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Merseburg
Merseburg
DOI 10.1007/s10098-016-1157-4
ORIGINAL PAPER
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X. Msila et al.
Ca10 PO4 6 F2 10H2 SO4 20H2 O nickel (Ni) (Dawson et al. 1996; Mar and Okazaki 2012;
! 10CaSO4 2H2 O + 6H3 PO4 2HF: 1 Meck et al. 2011). Phosphogypsum as the by-product of
apatite ore digestion contains some of these impurities
Every tonne of phosphoric acid produced generates 1.7 (Rajkovic and Toskovic 2002). Since ammonium sulphate
tonnes of gypsum or specifically phosphogypsum as a by- is used in fertilisers (Liske et al. 2001; Robinson 1953) and
product. Approximately, 500 kilotonnes of phosphogyp- chemical fertilisers are known to contribute heavy metals
sum is produced annually from the phosphoric acid pro- into the soils they are applied to (Atafar et al. 2010; Savci
duction plant in the Lowveld of South Africa. 2012). High concentration of heavy metals in agricultural
soil results in high concentrations in food grown in such
Ammonium sulphate and precipitated calcium soil (Orisakwe et al. 2012). For these reasons, the fate of
carbonate production the heavy metal impurities during the conversion of
phosphogypsum to ammonium sulphate must be
There are two known processes of producing ammonium understood.
sulphate: (a) the direct reaction of ammonia, ammonia
solution or ammonia containing gas with sulphuric acid (b)
the gypsum process where calcium sulphate is reacted with PCC
ammonium carbonate (Robinson 1953) solution to form
ammonium sulphate and the precipitated calcium carbonate PCC is a multi-functional mineral filler extensively used in
(PCC). The later process also known as the Merseburg pro- paper, paint, plastics, cosmetics, food, rubber, pharma-
cess was originally developed in Germany and was used in ceutical and textile industries (Liske et al. 2001;
Austria, India, Pakistan and the UK (Alienov 1998; Kontrec Unkrainczyk et al. 2007). Paper made from PCC as a filler
et al. 2011). The Merseburg process is described by Eq. 2. has better optical qualities as measured by brightness,
whiteness, yellowness and opacity and better physical
CaSO4 2H2 O CO2 2NH4 OH
qualities as measured by breaking length, tear index and
! CaCO3 NH4 2 SO4 3H2 O: 2
burst index, than that produced with ground calcium car-
Stoichiometrically, for every 1.0 tonne of ammonium bonate as a filler (Tutus et al. 2013). The particle size and
sulphate produced, 0.9 tonnes of PCC is also produced and shape affects both the rheology (Michel-Sanchez 2005) and
1.6 tonnes of gypsum and 0.4 tonnes CO2 are consumed. the optical properties (Tutus et al. 2013) of PCC-based
South Africa has an opportunity to sequestrate up to 0.2 % coating. Amaya et al. (2011) showed that the particle size
of its CO2 emission and 100 % of its phosphogypsum and crystal morphology of pigments used as either filler or
generation through the Merseburg. Chou et al. (1995) are in coating can have significant effect on optical perfor-
the latest to evaluate the Merseburg process on pilot scale mance of paper. In turn, the size and shape of solution
and the concluded that the process is technically feasible grown crystals are influenced by amongst other parameters:
for flue gas desulfurization gypsum. In a follow up study, the degree of supersaturation, concentration and the type of
Chou et al. (1996) concluded that the Merseburg process impurities in solution and the pH of the solution (Kubota
was also economically viable, although the crystal size of et al. 2000; Loffelmann and Mersmann 2002; Vedantham
ammonium sulphate produced was in the range 1.23.3 2004).The worldwide consumption of PCC has been
mm. They also estimated that a compaction unit to produce reported by de Beers (2014) to be 74 mega tonnes in 2011.
granules of ammonium sulphate as usually required by the The crystal morphology of PCC produced from a
fertiliser industry would make the process uneconomical. Merseburg process has not been reported before. The
In this study, we carried out a bench scale technical fea- polymorphs of calcium carbonate are vaterite, aragonite
sibility of the Merseburg process modified by omitting the and calcite (Vedantham 2004). Vaterite is the least ther-
CO2 scrubbing towers in an attempt to reduce the capital modynamically stable form with hexagonal crystals and is
layout. In this modified process, the ammonium carbonate rarely seen in naturally occurring minerals (Piskin and
is formed directly in the gypsum conversion reactor. The Ozdemir 2012). Aragonite is the metastable form that
modified process products ammonium sulphate and PCC belongs to orthorhombicbipyramidal, space groupPm-
were also characterised with regards to metal impurities cnn (de Villiers 1971; Jarosch and Heger 1986; Kostov and
and the crystal morphology, respectively. Kostov 2006; Skinner et al. 1994). It slowly degrades to
calcite. Calcite belongs to the trigonalrhombohedral,
Impurities in ammonium sulphate space groupR3c (Skinner et al. 1994). It is the most
important of the three polymorphs in industrial applications
The apatite ore is a host to heavy metals impurities such as (Reksten 1990; Scheetz and White 1977; Smyth 1997).
cadmium (Cd), lead (Pb), arsenic (As), mercury (Hg) and According to Kontrec et al. (2011), calcite appears in
123
Capture and storage of CO2 into waste phosphogypsum
various crystal forms: scalenohedral, rhombohedral, sphe- Table 2 The main ICP-OES conditions for measurement of metals in
riohedral, etc., but the scalenohedral is favoured in most phosphogypsum
industrial applications. Nebulizer Glass concentric
Spray chamber Glass cyclonic
Nebulizer gas flow (dm3 min-1) 0.7
Experimental Power (W) 1150
3 -1
Plasma gas flow (dm min ) 12
Ammonium hydroxide solution (17 %) was prepared by Auxiliary gas flow (dm3 min-1) 0.5
diluting a commercial 30 % solution. The reactions were
carried out at atmospheric pressure in a bench scale
0.5 dm3 reactors fitted with a mechanical stirrer and a Table 3 The NICOMP AccuSizer 780 settings
thermo-couple, connected to water bath circulation for
Detection method Light extinction
temperature control. The variables in the experiments
Stirring rate (r.p.m.) 1500
carried out are shown in Table 1.
Diluent flow rate (cm3 min-1) 60
The measurements in Runs #13 were taken every 5 min
Calculation range (lm) 1.5500
for 60 min. Run #4 was sampled after 0, 2, 3, 4, 5 and 7 h.
The samples were filtered through a Whatman filter paper
and the solids were washed with water. The filtrate from the Table 4 Bruker Raman spec-
Wavelength (nm) 532
7 h reaction was acidified with 0.1 N sulphuric acid to pH 3.0 trometer settings
Power (mV) 10
before the reactor was heated to 368 K for the concentration Scan time (s) 15
for the precipitation of ammonium sulphate. The ammonium
sulphate was filtered through the Whatman filter paper. The
solid contents samples and the recovered ammonium sul- by omitting the CO2 scrubber. This section reports on the
phate were dried in an oven at 373 K. Samples of the solid effect of the modification on the reactor temperature and
contents, phosphogypsum were dissolved using nitric acid the pH. The process products are characterised against their
and the ammonium sulphate was dissolved in water. The potential use.
solutions were analysed by ICP-OES in the general condi-
tions shown in Table 2. Temperature in the gypsum conversion reactor
The PCC was analysed by (a) a NICOMPs AccuSizer
780 (dynamic light scattering combined with zeta potential Figure 1 shows temperature increase (DT) in the reactor
technique) for particle side distribution (PSD) under the due to the ammonium carbonate formation during the
conditions given in Table 3 and (b) a Raman spectrometer reaction of NH4OH and CO2. This temperature profile is
equipped with charge coupled device detector under the the reflection of the ammonium carbonate scrubbing tower
experimental conditions in Table 4. (c) SEM (mag. = 9 in the original Merseburg process. The ammonium car-
5000, EHT = 3.00 kV and WD 5.5 mm). bonate formation is an exothermic reaction, DH =
-674 kJ mol-1. The DT for ammonium carbonate forma-
tion was compared with the DT when either gypsum or
Results and discussion anhydrite was added during the ammonium carbonate
formation. This temperature profile is the reflection of the
The Merseburg has been previously proven to be techni- ammonium carbonate in the gypsum convertor in the
cally feasible. The purpose of this study was to evaluate the modified Merseburg process. The error bars in the
technical feasibility after the original process was modified chart indicates the standard deviation (r) of triplicate
Table 1 Experimental
Run #1 Run #2 Run #3 Run #4
conditions and materials for
Merseburg process Phosphogypsum 0 0 80 80
Anhydrite 0 63 0 0
NH4OH 100 g (17 %)
CO2 flow rate l0 dm3 min-1 (excess)
Temperature No heating 343 K
Measurements T and pH T, pH, % gypsum conversion
123
X. Msila et al.
Ammonium sulphate precipitation There are five Raman peaks and eight IR predicted active
vibration modes for calcite as defined by the irreducible
The pH in the gypsum conversion reactor was monitored representation in Eq. 3:
over the 7 h of reaction as the solids in the reactor changed
from phosphogypsum to mainly PCC. The results are
shown in Fig. 2. The error bars depicts a standard deviation
(r) of triplicate measurements. The pH of the mother liquor
dropped from 12 to about 8.
The conversion of gypsum was calculated to be 95 %
after 7 h of reaction. The optimal design of the gypsum
convertor may result in less ammonia gas loses and more
conversion efficiencies such as the 98 % reported by Chou
et al. (1995). The consumption of all phosphogypsum
waste produced annually in the Lowveld, South Africa
would reduce the CO2 emission by 0.2 %.
The pH of 8 is not suitable for the precipitation of
ammonium sulphate and therefore after the separation of
the PCC the mother liquor was acidified with a weak
H2SO4 solution to a pH of 3.5 and the temperature of the
reactor contents was increased to 353 K. Fig. 3 PSD of the Merseburg PCC
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Capture and storage of CO2 into waste phosphogypsum
Cvib AR1g 2Ainactive 3Ainactive 3AIR R IR The Raman spectrum of the PCC formed in the modified
1u 2g 2u 4Eg 5Eu :
Merseburg process is shown in Fig. 4.
3
The following Raman active bands are observed: 281,
There are 30 predicted Raman active modes for arago- 713, 1086 and 1473 cm-1 m3CO3. These Raman active
nite as defined by the irreducible representation in Eq. 4: bands for the stable polymorphs of CaCO3 are reported in
literature (Suito et al. 2001) at: C290 cm-1 or A207 cm-1
Cvib 9AR1g 6Ainactive 6BR1g 8BIR R
1u 9B2g
u
4 m4CO3, C714 cm-1 and C715 cm-1 or A704 cm-1 m4CO3,
5BIR R IR
2u 6B3g 8B3u :
C
1088 cm-1 and C1092 cm-1 m1CO3 and C1415 cm-1 or
A
1462 cm-1 m3CO3, where the superscripts A and C indi-
cate aragonite and calcite, respectively. These results
confirm that the CaCO3 produced in the modified Merse-
burg process is calcite as clearly distinguished by the
Raman band at 281 cm-1. A non-fundamental shift is
observed at 1751 cm-1.
Conclusions
123
X. Msila et al.
production of granular ammonium sulphate. This study has Jarosch D, Heger G (1986) Neutron diffraction refinement of the
demonstrated that 95 % conversion efficiency of the crystal structure of Aragonite. Mineral Petrogr Mitt 35:127131
Jung WM, Kang SH, Kim W, Choi CK (2000) Particle morphology of
phosphogypsum from the Lowveld of South Africa is calcium carbonate precipitated by gasliquid reaction in a
technically feasible in the modified Merseburg process. CouetteTaylor reactor. Chem Eng Sci 55:733747
The efficiencies may be improved by minimising the Kanniche M, Gros-Bonnivard R, Jaud P, Valle-Marcos J, Amann J-M,
ammonia gas loses in the gypsum conversion reactor. The Bouallou C (2010) Pre-combustion, post-combustion and oxy-
combustion in thermal power plant for CO2 capture. Appl Therm
ammonium sulphate produced is comparable in metal Eng 30:5362
impurities to the commercially available grades. The PCC Kontrec J, Ukrainczyk M, Babic-Ivancic V, Kralj D (2011) Synthesis
produced is the industrially preferred calcitic scalenohedral of calcium carbonate by semi-continuous carbonation method in
polymorph with average diameter of 3.4 lm. These are the presence of dextrans. Croat Chem Acta 84(1):2532
Kostov I, Kostov RI (2006) Systematics and crystal genesis of
important results in the quest for technologies for carbon carbonate minerals. Geol Geophys 49(1):111118
capture and storage in South Africa and the world. KPMG (2010) Carbon disclosure project. http://www.cdproject.net.
Accessed 1 March 2016
Kubota N, Yokota M, Mullin JW (2000) Combined influence of
supersaturation and impurity concentration on crystal growth.
References J Cryst Growth 212:480488
Li Y, Markley B, Mohan AR, Rodriguez-Santiago V, Thompson D,
Abidin V, Bouallou C, Clodic D (2011) Valorization of CO2 Niekerk DV (2006) Utilization of carbon dioxide from coal-fired
emissions into ethanol by an innovative process. Chem Eng power plant for the production of value-added products. Penn
Trans 25:16 State College of Earth and Mineral Sciences. http://www.ems.
Alienov DP (1998) Fertilizer manual. Kluwer Academic Publishers, psu.edu/*elsworth/courses/egee580/Utilization_final_report.pdf.
Norwell Accessed 1 March 2016
Al-Jundi J, Al-Ahmad N, Shehadeh H, Afaneh F, Maghrabi M, Liske Y, Kapila S, Flanigan V, Nam P, Lorbert S (2001) Production
Gerstmann U (2008) Investigation on the activity concentrations of feedstock chemicals from ammonium sulfate and ammonium
of 238U, 226Ra, 228Ra, 210Pb and 40K in Jordan phosphogypsum bisulfate. J Hazard Subst Res 2:811
and fertilizers. Radiat Prot Dosim 131(4):449454 Loffelmann M, Mersmann A (2002) Prediction of crystallization
Amaya JJ, Doelle K, Mahmud S (2011) A comparative study of coefficients of the population balance. Chem Eng Sci
different fillers on uncoated eucalyptus digital printing paper 57:43014310
properties: a pilot scale approach. Paper Con., p 2941. http:// Mar SS, Okazaki M (2012) Investigation of Cd contents in several
www.tappi.org/content/events/11papercon/documents/Mahmud% phosphate rocks used for the production of fertilizer. Microchem
20pptA.pdf. Accessed 1 March 2016 J 104:1721
Atafar Z, Mesdaghinia A, Nouri J, Homaee M, Yunesian M, Meck ML, Althopeng J, Masamba WRL, Ringrose S, Diskin S (2011)
Ahmadimoghaddam M, Mahvi AH (2010) Effect of fertilizer Minerals that host metals at Dorowa Rock Phosphate Mine,
application on soil heavy metal concentration. Environ Monit Zimbabwe. Open Mineral J 4:2028
Assess 160:8389 Mendes L, de Menderios JL, Alves RMB, Araujo OQF (2014)
Boden TA, Marland G, Andres RJ (2011) Global, regional, and Production of methanol and organic carbonates for chemical
national fossil-fuel CO2 emissions. Carbon Dioxide Information sequestration of CO2 from an NGCC Power Plant. Clean
Analysis Center, Oak Ridge National Laboratory, U.S. Depart- Technol Environ Policy 16:10951105. doi:10.1007/s10098-
ment of Energy, Oak Ridge. doi:10.3334/CDIAC/00001_V2011 014-0712-0
Boden TA, Marland G, Andres RJ (2015) Global, regional, and Michel-Sanchez E (2005) Impact of particle morphology on the
national fossil-fuel CO2 emissions. Carbon Dioxide Information rheology of PCC-based coating. Thesis, Georgia Institute of
Analysis Center, Oak Ridge National Laboratory, U.S. Depart- Technology
ment of Energy, Oak Ridge. doi:10.3334/CDIAC/00001_V2015 Orisakwe OE, Nduka JK, Amadi CN, Dike DO, Bede O (2012) Heavy
Chou MIM, Bruinius JA, Li YC, Rostam-Abadi M, Lytle JM (1995) metals health risk assessment for population via consumption of
Manufacture of ammonium sulfate fertilizer from FGD-gypsum. food crops and fruits in Owerri, South Eastern, Nigeria. Chem
American Chemical Society Fuel Chem Div., Chicago. http:// Cent J 6:7784
web.anl.gov/PCS/acsfuel/files. Accessed 20 Feb 2016 Pereira F, Bilal E (2012) Phosphoric acid extraction and rare earth
Chou MIM, Rosam-Abadi M, Lytle JM (1996) Manufacture of recovery from apatites of the Brazilian phosphatic ore. Rom J
ammonium sulfate fertilizer from gypsum-rich by-product of flue Miner Depos 85(2):4952
gas desulfurisationa prefeasibility cost estimate. https://web. Piskin S, Ozdemir OD (2012) Effect of process conditions on crystal
anl.gov/PCS/acsfuel/preprint%20archive/Files/41_2_NEW%20OR structure of precipitated calcium carbonate (CaCO3) from fly
LEANS_03-96_0579.pdf. Accessed 30 Nov 2015 ash: Na2CO3 preparation conditions. IJBEES 1(6):192195
Dawson JB, Steele IM, Smith JV, Rivers ML (1996) Minor and trace Rajkovic MB, Toskovic DV (2002) Determination of inorganic
element chemistry of carbonates, apatites and magnetites in compounds in drinking water on the basis of household water
some African carbonatites. Mineral Mag 60:415425 heater scale. APTEFF 33:7192
De Beers (2014) The production of precipitated calcium carbonate Reksten K (1990) Superstructures in calcite. Am Mineral 75:807812
from industrial gypsum wastes. Thesis, University of the North Robinson P (1953) US Patent 2631084A
West Savci S (2012) An agricultural pollutant chemical fertilizer. Int J
De Villiers JPR (1971) Crystal structures of aragonite, strontianite, Environ Sci Technol 3(1):7780
and witherite. Am Mineral 56:758767 Scheetz BE, White B (1977) Vibrational spectra of the alkaline earth
IHS, Chemical Economic Handbook, China report. https://www.ihs. double carbonates. Am Mineral 62:3650
com/products/phosphoric-acid-chemical-economics-handbook. Skinner AJ, LaFemina JP, Jansen HJF (1994) Structure and bonding
html. Accessed 30 Jan 2016 of calcite, a theoretical study. Am Mineral 79:205214
123
Capture and storage of CO2 into waste phosphogypsum
Smyth JR (1997) The crystal structure of calcite III. Geophys Res Lett Unkrainczyk M, Kontrec J, Babic-Ivancic V, Brecevic L, Kralj D
24(13):15951598 (2007) Experimental design approach to calcium carbonate
Suito K, Namba J, Horikawa T, Taniguchi Y, Sakurai N, Kobayashi precipitation in a semi-continuous process. Powder Technol
M, Onodera A, Shimomura O, Kikegawa T (2001) Phase 171:192199
relations of CaCO3 at high pressure and high temperature. Am Vedantham K (2004) Effect of operating parameters on the growth
Mineral 86:9971002 rate of solution grown crystals. Thesis, Mississippi State
Tutus A, Cicekler M, Ozdemir A, Okan TO (2013) Effects of University
precipitated calcium carbonate (PCC) on optical properties of
waste paper. In: International Caucasian forestry symposium,
Artvin, Turkey, p 884887
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