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Valorization and potential uses of Phosphogypsum:

Overview and proposals

Amjad KALLEL and Takahiko OKURA

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Introduction

Phosphogypsum (PG) is a by-product of the


chemical reaction called the "wet process," in
which finely ground phosphate rock is dissolved
to form a monocalcium phosphate slurry. Sulfuric
acid is added to the slurry to produce phosphoric
acid (H3PO4) needed for fertilizer production and
a phosphogypsum (hydrated calcium sulfate) by-
product, according to the following reaction: Fig. 1: PG stack in Sfax city (covering an area
of more than 50 ha).
Ca10(PO4)6F2 + 10 H2SO4 + 20 H2O

As PG retains the basic chemical and physical
6 H3PO4 + 10 CaSO4,2H2O + 2 HF (1)
properties of the natural gypsum used to
For every tonne of phosphoric acid as P2O5 manufacture commercial products for the
produced using the wet process, from 4.5 to more agricultural, construction and chemical industries,
than 5.5 tonnes of phosphogypsum are generated, the synthetic gypsum can frequently be
depending on the quality of the phosphate rock. substituted for natural gypsum in many of these
The annually worldwide production of PG is manufacturing processes. Since the 70’s
possibly up to 100 Mtpy [1]. researches are multiplied seeking beneficial uses
of PG, however most of the practices were found
Tunisia is a leading country worldwide, as far as to be inappropriate because of environmental
natural phosphate and mineral fertilizers are legislation or because of economical feasibility.
concerned. Annual production of merchant
phosphate in 1999 reached 8 millions, where 85% In this “paper” we are reporting some of the past
of it is processed locally [2]. Sfax city, major and current uses of PG and we are also proposing
industrial and commercial city in the southern part some innovative approaches to be developed and
of Tunisia located at the north shore of the gulf of subject for research.
Gabes, has been form the early 50’s a main pole
for phosphate processing. By far one of the Characteristics of phosphogypsum

biggest issues facing this city today is the massive


Phosphogypsum is generated as a filter cake in
accumulation of PG piles which are unprotected
the "wet process" and is typically pumped in
as shown in Figure 1.
slurry form to large holding ponds (stack), where
the phosphogypsum particles are allowed to settle.
The resulting product is a moist gray, powdery

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material that is predominantly silt sized and has During the past few decades, researches were
little or no plasticity [3]. multiplied seeking different beneficial uses of PG.
The composition and characteristics of PG depend According to the literature [5,6,7], the most
upon the source of rock phosphate and vary a common uses reside from the fact of the valuable
little with the process for manufacturing chemical/physical characteristics of PG among
phosphoric acid as well as the age, location and which we recite the followings:
depth within the stack in which the gypsum is
placed. Agriculture and land uses
As a cheap product, PG can successfully
Physical properties substitute the use of natural gypsum for soil and
agricultural purposes when it is applied in
The raw PG of Sfax is a silt or silty-sand material appropriate quantities and doses according to the
with a median grain size of approximately 77 m. local climate, soil characteristics and the targeted
It is almost free of fine fraction (< 1 m) [4]. crop.
Other physical and engineering properties of PG It has been reported [7] that the PG can be used
are summarized in Table 1. for the followings:
Table 1: Typical physical and engineering  as an ameliorant for sodium-affected (sodic)
properties of PG [3]. soils which occur mainly in arid areas,
Property Value  as a source of the nutrients calcium (Ca) and
Specific Gravity 2.3 - 2.6 sulfur (S) required by all crops,
Dry Density 1470 - 1670 kg/m3
Optimum  as an ameliorant for the subsoil acidity
15 - 20%
Moisture syndrome,
Friction Angle 32°
Cohesion Values 125 kPa  as an ameliorant for crust and seal formation at
Permeability 1.3 E-4 - 2.1E-5 cm/sec
the soil surface.

Chemical properties Construction and building material


All the attempts concentrated on processes
PG exhibits acidic properties and consists utilizing phosphogypsum to produce cement,
primarily of calcium sulfate dihydrate with small
amounts of silica, usually as quartz, and unreacted
phosphate rock. Radionuclides, as well as minor (%) (ppm)
amounts of toxic metals and other impurities are CaO 30.6 Cl 450
also present, as shown in Table. 2. SO3 44.3 Cd 5-20
P2O5 1-1.5 Zn 50-100
Table 2: Chemical composition of PG [4] Fe2O3 0.05 Cu 5-18
Al2O3 0.11 Pb <5
SiO2 1.7 Cr 10-30
Past and current uses of PG MgO 0.02 V <5
Na2O 0.7 Ni 3-5

3 K2O 0.02 Mn 5-7


F 1.3 Ti 50-60
C Org. 0.037-0.77 Sr 1100
H2O (Cris.) 19.25 Th <2
wallboard, plaster products and building blocks or MSW in landfills. A laboratory and lysimeter
glass type ceramic materials [5]. scale research [13] proved the following benefits
Owing to its mechanical and engineering of such application for both landfills and PG:
properties, PG can also be used as a roadbase or  enhance the biological decomposition of
subbase material through stabilization with either municipal solid waste,
portland cement, fly ash or combinations of both  extend the life of the landfill site,
[8] or for use as an embankment material [9].  rapid improve and decrease of leachate quality
and quantity,
Chemical processing  reduce the accumulation of PG as it is being
The majority of chemical processing dealt with used,
some type of thermal decomposition yielding  reduce of the cover material remaining in the
CaS, H2S, SO2 or elemental sulfur as the main landfill site.
product. However this research remains uncompleted as
As example, we mention the Merseberg Process the full-scale field study couldn’t be achieved due
[10] which consists of the conversion of PG to the to the EPA regulations in the USA.
two end products (calcium carbonate and
ammonium sulfate) according to the following Innovative proposals for PG use
reaction:
The above mentioned solutions for the PG use,
CaSO4, 2H2O + (NH2)2CO3 couldn’t be largely commercialized. In fact when
 the direct use of PG is proposed such as for
(NH4)2S04 + CaCO3 + 2H2O (2) agriculture, either the abundance of natural
gypsum or the environmental regulations was
The disadvantage of these processes is the intense faced. And when refining, purification and
energy requirement, which is not economically processing were proposed, the high energy cost
feasible due to high fuel costs. However, this can was a major constraint.
be mitigated with the use of alternate sources of
energy. In this section we are presenting some innovative
proposals for PG in which we will be trying to
Other uses mitigate the above mentioned problems,
Aquatic application: it consists mainly in the use especially the energy cost.
of PG for marine applications as artificial reefs
and colonizing substrate for oyster culch [11,12]. Leaching
In order to investigate on the leachibility potential
Landfill application: as PG is a sulfate enriched and characterization of the raw material, batch
material, it is reasonable to assume that it can be leaching experiments will be carried out.
used as an oxygen source for sulfate-reducing Different solutions will be used such as H2SO4,
bacteria, thus it will enhance the decomposition of

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HCl, NaOH, H2O2 and ferric solution. The preliminary thermodynamics calculations, it has
analyses concern the leached elements and the been found that CaS and CaO can be produced by
effect of leaching on the residue. Parameters such a thermal reduction of gypsum (CaSO4) with
as the leaching time, temperature, solution plastics (polyethylene, CH2) as shown in Figure 2.
concentration and the liquid/solid ratio will be 4 1 1
CaSO4  CH 2  CaCO3  H 2 S  H 2O  CO2
investigated. 3 3 3
(4)
Mechano-chemical activation
1 1 1
The mechano-chemical process consists on a ball
CaSO4  CH 2  CaO  SO2  H 2 O  CO2
3 3 3
mill grinding which permit a partial dehydration, (5)
an increase of the specific surface and an
4 4 4
alteration of the bonded element with host crystal.
CaSO4  CH 2  CaS  H 2O  CO2
3 3 3
Todorovsky et al. [14] had conducted preliminary (6) The combustion of polyethylene (PE) will
studies for the influence of the mechano- supply the heat necessary for the reaction to occur
activation on the overall solubility of PG in water so that CaS will be formed at a temperature
and diluted acids as well as on the leaching of rare around 800 C and CaO will be formed at a
earths from PG.
1.0
Zhang et al. [15] had investigated on a mechano- CaO
SO2
Equilibrated species / mol

chemical sulfidization and flotation in the 0.8

CaSO4
presence of iron in order to recover the nonferrous
0.6
metals or to remove heavy metals from their
contaminated wastes according to the following 0.4 CaCO3, H2S
H2O, CO2
reaction:
0.2 CaS
4MO + 4S +3Fe 4MS + Fe3O4 (M = zn, Pb,
Cd, Cu) (3) In our approach we CO
0.0
600 700 800 900 1000 1100 1200 1300 1400 1500
will be investigating on the same aspects, Temp. / K

however wastes (incineration ash, slag, etc.) will temperature around 1400 C.
be used as the metal source and PG will be used
as a sulfur source.

Thermal processing of PG with plastic waste


Ueda et al. [16] proposed an experimental
approach for reducing the gypsum waste of
construction material with plastic wastes.
Fig. 2: Equilibrated species formed from CH2:
According to the following reactions and
CaSO4 =1: 3 mixture [16].

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Fig. 3: Thermal processing of PG with plastic waste.

6
We will be following regarding the massive http://www. Evaluation of
the same approach amount of stocked giiexpress.com/pr potential
with PG as gypsum PG, the efforts have to oducts/ros18601; commercial
waste as showed in be multiplied to purify internet; accessed processed for the
Figure 3. or convert it into February 2006. production of
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conditions such as and commercially industry in phosphogypsum.
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ratio, atmosphere and The thermal from 002-018 of Florida
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