"I SEMiNAlIPTEK NUKUR DAN PENGELO~ SUMlER DAYA TMBANG jAKA~~

ZEOLITE FROM CIKANCRA TASIKMALAYA, WEST JAVA:A REVIEW OF ITS PROPERT1ES

Lenny Marilyn Estiaty *, Heny Prijatama *, Yoshiaki Goto **,Szuciya ***, Iskandar Zulkamain *, Dew; F. Kumia *, lis Nur1e1a *

* Reseamh Center for Geotechnology, LIPI** Ryukoku University, Japan*** Hokaido University, Japan

ABSTRACT

Samples from natural zeolite deposit in Cikancra village, T asikmalaya, West Java were investigated for its m ~inproperties. Chemical canposition was analyzed by X-ray Fluorescence (XRF) and Atcmic Absorption Spectrome try(MS) methods. Mineralogical analyses were carried out using X-ray Diffraction (XRD) and Scanning ElectionMicroscopy (SEM) methods. Furthermore, continuous flow method was applied for cation exchange capacity (CE C)determination and TG-DTA (the~al gravimetry -dfferential the~al analysis) was carried out to see the therrlalbehaviour of the zedite.. Analysis results sh<7Ned that the chemical composition was dominated by silica and allBnilla,while other elements like sodum, iron, potassium and titanium were present in lesser amounts. The zedite type \\asidentified as mordenite and clinoptilolite. SEM photographs indicated crystals of mordenite in fibrous or needle fOIl nsand platy cfinoptilolite. Zedite Cikancra was also found to have a relatively high exChange capacity with a CEC value of143.58 meq/100g. Thermal analysis revealed that water vapor was released from zeolite at temperatures of BO.5 to148°C with a weight loss of 9.4%. Furthermore, crystal water was released at 481.8°C, which was indicated witt aweight loss of 4.3%. Based on those determined properties, Zedite Cikancra has the ability to be used for wastewatertreatment, agriculture or animal nutrient applications, drying and odorless.

ABSTRAK

Zeolit alam dari deposit desa Cikancra, Tasikmalaya, Jawa Barat telah dkarakterisasi baik komposisi kimia, Jellisdan bentuk mineral, analisa the~aI (TG-DT A ) dan kapasitas tukar kation. Analisa komposisi kimia dlakukanoongan X-Ray fluorescene (XRF) dan Atomic Absorption Spectrofotometer (MS). Struktur mineral dianalisis dengan alat X-RayDiffraction (XRD) dan bentuk mineral danalisis dengan alat Scanning electron Microscope (SEM) pada pelbesar3n5000 dan 7500 kali. Analisis nilai kapasitas pertukaran kation (KTK) dilakukan dengan care aliran kontinyu. Uji karak1erpanas (the~al Behaviour) dilakukan dengan alat TG-DTA (The~1 Gravimetric- Differential ThemlalAnalysis).Didapatkan has;1 analisis berturut- turut sebagai berikut : susunan kimia didominasi oleh senyawa silik,~~aluminat, natrium, senyawa besi, kalium Can titan. Mineral utama pembentukan adalah dari type mordenit d3nklinoptilolit Bentuk mineral dari toto SEM dihasi!kan dalam bentuk krista! fibrous dan neede mordef1it dan pia 1yclinoptilolit Sedangkan ni!ai kapasitas pertukaran kationnya adalah sebesar 143 meql100 gram. Dari uji karakter pan3steriihat bahwa air bebas dari zeolit keluar pada suhu 00,5 0 C-140,4oCdengan kehilangan beret sebanyak 9,4 %,i~rkristal dapat terbebaskan pada suhu 481,6oC dengan kehilangan berat sebanyak 4,3 "AI. Dari karakterisasi tersel:utzeolit Ckancra, Tasikmalaya dapat dgunakan untuk pengo!ah air, pertanian, petemakan, pengering dan penghilailgbau.

INTRODUCTION

properties, zeolites have been utilised in agriculture,

environmental protectioo and industries, includng agIO-

industry.

Zeolites are found in many areas in Indonesia,

which is related to the volcanic activity in large pa.1s of

the country. At present there are forty-seven zeolite

mines ~ting in Indonesia.

Zeolites have cavities and channel structures

which can be occupied by water and exchangeable free

cation with certain molecular sizes. According to that

zeolite has the abiiity to be used as molecular sieves, ion

exchanger, absorbent and catalyst Based on these

In order to ~timse the use of zeolites, th~y

should be characterised physically and chemically to fir Kj

their ~ use.

Every zeolite deposit in Indonesia has uniq11e

characteristics of the properties. Variation can be fOUlld

in mneralogy, i"1>lJrities, cation exchange ~1YJ-

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Zeolite identification was carried out using X-ray

Diffractometer type Rint 2000, Rigaku with Cu-Ka 1; 40

kV, current of 30 mA and speed 4. per minute.

Scanning Electron Microscope type Jeol JSM-

T330A was used for mineral characterisation. Qualitative

chemical analysis has been conducted using X-ray

Fluorescence Spectrometer type Rix 2000, Rigaku, while

Atomic Absorption Spectrometer type Shimadzu was

being used for quantitative chemical analysis. Cation

exchange capacity (CEC) was measured by continue

flow method and TG-DTA was applied to analyse the

thermal properties of zeolites

chemical composition, crystal structure and thermal

property. All of them can inftuence the use of zeolites.

Physical and chemical characterisation of zeolite

from Cikancra, Tasikmalaya, West Java may be useful

for prospective zeolite users or people interested in

zeolite studes. This study can also contribute to the

inventory of rare information of Indonesian natural

zeolites.

MATERIAL AND METHODS

Material

Natural zeolite samples were collected directly

from a d6p0$it in Cikancra village, Tasikrnalaya, West

Java.

Characterisation

w

[=~!~~J

Flowchart Characterization of Zeolite Cikancra

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RESULTS AND DISCUSSION

Figure 3. SEM Photograph of Needle and Fibrous atsame crystal (magnificatjonSOOO X)

The mineral oonposition of zeolite identified by

XRD is presented in X- Ray Diffractogram in Rgure 2.

The presence of two different groups of peak sha.ved

that the sample contained both mordenite and

clinoptilolite. Detailed examination showed that the

sample also contained contamination of quartz (d =

4.2509 and 3.3657) and montmorillonite (d = 16.9154).

Mordenite and clinoptilolite are two major zeolites found

in Indonesia so far. The two minerals have been

obtained together in varied proportion. In general the

presence of mordenite is more dominant than

clinoptilolite.

Figure 4. SEM Photograph of growing mordeniteneedles (magnification 7500 X)

Table 1.SEM Analysis

Mineral

ClinoptilditeMordenite

Quartz

Length,width and thickness (JJ.n1)

5,3,14, 0.05.0.4

6,4,2

Figure 2. SEM Photograph of Clinoptilolite con~ctaround Mordenite Needles (magnification 5000 X)

Microscopical investigation using SEM confirnld

the XRD ana/'y'Sis results that Cikancara natuiral zeolite

was formed by both morOOnite and clinoptilolite.

MorOOnit was found in the fOml of neede slId

fibrous crystals, while ciinoptiloljte was in t"Je cutic

forms. In Figure 3, ~ite needle and fibrous were

four.d on the same crJStai. Figure 4 showed gl'O'Nillg

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mordenite needle crystals. Dimensons of the zeolite

crystal~ measeured from the SEM microphotogrnphs are

given in Table 1.

Table 2. Chemical Composition of Natural ZeoliteCikancra. Tasikmalava iAAS Measurements\I No. I Compotition ~~ncentration ('t. wt\

SiO2

~~F6203MnOTiO2P20sCaO

~Na20K2OLOIH20-H20+Total

67.4311.104-

0.9970.0004

I-LI

2.!~iT-

~~6.7.I 8:--.

I~I 10.I

OI=:I 12.~~

main cation in mordenite and clinoptilolite structures.

Other elements present in zeolites were potassium,

calscium and magnesiurn. Those elements are

contamination in zeolite structure and can be exchanged.

Other col1taminant in zeolites is iron. Iron contamination

can be diluted by acid (H2SO4 I HCI) or base (NaOH)

trr'.atments, which can increase the surface area and

allow the restructuring of atom positions in ze<..lites to be

exchanged with other cation. Washing with water is

required after acid or base activation to neutralise the

zeolites, followed by drying.

Table 3. Cation Exchange Capacity of Natural ZeoliteCikancra, Tasikmalaya

Material--Zeolite

Cikancra

-C.~.C(meq/100 gr)143

Cation exchange capacity (CEC) value of natural

zeolites from Cikancra was 143 meqt 1 10gr. This is the

number of cation that can be exchanged by zeolites

withorrt activation. CEC value above 1uo mecV100g can

be considered as high for natuml Ze<"lite and it reflects

the good quality of Zeolite Cikallcra. This cation

exchange property may be used for several zeolite

aJ:plications in agri<.;ulture (fertilizer, releasing agen~

etc.), animal nutrients, odor control or environment

(water treatment

Quantitative chemical analysis was carried out

using MS, while XRF analysis was qualitative due to the

lack of standard samples. Results of chemical analysis

are presented in Table 2 anc 4. Silica and alumina are

fo~ing the major composition of zeolites. Zeolites are

known to have a base tetrahedral structure of SiO., ,

where Si4+ ions are commonly exchanged by Al3+ ions to

form tetrahedral of AI 0.-. The nElgative charye is

nelJtralized by a presence of alkali cations, which ca.l !

move freely in the structure and can be exchanged.

Based on chemical analysis, sodum was the main catiOil

in Zeolite Cikancras. Sodum has been known as thJ

:-:.."

:.,i"..)t

U

7".I .;1 ~ (, II ~.

I ~ ~-, ,-iI c

31

:.7

c 200 600 6:xJ I COO~oo

T."",rCi

Figure 5. TG-DTA Curves of Zec-lite Cikancra,

Tasikma/aya

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II

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01

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.Due to its high LOI, zeolite Cikancra can be used as

a drying, ocbur control and adsorbent of air

pollutant.

REFFERENCE

1. Barrer R.M. (1978) Zeolites and Clay Minerals as

Sorbent and Molecular Sieves. Academic Press,

London.

2. L.B. Sand and F.A Mumpton (1978) Natural

Zeolite, Occurrence Properties, use. Pergamon 4!i1

-462

3. Mursi Sutarti & Minta Rachmawati (1994) Zeolit

Tinjauan Uteratur. Pusat dokumentasi dan inform,lsi

ilmiah, Lembaga IImu Pengetahuan Indonesia

(LIPI).

4. Tsitsishvili, G.V. etal. (1992) Natural Zeolites,

England; Ellis HONard Limited.

Diskusi :

1. Akhmad Muktaf Haifari (BAPETEN)

a. Apakah perbedaan kenampakan secara pasti antc ra

zeolit mordenit dan zeo/it klinopsilolit

b. Syarat -syarat apa yang dapat dgunakan at,!u

sebagai Giri bahwa zeolit dapat dgunakan ~ ai

bahan katalis.

Heri Priyatama

a. Wafila klinopsilolit putih, warna mordenit hijau.

b. Zeolit harus bersifat asarn dan selektif tahan temadc tp

reagent katalis.

2. MantoWidodo (P2BGGN -BATAN)

Karakter/dasar yang membedakarl antara mordellit

dan klinopsilolit

Hori Priyatama

-Warna klinopsilolit putih, sedang moidenit hijau

-Struktur dan komposisi kimia juga berbeda.

The result of thennal characteristic analaysis is

shown in Figure 5. In the first instance, water was

evaporated at temperatur between 80.5 -140.4'C (9.4%

weight decrease). Another 4.3% weight drop at 481.8.C

indicated tfJe release of crystal water. The number of

water molecules in crystal structure is agreeable with

pore or crystal space volumes when the crystal unit cell

is heated at that temperature. The total weight loss of

16.5% can be assumed as the Loss on Ignition value.

High Lal value is also an indication of high zeolite

content in rocks and low Lal is related with ION zeolite

content.

Zeolite with high Lal can be expected to have a

good capability to be used as absorbent. Adsorption

prf:f)erty of zeolite is useful for application as dryer, air

pollution cleaning or odor control.

Proper activation temperature of zeolites can be

found from the thermal characteristic. Based on the

analysis result, activation temperature for Zeolite

Cikancra is between 80.5 -140.5.C to evaporate the free

water and between 400 -SOO"C to release the crystal

water.

CONCLUSION

The foiloYfing conclusion can bestated for Zeolite

Cikancra:

.Zeolite Cikancra consists of mordenite and

clinoptiloiite Yfith some impurities of quartz and

montmorillonite.

.CEC value is 143 meq'100g, which means that

Zeolite Cikancra is a good quality natural zeolite.

.La! is 13.5 % -16.5 % and it reflects the high

content of zeolite mineral in rocks.

RECOMMENDATION:

e Due to its high CEC value, zeolite Cikancra can be

used in waste water treatmen~ agriculture and

animal nutrients applications.

3. Rusyd S (P2BGGN -BATAN)

Bagaimana cara pemumian zeolit alam agar ~ at

dipakai untuk katalis atau untuk industli.

Heri Priyatama :-

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dijelaskan mengapa dapat berbeda dan dari kedua

analisis tersebut mana yang lebih baik.

Heri Priyatama :

a. Rowchart tidak kami beri no gambar sehingga XRD

menjadi Gambar 1.

b. Ana/isa XRF tidak memakai standar zeo/it, sehingga

hasilnya hanya merupakan indikasi kualitatif, untuk

komposisi kimia secara kwantitatif. Komposisi kimia

zeolit adalah dari hasil ana/isa MS.

Antara lain dengan aluminasi, pencucian dengan asam,

dsb. Topik merupakan program penelitian kami 2002 -

2003, sehingga diharapkan dapat dtentukan metode

yang paling tepat untuk itu selama masa penelitian.

3. Soeprapto (P2BGGN -BATAN)

a. Halaman 5 kanposisi dari leo/it Cikancra diidentifikasi

dengan XRD yang dtampilkan pada Gambar 1,

apakah bukan Gambar 2.

b. Kanposisi kimia dianalisa dengan AAS (Tabel 2) dan

XRF (T abel 3) berbeda cukup signifikan. Mohon