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Recycling of Waste FGD Gypsum Recycling of Waste FGD Gypsum: Conference Paper
Recycling of Waste FGD Gypsum Recycling of Waste FGD Gypsum: Conference Paper
Recycling of Waste FGD Gypsum Recycling of Waste FGD Gypsum: Conference Paper
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V. Logar
University of Belgrade
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All content following this page was uploaded by Slobodanka Radomir Marinkovic on 16 July 2014.
University of Belgrade, Faculty of Mining and Geology, Djusina 7, 11000 Belgrade, Serbia and
Montenegro, Tel: (38111)3219-108, Fax: (38111)3235-539, timar@eunet.yu
Key words: recycling, FGD gypsum, sulphogypsum, β-calcium sulphate hemihydrate, construction
industry
FGD gypsum (sulphogypsum) is a principal residue from coal-fired power plant fitted with flue
gas desulphurization (FGD) equipment. This is the product of the reaction between SO2 in the flue
gases and limestone used to separate it from the flue gases.
FGD gypsum can be used to make a range of materials employed in the building works and
construction industry (floors screeds, plaster boards, gypsum blocks). Before FGD gypsum can be
used for that purpose, it must be converted into hemihydrate or anhydrite – binder products that
harden after water has been added.
In this study, the possibility of recycling FGD gypsum from lignite Bohemian power plant-
Hvaletice for obtaining β-calcium sulphate hemihydrate was investigated. There are many lignite
power plants in Serbia which have not an FGD system installed yet. Nevertheless, it will be
obligatory to install this system soon. Therefore, the results of these examinations would be a
contribution to the future solution of environmental and economic problems in connection with
waste FGD gypsum in Serbian power plants.
In order to obtain β-calcium sulphate hemihydrate (β-CaSO4⋅0.5H2O) three kinds of starting
materials were heated in a dryer at 130 oC: 1. raw FGD gypsum, 2. washed in water FGD gypsum
(to eliminate soluble in water impurities) and 3. treated in H2SO4 solution (to eliminate carbonates)
and than washed in water FGD gypsum. The three obtained products were investigated by
qualitative IR analysis. These results have shown that β-CaSO4⋅0.5H2O obtained from raw FGD
gypsum (product 1.) and washed in water FGD gypsum (product 2.) contained carbonates
(impurities), contrary to β-CaSO4⋅0.5H2O obtained from treated in acid solution FGD gypsum
(product 3.).
When three products (β-CaSO4⋅0.5H2O) were mixed with water at a standard Water/Powder
ratio (W/P of 0.8), pastes, that got hardened by storage, were formed. The compressive strength of
the hardened samples was measured 7 days after and their composition was determined by
qualitative IR analysis. The experimental results show that β-calcium sulphate hemihydrate (β-
CaSO4⋅0.5H2O) completely recrystallize to dihydrate (CaSO4⋅2H2O) in all the hardened samples
and that all the hardened samples are sufficiently resistant to compression for usage in the building,
sculpturing and modeling. Because of the unsuitable color (light – gray), the presence of impurities
and the lowest compressive strength value (2.58 MPa) β -hemihydrate from raw FGD gypsum
could have very limited application. Contrary, β -hemihydrates from previous prepared FGD
gypsum (washed in water-product 2., as well as treated in acid solution and than washed in water
FGD gypsum-product 3.) could have a great practical application, because of their white color, the
amount of impurities (small amount only in product 2) and the great compressive strength (4.33 and
7,79 MPa of products 2.and 3., respectively).
Therefore the best scheme for production of β-calcium sulphate hemihydrate from FGD gypsum
is:
raw FGD gypsum → treating in 0.05 M H2SO4 → filtration → washing in water →
filtration→ heating in drier,
054–1
32nd International Conference of SSCHE
May 23–27, 2005, Tatranské Matliare, Slovakia Po-We-4, 054p.pdf
University of Belgrade, Faculty of Mining and Geology, Djusina 7, 11000 Belgrade, Serbia and
Montenegro, Tel: (38111)3219-108, Fax: (38111)3235-539, timar@eunet.yu
Key words: recycling, FGD gypsum, sulphogypsum, β-calcium sulphate hemihydrate, construction
industry
INTRODUCTION
The burning of coal in electric power plants produces sulphur dioxide (SO2) gas emission. The
1990 Clain Air Act Amendments (in U. S. A) and the regulations in the European Union (the low
No.218/1992 in Czech Republic, for example) mandated the reduction of power plant SO2 emission
by so called flue gas desulphurization (FGD) processes (1, 2). These processes are based on SO2
absorption by an alkaline sorbent consisting of lime or limestone. The final consequence of the use
of FGD processes is the formation of large quantities of FGD gypsum (sulphogypsum) – waste
material.
For economic and environmental reasons, it is always preferable to utilize a waste rather than
dispose of it. The utilization of waste gypsum as raw material for production of commercial binders
(hemihydrate and anhydrite), as well as other new binders (fly ash-lime-gypsum binders, for
example) has been considered widely (3-9). These binders harden after water has been added and
have application in the building works and in construction industry for the production of
prefabricated products (floor screeds, plaster boards, blocks, bricks). The construction (building)
uses large tonnages of hemihydrate plaster and anhydrite, that is outlet for large quantities of FGD
gypsum.
The acceptability of FGD gypsum for the industrial reutilization depends of its characteristics,
primary of the presence of the impurities in it. The impurities may be constituted by the coal ash
(which negatively influence the colour), by the impure substances found in the limestone or lime at
origin, by the non oxidized calcium sulphite and by mineral salts (principally chlorides) deriving
from the burnt coal. It is necessary to keep the coal ash quantities in the FGD gypsum under control
as these can alter the gradation of white in the manufactures. Also, the chloride contents must be
controlled as these may produce deterioration in the adhesion in the lining used in plasterboard
manufactures. The specification limits for the characteristics of FGD gypsum, according to the
Italian and German recommendations (3), are reported in Table 1.
Serbian plants (mainly lignite power plants) have not a FGD system installed yet, but it will be
obligatory to install this system soon. This will generate great amounts of waste FGD gypsum. The
aim of this work was to investigate the possibility of recycling FGD gypsum. The results of these
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32nd International Conference of SSCHE
May 23–27, 2005, Tatranské Matliare, Slovakia Po-We-4, 054p.pdf
EXPERIMENTAL
FGD gypsum from lignite Bohemian power plant-Hvaletice-Czech (no Serbian plants have a
FGD system installed yet) was used in this study. This material was examined in order to determine
its chemical composition and some physical properties. The chemical composition of FGD gypsum
was determined by quantitative chemical analysis (Table 2). Also, it was subjected to qualitative IR
analysis in the range from 4000 to 400 cm-1(Table.3). The IR spectrum was recorded on a Perkin
Elmer Spectrophotometer 782 using the pressed KBr technique (the same spectrophotometer and
the same technique were also used to record all the other IR spectra in this study). The physical
properties of FGD gypsum: density by pycnometer and granulometric composition by wet sieving
through Tyler sieves were determined (Table 4).
On the basis of the results of the chemical analysis of FGD gypsum (Table 2) it is apparent that it
is essentially a pure substance (about 5 % of impurities).
The IR spectrum of FGD gypsum (Table 3) contains the absorption bands (3560, 3420, 1680,
1625, 1160, 1120, 670 and 600 cm-1), which are characteristic for CaSO4·2H2O, i.e. gypsum (11,
12). Beside these bands, the IR spectrum contains weak band at 1450 cm-1, which confirms the
presence of some carbonates in FGD gypsum (13). This result is in accordance with the chemical
analysis of FGD gypsum (1,16 % CO2, Table 2).
054–3
32nd International Conference of SSCHE
May 23–27, 2005, Tatranské Matliare, Slovakia Po-We-4, 054p.pdf
The results of the granulometric composition determination (Table 4) show that FGD gypsum
has a suitable particle size distribution, because the smallest fraction (particle size smaller than
0.074 mm, e.g. 74 µm) is the major fraction in it (96.66 %). Consequently, it could be used without
preliminary grinding, for β-calcium sulphate hemihydrate production.
Because of the unsuitable colour (light – gray, Table 4) and greater contents of carbonates and
Cl – (compare Table 2 and Table 1) it is evident that FGD gypsum from Bohemian power plant-
Hvaletice-Czech is not suitable for direct use in construction industry. To purify FGD gypsum,
before its heating and transformation into β-hemihydrate, this material is washed in water (to
remove any traces of Cl – ions an to attain white colour of material) and treated in 0,05M solution of
H2SO4 (to eliminate carbonates). Also, raw FGD gypsum (unwashed and untreated in 0,05M
solution of H2SO4) is heated and transformed into β-calcium sulphate hemihydrate and such
obtained product (β-CaSO4⋅0.5H2O) is compared with those obtained from purified FGD gypsum.
Three ways of β-CaSO4⋅0.5H2O obtaining, used in this study, are shown by following schemes:
Raw FGD gypsum , FGD gypsum washed in water and FGD gypsum treated in H2SO4 and than
washed in water were heated in a drier at 130 oC and. the dehydration was monitored by qualitative
IR analysis in order to confirm the complete transformation of CaSO4⋅2H2O into β-CaSO4⋅0.5H2O.
The disappearance of bands corresponding to gypsum crystallization water (at 3420 and 1680 cm-1)
and the appearance of bands characteristic for hemihydrate (at about 3615 and 1005 cm-1) in IR
spectra of gypsum heated products indicated that the transformation occurred.
In order to investigate the resistance to compression of the products, standard pastes were
prepared by mixing β-calcium sulphate hemihydrate (obtained by three mentioned ways) with
water at a W/P ratio (water volume/mass of β-CaSO4⋅0.5H2O power) of 0.8 cm3/g. The compressive
strength of the hardened standard pastes was tested after 7 days. The preparation of standard pastes
and the testing of hardened standard pastes were carried out by procedures reported in the literature
(14) (in accordance with Yugoslav Standard requirements). The compressive strength determined
for hardened standard pastes was compared with those which are required for different kinds of
gypsum according to Yugoslav standard (14) (Table 5.).
Table 5. Required compressive strength for different kinds of gypsum according to Yugoslav
Standard
The stucco gypsum has application in building, alabaster gypsum in building and sculpturing and
modeling gypsum for manufacture of different models.
Finally, all the hardened pastes were pulverized after 7 days and examined by qualitative IR
analysis for their chemical composition.
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32nd International Conference of SSCHE
May 23–27, 2005, Tatranské Matliare, Slovakia Po-We-4, 054p.pdf
The results of IR analysis of the products obtained on the mentioned three different ways are
presented in Table 6.
. In the IR spectrum of product 3. (from FGD gypsum treated in acid solution and than washed in
water) all the present bands are characteristic for calcium sulphate hemihydrate (CaSO4⋅0.5H2O),
according to literature (11,12). Beside the bands which are characteristic of CaSO4⋅0.5H2O, in the
IR spectra of product 2 (from FGD gypsum only washed in water) and product 1 (from raw FGD
gypsum) there are small bands at 1440 cm-1which confirmed that carbonates (the impurities in raw
FGD gypsum) did not disappear during FGD gypsum heating at 130 oC.
The compressive test results and colour for samples prepared with hemihydrate (product 1, 2 and
3.) and water, using the standard W/S ratio of 0.8 (after 7 days) are given in Table 7.
Table 7. Compressive strength and colour of hardened hemihydrate samples prepared using the
standard ratio (W/S = 0.8)
The results in Table 7 show that all three samples have compressive strength values higher than
the lowest value according to the Yugoslav Standard (Table 5) necessary for application in the
construction industry, sculpturing and modeling (14).
A comparison of the compressive strength of the samples (Table 7) indicted that the sample
prepared with hemihydrate from raw FGD gypsum was less resistant than those prepared with
hemihydrate from washed in water FGD gypsum (by 40.4 %) and with hemihydrate prepared from
treated in acid solution and washed in water FGD gypsum (by 66.9 %).
A comparison of the compressive strength of the samples 2 and 3 (Table 7) indicted that the
sample prepared with hemihydrate from washed in water FGD gypsum was less resistant than that
prepared with hemihydrate from treated in acid solution and washed in water FGD gypsum (by
44.4%).
Also, it is evident (Table 7) that washing of FGD gypsum in water is necessary to attain the
white colour of products.
The results of IR analysis of hardened samples (powdered after 7 days) are presented in Table 8.
054–5
32nd International Conference of SSCHE
May 23–27, 2005, Tatranské Matliare, Slovakia Po-We-4, 054p.pdf
CONCLUSION
The present study has shown that FGD gypsum, formed by flue gas desulphurozation (FGD)
process in power plant, can be used as raw material for β-calcium sulphate hemihydrate production.
When raw FGD gypsum is used, without any previous preparation, the obtained product
(β-CaSO4⋅0.5H2O) is suitable regarding the compressive strength, but not applicable (or low
applicable) because of its colour (light – gray) and the presence of impurities (chloride, carbonates).
The product (β-CaSO4⋅0.5H2O) from washed in water FGD gypsum is very satisfactory
regarding the compressive strength and colour (white). Small amount of carbonates in this material
should not disturb its application.
Finally, when FGD gypsum is treated with 0.05 M H2SO4 solution (in other to eliminate
carbonates) and washed in water (to eliminate soluble in water impurities), the obtained β-calcium
sulphate hemihydrate has the best quality (the highest compressive strength, white colour).
Therefore, the very best scheme for recycling waste FGD gypsum into β-calcium sulphate
nemihydrate is:
raw FGD gypsum → treating in 0.05 M H2SO4 → filtration → washing in water →
filtration→ heating in drier,
but it requires the highest cost.
REFERENCES
054–6
32nd International Conference of SSCHE
May 23–27, 2005, Tatranské Matliare, Slovakia Po-We-4, 054p.pdf
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