacity of
adsorbent that adsorbed the adsorbate. In this study, Langmuir and freundlich
were used to describe the equilibrium of hydrogel composite adsorbed copper
at various temperature, 30 oC, 50 oC, and 70 oC.
Experimental adsorption equilibrium data of copper sorption onto
hydrogel composite at different temperature are depicted in figure IV. 13 and
figure IV.14. Model parameters were determined using non-linier regression
toolbox in Sigma Plot V.12,5.

Figure IV.13 Isotherm Adsorption Freundlich model Ce (mg/L) vs Qe

(mg/g)
 55

Figure IV.14 Isotherm Adsorption Langmuir model Ce (mg/L) vs Qe

(mg/g)
Table IV.7 Freundlich Isotherm Adsorption Parameter

T oC Freundlich
Kf n R2
(mg/g*(L/mg)^1/n
30 oC 1.2185 2.855 0.9099
50 oC 0.5317 1.7568 0.9934
70 oC 0.2649 1.2745 0.9849
Table IV.8 Langmuir Isotherm Adsorption Parameter
T oC Langmuir
Kl (L/mg) Qmax (mg/g) R2
o
30 C 0.0461 7.1208 0.8799
50 oC 0.0149 11.8125 0.9917
70 oC 0.0057 26.1471 0.9816
 56

Both of model adsorption isotherm were used to study model of

adsorption. The parameter was described at Table IV.7 and IV.8, and figure
IV. 13 & IV.14. For Langmuir model the adsorption affinity is determined by
how strong the composite can adsorb the metal, for freundlich model K f show
the adsorption capacity adsorbent and n show the heterogenity of adsorbent.
Two model of adsorption depends on the temperature at adsorption process,
and the higher temperature indicated the higher adsorption capacity it is
shown by the rise KL and qmax parameter at Langmuir.
From the resulting above, it was found that both adsorption models
can be described interaction between Cu and Hydrogel Composite. But, to
determine which model could be better describe depends on R2. At the table
showed that freundlich could be very well experiment data compared to
Langmuir model. This is proven from SEM hydrogel composite that, the
adsorbent has heterogeneity adsorbent (surface of SEM hydrogel composite
has rough surface). Kf parameter shown in table IV.7 where temperature has
increased, Kf decreased. It was because of chemicalsoprtion proved at
kinetics adsorption. Therefore, freundlich could be very well experiment to
described isotherm model.
Zendelska research at 2015 was studied about zeolite to adsorp Cu
in aqueous solution. It was found with Langmuir parameter that Qmax =
14.75 mg/g. Compared with the hydrogel composite, at 70 oC Qmax result
26.14 mg/g. As the temperature increase shown through the langmuir and
freundlich equations Qe has increased as well, as Qmax. An increase in
temperature generally results in an increase in the amount of copper adsorbed
with hydrogel composite described in Qmax in Langmuir. This may be a
result of an increase of collisions between the Cu and hydrogel composite due
to higher temperature. Compared with zeolite only Qmax has 14.75 mg/g, but
in hydrogel composite Qmax 26.14 mg/g. It was because of hydrogel
 57

composite absorb water that containing Cu inside where adsorb by zeolite.

Hydrogel may be adsorb the Cu, but zeolite inside hydrogel adsorbed the Cu.
From both of adsorption (kinetic, and isotherm), hydrogel composite
that applied to adsorbed Cu has advantage and disadvantage, but most of
adsorption studied was shown that Qmax from Langmuir and described with
freundlich, this composite has a potential to adsorbed Cu in aqueous solution.
However, it required to be further research to modified in adsorption
application to get trendline data of adsorption for studied adsorption
application.

IV.3.3. pH Effect Adsorption with Adsorption Capacity (mg/g)

pH effect adsorption of Cu is crucial parameter, due to the pH can
control or effect in adsorbate and affected to adsorbent. Effect of pH
was studied at 1,3 5 and 7. Initial Concentration used 200 ppm Cu in 25
mL, and 1 gram hydrogel composite 4:4.
In this study used equilibrium state until 300 minutes. The resulting
of adsorption pH vs Qe shown in figure IV. 15. When pH was acidic,
the resulting of Qe was a weak adsorption between Cu with Hydrogel
Composite, it caused by amount of H + made the solution into an acidic
and the hydrogel composite also in acidic. If the adsorbent was in an
acidic, the hydrogel composite would be positively charged. Therefore,
if adsorbate and adsorbent at positive charged, adsorption capacity was
decreased. That indicate from figure IV. 15 shown, where pH raised,
adsorption capacity also increased. Due to hydrogel composite would
 58

be negatively charged. From figure IV. 15 shown that best pH

adsorption is at 7 where Qe = 4.3818 mg/g

Figure IV.15 Effect of pH to adsorbed Cu (pH vs Qe)

 59

CHAPTER V

CONCLUSION AND RECOMMENDATION

V.5.1. Conclusion
1. From this study, it was found that best ratio between
cellulose/urea/sodium hydroxide/ECH in producing hydrogel at 4
gram cellulose, 7:12:81 NaOH/urea/aquadest, 25 mL 9%(v/v),
where the %SR has high resulting (52.4%). Where cellulose
increased, structure of hydrogel has a hardest. It caused by
cellulose structure of rice husk.
2. Adsorption of Cu in hydrogel composite performed in
chemicalsorption and it was proved at isotherm adsorption that
when temperature increase from 30 oC to 70 oC Adsorption
capacity also increased.
3. Equlibirium state in copper adsorption reached at 300 minutes.
4. Best pH to adsorbed copper is at 7 pH Qe = 4.3818 mg/g

V.5.2. Recommendation
Adsorption Kinetics should performed at different temperature at 50
o
C, 70oC and with different mass of hydrogel composite. This study also
has potentially to study the other metal like Pb 2+, Cr2+ to aim the
characteristic of adsorbent.
Characterization SEM, XRD, FTIR-ATR after adsorption should be
studied to compared with before adsorption, and study properties of
hydrogel composite after and before adsorption
 60

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 63

APPENDIX A
PREPARATION OF SOLUTIONS

A.1. Preparation of Solutions in Delignification Process

1. 200 mL 11% NaOH (m/v)
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑁𝑎𝑂𝐻
11% = 𝑥100%
𝑉𝑜𝑙𝑢𝑚 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑚𝑎𝑠𝑠𝑎 𝑁𝑎𝑂𝐻
11% = 𝑥100%
200 𝑚𝐿
11
Mass of NaOH = 𝑥 200
100

Mass of NaOH = 22 gram

1. 22 gram NaOH is weighed by analytical balance then put in
glass beaker.
2. 200 mL of aquadest is measured using a measuring glass to
dissolved 22 gram NaOH in beaker glass.
3. The NaOH solution is stirred until homogeneous.
2. 5% NaClO 50 mL (v/)
M1 x V1 = M2 x V2
5% x V1 = 12% x 50 mL
Volume of NaClO = 20, 83 = 21 mL
3. 21 mL of NaClO is measured using a measuring glass
4. Dsisolve into 50 mL of solution and stirred until homogeneous
in beaker glass.
3. 240 mL 3% H2O2 (v/v)
M1 x V1 = M2 x V2
50% x V1 = 3% x 240 mL
Volume of H2O2 = 14.4 mL
 64

1. 14.4 mL of hydrogen peroxide is measured using a measuring

glass.
2. Dissolve into 240 mL of solution and stirred until
homogeneous in beaker glass.
A.2. Synthesis of Hydrogel
1. NaOH/Urea dissolved in 81 mL distilled water
1. 7 grams of NaOH and 12 grams of NaoH prepared, then
dissolved into 81mL distilled water and freezed 24 hours.
2. 25 mL solution were used for dissolved the 4 gram cellulose
and stirred homogenous.
A.3. Zeolite Activation Process
1. H2O2 3% 300 mL
M1 x V1 = M2 x V2
50% x V1 = 3% x 300 mL
V1 = 18 mL
1. 18 mL of hydrogen peroxide is measured using a measuring
glass.
2. Dissolve into 300 mL of solution and stirred until
homogeneous in beaker glass.
2. 10% H2SO4 (v/v)
M1 x V1 = M2 x V2
98% x V1 = 10% x 300 mL
V1 =10.2 mL
1. 10.2 mL of sulfate acid is measured using a measuring glass.
2. Dissolve into 300 mL of solution and stirred until
homogeneous in beaker glass.
 65

A.4. Chesson Method

72% H2SO4 (v/v)
M1 x V1 = M2 x V2
98% x V1 = 72% x 10 mL
V1 =7.34 mL = 7.3 mL
1. 7.3 mL of sulfate acid is measured using a measuring glass.
2. Dissolve into 10 mL of solution and stirred until homogeneous
in beaker glass.

A.5. Synthesis 1 L 2000 ppm Cu Metal from CuSO4

𝑚𝑔
2000 ppm = 2000 mg/L =
1𝐿

gram CuSO4 = 2000 mg = 2 gram

1. CuSO4 powder is weighed 2 grams using an analytical balance.
2. That powder is dissolved into a little aquades in a beaker.
3. The solution is poured into a 1000 mL measuring flask and aquadest
is added inside until boundary line.
 66

APPENDIX B
RAW CURVE OF COPPER FOR CONCENTRATION ANALYSIS
KINETICS, ISOTHERM ADSORPTION AND PH EFFECT

B.1. Synthesis Raw Curve of Copper Metal from 2000 ppm to 2 ppm, 4
ppm, 6 ppm, 8 ppm, and 10 ppm in 100 mL
1. Firstly, 2000 ppm solution is diluted to 100 ppm in 100 mL
C1 x V1 = C2 x V2
2000 ppm x V1 = 100 ppm x 100 mL
V1 = 5 mL
2. Dilution of 100 ppm solution to 2 ppm in 100 mL
C1 x V1 = C2 x V2
2 ppm x 100 mL = 100 ppm x V2
V2 = 2 mL
3. Dilution of 100 ppm solution to 4 ppm in 100 mL
C1 x V1 = C2 x V2
4 ppm x 100 mL = 100 ppm x V2
V2 = 4 mL
4. Dilution of 100 ppm solution to 6 ppm in 100 mL
C1 x V1 = C2 x V2
6 ppm x 100 mL = 100 ppm x V2
V2 = 6 mL
5. Dilution of 100 ppm solution to 8 ppm in 100 mL
C1 x V1 = C2 x V2
8 ppm x 100 mL = 100 ppm x V2
V2 = 8 mL
6. Dilution of 100 ppm solution to 10 ppm in 100 mL
C1 x V1 = C2 x V2
 67

10 ppm x 100 mL = 100 ppm x V2

V2 = 10 mL
1. Each volume required is taken and measured with a measuring
cup (2, 4, 6, 8, and 10 mL)
2. Each measured volume was put into a 100 mL pitcher and
added aquadest until the boundary line.
B.2. Determine Maximum Wavelength and Curve Raw
Standard solution for CuSO4 used to determine the maximum
wavelength is 6 ppm 100 mL of CuSO4 Solution. Blank solution used
is Benzene, found at 550 nm.

Curve Raw
0,7 0,643
y = 0,0602x + 0,0068
0,6
R² = 0,9732
0,5 0,446

0,4 0,339
0,293
0,3
0,2
0,1
0
0
0 2 4 6 8 10 12

B.3. Determine Best Removal of Copper in Aqueous with Variation of

Hydrogel Composite
There are 5 variotion hydrogel composite, 4:0, 4:1, 4:2, 4:3, 4:4, and
experiment was performed 2 times. The results of experiment is shown in
table below. Adsorbat Concentration = 100 ppm, and hydrogel composite =
1 gram.
 68

Variation Absorbance Concentration Absorbance Concentration

Hydrogel (1) (1) 20 X (2) (2) 20 X
Composite
4:0 0.298 96.7441 0.291 94.4186
4:1 0.268 86.7774 0.254 82.1262
4:2 0.168 53.5548 0.159 50.5647
4:3 0.195 62.5249 0.151 52.093
4:4 0.143 45.2491 0.138 43.588
From the experimental result, 4:4 hydrogel composite provided the
best removal copper in aquaeous, 100 ppm - 44.4185 ppm = 55.581 ppm is
adsorbed. This comparation of hydrogel composite will be used in adsorption
kinetic. The Qe shown at figure below :
 69

B.4. Adsorption Kinetics

Mass of Adsorben = 1 gram
Adsorbate Concentration = 200 ppm
Volume Adsorbate = 0.025 L
B.4.1 First Experiment
Time C real
(Minutes) Absorbance C (ppm) (ppm) qt (mg/g)
30 0.161 2.561462 51.22924 3.719269
60 0.133 2.096346 41.92691 3.951827
90 0.119 1.863787 37.27575 4.068106
120 0.112 1.747508 34.95017 4.126246
150 0.08 1.215947 24.31894 4.392027
180 0.078 1.182724 23.65449 4.408638
210 0.075 1.13289 22.65781 4.433555
240 0.072 1.083056 21.66113 4.458472
270 0.072 1.083056 21.66113 4.458472
300 0.071 1.066445 21.3289 4.466777
B.4.2 Second Experiment
Time C real Qt
(minutes) Absorbance C (ppm) (ppm) (mg/g)
30 0.17 2.710963 54.21927 3.644518
60 0.139 2.196013 43.92027 3.901993
90 0.123 1.930233 38.60465 4.034884
120 0.119 1.863787 37.27575 4.068106
150 0.082 1.249169 24.98339 4.375415
180 0.078 1.182724 23.65449 4.408638
210 0.077 1.166113 23.32226 4.416944
 70

B.5. Isotherm Adsorption

Concentration Adsorbate 200 ppm | t = 300 minutes | V = 0,025 L

T = 30 oC

C real
Mass (g) A (1) A (2) Ce (ppm) (ppm) Qe (mg/g)
0.2002 0.532 0.511 8.375415 119.6487 10.03388
0.4003 0.412 0.401 6.548173 93.54523 6.648437
0.6012 0.324 0.343 5.584718 79.7816 4.999102
0.8014 0.245 0.257 4.156146 59.37346 4.386902
1.021 0.082 0.085 1.299003 18.55717 4.442772
1.2003 0.119 0.123 1.930233 27.57472 3.591295
1.4024 0.11 0.104 1.614618 23.06595 3.15413

T = 50 oC

Ce real
Mass (g) A (1) A (2) Ce (ppm) (ppm) Qe (mg/g)
0.2024 0.493 0.501 8.076412 115.3772 10.45242
0.4053 0.385 0.382 6.282392 89.74837 6.800619
0.6006 0.267 0.289 4.322259 61.7465 5.754808
0.8001 0.201 0.198 3.225914 46.08443 4.80926
1 0.175 0.178 2.79402 39.91453 4.002137
1.2009 0.12 0.147 1.880399 26.86281 3.604322
1.4012 0.105 0.124 1.631229 23.30325 3.152597
 71

T = 70 oC

Ce real
Mass (g) A (1) A (2) Ce (ppm) (ppm) Qe (mg/g)
0.2012 0.367 0.385 5.983389 85.4769 14.23001
0.4052 0.314 0.343 5.10299 72.89978 7.84182
0.6008 0.233 0.285 3.757475 53.67816 6.088625
0.8004 0.202 0.189 3.242525 46.32174 4.800046
1.002 0.134 0.143 2.112957 30.18507 4.2369
1.2019 0.128 0.119 2.013289 28.76124 3.561835
1.4002 0.102 0.089 1.581395 22.59134 3.167559

B.6. pH effect Adsorption

Adsorbate Concentration = 200 ppm
Mass of Adsrobent = 1 gram
V = 0.025 L

C real Qe
pH A C (ppm) (ppm) (mg/g)
1 0.647 10.63455 151.922 1.20195
3 0.444 7.262458 103.7493 2.406267
5 0.346 5.634551 80.49351 2.987662
7 0.111 1.730897 24.72708 4.381823

Example Calculating Qe at pH 7
𝐶𝑜−𝐶𝑒
Qe = ∗𝑉
𝑚

(200−24.727)𝑝𝑝𝑚
Qe = ∗ 0.025 𝐿
1𝑔

Qe = 4.3818
 72

APPENDIX C

ANALYSIS OF CELLULOSE HEMICELLULOSE LIGNIN ASH

WATER CONTENT AND SYNTHESIS HYDROGEL COMPOSITE
C.1. Calculate Cellulose lignin hemicellulose, ash, water content at rice
husk
Before Delignification
Mass a = 1.0026 gram
Mass b = 0.8988 gram
Mass c = 0.7766 gram
Mass d = 0.2797 gram
Mass e = 0.1971 gram
%water = a-b/b x 100 % = (1.0026 – 0.8988)/1.0026*100% = 10.3530%
%ash = e/a x 100% = 0.1971/1.0026 x 100% = 19.6588%
%cellulose = c-d/a x 100% = 0.7766 – 0.2797/1.0026 * 100% = 49.5611 %
%lignin = d-e/a x 100% = 0.2792 – 0.1971/1.0026 * 100% = 8.1887%
%hemicellulose = 100% - 10.3530% – 19.6588% - 49.5611% - 8.1887% =
12.2384 %
After Deliginfication
Mass a = 0.6871 gram
Mass b = 0.6396 gram
Mass c = 0.5657 gram
Mass d = 0.0025 gram
Mass e = 0.0005 gram
It was same at the first step calculate where content has :
%cellulose = 81.9676% Ash = 7.2769%
%Hemicellulose 3.5514% Water = 6.9131%
%lignin = 0.291%
 73

C.2. Optimum Time of Synthesis Hydrogel Composite with Microwave

Method
Temperature microwave at medium, and the resulting of hydrogel shown in
table below :
Time (minute) Crossllink Color
2 - Orange
4 - Orange
6 + Orange
8 + Dark Orange (due to
burn)
 74

APPENDIX D
CHARACTERIZATION HYDROGEL HYDROGEL COMPOSITE
ZEOLITE RICE HUSK CELLULOSE RICE HUSK

D.1 X-Ray Diffraction (XRD)

1. The sample is pressed into a powder in the sample holder.
2. XRD patterns recorded using CuKα radiation (λ = 1.54056 Ǻ).

D.2 Fourir Transform Infra-Red (FT-IR)

FT-IR will was performing in NTUST Taipe, taiwan.
1. The solid KBr pulverized in agate mortar into a fine powder. A small
amount of powder samples (0.2-1%) is added to the KBr powder.
2. The mixture is then ground into a fine powder and pressed to obtain
a homogeneous and transparent pellets. Data collected sample
spectrum in the wavelength range of the mid-IR absorbance mode.

D.3 Scanning Electron Microscopy (SEM)

1. Hydrogel and hydrogel composite samples frozen in liquid nitrogen
were fractured immediately, and then a thin film of gold was sprayed
on their surface.
2. The samples were then placed in a room lined SEM specimen and
scanned at a voltage of 15 kV and then the images were captured at
a manification 150x and 1500x.