ISSN 2314-5609

Nuclear Sciences Scientific Journal

9A, 33- 42
2020
http://www.ssnma.com

NON-CONVENTIONAL APPROACH FOR IMPURITIES REDUCTION

DURING AND AFTER MANUFACTURING OF PHOSPHORIC ACID
MOHAMMAD M. FAWZY
Nuclear Materials Authority, Cairo, Egypt

ABSTRACT
A non-conventional method to reduce the impurities in the wet process phosphoric acid (WPPA) was
applied which divided into two parts: The first part deals with a process which utilizes phosphate rock,
fluorosilicic acid, and sulfuric acid to produce phosphoric acid, calcium fluorosilicate, and calcium sulfate
slurry by wet method. The second part studied the influence of hydroxyl-apatite (HAP) added to the
produced acid for adsorption of uranium, fluorine, rare earth elements (ΣREE), organic matter, and other
undesirable components those affected the quality of phosphoric acid. The relevant conditions in the
production and absorption processes have been optimized. The results show that, the obtained acid contains
low values of suspended & organic matter (191.7 ppm), and fluorine (0.5%). The addition of HAP, in the
form of bone powder, produce phosphoric acid contains low concentration of uranium, fluorine, and rare
earth elements equals 85, 94.6 and 79% respectively.

INTRODUCTION The amount of H2SO4 required is consid-

The major constituent of phosphate rock, erable being equivalent to the amount of cal-
commonly known as apatite or fluorapatite, cium sulfate formed regardless of the source
is represented by the formula Ca3(PO4)2.CaF2. of the calcium, but the impure CaSO4 formed
Impurities are commonly present also, such as has practically no use whatever and in most
iron, aluminum compounds, calcium carbon- cases creates a severe disposal problem. Thus
ate, and silica, but such impurities are of little acidulation of phosphate rock with H2SO4
or no effective value and are substantially brings about a substantial economic loss, and
eliminated in the process of phosphoric acid many trials were performed to avoid this loss
production. Such phosphate rock is common- by eliminating the use of H2SO4 for this pur-
ly used as a starting material in the manufac- pose (Abdel Aal, 1989; Abdel-Gawwad, 2003;
ture of phosphate fertilizers (Becker, 1983). Abdel Aal, 2000 and Singh and Vijayalak-
In making the so-called “triple-phosphate” shmi, 2001). Hechenbleikner, (1991) states
for example, the rock is acidulated with (70%) that when phosphate rock is acidulated with
sulfuric acid in which the following reaction hydro-fluorosilicic acid, the phosphoric acid
takes place: obtained is easily filtered and is of greater pu-
rity than that obtained in commercial WPPA
3Ca3(PO4)2.CaF2 + 10H2SO4→
• 10CaSO4 +6H3PO4 +2HF plant. Recovering of the calcium, large part

Absorption efficiency (E) % = [(Co – Cf)/Co] × 100

4HF + SiO2 • SiF4 + 2H2O

3SiF4 + 2H2O • 2H2SiF6 + SiO2

3{3Ca3(PO4)2CaF2} + 29H2SiF6 + SiO2 • 30CaSiF6 + 18H3PO4 + 2H2O

 34 MOHAMMAD M. FAWZY
of the fluorine from the phosphate rock in the ride which is later reacted with sulfuric acid
form of valuable by-products (instead of the to produce hydrogen fluoride and calcium sul-
relatively worthless and discarded calcium fate. The hydrogen fluoride is then stripped
sulfate), and the excess hydro-fluorosilicic from the phosphoric acid and recovered as
acid was achieved. It is known that phosphate either anhydrous hydrogen fluoride or con-
rock, which generally contains phosphorus in centrated hydrofluoric acid or reacted with
the form of Ca10F2(PO4)6 can be acidulated with sodium carbonate to produce sodium fluoride/
sulfuric acid to recover phosphoric acid by bi-fluoride.
means of the “wet acid” process. The result- Zhang et al. (2014) studied the mechanism
ing phosphoric acid product, termed “Green
and removal effect of uranium by HAP from
acid” is suitable for use in fertilizer applica-
acidic media. The effect of reaction time,
tions, but is not suitable for most other ap-
pH value, initial concentration of uranium,
plications because of its high impurity level
dosage of apatite on adsorption of HAP for
(Sweat et al., 2004; Lapple and Mountainside,
uranium was studied. The adsorption pro-
1967; Erickson and Bouffard, 1993; Oneill, cess was analyzed by thermodynamics and
1980 and Vernooy and Michel, 2001). kinetics, and the adsorption mechanisms were
One method for overcoming the problems determined by infrared spectroscopy, X-ray
of acidulation with sulfuric acid is described diffraction and scanning electron microscope.
by Winter (1953). The process is carried out The result show that the removal capacity
by acidulating phosphate rock containing sil- of uranium increases with initial concentra-
ica with hydro-fluorosilicic acid (H2SiF6) to tion and the adsorption rate of HAP on UO22+
obtain CaSiF6 and H3PO4 as products of the reaches 85%. Gauglitz et al. (1992) performed
reaction. The resultant phosphoric acid solu- a process for immobilization of heavy met-
tion is then heated to volatilize any remaining als by hydroxyl-apatite. The results indicate
hydro-fluorosilicic acid. This process also that, HAP immobilizes uranium and rare
has serious drawbacks in which it is difficult earth elements by forming different phosphate
to crystallize the calcium fluorosilicate from phases. Some of these phases can be identi-
the phosphoric acid solution on a plant scale fied by X-ray diffraction analysis (XRD), e.g.
by merely volatilizing water from the hot saleeite Mg(UO2)2.9H2O or meta-autunite
H3PO4 solution without encountering serious Ca(UO2)2(PO4)2.6H2O.
operational difficulties. This is due to the high
Mourabet et al. (2015) studied the re-
solubility of CaSiF6-2H2O in H2SiF6 present moval of fluoride from aqueous solution by
in the phosphoric acid solution, which hin-
adsorption on hydroxyapatite (HAP) using
ders recovery by crystallization (Laesen and
response surface methodology. Fluoride re-
Ravenholf, 1994).
moval efficiency was 86.3% at the optimum
Additional processes have also been sug- combination of process parameters. Dynamic
gested in which acidulation of the phosphate adsorption data were applied to pseudo-first-
rock is carried out with other mineral acids, order and pseudo-second-order rate equations,
including hydrofluoric acid. A hydrofluoric and the result shows that, the time data fitted
acid-based process is generally impractical well to pseudo second order kinetic model.
for commercial operation because the rate of According to the correlation coefficients, the
rock attack with an acid of practical strength adsorption of fluoride on the hydroxyapatite
is too slow and because of the high cost of this was correlated well with the Langmuir and
acid (Schorr et al., 2013). Erickson and Bouf- Freundlich models.
fard (1996) studied the reaction of fluorosilicic Separative recovery with lime of phosphate
acid with phosphate rock in order to produce and fluoride from an acidic effluent containing
wet process phosphoric acid and calcium fluo- H3PO4, HF and/or H2SiF6 was carried out by
 NON-CONVENTIONAL APPROACH FOR IMPURITIES REDUCTION 35
Gouider et al. (2009). The data showed that tions were carried out using Metertech UV/
fluoride has a beneficial effect on phosphate VIS SP8001 spectrophotometer, China. This
removal. Moreover, by acting on the precipi- spectrophotometer covers wave length from
tation pH, a selective recovery of fluoride and 200-1100 nm. Trace element analysis was
phosphate ions was possible either from phos- obtained using Unicam 929 atomic absorption
phoric acid/hydrofluoric acid or phosphoric spectrophotometer (AAS), England. Calcium
acid/hexafluorosilicic acid mixtures. The fluorosilicate samples were analyzed using
recovery process led to a fluoride removal ef- energy dispersive X-ray spectroscopy (EDX),
ficiency of 97–98% from phosphoric acid/hy- JSM–84OA, JEOL, Tokyo, Japan. The analy-
drofluoric acid mixture. Yulun et al. (2012) sis of bone powder (HAP) was presented in
enhanced the adsorption of fluoride using Al Table (1).
modified calcium hydroxy-apatite, which pos-
The (HAP) bone powder {Ca5(OH)(PO4)3}
sessed higher defluoridation capacity (DC) of
contains about 55.8% CaO, 43.2% P2O5,
32.57 mgF−/g than unmodified HAP that have
1.79% water and very small traces of heavy
DC of 16.38 mgF /g. The pH changes during
-
metals, chloride, nitrogen, sulfate and iron.
the adsorption process suggested that the OH
groups on the surface of Al-HAP acts as the
adsorption sites. Table
The more adsorptionofsites
1: Analysis hydroxyl apatite in the form of bone powder
were formed on Al modified HAP, which pos- Table 1: Analysis of hydroxyl apatite in
sessed abundant surface hydroxyl groups, re- the form of bone powder
•••••••••
sulting in higher efficiency of F removal.
- Tests Specification
•
The present work was oriented to reduce Appearance White solid
the undesirable impurities during the manufac-
CaO 55.8%
turing of phosphoric•acid by the addition of
P2O5 41.2%

H2SiF6 to the rock, and to absorb the unwanted

Water 1.79%

matter after the production

• of the phosphoric
Heavy metals 0.008%

acid by the addition of hydroxy-apatite (HAP,

Total N 0.007%

in the form of bone powder).

• The main goal
Chloride 0.003%

tends to minimize the environmental pollution

Sulfate 0.003%

during storage of byproducts, transportation

Iron 0.001%
•
and usage, as well as to achieve a decontami-
nated product that can•be safely used in many
industrial applications to prepare low cost use- Qualification Procedure
ful products. • The acidulation of phosphate ore was
carried out by addition of sulfuric acid,
EXPERIMENTAL
• hydro-fluorosilicic acid, and sufficient amount
Materials and Instruments of water. The produced acid was analyzed
• for determination of P2O5, its clarification,
The working phosphate ore has been sup- and other involved materials. The produced
plied from the Sebaiya • region which was CaSiF6 was evaporated, crystallized, and un-
mixed with another one from the Abu-Tarture dergone chemical analysis. The absorption
region, Egypt. Hydroxy-apatite
• (HAP) in of U, F, ΣREE, and undesirable materials was
the form of bone powder was provided from performed by the addition of bone powder. The
Pratap Chemical Industries LTD, India. Sul- optimum conditions such as: reaction time,
•
furic acid, silicon di-oxide and hydro-fluoride concentration of reactants, solid/ liquid ratio,
were provided from Sigma-Aldrich Chemie, and agitation speed were studied. For the
Germany. •
Spectrophotometric determina- analysis of uranium and heavy rare earths, the
•

•
 3Ca3(PO4)2.CaF2 + 10H2SO4 • 10CaSO4 +6H3PO4 +2HF

Absorption efficiency (E) % = [(Co – Cf)/Co] × 100

36 MOHAMMAD M. FAWZY
concentration of initial sample was measured Using proportions of rock and sufficient vol-
2 • SiF4 + 2H2O
(Co) before absorption process. After each ume of two applied acids those are preferred
4HF + SiO
process,
3Ca3(PO 4)2.CaF2 the
+ 10H 2SO4 • solution
aqueous was3PO
10CaSO4 +6H separated
4 +2HF in most cases, the general reaction is repre-
and analyzed for uranium and total rare earths sented by the following equation to produce
contents (ΣREE). The absorption efficiency the so-called triple super-phosphate (Winter,
3SiF4 + 2H2O • 2H2SiF6 + SiO2
percent (E) % was calculated as follows: 1953):

Absorption efficiency (E) % = [(Co – Cf)/Co] × 100 3{3Ca3(PO4)2CaF2} + 29H2SiF6 + SiO2→

• 30CaSiF6 + 18H3PO4 + 2H2O

The analysis of major contents (%) and

Where, Co is the conc. of the initial sample and
other trace elements (ppm) in mixed phos-
Cf is the conc. of treated one. The absorption ef-
phate ore as well as manufactured phosphoric
ficiency (E) was expressed as enrichment percent
• 10CaSO
+ SiO24•+6H acid was shown in Table (2) and Figs (1&2).
(%) of studied materials.
3Ca3(PO4)2.CaF2 + 10H2SO4 4HF 3PO
SiF 4 +2HF
4 + 2H2O
Table 2 shows that, the produced acid have
3Ca3(PO4)2.CaF2 + 10H2SO4 • 10CaSO4 +6H3PO4 +2HF 29.6% P2O5, 3.95% Fe2O3, 3.25% SiO2, 6.41%
RESULTS AND DISCUSSION
CaO, 0.5% F, and certain values of ΣREE, U,
Manufacturing
3SiF4 + 2HProcedure
2O • 2H2SiF6 + SiO2 organic matter (OM) equal 410, 34.2, 191.7
The hydro-fluorosilicic acid was prepared ppm less than those in the commercial acid
Absorption efficiency (E) % = [(Co – Cf)/Co] × 100
3{3Ca3(POby the 2reaction
4)2CaF } + 29H2SiF + SiO2 •dioxide
of 6silicon 30CaSiFwith 18H3PO4 +(607,
6 + hydro- 2H2O 39.5, 472 ppm) respectively.
fluoric
Absorption acid(E)
efficiency according
% = [(Co –toCfthe
)/Co]following
× 100 reac- Calcium fluorosilicate is separated from
tion: the phosphoric acid by evaporating the solu-
4HF + SiO2 → • SiF4 + 2H2O tion and crystallizing the calcium salt. Cal-
cium fluorosilicate is immediately available
The formed silicon tetra-fluoride is par- in most volumes, high purity, submicron and
4HF + SiO2 • SiF4 + 2H2O
tially volatized. The remainder would be hy- nano-powder forms. The analysis of major
drolyzed
4 + 2H2to
O •form2H2hydro-fluorosilicic acid and and trace contents in CaSiF6 & CaSO4, the by-
products from the acidulation of phosphate
3SiF SiF6 + SiO2
silica, as follows:
rock, was shown in Table (3).
3{3Ca3(PO4)2CaF2} +3SiF
29H42SiF 6+2O →
SiO • 230CaSiF
• 2 2H 6 +2 18H3PO4 + 2H2O
Both of calcium salts contains a small
+ 2H SiF6 + SiO
Hexa-fluorosilicic acid is also
3{3Ca3(PO4)2CaF2} + 29H2SiF6 + SiO2 • 30CaSiF6 + 18H3PO4 + 2H2O converted amount of trace elements such as Cr, Ba, Co,
to a variety of useful hexa-fluorosilicate salts. Sr, Pb, Zn and V. The EDX analysis of CaSiF6
During the process by-product fluorosilicic was shown on Figure (3).
acid is intermittently recovered while the re-
Absorption Investigation
maining acid is recycled (Erickson et al., 1993).
The first step in the process comprises mix- Hydroxy-apatite (HAP) is a calcium
ing hydro-fluorosilicic acid and sulfuric acid phosphate similar to the human hard tissues
with phosphate rock to dissolve a substantial in morphology and composition. An impor-
part of all its P2O5 content and a substantial tant characteristic of hydroxyl-apatite is its
part of essentially all of its CaO content. The stability when compared to other calcium
production of phosphoric acid from phosphate phosphates. Thermodynamically, hydroxy-
rock was achieved by applying certain condi- apatite is the most stable calcium phosphate
tions such as: stirring time 8 hrs, temperature compound under physiological conditions as
70ºC, H2SO4: Ca3(PO4)2 ratio is 1:1, added temperature, pH and composition of the body
water H2O: Ca3(PO4)2 ratio is 15:1, added fluids (Deng et al., 2013). The addition of
phosphoric acid (15% P2O5) H3PO4: Ca3(PO4)2 HAP in the form of bone powder to the phos-
ratio 10:1, (El-Shafie, 2008) and added hydro- phoric acid was studied. The factors affect
fluorosilicic acid H2SiF6: Ca3(PO4)2 ratio 5:1. the absorption process such as: time, conc.
of phosphoric acid, amount of bone powder,
 •

•
NON-CONVENTIONAL APPROACH FOR IMPURITIES REDUCTION 37
Table 2: Analysis of the mixed phosphate ore and Table 3: Analysis of by-products CaSiF6 and
• Table 2: Analysis of the mixed phosphate ore and produced phosphoric CaSO
produced phosphoric acid
Tableacid
3: Analysis of by-products CaSiF6 and CaSO4
4
Components Phosphate ore Produced acid Commercial acid Components CaSiF6 CaSO4
Conc. (%) Conc. (%)
CaO 37.9 6.41 4.92 CaO 24.7 26.4
SO3 6.77 2.52 7.11 Si 51.2 8.36
SiO2 12.1 3.25 4.75 F 19.5 0.01
P2O5 27.4 29.6 23.6 SO3 1.17 39.2
Fe2O3 9.03 3.95 6.85 Fe2O3 8.52 5.26
K2O 0.17 0.04 0.08 Conc. (ppm)
Na2O 0.14 0.61 0.06 Cr 36 62
Ba 17 19
•
MnO 0.12 0.07 0.12
Co 20 16
F•
MgO 0.84 0.52 0.84
2.11 0.50 0.91• Sr 12 8.0
∑• Traces 0.18 0.06 0.17 Pb 16 11
• (ppm)
Conc. •
Zn 53 74
∑• REE 1410 410 607 V 23 18
U• 95.6 34.2 39.5• U 41 23
Organic matter 504 191.7 472 ∑• REE 321 542
• •
• •
•
•
•
•
9
• 8 Produced Acid
7 Commercial Acid
•
Content %

6
5
• 4
3
• 2

•
1
0

•
CaO SO3
SO3 Fe2O3
Fe2O3 SiO2
SiO2 F
Components

• • •••••••• •
Fig. 1: Comparison between different••••••••••••••••••••••••••••••••
Fig. 3:••• •EDX analysis
• •• • • •• •••••• •••• • •• •• • • •• •for
••• •••• •the
•••• • ••produced
•••••• •• • calcium
•
components (%) in the produced phosphoric fluorosilicate
•
acid •(29.6% P2O5) and commercial one (23.6%•
P2•O5) •
•
• •
••••• ••• • • • ••••• • •• • •• • • • •• •• • •• • •••• • • • • • • ••••• •••• ••• • •• •• • • •• • •• • • •• • • •••••••• ••• • •• • •
• agitation
speed, and solid/liquid mass ratio
• • • • •••• • ••• • • • ••••••• • • ••• • •• • •• • • • ••
600 Produced Acid
• were optimized as following:
500• Commercial Acid
• Reaction time
conc., ppm

•
At room temperature, the reaction time
400
•
300
• • for the addition of HAP to the produced
200
•
phosphoric acid was studied during 10-30 min.
•
100 Agitation speed was 150 rpm. To 1L of phos-
0• phoric acid, 10 g of bone powder was added.
U OM • REE The result was plotted on Figure (4).
•
The result indicates that, by increasing the
Components
•••• • •
Fig. 2: Comparison between different trace time up to 20 min., the absorption efficiency
(ppm) in the produced phosphoric acid increases
•••••• ••••• • • ••••• • •• • •• •• • •• •••• •• • ••••••• •• •• • • • ••••• • • •••• ••• • •• •• • • •• • •• • • •• • • ••••••••
elements • to reach 41, 55 and 32% for U, F,
(29.6% • • ••••) •and
•• • •• •P•• •O ••• • • •commercial
••••••• • • ••• • •• • •• • • • ••one (23.6% P O ) and ΣREE respectively. The time 20 min. was
2 5 2 5
•
•
•

• •

•
 •

•
•
•
•
•
•
•
•
•
• 38 MOHAMMAD
•
M. FAWZY

70 60
U U
60 F F
50
50 • REE • REE
40
40
E%

E%
30
30
20
20
10
10
0 0
10 15 20 25 30 1L 2L 3L 4L
• Phosphoric Acid volume, L
Time, min.
• •
•
Fig. 4: Effect of time on the absorption ••••••••••••••
•
Fig. 5: Effect of phosphoric acid volume on
•• ••• • • •••• ••• • • •• • • ••••• ••• •• • •• • • •• • ••• • •• • •• •• ••• • •• •••••• • •• ••• ••• ••
••••••••••••••••• ••• ••• •••• ••••• • •• • ••• • •• • •• •• ••• • •• •••••• • •• ••• ••• •• • •• • • •• • • ••••• ••• •
efficiency (E) % on phosphoric acid the absorption efficiency (E) %
• •
•
•
•
the optimum one for absorption of undesir-
• able impurities from phosphoric acid. 90 U
F
• Phosphoric acid volume
80
• REE
70
•
Different volumes of acid (1- 4L) were 60
E%

• subjected to 10g of HAP addition for 20 min. 50

•
at room temperature and standard conditions. 40
The effect of phosphoric acid volume on the 30
• absorption process was shown on Figure (5). 20

• The data show that, the absorption effi-

10 g 20 g 30 g 40 g 50 g

ciency for U, F and ΣREE was decreased with ••

Amount of HAP added, g
• •
the volume of acid. The viscosity of acid was Fig.6:
••• • • •••• ••• •Effect
• • • ••• ••• • • ••of
• ••• • ••amount
• •• •• ••• • •• ••••••of HAP on the
• ••••••••••••••••••••• •• • •• ••• ••• ••
increased with concentration. The mobility of absorption efficiency (E) %
• HAP and the mass transfer was districted •and
immobilized (Gauglitz et al., 1992). •
sorption process was studied in range 150-300
•
Solid/liquid ratio rpm. At room temperature, 30g of HAP were
•
added to 1L of phosphoric acid during 20min.
The amount of HAP, which added to• 1L
The effect of agitation speed was shown on
of phosphoric acid, was varied between 10-
Figure (7).
50g. The absorption process was carried • out
The result shows that, by increasing the
during 20 min. at room temperature with agi-
•
agitation speed to 250 rpm, the absorption
tation speed of 150 rpm. The effect of amount
•
efficiency % was increased to become 80,
of HAP was illustrated on Figure (6). •
93 and 76% for U, F and ΣREE respectively,
The data show that, by increasing • the which give rise to good and high mass transfer
amount of HAP to 30 gm, the absorption • between the reactants (Savova et al., 2005).
efficiency (E) % was increased to reach 74,
Choice of optimum conditions
85, and 67% for U, F and ΣREE respectively.
After this value the acid became saturated Based on the results, the optimum con-
with high amount of HAP (Chopey, 2004). ditions required for absorption of U, F and
ΣREE from produced phosphoric acid were:
Agitation speed
contact time of 20 min., 30g of hydroxy-apa-
The effect of agitation speed on the ab- tite (in the form of bone powder) to 1L of
 •

• •

• •

• •

• •

• NON-CONVENTIONAL APPROACH
• FOR IMPURITIES REDUCTION 39

95 100
U U
90 95 F
F
85 • REE • REE
90

E %
80
E%

85
75
80
70
65 75

60 70
150 200 250 300 1 st 2 nd 3 rd
Agitation Speed, rpm Successive absorption steps
• •
Fig. 7: Effect of agitation speed on the Fig. 8: Effect of successive step on absorption
••••••••••••••••••••• •• ••• • • •••• ••• • ••• • • • ••• • • • •• • ••• • •• • •• •• ••• • •• •••••• • •• ••• •••••••••••••••••••••••••••••••••••••••
•
absorption efficiency (E) % •••••••••••••••• •• ••• • • •••• •••• ••• •••• • •••• • •• • •• • •• •• • • • •• •• •• ••• ••
processes
• •

•
phosphoric acid, and agitation speed of 250 • phosphoric acid, produced by acidulation of
• rpm. This conditions lead to absorb of 80, 93
• phosphate rock with hydro-fluorosilicic acid
• and 76% of U, F and ΣREE respectively. and sulfuric acid in the so-called wet process
•
phosphoric acid (WPPA), has been devel-
• Successive absorption step • oped in the present work. This was possible
• In the successive absorption processes, •
through absorption of U, F and ΣREE by using
•
the treatment of residual U, F, and ΣREE in hydroxy-apatite in the form of bone powder.
the phosphoric acid was carried out on 3 steps. The corresponding relevant factors were stud-
Under the optimum experimental conditions, ied and the conclusions can be summarized as
the treated phosphoric acid samples were sub- follows:
jected to successive absorption process. The
1- A method for manufacture of substan-
results are represented on Figure (8).
tially pure calcium fluorosilicate and phos-
From the results, the absorption efficiency phoric acid, from mixed phosphate rock
for U, F and ΣREE increases in the second acidulated by hydro-fluorosilicic acid and
step of process to reach the value of 85, 94.6 sulfuric acid, leads to produce acid contains
and 79 % respectively. On the other hand, the 29.6% P2O5, 3.95% Fe2O3, 6.41% CaO, 0.5%
third step has no effect on the absorption of U, F and traces of some undesirable elements.
F and ΣREE from phosphoric acid that pro- The acid contains also 34.2 and 410 ppm of
duced by non-conventional approach. U & ΣREE respectively, with low values of
The proposal flow sheet for the overall organic matters, humic acids (191.7 ppm), and
process included the production and absorp- unwanted suspended materials.
tion step was illustrated on Figure (9) . 2- The absorption of U, F and ΣREE by
The physical properties indicate that the Hydroxy-apatite (HAP) in the form of bone
obtained acid from non-conventional ap- powder was carried out at room temperature
proach have green clear color with high den- during 20 min. by the addition of 30 gm of
sity in comparison with the commercial one HAP to 1L of the phosphoric acid produced
of dark brown color of high amount of humic by non-conventional approach. The absorp-
acid (Table 4) produced in Abu-Zaabal Com- tion process gives rise to absorb of 85, 94.6
pany for chemicals and fertilizers. and 79% of U, F and ΣREE respectively after
two successive steps. Most of uranium un-
CONCLUSIONS dergoes into CaSiF6 and CaSO4 residue due to
the ionic radii similarity of calcium and ura-
A successful absorption procedure of nium.
•

• 40 MOHAMMAD M. FAWZY

•
Fig. 9: Proposal flow sheet for manufacturing and absorption process
Table 4: The•physical
•• •• ••• •• •properties
• •• ••••• • •••
of•the
• ••••produced
••• • • • •• and
••• ••• • •• • • •• • •• phosphoric
commercial •• ••• • •• •• ••acid
•••
Table 4: The physical properties of the produced and commercial phosphoric acid
•
Specification •
•
Character
•
Produced phosphoric acid Commercial phosphoric acid
Appearance green dark brown
• Odor Slight acid odor Slight acid odor •
• pH < 2 <1
Density 1.67 1.53 •

•
 NON-CONVENTIONAL APPROACH FOR IMPURITIES REDUCTION 41
Acknowledgements G., 1992. Immobilization of heavy metals by
hydroxyl apatite. Radiochimica Acta, 58 (59),
The author wish to thank the collaboration
253-257.
from Abu-Zaabal Company for fertilizers and
Chemicals, Prof. Mohsen M. Ali, Ex-President Gouider, M.; Feki, M., and Sayadi, S., 2009. Sepa-
of Nuclear Materials Authority, (NMA) and rative recovery with lime of phosphate and flu-
Prof. Hisham F. Aly, Ex-President of Egyptian oride from an acidic effluent containing H3PO4,
Atomic Energy Authority, (EAEA). HF and/or H2SiF6. J. Hazardous Materials,
170(2), 962-968.
REFERENCES Hechenbleikner, I., 1991. Process of making phos-
Abdel Aal, E.A., 1989. Industrial simulation for phoric acid. U.S. Patent, No.1313379
wet process phosphoric acid production. Ph.D.
Thesis, Fac. Sci., Cairo Univ., Egypt. Laesen, M., and Ravenholf, G., 1994. Dissolution
of various calcium fluoride preparations in in-
Abdel Aal, E.A., 2000. Recovery of phosphoric organic solutions and stimulated human saliva.
acid from Egyptian Nile Valley phosphate tail- Caries Research, 28 (6), 447-454.
ings. Mineral. Engin. J., 13, 223-226.
Lapple, W.C., and Mountainside, N.J., 1967. Pro-
Abdel-Gawwad, E.E., 2003. Development of duction of phosphoric acid from a phosphatic
uranium recovery process from the purifica- ore. U.S. Patent, No. 3323864.
tion phosphoric acid pilot plant at Inchass
site. M.Sc. Thesis, Fac. Sci., Alexandria Univ., Mourabet, M.; Rhilassi, A.E.; Boujaady, H.E.; Ben-
Egypt, 145p. nani-Ziatni; Hamri, R.E., and Taitai, A., 2015.
Removal of fluoride from aqueous solution by
Becker, P., 1983. Phosphates and phosphoric adsorption on hydroxy-apatite (HAP) using re-
acid: raw materials, technology, and economics sponse surface methodology. J. Saudi Chemical
of the wet process. Fertilizer Science and Tech- Society, 19 (6), 603-615.
nology Series, 3, New York, Marcel Dekker.
Oneill, P.S., 1980. Calcium fluoride production in
Chopey, N., 2004. Handbook of Chemical Engi- a phosphoric acid plant. Ind. Eng. Chem. Prod.
neering Calculations. 3rd Edition, McGraw- Res. Dev., 19 (2), 250-255.
Hill.
Savova, M.; Bart, H., and Seikova, I., 2005. En-
Deng, S.B.; Jiang, B.H.Y., and Wang, H.Y., 2013. hancement of mass transfer in solid-liquid
Adsorption of UO2+2 on hydroxy-apatite. J. extraction by pulsed electric field. J. Univ. of
Nucl. Radio., 35 (1), 46-53. Chemical Technology and Metallurgy, 40 (4),
El-Shafie, A.S., 2008. Studies on the production 329-334.
of phosphoric acid fron Abu-Tartur phosphate Schorr, M.; Valdez, B.; Zlatev, R., and Stoytcheva,
ore deposits. Ph.D. Thesis, Fac. Sci., Zagazig M., 2013. Phosphate ore processing for phos-
Univ., Egypt, 121p. phoric acid production: classical and novel
Erickson, W.R., and Bouffard, L.E., 1993. Process technology. Mineral Processing and Extractive
for the production of phosphoric acid and hy- Metallurgy, 119 (3), 125-129.
drogen fluoride from phosphate rock and fluo- Singh, H., and Vijayalakshmi, R., 2001. Studies
rosilicic acid. U.S. Patent, No. 5180569. on uranium extraction from phosphoric acid
Erickson, W.R., and Bouffard, L.E., 1996. Process using di-nonyl phenyl phosphoric acid-based
for the production of phosphoric acid and cal- synergistic mixtures, Hydrometallurgy, 59(1),
cium fluoride. U.S. Patent. No. 5531975. 69-76.

Gauglitz, R.; Holterdorf, M.; Franke, W., and Marx, Sweat, S.F.; Breed, C.E., and McGill, K.E., 2004.
 ‫‪42‬‬ ‫‪MOHAMMAD M. FAWZY‬‬
‫‪Phosphate acidulation utilizing HF acid. U.S.‬‬ ‫‪U.S. Patent, No. 2636806.‬‬
‫‪Patent. No. 6,676,914 B1.‬‬
‫‪Zhang, X.; Chen, D.; Tu, G.X., and Huang, X.,‬‬
‫‪Vernooy, P.D., and Michel, J.B., 2001. Process for‬‬ ‫‪2014. Study on removal effect and mechanism‬‬
‫‪the production of calcium fluoride, U.S. Patent.‬‬ ‫‪of uranium by hydroxyapatite and natural apa-‬‬
‫‪No. 6224844 B1.‬‬ ‫‪tite, Yuanzineng Kexue Jishu, 48, 56-63.‬‬
‫‪Winter, E.A., 1953. Acidulation of phosphate rock.‬‬

‫ﻣﻘﺎﺭﺑﺔ ﻏﻴﺮ ﺗﻘﻠﻴﺪﻳﺔ ﻟﺨﻔﺾ ﺍﻟﺸﻮﺍﺋﺐ ﺃﺛﻨﺎء ﻭﺑﻌﺪ ﺗﺼﻨﻴﻊ ﺣﻤﺾ ﺍﻟﻔﻮﺳﻔﻮﺭﻳﻚ‬
‫ﻣﺤﻤﺪ ﻣﺤﻤﺪ ﻓﻮﺯﻯ‬
‫ﺗﻢ ﺗﻄﺒﻴﻖ ﻁﺮﻳﻘﺔ ﻏﻴﺮ ﺗﻘﻠﻴﺪﻳﺔ ﻟﺨﻔﺾ ﻧﺴﺒﺔ ﺍﻟﺸﻮﺍﺋﺐ ﺍﻟﻨﺎﺗﺠﺔ ﺧﻼﻝ ﻋﻤﻠﻴﺔ ﺗﺼﻨﻴﻊ ﺣﻤﺾ‬
‫ﺍﻟﻔﻮﺳﻔﻮﺭﻳﻚ ﺑﺎﻟﻄﺮﻳﻘﺔ ﺍﻟﺮﻁﺒﺔ‪ .‬ﻭﻟﻘﺪ ﺍﻧﻘﺴﻤﺖ ﺍﻟﺪﺭﺍﺳﺔ ﺇﻟﻲ ﺟﺰﺋﻴﻦ ﺍﺳﺎﺳﻴﻦ ‪ ،‬ﺍﻟﺠﺰء ﺍﻻﻭﻝ ﻳﺘﻨﺎﻭﻝ‬
‫ﻋﻤﻠﻴﺔ ﺇﺫﺍﺑﺔ ﺻﺨﻮﺭ ﺍﻟﻔﻮﺳﻔﺎﺕ ﻓﻲ ﺣﻤﺾ ﺍﻟﻬﻴﺪﺭﻭﻓﻠﻮﺭﺳﻠﻴﻜﺎﺕ ﻭﺣﻤﺾ ﺍﻟﻜﺒﺮﻳﺘﻚ ﺍﻟﻤﺮﻛﺰﻳﻦ ﻹﻧﺘﺎﺝ‬
‫ﺣﻤﺾ ﻓﻮﺳﻔﻮﺭﻳﻚ ﻭﻓﻠﻮﺭﻭﺳﻴﻠﻜﺎﺕ ﺍﻟﻜﺎﻟﺴﻴﻮﻡ ﺍﻟﺴﺪﺍﺳﻴﺔ ﺍﻟﺘﻰ ﺗﺘﻔﺎﻋﻞ ﻣﻊ ﺣﻤﺾ ﺍﻟﻜﺒﺮﻳﺘﻚ ﻟﺘﺮﺳﻴﺐ‬
‫ﻛﺒﺮﻳﺘﺎﺕ ﺍﻟﻜﺎﻟﺴﻴﻮﻡ )ﺍﻟﻔﻮﺳﻔﻮﺟﺒﺲ(‪ .‬ﺃﻣﺎ ﺍﻟﺠﺰء ﺍﻟﺜﺎﻧﻰ ﻓﻴﺘﻨﺎﻭﻝ ﻋﻤﻠﻴﺔ ﺍﻣﺘﺼﺎﺹ ﺍﻟﻴﻮﺭﺍﻧﻴﻮﻡ ﻭﺍﻟﻔﻠﻮﺭ‬
‫ﻭﺍﻟﻌﻨﺎﺻﺮ ﺍﻻﺭﺿﻴﺔ ﺍﻟﻨﺎﺩﺭﺓ ﺑﻮﺍﺳﻄﺔ ﻣﺮﻛﺐ ﺍﻟﻬﻴﺪﺭﻭﻛﺴﻲ ﺍﺑﺎﺗﻴﺖ ﺍﻟﻤﺴﺘﺨﺪﻡ ﻓﻲ ﺷﻜﻞ ﻣﺴﺤﻮﻕ‬
‫ﻋﻈﺎﻡ‪ .‬ﻭﺗﻤﺖ ﺩﺭﺍﺳﺔ ﺟﻤﻴﻊ ﺍﻟﻈﺮﻭﻑ ﺍﻟﻤﻨﺎﺳﺒﺔ ﺍﻟﻤﺆﺛﺮﺓ ﻋﻠﻲ ﻋﻤﻠﻴﺘﻰ ﺍﻻﻧﺘﺎﺝ ﻭﺍﻻﻣﺘﺼﺎﺹ‪ ،‬ﻭﻗﺪ‬
‫ﺍﻅﻬﺮﺕ ﺍﻟﻨﺘﺎﺋﺞ ﺃﻥ ﺍﻟﺤﺎﻣﺾ ﺍﻟﻨﺎﺗﺞ ﻳﺤﺘﻮﻯ ﻋﻠﻰ ﺍﻗﻞ ﻛﻤﻴﺔ ﻣﻦ ﺍﻟﻤﻮﺍﺩ ﺍﻟﻌﻀﻮﻳﺔ ﻭﺍﻟﻌﻮﺍﻟﻖ )‪(۱۹۱٫۷‬‬
‫ﺟﺰء ﻓﻲ ﺍﻟﻤﻠﻴﻮﻥ ﻭﻧﺴﺒﺔ ﻗﻠﻴﻠﺔ ﻣﻦ ﺍﻟﻔﻠﻮﺭ)‪ ،(٪۰٫٥‬ﺑﺎﻹﺿﺎﻓﺔ ﺇﻟﻲ ﺇﻣﺘﺼﺎﺹ ﻣﺎ ﻳﻌﺎﺩﻝ ‪ % 85‬ﻣﻦ‬
‫ﺍﻟﻴﻮﺭﺍﻧﻴﻮﻡ ﻭ‪ ٪ ۹٤٫٦‬ﻣﻦ ﺍﻟﻔﻠﻮﺭ ﻭ‪ ٪۷۹‬ﻣﻦ ﺍﻟﻌﻨﺎﺻﺮ ﺍﻻﺭﺿﻴﺔ ﺍﻟﻨﺎﺩﺭﺓ ﺑﺈﺳﺘﺨﺪﺍﻡ ﻣﺴﺤﻮﻕ ﺍﻟﻌﻈﺎﻡ‬
‫ﻋﻨﺪ ﺍﻓﻀﻞ ﻭﺍﻧﺴﺐ ﺍﻟﻈﺮﻭﻑ‪.‬‬