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LAPORAN AKHIR
PENELITIAN UNGGULAN DASAR
DANA ITS 2020
Inovasi Teknologi untuk Mengolah Air Tua (Bittern) menjadi
Produk Bahan Kimia Bernilai Tambah dalam Mendukung
Konsep Garam Industri Terintegrasi
Tim Peneliti :
Arseto Yekti Bagastyo, ST., MT., MPhil., PhD (Teknik Lingkungan/FTSPK)
Ervin Nurhayati, ST., MT., PhD (Teknik Lingkungan/FTSPK)
Diah Susanti, ST., MT., PhD (Teknik Material dan Metalurgi/FTI)
IDAA Warmadewanthi, ST., MT., PhD (Teknik Lingkungan/FTSPK)
DIREKTORAT RISET DAN PENGABDIAN KEPADA MASYARAKAT
INSTITUT TEKNOLOGI SEPULUH NOPEMBER
SURABAYA
2020
Sesuai Surat Perjanjian Pelaksanaan Penelitian No: 801/PKS/ITS/2020
LEMBAR PENGESAHAN LAPORAN AKHIR
1. Judul Penelitian : Inovasi Teknologi untuk Mengolah Air Tua (Bittern)
menjadi Produk Bahan Kimia Bernilai Tambah dalam
Mendukung Konsep Garam Industri Terintegrasi
2. Ketua Tim
a. Nama : Arseto Yekti Bagastyo S.T., M.T., M.Phil,
b. Jenis Kelamin : Laki-laki
c. NIP : 198208042005011001
d. Jabatan Fungsional : Lektor
e. Pangkat/Golongan : Penata Muda
f. Fakultas/Jurusan : Fakultas Teknik Sipil, Perencanaan, dan
Kebumian/Departemen Teknik Lingkungan
g. Laboratorium : Pengelolaan Limbah Padat dan Limbah B3
h. Tim :
No Nama Lengkap Peran
Dalam Tim Fakultas/Jurusan/Unit Instansi/Perguruan Tinggi
1
Diah Susanti
ST.,MT.,Ph.D
Anggota
Fakultas Teknologi Industri dan Rekayasa
Sistem/Departemen Teknik Material dan
metalurgi
Institut Teknologi
Sepuluh Nopember
2 Ervin Nurhayati
S.T.,M.T.,Ph.D Anggota
Fakultas Teknik Sipil, Perencanaan, dan
Kebumian/Departemen Teknik Lingkungan
Institut Teknologi
Sepuluh Nopember
3
I D A A
Warmadewanthi ST,
MT, Ph.D
Anggota
Fakultas Teknik Sipil, Perencanaan, dan
Kebumian/Departemen Teknik Lingkungan
Institut Teknologi
Sepuluh Nopember
3. Dana dan Waktu :
a. Jangka waktu program yang diusulkan : 3 tahun
b. Biaya yang diusulkan : Rp 321.780.000,-
c. Biaya yang disetujui tahun 2020 : Rp 100.000.000,-
Mengetahui, Surabaya, 22 November 2020
Kepala Pusat Penelitian
Infrastruktur dan Lingkungan
Berkelanjutan
Ketua tim peneliti
IDAA Warmadewanthi, S.T., M.T., PhD Arseto Y Bagastyo S.T., M.T., M.Phil, PhD
NIP. 197502121999032001 NIP. 198208042005011001
Mengesahkan, Menyetujui,
Kepala LPPM ITS
Agus Muhamad Hatta , ST, MSi,Ph.D
NIP. 197809022003121002 NIP.
i
Daftar Isi
Daftar Isi ............................................................................................................................................ i
Daftar Tabel ...................................................................................................................................... ii
Daftar Gambar ................................................................................................................................. iii
Daftar Lampiran ............................................................................................................................... iv
BAB I RINGKASAN ....................................................................................................................... 1
BAB II HASIL PENELITIAN.......................................................................................................... 2
2.1. Kajian Literatur .................................................................................................................. 2
2.1.1. Karakteristik Limbah Bittern ...................................................................................... 2
2.1.2. Contoh Pemanfaatan Bittern ....................................................................................... 3
2.1.3. Elektrodialisis dan Aplikasinya .................................................................................. 3
2.1.4. Penelitian Terdahulu ................................................................................................... 6
2.2. Hasil Penelitian Awal (Uji Pendahuluan) .......................................................................... 7
2.2.1. Karakteristik Limbah Bittern ...................................................................................... 7
2.2.2. Perubahan Parameter Uji Limbah Cair Bittern ........................................................... 9
2.2.3. Pembentukan Presipitat ............................................................................................. 13
2.3. Hasil Kajian Pustaka (Literature Review) ........................................................................ 16
BAB III STATUS LUARAN.......................................................................................................... 20
BAB IV PERAN MITRA ............................................................................................................... 21
BAB V KENDALA PELAKSANAAN PENELITIAN ................................................................. 22
BAB VI RENCANA TAHAPAN SELANJUTNYA ..................................................................... 24
BAB VII DAFTAR PUSTAKA ..................................................................................................... 26
BAB VIII LAMPIRAN................................................................................................................... 27
LAMPIRAN 1 Tabel Daftar Luaran ............................................................................................... 28
ii
Daftar Tabel
Tabel 2.1. Karakteristik Limbah Bittern .......................................................................................... 2
Tabel 2.2. Aplikasi Industri dengan Teknologi Elektrodialisis ........................................................ 6
Tabel 2.3. Penelitian Terdahulu ........................................................................................................ 6
Tabel 2.4. Karakteristik Limbah Bittern Industri Permunian Garam ............................................... 8
Tabel 2.5. Kandungan Ion pada Limbah Bittern Industri Permunian Garam ................................... 9
Tabel 2.6. Prediksi Senyawa Presipitat pada Anoda ....................................................................... 16
Tabel 2.7. Prediksi Senyawa Presipitat pada Katoda ...................................................................... 16
Tabel 6.1. Jadwal Penyelesaian Tahapan Penelitian Tahap I dan Persiapan Tahap II.................... 24
iii
Daftar Gambar
Gambar 2.1. Skema Proses Elektrodialisis ....................................................................................... 4
Gambar 2.2. Susunan Reaktor Elektrodialisis .................................................................................. 5
Gambar 2.3. Skema Mode Operasi Elektrodialisis ........................................................................... 5
Gambar 2.4. Perubahan DHL Air Limbah dan Produk Selama Proses Electrodialysis .................. 10
Gambar 2.5. Perubahan TDS dalam Air Limbah dan Produk Selama Proses Electrodialysis ....... 10
Gambar 2.6. Perubahan Konsentrasi Klorida (Cl) dalam Air Limbah dan Produk Selama Proses
Electrodialysis ................................................................................................................................. 11
Gambar 2.7. Perubahan Konsentrasi Kalsium (Ca) dalam Air Limbah Selama Proses
Electrodialysis ................................................................................................................................. 12
Gambar 2.8. Perubahan Konsentrasi Magnesium (Mg) dan Sulfat (SO4) dalam Air Limbah Selama
Proses Electrodialysis ..................................................................................................................... 12
Gambar 2.9. Perubahan COD Air Limbah Selama Proses Electrodialysis ..................................... 13
Gambar 2.10. SEM Presipitat dalam Kompartemen Anoda dengan Pembesaran .......................... 14
Gambar 2.11. SEM Presipitat dalam Kompartemen Katoda dengan Pembesaran ......................... 14
Gambar 2.12. Hasil Uji EDX Presipitat dalam Kompartemen Anoda ............................................ 15
Gambar 2.13. Hasil Uji EDX Presipitat dalam Kompartemen Katoda ........................................... 15
Gambar 2.14. Hasil Uji XRD Presipitat dalam Kompartemen Anoda ........................................... 15
Gambar 2.15. Hasil Uji XRD Presipitat dalam Kompartemen Katoda .......................................... 16
Gambar 2.16. Roadmap Hasil Penelusuran Perkembangan Penelitian dalam Penerapan Teknologi
Recovery dan Pemanfaatan Limbah Air Tua (Bittern) ................................................................... 17
Gambar 2.17. Metode Penelusuran Pencarian Artikel dan Proses Kajian Literatur Topik
Pemanfaatan dan Recovery Limbah Air Tua (Bittern) ................................................................... 18
iv
Daftar Lampiran
Lampiran 1 Tabel Daftar Luaran……………………………………………………………….25
1
BAB I RINGKASAN
Tingginya konsumsi garam di Indonesia khususnya untuk sektor industri masih belum sejalan
dengan tingkat kemampuan produksi garam yang memadahi baik dari sisi kualitas maupun
kuantitas. Masih dominannya pemakaian teknologi konvensional dalam produksi garam
menjadikan garam nasional sebagian besar berkualitas rendah dan laju produksi tidak bisa
memenuhi kebutuhan pasar. Pemerintah menggulirkan program Garam Industri Terintegrasi yang
diklaim mampu meningkatkan kualitas produk garam lokal dari NaCl 88 persen menjadi garam
industri. Di sisi lain, program tersebut harus juga mampu meminimalisir buangan sebagai
konsekuensi proses produksi tersebut. Limbah air tua yang merupakan air buangan sisa produksi
garam mengandung bahan-bahan yang bisa menjadi polutan jika dibuang langsung ke laut.
Walaupun sebenarnya kandungan dalam air tua (bittern) masih bisa bernilai guna dan mempunyai
ekonomi tinggi bila bisa direcovery. Oleh karena itu, penelitian ini bertujuan untk mengembangkan
inovasi teknologi untuk mengolah/merecovery limbah air tua yang berpotensi menjadi produk
bernilai tambah dalam mendukung program pemerintah tersebut.
Penelitian ini dilakukan dalam 3 tahapan penelitian, yaitu Tahap I (tahun 1- 2020) difokuskan pada
karakterisasi awal limbah bittern yang dihasilkan dari beberapa sumber maupun proses produksi
garam dan potensi valuable products hasil recovery berdasarkan karakteristik limbah tersebut dan
teknologi yang tersedia, salah satunya yang akan dikaji adalah elektrodialisis. Kemudian pada
Tahap II (tahun 2 – 2021), penelitian akan difokuskan pada inovasi teknologi/metode untuk
meningkatkan efisiensi proses recovery limbah bittern sehingga didapatkan tingkat kemurnian
tinggi produk yang bernilai tambah hasil recovery serta efluen limbah bittern yang memenuhi
persyaratan baku mutu. Pada akhirnya di Tahap III (tahun terakhir – 2022), penelitian difokuskan
pada pemantapan/pembuktian konsep (proof-of-concept) pengolahan dan recovery limbah bittern
secara terintegrasi sehingga memiliki kelayakan teknis untuk dapat diterapkan serta dikaji lebih
lanjut terkait kesiapan teknologi termasuk kajian pengelolaan residunya. Luaran yang ditargetkan
adalah publikasi 1 (satu) makalah/paper pada jurnal internasional terindeks Scopus berkategori Q2.
Kata kunci: Bittern, Elektrodialisis, Garam Industri Terintegrasi, Limbah Air Tua, Recovery
Materi
2
BAB II HASIL PENELITIAN
Pada Tahap I (2020), penelitian lebih menitik beratkan pada proses karakterisasi awal dan
memetakan kandungan limbah bittern yang berpotensi untuk dilakukan proses recovery. Selain itu,
dilakukan kajian terhadap beberapa opsi teknologi/metode yang dapat diterapkan dalam proses
recovery limbah bittern. Oleh karena itu, dalam mendukung pelaksanaan tahap 1, maka kajian
literatur dan beberapa skema kerja analisis dasar penelitian dilakukan di tahun pertama (2020).
Berikut ini kemajuan dari pelaksanaan kajian literatur dan hasil penelitian awal.
2.1. Kajian Literatur
Kajian literatur mengacu pada referensi pada jurnal nasional dan jurnal internasional diutamakan
dalam kurun waktu 10 tahun terakhir. Namun tidak menutup kemungkinan untuk membahas
referensi yang terpublikasi > 10 tahun pada topik tertentu yang sangat terbatas akses perolehannya.
Berikut ini adalah ringkasan hasil kajian literatur yang telah dilakukan, meliputi karakteristik
limbah bittern, contoh pemanfaatan linbah bittern, teknologi elektrodialisis dan beberapa penelitian
terdahulu.
2.1.1. Karakteristik Limbah Bittern
Bittern adalah sisa kristalisasi pada proses industri garam yang berbentuk larutan berwarna kuning
agak kecoklatan dengan kepekatan >30 ˚Be. Bittern memiliki berbagai kandungan mineral (seperti
magnesium, natrium, kalium, kalsium, klorida, sulfur dan mineral mikro lainnya), yang tidak dapat
mengkristal saat proses pembuatan garam. Pada umumnya, bittern akan dibuang atau diresirkulasi
kembali ke area penguapan untuk mendapatkan kristal garam dengan kandungan NaCl lebih rendah.
Karakteristik bittern berbeda-beda tergantung dari komposisi yang terkandung di dalamnya, seperti
terlihat pada Tabel 2.1.
Tabel 2.1. Karakteristik Limbah Bittern
Parameter Satuan Air bittern PT Garam
Sumenep (Madura)
Air bittern perusahaan
garam rakyat (NTB)
pH - 7,08 8,69
Magnesium (Mg) mg/L 51,54 30,54
Natrium (Na) mg/L 46,17 69,53
Kalium (K) mg/L 14,49 7,78
Kalsium (Ca) mg/L 103,15 180,01
Khlor (Cl) mg/L 69,40 70,01
Sulfat (SO4) mg/L < 0,59 < 0,59
Posfat (PO4) mg/L 0,04 0,04
Besi (Fe) mg/L < 0,027 < 0,027
Mangan (Mn) mg/L 0,29 0,47
Tembaga (Cu) mg/L 0,063 0,012
3
Parameter Satuan Air bittern PT Garam
Sumenep (Madura)
Air bittern perusahaan
garam rakyat (NTB)
Boron (B) mg/L 87,28 51,50
Kobalt (Co) mg/L 0,008 0,008
Krom (Cr) mg/L 0.018 0,026
Nikel (Ni) mg/L 0,006 0,007
Kadmium (Cd) mg/L 0,083 0,002
Timah (Sn) mg/L < 0,0003 0,007
Timbal (Pb) mg/L 0,297 0,022
Air raksa (Hg) mg/L < 0,0004 < 0,0004
Arsen (As) mg/L 0,014 0,017
(Sudibyo dan Irma, 2011)
2.1.2. Contoh Pemanfaatan Bittern
Kandungan mineral yang cukup banyak dalam bittern menjadikannya layak untuk direcovery.
Penelitian terdahulu menunjukkan bahwa dengan penambahan NaAlO2 500 mg/L Al3+ dalam pH
13 dan waktu reaksi selama 3 jam, sebesar 96,88% kandungan lithium dalam bittern dapat
direcovery dalam bentuk senyawa LiH(AlO2)2.5H2O (Manao et al., 2012). Selain itu, beberapa
mineral lain yang dapat direcovery dari bittern antara lain boron, magnesium, natrium dengan
menggunakan beberapa proses fisik-kimia seperti koagulasi-flokulasi, elektrokimia, evaporasi, dan
kristalisasi fraksional.
Bittern dapat dimanfaatkan sebagai supplemen mineral ionik pada air minum, elektrolit alternatif
untuk sel aki bekas, serta koagulan pada industri kertas ataupun pengolahan limbah tepung ikan.
Dengan penambahan bittern sebanyak 40-50 ml dan pengadukan selama 50 detik, nilai TSS yang
dapat diturunkan berkisar antara 72,09 – 72,38% (Nugraha et al., 2018).
2.1.3. Elektrodialisis dan Aplikasinya
Elektrodialisis adalah proses penyisihan yang digerakkan dengan listrik menggunakan membran
penukar ion selektif untuk menyisihkan ion dalam larutan air (Gurreri et al., 2020). Pada prinsipnya,
elektroda dan membran penukar ion (anion exchange membran dan cation exchange membrane)
disusun secara bergantian, dengan elektroda diletakkan paling ujung. Elektroda ini berfungsi
sebagai konduktor untuk mengalirkan arus listrik. Skema proses dan susunan reaktor elektrodialisis
dapat dilihat pada Gambar 2.1 dan Error! Reference source not found..
4
Gambar 2.1. Skema Proses Elektrodialisis
(Gurreri et al., 2020)
Sistem operasi dalam proses elektrodialisis dapat digunakan dengan mode batch, feed and bleed,
serta kontinyu (Wenten et al., 2014). Mode batch umumnya digunakan untuk proses elektrodialisis
dengan kapasitas kecil. Pada mode ini, proses demineralisasi cukup tinggi dan tidak bergantung
pada fluktuasi komposisi umpan. Mode feed and bleed umumnya digunakan untuk kapasitas
menengah sampai besar. Sistem feed and bleed ini mudah beradaptasi dengan fluktuasi laju alir dan
komposisi umpan dan demineralisasi yang tinggi. Namun kelemahannya, konsumsi energinya
menjadi lebih tinggi, demikian pula dengan laju resirkulasinya, akibat sistem perpipaan yang lebih
kompleks. Mode kontinyu dapat digunakan untuk proses elektrodialisis dengan kapasitas besar.
Dalam mode ini, konsumsi energi menjadi lebih murah. Selain itu, biaya perpipaan, tangki
penyimpanan, serta kontrol juga dapat ditekan menjadi lebih murah. Akan tetapi, efektifitas proses
menjadi lebih rentan, akibat adanya keterkaitan sistem antara konsentrasi umpan, laju
demineralisasi, serta fluktuasi pada laju aliran. Skema mode operasi elektrodialisis dapat dilihat
pada Gambar 2.3. .
5
Gambar 2.2. Susunan Reaktor Elektrodialisis
(Gurreri et al., 2020)
Gambar 2.3. Skema Mode Operasi Elektrodialisis
(Wenten et al, 2014)
6
Menurut Huang (2007), terdapat 4 (empat) elemen yang berpengaruh dalam proses elektrodialisis,
yaitu: DC Supply, jenis elektroda, membran penukar ion, serta pelarut dan elektrolit. Kelebihan
proses elektrodialisis antara lain recovery pengolahannya tinggi, masa pakai membran yang
digunakan lebih lama, serta operasional prosesnya dapat dilakukan hingga suhu 50 ˚C. Sedangkan
kekurangannya antara lain tidak dapat menyisihkan bakteri atau virus, serta sangat sensitif terhadap
membrane fouling.
Aplikasi industri dengan teknologi elektrodialisis dapat dilihat pada
Tabel 2.2.
Tabel 2.2. Aplikasi Industri dengan Teknologi Elektrodialisis
Aplikasi Industri Desain Stack dan
Proses
Status
Aplikasi
Hambatan Permasalahan
Desalinasi air payau Sheet dan tortuous,
reverse polarity
Komersial Biaya proses Biaya
Air umpan boiler
dan air umpan
proses
Sheet dan tortuous,
reverse polarity
Komersial Kualitas
produk dan
biaya
Biaya
Pengolahan limbah Sheet dan tortuous,
reverse polarity
Komersial Karakteristik
membran
Fouling
Demineraalisasi
produk makanan
Sheet dan tortuous,
reverse polarity
Komersial
pilot plant
Selektivitas
membran
Fouling
Produksi gram meja Sheet dan tortuous,
reverse polarity
Komersial Biaya proses Fouling
(Strathmann, 2010)
2.1.4. Penelitian Terdahulu
Sebagai referensi dalam pelaksanaan penelitian, beberapa penelitian terdahulu dirangkum dalam
Tabel 2.3.
Tabel 2.3. Penelitian Terdahulu
Penulis Hasil
Hapsari, 2008 Penelitian dilakukan untuk memisahkan ion Natrium (Na) dan
ion Magnesium (Mg), menggunakan variasi operasi waktu
operasi. Waktu operasi yang dilakukan adalah 30, 60, 90, 120
dan 150 menit. Hasil diperoleh untuk ion Na rejeksi 78,43%
dengan waktu 30 menit dan untuk ion Mg rejeksi sebesar
97,02% selama waktu 150 menit.
7
Penulis Hasil
Astuti, 2014 Variasi tegangan yang digunakan dalam penelitian ini adalah 6
V, 9 V dan 12 V. Hasil dari penelitian yang paling efektif adalah
debit 0,13 L/jam (waktu detensi 38 jam) pada tegangan 6V dan
lama pemaparan ozon selama 5 menit. Removal TDS sebesar
35,68%, salinitas 36,65% dan klorida 34,75%.
Elazhar et al, 2014 Penelitian dilakukan secara batch. Hasil penelitian ini
digunakan untuk menyisihkan garam dalam air payau.
Yusuf, 2015 Penelitian dilakukan dengan 3 dan 5 kompartemen. Hasil
recovery garam pada parameter salinitas terbesar adalah pada
rapat arus 2,5 mA/cm2 dengan 5 kompartemen yaitu 29,28%
dan total chlorine sebesar 50,83 mg/L.
Hassan et al, 2019 Penelitian ini menggunakan sistem kontinyu dengan reaktor
biohidrogen. Hasil penelitian untuk memisahkan VFA dengan
elektrodialisis meningkatkan hasil hidrogen dengan faktor 3,5
dan produksi VFA meningkat dari 1894 mg/L menjadi 4678
mg/L. Selama fase fermentasi removal COD sebesar 49,07%
dan VS sebesar 60,52%.
Scarazzato et al, 2015 penelitian menggunakan limbah elektroplating yang
mengandung 1-hydroxyethane-1,1-diplhosphonic aacid
(HEDP), proses elektrodialisis (ED) yang digunakan untuk
menentukan batas arus listrik. Sistem menggunakan 5
kompartemen, menggunakan kationik (HDX 100, warna pink)
dan membran anion (HDX 200, warna hijau).Kurva tegangan
arus digunakan untuk menentukan arus menghasilkan nilai
antara 29,4 mA dan 33,6 mA (1,8 mA/cm2 dan 2,1 mA/cm2).
Guo et al, 2018 Recovery Lithium klorida menggunakan air laut dengan
menggunakan variasi tegangan 3 V-9 V. Hasil dalam penlitian
ini pada 7 V merupakan tegangan yang optimum 62,70%.
2.2. Hasil Penelitian Awal (Uji Pendahuluan)
2.2.1. Karakteristik Limbah Bittern
Sampel limbah bittern didapatkan dari salah satu perusahaan industri pemurnian garam yang
berlokasi di Surabaya. Pada Tabel 2.4 berikut ini dilaporkan data sekunder karakteristik limbah
bittern hasil analisis bulan Januari-Mei 2020.
8
Tabel 2.4. Karakteristik Limbah Bittern Industri Permunian Garam
No Test Description Unit Hasil Analisis
Baku
Mutu
Jan Feb Maret April Mei
Physical Properties
1 Temperature ˚ C 25.3 24.8 26.2 25.9 27.9 40
2 Total dissolved Solid, TDS mg/L 14700 36150 30800 6280 23300 4000
3 Total Suspended Solid, TSS mg/L > 7.5 109 190 48 37 400
Chemical Properties
1 pH pH
units 7.54 7.75 8.13 7.05 7.68 6 – 9
2 Dissolved Iron, Fe mg/L < 0.02 0.21 0.1 0.04 0.03 10
3 Dissolved Manganese, Mn mg/L 0.08 0.43 0.12 0.22 0.2 5
4 Barrium, Ba mg/L 0.25 2.31 2.09 1.43 1.32 3
5 Cupper, Cu mg/L 0.03 0.08 0.07 0.008 0.006 3
6 Zinc, Zn mg/L 0.14 < 0.04 0.12 0.04 0.03 10
7 Haxavalent Chromium, Cr6+ mg/L < 0.005 < 0.005 0.007 < 0.005 < 0.005 0.5
8 Total Chromium, Cr mg/L < 0.108 < 0.108 < 0.108 < 0.108 < 0.108 1
9 Cadmium, Cd mg/L 0.009 0.005 < 0.003 0.006 0.005 0.1
10 Mercury, Hg mg/L < 0.00007 < 0.00007 0.00007 0.00012 0.00022 0.005
11 Lead, Pb mg/L < 0.006 < 0.006 0.046 0.071 0.056 1
12 Stanum, Sn mg/L < 0.00008 < 0.00008 < 0.00008 0.04 0.007 3
13 Arsenic, As mg/L < 0.00004 0.25 0.002 0.11 0.003 0.5
14 Selenium, Se mg/L < 0.006 < 0.006 < 0.006 < 0.006 < 0.006 0.5
15 Nickel, Ni mg/L 0.093 0.45 < 0.08 < 0.08 < 0.08 0.5
16 Cobalt, Co mg/L < 0.13 0.34 < 0.13 < 0.13 < 0.13 0.6
17 Cyanide, CN mg/L 0.01 < 0.005 < 0.005 0.006 0.005 0.5
18 Sulfide, H2S mg/L < 0.015 < 0.015 < 0.015 0.017 0.012 0.1
19 Flouride, F mg/L 1.02 0.9 0.74 0.4 0.32 3
20 Free Chlorine, Cl2 mg/L < 0.04 0.15 0.05 0.04 0.04 2
21 Free Ammonia, NH3-N mg/L 0.014 0.063 0.067 < 0.01 < 0.01 5
22 Nitrate, NO3-N mg/L 1.19 2.22 2.19 0.86 0.73 30
23 Nitrite, NO2-N mg/L 0.008 0.017 0.013 0.05 0.04 3
24
Biochemical Oxygen Demand, BOD5 mg/L 105 566 86 39 17 150
25 Chemical Oxygen Demand, COD mg/L 316 1160 276 151 42 300
26 Surfactants, MBAS mg/L 0.29 0.8 0.033 0.17 0.15 10
27 Phenol mg/L < 0.005 < 0.005 0.01 < 0.005 < 0.005 1
28 Oil and Grease mg/L < 2.4 2.9 < 2.4 3.9 3.4 -
29 Vegetable Oil mg/L < 2.4 < 2.4 < 2.4 2.5 < 2.4 10
9
No Test Description Unit Hasil Analisis
Baku
Mutu
Jan Feb Maret April Mei
30 Mineral Oil mg/L < 2.4 < 2.4 < 2.4 < 2.4 < 2.4 50
Parameter-parameter yang diuji pada Tabel 2.4 didasarkan pada Peraturan Gubernur Jawa Timur
Nomor 72 Tahun 2013 tentang Baku Mutu Air Limbah bagi Industri dan/atau kegiatan Usaha
Lainnya untuk kategori Baku Mutu bagi Kegiatan Industri Lain. Selain parameter-parameter
tersebut, kandungan-kadungan ion penting dan/atau dominan dalam bittern ditampilkan pada Tabel
2.5. Dapat dilihat bahwa kandungan TDS yang tinggi (Tabel 2.4), sebagian besar disebabkan karena
kandungan ion-ion khususnya Na dan Cl (Tabel 2.5). Kandungan TDS yang tinggi inilah yang
selama ini menjadi tantangan bagi industri garam dalam mengolah air limbahnya (bittern) sehingga
memenuhi baku mutu aman dibuang ke badan air.
Tabel 2.5. Kandungan Ion pada Limbah Bittern Industri Permunian Garam
No Parameter Konsentrasi
(mg/L)
Test Method
1 Magnesium (Mg) 2840 APHA 3120 B
2 Natrium (Na) 22825 APHA 3120 B
3 Calcium (Ca) 217 APHA 3120 B
4 Kalium (K) 840 APHA 3120 B
5 Chloride (Cl) 60804 4500-Cl-B
6 Sulfat (SO4) 4518 4500-SO42--E
2.2.2. Perubahan Parameter Uji Limbah Cair Bittern
Selain karakterisasi bittern, pada percobaan pendahuluan dilakukan juga beberapa eksperimen
untuk mendapat gambaran awal fenomena yang terjadi terhadap beberapa parameter uji, seperti
DHL (daya hantar listrik), TDS (total dissolved solid), konsentrasi klorida, calsium, magnesium,
sulfat dan COD (chemical oxygen demand) selama proses elektrodialisis dijalankan.
10
Gambar 2.4. Perubahan DHL Air Limbah dan Produk Selama Proses Electrodialysis
Gambar 2.5. Perubahan TDS dalam Air Limbah dan Produk Selama Proses Electrodialysis
11
Gambar 2.6. Perubahan Konsentrasi Klorida (Cl) dalam Air Limbah dan Produk Selama
Proses Electrodialysis
Parameter uji khususnya DHL, TDS dan konsentrasi klorida diukur pada air limbah dan produk
untuk melihat terjadinya perpindahan ion dari kompartemen anoda dan katoda (air limbah) ke dalam
kompartemen produk. Dapat dilihat pada Gambar 2.4 hingga Gambar 2.6, parameter DHL, TDS,
dan konsentrasi klorida dalam kompartemen produk mengalami peningkatan. Hal ini menunjukkan
bahwa transport ion dari kompartemen anoda dan katoda menuju kompartemen produk terjadi
sebagaimana diharapkan. Peningkatan konsentrasi di kompartemen produk ini seharusnya diiringi
dengan menurunnya kandungan yang sama di dalam air limbah. Namun sebagai mana terlihat pada
Gambar 2.5 dan Gambar 2.6, TDS dan konsentrasi klorida dalam air limbah cenderung tidak
terjadi perubahan. Hal ini kemungkinan disebabkan karena TDS dan konsentrasi klorida awal di
dalam air limbah yang sangat tinggi sehingga perubahan yang relatif kecil tidak terdeteksi dengan
metode analisis yang diterapkan dalam percobaan ini. Sementara itu, DHL air limbah terlihat sedikit
meningkat walaupun DHL dalam produk juga meningkat (Gambar 2.4). Hal ini dikarenakan
walaupun terjadi transport ion dari air limbah ke produk, kemungkinan juga terjadi penguraian
polutan (kandungan organik) dalam air limbah yang menghasilkan spesies terlarut yang bisa
meningkatkan DHL air limbah.
12
Gambar 2.7. Perubahan Konsentrasi Kalsium (Ca) dalam Air Limbah Selama Proses
Electrodialysis
Gambar 2.8. Perubahan Konsentrasi Magnesium (Mg) dan Sulfat (SO4) dalam Air Limbah
Selama Proses Electrodialysis
13
Kandungan magnesium dan sulfat di dalam air limbah diukur untuk mengetahui potensi removal
magnesium dalam air limbah (selain transport menuju ke kompartemen produk) sebagai presipitat
garam magnesium sulfat. Dalam Gambar 2.8 terlihat bahwa magnesium konsisten mengalami
penurunan selama proses namun kandungan sulfat terlihat fluktuatif. Pada analisis selanjutnya
(Tabel 2.6 dan Tabel 2.7) didapatkan bahwa probabilitas terbentuknya presipitat magnesium lebih
pada pembentukan magnesium hidroksida. Adapun untuk kandungan kalsium dalam air limbah
(Gambar 2.7) terlihat fluktuatif dan tidak menunjukkan trend.
Gambar 2.9. Perubahan COD Air Limbah Selama Proses Electrodialysis
Gambar 2.9 menunjukkan perubahan COD air limbah selama proses percobaan. Terlihat bahwa
kandungan organik terukur fluktuatif selama proses. Hal ini dikarenakan selain proses
electrodialysis terjadi juga proses oxidasi di dalam kompartemen anoda. Proses oksidasi ini dapat
mengkonversi kandungan awal senyawa organik menjadi senyawa organik lain dan/atau mineral.
Tingkat okisidasi senyawa produk antara ini bervariasi sehingga dalam pengukuran COD terbaca
fluktuatif. Selain itu, kandungan ion-ion seperti klorida dan besi juga merupakan penggangu dalam
pengukuran COD. Dalam pelaksanaan analysis COD pada percobaan selanjutnya hal ini perlu
diantisipasi.
2.2.3. Pembentukan Presipitat
Kandungan ion-ion dalam air limbah berpotensi membentuk presipitat. Gambar 2.10 dan Gambar
2.11 menunjukkan SEM image presipitat yang terakumulasi di kompartemen anoda dan katoda.
Dari gambar-gambar tersebut terlihat secara morfologi presipitat dalam kompartemen katoda
berukuran lebih besar dibandingkan presipitat dalam kompartemen katoda. Namun, analisis lebih
lanjut untuk mengetahui penyusun presipitat melalui analisis EDX (Gambar 2.13, Gambar 2.14)
terlihat bahwa kandungan kedua presipitat tersebut hampir sama. Secara umum elemen yang
14
dominan ada adalah Cl, Mg, Na, K, Ca, O. Perbedaan paling mencolok yang terlihat adalah adanya
elemen Fe dalam kompartemen anoda. Hal ini diperkirakan karena terjadi disolusi ion Fe dari
konektor anoda ke dalam larutan yang kemudian mengalami proses presipitasi (Gambar 2.14).
Hal ini sejalan dengan hasil analisis XRD yang dilakukan (Gambar 2.14, Gambar 2.15; Tabel
2.6, 2.7) bahwa pada presipitat anoda diperkirakan terdapat senyawa FeCl2 yang tidak ditemui
dalam presipitat di kompartemen katoda. Berdasarkan hasil uji XRD tersebut didapatkan bahwa
probabilitas tertinggi presipitat yang terbentuk baik di kompartemen anoda maupun katoda adalah
NaCl, CaCO3, Mg(OH)2 dan HgCl. Sementara untuk presipitat Ca, terjadi perbedaan antara anoda
dan katoda; di mana di anoda terbentuk Ca3(PO4)2 sementara di katoda terbentuk Ca5O13P3. Sebagai
pengganti FeCl2, dikarenakan di katoda tidak terdapat ion Fe, maka terbentuk presipitat HgCl2.
(a) (b) (c) (d)
Gambar 2.10. SEM Presipitat dalam Kompartemen Anoda dengan Pembesaran
(a) 150x; (b) 250x; (c) 500x; (d) 2500x
(a) (b) (c) (d)
Gambar 2.11. SEM Presipitat dalam Kompartemen Katoda dengan Pembesaran
(a) 150x; (b) 250x; (c) 500x; (d) 2500x
15
Gambar 2.12. Hasil Uji EDX Presipitat dalam Kompartemen Anoda
Gambar 2.13. Hasil Uji EDX Presipitat dalam Kompartemen Katoda
Gambar 2.14. Hasil Uji XRD Presipitat dalam Kompartemen Anoda
16
Gambar 2.15. Hasil Uji XRD Presipitat dalam Kompartemen Katoda
Tabel 2.6. Prediksi Senyawa Presipitat pada Anoda
No Presipitat Formula Persentase (%)
1 Natrium klorida NaCl 35,3
2 Aragonite CaCO3 30,2
3 Magnesium hydroxide (Brucite) Mg(OH)2 17,2
4 Kalsium fosfat Ca3(PO4)2 10
5 Lawrencite FeCl2 6,1
6 Calomel HgCl 1,1
Tabel 2.7. Prediksi Senyawa Presipitat pada Katoda
No Presipitat Formula Persentase (%)
1 Natrium klorida NaCl 36,5
2 Aragonite CaCO3 27,6
3 Magnesium hydroxide (Brucite) Mg(OH)2 16,1
4 Hydroxylapatite Ca5O13P3 9,2
5 Raksa (II) klorida HgCl2 7,9
6 Sylvite HgCl 2,6
2.3. Hasil Kajian Pustaka (Literature Review)
Kajian pustaka dilakukan untuk mendapatkan informasi dan data-data efektifitas dan efisiensi
beberapa aplikasi teknologi recovery dan pemanfaatan limbah air tua yang didapatkan dari
penelitian-penelitian terdahulu. Penelusuran perkembangan teknologi dilakukan untuk memetakan
17
“key results” yang sudah dapat dibuktikan secara ilmiah dan mengetahui “research gaps” yang
perlu diteliti lebih lanjut. Selain itu juga, didapatkan potensi penerapan teknologi yang sesuai
dengan karateristik limbah air tua yang dihasilkan dari suatu industry garam maupun dari petani
tambak garam tradisional. Pada Gambar 2.16 berikut ini dapat dilihat bahwa hasil penelitian
mengenai bittern resource recovery pertama kali dipublikasikan pada tahun 1918 melalui penerapan
teknologi evaporasi dan presipitasi. Beberapa produk recovery yang dominan adalah berbasis Mg.
Beberapa dekade setelahnya (diantara 1920-1960) sulit ditemukan artikel yang dipublikasikan,
walaupun kemungkinan penelitian serupa masih terus dilakukan. Pada tahun era 1960, beberapa
penerapan teknologi dan paten proses telah ada untuk recovery limbah air tua (bittern) untuk
mendapatkan garam berbasis K, Mg, dan beberapa produk lain seperti Li dan Br dengan teknologi
evaporasi, presipitasi dan solvent extraction.
Gambar 2.16. Roadmap Hasil Penelusuran Perkembangan Penelitian dalam Penerapan
Teknologi Recovery dan Pemanfaatan Limbah Air Tua (Bittern)
Perkembangan penelitian selanjutnya adalah kombinasi proses evaporasi dengan proses ion
exchange pada tahun 1970-an dan pemanfaatan limbah air tua secara langsung sebagai koagulan
untuk mengolah air limbah lain, misalnya limbah domestik, yang sudah mulai diperkenalkan pada
tahun 1980-an. Seiring berjalannya waktu dan perkembangan teknologi pengolahan air limbah
secara umum, maka aplikasi proses recovery limbah air tua dengan menggunakan teknologi
membrane dan elektrodialisis mulai dikembangkan pada tahun 2000-an sebagai alternatif teknologi
recovery. Di era yang sama, pemanfaatan limbah air tua dengan mengambil produk berbasis Mg
juga dilakukan dimana dikombinasikan dengan proses presipitasi untuk menghasilkan produk
struvite. Pada akhirnya, di dekade terakhir (2010-2020), penelitian serupa banyak dilakukan untuk
mengkaji dan mengoptimalkan proses recovery untuk meningkatkan efisiensi produksi dan
kemurnian produk hasil recovery. Selain itu juga, di era ini, perkembangan penelitian dengan
18
mengkaji alternative proses lain juga dilakukan, yaitu proses recovery dengan menggunakan proses
elektrokimia dan kalsinasi, maupun pemanfaatan produk hasil recovery bittern sebagai absorben
polutan gas CO.
Gambar 2.17. Metode Penelusuran Pencarian Artikel dan Proses Kajian Literatur Topik
Pemanfaatan dan Recovery Limbah Air Tua (Bittern)
Selanjutnya, artikel-artikel terdahulu yang dipublikasikan di jurnal internasional dikaji berdasarkan
sub topik-sub topik pembahasan yang meliputi: karakteristik bittern, produk hasil recovery dan
kemurniannya, teknologi-teknologi alternatif untuk proses recovery dan perkembangannya
(Gambar 2.17). Pembahasan selanjutnya adalah konsep strategi yang dapat direkomendasikan
untuk potensi penerapan teknologi tersebut di skala petani tambak garam tradisional maupun skala
industri garam.
Kajian yang diawali dengan pembahasan mengenai prospek perkembangan industri garam dan
proyeksi peningkatan produktifitas garam dari tambak garam tradisional maupun industri garam
yang berimplikasi pada potensi peningkatan limbah air tua (bittern). Kajian selanjutnya adalah
mengenai pemetaan karakteristik limbah air tua (bittern), potensi produk yang dominan didapatkan
dari recovery limbah bittern serta distribusi sumber limbah tersebut. Kemudian dilanjutkan dengan
kajian utama mengenai teknologi recovery dan pemanfaatan limbah bittern yang sudah diteliti
hingga saat ini serta perkembangannya. Kajian literature diakhiri dengan analisis mengenai poteni
penerapan teknologi pada skala tambak garam tradisional maupun industry garam serta konsep
strategi penerapannya. Sehingga, secara keseluruahn susunan (outline) dari kajian literatur adalah
sebagai berikut:
1. Introduction
2. Bittern By-products Generated from Salt Production
2.1. Characteristic of Bittern
2.2. Potential Product of Bittern Recovery
2.3. Distribution of Mg-rich Bittern
3. Resource Recovery and Utilization of Bittern Wastewater
3.1. Resource Recovery Process
19
3.1.1. Membrane Separation
3.1.2. Electrolysis
3.1.3. Electrodialysis
3.1.4. Precipitation and Crystallization
3.1.5. Others
3.1.6. Combined Processes
3.2. Potential Utilization of Bittern for Environmental Processes
3.2.1. Bittern as a Coagulant
3.2.2. Bittern as an absorbent
3.2.3. Bittern as an Mg-source in Struvite Precipitation
4. Conclusions and Future Outlook
4.1. Possible Recovery Technology
4.2. The Concept of Strategy in Technology Implementation
20
BAB III STATUS LUARAN
Status luaran wajib berupa publikasi artikel dalam jurnal internasional (min Q2) hingga saat ini
adalah finalisasi draft artikel yang telah siap untuk dilakukan submission. Adapun draft artikel yang
disusun adalah literature review, bukan berupa research article. Hal ini dikarenakan pelaksanaan
penelitian sedang berlangsung. Pelaksanaan penelitian di laboratorium mengalami hambatan berupa
keterlambatan dalam pembuatan reaktor uji, sehingga data primer penelitian yang didapatkan
kurang mencukupi untuk dapat dilakukan analisis/pembahasan. Detail status luaran dapat dilihat
pada isian ketercapaian luaran di bagian Lampiran 1.
21
BAB IV PERAN MITRA
Tidak ada realisasi kerjasama dan realisasi kontribusi mitra, baik in-kind dan in-cash dalam skema
penelitian unggulan dasar multidisiplin ini.
22
BAB V KENDALA PELAKSANAAN PENELITIAN
Tidak dapat dipungkiri, kondisi pandemi (hingga saat ini) mempengaruhi pelaksanaan penelitian
secara umum. Tahun 2020 adalah tahun pertama penelitian dimana segala sesuatunya termasuk
tahap persiapan mengalami hambatan berupa keterlambatan dalam pelaksanaan yang sesuai dengan
jadwal rencana semula.
Adapun kendala-kendala/tantangan yang dihadapi selama pelaksanaan penelitian pada tahap 1 ini
meliputi tahapan kegiatan:
1. Pengambilan sampel limbah bittern
Salah satu tujuan pelaksanaan penelitian Tahap I adalah karakterisasi limbah bittern. Dalam hal ini
diperlukan sampel limbah bittern. Namun proses pengambilan sampel limbah bittern mengalami
keterlambatan 1-2 bulan dari rencana dikarenakan industri pemurnian garam tidak beroperasi karena
status PSBB Kota Surabaya. Sebagai antisipasi, maka dilakukan pengumpulan data sekunder secara
paralel untuk dapat menganalisis data dan menentukan parameter uji yang menjadi analisis
parameter utama. Saat ini, sampel limbah bittern telah dilakukan.
2. Pengadaan material untuk rancang bangun reaktor skala laboratosium dan reactor uji
skala pilot
Seperti halnya kegiatan pengambilan sampel, kegiatan pengadaan material untuk proses rancang
bangun reaktor uji juga mengalami keterlambatan 1-2 bulan dikarenakan tidak beroperasionalnya
vendor penyedia bahan/material karena status PSBB Kota Surabaya. Selain itu juga, beberapa
material harus dipesan dan didatangkan dari luar kota (Jakarta/Jawa Barat) dan mengalami
penundaan, misalnya akrilik, elektroda dan membran. Saat ini, material telah tersedia sesuai
kebutuhan.
3. Pelaksanaan penelitian di laboratorium dan analisis uji laboratorium untuk parameter
kimia
Pelaksanaan penelitian di laboratorium meliputi penelitian karakterisasi limbah bittern dan uji
pendahuluan dengan menggunakan reaktor uji (bench scale). Dengan adanya keterlambatan
pengambilan sampel limbah bittern dan kendala ketersediaan material untuk reaktor uji di
laboratorium, maka pelaksanaan penelitian untuk mendapatkan data primer baru dapat dilaksanakan
pada awal bulan Juni. Selain itu, adanya kebijakan tidak dioperasikannya laboratorium di
Departemen Teknik Lingkungan sebagai lokasi penelitian menyebabkan tertundanya pelaksanaan
penelitian. Uji pendahuluan hanya dapat dilaksanakan selama 7-10 hari, sebelum akhirnya
diberlakukan kebijakan serupa hingga pertengahan bulan Juli. Saat ini, uji pendahuluan sudah
dimulai kembali dan sedang berlanjut tahap pelaksanaan penelitian (pengoperasian reaktor uji skala
laboratorium). Kebijakan pembatasan waktu operasional kegiatan di laboratorium juga memberikan
dampak pada keterlambatan analisis sampel untuk menguji parameter kimia, misalnya uji SEM-
EDX dan XRD yang dilakukan di laboratorium eksternal. Namun saat ini, walaupun terdapat
keterlambatan, pelaksanaan penelitian sudah dapat menyesuaikan dengan kondisi dan situasi yang
ada.
23
4. Proses desain dan perakitan reaktor uji skala pilot
Proses desain reaktor uji skala pilot seharusnya dilakukan setelah mendapatkan data karakteristik
awal limbah bittern dan uji pendahuluan dengan proses elektrodialisis skala laboratorium
menggunakan sistem batch (bench scale). Akan tetapi, dikarenakan adanya keterlambatan
pelaksanaan penelitian sebagaimana pada poin 1 hingga poin 3 di atas, maka desain reaktor uji skala
pilot dilakukan terlebih dahulu sebagai antisipasi pergeseran jadwal penelitian. Desain yang
dilakukan adalah berdasarkan data sekunder dan dengan perhitungan dimensi yang disesuaikan
dengan kondisi ketersediaan alat dan bahan. Sehingga nantinya diperlukan validasi perhitungan
efektifitas proses recovery setelah didapatkan data primer yang lengkap dari hasil uji di
laboratorium. Adapun proses perakitan reaktor uji skala pilot saat ini sudah selesai dan siap untuk
dilakukan pengujian di laboratorium untuk Tahap II di Tahun 2021.
5. Penyusunan draft artikel luaran wajib
Dengan adanya kendala di atas, maka penyusunan draft artikel yang direncanakan berupa research
article masih belum dapat dilaksanakan karena sangat terbatasnya data primer hasil penelitian di
laboratorium. Sehingga draft artikel yang dipersiapkan adalah berupa literature review mengenai
topik penelitian. Artikel ini membahas potensi pemanfaatan limbah bittern dan aplikasi teknologi
berdasarkan data sekunder hasil penelurusan studi terdahulu. Saat ini, draft artikel untuk luaran
wajib sudah dalam tahap finalisasi persiapan untuk dapat dilakukan submission.
24
BAB VI RENCANA TAHAPAN SELANJUTNYA
Dalam mencapai luaran yang dijanjikan, rencana penyelesaian penelitian Tahap I, meliputi:
1. Penyelesaian penelitian di laboratorium dan analisis uji laboratorium untuk parameter
kimia
Saat ini, pelaksanaan penelitian sudah dapat menyesuaikan dengan kondisi dan situasi yang ada.
Dengan sisa waktu yang ada di tahun pertama hingga bulan November 2020, penelitian akan
difokuskan pada karakterisasi limbah bittern dan uji pendahuluan menggunakan reaktor bench scale
untuk mendapatkan data primer mengenai potensi produk yang dapat dihasilkan dari proses
recovery limbah bittern menggunakan teknologi elektrodialisis. Adapun tahapan penelitian
mengenai proses permurnian produk dengan reaktor bench scale akan dilaksanakan pada Tahap II
di tahun 2021. Keterlibatan beberapa asisten peneliti diharapkan mampu untuk mengejar
ketertinggalan mendapatkan data primer uji laboratorium.
2. Penyelesaian rancang bangun prototype reaktor uji sakala pilot laboratorium untuk
pelaksanaan penelitian Tahap II
Proses rancang bangun reaktor uji skala pilot laboratorium dengan kapasitas 10-15 L telah selesai
dipersiapkan. Reaktor ini digunakan pada pelaksanaan penelitian Tahap II. Sehingga, penelitian
berupa recovery limbah bittern dengan menggunakan reaktor uji ini dapat dilaksanakan dengan
kondisi operasional yang telah didaptkan pada eksperimen menggunakan reaktor bench scale.
3. Pengiriman draft artikel luaran wajib
Draft artikel berupa kajian literature (literature review) dengan judul “Resource Recovery and
Utilization of Bittern Wastewater Generated from Salt Production: A Review on Technologies and
Potential Application” sudah dalam tahap finalisasi dan siap dikirim ke jurnal “Sustainable
Environment Research” (Q1). Draft artikel ini memuat pembahasan mengenai teknologi-teknologi
dan research gaps terkait potensi pemanfaatan limbah bittern dan aplikasi teknologi. Kajian yang
dilakukan meliputi, efektifitas dan efisiensi proses recovery, mekanisme recovery, kemurnian
produk hasil recovery, roadmap pengembangan teknologi recovery untuk bittern wastewater serta
strategi dan potensi aplikasinya untuk di salt farm and salt industries. Pada Tabel 6.1. berikut ini
disajikan jadwal penyelesaian Tahapan Penelitian pada Tahap I (Tahun pertama di Tahun 2020).
.
Tabel 6.1. Jadwal Penyelesaian Tahapan Penelitian Tahap I dan Persiapan Tahap II
No Nama Kegiatan
Bulan/Minggu
November Desember
Januari 2021
(Tahap II) dst.
1 2 3 4 1 2 3 4 1 2 3 4
1 Penyelesaian penelitian dengan menggunakan reaktor bench scale. X X X X X X X
2 Finalisasi laporan:
-Log book X X X
-Laporan akhir X X X
-Laporan keuangan/SPJ X X X
25
No Nama Kegiatan
Bulan/Minggu
November Desember
Januari 2021
(Tahap II) dst.
1 2 3 4 1 2 3 4 1 2 3 4
3 Publikasi Ilmiah: (luaran wajib)
-Penulisan draft artikel (Literatur review) X X X
-Target article submission X X
-Proses review artikel oleh jurnal X X X X X X X X
4 Persiapan penelitian Tahap II X X X
5 Pelaksanaan penelitian Tahap II X X X
26
BAB VII DAFTAR PUSTAKA
Astuti, U.P., 2014. Pengolahan air payau menggunakan elektrodialisis dan ozon. Tesis. Teknik
Lingkungan. Institut Teknologi Sepuluh Nopember.
Elazhar, F., Elazhar, M., Hafsi, M., Taky, M., El Midaoni, A., 2014. Performances of electrodialysis
process in desalination of brackish waters at various salinities and voltage. International
Journal of Advanced Chemistry 2(2), 49-52.
Guo Z.H., Ji, Z.Y, Chen, Q.B., Liu, J., Zhao, Y.Y., Li, F., Liu, Z.Y., Yuan. J.S., 2018.
Prefractionation of LiCl from concentrated seawater/ salt lake brines by electrodialysis with
monovalent selective ion exchange membranes. Journal of Cleaner Production 193, 338-350.
Gurreri, L., Cipollina, A., Tamburini, A., Micale, G., 2020. Chapter 6- Electrodialysis for
wastewater treatment-Part I: Fundamentals and municipal effluents. Current Trends and
Future Development on (Bio-) Membranes, 141-192.
Hapsari, N., 2008. Proses pemisahan ion Natrium (Na) dan Magnesium (Mg) dalam bittern
(buangan) industri garam dengan membran elektrodialisis. Jurnal Teknik Kimia 3(1), 192-
198.
Hassan, G.K., Nicolau, J.M., Dinsdale, R., Jones, R.J., Abo-Aly, M.M., El-Gohary, F.A., Guwy,
A., 2019. A novel method for increasing biohydrogen production from food waste using
electrodialysis. International Journal of Hydrogen Energy 44(29), 14715-14720.
Manao, R.D., Alfianto, R., Sumarno. 2012. Recovery garam lithium pada air tua (bittern) dengan
metode presipitasi. Jurnal Teknologi Kimia dan Industri 1(1), 292-297.
Nugraha, K.A., Wesen, P., Mirwan, M., 2018. Pemanfaatan bittern sebagai koagulan alternatif
pengolahan limbah tepung ikan. Jurnal Ilmiah Teknik Lingkungan 8(1), 1-9.
Scarazzato, T., Buzzi, D.C., Bernades, A.M., Tenorio, J.A.S., Espinosa, D.C.R., 2015. Current-
voltage curves for treating effluent containing HEDP: determination of the limiting current.
Brazillian Journal of Chemical Engineering 32(4), 831-836.
Strathmann, H., 2010. Electrodialysis, a mature technology with a multitude of new applications.
Desalination 264(3), 268-288.
Sudibyo, A, Susanti, I., 2011. Studi Pemanfaatan Air Bittern Sebagai Suplemen Dan Pengawetan
Produk Pangan. Jurnal Hasil Penelitian Industri 24(2), 67-83.
Wenten, I.G., Hakim, A.N., Khoiruddin., 2014. Elektrodialisis. Diktat. Teknik Kimia, Institut
Teknologi Bandung.
27
BAB VIII LAMPIRAN
Lampiran berisi table daftar luaran (Format sesuai lampiran 1) dan bukti pendukung luaran wajib
dan luaran tambahan (jika ada) sesuai dengan target capaian yang dijanjikan.
28
LAMPIRAN 1 Tabel Daftar Luaran
Program : Penelitian Unggulan Dasar Dana Lokal ITS
Nama Ketua Tim : Arseto Yekti Bagastyo, PhD
Judul : Inovasi Teknologi untuk Mengolah Air Tua (Bittern)
menjadi Produk Bahan Kimia Bernilai Tambah dalam
Mendukung Konsep Garam Industri Terintegrasi
1.Artikel Jurnal
No Judul Artikel Nama Jurnal Status Kemajuan*)
1 Resource Recovery and Utilization
of Bittern Wastewater Generated
from Salt Production: A Review on
Technologies and Potential
Application
Sustainable Environment
Research
Draft artikel siap
disubmit
*) Status kemajuan: Persiapan, submitted, under review, accepted, published
2. Artikel Konferensi
No Judul Artikel Nama Konferensi (Nama
Penyelenggara, Tempat, Tanggal)
Status Kemajuan*)
N/A
*) Status kemajuan: Persiapan, submitted, under review, accepted, presented
3. Paten
No Judul Usulan Paten Status Kemajuan
N/A
*) Status kemajuan: Persiapan, submitted, under review
4. Buku
No Judul Buku (Rencana) Penerbit Status Kemajuan*)
1 Judul Book Chapter:
Kajian potensi pemanfaatan limbah
air tua menjadi bahan baku kimia
dengan menggunakan teknologi
presipitasi dan elektrodialisis
Persiapan
*) Status kemajuan: Persiapan, under review, published
5. Hasil Lain
No Nama Output Detail Output Status Kemajuan*)
1 Prototipe Reaktor Elektrodialisis
untuk Recovery Limbah Bittern
Rancang Bangun Peralatan
untuk Proses Recovery
Reaktor siap dilakukan
pengujian
*) Status kemajuan: cantumkan status kemajuan sesuai kondisi saat ini
29
6. Disertasi/Tesis/TugasAkhir/PKM yang dihasilkan
No Nama Mahasiswa NRP Judul Status*)
1 Afrah Zhafirah
Sinatria
03211950010006 Recovery Garam dari Limbah
Bittern Menggunakan Metode
Elektrodialisis
In progress
*) Status kemajuan: cantumkan lulus dan tahun kelulusan atau in progress
Resource Recovery and Utilization of Bittern Wastewater 1
Generated from Salt Production: A Review on Technology and Its 2
Potential Application 3
4
Arseto Yekti Bagastyoab*, Komala Affiyanti Affandia, Sucahyaning Wahyu Trihasti Kartikaa, Syaima 5
Gatneha, Ervin Nurhayatiab 6
7
aDepartment of Environmental Engineering, Faculty of Civil, Planning, and Geo Engineering, Institut 8
Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia 9
10
bResearch Centre for Infrastructure and Sustainable Environment, Institut Teknologi Sepuluh 11
Nopember, Surabaya 60111, Indonesia 12
13
14
*Corresponding author: 15
Arseto Yekti Bagastyo 16
Department of Environmental Engineering, Faculty of Civil, Planning, and Geo Engineering, Institut 17
Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia 18
Research Centre for Infrastructure and Sustainable Environment, Institut Teknologi Sepuluh 19
Nopember, Surabaya 60111, Indonesia 20
21
(E-mail: [email protected]) 22
23
24
25
26
Abstract 27
The process of salt production either from traditional salt farm/ industry or desalination plant produces 28
substantial amount of brine and bittern which considered as a waste. Brine and bittern have negative 29
impact to the environment as it contains high salt concentration and other metal pollutants such as 30
calcium, magnesium, potassium, lithium, boron, bromine, etc. Due to increasing research related on 31
resource recovery and potential use of bittern, extracting valuable mineral from bittern becoming an 32
attractive option. This paper provides a comprehensive review related on bittern characteristic, potential 33
recovery product, recovery technology, and direct utilization, in order to understand possible 34
technology applied in the developing countries, and future outlook. Several recovery technology, i.e., 35
membrane separation, electrolysis, electrodialysis, precipitation and crystallization, and combined 36
treatment, were discussed in this paper, includes the potential use of bittern as coagulant, absorbent, 37
and Mg-source for struvite production. 38
39
Keywords: bittern, extraction, resource recovery, salt production, direct utilization. 40
41
42
43
1. Introduction 44
Annual global salt production have exceeded 290 million tonnes in 2019 (U.S Geological Survey, 45
2020). A 60% of the total salt production is consumed by chemical industry, followed by food-46
processing industry at 30% and other uses,i.e., ice control and road stabilization, water treatment, etc., 47
at 10% (Sedivy, 2009). The common methods used in the global salt production may involve: (i) 48
evaporation system, i.e. artificial (open-pans and vacuum evaporation) or natural (solar evaporation); 49
(ii) brine purification, i.e.,by addinglime, gypsum or other alkaline sources, applying decantation 50
process, mother liquor concentration, or nanofiltration; (iii) solid salt purification, i.e. flotation, 51
electrostatic separation, thermo adhesive process; and (iv) rock salt mining (Spanish Association of Sea 52
Salt Producers (SALIMAR), 2019). 53
Nevertheless, solar evaporation method is widely implemented by most salt producers to date, 54
traditionally in acommunity-based salt farm) or in an industrial scale in arid regions due to its high 55
evaporative rates and where the land is available and affordable (Loganathan et al., 2017). This method 56
is conducted by exposing natural salty water such asseawater, salt lake water, or salt water spring to the 57
open solar light and wind until the crystallized salt is obtained. However, this salt production yields 58
high amounts of concentrated brine wastewater called bittern as by-product. 59
Bittern refers to the concentrated brine which has density between 28-30ºBé, that remaining in the pond 60
as residue after evaporation and crystallization processes of sodium chloride (Nayak, 2018). This stream 61
contains major elements,,i.e. chloride, magnesium, sulphate, sodium, potassium, and calcium ions and 62
other minor elements, such as bromide, boron, cobalt, chromium, ferric, manganese, nickel, and 63
antimon (Davies & Knowles, 2006; Estefan, 1983; Nayak, 2018). Despite some environmental 64
regulations, direct disposal of bittern back into the sea has been recognized as the common management 65
applied worldwide due to the low in capital, operational, and maintenance costs (Ahmad & Baddour, 66
2014; Ariono et al., 2016). However, previous studies reported that the direct disposal of bittern into 67
water body appears to be acutely toxic and potentially lethal to the marine life and ecosystem (i.e., 68
seagrass, mangrove, coral, clam, oyster, fish, green turtle, etc.) particularly in the long term of exposure 69
(Einav et al., 2002; Gacia et al., 2007; Roberts et al., 2010; Tewari et al., 2003; Tovar et al., 2002). 70
Alternative methods of bittern management other than conventional disposal are available, starting 71
small evaporation shed, membrane re-concentration, direct waste utilization and high recovery 72
treatments (i.e., zero liquid discharge or selective salt recovery). These methods aims to reduce the 73
volume of the wastewater so that minimizing the environmental impact. Among these alternative 74
methods, the selective salt recovery has been introduced as the promising sustainable solution for long 75
term application due to the potential added-value products resulted from the residual stream (Mickley, 76
2009). Moreover, the salt recovery approach has potential advantages, i.e., lower disposal cost, provide 77
income from each recovered salt products through one or multiple processing steps, and possible 78
recovery additional water stream. 79
Therefore, this review focuses on discussing applicable technologies for resource recovery of bittern to 80
produce added valuable products. Direct utilization of bittern was also analysed to gen an insight of its 81
beneficial and potential use compared to the processed bittern recovery. Furthermore, the typical 82
characteristics of bittern generated from traditional salt farms and industrial salt production as well as 83
the technology development and challenges of bittern recovery were discussed to point out and 84
formulate the concept of strategies offered for possible technology application. 85
The literature research strategy was to search high quality scientific papers from the science direct, 86
research-gate, and google scholar databases. 87
88
89
Figure 1. Literature search process in this review article 90
The paper published in 1918 to date (2020) was included and reviewed in this study to track the research 91
roadmap of bittern recovery and utilization. Figure 1 highlights keywords and topics that were discussed 92
in this review article. 93
2. Bittern By-products Generated from Salt Production 94
2.1. Characteristics of Bittern 95
Characteristic of bittern depends on the chemical composition of salinewater sources , e.g., seawater, 96
salt lake and salt water spring, the evaporation and precipitation of salt production methods, climate 97
condition, e.g.,temperature, evaporation rate, seasonal variation, and other local variation such as 98
biological activity that can mobilize trace element or adsorb organic and mineral particle during the 99
evaporation process (Amdouni, 2009; Javor, 2002). Nevertheless, the major elements found in bittern 100
is typically the same, either taken from traditional salt farm or from industrial salt manufacture, in 101
several countries (Table 1). 102
It can be seen from Table 1 that bittern has significant amounts of Cl- ion (> 100 g/L) in almost all 103
reported locations, except in some locations in Indonesia, which has lower than 50 g/L (Albuquerque 104
et al., 2013; Apriani et al., 2018a; Ayoub et al., 2011; Baati et al., 2011; BinAhmed et al., 2015; Kilic 105
& Kilic, 2005; Rafie & Mohamed, 2014). This could be due to the high rate of salt production. 106
Interestingly, bittern generated from the evaporation of Eastern Mediterranean seawater was reported 107
to be rich in calcium, sodium, and magnesium ions, i.e., 53.47 g/L to 58.00 g/L (Ayoub et al., 2000). 108
In addition, the same water source that was processed by Camalty Saltwork industrial in Turkey 109
contained 47.4 g/L Mg2+ and 0.0159 g/L B3+ ions (Gurbuz et al., 1996). In the East Asia, a traditional 110
salt farm in Hongkong produced bittern containing high concentrations of Na+ ion, starting from 62.1 111
g/L to 78.1 g/L (X. Z. Li & Zhao, 2002). Another traditional salt farm in Pamekasan and Sampang, 112
Madura, Indonesia, reported Mg-rich bittern i.e., 53.37 – 56.4 g/L, compared to the large-scale industrial 113
salt production, i.e., 15.79 – 31.50 g/L. Bittern wastewater generated from industrial salt production has 114
lower Mg2+ because of the production of magnesium sulphate salts, whereas Cl- is still quite high in the 115
dissolved rejected bittern (Hapsari, 2008b). Apart from the major elements, trace metals such as boron, 116
lithium, bromine, iodine were also identified in bittern with less than 1 g/L (Ismail et al., 2014; Rafie 117
et al., 2013). 118
Tab
le 1
. B
itte
rn c
hara
cter
isti
cs a
t se
vera
l are
as a
roun
d th
e w
orld
1
19
Sa
mp
lin
g l
oca
tio
n
Bit
tern
Ch
ara
cter
isti
c
Sa
lt F
arm
R
aw
M
ate
ria
l R
efer
ence
s P
hy
sica
l p
ara
met
ers
Ma
jor
Ele
men
t (g
/L)
Co
un
try
C
ity
/Co
mp
an
y
pH
S
ali
nit
y
(g/L
)
Sp
ecif
ic
gra
vit
y
Den
sity
(⁰ ⁰⁰⁰B
é)
TD
S
(g/L
) N
a+
K+
Ca
2+
Mg
2+
Cl-
SO
42-
Bra
zil
Gal
inho
s 7.
37
n/a
1.30
n/
a n/
a n/
a 4.
5 0.
04
13.0
0 23
5.91
n/
a In
dust
rial
S
eaw
ater
(A
lbuq
uerq
ue
et
al.,
2013
)
Leb
anon
B
eiru
t 6.
47
n/a
1.29
n/
a 38
2.00
n/
a n/
a 0.
00
68.7
7 25
8.31
54
.50
n/a
Sea
wat
er
(Bin
Ahm
ed
et
al.,
2015
)
Leb
anon
B
eiru
t n/
a n/
a 1.
29
n/a
311.
30
64.9
0 n/
a 0.
00
58.0
0 38
5.00
35
.66
n/a
Sea
wat
er
(Ayo
ub e
t al
., 20
11)
Tur
key
Ana
toli
a
7.2
n/a
1.24
n/
a n/
a 57
.33
19.6
5 1.
27
54.2
6 20
1.68
9.
34
Tra
diti
onal
S
alt L
ake
(Kil
ic &
Kil
ic, 2
005)
Uga
nda
Rub
iriz
i a
9.94
19
6 1.
29
n/a
n/a
144.
00
34.4
0 0.
00
0.00
14
3.00
58
.10
n/a
Sal
t Lak
e (K
ased
de e
t al.
, 201
4)
Uga
nda
Rub
iriz
i b
10.5
17
4 1.
30
n/a
n/a
152.
00
51.1
0 0.
00
0.01
13
1.00
27
.90
n/a
Sal
t Lak
e (K
ased
de e
t al.
, 201
4)
Tun
isia
S
fax
5.40
38
0 1.
30
n/a
n/a
2.70
1.
60
0.00
96
.70
256.
90
33.6
0 In
dust
rial
S
eaw
ater
(B
aati
et
al.,
2011
)
Egy
pt
Ale
xand
ria
n/a
n/a
n/a
n/a
n/a
21.7
0 9.
80
1.60
73
.80
218.
00
3.20
In
dust
rial
S
eaw
ater
(R
afie
&
M
oham
ed,
2014
)
Egy
pt
Fay
oum
/Em
isal
7.
5 n/
a 1.
24
n/a
340.
00
83.5
0 4.
50
0.15
26
.00
185.
00
31.5
0 In
dust
rial
S
alt L
ake
(Ism
ail
et a
l., 2
014)
Indi
a G
anja
m
6.71
n/
a n/
a 29
n/
a 53
.75
10.8
7 0.
10
49.6
1 19
1.98
64
.70
Tra
diti
onal
S
eaw
ater
(N
ayak
, 201
8)
Indi
a G
hogh
a 6.
95
n/a
1.24
28
.5
n/a
77.8
9 7.
63
0.15
31
.74
191.
16
43.2
3 In
dust
rial
S
eaw
ater
(T
ewar
i et
al.
, 200
3)
Sou
th
Kor
ea
Yeo
nggw
ang-
gun
n/a
n/a
n/a
n/a
n/a
55.8
4 14
.32
0.04
41
.77
125.
69
63.9
7 In
dust
rial
S
eaw
ater
(N
a et
al.
, 201
7)
Chi
na
Wei
fang
/Sha
ndon
g H
aihu
a C
o. L
td
n/a
n/a
n/a
n/a
n/a
48.8
0 8.
93
0.06
51
.62
183.
57
71.1
1 In
dust
rial
S
eaw
ater
(X
iao-
Fu
et a
l., 2
020)
Indo
nesi
a S
umen
ep
6.5
92.6
n/
a 29
n/
a 16
6.06
32
.60
0.00
14
.91
256.
00
46.9
2 T
radi
tion
al
Sea
wat
er
(Apr
iani
et a
l., 2
018a
)
Indo
nesi
a G
resi
k 6.
7 10
0 n/
a 28
.5
n/a
181.
64
23.2
3 0.
00
28.7
1 28
0.00
17
.72
Tra
diti
onal
S
eaw
ater
(A
pria
ni e
t al.
, 201
8a)
Indo
nesi
a M
adur
a/P
T G
aram
c n/
a n/
a n/
a n/
a n/
a n/
a 28
.42
4.93
n/
a n/
a n/
a In
dust
rial
S
eaw
ater
(H
apsa
ri, 2
007)
Indo
nesi
a M
adur
a/P
T G
aram
d n/
a n/
a n/
a n/
a n/
a n/
a 57
.35
10.1
0 n/
a n/
a n/
a In
dust
rial
S
eaw
ater
(H
apsa
ri, 2
007)
Sa
mp
lin
g l
oca
tio
n
Bit
tern
Ch
ara
cter
isti
c
Sa
lt F
arm
R
aw
Ma
teri
al
Ref
eren
ces
Ph
ysi
cal
pa
ram
eter
s M
ajo
r E
lem
ent
(g/L
)
Co
un
try
C
ity
/Co
mp
an
y
pH
S
ali
nit
y
(g/L
)
Sp
ecif
ic
gra
vit
y
Den
sity
( ⁰ ⁰⁰⁰B
é)
TD
S
(g/L
) N
a+
K+
Ca
2+
Mg
2+
Cl-
SO
42-
Indo
nesi
a M
adur
a/P
T G
aram
e n/
a n/
a n/
a n/
a n/
a n/
a 86
.82
15.2
7 n/
a n/
a n/
a In
dust
rial
S
eaw
ater
(H
apsa
ri, 2
007)
Indo
nesi
a M
adur
a/P
T G
aram
f n/
a n/
a n/
a n/
a n/
a 21
.426
28
.42
4.93
15
.79
16.4
9 8.
47
Indu
stri
al
Sea
wat
er
(Hap
sari
, 200
8a)
Indo
nesi
a M
adur
a/P
T G
aram
g n/
a n/
a n/
a n/
a n/
a 43
.355
57
.35
10.1
0 31
.50
31.9
2 17
.91
Indu
stri
al
Sea
wat
er
(Hap
sari
, 200
8a)
Tur
key
Cam
alti
Sal
twor
k n/
a n/
a n/
a n/
a n/
a 56
.00
12.0
0 n/
a 47
.40
183.
20
59.2
0 In
dust
rial
S
eaw
ater
(G
urbu
z et
al.
, 199
6)
Chi
na
Xia
men
/Fuj
ian
Sal
t C
ompa
ny
n/a
n/a
n/a
n/a
n/a
n/a
n/a
0.81
31
.60
n/a
n/a
Indu
stri
al
Sea
wat
er
(Z. L
. Ye
et a
l., 2
011)
Egy
pt
Ale
xand
ria
n/a
n/a
n/a
n/a
0.02
0.
29
0.01
1.
6 0.
07
0.21
0.
003
Indu
stri
al
Sea
wat
er
(Raf
ie e
t al
., 20
13)
Indo
nesi
a P
amek
asan
n/
a n/
a n/
a 30
n/
a 0.
04
0.02
0.
002
0.19
0.
22
0.07
T
radi
tion
al
Sea
wat
er
(Sid
ik, 2
013)
Indo
nesi
a S
urab
aya
n/a
n/a
n/a
n/a
n/a
n/a
n/a
n/a
4.04
0.
002
12.5
0 T
radi
tion
al
Sea
wat
er
(Sut
iyon
o, 2
006)
Indo
nesi
a S
ampa
ng
n/a
n/a
n/a
n/a
n/a
n/a
0.32
n/
a 56
.49
n/a
n/a
Tra
diti
onal
S
eaw
ater
(N
adia
et
al.,
2015
)
Indo
nesi
a P
amek
asan
n/
a n/
a n/
a 32
n/
a 17
.31
57.5
7 30
.15
53.3
7 n/
a n/
a T
radi
tion
al
Sea
wat
er
(Am
rull
oh
et
al.,
2019
)
Leb
anon
B
eiru
t 6.
67
n/a
1.27
n/
a 34
2 n/
a n/
a 0.
00
53.6
0 22
2.50
46
.30
Tra
diti
onal
S
eaw
ater
(A
youb
et
al.,
2011
)
Leb
anon
B
eiru
t n/
a n/
a n/
a n/
a 31
1.30
64
.90
n/a
0.00
58
.00
385.
00
35.6
6 T
radi
tion
al
Sea
wat
er
(Ayo
ub
&
Mer
hebi
, 20
02)
Sou
th
Kor
ea
Chu
ngju
n/
a n/
a n/
a n/
a n/
a n/
a n/
a 8.
00
32.0
0 n/
a n/
a n/
a S
eaw
ater
(L
ee e
t al
., 20
03)
Hon
gkon
g S
eash
ore
Vic
tori
a H
arbo
urh
7.67
n/
a n/
a n/
a 15
2.00
78
.10
2.98
0.
65
9.22
n/
a n/
a T
radi
tion
al
Sea
wat
er
(X.
Z.
Li
&
Zha
o,
2002
)
Hon
gkon
g S
eash
ore
Vic
tori
a H
arbo
ur i
8.19
n/
a n/
a n/
a 20
5.00
62
.10
8.47
0.
01
24.9
0 n/
a n/
a T
radi
tion
al
Sea
wat
er
(X.
Z.
Li
&
Zha
o,
2002
)
Leb
anon
B
eiru
t 6.
78
n/a
n/a
n/a
396.
00
70.8
8 14
.00
0.00
53
.47
297.
91
46.2
7 T
radi
tion
al
Sea
wat
er
(Ayo
ub e
t al
., 20
01)
1
20
Note: a rainy season; b dry season; c bittern 1; d bittern 2; ebittern 3; f bittern 1; g bittern 2; h bittern from 121
evaporated 12% initial volume; i bittern from evaporated 4% initial volume; n/a not applicable. 122
123
2.2. Potential product of bittern recovery 124
Several valuable minerals which can be recovered from bittern is described in Table 2. 125
Table 2. Potential product of bittern recovery 126
Recovered mineral Potential Uses References
Na (NaCl, Na2CO3, Na2SO4) Food, glass, soap, detergent, textiles, pulp and paper industries, road de-icing
(Petersen, 1994)
Mg (Mg, MgCl2, MgSO4, MgCO3)
Al, steel, chemical and construction industries, fertiliser, rubber, textile
(Petersen, 1994; Schwochau, 1984)
Ca (CaCO3, CaSO4) Soil amendment, construction industries, fertiliser, calsium and magnesium removal in water treatment
(Petersen, 1994; Schwochau, 1984)
K (KCl, K2SO4) Fertiliser (Petersen, 1994)
Br Fire retardant, agriculture, well-drilling fluids, petroleum additives
(Petersen, 1994)
B Glass products, soap and detergents, fire retardants, fertiliser
(Petersen, 1994)
Li Batteries, glass manufacturing, lubricants and greases, pharmaceutical products, ceramic, metallurgy, air conditioning
(Petersková et al., 2012)
127
The main content of bittern is magnesium which can be reused into other products based magnesium as 128
the source. The product that can be produced from the bittern recovery process with magnesium ion as 129
the main source is solid magnesium hydroxide (Mg(OH)2. Magnesium hydroxide can be produced 130
either from precipitation or electrochemical processes. magnesium hydroxide which is produced from 131
the precipitation process can be done by adding NaOH as alkaline agent. The formation of magnesium 132
hydroxide from the precipitation process was when the magnesium ion inside the bittern reacts with 133
NaOH to form a magnesium hydroxide precipitate. The drawback of the precipitation method is the 134
large amount of sludge, so another method in the process of recovering magnesium ions in bittern to 135
produce magnesium hydroxide products is the electroysis method (Na et al., 2017). Electrolysis method 136
is another method in the process of forming magnesium hydroxide from magnesium contained in 137
bittern. in the process (Hidayah, 2014). A bittern dilution is needed which functions to increase the 138
purity of the product produced. Dilution of 4 times is the best result in the formation of magnesium 139
hydroxide through the electrolysis process resulting in a product purity of 63.84% (Amrulloh et al., 140
2019) compared without going through the dilution process, namely 34.77% (Amrulloh et al., 2016). 141
A combined process is needed to produce magnesium oxide and magnesium chloride which is a 142
magnesium recovery product derived from bittern. Magnesium oxide can be obtained from a 143
combination of processes between electrolysis and calcination(Amrulloh et al., 2020), while magnesium 144
chloride can be obtained from a combination of precipitation and calcination processes (Zuchrillah & 145
Julaika, 2017). The resulting magnesium oxide can then be used as an insulator, fertilizer, material for 146
rayon textile processing, water treatment, paper making, alkalis and pharmaceuticals (Marihati, 2007), 147
thus magnesium chloride products can be used in the pharmaceutical industry, raw materials 148
magnesium, erosion and dust control, ice control, storage materials for hydrogen, and the culinary 149
industry. For the pharmaceutical industry, magnesium chloride is used as medicine (Zuchrillah & 150
Julaika, 2017). 151
Another product that is obtained from the recovery process of magnesium contained in bittern is 152
magnesium carbonate. Magnesium carbonate is produced from the bittern precipitation process with 153
the addition of sodium pentaborate (Apriani et al., 2018b).The process of recovery of potassium, 154
magnesium and sulfate together through the precipitation method is carried out to produce potassium 155
magnesium sulfate double salt (PMS) as a product of the bittern recovery process. The addition of 70% 156
methanol at 30° C is the best result of the PMS product which produces 155.65 g / L (Fernández-Lozano, 157
1996).The magnesium ion in bittern can be recovered by electrodialysis method. The magnesium ions 158
generated can be reused as a supplement ion in drinking water (Hapsari, 2007, 2008b). 159
The products MgKPO4 and Mg2(NH4)2(PO4)2 are products produced from the bittern precipitation 160
process with sources containing ammonium and phosphate. Bittern acts as a source of magnesium in 161
the precipitation process (Nadia et al., 2015; Sidik, 2013). Product MgKPO4then used as fertilizer in 162
milkfish cultivation.The results showed that the ponds that were given with fertilizer from recovery 163
bittern have positif result (changes in weight and length of fish) than without applying fertilizer (Nadia 164
et al., 2015). 165
Another fertilizer product that is the result of bittern recovery with ammonium and phosphate-in 166
wastewater is struvite. In the process of forming struvite the molar ratio between Mg: NH4: PO4 and the 167
pH of the solution must be considered in order to produce struvite with high purity. From several studies 168
it was found that the best molar ratio in the struvite formation process is 1: 1: 1 with a pH range of 8 to 169
9.6 (El Diwani et al., 2007; Lee et al., 2003; Z. L. Ye et al., 2011). In addition, struvite is then can be 170
reused as a slow release fertilizer which is beneficial for plant growth (Alessio Siciliano et al., 2020). 171
Lithium ion is a small part contained in bittern. The lithium content contained in bittern can be recovered 172
by the precipitation method with the help of sodium aluminate (Manao et al., 2012). Beside from 173
precipitation method, the lithium content in bittern can be separated through a membrane separation 174
process, including nanofiltration and reverse osmosis (Sun et al., 2015; Wen et al., 2006). The smaller 175
the rejection percentage of lithium indicates that the lithium ion has separated from bittern.The lithium 176
products obtained can then be reused as raw material for rechargeable batteries (Satriady et al., 2016). 177
Potassium is one of the ions contained in bittern which can be recovered, either through electrodialysis 178
or crystallization (Hapsari, 2008a). The crystallization process of potassium can use the method of 179
adding sodium pentaborate to produce lithium pentaborate precipitates. the result is that 65% of the 180
lithium contained in bittern can be recovered as potassium pentaborate (Gurbuz et al., 1996). 181
182
2.3. Distribution of Mg-rich Bittern 183
A number of studies have shown that the major constituent of bittern is magnesium. High concentration 184
of Mg2+ found in most of research from different countries. Figure 1 shows the distribution map of Mg 185
content in the bittern from respective areas. Camalti Saltwork in Turkey and Shandong Haihua Group 186
Co, in China (Figure 2) exhibited high magnesium content bittern. Meanwhile, in Pamekasan, Madura 187
Island, of Indonesia, magnesium content in bittern was low particularly in traditional salt farm 188
production. 189
190
191
Figure 2. Map showing major countries (Turkey, China, and Indonesia) with magnesium-rich bittern 192
reported research (modified from Google Earth, 2020) 193
194
195
Figure 3. Map showing major countries (Korea, Hongkong, Indonesia, East Mediterranean Sea) with 196
magnesium-rich bittern reported research (modified from Google Earth, 2020) 197
198
Figure 4. Map showing major countries (Tunisia, South Korea, Brazil, and Turkey) with magnesium-199
rich bittern reported research (modified from Google Earth, 2020) 200
201
Figure 5. Map showing major countries (Egypt and India) with magnesium-rich bittern reported 202
research (modified from Google Earth, 2020) 203
204
3. Resource Recovery and Utilization of Bittern Wastewater 205
The first recovery experiment on bittern successfully recovered Epsom salt (MgSO4.7H2O), solid KCl 206
and solid MgCl2.H2O (Hildebrand, 1918). The work on recovering minerals from concentrated brines 207
and bittern started to flourish in 1960s and some of them had been granted patent and applied for field 208
applications, i.e. recovery lithium (Averill & Olson, 1978), potassium (Epstein & Feist, 1975), 209
magnesium, bromine, and other salts (Hanson & Hughes, 1975; Mero, 1965). In this period, the 210
recovery processes were mostly combination process of evaporation, precipitation, and solvent 211
extraction. The timeline of bittern recovery process and the utilization of bittern can be seen in Figure 212
6. 213
The application of evaporation, precipitation, and crystallization methods to recover minerals is still 214
popular in the 1970s. In 1973 for example, potassium recovery was conducted by mixing bittern 215
solutions with gypsum and sodium chloride, followed by magnetic stirring at 80°C temperature for 2 216
hours and dried overnight at 84°C. The potassium recovered from this method ranging from 26.67-217
42.67% (Al-Awadi & Al-Mahdi, 1973). Next, other precipitation process which utilized ethanol 218
generate better potassium magnesium sulfate double salt (PMS) production, i.e. 160.18 g/L rather than 219
the utilization of methanol (Fernandez Lozano, 1976). Over years, the development of other recovery 220
methods are increasing with the use of combined treatment (evaporation-ion exchange) to recover 221
potassium, lithium, and magnesium (Schwochau, 1984). 222
223
Figure 6. Roadmap of product recovery and direct utilization of bittern 224
The experiment on bittern as an alternative coagulant started on 1980s. Previous study presented that 225
the utilization of bittern as a coagulant for industrial wastewater have reduced color contaminant by 80-226
85% (S.-B. Wang & Chen, 1984). The work on bittern recovery process continues in 1990s using 227
different combination of method on possible recovered mineral. In 1993, recovery lithium ions were 228
conducted by precipitation and solvent extraction methods. The precipitation process is carried out with 229
the addition of various types of extractants and sodium aluminate to produce lithium and lithium 230
aluminate precipitates (Bukowsky & Uhlemann, 1993; Manao et al., 2012). In 2010s, the recovery 231
technology developed further using membrane separation methods (i.e., nanofiltration or forward 232
osmosis) and electrodialysis (Hapsari et al., 2008; Somrani et al., 2013; Sun et al., 2015; Wen et al., 233
2006). Some minerals that succesfully recovered by electrodialysis were calcium, potassium sodium, 234
and magnesium ions (Hapsari, 2007; Hapsari et al., 2008). Moreover, the researches on bittern as an 235
alternative absorbent were noticeable in 2010s. In this experiment, bittern is effectively be used as Mg 236
source and CO2 absorbent (Na et al., 2017). The precipitation of Mg(OH)2 increases simultaneously by 237
the addition of NaOH into bittern solution. On the other hand, the absorption of CO2 is more effective 238
with higher concentration of Na+ in the solution. Recently, combined treatment using electrochemical 239
and calcination process were conducted to produce nano-magnesium oxide (Amrulloh et al., 2020). 240
241
3.1. Resource recovery process 242
3.1.1. Membrane separation 243
Membrane separation is one of the ion recovery methods contained in bittern. Membrane separation 244
method is a conventional method which in the separation process can be distinguished based on physico-245
chemical characteristics.Based on the size of the particles or dissolved molecules the separation process 246
can be done through filtration, microfiltration, ultrafiltration and nanofiltration. Meanwhile, reverse 247
osmosis is a method of separating dissolved molecules based on their affinity (Chisti, 2007; Katalin, 248
2000). The separation method using membrane has several advantages including: easy to combine with 249
other methods, does not require additional materials, easy up-scaling, and mild conditions(Katalin, 250
2000).One of the methods utilizing membrane as media separation is the lithium ion recovery process 251
which is found in bittern using the nanofiltration method. 252
The recovery of lithium chloride contained in bittern with a TDS concentration of 500,000 mg/L has 253
been carried out using the nanofiltration method (Wen et al., 2006). Pre-tretment is needed before the 254
recovery process takes place namely by passing the bittern on the multimedia filter and manganese 255
dioxide sand filter to produce turbidity of less than 1 NTU and ferrous and manganese less than 0.1 256
mg/L respectively.After that, bittern dilution is carried out due to the high TDS concentration in bittern 257
so it is not suitable for direct recovery.The material used in the recovery process is a spiral wound Desal-258
5 DL 2540C model which is a type of polyamide composite with an area of 1.77 m2 with an operating 259
condition of 1.10 MPa of feed pressure, a flow rate of 120 L/hour, and temperature is kept below 40° C 260
.From this research, it is known that the Nanofiltration method with the Desal 5-DL membrane type is 261
not effective in the recovery process of lithium chloride with high magnesium and boron content in 262
bittern. The recovery percentage of lithium chloride was 55%, which is lower than the recovery process 263
of lithium chloride using the electrodialysis method that has a recovery percentage of 80%.The low 264
selectivity of the membrane to boron is one of the disadvantages of the recovery method using 265
membrane separation (Katalin, 2000). 266
High magnesium concentration in bittern will result smaller recovery of lithium, this is supported by 267
the research of Sun et al. (2015) that has conducted research with variating the ratio of Mg2+/Li+ to the 268
resulting magnesium and lithium rejection and resulted separation factor (SF) close to 1 when 269
concetration magnesium is high.The type of membrane for separating magnesium and lithium is DL-270
2540 with a membrane area of 2.51 m2 and the percentage of rejection to MgSO4 is 96%.The research 271
conditions were carried out with a flow rate of 600 L/hour and varying temperature (i.e, 25, 30, 35), 272
pressure (i.e, 1.0 MPa-2.0 MPa), pH (i.e, 3-6) and Mg2+/Li+ ratio (i.e, 50-80). The best results were 273
obtained when the research conditions with a Mg/Li 60 ratio were pH 3.1 and a pressure of 2.0 MPa 274
which resulted in a lithium rejection of -160% and a magnesium rejection of 80% with a separation 275
factor (SF) of 0.08.The effect of the Mg/Li ratio was obtained the best percentage of magnesium ion 276
rtejction when the Mg/Li ratio was 50 and decreases when Mg2+/Li+was 80, namely 65% and 50% 277
respectively with percentage rejection of lithium -70% and -55%, respectively, at the same pressure 1.8 278
Mpa(Sun et al., 2015). From all of the variations carried out in the study, the percentage of lithium ion 279
rejection was always negative while the percentage rejction of magnesium ion was positive, this 280
indicates that lithium ions have succeeded in penetrating the membrane but not magnesium, so that the 281
magnesium and lithium ions can separate. 282
The process of separating the lithium contained in bittern can also be carried out using the reverse 283
osmosis method with low pressure and compared to the nanofiltration method. However, the best result 284
obtained is the separation process of lithium contained in bittern using the nanofiltration method rather 285
than reverse osmosis. The percentage of magnesium rejection obtained when the pressure condition was 286
<15 bar and with a dilution of ten times was 100%, while the percentage of lithium rejection obtained 287
was 15%.Nanofiltration is considered to be an effective method of separating monovalent ions from 288
systems containing multivalent ions(Wen et al., 2006). 289
290
3.1.2. Electrolysis 291
Magnesium hydroxide (Mg(OH)2) and magnesium oxide (MgO) are products from recovery process of 292
magnesium ions in bittern using electrochemical methods. The product of magnesium hydroxide from 293
the bittern recovery process is based on the electrolysis reaction that occurs at the cathode where the 294
OH- ion reacts with Mg2+ so that it will form solid magnesium hydroxide based on the reaction 295
(Amrulloh et al., 2016): 296
2H2O(l) + 2e- H2(g) + 2OH-(aq) (1) 297
Mg2+(aq) + 2OH-
(aq) Mg(OH)2 (s) (2) 298
Researchs for the recovery process of magnesium hydroxide using electrolysis method have been 299
carried out(Amrulloh et al., 2016)(Amrulloh et al., 2019)and Hidayah (Hidayah, 2014). Magnesium 300
hydroxide was obtained as a product with an anion compartment configuration filled with KOH that 301
have variations of 0.1 M, 0.2 M, 0.4 M, 0.6 M, 0.8 M and 1 M while cation compartment was filled 302
with bittern with each volume 15 ml. The mass of magnesium hydroxide obtained 0.1 g with a purity 303
of 51.26% when the concentration of concentration was 0.25 M under the electrolysis time of 2 hours 304
and the voltage of 9 volts (Hidayah, 2014). 305
In addition, study on the effect of voltage on Mg(OH)2 produced with an electrolysis time of 10 hours 306
was conducted. The best results indicated by the percentage of Mg(OH)2 contained in the solid was 307
34.77% with a weight of 15.98 g of 100 mL of bittern solution treated when the voltage used was 18 308
volts(Amrulloh et al., 2016). However, from these results it is known that the purity of the resulting 309
magnesium hydroxide is low, so that Amrulloh et al.(2019) conducted another study on bittern recovery 310
using electrochemical methods by diluting bittern with a variation of 0 to 8 times and operating time 311
variations of 1 to 13 hours. The voltage used in this study is the optimal voltage from previous studies, 312
which is 18 volts. XRD results showed that the content of Mg(OH)2 contained in the solid was 63.84% 313
and had impurities in the form of 25.47% CaCO3 and 10.69% NaCl with a weight of 3.04 g when the 314
dilution was 4 times and the operating time was 4 hours. 315
316
3.1.3. Electrodialysis 317
Membrane electrodialysis is a method of bittern recovery by utilizing a semipermeable membrane to 318
certain ions in the presence of an electric current as a driving force. Concentration, operating time and 319
voltage affect the percentage of rejection of an ion. Recovery of potassium, sodium, magnesium, and 320
calcium ions in bittern which can be used as ion supplements in drinking water was done (Hapsari, 321
2008a). The variation of the operating time is 30- 150 minutes with a variation of the voltage given 2.3 322
volts, 2.5 volts, 2.7 volts and 2.9 volts. The optimal voltage was 2.3 volts for potassium ions with a 323
rejection percentage of 92.88%, sodium and magnesium ion have rejection percentage 74.66% and 324
91.9% respectively with the voltage of 2.5 volts, while calcium ion rejection is 96.19% with 2.7 volts. 325
The highest rejection percentage for all ions was obtained when the operating time was 150 minutes. 326
Another result to obtain 78.43% and 98.93% percentage of rejection sodium and calcium ions need the 327
voltage 2.8 volts and 2.9 volts respectively with operation time 30 minute (Hapsari, 2007)(Hapsari, 328
2008b). From these results, it can be seen that the greater the voltage, the shorter the operating time 329
required and produce a higher percentage of rejection at the same initial concentration. 330
331
3.1.4. Precipitation and Crystallization 332
One of the recovery methods of magnesium contained in bittern is precipitation (Alessio Siciliano et 333
al., 2020).Magnesium is recovered by adding sodium carbonate (Na2CO3) to yield a product in the form 334
of magnesium carbonate (Apriani et al., 2018b). Concentration of Mg and the pH of bittern play 335
important role in producing high purity solid magnesium carbonate. A study variying concentration of 336
Mg in bittern (10,000; 20,000; and 40,000 ppm) and pH (8, 9 and 10) found that 100 % magnesium 337
carbonate crystals can be form when Mg concentration was 10,000 and pH was 8 and 9). The pH affects 338
the form of the crystal, which in this case was plates-shape (Apriani et al., 2018b). 339
Magnesium hydroxide solids can be produced from the precipitation process by mixing bittern with 340
NaOH. The precipitation process is carried out by adjusting the pH of 9.5-10 and varying the molar 341
ratio of NaOH/Mg (0.7 to 2.8). The mixture then stirred for 2 hours followed by the precipitation process 342
for 12 hours. The optimal results obtained when the molar ratio of NaOH/Mg was 2.53 (Na et al., 2017). 343
Magnesium potassium phosphate (MgKPO4) is a form of fertilizer product produced from bittern 344
precipitation with NaOH and Na2HPO4 which is utililized as added value in milkfish cultivation. A 345
82.9973 g of MgKPO4 was produced by mixing 400 mL of Na2HPO4, 350 mL of NaOH and 250 mL 346
of bittern(Nadia et al., 2015). 347
348
Different precipitate products were obtained from different precipitation method, i.e.,when different 349
alkaline was added into the bittern. The addition of Ca(OH)2 base will produce more precipitates than 350
KOH and NaOH and produce Mg2(NH4)2(PO4) 2.4H2O precipitates; KMg(NH4)(PO4)2.4H2O; NaMg 351
(NH4)(PO4) 2.4H2O sequentially under conditions of Mg2+: NH4+ molar ratio: PO4
3-1: 1: 1 and pH 9.5 352
(Sidik, 2013). 353
Another product produced from the precipitation process is the recovery process of lithium contained 354
in bittern to become lithium aluminate by adding sodium aluminate (NaAlO2). The process of forming 355
lithium aluminate was influenced by pH, stirring time and concentration of sodium aluminate added. 356
The pH factor affects the recovery results because if the pH of the solution is too alkaline, the lithium 357
that has been deposited will dissolve back into NaAlO2 and H2O as LiOH. The longer and greater the 358
concentration of sodium aluminate added, the greater the recovery of lithium. The optimum conditions 359
for lithium recovery process was solution of pH 13, stirring time of 3 hours and the concentration of 360
sodium aluminate added was 500 mg/L to produce 2.17 g of lithium (Manao et al., 2012). Lithium 361
products can be used as raw material for rechargeable batteries (Satriady et al., 2016) metal alloys for 362
aircraft, and for fusion nuclear fuel (Manao et al., 2012) 363
3.1.5. Others 364
The recovery process of minerals contained in bittern used different of temperature as a method of 365
recovery.The method used is heating and cooling. Recovery was carried out sequentially to obtain 366
magnesium sulphate, sodium sulphate, potassium salt, and potassium chloride in bittern. In the process 367
of recovering magnesium sulphate recrystallization is carried out by a separation process using a 368
centrifuge which is then separated and dried at 70°C. After the magnesium sulphate recovery process, 369
it is followed by the sodium sulphate recovery process separate by a centrifuge and washing it using 370
cold water and then drying it at 110° C. the resulting purity reaches 98.2%.Potassium salt is done by 371
neutralizing the bitterninto pH of 7 which is then heated at a temperature of 125° C. After the heating 372
process, the product of potassium salt is separated by cooling naturally to a temperature of 100° C.The 373
last recovery process is the process of recovering potassium chloride, namely by washing hot water and 374
cooling it to 20°C, the resulting mixture is separated using a centrifuge and the resulting solid is dried 375
at a temperature of 110° C. The resulting potassium chloride has a purity of up to 99 %(Estefan, 1983). 376
377
3.1.6. Combined processes 378
The development of technology makes bittern recovery process not only done by one method, but also 379
it can be combined with other methods to get the product, such as electrolysis - calcination and 380
precipitation - calcination. The purpose from combined methode between electrolysis-calcination in the 381
recovery process of bittern with high magnesium is to obtain magnesium oxide as products. The 382
calcination process has a function to obtain magnesium oxide products after the electrolysis process. In 383
the process, the dilution carried out in the study resulted in the purity of magnesium hydroxide. 384
Magnesium oxide which is formed after electrochemical processes using the best variables in studies 385
(Amrulloh et al., 2019) and (Amrulloh et al., 2016) and calcined at a temperature of 500° C for 4 hours 386
yields 91.21% purity of magnesium hydroxide (Amrulloh et al., 2020). 387
In addition, magnesium chloride (MgCl) is a product that results from the combined precipitation-388
calcination method.The precipitation process was carried out by mixing 8.5% bittern with 7.51% NaOH 389
with 300 rpm stirring for 1 hour. Product from this method is precipitate of 11.48% magnesium 390
hydroxide. Magnesium chloride (MgCl) is produced by adding 3.5% sodium chloride (NaCl) to the 391
precipitate by stirring at 110°C for 3 hours then rinsing and drying. The next process is to calcinate 392
solids with temperature variations of 150° C, 200° C and 250° C for 60, 90 and 120 minutes. The best 393
product with content of 100% MgCl2.6H2O was obtained when the calcination temperature was 150 ° 394
C for 60 minutes. The longer the time and the higher the calcination temperature, the less recovery of 395
magnesium chloride produced(Zuchrillah & Julaika, 2017). 396
397
3.2. Potential Utilization of Bittern for Environmental Processes 398
3.2.1. Bittern as a coagulant in wastewater treatment 399
High magnesium content in bittern makes this waste potential to be used as a coagulant in wastewater 400
treatment. The use of bittern as a coagulant can reduce COD, BOD, TSS, colour, TSS, total phosphate, 401
total nitrogen to heavy metals.The concentrations of COD, BOD, and TSS in fish processing wastewater 402
were successfully reduced by the coagulation-flocculation method with bittern as a magnesium source. 403
The condition of the research carried out by adjusting the pH in the wastewater until the pH reache 9 404
with the addition of NaOH that continue to add of bittern as a source of magnesium with a variation of 405
the bittern volume of 10% - 50%. The mixture of bittern and waste water is left to stand for 1 hour, then 406
followed by a fast stirring process of 100 rpm for 3 minutes and slow stirring of 50 rpm according to 407
the variations carried out, namely the range of 15-75 minutes. The best results from the variation in the 408
research were successful in reducing COD by 74.70%, BOD 76.25%, and TSS by 84% when the added 409
bittern volume was 40% with a slow mixing time of 30 minute (Yanuarita et al., 2017). 410
TSS removal obtained reached 92% with the initial pollutant conditions smaller than 500 mg /L, namely 411
99 mg / L at the same of pH that was 11. This removal efficiency was obtained when the research 412
conditions were carried out in fast stirring of 100 rpm in 1 minute, slow stirring of 30 rpm in 75 minutes 413
and the settling time of 60 minutes. The addition of bittern as a source of magnesium was varied in 414
order to get the best results that variations of bittern added volume was 1-4 mL and the best result was 415
4 mL (Sutiyono, 2006). 416
Beside TSS, COD, and BOD removal in the coagulation-flocculation process with bittern as a source 417
of magnesium, it was able to reduce the concentration of total phosphate, total nitrogen, and color in 418
tannery wastewater. The addition of 5 mL / L bittern into 1 L of tannery waste was able to reduce total 419
phosphate by 87% and total nitrogen by 75% with the initial pollutant conditions of 302 mg / L and 420
34.2 mg / L, respectively. The removal of color in the waste reaches 99.5% when the initial conditions 421
of the pollutant are 5800 NTU and at the pH of the solution is 11.3 (Ayoub et al., 2011). 422
Bitterns have been proven to effectively reduce colour from colour effluents in pulp and textile 423
industries. A colour removal approximately 80% is achieved at a lime dosage of 400 mg/L and of 20 424
mL of bittern to 1000 mL of the acid dye effluent(S.-B. Wang & Chen, 1984). 425
Comparison between bittern as a coagulant with commercial coagulants, namely MgCl2 and Al2(SO4)3 426
has been carried out to compare the ability of bittern with commercial coagulants in the process of 427
removing turbidity and color in dyestuff wastewater.The research conditions were carried out with a 428
solution of pH 11 and varying concentrations of cations in the added coagulants that were from 0 mg/L 429
to 200 mg/L.The best results in the turbidity removal process were obtained under the conditions of 430
adding the concentration of Mg2 + 100 mg / L in the use of bittern and MgCl2 with a removal efficiency 431
of 92%, while koagulant Al2(SO4)3 needed the greater added concentration of Al , namely 200 mg/L for 432
the same efficiency of removal.In addition, the color removal process in wastewater using bittern and 433
MgCl2at a concentration of 100 mg/L had a removal efficiency of 80% and 70%, respectively, while 434
Al2(SO4)3at a concentration of 200 mg/L had a removal efficiency of 82%.From the results obtained, 435
the use of bittern as a coagulant has a positive result when compared to other commercial coagulants, 436
namely by producing greater removal efficiency(Albuquerque et al., 2013). 437
From several Researche, it has been shown that the pH adjustment in the solution was an alkaline pH, 438
which was in the pH range 11. Therefore, the pH adjustment requires more bases than acids as pH 439
control which can be done by adding alkaline agents into solutions such as NaOH or Ca(OH)2. the 440
addition of an alkaline agent into the solution will result in different removal efficiencies in heavy metal 441
removal or the resulting sludge production.In the heavy metal removal process by utilizing an alkaline 442
agent NaOH or Ca(OH)2as a pH controller, the optimal removal efficiency is achieved when using 443
Ca(OH)2 as a pH controller. Research conditions by adding 6.6 Ca(OH)2 to 1 L of wastewater and 444
variations in the addition of added magnesium concentrations to solution were 0 mg/L, 53.5 mg/L, 107 445
mg/L, 160.5 mg/L, 214 mg/L and 267.5 mg/L. The best results were shown by the addition of Mg2+ 446
concentration was 107 mg/L which resulted in removal efficiency of arsenic, cadmium, chromium, 447
copper, lead, mercury, nickel, and zinc of 71.3%, 99.1%, 98.7%, 82.8%, 95.9%, 99.5% , 75.5%, and 448
91.5% respectively (Ayoub et al., 2001). 449
Total coliform and fecal coliform counts before and after the application of coagulation of the optimum 450
dose to Ca(OH)2 or NaOH alkalinized wastewater is effectively reduced. In the optimum dose of liquid 451
bittern, total and fecal coliform counts dropped from 9 x 1012 and 3.4 x 1011 cfu/ml, respectively, to 6.0 452
x 103 and 2.0 x 103 after ½ hour on alkalinization with Ca(OH)2. This indicates that complete destruction 453
of bacteria is achieved by raising the pH of wastewater to 11.2 or 11.5(Diwani & Rafie, 2002). 454
The addition of bittern into wastewater alkalinized with Ca(OH)2 tends to have a lower rise in Total 455
Dissolved Solid (TDS) by 42.25% in liquid bittern and 79.7% in dry bittern compared to the values 456
when NaOH is added to the wastewater sample (Diwani & Rafie, 2002). 457
The main disadvantage of coagulation process using bittern as a source of magnesium and Ca(OH)2 or 458
NaOH is the large amounts of sludge that is generated compared to conventional secondary chemical 459
process using alum or ferric chloride as coagulants. However, sludge generated from lime treatment 460
process have superior dewatering characteristics and can be processed with filter pressing at lower cost 461
than sludge generated from chloride or alum (Diwani & Rafie, 2002). 462
The estimation of sludge resulting from the coagulation process using bittern as a source of magnesium 463
and Ca(OH)2 or NaOH as alkaline agent resulted sludge thickness (i.e , settle sludge volume , sludge 464
volume index, and water content greater using NaOH as a pH controller than Ca (OH) 2 (Ayoub 465
&Merhebi, 2002). This result proved that utilization Ca(OH)2 as an alkaline agent produces less sludge 466
than NaOH. 467
To maintain the effluent discharge pH standards, carbonation by the addition of O2 is needed in 468
concentration ranging from 3.26 to 80 ml/L depending on the initial levels of pH, alkalinity, and the 469
nature of the alkalinizing agent used (Diwani & Rafie, 2002). 470
471
3.2.2. Bittern as an adsorbent 472
The utilization of bittern as an absorbent is rarely applied. However, the research of bittern as an 473
alternative technology in carbon dioxide (CO2) capture and storage (CCS) has gaining attention in the 474
last decade followed the rapid progression of global warming and the need to search for the next 475
generation absorbent. Na et al.(2017) studied the potential use of bittern as CO2 absorbent by 476
precipitating Mg2+ ions as Mg (OH)2 using chemical that can supply the production of hydroxide ions 477
(OH−), such as NaOH, CaO, and Ca(OH)2. The experiment show an increasing Mg2+ removal up to > 478
99% at [NaOH]/[Mg] molar ratios of 2.7–2.75 (pH 9.5–10.0). Higher Na+ concentration has verified to 479
have better performance on CO2 absorption process by capturing them into NaHCO3. Moreover, the 480
addition of NH4OH during process can be acted as catalyst to increase the formation of NaHCO3 and 481
hinder the faster dissolution of CO2. 482
483
3.2.3. Bittern as an Mg-source in struvite crystallization 484
Struvite is a slow release fertilizer which contains magnesium, ammonium, and phosphate 485
(MgNH4PO4.6H2O) in equal molar concentration (Lee et al., 2003). Many wastewaters are high in 486
ammonium and phosphate, but tend to be low in magnesium concentration (El Diwani et al., 2007). 487
Furthermore, some wastewater may have precursor ions such as, Ca2+, Na+, K+, Al3+, Fe3+, CO3-etc, 488
which could react with Mg2+ and PO43- and interfere the precipitation of struvite (Alessio Siciliano et 489
al., 2020; Tao et al., 2016). For this reason, the addition of Mg reagents has to be overdose to increase 490
the chance of struvite formation. The determination of Mg source and type has to be carefully 491
considered as it accounts for major costs, which eventually affects the overall cost of struvite recovery 492
and product quality (El Diwani et al., 2007; Y. Ye et al., 2020). At this point, the use of pure Mg reagents 493
would not be a wise option, as it will results in a very expensive treatment. 494
Bittern, on the other hand, is a by-product which could be achieved for free. It is also very rich in 495
magnesium chloride with small trace of other inorganic compounds. Indeed, it could be use as an 496
alternative for low-cost Mg source. The feasibility of bittern in struvite crystallization have been 497
investigated by some authors to recover ammonia and phosphate from landfill leachate, anaerobic 498
digestate, human urine, pigment industry and swine wastewater (Etter et al., 2011; Sanghavi et al., 2020; 499
A. Siciliano & De Rosa, 2014; Alessio Siciliano, 2016; J. Wang et al., 2018). The best performance on 500
the recovery of nitrogen (>90%) and phosphate (up to 99%) was noted in the range pH of 8.5-9.0 and 501
stoichiometric molar ratio of 1-1.3 (Sanghavi et al., 2020; A. Siciliano & De Rosa, 2014). However, 502
since every wastewater has a unique characteristic related to type of ionic species, direct investigation 503
should be conducted to optimize the removal and recovery process. Compared to other different 504
magnesium sources (i.e., MgO, Mg(OH)2, MgCl2, and MgSO4), the use of bittern did not significantly 505
affect the removal efficiency and product quality (J. Wang et al., 2018). Comparation on different Mg 506
source and size particle showed that each struvite product seems identical and almost spherical. Despite 507
the fact that bittern is possible for struvite formation, its transportation cost has to be accounted for in 508
the total cost estimation; otherwise it could be inefficient and limited for field application. 509
510
3.2.4. Other direct utilization of Bittern 511
Besides for environmental process, bittern have also been used as coagulant for tofu production, 512
alternative cooling agent for agricultural purposes, flame retardants material, etc. (Davies & Knowles, 513
2006; J. Li et al., 2014; L. Li et al., 2019; Lychnos et al., 2010; Xu & Deng, 2006). As in tofu production, 514
bittern is the oldest traditional coagulant for tofu processing (J. Li et al., 2014). It is also the most popular 515
coagulants to use as it create natural flavour and retains original taste of soybeans. However, the use is 516
now limited due to bittern rapid coagulation process, which could make tofu hard and nonuniform. 517
Meanwhile, other researchers have investigated the possibility of bittern as a liquid dessicant in 518
refrigeration system. Although MgCl2 contained in bittern is classified as weaker dessicant (compared 519
to CaCl2, LiBr, LiCl, and triethylene glycol), it is low cost, significantly less toxic both to humans and 520
the environment, and available in abundant quantity in seawater (Davies & Knowles, 2006; Lychnos et 521
al., 2010). Moreover, the result showed that the equilibrium relative humidity (ERH) could decrease to 522
less than 40% at a concentration of up to 37% by mass (corresponding to bittern relatively concentrated 523
80 times than raw seawater). It is also clarify that the utilization of bittern could improve cooling effect 524
on greenhouses, particularly in hot and humid climate. 525
Next, Mg(OH)2 precipitated from seawater bittern could also be use as inorganic flame retardants 526
additives, since it have some advantages such as excellent smoke-repressive, non toxic, and low cost 527
compared to organic bromic flame retardants (Xu & Deng, 2006). From previous study, it is noticeable 528
that utilization of Mg(OH)2 as an additive agents of polyethylene material has significantly improved 529
limiting oxygen index (LOI) to 32.5%, while the combination of Ethylene Vinyl Acetate-MgAl layered 530
double hydroxides (EVA/MgAl-LDHs) composites has increased limiting oxygen index (LOI) to 29.8% 531
(L. Li et al., 2019) 532
533
4. Conclusions and Future Outlook 534
4.1. Possible Recovery Technology (Strategy, economic value, Case study/pilot project example that 535
has been conducted) 536
The need to recover valuable mineral from bittern rise gradually with the increasing salt production, 537
depleting easy available high-grade mineral ores, and environmental issue related to bittern disposal. 538
Some possible bittern recovery technology that have been evaluated for more than nine decades are 539
evaporation, precipitation, crystallization, solvent extraction, ion exchange, membrane separation, 540
electrodialysis, electrochemical method, and calcination. The application of single treatment or 541
combined treatment have verified to successfully some minerals (Na, Ca, Mg, Cl, K, Li, B, Br) for 542
further use as raw materials in chemical industry, food-processing, agriculture, energy-based industry, 543
and many more. Combined treatment of evaporation-precipitation-crystallization have been mostly 544
used to recover mineral as it is relatively easy and low cost compared to other technologies. Moreover, 545
the direct utilizations of bittern have also show potential result. It is noticeable that bittern could be use 546
as a coagulant, either in water treatment or food-processing industry. In addition, bittern could also be 547
used as a source alternative for CO2 absorbent. It can be concluded that direct utilization of bittern could 548
be used for conserving resource as well as protecting the environment quality. 549
In future look, some strategies that can be proposed in bittern management are: a) to recover all possible 550
valuable mineral from bittern; b) the quality of recovered products have to meet standard requirement 551
from targeted market; c) the technology used for recovery mineral has to be effective, efficient, and 552
correspond with targeted recovery product on each area. 553
554
4.2. Challenges (in developed country and particularly in developing country) 555
The advancements in recovery technology show potential application on mineral extraction from 556
bittern. However, it is still a challenge to apply this technology at field application, particularly related 557
to recovery cost, operation and maintenance cost, quality of the recovered product, and the need to 558
search business partner/company who willing to buy recovered product from waste bittern. Those 559
challenge possibly minimal in the developed country rather than in developing country. Nonetheless, 560
more research needs to be conducted to enhance the performance of bittern recovery as well as improve 561
its feasibility on direct utilization. 562
563
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Tewari, A., Joshi, H. V, Ragunathan, C., Trivedi, R. H., & Ghosh, P. K. (2003). The effect of sea brine 765
and bittern on survival and growth of mangrove Avicennia marina (Dicotyledones : 766
Avicenniaceae) Organocatalysis View project Ecology of the inter-tidal zone of the Saurashtra 767
Coast View project. Indian Journal of Marine Sciences, 32(1), 52–56. 768
https://www.researchgate.net/publication/242206751 769
Tovar, L. R., Gutierrez, M. E., & Cruz, G. (2002). Fluoride content by ion chromatography using a 770
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805
806
12
B
un
ga
Ra
mp
ai
……
……
.
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uli
s
Ars
eto
Yekti
B
ag
ast
yo
ad
ala
h
seo
ran
g d
ose
n d
an
pen
elit
i b
era
filiasi
di
Dep
art
em
en
Tekn
ik
Lin
gku
ng
an
,
Faku
ltas
Tekn
ik S
ipil,
Pere
nca
naan
dan
Keb
um
ian
(C
ivp
lan
),
Inst
itu
t Tekn
olo
gi
Sep
ulu
h
No
pem
ber
(ITS),
Su
rab
aya
.
Pen
ulis
m
en
yele
saik
an
st
ud
i p
rog
ram
sarj
an
a t
ah
un
2004 d
an
mag
iste
r ta
hu
n
2006 b
idan
g T
ekn
ik L
ing
ku
ng
an
di
ITS,
sert
a p
rog
ram
MP
hil
tah
un
2009 d
an
Ph
D t
ah
un
2013 b
idan
g T
ekn
ik K
imia
di
the U
niv
ers
ity
of
Qu
een
slan
d, A
ust
ralia.
Saat
ini
(2020), m
en
gem
ban
am
an
ah
seb
ag
ai
kep
ala
Lab
ora
tori
um
Pen
gelo
laan
Lim
bah
Pad
at
dan
Lim
bah
B3 d
i D
ep
art
em
en
Tekn
ik L
ing
ku
ng
an
ITS.
Pen
ulis
b
erp
era
n
akti
f d
ala
m
berb
ag
ai
pen
eliti
an
d
an
p
roje
ct
kerj
asa
ma
dala
m
neg
eri
m
au
pu
n
luar
neg
eri
b
aik
se
bag
ai
ketu
a
mau
pu
n
an
gg
ota
. B
eb
era
pa
hasi
l p
en
elit
ian
ya
ng
d
ihasi
lkan
te
lah
dip
ub
likasi
kan
dala
m ju
rnal n
asi
on
al m
au
pu
n in
tern
asi
on
al b
ere
pu
tasi
,
sert
a
dala
m
sem
inar/
ko
nfe
ren
si
ilmia
h
nasi
on
al
dan
in
tern
asi
on
al.
Bid
an
g p
en
gaja
ran
, p
en
eliti
an
dan
pen
gab
dia
n p
ad
a m
asy
ara
kat
yan
g
dit
eku
ni
an
tara
la
in:
pen
go
lah
an
fisi
k
dan
kim
iaw
i lim
bah
in
du
stri
,
tekn
olo
gi
ele
ktr
okim
ia
dala
m
pen
era
pan
nya
d
i b
idan
g
tekn
ik
ling
ku
ng
an
, re
sou
rce
reco
very
, w
ast
e(w
ate
r)
reu
se
an
d
recy
clin
g,
pen
gelo
laan
lim
bah
pad
at
dan
pen
gelo
laan
lim
bah
B3.
Pen
ulis
dap
at
dih
ub
un
gi m
ela
lui ala
mat
e-m
ail b
ag
ast
yo@
en
viro
.its.
ac.
id.
KA
JIA
N P
OT
EN
SI
PEM
AN
FA
AT
AN
LIM
BA
H A
IR T
UA
MEN
JA
DI
BA
HA
N
BA
KU
KIM
IA D
EN
GA
N M
EN
GG
UN
AK
AN
TEK
NO
LO
GI
ELEK
TR
OD
IALIS
IS D
AN
PR
ES
IPIT
AS
I
Ars
eto
Yekt
i B
agast
yo, P
hD
; D
iah S
usa
nti
, P
hD
; E
rvin
Nurh
ayati
, P
hD
; ID
AA
Warm
adew
anth
i, P
hD
;
1. P
en
da
hu
lua
n
Seca
ra
um
um
, p
rose
s p
rod
uksi
d
i in
du
stri
g
ara
m
men
gh
asi
lkan
lim
bah
beru
pa l
aru
tan
peka
t, y
an
g d
iseb
ut
den
gan
air
tu
a,
seb
ag
ai
pro
du
k s
am
pin
g s
ete
lah
pro
ses
pen
gu
ap
an
d
an
kri
stalis
asi
g
ara
m.
Pem
bu
an
gan
se
cara
lan
gsu
ng
ke
ling
ku
ng
an
p
era
iran
akan
m
em
beri
kan
dam
pak n
eg
ati
f te
rhad
ap
kese
imb
an
gan
osm
oti
k b
iota
air
,
teru
tam
a
pad
a
eko
sist
em
d
i se
kit
ar
titi
k
pem
bu
an
gan
akib
at
pen
ing
kata
n k
on
sen
trasi
gara
m m
inera
l (T
ew
ari
et
al.,
2003).
Pili
han
te
kn
olo
gi
pen
go
lah
an
p
un
sa
ng
at
terb
ata
s d
ikare
naka
n ad
an
ya ko
nse
ntr
asi
to
tal
pad
ata
n
terl
aru
t ya
ng
cu
kup
ti
ng
gi
dala
m
limb
ah
air
tu
a
mem
bu
tuh
kan
en
erg
i m
au
pu
n t
eka
nan
yan
g c
uku
p b
esa
r
un
tuk m
en
gh
ilan
gka
n p
olu
tan
ters
eb
ut.
Di
sisi
la
in,
limb
ah
air
tu
a
ini
seb
en
arn
ya
mem
iliki
kan
du
ng
an
m
ag
nesi
um
, n
atr
ium
, kaliu
m
dan
kals
ium
2
Bu
ng
a R
am
pa
i …
……
….
dala
m k
on
sen
trasi
tin
gg
i (H
ap
sari
, 2008a;
Xia
o-F
u e
t al.,
2020).
Seb
ag
ai
con
toh
, ko
nse
ntr
asi
kaliu
m
dan
mag
nesi
um
masi
ng
-masi
ng
bis
a m
en
cap
ai 86 g
/L d
an
32
g/L
pad
a li
mb
ah
air
tu
a d
ari
ind
ust
ri g
ara
m (H
ap
sari
, 2007;
2008a;
2008b
). K
an
du
ng
an
min
era
l in
i b
erp
ote
nsi
un
tuk
dap
at
dim
an
faatk
an
kem
bali
men
jad
i p
rod
uk l
ain
yan
g
mem
iliki
added
va
lue,
se
hin
gg
a
ko
nse
p
pen
go
lah
an
limb
ah
air
tu
a
dap
at
berf
oku
s p
ad
a
pro
ses
reco
very
min
era
l g
ara
m y
an
g m
asi
h t
ers
isa d
ala
m lim
bah
ters
eb
ut.
Seh
ing
ga,
dih
ara
pkan
lim
bah
air
tu
a
sud
ah
akan
men
gala
mi
pen
uru
nan
ko
nse
ntr
asi
min
era
l d
an
vo
lum
e
un
tuk
dap
at
mem
en
uh
i b
aku
m
utu
lin
gku
ng
an
ya
ng
dip
ers
yara
tkan
.
Beb
era
pa t
ekn
olo
gi r
ecove
ry li
mb
ah
meru
pakan
pro
ses
fisi
k-k
imia
wi
beru
pa
pro
ses
pem
isah
an
se
nya
wa
ion
ik,
pro
ses
kri
stalis
asi
, dan
pro
ses
pem
isah
an
pad
ata
n. B
eri
ku
t
ini
ula
san
m
en
gen
ai
tekn
olo
gi
ele
ktr
od
ialis
is
dan
pre
sip
itasi
yan
g d
ap
at
dig
un
akan
seb
ag
ai a
ltern
ati
f p
rose
s
reco
very
lim
bah
air
tu
a.
2.
Alt
ern
ati
f T
ek
no
log
i Recovery
Lim
ba
h A
ir
Tu
a
2.1
. M
em
bra
n E
lek
tro
dia
lisi
s
Mem
bra
ne
ele
ktr
od
ialis
is
meru
pakan
sa
lah
sa
tu
meto
de re
cove
ry lim
bah
air
tu
a d
en
gan
m
en
gg
un
akan
mem
bra
n s
em
iperm
eab
el
terh
ad
ap
io
n t
ert
en
tu d
en
gan
Bu
ng
a R
am
pa
i …
……
…. 1
1
TE
KN
IK –
Ju
rna
l Il
mia
h B
ida
ng
Ilm
u K
ere
ka
ya
saa
n,
33
(2).
66
–7
0.
Te
wa
ri,
A.,
H.V
. Jo
shi,
C.
Ra
gu
na
tha
n,
R.H
. T
riv
ed
i, d
an
P.K
.
Gh
osh
(2
00
3).
Th
e e
ffe
ct o
f se
a b
rin
e a
nd
bit
tern
on
surv
iva
l a
nd
g
row
th
of
ma
ng
rov
e
Av
ice
nn
ia
ma
rin
a
(Dic
oty
led
on
es
: A
vic
en
nia
cea
e).
In
dia
n J
ou
rna
l o
f G
eo
-
Ma
rin
e S
cie
nce
s, 3
2(1
). 5
2–
56
.
Xia
o-F
u,
G.,
L. D
an
, L.
Jia
n-L
u,
W.
Zo
ng
-Ru
i, W
. Ju
n,
Z.
Yin
g-Y
ing
,
da
n
Y.
Jun
-Sh
en
g
(20
20
).
Se
pa
rati
on
o
f so
diu
m
an
d
po
tass
ium
u
sin
g
ad
sorp
tio
n
–
elu
tio
n/c
ryst
all
iza
tio
n
sch
em
e
fro
m
bit
tern
. C
he
mic
al
En
gin
ee
rin
g
Re
sea
rch
an
d D
esi
gn
, 1
61
. 7
2–
81
.
Ye
, Z
.L.,
S.H
. C
he
n,
M.
Lu,
J.W
. S
hi,
L.F
. Li
n,
da
n S
.M.
Wa
ng
(20
11
).
Re
cov
eri
ng
p
ho
sph
oru
s a
s st
ruv
ite
fr
om
th
e
dig
est
ed
sw
ine
wa
ste
wa
ter
wit
h b
itte
rn a
s a
ma
gn
esi
um
sou
rce
. W
ate
r S
cie
nce
an
d T
ech
no
log
y,
64
(2).
33
4–
34
0.
Zu
chri
lla
h,
D.R
.,
da
n
S.
Jula
ika
(2
01
7).
P
en
ga
ruh
su
hu
d
an
wa
ktu
fu
rna
ce
da
lam
p
em
bu
ata
n
Mg
Cl 2
.6H
2O
d
ari
bit
tern
. Se
min
ar
Na
sio
na
l S
ain
s d
an
Te
kn
olo
gi
Te
rap
an
V.
18
9–
19
4.
10
B
un
ga
Ra
mp
ai
……
……
.
Ha
psa
ri,
N.
(20
07
). P
rose
s p
em
isa
ha
n i
on
K (
ka
liu
m)
da
n C
a
(ca
lsiu
m)
da
lam
bit
tern
de
ng
an
me
mb
ran
ele
ktr
od
iali
sis.
Jurn
al
Re
ka
ya
sa P
ere
nca
na
an
, 4
(1).
1–
11
.
Ha
psa
ri, N
. (2
00
8a
). P
en
ga
mb
ila
n m
ine
ral e
lekt
roli
t d
ari
lim
ba
h
ga
ram
(b
itte
rn)
un
tuk
sup
lem
en
min
era
l io
nik
pa
da
air
min
um
. Ju
rna
l T
ek
nik
Kim
ia,
2(2
). 1
41
–1
46
.
Ha
psa
ri,
N.
(20
08
b).
Pro
ses
pe
mis
ah
an
io
n n
atr
ium
(N
a)
da
n
ma
gn
esi
um
d
ala
m
bit
tern
(b
ua
ng
an
) in
du
stri
g
ara
m.
Jurn
al
Te
kn
ik K
imia
, 3
(1).
19
2–
19
8.
Lee
, S.I
., S
.Y. W
eo
n, C
.W. L
ee
, da
n B
. Ko
op
ma
n (
20
03
). R
em
ov
al
of
nit
rog
en
an
d p
ho
sph
ate
fro
m w
ast
ew
ate
r b
y a
dd
itio
n
of
bit
tern
. C
he
mo
sph
ere
, 5
1(4
). 2
65
–2
71
.
Ma
rih
ati
(2
00
7).
Pe
mis
ah
an
ma
gn
esi
um
da
ri l
aru
tan
bit
tern
de
ng
an
ca
ra
ele
ktro
lisa
u
ntu
k
me
ng
ha
silk
an
se
ny
aw
a
ma
gn
esi
um
hid
rok
sid
a.
Jou
rna
l o
f In
du
stri
al
Re
sea
rch
,
1(1
), 1
–6
.
Na
, C
.K.,
H.
Pa
rk,
da
n E
.H.
Jho
(2
01
7).
Uti
liza
tio
n o
f w
ast
e
bit
tern
fro
m s
alt
ern
as
a s
ou
rce
fo
r m
ag
ne
siu
m a
nd
an
ab
sorb
en
t fo
r ca
rbo
n
dio
xid
e
cap
ture
. E
nvir
on
me
nta
l
Sci
en
ce a
nd
Po
llu
tio
n R
ese
arc
h,
24
(2),
22
98
0–
22
98
9.
Na
dia
, M
., M
. Z
ain
uri
, d
an
M.
Efe
nd
y (
20
15
). P
roto
typ
e p
up
uk
mu
ltin
utr
ien
t b
erb
asi
s p
ho
spa
te b
erb
ah
an
da
sar
limb
ah
ga
ram
(b
itte
rn)
seb
ag
ai
alt
ern
ati
f so
lusi
p
en
um
bu
h
pa
ka
n a
lam
i. J
urn
al
Ke
lau
tan
, 8
(2).
77
–8
2.
Sa
ng
ha
vi,
R.J
., R
. D
ob
ari
ya,
S.
Bh
att
i, d
an
A.
Ku
ma
r (2
02
0).
Pre
pa
rati
on
o
f h
igh
-pu
rity
m
ag
ne
siu
m-a
mm
on
ium
-
ph
osp
ha
te
fert
iliz
er
usi
ng
se
a
bit
tern
a
nd
in
du
stri
al
wa
ste
st
rea
ms.
E
nvir
on
me
nta
l S
cie
nce
a
nd
P
oll
uti
on
Re
sea
rch
, 2
7.
77
20
–7
72
8.
Su
ma
rno
, R
atn
aw
ati
, d
an
A.
Nu
gro
ho
(2
01
2).
Re
cov
ery
ga
ram
lith
ium
da
ri a
ir a
sin
(b
rin
e)
de
ng
an
me
tod
a p
resi
pit
asi
.
Bu
ng
a R
am
pa
i …
……
…. 3
ban
tuan
aru
s lis
trik
se
bag
ai
dri
vin
g
forc
e.
Besa
ran
ko
nse
ntr
asi
, w
aktu
o
pera
si,
luas
pen
am
pan
g m
em
bra
n,
sert
a
aru
s lis
trik
m
au
pu
n
teg
an
gan
m
em
pen
garu
hi
besa
rnya
p
ers
en
tase
re
cove
ry su
atu
io
n.
Hap
sari
(2
007;
2008b
) m
en
gu
ji efe
kti
fita
s p
rose
s ele
ktr
od
ialis
is
un
tuk
reco
very
io
n k
aliu
m,
natr
ium
, m
ag
nesi
um
, se
rta k
als
ium
dari
lim
bah
air
tu
a
ind
ust
ri
gara
m,
yan
g
dap
at
dim
an
faatk
an
se
bag
ai
sum
ber
alt
ern
ati
f su
ple
men
io
n
min
era
l p
ad
a
air
m
inu
m.
Den
gan
en
erg
i lis
trik
bert
eg
an
gan
op
tim
um
seb
esa
r 2.3
vo
lt s
ela
ma 3
0 m
en
it,
did
ap
atk
an
rec
ove
ry i
on
kaliu
m d
an
io
n n
atr
ium
seb
esa
r
masi
ng
-masi
ng
92.9
%
dan
74.7
%.
Sed
an
gka
n
un
tuk
reco
very
io
n m
ag
nesi
um
d
an
io
n kals
ium
, en
erg
i lis
trik
op
tim
um
ad
ala
h s
eb
esa
r 2.5
vo
lt d
an
2.7
vo
lt s
ela
ma 6
0-
90 m
en
it d
en
gan
m
asi
ng
-masi
ng
m
en
cap
ai
91.9
% d
an
96.2
%
reco
very
. A
dap
un
d
en
gan
w
aktu
o
pera
si
pro
ses
dip
erp
an
jan
g
hin
gg
a
150
men
it
men
un
jukkan
pen
ing
kata
n e
fekti
fita
s re
cove
ry, n
am
un
tid
ak m
em
beri
kan
hasi
l ya
ng
si
gn
ifik
an
. H
al
yan
g
sam
a
berl
aku
b
ah
wa
sem
akin
b
esa
r te
gan
gan
, m
aka
waktu
o
pera
si
yan
g
dib
utu
hkan
akan
se
makin
si
ng
kat,
d
an
m
en
ing
katk
an
efe
kti
fita
s re
cove
ry w
ala
up
un
tid
ak t
erl
alu
sig
nif
ikan
.
Sela
in
pro
du
k
reco
very
m
inera
l d
ari
lim
bah
air
tu
a
dala
m b
en
tuk io
n t
erl
aru
t, p
rose
s m
em
bra
n e
lektr
od
ialis
is
jug
a
berp
ote
nsi
m
en
gh
asi
lkan
p
rod
uk
reco
very
d
ala
m
ben
tuk
pad
ata
n
min
era
l o
ksi
da,
seb
ag
ai
con
toh
mag
nesi
um
hid
oksi
da, M
g(O
H) 2
d
an
mag
nesi
um
oksi
da,
Mg
O.
Sela
nju
tnya
, b
aik
Mg
(OH
) 2
mau
pu
n M
gO
dap
at
dig
un
akan
se
bag
ai
iso
lato
r,
pu
pu
k,
bah
an
b
aku
kim
ia
4
Bu
ng
a R
am
pa
i …
……
….
un
tuk
pro
ses
ind
ust
ri
tekst
il ra
yon
, p
en
go
lah
air
,
pem
bu
ata
n kert
as,
b
ah
an
alk
alis
d
an
fa
rmasi
(M
ari
hati
,
2007).
P
rod
uk r
ecove
ry t
ers
eb
ut
dap
at
dih
asi
lkan
dari
reaksi
an
tara
io
n m
ag
nesi
um
dari
lim
bah
den
gan
io
n h
idro
ksi
da
yan
g d
ihasi
lkan
dari
pro
ses
red
uksi
ele
ktr
olis
is a
ir, s
eb
ag
ai
pen
yeim
ban
g d
ihasi
lkan
nya
gas
hid
rog
en
, p
ad
a b
ag
ian
kato
da
(berm
uata
n
neg
ati
f).
Am
rullo
h
et
al.
(2019)
men
dap
atk
an
h
asi
l re
cove
ry
beru
pa
pad
ata
n
Mg
(OH
) 2
seb
esa
r 34.8
% (
seta
ra d
en
gan
15.9
g d
ari
100 m
L lim
bah
air
tu
a p
ekat)
yan
g d
iola
h d
en
gan
teg
an
gan
18 v
olt
sela
ma
10
jam
. Sela
nju
tnya
, kem
urn
ian
p
rod
uk
reco
very
ya
ng
leb
ih
tin
gg
i, ya
itu
63.8
%,
did
ap
atk
an
keti
ka
dila
ku
kan
pro
ses
pad
a li
mb
ah
air
tu
a e
nce
r d
en
gan
teg
an
gan
18 v
olt
sela
ma 1
3 j
am
. A
dap
un
pro
du
k s
am
pin
gan
(by-
pro
du
cts)
lain
ad
ala
h
beru
pa
pad
ata
n
CaC
O3
dan
N
aC
l m
asi
ng
-
masi
ng
seb
esa
r 25.4
7%
dan
10.6
9%
.
Sete
lah
did
ap
atk
an
pro
du
k r
ecove
ry y
an
g t
erp
isah
dari
limb
ah
air
tu
a,
maka u
ntu
k le
bih
m
em
urn
ikan
p
rod
uk
dap
at
dila
ku
kan
p
rose
s akh
ir b
eru
pa kals
inasi
. Seb
ag
ai
con
toh
, p
rose
s ele
ktr
oki
mia
ya
ng
d
ilan
jutk
an
d
en
gan
pro
ses
kals
inasi
p
ad
a
suh
u
500°C
se
lam
a
4
jam
men
gh
asi
lkan
kem
urn
ian
mag
nesi
um
hid
roksi
da s
eb
esa
r
91.2
% (A
mru
lloh
et al.,
2020). N
am
un
dem
ikia
n, e
nerg
i dan
bia
ya p
rose
s p
erl
u m
en
jad
i p
erh
ati
an
dan
pert
imb
an
gan
dari
seg
i eko
no
mi.
Bu
ng
a R
am
pa
i …
……
…. 9
P
rose
s p
resi
pit
asi
ju
ga
dap
at
dila
kukan
m
ela
lui
pen
cam
pu
ran
lim
bah
air
tu
a t
ers
eb
ut
den
gan
air
lim
bah
lain
yan
g m
en
gan
du
ng
am
on
ium
dan
fo
sfat
den
gan
do
sis
tert
en
tu u
ntu
k m
em
ben
tuk p
rod
uk s
tru
vite
. Pem
ben
tukan
stru
vite
dap
at
dija
dik
an
sala
h s
atu
alt
ern
ati
f p
en
go
lah
an
limb
ah
ya
ng
ti
dak
han
ya
men
gu
ran
gi
volu
me
dan
ko
nse
ntr
asi
po
luta
n l
imb
ah
hasi
l p
rod
uksi
gara
m,
teta
pi
men
gu
ran
gi p
en
cem
ar
lain
nya
yan
g b
eru
pa a
mo
niu
m d
an
fosf
at
ag
ar
tid
ak m
en
yeb
ab
kan
perm
asa
lah
an
lin
gku
ng
an
yan
g b
aru
.
N
am
un
dem
ikia
n,
ko
nse
p t
ekn
olo
gi
reco
very
in
i p
erl
u
dik
aji
leb
ih
lan
jut
ag
ar
dap
at
dik
em
ban
gkan
d
ala
m
pen
era
pan
bers
kala
besa
r. S
eh
ing
ga, p
ad
a a
kh
irn
ya d
ap
at
men
du
ku
ng
p
em
ban
gu
nan
in
frast
ruktu
r in
du
stri
ya
ng
berw
aw
asa
n lin
gku
ng
an
dan
berk
ela
nju
tan
.
Da
fta
r P
ust
ak
a
Am
rull
oh
H.,
W.
Sim
an
jun
tak
, R
.T.M
. S
itu
me
an
g,
S.L
. S
ag
ala
, R
.
Bra
ma
wa
nto
, d
an
R.
Na
hro
wi
(20
19
). E
ffe
ct o
f d
ilu
tio
n
an
d e
lect
roly
sis
tim
e o
n r
eco
ve
ry o
f M
g2
+ a
s M
g(O
H) 2
fro
m b
itte
rn b
y e
lect
roch
em
ica
l m
eth
od
. T
he
Jo
urn
al
of
Pu
re a
nd
Ap
pli
ed
Ch
em
istr
y R
ese
arc
h,
8(1
). 8
7–
95
.
Am
rull
oh
H.,
W.
Sim
an
jun
tak
, R
.T.M
. S
itu
me
an
g,
S.L
. S
ag
ala
, R
.
Bra
ma
wa
nto
, A
. F
ati
qin
, R
. N
ah
row
i,
da
n
M.
Zu
nia
ti
(20
20
).
Pre
pa
rati
on
o
f n
an
o-m
ag
ne
siu
m
oxi
de
fr
om
Ind
on
esi
a
loca
l se
aw
ate
r b
itte
rn
usi
ng
th
e
ele
ctro
che
mic
al
me
tho
d.
Ino
rga
nic
a
nd
N
an
o-M
eta
l
Ch
em
istr
y,
50
(8).
69
3–
69
8.
8
Bu
ng
a R
am
pa
i …
……
….
dan
p
resi
pit
asi
se
bag
ai
alt
ern
ati
f te
kn
olo
gi
reco
very
limb
ah
air
tu
a
dan
b
eb
era
pa
po
ten
si
pro
du
k
pem
an
fata
an
nya
.
Gam
bar
1. K
on
sep
rec
ove
ry lim
bah
air
tu
a d
an
po
ten
si p
rod
uk
pem
an
faata
nn
ya
P
rose
s m
em
bra
n e
lektr
od
ialis
is m
em
an
faatk
an
en
erg
i
listr
ik
un
tuk
men
ing
katk
an
se
lekti
fita
s io
n-i
on
m
inera
l
terl
aru
t ya
ng
mam
pu
mem
isah
kan
an
tara
targ
et
pro
du
k
reco
very
d
en
gan
io
n-i
on
“p
en
go
tor”
la
inn
ya,
seh
ing
ga
dap
at
men
ing
katk
an
ke
mu
rnia
n
pro
du
k.
Bila
p
rod
uk
reco
very
dik
eh
en
daki d
ala
m b
en
tuk p
ad
ata
n, m
aka
pro
ses
ini
dap
at
dik
om
bin
asi
kan
d
en
gan
p
rose
s p
resi
pit
asi
kim
iaw
i d
en
gan
men
gatu
r ko
nd
isi
pH
, p
en
gad
ukan
dan
rasi
o m
ola
r p
rod
uk.
Seb
ag
ai
alt
ern
ati
f, p
rose
s kals
inasi
den
gan
m
en
gatu
r p
em
an
faata
n
en
erg
i p
an
as
dap
at
dig
un
akan
.
Bu
ng
a R
am
pa
i …
……
…. 5
2.2
. P
resi
pit
asi
P
ad
ata
n m
ag
nesi
um
ju
ga d
ap
at
dih
asi
lkan
dari
pro
ses
pre
sip
itasi
an
tara
lim
bah
air
tu
a
den
gan
p
en
am
bah
an
NaO
H
(Na
et
al.,
2017).
Pro
ses
pre
sip
itasi
d
ilaku
kan
den
gan
p
en
gatu
ran
p
H
9.5
-10
den
gan
p
en
am
bah
an
NaO
H u
ntu
k m
en
dap
atk
an
rasi
o m
ola
r N
aO
H:M
g p
ad
a
ren
tan
g 0
.7-2
.8.
Sete
lah
pen
gad
uka
n s
ela
ma 2
jam
dan
dila
nju
tkan
p
rose
s p
en
gen
dap
an
se
lam
a
12
jam
,
did
ap
atk
an
mag
nesi
um
hid
roksi
da s
eb
esa
r 100.3
g p
er
liter
limb
ah
den
gan
rasi
o o
pti
mu
m N
aO
H:M
g a
dala
h 2
.53.
Ko
mb
inasi
p
rose
s p
resi
pit
asi
d
en
gan
kals
inasi
ju
ga
dap
at
dila
kukan
u
ntu
k
men
dap
atk
an
p
rod
uk
reco
very
.
Seb
ag
ai
con
toh
, p
resi
pit
asi
8.5
%
limb
ah
air
tu
a
dan
pen
am
bah
an
NaO
H 7
.51%
den
gan
pen
gad
ukan
sela
ma 1
jam
pad
a k
ece
pata
n 3
00 r
pm
, dap
at
men
gh
asi
lkan
ad
ala
h
11.4
8%
en
dap
an
M
g(O
H) 2
. Sela
nju
tnya
, p
en
am
bah
an
NaC
l 3.5
%
ke
dala
m
en
dap
an
te
rseb
ut
den
gan
ca
ra
pen
gad
uka
n p
ad
a s
uh
u 1
10°C
sela
ma 3
jam
kem
ud
ian
dib
ilas
dan
dik
eri
ng
kan
, akan
men
gh
asi
lkan
Mg
Cl 2
. Pro
ses
kals
inasi
d
en
gan
su
hu
o
pti
mu
m
terj
ag
a
pad
a
150°C
sela
ma 6
0 m
en
it m
en
gh
asi
lkan
100%
Mg
Cl 2
.6H
2O
. Pro
du
k
ini
dap
at
dig
un
akan
seb
ag
ai
bah
an
baku
pad
a i
nd
ust
ri
farm
asi
, p
en
go
ntr
ol
ero
si
dan
d
eb
u,
pen
gen
dalia
n
es,
mate
rial
pen
yim
pan
an
u
ntu
k
hid
rog
en
, d
an
in
du
stri
makan
an
min
um
an
(Z
uch
rilla
h d
an
Ju
laik
a, 2
017).
Mag
nesi
um
kaliu
m f
osf
at
(Mg
KP
O4)
meru
paka
n s
ala
h
satu
ben
tuk p
rod
uk p
up
uk y
an
g d
ihasi
lkan
dari
pre
sip
itasi
limb
ah
air
tu
a m
ela
lui
pen
am
bah
an
NaO
H d
an
Na
2H
PO
4.
6
Bu
ng
a R
am
pa
i …
……
….
Pro
ses
pen
cam
pu
ran
Na
2H
PO
4 4
00 m
L, N
aO
H 3
50 m
L d
an
limb
ah
air
tu
a 2
50 m
L d
ap
at
men
gh
asi
lkan
mass
a M
gK
PO
4
seb
esa
r 82.9
973 g
(N
ad
ia e
t al.,
2015)
yan
g d
iman
faatk
an
seb
ag
ai n
ilai ta
mb
ah
dala
m b
ud
idaya
ikan
ban
den
g. H
asi
l
pen
elit
ian
m
en
un
jukka
n b
ah
wa ta
mb
ak ya
ng
d
iberi
kan
pro
du
k
reco
very
p
up
uk
Mg
KP
O4
mem
beri
kan
pert
um
bu
han
ya
ng
b
aik
, ya
itu
p
en
ing
kata
n b
era
t d
an
pan
jan
g ikan
ban
den
g.
Seb
ag
ai
tam
bah
an
, kan
du
ng
an
m
ag
nesi
um
ya
ng
tin
gg
i d
i d
ala
m lim
bah
air
tu
a b
erp
ote
nsi
seb
ag
ai s
um
ber
mag
nesi
um
dala
m p
rose
s p
resi
pit
asi
un
tuk m
en
gh
asi
lkan
pro
du
k
min
era
l st
ruvi
te,
Mg
NH
4.P
O4.6
H2O
, su
mb
er
alt
ern
ati
f p
up
uk f
osf
at
bers
ifat
slow
rel
ease
fer
tilize
r, y
an
g
berm
an
faat
bag
i p
ert
um
bu
han
ta
nam
an
. P
em
ben
tukan
stru
vite
berg
an
tun
g d
en
gan
fakto
r p
H d
an
rasi
o m
ola
r.
Str
uvi
te d
ap
at
terb
en
tuk
an
tara
ren
tan
g p
H 8
hin
gg
a 9
.6
(Lee e
t al.,
2003; Y
e e
t al.,
2011)
. Sem
akin
tin
gg
i p
H a
kan
men
gu
ran
gi
kem
urn
ian
d
ari
st
ruvi
te
yan
g
terb
en
tuk
kare
na
mem
iliki
kem
un
gkin
an
d
en
gan
te
rben
tukn
ya
pre
sip
itat
lain
se
pert
i kals
ium
fo
sfat
(Ye
et
al.,
2011).
Str
uvi
te
dap
at
terb
en
tuk
den
gan
p
en
am
bah
an
b
itte
rn
den
gan
ju
mla
h
tert
en
tu
ked
ala
m
air
lim
bah
ya
ng
men
gan
du
ng
am
on
ium
d
an
fo
sfat
sep
ert
i bio
logic
ally
trea
ted s
win
e w
ast
ewate
r, l
imb
ah
in
du
stri
pu
pu
k m
au
pu
n
limb
ah
in
du
stri
zat
warn
a (
Lee e
t al.,
2003; Y
e e
t al.,
2011;
San
gh
avi
et
al.,
2020). S
tru
vite
yan
g d
ihasi
lkan
den
gan
rasi
o m
ola
r M
g2+:N
H4+:P
O43- 1
:1:1
ad
ala
h 7
6 g
, sed
an
gkan
den
gan
rasi
o 1
:0.5
:1 m
en
gh
asi
lkan
str
uvi
te 7
0 g
.
Bu
ng
a R
am
pa
i …
……
…. 7
Pro
du
k la
in ya
ng
d
ihasi
lkan
d
ari
p
rose
s p
resi
pit
asi
limb
ah
air
tu
a
ad
ala
h
reco
very
lit
ium
se
bag
ai
litiu
m
alu
min
at
den
gan
m
en
am
bah
kan
n
atr
ium
alu
min
at
NaA
lO2.
Fakto
r p
H b
erp
era
n p
en
tin
g d
i m
an
a p
H l
aru
tan
terl
alu
b
asa
m
aka lit
ium
ya
ng
te
lah
te
ren
dap
kan
akan
terl
aru
t kem
bali
men
jad
i N
aA
lO2 d
an
H2O
seb
ag
ai
LiO
H.
Sem
akin
la
ma d
an
b
esa
r ko
nse
ntr
asi
n
atr
ium
alu
min
at
yan
g
dit
am
bah
kan
m
aka
aka
n
men
gh
asi
lkan
re
cove
ry
litiu
m y
an
g s
em
akin
besa
r. P
rose
s o
pti
mu
m r
ecove
ry li
tiu
m
seb
esa
r 2.1
7 g
lit
ium
ad
ala
h p
ad
a p
H 1
3,
den
gan
waktu
pen
gad
uka
n 3 ja
m se
rta ko
nse
ntr
asi
n
atr
ium
alu
min
at
seb
esa
r 500
mg
/L.
Pro
du
k
litiu
m
sela
nju
tnya
d
ap
at
dim
an
faatk
an
se
bag
ai
bah
an
b
aku
in
du
stri
b
ate
rai
rech
arg
eable
, lo
gam
allo
y u
ntu
k p
esa
wat,
dan
bah
an
baka
r
nu
klir
fu
si (
Su
marn
o e
t al.,
2012).
3.
Rin
gk
asa
n
K
on
sep
pen
go
lah
an
lim
bah
sela
yakn
ya b
erf
oku
s p
ad
a
pro
ses
reco
very
ke
tika lim
bah
te
rseb
ut
masi
h m
em
iliki
kan
du
ng
an
m
inera
l ya
ng
cu
ku
p
tin
gg
i, d
ala
m
hal
ini
limb
ah
air
tu
a y
an
g d
ihasi
lkan
dari
pro
ses
ind
ust
ri g
ara
m.
Den
gan
men
era
pkan
tekn
olo
gi re
cove
ry y
an
g t
ep
at,
maka
dih
ara
pka
n l
imb
ah
air
tu
a d
ap
at
dim
an
faatk
an
men
jad
i
added
-valu
e pro
du
cts
beru
pa
bah
an
b
aku
kim
ia
yan
g
men
du
ku
ng
p
rose
s in
du
stri
la
in
dan
lim
bah
ya
ng
mem
en
uh
i b
aku
m
utu
lin
gku
ng
an
. G
am
bar
1
men
un
jukka
n k
on
sep
pen
era
pan
mem
bra
n e
lektr
od
ialis
is
