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MODIFIKASI DAN KARAKTERISASI ZEOLITE ALAM INDONESIA
UNTUK APLIKASI PENYIMPANAN ENERGI PANAS SISTEM ADSORPSI
(Adsorption Thermal Energy Storage)
Euis Djubaedah
Introduction2
Thermal Energy Storage Application
3
TES APPLICATION
HVAC
COLD STORAGE
DESALINATION PROCESS
POWER
4Classification of thermal energy storage systems
5
Thermal Energy Storage
• Base on chemical reaction
• Could saving heat at room
temperature
• More complex system
• Energy Density 200-500 kWh/m3
• Base on Specific Heat
Capacity and temperature
difference
• Cheap and user friendly
• High heat loss potency
• Needed Big Volume
• Energy density10-54 kWh/m3
• Base on energy sorption and
desorption while phase change
• Generally used at low
temperature
• Depends on chemical material
• High cost
• Energy Density 90-100 kWh/m3
example: Paraffin Phase Change Materialexample: closed system Adsorption-TES
example: hot water storage
Latent Energy StorageSensible Energy Storage Thermo-chemical Heat Storage
6
7 Maturity of thermal energy storage technologies [12]
8 Operation principle of sorption thermal storage system.
Previous Research :
Working pairs Reasearcher
Activated
Carbon/Methanol
Wang et al. 2006
Wu, Cheng et al. 1997
Allouhi, Kousksou et al. 2015Henninger, Schicktanz et al. 2012,
El-Sharkawy, Hassan et al. 2009, etc
Activated Carbon/ethanol El-Sharkawy et.al, 2014
Uddin et al. 2014
Frazzika et.al, 2016, etc
Silica gel/ water (Wang, Zhang et al. 2012)
(Solmuş, Yamalı et al. 2010)
(Goldsworthy 2014)
Zeolite /water Wang et.al, 2009Solmus et al, 2010
Kayal et.al, 2016
9
10
Indonesian Natural Zeolite potency (ton)
Source: Neraca Sumber Daya Mineral Non-Logam Nasional tahun 2008 (PSDG)
Lebak, Banten
123,000,000
Bogor, Jawa Barat
25,000,000
Ciamis, Jawa Barat
520,000
Sukabumi, Jawa Barat
124,151,000
Tasikmalaya, Jawa Barat
12,924,160
Lampung Selatan,
Lampung
2,200,000
Tanggamus, Lampung
41,600,000
Tana Toraja, Sulsel
168,480,000Ende, NTT
6,115,000
Majene, Sulbar
26,400,000
Tapanuli Utara, Sumut
16,200,000
Bone, Sulsel
1,400,000
Persyaratan Adsorben untuk diaplikasikan pada Adsorption Thermal Energy Storage (ATES )
• Mampu menyerap adsorbate dalam jumlah yang banyak
• Reversible / mampu melepaskan adsorbate dalam jumlah banyak
• Memiliki densitas energi yang tinggi
• Tiidak beracun dan ramah lingkungan
• Tidak korosif
• Memiliki kestabilan yang cukup baik
• Murah13
(Lefebvre and Tezel 2017)
12
METODOLOGI
1. Pengumpulan Zeolite alam
Bayah diberi kode (NZ-A)
Gunung Kidul diberi kode (NZ-B)
Lampung diberi kode (NZ-C)
Cikembar diberi kode (NZ-D)
Blitar diberi kode (NZ-E)
Cipatujah diberi kode (NZF)
Pangandaran diberi kode (NZ-G) dan
Klaten diberi kode (NZ-H)
15
Pemilihan material adsorben
2. Pre- treatment16
Gambar 3.2 Tahapan treatment zeolite alam; (a) penimbangan zeolite mentah
yang sudah dihaluskan, (b) pencucian dan pengadungan zeolite + air (1:3) selama
3 jam, (c) pengendapan dan pemisahan, (d) pengeringan pd room temperature, (e)
Kalsinasi pd T 150 oC
3. Karakterisasi17
1.BET untuk mengukur surface area, ukuran pori, dan volume pori
2.XRD untuk mengetahui jenis dan fase kristalinnya
3.SEM untuk mengetahui morfologi dari setiap sampel zeolite yang diuji
4.EDS untuk mengetahui unsur-unsur yang terkandung zeolite alam
5.TGA untuk mengetahui kestabilan thermal dari sampel zeolite yang diuji
6.FTIR untuk mengetahui gugus fungsi dari sampel zeolite yang diuji
A.Uji BET B. Uji XRD
Hasil Karakterisasi
18
Sample Luas
Permukaan
(m2/g)
Ukuran pori
(nm)
Volume Pori
(cm³/g)
NZ-A 54.39 12.15 0.072
NZ-B 50.53 12.22 0.031
NZ-C 55.93 9.66 0.098
NZ-D 64.5 9.74 0.062
NZ-E 214.29 2.85 0.15
NZ-F 49.99 13.56 0.087
NZ-G 132.32 9.89 0.071
NZ-H 27.46 13.68 0.076
C. Uji EDS
D. Uji SEM
19
UnsurNZA NZB NZC NZD NZE NZF NZG NZH
Wt% Wt% Wt% Wt% Wt% Wt% Wt% Wt%
C 35.9 2.12 29 8.02 19.4 1.9 44.6
O 36.0 45.1 40.7 48.5 43.5 45.2 49.1 30.2
Na 0.64 1.93 1.35 2.25 0.93
Mg 0.32 0.78 0.33 0.62 0.64 0.53 0.85
Al 2.78 7.14 5.07 4.91 8.59 4.91 7.98 3.5
Si 20.31 35.41 21.12 33.13 39.62 26.28 35.28 18.51
K 1.43 0.93 1.48 1.84 2.06 2.88 0.44 2.19
Ca 2.5 0.71 1.65 2.42 0.83 2.51 1.06
Fe 2.63 4.11 1.61 1.88 1.04
Total: 100 100 100 100 100 100 100 100
Si/Al 7.31 4.96 4.17 6.75 4.61 5.35 4.42 5.29
Metode modifikasi
21Peneliti ,Tahun Material Aplikasi
(Xu, Lemington et al. 2018) 13X + MgSO4 ATES
(Xu, Yu et al. 2018) 13X + MgSO4 ATES
(Mahon, Claudio et al. 2019) 13X + MgSO4 ATES
(Hongois, Kuznik et al. 2011) 13X + MgSO4 ATES
(Brancato, Calabrese et al. 2018) Zeolite 13X + MgSO4.7H2O Thermochemical
TES
(Chan, Chao et al. 2012) 13X + CaCl2 TES
(Tso, Chan et al. 2015) 13X + CaCl2 TES
(Zhao, Jia et al. 2017) 13X + CaCl2
(Lin, Lei et al. 2013) Natural Zeolite + NaCl Ammonium
Capture
(Nurliati, Krisnandi et al. 2015) Natural Zeolite + NaCl Thorium Capture
(Sun, Shi et al. 2017) Clay, zeolite + Ionic Liquids Chloramphenicol
uptake
(Liu and Yu 2019) Ionic Liquids TES
Natural Zeolite + CaCl2
22
Modifikasi Zeolite terpilih
Natural Zeolite + MgSO4 (Xu, Yu et al. 2018)
- Mix Dry zeolite + % salt solution (1:10)
- Stirrer 12 h, at room temperatur
- Filter and drying at room temperature for 4h
- The zeolite was then dried at 150 °C for 5h and then 300 oC for 2 h, respectively
Natural Zeolite + NaCl (Djubaedah, Wulandari et al. 2020)
- Mix Dry zeolite + 0.5 M NaCl solution (1:10)
- Stirrer 2x8 h, at 80oC
- Filter and washing by aquadest, drying at room temperature before calcination
- The zeolite was then dried at 80 °C for 1,5 h
24
Modifikasi Zeolite terpilih
Uji Karakterisasi Zeolit Modifikasi
Karakterisasi BET
25
Material Surface Area
m2/g
Pore Size
nm
Pore Volume
Cm3/g
Raw Material 214.29 2.85 0.15
Activated 227.64 2.75 0.15
NZE + MgSO4 21.41 10.6 0.056
NZE + CaCl2 8.52 20.84 0.044
NZE + NaCl 297.49 2.92 0.21
NZE + Ionic Liquids (Emim
Acetate)
24.43 8.71 0.053
Karakterisasi XRD
26
0
200
400
600
800
1000
1200
1400
1600
1800
2000
0 10 20 30 40 50 60 70 80 90 100
Inte
nsi
ty
2 thetaActivated
Modification NaCl
Uji Karakterisasi Zeolit Modifikasi
Uji SEM
27
Uji Karakterisasi Zeolit Modifikasi
Uji EDS
Unsur
NZ-E
activated
NZ-E +
MgSO4
NZ-E +
CaCl2
NZ-E +
NaCl
NZ-E + IL
Emim
Acetate
Wt% Wt% Wt% Wt% Wt%
C 13.68 27.79 27.79
O 39.78 43.74 36.66 48.77 43.74
Na 1.16 0.7 1.51 4.19 0.7
Mg 0.07 0.22 0.21 0.22
Al 4.5 4 5.22 6.73 4
Si 26.41 20.53 27.93 37.62 20.53
Cl 0.16 15.19 0.17
K 2.87 0.32 0.5 0.51 0.32
Ca 4.93 0.96 10.66 0.85 0.96
Fe 6.44 1.73 2.12 1.15 1.73
Total: 100 99.99 100 99.99 99.99
Si/Al 5.87 5.13 5.35 5.59 5.13
FTIR
24
Uji Karakterisasi Zeolit Modifikasi
Uji FTIR
25
Uji Karakterisasi Zeolit Modifikasi
Uji TGA
26
Uji Thermal Conductivity Zeolit Modifikasi
27
Uji Kinerja Zeolit Alam murni dan Modifikasi
28
Siklus pengujian dengan massa zeolite 300 gr
UNIVERSITAS INDONESIA Zeolit Murni Zeolit Modifikasi
29
Siklus pengujian dengan massa zeolite 600 gr
Zeolit Murni Zeolit Modifikasi
Siklus pengujian Zeolite Alam dengan massa 900 gr
30 Zeolit Murni Zeolit Modifikasi
Temperature Lift pada proses adsorpsi untuk setiap variasi massa zeolit
31
32
Perbandingan jumlah adsorbat yang teradsorpsi dan terdesorpsi untuk
setiap variasi massa zeolit
Sampel zeolit ΔX Proses
adsorpsi
ΔX Proses
desorpsi
ΔX sisa di adsorber
NZE activated 300gr 30 20 33%
NZE activated 600gr 150 130 13 %
NZE activated 900gr 130 120 8 %
NZ_NaCl 300gr 70 60 14 %
NZ_NaCl 600gr 180 170 6 %
NZ_NaCl 900gr 80 70 13 %
33 Kinerja
34
177.1
199.9
200.4
224.1
290.6
233.6
NZ murni _ 300 gr
NZ murni _ 600 gr
NZ murni _ 900 gr
NZ modif by NaCl _ 300 gr
NZ modif by NaCl _ 600 gr
NZ modif by NaCl _ 900 gr
ESD kWh/m3
35
0.70
0.4
0.26
0.9
0.58
0.3
NZ murni _ 300 gr
NZ murni _ 600 gr
NZ murni _ 900 gr
NZ modif by NaCl _ 300 gr
NZ modif by NaCl _ 600 gr
NZ modif by NaCl _ 900 gr
ESC kWh/kg
36
48.88
52
63
104.9
110
116
128
160
160
172
177.06
180
199.93
200.40
224.11
228
233.57
290.56
309
0 50 100 150 200 250 300 350
Silica Gel
Water Sensible Heat Storage
Paraffin Latent Heat Storage
Zeolite 13X/MgSO4/ENG-TSA (Expanded Natural Graphite treated…
Zeolite NaX
CaNaA-60 (zeolite)
MgNaX (Impregnated zeolited)
Zeolite 4A
Zeolite LiX
AS/CaCl2 (Impragnated aluminosilicate)
NZE activated (300gr)
Zeolite 13X
NZE activated (600gr)
NZE activated (900gr)
NZE_NaCl (300gr)
Silica gel impregnated with CaCl
NZE_NaCl (900gr)
NZE_NaCl (600gr)
Hybrid of zeolite 13X and AA Impregnated with LiCl
(kWh/m3)
Comparison of Energy Storage Density (kWh/m3)
37 1. Hasil uji karakterisasi pada zeolite alam murni menunjukkan bahwa zeolite alam asal blitar memiliki luas
permukaan yang tinggi, memiliki kerangka kerja tipe mordenite dengan komposisi yang lebih banyak,
memiliki rasio Si/Al yang rendah sehingga akan banyak kation yang dapat ditukarkan dengan kation Na+
Kesimpulan
2. Metode modifikasi dengan penjenuhan kation Na+ terbukti dapat meningkatkan kualitas zeolite alam. Hal ini
terlihat dari meningkatnya luas permukaan dan volume pori, struktur kristalin yang lebih stabil, thermal
conductivity yg lebih baik, serta kemampuan adsorpsi dan desorpsi yang lebih baik dibandingkan dengan
zeolite alam tanpa modifikasi
3. Pengujian ATES dengan menggunakan zeolite alam hasil modifikasi menunjukkan kinerja yang lebih
baik.
4. Pengembangan adsorben yang berbahan dasar zeolit alam berhasil menjawab tantangan Pengembangan
adsorben berbahan dasar mineral alam asli indonesia
Modifikasi Zeolite alam dengan Penjenuhan Na+ menjadi PROOF of CONCEPT dalam
meningkatkan kualitas zeolite alam Indonesia
Daftar Publikasi 1. Experimental performance of adsorption chiller with fin and tube heat exchanger
A. Taufan, E. Djubaedah, A. Manga, and Nasruddin
AIP Conference Proceedings 2001, 020012 (2018); doi: 10.1063/1.5049972
2. Design and performance prediction of solar adsorption cooling for mobile vaccine refrigerator
Euis Djubaedah, Andi Taufan, Nadhira Ratnasari, Adjie Fahrizal, Qayyum Hamidi, and Nasruddin
AIP Conference Proceedings 1826, 020013 (2017); doi: 10.1063/1.4979229
3. Preliminary study of natural zeolite from Bayah for solar powered cooling application
Djubaedah1,2, Wulandari1,3, Nasruddin4,a
IOP Conf. Series: Earth and Environmental Science 105 (2018) 012001 doi :10.1088/1755-1315/105/1/012001
4. Performance prediction of vaccine carrier using adsorption process and 13x/cacl2 composite zeolite as adsorbent
Nasruddin1,a, Q H Alius1, Djubaedah1,2, A Taufan3, R G Gurky1, and A P Arsyad1
IOP Conf. Series: Earth and Environmental Science 105 (2018) 012003 doi :10.1088/1755-1315/105/1/012003
5. Design, development and performance prediction of solar heater for regeneration of adsorbent chamber
Nasruddin1,a, Djubaedah1,2, R G Gurky1, Q H Alius1, and A P Arsyad1
IOP Conf. Series: Earth and Environmental Science 105 (2018) 012004 doi :10.1088/1755-1315/105/1/012004
6. Multi-Objective Optimization of Two-Bed Solar Adsorption Chiller Based in Energy and Economic
E. Djubaedah, A. Rachmat, Nasruddin, A. Kurniawan
IJTech (International Journal of Technology)
7. Surface Area Modification of Natural Zeolite Through NaCl Counterbalanced Treatment to Apply in Adsorption Heat Storage System.
Euis Djubaedah, Dyah Arum, Nasruddin, Yuni k
EVERGREEN Joint Journal of Novel Carbon Resource Sciences & Green Asia Strategy, 2019. 06(03): p. pp225-229.
8. Characterization and potential use of Indonesian natural zeolite from Pangandaran-West Java for thermal energy storage application.
Nasruddin, E. Djubaedah, and D. Wulandari
AIP Conference Proceedings. 2020. AIP Publishing LLC.
9. Thermal Behavior and Characteristic of Pangandaran Natural Zeolites
Dyah Arum Wulandari, N., Euis Djubaedah
EVERGREEN Joint Journal of Novel Carbon Resource Sciences & Green Asia Strategy, 2019
10. Selectivity of Water Adsorbent Characteristic on Natural Zeolite in Cooling Application.
Wulandari, D.A. and E.D. Nasruddin
Journal of Advanced Research in Fluid Mechanics and Thermal Sciences, 2019
38
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TERIMAKASIH
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