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Banyak metode yang dapat digunakan untuk menghilangkan kandungan logam berat,
diantaranya adalah dengan cara chemical precipitation, adsorbsi, ion exchange, filtrasi
dengan membran, teknologi treatmen elektrokimia, dan metode-metode lainnya. Ho,
Y.S. dkk (2014) menyebutkan bahwa logam berat yang terkandung dalam air dan
beberapa variasi fraksi dalam tanah yang biasanya dapat dipisahkan dengan
menggunakan metode yang memanfaatkan gravitasi dapat diterapkan metode
konvensional, diantaranya chemical precipitation, ion exchange, dan pemisahan secara
elektrokimia.
Chemical precipitation merupakan metode yang umum dan secara luas digunakan untuk
menghilangkan logam berat dari efluen inorganik, namun tidak memiliki nilai ekonomis
yang baik karena menghasilkan sludge yang banyak dan memerlukan penangangan
tambahan. Pada proses presipitasi yang bertujuan untuk menyisihkan partikel yang
sangat halus, proses dilakukan dengan menggunakan aliran elekstrostatik dengan
menambahkan koagulan dan proses flokulasi untuk meningkatkan ukuran agregat agar
dapat diendapkan. Karena adanya penambahan material, maka jumlah sludge yang
terbentuk juga akan meningkat. Namun, penggunaan metode ini luas karena memiliki
nilai efektivitas tinggi dan relatif mudah untuk dioperasikan, serta efektif untuk tipe
limbah cair yang mengandung konsentrasi ion logam berat yang tinggi.
Beberapa metode dari presipitasi dapat dilihat pada list berikut ini:
1. Hydroxide Precipitation
Merupakan metode presipitasi konvensional. Pada presipitasi untuk penyisihan
logam, proses nya adalah dimana senyawa kimia akan bereaksi dengan logam berat
yang akan disisihkan, kemudian membentuk presipitat insoluble, termasuk
didalamnya hydroxide precipitation dan sulfide precipitation.
Pada proses presipitasi hidroksida, penambahan koagulan seperti alum, garam besi,
dan polimer organik dapat meningkatkan penyisihan logam berat dari limbah cair.
Namun, dari proses ini dihasilkan volume sludge yang tinggi dengan densitas rendah
sehingga sulit untuk terendapkan. Juga, prosesnya akan berjalan lama apabila ukuran
partikel sangat kecil.
2. Sulfide Precipitation
Logam sulfida biasanya sangat insoluble. Namun, logam dapat dipresipitasikan
dengan menambahkan ion sulfide (S2-). Presipitat sulfide condong untuk membentuk
partikel koloid, sehingga membutuhkan koagulan agar terbentuk flok yang lebih
besar.
Coagulation that is brought about by the reduction of the net surface charge of the
colloidal particles to a point where the stabilized colloidal particles by electrostatic
repulsion can approach closely enough for vander Waals forces to hold them together
and allow aggregation is the destabilization of colloids by charge neutralization of
particles and by enmeshment of the impurities on the formed amorphous metal
hydroxide precipitates [17]. Coagulants with charges opposite to those of the discrete
solids are added to the water to neutralize the negative charges on dispersed non-
settable solids such as clay and organic substances [18]. The reduction of the surface
charge is a result of the decrease of the repulsive potential of the electrical double
layer by the presence of an electrolyte having opposite charge. Once charged, the
particles bond together like small magnets to form a mass. Therefore, the addition of
chemical coagulants which is followed by low-sheer mixing in a flocculator to
promote contact between the particles are often to overcome the repulsive forces of
the particles [19].
Flocculation, a gentle mixing stage to form bridges between the flocs and bind the
particles, continually increases the particle size to grow submicroscopic microfloc to
visible discrete particles through additional collisions and interaction with inorganic
polymers formed by the coagulant or with organic polymers added [20]. Once discrete
particles are flocculated into larger particles, they can usually be removed or separated
by filtration, straining or floatation. Disadvantages are input of chemicals required and
transfer of toxic compounds into solid phase and formation of sludge that has to be
treated subsequently.
Precipitation processes are particularly suitable for the treatment of large volumes of
liquid waste which contain relatively low concentrations of radioactive elements. These
processes are fairly versatile and may be used to treat a wide variety of different waste
streams, including those containing large amounts of particulates or high concentrations
of salts. However, high salt concentration in effluents can reduce the options for a
secondary treatment such as ion exchange and may be undesirable in discharges because
of the environmental protection aspect. Usually, the processes use readily available
chemical reagents and are economically attractive when compared with some alternative
processes, e.g. evaporation. Existing treatment plants achieve relatively lower
decontamination factors (10-100) than othertreatment methods. Recent developments in
absorber materials and in solid-liquid separation technology [3-6] are providing
improvements in decontamination as well as compliance with tightening restrictions on
the discharge of hazardous materials such as metals, nitrates, phosphates, etc.
This section describes conditioning processes that may be used before the formation of
a precipitate in order to improve the decontamination achieved by the precipitation
stage. These processes may be carried out to oxidize organic contaminants, decompose
complexed species or residual complexing agents, alter the valency state of elements or
adjust the ionic species in solution to those with a greater affinity for the precipitate.
Some waste streams may require physical pretreatment before chemical treatment. Such
pretreatment may include coarse filtering and oil/solvent removal. For example, floor
drain wastes may contain general debris which could damage pumps, clog pipes and
otherwise interfere with subsequent treatment steps. In considering pH adjustment,
oxidation or reduction processes for pretreatment of a adioactive waste stream, it must
be appreciated that a particular treatment may produce both desirable and undesirable
effects
2. Elektrokoagulasi
2. 1. Reaksi Elektrokoagulasi
Elektrokoagulasi merupakan metode pengolahan air secara elektrokimia yaitu
gejala dekomposisi elektrolit, dimana pada anoda terjadi pelepasan koagulan aktif
berupa ion logam (biasanya alumunium atau besi) ke dalam larutan, sedangkan pada
katoda terjadi reaksi elektrolisis berupa pelepasan gas hidrogen. Dalam proses ini akan
terjadi proses reaksi reduksi dimana logam-logam akan direduksi dan diendapkan di
kutub negatif, sedangkan elektroda positif (Al3+) akan teroksidasi menjadi [Al(OH)3]
yang berfungsi sebagai koagulan (Holt et al, 2004). Proses elektrokoagulasi meliputi
beberapa tahap yaitu proses equalisasi, proses elektrokimia (flokulasi-koagulasi) dan
proses sedimentasi. Proses equalisasi dimaksudkan untuk menyeragamkan limbah cair
yang akan diolah terutama kondisi pH, pada tahap ini tidak terjadi reaksi kimia.
Elektrokoagulasi seringkali dapat menetralisir muatan-muatan partikel dan ion,
sehingga bisa mengendapkan kontaminan-kontaminan, menurunkan konsentrasi lebih
rendah dari yang bisa dicapai dengan pengendapan kimiawi, dan dapat menggantikan
dan/atau mengurangi penggunaan bahan-bahan kimia yang mahal (garam logam,
polimer). Meskipun mekanisme elektrokoagulasi mirip dengan koagulasi kimiawi
dalam hal spesies kation yang berperan dalam netralisasi muatan-muatan permukaan,
tetapi karakteristik flok yang dihasilkan oleh elektrokoagulasi berbeda secara dramatis
dengan flok yang dihasilkan oleh koagulasi kimiawi. Flok dari elektrokoagulasi
cenderung mengandung sedikit ikatan air, lebih stabil dan lebih mudah disaring
(Woytowich, 1993 dalam Hendrianti, 2011).
Nanti akan ditambahi penjelasan elekrokoagulasi monopolar dan bipolar…..
Ada beberapa macam interaksi spesies dalam larutan pada proses elektrokoagulasi,
yaitu :
1. Migrasi ke elektroda yang bermuatan berlawanan (electrophoresis) dan
penggabungan (aggregation) untuk membentuk senyawa netral.
2. Kation atau ion hidroksi (OH-) membentuk endapan dengan polutan.
3. Logam kation berinteraksi dengan OH membentuk hidroksi, yang mempunyai
sisi yang mengadsorbsi polutan (bridge coagulation)
4. Hidroksi membentuk struktur besar dan membersihkan polutan (sweep
coagulation)
5. Oksidasi polutan sehingga mengurangi toxicitinya
6. Penghilangan melalui elektroflotasi dan adhesi gelembung udara.
f. Pengaruh pH awal
pH adalah parameter kunci karena mempengaruhi konduktivitas larutan, potensi zeta
dan pelarutan elektroda. Namun sulit mencari hubungan/korelasi antara pH larutan dan
efisiensi elektrokoagulasi karena pH air berubah saat diolah selama proses EC, oleh karena itu
biasanya disebut pH larutan awal (Mansoorian et al, 2014).
Perkembangan penelitian:
Bazrafshan et al. (2016) combined chemical coagulation, electrocoagulation
and adsorption for treating real textile wastewater
in a pilot scale study. Chemical coagulation was performed using
poly aluminum chloride “PAC” as coagulant followed by electrocogulation
with four aluminum electrodes in a bipolar parallel
connection mode and finally adsorption using pistachio nut shell
ash was used to meet the required standards
Deghles and Kurt (2016) used a hybrid electrocoagulation/
electrodialysis process to treat tannery effluent. The authors have
optimized the electrocoagulation process by controlling various
process parameters and then the effluent from electrocoagulation
process was further treated using electrodialysis.
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The technology has been optimized to minimize electrical power consumption and
maximize effluent throughput rates. This approach, which provides little insight into the
fundamental chemical and physical mechanisms, does not allow modeling of the
process or the design of improved systems, process control and optimization from
fundamental physico-chemical principles.
The chemical precipitation is a widely used for an effective treatment process for
removal of dissolvedmetals fromwastewater solution containing toxic metals.
Effectiveness of the chemical precipitation process is dependent on several factors,
including concentration of ionic metals present in the solution, the precipitant used and
the presence of other constituents that may inhibit the precipitation reaction. The
chemical precipitation in water treatment involves the addition of chemical to alter the
physical state of dissolved and suspended solids and to facilitate their removal by
sedimentation or filtration.
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The electrocoagulation process using electrical energy, similar to the typical physical
and chemical treatments of emulsified oil, total petroleum hydrocarbons, discrete solids,
and heavy metals, is the electrochemical production of destabilization agents such as Al
and Fe that bring about neutralization of electric charge to remove pollutant that are not
easy to remove by filtration or chemical treatment systems. In the EC process, the
coagulant is generated in situ by electrolytic oxidation of an appropriate anode material.
In this process, charged ionic metal species are removed from wastewater by allowing it
to react with anion having an opposite charge, or with floc of metallic hydroxides
generated within the effluent. This process is characterized by reduced sludge
production, no requirement for chemical use, and ease of operation. Colloiddestabilizing
agents that effect on-charge neutralization are produced by electrolysis in the
electrocoagulation process [24] [25]. Holt et al. [26] [27] reported that there were three
operating stages in the removal of clay particles or colloidal matters by EC:
i) lag where no significant change in clay removal takes place;
ii) reactive stage in which most of clay removal occurs and finally
iii) stable stage where clay removal is approximately constant.
Mollah et al. (2001) [25] and Canizares et al. (2010) [28] indicated that the main
mechanisms responsible for the clay or colloidal matters removal during EC are:
1) Charge neutralization of negatively charged particles of the clay particles
through the electrophoresis migration of those particles towards the anode under
the influence of electrical field.
2) Charge neutralization of the negatively charged clay particles by adsorption of
monomeric and polymeric hydrolysis species of Al3+.
3) The charge neutralized clay particles coalesce upon collision as a result of their
Brownian movement or their electrophoretic migration to form a larger floc
which can be easily removed.
4) Sweep flocculation which takes place as the Al(OH)3 reaches its minimum
solubility and precipitates and during its precipitation clay particles may be
enmeshed between Al(OH)3 and removed from the bulk.
5) The coalesced clay particles may adhere to H2 bubbles generated at the cathode
and float to the surface and can be easily removed.
6)
All the above mechanisms can contribute in the removal of clay particles during
reactive stages. However, the concentration of clay particles may decreases and charge
neutralization through electrophoretic migration can also diminishes during stable stage;
on the other hand the pH reaches neutrality with precipitation of Al(OH)3 [26].
Referensi:
Harif, T, Khai, M, dan Adin. Electrocoagulation versus chemical coagulation:
Coagulation/flocculation mechanisms and resulting floc characteristics. Jurnal
water research 46 (2012) 3177-3188
Ho, Y.S., dkk. Application of Electrocoagulation and Electrolysis on the Precipitation
of Heavy Metals and Particulate Solids in Washwater from the Soil Washing.
Journal of Agricultural Chemistry and Environment, 2014, 3, 130-138
International Atomic Energy Agency Vienna. 1992. Chemical Precipitation Processes
For The Treatment Of Aqueous Radioactive Waste. Technical Reports Series No
337
Mollah, M.Y.A., dkk. Electrocoagulation (EC)—science and applications. Journal of
Hazardous Materials B84 (2001) 29–41
Moussa, D.T., dkk. A comprehensive review of electrocoagulation for water treatment:
Potentials and challenges. Journal of Environmental Management 186 (2017) 24-
41
Oncel, dkk. A comparative study of chemical precipitation and electrocoagulation for
treatment of coal acid drainage wastewater. Journal of Environmental Chemical
Engineering 1 (2013) 989–995