Fluoride Recovery in Fluidized Bed:

Crystallization of Calcium Fluoride on

Silica Sand

Muhammad Aaron S. (02211840000026)

Muhammad Fakhri J. (02211840000027)
Sahirah Zahraindy (02211840000036)
Miftahul Hidayah N (02211840000046)
Jericho Immanuel (02211840000049)
 Daftar Isi

01 02
Material and
Introduction
Methods

03 04
Results and
Conclusions
Discussion
 01
Introduction
 Introduction

 Fluoride containing wastewater is an industrial effluent

requiring neutralization due to acidity and fluoride concentration
control.
 Fluoride is a pollutant and need to be reduced by some treatment.
 Precipitation is the most common treatment.
 Precipitation generates large amounts of water rich sludge which
must be disposed. It will increase costs.

 Many alternatives treatment for fluoride removal from industrial

wastewater have been suggested.
 Alternative treatment which utilizes the reaction of fluoride with
granular particles.
 This treatment allows high efficiencies of fluoride removal without sludge
generation.
 Fluidized Bed Crystallization
 The use of pellet reactor, which is reactive fluidized bed growth-type
crystalizer has been reported for fluoride removal.
 The major advantages of this technology:
The elimination of sludge formation
The recovery of materials
The reduction of solid wastes

H+ + F- ↔ HF
Ca2+ +2OH- ↔ Ca(OH)2
Ca2+ + 2F- ↔ CaF2 (s)
 Precipitation mechanism upon
silica sand in a fluidized bed reactor
 Calcium fluoride crystallization upon silica sand is referred to as
the electrical attraction between the sand surface.
 02
Materials and
Methods
 Experimental Setup

 Reaktor terdiri dari silinder metil metakrilat vessel dengan tinggi 500 mm
dan diameter 36 mm diisi sebagian dengan pasir silika (0,15-0,30 mm)
sebagai seed dari material di mana air fluorida dan pereaksi kalsium
larutan dipompa ke atas melalui reaktor dengan kecepatan yang
memastikan fluidisasi pada pelet sehingga cementing of grains dapat
dicegah. Alirannya sedemikian rupa sehingga seed tidak akan mengendap
dan mengalir keluar dari bejana kristalisasi. Kecepatan superfisial, SV,
dan bilangan Reynolds partikel, Rep, masing-masing adalah 30 m‚-1 dan
1,9
 Di gambar (ii), a sand filter bed digunakan saringan partikel halus yang
terbentuk dalam fluidized bed reactor sebelum fluoride pengenceran dan
pemberian kalsium. Filter sand bed terdiri dari bejana silinder berisi
pasir (0,5-1,0 mm). Reagen kalsium dan larutan fluorida diinjeksikan ke
dalam Fluidized bed reactor menggunakan pompa peristaltik yang
berbeda
 Experimental Setup
 Fluidized bed reactor dilengkapi dengan dua saluran masuk nozel. Nozel utama
(diameter 6 mm) berada vertikal pada sumbu simetri reaktor. Kecepatan fluida
larutan fluorida melalui nosel ini berada dalam kisaran antara 0,15 dan 0,18 m‚s-
1. Larutan kalsium dipompa ke dalam reaktor melalui nozel sekunder (diameter 6
mm) ditempatkan secara horizontal di dinding pada ketinggian 15 mm dari bagian
bawah reaktor. Kecepatan cairan larutan kalsium adalah 0,12-0,15 m‚s-1.
 Materials
 Larutan fluorida digunakan sebagai aliran feed yang diperoleh dengan
mengencerkan larutan asam fluorida pekat.
 Chemical grade reactants (kapur terhidrasi sebagai kalsium reagen (Ca2
+)) dan air demineralisasi digunakan. Beberapa penelitian menunjukkan
kapur terhidrasi sebagai sumber kalsium yang cukup untuk netralisasi
fluorida yang mengandung air limbah. Selain itu, partikel Ca (OH) 2
cenderung larut di sepanjang bed, mendistribusikan supersaturasi lebih
merata ke seluruh bed
 Analytical Techniques
 Sampel diambil dari limbah cair reaktor pada interval waktu yang berbeda.
 Kekeruhan dan pH diukur dengan turbidimeter (Turbiquant 3000IR, Merck)
dan pH meter (Crison GLP 22)
 Efisiensi penghilangan fluorida dapat dihitung dengan mengukur
konsentrasi zat halus dan fluorida terlarut aliran outlet fluorida terlarut
dianalisis dengan Specific fluoride ion electrode (Crison 120 / S7) yang
disediakan dengan elektroda referensi (Crison 5240).
 Padatan tersuspensi di aliran outlet disaring dengan 0,45 µm filter, dan
keseimbangan massa diterapkan pada padatan untuk memperkirakan jumlah
fluorida yang dilepaskan sebagai zat halus.
 Analysis of Fluoride-Coated sand

 Pasir berlapis fluoride butiran dibuang dari dasar reaktor pada perbedaan
interval. Pelet dikeringkan dengan udara dan dianalisis untuk menentukan
morfologi menggunakan mikroskop elektron scanning (SEMJSM 5800LV,
JEOL)
 Komposisi butiran pasir kalsium fluoride dianalisis setelah distilasi dengan
metode potensiometri menggunakan elektroda sensitif ion fluorida (Crison 120
/ S7) menurut metode standar (ISO 5439: 1978) untuk menentukan
ketersediaan kandungan fluor di fluorspar acid grade. Kristal putih yang
diperoleh dalam proses dianalisis dengan difraksi sinar-Xpenganalisis (XRD-
PW 1729, Philips).
 03
Results and
Discussion
An Results and Supersaturation Influence
Experiment
Analysis Influence of Supersaturation

Primary nucleation and the formation of fines

 To describe the formation of fines, it is necessary to establish the relationship

between supersaturation and the rate of fines formation.
 Levels of supersaturation in aqueous solution of sparingly soluble electrolytes
are expressed in terms of solubility products as :

S = Solubility, IP = ion activity product of the lattice ions in solution, Ka =

activity solubility product of the salt, and v =number of ions in a formula unit
of the salt
Supersaturation can be defined for a calcium fluoride system at room temperature
as :

at a given pH value and under an excess of calcium, the supersaturation defined

depends only on the fluoride concentration, and the influence of supersaturation
can be studied in terms of the inlet fluoride concentration in the reactor
 The theory of primary homogenous nucleation assumes that in supersaturated
solutions, solute atoms or molecules combine in a series of bimolecular
reactions to produce ordered aggregates.
 The overall energy of these aggregates reaches maximum at some critical sizes,
which can be shown to be inversely proportional to the logarithm of the
supersaturation.
 Aggregates that are larger than the critical size are called “stable nuclei” and
grow to form macroscopic crystals.
The kinetic nucleation equation of new nuclei formation is expressed in equations
below :

where,
B1 = is the number of nuclei formed per unit time per unit volume (nuclei/m3.min)
V = molecular volume
k = Boltzmann constant (1,38.10^-23 J/K)
T = temperature (K)
S = supersaturation
C1 = constant
The nucleation rate can be related to the fines’ formation per unit reactor volume
(neglecting heterogenous nucleation, secondary nucleation, and abrasion at the
bottom of the reactor) according to the following equation :

Where,
Rf = fines’ formation per unit of reactor volume (mg/L.min)
Mf = mass flow of fluoride (mg/min)
Vr = reactor volume (L)
Kf & Ks = constant
ϒ = interfacial tension (J/m^2)
That assumption can be taken into account  considering the particles size of sillica
sand (0.15-0.3mm), wich is bif=g enough to make the formation of fines by
heterogeneous nucleation negligible.

The temperature and interfacial tension from (eq 10) can be included in a constant,
Cs, taking into account a constant interfacial tension in the studied
supersaturation range and a constant temperature, according to the following
equation :
From figure 4, it is possible to verify the strong influence of the supersaturation
on the generation of fines. The formation of fines is, therefore, highly
nonlinear in solution supersaturation, being near zero for low values of S
but increasing rapidly once some criticall supersaturation is reached.

From these results, it is possible to define the equation that describes the
formation of fines in the fluidized bed reactor as a function of fluoride inlet
concetration in the reaction in terms of the supersaturation :
It is important to control the system under suitable supersaturation values. The
fluoride concentration at the bottom of the reactor must be keep below
critical value in order to prevent discrete precipitation.
 Influence of Recycling : Secondary Nucleations

To get a fluoride concentration lower   than starting from a concentrated

wastewater, a recyling ratio is applied to dilute the fluoride concentration
in the feed stream of the ractor. Consequently, the effluent concentration is
lowered and it is possible to control the supersaturation in the reactor
according to the previous results.

From these results it is possible to deduce that the nucleation in the

supersaturated solution is much faster when crylstals of of the recycled
calcium fluoride are present.
The recycling of fines could be the reason for the additional nucleation of new
fines , contributing thereby to secondary nucleation, wich results from the
presence of crystals in the supersaturated condition.
Influence Of The Sand
Filter
 A sand filter bed has been used after the reactor in order to
reduce discrete precipitation (secondary nucleation) and to
improve the efficiency of the process

• The sand filter bed retains suspended solids, increasing the

efficiency of the process, as has been suggested previously.
• After filtration, the fines are negligible and therefore, secondary nucleation
is reduced
• The available fluoride for crystal growth in the fluidized bed reactor is
greater, increasing the calcium fluoride precipitation upon the silica sand.
• The use of a sand filter bed allows one to obtain similar efficiencies without
recycling, as is shown in the comparative results of Figure 6. Under these
conditions, process efficiencies close to 80% have been obtained.
Characterization of Calcium-
Fluoride-Coated Sand Grains
• Low supersaturation and the filtration of fines increase the
precipitation on the seed, favoring crystal growth, i.e., the
enlargement of the size of the pellets.
• A characterization of the recovered pellets is performed in
order to evaluate the reuse of synthetic fluorite as a raw
material in technical application.
 • When calcium fluoride precipitation takes place upon the
• The composition of the pellets seed material, the pellet growth and the silica composition
is dependent on the size of are reduced, increasing the calcium fluoride composition.
the pellets.
• The maximum pellet growth will be limited by the adequate
selection of the hydraulic load allowing the fluidization of
the particles in the reactor and avoiding pellets being washed
out.
This is the photography and the SEM
microphotography of grains where the particle
sizes of the silica sand and the pellets of calcium
fluoride are compared.
• The calcium fluoride content of the product was 88% and
the particle size was 800 µm after 110 h of continuous
operation.

• The X-ray diffraction data of the standard CaF2 is close to

that of the pellets (Figure.9)
Pellets with calcium fluoride content higher than
According to the composition and the low
97% and a particle size of about 1200 µm could
water content, calcium fluoride from
be obtained at higher hydraulic loads.
the fluidized bed reactor is able to be
reused as :
• A raw material for the production of
hydrofluoric acid
• filler material in concrete
• Enamels for ceramic substrates
• Flux in the manufacturing of steel and
cast iron.
 04
Conclusions
 Conclusions

1 2 3 4
Supersaturation plays the Due to the
main role in the process composition and the
The use of a sand
due to the primary low water content,
filter bed improves the
nucleation mechanism, It is not possible to reuse of the
efficiency of the
leading to the formation of obtain efficiencies recovered calcium
process when
fines and a decrease in the greater than 40% under fluoride is possible for
recycling of the
efficiency of the recovery. technical conditions, technical applications
effluent is necessary.
when high fluoride of synthetic fluorite,
concentrations are used. avoiding the sludge
formation and leading
to a reduction of solid
waste
Awesome
Words
“Tugas kita bukanlah untuk
berhasil, tugas kita adalah
untuk mencoba karena di
dalam mencoba, itulah kita
menemukan kesempatan
untuk berhasil“ –Buya
Hamka
Bibliographical References
Thank You